Method of polyurethanedi(met)acrylates production

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyurethanedi(met)acrylates applicable as binders for powder coatings applied on metal substrates, plastic parts, fiber-reinforced plastic parts. Polyurethanedi(met)acrylates are obtained by interaction of diisocyanate component, diol component and hydroxy-C2-C4-alkyl(met)acrylate at mol ratio of x:(x-1):2, where x takes any value from 2 to 5. 1,6-hexanediisocyanate comprises 50 to 80 mol % of diisocyanate component, and one or two diisocyanates selected out of defined diisocyanate group where mol content of respective diisocyanates amount to 100 mol % comprise(s) 20 to 50 mol %, so that each diisocyanate comprises at least 10 mol % of diisocyanate component. Diol component includes not more than four different diols, and at least one linear aliphatic alpha, omega-C2-C12-diol comprises 20 to 100 mol % of diol component, while at least one (cyclo)aliphatic diol different from linear aliphatic alpha, omega-C2-C12-diols comprises 0 to 80 mol %. Each diol of the diol component comprises at least 10 mol % of diol component, and mol content or respective diols amounts to 100 mol %. Due to the absence of solvent in polyurethanedi(met)acrylate production, further cleaning of end product is not required, thus increasing process product output.

EFFECT: higher acid resistance of coating films applied and solidified with the use of powder coatings containing claimed polyurethanedi(met)acrylates.

6 cl, 15 ex, 3 tbl

 

The prior art to which the invention relates

The present invention relates to a method of manufacturing polyurethane(meth)acrylate, polyurethane(meth)acrylates obtained by the method according to the invention, and compositions of powder coating (powder coating), which contain polyurethane(meth)acrylate as a binder.

Description of the prior art

The polyurethane(meth)acrylates used as a binder for the production of powder coating compositions known from WO 01/25306. They are obtained by reacting at least one linear aliphatic diisocyanate, at least one aliphatic compound c, at least two functional groups capable of reacting with isocyanate groups and/or water, and at least one olefin-unsaturated compounds with a functional group capable of reacting with isocyanate groups. WO 01/25306 recommends carrying out the reaction in an organic solvent or solvent mixture(s) is(are) reactive(s) with respect to isocyanate groups. Then the polyurethane(meth)acrylate can be obtained by evaporation and/or crystallization and/or recrystallization. All the syntheses described in the section "Examples" WO 01/25306 are in methylethylketone to the to the inert solvent, followed by cooling the resulting solution at 3°C for 12 hours, from which polyurethanebased isolated in the form of precipitated solids by filtration under suction, washing and drying in vacuum.

Despite the fact that the reaction in an organic solvent, really results in is suitable for use as binders for powder coatings products, it is disadvantageous in various respects. The solvent must be completely separated from the product that you want to use as a binder for powder coating. The output decreases from cleanup.

The repetition of the examples of WO 01/25306 in the absence of organic solvent is problematic either because you need to use an excessively high melting point, leading to the risk of thermal free-radical polymerization of olefinic double bonds, or because they get products that are unsuitable as binders for powder coatings, as their melting point or melting range is too high (high) or too low (low). Excessively low melting point does not allow processing to form a powder coating: grinding, for example, becomes more difficult or impossible. An excessively high melting point, for example, are incompatible with the associated with oskouie coating processes, which include the curing process for which is listed lower the melting temperature. An excessively high melting point also often have a negative impact on the alignment of the powder coating in the molten state during the curing process.

There was a requirement to develop a production method suitable as binders for powder coatings, polyurethane(meth)acrylates, which avoids the above disadvantages.

Accordingly, according to the invention was developed process occurring in the absence of solvents and without loss of output and allows you to get polyurethane(meth)acrylates, which, even without treatment can successfully be used as binders for powder coatings.

