Ethylene-cyclic olefin copolymers and their preparation methods

Abstract

This invention relates to the field of olefin polymerization and discloses an ethylene-cyclic olefin copolymer and its preparation method. The method for preparing the ethylene-cyclic olefin copolymer provided by the invention includes: using a catalyst composition to copolymerize ethylene with a cyclic olefin, wherein the catalyst composition comprises: a) a monometallic compound with the structure shown in formula (1), and b) a co-catalyst component. According to the method for preparing the ethylene-cyclic olefin copolymer of the present invention, the obtained ethylene-cyclic olefin copolymer has a high molecular weight.

Description

Technical Field

[0001] This invention relates to the field of olefin polymerization, and more specifically, to an ethylene-cycloolefin copolymer and its preparation method. Background Technology

[0002] Group IV transition metal organometallic compounds (GMMCs) have been extensively developed as catalysts for olefin polymerization in recent years. To expand their application range and overcome their susceptibility to poisoning, the structures of GMMC catalysts have been extended from metallocene catalysts to monometallocene and nonmetallocene catalysts. Metallocene catalysts are typically four-coordinate organometallic complexes, whose cyclopentadienyl groups are beneficial for controlling polymerization behavior and ensuring high activity; while nonmetallocene catalysts are six-coordinate organometallic complexes, with more stable structures. Combining the advantages of metallocene and nonmetallocene catalysts to obtain six-coordinate monometallocene catalysts will possess the advantages of both classic catalysts (Macromolecules, 2002, 35, 4871-4874; Organometallics, 2004, 23, 5324-5331.), and are expected to exhibit unique advantages in the field of olefin polymerization, preparing polyolefins with new compositions and structures, thus demonstrating new performance and application prospects.

[0003] Cycloolefin copolymers (COCs) obtained by copolymerizing ethylene with cycloolefins have wide applications, including optical and medical materials. Current research on COCs focuses on improving polymerization activity, polymer molecular weight, comonomer insertion rate, and conversion rate, while reducing the probability of chain transfer reactions. The first application of a six-coordinate monometallic catalyst with greater steric hindrance to the polymerization of cycloolefins with higher steric requirements will reveal new polymerization behaviors and further elucidate the structure-activity relationship of catalysts. Applying new catalytic systems to the copolymerization of ethylene and cycloolefins will yield COC materials with different chemical compositions and physical properties, exploring the application potential of COC materials. Summary of the Invention

[0004] The purpose of this invention is to provide a new method for copolymerizing ethylene with cyclic olefins and the ethylene-cyclic olefin copolymer prepared therefrom. According to the method for preparing the ethylene-cyclic olefin copolymer of this invention, the molecular weight of the obtained ethylene-cyclic olefin copolymer can be increased.

[0005] To achieve the above objectives, the present invention provides a method for preparing an ethylene-cyclic olefin copolymer, wherein the method comprises: using a catalyst composition to copolymerize ethylene with a cyclic olefin.

[0006] The catalyst composition comprises the following components:

[0007] a) Monocerometallic compounds with the structure shown in formula (1),

[0008]

[0009] In formula (1), Cp' is a cyclopentadienyl or unsubstituted cyclopentadienyl group with 1-20 carbon atoms, a cyclopentadienyl or unsubstituted indenyl group with 1-20 carbon atoms, or a fluorenyl or unsubstituted fluorenyl group with 1-20 carbon atoms.

[0010] R 1 R 2 R 3 R 4 R 5 and R 6 Hydrocarbon groups, which are each independently composed of hydrogen atoms, halogen atoms, or 1-20 carbon atoms;

[0011] X is a halogen atom;

[0012] b) Co-catalyst components.

[0013] Preferably, in formula (1), Cp' is a cyclopentadienyl or unsubstituted cyclopentadienyl with 1-16 carbon atoms, a cyclopentadienyl or unsubstituted indenyl with 1-16 carbon atoms, or a fluorenyl or unsubstituted fluorenyl with 1-16 carbon atoms, either monosubstituted or polysubstituted.

[0014] R 1 R 2 R 3 R 4 R 5 and R 6 Hydrocarbon groups, which are each independently composed of hydrogen atoms, halogen atoms, or 1-16 carbon atoms;

[0015] X is F, Cl, Br, or I.

[0016] Preferably, in formula (1), Cp' is an alkyl group with 1-10 carbon atoms and / or an aryl mono- or poly-substituted cyclopentadienyl group or an unsubstituted cyclopentadienyl group, an alkyl group with 1-10 carbon atoms and / or an aryl mono- or poly-substituted indenyl group or an unsubstituted indenyl group, or an alkyl group with 1-10 carbon atoms and / or an aryl mono- or poly-substituted fluorenyl group or an unsubstituted fluorenyl group;

[0017] R 1 R 2 R 3 R 4 R 5 and R 6 Alkyl groups, each consisting independently of a hydrogen atom, a halogen atom, or 1-10 carbon atoms;

[0018] X is F, Cl, or Br.

[0019] Preferably, in formula (1), Cp' is a mono- or poly-substituted cyclopentadienyl or unsubstituted cyclopentadienyl of 1-6 carbon atoms, a mono- or poly-substituted indole or unsubstituted indole of 1-6 carbon atoms, or a mono- or poly-substituted fluorenyl or unsubstituted fluorenyl of 1-6 carbon atoms.

[0020] R 1 R 2 R 3 R 4 R 5 and R 6 Alkyl groups consisting of hydrogen atoms, halogen atoms, or 1-6 carbon atoms, respectively;

[0021] X is either F or Cl.

[0022] Preferably, in formula (1), Cp' is a mono- or poly-substituted cyclopentadienyl or unsubstituted cyclopentadienyl of 1-3 carbon atoms, a mono- or poly-substituted indole or unsubstituted indole of 1-3 carbon atoms, or a mono- or poly-substituted fluorenyl or unsubstituted fluorenyl of 1-3 carbon atoms.

[0023] R 1 R 2 R 3 R 4 R 5 and R 6 Alkyl groups, each consisting independently of a hydrogen atom, a halogen atom, or 1-3 carbon atoms;

[0024] X is Cl.

[0025] Preferably, the monocerometallic compound is selected from one or more of the following compounds:

[0026] In formula (1), Cp' is cyclopentadienyl, R 1 R 2 R 3 R 4 R 5 and R 6 X is a hydrogen atom, and Cl is a hydrogen atom.

[0027] In equation (1), Cp' is indenyl, R 1 R 2 R 3 R 4 R 5 and R 6 X is a hydrogen atom, and Cl is a hydrogen atom.

[0028] In equation (1), Cp' is a fluorene group, R 1 R 2 R 3 R 4 R 5 and R 6 X is a hydrogen atom, and Cl is a hydrogen atom.

[0029] In formula (1), Cp' is cyclopentadienyl, R 1 R 2 R 3 R 4 and R 5 For hydrogen atoms, and R 6 X is a methyl group, and Cl is a methyl group.

