Hydrogenation catalyst composition and application thereof as well as hydrogenated butadiene-acrylonitrile rubber and preparation method thereof

Abstract

The invention discloses a hydrogenation catalyst composition and an application thereof, and hydrogenated nitrile rubber and a preparation method thereof, the hydrogenation catalyst composition contains a hydrogenation catalyst, a ligand and an auxiliary agent, and the auxiliary agent is selected from one or more than two of compounds represented by a formula II. The preparation method of the hydrogenated butadiene-acrylonitrile rubber comprises the step of contacting a rubber solution containing butadiene-acrylonitrile rubber with hydrogen under hydrogenation reaction conditions in the presence of the hydrogenation catalyst composition. The hydrogenation catalyst composition disclosed by the invention has obviously improved hydrogenation reaction activity, can be used for hydrogenation reaction of nitrile rubber, can effectively improve the reaction speed and shorten the reaction time, can improve the hydrogenation degree of a product, and is relatively low in comprehensive application cost. (AoM) pYq (Formula II).

Description

Technical Field

[0001] The invention relates to a hydrogenation catalyst composition and application thereof, and also relates to a method for preparing hydrogenated nitrile rubber using the hydrogenation catalyst composition and the hydrogenated nitrile rubber prepared by the method. Background Art

[0002] Hydrogenated nitrile rubber is a highly saturated nitrile rubber, which is mainly produced by hydrogenating the double bonds of nitrile rubber. Hydrogenated nitrile rubber not only has good wear resistance, low temperature resistance (-40℃), oxidation resistance, ozone resistance and other properties, but more importantly, it has excellent thermal stability. It plays an irreplaceable role in the national economy and national defense construction. It is an important strategic material resource that is indispensable in key areas such as aerospace, high-speed rail shipping, deep-sea diving, and deep drilling and oil production.

[0003] In the manufacture of hydrogenated nitrile rubber, catalytic hydrogenation of nitrile rubber is the key technology. The main challenge in producing hydrogenated nitrile rubber is to achieve the selective hydrogenation of carbon-carbon units while maintaining the integrity of the cyanide group in the rubber, which is mainly achieved by using precious metal catalysts. Over the years, the focus of hydrogenated nitrile rubber technology development has been on: how to use a new, cheap, and efficient catalyst system to prepare a hydrogenated nitrile rubber product with high saturation and low gel content; how to achieve more efficient selective hydrogenation of carbon-carbon double bonds (C=C) by continuously improving the method based on the existing catalyst system.

[0004] At present, the hydrogenation method of hydrogenated nitrile rubber homogeneous solution still mainly uses rhodium metal organic complex as hydrogenation catalyst. Although this catalytic system has very high hydrogenation selectivity and reaction activity for carbon-carbon double bonds (C=C) in nitrile rubber, the catalyst is expensive and the product price has remained high. Through continuous research on hydrogenation systems, developing a cheap and efficient catalyst system to improve hydrogenation activity and avoid unnecessary side reactions is the focus and difficulty of research in this field. Summary of the invention

[0005] The purpose of the present invention is to overcome the shortcomings of the existing homogeneous solution hydrogenation method, that is, the efficiency of the hydrogenation reaction needs to be further improved and the cost is high, and to provide a hydrogenation catalyst composition, the hydrogenation reaction activity of the composition is significantly improved, and the hydrogenation degree of the product can be significantly improved when used in the hydrogenation reaction of nitrile rubber, thereby effectively reducing the cost of the hydrogenation reaction.

[0006] The inventors of the present invention have found in their research that the use of a hydrogenation catalyst and a ligand in combination with a phosphorus or arsenic-containing additive can effectively improve the hydrogenation reaction activity of the hydrogenation catalyst, increase the hydrogenation reaction rate and the hydrogenation degree of the product, and thus effectively reduce the cost of the hydrogenation reaction. This has led to the completion of the present invention.

[0007] According to a first aspect of the present invention, the present invention provides a hydrogenation catalyst composition, the composition comprising a hydrogenation catalyst, a ligand and an auxiliary agent.

