Hydrogenated nitrile rubber and compositions thereof, vulcanizates

Abstract

The application relates to the field of butadiene-acrylonitrile rubber, and discloses a hydrogenated butadiene-acrylonitrile rubber, a composition of the hydrogenated butadiene-acrylonitrile rubber and vulcanized rubber. The hydrogenated butadiene-acrylonitrile rubber contains a compound of formula I, a compound of formula II and a ruthenium metal-containing compound; (L o M) p Y q The content of the compound of formula I is less than or equal to 2 wt% based on the weight of the hydrogenated butadiene-acrylonitrile rubber; the content of the compound of formula II is less than or equal to 1 wt% based on the weight of the hydrogenated butadiene-acrylonitrile rubber; and the content of the ruthenium metal is 0.0001-1 wt% based on the weight of the hydrogenated butadiene-acrylonitrile rubber. The hydrogenated butadiene-acrylonitrile rubber can make the vulcanized rubber prepared from the hydrogenated butadiene-acrylonitrile rubber obtain better mechanical properties and meanwhile maintain good aging resistance in the case that the metal catalyst and the phosphine ligand are not removed or are incompletely removed, that is, in the case that a certain amount of the metal catalyst and the phosphine ligand, especially a certain amount of the ruthenium metal-containing compound and the phosphine ligand, are contained.

Description

Technical Field

[0001] This invention relates to the field of nitrile rubber, specifically to a hydrogenated nitrile rubber and its composition, and a vulcanized rubber. Background Technology

[0002] Hydrogenated nitrile butadiene rubber (HNBR) is a highly saturated nitrile butadiene rubber with excellent oil resistance, abrasion resistance, and low-temperature resistance. Its vulcanizate also shows excellent tolerance to high and low temperatures and oil, and is widely used in petroleum, aerospace, automotive and other fields.

[0003] Hydrogenated nitrile butadiene rubber (NBR) is mainly obtained by selectively hydrogenating the carbon-carbon double bonds in NBR. Commonly used hydrogenation catalysts include rhodium, ruthenium, and palladium. Besides the use of precious metal catalysts, phosphine-containing ligands such as PPh3 are often required as co-catalysts to improve catalyst stability and reactivity. However, the use of phosphine ligands such as PPh3 can also affect the hardness and compression set of hydrogenated NBR.

[0004] Researchers have long sought methods to avoid the negative impact of phosphine-containing ligands such as PPh3 on the performance of hydrogenated nitrile butadiene rubber (NBR) products. CN105873957A discloses a hydrogenated NBR containing phosphine oxide or diphosphine oxide. This patent improves the modulus and compression set of the hydrogenated NBR by converting triphenylphosphine in the product to triphenylphosphine oxide. CN105873956A discloses a hydrogenated NBR containing phosphine sulfide and / or diphosphine sulfide. This patent improves the modulus of the hydrogenated NBR under different tensile stresses and the compression set after high-temperature storage by converting triphenylphosphine in the product to triphenylphosphine sulfide. Summary of the Invention

[0005] The purpose of this invention is to provide a hydrogenated nitrile butadiene rubber and its composition, as well as a vulcanized rubber. This hydrogenated nitrile butadiene rubber can still produce vulcanized rubber with better mechanical properties and good aging resistance even when the metal catalyst and phosphine ligand are not removed or are not completely removed, i.e., when it contains a certain amount of metal catalyst and phosphine ligand, especially a certain amount of ruthenium-containing metal compound and phosphine ligand.

[0006] To achieve the above objectives, the first aspect of the present invention provides a hydrogenated nitrile butadiene rubber, characterized in that the hydrogenated nitrile butadiene rubber contains a compound represented by Formula I, a compound represented by Formula II, and a ruthenium-containing metal compound;

[0007] Formula I,

[0008] In Formula I, R1, R2, and R3 are each independently selected from C1-C8 alkyl groups, C4-C8 cycloalkyl groups, and C6-C8 alkyl groups. 15 aryl or C7-C 15 Aryl groups;

[0009] (L o M) p Y q Formula II,

[0010] In Formula II, the o Ls may be the same or different, and each is independently a C1-C8 alkyl, C4-C8 cycloalkyl, or C6-C 15 aryl or C7-C 15 Aryl groups,

[0011] M is phosphorus or arsenic.

[0012] Each of the q Y atoms may be the same or different, and each is an anion independently.

[0013] o is 3, 4, 5 or 6, p is 1, 2 or 3, and q is 1, 2 or 3;

[0014] Based on the weight of hydrogenated nitrile butadiene rubber, the content of the compound shown in Formula I is less than or equal to 2 wt%;

[0015] Based on the weight of hydrogenated nitrile butadiene rubber, the content of the compound shown in Formula II is less than or equal to 1 wt%;

[0016] Based on the weight of hydrogenated nitrile butadiene rubber, the ruthenium content is 0.0001 wt%-1 wt%.

[0017] A second aspect of the present invention provides a method for preparing the above-mentioned hydrogenated nitrile butadiene rubber, characterized in that the preparation method includes:

[0018] The hydrogenated nitrile butadiene rubber is obtained by adding the compound shown in Formula I, the compound shown in Formula II, optionally a ruthenium-containing metal compound, optionally phosphine, and optionally phosphine oxide to the hydrogenated nitrile butadiene rubber solution, followed by stirring, coagulation, and drying.

[0019] The hydrogenated nitrile butadiene rubber is obtained by adding the compound shown in Formula I, the compound shown in Formula II, optionally a ruthenium metal compound, optionally phosphine, and optionally phosphine oxide to hydrogenated nitrile butadiene rubber and then mixing them.

[0020] A third aspect of the present invention provides a hydrogenated nitrile butadiene rubber composition, characterized in that the hydrogenated nitrile butadiene rubber composition comprises the above-mentioned hydrogenated nitrile butadiene rubber.

[0021] A fourth aspect of the present invention provides a vulcanized rubber, characterized in that the vulcanized rubber is obtained by mixing and vulcanizing the above-mentioned hydrogenated nitrile rubber composition.

