A cycloolefin polymer and a method for preparing the same

Abstract

The present invention provides a cycloolefin polymer and a preparation method thereof, relating to the field of cycloolefin polymers. The preparation method includes: preheating the solution of the cycloolefin polymer monomer, the solution of the chain transfer agent, and the solution of the ruthenium-based catalyst to 45-200 °C respectively and then mixing them to obtain a mixed solution, subjecting the mixed solution to ring-opening polymerization reaction at 45-250 °C, wherein the time of the ring-opening polymerization reaction is 55-65 min; after the ring-opening polymerization reaction ends, introducing a hydrogen source into the mixed solution for hydrogenation reaction, wherein the time of the hydrogenation reaction is 6-12 h; after the hydrogenation reaction ends, adding a terminator, an adsorbent, and a poor solvent to the mixed solution in sequence, and separating to obtain the cycloolefin polymer. The present invention can obtain a cycloolefin polymer with controllable molecular weight, narrow molecular weight distribution, and good optical properties.

Description

Technical Field

[0001] The present invention relates to a cycloolefin polymer and a preparation method thereof, belonging to the field of cycloolefin polymers. Background Art

[0002] Cycloolefin polymer, abbreviated as COP, is a polymer material obtained by ring-opening polymerization of cycloolefin monomers followed by hydrogenation, having advantages such as high light transmittance, low birefringence, and high water vapor barrier, and having good application prospects in the fields of optical lenses, medical packaging, electronic devices, etc. However, limited by factors such as the preparation process of cycloolefin polymers, cycloolefin polymers generally have defects such as wide molecular weight distribution and poor optical properties.

[0003] For example, the catalysts for ring-opening polymerization of cycloolefins mainly include W, Mo-based catalysts and Ru-based catalysts. For example, the patent document with the publication number CN1186080A discloses a method for preparing cycloolefin polymers using a ruthenium-based catalyst (Ru-based catalyst), and the polymerization and hydrogenation are completed simultaneously using the Ru-based catalyst; the patent document with the publication number CN117417512A discloses a method for preparing cycloolefin polymers using W, Mo-based catalysts, and the obtained cycloolefin polymers can be used in the field of medical packaging; the patent document with the publication number CN117050276A discloses a method for preparing a tetracyclo[6.2.1.13,6.02,7]dodec-4-ene ring-opening polymer, using a W-based catalyst as the ring-opening polymerization catalyst and a Ru-based catalyst as the hydrogenation catalyst.

[0004] Compared with W, Mo-based catalysts, Ru-based catalysts have better water and oxygen and functional group tolerance (for example, as recorded in the following non-patent literature: Kong Yong, Yang Xiaohua, Wang Lin, etc. Research progress of ring-opening metathesis polymerization [J]. Science Technology and Engineering, 2015, 15(30): 71-78), and can be used simultaneously in the polymerization and hydrogenation processes, which greatly reduces the operation difficulty and cost. However, the cost of Ru-based catalysts is relatively high, which limits their industrial application. And although the activity of Ru-based catalysts is extremely high, too little addition of Ru-based catalysts will lead to too high viscosity of the polymerization system, difficult control of the polymerization process, too wide molecular weight distribution of the polymer, making the quality of the polymer uncontrollable, and even using the method of adding a large amount of chain transfer agent is difficult to completely solve the above problems. Summary of the Invention

[0005] The present invention provides a cycloolefin polymer and a preparation method thereof. The method uses a ruthenium-based catalyst (Ru-based catalyst) to prepare cycloolefin polymers, and can obtain cycloolefin polymers with controllable molecular weight, narrow molecular weight distribution, and good optical properties, thereby realizing the economic, efficient, and controllable preparation of cycloolefin polymers with good properties.

[0006] The present invention provides a method for preparing a cycloolefin polymer, comprising the following steps: separately preparing a solution of a cycloolefin polymer monomer, a solution of a chain transfer agent, and a solution of a ruthenium-based catalyst; preheating the solution of the cycloolefin polymer monomer, the solution of the chain transfer agent, and the solution of the ruthenium-based catalyst to 45-200 °C respectively; mixing the preheated solution of the cycloolefin polymer monomer, the solution of the chain transfer agent, and the solution of the ruthenium-based catalyst to obtain a mixed solution, and carrying out a ring-opening polymerization reaction on the mixed solution at 45-250 °C, wherein the time of the ring-opening polymerization reaction is 5-65 min; after the ring-opening polymerization reaction is completed, adding a hydrogen source to the mixed solution for a hydrogenation reaction, wherein the time of the hydrogenation reaction is 6-12 h; after the hydrogenation reaction is completed, adding a terminator, an adsorbent, and a poor solvent to the mixed solution in sequence, and separating to obtain the cycloolefin polymer.

[0007] Optionally, the cycloolefin polymer monomer includes one or more of the compounds represented by formula (1) and the compounds represented by formula (2):

[0008] Formula (1), Formula (2),

[0009] In the formula (1), R 1 ~R 4 are each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1-15 carbon atoms, a cycloalkyl group, an aryl group having 6-10 carbon atoms with substituents, or a substituent containing a first heteroatom; in the formula (2), R 5 ~R 6 are each independently selected from an alkyl group having 1-15 carbon atoms, a substituted or unsubstituted aryl group having 6-10 carbon atoms, or a substituent containing a second heteroatom, R 7 is selected from an alkyl group having 1-15 carbon atoms, a substituted or unsubstituted aryl group having 6-12 carbon atoms, or a substituent containing a third heteroatom, R 8 ~R 9 are each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1-15 carbon atoms, a substituted or unsubstituted aryl group having 6-10 carbon atoms, or a substituent containing a fourth heteroatom;

[0010] And / or, the chain transfer agent includes an olefin and / or a halogenated olefin having 3-30 carbon atoms; and / or, the concentration of the cycloolefin polymer monomer in the solution of the cycloolefin polymer monomer is 0.001-10 mol / L; and / or, the concentration of the chain transfer agent in the solution of the chain transfer agent is 0.001-10 mol / L; and / or, the concentration of ruthenium element in the solution of the ruthenium-based catalyst is 0.001-10 mol / L.

[0011] Optionally, in the formula (1), the R 1 and R 2 are combined with each other to form a ring; and / or, in the formula (1), the first heteroatom includes one or more of a silicon atom, a nitrogen atom, and an oxygen atom; and / or, in the formula (2), the second heteroatom includes one or more of a silicon atom, a nitrogen atom, and an oxygen atom; the third heteroatom includes one or more of a silicon atom, a nitrogen atom, and an oxygen atom; the fourth heteroatom includes one or more of a silicon atom, a nitrogen atom, and an oxygen atom.

[0012] Optionally, the compound represented by the formula (1) includes one or more of cyclododecene, 8-methylcyclododecene, 8-ethylcyclododecene, 8-isopropylcyclododecene, 8-n-butylcyclododecene, 8-isobutylcyclododecene, 8-cyclopentylcyclododecene, 8-cyclohexylcyclododecene, 8-chloro-cyclododecene, 8-bromo-cyclododecene, 8-methoxycyclododecene, 8-carbonyl-cyclododecene, 8-hydroxycyclododecene, 8-carboxycyclododecene, 8-aminocyclododecene, 8-phenoxycyclododecene, 8-cyanocyclododecene, 8-phenylcyclododecene, 12-methylcyclododecene, 12-phenoxycyclododecene, 12-chloro-cyclododecene; and / or, the compound represented by the formula (2) includes one or more of 5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2,3-dicarboximide, methyl-5-norbornene-2,3-dicarboxylic anhydride, ethyl-5-norbornene-2,3-dicarboxylic anhydride, isopropyl-5-norbornene-2,3-dicarboxylic anhydride, isobutyl-5-norbornene-2,3-dicarboxylic anhydride, cyclohexyl-5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboximide, ethyl-5-norbornene-2,3-dicarboximide, isopropyl-5-norbornene-2,3-dicarboximide, isobutyl-5-norbornene-2,3-dicarboximide, N-hydroxy-5-norbornene-2,3-dicarboximide, N-phenyl-5-norbornene-2,3-dicarboximide, N-benzyl-5-norbornene-2,3-dicarboximide, N-naphthyl-5-norbornene-2,3-dicarboximide, norbornene-2,3-dicarboximido tert-butyl carbonate, norbornene-2,3-dicarboximido p-nitrobenzyl carbonate;

[0013] And / or, the chain transfer agent includes one or more of aliphatic olefins, aromatic olefins, and halogenated olefins; the aliphatic olefins include one or more of 1-pentene, 2-pentene, 1-hexene, 2-hexene, 4-octene, 1-octene, and 1-heptene; the aromatic olefins include one or more of styrene, triphenylethylene, 4-phenyl-1-butene, and 6-phenyl-1-hexene; the halogenated olefins include one or more of 4-bromo-1-butene, 2-bromo-2-butene, 6-bromo-1-hexene, 5,6-dibromo-1-hexene, 6-chloro-1-hexene, and 8-chloro-1-octene.

[0014] Optionally, in the mixed solution, the molar ratio of the cycloolefin polymer monomer to ruthenium element is 1:(1×10 -5 ~5×10 -4 ); and / or, in the mixed solution, the molar ratio of the cycloolefin polymer monomer to the chain transfer agent is 1:(1×10 -4 ~5×10 -2 ); and / or, the temperature of the ring-opening polymerization reaction is greater than or equal to the preheating temperature; and / or, the pressure of the ring-opening polymerization reaction is 0.1~5 MPa.

[0015] Optionally, the hydrogen source includes hydrogen and / or hydrazine compounds; the hydrazine compounds include one or more of hydrazine, phenylhydrazine, formylhydrazine, acetylhydrazine, valerylhydrazine, hexanoylhydrazine, benzenesulfonylhydrazine, p-toluenesulfonylhydrazine, and phenylmethanesulfonylhydrazine; and / or, the temperature of the hydrogenation reaction is -10~210 °C, and the pressure of the hydrogenation reaction is 0.05~15 MPa.

