RU2325418C1 - Method of coating composition production - Google Patents

Abstract

FIELD: inorganic chemistry.

SUBSTANCE: method is applied for production of coating compositions for run tracks, gyms, roof and hydraulic insulating coatings. Mixture of oligodienediol, mineral filler, plasticizer, urethane catalyst-organotin catalyst and 2,4,6-tri-tret-butyl phenol are added to premixed composition of trifunctional low-molecular alcohol and polysulphide oligomer with further after-mixture addition of polymethylenepolyphenylenepolypolyisocyanate with isocyanate groups content 29.5-31.0%. Technical result is improved dynamic parameters and physical-mechanical properties of coating.

EFFECT: improvement of dynamic parameters and physical-mechanical properties of coating.

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Description

The invention relates to methods for producing compositions intended for the manufacture of coatings for athletics treadmills, gyms, playgrounds, as well as roofing and waterproofing coatings.

A known method of obtaining a composition for the manufacture of elastic coatings by mixing low molecular weight butadiene-piperylene rubber with calcium oxide, chalk, glycerin, a urethane catalyst, polyisocyanate and triethylbenzylammonium chloride [RF Patent 2211850 C1, Cl. 6 C09D 109/00, publ. 1999].

The wide distribution of the type of functionality of the butadiene-piperylene oligomer results in the defectiveness of the three-dimensional network formed during its curing with polyisocyanate, which is a consequence of the low level of dynamic and physico-mechanical properties of the coating.

A known method of producing compositions for coating sports fields and waterproofing coatings by mixing a hydroxyl-containing copolymer of polybutadiene and isoprene with a plasticizer, mineral filler, trifunctional low molecular weight alcohol, polyisocyanate, a urethane formation catalyst and 2,4,6-tri-tert-butylphenol [RF Patent 2186812 C2. 7 C09D 109/00, publ. 2002].

The disadvantage of this method is the low level of dynamic and physico-mechanical indicators.

Closest to the proposed method is a composition by mixing oligobutadiene diol with a plasticizer, a mineral filler, a trifunctional low molecular weight alcohol, polyisocyanate, an organotin catalyst, 2,4,6-tri-tert-butylphenol and ethyl silicate in the following ratio of components:

Oligobutadiene diol one hundred Plasticizer 5-30 Mineral filler 90-150 Trifunctional low molecular weight alcohol 1-5, Polyisocyanate 12-24 Organotin catalyst 0.01-1.10 2,4,6-tri-tert-butylphenol 0.5-1.5 Ethyl silicate 0.8-1.6

[RF patent 2190002, Cl. 7 C09D 109/00, publ. 2002].

The disadvantage of the coating formed by the specified method of obtaining the composition is a low level of dynamic and physico-mechanical properties. This is due to the fact that the trifunctional low molecular weight alcohol, being a strongly polar compound, is limitedly compatible with the oligodiene binder. When mixing the components of the composition, the triol is distributed in the form of microdrops, forming a colloidal system. Therefore, the cross-linking density of the elastomeric material (triol acts as a chain branching agent) is low, which does not allow to provide the necessary level of sports-technical and physical-mechanical properties of elastic coatings.

The technical result implemented using the proposed method is to obtain a composition for coating with high dynamic and physico-mechanical properties.

The technical result is solved by mixing oligobutadiene diol with a mineral filler, a plasticizer, an urethane formation catalyst — an organotin catalyst, 2,4,6-tri-tert-butylphenol, a trifunctional low molecular weight alcohol and polymethylene polyphenylene polyisocyanate with an isocyanate content of 29.531% that in a mixture of oligobutadiene diol, a mineral filler, a plasticizer, an urethane formation catalyst — an organotin catalyst and 2,4,6-tri-tert-butylpheno a preformed mixture of a trifunctional low molecular weight alcohol and a polysulfide oligomer is introduced, followed by the introduction of the specified polyisocyanate after stirring in the following ratio of components, parts by weight:

Oligobutadiene Diol - 100

Softener - 5-30

Mineral filler - 90-150

Trifunctional low molecular weight alcohol - 1-5

The specified polyisocyanate - 14-24

Organotin catalyst - 0.01-1.10

2,4,6-tri-tert-butylphenol - 0.5-1.5

Polysulfide Oligomer - 5 -15

The essence of the proposed method for producing the composition is as follows.