The invention

The new method according to this invention includes a method of obtaining polyurethane(meth)acrylates, in which diisocyanate component, a diol component and hydroxy-C2-C4the alkyl(meth)acrylate, preferably hydroxy-C2-C4-alkylacrylate, react in the absence of a solvent and without subsequent action to clean up in a molar ratio x:(x-1):2, where x is any value from 2 to 5, preferably from 2 to 4, in which from 50 to 80 mol % diisocyanate component is 1,6-hexadienal, and from 20 to 50 mol % is(are) one or two diisocyanate, each of them is at least 10 mol % diisocyanate component and is selected from the group consisting of toluylene diisocyanate, diphenylmethanediisocyanate, dicyclohexylmethane, isophorondiisocyanate, trimethylhexanoate, cyclohexanebutyrate, cyclohexyldimethylamine and tetramethylethylenediamine, where the mol % of the respective diisocyanates total 100 mol %, in which the diol component comprises no more than four different diols and from 20 to 100 mole percent diol component is at least one linear aliphatic alpha, omega2-C12-diol, and 0 to 80 mol % of at least one (cyclo)aliphatic diol that is different from linear aliphatic alpha, omega2-C12-diols, where each of the diols diol component is at least 10 mole % diol component, and where the mol % of the respective diols total 100 mole %.

Detailed description of embodiments

In the method according to the invention diisocyanate component, a diol component and hydroxy-C2-C4the alkyl(meth)acrylate stoichiometrically react with each other in a molar ratio x mol of diisocyanate: x-1 moles of a diol: 2 mole of hydroxy-C2-C4the alkyl(meth)acrylate, where x is any value from 2 to 5, preferably from 2 to 4. When the values of x>5 it is often necessary to use a fusion temperature that is so high that there is a risk of free-radical polymerization during synthesis and/or derived products, which use as binders for powder coatings have excessively high points or melting ranges, for example above 120°C. moreover, it is impossible to achieve sufficient density of crosslinking in the case of powder coatings produced using as a binder, polyurethane(meth)acrylates, which were synthesized at x>5.

From 50 to 80 mol % diisocyanate component used in the method according to the invention, 1,6-hexadienal, and from 20 to 50 mol % is(are) one or two diisocyanate selected from the group consisting of toluylene diisocyanate, diphenylmethanediisocyanate, dicyclohexylmethane, isophorondiisocyanate, trimethylhexanoate, cyclohexanebutyrate, cyclohexyldimethylamine and tetramethylethylenediamine, where in the case when you choose two diisocyanate, every diisocyanate is at least 10 mol % of the diisocyanate diisocyanate component. Preferably, when the diisocyanate or two diisocyanate, the cat is who(s) is(are) generally from 20 to 50 mol % diisocyanate component, choose from dicyclohexylthiourea, isophorondiisocyanate, trimethylhexanoate, cyclohexanebutyrate, cyclohexyldimethylamine and tetramethylethylenediamine.

From 20 to 100 mol %, preferably from 80 to 100 molar %, of the diol component consisting of from one to four, preferably from one to three of the diols makes up at least one linear aliphatic alpha, omega2-C12-diol, and 0 to 80 mol %, preferably from 0 to 20 molar %of at least one (cyclo)aliphatic diol that is different from linear aliphatic alpha, omega2-C12-diols and preferably also from alpha, omega-diols, includes more than 12 carbon atoms. Each diol diol component is at least 10 mole % diol component.

Most preferably diol component is not included in any of the diols, which are different from linear aliphatic alpha, omega2-C12-diols, preferably consisted of from one to four, preferably from one to three, and in particular, only one linear aliphatic alpha, omega2-C12-diol(s).

Examples of the linear aliphatic alpha, omega2-C12diols that can be used in the diol component, VK is ucaut ethylene glycol, 1,3-propandiol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol.

Examples of (cyclo)aliphatic diols, which are different from linear aliphatic alpha, omega2-C12-diols that can be used in the diol component include the isomers of propane diol and butanediol, which differ from the isomers of propane diol and butanediol, described in the previous paragraph, as well as neopentylglycol, butylaminoethyl, isomeric cyclohexanediol, isomeric cyclohexanedimethanol, hydrogenated bisphenol a and tricyclopentadiene.

