Polyurethane composition

FIELD: polymer materials.

SUBSTANCE: invention relates to polymer compositions including at least one polyurethane prepolymer A with isocyanate terminal groups obtained from at least one polyisocyanate with at least one polyol A1 and, if necessary, with at least one polyol A2. wherein A1 is linear polyoxyalkylenepolyol with unsaturation degree ,less than 0.04 m-equ/g; A2 is polyol, which is present in amount 0-30%, preferably 0-20%, in particular 0-10% based on total amount A1+A2; and at least one polyaldimine B. Composition is a mixture of polyurethane prepolymer A with polyaldimine B. In absence of moisture, such compositions are stable on storage. When being applied, such compositions are brought into contact with moisture, after which polyaldimines are hydrolyzed into aldehydes and polyamines, and polyamines react with polyurethane prepolymer containing isocyanate groups. Products obtained from such composition possess very wide spectrum of properties, including tensile strength varying within a range from 1 to 20 MPa and ultimate elongation above 1000%. Composition may be used as glue, hermetic, coating, or facing.

EFFECT: expanded possibilities of polyurethanes.

3 cl, 7 tbl, 34 ex

 

The invention relates to compositions containing a special high molecular weight polyurethane prepolymers obtained from the special, mostly linear, long chain of polyoxyethyleneglycol with a low degree of unsaturation and polyaluminum.

Polyurethanes are used, inter alia, as a one-component, moisture curing, elastic sealants, adhesives and coatings. Usually they contain a polyurethane prepolymer derived from polyols and polyisocyanates in stoichiometric excess, which is then mixed with other components and to use the store in the absence of moisture. These known systems have several disadvantages. When the interaction of the isocyanate groups with water, for example, from air (air moisture) produces a certain amount of gas CO2depending on the content of the isocyanate in the mixture. Depending on the recipe and conditions of application of the resulting gas CO2leads to the appearance of bubbles in the cured product. This undesirable appearance of bubbles is facilitated by a number of factors, namely, the high content of isocyanate groups in the composition, a relatively low viscosity, fast curing, as well as the porous substrate. Another disadvantage is the relatively narrow limits of mechanical strength, which is achieved when using the their one-component compositions after curing. On the one hand, limited mechanical strength that can be achieved through a prepolymer. For noticeable changes in the values of mechanical strength in the direction of increase or decrease shall be applied to concrete, obtained specifically to provide these desirable mechanical properties of the prepolymer. On the other hand, the formulation of the compositions with the highest levels of strength because of the emergence of bubbles and high viscosities are imposed significant limitations. The prepolymers required to achieve high strengths, show, or because of the high functionality (notably higher of the two), or because prelink short-chain diols with the formation of long-chain through diisocyanates (and because of this high concentration of urethane groups) very high viscosity, which greatly hinders their processing, or have a high content of free isocyanate groups, resulting in curing they are very prone to bubble formation, or both. It is therefore very high tensile strength, for example, of the order of 10 MPa or more, in the case of one-component moisture curing polyurethane with today's level of technology in practice hardly achievable.

Another disadvantage occurs when the application poliuretano is as megabacteria construction sealants, used for sealing joints in building construction. Such sealant should, on the one hand, to have a very low modulus of elasticity and very high elongation and good ability to recover. Such products typically have, according to the prior art, fairly sticky surface, which is prone to unsightly dirt.

Alternatively, discusses the two-component system, which, however, also have the known disadvantage associated with the process of mixing, which leads to excessive for the user and is a source of error that cannot be underestimated when applying products.

As polyols to obtain polyurethane prepolymers for very flexible compositions are typically used polyoxyalkylene, mainly polypropylenglycol. Usually they are obtained by basic catalysis. In catalyzed by bases polymerization processes receive, however, the polyols with relatively high share monoperoxyphthalic molecules, the so-called monali that at one end of the chain have a double bond. With increasing molecular weight polyol greatly increases the amount monola and, thereby, the degree of unsaturation. When applying linear polyols low OH-functionality (i.e. significantly below the ideal value 2) the Veda is to a high degree of unsaturation, to poor mechanical properties in the cured state. Therefore, in the case of polyols, which receive basic catalysis, the achievement of high molecular mass polyurethane prepolymers is only possible by linking the relatively short-chain diols with polyisocyanates, resulting prepolymers with undesirable high viscosities.

Special polyoxyalkylene with high molecular weight and very low unsaturation derived using the so-called bimetallic cyanide complex catalysts, abbreviated as DMC catalysts have been developed in the 60-ies and described in patents US 3,427,256, US 3,427,334, US 3,427,335, US 3,829,505 and US 3,941,849. These polyols have a very low degree of unsaturation, as well as OH-functionality is only slightly less than 2.

Since then, the technology of DMC-catalyzed continuously improved, and the products were on sale. Description patent WO99/29752, US 5,849,944 and US 6,036,879, for example, disclose the use of such polyols as a two-component injection moulding of elastomers.

Indeed, the application of these special polyols in a single component, moisture curing, elastic sealants and adhesives can be obtained high molecular weight polyurethane prepolymers with a low viscosity. However, there are other difficulties, which were hitherto not been able in order to be solved. Thus, high molecular weight prepolymers synthesized from the above-mentioned high-molecular polyols, though, and have a low viscosity compared with the corresponding high molecular weight of the prepolymers, in which short-chain polyols are connected with a diisocyanate in a longer chain; however, they are mainly hydrophobic due to the low concentration of urethane groups. This leads to a more hydrophobic prepolymers noticeably slower otverzhdajutsja moisture, as water is present in smaller quantity, and, on the other hand, a predisposition to the formation of bubbles due to removal during curing moisture gas CO2above, as it significantly worse than more soluble in a hydrophobic polymer. Adhesive, suitable for industrial applications should, however, be cured quickly, and in most cases with only a small free surface to absorb the necessary water from the air. To achieve the required high mechanical strength is required, in addition, the high content of isocyanate. Because of this, when cured forms a relatively greater amount of CO2that, as has already been written, leads to the formation of bubbles during curing.

Patent US 5,124,425 describes the use of such polyols obtained by DMC-catalyzed, including in the form of a single component is moisture curing or two-component polyurethanes. In the examples, the tensile strength reaches of 1.7 MPa. Significantly higher strength than can be achieved using the described method, since the problem of bubble formation at higher concentrations of isocyanate groups are not resolved.

To prevent bubble formation in a one-component polyurethane sealants and adhesives are various possibilities. On the one hand, part or all of the isocyanate end groups of the prepolymer can interact with the receiving end alkoxysilane groups because they can, for example, to react with aminoalkylsilane. This forms a prepolymer with terminal alkoxysilane group, which also cures upon contact with moisture through hydrolysis alkoxysilane groups and subsequent condensation of silanol groups with the formation of siloxane groups. When this curing mechanism is not formed CO2and consequently produce less or no bubbles formed. However, the stitching alkoxysilane groups leads to products with a lower ultimate elongation and low strengths. Patent EP 1 093 482 describes a polyurethane-based polyols with high molecular weight, narrow molecular weight distribution and an OH functionality is close to 2. To prevent the formation of bubbles isocyanate end groups fo the polymer can completely or partially be subjected to interaction with organosilane, as, for example, aminoalkylsilane. As already mentioned, thus it is impossible to obtain polyurethanes with high movements and strength. Therefore, there is only one example in this patent description, one system that cures mainly alkoxysilane having a tensile strength of all of 0.49 MPa at maximum elongation 276%.

Polyamidimide are the compounds known in polyurethane chemistry and described, for example, in patents US 3,420,800 and US 3,567,692. From containing isocyanate groups of the polyurethane prepolymers and polyaluminum receive one-component products. Upon contact with moisture polyamidimide hydrolyzed with formation of the corresponding aldehydes and polyamines, which then react with the isocyanate groups of the prepolymer and otverzhdajutsja without allocation of CO2. Such systems have been described, for example, in patents US 3,932,357, US 4,009,307, US 4,720,535, US 4,853,454, US 5,087,661 and EP 985 693.

The objective of the present invention are compositions that are based on only one or more high molecular weight polyurethane prepolymers cover a wide range of mechanical strength in comparison with the prior art have additional benefits. So, on the one hand, the desired products at low module of elasticity, high elongation and good R & d ability and return deformation have very dry surface and thus suitable as construction sealants for sealing joints; on the other hand, there is a need for a very flexible product that otverzhdajutsja quickly and without bubbles, have high and very high mechanical strength and is suitable as adhesives for various industrial applications. These compositions must have a very low technical viscosity, so that could be the prepared foods that can be applied with relatively little effort, the coating having a short gap between the threads (so the environment is not contaminated by the product when OTDELENIE tip applicator after application) and does not contain solvents and plasticizers or contain a small number, which is favourable for the adhesion properties of the product, and from the point of view of ecology as solvents (VOC = volatile organic compounds), and plasticizers, most commonly phthalates, present a problem for the environment. In addition, possible present plasticizers prone when applied to porous substrates, such as natural stones, and when the coating paint to migrate from the composition. Because of this, for example, the seams may appear unsightly discoloration, or painting will become soft and sticky.

