Catalyst composition, olefin polymerization process and use

Abstract

The present application relates to the field of olefin polymerization, and discloses a catalyst composition, an olefin polymerization method using the catalyst composition, and application of the catalyst composition in olefin polymerization. The catalyst composition comprises: a) a metallocene compound, b) a steric alcohol, and c) a cocatalyst component. By using the catalyst composition, the molecular weight of the polymer can be increased, thereby improving product quality and expanding product grades.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of olefin polymerization, in particular, to a catalyst composition, an olefin polymerization method using the catalyst composition and the application of the catalyst composition in olefin polymerization. BACKGROUND

[0002] Metallocene catalysts for olefin polymerization have been a research hotspot in the fields of organometallic chemistry, catalysis, polymer chemistry and materials science in recent decades. Metallocene catalysts have strong copolymerization ability, which is reflected in two aspects: on the one hand, under the same polymerization conditions, the copolymer obtained by metallocene catalysts contains a higher content of comonomers than other catalysts, which is the high efficiency of copolymerization; on the other hand, some monomers that cannot be polymerized by other catalysts can also be used as comonomers for metallocene catalyst systems, which is the broad spectrum of copolymerization (Chemistry Select, 2020, 5, 7581-7585). Due to the high efficiency and broad spectrum of copolymerization of metallocene catalysts, many new copolymers can be obtained, which have new compositions and structures compared with copolymers obtained by other catalysts, and thus may have new properties, thereby realizing the application of polyolefin materials in new fields.

[0003] The production of polymers with high comonomer content requires high comonomer feed concentration, such as polyolefin elastomer (POE) and cyclic olefin copolymer (COC), which usually have a comonomer content of more than 30%, and some even up to 80%. This requires a very high concentration of comonomer in the polymerization reaction system, which greatly increases the probability of polymerization growth chain transfer to comonomer, which is extremely unfavorable for the production of high molecular weight polymers.

[0004] Metallocene catalysts need to be activated in the presence of a cocatalyst to effectively polymerize. The most effective and widely used cocatalyst is a combination of methylaluminoxane and organoboron compounds and organoaluminum compounds. In olefin polymerization with coordination polymerization mechanism, organoaluminum compounds are a highly efficient chain transfer agent. This means that during the olefin polymerization process, there will be a transfer of polymerization active chains to aluminum atoms, thereby reducing the molecular weight of the polymer.

[0005] Therefore, it is a key issue for the production of high-end polyolefin materials to modify the existing catalyst system to inhibit the transfer of polymerization growth chains to comonomers and cocatalysts, and thus obtain high molecular weight polyolefin products. SUMMARY

[0006] The present application aims to overcome the problem of the prior art that the molecular weight of the polymer is reduced, and to provide a catalyst composition, an olefin polymerization method using the catalyst composition, and the use of the catalyst composition in olefin polymerization. By using the catalyst composition, the molecular weight of the polymer can be increased, thereby improving the product quality and expanding the product grade.

[0007] The reason why the molecular weight of the polymer can be increased by using the catalyst composition of the present application is not very clear, but it is speculated that, in the metallocene-methylaluminoxane catalyst system or the like for olefin polymerization of the present application, a specific alcohol having a large steric hindrance is added, which reacts with the free alkylaluminum or the organic aluminum compound in the combination of the organic boron compound and the organic aluminum compound in the methylaluminoxane or its solution to form a new aluminoxane or alkylaluminum containing a large steric hindrance group, causing a mass transfer resistance to the chain transfer reaction to the aluminum atom, thereby inhibiting the chain transfer reaction and achieving the purpose of increasing the molecular weight of the polymer. At the same time, the specific alcohol having a large steric hindrance of the present application can also act on the catalyst to form a large steric hindrance near the active center, thereby inhibiting the transfer of the polymerization growth chain to the aluminum atom or the comonomer.

[0008] Thus, the first aspect of the present application provides a catalyst composition, wherein the catalyst composition comprises the following components:

[0009] a) a metallocene compound having the structure represented by Formula (I) and / or Formula (II),

[0010]

[0011] In Formula (I) and Formula (II),

[0012] Cp 1 and Cp 2 are each independently a hydrocarbyl mono- or poly-substituted cyclopentadienyl group or an unsubstituted cyclopentadienyl group, a hydrocarbyl mono- or poly-substituted indenyl group or an unsubstituted indenyl group, or a hydrocarbyl mono- or poly-substituted fluorenyl group or an unsubstituted fluorenyl group having 1-20 carbon atoms;

[0013] M is titanium, zirconium or hafnium;

[0014] X 1 and X 2 are each independently a halogen atom, an alkoxy group, an aryloxy group or a hydrocarbyl group;

[0015] In Formula (II), Q is an atom or a group connecting Cp 1 and Cp 2 ;

[0016] b) an alcohol having the structure represented by Formula (III) and / or Formula (IV),

[0017]

[0018] c) a cocatalyst component.

[0019] Preferably, in formula (I) and formula (II), Cp 1 and Cp 2 are each independently a hydrocarbyl mono- or poly-substituted cyclopentadienyl group or an unsubstituted cyclopentadienyl group, a hydrocarbyl mono- or poly-substituted indenyl group or an unsubstituted indenyl group, a hydrocarbyl mono- or poly-substituted fluorenyl group or an unsubstituted fluorenyl group having 1 to 16 carbon atoms; M is titanium or zirconium; X 1 and X 2 are each independently a halogen atom.

[0020] Preferably, in formula (II), Q is -CH2CH2-, Cp 1 and Cp 2 are each an indenyl group, M is zirconium, X 1 and X 2 are each a chlorine atom.

[0021] Preferably, in formula (II), Q is -SiR 1 R 2 , Cp 1 and Cp 2 are each an indenyl group, M is zirconium, X 1 and X 2 are each a chlorine atom, R 1 and R 2 are each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.

[0022] Preferably, in formula (II), Q is -SiR 3 R 4 , Cp 1 and Cp 2 are each a 2-methyl-4-phenyl-indenyl group, M is zirconium, X 1 and X 2 are each a chlorine atom, R 3 and R 4 are each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.

[0023] Preferably, in formula (II), Q is -CR 5 R 6 , Cp 1 is a cyclopentadienyl group, Cp 2 is a fluorenyl group, M is zirconium, X 1 and X 2 are each a chlorine atom, R 5 and R 6 are each a methyl group or a phenyl group.

[0024] Preferably, in formula (II), Q is -CR 7 R 8 -, Cp 1 is cyclopentadienyl, Cp 2 is 2,7-di-tert-butyl-fluorenyl, M is zirconium, X 1 and X 2 are chlorine atoms, R 7 and R 8 are methyl or phenyl groups.