[0008] The hydrogenation catalyst is one or more compounds selected from the group consisting of:

[0009] M 1 a M 2 b X m L n (Formula I)

[0010] In Formula I, M 1 Rhodium, M 2 For ruthenium,

[0011] n L are the same or different and are independently selected from an organic phosphine, an organic cerium, a nitrogen-containing organic compound, a sulfur-containing organic compound or an oxygen-containing organic compound,

[0012] m X are the same or different and are each independently chlorine, bromine or hydrogen,

[0013] 1≤a≤6, 1≤b≤3, 3≤m≤7, 6≤n≤21;

[0014] The auxiliary agent is one or more compounds selected from the group consisting of:

[0015] (A o M) p Y q (Formula II)

[0016] In formula II, o A's 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,

[0017] M is phosphorus or arsenic,

[0018] q Y are the same or different and are each independently an anion,

[0019] o is 3, 4, 5 or 6, p is 1, 2 or 3, and q is 1, 2 or 3.

[0020] According to a second aspect of the present invention, the present invention provides use of the catalyst composition described in the first aspect of the present invention as a catalyst for hydrogenation of nitrile rubber.

[0021] According to the third aspect of the present invention, the present invention provides a method for preparing hydrogenated nitrile rubber, the method comprising contacting a rubber solution containing nitrile rubber with hydrogen under hydrogenation reaction conditions in the presence of a hydrogenation catalyst composition to obtain a hydrogenation reaction mixture, wherein the hydrogenation catalyst composition is the composition described in the first aspect of the present invention.

[0022] According to a fourth aspect of the present invention, the present invention provides a hydrogenated nitrile rubber prepared by the method described in the third aspect of the present invention.

[0023] The hydrogenation catalyst composition of the invention has significantly improved hydrogenation reaction activity and is used for hydrogenation reaction of nitrile rubber, which can not only effectively increase the reaction speed and shorten the reaction time, but also increase the hydrogenation degree of the product, and the comprehensive application cost is low.

[0024] Other features and advantages of the present invention will be described in detail in the following detailed description. DETAILED DESCRIPTION

[0025] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0026] According to a first aspect of the present invention, the present invention provides a hydrogenation catalyst composition, which comprises a hydrogenation catalyst, a ligand and an auxiliary agent.

[0027] According to the hydrogenation catalyst composition of the present invention, the hydrogenation catalyst is one or more selected from the compounds represented by formula I.

[0028] M 1 a M 2 b X m L n (Formula I).

[0029] In Formula I, M 1 Rhodium, M 2 For ruthenium.

[0030] In formula I, n L 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. The organic phosphine may be an organic monophosphine or an organic diphosphine. Preferably, in formula I, L is an organic monophosphine. More preferably, in formula I, L is triphenylphosphine.

[0031] In formula I, m Xs are the same or different and are independently chlorine, bromine or hydrogen. Preferably, in formula I, X is chlorine.

[0032] In Formula I, a, b, m and n are each integers, wherein 1≤a≤6, 1≤b≤3, 3≤m≤7, 6≤n≤21. Preferably, in Formula I, a:b is 1-3:1. More preferably, in Formula I, a:b is 2:1.

[0033] In a preferred embodiment, in Formula I, M 1 Rhodium, M 2 is ruthenium, X is chlorine, L is triphenylphosphine, a is 2, b is 1, m is 4, and n is 9. In another preferred embodiment, in Formula I, M 1 Rhodium, M 2 is ruthenium, X is chlorine, L is triphenylphosphine, a is 3, b is 1, m is 5, and n is 12. In another preferred embodiment, in Formula I, M 1 Rhodium, M 2 is ruthenium, X is chlorine, L is triphenylphosphine, a is 1, b is 1, m is 3, and n is 6.

[0034] According to the hydrogenation catalyst composition of the present invention, the hydrogenation catalyst can be commercially available, or can be prepared by a method comprising the following steps:

[0035] (1) Add L and solvent into a reaction flask and reflux to dissolve under stirring;

[0036] (2) M 1 and M 2 The metal halides are mixed and dissolved in a hot solvent, and added into a reaction flask for reaction at reflux temperature;

[0037] (3) Removing the solvent to obtain a crystalline or powdery hydrogenation catalyst.

