Hydrogenated nitrile rubber and composition thereof, and vulcanized rubber

Abstract

The invention relates to the field of nitrile rubber, and discloses a hydrogenated nitrile rubber composition and vulcanized rubber. The hydrogenated butadiene-acrylonitrile rubber composition comprises a compound A as shown in a formula I and a compound B as shown in a formula II: # imgabs0 # (LoM) pYq, based on the weight of the hydrogenated nitrile rubber, the content of the compound A is less than or equal to 2wt%; the content of the compound B is less than or equal to 1wt% based on the weight of the hydrogenated nitrile rubber. According to the nitrile rubber composition, the vulcanized rubber prepared from the hydrogenated nitrile rubber composition can still keep good mechanical properties under the condition that the hydrogenation catalyst and the phosphine ligand of the hydrogenated nitrile rubber are not removed or are not completely removed, namely a certain amount of hydrogenation catalyst and phosphine ligand are contained.

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 elastomer. Due to the special structure of HNBR, it not only has the oil resistance, wear resistance, low temperature resistance and other properties of NBR, but also has better thermal stability and oil resistance. Its vulcanized rubber also shows excellent tolerance to high and low temperatures and oil. Due to a series of product characteristics, HNBR is widely used in the fields of automobiles, petroleum, aerospace, etc.

[0003] Hydrogenated nitrile rubber is mainly prepared by selectively hydrogenating the carbon-carbon double bonds on nitrile rubber. Commonly used hydrogenation catalysts include rhodium, ruthenium, palladium, etc. DE2539132A, US4503196A, etc. reported methods for preparing hydrogenated nitrile rubber, and both achieved good hydrogenation effects.

[0004] The catalyst for hydrogenation of nitrile rubber is expensive, and remains in the rubber after the reaction is completed, which can cause serious waste of precious metals. Meanwhile, the residue of the catalyst affects the processing properties, mechanical properties and aging resistance of HNBR and its vulcanizate to a certain extent. The residue of PPh3 in hydrogenated nitrile rubber also has a certain impact on rubber performance. EP0134023A1 discloses the existence of a certain amount of PPh3, which has caused the decline of product performances such as hydrogenated nitrile rubber hardness. Based on the above reasons, after the scientific research personnel hope to hydrogenate NBR to prepare HNBR, they can remove the catalyst and PPh3 by a certain method to ensure the performance of HNBR products, and recycle the catalyst to realize reuse. From HNBR glue, the common method for removing the catalyst is extraction, sedimentation and adsorption. The extraction method generally adopts to add ligand and catalyst to the HNBR glue to make it become a water-soluble catalyst, and then removes the catalyst by washing with water, but this method often causes a large amount of residues of ligand in HNBR, affecting the performance of HNBR products. Sedimentation method is to add sedimentation agent to HNBR glue, and its catalyst becomes insoluble solid, and then removes by centrifugation, filtration and other methods, but the precipitation particles generated by sedimentation method are small, centrifugation and filtration are difficult. Adsorption method is to contact HNBR glue with materials such as resin, and adsorb the catalyst on adsorption materials such as resin. This method has strict structural requirements on the pore size of all materials such as resin, and the removal cost is high. There are fewer reports on removing PPh3 from HNBR rubber. US5244965A discloses a method for removing phosphine ligands from hydrogenated nitrile rubber, but the phosphine precipitation particles generated by this method are extremely small, and it is difficult to remove them conveniently from the glue. On the whole, because the molecular weight of HNBR is large, the glue has a certain viscosity, and the removal of catalyst and PPh3 is complicated and costly.

[0005] 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. However, these two patents do not give any technical tips for hydrogenated nitrile rubber containing onium salt and phosphine sulfide, its composition, and vulcanized rubber. Summary of the invention

[0006] 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 maintain good mechanical properties when the hydrogenation catalyst and the phosphine ligand of the hydrogenated nitrile rubber are not removed or are not completely removed, that is, when the hydrogenation catalyst and the phosphine ligand are contained in a certain amount, the vulcanized rubber prepared from the hydrogenated nitrile rubber composition can still maintain good mechanical properties.

