Shock resistant polyurethane and poly(ureaurethane) articles and production method thereof

FIELD: chemistry.

SUBSTANCE: polyurethane material contains a first part of crystalline particles, having self-orientation and bonded so as to keep their orientation along a first crystallographic line at least in two directions, a second part of crystalline particles having self-orientation and bonded so as to keep their orientation along a second crystallographic line at least in two directions, wherein the first crystallographic line is different from the second crystallographic line and where the said crystalline particles constitute more than approximately 30% of the total volume of the polyurethane material, and where the polyurethane contains a product of reaction of components comprising: (a) approximately 1 equivalent of 4,4'-methylene-bis(cyclohexylisocyanate); (b) approximately 0.3 of a trimethylolpropane equivalent; and (c) approximately 0.7 of a butanediol or pentanediol equivalent, and where the polyurethane material undergoes thermal treatment at temperature ranging from approximately 35°C to approximately 150°C or holding.

EFFECT: production of polyurethane material, products of which are made through casting or reaction injection moulding and have good optical properties, high resistance to impact loads, high impact resistance, high K-ratio, good ballistic stability, good resistance to solvents and good weather resistance.

26 cl, 110 ex, 33 tbl, 26 dwg

 

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a partial continuation of the patent application in the United States, reg. No. 10/932641 aimed for review September 1, 2004, and patent applications in the United States, reg. No. 11/303670, 11/303422, 11/303892, 11/303671 and 11/303832, which were submitted on December 16, 2005, Each of the above applications are incorporated by reference.

The LEVEL of TECHNOLOGY

I. technical FIELD

The present invention relates to polyurethanes and poly(motivirovana)derived from branched polyols, branched polyisocyanates and/or trimers of polyisocyanates, for products and coatings made from them, as well as to methods of their production.

II. TECHNICAL PROPOSAL

A number of organic polymeric materials, for example plastics such as polycarbonates and acrylic polymers, developed as alternatives and substitutes of glass for such applications as optical lenses, fiber optics, Windows and cars, marine and aviation transparent products. For example, when the glazing aircraft has been widely recognized as the polycarbonates, such as LEXAN®and acrylic polymers. Such polymeric materials can provide advantages relative to the glass, including resistance to breaking or ustoichivost is to be penetrated; lighter weight for this application, flexibility, easy formability and abrasivejet. Unfortunately, there are some serious disadvantages associated with polycarbonates, and acrylic polymers. Polycarbonates easily scratched and, if they are exposed to direct sunlight and harmful to the environment, it quickly becomes difficult to look through them. Acrylic polymers although not as prone to scratching as polycarbonates, do not have the physical properties of the polycarbonates, such as temperature deformation due to thermal heating and resistance to shock loads. Some "vysokozharoprochnyh" the polycarbonates can have a volatile impact strength, which can fall over time, poor resistance to crack propagation (K-factor K-factor), poor optics, poor resistance to solvents and poor resistance to weathering. Even if the polycarbonates can show good resistance to impact at impact at low speeds, at high impact velocities above approximately 1100 ft/sec (335,3 m/s), such as speed, shown in ballistics, 9 mm bullet (125 GP), released approximately 20 feet (6.1 m) at a speed of approximately 1350 ft/sec (411 m/sec), can easily pass through the polycarbonate layer is to a thickness of 1 inch (2.5 cm).

In addition, as a rule, polycarbonates ekstragiruyut that can give the optical distortions in the extrudate in the direction of extrusion. For optical applications, such as the canopy of the cockpit of the fighter, polycarbonates typically must undergo additional process steps to remove the distortion, which increases costs. In addition, some polycarbonates are birefringent, which can also cause optical distortion. For example, the Abbe number LEXAN 34. A higher value of the Abbe number indicates a better visual image sharpness and reduced chromatic aberration.

Therefore, in this technical field, there is a need to develop polymers that can be used for the production of articles having good optical properties, high impact resistance, high impact strength, high coefficient K, good ballistic resistance, good resistance to solvents and good resistance to weathering. Also is desirable ability to manufacture products by casting or reaction injection molding, instead of extrusion.

The ESSENCE of the INVENTION

The discussion of various aspects and embodiments of the polyurethanes and poly(macawesomeshow) of the present invention is grouped below. Although various aspects of the invention are organized into groups to discuss, this grouping is not intended to limit the scope of the present invention, and aspects of one of the groups may relate to the subject matter of other groups.

Group a

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes including a reaction product of components including:

(a) about 1 equivalent of at least one MDI;

(b) from about 0.05 to 0.9 equivalents of at least one branched polyol containing from 4 to 12 carbon atoms and at least 3 hydroxyl groups; and

(C) from about 0.1 to 0.95 equivalent of at least one diol containing from 2 to 18 carbon atoms;

where the reaction product components are essentially does not contain complex polyetherpolyols and simple polyetherpolyols and where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

In other non-limiting embodiments, the implementation of the present invention provides polyurethanes including a reaction product of components including:

(a) about 1 equivalent of 4,4'-methylene-bis-(cyclohexylsulfamate);

(b) from about 0.3 to 0.5 equiv of the tape trimethylolpropane; and

(C) from about 0.3 to 0.7 equivalent of 1,10-dodecanediol, butanediol or pentanediol;

where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

In some non-limiting embodiments implementing the present invention features a product consisting of polyurethane, vklyuchayuschego the reaction product of components including:

(a) about 1 equivalent of at least one MDI;

(b) from about 0.1 to 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(C) from about 0.1 to 0.9 equivalents of at least one diol containing from 2 to 12 carbon atoms;

where the reaction product components are essentially does not contain complex polyetherpolyols and simple polyetherpolyols and where the product has impact on Gardner, at least about 200 DM·lb (23 j) in accordance with ASTM-D 5420-04.

In some non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane comprising the stage of interaction in a process vessel components, including:

(a) about 1 equivalent of at least one on isocyanate;

(b) from about 0.1 to 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(C) from about 0.1 to 0.9 equivalents of at least one diol containing from 2 to 12 carbon atoms;

where the components are essentially not contain complex polyetherpolyols and simple polyetherpolyols and where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

In other non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane, which include stages:

(a) interaction of at least one MDI and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of polyurethane prepolymer, and

(b) interaction of polyurethane prepolymer at least one diola containing from 2 to 12 carbon atoms, with the formation of polyurethane,

where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

Group

In some non-limiting embodiments implementing the present invention prex is assumed polyurethanes, comprising the reaction product of components including:

(a) urethane prepolymer with isocyanate functionality, containing the reaction product of components including:

(i) about 1 equivalent of at least one MDI; and

(ii) from about 0.1 to 0.5 equivalent, of at least one diol containing from 2 to 18 carbon atoms, and

(b) from about 0.05 to 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(C) until about 0.45 equivalents of at least one diol containing from 2 to 18 carbon atoms,

where the reaction product components are essentially does not contain complex polyetherpolyols and simple polyetherpolyols.

Group

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes including a reaction product of components including:

(a) at least one polyisocyanate selected from the group comprising trimers MDI and branched polyisocyanates, the polyisocyanate has at least three isocyanate functional groups; and

(b) at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least two hydroxyl groups; and

where the product Rea is the component essentially does not contain complex polyetherpolyols and simple polyetherpolyols.

In other non-limiting embodiments, the implementation of the present invention provides polyurethanes including a reaction product of components including:

(a) about 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate);

(b) about 1.1 equivalents of butanediol; and

(C) about 0.1 equivalent of a trimer of isophorondiisocyanate.

In some non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane comprising the stage of interaction in a process vessel components, including:

(a) at least one trimer MDI or branched polyisocyanate, the polyisocyanate has at least three isocyanate functional groups; and

(b) at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least two hydroxyl groups; and

where the reaction product components are essentially does not contain complex polyetherpolyols and simple polyetherpolyols.

Group D

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes including a reaction product of components including:

(a) at least one polyisocyanate;

(b) at least one branched polyol containing from 4 to 18 carbon atoms and at least hydroxyine group; and

(C) at least one polyol containing one or more bromine atoms, one or more phosphorus atoms or combinations thereof.

In other non-limiting embodiments, the implementation of the present invention provides polyurethanes including a reaction product of components including:

(a) about 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate);

(b) from about 0.3 to 0.5 equivalents of trimethylolpropane;

(C) from about 0.2 to 0.5 equivalent of bis(4-(2-hydroxyethoxy)for 3,5-dibromophenyl)sulfone;

(d) from about 0.2 to 0.5 equivalent of 1,4-cyclohexanedimethanol; and

(e) from about 0.2 to 0.5 equivalent of 3.6-dithia-1,2-octanediol.

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes including a reaction product of components including:

(a) at least one polyisocyanate selected from the group comprising trimers MDI and branched polyisocyanates, the polyisocyanate has at least three isocyanate functional groups; and

(b) at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups; and

(C) at least one polyol containing one or more bromine atoms, one or more phosphorus atoms or combinations thereof.

<> In some non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane comprising the stage of interaction in a process vessel components, including:

(a) at least one polyisocyanate;

(b) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(C) at least one polyol containing one or more bromine atoms, one or more phosphorus atoms or combinations thereof.

In other non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane, which include stages:

(a) interaction of at least one MDI and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of polyurethane prepolymer, and

(b) interaction of polyurethane prepolymer at least one polyol containing one or more bromine atoms, one or more phosphorus atoms or combinations thereof, with the formation of polyurethane.

Group E

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes including a reaction product of components including:

(a) app is siteline 1 equivalent, at least one MDI;

(b) from about 0.3 to 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(C) from about 0.01 to 0.3 equivalent, of at least one polycarbonate diol;

where the reaction product components are essentially does not contain a simple polyetherpolyols and amine curing agent and where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

In other non-limiting embodiments, the implementation of the present invention provides polyurethanes including a reaction product of components including:

(a) about 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate);

(b) about 0.3 equivalents of trimethylolpropane;

(C) from about 0.5 to 0.55 equivalents of butanediol or pentanediol; and

(d) from about 0.15 to 0.2 equivalent of polyacyladipate diol;

where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

In some non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane comprising the stage of interaction in one the th technological capacity components, including:

(a) about 1 equivalent of at least one MDI;

(b) from about 0.3 to 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(C) from about 0.01 to 0.3 equivalent, of at least one polycarbonate diol;

where the reaction product components are essentially does not contain a simple polyetherpolyols and amine curing agent and where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

In other non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane, which include stages:

(a) interaction of at least one MDI and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of polyurethane prepolymer, and

(b) interaction of polyurethane prepolymer at least one polycarbonate diol with the formation of polyurethane.

Group F

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes including a reaction product of components including:

(a) p is blithedale 1 equivalent, at least one MDI;

(b) from about 0.3 to 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

(C) from about 0.01 to 0.3 equivalent, of at least one polycarbonate diol; and

(d) from about 0.1 to 0.9 equivalents of at least one diol containing from 2 to 18 carbon atoms;

where the reaction product components are essentially does not contain a simple polyetherpolyols and where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

In some non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane comprising the stage of interaction in a process vessel components, including:

(a) about 1 equivalent of at least one MDI;

(b) from about 0.3 to 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

(C) from about 0.01 to 0.3 equivalent, of at least one polycarbonate diol; and

(d) from about 0.1 to 0.9 equivalents of at least one diol containing from 2 to 18 atoms of the angle of the ode;

where the reaction product components are essentially does not contain a simple polyetherpolyols and where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

In other non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane, which include stages:

(a) interaction of at least one MDI and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of polyurethane prepolymer, and

(b) interaction of polyurethane prepolymer at least one polycarbonate diol and at least one diola containing from 2 to 18 carbon atoms, with the formation of polyurethane;

where the reaction product components are essentially does not contain a simple polyetherpolyols.

Group G

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes comprising the reaction products of components, including:

(a) about 1 equivalent of at least one MDI;

(b) from about 0.3 to 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydrox the global group;

(C) from about 0.01 to 0.3 equivalent, of at least one polyol selected from the group comprising complex polyetherpolyols, polycaprolactone polyol and mixtures thereof; and

(d) from about 0.1 to 0.7 equivalent of at least one aliphatic diol;

where the reaction product components are essentially does not contain a simple polyetherpolyols and amine curing agent and where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

In other non-limiting embodiments, the implementation of the present invention provides polyurethanes including a reaction product of components including:

(a) about 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate);

(b) about 0.3 equivalents of trimethylolpropane;

(C) from about 0.5 equivalent decandiol; and

(d) about 0.2 equivalent polycaprolactone polyol;

where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

In some non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane comprising the stage of interaction in a process vessel components, including:

(a) approximately what about 1 equivalent, at least one MDI;

(b) from about 0.3 to 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(C) from about 0.01 to 0.3 equivalent, of at least one polyol selected from the group comprising complex polyetherpolyols, polycaprolactone polyol and mixtures thereof; and

(d) from about 0.1 to 0.7 equivalent of at least one aliphatic diol;

where the reaction product components are essentially does not contain a simple polyetherpolyols and amine curing agent.

In other non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane, which include stages:

(a) interaction of at least one MDI and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of polyurethane prepolymer, and

(b) interaction of polyurethane prepolymer at least one polyol selected from the group comprising complex polyetherpolyols, polycaprolactone polyol and mixtures thereof, and from about 0.1 to 0.7 equivalent of at least one aliphatic diol with the formation of polyurethane.

Group H

In some the non-limiting embodiments, the implementation of the present invention provides polyurethanes, comprising the reaction product of components including:

(a) prepolymer, which is a reaction product of components including:

(1) at least one polyisocyanate;

(2) at least one polycaprolactone polyol;

(3) at least one polyol selected from the group comprising polyalkyleneglycol, simple polyetherpolyols and mixtures thereof; and

(b) at least one diol containing from 2 to 18 carbon atoms.

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes including a reaction product of components including:

(a) prepolymer, which is a reaction product of components including:

(1) aliphatic or cycloaliphatic diisocyanate;

(2) polycaprolactone diol;

(3) polyethylene glycol; and

(4) a copolymer of polyoxyethylene and polyoxypropylene; and

(b) at least one diol containing from 2 to 18 carbon atoms.

In some non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane, which include stages:

(a) interaction of components, including:

(1) at least one polyisocyanate;

(2) at least one polycaprolactone polyol; and

(3) at least one polyol selected from the group comprising polyalkyleneglycol, Rostow polyetherpolyols and mixtures thereof;

with the formation of polyurethane prepolymer; and

(b) interaction of prepolymer at least one diola containing from 2 to 18 carbon atoms, with the formation of polyurethane.

Group I

In some non-limiting embodiments, the implementation of the present invention provides poly(mochevinoi), comprising the reaction product of components including:

(a) at least one urea prepolymer with isocyanate functionality, containing the reaction product of:

(1) at least one MDI; and

(2) water; and

(b) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

where the reaction product components are essentially does not contain amine curing agent.

In some non-limiting embodiments, the implementation of the present invention provides methods for obtaining poly(mochevinoi), which include stages:

(a) interaction of at least one MDI and water with the formation of urea prepolymer with isocyanate functionality; and

(b) interaction of the reaction product of components containing urea prepolymer with isocyanate functionality of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 Hydra is cselenyi group;

where the reaction product components are essentially does not contain amine curing agent.

Group J

In some non-limiting embodiments, the implementation of the present invention provides poly(mochevinoi)containing the reaction product of components including:

(a) at least one urea prepolymer with isocyanate functionality, containing the reaction product of:

(1) at least one MDI selected from the group comprising trimers MDI and branched polyisocyanates, the polyisocyanate contains at least three isocyanate functional groups; and

(2) water; and

(b) at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups.

In some non-limiting embodiments, the implementation of the present invention provides methods for obtaining poly(mochevinoi), which include stages:

(a) interaction of at least one MDI selected from the group comprising trimers MDI and branched polyisocyanates, and water with the formation of urea prepolymer with isocyanate functionality; and

(b) interaction of the reaction product of components containing urea prepolymer with isocyanate functionality of at least one and OfficeScan a polyol, containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups;

where the reaction product components are essentially does not contain amine curing agent.

Group By

In some non-limiting embodiments, the implementation of the present invention provides poly(mochevinoi)containing the reaction product of components including:

(a) at least one motivirovochnuyu prepolymer with isocyanate functionality, containing the reaction product of:

(1) at least one urethane prepolymer with isocyanate functionality, containing the reaction product of:

(i) a first amount of at least one MDI; and

(ii) a first amount of at least one branched polyol; and

(2) water;

with the formation of motivirovannogo of prepolymer with isocyanate functionality; and

(b) a second amount of at least one MDI and a second amount of at least one branched polyol.

In some non-limiting embodiments, the implementation of the present invention provides methods for obtaining poly(mochevinoi), which include stages:

(a) interaction of at least one MDI and at least one branched polyol containing from 4 to 18 carbon atoms and at least hydroxyine group, with the formation of urethane prepolymer with isocyanate functionality;

(b) interaction urethane prepolymer with isocyanate functionality of water and polyisocyanate, with the formation of motivirovannogo of prepolymer with isocyanate functionality; and

(C) interaction of the reaction product of components containing motivirovochnuyu prepolymer with isocyanate functionality of at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups;

where the reaction product components are essentially does not contain amine curing agent.

Group L

In some non-limiting embodiments, the implementation of the present invention provides poly(mochevinoi)containing the reaction product of components including:

(a) at least one motivirovochnuyu prepolymer with isocyanate functionality, containing the reaction product of:

(1) at least one urethane prepolymer with isocyanate functionality, containing the reaction product of:

(i) a first amount of at least one MDI selected from the group comprising trimers MDI and branched polyisocyanates, the polyisocyanates containing at least three isocyanate functional groups; and

(ii)the first number, at least one aliphatic polyol; and

(2) water;

with the formation of motivirovannogo of prepolymer with isocyanate functionality; and

(b) a second amount of at least one MDI and a second amount of at least one aliphatic polyol.

In some non-limiting embodiments, the implementation of the present invention provides methods for obtaining poly(mochevinoi), which include stages:

(a) interaction of at least one MDI selected from the group comprising trimers MDI and branched polyisocyanates, and at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups, with the formation of urethane prepolymer with isocyanate functionality;

(b) interaction urethane prepolymer with isocyanate functionality of water and polyisocyanate with education motivirovannogo of prepolymer with isocyanate functionality; and

(C) interaction of the reaction product of components containing motivirovochnuyu prepolymer with isocyanate functionality of at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups;

where the reaction product components are essentially the e contains amine curing agent.

Group M

In some non-limiting embodiments, the implementation of the present invention provides poly(mochevinoi)containing the reaction product of components including:

(a) about 1 equivalent of at least one MDI;

(b) from about 0.1 to 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

(C) from about 0.1 to 0.9 equivalents of at least one aliphatic diol containing from 2 to 18 carbon atoms; and

(d) at least one amine curing agent,

where the reaction product components are essentially does not contain complex polyetherpolyols and simple polyetherpolyols.

In other non-limiting embodiments, the implementation of the present invention provides methods for obtaining poly(mochevinoi), which include the stage of interaction in a process vessel components, including:

(a) at least one polyisocyanate;

(b) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

(C) at least one aliphatic diol containing from 2 to 18 carbon atoms; and

(d) amine curing agent,

where the reaction product components are essentially not with the complex holds polyetherpolyols and simple polyetherpolyols.

Group N

In some non-limiting embodiments, the implementation of the present invention provides poly(mochevinoi)containing the reaction product of components including:

(a) at least one polyisocyanate selected from the group comprising trimers MDI and branched polyisocyanates, the polyisocyanate contains at least three isocyanate functional groups;

(b) from about 0.1 to 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups;

(C) at least one amine curing agent;

where the reaction product components are essentially does not contain complex polyetherpolyols and simple polyetherpolyols.

In some non-limiting embodiments, the implementation of the present invention provides methods for obtaining poly(mochevinoi), which include the stage of interaction in a process vessel components, including:

(a) at least one polyisocyanate selected from the group comprising trimers MDI and branched polyisocyanates;

(b) at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

(C) at least one aliphatic diol containing from 2 to Alimov carbon; and

(d) amine curing agent,

where the reaction product components are essentially does not contain complex polyetherpolyols and simple polyetherpolyols.

Group Of

In some non-limiting embodiments, the implementation of the present invention provides a polyurethane material comprising the first portion of the crystalline particles with semioriental and connected together to commit their orientation along a first crystallographic direction, and the second part of the crystalline particles with semioriental and connected together to commit their orientation along a second crystallographic direction, and the first crystallographic direction is different from the second crystallographic direction, and where these crystalline particles comprise more than about 30% of the total volume of the polyurethane material.

Group f

In some non-limiting embodiments, the implementation of the present invention provides methods of obtaining polyurethane powder covering compositions which include stage: communicating at least one MDI, at least one aliphatic polyol with education, as a rule, solid prepolymer with a hydroxyl functionality; melting prepolymer with a hydroxyl function the software; melting at least one normally solid MDI with the formation of molten MDI; mixing prepolymer with hydroxyl functionality and molten MDI with the formation of the mixture; and curing the mixture with the formation, usually solid powder covering composition.

In other non-limiting embodiments, the implementation of the present invention provides methods of obtaining polyurethane powder covering compositions which include stage: communicating at least one MDI, at least one aliphatic polyol with education, as a rule, solid prepolymer with a hydroxyl functionality; dissolution of prepolymer with a hydroxyl functionality in the first solvent from the first solution; dissolving at least one normally solid MDI in the second solvent, which is the same solvent or compatible with the first solvent, with the formation of the second solution; mixing the first and second solutions; and remove essentially all of the solvent to form normally solid powder covering composition.

Group Q

In some non-limiting embodiments, the implementation of the present invention provides polyurethane is oppozitsii, containing at least one polyurethane containing the reaction product of components including:

(a) (i) at least one polyisocyanate;

(ii) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(iii) at least one diol containing from 2 to 18 carbon atoms; and

(b) at least one reinforcing material selected from the group comprising polymeric inorganic materials, polimernye inorganic materials, polymeric organic materials, polimernye organic materials, their composites, and combinations thereof.

In other non-limiting embodiments, the implementation of the present invention provides polyurethane compositions containing:

(a) at least one polyurethane containing the reaction product of components including:

(i) at least one polyisocyanate;

(ii) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(iii) at least one polyol containing one or more bromine atoms, one or more phosphorus atoms or combinations thereof; and

(b) at least one reinforcing material selected from the group comprising polymeric inorganic materials, polimernye inorganic materials, poly is Ernie organic materials, polimernye organic materials, their composites and mixtures thereof.

In other non-limiting embodiments, the implementation of the present invention provides polyurethane compositions containing:

(a) the polyurethane containing the reaction product of components including:

(i) prepolymer, which is a reaction product of components including:

(1) at least one polyisocyanate;

(2) at least one polycaprolactone polyol; and

(3) at least one polyol selected from the group comprising polyalkyleneglycol, simple polyetherpolyols and mixtures thereof; and

(ii) at least one diol containing from 2 to 18 carbon atoms; and

(b) at least one reinforcing material selected from the group comprising polymeric inorganic materials, polimernye inorganic materials, polymeric organic materials, polimernye organic materials, their composites and mixtures thereof.

In other non-limiting embodiments, the implementation of the present invention provides polyurethane compositions containing:

(a) at least one polyurethane containing the reaction product of components including:

(i) at least one polyisocyanate selected from the group comprising trimers MDI or branched polyisocyanates, the polyisocyanate contains at IU is e, three isocyanate functional groups; and

(ii) at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least two hydroxyl groups; and

(b) at least one reinforcing material selected from the group comprising polymeric inorganic materials, polimernye inorganic materials, polymeric organic materials, polimernye organic materials, their composites and mixtures thereof.

In other non-limiting embodiments, the implementation of the present invention provides a composition of poly(macawesomeshow)containing:

(a) at least one poly(mochevinoi)containing the reaction product of components including:

(i) at least one prepolymer with isocyanate functionality, containing the reaction product of:

1) at least one MDI; and

2) water; and

(ii) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

where the reaction product components are essentially does not contain amine curing agent;

and

(b) at least one reinforcing material selected from the group comprising polymeric inorganic materials, polimernye inorganic materials, polymeric organic materials, polimernye organic materials, HDMI is you and mixtures thereof.

In other non-limiting embodiments, the implementation of the present invention provides a composition of poly(macawesomeshow)containing:

(a) at least one poly(mochevinoi)containing the reaction product of components including:

(i) at least one urethane prepolymer with isocyanate functionality, containing the reaction product of:

1) the first amount of at least one MDI; and

2) the first amount of at least one branched polyol; and

(ii) water,

with the formation of motivirovannogo of prepolymer with isocyanate functionality; and

(b) a second amount of at least one MDI and a second amount of at least one branched polyol;

(C) at least one reinforcing material selected from the group comprising polymeric inorganic materials, polimernye inorganic materials, polymeric organic materials, polimernye organic materials, their composites and mixtures thereof.

In some non-limiting embodiments, the implementation of the present invention provides methods for obtaining enhanced polyurethane compositions which include stage: mixing a solution of the precursor reaction product of the components described above polyurethane or poly(mochevinoi) with predshestvennika the nanostructures; the formation of nanostructures of the precursor nanostructures in a polyurethane matrix; and polymerization of the precursor reaction product of components with the formation of polyurethane.

The group R

In some non-limiting embodiments, the implementation of the present invention provides a laminate containing:

(a) at least one layer of at least one polyurethane containing the reaction product of components including:

(i) at least one polyisocyanate;

(ii) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(iii) at least one diol containing from 2 to 18 carbon atoms; and

(b) at least one layer of a base, selected from the group comprising paper, glass, ceramics, wood, masonry, textile, metal or organic polymeric material and combinations thereof.

In other non-limiting embodiments, the implementation of the present invention provides a laminate containing:

(a) at least one layer of at least one polyurethane containing the reaction product of components including:

(i) at least one polyisocyanate;

(ii) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(iii) at least is in the polyol, containing one or more bromine atoms, one or more phosphorus atoms or combinations thereof; and

(b) at least one layer of a base, selected from the group comprising paper, glass, ceramics, wood, masonry, textile, metal or organic polymeric material and combinations thereof.

In other non-limiting embodiments, the implementation of the present invention provides a laminate containing:

(a) at least one layer of at least one polyurethane containing the reaction product of components including:

(i) prepolymer, which is a reaction product of components including:

(1) at least one polyisocyanate;

(2) at least one polycaprolactone polyol; and

(3) at least one polyol selected from the group comprising polyalkyleneglycol, simple polyetherpolyols and mixtures thereof; and

(ii) at least one diol containing from 2 to 18 carbon atoms; and

(b) at least one layer of a base, selected from the group comprising paper, glass, ceramics, wood, masonry, textile, metal or organic polymeric material and combinations thereof.

In other non-limiting embodiments, the implementation of the present invention provides a laminate containing:

(a) at least one layer of at least one polyurethane containing product re the work of the component, including:

(i) at least one polyisocyanate selected from the group comprising trimers MDI or branched polyisocyanates, the polyisocyanate contains at least three isocyanate functional groups; and

(ii) at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least two hydroxyl groups; and

(b) at least one layer of a base, selected from the group comprising paper, glass, ceramics, wood, masonry, textile, metal or organic polymeric material and combinations thereof.

In other non-limiting embodiments, the implementation of the present invention provides a laminate containing:

(a) at least one layer of at least one poly(mochevinoi)containing the reaction product of components including:

(i) at least one prepolymer with isocyanate functionality, containing the reaction product of:

1) at least one MDI; and

2) water; and

(ii) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

where the reaction product components are essentially does not contain amine curing agent; and

(b) at least one layer of a base, selected from the group comprising paper, glass, ceramics, wood, Kameno the clutch, fabric, metal or organic polymeric material and combinations thereof.

In other non-limiting embodiments, the implementation of the present invention provides a laminate containing:

(A) at least one layer of at least one poly(mochevinoi)containing the reaction product of components including:

(a) at least one motivirovochnuyu prepolymer with isocyanate functionality, containing the reaction product of components including:

(1) at least one urethane prepolymer with isocyanate functionality, containing the reaction product of:

a) a first amount of at least one MDI; and

b) the first amount of at least one branched polyol; and

(2) water;

with the formation of motivirovannogo of prepolymer with isocyanate functionality; and

(b) a second amount of at least one MDI and a second amount of at least one branched polyol; and

(C) at least one layer of a base, selected from the group comprising paper, glass, ceramics, wood, masonry, textile, metal or organic polymeric material and combinations thereof.

Also the present invention provides solid compositions, products, laminates and methods of making and using the compositions, products and laminates, aderrasi the above-described polyurethanes and poly(mochevinoi).

BRIEF DESCRIPTION of DRAWINGS

The above is the essence of the invention and the following detailed description easier to understand when considering the accompanying drawings.

FIGURE 1 is a graph G' and G” as a function of temperature measured using dynamic mechanical analysis (DMA, DMA), and this graph shows the dynamic modulus, loss modulus and tangent Delta (tan. Delta tan Delta) for casting of a polyurethane according to example A, formulation 1 of the present invention.

FIGURE 2 is a graph G' and G” as a function of temperature measured using dynamic mechanical analysis (DMA, DMA), and this graph shows the dynamic modulus, loss modulus and tan. The Delta for the casting of a polyurethane according to example A, formulation 2 of the present invention.

FIGURE 3 is a graph G' and G” as a function of temperature measured using dynamic mechanical analysis (DMF, DMA), and this graph shows the dynamic modulus, loss modulus and tan. The Delta for the casting of a polyurethane according to example A, formulation 40 of the present invention.

FIGURE 4 is a micrograph in PAM (THE), showing the casting of a polyurethane according to example A, formulation 2, proanalizirovannye two weeks after receipt in accordance with the present invention.

FIGURE 5 is a micrograph in TEM, showing the casting of a polyurethane according to example A, formulation 2, analyzed three weeks after receipt in accordance with the present invention.

6 is a micrograph in TEM, showing the casting of a polyurethane according to example A, formulation 2, analyzed seven months after receipt in accordance with the present invention.

7 is an electron diffraction pattern casting of the polyurethane of example A, formulation 2 with 6.

FIG is a micrograph in TEM, showing the second part of the casting of polyurethane with 6 in accordance with example A, formulation 2, obtained after keeping under normal conditions for about seven months in accordance with the present invention.

FIGURE 9 is a micrograph in TEM, showing the first part of the casting of a polyurethane according to example A, formulation 2, obtained after keeping at room temperature for about two to four weeks.

FIGURE 10 is a micrograph in TEM, showing the second part of the casting of a polyurethane according to example A, formulation 2 shown in FIG.9.

11 is a micrograph in PAM, on asiausa casting of a polyurethane according to example A, recipe 2.

FIG is a micrograph in TEM, showing the first part of the casting of a polyurethane according to example A, formulation 2, obtained after keeping at room temperature for approximately seven months.

FIG is a micrograph in TEM, showing the second part of the casting of a polyurethane according to example A, formulation 2 shown in FIG.

FIG is a graph of heat flow as a function of temperature using differential scanning calorimetry, DSC) for castings made of polyurethane according to example A, formulation 2, obtained after keeping under normal conditions for two weeks, three months and seven months, respectively, in accordance with the present invention.

FIG is a graph showing the impact on Gardner as a function of young's modulus for casting polyurethane according to example A, formulation 1 and 2, obtained after keeping under normal conditions for a period of seven months and one year, respectively, in accordance with the present invention.

FIG is a graph of the dynamic modulus, loss modulus and tan. Delta as a function of temperature, measured using DMA, for castings made of polyurethane obtained in the accordance with example A, the recipe 114, in accordance with the present invention.

FIG is a picture in perspective of the test sample of the formulation 2, the sample And, after the bombardment of the sample with bullets caliber 0,40 from a distance of 30 feet (9.2 m) at a speed of 987 ft/sec (300,8 m/sec).

FIG is a photograph of a front view of the test sample of the formulation 2, the sample And, after the bombardment of the sample by using a 12 gauge shotgun from a distance of 20 feet (6.1 m) at a speed of 1290 ft/sec (393,2 m/s) with heavy sports lead drobin.

FIG is a photograph of a front view of the test sample recipes 93, example And, after the bombardment of a sample of 9 mm bullets from a distance of 20 feet (6.1 m) if the initial velocity of 1350 ft/sec (411,5 m/sec).

FIG is a picture in perspective of the test sample recipes 94, example And, after the bombardment of the sample 9 mm bullet from a distance of 20 feet (6.1 m) if the initial velocity of 1350 ft/sec (411,5 m/sec).

FIG is a side view of the sample shown in FIG.

FIG is a front view of part of a composite in accordance with the present invention after the bombardment of the sample by four bullets of 7.62×39 mm, with steel core, from rifled rifle AK-47 from a distance of 30 yards (27.4 m) when the initial velocity of 2700 ft/s (823 m/s).

FIG is a rear view of the sample with FIG.

p> FIG is a graph of heat flow as a function of temperature using differential scanning calorimetry (DSC) for castings made of polyurethane according to example A, formulation 2, of the present invention.

FIG is a graph of heat flow as a function of temperature measured using DSC for castings made of polyurethane obtained according to example A, formulation 136, of the present invention.

FIG is a graph of mass loss as a function of temperature measured using thermogravimetric analysis (TGA, TGA) for castings made of polyurethane obtained according to example A, formulation 136, of the present invention.

DETAILED DESCRIPTION

Used in this description of spatial definitions, directions, such as "inside", "left", "right", "up", "down", "horizontal", "vertical", etc. relate to the invention as it is described. However, it should be understood that the invention may assume various alternative orientations and, therefore, such definitions should not be construed as limiting. For the purposes of the present description, unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, dimensions, physical characteristics the Tiki etc., used in the description and in the claims, should be understood as modified in all instances by defining "approximately". Accordingly, unless otherwise indicated, the numerical parameters presented in the following description and the attached claims are approximations that may vary depending on the desired properties, which are believed, should be obtained using the present invention. In an extreme case, but not as an attempt to limit the application of the system of equivalents of the scope of the claims, each numerical parameter should at least be interpreted taking into account the number of significant digits and by applying ordinary rounding techniques values.

Notwithstanding that the numerical ranges and parameters setting broad scope of the invention are approximations, the numerical values shown in the specific examples presented as closely as possible. Any numerical values, however, internally contain some errors inevitably resulting from the standard deviation inherent to the corresponding measurements in the tests.

In addition, it should be understood that the numerical intervals given in the work, is meant to include all potentially in them. For example, the interval from 1 to 10", as meaning odevaetsa, includes any and all potentially between the specified minimum value of 1 and the specified maximum value of 10, including these values; that is, all putinterval, beginning with a minimum value equal to or greater than 1, and ending with a maximum value of equal to or less than 10, and all potentially between them, for example from 1 to 6.3, 5.5 to 10, or from 2.7 to 6.1.

"Alkyl" means an aliphatic hydrocarbon group which may be linear or branched and may contain in the chain from about 1 to 20 carbon atoms. Non-limiting examples of suitable alkyl groups contain in the chain from about 1 to 18 carbon atoms, or from about 1 to 6 carbon atoms in the chain. "Branched" means that one or more lower alkyl groups such as methyl, ethyl or propyl, are attached to a linear alkyl chain. "Lower alkyl" or "short-chain alkyl" means a group containing from 1 to 6 carbon atoms in the chain, which may be linear or branched. "Alkyl" may be unsubstituted or optionally substituted by one or more substituents, which may be the same or different, and each Deputy independently from each other selected from the group comprising halogen atom, alkyl, aryl, cycloalkyl, cyano-, hydroxy-, alkoxy-group, is kiltia-, amino group, -NH-(alkyl), -NH(cycloalkyl), -N(alkyl)2, carboxy-group, and-C(O)O-alkyl. Non-limiting examples of suitable alkyl groups are methyl, ethyl, n-propyl, isopropyl and tert.-butyl.

"Alkylene" means difunctional group obtained by removing hydrogen atom from the alkyl group that is defined above. Non-limiting examples of alkylene are methylene, ethylene and propylene.

"Aryl" means an aromatic monocyclic or polycyclic ring system containing from about 6 to 14 carbon atoms, or from about 6 to 10 carbon atoms. Aryl group optionally may be substituted by one or more "ring system substituents"which may be the same or different and which have a certain value. Non-limiting examples of suitable aryl groups are phenyl and naphthyl.

"Heteroaryl" means an aromatic monocyclic or polycyclic ring system containing from about 5 to 14 carbon atoms in the cycle, or approximately 5 to 10 atoms in the cycle, in which one or more atoms of the cycle represent an element other than carbon atom, such as nitrogen atom, oxygen or sulfur, alone or in combination. In some non-limiting embodiments, the implementation of heteroarm the crystals contain approximately 5 to 6 atoms in the cycle. "Heteroaryl" optionally may be substituted by one or more "ring system substituents"which may be the same or different and have the meanings given to them in the work. The prefix Aza-, oxa - or thia - before the root name heteroaryl means that at least one atom of nitrogen, oxygen or sulfur, respectively, present as atoms of the cycle. The nitrogen atom of heteroaryl optional can be oxidized to the corresponding N-oxide. Non-limiting examples of suitable heteroaryl are pyridyl, pyrazinyl, furanyl, thienyl, pyrimidinyl, pyridone (including N-substituted pyridone), isoxazolyl, isothiazolin, oxazolyl, thiazolyl, pyrazolyl, furutani, pyrrolyl, pyrazolyl, thiazolyl, 1,2,4-thiadiazolyl, pyrazinyl, pyridazinyl, honokalani, phthalazine, oxindoles, imidazo[1,2-a]pyridinyl, imidazo[2,1-b]thiazolyl, benzofuranyl, indolyl, isoindolyl, benzimidazolyl, benzothiazyl, chinoline, imidazolyl, cyanopyridyl, hintline, thienopyrimidine, pyrrolopyridine, imidazopyridine, ethenolysis, benzoxazinones, 1,2,4-triazinyl, benzothiazolyl etc. the Definition of "heteroaryl" also refers to partially saturated heteroaryl residues, such as, for example, tetrahydroisoquinoline, tetrahydroquinoline etc.

"Aralkyl" or "arylalkyl" means arylalkyl group, in which the reel and the alkyl accept the previously described values. In some non-limiting embodiments, the implementation of aralkyl include lower alkyl groups. Non-limiting examples of suitable Uralkalij groups are benzyl, 2-phenethyl and naphthaleneacetic. The principal balance through alkyl.

"Alkylaryl" means alcylaryl group in which the alkyl and aryl have the previously defined meanings. In some non-limiting embodiments, the implementation of alkylaryl include lower alkyl groups. A non-limiting example of a suitable alcylaryl group is tolyl. The principal balance through aryl.

"Cycloalkyl" means a non-aromatic mono - or polycyclic ring system containing from approximately 3 to 10 carbon atoms, or from about 5 to 10 carbon atoms. In some non-limiting embodiments, the implementation cycloalkyl ring contains from about 5 to 7 atoms of the cycle. Cycloalkyl optionally may be substituted by one or more "ring system substituents"which may be the same or different and which take the above specified values. Non-limiting examples of suitable monocyclic cycloalkyl are cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl etc. non-limiting examples of suitable polycyclic what Cloudkill are 1-decaline, norbornyl, substituted and others

"Halogen atom" or "halogen" means fluorine, chlorine, bromine or iodine. In some non-limiting embodiments, the halogen groups are fluorine, chlorine or bromine.

"Deputy ring system" means the Deputy attached to aromatic or non-aromatic ring system which, for example, replaces an available hydrogen atom of the ring system. The ring system substituents may be the same or different, each independently selected from the group including alkyl, alkenyl, quinil, aryl, heteroaryl, aralkyl, alkylaryl, heteroalkyl, heteroaryl-alkenyl, heteroallyl, alkylether, hydroxy group, hydroxyalkyl, alkoxy, aryloxy, Alcoxy group, acyl, aroyl, halogen, nitro-, cyano-, carboxy-group, alkoxycarbonyl, aryloxyalkyl, arelaxation, alkylsulfonyl, arylsulfonyl, heteroarylboronic, alkylthio, aaltio, heteroaromatic, Uralkali, heteroalkyl group, cycloalkyl, heterocyclyl, -C(=N-CN)-NH2, -C(=NH)-NH2, -C(=NH)-NH(alkyl), Y1Y2N, Y1Y2N-alkyl, Y1Y2NC(O)-, Y1Y2NSO2- and-SO2NY1Y2where Y1and Y2may be the same or different and independently from each other selected from the group comprising a hydrogen atom, alkyl, aryl, cycloalkyl and alkyl. "Deputy ring system" may also mean a single residue, which simultaneously replaces two available hydrogen atoms on two adjacent carbon atoms (one H on each carbon atom in the ring system. Examples of such residues are methylendioxy, Ethylenedioxy-, -C(CH3)2- etc. that form these residues, as for example:

"Heterocyclyl" means a non-aromatic saturated monocyclic or polycyclic ring system containing from about 3 to 10 atoms in the cycle, or approximately 5 to 10 atoms in the cycle, in which one or more atoms of the ring system is an element other than carbon atom, such as nitrogen atom, oxygen or sulfur, alone or in combination. In the ring system there are no adjacent oxygen atoms and/or sulfur. In some non-limiting embodiments, the implementation heterocyclyl contains approximately 5 to 6 atoms in the cycle. The prefix Aza-, oxa - or thia - before the root name heterocyclyl means that at least one atom of nitrogen, oxygen or sulfur, respectively, present as atoms of the cycle. Any fragment-NH in heterocyclyl ring may be protected by such groups as, for example, -N(Boc), -N(CBz), -N(Tos) and so on; such protection is also considered as part of the data is of the first invention. Heterocyclyl optionally may be substituted by one or more ring system substituents, which may be the same or different and are as defined above values. The nitrogen atom or sulfur heterocyclyl optional can be oxidized to a corresponding N-oxide, S-oxide or S,S-dioxide. Non-limiting examples of suitable monocyclic heterocyclyl rings are piperidyl, pyrrolidinyl, piperazinil, morpholinyl, thiomorpholine, thiazolidine, 1,4-dioxane, tetrahydrofuranyl, tetrahydrothiophene, lactam, lactone, etc.

It should be noted that in the containing heteroatom ring systems of the present invention lacks a hydroxyl group on the carbon atoms adjacent to the atoms N, O or S, and no N - or S-group on the carbon atom adjacent to another heteroatom. That is, for example, in the ring:

there is no group-HE attached directly to carbon atoms, numbered 2 and 5.

It should also be noted that tautomeric forms, such as, for example, fragments:

in some embodiments of the invention are equivalent.

"Heteroalkyl" means heteroallyl group, in which heteroaryl and alkyl accept the previously described values. In some neogranichena the appropriate options for implementation of heteroalkyl contains lower alkyl group. Non-limiting examples of suitable heteroaryl groups include pyridylmethyl and quinoline-3-ylmethyl. The principal balance through alkyl.

"Hydroxyalkyl" means BUT is an alkyl group in which the alkyl takes the previously defined values. In some non-limiting embodiments, hydroxyalkyl contains lower alkyl group. Non-limiting examples of suitable hydroxyalkyl groups include hydroxymethyl and 2-hydroxyethyl.

"Alkoxy group" means an alkyl-O-group in which the alkyl group adopts the previously described values. Non-limiting examples of suitable alkoxy groups are methoxy, ethoxy-, n-propoxy, isopropoxy - and n-butoxy group. The principal balance is through the etheric oxygen atom.

"Aryloxy group" means aryl-O-group in which the aryl group adopts the previously described values. Non-limiting examples of suitable, aryloxy groups are phenoxy and naphthoxy group. The principal balance is through the etheric oxygen atom.

"Alkylthio group" means an alkyl-S-group in which the alkyl group adopts the previously described values. Non-limiting examples of suitable, alkylthio groups are methylthio and ethylthio group. The principal balance is carried out is via the sulfur atom.

"Aaltio group" means an aryl-S-group in which the aryl group adopts the previously described values. Non-limiting examples of suitable, aaltio groups are phenylthio and naphthylthio group. The principal balance is through the sulfur atom.

"Uralkali group" means aralkyl-S-group in which kalkilya the group takes the previously described values. A non-limiting example of a suitable, Uralkali group is benzylthio group. The principal balance is through the sulfur atom.

"Alkoxycarbonyl" means alkyl-O-CO-group. Non-limiting examples of suitable alkoxycarbonyl groups are methoxycarbonyl and etoxycarbonyl. The principal balance is through the carbonyl.

"Aryloxyalkyl" means aryl-O-C(O)-group. Non-limiting examples of suitable aryloxyalkyl groups are phenoxycarbonyl and mattoxicator. The principal balance is through the carbonyl.

"Arelaxation" means aralkyl-O-C(O)-group. A non-limiting example of a suitable alcoxycarbenium group is benzyloxycarbonyl. The principal balance is through the carbonyl.

"Alkylsulfonyl" means an alkyl-S(O2)group. In some non-limiting embodiments, alkyls Honiley group includes a lower alkyl group. The principal balance through sulfonyl.

"Arylsulfonyl" means an aryl-S(O2)group. The principal balance through sulfonyl.

The definition of "substituted" means that one or more hydrogen atoms on the desired atom substituted by selection from the indicated group, provided that the normal valency of the atom marked with the existing cases are not exceeded and that the substitution results in a stable connection. Combinations of substituents and/or variables are permissible only if such combinations result in stable compounds.

The definition of "optionally substituted" means an optional substitution of certain groups, radicals or residues.

It should be understood that any atom of carbon and heteroatom unfilled valences in the text, schemes, examples and tables, as is implied, has a sufficient number of hydrogen atoms to complement valence.

When the functional group in connection named "protected", this means that the group is in modified form to prevent unwanted side reactions at the protected site when the connection is introduced into the reaction. Suitable protective groups can be defined by experts in the field of technology and also using the standard at which enikov, such as, for example, by T.W. Greene et al.,Protective Groups in Organic Synthesis(1991), Wiley, New York.

When any variable (e.g. aryl, heterocycle, R2and others) occurs more than one time in any constituent, its definition in each case depends on its definition at every other case.

Used in this case, the definition of "composition", as implied, covers the product contains certain ingredients in certain amounts, as well as any product which results, directly or indirectly, from the combination of certain ingredients in certain amounts.

Used in this case, the expression "made up of" or "derived from" means open, for example, "contains" linguistic approval. In itself, this expression implies that the composition is made up of" or "derived from" a list of components which will provide a composition containing, at least, these listed components or the reaction product of at least these listed components, and may additionally include other, non-listed components, during education or obtain a composition. Used in this case, the expression "reaction product" means the product(s) chemical reaction of the listed components and may include products of incomplete re the functions, products full response.

Used in this case, the definition of "polymer", as implied covers oligomers and includes, without limitation, as homopolymers and copolymers. The definition of "prepolymer" means a compound, monomer or oligomer to be used to obtain polymer, and includes, but without limitation, the oligomers as homopolymer and copolymer.

The expression "thermoplastic polymer" means a polymer that becomes liquid when heated and can be soluble in solvents.

The expression "thermosetting polymer" means a polymer that solidifies or "sets" during curing or cross-linking. Once cured, crosslinked thermosetting polymer will not melt upon application of heat and, as a rule, insoluble in solvents.

Used in this case, the definition of "curing"used with regard to the composition, for example, the composition, when she overiden" or "cured composition", will mean that any capable of curing or capable of cross-linking of components of the composition are at least partially otverzhdennye or cross stitched. In some non-limiting embodiments of the present invention, the density of cross-linkage is capable of blending components, i.e. the degree to pop the river stitching, is in the range from about 5 to 100% of complete crosslinking. In other non-limiting embodiments of the present invention, the density of cross-linkage is in the range from about 35 to 85% of full crosslinking. In other non-limiting embodiments of the present invention, the density of cross-linkage is in the range from about 50 to 85% of full crosslinking. Qualified in this field specialist will be clear that the presence and degree of crosslinking, i.e., the density of crosslinking can be determined using a variety of methods, such as dynamic mechanical thermal analysis (DMA, DMA) using TMA analyzer, TA Instruments DMA 2080 within the temperature range from -65 to 350°F (-18 to 177oC)carried out in nitrogen atmosphere in accordance with ASTM D 4065-01. In this method, determine the glass transition temperature and the density of knitting free films, coatings or polymers. Such physical properties of the cured material associated with the structure of a crosslinked polymer network. In one embodiment of the present invention adequacy of curing judged by resistance to solvents utverzhdenii polymer films. For example, resistance to solvents can be measured by determining the number of double acetone of proteron. For the purpose of this image is etenia, coverage is considered "utverzhdennym"when the film can withstand at least 100 double proteron acetone without significant softening of the film and without removing the foil.

Curing capable of polymerization composition can be obtained due to the impact on the composition of the curing conditions, such as, but without limitation, thermal curing, irradiation, etc. leading to reactions between the reactive groups of the composition and leading to polymerization and formation of a hard polymerizate. When capable of polymerization composition is subjected to curing conditions, after polymerization and after cooperation of most of the reactive groups in the reaction rate of the remaining unreacted reactive groups gradually slows down. In some non-limiting embodiments, the implementation is capable of polymerization, the composition may be subjected to curing conditions, while she, at least, will not become partially utverzhdenii. The definition of "at least partially cured" means the impact on capable of curing the composition to curing conditions, where the reaction takes place at least part of the reactive groups of the composition by formation of solid polymerizate. At least partially cured polymerizate can b is to be extracted from the form and used for example, for the preparation of products such as Windows, cut in pieces for testing or subjected to mechanical operations, such as processing in optical lenses. In some non-limiting embodiments, the implementation is capable of polymerization, the composition may be subjected to curing conditions, which is achieved essentially complete curing and where additional exposure to curing conditions does not lead to significant additional improvement in polymer properties, such as strength or hardness.

The term "polyurethane"as implied, includes not only the polyurethane, which is formed by the reaction of polyisocyanates and polyols, but also poly(mochevinoi), which is obtained by the reaction of polyisocyanates with polyols and water and/or polyamines.

The polyurethanes and poly(mochevinoi) of the present invention can be used in such cases where you need one or more of the following properties: transparency, high optical performance, high Abbe number, low staining, energy absorption, stiffness, resistance to moisture, resistance to ultraviolet light, resistance to weathering, low water absorption, hydrolytic stability and resistance to the bullet or explosion.

In some embodiments of the invention overide the major products, derived from polyurethanes and poly(macawesomeshow) of the present invention, are usually transparent, can have a transmittance of at least about 80%, the turbidity of less than about 2% and do not show visible changes after exposure to light and water for 1000 hours in accordance with ASTM D-1499-64.

The polyurethanes and poly(mochevinoi) of the present invention can be converted to products having different shapes and sizes, such as flat sheets or curved sheets. Non-limiting examples of acceptable methods of obtaining products are heat treatment, injection molding or pouring liquid polyurethane or poly(mochevinoi) in the form and cure the product with the formation of molded products.

