Metallocene compound, catalyst composition ,and method for preparing ethylene-cyclic olefin copolymer

Abstract

The present invention relates to the field of olefin polymerization, and discloses a metallocene compound, a catalyst composition, and a method for preparing an ethylene-cyclic olefin copolymer. The metallocene compound has a structure as shown in formula (1), and in formula (1), M is a tetravalent transition metal atom, and X1 and X2 are each independently a halogen atom, an alkyl group having 1-10 carbon atoms, an aromatic group having 6-12 carbon atoms or an N,N-dialkylamine group having 2-8 carbon atoms. Using the catalyst composition of the present invention in the preparation of an ethylene-cyclic olefin copolymer has the advantages of high catalytic activity, good copolymerization performance, and high molecular weight of an obtained polymer.

Description

Metallocene compound, catalyst composition and method for preparing ethylene-cycloolefin copolymer

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Chinese patent applications 202311035351.1 and 202311034962.4 filed on August 16, 2023, the contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to the field of olefin polymerization, and in particular to a metallocene compound, a catalyst composition using the metallocene compound, and a method for preparing an ethylene-cycloolefin copolymer using the catalyst composition. Background Art

[0004] Metallocene compounds for olefin polymerization have been a research hotspot in organometallic chemistry, catalysis, polymer chemistry, and materials science for decades. Using this type of catalyst, olefin polymers with uniform molecular weight and chemical composition distributions can be obtained. The molecular structure and molecular weight of the polymers can also be highly controlled by adjusting the catalyst structure. Metallocenes have strong copolymerization capabilities, which are reflected in two aspects (Chemistry Select 2020, 5, 7581–7585): On the one hand, under the same polymerization conditions, the copolymers obtained by metallocenes contain a higher content of comonomer than those obtained by other catalysts, which reflects their high copolymerization efficiency. On the other hand, some monomers that cannot be polymerized by other catalysts can also serve as comonomers in metallocene compound systems, which reflects their broad copolymerization spectrum. Due to the high efficiency and broad spectrum of metallocene compounds, they can catalyze the production of many new copolymers. Compared with copolymers obtained by other catalysts, these copolymers have new compositions and structures, and thus may have new properties, thereby enabling the application of polyolefin materials in new fields.

[0005] Cyclic olefin copolymer (COC) not only has good processability but also possesses excellent thermal, optical, and mechanical properties, such as superior heat and chemical resistance, excellent transparency, high refractive index, high hardness or flexibility, and low permeability to gases and water. These outstanding properties make COC a new type of engineering plastic with potential commercial applications in video and compact discs, optical lenses, optical fibers, foam foil, medical devices, and capacitors. Due to its excellent optical and mechanical properties, COC is used in the manufacture of optical discs, magneto-optical storage discs, gratings, and other optical devices.

[0006] Although COC has excellent performance and a wide range of uses, its high production cost restricts its further market expansion. Therefore, developing a more economical and effective catalyst system is the key to enabling this material to play a greater role in more occasions.

[0007] The structure of a metallocene catalyst determines its catalytic performance. Small structural changes can lead to significant changes in catalytic performance. When designing a metallocene catalyst, structural design is employed to maximize the catalyst's polymerization activity and copolymerization performance, as well as the molecular weight of the polymer, thereby broadening the production operating space and improving production economics.

[0008] Existing metallocene catalysts still have problems such as catalyst activity, copolymerization performance and polymer molecular weight that need to be improved.

[0009] Summary of the Invention

[0010] The present invention aims to provide a novel metallocene compound, a catalyst composition using the metallocene compound, and a method for preparing an ethylene-cycloolefin copolymer using the catalyst composition. The catalyst composition of the present invention has the advantages of high catalytic activity, good copolymerization performance, and high molecular weight of the obtained polymer in the preparation of the ethylene-cycloolefin copolymer.

[0011] In order to achieve the above object, the present invention provides a metallocene compound, wherein the metallocene compound has a structure shown in formula (1),

[0012] In formula (1), M is a tetravalent transition metal atom; X 1 and X 2 Each is independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or an N,N-dialkylamino group having 2 to 8 carbon atoms.

[0013] 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.

[0014] Preferably, X 1 and X 2 Each independently represents 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-dialkylamino group having 2 to 6 carbon atoms; more preferably, X 1 and X 2 Each is 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; further preferably, X 1 and X 2Each is independently F, Cl, Br, I, methyl, ethyl, propyl, phenyl, benzyl, N,N-dimethylamino, N,N-diethylamino or N,N-dipropylamino; more preferably, X 1 and X 2 Each is independently Cl, methyl, benzyl or N,N-dimethylamino.

[0015] According to a second aspect of the present invention, a catalyst composition is provided, wherein the catalyst composition comprises the following components:

[0016] a) the metallocene compound according to the first aspect of the present invention;

[0017] b) Co-catalyst component.

[0018] Preferably, the co-catalyst component comprises an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound; more preferably, the co-catalyst component is a combination of an alkylaluminoxane or an organoboron compound and an organoaluminum compound.

[0019] Preferably, the alkylaluminoxane is a compound selected from the structure shown in formula (2) and / or formula (3),

[0020] In formula (2) and formula (3), R is selected from an alkyl group having 1 to 15 carbon atoms, and n represents an integer of 4 to 30; more preferably, R is selected from an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 10 to 30.

[0021] Preferably, the alkylaluminoxane is methylaluminoxane.

[0022] Preferably, the organic boron compound is [B(C6F5)4] - Z + , Z + Having the structure shown in formula (4) or formula (5),

[0023] Preferably, the organoaluminum compound is a compound having a structure represented by the general formula AlX1X2X3, wherein X1, X2 and X3 are respectively a halogen atom or an alkyl group with 1-12 carbon atoms, X1, X2 and X3 may be the same or different, and at least one is an alkyl group with 1-12 carbon atoms.

[0024] Preferably, 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.

[0025] Preferably, the co-catalyst component is alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane calculated as aluminum is 1:(100-50000), preferably 1:(500-10000), and more preferably 1:(500-2000).

[0026] 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).

[0027] According to a third aspect of the present invention, a method for preparing an ethylene-cycloolefin copolymer is provided, which comprises copolymerizing ethylene and cycloolefin using a catalyst composition, wherein the catalyst composition is the catalyst composition described in the second aspect of the present invention.

[0028] Preferably, the concentration of the metallocene compound in the copolymerization reaction system is 1×10 -8 mol / L~1×10 -2 mol / L, preferably 1×10 -6 mol / L~1×10 -3 mol / L.

[0029] Preferably, the cycloolefin is one or more of cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, and tetracyclo[6.2.1.13,6.2,7]dodecene.