Unexpectedly, it was found that this problem can be solved by combining a special, linear polymer sciense ser the regular polyurethane prepolymers A, derived from a special, mainly long chain of polyoxyethyleneglycol with a low degree of unsaturation and polyamidimide B.

Using the described combination of a special high molecular weight polyurethane prepolymer derived from the special linear long chain of polyoxyethyleneglycol with a low degree of unsaturation and polyaluminum, by changing and combining different polyaluminum with few prepolymers to obtain various very flexible products with a very wide range of mechanical strength (tensile strength, for example, in the range of from about 1 up to 20 MPa), and ultimate elongation of more than 1000%, which in the absence of moisture stable when stored in suitable packaging, have low technical viscosity upon contact with moisture quickly and without bubbles otverzhdajutsja and in dry condition have very dry the surface.

Such compositions can greatly reduce the number of prepolymers, for various polyurethane sealants, adhesives and coatings, which from the point of view of the profile of mechanical properties meet the most different requirements. Since the processing and storage of different prepolymers due to their high viscosity, sensitivity to moisture and needs in the areas for industrial Ave is in the production associated with high costs, the decrease in the number of prepolymers, for various products, is a great advantage is the progress in technology. In addition, such compositions can with a minimal set of prepolymers to prepare as megabacteria construction sealants with high elongation and good elastic consequence, and a very dry surface, as well as high-strength elastic adhesives with tensile strength up to 20 MPa or more, which otverzhdajutsja quickly and without bubbles. Always having a low viscosity of such compositions also allow you to get a well-processed products, not containing or containing slightly solvents and plasticizers, which is favourable from the point of view of their adhesive properties, resistance to migration, as well as from the point of view of ecology.

An additional advantage compared with the prior art is that described cured compositions are more hydrophobic than compositions based on conventional polyols. Therefore, they have less unwanted water absorption, making less swelling and less sensitive to hydrolysis.

In addition, according to a preferred variant implementation of the compositions can completely abandon the use of ORGANOMETALLIC, in particular, tin-containing catalysts. Thanks acomparatively higher thermal stability of the cured material due to a slower reverse cleavage of urethane; and besides, this is an advantage from the point of view of ecology, because of the potential toxicity and environmental threats from metals, in particular ORGANOTIN compounds.

The present invention relates to compositions comprising at least one polyurethane prepolymer A with isocyanate terminal groups and at least one polyamidimide B, and the polyurethane prepolymer A is derived from at least one polyol A1 and optionally at least one polyol A2, and polyisocyanates. Polyol A1 is a linear polyoxyalkylene and has a degree of unsaturation <0.04 m-equiv/g, while the polyol A2 is present in an amount of 0-30 wt.%, preferably 0-20 wt.%, in particular, 0-10 wt.%, in calculating the total number of A1+A2. In addition to the aforesaid components of the composition according to the preferred embodiment may contain one or more of the following components: plasticizers, solvents, fillers, pigments, catalysts, rheology modifiers, such as, for example, thickeners, adhesion promoters, dehumidifiers, antioxidants, light stabilizers and other customary in the industry polyurethane additives.

Additionally describes the use of this composition as an adhesive, sealant, coating or lining. Next featur what is the method of obtaining the composition, and also a way of bonding, sealing or coating. Finally, of the product described, the surface of which is at least partially in contact with such a composition.

Method of execution of the invention

The present invention relates to compositions that include at least one polyurethane prepolymer A with isocyanate terminal groups and at least one polyamidimide B, and the polyurethane prepolymer A is derived from at least one polyol A1 and optionally at least one polyol A2, and polyisocyanates. Polyol A1 is a linear polyoxyalkylene and has a degree of unsaturation <0.04 m-equiv/g, while the polyol A2 is the amount of 0-30 wt.%, preferably 0-20 wt.%, in particular, 0-10 wt.%, in calculating the total number of A1+A2.

A polyurethane prepolymer obtained by the interaction between a polyol with a polyisocyanate, and a polyol to 70 wt.%, preferably 80 wt.% consists of at least one linear polyol A1. This interaction may occur through the fact that the polyol and the polyisocyanate in the usual way, for example, at temperatures of from 50 to 100°C, optionally with the additional use of suitable catalysts, enter into reaction with the polyisocyanate is used in stoichiometric excess. As a product of the reaction to form the I PU A prepolymer with isocyanate end groups.

Polyol A1 is a linear polyoxyalkylene with a total degree of unsaturation <0.04 m-equiv/g, preferably <0.02 m-equiv/g and particularly preferably <0,017 m-equiv/g Polyol A1 is in the preferred embodiment, the molecular weight from 2,000 to 30,000 g/mol.

Under linear polyoxyalkylene refers to the reaction products of bifunctional original molecules in the form of short diols with acceleratedly as 1,2-propylene oxide or ethylene oxide, and alkalinity can be used individually, sequentially, or in the form of a mixture. The catalyst for polymerization is usually of the so-called bimetallic cyanide complex, commonly referred to as the DMC catalyst. Such polyols are commercially available, for example under the name Acclaim® and Arcol® Bayer, Preminol® Asahi Glass company, Alcupol® firm Repsol, as well as Poly-L® company Arch Chemicals. Due to the application when receiving DMC-catalyst polyols detect very low degree of unsaturation. This means that the content of these polyols in polyoxypropylene that at one end of the chain have a double bond, and at the other end of the OH-group (so-called "Manoli"), is very low. Monali are formed due to the fact that the propylene oxide during profilirovaniya isomerized in allyl alcohol, which formed as a result of polyoxypropylene with alliminium groups. Unsaturation is measured according to ASTM D-2849-69, "Testing Uretane Foam Polyol Raw Materials, and indicate in milliequivalent unsaturation per gram of polyol (m-equiv/g). The total degree of unsaturation (m-equiv/g) of these polyols corresponds to the content monola. The average molecular weight (or also of the overall content of Oh-groups) and the total degree of unsaturation is possible to calculate the average OH-functionality of the polyol. The preferred polyols are pure polyoxypropylene, as well as the so-called "EO-end" Polyoxypropylenediamine (i.e. with integral ethyleneoxide groups). The latter are special Polyoxypropylenediamine that can be obtained so that the net polyoxypropylene after polipropilenovaya alkoxylated with ethylene oxide and due to this have primary hydroxyl groups. Can also be used mixtures of these polyols.

For the remaining polyols comprising from 0 to 30 wt.%, take into account the following, well known in the chemistry of polyurethane polyols A2 that are not related to the type of polyols A1:

- polyoxyalkylene with an overall higher degree of unsaturation than 0.04 m-equiv/g and/or a low molecular weight and/or an OH functionality of more than 2, in particular, those which have a total degree of unsaturation <0.1 m-equiv/g and/or Molek is popular weight from 400 to 2000 and/or have an OH functionality of more than 2 and up to 3, which are the products of polyalkoxysiloxanes source of molecules with ethylene oxide, 1,2-propylene oxide, 1,2 - and 2,3-butyleneglycol, tetrahydrofuran or mixtures thereof;

- polybutadiene with polyhydroxyalkane terminal groups;

the polyether polyols obtained, for example, two - or trivalent alcohols, such as 1,2-ethanediol, diethylene glycol, 1,2-propandiol, dipropyleneglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, glycerol, 1,1,1-trimethylolpropane or mixtures of the aforementioned alcohols with organic dicarboxylic acids or their anhydrides or esters, such as, for example, succinic acid, glutaric acid, adipic acid, cork acid, sabotinova acid, decanedicarbonitrile acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and hexahydrophthalic acid or mixtures of the aforementioned acids, and also the polyether polyols from lactones, for example, ε-caprolacton;

- polycarbonatediol, which can be obtained by the reaction of, for example, the above - used for the synthesis of polyether polyols - alcohols with diallylmalonate, dellcorporate or phosgene;

in addition, low molecular weight compounds containing hydroxyl groups, such as 1,2-ethanediol, 1,2 - and 1,3-propandiol, neopentylglycol, e is ethylene glycol, triethylene glycol, the isomeric dipropyleneglycol and dipropyleneglycol, isomeric butandiol, pentandiol, hexandiol, heptanediol, octanediol, nonanediol, decanediol, undemandingly, 1,3 - and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 1,1,1-trimethyloctane, 1,1,1-trimethylolpropane and glycerin,

- as well as mixtures of the above-mentioned compounds containing hydroxyl groups.

To obtain a polyurethane prepolymer used polyisocyanates. The preferred polyisocyanates are the diisocyanates. As examples we mention the following, well known in polyurethane chemistry isocyanates:

2,4 - and 2,6-toluenediisocyanate (TDI) and any mixtures of these isomers, 4,4'-diphenylmethanediisocyanate (DHS), diphenylmethanediisocyanate, which are position isomers and oligomers and polymers of these isocyanate, 1,3 - and 1,4-delete the entry, 1,6-hexamethylenediisocyanate, 2,2,4 - and 2,4,4-trimethyl-1,6-hexamethylenediisocyanate, 1,12-dodecyltrimethoxysilane, cyclohexane-1,3 - and 1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl (= isophorondiisocyanate or IPDI), perhydro-2,4'- and -4,4'-di-phenylmethanesulfonyl, 1,3 - and 1,4-tetramethylcyclopentadiene, as well as any mixtures of the aforementioned isocyanates.