Typically, polyurethane or poly(mochevinoi) of the present invention include the reaction product of components comprising at least one polyisocyanate and at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 or at least 3 hydroxyl groups, where at least one of the MDI(s) and/or aliphatic(s), polyol(s) one(s)extensive(and).

In the present invention, at least one isocyanate and/or at least one polyol are branched. COI is ltheme in this case, the definition of "branched" means a chain of atoms with one or more side chains, attached to her. Branching is done by substitution of substituent such as a hydrogen atom, covalently linked by a Deputy or a residue such as alkyl group. Not being tied to any theory, I believe that the branching MDI and/or polyol may increase the free volume within the polymer matrix, resulting in a space for the movement of molecules. Molecules can Orient and rotate configurations and locations, with the preferred energy state that can provide good impact properties and/or high modulus of elasticity for utverzhdenii polymer matrix. As shown in figures 1, 2 and 3, dynamogenesis analysis (DMA) of polyurethane castings prepared in accordance with examples 1, 2 and 40, respectively, for the loss modulus as a function of temperature shows a low temperature phase transition at approximately -70°C. DMA is carried out in the temperature range from -65 to 350°F (-18 to 177°C) in nitrogen atmosphere in accordance with ASTM D 4065-01. Not being tied to any theory, I believe that the low temperature phase transition from the molecular torsional mobility at this temperature and is thought to contribute to the high impact strength of such polymers.

When a viscoelastic material is subjected to stake athelney vibration, in the polymer accumulating a certain amount of energy, which is proportional to the elastic component of the modulus G' or the dynamic modulus of elasticity, and some energy is converted into heat through internal friction, or viscous dissipation, which is expressed in the value of the loss modulus G”. The maximum value of the loss modulus is denoted by tan. Delta (tangent Delta tan delta), which represents the maximum of internal friction, damping or viscous energy dissipation.

Glassy polymers with high transmittance rarely exhibit high impact strength. Polycarbonate plastic such as LEXAN, can show similar low temperature phase transition, but may have lower impact strength and lower young's modulus.

The physical properties of the polyurethanes and poly(macawesomeshow) of the present invention derived from their molecular structure and is defined by choosing the structural blocks, such as choice of reagents, the ratio of hard crystalline and amorphous soft segments and supramolecular structures due to the atomic interactions between the chains.

The hard segment that is crystalline and semi-crystalline region urethane polymer formed by the reaction of the isocyanate and deinitely circuit, such as aliphatic polyol containing from 4 to 18 carbon atoms, or a low molecular weight polyol having a molecular weight of less than about 200, which is considered in the work. Typically, the soft segment that is amorphous kauchukopodobnoe region urethane polymer formed by the reaction of the isocyanate component and the main chain of the polymer, for example complex polyetherpolyols (such as polycarbonate polyol) or simple polyetherpolyols or short-chain diols, which do not form a crystalline region.

The qualitative contribution of specific organic polyol or hard, or soft segment, when it is mixed and injected into reaction with other polyurethane-forming components can easily be determined by measuring the microhardness Fisher received the cured polyurethane in accordance with ISO 14577-1:2002.

In some non-limiting embodiments, the implementation of the content of hard segments in the polyurethane is in the range from about 10 to 100 wt. -%, or from about 50 to 100 wt. -%, or from about 70 to 100% of the mass. The content of hard segments represents a mass percentage relationships of the hard segments present in the polymer, and can be calculated by determining the total number of equivalents, and from this the total mass of all reactants, and dividing the total mass of the links of the hard segments, which can be obtained from these reagents on the total weight of the reactants. The following additional example explains this calculation. In example 1, formulation 1, which follows, polyurethane product in accordance with the present invention is obtained by introducing into the reaction 0.7 equivalent of 1,4-butanediol, 0.3 equivalents of trimethylolpropane and one equivalent of 4,4'-methylene-bis(cyclohexylsulfamate) (DESMODUR W). Equivalent weight of 1,4-butanediol is 45 g/EQ., equivalent weight of trimethylolpropane equal to 44.7 g/EQ. (with a correction for impurities) and the equivalent weight of DESMODUR W is 131.2 g/EQ. Consequently, the actual weight of the ingredients used is 31,54 mass part of 1,4-butanediol, 13,2 mass parts of trimethylolpropane and 131,2 mass parts of DESMODUR W, or the total mass of the reactants is 175 mass parts. One equivalent of 1,4-butanediol to give one equivalent connection of the hard segment, where the hard segment is a dimer, 1,4-butanediol/DESMODUR W. the Equivalent mass communication dimer 1,4-butanediol/DESMODUR W is 176 g/EQ., so that the total weight relationships of the hard segments defined by multiplying the equivalent mass of the dimer hard segments on the number of equivalents of 1,4-butanediol, will be of 123.2 g/EQ. The trail is therefore the total mass communications dimer 1,4-butanediol/DESMODUR W, of 123.2 divided by the total mass of the reactants, 175,7 multiplied by 100 to convert this to a percent, will give the mass percentage of connection of the hard segment 70% of the mass.

As plexiglass (Plexiglas), and extruded acrylic polymer absorb huge amounts of water from the atmosphere. In accelerated tests, such as QUV-B or soaking in water at room temperature, the polyurethanes in accordance with the present invention, including short-chain diols, such as butanediol and pentanediol, unexpectedly essentially do not absorb water from studies of the rate of passage of water vapor and after soaking in water for about 24 hours. Not being tied to any theory, I believe that even if these plastics are polar, hydrogen binding domains of the hard segments is strong enough to block the passage of water vapor and water absorption. For comparison, extruded acrylic polymer will absorb enough water to cause severe swelling of the plastic to the point where it cracks in the plane, like layers of onion skins, separated, until you disappear. Low water absorption can also mitigate any damage due to hydrolysis of the urethane groups in the polymer.

The discussion of various aspects and options about what westline polyurethanes and poly(macawesomeshow) of the present invention are grouped as a rule, And-Q, are presented below. As mentioned above, this assignment is not intended to limit the scope of the invention and aspects of one group can be attributed to the objects of the invention other groups. In addition, restrictions regarding the amounts of reagents in one group do not necessarily imply the limitation of quantities of the same component in the other groups, though the number may be the same for different groups, unless otherwise stated.

Group a

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes including a reaction product of components including:

(a) about 1 equivalent of at least one MDI;

(b) from about 0.05 to 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(C) from about 0.1 to 0.95 equivalent of at least one diol containing from 2 to 18 carbon atoms;

where the reaction product components are essentially does not contain complex polyetherpolyols and simple polyetherpolyols and where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

Used in this case is the distribution of the "equivalent" means the mass of substance in grams, which will react with one mole (6,022×1023electrons) other substance. Used in this case, the definition of "equivalent weight" is actually equal to the amount of substance in moles divided by the valence or the number of functional reactive groups of substances.

Used in this case, the definition of "isocyanate" includes compounds, monomers, oligomers and polymers containing at least one or at least two-N=C=O functional group and/or at least one or at least two-N=C=S (isothiocyanate) group. Monofunctional isocyanates can be used as agents breaking a chain, or for the creation of end groups during polymerization. Used in this case, the term "polyisocyanate" means an isocyanate containing at least two-N=C=O functional group and/or at least two-N=C=S (isothiocyanate) group, such as diisocyanates or triisocyanate, as well as dimers and trimers or biuret isocyanates, considered in the paper. Suitable isocyanates are capable of forming covalent bond with a reactive group such as hydroxyl, Tolna or amine functional group. The isocyanates which can be used in the present invention can be branched or prosvetlennye discussed above, the use of branched isocyanates may be desirable to increase the free volume within the polymer matrix to create space for the movement of molecules.

The isocyanates which can be used in the present invention include "modified", "unmodified" and mixtures "modified" and "unmodified" isocyanates. Isocyanates can have "free", "blocked, or partially blocked isocyanate group. The definition of "modified" means that the above-mentioned isocyanates modified in a known manner, to enter buraitou, urea, carbodiimide, urethane, or which group or a blocking group. In some non-limiting embodiments of the invention "modified" isocyanate produced using the processes cycloaddition with getting dimers and trimers isocyanate, i.e. polyisocyanates. The free isocyanate groups are extremely reactive. To control the reactivity containing isocyanate component group, NCO-groups can be blocked with the help of some selected organic compounds, which makes isocyanate group inert to the compounds with reactive hydrogen at room temperature. When heated to elevated temperatures, n is the sample, in the range from about 90 to 200°C, blocked isocyanates release of the blocking agent and react the same way as the original unlocked or free isocyanate.

Generally, the compounds used to block isocyanates, are organic compounds which have active hydrogen atoms, such as volatile alcohols, Epsilon-caprolactam or ketoxime connection. Non-limiting examples of suitable blocking compounds are phenol, cresol, Nonylphenol, Epsilon-caprolactam, methylethylketoxime.

As used in this description, NCO in respect of NCO:HE means free isocyanate material containing free isocyanate and blocked or partially blocked isocyanate-containing materials after the release of the blocking agent. In some cases it is impossible to remove all the blocking agent. In such situations it is necessary to use more blocked isocyanate-containing material to obtain the desired level of free NCO-groups.

Molecular weight isocyanate and isothiocyanate can vary widely. In alternate non-limiting embodiments, the implementation Brednikova molecular weight (Mn) of each can be at least about 100 g/mol, or at least about 150 g/m is al, or less than about 15000 g/mol, or less than about 5000 g/mol. Brednikova molecular weight can be determined using known methods, such as helpanimals chromatography (GPC, GPC) using polystyrene standards.

Non-limiting examples of suitable isocyanates are aliphatic, cycloaliphatic, aromatic and heterocyclic isocyanates, their dimers and trimers, and mixtures thereof. Useful cycloaliphatic isocyanates are diisocyanates, in which one or more isocyanate groups directly attached to a cycloaliphatic ring, and cycloaliphatic isocyanates, in which one or more isocyanate groups are not attached directly to the cycloaliphatic ring. Useful aromatic isocyanates are diisocyanates, in which one or more isocyanate groups attached directly to aromatic ring, and aromatic isocyanates, in which one or more isocyanate groups are not attached directly to the aromatic ring. Useful heterocyclic isocyanates are diisocyanates, in which one or more isocyanate groups attached directly to the heterocyclic ring, and heterocyclic isocyanates, in which one or more isocyanate is RUPE not attached directly to the aromatic ring.

Cycloaliphatic diisocyanates are desirable for use in the present invention, as it does not affect them adversely ultraviolet radiation, and they can provide polyurethanes having high levels of absorption of impact energy, which makes them attractive for replacement of glass and for use in two-layer shatterproof glass. In addition, the polyurethanes derived from a cycloaliphatic diisocyanate, not adversely impacted normal process temperatures. When using aromatic polyisocyanates in General, you should carefully approach the selection of a material which does not cause staining of polyurethane (e.g., yellow).

In some non-limiting embodiments, the implementation of aliphatic and cycloaliphatic diisocyanates may contain from about 6 to 100 carbon atoms connected in a linear chain or cycloterpenic and having two isocyanate reactive end groups.

Non-limiting examples of suitable aliphatic isocyanates are linear isocyanates, such as atlantaatlanta, trimethylindolenine, 1,6-hexamethylenediisocyanate (HMDI, HDI), tetramethyldisilane, hexamethylenediisocyanate, octamethyltrisiloxane, monomethylaniline, decamethylenediamine, 1,6,11-undecane Socionet, 1,3,6-hexamethylenediisocyanate, bis(isocyanatomethyl)carbonate, bis(isocyanatomethyl) ether.

Other non-limiting examples of suitable aliphatic isocyanates include branched isocyanates, such as trimethylhexamethylene, trimethylhexamethylenediamine (TMDI, TMDI), 2,2'-dimethylpentanenitrile, 2,2,4-trimethylhexamethylene, 2,4,4-trimethylhexamethylenediamine, 1,8-diisocyanato-4-(isocyanatomethyl)octane, 2,5,7-trimethyl-1,8-diisocyanato-5-(isocyanatomethyl)octane, 2-isocyanatopropyl-2,6-diisocyanatohexane, methyl ester lizenzierte and methyl ether disinclination.

Non-limiting examples of suitable cycloaliphatic isocyanates are dual connections, connected by bridge with isopropylidene group or alkilinity group of 1-3 carbon atoms. Non-limiting examples of suitable cycloaliphatic isocyanates are 1,1'-methylene-bis(4-isocyanatobenzene) or 4,4'-methylene-bis(cyclohexylidene) (e.g., DESMODUR W, a commercial product from Bayer Corp., Pittsburgh, Pennsylvania), 4,4'-isopropylidene-bis(cyclohexylidene), 1,4-cyclohexyldiamine (CGDI, CHDI), 4,4'-dicyclohexylmethane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (branched isocyanate also known as isophorondiisocyanate or IPDI (IPDI)), which is the commercial environments product company Arco Chemical Co., Newtown Square, Pennsylvania, and meta-tetramethylcyclopentadiene (branched isocyanate also known as 1,3-bis(1-isocyanato-1-methylethyl)benzene, which is a commercial product of the company Cytec Industries Inc., West Patterson, New Jersey, under the trade name TMXDI®(Meta) Aliphatic Isocyanate), and mixtures thereof.

Other useful dual cycloaliphatic diisocyanates include isocyanates formed through alkylenes group of 1-3 carbon atoms, inclusive, and which may be substituted, nitro group, chlorine, alkyl, alkoxy group and other groups which do not react with hydroxyl groups or active hydrogen atoms), provided that they are not located so as to turn the isocyanate group in directionspanel group. In addition, can be used hydrogenated aromatic diisocyanates such as hydrogenated, colorvision. Can also be used a dual-diisocyanate in which one ring is saturated and the other unsaturated, which are obtained by partial hydrogenation of aromatic diisocyanates, such as diphenylmethanediisocyanate, diphenylmethanediisocyanate and diphenyldiisocyanate.

Can also be used mixtures of cycloaliphatic diisocyanate with aliphatic diisocyanates and/or aromatic diisocyanates. For example,you can use 4,4'-methylene-bis(cyclohexylidene) with commercial mixtures of isomers colordistance or meta-phenylenediamine.

Can be used diisocyanate corresponding to the above diisocyanates, and mixed compounds containing both isocyanate and thioisocyanate group.

Non-limiting examples of suitable isocyanates can be, but without limiting them, DESMODUR W, DESMODUR N 3300 (trimer of hexamethylenediisocyanate), DESMODUR N 3400 (60% dimer of hexamethylenediisocyanate and 40% of the trimer of hexamethylenediisocyanate), which are commercial products from Bayer Corp.

In some non-limiting embodiments of the invention, the isocyanate can be a 1,1'-methylene-bis(4-isocyanatobenzene) (also known as 4,4'-methylene-bis(cyclohexylidene) and its isomeric mixture. Used in this case, the definition of "isomeric mixture" refers to a mixture of CIS-CIS, TRANS-TRANS and CIS-TRANS isomers of isocyanate. Non-limiting examples of isomeric mixtures suitable for use in the present invention, can be TRANS-TRANS isomer of 4,4'-methylene-bis(cyclohexylsulfamate), hereafter referred to as "PICM" (PICM) (pair-socialecological-methane), CIS-TRANS isomer PICM, CIS-CIS isomer PICM and mixtures thereof. Three suited for use in the present invention isomer 4,4'-methylene-bis(cyclohexylsulfamate) (also known as 1,1'-methylene-bis(4-isocyanatobenzene)) is presented below.

In some non-limiting embodiments of the invention PICM used in the present invention, can be obtained by postironium 4,4'-methylene-bis(cyclohexylamine) (PACM, RASM) by methods well known in the art, for example according to the methods described in U.S. patent No. 2644007 and 2680127, which are included as references. Mixture of isomers PACM when vosganian can give PICM in the liquid phase and partly in the liquid phase or in solid phase at room temperature. Mixture of isomers PCM can be obtained by hydrogenation methylenedianiline and/or by fractional crystallization of the mixture of isomers PACM in the presence of water and alcohols, such as methanol and ethanol.

In some non-limiting embodiments of the invention isomeric mixture may contain from about 10 to 100 wt%. the TRANS-TRANS isomer of 4,4'-methylene-bis(cyclohexyl isocyanate) (PICM), or from about 30 to 100 wt. -%, or from about 50 to 100 wt. -%, or from about 75 to 100% of the mass. In other non-limiting embodiments of the invention cycloaliphatic isocyanate may consist essentially of the TRANS-TRANS isomer of 1,1'-methylene-bis(4-isocyanatobenzene) (also known as 4,4'-methylene-bis(cyclohexylidene)), for example, at least about 80% of the mass. the TRANS-TRANS isomer of 1,1'-methylene-bis(4-isocyanatobenzene), and the and, at least about 90% of the mass. the TRANS-TRANS isomer of 1,1'-methylene-bis(4-isocyanatobenzene), or at least about 95% of the mass. the TRANS-TRANS isomer of 1,1'-methylene-bis(4-isocyanatobenzene), and in other non-limiting embodiments, the implementation contains approximately 100% of the mass. the TRANS-TRANS isomer of 1,1'-methylene-bis(4-isocyanatobenzene).

Non-limiting examples of suitable polyisocyanates for use in the present invention are polyisocyanates and polyisocyanate with fixed bridges, such as urethane bridges (-NH-C(O)-O-), thiourethane bridges (-NH-C(O)-S-), THIOCARBAMATE bridges (-NH-C(S)-O-), dithiolane bridges (-NH-C(S)-S-), polyamide bridges, and combinations thereof.

Other non-limiting examples of suitable polyisocyanates include ethylene-unsaturated polyisocyanates and polyisocyanate; alicyclic polyisocyanates and polyisocyanate; aromatic polyisocyanates and polyisocyanate, where the isocyanate groups are not bonded directly to an aromatic ring, such as α,α'-xylylenediisocyanate; aromatic polyisocyanates and polyisocyanate, where the isocyanate groups are bonded directly to aromatic ring, for example benzodiazelines; aliphatic polyisocyanates and polyisocyanate containing sulfide bridges; aromaticheski the polyisocyanates and polyisocyanate, containing sulfide or disulfide bridges; aromatic polyisocyanates and polyisocyanate containing sulfonic bridges; polyisocyanates and polyisocyanate type sulfonic ester such as an ester of 4-methyl-3-isocyanatomethyl-4'-isocyanatophenyl; aromatic polyisocyanates and polyisocyanate sulfonamidnuyu type; sulfur-containing heterocyclic polyisocyanates and polyisocyanate, such as thiophene-2,5-diisocyanate; halogenated, alkylated, alkoxysilane, nitrated modified with carbodiimide modified with urea and modified bureta derivatives of isocyanates; and diarizonae and trimeresurus products of isocyanates.

Non-limiting examples of suitable ethylene-unsaturated polyisocyanates are potentisation and 1,3-butadiene-1,4-diisocyanate. Non-limiting examples of suitable alicyclic polyisocyanates are isophorondiisocyanate, cyclohexanediethanol, methylcyclohexylamine, bis(isocyanatomethyl)cyclohexane, bis(isocyanatophenyl)-methane, bis(isocyanatophenyl)-2,2-propane, bis(isocyanatophenyl)-1,2-ethane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl[2.2.1]heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-from cyanopropyl)-5-isocyanatomethyl[2.2.1]heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl[2.2.1]heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatomethyl)-bicyclo[2.2.1]heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatomethyl)bicyclo[2.2.1]heptane and 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-(2-isocyanatomethyl)-bicyclo[2.2.1]heptane.

Non-limiting examples of suitable aromatic polyisocyanates, where the isocyanate groups are not bonded directly to an aromatic ring, are α,α'-xradiation, bis(isocyanatomethyl)benzene, α,α,α',α'-tetramethyldisilane, 1,3-bis(1-isocyanato-1-methyl-ethyl)benzene, bis(isocyanatomethyl)benzene, bis(isocyanatomethyl)-naphthalene, bis(isocyanatomethyl)diphenyl ether, bis(isocyanatomethyl)phthalate, mesitylenesulfonic and 2,5-di(isocyanatomethyl)furan.

Non-limiting examples of suitable aromatic polyisocyanates having isocyanate groups connected directly to the aromatic ring, are, delete the entry, ativanindications, isopropylidenediphenol, dimethylphenylsilane, diethylphenylphosphine, diisopropylaminoethanol, trimethylbenzenesulfonyl, benzodiazelines, benzotriazolyl, naphthalenedisulfonate, methylnaphthalene, biphenylmethane, ortho-toluylenediisocyanate, ortho-collideinvestment, EO is o-tolylenediisocyanate, 4,4'-diphenylmethanediisocyanate, bis(3-methyl-4-isocyanatophenyl)methane, bis(isocyanatophenyl)ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, triphenyltetrazolium, polymeric 4,4'-diphenylmethanediisocyanate, naphthalenesulfonate, difenilmetana-2,4,4'-triisocyanate, 4-methyldiphenylamine-3,5,2',4',6'-pentazocine, diisocyanate diphenyl ether, bis(isocyanatophenyl)glycol, bis(isocyanatophenyl-ester)-1,3-propylene glycol, benzophenantridin, karbasian, ethylcarbodiimide and dichlorobutadiene.

In some non-limiting embodiments, the implementation can be used sulfur-containing isocyanates following General formula (I):

where R10and R11each independently from each other represents C1-C3-alkyl.

Non-limiting examples of suitable aliphatic polyisocyanates containing sulfide bridges are codetermination, thiodipropionate, dithiodimorpholine, dimethylsulfoniopropionate, datetimedigitized, datetimedigitized, dithiodipropionic and dicyclohexylmethane-4,4'-diisocyanate. Non-limiting examples of suitable aromatic polyisocyanates containing sulfide or disulfide bridges are, but are not limited to, diphenylsulfide-2,4'-isocyanate, diphenylsulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatomethyl, bis(4-isocyanatobenzyl)-sulfide, diphenyldisulfide-4,4'-diisocyanate, 2,2'-dimethyldiphenylamine-5,5'-diisocyanate, 3,3'-dimethyldiphenylamine-5,5'-diisocyanate, 3,3'-dimethyldiphenylamine-6,6'-diisocyanate, 4,4'-dimethyldiphenylamine-5,5'-diisocyanate, 3,3'-dimethoxypyrimidine-4,4'-diisocyanate and 4,4'-dimethoxypyrimidine-3,3'-diisocyanate.

Non-limiting examples of suitable aromatic polyisocyanates containing sulfonic bridges are diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, residencelife-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 4-methyldiphenylamine-2,4'-diisocyanate, 4,4'-dimethoxyphenylacetone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatobutane, 4,4'-dimethyldiphenylamine-3,3'-diisocyanate, 4,4'-di-tert.-butyldiphenylsilyl-3,3'-diisocyanate and 4,4'-dichlorodiphenylmethane-3,3'-diisocyanate.

Non-limiting examples of aromatic polyisocyanates sulfonamidnuyu type is 4-methyl-3-isocyanatobenzotrifluoride-3'-methyl-4'-isocyanate, dibenzylpiperazine-4,4'-diisocyanate, 4,4'-methoxybenzenesulfonamide-3,3'-diisocyanate and 4-methyl-3-isocyanatobenzotrifluoride-4-ethyl-3'-isocyanate.

Non-limiting examples of podhodyaschuyu are cyclohexanemethylamine; aromatic isothioscyanates where isothiocyanate(s) group(s) not bound(s) directly to the aromatic ring; aromatic isothiocyanates, where isothiocyanate(s) group(s) bound(s) directly to the aromatic ring; heterocyclic isothiocyanates; carbonylation; aliphatic polyisocyanate containing sulfide bridges and mixtures thereof.

Other non-limiting examples of suitable isothioscyanates are aromatic polyisocyanate where isothiocyanate group bonded directly to an aromatic ring, such as phenylenedimethylene; heterocyclic polyisocyanate, such as 2,4,6-triisocyanate-1,3,5-triazine and thiophene-2,5-diisothiocyanate; carbonyl-polyisocyanate; aliphatic polyisocyanate containing sulfide bridges, such as THIOBIS(3-isothiocyanatopropionate); aromatic polyisocyanate containing sulfur atoms, in addition to the sulfur atoms isothiocyanate groups; halogenated, alkylated, alkoxysilane, nitrated modified with carbodiimide modified with urea and modified bureta derivatives such polyisocyanates; and diarizonae and trimeresurus products such isothioscyanates.

Non-limiting examples of suitable aliphatic of polyisocyanates are 1,2-di is socialentity, 1,3-diisothiocyanate, 1,4-diisocyanatobutane and 1,6-diisocyanatohexane. Non-limiting examples of aromatic polyisocyanates containing isothiocyanate groups connected directly to the aromatic ring, are 1,2-diisothiocyanate, 1,3-diisothiocyanate, 1,4-diisothiocyanate, 2,4-diisothiocyanate, 2,5-diisothiocyanato-m-xylene, 4,4'-diisothiocyanato-1,1'-biphenyl, 1,1'-methylene-bis(4-isothiocyanatobenzene), 1,1'-methylene-bis(4-isothiocyanato-2-methylbenzoyl), 1,1'-methylene-bis(4-isothiocyanato-3-methylbenzoyl), 1,1'-(1,2-ethandiyl)bis(4-isothiocyanatobenzene), 4,4'-diisocyanatobutane, 4,4'-diisothiocyanato-3,3'-dimethylbenzophenone, benzanilide-3,4'-diisocyanate, diphenyl ether-4,4'-diisothiocyanate and diphenylamine-4,4'-diisothiocyanate.

Non-limiting examples of suitable carbonyl-isothioscyanates are hexanediamine, nonanediol-diisocyanate, diisothiocyanate carbonic acid, 1,3-benzoldicarbonic, 1,4-benzoldicarbonic and (2,2'-bipyridine)-4,4'-decarbonisation. Non-limiting examples of suitable aromatic polyisocyanates containing sulfur atoms in addition to the sulfur atoms isothiocyanate groups are 1-isothiocyanato-4-[(2-isothiocyanato)sulfonyl]benzene, THIOBIS(4-isothiocyanatobenzene), sulfanilic(4-isothiocyanatobenzene), sulfinyl the s(4-isothiocyanatobenzene), dithiobis(4-isothiocyanatobenzene), 4-isothiocyanato-1-[(4-isothiocyanatobenzene)sulfonyl]-2-methoxy-benzene, phenyl ether 4-methyl-3-isothiocyanatobenzene-4'-isothiocyanate and 4-methyl-3-isothiocyanatobenzene-3'-methyl-4'-isothiocyanate.

Other non-limiting examples of isocyanates with isocyanate and isothiocyanate groups represent materials, including aliphatic, alicyclic, aromatic or heterocyclic groups and which optionally may contain sulfur atoms in addition to the sulfur atoms isothiocyanate groups. Non-limiting examples of such materials are 1-isocyanato-3-isothiocyanatopropionate, 1-isocyanato-5-isothiocyanatobenzene, 1-isocyanato-6-isothiocyanates, isocyanatobenzene, 1-isocyanato-4-isothiocyanatobenzene, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-isocyanato-1-isothiocyanatobenzene, 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, 4-isocyanato-4'-isothiocyanatobenzene and 2-isocyanato-2'-isothiocyanatobenzene.

In some non-limiting embodiments, the implementation of the isocyanate contains at least one triisocyanate or at least one trimer MDI. Non-limiting examples of such isocyanates are aromatic triisocyanate, such as Tris(4-isocyanatophenyl)methane (DESMODUR R), 1,3,5-Tris(3-what sociando-4-were)-2,3,6-trioxosilicate-1,3,5-triazine (DESMODUR IL); adducts of aromatic diisocyanates, such as adduct of 2,4-tolylenediisocyanate (TDI, TDI, 2,4-diisocyanate) and trimethylolpropane (DESMODUR L); and aliphatic triisocyanate, such as N-isocyanatohexylaminocarbonylamino-N,N'-bis(isocyanatophenyl)urea (DESMODUR N), 2,4,6-trioxo-1,3,5-Tris(6-isocyanatophenyl)hexahydro-1,3,5-triazine (DESMODUR N3390), 2,4,6-trioxo-1,3,5-Tris(5-isocyanato-1,3 .3m-trimethyl-cyclohexylmethyl)hexahydro-1,3,5-triazine (DESMODUR Z4379) and 4-(isocyanatomethyl)-1,8-octadienal. The above DESMODUR products are commercial products of Bayer Corp. Can also be used biuret exanguination, polymer mechanisation and polymer isophorondiisocyanate, trimers of hexamethylenediisocyanate, isophoronediisocyanate and tetramethylethylenediamine.

In some non-limiting embodiments, the implementation of the polyisocyanate used as a precursor for obtaining prepolymer poliuretanovye is a cycloaliphatic compound, such as a dual connection, connected by bridge with isopropylidene group or alkilinity group of 1-3 carbon atoms.

The reaction components for the preparation of polyurethane Groups And also include from about 0.1 to 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and, at least 3 hydroxyl groups. As discussed above, the branched polyol may increase the free volume within the polymer matrix to provide space for movement or rotation of molecules at impact.

Used in this case, the term "polyol" includes compounds, monomers, oligomers and polymers containing at least two hydroxyl groups (e.g., diols) or at least three hydroxyl groups (for example, triola), higher functional polyols and mixtures thereof. Acceptable polyols capable of forming a covalent bond with reactive groups such as isocyanate functional group.

Non-limiting examples of suitable polyols are aliphatic, cycloaliphatic, aromatic, heterocyclic, oligomeric and polymeric polyols and mixtures thereof. In some embodiments, implement, for example, in the case of transparent products, or Windows exposed to sunlight, can be used aliphatic or cycloaliphatic polyols.

The number of carbon atoms in the polyol described above for the Group a may be in the range from 4 to 18, or from 4 to 12, or from 4 to 10, or from 4 to 8, or from 4 to 6 carbon atoms. In some non-limiting embodiments of the invention one or more of the carbon atoms in the polyol can is to be substituted by one or more heteroatoms, such as N, S or O.

As discussed above, the branched polyol that can be used as the reaction product to obtain a polyurethane Group And contains from 4 to 18 carbon atoms and at least 3 hydroxyl groups. Non-limiting examples trifunctionally, tetrafunctional and higher polyols for use as the branched polyols are albanology branched chain, such as glycerin, tetramethyllead, trimethylated (for example, 1,1,1-trimethylated), trimethylolpropane (TMP, str) (for example, 1,1,1-trimethylolpropane), aritra, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitan, alkoxysilane derivatives (described below), as well as mixtures thereof.

In some non-limiting embodiments of the invention, the polyol can be cycloalkenyl, such as trimethylene-bis(1,3,5-cyclohexanediol).

In some non-limiting embodiments of the invention, the polyol can be an aromatic polyol such as trimethylene-bis(1,3,5-sensation).

Other non-limiting examples of suitable polyols include the above-mentioned polyols, which can be alkoxysilane derivatives, for example ethoxylated, propoxycarbonyl and butoxycarbonyl derivatives. In alternate non-limiting is the option of implementing these polyols can be alkoxysilane using 1-10 alkoxy groups include glycerol, trimethylated, trimethylolpropane, sensation, cyclohexanethiol, aritra, pentaerythritol, sorbitol, mannitol, sorbitan, dipentaerythritol and tripentaerythritol. In alternate non-limiting embodiments, the implementation alkoxysilane, ethoxylated and propoxycarbonyl polyols and mixtures thereof can be used alone or in combination with alkoxycarbonyl, methoxycarbonyl and neproporcionalnimi polyols containing at least three hydroxyl groups, and mixtures thereof. The number of alkoxy groups can be from 1 to 10, or from 2 to 8, or any suitable number between 1 and 10. In a non-limiting embodiment, the alkoxy group can be ethoxy group and the number of ethoxy groups can be from 1 to 5 units. In another non-limiting embodiment of the invention, the polyol may be trimethylolpropane containing up to 2 ethoxy groups. Non-limiting examples of suitable alkoxysilane ethoxylated polyols are trimethylolpropane, propoxycarbonyl trimethylolpropane, the ethoxylated trimethylated and mixtures thereof.

Can be used mixtures of any of the above polyols.

In some embodiments of the invention, the polyurethanes of the present invention may be a thermoplastic, such as polyurethane, having a molecular weight per cross with whom ivko, at least about 6000 g/mol.

In some non-limiting embodiments of the invention the branched polyol containing from 4 to 18 carbon atoms that may have srednecenovogo molecular weight of approximately from 100 to 500 g/mol. In some non-limiting embodiments of the invention, the polyol can have srednecenovogo molecular weight of less than about 450 g/mol. In other non-limiting embodiments of the invention, the polyol can have srednecenovogo molecular weight less than about 200 g/mol.

The reaction components for the production of polyurethane Groups And contain from approximately 0.1 to 0.9 equivalents of at least one diol containing from 2 to 18 carbon atoms, or from about 2 to 14 carbon atoms, or from 2 to 10 carbon atoms, or from 2 to 6 carbon atoms. In some non-limiting embodiments, one or more carbon atoms in diola can be substituted by one or more heteroatoms, such as N, S or O.

Non-limiting examples of suitable diols are linear arcangioli, such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol; 1,2-ethanediol; propandiol, such as 1,2-propandiol and 1,3-propandiol; butandiol, such as 1,2-butanediol, 1,3-butanediol and 1,4-butanediol; pentanediol, such as 1,5-pentanediol, 1,3-pentandiol and 2,4-pentanediol; hexandiol, such as 1,6-hexanediol and 2,5-hexanediol; heptanediol, such as 2,4-heptanediol; octandiol, such as 1,8-octanediol; nonanediol, such as 1,9-nonanediol; decandiol, such as 1,10-decanediol; dodecanediol, such as 1,12-dodecanediol; octadecanol, such as 1,18-octadecanol; sorbitol, mannitol and mixtures thereof. In some non-limiting embodiments, the implementation of the diol is a propandiol, such as 1,2-propandiol and 1,3-propandiol, or butanediol, such as 1,2-butanediol, 1,3-butanediol and 1,4-butanediol. In some non-limiting embodiments of the invention one or more of the carbon atoms in the polyol may be substituted by one or more heteroatoms, such as N, S or O; for example, from sulphonated polyols, such as dithioketal-bettiol, thiodiethanol, such as 2,2-thiodiethanol or 3,6-dithia-1,2-octanediol.

Other non-limiting examples of suitable diols include diols represented by the following formula:

where R represents a C0-C18-divalent linear or branched, aliphatic, cycloaliphatic, aromatic, heterocyclic, or oligomeric saturated alkalinity radical or mixtures thereof; C2-C18is a divalent organic radical containing at least one element selected from the group comprising a sulfur atom,oxygen and silicon, in addition to carbon atoms and hydrogen; C5-C18-bivalent saturated cycloalkenyl radical; or (C5-C18-bivalent saturated heterozygosity radical; and R' and R” may be present or absent and, if present, each independently from each other represents C1-C18-divalent linear or branched, aliphatic, cycloaliphatic, aromatic, heterocyclic, polymeric, or oligomeric saturated alkalinity radical or mixtures thereof.

Other non-limiting examples of suitable diols are branched arcangioli, such as propylene glycol, dipropyleneglycol, tripropyleneglycol, neopentylglycol, 2-methylbutanol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,3-propandiol, 2,2-dimethyl-1,3-propandiol, dibutil-1,3-propandiol, polyalkylene glycols such as polyethylene glycol and mixtures thereof.

In some non-limiting embodiments of the invention, the diol can be cycloalkenyl, such as cyclopentanediol, 1,4-cyclohexanediol; cyclohexanedimethanol (CHDM, CHDM), such as 1,4-cyclohexanedimethanol, cyclododecanol, 4,4'-isopropylidenedicyclohexanol, hydroxypropylcellulose, cyclohexanedimethanol, 1,2-bis(hydroxymethyl)cyclohexane, 1,2-bis(hydroxyethyl)cyclohex is h, 4,4'-isopropylidenedicyclohexanol, bis(4-hydroxycyclohexyl)-methane and mixtures thereof.

In some non-limiting embodiments, the implementation of the diol can be an aromatic diol, such as dihydroxybenzene, 1,4-benzylimidazole, xianglian, hydroxybenzoyl alcohol and dihydroxytoluene; bisphenol, such as 4,4'-isopropylidenediphenol, 4,4'-oxybisethanol, 4,4'-dihydroxybenzophenone, 4,4'-thiobisphenol, phenolphthalein, bis(4-hydroxyphenyl)methane, 4,4'-(1,2-ethandiyl)bisphenol and 4,4'-sulfonylurea; halogenated bisphenol, such as 4,4'-isopropylidenebis(2,6-dibromophenol), 4,4'-isopropylidenebis(2,6-dichlorophenol) and 4,4'-isopropylidenebis(2,3,5,6-tetrachlorophenol); alkoxysilane bisphenola, which may be, for example, ethoxy-, propoxy-, α-butoxy - and β-butoxy group; and bicyclohexyl, which can be obtained by hydrogenation of the corresponding bisphenols, such as 4,4'-isopropylidenedicyclohexanol, 4,4'-oxybisethanol, 4,4'-diabeticmedicine and bis(4-hydroxycyclohexyl)methane, the product of alkylation of 1 mole of 2,2-bis(4-hydroxyphenyl)propane (bisphenol-A) and 2 moles of propylene oxide; hydroxyalkylated such as meta - or para-bis(2-hydroxyethyl)terephthalate, bis(hydroxyethyl)hydroquinone, and mixtures thereof.

In some non-limiting embodiments of the invention, the diol may be a hetero who Ilichevsky diol, for example dihydroxypyridine, such as 1,4-bis(hydroxyethyl)piperazine.

In some non-limiting embodiments of the invention, the diol can be an amide or alinamin (such as academic (oksamid)), for example N,N'-bis(2-hydroxyethyl)-oksamid.

In some non-limiting embodiments of the invention, the diol can be a diol propionate, for example 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate.

In some non-limiting embodiments of the invention, the diol can be a diol as such as bishydroxycoumarin.

In some non-limiting embodiments of the invention, the diol can be a diol phthalate, such as meta - or para-bis(2-hydroxyethyl)terephthalate.

In some non-limiting embodiments of the invention, the diol may be a diol, hydroquinone, such as dihydroxytryptamine.

In some non-limiting embodiments of the invention, the diol can be a diol of isocyanurate, such as dihydroxyethylene.

In some non-limiting embodiments, the implementation of the diol for use in the present invention may be a SH-containing material, such as politiely having at least three tirinya group and from 4 to 18 carbon atoms. Non-limiting examples of suitable policylaw what there might be, but without their limitations, aliphatic politely, cycloaliphatic politely, aromatic politely, heterocyclic politely, polymer politely, oligomeric politely and mixtures thereof. Containing sulfur and containing an active hydrogen atom, the material can have bridges, including, but without limiting them, ether bridges (-O-), sulfide bridges (-S-), polysulfide bridges (-Sx-where x has a value of at least 2, or from 2 to 4) and combinations of such bridges. Used in this case, the definition of "thiol", "Tolna group", "mercapto" or "mercapto group" refer to the SH-group, which can form touracademy bridge (that is-NH-C(O)-S-) with the isocyanate group or detiorating bridge (that is-NH-C(S)-S-) with isothiocyanato group.

In some non-limiting embodiments, the implementation of the polyurethane components are essentially not include SH-containing materials, i.e. contain less than about 5% of the mass. SH-containing material, in other non-limiting embodiments, they contain less than about 2% of the mass. SH-containing materials, and in other non-limiting embodiments, SH-containing materials are not available.

In some non-limiting embodiments of the invention diol containing from 4 to 18 carbon atoms that may have srednecenovogo molecular mass approximately the nutrient from 200 to 10000 g/mol, or less than about 500 g/mol, or less than about 200 g/mol.

Can be used mixtures of any of the above diols.

In some non-limiting embodiments of the invention, the reaction components for the production of polyurethane group And may additionally include one or more unbranched triolo and/or one or more unbranched more highly functional polyols.

Non-limiting examples of suitable unbranched triolo and unbranched more highly functional polyols are aliphatic, cycloaliphatic, aromatic, heterocyclic, oligomeric and polymeric polyols, and mixtures thereof.

In some non-limiting embodiments of the invention, the polyol can be cycloalkenyl, such as cyclohexanediol (for example,1,3,5-cyclohexanediol).

In some non-limiting embodiments of the invention, the polyol can be an aromatic polyol, such as sensation (e.g., 1,2,3-sensation, 1,2,4-benzothia and 1,3,5-sensation) and phenolphthalein.

In some non-limiting embodiments of the invention, the polyol may be a polyol isocyanurate, such as Tris(hydroxyethyl)isocyanurate.

In some non-limiting embodiments of the invention, the reaction components for polio ETANA Group And may additionally include one or more branched or non-branched polyols (diols, triolo and/or more highly functional polyols containing more than 18 carbon atoms.

Non-limiting examples of suitable polyols containing more than 18 carbon atoms, a linear or branched aliphatic polyols, cycloaliphatic polyols, aromatic polyols, heterocyclic polyols, oligomeric polyols, polymer polyols, and mixtures thereof.

Non-limiting examples of suitable linear or branched aliphatic polyols containing more than 18 carbon atoms are 1,18-eicosanol and 1,24-Tatralandia.

Other non-limiting examples of suitable polyols containing more than 18 carbon atoms, polyols are represented by the following formula:

where R represents a C0-C30-divalent linear or branched, aliphatic, cycloaliphatic, aromatic, heterocyclic, or oligomeric saturated alkalinity radical or mixtures thereof; C2-C30is a divalent organic radical containing at least one element selected from the group comprising a sulfur atom, oxygen and silicon in addition to carbon atoms and hydrogen; C5-C30-bivalent saturated cycloalkenyl radical; or (C5-C30-bivalent saturated heterozygosity radika is; and R' and R” may be present or absent and, if present, each independently represents a C1-C30-divalent linear or branched, aliphatic, cycloaliphatic, aromatic, heterocyclic, polymeric, or oligomeric saturated alkalinity radical or mixtures thereof.

Non-limiting examples of suitable cycloaliphatic polyols containing more than 18 carbon atoms are bicyclohexyl containing more than 18 carbon atoms, which may be obtained by hydrogenation of the corresponding bisphenols.

Non-limiting examples of suitable aromatic polyols containing more than 18 carbon atoms are bisphenola, alkoxysilane bisphenol, such as alkoxycarbonyl 4,4'-isopropylidenediphenol, which may contain from 3 to 70 alkoxy groups.

Other non-limiting examples of suitable oligomeric and polymeric polyols having more than 18 carbon atoms include higher polyalkylene glycols such as polyethylene glycols, having Srednekanskaya molecular weight in the range from about 200 to 2000 g/mol, and mixtures thereof.

In some non-limiting embodiments, the implementation of the polyol for use in the present invention may be a SH-containing material, such as politiely, soda is official at least two tirinya group or, at least, three tirinya group, and at least 18 carbon atoms. Non-limiting examples of suitable policylaw can be, but not limited to, aliphatic politely, cycloaliphatic politely, aromatic politely, heterocyclic politely, polymer politely, oligomeric politely, and mixtures thereof. Containing sulfur and containing an active hydrogen atom, the material can have bridges, including, but without limiting them, ether bridges (-O-), sulfide bridges (-S-), polysulfide bridges (-Sx-where x has a value of at least 2, or from 2 to 4) and combinations of such bridges. Used in this case, the definition of "thiol", "Tolna group", "mercapto" or "mercapto group" refer to the SH-group, which can form touracademy bridge (that is-NH-C(O)-S-) with the isocyanate group or detiorating bridge (that is-NH-C(S)-S-) with isothiocyanato group.

In some non-limiting embodiments, the implementation of the polyurethane components are essentially not include SH-containing material, i.e. contain less than about 5% of the mass. SH-containing material, in other non-limiting embodiments, they contain less than about 2% of the mass. SH-containing materials, and in other non-limiting variant of the SH-containing materials are not available.

In some non-limiting embodiments, the implementation of a polyol containing at least 18 carbon atoms that may have srednecenovogo molecular weight of from about 200 to 5000 g/mol, or from about 200 to 4000 g/mol, or at least about 200 g/mol, or at least about 400 g/mol, or at least about 1000 g/mol, or at least about 2000 g/mol. In some non-limiting embodiments of the invention, the polyol can have srednecenovogo molecular weight less than about 5000 g/mol, or less than about 4000 g/mol, or less than about 3,000 g/mol, or less than about 2000 g/mol, or less than about 1000 g/mol, or less than about 500 g/mol.

Can be used mixtures of any of the above polyols. For example, the polyol may include trimethylolpropane and diol may include butanediol and/or pentanediol.

As discussed above, the number of branched polyol used to obtain polyurethane Groups And ranged from approximately 0.1 to 0.9 equivalent. In some non-limiting embodiments of the invention, the number of branched polyol used to obtain the polyurethane is from about 0.3 to 0.9 equivalent. In other non-limiting embodiments, from whom retene number of branched polyol, used to obtain the polyurethane is about 0.3 equivalent.

As discussed above, the amount of diol used to obtain polyurethane Groups And ranged from approximately 0.1 to 0.9 equivalent. In some non-limiting embodiments of the invention, the amount of diol used to obtain the polyurethane is from about 0.3 to 0.9 equivalent. In other non-limiting embodiments of the invention, the amount of diol used to obtain the polyurethane is about 0.3 equivalent.

In some non-limiting embodiments, the implementation of the polyurethanes of Group a reaction components contain from about 0.1 to 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, and from about 0.1 to 0.9 equivalents of at least one diol containing from 2 to 18 carbon atoms per 1 equivalent of at least one MDI, where the reaction product components are essentially does not contain complex polyetherpolyols and simple polyetherpolyols and where the components of the reaction is maintained at a temperature of at least approximately 100°C for at least about 10 minutes.

In some embodiments of the invention the polyurethane content is t the reaction product components, includes: about 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate); approximately 0.3 to 0.5 equivalents of trimethylolpropane; and from about 0.3 to 0.7 equivalents of butanediol or pentanediol, or about 0.7 equivalents of butanediol or pentanediol; where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

In another embodiment, the present invention provides polyurethanes of Group a, containing the reaction product of components comprising: about 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate); about 0.3 equivalents of trimethylolpropane; and about 0.7 equivalents of 1,10-dodecanediol; where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

In another embodiment, the present invention provides polyurethanes of Group a, containing the reaction product of components comprising: about 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate); about 0.3 equivalents of trimethylolpropane; and about 0.7 equivalents of 1,5-pentanediol; where the components of the reaction is maintained at a temperature of at least about 100°C., at least within about 10 mi the ut.

In another embodiment, the present invention provides polyurethanes of Group a, containing the reaction product of components comprising: about 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate); about 0.3 equivalents of trimethylolpropane; and about 0.7 equivalents of 1,4-butanediol; where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

In another embodiment, the present invention provides polyurethanes of Group a, containing the reaction product of components comprising: about 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate); about 0.4 equivalents of trimethylolpropane; and about 0.6 equivalent of 1.18-octadecanol; where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

The polyurethanes of Group a can be a good ballistic resistance, such as resistance to penetration, resistance to penetration or cracking due to impact from a projectile such as a bullet or shot, which is produced from a gun, guns, rifle, AK-47 or other shooting devices or explosives. In some embodiments of the invention, the polyurethanes of Group a tol the other of 0.75” (1.9 cm) or more will stop and reflect: 9 mm (125 GP) bullet, released with an initial velocity of 1350 ft/sec (411,5 m/s) from a distance of 20 feet; the bullet 0.40 caliber, released with initial velocity 987 ft/sec (300,8 m/s) from a distance of 20 feet (6.1 m); and/or gun shell 12 gauge, released with initial velocity of 1290 ft/sec (393,2 m/s) from a distance of 20 feet (6.1 m).

Group

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes of group b, containing the reaction product of components comprising: (a) urethane prepolymer with isocyanate functionality, containing the reaction product of components comprising: (i) about 1 equivalent of at least one MDI; and (ii) from about 0.1 to 0.5 equivalent, of at least one diol containing from 2 to 18 carbon atoms, and (b) from about 0.05 to 0.9 equivalents of at least one polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and (C) until about 0.45 equivalents of at least one diol containing from 2 to 18 carbon atoms, where the reaction product components are essentially does not contain complex polyetherpolyols and simple polyetherpolyols.

Non-limiting examples and the number of suitable polyisocyanates, diols and polyols for use in the reaction products to obtain polyurethanes of Group b, the detail is discussed above in the consideration of Group A. Methods of obtaining polyurethanes Group discussed in more detail below.

Group

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes of Group-containing reaction product of components comprising: at least one polyisocyanate selected from the group comprising trimers MDI and branched polyisocyanates, the polyisocyanate contains at least three isocyanate functional groups; and at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least two hydroxyl groups, where the reaction product components are essentially does not contain complex polyetherpolyols and simple polyetherpolyols.

In other non-limiting embodiments, the implementation of the present invention provides polyurethanes of Group-containing reaction product of components comprising: about 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate); about 1.1 equivalents of butanediol; and about 0.1 equivalent of a trimer of isophorondiisocyanate.

Non-limiting examples of suitable trimers MDI, branched polyisocyanates and aliphatic polyols (including, but without limiting them, linear, branched or cycloaliphatic polyols for use as the reaction Ave the products to obtain polyurethanes Group discussed in detail above for the Group A. Can be used number of trimer(s) of MDI and/or branched(s) MDI(s), similar to the amounts described above for the MDI Group A. in Addition, to obtain polyurethanes Group can be used a mixture of trimer(s) of MDI and/or branched(s) MDI(s) with other unbranched or detrimentally the polyisocyanates described above.

In some non-limiting embodiments, the implementation of the polyurethane Group With the reaction components contain from about 0.1 to 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups per 1 equivalent of at least one MDI, and in other non-limiting embodiments, the implementation of approximately 0.3 to 0.9 equivalent of at least one aliphatic polyol containing from 2 to 18 carbon atoms, where the reaction product components are essentially does not contain complex polyetherpolyols and simple polyetherpolyols.

As discussed above, in some non-limiting embodiments, the implementation of Group a, group b and Group From the reaction product components are essentially does not contain complex polyetherpolyols and simple polyetherpolyols. Used in this case, the expression "essentially no content the t complex polyetherpolyols and simple polyetherpolyols" means, what is the reaction product of components contains less than about 10% of the mass. complex polyetherpolyols and/or simple polyetherpolyols, or less than about 5% of the mass. complex polyetherpolyols and/or simple polyetherpolyols, or less than about 2% of the mass. complex polyetherpolyols and/or simple polyetherpolyols, or do not contain complex polyetherpolyols and/or simple polyetherpolyols.