If diol component consists of several diols, diols can be used in the form of a mixture in the synthesis method according to the invention or diols comprising the diol component used in the course of the synthesis in each case individually. It is also possible to use part of the diols in the mixture, and the remaining part (s) in the form of pure diol.

Preferably, when the method according to the invention using only one hydroxy-C2-C4the alkyl(meth)acrylate. Examples of hydroxy-C2-C4the alkyl(meth)acrylates are hydroxyethyl(meth)acrylate, one of the isomeric hydroxypropyl(meth)acrylate or one of the isomeric hydroxybutyl(meth)acrylates; in each case, it is preferable acrylate connection.

The way is according to the invention, the diisocyanates diisocyanates component, diol or diols diol component and hydroxy-C2-C4the alkyl(meth)acrylate to react essentially to each other, i.e. in the absence of solvent. In this process, the reagents can react with each other all at once or in two or more stages of the synthesis. When the synthesis is carried out in many stages, the reagents can be added in the most diverse manner, for example also in a row or alternating way. For example, the diisocyanates diisocyanates component may initially react with hydroxy-C2-C4the alkyl(meth)acrylate, and then diola or dialami diol component or first diola or dialami diol component, and then with hydroxy-C2-C4the alkyl(meth)acrylate. However, the diol component can also be divided, for example, into two or more parts or individual diols, for example, so that the diisocyanate reacted first with a part of the diol component to posleduushie reaction with hydroxy-C2-C4the alkyl(meth)acrylate, and at the end, for example, with the remaining part of the diol component. While equally diisocyanate component can, for example, also be divided into two or more parts or individual diisocyanates, for example, so that hydroxycobalamin components are first reacted with a part diisocyanate component, and p is on the end, for example, with the rest diisocyanate component. In each case, the individual reagents can be added entirely or two or more portions.

The reaction is exothermic and proceeds at a temperature above the melting temperature of the reaction mixture, but below the temperature which leads to free-radical polymerization of the double bonds of (meth)acrylate.

The reaction temperature is, for example, from 60 to 120°C maximum. The rate of addition or the number of added reagents are determined respectively on the basis of the degree of ekzotermicheskie and liquid (molten), the reaction mixture can be kept within the desired temperature range by heating or cooling.

After completion of the reaction and cooling of the reaction mixture get solid polyurethane(meth)acrylates with the calculated molar masses in the range from 628 or higher, e.g. up to 2000. Polyurethane(meth)acrylates take the form of a mixture, characterized by a molecular weight distribution. However, polyurethane(meth)acrylates do not require processing, and can directly be used as binders for powder coatings. Their melting points are, in particular, in the range from 80 to 120°C.; generally speaking, the melting temperature are not clear melting points, novesta this represents the upper limit of the melting ranges of the width, for example, from 30 to 90°C.

Polyurethane(meth)acrylates can be used in powder coatings, not only as the sole binder or as a main binder, comprising at least 50 wt.% the solid content of the resin, but also in smaller portions as sovetuyesh. It is a remarkable high resistance of coating films applied and hardened from powder coatings, in relation to acids.

Powder coating manufactured using polyurethane(meth)acrylates obtained according to the invention as binders for powder coatings may include powder coating, cured solely by free-radical polymerization of the double bonds of olefins, which otverzhdajutsja thermally or by irradiation with high energy radiation, in particular UV-irradiation. They, however, can also include powder coating dual-cure, which additionally otverzhdajutsja through an additional mechanism of cross-linking caused in most cases by the action of temperature.

Depending on the nature of powder coatings, the composition of the solid resins may also include in addition to obtained according to the invention, polyurethane(meth)acrylate additional binder and/or cross-linking reagents. Complete the performance communications binders and/or crosslinking reagents can be cured in these coatings thermally and/or by exposure to high energy radiation.

While thermally curable powder coatings contain initiators of free-radical polymerization, splitting under the action of temperature, curing by means of UV irradiation powder coatings contain photoinitiator.

Depending on the selected curing conditions (purely thermal curing or a combination of curing under the action of UV radiation and temperature) powder coating dual-cure may contain initiators of free-radical polymerization, splitting under the action of temperature, or photoinitiator.

