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 carbonyl-containing phenol, b) a metallocene compound, 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 application of the catalyst composition in olefin polymerization. BACKGROUND

[0002] Human beings have used polyolefin materials for several decades, and polyolefins have become the most widely used synthetic material in the world. In the past 30 years, metallocene catalysts have brought great progress to the polyolefin industry. They have strong copolymerization ability, not only can efficiently copolymerize comonomers, but also greatly expand the use range of comonomers (Chemistry Select, 2020, 5, 7581-7585). In this way, many new copolymers can be obtained through metallocene catalysts, and the application of polyolefin materials in new fields is realized.

[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 requires a very high concentration of comonomer in the polymerization reaction system. This reaction condition 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 chain to aluminum atom, thereby reducing the molecular weight of the polymer.

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

[0006] The purpose of the present application is to overcome the problem of reducing the molecular weight of the polymer in the prior art, and to provide a catalyst composition, an olefin polymerization method using the catalyst composition and application 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 using the catalyst composition of the present application is not very clear, but it is presumed that the present application adds the carbonyl group-containing phenol represented by the structure of formula (I) (hereinafter, also referred to as carbonyl group-containing phenol) to the metallocene-methylaluminoxane catalyst system or the like for the polymerization of olefins, and the latter reacts with the free aluminum alkyl or the organic boron compound in the methylaluminoxane or the solution thereof or the organic aluminum compound in the combination of the organic aluminum compound, thereby forming a new aluminoxane or aluminum alkyl containing a bulky group, causing a mass transfer resistance to the chain transfer reaction, thereby inhibiting the chain transfer reaction, and achieving the purpose of increasing the molecular weight of the polymer. At the same time, the carbonyl group-containing phenol having a large steric hindrance can also act on the catalyst, forming a large steric hindrance around the active center, and inhibiting the transfer of the polymerization growth chain to the aluminum atom or the comonomer.

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

[0009] a) a carbonyl group-containing phenol represented by the structure of formula (I),

[0010]

[0011] In formula (I), R 1 , R 2 , and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms or a halogen atom,

[0012] b) a metallocene compound represented by the structure of formula (II) and / or formula (III),

[0013]

[0014] In formula (II) and formula (III),

[0015] Cp 1 and Cp 2 are each independently a hydrocarbon group having 1 to 20 carbon atoms, which is mono- or poly-substituted or unsubstituted cyclopentadienyl, a hydrocarbon group having 1 to 20 carbon atoms, which is mono- or poly-substituted or unsubstituted indenyl, or a hydrocarbon group having 1 to 20 carbon atoms, which is mono- or poly-substituted or unsubstituted fluorenyl;

[0016] M is titanium, zirconium, or hafnium;

[0017] X 1 and X 2 are each independently a halogen atom, an alkoxy group, an aryloxy group, or a hydrocarbon group;

[0018] In formula (III), Q is an atom or a group that connects Cp 1 and Cp 2 ,

[0019] c) a cocatalyst component.

[0020] Preferably, in formula (I), R 1 , R 2 and R 3 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 6 to 10 carbon atoms; more preferably, R 1 and R 2 are each a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, and R 3 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aralkyl group having 6 to 10 carbon atoms.

[0021] Preferably, the carbonyl-containing phenol is one or more of 3,5-di-tert-butylsalicylaldehyde, 3,5-dichlorosalicylaldehyde and 2'-hydroxy-3-phenylpropiophenone.

[0022] Preferably, in formula (III), 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.

[0023] Preferably, in formula (III), Q is -SiR 4 R 5 , Cp 1 and Cp 2 are each an indenyl group, M is zirconium, X 1 and X 2 are each a chlorine atom, and R 4 and R 5 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0024] Preferably, in formula (III), Q is -SiR 6 R 7 , 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, and R 6 and R 7 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0025] Preferably, in formula (III), Q is -CR 8 R 9 , 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 is a chlorine atom. 8 and R 9 It can be methyl or phenyl.

[0026] Preferably, in formula (III), Q is -CR 10 R 11 -,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. 10 and R 11 It can be methyl or phenyl.

[0027] 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.

[0028] 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.

[0029] Preferably, the alkylaluminoxane is a compound selected from the structures represented by Formula (IV) and / or Formula (V),

[0030]

[0031] In Formula (IV) and Formula (V), 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.

[0032] Preferably, the alkylaluminoxane is methylaluminoxane.

[0033] Preferably, the organoboron compound is one or more of triphenylmethyl tetra(pentafluorophenyl)borate, N,N-dimethylanilinium tetra(pentafluorophenyl)borate, and tris(pentafluorophenyl)boron.

[0034] Preferably, the organoaluminum compound is a compound represented by the general formula AlX1X2X3, 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, an aryloxy group having 6-12 carbon atoms, X1, X2, and X3 can be the same or different, and at least one is an alkyl group having 1-8 carbon atoms.

[0035] Preferably, the organoaluminum compound is triisobutylaluminum.

[0036] 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).

[0037] Preferably, the cocatalyst 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).

[0038] Preferably, the molar ratio of the metallocene compound to the carbonyl-containing phenol is 1:(1-1000), preferably 1:(10-500).

[0039] 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.

[0040] 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.

[0041] 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.

[0042] Preferably, the partial pressure of the olefin is 0.1-10 MPa, preferably 0.1-4.0 MPa.

[0043] Preferably, the olefin is ethylene, or is ethylene and a second olefin as a comonomer.

[0044] Preferably, 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-nonene-1-ol, 9-decene-1-ol, and 10-undecene-1-ol.

[0045] 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.

[0046] According to the present application, by using a catalyst composition comprising a carbonyl-containing phenol, the molecular weight of the obtained polymer is significantly higher than that of a polymer obtained without using a catalyst composition comprising a carbonyl-containing phenol, which can broaden the regulation range of polyolefin products, and improve the quality and types of polyolefin products. DETAILED DESCRIPTION

[0047] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not considered critical for the purposes of the application. The endpoints of the ranges and any values are provided as approximations only and are understood to encompass values approximately the same as the endpoints. Various exemplary dimensions are provided in the following detailed description, which values are by way of example and not by way of limitation.

