Liquid hydrogenated nitrile rubber and preparation method thereof

Abstract

The invention relates to liquid hydrogenated butadiene-acrylonitrile rubber and a preparation method thereof, and relates to the technical field of rubber materials, and the physicochemical property parameters of the liquid hydrogenated butadiene-acrylonitrile rubber are as follows: the weight-average molecular weight is 10000-300000, the molecular weight distribution index is 1.5-6.0, the weight percentage content of acrylonitrile is 15%-50%, and the Mooney viscosity is 10-60. The lithium-electrode liquid hydrogenated nitrile rubber provided by the invention has the characteristics of relatively low molecular weight, relatively narrow molecular weight distribution and the like, has relatively good compatibility with other high polymer materials, well disperses multi-walled carbon nanotubes, well reduces the viscosity of positive electrode slurry, increases the content of a conductive material in lithium ion battery slurry, and improves the conductivity of the lithium ion battery slurry. The excellent conductivity of the conductive agent is ensured, and the cycle performance of the battery is improved; the preparation method provided by the invention is simple and feasible in process, and solves the problem that the molecular weight and molecular weight distribution are difficult to control in the prior art.

Description

Technical Field

[0001] The invention relates to the technical field of rubber materials, and in particular to a liquid hydrogenated nitrile rubber and a preparation method thereof. Background Art

[0002] Hydrogenated nitrile rubber (HNBR) plays a vital role in many key industries such as aviation, petroleum, automobiles and energy due to its outstanding performance characteristics. This high-performance elastomer is made by selectively converting the unsaturated carbon-carbon double bonds in the nitrile rubber (NBR) molecular chain into saturated carbon-carbon single bonds. In this conversion process, since the highly polar nitrile group is retained, HNBR not only inherits the oil resistance of NBR, but also exhibits excellent heat resistance, aging resistance, ozone resistance, chemical corrosion resistance, as well as high strength and high tear strength and other excellent properties.

[0003] Liquid hydrogenated nitrile rubber (LHNBR), as a special category of HNBR, occupies an important position in the manufacture of special adhesives, sealing materials and elastic products of complex shapes. Especially in the field of new energy of lithium batteries, the application of LHNBR as a dispersant has attracted much attention. Dispersants are an indispensable component of lithium-ion battery slurry, and polyvinylidene fluoride (PVDF) and polyvinyl pyrrolidone (PVP) are the mainstream dispersants commonly used in positive electrode slurry systems. If the conductive agent is unevenly dispersed in the electrode slurry, it will directly affect the coating performance of the electrode slurry. The use of a pre-dispersant composition containing HNBR can significantly improve the uniformity of the dispersion of the conductive agent in the electrode slurry, thereby preparing an electrode slurry with excellent processing performance. The electrode slurry using HNBR as a dispersant not only helps the penetration of the electrolyte solution, but also ensures that the conductive agent exerts excellent conductivity, thereby reducing the electrode resistance and significantly improving the cycle performance of the battery.

[0004] However, despite the broad application prospects of LHNBR, its preparation technology still has certain limitations. At present, the preparation of LHNBR mainly follows two technical routes: one is to prepare by solution catalytic hydrogenation of liquid nitrile rubber (LNBR); the other is to prepare by corresponding treatment of solid nitrile rubber. For example, patent CN104231118A discloses a hydrogenated hydroxyl-terminated liquid nitrile rubber and a preparation method thereof, which adopts a hydrazine hydrate-boric acid-hydrogen peroxide composition catalytic hydrogenation system to hydrogenate liquid hydroxyl-terminated nitrile rubber to obtain a gel-free product with a hydrogenation degree of more than 90%. Another example is patent CN102481562A discloses a preparation method of liquid hydrogenated nitrile rubber, the molecular weight of the obtained product is between 10000 and 50000, and the molecular weight distribution index (PDI) is less than 2. However, these methods only hydrogenate the carbon-carbon double bonds in NBR when using certain hydrogenation reduction catalysts, and cannot change the molecular weight distribution index (PDI) of LHNBR.

[0005] Existing LHNBR preparation technologies, such as the two-step strategy, can produce H-NBR with controllable molecular weight and narrow molecular weight distribution, but the process is cumbersome, and it is difficult to accurately grasp the controllability of molecular weight and molecular weight distribution. For example, the method disclosed in CN102481562A requires two steps of double decomposition degradation and hydrogenation in the entire preparation process, using different metals and catalysts for different purposes, resulting in a complex synthesis process, cumbersome procedures, and a narrow molecular weight distribution range of the final product (PDI <2), which is difficult to meet the increasingly diverse product performance and application requirements.

[0006] Therefore, there is an urgent need to develop a new liquid hydrogenated nitrile rubber and a preparation method thereof to overcome the deficiencies of the prior art, improve the performance and application diversity of the product, and meet the use requirements in the field of lithium-ion batteries. Summary of the invention

[0007] In order to solve the above problems, the present invention provides a liquid hydrogenated nitrile rubber and a preparation method thereof.

[0008] In a first aspect, the present invention provides a liquid hydrogenated nitrile rubber, wherein the physical and chemical property parameters of the liquid hydrogenated nitrile rubber include: a weight average molecular weight of 60,000-300,000, a molecular weight distribution index of 2.0-6.0, a weight percentage content of acrylonitrile of 15%-50%, and a Mooney viscosity of 30-60.

[0009] Furthermore, the molecular weight distribution index of the liquid hydrogenated nitrile rubber is 2.0-4.0.

[0010] Furthermore, the Mooney viscosity of the liquid hydrogenated nitrile rubber is 35-50.

[0011] Furthermore, the weight average molecular weight of the liquid hydrogenated nitrile rubber is 60,000-300,000.

[0012] Furthermore, the weight percentage of acrylonitrile in the liquid hydrogenated nitrile rubber is 17% to 45%.