[0030] Preferably, the ethylene partial pressure is 0.1-6 MPa, preferably 0.1-3 MPa.

[0031] Preferably, the copolymerization reaction is carried out in the presence of an organic solvent, and the organic solvent is one or more of toluene, cyclohexane and hexane.

[0032] Preferably, the copolymerization reaction temperature is -50 to 200° C., and the copolymerization reaction time is 1 to 300 minutes.

[0033] Through the above technical solution, the present invention provides a new metallocene compound, a catalyst composition using the metallocene compound, and a method for preparing an ethylene-cycloolefin copolymer using the catalyst composition. The catalyst composition of the present invention has the advantages of high catalytic activity, good copolymerization performance, and high molecular weight of the obtained polymer in the preparation of the ethylene-cycloolefin copolymer. DETAILED DESCRIPTION

[0034] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0035] The first aspect of the present invention provides a metallocene compound, wherein the metallocene compound has a structure shown in formula (1),

[0036] In formula (1), M is a tetravalent transition metal atom; X 1 and X 2 Each is independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or an N,N-dialkylamino group having 2 to 8 carbon atoms.

[0037] 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; particularly preferably, M is a zirconium atom.

[0038] According to the metallocene compound of the present invention, in formula (1), X 1 and X 2 Each is independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or an N,N-dialkylamino group having 2 to 8 carbon atoms.

[0039] Examples of the halogen atom include fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine or bromine, more preferably chlorine or bromine, and particularly preferably chlorine.

[0040] Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Among these, methyl, ethyl, propyl, and isopropyl are preferred, and methyl or ethyl are more preferred.

[0041] Examples of the aromatic group having 6 to 12 carbon atoms include phenyl, benzyl, and phenethyl, among which benzyl is preferred.

[0042] In the present invention, preferably, in formula (1), X 1 and X 2 Each independently represents 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-dialkylamino group having 2 to 6 carbon atoms; more preferably, X 1 and X 2Each is 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; further preferably, X 1 and X 2 Each is independently F, Cl, Br, I, methyl, ethyl, propyl, phenyl, benzyl, N,N-dimethylamino, N,N-diethylamino or N,N-dipropylamino; particularly preferably, X 1 and X 2 Each is independently Cl, methyl, benzyl or N,N-dimethylamino.

[0043] In a particularly preferred embodiment of the present invention, X 1 and X 2 Same as Cl.

[0044] In another particularly preferred embodiment of the present invention, X 1 and X 2 Both are methyl groups.

[0045] In another particularly preferred embodiment of the present invention, X 1 and X 2 Both are benzyl.

[0046] In another particularly preferred embodiment of the present invention, X 1 and X 2 Both are N,N-dimethylamino groups.

[0047] Specific preferred metallocene compounds include the following compounds:

[0048] In formula (1), M is a titanium atom, X 1 and X 2 Same as Cl;

[0049] In formula (1), M is a titanium atom, X 1 and X 2 Same as methyl;

[0050] In formula (1), M is a titanium atom, X 1 and X 2 Same as benzyl;

[0051] In formula (1), M is a titanium atom, X 1 and X 2 The same is N,N-dimethylamino;

[0052] In formula (1), M is a zirconium atom, X 1 and X 2 Same as Cl;

[0053] In formula (1), M is a zirconium atom, X 1 and X2 Same as methyl;

[0054] In formula (1), M is a zirconium atom, X 1 and X 2 Same as benzyl;

[0055] In formula (1), M is a zirconium atom, X 1 and X 2 The same is N,N-dimethylamino;

[0056] In formula (1), M is a hafnium atom, X 1 and X 2 Same as Cl;

[0057] In formula (1), M is a hafnium atom, X 1 and X 2 Same as methyl;

[0058] In formula (1), M is a hafnium atom, X 1 and X 2 Same as benzyl;

[0059] In formula (1), M is a hafnium atom, X 1 and X 2 Both are N,N-dimethylamino groups.

[0060] The metallocene compound according to the present invention can be synthesized according to conventional methods in the art.

[0061] In the present invention, X 1 and X 2 The method for preparing a metallocene compound having an N,N-dialkylamine group having 2 to 8 carbon atoms preferably comprises the following steps:

[0062] 1) In the presence of a catalyst C and a first solvent, compound A and compound B are subjected to a first contact reaction to obtain an intermediate product D;

[0063] 2) in the presence of a second solvent, subjecting the intermediate product D to a second contact reaction with the compound E to obtain the intermediate product F;

[0064] 3) in the presence of a third solvent, subjecting the intermediate product F to a third contact reaction with M(NA2)4 to obtain compound H,

[0065] Wherein, A is a hydrocarbon group with 1 to 4 atoms; n is an integer of 1 to 5; R 1 、R 2 、R 3 、R 4 Each is independently a hydrogen atom, a methyl group, an ethyl group, an isopropyl group or a tert-butyl group.

[0066] The following steps are explained.

[0067] Step 1): In the presence of a catalyst C and a first solvent, compound A and compound B are subjected to a first contact reaction to obtain an intermediate product D.

[0068] In the above step 1), in the catalyst C, n is preferably 2 or 3.

[0069] As the catalyst C, preferably one or more of pyrrolidine, 2-methylpyrrolidine, 2,5-dimethylpyrrolidine, 2,2,5,5-tetramethylpyrrolidine, piperidine and 2,2,6,6-tetramethylpiperidine are mentioned.

[0070] The amount of the catalyst C can be selected according to the compound A. Preferably, the molar ratio of the reactant A to the catalyst C is 1:1-5, more preferably 1:1.1-3.

[0071] In the above step 1), the first solvent is preferably methanol, more preferably anhydrous methanol.

[0072] The amount of the first solvent can be selected according to the compound A. For example, relative to 1 mol of the compound A, the amount of the first solvent can be 0.5-10 L, preferably 0.8-5 L, and more preferably 0.8-2 L.

[0073] In the above step 1), the amount of the compound B can be selected according to the compound A. Preferably, the molar ratio of the reactant A to the compound B is 1:1.2-10, more preferably 1:1.5-5, and even more preferably 1:2-4.

[0074] In the above step 1), the contact method of the first contact reaction is not particularly limited, as long as the intermediate product D can be obtained. Preferably, the catalyst C is mixed with the first solvent and then subjected to the first contact reaction with the compound B.

[0075] The conditions of the first contact reaction may include: a temperature of 10-25° C. and a time of 8-90 h.

[0076] After the first contact reaction, conventional refining methods in the art can be used for purification. In a preferred embodiment of the present invention, after the first contact reaction is completed, the first contact reaction product is subjected to solid-liquid separation to remove the first solvent and unreacted catalyst, and then the solid obtained by solid-liquid separation is washed with the first solvent and dried to obtain the intermediate product D.

