The oligomer of unilaterality and polimerproduct of curing

 

(57) Abstract:

Usage: for curing under the action of irradiation of the coating. The inventive oligomer of unilaterality produced by interaction of (a) a complex of the polyester of the formula , where n = 2-6, Z: n' = 2-4, or 1,2-phenylene, 1,3-phenylene or 1,4-phenylene, m = 1-100 c (b) di - or polyisocyanate with the number of isocyanate groups 2 and (S) - oxymoronically simple polyester of the formula: R1CH = CR4O-Z-OH, where R1and RII:H; alkyl groups WITH1-C10Z: bivalent residue from diatomic alcohol. Based oligomer get polymer - product of curing. The coating has high characteristics of elasticity, hardness, moisture resistance. 2 C. p. F.-ly, 7 PL.

The invention relates to oligomers, which can be used for many purposes, in particular for coatings cured under the action of electron beam, ultraviolet light, heat or other various effects already known in the art.

Calironia urethanes are widely used for coating. However, these monomers harmful and desirable to replace them with resins, which eliminate the use of acrylate monomers. In this regard, interest is icause from each other, that the derivatives of acrylate are polymerized in reticulosarcoma mechanism, while simple derivatives of vinyl ether is polymerized by cationic mechanism type. The advantage of vinyl ethers is that no oxygen inhibits the polymerization and the polymerization process is simplified.

In U.S. patent N 4751273 one of the authors of this invention have been described urethane resin with terminal groups of simple vinyl ether used for coatings. In the reaction of acetylene with a polyhydric alcohol was obtained oxymoronically simple ether and the product reacted with the isocyanate, the resulting resin (oligomer). It was suggested the possibility of replacing the isocyanate prepolymers, but it's not led to any improvement of these products, or to opportunities for beneficial use of these polyesters.

In the related U.S. patent N 4749807 describes the oligomer of ester end groups simple vinyl ether; oxymoronically simple ether interacted with carboxylic acid, especially with the activated derivative, such as chloride or ester. These oligomers do not include urethanes.

It was the mouth of onlinelove ethers, used to get as esters with terminal groups of simple ether, and urethanes, see U.S. patent N 4775732. In particular, it was found that bis(oxyalkyl) cycloalkanes provide an opportunity to obtain coatings with improved adhesion to metal substrates. Although there have been suggested as esters and urethanes, they were considered as products of different technologies.

In another patent (U.S. patent N 4845265) describes the benefits of using tricarboxylic acids or more high molecular weight acids to obtain oligomers of ester end groups simple vinyl ether, having excellent resistance to solvents. In this case, these oligomers also will not include urethanes.

The closest analogue of the invention is French patent N 2355794, class C 07 C 43/16, publ. 1978), which describes the use of compounds such as the compound (a) complex polyester with terminal hydroxyl groups (the product of the interaction of adipic, phthalic acid with trimethylolpropane or propylene glycol), connection (in) isophorondiisocyanate and connection (s) - vinyl ester 3-methylpentanediol to 1.5. Specified oligomer is cured by ultraviolet or S="ptx2">

The ongoing development of new coatings on the basis of the above oligomers showed that for some applications further improvements are required.

The aim of the invention is the improvement of the characteristics of elasticity, hardness, water resistance and color coatings on the basis of the following oligomers.

Oligomer simple vinyl ether, used in particular for the preparation of coatings, obtained by the reaction of (a) a complex of the polyester with terminal hydroxyl group of the formula

< / BR>
where

< / BR>
where n is 2-6

y: -(CH2)n-, n is 2-4, or 1,2-phenylene, 1,3-phenylene or 1,4-phenylene, m has an average value from 1 to 100,

with the diisocyanate (b) selected from the group comprising: colorvision, 4,4'-diphenylmethanediisocyanate, tetramethyldisilane, isophorone, diisocyanate, 4,4'-dicyclohexylmethane and n-hexadienal, or other polyisocyanates having two or more functional groups, and with oxymoronically simple ether (s) of the formula: R CH CR O Z OH,

where R' and R": H, alkyl groups with 1 to 10 carbon atoms;

Z: bivalent residue from butanediol, 1,4-bis(methyl)cyclohexanol, ethylene glycol, diethylene glycol, chrysoidine (a) to hydroxyl groups (C), 0.5:5, when the ratio of hydroxyl groups of the compounds (a) and (C) to the isocyanate groups of the compound (b) is 1:1, and the remainder neproreagirovavshikh hydroxyl groups in vinylethylene is less than 1 mol. from initially participating in the reaction.

