RU2755481C1 - Elastomeric composition and method for production thereof - Google Patents

Abstract

FIELD: gas production.

SUBSTANCE: present invention relates to the gas production industry, namely to elastomeric compositions intended for production of seals based thereon, as well as to a method for producing elastomeric compositions based on hydrogenated butadiene-nitrile rubbers. Proposed is an elastomeric composition based on hydrogenated butadiene-nitrile rubber with an acrylonitrile content of 18 to 52 wt.%, containing organic peroxide and a peroxide vulcanisation accelerator, a filler, an anti-aging agent, plasticising additives, as well as a salt of polyvalent metals of acrylic or methacrylic acid, as vulcanising agents; also proposed is a method for producing an elastomeric composition based on hydrogenated butadiene-nitrile rubber, wherein the elastomeric composition is prepared by mixing in two stages.

EFFECT: technical result of the proposed invention consists in increasing the operating life of seals in the medium of a formation fluid including a hydrocarbon fraction as well as gaseous hydrogen sulphide and carbon dioxide; increasing the heat resistance, acquiring a high degree of adhesion to metals.

8 cl, 3 tbl

Description

SCOPE OF THE INVENTION

The proposed invention relates to the gas industry, in particular to elastomeric compositions intended for the manufacture on their basis, including seals operating at high temperatures and pressures in direct contact with corrosive media and used in the equipment of the subsea hydrocarbon production system. The present invention discloses a recipe, a method for producing and processing such compositions and products. In particular, the invention relates to a method for producing elastomeric compositions based on hydrogenated nitrile butadiene rubbers used for the manufacture of seals reinforced with metal reinforcement, synthetic, mineral or natural fibers.

BACKGROUND OF THE INVENTION

In general, rubber elastomeric materials, in particular, rubber based on acrylonitrile-budadiene copolymer, are used as materials for the manufacture of seals for movable and fixed joints and elements of equipment for a subsea production system. Additionally, products made from the proposed material can be used in gas processing, oil production and oil refining industries, energy and other industries.

From patent RU 2309962, IPC C08L 9/02, publ. 11/10/2007 known rubber compound for the manufacture of lip seals for oil equipment. A mixture based on nitrile butadiene rubber, including stearic acid, zinc whitewash, carbon black, fiber, and containing nitrile butadiene rubber of BNKS-40 AM, BNKS-40 AMN and hydrogenated butadiene-nitrile rubber of BNKV-4030, Terban, as well as technical carbon grade P-803 and grade P-245, aramid or polyamide fiber, and additionally contains sulfur, sulfenamide M, altax, rosin, dibutoxyethyl adipate, white carbon, diafen FP and modifier RU-D.

The disadvantage of the composition according to RU2309962 is low thermal stability, the inability to operate at temperatures above 100 ° C, which is due to the presence in the composition of unsaturated nitrile butadiene rubbers, which are prone to degradation at elevated temperatures.

Further, from patent RU 2495061, publ. 10.10.2013, IPC C08L 9/02, a heat-resistant rubber compound based on a combination of nitrile butadiene rubber is known, including a vulcanizing agent, a peroxide vulcanization co-agent, zinc oxide, a processing aid for rubber compounds and carbon black, while this known mixture contains a vulcanizing agent novoperox BP-40, coagent of peroxide vulcanization deltagran HVA-2 70GE, technological additive for rubber compounds in the form of softener RS-1 and additionally 2-mercaptobenzthiazole, burnt magnesia, stearic acid, naugard 445, novatox 8PFDF-22, technical additive for rubber compounds N 220, carbon black P 514, oligoestercrylates MGF-9 and THM.

The disadvantage of the composition according to the patent RU2495061 is low thermal stability, insufficient resistance to the action of hydrogen sulfide, as well as a short service life at elevated temperatures, due to the presence of hydrogenated nitrile butadiene rubber in the composition.

