RU2507224C1 - Vulcanisable rubber mixture - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to production of a vulcanisable rubber mixture based on hydrogenated butadiene-nitrile rubber used to make industrial rubber articles for the oil extraction industry, oil refining industry and mechanical engineering. The rubber mixture contains the following components, pts.wt: hydrogenated butadiene-nitrile rubber - 100, quinol ether EX-1 - 3-7, technical carbon - 40-50, plasticiser - 6-10, stearic acid - 1-2, antioxidant - 1-3, fatty acid salt - sodium stearate, sodium oleate or zinc stearate - 1-3.

EFFECT: invention increases the rate of vulcanising the rubber mixture, enables to obtain rubber with an improved system of mechanical properties, high heat-resistance and resistance to liquid aggressive media.

6 tbl, 68 ex

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 for the oil, oil refining, engineering industries.

Known elastomeric composition containing up to 95 parts by weight hydrogenated nitrile butadiene rubber and as a vulcanizing agent including bis- (tert.butyl-peroxyisopropyl) -benzene, peroxide vulcanization co-agent (triallyl isocyanurate), stearic acid, filler, antioxidant [SU 2006116224/04, MGZh C08L 9/00, . 2007.11.20].

A disadvantage of the known composition is the need for vulcanization at elevated temperature (163-183 ° C).

Known rubber mixture based on hydrogenated nitrile butadiene rubber 100 wt.h. [Rubber and rubber, 2007, No. 1, pp. 4-7], including bis- (tert-butyl-peroxyisopropyl) -benzene as vulcanizing agent, vulcanization co-agent (triallyl isocyanurate), carbon black filler P 324, dibutyl-hydroxyethyl adipate plasticizer , antioxidant naphtha, dispersant.

A disadvantage of the known rubber composition is that the vulcanization process occurs at elevated temperatures and is explosive. Increased safety requirements when working with peroxides, especially at the stages of manufacturing rubber compounds and vulcanization, carried out at sufficiently high temperatures (160-180 ° C), limits the possibility of their use in the manufacture of rubber technical products. The vulcanization of this mixture at lower temperatures does not allow to obtain rubber with a sufficient level of required performance.

Close to the proposed rubber composition in technical essence and the technical result achieved is a rubber mixture based on hydrogenated nitrile butadiene rubber, including: curing agent o, o'-bis (1,3,5-three-tert-butylcyclohexadiene-2, 5-on-4-yl) -n-benzoquinone dioxime quinol ether (EC-1) 3.0-7.0 parts by weight; filler 40.0-50.0 parts by weight; plasticizer 6.0-10.0 parts by weight; stearic acid 1.0-2.0 parts by weight; antioxidant 1.0-3.0 parts by weight [Patent RU 2380386 C1]. This rubber compound is vulcanized at a lower temperature (143 ° C) and has significantly better indicators of relative residual compressive strain, which will allow it to be successfully used in lip seals for oil equipment, as well as in other rubber products.

The disadvantage of this rubber compound is its low vulcanization rate.

The problem solved by the invention: increasing the vulcanization rate of rubber compounds based on hydrogenated nitrile butadiene rubber, obtaining rubbers with good strength characteristics, a low level of accumulation of the relative residual deformation of static compression at elevated temperatures, in combination with high heat resistance, resistance to aggressive liquid wednesday

The technical result is to increase the vulcanization rate of rubber compounds based on hydrogenated nitrile butadiene rubber, rubber production with an improved set of indicators.

The specified technical result is achieved by the fact that the rubber mixture is based on hydrogenated nitrile butadiene rubber, including o, o'-bis (1,3,5-tri-tert-butylcyclohexadiene-2,5-one-4-yl as a vulcanizing agent ) -n-benzoquinone dioxime - quinol ether (EX-1), filler - carbon black, plasticizer, acid, antioxidant, additionally contains a salt of a fatty acid - sodium stearic acid, or zinc stearic acid, or sodium oleic acid, in the following ratio, wt.h .:

hydrogenated nitrile butadiene rubber 100.0 quinol ether [o, o'-bis (1,3,5-tri-tert. butylcyclohexadiene-2,5-one-4-yl) - -n-benzoquinone dioxime] 3.0-7.0 carbon black filler 40.0-50.0 plasticizer 6.0-10.0 antioxidant 1.0-3.0 fatty acid salt 1.0-3.0

The proposed mixture can be used hydrogenated nitrile butadiene rubbers of the brands Therban C3446 and Therban A4307, characterized by unsaturation and the number of units of acrylic acid nitrile.

