Polymer composition

FIELD: chemistry.

SUBSTANCE: invention relates to a polymer composition for elastomeric waterproofing, roof coating, floor and sports field coatings. The composition contains 100 pts. wt isocyanate prepolymer and 11-31 pts. wt hardener. The isocyanate prepolymer used is obtained by reacting four moles of 4,4'-diphenylmethane diisocyanate and one mole of oligobutadiene diol with molecular weight of 2800-3200, containing 0.9-1.3% hydroxyl groups, while the prepolymer contains 8.0-9.7% isocyanate groups. The hardener used is 3,3'-dichloro-4,4'-diaminodiphenylmethane or a mixture of 2,4 and 2,6 isomers of 3,5-dimethylthiotoluylenediamine in ratio of 80:20.

EFFECT: polymer composition provides improved strength properties of elastomers and coatings obtained from it, specifically higher strength, hardness, relative elongation and adhesion properties of the coating.

1 tbl

 

The invention relates to polymeric compositions based on liquid hydrocarbon rubbers designed for elastic waterproofing, roofing, flooring floors and playgrounds.

Known composition for coating comprising isocyanate oligobutadienediol the prepolymer with srednekamennogo molecular weight 2500-3500, content of isocyanate groups of 1.9-2.3% 1,4-CIS 18-28%, 1,4-TRANS 58-62%of 1,2-units of 15-20%, the accelerator, oligodendrocytical, chalk, calcium oxide and diglycidylether [RF Patent № 1528781, CL C09D No.3 / 72, publ. 15.12.89, bull. No. 46].

A disadvantage of known composition is a low strength of elastomeric materials and coatings based on it.

Known polymer composition comprising oligosaccharyltransferase, a curing accelerator, mastic "Couplet", chalk, calcium oxide [RF Patent № 1509385, CL C09D No.3 / 72, publ. 23.09.1989, bull. No. 35].

The disadvantage of this composition is the low strength of the hardened elastomers and coatings based on it.

The closest solution to the claimed composition to the technical nature (taken as a prototype) is a composition comprising the isocyanate prepolymer and the hardener. As the prepolymer composition contains oligosaccharyltransferase with srednekamennogo molecular weight 2500-3500, nigerianisation CIS-1,4 18-28%, TRANS-1,4 58-62% and 1,2-units of 15-20%, a content of isocyanate groups in the prepolymer of 1.9-2.3% - 100 parts by weight; as a hardener - dimethylbenzylamine or dibutylthiourea tin is 0.05 to 5.0 parts by weight, and optionally oligobutadienediol with molecular weight of 1500-3000 1-5 parts by weight, chalk 10-70 parts by weight, calcium oxide 5-10 parts by weight of [the Patent of the Russian Federation No. 1514754, CL C09D No.3 / 72, publ. 15.10.1989, bull. No. 38].

The disadvantage of this known arrangement is the low durability of elastomeric materials based on it, limiting the possibility of wide use.

The reason for the low strength of elastomeric materials of this composition is broad molecular weight distribution of the macromolecules used in the prepolymer, the structural heterogeneity of macromolecules functionality, namely, that the content of the bifunctional macromolecules does not exceed 50-60%, and the proportion of monofunctional and misfunctioning molecular chains, is not capable of binding in a single up the totals, respectively, and 20-30 10-15%. Additional introduction in the composition of 1-5 parts by weight of oligomeric rubber without functional groups increases the degree of structural heterogeneity and an even greater extent affects the distribution by type of functionality. Also used in famous songs of the prepolymer is the product of the interaction of 1 mole of Oligopeptide novogo hydroxyl-containing rubber with 2 moles of diisocyanate, that does not allow creating of rubber with similar molecular characteristics of the solid mesh physical links. As a result, when the cured composition is formed heterogeneous vulcanizing mesh with an uneven distribution of chemical cross-linking in the volume of the vulcanizate and a low share of elasticise-active chains. This structure vulcanizing grid cannot provide a uniform redistribution of stresses and their alignment under load, which does not allow to obtain a material with high strength.

The technical result of the present invention is to provide a composition with a higher strength, hardness and elongation.