[0025] Preferably, the metallocene compound is selected from one or more of dicyclopentadienyl zirconium dichloride, di(n-butylcyclopentadienyl)zirconium dichloride, di(l-methyl-3-n-butylcyclopentadienyl)zirconium dichloride, diindenyl zirconium dichloride, diphenyl methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diphenyl methylene(cyclopentadienyl)(2,7-di-tert-butyl-9-fluorenyl)zirconium dichloride, isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride, (4,4'-tert-butyl-diphenyl methylene)- cyclopentadienyl-(l-indenyl)-titanium dichloride, (4,4'-tert-butyl-diphenyl methylene)- cyclopentadienyl-(l-indenyl)-zirconium dichloride, (4,4'-tert-butyl-diphenyl methylene)- cyclopentadienyl-(l-indenyl)-hafnium dichloride, (4,4'-methoxy-diphenyl methylene)- cyclopentadienyl-(l-indenyl)-zirconium dichloride, (4,4'-methoxy-diphenyl methylene)- cyclopentadienyl-(l-indenyl)-hafnium dichloride, (4,4'-methyl-diphenyl methylene)- cyclopentadienyl-(l-indenyl)-zirconium dichloride, (4-methyl-4'-tert-butyl-diphenylMore preferably, the metallocene compound is one or more of dicyclopentadienyl zirconium dichloride, di(n-butylcyclopentadienyl)zirconium dichloride, di(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride, diindenyl zirconium dichloride, diphenyl methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diphenyl methylene(cyclopentadienyl)(2,7-di-tert-butyl-9-fluorenyl)zirconium dichloride, isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride, rac-ethylenediindenyl zirconium dichloride, rac-dimethylsilyl diindenyl zirconium dichloride, and rac-dimethylsilyl di(2-methyl-4-indenyl)zirconium dichloride.

[0026] Preferably, the cocatalyst component comprises one or more of an alkylaluminoxane, an organoboron compound, and an organoaluminum compound; more preferably, the cocatalyst component is an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound.

[0027] Preferably, the alkylaluminoxane is a compound selected from the structures represented by Formula (V) and / or Formula (VI),

[0028]

[0029] In Formula (V) and Formula (VI), R is selected from an alkyl group having 1-15 carbon atoms, and n represents an integer of 4-30; more preferably, R is selected from an alkyl group having 1-5 carbon atoms, and n represents an integer of 10-30.

[0030] Preferably, the alkylaluminoxane is methylaluminoxane.

[0031] Preferably, the organoboron compound is one or more of triphenylmethyl tetra(pentafluorophenyl)borate, N,N-dimethylanilinium tetra(pentafluorophenyl)borate, and tris(pentafluorophenyl)boron.

[0032] Preferably, the organoaluminum compound is a compound represented by the general formula AlX1X2X3, wherein X1, X2, and X3 are each a halogen atom, an alkyl group having 1-8 carbon atoms, an alkoxy group having 1-8 carbon atoms, or an aryloxy group having 6-12 carbon atoms, X1, X2, and X3 can be the same or different, and at least one of X1, X2, and X3 is an alkyl group having 1-8 carbon atoms.

[0033] Preferably, the organoaluminum compound is triisobutylaluminum.

[0034] Preferably, the cocatalyst is an alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane on an aluminum basis is 1:(50-20000), preferably 1:(200-10000), and more preferably 1:(500-3000).

[0035] Preferably, the co-catalyst is a combination of an organoboron compound and an organoaluminum compound, the molar ratio of the metallocene compound to the organoboron compound is 1:(1-5), preferably 1:(1-2), and the molar ratio of the metallocene compound to the organoaluminum compound is 1:(10-1000), preferably 1:(10-200).

[0036] Preferably, the molar ratio of the metallocene compound to the alcohol is 1:(1-1000), preferably 1:(10-500).

[0037] According to a second aspect of the present application, there is provided a method for polymerizing an olefin, comprising contacting the olefin with the catalyst composition according to the first aspect of the present application.

[0038] Preferably, the concentration of the metallocene compound in the polymerization system is 1 x 10 -9 mole / liter to 1 x 10 -3 mole / liter, preferably 1 x 10 -8 mole / liter to 1 x 10 -4 mole / liter.

[0039] Preferably, the temperature of the polymerization reaction is 0-200°C, and the time of the polymerization reaction is 1-300 minutes; more preferably, the temperature of the polymerization reaction is 50-160°C, and the time of the polymerization reaction is 5-60 minutes.

[0040] Preferably, the partial pressure of the olefin is 0.1-10 MPa, preferably 0.1-4.0 MPa.

[0041] Preferably, the olefin is ethylene, or is ethylene and a second olefin as a comonomer.

[0042] Preferably, the second olefin is one or more of propylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene, norbornene, cyclopentene, cycloheptene, 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, 7-octen-1-ol, 8-nonene-1-ol, 9-decene-1-ol and 10-undecene-1-ol.

[0043] According to a third aspect of the present application, there is provided the use of the catalyst composition according to the first aspect of the present application in the polymerization of an olefin.

[0044] According to the present application, by using a catalyst composition comprising an alcohol with a large steric hindrance, the molecular weight of the obtained polymer is significantly higher than that of a polymer obtained by using a catalyst composition without the alcohol with a large steric hindrance, which can broaden the regulation range of polyolefin products, and improve the quality and types of polyolefin products. DETAILED DESCRIPTION

[0045] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not critical to the invention. Any numeric range recited is intended to include all values between the recited upper and lower values. In this sense, the phrase "between X and Y" is intended to encompass all values between and including X and Y. In the numeric range recited, the endpoints are included in the range, unless indicated otherwise. Numeric ranges include endpoints.

[0046] The first aspect of the present invention provides a catalyst composition comprising the following components:

[0047] a) a metallocene compound represented by the following formula (I) and / or formula (II),

[0048]

[0049] In formula (I) and formula (II),

[0050] Cp 1 and Cp 2 are each independently a hydrocarbyl mono- or poly-substituted or unsubstituted cyclopentadienyl group having 1 to 20 carbon atoms, a hydrocarbyl mono- or poly-substituted or unsubstituted indenyl group having 1 to 20 carbon atoms, or a hydrocarbyl mono- or poly-substituted or unsubstituted fluorenyl group having 1 to 20 carbon atoms;

[0051] M is titanium, zirconium or hafnium;

[0052] X 1 and X 2 are each independently a halogen atom, an alkoxy group, an aryloxy group or a hydrocarbyl group;

[0053] In formula (II), Q is an atom or a group linking Cp 1 and Cp 2 ;

[0054] b) an alcohol represented by the following formula (III) and / or formula (IV),

[0055]

[0056] c) a cocatalyst component.

[0057] According to the catalyst component of the present invention, preferably, in formula (I) and formula (II), Cp 1 and Cp 2 are each independently a hydrocarbyl mono- or poly-substituted or unsubstituted cyclopentadienyl group having 1 to 16 carbon atoms, a hydrocarbyl mono- or poly-substituted or unsubstituted indenyl group having 1 to 16 carbon atoms, or a hydrocarbyl mono- or poly-substituted or unsubstituted fluorenyl group having 1 to 16 carbon atoms; M is titanium or zirconium; X 1 and X2 Each is an independent halogen atom.

[0058] The hydrocarbon group is more preferably an alkyl group with 1-10 carbon atoms or an aryl group with 6-12 carbon atoms, and even more preferably an alkyl group with 1-6 carbon atoms.

[0059] 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.

[0060] Examples of aryl groups with 6-12 carbon atoms include phenyl, benzyl, phenethyl, diphenylmethylene, and diphenylethylene.

[0061] In the compounds represented by formulas (I) and (II) of this invention, X 1 and X 2 Each can be independently a halogen atom, alkoxy group, aryloxy group, or hydrocarbon group.