[0030] In equation (1), Cp' is indenyl, R 1 R 2 R 3 R 4 and R 5 For hydrogen atoms, R 6 X is a methyl group, and Cl is a methyl group.

[0031] In equation (1), Cp' is a fluorene group, R 1 R 2 R 3 R 4 and R 5 For hydrogen atoms, R 6 X is a methyl group, and Cl is a methyl group.

[0032] In formula (1), Cp' is pentamethylcyclopentadienyl, R 1 R 2 R 3 R 4 and R 5 For hydrogen atoms, R 6 X is a methyl group, and Cl is a methyl group.

[0033] In formula (1), Cp' is pentamethylcyclopentadienyl, R 1 R 2 R 3 R 4 R 5 and R 6 X is a hydrogen atom, and Cl is a chlorine atom.

[0034] Preferably, the cocatalyst component includes one or more of alkylaluminoxanes, organoboron compounds, and organoaluminum compounds.

[0035] Preferably, the cocatalyst component is an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound.

[0036] Preferably, the alkylaluminoxane is a compound selected from the structures shown in formula (2) and / or formula (3).

[0037]

[0038] In formulas (2) and (3), R is selected from alkyl groups having 1-15 carbon atoms, and n is an integer from 4 to 30.

[0039] Preferably, R is selected from alkyl groups having 1-5 carbon atoms, and n represents an integer from 10 to 30.

[0040] Preferably, the alkylaluminoxane is methylaluminoxane.

[0041] Preferably, wherein, in b), the organoboron compound is [B(C6F5)4]. - Z + Z + Having the structure shown in equation (4) or equation (5),

[0042]

[0043] Preferably, the organoaluminum compound is a compound with the general formula AlX1X2X3, where X1, X2, and X3 are a halogen atom, an alkyl group with 1-8 carbon atoms, an alkoxy group with 1-8 carbon atoms, and an aryloxy group with 6-12 carbon atoms, respectively. X1, X2, and X3 can be the same or different, and at least one of them is an alkyl group with 1-8 carbon atoms. More preferably, the organoaluminum compound is triisobutylaluminum.

[0044] Preferably, the cocatalyst is a combination of organoboron compound and organoaluminum compound, wherein the molar ratio of the monometallocene compound to the organoboron compound is 1:(1-20), preferably 1:(1-10); and the molar ratio of the monometallocene compound to the organoaluminum compound is 1:(10-5000), preferably 1:(50-1000).

[0045] Preferably, the cocatalyst is an alkylaluminoxane, and the molar ratio of the monometallocene compound to the alkylaluminoxane (calculated as aluminum) is 1:(100-50000), more preferably 1:(1000-30000).

[0046] Preferably, the concentration of cyclic olefins in the polymerization reaction system is 0.001-8 mol / L, and more preferably 0.01-4 mol / L.

[0047] Preferably, the concentration of the metallocene compound in the polymerization reaction system is 1 × 10⁻⁶. -8 mol / L ~ 1×10 -2 mol / L, preferably 1×10 -7 mol / L ~ 5×10-3 Moles per liter.

[0048] Preferably, the copolymerization temperature is -50 to 200°C and the copolymerization time is 1 to 300 minutes; more preferably, the copolymerization temperature is -20 to 150°C and the copolymerization time is 5 to 60 minutes.

[0049] Preferably, the partial pressure of the ethylene is 0.1-6 MPa, and more preferably 0.1-3 MPa.

[0050] Preferably, the cyclic olefin is a cyclic olefin containing 5-20 carbon atoms.

[0051] Preferably, the cycloolefin is one or more of cyclopentene, cycloheptene, cyclooctene, norbornene, and tetracyclo[6.2.1.13,6.02,7]dodecyl-4-ene.

[0052] Preferably, the cyclic olefin is norbornene.

[0053] Preferably, the polymerization reaction is carried out in the presence of an organic solvent, which is one or more of toluene, cyclohexane, and hexane.

[0054] According to a second aspect of the present invention, an ethylene-cycloolefin copolymer prepared by the method for preparing the ethylene-cycloolefin copolymer described in the first aspect of the present invention is provided.

[0055] Through the above technical solution, the present invention provides a novel method for copolymerizing ethylene and cyclic olefins, and the ethylene-cyclic olefin copolymer prepared therefrom. The method for preparing the ethylene-cyclic olefin copolymer according to the present invention can increase the molecular weight of the obtained ethylene-cyclic olefin copolymer. Furthermore, since the ethylene-cyclic olefin copolymer will have a higher glass transition temperature, it has more potential applications. Detailed Implementation

[0056] The endpoints and any values ​​of the ranges 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 endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0057] According to one aspect of the present invention, a method for preparing an ethylene-cyclic olefin copolymer is provided, wherein the method comprises: using a catalyst composition to copolymerize ethylene with a cyclic olefin.

[0058] The catalyst composition comprises the following components:

[0059] a) Monocerometallic compounds with the structure shown in formula (1),

[0060]

[0061] In formula (1), Cp' is a cyclopentadienyl or unsubstituted cyclopentadienyl group with 1-20 carbon atoms, a cyclopentadienyl or unsubstituted indenyl group with 1-20 carbon atoms, or a fluorenyl or unsubstituted fluorenyl group with 1-20 carbon atoms.

[0062] R 1 R 2 R 3 R 4 R 5 and R 6 Hydrocarbon groups, which are each independently composed of hydrogen atoms, halogen atoms, or 1-20 carbon atoms;

[0063] X is a halogen atom;

[0064] b) Co-catalyst components.

[0065] According to the present invention, preferably, in formula (1), Cp' is a mono- or poly-substituted cyclopentadienyl or unsubstituted cyclopentadienyl with 1-16 carbon atoms, a mono- or poly-substituted indenyl or unsubstituted indenyl with 1-16 carbon atoms, or a mono- or poly-substituted fluorenyl or unsubstituted fluorenyl with 1-16 carbon atoms; more preferably, in formula (1), Cp' is an alkyl with 1-10 carbon atoms and / or an aryl with 6-12 carbon atoms, a mono- or poly-substituted cyclopentadienyl or unsubstituted cyclopentadienyl with 1-10 carbon atoms and / or an aryl with 6-12 carbon atoms, a mono- or poly-substituted indenyl or unsubstituted indenyl with 1-10 carbon atoms, or an alkyl with 1-10 carbon atoms and / or a carbon atom The aryl mono- or poly-substituted fluorenyl or unsubstituted fluorenyl groups having 6-12 carbon atoms; more preferably, in formula (1), Cp' is an alkyl mono- or poly-substituted cyclopentadienyl or unsubstituted cyclopentadienyl group having 1-6 carbon atoms, an alkyl mono- or poly-substituted indenyl or unsubstituted indenyl group having 1-6 carbon atoms, or an alkyl mono- or poly-substituted fluorenyl or unsubstituted fluorenyl group having 1-6 carbon atoms; particularly preferably, in formula (1), Cp' is an alkyl mono- or poly-substituted cyclopentadienyl or unsubstituted cyclopentadienyl group having 1-3 carbon atoms, an alkyl mono- or poly-substituted indenyl or unsubstituted indenyl group having 1-3 carbon atoms, or an alkyl mono- or poly-substituted fluorenyl or unsubstituted fluorenyl group having 1-3 carbon atoms.