[0022] Through the above technical solutions, the hydrogenated nitrile butadiene rubber and its composition, as well as the vulcanized rubber provided by the present invention, achieve the following beneficial effects:

[0023] The hydrogenated nitrile butadiene rubber and its composition, as well as the vulcanized rubber provided by the present invention, can still achieve better mechanical properties and maintain good aging resistance even when the hydrogenation catalyst and phosphine ligand are not removed or are not completely removed, i.e., when a certain amount of metal catalyst and phosphine ligand, especially a certain amount of ruthenium metal compound and phosphine ligand, are contained. Detailed Implementation

[0024] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0025] In this invention, the C1-C8 alkyl groups include straight-chain alkyl groups of C1-C8 and branched alkyl groups of C3-C8. Specific examples may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-methylhexyl, 2,4-methylhexyl, 2,4-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-methylhexyl, 2,4-methylhexyl, 2,3-dimethylpentyl, 2,4-methylhexyl, 2,3 ... -Dimethylpentyl, 3,3-dimethylpentyl, 3,4-dimethylpentyl, 4,4-dimethylpentyl, 2-ethylpentyl, 3-ethylpentyl, n-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2,2-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 3,3-dimethylhexyl, 3,4-dimethylhexyl, 3,5-dimethylhexyl, 4,4-dimethylhexyl, 4,5-dimethylhexyl, 5,5-dimethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-n-propylpentyl, and 2-isopropylpentyl.

[0026] In this invention, specific examples of C4-C8 cycloalkyl groups may include, but are not limited to: cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, and 4-n-butylcyclohexyl.

[0027] In this invention, C6-C 15 Specific examples of aryl groups may include, but are not limited to: phenyl, naphthyl, 2-methylphenyl, 2-ethylphenyl, 4-methylphenyl, and 4-ethylphenyl.

[0028] In this invention, the term "aryl group" can be represented as Ar. x -T-, where x Ar atoms are the same or different, each independently being an aryl group, T is an alkyl group, and x is an integer from 1 to 3. In this invention, C7-C 15 Specific examples of aralkyl groups may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-tert-butyl, phenylisopropyl, phenyl-n-pentyl, and phenyl-n-butyl.

[0029] The first aspect of the present invention provides a hydrogenated nitrile butadiene rubber, characterized in that the hydrogenated nitrile butadiene rubber contains a compound represented by Formula I, a compound represented by Formula II, and a ruthenium-containing metal compound;

[0030] Formula I,

[0031] In Formula I, R1, R2, and R3 are each independently selected from C1-C8 alkyl groups, C4-C8 cycloalkyl groups, and C6-C8 alkyl groups. 15 aryl or C7-C 15 Aryl groups;

[0032] (L o M) p Y q Formula II,

[0033] In Formula II, the o Ls may be the same or different, and each is independently a C1-C8 alkyl, C4-C8 cycloalkyl, or C6-C 15 aryl or C7-C 15 Aryl groups,

[0034] M is phosphorus or arsenic.

[0035] Each of the q Y atoms may be the same or different, and each is an anion independently.

[0036] o is 3, 4, 5 or 6, p is 1, 2 or 3, and q is 1, 2 or 3;

[0037] Based on the weight of hydrogenated nitrile butadiene rubber, the content of the compound shown in Formula I is less than or equal to 2 wt%;

[0038] Based on the weight of hydrogenated nitrile butadiene rubber, the content of the compound shown in Formula II is less than or equal to 1 wt%;

[0039] Based on the weight of hydrogenated nitrile rubber, the ruthenium content is 0.0001wt%-1wt%.

[0040] In this invention, the hydrogenated nitrile butadiene rubber is a product of the hydrogenation reaction of nitrile butadiene rubber. Moreover, even when the metal catalyst and phosphine ligand are not removed or are not completely removed, that is, when the hydrogenated nitrile butadiene rubber contains the above-mentioned specific amounts of ruthenium-containing metal compounds and phosphine ligands, the vulcanized rubber made from the hydrogenated nitrile butadiene rubber can still obtain better mechanical properties while maintaining good aging resistance.

[0041] Furthermore, in Equation I, R1, R2, and R3 are each independently selected from C6-C 15 aryl or C7-C 15 Aryl groups.

[0042] In one specific embodiment of the present invention, the compound represented by Formula I is triphenylphosphine (R1, R2, and R3 are phenyl) and / or o-methyltriphenylphosphine (R1, R2, and R3 are phenyl) (Methylphenyl)).

[0043] Furthermore, based on the weight of hydrogenated nitrile butadiene rubber, the content of the compound shown in Formula I is less than or equal to 1 wt%.

[0044] Furthermore, based on the weight of hydrogenated nitrile butadiene rubber, the content of the compound shown in Formula I is 0.0001wt%-0.8wt%.

[0045] Furthermore, in Equation II, each of the o L's is either the same or different, and each is independently C6-C. 15 The aryl group. Furthermore, in Formula II, all o L are phenyl groups.

[0046] Furthermore, in Formula II, M represents phosphorus.

[0047] Furthermore, in Formula II, Y is a halide ion. Even further, in Formula II, Y is a chloride ion or a bromide ion. Even further, in Formula II, Y is a chloride ion.

[0048] In one specific embodiment of the present invention, the compound of formula II is (PPh4)Cl and / or (PPh4)Br.

[0049] Furthermore, based on the weight of hydrogenated nitrile butadiene rubber, the content of the compound shown in Formula II is less than or equal to 0.9 wt%.

[0050] Furthermore, based on the weight of hydrogenated nitrile butadiene rubber, the content of the compound shown in Formula II is 0.0001-0.8 wt%.

[0051] Furthermore, based on the weight of hydrogenated nitrile rubber, the ruthenium content is 0.0001 wt%-0.8 wt%.

[0052] Furthermore, based on the weight of hydrogenated nitrile rubber, the ruthenium content is 0.0001 wt%-0.5 wt%.

[0053] Furthermore, the ruthenium-containing metal compound is a ruthenium metal compound and / or a rhodium-ruthenium metal compound.

[0054] In one specific embodiment of the present invention, when the ruthenium-containing metal compound includes a rhodium-ruthenium compound, based on the weight of the hydrogenated nitrile rubber, the content of ruthenium is 0.0001 wt%-1 wt%, preferably 0.0001 wt%-0.5 wt%, more preferably 0.0001 wt%-0.1 wt%; the content of rhodium is 0.0001 wt%-1 wt%, preferably 0.0001 wt%-0.5 wt%, more preferably 0.0001 wt%-0.1 wt%.