[0007] In order to achieve the above object, the first aspect of the present invention provides a hydrogenated nitrile rubber, characterized in that the hydrogenated nitrile rubber composition comprises a compound A shown in formula I and a compound B shown in formula II;

[0008]

[0009] 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;

[0010] (L o M) p Y q Formula II,

[0011] 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,

[0012] M is phosphorus or arsenic,

[0013] q Y are the same or different and are each independently an anion,

[0014] o is 3, 4, 5 or 6, p is 1, 2 or 3, q ​​is 1, 2 or 3;

[0015] Based on the weight of the hydrogenated nitrile rubber, the content of the compound A is less than or equal to 2wt%;

[0016] Based on the weight of the hydrogenated nitrile rubber, the content of the compound B is less than or equal to 1wt%.

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

[0018] Adding compound A represented by formula I, compound B represented by formula II, optionally phosphine and optionally phosphine oxide to hydrogenated nitrile rubber solution, stirring, coagulating and drying to obtain the hydrogenated nitrile rubber, or;

[0019] Compound A represented by formula I, compound B represented by formula II, optionally phosphine and optionally phosphine oxide are added to hydrogenated nitrile rubber, and the mixture is kneaded to obtain the hydrogenated nitrile rubber.

[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 provided by the present invention can maintain good mechanical properties of a vulcanized rubber prepared from a composition containing the hydrogenated nitrile rubber when the hydrogenation catalyst and the phosphine ligand of the hydrogenated nitrile rubber are not removed or are incompletely removed, that is, when a certain amount of the hydrogenation catalyst and the 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" means that at least one hydrogen atom in an alkyl group is replaced by an aryl group, which can be represented by Ar x -N-, wherein x Ar are the same or different and are independently aryl, N is an 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] A first aspect of the present invention provides a hydrogenated nitrile rubber, characterized in that the hydrogenated nitrile rubber comprises a compound A represented by formula I and a compound B represented by formula II;

[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 A is less than or equal to 2wt%;

[0038] Based on the weight of the hydrogenated nitrile rubber, the content of the compound B is less than or equal to 1wt%.

[0039] Further, in Formula I, R1, R2 and R3 are each independently selected from C6-C 15 Aryl or C7-C 15 of aralkyl.

[0040] In a specific embodiment of the present invention, the compound A is selected from triphenylphosphine (R1, R2 and R3 are phenyl) and / or o-methyltriphenylphosphine (R1, R2 and R3 are ).

[0041] 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.

[0042] Furthermore, in Formula II, M is phosphorus.

[0043] 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.

[0044] In a specific embodiment of the present invention, the compound B is selected from (PPh4)Cl and / or (PPh4)Br.

[0045] Furthermore, based on the weight of the hydrogenated nitrile rubber, the content of the compound A is less than or equal to 1 wt %.

[0046] Furthermore, based on the weight of the hydrogenated nitrile rubber, the content of the compound A is 0.0001 wt%-0.8 wt%.

[0047] Furthermore, based on the weight of the hydrogenated nitrile rubber, the content of the compound B is less than or equal to 0.9 wt %.

[0048] Furthermore, based on the weight of the hydrogenated nitrile rubber, the content of the compound B is 0.0001wt%-0.8wt%.

[0049] According to the present invention, the hydrogenated nitrile rubber further contains at least one of a metal compound, a phosphine and a phosphine oxide.

[0050] Furthermore, based on the weight of the hydrogenated nitrile rubber, the content of the metal compound is 0.0001wt%-1wt%, the content of the phosphine is 0.001wt%-10wt%, and the content of the phosphine oxide is 0.001wt%-10wt%.

[0051] Furthermore, based on the weight of the hydrogenated nitrile rubber, the content of the metal compound is 0.0001wt%-0.8wt%, the content of the phosphine is 0.05wt%-5wt%, and the content of the phosphine oxide is 0.02wt%-5wt%.

[0052] Furthermore, based on the weight of the hydrogenated nitrile rubber, the content of the metal compound is 0.0001wt%-0.5wt%, the content of the phosphine is 0.1wt%-3wt%, and the content of the phosphine oxide is 0.02wt%-3wt%.