[0077] The solid-liquid separation is not particularly limited, and various methods commonly used in the art for separating solids and liquids can be used. For example, the solid-liquid separation can be performed by filtration and / or centrifugation.

[0078] The drying may be performed using a solvent removal method commonly used in the art. In a preferred embodiment of the present invention, the solvent is removed by vacuum removal at 10-25°C.

[0079] Step 2): In the presence of a second solvent, the intermediate product D is subjected to a second contact reaction with compound E to obtain an intermediate product F.

[0080] In the above step 2), the amount of the compound E can be selected according to the amount of the intermediate product D. Preferably, the molar ratio of the intermediate product D to the compound E is 1:0.9-1.1, more preferably 1:0.95-1.05.

[0081] In the above step 2), the second solvent is one or more of aromatic hydrocarbons, ethers and halogenated alkanes, preferably one or more of diethyl ether, tetrahydrofuran, toluene, dichloromethane and 1,2-dichloroethane.

[0082] The amount of the second solvent can be selected according to the intermediate product D. For example, relative to 1 mol of the intermediate product D, the amount of the second solvent can be 1-30 L, preferably 5-20 L, and more preferably 12-18 L.

[0083] In the above step 2), the contact method of the second contact reaction is not particularly limited, as long as the intermediate product F can be obtained. Preferably, under an inert atmosphere (for example, it can be carried out under a nitrogen atmosphere or an argon atmosphere), the compound E is dispersed in part of the second solvent, and then a solution in which the intermediate product D is dissolved in another part of the solvent is added dropwise to the solution in which the compound E is dispersed to carry out the second contact reaction.

[0084] Preferably, the operation of dispersing the compound E in part of the second solvent is performed at a temperature of -30 to 0°C, for example, stirring at -20°C for about 30 minutes.

[0085] The conditions of the second contact reaction may include: a temperature of 10-40° C. and a time of 8-40 h.

[0086] After the second contact reaction, the product can be purified by conventional purification methods in the art. In a preferred embodiment of the present invention, after the second contact reaction is completed, the product of the second contact reaction is poured into a saturated aqueous solution of ammonium chloride, the organic phase is separated, and the aqueous phase is extracted with, for example, diethyl ether. The organic phases are combined and dried with a desiccant (for example, anhydrous sodium sulfate), and the organic solvent is removed (for example, the organic solvent is removed in vacuo) to obtain the intermediate product F.

[0087] Step 3): In the presence of a third solvent, the intermediate product F is subjected to a third contact reaction with M(NA2)4 to obtain compound H.

[0088] In the above-mentioned 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.

[0089] In the above-mentioned M(NA2)4, M is preferably a tetravalent transition metal atom, more preferably a titanium atom, a zirconium atom or a hafnium atom, further preferably a titanium atom or a zirconium atom, and particularly preferably a zirconium atom.

[0090] In the above step 3), the amount of M(NA2)4 can be selected according to the amount of the intermediate product F. Preferably, the molar ratio of the intermediate product F to M(NA2)4 is 1:0.95-1.05, more preferably 1:0.98-1.02.

[0091] In the above step 3), the third solvent may be, for example, toluene.

[0092] The amount of the third solvent can be selected according to the intermediate product F. For example, relative to 1 mol of the intermediate product F, the amount of the third solvent can be 1-30 L, preferably 5-20 L, and more preferably 12-18 L.

[0093] The conditions of the third contact reaction may include: reacting under reflux for 12-36 hours.

[0094] Preferably, the third contact reaction is carried out under an inert atmosphere, for example, under a nitrogen atmosphere or an argon atmosphere.

[0095] After the third contact reaction, conventional refining methods in the art can be used for purification. In a preferred embodiment of the present invention, after the third contact reaction is completed, the third contact reaction product is cooled and subjected to solid-liquid separation, and then the solvent is removed in vacuo to obtain compound H.

[0096] The solid-liquid separation is not particularly limited, and various methods commonly used in the art for separating solids and liquids can be used. For example, the solid-liquid separation can be performed by filtration and / or centrifugation.

[0097] In the present invention, X 1 and X 2 The method for preparing a metallocene compound containing a halogen atom preferably comprises the following steps:

[0098] 4) in the presence of a fourth solvent, subjecting the intermediate product F to a fourth contact reaction with n-butyl lithium, and then subjecting the product of the fourth contact reaction to a fifth contact reaction with MX4 to obtain compound I.

[0099] In MX4 and compound I, X is a halogen atom and M is a tetravalent transition metal atom.

[0100] Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, preferably fluorine, chlorine, or bromine, more preferably chlorine or bromine, and particularly preferably chlorine.

[0101] Preferably, M is a titanium atom, a zirconium atom, or a hafnium atom, more preferably a titanium atom or a zirconium atom, particularly preferably a zirconium atom.

[0102] Specific examples of MX4 compounds include zirconium tetrafluoride, zirconium tetrachloride, zirconium tetrabromide, zirconium tetraiodide, titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, hafnium tetrafluoride, hafnium tetrachloride, hafnium tetrabromide, and hafnium tetraiodide, with zirconium tetrachloride being preferred.

[0103] In the above step 4), the fourth solvent is one or more of alkanes, aromatic hydrocarbons, ethers and halogenated alkanes, preferably one or more of n-hexane, diethyl ether, tetrahydrofuran, toluene, dichloromethane and 1,2-dichloroethane.

[0104] In the above step 4), the amount of the fourth solvent can be selected according to the intermediate product F. For example, relative to 1 mol of the intermediate product F, the amount of the fourth solvent can be 1-30 L, preferably 5-20 L, and more preferably 12-18 L.

[0105] In the above step 4), the fourth contact reaction is preferably carried out by dispersing the intermediate product F in the fourth solvent under an inert atmosphere (for example, a nitrogen atmosphere or an argon atmosphere), and then adding an n-butyllithium solution (for example, an n-butyllithium hexane solution) dropwise to the solution in which the intermediate product F is dispersed to carry out the fourth contact reaction.

[0106] Preferably, the operation of dispersing the intermediate product F in the fourth solvent is performed at a temperature of -30 to 0°C, for example, stirring at -20°C for about 30 minutes.

[0107] The conditions of the fourth contact reaction may include: temperature of 10-40° C. and time of 8-40 h.

[0108] In the above step 4), preferably, the molar ratio of the intermediate product F to n-butyl lithium is 1:2-2.4, preferably 1:2.1-2.2.

[0109] In the above step 4), the fourth contact reaction product is subjected to a fifth contact reaction with MX4. In the fifth contact reaction, MX4 can be directly added to the fourth contact reaction product in the form of a solid, or can be used in the form of a dispersion in a fifth solvent.

[0110] Examples of the fifth solvent include the same solvents as those mentioned above for the fourth solvent.

