Ethylene-cycloolefin copolymer and preparation method thereof

Abstract

The present invention relates to the field of olefin polymerization, and discloses an ethylene-cycloolefin copolymer and a preparation method thereof, the method comprises the following steps: ethylene and cycloolefin are subjected to a copolymerization reaction by using a catalyst composition, and the catalyst composition comprises the following components: a) a metallocene compound having a structure represented by a formula (1); b) a cocatalyst component, in the formula (1), M is a tetravalent transition metal atom; x1 and X2 are respectively and independently a halogen atom, an alkyl group with a carbon atom number of 1-10, an aryl group with a carbon atom number of 6-12 or an N, N-dialkyl amino group with a carbon atom number of 2-8. The catalyst composition provided by the invention has the advantages of high catalytic activity, good copolymerization performance and high molecular weight of the obtained polymer. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the field of olefin polymerization, in particular to an ethylene-cycloolefin copolymer and a preparation method thereof. Background Art

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

[0003] Cyclic olefin copolymer (COC) not only has good processability, but also has excellent thermal, optical and mechanical properties, such as excellent heat and chemical resistance, excellent transparency, high refractive index, high hardness or softness, and low permeability to gas and water. These excellent properties make COC a new type of engineering plastic with potential commercial applications in video and compact discs, optical lenses, light-guiding 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, gratings and other optical devices.

[0004] 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 making this material play a greater role in more occasions.

[0005] The structure of metallocene catalysts determines their catalytic performance. A small change in the structure may lead to a huge change in the catalytic performance. When designing metallocene catalysts, the polymerization activity and copolymerization performance of the catalyst, as well as the molecular weight of the polymer, will be improved as much as possible through structural design, thereby broadening the operating space of production and improving the economic efficiency of production.

[0006] Existing metallocene catalysts still have the problem of catalyst activity, copolymerization performance and polymer molecular weight needing to be improved. 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, high molecular weight of the obtained copolymer, good copolymerization performance and high glass transition temperature of the polymer.

[0008] In order to achieve the above object, the present invention provides a method for preparing an ethylene-cycloolefin copolymer, the method comprising: 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 of them 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-dialkylamine 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; more preferably, X 1 and X 2 Each is independently Cl, methyl, benzyl or N,N-dimethylamino.

[0016] Preferably, the co-catalyst component comprises a combination of an alkylaluminoxane or 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 represented by 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 is an integer of 4 to 30; more preferably, R is selected from an alkyl group having 1 to 5 carbon atoms, and n is an integer of 10 to 30.

[0020] Preferably, the alkylaluminoxane is methylaluminoxane.

[0021] Preferably, the organic boron compound is [B(C6F5)4] - Z + , Z + Having a structure represented by formula (4) or formula (5),

[0022]

[0023] Preferably, 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, and X1, X2 and X3 may be the same or different, and at least one is an alkyl group having 1 to 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 on the basis of 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 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).

[0027] Preferably, the concentration of the metallocene compound in the polymerization reaction system is 1×10 -8 mol / L~1×10 -2 mol / L, preferably 1×10 -6 mol / L~1×10 -3 mol / L.

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

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

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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, high molecular weight of the obtained copolymer, good copolymerization performance and high glass transition temperature of the polymer. DETAILED DESCRIPTION

[0034] The endpoints and any values ​​of the ranges disclosed in this article 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 endpoint values ​​of each range, the endpoint values ​​of each range and the 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 as specifically disclosed in this article.

[0035] 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 a cycloolefin,

[0036] Wherein, the catalyst composition comprises the following components:

[0037] a) a metallocene compound having a structure represented by formula (1);

[0038] b) a co-catalyst component,

[0039]

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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 them, methyl, ethyl, propyl, and isopropyl are preferred, and methyl or ethyl are more preferred.

[0045] Examples of the aromatic group having 6 to 12 carbon atoms include phenyl, benzyl, and phenethyl. Among them, benzyl is preferred.

[0046] In the present invention, preferably, in formula (1), X 1 and X 2 Each of them 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-dialkylamine 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; particularly preferably, X 1 and X 2 Each is independently Cl, methyl, benzyl or N,N-dimethylamino.

[0047] In a particularly preferred embodiment of the present invention, X 1 and X 2 Same as Cl.