[0055] According to the present invention, the ruthenium compound is a compound represented by Formula III and / or a ruthenium-containing olefin metathesis catalyst;

[0056] (R 2 j A 2 ) m RuX 2 n Formula III,

[0057] Among them, j R 2 Same or different, R 2 Each is independently selected from C1-C8 alkyl groups, C4-C8 cycloalkyl groups, and C6-C6 alkyl groups. 15 aryl or C7-C 15 Aryl group; A 2 Selected from phosphorus, arsenic, sulfur, or sulfoxide groups S=O; X 2 Selected from hydrogen or anions; m is 2, 3 or 4; j is 2 or 3; n is 1, 2 or 3.

[0058] Furthermore, in Equation III, j R 2 Whether they are the same or different, each is independently C6-C. 15 The aryl group. More preferably, in formula I, j R groups 2 All are phenyl.

[0059] Furthermore, in Equation III, A 2 It is phosphorus, arsenic, sulfur, or sulfoxide. More preferably, in formula III, A 2 It is phosphorus.

[0060] Furthermore, in Equation III, n X 2 Whether the two are the same or different, each is independently a hydrogen or anion. More preferably, in Formula III, X2 It is an anion. More preferably, in formula III, X... 2 It is a halide ion. More preferably, in formula III, X 2 It is a chloride ion or a bromide ion. Particularly preferably, in formula III, X... 2 It is a chloride ion.

[0061] Furthermore, in Equation III, m is 2, 3, or 4. In Equation III, j is 2 or 3. In Equation III, n is 1, 2, or 3.

[0062] In one specific embodiment of the present invention, the ruthenium compound is at least one of (PPh3)3RuCl2, Grubbs I, and Grubbs II.

[0063] According to the present invention, the rhodium-ruthenium compound is a compound represented by Formula IV:

[0064] M 1 a M 2 b Z c N d Formula IV

[0065] Among them, M 1 Rhodium, M 2 For ruthenium,

[0066] The d Ns may be the same or different, and each N is independently an organophosphorus, organocerium, nitrogen-containing organic compound, sulfur-containing organic compound or oxygen-containing organic compound. Preferably, N is an organophosphorus monophosphorus; more preferably, N is triphenylphosphorus.

[0067] c Z may be the same or different, and each can independently be chlorine, bromine, or hydrogen.

[0068] 1≤a≤6, 1≤b≤3, 3≤c≤7, 6≤d≤21.

[0069] Furthermore, in Formula IV, the c Zs are the same or different, and each is independently chlorine or bromine.

[0070] Furthermore, in equation IV, 1≤a≤4, 1≤b≤2, 3≤c≤6, and 6≤d≤15.

[0071] In one specific embodiment of the present invention, in IV, a:b:c:d=2:1:4:9, or a:b:c:d=3:1:5:12, or a:b:c:d=1:1:3:6.

[0072] According to the present invention, the hydrogenated nitrile rubber further comprises phosphine and / or phosphine oxide.

[0073] Furthermore, based on the hydrogenated nitrile rubber, the content of phosphine is 0.001wt%-10wt%, and the content of phosphine oxide is 0.001wt%-10wt%.

[0074] Furthermore, based on the hydrogenated nitrile rubber, the content of phosphine is 0.05wt%-5wt%, and the content of phosphine oxide is 0.02wt%-5wt%.

[0075] More preferably, based on the hydrogenated nitrile rubber, the content of phosphine is 0.1 wt%-3 wt%, and the content of phosphine oxide is 0.02 wt%-3 wt%.

[0076] In this invention, there is no particular limitation on the type of phosphine. Generally, it is a phosphine ligand used in the hydrogenation of nitrile rubber in the art. Preferably, the phosphine is selected from organic monophosphine and / or organic bisphosphine.

[0077] Furthermore, in this invention, the phosphine is a compound represented by formula V and / or a compound represented by formula VI:

[0078] Formula V Formula VI;

[0079] Among them, L1-L7 are each independently selected from C1-C8 alkyl groups, C4-C8 cycloalkyl groups, and C6-C6 alkyl groups. 15 aryl or C7-C 15 The aralkyl group, where Y is selected from alkyl, alkenyl or ynyl groups.

[0080] Furthermore, L1-L7 are each independently selected from C6-C 15 aryl or C7-C 15 aryl alkyl group, where Y is an alkyl group.

[0081] Further, the phosphine is selected from triphenylphosphine (in formula V, L1-L3 are phenyl) and o-methyltriphenylphosphine (in formula V, L1-L3 are phenyl)... At least one of 1,3-bis(diphenylphosphine)propane (in Formula VI, L1-L4 are phenyl and Y is propane) and 1,4-bis(diphenylphosphine)butane (in Formula VI, L1-L4 are phenyl and Y is butane).

[0082] In a preferred embodiment of the present invention, the phosphine is triphenylphosphine.

[0083] In this invention, the type of phosphine oxide is not particularly limited. Generally, it is the phosphine oxide generated by oxidizing phosphine ligands used in the hydrogenation of nitrile rubber in the art. Preferably, the phosphine oxide is selected from organic monooxyphosphine and / or organic dioxyphosphine. More preferably, the phosphine oxide is a compound represented by formula VII and / or a compound represented by formula VIII.

[0084] Equation VII Formula VIII;

[0085] Among them, M1-M7 are each independently selected from C1-C8 alkyl groups, C4-C8 cycloalkyl groups, and C6-C6 alkyl groups. 15 aryl or C7-C 15 The aralkyl group, where Y is selected from alkyl, alkenyl or ynyl groups.

[0086] Furthermore, M1-M7 are each independently selected from C6-C 15 aryl or C7-C 15 aryl alkyl group, where Y is an alkyl group.

[0087] Further, the phosphine oxide is selected from triphenylphosphine oxide (in formula VII, M1-M3 are phenyl) and o-methyltriphenylphosphine oxide (in formula VII, M1-M3 are phenyl). At least one of 1,3-bis(diphenylphosphine oxide)propane (in Formula VIII, M1-M4 are phenyl and Y is propane) and 1,4-bis(diphenylphosphine oxide)butane (in Formula VIII, M1-M4 are phenyl and Y is butane).

[0088] In a preferred embodiment of the present invention, the phosphine oxide is triphenylphosphine oxide.

[0089] In this invention, there is no particular limitation on the type of hydrogenated nitrile rubber. It can be hydrogenated nitrile rubber prepared by hydrogenating various nitrile rubbers containing carbon-carbon double bonds (C=C) and cyano groups (CN). Preferably, the hydrogenated nitrile rubber is obtained by hydrogenating binary nitrile rubber and / or ternary nitrile rubber.