[0016] Optionally, the terminator includes an olefin with 3 to 30 carbon atoms containing a sixth heteroatom, and the sixth heteroatom includes one or more of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom, and a halogen atom; and / or, the adsorbent includes one or more of thiourea resin, activated carbon, silica gel, diatomaceous earth, and alumina; and / or, the poor solvent includes one or more of alcohol solvents, aldehyde-ketone solvents, ether solvents, and phenol solvents; the alcohol solvents include one or more of methanol, ethanol, isopropanol, ethylene glycol, and n-butanol; the aldehyde-ketone solvents include one or more of acetone, pyruvaldehyde, bromoacetone, propionaldehyde, and isobutyraldehyde; the ether solvents include one or more of diethyl ether, methyl ethyl ether, dibutyl ether, and tetrahydrofuran; the phenol solvents include one or more of phenol, o-cresol, and isopropylphenol.

[0017] Optionally, the terminator includes one or more of 1,1 - diethoxyethylene, 1 - bromo - 2 - ethoxyethylene, methoxyethylene, ethoxyethylene, 2 - methoxypropylene, 3,3 - dimethoxypropylene, 3 - methoxyacrylic acid, ethyl propenyl ether, 3 - ethoxyacrylic acid; and / or, after the hydrogenation reaction is terminated, adding the terminator, the adsorbent and the poor solvent to the mixed solution in sequence, the process of separating the cycloolefin polymer includes: after the hydrogenation reaction is terminated, adding the terminator to the mixed solution, controlling the temperature of the mixed solution to be 45 - 250 °C, and controlling the temperature of the mixed solution to be greater than or equal to the temperature of the ring - opening polymerization reaction, after 1 - 60 min; adding the adsorbent thereto to remove the ruthenium - based catalyst; then dropping the poor solvent thereto to precipitate the cycloolefin polymer, and separating the cycloolefin polymer; wherein, the molar ratio of the terminator to the ruthenium element in the mixed solution is (1 - 100):1; and / or, after the hydrogenation reaction is terminated, adding the terminator, the adsorbent and the poor solvent to the mixed solution in sequence, the process of separating the cycloolefin polymer includes: after the hydrogenation reaction is terminated, adding the solution of the terminator, the adsorbent and the solution of the poor solvent to the mixed solution in sequence, and separating the cycloolefin polymer; wherein, the concentration of the terminator in the solution of the terminator is 0.001 - 10 mol / L; the solution of the poor solvent includes a pH regulator, and the pH regulator includes one or more of hydrochloric acid, sulfuric acid, lactic acid, acetic acid, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate.

[0018] The present invention also provides a cycloolefin polymer obtained by the preparation method as described above.

[0019] Optionally, the glass transition temperature of the cycloolefin polymer is 100 - 300 °C, the hydrogenation rate of the unsaturated bond is not less than 95%, and the refractive index is 1.5 - 2.1.

[0020] The present invention provides a cycloolefin polymer and a preparation method thereof. By preheating the solutions of the cycloolefin polymer monomer, the chain transfer agent and the ruthenium - based catalyst respectively and then mixing them for ring - opening polymerization reaction, hydrogenation reaction and other processes to prepare the cycloolefin polymer, it is beneficial to reduce the dosage of the ruthenium - based catalyst without affecting the quality of the cycloolefin polymer, helps to reduce production costs, and obtain a cycloolefin polymer with controllable molecular weight, narrow molecular weight distribution, good thermal stability and good optical properties, thereby realizing the economic, efficient and controllable preparation of cycloolefin polymers with good properties. Description of the Drawings

[0021] Figure 1High-temperature gel permeation chromatogram of the cycloolefin polymer obtained in Example 1 (the left vertical axis dNf / dLogM refers to the number distribution of polymer chains in different molecular weight ranges, the horizontal axis LogM refers to the logarithm of the molecular weight, and the right vertical axis SCB / 1000TC refers to the number of short-chain branches per 1000 carbon atoms);

[0022] Figure 2 High-temperature gel permeation chromatogram of the cycloolefin polymer obtained in Comparative Example 1 (the left vertical axis dNf / dLogM refers to the number distribution of polymer chains in different molecular weight ranges, the horizontal axis LogM refers to the logarithm of the molecular weight, and the right vertical axis SCB / 1000TC refers to the number of short-chain branches per 1000 carbon atoms). Detailed implementation manners

[0023] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0024] The embodiments of the present invention provide a method for preparing a cycloolefin polymer, comprising the following steps: separately preparing solutions of cycloolefin polymer monomers, chain transfer agents, and ruthenium-based catalysts; preheating the solutions of cycloolefin polymer monomers, chain transfer agents, and ruthenium-based catalysts to 45 - 200°C respectively; mixing the preheated solutions of cycloolefin polymer monomers, chain transfer agents, and ruthenium-based catalysts to obtain a mixed solution, and subjecting the mixed solution to ring-opening polymerization reaction at 45 - 250°C for 5 - 65 minutes; after the ring-opening polymerization reaction is completed, adding a hydrogen source to the mixed solution for hydrogenation reaction for 6 - 12 hours; after the hydrogenation reaction is completed, adding a terminator, an adsorbent, and a poor solvent to the mixed solution in sequence, and separating to obtain the cycloolefin polymer.

[0025] According to the research and analysis of the inventors: after separately preheating the solutions of cycloolefin polymer monomers, chain transfer agents, and ruthenium-based catalysts (Ru-based catalysts) to 45 - 200°C, and then mixing the above three preheated solutions for ring-opening polymerization reaction, it is beneficial to reduce the amount of ruthenium-based catalyst used without affecting the quality of the cycloolefin polymer, which helps to reduce production costs, and at the same time obtain a cycloolefin polymer with controllable molecular weight, narrow molecular weight distribution, and good optical properties, thereby realizing the economic, efficient, and controllable preparation of cycloolefin polymers with good properties.

[0026] The process of preparing a solution of a cycloolefin polymer monomer may at least include the following process: dissolving the cycloolefin polymer monomer in an inert solvent at room temperature (e.g., 12 - 40 °C) to obtain a solution of the cycloolefin polymer monomer.

[0027] The process of preparing a solution of a chain transfer agent may at least include the following process: dissolving the chain transfer agent in an inert solvent at room temperature (e.g., 12 - 40 °C) to obtain a solution of the chain transfer agent.

[0028] The process of preparing a solution of a ruthenium-based catalyst may at least include the following process: dissolving the ruthenium-based catalyst in an inert solvent at room temperature (e.g., 12 - 40 °C) to obtain a solution of the ruthenium-based catalyst.

[0029] The processes of preparing the solution of the cycloolefin polymer monomer, the solution of the chain transfer agent, and the solution of the ruthenium-based catalyst described above can all be carried out under the protection of an inert gas. Specifically, when implementing, a flask can be used as a container, and the above preparation processes can be carried out in a glove box.

[0030] In the embodiments of the present invention, no special limitation is imposed on the above-mentioned inert solvent. The above-mentioned inert solvent only needs to be a solvent that can dissolve or disperse the cycloolefin polymer and does not affect various reactions such as ring-opening polymerization reactions. For example, the inert solvent may include one or more of aliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, nitrogen-containing hydrocarbons, and ethers. Specifically, the aliphatic hydrocarbons may include one or more of pentane, hexane, heptane, 2,4-dimethylpentane, and 3-methylhexane; the cycloaliphatic hydrocarbons may include one or more of cyclopentane, cyclohexane, cycloheptane, cyclodecane, methylcyclohexane, and cyclooctane; the aromatic hydrocarbons may include one or more of benzene, toluene, xylene, and butylbenzene; the halogenated aliphatic hydrocarbons may include one or more of dichloromethane, chloroform, and 1,2-dichloroethane; the nitrogen-containing hydrocarbons may include one or more of nitromethane, nitrobenzene, and acetonitrile; the ethers may include one or more of diethyl ether, dibutyl ether, and tetrahydrofuran. Preferably, the above-mentioned inert solvent may include one or more of toluene, xylene, pentane, hexane, cyclopentane, and cyclohexane.

[0031] The concentration of the cycloolefin polymer monomer in the above-mentioned solution of the cycloolefin polymer monomer may be 0.001 - 10 mol / L, such as 0.001 mol / L, 0.01 mol / L, 1 mol / L, 2 mol / L, 3 mol / L, 5 mol / L, 7 mol / L, 9 mol / L, 10 mol / L, or the range composed of any two of them. Preferably, it is 0.01 - 5 mol / L.

[0032] The concentration of the chain transfer agent in the solution of the chain transfer agent may be 0.001 to 10 mol / L, such as 0.001 mol / L, 0.01 mol / L, 1 mol / L, 2 mol / L, 3 mol / L, 5 mol / L, 7 mol / L, 9 mol / L, 10 mol / L, or a range composed of any two of them, preferably 0.01 to 5 mol / L.

[0033] The concentration of ruthenium element in the solution of the ruthenium-based catalyst may be 0.001 to 10 mol / L, such as 0.001 mol / L, 0.01 mol / L, 1 mol / L, 2 mol / L, 3 mol / L, 5 mol / L, 7 mol / L, 9 mol / L, 10 mol / L, or a range composed of any two of them, preferably 0.01 to 5 mol / L.

[0034] In some embodiments, the cycloolefin polymer monomer includes one or more of the compounds represented by formula (1) and the compounds represented by formula (2):

[0035] Formula (1), Formula (2),

[0036] In formula (1), R 1 ~R 4 are each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group, an aryl group having 6 to 10 carbon atoms with substituents, or a substituent containing a first heteroatom; in formula (2), R 5 ~R 6 are each independently selected from an alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a substituent containing a second heteroatom, and R 7 is selected from an alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a substituent containing a third heteroatom, and R 8 ~R 9 are each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a substituent containing a fourth heteroatom. In the system of the preparation method of the embodiments of the present invention, the above cycloolefin polymer monomer can ensure that under the premise of less consumption of the ruthenium-based catalyst, a cycloolefin polymer with controllable molecular weight, narrow molecular weight distribution, and good optical properties can be obtained.