These oligomers can be obtained by jointly reactions of all three components (a), (b) and (C), or by reaction of the first component (a) with component (b) or component (C), and then reaction with the third component.

The number of components (a), (b) and (C) must be regulated so that the ratio of hydroxyl groups of components (a) and (C) to the isocyanate groups of component (b) was 1:1. The ratio of the total number of hydroxyl groups of component (a) to the total number of hydroxyl groups of component (C) should be in the range of from 0.5 to 5. In the ideal case there should be no excess of hydroxyl groups, it is desirable that the number was less than 10 mol. most preferably less than 1 mol. from initially present groups. In addition, there should be no excess isocyanate groups in the oligomer, it is desirable that the number of such groups was less than 1 mol. from the original prisutstvie ways, for example, when exposed to the electron beam, ultraviolet radiation and heat.

Description of the preferred principles of the invention.

The reagents.

Polyesters.

Polyesters used in the invention are compounds with terminal hydroxyl group, and they can be represented by the General formula:

< / BR>
in which X and Y are divalent radicals with a molecular weight of from 28 to 500, and selected from among the following groups: alkylen, Allen, arankele and cycloalkyl, m has an average value from 1 to 100.

X and Y may represent a group of alkylene, especially alkylene containing up to 20 carbon atoms, a group of cycloalkene, arylene or kalkilia. Examples used alkilinity groups are methylene, ethylene, propylene, butylene, pentile, hexylen, oxilan, Nonlin, deciles, undecided, modellen, tridesilon, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octagoncito, nonadecane and akosile. Examples arenovich groups are phenylene, naftilan, entrylen, phenanthrolin, etc. Cycloalkene group include cyclopentyl, cyclohexyl, cycloheptyl, qi is, used as group, may also comprise one or more alkyl groups in the aromatic nucleus, especially in the case when such alkyl groups include up to 6 carbon atoms. Examples Arakelova groups are benzilan, 1-venetien, 2-venetien, 3-phenylpropyl, 2-phenylpropyl, 1-phenylpropyl and so on, Especially suitable for The groups are the group -(CH2)n0, where n is 2,3 or 2; band 1,2-1,3-, or 1,4-phenylene, and a group of 1,4-cyclohexene. Particularly suitable as X groups are -- CH2CH2-, -CH2CH2-O-CH2CH2-, -CH20(CH3)CH-, -(CH2)n-, where n is 4 or 6. -CH2-(CH3)2C-CH2; 1,4-bis(methyl)phenylene. M will be an integer from 1 to 100, preferably from 1 to 10.

Especially preferred polyesters with terminal hydroxyl group include poly (propylenediene), poly(neopentylene), poly(1,4-butanediol), poly(1,6-hexanediol), poly(neopentecostal), and poly(1,6-hexanicotinate). Can be successfully used polyesters formed from mixed diatomic alcohols or acids. The preferred molecular weight polyesters is from 500 dni General formula ON-Q-NCO, in which Q is a divalent radical selected from among the following: alkylene, Allen, arankele, and cycloalkyl.

Can be used with various diisocyanates, examples of which include compounds such as colordistance (TD), para - and meta-delete the entry, 1,4-tetramethyldisilane, 1,6-hexamethylenediisocyanate, 4,4'-dicyclohexylmethane (Desmodur W), 4,4'-diphenylmethanediisocyanate (MDI), 3,3-dimethyl-4,4-diphenylmethanediisocyanate, 1,5-tetrahydronaphthalene, naphthalene-1,5'-diisocyanate, bis(2-methyl-3-isocyanatophenyl)methane, 4,4'-diphenylmethanediisocyanate, tetramethylethylenediamine (DI), isophorondiisocyanate (IPDP).