[0048] In another particularly preferred embodiment of the present invention, X 1 and X 2 The same is methyl.

[0049] In another particularly preferred embodiment of the present invention, X 1 and X 2 Same as benzyl.

[0050] In another particularly preferred embodiment of the present invention, X 1 and X 2 The same is N,N-dimethylamino.

[0051] As specific metallocene compounds, preferably the following compounds can be mentioned:

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

[0053] In formula (1), M is a titanium atom, X 1 and X 2 Same as methyl;

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

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

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

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

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

[0059] In formula (1), M is a zirconium atom, X 1 and X 2 The same is N,N-dimethylamino;

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

[0061] In formula (1), M is a hafnium atom, X 1 and X 2 Same as methyl group;

[0062] In formula (1), M is a hafnium atom, X 1 and X 2 Same as benzyl;

[0063] In formula (1), M is a hafnium atom, X 1 and X 2 The same is N,N-dimethylamino.

[0064] According to the present invention, it can be synthesized according to conventional methods in the art.

[0065] 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:

[0066] 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;

[0067] 2) in the presence of a second solvent, subjecting the intermediate product D to a second contact reaction with the compound E to obtain an intermediate product F;

[0068] 3) in the presence of a third solvent, subjecting the intermediate product F to a third contact reaction with M(NA2)4 to obtain a compound H,

[0069]

[0070]

[0071] Wherein, A is a hydrocarbon group having 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.

[0072] The following is a step-by-step explanation.

[0073] Step 1): In the presence of a catalyst C and a first solvent, compound A and compound B are reacted to form a first A contact reaction to obtain intermediate product D .

[0074] In the above step 1), in the catalyst C, n is preferably 2 or 3.

[0075] As the catalyst C, one or more of pyrrolidine, 2-methylpyrrolidine, 2,5-dimethylpyrrolidine, 2,2,5,5-tetramethylpyrrolidine, piperidine and 2,2,6,6-tetramethylpiperidine are preferably used.

[0076] 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.

[0077] In the above step 1), the first solvent is preferably methanol, more preferably anhydrous methanol.

[0078] 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.

[0079] 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 further preferably 1:2-4.

[0080] 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.

[0081] The conditions of the first contact reaction may include: a temperature of 10-25° C. and a time of 8-90 h.

[0082] After the first contact reaction, the conventional refining method in the art can be used for refining. 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 the solid-liquid separation is washed with the first solvent and dried to obtain the intermediate product D.

[0083] The solid-liquid separation is not particularly limited, and various methods commonly used in the art for separation of solids and liquids may be used. For example, the solid-liquid separation may be performed by filtration and / or centrifugation.

[0084] The drying may be performed by a method for removing solvents commonly used in the art. In a preferred embodiment of the present invention, the solvent is removed by vacuum removal at 10-25°C.

[0085] Step 2): In the presence of a second solvent, the intermediate product D is subjected to a second contact reaction with the compound E to obtain the intermediate product D. Intermediate product F .

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] The conditions of the second contact reaction may include: a temperature of 10-40° C. and a time of 8-40 h.

[0092] 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, the aqueous phase is extracted with, for example, ether, the organic phases are combined, 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 an intermediate product F.

[0093] 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 a compound Compound H .

[0094] 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.

[0095] 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.

[0096] 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.

[0097] In the above step 3), the third solvent may be, for example, toluene.

[0098] 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.

[0099] The conditions of the third contact reaction may include: reacting under reflux for 12-36 hours.

[0100] Preferably, the third contact reaction is carried out under an inert atmosphere, for example, under a nitrogen atmosphere or an argon atmosphere.

[0101] After the third contact reaction, the conventional refining method 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 solid-liquid separation is performed, and then the solvent is removed in vacuo to obtain compound H.

[0102] The solid-liquid separation is not particularly limited, and various methods commonly used in the art for separation of solids and liquids may be used. For example, the solid-liquid separation may be performed by filtration and / or centrifugation.

[0103] 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:

[0104] 4) in the presence of a fourth solvent, subjecting the intermediate product F to a fourth contact reaction with n-butyl lithium, and subjecting the fourth contact reaction product to a fifth contact reaction with MX4 to obtain compound I,

[0105]

[0106] In MX4 and compound I, X is a halogen atom and M is a tetravalent transition metal atom.

