Polymer composition

FIELD: chemistry.

SUBSTANCE: invention relates to polymer compositions for elastomeric waterproofing, roof coating, floor and sports field coatings. The said composition contains 100 pts. wt isocyanate prepolymer, 3-30 pts. wt ethoxylated glycerin or glycerin, or trimethylol propane as a hardener and 0.005-0.01 pts. wt tin dibutyl dilurate. 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.

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

1 tbl

 

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

Known polymer composition including a prepolymer isocyanate - oligobutadienediol the prepolymer with srednekamennogo molecular weight 2500-3500, content of isocyanate groups of 1.9-2.3% content links: CIS-1,4 18-28%, TRANS-1,4 58 - 62%of 1,2-units of 15-20%, the curing accelerator - dimethylbenzylamine or dibutylthiourea tin, mastic "Couplet", chalk and calcium oxide [RF Patent №1509385, CL C09D No.3 / 72; publ. 23.09.1989, bull. No. 35].

The disadvantage of this polymer composition is a low strength of elastomers and coatings based on it.

Known polymer composition comprising oligosaccharyltransferase with a molecular mass of 2500-3500, content of isocyanate groups of 1.9-2.3% and parts of CIS-1,4 18-28%, TRANS-1,4 58-62%, 1,2 15-20% hardener 2,4-toluylenediisocyanate or polyisocyanate-based diphenylmethanediisocyanate with the content of isocyanate groups of 29.5-30%, mastic "Couplet", chalk, calcium oxide and dimethylbenzylamine or dibutylthiourea tin. [RF patent №1509386, CL C09D No.3 / 72; publ. 23.09.1989, bull. No. 35].

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

The closest solution to the claimed composition to the technical nature (taken as a prototype) is a composition comprising in parts by weight: a prepolymer isocyanate - oligosaccharyltransferase with srednekamennogo molecular weight 2500-3500, content of isocyanate groups of 1.9-2.3% and parts of CIS-1,4 18-28%, TRANS-1,4 58-62%, 1,2 15-20% - 100; hardener dimethylbenzylamine or dibutylthiourea tin 0,05-5,0; oligobutadienediol with molecular weight of 1500-3000 1-5; chalk 10-70; calcium oxide 5-10 [RF Patent №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 bifunctional macromolecules does not exceed 50-60%, and the proportion of monofunctional and misfunctioning molecular chains reaches, 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 affects the distribution by type functional the spine. The prepolymer is obtained by interaction oligobutadienediol rubber having hydroxyl groups with a diisocyanate at a ratio of NCO and Oh groups is 2:1. 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 uniform distribution of stresses and their redistribution and 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 the polymer composition comprising the isocyanate prepolymer and the curing agent, in which the isocyanate prepolymer is used, the prepolymer obtained by the interaction of four moles of 4,4'-diphenylmethanediisocyanate and one mole oligonucleotide with srednekamennogo molecular weight 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 ethoxylated glycerol or glycerin, or trimethylolpropane and dibutylthiourea tin when the trail the next ratio of the components, parts by weight of:

Specified isocyanate
the prepolymer100
Ethoxylated glycerol or
glycerin, or trimethylolpropane3-30
Dibutyltin tin0,005-0,1

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, srednekamennogo molecular weight 2800-3200, the content of terminal hydroxyl groups of 0.9 to 1.3%. Microstructure is aucuba: 1,4-CIS 10-18%, 1,4-TRANS 18-28%, 1,2-links 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 glycerol, trimethylolpropane or ethoxylated glycerol and dibutyltindilaurate tin, leads to the formation of microheterogeneous grid with alternating flexible oligonucleotide blocks and rigid urethane blocks. The presence in the structure of the cured product of microvas flexible and rigid blocks determines the peculiarities of his Holiness ist: high strength, hardness in combination with elasticity. Urethane blocks create a continuous physical grid due to the 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 as such, the net physical links are mobile enough at high voltages, and when the local overvoltage physical links can break and form again.