Non-limiting examples of such complex polyether polyols are polyesters of glycols, polycaprolactone, polycarbonatediol and mixtures thereof. Polyesters of glycols can include the products of esterification of one or more dicarboxylic acids containing from four to ten carbon atoms, for example, but without limiting them, amber and sabatinovka acids, with one or more low molecular weight glycols containing from two to ten carbon atoms, such as, but without limitation, ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentylglycol, 1,6-hexanediol and 1,10-decanediol. Methods of esterification for the production of complex polyether polyols are described, for example, in the article: D.M. Young, F. Hostettler et al., “Polyesters from Lactone”, Union Carbide F-40, p. 147.

Non-limiting examples of polycaprolactone are polyols obtained by the condensation of caprolactone in the presence of difunctional the aqueous material with an active hydrogen atom, such as water or low molecular weight glycols, such as ethylene glycol and propylene glycol. Non-limiting examples of suitable polycaprolactone can be commercially available materials, denoted as series SARA company Solvay Chemical of Houston, Texas, such as SARAH A and SARAH A, and a series of TONE Dow Chemical of Midland, Michigan, such as TONE 0201, 0210, 0230 0241 and. In some non-limiting embodiments polycaprolactone has a molecular weight in the range from about 500 to 2000 g / mol, or from about 500 to 1000 g/mol.

Non-limiting examples of polycarbonatediol are aliphatic polycarbonate diols, for example diols based alkalophile, ethers of glycols, alicyclic glycols or mixtures thereof. In some embodiments alkylene groups to receive polycarbonatediol can contain from 5 to 10 carbon atoms and can be linear, cycloalkanones or their combinations. Non-limiting examples of such alkilinity groups are hexylen, octiles, deciles, cyclohexyl and cyclohexylmethyl. Suitable polycarbonate polyols can be obtained in non-limiting examples, the reaction is terminated with hydroxy group alkalophilus with dialkylammonium, such as methyl-, ethyl-, n-propyl or n-BUTYLCARBAMATE, or diallerbutton, such as diphenyl or Dean shall talkabout, or by reaction of hydroxy-terminated group Allendale with phosgene or bischloromethyl, by methods known to experts in this field of technology. Non-limiting examples of such polycarbonate polyols are polycarbonatediol, commercially available as RavecarbTM107 firm Enichem S.p.A. (Polimeri Europa (Italy), and polyacrylonitrile with srednetsenovoj molecular weight of approximately 1000, such as polycarbonatediol CM-1733 obtained from hexandiol, commercial product Stahl. Examples of other suitable polycarbonatediol, which are commercially available, are CM-1122, KM-1667 (obtained from a mixture of 50/50 wt%. cyclohexanedimethanol and hexandiol) (commercially available from Stahl USA Inc. of Peabody, Massachusetts) and DESMOPHEN 2020E (commercial product of Bayer Corp.).

Polycarbonatediol can be obtained by the reaction of diol, such as described above, and diallylmalonate, such as described in U.S. patent No. 4160853. Polycarbonatediol may include polyhexamethylenediamine, such as BUT-(CH2)6-[O-C(O)-O-(CH2)6]nIs HE, where n takes integer values from 4 to 24, or from 4 to 10, or from 5 to 7.

Non-limiting examples of polyether polyols are poly(oxyalkylene)polyols or polyalkoxysiloxanes polyols. Poly(oxyalkylene)polyols can be obtained in accordance with known methods. Neogranichinymi embodiment, poly(oxyalkylene)polyol can be obtained by condensation of accelerated or mixture of alkalisation using acid catalyzed or base mounting with a polyhydric initiator or a mixture of polyhydric initiators such as ethylene glycol, propylene glycol, glycerin and sorbitol. Compatible simple mixture of polyether polyols can also be used. Used in this case, the definition of "compatible" means that two or more materials can be mutually dissolve each other so that essentially form one phase. Non-limiting examples of alkalisation may include ethylene oxide, propylene oxide, butylenes, amelanotic, aralkylated, such as stimulated, a mixture of ethylene oxide and propylene oxide. In some non-limiting embodiments, the implementation polyoxyalkylene can be obtained with mixtures of accelerated using statistical or stepped oxyalkylene. Non-limiting examples of such poly(oxyalkylene)polyols are polyoxyethyleneglycol, such as polyethylene glycol, and polyoxypropyleneamine, such as polypropyleneglycol.

Other simple polyether polyols are block polymers, such as block polymers having units of the ethylene oxide-propylene oxide and/or ethylene oxide-butylenes. In some non-limiting embodiments of the invention a simple polyether polyols include a block copolymer of the following formula:

BUT-(CHR1CHR2-O)a-(CHR3CHR4-O)b-(CHR5CHR6-O)c/sub> -H

where R1-R6each independently of one another may be a hydrogen atom or methyl; and the indices a, b and c each independently of one another may be selected from integers from 0 to 300, where a, b and c are chosen so that Brednikova molecular weight of the polyol is less than about 32000 g/mol, or less than approximately 10000 g/mol, when determining by using GPC. In other non-limiting embodiments, the implementation of a, b and c each independently from each other may be an integer from 1 to 300. In other non-limiting embodiments, R1, R2, R5and R6can represent a hydrogen atom, and R3and R4each independently from each other selected from a hydrogen atom and methyl, provided that R3and R4differ from each other. In other non-limiting embodiments, R3and R4can represent a hydrogen atom, and R1and R2each independently of one another may be selected from a hydrogen atom and methyl, provided that R1and R2differ from each other, and R5and R6each independently of one another may be selected from a hydrogen atom and methyl, provided that R5and R6differ from each other.

In some non-limiting embodiments, the implementation polyalkoxysiloxanes polyols can b shall be represented by the following General formula:

Formula (I')

where m and n each can be an integer positive values, and the sum of m and n is from 5 to 70; R1and R2each represents a hydrogen atom, methyl or ethyl; and a is a divalent linking group such as linear or branched alkylene, which may contain from 1 to 8 carbon atoms, phenylene and C1-C9-alkyl-substituted phenylene. The values of m and n, in combination with the selected divalent linking group, determine the molecular weight of the polyol. Polyalkoxysiloxanes polyols can be obtained by methods which are well known in this field. In non-limiting embodiments, the implementation of a polyol, such as 4,4'-isopropylidenediphenol, may be introduced into reaction with oxirane-containing material, such as ethylene oxide, propylene oxide or butylenes, education material, usually referred to as ethoxylated, propoxycarbonyl or butoxycarbonyl a polyol having hydroxyl functionality. Non-limiting examples of polyols suitable for use in preparation of polyalkoxysiloxanes polyols can be polyols, which are described in U.S. patent No. 6187444 B1, column 10, lines 1-20, which is included in the description by reference.

In some non-limiting embodiments implement the program simple polyetherpolyols can be an ethylene oxide/propylenoxide PLURONIC block copolymers, such as PLURONIC R and PLURONIC L62D, and/or tetrafunctional block copolymers based on ethylene oxide and propylene oxide TETRONIC, such as TETRONIC R, which are commercial products BASF Corp. of Parsippany, New Jersey.

Used in this case, the expression "simple polyether polyols may also include poly(oxytetracyline)-diols obtained by polymerization of tetrahydrofuran in the presence of catalysts, Lewis acids, such as, but without limiting them, boron TRIFLUORIDE, tin chloride(IV) and sulphonylchloride.

Group D

In some non-limiting embodiments, the present invention provides polyurethanes of Group D, containing the reaction product of components comprising: at least one polyisocyanate; at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and at least one polyol containing one or more bromine atoms, one or more phosphorus atoms or combinations thereof. Brominated and Vospominanie polyols can give a polyurethane with high fire resistance. The resistance of the polyurethanes of the present invention can be determined by simple exposure to the flame, to determine whether the polymer self-extinguishing or will it burn more slowly than the polymer in the absence of a brominated or postnatalnogo polyol is, or in accordance with the test Underwritter's Laboratory Test UL-94.

In other non-limiting embodiments, the present invention provides polyurethanes of Group D, containing the reaction product of components comprising: about 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate); approximately 0.3 to 0.5 equivalents of trimethylolpropane; from about 0.2 to 0.5 equivalent of bis(4-(2-hydroxyethoxy)for 3,5-dibromophenyl)-sulfone; from about 0.2 to 0.5 equivalent of 1,4-cyclohexanedimethanol; and from about 0.2 to 0.5 equivalent of 3.6-dithia-1,2-octanediol.

Non-limiting examples of suitable polyisocyanates and branched polyols containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, for use as the reaction products to obtain polyurethanes of Group D discussed in detail above for the Group A.

Non-limiting examples of suitable polyols containing one or more bromine atoms, one or more phosphorus atoms or combinations thereof, are 4,4'-isopropylidene-bis(2,6-dibromophenol), isopropylidene bis[2-(2,6-dibromophenoxy)ethanol], bis(4-(2-hydroxyethoxy)for 3,5-dibromophenyl)sulfon, heptanes(dipropyleneglycol)triphosphate, Tris(dipropyleneglycol)phosphate, diethyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate and mixtures thereof. Non-limiting examples of suitable fo tonirovannykh polyols are polyols of the formula HO-Y-O[POOR-O-Y-O][POOR-O-Y-OH], where each R independently from each other selected from alkalinous group having 1-10 repeating units, for example from CH2until (CH2)10and each Y independently from each other selected from alkalinous group having from 1 to 6 repeating units, for example, from CH2until (CH2)6.

The amount of brominated polyols and/or fosforilirovannyh polyols used to obtain the polyurethane of group D may be approximately from 0.1 to 0.9 equivalent, or approximately 0.3 to 0.9 equivalent, or about 0.3 equivalent.

In some non-limiting embodiments of the invention, the reaction components may also include one or more simple polyether polyols and/or complex polyether polyols described above. If they are present, the number of ordinary polyether polyols and/or complex polyether polyols used to obtain the polyurethane of group D may be approximately from 0.1 to 0.9 equivalent, or approximately 0.3 to 0.9 equivalent, or about 0.3 equivalent.

Groups A-D

In some non-limiting embodiments, the implementation of the polyurethanes of group a-D, the reaction products can further comprise one or more components selected from among the following: poliuretanoviy, (meth)acrylamide, hydroxy(meth)acrylamide, polyvinylbutyrate, polymers containing (meth)acrylate with a hydroxyl functionality, polymers containing allyl alcohols, polyetherimide and mixtures thereof. In some embodiments, the implementation of polymerization acrylamide can give interpenetrating polymer network having a high transparency, good impact strength and high young's modulus.

Non-limiting examples of suitable poliuretanovuyu are the reaction products of an excess of MDI and branched or linear polyol. The equivalent ratio of MDI to the polyol may be in the range from about 1.0 to:0,05 to 1,0:0.3 or is approximately 1.0:0.7 to. The number of poliuretanovuyu can be in the range from about 1 to 90 wt. -%, from about 5 to 70 wt. -%, or from about 20 to 50 wt%. based on the total weight of components.

Non-limiting examples of suitable acrylamides are acrylamide, methacrylamide and dimethylacrylamide. Acrylamide may be added together with all other components of the reaction, or it can be dissolved in diola and then mixed with other components of the reaction. The amount of acrylamide can be in the range from about 5 to 70 wt. -%, from about 10 to 50 wt. -%, or from about 10 to 30% of the mass. based on the total weight of the computer is required.

Non-limiting examples of suitable polyvinyl alcohols include polyvinyl alcohol. The amount of polyvinyl alcohol may be in the range from about 5 to 90 wt. -%, from about 10 to 70 wt. -%, or from about 10 to 40 wt%. based on the total weight of components.

Non-limiting examples of suitable polymers containing (meth)acrylate with a hydroxyl functionality are hydroxypropylamino; hydroxyethylacrylate; hydroxypropylmethacrylate; hydroxyethylmethacrylate; and copolymers containing hydroxyl functional (meth)acrylates with acrylamide, cyanoethyl(meth)acrylates, methylmethacrylate, methacrylates, ethacrylate, propylacetate and vinyl pyrrolidone. The number of (meth)acrylate with a hydroxyl functionality may be in the range from about 10 to 90 wt. -%, from about 10 to 70 wt. -%, or from about 10 to 30% of the mass. based on the total weight of components.

Non-limiting examples of suitable polymers containing allyl alcohols, are diethylene glycol bis(allylcarbamate), allelochemicals and diallylmalonate. The number of allyl alcohols can be in the range from about 5 to 70 wt. -%, from about 10 to 50 wt. -%, or from about 10 is about 30% of the mass.

Non-limiting examples of suitable polyetherimides are afieromeno polymers obtained by the reaction of bis-examination, such as N,N'-bis(omega-hydroxyalkyl)-oksamid, with a dicarboxylic acid or complex fluids, such as diethyloxalate, diethylamine, dietilsera or terephthalate. The number polyaminoamide can be in the range from about 10 to 80 wt. -%, approximately from 20 to 60 wt. -%, or from about 30 to 50 wt%. based on the total weight of components.

In some non-limiting embodiments of the polyurethanes of Group a-C, the reaction products can further comprise one or more amine curing agents. Amine curing agent, if present in the polymerization reaction can act as a catalyst may be introduced into the received polymerizat and can form poly(mochevinoi). The amount of amine curing agent may be in the range from about 0.05 to 0.9 equivalent, approximately from 0.1 to 0.7 equivalent, or approximately 0.3 to 0.5 equivalent.

Non-limiting examples of such amine curing agents are aliphatic polyamine, cycloaliphatic polyamine, aromatic polyamine and mixtures thereof. In some non-limiting embodiments, izopet is of amine curing agent may be, at least two functional groups selected from primary amine (-NH2), secondary amine (-NH -), and combinations thereof. In some non-limiting embodiments, amine curing agent can have at least two primary amine groups. In some non-limiting embodiments, all amino groups are primary groups.

Examples of such amine curing agents are compounds having the following formula:

where R1and R2each independently from each other selected from methyl, ethyl, sawn and ISO-propyl groups, and R3selected from a hydrogen atom and chlorine; for example, the following compounds produced by Lonza Ltd. (Basel, Switzerland): LONZACURE®M-DIPA, in which R1= C3H7; R2= C3H7; R3= H; LONZACURE®M-DMA, in which R1= CH3; R2= CH3; R3= H; LONZACURE®M-MEA, in which R1= CH3; R2= C2H5; R3= H; LONZACURE®M-DEA, in which R1= C2H5; R2= C2H5; R3= H; LONZACURE®M-MIPA., where R1= CH3; R2= C3H7; R3= H; LONZACURE®M-CDEA, in which R1= C2H5; R2= C2H5; R3= Cl; each of which is a commercial product Air Product and Chemicals, Inc., of Allentown, PA.

Such amine curing agents may include diamines curing agent such as 4,4'-methylene-bis(3-chloro-2,6-diethylaniline), (LONZACURE®M-CDEA); 2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene and mixtures thereof (collectively, the "diethyltoluenediamine" or "DETDA" ("DETDA"), which is a commercial product of Albemarle Corporation with the trade name ETHACURE 100; diethyltoluenediamine (DMTDA, DMTDA) (commercially available as ETHACURE 300); stable color version of ETHACURE 100 (that is, the formulation containing the additive to reduce the yellow staining), which is available under the name ETHACURE 100S; 4,4'-methylene-bis(2-Chloroaniline) (commercially available from the company Kingyorker Chemicals called ILAC). DATA can be liquid at room temperature with a viscosity of 156 CP (centipoise) at 25°C. DATA can be isomeric, and the amount of 2,4-isomer is from 75 to 81%, while the number of 2,6-isomer can be from 18 to 24%.

Other non-limiting examples of amine curing agents are ethylenamine, such as Ethylenediamine (EDA, EDA), Diethylenetriamine (DETA, DETA), Triethylenetetramine (THETA, THETA), tetraethylenepentaamine (TAP, TERA), pentametilmelamin (PAGE, REN), piperazine, morpholine, substituted morpholine, piperidine, substituted piperidine, diethylenediamine (DEDA, DEDA) and 2-amino-1-ethylpiperazin. In some Neogene ivalsa variants of implementation of the amine curing agent may be selected from one or more isomers With 1-C3-dialkylacrylamide, such as 3,5-dimethyl-2,4-toluidine, 3,5-dimethyl-2,6-toluidine, 3,5-diethyl-2,4-toluidine, 3,5-diethyl-2,6-toluidine, 3,5-aminobutiramida 2,4-toluidine, 3,5-aminobutiramida 2,6-toluidine and mixtures thereof. In some non-limiting embodiments, the implementation of the amine curing agent can be methylenedianiline or triethyleneglycol di(para-aminobenzoate).

Other non-limiting examples of amine curing agents include compounds having the following General structure (XIII-XV):

Other non-limiting examples of amine curing agents include one or more methylene-bis(anilines), represented by the General formula XVI-XX, one or more sulfides of aniline represented by the General formula XXI-XXV, and/or one or more bianjing represented by the General formula XXVI-XXVIX:

where R3and R4each independently from each other represent a1-C3-alkyl, and R5selected from a hydrogen atom and halogen, such as chlorine or bromine. The diamine represented by General formula XV can be described as 4,4'-methylene-bis(dialkylamide). Suitable non-limiting examples of the diamines, which can be represented by the General formula XV are, but are not limited to, 4,4'-methylene-bis(2,6-dimethylaniline), 4,4'-methylene-bis(2,6-diethylaniline), 4,4'-methylene-bis(2-ethyl-6-methylaniline), 4,4'-methylene-bis(2,6-diisopropylaniline), 4,4'-methylene-bis(2-isopropyl-6-methylaniline) 4,4'-methylene-bis(2,6-diethyl-3-Chloroaniline).

Amine curing agent may include compounds represented by the following General structure (XXX):

where R20, R21, R22and R23each independently from each other selected from H, C1-C3-alkyl, CH3-S -, and halogen, such as chlorine or bromine. Amine curing agent represented by the General formula XXX may include diethyltoluenediamine (DETDA), where R23represents methyl, R20and R21each represents ethyl and R22represents a hydrogen atom. In addition, the amine curing agent may include 4,4'-methylene-dianiline.

In the embodiment of the invention where it is desirable to produce poly(mochevinoi), low staining, amine curing agent can be selected so that it had a relatively low staining and/or could be made and/or could be stored in such a way as to prevent staining amine (for example, yellow).

In some non-limiting options is the ants polyurethanes Groups A-D, the reaction products are essentially may not contain amine curing agent. Used in this case, the expression "essentially do not contain amine curing agent" means that the reaction product component contains less than about 10% of the mass. amine curing agent, or less than about 5% of the mass. amine curing agent or less than approximately 2% of the mass. amine curing agent, or in other non-limiting embodiments, amine curing agent is absent.

Group E

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes of Group E containing the reaction product of components comprising: about 1 equivalent of at least one MDI; approximately 0.3 to 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and from about 0.01 to 0.3 equivalent, of at least one polycarbonate diol; where the reaction product components are essentially does not contain complex polyetherpolyols and simple polyetherpolyols and where the components of the reaction is maintained at a temperature, least about 100°C., at least, for about 10 minutes.

Non-limiting examples of suitable polyisocyanates, branched polyols containing from 4 to 18 carbon atoms and, IU the greater extent, 3 hydroxyl groups, polycarbonate diols and diol containing from 2 to 18 carbon atoms for use as the reaction products to obtain polyurethanes of Group E discussed in more detail above for the Group A.

In some non-limiting embodiments, the amount of branched polyol to form the polyurethane of Group E may be in the range from about 0.3 to 0.98 equivalent, or about 0.5 to 0.98 equivalent, or about 0.3 equivalent, or from about 0.9 to 0.98 equivalent.

In some non-limiting embodiments, the amount of the polycarbonate diol to form the polyurethane of Group E may be in the range from about 0.01 to 0.1 equivalent, or approximately from 0.05 to 0.1 equivalent, or approximately 0.1 equivalent.

In another embodiment, the present invention provides polyurethanes of Group E containing the reaction product of components comprising: about 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate); about 0.3 equivalents of trimethylolpropane; about 0.55 equivalent of 1,5-pentanediol and about 0.15 equivalent of the polycarbonate diol CM-1733 obtained from hexandiol, available from Stahl, where the components of the reaction is maintained at ambient temperature is re, at least approximately 100°C at least for about 10 minutes

In another embodiment, the present invention provides polyurethanes of Group E containing the reaction product of components comprising: about 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate); about 0.3 equivalents of trimethylolpropane; about 0.5 equivalent of 1,5-pentanediol and about 0.2 equivalent of the polycarbonate diol CM-1733 obtained from hexandiol, available from Stahl, where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

The polyurethanes of Group E can be a good ballistic resistance.

The polyurethanes of group E does not inherently contain a simple polyetherpolyols and amine curing agent, and the types and amounts of simple polyetherpolyols and amine curing agent described above for the Groups A-D.

In some non-limiting embodiments, the implementation of the polyurethanes of Group E of the reaction products can further comprise one or more of the following components: poliuretanoviy, acrylamide, polyvinyl alcohols, polymers containing (meth)acrylate with a hydroxyl functionality, polymers containing allyl alcohols, complex poliey the amides and mixtures thereof, as described, in the amounts presented above, when considering Groups A-D.

Group F

In some non-limiting embodiments, the present invention provides polyurethanes of Group F containing the reaction product of components comprising: (a) about 1 equivalent of at least one MDI; (b) from about 0.3 to 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; (C) from about 0.01 to 0.3 equivalent, of at least one polycarbonate diol; and (d) from about 0.1 to 0.9 equivalent of at least one diol containing from 2 to 18 carbon atoms; where the reaction product components are essentially does not contain complex polyetherpolyols and simple polyetherpolyols and where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes. Diol containing from 2 to 18 carbon atoms, chemically different from the polycarbonate diol, for example, diol has at least one other atom, or a different arrangement of the atoms, in comparison with the polycarbonate diol.

Non-limiting examples of suitable polyisocyanates, branched polyols containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, for whom carbonate diols and diols, containing from 2 to 18 carbon atoms, for use as the reaction products to obtain polyurethanes of Group F, described in detail above for the Group A.

In some non-limiting embodiments, the implementation of a number of branched polyol used to obtain the polyurethane of Group F, can be in the range from about 0.3 to 0.98 equivalent, or about 0.5 to 0.98 equivalent, or from about 0.9 to 0.98 equivalent.

In some non-limiting embodiments, the implementation of a number of the polycarbonate diol used to obtain the polyurethane of Group F, can be in the range from about 0.01 to 0.1 equivalent, or approximately from 0.05 to 0.1 equivalent, or may be about 0.1 equivalent.

In some non-limiting embodiments, the implementation of a number of diol used to obtain the polyurethane of Group F, can be in the range from about 0.01 to 0.1 equivalent, or approximately from 0.05 to 0.1 equivalent, or may be about 0.1 equivalent.

The polyurethanes of Group F is not essentially contain simple polyetherpolyols, and the types and amounts of simple polyetherpolyols described above for the Groups A-D.

In some non-limiting embodiments, the implementation of polyurethanes G is uppy F the reaction products can further comprise one or more of the following components: poliuretanoviy, acrylamide, polyvinyl alcohols, polymers containing (meth)acrylate with a hydroxyl functionality, polymers containing allyl alcohols, complex polyetherimide and their mixtures, as described, and in the amounts presented above, when considering Groups A-D.

In some non-limiting embodiments, the implementation of the polyurethanes of Group F, the reaction products can further comprise one or more amine curing agents discussed above for the Group that is In other non-limiting embodiments, the reaction products to obtain polyurethanes of Group F can essentially do not contain amine curing agent or may not include amine curing agent, as discussed above for the Groups A-D.

Group G

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes of Group G containing the reaction product of components comprising: about 1 equivalent of at least one MDI; approximately 0.3 to 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; from about 0.01 to 0.3 equivalent, of at least one polyol selected from the group comprising complex polyetherpolyols, polycaprolacton on Iola and mixtures thereof; and from about 0.1 to 0.7 equivalent of at least one aliphatic diol; where the reaction product components are essentially does not contain a simple polyetherpolyols and amine curing agent and where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

Non-limiting examples of suitable polyisocyanates, branched polyols containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, complex polyether polyols, consistent polyols and aliphatic diols for use as the reaction products to obtain polyurethanes of Group G, described in detail above for the Group A. Aliphatic diol chemically different from the complex polyetherpolyols and polycaprolactone polyol, such as diol has at least one other atom, or a different arrangement of the atoms in comparison with polyetherpolyols and polycaprolactone polyol.

In some non-limiting embodiments, the implementation of a number of branched polyol used to obtain the polyurethane of Group G may be in the range from about 0.3 to 0.9 equivalent, or approximately 0.3 to 0.7 equivalent, or about 0.4 to 0.6 equivalent, or approximately 0.7 equivalent.

what some non-limiting embodiments, the implementation of a number of polyester and/or polycaprolactone polyol, used to obtain a polyurethane Group G may be in the range from about 0.01 to 0.1 equivalent, or approximately from 0.05 to 0.1 equivalent, or may be about 0.1 equivalent.

In some non-limiting embodiments, the implementation of a number of aliphatic diol used to obtain the polyurethane of Group G may be in the range from about 0.1 to 0.6 equivalent, or approximately from 0.1 to 0.5 equivalent, or may be approximately 0.5 equivalent.

The polyurethanes of Group G does not inherently contain or do not contain a simple polyetherpolyols and/or amine curing agent, and the types and amounts of simple polyetherpolyols and amine curing agent described above for the Groups A-D.

In some non-limiting embodiments, the implementation of the polyurethanes of Group G of the reaction products can further comprise one or more of the following components: poliuretanoviy, acrylamide, polyvinyl alcohols, polymers containing (meth)acrylate with a hydroxyl functionality, polymers containing allyl alcohols, complex polyetherimide and their mixtures, as described, and in the amounts presented above, when considering Groups A-D.

In other non-limiting embodiments implementing the present invention offers the offers the polyurethanes of Group G, containing the reaction product of components comprising: about 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate); about 0.3 equivalents of trimethylolpropane; about 0.5 equivalent decandiol; and about 0.2 equivalent polycaprolactone, such as polycaprolactone Dow TONE 0210 having srednecenovogo molecular weight of approximately 1000 g/mol, where the components of the reaction is maintained at a temperature of at least approximately 100°C at least for about 10 minutes.

In other non-limiting embodiments, the implementation of the present invention provides polyurethanes of Group G, obtained from prepolymer, which is a reaction product of components including: (1) approximately 0.4 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate) (such as DESMODUR W); (2) about 0.3 equivalent polycaprolactone (such as polycaprolactones diol SARAH 2047 and SARAH A obtained from hexandiol); (3) about 0.05 equivalent of trimethylolpropane. Prepolymer enter into reaction with at least one aliphatic diola containing from 2 to 18 carbon atoms, as described above, for example, butanediol or pentanediol.

Group H

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes of Gr is PPI N, containing the reaction product of components comprising: (a) prepolymer, which is a reaction product of components including: (1) at least one polyisocyanate; (2) at least one polycaprolactone polyol; and (3) at least one polyol selected from the group comprising polyalkyleneglycol, simple polyetherpolyols and mixtures thereof; and (b) at least one diol containing from 2 to 18 carbon atoms.

Non-limiting examples of suitable polyisocyanates, polycaprolactones, polyalkyleneglycol, simple polyether polyols and diols containing from 2 to 18 carbon atoms, for use as the reaction product to obtain polyurethanes of G discussed in detail above for the Group A. non-limiting examples of suitable polyalkyleneglycol are the glycols, polypropylenglycol and mixtures thereof. Polyalkyleneglycol may have srednecenovogo molecular weight in the range from about 200 to 1000 g/mol, or from about 200 to 4000 g/mol.

Diol chemically different from polyalkyleneglycol and simple polyetherpolyols, for example, diol has at least one other atom, or a different arrangement of the atoms in comparison with polyalkyleneglycol and simple polyetherpolyols.

In some non-limiting embodiments, the implementation of the number of times tsennogo polycaprolactone, used to obtain a polyurethane Group N, may be in the range from about 0.05 to 0.8 equivalent, or approximately from 0.1 to 0.6 equivalent, or approximately from 0.1 to 0.4 equivalent, or approximately 0.3 equivalent.

In some non-limiting embodiments, the implementation of a number polyalkyleneglycol and/or simple polyetherpolyols used to obtain the polyurethane Group N, may be in the range from about 0.1 to 0.9 equivalent, or approximately 0.2 to 0.6 equivalent, or approximately 0.4 equivalent.

In some non-limiting embodiments, the implementation of a number of diol used to obtain the polyurethane Group N, may be in the range from about 0.1 to 0.9 equivalent, or approximately 0.3 to 0.8 equivalent, or approximately 0.7 equivalent.

The polyurethanes of Group H is obtained by reaction of the components of the reaction product, including: (1) at least one polyisocyanate; (2) at least one polycaprolactone; and (3) at least one polyol selected from the group comprising polyalkyleneglycol, simple polyetherpolyols and mixtures thereof; with the formation of prepolymer. Prepolymer then injected into the reaction, at least one diola containing from 2 to 18 carbon atoms, and any other who objazatelnye reaction components, described below.

In some non-limiting embodiments of the polyurethanes of Group H of the reaction products can further comprise one or more of the following components: branched polyols containing at least three hydroxyl groups, poliuretanoviy, acrylamide, polyvinyl alcohols, polymers containing (meth)acrylate with a hydroxyl functionality, polymers containing allyl alcohols, complex polyetherimide and their mixtures, as described, and in the amounts presented above for the Groups A-D.

In some non-limiting embodiments, the implementation of the polyurethanes of Group H of the reaction products can further comprise one or more amine curing agents discussed above for the Group that is In other non-limiting embodiments, the reaction products to obtain polyurethanes of Group H can essentially do not contain amine curing agent or may not include amine curing agent, as discussed above for the Groups A-D.

In other non-limiting embodiments, the present invention provides polyurethanes of Group H containing the reaction product of components comprising: (a) prepolymer, which is a reaction product of components including: (1) aliphatic or cycloaliphatic dies the cyanate; (2) polycaprolactone; (3) polyethylene glycol; and (4) polyoxyethylene and polyoxypropylene copolymer; and (b) at least one diol containing from 2 to 18 carbon atoms.

In other non-limiting embodiments, the implementation of the present invention provides polyurethanes of Group H obtained from prepolymer, which is a reaction product of components including: (1) approximately 0.4 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate) (such as DESMODUR W); (2) approximately 0,003 equivalent polycaprolactone (such as polycaprolactone diol A obtained from hexandiol); (3) approximately 0,025 equivalent of polyethylene glycol (such as PLURACOL E400NF); (4) approximately 0,029 equivalent polyoxyethylenated and polyoxypropylene copolymer (such as ethylene oxide/propyleneoxide block copolymers PLURONIC L62D); (5) about 0.05 equivalents of trimethylolpropane; and additives such as a catalyst (for example, dibutyltindilaurate), an antioxidant such as IRGANOX 1010 and IRGANOX MD 1024), as well as ultraviolet light stabilizers, such as CYASORB UV 5411 and TINUVIN 328 (each described below).

Prepolymer with terminal isocyanate group is introduced into the reaction, at least one diola containing from 2 to 18 carbon atoms, such as 1,4-butanediol and/or 1,4-cyclohexanedimethanol, in an equivalent ratio of 1,4-butand the Ola to 1,4-cyclohexanedimethanol about to 0.75:0.25 in. The equivalent ratio of prepolymer to dealu is approximately 1:1.

Group a-H

As for Groups a to H, the polyurethanes of the present invention can be polymerized using a variety of techniques. In some non-limiting embodiments, implementation, described in more detail below, the polyisocyanate and the polyol can be introduced into reaction with each other in a process vessel with the formation of polyurethane. Sulfur-containing polyurethane of the present invention can be obtained by mixing isocyanate and/or isothiocyanate and polyol and/or politial.

In other non-limiting embodiments of the invention, the polyurethanes can be obtained by the reaction of MDI(s) and polyol(s) with the formation of polyurethane prepolymer, and then by introducing diol(s) and optional catalyst and other optional components of the reaction.

In other non-limiting embodiments, implementation, such as the Group, the polyurethane can be obtained by the reaction of MDI(s) and diol(s) with the formation of urethane prepolymer with isocyanate functionality, and then the introduction of the diol(s), polyols and optionally a catalyst and other optional components of the reaction. In some embodiments of the invention urethane prepolymer with isocyanate functionality of the polyol and the second h is here diol component of the reaction is maintained at a temperature, at least approximately 100°C for at least about 10 minutes, or at least approximately at s within at least about 10 or 20 minutes.

Regardless of the receiving process, consisting of a single operation, or in a multistage process using prepolymer in some non-limiting embodiments of the invention to conduct the reaction of each of the above-mentioned ingredients may be degassed (obesogen). In some non-limiting embodiments of the invention prepolymer can be degassed, disfunctionally material may be degassed, and then two materials can be mixed.

In the method of "one operation" or during polymerization in the amount of all the ingredients, that is, isocyanate, polyol and diol are mixed simultaneously. This method is usually satisfactory when all the active hydrogen atoms react with approximately the same speed, for example, when all contain hydroxyl groups as the sole reactive sites. Urethane reaction can be carried out in anhydrous conditions with dry reactants, for example, in a nitrogen atmosphere at atmospheric pressure and at a temperature in the range from about 75 to 140°C. If used polycarbonatediol or any other compounds with hydroxyl functionality, they usually before carrying out the reaction is dried, usually to a moisture content in the range of approximately from 0.01 to 0.05%.

To obtain the desired statisticheski and generally transparent polymer diol, for example anhydrous 1,4-butanediol (containing a maximum of 0.04% of water)may be added to the polyol in a nitrogen atmosphere to exclude moisture, and the temperature of the support is high enough so that phase separation is absent and obtain a homogeneous mixture. The polyisocyanate such as 4,4'-methylene-bis(cyclohexylidene), can be added quickly and the mixture can be maintained at a temperature of at least about 75°C., or at least about 85°C, or at least about 90°C., or at least approximately 95°C for at least about 10 minutes, or at least about 20 minutes. In some embodiments, the implementation of the mixture is maintained at a temperature of at least about 100°C., or at least about 105°C., or at least about 110°C for at least about 10 minutes, or at least about 20 minutes so that the separation of the phases is missing, and the mixture remains homogeneous. The mixture can be maintained at a pressure in the range from about 2 to 6 mm Hg (approximately 266,6 to 800 Pascals (PA)) is whether at approximately 266,6 PA during the period of time from about 10 minutes to 24 hours, or from about 10 minutes to 4 hours.

In some non-limiting embodiments, the implementation of the mixture is intensively stirred at a temperature of at least about 75°C., or at least about 85°C, or at least about 95°C., or at least about 100°C., or at least about 105°C., or at least about 110°C, and Tegaserod during the period of time of at least about 3 minutes, and during this time the pressure is reduced from atmospheric pressure to approximately to 3 mm Hg Reduction in pressure facilitates the removal of dissolved gases, such as nitrogen and carbon dioxide, and then the ingredients can be introduced into the reaction at a temperature in the range from about 100 to 140°C., or from about 110 to 140°C., in the presence of a catalyst, and the reaction continued until until essentially will not remain isocyanate groups, in some embodiments for at least about 6 hours. In the absence of catalyst, the reaction can be carried out for at least about 24 hours, for example, in nitrogen atmosphere.

In some non-limiting embodiments, the implementation of which can be molded window capable of polymerization mixture, which may not necessarily be degassed, you can enter in the melt and dissolved, and the AB can be heated (i.e., the cycle thermal curing) using a number of conventional techniques, known in the art. Cycle thermal curing may vary depending on the reactivity and the molar ratio of the reagents. In a non-limiting embodiment, the cycle thermal curing may include heating a mixture of prepolymer and diol and optionally a diol and dithiol; or heating a mixture of MDI, polyol and/or politial and diol and/or diol/dithiol from room temperature to a temperature of approximately 200°C for a period of time from about 0.5 to 72 hours; or from about 80°C to 150°C for a period of time from about 5 to 48 hours.

In other non-limiting embodiments, implementation, described in more detail below, the isocyanate and the polyol can react with each other to form polyurethane prepolymer and prepolymer may be introduced into reaction with a large number of the same or another(their) polyol(s) and/or diol(s) with the formation of sulfur-containing polyurethane or polyurethane. When using a pre-polymer method prepolymer and diol(s) can be heated to reduce the viscosity of prepolymer approximately 200 centipoise or, at most, to a few thousand SDRs to facilitate stirring. As with polymerization in the volume, the reaction must be performed in betwo the conditions with dry reactants.

Polyurethane prepolymer may have srednecenovogo molecular weight (Mn) of less than approximately 50,000 g/mol, or less than about 20000 g/mol, or less than approximately 10000 g/mol, or less than about 5000 g/mol, or at least about 1000 g/mol, or at least about 2000 g/mol, including any interval between them.

When forming the polyurethane components such as polyols and isocyanates, are mixed with obtaining polyurethanes, the relative quantities of ingredients, usually expressed as the ratio of the number of available reactive isocyanate groups to the number of available reactive hydroxyl groups, that is, the equivalent ratio of NCO:OH. For example, the ratio of NCO:OH of 1.0:1.0 to receive, when one equivalent of NCO filed form isocyanate component is reacted with a mass of one equivalent of OH of submitted form organic polyol as one component. The polyurethanes of the present invention can have the equivalent ratio of NCO:OH that are in the range of approximately from 0.9:1.0 to 1.1 to 1.0 second, or approximately 1,0:1,0.

In some non-limiting embodiments, implementation, when the isocyanate and the polyol is introduced into the reaction with the formation of prepolymer, the isocyanate is present in excess, such as the number of isocyanate and the number of polio is in the isocyanate prepolymer can be selected so that the equivalent ratio (NCO):(OH) could be in the range of approximately from 1.0:0.05 to 1.0 to:0,7.

In some non-limiting embodiments, the implementation of the number of isocyanate and the amount of polyol used to obtain polyurethane prepolymer with terminal isocyanate group or sulfur-containing polyurethane prepolymer with terminal isocyanate group can be chosen so that the equivalent ratio (NCO):(SH+OH) can be at least approximately 1.0:1.0 in, or at least approximately 2,0:1,0, or at least about 2.5:1.0 to, or less than about 4.5:1.0 to or less than approximately 5.5:1,0; or the number of isothiocyanate and the amount of polyol used to obtain the sulfur-containing polyurethane prepolymer with end isothiocyanato group can be chosen so that the equivalent ratio (NCS):(SH+OH) can be at least approximately 1.0:1.0 in, or at least approximately 2,0:1,0, or at least about 2.5:1.0 to, or less than about 4.5:1.0 to or less than approximately 5.5:1,0; or the number of combinations of isothiocyanate and isocyanate and the amount of polyol used to obtain the sulfur-containing polyurethane prepolymer with end isothiocyanates/isocyanate group, may be selected so that the equivalent ratio (NCS+NCO):(SH+OH) can be at least approximately 1.0:1.0 in, or at least approximately 2,0:1,0, or at least about 2.5:1.0 to, or less than about 4.5:1.0 to or less than approximately 5.5:1,0.

Ratio and proportions of diol and polyol can have an impact on the viscosity of prepolymer. The viscosity of such prepolymers can be improved, for example, if they are designed for applications covering compositions, for example compositions for processes of coating, inkjet bulk. The solids content of such prepolymers, however, may also have value as a higher solids content can be achieved desired properties for coatings, such as resistance to weathering, resistance to scratching and other conventional coating covering the composition with a higher solids content usually require higher amounts of solvent to dilute the coating to reduce the viscosity for the respective processes of coating, inkjet bulk. The use of such solvents, however, may adversely affect the surface of the base, especially when the base surface is a polymeric material. In the present invention the viscosity of prepolymer can be properly adjusted to obtain the shape of the material with lower viscosity at higher solids contents, resulting in getting effective coverage without the need for extremely large quantities of solvents, which may adversely affect the surface of the base.

In some non-limiting embodiments of the present invention, which uses the optional amine curing agent, the amount of polyurethane prepolymer with terminal isocyanate group or sulfur-containing polyurethane prepolymer with terminal isocyanate group and the amount of amine curing agent used to obtain the sulfur-containing polyurethane can be chosen so that the equivalent ratio (NH+SH+OH):(NCO) could be in the range approximately from 0.80:1.0 to 1,1:1,0, or approximately from 0.85:1.0 to 1,0:1,0, or approximately from about 0.90:1.0 to 1,0:1,0, or from about 0,90 are:1.0 to 0.95:1.0 to, or approximately from 0.95:1.0 to 1,0:1,0.

In some non-limiting embodiments of the present invention, the amount of sulfur-containing polyurethane prepolymer with end isothiocyanates or isothiocyanato/isocyanate group and the amount of amine curing agent used to obtain the sulfur-containing polyurethane can be chosen so that the equivalent ratio (NH+SH+OH):(NCO+ NCS) could be in the range approximately from 0.80:1.0 to 1,1:1,0, or approximately from 0.85:1.0 to 1,0:1,0, or PR is approximately from about 0.90:1.0 to 1,0:1,0, about 0,90 are:1.0 to 0.95:1.0, or about from 0.95:1.0 to 1,0:1,0.

I believe that the unusual characteristics of energy absorption and transparency of the polyurethanes of the present invention may not only depend on the ingredients and proportions of urethane, but may also depend on the method of obtaining. More specifically, suppose that the presence of the polyurethane ordered block segments may adversely affect the characteristics of transparent polyurethane and energy absorption, and, therefore, believe that statistical segments within the polymer can give optimal results. Therefore, does the urethane statistical or ordered block-segments depends on the particular reactants and their relative reactivity, and reaction conditions. In General, the polyisocyanate will be more reactive with molecular diola or polyol, for example, 1,4-butanediol, than with a polymeric polyol; and therefore, in some non-limiting embodiments of the invention, it is desirable to inhibit the preferred reaction between low molecular weight diola or polyol and polyisocyanate, for example, by rapidly adding MDI to a well stirred mixture of low molecular weight diol or polyol and polymer polyol with intensive mixing, for example, when the temperature, at least about 75°C when not in use the catalyst, and then by keeping at the reaction temperature of at least approximately 100°C. or 110°C, just after the exothermic reaction. When using the catalyst of the initial temperature of the mixture may be lower, for example about 60°C to ectothermy did not increase the temperature of the mixture substantially above the desired reaction temperature. Although polyurethanes are thermally stable, however, the reaction temperature can reach approximately up to 200°C and to be below approximately 60°C., and in some non-limiting embodiments are in the range from about 75 to 130°C. using a catalyst, or in the range from about 80 to 100°C. When a catalyst is not used in some non-limiting embodiments of the invention, the reaction temperature may be in the range from about 130 to 150°C.

It is also desirable to quickly reach the temperature of the reaction after a homogeneous mixture when not in use the catalyst to the polymer does not become turbid due to phase separation. For example, some of the mixture without catalyst can become muddy in less than half an hour at a temperature less than 80°C. Therefore, it may be desirable to use a catalyst or introduction reagent is, for example, using a high shear intensive mixing head in order to quickly achieve the reaction temperature above about 100°C., or about 110°C., or about 130°C. so that the polymer does not become muddy. Suitable catalysts may be selected from catalysts known in the art. In some non-limiting embodiments of the invention, before or after addition of the catalyst can be carried out degassing

In some non-limiting embodiments, the urethane-forming catalyst can be used in the present invention, in order to accelerate the reaction of the polyurethane-forming materials. Suitable urethane-forming catalysts are catalysts that may be useful for the formation of urethane by reaction of NCO - and HE-containing materials and which have little tendency to accelerate side reactions leading to the formation of allophanate and isocyanate. Non-limiting examples of suitable catalysts are selected from Lewis bases, Lewis acids and catalysts inclusions, which are described in the publicationUllmann''s Encyclopedia of Industrial Chemistry, 5-th Edition, 1992, Volume A21, pp. 673-674.

In some non-limiting embodiments, the implementation of the catalyst may be a tin salt of an organic acid, such as octanoate tin and utilityname acid. Other non-limiting examples of suitable catalysts include catalysts based on tertiary amines, tertiary ammonium salts, tin catalysts, phosphine, or a mixture thereof. In some non-limiting embodiments of the invention the catalyst may represent dimethylcyclohexylamine, dibutyltindilaurate, dibutylaminoethanol, dibutylformamide, dibutylaminoethanol, dibutyltindilaurate, dimethylaminoacetyl, dimethylglutaric, 1,4-diazabicyclo[2.2.2]octane, bismuth carboxylates, zirconium carboxylates, octoate zinc, iron acetylacetonate, and mixtures thereof. The amount of catalyst may vary depending on the number of components, for example from about 10 to 600 h/million

In alternate non-limiting embodiments of the invention, various additives can be included in compositions containing polyurethane(s) of the present invention. Such additives are light stabilizers, thermal stabilizers, antioxidants, colorants, flame retardants, ultraviolet absorbers of radiation, light stabilizers such as light stabilizers based on difficult amines, agents, helps to release from the mold, static (non -) dyes, fluorescent agents, pigments, surfactants, softening agents, is such as, but without limitation, alkoxysilane provenzale and dibenzoate poly(alkalophiles), and mixtures thereof. Non-limiting examples of additives that prevent yellowing, are 3-methyl-2-butanol, organic pyrocarbonate and triphenylphosphite (Reg. CAS No. 101-02-0). Examples of useful antioxidants include IRGANOX 1010, IRGANOX 1076 and IRGANOX MD 1024, each of which is a commercial product of Ciba Specialty Chemicals of Tarrytown, New York. Examples of suitable UV absorbers are CYASORB UV 5411, TINUVIN 130 and TINUVIN 328, which are commercially available from the company Ciba Specialty Chemicals, as well as SANDOVAR 3206, which is a commercial product of Clariant Corp. Of Charlotte, North Carolina. Examples of useful light stabilizers based on amines are difficult SANDOVAR 3056, which are commercially available from the company Clariant Corp. of Charlotte, North Carolina. Examples of useful surfactants are BYK 306, which are commercially available from the company BYK Chemie of Wesel, Germany.

The mentioned additives may be present in such quantities that the additive gave less than about 30 wt. -%, or less than about 15 wt. -%, or less than about 5 wt. -%, or less than about 3 wt. -%, based on the total weight of the polymer. In some non-limiting embodiments, the aforementioned optional additives can be pre-mixed with the polyisocyanate(s) or with preprime the ohms with isocyanate functionality. In other non-limiting embodiments of the invention the optional additives can be pre-mixed with the polyol(s) or the urethane prepolymer.

In some non-limiting embodiments, the implementation of the present invention provides methods of obtaining polyurethanes of Group a, which includes the stage of interaction in a single reaction vessel components, comprising: about 1 equivalent of at least one MDI; from about 0.1 to 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and from about 0.1 to 0.9 equivalents of at least one diol containing from 2 to 18 carbon atoms, where the components are essentially not contain complex polyetherpolyols and simple polyetherpolyols.

In other non-limiting embodiments, the present invention provides methods of obtaining polyurethanes of Group a, which includes stage: communicating at least one MDI and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of polyurethane prepolymer; and interaction polyurethane prepolymer at least one diola containing from 2 to 18 carbon atoms, with about the education of polyurethane.

In other non-limiting embodiments, the implementation of the present invention provides methods of obtaining polyurethanes of Group b, which includes stages:

(a) interaction (i) about 1 equivalent of at least one MDI; and (ii) from about 0.1 to 0.5 equivalent, of at least one diol containing from 2 to 18 carbon atoms, with formation of urethane prepolymer with isocyanate functionality;

(b) interaction urethane prepolymer with isocyanate functionality and approximately from 0.05 to 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, and until about 0.45 equivalents of at least one diol containing from 2 to 18 carbon atoms, where the components of the reaction product essentially does not contain complex polyetherpolyols and simple polyetherpolyols.

In some non-limiting embodiments, the present invention provides methods of obtaining polyurethanes Group, which include the stage of interaction in a process vessel components, comprising: at least one trimer MDI or branched polyisocyanate, the polyisocyanate has at least three isocyanate functional groups; and at least one Alif is political polyol, containing from 4 to 18 carbon atoms and at least two hydroxyl groups; where the components of the reaction product essentially does not contain complex polyetherpolyols and simple polyetherpolyols.

In some non-limiting embodiments, the present invention provides methods of obtaining polyurethanes of Group D, which includes the stage of interaction in a single reaction vessel components, comprising: at least one polyisocyanate; at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and at least one polyol containing one or more bromine atoms, one or more phosphorus atoms or combinations thereof.

In other non-limiting embodiments, the present invention provides methods of obtaining polyurethanes of Group D, which includes the stages of: communicating at least one MDI and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of polyurethane prepolymer; and interaction polyurethane prepolymer at least one polyol containing one or more bromine atoms, one or more phosphorus atoms or combinations thereof, with the formation of polyurethane. In some non-limiting embodiments, p is blithedale from 0.1 to 0.15 equivalent branched polyol reacts with approximately 1 equivalent of MDI at the stage (a), and stage (b) further includes the interaction of polyurethane prepolymer with polyol and from about 0.15 to 0.9 equivalent of a branched polyol to form polyurethane.

In some non-limiting embodiments, the present invention provides methods of obtaining polyurethanes of Group E, which includes the stage of interaction in a single reaction vessel components, comprising: about 1 equivalent of MDI; approximately 0.3 to 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and from about 0.01 to 0.3 equivalent, of at least one polycarbonate diol, where the components of the reaction product essentially does not contain a simple polyetherpolyols and amine curing agent.

In other non-limiting embodiments, the present invention provides methods of obtaining polyurethanes of Group E, which includes the stages of: communicating at least one MDI and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of polyurethane prepolymer; and interaction polyurethane prepolymer at least one polycarbonate diol, with the formation of polyurethane.

In some is, some non-limiting embodiments, the present invention provides methods of obtaining polyurethanes of Group F, which include stage of interaction in a single reaction vessel components, including: (a) about 1 equivalent of at least one MDI; (b) from about 0.3 to 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; (C) from about 0.01 to 0.3 equivalent, of at least one polycarbonate diol; and (d) from about 0.1 to 0.9 equivalents of at least one diol containing from 2 to 18 carbon atoms; where the components of the reaction product essentially does not contain a simple polyetherpolyols.

In other non-limiting embodiments, the present invention provides methods of obtaining polyurethanes of Group F, which include stages: (a) interaction of at least one MDI and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of polyurethane prepolymer; and (b) interaction of polyurethane prepolymer at least one polycarbonate diol and at least one diola containing from 2 to 18 carbon atoms, with the formation of polyurethane; where the components the reaction product essentially does not contain a simple polyetherpolyols.

In some non-limiting variations on toadie the invention provides methods of obtaining polyurethanes of Group G, which include stage of interaction in a single reaction vessel components, comprising: about 1 equivalent of at least one MDI; approximately 0.3 to 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and from about 0.01 to 0.3 equivalent, of at least one polyol selected from the group comprising complex polyetherpolyols, polycaprolactone and mixtures thereof, and from about 0.1 to 0.7 equivalent of at least one aliphatic diol; where components of the reaction product essentially does not contain a simple polyetherpolyols and amine curing agent.