[0048] The first aspect of the present application provides a catalyst composition comprising the following components:

[0049] a) a carbonyl group-containing phenol represented by the following formula (I),

[0050]

[0051] In formula (I), R 1 , R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms or a halogen atom,

[0052] b) a metallocene compound represented by the following formula (II) and / or formula (III),

[0053]

[0054] In formula (II) and formula (III),

[0055] Cp 1 and Cp 2 are each independently a hydrocarbyl mono- or poly-substituted cyclopentadienyl group or an unsubstituted cyclopentadienyl group having 1 to 20 carbon atoms, a hydrocarbyl mono- or poly-substituted indenyl group or an unsubstituted indenyl group having 1 to 20 carbon atoms, a hydrocarbyl mono- or poly-substituted fluorenyl group or an unsubstituted fluorenyl group having 1 to 20 carbon atoms;

[0056] M is titanium, zirconium or hafnium;

[0057] X 1 and X 2 are each independently a halogen atom, an alkoxy group, an aryloxy group or a hydrocarbyl group;

[0058] In formula (III), Q is an atom or a group linking Cp 1 and Cp 2 ;

[0059] c) a cocatalyst component.

[0060] According to the catalyst component of the present application, preferably, in formula (II) and formula (III), Cp 1 and Cp 2hydrocarbyl group of 1 to 16 carbon atoms, a hydrocarbyl group of 1 to 16 carbon atoms, an unsubstituted cyclopentadienyl group, an unsubstituted indenyl group, an unsubstituted fluorenyl group, M is titanium or zirconium, X 1 and X 2 each independently is a halogen atom.

[0061] As the above hydrocarbyl group, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is further preferable.

[0062] As the above alkyl group having 1 to 10 carbon atoms, an alkyl group having a total of 1 to 10 carbon atoms is meant, including a straight chain alkyl group, a branched chain alkyl group or a cyclic alkyl group, and for example, a straight chain alkyl group, a branched chain alkyl group or a cyclic alkyl group having a total of 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms can be mentioned, and 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 and the like can be mentioned.

[0063] As the above aryl group having 6 to 12 carbon atoms, for example, phenyl, benzyl, phenethyl, diphenylmethylene, diphenylethylene and the like can be mentioned.

[0064] In the compounds represented by formula (II) and formula (III) of the present application, X 1 and X 2 each independently is a halogen atom, an alkoxy group, an aryloxy group or a hydrocarbyl group.

[0065] As the above halogen atom, for example, fluorine, chlorine, bromine or iodine can be mentioned, and fluorine, chlorine or bromine is preferable, and chlorine or bromine is more preferable, and chlorine is particularly preferable.

[0066] As the above alkoxy group, for example, an alkoxy group having 1 to 8 carbon atoms can be mentioned, and an alkoxy group having 1 to 6 carbon atoms is more preferable, and an alkoxy group having 1 to 3 carbon atoms is further preferable.

[0067] As the above alkoxy group having 1 to 8 carbon atoms, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, sec-butoxy, isobutoxy, pentoxy, hexyloxy, heptyloxy, octyloxy and the like can be mentioned.

[0068] As the above aryloxy group, for example, an aryloxy group having 6 to 12 carbon atoms can be mentioned, and specifically, phenoxy, methylphenoxy, ethylphenoxy, naphthoxy and the like can be mentioned.

[0069] 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.

[0070] In another preferred embodiment of the present application, in the formula (III), Q is -CH2CH2-, Cp n - (n is an integer of 2 to 20), Cp 1 and Cp 2 are each an indenyl group, M is zirconium, X 1 and X 2 are each a chlorine atom.

[0071] In another preferred embodiment of the present application, in the formula (III), 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.

[0072] In another preferred embodiment of the present application, in the formula (III), Q is -SiR 4 R 5 -, Cp 1 and Cp 2 are each an indenyl group, M is zirconium, X 1 and X 2 are each a chlorine atom, R 4 and R 5 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0073] In another preferred embodiment of the present application, in the formula (III), Q is -SiR 6 R 7 -, 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 6 and R 7 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0074] In another preferred embodiment of the present application, in the formula (III), Q is -CR 8 R 9 -, Cp 1is cyclopentadienyl, Cp 2 is fluorenyl, M is zirconium, and X 1 and X 2 is a chlorine atom, R 8 and R 9 is a methyl group or a phenyl group.

[0075] In another preferred embodiment of the present application, in the formula (III), Q is -CR 10 R 11 -, 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 10 and R 11 is a methyl group or a phenyl group.

[0076] 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.

[0077] 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.Among them, more preferable are one or more of the following: zirconium dicyclopentadienyl dichloride, zirconium di(n-butylcyclopentadienyl) dichloride, zirconium di(l-methyl-3-n-butylcyclopentadienyl) dichloride, zirconium diindenyl dichloride, zirconium diphenylmethylenecyclopentadienyl (fluorenyl) dichloride, zirconium diphenylmethylenecyclopentadienyl (2,7-di-t-butyl-9-fluorenyl) dichloride, zirconium isopropyl (cyclopentadienyl) (fluorenyl) dichloride, rac-ethylenediindenyl zirconium dichloride, rac-dimethylsilyl diindenyl zirconium dichloride, and rac-dimethylsilyl di(2-methyl-4-indenyl) zirconium dichloride.

[0078] The cocatalyst component of the catalyst composition according to the present application can be various cocatalyst components generally used in the art. Preferably, the cocatalyst component includes 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.

[0079] As the above alkylaluminoxane, a compound selected from the structures represented by Formula (IV) and / or Formula (V) is preferable,

[0080]

[0081] In Formula (IV) and Formula (V), R is selected from an alkyl group having 1 to 15 carbon atoms, and n represents an integer of 4 to 30; more preferably, R is selected from an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 10 to 30.

[0082] As specific examples of the above alkyl group, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, isobutyl, pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl, etc. can be given.