The technical result is achieved in that the polymer composition comprising the isocyanate prepolymer and curing agent, as the isocyanate prepolymer is used, the prepolymer obtained by the interaction of four moles of 4,4'-diphenylmethanediisocyanate and one mole oligonucleotide with a molecular mass of 2800-3200, the content of hydroxyl groups of 0.9 to 1.3%, a content of isocyanate groups in the prepolymer 8.0 to 9.7 per cent, and as a hardener 3,3'-dichloro-4,4'-diaminodiphenylmethane or a mixture of 2,4 - and 2,6-isomers of 3,5-diethyltoluenediamine in the ratio of 80:20 in the following ratio of components, parts by weight:

Specified the isocyanate prepolymer100
3,3'-dichloro-4,4'-diaminodiphenylmethane
or a mixture of 2,4 - and 2,6-isomers
3.5-diethyltoluenediamine
in the ratio of 80:2011-31

The technical result is achieved due to the fact that in contrast to the known composition the proposed composition contains the isocyanate prepolymer obtained by the interaction of the hydroxyl-containing oligonucleotide rubber with a large excess of 4,4'-diphenylmethanediisocyanate. Oligobutadienes hydroxyl-containing rubber has a high degree of functionality, almost equal to two, a narrow molecular weight distribution and perfect distribution by type of functionality. The proportion of bifunctional macromolecules reaches 92%, when the content misfunctioning molecules not more than 2%. Hydroxyl-containing oligobutadienes rubber is a product of anionic polymerization, has a linear structure, srednekislye molecular weight 2800-3200, the content of terminal hydroxyl groups of 0.9 to 1.3%. The microstructure of the rubber is 1,4-CIS 10-18%, 1,4-TRANS 18-28%, of 1,2-C is egnew 58-70%. Chemical structure

where R is H, CH3.

The isocyanate prepolymer obtained by the interaction of the specified oligonucleotide with excess 4,4'-diphenylmethanediisocyanate contains 8.0 to 9.7 percent isocyanate groups. The resulting prepolymer also differs perfect distribution of macromolecules by type functionality. The use of 4,4'-diphenylmethanediisocyanate when the ratio of functional groups NCO:OH=4:1 upon receipt of the prepolymer provides increased functionality due to the interaction of urethane and isocyanate groups, creating additional stitching cross regular patterns. The structure of the prepolymer has the following form:

where R1- oligobutadienes block;

R2- fragment of 4,4'-diphenylmethanediisocyanate.

This structure of the prepolymer, functionality and distribution of functional groups when used for curing aromatic diamines diameter X or itakura leads to the formation of microheterogeneous grid with alternating flexible oligonucleotide blocks and rigid urea-urethane blocks. The presence in the structure of the cured product of microvas flexible and rigid blocks determines the characteristics of its properties: high strength, hardness, combined with elasticity. retino-urea blocks create a continuous physical grid due to extremely strong intermolecular interactions. While elastic properties are preserved thanks to the microstructure of the oligomeric unit with a high proportion (58-70%) of 1,2-units. The microstructure of the prepolymer used ensures the preservation of the amorphous highly elastic to plastic state rubber flexible microblock, despite the high density of crosslinking and regularity chemical break ties. This enables the development of highly elastic to plastic deformation and orientation of chains in the elastic microblock.

As a result, when curing is implemented close to the ideal, the more dense and uniform spatial grid of cross-linked elastomer with minor defects and a high content of elasticise active circuits. Strength increases due to more uniform distribution of stresses during deformation, as well as their redistribution. Such a net physical links are mobile enough, at high voltages and at the local overvoltage physical communication can break down and formed again, thereby equalizing the voltages.

The technical result of the increased strength of a polymer composition comprising the isocyanate prepolymer of this structure, curing 3,3'-dichloro-4,4'-diaminodiphenylmethane is not obvious, since the analysis of the known solutions do not give the SnoVanis to assume, the combination of these components should lead to hardening of the proposed composition.

As the isocyanate prepolymer is used, the prepolymer with a content of 8.0 and 9.7% of the isocyanate groups. As the hardener used was 3,3'-dichloro-4,4'-diaminodiphenylmethane (diameter X, TU-6-14-980-84, ILAC, Kuralon) or a mixture of 3,5-dimethyldi-2,4-toluylenediamine and 3.5-dimethyldi-2,6-toluylenediamine in the ratio of 80:20 (atakor 300).

The prepolymer receive the following procedure: a sample of 200 g oligonucleotide rubber Krasol LBH 3000 with the content of 1.1% of hydroxyl groups are placed in a flask, heated to 80°C. with stirring, maintained at this temperature under vacuum at a residual pressure of not higher than 10 mm Hg for 60 minutes, enter to 64.8 g of 4,4'-diphenylmethanediisocyanate and incubated at 80°C under stirring for 2 hours. The resulting prepolymer is poured, cooled.