[0037] In formula (1), R 1 、R 2They can combine with each other to form a ring or not; the first heteroatom may include one or more of silicon atoms, nitrogen atoms, and oxygen atoms. In formula (2), the second heteroatom, the third heteroatom, and the fourth heteroatom each independently include one or more of silicon atoms, nitrogen atoms, and oxygen atoms.

[0038] Specifically, the compound shown in the above formula (1) may include one or more of cyclododecene, 8-methylcyclododecene, 8-ethylcyclododecene, 8-isopropylcyclododecene, 8-n-butylcyclododecene, 8-isobutylcyclododecene, 8-cyclopentylcyclododecene, 8-cyclohexylcyclododecene, 8-chloro-cyclododecene, 8-bromo-cyclododecene, 8-methoxycyclododecene, 8-carbonyl-cyclododecene, 8-hydroxycyclododecene, 8-carboxycyclododecene, 8-aminocyclododecene, 8-phenoxycyclododecene, 8-cyanocyclododecene, 8-phenylcyclododecene, and preferably one or more of cyclododecene, 8-methylcyclododecene, 8-ethylcyclododecene, -isopropylcyclododecene, 8-n-butylcyclododecene, 8-isobutylcyclododecene, 8-phenylcyclododecene, 12-methylcyclododecene, 12-phenoxycyclododecene, 12-chloro-cyclododecene.

[0039] Among them, the structural formula of 8-methylcyclododecene is as shown in formula (1-1), the structural formula of cyclododecene is as shown in formula (1-2), the structural formula of 8-chloro-cyclododecene is as shown in formula (1-3), the structural formula of 8-phenoxycyclododecene is as shown in formula (1-4), the structural formula of 12-methylcyclododecene is as shown in formula (1-5), the structural formula of 12-phenoxycyclododecene is as shown in formula (1-6), and the structural formula of 12-chloro-cyclododecene is as shown in formula (1-7).

[0040]

[0041] The compound shown in formula (2) may include one or more of 5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2,3-dicarboximide, methyl-5-norbornene-2,3-dicarboxylic anhydride, ethyl-5-norbornene-2,3-dicarboxylic anhydride, isopropyl-5-norbornene-2,3-dicarboxylic anhydride, isobutyl-5-norbornene-2,3-dicarboxylic anhydride, cyclohexyl-5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboximide, ethyl-5-norbornene-2,3-dicarboximide, isopropyl-5-norbornene-2,3-dicarboximide, isobutyl-5-norbornene-2,3-dicarboximide, N-hydroxy-5-norbornene-2,3-dicarboximide, N-phenyl-5-norbornene-2,3-dicarboximide, N-benzyl-5-norbornene-2,3-dicarboximide, N-naphthyl-5-norbornene-2,3-dicarboximide, norbornene-2,3-dicarboximido tert-butyl carbonate, norbornene-2,3-dicarboximido p-nitrobenzyl carbonate, preferably one or more of 5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2,3-dicarboximide, methyl-5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboximide, ethyl-5-norbornene-2,3-dicarboximide, N-phenyl-5-norbornene-2,3-dicarboximide, N-benzyl-5-norbornene-2,3-dicarboximide, N-naphthyl-5-norbornene-2,3-dicarboximide.

[0042] Among them, the structural formula of N-phenyl-5-norbornene-2,3-dicarboximide is shown in formula (2-1), and the structural formula of 5-norbornene-2,3-dicarboxylic anhydride is shown in formula (2-2).

[0043]

[0044] Formula (2-1) Formula (2-2)

[0045] In some embodiments, the ruthenium-based catalyst can be prepared by referring to the following process: Dissolve 1 g of Grubbs second-generation catalyst [CAS: 246047-72-3] (Adamas Reagent Co., Ltd., purity 98%) in 50 mL of dichloromethane (Adamas Reagent Co., Ltd., 99.9%) to obtain a first mixed solution; separately prepare ligand B 1Dissolve it in 30 mL of dichloromethane to form a solution, obtaining a second mixed solution; then, mix the above-mentioned first mixed solution and the second mixed solution at 40 °C, add 0.1 g of copper chloride (Adamas Reagent Co., Ltd. (adamas), 98%), stir and react for 5 h, let it stand overnight at -30 °C, and then filter. The obtained solid is the ruthenium-based catalyst. Among them, ligand B can be prepared by referring to the following process 1 : In a glove box, dissolve 1 g of 2-isopropoxystyrene (Sinopharm Chemical Reagent Co., Ltd., 97%) in 10 mL of toluene to obtain a third mixed solution; add 0.1 g of anhydrous aluminum chloride (Sinopharm Chemical Reagent Co., Ltd., 98%) to this third mixed solution, and then introduce chloromethane gas (Shanghai Weichuang Standard Gas Co., Ltd., 99%), react for 3 h to obtain a reaction solution; then, dropwise add the above reaction solution to 0.7 g of metallic lithium (Sinopharm Chemical Reagent Co., Ltd., 99%) at -78 °C to obtain a toluene solution containing alkyllithium; take 2 mL of this toluene solution containing alkyllithium and drop it into 3 g of 3,5-dibromopyridine (Adamas Reagent Co., Ltd. (adamas), 98%), stir and react for 3 h, and then perform recrystallization at -30 °C. The precipitated solid is the ligand B used 1 .

[0046] In some other embodiments, the ruthenium-based catalyst can be prepared by referring to the following process: Dissolve 1 g of Grubbs second-generation catalyst [CAS: 246047-72-3] (Adamas Reagent Co., Ltd. (adamas), 98%) in 60 mL of toluene (Adamas Reagent Co., Ltd. (adamas), 99.5%) to obtain a fourth mixed solution; dissolve ligand A in 45 mL of toluene to obtain a fifth mixed solution; then mix the fourth mixed solution and the fifth mixed solution at room temperature, stir and react for 10 h, add an equal volume of n-hexane (Fischer Scientific International Inc., HPLC), and let it stand overnight at -30 °C, and then filter to collect the precipitated solid; dissolve the precipitated solid in 80 mL of dichloromethane to form a sixth mixed solution; dissolve ligand B in 30 mL of dichloromethane to form a seventh mixed solution, then mix the sixth mixed solution and the seventh mixed solution at 40 °C, then add 0.1 g of copper chloride, stir and react for 8 h, then let it stand overnight at -30 °C, and filter. The obtained solid is the ruthenium-based catalyst;

[0047] Among them, ligand A may include 1,3-bis(2,4,6-triisopropylphenyl)imidazole (Sinopharm Chemical Reagent Co., Ltd., 98%); ligand B can be prepared by referring to the following process: In a glove box, dissolve 1.3 g of 2-methoxystyrene (Sinopharm Chemical Reagent Co., Ltd., 97%) in 10 mL of toluene to obtain an eighth mixed solution. Then, add 0.1 g of anhydrous aluminum chloride (Sinopharm Chemical Reagent Co., Ltd., 98%) to the eighth mixed solution, and then introduce chloromethane gas (Shanghai Weichuang Standard Gas Co., Ltd., 99%). React for 3 h to obtain a reaction solution. Dropwise add the above reaction solution to 0.7 g of metallic lithium (Sinopharm Chemical Reagent Co., Ltd., 99%) at -78 °C to obtain a toluene solution containing alkyllithium. Take 2 mL of the toluene solution containing alkyllithium and drop it into 3 g of 3,5-dibromopyridine. After stirring and reacting for 5 h, perform recrystallization at -30 °C, and the precipitated solid is ligand B;

[0048] Alternatively, ligand A may include 1,3-bis(2,4,6-triisopropylphenyl)imidazole (Sinopharm Chemical Reagent Co., Ltd., 98%); ligand B can be prepared by referring to the following process: Dissolve 1 g of 2-isopropoxystyrene (Sinopharm Chemical Reagent Co., Ltd., 97%) in 10 mL of toluene to obtain a ninth mixed solution. Add 0.1 g of anhydrous aluminum chloride (Sinopharm Chemical Reagent Co., Ltd., 98%) to the ninth mixed solution, and then introduce chloromethane gas (Shanghai Weichuang Standard Gas Co., Ltd., 99%). React for 3 h to obtain a reaction solution. Dropwise add the above reaction solution to 0.7 g of metallic lithium (Sinopharm Chemical Reagent Co., Ltd., 99%) at -78 °C to obtain a toluene solution containing alkyllithium. Take 2 mL of the toluene solution containing alkyllithium and drop it into 3 g of 3,5-dibromopyridine. After stirring and reacting for 3 h, perform recrystallization at -30 °C, and the precipitated solid is ligand B;

[0049] Alternatively, ligand A may include 1,3-bis(2,4,6-triisopropylphenyl)imidazole (Sinopharm Chemical Reagent Co., Ltd., 98%); ligand B can be prepared with reference to the following process: Dissolve 1 g of 2-isopropoxystyrene (Sinopharm Chemical Reagent Co., Ltd., 97%) in 10 mL of toluene to obtain a tenth mixed solution. Add 0.1 g of anhydrous aluminum chloride (Sinopharm Chemical Reagent Co., Ltd., 98%) to this tenth mixed solution, then add 0.3 g of 1-chlorobutan-2-one (Adamas Reagent Co., Ltd., 98%), react for 3 h to obtain a reaction solution. Then, dropwise add the above reaction solution to 0.7 g of metallic lithium (Sinopharm Chemical Reagent Co., Ltd., 99%) at -78°C to obtain a toluene solution containing alkyllithium. Take 2.5 mL of this toluene solution containing alkyllithium and drop it into 3 g of 3,5-dibromopyridine, stir and react for 3 h, and then perform recrystallization at -30°C. The precipitated solid is ligand B;

