The rubber mixture (options)

 

(57) Abstract:

The invention relates to the field of production of rubber mixtures tire purpose and can be used in the manufacture of tires, rubber and rubber products. Prepare the rubber mixture comprising, by weight.h: polybutadiene rubber, solution polymerization 30-50, a copolymer of butadiene with vinylaromatic monomer emulsion polymerization 50-70, sulfur 0.5 to 1.5, zinc oxide 1-5, carbon 40-80, targeted supplements 8,5-23,0. In the first embodiment as butadiene rubber mortar polymerization mixture contains block copolymers of butadiene with styrene linear structure polystyrene-polybutadiene with a mass content of block polystyrene 3-10%, and 1,2-butadiene units in part 8-25% when the mass ratio of the specified block copolymers of butadiene with styrene, a copolymer of butadiene 1:1,0-2,33. On the second version while maintaining the same components as a copolymer of butadiene with vinylaromatic monomer emulsion polymerization enter a copolymer of butadiene, styrene and Acrylonitrile with a mass content of the bound styrene 16-20% bound Acrylonitrile 4-6%, or a copolymer of butadiene, styrene and methyl methacrylate with mass soderjaniu of butadiene with styrene, a copolymer of butadiene with vinylaromatic monomer emulsion polymerization 1:1,00 - 2,33. The rubber mixtures are prepared in 2 stages. The technical result of the invention consists in the improvement of physico-mechanical, dynamic characteristics of the vulcanizates, wear resistance and traction tread rubber of a mixture according to the invention with a wet road surface. 2 N. p. F.-ly, 2 tab.

The invention relates to the field of production of rubber mixtures tire purpose and can be used in the manufacture of tires, rubber and rubber products.

To obtain tire rubber for different purposes use buta-dienstelle (-methylstyrene) rubber emulsion polymerization with their content of about 30 wt. including styrene (including oil); however, for this type of rubber is characterized by high hysteresis loss and high heat build-up while rolling. Unlike the best choice rubbers irregular structures used in the manufacture of tire rubbers the best choice rubber solution polymerization have a narrower molecular weight distribution and the prevailing content of parts of 1,4-CIS-polybutadiene, allowing you to get to their base rubber with high tear resistance, abrasion and cracking, strength and pace is adiantifolia rubber solution polymerization yield the best choice rubber emulsion polymerization technological properties. In the manufacture of rubber tire purpose use butadiene rubbers regular structure, containing 95% or more of the parts of 1,4-CIS, characterized by high resistance to abrasion, elasticity, resistance and resistance to cracking, low hysteresis loss and heat buildup; however, poor technological properties and low towing characteristics allow the use of polybutadiene only in blends with other rubbers (A. C. Saltykov. The foundations of modern technologies of automobile tires. M: Chemistry, 1974, S. 91-93).

Known rubber compound for the manufacture of treads on the basis of 68.5 wt. including CIS-1,4-polybutadiene solution polymerization (Europen CIS) and 50 wt. including the best choice of rubber emulsion polymerization from 22.5 and 24.5 wt.% styrene, filled 37.5 wt.% reference to ha oils (Europen 1712), comprising 80 wt. including carbon black 3 wt. including zinc oxide, 2 wt. including stearic acid, 2 wt. including antioxidant, 1.4 wt. hours of a vulcanization accelerator, 1.8 wt. including sulfur, 0.5. PM moderator of podocarpaceae, of 25.7 wt. including reference to ha oil (Alary D. Synthetic rubbers for the tire industry. Proceedings of the international conference on rubber and rubber. Moscow, November 1 and high heat buildup.

Known rubber mixture based on the best choice of rubber modified ester groups, which contains 30% styrene and ethylcarboxylate 5 and 10% with 2 wt. including stearic acid, 5 wt. including zinc oxide, 1 wt. including triethanolamine, 3 wt. including glycerol, 6 wt. including technical vaseline, 35 wt. including black carbon, 5 wt. including chalk, 5 wt. including gypsum, 5 wt. including calcium hydroxide, N,N-dithiodimorpholine and sulfur (Smirnova T. A., Azrieli A. I. and others On some properties of the best choice of rubber with ester groups. The production of tires, rubber products. M: Tsniiteneftehim, 1973, No. 1, S. 1-3).

Known rubber compound has slowed vulcanization, high rigidity, low tear resistance and dynamic endurance and requires the use of significant quantities of complex vulcanizing agents, sulfur and salt.