[0038] According to the hydrogenation catalyst composition of the present invention, the auxiliary agent is one or more compounds selected from the group consisting of:

[0039] (A o M) p Y q (Formula II).

[0040] In formula II, o A's are the same or different and are independently C1-C8 alkyl, C4-C8 cycloalkyl, C6-C 15 Aryl or C7-C 15 of aralkyl.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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 alkyl, and x is an integer of 1-3.

[0045] In the present invention, C7-C 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.

[0046] Preferably, in Formula II, o A's are the same or different and are each independently C6-C 15 More preferably, in Formula II, o A's are all phenyl.

[0047] In formula II, M is phosphorus or arsenic. Preferably, in formula II, M is phosphorus.

[0048] In formula II, q Y are the same or different and are each independently an anion. Preferably, in formula II, q Y are the same or different and are each independently a halogen ion. More preferably, in formula II, q Y are the same or different and are each independently a chloride ion or a bromide ion. Further preferably, in formula II, Y is a chloride ion.

[0049] In Formula II, o is 3, 4, 5 or 6. In Formula II, p is 1, 2 or 3. In Formula II, q is 1, 2 or 3.

[0050] In a preferred embodiment, the auxiliary agent is (PPh4)Cl and / or (PPh4)Br.

[0051] According to the hydrogenation catalyst composition of the present invention, the auxiliary agent can be commercially available.

[0052] According to the hydrogenation catalyst composition of the present invention, the content of the auxiliary agent can be selected according to the content of the hydrogenation catalyst. The mass of the auxiliary agent is preferably 0.001-200% of the mass of the hydrogenation catalyst (that is, relative to 100 parts by mass of hydrogenation catalyst, the mass of the auxiliary agent is 0.001-200 parts by mass), which can more effectively improve the catalytic activity of the hydrogenation catalyst so that the hydrogenation product has a higher degree of hydrogenation. More preferably, the auxiliary agent mass is 0.005-160% of the mass of the hydrogenation catalyst. Further preferably, the auxiliary agent mass is 0.05-100% of the mass of the hydrogenation catalyst. Further preferably, the auxiliary agent mass is 0.1-50% of the mass of the hydrogenation catalyst. In a preferred embodiment, the auxiliary agent mass is 0.5-30% of the mass of the hydrogenation catalyst. In a more preferred embodiment, the auxiliary agent mass is 1-20% of the mass of the hydrogenation catalyst, for example, it can be 5-15%.

[0053] According to the hydrogenation catalyst composition of the present invention, the ligand may be one or more of an organic phosphine, an organic cerium, a nitrogen-containing organic compound, a sulfur-containing organic compound and an oxygen-containing organic compound. The organic phosphine may be an organic monophosphine or an organic diphosphine. The ligand may be the same as L in the hydrogenation catalyst or may be different from L in the hydrogenation catalyst. Preferably, the ligand is the same as L in the hydrogenation catalyst. In a preferred embodiment, the ligand is an organic monophosphine and / or an organic diphosphine, and specific examples thereof may include but are not limited to one or more of triphenylphosphine, 1,3-bis(diphenylphosphino)propane and 1,4-bis(diphenylphosphino)butane. In a more preferred embodiment, the ligand is an organic monophosphine, which can further improve the degree of hydrogenation of the hydrogenation product. In a particularly preferred embodiment, the ligand is triphenylphosphine, which can not only further improve the degree of hydrogenation of the hydrogenation product, but also effectively reduce the production cost of the hydrogenation catalyst.

[0054] According to the hydrogenation catalyst composition of the present invention, the content of the ligand can be selected according to the content of the hydrogenation catalyst. In a preferred embodiment, the mass ratio of the ligand to the hydrogenation catalyst is 1-20:1, preferably 2-15:1, more preferably 3-10:1, such as 5-10:1.

[0055] The hydrogenation catalyst composition according to the present invention is particularly suitable as a catalyst for the hydrogenation reaction of nitrile rubber.

[0056] Therefore, according to the second aspect of the present invention, the present invention provides the use of the catalyst composition described in the first aspect of the present invention as a catalyst for the hydrogenation reaction of nitrile rubber.