[0107] 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.

[0108] 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.

[0109] 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, and zirconium tetrachloride is preferred.

[0110] 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.

[0111] 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.

[0112] 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, it can be carried out under a nitrogen atmosphere or an argon atmosphere), and then dropping an n-butyl lithium solution (for example, an n-butyl lithium hexane solution) into the solution in which the intermediate product F is dispersed to carry out the fourth contact reaction.

[0113] 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.

[0114] The conditions of the fourth contact reaction may include: a temperature of 10-40° C. and a time of 8-40 h.

[0115] 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.

[0116] 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.

[0117] Examples of the fifth solvent include the same solvents as those described above for the fourth solvent.

[0118] 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.

[0119] In the above step 4), the fifth contact method is preferably: in an inert atmosphere (for example, it can be carried out in a nitrogen atmosphere or an argon atmosphere), the MX4 solution is added dropwise to the fourth contact reaction product at -80 to -60°C and then the fifth contact reaction is carried out.

[0120] The conditions of the fifth contact reaction may include: temperature of 10-40° C. and time of 8-96 h.

[0121] After the fifth contact reaction, the conventional refining method in the art can be used for refining. In a preferred embodiment of the present invention, after the fifth contact reaction is completed, the fifth contact reaction product 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.

[0122] In the present invention, the method for preparing compound I can also be such that the second contact reaction product obtained in the above step 2) is directly subjected to a fifth contact reaction with MX4 to obtain compound I.

[0123] 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:

[0124] 5) in the presence of a sixth solvent, the compound I and R 0 MgY is subjected to a sixth contact reaction to obtain compound J,

[0125]

[0126] R 0 MgY, R 0 It is an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 12 carbon atoms; Y is a chlorine atom or a bromine atom.

[0127] The alkyl group having 1 to 10 carbon atoms or the aromatic group having 6 to 12 carbon atoms are as described above.

[0128] In the above step 5), preferably, the compound I and R 0The molar ratio of MgY is 1:2-3, preferably 1:2.2-2.5.

[0129] 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.

[0130] 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.

[0131] In the above step 5), the sixth contacting method is preferably: in an inert atmosphere (for example, it can be carried out 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.

[0132] The conditions of the sixth contact reaction may include: a temperature of 10-40° C. and a time of 10-30 h.

[0133] After the sixth contact reaction, the conventional refining method 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 obtained solid is vacuum-dried to remove the solvent to obtain compound J.

[0134] According to the present invention, preferably, the co-catalyst component comprises a combination of an alkylaluminoxane or 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.

[0135] The alkylaluminoxane is preferably a compound selected from the group consisting of compounds represented by formula (2) and / or formula (3).

[0136]

[0137] In formula (2) and formula (3), R is selected from an alkyl group having 1 to 15 carbon atoms, and n is an integer of 4 to 30; more preferably, R is selected from an alkyl group having 1 to 5 carbon atoms, and n is an integer of 10 to 30.

[0138] 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.

[0139] 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.

[0140] Specific examples of the alkylaluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, and the like. Among them, methylaluminoxane is preferred.

[0141] According to the present invention, preferably, the organic boron compound is [B(C6F5)4] - Z + , Z + Having a structure represented by formula (4) or formula (5),

[0142]

[0143] According to 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 halogen atoms or alkyl groups having 1 to 12 carbon atoms, and X1, X2 and X3 may be the same or different, and at least one is an alkyl group having 1 to 12 carbon atoms.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] According to the present invention, 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), preferably 1:(500-10000), and more preferably 1:(500-2000).

[0148] 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).

[0149] According to the present invention, preferably, the concentration of the metallocene compound in the polymerization reaction system is 1×10 -8 mol / L~1×10 -2 mol / L, preferably 1×10 -6 mol / L~1×10 -3 mol / L.

[0150] According to the present invention, preferably, the polymerization reaction is carried out in an inert organic solvent. As the inert organic solvent, it can be a mixture of one or more of a straight-chain aliphatic hydrocarbon, a branched aliphatic hydrocarbon, a substituted or unsubstituted cyclic aliphatic hydrocarbon, a substituted or unsubstituted aromatic hydrocarbon. As specific examples of the inert organic solvent, hexane, heptane, cyclohexane, cyclooctane, toluene, and xylene can be cited, among which one or more of toluene, cyclohexane and hexane are preferred. In addition, the amount of organic solvent can be determined according to the reaction activity to ensure that the produced polymer is well dissolved in the system, at least without affecting dispersion.