[0062] 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.

[0063] The alkoxy group can be, for example, an alkoxy group having 1-8 carbon atoms, more preferably an alkoxy group having 1-6 carbon atoms, and even more preferably an alkoxy group having 1-3 carbon atoms.

[0064] Examples of alkoxy groups with 1-8 carbon atoms include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, sec-butoxy, isobutoxy, pentoxy, hexoxy, heptoxy, octoxy, etc.

[0065] As an aryloxy group, it can be an aryloxy group with 6-12 carbon atoms, specifically including phenoxy, methylphenoxy, ethylphenoxy, naphthoxy, etc.

[0066] As the above hydrocarbon group, a hydrocarbon group (preferably an alkyl group) having 1 to 20 carbon atoms is preferred, a hydrocarbon group (preferably an alkyl group) having 1 to 12 carbon atoms is more preferred, and a hydrocarbon group (preferably an alkyl group) having 1 to 6 carbon atoms is further preferred. As specific examples, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, sec-butyl group, isobutyl group, pentyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, neopentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, hexyl group, phenyl group, benzyl group, phenethyl group, and the like can be given.

[0067] In another preferred embodiment of the present application, in the formula (II), Q is -CH2CH2-, Cp n - (n is an integer of 2 to 20), Cp 1 is an indenyl group, M is zirconium, X 2 and X 1 are chlorine atoms. 2

[0068] In another preferred embodiment of the present application, in the formula (II), Q is -CH2CH2-, Cp 1 - (n is an integer of 2 to 20), Cp 2 is an indenyl group, M is zirconium, X 1 and X 2 are chlorine atoms.

[0069] In another preferred embodiment of the present application, in the formula (II), Q is -SiR 1 R 2 -, Cp 1 and Cp 2 is an indenyl group, M is zirconium, X 1 and X 2 are chlorine atoms, R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0070] In another preferred embodiment of the present application, in the formula (II), Q is -SiR 3 R 4 -, Cp 1 and Cp 2 is an indenyl group, M is zirconium, X 1 and X 2 are chlorine atoms, R 3 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0071] In another preferred embodiment of the present application, in the formula (II), Q is -CR 5 R 6 -, Cp 1 ​is cyclopentadienyl, Cp 2 is fluorenyl, M is zirconium, and X 1 and X 2 is a chlorine atom, R 5 and R 6 is a methyl group or a phenyl group.

[0072] In another preferred embodiment of the present application, in formula (II), Q is -CR 7 R 8 is cyclopentadienyl, Cp 1 is cyclopentadienyl, Cp 2 is 2,7-di-tert-butyl-fluorenyl, M is zirconium, and X 1 and X 2 is a chlorine atom, R 7 and R 8 is a methyl group or a phenyl group.

[0073] As the above hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is further preferred.

[0074] As specific examples of the metallocene compound, for example, one or more of dicyclopentadienylzirconium dichloride, di(n-butylcyclopentadienyl)zirconium dichloride, di(l-methyl-3-n-butylcyclopentadienyl)zirconium dichloride, diindenylzirconium dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconium dichloride, isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride, (4,4'-t-butyl-diphenylmethylene)-cyclopentadienyl-(l-indenyl)-titanium dichloride, (4,4'-t-butyl-diphenylmethylene)-cyclopentadienyl-(l-indenyl)-zirconium dichloride, (4,4'-t-butyl-diphenylmethylene)-cyclopentadienyl-(l-indenyl)-hafnium dichloride, (4,4'-methoxy-diphenylmethylene)-cyclopentadienyl-(l-indenyl)-zirconium dichloride, (4,4'-methoxy-diphenylmethylene)-cyclopentadienyl-(l-indenyl)-hafnium dichloride, (4,4'-methyl-diphenylmethylene)-cyclopentadienyl-(l-indenyl)-zirconium dichloride, (4-methyl-4'-t-butyl-diphenylmethylene)-cyclopentadienyl-(l-indenyl)-zirconium dichloride, (3,3'-trifluoromethyl-diphenylmethylene)-cyclopentadienyl-(l-indenyl)-titanium dichloride, (3,3'-trifluoromethyl-diphenylmethylene)-cyclopentadienyl-(l-indenyl)-zirconium dichloride, (3,3'-trifluoromethyl-diphenylmethylene)-cyclopentadienyl-(l-indenyl)-hafnium dichloride, (4,4'-fluoro-diphenylmethylene)-cyclopentadienyl-(l-indenyl)-titanium dichloride, (4,4'-fluoro-diphenylmethylene)-cyclopentadienyl-(l-indenyl)-zirconium dichloride, (4,4'-fluoro-diphenylmethylene)-cyclopentadienyl-(l-indenyl)-hafnium dichloride, (4,4'-chloro-diphenylmethylene)-cyclopentadienyl-(l-indenyl)-titanium dichloride, (4,4'-chloro-diphenylmethylene)-cyclopentadienyl-(l-indenyl)-zirconium dichloride, or (4,4'-chloro-diphenylmethylene)-cyclopentadienyl-(l-indenyl)-hafnium dichloride, rac-vinylindenylzirconium dichloride, rac-dimethylsilylindenylzirconium dichloride, rac-dimethylsilyl di(2-methyl-indenyl)zirconium dichloride, and rac-dimethylsilyl di(2-methyl-4-phenylindenyl)zirconium dichloride can be mentioned.More preferably, they are one or more of dicyclopentadienyl zirconium dichloride, di(n-butylcyclopentadienyl) zirconium dichloride, di(1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride, diindyl zirconium dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl) zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, isopropyl(cyclopentadienyl)(fluorenyl) zirconium dichloride, racemic-vinyldiindyl zirconium dichloride, racemic-dimethylsilyldiindyl zirconium dichloride, and racemic-dimethylsilyldi(2-methyl-4-indyl) zirconium dichloride.

[0075] According to the catalyst composition of the present invention, the co-catalyst component can be any of the various co-catalyst components commonly used in the art. Preferably, the co-catalyst component includes one or more of alkylaluminoxanes, organoboron compounds, and organoaluminum compounds; more preferably, the co-catalyst component is an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound.

[0076] The alkylaluminoxanes described above are preferably compounds selected from those shown in formula (IV) and / or formula (V).

[0077]

[0078] In formulas (IV) and (V), R is selected from alkyl groups having 1-15 carbon atoms, and n represents an integer from 4 to 30; more preferably, R is selected from alkyl groups having 1-5 carbon atoms, and n represents an integer from 10 to 30.

[0079] 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.

[0080] 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.

[0081] Specific examples of the alkylaluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, etc., with methylaluminoxane being preferred.

[0082] The organic boron compound in the catalyst composition according to the present application can be various organic boron compounds used as a cocatalyst in the art, and one or more of, for example, triphenylmethyl tetra(pentafluorophenyl) borate, N,N-dimethylanilinium tetra(pentafluorophenyl) borate, and tris(pentafluorophenyl) boron can be mentioned.

[0083] The organic aluminum compound in the catalyst composition according to the present application can be various organic aluminum compounds used as a cocatalyst in the art. Preferably, the organic aluminum compound is a compound represented by the general formula AlX1X2X3, wherein X1, X2, and X3 are each a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms, and X1, X2, and X3 can be the same or different and at least one of them is an alkyl group having 1 to 8 carbon atoms.

