Olefin Polymerization Metallocene Catalyst Composition and Its Preparation and Use

Abstract

An olefin polymerization catalyst composition comprising a main catalyst and a carrier, wherein the carrier is fluorinated silica gel particles and the main catalyst is a metallocene complex represented by the general formula (I). The present invention also discloses the preparation of the composition and its use in the olefin polymerization reaction. The present invention provides a composition capable of improving the form of the polymer while reducing or avoiding the use of methylaluminoxane or borate reagents. 【Chemical 1】 TIFF2025521351000025.tif26170

Description

Technical Field

[0001] The present invention relates to a metallocene catalyst composition, a preparation method and its use in olefin polymerization.

Background Art

[0002] Based on the rich substitution chemistry on the indenyl ring (Halterman, R.L. Chem. Rev. 1992, 92, 965), the infinite combinations of substituents at the 1st to 7th positions on the indenyl ring, and its potential scientific, technical and commercial values, Group 3 and Group 4 metallocene complex olefin polymerization catalysts mainly composed of substituted indenyls, especially bridged Group 4 transition metallocene complex olefin polymerization catalysts, have received extremely great attention in the past 30 years (Luigi Resconi, Luigi Cavallo, Anna Fait, and Fabrizio Piemontesi, Chemical Reviews 2000, 100, 1253). The Group 4 transition metallocene complex with bridged substituted indenyl as the ligand has actually become the mainstream of metallocene chemistry, providing not only a lot of powerful experimental evidence for developing the theory of organometallic chemistry, but also catalysts with many special properties for the polyolefin industry and highly selective organic synthetic chemistry (Metallocenes in Regio - and Stereoselective Synthesis, T. Takahashi Ed, Springer, 2005). Briefly speaking, the development of metallocene complex catalysts has greatly contributed to elucidating the mechanism of stereospecific polymerization of α - olefins, enriching the varieties and specifications of polyolefin materials, and providing new polyolefin materials with special properties (-Based Polyolefin; J. Scheirs and W. Kaminsky Eds. Wiley, 2000.).

[0003] In the development process of metallocene catalysts, in addition to typical bridged-substituted cyclopentadienyl (substituted-Cyclopentadienyl, Cp'), bridged-substituted indenyl (substituted-Indenyl, Ind'), bridged-substituted fluorenyl (substituted fluorenyl, Flu'), and a large number of metallocene complexes formed by combinations with each other among Cp' / Ind' / Flu' (Metallocenes: Synthesis, Reactivity, Applications, A. Togni and R.L. Halterman Eds, Wiley, 1998), in recent years, some metallocene complexes have heteroatoms such as nitrogen, phosphorus, oxygen, sulfur, etc. introduced into the cyclopentadienyl ring (Cp) or a saturated or unsaturated ring adjacent to the Cp ring. Metallocene complexes containing heteroatom rings have special polymerization activities for olefins or special regioselectivities or stereoselectivities (C. De Rosa, F. Auriema, A. Di Capua, L. Resconi, S. Guidotti, I. Camurati, I.E. Nifant'ev, I.P. Laishevtsev, J. Am. Chem. Soc. 2004, 12, 17040). For example, CA2204803 describes a phosphorus (i.e., heteroatom)-containing metallocene complex and its activity for catalyzing ethylene polymerization, molecular weight distribution, and excellent high-temperature catalytic activity. The Group 4 element metallocene catalyst system related to this can catalyze ethylene polymerization at high temperatures to produce high-molecular-weight polyethylene. WO9822486 and EP9706297 describe metallocene complexes containing oxygen or / and sulfur or / and nitrogen in the five-membered ring adjacent to Cp. Such complexes have extremely high polymerization activities for propylene when combined with methylaluminoxane (MAO). WO0144318 describes a metallocene complex of a sulfur-containing π-ligand and its ethylene / propylene catalytic copolymerization process, but since the molecular weight of the obtained ethylene-propylene copolymer is low, it has no practical application value.WO03045964 describes a process for preparing zirconocene complexes of dimethylsilicon-crosslinked substituted thiopentalene and substituted indene, and a process for catalyzing the copolymerization of ethylene and propylene therewith. In the process described in WO03045964, such zirconocene complexes have very high polymerization activity, the resulting ethylene-propylene copolymer has a relatively high molecular weight, and the ethylene content in the copolymer is between 4% and 13% by percentage, and its material properties are between RCP and TPE.

[0004] US6756455 describes a nitrogen-containing π-ligand zirconocene complex, particularly a zirconocene complex catalyst coordinated with a crosslinked indolopyrrole derivative and a crosslinked indoloindole derivative. Such a zirconocene complex catalyst has high activity, high molecular weight, and a bimodal molecular weight distribution under appropriate conditions when used in ethylene homopolymerization. US6683150 discloses many examples of producing high molecular weight polypropylene by catalyzing propylene polymerization with a Group 4 transition metallocene complex catalyst having a crosslinked indoloindole derivative as a ligand over a wide temperature range. WO03089485 provides a catalyst system comprising a nitrogen-containing π-ligand Group 4 transition metallocene complex and methylaluminoxane (MAO) which uses a very low aluminum / metal ratio, has high activity, and can produce high molecular weight linear low density polyethylene (mLLDPE) when combined with a suitable carrier. WO9924446 describes a metallocene complex formed from a nitrogen heteroatom-containing π-ligand and a Group 4 transition metal. Such a metallocene complex is not only simple to synthesize and has a high yield, but also an excellent olefin polymerization catalyst after activation with methylaluminoxane (MAO), modified methylaluminoxane (MMAO) or a borate reagent, and can polymerize to produce high molecular weight polyethylene and polypropylene respectively.

[0005] In the application of copolymer production, in order to obtain high catalytic activity, the amount of aluminoxane reagent or borate reagent used in combination with the metallocene complex is large, and the molar ratio to the metallocene complex often reaches 500 times or more, and in some cases, it may reach several thousand times. Since the aluminoxane reagent or borate reagent is expensive and the amount used is large, the production cost of the metallocene catalyst becomes high. Furthermore, the metallocene catalyst is a homogeneous catalyst, and the form of the produced polymer product is poor. In the polymerization and product transportation processes, it is likely to cause clogging of the polymerization tank and equipment, and its adaptability to industrial equipment is poor, making industrial use difficult. Therefore, ensuring the polymerization activity level of the metallocene catalyst, reducing the amount of aluminoxane reagent and borate reagent used, and thus avoiding the use of aluminoxane reagent and borate reagent, and improving the form of the polymer are technical problems that should be urgently improved or solved in the industrial application process of such catalysts.

Summary of the Invention

Problems to be Solved by the Invention

[0006] One object of the present invention is to provide an olefin polymerization catalyst composition that improves the form of the polymer while reducing or avoiding the use of methylaluminoxane or borate reagent. Another object of the present invention is to provide a method for preparing the olefin polymerization catalyst composition. A further object of the present invention is to provide the use of the olefin polymerization catalyst composition in olefin polymerization.

Means for Solving the Problems

[0007] Embodiments of the present invention relate to an olefin polymerization catalyst composition, which comprises a main catalyst and a carrier. The carrier is fluorinated silica gel particles, and the main catalyst is a metallocene complex represented by the general formula (I).

[0008]

Chemical Formula

[0009] Here, M is a Group 3, 4, 5, or 6 transition metal element in the periodic table, including lanthanoid elements and actinide elements.