[0111] In the above step 4), the amount of MX4 can be selected according to the intermediate product F. Preferably, the molar ratio of the intermediate product F to MX4 is 1:0.95-1.

[0112] In the above step 4), the fifth contacting method is preferably: under an inert atmosphere (for example, nitrogen atmosphere or argon atmosphere), at -80 to -60°C, the MX4 solution is added dropwise to the fourth contact reaction product and then the fifth contact reaction is carried out.

[0113] The conditions of the fifth contact reaction may include: a temperature of 10-40° C. and a time of 8-96 hours.

[0114] After the fifth contact reaction, the product can be purified by conventional purification methods in the art. In a preferred embodiment of the present invention, after the fifth contact reaction is completed, the product of the fifth contact reaction is subjected to solid-liquid separation, and the solid obtained by solid-liquid separation is extracted 3-5 times with an organic solvent (preferably toluene), and then the liquid phase obtained by solid-liquid separation is combined with the extract, and the solvent is removed under vacuum and then washed (for example, with n-hexane), and then the residual solvent in the solid is removed under vacuum to obtain Compound I.

[0115] In the present invention, the method for preparing compound I can also be such that the second contact reaction product obtained in step 2) above is directly subjected to a fifth contact reaction with MX4 to obtain compound I.

[0116] In the present invention, X 1 and X 2 The method for preparing a metallocene compound which is an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 12 carbon atoms preferably comprises the following steps:

[0117] 5) in the presence of a sixth solvent, the compound I and R 0 MgY undergoes a sixth contact reaction to obtain compound J,

[0118] R0 MgY, R 0 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.

[0119] The alkyl group having 1 to 10 carbon atoms or the aromatic group having 6 to 12 carbon atoms are as described above.

[0120] In the above step 5), preferably, the compound I and R 0 The molar ratio of MgY is 1:2-3, more preferably 1:2.2-2.5.

[0121] In the above step 5), preferably, the sixth solvent is one or more of alkanes, aromatic hydrocarbons, ethers and halogenated alkanes, more preferably one or more of n-hexane, diethyl ether, tetrahydrofuran, toluene, dichloromethane and 1,2-dichloroethane.

[0122] The amount of the sixth solvent can be selected according to the compound I. For example, relative to 1 mol of the intermediate product I, the amount of the sixth solvent can be 5-60 L, preferably 10-40 L, and more preferably 25-32 L.

[0123] In the above step 5), the sixth contacting method is preferably: in an inert atmosphere (for example, in a nitrogen atmosphere or an argon atmosphere), R 0 The MgY solution is added dropwise to the mixture of the compound I and the sixth solvent to perform the sixth contact reaction.

[0124] The conditions of the sixth contact reaction may include: a temperature of 10-40° C. and a time of 10-30 h.

[0125] After the sixth contact reaction, conventional refining methods in the art can be used for purification. In a preferred embodiment of the present invention, after the sixth contact reaction is completed, the fifth contact reaction product is subjected to solid-liquid separation, and then the solvent is removed from the obtained solid in vacuo to obtain compound J.

[0126] According to a second aspect of the present invention, a catalyst composition is provided, wherein the catalyst composition comprises the following components:

[0127] a) the metallocene compound according to the first aspect of the present invention;

[0128] b) Co-catalyst component.

[0129] According to the catalyst composition of the present invention, preferably, the co-catalyst component includes a combination of alkylaluminoxane or an organoboron compound and an organoaluminum compound; more preferably, the co-catalyst component is a combination of alkylaluminoxane or an organoboron compound and an organoaluminum compound.

[0130] The alkylaluminoxane is preferably a compound selected from the group consisting of compounds represented by formula (2) and / or formula (3).

[0131] In formula (2) and formula (3), R is selected from an alkyl group having 1 to 15 carbon atoms, and n represents an integer of 4 to 30; more preferably, R is selected from an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 10 to 30.

[0132] Specific examples of the above-mentioned alkyl group include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, isobutyl, pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl and pentadecyl.

[0133] Examples of n 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, and 30.

[0134] Specific examples of the alkylaluminoxane include methylaluminoxane, ethylaluminoxane, and propylaluminoxane. Among them, methylaluminoxane is preferred.

[0135] According to the catalyst composition of the present invention, preferably, the organic boron compound is [B(C6F5)4] - Z + , Z + Having the structure shown in formula (4) or formula (5),

[0136] 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, wherein X1, X2 and X3 are respectively a halogen atom or an alkyl group having 1 to 12 carbon atoms, X1, X2 and X3 may be the same or different, and at least one is an alkyl group having 1 to 12 carbon atoms.

[0137] Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, isobutyl, pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.

[0138] Examples of the halogen atom include fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine or bromine, more preferably chlorine or bromine, and particularly preferably chlorine.

[0139] In the present invention, specific examples of the organoaluminum compound include diethylaluminum chloride, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum, or a mixture of two or more thereof, preferably triisobutylaluminum.

[0140] According to the catalyst composition of the present invention, the co-catalyst component is alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane calculated as aluminum is 1:(100-50000), preferably 1:(500-10000), and more preferably 1:(500-2000).

[0141] According to the catalyst composition of the present invention, when the co-catalyst component is a combination of an organic boron compound and an organic aluminum compound, the molar ratio of the metallocene compound to the organic boron compound is 1:(1-20), preferably 1:(1-5), more preferably 1:(1-2), and the molar ratio of the metallocene compound to the organic aluminum compound is 1:(10-5000), preferably 1:(50-1000), more preferably 1:(50-500).

[0142] According to a third aspect of the present invention, a method for preparing an ethylene-cycloolefin copolymer is provided, which comprises copolymerizing ethylene and cycloolefin using a catalyst composition, wherein the catalyst composition is the catalyst composition described in the second aspect of the present invention.

[0143] According to the method of the present invention, preferably, the concentration of the metallocene compound in the copolymerization reaction system is 1×10 -8 mol / L~1×10 -2 mol / L, preferably 1×10 -6 mol / L~1×10 -3 mol / L.

[0144] According to the method of the present invention, the copolymerization reaction is preferably carried out in an inert organic solvent. The inert organic solvent can be a linear aliphatic hydrocarbon, a branched aliphatic hydrocarbon, a substituted or unsubstituted cyclic aliphatic hydrocarbon, or a mixture of substituted or unsubstituted aromatic hydrocarbons, or more thereof. Specific examples of the inert organic solvent include hexane, heptane, cyclohexane, cyclooctane, toluene, and xylene, with one or more of toluene, cyclohexane, and hexane being preferred. Furthermore, the amount of organic solvent can be determined based on the reaction activity to ensure that the resulting polymer dissolves well in the system, or at least does not affect dispersion.

