Metallocene compounds, catalyst compositions, olefin polymerization methods, and ethylene-cycloolefin copolymers, and methods for producing the same.

Abstract

The present invention discloses a metallocene compound, a catalyst composition using the metallocene compound, an olefin polymerization method using the catalyst composition, and an ethylene-cycloolefin copolymer, as well as a method for producing the same. The metallocene compound has the structure shown in formula (1). The catalyst composition has the advantages of high catalytic activity, good copolymerization performance, and a high molecular weight of the resulting polymer. [Formula 1] JPEG2026523272000016.jpg47169 (In equation (1), M is a tetravalent transition metal atom, and X 1 and X 2 Each of these is independently a halogen atom, a C1-C10 alkyl group, a C6-C12 aromatic group, or a C2-C8 N,N-dihydrocarbylamino group.

Description

[Technical Field]

[0001] [Cross-reference of related applications] This application claims the benefits of Chinese Patent Applications No. 202310961989.1 and No. 202310961997.6, filed on August 1, 2023, the contents of which are incorporated herein by reference.

[0002] The present invention relates to the field of olefin polymerization, and more specifically to metallocene compounds, catalyst compositions using the metallocene compounds, methods for olefin polymerization using the catalyst compositions, and ethylene-cycloolefin copolymers, as well as methods for producing the same. [Background technology]

[0003] Metallocene compounds for olefin polymerization have been a hotspot in research in organometallic chemistry, catalysis, polymer chemistry, and materials science for the past few decades. Using this type of catalyst, olefin polymers with uniform molecular weight and chemical composition distributions can be obtained, and by adjusting the catalyst structure, the molecular structure and molecular weight of the polymer can be highly controlled. Metallocenes exhibit high copolymerization capabilities, which are reflected in two aspects (ChemistrySelect 2020, 5, 7581-7585). First, under the same polymerization conditions, copolymers obtained with metallocenes have a higher comonomer content than copolymers obtained with other catalysts, indicating high copolymerization efficiency. Second, monomers that cannot be polymerized with other catalysts can also be used as comonomers in metallocene compound systems, indicating a broad copolymerization range. Due to their high copolymerization efficiency and broad copolymerization range, metallocene compounds can be used as catalysts in the production of many novel copolymers. These copolymers have novel compositions and structures compared to copolymers obtained with other catalysts, potentially resulting in new properties and enabling new applications in areas of polyolefin materials.

[0004] The structure of a metallocene catalyst determines its catalytic performance. Even slight structural changes can lead to significant changes in catalytic performance. When designing metallocene catalysts, improving the polymerization activity and copolymerization performance of the catalyst, as well as the molecular weight of the polymer, through structural design enhances the operability of production and improves the economic efficiency of production.

[0005] Existing metallocene catalysts still have issues that need improvement, such as catalytic activity, copolymerization performance, and polymer molecular weight. [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention aims to provide a novel metallocene compound, a catalyst composition using the metallocene compound, an olefin polymerization method using the catalyst composition, and an ethylene-cycloolefin copolymer, as well as a method for producing the same. The catalyst composition of the present invention has the advantages of high catalytic activity, good copolymerization performance, and a high molecular weight of the resulting polymer. Furthermore, the catalyst is easy to synthesize and has a relatively low synthesis cost. [Means for solving the problem]

[0007] To achieve the above objective, one aspect of the present invention provides a metallocene compound having a structure represented by formula (1). [ka] (In equation (1), M is a tetravalent transition metal atom, and X 1 and X 2 Each of these is independently a halogen atom, a C1-C10 alkyl group, a C6-C12 aromatic group, or a C2-C8 N,N-dihydrocarbylamino group.

[0008] Preferably, M is a titanium atom, a zirconium atom or a hafnium atom, preferably a titanium atom or a zirconium atom, more preferably a zirconium atom.

[0009] Preferably, X 1 and X 2 are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or an N,N-dihydrocarbylamino group having 2 to 6 carbon atoms, more preferably, X 1 and X 2 are each independently a halogen atom, an alkyl group having 1 to 3 carbon atoms, an aromatic group having 6 to 8 carbon atoms, or an N,N-dialkylamino group having 2 to 6 carbon atoms, still more preferably, X 1 and X 2 are each independently F, Cl, Br, I, a methyl group, an ethyl group, a propyl group, a phenyl group, a benzyl group, an N,N-dimethylamino group, an N,N-diethylamino group, or an N,N-dipropylamino group, even more preferably, X 1 and X 2 are each independently Cl, a methyl group, a benzyl group, or an N,N-dimethylamino group.

[0010] According to the second aspect of the present invention, there is provided a catalyst composition which comprises, as components, a) the metallocene compound according to the first aspect of the present invention, and b) a cocatalyst component.

[0011] Preferably, the cocatalyst component comprises a combination of an alkylaluminoxane or an organoboron compound and an organoaluminum compound, more preferably, the cocatalyst component is a combination of an alkylaluminoxane or an organoboron compound and an organoaluminum compound.

[0012] Preferably, the alkylaluminoxane is selected from compounds having the structures represented by formula (2) and / or formula (3).

Chemical formula

[0013] Preferably, the alkylaluminoxane is a methylaluminoxane.

[0014] Preferably, the organoboron compound is [B(C6F5)4] - Z + Z + It has the structure shown by formula (4) or formula (5). [ka]

[0015] Preferably, the organoaluminum compound is a compound having a structure represented by the general formula AlX1X2X3, where X1, X2, and X3 are each a halogen atom or an alkyl group having 1 to 12 carbon atoms, and X1, X2, and X3 may be the same or different, and at least one of them is an alkyl group having 1 to 12 carbon atoms.

[0016] Preferably, the organoaluminum compound is a mixture of one or more of diethylaluminum chloride, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum, preferably triisobutylaluminum.

[0017] Preferably, the co-catalyst component is an alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane in terms of aluminum is 1:(100~50000), preferably 1:(500~10000), and more preferably 1:(500~2000).

[0018] Preferably, the co-catalyst component is a combination of an organoboron compound and an organoaluminum compound, the molar ratio of the metallocene compound to the organoboron compound is 1:(1~20), preferably 1:(1~5), more preferably 1:(1~2), and the molar ratio of the metallocene compound to the organoaluminum compound is 1:(10~5000), preferably 1:(50~1000), more preferably 1:(50~500).

[0019] A third aspect of the present invention provides an olefin polymerization method, which comprises contacting an olefin with a catalyst composition described in the second aspect of the present invention to cause a polymerization reaction.

[0020] Preferably, the concentration of the metallocene compound in the polymerization reaction system is 1 × 10⁻⁶ -8 moles / liter ~ 1 × 10⁻⁶ -2 moles / liter, preferably 1 × 10⁻⁶ -6 moles / liter ~ 1 × 10⁻⁶ -3 It is expressed as moles per liter.

[0021] Preferably, the olefin is ethylene or a combination of ethylene and α-olefin.

[0022] Preferably, the α-olefin is one or more selected from propylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene.

[0023] Preferably, the partial pressure of the ethylene is 0.1 to 6 MPa, preferably 0.1 to 3 MPa.

[0024] Preferably, the polymerization reaction is carried out in the presence of an organic solvent, the organic solvent being one or more of toluene, cyclohexane, and hexane.

[0025] Preferably, the polymerization reaction temperature is -50 to 200°C and the polymerization reaction time is 1 to 300 minutes, and more preferably, the polymerization reaction temperature is -20 to 150°C and the polymerization reaction time is 5 to 60 minutes.

[0026] A fourth aspect of the present invention provides a method for producing an ethylene-cycloolefin copolymer, the method comprising copolymerizing ethylene and a cycloolefin using the catalyst composition described in the second aspect of the present invention.

[0027] Preferably, the concentration of the metallocene compound in the copolymerization reaction system is 1 × 10⁻⁶ -8 moles / liter ~ 1 × 10⁻⁶ -2 moles / liter, preferably 1 × 10⁻⁶ -6 moles / liter ~ 1 × 10⁻⁶ -3 It is expressed as moles per liter.

[0028] Preferably, the cycloolefin is one or more of cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, and tetracyclo[6.2.1.13,6.2,7]dodeca-4-ene.

[0029] Preferably, the partial pressure of the ethylene is 0.1 to 6 MPa, preferably 0.1 to 3 MPa.

[0030] Preferably, the copolymerization reaction is carried out in the presence of an organic solvent, the organic solvent being one or more of toluene, cyclohexane, and hexane.

[0031] Preferably, the copolymerization reaction temperature is -50 to 200°C and the copolymerization reaction time is 1 to 300 minutes, and more preferably, the copolymerization reaction temperature is -20 to 150°C and the copolymerization reaction time is 5 to 60 minutes.

[0032] According to a fifth aspect of the present invention, an ethylene-cycloolefin copolymer is provided, which is produced by the method described in a fourth aspect of the present invention. [Effects of the Invention]

[0033] The present invention aims to provide, through the above technical solutions, a novel metallocene compound, a catalyst composition using the metallocene compound, an olefin polymerization method using the catalyst composition, and an ethylene-cycloolefin copolymer, as well as a method for producing the same. The catalyst composition of the present invention has the advantages of high catalytic activity, good copolymerization performance, and a high molecular weight of the resulting polymer. Furthermore, the catalyst is easy to synthesize and has a relatively low synthesis cost. [Modes for carrying out the invention]

[0034] The endpoints and any values ​​of the ranges disclosed herein should be understood to include values ​​close to those exact ranges or values, rather than being limited to those exact ranges or values. With respect to numerical ranges, one or more new numerical ranges can be obtained by combining the endpoint values ​​of each range, the endpoint values ​​of each range with individual dot values, and individual dot values, and these numerical ranges are deemed to be specifically disclosed herein.