Polyamidimide B derived from polyamines and aldehydes by the reaction of condensation of the water separation. Such condensation reaction is well known and is described, for example, in Houben-Weyl, "Methods der organische Chemie", Vol. XI/2, page 73 and later. Thus interact equivalent to the number of aldehyde groups R1-CH=O with the primary amino groups of R2-NH2with the formation of alvinovich groups R1-CH=N-R2. R1and R2mean, for example, aliphatic, cycloaliphatic or aromatic residue, which, for example, may contain ester groups, carboxylic acid groups of simple ether and heteroatoms, and other aminogroup.

For example, R1and R2mean residues following polyamines (R2) or aldehydes (R1).

As polyamidimide B) can also be mixtures of different polyaluminum, in particular, mixtures of different polyaluminum obtained with different polyamines, reacted with different or the same aldehydes, in particular, also polyaluminum obtained using polyamines with different amidofunctional.

As polyamines we are talking about well known in polyurethane chemistry the polyamines, as they, among others, are used for two-component polyurethanes. In the examples should include the following:

aliphatic polyamine, such as Ethylenediamine, 1,2 - and 1,3-propandiamine, 2-methyl-1,2-propandiamine 2,2-dimethyl-1,3-propandiamine, 1,3 - and 1,4-butanediamine, 1,3 - and 1,5-pentanediamine, 1,6-hexanediamine, 2,2,4 - and 2,4,4-trimethylhexamethylenediamine and mixtures thereof, 1,7-heptadien, 1,8-octanediamine, 4-aminomethyl-1,8-octanediamine, 1,9-enantiomer, 1,10-decontamin, 1,11-undecanedioic, 1,12-dodecandioic, methyl-bis-(3-aminopropyl)amine, 1,5-diamino-2-methylpentane, 1,3-diaminopentane (DUMP), 2,5-dimethyl-1,6-hexamethylenediamine were, cycloaliphatic polyamine as 1,3- and 1,4-diaminocyclohexane, bis-(4-aminocyclohexane)methane, bis-(4-amino-3-methylcyclohexyl)methane, bis-(4-amino-3-ethylcyclohexyl)methane, bis-(4-amino-3,5-dimethylcyclohexyl)methane, 1-amino-3-aminomethyl-3,5,5-tri-methylcyclohexane (= ISOPHORONEDIAMINE or IPDA), 2 - and 4-methyl-1,3-diaminocyclohexane and mixtures thereof, 1,3 - and 1,4-bis-(aminomethyl)cyclohexane, 1-cyclohexylamino-3-aminopropane, 2,5(2,6)-bis-(aminomethyl)bicyclo[2.2.1]heptane (NBDA, produced Mitsui Chemicals), 3(4),8(9)-bis-(aminomethyl)tricyclo[5.2.1.02,6]decane (TCD-Diamin®production Celanese Chemicals), 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]-undecane, 1,3 - and 1,4-xylylenediamine, aliphatic polyamine containing groups of simple ester as the bis-(2-amino-ethyl)ether, 4,7-dioctadecyl-1,10-diamine, 4,9-dioxadodecane-1,12-diamine and their more high-molecular oligomers, polyoxyalkylene with theoretical amidofunctional 2 or 3, sold under the name Jeffamine®production Huntsman Chemicals as well as mixtures of the above floor is amines.

The preferred polyamines are 1,6-hexamethylenediamine were, 1,5-diamino-2-methylpentane, DUMP, IFDA, 4-aminomethyl-1,8-octanediamine, 1,3-xylylenediamine, 1,3-bis-(aminomethyl)cyclohexane, bis-(4-aminocyclohexane)methane, bis-(4-amino-3-methylcyclohexyl)methane, TCD-Diamin®different types of Jeffamine®: Jeffamine® EDR-148, Jeffamine® D-230, Jeffamine® D-400 and Jeffamine® T-403, and, in particular, a mixture of two or more of the aforementioned polyamines.

Under the aldehydes for the condensation reaction with the polyamines are meant, for example, the following:

aliphatic or cycloaliphatic aldehydes, as propanal, pavlinovic aldehyde (=trimethyloxonium aldehyde), Isobutyraldehyde, hexanal, 2-ethylhexanal, 2-methylbutanal, 2-ethylbutanal, octillery, valeric aldehyde, isovalerianic aldehyde, 2-methylvaleramide aldehyde, 2,3-dimethylarsinoyl aldehyde, 2-methylundecanal, cyclohexanecarboxaldehyde, methoxyacetanilide, 2-alkoxy-2-methylpropanal, as, for example, 2-methoxy-2-methylpropanal, ester of organic carboxylic acid and 2-hydroxy-2-methylpropanal, as, for example, 2-acetoxyisobutyryl, 3-alkoxy-2,2-DIMETHYLPROPANE, as, for example, 3-n-butoxy-2,2-dimethylpropyl, ester 2,2-dimethyl-3-hydroxypropyl and short-chain organic carboxylic acids, such as 2,2-dimethyl-3-acetylaminophenol and 2,2-d is methyl-3-isobutylacetophenone, cyclopropanecarboxaldehyde, 9-ethyl-3-carbonylchloride, 10-methylanthracene-9-carboxaldehyde, pyrocarbonate, benzaldehyde, o-, m - and p-tolylaldehyde, 2 - and 4-methylbenzaldehyde, 2 - and 4-ethylbenzaldehyde, 2 - and 4-propylbenzamide, 2 - and 4-butylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,4,5-trimethylbenzaldehyde, p-anisaldehyde, 3-methyl-p-anisaldehyde, m - and p-ethoxybenzaldehyde, m - and p-phenoxybenzaldehyde, nicotinamidase, terephthalic aldehyde, isophthalic aldehyde and diphenylacetaldehyde, as well as mixtures of the above aldehydes.

For use with highly aromatic isocyanates, such as TDI and MDI, the preferred aldehydes that do not form tautomeric enelow. With polyaluminum obtained from such setautoresize aldehydes, and prepolymers derived from aromatic polyisocyanates, can be prepared compositions, which are particularly stable in storage. Aldehydes, which can not form a tautomeric enelow are such that α-position to the carbonyl group does not contain C-H groups. This refers to aromatic aldehydes and aliphatic aldehydes with tertiary C atom in α-position to a carbonyl group.

Particularly preferred aldehydes are benzaldehyde, m-phenoxybenzaldehyde, isophthalic aldehyde, terephthalic al is Devid; in addition, pavlinovic aldehyde, and ester 2,2-dimethyl-3-hydroxypropyl and short-chain organic carboxylic acids, such as 2,2-dimethyl-3-acetylaminophenol and 2,2-dimethyl-3-isobutylacetophenone.

The polyurethane prepolymer A and polyamidimide B are mixed with each other, and polyamidimide B is dosed in an amount of from 0.1 to 1.1 equivalent alvinovich groups to the equivalent of isocyanate groups of the prepolymer A. Advanced to hydrolysis polyaniline can be used catalyst, for example, organic carboxylic acid, benzoic acid or salicylic acid, an anhydride of an organic carboxylic acid, as the anhydride of phthalic acid or anhydride hexahydrophthalic acid, silloway ester of organic carboxylic acids, organic sulfonic acids as p-toluensulfonate, or other organic or inorganic acids, or mixtures of the aforementioned acids.

By changing polyamidimide B in combination with the polyurethane prepolymer A, you can get the products with highly variable mechanical properties. Polyamidimide, which can lead to products with a particularly magkoelasticna properties are, for example, polyamidimide on the basis of different types of Jeffamine® or 1,5-diamino-2-methylpentane. Polyaluminum that lead to the receipt of the products osobenno high strength, are, for example, polyamidimide based on 1,6-diamine or 1,3-xylylenediamine, possibly mixed with more highly functional amines, such as 4-aminomethyl-1,8-octanediamine or Jeffamine® T-403. The correct selection of polyamidimide B, possibly in the form of a mixture of different polyaluminum, in combination with the described polyurethane prepolymers A, it is possible to provide desired mechanical properties of the solidified macromolecular compositions, for example, limit the elongation of up to 1000% and a tensile strength of about 1 MPa to 20 MPa.

Due to the possibility of variation polyamidimide B and the use of special high-molecular polyurethane prepolymer A can significantly reduce the number required in the industrial production of prepolymers for various polyurethane sealants, adhesives and coatings and linings, in particular floor coverings, which from the point of view of the complex mechanical properties satisfy an extremely wide requirements. Since the processing and storage of different prepolymers, taking into account their viscosity, moisture sensitivity and the requirement in industrial production, associated with high costs, reducing the number of prepolymers, for various products, is appropriate. In addition to t the th, such compositions allow as megabacteria construction sealants with very dry surface and elastomeric adhesives with a tensile strength of 20 MPa or more, which have low technical viscosity and quickly otverzhdajutsja without the formation of bubbles.