[0083] As the above n, for example, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, etc. can be given.

[0084] As specific examples of the above alkylaluminoxane, for example, methylaluminoxane, ethylaluminoxane, propylaluminoxane, etc. can be given, among which methylaluminoxane is preferable.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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,

[0089] As the halogen atom, for example, fluorine, chlorine, bromine, or iodine can be mentioned, and preferably, fluorine, chlorine, or bromine, and more preferably, chlorine or bromine, and particularly preferably, chlorine can be mentioned.

[0090] In the present application, as specific examples of the organic aluminum compound, 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.

[0091] In the catalyst composition according to the present application, in the formula (I), R 1 , R 2 , and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms or a halogen atom; preferably, in the formula (I), R 1 , R 2 , and R 3 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 10 carbon atoms; and more preferably, R 1 and R 2R is a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, R 3 R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aralkyl group having 6 to 10 carbon atoms.

[0092] Here, as the alkyl group having 1 to 8 carbon atoms, the groups listed in the above "alkyl group having 1 to 8 carbon atoms" can be given.

[0093] Here, as the halogen atom, the groups listed in the above "halogen atom" can be given.

[0094] Here, as the aralkyl group having 6 to 10 carbon atoms, for example, a benzyl group, a phenethyl group, a phenylpropyl group and the like can be given.

[0095] In the present application, as specific examples of the carbonyl group-containing phenol, for example, one or more of 3,5-di-tert-butylsalicylaldehyde, 3,5-dichlorosalicylaldehyde and 2'-hydroxy-3-phenylpropiophenone can be given.

[0096] According to the catalyst composition of the present application, when the co-catalyst is an alkylaluminoxane, the molar ratio of the metallocene compound to the alkylaluminoxane in terms of aluminum is 1 : (50-20000), more preferably 1 : (200-10000), more preferably 1 : (500-3000).

[0097] When 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).

[0098] According to the catalyst composition of the present application, preferably, the molar ratio of the metallocene compound to the carbonyl group-containing phenol is 1 : (1-1000), more preferably 1 : (10-500), further preferably 1 : (20-200), further preferably 1 : (50-150), more further preferably 1 : (100-150).

[0099] According to the second aspect of the present application, there is provided an olefin polymerization method, which comprises causing an olefin to undergo a polymerization reaction in contact with the catalyst composition according to the first aspect of the present application.

[0100] According to the method of the present application, the metallocene compound in the polymerization reaction system can be used in an amount generally used in the synthesis of polyolefins in the art. Preferably, the concentration of the metallocene compound in the polymerization reaction system is 1 x 10 -9 mole / liter to 1 x 10 -3 mole / liter, more preferably 1 x 10-8 Mol / liter ~ 1 x 10 -4 Mol / liter.

[0101] According to the method of the present application, preferably, the polymerization reaction 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 organic solvent amount can be determined according to the reactivity, ensuring good dissolution of the polymer in the system, at least not affecting the dispersion.

[0102] According to the method of the present application, the polymerization reaction conditions can be the conditions generally used in the art for the synthesis of polyolefins. Preferably, the temperature of the polymerization reaction is from 0 to 200°C and the time of the polymerization reaction is from 1 to 300 minutes; more preferably, the temperature of the polymerization reaction is from 50 to 160°C and the time of the polymerization reaction is from 5 to 60 minutes.

[0103] According to the method of the present application, preferably, the partial pressure of the olefin is from 0.1 to 10 MPa, preferably from 0.1 to 4.0 MPa.

[0104] According to the method of the present application, preferably, the olefin is ethylene or is ethylene with a second olefin as comonomer.

[0105] Preferably, the second olefin as comonomer 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-nonene-1-ol, 9-decene-1-ol and 10-undecene-1-ol.

[0106] In a preferred embodiment of the present application, when the cocatalyst component is an alkylaluminoxane, the method for its preparation comprises: vacuuming a sufficiently dried polymerization apparatus, flushing with nitrogen, repeating several times, then vacuuming again, charging with ethylene, sequentially adding a reaction solvent, a carbonyl-containing phenol and an alkylaluminoxane, then heating to the polymerization temperature, then adding a metallocene compound to carry out the polymerization reaction, during the polymerization, continuously feeding ethylene to make up for the ethylene consumed due to polymerization, after the completion of the polymerization reaction, closing the ethylene, adding acidified ethanol to the reaction liquid, stirring and then filtering to obtain the polymer.

[0107] In another preferred embodiment of the present application, the method for preparing the cocatalyst component, which is a combination of organoboron compound and organoaluminum compound, comprises the following steps: vacuumizing, nitrogen flushing repeatedly for several times, and then vacuumizing again a sufficiently dried polymerization device, charging ethylene, sequentially adding reaction solvent, 1-octene, carbonyl-containing phenol and organoaluminum compound, and then raising the temperature to the polymerization temperature, and then sequentially adding metallocene compound and organoboron compound, and then performing polymerization reaction, during which ethylene is continuously charged to make up the ethylene consumed due to polymerization, after the polymerization reaction is completed, the ethylene is shut off, acidified ethanol is added into the reaction solution, and then the polymer is obtained after filtration after stirring.

[0108] According to a third aspect of the present application, the catalyst composition according to the first aspect of the present application is used in the polymerization of olefins.

[0109] The present application will be described in detail below by way of examples, but the present application is not limited to the following examples.

[0110] The raw materials used in the following examples and comparative examples are, if not particularly limited, publicly known in the art, for example, can be directly purchased or prepared according to the publicly known preparation methods.

[0111] Polymer test method:

[0112] Weight average molecular weight and molecular weight distribution test

[0113] The molecular weight and molecular weight distribution of the sample are determined by using a PL-GPC 220 GPC of Polymer Laboratories, UK, 3 Plgel 10 μm MIXED-B columns are connected in series, the solvent and mobile phase are 1,2,4-trichlorobenzene containing 0.025 wt% antioxidant 2,6-dibutyl-p-cresol, the column temperature is 150°C, the flow rate is 1.0 ml / min, the sample concentration is 1 mg / ml, an IR5 infrared concentration detector is equipped, and a narrow distribution polystyrene standard is used for universal calibration.