[0013] In a second aspect, the present invention provides a method for preparing the liquid hydrogenated nitrile rubber according to any one of the first aspects, the preparation method comprising the following steps:

[0014] Obtaining nitrile rubber;

[0015] The nitrile rubber, the catalyst and the organic solvent are mixed, and then an olefin metathesis reaction is carried out under an inert gas atmosphere to obtain a first reaction system;

[0016] Passing hydrogen into the first reaction system, and then continuing to perform a hydrogenation reduction reaction under an inert gas atmosphere to obtain a second reaction system;

[0017] The second reaction system is subjected to purification and post-treatment to obtain the liquid hydrogenated nitrile rubber.

[0018] Furthermore, in terms of weight percentage, the amount of the catalyst is 0.005% to 0.1% of the weight of the nitrile rubber; in terms of g / L, the weight-to-volume ratio of the nitrile rubber to the organic solvent is (100 to 300):1, and the organic solvent includes at least one of chloroform, ethylene dichloride, acetone and chlorobenzene.

[0019] Furthermore, the general structural formula of the catalyst is as shown in Formula I;

[0020] The formula I:

[0021] wherein R1 and R2 are the same or different and are each hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonyl, or alkylsulfinyl;

[0022] L is a phosphine, sulfonated phosphine, phosphate, phosphinite, phosphinate, arsine, ether, amine, amide, sulfonate, sulfoxide, carboxyl, nitrosyl, pyridine, thioether, imidazoline or imidazolidine ligand;

[0023] X1 and X2 are the same or different and are two ligands selected from the group consisting of hydrogen, halogen, pseudohalogen, straight or branched C1-C 30 -alkyl, C6-C 24 -Aryl, C1-C 20 -alkoxy, C6-C 24-Aryloxy, C3-C 20 -Alkyl diketonate, C6-C 24 -Aryl diketonate, C1-C 20 -Carboxylic acid ester, C1-C 20 -Alkyl sulfonate, C6-C 24 -Aryl sulfonate, C1-C 20 -Alkyl mercaptan, C6-C 24 -Aryl thiols, C1-C 20 -alkylsulfonyl or C1-C 20 -alkylsulfinyl;

[0024] E1, E2, E3, E4, and E5 are each independently hydrogen, halogen, nitro, nitrile, sulfoxide, sulfone, aldehyde, substituted or unsubstituted C1-C 20 Alkyl, C1-C 20 Alkylthio, C1-C 20 Alkylsilyl, C1-C 20 Alkylsilyloxy, substituted or unsubstituted C2-C 20 Heterocyclic group, substituted or unsubstituted amino group, aminoacyl group, substituted or unsubstituted C1-C 20 The carbonyl group of the alkylamino group, the substituted or unsubstituted C2-C 20 The carbonyl group of the heterocyclylamino group is connected to a substituted or unsubstituted C2-C 20 The carbonyl group of the heterocyclic group, the substituted or unsubstituted C1-C 20 The carbonyl group of the alkoxy group, the substituted or unsubstituted C6-C 20 The carbonyl, urea, substituted or unsubstituted C1-C 20 Alkylurea, substituted or unsubstituted C1-C 20 Alkylurea, substituted or unsubstituted C6-C 20 Arylurea or substituted or unsubstituted C2-C 20 Heterocyclyl urea, substituted or unsubstituted C6-C 20 Aryl, substituted or unsubstituted C6-C 20 Aryloxy.

[0025] Furthermore, the catalyst is selected from any of the following compounds:

[0026]

[0027] wherein R1 and R2 are the same or different and are each hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonyl, or alkylsulfinyl;

[0028] X1 and X2 are identical or different and are two ligands selected from the group consisting of hydrogen, halogen, pseudohalogen, linear or branched C1-C30-alkyl, C6-C24-aryl, C1-C20-alkoxy, C6-C24-aryloxy, C3-C20-alkyldiketonate, C6-C24-aryldiketonate, C1-C20-carboxylate, C1-C20-alkylsulfonate, C6-C24-arylsulfonate, C1-C20-alkylthiol, C6-C24-arylthiol, C1-C20-alkylsulfonyl or C1-C20-alkylsulfinyl;

[0029] E1, E3, and E5 are each independently hydrogen, halogen, nitro, nitrile, sulfoxide, sulfone, aldehyde, substituted or unsubstituted C1-C20 alkyl, C1-C20 alkylthio, C1-C20 alkylsilyl, C1-C20 alkylsiloxy, substituted or unsubstituted C2-C20 heterocyclyl, substituted or unsubstituted amino, aminoacyl, a carbonyl group connected to a substituted or unsubstituted C1-C20 alkylamino, a carbonyl group connected to a substituted or unsubstituted C2-C20 heterocyclylamino, a carbonyl group connected to a substituted or unsubstituted a substituted or unsubstituted C2-C20 heterocyclyl carbonyl group, a carbonyl group connected to a substituted or unsubstituted C1-C20 alkoxy group, a carbonyl group connected to a substituted or unsubstituted C6-C20 aryloxy group, a urea group, a substituted or unsubstituted C1-C20 alkylurea group, a substituted or unsubstituted C1-C20 alkylurea group, a substituted or unsubstituted C6-C20 arylurea group, or a substituted or unsubstituted C2-C20 heterocyclylurea group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C6-C20 aryloxy group;

[0030]

[0031] wherein X1 and X2 are the same or different and are two ligands selected from the group consisting of hydrogen, halogen, pseudohalogen, straight or branched C1-C 30 -alkyl, C6-C 24 -Aryl, C1-C 20 -alkoxy, C6-C 24 -Aryloxy, C3-C 20 -Alkyl diketonate, C6-C 24 -Aryl diketonate, C1-C 20 -Carboxylic acid ester, C1-C 20 -Alkyl sulfonate, C6-C 24 -Aryl sulfonate, C1-C 20 -Alkyl mercaptan, C6-C 24 -Aryl thiols, C1-C 20 -alkylsulfonyl or C1-C 20 -alkylsulfinyl;