As additional components in the described compositions can be used, in particular, the following well-known in the industry polyurethane components:

plasticizers, for example, esters of organic carboxylic acids or their anhydrides, phthalates, such as dioctylphthalate or diisodecylphthalate, adipinate, as, for example, dioctyladipate, esters of organic sulfonic acids, polybutene and others that do not react with isocyanate compounds, solvents, inorganic and organic fillers, such as calcium carbonate, optionally precipitated, if necessary, calcium carbonate, coated with stearates, carbon black, kaolin, aluminum oxide, silicic acid, PVC powder, fibers, for example, polyethylene, pigments, catalysts of hydrolysis polyamidimide, organic carboxylic acid as, for example, benzoic acid and salicylic acid, the anhydrides of organic carboxylic acids, such as phthalic anhydride and anhydride hexahydrophthalic acid, silloway ether organic carbon is s acids, organic sulfonic acids as p-toluensulfonate, or other organic or inorganic acids, other catalysts, for example, ORGANOTIN compounds, such as, for example, dibutyltindilaurate, dibutylaminoethanol or other customary in polyurethane chemistry catalysts for the reaction of isocyanate groups, rheology modifiers, such as thickeners, for example, compounds of urea, polyamide waxes, bentonites or pyrogenic silicic acid, adhesion promoters, for example, epoxysilane, vinylsilane, isocyanatobenzene and aminosilane, turn aldehydes in eliminazione, dehumidifiers, for example, p-totalitarian and other active isocyanates, ether orthomorphisms acid, calcium oxide or molecular sieves, stabilizers against heat, light and UV radiation, defoamers, surfactants, fungicides, and others commonly used in industry polyurethane substance.

Described composition was prepared and stored in the absence of moisture. Such compositions are stable during storage, i.e. can in suitable packaging or place, such as, for example, in a barrel, bag or cartridge stored until use in a few months (to a year or longer). When applying the polyurethane composition are brought into contact with moisture, after which polyamidimide gidrolizu the Xia to aldehydes and polyamines, and polyamine containing react with isocyanate groups of the polyurethane prepolymer. The water necessary for the reaction, comes either from the air (air moisture), or the composition may be in contact with water-containing component, for example, by obmazyvanija, for example, a polishing agent, by spraying or dipping, or the composition may be added a component containing water, for example, in the form of a water-containing paste, which, for example, can be added through the static mixer.

If polyamidimide used in the fault, i.e. the ratio of alvinovich groups to isocyanate groups is selected below the stoichiometric excess isocyanate groups react with available water. Due to the above-described reactions, the composition cures.

Described composition suitable as a variety of sealants, for example, for sealing joints in building construction, as adhesives for bonding various substrates, for example, for bonding of structural elements in the manufacture of cars, trains or other industrial facilities, as well as a coating or cladding for various products or substrates. Composition at least partially in contact with the surface of an arbitrary substrate. Preferably the desired uniform contact in VI is e sealants or adhesives, coating or lining, and it is in those areas that are intended for connection in the form of bonding or sealing, or for coating the substrate. May be indispensable to the substrate or product before contacting were subjected to physical and/or chemical pre-treatment, for example, by grinding, sandblasting, machining brushes or the like, or by treatment with cleaners, solvents, adhesion promoters, solvents adhesion promoters or primers, or by drawing bridges adhesion or sealing gaskets.

Examples

"concerns" means weight part. All percentages, means, unless otherwise specified, the weight percent. Under full functionality of prepolymer" refers to the average isocyanate functionality of applied prepolymer. Full functionality of polyaluminum" means the average eliminou functionality used polyaluminum. Compositions that do not contain polyamidimide (comparative examples)were overidealize then air moisture.

Used polyols:

Arcol® PPG 2000 N (Bayer): linear polipropilenovaya with theoretical an OH functionality of 2, an average molecular weight of about 2000, a hydroxyl number of about 56 mg KOH/g, an unsaturation of about 0.01 m-equiv/year

Acclaim® 4200 N (Bayer): linear polypropylene PP is Minoxidil with theoretical an OH functionality of 2, the average molecular weight of about 4000 and a hydroxyl number of about 28 mg KOH/g, an unsaturation of about 0.005 m-equiv/year

Acclaim® 12200 (Bayer): linear polipropilenovaya with theoretical an OH functionality of 2, an average molecular weight of 12,000, a hydroxyl number of about 11 mg KOH/g, an unsaturation of about 0.005 m-equiv/year

Caradol® ED 56-11 (Shell): linear polipropilenovaya with theoretical an OH functionality of 2, an average molecular weight of about 2000, a hydroxyl number of about 56 mg KOH/g, an unsaturation of about 0.05 m-equiv/year

Voranol® EP 1900 (Dow): linear polypropyleneglycol with ethylenoxide end group, with theoretical OH functionality of 2, an average molecular weight of about 4000 and a hydroxyl number of about 29 mg KOH/g, an unsaturation of about 0.08 m-equiv/year

Caradol® MD34-02 (Shell): nonlinear polypropyleneglycol with ethylenoxide end group, with theoretical an OH functionality of 3, an average molecular weight of about 4900, a hydroxyl number of about 35 mg KOH/g, an unsaturation of about 0.08 m-equiv/year

Description of test methods:

The viscosity was measured at 23°C on a rotating viscometer company Haake (PK100/VT-500).

During the formation of a surface film (the cure time to touch, "tack-free time") was determined at 23°C if otnositelbnosti air 50%.

Strength utverzhdenii film tensile strength, ultimate elongation and modulus E with the elongation of 0.5-5% was determined for 7 days at 23°C and at a relative humidity of 50% according to DIN EN 53504 (rate of pulling of 200 mm/min).

About the bubbles qualitatively judged by the number of bubbles formed during curing (23°C, relative humidity 50%) films used for testing of mechanical properties (thickness 2 mm).

The force required during extrusion, was installed on the aluminum cartridges with a diameter of 45 mm, and the sealant was squeezed out of the tip of the cartridge through the hole size of 3 mm, the Extrusion was performed using the machine for tensile test at a speed of 60 mm/min

Separation of the filaments was determined by the fact that the cylindrical indenter with a diameter of 2 cm was deepened by 0.5 cm sealant (layer thickness 1 cm, temperature 20°C) and after about 1 sec it again pulled with constant speed (25 cm per 4 sec). The length remaining on the indenter thread sealant, defined as the separation of the thread was measured with an accuracy of 1 mm, the Process was repeated three times, and as a result was taken as the average value.

The surface of the cured sealant was evaluated for adhesiveness by light touch of finger.

Speed full curing was determined PR is 23° C and relative humidity of 50% on a Teflon base.

Stress at 100% elongation were determined according to DIN EN 28340, method A.

Getting aldimines and prepolymers

Polyamidimide A1

In a round flask 100 concerns Jeffamine® D-230 (Huntsman Chemicals). With strong cooling and vigorous stirring was added dropwise 91 concerns benzaldehyde. After adding another 10 minutes was stirred at room temperature, then water was fully released to the water-jet vacuum pump. Thus obtained reaction product had a content aldimine determined as the amine content and 4.65 mmol NH2/g and was used without further purification.

Polyamidimide A2

In a round flask 25 concerns TCD-Diamin® (Celanese Chemicals). With strong cooling and vigorous stirring was added dropwise 41 concerns 2,2-dimethyl-3-acetylaminophenol. After adding another 10 minutes was stirred at room temperature, then water was fully released to the water-jet vacuum pump. Thus obtained reaction product had a content aldimine defined as the number of amine, 4,22 mmol NH2/g and was used without further purification.

Polyamidimide A3

In a round flask were placed 15 concerns 1,5-diamino-2-methylpentane. With strong cooling and vigorous stirring was added dropwise 40 century is. 2,2-dimethyl-3-acetylaminophenol. After adding another 10 minutes was stirred at room temperature, then water was fully released to the water-jet vacuum pump. Thus obtained liquid reaction product had a content aldimine defined as the amine content, 4,94 mmol NH2/g and was used without further purification.

Polyamidimide A4

In a round flask were placed 44 concerns 1,3-xylylenediamine. With strong cooling and vigorous stirring was added dropwise 98 concerns 2,2-dimethyl-3-acetylaminophenol. After adding another 10 minutes was stirred at room temperature, then water was fully released to the water-jet vacuum pump. Thus obtained reaction product had a content aldimine defined as the amine content, equal to 4.97 mmol NH2/g and was used without further purification.

Polyamidimide A5

In a round flask were placed 100 concerns 4-aminomethyl-1,8-octanediamine. With strong cooling and vigorous stirring was added dropwise 287 concerns 2,2-dimethyl-3-acetylaminophenol. After adding another 10 minutes was stirred at room temperature, then water was fully released to the water-jet vacuum pump. Thus obtained reaction product had a content aldimine defined as the amine content, to 4.92 mmol NH2/g and PR is changed without further purification.

