RU2470972C1 - Coating composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: coating composition contains low-molecular hydroxyl-containing rubber, polyisocyanate, a urethane-forming catalyst - tin dibutyl dilaurate, glycerine, polymeric petroleum resin obtained by polymerisation of fractions of liquid products of pyrolysis of straight-run gasoline with boiling range of 130-140°C while heating in the presence of an initiator - α,α'-dioxybenzyl peroxide.

EFFECT: improved dynamic and physical-mechanical properties.

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Description

The invention relates to rubber coatings based on liquid hydrocarbon rubbers intended for the device of coatings mainly for sports fields, floors, roofing and insulation coatings in construction.

A known composition for coatings, including copolymers of butadiene and piperylene with a molecular weight of 1200-3200 and 500-1200, glycerin, polyisocyanate, a urethane formation catalyst and rubber crumb (RF patent 1229214, MKI C09D 3/72, 1984). The disadvantage of the coating of this composition are low dynamic and elastic hysteresis properties.

Known composition for coatings, including low molecular weight butadiene-piperylene rubber with a molecular weight of 1200-3200, glycerin, polyisocyanate, a urethane formation catalyst, hydroxylated rubber crumb and calcium oxide (RF patent 2024564, IPC C09D 109/00, 1994).

The disadvantage of this composition is the low dynamic and elastic hysteresis properties due to the wide molecular weight distribution and low functionality of butadiene-piperylene rubber.

A known coating composition, including butadiene-piperylene rubber, glycerin, polyisocyanate, a urethane formation catalyst, calcium oxide, chalk, an antioxidant is a product of polymerization of isoprene production waste - decomposition stage 4.4 of dimethyldioxane-1,3 (RF patent 1775447, IPC С09D 109/00, 1990).

The disadvantage of this composition is the low dynamic and elastic hysteresis properties.

A known coating composition comprising a copolymer of butadiene with isoprene with a monomer ratio of 70:30, a molecular weight of 4000-5000, a hydroxyl content of 0.75-0.89 wt.%, A plasticizer, a mineral filler, a trifunctional low molecular weight alcohol, polyisocyanate, a urethane formation catalyst 2,4,6-tri-tert-butylphenol and ethyl silicate (RF patent 2186812, IPC С09D 109/00, 2000).

The coating of this composition has low dynamic and elastic hysteresis properties.

The closest solution to the proposed invention in technical essence is a coating composition (RF patent 2266935, IPC C09D 109/00, C09D 175/14, 12/27/2005), including low molecular weight rubber, polyisocyanate, a urethane formation catalyst as a low molecular weight rubber, contains a hydroxyl-containing isoprene copolymer with butadiene with a monomer ratio of 20:80, an average molecular weight of 3000-3500, a hydroxyl group content of 0.7-1.1 wt.% (PDI-1K), and the composition further comprises polycaproamide production waste, as follows component ratio, mass parts .:

Isoprene and Butadiene Copolymer (PDI-1K) one hundred Polyisocyanate 10-36 Polycaproamide Production Wastes 0.5-40 Urethane Catalyst 0.001-3.0

The composition further comprises moisture absorption components, a filler, a plasticizer, a solvent, a low molecular weight alcohol, an antioxidant, a pigment, a surfactant.

The coating of this composition has insufficient strength and deformation due to the low level of dynamic and elastic hysteresis properties. This is due to the defectiveness of the three-dimensional structure of the mesh formed during curing. Therefore, the polymer network formed during curing of the rubber has a significant number of defects in the form of free ends that do not absorb the load under impact. In addition, the weak adhesive interaction at the polymer-mineral interface does not allow coatings to be obtained with the required strength.

The technical result is an increase in the dynamic and physico-mechanical properties of the coating.