From patent CA2925928, IPC, C08L9 / 02, publ. 06/19/2018, an elastomeric composition is known containing a rubber selected from acrylonitrile butadiene, hydrogenated acrylonitrile butadiene, carboxylated acrylonitrile butadiene and a combination thereof; reinforcing fibers selected from aramid fibers, carbon fibers, polyester fibers, glass fibers, nylon fibers and mixtures thereof and / or nanofilament structures selected from the group of nanowires, nanorods, nanofibers, nanoribbons and nanotubes and combinations thereof. The compositions according to CA2925928 can be curable or non-curable and can be used to prepare various articles. CA2925928 also discloses methods for preparing the compositions.

The disadvantage of the composition according to CA2925928 is the lack of the possibility of long-term operation of products made from a known composition at high temperatures and high operating pressure.

From the source CN 106117658, IPC C08L 9/02, publ. 11/16/2016, known elastomeric composition with increased mechanical strength, high cold resistance and a wide range of performance. The composition according to CN106117658 is based on acrylonitrile butadiene rubber, ethylene propylene rubber, butadiene rubber, styrene butadiene rubber and polyethylene wax. The presence in the composition of a large amount of non-polar rubbers characterizes low stability to the action of hydrocarbons.

From the publication WO 2000004098 A1 known formulation of an elastomeric material based on hydrogenated nitrile butadiene rubber, containing 100 wt. including elastomer from 2 to 40 wt. including dispersed non-fibrous organic polymer material. This known elastomeric composition exhibits high abrasion resistance, tensile strength, elastic modulus as well as good aging resistance.

The disadvantage of the composition according to WO 2000004098 A1 is the limited operating temperature range, short service life, which is due to the content of unsaturated polymer material.

From publication WO 2003072650 A1, IPC C08L 9/02, publ. 04.09.2003, known polymer composition containing 100 wt. including nitrile copolymer rubber having an iodine number of 100 or less, and from 10 to 150 wt. including particles with an average diameter of 10 microns or less methyl methacrylate homopolymer or copolymer containing at least 50 wt. % methyl methacrylate units, The rubber composition is processed by heating the polymer composition at a temperature higher than at least 20 ° C than the glass transition temperature Tg of the polymer constituting these particles, The vulcanized rubber composition is obtained by including a vulcanizing agent in the rubber composition.

The disadvantage of the composition according to WO 2003072650 A1 is a low service life, insufficient resistance to hydrogen sulfide and carbon dioxide, due to the presence of unsaturated butadiene units in the rubber, as well as low frost resistance.

The closest analogue of the present invention is the source US20200002515, publ. 01/02/2020, IPC C08L 9/02, C08K 5/00, which discloses the formulation of an elastomeric composition based on hydrogenated nitrile butadiene rubber, maleinized polybutadiene and metal oxide, additionally including a vulcanizing group, fillers and other additives. In some embodiments of the invention according to US20200002515, the finished composition may contain one or more metal oxide compounds, for example: magnesium oxide, zinc oxide, hydrotalcite.

This known formulation of the elastomeric composition contains the following ingredients: Zetpol 2000L in an amount of 75.0 wt. hours, ZETPOL 2000EP in the amount of 25.0 wt. hours, N990 in the amount of 75.0 wt. including, Vanox CDPA in the amount of 1.5 wt. h., Vanox ZMTI in the amount of 1 wt. h., Vanox MVM in the amount of 1 wt. hours, SR517 in the amount of 2 wt. including, TRIGONOX 17-40 in the amount of 11 wt. including, LUPEROX DC40P-SP2 in the amount of 5.25 wt. h ..

Mixing of ingredients is carried out in two stages. At the first stage, the ingredients are mixed in a mixer with a volume of 1.5 liters to ensure their uniform distribution over the volume of the material. at a temperature of 140-150 ° C. The second stage of mixing is carried out on rollers. At this stage, a vulcanizing group is introduced.