[0066] As for the alkyl group with 1-10 carbon atoms mentioned above, it refers to an alkyl group with a total number of carbon atoms of 1-10, including straight-chain alkyl, branched alkyl or cycloalkyl. For example, it can be a straight-chain alkyl, branched alkyl or cycloalkyl group with a total number of carbon atoms of 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, isobutyl, pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl, etc.

[0067] Examples of aryl groups with 6-12 carbon atoms include phenyl, benzyl, phenethyl, diphenylmethylene, and diphenylethylene.

[0068] In the compound represented by formula (1) of the present invention, X is a halogen atom.

[0069] Examples of halogen atoms include fluorine, chlorine, bromine, or iodine, with fluorine, chlorine, or bromine being preferred, chlorine or bromine being more preferred, and chlorine being particularly preferred.

[0070] In the compound represented by formula (1) of the present invention, R 1 R 2 R 3 R 4 R 5 and R 6 Hydrocarbon groups consisting of hydrogen atoms, halogen atoms, or 1-20 carbon atoms, respectively.

[0071] Preferably, R 1 R 2 R 3 R 4 R 5 and R 6 Each is independently a hydrogen atom, a halogen atom, or an alkyl group having 1-10 carbon atoms; more preferably, R 1 R 2 R 3 R 4 R 5 and R 6 Each is independently a hydrogen atom, a halogen atom, or an alkyl group with 1-6 carbon atoms; particularly preferably, R 1 R 2 R 3 R 4 R 5 and R 6 Alkyl groups, which are each independently composed of a hydrogen atom, a halogen atom, or 1-3 carbon atoms.

[0072] Examples of hydrocarbon groups with 1-20 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, phenyl, benzyl, phenethyl, etc.

[0073] In a preferred embodiment of the present invention, in formula (1), Cp' is an alkyl group having 1-10 carbon atoms and / or an aryl group having 6-12 carbon atoms, either a monosubstituted or polysubstituted cyclopentadienyl group or an unsubstituted cyclopentadienyl group; an alkyl group having 1-10 carbon atoms and / or an aryl group having 6-12 carbon atoms, either a monosubstituted or polysubstituted indenyl group or an unsubstituted indenyl group; or an alkyl group having 1-10 carbon atoms and / or an aryl group having 6-12 carbon atoms, either a monosubstituted or polysubstituted fluorenyl group or an unsubstituted fluorenyl group; R 1 R 2 R 3 R 4 R 5 and R 6 Each is independently a hydrogen atom, a halogen atom, or an alkyl group with 1-10 carbon atoms; X is F, Cl, or Br; in this preferred embodiment, more preferably, in formula (1), Cp' is a mono- or poly-substituted cyclopentadienyl or unsubstituted cyclopentadienyl of an alkyl group with 1-6 carbon atoms, a mono- or poly-substituted indenyl or unsubstituted indenyl of an alkyl group with 1-6 carbon atoms, or a mono- or poly-substituted fluorenyl or unsubstituted fluorenyl of an alkyl group with 1-6 carbon atoms; R 1 R 2 R 3 R 4 R 5 and R 6 Each is independently a hydrogen atom, a halogen atom, or an alkyl group with 1-6 carbon atoms; X is F or Cl; in this preferred embodiment, particularly preferably, in formula (1), Cp' is a mono- or poly-substituted cyclopentadienyl or unsubstituted cyclopentadienyl of 1-3 carbon atoms, a mono- or poly-substituted indenyl or unsubstituted indenyl of 1-3 carbon atoms, or a mono- or poly-substituted fluorenyl or unsubstituted fluorenyl of 1-3 carbon atoms; R 1 R 2 R 3 R 4 R 5 and R 6 Each of the following is an alkyl group consisting of a hydrogen atom, a halogen atom, or 1-3 carbon atoms; X is Cl.

[0074] In another preferred embodiment of the present invention, in formula (1), Cp' is an alkyl group having 1-10 carbon atoms and / or an aryl group having 6-12 carbon atoms, which is monosubstituted or polysubstituted with cyclopentadienyl or unsubstituted; R 1 R 2 R 3 R 4 R 5 and R 6 Each is independently a hydrogen atom, a halogen atom, or an alkyl group with 1-10 carbon atoms; X is F, Cl, or Br; in this preferred embodiment, more preferably, in formula (1), Cp' is a mono- or poly-substituted cyclopentadienyl or unsubstituted cyclopentadienyl alkyl group with 1-6 carbon atoms; R 1 R 2 R 3 R 4 R 5 and R 6 Each is independently a hydrogen atom, a halogen atom, or an alkyl group with 1-6 carbon atoms; X is F or Cl; in this preferred embodiment, particularly preferably, in formula (1), Cp' is a mono- or poly-substituted cyclopentadienyl or unsubstituted cyclopentadienyl alkyl group with 1-3 carbon atoms; R 1 R 2 R 3 R 4 R 5 and R 6 Each of the following is an alkyl group consisting of a hydrogen atom, a halogen atom, or 1-3 carbon atoms; X is Cl.

[0075] According to the present invention, the monocerometallic compound is particularly preferably selected from one or more of the following compounds:

[0076] In formula (1), Cp' is cyclopentadienyl, R 1 R 2 R 3 R 4 R 5 and R 6 X is a hydrogen atom, and Cl is a hydrogen atom.

[0077] In equation (1), Cp' is indenyl, R 1 R 2 R 3 R 4 R 5 and R 6 X is a hydrogen atom, and Cl is a hydrogen atom.

[0078] In equation (1), Cp' is a fluorene group, R 1 R 2 R 3 R 4R 5 and R 6 X is a hydrogen atom, and Cl is a hydrogen atom.

[0079] In formula (1), Cp' is cyclopentadienyl, R 1 R 2 R 3 R 4 and R 5 For hydrogen atoms, R 6 X is a methyl group, and Cl is a methyl group.

[0080] In equation (1), Cp' is indenyl, R 1 R 2 R 3 R 4 and R 5 For hydrogen atoms, R 6 X is a methyl group, and Cl is a methyl group.

[0081] In equation (1), Cp' is a fluorene group, R 1 R 2 R 3 R 4 and R 5 For hydrogen atoms, R 6 X is a methyl group, and Cl is a methyl group.

[0082] In formula (1), Cp' is pentamethylcyclopentadienyl, R 1 R 2 R 3 R 4 and R 5 For hydrogen atoms, R 6 X is a methyl group, and Cl is a methyl group.

[0083] In formula (1), Cp' is pentamethylcyclopentadienyl, R 1 R 2 R 3 R 4 R 5 and R 6 X is a hydrogen atom, and Cl is a chlorine atom.