In other non-limiting embodiments, the present invention provides methods of obtaining polyurethanes of Group G, which includes stage: communicating at least one MDI and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of polyurethane prepolymer; and interaction polyurethane prepolymer at least one polyol selected from the group comprising complex polyetherpolyols, polycaprolactone polyol and mixtures thereof, and from about 0.1 to 0.7 equivalent of at least one aliphatics the CSOs diol, with the formation of polyurethane.

In some non-limiting embodiments, the present invention provides methods of obtaining polyurethanes of Group H, which include stage: interaction of components, comprising: at least one polyisocyanate; at least one polycaprolactone; and at least one polyol selected from the group comprising polyalkyleneglycol, simple polyetherpolyols and mixtures thereof, with the formation of polyurethane prepolymer; and interaction of prepolymer at least one diola containing from 2 to 18 carbon atoms, with the formation of polyurethane.

Poly(mochevinoi)

Poly(mochevinoi) can be obtained from any of the above-described polyurethanes Groups a to H by including one or more amine curing agents in the reaction components. Amine functionality of the amine curing agent can react with the isocyanate groups with the formation of urea bridges or links within the polyurethane matrix. The corresponding amount of amine curing agents and reaction conditions are discussed in detail below.

Synthesis: Poly(mochevinoi)

Alternative or additional urea bridges or links may be formed within the polymer matrix to the desired extent due to the interaction from analnyj functional groups of MDI with water. As shown in stage 1 of the reaction scheme of the synthesis of poly(mochevinoi) And below, isocyanate functional groups into urethane functional groups by reaction with water. In some non-limiting embodiments, the implementation of the equivalent ratio NCO:water is in the range from about 10:1 to 2:1, or from about 5:1 to 2:1 or about 3:1 to 2:1.

Isocyanate shown in stage 1, is a diisocyanate, in which R is any bridging group, such as aliphatic, cycloaliphatic, aromatic, heterocyclic, etc. that are described in detail above. However, qualified in this field specialist will be clear that the isocyanate may have one or more, two or more, three or more, or more isocyanate functional groups, if desired. Examples of suitable isocyanates can be any isocyanate discussed above. In some non-limiting embodiments, the implementation of the polyisocyanate is one or more aliphatic polyisocyanates. In some non-limiting embodiments of the invention, the polyisocyanate is a 4,4'-methylene-bis(cyclohexylidene) (such as DESMODUR W).

The removal of carbon dioxide facilitates the transformation of urethane groups in the mine group. The excess isocyanate is desirable to provide essentially complete consumption of the water. In addition, it is desirable to remove essentially all of the formed carbon dioxide to facilitate the conversion of amine groups. Water can react with the polyisocyanate or prioritypriority prepolymer at a temperature of about 60°C in vacuum. Negative pressure must be sufficiently low so as not to remove water from the system, and it can be in the range of, for example, from about 10 to 20 mm Hg (approximately from 1333 to 2666 PA) for about 10 to 30 minutes. After essentially complete the reaction, i.e. when the additional amount of carbon dioxide is not formed, the temperature may be increased at least approximately 100°C. or about 110°C., and heat for about 2 to 24 hours, or approximately 2 hours using 10 ppm or more of a catalyst, such as dibutylaminoethanol. After essentially all of the water will react with excess isocyanate, the resulting amine is reacted with the isocyanate essentially instantly.

Synthesis: Poly(mochevinoi).

Stage 1

Stage 2

Stage 3

Qualified in D. the authorized field technician is well known, some amine curing agents such as aliphatic amine curing agents containing from 2 to 18 carbon atoms, such as Ethylenediamine, diethylenediamine, diaminobutane, PACM, diaminohexane, 1,10-decontamin) are very reactive and are not suitable for use in normal industrial conditions, because the amine functionality very quickly begins to react with oxygen present in ambient air, changing color polymerizate. Aliphatic amine curing agents are usually very hygroscopic and difficult to keep dry. Typically, aliphatic amines are so reactive that they cannot be used for the manufacture containing 100% solids, transparent, malaekahana and has a small turbidity plastics.

Due to the formation of aminein situas discussed above and as shown in stage 2, amines can be generatedin situthat is usually not practical when applied under normal production conditions, without the formation of undesirable by-products, color or turbidity. In addition, the reaction rate can be more easily adjusted. This reaction can be used for any type MDI described above, but particularly useful for the conversion of aliphatic polyisocyanates in amines, as this description is about above.

As shown above in stage 2, the amine formedin situreacts with another isocyanate with formation of urea groups. The use of excess MDI allows the formation of urea prepolymer with isocyanate functionality. In some non-limiting embodiments implement the equivalent ratio of NCO functional groups:amine is in the range from about 1:0.05 to 1:0.7 and about 1:0.05 to 1:0.5, and or from about 1:0.05 to 1:0,3. A suitable reaction temperature may be in the range from about 25 to 60°C in the presence of a catalyst such as a tin catalyst. After the water will react and after removal of carbon dioxide, the reaction temperature can be increased to approximately 90°C for approximately 2 to 4 hours. On the other hand, the reaction can be conducted at approximately 25°C for approximately 8 hours to complete. Optional one or more polyols or diols described above, can be introduced in the reaction with the formation of urethane prepolymers with isocyanate functionality, as shown for the synthesis of poly(mochevinoi), described in more detail below.

As shown in stage 3 of reaction scheme of the synthesis of poly(mochevinoi) And polyol and/or diol can be established is by reaction with urea(and) prepolymer(s) with isocyanate functionality with the formation of poly(macawesomeshow) of the present invention. Polyol shown in stage 3 may be a diol (m = 2), triol (m = 3) or higher hydroxypentanal material (m = 4 or more), as described above, in which R is any bridging group, such as aliphatic, cycloaliphatic, aromatic, heterocyclic group, etc. that are described in more detail above for the polyols. Examples of suitable polyols may be any of the above polyols. In some non-limiting embodiments of the invention, the polyol may be trimethylolpropane and butanediol and/or pentanediol. Suitable amounts of polyols for interaction with the urea prepolymers with isocyanate functionality as MDI discussed in detail above. In the above poly(mochevinoi) x can be in the range from 1 to about 100, or from about 1 to 20.

In some non-limiting embodiments, the implementation for the formation of poly(mochevinoi) prepolymer with isocyanate functionality is heated to a temperature of about 90°C, add the polyol(s) and heated to approximately 90°C. the Temperature can be raised to approximately 100°C. or about 110°C., to facilitate the integration can then be attached to a vacuum of approximately 2 to 4 mm Hg during the rough is about 3 to 5 minutes.

To obtain product, for example, the mixture can be poured or shed under pressure in a coated adhesive grease molds for glass with the formation of the product of the desired thickness and desired dimensions. In some embodiments, molds preheated to a temperature of approximately 200°F (93,3°C). The completed form or the cell can be placed in a furnace at a temperature of from about 250 to 320°F (121 to 160°C) and cured, for example, for about 24 to 48 hours. The cell can be removed from the furnace and cooled to a temperature of about 25°C., and the cured polymer can be extracted from the mold.

Group I

In some non-limiting embodiments, the implementation of the present invention provides poly(mochevinoi) Group I, containing the reaction product of components comprising: (a) at least one urea prepolymer with isocyanate functionality, containing the reaction product of: (1) at least one MDI; and (2) water; and (b) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, where the reaction product components are essentially does not contain or contains amine curing agents. Suitable polyisocyanates and branched(e) polyol(s), contains(e) from 4 to 18 carbon atoms, adolescents who but described above. If amine(e) curing(e) agent(s) is(are)it(they) may(may) be present in a quantity which is defined above as "essentially does not contain". Any other optional polyols, catalysts or other additives described above can be included as reaction components in the amounts described above for the Groups A-H.

In some non-limiting embodiments, the implementation of the present invention provides methods for obtaining poly(macawesomeshow) Group I, which includes stages: (a) interaction of at least one MDI and water with the formation of urea prepolymer with isocyanate functionality; and (b) interaction of the reaction product of components containing urea prepolymer with isocyanate functionality of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, where the reaction product components are essentially does not contain amine curing agent. The reaction can be represented as described above for the synthesis of poly(mochevinoi) A. Optional part of one or more polyols or diols described above, can be introduced into the reaction with the formation of urethane prepolymer with isocyanate functionality, which is then injected into the reactions the other part of the polyol and/or diol, as shown for the synthesis of poly(mochevinoi), which is described in more detail below.

Group J

In some non-limiting embodiments, the implementation of the present invention provides poly(mochevinoi) Group J, containing the reaction product of components comprising: (a) at least one urea prepolymer with isocyanate functionality, containing the reaction product of: (1) at least one MDI selected from the group comprising trimers MDI and branched polyisocyanates, the polyisocyanate contains at least three isocyanate functional groups; and (2) water; and (b) at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups.

Examples of suitable trimers MDI and branched polyisocyanates and polyol(s) discussed above. Any other optional polyols, amine curing agent, catalyst and other additives described above may be included in the reaction components in the amounts described above for the above Groups A-N. In some non-limiting embodiments, the reaction components essentially do not contain or do not contain amine curing agents described above.

In other non-limiting embodiments implementing the present and the finding suggests ways of obtaining poly(macawesomeshow), which include stage: (a) interaction of at least one MDI selected from the group comprising trimers MDI and branched polyisocyanates, and water with the formation of urea prepolymer with isocyanate functionality; and (b) interaction of the reaction product of components containing urea prepolymer with isocyanate functionality of at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups, where the reaction product components are essentially does not contain amine curing agent.

The reaction can be represented as described above for the synthesis of poly(mochevinoi) A. Optional part of one or more polyols or diols described above, can be introduced into the reaction with the formation of urethane prepolymer with isocyanate functionality, which is then injected into the reaction with the other part of the polyol and/or diol, as shown for the synthesis of poly(mochevinoi), which is described in more detail below.

Synthesis: Poly(mochevinoi)

As shown in the generally lower for the synthesis of poly(macawesomeshow), in other non-limiting embodiments of the invention urea bridges or links may be formed within the polyurethane matrix to the desired extent due to the interaction of reisolate(s) and parts of polyol(s), education, at least one urethane prepolymer with isocyanate functionality, and then when the interaction urethane(s) prepolymer(s) with isocyanate functionality of water. As shown in stage 1 of the reaction scheme of the synthesis of poly(mochevinoi), part of the polyol(s) and/or diol(s) may be introduced into the reaction with the polyisocyanate(s) with the formation of at least one urethane prepolymer with isocyanate functionality. In some non-limiting embodiments, the equivalent ratio of NCO functional groups is in the range from about 1:0.05 to 1:0.7 and about 1:0.05 to 1:0.5, and or from about 1:0.05 to 1:0,3. It is desirable to use an excess of isocyanate to provide essentially complete conversion of hydroxyl groups in the urethane group.

Isocyanate shown in stage 1, is a diisocyanate, in which R is any bridging group, such as aliphatic, cycloaliphatic, aromatic, heterocyclic, and others, which are described in more detail below. However, the person skilled in the art will understand that the isocyanate may have one or more, two or more, three or more, or a higher number of isocyanate functional groups, if desired. Examples of suitable isocyanates can be any the s polyisocyanates, described above. In some non-limiting embodiments, the implementation of the polyisocyanate is one or more aliphatic polyisocyanates. In some non-limiting embodiments of the invention, the polyisocyanate is a 4,4'-methylene-bis(cyclohexylidene) (such as DESMODUR W).

Polyol shown in stage 1, may be a diol (m=2), triol (m=3) or higher hydroxypentanal material (m=4 or more), as described above, in which R is any bridging group, such as aliphatic, cycloaliphatic, aromatic, heterocyclic group, etc. that are described in more detail above for the polyols. Examples of suitable polyols may be any of the above polyols. In some non-limiting embodiments of the invention, the polyol may be trimethylolpropane and butanediol and/or pentanediol. Optionally one or more catalysts, such as described above can be used to facilitate the reaction. The polyisocyanate may be introduced into the reaction with the polyol with the formation of urethane prepolymer with isocyanate functionality by loading the reagents into the reactor and adding approximately 10 ppm or more of a catalyst, such as catalyst based on tin, bismuth or zirconium. The mixture can the unit's electric is at a temperature of approximately 100 or 110°C for approximately 2 to 4 hours, until all of the hydroxyl functionality does not react. To determine the extent of reaction, you can use the data of FTIR spectroscopy.

Urea bridges or links may be formed within the polyurethane matrix to the desired extent due to the interaction of water with isocyanate functional groups of the urethane prepolymer with isocyanate functionality. As shown in stage 2 scheme of reactions for the synthesis of poly(mochevinoi) below, isocyanate functional groups into urethane functional groups by reaction with water. In some non-limiting embodiments, the equivalent ratio of NCO:water is in the range from about 1:0.05 to 1:0.7 and about 1:0.05 to 1:0.5, and or from about 1:0.05 to 1:0,3.

The removal of carbon dioxide facilitates the transformation of urethane groups in the amine group. The excess isocyanate is desirable to provide essentially complete consumption of the water. In addition, it is desirable to remove essentially all of the formed carbon dioxide to facilitate the conversion to amine groups. To prevent removal of water under vacuum, the reaction may be initiated at a temperature of about 25°C., then the temperature was raised to about 60°C. while applying vacuum to remove carbon dioxide. After closing the stop formation of carbon dioxide the temperature may be increased, at least approximately to a temperature of 100 or 110°C for approximately 2 to 4 hours.

As discussed above, some amine curing agents such as aliphatic amine curing agents) are highly reactive and are unacceptable for use in normal production conditions. Due to the formation of aminein situas discussed above and as shown in stage 2, amines can be generatedin situthat is usually not implemented for use under normal production conditions, without the formation of undesirable side reaction products. In addition, the reaction rate can be more easily adjusted. This reaction can be used for any type MDI described above, but particularly useful for the conversion of aliphatic polyisocyanates in the amines as described above.

As shown in stage 3, the amine formedin situreacts with another isocyanate with formation of urea groups. The use of excess MDI provides education motivirovannogo of prepolymer with isocyanate functionality. Motivirovochnuyu prepolymer with isocyanate functionality can be obtained by the reaction of a stoichiometric excess of MDI with an amine, essentially in the anhydrous conditions at which the temperature in the range from about 25 to 150°C, or at approximately 110°C. until reaction between the isocyanate groups and amine groups is essentially complete. Polyisocyanate and an amine component can be introduced into the reaction in such proportions that the ratio of the number of isocyanate groups to the number of amine groups was in the range from about 1:0.05 to 1:0.7 to, or within the range from about 1:0.05 to 1:0,3.

As shown in stage 4 of reaction scheme of the synthesis of poly(mochevinoi), motivirovochnuyu prepolymer with isocyanate functionality can be introduced to react with another part of the polyol and/or diol with the formation of poly(macawesomeshow) of the present invention. Polyol shown in stage 4, may be a diol, triol or higher hydroxypentanal material, as described above, in which R is any bridging group, such as aliphatic, cycloaliphatic, aromatic, heterocyclic group, etc. that are described in more detail above for the polyols. Examples of suitable polyols may be any of the above polyols. In some non-limiting embodiments of the invention, the polyol may be trimethylolpropane and butanediol and/or pentanediol. The appropriate number of polyols to interact with motivirovochnuyu prepolymers with Isola atoi functionality as MDI discussed in detail above.

Motivirovochnuyu prepolymer with isocyanate functionality can be introduced to react with another part of the polyol and/or diol (n=2 or more) essentially in the anhydrous conditions at a temperature in the range from about 120 to 160°C. until the reaction between isocyanate groups and hydroxyl groups is substantially complete. Components motivirovannogo of prepolymer with isocyanate functionality and polyol(s) and/or diol(s) can be introduced into the reaction in such proportions that the ratio of the number of isocyanate groups to the number of hydroxyl groups was in the range of approximately from 1.05:1 to 1:1. In poly(mochevinoi) Group For y may be in the range from 1 to 500 and above, or from about 1 to 200.

The curing temperature depends on the glass transition temperature of the final polymer. In some embodiments, the implementation for full curing the curing temperature must be greater than the glass transition temperature. For example, the curing temperature may be in the range from about 140 to 180°C., or from about 143 to 180°C.

Synthesis: Poly(mochevinoi).

Stage 1

Stage 2

Stage 3

Stage 4

Group By

In not is which a non-limiting embodiments, the implementation of the present invention provides poly(mochevinoi) Group, containing the reaction product of components comprising: (a) at least one motivirovochnuyu prepolymer with isocyanate functionality, containing the reaction product of: (1) at least one urethane prepolymer with isocyanate functionality, containing the reaction product of: (i) a first amount of at least one MDI; and (ii) a first amount of at least one branched polyol; and (2) water; education motivirovannogo of prepolymer with isocyanate functionality; and (b) a second amount of at least one MDI and second amount of at least one branched polyol.

Examples of suitable polyisocyanates and polyol(s) discussed above. Any other optional polyols, amine curing agents, catalysts and other additives described above may be included in the reaction components in the amounts described above for the above Groups A-G. In some non-limiting embodiments, the reaction components essentially do not contain or do not contain amine curing agent described above, or do not contain amine curing agent.

In other non-limiting embodiments, the implementation of the present invention provides methods for obtaining poly(macawesomeshow) Groups, which include article is Hai: (a) interaction at least one MDI and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of urethane prepolymer with isocyanate functionality; and (b) interaction urethane prepolymer with isocyanate functionality of water and polyisocyanate with education motivirovannogo of prepolymer with isocyanate functionality; and (C) interaction of the reaction product of components containing motivirovochnuyu prepolymer with isocyanate functionality of at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least, 2 hydroxyl groups, where the reaction product components are essentially does not contain amine curing agent. The reaction can be represented as described above for the synthesis of poly(mochevinoi) Century

Group L

In other non-limiting embodiments, the implementation of the present invention provides poly(mochevinoi) Group L containing the reaction product of components comprising: (a) at least one motivirovochnuyu prepolymer with isocyanate functionality, containing the reaction product of: (1) at least one urethane prepolymer with isocyanate functionality, containing the reaction product of: (i) first to the icesta, at least one MDI selected from the group comprising trimers MDI and branched polyisocyanates, the polyisocyanate contains at least three isocyanate functional groups; and (ii) a first amount of at least one aliphatic polyol; and (2) water; education motivirovannogo of prepolymer with isocyanate functionality; and (b) a second amount of at least one MDI and a second amount of at least one aliphatic polyol.

Examples of suitable trimers and branched polyisocyanates polyisocyanates containing at least three isocyanate functional groups and polyol(s) discussed above. Any other optional polyols, amine curing agents, catalysts or other additives described above can be included as reaction components in the amounts described above for the above Groups A-G. In some non-limiting embodiments, the reaction components essentially do not contain or do not contain amine curing agent described above.

In some non-limiting embodiments, the implementation of the present invention provides methods for obtaining poly(macawesomeshow) group L, which include stages: (a) interaction of at least one poly is socyanate, selected from the group comprising trimers MDI and branched polyisocyanates, and at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups, with the formation of urethane prepolymer with isocyanate functionality; (b) interaction urethane prepolymer with isocyanate functionality of water and polyisocyanate with education motivirovannogo of prepolymer with isocyanate functionality; and (C) interaction of the reaction product of components containing motivirovochnuyu prepolymer with isocyanate functionality of at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups; where the reaction product components are essentially does not contain or does not contain an amine curing agent. The reaction can be represented as described above for the synthesis of poly(mochevinoi) Century

As discussed above, poly(mochevinoi) can be obtained by incorporating one or more amine curing agents in the components of the reaction. Amine functionality of the amine curing agent can be introduced into the reaction with the isocyanate groups with the formation of urea bridges or links within the polyurethane matrix.

Group M

p> In other non-limiting embodiments, the implementation of the present invention provides poly(mochevinoi) Group M containing the reaction product of components comprising: about 1 equivalent of at least one MDI; approximately from 0.1 to 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; from about 0.1 to 0.9 equivalents of at least one aliphatic diol containing from 2 to 18 carbon atoms; and at least one amine curing agent, where the reaction product components are essentially does not contain or do not contain complex polyetherpolyols and simple polyetherpolyols.

Non-limiting examples of suitable polyisocyanates, branched polyols containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, aliphatic diols and amine curing agents for use as reaction components to obtain polyurethanes of Group M, discussed in detail above for the Group A.

In some non-limiting embodiments, the implementation of a number of branched polyol used to obtain the polyurethane of Group M, can be from about 0.3 to 0.98 equivalent in other non-limiting embodiments priblizitel is but from 0.5 to 0.98 equivalent in other non-limiting embodiments of approximately 0.3 or ~ 0.9, or about 0.98 equivalent.

In some non-limiting embodiments, the implementation of a number of aliphatic diols used to obtain the polyurethane of Group M, can be approximately from 0.1 to 0.7 equivalent, in other non-limiting embodiments, from about 0.1 to 0.5 equivalent, and in other non-limiting embodiments is approximately 0.3 equivalent.

In some non-limiting embodiments, the implementation of a number of amine curing agent used to obtain the polyurethane of Group M, can be approximately from 0.1 to 0.9 equivalent, in other non-limiting embodiments, from about 0.1 to 0.7 equivalent, and in other non-limiting embodiments is approximately 0.3 equivalent.

As for poly(macawesomeshow) Group M, the expression "essentially does not contain complex polyetherpolyols and simple polyetherpolyols" means that complex polyetherpolyols and simple polyetherpolyols may be present as reaction components in appropriate amounts, as described above for polyurethane Group, or reactive components may not contain any complex polyetherpolyols or simple polyetherpolyols.

Any other optional polyol is, catalysts or other additives described above can be included as reaction components in the amounts described above in consideration of the above Groups A-H.

In other non-limiting embodiments, the implementation of the present invention provides methods for obtaining poly(mochevinoi), which include the stage of interaction in a process vessel components, comprising: at least one polyisocyanate; at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; at least one aliphatic diol containing from 2 to 18 carbon atoms; and amine curing agent, where the reaction product components are essentially does not contain or do not contain complex polyetherpolyols and simple polyetherpolyols.

Group N

In other non-limiting embodiments, the implementation of the present invention provides poly(mochevinoi) Group N containing the reaction product of components comprising: (a) at least one polyisocyanate selected from the group comprising trimers MDI and branched polyisocyanates, the polyisocyanate contains at least three isocyanate functional groups; (b) from about 0.1 to 0.9 equivalents of at least one polyol containing from 4 to 18 atoms of plastics technology : turning & the Yes and, at least 2 hydroxyl groups; and (C) at least one amine curing agent; where the reaction product components are essentially does not contain or do not contain complex polyetherpolyols and simple polyetherpolyols.

Non-limiting examples of suitable polyisocyanates, branched polyols containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, aliphatic diols and amine curing agents for use as reaction components to obtain polyurethanes of Group N, discussed in detail above for the Groups A-C.

In some non-limiting embodiments, the implementation of a number of branched polyol used to obtain the polyurethane Group N, may range from about 0.3 to 0.98 equivalent in other non-limiting embodiments, from about 0.5 to 0.98 equivalent, and in other non-limiting embodiments of approximately 0.3 or ~ 0.9, or about 0.98 equivalent.

In some non-limiting embodiments, the implementation of a number of aliphatic diols used to obtain the polyurethane Group N, may range from 0.1 to 0.7 equivalent, in other non-limiting embodiments, from about 0.1 to 0.5 equivalent, and in other non-limiting embodiments is approx the positive 0.3 equivalent.

In some non-limiting embodiments, the implementation of a number of amine curing agent used to obtain the polyurethane Group N, may range from 0.1 to 0.7 equivalent, in other non-limiting embodiments, from about 0.1 to 0.5 equivalent, and in other non-limiting embodiments is approximately 0.3 equivalent.

As for poly(macawesomeshow) Group N, the expression "essentially does not contain complex polyetherpolyols and simple polyetherpolyols" means that complex polyetherpolyols and simple polyetherpolyols may be present as reaction components in appropriate amounts, as described above for polyurethane Group, or reactive components may not contain any complex polyetherpolyols or simple polyetherpolyols.

Any other optional polyols, catalysts or other additives described above can be included as reaction components in the amounts described above in consideration of the above Groups A-H.

In other non-limiting embodiments, the implementation of the present invention provides methods for obtaining poly(mochevinoi), which include the stage of interaction in a process vessel components, comprising: at least one polyisocyanate selected from the group, including the ment trimers MDI and branched polyisocyanates; at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; at least one aliphatic diol containing from 2 to 18 carbon atoms; and amine curing agent, where the reaction product components are essentially does not contain or do not contain complex polyetherpolyols and simple polyetherpolyols.

In some embodiments, the implementation of poly(mochevinoi) Groups I-N of the present invention can be thermosetting.

Group Of

In some non-limiting embodiments, the implementation of the present invention provides a polyurethane material comprising the first portion of the crystalline particles with semioriental and connected together to commit their orientation along a first crystallographic direction, and the second part of the crystalline particles with semioriental and connected together to commit their orientation along a second crystallographic direction, and the first crystallographic direction is different from the second crystallographic direction, and where these crystalline particles comprise more than about 30% of the total volume of the polyurethane material.

Particles interact with each other or with the surface of the base, aligning their crystallographic axis in one is m, two or three directions. Used in this case, the definition of "leveling" or "aligned" relatively crystalline particles means that the particles of a specified crystalline parts are in the range of, usually, a fixed position and orientation. The preferred degree of alignment will depend on the intended application of the material. For alignment, it is desirable that the particles have the same shape with a dominant planar surfaces in a suitable orientation, such as perpendicular or parallel with respect to the desired direction of alignment.

In some non-limiting embodiments of the invention the first portion of the crystalline particles is aligned in two directions. In some non-limiting embodiments of the invention the first portion of the crystalline particles is aligned in three directions. In some embodiments, the crystalline particles are aligned along the line segment, which is in the range from about 1 to 50 nm along any direction.

In some non-limiting embodiments of the invention the second part of the crystalline particles is aligned in two directions. In some non-limiting embodiments of the invention the second part of the crystalline particles is aligned in three directions.

Crystalline particles of this izobreteny who have at least, "self-leveling" morphology. Used in this case, the definition of "self-levelling" morphology includes any particles that are capable of self-organization with the formation of a polycrystalline structure, where single particles are arranged along at least one crystallographic direction in the areas of higher density and order, such as slats. Examples of morphology crystalline particles with a self levelling morphology are cubic particles, hexagonal plates, hexagonal fiber, rectangular plate, rectangular particles, triangular plates, square plates, tetraene, Cuba, octagons, and mixtures thereof.

Self-levelling morphology can show the orientation, which may be approximately 10 degrees from the desired direction of alignment, while still capturing the desired properties to a sufficient degree. Therefore, particles having such morfologiya represent particles that essentially have the desired morphology. For example, for particles that are cubic, the particles do not have to be perfect cubes. The axis must not be ideally at an angle of 90°With nor be completely equal in length. The corners can also be cut from the particles. More then what about, the definition of "cube" or "cubic" are intended to make reference to morphology, and are not intended to limit particle systems cubic crystals. Indeed, the single-crystalline particles, which are orthorhombic, tetragonal or rhombohedral crystal structure, can also be used as cubes, if they have a certain cubic morphology. In other words, any essentially orthogonal single-crystal particles in which the surfaces are essentially square, essentially triangular or and those and others, which have essentially cubic morphology, from the standpoint of the present invention are cubic.

Crystalline particles can be aligned in a monolithic structure comprising a single crystal layer or multiple layers of crystals. The layer or layers usually are flat, although layers can conform to curved surfaces and complex geometries depending on the shape of the supports of the base material during formation and during curing of the polyurethane.

Polycrystalline materials of the present invention is obtained by compaction and alignment of many single-crystalline particles in a line, in order to achieve one-, two - or three-dimensional virani the project. In some non-limiting embodiments, the particles may have the ability to sonographically in line with the ageing (aging) or by heat treatment. In some non-limiting embodiments of implementation to obtain the level of diffusion in the solid state, sufficient to bind together adjacent particles, requires temperatures above approximately half of the melting temperature, which in most cases is usually in the range from about 35 to 100°C. the Selected temperature range will depend on the material that you want to connect, but can easily be determined by a qualified in this field specialist without holding excessive experiments within a given interval. The stage can be repeated with the formation of polycrystalline material having multiple layers of aligned particles. The resulting material is essentially three-dimensional object with one, two or three spatial alignments of single crystalline particles within the object.

FIGURE 4 is a micrograph in PAM (THE), showing the casting of the polyurethane obtained in accordance with example A, formulation 2. This casting analyzed using TEM two weeks after the polymerization of the polyurethane. Casting the storage which was at room temperature (approximately 25°C) for two weeks. As shown in figure 4, distinct regions arranged in a row of crystals does not occur.

FIGURE 5 is a micrograph in TEM, showing the casting of a polyurethane according to example A, formulation 2. This casting analyzed using TEM three weeks after polymerization of the polyurethane. Casting was kept at room temperature (approximately 25°C) for three weeks. As shown in FIGURE 5, there is initial formation of crystalline domains.

6 is a micrograph in TEM, showing the casting of a polyurethane according to example A, formulation 2. This casting analyzed using TEM seven months after polymerization of the polyurethane. Casting was kept at room temperature (approximately 25°C) for seven months. On the micrograph 6 visible region located in a number of crystals, generally parallel arrows.

7 is an electron diffraction pattern of the polyurethane of example A, formulation 2, stored at room temperature (approximately 25°C) for seven months. Bright spots in the picture are reflections from planes of the crystal lattice, which account for approximately 8×4 nm.

FIG is a micrograph in PAM, is providing a casting of a polyurethane according to example A, formula 2 obtained after keeping at room temperature for about 7 months. On the micrograph FIG seen a lot of areas or domains rows of crystals, generally parallel to the arrows, and the domains are oriented in different directions and exhibit higher density domains, compared to the samples aged for three weeks.

FIGURE 9 is a micrograph in TEM, showing the first part of the casting of a polyurethane according to example A, formulation 2, obtained after keeping at room temperature for about two to four weeks. The casting was kept at room temperature for two to four weeks. As shown in FIG.9, distinct regions arranged in a row of crystals does not occur.

FIGURE 10 is a micrograph in TEM, showing the second part of the casting of a polyurethane according to example A, formulation 2 shown in FIG.9. As can be seen in a limited area in figure 10, there is initial formation of crystalline domains.

The samples presented on figures 9 and 10, have an impact on Gardner 180 DM·lb.

11 is a micrograph in TEM, showing the casting of a polyurethane according to example A, formulation 2. This casting to address avana using TEM approximately two to four weeks after the polymerization of the polyurethane. The casting was kept at room temperature for two to four weeks. On the micrograph 11 on limited areas visible region located in a number of crystals.

FIG is a micrograph in TEM, showing the first part of the casting of a polyurethane according to example A, formulation 2, obtained after keeping at room temperature for about 7 months. On the micrograph FIG visible to a large area or a domain located in a number of crystals.

FIG is a micrograph in TEM, showing the second part of the casting of a polyurethane according to example A, formulation 2 shown in FIG. On the micrograph FIG seen a lot of areas and domains rows of crystals, and the domains are oriented in different directions and exhibit higher density domains, compared to the samples aged for a shorter period of time.

The samples presented on FIG and 13, have an impact on Gardner 640 DM·lb.

FIG is a graph of heat flow as a function of temperature using differential scanning calorimetry, DSC) for castings made of polyurethane according to example A, formulation 2, obtained after keeping under normal conditions for two weeks, which is months and seven months, respectively. The enthalpy of endothermic melting of the crystalline domains grow in time, showing the change in morphology of the polymer and microstructure in time, even if the polymer is glassy and highly crosslinked with a glass transition temperature of 235°F (113°C). As growth in the number and size of the crystalline domains, enthalpy of melting increases. Impact on Gardner grows with time. After two weeks, the impact on Gardner 180 DM·lb. Within three months, the impact on Gardner is 380 DM·lb. After seven months, the impact on Gardner is 640 DM·lb.

FIG is a graph showing the impact on Gardner as a function of young's modulus for casting polyurethane according to example A, formulation 2 and 1, obtained after keeping under normal conditions for a period of seven months and one year, respectively. After seven months in the case of formulation 2 impact on Gardner is 640 DM·lb. After one year in the case of formulation 1 impact on Gardner is 400 DM·lb.

In some non-limiting embodiments, the implementation of the polyurethane material comprises a monolithic sinter the first part of the crystalline particles with small-angle grain boundaries between them, connected together by a polymeric phase.

In some neogranichinymi the variants of implementation of the polyurethane material comprises a monolithic sinter the second part of the crystalline particles with small-angle grain boundaries between them, connected together by a polymeric phase.

In some non-limiting embodiments, the implementation of the polyurethane material comprises a monolithic sinter the first part of the crystalline particles with small-angle grain boundaries and, as a rule, with the amorphous phase between them.

In some non-limiting embodiments, the implementation of the polyurethane material comprises a monolithic sinter the second part of the crystalline particles with small-angle grain boundaries and, as a rule, with the amorphous phase between them.

In some non-limiting embodiments, the implementation of the thickness of the first portion of the crystalline particles is less than approximately 50 nm. In some non-limiting embodiments, the implementation of the thickness of the second portion of the crystalline particles is less than approximately 50 nm. The length and width, respectively, of the first part may vary, for example approximately 4 nm to 8 nm.

In some non-limiting embodiments, the implementation of the thickness of the first portion of the crystalline particles may be in the range from about 10 to 100 nm. In some non-limiting embodiments, the implementation of the thickness of the second portion of the crystalline particles may be in the range from about 4 to 50 nm. The length and width, respectively, of the second part may vary, for example approximately 4 nm to 8 nm.

In some non-limiting embodiments, the implementation of the crystalline particles comprise at least about 30% of the total material. In other non-limiting embodiments, the implementation of the crystalline particles comprise at least about 40%, or at least about 50%, or at least about 60%, or at least about 70%, or at least about 80%, or at least about 90% of the total material. The percentage of crystalline particles can be determined using DSC. For example, the product obtained from formulations 2, described below, stored under normal conditions (approximately 25°C) for 7 months, has a crystallinity of approximately 43% vol.

In some non-limiting embodiments, the implementation of the polyurethane contains a reaction product of components comprising: (a) about 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate); (b) about 0.3 equivalents of trimethylolpropane; and (C) about 0.7 equivalents of butanediol or pentanediol. In some non-limiting embodiments, butanediol represents 1,4-butanediol. In some non-limiting embodiments, pentanediol represents 1,5-pentanediol.

In some non-limiting embodiments, the implementation of resistance to shock loading the Cam described above polyurethanes and poly(macawesomeshow) Groups a-M in accordance with the present invention can be improved by curing or heat processing.

In some non-limiting embodiments, the implementation of the polyurethane material after the formation may be maintained at least for about 2 weeks. In some non-limiting embodiments, the implementation of the polyurethane material after the formation may be maintained at least for about 2 months. In some non-limiting embodiments, the implementation of the polyurethane material after the formation may be maintained at least for about 7 weeks.

In some non-limiting embodiments, the implementation of the polyurethane material after the formation is heated at a temperature of from about 90 to 150°C., or from about 200 to 290°F (about 93 to 143°C) for about 1 to 24 hours. In some non-limiting embodiments, the implementation of the polyurethane material is heated at a temperature sufficient to induce the mobility of the grain boundary so that the particles grow up until the collision with the grain boundaries of neighboring crystals will not prevent additional growth. The end result is a polycrystalline microstructure, grain which for all practical purposes are arranged in a row in two or three directions so that they behave like a single crystal classifies the flax certain desired properties.

The impact resistance or flexibility can be measured using a number of conventional techniques known to experts in this field of technology. Flexible materials can be measured using tests of strength when hitting the Gardner with the use of device Gardner for strength testing at impact in accordance with ASTM-D 5420-04, which consists of a 40-inch (101.6 cm) aluminum tube, in which 8 - or 16-pound (17,6 or 35,2 kg) weight falls from various heights on a metal dart, which is based subjected to the test, with sample sizes (2×2×1/8 DM) (5,1 x 5,1×0.3 cm). In a non-limiting embodiment, data on the impact resistance test of strength when hitting the Gardner constitute at least about 65 DM·lb (7,3 j), or from about 65 to 640 DM·lbs (7,3-72 j).

In another embodiment, the impact resistance can be measured using tests Dynatup Test in accordance with ASTM-D 3763-02, which is a high-speed test using a torque element, which measures the total energy absorption in the first microseconds of the blow. Impact strength can be measured in Joules. In a non-limiting embodiment, the base may have an impact strength of at least about 35 joules, or approximately 35 to 105 J.

Gr is the PAP R

In some non-limiting embodiments, the implementation of the present invention provides polyurethane powder covering the composition. Powder covering compositions can be prepared from any polyurethane or poly(macawesomeshow) Groups, And-N, described in detail above.

In non-limiting embodiments, the implementation of the present invention provides methods for preparing polyurethane powder covering compositions which include stage: communicating at least one MDI, at least one aliphatic polyol with education, as a rule, solid prepolymer with a hydroxyl functionality; melting prepolymer with a hydroxyl functionality; melting at least one normally solid MDI with the formation of molten MDI; mixing of molten prepolymer with hydroxyl functionality and molten MDI with the formation of the mixture; and curing the mixture with the formation, usually solid powder covering composition.

Usually solid prepolymer with a hydroxyl functionality can be obtained by the reaction of MDI(s) with an excess of aliphatic(s), polyol(s) and catalyst in amounts described above, and when heated prepolymer is at a temperature of approximately 140°C. or at a temperature of from about 150 to 180°C for about 1 to 24 hours, to contribute essentially to the full end of the reaction components and the formation of normally solid prepolymer.

In some non-limiting embodiments, the implementation of the polyisocyanate is a branched or represents a trimer, as discussed above, and the aliphatic polyol is an aliphatic diol containing from 4 to 18 carbon atoms, or 4 or 5 carbon atoms, such as propandiol, butanediol, cyclohexanedimethanol, 1,10-decandiol and/or 1,12-dodecanediol. In other non-limiting embodiments of the invention, the polyisocyanate may be any polyisocyanate, discussed above, and the aliphatic polyol may be a branched diol containing from 4 to 18 carbon atoms, such as trimethylolpropane.

The equivalent ratio of isocyanate functional groups to hydroxyl functional groups is in the range from about 1:0.9 to 1:1.1, the or is approximately 1:1.

Typically, the solid polyisocyanate may be melted, for example, by heating at a temperature of from about 35 to 150°C for about 2 to 24 hours with the formation of molten MDI. Molten prepolymer with hydroxyl functionality and melted polyisocyanate are mixed and utverjdayut with education is receiving generally homogeneous mixture, acceptable for forming a powder coating, which is discussed below. The equivalent ratio of isocyanate functional groups MDI to hydroxyl functional groups prepolymer may be in the range approximately from 1.05:1 to 0.95:1, or approximately 1:1.

In other non-limiting embodiments, the implementation of the present invention provides methods of obtaining polyurethane powder covering composition, comprising the stage of: communicating at least one MDI, at least one aliphatic polyol with education, as a rule, solid prepolymer with a hydroxyl functionality; dissolution of prepolymer with a hydroxyl functionality in the first solvent from the first solution; dissolving at least one normally solid MDI in the second solvent, which is the same solvent or compatible with the first solvent, with the formation of the second solution; mixing the first and second solutions; and remove essentially all of the solvent to form normally solid powder covering composition.

In some non-limiting embodiments, the implementation of the polyisocyanate(s) is(are) extensive(and) or a trimer, as this absurd the elk above, and the aliphatic polyol is an aliphatic diol containing from 4 to 18 carbon atoms, or 4 or 5 carbon atoms, such as propandiol and/or butanediol. In other non-limiting embodiments of the invention, the polyisocyanate may be any polyisocyanate, discussed above, and the aliphatic polyol may be a branched diol containing from 4 to 18 carbon atoms, such as trimethylolpropane.

Usually solid prepolymer with a hydroxyl functionality can be obtained by the reaction of MDI(s) with an excess of aliphatic(s), polyol(s) and catalyst, the types and amounts of which are described above. Prepolymer with a hydroxyl functionality is dissolved in the first solvent with the formation of the first solution. The solvent may be any solvent capable of dissolving prepolymer with hydroxyl functionality, such as dipolar aramony solvent, for example, m-pyrol (N-methyl-2-pyrrolidone), N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide (DMSO), methylene chloride, dichlorobutane, cyclohexanone, dimethylformamide and/or acetonitrile. The amount of solvent may be in the range from about 20 to 95% of the mass. based on the weight of solids of prepolymer with hydroxyl functionality.

As p is Avila, solid polyisocyanate is dissolved in the second solvent, which is the same solvent or compatible with the first solvent, to obtain a second solution. The solvent may be any solvent capable of dissolving the usually solid polyisocyanate, such as dipolar aramony solvent, such as m-pyrol (N-methyl-2-pyrrolidone), N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide (DMSO), methylene chloride, dimethylformamide and/or acetonitrile. The amount of solvent may be in the range from about 20 to 95% of the mass. based on the weight of solids MDI.

The first and second solutions are mixed and remove essentially all of the solvent, for example, with the help of vacuum in the furnace, with the formation of essentially solid powder suitable for use as a cover song. The powder can be divided or finely chopped, if necessary.

Capable of curing powder covering composition, which can be used in the present invention are usually obtained by first dry blending the polymer, for example polyurethane or moth(mochevinoi), crosslinking agent (if present), particles and additives, such as degassing agents, agents for improving the fluidity and catalysts, in a mixer, e.g. the measures in the blade Henshel mixer. The mixer runs for a period of time sufficient to obtain a dry homogeneous mixture of the loaded material. The dry homogeneous mixture is then mixed in the melt in the extruder, for example in a twin screw extruder with co-rotating screws, which operates in the temperature range sufficient to melt the components, but not to allow gel formation.

Not necessarily capable of curing powder covering the composition of the present invention may be mixed in the melt in two or more stages. For example, a mixture of the first melt is prepared in the absence of a curing catalyst. The mixture of the second melt is prepared at a lower temperature from the dry mixture of the first melt and curing catalyst. Mixed in the melt capable of curing powder covering composition, usually crushed to an average particle size of, for example from 15 to 30 microns.

On the other hand, powder covering compositions of the present invention can be obtained by mixing and extruding ingredients, as described above, but without particles. Particles can be added to the formulation as a post-additive by simple mixing of the particles in the crushed powder covering the composition, for example by mixing using a Henschel mixer. Some n is limiting embodiments of the invention the powder covering the composition suspended in a liquid medium, such as water, which may be applied by spraying.

Group Q

In some non-limiting embodiments, the compositions of the present invention may additionally include one or more types of reinforcing materials. Such reinforcing materials may be present in any desired physical form, for example in the form of particles, including, but without limiting them, in the form of nanoparticles, agglomerates, fibers, chopped fibers, mats, etc.

Reinforcing materials can be formed from materials selected from the group comprising polymeric inorganic materials, polimernye inorganic materials, polymeric organic materials, polimernye organic materials, their composites and their mixtures, which are chemically different from the polyurethane or poly(mochevinoi). Used in this case, the definition of "chemically different from the polyurethane or poly(mochevinoi) means that the reinforcing material is at least one other atom or has a different arrangement of the atoms in comparison with polyurethane or poly(motivirovannom).

Used in this case, the definition of "inorganic polymer material" means a polymeric material having a main chain of the repeating element based on the element or elements other than carbon. (See publ is by: James Mark et al., Inorganic Polymers, Prentice Hall Polymer Science and Engineering Series (1992), page 5, which is incorporated by reference). Moreover, used in this case, the definition of "organic polymer materials" means synthetic polymeric materials, synthetic polymeric materials and natural polymeric materials, all of which have a main chain of recurring level carbon-based.

Used the definition of "organic material" means a carbon-containing compounds where carbon, typically associated with himself and hydrogen and often with other elements, and also eliminates binary compounds, such as oxides of carbon, a carbide, a sulfide, carbon and so on; such ternary compounds as the cyanides of metals, CARBONYLS metals, phosgene, carbondisulfide and others; and the carbon-containing ionic compounds, such as metal carbonates, such as calcium carbonate and sodium carbonate. (See, for example, publications: R. Lewis, Sr.,Hawley's Condensed Chemical Dictionary(12-th Ed., 1993), pp. 761-762; and M. Silberberg,Chemistry The Molecular Nature of Matter and Change(1996), p. 586, which are included as a reference).

Used in this case, the definition of "inorganic material" means any material that is not organic material.

Used in this case, the definition of "composite material" means a combination of two or more different material is. For example, the composite particle may be formed from a primary material that is coated, plated or encapsulated by one or more secondary materials with the formation of composite particles, which has a softer surface. In some non-limiting embodiments, the implementation of the particles formed from composite materials, can be obtained from a primary material that is coated, plated or encapsulated with various forms of primary material. For more information on the particles, which can be used in the present invention, see publication G. Wypych, Handbook of Fillers, 2nd Ed., (1999), p. 15-202, which is incorporated by reference.

Reinforcing materials acceptable for use in the compositions of the present invention may include inorganic elements or compounds known in the art. Suitable polimernye, inorganic reinforcing materials can be formed from ceramic materials, metallic materials, and mixtures of any of these materials. Polimernye, inorganic materials, which can be useful when forming the reinforcing materials of the present invention include inorganic materials selected from the group comprising graphite, metals, oxides, carbides, nitrides, borides, sulfides, ilicate, carbonates, sulfates and hydroxides. Suitable ceramic materials are metal oxides, metal nitrides, metal carbides, sulfides of metals, silicates of metals, borides of metals, metal carbonates, and mixtures of any of the above. Non-limiting examples of suitable metals are molybdenum, platinum, palladium, Nickel, aluminum, copper, gold, iron, silver, alloys and mixtures of any of the above metals. Non-limiting examples of metal nitrides include, for example, boron nitride; non-limiting examples of metal oxides include, for example, zinc oxide; non-limiting examples of suitable sulfides of metals are, for example, molybdenum disulfide, tantalum disulfide, tungsten disulfide, and zinc sulfide; non-limiting examples of silicates of metals are, for example, aluminum silicates and magnesium silicates, for example, vermiculite. In some non-limiting embodiments, the implementation of the reinforcing material essentially does not contain less than 5% of the mass. or less than 1% of the mass.) or does not contain fillers, such as sodium carbonate, calcium carbonate, silicates, alginates, soot, and metal oxides such as titanium oxide, silicon dioxide and zinc oxide.

In some non-limiting embodiments, the implementation of the reinforcing material may include a core of essentially and the one inorganic oxide, such as silica in colloidal, colloidal or amorphous form, alumina or colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, Zirconia, for example, colloidal or amorphous Zirconia, and mixtures of any of these components; or an inorganic oxide of one type, on which is deposited an organic oxide of another type. In some non-limiting embodiments, the implementation of the reinforcing material should not significantly affect the optical characteristics of utverzhdenii composition. Used in this case, the definition of "transparent" means that utverjdenie floor has a turbidity (BYK Haze index of less than 50 when measured with the use of the device BYK/Haze Gloss Instrument.

The composition may include precursors suitable for forming particles of silicon dioxidein situusing the Sol-gel process. The composition in accordance with the present invention may contain alkoxysilane, which can be hydrolyzed with the formation of particles of silicon dioxidein situ. For example, tetraethylorthosilicate can be hydrolyzed with acid, such as hydrochloric acid, and condensed with the formation of particles of silicon dioxide. Other useful particles are surface modified silica, e.g. the, described in U.S. patent No. 5853809 (column 6, line 51 - column 8, line 43, are included in the description by reference).

In the present invention can be used sols, such as the organosol, the reinforcing particles. Such sols can represent a wide range of colloidal silica with small particles having an average particle size in the intervals described below. Colloidal silica can be surface modified during or immediately after the formation of particles. Such surface modified silica can have on their surface chemically bonded carbon-containing residues, as well as groups such as anhydrous SiO2groups and SiOH groups, various ionic groups, are physically associated or chemically bonded with the surface of the silicon dioxide adsorbed organic group, or a combination of any of the above components, depending on the desired characteristics of the particles of silicon dioxide. Such surface-modified silica is described in U.S. patent No. 4680204, which is included as a reference. Such colloidal silica with small particles easily accessible, essentially colorless and have refractive indexes which allow them to be included in the composition, which, without additional pigmentary components, which, as is known in the art, stained and/or reduce the transparency of such compositions, leads to a colorless, transparent compositions or coatings.

Other suitable non-limiting examples of reinforcing materials are colloidal silica, such as silica, which are commercial products of Nissan Chemical Company under the trade name ORGANOSILICASOLSTMsuch as ORGANOSILICASOLSTMMT-ST, and commercial products Clariant Corporation as HIGHLINKTM; colloidal oxides of aluminium, such as aluminium oxides, which are commercial products Nalco Chemical under the trade name NALCO 8676®; and colloidal Zirconia, such as oxides of zirconium offered by Nissan Chemical Company under the trade name HIT-32M®.

In some non-limiting embodiments of the present invention the reinforcing material has a nanostructure. Used in this case, the term "nanostructure" refers to a three-dimensional object, where the length of the longest size is in the range from 1 to 1000 nm, for example from 1 to 500 nm, or from 1 to 100 nm, or from 1 to 40 nm.

Nanostructured reinforcing materials can be introduced into a polymer matrix by pre-distribution of the obtained nanostructures, such as, for example, nanoglide, in the polymer solution. Alternative or additional nanostructured reinforcing materials can be introduced into the polymer matrix by forming nanostructures in situ. For example, nanostructured reinforcing materials can be formed byin situby mixing the solution of the precursor to obtain a polyurethane or poly(mochevinoi) with a precursor for the nanostructures with the formation of the mixture, the formation of nanostructures in the matrix polymer of the precursor nanostructures and polymer formation from a solution of the precursor polymer.

Used in this case, the expression "the solution of a precursor for polyurethane or poly(mochevinoi)" refers to any material that can be used as source material for the formation of polyurethane or poly(mochevinoi), as described above. For example, if the desired end product is an aliphatic polyurethane, suitable precursors of the polymer include, but are not limited to, 1,4-butanediol, trimethylolpropane and bis(4-isocyanatophenyl)methane and thiodiethanol.

Used in this case, the expression "precursor for the nanostructures" refers to any material that can be used as source material for the formation of nanostructures.

In some non-limiting embodiments of the invention added to the mixture solvent, such as water, ethanol, isopropanol, butanol, etc.

The nanostructures are formed, while the viscosity of the polymer at the table is to low, the nanostructures can be embedded in a polymer matrix. The formation of nanostructures can be initiated using a variety of techniques. In a non-limiting embodiment of the present invention, the nanostructures are formed by regulating the pH of the mixture. The acid or base, such as ammonia, can be used to adjust the pH of the solution. Depending on the solution of the precursor polymer and the precursor for the nanostructures there is an optimal interval of pH values, which will be formed nanostructures. Qualified in this field specialist is known that the optimal range of pH is determined by both its predecessors.

