Hydrogenated nitrile rubber and composition thereof, and vulcanized rubber

Abstract

The invention relates to the field of nitrile rubber, and discloses hydrogenated nitrile rubber, a composition thereof and vulcanized rubber. The hydrogenated butadiene-acrylonitrile rubber contains a compound as shown in a formula I, a compound as shown in a formula II and a ruthenium-containing metal compound, the formula II is imgabs0 # (LoM) pYq, and the content of the compound in the formula I is less than or equal to 2wt% on the basis of the weight of the hydrogenated butadiene-acrylonitrile rubber; on the basis of the weight of the hydrogenated nitrile rubber, the content of the compound in the formula II is less than or equal to 1wt%; on the basis of the weight of the hydrogenated nitrile rubber, the content of the metal ruthenium is 0.0001-1 wt%. The hydrogenated butadiene-acrylonitrile rubber has the advantages that under the condition that the metal catalyst and the phosphine ligand are not removed or are not completely removed, namely, the hydrogenated butadiene-acrylonitrile rubber contains a certain amount of metal catalyst and phosphine ligand, especially contains a certain amount of ruthenium-containing metal compound and phosphine ligand; vulcanized rubber prepared from the hydrogenated butadiene-acrylonitrile rubber can still obtain better mechanical properties, and meanwhile, good aging resistance is kept.

Description

Technical Field

[0001] The present invention relates to the field of nitrile rubber, and in particular to hydrogenated nitrile rubber and a composition thereof, and a vulcanized rubber. Background Art

[0002] Hydrogenated nitrile rubber (HNBR) is a highly saturated nitrile rubber with excellent oil resistance, wear resistance and low temperature resistance. Its vulcanized rubber also shows excellent tolerance to high and low temperatures and oil, and is widely used in the fields of petroleum, aerospace, automobiles, etc.

[0003] Hydrogenated nitrile rubber is mainly obtained by selectively hydrogenating the carbon-carbon double bonds on nitrile rubber. Commonly used hydrogenation catalysts include rhodium, ruthenium, palladium, etc. In addition to the use of precious metal catalysts, phosphine-containing ligands such as PPh3 are often required as co-catalysts in the preparation process to improve the stability and reaction activity of the catalyst. However, the use of phosphine ligands such as PPh3 will also have a certain impact on the hardness and compression set of hydrogenated nitrile rubber.

[0004] For a long time, researchers have been looking for methods to avoid the effects of phosphine-containing ligands such as PPh3 on the performance of hydrogenated nitrile rubber products. CN105873957A discloses a hydrogenated nitrile rubber containing phosphine oxide or diphosphine oxide. The patent improves the modulus and compression deformation of hydrogenated nitrile rubber by converting triphenylphosphine in the product into triphenylphosphine oxide. CN105873956A discloses a hydrogenated nitrile rubber containing phosphine sulfide and / or diphosphine sulfide. The patent improves the modulus of hydrogenated nitrile rubber under different tensile stresses and the compression deformation after storage at high temperature by converting triphenylphosphine in the product into triphenylphosphine sulfide. Summary of the invention

[0005] The object of the present invention is to provide a hydrogenated nitrile rubber and a composition thereof, and a vulcanized rubber. The hydrogenated nitrile rubber can enable the vulcanized rubber prepared from the hydrogenated nitrile rubber to obtain better mechanical properties while maintaining good aging resistance when the metal catalyst and the phosphine ligand are not removed or are incompletely removed, that is, when the hydrogenated nitrile rubber contains a certain amount of metal catalyst and phosphine ligand, especially a certain amount of ruthenium-containing metal compound and phosphine ligand.

[0006] In order to achieve the above-mentioned object, the first aspect of the present invention provides a hydrogenated nitrile rubber, characterized in that the hydrogenated nitrile rubber contains a compound represented by formula I, a compound represented by formula II and a ruthenium-containing metal compound;

[0007]

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

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

[0010] In formula II, o L are the same or different and are independently C1-C8 alkyl, C4-C8 cycloalkyl, C6-C 15 Aryl or C7-C 15 The aralkyl group,

[0011] M is phosphorus or arsenic,

[0012] q Y are the same or different and are each independently an anion,

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

[0014] Based on the weight of the hydrogenated nitrile rubber, the content of the compound represented by formula I is less than or equal to 2 wt %;