[0084] According to the present invention, the monometallic compounds with the structure shown in formula (1) can be obtained by conventional synthetic methods in the art, for example, by the method described in the preparation example below or similar methods.

[0085] According to the present invention, the cocatalyst component can be any of the cocatalyst components commonly used in the art. Preferably, the cocatalyst component includes one or more of alkylaluminoxanes, organoboron compounds, and organoaluminum compounds; more preferably, the cocatalyst component is an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound.

[0086] The alkylaluminoxanes described above are preferably compounds selected from those shown in formula (2) and / or formula (3).

[0087]

[0088] In formulas (2) and (3), R is selected from alkyl groups having 1-15 carbon atoms, and n is an integer from 4 to 30; preferably, R is selected from alkyl groups having 1-5 carbon atoms, and n represents an integer from 10 to 30.

[0089] Specific examples of the alkyl groups mentioned above 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, etc.

[0090] 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, 30, etc.

[0091] Specific examples of the alkylaluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, etc., with methylaluminoxane being preferred.

[0092] According to the present invention, the organoboron compound can be any organoboron compound used in the art as a cocatalyst, preferably, the organoboron compound is [B(C6F5)4]. - Z + Z + Having the structure shown in equation (4) or equation (5),

[0093]

[0094] According to the present invention, the organoaluminum compound can be any organoaluminum compound used as a cocatalyst in the art. Preferably, the organoaluminum compound is a compound with the general formula AlX1X2X3, where X1, X2, and X3 are a halogen atom, an alkyl group with 1-8 carbon atoms, an alkoxy group with 1-8 carbon atoms, and an aryloxy group with 6-12 carbon atoms, respectively. X1, X2, and X3 can be the same or different, and at least one of them is an alkyl group with 1-8 carbon atoms.

[0095] Examples of alkyl groups having 1-8 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, etc.

[0096] Examples of alkoxy groups having 1-8 carbon atoms include various alkoxy groups having "alkyl groups having 1-8 carbon atoms" as specifically exemplified above.

[0097] Examples of halogen atoms include fluorine, chlorine, bromine, or iodine, with fluorine, chlorine, or bromine being preferred, chlorine or bromine being more preferred, and chlorine being particularly preferred.

[0098] In this invention, specific examples of the organoaluminum compounds include one or more of the following: trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, trisec-butylaluminum, tricyclopentylaluminum, tri-n-pentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, and tripentylaluminum. Triisobutylaluminum is preferred among these.

[0099] According to the present invention, when the co-catalyst is an alkylaluminoxane, the molar ratio of the monometallocene compound to the alkylaluminoxane based on aluminum can be 1:(100-50000), preferably 1:(1000-30000).

[0100] When the cocatalyst is an alkylaluminoxane, specific examples of the molar ratio of the monometallocene compound to the alkylaluminoxane based on aluminum can be given, for example: 1:100, 1:250, 1:500, 1:750, 1:1000, 1:1250, 1:1500, 1:2000, 1:3000, 1:4000, 1:5000, 1:8000, 1:12000, 1:15000, 1:18000, 1:20000, 1:25000, 1:30000, 1:35000, 1:40000, 1:45000, 1:50000, etc., as well as any two of the above ranges.

[0101] According to the present invention, when the cocatalyst is a combination of an organoboron compound and an organoaluminum compound, the molar ratio of the monometallocene compound to the organoboron compound can be 1:(1-20), preferably 1:(1-10), more preferably 1:(1-2); the molar ratio of the monometallocene compound to the organoaluminum compound is 1:(10-5000), preferably 1:(50-1000), and most preferably 1:(200-1000).

[0102] When the cocatalyst is a combination of an organoboron compound and an organoaluminum compound, specific examples of the molar ratio of the monometallocene compound to the organoaluminum compound can be given, for example: 1:10, 1:50, 1:100, 1:150, 1:200, 1:250, 1:300, 1:350, 1:400, 1:450, 1:500, 1:550, 1:600, 1:650, 1:700, 1:750, 1:800, 1:850, 1:900, 1:950, 1:1000, 1:1500, 1:2500, 1:3000, 1:4000, 1:5000, etc., as well as any two of the above ranges.

[0103] When the cocatalyst is a combination of an organoboron compound and an organoaluminum compound, specific examples of the molar ratio of the monometallocene compound to the organoboron compound can be, for example, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, etc., as well as any two of the above ranges.

[0104] According to the method of the present invention, the amount of ethylene and the cyclic olefin can be the amount commonly used in the art for synthesizing ethylene-cyclic olefin copolymers, for example, the concentration of cyclic olefin in the polymerization reaction system is 0.001-8 mol / L, preferably 0.01-4 mol / L.

[0105] According to the method of the present invention, the metallocene compound in the polymerization reaction system can be used in amounts commonly employed in the art for the synthesis of ethylene-cycloolefin copolymers. Preferably, the concentration of the metallocene compound in the polymerization reaction system is 1 × 10⁻⁶. -8 mol / L ~ 1×10 -2 mol / L, preferably 1×10 -7 mol / L ~ 5×10 -3 Moles per liter.

[0106] According to the method of the present invention, preferably, the cyclic olefin is a cyclic olefin containing 5-20 carbon atoms; more preferably, the cyclic olefin is one or more of cyclopentene, cycloheptene, cyclooctene, norbornene, and tetracyclo[6.2.1.13,6.02,7]dodecyl-4-ene; even more preferably, the cyclic olefin is norbornene.

[0107] According to the method of the present invention, preferably, the polymerization reaction is carried out in an inert organic solvent. The inert organic solvent can be one or a mixture of several of the following: straight-chain aliphatic hydrocarbons, branched-chain aliphatic hydrocarbons, substituted or unsubstituted cyclic aliphatic hydrocarbons, and substituted or unsubstituted aromatic hydrocarbons. Specific examples of the inert organic solvent include: hexane, heptane, cyclohexane, cyclooctane, toluene, and xylene, preferably one or more of toluene, cyclohexane, and hexane. Furthermore, the amount of organic solvent can be determined according to the reactivity to ensure that the resulting polymer dissolves well in the system, or at least does not affect dispersion.

[0108] According to the method of the present invention, the conditions for the copolymerization reaction can be those commonly used in the synthesis of ethylene-cycloolefin copolymers. Preferably, the temperature of the copolymerization reaction is -50 to 200°C, and the time of the copolymerization reaction is 1 to 300 minutes; more preferably, the temperature of the copolymerization reaction is -20 to 150°C, and the time of the copolymerization reaction is...

[0109] The interval is 5-60 minutes. Additionally, the partial pressure of the ethylene can be 0.1-6 MPa, preferably 0.1-3 MPa.

[0110] The method for preparing the ethylene-cyclic olefin copolymer according to the present invention can increase the molecular weight of the obtained ethylene-cyclic olefin copolymer and further improve the polymerization activity.