In another non-limiting embodiment of the invention, the mixture can be heated to initiate the formation of nanoparticles. The mixture can be heated to any temperature, provided that the mixture is not heated to a temperature above the temperature at which the solution of the precursor will be destroyed. For example, a solution of a precursor containing a polyurethane or poly(mochevinoi), can not be heated above 200°C, as this temperature corresponds to the temperature at which the polyurethane or poly(mochevinoi) begin to decompose. As for the interval of pH, optimum temperature range which will clicks Sovietica particles, depends on the corresponding solution of the precursor of the polyurethane or poly(mochevinoi) and the appropriate precursor for the nanostructures. Qualified in this field specialist is known that the optimal temperature range is determined by both its predecessors. As a rule, the higher the temperature to which the mixture is heated, and/or longer heat the mixture, the greater the size of the nanostructures, which will be generated.

In another non-limiting embodiment of the invention the formation of nanostructures is carried out by heating the mixture after the establishment of the pH of the mixture. In another non-limiting embodiment of the invention the formation of nanostructures is carried out by heating the mixture, and then the regulation of the pH of the mixture.

In various other non-limiting embodiments of the invention, the nanostructures can be formed by using one or more of the following techniques: increasing pressure on the mixture, the change in the solution concentration of the precursor for polyurethane or poly(mochevinoi); the use of an initiator of the formation of nanostructures; and nucleation (adding no more than 5% of the desired nanostructured material based on the assumed mass of the formed nanostructures, which is well known in the art).

Educated nanost ucture are charged specimens. If the pH of the solution is adjusted to cause the formation of nanostructures, the charge is the result of regulating the pH. If during the stage of formation of nanostructures regulation of pH was not carried out, to create the charge may be added to polymeric stabilizer, such as, but without limitation, polymethacrylate sodium in water and polymethacrylate ammonium in the water, both of which are commercial products of the company R.T. Vanderbilt Company, Inc., Norwalk, CT, available as Darvan®7 and as Darvan®C, respectively.

The third stage involves the formation of polyurethane or poly(mochevinoi) from a mixture containing a solution of a precursor of the polyurethane or poly(mochevinoi). The formation of polyurethane or poly(mochevinoi) can be invoked through the use of various techniques (as discussed in detail above), based on the solution of the precursor of the polyurethane or poly(mochevinoi) and the precursor for the nanostructures.

In another embodiment of the present invention the second and third stages described above, changing places.

A method of producing polymers having nanostructures embedded in a polymer matrix in accordance with the present invention, referred to as process "in situ". This means that the nanostructures are formed during the same process by which it is formed and the polymer, in contrast to prior what about the formed nanostructures, which is dispersed in the polymer solution.

While some methods of the present invention in a mixture can be formed ions (cations and/or anions). The resulting ions and other process variables, such as system pressure, which can withstand the mixture can affect the final polymer. For example, the number of nanostructure formation and morphology of nanostructures will depend on the type and amount of ions present in the solution.

In the polymeric matrix nanostructures, as a rule, all the time to approach each other and collide, as they have kinetic energy. Under normal conditions, some nanostructures will connect with each other and will form agglomerates due to various forces, for example due to the interaction of van der Waals forces. As discussed above, the agglomerating is not desirable, because the nanostructures can actually become particles with the correct dimensions and the desired effect of the introduction of nanostructures decreases.

However, the above methods can give polymers having nanostructures in the polymer matrix, which do not form agglomerates to such an extent as to jeopardize the performance properties of the polymer, for example, to improve thermal stability of the polymer and/or lower chemical activity is any polymer. The nanostructures do not form agglomerates as they are stable. Stabilization can be achieved with electrostatic stabilization and/or steric stabilization.

Because the nanostructures in a polymer matrix are equally charged samples, they repel each other. This prevents the nanostructures to approach each other so closely that they form the agglomerate. This phenomenon is called electrostatic stabilization.

Because the nanostructures surrounded by a solution of the precursor polymer, the formation of nanostructures lose a degree of freedom, which they would have otherwise, because the nanostructures are converging with each other. Such a loss of degrees of freedom expressed in thermodynamic terms as the loss of entropy, which creates the necessary barrier to prevent the formation of agglomerates. This phenomenon is called steric stabilization. The same principle applies when the method includes the formation of the polymer prior to formation of nanostructures.

The concentration of nanostructures in a polymer matrix may be in the range from about 0.1 to 90%, for example from 3 to 85%, or from 15 to 80% based on the total amount. Nanostructures in a polymer matrix can have the following form: spherical, multi-faceted, cubic, triangular, p is tugaloo, diamond-shaped, needle-shaped, rod shape, a disk shape, and other Nanostructures in a polymer matrix can have an aspect ratio from 1:1 to 1:1000, for example from 1:1 to 1:100.

Non-limiting examples of suitable nanostructured materials are nanostructures of titanium oxide, aluminum oxide, mixed oxide of indium and tin (ITO), mixed oxides of antimony and tin (ATO), monobutylphthalate, acetate India and trichloride antimony, introduced in the polymer matrix. Suitable precursor for the nanostructures of titanium oxide include, but are not limited to, ISO-propoxy titanium chloride, titanium (IV) and citylocal potassium. Suitable precursor for the nanostructures of aluminum oxide include, but are not limited to, ISO-propoxy aluminum tri-tert.-piperonyl aluminum, tri-sec.-piperonyl aluminum, triethoxy aluminum and pentanedionate aluminum. Suitable precursor for the nanostructures zirconium oxide include, but are not limited to, ISO-propoxy zirconium tert.-piperonyl zirconium, piperonyl zirconium, atoxic zirconium 2,4-pentanedionate zirconium and cryptobenthic Zirconia.

In the first stage, a solution of a precursor for a polyurethane or poly(mochevinoi) is mixed with a precursor for the nanostructures.

In the second phase in the polymer matrix of the form nanostruct the s of the precursor nanostructures. The formation of nanostructures may be caused by adjustment of pH with subsequent heating. The pH value can be adjusted by introducing a mixture of the agent, such as ammonia. In the case of ITO nanostructures in aqueous solution of urethane or mochevinoi nanostructures begin to form at pH>8. After establishing the pH of the mixture is heated to a temperature up to 100°C. the Heated solution to a temperature higher than 100°C can cause decomposition of the polymer matrix. As discussed above, heating the mixture for a longer period of time may lead to an increase in the size of the nanostructures.

In the third stage, the solution of the precursor polymer is converted into a polymer, as described above, for the formation of polyurethane and poly(mochevinoi).

In a non-limiting embodiment of the invention obtained reinforced polymer is used as an intermediate layer in laminated glass for use in vehicles and in architecture. As is known in the art, laminated glass can be produced by applying an intermediate layer between two transparent glass sheets.

In this specific embodiment of the present invention as laminated glass for use in vehicles and in architecture it is important that the nanostructures do not form agglomerates. If the nanostructures form all the merlata and actually reach a diameter of more than 200 nm, nanostructures will diffuse the rays of visible light to such an extent that the transmission through the cushioning layer will be insufficient for the application. The polymer containing nanostructures having an acceptable size for this application, can be identified using the values of turbidity". Turbidity is associated with the degree to which there are barriers to transparency. The larger nanostructures present in the polymeric matrix, the higher the turbidity. In accordance with the present invention laminated glass for a vehicle and for use in the architecture has a turbidity less than or equal to about 1%, for example less than or equal to approximately 0.3%, or less than or equal to about 0.2%when measured using the system Hazeguard System (BYK-Gardner, Columbia, MD).

In a variant of the invention, which provides a polyurethane or poly(mochevinoi)with nanostructures of titanium oxide, embedded in a polymer matrix, the first stage may include a mixture of ISO-propoxide titanium with 1-10% of the mass. solution N2About2and suitable precursors of polyurethane or poly(mochevinoi), which are described above. H2About2acts as the initiator for nanostructures of titanium oxide; especially for nanostructures of titanium oxide in octahedrites form (in the form of anatase). The optional is that polymers such as polyoxyethylene(20)servicemanual, commercially available as Tween®80 (ICI Ltd., Bridgewater, NJ), can be added to the solution to help stabilize the nanostructure of titanium oxide.

In the second stage of the nanostructure of titanium oxide formed from the precursor by heating the mixture to a temperature up to 100°C.

In the third stage, the solution of the precursor polymer is converted into a polyurethane or poly(mochevinoi), which is discussed in detail above.

In a non-limiting embodiment of the present invention the polyurethane or poly(mochevinoi)containing nanostructures of titanium oxide, aluminum oxide or zirconium oxide, embedded in a polymer matrix, can be used as optical lenses. The polymer containing nanostructures having acceptable optical lens size may be detected using values of turbidity". In accordance with the present invention, the optical lens has a turbidity less than or equal to about 0.5%, for example less than or equal to about 0.2%when measured using the system Hazeguard System (BYK-Gardner, Columbia, MD).

In a non-limiting embodiment of the invention obtain a polyurethane having a structure of ITO or ATO, embedded in a polymer matrix. Such a polymer can be obtained in the following way. In the first stage the solution pre is restonica of trimethylolpropane, methylene-bis(4-cyclohexylsulfamate) and thiodiethanol mixed with the precursor nanostructures ITO or ATO.

A suitable solution of a precursor for polyurethane is trimethylolpropane, methylene-bis(4-cyclohexylidene) and thiodiethanol and includes, but without limitation, 1,4-butanediol. Suitable precursors for ITO nanostructures include trichloride monobutyl and acetate India. A suitable precursor for the nanostructures ATO is trichloride antimony.

In the second stage of the precursor nanostructures are formed of ITO or ATO. The formation of nanostructures can be caused by adjusting the pH of the solution with the introduction of the mixture of the agent, such as ammonia, followed by heating the mixture. In the case of ITO nanostructures nanostructures begin to form at pH>8. After establishing the pH of the mixture is heated to a temperature up to 100°C. As discussed above, heating the mixture for a longer period of time may lead to an increase in the size of the nanostructures.

At the third stage of 1,4-butanediol are mixed with trimethylolpropane, methylene-bis(4-cyclohexylsulfamate) and thiodiethanol, which is well known in the art. For example, 1,4-butanediol, thiodiethanol, trimethylolpropane (TMP, str) and DESMODUR®W can all be mixed in the reactor and heated to 180°F. the Mixture smesi the Ute in a vacuum for about 15 minutes, and then added to the mixture of a tin catalyst, such as dibutyltindilaurate, or carbonate of bismuth at a concentration of 25 h/million Then the mixture is poured into a glass form and utverjdayut for at least 20 hours at 250°F (121°C) c the formation of polyurethane.

In a non-limiting embodiment of the invention trimethylolpropane, methylene-bis(4-cyclohexylidene), thiodiethanol having nanostructures ITO or ATO, embedded in a polymer matrix, is used for the antistatic layer to the Windows of the plane. The polymer nanostructures has a modulus of elasticity greater than the modulus of elasticity standard trimethylolpropane, methylene-bis(4-cyclohexylsulfamate), thiodiethanol in the absence of nanostructures ITO/ATO.

In other non-limiting embodiments of the invention the reinforcing material is a nanostructured reinforcing material formed in situ due to the swelling of the polyurethane in a solvent containing a precursor for the nanostructures, and due to the formation of nanostructures in a matrix of polyurethane precursor nanostructures. Non-limiting examples of suitable solvents for the soft swelling of the polymer are methanol, methyl ether of propylene glycol, such as DOWANOL PM (commercially available from Dow Chemical Co., Midland, Michigan), datetoday alcohol, 2-propanol, 1-propanol and acetylphenol

The polymer containing nanostructures having an appropriate size for the Windows of the aircraft may be detected using values of turbidity". In accordance with the present invention a multilayer window for aircraft has a turbidity less than or equal to about 1%, for example less than or equal to about 0.5%, when measured with the use of the system Hazeguard System (BYK-Gardner).

In some non-limiting embodiments of the present invention the reinforcing materials have a hardness value higher than the value of hardness of materials, which can wear out the friction polymer coating or a polymer base. Examples of materials that can wear out the friction polymer coating or a polymer base, include, but are not limited to, soil, sand, bedrock, glass, automotive brushes, etc. Values of hardness of the particles and materials, which can wear out the friction polymer coating or a polymer base, can be determined using a conventional method of determining the instrumental hardness, for example, the method of determining the hardness Vickers or Brinell hardness; or can be defined on the original scale of hardness according to the Mohs scale, which shows the relative resistance of a material to scratch the surface on a scale from one to ten. Value is vergoti Mohs several non-limiting examples of particles, derived from inorganic materials suitable for use in the present invention are shown below in table A.

TABLE AND
Material particlesThe Mohs hardness (original scale)
The boron nitride21
Graphite0.5 to 12
Molybdenum disulfide13
Talc1-1,54
Mica2,8-3,25
Kaolinite2,0-2,56
Gypsum1.6 to 27
Calcite (calcium carbonate)38
Calcium fluoride49
Zinc oxide4,510
Aluminum2,511
Copper 2.5 to 312
Iron4-513
Gold2.5 to 314
Nickel515
Palladium4,816
Platinum4,317
Silver2.5 to 418
The zinc sulfide3.5 to 419

1K. Ludema,Friction, Wear. Lubrication.(1996) at page 27, is included as a reference.

2R. Weast (Ed.),Handbook of Chemistry and Physics.CRC Press (1975) at page F-22.

3R. Lewis, Sr.,Hawlev's Condensed Chemical Dictionary.(12th Ed. 1993) at page 793, included as a reference.

4Hawlev's Condensed Chemical Dictionary.(12th Ed. 1993) at page 1113 included as a reference.

5Hawlev's Condensed Chemical Dictionary.(12th Ed. 1993) at page 784, included as a reference.

6Handbook of Chemistry and Physicsat page F-22.

7Handbook of Chemistry and Physicsat page F-22.

8Friction. Wear. Lubricationat page 27.

9Friction. Wear, Lubricationat page 27.

10Friction. Wear, Lubricationat page 27.

11Friction. Wear. Lubricationat page 27.

12Handbook of Chemistry and Physicsat page F-22.

13Handbook of Chemistry and Phvsicsat page F-22.

14Handbook of Chemistry and Phvsicsat page F-22.

15Handbook of Chemistry and Phvsicsat page F-22.

16Handbook of Chemistry and Phvsicsat page F-22.

17Handbook of Chemistry and Phvsicsat page F-22.

18Handbook of Chemistry and Phvsicsat page F-22.

19R. Weast (Ed.),Handbook of Chemistry Phvsics.CRC Press (71 sup.st Ed. 1990) at page 4-158.

In some non-limiting embodiments, the reinforcing material can be formed from a primary material that is coated, plated or encapsulated with one or more secondary materials with the formation of the composite material, which has a more solid surface. In other non-limiting embodiments, the implementation of the particles of the amplifier can be obtained from a primary material that is coated, plated or encapsulated with various forms of primary material to form a composite material, which has a more solid surface.

In some non-limiting examples of inorganic particles derived from inorganic material such as silicon carbide or aluminum nitride can be obtained by using a coating of silicon dioxide, carbonate or nanoglide with the formation of useful composite particles. In other non-limiting embodiments, silane combining the agent with alkyl side chains can interact with the surface of norgani eskay particles, formed of inorganic oxide, obtaining useful composite particles having a "softer" surface. Other examples include cladding, encapsulation of particles or a coating on the particles, which are formed from polimernyh or polymeric materials, using different polimernyh and polymeric materials. One of neorganicheskoi examples of such composite particles is DUALITETMthat is a polymer particle coated calcium carbonate, and these composite particles are a commercial product of the firm Pierce and Stevens Corporation of Buffalo, N.Y.

In some non-limiting embodiments, the implementation of a particle form solid lubricants. Used in this case, the definition of "solid lubricant" means any solid substance that is used between two surfaces to provide protection from damage during relative movement and/or to reduce friction and abrasion. In some non-limiting embodiments of the invention the solid lubricant are inorganic solid lubricants. Used in this case, the definition of "inorganic solid lubricant" means that the solid lubricating substances have characteristic crystalline behavior that makes them the section is taken on thin, a flat plate, which easily slide one on the other and, consequently, produce antifriction lubricating action (See. publication: R. Lewis, Sr.,Hawley's Condensed Chemical Dictionary(12-th Ed., 1993), p. 712, which is incorporated by reference). Friction is the resistance to sliding of one solid material on the other (See. publication: F. Clauss,Solid Lubricants and Self-Lubricating Solids(1972), R. 1, which is incorporated by reference).

In some non-limiting embodiments of the invention the particles have a scaly structure. Particles having a scaly structure composed of layers or plates of atoms in a hexagonal arrangement with a strong binding within the reservoir and weak van der Waals bonding between the layers, which provides between layers of low shear strength. A non-limiting example of the scaly structure is a hexagonal crystal structure. Inorganic solid particles having a scaly structure of fullerene (i.e. baseball), can also be used.

Non-limiting examples of suitable materials having the scaly structure, which can be used to obtain particles of the present invention are boron nitride, graphite, metal dichalcogenides, mica, talc, gypsum, kaolinite, calcite, cadmium iodide, silver sulfide and mixtures of any of the category is kennyh above substances. Suitable dichalcogenides metals include molybdenum disulfide, diselenide molybdenum, tantalum disulfide, diselenide tantalum, tungsten disulfide, diselenide tungsten, and mixtures of any of these compounds.

In some non-limiting embodiments of the invention the reinforcing material may be a strand of fiberglass. Strands of fiberglass are obtained from the primary glass fibers, class of filaments, as it is recognized, based on oxide compositions, such as silicates, selectively modified other oxide and non-oxide compositions. Useful primary glass filaments can be obtained from any type capable of forming fiber glass composition known to the person skilled in the art and include yarn, obtained from capable of forming fiber glass compositions such as "E-glass, a-glass, C-glass, D-glass, R-glass, S-glass and derivatives "E-glass", which do not contain fluorine and/or boron. Used in this case, the definition of "capable of forming fiber" means material that can be molded, as a rule, continuous filament, fiber, strand or yarn. Used in this case, the definition of "derivative of E-glass" means glass composition, which includes naznacite the performance communications quantities of fluorine and/or boron or may not contain fluorine and/or boron. Also used in this case, the definition of "small amounts of fluorine" means less than 0.5% of the mass. fluorine, or less than 0.1% of the mass. fluorine, and the definition of "minor amounts of boron" means less than 5% of the mass. boron, or less than 2% of the mass. Bora. Basalt and mineral wool are examples of other capable of forming fiber glass materials that can be used in the present invention. Non-limiting examples of suitable not capable of forming the inorganic fiber materials are ceramic materials such as silicon carbide, carbon black, quartz, graphite, mullite, alumina and piezoelectric ceramic materials. In some non-limiting embodiments of the invention glass primary filaments obtained from E-glass. These compositions and methods of making them the primary glass fibers is well known to specialists in this field, and such glass compositions and methods of the fiberizing are discussed in the publication K. Loewenstein,The Manufacturing Technology of Continuous Glass Fibres, (3d Ed., 1993), pp. 30-44, 47-60, 115-122, 126-135, which is incorporated by reference.

Fiberglass can have a nominal filament diameter in the range from about 5.0 to about 30.0 μm (corresponding to the designation of the thread from D to Y). Typically, strands of fiberglass are pokr is that the strand composition, which is compatible with composition applied on at least part of the surfaces of the strands of fiberglass, such as essentially dried residue. Reinforcing materials of strands of glass fiber can be used in chopped form, in the form of a generally continuous strands, mats, etc.

The particles can be hollow particles formed from materials selected from polymeric and polimernyh inorganic materials, polymeric and polimernyh organic materials, composite materials and mixtures of any of these materials. Non-limiting examples of suitable materials from which can be obtained hollow particles discussed above. In some embodiments, the implementation of the hollow particles may be a hollow glass sphere.

In some non-limiting embodiments, the implementation of the reinforcing materials can be obtained from polimernyh organic materials. Non-limiting examples polimernyh organic materials that can be used in the present invention include, but are not limited to, stearates such as zinc stearate and aluminum stearate), diamond, carbon black and stearic acid amide.

In some non-limiting embodiments, the implementation of the particles can be derived from inorganic polymeric materials. Neogranichena the mi examples of useful inorganic polymeric materials are polyphosphazene, polysilane, polysiloxane, polygermane, polymeric sulfur, polymeric selenium, silicones and mixtures of any of these materials. Non-limiting examples of particles derived from inorganic polymer material that is acceptable for use in the present invention, is TOSPEARL1that is a particle obtained from cross-linked siloxanes, and which is a commercial product Toshiba Silicones Company, Ltd., Japan (1Cm. R.J. Perry “Applications for Cross-Linked Siloxane Particles”,Chemtech. February 1999, pp. 39-44).

Particles can be obtained from synthetic, organic, polymeric materials, which are chemically different from the polyurethane or poly(mochevinoi). Non-limiting examples of suitable organic polymeric materials include, but are not limited to, thermosetting materials and thermoplastic materials. Non-limiting examples of suitable thermoplastic materials are thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylenterephthalat, polycarbonates, polyolefins, such as polyethylene, polypropylene and polyisobutene, acrylic polymers such as copolymers of styrene and acrylic acid, and polymers containing methacrylate, polyamides, thermoplastic polyurethanes, vinyl polymers and mixtures of any of precisionmachined.

In some non-limiting embodiments, the implementation of the polymeric organic material is a (meth)acrylic polymer or copolymer containing at least one functional group selected from the group comprising silane groups, carboxyl groups, hydroxyl groups and amide groups. In some non-limiting embodiments, the implementation of such (meth)acrylic polymers or copolymers may be present in the form nanofibers having a diameter of approximately 5000 nm, for example approximately from 5 to 5000 nm, or having a diameter smaller than the wavelength of visible light, for example, 700 nm or less, for example approximately from 50 to 700 nm. The fibers may be in the form of a tape, and in this case, the diameter, as is implied, is the large amount of fiber. As a rule, the width of the ribbon-like fibers may be approximately 5000 nm, for example approximately from 500 to 5000 nm, and the thickness is approximately 200 nm, for example approximately from 5 to 200 nm. Fiber can be obtained by electrophoretogram ceramic melt, the polymer melt or polymer solution.

Suitable (meth)acrylic polymers can be obtained by polymerization attach unsaturated capable of polymerization materials which contain silane groups, carboxyl groups, guide axiline groups and amine or amide groups. Non-limiting examples of useful Milanovich groups are groups that have a structure Si-Xn(where n is an integer having a value from 1 to 3, and X is selected from chlorine atom, complex alkoxyamino and/or relaxiation). Such groups are hydrolyzed in the presence of water, including moisture in the air, with the formation of silanol groups, which are condensed with the formation of groups-Si-O-Si-. (Meth)acrylic polymer may contain hydroxyl functionality, for example, when using Ethylenediamine capable of polymerization monomer with a hydroxyl functionality, such as complex hydroxyalkyl esters of (meth)acrylic acid containing from 2 to 4 carbon atoms in the hydroxyalkyl group. (Meth)acrylic polymer optionally contains nitrogen functionality introduced from a nitrogen-containing Ethylenediamine monomers, such as amines, amides, urea, imidazoles and pyrrolidone. Additional information on such (meth)acrylic polymers and methods of forming fiber described in patent application U.S. reg No. ___/______, entitled "Transparent composite parts (Transparent Composite Articles), and in the patent application U.S. reg No. ___/______, entitled "Organic-inorganic polymer composites and retrieving them using the liquid introduction" (Organic-Inorganic Polymer Composites and Their Prparation by Liquid Infusion), each of which is located on the simultaneous consideration and is included as a reference.

Non-limiting examples of suitable fibre-forming organic materials are cotton, cellulose, natural rubber, flax, raps, hemp, sisal and wool. Non-limiting examples of suitable fibre-forming organic polymeric materials are materials obtained from polyamides (such as nylon and aramid) (such as aramid fiber KEVLARTM), thermoplastic polyesters (such as polyethylene terephthalate and polybutylene terephthalate), acrylic polymers (such as polyacrylonitrile), polyolefins, polyurethanes and vinyl polymers (such as polyvinyl alcohol). Desteklenen fiber-forming materials that can be used in the present invention, and methods of obtaining and processing such fibers are discussed in detail in the publication:Encyclopedia of Polymer Science and TechnologyVol. 6 (1967), pp. 505-712, which specifically included as a reference.

It is clear that mixtures or copolymers of any of the above materials and combinations of fibers formed from any of the above materials can be used in the present invention, if so desired. Moreover, the definition of "strand" may include at least two different fibers made from different in odnoobraznaya materials. Used in this case, the definition of "fibre-forming" means a material capable of forming, as a rule, continuous filament, fiber, strand or yarn.

Suitable thermoplastic fibers can be formed by using a number of methods for the extrusion of polymers and methods of forming fibers such as, for example, extractor hood, forming from the melt, dry molding, wet molding and forming an air gap. Such methods are well known to experts in the art and further discussion is believed, is not necessary in this description. If additional information is needed, such methods are discussed in the publicationEncyclopedia of Polymer Science and TechnologyVol. 6 (1967), pp. 507-508.

Non-limiting examples of useful polyamide fibers are nylon fibers, such as nylon 6 (a polymer of caprolactam), nylon 6,6 (the condensation product of adipic acid and diamine), nylon 12 (which may be derived from butadiene) and nylon 10, polyhexamethylenediamine, polyamidimide and aramids such as KEVLARTMthat is a commercial product of E.I. DuPont de Nemours, Inc., Wilmington, Del.

Non-limiting examples of useful thermoplastic, polifonik fibers are fibers composed of polyethylene terephthalate and polybutylene terephthalate.

Neo the limits examples of useful fibers, molded from acrylic polymers are polyacrylonitrile having at least about 35% of the mass. Acrylonitrile units, or at least about 85 wt. -%, which can be copolymerizable with other vinyl monomers such as vinyl acetate, vinyl chloride, styrene, vinylpyridine and others, acrylic esters or acrylamide. (SeeEncyclopedia of Polymer Science and TechnologyVol. 6, pp. 559-561).

Non-limiting examples of useful polyolefin fibers typically comprise at least about 85% of the mass. ethylene, propylene or of other olefins. (SeeEncyclopedia of Polymer Science and TechnologyVol. 6, pp. 561-564).

Non-limiting examples of useful fibers, molded from vinyl polymers, can be obtained from polyvinyl chloride, polyvinylidenechloride, polytetrafluoroethylene and polyvinyl alcohol.

Other non-limiting examples of thermoplastic fibre-forming materials, which are thought to be useful in the present invention are fiber-forming polyimides, simple polyethersulfone, polyphenylsulfone, polyetherketone, polyphenyleneoxides, polyphenylensulfide and Polyacetals.

It is clear that mixtures or copolymers of any of the above materials and combinations of fibers obtained from any of the above materials can be used in the present invention, if this is desirable. In addition, thermoplastic fibers may be deposited on them antistatic.

Suitable reinforcing materials include mats or fabrics composed of any of the above fibers. An increasingly popular process of forming composites is injection molding or stamping capable of forming a sheet of thermoplastic resin reinforced with fibers, such as Mat, often called thermoplastics reinforced with glass mats, or "GMT". Such composite sheets can be used to obtain products such as automotive parts and housings for computers. An example of a commercially successful sheet GMT is moldable composite sheet AZDEL®, which is obtained by extruding layers of the sheet of polypropylene resin with a needle Mat of continuous strands of fiberglass. Composite sheet

AZDEL®a commercial product Azdel, Inc., Shelby, N.C.

For hardening of the matrix resin in U.S. patent No. 3664909, 3713962 and 3850723 disclosed fiber mats from nesmith of filaments that can be sandwiched with the reinforcing mats of fiber strands.

In U.S. patent No. 4847140 disclosed an insulating medium, formed by stitching loosened layer of inorganic fibers such as fiberglass, connected together by a bearing cloth, totoraitis a mixture of inorganic and organic fibers, moreover, the support for the canvas contains approximately 10% of the mass. organic fibers.

In U.S. patent No. 4948661, 5011737, 5071608 and 5098624 disclosed reinforced with fibers of thermoplastic molded products produced by thorough mixing of the reinforcing fiber and thermoplastic fibers in the fabric and heating the fabric to the melting temperature of thermoplastic fibers with the use of canvas pressure to press the cloth to the merged structure.

A non-limiting example of a useful non-woven Mat of polypropylene fibers is commercially available product company Fiberweb N.A., Inc. Simponville, S.C.

Non-limiting examples of suitable thermosetting materials-amplifiers are thermosetting polyesters, vinyl esters, epoxy materials, phenolic plastics, aminos, thermosetting polyurethanes, and mixtures of any of these materials. Specific non-limiting example of a synthetic polymer particles obtained from the epoxy is epoxy microglia particle.

The concentration of particles amplifier present in the cured product or the coating can be determined, if necessary, by using various analytical techniques well known in the field, such as transmission electron microscopy (TEM), over osta scanning electron microscopy (X-SAM, "X-SEM"), atomic force microscopy (AFM, "AFM") and photoelectron spectroscopy.

In some non-limiting embodiments implementing the present invention relates to utverzhdennym compositions described previously, where the particles of the amplifier have an average particle size of less than about 100 microns prior to the introduction into the composition, or less than about 50 microns prior to the introduction into the composition. In other non-limiting embodiments implementing the present invention relates to utverzhdennym compositions described previously, where the particles of the amplifier have an average particle size that is in the range from about 1 to less than about 1000 nm prior to the introduction into the composition, or from about 1 to 100 nm prior to the introduction into the composition.

In other non-limiting embodiments implementing the present invention relates to utverzhdennym compositions described previously, where the particles have an average particle size in the range from about 5 to 50 nm prior to the introduction into the composition, or from about 5 to 25 nm prior to the introduction into the composition.

In the embodiment, where the average particle size is at least about one micron, the average particle size can be measured in accordance with known techniques of laser scattering. For example, the average size of such h is STIC measured using laser diffraction to determine the particle size Horiba Model LA 900, in which use helium-neon laser with a wavelength of 633 nm, to measure the particle size, and accept that the particles have a spherical shape; that is, the "particle size" refers to the smallest sphere that will completely cover the particle.

In the embodiment of the present invention, where the particle size is less than or equal to one micron, the average particle size can be determined by visual evaluation of image electron micrograph in the transmission electron microscope (TEM), by measuring the diameter of the particles in the image and calculating the average particle size based on the magnification of the TEM image. Ordinary skilled in the art it will be clear how to obtain such an image in TEM and description of one such method is disclosed in the examples below. In one non-limiting embodiment of the present invention receives the image in TEM with 105000-fold magnification, and the conversion factor is obtained by dividing the increase by 1000. A visual assessment of particle diameter is measured in millimeters, and the measurement result is transferred to nanometers using a conversion factor. Particle diameter refers to the small diameter of the sphere that will completely surround the particle.

The shape (or morphology) of the reinforcing material m which may vary depending on the specific variant of implementation of the present invention and its intended application. For example, can be generally used spherical morphology (such as solid beads, mikrobasic or hollow spheres), as well as particles, which are cubic, flat or needle-shaped (elongated or fiber-like). In addition, the particles can have an internal structure, which may be hollow, porous, or solid or a combination of any of the above, for example, a hollow center with a porous or solid walls. For more information on the characteristics of suitable particles can refer to the publication: H. Katz et al., (Ed.),Handbook of Fillers and Plastics(1987), pp. 9-10, which is incorporated by reference.

The person skilled in the art will understand that a mixture of one or more particles having different average particle sizes, can be introduced into the compositions in accordance with the present invention to give the composition the desired properties and characteristics. For example, in the compositions of the present invention can be used particles of varying size.

In some non-limiting embodiments of the invention enhance(s) material(s) present(s) in the composition in amount in the range from about 0.01 to 75 wt. -%, or from about 25 to 50 wt. -%, based on the total weight of the components that make up the composition.

Particles of the amplifier may be present in the var is rsii, suspension or emulsion in a carrier. Non-limiting examples of suitable carriers include, but are not limited to, water, solvents, surfactants or mixtures of any of the above materials. Non-limiting examples of suitable solvents include, but are not limited to, mineral oil, alcohols, such as methanol or butanol, ketones, such as methylmercaptan, aromatic hydrocarbons, such as xylene, ethers, glycols, such as monobutyl ether of ethylene glycol, esters, aliphatic compounds, and mixtures of any of the above substances.

Can be used in methods of dispersion, such as grinding, milling, microfluidizers, sonication, or any other dispersion techniques, well known in the field of formulations of coatings or molded products. On the other hand, particles may be dispersed by any other dispersion techniques known in the art. If desired, the particles in a form different from colloidal form, can be added to the mixture of other components of the composition later and dispersed therein using any dispersion techniques known in the art.

Another variant of the present invention relates to a covered auto is abundant basics, consisting of automotive fundamentals and utverzhdenii composition applied on at least part of the motor base, where the cured composition is selected from any of the above compositions. In yet another embodiment, the present invention relates to a method for producing a coated automotive basics, which includes the creation of automotive fundamentals and application, at least part of the car covering the basics of composition, selected from any of the above compositions. And again, the components used for forming utverzhdenii compositions can be selected from the above-described components, and additional components can also be selected from the above additional components.

Suitable flexible elastomeric bases can be any thermoplastic or thermosetting synthetic materials, well known in the art. Non-limiting examples of suitable materials for flexible elastomeric bases are polyethylene, polypropylene, thermoplastic polyolefin ("TPO", "TRO"), a polyurethane obtained by reaction injection molding ("RIM"), and thermoplastic polyurethane (TPU, "TPU").

Non-limiting examples of thermosetting materials which can be used as a basis for the cover comp is the dispositions of the present invention, are polyesters, epoxides, phenolic, polyurethane, such as thermosetting materials "RIM", and mixtures of any of the above materials. Non-limiting examples of suitable thermoplastic materials are thermoplastic polyolefins, such as polyethylene, polypropylene, polyamides, such as nylon, thermoplastic polyurethanes, thermoplastic polyesters, acrylic polymers, vinyl polymers, polycarbonates, Acrylonitrile-butadien-styrene (ABS) copolymers, ethylene-propylene-diene terpolymer (EPDM), copolymers and mixtures of any of the above examples.

Non-limiting examples of acceptable metal bases that can be used as a basis for the coating of the compositions of the present invention are iron-containing metals (e.g. iron, steel and its alloys), nesadurai iron metals (e.g. aluminum, zinc, magnesium and their alloys), as well as mixtures of any of the above materials. In a specific application for details of hire basis can be obtained from steel cold rolled, galvanized steel, such as galvanized steel, hot-dipping galvanized steel, aluminum and magnesium.

When bases are used as components for the manufacture of vehicles (including, but without the exhaust gas is anichini, cars, trucks and tractors), they can be of any shape and can be selected from metal and flexible framework described above. Typical shapes of the body parts of cars can be frames (frame), hoods, doors, fenders, racks mirrors, bumpers and metal finish of vehicles.

In embodiments implementing the present invention, which are used in cars, cured compositions can represent, for example, the coating deposited by the electroplating method, a primer coating, base coat and/or top fixing floor. Suitable upper reinforcing coatings are single component coatings and composites (basic coverage)/transparent layer. One-component coatings are produced from one or more layers of colored covering composition.

In some non-limiting embodiments, the implementation of the polyurethanes and poly(uretonimine) Groups, And-R can be reinforced with glass fibre with obtaining composite products, such as, for example, the blade of a propeller, a blast-proof combat panel, bulletproof panels and fairings.

The group R

In some non-limiting embodiments, the implementation of the polyurethanes and poly(mochevinoi) Groups, And-Q can be used as one or bore the channels at layers in multilayer product. If desired, the laminated product may be laminated.

In some non-limiting embodiments, the implementation of the polymer is cut until it is warm, granularit, ekstragiruyut and/or crushed and calandro in the leaves, collected in laminates and incubated for several days, weeks or a longer period at room temperature (approximately 25°C).

In some non-limiting embodiments, the implementation of the present invention provides articles having multiple layers of polyurethane and/or poly(macawesomeshow) of the present invention. The thickness of each layer and the total thickness of the product may vary, if necessary. Non-limiting examples of acceptable thicknesses of layers and products below. The layers can be laminated together, if so desired.

In some non-limiting embodiments, the implementation of the present invention provides a multilayer articles or laminates containing: (a) at least one polyurethane layer(s) or poly(mochevinoi)(s) of the present invention described above; and (b) at least one layer of a base, selected from the group comprising paper, glass, ceramics, wood, stone, fabric, metal or organic polymeric material and combinations thereof. In some non-limiting embodiments of the invention, the layer (a) polyurethane(s) or paragraph is whether(mochevinoi)(s) of the present invention is chemically or physically different from the organic polymer material layer (b), that is, it has at least one other atom, the arrangement of the atoms or configuration. In other embodiments, may be used two or more layers of the same(s) or similar(their) polyurethane(s) or poly(mochevinoi)s of the present invention.

In some non-limiting embodiments, the implementation of the framework is an optically clear polymerized organic material obtained from a thermoplastic polycarbonate resin, such as the carbonate-linked resin derived from bisphenol a and phosgene, which is sold under the trade name LEXAN®(GE Plastics of Pittsfield, Massachusetts); a complex of the polyester, such as the material sold under the trade name MYLAR (E.I. DuPont de Nemours Co., Wilmington, Delaware); poly(methyl methacrylate), such as the material sold under the trade name PLEXIGLAS (Altuglas International of Philadelphia, Pennsylvania); polyurethanes based polietilen-polycarbonate; polymerizaton polyol(allylcarbamate) monomer, especially diethylene glycol bis(allylcarbamate), and this monomer is sold under the trade name CR-39 (PPG Industries, Inc.), and polymerization copolymers of polyol(allylcarbamate), such as diethylene glycol-bis(allylcarbamate), with other capable of copolymerization of Monomeric materials, such as copolymers with vinyl acetate, and copolymers with a polyurethane having terminal is acrylato functionality which are described in U.S. patent No. 4360653 and 4994208; and copolymers with aliphatic urethanes, the terminal part of which contain allyl or grillini functional groups, which are described in U.S. patent No. 5200483; poly(vinylacetate), polyvinyl butyral, polyurethane and polymers of members of the group, including monomers, diethylene glycol dimethacrylate monomers of diisopropenylbenzene and ethoxylated monomers of the triacetate of trimethylolpropane; of cellulose acetates, propionates cellulose, butyrate cellulose, acetate-butyrate cellulose, polystyrene and copolymers of styrene with methyl methacrylate, vinyl acetate and Acrylonitrile.

A non-limiting example of a suitable polyurethane-based polietilen-polycarbonate can be obtained in the following way: get prepolymer with a hydroxyl functionality of from 0.2 equivalent of a carbonate diol-based hexandiol with a molecular weight of 1000 (MS-1733, a commercial product of the firm Stahl), 0.8 equivalent of 1.5-pentadione and 1.0 equivalent trimethylhexanoate. The components are heated up to 180°F (82°C) and as a catalyst using 100 ppm of dibutyltindilaurate. Prepolymer has an equivalent weight 218 g/equivalent. Trimers of prepolymer with the terminal hydroxyl group is dissolved in a solvent, cyclohexanone, and as a crosslinking agent was added 1 of equivalen the Desmodur 3390 (triisocyanurate the trimer exanguination), and mix. Covering solution contains 95% solids with a viscosity of 3000 centipoise. The solution may be applied by ink jet loading on any polycarbonate of bisphenol a, such as Lexan, and overiden in an oven at 250°F (212°C) for 4 hours. The coating thickness may be in the range from 2 to 5 mils, and the coating is elastomeric.

The number and thickness of layers may vary, if desired. For example, the thickness of one layer may be in the range from about 0.1 mm to 60 cm, or from about 2 mm to 60 cm, or from about 0.3 to 2.5, see the Number of layers may be in the range from 2 to 10, or from 2 to 4, if necessary. The total thickness of the multilayer product or laminate may be in the range from about 2 mm to 2 cm or more, or from approximately 2 mm to 5 cm In the case of ballistic applications total thickness of the polyurethane or poly(mochevinoi) of the present invention may be in the range from about 2 mm to 15 cm or more, or from approximately 2 mm to 5 cm in Addition, in the case of ballistic applications suitable basis for stratifying polyurethane(s) and/or poly(mochevinoi)(s) of the present invention are, for example, polyesters, polycarbonates or simple polyester thermoplastic elastomers. The layer(s) of polyurethane or poly(mochevinoi is) of the present invention may be located(s) on the outer side of the laminate (in the direction of a potential ballistic impact), on the inner side of the laminate or somewhere in another place between them.

Group a-R

In some non-limiting embodiments, the implementation of the polyurethanes and poly(mochevinoi) of the present invention may have a content of hard segments of from about 10 to 100 wt. -%, or from about 20 to 80 wt. -%, or from about 30 to 75 wt%. The calculation of the hard segments discussed above.

In some non-limiting embodiments, the implementation of the polyurethanes and poly(mochevinoi) of the present invention, generally have a content of the urethane (Wu) from about 20 to 40 wt. -%, or from about 21 to 36 wt. -%, approximately 30 to 40% of the mass. The content of the urethane represents the mass percentage of urethane bridges present in the polymer, and can be calculated by determining the total number of equivalents and from it the total mass of all reactants and dividing the total mass of urethane bridges, which can be obtained from these reactants, the total mass of the reactants. The following example additionally explains this calculation. In the example I formulation 1, which is described below, polyurethane products in accordance with the present invention receive when interacting 0.7 equivalent of 1,4-butadiene, 0.3 equivalents of trimethylolpropane and one equivalent of 4,4'-methylene-bi is(cyclohexylsulfamate) (DESMODUR W). Equivalent weight of 1,4-butanediol is 45, the equivalent weight of trimethylolpropane equal to 44.7 (with a correction for impurities) and the equivalent weight of DESMODUR W is 131.2. Consequently, the actual weight of the ingredients used is 31,54 masses. including 1,4-butanediol, 13.2 masses. hours of trimethylolpropane and 131.2 wt. including DESMODUR W, or the total mass of the reactants 175,9 masses. h One equivalent of DESMODUR W will give one equivalent urethane bridges. Equivalent weight of urethane bridge is 59, so the total mass of the urethane bridges determined by multiplying the equivalent weight by the number of equivalents will also be 59. Therefore, the total mass of the urethane bridges, 59, divided by the total mass of the reactants, 175,9 multiplied by 100 to convert to percent, will give the mass percentage of urethane bridges 33,49% of the mass.

Similarly can be calculated mass percentage of cyclic structures (Wc) (such as, for example, cyclohexyl). In example I, formula 1, the only material that gives tsiklogeksilnogo remains is DESMODUR W. One equivalent of DESMODUR W will give one equivalent tsiklogeksilnogo residue, which is the equivalent mass of 81. Therefore, the total mass tsiklogeksilnogo residues is equal to 81 and this value is divided by the total mass of the reactants or 175,9, budgetdebate W c46%. In some non-limiting embodiments, the implementation of the polyurethanes and poly(mochevinoi) of the present invention may have a content of cyclic groups of from about 10 to 80 wt. -%, from about 20 to 70 wt. -%, from about 30 to 70% of the mass. or from about 30 to 60% of the mass.

In some non-limiting embodiments, the implementation of the resulting polyurethanes and poly(mochevinoi) of the present invention when cured can be solid and essentially transparent. In some non-limiting embodiments, the implementation of the polyurethane may be partially overiden or fully overiden so that essentially the following reactions will not occur.

In some non-limiting embodiments, the implementation of the polyurethanes and poly(mochevinoi) the present invention generally have srednecenovogo molecular weight, which is examined by measuring the characteristic viscosity of at least about 20000 g/mol, or it is in the range from about 20000 to 1000000 g/mol, or in the range from about 20,000 to 800000 g/mol. The polyurethanes and poly(mochevinoi) of the present invention typically have an average molecular weight based on cross-linking of at least about 500 g/mole, in some embodiments of the invention in the range from about 500 to 15,000 gmol, or in the range from about 1800 to 15000 g/mol. The polyurethanes and poly(mochevinoi) of the present invention typically have a density of crosslinking of at least about 11000 g/mol.

In some non-limiting embodiments, the implementation of the polyurethanes and poly(mochevinoi) of the present invention when cured can have a low density. In some non-limiting embodiments, the density may be at least 0.9 to less than 1.25 g/cm3or, at least, from 1.0 to less than 1.45 g/cm3or from 1.08 to less than 1,37 g/cm3or from 1.08 to 1.13. In some non-limiting embodiments of the invention the density of the polyurethanes and poly(macawesomeshow) of the present invention may be less than the LEXAN (density approx 1,21 g/cm3and conventional extruded acrylic polymer (density is about 1.18 g/cm3). Density can be measured using a device DensiTECH production Tech Pro, Incorporated. In non-limiting embodiments, the implementation of the density measured in accordance with ASTM D 792-00.

In addition, some of optically pure polyurethanes and poly(mochevinoi) when heated show a low-temperature ectothermy at approximately -70°C. (differential thermal analysis can be carried out using a t is royalization Du Pont 900) and at approximately 11°C, indicating that the polymers are generally amorphous.

In some non-limiting embodiments of the invention when measured in nitrogen atmosphere are typical softening temperature from about 65 to 200°C, the melting temperature from about 80 to 220°C. and the decomposition temperature of approximately 280 to 330°C.

The polyurethanes and poly(mochevinoi) of the present invention can be used to obtain products having good impact resistance or flexibility, high impact strength, high ultimate tensile strength, resistance to deformation due to thermal heating, good hardness, high young's modulus, high modulus, good resistance to solvents, high purity or transparency, high transmittance, low turbidity, good resistance to weathering, good energy absorption, good resistance to moisture, good resistance to ultraviolet light and/or a good ballistic resistance.

Non-limiting examples of suitable methods and equipment for measuring the resistance to shock loads and impact strength discussed above.

In some embodiments of the invention, the temperature of deformation due to thermal heating of the hardened products of this image is etenia may be, at least approximately 190°F (88°C) or approximately 200°F (93°C) in determining in accordance with ASTM D-648.

The hardness of the polyurethanes and poly(macawesomeshow) can be determined using a shore hardness, and, accordingly, in some embodiments, articles of the present invention have a shore hardness D at room temperature (25°C) using a Durometer shore D, at least about 75, or at least about 80.

Ultimate tensile strength at yield or at break can be measured in accordance with ASTM D 638-03. In some non-limiting embodiments, the implementation of the limit tensile stress at yield is at least approximately 6800 psi (47 MPa)according to ASTM D 638-03, or approximately 6800 up to 20,000 psi (approximately 47 to 138 MPa), or about 12,000 to 20,000 psi (from about 83 to 138 MPa).

The young's modulus can be measured according to ASTM D 638-03. In some non-limiting embodiments, the implementation of the young's modulus is at least about 215000 psi (approximately 1482 MPa), or from about 215000 up to 600,000 psi (approximately from 1482 until 4137 MPa), or from about 355000 up to 600,000 psi (approximately from 2413 to 4137 MPa). For the ill is introw cabins of commercial aircraft, when the cabin pressure is 10 psi (0.07 MPa) or much more than the external pressure, the portholes of the cabin can be bent in the direction of air flow, resulting in increased noise and reduced fuel efficiency. Higher values of young's modulus indicate increased stiffness and less prone to bending of the window in the direction of air flow. In some non-limiting embodiments, the application for illuminators aircraft values of young's modulus may be at least approximately 350000 (approximately 2413 MPa). In a typical ballistic applications external layers are glass, which is strong enough to deform the bullet due to the stress distribution at the impact over a large area before it passes through the bottom layers. Poly(mochevinoi), obtained according to example A, formulation 125, in accordance with the present invention, having a thickness of approximately 0.125 inch (0.3 cm), flattens 9 mm bullet, released at 1350 ft/sec (411 m/sec) from a distance of 20 feet (6.1 m). Although the layer and destroyed 2 cracked area, it is not shattered over a large area, such as glass, which will provide higher visibility for passengers to avoid attacks on the vehicle.

The factor K is m is Roy propagation of cracks. Crack propagation can be measured in accordance with U.S. Dept. of Defense MIL-PRF-25690B (January 29, 1993). In some non-limiting embodiments, the implementation of the polyurethanes and poly(mochevinoi) of the present invention have a coefficient For the distribution of the cracks, at least about 1000 lb/DM3/2(1098800 N/m3/2), or from about 1000 to 4000 lb/DM3/2(from 1098800 to 4395200 N/m3/2), or from about 2000 to 4000 lb/DM3/2(from 2197600 to 4395200 N/m3/2).

Compositions suitable for use in windshields of the cars, meet the standard requirements of minimum light transmission of 70%or 86,5% or higher (the light source And a tungsten filament lamp C) or turbidity less than 2% (ANSI. CODE Z-26.1, 1966, Test No. 18). The percentage of light transmission, and the percentage of turbidity can be measured by turbidimeter Hunter Pivotable Sphere Haze Meter in accordance with ASTM E903-82.

The polyurethanes and poly(mochevinoi) of the present invention can have an outstanding performance portability weather conditions, as measured by resistance to ultraviolet light and hydrolytic stability. The impact of using a Fade-O-Meter®can be carried out in accordance with ASTM G-25-70, method A, using a Fade-O-Meter, Type FDA-R, Serial No. F02951 manufactured by Atlas Electric Devices Co., Chicago, Illinoi. The light source can be an arc lamp with carbon electrodes enclosed in a spherical shell made of quartz glass. Operating temperature Fade-O-Meter (black panel) may be 140°F (60°C), and the device operates in the absence of water in the spray site. The dimensions of the sample are 2½×1/8 DM (6,35×15,24×0,32 cm). The impact of using a Weather-O-Meter®can be carried out in accordance with ASTM D-1499-64 using a Weather-O-Meter, Type DMC Serial no WO-1305. The type of light source is an arc lamp with double carbon electrode encased in a spherical shell made of quartz glass. The working temperature of the black panel can reach 140°F (60°C). Spray deionized water at a temperature of approximately 70°F (21°C). The number and type of nozzles used for spraying water, correspond to the four nozzles No. 50. On the other hand, resistance to UV can be determined using a QUV test for 1000 hours in accordance with ASTM G-53.

Abrasion resistance can be measured using abrasive machine Tabera, which has an abrasive CS-10F weighing 500 g for sample sizes of 3×3×1/8 DM (7.62 cm × 7.62 cm × 0,32 cm) in accordance with ASTM D 1044-99. In some non-limiting embodiments, the implementation of 100 cycles on the abrasive machine of Tabera can lead to 30% turbidity extruded acrylic Polimeri to the turbidity of from 5 to 40%, or from 10 to 15%, or less than 5% polyurethane and poly(macawesomeshow) of the present invention.

