Ethylene-cycloolefin copolymer and preparation method thereof

Abstract

The present application relates to the field of olefin copolymerization, and discloses an ethylene-cycloolefin copolymer and a preparation method thereof.The method comprises the following steps: using a catalyst composition to perform copolymerization reaction on ethylene and a cycloolefin, wherein the catalyst composition comprises the following components: a) a metallocene compound with a structure shown in formula (1); and b) a cocatalyst component, wherein, in formula (1), M is a tetravalent transition metal atom; X 1 and X 2 each independently is a halogen atom, an alkyl group with 1-10 carbon atoms, an aromatic group with 6-12 carbon atoms, or an N,N-dihydrocarbylamine group with 2-8 carbon atoms. According to the method, the catalyst has the advantages of high catalytic activity, good copolymerization performance and high molecular weight of the obtained copolymer, and the catalyst is easy to synthesize and has low synthesis cost.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of olefin copolymerization, in particular, to an ethylene-cycloolefin copolymer and a preparation method thereof. BACKGROUND

[0002] Metallocene compounds for olefin polymerization have been a research hotspot in the fields of metal organic chemistry, catalysis, polymer chemistry and materials science in recent decades. Using such catalysts, olefin polymers with very uniform molecular weight distribution and chemical composition distribution can be obtained, and the molecular structure and molecular weight of the polymers can be highly controllable by adjusting the structure of the catalyst. The strong copolymerization ability of metallocenes is reflected in two aspects (Chemistry Select 2020, 5, 7581-7585): on the one hand, under the same polymerization conditions, the content of comonomers contained in the copolymer obtained by metallocene is higher than that obtained by other catalysts, which is the high efficiency of its copolymerization; on the other hand, some monomers that cannot be polymerized by other catalysts can also be used as comonomers for metallocene compound systems, which is the broad spectrum of its copolymerization. Due to the high efficiency and broad spectrum of copolymerization of metallocene compounds, it can catalyze to obtain many new copolymers, which have new composition and structure compared with copolymers obtained by other catalysts, and thus may have new properties, thereby realizing the application of polyolefin materials in new fields.

[0003] Cycloolefin copolymer (COC) not only has good processability, but also has excellent thermal, optical and mechanical properties, such as excellent heat resistance and chemical resistance, excellent transparency, high refractive index, high hardness or softness, and low permeability to gas and water. These outstanding properties make COC a new type of engineering plastic, which has potential commercial application prospects in the fields of video and compact discs, optical lenses, light guide fibers, foam foils, medical devices and capacitors. Due to its good optical and mechanical properties, COC is used to manufacture optical discs, magneto-optical storage discs, optical gratings and other optical devices.

[0004] Although COC has excellent performance and wide application, its high production cost restricts its further market expansion, so developing more economical and effective catalyst systems is the key to making this material play a greater role in more occasions.

[0005] The structure of metallocene catalyst determines its catalytic performance, and a slight change in structure may lead to a huge change in catalytic performance. When designing metallocene catalysts, the polymerization activity and copolymerization performance of the catalysts will be improved as much as possible through structural design, and the molecular weight of the polymers will be improved, so as to broaden the operation space of production and improve the economy of production.

[0006] Existing metallocene catalysts still have problems with catalyst activity, copolymerization performance and polymer molecular weight that need to be improved. To solve these problems, the design of metallocene compounds has become increasingly complex, and their synthesis cost has also become a major issue. Summary of the Invention

[0007] The object of the present invention is to provide a novel method for preparing an ethylene-cycloolefin copolymer and the ethylene-cycloolefin copolymer prepared therefrom. The method of the present invention has the advantages of high catalytic activity, good copolymerization performance, and high molecular weight of the obtained copolymer. At the same time, the catalyst is easy to synthesize and the synthesis cost is low.

[0008] In order to achieve the above object, the present invention provides a method for preparing an ethylene-cycloolefin copolymer, which comprises: using a catalyst composition to copolymerize ethylene and cycloolefin,

[0009] Wherein, the catalyst composition comprises the following components:

[0010] a) a metallocene compound having a structure represented by formula (1);

[0011] b) a co-catalyst component,

[0012]

[0013] 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.

[0014] 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.

[0015] 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 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 2Each is independently Cl, methyl, benzyl or N,N-dimethylamino.