[0114] List of carbonyl-containing phenols used in the comparative examples and examples:

[0115]

[0116] Comparative Example 1

[0117] A dry polymerization flask was purged with nitrogen three times. The flask was charged with 4.71 g of norbornene and purged with nitrogen three times. The flask was charged with 1 atm of ethylene and 26 mL of toluene, 3 mL of methylaluminoxane in toluene (5.0 mmol), and heated to 70°C. The reaction was started by adding 1 mL of catalyst solution in toluene (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride). The reaction was run for 20 minutes. The ethylene pressure was maintained at 1 atm by replenishing the ethylene as it was consumed. The reaction was stopped by removing the ethylene. The reaction mixture was poured into a beaker and acidified with ethanol. The polymer was isolated by stirring for 6 hours and filtering. The polymerization data and characterization results are shown in Table 1.

[0118] Comparative Example 2

[0119] A dry polymerization flask was purged with nitrogen three times. The flask was charged with 4.71 g of norbornene and purged with nitrogen three times. The flask was charged with 1 atm of ethylene and 26 mL of toluene, 3 mL of methylaluminoxane in toluene (5.0 mmol), and heated to 70°C. The reaction was started by adding 1 mL of catalyst solution in toluene (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride). The reaction was run for 20 minutes. The ethylene pressure was maintained at 1 atm by replenishing the ethylene as it was consumed. The reaction was stopped by removing the ethylene. The reaction mixture was poured into a beaker and acidified with ethanol. The polymer was isolated by stirring for 6 hours and filtering. The polymerization data and characterization results are shown in Table 1.

[0120] Comparative Example 3

[0121] A dry polymerization flask was purged with nitrogen three times. The flask was charged with 4.71 g of norbornene and purged with nitrogen three times. The flask was charged with 1 atm of ethylene and 26 mL of toluene, 3 mL of methylaluminoxane in toluene (5.0 mmol), and heated to 70°C. The reaction was started by adding 1 mL of catalyst solution in toluene (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride). The reaction was run for 20 minutes. The ethylene pressure was maintained at 1 atm by replenishing the ethylene as it was consumed. The reaction was stopped by removing the ethylene. The reaction mixture was poured into a beaker and acidified with ethanol. The polymer was isolated by stirring for 6 hours and filtering. The polymerization data and characterization results are shown in Table 1.

[0122] Comparative Example 4

[0123] A dry, oven-dried polymerization flask was evacuated and backfilled with nitrogen three times. The flask was again evacuated and charged with 1 atm of ethylene, 27 mL of toluene, 1 mL of triisobutylaluminum in toluene (1.0 mmol), and heated to 70°C. The flask was charged with 1 mL of catalyst in toluene (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) and 1 mL of triphenylphosphonium tetra(pentafluorophenyl)borate in toluene (6 μmol of triphenylphosphonium tetra(pentafluorophenyl)borate). 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 was poured into a beaker and acidified with ethanol. The polymer was isolated by stirring for 6 hours and filtering. The polymerization data and characterization results are shown in Table 1.

[0124] Comparative Example 5

[0125] A dry, oven-dried polymerization flask was evacuated and backfilled with nitrogen three times. The flask was again evacuated and charged with 1 atm of ethylene, 27 mL of toluene, 1 mL of triisobutylaluminum in toluene (1.0 mmol), and heated to 70°C. The flask was charged with 1 mL of catalyst in toluene (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) and 1 mL of triphenylphosphonium tetra(pentafluorophenyl)borate in toluene (6 μmol of triphenylphosphonium tetra(pentafluorophenyl)borate). 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 was poured into a beaker and acidified with ethanol. The polymer was isolated by stirring for 6 hours and filtering. The polymerization data and characterization results are shown in Table 1.

[0126] Comparative Example 6

[0127] A dry, oven-dried polymerization flask was evacuated and backfilled with nitrogen three times. The flask was again evacuated and charged with 1 atm of ethylene, 27 mL of toluene, 1 mL of triisobutylaluminum in toluene (1.0 mmol), and heated to 70°C. The flask was charged with 1 mL of catalyst in toluene (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) and 1 mL of triphenylphosphonium tetra(pentafluorophenyl)borate in toluene (6 μmol of triphenylphosphonium tetra(pentafluorophenyl)borate). 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 was poured into a beaker and acidified with ethanol. The polymer was isolated by stirring for 6 hours and filtering. The polymerization data and characterization results are shown in Table 1.

[0128] Comparative Example 7

[0129] A dry, oven-dried 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 a solution of phenol 1 in toluene (0.5 mmol of phenol 1), 3 mL of a solution of methylaluminoxane in toluene (5.0 mmol of methylaluminoxane), and the temperature was raised to 70 °C. A solution of the catalyst (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added and the reaction was timed. During the course of the reaction, the pressure of ethylene in the polymerization flask decreased due to ethylene consumption and was replenished to maintain a pressure of 1 atm. After 20 min, the ethylene was turned off and the reaction was quenched by pouring the reaction mixture into a flask containing acidified ethanol. The polymer was isolated by filtration after stirring for 6 h. The polymerization data and characterization results are shown in Table 1.

[0130] Example 1

[0131] A dry, oven-dried 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 a solution of phenol 1 in toluene (0.5 mmol of phenol 1), 3 mL of a solution of methylaluminoxane in toluene (5.0 mmol of methylaluminoxane), and the temperature was raised to 70 °C. A solution of the catalyst (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added and the reaction was timed. During the course of the reaction, the pressure of ethylene in the polymerization flask decreased due to ethylene consumption and was replenished to maintain a pressure of 1 atm. After 20 min, the ethylene was turned off and the reaction was quenched by pouring the reaction mixture into a flask containing acidified ethanol. The polymer was isolated by filtration after stirring for 6 h. The polymerization data and characterization results are shown in Table 1.