[0084] As the alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, isobutyl, pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl, heptyl, octyl, and the like can be mentioned.

[0085] As the alkoxy group having 1 to 8 carbon atoms, for example, various alkoxy groups having the above-described specific examples of "alkyl group having 1 to 8 carbon atoms" can be mentioned,

[0086] As the halogen atom, for example, fluorine, chlorine, bromine, or iodine can be mentioned, and preferably, fluorine, chlorine, or bromine, more preferably, chlorine or bromine, and particularly preferably, chlorine can be mentioned.

[0087] As specific examples of the organic aluminum compound in the present application, for example, one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tri-n-pentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, and triamylaluminum can be mentioned. Among them, triisobutylaluminum is preferably used.

[0088] The catalyst composition according to the present application preferably uses independently either of formula (III) and formula (IV), or both of them.

[0089] In the catalyst composition according to the present application, when the cocatalyst is an alkylaluminoxane, the cocatalyst is an alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane in terms of aluminum is 1 : (50 to 20,000), more preferably 1 : (200 to 10,000), and more preferably 1 : (500 to 3,000).

[0090] When the cocatalyst is a combination of an organoboron compound and an organoaluminum compound, the mole ratio of the metallocene compound to the organoboron compound is 1:(1-5), preferably 1:(1-2), and the mole ratio of the metallocene compound to the organoaluminum compound is 1:(10-1000), preferably 1:(10-200).

[0091] According to the catalyst composition of the present application, preferably, the mole ratio of the metallocene compound to the alcohol is 1:(1-1000), more preferably 1:(10-500), further preferably 1:(20-200), further preferably 1:(50-150), and more further preferably 1:(100-150).

[0092] According to the second aspect of the present application, there is provided a method for polymerizing an olefin, which comprises contacting an olefin with the catalyst composition according to the first aspect of the present application.

[0093] According to the method of the present application, the metallocene compound in the polymerization system can be used in an amount generally used in the art for synthesizing polyolefins. Preferably, the concentration of the metallocene compound in the polymerization system is 1 x 10 -9 mole / liter to 1 x 10 -3 mole / liter, more preferably 1 x 10 -8 mole / liter to 1 x 10 -4 mole / liter.

[0094] According to the method of the present application, preferably, the polymerization is carried out in an inert organic solvent. As the inert organic solvent, one or a mixture of several of linear aliphatic hydrocarbons, branched aliphatic hydrocarbons, substituted or unsubstituted cyclic aliphatic hydrocarbons, substituted or unsubstituted aromatic hydrocarbons can be used. As specific examples of the inert organic solvent, hexane, heptane, cyclohexane, cyclooctane, toluene, xylene can be mentioned. In addition, the amount of the organic solvent can be determined according to the reactivity, ensuring good dissolution of the polymer in the system, at least not affecting the dispersion.

[0095] According to the method of the present application, the polymerization conditions can be the conditions generally used in the art for synthesizing polyolefins. Preferably, the temperature of the polymerization is 0-200°C, and the time of the polymerization is 1-300 minutes; more preferably, the temperature of the polymerization is 50-160°C, and the time of the polymerization is 5-60 minutes.

[0096] According to the method of the present application, preferably, the partial pressure of the olefin is 0.1-10 MPa, preferably 0.1-4.0 MPa.

[0097] According to the method of the present application, preferably, the olefin is ethylene, or ethylene and a second olefin as a comonomer;

[0098] Preferably, the second olefin as a comonomer is one or more of propylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene, norbornene, cyclopentene, cycloheptene, 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, 7-octen-1-ol, 8-nonene-1-ol, 9-decene-1-ol and 10-undecene-1-ol.

[0099] In a preferred embodiment of the present application, when the cocatalyst component is alkylaluminoxane, the preparation method comprises: vacuumizing the polymerization device which has been dried sufficiently, flushing with nitrogen for several times, then vacuumizing again, filling with ethylene, adding the reaction solvent, alcohol and alkylaluminoxane in sequence, then heating to the polymerization temperature, then adding the metallocene compound to carry out the polymerization reaction, during the polymerization, continuously feeding ethylene to make up the ethylene consumed by the polymerization, after the polymerization is completed, closing the ethylene, adding acidified alcohol into the reaction solution, stirring and then filtering to obtain the polymer.

[0100] In another preferred embodiment of the present application, when the cocatalyst component is the combination of organoboron compound and organoaluminum compound, the preparation method comprises: vacuumizing the polymerization device which has been dried sufficiently, flushing with nitrogen for several times, then vacuumizing again, filling with ethylene, adding the reaction solvent, 1-octene, alcohol and organoaluminum compound in sequence, then heating to the polymerization temperature, then adding the metallocene compound and organoboron compound in sequence to carry out the polymerization reaction, during the polymerization, continuously feeding ethylene to make up the ethylene consumed by the polymerization, after the polymerization is completed, closing the ethylene, adding acidified alcohol into the reaction solution, stirring and then filtering to obtain the polymer.

[0101] According to the third aspect of the present application, the catalyst composition of the first aspect of the present application is used in the polymerization of olefins.

[0102] The present application will be described in detail by the following examples, but the present application is not limited to the following examples.

[0103] The raw materials used in the following examples and comparative examples are, if not particularly limited, disclosed in the prior art, for example, can be directly purchased or prepared according to the preparation method disclosed in the prior art.

[0104] Polymer test method:

[0105] Test of weight average molecular weight and molecular weight distribution

[0106] The molecular weight and molecular weight distribution of the sample were determined by GPC using a PL-GPC 220 from Polymer Laboratories, UK, with three Plgel 10 μm MIXED-B columns in series. The solvent and mobile phase were 1,2,4-trichlorobenzene (containing 0.025 wt% of the antioxidant 2,6-di- butyl-p-cresol), the column temperature was 150 °C, the flow rate was 1.0 ml / min, the sample concentration was 1 mg / ml, and an IR5 infrared concentration detector was used, with a universal polystyrene calibration using narrow distribution polystyrene standards.

[0107] Abbreviations used for the alcohols in the examples:

[0108] Abbreviations Substance name Structural formula Alcohol 1 Triphenylmethanol Formula (III) Alcohol 2 2-Ethyl-2-adamantanol Formula (IV)

[0109] Comparative Example 1

[0110] A dry polymerization flask was evacuated and flushed with nitrogen three times. The flask was evacuated and charged with 1 atm of ethylene, 25 ml of toluene, 1 ml of 1-octene, and 3 ml of methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane). The temperature was raised to 70 °C and 1 ml of catalyst toluene solution (containing 5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added. Timing was started and during the course of the reaction, the pressure of ethylene in the polymerization flask decreased due to ethylene consumption. Ethylene was replenished to maintain a pressure of 1 atm. After 20 minutes, the ethylene was turned off and the reaction mixture was poured into a beaker and acidified ethanol was added. The mixture was stirred for more than 6 hours and the polymer was filtered. The polymerization data and characterization results are shown in Table 1.

