The polyisocyanate polymers on the basis of obtained from compositions comprising asilicone surfactants, and a method of production thereof

 

(57) Abstract:

Polyurethane, polyisocyanurate and primocanale polymers, in particular foamed polymers, are obtained from compositions comprising asilicone polyester surfactants. Asilicone polyester surfactants are polyethers containing from about 10 to about 90 wt.% oxyethylene units and from about 10 to about 90 wt.% oxyalkylene units, including at least 4 carbon atoms. These asilicone polyester surfactants can be used for the preparation of foamed materials, whose properties are almost identical to the properties of foamed materials obtained using well-known surface-active substances based on silicone. 5 C. and 12 C.p. f-crystals, 9 PL.

This patent application is a partial continuation of U.S. application serial number 08/169477, filed December 17, 1993, entitled "polyisocyanate Polymers on the basis of obtained from compositions comprising asilicone surfactants, and a method for their preparation, currently under consideration by the Agencies The present invention relates to polyisocyanate polymers on the basis of, obtained from compositions comprising asilicone surfactants. The present invention specifically relates to polyurethane, polyisocyanurate and poliocephalum foamed materials obtained from compositions comprising asilicone surfactants.

The usefulness of the polymers on the basis of known polyisocyanate. Useful monomers for polyisocyanates are methylenedianiline (DHS) and toluenediisocyanate (TDI). Polymeric isocyanates, in particular polymer methylenedianiline (sometimes also called polymethylenepolyphenylisocyanate, hereinafter designated as PMDI), represent a very useful intermediate polymer materials. They are used primarily as components in thermosetting and thermoplastic polymeric elastomers, rigid and flexible polyurethane, primecasino and polyisocyanurate foams. Elastomers polyisocyanate basis are used in such fields as the manufacture of car parts reaction injection molding, die casting wheels for skateboards and extrusion components of disposable nappies.

Flexible polyurethane foam materials are widely used, such as the manufacture of mattresses, parts of upholstered furniture, car seats, headrests, instrument panels, packing accessories, toys and the like. Such foam materials are usually prepared by the reaction of nominally bi - or trifunctional polyol high equivalent weight with polyisocyanate in the presence of a blowing agent, and sometimes also in the presence of a small amount of a crosslinking agent.

Depending on the method of manufacture of these foamed materials are usually divided into two types. Molded foam is prepared by the interaction polyurethanebased components in closed form, getting foamed materials having a specified form. In contrast foamed materials in the form of sheet blanks are produced, allowing forming foamed materialmix foam, when one of the reagents is a polyisocyanate, know the use of surfactants to ensure Miscibility of the components of the reaction mixture and stabilize the formation of foam. Often, these surfactants are products based on silicone. For example, in U.S. patent N 5064872, issued in the name Monstrey and others described the preparation polyisocyanurate foamed materials of compositions, including polyalkyloxy polyester copolymer foam stabilizer. In the American patents NN 4097406 and 4172187, issued in the name of Scott and others , describes the preparation of polyurethane foam from compositions comprising the reaction product of tetrachloride silicon with water and alcohol, followed by transesterification with polyetherpolyols.

Although the use of silicone surfactants as stabilizers in polymer compositions is very well known, it is not always the best technical solution in any area of application. One of the drawbacks of silicone surfactants is their cost. Silicone surfactants are often the moat of the compositions, including the polyisocyanates, it would be desirable to enter into such a composition asilicone surfactant, which is significantly cheaper silicone surfactants, giving it almost the same properties as the foam made with their use.

A brief statement of the substance of the invention

In one aspect of the subject of the present invention is containing active hydrogen composition comprising (A) a polyfunctional containing active hydrogen compound, (B) an optional blowing agent, (C) an optional catalyst, and (D) asilicone surfactant, where the surface-active substance is a simple polyester containing from about 10 to about 90 wt.% oxyethylene units and from about 10 to about 90 wt.% oxyalkylene units, including at least 4 carbon atoms, and practically free from oxypropylene links. The composition may also contain silicone surfactant.

In another aspect, a subject of the present invention is a polymer obtained from the composition comprising (1) a polyisocyanate, (2) polyfunctional, which contains ilikonovoi surfactant, where surface-active agent is a simple polyester containing from about 10 to about 90 wt.% oxyethylene units and from about 10 to about 90 wt.% oxyalkylene units, including at least 4 carbon atoms, and mostly free from oxypropylene links.

Another object of the present invention is a method of obtaining a polymer consisting in mixing a polymer composition comprising (1) a polyisocyanate, (2) a polyfunctional containing active hydrogen compound, (3) an optional blowing agent, (4) an optional catalyst, and (5) asilicone surfactant, where the surface-active substance is a simple polyester containing from about 10 to about 90 weight. % oxyethylene units and from about 10 to about 90 wt.% oxyalkylene units, including at least 4 carbon atoms, and mostly free from oxypropylene links.

