Butadiene-methylstyrene rubber based rubber mixture

FIELD: chemistry.

SUBSTANCE: invention relates to the rubber industry and can be used in making industrial rubber articles. The butadiene-methylstyrene rubber based rubber mixture contains sulphur, diphenyl guanidine, a vulcanisation accelerator, technical carbon, zinc oxide, stearic acid, an anti-ageing agent and a modifier. The vulcanisation accelerator used is sulphenamide Ts, the anti-ageing agent and modifier are 2-(dibutylaminomethyl)-4-methyl-6-(1,7,7-trimethylbicyclo[2.2.1]hept-exo-2-yl)phenol.

EFFECT: high building tack while maintaining high ageing resistance of the butadiene-methylstyrene rubber based rubber mixture.

3 tbl, 4 ex

 

The invention relates to the rubber industry, in particular rubber compound on the basis of butadiene-methylstyrene rubber, and can be used for the manufacture of rubber products in various industries.

Known rubber compound on the basis of butadiene-methylstyrene rubber containing vulcanizing group, filler, zinc oxide and stearin technical (Koshelev FF General technology of rubber / PHEV, Amochaev, Aesome / M.: Chemistry, 1978. - 528 S., p.67). The disadvantage of this rubber compound is the absence of antioxidant and additives that increase confection tackiness of the rubber. Low confection tackiness is a technological disadvantage rubber mixtures based on butadiene-styrene rubber.

The closest is the rubber mixture on the basis of butadiene-methylstyrene rubber containing vulcanizing group - sulfur, captax, diphenylguanidine, the filler is carbon black, zinc oxide, stearin technical, antioxidant and inhibitor of premature vulcanization - imide 2-sulfobenzoic acid (patent No. 2307133/00, CL C08L 21; publ. 27.09.2007), selected as a prototype. The disadvantages of this rubber compound is insufficient confection tackiness.

Task: development of rubber compound on the basis of the e butadiene-methylstyrene rubber, which provides vulcanizates high resistance to ageing and has a high produts adhesion.

The technical result is to increase produts stickiness maintain high aging resistance of the rubber based on butadiene-methylstyrene rubber.

The technical result is achieved by the use of the rubber based on butadiene-methylstyrene rubber, including sulfur, vulcanization accelerator, diphenylguanidine, carbon black, zinc oxide, stearic acid, antioxidant and modifier, characterized in that the quality of a vulcanization accelerator used sulfenamid C, as an antioxidant and modifier - 2-(dibutylamino)-4-methyl-6-(1,7,7-trimethylbicyclo[2.2.1]hept-Exo-2-yl)phenol, in the following ratio of components, parts by weight: butadiene - methylstyrene rubber 100,0; sulfur 2,0; sulfenamid C 1,5; diphenylguanidine 0,3; zinc oxide 5,0; stearic acid 2,0; carbon 50,0; 2-(dibutylamino)-4-methyl-6-(1,7,7-trimethylbicyclo[2.2.1]hept-Exo-2-yl)phenol 3,0-4,0.

2-(Dibutylamino)-4-methyl-6-(1,7,7-trimethylbicyclo[2.2.1]hept-Exo-2-yl)phenol obtained by the known method (buravlev E.V., Chumichev YOU, suponitskiy KU, Kuchin AV New tertiary aminomethylphenol with isobornylic Deputy // Journal of General chemistry. 2008. No. 7. S-1183) and is the tsya polyfunctional molecule, which leads to the affinity with any other surface. In addition, for aminomethylphenol characterized by the formation of a fairly stable hydrogen bonds as intramolecular and intermolecular. So adding 2-(dibutylamino)-4-methyl-6-(1,7,7-trimethylbicyclo[2.2.1]hept-Exo-2-yl)phenol in the rubber mixture on the basis of butadiene-methylstyrene rubber increases confection tackiness of the rubber.

2-(Dibutylamino)-4-methyl-6-(1,7,7-trimethylbicyclo[2.2.1]hept-Exo-2-yl)phenol exhibits antioxidant properties, inhibiting the oxidation reactions in the chains of the rubber. The molecule structure of 2-(dibutylamino)-4-methyl-6-(1,7,7-trimethylbicyclo[2.2.1]hept-Exo-2-yl)phenol provides ease of separation of the hydrogen atom of the hydroxyl group and formed part of the radical in cooperation with peroxy radicals with the formation of stable reaction products. Thus, 2-(dibutylamino)-4-methyl-6-(1,7,7-trimethylbicyclo[2.2.1]hept-Exo-2-yl)phenol interrupts chain radical processes initiated getoperationname radicals, which contributes to maintaining a high resistance to aging of the rubber.

For testing 2-(dibutylamino)-4-methyl-6-(1,7,7-trimethylbicyclo[2.2.1]hept-Exo-2-yl)phenol as an antioxidant and a modifier that increases the stickiness of the rubber mixtures, the selected interval is l dosages of 3.0 to 4.0 parts by weight of

Butadiene-methylstyrene the caoutchouc ckmc-30-apkm-15 (GOST 11138-78).

Sulfur - vulcanizing agent (GOST 127.4-93).

Zinc oxide as an activator of a vulcanization accelerator (GOST 202-84).

Stearic acid - a vulcanization activator (GOST 6484-96).

Carbon black P-514 - filler (GOST 7885-86).

Sulfenamid C (dibenzothiazoledisulphide) of a vulcanization accelerator (THE 113-00-05761637-02-95).

Diphenylguanidine accelerator of vulcanization (GOST 40-80).