[0111] Comparative Example 2

[0112] A dry polymerization flask was evacuated and flushed with nitrogen three times. The flask was evacuated and charged with 1 atm of ethylene, 25 ml of toluene, 1 ml of 1-octene, and 3 ml of methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane). The temperature was raised to 70 °C and 1 ml of catalyst toluene solution (containing 5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added. Timing was started and during the course of the reaction, the pressure of ethylene in the polymerization flask decreased due to ethylene consumption. Ethylene was replenished to maintain a pressure of 1 atm. After 20 minutes, the ethylene was turned off and the reaction mixture was poured into a beaker and acidified ethanol was added. The mixture was stirred for more than 6 hours and the polymer was filtered. The polymerization data and characterization results are shown in Table 1.

[0113] Comparative Example 3

[0114] A dry polymerization flask was purged with nitrogen three times. The flask was charged with 4.71 g of norbornene, purged with nitrogen three times, and then vacuumed. The flask was charged with 1 atm of ethylene, 26 mL of toluene, 3 mL of methylaluminoxane in toluene (containing 5.0 mmol of methylaluminoxane), and heated to 70°C. The reaction was started by adding 1 mL of catalyst in toluene (containing 5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride). The reaction was run for 20 minutes, and then the ethylene was turned off. The reaction was quenched by adding acidified ethanol. The polymer was isolated by stirring for 6 hours or more and then filtering. The polymerization data and characterization results are shown in Table 1.

[0115] Comparative Example 4

[0116] A dry polymerization flask was purged with nitrogen three times. The flask was charged with 4.71 g of norbornene, purged with nitrogen three times, and then vacuumed. The flask was charged with 1 atm of ethylene, 26 mL of toluene, 3 mL of methylaluminoxane in toluene (containing 5.0 mmol of methylaluminoxane), and heated to 70°C. The reaction was started by adding 1 mL of catalyst in toluene (containing 5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride). The reaction was run for 20 minutes, and then the ethylene was turned off. The reaction was quenched by adding acidified ethanol. The polymer was isolated by stirring for 6 hours or more and then filtering. The polymerization data and characterization results are shown in Table 1.

[0117] Comparative Example 5

[0118] A dry polymerization flask was purged with nitrogen three times. The flask was charged with 4.71 g of norbornene, purged with nitrogen three times, and then vacuumed. The flask was charged with 1 atm of ethylene, 26 mL of toluene, 3 mL of methylaluminoxane in toluene (containing 5.0 mmol of methylaluminoxane), and heated to 70°C. The reaction was started by adding 1 mL of catalyst in toluene (containing 5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride). The reaction was run for 20 minutes, and then the ethylene was turned off. The reaction was quenched by adding acidified ethanol. The polymer was isolated by stirring for 6 hours or more and then filtering. The polymerization data and characterization results are shown in Table 1.

[0119] Comparative Example 6

[0120] A dry polymerization bottle was oven dried, vacuumed, and flushed with nitrogen three times. The bottle was vacuumed and charged with 1 atm of ethylene, 25 mL of toluene, 1 mL of alcohol 1 in toluene (0.125 mmol), 3 mL of methylaluminoxane in toluene (5.0 mmol), heated to 70 °C, and 1 mL of catalyst in toluene (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added. The reaction was started by timing and the ethylene pressure decreased due to ethylene consumption during the reaction. The ethylene pressure was maintained at 1 atm by replenishing ethylene. After 20 minutes, the ethylene was turned off and the reaction was poured into a jar and acidified with ethanol. The polymer was stirred for 6 hours and filtered. The polymerization data and characterization results are shown in Table 1.

[0121] Comparative Example 7

[0122] A dry polymerization bottle was oven dried, vacuumed, and flushed with nitrogen three times. The bottle was vacuumed and charged with 1 atm of ethylene, 25 mL of toluene, 1 mL of alcohol 1 in toluene (0.125 mmol), 3 mL of methylaluminoxane in toluene (5.0 mmol), heated to 70 °C, and 1 mL of catalyst in toluene (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added. The reaction was started by timing and the ethylene pressure decreased due to ethylene consumption during the reaction. The ethylene pressure was maintained at 1 atm by replenishing ethylene. After 20 minutes, the ethylene was turned off and the reaction was poured into a jar and acidified with ethanol. The polymer was stirred for 6 hours and filtered. The polymerization data and characterization results are shown in Table 1.

[0123] Example 1

[0124] A dry polymerization bottle was oven dried, vacuumed, and flushed with nitrogen three times. The bottle was vacuumed and charged with 1 atm of ethylene, 25 mL of toluene, 1 mL of alcohol 1 in toluene (0.125 mmol), 3 mL of methylaluminoxane in toluene (5.0 mmol), heated to 70 °C, and 1 mL of catalyst in toluene (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added. The reaction was started by timing and the ethylene pressure decreased due to ethylene consumption during the reaction. The ethylene pressure was maintained at 1 atm by replenishing ethylene. After 20 minutes, the ethylene was turned off and the reaction was poured into a jar and acidified with ethanol. The polymer was stirred for 6 hours and filtered. The polymerization data and characterization results are shown in Table 1.

[0125] Example 2

[0126] A dry polymerization flask was evacuated and backfilled with nitrogen three times. The flask was again evacuated and charged with 1 atm of ethylene. The flask was charged with 25 mL of toluene, 1 mL of alcohol 1 in toluene (0.25 mmol of alcohol 1), 3 mL of methylaluminoxane in toluene (5.0 mmol of methylaluminoxane), and the temperature was raised to 70 °C. The reaction was started by adding 1 mL of catalyst in toluene (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride). The reaction was run at 1 atm of ethylene pressure by replenishing the ethylene as it was consumed. After 20 minutes, the ethylene was turned off and the reaction was quenched by pouring the reaction mixture into a beaker containing acidified ethanol. The polymer was isolated by stirring for 6 hours or more and filtering. The polymerization data and characterization results are shown in Table 1.

[0127] Example 3

[0128] A dry polymerization flask was evacuated and backfilled with nitrogen three times. The flask was again evacuated and charged with 1 atm of ethylene. The flask was charged with 25 mL of toluene, 1 mL of alcohol 1 in toluene (0.25 mmol of alcohol 1), 3 mL of methylaluminoxane in toluene (5.0 mmol of methylaluminoxane), and the temperature was raised to 70 °C. The reaction was started by adding 1 mL of catalyst in toluene (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride). The reaction was run at 1 atm of ethylene pressure by replenishing the ethylene as it was consumed. After 20 minutes, the ethylene was turned off and the reaction was quenched by pouring the reaction mixture into a beaker containing acidified ethanol. The polymer was isolated by stirring for 6 hours or more and filtering. The polymerization data and characterization results are shown in Table 1.

[0129] Example 4

[0130] A dry polymerization flask was evacuated and backfilled with nitrogen three times. The flask was again evacuated and charged with 1 atm of ethylene. The flask was charged with 25 mL of toluene, 1 mL of alcohol 1 in toluene (0.25 mmol of alcohol 1), 3 mL of methylaluminoxane in toluene (5.0 mmol of methylaluminoxane), and the temperature was raised to 70 °C. The reaction was started by adding 1 mL of catalyst in toluene (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride). The reaction was run at 1 atm of ethylene pressure by replenishing the ethylene as it was consumed. After 20 minutes, the ethylene was turned off and the reaction was quenched by pouring the reaction mixture into a beaker containing acidified ethanol. The polymer was isolated by stirring for 6 hours or more and filtering. The polymerization data and characterization results are shown in Table 1.