[0145] According to the method of the present invention, preferably, the olefin is ethylene or a combination of ethylene and α-olefin.

[0146] According to the method of the present invention, preferably, the α-olefin is selected from one or more of propylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene.

[0147] According to the method of the present invention, when the olefin is ethylene, the partial pressure of the ethylene is 0.1-6 MPa, preferably 0.1-3 MPa.

[0148] According to the method of the present invention, when the olefin is a combination of ethylene and an α-olefin, the amounts of ethylene and the α-olefin used can be the amounts commonly used in the art for synthesizing ethylene-α-olefin copolymers. For example, the α-olefin concentration in the copolymerization reaction system is 0.001-8 mol / L, preferably 0.005-4 mol / L. In addition, the ethylene partial pressure is 0.1-6 MPa, preferably 0.1-3 MPa.

[0149] According to the method of the present invention, the copolymerization reaction conditions can be the conditions commonly used in the art for synthesizing polyolefins. Preferably, the copolymerization reaction temperature is -50 to 200°C, and the copolymerization reaction time is 1 to 300 minutes; more preferably, the copolymerization reaction temperature is -20 to 150°C, and the copolymerization reaction time is 5 to 60 minutes.

[0150] The present invention will be described in detail below through examples, but the present invention is not limited to the following examples.

[0151] Unless otherwise specified, the raw materials used in the following examples and comparative examples are all disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0152] In the following examples and comparative examples, the compounds synthesized 1 H NMR ( 1 H-NMR) was performed on a Bruker AVANCE III-400 MHz spectrometer using CDCl 3 as solvent at 25°C.

[0153] Polymer molecular weights were determined by gel permeation chromatography (GPC) at 150°C with 1,2,4-trichlorobenzene as solvent on a Waters Alliance GPCV2000.

[0154] The comonomer content in the polymer was determined by solution 13 C NMR ( 13C-NMR) experiments were performed on a Bruker AVANCEIII-400 MHz spectrometer equipped with a 10 mm PASEX 13C-1H / D Z-GRD probe. 13 The C resolution was 0.09 Hz. Sample solutions were prepared by dissolving 200 mg of polymer material in 2.5 mL of D4-o-dichlorobenzene (ODCB-d4) in a 10 mm test tube at 130°C. 13 C-NMR measurements were performed at 125°C, a 20 Hz spin rate, a 90° pulse angle, continuous Waltz-16 decoupling, a 120 ppm spectral width, a 5 s acquisition time, and a 10 s relaxation delay. The recurring backbone methylene peak was set to 30.0000 ppm as a chemical shift reference.

[0155] Example 1

[0156] This example is used to illustrate the synthesis of metallocene compound H-1

[0157] Metallocene compound H-1: In the above compound H, M is zirconium and NA2 is a dimethylamino group.

[0158] 1) Synthesis of intermediate D

[0159] Catalyst C (pyrrolidine, 12 mmol) and 30 ml of anhydrous methanol were added to a 250 ml three-necked flask with magnetic stirring at 15°C. The mixture was stirred for 5 minutes, followed by the addition of compound A (1.8 g, 11.98 mmol). The mixture was stirred for 5 minutes, followed by the addition of compound B (2.0 g, 30.26 mmol). The reaction was stirred for 24 hours, maintaining the reaction temperature at no more than 25°C. The solvent and catalyst were removed by filtration, and the resulting product was washed with anhydrous methanol. The residual solvent was removed in vacuo at room temperature to obtain 2.26 g of a yellow solid, with a yield of 94%.

[0160] 1 H-NMR (CDCl3): 6.62-6.55ppm (2H), 6.55-6.48ppm (2H), 3.33-3.24ppm (2H), 2.14-1.85ppm (12H).

[0161] 2) Synthesis of intermediate product F

[0162] Under a nitrogen atmosphere, 344 mg (2.0 mmol) of reactant E (fluorenyl lithium) 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 fluorenyl lithium tetrahydrofuran solution. After the addition was complete, the temperature was slowly raised to room temperature and the reaction was stirred for 24 hours. The reaction mixture was poured into a saturated aqueous solution of ammonium chloride, the organic phase was separated, and the aqueous phase was extracted with ether. The organic phases were combined, dried over anhydrous sodium sulfate, and the organic solvent was removed in vacuo to obtain 622 mg of a yellow solid (yield 81%).

[0163] 3) Synthesis of Metallocene Compound H-1

[0164] Under nitrogen atmosphere, 383 mg of intermediate product F (1 mmol) was dissolved in 15 ml of toluene, and 267 mg of reactant Zr(NMe2)4 (1 mmol) was added. The mixture was refluxed at 110°C for 24 hours. After cooling, the mixture was filtered and the solvent was removed in vacuo to obtain 461 mg of an orange solid with a yield of 85%.

[0165] 1 H-NMR (CDCl3): 8.25-8.15ppm (2H), 7.83-7.75ppm (2H), 7.65-7.55ppm (2H), 7.23-7.14ppm (2H), 6. 43-6.35ppm(2H), 5.78-5.70ppm(2H), 2.55-2.51ppm(12H), 2.40-2.25ppm(6H), 2.06-1.88ppm(8H).

[0166] Example 2

[0167] Synthesis of Metallocene Compound I-1

[0168] Metallocene compound I-1: In compound I, M is zirconium and X is a chlorine atom.

[0169] Fluorene (499 mg, 3 mmol) was weighed into a 250 mL three-necked flask A. After vacuum-purging with nitrogen three times, 10 mL of previously dehydrated and deoxygenated anhydrous ether was added to dissolve the product. Flask A was placed in a -20°C oil bath and stirred for 15 minutes. At -20°C, n-butyl lithium (1.05 equivalents, 2.5 mol / L hexane solution) was added dropwise to flask A. After completion, 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-necked flask B. After nitrogen-purging three times, 10 mL of previously dried molecular sieve-treated anhydrous ether was added to dissolve the product. Flask A was placed in a -20°C oil bath and stirred for 15 minutes. The solution in flask B was added dropwise to flask A. After completion, flask A was transferred to room temperature and stirred for 24 hours. Flask A was placed in a -20°C oil bath and stirred for 15 minutes. n-Butyl lithium (1.05 equivalents, 2.5 mol / L hexane solution) was added dropwise to flask A. After completion, flask A was transferred to room temperature and stirred for 8 hours. Flask A was placed in a -70°C oil bath and stirred for 30 minutes. Under nitrogen, zirconium tetrachloride (700 mg, 3 mmol) was added as a solid in three portions to flask A and stirred at room temperature for 72 hours. The reaction mixture was transferred to a centrifuge tube and centrifuged (3500 rpm). The supernatant was removed and the residual solid was extracted with 5 ml of anhydrous ether. This was centrifuged (3500 rpm) three times, and the supernatant was removed. The residual solid was discarded. The supernatant and extract were combined, and the ether was removed under vacuum. The resulting solid was dissolved in a small amount of toluene, filtered into a sample bottle, and an equal volume of ultra-dry n-hexane was added. After standing in a nitrogen box at room temperature for 24 hours, the sample was centrifuged to yield 471 mg of the solid compound, a 30% yield.