[0090] In this invention, the binary nitrile rubber is selected from at least one of butadiene-acrylonitrile rubber, butadiene-(methyl)acrylonitrile rubber, 2-methyl-1,3-butadiene-acrylonitrile rubber and 2-methyl-1,3-butadiene-(methyl)acrylonitrile rubber.

[0091] In this invention, the ternary nitrile rubber is selected from butadiene-acrylonitrile-acrylic rubber, butadiene-acrylonitrile-methyl acrylate rubber, butadiene-acrylonitrile-ethyl acrylate rubber, butadiene-acrylonitrile-tert-butyl acrylate rubber, butadiene-acrylonitrile-butyl acrylate rubber, butadiene-acrylonitrile-(meth)acrylate rubber, butadiene-acrylonitrile-(meth)acrylate-methyl acrylate rubber, butadiene-acrylonitrile-(meth)acrylate-ethyl acrylate rubber, butadiene-acrylonitrile-(meth)acrylate-tert-butyl acrylate rubber, butadiene-acrylonitrile-(meth)acrylate-butyl acrylate rubber, and butadiene-(meth)acrylonitrile-acrylic rubber. The rubber, butadiene-(meth)acrylonitrile-methyl acrylate rubber, butadiene-(meth)acrylonitrile-ethyl acrylate rubber, butadiene-(meth)acrylonitrile-tert-butyl acrylate rubber, butadiene-(meth)acrylonitrile-butyl acrylate rubber, butadiene-(meth)acrylonitrile-(meth)acrylate rubber, butadiene-(meth)acrylonitrile-(meth)acrylate-methyl acrylate rubber, butadiene-(meth)acrylonitrile-(meth)acrylate-ethyl acrylate rubber, butadiene-(meth)acrylonitrile-(meth)acrylate-tert-butyl acrylate rubber, and butadiene-(meth)acrylonitrile-(meth)acrylate-butyl acrylate rubber.

[0092] In this invention, there is no particular limitation on the degree of hydrogenation of the hydrogenated nitrile butadiene rubber, for example, the degree of hydrogenation of the hydrogenated nitrile butadiene rubber is 80-100%.

[0093] In this invention, the hydrogenated nitrile butadiene rubber contains hydrogenation catalyst and phosphine ligand that were not removed or were not completely removed during the preparation process. Specifically, based on the weight of the hydrogenated nitrile butadiene rubber, the content of residual hydrogenation catalyst is less than or equal to 0.5 wt%, and the content of residual phosphine ligand is less than or equal to 5 wt%.

[0094] In one specific embodiment of the present invention, the hydrogenation catalyst has M 1 a M 2 b Z c N d The structure shown.

[0095] In this invention, the compounds represented by Formula I, Formula II, ruthenium metal, optional phosphine, and optional phosphine oxide contained in the hydrogenated nitrile butadiene rubber can be derived from hydrogenation catalysts and phosphine ligands that have not been removed or have not been completely removed during the preparation of the hydrogenated nitrile butadiene rubber, or they can be added additionally, as long as the content of the compounds represented by Formula I, Formula II, ruthenium metal, optional phosphine, and optional phosphine oxide in the hydrogenated nitrile butadiene rubber meets the requirements of this invention.

[0096] A second aspect of the present invention provides a method for preparing the above-mentioned hydrogenated nitrile butadiene rubber, comprising:

[0097] The hydrogenated nitrile butadiene rubber is obtained by adding the compound shown in Formula I, the compound shown in Formula II, optionally a ruthenium-containing metal compound, optionally phosphine, and optionally phosphine oxide to the hydrogenated nitrile butadiene rubber solution, followed by stirring, coagulation, and drying.

[0098] The hydrogenated nitrile butadiene rubber is obtained by adding the compound shown in Formula I, the compound shown in Formula II, optionally a ruthenium metal compound, optionally phosphine, and optionally phosphine oxide to hydrogenated nitrile butadiene rubber and then mixing them.

[0099] In this invention, there are no particular limitations on the amount of compounds represented by Formula I, compounds represented by Formula II, ruthenium-containing metal compounds, phosphine, and phosphine oxide added, as long as the content of compounds represented by Formula I, compounds represented by Formula II, ruthenium metal, rhodium metal, phosphine, and phosphine oxide in the prepared hydrogenated nitrile rubber meets the requirements of this invention.

[0100] In this invention, there are no special requirements for the stirring conditions, as long as the hydrogenated nitrile rubber solution is fully and evenly mixed with the compound shown in Formula I, the compound shown in Formula II, the ruthenium-containing metal compound, the phosphine, and the phosphine oxide, for example, stirring at 10-10000 rpm for 1-60 min.

[0101] In this invention, there is no particular limitation on the method of coagulation. Gel formation can be carried out in a conventional manner in the art, such as adding ethanol to the stirred product.

[0102] In this invention, there are no particular limitations on the drying conditions and methods, as long as the hydrogenated nitrile rubber can be fully dried, for example, drying at 50-80°C for 0.5-6 hours under vacuum conditions.

[0103] In this invention, there are no particular limitations on the equipment used for mixing; conventional mixing equipment in the art, such as open mills and / or internal mixers, can be used. There are also no particular limitations on the mixing conditions, as long as the hydrogenated nitrile rubber is thoroughly and uniformly mixed with the compound shown in Formula I, the compound shown in Formula II, the ruthenium-containing metal compound, optionally phosphine, and optionally phosphine oxide, for example, mixing at 25-200°C for 2-300 minutes.

[0104] In this invention, the hydrogenated nitrile butadiene rubber solution or the hydrogenated nitrile butadiene rubber is a product of the hydrogenation reaction of nitrile butadiene rubber.

[0105] In one embodiment of the present invention, based on the weight of hydrogenated nitrile butadiene rubber, the content of the compound shown in Formula I is less than or equal to 2 wt%, the content of the compound shown in Formula II is less than or equal to 1 wt%, the content of ruthenium metal is 0.0001-1 wt%, the content of rhodium metal is 0.0001 wt%-1 wt%, the content of phosphine is 0.001 wt%-10 wt%, and the content of phosphine oxide is 0.001 wt%-10 wt%.