[0053] In the present invention, there is no particular limitation on the type of the metal compound, which is generally a metal compound used for hydrogenation of nitrile rubber in the art. Preferably, the metal compound is a metal rhodium compound. Further preferably, the metal compound has the general formula shown in Formula III:

[0054] (R m A) z RxF n Formula III,

[0055] wherein R is independently selected from C1-C8 alkyl, C4-C8 cycloalkyl, C6-C 15 Aryl or C7-C 15A is selected from phosphorus, arsenic, sulfur or sulfoxide group S = O; X is selected from hydrogen or an anion; z is 2, 3 or 4; m is 2 or 3; n is 1, 2 or 3.

[0056] Furthermore, in Formula III, m R are the same or different and are each independently C6-C 15 More preferably, in Formula III, m R's are all phenyl.

[0057] Furthermore, in Formula III, A is phosphorus.

[0058] Further, in formula III, X is an anion. Further preferably, in formula III, X is a halogen ion. Even further preferably, in formula III, X is a chloride ion or a bromide ion. Particularly preferably, in formula III, X is a chloride ion.

[0059] In a preferred embodiment of the present invention, the metal rhodium compound is (PPh3)3RhCl.

[0060] 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.

[0061] In the present invention, the phosphine has the general formula shown in Formula IV and / or Formula V.

[0062]

[0063] 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.

[0064] Further, L1-L7 are each independently selected from C6-C 15 Aryl or C7-C 15 The aralkyl group is selected from an alkyl group.

[0065] Furthermore, the phosphine is selected from triphenylphosphine (in Formula IV, L1-L3 are phenyl), o-methyltriphenylphosphine (in Formula IV, L1-L3 are ), at least one of 1,3-bis(diphenylphosphino)propane (in Formula V, L1-L4 are phenyl groups and Y is a propane group) and 1,4-bis(diphenylphosphino)butane (in Formula V, L1-L4 are phenyl groups and Y is a butane group).

[0066] In a preferred embodiment of the present invention, the phosphine is triphenylphosphine.

[0067] 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 has the general formula shown in Formula VI and / or Formula VII:

[0068]

[0069] 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.

[0070] Further, M1-M7 are each independently selected from C6-C 15 Aryl or C7-C 15 The aralkyl group is selected from an alkyl group.

[0071] Furthermore, the phosphine oxide is selected from triphenylphosphine oxide (in formula VI, M1-M3 are phenyl), o-methyltriphenylphosphine oxide (in formula VI, M1-M3 are ), 1,3-bis(diphenylphosphine oxide)propane (in Formula VII, M1-M4 are phenyl groups and Y is a propane group) and 1,4-bis(diphenylphosphine oxide)butane (in Formula VII, M1-M4 are phenyl groups and Y is a butane group) at least one of the above.

[0072] In a preferred embodiment of the present invention, the phosphine oxide is triphenylphosphine oxide.

[0073] 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.

[0074] 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 total weight of the hydrogenated nitrile rubber, the content of the residual hydrogenation catalyst is less than or equal to 0.1wt%, and the content of the residual phosphine ligand is less than or equal to 1wt%.

[0075] In one specific embodiment of the present invention, the hydrogenation catalyst is RhCl(PPh3)3.

[0076] In the present invention, the residual phosphine ligand comprises at least one of phosphine, phosphine oxide and compound A shown in formula I. Wherein, based on the total weight of the hydrogenated nitrile rubber, the content of residual phosphine is less than or equal to 1wt%, the content of residual phosphine oxide is less than or equal to 0.8wt%, and the content of residual compound A is less than or equal to 0.5wt%.

[0077] In a specific embodiment of the present invention, the phosphine is triphenylphosphine, the phosphine oxide is triphenylphosphine oxide, and the compound A is triphenylphosphine sulfide.

[0078] In the present invention, the compound A, compound B, optional metal compound, 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 contents of the compound A, compound B, optional metal compound, optional phosphine and optional phosphine oxide in the hydrogenated nitrile rubber meet the requirements of the present invention.