The technical result is achieved in that the coating composition, including low molecular weight hydroxyl-containing rubber, polyisocyanate, a urethane formation catalyst — tin dibutyl dilaurate, glycerin, characterized in that the composition further comprises an oil polymer resin obtained by polymerizing a fraction of liquid pyrolysis products of straight-run gasolines from 140 ° C when heated in the presence of an initiator of α, α'-dioxibenzyl peroxide, in the following ratio of components, parts by weight:

Low molecular weight hydroxyl-containing rubber one hundred Polyisocyanate 12-24 Tin Dibutyl Dilaurate 0.001-0.1 Glycerol 1-5 Petroleum Resin 10-60

As a low molecular weight hydroxyl-containing rubber, rubbers of the PDI 1K and Krasol LBH brands are used. PDI-1K is a copolymer of isoprene with butadiene with a butadiene content of 80% and 20% isoprene (TU 38. 103342-88). It has the following characteristics: molecular weight 2600-3500, the content of hydroxyl groups 0.7-1.1 wt.%, Viscosity at 25 ° C 2.9-3.4 Pa.s, glass transition temperature minus 64 ° C, density 900 kg / m ³ , the proportion of bifunctional macromolecules reaches 75%.

Rubber Krasol LBH is a low molecular weight polybutadiene, a molecular weight of 2000-5000, a hydroxyl content of 0.6-1.7 wt.%, A viscosity at 25 ° C of 2.2-3.5 Pa.s, a glass transition temperature of minus 68 ° C , density 900 kg / m, the proportion of bifunctional macromolecules reaches 70%. It is possible to use various rubbers containing hydroxyl groups.

Polymethylene - polyphenyl isocyanates based on 4,4-diphenylmethanediisocyanate (TU - 6-03-375-75, 113-03-38-106-90, 113-03-603-86, 2224-152-04691277, are used as a polyisocyanate in the composition) -96).

Tin dibutyl dilaurate (TU 6-02-818-73) is used as a catalyst for urethane formation.

The petroleum polymer resin contains polymer fractions containing hydroxyl groups. The introduction of an oil-polymer resin with hydroxyl groups in hydroxyl-containing rubbers helps to increase the degree of crosslinking of the resulting elastomers upon curing with a polyisocyanate. This provides an increase in the dynamic and physico-mechanical properties of the coating.

The oil-polymer resin is prepared as follows: liquid pyrolysis products (GIP) in the presence of α, α'-dioxibenzyl peroxide initiator are heated in a glycerin bath to 140-150 ° C for 1.5-2 hours. To isolate petroleum resins, unreacted hydrocarbons are distilled off under a vacuum of 25-30 mm Hg. at a temperature of 130 ° C. The composition of the fraction of liquid pyrolysis products of straight-run gasolines with a boiling range of 130-190 ° C is presented in Table 1 [O. Bondaletov. Copolymerization of liquid pyrolysis products and acrylic monomers. / Bondaletov OV, L. I. Bondaletova, I. V. Tyumentseva, V. G. Bondaletov, V. M. Sutyagin. / Polzunovsky Bulletin, 2009, No. 3, pp. 24-28].

Absorption bands corresponding to aromatic radicals present in the composition of the oil polymer are visible on the IR spectrum of the obtained polymer. The absorption intensity in the region of 3400 cm ^-1 , characteristic of the stretching vibrations of the HO group, varies insignificantly, which is important when using the copolymer to obtain polyurethanes based on it.

Table 1 The composition of ZhPP straight-run gasolines with boiling limits of 130-190 ° C Components The composition of the ZhPP,% Cyclopentadiene 4.3 Benzene 3.0 Toluene 8.8 Ethylbenzene 5.7 Xylene 23.7 Styrene 16.6 Methyl ethyl benzene 6.8 α-methyl styrene 3.0 Dicyclopentadiene 20.1 Inden 3.2 Indena derivatives 2,3 Methyl cyclopentadiene dimer 1.7 Unidentified hydrocarbons 0.8 Including unsaturated hydrocarbons 51,2

An example of obtaining a petroleum polymer resin.

Into the reactor, 20 g of GLP and 0.4 g of α, α'-dioxibenzyl peroxide (2.0% by weight) were charged. Then heated in a glycerin bath to 140-150 ° C for 2 hours. After distillation of the unreacted hydrocarbons under vacuum of 25-30 mm Hg (14.2 g is distilled off), 6.2 g of oil tar are obtained, which is 30.4% of the initial mixture taken. Since the FGP fraction contains 51.2% of unsaturated hydrocarbons capable of entering into the polymerization reaction, in terms of unsaturated hydrocarbons, the yield of oil tar is 58.3%.