[0035] A first aspect of the present invention provides a metallocene compound having a structure represented by formula (1). [ka] (In equation (1), M is a tetravalent transition metal atom, and X 1 and X 2 Each of these is independently a halogen atom, a C1-C10 alkyl group, a C6-C12 aromatic group, or a C2-C8 N,N-dihydrocarbylamino group.

[0036] According to the metallocene compound of the present invention, in formula (1), M is a tetravalent transition metal atom, preferably M is a titanium atom, a zirconium atom, or a hafnium atom, more preferably M is a titanium atom or a zirconium atom, and particularly preferably M is a zirconium atom.

[0037] According to the metallocene compound of the present invention, in formula (1), X 1 and X 2 Each of these is independently a halogen atom, a C1-C10 alkyl group, a C6-C12 aromatic group, or a C2-C8 N,N-dihydrocarbylamino group.

[0038] Examples of the halogen atoms mentioned above include fluorine, chlorine, bromine, or iodine, but preferably fluorine, chlorine, or bromine, more preferably chlorine or bromine, and particularly preferably chlorine.

[0039] Examples of the C1-C10 alkyl groups mentioned above include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl groups. Of these, methyl, ethyl, propyl, or isopropyl groups are preferred, and methyl or ethyl groups are preferred.

[0040] Examples of the above-mentioned aromatic groups having 6 to 12 carbon atoms include phenyl groups, benzyl groups, and phenylethyl groups. Of these, benzyl groups are preferred.

[0041] In the present invention, preferably, in formula (1), X 1 and X 2 Each of these is independently a halogen atom, a C1-C6 alkyl group, a C6-C10 aromatic group, or a C2-C6 N,N-dihydrocarbylamino group, more preferably X 1 and X 2Each of these is independently a halogen atom, a C1-C3 alkyl group, a C6-C8 aromatic group, or a C2-C6 N,N-dialkylamino group, and more preferably X 1 and X 2 Each of these is independently F, Cl, Br, I, methyl group, ethyl group, propyl group, phenyl group, benzyl group, N,N-dimethylamino group, N,N-diethylamino group, or N,N-dipropylamino group, and is particularly preferably X 1 and X 2 These are, independently, Cl, a methyl group, a benzyl group, or an N,N-dimethylamino group.

[0042] In one particularly preferred embodiment of the present invention, X 1 and X 2 It is also Cl.

[0043] In another particularly preferred embodiment of the present invention, X 1 and X 2 It is also a methyl group.

[0044] In another particularly preferred embodiment of the present invention, X 1 and X 2 It is also a benzyl group.

[0045] In another particularly preferred embodiment of the present invention, X 1 and X 2 It is also an N,N-dimethylamino group.

[0046] The following compounds are preferred as specific metallocene compounds.

[0047] In equation (1), M is a titanium atom, and X 1 and X 2 It is also Cl, In equation (1), M is a titanium atom, and X 1 and X 2 It is also a methyl group, In equation (1), M is a titanium atom, and X1 and X 2 It is also a benzyl group, In equation (1), M is a titanium atom, and X 1 and X 2 It is also an N,N-dimethylamino group, In equation (1), M is a zirconium atom, and X 1 and X 2 It is also Cl, In equation (1), M is a zirconium atom, and X 1 and X 2 It is also a methyl group, In equation (1), M is a zirconium atom, and X 1 and X 2 It is also a benzyl group, In equation (1), M is a zirconium atom, and X 1 and X 2 It is also an N,N-dimethylamino group, In equation (1), M is a hafnium atom, and X 1 and X 2 It is also Cl, In equation (1), M is a hafnium atom, and X 1 and X 2 It is also a methyl group, In equation (1), M is a hafnium atom, and X 1 and X 2 It is also a benzyl group, In equation (1), M is a hafnium atom, and X 1 and X 2 It is also an N,N-dimethylamino group.

[0048] According to the metallocene compounds of the present invention, they can be synthesized according to conventional methods of the art.

[0049] Due to its ease of synthesis and high yield, X 1 and X 2 A metallocene compound in which both simultaneously have an N,N-dimethylamino group is preferred.1 and X 2 The presence of an N,N-dimethylamino group simultaneously improves the synthesis yield and simplifies post-processing.

[0050] In this invention, X 1 and X 2 A method for producing a metallocene compound in which is an N,N-dihydrocarbylamino group having 2 to 8 carbon atoms is preferably: Step 1) involves carrying out a first catalytic reaction between compound A and compound B in the presence of catalyst C and a first solvent to obtain intermediate product D, Step 2) involves carrying out a second catalytic reaction between intermediate product D and compound E in the presence of a second solvent to obtain intermediate product F, The method includes step 3), in which intermediate product F and M(NA2)4 undergo a third catalytic reaction in the presence of a third solvent to obtain compound H. [ka] (Here, A is a hydrocarbyl group with 1 to 4 atoms, n is an integer from 1 to 5, and R 1 , R 2 , R 3 , R 4 These are, independently, a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a t-butyl group.

[0051] The following explains each step.

[0052] Step 1): Compound A and compound B undergo a first catalytic reaction in the presence of catalyst C and a first solvent to obtain intermediate product D.

[0053] In step 1) above, n is preferably 2 or 3 in the catalyst C.

[0054] The catalyst C is preferably one or more of the following: pyrrolidine, 2-methylpyrrolidine, 2,5-dimethylpyrrolidine, 2,2,5,5-tetramethylpyrrolidine, piperidine, and 2,2,6,6-tetramethylpiperidine.

[0055] The amount of catalyst C used can be selected according to compound A, and preferably the molar ratio of reactant A to catalyst C is 1:1 to 5, more preferably 1:1.1 to 3. In step 1) above, the first solvent is preferably methanol, more preferably anhydrous methanol.

[0056] The amount of the first solvent used can be selected according to compound A. For example, per mole of compound A, the amount of the first solvent used may be 0.5 to 10 L, preferably 0.8 to 5 L, and more preferably 0.8 to 2 L.

[0057] In step 1) above, the amount of compound B used can be selected according to compound A, preferably the molar ratio of reactant A to compound B is 1:1.2 to 10, preferably 1:1.5 to 5, and more preferably 1:2 to 4.

[0058] In step 1) above, the contact method for the first catalytic reaction is not particularly limited, and it is sufficient to obtain the intermediate product D. Preferably, the catalyst C is mixed with the first solvent before the first catalytic reaction with compound B is carried out.

[0059] The conditions for the first contact reaction may include a temperature of 10-25°C and a duration of 8-90 hours.

[0060] After contact by the first catalytic reaction, the product may be purified by conventional purification methods in the art. In one preferred embodiment of the present invention, after the first catalytic reaction is completed, the first solvent and unreacted catalyst are removed by solid-liquid separation of the first catalytic reaction product, and then the solid obtained by solid-liquid separation is washed with the first solvent and dried to obtain intermediate product D.

[0061] The above solid-liquid separation is not particularly limited, and various methods commonly used for solid-liquid separation in this field can be used. For example, the above solid-liquid separation can be performed by filtration and / or centrifugation.

[0062] The above drying can employ solvent removal methods commonly used in the field, and in one preferred embodiment of the present invention, the solvent is removed by vacuum at 10-25°C.

[0063] Step 2): In the presence of the second solvent, intermediate product D and compound E undergo a second catalytic reaction to obtain intermediate product F.

[0064] In step 2) above, the amount of compound E used can be selected according to the amount of intermediate product D used, preferably the molar ratio of intermediate product D to compound E is 1:0.9 to 1.1, more preferably 1:0.95 to 1.05.

[0065] In step 2) above, the second solvent is one or more of aromatic hydrocarbons, ethers, and haloalkanes, preferably one or more of ethyl ether, tetrahydrofuran, toluene, dichloromethane, and 1,2-dichloroethane.

[0066] The amount of the second solvent used can be selected according to the intermediate product D. For example, per mole of the intermediate product D, the amount of the second solvent used may be 1 to 30 L, but preferably 5 to 20 L, more preferably 12 to 18 L.

[0067] In step 2) above, the contact method for the second contact reaction is not particularly limited, and it is sufficient to obtain the intermediate product F. Preferably, the compound E is dispersed in a portion of the second solvent in an inert atmosphere (for example, in a nitrogen atmosphere or an argon atmosphere), and then the second contact reaction is carried out by adding a solution in which the intermediate product D is dissolved in the remaining solvent dropwise to the solution in which the compound E is dispersed.

[0068] Preferably, the operation of dispersing compound E in a portion of the second solvent is carried out at a temperature of -30 to 0°C, and can be stirred, for example, at -20°C for about 30 minutes.

[0069] The conditions for the second catalytic reaction may include a temperature of 10-40°C and a duration of 8-40 hours.

[0070] After contact by the second catalytic reaction, the product may be purified by conventional purification methods of the art. In one preferred embodiment of the present invention, after the second catalytic reaction is completed, the second catalytic reaction product is injected into a saturated aqueous solution of ammonium chloride, the organic phase is separated, the aqueous phase is extracted with, for example, ethyl ether, the organic phase is combined, dried with a drying agent (for example, anhydrous sodium sulfate), and then the organic solvent is removed (for example, by vacuum removal of the organic solvent) to obtain the intermediate product F.

[0071] Step 3): In the presence of a third solvent, the intermediate product F and M(NA2)4 undergo a third catalytic reaction to obtain compound H.