The formulation and preparation of the composition is described in more detail in the following example: in closed type mixers (Banbury type mixer) a mixture is prepared in the following sequence. At a temperature of 140 ° C, hydrogenated nitrile-butadiene rubber Zetpol 2000L (100 parts by weight) is loaded into the mixer and mixed for 7 minutes. Next, 100 wt. including methyl methacrylate homopolymer with an average particle diameter of 10 microns and mix for 10 minutes. After preparation, the mixture is cooled and aged for several hours. Then, a vulcanizing group is introduced into the rubber mixer at a temperature of 80 ° C, including organic peroxide LUPEROX F40P (12 parts by weight) and TAIC (8 parts by weight), mixing is carried out for 12 minutes.

Further, the resulting composition is vulcanized in the form of standard test pieces, as well as control samples with metal reinforcement in a hydraulic press at a temperature of 160 ° C for 30 minutes. Then the obtained samples are thermostated at a temperature of 150 ° C for 6 hours. The obtained samples were subjected to tests, the results of which are presented in table 3 (see example 10) in order to provide an illustration of the advantages of the claimed technical solution over the prior art.

The main disadvantage of the described analogue in the manufacture on its basis of sealing products and elements of subsea production systems operating in direct contact with aggressive media under the influence of high temperatures is insufficient resistance to thermo-oxidative destruction, as well as high values of the residual compression deformation, which are unacceptable for real operating conditions in the equipment of the gas production industry.

The problem to be solved by the proposed technical solution is to eliminate at least some of the shortcomings of technical solutions of the prior art, as well as to create an elastomeric composition for the production of seals on its basis, used in the system of subsea hydrocarbon production.

DISCLOSURE

The technical result of the proposed invention is to increase the service life in a formation fluid environment, including a hydrocarbon fraction, as well as gaseous hydrogen sulfide and carbon dioxide; increased heat resistance, high adhesion to metals.

According to a first embodiment of the present invention, there is provided an elastomeric composition based on hydrogenated nitrile butadiene rubber with an acrylonitrile content in an amount of 18% to 52%, containing organic peroxide and a peroxide vulcanization accelerator as vulcanizing agents, a filler, an antioxidant, an antioxidant, plasticizing additives , an elastomeric composition containing:

salt of polyvalent metals of acrylic or methacrylic acids with the following ratios of components wt. h .:

hydrogenated nitrile butadiene rubber 100.0;

polyvalent metal salt of acrylic or methacrylic acid 45.0-85.0;

in combination with a complex of stabilizing additives, including the zinc salt of methylmercaptobenzimidazole, 4,4'-bis (alpha-, alpha-demethylbenzyl) definylamine, trimethylolpropane trimethacrylate in the following ratios of components, wt. h .:

hydrogenated nitrile butadiene rubber 100.0;

zinc salt of methyl mercaptobenzimidazole 1.0-2.0;

4,4'-bis (alpha-, alpha-demethylbenzyl) definylamine 1.5-2.5;

trimethylolpropane trimethacrylate 1.0-2.5;

with a total ratio of components, wt. h .:

hydrogenated nitrile butadiene rubber 100.0;

polyvalent metal salt of acrylic or methacrylic acid 45.0-85.0;

organic peroxide 8.0-12.0;

peroxide vulcanization accelerator 10.0-14.0;

zinc oxide 5.0;

stearic acid 1.0-15.0;

filler 50.0-70.0;

plasticizer 5.0-15.0;

zinc salt of methyl mercaptobenzimidazole 1.0-2.0;

4.4'-bis (alpha-, alpha-demethylbenzyl) definylamine 1.5-2.5;

trimethylolpropane trimethacrylate 1.0-2.5.

The proposed elastomeric composition is characterized in that the salt of polyvalent metals of acrylic and methacrylic acids is a reaction product of an oxide or hydroxide of a polyvalent metal, introduced in an amount of 35.0-40.0 wt. including, and acrylic or acrylic and methacrylic acids, introduced in the amount of 15.0-55.0 wt. h ..

In the proposed elastomeric composition, the organic peroxide can be selected from the group including:

2.5-di (tert-butylperoxy) -2,5-dimethylhexane;

tert-butylcumyl peroxide;

1,3 and 1,4-di (tert-butylperoxyisopropyl) benzene;

dicumyl peroxide;

n-butyl 4,4-di (tert-butylperoxy) valerate;

1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane.