[0050] Alternatively, ligand A may include tricyclohexylphosphine (Adamas Reagent Co., Ltd., 98%); ligand B can be prepared with reference to the following process: Dissolve 1 g of 2-isopropoxystyrene (Sinopharm Chemical Reagent Co., Ltd., 97%) in 10 mL of toluene to obtain an eleventh mixed solution. Add 0.1 g of anhydrous aluminum chloride (Sinopharm Chemical Reagent Co., Ltd., 98%) to this eleventh mixed solution, then add 0.5 mL of tert-butyl chloride (Adamas Reagent Co., Ltd., 99%), react for 3 h to obtain a reaction solution; then, dropwise add the above reaction solution to 0.7 g of metallic lithium (Sinopharm Chemical Reagent Co., Ltd., 99%) at -78°C to obtain a toluene solution containing alkyllithium. Take 1.5 mL of this toluene solution containing alkyllithium and drop it into 3 g of 3,5-dibromopyridine, stir and react for 6 h, and then perform recrystallization at -30°C. The precipitated solid is ligand B;

[0051] Alternatively, ligand A may include 1,3-bis(2,4,6-triisopropylphenyl)imidazole (Sinopharm Chemical Reagent Co., Ltd., 98%); ligand B can be prepared by referring to the following process. Dissolve 1 g of 2-isopropoxystyrene (Sinopharm Chemical Reagent Co., Ltd., 97%) in 10 mL of toluene to obtain the twelfth mixed solution. Add 0.1 g of anhydrous aluminum chloride (Sinopharm Chemical Reagent Co., Ltd., 98%) to the twelfth mixed solution, and then add 0.5 mL of tert-butyl chloride (Adamas Reagent Co., Ltd., 99%). React for 3 h to obtain a reaction solution. Then, dropwise add the above reaction solution to 0.7 g of metallic lithium (Sinopharm Chemical Reagent Co., Ltd., 99%) at -78 °C to obtain a toluene solution containing alkyllithium. Take 1.5 mL of the toluene solution containing alkyllithium and drop it into 3 g of 3,5-dibromopyridine. After stirring and reacting for 7 h, perform recrystallization at -30 °C, and the precipitated solid is ligand B.

[0052] It is understandable that the masses of the raw materials and the reaction conditions in the above process for preparing the ruthenium-based catalyst are all average values.

[0053] The preparation process of the ruthenium-based catalyst in the embodiments of the present invention is not limited to the above process.

[0054] The above ruthenium-based catalyst can be supported on a carrier to form a supported catalyst. At this time, it is not necessary to prepare the ruthenium-based catalyst into a solution, and it can be directly added to the mixed solution (for example, directly added to the reaction kettle). As the carrier of the supported catalyst, it can include one or more of activated carbon, silica gel, diatomite, and aluminum oxide.

[0055] In some embodiments, the chain transfer agent includes an olefin and / or a halogenated olefin having 3 to 30 carbon atoms, and the above olefin may include an aliphatic olefin and / or an aromatic olefin.

[0056] The above aliphatic olefins may include one or more of 1-pentene, 2-pentene, 1-hexene, 2-hexene, 4-octene, 1-octene, and 1-heptene; the aromatic olefins may include one or more of styrene, triphenylethylene, 4-phenyl-1-butene, and 6-phenyl-1-hexene; the halogenated olefins may include one or more of 4-bromo-1-butene, 2-bromo-2-butene, 6-bromo-1-hexene, 5,6-dibromo-1-hexene, 6-chloro-1-hexene, and 8-chloro-1-octene.

[0057] Preferably, the above chain transfer agent may include an aliphatic olefin and / or an aromatic olefin.

[0058] The solutions of cycloolefin polymer monomers, chain transfer agents, and ruthenium-based catalysts are preheated to 45-200 °C, such as 45 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 120 °C, 150 °C, 200 °C, or the range composed of any two of them. Preferably 50-80 °C, which helps to reduce the dosage of ruthenium-based catalysts (Ru-based catalysts), and at the same time ensures the obtained cycloolefin polymer has a narrow molecular weight distribution, good thermal stability and optical properties. That is, while reducing costs, excellent products (cycloolefin polymers) are ensured. The reason for analysis is that when the preheating temperature is higher than 200 °C, the ruthenium-based catalyst may be deactivated, and when the preheating temperature is lower than 45 °C, polymers may precipitate from the solvent, resulting in a wider molecular weight distribution of the final product (cycloolefin polymer).

[0059] In some embodiments, the preheated solutions of cycloolefin polymer monomers, chain transfer agents, and ruthenium-based catalysts are mixed to obtain a mixed solution according to the molar ratio of cycloolefin polymer monomers, chain transfer agents, and ruthenium element of 1:(1×10 -4 ~5×10 -2 ):(1×10 -5 ~5×10 -4 ). That is, in the mixed solution, the molar ratio of cycloolefin polymer monomers, chain transfer agents, and ruthenium element is 1:(1×10 -4 ~5×10 -2 ):(1×10 -5 ~5×10 -4 ), preferably 1:(3×10 -4 ~8×10 -4 ):(5×10 -5 ~1×10 -4 ).

[0060] In the mixed solution, the molar ratio of cycloolefin polymer monomers to ruthenium element can be 1:(1×10 -5 ~5×10 -4 ).

[0061] In the mixed solution, the molar ratio of cycloolefin polymer monomers to chain transfer agents can be 1:(1×10 -4 ~5×10 -2 ).

[0062] During specific implementation, the preheated solutions of cycloolefin polymer monomers, chain transfer agents, and ruthenium-based catalysts can be added to a reaction kettle (such as a reaction kettle purged with nitrogen three times) to obtain a mixed solution.

[0063] Next, carry out ring-opening polymerization reaction on the above-mentioned mixed solution at 45-250 °C, and the time of the ring-opening polymerization reaction is 5-65 min. Exemplarily, the temperature of the above-mentioned ring-opening polymerization reaction can be 45 °C, 50 °C, 60 °C, 80 °C, 100 °C, 120 °C, 150 °C, 200 °C, 250 °C or the range composed of any two of them, preferably 50-100 °C, and the time of the ring-opening polymerization reaction can be 5 min, 10 min, 20 min, 30 min, 40 min, 50 min, 55 min, 56 min, 57 min, 58 min, 59 min, 60 min, 61 min, 62 min, 63 min, 64 min, 65 min or the range composed of any two of them.

[0064] In specific implementation, the temperature of the above-mentioned ring-opening polymerization reaction should be greater than or equal to (i.e., not lower than) the temperature of the above-mentioned preheating, so as to avoid the precipitation of the product (polymer) of the ring-opening polymerization reaction, which may lead to the problem of broadening the molecular weight distribution of the final product (cycloolefin polymer), and thus ensure the cycloolefin polymer with a narrow molecular weight distribution, good thermal stability and optical properties.

[0065] In some embodiments, the pressure of the above-mentioned ring-opening polymerization reaction can be 0.1-5 MPa, such as 0.1 MPa, 0.5 MPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa or the range composed of any two of them, preferably 0.1-2 MPa.

[0066] After the above-mentioned ring-opening polymerization reaction is completed, add a hydrogen source to the above-mentioned mixed solution for hydrogenation reaction, and the time of this hydrogenation reaction is 6-12 h, such as 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h or the range composed of any two of them.

[0067] The processes of the above-mentioned preheating, mixing and ring-opening polymerization reaction can all be carried out under the protection of inert gas.

[0068] The above-mentioned hydrogen source includes hydrogen and / or hydrazine compounds. For example, after the above-mentioned ring-opening polymerization reaction is completed, hydrogen can be introduced into the above-mentioned mixed solution for hydrogenation reaction; and / or, after the above-mentioned ring-opening polymerization reaction is completed, hydrazine compounds can be added (or introduced) into the above-mentioned mixed solution for hydrogenation reaction.

[0069] The above-mentioned hydrazine compounds can include one or more of hydrazine, phenylhydrazine, formylhydrazine, acetylhydrazine, valerylhydrazine, hexanoylhydrazine, benzenesulfonylhydrazine, p-toluenesulfonylhydrazine, phenylmethanesulfonylhydrazine.

[0070] During the above-mentioned hydrogenation reaction process, a hydrogenation catalyst can be added to the mixed solution to improve the efficiency of the hydrogenation reaction (the reaction activity of various reactants in the hydrogenation reaction).

[0071] The above hydrogenation catalyst can be optionally a heterogeneous catalyst or a homogeneous catalyst. The above heterogeneous catalyst can include a heterogeneous catalyst prepared by loading one or more metals selected from nickel, palladium, platinum, rhodium, and ruthenium on a carrier, such as nickel / silica, ruthenium / diatomaceous earth, palladium / carbon, palladium / silica, nickel / carbon, nickel / aluminum oxide, platinum / silica, platinum / carbon, palladium / aluminum oxide, ruthenium / carbon, ruthenium / aluminum oxide, nickel / diatomaceous earth, ruthenium / silica. The above homogeneous catalyst can include one or more of a catalyst composed of a combination of a transition metal compound and an organoaluminum compound, a catalyst composed of a metallocene compound and an organoalkali metal compound, a catalyst composed of a combination of a transition metal compound and an organomagnesium compound, and a noble metal carbene catalyst. For example, the catalyst composed of a combination of a transition metal compound and an organoaluminum compound can be selected from nickel acetate / triisobutylaluminum, cobalt acetate / trimethylaluminum, nickel acetylacetonate / triethylaluminum, or cobalt acetylacetonate / triisobutylaluminum. The catalyst composed of a metallocene compound and an organoalkali metal compound can be selected from dichlorodicyclopentadienyltitanium / tert-butyllithium or dichlorodicyclopentadienylzirconium / n-butyllithium. The catalyst composed of a combination of a transition metal compound and an organomagnesium compound can be selected from tetrabutoxytitanate / dimethylmagnesium or tetrabutoxytitanate / diethylmagnesium. The noble metal carbene catalyst can be selected from bis(triphenylphosphine)palladium dichloride, chlorohydridocarbonyltris(triphenylphosphine)ruthenium, chlorohydridocarbonylbis(tricyclohexylphosphine)ruthenium, bis(tricyclohexylphosphine)benzylidene ruthenium dichloride, or tris(triphenylphosphine)rhodium chloride.