[0015] Based on the weight of the hydrogenated nitrile rubber, the content of the compound represented by formula II is less than or equal to 1wt%;

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

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

[0018] Adding the compound represented by formula I, the compound represented by formula II, optionally a ruthenium-containing metal compound, optionally a phosphine and optionally a phosphine oxide to a hydrogenated nitrile rubber solution, and obtaining the hydrogenated nitrile rubber after stirring, coagulation and drying; or;

[0019] The hydrogenated nitrile rubber is obtained by adding the compound represented by formula I, the compound represented by formula II, optionally a ruthenium-containing metal compound, optionally a phosphine and optionally a phosphine oxide into the hydrogenated nitrile rubber and mixing them.

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

[0022] Through the above technical scheme, the hydrogenated nitrile rubber and its composition, and the vulcanized rubber provided by the present invention obtain the following beneficial effects:

[0023] The hydrogenated nitrile rubber and its composition and vulcanized rubber provided by the present invention can enable the vulcanized rubber prepared from the hydrogenated nitrile rubber to obtain better mechanical properties while maintaining good aging resistance when the hydrogenation catalyst and the phosphine ligand are not removed or are incompletely removed, that is, when a certain amount of metal catalyst and phosphine ligand are contained, especially a certain amount of metal ruthenium compound and phosphine ligand are contained. DETAILED DESCRIPTION

[0024] The endpoints and any values ​​of the ranges disclosed in this article 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 each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0025] In the present invention, the C1-C8 alkyl group includes a C1-C8 straight-chain alkyl group and a C3-C8 branched-chain alkyl group, and specific examples thereof 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 -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 the present invention, specific examples of the C4-C8 cycloalkyl group may include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.

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

[0028] In the present invention, the term "aralkyl" can be represented by Ar x -T-, wherein x Ar are the same or different and are independently aryl, T is alkyl, and x is an integer from 1 to 3. 15 Specific examples of the aralkyl group may include, but are not limited to, phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl, phenyl-isopropyl, phenyl-n-pentyl, and phenyl-n-butyl.

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

[0030]

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

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

[0033] In formula II, o L are the same or different and are independently C1-C8 alkyl, C4-C8 cycloalkyl, C6-C 15 Aryl or C7-C 15 The aralkyl group,

[0034] M is phosphorus or arsenic,

[0035] q Y are the same or different and are each independently an anion,

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

[0037] Based on the weight of the hydrogenated nitrile rubber, the content of the compound represented by formula I is less than or equal to 2 wt %;

[0038] Based on the weight of the hydrogenated nitrile rubber, the content of the compound represented by formula II is less than or equal to 1wt%;

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

[0040] In the present invention, the hydrogenated nitrile rubber is a product of the hydrogenation reaction of nitrile rubber, and the hydrogenated nitrile rubber can, when the metal catalyst and the phosphine ligand are not removed or are not completely removed, that is, when the hydrogenated nitrile rubber contains the above-mentioned specific content of the ruthenium-containing metal compound and the phosphine ligand, still enable the vulcanized rubber prepared from the hydrogenated nitrile rubber to obtain better mechanical properties while maintaining good aging resistance.

[0041] Further, in Formula I, R1, R2 and R3 are each independently selected from C6-C 15 Aryl or C7-C 15 of aralkyl.

[0042] In one 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 (methylphenyl)).

[0043] Furthermore, based on the weight of the hydrogenated nitrile rubber, the content of the compound represented by formula I is less than or equal to 1 wt %.

[0044] Furthermore, based on the weight of the hydrogenated nitrile rubber, the content of the compound represented by formula I is 0.0001 wt%-0.8 wt%.

[0045] Further, in Formula II, o L are the same or different and are each independently C6-C 15 Furthermore, in Formula II, o L are all phenyl.

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

[0047] Further, in Formula II, Y is a halogen ion. Further, in Formula II, Y is a chloride ion or a bromide ion. Further, in Formula II, Y is a chloride ion.

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

[0049] Furthermore, based on the weight of the hydrogenated nitrile rubber, the content of the compound represented by formula II is less than or equal to 0.9 wt %.

[0050] Furthermore, based on the weight of the hydrogenated nitrile rubber, the content of the compound represented by formula II is 0.0001-0.8 wt %.

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

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

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

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

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

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

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

[0058] Further, in Formula III, j R 2 The same or different, each independently C6-C 15 More preferably, in Formula I, j R 2 All are phenyl.