Yet another object of the present invention is an improvement in a method of producing a polymeric foamed material from a composition comprising (1) a polyisocyanate, (2) a polyfunctional containing active hydrogen compound, (3) proobrazuya, including asilicone surfactant, where the surface-active substance is a simple polyester containing from about 10 to about 90 wt.% oxyethylene units and from about 10 to about 90 wt.% oxyalkylene units, including at least 4 carbon atoms, and mostly free from oxypropylene links.

The present invention relates also to the compound prepared by the method consisting in blocking polyether containing from about 10 to about 90 wt.% oxyethylene units and from about 10 to about 90 wt.% oxyalkylene units, including at least 4 carbon atoms, and mostly free from oxypropylene links, capable of interacting with the amine or hydroxyl material.

Another object of the present invention is a substance that meets the General formula

,

where I denotes not able to interact with alkoxyl fragment of the initiator; each of A and A' independently represents O, N or NH; E denotes oxyethylene group; B denotes oxybutylene group; P denotes oxypropylene group; x and y represent such quantities that the ratio of the 10% of the combined weight oxyethylene links and oxybutylene links; R denotes a number from 1 to 8 depending on the functionality of the initiator; each of Q or Q' independently denotes 1 if A or A' denotes O or NH, and each of Q and Q' denotes 2, if A or A' denotes N; the total molecular weight of the compound ranges from 750 to 11000; C denotes the residue of a blocking compound; and E and B are mostly in blocks.

Description of the preferred embodiments

In one embodiment, the present invention is a polymer obtained from the composition comprising (1) a polyisocyanate, (2) a polyfunctional containing active hydrogen compound, (3) an optional blowing agent, (4) an optional catalyst, and (5) asilicone surfactant. The polymers which can be obtained from the compositions of the present invention include, but are not limited to, polyurethanes, polyisocyanates, modified polyurethanes of the polyisocyanates, polyureas, and the like. Such polymers may be elastomers, rigid foamed materials or elastic foamed materials. All such materials can be prepared by reaction of MDI with containing active hydrogen material, not necessarily in Prisma components, of critical importance. Asilicone surfactants of the present invention can perform at least two important functions. Surfactant is able to take action to help ensure compliance MDI with other components of the composition. This is especially important in the foamed compositions, in which the necessary pores of small size, such as in the case of foamed materials for household appliances, where the foamed material can perform the insulating function. The effect of surfactants is to provide a thorough mixture of MDI and other components of the composition with a blowing agent, in particular distribution throughout the reaction mixture so that the foam form very fine bubbles, which create a homogeneous foam.

Surfactants can stabilize the foam. This is especially important in applications of rigid foam. As foaming in the reaction mixture, it is subjected to destabilization even before the molecular weight of the polymer is sufficient to support the foam. In unstabilized to the mu material insulating properties. In addition, the weight of rising forming foam can grow too quickly, causing the destruction of non-stabilized foams of such compositions under their own weight. When stabilization of the foam asilicone surfactants of the present invention can exhibit the effect of preventing the destruction of the bubbles of the foam. Such surfactants can also give the foam some dimensional stability up until the molecular weight of the resulting polymer will not be sufficient for self-maintenance material.

Surfactants of the present invention is not silicone-based. The surfactants of the present invention are polyethers containing from about 10 to about 90 wt.% oxyethylene units and from about 10 to about 90 wt.% oxyalkylene units, including at least 4 carbon atoms. This weight percentage calculated without taking into account the weight of the initiator. The preferred weight ratio between oxyethylene links and other oxyalkylene links in surface-active substance is from about 1:4 to about 4:1. More preferred is surface-active substance is from about 1:3 to about 3:1. However, even more preferred weight ratio between oxyethylene links and other oxyalkylene links in surface-active substance is from about 1: 2 to about 2:1. The most preferred weight ratio between oxyethylene links and other oxyalkylene links in surface-active substance is from about 1.5:2.0 to 2.0 to: 1,5.

Polyester surfactant of the present invention is almost free from oxypropylene links. Introduction oxypropylene links in the main molecular chain polyether surfactants of the present invention can drastically reduce their surface-active properties. Preferred polyether surfactants of the present invention comprise less than 10 weight. % oxypropylene units, more preferably less than 5 wt.% oxypropylene units, even more preferably less than 1 wt.% oxypropylene units, and most preferably no oxypropylene links.

Molecular weight asilicone polyether surfactants of the present invention is from about 750 to about Calera weight is from about 2000 to about 7000. Nominal functionality such asilicone surfactants is from about 1 to about 8, preferably from about 2 to about 4, and most preferably from about 2 to about 3.

Asilicone surfactants of the present invention is obtained using ethylene oxide and at least one other oxide alkylene containing at least 4 carbon atoms. Preferred another oxide alkylene contains from 4 to about 8 carbon atoms, more preferably from 4 to about 6 carbon atoms. The most preferred another oxide alkylene used to obtain asilicone surfactants of the present invention, is a butylene oxide.