[0016] 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.

[0017] Preferably, the alkylaluminoxane is a compound selected from the structure shown in formula (2) and / or formula (3),

[0018]

[0019] 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; particularly preferably, the alkylaluminoxane is methylaluminoxane.

[0020] 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).

[0021] 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; more 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.

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

[0023]

[0024] 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).

[0025] 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.

[0026] Preferably, the cycloolefin is one or more of cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, and tetracyclo[6.2.1.13,6.2,7]dodecene.

[0027] Preferably, the ethylene partial pressure is 0.1-6 MPa, preferably 0.1-3 MPa.

[0028] 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.

[0029] 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.

[0030] According to a second aspect of the present invention, there is provided an ethylene-cycloolefin copolymer prepared by the method for preparing the ethylene-cycloolefin copolymer according to the first aspect of the present invention.

[0031] Through the above technical scheme, the present invention provides a new method for preparing ethylene-cycloolefin copolymer and the ethylene-cycloolefin copolymer prepared therefrom. According to the method of the present invention, the ethylene-cycloolefin copolymer has the advantages of high catalytic activity, good copolymerization performance, and high molecular weight of the obtained copolymer. At the same time, the catalyst is easy to synthesize and the synthesis cost is low. DETAILED DESCRIPTION

[0032] 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.

[0033] The first aspect of the present invention provides a method for preparing an ethylene-cycloolefin copolymer, the method comprising: using a catalyst composition to copolymerize ethylene and cycloolefin,

[0034] Wherein, the catalyst composition comprises the following components:

[0035] a) a metallocene compound having a structure represented by formula (1);

[0036] b) a co-catalyst component,

[0037]

[0038] 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.

[0039] According to 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.

[0040] According to 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.

[0041] 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.

[0042] 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.

[0043] Examples of the aromatic group having 6 to 12 carbon atoms include phenyl, benzyl, and phenethyl, among which benzyl is preferred.

[0044] 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 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 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 X2 Each is independently Cl, methyl, benzyl or N,N-dimethylamino.

[0045] In a particularly preferred embodiment of the present invention, X 1 and X 2 Same as Cl.

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

[0047] In another particularly preferred embodiment of the present invention, X 1 and X 2 Both are benzyl.

[0048] In another particularly preferred embodiment of the present invention, X 1 and X 2 Both are N,N-dimethylamino groups.

[0049] Specific preferred metallocene compounds include the following compounds:

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

[0051] In formula (1), M is a titanium atom, X 1 and X 2 Same as methyl;

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

[0053] In formula (1), M is a titanium atom, X 1 and X 2 The same is N,N-dimethylamino;

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

[0055] In formula (1), M is a zirconium atom, X 1 and X 2 Same as methyl;

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

[0057] In formula (1), M is a zirconium atom, X 1 and X 2 The same is N,N-dimethylamino;

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

[0059] In formula (1), M is a hafnium atom, X 1 and X 2 Same as methyl;

[0060] In formula (1), M is a hafnium atom, X 1 and X 2 Same as benzyl;

[0061] In formula (1), M is a hafnium atom, X 1 and X 2 Both are N,N-dimethylamino groups.

[0062] According to the present invention, the metallocene compound can be synthesized according to conventional methods in the art.

[0063] In the present invention, X 1 and X 2 The method for preparing a metallocene compound having an N,N-dialkylamine group with 2 to 8 carbon atoms preferably comprises the following steps:

[0064] 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;

[0065] 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;

[0066] 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,

[0067]

[0068]

[0069] 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.

[0070] The following steps are explained.

[0071] Step 1): first contact reaction of compound A and compound B in the presence of catalyst C in the presence of a first solvent, to obtain intermediate product D Step 2): second contact reaction of intermediate product D with compound E in the presence of a second solvent, to obtain intermediate product F .

[0072] In the above step 1), in the catalyst C, n is preferably 2 or 3.

[0073] 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.

[0074] 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, preferably 1:1.1-3.

[0075] In the above step 1), the first solvent is preferably methanol, more preferably anhydrous methanol.

[0076] 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.

[0077] 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, preferably 1:1.5-5, and more preferably 1:2-4.

[0078] 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.