[0059] Further, in Formula III, A 2 is phosphorus, arsenic, sulfur or sulfoxide. More preferably, in formula III, A 2 For phosphorus.

[0060] Further, in Formula III, n X 2 The same or different, each independently is hydrogen or an anion. More preferably, in Formula III, X2 Preferably, in Formula III, X 2 is a halogen ion. More preferably, in Formula III, X 2 is a chloride ion or a bromide ion. Particularly preferably, in formula III, X 2 For chloride ion.

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

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

[0063] According to the present invention, the metal rhodium ruthenium compound is a compound shown in 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] d N are the same or different, and are each independently an organic phosphine, an organic cerium, a nitrogen-containing organic compound, a sulfur-containing organic compound or an oxygen-containing organic compound. Preferably, N is an organic monophosphine; more preferably, N is triphenylphosphine;

[0067] c Z are the same or different and are independently chlorine, bromine or hydrogen,

[0068] 1≤a≤6, 1≤b≤3, 3≤m≤7, 6≤n≤21.

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

[0070] Furthermore, in Formula IV, 1≤a≤4, 1≤b≤2, 3≤m≤6, 6≤n≤15.

[0071] In a specific embodiment of the present invention, in IV, a:b:m:n=2:1:4:9, or a:b:m:n=3:1:5:12, or a:b:m:n=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 the phosphine is 0.001wt%-10wt%, and the content of the phosphine oxide is 0.001wt%-10wt%.

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

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

[0076] In the present invention, there is no particular limitation on the type of the phosphine, which is generally a phosphine ligand used for hydrogenation of nitrile rubber in the art. Preferably, the phosphine is selected from organic monophosphine and / or organic diphosphine.

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

[0078]

[0079] Wherein, L1-L7 are each independently selected from C1-C8 alkyl, C4-C8 cycloalkyl, C6-C 15 Aryl or C7-C 15 wherein Y is selected from an alkyl group, an alkenyl group or an alkynyl group.

[0080] Further, L1-L7 are each independently selected from C6-C 15 Aryl or C7-C 15 The aralkyl group of , Y is an alkyl group.

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

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

[0083] In the present invention, there is no particular limitation on the type of the phosphine oxide, which is generally a phosphine oxide generated by oxidation of a phosphine ligand used for hydrogenation of nitrile rubber in the art. Preferably, the phosphine oxide is selected from organic monophosphine oxides and / or organic diphosphine oxides. Further preferably, the phosphine oxide is a compound represented by formula VII and / or a compound represented by formula VIII:

[0084]

[0085] Wherein, M1-M7 are each independently selected from C1-C8 alkyl, C4-C8 cycloalkyl, C6-C 15 Aryl or C7-C 15 wherein Y is selected from an alkyl group, an alkenyl group or an alkynyl group.

[0086] Further, M1-M7 are each independently selected from C6-C 15 Aryl or C7-C 15 The aralkyl group of , Y is an alkyl group.

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

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

[0089] In the present invention, there is no particular limitation on the type of hydrogenated nitrile rubber. It may be a 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 the present invention, the binary nitrile rubber is at least one selected from butadiene-acrylonitrile rubber, butadiene-(meth)acrylonitrile rubber, 2-methyl-1,3-butadiene-acrylonitrile rubber and 2-methyl-1,3-butadiene-(meth)acrylonitrile rubber.

[0091] In the present 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)acrylic rubber, butadiene-acrylonitrile-methyl (meth)acrylate rubber, butadiene-acrylonitrile-ethyl (meth)acrylate rubber, butadiene-acrylonitrile-tert-butyl (meth)acrylate rubber, butadiene-acrylonitrile-butyl (meth)acrylate rubber, butadiene-acrylonitrile-(meth)acrylate rubber, At least one of rubber, butadiene-(meth)acrylonitrile-methyl acrylate rubber, butadiene-(meth)acrylonitrile-ethyl acrylate rubber, butadiene-(meth)acrylonitrile-t-butyl acrylate rubber, butadiene-(meth)acrylonitrile-butyl acrylate rubber, butadiene-(meth)acrylonitrile-(meth)acrylic acid rubber, butadiene-(meth)acrylonitrile-methyl (meth)acrylate rubber, butadiene-(meth)acrylonitrile-ethyl (meth)acrylate rubber, butadiene-(meth)acrylonitrile-t-butyl (meth)acrylate rubber and butadiene-(meth)acrylonitrile-butyl (meth)acrylate rubber.