[0151] 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.

[0152] 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 partial pressure of ethylene is 0.1-6 MPa, preferably 0.1-3 MPa.

[0153] According to the method of the present invention, the copolymerization reaction conditions can be the common conditions used in the field 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.

[0154] 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.

[0155] The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.

[0156] The raw materials used in the following examples and comparative examples, unless otherwise specified, are all disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation method disclosed in the prior art.

[0157] In the following examples and comparative examples, the synthesized compounds 1 H NMR ( 1 H-NMR) was performed on a Bruker AVANCE III-400 MHz spectrometer with CDCl 3 as solvent at 25 °C.

[0158] 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.

[0159] 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. The sample solution was prepared by dissolving 200 mg of polymer material in 2.5 mL of D4-o-o-dichlorobenzene (ODCB-d4) in a 10 mm test tube at 130 °C. 13 C-NMR measurements were performed at 125°C, 20 Hz spin rate, 90° pulse angle, continuous Waltz-16 decoupling, 120 ppm spectral width, 5 s acquisition time, and 10 s relaxation delay. The repeating main chain methylene peak was set to 30.0000 ppm as a chemical shift reference.

[0160] The glass transition temperature of the polymer was measured on a differential scanning calorimeter TAQ 100 (DSC). In a nitrogen atmosphere, a polymer sample of about 2 mg was heated from 50°C to 200°C at a heating rate of 10°C per minute. After 1 minute of heating, the sample was cooled to 50°C at a cooling rate of 10°C per minute and kept at this temperature for another 1 minute. The sample was then heated to 200°C at a heating rate of 10°C per minute and the data was recorded.

[0161] Preparation Example 1

[0162] This example is used to illustrate the synthesis of metallocene compound H-1

[0163] Metallocene compound H-1: In the above compound H, M is zirconium and NA2 is dimethylamino.

[0164] 1) Synthesis of intermediate D

[0165] At 15°C, in a 250 ml three-necked flask with magnetic stirring, add catalyst C (pyrrolidine, 12 mmol) and 30 ml of anhydrous methanol, stir for 5 minutes, add compound A (1.8 g, 11.98 mmol), stir for 5 minutes, add compound B (2.0 g, 30.26 mmol), stir and react for 24 hours, keeping the reaction temperature not higher than 25°C. Filter to remove the solvent and catalyst, and wash the product with anhydrous methanol. Remove the residual solvent in vacuo at room temperature to obtain 2.26 g of yellow solid, with a yield of 94%.

[0166] 1 H-NMR (CDCl3): 6.62-6.55ppm (2H), 6.55-6.48ppm (2H), 3.33-3.24ppm (2H), 2.14-1.85ppm (12H).

[0167] 2) Synthesis of intermediate F

[0168] Under 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 the solution was slowly added dropwise to the fluorenyl lithium tetrahydrofuran solution; after the addition, the temperature was slowly raised to room temperature and stirred for 24 hours; the reaction mixture was poured into a saturated aqueous solution of ammonium chloride, the organic phase was separated, 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 with a yield of 81%.

[0169] 3) Synthesis of Metallocene Compound H-1

[0170] Under nitrogen atmosphere, 383 mg of intermediate 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-yellow solid with a yield of 85%.

[0171] 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).

[0172] Preparation Example 2

[0173] Synthesis of Metallocene Compound I-1

[0174] Metallocene compound I-1: In compound I, M is zirconium and X is a chlorine atom.