Polyamidimide A6

In a round flask was placed 67 concerns Jeffamine® D-230 (Huntsman Chemicals). With strong cooling and vigorous stirring was added dropwise 100 concerns 2,2-dimethyl-3-acetylaminophenol. After adding another 10 minutes was stirred at room temperature, then water was fully released to the water-jet vacuum pump. Thus obtained reaction product had a content aldimine defined as the amine content, of 3.56 mmol NH2/g and was used without further purification.

Polyamidimide A7

In a round flask were placed 100 concerns Jeffamine® T-403 (Huntsman Chemicals). With strong cooling and vigorous stirring was added dropwise 76 concerns benzaldehyde. After adding another 10 minutes was stirred at room temperature, then water was fully released to the water-jet vacuum pump. Thus obtained reaction product had a content aldimine defined as the amine content, 3.90 mmol NH2/g and was used without further purification.

The prepolymer P1

530 concerns polyol Acclaim® 4200 N and 72 concerns 4,4'-etilendiamindisuktsinatov (MDI; Desmodur® 44 MC L, Bayer) by a known method was made in the 80°C prepolymer with terminal NCO-groups. The reaction product had a content of free isocyanate groups defined by titrimetric method of 2.00% and a viscosity at 23°C 28 PA·C.

p> The prepolymer P2

661 concerns polyol Caradol® ED56-11 and 139 concerns 4,4'-etilendiamindisuktsinatov (MDI; Desmodur® 44 MC L, Bayer) by a known method was made in the 80°C prepolymer with terminal NCO-groups. The reaction product had a content of free isocyanate groups defined by titrimetric method of 2.06% and a viscosity at 23°C 102 PA·C.

The prepolymer P3

1262 concerns polyol Arcol® PPG 2000 n and 338 concerns 4,4'-etilendiamindisuktsinatov (MDI; Desmodur® 44 MC L, Bayer) by a known method was made in the 80°C prepolymer with terminal NCO-groups. The reaction product had a content of free isocyanate groups defined titrimetric method, 3,61% and a viscosity at 23°C 37 PA·C.

The prepolymer P4

627 concerns polyol Caradol® ED56-11 and 172 concerns 4,4'-etilendiamindisuktsinatov (MDI; Desmodur® 44 MC L, Bayer) by a known method was made in the 80°C prepolymer with terminal NCO-groups. The reaction product had a content of free isocyanate groups defined titrimetric method, 3,59% and a viscosity at 23°C 38 PA·C.

The prepolymer P5

259 concerns polyol Acclaim® 4200 N, 517 concerns polyol Caradol® MD34-02 and 124 concerns 4,4'-etilendiamindisuktsinatov (MDI; Desmodur® 44 MC L, Bayer) by a known method was made in the 80°C prepolymer with terminal NCO-groups. The reaction product had a content of free isocyanate groups, a certain titrimetry the definition method 2,30% and a viscosity at 23°C 92 PA·C.

The prepolymer P6

540 concerns polyol Acclaim® 4200 N, 245 concerns polyol Caradol® MD34-02 and 115 concerns 4,4'-etilendiamindisuktsinatov (MDI; Desmodur® 44 MC L, Bayer) by a known method was made in the 80°C prepolymer with terminal NCO-groups. The reaction product had a content of free isocyanate groups defined titrimetric method, 2,22% and a viscosity at 23°C 47 PA·C.

The prepolymer P7

1462 concerns polyol Acclaim® 4200 N and 138 concerns diisocyanate (TDI; Desmodur® T-80 P L, Bayer; a mixture of 80:20 2,4 - and 2,6-isomers) by a known method were made at 100°C prepolymer with terminal NCO-groups. The reaction product had a content of free isocyanate groups defined titrimetric method, 2,12% and a viscosity at 23°C 11 PA·C.

The prepolymer P8

1710 concerns polyol Acclaim® 12200 and 91 concerns 4,4'-etilendiamindisuktsinatov (MDI; Desmodur® 44 MC L, Bayer) by a known method were made at 100°C prepolymer with terminal NCO-groups. The reaction product had a content of free isocyanate groups defined titrimetric method, 0.88% and a viscosity at 23°C 58 PA·C.

The prepolymer P9

221 concerns polyol Acclaim® 4200 N, 13 concerns tripropyleneglycol and 67 concerns 4,4'-etilendiamindisuktsinatov (MDI; Desmodur® 44 MC L, Bayer) by a known method was made in the 80°C prepolymer with terminal NCO-groups. Productregcom had a content of free isocyanate groups, certain titrimetric method, 3,70% and a viscosity at 23°C 38 PA·C.

The prepolymer P10

684 concerns polyol Acclaim® 4200 N, 15 concerns 1,2-propane diol and 200 concerns 4,4'-etilendiamindisuktsinatov (MDI; Desmodur® 44 MC L, Bayer) by a known method was made in the 80°C prepolymer with terminal NCO-groups. The reaction product had a content of free isocyanate groups defined titrimetric method, 3,76% and a viscosity at 23°C 46 PA·C.

The prepolymer P11

606 concerns polyol Acclaim® 4200 N, 56 concerns tripropyleneglycol and 238 concerns 4,4'-etilendiamindisuktsinatov (MDI; Desmodur® 44 MC L, Bayer) by a known method was made in the 80°C prepolymer with terminal NCO-groups. The reaction product had a content of free isocyanate groups defined titrimetric method, a 4.53% and a viscosity at 23°C 58 PA·C.

The prepolymer P12

565 concerns polyol Acclaim® 4200 N, 35 concerns neopentyl glycol and 255 concerns 4,4'-etilendiamindisuktsinatov (MDI; Desmodur® 44 MC L, Bayer) by a known method was made in the 80°C prepolymer with terminal NCO-groups. The reaction product had a content of free isocyanate groups defined titrimetric method, 5,01% and a viscosity at 23°C 48 PA·C.

The prepolymer P13

518 concerns polyol Acclaim® 4200 N and 41 concerns diisocyanate (TDI; Desmodur® T-80 P L, Bayer; a mixture of 80:20 2,4 - and 2,6-isomers) by a known method become and at 100° C prepolymer with terminal NCO-groups. The reaction product had a content of free isocyanate groups defined by titrimetric method of 1.50% and a viscosity at 23°C 18 PA·C.

The prepolymer P14

660 concerns polyol Acclaim® 4200 N, 330 concerns polyol Caradol® MD34-02 and 84 concerns diisocyanate (TDI; Desmodur® T-80 P L, Bayer; a mixture of 80:20 2,4 - and 2,6-isomers) by a known method was made in the 80°C prepolymer with terminal NCO-groups. The reaction product had a content of free isocyanate groups defined by titrimetric method of 1.50% and a viscosity at 23°C 27 PA·C.

The prepolymer P15

673 concerns polyol Voranol® EP 1900 and 55 concerns diisocyanate (TDI; Desmodur® T-80 P L, Bayer; a mixture of 80:20 2,4 - and 2,6-isomers) by a known method was made in the 80°C prepolymer with terminal NCO-groups. The reaction product had a content of free isocyanate groups defined by titrimetric method and 1.51% and a viscosity at 23°C 21 PA·C.

Examples 1-4 (according to the invention) and examples 5 and 6 (comparison)

The prepolymers and aldimine listed in table 1, homogeneous mixed at the ratio of NH2/NCO (i.e. equivalent alvinovich groups to the equivalent of isocyanate groups of the prepolymer)0.9/1.0 in. To the mixture was added benzoic acid (350 mg/100 g of prepolymer), again uniformly mixed and immediately poured into a sealed tubes, which videri the Ali 15 hours at 60° C. Then the portion of the mixture was poured into PTFE coated steel sheet (thickness about 2 mm), utverjdali within 7 days at 23°C and relative humidity of 50% and then measured the mechanical properties of fully utverzhdenii film. With the remaining contents of the tube were determined by high storage stability by measuring the viscosity before and after storage for 7 days at 60°C. the Results are given in table 1.

The results show that the compositions according to the invention of examples 1-4 (prepolymer based on a linear polyol with a low degree of unsaturation, cured by polyaluminum) depending on used polyamidimide are changing in a wide range of mechanical strength and modulus, as well as a very low viscosity, good storage stability, high activity and otverzhdajutsja without bubbles. Comparative example 5 according to the prior art (prepolymer based on the normal linear polyol pre-elongated-diisocyanate, cured by polyaluminum) is in contrast greatly increased viscosity and applying the same polyamidimide (example 5 as compared with example 4) significantly lower tensile strength. Comparative example 6 according to the prior art (prepolymer based on a linear polyol with a low degree is d unsaturation, cured by moisture in air) detects an insufficient activity (slow time of the formation of a crust) and a distinct tendency to the formation of bubbles.