It can also use polyisocyanates having two or more functional groups, such as described in U.S. patent N 4433067, especially polyisocyanates based on etilendiamindisuktsinatov, especially the 4,4'-isomer and modified oregoniana DI, as described in this patent. The concept of the polyisocyanate includes quasilocality polyisocyanates containing compounds with active hydrogen, where the polyisocyanate is usually communicates from 0.05 to 0.3 equivalents of a polyhydric alcohol. Although there may be used various polyisocyanates, site is aliphatic isocyanates do not serve yellowing, that is especially important for coatings.

Among the most desired isocyanates can be mentioned 4,4'-diphenylmethanediisocyanate, colorvision, isophorondiisocyanate, betteremailnotifications, 4,4'-dicyclohexylmethane (Desmodur W) and 1,6-hexamethylenediisocyanate.

Hydroxy-monovinyl ethers.

Alcohols with end group of simple vinyl ether, which are used to produce the oligomeric esters conforming to this invention have a structure corresponding to the product of the merger of alkyne and a polyhydric alcohol. However, these alcohols with end group of simple vinyl ether can be obtained in other ways, and the way they are received may not be considered as an integral part of the present invention. Alkylen has the General formula R CaCR", and diatomic alcohol has the General formula BUT-Z-OH. The General formula of alcohols with end group of simple vinyl ether, responsive to the invention, is as follows:

R CH CR"O ZOH

Groups R' and R" independently of one another are selected from among the following: hydrogen and groups of the lower alkyl with 1 to 10 carbon atoms, although preferred are those which contain from 1 to 4 carbon atoms. Chelation is the higher of alkyl, undesired decrease in the rate of polymerization of the oligomer corresponding to this invention. When R' is an alkyl group, preferably R" is a hydrogen, and Vice versa, when R' is hydrogen, it is desirable that R" represents alkyl with the content of 1-4 carbon atoms. In the preferred case, R' or R" represents a methyl group, and R" and R' represents hydrogen. Even more preferably, R' and R" both represent hydrogen.

Z is a divalent radical with a molecular mass of 28-500, and selected from among alkilinity or cycloalkenes radicals.

Among diatomic alcohols one of the most important class excludes alkalophile. BUT (CnH2n)OH, where n is an integer from 2 to 10. Preferred are linear alkalophilus, BUT(CH2)nOH polimetilenovye, in which n is an integer from 2 to 10, especially those in which n is from 2 to 6. Examples of such groups are diatomic alcohols as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol and 1,10-decanediol (geometallurgical).

Can also be used Neli is. what reamers are 1,2-propylene glycol, 2,3-butanediol, 2,3-dimethyl-2,3-butanediol, 2,3-dimethyl-1,4-butanediol, 2,2-dimethyl-1,3-propandiol (neopentylglycol).

Another useful class of diatomic alcohols are alkylene glycols, especially poly(ethylene)glycols, BUT[0CH2CH2O-] mOH, and poly(propylene)glycol, HO[-CH(CH3)CH2O-]mOH, where m is an integer from 1 up to 10, and most preferably is from 1 up to 5. Examples of these glycols include diethylene glycol, triethylene glycol, tetraethylene glycol, pentachlorphenol, hexamethyleneimine, etc. along with analogues of propylene glycols.

The most important class of compounds in which Z is a divalent radical formed from cycloalkanes, such as cyclopentane, cyclohexane, Cycloheptane, or cyclooctane, preferably biaxially derivatives. Preferred diatomic alcohols (dialami) are 1,3-bis(oxyalkyl)cyclopentane and 1,4-bis(oxyalkyl)cyclohexane-Cycloheptane, and cyclooctane, especially cyclohexane. According to the invention can be used diatomic alcohols, substituted in positions other than those defined above, but not necessarily with regnoanimale recovery of the corresponding phthalic acid, and which one is preferable 1,4-bis(oxymethyl)cyclohexane.