In terms of solubility, polysulfide oligomers are intermediate between oligodienediols and triols, for example glycerol, trimethylolpropane, triethanolamine. Preliminary mixing of the polysulfide oligomer with a trifunctional low molecular weight alcohol makes it possible to obtain a homogeneous mixture that is well compatible with the oligodienediol binder. When the composition is cured, a regular network structure with a narrow molecular weight distribution of interstitial chains is formed. In addition, the sulfhydryl groups of the polysulfide oligomer interact with an isocyanate hardener, which leads to additional crosslinking of the elastomeric matrix.

As the oligobutadiene diol, the composition uses a copolymer of butadiene and isoprene PDI-1K (TU 38.103342-88) with a monomer ratio of 70:30; molecular weight 4000-5000; the content of hydroxyl groups, wt.% 0.75-0.89 and oligodienediols with a molecular weight of 2000-5000; a polydispersity index of 1.20-1.35; Brookfield viscosity, Pa · s (25 ° C) 8.5-22; the content of terminal hydroxyl groups,% 0.7-1.7; microstructure,% 1,4-cis 10-15, 1,4-trans 20-25, 1,2- (vinyl) 60-70; distribution by OH groups (RTF),% non-functional 2, monofunctional 6, bifunctional 92; density, kg / m ³ 900-910 (oligodienediols Krasol LBH manufactured by Sartomer).

As a plasticizer, the composition contains compounds used in the manufacture of elastomeric materials based on diene rubbers: alkyl (aryl) esters of phthalic or phosphoric acid, chloroparaffins.

Fillers of the composition are mineral powders of medium dispersion, for example, chalk, lime-screenings, kaolin, talc.

2,4,6-Tri-tert-butylphenol is a crystalline powder with a greenish-yellow tint, it is soluble in hydrocarbons and has the following characteristics: melting point 129-131 ° C, mass fraction of ash - not more than 0.05%. Obtained by alkylation of phenol with isobutylene in the presence of a catalyst. Trade name - antioxidant P-23 (TU 6-14-26-77).

As the polysulfide oligomer, liquid thiocols of grades I, II and NVB-2 are used, characterized by a number average molecular weight of 1700-5500; number average functionality 2.22-2.68; the content of SH groups of 1.6-4.3; viscosity, Pa · s (25 ° C) 7.5-50 (GOST 12812-80, TU 38.50309-93).

As a low molecular weight tri-functional alcohol, glycerin, triethanolamine or trimethylolpropane are used in the composition.

As the polyisocyanate in the composition, polymethylene polyphenylene polyisocyanates are obtained, obtained by phosgenation of the condensation product of aniline with formaldehyde (TU 2224-152-04691277-96). The content of isocyanate groups 29.5-31%.

As the organotin catalyst, tin octoate and tin dibutyldylaurinate (TU 6-02-818-78) are used, and other organotin compounds used for the synthesis of polyurethanes can be used.

Additives may be added to the composition to give other advantages to the coating material. As a component that ensures a reduction in the consumption of the composition for the manufacture of a unit of coating area, rubber crumb is used. To improve the appearance of the composition can be introduced pigments.

For the manufacture of the composition, mixing equipment is used to ensure a homogeneous suspension of the filler in the volume of the composition with a milling degree of solid particles of not more than 100 microns. The polyisocyanate and the urethane formation catalyst are supplied complete with the composition and added to it at the place of laying the coating. The crumb rubber is mixed into the composition before the introduction of the hardener.

The invention is illustrated by examples 1-8 (composition 1, table 1).

Example 1. In a mixer with an anchor mixer of 0.05 L volume, 15 g of a polysulfide oligomer, 5 g of a trifunctional low molecular weight alcohol are charged and mixed for 10 minutes. The resulting mixture is unloaded into a glass and incubated for 30 minutes. At the same time, 100 g of Krasol oligobutadiene diol with a molecular weight of 3000 and a content of hydroxyl groups of 1.7%, 80 g of chalk, 10 g of lime screenings, 5 g of dibutyl phenyl phosphate, 0.1 g of tin octoate, 2, are loaded into a mixer with a 1 L volume of 1 liter. 4,6-tri-tert-butylphenol. The components are mixed for 30 minutes, and then a seasoned mixture of polysulfide oligomer and trifunctional low molecular weight alcohol is added and mixed for another 10 minutes. To the resulting mixture was added 10 g of rubber crumb, 24 g of polyisocyanate and mixed again for 8 minutes. The resulting mass is poured into molds and incubated for 20-25 days at a temperature of 18-25 ° C.