[0072] In particular, when the hydrogenation catalyst is a heterogeneous catalyst, the hydrogenation catalyst can be separated and recovered by means such as filtration after the hydrogenation reaction (hydrogenation reaction) is completed, which is convenient for reuse. It is understandable that the conditions of the hydrogenation reaction (hydrogenation reaction) are also different when different hydrogenation catalyst systems are selected.

[0073] In some embodiments, the temperature of the hydrogenation reaction is -10 to 210 °C, such as -10 °C, -5 °C, 0 °C, 10 °C, 50 °C, 100 °C, 150 °C, 200 °C, 210 °C, or a range composed of any two of them. Preferably, it is -5 to 200 °C, and more preferably 25 to 190 °C.

[0074] In some embodiments, the pressure of the hydrogenation reaction is 0.05 to 15 MPa, such as 0.05 MPa, 0.1 MPa, 0.5 MPa, 1 MPa, 2 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, 12 MPa, 13 MPa, 14 MPa, 15 MPa, or a range composed of any two of them. Preferably, it is 0.1 to 10 MPa, and more preferably 0.5 to 8 MPa.

[0075] After the above hydrogenation reaction is completed, a terminator, an adsorbent, and a poor solvent are sequentially added to the above mixed solution. In the process of separating the cycloolefin polymer, the function of the terminator is to terminate the ring-opening polymerization reaction and the hydrogenation reaction (i.e., the formation reaction of the cycloolefin polymer), ensuring the obtained cycloolefin polymer has a narrow molecular weight distribution, good thermal stability, and optical properties. The function of the adsorbent is to remove the ruthenium-based catalyst. The poor solvent needs to have good compatibility with the aforementioned inert solvent (the solvent for the ring-opening polymerization reaction and the hydrogenation reaction) and be immiscible with the cycloolefin polymer, facilitating the precipitation of the cycloolefin polymer from the solution and the separation of the cycloolefin polymer.

[0076] The above terminator may include olefins with 3 to 30 carbon atoms containing a sixth heteroatom. The sixth heteroatom may include one or more of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom, and a halogen atom. Specifically, it may include one or more of 1,1-diethoxyethylene, 1-bromo-2-ethoxyethylene, methoxyethylene, ethoxyethylene, 2-methoxypropylene, 3,3-dimethoxypropylene, 3-methoxyacrylic acid, ethyl propylene ether, and 3-ethoxyacrylic acid. The addition amount of the terminator may satisfy that the amount of substance of the terminator is 1 to 100 times, preferably 10 to 50 times, the amount of substance of the ruthenium-based catalyst.

[0077] The above adsorbent generally uses a solid adsorbent with a large specific surface area and insoluble in the aforementioned inert solvent (the solvent for the ring-opening polymerization reaction and the hydrogenation reaction), such as one or more of thiourea resin, activated carbon, silica gel, diatomaceous earth, and alumina. In specific implementation, after the above adsorbent fully adsorbs the ruthenium-based catalyst, the adsorbent can be removed (separated) by filtration, leaving the supernatant (upper clear liquid) without the catalyst; then a poor solvent is added to the supernatant or the supernatant is added dropwise to the poor solvent to promote the precipitation of the cycloolefin polymer (forming a white suspension), and then the cycloolefin polymer is separated.

[0078] The above poor solvent may include one or more of alcohol solvents (such as one or more of methanol, ethanol, isopropanol, ethylene glycol, and n-butanol), aldehyde-ketone solvents (such as one or more of acetone, pyruvaldehyde, bromoacetone, propionaldehyde, and isobutyraldehyde), ether solvents (such as one or more of diethyl ether, methyl ethyl ether, dibutyl ether, and tetrahydrofuran), and phenol solvents (such as one or more of phenol, o-cresol, and isopropylphenol), preferably alcohol solvents (such as one or more of methanol, ethanol, and isopropanol). The addition amount of the above poor solvent can exceed the required amount, which is beneficial to the precipitation of the cycloolefin polymer.

[0079] In some embodiments, after the above hydrogenation reaction is completed, a terminator, an adsorbent, and a poor solvent are sequentially added to the above mixed solution. The process of separating the cycloolefin polymer includes: after the hydrogenation reaction is terminated, adding a terminator to the mixed solution, and controlling the temperature of the mixed solution to be 45-250 °C, and controlling the temperature of the mixed solution to be greater than or equal to (not lower than) the temperature of the ring-opening polymerization reaction. After 1-60 minutes; adding an adsorbent thereto to remove the ruthenium-based catalyst; then dropping a poor solvent thereto to precipitate the cycloolefin polymer, and separating to obtain the cycloolefin polymer; wherein, the molar ratio of the terminator to the ruthenium element in the mixed solution is (1-100):1. In the above process, the temperature of the mixed solution is controlled to be 45-250 °C, such as 45 °C, 50 °C, 60 °C, 70 °C, 90 °C, 100 °C, 150 °C, 200 °C, 250 °C or the range composed of any two of them, preferably 50-100 °C, and maintaining and controlling the temperature of the mixed solution to be greater than or equal to the temperature of the ring-opening polymerization reaction, while ensuring that the terminator fully plays the role of terminating the reaction and avoiding the precipitation problem of the hydrogenation reaction product, thereby avoiding affecting the molecular weight of the final product (cycloolefin polymer), and ensuring that a cycloolefin polymer with a narrow molecular weight distribution, good thermal stability and optical properties is obtained; further, controlling the temperature of the above mixed solution to 45-250 °C and maintaining it for 1-60 minutes, such as 1 minute, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes or the range composed of any two of them, preferably 5-30 minutes, can ensure that the ring-opening polymerization reaction and the hydrogenation reaction (i.e., the formation reaction of the cycloolefin polymer) are completely terminated.

[0080] The terminator can be directly added to the mixed solution (such as a reaction kettle), or can be dissolved in an organic solvent to form a solution of the terminator, and the solution of the terminator is added to the mixed solution. For example, after the hydrogenation reaction is terminated, the process of separating the cycloolefin polymer by sequentially adding a terminator, an adsorbent, and a poor solvent to the mixed solution may include: after the hydrogenation reaction is terminated, sequentially adding a solution of the terminator, an adsorbent, and a solution of the poor solvent to the mixed solution, and separating to obtain the cycloolefin polymer. The above organic solvent only needs to be able to dissolve or disperse the terminator and does not affect the structure of the products (polymers) of the ring-opening polymerization reaction and the hydrogenation reaction. For example, one or more of aliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, and ethers can be used. The above aliphatic hydrocarbons may include one or more of pentane, hexane, and heptane. The above cycloaliphatic hydrocarbons may include one or more of cyclopentane, cyclohexane, cyclodecane, hexahydroindane cyclohexane, and cyclooctane. The aromatic hydrocarbons may include one or more of benzene, toluene, and xylene. The halogenated aliphatic hydrocarbons may include one or more of dichloromethane, chloroform, and 1,2-dichloroethane. The nitrogen-containing hydrocarbons may include one or more of nitromethane, nitrobenzene, and acetonitrile. The ethers may include one or more of diethyl ether and tetrahydrofuran.

[0081] The concentration of the terminator in the solution of the terminator described above can be 0.001 - 10 mol / L, such as 0.001 mol / L, 0.01 mol / L, 0.1 mol / L, 1 mol / L, 2 mol / L, 4 mol / L, 6 mol / L, 8 mol / L, 10 mol / L, or the range composed of any two of them. Preferably, it is 0.01 - 5 mol / L.

[0082] The solution of the poor solvent described above may include a pH regulator. These pH regulators can adjust the pH value, and further control the solubility of impurities, so as to achieve the purpose of removing impurities in the cycloolefin polymer.

[0083] The pH regulator includes acidic substances and / or basic substances. The above acidic substances may include one or more of hydrochloric acid, sulfuric acid, lactic acid, and acetic acid. Preferably, they are hydrochloric acid and / or lactic acid. The above basic substances may include one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, and potassium carbonate. Preferably, they are sodium hydroxide and / or sodium carbonate.

[0084] The embodiment of the present invention also provides a cycloolefin polymer obtained according to the above preparation method.

[0085] In some embodiments, the glass transition temperature of the cycloolefin polymer is 100 - 300 °C, preferably 100 - 200 °C, and more preferably 140 - 155 °C, indicating that the cycloolefin polymer has good thermal stability.

[0086] In some embodiments, the hydrogenation rate of the unsaturated bonds of the cycloolefin polymer is not less than 95%, preferably more than 95%, more preferably more than 98%, further preferably more than 99.5%, and particularly preferably more than 99.8%, indicating that the cycloolefin polymer has good light transmittance.

[0087] In some embodiments, the refractive index of the cycloolefin polymer is 1.5 - 2.1. Preferably, the refractive index is 1.52 - 1.6, and more preferably, the refractive index is 1.54 - 1.56. The cycloolefin polymer has good optical properties.

[0088] Hereinafter, the present invention will be introduced in more detail through specific examples.

[0089] The raw materials of petroleum in each example and comparative example can be commercially available or prepared according to the conventional methods in the art.

[0090] The ruthenium-based catalysts used in Comparative Example 1 and Comparative Example 2 are both commercial catalysts, which can be purchased from Adamas Reagent Co., Ltd. (adamas), and the purity of both is 98%.