There are several ways to obtain asilicone surfactants of the present invention. In one embodiment, the surfactants of the present invention is prepared by obtaining poliatilenaksidna polyether blend of propylene glycol initiator with butylene oxide in the presence of a basic catalyst. Then, the block copolymer is prepared by the combination of the polybutylene oxide with ethylene oxide in the presence of active substances of the present invention can be prepared by first obtaining polietilenoksidnoy polyester and then obtaining a block copolymer blend of polyethylene oxide with butylene oxide in the presence of a basic catalyst. Block copolymers can be used to produce polyesters with relatively low molecular weights, but may be desirable introduction of some level of disorder to obtain polyesters, of molecular weight greater than about 2000. For example, in another embodiment, a surfactant of the present invention can be obtained by first obtaining poliatilenaksida, as described above, and then the combination of poliatilenaksida with a mixture of the original ethylene oxide with butylene oxide in the presence of a basic catalyst.

Nominal functionality asilicone surfactants of the present invention can be from about 1 to about 8. Although surfactants of the present invention can be obtained by any means that is known as useful for obtaining polyethers, usually they are a combination of initiator oxide alkylene in the presence of a basic catalyst. The choice of initiator is important when determining the nominal functionality of the resulting surface-active substances. So, for example, as an initiator to obtain a surface-active substances in the aqueous substance, highly rated functionality equal to 8, you can use sucrose. You can also apply a mixture of initiators.

Asilicone surfactant of the present invention the special properties can be given a careful choice of initiators. So, for example, as an initiator, you can use the Ethylenediamine. To obtain a surface-active substances having catalytic properties, you can also use other initiators, including catalytic group. Initiators useful for the implementation of the present invention include those that are typically used to obtain polyether polyols, such as alkanolamine, alcohols, amines and the like. Such initiators include, but are not limited to, 2-aminoethanol, ethylene glycol, propylene glycol, 1,3-dihydroxypropane, 1,4-dihydroxybutyl and 1,6-digitoxigenin, glycerol, 1,2,4-trihydroxybutane, 1,2,6-digitoxigenin, 1,1,1-trimethyloctane, 1,1,1-trimethylolpropane, pentaerythritol, polycaprolactone, xylitol, Arabic, sorbitol, mannitol, Ethylenediamine, glycerin, ammonia, 1,2,3,4-tetrahydroquinolin, fructose, sucrose and the like.

Surfactants of the present invention may contain what should be entered in the prepolymers or block with aminovymi or able to interact with the hydroxyl materials. So, for example, surfactants of the present invention can be introduced into the prepolymer with terminal isocyanate groups by reaction of the surface-active substance with a stoichiometric excess of MDI. Similarly, you can block, for example, low-molecular haloalkane, hydrides, organic acids and the like. Preferred blocking material does not include able to interact with polyisocyanate groups. Blocking compounds, resulting in the formation of surface-active substance does not interact with polyisocyanate, allows you to mix the surfactant with polyisocyanates with no response in those cases when such a mixture is desirable. Blocking is achieved by mixing naselyonnogo surfactants with a blocking compound under reaction conditions sufficient to interact blocking compounds with amine or hydroxyl group naselyonnogo polyester surfactants.

Blocked polyether surfactants of the present invention meet the following General formula:

,

guasimo from the other signifies O, N or NH; E denotes oxyethylene group; B denotes oxybutylene group; P denotes oxypropylene group; X and Y represent such quantities that the ratio of X:Y is from 1:4 to 4:1; Z denotes a magnitude that the total weight oxypropylene links is less than 10% of the combined weight oxyethylene links and oxybutylene links; R denotes a number from 1 to 8 depending on the functionality of the initiator; each of Q and Q' independently denotes 1 if A or A' denotes O or NH, and each of Q and Q' denotes 2, if A or A' denotes N; the total molecular weight of the compound ranges from 750 to 11000; C denotes the residue of a blocking compound; and E and B are in blocks. For example, when the polyester is prepared using propylene glycol initiator, at a ratio of oxyethylene and oxybutylene 1:1, and blocked with acetic anhydride, A and A' denote O; the ratio of X and Y is 1:1; Z is O; each of Q and Q' denotes 1; R is 2; I corresponds to the formula

< / BR>
and C corresponds to the formula

< / BR>
One of the variants of the present invention is a polymer formed by the interaction of MDI with polyfunctional containing active hydrogen, m is skilled polyisocyanates, the prepolymers on isocyanate-based and mixtures thereof. They may include aliphatic and cycloaliphatic isocynate, but aromatic and in particular polyfunctional aromatic isocyanates are preferred. Preferred are 2,4 - and 2,6-toluenediisocyanate and the corresponding isomeric mixtures; 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanate and the corresponding isomeric mixtures; mixtures of 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanate and polyvinylpolypyrrolidone PMDI; and mixtures of PMDI and toluylenediisocyanate. To obtain in accordance with the present invention are useful, in addition, aliphatic and cycloaliphatic isocyanate compounds such as 1,6-hexamethylenediisocyanate; 1-isocyanato-3,5,5-trimethyl-1,3-isocyanatomethyl; 2,4 - and 2,6-hexahydrotriazine, as well as the corresponding isomeric mixtures; 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane, as well as the corresponding isomeric mixtures.