The polyurethanes and poly(mochevinoi) of the present invention can have good resistance to the formation of hairline cracks under the action of solvents and acids. Resistance to the formation of hairline cracks can be measured in accordance with U.S. Dept. of Defense MIL-PRF-25690B (January 29, 1993). Non-limiting examples of solvents and acids for testing for resistance to the formation of hairline cracks at voltages are methanol, isopropanol, ethylene glycol, propylene glycol, ethyl acetate, acetone, toluene, isopropylacetate, Skydrol (hydraulic fluid), jet fuel, such as JP-4, and 75%aqueous solution of sulfuric acid. In some non-limiting embodiments, the implementation of uncoated products derived from polyurethanes and poly(macawesomeshow) of the present invention have a resistance to the formation of hairline cracks at a voltage in an organic solvent and 75%aqueous solution of sulfuric acid of at least about 1000 psi (6,9 MPa) tensile stress, or from about 1000 to 4000 psi (6.9 to 27.6 MPa), or from about 2000 to 4000 psi (from 13.8 to 27.6 MPa). In some non-limiting embodiments, the implementation of the polyurethanes and poly(mochevinoi) of the present invention when they are not coated, can withstand 75%sulfuric acid for up to thirty days or any organic solvent in the membrane voltage from 1000 to 4000 psig (6,9 to 27.6 MPa).

In some non-limiting embodiments of the invention, the polyurethanes and poly(mochevinoi) of the present invention in the polymerization can give polymerizate having a refractive index of at least 1.55V, or, at least, 1,56, or, at least, 1,57, or, at least, 1,58, or, at least, 1,59, or, at least, 1,60, or, at least, 1,62, or, at least, of 1.65. In other non-limiting embodiments, the implementation of poly(mochevinoi) of the present invention in the polymerization can give polymerizate having an Abbe number of at least 32, or at least 35, or at least 38, at least 39, or at least 40, or at least 44. The refractive index and Abbe number can be determined using methods known in the art, such as test method according to the American standards (American Standard Test Method) ASTM D 542-00. In addition, the refractive index and Abbe number can be determined using various known devices. In a non-limiting embodiment of the present invention, the refractive index and Abbe number can be measured in accordance with ASTM D 542-00 with follow what their exceptions: (i) test one two samples/examples instead of at least three examples defined in section 7.3; and (ii) the samples not subjected to conditioning instead of conditioning the samples/examples before conducting the tests, as defined in section 8.1. In addition, non-limiting embodiment of the invention for measuring the refractive index and Abbe number of samples/examples can be used multiwave digital Refractometer Atago, model DR-M2.

Solid product, which can be obtained using polyurethane or poly(macawesomeshow) of the present invention include, but are not limited to, optical products or lenses, photochromic articles or lenses, Windows, portholes, such as conventional transparent window, windshield, sidelights and headlights rear lights, portholes aircraft, ballisticheskih sustainable products, parts, aircraft engines, such as blades, and glass.

In some non-limiting embodiments, the implementation of the polymeric base material, including a deposited covering the composition may be in the form of optical elements such as Windows, flat and corrective vision lenses, visible surfaces of exterior liquid crystal displays, cathode ray tubes, etc., monitors, TVs and computers, transparent polymers the x films transparent products, for example, front Windows, portholes aircraft, plastic sheeting and other

The polyurethanes and poly(mochevinoi) of the present invention necessary for a wide range of applications. They are particularly useful as materials glazing for Windows aircraft with safety glasses. In addition glazing aircraft polyurethanes and poly(mochevinoi) of the present invention in sheet form can be used in architecture and can be tinted or opaque due to pigmentation, if this is desirable. In such embodiments, the applications of polyurethanes and poly(mochevinoi) of the present invention may be in sheet form and can be used separately or can be laminated with other material, as discussed above. The layers in the composite may have the same or different values of modulus of elasticity, if this is desirable. In addition, in some embodiments, the polyurethanes and poly(mochevinoi) of the present invention can be used for optical lenses, as they may be optically transparent, not exposed to UV light and moisture and abrasion resistant.

In other non-limiting embodiments, the implementation of the polyurethanes and poly(mochevinoi) of the present invention can be the used as bases with low thermal expansion for the deposition of conductive films for electrochromic applications, absorbent microwave films and low-resistance films. In other non-limiting embodiments, the implementation of extruded acrylic base can be covered with cyanoacrylat/acrylic copolymer, and optionally coated with polyurethanes and poly(motivirovanni) of the present invention.

The polyurethanes and poly(mochevinoi) of the present invention can be used in sheet form and can vary in thickness from approximately 2 to 500 mils, although sometimes can be used in thinner and thicker sheets depending on the application. In the case of applications for aircraft in some embodiments, the thickness may vary between 1/8 DM and 1/2 DM (from 0.32 to 1.27 cm).

In some embodiments, the implementation of car Windows can be obtained from a thermoplastic polycarbonate resin, such as resin, which is sold under the trade name LEXAN, with the cover composition of the present invention, applied as protection from weathering layer on the outer side of the window to increase the resistance of the window to weathering. On the other hand, the car window can be obtained in the form of a laminate of glass/LEXAN glass as the outer layer and covering compositions of the present invention, applied as a layer on the inner side of the laminate.

Covering the composition I of the present invention can be applied to the surface of the base using any known methods of coating. Preferably covering the composition to cause the jet bulk to the surface of the substrate with the help of automated blasting systems of loading, in which the surface tension of the fluid stretches the coherent fabric of the liquid on the substrate surface, while a mechanical device for inkjet loading crosses the leaf bases. Automatic device for inkjet filling usually consists of a hinged bracket that holds the nozzle connected to a pressurized vessel where the resin solution. The bracket makes passes over the guiding device on the sheet to be coated. The rate of fluid flow regulate using a pressurized vessel. The speed of movement of the hinge bracket set using the potentiometer. The distance of the nozzle from the leaf optimize and maintain constant using the adjustable bracket. This is especially important for curved sheets. The thickness of the coating is determined by the initial solution viscosity of the resin and evaporation of the solvent. The evaporation rate is mainly controlled by the choice of solvent and air flow in CFM/min in a ventilated booth coating. On the other hand, covering compositions can be prepared and poured into the appropriate formus obtaining the desired structure, which can then be applied as a layer on a suitable base, for example, due to the lamination process, or can be used in the form of a monolithic structure.

Covering composition, as a rule, it can be applied on the basis of transparent or pigmented monolayer, or in the form of a pigmented base layer and/or transparent top layer in the colored-plus-clear composite coating, which is known to the person skilled in the art. In some embodiments, the implementation of the coating can be applied before isocyanate and hydroxyl groups are completely reacts, for example, by spraying isocyanate and hydroxyl components through a mixing nozzle for applying the coating to the substrate. On the other hand, the coating can be partially overiden in the furnace and then subjected to an environment with high moisture content, such as environments with high humidity or water-dust, for further interaction and curing of the coating. If desirable, the cover composition may include additional materials, well known in the art, developing surface coatings, such as surfactants, agents, controlling fluidity, thixotropic agents, fill and, agents that prevent the generation of gases, organic co-solvents, catalysts, and other customary auxiliaries. Such materials can comprise up to 40% of the mass. from the total mass of the covering composition.

As mentioned above, although the cured composition can be obtained from a liquid coating compositions, they may also be obtained from the coating compositions prepared in the form of powder coating compositions.

In another non-limiting embodiment, cured compositions of the present invention can also be used as decorative or protective coatings for pigmented plastic (elastomeric) basis or "mold-in-color (MIC) plastic bases. In such embodiments, application of the composition can be applied directly to the plastic base or may be included in forming the matrix. Not necessarily directly on plastic or elastomer base may be initially applied stimulator of adhesion, the composition may be applied over the top layer.

In another non-limiting embodiment, the compositions of the present invention can also be used as protection from cracking layer, antifracture covering layer or preventing the destruction layer of glass or other fundamentals.

Neogranichinymi embodiment, the polyurethane polymerizate of the present invention can be used to obtain a photochromic products. In another embodiment of the invention polymerizate may be transparent to the portion of the electromagnetic spectrum which activates the photochromic(s) substance(s), i.e., that wavelength of ultraviolet (UV) radiation, which gives the painted or open form of the photochromic substance and that part of the visible spectrum that includes the wavelength of maximum absorption of the photochromic substance in its UV activated form, i.e. the open form.

Photochromic compounds exhibit a reversible color change when exposed to light radiation, including ultraviolet rays, such as ultraviolet radiation of sunlight or radiation from a mercury lamp. Synthesized various classes of photochromic compounds and proposed for applications in which preferably is induced by sunlight reversible color change or darkening. The most widely described classes of photochromic compounds are oxazine, Pirani and fulgide.

The General mechanism responsible for the reversible color change, i.e. the change in absorption spectrum in the visible region of light (400-700 nm), show different types of photochromic compounds described and grouped according to common characteristics. (See John C. Crano, “Chromogenic Material (Photochromic)”, Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, 1993, pp. 321-332). A common mechanism for most and is known classes of photochromic compounds, for example, endosonography and indolinecarboxylic includes elektrotechnichesky mechanism. When exposed to activating radiation, these compounds pass from colorless connection with a closed cycle in the painted samples with open loop. On the other hand, the painted form polygenic photochromic compounds generated using electrotechnicheskogo mechanism involving the conversion of the colorless form an open loop in painted form a closed loop.

In the present invention can be used with a wide range of photochromic compounds. In a non-limiting embodiment, can be used organic photochromic compounds or substances. In alternate non-limiting embodiments can be entered photochromic compounds, for example, dissolved, dispersed or diffonderanno in polymerizat or applied thereto in the form of a coating.

In a non-limiting embodiment, the organic photochromic substance can be activated absorption maximum within the visible area of greater than 590 nm. In another non-limiting embodiment, the activated absorption maximum within the visible region may be in the range of at least from 590 to 700 nm. Such materials can give a blue, bluish-green or bluish-purple is the color when exposed to ultraviolet light in an appropriate solvent or in the matrix. Non-limiting examples of such substances that can be used in the present invention include, but are not limited to, Spiro(indoline)nafoxidine and Spiro(indoline)benzoxazines. These and other acceptable photochromic substances described in U.S. patents: 3562172, 3578602, 4215010, 4342668, 5405958, 4637698, 4931219, 4816584, 4880667, 4818096.

In another non-limiting embodiment, the organic photochromic substances may have at least one maximum absorption within the visible region in the range from 400 to less than 500 nm. In another non-limiting embodiment, the substance may have two maximum absorption within the visible range. Such materials can give a yellow-orange color when exposed to ultraviolet light in an appropriate solvent or in the matrix. Non-limiting examples of such materials may be some chromenes, such as, but without limitation, benzopyrene and naphthopyrane. Many of these chromenes described in U.S. patents: 3567605, 4826977, 5066818, 4826977, 5066818, 5466398, 5384077, 5238931 and 5274132.

In another non-limiting embodiment, the photochromic substance can have a maximum absorption in the visible region in the range from 400 to 500 nm and the maximum absorption within the visible region in the range from 500 to 700 nm. Such materials provide color(s) in the range from yellow/brown to purple the CSOs/gray when exposed to ultraviolet light in an appropriate solvent or in the matrix. Non-limiting examples of such substances may be some benzopyrene compounds having substituents in the 2-nd position Pyrenophora cycle and substituted or unsubstituted heterocyclic ring, for example benzothieno or benzofuranol ring condensed with the benzene part of benzopyrene. Other non-limiting examples of such compounds are disclosed in U.S. patent No. 5429774.

In some non-limiting embodiments, the implementation of the photochromic substance for use in the present invention may be a photochromic the ORGANOMETALLIC dithizonate, such as, but without limitation, arylhydrazines (arylazo)tiarawine acid, such as, but without limitation, dithizonate mercury, which are described, for example, in U.S. patent No. 3361706. Fulgide and fulginiti, such as, but without limiting them, 3-furyl and 3-toilfully and fulginiti, which are described in U.S. patent No. 4931220 (column 20, line 5 to column 21, line 38), can be used in the present invention. The relevant portions of the above patents incorporated by reference.

In other non-limiting embodiments, the implementation of the photochromic articles of the present invention can include one photochromic substance or a mixture of several photochromic compounds. In other non-limiting embodiments, the implementation of the various who's a mixture of photochromic substances may be used, to get activated colors such as a near neutral gray or brown.

The amount of photochromic substance may vary. In some non-limiting embodiments, the implementation of a number of photochromic substances and the ratio of substances (for example, when the mixture is used) can be such that polymerizat, which caused a substance or in which the substance is included, upon activation of direct sunlight gave the desired color, for example essentially neutral color such as shades of gray or brown, that is, as much as possible close to the neutral color data of the colors of the activated photochromic compounds. In some non-limiting embodiments, the amount of photochromic substance may depend on the color intensity of the activated samples and the desired base color.

In some non-limiting embodiments, the implementation of the photochromic substance may be applied to polymerizat or included in polymerizat various methods known in the art. In a non-limiting embodiment, the photochromic substance can be dissolved or dispersed within polymerizate. In other non-limiting embodiments, the implementation of the photochromic substance can be absorbed into polymerized using way is, known in the art. The definition of "absorption" or "absorb" includes the penetration of the photochromic substances without assistance in polymerizat, transfer by absorption with the assistance of the solvent photochromic substance into a porous polymer, the transfer of vapor phase and other such transfer mechanisms. In a non-limiting embodiment, the method of absorption may include a coating on the photochromic article of photochromic substances; heating the surface of the photochromic product; and removing the remaining coating from the surface of the photochromic product. In alternate non-limiting embodiments, the implementation of the absorption process may include immersing polymerizate in a hot solution of the photochromic substance or by thermal transfer.

In some non-limiting embodiments, the implementation of the photochromic substance may be a separate layer between adjacent layers of polymerizate, for example, as part of the polymer film; or photochromic substance may be applied in the form of a coating or as part of a coating placed on the surface of polymerizate.

The amount of photochromic substance or composition containing the photochromic substance deposited or embedded in polymerized may vary. In some non-limiting embodiments of the invention can be such Tobari activation occurred photochromic effect, visible to the naked eye. This number can usually be described as a photochromic amount. In some non-limiting embodiments, the implementation used, the number may depend on the intensity of color desired upon irradiation, and the method of implementation or application of photochromic substances. In General, the more applied or implemented photochromic substances, the higher the intensity of the color. In some non-limiting embodiments, the implementation of a number of photochromic substances embedded in photochromic optical polymerizat or applied thereto, can be from 0.15 to 0.35 mg per square centimeter of surface to which the photochromic substance is introduced or applied.

In another non-limiting embodiment, the photochromic substance can be added to the polyurethane prior to polymerization and/or curing of the material in bulk. This version used the photochromic substance may be selected so that it is resistant to potentially harmful interactions, for example, to the presence of the isocyanate. Such harmful interactions can lead to deactivation of the photochromic substances, for example, by trapping him in open or in closed form.

Other non-limiting examples of suitable photochromic substances for use in the present and the finding may include photochromic pigments and organic photochromic substances, encapsulated in metal oxides, such as described in U.S. patent No. 4166043 and 4367170; organic photochromic substances encapsulated in organic polymerizate, such as described in U.S. patent No. 4931220.

Further, the invention is additionally described with reference to the following examples. Unless otherwise noted, all parts and percentages are mass.

EXAMPLES

The physical properties shown below, is measured as follows.

The transmittance (%) measured in accordance with ASTM A-82.

The yellowing index is measured in accordance with ASTM D 1925-70.

The refractive index is measured on multiwave the Abbe Refractometer, model DR-M2 manufactured by ATAGO Co., Ltd.; the refractive index of liquids measured in accordance with ASTM D1218; and the refractive index of solids is measured in accordance with ASTM D 542.

Density (g/cm3) solids is measured in accordance with ASTM-D 792-00.

Abrasion on Taberu (% opacity) are measured for up to 100 cycles with the abrasive machine of Tabera, which has an abrasive CS-10F weighing 500 g for sample sizes of 3×3×1/8 DM (7.62 cm × 7.62 cm × 0,32 cm) according to ASTM-D 1044-99.

Abrasion by Bauer (% turbidity) measured in accordance with ASTM F 735-94 (povorotny in 2001).

The coefficient For the resistance to crack propagation is measured in accordance with U.S. Dept. of Defense MIL-PRF-25690B (January 29, 1993).

Ultimate tensile strength at yield,% elongation at yield stress and young's modulus measured at approximately 25°C. in accordance with ASTM D 638-03.

Impact on Gardner measured in accordance with ASTM-D 5420-04.

Multi-Dynatup impact strength measured in accordance with ASTM-D 3763-02.

The shore hardness is measured in accordance with the guide for Durometer shore D.

Test QUV-B carried out for 1000 hours in accordance with ASTM G-53.

The glass transition temperature (Tarticlemeasure using dynamometrical analysis.

Linear coefficient of thermal expansion was measured using a thermomechanical analyzer (TMA) duPont in accordance with ASTM E 228-95.

Use the following abbreviations:

CGDM (CHDM): 1,4-cyclohexanedimethanol;

Des N 3400: 60% dimer of hexamethylenediisocyanate and 40% of the trimer of hexamethylenediisocyanate, commercial product from Bayer;

Des W: 4,4'-methylene-bis(cyclohexylidene), commercial product from Bayer;

MDI (MDI): Methylenediphenyl-4,4'-diisocyanate;

Polycaprolactones: Polycaprolactone diol Tone 0210 having a molecular weight of 1000 g/mol, a commercial product of the firm Solvay;

P is recarbonation 1: polycarbonate diol KM-10-1733, obtained from hexandiol having a molecular weight of 1000 g/mol, a commercial product of the firm Stahl;

Polycarbonatediol 2: polycarbonate diol KM-10-1667 obtained from hexandiol having a molecular weight of 1000 g/mol, a commercial product of the firm Stahl;

TMDI (TMDI): trimethylhexamethylenediamine;

TDM (TSR): trimethylolpropane; and

TMTDI (TMXDI): a meta-tetramethylcyclopentadiene.

An example of a

The polyurethanes and poly(mochevinoi) formulations 1-133 obtained from the components in the amounts listed in tables 1-18.

Polyurethane (formulation not containing water) get in a glass reactor under nitrogen atmosphere with stirring. The polyisocyanate before adding the other components is heated to a temperature of approximately 100°C. the Mixture is heated to a temperature of approximately 110°C for about 10 minutes and kept at this temperature for about 30 minutes.

Poly(mochevinoi) (formulation containing water) also get in a glass reactor under nitrogen atmosphere with stirring. The polyisocyanate is heated to a temperature of approximately 60°C.

In the case of formulations 123-127, 131, 132 and 133 to the polyisocyanate, water is added and the temperature of the support is approximately 30 minutes, get urea prepolymer with isocyanate functionality. Add the other components, the mixture is heated to a temperature of approximately 90°C for about 10 minutes and kept at this temperature for about 30 minutes.

In the case of formulations 128-130 to the polyisocyanate add about 0.15 equivalent of trimethylolpropane and the temperature was kept for approximately 120 minutes with the formation of motivirovannogo of prepolymer with isocyanate functionality. Add other ingredients, the mixture is heated to a temperature of approximately 110°C for 120 minutes and kept at this temperature for approximately 4 hours.

Each mixture of polyurethane and poly(mochevinoi) desirous to remove carbon dioxide and poured into a casting cell sizes 12”×13”×0,125” (30,5 cm × 33 cm ×0.3 cm), which is preheated to a temperature of approximately 121°C. the Filled cell then utverjdayut in the oven for about 48 hours at about 121°C.

Table 1
Prescriptions-round, No.The polyisocyanateBranched polyolDiolThe content of the urethane, (% wt.)the contents of the
cyclic
groups
(% wt.)
Mol. weight
the stitching
(g/mol)
The content of hard segments
(% wt.)
TypeEQ.TypeEQ.TypeEQ.
1Des W1,00TMP0,31,4-Butanediol0,733,4945,98176270,00
2Des W1,00TMP0,31,5-Pentanediol0,732,5944,74181071,00
3Des W1,00TMP0,61,5-Pentanediol0,4 32,9945,29178841,00
4Des W1,00TMP0,31,6-Hexanediol0,731,7343,56186071,00
5Des W1,00TMP0,3Xianglian0,3530,41at 76.00194071,00
CGDM0,35
6Des W1,00TMP0,31,5-Pentanediol0,3531,3758,001881 72,00
CGDM0,35
7Des W1,00TMP0,31,6-Hexanediol0,3530,9757,34190572,00
CGDM0,35
8Des W1,00TMP0,31,8-Octandiol0,730,1441,37195873,00
9Des W1,00TMP0,31,10-Decandiol0,7increased by 28.7039,40205674,00
10 Des W1,00TMP0,31,8-Octandiol0,3529,4040,36200774,00
1,10-Decandiol0,35
11Des W1,00TMP0,8CGDM0,232,5353,60181422,00
12Des W1,00TMP0,3CGDM0,730,2470,50195173,00
13Des W1,00TMP0,81,5-Pentanediol 0,2of 33.2645,67177421,00
14Des W1,00TMP0,31,7-Heptanediol0,730,9142,44190972,00
15Des1,00TMP0,31,9-Nonanediol0,729,4040,36200773,00
16Des W1,00TMP0,31,12-Dodecanediol0,727,3937,60215475,60
17Des W1,00TMP 0,61,10-Decandiol0,430,5942,00192945,00
18Des W1,00TMP0,41,10-Decandiol0,429,7540,84198345,00
CGDM0,2
19Des W1,00TMP0,31,10-Decandiol0,6526,5236,40222563,00
Polycarbonatediol 10,05
20TMDI1,00TMP 0,3CGDM0,734,9147,92169073,00

td align="justify" morerows="1"> 39,69
Table 2
Prescriptions-round, No.The polyisocyanateBranched polyolDiolThe content of the urethane, (% wt.)Table of contents
cyclic
groups
(% wt.)
Mol. weight
the stitching
(g/mol)
The content of hard segments
(% wt.)
TypeEQ.TypeEQ.TypeEQ.
21Des W1,00TMP0,31,4-Butanediol0,627,54 37,81214249,00
Polycarbonatediol 10,1
22Des W1,00TMP0,3Isopropylidene-dicyclohexano0,725,7935,41228777,00
23Des W1,00TMP0,41,10-Decandiol0,525,0834,44235246,00
Polycarbonatediol 10,1
24Des W1,00TMP0,31,10-Decandiol0,6 24,6433,83239546,00
Polycarbonatediol 10,1
25Des W1,00TMP0,31,4-Butanediol0,523,3832,10252354,00
Polycarbonatediol 10,2
26Des W1,00TMP0,41,10-Decandiol0,629,3040,23201365,00
27Des W0,5TMP0,31,10-Decandiol0,7 29,1339,992025
MDI0,5
28Des W1,00TMP0,31,12-Cyclododecanol0,727,4837,722147
29TMDI1,00TMP0,2CGDM0,834,3547,16171873,00
301,00TMP0,3Decandiol0,4529,3440,282011
Xianglian 0,25
31Des W0,3TMP0,31,10-Decandiol0,731,5043,241873
TMDI0,7
32Des W0,8TMP0,31,10-Decandiol0,527,6237,92213675,00
Bis(2-hydroxyethyl)-terephthalate0,2
34Des W0,75TMP0,31,10-Decandiol0,728,912041
MDI0,25

Table 8
Recipe №The transmittance (%)The rate of yellowingRefractive indexDensity (g/cm3)
191,840,441,5241,1417
291,910,341,5311,1307
391,90,331,5311,1388
491,880,41,5311,1209
591,580,661,5441,1346
691,840,371,5331,1261
791,870,341,5311,1144
891,81,651,5241,1051
991,930,51,5271,0912
1091,721,71,5271,0929
151,5241,0969
161,521,0685
17 1,5251,1002
181,5171,0976
19at 1.5211,0886
201,5171,0979
211,5171,1327
231,5231,1043
241,5171,0971
25at 1.5211,1372
261,5251,0876
29 1,5121,0984
301,5311,1049
311,5081,072
321,5271,1123
371,5221,086
381,5221,0831
391,5241,0921
401,5251,0846
411,5221,0866
421,5241,0928
431,5251,076
441,5261,0796
581,145

Table 9
Recipe №Abrasion on TaberuAbrasion by Bayer,
Turbidity (%)
The K-factorThe modulus of elasticity tensile at yield
(pounds/square inch)
Elongation at yield
(%)
Impact on Gardner
(DM·lb)
The number of cyclesTurbidity (%)
1/td> 10028,529,451245,633600041427
260+30,831,481362,436700019/38628
310020,522,55781,833500003,9/19100
41002935,871313,631100056595
510027,826,53902,82338000the 4.7168
610024,7 28,751152,133900032214
710028,633,051230,132700034236
8100+31,139,921522,328700055584
9100+32,447,73564,825100014576
10100+3144,753104,125800017593
1560+32,742,172073259000512
166045,945,5362123800019365
1710028,732,79402950008,4158
1826,434,681227with 286,00014220
1933,945,9430926000014595
2025,142,8817653780004,3553
21 2840,77321131200014536
233843,08462826500012461
2439,143,17486925100015497
2524,537,83452824600014627
2638,138,78141526200019179
2842,6834 3270003
2940,433,8823513690004,4146
3022,438,78115027400016204
3141,825,322252216000433
3241,8346,55185227800014518

Table 11
Recipe №Abrasion on Taberu Abrasion by Bayer,
Turbidity (%)
The K-factorThe modulus of elasticity tensile at yield
(pounds/square inch)
Elongation at yield
(%)
Impact on Gardner
(DM·lb)
The number of cyclesTurbidity (%)
68203
69133
7080
71 56
72106
73136
7440
7538
7663
77 64
78125
79333
80376
81376
82346
832235
842185
86317
87328
88451
8922700015472
9024400011445
9125500021411
9226300019426
932660009443
9427000012403
95 25900013406
9628000019255
972990005290
9827200013405
99346
100333
101 363
102364

Table 12
Recipe №Abrasion on TaberuAbrasion by Bayer,
Turbidity (%)
The K-factorThe modulus of elasticity tensile at yield
(pounds/square inch)
Elongation at yield
(%)
Impact on Gardner
(DM·lb)
The number of cyclesTurbidity (%)
103367
104367
105360
106404
107362
108371
109 327
11097
113334
114552
11882

Table 13
Recipe №Impact strength
Dynatup
The shore hardnessTemperature
vitrification
Ratio
heat
extensions
(inch/inch)
117,679126
224,288811981,91
34,0488140
425,486117,1
58,688156
615,286132
727,286129, 9mm
831,582106
938,4 80of 99.194,65
1035,581102
1524,880105
1634,47993
1713,988123,9
18of 40.983119
1944,381of 89.1
2026,18375,170,01
2139,68197
2317,97987101,11
24the 33.48079,297,2
2544,97876,195,66
2628,684106
295,348571,172,36
3030,785120,1
31417952,196,91
3246,582104
3833,281111,1
3932,981103,9
4041,981101,1
4127,580
4225,181
4335,38097
443,1586
4825,2
494,24
5026,3
5121,6
5231,6
5322,2
5426,7
5541,6
5620,7

Table 14
Recipe №Impact strength
Dynatup
The shore hardnessThe glass transition temperatureThe coefficient of thermal expansion (inch/inch)
5717,2
5862,366
5936,6
6037,4
6138,9
62152
63134
64150
65174
166
67161
8942,6
9048,4
9150,2
9248
9356,5
9445,1
9547,5
9647,5
9734,3
9839,2

Table 16
Recipe №The transmittance (%)The rate of yellowingRefractive indexDensity (g/cm3)
1251,119
1261,125
1271,133
128 1,113
1291,128
1301,113
1311,127
1321,129

Table 17
Recipe №Abrasion on TaberuAbrasion by Bayer,
Turbidity (%)
The K-factorThe modulus of elasticity tensile at yield
(pounds/square inch)
Elongation at yield
(%)
Impact on Gardner
(DM·lb)
The number of cycles Turbidity (%)
1253550001351
1261113305000424
127155128200012244
1288533690001656
1296864410007,58
130 7663890001537
1312900007,7126
13228900019328
13328900011224

Table 18
Recipe №Impact strength
Dynatup
The shore hardnessThe glass transition temperatureThe coefficient of thermal expansion (inch/inch)
125 137
12614,6115
1273067
1283,31161
1293
1308,67153
13132,5
132
1339,29

The above samples show a low yellowness, high light transmission,high impact resistance and good ballistic resistance.

Laminate 6”×6” (15.2 cm × 15.2 cm) 2”-layer (5.1 cm) molded recipe 2 described below, the front surface of the output superimposed on a 1” (2.5 cm) layer molded formulations 9, described below, and 0.5” (1.3 cm) layer molded recipe 60, stops or deflects four consecutive shots from AK-47 (cartridge 7.62 mm × 39 mm) with a distance of 150 feet (45,7 m). Each layer is formed as described above. The glass layer in the laminate is not used. The laminate is heated in an autoclave at approximately 300°F (149°C) for approximately 2 hours.

Samples aerospace extruded acrylic polymer Polycast 84 (commercial product Spartech of Clayton, Missouri) and samples of polymer A, formulation 2 (synthesized at 110°C and solidified at 143°C, as described above), judged by their physical properties, which are presented below in table 19. The sample of example A, formulation 2, has a lower density, higher impact resistance and elongation and is more severe than the tested sample extruded acrylic polymer. Polycarbonate LEXAN #8574K26 (commercial product McMaster Carr Supply Co., Cleveland, Ohio) and samples of the polymer of example A, formulation 84 (synthesized at 110°C and solidified at 143°C, as described above), judged by their physical properties, which are presented below in table 20. Example A, formulation 84, has a good resistance to the action is rastvoritelei, resistance to UV radiation and a higher resistance than the tested sample LEXAN.

Table 19
PropertiesExtruded acrylic polymerA sample of the formulation 2, the sample And
The transmittance9292
Turbidity,%<1%<0,1%
Density1,181,13
Resistance to solvent/75% aqueous sulfuric acidLoad 1000-4000 pound/square inch
The K-factor24001500
The test for resistance to Gardner (DM·lb)16628
High speed multiaxial impact strength3,6 (raw)26,5
Elongation at break (%)<5 38%
Elongation (1000 hours QUV-B) (%)<540%
Tensile strength tensile1125011800
The modulus of tensile elasticity450000367000
The glass transition temperature205247°F (119°C)
The temperature of deformation due to thermal heatingPuckering at t-re 180°F235F°F(113°C)
Abrasion resistance: turbidity (%), 100 cycles on the abrasive machine of Taber3015
Refractive index1,491,519
The shore hardness (Durometer shore D)9490

Table 20
PropertiesPolycarbonate Sample recipes 84, example And
The transmittance8892
Density1,21,8
Resistance to solventsThe lack of HE, N+AcetoneRather HE, N.+Acetone
The resistance according to Gardner, the average energy of destruction588 DM·lb>640 DM·lb (>72 j)
High speed multiaxial impact strength72 J.105 j
Turbidity (%), 100 cycles on the abrasive machine of Taber60%15%
Refractive index1,5861,519
The modulus of tensile elasticity320000300000
Tensile strength tensile8000 pound/square inch8500 pound/square inch
Relative the linnie at break (%) 100%200%
Elongation (1000 hours QUV-B) (%)Strong fracture, brittle, yellow97%
The temperature of deformation due to thermal heating275°F220°F
The glass transition temperature305F240F
The shore hardness (Durometer shore D)8580

Test DMA

Sample recipes 114 (obtained from 0.95 equivalent of 1,10-decandiol, 0.05 equivalents of trimethylolpropane and 1.0 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate) (DESMODUR W) is estimated using dynamometrical analysis (DMA) to determine the dynamic modulus, loss modulus and tangent Delta (tan delta). DMA conducted on a firm, fixed sample size (2”×2”×1/8”) (5.1 cm × 5.1 cm × 0.3 cm), which oscillates with a frequency of 1 Hz within a wide temperature range, which increases with the speed of 3°C/min, As shown in FIG, the sample shows a low temperature phase transition when the module losses at approximately -70°C, which is unusual for an article is celebratng polymers and indicates the molecular mobility in torsion at such low temperatures. The second transition is present at approximately 14°C. the glass transition Temperature of this polymer is 71°C, which is expressed by a peak on the graph tendency. At this temperature the polymer is most effectively converts mechanical vibrations into heat, i.e. it is at this temperature the polymer reaches its maximum damping characteristics. Dynamic modulus of elasticity represents the energy stored by the polymer, and may be associated with the young's modulus or stiffness of the polymer.

Ballistic tests

Example AA

Thick sample of the formulation 2 the above example And sizes 6”×6”×1” (15,2 cm × 15.2 cm × 2.5 cm) utverjdayut by heating at 290°F (143°C) within 48 hours. Four bullets 0.40 caliber, released from a distance of 30 feet (9.1 m) at a speed of 987 ft/sec (300 m/s), ricocheted from the sample surface and the plastic does not crack. The picture in perspective of the test sample shown in FIG.

Example AB

Thick sample of the formulation 2 the above example And dimensions of 6”×6”×3/8” (15.2 cm × 15.2 cm ×1 cm) utverjdayut by heating at 290°F (143°C) within 48 hours. The bullet, shot from a 12 gauge shotgun from a distance of 20 feet (6.1 m) at a speed of 1290 ft/sec (393 m/sec) using heavy sports lead drobin, bounces from the sample surface and plastic doesnt crack the I. The picture in perspective of the test sample shown in FIG.

Example AC

Thick sample recipes 93 the above example And sizes 6”×6”×1” (15,2 cm ×15.2 cm × 2.5 cm) utverjdayut by heating at 290°F (143°C) within 48 hours. Three bullet caliber 9 mm, released from a distance of 20 feet (6.1 m) at a speed of 1350 ft/sec (411 m/sec), stuck in the sample. Photograph of front view of the specimen shown in FIG.

Example AD

Thick sample recipes 94 above example And sizes 6”×6”×1” (15,2 cm × 15.2 cm ×2.5 cm) utverjdayut by heating at 290°F (143°C) within 48 hours. Bullet caliber 9 mm, released from a distance of 20 feet (6.1 m) if the initial velocity of 1350 ft/sec (411 m/sec), stuck in the sample. Pictures of the test sample presented on FIG and FIG. FIG represents a perspective view of the sample showing the bullet stuck in the surface of the sample. FIG is a side view of the sample showing the occurrence of the bullets in the sample.

Example AE

Thick sample of the formulation 2 the above example And sizes 6”×6”×1” (15,2 cm × 15.2 cm × 2.5 cm) utverjdayut by heating at 290°F (143°C) within 48 hours. Thick sample recipes 9 the above example And dimensions of 6”×6”×1” utverjdayut by heating at 290°F (143°C) within 48 hours. A thick sample, R is capture 58 above example And sizes 6”×6”×0,5” (15,2 cm ×15.2 cm × 1,75 cm) utverjdayut by heating at 290°F (143°C) within 48 hours. The composite is prepared by Assembly 1” (2.5 cm) thick layer of sample formulations 2, 1” (2.5 cm) thick layer of sample formulations 9 and 0.5” (1.25 cm) thick layer of sample formulations 58 so that the layer formulation 2 was converted to the rifle.

Four cartridge of 7.62×39 mm, with steel core, are produced from a rifle AK-47 from a distance of 30 yards (27.4 m) when the initial velocity of 2700 ft/s (823 m/s). The first bullet is delayed in the middle layer formulation 9 generally parallel to the initial direction of the shot. Bullets from the second to the fourth stop away from the layer 58 generally parallel to the initial direction of the shot. Pictures of the test sample presented on FIG and 23. FIG is a front view of the sample showing the entry point bullets and two bullet stuck in the surface of the sample. FIG is a rear view of the sample showing two facing bullets stuck in the layer formulations 58 sample.

Example AF

Samples obtained from the formula 58 and 89-97 of the above example And behave similarly, that is all "catch" the bullet. The sample, prepared from recipe 94 shows the least amount of penetration into the sample, with approximately 1/8” of the rear wall of the bullet exiting surface. Not observed viscoplastic thickening in the back surface of the sample, receive the frame from the formulation of 94. Penetration is significantly reduced compared to samples prepared from formulations 58 and 89-92.

The example In

Comparative non-limiting example temperature processing 80°C compared to the temperature of 110°C

Short-chain diols (aliphatic diols having from 4 to 8 carbon atoms, which are discussed above), as a rule, do not mix with isocyanates due to the different polarity and difference in surface tension between the two materials. Found that when short-chain diol and isocyanate are mixed at 80°C. or less, more time is required to form a clear solution, than at 110°C or higher. Although both solution may seem transparent, it was found that the inhomogeneity, which manifests itself in the hardened products with a much lower impact than in the preparation of solutions at 110°C or higher. In addition, when loading or reaction injection molding in the glass form any cooling that takes place in the pouring and exposure to air, or mold temperature below 100°C, exacerbate the problem of inhomogeneity, since additional cooling increases such inhomogeneity. If the temperature drops even lower, short-chain diol and the isocyanate will be divided into phases and look as mu is nye. This turbidity will not be dealt with in a furnace, heated to 120-140°C. after pouring into shape and heating for 24 to 48 hours. Higher vibrations shock also detected when the process temperature falls below 100°C. if the temperature is above 110°C the values of the initial shock on Gardner for polymers of the present invention are higher initially, and they exhibit less fluctuation in shock from boot to boot, when they are processed at temperatures above 110°C. the following examples illustrate the considered temperature effect.

Example B1

The following components: 20,1 g 1,5-pentanediol, 7.5 g of trimethylolpropane and 72,45 g DESMODUR W, containing 20% TRANS-TRANS isomer of 4,4'-methylene-bis(cyclohexylsulfamate), loaded into a glass reactor equipped with a thermocouple and an external mixer. The load is brought to a temperature of from 110 to 120°C with stirring and applying vacuum (2 mm TST (266 PA)) to remove bubbles. After reaching a temperature of 110-120°C load stirred for 10-20 minutes.

Download pour in the heated glass form, which is pre-heated in an oven at 140°C. the Polymer utverjdayut 48 hours at 140°C without a catalyst. After curing, the form is removed from the oven and allow to cool to room temperature. Then from the glass form zavlekayut plastic sheet and cut into samples with dimensions of 2”×2”×1/8” (5.1 cm × 5.1 cm × 0.3 cm) for testing the impact resistance according to Gardner. Initial resistance on the Gardner average of 260 DMPORT (30 j).

Example B2

The following components: 20,1 g 1,5-pentanediol, 7.5 g of trimethylolpropane and 72,45 g DESMODUR W, containing 20% TRANS-TRANS isomer of 4,4'-methylene-bis(cyclohexylsulfamate), loaded into a glass reactor equipped with a thermocouple and an external mixer. The load is brought to a temperature of from 80 to 90°C under stirring and applying vacuum (2 mm Hg (266 PA)) to remove bubbles. After reaching a temperature of 80-90°C load is stirred for 1-2 hours until the download is not clear.

Download pour in the heated glass form, which is pre-heated in an oven at 140°C. the Polymer utverjdayut 48 hours at 140°C without a catalyst. After curing, the form is removed from the oven and allow to cool to room temperature. Then from the glass forms remove the plastic sheet and cut into samples with dimensions (2”×2”×1/8”) (5.1 cm × 5.1 cm × 0.3 cm) for testing the impact resistance according to Gardner. Initial resistance on the Gardner average of 62 DM·lb (7 j).

Example B3

The following components: 17.9 g of 1,4-butanediol, and 7.4 g of trimethylolpropane and 74,47 g DESMODUR W, containing 20% TRANS-TRANS isomer of 4,4'-methylene-bis(cyclohexylsulfamate), loaded into a glass reactor equipped with a thermocouple and an external mixer. The load is brought to a temperature of from to 120°C under stirring and applying vacuum (2 mm Hg (266 PA)) to remove bubbles. After reaching a temperature of 110-120°C load stirred for 10-20 minutes.

Download pour in the heated glass form, which is pre-heated in an oven at 140°C. the Polymer utverjdayut 48 hours at 140°C without a catalyst. After curing, the form is removed from the oven and allow to cool to room temperature. Then from the glass forms remove the plastic sheet and cut into samples with dimensions of 2”×2”×1/8” (5.1 cm × 5.1 cm × 0.3 cm) for testing the impact resistance according to Gardner. Initial resistance on the Gardner average of 180 DM·lb (21 j).

Example B4

The following components: 17.9 g of 1,4-butanediol, and 7.4 g of trimethylolpropane and 74,47 g DESMODUR W, containing 20% TRANS-TRANS isomer of 4,4'-methylene-bis(cyclohexylsulfamate), loaded into a glass reactor equipped with a thermocouple and an external mixer. The load is brought to a temperature of from 80 to 90°C under stirring and applying vacuum (2 mm Hg (266 PA)) to remove bubbles. After reaching a temperature of 80-90°C load is stirred for 1-2 hours until the download is not clear.

Download pour in the heated glass form, which is pre-heated in an oven at 140°C. the Polymer utverjdayut 48 hours at 140°C without a catalyst. After curing, the form is removed from the oven and allow to cool to room temperature. Then from stealin the th form remove the plastic sheet and cut into samples with dimensions of 2”×2”×1/8” (5.1 cm × 5.1 cm × 0.3 cm) for testing the impact resistance according to Gardner. Initial resistance by Gardner on average 10-15 DM·lb (1-1,5 j).

Example With

To estimate the total percentage located in a number of crystalline domains in samples of polyurethanes in accordance with the present invention, samples of formulation No. 2 (0.7 equivalent of 1,5-pentanediol (PDO, PDO), 0.3 equivalents of trimethylolpropane (TMP) and 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate) (DESMODUR W)) and formulation No. 136 (0.95 equivalent DTP, 0.05 equivalent TDM and 1 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate) (DESMODUR W)) experience using differential scanning calorimetry (DSC) at a speed of 2°C/min and using thermogravimetric analysis (TGA).

Each sample was prepared as follows: mix all the components in the corresponding recipe at approximately 110°C for about 30 minutes, Tegaserod in vacuum for about 5 to 10 minutes; then pour in glass form, heated to approximately 200°F (93°C), and utverjdayut approximately 48 hours, cooled to room temperature (25°C) and then removed from the form. Sample recipe No. 2 incubated at approximately 25°C for approximately seven months.

Sample recipe No. 136 (aged approximately at 25°C for approximately two weeks) is used as the control sample, and it is recent located in a number of crystalline domains use as a reference point for 100% crystallinity. About 100% of the crystallinity of the sample formulations No. 136 share located in a number of crystalline domains in recipe No. 2, as calculated, is 42%. In the case of both samples detected endothermic peak around ~260°C, and this peak is attributed to melting them ordered domains. Data DSK for each of the sample formulations # 2 and # 136 presented below in table 21 and FIG and 25, respectively. Thermogravimetric analysis (TGA) for sample formulation No. 136 presented on FIG.

Table 21
The aggregated results of DSC
Sample No.1362
Equivalents and
components recipe
0,95 PDO + 0,05 TMP + 1 Des W0.7 DTP + 0,3 TMP + 1 Des W
Tarticle(aboutC)99
Peak endothermy (aboutC)260260
Heat capacity (j/g)of 3.771,63
Calculated crystal to the ENES (%) 100 (Control)42

Example D: Ballistic tests

Example D1

The polyurethane polymer in accordance with the present invention is obtained from the components listed below in table 22.

Table 22
SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer1,10-decandiolTMPDes W205,30300,00
HE#---
Acid#---
Equivalent weight8744,00131,2
Specified equivalents0,70,31,0
The weight of the monomer60,9013,20131,20
Mass % of the monomer29,66%to 6.43%63,91%
Weight of the monomers during the experience88,9919,29191,72
Mass % of the hard segments74,40
Mass % urethane28,74
The molecular mass on the stitching (g/mol) (Mwith)2053,00

1,10-Decandiol, trimethylolpropane and DESMODUR W is heated to 80°C and added to a glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~115°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30,5 cm × 30.5 cm × 0.3 cm), preheated to 121°C. the Filled cell utverjdayut within 48 hours at 143°C.

This recipe thickness 6”×6”×1” (15,2 cm × 15.2 cm × 2.5 cm) holds up a pistol caliber 0,40 from a distance of 30 feet (9.1 m) and speed 987 ft/sec without cracking. At a distance of 20 feet (6.1 m) bullet stops and cracking is not observed. Without cracking maintained multiple shots bullet 9 mm, 1350 ft/sec (411 m/sec) from 20 feet (6.1 m). The recipe also withstand 3 on sledovatelya shot from a 12 gauge shotgun (1290 ft/sec) from a distance of 30 feet (9.1 m) with 3/8” thick (18”×12”×3/8”) (46 cm × 30 cm × 1 cm) using heavy sports lead bullets. In each test bullets ricocheted from the target.

Example D2

The polyurethane polymer in accordance with the present invention is obtained from the components listed below in table 23.

Table 23
SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerPC-17331,5-pentanediolTMPDes W239,04300,00
HE#----
Acid#----
Equivalent weight44052,0844,00131,2
Specified equivalents0,150,550,31,0
The weight of the monomerof 66.0028,6413,20131,20
Mass % of the monomer27,61%11,98%5,52%54,89%
Weight of the monomers during the experience82,8335,9516,57164,66
Mass % of the hard segments35,84
Mass % urethane24,68
The molecular mass on the stitching (g/mol) (Mwith)2390,4

1,5-Pentanediol, MS-1733, trimethylolpropane and DESMODUR W, preheated to 80°C, add in a glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30,5 cm × 30.5 cm × 0.3 cm), preheated to 121°C. the Filled cell utverjdayut within 48 hours at 143°C.

This recipe can withstand multiple shots bullet 9 mm (115 Grand), 1350 ft/sec, by "capturing" the scope poly the EPA in samples sizes 6"×6"×1" (15,2 cm × 15.2 cm × 2.5 cm). The bullet penetration is approximately 0.25” (0.6 cm) in the absence of viscoelastic swelling in the back of the sample. The same recipe with dimensions 4”×4”×1” (10,1 cm × 10.1 cm × 2.5 cm) also withstands multiple shots 0.40 caliber at which the bullet is neither captured nor bounces. Bullet settles slightly deformed at the base of the sample. When the thickness of 3/8” (1 cm) this formulation can withstand 3 shot 12 gauge shotgun from a distance of 30 feet (9.1 cm). Most of the bullets buried in the surface of the sample.

Example D3

The polyurethane polymer in accordance with the present invention is obtained from the components listed below in table 24.

Table 24
SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer1,4-butanediolTMPDes W175,94300,00
HE#---
Acid#---
Equivalent weight45,0644,00131,2
Specified equivalents0,70,31,0
The weight of the monomer31,5413,20131,20
Mass % of the monomer17,93%7,50%74,57%
Weight of the monomers during the experience53,7822,51223,71
Mass % of the hard segments70,13
Mass % urethane33,53
The molecular mass on the stitching (g/mol) (Mwith)1759,42

1,4-Butanediol, trimethylolpropane and DESMODUR W, preheated to 80°C, add in a glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell(12”×12”×0,125”) (30,5 cm × 30.5 cm × 0.3 cm), preheated to 121°C. the Filled cell utverjdayut within 48 hours at 143°C.

This recipe in the sample razmere”×6”×1” (15.2 cm × 15.2 cm ×2.5 cm) withstands multiple shots caliber 0,40 from a distance of 30 feet (9.1 m) without cracking. The speed of 0.40 caliber is 987 ft/sec (300 m/sec). When the thickness of 3/8” (1 cm) at a distance of 60 feet (18.2 m) formulation can withstand repeated blows from a 12 gauge shotgun big bullets initial speed of the bullet 1290 ft/sec (393 m/sec). From a distance of 20 feet (6.1 m) and 30 ft (9.1 m) this recipe at a thickness of 1” (2.5 cm) down to 9 mm (115 Grand) pistol bullet at a speed of 1350 ft/sec (411 m/sec).

Example D4

The polyurethane polymer in accordance with the present invention is obtained from the components listed below in table 25.

Table 25
SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer1,5-pentanediolTMPDes W180,85300,00
HE#---
Acid#-- -
Equivalent weight52,07544,00131,2
Specified equivalents0,70,31,0
The weight of the monomer36,4513,20131,20
Mass % of the monomer20,16%7,30%72,55%
Weight of the monomers during the experience60,4721,90217,64
Mass % of the hard segmentsis 70.94
Mass % urethane32,62
The molecular mass on the stitching (g/mol) (Mwith)1808,53

1,5-Pentanediol, trimethylolpropane and DESMODUR W, preheated to 80°C, add in a glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~115°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell(12”×12”×0,125”) (30,5 cm × 30.5 cm × 0.3 cm), preheated to 121°C. the Filled cell utverjdayut within 48 hours at 143°C.

This recipe is the sample size 6”×6”×1” (15,2 cm × 15.2 cm × 2.5 cm) holds up a pistol 0.40 caliber from a distance of 30 feet (9.1 m) and at a speed ft/sec (300 m/sec) without cracking. At a distance of 20 feet (6.1 m) bullet stops, but there is a certain amount of small cracks. Without cracking maintained multiple rounds of 9 mm, 1350 ft/sec (411 m/sec), from a distance of 20 feet (6.1 m). The recipe also withstands 3 consecutive shots from a 12 gauge shotgun (1290 ft/sec) (393 m/sec) from a distance of 30 feet (9.1 m) at a thickness of 3/8” (1 cm) and using a heavy sports lead bullets.

Example D5

The polyurethane polymer in accordance with the present invention is obtained from the components listed below in table 26.

Table 26
SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerCM-17331,5-pentanediolTMPDes W258,44300,00
HE#----
Acid#----
Equivalent weight44052,07544,00131,2
Specified equivalents0,20,50,31,0
The weight of the monomer88,00to 26.0413,20131,20
Mass % of the monomer34,05%10,07%5,11%50,77 %
Weight of the monomers during the experience102,1530,2215,32152,30
Mass % of the hard segments44,20
Mass % urethaneto 22.83
The molecular mass on the stitching (g/mol) (Mwith)2584,38

1,5-Pentandiol, polycarbonate diol CM-1733, trimethylolpropane and DESMODUR W, preheated to 80°C, add in a glass reactor. In the atmosphere of nitrogen is with constant stirring, the mixture is heated to ~105°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell(12”×12”×0,125”) (30,5 cm ×30.5 cm ×0.3 cm), pre-heated to 143°C. the Filled cell utverjdayut within 48 hours at 121°C.