Examples of initiators of free-radical polymerization, splitting under the action of temperature, are azo compounds, peroxide compounds and initiators, fissile C-C bond.

Examples of photoinitiators are benzoin and its derivatives, acetophenone and its derivatives such as 2,2-diacetoxyscirpenol, benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone, 1-benzoylecognine, organophosphorus compounds, such as acylphosphatase.

Initiators for curing by free radical polymerization using, for example, in proportions of from 0.1 to 7 wt.%, preferably from 0.5 to 5 wt.%, relative to the total solid content of the resin and initiator. Initiate the s can be used individually or in combination.

Besides the already stated initiators powder coating can contain additional conventional additives for coatings, for example, inhibitors, catalysts, levelling agents, degassing agents, moisturizing agents, reagents that prevent the formation of surface defects, antioxidants and light stabilizers. Additives are used in conventional amounts known to the skilled in this technical field specialist.

Powder coating can also contain transparent pigments, the pigments that give color and/or special effects, and/or fillers, for example, with a ratio of the weight content of the pigment plus filler: solid resin in the range of from 0:1 to 2:1. Examples of inorganic or organic pigments that give color, are titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, chinaredorbit or pyrrolopyrazole pigments. Examples of pigments that give special effects are metal pigments, for example, made of aluminum, copper or other metals, interference pigments, such as metal pigments coated with metal oxides, for example, coated titanium dioxide or mixed oxides of aluminum, coated mica, such as, for example, coated titanium dioxide mica. An example is the mi of suitable fillers are silicon dioxide, aluminum silicate, barium sulfate, calcium carbonate and talc.

Powder coatings can be prepared using conventional methods known to the skilled in this technical field specialist, in particular, for example, by extrusion powder coating, which has already been completely made by dry blending all of the required components, in the form of a viscous melt, cooling the melt, rough grinding, fine grinding, and then split on the sieves to obtain the desired fineness of the grains, for example, to obtain average particle size from 20 to 90 μm.

Powder coating can be used for any desired purpose associated with industrial coatings and apply using conventional methods, preferably by spraying. Bases that can be considered are, in particular, not only the metallic base, but also plastic parts, for example, also reinforced fiber plastic parts. Examples are automobile bodies and parts of bodies, such as the valve body.

Powder coatings preferably include compositions non-pigmented powder coatings, which are used for making the outer layer of non-pigmented powder coatings for imparting color and/or special event the e effects of the primary coating layer. For example, to give the color and/or special effects, the main layer of the coating can be applied to automotive body, provided traditional primer, and, if desired, otvetit, and after that you can apply and cure non-pigmented powder coating composition non-pigmented powder coatings. If the primary coating layer is not overiden before applying the non-pigmented powder coatings, powder non-pigmented coating is applied by a process of "wet on wet".

The method used for applying powder coatings may, for example, consist of applying a first powder coating on an individual basis and melting by heating the applied powder coating to a temperature above the melting temperature, for example, in the range from 80 to 150°C. After melting by heat, for example, when convective and/or radiative heating, and if desired, provide the received phase possible alignment curing may occur when exposed to radiation of high energy and/or for the purpose of thermal energy. As the high energy emission is possible to use UV-radiation or radiation of the electron beam. Preferred is UV radiation.

The following examples illustrate the invention. The abbreviation “pbw” so, it is used to lower means weight part.

EXAMPLES

Examples c 1a through 1i (getting polyurethanecoated for comparative purposes)

Polyurethaneacrylate was obtained by reacting 1,6-exanguination with dialami and hydroxyethylacrylate in accordance with the following General method of synthesis:

First in a 2-liter chetyrehmetrovuyu flask equipped with stirrer, thermometer and column, introduced 1,6-hexadienal (HDI) was added 0.1 wt.% methylhydroquinone and 0.01 wt.% dilaurate dibutylamine, in each case relative to the initially introduced amount of HDI. The reaction mixture was heated to 60°C. Then they dosaged hydroxyethylacrylate in such a way that the temperature did not exceed 80°C. the Reaction mixture was stirred at 80°C until then, until reaching theoretical NCO content. Once theoretical NCO content was reached, one after another was added diols And, in each case in such a way that the temperature was maintained between 75 to 120°C. In each case, subsequent diol was not added until, until reaching theoretical NCO content. The reaction mixture was stirred at 120°C until then, until reaching the total absence of free isocyanate. The hot melt was poured and he was allowed to cool.

