RU2709874C1 - Vulcanizable rubber mixture - Google Patents

Abstract

FIELD: technological processes.

SUBSTANCE: invention relates to rubber industry and can be used in machine building, oil producing and oil refining industry. Rubber mixture contains the following components, pts. wt.: hydrogenated butadiene-nitrile rubber 100, vulcanizing agent N,N'-bis-n-nitrosophenylderivative of alkanediamine 3–7, technical carbon 40–50, plasticizer 6–10, stearic acid 1–2, antioxidant 0–1.

EFFECT: higher speed of vulcanization of rubber mixtures based on hydrogenated butadiene-nitrile rubber, obtaining rubber with low level of accumulation of relative static deformation of static compression under conditions of high temperatures, resistance to aging processes, heat resistance and resistance to action of liquid aggressive media.

1 cl, 24 ex, 4 tbl

Description

The invention relates to the production of a vulcanizable rubber mixture based on hydrogenated nitrile butadiene rubber used for the manufacture of rubber technical products intended for mechanical engineering, oil production, oil refining industry.

Known rubber mixture based on hydrogenated nitrile butadiene rubber, including sulfur, sulfenamide C, tiuram, filler [Rubber and rubber No. 2, 2006, p. 6-9].

A disadvantage of the known composition is the need to carry out vulcanization at elevated temperatures of more than 160 ° C, at which the rate of destruction processes increases significantly, resulting in a decrease in the heat resistance of rubbers, and an increased level of accumulation of residual deformations when tested under conditions of static compression.

Known elastomeric composition based on hydrogenated nitrile butadiene rubber - 100 wt. hours including 4.0-8.0 wt. including bis- (tert.butylperoxyisopropyl) -benzene, 2.0 wt. including coagent peroxide vulcanization (triallylisocyanurate). [Rubber and rubber, 2007, No. 1, p. 4-7]

A disadvantage of the known composition is the need for vulcanization at elevated temperatures (160-180 ° C). Carrying out vulcanization at lower temperatures (140 ° C) does not allow to obtain rubber with a sufficient level of required performance.

Closest to the proposed rubber compound in technical essence and the achieved technical result is a rubber mixture containing up to 95 wt. including hydrogenated nitrile butadiene rubber, nitrile butadiene rubber - 5 wt. hours and as a vulcanizing agent, including bis- (tert.butylperoxyisopropyl) -benzene as a vulcanizing agent - 4.0-8.0 wt. hours, vulcanization coagent (triallyl isocyanurate) - 0.5-2 wt. o'clock, filler - 40-60 wt. hours, plasticizer up to 20 wt. hours, antioxidant 1-3 wt. h, stearic acid - 1-3 wt. h (RU Patent No. 2322462, publ. 2007.11.20].

A disadvantage of the known rubber mixture is that the process of vulcanization with peroxides occurs at an elevated temperature of 180 ° C and is explosive, which limits the possibility of their use in the production of rubber products.

The task of the invention is to reduce the temperature of vulcanization of rubber compounds based on hydrogenated nitrile butadiene rubber while improving their performance properties.

The technical result of the invention is to increase the rate of vulcanization of rubber compounds based on hydrogenated nitrile butadiene rubber, which will allow the process to be carried out at lower temperatures, the production of rubbers with a low level of accumulation of the relative residual deformation of static compression at elevated temperatures, in combination with resistance to aging processes, high rates of heat resistance, resistance to the action of liquid aggressive environments.

The specified technical result is achieved in that the rubber mixture comprising hydrogenated nitrile butadiene rubber, a vulcanizing agent, a filler is carbon black, a plasticizer, stearic acid, an antioxidant according to the invention, contains N, N'-bic-n-nitrosophenyl as a vulcanizing agent an alkanediamine derivative such as N ¹ , N ² bis (4-nitrosophenyl) ethane-1,2-diamine or N ¹ , N ⁶ bis (4-nitrosophenyl) hexane-1,6-diamine, with the following ratios of components, wt. hours:

hydrogenated nitrile butadiene rubber 100.0 N, N'-bis-n-nitrosophenyl derivative alkandiamine 3.0-7.0 carbon black filler 40.0-50.0 plasticizer 6.0-10.0 stearic acid 1.0-2.0 antioxidant 0-1.0

The proposed mixture can be used hydrogenated nitrile butadiene rubbers of the brands: Terban from Bayer, Tornak from Polysar, Zetpol from Zeon with a residual double bond content of from 0.9 to 5.5%. grades Therban 3446 (with acrylic acid nitrile content ~ 34%, unsaturation ~ 4%) and Therban 4307 (acrylic acid nitrile contents ~ 43%, unsaturation ~ 0.9%).