[0072] In the above M(NA2)4, A is preferably a methyl group, an ethyl group, or a propyl group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

[0073] In the above M(NA2)4, M is preferably a tetravalent transition metal atom, more preferably a titanium atom, a zirconium atom, or a hafnium atom, even more preferably a titanium atom or a zirconium atom, and particularly preferably a zirconium atom.

[0074] In step 3) above, the amount of M(NA2)4 used can be selected according to the amount of the intermediate product F used, preferably the molar ratio of the intermediate product F to M(NA2)4 is 1:0.95 to 1.05, more preferably 1:0.98 to 1.02.

[0075] In step 3) above, the third solvent may be, for example, toluene.

[0076] The amount of the third solvent used can be selected according to the intermediate product F. For example, per mole of the intermediate product F, the amount of the third solvent used may be 1 to 30 L, but preferably 5 to 20 L, more preferably 12 to 18 L.

[0077] The conditions for the third contact reaction may include carrying out the reaction under reflux for 12 to 36 hours.

[0078] Preferably, the third catalytic reaction is carried out in an inert atmosphere, for example, in a nitrogen atmosphere or an argon atmosphere.

[0079] After contact by the third contact reaction, the product may be purified by conventional purification methods in the art. In one preferred embodiment of the present invention, after the third contact reaction is completed, the third contact reaction product is cooled and then separated into solid and liquid, and the solvent is removed by vacuum to obtain compound H.

[0080] The above solid-liquid separation is not particularly limited, and various methods commonly used for solid-liquid separation in this field can be used. For example, the above solid-liquid separation can be performed by filtration and / or centrifugation.

[0081] In this invention, X 1 and X 2 A method for producing a metallocene compound in which is a halogen atom is preferably, The process includes step 4), in which, in the presence of a fourth solvent, the intermediate product F and n-butyllithium undergo a fourth catalytic reaction, and then the product of the fourth catalytic reaction undergoes a fifth catalytic reaction with MX4 to obtain compound I. [ka] (In MX4 and compound I, X is a halogen atom and M is a tetravalent transition metal atom.)

[0082] Examples of the halogen atoms mentioned above include fluorine, chlorine, bromine, or iodine, but preferably fluorine, chlorine, or bromine, more preferably chlorine or bromine, and particularly preferably chlorine.

[0083] Preferably, M is a titanium atom, a zirconium atom, or a hafnium atom, more preferably a titanium atom or a zirconium atom, and particularly preferably a zirconium atom.

[0084] Examples of specific compounds for MX4 include zirconium tetrafluoride, zirconium tetrachloride, zirconium tetrabromide, zirconium tetraiodide, titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, hafnium tetrafluoride, hafnium tetrachloride, hafnium tetrabromide, or hafnium tetraiodide, but zirconium tetrachloride is preferred.

[0085] In step 4) above, the fourth solvent is one or more of alkanes, aromatic hydrocarbons, ethers, and haloalkanes, preferably one or more of n-hexane, ethyl ether, tetrahydrofuran, toluene, dichloromethane, and 1,2-dichloroethane.

[0086] In step 4) above, the amount of the fourth solvent used can be selected according to the intermediate product F. For example, per mole of the intermediate product F, the amount of the fourth solvent used may be 1 to 30 L, but preferably 5 to 20 L, more preferably 12 to 18 L.

[0087] In step 4) above, the method of the fourth catalytic reaction is preferably to disperse the intermediate product F in the fourth solvent in an inert atmosphere (for example, in a nitrogen atmosphere or an argon atmosphere), and then to carry out the fourth catalytic reaction by dropping an n-butyllithium solution (for example, an n-butyllithium hexane solution) onto the solution in which the intermediate product F is dispersed.

[0088] Preferably, the operation of dispersing the intermediate product F in the fourth solvent is carried out at a temperature of -30 to 0°C, and may be performed by stirring at, for example, -20°C for about 30 minutes.

[0089] The conditions for the fourth catalytic reaction may include a temperature of 10 to 40°C and a duration of 8 to 40 hours.

[0090] In step 4) above, preferably the molar ratio of the intermediate product F to n-butyllithium is 1:2 to 2.4, more preferably 1:2.1 to 2.2.

[0091] In step 4) above, the fourth catalytic reaction product and MX4 undergo a fifth catalytic reaction. In the fifth catalytic reaction, MX4 may be added directly to the fourth catalytic reaction product in solid form, or it may be used in a dispersed form in the fifth solvent.

[0092] The fifth solvent mentioned above is the same solvent as the fourth solvent mentioned above.

[0093] In step 4) above, the amount of MX4 used can be selected according to the intermediate product F, and preferably the molar ratio of the intermediate product F to MX4 is 1:0.95 to 1.

[0094] In step 4) above, the fifth contact method is preferably to add the MX4 solution dropwise to the fourth contact reaction product in an inert atmosphere (for example, a nitrogen atmosphere or an argon atmosphere) at -80 to -60°C, and then carry out the fifth contact reaction.

[0095] The conditions for the fifth contact reaction may include a temperature of 10 to 40°C and a time of 8 to 96 hours.

[0096] After contact by the fifth contact reaction, the product may be purified by conventional purification methods in the art. In one preferred embodiment of the present invention, after the fifth contact reaction is completed, the fifth contact reaction product is subjected to solid-liquid separation, the solid obtained by solid-liquid separation is extracted 3 to 5 times with an organic solvent (preferably toluene), the liquid phase obtained by solid-liquid separation and the extract are combined, the solvent is removed by vacuum, and the mixture is washed (for example, by washing with n-hexane), and any remaining solvent in the solid is removed by vacuum to obtain compound I.

[0097] In the present invention, the method for producing compound I may involve directly carrying out a fifth contact reaction with MX4 using the second contact reaction product obtained in step 2) above to obtain compound I.

[0098] In this invention, X 1 and X 2 A method for producing a metallocene compound in which is an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 12 carbon atoms is preferably: In the presence of the sixth solvent, the compounds I and R 0 The procedure includes step 5) of subjecting MgY to a sixth catalytic reaction to obtain compound J. [ka] (R 0 In MgY, R 0 (where Y is an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 12 carbon atoms, and Y is a chlorine atom or a bromine atom.)

[0099] The alkyl groups having 1 to 10 carbon atoms, or the aromatic groups having 6 to 12 carbon atoms, are as described above.

[0100] In step 5) above, preferably, the compounds I and R 0 The molar ratio with MgY is 1:2 to 3, preferably 1:2.2 to 2.5.

[0101] In step 5) above, preferably, the sixth solvent is one or more of alkanes, aromatic hydrocarbons, ethers, and haloalkanes, preferably one or more of n-hexane, ethyl ether, tetrahydrofuran, toluene, dichloromethane, and 1,2-dichloroethane.

[0102] The amount of the sixth solvent used can be selected according to the compound I. For example, per mole of the intermediate product I, the amount of the sixth solvent used may be 5 to 60 L, but preferably 10 to 40 L, and more preferably 25 to 32 L.

[0103] In step 5) above, the sixth contact method is preferably in an inert atmosphere (for example, a nitrogen atmosphere or an argon atmosphere) at -30 to 0°C. 0 The MgY solution is added dropwise to the mixture of compound I and the sixth solvent, and then the sixth contact reaction is carried out.

[0104] The conditions for the sixth contact reaction may include a temperature of 10 to 40°C and a time of 10 to 30 hours.

[0105] After contact by the sixth contact reaction, the product may be purified by conventional purification methods of the art. In one preferred embodiment of the present invention, after the sixth contact reaction is completed, the sixth contact reaction product is separated by solid-liquid separation, and then the solvent is removed from the obtained solid by vacuum to obtain compound J.

[0106] According to a second aspect of the present invention, a catalyst composition is provided, the catalyst composition comprising, a) A metallocene compound according to the first aspect of the present invention, b) Includes a co-catalyst component.

[0107] According to the catalyst composition of the present invention, preferably, the co-catalyst component comprises a combination of an alkylaluminoxane or organoboron compound and an organoaluminum compound, and more preferably, the co-catalyst component comprises a combination of an alkylaluminoxane or organoboron compound and an organoaluminum compound.

[0108] The alkylaluminoxanes mentioned above are preferably selected from compounds having the structures represented by formula (2) and / or formula (3). [ka] (In formulas (2) and (3), R is selected from alkyl groups having 1 to 15 carbon atoms, n represents an integer from 4 to 30, and more preferably, R is selected from alkyl groups having 1 to 5 carbon atoms, and n represents an integer from 10 to 30.)

[0109] Specific examples of the alkyl groups mentioned above include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, s-butyl group, isobutyl group, pentyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, neopentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, and pentadecyl group.

[0110] Examples of n above include 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, and so on.

[0111] Specific examples of the alkylaluminoxane include, for example, methylaluminoxane, ethylaluminoxane, and propylaluminoxane, but among these, methylaluminoxane is preferred.

[0112] According to the catalyst composition of the present invention, preferably, the organoboron compound is [B(C6F5)4] - Z + Z + It has the structure shown by formula (4) or formula (5). [ka]

[0113] According to the catalyst composition of the present invention, preferably, the organoaluminum compound is a compound having a structure represented by the general formula AlX1X2X3, where X1, X2, and X3 are each a halogen atom or an alkyl group having 1 to 12 carbon atoms, and X1, X2, and X3 may be the same or different, and at least one of them is an alkyl group having 1 to 12 carbon atoms.

[0114] Examples of the C1-C12 alkyl groups mentioned above include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, s-butyl, isobutyl, pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups.