The behavior of the resulting polyurethanecoated melting b is lo investigated using DSC (differential scanning calorimetry, the heating rate 10 K/min).

Table 1 shows comparative examples 1a through 1i. Table notes on the ingredients in any molar ratios reacted with each other, and the result that was achieved. In particular, the final temperature of the melting process measured by DSC indicated in °C.

Table 1
ExampleMoth HDIMoles of hydroxyethylacrylateMoles of diol AndMoles of diol InMoles of diolResults
1a22 HEA0,8 NPG0,2 HEX90°C; susceptible to crushing, chilled
1b32 HEA1,7 NPG0,3 HEX88°C; susceptible to crushing, chilled
1c32 HEA1,5 NPG 0,5 HEX99°C; susceptible to crushing
1d42 HEA2,2 NPG0,8 HEX100°C; susceptible to crushing
1e32 HBA0,7 MPD0,7 PENT0,6 DEK117°C; susceptible to crushing
1f32 HBA1 CHDM1 PROP118°C; susceptible to crushing
1g32 HBA1,3 CHDM0,7 PENT120°C; susceptible to crushing
1h32 HPA1 CHDM0,5 PROP0,5 PENT118°C; susceptible to crushing
1i3 2 HPA0,6 HEX0,7 PENT0,7 PROP112°C; susceptible to crushing
HDI: 1,6-hexadienal
HBA: 4-hydroxyethylacrylate
HEA: hydroxyethylacrylate
HPA: 2-hydroxypropylamino
CHDM: 1,4-cyclohexanedimethanol
DEK: 1,10-decandiol
HEX: 1,6-hexanediol
MPD: 2-methyl-1,3-propandiol
NPG: neopentylglycol
PENT: 1,5-pentanediol
PROP: 1,3-propandiol

Examples c 2a through 2f (getting polyurethanecoated according to the invention)

Polyurethaneacrylate was obtained by reacting 1,6-exanguination, additional diisocyanate, diol component and hydroxy-C2-C4-alkylacrylate in accordance with the following General method of synthesis.

First in a 2-liter chetyrehmetrovuyu flask equipped with stirrer, thermometer and column, introduced 1,6-hexadienal (HDI), as well as additional diisocyanate was added 0.1 wt.% methylhydroquinone and 0.01 wt.% dilaurate dibutylamine, in each case relative to the initially introduced amount of the diisocyanate. The reaction mixture was heated to 60°C. Then hydroxyethylacrylate were dosed out in such a way that the temperature did not exceed 80°C. the Reaction mixture was stirred at 80°C until then, until reaching theoretical with the actual content of the NCO. Once theoretical NCO content was reached, one after another was added diols and, if desired, in each case in such a way that the temperature was maintained between 75 to 120°C. In each case, subsequent diol was not added until, until reaching theoretical NCO content. The reaction mixture was stirred at 120°C until then, until reaching the total absence of free isocyanate. The hot melt was poured and he was allowed to cool.

The behavior of the resulting polyurethanecoated melting was investigated using DSC (heating rate 10 K/min).

Examples 2a through 2f are shown in table 2. The table shows the ingredients in any molar ratios reacted with each other and the result that was achieved. In particular, the final temperature of the melting process measured by DSC indicated in °C.

