RU2550195C1 - Coating composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: coating composition, which includes low-molecular weight hydroxyl-containing butadiene-based rubber and an isocyanate curing agent - polyisocyanate. The rubber is hydroxyl-containing polybutadiene rubber or isoprene and butadiene copolymer rubber. The composition additionally contains an acrylate-containing cross-linking agent selected from: methyl methacrylate, butyl methacrylate, dimethacrylic ester of triethylene glycol and oligoester acrylate MGF-9, a peroxide initiator and N,N,4-trimethylaniline.

EFFECT: high hardness and strength of coating elastomers.

1 tbl, 1 ex

Description

The invention relates to compositions based on liquid hydrocarbon rubbers for the manufacture of sports field coatings, floors, roofing and waterproofing coatings.

A known coating composition, including oligodienediol - isoprene-butadiene copolymer, plasticizer, filler, trifunctional low molecular weight alcohol, urethane formation catalyst, 2,4,6-tri-tert-butylphenol, hardener polyisocyanate and additionally ethyl silicate (see patent RF 2186812, C09D 109/09/09/09/00 Publish. 08/10/2002).

A known coating composition comprising a low molecular weight hydroxyl-containing rubber — an isoprene-butadiene copolymer, a polyisocyanate, a urethane formation catalyst, a desiccant, a filler, a plasticizer, a low molecular weight alcohol, a pigment, an alkyl phenol antioxidant, and a rheological additive (see Patent No. C09L 0968, patent no. / 00. Published on November 27, 2006, Bull. No. 2).

The disadvantage of these compositions is the low hardness and strength of the cured elastomeric coatings.

A known composition for coatings, including oligobutadiene diol, a plasticizer, a mineral filler, a trifunctional low molecular weight alcohol, a urethane formation catalyst, 2,4,6-tri-tert-butylphenol, polyisocyanate and ethyl silicate (see RF patent 2190002, C09D 175/08. Publish. 09.27.2002. )

The disadvantage of this composition is the low hardness and strength of the elastomeric coating material.

The closest solution to the proposed invention (prototype) is a composition (see RF patent 2433155, C09D 175/14, C09D 109/00. Publ. 10.11.2011, Bull. No. 31), comprising isocyanate hardener-polyisocyanate, a urethane formation catalyst and a base - hydroxyl-containing polybutadiene rubber of the microstructure,%: 1,4-trans 10-15 and 1,2-units 85-90, molecular weight 1250-3200 and the content of hydroxyl groups of 0.82-2.36% and an additional mixture of isomers 3,5 -dimethylthio-2,4-toluylene diamine and 3,5-dimethylthio-2,6-toluylene diamine in a ratio of 75.5-81: 18-20 or a mixture of 3,5-diethyl-2,4-toluyl ndiamina and 3,5-diethyl-2,6-toluenediamine in a ratio 75,5-81: 18-20 in the following ratio, mass parts .:

The specified hydroxyl-containing polybutadiene rubber one hundred Isocyanate Hardener-Polyisocyanate 12-36 Urethane Catalyst 0.01-1 A mixture of isomers of 3,5-dimethylthio-2,4-toluylene diamine and 3,5-dimethylthio-2,6-toluene diamine or a mixture of 3,5-diethyl-2,4-toluylene diamine and 3,5-diethyl-2,6-toluene diamine in the ratio of 75.5-81: 18-20 0.7-8.4

Represented in the prototype hydroxyl-containing polybutadiene rubber is a low molecular weight hydroxyl-containing rubber based on butadiene.

Coatings from this composition are characterized by insufficient hardness and strength.

The present invention is to develop a composition for coatings based on low molecular weight hydroxyl-containing rubber with improved strength characteristics.

The technical result is to increase the hardness and strength of elastomers for coatings.

The technical result is achieved in that the coating composition comprising a low molecular weight hydroxyl-containing rubber based on butadiene, an isocyanate hardener-polyisocyanate, contains rubber as a hydroxyl-containing polybutadiene rubber or a rubber copolymer of isoprene and butadiene, and additionally contains an acrylate-methyl acrylate-acrylate-methyl-acrylate , triethylene glycol dimethacrylic ester and MGF-9 oligoester acrylate, peroxide initiator and N, N, 4-trimethylaniline with the following in relation to components, parts by weight:

The specified hydroxyl-containing rubber one hundred Isocyanate Hardener-Polyisocyanate 8-20 Acrylate Crosslinking Agent 5-100 Peroxide initiator 0.05-5 N, N, 4-trimethylaniline 0.01-0.1

The essence of the invention lies in the fact that the presented hydroxyl-containing rubber is additionally crosslinked by double bonds with an acrylate-containing agent. Double bond crosslinking of the rubber is initiated and activated by peroxide and N, N, 4-trimethylaniline. N, N, 4-trimethylaniline is used to lower the decomposition temperature of peroxide. This is because the compositions cure at room temperature. Curing by double bonds in the presence of a crosslinking agent proceeds together with curing by the urethane formation mechanism involving terminal hydroxyl groups. Such a combined curing system while extending the chains along urethane bonds and forming cross bonds with an acrylate-containing agent increases the crosslinking density of the elastomer, which increases its strength properties.

Used low molecular weight hydroxyl-containing polybutadiene rubber is similar to the rubber used in the prototype, NISSO PB G-3000 with a hydroxyl content of 0.9-1.2%, a molecular weight of 2600-3200. Also used are the hydroxyl-containing polybutadiene rubber Krasol LBH 3000 with a hydroxyl content of 0.9-1.2%, a molecular weight of 2800-3200, a rubber copolymer of isoprene and butadiene PDI-1K with a monomer ratio of 20:80, with an average molecular weight of 3000 -3500 and the content of hydroxyl groups of 0.7-1.1% (TU38.103342-88).