[0057] According to the third aspect of the present invention, the present invention provides a method for preparing hydrogenated nitrile rubber, the method comprising contacting a rubber solution containing nitrile rubber with hydrogen under hydrogenation reaction conditions in the presence of a hydrogenation catalyst composition to obtain a hydrogenation reaction mixture, wherein the hydrogenation catalyst composition is the hydrogenation catalyst composition described in the first aspect of the present invention.

[0058] The hydrogenation catalyst composition and its composition have been described in detail above and will not be described in detail here.

[0059] According to the method of the present invention, the consumption of the hydrogenation catalyst can be selected according to the consumption of the acrylonitrile-butadiene rubber. In a preferred embodiment, the consumption of the hydrogenation catalyst is 0.01-5% of the acrylonitrile-butadiene rubber quality. In this more preferred embodiment, the consumption of the hydrogenation catalyst is more preferably 0.02-1% of the acrylonitrile-butadiene rubber quality, preferably 0.06-0.5%, when the consumption of the hydrogenation catalyst is within the scope, the degree of hydrogenation can be further improved. In a particularly preferred embodiment, the consumption of the hydrogenation catalyst is 0.08-0.3% of the acrylonitrile-butadiene rubber quality, for example 0.1-0.2%, according to this particularly preferred embodiment, not only the degree of hydrogenation improved can be obtained, but also the gel content of the hydrogenated product can be effectively reduced.

[0060] According to the method of the present invention, the hydrogenation reaction can be carried out under normal conditions. The temperature of the hydrogenation reaction can be 50-180°C, preferably 80-150°C, and more preferably 90-120°C. The hydrogen pressure can be 0.1-15MPa, preferably 4-12MPa, and more preferably 5-10MPa, and the pressure is a gauge pressure. The duration of the hydrogenation reaction can be selected according to the temperature of hydrogenation and the amount of hydrogen. Generally, the duration of the hydrogenation reaction can be 1-20 hours, preferably 4-16 hours, and more preferably 6-10 hours.

[0061] According to the method of the present invention, the content of nitrile rubber in the glue solution can be a conventional content. Generally, the mass percentage concentration of nitrile rubber in the glue solution can be 2-15%, preferably 4-12%, and more preferably 5-10%.

[0062] The solvent of the glue containing nitrile rubber can be an organic solvent sufficient to dissolve the nitrile rubber, and its specific examples can include but are not limited to: one or more of aromatic hydrocarbons, aromatic hydrocarbons substituted by halogens, halogenated alkanes, ketones and amides. In a preferred embodiment, the solvent of the glue is one or more of benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, acetone, butanone and N, N-dimethylformamide. In a more preferred embodiment, the solvent of the glue is one or more of toluene, xylene, chlorobenzene, dichlorobenzene and trichlorobenzene. In a particularly preferred embodiment, the solvent of the glue is one or more of toluene, xylene and chlorobenzene.

[0063] According to the method of the present invention, the preparation method of the glue containing nitrile rubber preferably comprises: the nitrile rubber is dissolved in a solvent, and then the nitrile rubber is charged and degassed. The nitrile rubber glue can be degassed by charging an inert gas into a container that holds the nitrile rubber glue, and then exhausting the gas, and repeating the charging and exhausting at least three times, thereby the nitrile rubber glue is rearranged and degassed.

[0064] According to the method of the present invention, the nitrile rubber can be various nitrile rubbers containing carbon-carbon double bonds (C=C) and cyano groups (-CN), and can be binary nitrile rubber and / or ternary nitrile rubber.

[0065] Preferably, the nitrile rubber is butadiene-acrylonitrile rubber, butadiene-(meth)acrylonitrile rubber, 2-methyl-1,3-butadiene-acrylonitrile rubber, 2-methyl-1,3-butadiene-(meth)acrylonitrile rubber, 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 One or more of nitrile-(meth)acrylate butyl rubber, butadiene-(meth)acrylonitrile-acrylic 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 rubber, butadiene-(meth)acrylonitrile-methyl (meth)acrylate rubber, butadiene-(meth)acrylonitrile-ethyl (meth)acrylate rubber, butadiene-(meth)acrylonitrile-tert-butyl (meth)acrylate rubber and butadiene-(meth)acrylonitrile-butyl (meth)acrylate rubber.