In addition, as a polyisocyanate component, it is advantageous to use the so-called modified polyfunctional isocyanates, i.e. products that are produced by chemical reactions of the above diisocyanates and/or polyisocyanates. Examples of SL is s and/or uretonimine; contains, which is and/or urethane group diisocyanates and polyisocyanates. Can be also used liquid polyisocyanates comprising carbodiimide groups, uretonimine group and/or which ring, the content of isocyanate groups (NCO) is from 10 to 40 wt.%, more preferably from 10 to 35 wt.%. They include, for example, polyisocyanates based on 4,4'-, 2,4'- and/or 2,2'-diphenylmethanediisocyanate and the corresponding isomeric mixtures, 2,4 - and/or 2,6-toluylene diisocyanate and the corresponding isomeric mixtures 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanate and the corresponding isomeric mixtures; mixtures of diphenylmethanediisocyanate, PMDI, a mixture of toluylenediisocyanate, PMDI and/or diphenylmethanediisocyanate.

Acceptable to the prepolymers, the NCO content is from 5 to 40 weight. %, more preferably from 15 to 30 wt.%. These prepolymers are prepared by the reaction of polyisocyanates with materials, which include low molecular weight diols, triola, but they can also be obtained by using polyvalent containing active hydrogen compounds, such as di - and triamine, di - and tricoli. Some examples are aromatic polyisocyanates comprising urethane groups, prepost is by the reaction of diisocyanates and/or polyisocyanates, for example, low-molecular dialami, triolisme, oxyalkylene, dioxyalkylene or polyoxyethyleneglycol, a molecular weight of up to about 800. These polyols can be used individually or in mixtures in the form of di - and/or polyoxyethyleneglycol. For example, you can apply diethylenglycol, dipropyleneglycol, polyoxyethyleneglycol, polyoxypropyleneglycol and polyoxypropyleneglycol.

When implementing the present invention is particularly useful are (I) polyisocyanates with an NCO content of from 8 to 40 wt.%, containing carbodiimide groups and/or urethane groups, from 4,4'-diphenylmethanediisocyanate or a mixture of 4,4'- and 2,4'-diphenylmethanediisocyanate; (II) prepolymers, including NCO, the content of NCO which is from 20 to 35 wt.% the total weight of the prepolymer, obtained by the interaction of polyoxyethyleneglycol, the preferred functionality of which is equal to from 2 to 4 and molecular weight is from about 800 to about 15000, with 4,4'-diphenylmethanediisocyanate or a mixture of 4,4'- and 2,4'-diphenylmethanediisocyanate and mixtures (I) and (II); and (III) 2,4 - and 2,6-toluenediisocyanate and the corresponding isomeric mixtures. You can also use the Naya weight is in the range from about 125 to about 3000, more preferably from about 150 to about 175, and the average functionality greater than about 2. A more preferred average functionality of from about 2.0 to about 3.5. The preferred viscosity of the polyisocyanate component comprises from about 25 to about 5,000 centipoise (SDR) (from 0.025 to about 5 Pass), but because of the ease of processing the preferred value of from about 100 to about 1000 centipoise for the 25oC (from 0.1 to 1 Pass). In those cases, when you choose other polyisocyanate components, preferable similar viscosities.

Upon receipt of the polymers of the present invention, the component "A" (which includes the polyisocyanate) is mixed with component B, which is containing the active hydrogen compound. As component "B" can be used containing an active hydrogen compounds, or similar to those used in obtaining the prepolymer component "A", if component a is a prepolymer, or other compounds. The most commonly used containing active hydrogen compounds are those compounds that include at least two hydroxyl groups. These combinations are called polyols. the XVI, "Polyurethanes, Chemistry and Technology", by Saunders and Frisch, Interscience Publishers, new York, volume I, SS. 32-42, 44-54 (1962) and volume II SS. 5-6, 198-199 (1964); Organic Polymer Chemistry, the authors K. J. Saunders, Chapman and Hall, London, SS. 323-525 (1973) and Developments in Polyurethanes, volume I, J. M. Burst, ed. Applied Science Publishers, SS. 1-76 (1978). However, when implementing the method of the present invention can use any containing active hydrogen compound. Examples of such materials include those selected from the following classes of compounds individually or as a mixture: (a) acceleratedly adducts of polyhydroxyalkane; (b) acceleratedly adducts nereguliruemyi sugars and derivatives of sugars; (b) acceleratedly adducts of phosphoric and polyphosphoric acids and (g) acceleratedly adducts of polyphenols. The polyols of these types are called "base polyols". Examples alkalinising adducts of polyhydroxyalkane, which can be used for this purpose are the adducts of ethylene glycol, propylene glycol, 1,3-dihydroxypropane, 1,4-dihydroxybutyl, 1,6-digitoxigenin, glycerol, 1,2,4-trihydroxybutane, 1,2,6-trihydroxybenzene, 1,1,1-trimethylamine, 1,1,1-trimethylolpropane, pentaerythritol, polycaprolactone, xylitol, Arabica, sorbitol, mannitol and the like. Among them, preferred etkilenecegini include Ethylenediamine, glycerin, ammonia, 1,2,3,4-tetrahydroquinolin, fructose and sucrose.

