RU2434917C1 - Coating composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: coating composition contains a base in form of hydroxyl-containing polybutadiene rubber with a microstructure, %: 1,4-trans 10-15 and 1,2-links 85-90, molecular weight 1250-3200 and content of hydroxyl groups 0.82-2.36%; plasticiser, filler, antiageing agent, isocyanate curing agent - polyisocyanate, urethane-formation catalyst and additionally 3,5-dimethylthio-toluylne diamine or 3,5-diethylthio-toluylene diamine.

EFFECT: high level of strength properties - strength, hardness and relative elongation.

4 cl, 2 tbl

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 RF patent 2186812, C09D 109/09/09/09/00 , published on 08/10/2002).

A known composition for coatings, including low molecular weight hydroxyl-containing rubber - isoprene-butadiene copolymer, polyisocyanate, urethane formation catalyst, desiccant, filler, plasticizer, low molecular weight alcohol, pigment, alkylphenol antioxidant and rheological additive (see RF Patent No. 09, No. 27 patent No. 229, patent no. November 27, 2006, Bull. No. 2).

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

A known coating composition comprising 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, published on 09.27.2002 )

The disadvantage of this composition is the low strength of the elastomeric material for coatings.

The closest solution to the proposed invention (prototype) is a composition (see RF patent 2285026, C09D 175/14, publ. 10.10.2006, Bull. No. 28), including an isocyanate hardener - polyisocyanate, a urethane formation catalyst and a base, hydroxyl-containing polybutadiene rubber microstructure %: 10-18 1,4-cis, 18-28 trans-1,4, 58-70 1,2-units with a molecular weight of 2100 and a hydroxyl content of 1.2-1.9%, or a molecular weight of 3000- 3200 and a content of hydroxyl groups of 0.88-1.36%, or a molecular weight of 5000-5300 and a content of hydroxyl groups of 0.6-0.8%, respectively components, parts by weight:

The specified hydroxyl-containing polybutadiene rubber one hundred Isocyanate Hardener - Polyisocyanate 10-36 Urethane Catalyst 0.001-3.0

Additionally, the composition may contain:

Desiccant (calcium oxide, gypsum, cement) 5-20 Filler (chalk, talc, lime-screenings, kaolin) 50-250 Plasticizer 20-100 Low molecular weight alcohol with at least two 1-8 hydroxyl groups or component AF-2 Alkylphenol Antioxidant 0.5-2.0 Pigment 0.5-10.0 Rheological properties modifier - surfactant 0.5-5.0

Coatings from this composition are characterized by an insufficient level of strength properties. This is due to the heterogeneous nature of the morphology of the supramolecular structure of crosslinked rubber that occurs during the curing of the composition. The heterogeneity of the supramolecular structure is caused by the heterogeneity of the microstructure of the rubber base of the composition, in which all heterogeneous types of structures are present at the same time without any prevailing (1,4-cis, 1,4-trans, 1,2-structure).

The technical result of the present invention is to increase the level of strength properties, especially the strength of the coating.

The technical result is achieved in that the coating composition comprising an isocyanate hardener - polyisocyanate, a urethane formation catalyst - a hydroxyl-containing polybutadiene rubber, a plasticizer, a filler and an antioxidant, characterized in that it contains microstructure rubber,%: 1,4-trans 10 -15 and 1,2 units of 85-90, with a molecular weight of 1250-3200 and a hydroxyl content of 0.82-2.36% and additionally 3,5-dimethylthiotoluylenediamine or 3,5-diethylthiotoluylene diamine in the following ratio components, parts by weight:

The specified hydroxyl-containing polybutadiene rubber one hundred Plasticizer 70-140 Filler 80-340 Antioxidant 1-2 Isocyanate Hardener-Polyisocyanate 8-28 Urethane Catalyst 0.01-0.1 3,5-dimethylthiotoluylenediamine or 3,5-diethylthiotoluylenediamine 1.7-8.0

The coating composition according to claim 1, characterized in that it contains dibutyl phthalate, chlorine paraffin HP-470, oil of non-petroleum origin netoxol or PM oil as a plasticizer.

