Hydrogenated nitrile rubber and compositions thereof, vulcanizates

Abstract

This invention relates to the field of nitrile butadiene rubber, and discloses a hydrogenated nitrile butadiene rubber composition and a vulcanized rubber. The hydrogenated nitrile butadiene rubber composition comprises compound A of formula I and compound B of formula II: (L o M) p Y q Formula II; based on the weight of hydrogenated nitrile butadiene rubber, the content of compound A is less than or equal to 2 wt%; based on the weight of hydrogenated nitrile butadiene rubber, the content of compound B is less than or equal to 1 wt%. This nitrile butadiene rubber composition allows the vulcanized rubber obtained from the hydrogenated nitrile butadiene rubber composition to maintain good mechanical properties even when the hydrogenation catalyst and phosphine ligand in the hydrogenated nitrile butadiene rubber are not completely removed or are only partially removed, i.e., when a certain amount of hydrogenation catalyst and phosphine ligand are present.

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 elastomer. Due to its unique structure, HNBR not only possesses the oil resistance, abrasion resistance, and low-temperature resistance of NBR, but also exhibits superior thermal stability and oil resistance. Its vulcanizates also demonstrate excellent tolerance to high and low temperatures and oil. Because of these characteristics, HNBR is widely used in the automotive, petroleum, and aerospace industries.

[0003] Hydrogenated nitrile butadiene rubber (NBR) is mainly prepared by selectively hydrogenating the carbon-carbon double bonds in NBR. Commonly used hydrogenation catalysts include rhodium, ruthenium, and palladium. Methods for preparing hydrogenated NBR have been reported in DE2539132A and US4503196A, and all have achieved good hydrogenation results.

[0004] The catalysts used in the hydrogenation of nitrile butadiene rubber (NBR) are expensive, and their residues in the rubber after the reaction result in a significant waste of precious metals. Furthermore, the catalyst residues negatively impact the processing properties, mechanical properties, and aging resistance of hydrogenated NBR and its vulcanizates. The residual PPh3 in hydrogenated NBR also affects rubber properties; EP0134023A1 discloses the presence of a certain amount of PPh3, which causes a decrease in the hardness and other properties of hydrogenated NBR. For these reasons, researchers aim to remove the catalyst and PPh3 after hydrogenating NBR to produce HNBR, ensuring the performance of the HNBR product and recovering the catalyst for reuse. Common methods for removing the catalyst from the HNBR solution include extraction, sedimentation, and adsorption. Extraction typically involves adding ligands to the HNBR solution to react with the catalyst, making it water-soluble, followed by washing to remove the catalyst. However, this method often results in a large amount of ligand residue in the HNBR, affecting the product's performance. Sedimentation involves adding a sedimentation agent to the HNBR solution, causing the catalyst to become an insoluble solid, which is then removed by centrifugation and filtration. However, the precipitate particles produced by sedimentation are small, making centrifugation and filtration difficult. Adsorption involves contacting the HNBR solution with resins or other materials, adsorbing the catalyst onto them. This method has stringent requirements on the pore size and structure of all resins and other materials, resulting in high removal costs. Reports on the removal of PPh3 from HNBR rubber are scarce. US5244965A discloses a method for removing phosphine ligands from hydrogenated nitrile butadiene rubber, but the phosphine precipitate particles generated by this method are extremely small, making them difficult to remove easily from the solution. In summary, due to the large molecular weight of HNBR and the viscosity of the solution, the removal of catalysts and PPh3 is complex and costly.

[0005] CN105873957A discloses a hydrogenated nitrile butadiene rubber containing phosphine oxide or diphosphine oxide. This patent improves the modulus and compression set of the hydrogenated nitrile butadiene rubber by converting triphenylphosphine in the product to triphenylphosphine oxide. CN105873956A discloses a hydrogenated nitrile butadiene rubber containing phosphine sulfide and / or diphosphine sulfide. This patent improves the modulus of the hydrogenated nitrile butadiene rubber under different tensile stresses and the compression set after storage at high temperatures by converting triphenylphosphine in the product to triphenylphosphine sulfide. However, neither of these patents provides any technical hints regarding hydrogenated nitrile butadiene rubber containing onium salts and phosphine sulfide, their compositions, or vulcanized rubber. Summary of the Invention

[0006] The purpose of this invention is to provide a hydrogenated nitrile butadiene rubber and its composition, as well as a vulcanized rubber, which can maintain good mechanical properties even when the hydrogenation catalyst and phosphine ligand in the hydrogenated nitrile butadiene rubber are not removed or are not completely removed, i.e., when a certain amount of hydrogenation catalyst and phosphine ligand are present.