[0079] The conditions of the first contact reaction may include: a temperature of 10-25° C. and a time of 8-90 h.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] Step 3): third contact reaction of intermediate product F with M(NA2)4 in the presence of a third solvent, to obtain compound H ​ .

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] The conditions of the second contact reaction may include: a temperature of 10-40° C. and a time of 8-40 h.

[0090] 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.

[0091] ​ ​ .

[0092] 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.

[0093] 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.

[0094] 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.

[0095] In the above step 3), the third solvent may be, for example, toluene.

[0096] 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.

[0097] The conditions of the third contact reaction may include: reacting under reflux for 12-36 hours.

[0098] Preferably, the third contact reaction is carried out under an inert atmosphere, for example, under a nitrogen atmosphere or an argon atmosphere.

[0099] 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.

[0100] 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.

[0101] 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:

[0102] 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.

[0103]

[0104] In MX4 and compound I, X is a halogen atom and M is a tetravalent transition metal atom.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] The conditions of the fourth contact reaction may include: temperature of 10-40° C. and time of 8-40 h.

[0113] 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.

[0114] 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.

[0115] Examples of the fifth solvent include the same solvents as those mentioned above for the fourth solvent.

[0116] In the above-mentioned step 4), the amount of MX4used can be selected according to the intermediate product F, preferably, the molar ratio of the intermediate product F to MX4is 1:0.95-1.

[0117] In the above-mentioned step 4), the fifth contact method is preferably that the fifth contact reaction is carried out after the solution of MX4is added dropwise to the fourth contact reaction product under an inert atmosphere (for example, it can be carried out under a nitrogen atmosphere or an argon atmosphere) at -80 to -60°C.

[0118] The conditions of the fifth contact reaction can include that the temperature is 10-40°C and the time is 8-96h.

[0119] After the fifth contact reaction, a conventional refining method in the art can be used for refining, in a preferred embodiment of the present application, after the end of the fifth contact reaction, the fifth contact reaction product is subjected to solid-liquid separation, the solid obtained by the solid-liquid separation is extracted 3-5 times using an organic solvent (preferably toluene), then the liquid phase obtained by the solid-liquid separation is combined with the extraction liquid, after the solvent is removed under vacuum, washing (for example, using n-hexane) is carried out, and then the residual solvent in the solid is removed under vacuum to obtain compound I.

[0120] In the present application, the preparation method of compound I can also directly use the second contact reaction product obtained in the above-mentioned step 2) to carry out the fifth contact reaction with MX4to obtain compound I.

[0121] In the present application, X 1 and X 2 The preparation method of the metallocene compound in which X

[0122] 5) the step of carrying out the sixth contact reaction between the compound I and R 0 MgY in the presence of a sixth solvent to obtain compound J,

[0123]

[0124] R 0 MgY, in which R 0 is an alkyl group having 1-10 carbon atoms or an aromatic group having 6-12 carbon atoms; and Y is a chlorine atom or a bromine atom.

[0125] The alkyl group having 1-10 carbon atoms or the aromatic group having 6-12 carbon atoms is as described above.

[0126] In the above-mentioned step 5), preferably, the molar ratio of the compound I to R 0 MgY is 1:2-3, preferably 1:2.2-2.5.

[0127] In the above step 5), preferably, the sixth 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.

[0128] The amount of the sixth solvent can be selected according to the compound I, for example, the amount of the sixth solvent can be 5 to 60 L, preferably 10 to 40 L, more preferably 25 to 32 L, per 1 mole of the intermediate product I.

[0129] In the above step 5), the sixth contacting method is preferably that R 0 The sixth contacting reaction is performed after the solution of MgY is dropped into the mixture of the compound I and the sixth solvent.

[0130] The conditions of the sixth contacting reaction can include a temperature of 10 to 40°C and a time of 10 to 30 h.

[0131] After the sixth contacting reaction, a conventional refining method in the art can be used for refining, and in a preferred embodiment of the present application, after the sixth contacting reaction, the fifth contacting reaction product is subjected to solid-liquid separation, and then the obtained solid is subjected to solvent removal under vacuum to obtain the compound J.

[0132] According to the present application, preferably, the cocatalyst component includes an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound; more preferably, the cocatalyst component is an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound.