Preferable poly(oxypropylene)-glycols, triola, thetruly and sexaly, as well as any of those that interlock with ethylene oxide. These polyols include poly-(oxopropanenitrile)-polyols. The preferred content oxyethylene links should be less than about 80 weight. % by weight, more preferably less than about 40 wt.%. When using ethylene oxide, it is possible to enter in any way along the polymer chain, for example in the form of internal blocks, terminal blocks, disordered placed blocks, or any combination thereof.

For the implementation of the present invention is also suitable polyamine, aromatic polyether polyols, aliphatic polyether polyols, the polyols with integral aminovymi groups, polymercaptan and others interact with isocyanate compounds. For use in the implementation of the present invention is particularly preferable containing active hydrogen polyaddition products of MDI (PPI). Prisoedinenia are usually the products of interactions between TDI and triethanolamine. Description of the method of obtaining Prisoedinennym class of polyols are the "copolymer polyols", which are containing the base polyols, stably dispersed polymers such as Acrylonitrile-styrene copolymers. Such copolymer polyols can be obtained from reaction mixtures containing a variety of other materials, including, for example, catalysts such as azo-visitbotanical; copolymer Paleologue stabilizers and regulators degree of polymerization, such as isopropanol.

Polymeric foam materials of the present invention prepared using the pore-formers. The reaction of the polyisocyanates of the present invention containing the active hydrogen compounds are recommended in the presence of a blowing agent. In the practical implementation of the present invention is acceptable to use any pore-forming substance or a mixture. Suitable pore-formers include inorganic pore-formers, such as water, an organic pore-formers, which are volatile at the reaction temperature, and dissolved inert gases. Suitable organic pore-formers include acetone; ethyl acetate; methanol; ethanol; golozhabernyi alkanes, such as methylene chloride, chloroform, utilitare, Trichlorofluoromethane, 1,1-di is heptane; diethyl ether and the like. As pore-formers can also be used gases inert with respect to source components, such as nitrogen, air, carbon dioxide, and the like. In addition, it is possible to use compounds such as azides, which at a suitable temperature decompose, forming gases, such as nitrogen. Preferred pore-formers are compounds that boil in the range between about -50 and 100oC, more preferably between about -40 and 50oC.

The amount of blowing agent to the invention, not decisive, but in the preferred embodiment, it should be sufficient for foaming of the reaction mixture. This number varies depending on such factors as the desired density of the foamed product.

For the practical execution of the invention useful blowing agent is water. In addition to the selection of gaseous carbon dioxide for foaming water quickly reacts with polyisocyanate components, thus at an early stage to give a polymer of the strength needed to hold the gas. Usually in the case of water, it is the content the component B. In combination with water may be used other pore.

The scope of the present invention include polymers such as polyurethanes, polyisocyanurates and polyurea. Primocanale composition can often be samoktirika. Polyurethane and polyisocyanurate foaming compositions typically include a catalyst. When carrying out the present invention it is acceptable to use polyurethane catalysts. This catalyst is preferably introduced into the composition in an amount acceptable to increase the speed of interaction between the isocyanate groups of the composition of the present invention and hydroxyl-containing reactive components. Although it is known that this purpose can be used with a wide variety of materials, the most commonly used and preferred catalysts are tertiary amine catalysts and ORGANOTIN catalysts.

Examples of tertiary amine catalysts include, in particular, triethylenediamine, pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, diethylethanolamine, N,N-dimethylcyclohexylamine, dimethylethanolamine, N-cocomotion, 1-methyl-4-diethylaminocoumarin, 3-the amine catalysts are preferably used in quantities of from about 0.01 to about 5 wt.% paleologou composition.

Examples of ORGANOTIN catalysts include dimethylglutaric, dibutyltindilaurate, dioctyladipate, octout divalent tin and the like. Other examples of effective catalysts include, in particular, those listed in U.S. patent N 2846408. ORGANOTIN catalyst is preferably used in an amount of from about 0.001 to about 0.5 wt.% from paleologou composition.

Catalysts suitable for use in the implementation of the present invention include those that catalyze the formation of isocyanurates, such as mentioned in the work of Saunders and Frisch in Polyurethans, Chemistry and Technology 1 High Poiymers, volume XVI, SS. 94-97 (1962). Such catalysts called here the trimerization catalysts. Examples of these catalysts include aliphatic and aromatic tertiary amine catalysts, ORGANOMETALLIC compounds, alkali metal salts of carboxylic acids, phenols and symmetrical triazine derivatives. The preferred catalysts are potassium salts of carboxylic acids, such as octoate potassium and the potassium salt of 2-ethylhexanoic acid, and tertiary amines, such as, for example, 2,4,6-Tris-(dimethylaminomethyl)-phenol.