[0032]

[0033] E1, E3, and E5 are each independently hydrogen, halogen, nitro, nitrile, sulfoxide, sulfone, aldehyde, substituted or unsubstituted C1-C20 alkyl, C1-C20 alkylthio, C1-C20 alkylsilyl, C1-C20 alkylsiloxy, substituted or unsubstituted C2-C20 heterocyclyl, substituted or unsubstituted amino, aminoacyl, a carbonyl group connected to a substituted or unsubstituted C1-C20 alkylamino, a carbonyl group connected to a substituted or unsubstituted C2-C20 heterocyclylamino, a carbonyl group connected to a substituted or unsubstituted The invention also includes a substituted C2-C20 heterocyclyl carbonyl group, a carbonyl group connected to a substituted or unsubstituted C1-C20 alkoxy group, a carbonyl group connected to a substituted or unsubstituted C6-C20 aryloxy group, a urea group, a substituted or unsubstituted C1-C20 alkylurea group, a substituted or unsubstituted C1-C20 alkylurea group, a substituted or unsubstituted C1-C20 alkylurea group, a substituted or unsubstituted C6-C20 arylurea group, or a substituted or unsubstituted C2-C20 heterocyclylurea group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C6-C20 aryloxy group.

[0034] Furthermore, the condition parameters of the olefin metathesis reaction include: reaction temperature of 80-110° C., reaction time of 0.5-2 h; the condition parameters of the hydrogenation reduction reaction include: reaction temperature of 80-200° C., hydrogen pressure of 5 MPa-9 MPa, reaction time of 2-6 h.

[0035] The above technical solution provided by the embodiment of the present invention has at least the following advantages compared with the prior art:

[0036] The embodiment of the present invention provides a liquid hydrogenated nitrile rubber and a preparation method thereof. The present invention provides a lithium-grade liquid hydrogenated nitrile rubber, which has the characteristics of low molecular weight and narrow molecular weight distribution, and has good compatibility with other polymer materials, well disperses multi-walled carbon nanotubes, and well reduces the viscosity of the positive electrode slurry, increases the content of the conductive material in the lithium-ion battery slurry, ensures the excellent conductivity of the conductive agent, and improves the cycle performance of the battery; and the preparation method of the present invention is simple and feasible, and solves the problems of the molecular weight and its molecular weight distribution being difficult to control in the prior art. Specifically:

[0037] 1) The present invention provides a lithium-grade liquid hydrogenated nitrile rubber, whose physical and chemical property parameters include: a weight average molecular weight of 10,000-300,000, preferably 60,000-250,000; a molecular weight distribution index of 1.5-6.0, preferably 2.0-4.0; a weight percentage content of acrylonitrile of 15%-50%, preferably 17%-45%, for example 35% or 43%; and a Mooney viscosity of 10-60, preferably 35-50. The liquid hydrogenated nitrile rubber has the characteristics of low molecular weight, narrow molecular weight distribution, etc., and has good compatibility with other polymer materials, well disperses multi-walled carbon nanotubes, and well reduces the viscosity of positive electrode slurry, increases the content of conductive material in lithium ion battery slurry, ensures the excellent conductivity of the conductive agent, reduces electrode resistance, and improves the cycle performance of the battery; the prepared liquid hydrogenated nitrile rubber can be used as a lithium ion battery dispersant to inhibit the aggregation of conductive material carbon nanotubes in the electrode, and form an electrode active material layer with uniform thickness during the manufacture of the electrode without the problem of collapse or cracking, thereby improving the performance of the battery, especially the capacity characteristics;

[0038] 2) Compared with the prior art, the present invention constructs a strategy for preparing lithium-grade liquid hydrogenated nitrile rubber. First, the NBR product is subjected to olefin metathesis degradation, and then the NBR is catalytically hydrogenated under certain reaction conditions to prepare liquid hydrogenated nitrile rubber with controllable molecular weight, molecular weight distribution and degree of hydrogenation, thereby solving the problem of the prior art that the molecular weight and its molecular weight distribution are difficult to control. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.

[0040] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0041] Figure 1 A schematic flow chart of a method for preparing liquid hydrogenated nitrile rubber provided in an embodiment of the present invention.

[0042] Figure 2 This is a diagram of the self-decomposition process of nitrile rubber.

[0043] Figure 3 It is a reaction equation diagram in the preparation process of the liquid hydrogenated nitrile rubber of the present invention. DETAILED DESCRIPTION

[0044] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0045] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0046] In a first aspect, the present invention provides a liquid hydrogenated nitrile rubber, wherein the physical and chemical property parameters of the liquid hydrogenated nitrile rubber include: a weight average molecular weight of 60,000-300,000, a molecular weight distribution index of 2.0-6.0, a weight percentage content of acrylonitrile of 15%-50%, and a Mooney viscosity of 30-60.

[0047] The embodiment of the present invention provides a liquid hydrogenated nitrile rubber, which has the characteristics of low molecular weight, narrow molecular weight distribution, etc., and has good compatibility with other polymer materials, well disperses multi-walled carbon nanotubes, and effectively reduces the viscosity of the positive electrode slurry, increases the content of the conductive material in the lithium-ion battery slurry, ensures the excellent conductivity of the conductive agent, and improves the cycle performance of the battery.

[0048] In some specific embodiments, the lithium-grade liquid hydrogenated nitrile rubber provided by the present invention has physical and chemical property parameters including: weight average molecular weight of 60,000-300,000, preferably 200,000-250,000; molecular weight distribution index of 2.0-6.0, preferably 2.0-4.0; weight percentage content of acrylonitrile of 15% to 50%, preferably 17% to 45%, for example 35% or 43%; Mooney viscosity of 30 to 60, preferably 35-50.