[0106] In a preferred embodiment of the present invention, based on the weight of hydrogenated nitrile rubber, the content of the compound represented by Formula I is less than or equal to 1 wt%, the content of the compound represented by Formula II is less than or equal to 0.9 wt%, the content of ruthenium metal is 0.0001 wt%-0.8 wt%, the content of rhodium metal is 0.0001-0.8 wt%, the content of phosphine is 0.05 wt%-5 wt%, and the content of phosphine oxide is 0.02 wt%-5 wt%.

[0107] In a preferred embodiment of the present invention, based on the weight of hydrogenated nitrile rubber, the content of the compound represented by Formula I is 0.0001wt%-0.8wt%, the content of the compound represented by Formula II is 0.0001wt%-0.8wt%, the content of metallic ruthenium is 0.0001wt%-0.5wt%, the content of metallic rhodium is 0.0001wt%-0.5wt%, the content of phosphine is 0.1wt%-3wt%, and the content of phosphine oxide is 0.02wt%-3wt%.

[0108] A third aspect of the present invention provides a hydrogenated nitrile butadiene rubber composition, characterized in that the hydrogenated nitrile butadiene rubber composition comprises the above-mentioned hydrogenated nitrile butadiene rubber.

[0109] In this invention, the hydrogenated nitrile rubber composition also includes other commonly used additives in the art, such as fillers, plasticizers, activators, coupling agents, antioxidants, dispersants, vulcanizing agents, crosslinking agents, and accelerators. The dosage of each additive can be added according to the conventional dosage in the art.

[0110] A fourth aspect of the present invention provides a vulcanized rubber, characterized in that the vulcanized rubber is obtained by mixing and vulcanizing the above-mentioned hydrogenated nitrile rubber composition.

[0111] In this invention, there is no particular limitation on the mixing method, as long as the components in the hydrogenated nitrile rubber composition are fully and uniformly mixed.

[0112] The present invention will be described in detail below through embodiments. In the following embodiments,

[0113] The contents of the compounds represented by Formula I, phosphine, and phosphine oxide in hydrogenated nitrile butadiene rubber were determined by liquid chromatography (UPLC-iclass, Waters Corporation, USA).

[0114] The contents of ruthenium and rhodium in hydrogenated nitrile rubber were determined by inductively coupled plasma atomic emission spectrometry (Optima 8300, PE Corporation, USA).

[0115] Hardness: Shore A hardness was determined using a Shore hardness tester (HT 3000, Montech GmbH, Germany) according to GB / T 531.1-2008.

[0116] Tensile properties and tear strength: The tensile test was conducted using a material testing machine according to GB / T 528-2009 and GB / T 529-2008 respectively. The tensile rate was 500 mm / min, the test temperature was (23±2)℃, the specimen length was 25 mm, and the width was 6 mm. For each group of specimens, 10 parallel tests were conducted, and the median value of the results was taken.

[0117] Compression set: The compression set of vulcanized rubber was tested according to GB / T 7759.1-2015. The test used the type A specimen recommended in the standard, and the test conditions were 150℃×70h.

[0118] All raw materials used in the examples and comparative examples are commercially available products.

[0119] Preparation Example P1

[0120] This preparation example is used to illustrate the hydrogenation catalyst M. 1 a M 2 b Z c N d The preparation method of (P1), wherein M 1 Rhodium, M 2 For ruthenium, Z is chlorine, N is triphenylphosphine, a:b is 2:1, c is 4, and d is 9.

[0121] 4.5 g of PPh3 was dissolved in a 70°C hot ethanol solution under argon protection, and the dissolved solution was added to a reaction flask and heated to reflux. 0.5 g of RhCl3·H2O and 0.23 g of RuCl3·H2O were weighed and dissolved in an ethanol solution under argon protection, and the ethanol solutions of RhCl3·H2O and RuCl3·H2O were added dropwise to the reaction flask. The reaction was kept under reflux for 2.5 hours, then cooled to 25°C. The reaction mixture was filtered, and the resulting solid was washed with diethyl ether to obtain a powdered hydrogenation catalyst in which Rh:Ru = 2:1 (molar ratio).

[0122] Preparation Example P2

[0123] This preparation example is used to illustrate the hydrogenation catalyst M. 1 a M 2 b Z c N d The preparation method of (P2), wherein M 1 Rhodium, M 2 For ruthenium, Z is chlorine, N is triphenylphosphine, a:b is 3:1, c is 5, and d is 12.

[0124] 6 g of PPh3 was dissolved in a 70°C hot ethanol solution under argon protection, and the dissolved solution was added to a reaction flask and heated to reflux. 0.75 g of RhCl3·H2O and 0.23 g of RuCl3·H2O were weighed and dissolved in an ethanol solution under argon protection, and the ethanol solutions of RhCl3·H2O and RuCl3·H2O were added dropwise to the reaction flask. The reaction was kept under reflux for 2.5 hours, then cooled to 25°C. The reaction mixture was filtered, and the resulting solid was washed with diethyl ether to obtain a powdered hydrogenation catalyst with a molar ratio of Rh:Ru of 3:1.

[0125] Preparation Example P3

[0126] This preparation example is used to illustrate the hydrogenation catalyst M. 1 a M 2 b Z c N d The preparation method of (P3), wherein M 1 Rhodium, M 2 For ruthenium, Z is chlorine, N is triphenylphosphine, a:b is 1:1, c is 3, and d is 6.

[0127] 3 g of PPh3 was dissolved in a 70°C hot ethanol solution under argon protection, and the dissolved solution was added to a reaction flask and heated to reflux. 0.25 g of RhCl3·H2O and 0.23 g of RuCl3·H2O were weighed and dissolved in an ethanol solution under argon protection, and the ethanol solutions of RhCl3·H2O and RuCl3·H2O were added dropwise to the reaction flask. The reaction was kept under reflux for 2.5 hours, then cooled to 25°C. The reaction mixture was filtered, and the resulting solid was washed with diethyl ether to obtain a powdered hydrogenation catalyst in which Rh:Ru = 1:1 (molar ratio).

[0128] The following preparation examples illustrate the preparation of hydrogenated nitrile butadiene rubber.

[0129] Preparation Example A1

[0130] (1) Dissolve nitrile rubber (grade 3335 (Ruweng) and N21L (Lanhua) in chlorobenzene at a mass ratio of 1:1 to obtain a rubber solution, add it to the reaction vessel, and purge and degas;

[0131] (2) Add hydrogenation catalyst P1 (0.12 wt% of the mass of nitrile rubber) and PPh3 (1 wt% of the mass of nitrile rubber).