[0132] Example 2

[0133] A dry, oven-dried 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 a solution of phenol 1 in toluene (0.5 mmol of phenol 1), 3 mL of a solution of methylaluminoxane in toluene (5.0 mmol of methylaluminoxane), and the temperature was raised to 70 °C. A solution of the catalyst (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added and the reaction was timed. During the course of the reaction, the pressure of ethylene in the polymerization flask decreased due to ethylene consumption and was replenished to maintain a pressure of 1 atm. After 20 min, the ethylene was turned off and the reaction was quenched by pouring the reaction mixture into a flask containing acidified ethanol. The polymer was isolated by filtration after stirring for 6 h. The polymerization data and characterization results are shown in Table 1.

[0134] Example 3

[0135] 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 24 mL of toluene, 1 mL of 1-octene, 1 mL of a 0.5 M solution of phenol 2 in toluene, and 3 mL of a 5.0 M solution of methylaluminoxane in toluene. The flask was heated to 70 °C and charged with 1 mL of a 5.0 x 10"6M solution of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride in toluene. The reaction was started by timing and the ethylene pressure was maintained at 1 atm 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 the mixture for 6 hours or more and filtering. The polymerization data and characterization results are shown in Table 1.

[0136] Example 4

[0137] 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 24 mL of toluene, 1 mL of 1-octene, 1 mL of a 0.5 M solution of phenol 2 in toluene, and 3 mL of a 5.0 M solution of methylaluminoxane in toluene. The flask was heated to 70 °C and charged with 1 mL of a 5.0 x 10"6M solution of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride in toluene. The reaction was started by timing and the ethylene pressure was maintained at 1 atm 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 the mixture for 6 hours or more and filtering. The polymerization data and characterization results are shown in Table 1.

[0138] Example 5

[0139] 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 24 mL of toluene, 1 mL of 1-octene, 1 mL of a 0.5 M solution of phenol 2 in toluene, and 3 mL of a 5.0 M solution of methylaluminoxane in toluene. The flask was heated to 70 °C and charged with 1 mL of a 5.0 x 10"6M solution of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride in toluene. The reaction was started by timing and the ethylene pressure was maintained at 1 atm 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 the mixture for 6 hours or more and filtering. The polymerization data and characterization results are shown in Table 1.

[0140] Example 6

[0141] A dry polymerization flask was charged with 4.71 g of norbornene, 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 a 0.5 M solution of phenol 1 in toluene, and 3 mL of a 5.0 M solution of methylaluminoxane in toluene. The temperature was raised to 70 °C, and 1 mL of a 5.0 x 10"6M solution of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride in toluene was added. The reaction was timed, and the pressure of ethylene was allowed to decrease as the ethylene was consumed during the reaction. The pressure was maintained at 1 atm by the addition of ethylene. After 20 minutes, the ethylene was turned off, and the reaction was quenched by the addition of acidified ethanol. The polymer was isolated by stirring for 6 h and filtration. The polymerization data and characterization results are shown in Table 1.

[0142] Example 7

[0143] A dry polymerization flask was charged with 4.71 g of norbornene, 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 a 0.5 M solution of phenol 1 in toluene, and 3 mL of a 5.0 M solution of methylaluminoxane in toluene. The temperature was raised to 70 °C, and 1 mL of a 5.0 x 10"6M solution of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride in toluene was added. The reaction was timed, and the pressure of ethylene was allowed to decrease as the ethylene was consumed during the reaction. The pressure was maintained at 1 atm by the addition of ethylene. After 20 minutes, the ethylene was turned off, and the reaction was quenched by the addition of acidified ethanol. The polymer was isolated by stirring for 6 h and filtration. The polymerization data and characterization results are shown in Table 1.

[0144] Example 8

[0145] A dry polymerization flask was charged with 4.71 g of norbornene, 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 a 0.5 M solution of phenol 1 in toluene, and 3 mL of a 5.0 M solution of methylaluminoxane in toluene. The temperature was raised to 70 °C, and 1 mL of a 5.0 x 10"6M solution of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride in toluene was added. The reaction was timed, and the pressure of ethylene was allowed to decrease as the ethylene was consumed during the reaction. The pressure was maintained at 1 atm by the addition of ethylene. After 20 minutes, the ethylene was turned off, and the reaction was quenched by the addition of acidified ethanol. The polymer was isolated by stirring for 6 h and filtration. The polymerization data and characterization results are shown in Table 1.

[0146] Example 9

[0147] A dry, oven-dried polymerization flask was evacuated and backfilled with nitrogen three times. The flask was again evacuated and charged with 1 atm of ethylene, 21.7 mL of toluene, 1 mL of a toluene solution of phenol 1 (0.5 mmol of phenol 1), 0.3 mL of 4-penten-l-ol, 3 mL of a toluene solution of triisobutylaluminum (1.0 mmol of triisobutylaluminum), 3 mL of a toluene solution of methylaluminoxane (5.0 mmol of methylaluminoxane), and the temperature was raised to 70 °C. The reaction was started by the addition of 1 mL of a toluene solution of the catalyst (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride). The reaction was timed and the pressure of ethylene was allowed to decrease as ethylene was consumed during the reaction. Ethylene was added to maintain a pressure of 1 atm. After 20 min, 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 filtration after stirring for 6 h. The polymerization results and characterization data are shown in Table 1.

[0148] Example 10

[0149] A dry, oven-dried polymerization flask was evacuated and backfilled with nitrogen three times. The flask was again evacuated and charged with 1 atm of ethylene, 21.7 mL of toluene, 1 mL of a toluene solution of phenol 1 (0.5 mmol of phenol 1), 0.3 mL of 4-penten-l-ol, 3 mL of a toluene solution of triisobutylaluminum (1.0 mmol of triisobutylaluminum), 3 mL of a toluene solution of methylaluminoxane (5.0 mmol of methylaluminoxane), and the temperature was raised to 70 °C. The reaction was started by the addition of 1 mL of a toluene solution of the catalyst (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride). The reaction was timed and the pressure of ethylene was allowed to decrease as ethylene was consumed during the reaction. Ethylene was added to maintain a pressure of 1 atm. After 20 min, 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 filtration after stirring for 6 h. The polymerization results and characterization data are shown in Table 1.