Similarly, the compositions are prepared according to examples 1-8.

Example 9. A 100 g oligobutadiene diol PDI-1, 100 g kaolin, 15 g dioctyl phthalate, 4 g trifunctional low molecular weight alcohol, 0.01 g tin dibutyl dilaurate, 1.0 g 2.4.6 tri- tert-butylphenol, 5 g of red C pigment and 15 g of polysulfide oligomer. 20 g of polyisocyanate are added to the resulting mixture and again stirred for 8 minutes. The resulting mass is poured into molds and incubated for 20-25 days at a temperature of 18-25 ° C.

Example 10. In a mixer with an anchor mixer of 1 liter volume, 100 g of Krasol oligobutadiene diol with a molecular weight of 4000 and a content of hydroxyl groups of 0.85%, 120 g of chalk, 20 g of lime sifting, 4 g of trifunctional low molecular weight alcohol, 1.0 g 2 are loaded , 4,6-tri-tert-butylphenol, 5 g of red C pigment, 0.06 g of tin dibutyldylaurinate and 10 g of polysulfide oligomer. 20 g of polyisocyanate are added to the resulting mixture and again stirred for 8 minutes. The resulting mass is poured into molds and incubated for 20-25 days at a temperature of 18-25 ° C.

An example of a prototype. 50 g of oligobutadiene diol with a molecular weight of 3000 and a content of hydroxyl groups of 1.3, 120 g of talc, 3 g of triethanolamine, 0.03 g of tin dibutyl dilaurate and 1.5 g of 2,4,6-three are loaded into a mixer with a 1 L volume mixer tert-butylphenol. The components are mixed for 20 minutes, after which another 50 g of oligobutadiene diol, 20 g of chloroparaffin KP-470 are added to the suspension, and the components are continued to mix for 10 minutes. Then, 16 g of polyisocyanate was added to the mixture and stirred again for 8 minutes. The resulting mass is poured into molds and incubated for 20-25 days at a temperature of 18-25 ° C.

Coating samples are tested according to GOST 263-75, GOST 275-75, GOST 6950-73, GOST 2678-88. The dynamic elastic modulus and the dielectric loss tangent are determined by the method of single shock compression on a pendulum elastometer (see Kuvshinsky E.V., Sidorovich E.A. Pendulum elastometer KS // Journal of Theoretical Physics, 1957, V. 26 4, p. 878- 886. Sidorovich EA, Kuvshinsky EV The study of shock compression of rubbers // Solid State Physics. 1961, T.3. 11, p.3487-3494). Ball rebound tests are performed according to DIN 18035, part 6 by determining the ratio of the ball rebound height from the coating compared to the concrete floor.

The composition and properties of the coating obtained by the proposed method are shown in tables 1 and 2.

As can be seen from tables 1 and 2, when the content of the polysulfide oligomer is less than 5 parts by weight the effect of increasing dynamic and physico-mechanical properties is not achieved. When the concentration of the polysulfide oligomer is more than 15 parts by weight the coating has a reduced level of complex properties due to the competing reaction of the sulfhydryl groups of the polysulfide oligomer and the hydroxyl groups of the oligodienediol with the polyisocyanate. When the content of polyisocyanate is less than 14 parts by weight strength properties of the coating are reduced. The excess content of polyisocyanate over 24 wt.h. leads to foaming of the composition.

Thus, the application of the proposed method for producing the composition allows to obtain elastic coatings with improved dynamic and physico-mechanical characteristics, compared with the prototype.