[0131] Example 5

[0132] A dry polymerization flask was evacuated and backfilled with nitrogen three times. The flask was again evacuated and charged with 1 atm of ethylene, 24 mL of toluene, 1 mL of 1-octene, 1 mL of alcohol 2 in toluene (0.5 mmol of alcohol 2), 3 mL of methylaluminoxane in toluene (5.0 mmol of methylaluminoxane). The temperature was raised to 70 °C and 1 mL of catalyst solution in toluene (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added. The reaction was started by timing and the ethylene pressure was maintained at 1 atm by replenishing the ethylene as it was consumed during the reaction. After 20 minutes, the ethylene was turned off and the reaction mixture was poured into a beaker and acidified with ethanol. The polymer was stirred for 6 hours and filtered. The polymerization data and characterization results are shown in Table 1.

[0133] Example 6

[0134] A dry polymerization flask was evacuated and backfilled with nitrogen three times. The flask was again evacuated and charged with 1 atm of ethylene, 24 mL of toluene, 1 mL of 1-octene, 1 mL of alcohol 2 in toluene (0.5 mmol of alcohol 2), 3 mL of methylaluminoxane in toluene (5.0 mmol of methylaluminoxane). The temperature was raised to 70 °C and 1 mL of catalyst solution in toluene (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added. The reaction was started by timing and the ethylene pressure was maintained at 1 atm by replenishing the ethylene as it was consumed during the reaction. After 20 minutes, the ethylene was turned off and the reaction mixture was poured into a beaker and acidified with ethanol. The polymer was stirred for 6 hours and filtered. The polymerization data and characterization results are shown in Table 1.

[0135] Example 7

[0136] A dry polymerization flask was evacuated and backfilled with nitrogen three times. The flask was again evacuated and charged with 1 atm of ethylene, 24 mL of toluene, 1 mL of 1-octene, 1 mL of alcohol 2 in toluene (0.5 mmol of alcohol 2), 3 mL of methylaluminoxane in toluene (5.0 mmol of methylaluminoxane). The temperature was raised to 70 °C and 1 mL of catalyst solution in toluene (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added. The reaction was started by timing and the ethylene pressure was maintained at 1 atm by replenishing the ethylene as it was consumed during the reaction. After 20 minutes, the ethylene was turned off and the reaction mixture was poured into a beaker and acidified with ethanol. The polymer was stirred for 6 hours and filtered. The polymerization data and characterization results are shown in Table 1.

[0137] Example 8

[0138] A dry polymerization bottle was charged with 4.71 g of norbornene, evacuated, and flushed with nitrogen three times. The bottle was evacuated and charged with 1 atm of ethylene, 25 mL of toluene, 1 mL of a toluene solution of alcohol 1 (0.5 mmol of alcohol 1), 3 mL of a toluene solution of methylaluminoxane (5.0 mmol of methylaluminoxane), and heated to 70 °C. A toluene solution of catalyst (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added and the reaction was timed. The pressure of ethylene decreased during the reaction due to ethylene consumption and was replenished to maintain 1 atm. After 20 min, the ethylene was turned off and the reaction was quenched by pouring into a flask containing acidified ethanol. The polymer was stirred for 6 h and filtered. The polymerization data and characterization results are shown in Table 1.

[0139] Example 9

[0140] A dry polymerization bottle was charged with 4.71 g of norbornene, evacuated, and flushed with nitrogen three times. The bottle was evacuated and charged with 1 atm of ethylene, 25 mL of toluene, 1 mL of a toluene solution of alcohol 1 (0.5 mmol of alcohol 1), 3 mL of a toluene solution of methylaluminoxane (5.0 mmol of methylaluminoxane), and heated to 70 °C. A toluene solution of catalyst (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added and the reaction was timed. The pressure of ethylene decreased during the reaction due to ethylene consumption and was replenished to maintain 1 atm. After 20 min, the ethylene was turned off and the reaction was quenched by pouring into a flask containing acidified ethanol. The polymer was stirred for 6 h and filtered. The polymerization data and characterization results are shown in Table 1.

[0141] Example 10

[0142] A dry polymerization bottle was charged with 4.71 g of norbornene, evacuated, and flushed with nitrogen three times. The bottle was evacuated and charged with 1 atm of ethylene, 25 mL of toluene, 1 mL of a toluene solution of alcohol 1 (0.5 mmol of alcohol 1), 3 mL of a toluene solution of methylaluminoxane (5.0 mmol of methylaluminoxane), and heated to 70 °C. A toluene solution of catalyst (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added and the reaction was timed. The pressure of ethylene decreased during the reaction due to ethylene consumption and was replenished to maintain 1 atm. After 20 min, the ethylene was turned off and the reaction was quenched by pouring into a flask containing acidified ethanol. The polymer was stirred for 6 h and filtered. The polymerization data and characterization results are shown in Table 1.

[0143] Example 11

[0144] A dry polymerization flask was evacuated and backfilled with nitrogen three times. The flask was again evacuated and charged with 1 atm of ethylene, 25 mL of toluene, 1 mL of 1-octene, 1 mL of a 0.5 M solution of alcohol 1 in toluene, 1 mL of a 1.0 M solution of triisobutylaluminum in toluene. The reaction mixture was heated to 70 °C and 1 mL of a 5 μM solution of the catalyst in toluene was added. The reaction mixture was charged with 1 mL of a 6 μM solution of triphenylphosphonium tetra(pentafluorophenyl)borate in toluene. The reaction was allowed to proceed and the pressure was maintained at 1 atm by the addition of ethylene as it was consumed. After 20 minutes, the ethylene was vented and the reaction mixture was poured into a beaker and stirred with acidified ethanol for 6 hours. The polymer was collected by filtration. The polymerization data and characterization results are shown in Table 1.

[0145] Example 12

[0146] A dry polymerization flask was evacuated and backfilled with nitrogen three times. The flask was again evacuated and charged with 1 atm of ethylene, 25 mL of toluene, 1 mL of 1-octene, 1 mL of a 0.5 M solution of alcohol 1 in toluene, 1 mL of a 1.0 M solution of triisobutylaluminum in toluene. The reaction mixture was heated to 70 °C and 1 mL of a 5 μM solution of the catalyst in toluene was added. The reaction mixture was charged with 1 mL of a 6 μM solution of triphenylphosphonium tetra(pentafluorophenyl)borate in toluene. The reaction was allowed to proceed and the pressure was maintained at 1 atm by the addition of ethylene as it was consumed. After 20 minutes, the ethylene was vented and the reaction mixture was poured into a beaker and stirred with acidified ethanol for 6 hours. The polymer was collected by filtration. The polymerization data and characterization results are shown in Table 1.