The coating composition according to claim 1, characterized in that as a filler it contains a filler selected from the group consisting of chalk, lime-screenings, calcium oxide, dolomite flour, granular rubber.

The coating composition according to claim 1, characterized in that as an antioxidant it contains an antioxidant selected from the group consisting of alkyl phenol compounds 2,6-ditretbutyl-4-methylphenol (agidol-1), 2,4,6-tritrebutylphenol, 2 , 2-methylene-bis- (4-methyl-6-tert-butylphenol) (product 2246).

The invention consists in the use of a composition of hydroxyl-containing polybutadiene rubber with a homogeneous structure as the basis, the content of 1,2-units reaches 85-90% with a small amount (10-15%) of 1,4-trans and the absence of 1,4-cis units.

The homogeneous microstructure of the rubber chains increases the flexibility of the interstitial blocks in the crosslinked elastomers, increases the compatibility with the isocyanate hardener, which increases the degree of crosslinking, improves the morphology of the structure of the crosslinked polymer, narrows the range and spread of stress relaxation time by reducing the diversity of structures and types of relaxation transitions. All this contributes to increased strength due to the redistribution of stresses, the elimination of overvoltages and the uniform redistribution of stresses on a larger number of chains and segments.

Hydroxyl-containing polybutadiene rubber obtained by anionic polymerization by the method of "live chains", is currently used as a film-forming in the paint industry and as a modifying additive in compositions based on solid rubbers, chemical structure [http: //www.Nisso PB.com.]:

Properties depend on the molecular weight of the rubber:

Marking G-1000 G-2000 G-3000 The average molecular weight of rubber 1250-1650 1800-2200 2600-3200 Microstructure,%: 1,2-vinyl, min 85 85 90 1,4-trans max fifteen fifteen 10 Viscosity at 45 ° C according to Brookfeld, Pa · s 3-10 8-25 25-45 Hydroxyl number,% 2.06-2.36 1.06-1.67 0.88-0.94 Density at 25 ° С, g / cm ³ 0.88 0.88 0.88

The microstructure with a predominant content of vinyl double bonds contributes to an increase in the reactivity of hydroxyl groups, which also leads to an increase in strength as a result of complete conversion and the formation of a denser vulcanization network.

The introduction of a low molecular weight trifunctional alcohol serves to further increase the strength due to additional hydroxyl groups, branching vulcanization structures and increasing the density of crosslinking. Polyols with at least two hydroxyl groups, such as glycerin, triethanolamine, trimethylolpropane, laprol polyester 373 (TU-2226-024-104885 7-95), obtained by condensation of glycerol and propylene oxide, can be used as a low molecular weight trifunctional alcohol.

As a plasticizer, the composition contains compounds used in the manufacture of elastomeric materials based on diol rubbers: phthalic acid alkyl esters, chloroparaffins, non-petroleum oils of net origin or PM oil.

Fillers for the composition are chalk, lime-screenings, calcium oxide, dolomite flour, granular rubber.

As an antioxidant, the coating composition mainly includes non-staining alkyl phenol or organophosphorus compounds 2,6-ditretbutyl-4-methylphenol (agidol-1), 2,4,6-tritrebutylphenol, 2,2-methylene bis- (4-methyl-6 tert-butylphenol) (product 2246).

Polyisocyanates, in particular polymethylene phenyl isocyanates based on 4,4'-diphenylmethane diisocyanate (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%.

Organometallic compounds or tertiary amines, for example, tin dibutyldylaurinate (TU-6-02-818-73), tin octoate, dimethylbenzylamine (TU-6-09-2974-78) and other organotin and amino compounds used in chemistry, are used as a urethane catalyst. polyurethanes.

For the manufacture of the coating composition, mixing equipment is used to ensure uniform distribution of the polyisocyanate and the urethane formation catalyst in the rubber and to obtain a homogeneous mixture.

The invention is illustrated by the following example (composition 1, table 1). 100 g of rubber, 70 g of plasticizer, 80 g of filler, 1 g of antioxidant, 1.7 g of 3,5-dimethylthiotoluene diamine are mixed into the mixer with an anchor mixer of 1 liter volume for 5 minutes and 0.01 g of urethane formation catalyst. Stirred for 5 min until smooth, then add a sample of 8 g of polyisocyanate and mix again for 5 minutes.