The mixture is vulcanized with o, o'-bis (1,3,5-tri-tert-butylcyclohexadiene-2,5-one-4-yl) -n-benzoquinone dioxime (EH-1) ester (TU 6-09-513- 76) together with a salt of a fatty acid: sodium stearic acid (sodium stearate) TU 6-09-17-275-90; sodium oleic acid (sodium oleate) TU6-09-1224-83; zinc stearic acid (zinc sterate) TU 2432-006-4860-2470-99.

For amplification, active carbon black of grade P 324 (GOST 7885-86) was used as a filler.

Plasticizers: dibutyloxyethyl adipate (TU 2493-127-96), dioctyl 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.

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

The use of a salt of a fatty acid in conjunction with a curing agent quinil ether (EX-1) allows you to accelerate the vulcanization process. An increase in speed at vulcanization temperatures leads to a significant decrease in the total number of destruction processes, as a result of which an increase in strength and a reduced level of accumulation of residual deformations are observed in rubbers when tested under conditions of static compression, vulcanizates have an improved set of indicators.

A distinctive feature of the proposed rubber compound is the use of a fatty acid salt as an accelerator in the vulcanization of hydrogenated nitrile butadiene rubbers with quinol ether (EC-1). For the vulcanization of hydrogenated nitrile butadiene rubbers, quinol esters together with salts of fatty acids have not been previously used.

The claimed combination of essential features exhibits new properties that make it possible to obtain changes in the quantitative measure of the result, namely: an increase in the rate of vulcanization of rubber compounds, a decrease in the relative residual strain under static compression at elevated temperatures in combination with good strength characteristics, a high level of heat resistance, and resistance to action liquid aggressive environments.

The novelty of the proposed technical solution lies in a new combination of well-known components used in various rubber compounds.

The possibilities of achieving a beneficial effect in the practice of the invention are illustrated by examples.

Examples 1-13

For the manufacture of rubber compounds using hydrogenated nitrile butadiene rubber brand Therban C3446 company Bayer. Rubber compounds were made on rollers by sequentially introducing components according to generally accepted technology. Vulcanization was carried out at 143 ° C. The properties of rubber compounds and rubber indicators were determined on standard equipment according to GOST 10722-76, GOST 270-75, GOST 262-93, GOST 9.029-74.

The rubber composition of example 1 (analogue) contains a peroxide vulcanizing system. The rubber composition of example 2 (prototype) includes quinol ether (EC-1) as a vulcanizing agent. Rubber compounds of known composition (examples 1 and 2) are made and tested for comparison. The rubber mixtures according to examples 3-13 include quinol ether EH-1 together with a salt of a fatty acid — sodium stearate, the mixtures according to examples 3-11 contain the recommended dosages of the ingredients, and according to examples 12-13 they contain prohibitive dosages. The composition of the rubber compounds and the test results of rubbers with different contents of the ingredients are shown in table 1.

Examples 14-24

For the manufacture of rubber compounds using hydrogenated nitrile butadiene rubber brand Therban C3446 company Bayer. The composition of the rubber compounds is shown in table 2. Rubber compounds are made, and tested according to the methodology described in examples 1-13.

The rubber mixtures according to examples 14-24 include quinol ether (EC-1) together with a fatty acid salt - zinc stearate: the mixtures according to examples 14-22 contain the recommended dosages of the ingredients, according to examples 23-24 - the prohibitive dosages.

The test results of rubbers with different contents of the ingredients are shown in table 2. For comparison, the test results of rubbers of known composition (examples 1 and 2).

Examples 25-35

For the manufacture of rubber compounds using hydrogenated nitrile butadiene rubber brand Therban C3446 company Bayer. Rubber compounds are made and tested according to the methodology described in examples 1-13.

The rubber compounds of examples 25-33 include quinol ether (EX-1) together with a fatty acid salt of sodium oleate: the mixtures of examples 25-33 contain recommended dosages of the ingredients, and examples 34-35 contain prohibitive dosages.

The composition of the rubber compounds and the test results of rubbers with different contents of the ingredients are shown in table 3. For comparison, the test results of rubbers of known composition (examples 1 and 2).

Examples 36-46

For the manufacture of rubber compounds using hydrogenated nitrile butadiene rubber brand Therban C4307 from Bayer. Rubber compounds are made and tested according to the methodology described in examples 1-13.

The rubber mixtures according to examples 36-46 include quinol ether (EX-1) together with a fatty acid salt - sodium stearate: the mixtures according to examples 36-44 contain the recommended dosages of the ingredients, according to examples 45-46 - the prohibitive dosages.