[0147] Example 13

[0148] A dry polymerization flask was evacuated and purged with nitrogen three times. The flask was again evacuated and charged with 1 atm of ethylene, 22.7 mL of toluene, 0.3 mL of 4-penten-l-ol, 1 mL of alcohol 1 in toluene (0.5 mmol of alcohol 1), 4 mL of triisobutylaluminum in toluene (1.0 mmol of triisobutylaluminum). The temperature was raised to 70 °C, 1 mL of catalyst in toluene (5 μmol of diphenylmethy(lcyclopentadienyl)(fluorenyl)zirconium dichloride) was added, 1 mL of triphenylphosphonium tetra(3,5-difluorophenyl)borate in toluene (6 μmol of triphenylphosphonium tetra(3,5-difluorophenyl)borate) was added, and the reaction was started. The ethylene pressure decreased during the reaction due to the consumption of ethylene, and ethylene was added to maintain the pressure at 1 atm. After 20 min, the ethylene was turned off, and the reaction mixture was poured into a beaker and stirred with acidified ethanol for more than 6 h. The polymer was collected by filtration. The polymerization results and characterization data are shown in Table 1.

[0149] Example 14

[0150] A dry polymerization flask was evacuated and purged with nitrogen three times. The flask was again evacuated and charged with 1 atm of ethylene, 22.7 mL of toluene, 0.3 mL of 4-penten-l-ol, 1 mL of alcohol 1 in toluene (0.5 mmol of alcohol 1), 4 mL of triisobutylaluminum in toluene (1.0 mmol of triisobutylaluminum). The temperature was raised to 70 °C, 1 mL of catalyst in toluene (5 μmol of diphenylmethy(lcyclopentadienyl)(fluorenyl)zirconium dichloride) was added, 1 mL of triphenylphosphonium tetra(3,5-difluorophenyl)borate in toluene (6 μmol of triphenylphosphonium tetra(3,5-difluorophenyl)borate) was added, and the reaction was started. The ethylene pressure decreased during the reaction due to the consumption of ethylene, and ethylene was added to maintain the pressure at 1 atm. After 20 min, the ethylene was turned off, and the reaction mixture was poured into a beaker and stirred with acidified ethanol for more than 6 h. The polymer was collected by filtration. The polymerization results and characterization data are shown in Table 1.

[0151] The polymerization characterization data are shown in the following table (the unit of polymerization activity in the table: kg-polymer / mole-catalyst / hour).

[0152] Table 1

[0153]

[0154] It can be seen from the comparison of Comparative Example 1 and Examples 1-5 that, by using the catalyst composition comprising an alcohol promoter according to the application, the molecular weight of the obtained polymer is higher than that of the polymer obtained without using the alcohol promoter composition, and the polymerization activity is slightly improved, which can broaden the regulation range of polyolefin products, improve the quality of polyolefin products, and improve the economy of production.

[0155] By comparing the comparative example 2 with the examples 6-7, it can be seen that by using the catalyst composition of the present application including alcohol promoter, the molecular weight of the obtained polymer is higher than that of the polymer obtained by using the catalyst composition without alcohol promoter, which can widen the regulation range of polyolefin products and improve the quality of polyolefin products.

[0156] By comparing the comparative example 3 with the examples 8-9, it can be seen that by using the catalyst composition of the present application including alcohol promoter, the molecular weight of the obtained polymer is higher than that of the polymer obtained by using the catalyst composition without alcohol promoter, and the molecular weight distribution is narrower, which can widen the regulation range of polyolefin products and improve the quality of polyolefin products.

[0157] By comparing the comparative example 4 with the example 10, it can be seen that by using the catalyst composition of the present application including alcohol promoter, the molecular weight of the obtained polymer is higher than that of the polymer obtained by using the catalyst composition without alcohol promoter, which can widen the regulation range of polyolefin products and improve the quality of polyolefin products.

[0158] By comparing the comparative example 5 with the example 11, it can be seen that by using the catalyst composition of the present application including alcohol promoter, the molecular weight of the obtained polymer is significantly higher than that of the polymer obtained by using the catalyst composition without alcohol promoter, which can widen the regulation range of polyolefin products and improve the quality of polyolefin products.

[0159] By comparing the comparative example 6 with the examples 12-13, it can be seen that by using the catalyst composition of the present application including alcohol promoter, the molecular weight of the obtained polymer is significantly higher than that of the polymer obtained by using the catalyst composition without alcohol promoter, which can widen the regulation range of polyolefin products and improve the quality of polyolefin products.

[0160] By comparing the comparative example 7 with the example 14, it can be seen that by using the catalyst composition of the present application including alcohol promoter, the molecular weight of the obtained polymer is significantly higher than that of the polymer obtained by using the catalyst composition without alcohol promoter, which can widen the regulation range of polyolefin products and improve the quality of polyolefin products.

[0161] The above describes the preferred embodiments of the present application in detail, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as the disclosed content of the present application and fall within the protection scope of the present application.

Claims

1. A catalyst composition, characterized in that, The catalyst composition comprises the following components: a) Metallocene compounds with structures shown in formula (I) and / or formula (II), In equations (I) and (II), Cp 1 and Cp 2 Each of the following is independently 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, either monosubstituted or polysubstituted. M represents titanium, zirconium, or hafnium; X 1 and X 2 Each can be independently a halogen atom, alkoxy group, aryloxy group, or hydrocarbon group; In equation (II), Q represents the connection of Cp. 1 and Cp 2 atoms or groups, b) Alcohols with structures shown in formula (III) and / or formula (IV), c) Co-catalyst components.

2. The catalyst composition according to claim 1, wherein, In equations (I) and (II), Cp 1 and Cp 2 Each of the following is independently a cyclopentadienyl or unsubstituted cyclopentadienyl group with 1-16 carbon atoms, a cyclopentadienyl or unsubstituted indenyl group with 1-16 carbon atoms, or a fluorenyl or unsubstituted fluorenyl group with 1-16 carbon atoms, either monosubstituted or polysubstituted. M represents titanium or zirconium; X 1 and X 2 Each is an independent halogen atom.

3. The catalyst composition according to claim 1 or 2, wherein, In equation (II), Q is -CH2CH2-, Cp 1 With Cp 2 All are indene-based, M is zirconium, and X is... 1 and X 2 It is a chlorine atom; Alternatively, in equation (II), Q is -SiR 1 R 2 -,Cp 1 and Cp 2 All are indene-based, M is zirconium, and X is... 1 and X 2 R is a chlorine atom. 1 and R 2 Each can be independently composed of a hydrogen atom or a hydrocarbon group with 1-20 carbon atoms; Alternatively, in equation (II), Q is -SiR 3 R 4 -,Cp 1 and Cp 2 All are 2-methyl-4-phenyl-indenyl, M is zirconium, X 1 and X 2 R is a chlorine atom. 3 and R 4 Each can be independently composed of a hydrogen atom or a hydrocarbon group with 1-20 carbon atoms; Alternatively, in equation (II), Q is -CR 5 R 6 -,Cp 1 It is cyclopentadienyl, Cp 2 It is fluorene-based, M is zirconium, X 1 and X 2 R is a chlorine atom. 5 and R 6 It is methyl or phenyl; Alternatively, in equation (II), Q is -CR 7 R 8 -,Cp 1 It is cyclopentadienyl, Cp 2 It is 2,7-di-tert-butyl-fluorene, M is zirconium, X 1 and X 2 R is a chlorine atom. 7 and R 8 It can be methyl or phenyl.