[0115] Examples of the halogen atoms mentioned above include fluorine, chlorine, bromine, or iodine, but preferably fluorine, chlorine, or bromine, more preferably chlorine or bromine, and particularly preferably chlorine.

[0116] In the present invention, specific examples of the organoaluminum compound include, for example, one or more of the following: diethylaluminum chloride, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum, but triisobutylaluminum is preferred.

[0117] According to the catalyst composition of the present invention, the cocatalyst component is an alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane in terms of aluminum is 1:(100 - 50000), preferably 1:(500 - 10000), more preferably 1:(500 - 2000).

[0118] According to the catalyst composition of the present invention, when the cocatalyst component is a combination of an organoboron compound and an organoaluminum compound, the molar ratio of the metallocene compound to the organoboron compound is 1:(1 - 20), preferably 1:(1 - 5), more preferably 1:(1 - 2), and the molar ratio of the metallocene compound to the organoaluminum compound is 1:(10 - 5000), preferably 1:(50 - 1000), more preferably 1:(50 - 500).

[0119] According to the third aspect of the present invention, an olefin polymerization method is provided, which includes contacting an olefin with the catalyst composition described in the second aspect of the present invention to carry out a polymerization reaction.

[0120] According to the method of the present invention, preferably, the concentration of the metallocene compound in the polymerization reaction system is 1×10 -8 mol / L to 1×10 -2 mol / L, preferably 1×10 -6 mol / L to 1×10 -3 mol / L.

[0121] According to the method of the present invention, the polymerization reaction is preferably carried out in an inert organic solvent. The inert organic solvent may be a mixture of one or more linear aliphatic hydrocarbons, branched aliphatic hydrocarbons, substituted or unsubstituted cyclic aliphatic hydrocarbons, or substituted or unsubstituted aromatic hydrocarbons. Specific examples of the inert organic solvent include hexane, heptane, cyclohexane, cyclooctane, toluene, and xylene, of which toluene, cyclohexane, and hexane are preferred, one or more of which are preferred. The amount of organic solvent can be determined according to the reaction activity to ensure that the resulting polymer dissolves well in the system and does not affect the dispersion.

[0122] According to the method of the present invention, preferably, the olefin is ethylene or a combination of ethylene and α-olefin.

[0123] According to the method of the present invention, preferably, the α-olefin is one or more selected from propylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene.

[0124] According to the method of the present invention, when the olefin is ethylene, the partial pressure of the ethylene is 0.1 to 6 MPa, preferably 0.1 to 3 MPa.

[0125] According to the method of the present invention, when the olefin is a combination of ethylene and α-olefin, the amounts of ethylene and α-olefin used may be amounts commonly used in the synthesis of ethylene-α-olefin copolymers in the art. For example, the concentration of α-olefin in the polymerization reaction system is 0.001 to 8 moles / liter, preferably 0.005 to 4 moles / liter. Furthermore, the partial pressure of ethylene is 0.1 to 6 MPa, preferably 0.1 to 3 MPa.

[0126] According to the method of the present invention, the polymerization reaction conditions may be conditions commonly used in the art for the synthesis of polyolefins. Preferably, the polymerization reaction temperature is -50 to 200°C and the polymerization reaction time is 1 to 300 minutes, and more preferably, the polymerization reaction temperature is -20 to 150°C and the polymerization reaction time is 5 to 60 minutes.

[0127] A fourth aspect of the present invention provides a method for producing an ethylene-cycloolefin copolymer, the method comprising copolymerizing ethylene and a cycloolefin using the catalyst composition described in the second aspect of the present invention.

[0128] According to the present invention, preferably, the concentration of the metallocene compound in the copolymer reaction system is 1 × 10⁻⁶ -8 moles / liter ~ 1 × 10⁻⁶ -2 moles / liter, preferably 1 × 10⁻⁶ -6 moles / liter ~ 1 × 10⁻⁶ -3 It is expressed as moles per liter.

[0129] According to the present invention, the copolymerization reaction is preferably carried out in an inert organic solvent. The inert organic solvent may be a mixture of one or more linear aliphatic hydrocarbons, branched aliphatic hydrocarbons, substituted or unsubstituted cyclic aliphatic hydrocarbons, or substituted or unsubstituted aromatic hydrocarbons. Specific examples of the inert organic solvent include hexane, heptane, cyclohexane, cyclooctane, toluene, and xylene, of which toluene, cyclohexane, and hexane are preferred, one or more of which are preferred. The amount of organic solvent can be determined according to the reaction activity so that the resulting copolymer dissolves well in the system and does not affect the dispersion.

[0130] According to the present invention, preferably the cycloolefin is a cycloolefin containing 5 to 18 carbon atoms, and more preferably the cycloolefin is one or more of cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, and tetracyclo[6.2.1.13,6.2,7]dodeca-4-ene.

[0131] According to the present invention, the amounts of ethylene and the cycloolefin used may be those commonly used in the synthesis of ethylene-cycloolefin copolymers in the art. For example, the concentration of cycloolefin in the copolymer reaction system may be 0.001 to 10 moles / liter, but preferably 0.05 to 5 moles / liter. Furthermore, the partial pressure of the ethylene is 0.1 to 6 MPa, preferably 0.1 to 3 MPa.

[0132] According to the method of the present invention, the copolymerization reaction conditions may be conditions commonly used in the art for the synthesis of polyolefins. Preferably, the copolymerization reaction temperature is ~50 to 200°C and the copolymerization reaction time is 1 to 300 minutes, and more preferably, the copolymerization reaction temperature is -20 to 150°C and the copolymerization reaction time is 5 to 60 minutes.

[0133] According to a fifth aspect of the present invention, an ethylene-cycloolefin copolymer is provided, which is produced by the method described in a fourth aspect of the present invention.

[0134] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.

[0135] Unless otherwise specified, the raw materials used in the following examples and comparative examples are all disclosed in the prior art and can be purchased as is or manufactured according to the manufacturing methods disclosed in the prior art.

[0136] In the following examples and comparative examples, the synthesized compound 11H nuclear magnetic resonance ( 1 1H-NMR) was carried out at 25 °C using a Bruker AVANCEIII-400 MHz spectrometer with CDCl3 as the solvent.

[0137] The polymer molecular weight was measured by gel permeation chromatography (GPC) at 150 °C using Waters Alliance GPCV2000 with 1,2,4-trichlorobenzene as the solvent.

[0138] The content of the copolymer in the polymer was measured by solution 13 13C nuclear magnetic resonance ( 13 13C-NMR) experiments performed on a Bruker AVANCEIII-400 MHz spectrometer equipped with a 10 mm PASEX 13C-1H / D Z-GRD probe. The 13 13C resolution of the spectrometer is 0.09 Hz. The sample solution was prepared by dissolving 200 mg of the polymer material in 2.5 mL of D4-o-dichlorobenzene (ODCB-d4) in a 10 mm test tube at 130 °C. 13 The 13C-NMR measurement experiment was carried out at 125 °C, spin rate 20 Hz, pulse angle 𝜃 90°, continuous Waltz-16 decoupling, spectral width 120 ppm, acquisition time 5 s, relaxation delay 10 s. The repeating backbone methylene peak was set at 30.0000 ppm as the chemical shift reference. Example 1

[0139] This example is used to illustrate the synthesis of the metallocene compound H-1. Metallocene compound H-1: In the above compound H, M is zirconium and NA2 is a dimethylamino group. 1) Synthesis of intermediate product D

[0140] At 15°C, catalyst C (pyrrolidine, 12 mmol) was added to a 250 mL three-necked flask equipped with a magnetic stirrer, followed by 30 mL of anhydrous methanol. The mixture was stirred for 5 minutes, then compound A (1.8 g, 11.98 mmol) was added. The mixture was stirred for another 5 minutes, then compound B (2.0 g, 30.26 mmol) was added. The mixture was reacted with stirring for 24 hours, maintaining the reaction temperature below 25°C. The solvent and catalyst were removed by filtration, and the resulting product was washed with anhydrous methanol. The residual solvent was removed by vacuum at room temperature to obtain 2.26 g of a yellow solid in 94% yield. 1 H-NMR (CDCl3): 6.62-6.55ppm (2H), 6.55-6.48ppm (2H), 3.33-3.24ppm (2H), 2.14-1.85ppm (12H). 2) Synthesis of intermediate product F

[0141] Under a nitrogen atmosphere, 244 mg (2.0 mmol) of reactant E (lithium indenyl) was dispersed in 30 mL of tetrahydrofuran and stirred at -20°C for 30 minutes. 400 mg of intermediate product D (2.0 mmol) was dissolved in 10 mL of tetrahydrofuran, and this solution was slowly added dropwise to the lithium indenyl tetrahydrofuran solution. After the addition was complete, the temperature was slowly raised to room temperature and the reaction was allowed to proceed for 24 hours with stirring. The reaction mixture was poured into a saturated aqueous solution of ammonium chloride to separate the organic phase, the aqueous phase was extracted with ethyl ether, the organic phases were combined, dried over anhydrous sodium sulfate, and the organic solvent was removed by vacuum to obtain 597 mg of a yellow solid in 90% yield. 3) Synthesis of metallocene compound H-1