Table 2
ExampleMoth HDIMoles of diisocyanate AndMoles of diisocyanate BMoles of hydroxyethylacrylateMoles of diol AndMoles of diol BResults
2a21 MDI2 HBA2 PENT120°C; susceptible to crushing
2b1,51,5 MDI2 HBA2 PENT115°C; susceptible to crushing
2c32 IPDI2 HEA3 NPG1 HEX120°C; susceptible to crushing
2d31 IPDI2 HEA2 NPG1 PROP110°C; susceptible to crushing
2e21 DCMDI2 HEA0,8 PROP1,2 PENT95°C; susceptible to crushing
2f 20,5 MDI0,5 DCMDI2 HEA2 PENT112°C; susceptible to crushing
MDI: diphenylmethanediisocyanate
IPDI: isophorondiisocyanate
DCMDI: dicyclohexylmethane
see table 1 for other abbreviations

Examples 3a through 3p

The powder coating composition obtained was applied and utverjdali using polyurethanecoated binders of comparative examples 1a through 1i and using polyurethanecoated binders of examples 2a through 2f, using the following basic rules.

Fragmented mixture of the following components pre-mixed and extrudible:

96,5 weight. parts of one of polyurethanecoated of examples 1a through 1i or one of polyurethanecoated of examples 2a through 2f,

1 weight. part of Irgacure®2959 (photoinitiator from the company Ciba),

0,5 weight. part Powdermate®486 CFL (leveling agent from company Troy Chemical Company,

1 weight. part of Tinuvin®144 (HALS light from the company Ciba), and

1 weight. part of Tinuvin®405 (UV-absorber from the company Ciba),

to obtain the composition of the non-pigmented powder coatings in the traditional way after cooling, crushing, grinding and sifting.

The respective powders of the e non-pigmented coating was sprayed to a layer thickness of 80 μm in each case on steel sheets, covered with a commercially available paint done by way of deposition, the filler and the main floor (where the air bubbles are removed)were subjected to melt for 10 min at 140°C (oven temperature) and utverjdali by UV radiation corresponding to the radiation intensity of 500 mW/cm2and the dose of 800 MJ/cm2. The obtained coatings was studied with respect to their resistance to acids. In this purpose, 50 μl of 36% sulfuric acid was administered at 65°C on the paint film for 30 minutes at intervals of one minute (score: the destruction of the film after X (from 0 to 30 minutes). The results are shown in table 3.

Table 3
ExampleExample binderResistance to acids (min)
3a1a12
3b1b13
3c1c11
3d1d12
3e1e10
3f1f22
3g1g24
3h1h23
3i1i13
3k2a28
3l2b>30
3m2c>30
3n2d>30
3o2e27
3p2f29

It turned out that non-pigmented powder coatings made on the basis of polyurethanecoated binders of examples 2a through 2f are more resistant to acids than non-pigmented powder coatings made on the basis of polyurethanecoated binders of examples 1A through 1i.

1. The method of obtaining polyurethane(meth)acrylates, including interaction diisocyanate components the NTA, diol component and hydroxy-C2-C4the alkyl(meth)acrylate in the absence of a solvent and without subsequent action to clean up in a molar ratio x:(x-1):2, where x is any value from 2 to 5, in which from 50 to 80 mol.% diisocyanate component is 1,6-hexadienal, and from 20 to 50 mol.% is(are) one or two diisocyanate, and each is at least 10 mol.% diisocyanate component and selected from the group consisting of toluylene diisocyanate, diphenylmethanediisocyanate, dicyclohexylmethane, isophorondiisocyanate, trimethylhexanoate, cyclohexanebutyrate, cyclohexyldimethylamine and tetramethylaniline diisocyanate, where mol.% the corresponding diisocyanates are in the amount of 100 mol.%, in which the diol component comprises no more than four different diols and from 20 to 100 mol.% diol component is at least one linear aliphatic alpha, omega2-C12-diol, and 0 to 80 mol.% is at least one (cyclo)aliphatic diol that is different from linear aliphatic alpha, omega2-C12-diols, in which each diol diol component is at least 10 mol.% in the diol component, and where the mol.% the corresponding diols are in the amount of 100 mol.%.

2. The method according to the .1, in which 80 to 100 mol.% diol component is at least one linear aliphatic alpha, omega2-C12-diol, and 0 to 20 mol.% is at least one (cyclo)aliphatic diol that is different from linear aliphatic alpha, omega2-C12-diols.