When the implementation is represent inorganic materials, which can be used instead of more expensive organic components and sometimes improve some physical properties. For example, in the compositions of the present invention can be entered crushed glass, glass, kaolin and the like. Supplements usually are materials that are added to the polymer composition to specifically improve certain properties. For example, in the compositions according to the present invention it is possible to enter all such additives as a means of informing the conductivity, flame retardants, pigments and the like. When performing the present invention can use any filler or additive that is known to any expert in the art as useful for obtaining foamed polymeric materials.

Surfactants of the present invention can be used to obtain polyurethane polymers. In two (a and B) polyurethane polymer compositions unlocked asilicone surfactants can be entered in component B, where they are usually stable. Alternatively unlocked asilicone surfactants nastoyaniu surfactants of the present invention can be entered either in component a, or in component B. where appropriate, upon receipt surfactants that can be used to produce the prepolymer component B, it is possible to apply a locking compound containing able to interact with the active hydrogen group. In the case of a three-component polyurethane compositions, where the 3rd or component "B" is the catalyst can also enter any number or part naselyonnogo surfactants of the present invention.

Surfactants of the present invention is introduced into the polyurethane composition in a concentration suitable for imparting the desired properties of stability of the foamed material and the compatibility of the components of the reaction mixture. Due to fluctuations in a wide range of weight ratios of the components of the polyurethane composition in the technique of preparation of the polyurethanes of the content of the surfactant is expressed in parts of the surfactant per 100 parts of polyol in the B-component composition. Considering the purpose of the present invention, the concentration asilicone surfactants of the present invention in polyurethane the location of the connections in the component B excluding surfactants. In a preferred embodiment, asilicone surfactants of the present invention are contained in the reaction mixture in a concentration of from about 0.25 to about 20 hours to 100 hours containing active hydrogen compounds, more preferably from about 0.5 to about 10 hours 100 hours containing active hydrogen compounds, and even more preferably from about 1 to about 5 hours at 100 hours containing active hydrogen compounds.

For illustration being present invention provides the following examples. These examples are not intended to restrict the scope of the present invention, therefore, they cannot thus be interpreted. In all cases, except as specifically stated, quantities are expressed in parts by weight or weight percent.

Example 1. Asilicone surface-active substance is prepared by loading the reaction vessel with a closed system 656 g of 1,2-propylene glycol containing approximately 6% of potassium hydroxide. The reactor is sealed and heated to 130oC. In the reactor 5645 g 1,2-butilenica injected at a rate sufficient to avoid exceeding the excess pressure of 70 pounds per square inch (of 482.6 kPa), and while the subsequent fall of pressure is Then injected into the reactor 597 g of ethylene oxide. After stabilization of the pressure drop polyester surfactant analyze. The molecular weight of the obtained polyester surfactant is approximately 902, the weight percentage oxybutylene groups (hereinafter BO) is 72.5, the weight percentage oxyethylene groups (hereinafter EA) - 19,1, and a nominal functionality of 2.

Polymeric foamed material is prepared by mixing the composition shown in table 1, first, by carefully mixing the polyol, catalyst, surfactant and blowing agent in the plastic Cup. Then in the Cup and add PMDI and the mixture is stirred with a speed of 1500 rpm. /min using a 4-inch (10.2 cm) of the agitator, mounted on a drill press. Polymerizing the mixture is then poured into a box shape size 14 inches x 14 inches x 14 inches (35.6 cm x 35.6 cm x 35.6 cm) and left to rise. Determine the physical properties and reactivity profile of polymeric foam and reduce data in table 2.

Example 2. Polymer foam is prepared and feel almost identical set forth in example 1, except that the molecular weight of the used polyester powerha EA - 42,6, and a nominal functionality of 2. Determine the physical properties and reactivity profile of this polymeric foam and reduce data in table 2.

Example 3. Polymer foam is prepared and feel almost identical set forth in example 1, except that the molecular weight of the used polyester surfactants obtained by the use of triethylenemelamine ether is 1428, the weight percentage BO - 44,6, the weight percentage of EC - 50,0, and a nominal functionality of 2. Determine the physical properties and reactivity profile of this polymeric foam and reduce data in table 2.

Comparative example 4. Polymer foam is prepared and feel almost identical set forth in example 1, except that use a known surface-active agent based on silicone. Determine the physical properties and reactivity profile of this polymeric foam and reduce data in table 2.

Example 5. Polymer foam is prepared and feel almost identical set forth in example 1, except that use of the composition shown in table 3.

Molecular weight polyester p is the content of EC - 19,1, and a nominal functionality of 2. Determine the physical properties and reactivity profile of this polymeric foam and reduce data in table 4.