In the proposed elastomeric composition, the peroxide vulcanization accelerator is selected from the group consisting of triallyl isocyanurate or trimethylolpropane trimethacrylate.

In the proposed elastomeric composition, the filler is inactive carbon black.

In the proposed elastomeric composition, the plasticizing additive is selected from the group consisting of plasticizers based on phthalic acid esters or sebacate acid.

According to another embodiment of the present invention, there is provided a method for preparing an elastomeric composition based on hydrogenated nitrile butadiene rubber, in which the elastomeric composition is prepared by mixing in two stages,

and at the first stage

prepare a mixture of components, wt. h .:

hydrogenated nitrile butadiene rubber 100.0;

polyvalent metal salt of acrylic or methacrylic acid 45.0-85.0;

zinc oxide 5.0 as an antioxidant and / or antioxidant;

stearic acid 1.0-15.0 as an antioxidant and / or antioxidant;

filler 50.0-70.0;

plasticizer 5.0-15.0;

in closed type mixers at a temperature of 120-140 ° C with sequential injection of components with a total mixing time in the first stage of 40 ± 5 minutes; in the second stage, the following components are introduced:

zinc salt of methyl mercaptobenzimidazole 1.0-2.0;

4,4'-bis (alpha-, alpha-demethylbenzyl) definylamine 1.5-2.5;

trimethylolpropane trimethacrylate 1.0-2.5;

organic peroxide 8.0-12.0;

peroxide vulcanization accelerator 10.0-14.0;

in closed type mixers or on rollers with sequential injection of components.

In the proposed method for producing an elastomeric composition at the first stage, a modifier is obtained, a salt of a polyvalent metal of acrylic or methacrylic acid is carried out in the process of obtaining a composition by the reaction between an oxide or hydroxide of a polyvalent metal with acrylic or methacrylic acid, in the following ratios of components, wt. h .:

hydrogenated nitrile butadiene rubber 100.0;

oxide or hydroxide of a polyvalent metal 30.0-45.0;

acrylic or methacrylic acid 15.0-55.0;

in this case, the acid formation reaction takes place during the preparation of the composition or vulcanization at a temperature from 120 ° C to 140 ° C with a process duration of at least 10 minutes.

Preferably, in the proposed method for producing an elastomeric composition when performing the second stage on the rollers, the temperature of the rollers is 60-80 ° C with a total mixing time of 40 ± 5 minutes; and during the second stage in the mixer, the temperature of the rolls is 60-80 ° C with a total mixing time of 20 ± 5 minutes.

Preferably, in the proposed method, the elastomeric composition is prepared by mixing the components on rollers in two stages: in the first stage, a mixture of all components is prepared, except for the introduction of organic peroxide, followed by curing the mixture for 4 hours; the second stage is carried out by the introduction of organic peroxide on the rollers.

Compositions based on hydrogenated nitrile butadiene rubbers exhibit high resistance to the action of oil and petroleum products, and, in contrast to nitrile butadiene rubbers, are highly resistant to hydrogen sulfide due to the high saturation of the macromolecule chain, as well as higher resistance to thermal oxidative aging. Unfortunately, this type of rubbers, like nitrile butadiene rubbers, are prone to cyclization when exposed to high temperatures on acryl-nitrile groups. Therefore, for long-term operation, it is required to exclude the possibility of cyclization of acrylonitrile groups.

A typical solution to the problem is to use a combination of amine (diamine) and sterically hindered phenolic stabilizers. However, as the cyclic processes develop, the consumption of stabilizers occurs, which leads to their depletion, and in the future the aging process can develop.

In the proposed method, the problem is solved by blocking nitriacrylate groups by introducing compounds that provide non-covalent interactions. Thus, the combination of sterically hindered phenolic stabilizers and a salt of methylmercaptobenzimidazole with a polyvalent metal provides, due to non-covalent interactions, the formation of a complex that is not prone to cyclization to conditions under which the complex may not be destroyed. The destruction of such complexes can occur only when an energy is applied that exceeds the energy of covalent interactions.