[0133] As the above alkylaluminoxane, a compound selected from the structures represented by formula (2) and / or formula (3) is preferable,

[0134]

[0135] In formula (2) and formula (3), R is selected from alkyl groups having 1 to 15 carbon atoms, and n represents an integer of 4 to 30; more preferably, R is selected from alkyl groups having 1 to 5 carbon atoms, and n represents an integer of 10 to 30.

[0136] As specific examples of the above alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, sec-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, etc. can be mentioned.

[0137] As the n, for example, 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 the like can be given.

[0138] As the specific example of the alkylaluminoxane, for example, methylaluminoxane, ethylaluminoxane, propylaluminoxane, and the like can be given, and among them, methylaluminoxane is preferred.

[0139] According to the present application, 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), and more preferably 1 : (500-2000).

[0140] According to the present application, preferably, the organoaluminum compound is a compound represented by the general formula of AlX1X2X3, X1, X2, and X3 are each a halogen atom or an alkyl group having 1-12 carbon atoms, X1, X2, and X3 can be the same or different, and at least one is an alkyl group having 1-12 carbon atoms.

[0141] As the alkyl group having 1-12 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, isobutyl, pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and the like can be given.

[0142] As the halogen atom, for example, fluorine, chlorine, bromine, or iodine can be given, and preferably, fluorine, chlorine, or bromine, and more preferably, chlorine or bromine, and particularly preferably, chlorine.

[0143] In the present application, as the specific example of the organoaluminum compound, for example, one or a mixture of two or more of diethylaluminum chloride, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum can be given, and preferably, triisobutylaluminum.

[0144] According to the present application, preferably, the organoboron compound is [B(C6F5)4] - Z + , Z + has a structure represented by formula (4) or formula (5),

[0145]

[0146] According to 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).

[0147] According to 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.

[0148] According to the present invention, the copolymerization reaction is preferably carried out in an inert organic solvent. The inert organic solvent may 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 may be determined based on the reaction activity to ensure that the resulting copolymer dissolves well in the system, or at least does not affect dispersion.

[0149] According to the present invention, preferably, the cycloolefin is a cycloolefin containing 5-18 carbon atoms; more preferably, the cycloolefin is one or more of cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, and tetracyclo[6.2.1.13,6.2,7]dodec-4-ene.

[0150] According to the present invention, the amounts of ethylene and the cycloolefin used can be the amounts commonly used in the art for synthesizing ethylene-cycloolefin copolymers. For example, the cycloolefin concentration in the copolymerization reaction system can be 0.001-10 mol / L, preferably 0.05-5 mol / L. In addition, the ethylene partial pressure is 0.1-6 MPa, preferably 0.1-3 MPa.

[0151] 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.

[0152] According to a second aspect of the present invention, there is provided an ethylene-cycloolefin copolymer prepared by the method for preparing the ethylene-cycloolefin copolymer according to the first aspect of the present invention.

[0153] The present invention will be described in detail below through examples, but the present invention is not limited to the following examples.

[0154] 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.

[0155] 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.

[0156] 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.

[0157] The comonomer content in the polymer is determined by the solution 13 C NMR ( 13 C-NMR) experiments were performed on a Bruker AVANCE III-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.

[0158] Preparation Example 1

[0159] This example is used to illustrate the synthesis of metallocene compound H-1

[0160] Metallocene compound H-1: In the above compound H, M is zirconium and A is a dimethylamino group.

[0161] 1) Synthesis of intermediate D

[0162] 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%.

[0163] 1 H-NMR (CDCl3): 6.62-6.55ppm (2H), 6.55-6.48ppm (2H), 3.33-3.24ppm (2H), 2.14-1.85ppm (12H).

[0164] 2) Synthesis of intermediate product F

[0165] Under a nitrogen atmosphere, 244 mg (2.0 mmol) of reactant E (indenyl 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 indenyl 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 597 mg of a yellow solid (90% yield).

[0166] 3) Synthesis of Metallocene Compound H-1

[0167] Under nitrogen atmosphere, 333 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 reaction was refluxed at 110°C for 17 hours. After cooling, the mixture was filtered and the solvent was removed in vacuo to obtain 436 mg of an orange solid with a yield of 89%.

[0168] 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).

[0169] Preparation Example 2

[0170] Synthesis of Metallocene Compound I-1

[0171] Metallocene compound I-1: In compound I, M is zirconium and X is a chlorine atom.