Synthesis and spectral data (IR and NMR spectra) of 2-(dibutylamino)-4-methyl-6-(1,7,7-trimethylbicyclo[2.2.1]hept-Exo-2-yl)phenol described in the article of Cookieboy YOU, Buravleva E.V., Suponitskiy KU, Kuchin AV "New tertiary aminothiophenol with isobornylic Deputy" // Journal of General chemistry. 2008. T. VIP. S-1183.

Example preparation of rubber mixtures

Rubber (butadiene-methylstyrene rubber, zinc oxide, stearic acid, diphenylguanidine, sulfenamid C (or captax the prototype), carbon black P-514, an antioxidant and a modifier (or an antioxidant and inhibitor of podocarpaceae the prototype), sulfur) were prepared on a laboratory roll mill at a temperature of 50±5°C. the Duration of mixing was 35 minutes. Then the rubber mixture was vulcanizates in a hydraulic press EAP 400-100 2E heated plates according to GOST 11997 at a temperature of 143°C in those which begins 20 minutes. Physico-mechanical properties of the vulcanizates was determined according to GOST 270-75 on a tensile testing machine RMI-250 at a temperature of 23±2°C at a rate of elongation of 500 mm/min Test rubbers on accelerated thermal aging in air was carried out in accordance with GOST 9.0224-74 at 125°C for 24 hours.

Definition produts sticky rubber compounds was carried out on the device "tel " So" company "Monsanto" by method M 38 405495-81 (and GOODS). Measured the resistance to delamination of the sheets of raw rubber mixture. A strip of rubber attached to the Cup pre-loaded spring scales, which can directly be noted compressive and tensile loads. Another sample of the mixture were mounted on a drum with a diameter of 3.4 cm and a width of 2.5 cm and lowered by means of the motor. The drum was rotated at 25 rpm In the lower position, the sample mixtures were pressed against each other with force 565 g, and then dispersed again. Noted the maximum position of the left side of the scale when reverse motion of the actuator. The data obtained with allowance for the inertia of the system was given the magnitude of the forces required for separation of the samples, i.e. showed confection tackiness samples of the rubber.

Formulations of rubber compounds offer (2-3) and foreign composition (1), as well as the composition of the prototype are shown in table 1 physico-mechanical properties of the vulcanizates are shown in table 2.

From the presented data show that the preservation of the strength of the proposed rubber compounds most similar to the prototype (Kdurable=0,10%) have a mixture of # 2 and # 3 (Kdurable.2=0,11%, Kdurable.3=0,10%).

From table 3 it can be seen that a larger value of the index of sticky rubber compound is observed in the proposed rubber compound No. 2 (0,278 MPa/0,325 MPa) relative to the prototype (0,172 MPa/0,194 MPa).

The optimal dosage of the proposed antioxidant and modifier is 3-4 parts by weight per 100 parts by weight of butadiene-methylstyrene rubber. Introduction less than 3 parts by weight provides less protection of vulcanizates from aging relative to the prototype. Introduction 2-(dibutylamino)-4-methyl-6-(1,7,7-trimethylbicyclo[2.2.1]hept-Exo-2-yl)phenol in a quantity greater than 4 parts by weight per 100 parts by weight of butadiene-methylstyrene rubber, does not affect the increase in the stickiness of the rubber.

Table 1
IngredientThe content of the ingredient in rubber compounds, parts by weight
the placeholder123
The caoutchouc ckmc-30-apkm-15100,0 100,0100,0100,0
Stearic acid1,52,02,02,0
Zinc oxide5,05,05,05,0
Sulfur2,02,02,02,0
Diphenylguanidine0,50,30,30,3
Captax1,5---
Sulfenamid C-1,51,51,5
Carbon black P-51450,050,050,050,0
Imide 2-sulfobenzoic acid (saccharin) 0,5---
2-(Dibutylamino)-4-methyl-6-(1,7,7-trimethylbicyclo[2.2.1]hept-Exo-2-yl)phenol-2,03,04,0

Table 2
IndexRubber compound
the placeholder123
Conditional tensile strength, MPa18,418,318,818,4
Elongation at break, %380380380380
Residual elongation, %12141212
The coefficient of thermal aging on strength at 125°C for 24 h (durable) 0,100,130,110,10

Table 3
IndexRubber compound
the placeholder123
Stickiness on tel So, MPa,
Time duplicate: 6 seconds0,1720,2340,2780,272
- 15 sec0,1940,2820,3250,318

Thus, the achieved technical result by introducing 2-(dibutylamino)-4-methyl-6-(1,7,7-trimethylbicyclo[2.2.1]hept-Exo-2-yl)phenol, adding which increases confection tackiness and maintains a high resistance to aging of the rubber based on butadiene-methylstyrene rubber.

The rubber mixture on the basis of butadiene-methylstyrene ka the Chuck, including sulfur, diphenylguanidine, a vulcanization accelerator, carbon black, zinc oxide, stearic acid, antioxidant, characterized in that the quality of a vulcanization accelerator used sulfenamid C, as an antioxidant and modifier - 2-(dibutylamino)-4-methyl-6-(1,7,7-trimethylbicyclo [2.2.1]hept-Exo-2-yl)phenol in the following ratio of components, parts by weight:

butadiene-methylstyrene rubber100,0
sulfur2,0
sulfenamid C1,5
diphenylguanidine0,3
zinc oxide5,0
stearic acid2,0
carbon50,0
antioxidant and modifier3,0-4,0.



 

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19 cl, 6 tbl

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2 tbl

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