Polyisocyanates, in particular polymethylene phenyl isocyanates based on 4,4′-diphenylmethanediisocyanate (TU-6-03-375-75, 113-03-38-106-90, 113-03-603-86, 2224-152, are used as isocyanate hardener -04691277-96) or their imported analogues: desmodur, suprasek 5005, MR200 million and others with the content of isocyanate groups 29-32%.

Methyl methacrylate (GOST 20370-74), butyl methacrylate (TU 2435-025-55856863-2004), triethylene glycol dimethacrylate (TU 6-01-843-73) and MGF-9 oligoester acrylate (TU 2226-002-99176106) are used as the crosslinking agent. -2012).

Benzoyl peroxide (TU 2417-006-51764779-2007), ditretbutyl peroxide (TU 6-05-2026-86) and lauryl peroxide (TU6-05-1998-85) are used as the peroxide initiator.

For the manufacture of the coating composition, mixing equipment is used that ensures uniform distribution of the polyisocyanate, crosslinking agent, peroxide initiator and activator in the rubber, with a further homogeneous mixture being obtained.

The invention is illustrated by the following examples:

Example 1. 100 g of rubber, 12 g of polyisocyanate, 5 g of crosslinking agent are loaded into a mixer with a 1 L volume mixer, stirred for 5 minutes, then 0.05 g of peroxide initiator and 0.01 g of N, N, 4-trimethylaniline are added and stirred for another 1 minute.

The resulting mixture is applied to flat forms and kept at a temperature of at least 20 ° C for 3-5 days.

Composition and properties of the coating composition Name of components and indicators Composition in parts by weight and properties of compositions one 2 3 four 5 6 7 8 9 10 eleven 12 13 fourteen Prototype Pat RF 2433155 1. Low molecular weight hydroxyl-containing polydiene rubber: NISSOPBG-3000 one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred Krasol LBH 3000 one hundred PDI-1K one hundred 2. Crosslinking agent: Methyl methacrylate 5 40 40 40 40 70 one hundred 110 2 Butyl methacrylate 40 Triethylene glycol dimethacrylic ester 16 16 16 Oligoester acrylate MGF-9 twenty 3. Peroxide initiator Benzoyl peroxide 0.05 0.32 0.16 0.4 0.4 0.8 1.4 5,0 5.5 0.02 Ditretbutyl Peroxide 0.4 1,2 Lauryl peroxide 0.8 0.32 4. N, N, 4-trimegilaniline 0.01 0.01 0.01 0.01 0.01 0.01 0.1 0.05 0.01 0.01 0.01 0.01 0.01 0.01 5. Polyisocyanag 12 8 12 12 12 twenty 12 12 12 12 12 12 22 6 17 6. Urethane catalyst 0.05 7. A mixture of isomers of 3,5-dimethylthiotoluene diamine 3 Conditional tensile strength, kgf / cm ² 21 28 33 22 51 54 49 fifty thirty 24 fifty 29th 9 6 19 Relative extension, % 180 170 160 170 140 one hundred 140 140 250 150 80 70 40 200 240 Hardness Shore A., conv. 55 60 60 57 70 73 68 70 55 65 80 78 42 35 48

Similarly prepare compositions of composition 2-14.

The composition and properties of all studied compositions are shown in the table.

Coating samples were tested according to GOST 263-93, GOST-270-75.

As the crosslinking agent content increases, the hardness and strength of the cured products increase. Starting at 5 parts by weight crosslinking agent, the hardness increases, with large quantities, both the hardness and strength of the resulting products grow up to 100 parts by weight With a further increase in the crosslinking agent, an increase in strength indicators is not observed, which is associated with an excess of the crosslinking agent and the corresponding delamination of the system. When the content of acrylate-containing crosslinking agent is less than 5 parts by weight an increase in hardness and strength is not observed.

With an increase in the content of peroxide initiator, an increase in strength indicators is also observed, while the optimal amount of peroxide is 0.05-5 wt.h. (1-5% of crosslinking agent). A further increase in peroxide initiator does not lead to an increase in strength indicators. The nature of the initiator does not affect the properties of the resulting products.

When the content of polyisocyanate is less than 8 parts by weight the level of the complex of strength properties decreases due to a significant deviation of the NCO: OH ratio from stoichiometric and a decrease in the crosslink density. With large quantities of polyisocyanate more than 20 parts by weight strength properties are also reduced due to the excess of isocyanate groups, the tendency to foaming and increase the rigidity of the cured product.

Thus, the advantage of elastomers for coatings based on the proposed composition is a higher hardness and strength.

Claims (1)

Composition for coatings, including low molecular weight hydroxyl-containing rubber based on butadiene, isocyanate hardener-polyisocyanate, characterized in that the rubber contains hydroxyl-containing polybutadiene rubber or rubber-copolymer of isoprene and butadiene, and additionally contains acrylate-containing methyl acetate; triethylene glycol dimethacrylic ester and MGF-9 oligoester acrylate, peroxide initiator and N, N, 4-trimethylaniline in the following ratio of components mass parts:
The specified hydroxyl-containing rubber one hundred Isocyanate Hardener-Polyisocyanate 8-20 Acrylate Crosslinking Agent 5-100 Peroxide initiator 0.05-5 N, N, 4-trimethylaniline 0.01-0.1