[0079] According to 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.

[0080] According to 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.

[0081] 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%.

[0082] A second aspect of the present invention provides a method for preparing the above-mentioned hydrogenated nitrile rubber, characterized in that the method comprises:

[0083] Adding compound A represented by formula I, compound B represented by formula II, optionally phosphine and optionally phosphine oxide to hydrogenated nitrile rubber solution, stirring, coagulating and drying to obtain the hydrogenated nitrile rubber, or;

[0084] Compound A represented by formula I, compound B represented by formula II, optionally phosphine and optionally phosphine oxide are added to hydrogenated nitrile rubber, and the mixture is kneaded to obtain the hydrogenated nitrile rubber.

[0085] In the present invention, there is no particular requirement for the stirring conditions, as long as the hydrogenated nitrile rubber solution can be fully mixed with the compound A shown in formula I, the compound B shown in formula II, optionally the phosphine and optionally the phosphine oxide, for example, stirring at 10-10000 rpm for 1-60 min.

[0086] 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.

[0087] 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.

[0088] 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 A shown in formula I, the compound B shown in formula II, the phosphine and the phosphine oxide can be fully mixed and uniformly mixed, for example, mixing at 25-200° C. for 2-300 min.

[0089] In the present invention, the hydrogenated nitrile rubber solution or the hydrogenated nitrile rubber is a product of a hydrogenation reaction of nitrile rubber.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] In one specific embodiment of the present invention, the vulcanized rubber is prepared according to the following steps:

[0095] S1, mixing hydrogenated nitrile rubber, compound A shown in formula I, compound B shown in formula II, optionally a metal compound, optionally a phosphine and optionally a phosphine oxide to obtain a premix;

[0096] S2, mixing the premix with other components except the vulcanizing agent and the accelerator for the first time to obtain a rubber compound I;

[0097] S3, mixing the rubber mix, the vulcanizing agent and the accelerator for a second time to obtain a rubber mix II;

[0098] S4, performing secondary vulcanization on the rubber mix to obtain the vulcanized rubber.

[0099] In the present invention, there is no particular limitation on the mixing method in step S1, and a conventional mixing method in the art may be adopted, such as stirring mixing or mixing in an open mill. There is no particular limitation on the conditions for stirring mixing or mixing in an open mill, and the mixing may be carried out under conventional conditions in the art.

[0100] In the present invention, there is no particular limitation on the equipment used for the first mixing or the second mixing, and the first mixing or the second mixing can be performed 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 the first mixing or the second mixing, as long as the components can be fully mixed and uniformly mixed, for example, mixing at a temperature not higher than 100° C. for 2-300 min.

[0101] In the present invention, the secondary vulcanization may be a combination of conventional vulcanization methods in the art, such as primary vulcanization using a flat vulcanizer and secondary vulcanization using an aging box.

[0102] There is no particular limitation on the conditions of primary vulcanization or secondary vulcanization, and conventional vulcanization conditions in the art may be used. For example, the conditions of primary vulcanization include: vulcanization temperature of 100-180°C, vulcanization time of 5-100 min, and vulcanization pressure of 6-20 MPa. The conditions of secondary vulcanization include: vulcanization temperature of 80-180°C, and vulcanization time of 1-24 h.

[0103] The present invention will be described in detail below by way of examples. In the following examples,

[0104] The contents of the residual compound A shown in formula I, the residual phosphine and the residual phosphine oxide in the hydrogenated nitrile rubber were measured by liquid chromatography (UPLC-i class, Waters Company, USA);

[0105] The residual hydrogenation catalyst content (in terms of rhodium) in hydrogenated nitrile rubber was measured by inductively coupled plasma emission spectroscopy (Optima 8300, PE Company, USA);

[0106] Hardness: Shore A hardness was measured using a Shore hardness tester (HT 3000, Montech, Germany) according to GB / T531.1-2008.

[0107] 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.

[0108] 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.

[0109] The raw materials used in the examples and comparative examples are all commercially available.