[0172] Weigh pre-distilled indene (348.5 mg, 3 mmol) into a 250 mL flask A. After vacuum-purging with nitrogen three times, dissolve the product in 10 mL of previously dehydrated and deoxygenated anhydrous ether. Place flask A in a -20°C oil bath and stir for 15 minutes. Add n-butyllithium (1.05 equivalents, 2.5 mol / L hexane solution) dropwise to flask A at -20°C. Transfer flask A to room temperature and stir for 8 hours. Weigh intermediate product D (631 mg, 1.05 equivalents) into another 100 mL flask B. After nitrogen-purging three times, dissolve the product in 10 mL of previously dried molecular sieve-treated anhydrous ether. Place flask A in a -20°C oil bath and stir for 15 minutes. Add the solution from flask B dropwise to flask A. Transfer flask A to room temperature and stir for 24 hours. Flask A was placed in a -20°C oil bath and stirred for 15 minutes. n-Butyllithium (1.05 equivalents, 2.5 mol / L hexane solution) was then added dropwise to the mixture. After completion, the mixture 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 the mixture 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 n-hexane was added. After standing in a nitrogen box at room temperature for 24 hours, the mixture was centrifuged to yield 326 mg of the solid compound (23% yield).

[0173] 1 H-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).

[0174] Preparation Example 3

[0175] Synthesis of Metallocene Compound J-1

[0176] Metallocene compound J-1: M is zirconium, R 0It is benzyl.

[0177] Under a nitrogen atmosphere, 474 mg of the metallocene compound I-1 (1 mmol) was dissolved in 30 mL of toluene and stirred in an oil bath at -70°C for 30 minutes. 2.2 mL of a benzylmagnesium chloride solution (1 mol / L tetrahydrofuran solution) was added dropwise. The mixture 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 502 mg of an orange solid in an 85% yield.

[0178] 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), 6.55-6.51 ppm(2H), 6.16-6.11ppm(1H), 5.78-5.73ppm(1H), 5.68-5.64ppm(1H), 3.30-3.25ppm(1H), 2.8 3-2.74ppm(1H), 2.67-2.61(4H), 2.36-2.27ppm(2H), 2.24-2.13ppm(2H), 2.08-1.190ppm(8H).

[0179] Preparation Example 4

[0180] Synthesis of Metallocene Compound J-2

[0181] Metallocene compound J-2: M is zirconium, R 0 It is a methyl group.

[0182] Under a nitrogen atmosphere, 472 mg of metallocene compound I (1 mmol) was dissolved in 30 mL of toluene and stirred in an oil bath at -70°C for 30 minutes. 2 mL of methylmagnesium bromide solution (1 mol / L tetrahydrofuran solution) was added dropwise. The mixture 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 311 mg of an orange solid in a yield of 72%.

[0183] 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).

[0184] Example 1

[0185] This example is used to illustrate the copolymerization of ethylene and norbornene.

[0186] 3.77 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 to maintain a standard atmosphere of ethylene in the polymerization bottle. 25 ml of toluene and 3 ml of a methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) were added in sequence. After the temperature stabilized at 70°C, 2 ml of a catalyst toluene solution (containing 2 micromoles of metallocene compound I-1) was added and the timer was started. During the reaction, as ethylene was consumed, 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, 300 ml of ethanol and 5 ml of concentrated hydrochloric acid were added, and the mixture was stirred for more than 6 hours. The polymer was filtered and dried under vacuum at 60°C for 24 hours to obtain 2.87 g of polymer with a polymerization activity of 4305 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was 26.6 × 10 4 The molecular weight distribution (MWD) was 1.89. The norbornene unit content in the polymer was 54.3 mol % as determined by carbon-13 nuclear magnetic resonance spectroscopy.

[0187] Comparative Example 1

[0188] The method of Example 1 was followed, except that the metallocene compound I-1 was replaced by the same molar amount of dibenzylidene (cyclopentadiene) (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 carbon-13 nuclear magnetic resonance spectroscopy.

[0189] Example 2

[0190] This example is used to illustrate the copolymerization of ethylene and norbornene.