[0142] In a nitrogen atmosphere, 333 mg (1 mmol) of the intermediate product F was dissolved in 15 mL of toluene, and 4267 mg (1 mmol) of the reactant Zr(NMe2) was added. The mixture was refluxed at 110°C for 17 hours, cooled, filtered, and the solvent was removed by vacuum to obtain 436 mg of an orange-yellow solid in 89% yield. 1H-NMR(CDCl3):7.49-7.46ppm(1H),7.38-7.35ppm(1H),7.30-7.28ppm(1H),7.0 2-6.98ppm(1H),6.82-6.78ppm(1H),6.50-6.45ppm(2H),6.11-6.08ppm(1H),5. 74-5.71ppm(1H),5.66-5.63ppm(1H),3.29-3.24ppm(1H),2.80-2.74ppm(1H),2 .48-2.46ppm(12H), 2.36-2.29ppm(2H), 2.26-2.18ppm(2H), 2.06-1.84ppm(8H). Example 2

[0143] Synthesis of metallocene compound I-1 Metallocene compound I-1: In compound I, M is zirconium and X is a chlorine atom. Pre-distilled indene (348.5 mg, 3 mmol) was weighed into a 250 mL three-neck flask A, and after three vacuum-nitrogen purgings, 10 mL of pre-dehydrated and deoxygenated anhydrous ethyl ether was added and dissolved. Three-neck flask A was placed in an oil bath at -20°C and stirred for 15 minutes. At -20°C, n-butyllithium (1.05 equivalents, 2.5 mol / L hexane solution) was added dropwise to three-neck flask A, and after the addition was complete, three-neck flask A was transferred to room temperature and stirred for 8 hours. Intermediate product D (631 mg, 1.05 equivalents) was weighed into another 100 mL three-neck flask B, and after three nitrogen purgings, 10 mL of pre-treated anhydrous ethyl ether was added and dissolved using a dry molecular sieve. Three-neck flask A was placed in an oil bath at -20°C and stirred for 15 minutes. The solution in three-neck flask B was added dropwise to three-neck flask A. After the addition was complete, three-necked flask A was moved to room temperature and stirred for 24 hours. Three-necked flask A was placed in an oil bath at -20°C and stirred for 15 minutes. n-butyllithium (1.05 equivalents, 2.5 mol / L hexane solution) was added dropwise to three-necked flask A. After the addition was complete, three-necked flask A was moved to room temperature and stirred for 8 hours. Three-necked flask A was placed in an oil bath at -70°C and stirred for 30 minutes. Under nitrogen protection, zirconium tetrachloride (700 mg, 3 mmol) solid was added to three-necked flask A in three portions and stirred at room temperature for 72 hours. The reaction mixture was transferred to a centrifuge tube, centrifuged at (3500 rpm), and the supernatant was collected. The residual solid was extracted with 5 mL of anhydrous ethyl ether, centrifuged at (3500 rpm), and the supernatant was collected. A total of three extractions were performed, and the residual solid was discarded. The supernatant and extract were combined, and the ethyl ether was removed by vacuum. The obtained solid was dissolved in a small amount of toluene, filtered into a sample bottle, and the same volume of n-hexane was added. After standing in a nitrogen box at room temperature for 24 hours, it was centrifuged to obtain 326 mg of the solid compound in a yield of 23%. 1H-NMR(CDCl3):7.65-7.62ppm(1H),7.52-7.48ppm(1H),7.36-7.32ppm(1H),7.05-7.01ppm(1H),6.91-6.88ppm(1H),6.56-6.51ppm(2H),6.15-6.12p pm(1H),5.78-5.73ppm(1H),5.69-5.65ppm(1H),3.30-3.25ppm(1H),2.83- 2.76ppm (1H), 2.37-2.29ppm (2H), 2.27-2.18ppm (2H), 2.08-1.87ppm (8H). Example 3

[0144] Synthesis of metallocene compound I-1 Metallocene compound I-1: In compound I, M is zirconium and X is a chlorine atom. Under a nitrogen atmosphere, 333 mg (1 mmol) of intermediate product F was dissolved in 15 mL of toluene, and 0.84 mL (2.5 mol / L hexane solution) of n-butyllithium was added dropwise at -20°C. After the addition was complete, three-neck flask A was moved to room temperature and stirred for 8 hours. Three-neck flask A was placed in an oil bath at -70°C and stirred for 30 minutes. Under nitrogen protection, zirconium tetrachloride (233 mg, 1 mmol) solid was added to three-neck flask A in three portions, and the mixture was stirred at room temperature for 72 hours. The reaction mixture was transferred to a centrifuge tube, centrifuged at (3500 rpm), and the supernatant was collected. The residual solid was extracted with 5 mL of anhydrous ethyl ether, centrifuged at (3500 rpm), and the supernatant was collected again. A total of three extractions were performed, and the residual solid was discarded. The supernatant and extract were combined, and the ethyl ether was removed by vacuum. The obtained solid was dissolved in a small amount of toluene, filtered into a sample bottle, and an equal volume of ultra-dried n-hexane was added. After standing in a nitrogen box at room temperature for 24 hours, the sample was centrifuged to obtain 259 mg of the solid compound in a yield of 55%. Nuclear magnetic resonance (NMU) measurements confirmed that the obtained solid compound was metallocene compound I-1. Example 4

[0145] Synthesis of metallocene compound J-1 Metallocene compound J-1: In compound J, M is zirconium, and R 0This is a benzyl group. In a nitrogen atmosphere, 474 mg (1 mmol) of metallocene compound I-1 was dissolved in 30 mL of toluene and stirred in an oil bath at -70°C for 30 minutes. 2.2 mL of benzyl magnesium chloride solution (1 mol / L tetrahydrofuran solution) was added dropwise, the temperature was slowly raised to room temperature, and the mixture was reacted for 24 hours. The mixture was then filtered, the solvent was removed by vacuum, and 502 mg of an orange-yellow solid was obtained in 85% yield. 1 H-NMR(CDCl3):7.61-7.58ppm(1H),7.50-7.47ppm(1H),7.42-7.38ppm(4H),7.36-7.32ppm(1H),7.12-7.10ppm(4H),7.04-7.00ppm(1H),6.95-6.88ppm (2H),6.92-6.88ppm(1H),6.55-6.51ppm(2H),6.16-6.11ppm(1H),5.78-5.73ppm(1H),5.68-5.64ppm(1H),3.30- 3.25ppm(1H), 2.83-2.74ppm(1H), 2.67-2.61(4H), 2.36-2.27ppm(2H), 2.24-2.13ppm(2H), 2.08-1.190ppm(8H). Example 5

[0146] Synthesis of metallocene compound J-2 Metallocene compound J-2: In compound J, M is zirconium, and R 0 This is a methyl group. In a nitrogen atmosphere, 472 mg (1 mmol) of metallocene compound I was dissolved in 30 mL of toluene, stirred in an oil bath at -70°C for 30 minutes, and 2 mL of methylmagnesium bromide solution (1 mol / L tetrahydrofuran solution) was added dropwise. The temperature was slowly raised to room temperature and the mixture was allowed to react for 24 hours. The mixture was then filtered, the solvent was removed by vacuum, and 311 mg of an orange-yellow solid was obtained in 72% yield. 1H-NMR(CDCl3):7.64-7.60ppm(1H),7.50-7.47ppm(1H),7.35-7.32ppm(1H),7. 05-7.00ppm(1H),6.91-6.88ppm(1H),6.56-6.51ppm(2H),6.15-6.11ppm(1H), 5.76-5.71ppm(1H),5.68-5.65ppm(1H),3.30-3.24ppm(1H),2.83-2.76ppm(1H ), 2.37-2.29ppm (2H), 2.27-2.18ppm (2H), 2.08-1.87ppm (8H), -0.99ppm (6H). Example 6

[0147] This example is used to illustrate the homopolymerization of ethylene. A thoroughly dried 250 mL glass polymerization bottle was vacuum-suctioned and nitrogen flushing was repeated three times. Ethylene was introduced by vacuum suction and heated in an oil bath to 70°C, maintaining ethylene at 1 standard atmosphere in the polymerization bottle. 25 mL of toluene, 1 mL of toluene solution of triisobutylaluminum (containing 1.0 mmol of triisobutylaluminum), and 2 mL of toluene solution of the catalyst (containing 5 μmol of compound I-1) were added in sequence. After the temperature stabilized at 70°C, 2 mL of toluene solution of trityltetra(pentafluorophenyl)borate (containing 6.0 μmol of trityltetra(pentafluorophenyl)borate) was added, and the timer was started. During the reaction, as ethylene was consumed, ethylene was replenished to maintain the ethylene in the polymerization bottle at 1 standard atmosphere at all times. After 20 minutes, the ethylene was cut off, the reaction mixture was poured into a beaker, 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added, the mixture was stirred for more than 6 hours, filtered to obtain the polymer, and vacuum-dried at 60°C for 24 hours to obtain 0.72 g of polymer. The polymerization activity was 432 kg polymer / molar catalyst / hour. Gel permeation chromatography detected the weight-average molecular weight of the polymer, Mw = 6.5 × 10⁻⁶. 4 The molecular weight distribution MWD was 1.98. Example 7