Typically, this interaction can be overcome at high temperatures, around 200 ° C or exposure to strong acids, or both. In this case, sterically hindered phenolic stabilizers act as sorbents for free radicals, slowing down the process of rubber destruction.

An acrylic or methacrylic acid salt of a polyvalent metal is polyfunctional. Firstly, this salt, like the methylmercaptobenzimidazole salt, is capable of non-valent interactions with the acrylonitrile group, and secondly, it helps to increase the adhesion properties of the composition with metals. Thus, the salt of acrylic and methacrylic acids are capable of non-valent interactions and have adhesively active hydroxyl and carbonyl groups that exhibit high adhesion to metals.

As the saturated nitrile-butadiene rubber, rubbers with an acrylonitrile content of 18 to 52 wt. %, Mooney viscosity from 38 to 105 conv. units and an iodine number from 7 to 56 g / 100 g. For example, rubbers of the trade names Zetpol 2000, Zetpol 2000L, Zetpol 1010, Zetpol 4310, Therban 3406, Therban 4307 can be used.

As an organic peroxide, 2,5-di (tert-butylperoxy) -2,5-dimethylhexane - Luperox 101; tert-butylcumyl peroxide - Luperox 801; 1,3 and 1,4-di (tert-butylperoxyisopropyl) benzene - Luperox - F; dicumyl peroxide - Luperox - DC; n-butyl 4,4-di (tert-butylperoxy) valerate - Luperox 230; 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane - Luperox 231.

Triallyl isocyanourate or trimethylolpropane trimethacrylate can be used as an accelerator for peroxide vulcanization. Triallyl isocyanurate or trimethylolpropane trimethacrylate supported on calcium carbonate with a substance content of 50% to 70% can also be used, such as Actigran 50, Actigran 70, Taicros.

As the polyvalent metal salt, a zinc salt of acrylic and methacrylic acid and / or a magnesium salt of acrylic and methacrylic acid is used.

Trimethylolpropane trimethacrylate, marketed under the trade names Monomer X980, TMPTA, TAC, can also be used.

The zinc salt of methyl mercaptobenzimidazole can be used in the form of a powder at 100% concentration of the substance or in the form of granules on a polymer carrier with an 80% concentration of the substance, marketed under the trade names Rhenogran® ZMMBI-50, ALCHEM ZMMBI.

4,4'-bis (alpha-, alpha-demethylbenzyl) definylamine (BPH-80 / L) can be used as a powder with 100% concentration of the substance or in the form of granules on a polymer carrier with 80% concentration of the substance produced under trade names , ALCHEM OMB, Rhenogran® BPH-80 / L.

Carbon black is selected from the group including carbon black P-803, P-701, P-514, P-234, P-324 according to GOST 7885 or their analogues.

Dibutyl sebacate complies with GOST 8728.

Stearic acid complies with GOST 6484.

Zinc oxide complies with GOST 202.

Hardness was determined in accordance with GOST R ISO 76129-1 using a durometer A.

Conditional tensile strength and elongation at break were determined in accordance with GOST ISO 37-1 on type 1 specimens at a tensile speed of 500 mm / min.

Residual compression deformation was determined according to GOST R ISO 815-1 at a temperature of 100 ° C, a deformation of 25%, exposure for 168 hours.

The glass transition temperature was determined by the DMA method in accordance with GOST R ISO 56753.

The predicted service life was determined in accordance with GOST 9.707 in the environment of the simulated fluid presented in Table 1 with aging for 36 days at a pressure of 70 MPa.

The coefficient of change in physical and mechanical properties during aging was determined in accordance with GOST 9.024 during aging at a temperature of 120 ° C for 168 hours.

The force of separation of rubber from metal was determined in accordance with GOST 209 according to the method of V.

CARRYING OUT THE INVENTION

The invention is illustrated by the following examples.