[0175] Weigh fluorene (499 mg, 3 mmol) into a 250 ml three-necked flask A, replace the vacuum-nitrogen three times, and then add 10 ml of anhydrous ether that has been pre-dehydrated and deoxygenated to dissolve. Place the three-necked flask A in a -20°C oil bath and stir for 15 minutes. At -20°C, add n-butyl lithium (1.05 equivalents, 2.5 mol per liter of hexane solution) dropwise into the three-necked flask A, and after completion, transfer the three-necked flask A to room temperature and stir for 8 hours. Weigh the intermediate product D (631 mg, 1.05 equivalents) into another 100 ml three-necked flask B, replace the nitrogen three times, and then add 10 ml of anhydrous ether that has been pre-treated with dried molecular sieves to dissolve. Place the aforementioned three-necked flask A in a -20°C oil bath and stir for 15 minutes. Add the solution in the three-necked flask B dropwise into the three-necked flask A. After completion, transfer the three-necked flask A to room temperature and stir for 24 hours. The three-necked 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 the three-necked flask A. After completion, the three-necked flask A was transferred to room temperature and stirred for 8 hours. The three-necked flask A was placed in a -70°C oil bath and stirred for 30 minutes. Under nitrogen protection, zirconium tetrachloride (700 mg, 3 mmol) solid was added to the three-necked flask A three times and stirred at room temperature for 72 hours. The reaction mixture was transferred to a centrifuge tube, centrifuged (3500 rpm) to take the supernatant, the residual solid was extracted with 5 ml of anhydrous ether, centrifuged (3500 rpm) to take the supernatant, extracted three times in total, and the residual solid was discarded. The supernatant and the extract were combined and the ether was removed under vacuum. The obtained solid was dissolved with 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 obtain 471 mg of solid compound with a yield of 30%.

[0176] 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).

[0177] Preparation Example 3

[0178] Synthesis of Metallocene Compound I-1

[0179] Metallocene compound I-1: In compound I, M is zirconium and X is a chlorine atom.

[0180] Under nitrogen atmosphere, 383 mg of intermediate product F (1 mmol) was dissolved in 15 ml of toluene. At -20 ° C, 0.84 mL of n-butyl lithium (2.5 mol per liter of hexane solution) was added dropwise. After completion, the three-necked flask A was transferred to room temperature and stirred for 8 hours. The three-necked flask A was placed in a -70 ° C oil bath and stirred for 30 minutes. Under nitrogen protection, zirconium tetrachloride (233 mg, 1 mmol) solid was added to the three-necked flask A three times and stirred at room temperature for 72 hours. The reaction mixture was transferred to a centrifuge tube, centrifuged (3500 rpm) to take the supernatant, the residual solid was extracted with 5 ml of anhydrous ether, centrifuged (3500 rpm) to take the supernatant, extracted three times in total, and the residual solid was discarded. The supernatant and the extract were combined and the ether was removed under vacuum. The obtained 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 obtain 276 mg of solid compound with a yield of 53%.

[0181] The obtained solid compound was confirmed to be the metallocene compound I-1 by nuclear magnetic resonance measurement.

[0182] Preparation Example 4

[0183] Synthesis of Metallocene Compound J-1

[0184] Metallocene compound J-1: M is zirconium, R 0 It is benzyl.

[0185] Under 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 tetrahydrofuran solution) was added dropwise. The temperature was slowly raised to room temperature. The mixture was reacted for 24 hours, filtered, and the solvent was removed in vacuo to obtain 523 mg of an orange-yellow solid with a yield of 82%.

[0186] 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).

[0187] Preparation Example 5

[0188] Synthesis of Metallocene Compound J-2

[0189] Metallocene compound J-2: M is zirconium, R 0 It is methyl.

[0190] Under 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 raised to room temperature. The mixture was reacted for 24 hours, filtered, and the solvent was removed in vacuo to obtain 357 mg of an orange-yellow solid with a yield of 74%.

[0191] 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).

[0192] Example 1

[0193] This example is used to illustrate the copolymerization of ethylene-norbornene.

[0194] Add 4.71 g of norbornene to a fully dried 250 ml glass polymerization bottle, evacuate, flush with nitrogen, and repeat three times. Evacuate, fill with ethylene, heat the oil bath to 70°C, and keep 1 standard atmosphere of ethylene in the polymerization bottle. Add 25 ml of toluene and 3 ml of methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) in sequence. After the temperature stabilizes at 70°C, add 2 ml of catalyst toluene solution (containing 2 micromoles of compound I-1) and start timing. During the reaction, when ethylene is consumed, replenish ethylene to keep 1 standard atmosphere of ethylene in the polymerization bottle. After 20 minutes, turn off ethylene, pour the reaction solution into a beaker, add 300 ml of ethanol and 5 ml of concentrated hydrochloric acid, stir for more than 6 hours, filter to obtain a polymer, and vacuum dry at 60°C for 24 hours to obtain 2.76 g of polymer with an activity of 4140 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer detected by gel permeation chromatography is Mw=17.9×10 4 , molecular weight distribution MWD = 1.92. The content of norbornene units in the polymer was 55.7 mol % as detected by nuclear magnetic resonance carbon-13 spectrum. The glass transition temperature of the polymer was 167° C. as determined by DSC.