[0066] More preferably, the nitrile rubber is butadiene-acrylonitrile rubber and / or butadiene-(meth)acrylonitrile rubber.

[0067] According to the method of the present invention, the cyanide content in the nitrile rubber can be conventionally selected. Preferably, the cyanide content in the nitrile rubber is 20-50% by weight. The cyanide content is determined by nuclear magnetic resonance spectroscopy.

[0068] According to the method of the present invention, the organic solvent in the hydrogenation reaction mixture can be removed by conventional methods to obtain the hydrogenated nitrile rubber. For example, the organic solvent in the hydrogenation reaction mixture can be removed by a combination of one or more of methods such as ethanol condensation and steam distillation to obtain a hydrogenated product, and then the solvent on the hydrogenated product is removed to obtain a hydrogenated nitrile rubber. The present invention is not particularly limited to the method for removing the solvent on the hydrogenated product, and can be various methods commonly used by those skilled in the art. In one embodiment, the method for removing the solvent on the hydrogenated product is vacuum drying, and the temperature of the vacuum drying can be 50-100°C, preferably 55-80°C, and more preferably 60-70°C. The duration of the vacuum drying can be selected according to the temperature of the vacuum drying. Generally, the duration of the vacuum drying can be 1-10 hours, preferably 5-8 hours.

[0069] According to a fourth aspect of the present invention, the present invention provides a hydrogenated nitrile rubber prepared by the method described in the third aspect of the present invention.

[0070] The present invention is described in detail below with reference to the embodiments, but the scope of the present invention is not limited thereby.

[0071] In the following examples and comparative examples, butadiene-acrylonitrile rubber was purchased from Lanhua Company with a brand name of N21L and a cyanide content of 41% by mass.

[0072] In the following examples and comparative examples, the degree of hydrogenation of hydrogenated nitrile rubber is determined by nuclear magnetic resonance spectroscopy, and the degree of hydrogenation is calculated by the method described in "Nuclear magnetic resonance analysis method for microstructure and hydrogenation degree calculation of hydrogenated nitrile rubber [J]. Petrochemical Industry, 2014, 43: 403-405".

[0073] In the following examples and comparative examples, the method for determining the gel content is:

[0074] Weigh w1 grams of dry gelatin, add chlorobenzene to make a 1g / 100mL solution, dissolve for 24 hours, pour the solution into a 360-mesh filter with a constant weight (w2 grams), and then dry the 360-mesh filter with insoluble matter to a constant weight, and record the weight as w3 grams. Calculate the gel content according to the following formula:

[0075] Gel content = (w3-w2) / w1×10 6 ppm.

[0076] In the following examples and comparative examples, unless otherwise specified, pressures are gauge pressures.

[0077] Preparation Example 1

[0078] This preparation example is used to illustrate the hydrogenation catalyst M 1a M 2 b X m L n (P1) preparation method, wherein M 1 Rhodium, M 2 is ruthenium, X is chlorine, L is triphenylphosphine, a:b is 2:1, m is 4, and n is 9.

[0079] 4.5 g of PPh3 was dissolved in a hot ethanol solution at 70°C under argon protection, 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, the reflux reaction was maintained for 2.5 hours, and then the temperature was lowered to 25°C, the reaction mixture was filtered, and the obtained solid phase was washed with ether to obtain a powdered hydrogenation catalyst, in which Rh:Ru=2:1 (molar ratio).

[0080] Preparation Example 2

[0081] This preparation example is used to illustrate the hydrogenation catalyst M 1 a M 2 b X m L n (P2) preparation method, wherein M 1 Rhodium, M 2 is ruthenium, X is chlorine, L is triphenylphosphine, a:b is 3:1, m is 5, and n is 12.

[0082] 6 g of PPh3 was dissolved in a hot ethanol solution at 70°C under argon protection, 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, the reflux reaction was maintained for 2.5 hours, and then the temperature was lowered to 25°C, the reaction mixture was filtered, and the obtained solid phase was washed with ether to obtain a powdered hydrogenation catalyst, in which Rh:Ru=3:1 (molar ratio).