This recipe stands up to repeated rounds of 9 mm (115 Grand), 1359 ft/sec (393 m/sec) by "capturing" in the amount of polymer in the sample size 6"×6"×1" (15,2 cm × 15.2 cm × 2.5 cm). The bullet penetration is approximately 0.5” (1.2 cm) with negligible viscoelastic swelling in the back of the sample. The same sample size 4”×4”×1” (10,1 cm × 10.1 cm × 2.5 cm) also withstands multiple shots 0.40 caliber at which the bullet is neither captured nor bounces. Bullet settles slightly deformed at the base of the sample. When the thickness of 3/8” (1 cm) this formulation can withstand 3 shot 12 gauge shotgun from a distance of 30 feet (9.1 m). Most of the bullets buried in the surface of the sample.

All of the 9 mm rounds produced by bullets weighing 115 Grand, the initial velocity of 1350 ft/sec (411 m/sec), which are produced from a 9 mm pistol Ruger. All shots 0.40 caliber made pistol, Smith and Wesson" 0.40 caliber with the initial velocity 987 ft/sec (300 m/sec). All rifle 12 gauge made from a shotgun Remington 12 gauge with the use of lead bullets, major sporting bullets, when the initial velocity of the bullet 1290 ft/sec(393 m/sec). Fired samples, which are attached to a wooden block with thickness of 12” using Velcro®without a frame for holding the sample. Shooting produce on the street at a temperature in the range from about 60 to 80°F (15-27°C).

Example E

Prepare samples of formulation 2 of the above example and experience to determine the impact on Gardner as in example A. the Sample E1 obtained using 35% of the mass. TRANS,TRANS isomer of 4,4'-methylene-bis(cyclohexylsulfamate). Sample E2 obtained using 17% of the mass. TRANS,TRANS isomer of 4,4'-methylene-bis(cyclohexylsulfamate). Impact on Gardner sample E1 is 150 DM·lb (17 j). Impact on Gardner sample E2 is 40 DM·lb (5 Joule). Sample E1, obtained using a higher weight percent of the TRANS,TRANS isomer of 4,4'-methylene-bis(cyclohexylsulfamate)has a higher impact on Gardner, than the sample E2, which is obtained with a lower mass% TRANS,TRANS isomer of 4,4'-methylene-bis(cyclohexylsulfamate).

Example F

Samples obtained from the formulation 1 of the above example 1 with the additional inclusion of 3% of the mass. system liquid sitosterolemia CIBA TINUVIN B75 (commercial product of the firm Ciba Specialty Chemicals, which is a mixture of 20% of the mass. IRGANOX 1135, 40% of the mass. TINUVIN 571 and 40% of the mass. TIUVIN 765). Initial resistance on the Gardner 75 DM·lb (9 j). After 1000 hours QUV test-B impact on Gardner 75 DM·lb (9 j). Initial ultimate tensile strength is 13400 psi (92,4 MPa) and after 1000 hours QUV test-B is 13100 psi (90,3 MPa). The initial elongation is 40% after 1000 hours QUV test-B is 50%.

Example G

Examples elastoplastic polyurethane

Example G1

The following reagents: 131,2 g DESMODUR W, 13,41 g of trimethylolpropane, 26,015 g of 1,5-pentanediol and 81,712 g Stahl KM-1733, polycarbonate diol with a molecular weight of 1000 on the basis of hexandiol, mixed together, heated to 80°C and Tegaserod. Add 10 ppm of dibutyltindilaurate and stirred until the solution becomes homogeneous. The mixture is then poured into the glass shape and utverjdayut within 48 hours at 290°C (143°C). After curing, the form is allowed to cool down to room temperature (25°C) and the polymer extracted from the form. The polymer has a young's modulus 215000 psi (approximately 1482 MPa). The content of the urethane stands at 23.4% of the mass. The molecular weight of the stitching is 2548 g/mol. The content of cyclic groups is 32% of the mass.

Product dimensions 6”×6”×1” (15,2 cm × 15.2 cm × 2.5 cm), made from this polymer, stops 9 mm (125 GP) bullet, released with an initial velocity of 1350 ft/sec (m/sec) from a distance of 20 feet (6.1 m), by capturing bullets in the polymer. The rear part of the bullet penetrates approximately 1/8” (0.3 cm) in the sample with a very slight rise on the back wall.

Example G2

The following reagents: 131,2 g DESMODUR W, 13,41 g of trimethylolpropane, 28,096 g of 1,5-pentanediol and 65,370 g Stahl KM-1733, polycarbonate diol with a molecular weight of 1000 on the basis of hexandiol, mixed together, heated to 80°C and Tegaserod. Add 10 ppm of dibutyltindilaurate and stirred until the solution becomes homogeneous. The mixture is then poured into the glass shape and utverjdayut within 48 hours at 290°C (143°C). After curing, the form is allowed to cool down to room temperature (25°C) and the polymer extracted from the form. The polymer has a young's modulus 215000 psi (approximately 1482 MPa). The content of the urethane is 24.8% of the mass. The molecular weight of the stitching is 2404 g/mol. The content of cyclic groups is 34% of the mass.

Product dimensions 6”×6”×1” (15,2 cm × 15.2 cm × 2.5 cm), made from this polymer, stops 9 mm (125 GP) bullet, released with an initial velocity of 1350 ft/sec (411 m/sec) from a distance of 20 feet (6.1 m), by capturing bullets in the polymer. Four-fifths (4/5) of the length of the bullet penetrates into the sample, and the rear part of the bullet is approximately 1/8” (0.3 cm) from the exposed surface impact.

Example G3

The following reagents: 131,2 g DESMODUR W, 13,41 g of trimethylolpropane, 8,617 g of 1,5-pentanediol and 61,284 g Stahl KM-1733, the polycarbonate diol with a molecular weight of 1000 on the basis of hexandiol, mixed together, heated to 80°C and Tegaserod. Add 10 ppm of dibutyltindilaurate and stirred until the solution becomes homogeneous. The mixture is then poured into the glass shape and utverjdayut within 48 hours at 290°C (143°C). After curing, the form is allowed to cool down to room temperature (25°C) and the polymer extracted from the form. The polymer has a young's modulus 215000 psi (approximately 1482 MPa). The content of the urethane is to 25.15% of the mass. The molecular weight of the stitching is 2369 g/mol. The content of cyclic groups is 34,53% of the mass.

Product dimensions 6”×6”×1” (15,2 cm × 15.2 cm × 2.5 cm), made from this polymer, stops 9 mm (125 GP) bullet, released with an initial velocity of 1350 ft/sec (411 m/sec) from a distance of 20 feet (6.1 m), by capturing bullets in the polymer. Four-fifths (4/5) of the length of the bullet penetrates into the sample, and the rear part of the bullet is approximately 1/8” (0.3 cm) from the exposed surface impact.

Examples of poly(mochevinoi)

Example G4

The following reagents: 318,26 g of DESMODUR W and 0.84 g of trimethylolpropane containing 0.5% dibutyltindilaurate, loaded into a glass reactor, heated and stirred at 75°C. Add deionized water (4,37 g), mixed and performed the reaction with getting hard polyurea of Segmentum polyurethane prepolymer. Foam, carbon dioxide is removed in vacuum. Then increase the temperature to 80°C and carry out the reaction for 30 minutes. Output gases using a vacuum of 2 mm Hg and add 63,42 g of 1,5-pentanediol with 32.76ˆ g of trimethylolpropane. The mixture is stirred and slowly increase the vacuum. Exothermic temperature reaches 95°C and at this time the mixture is then poured into the glass shape with dimensions of 6”×6”×1/8” (15.2 cm × 15.2 cm × 0.3 cm). Material utverjdayut at 290°F (143°C) within 48 hours. The material is extracted from the mold at room temperature (25°C)receive transparent, good light transmissive plastic.

Example G5

The following reagents: 2,23 g of trimethylolpropane enter into reaction with 76,133 g DESMODUR W, containing 10 ppm of dibutyltindilaurate, at 80°C with the formation of branched polyurethane, isocyanate-terminated groups. To download add water (0.9 g) after lowering the temperature to 60°C., and the reaction is carried out for 2 hours, get the polyurea part polyurethanecontaining of prepolymer. Then carbon dioxide is removed in vacuo, add 38 g of trimethylolpropane, mixed, Tegaserod in vacuum and poured into the glass the form described above, at 75°C. After curing for 48 hours at 290°F (143°C) remove plastic from the mold at room temperature (25°C), receive a good transmission of light plastic with a high modulus of elasticity. Odul Jung is 441000 psi when measured on a tensile testing machine Instron when the velocity of the beam 6”/min

Example G6

The following reagents: 2,23 g of trimethylolpropane enter into reaction with 131,2 g DESMODUR W with 10 masses. h/million dibutyltindilaurate based on the entire load, get the branched-terminated isocyanate groups of the polyurethane prepolymer. Add deionized water (1,34 g) and the reaction is carried out at 60°C. to Remove carbon dioxide by degassing in a vacuum. The temperature was raised to 75°C and add 39,66 g cyclohexanedimethanol as an extension of the chains. After mixing and degassing, the liquid is poured into the glass the form described above, and utverjdayut at 290°F (143°C) within 48 hours. Removing from the mold is carried out at room temperature (25°C), get a sheet of plastic with high optical characteristics.

Example N

Example H1

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer1,4-ButanediolTMPDes W175,94300,00
HE#---
Acid#---
Equivalent weight45,0644,00131,2
Specified equivalents0,70000,3001,000
The weight of the monomer31,5413,20131,20
Mass % of the monomer17,93%7,50%74,57%
Weight of the monomers during the experience53,7822,51223,71

1,4-Butanediol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 cm × 30 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C and for 6 hours at 150°C. the Average impact on Gardner is 102 DM·lb (12 j).

Example H2

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer1,4-ButanediolTMPDes W175,94300,00
HE#- --
Acid#---
Equivalent weight45,0644,00131,2
Specified equivalents0,70000,3001,000
The weight of the monomer31,5413,20131,20
Mass % of the monomer17,93%7,50%74,57%
Weight of the monomers during the experience 53,7822,51223,71
Mass % of the hard segments70,13
Mass % urethane33,53
(Mwith)1759,42

1,4-Butanediol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C and enable the components to be combined. The mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 cm × 30 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average value of the shock is about the Gardner is 110 DM·lb (13 j).

Example H3

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer1,4-ButanediolTMPDes W175,94300,00
HE#---
Acid#---
Equivalent weight45,0644,00131,2
Specified equivalents0,70000,3001,000
The mass of the monomer is 31,5413,20131,20
Mass % of the monomer17,93%7,50%74,57%
Weight of the monomers during the experience53,7822,51223,71
Mass % of the hard segments70,13
Mass % urethane33,53
(Mwith)1759,42

1,4-Butanediol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C and enable the components to be combined. The mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 cm × 30 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner is 131 DM·lb (15 j).

Example H4

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer1,5-PentanediolTMPDes W180,85300,00
HE#---
Acid#---
Equivalent weight52,07544,00131,2
Specified equivalents0,70000,3001,000
The weight of the monomer36,4513,20131,20
Mass % of the monomer20,16%7,30%72,55%
Weight of the monomers during the experience60,4721,90217,64
Mass % of the hard segmentsis 70.94
Mass % urethane32,62
(Mwith)1808,53

1,5-Pentanediol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~115°C and enable the components to be combined. The mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 cm × 30 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner is 135 DM·lb (15 j).

Example H5

Prepare the polyurethane of following the ith components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer1,5-PentanediolTMPDes W178,43300,00
HE#---
Acid#---
Equivalent weight52,07544,00131,2
Specified equivalents0,40000,6001,000
The weight of the monomer20,836,40 131,20
Mass % of the monomer11,67%14,80%73,53%
Weight of the monomers during the experience35,0244,39220,59
Mass % of the hard segments41,09
Mass % urethane33,07
(Mwith)89,15

1,5-Pentanediol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~115°C and enable the components to be combined. The mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 cm × 30 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner is 71 DM·lb (8 j).

Example N6

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerCGDM1,5-pentanediolTMPDes W187,86300,00
HE#----
Acid#----
Equivalent weight72,1152,07544,00131,2
Specified equivalents0,35000,35000,3001,000
The weight of the monomer25,2418,2313,20131,20
Mass % of the monomer13,43%9,70%7,03%69,84%
Weight of the monomers during the experience40,3029,1121,08209,51
Mass % of the hard segments37,88
Mass % urethane31,41
(Mwith)1878,65

1,5-Pentanediol, CGDM, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, see the camping is heated to ~105°C and enable the components to be combined. The mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 cm × 30 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner is 143 DM·lb (16 j).

Example H7

Prepare the polyurethane of the following components:

tr>
SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerCGDMTMPDes W194,88352,00
HE#----
Acid#----
Equivalent weight72,1144,00131,2
Specified equivalents0,70000,3001,000
The weight of the monomer50,4813,20131,20
Mass % of the monomer25,90%6,77%67,32%
Weight of the monomers during the experience91,1723,84236,98
Mass % of the hard segments73,03
Mass % urethane30,28
(Mwith)1948,77

CHDM, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C and enable the components to be combined. The mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 cm × 30 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner is 63 DM·lb (7 j).

Example H8

Prepare the polyurethane of the following components:

185,41
SolidsThe mass of polymer (g)
The name of the monomerCGDM1,4-ButanediolTMPDes W
HE#----
Acid#----
Equivalent weight72,1145,0644,00131,2
Specified equivalents0,35000,35000,3001,000
The weight of the monomer25,2415,7713,20131,20
Mass % of the monomer13,61%8,51%7,12%70,76%
Weight of the monomers during the experience40,8425,5221,36212,29
Mass % of the hard segments38,38
Mass % urethane31,82
(Mwith)1854,10

1,4-Butanediol, CGDM, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C and enable the components to be combined. The mixture Tegaserod and poured into a casting cell sizes 2”×12”×0,125” (30 cm × 30 cm × 0.3 cm), the preparation is heated to about 121°C. Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner is 47 DM·lb (5 Joule).

Example H9

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer1,6-HexanediolTMPDes W185,76300,00
HE#---
Acid#---
Equivalent weight59,0944,00131,2
Specified equivalents0,70000,300 1,000
The weight of the monomer41,3613,20131,20
Mass % of the monomer22,27%7,11%br70.63%
Weight of the monomers during the experience66,80one-21.32211,88
Mass % of the hard segments71,71
Mass % urethane31,76
(Mwith)1857,63

1,6-Hexanediol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C and enable the components to be combined. The mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 cm × 30 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner is 130 DM·lb (15 j).

Example N10

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer1,6-Hexane-diol1,4-butane-diolTMPDes W180,85300,00
HE#----
Acid#----
Equivalent weight59,0945,0644,00131,2
Specified equivalents0,35000,35000,3001,000
The weight of the monomer20,6815,7713,20131,20
Mass % of the monomer11,44%8,72%7,30%72,55%
Weight of the monomers during the experience34,3126,1621,90217,64
Mass % of the hard segments91,09
Mass % urethane32,62
(Mwith)1808,53the

1,6-Hexanediol, 1,4-butanediol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~115°C and enable the components to be combined. The mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 cm × 30 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner is 53 DM·lb (6 j).

Example H11

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerCGDM1,6-HexanediolTMPDes W190,32300,00
HE#----
Acid#- ---
Equivalent weight72,1159,0944,00131,2
Specified equivalents0,35000,35000,3001,000
The weight of the monomer25,2420,6813,20131,20
Mass % of the monomer13,26%10,87%6,94%68,94%
Weight of the monomers during the experience/td> 39,7832.60 high.20,81206,81
Mass % of the hard segments96,51
Mass % urethane31,00
(Mwith)1903,20

1,6-Hexanediol, CGDM, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~115°C and enable the components to be combined. The mixture Tegaserod and nalivajut foundry cell sizes 12”×12”×0,125” (30 cm × 30 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner is 124 DM·lb (14 j).

Example H12

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer1,4-CyclohexanediolTMPDes W185,06352,00
HE#---
Acid#---
Equivalent weight58,0844,00131,2
Specified equivalents0,7000/td> 0,3001,000
The weight of the monomer40,6613,20131,20
Mass % of the monomer21,97%7,13%70,90%
Weight of the monomers during the experience77,3325,11249,56
Mass % of the hard segments71,60
Mass % urethane is 31,88
(Mwith)1850,56

1,4-Cyclohexanediol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~95°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell sizes 6”×6”×0,25” (15 cm × 15 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Resistance to Gardner is 7 DM·lb (1 j).

Example H13

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerEthylene glycolTMPDes W166,12 300,00
HE#---
Acid#---
Equivalent weight31,03544,00131,2
Specified equivalents0,70000,3001,000
The weight of the monomer21,7213,20131,20
Mass % of the monomer13,08%of 7.95%78,98%
Weight of the monomers during the experience39,2323,84236,93
Mass % of the hard segments68,36
Mass % urethane35,52
(Mwith)1661,25

Ethylene glycol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C and enable the components to be combined. The mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 cm × 30 is m × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner is 4 DM·lb (4 j).

Example H14

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer1,4-ButanediolThe pentaerythritolDes W172,95300,00
HE#---
Acid#---
Equivalent weight45,0634,04131,2
Specified equivalents 0,70000,3001,000
The weight of the monomer31,54of 10.21131,20
Mass % of the monomer18,24%5,90%75,86%
Weight of the monomers during the experience54,7117,71227,58
Mass % of the hard segments71,34
Mac is UNIX % urethane 34,11
(Mwith)2306,04

1,4-Butanediol, pentaerythritol, and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to about 150°C. Pentaerythritol not dissolved.

Example n

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer1,4-BenzylimidazoleTMPDes W192,76300,00
HE#---
Acid# ---
Equivalent weight69,08544,00131,2
Specified equivalents0,70000,3001,000
The weight of the monomer48,3613,20131,20
Mass % of the monomer25,09%6,85%68,06%
Weight of the monomers during the experience75,2620,54204,19
95,81
Mass % of the hard segments72,73
Mass % urethane30,61
(Mwith)1927,60

1,4-Benzylimidazole, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C and enable the components to be combined. The mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 hmm × 30 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. With ednie value shock on the Gardner is 63 DM·lb (7 j).

Example W16

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerCGDM1,4-Benzene-dimethanolTMPDes W193,82300,00
HE#----
Acid#----
Equivalent weight72,1169,08544,00131,2
Specified equivalents0,35000,3500 0,3001,000
The weight of the monomer25,2424,1813,20131,20
Mass % of the monomer13,02%12,48%for 6.81%67,69%
Weight of the monomers during the experience39,0737,4320,43203,08
Mass % of the hard segments98,38
Mass % urethane30,44
(Mwith)1938,18

1,4-Benzylimidazole, CGDM, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~115°C and enable the components to be combined. The mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 cm × 30 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner 75 DM·lb (9 j).

Example n

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g
The name of the monomer1,4-Benzene-dimethanol1,4-butane-diolTMPDes W184,35300,00
HE#----
Acid#----
Equivalent weight69,08545,0644,00131,2
Specified equivalents0,35000,35000,3001,000
The weight of the monomer24,1815,7713,20131,20
Mass % of the monomer13,12%8,55%7,16%71,17%
Weight of the monomers during the experience39,3525,6621,48213,51
Mass % of the hard segments93,16
Mass % urethane32,00
(Mwith)1843,51

1,4-Benzylimidazole, 1,4-butanediol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~115°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 cm × 30 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Resistance to Gardner is 62 DM·lb (7 j).

Example n

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)
The name of the monomer1,4-Benzylimidazole1,6-HexanediolTMPDes W189,26
HE#- ---
Acid#----
Equivalent weight69,08559,0944,00131,2
Specified equivalents0,35000,35000,3001,000
The weight of the monomer24,1820,6813,20131,20
Mass % of the monomer12,78%of 10.93%6,97%69,32%
Weight of the monomers during the experience 38,3332,7820,92207,97
Mass % of the hard segments95,93
Mass % urethane31,17
(Mwith)1892,61

1,4-Benzylimidazole, 1,6-hexanediol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~115°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 cm × 30 cm × 0.3 cm), preheated to 121°C. the Casting of hotwired the Ute for 48 hours at 121°C. Impact on Gardner is 64 DM·lb (7 j).

Example n

Prepare the polyurethane of the following components:

td align="left">
SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer4,4'-Trimethylene-dipiperidinoTMPDes W213,80300,00
HE#---
Acid#---
Equivalent weightschedule rate is now 99.1444,00131,2
Specified equivalents0,70000,3001,000
The weight of the monomer69,4013,20131,20
Mass % of the monomer32,46%6,17%61,37%
Weight of the monomers during the experience97,38holds 18.52184,10
Mass % of the hard segments75,42
Mass % urethane27,60
(Mwith)2137,98

4,4'-Trimethylenediamine, TMP and DESMODUR W (preheated to 80°C) is added to the glass reactor. The initial temperature is approximately 50°C, under stirring sharply rises up to 60°C and the reaction medium gelation in the white mass.

Example H20

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer1,4-bis(hydroxy-ethyl)piperazineTMPDes W205,38300,00
HE#---
Acid#---
Equivalent weight87,1244,00131,2
Specified equivalents0,70000,3001,000
The weight of the monomer60,9813,20131,20
Mass % of the monomer29,69%to 6.43%63,88%
Weight of the monomers during the experience89,0819,28191,64
Mass % of the hard segments74,41
Mass % urethane28,73
(Mwith)2053,84

1,4-bis(Hydroxyethyl)piperazine, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C, and the viscosity increases to the point when the mixture is no longer mixed. The mixture becomes transparent, and the mixture is fused 1,4-bis(hydroxyethyl)piperazine.

Example n

Prepare the polyurethane of the following components:

N,N'-bis(2-Hydroxy-ethyl)oksamid
Solids
The name of the monomer1,4-ButanediolTMPDes W
HE#----
Acid#----
Equivalent weight88,0845,0644,00131,2
Specified equivalents0,35000,35000,3001,000
The weight of the monomer30,8315,7713,20131,20
Mass % of the monomer16,14%compared to 8.26%6,91%68,69%
Weight of monomers in the time of experience 22,60to 11.569,6896,17
-to 11.61a 4.8347,94
Mass % of the hard segments40,18
Mass % urethane30,89
(Mwith)1909,99

N,N'-bis(2-hydroxyethyl)oksamid, 1,4-butanediol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C, and the viscosity increases to the point when the mixture is no longer mixed. The mixture becomes transparent, and the mixture is fused N,N'-bis(2-hydroxyethyl)oksamid.

Example n

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer3,6-Dithia-1,2-octanediolTMPDes W208,52300,00
HE#---
Acid#---
Equivalent weightto 91.644,00131,2
Specified equivalents0,70000,3001,000
The weight of the monomer64,1213,20131,20
Mass % of the monomer30,75%6,33%62,92%
Weight of the monomers during the experience92,2518,99188,76
-
Mass % of the hard segments74,79
Mass % urethane28,29
(Mwith)2085,20

3,6-Dithia-1,2-octanediol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C, and the viscosity increases to the point when the mixture is no longer mixed. The mixture Tegaserod and poured into a casting cell sizes 6”×6”×0,25” (15 cm × 15 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner is 81 DM·lb (9 j).

Example N

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)
The name of the monomer3,6-Dithia-1,2-octanediolbis(4-(2-Hydroxy-ethoxy)for 3,5-dibromophenyl)-sulfonCGDMTMPDes W258,90
HE#-----
Acid# -----
Equivalent weightto 91.6326,98572,1144,00131,2
Specified equivalents0,23330,23330,23330,3001,000
The weight of the monomer21,3776,30equal to 16.8313,20131,20
Mass % of the monomercompared to 8.26%29,47%6,50%5,10%50,68%
The mass of the monomers is about time experience 24,7788,4119,5015,30152,03300,00
Mass % of the hard segments99,10
Mass % urethane22,79
(Mwith)2588,96

3,6-Dithia-1,2-octanediol, bis(4-(2-hydroxyethoxy)for 3,5-dibromophenyl)sulfon, CGDM, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~115°C and allow for the feature components combined. The mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 cm × 30 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C.

Example N

Prepare the polyurethane polymer in accordance with the present invention of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer2.2-ThiodiethanolTMPDes W187,17200,00
HE#---
Acid#---
Equivalent weight61,1044,00131,2
Specified equivalents0,70000,3001,000
The weight of the monomer42,7713,20131,20
Mass % of the monomer22,85%7,05%70,10%
Weight of the monomers during the experience45,7014,11140,20
Mass % of the hard segments71,92
Mass % urethane31,52
(Mwith)1871,67

2.2-Thiodiethanol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~95°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell sizes 6”×6”×0,25” (15 cm × 15 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the value of the shock on Gardner is 5 DM·lb (1 j) and the sample is fragile.

Example N

Prepare the polyurethane of the following components:

td align="center"> 8,69%
SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerThiodiethanol 1,4-butane-diolTMPDes W181,56300,00
HE#----
Acid#----
Equivalent weight61,145,0644,00131,2
Specified equivalents0,35000,35000,3001,000
The weight of the monomer21,3915,7713,20131,20
Mass % of the monomer11,78%7,27%72,26%
Weight of the monomers during the experience35,34date 26,0621,81216,79
Mass % of the hard segments37,07
Mass % urethane32.50 to
(Mwith)1815,56the

Thiodiethanol, 1,4-butanediol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C and enable the components to be combined. The mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 cm × 30 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner is 39 DM·lb (4 j).

Example N

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerThiodiethanol1,6-HexanediolTMPDes W186,47300,00
HE#----
Acid#----
Equivalent weight61,159,0944,00131,2
Specified equivalents0,35000,35000,3001,000
The weight of the monomer21,3920,6813,20131,20
Mass % of the monomer11,47%11,09%7,08%70,36%
Weight of the monomers during the experience34,41for 33.2721,24211,08
Mass % of the hard segments36,09
Mass % urethane31,64
(Mwith)1864,67

Thiodiethanol, 1,6-hexanediol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant peremeci is offering the mixture is heated to ~105°C and enable the components to be combined. The mixture Tegaserod and poured into a casting cell sizes 12”×12”×0,125” (30 cm × 30 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner 55 DM·lb (6 j).

Example N

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer1,4-ButanediolDes N 3400Des W182,80300,00
HE#---
Acid#---
Equivalent weight45,06153,00131,2
Specified equivalents1,00000,3000,700
The weight of the monomer45,0645,9091,84
Mass % of the monomer24,65%25,11%50,24%
Weight of the monomers during the experience73,9575,33150,72
-
Mass % of the hard segments96,42
Mass % urethane32,28
(Mwith)1828,00

1,4-Butanediol, Des 3400 N and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to approximately 105°C. the Mixture Tegaserod and poured into a casting cell (size 6”×6”×0,25” (15 cm × 15 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner 35 DM·lb (4 j).

Example N

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerH2About1,4-ButanediolTMP Des W163,32300,00
HE#----
Acid#----
Equivalent weight9,0145,0644,00131,2
Specified equivalents0,35000,35000,3001,000
The weight of the monomer3,1515,7713,20131,20
Mass % of the monomer1,93%to 9.66%8,08% 80,33%
Weight of the monomers during the experience5,7928,9724,25240,99
Mass % of the hard segments79,41
Mass % urethane36,12
(Mwith)1633,25

1,4-Butanediol, TDM, DESMODUR W (preheated to 80°C) and deionized water added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C and enable the components to be combined. After combining the components on the walls of the reactor there is condensation (water).

Example N

Prepare the polyurethane of the following components:

ComponentEquivalent weightEquivalentsWeight (g)Weight (%)
TMP44,70,052,21,3
1,4-Butanediol450,9542,824,3
Des W1311,013174,4

1,4-Butanediol, TMP and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring a mixture agriauto ~110°C. The mixture Tegaserod and poured into a casting cell sizes 15”×15”×0,125” (38 cm × 38 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average value of the shock on the Gardner-300 DM·lb (35 j). Wuis 33.5%, Wcis 46% and Mwithis 10,569 g/mol.

Example N

Prepare the polyurethane of the following components:

ComponentEquivalent weightEquivalentsWeight (g)Weight (%)
TMP44,70,052,21,2
1,5-Pentanediol520,9549,527,1
Des W1311,013171,7

1,5-Pentanediol, TMP and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to approximately 110°C. the Mixture Tegaserod and pour writenow cell sizes 15”×15”×0,125” (38 cm × 38 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner is 400 DM·lb (46 J.). Wuis 32,3%, Wcmakes 44.3% and Mwithis 10,973 g/mol.

Example n

Prepare the polyurethane of the following components:

ComponentEquivalent weightEquivalentsWeight (g)Weight (%)
TMP44,70,052,21,0
1,10-Decandiol870,9582,8to 38.3
Des W1311,013160,6

1,10-Decandiol, TMP and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to approximately 110°C. the Mixture Tegaserod and poured into a casting cell sizes 15”×15”×0,125” (38 cm × 38 cm × 0.3 cm), preheated to 121 is C. Casting utverjdayut within 48 hours at 121°C. the Average impact on Gardner is >640 DM·lb (>74 j). Wuis 27,3%, Wcis 37.5% and Mwithis 12,974 g/mol. Toughness Denatup is 77 J.

Example N

Prepare the polyurethane of the following components:

ComponentEquivalent weightEquivalentsWeight (g)Weight (%)
TONE 210to 406.40,281,332,3
1,5-Pentanediol520,526,010,3
TMP44,70,3the 13.45,3
Des W1311,013152,0

TONE 210, 1,5-pentanediol, TMP and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere, and the ri constant stirring, the mixture is heated to approximately 110°C. The mixture Tegaserod and poured into a casting cell sizes 15”×15”×0,125” (38 cm × 38 cm × 0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. Wustands at 23.4%, Wcis 32% and Mwithis 2542 g/mol.

Example N

Prepare the polyurethane of the following components:

ComponentEquivalent weightEquivalentsWeight (g)Weight (%)
TONE 210to 406.40,1561,026,1
1,5-Pentanediol520,5528,612,2
TMP44,70,3the 13.4the 5.7
Des W1311,013156,0

TONE 210, 1,5-pentanediol, TMP and DESMODUR W (preheated to 80°C) is added to the glass reactor. In the atmosphere azo is a and with constant stirring, the mixture is heated to approximately 110°C. The mixture Tegaserod and poured into a casting cell sizes 15”×15”×0,125” (38 cm × 38 cm ×0.3 cm), preheated to 121°C. the Casting utverjdayut within 48 hours at 121°C. Wuis 25.2%, Wcis 34.6% and Mwithis 2342 g/mol.

Example I

Samples of formulations 1-10 example, plexiglass (Plexiglas from McMasterCarr, Poly 84, extruded acrylic polymer) and LEXAN industrial grade experience to determine the K-factor in accordance with the following conditions:

A torque sensor: 2000 lbs;

Humidity (%): 50;

Temperature: 73°F (23°C);

Test speed: 320 pound-force/min;

Thickness: 0,120”

Experience, №Sample
ID
WidthThicknessCrackLoadTimeThe K-factor
(inch)(inch)(inch)(lb)(s)
341A2,1380,1230,575345,800345,8001296,220
361B2,1440,1220,600318,400318,4001241,140
351C2,1350,1280,700294,200294,2001199,424
312A1,9950,1230,750304,400304,4001477,415
332B1,9900,1310,650322,100 1330,586
322C1,9650,1320,750278,700278,7001279,169
29FOR1,9860,125value (0.475)216,400216,400777,079
303B1,9720,1300,425228,200228,200746,028
13C1,988to 0.1270,750175,600117,067822,370
264A2,0170,1250,600327,500327,5001321,788
27 4B2,0090,1200,750276,500276,5001359,195
284C2,0230,1230,675283,500283,5001259,891
245A2,0230,1220,60020,9,4157,050866,505
235B2,0200,1200,750179,900107,940874,598
255C2,0560,1660,700205,100205,100967,357
146A2,0530,124 0,650291,000218,2501225,187
166B2,0390,1220,670245,900245,9001086,512
156C2,068to 0.1270,690271,100232,3711144,531
127A2,024to 0.1270,620277,600185,0671125,576
137B2,0340,1300,750288,300192,2001288,378
117C2,0190,1280,750278,700101,345 1276,297
108A2,0060,1240,960238,400158,9331388,038
98B2,0210,1240.800 to284,60087,5691402,845
28C2,009amount of 0.1180,750355,400266,5501776,120
69A2,003amount of 0.1180,5201179,000428,7274681,823
89B2,0200,1230,670345,800106,4001525,675
79C 1,992amount of 0.1180,4501220,000395,6764486,874
310A2,0100,1160,750782,300586,7253956,318
410B2,0210,1190,450742,600270,0362655,849
510C2,0230,1190,450756,000274,9092700,237
2111A2,0110,1320,650272,20098,9821106,454
2211B2,0060,1300,650115,148910,576
2011C2,0110,1300,650255,00078,4621048,797
1912A2,0190,1340,650873,600268,8003470,984
1712B2,0210,1320,680798,900290,5093313,758
1812C2,023of 0.1330,710863,400313,9643655,555
3713A2,0360,1251,5001435,000521,81815960,663
3813B2,0240,1261,5001401,000262,68815670,107
3913C2,024of 0.1331,5001456,000273,00015489,381

Example J

Prepare the polyurethane of the following components:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomer1.5 to
pentanediol
TMPDes W2100,00
HE#---
Acid#---
Equivalent weight52,07544,00131,2
Specified equivalents0,40000,6001,000
The weight of the monomer20,8326,40131,20178,43 (amount)
Mass % of the monomer11,67%14,80%73,53%
Weight of the monomers during the experience245,15310,711544,13
Mass % of the hard segments41,090,4(131 + 52)/178,43
Mass % urethane33,0759g/EQ./
178,43 g/EQ.
(Mwith)892,15178,43/
to 0.2 mole of TMP

1,5-Pentanediol, trimethylolpropane and DESMODUR W (preheated to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~115°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell with dimensions of 14”×14”×0,375”, preheated to 121°C. the First set of samples utverjdayut within 48 hours at 121°C. the Second set of samples utverjdayut within 48 hours at 121°C and for 12 hours at 145°C. Each set of samples evaluated for resistance to cracking under stress by immersing for 30 m the chickpeas in 75%aqueous solution of sulfuric acid. The second set of samples withstands 30 min at 4000 psi.

Example For

Trimethylolpropane (0.05 equivalent), 1,10-decandiol (0.95 equivalent) and DESMODUR W (1.0 equivalent, the pre-heated up to 80°C) is added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to 110°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell with dimensions of 12”×12”×0,125”, pre-heated to 143°C. the Filled cell utverjdayut within 48 hours at 121°C. Multiaxial impact strength Dynatup is 77 joules when measured in accordance with ASTM-D 3763-02. Multi-Dynatup impact strength of LEXAN sample is 72 J.

Example L

Urethane prepolymer with isocyanate functionality get in a glass reactor under vacuum using as reagents 0.3 equivalent of 1,5 pentanediol, 1.0 equivalent of Desmodur W and 10 ppm of dibutyltindilaurate. The temperature of the reaction support at 143°C for 10 hours and add 0.4 equivalents of 1,5-pentanediol and 0.3 equivalents of trimethylolpropane. After 30 minutes at 110°C. the mixture is poured between lubricated glass forms and utverjdayut within 72 hours at 290°F (143°C). The form is removed from the furnace and remove plastic. Impact on Granero 256 DM is the pound (29 J.).

Urethane prepolymer with isocyanate functionality get in a glass reactor under vacuum using as reagents 0.5 equivalent of 1,5-pentanediol, 1.0 equivalent of Desmodur W and 10 ppm of dibutyltindilaurate. The temperature of the reaction support at 143°C for 10 hours and add 0.2 equivalent of 1,5-pentanediol and 0.3 equivalents of trimethylolpropane. After 30 minutes at 110°C. the mixture is poured between lubricated glass forms and utverjdayut within 72 hours at 290°F (143°C). The form is removed from the furnace and remove plastic. Impact on Granero 256 DM·lb (29 J.).

The sample prepared from urethane prepolymer with isocyanate functionality with a higher number (0.5 equivalent) of 1,5-pentanediol, has a higher impact strength according to Gardner. Not being tied to any theory, I believe that the Miscibility between the components is improved by pre-interaction part of the short-chain diol with a polyisocyanate.

Examples M

Example M1

Prepolymer with isocyanate functionality (the ratio NCO/OH of 3.8), having an equivalent weight of 327 g/mol, obtained by reaction of the following components:

Component%mass Equivalent weightThe number of equivalents
DESMODUR W
(4,4'-methylene-bis(cyclohexylidene))
54,42131,20,42
DBT fastcat on 4202
(dibutyltindilaurate)
0,005
PLURACOL E400NF
(polyethylene glycol)
5,0952000,03
PLURONIC L62D
(ethylene oxide/propyleneoxide block copolymers)
33,9711800,03
TRIMETHYLOLPROPANE2,32450,05
SARAH A
Polycaprolactone
1,233750,003
IRGANOX 10100,49
CYASORB UV 54110,97
TINUVIN 328 1,46
IRGANOX MD 10240,05
ONLY100,000000

at a temperature of approximately 104°C for approximately 5 hours. All the components are mixed together, except stabilizers, which dissolve after prepolymer reacted.

Dissolve approximately 9 g of acrylamide approximately 45 g of 1,4-butanediol at a temperature of approximately 25°C. and mixed with about 365 g obtained above prepolymer and approximately 0.1% of the mass. azobisisobutyronitrile (AIBN) based on solids. The mixture is poured into a glass form and heated in a furnace at a temperature of approximately 80°C for approximately 48 hours with constant stirring. Formed transparent polymerized. A sample of the cured polymer are experiencing for the evaluation of light transmission and impact on Granero. The transmittance of the sample is 91%, and resistance to Gardner equal to 150 DM·lb (17 j).

Example M2

The polyurethane polymer in accordance with the present invention obtained from the above prepolymer with out yannatou functionality cyclohexanedimethanol (CHDM) and 1,4-butanediol, which are presented below:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerPrepolymerCGDM1,4-Butanediol417,53200,00
HE#---
Acid#---
Equivalent weight365,7172,1145,06
Specified equivalents1,000,250,75
The weight of the monomer365,7118,0333,80
Mass % of the monomer87,59%4,32%8,09%
Weight of the monomers during the experience175,188,6416,19

Prepolymer, CHDM (preheated to 80°C) and 1,4-butanediol added to the glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~40°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell sizes 6”×6”×0,25” (15 cm × 15 cm × 0.6 cm) and aluminum cups, pre-heated to 80°C. the Filled cell utverjdayut within 24 hours at 121°C.

Product dimensions 6”×6”×1” (15 cm × 15 cm × 2.5 cm), obtained from this polymer, stops 9 mm (25 GP) bullet, released with an initial velocity of 1350 ft/sec (411 m/sec) from a distance of 20 feet (6.1 m), with minimal damage to the surface. The same sample can withstand a shot 0.40 caliber with little damage to the surface. The bullets do not ricochet and does not penetrate into the polymer. Bullet drop, slightly deformed, at the bottom of the sample.

Example M3

The polyurethane polymer in accordance with the present invention obtained from the above prepolymer with isocyanate functionality, cyclohexanedimethanol (CHDM) and 1,4-butanediol, which are listed below:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerPrepolymerCGDM1,4-Butanediol424,30200,00
HE#---
Acid#---
Equivalent weight365,7172,1145,06
Specified equivalents1,000,500,50
The weight of the monomer365,7136,0622,53
Mass % of the monomer86,19%of 8.50%5,31%
Weight of the monomers during the experience172,3817,00to 10.62

Prepolymer, CHDM (preheated to 80°C) and 1,4-butanediol add in a glass the reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~40°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell sizes 6”×6”×0,25” (15 cm × 15 cm × 0.6 cm) and aluminum cups, pre-heated to 80°C. the Filled cell utverjdayut within 24 hours at 121°C.

Example M4

The polyurethane polymer in accordance with the present invention obtained from the above prepolymer with isocyanate functionality and bis(hydroxyethylamide ether) of hydroquinone, which are listed below:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerPrepolymerbis(Hydroxyethyloxy) ether of hydroquinone483,40250,00
HE#--
Acid#--the
Equivalent weight384,2999,11
Specified equivalents1,001,00
The weight of the monomer384,2999,11
Mass % of the monomer79,50%20,50%
Weight of the monomers during the experience198,7451,26

Prepolymer and bis(hydroxyethyloxy)ether of hydroquinone added to the glass reactor and placed in a heating jacket. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~85°C and enable the components to be combined. After the mixture becomes transparent is Oh, the mixture is placed in a vacuum and Tegaserod, then poured into a casting cell sizes 6”×6”×0,25” (15 cm × 15 cm × 0.6 cm), previously heated to 80°C. the Filled cell utverjdayut within 24 hours at 121°C. the Molded sample is transparent, but has shown some turbidity. Impact on Gardner is 320 DM·lb (37 J.).

Example N

Prepolymer with isocyanate functionality is obtained by reaction of the following components:

Component%massEquivalent weightThe number of equivalents
DESMODUR W
(4,4'-methylene-bis(cyclohexylidene))
54,42131,20,42
DBT fastcat on 4202
(dibutyltindilaurate)
0,005
PLURACOL E400NF
(polyethylene glycol)
5,0952000,03
PLURONIC L62D
(ethylene oxide/propyleneoxide block copolymers)
33,971180
TRIMETHYLOLPROPANE2,32450,05
SARAH A
Polycaprolactone
1,233750,003
ONLY100,000000

at a temperature of approximately 104°C for approximately 5 hours. All the components are mixed together, except stabilizers, which dissolve after will react prepolymer.

The polyurethane polymer in accordance with the present invention obtained from the above prepolymer and 1,4-butanediol, which are listed below:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerPrepolymer1,4-butanediol375,38100,00
HE#--
Acid#--
Equivalent weight330,3245,06
Specified equivalents1,001,00
The weight of the monomer330,3245,06
Mass % of the monomer88,00%12,00%
Weight of the monomers during the experience88,0012,00

Prepolymer and 1,4-butanediol added to the glass reactor. In nitrogen atmosphere and with constant stirring a mixture of heat is up to ~45°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell size (4”×4”×60 mil), preheated to 80°C. the Filled cell utverjdayut within 24 hours at 121°C.

Product dimensions 6”×6”×1” (15 cm × 15 cm × 2.5 cm), obtained from this polymer, stops 9 mm (125 GP) bullet, released with an initial velocity of 1350 ft/sec (411 m/sec) from a distance of 20 feet (6.1 m), with minimal damage to the surface. The same sample can withstand a shot 0.40 caliber with little damage to the surface.

Examples Of

Example O1

Prepolymer with isocyanate functionality is obtained by reaction of the following components:

Recipe of prepolymer
ComponentEQ.
weight
EquivalentsWeight (g)%,
mass.
Equivalents, normalized to Des WNormal-used weight (g)
SARAH 2047200,00,1427,827,8% 0,2856,68
SARAH 2077375,00,0186,656,7%being 0.03613.56MHz
TMP44,60,0271,21,2%0,0552,45
HE-0,1835,65-0,3772,69
Des W131,20,4964,3564,4%1,0000131,20
Total =78,5%Prepolymer, Mw=203,89
Prepolymer, W(urethane)= 28,94%
Prepolymer, Mc=11150
Prepolymer, Wb=7433

at a temperature of approximately 104°C for approximately 5 hours. All the components are mixed together, except stabilizers, which dissolve after reacted prepolymer.

The polyurethane polymer in accordance with the present invention obtained from the above prepolymer and CHDM, listed below:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerPrepolymerCGDM402,98800,00
HE#-
Acid#--
Equivalent weight330,8772,11
Specified equivalents1,001,0000
The weight of the monomer330,8772,11
Mass % of the monomer82,11%9,01%
Weight of the monomers during the experience656,85143,15

Prepolymer and CGMD add in a glass reactor. In nitrogen atmosphere and with constant AC is shivanie the mixture is heated to ~55°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell size 13”×13”×0,25”, preheated to 80°C. the Filled cell utverjdayut within 24 hours at 121°C.

Example O2

The polyurethane polymer in accordance with the present invention obtained from the above prepolymer and CHDM, listed below:

1,00
SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerPrepolymer2.2-Thiodiethanol391,97700,00
HE#--
Acid#--
Equivalent weight330,8761,10
Specified equivalents1,0000
The weight of the monomer330,8761,10
Mass % of the monomer84,41%15,59%
Weight of the monomers during the experience590,89109,11

Prepolymer and 2,2-thiodiethanol add in a glass reactor. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~55°C and enable the components to be combined. After the mixture becomes transparent, the mixture Tegaserod and poured into a casting cell size 13×13×0,25”, preheated to 80°C. the Filled cell utverjdayut within 24 hours at 121°C.

Example R

As a comparative example of preparing a thermoplastic polymer using 1.0 equivalent of 1,10-decandiol and 1.0 equivalent of Desmodur W as Rea the clients and 10 ppm of dibutyltindilaurate as a catalyst. The polymer is mixed at 110°C. in a glass reactor under vacuum. After about 30 minutes at 110°C. the mixture is poured between lubricated glass forms and utverjdayut within 72 hours at 290°F (143°C). The form is removed from the furnace and remove plastic. Impact on Granero is less than 40 DM·lb (5 Joule) and the average value is approximately 16 DM·lb (2 j).

The polymer in accordance with the present invention receive a similar way using a small amount of a branched polyol, namely: 0.05 equivalent of trimethylolpropane, and 0.95 equivalents of 1,10-decandiol and 1.0 equivalent of Desmodur W. the Impact on Gardner has an average of 640 DM·lb in the case of branched thermoplastic material with a molecular weight in the stitching approximately 12900 g/mol.

Example Q

Comparative example

For comparison serves prepolymer reaction about 0.1 equivalent of trimethylolpropane approximately from 1.0 equivalent of 4,4'-methylene-bis(cyclohexylsulfamate) (DESMODUR W) and education prioritypriority dissolved in excess (0.9 EQ.) DESMODUR W. Added as a catalyst to about 10 ppm of dibutyltindilaurate. With rapid stirring at room temperature, add about 0.1 equivalent of 4,4'-methylene-bis(cyclohexyl-amine), dia is affine analogue of DESMODUR W. Immediately a white flaky residue. The sediment concentration increases upon standing overnight, and the precipitate does not dissolve when heated to approximately 290°F (143°C). The above example is repeated in the same order, which is described above, but the polyisocyanate is heated to approximately 40°C. With rapid stirring diamine, formed similar to a white precipitate, which cannot be dissolved when heated to approximately 290°F (143°C).

In accordance with the present invention the same polyisocyanate as described above is heated to approximately 40°C. About 0.1 equivalent of water is rapidly added with stirring. Apply vacuum (4 mm Hg) to remove carbon dioxide and polyurea formed in the polyurethane gives polyurethaneisocyanourates, which has a slight turbidity. Diamines similar DESMODUR W is formed in situ when the water reacts. The mixture is then injected into the reaction with 0.8 equivalent of trimethylolpropane with the formation of plastic with high modulus and high optical transparency. The transmittance of the sample thickness 1/8” (0.3 cm) is 91.8% of the turbidity less than 0.1%. The glass transition temperature is 175°C.

In accordance with the present invention the same polyisocyanate is introduced into reaction with 0.2 equivalent of water at approximately 0°C, and carbon dioxide is removed in vacuum. Diamines similar DESMODUR W is formed in situ when the water reacts. Then about 0.5 equivalent of pentanediol and about 0.2 equivalent of trimethylolpropane injected into the reaction c polyurethaneisocyanourates with getting plastic with high optical transparency with transmittance 91,74% in the case of sample thickness 1/8” (0.3 cm) and a glass transition temperature of approximately 137°C.

Examples R

Example R1

In a glass reactor with a nitrogen atmosphere with stirring download: compared to 8.26% of the mass. 3,6-dithia-1,2-octanediol (to 91.6 EQ. weight); 29,47% of the mass. bis(4-(2-hydroxyethoxy)for 3,5-dibromophenyl)sulfone (326,985 EQ. weight); 6,50% of the mass. 1,4-cyclohexanedimethanol (CHDM) (72.1 EQ. weight); 5,10% of the mass. of trimethylolpropane (TMP) (44 EQ. weight); 50,68% of the mass. 4,4'-methylene-bis(cyclohexylsulfamate) (DESMODUR W) (131,2 EQ. mass), preheated to a temperature of 80°C. the Mixture is heated to a temperature of 115°C.

The mixture is then Tegaserod and poured into a casting cell sizes 12”×13”×0,125” (30 cm × 33 cm × 0.3 cm), pre-heated to a temperature of 121°C. the Filled cell then utverjdayut in the oven for 48 hours at 121°C.

The refractive index of the obtained lenses measured as nD= 1,5519.

Example R2

In a glass reactor with a nitrogen atmosphere with stirring download: 30,75% of the mass. 3,6-d is thia-1,2-octandiol (to 91.6 EQ. weight); 6,23% of the mass. TDM (44,0 EQ. weight) and 62,92% of the mass. DESMODUR W (131,2 EQ. mass), preheated to a temperature of 80°C. the Mixture is heated to a temperature of 105°C.

The mixture is then Tegaserod and poured into a casting cell sizes 12”×13”×0,125” (30 cm × 33 cm ×0.3 cm), pre-heated to a temperature of 121°C. the Filled cell then utverjdayut in the oven for 48 hours at 121°C.

The refractive index of the obtained lenses measured as nD= 1,5448, and the resistance is 82,0 DM·lb (9 j).

Example R3

In a glass reactor with a nitrogen atmosphere with stirring download: 9,70% of the mass. 1,5-pentanediol (52,1 EQ. weight); 7,03% of the mass. TDM (44,0 EQ. weight); 13,43% of the mass. GFMC (72.1 EQ. weight) and 69,84% of the mass. DESMODUR W (131,2 EQ. mass), preheated to a temperature of 80°C. the Mixture is heated to a temperature of 105°C.

The mixture is then Tegaserod and poured into a casting cell sizes 12”×13”×0,125” (30 cm × 33 cm × 0.3 cm), pre-heated to a temperature of 121°C. the Filled cell then utverjdayut in the oven for 48 hours at 121°C.

The resistance is 160,0 DM·lb (18 j).

Example R4

This example is carried out in accordance with the procedure of example 3 except that instead of 1,5-pentanediol use 1,4-butanediol (45,1 EQ. weight) and CHDM not present in the mixture. 17,18% 1,4-butanediol, of 7.23% of trimethylolpropane and 75,48% DESMODUR W.

DUROSTONE the ü is 120,0 DM·lb (14 j).

Example R5

This example is carried out in accordance with the method of example 4, except that instead of 1,4-butanediol using 1,4-benzylimidazole (69,1 EQ. mass). 25,09% of the mass. 1,4-benzylimidazole, 6,85% of the mass. of trimethylolpropane and 74,57% of the mass. DESMODUR W.

The resistance is 72,0 DM·lb (8 j). It is established that in fifteen minutes in the cycle of curing the material becomes cloudy. Therefore, during the rest of the curing cycle the temperature in the furnace is increased to 143°C, but the material remains murky.