[0091] Ruthenium-based catalyst I can be prepared by referring to the following process: Dissolve 1 g of Grubbs second-generation catalyst [CAS: 246047-72-3] (Adamas Reagent Co., Ltd., purity 98%) in 50 mL of dichloromethane (Adamas Reagent Co., Ltd., 99.9%) to obtain a first mixed solution; separately dissolve ligand B 1 in 30 mL of dichloromethane to form a solution, obtaining a second mixed solution; then, at 40 °C, mix the above first and second mixed solutions and add 0.1 g of copper chloride (Adamas Reagent Co., Ltd., 98%), stir and react for 5 h, let stand overnight at -30 °C, and then filter. The obtained solid is ruthenium-based catalyst I. Among them, ligand B can be prepared by referring to the following process 1 : In a glove box, dissolve 1 g of 2-isopropoxystyrene (Sinopharm Chemical Reagent Co., Ltd., 97%) in 10 mL of toluene to obtain a third mixed solution; add 0.1 g of anhydrous aluminum chloride (Sinopharm Chemical Reagent Co., Ltd., 98%) to this third mixed solution, and then introduce chloromethane gas (Shanghai Weichuang Standard Gas Co., Ltd., 99%), react for 3 h to obtain a reaction solution; then, at -78 °C, slowly add dropwise the above reaction solution to 0.7 g of metallic lithium (Sinopharm Chemical Reagent Co., Ltd., 99%) to obtain a toluene solution containing alkyllithium; take 2 mL of this toluene solution containing alkyllithium and add it dropwise to 3 g of 3,5-dibromopyridine (Adamas Reagent Co., Ltd., 98%), stir and react for 3 h, and then perform recrystallization at -30 °C. The precipitated solid is the used ligand B 1 .

[0092] Ruthenium-based catalysts II to VI can be prepared by referring to the following process: Dissolve 1 g of Grubbs second-generation catalyst [CAS: 246047-72-3] (Adamas Reagent Co., Ltd., 98%) in 60 mL of toluene (Adamas Reagent Co., Ltd., 99.5%) to obtain a fourth mixed solution; separately dissolve ligand A in 45 mL of toluene to obtain a fifth mixed solution; then mix the fourth mixed solution and the fifth mixed solution at room temperature, stir and react for 10 h, add an equal volume of n-hexane (Fischer Scientific, HPLC), and place it overnight at -30 °C, then filter to collect the precipitated solid; dissolve the precipitated solid in 80 mL of dichloromethane to form a sixth mixed solution; dissolve ligand B in 30 mL of dichloromethane to form a seventh mixed solution, then mix the sixth mixed solution and the seventh mixed solution at 40 °C, then add 0.1 g of copper chloride, stir and react for 8 h, then let it stand overnight at -30 °C, and filter. The obtained solid is ruthenium-based catalysts II to VI;

[0093] Among them, the ligand A corresponding to ruthenium-based catalyst II may include 1,3-bis(2,4,6-triisopropylphenyl)imidazole (Sinopharm Chemical Reagent Co., Ltd., 98%); the ligand B corresponding to ruthenium-based catalyst II can be prepared by referring to the following process: In a glove box, dissolve 1.3 g of 2-methoxystyrene (Sinopharm Chemical Reagent Co., Ltd., 97%) in 10 mL of toluene to obtain an eighth mixed solution, then add 0.1 g of anhydrous aluminum chloride (Sinopharm Chemical Reagent Co., Ltd., 98%) to the eighth mixed solution, and then introduce chloromethane gas (Shanghai Weichuang Standard Gas Co., Ltd., 99%), react for 3 h to obtain a reaction solution, dropwise add the above reaction solution to 0.7 g of metallic lithium (Sinopharm Chemical Reagent Co., Ltd., 99%) at -78 °C to obtain a toluene solution containing alkyllithium, take 2 mL of the toluene solution containing alkyllithium and drop it into 3 g of 3,5-dibromopyridine, stir and react for 5 h, and then perform recrystallization at -30 °C. The precipitated solid is the ligand B corresponding to ruthenium-based catalyst II.

[0094] The ligand A corresponding to ruthenium-based catalyst Ⅲ includes 1,3-bis(2,4,6-triisopropylphenyl)imidazole (Sinopharm Chemical Reagent Co., Ltd., 98%); the ligand B corresponding to ruthenium-based catalyst Ⅲ can be prepared by referring to the following process: Dissolve 1 g of 2-isopropoxystyrene (Sinopharm Chemical Reagent Co., Ltd., 97%) in 10 mL of toluene to obtain the ninth mixed solution. Add 0.1 g of anhydrous aluminum chloride (Sinopharm Chemical Reagent Co., Ltd., 98%) to the ninth mixed solution, and then introduce methyl chloride gas (Shanghai Weichuang Standard Gas Co., Ltd., 99%). React for 3 h to obtain a reaction solution. Dropwise add the above reaction solution to 0.7 g of metallic lithium (Sinopharm Chemical Reagent Co., Ltd., 99%) at -78 °C to obtain a toluene solution containing alkyllithium. Take 2 mL of the toluene solution containing alkyllithium and drop it into 3 g of 3,5-dibromopyridine. After stirring and reacting for 3 h, perform recrystallization at -30 °C, and the precipitated solid is the ligand B corresponding to ruthenium-based catalyst Ⅲ.

[0095] The ligand A corresponding to ruthenium-based catalyst Ⅳ can include 1,3-bis(2,4,6-triisopropylphenyl)imidazole (Sinopharm Chemical Reagent Co., Ltd., 98%); the ligand B corresponding to ruthenium-based catalyst Ⅳ can be prepared by referring to the following process: Dissolve 1 g of 2-isopropoxystyrene (Sinopharm Chemical Reagent Co., Ltd., 97%) in 10 mL of toluene to obtain the tenth mixed solution. Add 0.1 g of anhydrous aluminum chloride (Sinopharm Chemical Reagent Co., Ltd., 98%) to the tenth mixed solution, and then add 0.3 g of 1-chlorobutan-2-one (Adamas Reagents Ltd. (adamas), 98%). React for 3 h to obtain a reaction solution. Then, dropwise add the above reaction solution to 0.7 g of metallic lithium (Sinopharm Chemical Reagent Co., Ltd., 99%) at -78 °C to obtain a toluene solution containing alkyllithium. Take 2.5 mL of the toluene solution containing alkyllithium and drop it into 3 g of 3,5-dibromopyridine. After stirring and reacting for 3 h, perform recrystallization at -30 °C, and the precipitated solid is the ligand B corresponding to ruthenium-based catalyst Ⅳ.

[0096] The ligand A corresponding to the ruthenium-based catalyst V may include tricyclohexylphosphine (Adamas Reagent Co., Ltd., 98%); the ligand B corresponding to the ruthenium-based catalyst V can be prepared by referring to the following process: Dissolve 1 g of 2-isopropoxystyrene (Sinopharm Chemical Reagent Co., Ltd., 97%) in 10 mL of toluene to obtain the eleventh mixed solution. Add 0.1 g of anhydrous aluminum chloride (Sinopharm Chemical Reagent Co., Ltd., 98%) to this eleventh mixed solution, then add 0.5 mL of tert-butyl chloride (Adamas Reagent Co., Ltd., 99%), and react for 3 h to obtain a reaction solution; then, dropwise add the above reaction solution to 0.7 g of metallic lithium (Sinopharm Chemical Reagent Co., Ltd., 99%) at -78 °C to obtain a toluene solution containing alkyllithium. Take 1.5 mL of this toluene solution containing alkyllithium and drop it into 3 g of 3,5-dibromopyridine, stir and react for 6 h, and then perform recrystallization at -30 °C. The precipitated solid is the ligand B corresponding to the ruthenium-based catalyst V.

[0097] The ligand A corresponding to the ruthenium-based catalyst VI may include 1,3-bis(2,4,6-triisopropylphenyl)imidazole (Sinopharm Chemical Reagent Co., Ltd., 98%); the ligand B corresponding to the ruthenium-based catalyst VI can be prepared by referring to the following process. Dissolve 1 g of 2-isopropoxystyrene (Sinopharm Chemical Reagent Co., Ltd., 97%) in 10 mL of toluene to obtain the twelfth mixed solution. Add 0.1 g of anhydrous aluminum chloride (Sinopharm Chemical Reagent Co., Ltd., 98%) to this twelfth mixed solution, then add 0.5 mL of tert-butyl chloride (Adamas Reagent Co., Ltd., 99%), and react for 3 h to obtain a reaction solution; then, dropwise add the above reaction solution to 0.7 g of metallic lithium (Sinopharm Chemical Reagent Co., Ltd., 99%) at -78 °C to obtain a toluene solution containing alkyllithium. Take 1.5 mL of this toluene solution containing alkyllithium and drop it into 3 g of 3,5-dibromopyridine, stir and react for 7 h, and then perform recrystallization at -30 °C. The precipitated solid is the ligand B corresponding to the ruthenium-based catalyst VI.

[0098] Example 1

[0099] This example provides a method for preparing a cycloolefin polymer, including:

[0100] 1) Dissolve 5 g of 8-methyltetracyclododecene in 100 mL of cyclohexane to obtain a solution of the cycloolefin polymer monomer; dissolve 0.12 g of the ruthenium-based catalyst III in 100 mL of cyclohexane to obtain a solution of the ruthenium-based catalyst; dissolve 0.14 g of 1-octene in 200 mL of cyclohexane to obtain a solution of the chain transfer agent;

[0101] 2) Preheat the solutions of the above cycloolefin polymer monomers, the chain transfer agent, and the ruthenium-based catalyst at 70 °C for 30 min respectively;

[0102] 3) Under atmospheric pressure, mix 25 mL of the preheated solution of the cycloolefin polymer monomer, 45 mL of the preheated solution of the chain transfer agent, and 1.1 mL of the preheated solution of the ruthenium-based catalyst to obtain a mixed solution, and stir the above mixed solution at 70 °C for 60 min to carry out a ring-opening polymerization reaction;

[0103] 4) After the ring-opening polymerization reaction is completed, introduce hydrogen into the above mixed solution for a hydrogenation reaction, and carry out the hydrogenation reaction at 180 °C and 0.8 MPa for 12 h;

[0104] 5) After the hydrogenation reaction is completed, add 20 mL of a mixed solution of vinyl ethyl ether and cyclohexane (the volume ratio of vinyl ethyl ether to cyclohexane is 1:4) to the above mixed solution, and stir at 80 °C for 15 min; then add 5 g of thiourea resin to the mixed solution, stir for 10 min, filter to obtain the supernatant; dropwise add the supernatant to 1.5 L of acetone to form a white suspension, and filter the white suspension to obtain the cycloolefin polymer.