[0083] Preparation Example 3

[0084] This preparation example is used to illustrate the catalyst M for hydrogenation 1 a M 2 b X m L n (P3) preparation method, wherein M1 Rhodium, M 2 is ruthenium, X is chlorine, L is triphenylphosphine, a:b is 1:1, m is 3, and n is 6.

[0085] 3 grams of PPh3 were dissolved in a hot ethanol solution at 70°C under argon protection, 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 was washed with ether to obtain a powdered hydrogenation catalyst, in which Rh:Ru=1:1 (molar ratio).

[0086] Examples 1-12 are used to illustrate the hydrogenation catalyst composition and hydrogenated nitrile rubber and the preparation method thereof of the present invention.

[0087] Embodiment 1-12 adopts the following method to prepare hydrogenated nitrile rubber:

[0088] (1) dissolving the nitrile rubber in an organic solvent to obtain a nitrile rubber solution, and degassing the nitrile rubber solution;

[0089] (2) adding a hydrogenation catalyst, a ligand and an auxiliary agent to the nitrile rubber liquid, then charging hydrogen gas, and reacting with stirring, wherein the reaction conditions include: a reaction temperature of B°C, a hydrogen pressure of AMPa, and a reaction time of C hours;

[0090] (3) The hydrogenation reaction mixture was condensed with ethanol to precipitate a hydrogenation product, and the hydrogenation product was vacuum dried at 60° C. for 8 hours to obtain a hydrogenated nitrile rubber.

[0091] In Examples 1-12, the concentration of the rubber solution (i.e., the mass percentage concentration of the nitrile rubber in the rubber solution), the catalyst / nitrile rubber (i.e., the mass ratio of the hydrogenation catalyst to the nitrile rubber), the ligand / catalyst (i.e., the mass ratio of the ligand to the hydrogenation catalyst), the auxiliary agent / catalyst (i.e., the mass ratio of the auxiliary agent to the hydrogenation catalyst), the reaction conditions A, B and C, the hydrogenation degree of the obtained hydrogenated product, and the measurement results of the cyanide reduction are shown in Table 1.

[0092] Comparative Examples 1-5

[0093] Comparative Examples 1-5 use the same method as Examples 1-12 to prepare hydrogenated nitrile rubber, except that the reaction conditions are as shown in Table 1, and the hydrogenation degree and cyanide reduction of the prepared hydrogenated nitrile rubber are listed in Table 1.

[0094] Table 1

[0095]

[0096]

[0097] By comparing Example 1 with Comparative Example 1, Example 2 with Comparative Example 2, and Example 3 with Comparative Example 3, it can be seen that the hydrogenation catalyst composition according to the present invention has higher hydrogenation reaction activity, and within the same reaction time, a hydrogenated product with a higher degree of hydrogenation can be obtained, thereby effectively improving the hydrogenation efficiency and reducing the hydrogenation cost.

[0098] Comparing Example 1 with Comparative Example 4, it can be seen that Example 1 can obtain substantially the same degree of hydrogenation at a lower hydrogenation catalyst dosage by using the hydrogenation catalyst composition according to the present invention, which shows that the hydrogenation catalyst composition according to the present invention has improved hydrogenation reaction activity and can effectively reduce the amount of hydrogenation catalyst, thereby reducing costs. Comparing Example 1 with Comparative Example 5, it can be seen that, under the condition of the same hydrogenation catalyst dosage, using the hydrogenation catalyst composition according to the present invention can achieve a better hydrogenation effect in a shorter time, thereby reducing the possibility of gel formation in the hydrogenation product.

[0099] 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 hydrogenation catalyst composition comprising a hydrogenation catalyst, a ligand and an auxiliary agent, The hydrogenation catalyst is one or more compounds selected from the group consisting of: M 1 a M 2 b X m L n (Formula I) In Formula I, M 1 Rhodium, M 2 For ruthenium, n L 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, m X are the same or different and are each independently chlorine, bromine or hydrogen, 1≤a≤6, 1≤b≤3, 3≤m≤7, 6≤n≤21; The auxiliary agent is one or more compounds selected from the group consisting of: (A o M) p Y q (Formula II) In Formula II, o A's are the same or different and are each independently C 1 -C 8 Alkyl, C 4 -C 8 Cycloalkyl, C 6 -C 15 Aryl or C 7 -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, and q is 1, 2 or 3.