The technical result of the increased strength of a polymer composition comprising the isocyanate prepolymer of this structure, overide the first ethoxylated glycerol or glycerine, or trimethylolpropane and dibutyltindilaurate tin is not obvious, since the analysis of the known solutions do not give grounds to assume that 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 hardeners use glycerin; trimethylolpropane; ethoxylated glycerine (Laprol 373 - TO-024-1048857-95, the condensation product of glycerine and propylene oxide) and dibutylthiourea tin.

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 and define the content of NCO-groups.

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 is the sample diisocyanate;

And the content of hydroxyl groups in the rubber.

For the preparation of compositions using mixing equipment to ensure the homogenization of the resp is nitela in the prepolymer.

The feasibility of the invention is illustrated by the following examples. A portion of the prepolymer is mixed with a hardener for 2-3 minutes, then add dibutylthiourea tin and mix for another 1-2 minutes. The mixture is applied on the open forms and can stand up to full cure for three days at 20-25°C. the Amount of the prepolymer and the curing agent is calculated so that the molar ratio of NCO and Oh groups were in the range 0.5 to 2.0. The composition and properties of elastomeric coating is shown in the table. Materials testing coatings performed according to GOST 270-75, GOST 263-93, GOST 426-66.

From the table it is seen that the use as the basis of the composition claimed prepolymer in combination with the curing agent can significantly improve the strength of the coatings, which consequently increases their durability. The strength of elastomeric material is increased more than five times, increased hardness, improved deformation ability and elasticity.

6
The composition and properties of compositions
Name of the components and indicators1234578910111213The placeholder
Pat. Of the Russian Federation No. 1514754
Polybutyleneterephtalate-------------100
Chalk-------------50
Calcium oxide---- ---------10
Oligobutadienediol-------------2,0
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%, a content of isocyanate groups in the prepolymer to 8.0 and 9.7%100100100100100100100100100100100 100100
Ethoxylated glycerol (Laprol 373)302530---------50-
Glycerin---2,435,5681012,513,2---
Trimethylolpropane--------- -8,8--
Dibutylthiourea tin0,010,0050,010,0010,010,010,010,010,010,010,15ml0,010,05
The ratio of OH:NCO1,21,00,80,40,50,91,01,31,62,02,21,02,21
The tensile strength, MPa6,47,3the 4.72,63,0the 3.84,26,2 6,56,22,04,81,20,6
Elongation at break, %1208014024014080809010013027010060060
Hardness shore a, services. units8181753670737475737038732050
Ball rebound resilience, %464440223842 44456464028461238
Note: in compounds 1-3 prepolymer contains 8% of NCO-groups in the compounds 4-8 8.8% of NCO-groups in the compounds 8-13 9,7% of NCO-groups.

The decrease in the amount of hardener to less than 3 wt.% and increase to more than 30 parts by weight leads to deterioration of the complex structural characteristics of the coatings due to the significant deviation of the ratio of reactive groups from equimolecular for the prepolymer and hardener. The deviation of the content dibutyltindilaurate tin from the stated limits reduces the rate of curing or reducing the viability of the compositions due to the high speed of curing.

The claimed polymer composition, as proved by the examples, can improve the complex mechanical properties of the 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 the isocyanate prepolymer is used, the prepolymer obtained by the interaction of four moles of 4,4'-diphenylmethanediisocyanate and one mole oligonucleotide forefront of the popular weight 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 used ethoxylated glycerol, or glycerin, or trimethylolpropane and dibutylthiourea tin in the following ratio of components, parts by weight:

specified the isocyanate prepolymer100
ethoxylated glycerol, or
glycerin, or trimethylolpropane3-30
dibutyltin tin0,005-0,1



 

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2 ex, 3 tbl

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10 ex, 2 tbl

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10 ex, 2 tbl

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2 ex, 3 tbl

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.

EFFECT: coatings based on the disclosed composition have high strength, hardness and elasticity.

1 tbl

Polymer composition // 2397192

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

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