[0010] X may be the same as or different from each other, and is selected from a hydrogen element, a halogen, an alkyl group R, an alkoxy group OR, a mercapto group SR, a carboxyl group OCOR, an amine group NR2, a phosphino group PR2, -OR°O-, and OSO2CF3. R is a linear or branched alkyl group having C1-C 20 a saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group, or an alkyl group containing a heteroatom of an element from Group 13 to Group 17 in the periodic table, or a cycloalkyl group having C3-C 20 an aryl group having C6-C 30 an alkyl-substituted aryl group having C7-C 30 or an aryl-substituted alkyl group having C7-C 30 30 . R° is a divalent radical and includes an alkylene group having C2-C 40 an arylene group having C6-C 30 an alkyl-substituted arylene group having C7-C 40 or an aryl-substituted alkylene group having C7-C 40 40 . In the -OR°O- structure, the two oxygen atoms are at either position of the radical.

[0011] n is an integer from 1 to 4, and the total charge number of n Xs is the charge number of M - 2.

[0012] Q is a divalent radical and includes =CR'2, =SiR'2, =GeR'2, =NR', =PR', =BR'. Here, R' is a methyl group, an ethyl group, an isopropyl group, a trimethylsilyl group, a phenyl group, or a benzyl group.

[0013] A is a π-ligand and has a structure represented by Chemical Formula (II).

[0014]

Chemical formula

[0015] E is a divalent radical of a Group 16 or Group 15 element in the periodic table, including an oxygen radical, a sulfur radical, a selenium radical, NR", and PR", where R" is a C1-C 10 linear alkyl group, a phenyl group, a mono- or polysubstituted phenyl group, a benzyl group, a mono- or polysubstituted benzyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, or a 5-phenanthryl group.

[0016] L is a divalent radical having a structure represented by the following chemical formula (III), (IV), (V), (VI), (VII), or (VIII), where i is 2.

[0017]

Chemical formula

[0018] Z is a π-ligand, Z = A, or Z has a chemical structure represented by the following chemical formula (IX), (X), (XI), (XII), or (XIII).

[0019]

Chemical formula

[0020] Here, R 1 , R 12 are hydrogen, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a phenyl group, a benzyl group, a 2-furyl group, or a 2-thienyl group.

[0021] R 2 , R 3 and R 13 are each hydrogen, fluorine, or R, where R is a C1-C 20 linear or branched alkyl group, a saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group, or an alkyl group containing a heteroatom of a Group 13 to Group 17 element in the periodic table, or a C3-C 20 cycloalkyl group, a C6-C30 an aryl group, C7-C 30 an alkyl-substituted aryl group or C7-C 30 an aryl-substituted alkyl group.

[0022] R 4 is H, a methyl group, a trifluoromethyl group, an isopropyl group, a tert-butyl group, a phenyl group, a p-tert-butylphenyl group, a p-trimethylsilylphenyl group, a p-trifluoromethylphenyl group, a 3,5-dichloro-4-trimethylsilylphenyl group or a 2-naphthyl group.

[0023] R 5 is hydrogen, fluorine or a methyl group.

[0024] R 6 and R 7 are each hydrogen, fluorine or R, where R is a C1-C 20 linear or branched alkyl group, a saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group or an alkyl group containing a heteroatom of Group 13 to Group 17 elements in the periodic table, or a C3-C 20 cycloalkyl group, a C6-C 30 aryl group, a C7-C 30 alkyl-substituted aryl group or a C7-C 30 aryl-substituted alkyl group.

[0025] R 8 is a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or a phenyl group.

[0026] R 9 and R 9'is a phenyl group, a substituted phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, furan, thiophene, quinoline or pyrimidine, wherein the substituent in the substituted phenyl group is a cyano group, a nitro group, F, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a methoxy group, a tert-butyl group, a trifluoromethoxy group, Cl, a trifluoromethyl group, a carbonyl group or a trimethylsilyl group.

[0027] R 10 and R 10' are hydrogen, fluorine, chlorine, a methyl group, an ethyl group or a phenyl group.

[0028] R 11 and R 11' are hydrogen, fluorine, chlorine, an ester group, an alkoxy group, a thiol group, an amine group or a phosphino group.

[0029] Here, in the chemical structural formula (I), the monovalent anionic π-ligand of A has a chemical structure represented by the chemical formula (II)-Li + The chemical formula (II) contains a basic structure having a cyclopentadiene ring. The active hydrogen in the cyclopentadiene structure has electrophilic reactivity and can undergo an exchange reaction with a nucleophile to generate a compound represented by the chemical formula (II)-Li + and the basic reaction is as shown in the following reaction formula.

[0030]

Chemical formula

[0031] Here, the nucleophile in the reaction formula is an organolithium reagent LiR n wherein R n is a C1-C6 alkyl group or a C6-C 12 aryl group.

[0032] Here, in Chemical Formula (II), the symbol * is linked to a chemical bond, atom or radical, and indicates that a chemical single bond is formed between this point linked to * and a chemical bond, atom or radical of the same kind.

[0033] Here, X is chlorine, bromine, a C1-C 20 lower-carbon alkyl group or aryl group.

[0034] Specifically, in Chemical Formula (I),

[0035]

Chemical Formula

[0036] M is a Group 3, 4, 5 or 6 transition metal element in the periodic table, including lanthanoid elements and actinide elements. Among them, Group 3, 4 or lanthanoid element metal elements are preferred, and Group 4 zirconium, hafnium and titanium are most preferred.

[0037] X may be the same as or different from each other, and is selected from a hydrogen element, a halogen, an alkyl group R, an alkoxy group OR, a mercapto group SR, a carboxyl group OCOR, an amine group (NR2), a phosphino group (PR2), -OR°O- or OSO2CF3.

[0038] Here, R is a C1-C 20 linear or branched alkyl group, a saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group, an alkyl group selectively containing a heteroatom of Group 13 to Group 17 elements in the periodic table, or a C3-C 20 cycloalkyl group, a C6-C 30 aryl group, a C7-C 30 alkyl-substituted aryl group, a C7-C 30 aryl-substituted alkyl group. A C1-C 20Examples of saturated alkyl groups and halogenated alkyl groups include, but are not limited to, methyl group, trifluoromethyl group, ethyl group, 1,1,1-trifluoroethyl group, perfluoroethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-dodecyl group, n-octadecyl group, trimethylsilyl group, triethylsilyl group, triphenylsilyl group, etc. C1-C 20 Examples of unsaturated alkyl groups include, but are not limited to, vinyl group, propenyl group, allyl group, etc. C3-C 20 Examples of cycloalkyl groups include, but are not limited to, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, 1-adamantyl group, etc. C6-C 30 Examples of aryl groups of C7-C include, but are not limited to, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, etc. 30Examples of the alkyl-substituted aryl group include, but are not limited to, 2-methylphenyl group, 2,6-dimethylphenyl group, 2-fluoro-3-methylphenyl group, 2-fluoro-4-methylphenyl group, 2,6-difluoro-3-methylphenyl group, 2,6-difluoro-4-methylphenyl group, 2-chloro-3-methylphenyl group, 2-chloro-4-methylphenyl group, 2,6-dichloro-3-methylphenyl group, 2,6-dichloro-4-methylphenyl group, 2-ethylphenyl group, 2,6-diethylphenyl group, 2-isopropylphenyl group, 2,6-diisopropylphenyl group, 3-methylphenyl group, 3,5-dimethylphenyl group, 3-fluoro-4-methylphenyl group, 3,5-difluoro-4-methylphenyl group, 3,5-difluoro-4-ethylphenyl group, 3,5-difluoro-4-isopropylphenyl group, 3,5-difluoro-4-tert-butylphenyl group, 3,5-difluoro-4-trimethylsilylphenyl group, 3-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-methylphenyl group, 4-trifluoromethylphenyl group, 4-ethylphenyl group, 4-isopropylphenyl group, 4-tert-butylphenyl group, 4-trimethylsilylphenyl group, etc. C7-C 30 Examples of the aryl-substituted alkyl group of C7-C include, but are not limited to, benzyl group, p-methylbenzyl group, p-fluorobenzyl group, p-chlorobenzyl group, p-ethylbenzyl group, p-isopropylbenzyl group, p-tert-butylbenzyl group, p-trifluoromethylbenzyl group, p-trimethylsilylbenzyl group, 3,5-difluorobenzyl group, 3,4,5-trifluorobenzyl group, 3,5-bistrimethylbenzyl group, 3,5-bistrifluoromethylbenzyl group, phenethyl group, p-methylphenethyl group, p-fluorophenethyl group, p-chlorophenethyl group, p-isopropylphenethyl group, p-tert-butylphenethyl group, p-trimethylsilylphenethyl group, 2,6-difluorophenethyl group, 3,5-difluorophenethyl group, 3,4,5-trifluorophenethyl group, perfluorophenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, etc.