[0132] (3) Introduce hydrogen gas, stir, and carry out hydrogenation reaction. The reaction conditions include: reaction temperature of 110℃, hydrogen pressure of 8MPa, and reaction time of 10 hours.

[0133] (4) Add a chelating resin (brand name: CH-97, purchased from Kehaisi (Beijing) Technology Co., Ltd.) with a mass ratio of 1:1 to the hydrogenation product of step (3) to remove the hydrogenation catalyst and obtain HNBR solution.

[0134] (5) Remove 50% (by volume) of chlorobenzene by vacuum concentration, add ethanol to the solution, and condense hydrogenated nitrile rubber. Dry under vacuum at 60°C for 6 hours.

[0135] Tests showed that HNBR-A1 had a hydrogenation degree of 99.4%. Based on the weight of hydrogenated nitrile rubber, the residual rhodium content was 0.0003 wt%, the residual ruthenium content was 0.0004 wt%, the residual phosphine (triphenylphosphine) content was 0.43 wt%, and the residual phosphine oxide (triphenylphosphine oxide) content was 0.08 wt%.

[0136] Preparation Example A2:

[0137] (1) Dissolve nitrile rubber (grade 3335 (Ruweng) and N21L (Lanhua) in chlorobenzene at a mass ratio of 1:1 to obtain a rubber solution, add it to the reaction vessel, and purge and degas;

[0138] (2) Add hydrogenation catalyst P1 (0.12 wt% of the mass of nitrile rubber) and PPh3 (1 wt% of the mass of nitrile rubber).

[0139] (3) Introduce hydrogen gas, stir, and carry out hydrogenation reaction. The reaction conditions include: reaction temperature of 110℃, hydrogen pressure of 8MPa, and reaction time of 10 hours.

[0140] (4) Remove chlorobenzene under reduced pressure and dry under vacuum at 60°C for 6 hours.

[0141] Tests showed that HNBR-A2 had a hydrogenation degree of 99.4%, and based on the weight of hydrogenated nitrile rubber, the residual phosphine (triphenylphosphine) content was 0.88 wt% and the residual phosphine oxide (triphenylphosphine oxide) content was 0.10 wt%.

[0142] Preparation Example A3:

[0143] (1) Dissolve nitrile rubber (grade 3335 (Ruweng) and N21L (Lanhua) in chlorobenzene at a mass ratio of 1:1 to obtain a rubber solution, add it to the reaction vessel, and purge and degas;

[0144] (2) Add hydrogenation catalyst P2 (0.2 wt% of the mass of nitrile rubber) and PPh3 (1 wt% of the mass of nitrile rubber);

[0145] (3) Introduce hydrogen gas, stir, and carry out hydrogenation reaction. The reaction conditions include: reaction temperature of 110℃, hydrogen pressure of 8MPa, and reaction time of 8 hours.

[0146] (4) Remove chlorobenzene under reduced pressure and dry under vacuum at 60°C for 6 hours.

[0147] Tests showed that HNBR-A3 had a hydrogenation degree of 99.9%, a residual triphenylphosphine content of 0.84 wt%, and a residual triphenylphosphine oxide content of 0.13 wt%.

[0148] Preparation Example A4:

[0149] (1) Dissolve nitrile rubber (grade 3335 (Ruweng) and N21L (Lanhua) in chlorobenzene at a mass ratio of 1:1 to obtain a rubber solution, add it to the reaction vessel, and purge and degas;

[0150] (2) Add hydrogenation catalyst P3 (0.09 wt% of the mass of nitrile rubber) and PPh3 (0.8 wt% of the mass of nitrile rubber).

[0151] (3) Introduce hydrogen gas, stir, and carry out hydrogenation reaction. The reaction conditions include: reaction temperature of 110℃, hydrogen pressure of 8MPa, and reaction time of 12 hours.

[0152] (4) Remove chlorobenzene under reduced pressure and dry under vacuum at 60°C for 6 hours.

[0153] Tests showed that HNBR-A4 had a hydrogenation degree of 98.1%, a residual triphenylphosphine content of 0.59 wt%, and a residual triphenylphosphine oxide content of 0.16 wt%.

[0154] Preparation Example A5:

[0155] (1) Dissolve nitrile rubber (grade 3335 (Ruweng) and N21L (Lanhua) in chlorobenzene at a mass ratio of 1:1 to obtain a rubber solution, add it to the reaction vessel, and purge and degas;

[0156] (2) Add hydrogenation catalyst P3 (0.09 wt% of the mass of nitrile rubber), ruthenium compound (PPh3)3RuCl2 (0.02 wt% of the mass of nitrile rubber) and triphenylphosphine PPh3 (1 wt% of the mass of nitrile rubber).

[0157] (3) Introduce hydrogen gas, stir, and carry out hydrogenation reaction. The reaction conditions include: reaction temperature of 110℃, hydrogen pressure of 8MPa, and reaction time of 12 hours.

[0158] (4) Remove chlorobenzene under reduced pressure and dry under vacuum at 60°C for 6 hours.

[0159] Tests showed that HNBR-A5 had a hydrogenation degree of 97.0%, a residual triphenylphosphine content of 0.79 wt%, and a residual triphenylphosphine oxide content of 0.18 wt%.

[0160] Preparation Example A6:

[0161] (1) Dissolve nitrile rubber (grade 3335 (Ruweng) and N21L (Lanhua) in chlorobenzene at a mass ratio of 1:1 to obtain a rubber solution, add it to the reaction vessel, and purge and degas;

[0162] (2) Add Grubbs II catalyst (0.01 wt% of the mass of nitrile rubber) and 1-decene (1 wt% of the mass of nitrile rubber), and react at 60°C for 60 minutes;

[0163] (3) Add hydrogenation catalyst P3 (0.15 wt% of the mass of nitrile rubber) and PPh3 (1 wt% of the mass of nitrile rubber).

[0164] (4) Introduce hydrogen gas, stir, and carry out hydrogenation reaction. The reaction conditions include: reaction temperature of 110℃, hydrogen pressure of 8MPa, and reaction time of 12 hours.

[0165] (5) Remove chlorobenzene under reduced pressure and dry under vacuum at 60°C for 6 hours.

[0166] Tests showed that HNBR-A6 had a hydrogenation degree of 98.4%, a residual triphenylphosphine content of 0.78 wt%, and a triphenylphosphine oxide content of 0.17 wt%.