[0191] Add 3.77 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 metallocene 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 2.97 g of polymer with an activity of 4455 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer, Mw, was 27.1×10 4 The molecular weight distribution (MWD) was 1.96. The norbornene unit content in the polymer was 55.8 mol % as determined by carbon-13 nuclear magnetic resonance spectroscopy.

[0192] Comparative Example 2

[0193] The method of Example 2 was followed, except that the metallocene compound I-1 was replaced by the same molar amount of dibenzylidene (cyclopentadiene) (9-fluorenyl) zirconium dichloride. 2.51 g of polymer was obtained in the same manner, with a polymerization activity of 3765 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was 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 carbon-13 nuclear magnetic resonance spectroscopy.

[0194] Example 3

[0195] This example is used to illustrate the copolymerization of ethylene and norbornene.

[0196] 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 metallocene compound I-1). Once the temperature stabilizes at 70°C, add 2 ml of a toluene solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (containing 6.0 micromoles of N,N-dimethylanilinium tetrakis(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, 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 3.02 g of polymer. The polymerization activity was 4530 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer, Mw, was 7.3×10- 4 The molecular weight distribution (MWD) was 1.90. The norbornene unit content in the polymer was 55.0 mol % as determined by carbon-13 nuclear magnetic resonance spectroscopy.

[0197] Example 4

[0198] This example is used to illustrate the copolymerization of ethylene and norbornene.

[0199] 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 metallocene 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 11.95 g of polymer. The polymerization activity was 11950 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer, Mw, was 42.5×10- 4 The molecular weight distribution (MWD) was 2.00. The norbornene unit content in the polymer was 52.7 mol % as determined by carbon-13 nuclear magnetic resonance spectroscopy.

[0200] Example 5

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

[0202] 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 metallocene 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 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 16.37 g of polymer with an activity of 16,370 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was 46.8×10 4 The molecular weight distribution (MWD) was 1.98. The norbornene unit content in the polymer was 49.7 mol % as determined by carbon-13 nuclear magnetic resonance spectroscopy.

[0203] Example 6

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

[0205] The method of Example 1 was followed, except that the metallocene compound I-1 was replaced by the metallocene compound H-1 in the same molar amount. 2.80 g of polymer was obtained in the same manner. The polymerization activity was 4200 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was Mw=30.1×10 4 The molecular weight distribution (MWD) was 2.11. The norbornene unit content in the polymer was 55.0 mol % as determined by carbon-13 nuclear magnetic resonance spectroscopy.

[0206] Example 7

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

[0208] The method of Example 2 was followed, except that the metallocene compound I-1 was replaced by the metallocene compound H-1 in the same molar amount. 2.88 g of polymer was obtained in the same manner. The polymerization activity was 4320 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was Mw=31.5×10 4 The molecular weight distribution (MWD) was 1.99. The norbornene unit content in the polymer was 54.9 mol % as determined by carbon-13 nuclear magnetic resonance spectroscopy.

[0209] Example 8

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

[0211] The method of Example 1 was followed, except that the metallocene compound I-1 was replaced by the metallocene compound J-1 in the same molar amount. 3.23 g of polymer was obtained in the same manner. The polymerization activity was 4845 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was Mw=31.1×10 4 The molecular weight distribution (MWD) was 2.01. The norbornene unit content in the polymer was 55.0 mol % as determined by carbon-13 nuclear magnetic resonance spectroscopy.

[0212] Example 9

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

[0214] The method of Example 2 was followed, except that the metallocene compound I-1 was replaced by the metallocene compound J-1 in the same molar amount. 3.51 g of polymer was obtained in the same manner. The polymerization activity was 5265 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was Mw=31.9×10 4 The molecular weight distribution (MWD) was 2.11. The norbornene unit content in the polymer was 54.8 mol % as determined by carbon-13 nuclear magnetic resonance spectroscopy.

[0215] Example 10

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

[0217] The method of Example 1 was followed, except that the metallocene compound I-1 was replaced by the metallocene compound J-2 in the same molar amount. 3.15 g of polymer was obtained in the same manner. The polymerization activity was 4725 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was Mw=30.5×10 4 The molecular weight distribution (MWD) was 2.08. The norbornene unit content in the polymer was 54.6 mol % as determined by carbon-13 nuclear magnetic resonance spectroscopy.