[0111] According to a second aspect of the present invention, an ethylene-cycloolefin copolymer prepared by the method for preparing the ethylene-cycloolefin copolymer described in the first aspect of the present invention is provided.

[0112] The present invention will be described in detail below through embodiments, but the present invention is not limited to the following embodiments.

[0113] Unless otherwise specified, the raw materials used in the following examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0114] In the following examples and comparative examples, the compounds synthesized were... 1 H nuclear magnetic resonance (H nuclear magnetic resonance) 1 H-NMR was performed on a Bruker AVANCE III-500MHz spectrometer using CDCl3 as solvent at 25°C.

[0115] Polymer molecular weight (Mw) and molecular weight distribution (PDI) were determined by gel permeation chromatography (GPC) at 150 °C on an Agilent PL-GPC220 with 1,2,4-trichlorobenzene as solvent.

[0116] The monoceramic metal compound used has the following structure, abbreviated as A.

[0117]

[0118] Preparation Example 1

[0119] This example illustrates the synthesis of monometallic compound A1.

[0120] Monocerometallic compound A1: In the above compound A, X is chlorine, Cp' is cyclopentadiene, and R... 1 R 2 R 3 R 4 R 5 R 6 It is a hydrogen atom.

[0121] In a 100 mL Schlenk flask, zirconium dichlorophenocene (150 mg, 0.513 mmol) and 8-hydroxyquinoline (150 mg, 1.03 mmol) were added, followed by the addition of dichloromethane (7.5 mL) under a nitrogen atmosphere. The mixture was stirred at room temperature for 3 hours to obtain a yellow suspension. Upon addition of hexane (50 mL), a yellow precipitate formed. The precipitate was filtered at room temperature, and the residual solvent was removed. This process was repeated three times to yield 170 mg of a yellow solid, with a yield of 69%.

[0122] 1 H NMR (500.1MHz, CDCl3): δ=8.40 (ddd, J=111.4Hz, J=4.8Hz, J=1.4Hz, 2H), 7.92 (ddd, J=4 7.0Hz,J=8.2Hz,J=1.3Hz,2H),7.39(dt,J=32.0Hz,J=7.9Hz,2H),6.46(s,5H(Cp)),and 7.09-6.93ppm (6H, other quinoline protons). 13 C{ 1 H}NMR with DEPT-135 (125.7MHz, CDCl3): δ = 161.12 (d, J = 107.2Hz), 146.33 (d, J = 18.4Hz), 141.60 (d, J = 122.2Hz), 138.74 (d, J=100.7Hz),130.20(d,J=119.5Hz),130.05(s),121.88(d,J=10.2Hz),116.78(s,Cp),115.01(d,J=331.9Hz),and 114.50ppm(d,J=1.3Hz).

[0123] Preparation Example 2

[0124] This embodiment illustrates the synthesis of monometallic compound A2.

[0125] Monocerometallic compound A2: In the above compound A, X is chlorine, Cp' is pentamethylcyclopentadiene, and R... 1 R 2 R 3 R 4 R 5 R 6 It is a hydrogen atom.

[0126] In a 100 mL Schlenk flask, bis(pentamethylcyclopentadiene)zirconium dichloride (222 mg, 0.513 mmol) and 8-hydroxyquinoline (150 mg, 1.03 mmol) were added. Dichloromethane (7.5 mL) was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 3 hours to obtain a yellow suspension. Hexane (50 mL) was added, resulting in the precipitation of a yellow precipitate. The precipitate was filtered at room temperature, and the residual solvent was removed. This process was repeated three times to give 158 mg of a yellow solid, with a yield of 56%.

[0127] Similar to Preparation Example 1, the structure of the compound was confirmed by proton and carbon spectroscopy.

[0128] Preparation Example 3

[0129] This example illustrates the synthesis of monometallic compound A3.

[0130] Monocerometallic compound A3: In the above compound A, X is chlorine, Cp' is cyclopentadiene, and R... 1 R 2 R 3 R 4 R 5 For hydrogen atoms, R 6 It is a methyl group.

[0131] In a 100 mL Schlenk flask, zirconium dichlorophenocene (150 mg, 0.513 mmol) and 2-methyl-8-hydroxyquinoline (164 mg, 1.03 mmol) were added, followed by the addition of dichloromethane (7.5 mL) under a nitrogen atmosphere. The mixture was stirred at room temperature for 3 hours to obtain a yellow suspension. Upon addition of hexane (50 mL), a yellow precipitate formed. The precipitate was filtered at room temperature, and the residual solvent was removed. This process was repeated three times to yield 167 mg of a yellow solid, with a yield of 64%.

[0132] Similar to Preparation Example 1, the structure of the compound was confirmed by proton and carbon spectroscopy.

[0133] Example 1

[0134] This example illustrates the copolymerization of ethylene and norbornene.

[0135] 9.41 g of norbornene was added to a thoroughly dried 100 mL stainless steel polymerization reactor. The reactor was then evacuated, purged with nitrogen three times, and finally purged with ethylene. The reactor was heated to 100 °C. During heating, 57 mL of toluene and 3 mL of a methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) were added sequentially. After the temperature stabilized at 100 °C, 0.2 mL of a catalyst toluene solution (containing 0.2 μmol of compound A1) was added. The ethylene was rapidly pressurized to 10 atm, and the reactor was heated to 100 °C with timing initiated. During the reaction, ethylene was replenished as needed to maintain a total pressure of 10 atm in the polymerization flask. After 10 minutes, the ethylene was shut off, and 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 at least 6 hours. After filtration, the mixture was vacuum-dried at 60 °C for 24 hours to obtain the polymer. The polymer's glass transition temperature was 57.63 °C. The polymerization activity, weight-average molecular weight, and molecular weight distribution of the polymer, as determined by gel permeation chromatography, are shown in Table 1.

[0136] Example 2

[0137] This example illustrates the copolymerization of ethylene and norbornene.

[0138] 9.41 g of norbornene was added to a thoroughly dried 100 mL stainless steel polymerization reactor. The reactor was then evacuated, purged with nitrogen three times, and finally purged with ethylene. The reactor was heated to 100 °C. During heating, 57 mL of toluene and 3 mL of a methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) were added sequentially. After the temperature stabilized at 100 °C, 0.5 mL of a catalyst toluene solution (containing 0.5 μmol of compound A1) was added. The ethylene was rapidly pressurized to 10 atm, and the reactor was heated to 100 °C with timing initiated. During the reaction, ethylene was replenished as needed to maintain a total pressure of 10 atm in the polymerization flask. After 10 minutes, the ethylene was shut off, and 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 at least 6 hours. After filtration, the mixture was vacuum-dried at 60 °C for 24 hours to obtain the polymer. The polymer's glass transition temperature was 47.50 °C. The polymerization activity, gel permeation chromatography analysis of the polymer's weight-average molecular weight, and molecular weight distribution are shown in Table 1.