Active carbon black of grades: P - 324, P - 234, P - 514 was used as a filler for amplification.

Plasticizers: dibutyl phthalate, dibutyl sebacinate (GOST 8728-88) are introduced into the rubber mixture to improve processing, increase the frost resistance of rubbers, and reduce the level of swelling in aggressive environments.

Stearic acid (GOST 6484-96) is used to improve the dispersion of ingredients in the rubber compound, to facilitate its processing.

The following can be used as antioxidant: N-isopropyl-N'-phenyl-n-phenylenediamine - diafen FP (TU 2492-002-05761637-99), phenyl-β-naphthylamine - naphtham 2 (GOST 39-79), polymerized 2, 2, 4-trimethyl-1,2-dihydroquinoline-acetonanil R (TU 6-02-1116-82).

Use as a vulcanizing agent of nitrosophenyl derivatives of N, N'-bis-n-alkanediamine, such as N ¹ , N ² bis (4-nitrosophenyl) ethane-1,2-diamine, or N ¹ , N ⁶ bis (4- nitrosophenyl) hexane-1,6-diamine, instead of peroxides, leads to an increase in the rate of vulcanization and allows the process to be carried out at lower temperatures. A decrease in the vulcanization temperature leads to a significant decrease in the rate of destruction processes, the formation of a more stable network of strong chemical bonds, as a result of which the rubbers have sufficiently long guaranteed storage periods under conditions of static compression deformation at elevated temperatures.

The presence of spatially substituted amine groups in the composition of the proposed vulcanization agents has a stabilizing effect on rubber compounds and rubbers and helps to increase the resistance of the resulting rubbers to thermal aging, ensures the preservation of the necessary physical and mechanical properties during product operation. This allows you to reduce the dosage of the antioxidant, or completely eliminate it from the composition of rubber compounds.

A distinctive feature of the proposed rubber composition is the use of hydrogenated nitrile butadiene rubbers N, N'-bis-n-nitrosophenyl derivatives of alkanediamine, such as 1,2-ethanediamine or 1,6-hexanediamine, which have not been previously used as vulcanizing agents.

The claimed combination of essential features exhibits new properties that allow to obtain changes in the quantitative measure of the result, namely: a decrease in the vulcanization temperature of rubber compounds, a decrease in the relative residual strain under static compression at elevated temperatures.

The use of N, N'-bis-n-nitrosophenyl derivatives of alkanediamines (such as 1,2-ethylenediamine, 1,6-hexamethidenediamine) as rubber compounds of this qualitative and quantitative composition is not known for other technical solutions. That is, the claimed solution meets the criterion of "novelty." The evidence is the lack in the literature, including the patent, of information on the use of N ¹ , N ² bis (4-nitrosophenyl) ethane-1,2-diamine or N ¹ , N ⁶ bis (4-nitrosophenyl) hexane-1, 6-diamine in rubber compounds based on hydrogenated butadiene-nitrile rubbers.

The invention is illustrated by examples.

Examples 1-7.

Rubber mixtures based on hydrogenated nitrile butadiene rubber of Therban 3446 brand (with an acrylate content of ~ 34%, an unsaturation of ~ 4%) were made on rollers with sequential introduction of components according to standard technology. The composition of the proposed mixtures (examples 3-7) based on rubber 3446, in comparison with the known (examples 1,2), are presented in table 1.

The vulcanization of known mixtures was carried out at temperatures of 143, 151 and 163 ° C. The mixtures of examples 3-7 were vulcanized N ¹ , N ² -bis (4-nitrosophenyl) ethane-1,2-diamine at 143 ° C.

Physico-mechanical indicators were determined according to GOST 270-75, GOST 263-93 on standard equipment. The resistance of rubbers to the effects of liquid aggressive media during static compression deformation was determined according to GOST 9.070-76. For testing as a standard hydrocarbon medium, SZhR-1 oil (TU 38 10195-86) was used, which is a well-purified product of sulfur oils of residual origin.

