RU2625856C2 - Rubber modifier and rubber mixture on its basis - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: modifier is obtained by the interaction of fullerenes of fraction C₅₀-C₉₂, indolyl-3-butyric acid, methylbenzene, dimethyl ketone, sulfuric acid, paraform. The resulting mixture of synthesis products is combined with wollastonite in a weight ratio of 10: 100 by mechanical stirring. The resulting modifier is used for making rubber compounds. Rubber mixture contains SKEPT rubber, vaseline oil, zinc oxide, oleic acid, wollastonite, peroximone F40, modifier and phthalocyanine pigment.

EFFECT: invention allows to improve the complex of physicomechanical properties of the rubber compound.

2 cl, 5 tbl

Description

The invention relates to the production of modifiers for rubber compounds and rubber products based on them.

It is known to use carbon black as a modifier (filler) for rubber of increased wear resistance (in particular, used for the manufacture of tires) [for example, patent EP N 0159469, class. B60C 1/00, 1985, EP N 0224184, class. B60C 1/00, 1987]. The addition of carbon black during the vulcanization process leads to an increase in rubbers, i.e. increase strength, wear resistance of rubber, because particles of active soot, combining with rubber, form an additional network that penetrates the entire mass of rubber in various directions, i.e. carbon black is included in the spatial network of the polymer. However, the strength and wear resistance of rubber with a carbon black filler does not meet modern requirements.

Known filler for elastomers based on fullerene [patent EP N 0716044, class. C01B 31/02, 1996], which is an amino or hydroxyfullerene, for example C ₆₀ (OH) _x . In this case, the monomer or rubber molecules are bonded to each other by fullerene molecules. The rubbers and rubbers obtained using the specified filler also do not have sufficient strength properties, because fullerenes do not form a sufficient number of bonds in various directions.

As a prototype, the patent of the Russian Federation No. 2151781 [Petrik Viktor Ivanovich, publ. 06/27/2000]. The invention relates to the field of production of rubbers, synthetic rubbers and other elastomers. The filler for rubbers, rubbers and other elastomers consists of a mixture of fullerenes and a carbon mixture made of graphite treated with chromic acid with a ratio of the mass of graphite to the mass of acid from 1: 0.3 by resistive heating, and the carbon mixture is 80-95 wt. % filler, fullerenes - the rest. However, such a modifier creates difficulties in dispersing and further manufacturing the finished product based on the resulting rubber composition.

The technical task of the present invention is the development of a comprehensive modifier for the production of rubber compounds and rubber products based on them with an improved set of physico-chemical properties. To obtain the modifier used the following components in a ratio, wt.%:

Mixture of fullerenes of fraction C ₅₀ -C ₉₂ 0,033-0,094 Indolyl 3-butyric acid 0.163-0.469 Methylbenzene 31,269-32,616 Dimethyl ketone 62,569-65,232 Sulphuric acid 1,631-4,690 Paraform 0.326-0.938

The use of fillers in the vulcanization process leads to additional interaction during the vulcanization process and, as a rule, to the strengthening of vulcanizates. The use of the developed modifier leads to crosslinking of the chains of macromolecules in elastomers by fullerene molecules and to the formation of additional cross-links. In this case, it becomes possible to reduce the content of the curing agent.

The technical problem of the invention is solved in that the modifier based on a mixture of carbon fullerenes for rubber goods is synthesized as follows:

- at the first stage, solutions of indolyl-3-butyric or indolylacetic acids and paraform in dimethyl ketone and a mixture of fullerenes of fraction C ₅₀ -C ₉₂ in methylbenzene are mixed,

- the specified mixture of solutions is heated with constant stirring to the temperature of the reaction in the temperature range 58-60 ° C. The synthesis is carried out with a constant return of solvents through a reflux condenser cooled by running water until the temperature of the reaction medium begins to fall below the specified range,

- further, a catalyst (concentrated sulfuric acid with a density of 1.84 g / cm ³ ) is added dropwise to the reaction mixture until gas evolution from the reaction mixture is completely stopped. The end of the reaction is accompanied by a change in the color of the system and the formation of a dark red opaque stable colloidal system of a mixture of synthesis products.

To carry out the synthesis, three reagent compositions were prepared, which are presented in table 1.