[0167] The Grubbs II catalyst has the structure shown below.

[0168]

[0169] Examples and Comparative Examples

[0170] Compounds of Formula I (triphenylphosphine (S=PPh3)), compounds of Formula II ((PPh4)Cl, (PPh4)Br), ruthenium-containing metal compound RuCl(PPh3)3, triphenylphosphine (PPh3), and phosphine oxide (triphenylphosphine oxide O=PPh3) were added to the prepared HNBR-A1 to HNBR-A6, respectively. The mixtures were then homogenized on a two-roll mill at room temperature to obtain hydrogenated nitrile butadiene rubber. The specific amounts of compounds of Formula I, compounds of Formula II, ruthenium-containing metal compounds, triphenylphosphine, and phosphine oxide were used to ensure that the final contents of compounds of Formula I, compounds of Formula II, ruthenium metal, rhodium metal, phosphine, and phosphine oxide in the prepared HNBR were as shown in Table 1.

[0171] Table 1

[0172]

[0173] Test case

[0174] S1. Add dicumyl peroxide and triallyl isocyanurate (excluding those in Table 2) to the HNBR prepared in the examples and comparative examples, mix in an internal mixer for 20 minutes, let stand for 4 hours after discharge, add dicumyl peroxide and triallyl isocyanurate, mix in an internal mixer at a temperature not exceeding 100°C for 40 minutes to obtain the compound.

[0175] S2. The compound rubber was vulcanized under the following conditions: primary vulcanization (flat vulcanizing machine): 170℃×20min; 15MPa; secondary vulcanization (aging chamber): 150℃×4h. Vulcanized rubber was obtained, and the properties of the rubber before aging were tested. The test results are shown in Table 3.

[0176] The vulcanized rubber was aged in an aging chamber at 150℃ for 100 hours, and the properties of the aged rubber were tested. The test results are shown in Table 3.

[0177] Table 2

[0178]

[0179] Table 3

[0180]

[0181] Note: Change rate %* = (Performance before aging - Performance after aging) / Performance before aging × 100%.

[0182] By comparing samples AS1 and DS1, and AS3 and DS2 respectively, it can be seen that when hydrogenated nitrile butadiene rubber containing compounds of Formula I, Formula II, and ruthenium metal compounds is used to prepare vulcanized rubber, the elongation at break and tear strength of HNBR vulcanized rubber can be effectively improved, and the compression set of the product can be reduced. At the same time, the impact of hydrogenated nitrile butadiene rubber aging on elongation at break, tear strength, and compression set of the product is reduced, and the aging resistance of the product is improved.

[0183] Comparing samples AS3 with DS2, DS3, and DS4, it can be seen that when hydrogenated nitrile butadiene rubber containing compounds of Formula I, Formula II, and ruthenium metal compounds is used to prepare vulcanized rubber, the mechanical properties of HNBR vulcanized rubber are improved compared to hydrogenated nitrile butadiene rubber containing only compounds of Formula I or Formula II. At the same time, the effects of product aging on elongation at break, tear strength, and compression set are better mitigated, and the aging resistance is improved.

[0184] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A hydrogenated nitrile rubber, characterized by, The hydrogenated nitrile rubber contains a compound represented by Formula I, a compound represented by Formula II, and a ruthenium metal-containing compound; Formula I, In formula I, R1, R2and R3are each independently selected from C1-C8alkyl, C4-C8cycloalkyl, C6-C10aryl, or C7-C15aralkyl; 15 15 C7-C15aralkyl;​ (L o M) p Y q Formula II, In formula II, o L are identical or different, each independently a C1-C8 alkyl, a C4-C8 cycloalkyl, a C6-C10 aryl or a C7-C15 aralkyl, 15 15 aralkyl,​ M is phosphorus or arsenic, q Ys are the same or different, each independently a halogen ion, o is 3, 4, 5, or 6, p is 1, 2, or 3, and q is 1, 2, or 3; the content of the compound represented by Formula I is less than or equal to 2 wt% based on the total weight of the hydrogenated nitrile rubber; the content of the compound represented by Formula II is less than or equal to 1 wt% based on the total weight of the hydrogenated nitrile rubber; the content of the metal ruthenium is 0.0001 wt% to 1 wt% based on the total weight of the hydrogenated nitrile rubber; The hydrogenated nitrile rubber further contains a phosphine and / or an oxidized phosphine. The content of the phosphine is 0.001 wt% to 10 wt% and the content of the oxidized phosphine is 0.001 wt% to 10 wt% based on the total weight of the hydrogenated nitrile rubber.

2. The hydrogenated nitrile rubber according to claim 1, wherein, In formula I, R1, R2and R3are each independently selected from C6-C 15 aryl or C7-C 15 aralkyl.

3. The hydrogenated nitrile rubber of claim 1, wherein, the content of the compound represented by Formula I is less than or equal to 1 wt% based on the total weight of the hydrogenated nitrile rubber.

4. The hydrogenated nitrile rubber of claim 1, wherein, In formula II, o L are the same or different, each independently C6-C 15 aryl.

5. The hydrogenated nitrile rubber of claim 1, wherein, The compound represented by Formula II is (PPh4)Cl and / or (PPh4)Br.

6. The hydrogenated nitrile rubber of claim 1, wherein, the content of the compound represented by Formula II is less than or equal to 0.9 wt% based on the total weight of the hydrogenated nitrile rubber.

7. The hydrogenated nitrile rubber of claim 1, wherein, the content of the metal ruthenium is 0.0001 wt% to 0.8 wt% based on the total weight of the hydrogenated nitrile rubber.

8. The hydrogenated nitrile rubber as claimed in claim 1, wherein, The ruthenium metal-containing compound is a metal ruthenium compound and / or a metal rhodium ruthenium compound.

9. The hydrogenated nitrile rubber according to claim 8, wherein, When the ruthenium metal-containing compound contains a metal rhodium ruthenium compound, the content of the metal ruthenium is 0.0001 wt% to 1 wt% and the content of the metal rhodium is 0.0001 wt% to 1 wt% based on the total weight of the hydrogenated nitrile rubber.

10. The hydrogenated nitrile rubber of claim 8, wherein, When the ruthenium metal-containing compound contains a metal rhodium ruthenium compound, the content of the metal ruthenium is 0.0001 wt% to 0.5 wt% and the content of the metal rhodium is 0.0001 wt% to 0.5 wt% based on the total weight of the hydrogenated nitrile rubber.