[0007] To achieve the above objectives, a first aspect of the present invention provides a hydrogenated nitrile butadiene rubber, characterized in that the hydrogenated nitrile butadiene rubber composition comprises compound A of formula I and compound B of formula II;

[0008]

[0009] 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;

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

[0011] 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,

[0012] M is phosphorus or arsenic.

[0013] Each of the q Y atoms may be the same or different, and each is an anion independently.

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

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

[0016] Based on the weight of hydrogenated nitrile butadiene rubber, the content of compound B is less than or equal to 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 method comprises:

[0018] Compound A of Formula I, compound B of Formula II, optional phosphine and optional phosphine oxide are added to hydrogenated nitrile butadiene rubber solution, and after stirring, coagulation and drying, the hydrogenated nitrile butadiene rubber is obtained, or;

[0019] Compound A of Formula I, compound B of Formula II, optional phosphine and optional phosphine oxide are added to hydrogenated nitrile butadiene rubber, and the mixture is then kneaded to obtain the hydrogenated nitrile butadiene rubber.

[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 provided by the present invention can maintain good mechanical properties in vulcanized rubber made from a composition containing the hydrogenated nitrile butadiene rubber even when the hydrogenation catalyst and phosphine ligand in the hydrogenated nitrile butadiene rubber are not removed or are not completely removed, i.e. when a certain amount of hydrogenation catalyst and phosphine ligand are present. 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 "aralkyl" refers to an alkyl group in which at least one hydrogen atom is replaced by an aryl group, and can be represented as Ar. x -N-, where x Ar atoms are the same or different, each independently being an aryl group, N 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 comprises compound A of formula I and compound B of formula II;

[0030]

[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 compound A is less than or equal to 2 wt%.

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

[0039] Furthermore, in Equation I, R1, R2, and R3 are each independently selected from C6-C 15 aryl or C7-C 15 Aryl groups.

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

[0041] 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.

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

[0043] 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.

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

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

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

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

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

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

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

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

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

[0053] In this invention, the type of metal compound is not particularly limited; it is generally a metal compound used in the art for the hydrogenation of nitrile rubber. Preferably, the metal compound is a rhodium compound. More preferably, the metal compound has the general formula shown in Formula III:

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

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

[0056] Furthermore, in Equation III, the m R's are identical or different, and each is independently C6-C. 15 The aryl group. More preferably, in Formula III, all m Rs are phenyl groups.

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

[0058] Further, in Formula III, X is an anion. More preferably, in Formula III, X is a halide ion. Even more 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 rhodium compound is (PPh3)3RhCl.

[0060] 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.

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

[0062]

[0063] 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.

[0064] Furthermore, L1-L7 are each independently selected from C6-C 15 aryl or C7-C 15 The aralkyl group, where Y is selected from alkyl groups.

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

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

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

[0068]

[0069] 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.

[0070] Furthermore, M1-M7 are each independently selected from C6-C 15 aryl or C7-C 15 The aralkyl group, where Y is selected from alkyl groups.

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

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

[0073] 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.

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

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

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

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

[0078] In this invention, the compounds A, B, optional metal compounds, 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 compounds A, B, optional metal compounds, optional phosphine, and optional phosphine oxide in the hydrogenated nitrile butadiene rubber meets the requirements of this invention.

[0079] According to the present 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.

[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)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, butadiene-(meth)acrylonitrile-acrylonitrile-acrylate 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.

[0081] In this 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 butadiene rubber, characterized in that the method comprises:

[0083] Compound A of Formula I, compound B of Formula II, optional phosphine and optional phosphine oxide are added to hydrogenated nitrile butadiene rubber solution, and after stirring, coagulation and drying, the hydrogenated nitrile butadiene rubber is obtained, or;

[0084] Compound A of Formula I, compound B of Formula II, optional phosphine and optional phosphine oxide are added to hydrogenated nitrile butadiene rubber, and the mixture is then kneaded to obtain the hydrogenated nitrile butadiene rubber.

[0085] 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 compound A of Formula I, compound B of Formula II, optional phosphine, and optional phosphine oxide, for example, stirring at 10-10000 rpm for 1-60 min.

[0086] 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.

[0087] 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.

[0088] 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 compound A of Formula I, compound B of Formula II, optional phosphine, and optional phosphine oxide, for example, mixing at 25-200°C for 2-300 minutes.

[0089] 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.

[0090] 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.

[0091] 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.

[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-mentioned hydrogenated nitrile rubber composition.

[0093] 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.

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

[0095] S1. Hydrogenated nitrile rubber, compound A of formula I, compound B of formula II, optionally a metal compound, optionally phosphine and optionally phosphine oxide are mixed to obtain a premix;

[0096] S2. The premix is ​​first mixed with other components except for the vulcanizing agent and the accelerator to obtain compound I;

[0097] S3. The compound rubber, vulcanizing agent and accelerator are mixed for a second time to obtain compound rubber II;

[0098] S4. The compound is subjected to secondary vulcanization to obtain the vulcanized rubber.

