RU2603366C1 - Rubber mixture based on butadiene-methylstyrene rubber - Google Patents

Abstract

FIELD: rubber industry.

SUBSTANCE: invention relates to rubber industry, in particular to development of rubber mixture based on butadiene-methylstyrene rubber, products from which are characterized by higher heat and fire resistance. Rubber mixture based on butadiene-methylstyrene rubber contains curing agent, mixture of curing accelerators, zinc oxide, organic curing activator, modifying additive and filler, wherein as mixture curing accelerators mixture of dibenzothiazyl disulfide and diphenyl guanidine is used, and as modifying additive is pre-treated with aniline pearlite in following ratio of components, wt. parts: butadiene-methylstyrene rubber - 100.0; sulphur - 2.0; zinc oxide - 5.0; stearic acid - 2.0; dibenzothiazyl disulfide - 1.5; diphenylguanidine - 0.3; technical carbon P324 - 40.0; said pearlite - 10.0.

EFFECT: invention enables to produce vulcanizate based on butadiene-methylstyrene rubber, having higher heat- and fire-resistance.

1 cl, 2 tbl

Description

The invention relates to the rubber industry, in particular to the development of a rubber mixture based on butadiene-methylstyrene rubber, the products of which are characterized by increased heat and fire resistance.

Known rubber mixture containing styrene butadiene rubber, sulfur, zinc oxide, calcium carbonate, silicon dioxide and azodicarbonamide as a blowing agent (Koshelev F.F. and other General technology of rubber. M: Chemistry, 1978, S. 492-501 )

A disadvantage of the known technical solution is the great complexity and significant energy costs in the manufacture of products from the above rubber mixture, since the vulcanization process is two-stage and requires complex and traumatic production equipment. In addition, the resulting products have physical and mechanical properties that do not meet the requirements.

Known rubber mixture based on butadiene-methylstyrene rubber containing sulfur, dibenzothiazoldisulfide, diphenylguanidine, zinc oxide, stearic acid, carbon black and sodium alginate (RU 2428440, IPC C08L 9/06, C08K 3/04, C08K 3/06, C08K 3 / 22, C08K 5/09, C08K 5/31, C08K 5/47, publ. 09/10/2011).

However, this rubber compound does not have increased heat resistance.

Known rubber compound (RU 2052472, IPC C08L 9/06, C08K 13/02, C08L 97/00, C08K 3/04, C08K 3/06, C08K 3/22, C08K 5/09, C08K 5/31, C08K 5 / 47, publ. 20.01.1996) containing butadiene-methyl styrene rubber, sulfur, zinc oxide, altax, diphenylguanidine, stearic acid, carbon black and chlorinated epoxylignin.

However, this rubber compound does not have increased heat resistance.

Known rubber compound (RU 2044006, IPC C08L 9/06, C08L 9/00, C08K 13/02, C08K 3/06, C08K 3/22, C08K 3/34, C08K 3/36, C08K 5/09, C08K 5 / 3467, C08K 5/44, published September 20, 1995) containing butadiene-methylstyrene rubber, synthetic cis-1,4-polyisoprene rubber, sulfur, zinc oxide, N cyclohexyl-2-benzothiazolylsulfenamide, stearic acid, the molecular complex of resorcinol c hexamethylenetetramine, phthalic anhydride, white soot and kaolin.

However, this rubber mixture has low physical and mechanical properties and does not have increased heat resistance.

Known rubber compound (RU 2145616, IPC C08L 9/00, C08L 9/06, C08K 13/02, C08K 3/04, C08K 3/06, C08K 3/22, C08K 3/26, C08K 3/36, C08K 5 / 01, C08K 5/09, C08K 5/10, C08K 5/13, C08K 5/18, C08K 5/23, C08K 5/375, publ. 02.20.2000) containing butadiene-methyl styrene rubber, synthetic cis-1 , 4-polyisoprene rubber, sulfur, zinc oxide, stearic acid, phenyl-β-naphthylamine, filler and modifiers.

However, this rubber mixture has low physical and mechanical properties and does not have increased heat resistance.