[0150] Example 11

[0151] A dry, oven-dried polymerization flask was evacuated and backfilled with nitrogen three times. The flask was again evacuated and charged with 1 atm of ethylene, 21.7 mL of toluene, 1 mL of a toluene solution of phenol 1 (0.5 mmol of phenol 1), 0.3 mL of 4-penten-l-ol, 3 mL of a toluene solution of triisobutylaluminum (1.0 mmol of triisobutylaluminum), 3 mL of a toluene solution of methylaluminoxane (5.0 mmol of methylaluminoxane), and the temperature was raised to 70 °C. The reaction was started by the addition of 1 mL of a toluene solution of the catalyst (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride). The reaction was timed and the pressure of ethylene was allowed to decrease as ethylene was consumed during the reaction. Ethylene was added to maintain a pressure of 1 atm. After 20 min, 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 filtration after stirring for 6 h. The polymerization results and characterization data are shown in Table 1.

[0152] Example 12

[0153] A dry polymerization bottle was evacuated and flushed with nitrogen three times. The bottle was evacuated and charged with 1 atm of ethylene, 26 mL of toluene, 1 mL of a toluene solution of phenol 3 (0.25 mmol of phenol 3), 1 mL of a toluene solution of triisobutylaluminum (1.0 mmol of triisobutylaluminum), and the temperature was raised to 70 °C. A solution of the catalyst (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added and the reaction was started by adding 1 mL of a toluene solution of triphenylphosphonium tetra(pentafluorophenyl)borate (6 μmol of triphenylphosphonium tetra(pentafluorophenyl)borate). The pressure of ethylene was allowed to decrease during the reaction due to ethylene consumption and was maintained at 1 atm by the addition of ethylene. After 20 min, the ethylene was turned off and the reaction was quenched by the addition of acidified ethanol. The polymer was isolated by filtration after stirring for 6 h. The polymerization data and characterization results are shown in Table 1.

[0154] Example 13

[0155] A dry polymerization bottle was evacuated and flushed with nitrogen three times. The bottle was evacuated and charged with 1 atm of ethylene, 26 mL of toluene, 1 mL of a toluene solution of phenol 3 (0.25 mmol of phenol 3), 1 mL of a toluene solution of triisobutylaluminum (1.0 mmol of triisobutylaluminum), and the temperature was raised to 70 °C. A solution of the catalyst (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added and the reaction was started by adding 1 mL of a toluene solution of triphenylphosphonium tetra(pentafluorophenyl)borate (6 μmol of triphenylphosphonium tetra(pentafluorophenyl)borate). The pressure of ethylene was allowed to decrease during the reaction due to ethylene consumption and was maintained at 1 atm by the addition of ethylene. After 20 min, the ethylene was turned off and the reaction was quenched by the addition of acidified ethanol. The polymer was isolated by filtration after stirring for 6 h. The polymerization data and characterization results are shown in Table 1.

[0156] Example 14

[0157] A dry polymerization bottle was 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 1-octene, 1 mL of a toluene solution of phenol 2 (0.25 mmol of phenol 2), 1 mL of a toluene solution of triisobutylaluminum (1.0 mmol of triisobutylaluminum), and heated to 70 °C. A solution of the catalyst (5 μmol of bisphenylmethy(lcyclopentadienyl)(fluorenyl)zirconium dichloride) was added, followed by a solution of triphenylphosphonium tetra(pentafluorophenyl)borate (6 μmol of triphenylphosphonium tetra(pentafluorophenyl)borate). The reaction was timed and the pressure of ethylene was maintained at 1 atm by the addition of ethylene as it was consumed. After 20 minutes, the ethylene was turned off and the reaction was quenched by the addition of acidified ethanol. The polymer was isolated by filtration after stirring for 6 hours. The polymerization data and characterization results are shown in Table 1.

[0158] Example 15

[0159] A dry polymerization bottle was 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 1-octene, 1 mL of a toluene solution of phenol 2 (0.25 mmol of phenol 2), 1 mL of a toluene solution of triisobutylaluminum (1.0 mmol of triisobutylaluminum), and heated to 70 °C. A solution of the catalyst (5 μmol of bisphenylmethy(lcyclopentadienyl)(fluorenyl)zirconium dichloride) was added, followed by a solution of triphenylphosphonium tetra(pentafluorophenyl)borate (6 μmol of triphenylphosphonium tetra(pentafluorophenyl)borate). The reaction was timed and the pressure of ethylene was maintained at 1 atm by the addition of ethylene as it was consumed. After 20 minutes, the ethylene was turned off and the reaction was quenched by the addition of acidified ethanol. The polymer was isolated by filtration after stirring for 6 hours. The polymerization data and characterization results are shown in Table 1.

[0160] Example 16

[0161] A dry polymerization bottle was 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 1-octene, 1 mL of a toluene solution of phenol 2 (0.25 mmol of phenol 2), 1 mL of a toluene solution of triisobutylaluminum (1.0 mmol of triisobutylaluminum), and heated to 70 °C. A solution of the catalyst (5 μmol of bisphenylmethy(lcyclopentadienyl)(fluorenyl)zirconium dichloride) was added, followed by a solution of triphenylphosphonium tetra(pentafluorophenyl)borate (6 μmol of triphenylphosphonium tetra(pentafluorophenyl)borate). The reaction was timed and the pressure of ethylene was maintained at 1 atm by the addition of ethylene as it was consumed. After 20 minutes, the ethylene was turned off and the reaction was quenched by the addition of acidified ethanol. The polymer was isolated by filtration after stirring for 6 hours. The polymerization data and characterization results are shown in Table 1.