The composition of the rubber compounds and the test results of rubbers with different contents of the ingredients are shown in table 4. For comparison, the test results of rubbers of known composition (examples 1 and 2).

Examples 47-57

For the manufacture of rubber compounds using hydrogenated nitrile butadiene rubber brand Therban C4307 from Bayer. Rubber compounds are made and tested according to the methodology described in examples 1-13.

The rubber mixtures according to examples 47-57 include quinol ether (EX-1) together with a fatty acid salt - zinc stearate: the mixtures according to examples 47-55 contain the recommended dosages of the ingredients, according to examples 56-57 - the prohibitive dosages.

The composition of the rubber compounds and the test results of rubbers with different contents of the ingredients are shown in table 5. For comparison, the test results of rubbers of known composition (examples 1 and 2).

Examples 58-68

For the manufacture of rubber compounds using hydrogenated nitrile butadiene rubber brand Therban C4307 from Bayer. Rubber compounds are made and tested according to the methodology described in examples 1-13.

The rubber mixtures according to examples 58-68 include quinol ether (EX-1) together with a fatty acid salt of sodium oleate: the mixtures according to examples 58-66 contain the recommended dosages of the ingredients, and according to the examples 67-68, prohibitive dosages.

The composition of the rubber compounds and the test results of rubbers with different contents of the ingredients are shown in table 6. For comparison, the test results of rubbers of known composition (examples 1 and 2).

From the data given in tables 1-6, it can be seen that mixtures based on the studied hydrogenated nitrile butadiene rubbers containing salts of fatty acids together with quinol ether are characterized by a higher vulcanization rate (optimum vulcanization at 143 ° C is 20 minutes), compared with mixtures with peroxide system (optimum 50 minutes) and quinol ether without accelerator (optimum 30 minutes). At the same time, the resulting rubbers exhibit a higher level of strength indicators, a lower level of accumulation of the relative residual deformation of static compression at elevated temperatures, in combination with high heat resistance and resistance to liquid aggressive media.

The increase in the number of salts of fatty acids more than 3.0 wt.h. (examples 12, 23, 34, 45, 56, 67) does not give significant advantages in terms of speed of vulcanization of rubber and leads to unproductive consumption of the product. The introduction of 0.5 wt.h. salts of fatty acids (examples 13, 24, 35, 46, 57, 68) are insufficient to accelerate the vulcanization process and the rate of vulcanization of rubber compounds and the properties of rubbers become almost equal to the speed of vulcanization and the properties of the known rubber compound (example 2). The use of prohibitive dosages of ingredients in rubber compounds does not lead to an improvement in the performance of rubbers, and in some cases worsen them.

Thus, those dosages of the fatty acid salt that provide the rubber compounds and the rubbers of them with indicators that are not lower than the corresponding parameters of the known rubber compound are taken as boundary ones.

-6ис (1,3,5-три-трет.бутилциклогексадиен-2,5-он-4-ил)-n-бензохинондиоксим (ЭХ-1) совместно с солями жирных кислот (натрия стеариновокислого, цинка стеариновокислого, натрия олеиновокислого) характеризуются большой скоростью вулканизации, вулканизаты из них имеют улучшенный комплекс показателей, что позволит их успешно использовать изготовления резиновых технических изделий, предназначенных для нефтедобывающей, нефтеперерабатывающей промышленности, машиностроения.Analysis of the obtained data shows that the rubber compounds according to the invention, containing quinol ether $$o,o^{{\text{'}\text{'}}^{\text{'}\text{'}}}$$

-6is (1,3,5-tri-tert-butylcyclohexadiene-2,5-one-4-yl) -n-benzoquinone dioxime (EX-1) together with the salts of fatty acids (sodium stearic acid, zinc stearic acid, sodium oleic acid) are characterized high vulcanization rate, vulcanizates from them have an improved set of indicators, which will allow them to successfully use the manufacture of rubber technical products intended for the oil, oil refining, engineering industries.

Claims (1)

Vulcanizable rubber mixture containing hydrogenated nitrile butadiene rubber, vulcanizing agent - quinol ester EX-1, filler, plasticizer, antioxidant, characterized in that it additionally contains a fatty acid salt selected from the group of sodium stearate, sodium oleate, zinc stearate in the following the ratio of components, parts by weight:
hydrogenated nitrile butadiene rubber 100.0 quinol ether EC-1 3.0-7.0 carbon black filler 40.0-50.0 plasticizer 6.0-10.0 antioxidant 1.0-3.0 fatty acid salt 1.0-3.0