RU2452755C1 - Coating composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: coating composition contains oligobutadiene diol, glycerine, mineral filler, polyisocyanate, an organotin catalyst, 2,4,6-tri-tert-butylphenol, ethyl silicate, polysulphide oligomer, zinc oxide, diatomite, a modifying additive - 1',1',11,'-trihydroperfluoroundecaneoxy-(2"-hydroxy ethyl)-oligo-2-methyl-1-oxylidene of formula

EFFECT: high sedimentation resistance of the composition, dynamic and physical-mechanical, adhesion properties of the 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 composition for the manufacture of elastic coatings, including butadiene-piperylene rubber, calcium oxide, chalk, glycerin, a urethane formation catalyst, polyisocyanate and triethylbenzylammonium chloride [RF Patent 2211850 C1, cl. 6 C09D 109/00, publ. 1999].

A wide distribution of the type of functionality of the butadiene-piperylene oligomer causes a 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 composition for coating sports fields and waterproofing coatings, including a hydroxyl-containing copolymer of polybutadiene and isoprene, a plasticizer, a mineral filler, a trifunctional low molecular weight alcohol, polyisocyanate, a urethane formation catalyst and 2,4,6-tri-tert-butylphenol [RF Patent 2186812 C2, cl. 7 C09D 109/00, publ. 2002].

The disadvantage of the composition is the low sedimentation stability. The coating obtained from this composition is characterized by a low level of dynamic and physical-mechanical properties.

Closest to the proposed technical essence and the achieved result is a composition comprising oligobutadiene diol, a plasticizer, a mineral filler, a trifunctional low molecular weight alcohol, a polyisocyanate, an organotin catalyst, 2,4,6-tri-tert-butylphenol and ethyl silicate in the following ratio of components, wt. hours:

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 composition is the low sedimentation stability. The coating has 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 objective of the invention is to obtain a composition with high sedimentation stability for coatings with high dynamic, adhesive and physico-mechanical properties.

The technical result implemented using the proposed method is to increase the sedimentation stability of the composition, the dynamic, adhesive and physico-mechanical properties of the coating.

The technical result is solved by using a composition including oligobutadiene diol, glycerin, mineral filler, polyisocyanate, organotin catalyst, 2,4,6-tri-tert-butylphenol, ethyl silicate, and it additionally contains a polysulfide oligomer, zinc oxide, diatomite, modifying additive - 1 ′, 1 ′, 11, ′ - trihydroperfluorourodecaneoxy- (2 ″ -hydrosiethyl) -oligo-2-methyl-1-oxylidene of the formula

in the following ratio of components, parts by weight:

Oligobutadiene diol one hundred Glycerol 5-20 Mineral filler 60-100 Polyisocyanate 14-24 Organotin catalyst 0.01-1.10 2,4,6-tri-tert-butylphenol 0.5-1.5 Ethyl silicate 0.8-1.6 Polysulfide oligomer 5-15 Zinc oxide 10-20 Diatomite 20-30 Modifying additive 0.2-0.4

The essence of the proposed method for producing the composition is as follows. In terms of solubility, polysulfide oligomers occupy an intermediate position between oligodienediols and triols. Preliminary mixing of the polysulfide oligomer with glycerol 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 the polyisocyanate, which leads to additional crosslinking of the elastomeric matrix. The introduction of zinc oxide in the composition increases the degree of conversion of the mercapto groups of the polysulfide oligomer and the double bonds of oligobutadiene diol. The use of diatomite, which contains a significant amount of bound water (from 3-15 wt.%), Which has a developed surface and alkaline reaction of aqueous extract, contributes to a more efficient oxidation of mercapto groups of the polysulfide oligomer and an increase in the physicomechanical properties of the coating. The use of a modifying additive allows to increase the processability, adhesive indicators and sedimentation stability of the composition by increasing the adsorption interaction at the oligomeric binder - solid phase interface.

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 3000-3500; the content of hydroxyl groups, wt.%, 0.75-0.89 and oligobutadiene diols 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 (oligobutadiene diols Krasol LBH manufactured by Sartomer).

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, 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).

Ethyl silicate (TU 6-02-895-86) is a mixture of esters of orthosilicic acid. It is a reaction product of ethyl alcohol with silicon tetrachloride. Has the following characteristics: density, kg / m ³ 955-990; mass fraction of silicon dioxide,%, 31-34; mass fraction of tetraethoxysilane,%, 50-60; optical density at a wavelength of 600 nm 0.3-0.4.