[0162] Example 17

[0163] A dry polymerization bottle was evacuated and flushed with nitrogen three times. The bottle was evacuated and charged with 1 atm of ethylene, 22.7 mL of toluene, 0.3 mL of 4-penten-l-ol, 1 mL of a toluene solution of phenol 3 (0.5 mmol of phenol 3), 4 mL of a toluene solution of triisobutylaluminum (1.0 mmol of triisobutylaluminum), and heated to 70 °C. A solution of the catalyst (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride in toluene, 1 mL) was added, followed by a solution of triphenylphosphonium tetra(pentafluorophenyl)borate in toluene (6 μmol of triphenylphosphonium tetra(pentafluorophenyl)borate, 1 mL). The reaction was timed and ethylene was added to maintain a pressure of 1 atm. After 20 minutes, the ethylene was turned off and the reaction was quenched by pouring into acidified ethanol. The polymer was isolated by filtration after stirring for 6 h. The polymerization data and characterization results are shown in Table 1.

[0164] Example 18

[0165] A dry polymerization bottle was evacuated and flushed with nitrogen three times. The bottle was evacuated and charged with 1 atm of ethylene, 22.7 mL of toluene, 0.3 mL of 4-penten-l-ol, 1 mL of a toluene solution of phenol 3 (0.5 mmol of phenol 3), 4 mL of a toluene solution of triisobutylaluminum (1.0 mmol of triisobutylaluminum), and heated to 70 °C. A solution of the catalyst (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride in toluene, 1 mL) was added, followed by a solution of triphenylphosphonium tetra(pentafluorophenyl)borate in toluene (6 μmol of triphenylphosphonium tetra(pentafluorophenyl)borate, 1 mL). The reaction was timed and ethylene was added to maintain a pressure of 1 atm. After 20 minutes, the ethylene was turned off and the reaction was quenched by pouring into acidified ethanol. The polymer was isolated by filtration after stirring for 6 h. The polymerization data and characterization results are shown in Table 1.

[0166] Example 19

[0167] A dry, oven-dried polymerization flask was evacuated and backfilled 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-1-ol, 1 mL of a toluene solution of phenol 1 containing 0.125 mmol of phenol 1, 4 mL of a toluene solution of triisobutylaluminum containing 1.0 mmol of triisobutylaluminum, and the temperature was raised to 70 °C. A toluene solution of the catalyst (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added, and a toluene solution of triphenylphosphonium tetra(pentafluorophenyl)borate (6 μmol of triphenylphosphonium tetra(pentafluorophenyl)borate) was added. The reaction was timed and, during the course of the reaction, the pressure of ethylene was allowed to decrease due to ethylene consumption and was replenished to maintain a pressure of 1 atm. After 20 minutes, the ethylene was turned off and the reaction was quenched by pouring the reaction mixture into a flask containing acidified ethanol. The polymer was isolated by filtration after stirring for 6 h. The results of the polymerization and characterization data are shown in Table 1.

[0168] Example 20

[0169] A dry, oven-dried polymerization flask was evacuated and backfilled 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-1-ol, 1 mL of a toluene solution of phenol 1 containing 0.125 mmol of phenol 1, 4 mL of a toluene solution of triisobutylaluminum containing 1.0 mmol of triisobutylaluminum, and the temperature was raised to 70 °C. A toluene solution of the catalyst (5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride) was added, and a toluene solution of triphenylphosphonium tetra(pentafluorophenyl)borate (6 μmol of triphenylphosphonium tetra(pentafluorophenyl)borate) was added. The reaction was timed and, during the course of the reaction, the pressure of ethylene was allowed to decrease due to ethylene consumption and was replenished to maintain a pressure of 1 atm. After 20 minutes, the ethylene was turned off and the reaction was quenched by pouring the reaction mixture into a flask containing acidified ethanol. The polymer was isolated by filtration after stirring for 6 h. The results of the polymerization and characterization data are shown in Table 1.

[0170] Example 21

[0171] A dry polymerization bottle was sufficiently dried, vacuumed, flushed with nitrogen three times. Vacuumed, filled with 1 atm ethylene, added 22.7 mL of toluene, 0.3 mL of 4-penten-1-ol, 1 mL of phenol 1 toluene solution (containing 0.5 mmol of phenol 1), 4 mL of triisobutylaluminum toluene solution (containing 1.0 mmol of triisobutylaluminum), heated to 70 °C, added 1 mL of catalyst toluene solution (containing 5 μmol of bisphenylmethyl(cyclopentadienyl)(fluorenyl)zirconium dichloride), added 1 mL of triphenylphosphonium tetra(pentafluorophenyl)borate toluene solution (containing 6 μmol of triphenylphosphonium tetra(pentafluorophenyl)borate), started timing, during the reaction, the pressure of ethylene in the polymerization bottle decreased due to the consumption of ethylene, and ethylene was added to maintain the pressure at 1 atm. After 20 minutes, the ethylene was closed, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and the polymer was filtered. The polymerization results and characterization data are shown in Table 1.

[0172] The polymerization characterization data are shown in the following table (in the table: 1-octene feed 1 mL, concentration in the polymerization system 0.21 mol / L; norbornene feed 4.71 g, concentration in the polymerization system 1.33 mol / L; 4-penten-1-ol feed 0.3 mL, concentration in the polymerization system 0.10 mol / L; polymerization activity unit: kg-polymer / mol-catalyst / hour).

[0173] Table 1

[0174]

[0175] As can be seen from the comparison of Comparative Example 1 and Examples 1-3, by using the catalyst composition comprising the phenol containing carbonyl group according to the present application, the molecular weight of the obtained polymer is significantly higher than that of the polymer obtained without using the catalyst composition comprising the phenol containing carbonyl group, the phenol 1 can improve the polymerization activity, can broaden the regulation range of polyolefin products, and improve the quality of polyolefin products and the economy of production.

[0176] As can be seen from the comparison of Comparative Example 2 and Examples 4-6, by using the catalyst composition comprising the phenol containing carbonyl group according to the present application, the molecular weight of the obtained polymer is higher than that of the polymer obtained without using the catalyst composition comprising the phenol containing carbonyl group, can broaden the regulation range of polyolefin products, and improve the quality of polyolefin products.