Known rubber compound (SU 1728263, IPC C08L9 / 06, C08K 13/08, C08K 3/04, C08K 3/06, C08K 3/22, C08K 5/09, C08K 5/47, C08K 11/00, publ. 23.04 .1992) containing butadiene-methylstyrene rubber, sulfur, di- (2-benzthiazolyl) disulfide, zinc oxide, stearin, carbon black and distillation residue of rectification of tetrahydrofurfuryl alcohol.

However, this rubber composition has low heat resistance and is unstable during thermo-oxidative aging.

Known polymer composition (US 2005288422, IPC C08K 5/02, C08K 5/3492, C08L 9/02, C08L 9/06, publ. 12/29/2005) based on acrylbutadiene styrene, natural rubber, nitrite, neoprene, vinylpyridine, isoprene or their copolymers or ter-polymers containing a flame retardant, carbon black, sulfur, zinc oxide, zinc mercaptobutyl talate, zinc diethyl dithiocarbamate, antioxidant and microcrystalline wax.

However, this rubber compound has low physical and mechanical properties.

Known polymer composition (WO 2012113145, IPC C08K 3/32, C08L 25/06, C08L 25/12, C08L 27/06, C08L 55/02, C08L 61/06, C08L 63/00, C08L 71/12, C08L 9 / 06, published February 24, 2011) based on butadiene-methylstyrene rubber, containing the calcium salt of hypophosphite and other organic and inorganic phosphorus compounds.

However, this composition is characterized by low environmental friendliness.

Known polymer composition (US 5773501 IPC C08K13 / 02, C08K 3/00, C08K 3/22, C08K 5/00, C08K 5/02, C08K 5/06, C08K 5/109, C08K 5/1515, C08K 5/22 , C08L 25/04, C08L 25/12, C08L 55/02, C08L 63/00, C08L 69/00, C08L 9/06, publ. 06/30/1998) based on butadiene-methyl styrene rubber containing a halogen-containing flame retardant and optionally trioxide antimony.

However, this composition is characterized by low environmental friendliness and low values of physical and mechanical properties.

Known polymer composition (WO 2013176868, IPC C08K5 / 00, C08K 5/02, C08K 5/5333, C08L 25/04, C08L 27/18, C08L 55/02, C08L 9/06, publ. 28.11.2013) based butadiene-methylstyrene rubber containing brominated flame retardant, aluminum methylphosphonate and optionally antioxidant dyes.

However, it does not have increased heat and flame retardant characteristics.

Closest to the achievement of the technical result is a rubber mixture based on butadiene-methylstyrene rubber (RU 2010814, IPC C08L 9/06, C08K 13/02, C08L 27/06, C08L 79/00, C08K 3/22, C08K 5/18, publ. 04/15/1994) including sulfur (0.5), altax (2.5), zinc oxide (5.0), stearic acid (2.0), carbon black (40.0) and optionally poly- (N -3,5-ditretbutyl-4-hydroxytolyl) ethyleneimide (1.0-1.5).

However, this rubber composition has low elongation and low fire resistance.

The objective of the invention is to develop a rubber mixture based on butadiene-methylstyrene rubber, the vulcanizates of which are characterized by increased heat and fire resistance, while maintaining physical and mechanical properties.

The technical result is a vulcanizate based on butadiene-methylstyrene rubber, which has increased heat and fire resistance.

The technical result is achieved by the fact that in a rubber mixture based on butadiene-methyl styrene rubber, including a vulcanizing agent - sulfur, a vulcanization accelerator - zinc oxide, an organic vulcanization activator stearic acid, a modifying additive and a filler - carbon black P-324, while as mixtures of vulcanization accelerators use a mixture of dibenzothiazoldisulfide and diphenylguanidine, and perlite pretreated with aniline as the modifying additive in the following ratio Research Institute of components, wt. h: butadiene-methylstyrene rubber - 100.0; sulfur - 2.0; zinc oxide - 5.0; stearic acid - 2.0; dibenzothiazole disulfide - 1.5; diphenylguanidine - 0.3; carbon black P-324 - 40.0; the specified perlite is 10.0.