Table 1 shows the test results of rubbers of known composition (examples 1 and 2) and the proposed composition (examples 3-7) with different contents of ingredients.

Examples 8-12

Therban 3446 hydrogenated nitrile butadiene rubber compounds (with acrylic acid nitrile content of ~ 34%, unsaturation of ~ 4%) were manufactured on rollers by sequentially introducing components using conventional technology. N ¹ , N ⁶ -6 hc (4-nitrosophenyl) hexane-1,6-diamine was used as a curing agent. The composition of the proposed mixtures (examples 8-12) based on rubber 3446, in comparison with the known (examples 1,2), are presented in table 2.

Vulcanization of known mixtures was carried out at temperatures of 143, 151 and 163 ° C. The mixtures of Examples 8-12 were vulcanized with N ¹ , N ⁶ -bis (4-nitrosophenyl) hexane-1,6-diamine at 143 ° C.

The rubber compounds were made on rollers, vulcanized and tested in accordance with the methods described in examples 1-7.

Table 2 shows the test results of rubbers of known composition (examples 1 and 2) and the proposed composition (examples 8-12) with different contents of ingredients.

Examples 13-19

Therban 4307 hydrogenated nitrile butadiene rubber compounds (with an acrylic acid nitrile content of ~ 43%, an unsaturation of ~ 0.9%) were manufactured on rollers by sequentially introducing components using conventional technology. N ¹ , N ² bis (4-nitrosophenyl) ethane-1,2-diamine was used as a vulcanizing agent. The composition of the proposed mixtures (examples 15-19) based on rubber 4307, in comparison with the known (examples 13, 14), are presented in table 3.

Vulcanization of known mixtures was carried out at temperatures of 143, 151 and 163 ° C. The mixtures according to examples 15-19 were vulcanized by N ¹ , N ² bis (4-nitrosophenyl) ethane-1,2-diamine at 143 ° C.

The rubber compounds were made on rollers, vulcanized and tested in accordance with the methods described in examples 1-7.

Table 3 shows the test results of rubbers of known composition (examples 13 and 14) and the proposed composition (examples 15-19) with different contents of ingredients.

Examples 20-24

Therban 4307 hydrogenated nitrile butadiene rubber compounds (with an acrylic acid nitrile content of ~ 43%, an unsaturation of ~ 0.9%) were manufactured on rollers by sequentially introducing components using conventional technology. As the curing agent, N ¹ , N ⁶ bis (4-nitrosophenyl) hexane-1,6-diamine was used. The composition of the proposed mixtures (examples 20-24) based on rubber 4307, in comparison with the known (examples 13, 14), are presented in table 4.

Vulcanization of known mixtures was carried out at temperatures of 143, 151 and 163 ° C. The mixtures of examples 20-24 were vulcanized N ¹ , N ⁶ -bis (4-nitrosophenyl) hexane-1,6-diamine at 143 ° C.

The rubber compounds were made on rollers, vulcanized and tested in accordance with the methods described in examples 1-7.

Table 4 shows the test results of rubbers of known composition (examples 13 and 14) and the proposed composition (examples 20-24) with different contents of ingredients.

Analysis of the obtained data shows that the rubber mixture according to the invention containing N, N'-bis-n-nitrosophenyl derivative of alkanediamine as a vulcanizing agent, such as N ¹ , N ² bis (4-nitrosophenyl) ethane-1,2-diamine , or N ¹ , N ⁶ bis (4-nitrosophenyl) hexane-1,6-diamine, vulcanizes at lower temperatures and has significantly better accumulation of relative residual compressive deformation at elevated temperatures, has good heat resistance, and is resistant to action of liquid aggressive environments, resistant to aging processes.

Claims (2)

A vulcanizable rubber mixture containing hydrogenated nitrile butadiene rubber, a vulcanizing agent, a filler, a plasticizer, stearic acid, an antioxidant, characterized in that it contains N, N'-bis-n-nitrosophenyl alkanediamine derivative, such as N ¹ , N ^2- bis (4-nitrosophenyl) ethane-1,2-diamine or N ¹ , N ⁶ -bis (4-nitrosophenyl) hexane-1,6-diamine, in the following ratio, wt.h .: hydrogenated nitrile butadiene rubber 100.0 N, N'-bis-n-nitrosophenyl derivative alkandiamine 3-7 carbon black filler 40-50 plasticizer 6-10 stearic acid 1-2 antioxidant  0-1