[0148] This example is used to illustrate the homopolymerization of ethylene. A thoroughly dried 250 mL glass polymerization bottle was vacuum-suctioned and nitrogen flushing was repeated three times. Ethylene was introduced under vacuum suction and controlled by a solenoid valve, and the mixture was heated to 70°C in an oil bath to maintain ethylene at 1 standard atmosphere in the polymerization bottle. 25 mL of toluene, 1 mL of triisobutylaluminum toluene solution (containing 1.0 mmol of triisobutylaluminum), and 2 mL of catalyst toluene solution (containing 5 μmol of compound I-1) were added in sequence. After the temperature stabilized at 70°C, 2 mL of N,N-dimethylphenylanilinium tetrakis(pentafluorophenyl)borate toluene solution (containing 6.0 μmol of N,N-dimethylphenylanilinium tetrakis(pentafluorophenyl)borate) was added, and the timer was started. During the reaction, as ethylene was consumed, ethylene was replenished to maintain the ethylene in the polymerization bottle at 1 standard atmosphere at all times. After 20 minutes, the ethylene was cut off, the reaction mixture was poured into a beaker, 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added, the mixture was stirred for more than 6 hours, filtered to obtain the polymer, and vacuum-dried at 60°C for 24 hours to obtain 0.81 g of polymer. The polymerization activity was 486 kg polymer / molar catalyst / hour. Gel permeation chromatography detected the weight-average molecular weight of the polymer, Mw = 7.2 × 10⁻⁶. 4 The molecular weight distribution (MWD) was 2.03. Example 8

[0149] This example is used to illustrate the homopolymerization of ethylene. A thoroughly dried 250 mL glass polymerization bottle was vacuum-suctioned and nitrogen flushing was repeated three times. Vacuum suction was then used to introduce ethylene, which was heated to 70°C in an oil bath, maintaining ethylene at 1 standard atmosphere in the polymerization bottle. 25 mL of toluene and 3 mL of toluene solution of methylaluminoxane (containing 5.0 mmol of methylaluminoxane) were added sequentially. After the temperature stabilized at 70°C, 2 mL of toluene solution of the catalyst (containing 5 μmol of compound I-1) was added, and the timer was started. During the reaction, as ethylene was consumed, it was replenished to maintain the ethylene in the polymerization bottle at 1 standard atmosphere at all times. After 20 minutes, the ethylene was cut off, the reaction solution was poured into a beaker, 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added, and the mixture was stirred for more than 6 hours. The mixture was filtered to obtain the polymer, which was vacuum-dried at 60°C for 24 hours to obtain 0.68 g of polymer, with a polymerization activity of 408 kg polymer / molar catalyst / hour. The results detected by gel permeation chromatography showed that the weight-average molecular weight of the polymer was Mw = 6.7 × 10⁻⁶. 4 The molecular weight distribution MWD was 2.11. Example 9

[0150] This example is used to illustrate the homopolymerization of ethylene. A thoroughly dried 100 mL stainless steel polymerization vessel was vacuum-suctioned, nitrogen flushing was repeated three times, and finally ethylene was introduced. The temperature was set to 75°C for heating, and during heating, 50 mL of toluene and 1 mL of triisobutylaluminum toluene solution (containing 1.0 mmol of triisobutylaluminum) were added in sequence. After the temperature stabilized at 75°C, 2 mL of catalyst toluene solution (containing 2 μmol of compound I-1) was added, and after 5 minutes, 2 mL of trityltetra(pentafluorophenyl)borate toluene solution (containing 2.4 μmol of trityltetra(pentafluorophenyl)borate) was added, and the ethylene was rapidly increased to 6 standard atmospheres. The temperature was then set to 80°C for heating, and the timer was started. During the reaction, as ethylene was consumed, ethylene was replenished to maintain the total pressure in the polymerization vessel at 6 standard atmospheres at all times. After 30 minutes, the ethylene was cut off, the reaction mixture was poured into a beaker, 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added, the mixture was stirred for more than 6 hours, filtered to obtain the polymer, and vacuum-dried at 60°C for 24 hours to obtain 5.70 g of polymer. The polymerization activity was 5700 kg polymer / molar catalyst / hour. Gel permeation chromatography detected the weight-average molecular weight of the polymer, Mw = 14.7 × 10⁻⁶. 4 The molecular weight distribution (MWD) was 2.25. Example 10

[0151] This example is used to illustrate the homopolymerization of ethylene. The procedure was carried out according to the method of Example 8, except that the same molar amount of compound H-1 was used instead of compound I-1, yielding 0.65 g of polymer. The polymerization activity was 3890 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 6.9 × 10⁻¹⁶, was detected by gel permeation chromatography. 4 The molecular weight distribution MWD was 2.16. Example 11

[0152] This example is used to illustrate the homopolymerization of ethylene. The procedure was carried out according to the method of Example 8, except that the same molar amount of compound J-1 was used instead of compound I-1, yielding 0.93 g of polymer. The polymerization activity was 558 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 9.6 × 10⁻⁶, was detected by gel permeation chromatography. 4 The molecular weight distribution (MWD) was 2.25. Example 12

[0153] This example is used to illustrate the homopolymerization of ethylene. The procedure was carried out according to the method of Example 8, except that the same molar amount of compound J-2 was used instead of compound I-1, yielding 0.99 g of polymer. The polymerization activity was 594 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 8.2 × 10⁻¹⁶, was detected by gel permeation chromatography. 4 The molecular weight distribution (MWD) was 2.19. Comparative Example 1

[0154] A thoroughly dried 250 mL glass polymerization bottle was vacuum-suctioned and nitrogen flushing was repeated three times. Under vacuum suction and controlled by a solenoid valve, ethylene was introduced and heated to 70°C in an oil bath, maintaining ethylene at 1 standard atmosphere in the polymerization bottle. 25 mL of toluene and 3 mL of toluene solution of methylaluminoxane (containing 5.0 mmol of methylaluminoxane) were added sequentially. After the temperature stabilized at 70°C, 2 mL of toluene solution of the catalyst (containing 5 μmol of zirconocene dichloride) was added, and the timer was started. During the reaction, as ethylene was consumed, ethylene was replenished to maintain the ethylene in the polymerization bottle at 1 standard atmosphere at all times. After 20 minutes, the ethylene was cut off, the reaction solution was poured into a beaker, 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added, and the mixture was stirred for more than 6 hours. The mixture was filtered to obtain the polymer, which was vacuum-dried at 60°C for 24 hours to obtain 0.47 g of polymer, with a polymerization activity of 282 kg polymer / molar catalyst / hour. The results detected by gel permeation chromatography showed that the weight-average molecular weight of the polymer was Mw = 2.6 × 10⁻⁶. 4 The molecular weight distribution (MWD) was 1.99. Example 13

[0155] This example is used to illustrate the copolymerization of ethylene and 1-hexene. A thoroughly dried 250 mL glass polymerization bottle was vacuum-suctioned and nitrogen flushing was repeated three times. Vacuum suction was then used to introduce ethylene, which was then heated to 70°C in an oil bath, maintaining ethylene at 1 standard atmosphere within the polymerization bottle. 24 mL of toluene, 1 mL of 1-hexene, and 3 mL of toluene solution of methylaluminoxane (containing 5.0 mmol of methylaluminoxane) were added in sequence. After the temperature stabilized at 70°C, 2 mL of toluene solution of the catalyst (containing 5 μmol of compound I-1) was added, and the timer was started. During the reaction, as ethylene was consumed, it was replenished to maintain the ethylene in the polymerization bottle at 1 standard atmosphere at all times. After 20 minutes, the ethylene was cut off, the reaction solution was poured into a beaker, 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added, and the mixture was stirred for more than 6 hours. The mixture was then filtered to obtain the polymer, which was vacuum-dried at 60°C for 24 hours to obtain 1.82 g of polymer. The polymerization activity was 1092 kg polymer / molar catalyst / hour. The results detected by gel permeation chromatography showed that the polymer's weight-average molecular weight (Mw) was 3.7 × 10⁻⁶. 4 The molecular weight distribution MWD was 1.88, and detection by 13C-NMR spectroscopy revealed that the 1-hexene unit content in the polymer was 8.7 mol%. Example 14

[0156] This example is used to illustrate the copolymerization of ethylene and 1-hexene. The procedure was carried out according to the method of Example 13, except that the same molar amount of compound H-1 was used instead of compound I-1, yielding 1.52 g of polymer. The polymerization activity was 912 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 3.1 × 10⁻¹⁶, was detected by gel permeation chromatography. 4 The molecular weight distribution MWD was 1.91, and detection by 13C-NMR spectroscopy revealed that the 1-hexene unit content in the polymer was 9.1 mol%. Example 15

[0157] This example is used to illustrate the copolymerization of ethylene and 1-hexene. The procedure was carried out according to the method of Example 13, except that the same molar amount of compound J-1 was used instead of compound I-1, yielding 2.01 g of polymer. The polymerization activity was 1206 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 4.1 × 10⁻⁶, was detected by gel permeation chromatography. 4 The molecular weight distribution MWD was 1.90, and detection by 13C-NMR spectroscopy revealed that the 1-hexene unit content in the polymer was 8.9 mol%. Example 16

[0158] This example is used to illustrate the copolymerization of ethylene and 1-hexene. The procedure was carried out according to the method of Example 13, except that the same molar amount of compound J-2 was used instead of compound I-1, yielding 2.11 g of polymer. The polymerization activity was 1266 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 4.0 × 10⁻⁶, was detected by gel permeation chromatography. 4 The molecular weight distribution MWD was 1.86, and detection by 13C-NMR spectroscopy revealed that the 1-hexene unit content in the polymer was 9.4 mol%. Comparative Example 2

[0159] The procedure was carried out according to the method of Example 13, except that the same molar amount of zirconocene dichloride was used instead of compound I-1, yielding 1.01 g of polymer. The polymerization activity was 606 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 0.97 × 10⁻¹⁶, was detected by gel permeation chromatography. 4 The molecular weight distribution MWD was 1.94, and detection by 13C-NMR spectroscopy revealed that the 1-hexene unit content in the polymer was 7.8 mol%. Example 17