Glycerin (GOST 6259-75) is a low molecular weight tri-functional alcohol that is used as a plasticizer and also acts as a branching agent.

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

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

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).

Zinc oxide (GOST 202-84) - is used as a hardener and filler.

Diatomite (TU 5761-001-25310144-99) - is a light porous rock from white to yellowish-gray. The average density of diatomite ranges from 0.15 to 0.6 g / cm ³ . Diatomite for 96% consists of aqueous silica (opal) of the general formula SiO ₂ · nH ₂ O.

As a modifying additive, we used 1 ′, 1 ′, 11, ′ - trihydroperfluoroundecanoxy- (2 ″ -hydro-ethyl) -oligo-2-methyl-1-oxylidene (density ρ = 1267 kg / m ³ and surface tension value σ = 28, 3 mN / m ² ). It is an oligomeric product obtained by the reaction of propylene oxide with 1H, 1H, 11H-trihydroperfluorundecanol-1.

Synthesis of 1 ′, 1 ′, 11, ′ - trihydroperfluorourodecanoxy- (2 ″ -hydrosiethyl) -oligo-2-methyl-1-oxylidene was carried out according to the standard procedure for the addition of propylene oxide to alcohol [M.S. Malinovsky. Oxides of olefins and their derivatives. M .: 1951. - 552 p.]. 100 parts by weight of 1,1.11-trihydroperfluorofluorodecanol and 0.1-0.5% by weight are charged to the reactor. by weight of the alcohol of the proton donor catalyst. Air is pumped out from the reactor using a water-jet pump to a residual pressure of 30-50 mm Hg, after which the reaction mixture is heated to 80-90 ° C with stirring to obtain an alcohol melt. The required amount of propylene oxide through a bubbler is fed into the reactor. The polymerization reaction of propylene oxide is carried out at 90-120 ° C and an overpressure of 1.2-1.5 atm. During the polymerization, intense absorption of propylene oxide occurs. At the end of the reaction, the temperature is reduced to 80-90 ° C and the residual propylene oxide is blown off with nitrogen while pumping the gas mixture with a water-jet pump.

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. Polyisocyanate, zinc oxide and an organotin 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 composition and properties of the composition are shown in tables 1 and 2.

Example 1. The introduction of the components of the composition is as follows. 100 g of Krasol oligobutadiene diol with a molecular weight of 2000 and a content of hydroxyl groups of 1.7%, 5 g of glycerol, 15 g of a polysulfide oligomer — brand I thiokol, 0.2 g of a modifying additive, 50 g of chalk, are loaded into a mixer with a volume of 1 l; 10 g of lime screenings, 0.1 g of tin octoate, 0.5 g of 2,4,6-tri-tert-butylphenol, 0.8 g of ethyl silicate, 30 g of diatomite. The mixing of the components is carried out for 3 hours. To the resulting mixture was added 10 g of rubber crumb and stirred for 30 minutes, then 24 g of polyisocyanate, 20 g of zinc oxide were added 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 2-10.

An example of a prototype. 50 g of oligobutadiene diol with a molecular weight of 3000 and a hydroxyl group content of 1, 3, 120 g of talc, 3 g of triethanolamine, 0.03 g of tin dibutyl dilaurate, 1.5 g of 2,4,6-three are loaded into a mixer with a 1 liter volume mixer tert-butylphenol and 1.2 g of ethyl silicate. 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 modulus of elasticity 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. 264, p.878- 886. Sidorovich EA, Kuvshinsky EV The study of shock compression of rubbers // Solid State Physics. 1961 V.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.

Sedimentation stability was evaluated by the following method. The composition immediately after manufacture was poured into cylinders with a volume of 100 cm ³ . The cylinders were kept at a temperature of 45 ± 2 ° C for 60 days. After a specified exposure time, the top layer of the composition in the amount of 40 ml was selected. The sample was dissolved in white spirit and the solution was centrifuged until the solid phase was completely separated, the content of which was determined by the gravimetric method. Next, the amount of solid phase φ remaining in the selected layer was calculated: φ = x ₁ / x ₀ , where x ₀ is the content of fillers in the freshly prepared composition, wt.%, X ₁ is the content of fillers in the selected layer after holding the composition, wt.%.