[0139] Example 3

[0140] This example illustrates the copolymerization of ethylene and norbornene.

[0141] 9.41 g of norbornene was added to a thoroughly dried 100 mL stainless steel polymerization reactor. The reactor was then evacuated, purged with nitrogen three times, and finally purged with ethylene. The reactor was heated to 100 °C. During heating, 57 mL of toluene and 3 mL of a methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) were added sequentially. After the temperature stabilized at 100 °C, 1 mL of a catalyst toluene solution (containing 1 μmol of compound A1) was added. The ethylene was rapidly pressurized to 10 atm, and the reactor was heated to 100 °C with timing initiated. During the reaction, ethylene was replenished as needed to maintain a total pressure of 10 atm in the polymerization flask. After 10 minutes, the ethylene was shut off, and 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 at least 6 hours. After filtration, the mixture was vacuum-dried at 60 °C for 24 hours to obtain the polymer. The polymer's glass transition temperature was 53.86 °C. The polymerization activity, weight-average molecular weight, and molecular weight distribution of the polymer, as determined by gel permeation chromatography, are shown in Table 1.

[0142] Example 4

[0143] This example illustrates the copolymerization of ethylene and norbornene.

[0144] 4.71 g of norbornene was added to a thoroughly dried 100 mL stainless steel polymerization reactor. The reactor was then evacuated, purged with nitrogen three times, and finally purged with ethylene. The reactor was heated to 100 °C. During heating, 57 mL of toluene and 3 mL of a methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) were added sequentially. After the temperature stabilized at 100 °C, 0.5 mL of a catalyst toluene solution (containing 0.5 μmol of compound A1) was added. The ethylene was rapidly pressurized to 10 atm, and the reactor was heated to 100 °C with timing initiated. During the reaction, ethylene was replenished as needed to maintain a total pressure of 10 atm in the polymerization flask. After 10 minutes, the ethylene was shut off, and 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 at least 6 hours. After filtration, the mixture was vacuum-dried at 60 °C for 24 hours to obtain the polymer. The polymerization activity, weight-average molecular weight, and molecular weight distribution of the polymer, as determined by gel permeation chromatography, are shown in Table 1.

[0145] Example 5

[0146] This example illustrates the copolymerization of ethylene and norbornene.

[0147] 2.35 g of norbornene was added to a thoroughly dried 100 mL stainless steel polymerization reactor. The reactor was then evacuated, purged with nitrogen three times, and finally purged with ethylene. The reactor was heated to 100 °C. During heating, 57 mL of toluene and 3 mL of a methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) were added sequentially. After the temperature stabilized at 100 °C, 0.5 mL of a catalyst toluene solution (containing 0.5 μmol of compound A1) was added. The ethylene was rapidly pressurized to 10 atm, and the reactor was heated to 100 °C with timing initiated. During the reaction, ethylene was replenished as needed to maintain a total pressure of 10 atm in the polymerization flask. After 10 minutes, the ethylene was shut off, the reaction mixture was poured into a beaker, and 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added. The mixture was stirred for at least 6 hours, filtered, and then vacuum-dried at 60 °C for 24 hours to obtain the polymer. The polymerization activity, weight-average molecular weight, and molecular weight distribution of the polymer, as determined by gel permeation chromatography, are shown in Table 1.

[0148] Example 6

[0149] This example illustrates the copolymerization of ethylene and norbornene.

[0150] 1.18 g of norbornene was added to a thoroughly dried 100 mL stainless steel polymerization reactor. The reactor was then evacuated, purged with nitrogen three times, and finally purged with ethylene. The reactor was heated to 100 °C. During heating, 57 mL of toluene and 3 mL of a methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) were added sequentially. After the temperature stabilized at 100 °C, 0.5 mL of a catalyst toluene solution (containing 0.5 μmol of compound A1) was added. The ethylene was rapidly pressurized to 10 atm, and the reactor was heated to 100 °C with timing initiated. During the reaction, ethylene was replenished as needed to maintain a total pressure of 10 atm in the polymerization flask. After 10 minutes, the ethylene was shut off, the reaction mixture was poured into a beaker, and 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added. The mixture was stirred for at least 6 hours, filtered, and then vacuum-dried at 60 °C for 24 hours to obtain the polymer. The polymerization activity, weight-average molecular weight, and molecular weight distribution of the polymer, as determined by gel permeation chromatography, are shown in Table 1.

[0151] Example 7

[0152] This example illustrates the copolymerization of ethylene and norbornene.

[0153] 2.35 g of norbornene was added to a thoroughly dried 100 mL stainless steel polymerization reactor. The reactor was then evacuated, purged with nitrogen three times, and finally purged with ethylene. The reactor was heated to 80 °C. During heating, 57 mL of toluene and 3 mL of a methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) were added sequentially. After the temperature stabilized at 80 °C, 0.5 mL of a catalyst toluene solution (containing 0.5 μmol of compound A1) was added. The ethylene was rapidly pressurized to 10 atm, and the reactor was heated to 80 °C with timing initiated. During the reaction, ethylene was replenished as needed to maintain a total pressure of 10 atm in the polymerization flask. After 10 minutes, the ethylene was shut off, the reaction mixture was poured into a beaker, and 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added. The mixture was stirred for at least 6 hours, filtered, and then vacuum-dried at 60 °C for 24 hours to obtain the polymer. The polymerization activity, weight-average molecular weight, and molecular weight distribution of the polymer, as determined by gel permeation chromatography, are shown in Table 1.

[0154] Example 8

[0155] This example illustrates the copolymerization of ethylene and norbornene.

[0156] 2.35 g of norbornene was added to a thoroughly dried 100 mL stainless steel polymerization reactor. The reactor was then evacuated, purged with nitrogen three times, and finally purged with ethylene. The reactor was heated to 100 °C. During heating, 57 mL of toluene and 3 mL of a methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) were added sequentially. After the temperature stabilized at 100 °C, 0.2 mL of a catalyst toluene solution (containing 0.2 μmol of compound A1) was added. The ethylene was rapidly pressurized to 10 atm, and the reactor was heated to 100 °C with timing initiated. During the reaction, ethylene was replenished as needed to maintain a total pressure of 10 atm in the polymerization flask. After 10 minutes, the ethylene was shut off, the reaction mixture was poured into a beaker, and 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added. The mixture was stirred for at least 6 hours, filtered, and then vacuum-dried at 60 °C for 24 hours to obtain the polymer. The polymerization activity, weight-average molecular weight, and molecular weight distribution of the polymer, as determined by gel permeation chromatography, are shown in Table 1.

[0157] Example 9

[0158] This example illustrates the copolymerization of ethylene with tetracyclo[6.2.1.13,6.02,7]dodecyl-4-ene.

[0159] The method of Example 8 was followed, except that the comonomer was tetracyclic [6.2.1.13,6.02,7]dodecyl-4-ene, and the polymer was obtained in the same manner. The polymerization activity, the weight-average molecular weight and molecular weight distribution of the polymer as determined by gel permeation chromatography are shown in Table 1.