[0170] 1 H-NMR(CDCl3): 8.23-8.14ppm(2H), 7.79-7.70ppm(2H), 7.63-7.54ppm(2H), 7.24-7.15p pm(2H), 6.43-6.35ppm(2H), 5.77-5.68ppm(2H), 2.48-2.33ppm(6H), 2.15-1.97ppm(8H).

[0171] Example 3

[0172] Synthesis of Metallocene Compound I-1

[0173] Metallocene compound I-1: In compound I, M is zirconium and X is a chlorine atom.

[0174] Under a nitrogen atmosphere, 383 mg of intermediate F (1 mmol) was dissolved in 15 mL of toluene. At -20°C, 0.84 mL of n-butyllithium (2.5 mol / L hexane solution) was added dropwise. After completion, flask A was transferred to room temperature and stirred for 8 hours. Flask A was placed in a -70°C oil bath and stirred for 30 minutes. Under nitrogen, zirconium tetrachloride (233 mg, 1 mmol) was added as a solid in three portions to flask A and stirred at room temperature for 72 hours. The reaction mixture was transferred to a centrifuge tube and centrifuged (3500 rpm). The supernatant was removed and the residual solid was extracted with 5 mL of anhydrous ether. This was centrifuged three times (3500 rpm) and the supernatant was removed. The residual solid was discarded. The supernatant and extract were combined, and the ether was removed under vacuum. The resulting solid was dissolved in a small amount of toluene, filtered into a sample bottle, and an equal volume of ultra-dry n-hexane was added. After standing in a nitrogen box at room temperature for 24 hours, the sample was centrifuged to yield 276 mg of the solid compound, a 53% yield.

[0175] The obtained solid compound was confirmed to be metallocene compound I-1 by nuclear magnetic resonance analysis.

[0176] Example 4

[0177] Synthesis of Metallocene Compound J-1

[0178] Metallocene compound J-1: In compound J, M is zirconium, R 0 It is benzyl.

[0179] Under a nitrogen atmosphere, 525 mg of metallocene compound I (1 mmol) was dissolved in 30 mL of toluene and stirred in a -70°C oil bath for 30 minutes. 2 mL of benzylmagnesium chloride solution (1 mol / L in tetrahydrofuran) was then added dropwise. The temperature was slowly warmed to room temperature and allowed to react for 24 hours. The mixture was filtered and the solvent removed in vacuo to afford 523 mg of an orange solid in an 82% yield.

[0180] 1 H-NMR (CDCl3): 8.28-8.20ppm (2H), 7.82-7.74ppm (2H), 7.64-7.53ppm (2H), 7.32-7.08ppm (12H), 6.45-6.38p pm(2H), 5.77-5.67ppm(2H), 2.62-2.58ppm(4H), 2.55-2.51ppm(12H), 2.41-2.25ppm(6H), 2.09-1.90ppm(8H).

[0181] Example 5

[0182] Synthesis of Metallocene Compound J-2

[0183] Metallocene compound J-2: In compound J, M is zirconium, R0 It is a methyl group.

[0184] Under a nitrogen atmosphere, 472 mg of metallocene compound I (1 mmol) was dissolved in 30 mL of toluene and stirred in a −70° C. oil bath for 30 minutes. 2 mL of methylmagnesium bromide solution (1 mol / L tetrahydrofuran solution) was added dropwise. The temperature was slowly warmed to room temperature and allowed to react for 24 hours. The mixture was filtered and the solvent was removed in vacuo to afford 357 mg of an orange solid in a 74% yield.

[0185] 1 H-NMR (CDCl3): 8.24-8.15ppm (2H), 7.79-7.71ppm (2H), 7.62-7.54ppm (2H), 7.24-7.16ppm (2H), 6.43-6.35 ppm(2H), 5.77-5.67ppm(2H), 2.55-2.51ppm(12H), 2.40-2.25ppm(6H), 2.06-1.88ppm(8H), -0.97ppm(6H).

[0186] Example 6

[0187] This example is used to illustrate the copolymerization of ethylene and norbornene.

[0188] 4.71 g of norbornene was added to a thoroughly dried 250 ml glass polymerization bottle. The reaction was then evacuated and flushed with nitrogen three times. The reaction was then evacuated and filled with ethylene. The oil bath was heated to 70°C, maintaining a standard atmosphere of ethylene in the polymerization bottle. 25 ml of toluene and 3 ml of a toluene solution of methylaluminoxane (containing 5.0 mmol of methylaluminoxane) were added sequentially. After the temperature stabilized at 70°C, 2 ml of a toluene solution of the catalyst (containing 2 micromoles of compound I-1) was added, and the timer was started. As ethylene was consumed during the reaction, it was replenished to maintain a standard atmosphere of ethylene in the polymerization bottle. After 20 minutes, the ethylene was turned off, the reaction mixture was poured into a beaker, and 300 ml of ethanol and 5 ml of concentrated hydrochloric acid were added. The mixture was stirred for at least 6 hours, and the polymer was filtered to obtain a polymer. The polymer was vacuum dried at 60°C for 24 hours to yield 2.76 g of polymer with an activity of 4140 kg polymer / mol catalyst / hour. The polymer weight-average molecular weight (Mw) of the polymer, as determined by gel permeation chromatography, was 17.9 × 10 4 The molecular weight distribution (MWD) was 1.92. The norbornene unit content in the polymer was 55.7 mol % as determined by C-13 NMR spectroscopy. The glass transition temperature of the polymer was 167° C. as determined by DSC.

[0189] Comparative Example 1

[0190] The method of Example 6 was followed, except that the metallocene compound I-1 was replaced by the same molar amount of dibenzylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride. 2.01 g of polymer was obtained in the same manner. The polymerization activity was 3015 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was Mw = 12.6 × 10 4 The molecular weight distribution (MWD) was 2.27. The norbornene unit content in the polymer was 51.0 mol % as determined by C-13 NMR spectroscopy. The glass transition temperature of the polymer was 163° C. as determined by DSC.

[0191] Comparative Example 2

[0192] The method of Example 6 was followed, except that the metallocene compound I-1 was replaced by the same molar amount of ref-1. 2.01 g of polymer was obtained in the same manner, with an activity of 3015 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was 15.6×10 4 The molecular weight distribution (MWD) was 2.11. The norbornene unit content in the polymer was 47.1 mol % as determined by C-13 NMR spectroscopy. The glass transition temperature of the polymer was 153° C. as determined by DSC.