Known vulcanizates on the basis of butadiene--methylstyrene caoutchouc ckmc-30 using oligopyrroles General formula

where n is the number of hydroxyl groups substituted for residues of acrylic acid;

m is the degree of polymerization of oligoether;

R is the residue of a glycol or polyol;

Modification of unsaturated elastomers oligoadenylate is in the process of three-dimensional graft copolymerization, leading to the inclusion of one polymer in the structure of another.

Rubber with active Sagami based rubbers and polyfunctional oligoesters, playing the role of the modifier and curing agents possess a valuable combination of properties: relatively high strength and resistance to dynamic loads, low heat buildup.

However, when structuring butadiene--methylstyrene caoutchouc ckmc-30, the most widely used to obtain rubber tire purpose of the aqueous rubber with oligoadenylate.

Closest to the technical essence and the achieved result to the present invention is a rubber mixture comprising 70 wt. including the best choice of rubber emulsion polymerization (BSC), 30 wt. including butadiene rubber solution polymerization (ACS), 1.8 wt. including sulfur, 1.3 wt. hours of a vulcanization accelerator, a 0.7 wt. PM moderator of podocarpaceae, 3.0 mass. including antioxidant, 2.0 wt. including microcrystalline wax, of 11.0 wt. including plasticizer, 3.0 mass. hours of rubrics or coumarone-indene resins, 60,0 wt. including active carbon black, 3.0 mass. including zinc oxide, 2.0 wt. including stearic acid (A. C. Saltykov. The foundations of modern technologies of automobile tires. M.: Chemistry, 1974, S. 130).

The disadvantages of the known mixtures are low tear resistance and dynamic endurance is not very good traction on wet road surface.

The technical objective of the proposed invention is the improvement of physico-mechanical and dynamic characteristics of the vulcanizates, wear resistance and traction tread rubber on the basis of the inventive rubber mixture with a wet road surface.

The problem is solved in that the rubber mixture comprising polybutadiene rubber, mortar, polymerizati and targeted supplements, as a butadiene rubber solution polymerization includes block copolymers of butadiene with styrene, a linear structure with a mass content of block polystyrene 3-10%, and 1,2-butadiene units in part 8-25% when the mass ratio of the specified block copolymers of butadiene with styrene, a copolymer of butadiene with vinylaromatic monomer emulsion polymerization 1:1,00-2,33, respectively, and with the following content of components in the rubber mixture, wt. including:

The specified block copolymers of butadiene with styrene 30,0-50,0

The copolymer of butadiene with

vinylaromatic

the monomer emulsion

polymerization 50,0-70,0

Sulfur is 0.5-1.5

Zinc oxide 1,0-5,0

Carbon 40,0-80,0

Additives target of 8.5-23,0

According to the second variant of the invention the inventive rubber mixture as a copolymer of butadiene with vinylaromatic monomer emulsion polymerization contains a copolymer of butadiene, styrene and Acrylonitrile with a mass content of the bound styrene 16-20% bound Acrylonitrile 4-6%, or a copolymer of butadiene, styrene and methyl methacrylate with a mass content of the bound styrene 11-20% and associated metalmetal the styrene and Acrylonitrile or a copolymer of butadiene, styrene and methyl methacrylate 1:1,00-2,33 respectively and with the same content of components in the rubber mixture, as in the first embodiment of the invention.

As the target additives rubber mixture contains traditionally used ingredients: plasticizer (stearic acid, oil MO-6, rosin, resin strollerderby), of a vulcanization accelerator (sulfenamid C), the moderator of podocarpaceae (phthalic anhydride), antioxidant (acetonyl, deafen-P, protective wax SV-P).

In the implementation of the proposed technical solution in the first embodiment use

- butadiene rubber SKD-LS on THE 38.40332-97, which is the product of blockcopolymers of butadiene with styrene in solution in the presence of lithium catalysts;

- synthetic rubber butadiene-styrene SCS-30 ARKN according to GOST 23492-83 received by the joint polymerization of butadiene with styrene in emulsion at low temperature using as an emulsifier a mixture of Soaps of rosin and synthetic fatty acids;

- synthetic rubber butadiene-methylstyrene SKMS-30 apkm-15 and butadiene-styrene SCS-30 apkm-15 GOST 11138-78 received by the joint polymerization of butadiene with a-methylstyrene or styrene is Foley and synthetic fatty acids containing 14 to 17 wt. % reference to ha oil MO-6K.