Example 1. In a closed type mixer, in this case a Banbury type mixer, a mixture with the components is prepared in the following sequence. At a temperature of 140 ° C, hydrogenated nitrile butadiene rubber Zetpol 2000L is loaded into the mixer and plasticized at a rotary speed of 35-40 rpm for 10 minutes. The Vulkan N330 grade carbon black filler is then added to the mixer and mixing is continued for 5 minutes. Then the polyvalent metal salt of acrylic and methacrylic acid is added to the mixer and mixing is continued for 10 minutes. Next, zinc oxide is sequentially loaded into the mixer, after 3 minutes stearic acid is loaded and mixing is continued for 7 minutes. After that, the mixture is unloaded, rolled on rollers for 35 minutes and aged for 6 hours.

The second stage of mixing is carried out on rollers, while the mixing temperature is 60-70 ° C. The prepared mixture is plasticized on the rollers within 5 minutes. After that, the methyl mercaptobenzimidazole salt is added to the composition, after 3 minutes of mixing, 4,4'-bis (alpha-, alpha-demethylbenzyl) definitioninylamine is added, after another 3 minutes, trimethylolpropane trimethacrylate is added and mixing continues for 5 minutes. Then organic peroxide Luperox F-40 and peroxide vulcanization accelerator TAIC are added to the composition during mixing on rollers, mixing continues for 7 minutes. Upon completion of mixing, the mixture is removed from the rollers and aged for 24 hours.

Vulcanization of products and reference materials for testing is carried out in a hydraulic press at a temperature of 160 ° C for 30 minutes.

The obtained vulcanizates are thermostated at a temperature of 150 ° C for 6 hours. The specific ratios of the components are presented in Table 2. The test results of standard samples are presented in Table 3.

Examples 2-4 are performed in the same sequence and the only difference is in the compositions and concentrates of the substances. The composition and concentration of the compositions according to the examples are presented in table 2.

Example 5. In a closed type mixer, in this case a Banbury type mixer, a mixture is prepared in the following sequence. At a temperature of 140 ° C, hydrogenated nitrile butadiene rubber Zeptol 2000L is loaded into the mixer and mixing is carried out at a rotary speed of 35-40 rpm for 10 minutes. Then the filler is added to the mixer - carbon black grade P-514 and mixing is continued for 5 minutes, and then the plasticizer dibutyl sebacate is added and mixing continues for 5 minutes. Then the polyvalent metal salt of acrylic and methacrylic acid is added to the mixer and mixing is continued for 10 minutes. Next, zinc oxide is sequentially loaded into the mixer and after 3 minutes stearic acid and mixing continues for 7 minutes while the temperature drops to 100-110 ° C. Next, the zinc salt of methylmercaptobenzimidazole is added to the mixture, after 3 minutes of mixing, 4,4'-bis (alpha-, alpha-demethylbenzyl) definylamine is added, and after another 3 minutes, trimethylolpropane trimethacrylate is added and mixing continues for 5 minutes. Next, organic peroxide Luperox F-40 and peroxide vulcanization accelerator TAIC are added to the composition and mixing is continued for 7 minutes. Upon completion of mixing, the mixture is unloaded and rolled, aged for 24 hours. Next, the resulting composition is vulcanized in the form of standard test pieces, as well as control samples with metal reinforcement in a hydraulic press at a temperature of 160 ° C for 30 minutes. Then the obtained samples are thermostated in a thermostat at a temperature of 150 ° C for 6 hours. Specific ratios of components are presented in table 2. The obtained samples were subjected to tests, the results of which are presented in table 3. Example 6 is performed in the same sequence as example 5, the difference lies only in the composition and concentration of substances. The composition and concentration of the compositions according to the examples are presented in table 2. The properties of the compositions are presented in table 3.