[0193] Comparative Example 3

[0194] The method of Example 6 was followed, except that the metallocene compound I-1 was replaced by the same molar amount of ref-2. 1.92 g of polymer was obtained in the same manner, with an activity of 2880 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was 14.7×10 4 The molecular weight distribution (MWD) was 2.06. The norbornene unit content in the polymer was 49.2 mol % as determined by C-13 NMR spectroscopy. The glass transition temperature of the polymer was 157° C. as determined by DSC.

[0195] Example 7

[0196] This example is used to illustrate the copolymerization of ethylene and norbornene.

[0197] Add 4.71 g of norbornene to a thoroughly dried 250 ml glass polymerization bottle, evacuate, and flush with nitrogen three times. Evacuate the bottle, fill it with ethylene, and heat it in an oil bath to 70°C, maintaining an ethylene pressure of 1 atm. Sequentially add 25 ml of toluene, 1 ml of a toluene solution of triisobutylaluminum (containing 1.0 mmol of triisobutylaluminum), and 2 ml of a toluene solution of the catalyst (containing 2 micromoles of Compound I-1). Once the temperature stabilizes at 70°C, add 2 ml of a toluene solution of triphenyltetrakis(pentafluorophenyl)borate (containing 2.4 micromoles of triphenyltetrakis(pentafluorophenyl)borate), and start the timer. As ethylene is consumed during the reaction, replenish it to maintain a constant ethylene pressure of 1 atm in the polymerization bottle. After 20 minutes, the ethylene was turned off, and the reaction solution was poured into a beaker. 300 ml of ethanol and 5 ml of concentrated hydrochloric acid were added and stirred for more than 6 hours. The polymer was filtered and dried under vacuum at 60°C for 24 hours to obtain 3.15 g of polymer with an activity of 4725 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer, Mw, was 19.8×10 4 The molecular weight distribution (MWD) was 1.99. The norbornene unit content in the polymer was 56.8 mol % as determined by C-13 NMR spectroscopy. The glass transition temperature of the polymer was 167° C. as determined by DSC.

[0198] Comparative Example 4

[0199] The method of Example 7 was followed, except that the metallocene compound I-1 was replaced by the same molar amount of dibenzylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride. 2.51 g of polymer was obtained in the same manner. The polymerization activity was 3765 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was Mw = 18.5 × 10 4 The molecular weight distribution (MWD) was 2.07. The norbornene unit content in the polymer was 54.1 mol % as determined by C-13 NMR spectroscopy. The glass transition temperature of the polymer was 165° C. as determined by DSC.

[0200] Example 8

[0201] This example is used to illustrate the copolymerization of ethylene and norbornene.

[0202] Add 4.71 g of norbornene to a thoroughly dried 250 ml glass polymerization bottle, evacuate, and flush with nitrogen three times. Evacuate the bottle, fill it with ethylene, and heat it in an oil bath to 70°C, maintaining an ethylene pressure of 1 atm. Sequentially add 25 ml of toluene, 1 ml of triisobutylaluminum toluene solution (containing 1.0 mmol of triisobutylaluminum), and 2 ml of catalyst toluene solution (containing 2 micromoles of Compound I-1). Once the temperature stabilizes at 70°C, add 2 ml of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate toluene solution (containing 2.4 micromoles of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate) and start the timer. During the reaction, replenish ethylene as it is consumed to maintain a constant ethylene pressure of 1 atm in the polymerization bottle. After 20 minutes, the ethylene was turned off, and the reaction solution was poured into a beaker. 300 ml of ethanol and 5 ml of concentrated hydrochloric acid were added and stirred for more than 6 hours. The polymer was filtered and dried under vacuum at 60°C for 24 hours to obtain 3.28 g of polymer with an activity of 4920 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer, Mw, was 8.5×10- 4 The molecular weight distribution (MWD) was 1.90. The norbornene unit content in the polymer was 55.7 mol % as determined by C-13 NMR spectroscopy. The glass transition temperature of the polymer was 167° C. as determined by DSC.

[0203] Example 9

[0204] This example is used to illustrate the copolymerization of ethylene and norbornene.

[0205] A thoroughly dried 100 ml stainless steel polymerization kettle was charged with 20 g of norbornene. The mixture was then vacuumed and flushed with nitrogen three times, followed by the addition of ethylene. The reaction was set to 75°C. During the heating process, 30 ml of toluene and 1 ml of a toluene solution of triisobutylaluminum (containing 1.0 mmol of triisobutylaluminum) were added sequentially. After the temperature stabilized at 75°C, 2 ml of a toluene solution of the catalyst (containing 2 micromoles of Compound I-1) was added. Five minutes later, 2 ml of a toluene solution of triphenyltetrakis(pentafluorophenyl)borate (containing 2.4 micromoles of triphenyltetrakis(pentafluorophenyl)borate) was added. The ethylene pressure was rapidly increased to 2 standard atmospheres (ATM). The reaction was then set to 80°C and the timer was started. As ethylene was consumed during the reaction, it was continuously replenished to maintain a total pressure of 2 ATM in the polymerization vessel. After 30 minutes, ethylene was turned off, and the reaction solution was poured into a beaker. 300 ml of ethanol and 5 ml of concentrated hydrochloric acid were added and stirred for more than 6 hours. The polymer was filtered and dried under vacuum at 60°C for 24 hours to obtain 13.95 g of polymer with an activity of 13950 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, Mw, was 14.7×10 4The molecular weight distribution (MWD) was 2.09. The norbornene unit content in the polymer was 51.9 mol % as determined by C-13 NMR spectroscopy. The glass transition temperature of the polymer was 162° C. as determined by DSC.

[0206] Example 10

[0207] This example is used to illustrate the copolymerization of ethylene and norbornene.

[0208] A thoroughly dried 100 ml stainless steel polymerization kettle was charged with 20 g of norbornene. The mixture was then vacuumed and flushed with nitrogen three times, followed by the addition of ethylene. The reaction was set to 75°C. During the heating process, 30 ml of toluene and 1 ml of a toluene solution of triisobutylaluminum (containing 1.0 mmol of triisobutylaluminum) were added. After the temperature stabilized at 75°C, 2 ml of a toluene solution of the catalyst (containing 2 micromoles of Compound I-1) was added. Five minutes later, 2 ml of a toluene solution of triphenyltetrakis(pentafluorophenyl)borate (containing 2.4 micromoles of triphenyltetrakis(pentafluorophenyl)borate) was added. The ethylene pressure was rapidly increased to 4 standard atmospheres (ATM). The reaction was then set to 80°C and the timer was started. As ethylene was consumed during the reaction, it was continuously replenished to maintain a total pressure of 4 standard atmospheres in the polymerization flask. After 30 minutes, ethylene was turned off, and the reaction solution was poured into a beaker. 300 ml of ethanol and 5 ml of concentrated hydrochloric acid were added and stirred for more than 6 hours. The polymer was filtered and dried under vacuum at 60°C for 24 hours to obtain 17.26 g of polymer with an activity of 17260 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was 17.6×10 4 The molecular weight distribution (MWD) was 1.99. The norbornene unit content in the polymer was 48.6 mol % as determined by C-13 NMR spectroscopy. The glass transition temperature of the polymer was 159° C. as determined by DSC.