[0039] R° is a divalent radical such as an alkylene group of C2-C 40 an alkylene group of C6-C 30 an arylene group of C7-C 40 an alkyl-substituted arylene group of C7-C 40 an aryl-substituted alkylene group of C7-C. In the -OR°O- structure, the two oxygen atoms may be at any position of the radical, but the positions of the two oxygen atoms are preferably a combination of adjacent (α, β-position) and alternating (α, γ-position) positions of the radical. X is preferably a halogen such as chlorine and bromine, and a lower-carbon alkyl group and aryl group (for example, a methyl group, a phenyl group, a benzyl group, etc., but not limited thereto) in the above combination.

[0040] n is an integer from 1 to 4. The total charge number of n Xs is the charge number of M - 2.

[0041] Q is a divalent radical such as =CR'2, =SiR'2, =GeR'2, =NR', =PR', =BR'.

[0042] Here, R' is the same or different and is a straight-chain or branched alkyl group of C1-C 20 a saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group, an alkyl group selectively containing a heteroatom of Group 13 to Group 17 elements in the periodic table, or a cycloalkyl group of C3-C 20 an aryl group of C6-C 30 an alkyl-substituted aryl group of C7-C 30 an aryl-substituted alkyl group of C7-C 30 an aryl-substituted alkyl group of C7-C. C1-C 20Examples of saturated and halogenated alkyl groups include, but are not limited to, methyl group, trifluoromethyl group, ethyl group, 1,1,1-trifluoroethyl group, perfluoroethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-dodecyl group, n-octadecyl group, trimethylsilyl group, triethylsilyl group, triphenylsilyl group, etc. C1-C 20 Examples of unsaturated alkyl groups include, but are not limited to, vinyl group, propenyl group, allyl group, etc. C3-C 20 Examples of cycloalkyl groups include, but are not limited to, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, 1-adamantyl group, etc. C6-C 30 Examples of aryl groups of C7-C include, but are not limited to, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, etc. 30Examples of the alkyl-substituted aryl group include, but are not limited to, 2-methylphenyl group, 2,6-dimethylphenyl group, 2-fluoro-3-methylphenyl group, 2-fluoro-4-methylphenyl group, 2,6-difluoro-3-methylphenyl group, 2,6-difluoro-4-methylphenyl group, 2-chloro-3-methylphenyl group, 2-chloro-4-methylphenyl group, 2,6-dichloro-3-methylphenyl group, 2,6-dichloro-4-methylphenyl group, 2-ethylphenyl group, 2,6-diethylphenyl group, 2-isopropylphenyl group, 2,6-diisopropylphenyl group, 3-methylphenyl group, 3,5-dimethylphenyl group, 3-fluoro-4-methylphenyl group, 3,5-difluoro-4-methylphenyl group, 3,5-difluoro-4-ethylphenyl group, 3,5-difluoro-4-isopropylphenyl group, 3,5-difluoro-4-tert-butylphenyl group, 3,5-difluoro-4-trimethylsilylphenyl group, 3-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-methylphenyl group, 4-trifluoromethylphenyl group, 4-ethylphenyl group, 4-isopropylphenyl group, 4-tert-butylphenyl group, 4-trimethylsilylphenyl group, etc. C7-C 30 Examples of the aryl-substituted alkyl group of C7-C include, but are not limited to, benzyl group, p-methylbenzyl group, p-fluorobenzyl group, p-chlorobenzyl group, p-ethylbenzyl group, p-isopropylbenzyl group, p-tert-butylbenzyl group, p-trifluoromethylbenzyl group, p-trimethylsilylbenzyl group, 3,5-difluorobenzyl group, 3,4,5-trifluorobenzyl group, 3,5-bistrimethylbenzyl group, 3,5-bistrifluoromethylbenzyl group, phenethyl group, p-methylphenethyl group, p-fluorophenethyl group, p-chlorophenethyl group, p-isopropylphenethyl group, p-tert-butylphenethyl group, p-trimethylsilylphenethyl group, 2,6-difluorophenethyl group, 3,5-difluorophenethyl group, 3,4,5-trifluorophenethyl group, perfluorophenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, etc.

[0043] In the above combination, R' is preferably a methyl group, an ethyl group, an isopropyl group, a trimethylsilyl group, a phenyl group or a benzyl group. A is a π-ligand and has a general structure represented by Chemical Formula (II).

[0044]

Chemical formula

[0045] In General Formula (II), the symbol * represents that it may be linked to a chemical bond, an atom or a radical, and that point forms a single chemical bond with the same kind of chemical bond, atom or radical. Hereinafter, all symbols * have the same meaning.

[0046] E is a divalent radical of a Group 16 or Group 15 element in the periodic table such as an oxygen radical, a sulfur radical, an arsenic radical, NR", PR".