Among oxymoronically ethers, which are obtained by reaction of acetylene with the above diatomic alcohol, particularly preferred esters include 4-oxybutylene simple ether, 4-oxyethylenenitrilo simple ether, 2-acetylindole simple ether, triethylenemelamine simple ether and diethylethylenediamine simple ether;

Reaction conditions.

An important feature of the present invention is that all classes of compounds have multiple hydroxyl groups formed from a complex of the polyester or oxymoronish simple ether in the final product. In other words, less than 10% of the original hydroxyl groups remain unreacted.

Most preferably, the oligomeric product with end group of simple vinyl ether include undetectable the free hydroxyl group, i.e. to less than 1% of the original isocyanate groups of the reaction mixture remained unreacted. It is also important that the product left almost no free isocyanate groups. Usually the complex ratio of the polyester (a), DIIS the lo equivalents of hydroxyl and isocyanate groups.

Oligomers simple vinyl ether can be obtained by reaction of a complex of the polyester with terminal hydroxyl group of the (a) isocyanate compound (b) or by reaction of the isocyanate (b) oxyvinyls simple ether (C) followed by reaction of this product attach to the rest of the component; or it can happen the joint reaction of these three components. The ratio of (a), (b) and (C) are selected so that the ratio of the total number of hydroxyl groups of the compounds (a) and (C) to the number of isocyanate groups of the compound (b) was 1:1. The ratio of the number of hydroxyl groups of the compound (a) to the number of hydroxyl groups of compound (C) should be in the range from 0.5 to 5. The reaction may proceed at a temperature in the range from 0 to 150oC. Can be used, such solvents as simple diethyl ether, methylene chloride or toluene, which is then removed from the oligomers, or the components can react in the absence of solvents. As solvents can also be used monomers deviceloop simple ether such as 1,4-cyclohexanedimethanol simple ether or triethylenemelamine simple ether. Such compounds can be obtained as a side ol the SCP, they do not react with isocyanates, but can stay together with oligomers in the coating compositions.

The reaction can be carried out without a catalyst, but can be used tin catalyst, such as dilaurentiis.

Oligomers simple vinyl ether, responsive to the invention can be cured (or cure) is well known in the art methods and applied as a coating. For example, as a coating resin can be cured by radiation exposure, for example, exposed to electron beam with energy ranging from 50 up to 500 KEV with doses ranging from 0.1 to 10.0 Mrad. Curing with electron beam can be carried out successfully in the presence of idoneous or sulfonato salt for high-speed cationic polymerization. May also be the curing under the action of ultraviolet radiation in the presence of oneway salt, resulting in cationic polymerization. Radiation activated cationic polymerization initiators are described in the publication J. V. Grivello. Advances in Polymer 64, pp. 1-48, 1984

Other methods include thermal curing in the presence of strong acids, Taco catalysts, which when heated produce a strong acid, for example blocked sulfoxylate. All of these methods of polymerization are well known to specialists in this field.

Example 1. Synthesis of oligomer of minilaparotomy, elongated chain complex of the polyester.

1,4-cyclohexanedimethanol simple ether (CDDVE, 160,6 g) and MDI (to 140.5 g of 0.56 mol) was introduced into the reactor for the synthesis of the resin, which was heated to 50oC in dry nitrogen atmosphere. Poly(neopentylene) with a terminal hydroxyl group (Witco Formrez 55-225, 138,9 g, 0.56 EQ) was mixed with 10 drops of dibutyltindilaurate tin, and the mixture was injected dropwise into the reactor for the synthesis of the resin for approximately 1 h maintaining the reaction temperature in the range from 50 to 60oC. Then the mixture was introduced dropwise 4-oxyethylenenitrilo simple ether (CDMVE) (95,4 g of 0.56 mol). The reaction was traced by means of IR spectroscopy. After stirring the mixture at a temperature of 55-60oC for 2.5 h band of the IR spectrum corresponding to 2250 cm-1from the group NCO, was no longer found. The product was a transparent thick liquid. Analysis by gel permeation chromatography (GPC) using polystyrene as standard) showed Molinengo polyester chain.