Table 1
Example12345< / br>
against.
6< / br>
against.
The prepolymerP1P1P1P1P2P1
PolyamidimideA1A2A3A4A4-
The NCO content (wt.%)2,002,002,002,00to 2.062,00
Viscosity before storage (PA·)282726279128
The viscosity after storage (PA·)323329329631
The time of crust formation (min)5233433530600
The formation of bubblesNoN is t NoNoNoA lot
Tensile strength (MPa)4,28,38,812,1a 4.9nez.
Ultimate elongation (%)10001300130013001400nez.
Module E Of 0.5-5% (MPa)1,61,92,013,1the 15.6nez.
(NIS. = not measured)

Example 7 (according to the invention) and example 8 (comparison)

Songs from different prepolymers and aldimines obtained and tested according to example 1. Resulting prepolymers and aldimine, and the results are given in table 2.

The results show that the composition according to the invention of example 7 (linear polyol with a low degree of unsaturation) is compared with prepared according to the prior art comparative example 8 (normal linear polyol) is noticeably higher tensile strength, while that of other comparable properties.

Table 2
Example78 (comparison)
The prepolymerP3P4
PolyamidimideA4A4
The NCO content (wt.%)3,613,59
Viscosity before storage (PA·)3734
The viscosity after storage (PA·)3835
The time of crust formation (min)3230
The formation of bubblesNoNo
Tensile strength (MPa)11,37,2
Ultimate elongation (%)710700
Module E Of 0.5-5% (MPa)26,628,8

Examples 9, 12-14 (according to the invention) and examples 10, 11, 15, 16 (comparison)

Songs from different prepolymers and aldimines obtained and tested according to example 1. Resulting prepolymers and aldimine, and the results are given in table 3.

The results show that the compositions according to the invention of examples 9 and 12-14 (prepolymer based on a linear polyol with a low degree of unsaturation, curable mixture of polyaluminum full functionality >2) are compared with prepared according to the prior art comparative example and 10 and 15 (prepolymer with full functionality > 2 on the basis of a mixture of linear and non-linear polyol, curing polyaluminum full functionality >2) lower viscosity (example 10 in comparison with example 9 and example 15 in comparison with example 14). Prepared according to the prior art comparative examples 11 and 16 (prepolymer with full functionality >2 on the basis of a mixture of linear and non-linear polyol cured with moisture) is compared with other examples of insufficient activity (slow time of the formation of a crust), as well as the tendency to form bubbles.

Table 3
Example910 EUR.11 EUR.12131415 EUR.16 EUR.
The prepolymerP1P5P5P1P1P1P6P6
Polyamidimide(s), relationship (concerns/concerns)A2/A5, 2/1A2-A2/A5, 7/1A6/A5, 7/1A4/A5, 7/1A2-
The functionality of the prepolymers2,02,32,32,0 2,02,12,1
The overall functionality of polyaluminum2,32,0(2,0)2,12,12,12,0(2,0)
The NCO content (wt. %)2,002,302,302,002,002,002,222,22
Viscosity before storage (PA·)3087922825284849
The viscosity after storage (PA·)381081053529326358
The time of crust formation (min)241224023202315320
The formation of bubblesNoNoBitNoNoNoNoA lot
Tensile strength (MPa)2,32,62,34,12,85,03,7nez.
270230190620640450400nez.
Module E 0.5-5% (MPa)2,43,05,22,01,49,43,0nez.
(NIS. = not measured)

Example 17 (according to the invention) and example 18 (comparison)

Songs from different prepolymers and aldimines obtained and tested according to example 1. Resulting prepolymers and aldimine, and the results are given in table 4.

The results show that the composition according to the invention of example 17 (prepolymer based on a linear polyol with a low degree of unsaturation, curing polyaluminum) has a very low viscosity, good mechanical properties and high activity (fast formation of a crust) and cures without bubbles. On the contrary, comparative example 18 prepared according to the prior art (prepolymer based on a linear polyol with a low degree of unsaturation, moisture cured), has insufficient activity and tends to the formation of bubbles.

Table 4
Example 1718 EUR.
The prepolymerP7P7
PolyamidimideA4-
The NCO content (wt.%)2,122,12
Viscosity before storage (PA·)1111
The viscosity after storage (PA·)1212
The time of crust formation (min)37>600
The formation of bubblesNoBit
Tensile strength (MPa)10,2Remains sticky, soft;

nez.
Ultimate elongation (%)1300
Module E Of 0.5-5% (MPa)10,3
(NIS. = not measured)

Examples 19-20 (according to the invention) and example 21 (comparison)

Songs from different prepolymers and aldimines obtained and tested as described in example 1. Resulting prepolymers and aldimine, and the results are given in table 5.

The results show that the compositions according to the invention of example 19 or 20 (prepolymer based on long-chain linear polyol with a low degree ninasimone the tee, curable mixture of polyaluminum with full functionality 2 or >2) have good mechanical properties, high activity (short crust formation), as well as otverzhdajutsja without bubbles. Example 20 with a mixture of polyaluminum with full functionality >2 detects compared with example 19 a higher tensile strength. Comparative example 21, prepared according to the prior art (prepolymer based on long-chain linear polyol with a low degree of unsaturation, moisture cured), is compared with examples 19 and 20 according to the invention is insufficient activity and tends to bubble formation. The storage stability for these three examples in each case, good (slight increase in viscosity during storage).

Table 5
Example192021 EUR.
The prepolymerP8P8P8
Polyamidimide(s),relationship (concerns/concerns)A4A4/A5, 7/1-
The NCO content (wt. %)0,880,880,88
Viscosity before storage (PA·)58 6660
The viscosity after storage (PA·)728270
The time of crust formation (min)5248>600
The formation of bubblesNoNoSome
Tensile strength (MPa)4,2the 4.7Remains soft, pasty; nez.
Ultimate elongation (%)>13001040
Module E Of 0.5-5% (MPa)2,92,4
(NIS. = not measured)

Table 6
Example22232425 EUR.2627 EUR.2829 EUR.3031 EUR.
The prepolymerP9P9P9P9P10P10P11P11P12P12
Polyamidimide(s), relationship (concerns/concerns)A2A3A4- A2/A5, 7/1-A2/A5, 7/1-A2/A5, 3/1-
The NCO content (wt.%)3,703,703,703,703,763,764,534,535,015,01
Viscosity before storage (PA·)36353638434656584648
The viscosity after storage (PA·)43374043505165645552
The time of crust formation (min)415142360454204236041480
The formation of bubblesNoNoNoA lotNoA lotNoA lotNoA lot
Tensile strength (MPa)15,014,5of 17.0nez.14,1 nez.the 15.6nez.18,4nez.
Ultimate elongation (%)790770810nez.500nez.600nez.330nez.
Module E Of 0.5-5% (MPa)5,84,133,1nez.5,3nez.10,5nez.40,0nez.
(NIS. = not measured)

Examples 22-24, 26, 28, 30 (according to the invention) and examples 25, 27, 29, 31 (comparison)

Songs from different prepolymers and aldimines obtained and tested according to example 1. Resulting prepolymers with different content of isocyanates and aldimine, and the results are given in table 6.

The results show that the compositions according to the invention examples 22 to 24 or 26, 28 and 30 (prepolymers based on linear polyol with a low degree of unsaturation and low molecular weight diol, curing polyaluminum or a mixture of polyaluminum full functionality equal to or >2) have very good mechanical properties which can be varied by changing polyamidimide. The corresponding prepolymers in comparative examples 25, 27, 29 and moglena the prior art overidealize air moisture. Comparative examples detect very low activity (a great time and crust formation) and a strong tendency to the formation of bubbles. Values of mechanical properties for these samples because of the large number of bubbles could not be measured accurately.

Example 32 (sealant) (according to the invention)

30 concerns prepolymer P13, 25 concerns chalk powder Omyacarb® 5 GU (Omya), 20 concerns plasticizer Palatinol® Z (diisodecylphthalate, BASF), 10 concerns of PVC powder, Solvic® 373 MC (Solvay), 10 concerns thickener Crayvallac® super (Cray Valley), 3 concerns xylene, 0,2 concerns stabilizer Irganox® 1010 (Ciba), 0,2 concerns silane Silquest® A-187 (OSi Crompton), 0,1 concerns benzoic acid, 1,1 concerns polyamidimide A1 and 1.6 concerns polyamidimide A7 processed in a vacuum mixer until homogeneous, not containing lumps of paste, which was poured into a sealed cartridges.

The test results of the sealant are shown in table 7.

Example 33 (sealant) (comparison)

30 concerns prepolymer P14, 25 concerns chalk powder Omyacarb® 5 GU (Omya), 20 concerns plasticizer Palatinol® Z (diisodecylphthalate, BASF), 10 concerns of PVC powder, Solvic® 373 MC (Solvay), 10 concerns thickener Crayvallac® super (Cray Valley), 3 concerns xylene, 0,2 concerns stabilizer Irganox® 1010 (Ciba), 0,2 concerns silane Silquest® A-187 (OSi Crompton), 0,1 concerns benzoic acid and 2,2 concerns polyamidimide A1 processed in a vacuum mixer until homogeneous, not containing lumps of paste, which again is ivali in sealed cartridges.