The yield of the synthesis products was determined by the visible light transmittance of the resulting color solution using a KFK-ZKM single-beam spectrophotometer in the photometric measurement range. At a wavelength of visible light equal to 620 nm, this value was 11.25%; 9.22%; 10.56%, respectively, for compositions No. 1, No. 2 and No. 3. The minimum value of the transmittance corresponds to the highest degree of conversion of the starting materials, which was observed during the reaction with a ratio of reagents in composition No. 2.

To obtain a modifier, the resulting mixture of synthesis products is combined with a filler in a mass ratio of 10: 100 by mechanical stirring, where wollastonite is used as a filler in the following ratio, wt.%:

Mixture of fullerenes of fraction C ₅₀ -C ₉₂ 0.003-0.009 Indole derivatives 0.016-0.047 Methylbenzene 3,262-3,127 Dimethyl ketone 6,523-6,257 Sulphuric acid 0.163-0.469 Paraform 0,033-0,094 Wollastonite 90-90,185

Examples of the composition of the modifiers are presented in table 2.

Based on the degree of conversion of the synthesis products, the modifier corresponding to composition No. 2 possesses optimal properties. Based on the obtained modifier, a rubber mixture was made, which consisted of triple ethylene-propylene-diene rubber (SKEPT), vaseline oil, zinc oxide, oleic acid, wollastonite, peroximon F40, the developed modifier and phthalocyanine pigment in the following ratio of ingredients, wt.%. :

Rubber SKEPT 59,269-65,959 Vaseline oil 3,958-4,742 Zinc oxide 1,979-2,963 Oleic Acid 1,319-2,371 Wollastonite 26,383-29,635 Peroximon F40 0.329-0.889 Modifier 0.007-0.012 Phthalocyanine pigment 0,067-0,119

A method of preparing a rubber mixture is as follows. Rubber and other ingredients are weighed on technical scales. Rubber and other ingredients are weighed on technical scales. Rubber is pre-rolled on pre-warmed up to 50 ± 5 ° C, then the ingredients are added sequentially; the mixture is prepared for 20 minutes and removed in the form of a sheet at a temperature not exceeding 100 ° C; the resulting rubber sheet is cooled in air to 30 ° C and quenched with a clean pad.

The use of the developed modifier in the formulation allows to obtain a rubber mixture with high physical and mechanical properties of vulcanizates. The developed rubber mixture based on the modifier has good technological properties, can be easily processed on existing equipment, finished products will be highly resistant to oxygen aging, improved physicochemical parameters.

As examples, table 3 presents the composition of the rubber compounds based on the obtained modifiers.

Finished rubber compounds were analyzed and determined: conditional tensile strength, elongation at break (GOST 21751), hardness (GOST 263-75), rebound elasticity (GOST 27110-86). The analysis data are presented in table 4.

As follows from the data of table 4, the optimal properties are the rubber mixture made according to example 2, using a modifier composition No. 2 in the amount of 0.009 wt.%. The proposed rubber mixture has the best performance and can improve the operational properties of the finished rubber products based on it.

Claims (4)

1. A modifier for rubbers, characterized by the product of the interaction of fullerenes of fraction C ₅₀ -C ₉₂ , indolyl-3-butyric acid, methylbenzene, dimethyl ketone, sulfuric acid, paraform and wollastonite as a filler in the following ratio, wt.%: mixture of fullerene fractions C ₅₀ -C ₉₂ 0.003-0.009 indolyl 3-butyric acid             0.016-0.047 methylbenzene                                                 3,262-3,127 dimethyl ketone                                     6,523-6,257 sulphuric acid                                     0.163-0.469 paraform                                                 0,033-0,094 wollastonite                                                 90.0-90.185 2. Rubber compound based on rubber SKEPT, including vaseline oil, zinc oxide, oleic acid, wollastonite, peroximon F40, the modifier made according to claim 1, the phthalocyanine pigment in the following ratio, wt.%: rubber SKEPT                   59,269-65,959 liquid paraffin                   3,958-4,742 zinc oxide                               1,979-2,963 oleic acid                   1,319-2,371 wollastonite                               26,383-29,635 peroximon F40                   0.329-0.889 modifier                               0.007-0.012 phthalocyanine pigment       0,067-0,119