Table 1 Name of components Composition, parts by weight Prototype Pat. 2190002 one 2 3 four 5 6 7 8 9 10 PDI-1 one hundred one hundred Krasol LBH one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred Mineral filler: - a piece of chalk 80 - - 120 150 170 - - - 120 - - lime screenings 10 - - twenty - - - - - twenty - - kaolin - one hundred - - - - 120 - one hundred - - - talc - - 120 - - - - 60 - - 120 Plasticizer 5 fifteen twenty twenty thirty 40 fifteen 2,5 fifteen twenty twenty Trifunctional low molecular weight alcohol 5 four 3 2 one 0.5 3 6 four 2 3 Tin Octoate 0.1 - - - 0.05 - 0.10 0.15 - - - Tin Dibutyl Dilaurate - 0.01 0,03 0.06 - 0.005 - - 0.01 0.06 0,03 2,4,6-tri-tert-butylphenol 0.5 1,0 1,5 1,0 0.5 1,0 0.25 2.0 1,0 1,0 1,5 Rubber crumb 10 - - - 10 - - - - - Pigment red C - 5 - 5 - - - - 5 5 - Polyisocyanate 24 twenty 16 16 fourteen 16 10 28 twenty 16 16 Polysulfide oligomer fifteen fifteen 10 10 5 2,5 twenty 5 fifteen 10 - Note: 1. As a plasticizer in examples 1 and 6, dibutyl phenyl phosphate is used, in examples 2.8, dioctyl phthalate is used, in the remaining examples and prototype chloroparaffin KP-470 is used. 2. As a low molecular weight alcohol in examples 3,5 and prototype triethanolamine is used, in example 1 - trimethylolpropane, in the rest glycerol. 3. The molecular weight / content of hydroxyl groups (%) of oligobutadiene diol Krasol LBH in the examples is: 1, 3 and prototype - 3000 / 1.3; 4, 6, 10 - 4000 / 0.85; 5 - 5000 / 0.70; 7-5000 / 0.56; 8 - 1500 / 2.30. 4. As a PSO in example 1, 7, 8, a thiokol of brand I is used, in example 2, 3, 5 - a thiokol of brand II, in example 4, 6 - a thiokol of brand NVB-2. 5. In examples 9, 10, the polysulfide oligomer is introduced separately from the trifunctional low molecular weight alcohol, in other cases, in a mixture with trifunctional low molecular weight alcohol.

table 2 Coverage Ratios Indicator values Prototype Pat. 2190002 one 2 3 four 5 6 7 8 9 10 Shore A hardness, arb. 68 62 56 60 58 45 thirty The cured foam sample 58 56 56 Conditional Strength, MPa 3.4 3.6 3.3 3.4 3.2 1,1 0.5 3.0 2.9 1.9 Relative extension, % 210 200 220 230 190 90 400 190 210 180 Bounce Elasticity,% 56 46 49 42 38 32 12 44 40 44 Dynamic modulus of elasticity, MPa 6.0 5.8 5.9 5.7 5.5 3.6 2.6 5.5 5.3 4.8 Mechanical loss tangent 0,096 0,112 0.108 0,112 0.134 0.183 0,304 0.116 0,110 0,112 Basketball Rebound,% 120 116 110 116 112 96 80 114 112 110 Bounce the tennis ball,% 118 114 118 114 110 84 60 112 110 110

Claims (1)

A method of obtaining a coating composition by mixing oligobutadiene diol with a mineral filler, a plasticizer, an urethane formation catalyst — an organotin catalyst, 2,4,6-tri-tert-butylphenol, a trifunctional low molecular weight alcohol and polydimethylene polyphenylene polyisocyanate with an isocyanate group content of 29.5-31.0% that a mixture of oligobutadiene diol, a mineral filler, a plasticizer, an urethane formation catalyst — an organotin catalyst and 2,4,6-tri-tert-butylphenol is introduced a preformed mixture of low molecular weight trifunctional alcohol, and polysulfide oligomer, followed by introduction after mixing said polyisocyanate with the following component ratio, mass parts .: Oligobutadiene diol one hundred Plasticizer 5-30 Mineral filler 90-150 Trifunctional low molecular weight alcohol 1-5 Specified Polyisocyanate 14-24 Organotin catalyst 0.01-1.10 2,4,6-tri-tert-butylphenol 0.5-1.5 Polysulfide oligomer 5-15