The test results of the sealant are shown in table 7.

The sealant according to the invention of example 32 (prepolymer based on a linear polyol with a low degree of unsaturation, partially cured mixture of polyaluminum full functionality >2) is compared with the sealant of comparative example 33 according to the prior art (the prepolymer with the overall functionality >2 on the basis of a mixture of linear and non-linear polyol, partially curable polyaluminum overall functionality 2) lower extrusion force and the shorter lead of the thread, due to the lower viscosity of the prepolymer, with a dry surface quality and the rest with similar values of mechanical properties, activity and stability during storage.

Example 34 (sealant) (comparison)

30 concerns prepolymer P15, 25 concerns chalk powder Omyacarb® 5 GU (Omya), 20 concerns plasticizer Palatinol® Z (diisodecylphthalate, BASF), 10 concerns of PVC powder, Solvic® 373 MC (Solvay), 10 concerns thickener Crayvallac® super (Cray Valley), 3 concerns xylene, 0,2 concerns stabilizer Irganox® 1010 (Ciba), 0,2 concerns silane Silquest® A-187 (OSi Crompton), 0,1 concerns benzoic acid, 1,1 concerns polyamidimide A1 and 1.6 concerns polyamidimide A7 processed in a vacuum mixer until homogeneous, not containing lumps of paste, which was poured into a sealed cartridges.

The sealant test results are given in table the CE 7.

The sealant according to the invention of example 32 (prepolymer based on a linear polyol with a low degree of unsaturation, partially cured mixture of polyaluminum overall functionality >2) are compared with prepared according to the prior art sealant of comparative example 34 (prepolymer based on the normal linear polyol, partially cured mixture polyamidimide overall functionality >2) significantly better mechanical properties and dry surface quality.

Table 7
Example3233 EUR.34 EUR.
The quality of the surface after curingDryDrySticky
The time of crust formation (min)25090135
Speed full cure (mm/day)1,82,42,5
The shore hardness (A)474418
Separation of strands (mm)284015
The extrusion force (n)443558271
The storage stabilityRules./td> Standards.Standards.
Tensile strength (MPa)2,23,00,3
Ultimate elongation (%)8801080250
Stress at 100%elongation (MPa)0,980,810,18

1. The composition used as an adhesive, sealant, coating or lining and comprising at least one polyurethane prepolymer And isocyanate terminal groups derived from at least one MDI at least one polyol A1 and optionally at least one polyol A2, as defined herein A1: linear polyoxyalkylene with the degree of unsaturation <0.04 m-equiv/g; A2: polyol in an amount of 0-30 wt.%, preferably 0-20 wt.%, in particular, 0-10 wt.%, in calculating the total number of A1+A2; and at least one polyamidimide Century

2. The composition according to claim 1, characterized in that the polyol A1 has a molecular weight of 2000-30000 g/mol, in particular 2000-20000 g/mol.

3. Composition according to one of the preceding paragraphs, characterized in that the degree of unsaturation of the polyol A1 is <0.02 m-equiv/g, in particular <0,017 m-equiv/year

4. The composition according to claim 1, characterized in that the polyol A1 is a polyol obtained DMC-catalysis.

5. Composition p is 1, characterized in that the polyol A1 is Polyoxypropylenediamine or Polyoxypropylenediamine with integral ethyleneoxide groups.

6. The composition according to claim 1, characterized in that the polyol A2 is polyoxyethyleneglycol with the degree of unsaturation >0.04 m-equiv/mol.

7. The composition according to claim 1, characterized in that the polyol A2 is polyoxyethyleneglycol with a molecular weight of 400-2000 g/mol.

8. The composition according to claim 1, characterized in that the polyol A2 is polyoxyethyleneglycol with IT-functionality of more than 2 and up to about 3.

9. The composition according to claim 1, characterized in that the polyol A2 is selected from the group comprising 1,2-ethanediol, 1,2 - and 1,3-propandiol, neopentylglycol, diethylene glycol, triethylene glycol, the isomeric dipropyleneglycol and dipropyleneglycol, isomeric butandiol, pentandiol, hexandiol, heptanediol, octanediol, nonanediol, decanediol, undemandingly, 1,3 - and 1,4-cyclohexanedimethanol, hydrogenated bisphenol a, 1,1,1-trimethyloctane, 1,1,1-trimethylolpropane and glycerin.

10. The composition according to claim 1, characterized in that the polyisocyanate is a diisocyanate.

11. The composition according to claim 1, characterized in that the aldehyde, which is the basis polyamidimide In, α-position relative to the carbonyl group has a C-H group.

12. The composition according to claim 1, characterized in that the polyurethane prepolymer a and polyamidine who are in the ratio of 0.1 to 1.1 equivalent alvinovich groups to the equivalent of isocyanate groups.

13. Composition according to one of claims 1 to 12, characterized in that it is suitable as an adhesive.

14. Composition according to one of claims 1 to 12, characterized in that suitable as sealant.

15. Composition according to one of claims 1 to 12, characterized in that suitable as cover.

16. Composition according to one of claims 1 to 12, characterized in that suitable as lining.

17. Composition according to one of claims 1 to 12, characterized in that suitable for the manufacture of the device.

18. Composition according to one of claims 1 to 12, characterized in that suitable for the manufacture of the product.

19. The method of obtaining the composition according to one of claims 1 to 12, comprising a step for polyamidimide by reacting the aldehyde with the amine in a known manner.

20. Method of bonding, characterized in that it includes a step of contacting the surface of an arbitrary substrate with a composition according to one of claims 1 to 12.

21. The method according to claim 20, characterized in that it comprises the additional step of curing in air.

22. The method according to claim 20, characterized in that it further includes a step of contacting the surface of an arbitrary substrate with a water-containing component or adulteration.



 

Same patents:

FIELD: polymer materials.

SUBSTANCE: invention relates to compositions based on polyols and high-molecular weight diisocyanates with low monomer content as well as to a method for preparation of indicated compositions as binders for reactive glues. In particular, invention provides reactive polyurethane composition based on polyols and high-molecular weight diisocyanates prepared by reaction of diols having average number molecular weight mot higher than 2000 with monomeric diisocyanates having molecular weight not higher than 500. Thus obtained high-molecular weight diisocyanates have maximum monomer content 10%. Invention also describes a method for preparation of indicated composition. Thus obtained compositions are used as glues/hermetics imparting improved adhesion characteristics and having significantly reduced contents of health-detrimental monomeric diisocyanates having molecular weight below 500. For instance, resistance to detachment of film attached to surface using claimed glue is 4.3 N/mm, heat resistance lies at a level of 148°C, and frost resistance below -30°C.

EFFECT: improved adhesive characteristics.

13 cl, 3 tbl, 20 ex

Glue composition // 2271377

FIELD: adhesives.

SUBSTANCE: invention relates to compositions based of synthetic high-molecular weight compounds and, in particular, to composition comprising polyurethane-based preparation DESMOCOLL, perchlorovinyl resin, epoxide resin, aliphatic-series polyamine, and polar organic solvent.

EFFECT: enabled retention of high elasticity of glue joint and considerably increased gluing strength for siloxane-coated materials, kapron fabrics, and glass cloth.

1 tbl

FIELD: gluing compositions.

SUBSTANCE: invention relates to a composition that comprises polypropylene glycol glycerol adipinate as a polyester, monophenyl urethane, stabilizing agent, phenolformaldehyde resin, p-dinitrobenzene as a polymerization activating agent, urotropin as a cross-linking agent, a mixture of cyclohexanone, xylene and methyl ethyl ketone as a solvent. The composition can be used in applying on cold and hot surface. Invention is used for teasing articles made of industrial rubber, in preparing monocomponent polyurethane glues for teasing rubber surfaces by electrostatic flocculation method and can be used in industrial rubber and automobile industries. Invention provides conferring thermal stability, reducing vulcanization time and enhancing adhesion strength.

EFFECT: improved and valuable properties of composition.

5 tbl

FIELD: rocketry; development of a composition of binding substance for manufacture of the brush type products.

SUBSTANCE: the invention is pertaining to the field of rocketry, in particular, to development of a composition of binding substance for manufacture of the brush type products. The composition contains, in mass %: hydroxyl-containing polybutadiene rubber - 31.0-33.0; zinc oxide or carbon technical - 7.4-8.0; 1.4- butyleneglycol - 0.7-0.8; trimethylolpropane - 0.08-0.1; transformer oil - 5.2-5.6; stannous dibutyldilaurate - 0.013-0.036; a hardener - oligodiene urethane prepolymer in a combination with 20 % solution of triphenylmethanetriisocyanate in dichlorethane or 27 % solution of triphenylmethanetriisocyanate in ethylacetate with the contents of isocyanate groups of 3.5-4.5% and 53.0-55.5%. The technical result of the invention - manufacture of the composition of binding substance with the high mechanical, binding and operational characteristics and with provision of serviceability of the finished products in the range of temperatures from plus 50°C to minus 50°C at action of high loadings.