4. The catalyst composition according to claim 1, wherein, The metallocene compounds are selected from dicyclopentadienyl zirconium dichloride, di(n-butylcyclopentadienyl)zirconia dichloride, di(1-methyl-3-n-butylcyclopentadienyl)zirconia dichloride, diindylzirconia dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconia dichloride, diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butyl-9-fluorenyl)zirconia dichloride, isopropyl(cyclopentadienyl)(fluorenyl)zirconia dichloride, (4,4′-tert-butyl-diphenylmethylene)-cyclopentadienyl-(1-indyl)-titanium dichloride, and (4,4′-tert-butyl-diphenylmethylene)-cyclopentadienyl-(1-indyl)-titanium dichloride. (4,4′-tert-butyl-diphenylmethylene)-cyclopentadienyl-(1-indenyl)-hafnium dichloride, (4,4′-methoxy-diphenylmethylene)-cyclopentadienyl-(1-indenyl)-hafnium dichloride, (4,4′-methoxy-diphenylmethylene)-cyclopentadienyl-(1-indenyl)-hafnium dichloride, (4,4′-methyl-diphenylmethylene)-cyclopentadienyl-(1-indenyl)-hafnium dichloride, (4-methyl-4′-tert-butyl-diphenylmethylene)-cyclopentadienyl-(1-indenyl)-hafnium dichloride, (3,3′-... (3,3′-trifluoromethyl-diphenylmethylene)-cyclopentadienyl-(1-indenyl)-titanium dichloride, (3,3′-trifluoromethyl-diphenylmethylene)-cyclopentadienyl-(1-indenyl)-zirconium dichloride, (3,3′-trifluoromethyl-diphenylmethylene)-cyclopentadienyl-(1-indenyl)-hafnium dichloride, (4,4′-fluoro-diphenylmethylene)-cyclopentadienyl-(1-indenyl)-titanium dichloride, (4,4′-fluoro-diphenylmethylene)-cyclopentadienyl-(1-indenyl)-zirconium dichloride, (4,4′-fluoro-diphenylmethylene)-cyclopentadienyl-(1-indenyl)-zafnium dichloride, (4,4′-fluoro-diphenylmethylene)-cyclopentadienyl-(1-indenyl)-zafnium dichloride, (4,4′-fluoro-diphenylmethylene)-cyclopentadienyl-(1-indenyl)-hafnium dichloride The following are selected from one or more of the following: (4,4′-chloro-diphenylmethylene)-cyclopentadienyl-(1-indene)-titanium dichloride, (4,4′-chloro-diphenylmethylene)-cyclopentadienyl-(1-indene)-zirconium dichloride, (4,4′-chloro-diphenylmethylene)-cyclopentadienyl-(1-indene)-zirconium dichloride, racemic-vinyldiindenezirconium dichloride, racemic-dimethylsilyldiindenezirconium dichloride, racemic-dimethylsilyldi(2-methyl-indene)zirconium dichloride, and racemic-dimethylsilyldi(2-methyl-4-phenylindene)zirconium dichloride.

5. The catalyst composition according to claim 4, wherein, The metallocene compound is one or more of the following: dicyclopentadienyl zirconium dichloride, di(n-butylcyclopentadienyl) zirconium dichloride, di(1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride, diindyl zirconium dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl) zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, isopropyl(cyclopentadienyl)(fluorenyl) zirconium dichloride, racemic-vinyldiindyl zirconium dichloride, racemic-dimethylsilyldiindyl zirconium dichloride, and racemic-dimethylsilyldi(2-methyl-4-indyl) zirconium dichloride.

6. The catalyst composition according to any one of claims 1-5, wherein, The cocatalyst component includes one or more of alkylaluminoxanes, organoboron compounds, and organoaluminum compounds.

7. The catalyst composition according to any one of claims 1-5, wherein, The cocatalyst component is an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound.

8. The catalyst composition according to claim 7, wherein, The alkylaluminoxane is a compound selected from the structures shown in formula (V) and / or formula (VI). In formulas (IV) and (V), R is selected from alkyl groups having 1-15 carbon atoms, and n represents an integer from 4 to 30.

9. The catalyst composition according to claim 8, wherein, R is selected from alkyl groups with 1-5 carbon atoms, and n represents an integer from 10 to 30.

10. The catalyst composition according to claim 8, wherein, The alkylaluminoxane is methylaluminoxane.

11. The catalyst composition according to claim 7, wherein, The organoboron compound is one or more of tetra(pentafluorophenyl)borate, N,N-dimethylaniline tetra(pentafluorophenyl)borate, and tri(pentafluorophenyl)boron.

12. The catalyst composition according to claim 7, 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.

13. The catalyst composition according to claim 12, wherein, The organoaluminum compound is triisobutylaluminum.

14. The catalyst composition according to any one of claims 1-5, wherein, The cocatalyst is an alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane (calculated as aluminum) is 1:(50-20000).

15. The catalyst composition according to claim 14, wherein, The molar ratio of the metallocene compound to the alkylaluminoxane (calculated as aluminum) is 1:(200-10000).

16. The catalyst composition according to claim 15, wherein, The molar ratio of the metallocene compound to the alkylaluminoxane (calculated as aluminum) is 1:(500-3000).

17. The catalyst composition according to any one of claims 1-5, wherein, The cocatalyst is a combination of organoboron compounds and organoaluminum compounds, wherein the molar ratio of the metallocene compound to the organoboron compound is 1:(1-5), and the molar ratio of the metallocene compound to the organoaluminum compound is 1:(10-1000).

18. The catalyst composition according to claim 17, wherein, The molar ratio of the metallocene compound to the organoboron compound is 1:(1-2), and the molar ratio of the metallocene compound to the organoaluminum compound is 1:(10-200).

19. The catalyst composition according to any one of claims 1-5, wherein, The molar ratio of the metallocene compound to the alcohol is 1:(1-1000).

20. The catalyst composition according to claim 19, wherein, The molar ratio of the metallocene compound to the alcohol is 1:(10-500).

21. A method for olefin polymerization, characterized in that, The method includes contacting an olefin with the catalyst composition of any one of claims 1-20 to induce a polymerization reaction.

22. The method according to claim 21, wherein, The concentration of the metallocene compound in the polymerization reaction system is 1 × 10⁻⁶. -9 mol / L ~ 1×10 -3 Moles per liter.

23. The method according to claim 22, wherein, The concentration of the metallocene compound in the polymerization reaction system is 1 × 10⁻⁶. -8 mol / L ~ 1×10 -4 Moles per liter.

24. The method according to claim 21, wherein, The polymerization temperature is 0-200℃, and the polymerization time is 1-300 minutes.

25. The method according to claim 24, wherein, The polymerization reaction temperature is 50-160℃, and the polymerization reaction time is 5-60 minutes.

26. The method according to claim 21, wherein, The partial pressure of the olefin is 0.1-10 MPa.

27. The method according to claim 26, wherein, The partial pressure of the olefin is 0.1-4.0 MPa.

28. The method according to any one of claims 21-27, wherein, The olefin is ethylene, or ethylene and a second olefin as a comonomer.

29. The method according to claim 28, wherein, The second olefin is one or more of propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, cyclopentene, cycloheptene, 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, 7-octen-1-ol, 8-nonen-1-ol, 9-decen-1-ol, and 10-undecen-1-ol.

30. Use of the catalyst composition according to any one of claims 1-20 in olefin polymerization.

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