[0209] Example 11

[0210] This example is used to illustrate the copolymerization of ethylene and norbornene.

[0211] The method of Example 6 was followed, except that the metallocene compound I-1 was replaced by the metallocene compound H-1 in the same molar amount. 3.01 g of polymer was obtained in the same manner, with an activity of 4515 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was 16.2×10 4 The molecular weight distribution (MWD) was 1.96. The norbornene unit content in the polymer was 55.6 mol % as determined by C-13 NMR spectroscopy. The glass transition temperature of the polymer was 167° C. as determined by DSC.

[0212] Example 12

[0213] This example is used to illustrate the copolymerization of ethylene and norbornene.

[0214] The method of Example 7 was followed, except that the metallocene compound I-1 was replaced by the metallocene compound H-1 in the same molar amount, and the same reaction was performed to obtain the product.

[0215] Example 13

[0216] This example is used to illustrate the copolymerization of ethylene and norbornene.

[0217] The method of Example 6 was followed, except that the metallocene compound I-1 was replaced by the metallocene compound J-1 in the same molar amount. 2.99 g of polymer was obtained in the same manner, with an activity of 4485 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was 18.6×10 4 The molecular weight distribution (MWD) was 1.93. The norbornene unit content in the polymer was 55.6 mol % as determined by C-13 NMR spectroscopy. The glass transition temperature of the polymer was 167° C. as determined by DSC.

[0218] Example 14

[0219] This example is used to illustrate the copolymerization of ethylene and norbornene.

[0220] The method of Example 7 was followed, except that the metallocene compound I-1 was replaced by the metallocene compound J-1 in the same molar amount. 3.01 g of polymer was obtained in the same manner, with an activity of 4515 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was Mw = 21.1×10 4 The molecular weight distribution (MWD) was 2.01. The norbornene unit content in the polymer was 55.6 mol % as determined by C-13 NMR spectroscopy. The glass transition temperature of the polymer was 168° C. as determined by DSC.

[0221] Example 15

[0222] This example is used to illustrate the copolymerization of ethylene and norbornene.

[0223] The method of Example 6 was followed, except that the metallocene compound I-1 was replaced by the metallocene compound J-2 in the same molar amount. 3.41 g of polymer was obtained in the same manner, with an activity of 5115 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was 17.8×10 4 The molecular weight distribution (MWD) was 1.90. The norbornene unit content in the polymer was 56.1 mol % as determined by C-13 NMR spectroscopy. The glass transition temperature of the polymer was 169° C. as determined by DSC.

[0224] Example 16

[0225] This example is used to illustrate the copolymerization of ethylene and norbornene.

[0226] The method of Example 7 was followed, except that the metallocene compound I-1 was replaced by the metallocene compound J-2 in the same molar amount. 3.27 g of polymer was obtained in the same manner, with an activity of 4905 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was 19.2×10 4 The molecular weight distribution (MWD) was 1.96. The norbornene unit content in the polymer was 56.3 mol % as determined by C-13 NMR spectroscopy. The glass transition temperature of the polymer was 169° C. as determined by DSC.

[0227] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A metallocene compound, characterized in that The metallocene compound has a structure shown in formula (1), In formula (1), M is a tetravalent transition metal atom; X 1 and X 2 Each is independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or an N,N-dialkylamino group having 2 to 8 carbon atoms.

2. The metallocene compound according to claim 1, wherein M is a titanium atom, a zirconium atom or a hafnium atom; X 1 and X 2 Each is 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; or M is a titanium atom or a zirconium atom, more preferably a zirconium atom; X 1 and X 2 each independently represents F, Cl, Br, I, methyl, ethyl, propyl, phenyl, benzyl, N,N-dimethylamino, N,N-diethylamino or N,N-dipropylamino; or M is a zirconium atom; X 1 and X 2 Each is independently Cl, methyl, benzyl or N,N-dimethylamino.

3. A catalyst composition, characterized in that The catalyst composition comprises the following components, a) the metallocene compound according to claim 1 or 2; b) Co-catalyst component.

4. The catalyst composition according to claim 3, wherein The co-catalyst component comprises a combination of an alkylaluminoxane or an organic boron compound and an organic aluminum compound; or The co-catalyst component is an alkylaluminoxane or a combination of an organic boron compound and an organic aluminum compound.

5. The catalyst composition according to claim 4, wherein The alkylaluminoxane is a compound selected from the group consisting of compounds represented by formula (2) and / or formula (3), In formula (2) and formula (3), R is selected from an alkyl group having 1 to 15 carbon atoms, and n represents an integer of 4 to 30; or The alkylaluminoxane is methylaluminoxane.

6. The catalyst composition according to claim 4, wherein The organic boron compound is [B(C6F5)4] - Z + , Z + Having a structure represented by formula (4) or formula (5), 7. The catalyst composition according to claim 4, wherein The organoaluminum compound is a compound having a structure represented by the general formula AlX1X2X3, wherein X1, X2 and X3 are halogen atoms or alkyl groups having 1 to 12 carbon atoms, respectively; 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; or 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 catalyst composition according to claim 4, wherein The co-catalyst component is alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane calculated on the basis of aluminum is 1:(100-50000); or The co-catalyst component is alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane calculated on the basis of aluminum is 1:(500-2000).

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

10. A method for preparing an ethylene-cycloolefin copolymer, the method comprising using a catalyst composition to copolymerize ethylene and a cycloolefin, characterized in that: The catalyst composition is the catalyst composition according to any one of claims 2 to 9.

11. The method according to claim 10, wherein: The concentration of the metallocene compound in the copolymerization reaction system is 1×10 -8 mol / L~1×10 -2 mol / L, preferably 1×10 -6 mol / L~1×10 -3 mol / L.

12. The method according to claim 10, wherein: The cycloolefin is one or more of cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, and tetracyclo[6.2.1.13,6.2,7]dodecene.

13. The method according to claim 12, wherein: The partial pressure of ethylene is 0.1-6 MPa, preferably 0.1-3 MPa.

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

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

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