[0218] Example 11

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

[0220] The method of Example 2 was followed, except that the metallocene compound I-1 was replaced by the metallocene compound J-2 in the same molar amount. 3.25 g of polymer was obtained in the same manner. The polymerization activity was 4875 kg polymer / mole catalyst / hour. The weight-average molecular weight of the polymer, as determined by gel permeation chromatography, was Mw=32.2×10 4 The molecular weight distribution (MWD) was 2.02. The norbornene unit content in the polymer was 54.8 mol % as determined by carbon-13 nuclear magnetic resonance spectroscopy.

[0221] 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 method for preparing an ethylene-cycloolefin copolymer, characterized in that: The method comprises: using a catalyst composition to copolymerize ethylene and a cycloolefin, Wherein, the catalyst composition comprises the following components: a) a metallocene compound having a structure represented by formula (1); b) a co-catalyst component, Formula (1) In formula (1), 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 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 method according to claim 1, wherein M is a titanium atom or a zirconium atom.

3. The method according to claim 2, wherein: M is a zirconium atom.

4. The method according to claim 1, wherein X 1 and X 2 Each is 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-dialkylamino group having 2 to 6 carbon atoms.

5. The method according to claim 1, wherein 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.

6. The method according to claim 1, wherein 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.

7. The method according to claim 1, wherein X 1 and X 2 Each is independently Cl, methyl, benzyl or N,N-dimethylamino.

8. The method according to claim 1, wherein The cocatalyst component includes an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound.

9. The method according to claim 8, wherein The co-catalyst component is an alkylaluminoxane or a combination of an organic boron compound and an organic aluminum compound.

10. The method according to claim 9, wherein: The alkylaluminoxane is a compound selected from the structure represented by formula (2) and / or formula (3), Formula (2) 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.

11. The method according to claim 10, wherein: R is selected from an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 10 to 30.

12. The method according to claim 10, wherein: The alkylaluminoxane is methylaluminoxane.

13. The method according to claim 9, 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).

14. The method according to claim 13, 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:(500-10000).

15. The method according to claim 14, 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:(500-2000).

16. The method according to claim 9, wherein The organoaluminum compound is a compound having a structure represented by the general formula AlX1X2X3, wherein X1, X2 and X3 are respectively halogen atoms or alkyl groups 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.

17. The method according to claim 16, wherein The organic aluminum compound is one or a mixture of two or more of diethylaluminum chloride, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum.

18. The method according to claim 17, wherein The organic aluminum compound is triisobutylaluminum.

19. The method according to claim 9, wherein The organic boron compound is [B(C6F5)4] - Z + , Z + Having the structure shown in formula (4) or formula (5), Formula (4) Formula (5).

20. The method according to claim 9, 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).

21. The method according to claim 20, 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:(1-5), and the molar ratio of the metallocene compound to the organic aluminum compound is 1:(50-1000).

22. The method according to claim 21, 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:(1-2), and the molar ratio of the metallocene compound to the organic aluminum compound is 1:(50-500).

23. The method according to any one of claims 1 to 22, wherein: The concentration of the metallocene compound in the copolymerization reaction system is 1×10 -8 mol / L~1×10 -2 mol / L.

24. The method according to claim 23, wherein The concentration of the metallocene compound in the copolymerization reaction system is 1×10 -6 mol / L~1×10 -3 mol / L.

25. The method according to any one of claims 1 to 22, wherein: The cycloolefin is one or more of cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, and tetracyclo[6.2.1.13,6.2,7]dodecene.

26. The method according to any one of claims 1 to 22, wherein: The partial pressure of ethylene is 0.1-6 MPa.

27. The method according to claim 26, wherein The partial pressure of ethylene is 0.1-3 MPa.

28. The method according to any one of claims 1 to 22, wherein: The copolymerization reaction is carried out in the presence of an organic solvent, which is one or more of toluene, cyclohexane and hexane.

29. The method according to any one of claims 1 to 22, wherein: The temperature of the copolymerization reaction is -50 to 200° C., and the time of the copolymerization reaction is 1 to 300 minutes.

30. The method according to claim 29, wherein The temperature of the copolymerization reaction is -20 to 150° C., and the time of the copolymerization reaction is 5 to 60 minutes.

31. An ethylene-cycloolefin copolymer prepared by the method for preparing an ethylene-cycloolefin copolymer according to any one of claims 1 to 30.

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