Sulfur (GOST 127.4-93) was used as a vulcanizing agent in the rubber composition based on SKMS-30 ARKM-15 butadiene-methyl styrene rubber or SKS-30 ARKM-15 butadiene rubber (GOST 11138-78), as an activator of the accelerator vulcanization - zinc oxide (GOST 202-84), as a vulcanization activator - stearic acid (GOST 6484-96), as a filler - carbon black P234 or P324 (GOST 7885-86), as a vulcanization accelerator - diphenylguanidine (GOST 40 -80) and dibenzothiazole disulfide (GOST 7087-75) and as modifying add Application - perlite (GOST 30566-98) pretreated with aniline.

The claimed amount of pre-treated with aniline perlite (10.0) is optimal, because with a decrease in its amount, the fire-retardant efficiency of the vulcanizates decreases, and an increase in its dosage is impractical, since it does not significantly affect the complex of properties of rubber compounds.

Improving the heat, fire retardant characteristics of vulcanizates is achieved due to the layered structure of perlite particles, which creates a kind of micro-barriers in the surface layers of the material. The surface treatment of perlite with glycol, followed by modification, makes it possible to increase the hydrophobicity of perlite and its rubberiness.

An example of the preparation of the rubber compound

A mixture of SKMS-30 ARKM-15 butadiene-methyl styrene rubber, sulfur, zinc oxide, stearic acid, P324 carbon black, dibenzothiazole disulfide, diphenylguanidine and pre-treated aniline perlite is prepared on rollers at a roll temperature of 65-70 ° C.

The production time of the rubber compound is 25 minutes. Then it is vulcanized at a temperature of 155 ° C for 30 minutes.

Table 1 shows the compositions of the prepared mixtures and prototype.

The physicomechanical properties of the vulcanizate from the proposed rubber mixture were determined in accordance with GOST 270-75, GOST 267-73 and GOST 263-75, and fire resistance was determined by the decay time of the sample after it was removed from the burner flame.

Resistance to thermal oxidative aging was determined in accordance with GOST 23785.7-77.

Table 2 shows the physicomechanical and heat-flame retardant indicators characterizing the properties of vulcanizates obtained on the basis of the proposed rubber compound and prototype.

To evaluate the heat-shielding characteristics, the time of heating the reverse side of the sample, made in the form of a washer with a diameter of 30 mm and a thickness of 6 mm, to a temperature of 100 ° C was determined.

The sample was heated by an open flame of the plasmatron (a temperature of 2000 ° C was created on the surface). The sample was mounted in a tripod at an angle of 45 ° to the burner flame. To reduce the heat sink and reduce the experimental error, the sample was insulated with asbestos along the edge.

To measure the temperature on the unheated surface of the sample, we used a S-300.3 Photon pyrometer and a TPM-1 contact chromel-kopel thermocouple for the Aries controller.

Fire resistance was determined by the decay time of the sample after removing it from the burner flame.

Thus, a vulcanizate from a rubber mixture based on butadiene-methylstyrene rubber, including sulfur, zinc oxide, stearic acid, dibenzothiazoldisulfide, diphenylguanidine, P324 carbon black and pre-treated aniline perlite, has increased heat and fire resistance while maintaining high physical and mechanical characteristics.

Claims (1)

The rubber mixture based on butadiene-methyl styrene rubber, including a vulcanizing agent - sulfur, a vulcanization accelerator - zinc oxide, an organic vulcanization activator stearic acid, a modifying additive and a filler - carbon black P-324, characterized in that a mixture of dibenzotiazisulide is used as a mixture of vulcanization accelerators and diphenylguanidine, and as a modifying additive - perlite pretreated with aniline in the following ratio of components, wt. hours:
Butadiene-methylstyrene rubber - 100.0;
Sulfur - 2.0;
Zinc oxide - 5.0;
Stearic acid - 2.0;
Dibenzothiazole disulfide - 1.5;
Diphenylguanidine - 0.3;
Carbon black P-324 - 40.0;
The specified perlite is 10.0.