Example 7. On laboratory rollers (320) prepare the mixture in the following sequence. At a roll temperature of 80-90 ° C, the hydrogenated nitrile-butadiene rubber Zeptol 2000L is dispersed and mixed for 7 minutes, then a filler - carbon black grade P-514 is added and mixing is continued for 10 minutes. Next, the plasticizer dibutyl sebacate is added and mixing is continued for 5 minutes. Then add the salt of polyvalent metals acrylic and methacrylic acid and the mixing is continued for 7 minutes. Next, the zinc salt of methylmercaptobenzimidazole is added to the mixture, after 3 minutes of mixing, 4,4'-bis (alpha-, alpha-demethylbenzyl) definylamine is added and after 3 minutes, trimethylolpropane trimethacrylate, and mixing is continued for 5 minutes. The mixture is sheared off the rollers and cooled for 6 hours. Next, the rubber mixture is heated on rollers at temperatures of 70-80 ° C and organic peroxide Luperox F-40 and an accelerator of peroxide vulcanization TAIC are added to the composition and mixing continues for 7 minutes. Upon completion of mixing, the mixture is unloaded and rolled, aged for 24 hours. Next, the resulting composition is vulcanized in the form of standard test pieces, as well as control samples with metal reinforcement in a hydraulic press at a temperature of 160 ° C for 30 minutes. Then the obtained samples are thermostated in a thermostat at a temperature of 150 ° C for 6 hours. The specific ratios of the components are presented in table 2. The obtained samples were subjected to tests, the results of which are presented in table 3.

Example 8 In a closed type mixer, in this case a Banbury type mixer, a mixture is prepared in the following sequence. At a temperature of 140 ° C, hydrogenated nitrile butadiene rubber Zeptol 2000L is loaded into the mixer and mixing is carried out at a rotary speed of 35-40 rpm for 10 minutes. Then the filler is added to the mixer - carbon black grade P-514 and mixing is continued for 5 minutes, and then the plasticizer dibutyl sebacate is added and mixing is continued for 5 minutes. Then zinc methacrylic acid is added to the mixer and mixing is continued for 10 minutes. Next, zinc oxide is sequentially loaded into the mixer and after 3 minutes stearic acid and mixing continues for 7 minutes while the temperature drops to 100-110 ° C. Next, the zinc salt of methylmercaptobenzimidazole is added to the mixture, after 3 minutes of mixing, 4,4'-bis (alpha-, alpha-demethylbenzyl) definylamine is added, and after another 3 minutes, trimethylolpropane trimethacrylate is added and mixing continues for 5 minutes. Next, organic peroxide Luperox F-40 and peroxide vulcanization accelerator TAIC are added to the composition and mixing is continued for 7 minutes. Upon completion of mixing, the mixture is unloaded and rolled, aged for 24 hours. Next, the resulting composition is vulcanized in the form of standard test pieces, as well as control samples with metal reinforcement in a hydraulic press at a temperature of 160 ° C for 30 minutes. Then the obtained samples are thermostated in a thermostat at a temperature of 150 ° C for 6 hours. The specific ratios of the components are presented in table 2. The obtained samples were subjected to tests, the results of which are presented in table 3.

Example 9 is performed in the same sequence as example 5, the difference lies only in the composition and concentrations of substances. The composition and concentration of the compositions according to the examples are presented in table 2. The properties of the compositions are presented in table 3.

In terms of mechanical characteristics and service life, the compositions obtained according to the proposed invention are superior to the closest analogue, the implementation of which is presented in the prior art section.

Claims (55)