Example 6. Polymer foam is prepared and feel almost identical set forth in example 5, except that the molecular weight of the used polyester surfactant is 1836, the weight percentage BO - 53,2, the weight percentage of EC - 42,6, and a nominal functionality of 2. Determine the physical properties and reactivity profile of this polymeric foam and reduce data in table 4.

Example 7. Polymer foam is prepared and feel almost identical set forth in example 5, except that the molecular weight of the used polyester surfactants obtained by the use of triethylenemelamine ether is 1428, the weight percentage BO - 44,6, the weight percentage of EC - 50,0, and a nominal functionality of 2. Determine the physical properties and reactivity profile of this polymeric foam and reduce data in table 4.

Comparative example 8. Polymer foam is prepared and feel almost identical set forth in paragraph predelay physical properties and reactivity profile of this polymeric foam and reduce data in table 4.

Example 9. Polymer foam is prepared and feel almost identical set forth in example 1, except that use of the composition shown in table 5. Molecular weight polyether surfactants obtained by the use of Adduct of methanol (corresponding to the formula MeOCH2CH2OCH2CH2OCH2CH2OH), is 1550, the weight percentage BO - 33,4, the weight percentage of EC - 56,1, and a nominal functionality - 1. Determine the physical properties and reactivity profile of this polymeric foam and reduce data in table 6.

Comparative example 10. Polymer foam is prepared and feel almost identical set forth in example 9, except that use a known surface-active agent based on silicone. Determine the physical properties and reactivity profile of this polymeric foam and reduce data in table 6.

Example 11. Polymer foam is prepared almost identically described in example 1, except that use of the composition shown in table 7. Monostable approximately 6800, the weight percentage of the BO - 60,6, the weight percentage of EC - 38,3, and a nominal functionality of 2. Quality foam material define a visual study of this foam material. If the foamed material is characterized by small pore size and does not have excessive looseness, it passes the test of foamed material quality, as indicated in table 7, the symbol "+".

Example 12. Polymer foam is prepared and feel almost identical set forth in example 11, except that the molecular weight of the surfactant is approximately 4595, the weight percentage BO - to 78.9%, the weight percentage of EC - 19,6, and a nominal functionality of 2. The results of the foam test material are shown in table 7.

Comparative example 13. Polymer foam is prepared and feel almost identical set forth in example 11, except that the surface-active substance is a known silicone surfactant. The results of the foam test material are shown in table 7.

Comparative example 14. Polymer foam is prepared almost identically laid out punanny material is tested for quality, which he is not.

Comparative example 15. Polymer foam is prepared almost identically described in example 11, except that the use of ethylene oxide-propylenoxide polyether surfactant. Molecular weight surfactants is approximately 6600, the weight percentage of propylene oxide - 44,4, the weight percentage of EC - 52, and a nominal functionality of 2. Foamed material is tested for quality, which it is not.

Example 16. Blocked asilicone polyester surfactant is prepared according to the method, which includes the following stages:

1) 1013,2 g butylenes-ethylenoxide blokoviprema surfactants, obtained using propylene glycol, molecular weight which is approximately 4600, loaded into a 2-liter, 5-necked round bottom flask, equipped with a nozzle for vacuum distillation, a thermocouple, magnetic stirrer, heating jacket and an inlet pipe for nitrogen;

2) in this round-bottom flask is charged with 60 g of acetic anhydride;

3) polyester and acetic anhydride for 30 min) the contents of the flask incubated under reflux at 100oC for 2.5 h;

6) the flask is heated to 135oC under partial vacuum for 15 min, and to minimize the pulsating boiling in the introduced nitrogen;

7) the temperature of the flask was raised to 150oC and the contents incubated under full vacuum to visible termination of distillation;

8) the flask is kept under full vacuum at 150oC for another 15 min;

9) next, the product is rinsed with nitrogen under a pressure of 90 Torr (12 kPa) for 4 h;

10) the product is cooled to room temperature.

The final material is a simple transparent polyester, lacking any measurable activity active hydrogen.

Examples 17, 18 and comparative example 19. Polymeric foamed material is prepared as follows.

1) Polyester surfactant receive almost identical set forth in example 1, except that the molecular weight of this polyester surfactant is approximately 4600; the weight percentage of the BO - 86; the weight percentage of EC - 12; and to obtain this surface-active substances applied ethylene oxide mixed with butylene oxide in soochna described in example 16.

3) the Polymer foam is prepared and feel almost identical set forth in example 1, except that use blocked surfactant above the stage 2 and the composition shown in table 8, and part of the surface-active substances and pore initially mixed with polyisocyanate. Physical properties fix and bring to the table 9.

1. The composition containing the active hydrogen containing polyfunctional containing the active hydrogen compound, optionally a blowing agent, optionally a catalyst and asilicone surfactant containing oxyalkylene links, characterized in that as surface-active substances it contains a simple polyester containing from about 10 to about 90 wt.% oxyethylene units and from about 10 to about 90 wt.% oxyalkylene units, including at least 4 carbon atoms, and mostly free from oxypropylene links, when the weight ratio between oxyethylene links and other oxyalkylene links equal to from about 1:3 to about 3:1.