The product obtained as described in example 1, was mixed with triarylsulfonium salt serving as a catalyst (Jeneral Electric WVE-1016, 2 h/hundred) and was applied to the surface treated steel or on the surface of the pressed paper plate, covered with polyethylene, with a rod with a wire winding N 6.

The coating was subjected to curing under the action of ultraviolet radiation using the RPC model QC-1202 with two mercury lamps, medium pressure. The coating was subjected to curing under the influence of electron beam (EB) using the installation deposition Energy Sciences, model SV-150, equipped with linear cathode length of 15 cm (operating at 160 Kev). Immediately after irradiation was turned transparent, colourless or slightly coloured, neoplasia film. These coatings were investigated within 1 h after exposure. These coatings were investigated for resistance to solvents, using as solvent methyl ethyl ketone. Registered a double-abrasion required for the gap in the floor. Was carried out by reversed shock on steel plates using the impact testing device Gardner. Measurement was carried out by the method of ASTM D u the ASTM D 522. Adhesion was measured according to the method of ASTM D 3359, using masking tape, Scotch 610. Hardness was measured according to the method of ASTM D 3363. The results are summarized in table.1.

Example 3. The oligomer of minilaparotomy elongated polyester chain, was obtained by reaction DI (137,9 g to 0.55 mol), poly(PROPYLENEIMINE) with a terminal hydroxyl group (Formez 33-225, 139,1 g, 0.55 to EQ. HE and CDMBE (93,8 g to 0.55 mol) in 168,9 g CDDVE. The procedure was carried out in the same manner as described in example 1. The product was a thick, clear liquid. Analysis by gel permeation chromatography showed that Mn1900, Mw3200.

Example 4. The product obtained as described in example 3, was mixed with triarylsulfonium salt, and it is applied in the form of coatings and utverjdali in the same manner as described in example 2. The results are summarized in table.2.

Example 5. The oligomer of minilaparotomy elongated polyester chain, was obtained by reaction VDI (136,2 g of 0.54 Mol), poly(PROPYLENEIMINE) with a terminal hydroxyl group (137,4 g of 0.54 EQ) and 4-oxybutylene simple ether (62,7 g of 0.54 mol) in 112,1 g CDDVE. The procedure was carried out in the same manner as described in example 1. The product was a white solid waxy substance. Analysis is hydrated as described in example 5, mixed with triarylsulfonium salt and deposited in the form of coatings and utverjdala in the same manner as described in example 2. The results are summarized in table. 3.

Example 7. The oligomer of vinylidene elongated polyester chain, was obtained by reaction of isophorondiisocyanate with 72.9 g of 0.33 mol), poly(PROPYLENEIMINE) with a terminal hydroxyl group (82.7 g of 0.33 EQ. HE) and 4-hydroxy-butylaniline simple ether (of 37.7 g of 0.33 mol) in 64,4 g CDDVE. The product was a clear liquid. Analysis by gel permeation chromatography showed the following: Mw1500, and Mn2200.

Example 8. The product from example 7 were mixed with triarylsulfonium salt as catalyst and put it in the form of coatings and utverjdali in the same manner as described in example 2. The results are summarized in table.4.

Example 9. The synthesis product was carried out in the same manner as described in example 5 with the difference that as Monomeric diluent was used triethylenemelamine simple ester instead of CDDVE. The resulting product was a white soft waxy solid. Analysis by gel permeation chromatography showed that Mn1700, Mw3300.

Example 10. Product zoom, as described in example 2. The results are summarized in table.5.