[0099] In this invention, there is no specific limitation on the mixing method in step S1; conventional mixing methods in the art can be used, such as stirring or open mill mixing. There are no particular limitations on the conditions for stirring or open mill mixing; conventional conditions in the art can be followed.

[0100] In this invention, there are no particular limitations on the equipment used for the first or second mixing; conventional mixing equipment in the art, such as open mills and / or internal mixers, can be used. There are no particular limitations on the conditions for the first or second mixing, as long as the components are sufficiently and uniformly mixed, for example, mixing at a temperature not exceeding 100°C for 2-300 minutes.

[0101] In this invention, the secondary vulcanization can be a combination of conventional vulcanization methods in the art, such as performing a primary vulcanization using a flat vulcanizing machine and then performing a secondary vulcanization using an aging chamber.

[0102] There are no particular limitations on the conditions for primary or secondary vulcanization; conventional vulcanization conditions in this field can be followed. For example, primary vulcanization conditions include: vulcanization temperature of 100-180℃, vulcanization time of 5-100 min, and vulcanization pressure of 6-20 MPa. Secondary vulcanization conditions include: vulcanization temperature of 80-180℃ and vulcanization time of 1-24 h.

[0103] The present invention will be described in detail below through embodiments. In the following embodiments,

[0104] The contents of residual compound A (shown as formula I), residual phosphine, and residual phosphine oxide in hydrogenated nitrile butadiene rubber were determined by liquid chromatography (UPLC-i class, Waters Corporation, USA).

[0105] The content of residual hydrogenation catalyst (calculated as rhodium) in hydrogenated nitrile butadiene rubber was determined by inductively coupled plasma atomic emission spectrometry (Optima 8300, PE Corporation, USA).

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

[0107] Tensile properties and tear strength: The tensile test was conducted using a material testing machine according to GB / T 528-2009 and GB / T529-2008 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.

[0108] 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.

[0109] All raw materials used in the examples and comparative examples are commercially available products.

[0110] Preparation Example

[0111] Preparation of hydrogenated nitrile butadiene rubber:

[0112] (1) Dissolve nitrile rubber (purchased from Ruiwen Company, grade 3335, 4050, mixed at a mass ratio of 1:1) in chlorobenzene (nitrile rubber concentration 4wt%) to obtain a rubber solution, add it to the reaction vessel, and purge and degas it;

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

[0114] (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.

[0115] (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.

[0116] (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.

[0117] Tests showed that the degree of hydrogenation of HNBR was 99.1%. Based on the weight of hydrogenated nitrile rubber, the content of residual hydrogenation catalyst (calculated as rhodium) was 0.001 wt%, residual phosphine (triphenylphosphine) was 0.4 wt%, residual phosphine oxide (triphenylphosphine oxide) was 0.1 wt%, and residual compound A (triphenylphosphine thiosulfate) was 0 wt%.

[0118] Example 1

[0119] S1. Triphenylphosphine (S = PPh3), (PPh4)Cl or (PPh4)Br, metal compound (RhCl(PPh3)3), triphenylphosphine (PPh3), and phosphine oxide (triphenylphosphine oxide O = PPh3) were added to the HNBR rubber prepared in the preparation example. The mixture was then stirred evenly on a two-roll mill at room temperature to obtain a premix. The final contents of triphenylphosphine, (PPh4)Cl or (PPh4)Br, metal compound (RhCl(PPh3)3), triphenylphosphine (PPh3), and phosphine oxide (triphenylphosphine oxide O = PPh3) are shown in Table 1.

[0120] S2. Mix the premix with other components (excluding dicumyl peroxide and triallyl isocyanurate) in a mixer for 20 minutes. After discharge, obtain compound I and let it stand for 4 hours.

[0121] S3. Add dicumyl peroxide and triallyl isocyanurate to compound I, and mix in an internal mixer at a temperature not exceeding 100°C for 40 minutes to obtain compound II.

[0122] S4. Mixed rubber II is vulcanized under the following conditions: First vulcanization (flat vulcanizing machine): 170℃×20min; pressure 15MPa; Second vulcanization (aging chamber): 150℃×4h, to obtain vulcanized rubber AS1.

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

[0124] Vulcanized rubber was 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 DS1-DS5 were prepared respectively.

[0125] Table 1

[0126]

[0127]

[0128] Table 2

[0129] raw material Number of copies HNBR 100 precipitate 45 Zinc oxide 5 stearic acid 0.50 Titanium dioxide 5 Ethylene glycol 2 di(butoxy-ethoxy-ethyl) adipic acid 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 prepared in the examples and comparative examples were tested, and the results are shown in Table 3.