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

Compositions of other compositions are similarly prepared. The composition of the prototype is prepared at room temperature by successive introduction and mixing of rubber with all components. The composition of all investigated compositions is shown in table 1. The properties of the coating samples from the compositions are shown in table 2. The coating samples were tested according to GOST 263-93, GOST-270-75.

From the data of table 2 it can be seen that the use of the claimed hydroxyl-containing polybutadiene in combination with polyisocyanate, aromatic diamine and a urethane formation catalyst as a basis for the composition makes it possible to increase the strength of the coatings.

table 2 Properties of coating compositions The name of indicators Properties one 2 3 four 5 6 7 8 9 10 eleven 12 13 fourteen fifteen 16 Prototype Pat. RF 2285026 Conditional tensile strength, kgf / cm ² 10 12 17 27 22 27 24 26 27 13 12 13 16 7 8 8 9 Relative extension, % 220 140 130 120 120 110 120 120 110 180 200 110 140 300 220 300 one hundred Hardness, Shore A, conventional units 46 55 61 69 68 70 73 74 75 fifty 46 62 60 35 37 35 40

When the content of polyisocyanate is less than 8 parts by weight leads to a decrease in the level of the complex of strength properties due to a significant deviation of the NCO: OH ratio from stoichiometric and a decrease in the crosslinking density. With large quantities of polyisocyanate more than 28 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.

Similarly affects the amount of 3,5-diethylthiotoluene diamine or 3,5-dimethylthiotoluene diamine, in an amount of less than 0.7 parts by weight and in large quantities over 8.4 wt.h. stoichiometric equilibrium is violated towards the lack of hardener.

The amount of urethane formation catalyst has practically no effect on the physicomechanical characteristics and only controls the cure rate of the compositions.

An increase in the degree of filling creates difficulties in mixing and forming a monolithic structure of the coating due to the large proportion of dry components. Mixing is also difficult with small quantities of plasticizers, and the upper limit of plasticizers is limited by compatibility with polymers.

The antioxidant has little effect on the properties of cured coatings, usually used in the range of 1-2 parts by weight. Smaller amounts reduce the resistance to thermo-oxidative aging, and larger dosages can lead to deterioration of strength due to the possible deactivation of the isocyanate groups of the isocyanate hardener with hydroxyl groups of the antioxidant.

Thus, the advantage of coatings from the proposed composition is higher strength, hardness and elongation, which serves to increase the service life.

Claims (4)

1. Coating composition, comprising an isocyanate hardener - polyisocyanate, a urethane formation catalyst, a base - hydroxyl-containing polybutadiene rubber, a plasticizer, a filler and an antioxidant, characterized in that it contains a microstructure rubber,%: 1,4-trans 10-15 and 1 , 2-links 85-90, a molecular weight of 1250-3200 and a hydroxyl content of 0.82-2.36% and additionally 3,5-dimethylthiotoluylenediamine or 3,5-diethylthiotoluene diamine in the following ratio, wt.h .:
The specified hydroxyl-containing polybutadiene rubber one hundred Plasticizer 70-140 Filler 80-340 Antioxidant 1-2 Isocyanate Hardener - Polyisocyanate 8-28 Urethane Catalyst 0.01-0.1 3,5-dimethylthiotoluylenediamine or 3,5-diethylthiotoluylenediamine 1.7-8.0 2. The coating composition according to claim 1, characterized in that it contains dibutyl phthalate, chlorine paraffin XP-470, oil of non-petroleum origin, toxol or PM oil as a plasticizer. 3. The coating composition according to claim 1, characterized in that as a filler it contains a filler selected from the group consisting of chalk, lime sifting, calcium oxide, dolomite flour, granular rubber. 4. The coating composition according to claim 1, characterized in that as an antioxidant it contains an antioxidant selected from the group consisting of alkyl phenol compounds 2,6-ditretbutyl-4-methylphenol (agidol-1), 2,4,6-tritrebutylphenol , 2,2-methylene-bis- (4-methyl-6-tert-butylphenol) (product 2246).