[0047] Here, R" is a linear or branched alkyl group of C1-C 20 a saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group, an alkyl group selectively containing a heteroatom of an element from Group 13 to Group 17 in the periodic table, or a cycloalkyl group of C3-C 20 an aryl group of C6-C 30 an alkyl-substituted aryl group of C7-C 30 an aryl-substituted alkyl group of C7-C 30 an aryl-substituted alkyl group of C7-C 20 Examples of saturated and halogenated alkyl groups include, but are not limited to, methyl group, trifluoromethyl group, ethyl group, 1,1,1-trifluoroethyl group, perfluoroethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-dodecyl group, n-octadecyl group, trimethylsilylmethyl group, triethylsilylmethyl group, triphenylsilylmethyl group, etc. C1-C 20Examples of the unsaturated alkyl group include, but are not limited to, vinyl group, propenyl group, allyl group, etc. C3-C 20 Examples of the cycloalkyl group include, but are not limited to, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, 1-adamantyl group, etc. C6-C 30 Examples of the aryl group of C7-C include, but are not limited to, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, etc. 30 Examples of the alkyl-substituted aryl group include, but are not limited to, 2-methylphenyl group, 2,6-dimethylphenyl group, 2-fluoro-3-methylphenyl group, 2-fluoro-4-methylphenyl group, 2,6-difluoro-3-methylphenyl group, 2,6-difluoro-4-methylphenyl group, 2-chloro-3-methylphenyl group, 2-chloro-4-methylphenyl group, 2,6-dichloro-3-methylphenyl group, 2,6-dichloro-4-methylphenyl group, 2-ethylphenyl group, 2,6-diethylphenyl group, 2-isopropylphenyl group, 2,6-diisopropylphenyl group, 3-methylphenyl group, 3,5-dimethylphenyl group, 3-fluoro-4-methylphenyl group, 3,5-difluoro-4-methylphenyl group, 3,5-difluoro-4-ethylphenyl group, 3,5-difluoro-4-isopropylphenyl group, 3,5-difluoro-4-tert-butylphenyl group, 3,5-difluoro-4-trimethylsilylphenyl group, 3-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-methylphenyl group, 4-trifluoromethylphenyl group, 4-ethylphenyl group, 4-isopropylphenyl group, 4-tert-butylphenyl group, 4-trimethylsilylphenyl group, etc. C7-C 30Examples of the aryl-substituted alkyl group include, but are not limited to, benzyl group, p-methylbenzyl group, p-fluorobenzyl group, p-chlorobenzyl group, p-ethylbenzyl group, p-isopropylbenzyl group, p-tert-butylbenzyl group, p-trifluoromethylbenzyl group, p-trimethylsilylbenzyl group, 3,5-difluorobenzyl group, 3,4,5-trifluorobenzyl group, 3,5-bistrimethylbenzyl group, 3,5-bistrifluoromethylbenzyl group, phenethyl group, p-methylphenethyl group, p-fluorophenethyl group, p-chlorophenethyl group, p-isopropylphenethyl group, p-tert-butylphenethyl group, p-trimethylsilylphenethyl group, 2,6-difluorophenethyl group, 3,5-difluorophenethyl group, 3,4,5-trifluorophenethyl group, perfluorophenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, etc.

[0048] In the above combination, R” is preferably a C4-C 10 linear alkyl group, phenyl group, mono- or polysubstituted phenyl group, benzyl group, mono- or polysubstituted benzyl group, 1-naphthyl group, 2-naphthyl group, 2-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 5-phenanthryl group. Hereinafter, all R”s have the same meaning.

[0049] E is preferably sulfur element, oxygen element, NR” and PR”. Here, R” is as defined above.

[0050] R 1 is any one of a C1-C 40 saturated or unsaturated alkyl group, halogenated or non-halogenated alkyl group, alkyl group selectively containing a heteroatom of Group 13 to Group 17 elements in the periodic table or a C3-C 40 cycloalkyl group, a C6-C 40 aryl group, a C7-C 40 alkyl-substituted aryl group, a C7-C 40 aryl-substituted alkyl group. C1-C 40Examples of saturated and halogenated alkyl groups include, but are not limited to, methyl group, trifluoromethyl group, ethyl group, 1,1,1-trifluoroethyl group, perfluoroethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-dodecyl group, n-octadecyl group, trimethylsilylmethyl group, triethylsilylmethyl group, triphenylsilylmethyl group, etc. C1-C 20 Examples of unsaturated alkyl groups include, but are not limited to, vinyl group, propenyl group, allyl group, etc. C3-C 40 Examples of cycloalkyl groups include, but are not limited to, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, 1-adamantyl group, etc. C6-C 40 Examples of aryl groups of C7-C include, but are not limited to, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, etc. C7-C 40Examples of the alkyl-substituted aryl group include, but are not limited to, 2-methylphenyl group, 2,6-dimethylphenyl group, 2-fluoro-3-methylphenyl group, 2-fluoro-4-methylphenyl group, 2,6-difluoro-3-methylphenyl group, 2,6-difluoro-4-methylphenyl group, 2-chloro-3-methylphenyl group, 2-chloro-4-methylphenyl group, 2,6-dichloro-3-methylphenyl group, 2,6-dichloro-4-methylphenyl group, 2-ethylphenyl group, 2,6-diethylphenyl group, 2-isopropylphenyl group, 2,6-diisopropylphenyl group, 3-methylphenyl group, 3,5-dimethylphenyl group, 3-fluoro-4-methylphenyl group, 3,5-difluoro-4-methylphenyl group, 3,5-difluoro-4-ethylphenyl group, 3,5-difluoro-4-isopropylphenyl group, 3,5-difluoro-4-tert-butylphenyl group, 3,5-difluoro-4-trimethylsilylphenyl group, 3-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-methylphenyl group, 4-trifluoromethylphenyl group, 4-ethylphenyl group, 4-isopropylphenyl group, 4-tert-butylphenyl group, 4-trimethylsilylphenyl group, etc. C7-C 40 Examples of the aryl-substituted alkyl group of C7-C 40 include, but are not limited to, benzyl group, p-methylbenzyl group, p-fluorobenzyl group, p-chlorobenzyl group, p-ethylbenzyl group, p-isopropylbenzyl group, p-tert-butylbenzyl group, p-trifluoromethylbenzyl group, p-trimethylsilylbenzyl group, 3,5-difluorobenzyl group, 3,4,5-trifluorobenzyl group, 3,5-bistrimethylbenzyl group, 3,5-bistrifluoromethylbenzyl group, phenethyl group, p-methylphenethyl group, p-fluorophenethyl group, p-chlorophenethyl group, p-isopropylphenethyl group, p-tert-butylphenethyl group, p-trimethylsilylphenethyl group, 2,6-difluorophenethyl group, 3,5-difluorophenethyl group, 3,4,5-trifluorophenethyl group, perfluorophenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, etc.

[0051] R 1 is preferably hydrogen, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a phenyl group, a benzyl group, a 2-furyl group, or a 2-thienyl group. Hereinafter, all Rs 1 are synonymous.

[0052] R 2 and R 3 are hydrogen, fluorine, or R. R is as defined above. R 2 and R 3 are preferably hydrogen. Hereinafter, all Rs 2 and R 3 are synonymous.

[0053] R 4 is a C1-C 40 saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group, an alkyl group selectively containing a heteroatom of Group 13 to Group 17 elements in the periodic table, or a C3-C 40 cycloalkyl group, a C6-C 40 aryl group, a C7-C 40 alkyl-substituted aryl group, or a C7-C 40 aryl-substituted alkyl group. Examples of the C1-C 40 saturated and halogenated alkyl groups include, but are not limited to, a methyl group, a trifluoromethyl group, an ethyl group, a 1,1,1-trifluoroethyl group, a perfluoroethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-dodecyl group, an n-octadecyl group, a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, etc. Examples of the C1-C 20 unsaturated alkyl groups include, but are not limited to, a vinyl group, a propenyl group, a propyl group, etc. Examples of the C3-C 40Examples of the cycloalkyl group include, but are not limited to, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, 1-adamantyl group, etc. C6-C 40 Examples of the C6-C14 aryl group include, but are not limited to, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, etc. C7-C 40 Examples of the alkyl-substituted aryl group include, but are not limited to, 2-methylphenyl group, 2,6-dimethylphenyl group, 2-fluoro-3-methylphenyl group, 2-fluoro-4-methylphenyl group, 2,6-difluoro-3-methylphenyl group, 2,6-difluoro-4-methylphenyl group, 2-chloro-3-methylphenyl group, 2-chloro-4-methylphenyl group, 2,6-dichloro-3-methylphenyl group, 2,6-dichloro-4-methylphenyl group, 2-ethylphenyl group, 2,6-diethylphenyl group, 2-isopropylphenyl group, 2,6-diisopropylphenyl group, 3-methylphenyl group, 3,5-dimethylphenyl group, 3-fluoro-4-methylphenyl group, 3,5-difluoro-4-methylphenyl group, 3,5-difluoro-4-ethylphenyl group, 3,5-difluoro-4-isopropylphenyl group, 3,5-difluoro-4-tert-butylphenyl group, 3,5-difluoro-4-trimethylsilylphenyl group, 3-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-methylphenyl group, 4-trifluoromethylphenyl group, 4-ethylphenyl group, 4-isopropylphenyl group, 4-tert-butylphenyl group, 4-trimethylsilylphenyl group, etc. C7-C 40Examples of the aryl-substituted alkyl group include, but are not limited to, benzyl group, p-methylbenzyl group, p-fluorobenzyl group, p-chlorobenzyl group, p-ethylbenzyl group, p-isopropylbenzyl group, p-tert-butylbenzyl group, p-trifluoromethylbenzyl group, p-trimethylsilylbenzyl group, 3,5-difluorobenzyl group, 3,4,5-trifluorobenzyl group, 3,5-bistrimethylsilylbenzyl group, 3,5-bistrifluoromethylbenzyl group, phenethyl group, p-methylphenethyl group, p-fluorophenethyl group, p-chlorophenethyl group, p-isopropylphenethyl group, p-tert-butylphenethyl group, p-trimethylsilylphenethyl group, 2,6-difluorophenethyl group, 3,5-difluorophenethyl group, 3,4,5-trifluorophenethyl group, perfluorophenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, etc.