Calculation of the necessary quantity of 4,4'-diphenylmethanediisocyanate are according to the formula in grams per 100 g of rubber:

M=(42**100*4)/(17*33,6),

where M - hanging diisocyanate;

And the content of hydroxyl groups in the rubber.

For the preparation of compositions heated to a temperature of 50-60°C. the prepolymer is mixed with the melt 3,3'-dichloro-4,4'-diaminodiphenylmethane within 1-2 minutes. The ratio of NCO-groups and NH2groups of components varies from 0.5 to 1.2. The prepared composition is poured on revelation is taken form and incubated at 20-25°C for three days. During curing of the prepolymer with itakura the temperature of the prepolymer 20-25°C.

In the composition to reduce the viscosity can be entered plasticizers and solvents.

The composition of the prototype was prepared by sequential introduction of the components in the prepolymer and mixing.

The feasibility of the proposed solution and the optimality of the declared limits of the ratios of the components of the composition are confirmed by the following experimental data. The results of the experiments, the compositions and their properties, and the properties of the compositions according to the prototype shown in the table.

The composition and properties of compositions
Name of the component1234567891011The prototype, Pat. Of the Russian Federation No. 1514754
Polybutyleneterephthalate---- -------100
Chalk-----------50
Calcium oxide-----------10
Oligobutadienediol---------- -2,0
Dibutylthiourea tin or dimethylbenzylamine-----------0,05
The isocyanate prepolymer obtained by the interaction of four moles of 4,4'-diphenylmethanediisocyanate and one mole oligonucleotide with a molecular mass of 2800-3200, with a content of hydroxyl groups of 0.9 to 1.3%100100100100100100100100100100100
3,3'-Dichloro-4,4 diaminodiphenylmethane1622283134-- -----
A mixture of 2,4 - and 2,6-isomers of 3,5-diethyltoluenediamine in the ratio of 80:2091115172224-
The ratio of NCO:NH20,60,81,01,11,20,40,50,70,81,01,11
Conditional tensile strength, MPa51212,58,05,63,65,88,610,4 4,2the 3.80,6
Elongation, %608090110210607080110704060
Hardness, srvc. units609092907881889090908450
Adhesion to metals at break, %-3420,8-2343-0,6
See the definition. The composition of 1,6-prepolymer contains 8,0% NCO; composition 5,11-9,7% NCO; the remaining 8.8% of NCO.

Materials testing coatings performed according to GOST 263-93, GOST 270-75.

From the table it is seen that the use as the basis of the composition claimed prepolymer in combination with the curing agent provides a significant increase in the durability of the coatings, thereby increasing durability.

The decrease in the amount of hardener to less than 11 parts by weight or increase to more than 31 parts by weight leads to a decrease in strength due to significant deviations from equimolecular ratio of reactive functional groups.

The inventive polymer composition, as proved by the examples, allows to obtain elastomers and coatings with improved complex mechanical properties, increased strength, hardness, elongation and adhesion properties of coatings.

Polymer composition for elastomeric waterproofing roof coverings, floor coverings and sports grounds, including the isocyanate prepolymer and the curing agent, characterized in that as isocyanatobenzene prepolymer using a prepolymer obtained by the interaction of four moles of 4,4'-diphenylmethanediisocyanate and one mole oligonucleotide molecular weight 2800-3200, the content of hydroxyl groups of 0.9 to 1.3%, a content of isocyanate groups in the FMR is alimera 8.0 to 9.7 per cent, and as hardener - 3,3'-dichloro-4,4'-diaminodiphenylmethane or a mixture of 2,4 and 2,6 isomers of 3,5-diethyltoluenediamine in the ratio of 80:20 in the following ratio of components, parts by weight:

specified the isocyanate prepolymer100
3,3'-dichloro-4,4'-diaminodiphenyl-
methane or a mixture of 2,4 and 2,6 isomers
3.5-diethyltoluenediamine
the ratio 80:2011-31



 

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Polymer composition // 2393190

FIELD: chemistry.

SUBSTANCE: invention relates to a polymer composition for elastomer roof coatings, floor and sports field coatings. The composition contains the following in pts. wt: 100 - isocyanate prepolymer, 1.8-1.5 - ethoxylated glycerin or glycerin or trimethylolpropane and 0.01-0.05 - tin dibutyldilaurate. The isocyanate prepolymer used contains 4.0-5.0% isocyanate groups and is obtained by reacting two moles of 4,4'-diphenylmethanediisocyanate and one mole of oligobutadienediol with molecular weight of 1800-2200 and 1.2-1.9% content of hydroxyl groups.

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1 tbl

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