[0195] Comparative Example 1

[0196] The method of Example 1 was followed, except that the metallocene compound I-1 was replaced by the same molar amount of dibenzhydryl (cyclopentadiene) (9-fluorenyl) zirconium dichloride. 2.01 g of polymer was obtained in the same manner, and the polymerization activity was 3015 kg polymer / mol catalyst / hour. The weight average molecular weight of the polymer measured by gel permeation chromatography was Mw=12.6×10 4 The molecular weight distribution MWD is 2.27. The content of norbornene units in the polymer is 51.0 mol% as determined by nuclear magnetic resonance carbon-13 spectrum. The glass transition temperature of the polymer is 163°C as determined by DSC.

[0197] Example 2

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

[0199] Add 4.71 g of norbornene to a fully dried 250 ml glass polymerization bottle, evacuate, flush with nitrogen, and repeat three times. Evacuate, fill with ethylene, heat the oil bath to 70°C, and keep 1 standard atmosphere of ethylene in the polymerization bottle. 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) in sequence. After the temperature stabilizes at 70°C, add 2 ml of triphenyl carbon tetrakis (pentafluorophenyl) borate toluene solution (containing 2.4 micromoles of triphenyl carbon tetrakis (pentafluorophenyl) borate) and start timing. During the reaction, when ethylene is consumed, add ethylene to keep 1 standard atmosphere of ethylene in the polymerization bottle. After 20 minutes, ethylene was turned off, the reaction solution was poured into a beaker, 300 ml of ethanol and 5 ml of concentrated hydrochloric acid were added, and the mixture was stirred for more than 6 hours. The 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 measured by gel permeation chromatography was Mw=19.8×10 4 , molecular weight distribution MWD = 1.99. The content of norbornene units in the polymer was 56.8 mol % as detected by nuclear magnetic resonance carbon-13 spectrum. The glass transition temperature of the polymer was 167° C. as determined by DSC.

[0200] Comparative Example 2

[0201] The method of Example 2 was followed, except that the metallocene compound I-1 was replaced by the same molar amount of dibenzhydryl (cyclopentadiene) (9-fluorenyl) zirconium dichloride. 2.51 g of polymer was obtained in the same manner, and the polymerization activity was 3765 kg polymer / mol catalyst / hour. The weight average molecular weight of the polymer measured by gel permeation chromatography was Mw=18.5×10 4, molecular weight distribution MWD = 2.07. The content of norbornene units in the polymer was 54.1 mol % as detected by nuclear magnetic resonance carbon-13 spectrum. The glass transition temperature of the polymer was 165° C. as determined by DSC.

[0202] Example 3

[0203] This example is used to illustrate the copolymerization of ethylene-norbornene.

[0204] Add 4.71 g of norbornene to a fully dried 250 ml glass polymerization bottle, evacuate, flush with nitrogen, and repeat three times. Evacuate, fill with ethylene, heat the oil bath to 70°C, and keep 1 standard atmosphere of ethylene in the polymerization bottle. Add 25 ml of toluene, 1 ml of triisobutylaluminum toluene solution (containing 1.0 mmol triisobutylaluminum), and 2 ml of catalyst toluene solution (containing 2 micromoles of compound I-1) in sequence. After 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 timing. During the reaction, when ethylene is consumed, add ethylene to keep 1 standard atmosphere of ethylene in the polymerization bottle. After 20 minutes, ethylene was turned off, the reaction solution was poured into a beaker, 300 ml of ethanol and 5 ml of concentrated hydrochloric acid were added, and the mixture was stirred for more than 6 hours. The 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 measured by gel permeation chromatography was Mw=8.5×10 4 , molecular weight distribution MWD = 1.90. The content of norbornene units in the polymer was 55.7 mol % as detected by nuclear magnetic resonance carbon-13 spectrum. The glass transition temperature of the polymer was 167° C. as determined by DSC.