[0110] Preparation Example

[0111] Preparation of hydrogenated nitrile rubber:

[0112] (1) dissolving nitrile rubber (purchased from Ruiong Company, brand 3335 and 4050, mixed at a mass ratio of 1:1) in chlorobenzene (nitrile rubber concentration 4 wt%) to obtain a rubber solution, adding it into a reaction kettle, and degassing;

[0113] (2) adding hydrogenation catalysts RhCl(PPh3)3 (0.1 wt% of the mass of the nitrile rubber) and PPh3 (1 wt% of the mass of the nitrile rubber);

[0114] (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;

[0115] (4) adding a chelating resin (brand name: CH-97, purchased from Kehaisi (Beijing) Technology Co., Ltd.) in a ratio of 1:1 to the mass of the nitrile rubber to the hydrogenated product of step (3), removing the hydrogenation catalyst, and obtaining an HNBR glue solution;

[0116] (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.

[0117] After testing, the hydrogenation degree of HNBR is 99.1%. Based on the weight of hydrogenated nitrile rubber, the content of residual hydrogenation catalyst (in terms of rhodium) is 0.001wt%, the content of residual phosphine (triphenylphosphine) is 0.4wt%, the content of residual phosphine oxide (triphenylphosphine oxide) is 0.1wt%, and the content of residual compound A (triphenylphosphine sulfide) is 0wt%.

[0118] Example 1

[0119] S1. Add triphenylphosphine (S=PPh3), (PPh4)Cl or (PPh4)Br, a metal compound (RhCl(PPh3)3), triphenylphosphine (PPh3) and phosphine oxide (triphenylphosphine oxide O=PPh3) to the HNBR rubber obtained in the preparation example, and mix them evenly on an open mixing mill at room temperature to obtain a premix; wherein the final contents of triphenylphosphine, (PPh4)Cl or (PPh4)Br, a metal compound (RhCl(PPh3)3), triphenylphosphine (PPh3) and phosphine oxide (triphenylphosphine oxide O=PPh3) are as shown in Table 1.

[0120] S2, in the premix, except dicumyl peroxide and triallyl isocyanurate, other components (amounts as shown in Table 2) were mixed on an internal mixer for 20 minutes, and after discharging, a rubber mix I was obtained, which was allowed to stand for 4 hours;

[0121] S3, adding dicumyl peroxide and triallyl isocyanurate to the rubber mix I, and mixing for 40 minutes at a temperature not higher than 100° C. on an internal mixer to obtain a rubber mix II;

[0122] S4. The mixed rubber II was vulcanized according to the following conditions: primary vulcanization (flat vulcanizer): 170°C × 20 min; pressure 15 MPa; secondary vulcanization (aging box): 150°C × 4 h, to obtain vulcanized rubber AS1.

[0123] Examples 2-7 and Comparative Examples 1-6

[0124] Vulcanized rubbers were prepared according to the method of Example 1, except that the amounts of triphenylphosphine, (PPh4)Cl or (PPh4)Br, metal compound (RhCl(PPh3)3), triphenylphosphine (PPh3) and phosphine oxide (triphenylphosphine oxide O=PPh3) were different from those in Example 1, as shown in Table 1. Vulcanized rubbers AS2-AS5 and vulcanized rubbers DS1-DS5 were obtained, respectively.

[0125] Table 1

[0126]

[0127]

[0128] Table 2

[0129] raw material Number of copies HNBR 100 White Carbon Black 45 Zinc Oxide 5 Stearic acid 0.50 Titanium dioxide 5 Ethylene glycol 2 Di(butoxy-ethoxy-ethyl) adipate 5 Silane coupling agent A-172 1 Dicumyl Peroxide DCP 6 2,6-Di-tert-butyl-p-cresol 1.5 Triallyl isocyanurate 1.5 total 172.5

[0130] The properties of the vulcanized rubbers obtained in the examples and comparative examples were tested, and the results are shown in Table 3.