Example 11. This example illustrates the use of high molecular weight group extension polyester chain. Was used poly(propylenediene) with a terminal hydroxyl group (Mw2000, Mn500), the same that was used in the examples 4,5,7 and 9). The oligomer of minilaparotomy elongated polyester chain, was obtained by the reaction of MDI (66,9 g, 0,267 mol), poly(PROPYLENEIMINE) (Formrez 33-56, 276,1 g, 0,267 EQ. HE and CDMVE (45,5 g, 0,267 mol) in 68,5 CDDVE. The procedure was carried out in the same manner as described in example 1. The resulting product was a transparent thick liquid.

Example 12. This example illustrates how can regulated the properties of the cured coating by changing the number of oligomer VEU and vinyl ester monomer in the composition of the coating.

Oligomer in example 1.1 synthesized in the presence of 15% CDDVE monomer. The oligomer was injected for various number of additional CDDVE monomer together with triarylsulfonium salt (24/SRT). The mixture was applied in the form of coatings and utverjdali when exposed to ultraviolet radiation in the same manner as described in example 2 (table.6).

Coverage data stanovi the harsh impact of 160 inch/pound and elongation of 50% in the number of monomer 15% and impact strength of at reverse shot 5 inch/lb and elongation of 4%, while the number of monomer 65% ). These results can be attributed to the effect of the monomer, which determines the density of cross-linkage of the cured coating relative to the oligomer.

Example 13. This example illustrates the case when the group extension polyether chain obtained from a mixture of two different diatomic alcohols. Used polyhydric alcohol with a terminal hydroxyl group resulting from the reaction of adipic acid with a mixture of ethylene glycol and 1,4-butanediol (Witco Formrez e-56). Thus, minilaparotomy, elongated polyester chain, was obtained by reaction DI (68,9 g, 0,275 mol), poly(ethylene/butanedioate) (273,0 g, 0,275 EQ. HE) and 4-hydroxy-butylaniline simple ester (31.7 g, 0,275 mol) in 41.8 MDDVE. The procedure was carried out in the same manner as described in example 1. The product was a slightly turbid thick liquid.

Example 14. The product obtained as described in example 13 was mixed with triarylsulfonium salt and put it in the form of a coating, using the same procedure as described in example 2. The results are summarized in table.7.

Example 15. The oligomer was obtained in the absence of deliniating monomer. In the examples described above (1,3,5,7,9,11 and 13) oligomers were prepared in the presence of divine is Olga) was introduced into the reactor for the synthesis of the resin, which was heated to 60oC in dry nitrogen atmosphere. Poly(propylenediene) with a terminal hydroxyl group (Wirco Formrez 33-56, 219,6 g, 0,212 EQ. HE together with 8 drops of dibutyrate tin was introduced dropwise from a heated funnel to enter (70oC) for about 1 h the Mixture is stirred for another hour at a temperature of 60oC, after which the input was stopped. Then the mixture was introduced dropwise CDMVE (36,1 g, 0,212 mol) maintaining the temperature of 60oC. after another 2 hours (at 60oC) no longer showed the line of the IR spectrum, the corresponding NCO at 2250 cm-1. The product was a very viscous transparent liquid.

Example 16. The product from example 6 was mixed with triarylsulfonium salt, it is applied in the form of a coating on the test plate and utverjdali under the influence of ultraviolet radiation at 250 MJ/cm2as was described above. Utverjdenie floor had impact strength (reverse punch) 160 inch/pound and elongation of 50% Hardness by pencil was 2V and the coating withstood 40 dual friction with ethyl ketone.

Example 17 (comparative). This example compares the materials described in U.S. patent N 4751273, the materials, chatanim alcohol was used for the synthesis of the urethane resin with end group of simple vinyl ether (column 5, line 4-29). Was carried out, the reaction mixture triethylenemelamine simple ester (14.1 g, of 0.08 mol) and triethylene glycol (6.0 g, a 0.04 mole) 4,4'-diphenylmethanediisocyanate (20,0 g, of 0.08 mol). In a few minutes after putting 5 drops of dibutyltindilaurate tin as catalyst began exothermic reaction. The temperature is brought up to the maximum value 70oC using an ice-water bath. After stirring for 4 h the temperature was decreased to 30oC. infrared analysis has not detected the spectrum of the corresponding NCO in the sample. This product was a thick, clear liquid. Analysis by gel permeation chromatography using polystyrene as standard) showed: Mn462, Mw1464 (including the contribution from triethylenemelamine simple ether, 202 g/mol).