[0160] Example 10

[0161] This example illustrates the copolymerization of ethylene and cyclooctene.

[0162] The method of Example 8 was followed, except that the comonomer was cyclooctene, and the polymer was obtained in the same manner. The polymerization activity, the weight-average molecular weight and molecular weight distribution of the polymer as determined by gel permeation chromatography are shown in Table 1.

[0163] Example 11

[0164] This example illustrates the copolymerization of ethylene and norbornene.

[0165] Add 2.35 g of norbornene to a thoroughly dried 100 mL stainless steel polymerization reactor, evacuate, and purge with nitrogen three times, finally introducing ethylene. Set the temperature to 100 °C. During heating, add 56 mL of toluene and 1 mL of triisobutylaluminum toluene solution (containing 1.0 mmol of triisobutylaluminum). After 5 minutes, add 1 mL of catalyst toluene solution (containing 1 μmol of compound A1). Once the temperature stabilizes at 100 °C, add 2 mL of triphenylcarbazone (pentafluorophenyl)borate toluene solution (containing 10 μmol of triphenylcarbazone (pentafluorophenyl)borate). Rapidly pressurize the ethylene to 10 atm, set the temperature to 100 °C, and start timing. During the reaction, replenish ethylene as needed to maintain a total pressure of 10 atm in the polymerization flask. After 10 minutes, shut off the ethylene supply, pour the reaction mixture into a beaker, add 300 mL of ethanol and 5 mL of concentrated hydrochloric acid, stir for at least 6 hours, filter, and vacuum dry at 60 °C for 24 hours to obtain the polymer. The polymerization activity, weight-average molecular weight and molecular weight distribution of the polymer as determined by gel permeation chromatography are shown in Table 1.

[0166] Example 12

[0167] This example illustrates the copolymerization of ethylene and norbornene.

[0168] The polymerization was carried out according to the method of Example 11, except that the amount of the monometallic compound used was 2 micromoles, and polymerization was obtained in the same manner. The polymerization activity, the weight-average molecular weight and molecular weight distribution of the polymer as determined by gel permeation chromatography are shown in Table 1.

[0169] Example 13

[0170] This example illustrates the copolymerization of ethylene and norbornene.

[0171] The polymerization was carried out according to the method of Example 11, except that the monometallocene compound was A2, and polymerization was obtained in the same manner. The polymerization activity, the weight-average molecular weight and molecular weight distribution of the polymer as determined by gel permeation chromatography are shown in Table 1.

[0172] Example 14

[0173] This example illustrates the copolymerization of ethylene and norbornene.

[0174] The polymerization was carried out according to the method of Example 11, except that the monometallocene compound was A3, and polymerization was obtained in the same manner. The polymerization activity, the weight-average molecular weight and molecular weight distribution of the polymer as determined by gel permeation chromatography are shown in Table 1.

[0175] Comparative Example 1

[0176] The method of Example 8 was followed, except that the same molar amount of zirconium dichloroethylene was used instead of Al, and the polymer was obtained in the same manner. The polymerization activity, the weight-average molecular weight and molecular weight distribution of the polymer as determined by gel permeation chromatography are shown in Table 1.

[0177] Comparative Example 2

[0178] The method of Example 11 was followed, except that the same molar amount of zirconium dichloroethylene was used instead of A1, and the polymer was obtained in the same manner. The polymerization activity, the weight-average molecular weight and molecular weight distribution of the polymer as determined by gel permeation chromatography are shown in Table 1.

[0179] Table 1

[0180] Monometallic compounds Comonomer Mw(g / mol) PDI Polymerization activity Example 1 A1 norbornene <![CDATA[2.87×10 4 ]]> 3.53 9600 Example 2 A1 norbornene <![CDATA[3.91×10 4 ]]> 5.23 7080 Example 3 A1 norbornene <![CDATA[3.62×10 4 ]]> 5.50 4380 Example 4 A1 norbornene <![CDATA[5.23×10 4 ]]> 5.78 21960 Example 5 A1 norbornene <![CDATA[7.90×10 4 ]]> 4.88 30000 Example 6 A1 norbornene <![CDATA[10.0×10 4 ]]> 3.38 33360 Example 7 A1 norbornene <![CDATA[23.7×10 4 ]]> 10.20 3240 Example 8 A1 norbornene <![CDATA[12.1×10 4 ]]> 4.32 44100 Example 9 A1 Tetracyclo[6.2.1.13,6.02,7]dodecyl-4-ene <![CDATA[10.9×10 4 ]]> 3.82 35600 Example 10 A1 Cyclooctene <![CDATA[9.60×10 4 ]]> 4.13 22730 Example 11 A1 norbornene <![CDATA[11.5×10 4 ]]> 3.61 40500 Example 12 A1 norbornene <![CDATA[7.40×10 4 ]]> 4.69 29660 Example 13 A2 norbornene <![CDATA[12.0×10 4 ]]> 4.22 42730 Example 14 A3 norbornene <![CDATA[11.8×10 4 ]]> 4.58 41690 Comparative Example 1 Zirconium dichlorocerocene norbornene <![CDATA[3.91×10 4 ]]> 2.56 40200 Comparative Example 2 Zirconium dichlorocerocene norbornene <![CDATA[3.86×10 4 ]]> 2.84 35000

[0181] Note: The unit of polymerization activity is kg polymer / molar catalyst / hour.

[0182] By comparing Examples 8 and 13-14 with Comparative Example 1, it can be seen that the polymer obtained by the method of the present invention has a significantly increased molecular weight and high polymerization activity.

[0183] By comparing Example 11 with Comparative Example 2, it can be seen that the polymer obtained by the method of the present invention has a significantly increased molecular weight and high polymerization activity.

[0184] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto.

[0185] Within the scope of the technical concept of this invention, various simple modifications can be made to the technical solution of this invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be regarded as the content disclosed in this invention and are all within the protection scope of this invention.

Claims

1. A method for preparing an ethylene-cyclic olefin copolymer, characterized in that, The method includes: using a catalyst composition to copolymerize ethylene with cycloolefins. The catalyst composition comprises the following components: a) Monocerometallic compounds with the structure shown in formula (1), In formula (1), Cp' is a cyclopentadienyl or unsubstituted cyclopentadienyl group with 1-20 carbon atoms, a cyclopentadienyl or unsubstituted indenyl group with 1-20 carbon atoms, or a fluorenyl or unsubstituted fluorenyl group with 1-20 carbon atoms. R 1 R 2 R 3 R 4 R 5 and R 6 Hydrocarbon groups, which are each independently composed of hydrogen atoms, halogen atoms, or 1-20 carbon atoms; X is a halogen atom; b) Co-catalyst components.