In the implementation of the second variant of the proposed technical solution in addition to the above rubber SKD-drug use:

- synthetic rubber Reselect, which is a joint product of the polymerization of butadiene, styrene and Acrylonitrile using as emulsifier soap distilled tall oil; the way to obtain this rubber is described in the patent of Russian Federation №2064925 (IPC 08 F 236/10, 236/12, priority 16.02.95, publ. 10.08.96, bull. No. 22);

- synthetic rubber Reselect-M on THE other 38.403117-85, which, as the rubber Reselect, a joint product of the polymerization of butadiene, styrene and Acrylonitrile using as emulsifier soap distilled tall oil, but contains 11-14 wt.% reference to ha oil MO-6K; the method of producing rubber Reselect-M to the stage of filling the oil described in the above patent RF №2064925;

- synthetic rubber Reselect-2-1 on THE other 38.403122-97, which is the product of copolymerization of butadiene, styrene and methyl methacrylate using as emulsifier soap distilled tall oil; the way to obtain this rubber is described in the patent of Russian Federation №2115664 (IPC 08 F 236/10, priority 26.06. the ilast-2-1, a joint product of the polymerization of butadiene and methyl methacrylate using as emulsifier soap distilled tall oil filled 11-14 wt. % reference to ha oil MO-6K; the method of producing rubber Reselect-2M to the stage of filling the oil described in the above patent No. 2115664.

The rubber mixtures are prepared in two stages.

A mixture of 1-St stage is carried out in the rubber mixer for 8-10 minutes, consistently impose the following rubbers and ingredients:

- butadiene rubber SKD-LS on THE 38.40332-97, rubber butadiene-methylstyrene according to GOST 15627-79;

as antioxidant deafen-OP, acetonyl R, protective wax SV-P;

as a vulcanization activator is zinc oxide;

as the filler is carbon black P-M;

as the plasticizer is stearic acid, oil MO-6, pine rosin, resin sterlington;

as moderator of podocarpaceae - phthalic anhydride.

stage 2 - the mixture on the rolls for 15-20 min:

- Royal mixture of 1-stage mixing;

- sulfur - vulcanizing agent;

as the vulcanization accelerator, sulfenamid C.

- conditional stress at 300% elongation according to GOST 270-75;

- conditional tensile strength according to GOST 270-75;

- elongation according to GOST 270-75;

- tear resistance according to GOST 262-79;

- hardness shore a according to GOST 263-75;

- ball rebound resilience according to GOST 27110-86;

- resistance to repeated tension according to GOST 9983-74;

- abrasion on the instrument Shopper-Sabaha according to GOST 23509-79;

- ratio clutch wet asphalt determined by the method described [C. L., Kudikov L. D., Levin, Y. S. study of the clutch tires with a wet road. Sat. proceedings of NISP, M., 1974, S. 139-155.

The essence of the proposed invention is illustrated by examples of its implementation.

Example 1

For the preparation of rubber mixtures take the rubber and ingredients in the following proportions: 40.0 wt. including rubber SKD-HP with a mass content of 5% block polystyrene and 12% 1,2-diene units in part, by 60.0 wt. including rubber SKS-30 AMIS, 1 wt. including sulfur, 0.7 wt. including sulfenamide C, 60,0 wt. including carbon black P-234, 3.0 mass. including zinc oxide, 2.0 wt. including stearic acid, 3.0 mass. including oil MO-6, 4.0 m is anipoli pine.

The rubber mixture is prepared as described above. The finished rubber mixture vulcanized and determine the physical and mechanical properties.

Rubber compound shown in table 1, the results of the tests in table 2.

Example 2

The rubber mixture is prepared as in example 1. Take the rubber and ingredients in the following proportions: to 50.0 wt. including rubber SKD-HP with a mass content of 3% block polystyrene and 8% 1,2-diene units in part, to 50.0 wt. including caoutchouc ckmc-30 apkm-15, 1.5 wt. including sulfur, 0.4 wt. including sulfenamide C, 40.0 wt. including carbon black P-234, 1,0 wt. including zinc oxide, 1.5 wt. including stearic acid, 1.5 wt. including oil MO-6, 0.75 wt. including protective wax SV-P, 2.0 wt. including strollerderby resin, 0.1 wt. including phthalic anhydride, 0.5. hours of acetonemia, 0.75 wt. hours of diafine-OP, 1,0 wt. including pine rosin.

Rubber compound shown in table 1, the results of the tests in table 2.