As can be seen from tables 1 and 2 with a polysulfide oligomer content of less than 5 wt.h, the effect of increasing the dynamic and physico-mechanical properties is not achieved. At a polysulfide oligomer concentration of 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.

The use of a plasticizer of less than 5 parts by weight leads to a deterioration in processability, a decrease in the strength and deformation properties of coatings. With an increase in the concentration of plasticizer more than 20 parts by weight, the strength properties of the coatings decrease.

When the content of polyisocyanate less than 14 wt.h reduced strength properties of the coating. Exceeding the content of polyisocyanate over 24 wt.h leads to foaming of the composition.

The use of less than 0.01 parts by weight of an organotin catalyst leads to a decrease in the curing rate of the composition. When the content of the urethane formation catalyst is more than 1.10 parts by weight, the viability of the compositions is reduced.

When the concentration of the mineral filler is less than 60 parts by weight, the strength properties of the coating material are reduced. Using more than 100 parts by weight the amount of zinc oxide reduces the elongation of the cured material.

When the content of 2,4,6-tri-tert-butylphenol is less than 0.5 wt.h, the resistance of the coating to atmospheric aging is reduced. The use of 2,4,6-tri-tert-butylphenol in an amount of more than 1.5 wt.h leads to a decrease in the resistance of the coating to weathering.

The use of ethyl silicate in an amount of less than 0.8 wt.h leads to a decrease in the dynamic performance of the coating. When using more than 1.6 parts by weight of ethyl silicate, the strength properties of the coating are reduced.

When the concentration of zinc oxide is less than 10 wt.h reduced strength properties of the coating material. The use of more than 20 parts by weight of zinc oxide leads to a decrease in the elongation of the cured material.

The use of diatomite in an amount of less than 20 wt.h leads to a decrease in the hardness of the coating. When the concentration of diatomite more than 30 wt.h reduced strength properties of the coating.

When the concentration of the modifying additive is less than 0.2 wt.h, the sedimentation stability of the composition is reduced. The use of more than 0.4 parts by weight of the amount of modifying additive leads to a decrease in the strength properties of the coating.

table 2 Coverage Ratios Indicator values Prototype Pat. 2190002 one 2 3 four 5 6 7 8 9 10 The amount of solid phase in the sample,% 90 88 90 87 88 68 65 85 69 85 65 Shore A hardness 79 83 81 73 73 66 65 73 66 58 56 Conditional Strength, MPa 3.4 3.4 3,1 3,5 3,1 1,1 0.8 3,7 2.8 3.0 1.9 Relative extension, % 225 225 223 235 200 105 385 175 195 205 180 Bounce Elasticity,% 59 54 52 51 fifty 34 32 49 46 42 44 Dynamic modulus of elasticity, MPa 6.8 6.0 6.6 6.5 6.6 3.8 3.2 3.4 5.9 6.8 4.8 Mechanical loss tangent 0,094 0.108 0.113 0.108 0.113 0.185 0.302 0.115 0.115 0,120 0,112 Basketball Rebound,% 125 118 109 117 115 93 79 103 112 113 110 Bounce the tennis ball,% 123 118 122 114 109 82 65 104 109 112 110

Thus, the proposed composition is characterized by increased sedimentation stability and allows you to get elastic coatings with improved dynamic, adhesive and physico-mechanical characteristics in comparison with the prototype.

Claims (1)

Composition for coatings comprising oligobutadiene diol, glycerin, mineral filler, polyisocyanate, organotin catalyst, 2,4,6-tri-tert-butylphenol, ethyl silicate, characterized in that the composition further comprises a polysulfide oligomer - liquid thiols with a number average molecular weight of 1700-0055 and a viscosity at 25 ° C of 7.5-50 Pa · s, zinc oxide, diatomite, a modifying additive 1 ′, 1 ′, 11′-trihydroperfluoroundecanoxy- (2 ″ -hydroxyethyl) -oligo-2-methyl-1-oxylidene of the formula

in the following ratio of components, parts by weight:
Oligobutadiene diol one hundred Glycerol 5-20 Mineral filler 60-100 Polyisocyanate 14-24 Organotin catalyst 0.01-1.10 2,4,6-tri-tert-butylphenol 0.5-1.5 Ethyl silicate 0.8-1.6 Polysulfide oligomer 5-15 Zinc oxide 10-20 Diatomite 20-30 Modifying additive 0.2-0.4