[0054] R 4 is preferably H, methyl group, trifluoromethyl group, isopropyl group, tert-butyl group, phenyl group, p-tert-butylphenyl group, p-trimethylsilylphenyl group, p-trifluoromethylphenyl group, 3,5-dichloro-4-trimethylsilylphenyl group, 2-naphthyl group. And hereinafter, all Rs 4 are synonymous.

[0055] L is a divalent radical and has a structure of any one of the following general formulas (III), (IV), (V), (VI), (VII), (VIII).

[0056]

Chemical formula

[0057] The symbol * represents that even when it is linked to a chemical bond, atom or radical, that point forms a single chemical bond with the same kind of chemical bond, atom or radical. In the following, all symbols * are synonymous.

[0058] In general formulas (III) and (IV), i is an integer, i is not zero, and i is preferably 2.

[0059] R 5 are the same or different and are a C1-C 40 saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group, an alkyl group selectively containing a heteroatom of an element from Group 13 to Group 17 in the periodic table, and a C3-C 40 cycloalkyl group, a C6-C 40 aryl group, a C7-C 40 alkyl-substituted aryl group, a C7-C 40 aryl-substituted alkyl group, or any of these. Examples of C1-C 40 saturated and halogenated alkyl groups include, but are not limited to, methyl group, trifluoromethyl group, ethyl group, 1,1,1-trifluoroethyl group, perfluoroethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-dodecyl group, n-octadecyl group, trimethylsilyl group, triethylsilyl group, triphenylsilyl group, etc. Examples of C1-C 20 unsaturated alkyl groups include, but are not limited to, vinyl group, propenyl group, allyl group, etc. Examples of C3-C 40 cycloalkyl groups include, but are not limited to, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, 1-adamantyl group, etc. Examples of C6-C 40 aryl groups include, but are not limited to, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, etc. Examples of C7-C 40Examples of the alkyl-substituted aryl group include, but are not limited to, 2-methylphenyl group, 2,6-dimethylphenyl group, 2-fluoro-3-methylphenyl group, 2-fluoro-4-methylphenyl group, 2,6-difluoro-3-methylphenyl group, 2,6-difluoro-4-methylphenyl group, 2-chloro-3-methylphenyl group, 2-chloro-4-methylphenyl group, 2,6-dichloro-3-methylphenyl group, 2,6-dichloro-4-methylphenyl group, 2-ethylphenyl group, 2,6-diethylphenyl group, 2-isopropylphenyl group, 2,6-diisopropylphenyl group, 3-methylphenyl group, 3,5-dimethylphenyl group, 3-fluoro-4-methylphenyl group, 3,5-difluoro-4-methylphenyl group, 3,5-difluoro-4-ethylphenyl group, 3,5-difluoro-4-isopropylphenyl group, 3,5-difluoro-4-tert-butylphenyl group, 3,5-difluoro-4-trimethylsilylphenyl group, 3-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-methylphenyl group, 4-trifluoromethylphenyl group, 4-ethylphenyl group, 4-isopropylphenyl group, 4-tert-butylphenyl group, 4-trimethylsilylphenyl group, etc. C7-C 40 Examples of the aryl-substituted alkyl group of C7-C include, but are not limited to, benzyl group, p-methylbenzyl group, p-fluorobenzyl group, p-chlorobenzyl group, p-ethylbenzyl group, p-isopropylbenzyl group, p-tert-butylbenzyl group, p-trifluoromethylbenzyl group, p-trimethylsilylbenzyl group, 3,5-difluorobenzyl group, 3,4,5-trifluorobenzyl group, 3,5-bistrimethylsilylbenzyl group, 3,5-bistrifluoromethylbenzyl group, phenethyl group, p-methylphenethyl group, p-fluorophenethyl group, p-chlorophenethyl group, p-isopropylphenethyl group, p-tert-butylphenethyl group, p-trimethylsilylphenethyl group, 2,6-difluorophenethyl group, 3,5-difluorophenethyl group, 3,4,5-trifluorophenethyl group, perfluorophenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, etc.

[0060] R 5 is preferably hydrogen, fluorine, or a methyl group. Hereinafter, all Rs 5 are synonymous.

[0061] In general formulas (V), (VI), (VII), and (VIII), R 6 and R 7 are R 3 R 3 is as defined above. R 6 and R 7 are preferably hydrogen and fluorine elements. Hereinafter, all Rs 6 and R 7 are synonymous.

[0062] In general formula (I), Z is a π-ligand. Z = A, and A is as described above. Or, Z has a chemical structure represented by the following general formulas (IX), (X), (XI), (XII), (XIII), (XIV), and (XV).

[0063]

Chemical formula

[0064] The symbol * indicates that even when it is linked to a chemical bond, atom, or radical, that point forms a single chemical bond with the same kind of chemical bond, atom, or radical. Hereinafter, all symbols * are synonymous.

[0065] In the above general formulas (IX), (X), (XI), (XII), and (XIII),

[0066] R 1 is as defined above.

[0067] R 1 is preferably a methyl group, ethyl group, isopropyl group, tert-butyl group, phenyl group, benzyl group, 2-furyl group, or 2-thienyl group.

[0068] R2 is hydrogen, fluorine, R. R is as defined above. R 2 is preferably hydrogen.