[0049] In a second aspect, the present invention provides a method for preparing the liquid hydrogenated nitrile rubber according to any one of the first aspects, such as Figure 1 As shown, the preparation method comprises the following steps:

[0050] Obtaining nitrile rubber;

[0051] The nitrile rubber, the catalyst and the organic solvent are mixed, and then an olefin metathesis reaction is carried out under an inert gas atmosphere to obtain a first reaction system;

[0052] Passing hydrogen into the first reaction system, and then continuing to perform a hydrogenation reduction reaction under an inert gas atmosphere to obtain a second reaction system;

[0053] The second reaction system is subjected to purification and post-treatment to obtain the liquid hydrogenated nitrile rubber.

[0054] The olefin metathesis reaction of nitrile rubber is the cutting and reorganization of olefin molecules under the action of metal catalysts, and the new products are formed after rearrangement. Nitrile rubber is obtained by random copolymerization of butadiene and acrylonitrile. There are C=C double bonds on the main chain and side groups. Under the action of olefin metathesis catalyst, the double bonds are broken and reorganized. In the absence of external monomers, self-metathesis reaction generally occurs, which may form short chain or ring structure, such as Figure 2 shown.

[0055] First, the nitrile rubber is crushed and dissolved in a suitable solvent, and then hydrogenated in a high-temperature and high-pressure reactor; the selected hydrogenation catalyst only selectively hydrogenates the double bonds contained therein, and does not hydrogenate the cyano group -C≡N in the acrylonitrile unit. Regardless of whether it is homogeneous hydrogenation or heterogeneous hydrogenation, HNBR often undergoes side reactions such as crosslinking after hydrogenation, and the Mooney viscosity increases significantly, and the processability is limited by the relatively high Mooney viscosity. The olefin metathesis reaction can effectively regulate the molecular weight of the polymer and selectively hydrogenate the C=C double bond under hydrogen conditions.

[0056] Compared with the prior art, the present invention constructs a strategy for preparing lithium-grade liquid hydrogenated nitrile rubber. First, NBR products are subjected to olefin metathesis degradation, and then NBR is catalytically hydrogenated under certain reaction conditions to prepare liquid hydrogenated nitrile rubber with controllable molecular weight, molecular weight distribution and hydrogenation degree. The main reaction process is as follows: Figure 3 shown.

[0057] At the same time, the prepared liquid hydrogenated nitrile rubber as a lithium-ion battery dispersant can inhibit the aggregation of conductive material carbon nanotubes in the electrode, and form an electrode active material layer with uniform thickness during the manufacture of the electrode without the problem of collapse or cracking, thereby improving the performance of the battery, especially the capacity characteristics.

[0058] In some specific embodiments, the preparation method of liquid hydrogenated nitrile rubber provided by the present invention comprises the following steps: under the protection of inert gas, in an organic solvent, firstly, carrying out olefin metathesis reaction to prepare NBR with low molecular weight and narrow molecular weight distribution, and then under the action of a catalyst, at a certain temperature and a certain pressure of hydrogen, subjecting the nitrile rubber to a hydrogenation reduction reaction to obtain liquid hydrogenated nitrile rubber.

[0059] In the present invention, the acrylonitrile content of the nitrile rubber can be 15% to 50%, preferably 17% to 45%, for example 35% or 43%. The weight average molecular weight of the nitrile rubber is 60000-300000, preferably 200000-250000. The Mooney viscosity of the nitrile rubber is 30 to 60, preferably 35 to 50. The molecular weight distribution index (PDI) of the nitrile rubber can be 2.0 to 6.0, preferably 2.0 to 4.0.

[0060] In the present invention, the inert gas may be a commonly used inert gas for such reactions in the art, such as argon (Ar) or nitrogen.

[0061] The amount of the catalyst can be selected according to conventional methods in the art, preferably 0.005% to 0.1%, more preferably 0.02% to 0.05%, where the percentage is the mass percentage of the catalyst to the nitrile rubber.

[0062] The reaction temperature of the hydrogenation reduction reaction is the conventional temperature of this type of reaction, preferably 80-200° C., more preferably 100-180° C. The pressure of the hydrogen introduced can be the conventional pressure range of 5Mpa-9Mpa for this type of reaction in the art. The time of the hydrogenation reduction reaction can be selected according to the conventional method in the art, which can be 2-6h.

[0063] The organic solvent may be a commonly used solvent for such reactions in the art, for example, one or more of chloroform, ethylene dichloride, acetone and chlorobenzene; preferably one or more of chlorobenzene, ethylene dichloride and chloroform; more preferably chlorobenzene or ethylene dichloride; most preferably chlorobenzene. The amount of the organic solvent may be selected according to conventional methods in the art, preferably 100 to 300 g of nitrile rubber / 1 L of organic solvent, for example 120 g, 160 g, 200 g or 240 g of nitrile rubber / 1 L of organic solvent.

[0064] Wherein, the catalyst includes one or more of the catalysts shown in the general formula:

[0065]

[0066] R1 and R2 are the same or different and are each hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonyl, or alkylsulfinyl, wherein in each case these groups are unsubstituted or substituted with one or more alkyl, halogen, alkoxy, aryl or heteroaryl moieties, or alternatively, the two groups R are bridged together with the common carbon atom to which they are attached to form a cyclic structure which is aliphatic or aromatic in nature and which is unsubstituted or substituted and does not contain heteroatoms.