2. The composition containing the active hydrogen under item 1, in which preobrazovatele substance is a simple polyester, the functionality is from about 1 to about 8.

4. The composition containing the active hydrogen on p. 3, in which the surfactant is a simple polyester, the functionality of which is from about 2 to about 4.

5. The composition containing the active hydrogen on p. 4, in which the surfactant is a simple polyester, the functionality of which is from about 2 to about 3.

6. The composition containing the active hydrogen under item 1, in which the surfactant is a simple polyester comprising oxyethylene links and oxybutylene links.

7. The composition containing the active hydrogen on p. 6, in which the surfactant is obtained using the initiator in the presence of a catalyst.

8. The composition containing the active hydrogen under item 1, which contains the active hydrogen compound is a primary polyol.

9. The composition containing the active hydrogen under item 1, in which the containing active hydrogen composition comprises a silicone surfactant.

10. The polymer obtained from the on p. 10, where the polymer is a foamed material.

12. The polymer under item 10, where the polymer is a foamed water material.

13. The polymer under item 10, where the polyisocyanate is chosen from the group consisting of colorvision, methylenedianiline, polymethylenepolyphenylisocyanate, modified methylenedianiline, mediendienstestaatsvertrag the prepolymer, polymethylenepolyphenylisocyanate the prepolymer and mixtures thereof.

14. The polymer p. 13, where the polyisocyanate is a prepolymer obtained with the use of surfactants representing a simple polyester containing from about 10 to about 90 wt.% oxyethylene units and from about 10 to about 90 wt.% oxyalkylene units, including at least 4 carbon atoms, and mostly free from oxypropylene links.

15. A method of producing a polymer, comprising mixing the polyisocyanate composition and the composition containing an active hydrogen, characterized in that the use of a composition containing an active hydrogen, under item 1.

16. A method of obtaining a polymer foam material of the composition comprising the polyisocyanate, poverhnosti-active substance, characterized in that the use of a composition including asilicone surfactant, where the surface-active substance is a simple polyester containing from about 10 to about 90 weight. % oxyethylene units and from about 10 to about 90 wt.% oxyalkylene units, including at least 4 carbon atoms, and mostly free from oxypropylene links, and the weight ratio between oxyethylene links and other oxyalkylene links which ranges from about 1:3 to about 3:1.

17. The compound of General formula

< / BR>
where I refers to directionspanel towards alkoxyl the remainder of the initiator; each of a and a' independently denotes O, N or NH; E means oxyethylene group; means oxybutylene group; R means oxypropylene group; x and y represent such quantities that the ratio of x: y is from 1:4 to 4:1; Z means such amount that the total weight oxypropylene links is less than 10% of the combined weight oxyethylene links and oxybutylene units; R is a number from 1 to 8 depending on the functionality of the initiator; each of Q and Q' independently is 1 if a or a' osnet from 750 up to 11000; With mean residue blocking the connection; and E and are mostly in blocks.

Priority PP:

17.12.96 on PP.1 - 16;

23.11.94 on p. 17.

 

Same patents:
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Polymer composition // 2078781
The invention relates to the production of sealing compounds, adhesives, compounds for corrosion protection, bonding and sealing metal, concrete and wood structures

The invention relates to polyurethane chemistry and relates to hydroxyl-containing composition to obtain a flexible polyurethane foam (PUF) cold forming and can be used in the furniture, automotive and aviation industries

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The invention relates to the field of production of two-component compounds with increased strength and can be used to seal the membrane elements

FIELD: organic chemistry, polymer materials.

SUBSTANCE: polyester-polyols are obtained by double metalcyanide catalyzed polyaddition of alkylenoxide to starting material containing active hydrogen atoms. Alkylenoxide is continuously fed into reactor during induction period while maintaining constant pressure in reactor.

EFFECT: method for polyester-polyol production with decreased induction time.

2 ex, 1 dwg

FIELD: organic chemistry, in particular polyol composition for cold-cured polyurethane production.

SUBSTANCE: claimed composition contains (pts mass): polyethertriol or mixture of polyethertriol with molecular weight of 4500-6500 and average hydroxyl functionality of 3 - 100; ethylene glycol - 3.5-6.2; 1-4-butandiol - 3,5-8,0; triethylene diamine - 0.53-0.65; water - 0.25-0.50; organosilicate foam regulator - 0.002-0.004; and high boiling by-product from isoprene production based on alkyl- and oxyalkyl-substituted dioxacyclanes (e.g., 1,3-dioxane containing 1-4 mass % of hydroxyl groups) as organic filler - 2-100. Said filler may be used in mixture with oil plasticizer. Polyurethane obtained according to present method has Shore A hardness of 20-50, and is useful in automobile industry, and as material for gasket and sealing.

EFFECT: composition for production of polyurethane with increased hardness.

2 cl, 1 tbl, 3 ex

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