Example 3

The rubber mixture is prepared as in example 1. Take the rubber and ingredients in the following proportions: 30.0 wt. including rubber SKD-HP with a mass content of 10% block polystyrene and 25% of 1,2-units in the diene portion and 70.0 wt. including rubber SKS-30 apkm-15, 0.5. including sulfur, 5.0 wt. including zinc oxide as a vulcanization accelerator 1,0 is diafine-OP and 1.5 wt. including protective wax SV-P, as a plasticizer 3.0 mass. including oil MO-6, 3.0 mass. including stearic acid, 6.0 wt. including strollerderby resin, 4.0 wt. including rosin, 80,0 wt. including carbon black P-234.

Rubber compound shown in table 1, the results of the tests in table 2.

Example 4 (prototype)

The rubber mixture is prepared as in example 1. For the preparation of rubber mixtures according to the prototype take 70,0 wt. including rubber SKS-30 apkm-15, 30.0 wt. including butadiene rubber SKD, 1.8 wt. including sulfur, 3.0 mass. including zinc oxide as a vulcanization accelerator 1.3 wt. including sulfenamide C, retarder under-vulcanization of 0.7 wt. including phthalic anhydride, as an antioxidant and 1.0 wt. hours of diafine-OP, 2.0 wt. hours of acetonemia P, 2 wt. including wax protective SV-P, as a plasticizer 3.0 mass. including rosin, 60,0 wt. including carbon black P-234.

Rubber compound shown in table 1, the results of the tests in table 2.

Example 5

The rubber mixture is prepared as in example 1. Rubber and ingredients taken in the following ratio: by 60.0 wt. including rubber Reselect-1, containing 16 wt.% the bound styrene and 4 wt.% linked nitrile of acrylic acid (EAA), and 40.0 wt. including rubber SKD-HP with a mass content of 5% Namida C, 3.0 mass. including zinc oxide, 2.0 wt. including stearic acid, 3.0 mass. including oil MO-6, 1.0 wt. including protective wax SV-P, 4.0 wt. including strollerderby resin, 0.5. including phthalic anhydride, 1.0 wt. hours of acetonemia, 1.5 wt. hours of diafine-OP, 2.0 wt. including pine rosin.

Rubber compound shown in table 1, the results of the tests in table 2.

Example 6

The rubber mixture is prepared as in example 1. Rubber and ingredients taken in the following ratio: 50,0 wt. including rubber SKD-drug containing 3 wt.% a block of polystyrene and 8 wt.% 1,2-diene units in part, impose to 50.0 wt. including rubber Reselect-1 containing 20 wt.% the bound styrene and 6 wt.% linked nitrile of acrylic acid, 1.5 wt. including sulfur, 0.4 wt. including sulfenamide C, 40.0 wt. including carbon black P-234, 1,0 wt. including zinc oxide, 1.5 wt. including stearic acid, 1.5 wt. including oil MO-6, 0.75 wt. including protective wax SV-P, 2.0 wt. including strollerderby resin, 0.1 wt. including phthalic anhydride, 0.5. hours of acetonemia, 0.75 wt. h diaphana-OP, 1,0 wt. including pine rosin.

Rubber compound shown in table 1, the results of the tests in table 2.

Example 7

The rubber mixture is prepared as in example 1. For the preparation of rubber mixtures take 30.0 wt. including rubber SKD-PP, contains the th 18 wt.% the bound styrene, 5 wt.% linked nitrile of acrylic acid and 15 wt.% oil MO-6. In a mixture of rubbers enter 0.5. including sulfur, 1.0 wt. including sulfenamide C, 80,0 wt. including carbon black P-234, 5.0 wt. including zinc oxide, 3.0 mass. including stearic acid, 3.0 mass. including oil MO-6, 1.5 wt. including protective wax SV-P, 6.0 wt. including strollerderby resin, 1,0 wt. including phthalic anhydride, 1.5 wt. hours of acetonemia R, 2.0 wt. hours of diafine-OP, 4.0 wt. including pine rosin.

Rubber compound shown in table 1, the results of the tests in table 2.

Example 8

The rubber mixture is prepared as in example 1. For the preparation of rubber mixtures take 40.0 wt. including rubber SKD-drugs, containing 5 wt.% a block of polystyrene and 12 wt.% 1,2-diene units in part, by 60.0 wt. including rubber Reselect-2 containing 15 wt.% the bound styrene and 5 wt.% linked methyl methacrylate (MMA), in a mixture of rubber injected with 1.0 wt. including sulfur, 0.7 wt. including sulfenamide C, 60 wt. including carbon black P-234, 3.0 mass. including zinc oxide, 2.0 wt. including stearic acid, 3.0 mass. including oil MO-6, 1.0 wt. including protective wax SV-P, 4.0 wt. including strollerderby resin, 0.5. including phthalic anhydride, 1.0 wt. hours of acetonemia R, 1.5 wt. hours of diafine-OP, 2.0 wt. including pine rosin.