[0067] L can be a phosphine, sulfonated phosphine, phosphate, phosphinite, phosphite, arsine, ether, amine, amide, sulfonate, sulfoxide, carboxyl, nitrosyl, pyridine, thioether, imidazoline or imidazolidine ligand. Preferably, ligand L is a C6-C 24 -arylphosphines, C1-C5-alkylphosphines, a sulfonated C6-C 24 -Arylphosphine, a C6-C 24 -Aryl phosphite, a C6-C 24 -arylphosphonites, a C6-C 24 -Aryl phosphite, a C6-C 24 -Aryl arsenide, a C6-C 24 -arylamine, a pyridine ligand, a C6-C 24 -aryl sulfoxide, a C6-C 24 -aryl ether, or a C6-C 24 -Arylamide or C1-C 10 -alkylamide ligands, each of which may be substituted by a phenyl group, which in turn may be substituted by a halogen, a C1-C5 alkyl group or a C1-C5-alkoxy group. The term "phosphine" for ligand L includes PPh3, P(p-Tol)3, P(o-Tol)3, PPh(CH3)2, P(CF3)3, P(p-FC6H4)3, P(p-CF3C6H4)3, P(C6H4-SO3Na)3, P(CH2C6H4-SO3Na)3, P(iso-Pr)3, P(CHCH3(CH2CH3))3, P(cyclopentyl)3, P(cyclohexyl)3, P(neopentyl)3 and P(neophenyl)3.

[0068] X1 and X2 are the same or different and are two ligands selected from the group consisting of hydrogen, halogen, pseudohalogen, straight or branched C1-C 30 -alkyl, C6-C 24 -Aryl, C1-C 20 -alkoxy, C6-C 24-Aryloxy, C3-C 20 -Alkyl diketonate, C6-C 24 -Aryl diketonate, C1-C 20 -Carboxylic acid ester, C1-C 20 -Alkyl sulfonate, C6-C 24 -Aryl sulfonate, C1-C 20 -Alkyl mercaptan, C6-C 24 -Aryl thiols, C1-C 20 -alkylsulfonyl or C1-C 20 -alkylsulfinyl.

[0069] E1, E2, E3, E4, and E5 can each independently be hydrogen, halogen, nitro, nitrile, sulfoxide, sulfone, aldehyde, substituted or unsubstituted C1-C 20 Alkyl, C1-C 20 Alkylthio, C1-C 20 Alkylsilyl, C1-C 20 Alkylsilyloxy, substituted or unsubstituted C2-C 20 Heterocyclic group, substituted or unsubstituted amino group, aminoacyl group, substituted or unsubstituted C1-C 20 The carbonyl group of the alkylamino group, the substituted or unsubstituted C2-C 20 The carbonyl group of the heterocyclylamino group is connected to a substituted or unsubstituted C2-C 20 The carbonyl group of the heterocyclic group, the substituted or unsubstituted C1-C 20 The carbonyl group of the alkoxy group, the substituted or unsubstituted C6-C 20 The carbonyl, urea, substituted or unsubstituted C1-C 20 Alkylurea, substituted or unsubstituted C1-C 20 Alkylurea, substituted or unsubstituted C6-C 20 Arylurea or substituted or unsubstituted C2-C 20 Heterocyclyl urea, substituted or unsubstituted C6-C 20 Aryl, substituted or unsubstituted C6-C 20 Aryloxy.

[0070] In some specific embodiments, the catalyst preparation method is:

[0071] (1) Commercially available ruthenium trichloride reacts with a compound containing ligand X1 to obtain an intermediate;

[0072] (2) dissolving the intermediate in dichloromethane and adding the carbene ligand at low temperature to react for 1 h;

[0073] (3) After the reaction is completed, add X2 ligand compound at room temperature and react for 1 hour;

[0074] (4) The precipitated product is dried and mixed with a n-hexane solution containing the L ligand, reacted at a temperature range of 60-120° C. for 2 h, and the solid product is filtered;

[0075] (5) The product is dissolved in dichloromethane, and pyridine compounds with different substitutions are added, and the reaction is carried out at high temperature for 1 hour. After the reaction is completed, the target catalyst is precipitated using n-pentane, and the final product is obtained by freezing and filtering.

[0076] The final products obtained by the above preparation method were characterized and confirmed by characterization methods such as nuclear magnetic resonance and infrared, and the characterization data of each product were consistent with the chemical structure of the product.

[0077] It should be noted that the raw material components involved in the liquid hydrogenated nitrile rubber and the preparation method thereof provided in the embodiments of the present invention, unless otherwise specified or described in detail, can be directly purchased from the market or can be prepared in-house according to existing preparation methods; at the same time, the operating steps involved in the preparation method, unless otherwise specified or described in detail, can be carried out according to existing preparation methods or using existing equipment, and the present invention document will not describe them one by one.

[0078] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples that do not specify specific conditions are usually measured according to national standards. If there is no corresponding national standard, then the conditions recommended by the manufacturer are followed.

[0079] The following raw material nitrile rubber and product liquid hydrogenated nitrile rubber raw rubber and rubber material-related characteristic parameters of the present invention are tested according to the following method:

[0080] (1) Acrylonitrile content: The content of acrylonitrile was determined in accordance with the method specified in SH / T1157.2-2015 “Determination of bound acrylonitrile content in raw rubber acrylonitrile-butadiene rubber (NBR) Part 2: Kjeldahl method”, with nuclear magnetic resonance spectroscopy as an auxiliary verification method.

[0081] (2) Hydrogenation saturation: Tested according to the method specified in standard SH / T1763 "Determination of residual unsaturation in nitrile rubber hydrogenated nitrile rubber (HNBR) - iodine value method".

[0082] (3) Molecular weight and molecular weight distribution index (PDI): tested using ECS000113 room temperature gel permeation chromatograph (Z-1601) in accordance with the method specified in GB / T21863-2008 “Gel Permeation Chromatography (GPC) Using Tetrahydrofuran as Eluent”.