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

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

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

[0095] In the present invention, the compound represented by formula I, the compound represented by formula II, metal ruthenium, optional phosphine and optional phosphine oxide contained in the hydrogenated nitrile rubber may come from the hydrogenation catalyst and phosphine ligand that are not removed or not completely removed during the preparation process of the hydrogenated nitrile rubber, or may be added additionally, as long as the content of the compound represented by formula I, the compound represented by formula II, metal ruthenium, optional phosphine and optional phosphine oxide in the hydrogenated nitrile rubber meets the requirements of the present invention.

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

[0097] Adding the compound represented by formula I, the compound represented by formula II, optionally a ruthenium-containing metal compound, optionally a phosphine and optionally a phosphine oxide to a hydrogenated nitrile rubber solution, and obtaining the hydrogenated nitrile rubber after stirring, coagulation and drying; or;

[0098] The hydrogenated nitrile rubber is obtained by adding the compound represented by formula I, the compound represented by formula II, optionally a ruthenium-containing metal compound, optionally a phosphine and optionally a phosphine oxide into the hydrogenated nitrile rubber and mixing them.

[0099] In the present invention, there is no particular limitation on the amount of the compound represented by formula I, the compound represented by formula II, the ruthenium-containing metal compound, the phosphine and the phosphine oxide added, as long as the content of the compound represented by formula I, the compound represented by formula II, metal ruthenium, metal rhodium, phosphine and phosphine oxide in the prepared hydrogenated nitrile rubber meets the requirements of the present invention.

[0100] In the present invention, there is no special requirement for the stirring conditions, as long as the hydrogenated nitrile rubber solution and the compound shown in formula I, the compound shown in formula II, the optional ruthenium metal compound, the optional phosphine and the optional phosphine oxide can be fully mixed and uniformly mixed, for example, stirring at 10-10000 rpm for 1-60 min.

[0101] In the present invention, there is no particular limitation on the method of coagulation, and gelation can be carried out by conventional methods in the art, such as adding ethanol to the stirred product.

[0102] In the present invention, there is no particular limitation 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 h under vacuum conditions.

[0103] In the present invention, there is no particular limitation on the equipment used for mixing, and the mixing can be carried out using conventional mixing equipment in the art, such as an open mixer and / or an internal mixer. There is no particular limitation on the conditions for mixing, as long as the hydrogenated nitrile rubber, the compound shown in formula I, the compound shown in formula II, the ruthenium-containing metal compound, optionally the phosphine and optionally the phosphine oxide can be fully mixed and uniformly obtained, for example, mixing at 25-200° C. for 2-300 min.

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

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

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

[0107] In a preferred embodiment of the present invention, based on the weight of the hydrogenated nitrile rubber, the content of the compound shown in formula I is 0.0001wt%-0.8wt%, the content of the compound shown in formula II is 0.0001wt%-0.8wt%, the content of metal ruthenium is 0.0001wt%-0.5wt%, the content of metal 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 rubber composition, characterized in that the hydrogenated nitrile rubber composition comprises the above-mentioned hydrogenated nitrile rubber.

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

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

[0112] The present invention will be described in detail below by way of examples. In the following examples,

[0113] The contents of the compound represented by formula I, phosphine and phosphine oxide in the hydrogenated nitrile rubber were measured by liquid chromatography (UPLC-iclass, Waters, USA);

[0114] The contents of ruthenium and rhodium in hydrogenated nitrile rubber were measured by inductively coupled plasma emission spectroscopy (Optima 8300, PE Company, USA);

[0115] Hardness: Shore A hardness was measured using a Shore durometer (HT 3000, Montech, Germany) according to GB / T531.1-2008.

[0116] Tensile properties and tear strength: tested by material testing machine according to GB / T 528-2009 and GB / T529-2008, with a tensile rate of 500 mm / min, a test temperature of (23±2)°C, a sample length of 25 mm, and a width of 6 mm. For each group of samples, 10 parallel experiments were conducted and the median value was taken.

[0117] Compression set: Test the compression set of vulcanized rubber in accordance with GB / T 7759.1-2015. The test adopts the type A specimen recommended in the standard. The test conditions are 150℃×70h.