11. The hydrogenated nitrile rubber according to any one of claims 8 to 10, wherein The metal ruthenium compound is a compound represented by Formula III and / or a ruthenium-containing olefin metathesis catalyst. (R 2 j A 2 ) m RuX 2 n Formula III, Among them, j R 2 Whether the groups are the same or different, each is independently selected from C1-C8 alkyl groups, C4-C8 cycloalkyl groups, and C6-C6 alkyl groups. 15 aryl or C7-C 15 Aryl group; A 2 Selected from phosphorus, arsenic, sulfur, or sulfoxide groups S=O; n X 2 They are either the same or different, and are independently selected from hydrogen or anions; m is 2, 3 or 4; j is 2 or 3; n is 1, 2 or 3.

12. The hydrogenated nitrile rubber according to any one of claims 8 to 10, wherein, The metal rhodium ruthenium compound is a compound represented by Formula IV: M 1 a M 2 b Z c N d Formula IV, wherein M is Rh 1 is Rh, M 2 is Ru, d Ns are the same or different, each independently an organic phosphine, an organic cerium, a nitrogen-containing organic compound, a sulfur-containing organic compound, or an oxygen-containing organic compound; c Zs are the same or different, each independently chlorine, bromine, or hydrogen, 1≤a≤6, 1≤b≤3, 3≤c≤7, and 6≤d≤21.

13. The hydrogenated nitrile rubber of claim 12, wherein, In Formula IV, N is an organic monophosphine.

14. The hydrogenated nitrile rubber of claim 12, wherein, In Formula IV, N is triphenylphosphine.

15. The hydrogenated nitrile rubber according to any one of claims 1 to 10, wherein, The phosphine is selected from an organic monophosphine and / or an organic diphosphine.

16. The hydrogenated nitrile rubber of any one of claims 1-10, wherein, The phosphine is a compound represented by Formula V and / or a compound represented by Formula VI: Formula V Formula VI; Among them, L1-L7 are each independently selected from C1-C8 alkyl groups, C4-C8 cycloalkyl groups, and C6-C6 alkyl groups. 15 aryl or C7-C 15 The aralkyl group, where Y is selected from alkyl, alkenyl or ynyl groups.

17. The hydrogenated nitrile rubber of any one of claims 1-10, wherein, The oxidized phosphine is a compound represented by Formula VII and / or a compound represented by Formula VIII: Formula VII Formula VIII; wherein M1-M7are each independently selected from a C1-C8alkyl group, a C4-C8cycloalkyl group, a C6-C10aryl group or a C7-C15aralkyl group, and Y is selected from an alkyl, alkenyl or alkynyl group. 15 wherein M1-M7are each independently selected from a C1-C8alkyl group, a C4-C8cycloalkyl group, a C6-C10aryl group or a C7-C15aralkyl group, and Y is selected from an alkyl, alkenyl or alkynyl group. 15 wherein M1 18. The hydrogenated nitrile rubber of any one of claims 1-10, wherein, The hydrogenated nitrile rubber is a product from a hydrogenation reaction of a nitrile rubber.

19. The hydrogenated nitrile rubber of claim 18, wherein, The nitrile rubber is selected from a binary nitrile rubber and / or a ternary nitrile rubber.

20. The hydrogenated nitrile rubber of claim 19, wherein, The binary nitrile rubber is selected from at least one of butadiene-acrylonitrile rubber, butadiene-(meth)acrylonitrile rubber, 2-methyl-1,3-butadiene-acrylonitrile rubber, and 2-methyl-1,3-butadiene-(meth)acrylonitrile rubber.

21. The hydrogenated nitrile rubber of claim 19, wherein, The terpolybutylnitrile rubber is at least one of butadiene-acrylonitrile-acrylic acid rubber, butadiene-acrylonitrile-methyl acrylate rubber, butadiene-acrylonitrile-ethyl acrylate rubber, butadiene-acrylonitrile-tert-butyl acrylate rubber, butadiene-acrylonitrile-butyl acrylate rubber, butadiene-acrylonitrile-(meth)acrylic acid rubber, butadiene-acrylonitrile-(meth)acrylic acid methyl ester rubber, butadiene-acrylonitrile-(meth)acrylic acid ethyl ester rubber, butadiene-acrylonitrile-(meth)acrylic acid tert-butyl ester rubber, butadiene-acrylonitrile-(meth)acrylic acid butyl ester rubber, butadiene-(meth)acrylonitrile-acrylic acid rubber, butadiene-(meth)acrylonitrile-methyl acrylate rubber, butadiene-(meth)acrylonitrile-ethyl acrylate rubber, butadiene-(meth)acrylonitrile-tert-butyl acrylate rubber, butadiene-(meth)acrylonitrile-butyl acrylate rubber, butadiene-(meth)acrylonitrile-(meth)acrylic acid rubber, butadiene-(meth)acrylonitrile-(meth)acrylic acid methyl ester rubber, butadiene-(meth)acrylonitrile-(meth)acrylic acid ethyl ester rubber, butadiene-(meth)acrylonitrile-(meth)acrylic acid tert-butyl ester rubber, and butadiene-(meth)acrylonitrile-(meth)acrylic acid butyl ester rubber.

22. A process for the production of the hydrogenated nitrile rubber according to any one of claims 1 to 21, characterized in that The preparation method comprises: adding the compound shown in formula I, the compound shown in formula II, optionally a ruthenium metal-containing compound, optionally a phosphine, and optionally an oxidation phosphine to a hydrogenated butylnitrile rubber glue solution, stirring, coagulating, drying to obtain the hydrogenated butylnitrile rubber; or adding the compound shown in formula I, the compound shown in formula II, optionally a ruthenium metal-containing compound, optionally a phosphine, and optionally an oxidation phosphine to a hydrogenated butylnitrile rubber, mixing to obtain the hydrogenated butylnitrile rubber.

23. A hydrogenated nitrile rubber composition characterized in that, The hydrogenated butylnitrile rubber composition comprises the hydrogenated butylnitrile rubber as claimed in claims 1-21.

24. A vulcanizate characterized in that, The vulcanized rubber is prepared by mixing and vulcanizing the hydrogenated butylnitrile rubber composition as claimed in claim 23. The vulcanized rubber is prepared by mixing and vulcanizing the hydrogenated butylnitrile rubber composition as claimed in claim 23.

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