2. The catalyst composition according to claim 1, in, In formula I, X is chlorine, L is an organic monophosphine or an organic diphosphine, preferably an organic monophosphine, more preferably triphenylphosphine; In formula I, a:b is preferably 1-3:1, more preferably 2:

1.

3. The catalyst composition according to claim 1 or 2, in, The ligand is one or more of an organic phosphine, an organic cerium, a nitrogen-containing organic compound, a sulfur-containing organic compound and an oxygen-containing organic compound; Preferably, the ligand is an organic monophosphine; More preferably, the ligand is triphenylphosphine.

4. The catalyst composition according to any one of claims 1 to 3, in, The auxiliary agent is (PPh 4 )Cl and / or (PPh 4 )Br.

5. The catalyst composition according to any one of claims 1 to 4, in, The mass ratio of the ligand to the hydrogenation catalyst is 1-20:1, preferably 2-15:1, and more preferably 3-10:

1.

6. The catalyst composition according to any one of claims 1 to 5, in, The mass of the auxiliary agent is 0.001-200% of the mass of the hydrogenation catalyst, preferably 0.005-160%, more preferably 0.05-100%, further preferably 0.1-50%, and further preferably 1-20%.

7. Use of the catalyst composition described in any one of claims 1 to 6 as a catalyst for hydrogenation of nitrile rubber.

8. A method for preparing hydrogenated nitrile rubber, the method comprising contacting a rubber solution containing nitrile rubber with hydrogen under hydrogenation reaction conditions in the presence of a hydrogenation catalyst composition to obtain a hydrogenation reaction mixture, It is characterized in that The hydrogenation catalyst composition is the composition according to any one of claims 1 to 6.

9. The method according to claim 8, in, The amount of the hydrogenation catalyst in the hydrogenation catalyst composition is 0.01-5% of the mass of the nitrile rubber, preferably 0.02-1%, more preferably 0.06-0.5%, and further preferably 0.08-0.3%.

10. The method according to claim 8, in, The hydrogenation reaction conditions include: reaction temperature of 50-180°C, hydrogen pressure of 0.1-15MPa, reaction time of 1-20 hours, and the pressure is gauge pressure; Preferably, the hydrogenation reaction conditions include: reaction temperature of 80-150° C., hydrogen pressure of 4-12 MPa, reaction time of 4-16 hours, and the pressure is gauge pressure.

11. The method according to claim 8, in, The mass percentage concentration of the nitrile rubber in the rubber solution is 2-15%, preferably 4-12%.

12. The method according to claim 8 or 11, in, The solvent of the glue solution is one or more selected from aromatic hydrocarbons, halogen-substituted aromatic hydrocarbons, halogenated alkanes, ketones and amides; Preferably, the solvent of the glue solution is one or more of benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, acetone, butanone and N,N-dimethylformamide.

13. The method according to any one of claims 8, 11 and 12, in, The preparation method of the rubber solution comprises: dissolving the nitrile rubber in a solvent, and then performing filling and exhausting and degassing.

14. The method according to any one of claims 8 to 13, in, The nitrile rubber is a binary nitrile rubber and / or a ternary nitrile rubber; Preferably, the nitrile rubber is butadiene-acrylonitrile rubber, butadiene-(meth)acrylonitrile rubber, 2-methyl-1,3-butadiene-acrylonitrile rubber, 2-methyl-1,3-butadiene-(meth)acrylonitrile rubber, 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 One or more of nitrile-(meth)acrylate butyl rubber, butadiene-(meth)acrylonitrile-acrylic 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 rubber, butadiene-(meth)acrylonitrile-methyl (meth)acrylate rubber, butadiene-(meth)acrylonitrile-ethyl (meth)acrylate rubber, butadiene-(meth)acrylonitrile-tert-butyl (meth)acrylate rubber and butadiene-(meth)acrylonitrile-butyl (meth)acrylate rubber; More preferably, the nitrile rubber is butadiene-acrylonitrile rubber and / or butadiene-(meth)acrylonitrile rubber.

15. A hydrogenated nitrile rubber prepared by the method described in any one of claims 8 to 14.

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