For the manufacture of the composition using mixing equipment, ensuring the homogenization of the polyisocyanate and the catalyst in rubber. The degree of milling of solid particles should not exceed 100 microns. In the industrial use of the composition, the polyisocyanate is supplied complete with the composition and introduced into it immediately before coating.

The invention is illustrated by the following example. 300 g of low molecular weight PDI-1K rubber, 72 g of polyisocyanate (4,4-diphenylmethanediisocyanate), 0.3 g of urethane formation catalyst (tin dibutyl dilaurate), 15 g of glycerol, 30 g of petroleum resin are mixed in a mixer with a 1 L volume mixer; the mixture is mixed 10 minutes. The resulting mass is poured onto molds and kept at a temperature not lower than 20 ° C for 3-5 days. The composition corresponds to example 1 in table 2.

Other compositions of the prototype are similarly prepared, the compositions of which are shown in table 2.

Tests of the coating material are carried out in accordance with GOST 263-93, GOST 270-75.

The properties of the obtained coating samples are shown in table 3.

From the data of table 3 it is seen that the use of low molecular weight hydroxyl-containing rubber in combination with a petroleum resin, polyisocyanate, glycerin and a urethane formation catalyst (tin dibutyl dilaurate) provides a coating with higher strength and deformation than that of the prototype. Coatings from formulations 6-9 have the worst properties, which is associated with a deviation of the content of the components of the composition from the optimal.

The use of more than 60 parts by weight petroleum polymer resin in the composition leads to a sharp decrease in physical and mechanical properties, less than 10 wt.h. does not affect the properties of the composition.

The introduction of the urethane catalyst less than 0.001 wt.h. impractical due to the long curing time of the coating composition. An increase of more than 0.1 parts by weight reduces the pot life of the composition.

The decrease in the number of polyisocyanate less than 12 wt.h. leads to the formation of a weakly crosslinked structure and the formation of a gel-like product. An increase of over 24 parts by weight impractical due to the tendency to foaming during curing.

table 2 Name of components Composition, parts by weight Prototype Pat. RF 2266 935 one 2 3 four 5 6 7 8 9 10 1. Low molecular weight hydroxyl-containing rubber: PDI-1K one hundred one hundred one hundred one hundred one hundred one hundred one hundred Krasol LBH one hundred one hundred one hundred one hundred 2. Low molecular weight alcohol: glycerin 5 four 3 2 four one 7 0.5 3 four one 3. Polyisocyanate: 4,4-diphenylmethanediisocyanate 24 22 19 fifteen twenty 8 24 12 thirty twenty twenty 4. Urethane Catalyst: Tin Dibutyl Dilaurate 0.1 0.01 0.1 0.01 0.01 0.1 0.001 0.01 0.0001 0.2 0.5 5. Petroleum resin 10 fifteen 25 40 60 5 8 65 twenty - 6. Waste from polycaproamide production - 35

Table 3 The name of indicators The properties Prototype Pat. RF 2266935 one 2 3 four 5 6 7 8 9 10 1. Shore A hardness, cu 65 70 72 70 72 56 53 thirty 35 56 56 2. Conditional strength, kg / cm ² eighteen twenty 25 27 twenty fourteen 10 12 8 16 12 3. Elongation at break,% 95 140 110 90 85 55 70 65 60 68 60 4. The rebound elasticity,% 40 42 55 53 45 42 33 thirty 45 40 42

Thus, the claimed composition for coatings has enhanced dynamic and physico-mechanical properties.

Claims (1)

Composition for coatings, including low molecular weight hydroxyl-containing rubber, polyisocyanate, a urethane formation catalyst - tin dibutyl dilaurate, glycerin, characterized in that the composition further comprises an oil-polymer resin obtained by polymerizing a fraction of the liquid pyrolysis products of straight-run gasolines with a boiling range from 130-140 ° C from 130-140 ° C the presence of the initiator of α, α'-dioxibenzyl peroxide, in the following ratio of components, parts by weight:
Low molecular weight hydroxyl-containing rubber one hundred Polyisocyanate 12-24 Tin Dibutyl Dilaurate 0.001-0.1 Glycerol 1-5 Petroleum Resin 10-60