[0118] The raw materials used in the examples and comparative examples are all commercially available.

[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 (P1) preparation method, wherein M 1 Rhodium, M 2 is 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 hot ethanol solution at 70°C under argon protection, and the dissolved solution was added to a reaction bottle 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 solution of RhCl3·H2O and RuCl3·H2O was added dropwise to the reaction bottle, and the reflux reaction was maintained for 2.5 hours, then the temperature was lowered to 25°C, the reaction mixture was filtered, and the obtained solid phase material was washed with 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 (P2) preparation method, wherein M 1 Rhodium, M 2 is 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 hot ethanol solution at 70°C under argon protection, and the dissolved solution was added to a reaction bottle 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 solution of RhCl3·H2O and RuCl3·H2O was added dropwise to the reaction bottle, and the reflux reaction was maintained for 2.5 hours, then the temperature was lowered to 25°C, the reaction mixture was filtered, and the obtained solid phase material was washed with ether to obtain a powdered hydrogenation catalyst, in which Rh:Ru=3:1 (molar ratio).

[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 (P3) preparation method, wherein M 1 Rhodium, M 2 is ruthenium, Z is chlorine, N is triphenylphosphine, a:b is 1:1, c is 3, and d is 6.

[0127] 3 grams of PPh3 were dissolved in a hot ethanol solution at 70°C under argon protection, and the dissolved solution was added to a reaction bottle and heated to reflux; 0.25 grams of RhCl3·H2O and 0.23 grams of RuCl3·H2O were weighed and dissolved in an ethanol solution under argon protection, and the ethanol solution of RhCl3·H2O and RuCl3·H2O was added dropwise to the reaction bottle, and the reflux reaction was maintained for 2.5 hours, then the temperature was lowered to 25°C, the reaction mixture was filtered, and the obtained solid phase material was washed with ether to obtain a powdered hydrogenation catalyst, in which Rh:Ru=1:1 (molar ratio).

[0128] The following preparation example is used to illustrate the preparation of hydrogenated nitrile rubber

[0129] Preparation Example A1

[0130] (1) dissolving nitrile rubber (brand 3335 (Ruiong) and N21L (Lanhua), mixed in a mass ratio of 1:1) in chlorobenzene (nitrile rubber concentration 4 wt%) to obtain a rubber solution, adding the solution into a reaction kettle, and degassing the solution;

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

[0132] (3) charging hydrogen, stirring, and performing a hydrogenation reaction, wherein the reaction conditions include: a reaction temperature of 110° C., a hydrogen pressure of 8 MPa, and a reaction time of 10 hours;

[0133] (4) adding a chelating resin (brand name: CH-97, purchased from Kehaisi (Beijing) Technology Co., Ltd.) with a mass ratio of 1:1 to the nitrile rubber to the hydrogenated product of step (3), removing the hydrogenation catalyst, and obtaining an HNBR glue solution.

[0134] (5) The solution was concentrated under reduced pressure to remove 50% (volume) of chlorobenzene, and ethanol was added to the solution to condense hydrogenated nitrile rubber, which was then vacuum dried at 60° C. for 6 hours.

[0135] After testing, the degree of hydrogenation of HNBR-A1 is 99.4%. Based on the weight of hydrogenated nitrile rubber, the content of residual metal rhodium is 0.0003wt%, the content of residual metal ruthenium is 0.0004wt%, the content of residual phosphine (triphenylphosphine) is 0.43wt%, and the content of residual phosphine oxide (triphenylphosphine oxide) is 0.08wt%.

[0136] Preparation Example A2:

[0137] (1) dissolving nitrile rubber (brand 3335 (Ruiong) and N21L (Lanhua), mixed in a mass ratio of 1:1) in chlorobenzene (nitrile rubber concentration 4 wt%) to obtain a rubber solution, adding the solution into a reaction kettle, and degassing the solution;

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

[0139] (3) charging hydrogen, stirring, and performing a hydrogenation reaction, wherein the reaction conditions include: a reaction temperature of 110° C., a hydrogen pressure of 8 MPa, and a reaction time of 10 hours;

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

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

[0142] Preparation Example A3:

[0143] (1) dissolving nitrile rubber (brand 3335 (Ruiong) and N21L (Lanhua), mixed in a mass ratio of 1:1) in chlorobenzene (nitrile rubber concentration 4 wt%) to obtain a rubber solution, adding the solution into a reaction kettle, and degassing the solution;

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

[0145] (3) charging hydrogen, stirring, and performing a hydrogenation reaction, wherein the reaction conditions include: a reaction temperature of 110° C., a hydrogen pressure of 8 MPa, and a reaction time of 8 hours;

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

[0147] The test showed that the hydrogenation degree of HNBR-A3 was 99.9%, the residual triphenylphosphine content was 0.84wt%, and the residual triphenylphosphine oxide content was 0.13wt%.