[0069] R 8 are the same or different, C1-C 40 saturated or unsaturated alkyl group, halogenated or non-halogenated alkyl group, alkyl group selectively containing heteroatoms of elements from Group 13 to Group 17 in the periodic table, and C3-C 40 cycloalkyl group, C6-C 40 aryl group, C7-C 40 alkyl-substituted aryl group, C7-C 40 aryl-substituted alkyl group, any of C7-C 40 Examples of saturated and halogenated alkyl groups include, but are not limited to, methyl group, trifluoromethyl group, ethyl group, 1,1,1-trifluoroethyl group, perfluoroethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-dodecyl group, n-octadecyl group, trimethylsilyl group, triethylsilyl group, triphenylsilyl group, etc. C1-C 20 Examples of unsaturated alkyl groups include, but are not limited to, vinyl group, propenyl group, allyl group, etc. C3-C 40 Examples of cycloalkyl groups include, but are not limited to, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, 1-adamantyl group, etc. C6-C 40 Examples of aryl groups of C6-C include, but are not limited to, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, etc. C7-C 40Examples of the alkyl-substituted aryl group include, but are not limited to, 2-methylphenyl group, 2,6-dimethylphenyl group, 2-fluoro-3-methylphenyl group, 2-fluoro-4-methylphenyl group, 2,6-difluoro-3-methylphenyl group, 2,6-difluoro-4-methylphenyl group, 2-chloro-3-methylphenyl group, 2-chloro-4-methylphenyl group, 2,6-dichloro-3-methylphenyl group, 2,6-dichloro-4-methylphenyl group, 2-ethylphenyl group, 2,6-diethylphenyl group, 2-isopropylphenyl group, 2,6-diisopropylphenyl group, 3-methylphenyl group, 3,5-dimethylphenyl group, 3-fluoro-4-methylphenyl group, 3,5-difluoro-4-methylphenyl group, 3,5-difluoro-4-ethylphenyl group, 3,5-difluoro-4-isopropylphenyl group, 3,5-difluoro-4-tert-butylphenyl group, 3,5-difluoro-4-trimethylsilylphenyl group, 3-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-methylphenyl group, 4-trifluoromethylphenyl group, 4-ethylphenyl group, 4-isopropylphenyl group, 4-tert-butylphenyl group, 4-trimethylsilylphenyl group, etc. C7-C 40 Examples of the aryl-substituted alkyl group of C7-C 40 include, but are not limited to, benzyl group, p-methylbenzyl group, p-fluorobenzyl group, p-chlorobenzyl group, p-ethylbenzyl group, p-isopropylbenzyl group, p-tert-butylbenzyl group, p-trifluoromethylbenzyl group, p-trimethylsilylbenzyl group, 3,5-difluorobenzyl group, 3,4,5-trifluorobenzyl group, 3,5-bistrimethylsilylbenzyl group, 3,5-bistrifluoromethylbenzyl group, phenethyl group, p-methylphenethyl group, p-fluorophenethyl group, p-chlorophenethyl group, p-isopropylphenethyl group, p-tert-butylphenethyl group, p-trimethylsilylphenethyl group, 2,6-difluorophenethyl group, 3,5-difluorophenethyl group, 3,4,5-trifluorophenethyl group, perfluorophenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, etc.

[0070] R 8 is preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a phenyl group. Hereinafter, all Rs 8 are synonymous.

[0071] R 9 are the same or different and are each independently a C1-C 40 saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group, an alkyl group selectively containing a heteroatom of an element from Group 13 to Group 17 in the periodic table, and a C3-C 40 cycloalkyl group, a C6-C 40 aryl group, a C7-C 40 alkyl-substituted aryl group, or a C7-C 40 aryl-substituted alkyl group. Examples of the C1-C 40 saturated and halogenated alkyl groups include, but are not limited to, a methyl group, a trifluoromethyl group, an ethyl group, a 1,1,1-trifluoroethyl group, a perfluoroethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-dodecyl group, an n-octadecyl group, a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, and the like. Examples of the C1-C 20 unsaturated alkyl groups include, but are not limited to, a vinyl group, a propenyl group, an allyl group, and the like. Examples of the C3-C 40 cycloalkyl groups include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a 1-adamantyl group, and the like. Examples of the C6-C 40 aryl groups include, but are not limited to, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, and the like. Examples of the C7-C 40Examples of alkyl-substituted aryl groups include, but are not limited to, 2-methylphenyl group, 2,6-dimethylphenyl group, 2-fluoro-3-methylphenyl group, 2-fluoro-4-methylphenyl group, 2,6-difluoro-3-methylphenyl group, 2,6-difluoro-4-methylphenyl group, 2-chloro-3-methylphenyl group, 2-chloro-4-methylphenyl group, 2,6-dichloro-3-methylphenyl group, 2,6-dichloro-4-methylphenyl group, 2-ethylphenyl group, 2,6-diethylphenyl group, 2-isopropylphenyl group, 2,6-diisopropylphenyl group, 3-methylphenyl group, 3,5-dimethylphenyl group, 3-fluoro-4-methylphenyl group, 3,5-difluoro-4-methylphenyl group, 3,5-difluoro-4-ethylphenyl group, 3,5-difluoro-4-isopropylphenyl group, 3,5-difluoro-4-tert-butylphenyl group, 3,5-difluoro-4-trimethylsilylphenyl group, 3-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-methylphenyl group, 4-trifluoromethylphenyl group, 4-ethylphenyl group, 4-isopropylphenyl group, 4-tert-butylphenyl group, 4-trimethylsilylphenyl group, etc. C7-C 40 Examples of aryl-substituted alkyl groups include, but are not limited to, benzyl group, p-methylbenzyl group, p-fluorobenzyl group, p-chlorobenzyl group, p-ethylbenzyl group, p-isopropylbenzyl group, p-tert-butylbenzyl group, p-trifluoromethylbenzyl group, p-trimethylsilylbenzyl group, 3,5-difluorobenzyl group, 3,4,5-trifluorobenzyl group, 3,5-bistrimethylsilylbenzyl group, 3,5-bistrifluoromethylbenzyl group, phenethyl group, p-methylphenethyl group, p-fluorophenethyl group, p-chlorophenethyl group, p-isopropylphenethyl group, p-tert-butylphenethyl group, p-trimethylsilylphenethyl group, 2,6-difluorophenethyl group, 3,5-difluorophenethyl group, 3,4,5-trifluorophenethyl group, perfluorophenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, etc.

[0072] R 9 is preferably a linear or branched carbon radical, a saturated or unsaturated carbon radical, a carbon radical partially or fully halogenated, or a linear or cyclic carbon radical. Hereinafter, all Rs 20 are synonymous. 9