1. Elastomeric composition based on hydrogenated nitrile butadiene rubber with acrylonitrile content in an amount of 18 to 52 wt.%, Intended for the manufacture of seals, containing organic peroxide and peroxide vulcanization accelerator as vulcanizing agents, filler, antioxidant, antioxidant, plasticizing additives, contains in parts by weight: hydrogenated nitrile butadiene rubber 100.0; polyvalent metal salt of acrylic, or methacrylic, or acrylic and methacrylic acids 45.0-85.0; organic peroxide 8.0-12.0; peroxide vulcanization accelerator 10.0-14.0; zinc oxide 5.0 as an antioxidant and / or antioxidant; zinc salt of methyl mercaptobenzimidazole 1.0-2.0; 4,4'-bis (alpha-, alpha-dimethylbenzyl) diphenylamine 1.5-2.5; trimethylolpropane trimethacrylate 1.0-2.5 stearic acid 1.0-15.0 as an antioxidant and / or antioxidant; filler 50.0-70.0; plasticizer 5.0-15.0; characterized in that the polyvalent metal salt of acrylic, or methacrylic, or acrylic and methacrylic acids is a reaction product oxide or hydroxide of a polyvalent metal, introduced in an amount of 35.0-40.0 parts by weight, and acrylic, or methacrylic, or acrylic and methacrylic acids, introduced in the amount of 15.0-55.0 wt.h. 2. Elastomeric composition according to claim 1, characterized in that the organic peroxide is selected from the group consisting of: 2,5-di (tert-butylperoxy) -2,5-dimethylhexane; tert-butylcumyl peroxide; 1,3 and 1,4-di (tert-butylperoxyisopropyl) benzene; dicumyl peroxide; n-butyl 4,4-di (tert-butylperoxy) valerate; 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane. 3. Elastomeric composition according to claim 1, characterized in that the peroxide vulcanization accelerator is selected from the group consisting of triallyl isocyanurate or trimethylolpropane trimethacrylate. 4. The elastomeric composition of claim 1, wherein the filler is inactive carbon black. 5. Elastomeric composition according to claim 1, characterized in that the plasticizing additive is selected from the group consisting of plasticizers based on phthalic acid esters or sebacic acid. 6. A method of obtaining an elastomeric composition based on hydrogenated nitrile butadiene rubber, in which the elastomeric composition is prepared by mixing in two stages, moreover, at the first stage, a mixture of components is prepared, parts by weight: hydrogenated nitrile butadiene rubber 100.0; polyvalent metal salt of acrylic, or methacrylic, or acrylic and methacrylic acids 45.0-85.0; zinc oxide 5.0 as an antioxidant and / or antioxidant; stearic acid 1.0-15.0 as an antioxidant and / or antioxidant; filler 50.0-70.0; plasticizer 5.0-15.0; in closed type mixers at a temperature of 120-140 ° C with sequential injection of components with a total mixing time in the first stage of 40 ± 5 minutes; in the second stage introduce the following components: zinc salt of methyl mercaptobenzimidazole 1.0-2.0; 4,4'-bis (alpha-, alpha-dimethylbenzyl) diphenylamine 1.5-2.5; trimethylolpropane trimethacrylate 1.0-2.5; organic peroxide 8.0-12.0; peroxide vulcanization accelerator 10.0-14.0; in closed type mixers or on rollers with sequential injection of components; or in the first stage, a mixture of all components is prepared, with the exception of the introduction of organic peroxide, followed by curing the mixture for 4 hours, at the second stage, the introduction of organic peroxide on the rollers is carried out, wherein the polyvalent metal salt of acrylic, or methacrylic, or acrylic and methacrylic acids is a reaction product oxide or hydroxide of a polyvalent metal, introduced in an amount of 35.0-40.0 parts by weight, and acrylic, or methacrylic, or acrylic and methacrylic acids, introduced in the amount of 15.0-55.0 wt.h. 7. A method for producing an elastomeric composition according to claim 6, in which in the first stage the preparation of a modifier is carried out, a salt of a polyvalent metal of acrylic or methacrylic acid is carried out in the process of obtaining a composition by the reaction between an oxide or hydroxide of a polyvalent metal with acrylic or methacrylic acid, in the following ratios of components , wt.h .: hydrogenated nitrile butadiene rubber 100.0; oxide or hydroxide of a polyvalent metal 35.0-40.0; acrylic or methacrylic acid 15.0-55.0; the salt formation reaction takes place during the preparation of the composition or vulcanization at a temperature from 120 ° C to 140 ° C with a process duration of at least 10 minutes. 8. A method of obtaining an elastomeric composition according to claim 6, characterized in that when performing the second stage on the rollers, the temperature of the rolls is 60-80 ° C with a total mixing time of 40 ± 5 minutes; a when performing the second stage in the mixer, the temperature of the rolls is 60-80 ° C with a total mixing time of 20 ± 5 minutes.