[0148] Preparation Example A4:

[0149] (1) dissolving nitrile rubber (brand 3335 (Ruiong) and N21L (Lanhua), mixed in a mass ratio of 1:1) in chlorobenzene (nitrile rubber concentration 4 wt%) to obtain a rubber solution, adding the solution into a reaction kettle, and degassing the solution;

[0150] (2) adding 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) charging hydrogen, stirring, and performing a hydrogenation reaction, the reaction conditions including: a reaction temperature of 110° C., a hydrogen pressure of 8 MPa, and a reaction time of 12 hours;

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

[0153] The test showed that the hydrogenation degree of HNBR-A4 was 98.1%, the residual triphenylphosphine content was 0.59wt%, and the residual triphenylphosphine oxide content was 0.16wt%.

[0154] Preparation Example A5:

[0155] (1) dissolving nitrile rubber (brand 3335 (Ruiong) and N21L (Lanhua), mixed in a mass ratio of 1:1) in chlorobenzene (nitrile rubber concentration 4 wt%) to obtain a rubber solution, adding the solution into a reaction kettle, and degassing the solution;

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

[0157] (3) charging hydrogen, stirring, and performing a hydrogenation reaction, the reaction conditions including: a reaction temperature of 110° C., a hydrogen pressure of 8 MPa, and a reaction time of 12 hours;

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

[0159] The test showed that the hydrogenation degree of HNBR-A5 was 97.0%, the residual triphenylphosphine content was 0.79wt%, and the residual triphenylphosphine oxide content was 0.18wt%.

[0160] Preparation Example A6:

[0161] (1) dissolving nitrile rubber (brand 3335 (Ruiong) and N21L (Lanhua), mixed in a mass ratio of 1:1) in chlorobenzene (nitrile rubber concentration 4 wt%) to obtain a rubber solution, adding the solution into a reaction kettle, and degassing the solution;

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

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

[0164] (4) charging hydrogen, stirring, and performing a hydrogenation reaction, the reaction conditions including: a reaction temperature of 110° C., a hydrogen pressure of 8 MPa, and a reaction time of 12 hours;

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

[0166] The test showed that the hydrogenation degree of HNBR-A6 was 98.4%, the residual triphenylphosphine content was 0.78wt%, and the triphenylphosphine oxide content was 0.17wt%.

[0167] Among them, the Grubbs II catalyst has the structure shown below.

[0168]

[0169] Examples and Comparative Examples

[0170] To the prepared HNBR-A1 to HNBR-A6, the compound represented by formula I (triphenylphosphine (S=PPh3)), the compound represented by formula II ((PPh4)Cl, (PPh4)Br), the ruthenium metal compound RuCl(PPh3)3, triphenylphosphine (PPh3), and phosphine oxide (triphenylphosphine oxide O=PPh3) are added respectively, and the mixture is evenly mixed on an open mill at room temperature to obtain hydrogenated nitrile rubber, wherein the specific amounts of the compound represented by formula I, the compound represented by formula II, the ruthenium metal compound, triphenylphosphine and phosphine oxide are such that the final contents of the compound represented by formula I, the compound represented by formula II, metal ruthenium, metal rhodium, phosphine and phosphine oxide in the prepared HNBR are as shown in Table 1.

[0171] Table 1

[0172]

[0173] Test Case

[0174] S1. Add diisopropylbenzene peroxide and triallyl isocyanurate in Table 2 to the HNBR prepared in the examples and comparative examples, mix on an internal mixer for 20 minutes, leave for 4 hours after discharge, add diisopropylbenzene peroxide and triallyl isocyanurate, mix on an internal mixer at not more than 100° C. for 40 minutes to obtain a rubber compound.