2. The method according to claim 1, wherein, In formula (1), Cp' is a cyclopentadienyl or unsubstituted cyclopentadienyl with 1-16 carbon atoms, a cyclopentadienyl or unsubstituted indenyl with 1-16 carbon atoms, or a fluorenyl or unsubstituted fluorenyl with 1-16 carbon atoms, either monosubstituted or polysubstituted. R 1 R 2 R 3 R 4 R 5 and R 6 Hydrocarbon groups, which are each independently composed of hydrogen atoms, halogen atoms, or 1-16 carbon atoms; X is F, Cl, Br, or I; Preferably, in formula (1), Cp' is an alkyl group with 1-10 carbon atoms and / or an aryl mono- or poly-substituted cyclopentadienyl group or an unsubstituted cyclopentadienyl group, an alkyl group with 1-10 carbon atoms and / or an aryl mono- or poly-substituted indenyl group or an unsubstituted indenyl group, or an alkyl group with 1-10 carbon atoms and / or an aryl mono- or poly-substituted fluorenyl group or an unsubstituted fluorenyl group; R 1 R 2 R 3 R 4 R 5 and R 6 Alkyl groups, each consisting independently of a hydrogen atom, a halogen atom, or 1-10 carbon atoms; X is F, Cl, or Br; Preferably, in formula (1), Cp' is a mono- or poly-substituted cyclopentadienyl or unsubstituted cyclopentadienyl of 1-6 carbon atoms, a mono- or poly-substituted indole or unsubstituted indole of 1-6 carbon atoms, or a mono- or poly-substituted fluorenyl or unsubstituted fluorenyl of 1-6 carbon atoms. R 1 R 2 R 3 R 4 R 5 and R 6 Alkyl groups consisting of hydrogen atoms, halogen atoms, or 1-6 carbon atoms, respectively; X is either F or Cl; Preferably, in formula (1), Cp' is a mono- or poly-substituted cyclopentadienyl or unsubstituted cyclopentadienyl of 1-3 carbon atoms, a mono- or poly-substituted indole or unsubstituted indole of 1-3 carbon atoms, or a mono- or poly-substituted fluorenyl or unsubstituted fluorenyl of 1-3 carbon atoms. R 1 R 2 R 3 R 4 R 5 and R 6 Alkyl groups, each consisting independently of a hydrogen atom, a halogen atom, or 1-3 carbon atoms; X is Cl.

3. The method according to claim 1, wherein, The monocerometallic compound is selected from one or more of the following compounds. In formula (1), Cp' is cyclopentadienyl, R 1 R 2 R 3 R 4 R 5 and R 6 X is a hydrogen atom, and Cl is a hydrogen atom. In equation (1), Cp' is indenyl, R 1 R 2 R 3 R 4 R 5 and R 6 X is a hydrogen atom, and Cl is a hydrogen atom. In equation (1), Cp' is a fluorene group, R 1 R 2 R 3 R 4 R 5 and R 6 X is a hydrogen atom, and Cl is a hydrogen atom. In formula (1), Cp' is cyclopentadienyl, R 1 R 2 R 3 R 4 and R 5 For hydrogen atoms, and R 6 X is a methyl group, and Cl is a methyl group. In equation (1), Cp' is indenyl, R 1 R 2 R 3 R 4 and R 5 For hydrogen atoms, R 6 X is a methyl group, and Cl is a methyl group. In equation (1), Cp' is a fluorene group, R 1 R 2 R 3 R 4 and R 5 For hydrogen atoms, R 6 X is a methyl group, and Cl is a methyl group. In formula (1), Cp' is pentamethylcyclopentadienyl, R 1 R 2 R 3 R 4 and R 5 For hydrogen atoms, R 6 X is a methyl group, and Cl is a methyl group. In formula (1), Cp' is pentamethylcyclopentadienyl, R 1 R 2 R 3 R 4 R 5 and R 6 X is a hydrogen atom, and Cl is a chlorine atom.

4. The method according to any one of claims 1-3, wherein, The cocatalyst component includes one or more of alkylaluminoxanes, organoboron compounds, and organoaluminum compounds; Preferably, the cocatalyst component is an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound.

5. The method according to claim 4, wherein, The alkylaluminoxane is a compound selected from the structures shown in formula (2) and / or formula (3). In formulas (2) and (3), R is selected from alkyl groups having 1-15 carbon atoms, and n is an integer from 4 to 30; Preferably, R is selected from alkyl groups having 1-5 carbon atoms, and n represents an integer from 10 to 30; Preferably, the alkylaluminoxane is methylaluminoxane.

6. The method according to claim 4, wherein, b) The organoboron compound is [B(C6F5)4]. - Z + Z + Having the structure shown in equation (4) or equation (5), 7. The method according to claim 4, wherein, The organoaluminum compound is a compound with the general formula AlX1X2X3, where X1, X2 and X3 are respectively a halogen atom, an alkyl group with 1-8 carbon atoms, an alkoxy group with 1-8 carbon atoms, and an aryloxy group with 6-12 carbon atoms. X1, X2 and X3 can be the same or different, and at least one of them is an alkyl group with 1-8 carbon atoms. Preferably, the organoaluminum compound is triisobutylaluminum.

8. The method according to any one of claims 1-3, wherein, The cocatalyst is an alkylaluminoxane, and the molar ratio of the monometallocene compound to the alkylaluminoxane (calculated as aluminum) is 1:(100-50000), preferably 1:(1000-30000).

9. The method according to any one of claims 1-3, wherein, The cocatalyst is a combination of organoboron compounds and organoaluminum compounds, wherein the molar ratio of the monometallic compound to the organoboron compound is 1:(1-20), preferably 1:(1-10); and the molar ratio of the monometallic compound to the organoaluminum compound is 1:(10-5000), preferably 1:(50-1000).

10. The method according to any one of claims 1-3, wherein, The concentration of cyclic olefins in the polymerization reaction system is 0.001-8 mol / L, preferably 0.01-4 mol / L.

11. The method according to any one of claims 1-3, wherein, The concentration of the metallocene compound in the polymerization reaction system is 1 × 10⁻⁶. -8 mol / L ~ 1×10 -2 mol / L, preferably 1×10 -7 mol / L ~ 5×10 -3 Moles per liter.

12. The method according to any one of claims 1-3, wherein, The copolymerization reaction temperature is -50 to 200°C, and the copolymerization reaction time is 1 to 300 minutes. Preferably, the copolymerization temperature is -20 to 150°C, and the copolymerization time is 5 to 60 minutes.

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

14. The method according to any one of claims 1-3, wherein, The cyclic olefin is a cyclic olefin containing 5-20 carbon atoms; Preferably, the cycloolefin is one or more selected from cyclopentene, cycloheptene, cyclooctene, norbornene, and tetracyclo[6.2.1.13,6.02,7]dodecyl-4-ene; Preferably, the cyclic olefin is norbornene.

15. The method according to any one of claims 1-3, wherein, The polymerization reaction is carried out in the presence of an organic solvent, which is one or more of toluene, cyclohexane, and hexane.

16. The ethylene-cycloolefin copolymer prepared by the method of any one of claims 1-15.

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