This product was applied in the form of coatings and utverjdali under the influence of ultraviolet radiation at 75 MJ/cm2according to the procedure described in example 2. Utverjdenie floor was close to >100 MEK abrasion. The pencil hardness was 3H. Impact strength (reverse punch) was >160 inch-pounds and the elongation at break was >50% of These properties are comparable with the slightly yellow-brown staining within one week after curing, while materials in compliance with the invention, were found very little discoloration or it did not. In addition, coatings based on polyethers (such as triethylene glycol described in this example) had undesirable properties, manifested in the fact that they had a tendency to absorb moisture from the environment.

In U.S. patent N 4775732 describes urethane oligomers with functional groups simple vinyl ether-based bis(oxyalkyl)cycloalkanes such as 1,4-bis(oxymethyl)cyclohexane. These substances do not contain polyester structures and there are some problems with the absorption of moisture and discoloration, as described above in example 17. However, one problem associated with these materials is that they have poor characteristics of the curve. This is illustrated in example 3 of U.S. patent N 4775832, where it is shown that the elongation of the cured coating is only 14% and impact strength when the reverse shock is only 16 inch-pounds. Characteristics of bending of products that meets the invention were improved due to the introduction of the extension groups of a polyester chain, as can be seen from the data in examples 2,4,6,12,14 and 16.

1. The oligomer of unilaterality - (CH2)n,

where n' is 2 to 4, or 1,2-phenylene, 1,3-phenylene or 1,4-phenylene,

with the diisocyanate (b) is selected from the group including tolylenediisocyanate, 4,4'-diphenylmethanediisocyanate, tetramethyldisilane, isophoronediisocyanate, 4,4'-dicyclohexylmethane and n-hexadienal, or polyisocyanates having two or more functional groups, and with oxymoronically simple ether (s) of General formula

R CH CR O Z OH,

where R and R" are hydrogen, alkyl groups with 1 to 10 carbon atoms;

Z is the divalent residue butanediol, 1,4-bis(methyl)cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropyleneglycol and dipropyleneglycol, at a molar ratio of hydroxyl groups of compounds (a) and hydroxyl groups (C) is 0.5:5.0 when the molar ratio of hydroxyl groups of the compounds (a) and (C) and the isocyanate groups of the compound (C) 1: 1, and the remainder neproreagirovavshikh hydroxyl groups in vinylethylene is less than 1 mol. from initially participating in the reaction.

2. Polimerproduct curing oligomer of unilaterality on p. 1.

 

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7 cl, 2 tbl, 5 dwg, 8 ex

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: 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

FIELD: chemistry.

SUBSTANCE: described is a polyol composition containing polyol (a) and fine resin particles (b), dispersed in the polyol (a), where the fine resin particles (b) are polymer particles obtained by polymerising an ethylene unsaturated monomer (d) and content of particles with diametre of not less than 10 mcm in the fine polymer particles (b) is not greater than 2 vol %. The fine resin particles (b) are particles for which arithmetic standard deviation for particle size distribution per unit volume, obtained based on corresponding values in 85 intervals of the range from 0.020 to 2000 mcm, determined using a particle size distribution analyser through a laser radiation diffraction/scattering method, is not greater than 0.6. The resin has ultimate tensile strength of 1.54-1.65 kgf/cm2 and breaking elongation of 116-123%.

EFFECT: improved mechanical strength parametres.

17 cl, 6 tbl, 24 ex

FIELD: chemistry.