[0175] S2. The mixed rubber was vulcanized according to the following vulcanization conditions: primary vulcanization (flat vulcanizer): 170°C×20min; 15MPa; secondary vulcanization (aging box): 150°C×4h to obtain vulcanized rubber. The rubber properties before aging were tested. The test results are shown in Table 3.

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

[0177] Table 2

[0178]

[0179]

[0180] Table 3

[0181]

[0182] Note: Change rate %* = (performance before aging - performance after aging) / performance before aging × 100%.

[0183] By comparing samples AS1 and DS1, and AS3 and DS2 respectively, it can be seen that when the hydrogenated nitrile rubber containing the compound represented by Formula I, the compound represented by Formula II and the ruthenium metal compound is used to prepare vulcanized rubber, the elongation at break and tear strength of the HNBR vulcanized rubber can be effectively improved, and the compression permanent deformation of the product can be reduced. At the same time, the effect of aging of the hydrogenated nitrile rubber on the elongation at break and tear strength, and the compression permanent deformation of the product can be reduced, and the aging resistance of the product is improved.

[0184] By comparing samples AS3 with DS2, DS3, and DS4, it can be seen that when hydrogenated nitrile rubber containing the compound represented by formula I, the compound represented by formula II, and the ruthenium metal compound is used to prepare vulcanized rubber, compared with hydrogenated nitrile rubber containing only the compound represented by formula I or the compound represented by formula II, the mechanical properties of the HNBR vulcanized rubber can be improved, and at the same time, the effect of product aging on the elongation at break, tear strength, and compression permanent deformation can be better improved, and the aging resistance is improved.

[0185] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A hydrogenated nitrile rubber, characterized in that The hydrogenated nitrile rubber contains a compound represented by formula I, a compound represented by formula II and a ruthenium-containing metal compound; In Formula I, R1, R2 and R3 are each independently selected from C1-C8 alkyl, C4-C8 cycloalkyl, C6-C 15 Aryl or C7-C 15 Aralkyl; (L o M) p Y q Formula II In formula II, o L are the same or different and are independently C1-C8 alkyl, C4-C8 cycloalkyl, C6-C 15 Aryl or C7-C 15 The aralkyl group, M is phosphorus or arsenic, q Y are the same or different and are each independently an anion, o is 3, 4, 5 or 6, p is 1, 2 or 3, q ​​is 1, 2 or 3; Based on the weight of the hydrogenated nitrile rubber, the content of the compound represented by formula I is less than or equal to 2 wt %; Based on the weight of the hydrogenated nitrile rubber, the content of the compound represented by formula II is less than or equal to 1wt%; Based on the weight of hydrogenated nitrile rubber, the content of metal ruthenium is 0.0001wt%-1wt%.

2. The hydrogenated nitrile rubber according to claim 1, wherein In Formula I, R1, R2 and R3 are each independently selected from C6-C 15 Aryl or C7-C 15 Aralkyl; Preferably, based on the weight of the hydrogenated nitrile rubber, the content of the compound represented by formula I is less than or equal to 1 wt %.

3. The hydrogenated nitrile rubber according to claim 1 or 2, wherein In Formula II, o L are the same or different and are each independently C6-C 15 The aromatic group; Preferably, the compound represented by formula II is (PPh4)Cl and / or (PPh4)Br; Preferably, based on the weight of the hydrogenated nitrile rubber, the content of the compound represented by formula II is less than or equal to 0.9 wt %.

4. The hydrogenated nitrile rubber according to any one of claims 1 to 3, wherein Based on the weight of hydrogenated nitrile rubber, the content of metal ruthenium is 0.0001wt%-0.8wt%; Preferably, the ruthenium-containing metal compound is a metal ruthenium compound and / or a metal rhodium ruthenium compound; Preferably, when the ruthenium-containing metal compound comprises a metal rhodium ruthenium compound, based on the weight of the hydrogenated nitrile rubber, the content of metal ruthenium is 0.0001wt%-1wt%, preferably 0.0001wt%-0.5wt%; the content of metal rhodium is 0.0001wt%-1wt%, preferably 0.0001wt%-0.5wt%; Preferably, 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, o R 2 The same or different, each independently selected from C1-C8 alkyl, C4-C8 cycloalkyl, C6-C 15 Aryl or C7-C 15 Aralkyl; A 2 Selected from phosphorus, arsenic, sulfur or sulfoxide group S=O; n X 2 are the same or different and are each independently selected from hydrogen or an anion; m is 2, 3 or 4; j is 2 or 3; n is 1, 2 or 3. Preferably, the metal rhodium ruthenium compound is a compound represented by formula IV: M 1 a M 2 b Z c N d Formula IV Among them, M 1 Rhodium, M 2 For ruthenium, d N are the same or different, and are each independently an organic phosphine, an organic cerium, a nitrogen-containing organic compound, a sulfur-containing organic compound or an oxygen-containing organic compound, more preferably, N is an organic monophosphine; more preferably, N is triphenylphosphine; c Z are the same or different and are independently chlorine, bromine or hydrogen, 1≤a≤6, 1≤b≤3, 3≤m≤7, 6≤n≤21.