[0083] The structural formula of the catalyst used in the following examples of the present invention is as follows:

[0084]

[0085] Embodiment 1:

[0086] 30g of nitrile rubber [acrylonitrile mass content 35%, Mooney viscosity ML (1+4) 100°C 35] and 270g of anhydrous chlorobenzene were added to a 500ml stainless steel reactor, and a catalyst was added after complete dissolution, with the amount being 0.03% of the nitrile rubber, and nitrogen was replaced for half an hour, and the temperature was raised to 100°C for olefin metathesis reaction. After the reaction for 1 hour, the temperature was raised to 145°C, and then hydrogen was introduced until the pressure reached 7Mpa, so that the nitrile rubber was subjected to metathesis degradation and hydrogenation reduction reaction, and the reaction was carried out for 4 hours to obtain a liquid hydrogenated nitrile rubber solution. After flocculation, washing and drying, a liquid hydrogenated nitrile rubber raw rubber was obtained.

[0087] The characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are as follows: molecular weight (Mw) is 45176, molecular weight distribution index is 2.28, acrylonitrile content is 35%, and hydrogenation degree is 99%.

[0088] Embodiment 2:

[0089] 30g of nitrile rubber [acrylonitrile mass content 35%, Mooney viscosity ML (1+4) 100°C 35] and 270g of anhydrous chlorobenzene were added to a 500ml stainless steel reactor, and a catalyst was added after complete dissolution, with the amount being 0.04% of the nitrile rubber, and nitrogen was replaced for half an hour, and the temperature was raised to 100°C for olefin metathesis reaction. After the reaction for 1 hour, the temperature was raised to 145°C, and then hydrogen was introduced until the pressure reached 7Mpa, so that the nitrile rubber was subjected to metathesis degradation and hydrogenation reduction reaction, and the reaction was carried out for 4 hours to obtain a liquid hydrogenated nitrile rubber solution. After flocculation, washing and drying, a liquid hydrogenated nitrile rubber raw rubber was obtained.

[0090] The characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are: molecular weight (Mw) is 37753, molecular weight distribution index is 2.01, acrylonitrile content is 35%, and hydrogenation degree is 99%.

[0091] Embodiment 3:

[0092] 30g of nitrile rubber [acrylonitrile mass content 35%, Mooney viscosity ML (1+4) 100°C 35] and 270g of anhydrous chlorobenzene were added to a 500ml stainless steel reactor, and a catalyst was added after complete dissolution, with the amount being 0.05% of the nitrile rubber, and nitrogen was replaced for half an hour, and the temperature was raised to 100°C for olefin metathesis reaction. After the reaction for 1 hour, the temperature was raised to 145°C, and then hydrogen was introduced until the pressure reached 7Mpa, so that the nitrile rubber was subjected to metathesis degradation and hydrogenation reduction reaction, and the reaction was carried out for 4 hours to obtain a liquid hydrogenated nitrile rubber solution. After flocculation, washing and drying, a liquid hydrogenated nitrile rubber raw rubber was obtained.

[0093] The characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are as follows: molecular weight (Mw) is 31372, molecular weight distribution index is 2.02, acrylonitrile content is 35%, and hydrogenation degree is 99%.

[0094] Embodiment 4:

[0095] 30g of nitrile rubber [acrylonitrile mass content 35%, Mooney viscosity ML (1+4) 100°C 35] and 270g of anhydrous chlorobenzene were added to a 500ml stainless steel reactor, and a catalyst was added after complete dissolution, with the amount being 0.03% of the nitrile rubber, and nitrogen was replaced for half an hour, and the temperature was raised to 100°C for olefin metathesis reaction. After the reaction for 1 hour, the temperature was raised to 130°C, and then hydrogen was introduced until the pressure reached 7Mpa, so that the nitrile rubber was subjected to metathesis degradation and hydrogenation reduction reaction, and the reaction was carried out for 5 hours to obtain a liquid hydrogenated nitrile rubber solution. After flocculation, washing and drying, a liquid hydrogenated nitrile rubber raw rubber was obtained.

[0096] The characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are: molecular weight (Mw) is 37826, molecular weight distribution index is 2.38, acrylonitrile content is 35%, and hydrogenation degree is 99%.

[0097] Embodiment 5:

[0098] 30g of nitrile rubber [acrylonitrile mass content 35%, Mooney viscosity ML (1+4) 100°C 35] and 270g of anhydrous chlorobenzene were added to a 500ml stainless steel reactor, and a catalyst was added after complete dissolution, with the amount being 0.03% of the nitrile rubber, and nitrogen was replaced for half an hour, and the temperature was raised to 100°C for olefin metathesis reaction. After the reaction for 1 hour, the temperature was raised to 150°C, and then hydrogen was introduced until the pressure reached 7Mpa, so that the nitrile rubber was subjected to metathesis degradation and hydrogenation reduction reaction, and the reaction was carried out for 7 hours to obtain a liquid hydrogenated nitrile rubber solution. After flocculation, washing and drying, a liquid hydrogenated nitrile rubber raw rubber was obtained.

[0099] The characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are as follows: molecular weight (Mw) is 41896, molecular weight distribution index is 2.185, acrylonitrile content is 35%, and hydrogenation degree is 99%.

[0100] Embodiment 6:

[0101] 30g of nitrile rubber [acrylonitrile mass content 35%, Mooney viscosity ML (1+4) 100°C 35] and 270g of anhydrous chlorobenzene were added to a 500ml stainless steel reactor, and a catalyst was added after complete dissolution, with the amount being 0.03% of the nitrile rubber, and nitrogen was replaced for half an hour, and the temperature was raised to 100°C for olefin metathesis reaction. After the reaction for 1 hour, the temperature was raised to 145°C, and then hydrogen was introduced until the pressure reached 7Mpa, so that the nitrile rubber was subjected to metathesis degradation and hydrogenation reduction reaction, and the reaction was carried out for 2 hours to obtain a liquid hydrogenated nitrile rubber solution. After flocculation, washing, and drying, a liquid hydrogenated nitrile rubber raw rubber was obtained.

[0102] The characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are as follows: molecular weight (Mw) is 47186, molecular weight distribution index is 2.29, acrylonitrile content is 35%, and hydrogenation degree is 90%.