[0073] R 10 are the same or different and are any of a C1-C 40 saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group, an alkyl group selectively containing a heteroatom of Group 13 to Group 17 elements in the periodic table, and a C3-C 40 cycloalkyl group, a C6-C 40 aryl group, a C7-C 40 alkyl-substituted aryl group, a C7-C 40 aryl-substituted alkyl group. Examples of C1-C 40 saturated and halogenated alkyl groups include, but are not limited to, methyl group, trifluoromethyl group, ethyl group, 1,1,1-trifluoroethyl group, perfluoroethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-dodecyl group, n-octadecyl group, trimethylsilyl group, triethylsilyl group, triphenylsilyl group, etc. Examples of C1-C 20 unsaturated alkyl groups include, but are not limited to, vinyl group, propenyl group, allyl group, etc. Examples of C3-C 40 cycloalkyl groups include, but are not limited to, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, 1-adamantyl group, etc. Examples of C6-C 40 ​Examples of the aryl group include, but are not limited to, a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, etc. C7-C 40 Examples of the alkyl-substituted aryl group include, but are not limited to, 2-methylphenyl group, 2,6-dimethylphenyl group, 2-fluoro-3-methylphenyl group, 2-fluoro-4-methylphenyl group, 2,6-difluoro-3-methylphenyl group, 2,6-difluoro-4-methylphenyl group, 2-chloro-3-methylphenyl group, 2-chloro-4-methylphenyl group, 2,6-dichloro-3-methylphenyl group, 2,6-dichloro-4-methylphenyl group, 2-ethylphenyl group, 2,6-diethylphenyl group, 2-isopropylphenyl group, 2,6-diisopropylphenyl group, 3-methylphenyl group, 3,5-dimethylphenyl group, 3-fluoro-4-methylphenyl group, 3,5-difluoro-4-methylphenyl group, 3,5-difluoro-4-ethylphenyl group, 3,5-difluoro-4-isopropylphenyl group, 3,5-difluoro-4-tert-butylphenyl group, 3,5-difluoro-4-trimethylsilylphenyl group, 3-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-methylphenyl group, 4-trifluoromethylphenyl group, 4-ethylphenyl group, 4-isopropylphenyl group, 4-tert-butylphenyl group, 4-trimethylsilylphenyl group, etc. C7-C 40Examples of the aryl-substituted alkyl group include, but are not limited to, benzyl group, p-methylbenzyl group, p-fluorobenzyl group, p-chlorobenzyl group, p-ethylbenzyl group, p-isopropylbenzyl group, p-tert-butylbenzyl group, p-trifluoromethylbenzyl group, p-trimethylsilylbenzyl group, 3,5-difluorobenzyl group, 3,4,5-trifluorobenzyl group, 3,5-bistrimethylsilylbenzyl group, 3,5-bistrifluoromethylbenzyl group, phenethyl group, p-methylphenethyl group, p-fluorophenethyl group, p-chlorophenethyl group, p-isopropylphenethyl group, p-tert-butylphenethyl group, p-trimethylsilylphenethyl group, 2,6-difluorophenethyl group, 3,5-difluorophenethyl group, 3,4,5-trifluorophenethyl group, perfluorophenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, etc.

[0074] R 10 is preferably hydrogen, fluorine, chlorine, methyl group, ethyl group, or phenyl group. Hereinafter, all Rs 10 are synonymous.

[0075] R 11 are the same or different and are each independently hydrogen, fluorine, chlorine, bromine, OR, SR, OCOR, NR2, or PR2. Here, R is as described above. Or, Rs 11 are the same or different and are each independently a C1-C 40 saturated or unsaturated alkyl group, halogenated or non-halogenated alkyl group, alkyl group selectively containing a heteroatom of Group 13 to Group 17 elements in the periodic table, and a C3-C 40 cycloalkyl group, a C6-C 40 aryl group, a C7-C 40 alkyl-substituted aryl group, a C7-C 40 aryl-substituted alkyl group. C1-C 40Examples of saturated and halogenated alkyl groups include, but are not limited to, methyl group, trifluoromethyl group, ethyl group, 1,1,1-trifluoroethyl group, perfluoroethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-dodecyl group, n-octadecyl group, trimethylsilyl group, triethylsilyl group, triphenylsilyl group, etc. C1-C 20 Examples of unsaturated alkyl groups include, but are not limited to, vinyl group, propenyl group, allyl group, etc. C3-C 40 Examples of cycloalkyl groups include, but are not limited to, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, 1-adamantyl group, etc. C6-C 40 Examples of aryl groups of C7-C include, but are not limited to, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, etc. C7-C 40Examples of the alkyl-substituted aryl group include, but are not limited to, 2-methylphenyl group, 2,6-dimethylphenyl group, 2-fluoro-3-methylphenyl group, 2-fluoro-4-methylphenyl group, 2,6-difluoro-3-methylphenyl group, 2,6-difluoro-4-methylphenyl group, 2-chloro-3-methylphenyl group, 2-chloro-4-methylphenyl group, 2,6-dichloro-3-methylphenyl group, 2,6-dichloro-4-methylphenyl group, 2-ethylphenyl group, 2,6-diethylphenyl group, 2-isopropylphenyl group, 2,6-diisopropylphenyl group, 3-methylphenyl group, 3,5-dimethylphenyl group, 3-fluoro-4-methylphenyl group, 3,5-difluoro-4-methylphenyl group, 3,5-difluoro-4-ethylphenyl group, 3,5-difluoro-4-isopropylphenyl group, 3,5-difluoro-4-tert-butylphenyl group, 3,5-difluoro-4-trimethylsilylphenyl group, 3-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-methylphenyl group, 4-trifluoromethylphenyl group, 4-ethylphenyl group, 4-isopropylphenyl group, 4-tert-butylphenyl group, 4-trimethylsilylphenyl group, etc. C7-C 40 Examples of the aryl-substituted alkyl group of C7-C 40 include, but are not limited to, benzyl group, p-methylbenzyl group, p-fluorobenzyl group, p-chlorobenzyl group, p-ethylbenzyl group, p-isopropylbenzyl group, p-tert-butylbenzyl group, p-trifluoromethylbenzyl group, p-trimethylsilylbenzyl group, 3,5-difluorobenzyl group, 3,4,5-trifluorobenzyl group, 3,5-bistrimethylsilylbenzyl group, 3,5-bistrifluoromethylbenzyl group, phenethyl group, p-methylphenethyl group, p-fluorophenethyl group, p-chlorophenethyl group, p-isopropylphenethyl group, p-tert-butylphenethyl group, p-trimethylsilylphenethyl group, 2,6-difluorophenethyl group, 3,5-difluorophenethyl group, 3,4,5-trifluorophenethyl group, perfluorophenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, etc.

[0076] R 11 is preferably hydrogen, fluorine, chlorine, an ester group, an alkoxy group, a thiol group, an amine group, or a phosphino group. Hereinafter, all Rs 11 are synonymous.

[0077] In the general chemical structural formula (I), A is a monovalent anionic π-ligand. Also, the precursor of A is a neutral stable organic compound and has a chemical structure represented by the general formula (II).

[0078]

Chemical formula

[0079] In the general formula (II), R 1 , R 2 , R 3 , R 4 , L, and E are as defined above. The general formula (II) includes a basic structure composed of a cyclopentadiene ring. The active hydrogen in the cyclopentadiene structure has unique electrophilic reactivity and can undergo an exchange reaction with nucleophiles such as Grignard reagents and organolithium reagents. The basic reaction is as shown in the following reaction formula.

[0080]

Chemical formula

[0081] In the above reaction formula, the nucleophile is selected with the organolithium reagent R n Li as a special case, but in practice, it is not limited to using only organolithium reagents. R n is a C1-C6 alkyl group or a C6-C 12 aryl group.

[0082] Examples of the present invention relate to a method for synthesizing a metallocene complex represented by the general formula (I) and include the following.

[0083]

Chemical formula

[0084] Here, T is the same as or different from each other, and the T is a monodentate or bidentate neutral ligand.

[0085] LG is a leaving group, which is the same as or different from each other, and the LG is hydrogen, an alkali metal element or an organic radical of a heavy element of Group 14.

[0086] Here, the monodentate ligand includes ethers ROR, sulfides RSR, tertiary amines NR3, tertiary phosphines PR3, cyclic ethers, cyclic sulfides, ketones, substituted cyclic ketones, substituted pyridines, substituted pyrroles, substituted piperidines, esters, lactones, amides and lactams. Here, R is a linear or branched alkyl group of C1-C 20 , a saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group or an alkyl group containing a heteroatom of an element from Group 13 to Group 17 in the periodic table, or a cycloalkyl group of C3-C 20 an aryl group of C6-C 30 an alkyl-substituted aryl group of C7-C 30 or an aryl-substituted alkyl group of C7-C 30

[0087] Here, the bidentate ligand includes ortho-diethers, α,ω-diethers, ortho-diamines, α,ω-diamines, ortho-disulfides, α,ω-disulfides, ortho-diphosphines and α,ω-diphosphines. Here, x is an integer such as 0 or 1, 2 or 3.