[0205] Example 4

[0206] This example is used to illustrate the copolymerization of ethylene-norbornene.

[0207] Add 20 g of norbornene to a fully dried 100 ml stainless steel polymerization kettle, evacuate, flush with nitrogen, repeat three times, and finally fill with ethylene. Set the heating to 75°C. During the heating process, add 30 ml of toluene and 1 ml of triisobutylaluminum toluene solution (containing 1.0 mmol of triisobutylaluminum) in sequence. After the temperature stabilizes at 75°C, add 2 ml of catalyst toluene solution (containing 2 micromoles of compound I-1). After 5 minutes, add 2 ml of triphenyl carbon tetrakis (pentafluorophenyl) borate toluene solution (containing 2.4 micromoles of triphenyl carbon tetrakis (pentafluorophenyl) borate). Rapidly increase the pressure of ethylene to 2 standard atmospheres, set the heating to 80°C, and start timing. During the reaction, when ethylene is consumed, ethylene will be continuously replenished so that the total pressure in the polymerization bottle is always maintained at 2 standard atmospheres. After 30 minutes, ethylene was turned off, the reaction solution was poured into a beaker, 300 ml of ethanol and 5 ml of concentrated hydrochloric acid were added, and the mixture was stirred for more than 6 hours. The 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 / mol catalyst / hour. The weight average molecular weight of the polymer measured by gel permeation chromatography was Mw=14.7×10 4 , molecular weight distribution MWD = 2.09. The content of norbornene units in the polymer was 51.9 mol % as detected by nuclear magnetic resonance carbon-13 spectrum. The glass transition temperature of the polymer was 162° C. as determined by DSC.

[0208] Example 5

[0209] This example is used to illustrate the copolymerization of ethylene-norbornene.

[0210] Add 20 g of norbornene to a fully dried 100 ml stainless steel polymerization kettle, evacuate, flush with nitrogen, repeat three times, and finally fill with ethylene. Set the heating to 75°C. During the heating process, add 30 ml of toluene and 1 ml of triisobutylaluminum toluene solution (containing 1.0 mmol of triisobutylaluminum) in sequence. After the temperature stabilizes at 75°C, add 2 ml of catalyst toluene solution (containing 2 micromoles of compound I-1). After 5 minutes, add 2 ml of triphenyl carbon tetrakis (pentafluorophenyl) borate toluene solution (containing 2.4 micromoles of triphenyl carbon tetrakis (pentafluorophenyl) borate). Rapidly increase the pressure of ethylene to 4 standard atmospheres, set the heating to 80°C, and start timing. During the reaction, when ethylene is consumed, ethylene will be continuously replenished so that the total pressure in the polymerization bottle is always maintained at 4 standard atmospheres. After 30 minutes, ethylene was turned off, the reaction solution was poured into a beaker, 300 ml of ethanol and 5 ml of concentrated hydrochloric acid were added, and the mixture was stirred for more than 6 hours. The 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 / mol catalyst / hour. The weight average molecular weight of the polymer measured by gel permeation chromatography was Mw=17.6×10 4, molecular weight distribution MWD = 1.99. The content of norbornene units in the polymer was 48.6 mol% as detected by nuclear magnetic resonance carbon-13 spectrum. The glass transition temperature of the polymer was 159°C as determined by DSC.

[0211] Example 6

[0212] This example is used to illustrate the copolymerization of ethylene-norbornene.

[0213] 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. 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 measured by gel permeation chromatography was Mw=16.2×10 4 , molecular weight distribution MWD = 1.96. The content of norbornene units in the polymer was 55.6 mol% as detected by nuclear magnetic resonance carbon-13 spectrum. The glass transition temperature of the polymer was 167°C as determined by DSC.

[0214] Example 7

[0215] This example is used to illustrate the copolymerization of ethylene-norbornene.

[0216] 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. 3.22 g of polymer was obtained in the same manner, with an activity of 4830 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer measured by gel permeation chromatography was Mw=20.2×10 4 , molecular weight distribution MWD = 2.07. The content of norbornene units in the polymer was 54.9 mol % as detected by nuclear magnetic resonance carbon-13 spectrum. The glass transition temperature of the polymer was 165° C. as determined by DSC.