SUBSTANCE: multicomponent aqueous composition contains an aqueous dispersion and a component containing a material having functional groups. The components are mixed with each other before applying the composition onto the substrate. The aqueous dispersion contains a polycarbonate-polyurethane polymer and an acrylic polyol. The aqueous dispersion also contains an organic solvent. The material having functional groups reacts with functional groups of the acrylic polyol and/or polycarbonate-polyurethane polymer. The acrylic polyol has number-average molecular weight from 500 to 4000. The polycarbonate-polyurethane polymer is obtained via a reaction between hydroxy-functional carbonate-containing material and polyisocyanate. The hydroxy-functional carbonate-containing material contains a product of reaction between carbonic acid or derivative thereof and a diol. The diol is hexane-1,6-diol.

EFFECT: composition has low content of volatile substances, as well as high water resistance and hardness.

20 cl, 3 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a cross-linkable elastomeric thermoplastic polyurethane which does not contain urea, isocyanurate, oxozolinyl, functional side groups capable of radical polymerisation, and having on both ends terminal functional groups capable of radical polymerisation, obtained through reaction of polyfunctional isocyanate, polyfunctional polyol and monool, containing unsaturation and capable of radical polymerisation, and a diol chain extender, where the amount of monool containing unsaturation ranges from 0.001 mol/100 g to 0.016 mol/100 g, preferably from 0.002 mol/100 g to 0.01 mol/100 g of the polymer composition. The invention also describes a method of producing such a thermoplastic polyurethae, a composition containing said polyurethane and a method of cross-linking such a composition, heat-cured polyurethane obtained from thermoplastic polyurethane according to the invention and a method of producing heat-cured polyurethane, as well as use of the disclosed cross-linkable elastomeric thermoplastic polyurethane or composition to make moulded articles, protective films, coatings for motorcars and extruded articles, tubes or cable sheathing.

EFFECT: thermoplastic polyurethane with improved stability at high temperature, wear resistance, creep resistance, dynamic characteristics and resistance to organic solvents.

22 cl, 4 ex, 8 tbl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to oligomeric urethane acrylates whose molecules contain a statistic average of at least two structural units of general formula I: R{-X-CH2-CH(-CH2-O-(O)-CR1=CH2)[-O-C(O)-NH-]}n, where n is a number from 1 to 6; R is an organic low-molecular or oligomeric radical, from monovalent to hexavalent; X is an oxygen atom or a -C(O)-O- group, a radical which is bonded to radical R through a carbon atom; and R1 is a hydrogen atom or a substituted or unsubstituted alkyl group containing 1-6 carbon atoms. The invention also describes a method of producing said compounds and use thereof as materials which are cured radically through activation with actinic radiation and/or thermal activation or for obtaining such materials.

EFFECT: obtaining novel oligomeric urethane acrylates which are activated with actinic radiation, have low viscosity and enable to obtain coatings with very good mechanical qualities, particularly high hardness, flexibility and deformability, considerable adhesion to different substrates, especially sheet metal, high resistance to the effect of chemical products and atmospheric corrosion, and also having remarkable effect from dull to satin gloss.

26 cl, 14 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to radiation-curable compositions, as well as a coating containing said composition for protecting metal substrates from corrosion. The composition consists of radiation-curable urethane(meth)acrylate with OH number ≥ 10 mg KOH/g, a monofunctional, radiation-curable reactive diluent, an acidic adhesion promoter, a photoinitiator, a multifunctional reactive diluent, radiation-curable resins and other inert additives. The adhesion booster used is phosphoric or phosphonic acid or products of their conversion with functionalised acrylates.

EFFECT: radiation-curable compositions, having good corrosion-protective properties for metal substrates, which are elastic and capable of being well moulded.

15 cl, 2 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: composition contains 20-70 pts. wt polymer cross-linking agent which contains a product of a reaction between a polyol compound, obtained from glycidyl ether and amine, and a derivative of a polyisocyanate compound whose functional groups are blocked, 30-80 pts. wt main resin and 0.1-10 pts. wt polymer curing agent which contains a metal, wherein the polyol compound, obtained from glycidyl ether and amine, is a product of a Mannich reaction between a derivative of a phenol compound, a derivative of an amine compound and formalin.

EFFECT: obtaining a polymer composition which exhibits high corrosion resistance and curing behaviour when applied, using conventional installations.

20 cl, 9 tbl

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