[0105] Comparative Example 1

[0106] This comparative example provides a method for preparing a cycloolefin polymer, including:

[0107] 1) Dissolve 1.25 g of 8-methyltetracyclododecene, 0.05 g of 1-octene, and 12 mg of 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(dichlorobenzylidene)(tricyclohexylphosphine)ruthenium in 70 mL of cyclohexane to obtain a mixed solution, and stir the above mixed solution at 70 °C for 60 min to carry out a ring-opening polymerization reaction;

[0108] 2) After the ring-opening polymerization reaction is completed, introduce hydrogen into the above mixed solution for a hydrogenation reaction, and carry out the hydrogenation reaction at 150 °C and 0.8 MPa for 10 h;

[0109] 3) After the hydrogenation reaction is completed, add 20 mL of a mixed solution of vinyl ethyl ether and cyclohexane (the volume ratio of vinyl ethyl ether to cyclohexane is 1:4) to the above mixed solution, and stir at room temperature for 15 min; then add 5 g of thiourea resin to the mixed solution, stir for 10 min, filter to obtain the supernatant; dropwise add the supernatant to 1.5 L of acetone to form a white suspension, and filter the white suspension to obtain the cycloolefin polymer.

[0110] Comparative Example 2

[0111] This comparative example provides a method for preparing a cycloolefin polymer, including:

[0112] 1) Dissolve 1.25 g of 8-methyltetracyclododecene, 0.36 g of N-phenyl-5-norbornene-2,3-dicarboximide, 0.05 g of 1-octene, and 12 mg of 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(dichlorobenzylidene)(tricyclohexylphosphine)ruthenium in 70 mL of cyclohexane to obtain a mixed solution. Stir the above mixed solution at 70 °C for 60 min to carry out a ring-opening polymerization reaction;

[0113] 2) After the ring-opening polymerization reaction is completed, introduce hydrogen into the above mixed solution for a hydrogenation reaction. Carry out the hydrogenation reaction at 150 °C and 0.8 MPa for 10 h;

[0114] 3) After the hydrogenation reaction is completed, add a mixed solution of 5 mL of vinyl ethyl ether and cyclohexane (the volume ratio of vinyl ethyl ether to cyclohexane is 1:4) to the above mixed solution. Stir at room temperature for 15 min; then add 5 g of thiourea resin to the mixed solution, stir for 10 min, and filter to obtain the supernatant; dropwise add the supernatant to 1.5 L of acetone to form a white suspension, and filter the white suspension to obtain a cycloolefin polymer.

[0115] Comparative Example 3

[0116] This comparative example provides a method for preparing a cycloolefin polymer, including:

[0117] 1) Dissolve 5 g of 8-methyltetracyclododecene in 100 mL of cyclohexane to obtain a solution of cycloolefin polymer monomer; dissolve 0.12 g of ruthenium-based catalyst III in 100 mL of cyclohexane to obtain a solution of ruthenium-based catalyst; dissolve 0.14 g of 1-octene in 200 mL of cyclohexane to obtain a solution of chain transfer agent;

[0118] 2) Preheat the above solutions of cycloolefin polymer monomer, chain transfer agent, and ruthenium-based catalyst at 30 °C for 30 min respectively;

[0119] 3) Under atmospheric pressure, mix 25 mL of the solution of cycloolefin polymer monomer, 45 mL of the solution of chain transfer agent, and 1.1 mL of the solution of ruthenium-based catalyst to obtain a mixed solution. Stir the above mixed solution at 70 °C for 60 min to carry out a ring-opening polymerization reaction;

[0120] 4) After the ring-opening polymerization reaction is completed, introduce hydrogen into the above mixed solution for a hydrogenation reaction. Carry out the hydrogenation reaction at 180 °C and 0.8 MPa for 12 h;

[0121] 5) After the hydrogenation reaction is completed, add 20 mL of a mixed solution of vinyl ethyl ether and cyclohexane (the volume ratio of vinyl ethyl ether to cyclohexane is 1:4) to the above-mentioned mixed solution. Stir for 15 min at 80 °C. Then add 5 g of thiourea resin to the mixed solution. After stirring for 10 min, filter to obtain the supernatant. Dropwise add the supernatant into 1.5 L of acetone to form a white suspension. Filter the white suspension to obtain the cycloolefin polymer.

[0122] Referring to the process of Example 1, the preparation of cycloolefin polymers of Examples 2-22 and Comparative Examples 3-8 was carried out respectively. The cycloolefin polymer monomers, the concentration of the cycloolefin polymer monomers in the solution of the cycloolefin polymer monomers, the ruthenium-based catalyst, the concentration of ruthenium element in the solution of the ruthenium-based catalyst, the chain transfer agent, the concentration of the chain transfer agent in the solution of the chain transfer agent, the molar ratio of the cycloolefin polymer monomers and the chain transfer agent in the mixed solution, the molar ratio of the cycloolefin polymer monomers and ruthenium element in the mixed solution, the inert solvent, etc. are summarized in Tables 1, 2 and 3; the preheating temperature and time, the ring-opening polymerization reaction temperature and time, the hydrogen source, the hydrogenation reaction temperature, pressure and time, the terminator and the termination reaction temperature and time, the adsorbent, the poor solvent, etc. of each example and comparative examples 3-8 are summarized in Tables 4 and 5.

[0123] Table 1

[0124]

[0125] Table 2

[0126]

[0127] Table 3

[0128]

[0129] Table 4

[0130]

[0131] Table 5

[0132]

[0133] Test Example

[0134] 1. Detect the following parameters for the above examples and comparative examples:

[0135] 1) The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (PDI) of the cycloolefin polymer were determined using a high-temperature gel permeation chromatograph, with 1,2,4-trichlorobenzene as the mobile phase and narrow-distribution polystyrene as the standard. The specific results are shown in Tables 6 and 7; among them, the high-temperature gel permeation chromatograms of the cycloolefin polymers in Example 1 and Comparative Example 1 are shown in Figure 1 and Figure 2 ( Figure 1 and Figure 2 where A refers to the number distribution curve of polymer chains in different molecular weight ranges, and B refers to the number curve of short-chain branches per 1000 carbon atoms in polymer chains in different molecular weight ranges).

[0136] 2) The glass transition temperature of the cycloolefin polymer was measured using a differential scanning calorimeter (DSC) under the condition of a heating rate of 20 °C / min. The specific results are shown in Tables 6 and 7;

[0137] 3) The hydrogenation rate of the cycloolefin polymer was measured by H-NMR spectroscopy, and deuterated chloroform was selected as the solvent. The specific results are shown in Tables 6 and 7;

[0138] 4) The refractive index of the cycloolefin polymer was measured using a precision refractometer. A thin film sample with a thickness of 4 mm was prepared from the cycloolefin polymer, and the light source was a He lamp (wavelength 587.6 nm). The refractive index at 25 °C was measured. The specific results are shown in Tables 6 and 7;

[0139] 5) The light transmittance of the cycloolefin polymer was measured using a spectrophotometer. A thin film with a thickness of 3 mm was prepared from the cycloolefin polymer, and the test wavelength was 430 nm. The specific results are shown in Tables 6 and 7;

[0140] 6) Calculate the unit dosage of the ruthenium-based catalyst (ruthenium-based catalyst / cycloolefin monomer): The content of ruthenium element in the ruthenium-based catalyst solution was detected by ICP-AES (radio frequency power 1150 W; auxiliary gas flow rate 0.5 L / min; nebulizer gas flow rate 0.75 L / min; cooling water flow rate 12 L / min; peristaltic pump speed 50 r / min). The dosage of the ruthenium-based catalyst was represented by the content of ruthenium element, and then the content of ruthenium element (dosage of the ruthenium-based catalyst) was divided by the dosage of cycloolefin monomer (molar ratio) to obtain the unit dosage of the ruthenium-based catalyst (ruthenium-based catalyst / cycloolefin monomer).

[0141] 2. Test Results

[0142] Table 6 Properties of Cycloolefin Polymers in Examples 1 - 16

[0143]

[0144] Table 7 Properties of Cycloolefin Polymers in Examples 17 - 22 and Comparative Examples 1 - 8

[0145]

[0146] Data analysis:

[0147] By using the method for preparing cycloolefin polymers in the embodiments of the present invention, it is possible to obtain cycloolefin polymers with a narrow molecular weight distribution, good thermal stability and optical properties on the premise that the amount of ruthenium-based catalyst (Ru-based catalyst) is small (judged in combination with the conversion rate and the amount of ruthenium-based catalyst). While greatly reducing the cost, cycloolefin polymers with excellent properties are obtained, thereby realizing the economical, efficient and controllable preparation of cycloolefin polymers with good properties.