[0160] This example is used to illustrate the copolymerization of ethylene-norbornene. 3.77 g of norbornene was added to a thoroughly dried 250 mL glass polymerization bottle, and the mixture was vacuum-suctioned and nitrogen flushed three times. Ethylene was introduced by vacuum suction, and the mixture was heated to 70°C in an oil bath, maintaining ethylene at 1 standard atmosphere in the polymerization bottle. 25 mL of toluene and 3 mL of toluene solution of methylaluminoxane (containing 5.0 mmol of methylaluminoxane) were added in sequence. After the temperature stabilized at 70°C, 2 mL of toluene solution of the catalyst (containing 2 μmol of metallocene compound I-1) was added, and the timer was started. During the reaction, as ethylene was consumed, ethylene was replenished to maintain the ethylene in the polymerization bottle at 1 standard atmosphere at all times. After 20 minutes, the ethylene was cut off, the reaction mixture was poured into a beaker, 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added, and the mixture was stirred for more than 6 hours. The mixture was filtered to obtain the polymer, which was vacuum-dried at 60°C for 24 hours to obtain 2.87 g of polymer, with a polymerization activity of 4305 kg polymer / molar catalyst / hour. The weight-average molecular weight of the polymer, Mw = 26.6 × 10⁻¹⁴, was detected by gel permeation chromatography. 4 The molecular weight distribution MWD was 1.89. Detection by 13C-NMR spectroscopy revealed that the norbornene unit content in the polymer was 54.3 mol%. Comparative Example 3

[0161] The procedure was carried out according to the method of Example 17, except that metallocene compound I-1 was replaced with the same molar amount of diphenylmethylene (cyclopentadienyl)(9-fluorenyl)zirconium dichloride, yielding 2.01 g of polymer. The polymerization activity was 3015 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 12.6 × 10⁶, was detected by gel permeation chromatography. 4 The molecular weight distribution MWD was 2.27, and detection by 13C-NMR spectroscopy revealed that the norbornene unit content in the polymer was 51.0 mol%. Example 18

[0162] This example is used to illustrate the copolymerization of ethylene-norbornene. 3.77 g of norbornene was added to a thoroughly dried 250 mL glass polymerization bottle, and the mixture was vacuum-suctioned and nitrogen flushed three times. Ethylene was then introduced by vacuum suction and the mixture was heated to 70°C in an oil bath to maintain ethylene at 1 standard atmosphere in the polymerization bottle. 25 mL of toluene, 1 mL of toluene solution of triisobutylaluminum (containing 1.0 mmol of triisobutylaluminum), and 2 mL of toluene solution of the catalyst (containing 2 μmol of metallocene compound I-1) were added in sequence. After the temperature stabilized at 70°C, 2 mL of toluene solution of trityltetra(pentafluorophenyl)borate (containing 2.4 μmol of trityltetra(pentafluorophenyl)borate) was added, and the timer was started. During the reaction, as ethylene was consumed, ethylene was replenished to maintain the ethylene in the polymerization bottle at 1 standard atmosphere at all times. After 20 minutes, the ethylene was cut off, the reaction mixture was poured into a beaker, 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added, the mixture was stirred for more than 6 hours, filtered to obtain the polymer, and vacuum-dried at 60°C for 24 hours to obtain 2.97 g of polymer, with a polymerization activity of 4455 kg polymer / molar catalyst / hour. The weight-average molecular weight of the polymer, Mw = 27.1 × 10⁻¹⁵, was detected by gel permeation chromatography. 4 The molecular weight distribution MWD was 1.96. Detection by 13C-NMR spectroscopy revealed that the norbornene unit content in the polymer was 55.8 mol%. Comparative Example 4

[0163] The procedure was carried out according to the method of Example 18, except that metallocene compound I-1 was replaced with the same molar amount of diphenylmethylene (cyclopentadienyl)(9-fluorenyl)zirconium dichloride, yielding 2.51 g of polymer. The polymerization activity was 3765 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 18.5 × 10⁻¹⁵, was detected by gel permeation chromatography. 4 The molecular weight distribution MWD was 2.07, and detection by 13C-NMR spectroscopy revealed that the norbornene unit content in the polymer was 54.1 mol%. Example 19

[0164] This example is used to illustrate the copolymerization of ethylene-norbornene. 4.71 g of norbornene was added to a thoroughly dried 250 mL glass polymerization bottle, and the mixture was vacuum-suctioned and nitrogen flushed three times. Ethylene was then introduced by vacuum suction and the mixture was heated to 70°C in an oil bath to maintain ethylene at 1 standard atmosphere in the polymerization bottle. 25 mL of toluene, 1 mL of toluene solution of triisobutylaluminum (containing 1.0 mmol of triisobutylaluminum), and 2 mL of toluene solution of the catalyst (containing 2 μmol of metallocene compound I-1) were added in sequence. After the temperature stabilized at 70°C, 2 mL of toluene solution of N,N-dimethylphenylanilinium tetrakis(pentafluorophenyl)borate (containing 6.0 μmol of N,N-dimethylphenylanilinium tetrakis(pentafluorophenyl)borate) was added, and the timer was started. During the reaction, as ethylene was consumed, ethylene was replenished to maintain the ethylene in the polymerization bottle at 1 standard atmosphere at all times. After 20 minutes, the ethylene was cut off, the reaction mixture was poured into a beaker, 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added, the mixture was stirred for more than 6 hours, filtered to obtain the polymer, and vacuum-dried at 60°C for 24 hours to obtain 3.02 g of polymer. The polymerization activity was 4530 kg polymer / molar catalyst / hour. Gel permeation chromatography detected the weight-average molecular weight of the polymer, Mw = 7.3 × 10⁻⁶. 4 The molecular weight distribution MWD was 1.90. Detection by 13C-NMR spectroscopy revealed that the norbornene unit content in the polymer was 55.0 mol%. Example 20

[0165] This example is used to illustrate the copolymerization of ethylene-norbornene. 20 g of norbornene was added to a thoroughly dried 100 mL stainless steel polymerization vessel, vacuum suction was applied, nitrogen flushing was repeated three times, and finally ethylene was introduced. The temperature was set to 75°C for heating, and during heating, 30 mL of toluene and 1 mL of toluene solution of triisobutylaluminum (containing 1.0 mmol of triisobutylaluminum) were added in sequence. After the temperature stabilized at 75°C, 2 mL of toluene solution of catalyst (containing 2 μmol of metallocene compound I-1) was added, and after 5 minutes, 2 mL of toluene solution of trityltetra(pentafluorophenyl)borate (containing 2.4 μmol of trityltetra(pentafluorophenyl)borate) was added, and the ethylene was rapidly increased to 2 standard atmospheres. The temperature was then set to 80°C for heating, and the timer was started. During the reaction, as ethylene was consumed, ethylene was continuously replenished to maintain the total pressure in the polymerization vessel at 2 standard atmospheres at all times. After 30 minutes, the ethylene was cut off, the reaction mixture was poured into a beaker, 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added, the mixture was stirred for more than 6 hours, filtered to obtain the polymer, and vacuum-dried at 60°C for 24 hours to obtain 11.95 g of polymer. The polymerization activity was 11950 kg polymer / molar catalyst / hour. Gel permeation chromatography detected the weight-average molecular weight of the polymer, Mw = 42.5 × 10⁻⁶. 4 The molecular weight distribution MWD was 2.00. Detection by 13C-NMR spectroscopy revealed that the norbornene unit content in the polymer was 52.7 mol%. Example 21

[0166] This example is used to illustrate the copolymerization of ethylene-norbornene. 20 g of norbornene was added to a thoroughly dried 100 mL stainless steel polymerization vessel, vacuum suction was applied, nitrogen flushing was repeated three times, and finally ethylene was introduced. The temperature was set to 75°C for heating, and during heating, 30 mL of toluene and 1 mL of triisobutylaluminum toluene solution (containing 1.0 mmol of triisobutylaluminum) were added in sequence. After the temperature stabilized at 75°C, 2 mL of catalyst toluene solution (containing 2 μmol of metallocene compound I-1) was added, and after 5 minutes, 2 mL of trityltetra(pentafluorophenyl)borate toluene solution (containing 2.4 μmol of trityltetra(pentafluorophenyl)borate) was added to rapidly increase the ethylene to 4 standard atmospheres. The temperature was then set to 80°C for heating, and the timer was started. During the reaction, as ethylene was consumed, ethylene was continuously replenished to maintain the total pressure in the polymerization vessel at 4 standard atmospheres at all times. After 30 minutes, the ethylene was cut off, the reaction mixture was poured into a beaker, 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added, the mixture was stirred for more than 6 hours, filtered to obtain the polymer, and vacuum-dried at 60°C for 24 hours to obtain 16.37 g of polymer, with a polymerization activity of 16370 kg polymer / molar catalyst / hour. Gel permeation chromatography detected the weight-average molecular weight of the polymer, Mw = 46.8 × 10⁻⁶. 4 The molecular weight distribution MWD was 1.98. Detection by 13C-NMR spectroscopy revealed that the norbornene unit content in the polymer was 49.7 mol%. Example 22

[0167] This example is used to illustrate the copolymerization of ethylene-norbornene. The procedure was carried out according to the method of Example 17, except that metallocene compound I-1 was replaced with the same molar amount of metallocene compound H-1, yielding 2.80 g of polymer. The polymerization activity was 4200 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 30.1 × 10⁻¹⁶, was detected by gel permeation chromatography. 4 The molecular weight distribution MWD was 2.11, and detection by 13C-NMR spectroscopy revealed that the norbornene unit content in the polymer was 55.0 mol%. Example 23