[0103] Embodiment 7:

[0104] 30g of nitrile rubber [acrylonitrile mass content 35%, Mooney viscosity ML (1+4) 100°C 35] and 270g of anhydrous chlorobenzene were added to a 500ml stainless steel reactor, and a catalyst was added after complete dissolution, with the amount being 0.03% of the nitrile rubber, and nitrogen was replaced for half an hour, and the temperature was raised to 100°C for olefin metathesis reaction. After the reaction for 1 hour, the temperature was raised to 145°C, and then hydrogen was introduced until the pressure reached 7Mpa, so that the nitrile rubber was subjected to metathesis degradation and hydrogenation reduction reaction, and the reaction was carried out for 3 hours to obtain a liquid hydrogenated nitrile rubber solution. After flocculation, washing, and drying, a liquid hydrogenated nitrile rubber raw rubber was obtained.

[0105] The characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are as follows: molecular weight (Mw) is 46326, molecular weight distribution index is 2.32, acrylonitrile content is 35%, and hydrogenation degree is 95%.

[0106] Embodiment 8:

[0107] 30g of nitrile rubber [acrylonitrile mass content 35%, Mooney viscosity ML (1+4) 100°C 35] and 270g of anhydrous chlorobenzene were added to a 500ml stainless steel reactor, and a catalyst was added after complete dissolution, with the amount being 0.03% of the nitrile rubber, and nitrogen was replaced for half an hour, and the temperature was raised to 100°C for olefin metathesis reaction. After the reaction for 1 hour, the temperature was raised to 145°C, and then hydrogen was introduced until the pressure reached 6.5Mpa, so that the nitrile rubber was subjected to metathesis degradation and hydrogenation reduction reaction, and the reaction was carried out for 4 hours to obtain a liquid hydrogenated nitrile rubber solution. After flocculation, washing and drying, a liquid hydrogenated nitrile rubber raw rubber was obtained.

[0108] The characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are as follows: molecular weight (Mw) is 51098, molecular weight distribution index is 2.65, acrylonitrile content is 35%, and hydrogenation degree is 99%.

[0109] Embodiment 9:

[0110] 30g of nitrile rubber [acrylonitrile mass content 35%, Mooney viscosity ML (1+4) 100°C 35] and 270g of anhydrous chlorobenzene were added to a 500ml stainless steel reactor, and a catalyst was added after complete dissolution, with the amount being 0.03% of the nitrile rubber, and nitrogen was replaced for half an hour, and the temperature was raised to 100°C for olefin metathesis reaction. After the reaction for 1 hour, the temperature was raised to 145°C, and then hydrogen was introduced until the pressure reached 7.5Mpa, so that the nitrile rubber was subjected to metathesis degradation and hydrogenation reduction reaction, and the reaction was carried out for 4 hours to obtain a liquid hydrogenated nitrile rubber solution. After flocculation, washing and drying, a liquid hydrogenated nitrile rubber raw rubber was obtained.

[0111] The characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are as follows: molecular weight (Mw) is 61378, molecular weight distribution index is 2.67, acrylonitrile content is 35%, and hydrogenation degree is 99%.

[0112] Various embodiments of the present invention may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present invention; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0113] The foregoing is merely a specific embodiment of the present invention, which enables those skilled in the art to understand or implement the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A liquid hydrogenated nitrile rubber, characterized in that The physical and chemical property parameters of the liquid hydrogenated nitrile rubber include: a weight average molecular weight of 10,000-300,000, a molecular weight distribution index of 1.5-6.0, a weight percentage content of acrylonitrile of 15%-50%, and a Mooney viscosity of 10-60.

2. The liquid hydrogenated nitrile rubber according to claim 1, characterized in that The molecular weight distribution index of the liquid hydrogenated nitrile rubber is 2.0-4.

0.

3. The liquid hydrogenated nitrile rubber according to claim 1, characterized in that The Mooney viscosity of the liquid hydrogenated nitrile rubber is 35-50.

4. The liquid hydrogenated nitrile rubber according to claim 1, characterized in that The weight average molecular weight of the liquid hydrogenated nitrile rubber is 60,000-300,000.

5. The liquid hydrogenated nitrile rubber according to claim 1, characterized in that The weight percentage of acrylonitrile in the liquid hydrogenated nitrile rubber is 17% to 45%.

6. A method for preparing the liquid hydrogenated nitrile rubber according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: Obtaining nitrile rubber; The nitrile rubber, the catalyst and the organic solvent are mixed, and then an olefin metathesis reaction is carried out under an inert gas atmosphere to obtain a first reaction system; Passing hydrogen into the first reaction system, and then continuing to perform a hydrogenation reduction reaction under an inert gas atmosphere to obtain a second reaction system; The second reaction system is subjected to purification and post-treatment to obtain the liquid hydrogenated nitrile rubber.

7. The method for preparing liquid hydrogenated nitrile rubber according to claim 6, characterized in that: In terms of weight percentage, the amount of the catalyst is 0.005% to 0.1% of the weight of the nitrile rubber; in terms of g / L, the weight volume ratio of the nitrile rubber to the organic solvent is (100 to 300):1, and the organic solvent includes at least one of chloroform, ethylene dichloride, acetone and chlorobenzene.