EFFECT: the invention ensures production of the binding substance composition with high mechanical, binding and operational characteristics and serviceability of the finished products at the temperatures of plus 50°C - minus 50°C at action of high loadings.

1 tbl

Glue composition // 2259381

FIELD: rocket engineering and adhesives.

SUBSTANCE: invention provides composition for attaching solid fuel charge to rocket engine body, said composition being constituted by oxidant, fuel, binder based on synthetic rubber plasticized with mineral plasticizer, transformer and vaseline oils, curing additives, and catalysts. More specifically, glue composition contains urethane rubber with intrinsic viscosity [η] = 0.3-1.3 Dl/g and weight percentage of double bonds 0.5-2.5%, curing agent of the type of dinitrile oxides reactive to double bonds, and solid epoxide resin from diphenylolpropane and epychlorhydrin as active filler.

EFFECT: increased resistance to diffusion of oils from fuel and optimized curing regime regarding curing temperature and duration synchronization.

9 tbl, 7 ex

The invention relates to a stable form, adhesive pencil, which can be used not only for bonding paper, but as a universal adhesive, and method of its manufacture

Drogenase floor // 2220178
The invention relates to the field of compositions used as coatings in the equipment of playgrounds in the courtyards of houses, parks, stadiums, flooring in sports facilities

Disperse system // 2204570
The invention relates to one-component dispersion, which has the ability of blending at low (room) temperatures

The invention relates to adhesives, and more particularly to free of water or contains little water, partially crystalline, solid at room temperature glue

The invention relates to the production of a composition for binding the bundle of the fuel elements of solid fuel elements starting of the engine of hand grenades and anti-tank guided relates to rocket technology

FIELD: composite materials.

SUBSTANCE: in particular, invention relates to employment of polyisocyanates compositions as binders for composites containing lignocellulose fibers such as oriented wood chipboard.

EFFECT: improved performance characteristics regarding detachment of product as compared to conventional polyisocyanates employed for binding lignocellulose material.

11 cl, 7 tbl, 8 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to polyurethane-polyol compositions comprising product of reaction of a polyol and Herbert alcohol, the two containing In average 12 carbon atoms. Preferred polyols are α,β-diols and α,β-diols. Polyurethane-polyol compositions exhibit very low viscosity and are particularly suitable in coating compositions with very low content of volatile organics. Hardened coating obtained from claimed compositions ensure high resistance to cracking and can be applied on various substrates such as metal, plastic, wood, glass, ceramics.

EFFECT: increased strength of coatings on a variety of substrates.

5 cl, 3 tbl

FIELD: coating compositions.

SUBSTANCE: invention relates to composition used for coating applying and comprising polyisocyanate compound, hydroxyl-functional film-forming polymer and nonvolatile branched monoatomic alcohol wherein the aliphatic branched monoatomic alcohol is preferable but long-chain nonvolatile branched monoatomic alcohols are more preferable. This provides preparing compositions for applying coatings that possess the improved indices of fluidity and can be used for preparing coatings with the improved appearance and without the negative effect on other properties. Also, invention relates to the multiple composition fir applying coatings. The multicomponent composition for applying coatings represents the bicomponent composition for applying coatings preferably that comprises the polyisocyanate component in addition to hydroxyl-functional film-forming polymer comprising nonvolatile branched monoatomic alcohol also. Also, invention relates to a method for car finishing comprising applying compositions for applying coating on car and to a method for preparing the multilayer coating.

EFFECT: valuable properties of composition.

30 cl, 1 tbl, 2 ex

FIELD: chemistry of polymers.

SUBSTANCE: invention relates to aromatic polyurethane polyols used as components of priming compositions. Invention describes the priming composition comprising aromatic polyurethane polyol including product of reaction: (a) at least one diol component among number of α,β-diols, α,γ-diols and their mixtures; (b) at least one triisocyanate; (c) at least one diisocyanate wherein at least one isocyanate is aromatic one, and molecular mass or aromatic polyurethane polyol is 3000 Da, not above, and a cross-linking agent also. Prepared aromatic polyurethane polyol shows viscosity value by Brookfield at the level 8260 centipoises, OH-number 192.6 KOH/g and the dispersity (Mn/Mw) at the level 3.0. Priming compositions prepared by using indicated aromatic polyurethane polyol are useful in finishing large means of transportation, for example, trains, trucks, buses and airplanes, in particular, in vehicle body works. Also, invention relates methods for applying priming compositions on support comprising applying indicated compositions, and to a method for finishing car in repairs comprising applying the indicated priming composition.

EFFECT: improved and valuable properties of composition.

11 cl, 5 tbl, 12 ex

FIELD: protective coatings.

SUBSTANCE: invention relates to a method for applying onto wood substrate coating with increased resistance to effects of chemical products. Method comprises following stages: (i) addition, to aqueous polyatomic alcohol suspension, of composition based on isocyanate(s) and anionic surfactant having hydrophilic portion containing anionic group and lipophilic portion containing hydrocarbon radical, isocyanate(s)-based composition containing no more than 30% surfactant bound to isocyanate group, to form aqueous emulsion of isocyanate(s) and surfactant; (ii) applying resulting mixture onto wood surface of substrate; and (iii) aging to complete reaction of isocyanate(s) with polyatomic alcohol required to form polyurethane coating.

EFFECT: increased strength of coating (at a level of 90 units) and acquired resistance to a variety of chemical, cosmetic, and woof products according to corresponding standard.

18 cl, 4 dwg, 5 ex

FIELD: protective coatings.

SUBSTANCE: invention relates to methods for protecting metallic surfaces of geophysical instruments for exploring wells against combined action of generated acoustic field, drilling mud components, and formation fluids causing rapid wear of well instrument body. Gluing of protective polyurethane coating to cleaned and degreased metallic surface is effected by a way wherein glue composition based on triphenylmethanetriisocyanate in organic solvent is preliminarily applied onto surface as a layer with thickness 0.5-5 μm, preferably 1-3 μm, after which applied film is aged for 15-30 min at 100°C or for 12-18 h at 20-25°C and relative air humidity 30 to 98% and then protective coating based on lacquer polyurethane and/or poured polyurethane composition is deposited and hardened by a known method.

EFFECT: improved quality of received acoustic signal.

4 cl, 1 tbl, 3 ex

FIELD: building materials.

SUBSTANCE: invention relates to polyisocyanate compositions used for impregnation of concrete construction surfaces for aims of their anti-corrosive protection, and to a method for concrete impregnating by using the indicated composition. The claimed composition comprises earth-alkali metal salt dissolvable in polyisocyanate taken in the amount 0.1-5 mas. p. p. per 100 mas. p. p. of polyisocyanate. Except for, the composition can comprise additionally a hydrophobic solvent and a hydrophobic plasticizer. The claimed composition provides the deep penetration of impregnation up to 9.5 mm. The composition can be used in impregnation of brick masonry, sandy-cement covering for floors, in reconstruction of reservoirs for liquids storage and ferroconcrete constructions.

EFFECT: improved and valuable properties of composition.

6 cl, 1 tbl, 27 ex

FIELD: protective coatings.

SUBSTANCE: invention provides coating composition comprising first compound containing at least one bicyclo-ortho-ester functional group, second compound containing at least two isocyanate groups, and third compound containing at least one thiol group.

EFFECT: enlarged assortment of coatings.

19 cl, 10 tbl, 30 ex

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

FIELD: protective coatings.

SUBSTANCE: invention relates to composition to form coatings with quick-setting surface at ambient temperature for use in re-finishing industry, in manufacture of clear coating, and as primer layer in multilayer coating. Composition contains at least one latent base-type photoactivator and base-catalyzed polymerizable or hardenable organic material including isocyanate-reactive groups bearing at least one thiol group.

EFFECT: enabled preparation of compositions, which can be UV hardened and are characterized by acceptable setting velocity at ambient temperature in locations not easily accessible for UV emission.

15 cl, 11 tbl, 10 ex

FIELD: tools for grinding.

SUBSTANCE: composition comprises abrasive and polyurethane binder that comprises polyol and polyisocyanate. The ratio of polyol to polyisocyanate is from 1:1 to 1:1.5. The limit ratio of abrasive to polyurethane binder is from 80:20 to 10:90. The optimal ratio of the abrasive filler to the binder is 50:50. The polyurethane binder comprises polyol and polyisocyanate. Polyol is composed of simple polyester triol with a molecular mass of 5000, polyester diol with a molecular mass of 400-700, activator, crystalline hydrate, and surface-active agent. The method of manufacturing flexible abrasive tool comprises combining the abrasive with the polyurethane binder, mixing the mixture, filling into the mould, and solidifying. The components of the binder are made of polyol and polyisocyanate. The abrasive filler is separated into two parts proportional to the ratio of polyol to polyisocyanate. The components of each part are mixed and the parts are combined and mixed for 0.5-2 min and are then supplied to the moulds for solidification.

EFFECT: improved quality and simplified manufacturing.

3 cl, 6 dwg

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