3. The method according to claim 1, in which the diol component consists of from one to four linear aliphatic alpha, omega2-C12-diols.

4. The method according to claim 1, in which the diol component consists of one linear aliphatic alpha, omega2-C12-diol.

5. Polyurethane(meth)acrylates obtained according to any of the preceding paragraphs.

6. Composition of powder coatings containing polyurethane(meth)acrylates obtained according to the method according to any one of claims 1 to 4, as a binder.



 

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2 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention pertains to polyurethane resin, which is a product of a reaction between at least one diisocyanate and components, containing functional groups, which have capacity to react with isocyanates, with the following composition: (a) first group, which is formed by one or more polyester-polyols based on ethers, each of which has average molecular mass ranging from 400 to 12000 g/mol, (b) second group, formed by one or more poly hydroxilated resins, chosen from a defined group of resins, (c) optional third group, formed by one or more polyols, each of which has average molecular mass, equal to or less than 800 g/mol, which are also chosen from a defined group of polyols, and (d) at least one amine and a reaction chain-stopping agent. The ratio of equivalent masses of diisocyanate and components, containing functional groups, with capacity to react with isocyanates, is chosen such that, naturally all isocyanate groups of diisocyanate are present as a product of the reaction with one of the above mentioned functional groups, with capacity to react with isocyanates. The invention also relates to the method of obtaining the above mentioned polyurethane resin, to polyurethane resin obtained through such methods, to coating for plastic substrates, containing the proposed resin, as a polyolefin binding substance, to use of such a polyurethane resin as a film forming substance in printing ink for printing on plastic substrates, as well as to the method of obtaining a laminate, which has a layer obtained when printing an image, including stages (a)-(d), with use of coating from polyurethane resin, and to a laminate, obtained using such a method.

EFFECT: obtaining a coating from polyurethane resin, with good heat resistance and excellent initial adhesiveness.

20 cl

FIELD: polymer materials.

SUBSTANCE: invention relates to compositions of molded polyurethane elastomers showing high physico-mechanical characteristics and providing high cyclic stability of products at alternate loadings within a wide operation temperature range. Invention may be used in rubber industry to manufacture cast tires and rolls for monorail vehicles. Composition according to invention contains polyoxytetramethylene glycol, mixture of 2,4-tolylenediisocyanate and 1,6-hexamethylenediisocyanate at molar ratio (0.8-0.9):0.1, and 3,3'-dichloro-4,4'-diaminodiphenylmethane in the form of solution in polyoxytetramethylene glycol at molar ratio (0.67-0.7):(0.29-0.30) as liquid hardener.

EFFECT: enabled use of polyurethane composition for molded elastomers.

2 cl, 2 tbl, 11 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

The invention relates to the production of a mixture of polyfunctional isocyanates and use it as an isocyanate component and simultaneously cross-linking agent when receiving both hard and flexible foams

The invention relates to polyurethane chemistry and relates to a method of producing elastic polyurethane foam product of more than 0.15 m3used in the furniture industry, vehicles, toys and t

FIELD: chemistry.

SUBSTANCE: powdered coating agent contains solid particles of a resin-polyurathane binding substance with equivalent mass of olefinic double bonds ranging from 200 to 2000 and content of silicon bonded in alkoxy silane groups ranging from 1 to 10 mass % and a photoinitiator. In the method of obtaining a single layered or multilayered coating on substrates, in particular when obtaining multilayered coating for transportation equipment and their components (car body or car body components coating), at least one layer of this coating is deposited from a powdered coating agent. In that case, solidification of at least one layer of the above mentioned powdered coating is achieved through free-radical polymerisation of olefinic double bonds when irradiated with high energy radiation and through formation of siloxane atomic bridges under the effect of moisture.

EFFECT: obtaining a powdered coating, which is hard, has scratch resistance and good resistance to chemical effects.

8 cl, 1 tbl

FIELD: glue compositions.