[0148] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a cycloolefin polymer, characterized in that: The following steps are involved: preparing a solution of a cycloolefin polymer monomer, a solution of a chain transfer agent, and a solution of a ruthenium-based catalyst respectively; Preheating the cycloolefin polymer monomer solution, the chain transfer agent solution, and the ruthenium catalyst solution to 60-70° C. respectively; The preheated solution of the cycloolefin polymer monomer, the solution of the chain transfer agent, and the solution of the ruthenium-based catalyst are mixed to obtain a mixed solution, and the mixed solution is subjected to a ring-opening polymerization reaction at 60 to 200° C. The time of the ring-opening polymerization reaction is 5 to 65 minutes, and the temperature of the ring-opening polymerization reaction is greater than or equal to the preheating temperature; After the ring-opening polymerization reaction is completed, a hydrogen source is added to the mixed solution to carry out a hydrogenation reaction, and the hydrogenation reaction time is 6 to 12 hours; After the hydrogenation reaction is completed, a terminator, an adsorbent and a poor solvent are sequentially added to the mixed solution to separate and obtain the cycloolefin polymer; The ruthenium catalyst is prepared according to the following process: dissolving the second-generation Grubbs catalyst in dichloromethane to obtain a first mixed solution, wherein the CAS number of the second-generation Grubbs catalyst is 246047-72-3; dissolving the ligand B1 in dichloromethane to obtain a second mixed solution; then mixing the first mixed solution and the second mixed solution, adding cuprous chloride, stirring the reaction, standing at -30°C overnight, and then filtering to obtain the ruthenium catalyst; wherein, The ligand B1 is prepared by the following process: dissolving 2-isopropoxystyrene in toluene to obtain a third mixed solution; adding anhydrous aluminum chloride to the third mixed solution, and then introducing methyl chloride gas to obtain a reaction solution after reaction; then, dropping the reaction solution dropwise into metallic lithium at -78°C to obtain a toluene solution containing alkyl lithium; dropping the toluene solution containing alkyl lithium into 3,5-dibromopyridine, stirring for reaction, and then recrystallizing at -30°C, and the precipitated solid is the ligand B1; Alternatively, the ruthenium-based catalyst is prepared according to the following process: dissolving the Grubbs second-generation catalyst in toluene to obtain a fourth mixed solution, wherein the CAS number of the Grubbs second-generation catalyst is 246047-72-3; dissolving ligand A in toluene to obtain a fifth mixed solution; then mixing the fourth mixed solution and the fifth mixed solution at room temperature, stirring for reaction, adding an equal volume of n-hexane, and leaving it at -30°C overnight, then filtering, and collecting the precipitated solid; then dissolving the precipitated solid in dichloromethane to prepare a sixth mixed solution; dissolving ligand B in dichloromethane to prepare a seventh mixed solution, then mixing the sixth mixed solution and the seventh mixed solution, then adding cuprous chloride, stirring for reaction, then leaving it at -30°C overnight, filtering, and collecting the precipitated solid; The obtained solid is the ruthenium-based catalyst; wherein the ligand A is selected from 1,3-bis(2,4,6-triisopropylphenyl)imidazole or tricyclohexylphosphine; the ligand B is prepared according to the following process: the first material is dissolved in toluene to obtain an eighth mixed solution, and then anhydrous aluminum chloride is added to the eighth mixed solution, and then a second raw material is added, and after reaction, a reaction liquid is obtained, and the reaction liquid is added dropwise to metallic lithium at -78°C to obtain a toluene solution containing alkyl lithium, and the toluene solution containing alkyl lithium is added dropwise to 3,5-dibromopyridine, and after stirring for reaction, recrystallization is carried out at -30°C to precipitate a solid, which is the ligand B, wherein the first material is selected from 2-methoxystyrene or 2-isopropoxystyrene, and the second material is selected from methyl chloride gas, 1-chlorobutanol-2-one or tert-butyl chloride.

2. The preparation method according to claim 1, characterized in that: The cycloolefin polymer monomer includes one or more of the compound represented by formula (1) and the compound represented by formula (2): Formula (1) Formula (2), In the formula (1), R 1 ~R 4 Each is independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group, an aryl group having 6 to 10 carbon atoms with a substituent, or a substituent containing a first heteroatom; the first heteroatom includes one or more of a silicon atom, a nitrogen atom, and an oxygen atom; In the formula (2), R 5 ~R 6 are each independently selected from an alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a substituent containing a second heteroatom, R 7 is selected from an alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a substituent containing a third heteroatom, R 8 ~R 9 Each is independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a substituent containing a fourth heteroatom; the second heteroatom includes one or more of a silicon atom, a nitrogen atom, and an oxygen atom; the third heteroatom includes one or more of a silicon atom, a nitrogen atom, and an oxygen atom; the fourth heteroatom includes one or more of a silicon atom, a nitrogen atom, and an oxygen atom; And / or, the chain transfer agent comprises an olefin and / or a halogenated olefin having 3 to 30 carbon atoms; and / or, the concentration of the cycloolefin polymer monomer in the solution of the cycloolefin polymer monomer is 0.001 to 10 mol / L; and / or, the concentration of the chain transfer agent in the chain transfer agent solution is 0.001 to 10 mol / L; And / or, the concentration of ruthenium element in the solution of the ruthenium-based catalyst is 0.001 to 10 mol / L.

3. The preparation method according to claim 2, characterized in that: In the formula (1), R 1 and R 2 Combined with each other into a ring.

4. The preparation method according to claim 2, characterized in that: The compound represented by formula (1) includes one or more of tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-isopropyltetracyclododecene, 8-n-butyltetracyclododecene, 8-isobutyltetracyclododecene, 8-cyclopentyltetracyclododecene, 8-cyclohexyltetracyclododecene, 8-chlorotetracyclododecene, 8-bromotetracyclododecene, 8-methoxytetracyclododecene, 8-carbonyltetracyclododecene, 8-hydroxytetracyclododecene, 8-carboxytetracyclododecene, 8-aminotetracyclododecene, 8-phenoxytetracyclododecene, 8-cyanotetracyclododecene, 8-phenyltetracyclododecene, 12-methyltetracyclododecene, 12-phenoxytetracyclododecene and 12-chlorotetracyclododecene; and / or, the compound represented by formula (2) includes 5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2,3-dicarboximide, methyl-5-norbornene-2,3-dicarboxylic anhydride, ethyl-5-norbornene-2,3-dicarboxylic anhydride, isopropyl-5-norbornene-2,3-dicarboxylic anhydride, isobutyl-5-norbornene-2,3-dicarboxylic anhydride, cyclohexyl-5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboximide, ethyl-5-norbornene-2,3-dicarboxylic anhydride One or more of amine, isopropyl-5-norbornene-2,3-dicarboximide, isobutyl-5-norbornene-2,3-dicarboximide, N-hydroxy-5-norbornene-2,3-dicarboximide, N-phenyl-5-norbornene-2,3-dicarboximide, N-benzyl-5-norbornene-2,3-dicarboximide, N-naphthyl-5-norbornene-2,3-dicarboximide, norbornene-2,3-dicarboximido tert-butyl carbonate, norbornene-2,3-dicarboximido p-nitrobenzyl carbonate; And / or, the chain transfer agent includes one or more of aliphatic olefins, aromatic olefins, and halogenated olefins; The aliphatic olefins include one or more of 1-pentene, 2-pentene, 1-hexene, 2-hexene, 4-octene, 1-octene, and 1-heptene; the aromatic olefins include one or more of styrene, triphenylethylene, 4-phenyl-1-butene, and 6-phenyl-1-hexene; the halogenated olefins include one or more of 4-bromo-1-butene, 2-bromo-2-butene, 6-bromo-1-hexene, 5,6-dibromo-1-hexene, 6-chloro-1-hexene, and 8-chloro-1-octene.

5. The preparation method according to claim 1, characterized in that: In the mixed solution, the molar ratio of the cycloolefin polymer monomer to the ruthenium element is 1:(1×10 -5 ~5×10 -4 ); And / or, in the mixed solution, the molar ratio of the cycloolefin polymer monomer to the chain transfer agent is 1:(1×10 -4 ~5×10 -2 ); And / or, the pressure of the ring-opening polymerization reaction is 0.1-5 MPa.

6. The preparation method according to claim 1, characterized in that: The hydrogen source includes hydrogen and / or hydrazine compounds; The hydrazine compound includes one or more of hydrazine, phenylhydrazine, formic hydrazide, acetic hydrazide, valeric hydrazide, hexanoic hydrazide, benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide and phenylmethanesulfonyl hydrazide; And / or, the temperature of the hydrogenation reaction is -10 to 210° C., and the pressure of the hydrogenation reaction is 0.05 to 15 MPa.

7. The preparation method according to claim 1, characterized in that: The terminator includes an olefin having 3 to 30 carbon atoms and containing a sixth heteroatom, wherein the sixth heteroatom includes one or more of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom, and a halogen atom; and / or, the adsorbent comprises one or more of thiourea resin, activated carbon, silica gel, diatomaceous earth, and alumina; And / or, the poor solvent includes one or more of alcohol solvents, aldehyde and ketone solvents, ether solvents, and phenol solvents; The alcohol solvent includes one or more of methanol, ethanol, isopropanol, ethylene glycol, and n-butanol; the aldehyde and ketone solvent includes one or more of acetone, acetone aldehyde, bromoacetone, propionaldehyde, and isobutyraldehyde; the ether solvent includes one or more of ethyl ether, methyl ethyl ether, dibutyl ether, and tetrahydrofuran; the phenol solvent includes one or more of phenol, o-cresol, and propofol.

8. The preparation method according to claim 1, characterized in that: The terminator includes one or more of 1,1-diethoxyethylene, 1-bromo-2-ethoxyethylene, methoxyethylene, ethoxyethylene, 2-methoxypropylene, 3,3-dimethoxypropylene, 3-methoxyacrylic acid, ethyl propylene ether, and 3-ethoxyacrylic acid; And / or, after the hydrogenation reaction is terminated, the terminator, the adsorbent and the poor solvent are sequentially added to the mixed solution to separate and obtain the cycloolefin polymer, the process comprising: After the hydrogenation reaction is terminated, the terminator is added to the mixed solution, and the temperature of the mixed solution is controlled to be 45-250°C, and the temperature of the mixed solution is controlled to be greater than or equal to the temperature of the ring-opening polymerization reaction, and after 1-60 minutes; the adsorbent is added thereto to remove the ruthenium catalyst; then the poor solvent is added thereto to precipitate the cycloolefin polymer, and the cycloolefin polymer is separated; wherein the molar ratio of the terminator to the ruthenium element in the mixed solution is (1-100):1; And / or, after the hydrogenation reaction is terminated, the terminator, the adsorbent and the poor solvent are sequentially added to the mixed solution to separate and obtain the cycloolefin polymer, the process comprising: After the hydrogenation reaction is terminated, the solution of the terminator, the adsorbent and the solution of the poor solvent are sequentially added to the mixed solution to separate and obtain the cycloolefin polymer; wherein the concentration of the terminator in the solution of the terminator is 0.001 to 10 mol / L; the solution of the poor solvent includes a pH adjuster, and the pH adjuster includes one or more of hydrochloric acid, sulfuric acid, lactic acid, acetic acid, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide and potassium carbonate.

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