Example R6

This example is carried out in accordance with the procedure of example 5 except that the mixture also add 1,4-butanediol (45,1 EQ. weight) and the mixture is heated to a temperature of 115°C. instead of 105°C. 13,12% of the mass. 1,4-benzylimidazole, 8,55% of the mass. 1,4-butanediol, 71,17% of the mass. DESMODUR W.

The resistance is 72,0 DM·lb (8 j).

Example R7

This example is carried out in accordance with the method of example 6 except that instead of 1,4-butanediol using 1,6-hexanediol (59,1 EQ. weight): 12,67% of the mass. 1,4-benzylimidazole, of 10.93% of the mass. 1,6-hexandiol and 69,32% of the mass. DESMODUR W.

The resistance is 64,0 DM·lb (7 j).

Example R8

This example is carried out in accordance with the method of example 7 except that thiodiethanol (61,1 EQ. weight) is used instead of 1,4-benzylimidazole and the mixture is heated to a temperature which measures 105°C instead of 115°C. 11,78% wt. 2,2-thiodiethanol, 8,69% of the mass. 1,4-butanediol, 7,27% of the mass. of trimethylolpropane and 70,10% of the mass. DESMODUR W.

The resistance is 72,0 DM·lb (8 j).

Example R9

This example is carried out in accordance with the procedure of example 3 except that CGDM not present in the mixture and the mixture is heated to a temperature of 115°C. instead of 105°C. 20,16% of the mass. 1,5-pentanediol, 7.3% of the mass. of trimethylolpropane and 72,55% of the mass. DESMODUR W.

The resistance is 200.0 DM·lb (23 j).

Example R10

This example is carried out in accordance with the procedure of example 9 except that instead of 1,5-pentandiol use a 1.8-octandiol (73,1 EQ. mass). 26,14% of the mass. 1,8-octandiol, to 6.75% of the mass. of trimethylolpropane and 67,11% of the mass. DESMODUR W.

The resistance is 624,0 DM·lb (72 J.).

Example R11

This example is carried out in accordance with the method of example 10 except that instead of 1,8-octandiol use 1,10-decandiol (87,1 EQ. mass). 29,66% of the mass. 1,10-decandiol, to 6.43% of the mass. of trimethylolpropane and 63,9% of the mass. DESMODUR W.

The resistance is 624,0 DM·lb (72 J.).

Example R12

This example is carried out in accordance with the method of example 11 except that instead of 1,10-decandiol use ethylene glycol (31,0 EQ. weight) and the mixture is heated to a temperature of 105°C instead of 115°C. 13,06% of the mass. of ethylene glycol, of 7.95% of the mass. of trimethylolpropane and 78,99% of the mass. DESMODUR W.

drastically 8.0 DM·lb (1 j).

Example R13

This example is carried out in accordance with the method of example 11 except that instead of 1,10-decandiol use 1,12-dodecanediol. 32,87% of the mass. 1,12-dodecanediol, 6,14% of the mass. of trimethylolpropane and 60,99% of the mass. DESMODUR W.

The resistance is 624,0 DM·lb (72 J.).

Example R14

This example is carried out in accordance with the procedure of example 13 except that instead of 1,12-dodecanediol use of 1,6-hexanediol (59,1 EQ. weight) and the mixture is heated to a temperature of 105°C instead of 115°C. 22,24% of the mass. 1,6-hexandiol, 7,11% of the mass. of trimethylolpropane and 70,65% of the mass. DESMODUR W.

The resistance is 144, 0mm DM·lb (17 j).

Example R15

This example is carried out in accordance with the method of example 9. The resistance is 80,0 DM·lb (9 j).

Example R16

This example is carried out in accordance with the method of example 11 except that use 101,2 EQ. mass 1,10-decandiol and KM-1733 (carbonate diol with 1000 MM, made of hexandiol and diethylmalonate and is a commercial product of ICI) (428 EQ. mass). 28,29% of the mass. 1,10-decandiol, 9,48% of the mass. MS-1733, 5,69% of the mass. of trimethylolpropane and 56,54% of the mass. DESMODUR W.

The resistance is 640,0 DM·lb (74 J.).

Example 17

Recipe 1-11 receive in accordance with the method of example 3, except that to get a reaction mixture using com is onesty, listed in table 21. Derived properties (ultimate tensile strength at yield, % relative elongation at yield, tensile strength at elongation at break, % relative elongation at break and young's modulus is measured in accordance with ASTM D 638-03; impact on Gardner measured in accordance with ASTM-D 5420-04; Tarticlemeasured using dynamometrical analysis; and the density is measured in accordance with ASTM-D 792) for formulations 1-11 presented in tables 27-29.

1,10-Dodecanediol
Table 27
Recipe
No.
ComponentEquivalent
weight
(g/EQ.)
EquivalentsWeight%,
mass.
Wu
(%)
Wc
(%)
Mc(g/mol)
1TMP44,70,313,406,528,739,42055
87,10,760,9729,7
DESMODUR W131,01,0131,063,8
2TMP44,70,313,406,729,440,42006
1,10-Dodecanediol87,10,3530,4815,2
1,8-Octandiol73,10,3525,58a 12.7
DESMODUR W131,01,0131,065,4
3TMP44,70,313,40to 7.6133,546,041759
1,4-Butanediol45,00,731,517,9
DESMODUR W131,01,0131,074,49
4TMP44,70,313,407,4032,644,81808
1,5-Pentanediol52,00,736,420,13
DESMODUR W131,01,0131,072,47
5TMP44,70,626,8211,6433,045,811786
1,5-Pentanediol52,00,420,815,06
DESMODUR W131,01,0131,073,3
6TMP44,70,313,407,2031,7743,621857
1,6-Hexanediol59,00,741,322,26
DESMODUR W131,01,0131,070,54
7TMP44,70,313,40for 6.81 30,441938
1,4-CHDM72,110,3525,2413,02
the 1.6-PM69,080,3524,1812,48
DESMODUR W131,01,0131,0131,0

Table 28
Recipe,
No.
Equivalent mass
(g/EQ.)
EquivalentsWeight%,
mass.
Wu
(%)
Wc
(%)
Mc(g/mol)
8TMP44,70,313,407,0331,41to 43.11879
1,4-CGMD72,110,3525,2413,43
1,5-Pentanediol52,00,3518,239,70
9TMP44,70,313,406,9431,042,551903
1,4-CHDM72,110,3525,2413,26
1,6-Hexanediol59,090,3520,6810,87
DESMODUR W131,01,0131,068,94
10TMP44,70,313,206,730,241,41956
1,8-Octandiol73,10,751,1726,2
DESMODUR W131,01,01,067,1
11TMP44,70,313,40633 28,2938,842085
3,6-Dithia-1,2-octanediolto 91.60,764,1230,75
DESMODUR W131,01,0131,062,92
Note: the Recipe 11 has a refractive index of 1.55 and impact on Gardner 65 DM·lb.

Table 29
R-RA No.The limit tensile stress at yield
(lb/DM2)
Elongation at yield
(%)
Tensile strength at elongation at break
(lb/DM2)
Elongation at break
(%)
The young's modulus, lb/DM2 Impact on Gardner, DM.lbTarticleDensity,
g/cm3
191907,4671057268,000600of 99.11,091
295307,5703065282,0005921021,093
3121009,2904041336,0001201261,14
4112008,7823038321,0001901191,13
5131009,6 1100019351,000711401,13
6110008,7830056311,0001301171,12
7136001012,10018360,000751561,13
8121009,8938032339,0001431321,12
9119009,4888034327,0001241301,14
109880 7,9748055287,0006001061,10
11-----65--

Example R18

This example is carried out in accordance with the procedure of example 12 except that instead of ethylene glycol used 53,0 EQ. mass of diethylene glycol and the mixture is heated to a temperature of 115°C. instead of 105°C.

The resistance is 6.0 DM·lb.

Example R19

This example is carried out in accordance with the method of example 18 except that instead of diethylene glycol used 67,0 EQ. mass dipropyleneglycol.

The resistance is 8.0 DM·lb.

After curing the set of leaves covered by each of the polymers A-D, are tested for abrasion using standard tests abrasion on Taberu with grinding wheels CS10F (one pair for all samples), each circle 500, the Grinding wheel pereshlifovyvayut before each cycle (25 cycles). Testing is carried out at a temperature in the range of approximately about the 70 to 75°F and at a relative humidity of approximately 50 to 60%. Determine the average turbidity of ambient light for a given number of cycles of Taber, the results obtained are presented below.

Standard test method effects QUV-B for 1000 hours corresponds to approximately three years of external influences. The results obtained are presented below.

Samples subjected to: - 1000 hours exposure to QUV-B - 3 year external influences

Coated sampleTurbidity (%) when the number of cycles
01003005001000
Polymer And
The polymer In
The polymer
Polymer D

Examples S: fire Test

Example S1

The polyurethane polymer in accordance with the present invention is obtained from the components listed below:

SolidsThe mass of polymer (g)Given the size of the boot
(g)
The name of the monomerBis(2-hydroxy-ethyl) ether tetrabromo-phenol And1,6-hexane-diolTMPDes W291,54100,00
HE#----
Acid#----
Equivalent weight 315,9959,0944,00131,2
Specified equivalents0,40000,50000,1001,000
The weight of the monomer126,4029,554,40131,20
Mass %
monomer
43,35%10,13%1,51%45,00%
Weight of the monomers during the experience43,3510,131,5145,00
-
Mass %
urethane
20,24
The molecular mass on the stitching (g/mol) (Mwith)8746,23

1,6-Hexanediol, trimethylolpropane and DESMODUR W, preheated to 80°C, add in chemical glass with solid bis(2-hydroksyetylowy) air tetrabromobisphenol A. With stirring on a hot tile mixture is heated until then, until it becomes transparent and all solid bis(2-hydroxyethyloxy) ether tetrabromobisphenol And dissolves/melts.

Data for the initial shock to Gardner show higher resistance than extruded acrylic polymer (>16 DM·lb) and much higher than PLAXIGLAS (2 DM·lb). Fire test using a Bunsen burner show that the flame immediately Podwale is paid to the self-extinguishing.

Example S2

The polyurethane polymer in accordance with the present invention is obtained from the components listed below:

SolidsGiven the size of the boot
(g)
The name of the monomerBis(2-hydroxyethyloxy) ether tetrabromobisphenol And1,6-hexanediolTMPDes W475,00
HE#----
Acid#----
Equivalent weight315,9959,0944,00131,2
Specified equivalents0,45000,45000,100 1,000
The weight of the monomer142,2026,594,40131,20
Mass %
monomer
46,72%a total of 8.74%1,45%43,10%
Weight of the monomers during the experience221,9041,496,87204,74
-
Mass %
urethane
19,38
The molecular mass on the stitching (g/mol) (Mwith)9131,58

The weight of the polymer is 304,39, 1,6-Hexanediol, trimethylolpropane and DESMODUR W, preheated to 80°C, add in chemical glass with solid bis(2-hydroksyetylowy) air tetrabromobisphenol A. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C until it becomes transparent and all solid bis(2-hydroxyethyloxy) ether tetrabromobisphenol And dissolves/melts. After the mixture becomes transparent, the mixture Tegaserod and poured into a mold cell dimensions 12”×12”×0,125”, preheated to 121°C. the Filled cell utverjdayut within 48 hours at 121°C. Data for the initial shock of evidence of very poor properties (<16 DM·lb). Fire test using a Bunsen burner show that the flame immediately undergoes self-extinguishing.

Example S3

The polyurethane polymer in accordance with the present invention is obtained from the components listed below:

SolidsGiven the size of the boot
(g)
The name of the monomer Bis(2-hydroxyethyloxy) ether tetrabromobisphenol And1,6-hexanediolTMPDes W300,00
HE#----
Acid#----
Equivalent weight315,9959,0944,00131,2
Specified equivalents0,10000,80000,1001,000
The weight of the monomer31,6047,274,40131,20
Mass %
monomer
14,73%22,04%2,05% 61,17%
Weight of the monomers during the experience44,2066,126,15183,52
-
Mass %
urethane
allocates 27,51
The molecular mass on the stitching (g/mol) (Mwith)6434,13

The weight of the polymer is 214,47, 1,6-Hexanediol, trimethylolpropane and DESMODUR W, preheated to 80°C, add in chemical glass with solid bis(2-hydroksyetylowy) air tetrabromobisphenol A. In nitrogen atmosphere and with constant stirring, the mixture is heated to ~105°C, Pocono will not become transparent and all solid bis(2-hydroxyethyloxy) ether tetrabromobisphenol And dissolves/melts. After the mixture becomes transparent, the mixture Tegaserod and poured into a mold cell dimensions 12”×12”×0,125”, preheated to 121°C. the Filled cell utverjdayut within 48 hours at 121°C. fire Test using a Bunsen burner show that the polymer chars and burns approximately 7 seconds after removal of the flame.

Example T

Polyurethane, reinforced with fiberglass

The following reagents: 208 g of 1,10-decandiol (2.39 equivalent) and of 45.7 g of trimethylolpropane (1.02 equivalents) are loaded into a flask and heated to 125°C. in a nitrogen atmosphere with stirring. When there is a clear, homogeneous melt, the mixture is cooled to 105°C and add 446 g (3.41 equivalent) DESMODUR W. After stirring for 15 minutes and re-heating to approximately 90°C, the mixture becomes transparent. After keeping at 90°C for approximately 10 minutes to approximately 50% of the liquid is transferred with the help of vacuum in the form of 20”×20”×1/8” (50.8 cm × 50.8 cm × 0.3 cm)containing 4 layers of bi-directional Mat E-glass fiber with the removed tissue and cells for flow inside the vacuum bag. The shape and glass before beginning the migration pre-heated to 105°C.

Approximately 15 minutes is a sufficient amount of material transferred in the completely filled the first bag and impregnates the fiber. The bag and the form is then heated at 143°C for 48 hours. The temperature of the obtained composite fiber-polyurethane is then reduced to 120°C and maintained for 1 hour, after which the temperature is further reduced to 38°C. After 1 hour at 38°C the system is cooled to room temperature and disassembled. The item received is a hard, colorless and solid.

Example U

Multilayer composite cast film in accordance with the present invention in a stretched acrylic polymer

Casting cell is collected using a 0.5” extruded acrylic polymer Polycast 84®and 0.25” glass, which is coated to release the clear. For good adhesion of the polyurethane extruded acrylic polymer is applied primer. The cell has dimensions of 6”×6” to 0.060” gap between the glass and extruded acrylic polymer, which is held constant by using a silicone rubber gasket. Edge clamp. Composition using 0.3 equivalents of trimethylolpropane, 0.7 equivalents of 1,5-pentanediol and 1.0 equivalent DESMIDUR W mix and Tegaserod at 210°F and pour in the described casting cell. Composition utverjdayut at 180°F for 3 days, allowed to cool to room temperature and then molded the plastic film is separated from the release sheet of glass. Receive a composite with high optical characteristics of the mi, which has excellent adhesion to the base and high resistance to crack propagation under stress and when exposed to solvents.

The composite is exposed to a load of 4000 psi with polyurethane plastic in tensile strain and put in ethyl acetate, cover glass slide and incubated for 30 minutes. In the study under the microscope is not observed the formation of cracks. The same test is carried out on uncoated extended acrylic polymer, which immediately observed the formation of cracks that are visible without a microscope. The same test is carried out on uncoated extended acrylic polymer, subjected to a load of 1000 psi. Cracks that are visible without a microscope, also occurs immediately.

Examples V

Reinforced composites

With regard to table 30, thermosetting polyurethanes obtained as follows.

A reactor provided with a stirrer, thermocouple, input of nitrogen, receiver and vacuum pump. Then add load And stirred with heating to 80-100°C in vacuum and allowed to stand for 1 hour. Then the reaction mixture is cooled to 80°C., the vacuum is cut off and added to the reactor loading C. Then the reaction mixture is heated up to 80°C in vacuum and give undergo an exothermic reaction with increasing temperature from 110 to 120°C. Reactio the ing mixture is poured into the space between the two plates with dimensions of 5”×5”×3/16” from float glass, which are equipped with gaskets on three sides and held together by clamps. Both glass plates are silane grease deposited on their surface in contact with the polyurethane. The space between the plates is approximately three-sixteenth inch. Foundry cell before the casting is heated to a temperature of approximately 120°C. After casting Assembly is subjected to a 24-hour curing at 120°C, and then 16-hour curing at 143°C. after curing the cell is subjected to two-hour cycle of gradual cooling from 143°to 45°C, leaving it in the oven. The cell is then removed from the furnace, and the glass plates are separated from polyurethane.

Table 30
Download AndMass parts
1,10-Decandiol61,00
Trimethylolpropane13,41
Download
Desmodur W1131,00
1bis(4-isocyanatophenyl)methane, Bayer Material Science

Example V

The following examples illustrate the implementation of various inorganic phases in the form of particles in a thermosetting polymer phase. Thermosetting polymers are introduced into contact with different causing swelling solvents and various precursors, which form in situ inorganic phase in the form of particles.

Example V1

The introduction of tetraethylorthosilicate in methanol

Thermosetting polyurethane of example And immersed in a solution containing 20.3% of the mass. (25% vol.) anhydrous methanol and 79.7 per cent of the mass. (75% vol.) tetraethylorthosilicate (TMOS, TMOS), for 24 hours. Polyurethane is removed from solution of a mixture of methanol/TMOS and placed in deionized water for three days. The polyurethane is then placed in a vacuum oven at 100°C for 2 hours. Data transmission electron microscopy (TEM) show that the particles of silicon dioxide are introduced into the polyurethane phase. In the polyurethane particles are formed of silicon dioxide 250 μm. The morphology of nanoparticles of silicon dioxide, typically spherical and the particle size is in the range from 10 to 20 nm. In this sample are observed discrete particles and clusters.

Example V2

The introduction of tetraethylorthosilicate in ethanol

Thermosetting floor the urethane of example And are immersed in the solution, containing 21.9% of mass. (25% vol.) anhydrous ethanol and 78,1% of the mass. (75% vol.) tetraethylorthosilicate (TEOS, TEOS), for 24 hours. Polyurethane is removed from solution of a mixture of ethanol/TEOS and placed in a 14%aqueous solution of ammonium hydroxide for four hours. Polyurethane washed with water and placed in an oven at 143°C for four hours. Data TEM show that nanoparticles of silicon dioxide are introduced into the polyurethane phase. The size of the nanoparticles is in the range from 10 to 70 nm, and the larger part is in the 10 nm range.

Example V3

The introduction of tetraethylorthosilicate in xylene

Thermosetting polyurethane of example And immersed in a solution containing 21,7% of the mass. (25% vol.) anhydrous xylene and 78.3% of the mass. (75% vol.) tetraethylorthosilicate (TMOS), for 24 hours. Polyurethane is removed from solution of a mixture of xylene/TMOS and placed in a 14%aqueous solution of ammonium hydroxide for four hours. Polyurethane washed with water and placed in an oven at 143°C for four hours. Data TEM show that nanoparticles of silicon dioxide are introduced into the polyurethane phase. The size of the nanoparticles is in the range from 7 to 40 nm.

Example V4

The introduction of tetraethylorthosilicate in ethyl acetate

Thermosetting polyurethane of example And immersed in a solution containing 22.4% of the mass. (25% vol.) anhydrous ethyl acetate and 77.6% of the mass. (75% vol.) tetraethylorthosilicate (TMOS), for 24 hours. poliuretan removed from solution of a mixture of ethyl acetate/TMOS and placed in a 14%aqueous solution of ammonium hydroxide for four hours. Polyurethane washed with water and placed in an oven at 143°C for four hours. Data TEM show that nanoparticles of silicon dioxide are introduced into the polyurethane phase.

Example V5

The introduction of tetraethylorthosilicate in dimethyl sulfoxide

The polyurethane of example And immersed in a solution containing 25% of the mass. (25% vol.) anhydrous dimethyl sulfoxide (DMSO) and 75% of the mass. (75% vol.) tetraethylorthosilicate (TMOS), for 24 hours. Polyurethane is removed from solution of a mixture of DMSO/TMOS and placed in a 14%aqueous solution of ammonium hydroxide for four hours. Polyurethane washed with water and placed in an oven at 143°C for four hours. Data TEM show that nanoparticles of silicon dioxide are introduced into the polyurethane phase. The size of the nanoparticles is in the range from 7 to 30 nm.

Example V6

The introduction of tetraethylorthosilicate crosslinked polyester film

Piece sewn polyester film is dipped in a solution containing 20.3% of the mass. (25% vol.) anhydrous methanol and 79.7 per cent of the mass. (75% vol.) tetraethylorthosilicate (TMOS), for two hours. The film is removed from solution of a mixture of methanol/TMOS and placed in a 14%aqueous ammonium hydroxide solution for two hours. The film is washed with water for 15 minutes and dried at room temperature for 17 hours. Silicon dioxide in the form of particles embedded in the polymer phase. Data TEM shows that the size of nanocast the C is in the range from 7 to 300 nm.

Example V7

Introduction bis(ethylacetoacetate)diisopropoxide titanium in ethyl acetate

Thermosetting polyurethane of example And immersed in a solution containing 80.1% of the mass. anhydrous ethyl acetate and 19.9% of the mass. bis(ethylacetoacetate)diisopropoxide titanium, for 24 hours. Polyurethane is removed from solution of a mixture of ethyl acetate/(bis(ethylacetoacetate)diisopropoxide titanium) and placed in a 14%aqueous solution of ammonium hydroxide for four hours. Polyurethane washed with water and placed in an oven at 143°C for four hours. Phase titanium oxide in the form of particles embedded in the polyurethane phase. Data TEM shows that the size of the nanoparticles is in the range from 5 to 200 nm.

Example V8

Introduction acetylacetonate, zirconium (IV) acetate

Thermosetting polyurethane of example And immersed in a solution containing 91.2% in mass. anhydrous ethyl acetate and 8.8% of the mass. acetylacetonate, zirconium (IV), for 24 hours. Polyurethane is removed from solution of a mixture of ethyl acetate/(acetylacetonate zirconium (IV)) and placed in a 14%aqueous solution of ammonium hydroxide for four hours. Polyurethane washed with water and placed in an oven at 143°C for four hours. The phase of the zirconium oxide in the form of particles embedded in the polyurethane phase.

Example W

Synthesis acrylsilicone polymers

In the case of each of examples a-C, are shown in table 23, reacciona the flask provided with a stirrer, thermocouple input of nitrogen and refrigerator. Then add load and stirred at the boiling temperature under reflux (75-80°C) in nitrogen atmosphere. To the boiling ethanol simultaneously for three hours add load In and load C. the Reaction mixture is refluxed for two hours. Then add load D within 30 minutes. The reaction mixture is refluxed for two hours and then cooled to 30°C.

Table 31
ExampleThe example InExample
Download (weight in grams)
Ethanol SDA 40B1360,1752,81440,2
Loading (weight in grams)
The methyl methacrylate 12,841,8137,9
Acrylic acid8,718,134,6
Silquest A-1742101,4211,9405,4
2-Hydroxyethylmethacrylate14,50,30,64
n-butyl Acrylate0,20,30,64
Acrylamide7,2--
Sartomer SR 3553-30,3-
Ethanol SDA 40B155,7325,5622,6
Download (weight in grams)
Vazo 7 46,112,824,5
Ethanol SDA 40B76,7of 160.4306,8
Download D (weight in grams)
Vazo 671,52,16,1
Ethanol SDA 40B9,118,936,2
% Solids17,919,519,1
Acid number (100% solids resin)51,9645,6445,03
Mn--302155810

1 Denatured ethyl alcohol, the degree of the fortress 200, Archer Daniel Midland Co.

2gamma Methacryloxypropyltrimethoxysilane, GE silicones.

3Diameteroperating, Sartomer Company Inc.

42,2'-Azobis(2-methylbutyronitrile), E.I. DuPont de Nemours & Co., Inc.

5Mn soluble part; the polymer does not dissolve completely in tetrahydrofuran.

Example W1

Acrylsilicone resin of example A (8.5 g) is mixed with polyvinylpyrrolidone (0.1 g) and water (1.5 g). The formulation stored at room temperature 225 minutes. Part of the resulting solution is loaded into a 10-ml syringe and release via syringe pump at a speed of 1.6 ml/h in a multi-channel mouthpiece described in example 1. Conditions electrotorture described in example 1. Nanofibers in the form of a tape having a thickness of 100-200 nm and width 1200-5000 nm, collected on powdered aluminum foil and characterized using optical microscopy and scanning electron microscopy. Sample nanofibres dried in an oven at 110°C for two hours. Measurable weight loss is not observed. This indicates that nanofibers are fully sewn.

Examples of W2 and W3

Transparent composite articles containing polyurethane matrix and electrogalvanize fiber of example 1 was prepared as follows.

In the case of each of examples 2 and 3 (see below table 32) reactor supply m is szalkai, thermocouple input nitrogen, receiver and vacuum pump. Then add load And stirred while heating to 80-100°C in vacuum and allowed to stand for 1 hour. The reaction mixture is cooled to 80°C., the vacuum is shut off and the reactor add load C. Then the reaction mixture is heated up to 80°C in vacuum and hold the exothermic reaction raising the temperature to 110-120°C. Then the reaction mixture was poured between two plates of float glass with dimensions of 5”×5”×3/16”, which are equipped with gaskets on three sides and held together by clamps. Both glass plates are silane grease deposited on their surfaces that are in contact with elektroprovodnyi fibers and polyurethane. Fibers formed over the treated plates before Assembly in a mold cell. Casting cell is collected from electroforming fiber, covered with a plate on the inner side of the casting cell. The space between the plates is approximately three-sixteenth inch. Foundry cell before the casting is heated to a temperature of approximately 120°C. After casting Assembly is subjected to curing for 24 hours at 120°C. and then 16 hours at 143°C. after curing the cell is subjected to two-hour cycle of gradual cooling from 143°to 45°C, leaving them in the oven. The cell extract and the furnace, and the glass plate is separated from the composite product.

The polyurethane of examples 2 and 3

Table 32
Download (weight in grams)Example 2Example 3
1,4-Butanediol31,54-
1,10-Decandiol-61,00
Trimethylolpropane13,4113,41
Loading (weight in grams)
DESMODUR W1131,00131,00
1bis(4-Isocyanatophenyl)methane, Bayer Material Science.

Each composite product are tested for resistance to scratching, putting it to the test by scratching through the longitudinal scratching the surface with loaded abrasive paper for ten double friction with the COI is by whether an instrument for determining the hardness by scratching Atlas ATCC Scratch Tester, Model CM-5 (Atlas Electrical Devices Company of Chicago, Illinois). Used emery paper is a sheet of 9 μm abrasives 3M 281Q WETORDRYTMPRODUCTIONTMwhich is commercially available from 3M Company, St. Poul, Minnesota).

At the end of the test on the determination of hardness by scratching with the help of the device Crockmeter using 9 micron abrasive increase in the average roughness in the surface of the scratched area was measured using an optical profilometer. The surface of the scratched area is scanned perpendicular to the direction of scratching device Crockmeter; i.e. crosswise scratches. Identical view get rezerpinom plot for the measurement of average surface roughness of the product. The change in the average surface roughness for each product calculated by subtracting the average roughness nasarapan surface average roughness scratched the surface. Transparent products without nanofibers compared to the transparent composite products containing electrogalvanize fiber of example 3.

In addition, for comparison purposes receive the composite product as a whole, as described in example 3, but in this case are electroforming polyvinylidene fluoride (KYNAR) and fibers of nylon 6 and is placed instead of the fibers of example 3. Composite products are appreciated for resistance to scratching, ka is described above. The results are presented below in table 33.

Table 33
ExampleElectroforming fiberThe change in average surface roughness
(nm)
ControlNo74,54
Example 4Example 36,93
Example 4 (repeat)Example 3-7,28
Control (repeat)No81,48
Example 5Example 3-4,91
ComparativeKYNAR90,2
ComparativeNylon-666,96

The results presented in table 33, illustrate the improved resistance to scratching, which is provided acrylsilicone fibers obtained by electrophoretogram.

Example X

The sample powder

In a dry glass container mix together 1,4-butanediol (vs. 5.47 g, 0,122 equivalent) and 4,4'-methylene-bis(cyclohexylidene) (DESMODUR W, Bayer Corporation; equivalent weight NCO 131; 14,52 g, 0,111 equivalent). Add one drop of dibutyltindilaurate. The turbid mixture is heated spontaneously and becomes transparent. The mixture is placed in an oven at 120°C for 6 hours.

A portion of the weight of 1.88 g obtained, glassy, rigid polyurethane dissolved in 5,23 g M-Pyrol boiling on a hot tile. Similarly, in 3,68 g M-Pyrol dissolve the trimer of isophorondiisocyanate (0,23 g). The two solutions are mixed in an aluminum Cup and fired at 145°C for 35 minutes. The obtained film is a transparent, dense and hard. Wiping with methyl ethyl ketone not soften the film or not makes it sticky, indicating its full stitching.

Example Y

Fluid inclusion inorganic precursor in the urethane obtained by forming in situ nanoparticles

Sample urethane plastic receive the following way. The clear is applied by vapor deposition on the surface of two pieces of tempered glass, and the excess washed with isopropanol. Rubber gasket (diameter 3/16”) placed between two pieces of glass, and pieces of glass are fixed together so that one end forms was the of Tcrit. Prepolymer obtained by heating 504 g of 1,10-decandiol (3,55 mol, 0.7 equivalent) and 111 g of trimethylolpropane (0.83 mol, 0.3 equivalent) up to 120°C in vacuum in a three-neck round bottom flask, where it can withstand 30 minutes. The contents of the flask cooled to 80°C and add 1084 g dicyclohexylcarbodiimide (4.14 mol, 1 equivalent). Exothermic reaction increases the temperature to 105°C, and the solution is poured into the open end of the glass shape. The form is placed in an oven at 120°C for 24 hours and at 143°C for 16 hours. The temperature is reduced to 43°C for one hour and the form is removed from the furnace. The form is dismantled to retrieve casting parts made of urethane plastic.

In a closed container, prepare a solution containing 75% by vol. tetraethylorthosilicate (TMOS) and 25% vol. of methanol. Sample urethane plastic is placed in a closed container, and the container was washed with dry nitrogen. Urethane plastic soaked in a solution of TMOC/methanol for 4 or 24 hours. Urethane plastic is extracted and immersed in: 1) water for 72 hours; 2) 2 M HCl for one hour and water for one hour, or 3) 15% solution (about./about.) NH4OH in water for one hour and water for one hour. Then the samples annealed at 143°C for 4 hours. Soaking immersion leads to the hydrolysis and condensation of liquid inorganic precursor (TMOS), which is embedded in plastic. Each soaking leads to nanocast the persons of different size, and these particles are placed in the plastic at different depths.

Qualified in this field specialist will be understood that in embodiments of the invention described above can be carried out modifications without deviating from the scope of the claimed concept. Thus, it is clear that this invention is not limited to the specific described variants, and, as implied, cover modifications that are within the essence and scope of the present invention defined in the claims.

1. Polyurethane material comprising the first portion of the crystalline particles with semioriental and connected together to commit their orientation along a first crystallographic direction, in at least two directions, and the second part of the crystalline particles with semioriental and connected together to commit their orientation along a second crystallographic direction, in at least two directions, and the first crystallographic direction is different from the second crystallographic direction, and where these crystalline particles comprise more than about 30% of the total volume of the polyurethane material, and
where the polyurethane contains a reaction product of components including:
(a) about 1 equivalent of 4,4'-methylene-bis(CEC alexissalaam);
(b) about 0.3 equivalents of trimethylolpropane; and
(c) about 0.7 equivalents of butanediol or pentanediol, and where the polyurethane material is subjected to heat treatment at a temperature of from about 35°to about 150°C or the shutter speed.

2. The polyurethane material according to claim 1, where the first portion of the crystalline particles aligned in a row in three directions.

3. The polyurethane material according to claim 1, where the second part of the crystal particles are aligned in a row in three directions.

4. The polyurethane material according to claim 1, where the first portion of the crystalline particles have a morphology selected from the group comprising triangular plates, square plates, rectangular plates, hexagonal plates, tetrahedral plates, cubes, octagons, and mixtures thereof.

5. The polyurethane material according to claim 1, where the second part of the crystalline particles have a morphology selected from the group comprising triangular plates, square plates, rectangular plates, hexagonal plates, tetrahedral plates, cubes, octagons, and mixtures thereof.

6. The polyurethane material according to claim 1, containing monolithic sinter the first part of the crystalline particles with small-angle grain boundaries between them, connected together by a polymeric phase.

7. The polyurethane material according to claim 1, containing monolithic sinter W the Roy part of the crystalline particles with small-angle grain boundaries between them, connected together by a polymeric phase.

8. The polyurethane material according to claim 1, containing monolithic sinter the first part of the crystalline particles with small-angle grain boundaries and generally amorphous phase between them.

9. The polyurethane material according to claim 1, containing monolithic sinter the second part of the crystalline particles with small-angle grain boundaries and generally amorphous phase between them.

10. The polyurethane material according to claim 1, where the thickness of the first portion of the crystalline particles is approximately less than 50 nanometers.

11. The polyurethane material according to claim 1, where the thickness of the second portion of the crystalline particles is approximately less than 50 nanometers.

12. The polyurethane material according to claim 1, where the thickness of the first portion of the crystalline particles is from about 10 to 100 nanometers.

13. The polyurethane material according to claim 1, where the thickness of the first portion of the crystalline particles is from about 10 to 100 nanometers.

14. The polyurethane material according to claim 1 where the crystalline particles comprise more than about 30% of the total volume of the material.

15. The polyurethane material according to claim 1 where the crystalline particles comprise more than about 40% of the total volume of the material.

16. The polyurethane material according to claim 1, where butanediol represents 1,4-butanediol.

17. The floor of the urethane material according to claim 1, where pentanediol represents 1,5-pentanediol.

18. The polyurethane material according to claim 1 where the polyurethane material can withstand at least about 2 weeks after its formation.

19. The polyurethane material according to claim 1 where the polyurethane material can withstand at least about 2 months after its formation.

20. The polyurethane material according to claim 1 where the polyurethane material can withstand at least about 7 months after its formation.

21. The polyurethane material according to claim 1 where the polyurethane material is heated to a temperature of about from 90 to 145°C. for about 1 to 24 hours after its formation.

22. Products, including polyurethane material according to claim 1.

23. Article by article 22, where the product is a molded product.

24. Article by article 22 of the product is selected from the group comprising a transparent products, optical products, photochromic articles, ballisticheskih sustainable products and glazing.

25. Laminate, including:
(a) at least one layer of polyurethane material according to claim 1; and
(b) at least one layer of a base, selected from the group comprising paper, glass, ceramics, wood, stone, fabric, metal or organic polymeric material and combinations thereof.

26. Covering composition comprising a polyurethane material according to claim 1.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: disclosed is an aqueous polyurethane dispersion which does not contain N-methylpyrrolidone and solvents and contains a product of reaction of a mixture of 1-isocyanate-3,3,5-trimethyl-5-isocyanatemethylcyclohexane and 4,4'-diisocyanatedicyclohexylmethane, one or more polyols with average molecular weight of 500-3000, one or more compounds with at least one OH- or NH- functional group, which contain a carboxyl and/or carboxylate group, where at least 50 mol % acid incorporated in the overall resin consists of dimethylol propionic acid, one or more polyols and/or polyamines with average molecular weight less than 500 and, if necessary, one or more monoalcohols and/or monoamines, as well as preparation method thereof and use thereof as an agent for coatings having good resistance characteristics.

EFFECT: obtaining a polyurethane dispersion which does not contain N-methylpyrrolidone and solvents, and contains a hydrophilization agent in form of dimethylol propionic acid, which can be stored for over 8 weeks and is suitable for making transparent shining coatings with high resistance to dyes.

8 cl, 2 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to aqueous coating compositions with low content of volatile organic compounds. The aqueous coating composition contains water, oxidative-curable resin, at least 1.5% of the weight of the composition of a non-structured alkali-soluble acrylate, having weight-average molecular weight Mw of 200000 g/mol or lower, and acid number of at least 15 mg KOH/g; and an emulsified second acrylate having Mw of at least 300000 g/mol. Content of the alkali-soluble acrylate in the composition is equal to at least 3 wt %. The weight ratio of the alkali-soluble acrylate to the second emulsified acrylate ranges from 1:0.5 to 1:5, and the weight ratio of the alkali-soluble acrylate to the oxidative-curable resin ranges from 1:0.5 to 1:10. The oxidative curable resin is an alkyd resin, alkyd-urethane resin. The second acrylate is cross-linkable, for example azomethine cross-linkable links.

EFFECT: aqueous coating composition has good physical and mechanical properties.

9 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyurethanes and articles made from said polyurethanes, as well as to laminated material and coating composition containing such polyurethanes. The polyurethane is a product of a reaction between components which contains less than approximately 10 wt % polyesterpolyol and/or polyetherpolyol, where the components are selected from: (a) approximately 1 equivalent of at least one polyisocyanate; (b) approximately 0.05-0.9 equivalent of at least one branched polyol which contains 3-18 carbon atoms and at least 3 hydroxyl groups; and (c) approximately 0.1-0.95 equivalent of at least one diol which contains 2-18 carbon atoms, where during mixing, the reaction components are held at reaction temperature of at least approximately 100°C for at least approximately 10 minutes.

EFFECT: production of polyurethanes, articles of which are made through casting or reaction injection moulding and have good optical properties, high resistance to impact loads, high impact resistance, high K-ratio, good ballistic stability, good resistance to solvents and good weather resistance.

37 cl, 113 ex, 82 tbl, 26 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a moisture-curable composition for adhesive compounds, sealing compounds, coatings or linings, application thereof as an adhesive, sealing compound or coating, a cured composition obtained by reacting water with such a composition, methods of gluing bases and sealing using said composition, as well as adhesive and sealed articles made using said methods, respectively. The moisture-curable composition contains (i) at least one isocyanate-containing polyurethane polymer P, which is obtained from at least one polyisocyanate and at least one polyol, and (ii) at least one aldimine-containing compound of formula (I): .

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25 cl, 34 ex, 10 tbl

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to coating composition, applied, for instance, as transparent coatings, base coatings, pigmented coating layers, used, prime coatings, etc. Composition contains polyisocyanate, polyol, metal-based catalyst for carrying out reaction of addition reaction between isocyanate groups and hydroxyl groups, thiol-functioning compound and carboxylic acid, carbonyl group of carboxylic acid being in connection with π-electronic system.

EFFECT: creation of novel coating composition, demonstrating presence of favourable property balance, namely, low level of volatile organic solvent content with operation viscosity, high rate of hardening and long viability, which results in obtaining coatings, which demonstrate good outlook characteristics, in particular, low liability to formation of pinholes, and good hardness.

14 cl, 2 tbl

FIELD: construction.

SUBSTANCE: composition for coats contains isocyanate prepolymer produced by interaction of 4,4'-diphenylmethanediisocyanate and oligodiendiol with molecular weight of 2800-3200, content of hydroxyl groups 0.88-1.3% at the ratio of isolcyanate and hydroxyl groups of 4:1 with content of isocyanate groups in prepolymer of 8.0-9.7%, wt parts - 15-70, base - rubber composition from low-molecular hydroxyl-containing rubber, plasticiser, filler, anti-ageing agent and pigment - 100, catalyst of urethane production - 0.05-0.15 and glycerin 0.7-3.0.

EFFECT: higher strength, hardness and relative extension of coats.

2 tbl

FIELD: chemistry.

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EFFECT: obtained belt increases resistance to bending fatigue, resistance to development of cracks, resistance to joining of grooves and wear resistance of urethane coatings of belts and shafts, increases water resistance and oil resistance of belts and shafts with urethane coating.

18 cl, 2 ex, 4 tbl, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a water-soluble coating composition containing a) polyol, b) polyisocyanate cross-linking agent and c) a compound with a thiol functional group in which molar ratio of isocyanate groups to thiol groups lies between 1:0.0001 and 1:0.4. The invention also relates to use of the coating composition as a transparent or pigmented external coating, basic coating, filler, prime coating or binding material, in painting or repainting automobiles and large vehicles, and to a set for preparing the coating composition.

EFFECT: obtaining a composition which provides a balance between high rate of solidification, long life and good appearance of the coating film made from the said composition.

17 cl, 3 dwg, 7 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to obtaining new aspartates. Aspartates are obtained by reacting di- or polyamine with an unsaturated ester and then by reacting the obtained product with maleinimide.

EFFECT: obtaining new aspartates and their use as reactive components for polyiisocyanates in two-component compositions for polyurethane coatings.

4 cl, 3 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to undercoating compositions containing at least one polyurethane prepolymer A with isocyanate groups; at least one aliphatic polyisocyanate B; at least one aromatic polyisocyanate C; at least one reaction product D, obtained from at least one epoxysilane and at least one aminosilane with quantitative ratio of atoms of active hydrogen of the amine to the number of epoxy groups of the epoxysilane equal to 3:1-1:3, or at least one epoxysilane and at least one mercaptosilane with quantitative ratio of mercapto groups to epoxy groups equal to 1.5:1-1:1.5, with content of product D equal to 0.5-15 wt % of the total weight of A+B+C+D. The invention also relates to use of the undercoating composition as an undercoating for adhesives, sealants and floor coatings.

EFFECT: good adhesion to problematic substrates with long open time.

24 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: disclosed is an aqueous polyurethane dispersion which does not contain N-methylpyrrolidone and solvents and contains a product of reaction of a mixture of 1-isocyanate-3,3,5-trimethyl-5-isocyanatemethylcyclohexane and 4,4'-diisocyanatedicyclohexylmethane, one or more polyols with average molecular weight of 500-3000, one or more compounds with at least one OH- or NH- functional group, which contain a carboxyl and/or carboxylate group, where at least 50 mol % acid incorporated in the overall resin consists of dimethylol propionic acid, one or more polyols and/or polyamines with average molecular weight less than 500 and, if necessary, one or more monoalcohols and/or monoamines, as well as preparation method thereof and use thereof as an agent for coatings having good resistance characteristics.

EFFECT: obtaining a polyurethane dispersion which does not contain N-methylpyrrolidone and solvents, and contains a hydrophilization agent in form of dimethylol propionic acid, which can be stored for over 8 weeks and is suitable for making transparent shining coatings with high resistance to dyes.

8 cl, 2 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyurethanes and articles made from said polyurethanes, as well as to laminated material and coating composition containing such polyurethanes. The polyurethane is a product of a reaction between components which contains less than approximately 10 wt % polyesterpolyol and/or polyetherpolyol, where the components are selected from: (a) approximately 1 equivalent of at least one polyisocyanate; (b) approximately 0.05-0.9 equivalent of at least one branched polyol which contains 3-18 carbon atoms and at least 3 hydroxyl groups; and (c) approximately 0.1-0.95 equivalent of at least one diol which contains 2-18 carbon atoms, where during mixing, the reaction components are held at reaction temperature of at least approximately 100°C for at least approximately 10 minutes.

EFFECT: production of polyurethanes, articles of which are made through casting or reaction injection moulding and have good optical properties, high resistance to impact loads, high impact resistance, high K-ratio, good ballistic stability, good resistance to solvents and good weather resistance.

37 cl, 113 ex, 82 tbl, 26 dwg

FIELD: chemistry.

SUBSTANCE: perfluoro-elastomers have Tg below -10°C and amount of terminal -COF groups less than 0.05 mmol/kg. Perfluoro-elastomers contain: (A) from 1% to 100% monomer of formula CF2=CFOCF2OCF3 and (B) from 0% to 100% one or more perfluorinated comonomers with at least one ethylene unsaturation. Comonomer (B) is TFE, or a mixture of comonomers (B) contains TFE.

EFFECT: improved mechanical properties and compression set.

5 cl, 18 ex, 1 tbl

FIELD: polymer production.

SUBSTANCE: coating composition comprising at least one compound with at least two isocyanate functional groups; at least one compound reactive to isocyanate and having at least two groups reactive to isocyanate groups, which are selected from mercapto groups, hydroxyl groups and combinations thereof; and cocatalyst consisting of phosphine and Michael acceptor, amount of catalyst constituting from 0.05 to 20% of the weight of dry residue. Invention also describes a method for coating substance with indicated composition as well as coated substrate, and adhesive containing at least one compound with at least two isocyanate functional groups and at least one compound containing at least two above defined groups reactive to isocyanate groups. Moreover, invention discloses employment of composition for finishing of great vehicles and refinishing of motor cars. Composition is characterized by drying time at a level of 20 min, modulus of elasticity 1904, Persose hardness 303, and brightness (85°C) at a level of 100.

EFFECT: expanded coating assortment.

16 cl, 16 tbl, 48 ex

The invention relates to the field of polyurethane materials and method of production thereof

FIELD: chemistry.

SUBSTANCE: invention relates to polyurethanes and articles made from said polyurethanes, as well as to laminated material and coating composition containing such polyurethanes. The polyurethane is a product of a reaction between components which contains less than approximately 10 wt % polyesterpolyol and/or polyetherpolyol, where the components are selected from: (a) approximately 1 equivalent of at least one polyisocyanate; (b) approximately 0.05-0.9 equivalent of at least one branched polyol which contains 3-18 carbon atoms and at least 3 hydroxyl groups; and (c) approximately 0.1-0.95 equivalent of at least one diol which contains 2-18 carbon atoms, where during mixing, the reaction components are held at reaction temperature of at least approximately 100°C for at least approximately 10 minutes.

EFFECT: production of polyurethanes, articles of which are made through casting or reaction injection moulding and have good optical properties, high resistance to impact loads, high impact resistance, high K-ratio, good ballistic stability, good resistance to solvents and good weather resistance.

37 cl, 113 ex, 82 tbl, 26 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to novel foam modifiers for producing flexible foam. Flexible foamed polyurethane with density of less than 128 kg/m3 is obtained by reacting an aromatic polyisocyanate component with functionality of at least approximately 2.0, with a component capable of reacting with isocyanate, which contains one or more polyoxyalkylenepolyester polyols having 2-8 hydroxyl groups with OH number between approximately 11 and approximately 280, and containing less than 30 wt % copolymerised oxyethylene from the weight of oxyethylene, and a foam modifier. The foam modifier contains 35-75 wt % of at least one low-molecular weight compound selected from a group consisting of 1,3-propanediol, 1,3-butanediol and 1,4-butanediol and their mixture, 20-60 wt % of one or more polyester polyols containing 2-8 hydroxyl groups per molecule with OH number from approximately 11 to approximately 280, and containing more than 50 wt % compolymerised oxyethylene from the weight of oxyethylene, and 5-25 wt % dipropylene glycol. The reaction takes place in the presence of one or more foaming agents, one or more catalysts and one or more surfactants.

EFFECT: improved operational characteristics and properties of flexible foam.

25 cl, 11 tbl

FIELD: organic chemistry, chemistry of polymers.

SUBSTANCE: invention relates to chemistry of polyurethans, namely, to spandex improved composition. Spandex is product of reaction of at least one polymeric glycol and at least one polyol comprising alkoxylated aromatic functional group with at least one organic diisocyanate followed by the polymerization process of synthesized protected glycol with at least one diamine. Alkoxylated diphenol or alkoxylated dihydrophenol is used as polyol comprising alkoxylated aromatic functional group. Also, invention describes a method for synthesis of spandex that comprises (with exception for steps in preparing isocyanate-protected polyols and their polymerization with diamines) molding steps from reaction mixture, molding from a melt, dry molding or wet molding of polyurethane also. Spandex possesses the best stability to high-temperature coloring and minimal loss of physical properties, such as elastic recovery of form.

EFFECT: improved method of synthesis.

16 cl, 4 tbl, 5 dwg

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to a method for preparing polyurethane material, and to material made of in relation with the indicated method. Invention describes a method for preparing polyurethane material showing the vitrification point 25°C, not below. Polymer is prepared by interaction of polyisocyanate component consisting of the following components: a) 80-100 wt.-% of diphenylmethane diisocyanate comprising 4,4'-diphenylmethane diisocyanate and/or variant of indicated diphenylmethane diisocyanate, 40 wt.-%, not less, and 0-20 wt.-% of another polyisocyanate with the isocyanate-reaction composition consisting of the following components: a) 80-100 wt.-% of simple polyetherpolyol with the average nominal polyfunctionality 3-8, average equivalent mass 200-2000 Da, average molecular mass 600-8000 Da, the oxyethylene content 50-100% and the content of primary hydroxyl groups 70-100%; b) reaction elongating agent and/or cross-linking agent taken in the amount wherein the ratio of hardness blocks = 0.60; and c) 0-20 wt.-% of one or some other isocyanate-reaction compounds but excluding water, and material made of the indicated method. Polyurethanes made of the proposed method show density value 957 kg/m3, the Shore hardness value 77 and the virtification temperature 87°C that can be used in making show footings, arm rests, door panels an car sun glass baffle plates.

EFFECT: improved preparing method.

5 cl, 1 tbl, 2 ex

FIELD: chemical industry; methods of production of a thermosetting elastomers.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the methods of production of a thermosetting polyurethane elastomer and also to the elastomer produced according to the given method. The invention presents the method of production of the polyurethane elastomer having a total apparent density exceeding 150 kg/m3 and providing for an interaction of polyisocyanate and a reactive to isocyanate composition not necessarily at presence of water, according to which the reaction conduct at an isocyanate index of 85-120. At that the polyisocyanate component is composed of: al) 80-100 mass % of diphenylmethanediisocyanate containing at least 40 mass % of 4.4'- diphenylmethanediisocyanate and-or a derivative of the indicated diphenylmethanediisocyanate, which (the derivative) is a may be a liquid at the temperature of 25°C and has NCO value of no less than 20 mass % and a2) 20 mass % of the other polyisocyanate; the reactive to isocyanate composition b) consists of b1) 80-100 mass % of a simple polyol polyester having an average nominal functionality - 2-8, average reactive equivalent weight of 750-5000, an average molecular mass of 2000-12000, the share of oxyethylene - 60-90 mass % and the share of the primary hydroxyl groups of 70-100 mass % calculated for the total number of the primary and the secondary hydroxyl groups in polyol; b2) a reactive to isocyanate extender of the chain in such a quantity, that the ratio of the rigid block makes less than 0.45; and b3) - 20-0 mass % of one or more of other reactive to isocyanate composition excluding water. At that the amount of the polyol of 61) and the reactive to isocyanate composition 63) is calculated from the total amount of the indicated polyol 61) and the composition 63). The invention presents also description of the thermosetting elastomer produced according to the indicated method.

EFFECT: the invention ensures production of a thermosetting polyurethane elastomer.

10 cl, 2 ex

The invention relates to a method for producing porous vodosbornich rigid polyurethane foam and/or polyisocyanurates by reacting polyisocyanates with a polyol as one component in the form of an emulsion
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