5. The hydrogenated nitrile rubber according to any one of claims 1 to 4, wherein The hydrogenated nitrile rubber further comprises phosphine and / or phosphine oxide; Preferably, based on the weight of the hydrogenated nitrile rubber, the content of the phosphine is 0.001 wt%-10 wt%, and the content of the phosphine oxide is 0.001 wt%-10 wt%.

6. The hydrogenated nitrile rubber according to claim 5, wherein The phosphine is selected from organic monophosphines and / or organic diphosphines; Preferably, the phosphine is a compound represented by formula V and / or a compound represented by formula VI: Wherein, L1-L7 are each independently selected from C1-C8 alkyl, C4-C8 cycloalkyl, C6-C 15 Aryl or C7-C 15 wherein Y is selected from an alkyl group, an alkenyl group or an alkynyl group.

7. The hydrogenated nitrile rubber according to claim 5 or 6, wherein The phosphine oxide is a compound represented by formula VII and / or a compound represented by formula VIII: Wherein, M1-M7 are each independently selected from C1-C8 alkyl, C4-C8 cycloalkyl, C6-C 15 Aryl or C7-C 15 wherein Y is selected from an alkyl group, an alkenyl group or an alkynyl group.

8. The hydrogenated nitrile rubber according to any one of claims 1 to 7, wherein The hydrogenated nitrile rubber is a product of hydrogenation reaction of nitrile rubber; Preferably, the nitrile rubber is selected from binary nitrile rubber and / or ternary nitrile rubber; Preferably, 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; Preferably, the ternary nitrile rubber is selected from the group consisting of 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)acrylic rubber, butadiene-acrylonitrile-methyl (meth)acrylate rubber, butadiene-acrylonitrile-ethyl (meth)acrylate rubber, butadiene-acrylonitrile-tert-butyl (meth)acrylate rubber, butadiene-acrylonitrile-butyl (meth)acrylate rubber, butadiene-acrylonitrile-(meth)acrylate rubber At least one of rubber, butadiene-(meth)acrylonitrile-methyl acrylate rubber, butadiene-(meth)acrylonitrile-ethyl acrylate rubber, butadiene-(meth)acrylonitrile-t-butyl acrylate rubber, butadiene-(meth)acrylonitrile-butyl acrylate rubber, butadiene-(meth)acrylonitrile-(meth)acrylic rubber, butadiene-(meth)acrylonitrile-methyl (meth)acrylate rubber, butadiene-(meth)acrylonitrile-ethyl (meth)acrylate rubber, butadiene-(meth)acrylonitrile-t-butyl (meth)acrylate rubber and butadiene-(meth)acrylonitrile-butyl (meth)acrylate rubber.

9. A method for preparing the hydrogenated nitrile rubber according to any one of claims 1 to 8, characterized in that: The preparation method comprises: Adding the compound represented by formula I, the compound represented by formula II, optionally a ruthenium-containing metal compound, optionally a phosphine and optionally a phosphine oxide to a hydrogenated nitrile rubber solution, and obtaining the hydrogenated nitrile rubber after stirring, coagulation and drying; or; The hydrogenated nitrile rubber is obtained by adding the compound represented by formula I, the compound represented by formula II, optionally a ruthenium-containing metal compound, optionally a phosphine and optionally a phosphine oxide into the hydrogenated nitrile rubber and mixing them.

10. A hydrogenated nitrile rubber composition, characterized in that The hydrogenated nitrile rubber composition comprises the hydrogenated nitrile rubber according to claims 1-8.

11. A vulcanized rubber, characterized in that: The vulcanized rubber is obtained by mixing and vulcanizing the hydrogenated nitrile rubber composition according to claim 10.

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