[0131] Table 3

[0132]

[0133]

[0134] As shown in Table 3, comparing vulcanized rubbers AS1 and DS1, AS2 and DS2, and AS4 and DS3, it can be seen that the vulcanized rubber prepared from the hydrogenated nitrile rubber composition containing compound A of Formula I and compound B of Formula II can effectively improve the elongation at break and tear strength of HNBR vulcanized rubber, and reduce the compression set of the product. Comparing vulcanized rubbers AS4 and DS3, DS4, and DS5, compared to vulcanized rubbers DS3-DS6 containing only compound A of Formula I or compound B of Formula II, without both compound A of Formula I and compound B of Formula II, and with excessive amounts of compound A and compound B, vulcanized rubber AS4 prepared from the nitrile rubber composition containing both compound A of Formula I and compound B of Formula II has higher elongation at break, tear strength, and lower compression set. This indicates that the addition of compound A of Formula I and compound B of Formula II significantly improves the mechanical properties of HNBR vulcanized rubber.

[0135] 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 comprises a compound A shown in formula I and a compound B shown in formula II: 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, q is 1, 2 or 3; 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% based on the weight of the hydrogenated nitrile rubber; The hydrogenated nitrile rubber further comprises at least one of a metal compound, a phosphine and a phosphine oxide; 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% 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 compound A is selected from triphenylphosphine sulfide and / or methyl triphenylphosphine sulfide.

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, In formula II, M is phosphorus.

6. The hydrogenated nitrile rubber of claim 1, wherein, The compound B is selected from (PPh4)Cl and / or (PPh4)Br.

7. The hydrogenated nitrile rubber according to any one of claims 1 to 6, wherein The content of the compound A is less than or equal to 1wt% based on the total weight of the hydrogenated nitrile rubber.

8. The hydrogenated nitrile rubber according to any one of claims 1 to 6, wherein, The content of the compound B is less than or equal to 0.9wt% based on the weight of the hydrogenated nitrile rubber.

9. The hydrogenated nitrile rubber according to any one of claims 1 to 6, wherein, The metal compound is a metal rhodium compound.

10. The hydrogenated nitrile rubber according to any one of claims 1 to 6, wherein, The metal compound has a general formula shown in formula III: (R m A) z RhX n formula III, In this context, m Rs may be identical or different, and each R is independently selected from C1-C8 alkyl groups, C4-C8 cycloalkyl groups, C6-C8 cycloalkyl groups, and C6-C8 cycloalkyl groups. 15 aryl or C7-C 15 Aryl group; A is selected from phosphorus, arsenic, sulfur or sulfoxide group S=O; n X are the same or different, each being a hydrogen or anion independently; z is 2, 3 or 4; m is 2 or 3; n is 1, 2 or 3.

11. The hydrogenated nitrile rubber according to any one of claims 1 to 6, wherein, The phosphine is selected from an organic monophosphine and / or an organic diphosphine.

12. The hydrogenated nitrile rubber according to any one of claims 1 to 6, wherein, The phosphine has a general formula shown in formula IV and / or formula V: Formula IV Formula V; 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.

13. The hydrogenated nitrile rubber according to any one of claims 1 to 6, wherein, The phosphine oxide has a general formula shown in formula VI and / or formula VII: Formula VI Formula VII; 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 14. The hydrogenated nitrile rubber according to any one of claims 1 to 6, wherein, The hydrogenated nitrile rubber is obtained by hydrogenation of a nitrile rubber.

15. The hydrogenated nitrile rubber of claim 14, wherein, The nitrile rubber is selected from a binary nitrile rubber and / or a ternary nitrile rubber.

16. The hydrogenated nitrile rubber of claim 15, 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.

17. The hydrogenated nitrile rubber of claim 15, 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.

18. A process for the production of the hydrogenated nitrile rubber according to any one of claims 1 to 17, characterized in that The method comprises: adding compound A shown in formula I, compound B shown in formula II, optionally phosphine and optionally phosphine oxide to hydrogenated butylnitrile rubber glue solution, after stirring, coagulation, drying, obtaining the hydrogenated butylnitrile rubber, or; adding compound A shown in formula I, compound B shown in formula II, optionally phosphine and optionally phosphine oxide to hydrogenated butylnitrile rubber, after mixing, obtaining the hydrogenated butylnitrile rubber.

19. A hydrogenated nitrile rubber composition characterized in that, The hydrogenated butylnitrile rubber composition comprises the hydrogenated butylnitrile rubber according to any one of claims 1-17.

20. A vulcanizate characterized in that, The vulcanized rubber is prepared by mixing and vulcanizing the hydrogenated butylnitrile rubber composition according to claim 19. The vulcanized rubber is prepared by mixing and vulcanizing the hydrogenated butylnitrile rubber composition according to claim 19.

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