SUBSTANCE: invention relates to UV-strengthening glue compositions used for gluing substrates metal-silicate glass in electronic devices, such as optical reading head, thin-film transistor - semiconducting mesomorphic display, organic luminescent unit. The composition comprises oligourethaneacrylate - a mixture of oligourethaneacrylates of two type: the first is prepared by interaction of oligooxyalkylenepolyol of molecular mass 1000-5000 Da, diisocyanate of aliphatic or aromatic structure and alkylene glycol monomethacrylate, and the second based on oligobutadienediol of molecular mass 2000-3000 Da, diisocyanate of aliphatic or aromatic structure and alkylene glycol monomethacrylate in the mass ratio of the first to the second = (1.0-4.0):1, reactive monomer as a diluting agent, silicate filling agent, organic tert.-butylperbenzoate, thixotropic agent - aerosil and photoinitiating agent, and, additionally, it comprises oxalic acid as adhesion promoter, silane dressing agent and antioxidant of phenolic type. Invention provides the development of UV-strengthening glue composition possessing thixotropy, high strengthening rate, high adhesion strength being especially at effect of heat and moisture, temperature drop, low shrinkage and stability in storage.

EFFECT: improved and valuable properties of composition.

7 cl, 2 tbl, 5 dwg, 8 ex

FIELD: glue compositions.

SUBSTANCE: invention relates to UV-strengthening glue compositions used for gluing polymethylmethacrylate with metal. Proposed composition comprises oligourethane-acrylate representing product of interaction of oligobutadienediol of molecular mass 2000-3000 Da, aliphatic or aromatic diisocyanate and hydr(o)oxyalkylmethacrylate taken in the molar ratio = 1:2:2, reactive monomer-diluting agent representing a mixture of mono- and polyfunctional methacrylate, polymeric filling agent - polyethylene of high density with particles size below 50 mcm, photoinitiating agent, antioxidant of phenolic type and adhesion promoter - a mixture of chlorinated polyvinyl chloride with chlorine content 62-64 wt.-% and oxalic acid, and the composition comprises additionally thixotropic agent - aerosil with specific surface 175-380 m2/g and ester plasticizing agent. Invention provides the development of UV-strengthening glue composition showing the thixotropy coefficient K = 2-3, shrinkage 4%, not above, break off strength both in the parent state and after heat effect, moisture and temperature drop 1.5 MPa, not less, and stability in storage above one year. The composition can be used as adhesive in electronic devices, such as optical reading head, thin-film transistor - mesomorphic display and organic electroluminescent unit.

EFFECT: valuable properties of composition.

5 cl, 2 tbl, 5 dwg, 8 ex

FIELD: polymers, covering compositions.

SUBSTANCE: invention relates to photoactivating aqueous-base covering composition. The proposed composition comprises the following components: a)(meth)acryloyl-functional polyurethane dispersion wherein this (meth)acryloyl-functional polyurethane comprises from 5 to 18 weight % of alkylene-oxide groups and (meth)acryloyl functionality represents a value in the range from 2 to 40, and b) UV-initiating agent. The presence of reactive diluting agent in the covering composition is preferable. (Meth)acryloyl-functional polyurethane can be prepared by carrying out the following interactions: a) at least one organic polyisocyanate; b) optionally, at least one organic compound comprising at least two isocyanate-reactive groups and having an average molecular mass in the range from 400 to 6000 Da; c) at least one isocyanate-reactive and/or isocyanate-functional compound comprising non-ionogenic dispersing groups; d) at least one isocyanate-reactive (meth)acryloyl-functional compound; e) optionally, at least one chain elongating agent comprising active hydrogen, and f) optionally, at least one compound comprising active hydrogen and ionic groups. Aqueous-base covering composition is useful especially for applying as a clear cover. Covers based on the proposed composition show resistance to water, solvents and scratches and flexibility and high adhesion also.

EFFECT: improved and valuable properties of composition.

15 cl, 12 tbl, 17 ex

The invention relates to the field of rocket technology and concerns a method for obtaining a modifier, which is the basis for unsaturated polyester compounds

The invention relates to methods for elastomeric materials and may be used in the manufacture of sealants, coatings and molded articles
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