[0131] Table 3

[0132]

[0133]

[0134] As can be seen from Table 3, by comparing the vulcanized rubbers AS1 and DS1, AS2 and DS2, AS4 and DS3, respectively, it can be seen that the vulcanized rubber prepared from the hydrogenated nitrile rubber composition containing the compound A described in Formula I and the compound B shown in Formula II can effectively improve the elongation at break and tear strength of the HNBR vulcanized rubber and reduce the compression permanent deformation of the product. Comparing the vulcanized rubbers AS4 and DS3, DS4, and DS5, compared with the vulcanized rubbers DS3-DS6 containing the compound A shown in Formula I or the compound B shown in Formula II alone, not containing the compound A shown in Formula I and the compound B shown in Formula II at the same time, and having too high a dosage of the compound A and the compound B, the vulcanized rubber AS4 prepared from the nitrile rubber composition containing the compound A shown in Formula I and the compound B shown in Formula II has a higher elongation at break, tear strength and low compression permanent deformation, indicating that the addition of the compound A shown in Formula I and the compound shown in Formula II significantly improves the mechanical properties of the HNBR vulcanized rubber.

[0135] 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 comprises a compound A shown in formula I and a compound B shown in formula II: 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 A is less than or equal to 2wt%; Based on the weight of the hydrogenated nitrile rubber, the content of the compound B is less than or equal to 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, the compound A is selected from triphenylphosphine and / or methyltriphenylphosphine.

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, in formula II, M is phosphorus; Preferably, in formula II, Y is a halogen ion; More preferably, the compound B is selected from (PPh4)Cl and / or (PPh4)Br.

4. The hydrogenated nitrile rubber according to any one of claims 1 to 3, wherein Based on the weight of the hydrogenated nitrile rubber, the content of the compound A is less than or equal to 1wt%; Preferably, based on the weight of the hydrogenated nitrile rubber, the content of the compound B is less than or equal to 0.9 wt %.

5. The hydrogenated nitrile rubber according to any one of claims 1 to 4, wherein The hydrogenated nitrile rubber further contains at least one of a metal compound, a phosphine and a phosphine oxide; Preferably, based on the weight of the hydrogenated nitrile rubber, the content of the metal compound is 0.0001wt%-1wt%, the content of the phosphine is 0.001wt%-10wt%, and the content of the phosphine oxide is 0.001-10wt%.

6. The hydrogenated nitrile rubber according to claim 5, wherein The metal compound is a metal rhodium compound; Preferably, the metal compound has the general formula shown in Formula III: (R m A) z RxF n Formula III, wherein m R are the same or different and are independently selected from C1-C8 alkyl, C4-C8 cycloalkyl, C6-C 15 Aryl or C7-C 15 A is selected from phosphorus, arsenic, sulfur or sulfoxide group S = O; n X are the same or different, each independently hydrogen or an anion; z is 2, 3 or 4; m is 2 or 3; n is 1, 2 or 3.

7. The hydrogenated nitrile rubber according to claim 5 or 6, wherein The phosphine is selected from organic monophosphines and / or organic diphosphines; Preferably, the phosphine has the general formula shown in Formula IV and / or Formula V: 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.

8. The hydrogenated nitrile rubber according to any one of claims 5 to 7, wherein The phosphine oxide has the general formula shown in Formula VI and / or Formula VII: 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.

9. The hydrogenated nitrile rubber according to any one of claims 1 to 8, wherein The hydrogenated nitrile rubber is obtained by hydrogenating the 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.

10. A method for preparing the hydrogenated nitrile rubber according to any one of claims 1 to 9, characterized in that: The method comprises: Adding compound A represented by formula I, compound B represented by formula II, optionally phosphine and optionally phosphine oxide to hydrogenated nitrile rubber solution, stirring, coagulating and drying to obtain the hydrogenated nitrile rubber, or; Compound A represented by formula I, compound B represented by formula II, optionally phosphine and optionally phosphine oxide are added to hydrogenated nitrile rubber, and the mixture is kneaded to obtain the hydrogenated nitrile rubber.

11. A hydrogenated nitrile rubber composition, characterized in that The hydrogenated nitrile rubber composition comprises the hydrogenated nitrile rubber according to any one of claims 1 to 9.

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

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