[0168] This example is used to illustrate the copolymerization of ethylene-norbornene. The procedure was carried out according to the method of Example 18, except that metallocene compound I-1 was replaced with the same molar amount of metallocene compound H-1, yielding 2.88 g of polymer. The polymerization activity was 4320 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 31.5 × 10⁻⁶, was detected by gel permeation chromatography. 4 The molecular weight distribution MWD was 1.99, and detection by 13C-NMR spectroscopy revealed that the norbornene unit content in the polymer was 54.9 mol%. Example 24

[0169] This example is used to illustrate the copolymerization of ethylene-norbornene. The procedure was carried out according to the method of Example 17, except that metallocene compound I-1 was replaced with the same molar amount of metallocene compound J-1, yielding 3.23 g of polymer. The polymerization activity was 4845 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 31.1 × 10⁻¹⁵, was detected by gel permeation chromatography. 4 The molecular weight distribution MWD was 2.01, and detection by 13C-NMR spectroscopy revealed that the norbornene unit content in the polymer was 55.0 mol%. Example 25

[0170] This example is used to illustrate the copolymerization of ethylene-norbornene. The procedure was carried out according to the method of Example 18, except that metallocene compound I-1 was replaced with the same molar amount of metallocene compound J-1, yielding 3.51 g of polymer. The polymerization activity was 5265 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 31.9 × 10⁻¹⁵, was detected by gel permeation chromatography. 4 The molecular weight distribution MWD was 2.11, and detection by 13C-NMR spectroscopy revealed that the norbornene unit content in the polymer was 54.8 mol%. Example 26

[0171] This example is used to illustrate the copolymerization of ethylene-norbornene. Except for replacing metallocene compound I-1 with the same molar amount of metallocene compound J-2, the procedure was carried out according to Example 17, yielding 3.15 g of polymer. The polymerization activity was 4725 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 30.5 × 10⁻⁶, was detected by gel permeation chromatography. 4 The molecular weight distribution MWD was 2.08, and detection by 13C-NMR spectroscopy revealed that the norbornene unit content in the polymer was 54.6 mol%. Example 27

[0172] This example is used to illustrate the copolymerization of ethylene-norbornene. The procedure was carried out according to the method of Example 18, except that metallocene compound I-1 was replaced with the same molar amount of metallocene compound J-2, yielding 3.25 g of polymer. The polymerization activity was 4875 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 32.2 × 10⁻¹⁶, was detected by gel permeation chromatography. 4 The molecular weight distribution MWD was 2.02, and detection by 13C-NMR spectroscopy revealed that the norbornene unit content in the polymer was 54.8 mol%. Comparative Example 5

[0173] Except for replacing metallocene compound I-1 with the same molar amount of ref-1, the procedure was carried out according to the method of Example 17, yielding 1.82 g of polymer. The polymerization activity was 2730 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 14.8 × 10⁻⁶, was detected by gel permeation chromatography. 4 The molecular weight distribution MWD was 2.32, and detection by 13C-NMR spectroscopy revealed that the norbornene unit content in the polymer was 44.2 mol%. [ka] Comparative Example 6

[0174] The procedure was carried out according to the method of Example 17, except that metallocene compound I-1 was replaced with the same molar amount of ref-2, yielding 1.56 g of polymer. The polymerization activity was 2340 kg polymer / molar catalyst / hour, and the weight-average molecular weight of the polymer, Mw = 13.9 × 10⁻⁶, was detected by gel permeation chromatography. 4 However, the molecular weight distribution MWD = 2.28 and the norbornene unit content in the polymer, as detected by 13C-NMR spectroscopy, differ from the previous findings. [ka]

[0175] Although preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, several simple modifications can be made to the technical solutions of the present invention, including combining each technical feature in any other suitable manner, and these simple modifications and combinations should also be considered as part of the disclosure of the present invention and all fall within the scope of protection of the present invention.

Claims

1. A metallocene compound, characterized in that the metallocene compound has a structure represented by formula (1). 【Chemistry 1】 (In equation (1), M is a tetravalent transition metal atom, and X １ and X ２ Each of these is independently a halogen atom, a C1-C10 alkyl group, a C6-C12 aromatic group, or a C2-C8 N,N-dihydrocarbylamino group.

2. M is a titanium atom, a zirconium atom, or a hafnium atom, preferably a titanium atom or a zirconium atom, more preferably a zirconium atom, and X １ and X ２ Each of these is independently a halogen atom, a C1-C6 alkyl group, a C6-C10 aromatic group, or a C2-C6 N,N-dihydrocarbylamino group, or M is a titanium atom or a zirconium atom, X １ and X ２ These are, independently, F, Cl, Br, I, methyl group, ethyl group, propyl group, phenyl group, benzyl group, N,N-dimethylamino group, N,N-diethylamino group, or N,N-dipropylamino group, or M is a titanium atom or a zirconium atom, X １ and X ２ The metallocene compound according to claim 1, wherein each of them is independently Cl, a methyl group, a benzyl group, or an N,N-dimethylamino group.

3. A catalyst composition comprising, a) A metallocene compound according to claim 1 or 2, b) A catalyst composition characterized by comprising a co-catalyst component.

4. The aforementioned co-catalyst component includes an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound, or The catalyst composition according to claim 3, wherein the co-catalyst component is a combination of an alkylaluminoxane or an organoboron compound and an organoaluminum compound.

5. The alkylaluminoxane is selected from compounds having the structure shown in formula (2) and / or formula (3), or The catalyst composition according to claim 4, wherein the alkylaluminoxane is methylaluminoxane. 【Chemistry 2】 (In formulas (2) and (3), R is selected from alkyl groups having 1 to 15 carbon atoms, and n represents an integer from 4 to 30.)

6. The organic boron compound is [B(C ６ F ５ )( ４ ) － Z ＋ where Z ＋ has a structure represented by formula (4) or formula (5), and the catalyst composition according to claim 4. 【Transformation 3】

7. The aforementioned organoaluminum compound has the general formula AlX １ X ２ X ３ A compound having the structure shown by X １ , X ２ and X ３ Each of these is a halogen atom or an alkyl group having 1 to 12 carbon atoms, X １ , X ２ and X ３ These may be the same or different, and at least one of them is an alkyl group having 1 to 12 carbon atoms, or The catalyst composition according to claim 4, wherein the organoaluminum compound is one or a mixture of two or more of diethylaluminum chloride, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum, preferably triisobutylaluminum.

8. The aforementioned co-catalyst component is an alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane in terms of aluminum is 1:(100 to 50000), or, The catalyst composition according to claim 4, wherein the co-catalyst component is an alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane in terms of aluminum is 1:(500 to 2000).

9. The aforementioned co-catalyst component is a combination of an organoboron compound and an organoaluminum compound, the molar ratio of the metallocene compound to the organoboron compound is 1:(1 to 20), the molar ratio of the metallocene compound to the organoaluminum compound is 1:(10 to 5000), or, The catalyst composition according to claim 4, wherein the co-catalyst component is a combination of an organoboron compound and an organoaluminum compound, the molar ratio of the metallocene compound to the organoboron compound is 1:(1-2), and the molar ratio of the metallocene compound to the organoaluminum compound is 1:(50-500).

10. A method for olefin polymerization, characterized in that the method comprises contacting an olefin with a catalyst composition described in any one of claims 3 to 9 to carry out a polymerization reaction.

11. The concentration of the metallocene compound in the polymerization reaction system is 1 × 10 －８ moles / liter ~ 1 x 10⁻⁶ －２ It is moles / liter, or, The concentration of the metallocene compound in the polymerization reaction system is 1 × 10 －６ moles / liter ~ 1 x 10⁻⁶ －３ The method according to claim 10, wherein the value is moles / liter.

12. The olefin is ethylene or a combination of ethylene and α-olefin, or The method according to claim 10, wherein the α-olefin is one or more selected from propylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene.

13. The method according to claim 12, wherein the partial pressure of the ethylene is 0.1 to 6 MPa.

14. The method according to claim 10, wherein the polymerization reaction is carried out in the presence of an organic solvent, the organic solvent being one or more of toluene, cyclohexane, and hexane.

15. The method according to any one of claims 10 to 14, wherein the polymerization reaction temperature is -50 to 200°C, and the polymerization reaction time is 1 to 300 minutes.

16. A method for producing an ethylene-cycloolefin copolymer, characterized in that the method comprises copolymerizing ethylene and a cycloolefin using a catalyst composition described in any one of claims 3 to 9.

17. The concentration of the metallocene compound in the copolymerization reaction system is 1 × 10 －８ moles / liter ~ 1 x 10⁻⁶ －２ It is moles / liter, or, The concentration of the metallocene compound in the copolymerization reaction system is 1 × 10 －６ moles / liter ~ 1 x 10⁻⁶ －３ The method according to claim 16, wherein the value is moles / liter.

18. The method according to claim 16, wherein the cycloolefin is one or more of cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, and tetracyclo[6.2.1.13,6.2,7]dodeca-4-ene.

19. The method according to any one of claims 16 to 18, wherein the partial pressure of the ethylene is 0.1 to 6 MPa.

20. The method according to any one of claims 16 to 18, wherein the copolymerization reaction is carried out in the presence of an organic solvent, the organic solvent being one or more of toluene, cyclohexane, and hexane.

21. The method according to any one of claims 16 to 18, wherein the copolymerization reaction temperature is -50 to 200°C, and the copolymerization reaction time is 1 to 300 minutes.

22. An ethylene-cycloolefin copolymer, characterized in that the copolymer is produced by the method described in any one of claims 16 to 21.

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