8. The method for preparing liquid hydrogenated nitrile rubber according to claim 6, characterized in that: The general structural formula of the catalyst is shown in Formula I; The formula I: wherein R1 and R2 are the same or different and are each hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonyl, or alkylsulfinyl; L is a phosphine, sulfonated phosphine, phosphate, phosphinite, phosphinate, arsine, ether, amine, amide, sulfonate, sulfoxide, carboxyl, nitrosyl, pyridine, thioether, imidazoline or imidazolidine ligand; X1 and X2 are the same or different and are two ligands selected from the group consisting of hydrogen, halogen, pseudohalogen, straight or branched C1-C 30 -alkyl, C6-C 24 -Aryl, C1-C 20 -alkoxy, C6-C 24 -Aryloxy, C3-C 20 -Alkyl diketonate, C6-C 24 -Aryl diketonate, C1-C 20 -Carboxylic acid ester, C1-C 20 -Alkyl sulfonate, C6-C 24 -Aryl sulfonate, C1-C 20 -Alkyl mercaptan, C6-C 24 -Aryl thiols, C1-C 20 -alkylsulfonyl or C1-C 20 -alkylsulfinyl; E1, E2, E3, E4, and E5 are each independently hydrogen, halogen, nitro, nitrile, sulfoxide, sulfone, aldehyde, substituted or unsubstituted C1-C 20 Alkyl, C1-C 20 Alkylthio, C1-C 20 Alkylsilyl, C1-C 20 Alkylsilyloxy, substituted or unsubstituted C2-C 20 Heterocyclic group, substituted or unsubstituted amino group, aminoacyl group, substituted or unsubstituted C1-C 20 The carbonyl group of the alkylamino group, the substituted or unsubstituted C2-C 20 The carbonyl group of the heterocyclylamino group is connected to a substituted or unsubstituted C2-C 20 The carbonyl group of the heterocyclic group, the substituted or unsubstituted C1-C 20 The carbonyl group of the alkoxy group, the substituted or unsubstituted C6-C 20 The carbonyl, urea, substituted or unsubstituted C1-C 20 Alkylurea, substituted or unsubstituted C1-C 20 Alkylurea, substituted or unsubstituted C6-C 20 Arylurea or substituted or unsubstituted C2-C 20 Heterocyclyl urea, substituted or unsubstituted C6-C 20 Aryl, substituted or unsubstituted C6-C 20 Aryloxy.

9. The method for preparing liquid hydrogenated nitrile rubber according to claim 6, characterized in that: The catalyst is selected from any of the following compounds: wherein R1 and R2 are the same or different and are each hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonyl, or alkylsulfinyl; X1 and X2 are identical or different and are two ligands selected from the group consisting of hydrogen, halogen, pseudohalogen, linear or branched C1-C30-alkyl, C6-C24-aryl, C1-C20-alkoxy, C6-C24-aryloxy, C3-C20-alkyldiketonate, C6-C24-aryldiketonate, C1-C20-carboxylate, C1-C20-alkylsulfonate, C6-C24-arylsulfonate, C1-C20-alkylthiol, C6-C24-arylthiol, C1-C20-alkylsulfonyl or C1-C20-alkylsulfinyl; E1, E3, and E5 are each independently hydrogen, halogen, nitro, nitrile, sulfoxide, sulfone, aldehyde, substituted or unsubstituted C1-C20 alkyl, C1-C20 alkylthio, C1-C20 alkylsilyl, C1-C20 alkylsiloxy, substituted or unsubstituted C2-C20 heterocyclyl, substituted or unsubstituted amino, aminoacyl, a carbonyl group connected to a substituted or unsubstituted C1-C20 alkylamino, a carbonyl group connected to a substituted or unsubstituted C2-C20 heterocyclylamino, a carbonyl group connected to a substituted or unsubstituted a substituted or unsubstituted C2-C20 heterocyclyl carbonyl group, a carbonyl group connected to a substituted or unsubstituted C1-C20 alkoxy group, a carbonyl group connected to a substituted or unsubstituted C6-C20 aryloxy group, a urea group, a substituted or unsubstituted C1-C20 alkylurea group, a substituted or unsubstituted C1-C20 alkylurea group, a substituted or unsubstituted C6-C20 arylurea group, or a substituted or unsubstituted C2-C20 heterocyclylurea group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C6-C20 aryloxy group; wherein X1 and X2 are the same or different and are two ligands selected from the group consisting of hydrogen, halogen, pseudohalogen, straight or branched C1-C 30 -alkyl, C6-C 24 -Aryl, C1-C 20 -alkoxy, C6-C 24 -Aryloxy, C3-C 20 -Alkyl diketonate, C6-C 24 -Aryl diketonate, C1-C 20 -Carboxylic acid ester, C1-C 20 -Alkyl sulfonate, C6-C 24 -Aryl sulfonate, C1-C 20 -Alkyl mercaptan, C6-C 24 -Aryl thiols, C1-C 20 -alkylsulfonyl or C1-C 20 -alkylsulfinyl; E1, E3, and E5 are each independently hydrogen, halogen, nitro, nitrile, sulfoxide, sulfone, aldehyde, substituted or unsubstituted C1-C20 alkyl, C1-C20 alkylthio, C1-C20 alkylsilyl, C1-C20 alkylsiloxy, substituted or unsubstituted C2-C20 heterocyclyl, substituted or unsubstituted amino, aminoacyl, a carbonyl group connected to a substituted or unsubstituted C1-C20 alkylamino, a carbonyl group connected to a substituted or unsubstituted C2-C20 heterocyclylamino, a carbonyl group connected to a substituted or unsubstituted The invention also includes a substituted C2-C20 heterocyclyl carbonyl group, a carbonyl group connected to a substituted or unsubstituted C1-C20 alkoxy group, a carbonyl group connected to a substituted or unsubstituted C6-C20 aryloxy group, a urea group, a substituted or unsubstituted C1-C20 alkylurea group, a substituted or unsubstituted C1-C20 alkylurea group, a substituted or unsubstituted C1-C20 alkylurea group, a substituted or unsubstituted C6-C20 arylurea group, or a substituted or unsubstituted C2-C20 heterocyclylurea group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C6-C20 aryloxy group.

10. The method for preparing liquid hydrogenated nitrile rubber according to claim 6, characterized in that: The condition parameters of the olefin metathesis reaction include: reaction temperature of 80-110° C., reaction time of 0.5-2 h; the condition parameters of the hydrogenation reduction reaction include: reaction temperature of 80-200° C., hydrogen pressure of 5 Mpa-9 Mpa, reaction time of 2-6 h.

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