[0217] Example 8

[0218] This example is used to illustrate the copolymerization of ethylene-norbornene.

[0219] 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. The polymer 2.99 g was obtained in the same manner, with an activity of 4485 kg polymer / mol catalyst / hour. The weight average molecular weight of the polymer measured by gel permeation chromatography was Mw=18.6×10 4 , molecular weight distribution MWD = 1.93. The content of norbornene units in the polymer was 55.6 mol % as detected by nuclear magnetic resonance carbon-13 spectrum. The glass transition temperature of the polymer was 167° C. as determined by DSC.

[0220] Example 9

[0221] This example is used to illustrate the copolymerization of ethylene-norbornene.

[0222] 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. 3.01 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 measured by gel permeation chromatography was Mw=21.1×10 4 , molecular weight distribution MWD = 2.01. The content of norbornene units in the polymer was 55.6 mol % as detected by nuclear magnetic resonance carbon-13 spectrum. The glass transition temperature of the polymer was 168° C. as determined by DSC.

[0223] Example 10

[0224] This example is used to illustrate the copolymerization of ethylene-norbornene.

[0225] 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. 3.41 g of polymer was obtained in the same manner, with an activity of 5115 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer measured by gel permeation chromatography was Mw=17.8×10 4 , molecular weight distribution MWD = 1.90. The content of norbornene units in the polymer was 56.1 mol % as detected by nuclear magnetic resonance carbon-13 spectrum. The glass transition temperature of the polymer was 169° C. as determined by DSC.

[0226] Embodiment 11

[0227] This example is used to illustrate the copolymerization of ethylene-norbornene.

[0228] 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. 3.27 g of polymer was obtained in the same manner, with an activity of 4905 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer measured by gel permeation chromatography was Mw=19.2×10 4 , molecular weight distribution MWD = 1.96. The content of norbornene units in the polymer was 56.3 mol % as detected by nuclear magnetic resonance carbon-13 spectrum. The glass transition temperature of the polymer was 169° C. as determined by DSC.

[0229] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope 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, 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 method according to claim 1, wherein: 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; Preferably, 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-dialkylamine group having 2 to 6 carbon atoms; 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; 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; Preferably, X 1 and X 2 Each is independently Cl, methyl, benzyl or N,N-dimethylamino.

3. The method according to claim 1, wherein: The co-catalyst component includes a combination of an alkylaluminoxane or an organic boron compound and an organic aluminum compound; Preferably, the co-catalyst component is an alkylaluminoxane or a combination of an organic boron compound and an organic aluminum compound.

4. The method according to claim 3, 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; Preferably, R is selected from an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 10 to 30; Preferably, the alkylaluminoxane is methylaluminoxane.

5. The method according to claim 3, wherein: The organic boron compound is [B(C6F5)4] - Z + , Z + Having a structure represented by formula (4) or formula (5), 6. The method according to claim 3, 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; 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.

7. The method according to claim 3, 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), preferably 1:(500-10000), and more preferably 1:(500-2000).

8. The method according to claim 3, 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), preferably 1:(1-5), more preferably 1:(1-2), 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).

9. The method according to any one of claims 1 to 8, wherein: The concentration of the metallocene compound in the polymerization reaction system is 1×10 -8 mol / L~1×10 -2 mol / L, preferably 1×10 -6 mol / L~1×10 -3 mol / L.

10. The method according to any one of claims 1 to 8, wherein: The cycloolefin is one or more of cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, and tetracyclo[6.2.1.13,6.2,7]dodecene.

11. The method according to any one of claims 1 to 8, wherein: The partial pressure of ethylene is 0.1-6 MPa, preferably 0.1-3 MPa.

12. The method according to any one of claims 1 to 8, 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.

13. The method according to any one of claims 1 to 8, wherein: The copolymerization reaction temperature is -50 to 200°C, and the copolymerization reaction time is 1 to 300 minutes; Preferably, the copolymerization reaction temperature is -20 to 150° C., and the copolymerization reaction time is 5 to 60 minutes.

14. The ethylene-cycloolefin copolymer prepared by the method for preparing the ethylene-cycloolefin copolymer according to any one of claims 1 to 13.

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