[0177] As can be seen from the comparison of Comparative Example 3 and Examples 7-8, by using the catalyst composition comprising the phenol containing carbonyl group according to the present application, the molecular weight of the obtained polymer is significantly higher than that of the polymer obtained without using the catalyst composition comprising the phenol containing carbonyl group, the weight average molecular weight of the polymer is improved to 2-4 times of that of the latter, and the molecular weight distribution is narrowed, can broaden the regulation range of polyolefin products, and improve the quality of polyolefin products.

[0178] As can be seen from the comparison between Comparative Example 4 and Examples 9-11, by using the catalyst composition comprising the carbonyl-containing phenol according to the present application, the molecular weight of the obtained polymer is higher than that of the polymer obtained without using the catalyst composition comprising the carbonyl-containing phenol, which can broaden the regulation range of the polyolefin product and improve the quality of the polyolefin product.

[0179] As can be seen from the comparison between Comparative Example 5 and Examples 12-14, by using the catalyst composition comprising the carbonyl-containing phenol according to the present application, the molecular weight of the obtained polymer is higher than that of the polymer obtained without using the catalyst composition comprising the carbonyl-containing phenol, which can broaden the regulation range of the polyolefin product and improve the quality of the polyolefin product.

[0180] As can be seen from the comparison between Comparative Example 6 and Examples 15-17, by using the catalyst composition comprising the carbonyl-containing phenol according to the present application, the molecular weight of the obtained polymer is higher than that of the polymer obtained without using the catalyst composition comprising the carbonyl-containing phenol, which can broaden the regulation range of the polyolefin product and improve the quality of the polyolefin product.

[0181] As can be seen from the comparison between Comparative Example 7 and Examples 18-21, by using the catalyst composition comprising the carbonyl-containing phenol according to the present application, the molecular weight of the obtained polymer is higher than that of the polymer obtained without using the catalyst composition comprising the carbonyl-containing phenol, which can broaden the regulation range of the polyolefin product and improve the quality of the polyolefin product.

[0182] 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) Carbonyl-containing phenols with the structure shown in formula (I), Formula (I) In equation (I), R 1 and R 2 R represents hydrogen atoms, halogen atoms, or alkyl groups having 1-6 carbon atoms. 3 It consists of hydrogen atoms, alkyl groups having 1-6 carbon atoms, or aralkyl groups having 6-10 carbon atoms. b) Metallocene compounds with structures shown in formula (II) and / or formula (III), Equation (II) Equation (III) In equations (II) and (III), 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 (III), Q represents the connection of Cp. 1 and Cp 2 atoms or groups, c) Co-catalyst components, The cocatalyst component is an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound.

2. The catalyst composition according to claim 1, wherein, The carbonylphenol is one or more of 3,5-di-tert-butylsalicylaldehyde, 3,5-dichlorosalicylaldehyde, and 2'-hydroxy-3-phenylacetone.

3. The catalyst composition according to claim 1, wherein, In equations (II) and (III), 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.

4. The catalyst composition according to any one of claims 1-3, wherein, In equation (III), 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 (III), Q is -SiR 4 R 5 -,Cp 1 and Cp 2 All are indene-based, M is zirconium, and X is... 1 and X 2 R is a chlorine atom. 4 and R 5 Each can be independently composed of a hydrogen atom or a hydrocarbon group with 1-20 carbon atoms; Alternatively, in equation (III), Q is -SiR 6 R 7 -,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. 6 and R 7 Each can be independently composed of a hydrogen atom or a hydrocarbon group with 1-20 carbon atoms; Alternatively, in equation (III), Q is -CR 8 R 9 -,Cp 1 It is cyclopentadienyl, Cp 2 It is fluorene-based, M is zirconium, X 1 and X 2 R is a chlorine atom. 8 and R 9 It is methyl or phenyl; Alternatively, in equation (III), Q is -CR 10 R 11 -,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. 10 and R 11 It can be methyl or phenyl.

5. The catalyst composition according to any one of claims 1-3, 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.

6. The catalyst composition according to any one of claims 1-3, wherein, The molar ratio of the metallocene compound to the carbonyl phenol is 1:(1-1000).

7. The catalyst composition according to claim 6, wherein, The molar ratio of the metallocene compound to the carbonyl phenol is 1:(10-500).

8. The catalyst composition according to claim 1, wherein, The alkylaluminoxane is a compound selected from the structures shown in formula (IV) and / or formula (V). Formula (IV) Equation (V) 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 9, wherein, The alkylaluminoxane is methylaluminoxane.

11. The catalyst composition according to claim 1, 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 1, 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 1-3, 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 cocatalyst is an alkylaluminoxane, and 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 cocatalyst is an alkylaluminoxane, and 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 1-3, 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 cocatalyst is a combination of organoboron compounds and organoaluminum compounds, wherein the molar ratio of the metallocene compound to the organoboron compound is 1:(1-2), and the molar ratio of the metallocene compound to the organoaluminum compound is 1:(10-200).

19. A method for olefin polymerization, characterized in that, The method includes contacting an olefin with the catalyst composition of any one of claims 1-18 to induce a polymerization reaction.

20. The method according to claim 19, 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.

21. The method according to claim 20, 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.

22. The method according to claim 19, wherein, The polymerization temperature is 0-200℃, and the polymerization time is 1-300 minutes.

23. The method according to claim 22, wherein, The polymerization reaction temperature is 50-160℃, and the polymerization reaction time is 5-60 minutes.

24. The method according to claim 19, wherein, The partial pressure of the olefin is 0.1-10 MPa.

25. The method according to claim 24, wherein, The partial pressure of the olefin is 0.1-4.0 MPa.

26. The method according to any one of claims 19-25, wherein, The olefin is ethylene, or ethylene and a second olefin as a comonomer.

27. The method according to claim 26, 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.

28. Use of the catalyst composition according to any one of claims 1-18 in olefin polymerization.

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