Rubber compound shown in table 1, the results of the tests - th mixture take to 50.0 wt. including rubber SKD-HP with a mass content of 3% block polystyrene and 8% 1,2-diene units in part, to 50.0 wt. including rubber Reselect-2 containing 11 wt.% the bound styrene and 4 wt.% linked methyl methacrylate, and injected 1.5 wt. including sulfur, 0.4 wt. including sulfenamide C, 40.0 wt. including carbon black P-234, 1,0 wt. including zinc oxide, 1.5 wt. including stearic acid, 1.5 wt. including oil MO-6, 0.75 wt. including protective wax SV-P, 2.0 wt. including strollerderby resin, 0.1 wt. including phthalic anhydride, 0.5. hours of acetonemia R, 0.75 wt. hours of diafine-OP, 1,0 wt. including pine rosin.

Rubber compound shown in table 1, the results of the tests in table 2.

Example 10

The rubber mixture is prepared as in example 1. For the preparation of rubber mixtures take 30.0 wt. including rubber SKD-drugs, containing 10 wt.% a block of polystyrene and 25 wt.% 1,2-diene units in part, 70,0 wt. including rubber Reselect-2M, containing 20 wt.% the bound styrene, 7 wt.% linked methyl methacrylate and 13 wt.% oil MO-6, and enter 0.5. including sulfur, 1.0 wt. including sulfenamide C, 80,0 wt. including carbon black P-234, to 50.0 wt. including zinc oxide, 3.0 mass. including stearic acid, 3.0 mass. including oil MO-6, 1.5 wt. including protective wax SV-P, 6.0 wt. including strollerderby resin, 1,0 wt. including phthalic anhydride, 1.5 wt. hours of acetonemia R, 2.0 ATA test - in table 2.

The examples 1-10 and tables 1-2 data confirm that the claimed invention allows to achieve the desired technical result is to obtain a rubber compound, the vulcanizates on the basis of which possess high physical-mechanical and dynamic characteristics, wear resistance and grip.

1. Rubber mixture comprising polybutadiene rubber, solution polymerization, a copolymer of butadiene with vinylaromatic monomer emulsion polymerization, sulfur, zinc oxide, carbon black and additives target, characterized in that as butadiene rubber solution polymerization, the rubber mixture contains block copolymers of butadiene with styrene linear structure polystyrene-polybutadiene with a mass content of block polystyrene - 3-10%, and 1,2-butadiene units in part - 8-25% when the mass ratio of the specified block copolymers of butadiene with styrene, a copolymer of butadiene with vinylaromatic monomer emulsion polymerization 1:1,00-2,33, respectively, and with the following content of components in the rubber mixture, wt.h.:

The specified block copolymers

of butadiene with styrene 30-50

Sulfur is 0.5-1.5

Zinc oxide 1,0-5,0

Carbon 40,0-80,0

Additives target of 8.5-23,0

2. Rubber mixture comprising polybutadiene rubber, solution polymerization, a copolymer of butadiene with vinylaromatic monomer emulsion polymerization, sulfur, carbon black and additives target, characterized in that as butadiene rubber solution polymerization, the rubber mixture contains block copolymers of butadiene with styrene linear structure polystyrene-polybutadiene with a mass content of block polystyrene - 3-10%, and 1,2-butadiene units in part - 8-25%, and the copolymer with vinylaromatic monomer emulsion polymerization copolymer of butadiene, styrene and Acrylonitrile with a mass content of the bound styrene - 16-20% bound Acrylonitrile - 4-6%, or a copolymer of butadiene, styrene and methyl methacrylate with a mass content of the bound styrene - 11-20% and linked methyl methacrylate - 4-7% when the mass ratio of the above block copolymers of butadiene with styrene, a copolymer of butadiene, styrene and Acrylonitrile or a copolymer of butadiene, styrene and methyl methacrylate 1:1,0-2,33, respectively, with the following content of components in the rubber mixture, the EP butadiene,

styrene and Acrylonitrile or

a copolymer of butadiene, styrene and methyl

methacrylate 50-70

Sulfur is 0.5-1.5

Zinc oxide 1,0-5,0

Carbon 40,0-80,0

Additives target of 8.5-23,0

 

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