[0088] Here, the alkali metal elements include lithium, sodium and potassium. The organic radicals of the heavy elements of Group 14 include SiR3, GeR3, SnR3, PdR3, ZnR, BaR, MgR and CaR. Here, R is a linear or branched alkyl group of C1-C 20 ​a linear or branched alkyl group, a saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group, or an alkyl group containing a heteroatom of Group 13 to Group 17 elements in the periodic table, or C3-C 20 a cycloalkyl group of C6-C 30 an aryl group of C7-C 30 an alkyl-substituted aryl group of C7-C 30 or an aryl-substituted alkyl group of C7-C

[0089] Here, the reaction medium in the synthesis process is a saturated C5-C 15 alkane, cycloalkane or a mixture of two or more of them.

[0090] Here, the reaction medium in the synthesis process is hexane, heptane, octane, toluene or xylene. Here, the reaction temperature range is -100 °C to +300 °C.

[0091] Here, the reaction temperature range is -75 °C to +250 °C.

[0092] Here, the reaction temperature range is -50 °C to +150 °C.

[0093] The present invention relates to a method for preparing a fluorinated silica gel carrier obtained by reacting silica gel with a fluoride and then heating in an oxygen and argon atmosphere.

[0094] Alternatively, the fluorinated silica gel carrier is obtained by reacting silica gel with a fluoride and a fatty alcohol and then heating in an oxygen and argon atmosphere.

[0095] Among them, in one preferred form, the fluorinated silica gel carrier is obtained by reacting silica gel with a fluoride and phenol and then heating in an oxygen and argon atmosphere.

[0096] Specifically, the method for preparing the fluorinated silica gel support involves dispersing silica gel dehydrated at a dispersion temperature of -30°C to 120°C in an organic solvent, contacting it with a fluoride (or a fluoride and a fatty alcohol) at this temperature for 0.5 to 10 hours, filtering the solid, washing it with the organic solvent, drying it, then heating it at 200°C to 500°C for 1 to 6 hours in an oxygen atmosphere, and further heating it at 200°C to 500°C for 1 to 6 hours in an argon atmosphere, and then obtaining the support.

[0097] Here, the dehydration was carried out under the conditions of 200°C to 700°C and vacuum suction.

[0098] Here, the organic solvent is toluene, hexane, or heptane.

[0099] Here, the fluoride is dialkylaluminum fluoride, preferably diethylaluminum fluoride, diisopropylaluminum fluoride, or dibutylaluminum fluoride.

[0100] Here, the charging ratio of the fluoride to the silica gel is 1 to 100 mmol / g.

[0101] Here, the weight / mole ratio of the support to the metallocene complex is 1 to 50 kg / mol.

[0102] Examples of the present invention relate to a method for preparing the catalyst composition, which includes mixing and reacting a main catalyst and a fluorinated silica gel support in a homogeneous liquid medium. The homogeneous liquid medium includes a saturated alkane liquid medium containing pentane and its isomers, hexane and its isomers, heptane and its isomers, and octane and its isomers, and an aromatic liquid medium containing benzene, toluene, xylene and isomers, trimethylbenzene and isomers, chlorobenzene, dichlorobenzene and isomers, fluorobenzene, difluorobenzene and isomers, and polyfluorobenzene and isomers.

[0103] Embodiments of the present invention also relate to an olefin polymerization catalyst composition containing a Lewis acidic substance LA in addition to the main catalyst and the fluorinated silica gel carrier.

[0104] Here, LA is a polymethylaluminoxane or a modified polymethylaluminoxane or an organoboron reagent having a chain, cyclic and cage structure equilibrium state simultaneously in solution.

[0105] LA is a bulky, electron delocalized, poorly coordinating Lewis acidic substance. Typical examples of such substances are polymethylaluminoxane (PMAO) having a chain, cyclic and cage structure equilibrium state simultaneously in solution and polymethylaluminoxane (MMAO) obtained by modifying the same.

[0106] [Chemical formula]

[0107] Many examples can be given as the bulky, electron delocalized, poorly coordinating anions described in the present invention. For example, [B(C6H5)4] - , [(CH3)B(C6F5)3] - , [B(C6F5)4] - , [B(2,6-(CH3)2-C6H3)4] - , [B(2,4,6-(CH3)3-C6H2)4] - , [B(2,3,5,6-(CH3)4-C6H)4] - , [B(2,6-(CF3)2-C6H3)4] - , [B(2,4,6-(CF3)3-C6H2)4] - , [B(2,3,5,6-(CF3)4-C6H)4] - , [B(3,5-(CH3)2-C6H3)4] - , [B(3,4,5-(CH3)3-C6H2)4] - , [B(3,5-(CF3)2-C6H3)4] - , [B(3,4,5-(CF3)3-C6H2)4] - , [B(2,6-(CF3)2-C6F3)4]- , [B(2,4,6-(CF3)3-C6F2)4] - , [B(2,3,5,6-(CF3)4-C6F)4] - , [B(3,5-(CF3)2-C6F3)4] - , [B(3,4,5-(CF3)3-C6F2)4] - , [Al(C6H5)4] - , [(CH3)Al(C6F5)3] - , [Al(C6F5)4] - , [Al(2,6-(CH3)2-C6H3)4] - , [Al(2,4,6-(CH3)3-C6H2)4] - , [Al(2,3,5,6-(CH3)4-C6H)4] - , [Al(3,5-(CH3)2-C6H3)4] - , [Al(3,4,5-(CH3)3-C6H2)4] - , [Al(2,6-(CH3)2-C6F3)4] - , [Al(2,4,6-(CH3)3-C6F2)4] - , [Al(2,3,5,6-(CH3)4-C6F)4] - , [Al(3,5-(CH3)2-C6F3)4] - , [Al(3,4,5-(CH3)3-C6F2)4] - , [Al(2,6-(CF3)2-C6H3)4] - , [Al(2,4,6-(CF3)3-C6H2)4] - , [Al(2,3,5,6-(CF3)4-C6H)4] - , [Al(3,5-(CF3)2-C6H3)4] - , [Al(3,4,5-(CF3)3-C6H2)4] - , [Al(2,6-(CF3)2-C6F3)4] - , [Al(2,4,6-(CF3)3-C6F2)4] - , [Al(2,3,5,6-(CF3)4-C6F)4] - , [Al(3,5-(CF3)2-C6F3)4] - , [Al(3,4,5-(CF3)3-C6F2)4] -, [t-Bu-CH=C[B(C6F5)2]2(CH3)] - , [Ph-CH=C[B(C6F5)2]2(CH3)] - , [(C6F5)-CH=C[B(C6F5)2]2(CH3)] - , [t-Bu-CH=C[Al(C6F5)2]2(CH3)] - , [Ph-CH=C[Al(C6F5)2]2(CH3)] - , [(C6F5)-CH=C[Al(C6F5)2]2(CH3)] - , [1,1'-C 12 F8-2,2'=B(C6F5)2] - , [1,1'-C 12 F8-2,2'=Al(C6F5)2] - , [FB(1-C6F4-2-C6F5)3] - , [(CH3)B(1-C6F4-2-C6F5)3] - , [(C6F5)B(1-C6F4-2-C6F5)3] - , [(C6F5)Al(1-C6F4-2-C6F5)3] - , [FAl(1-C6F4-2-C6F5)3]-, [(CH3)Al(1-C6F4-2-C6F5)3]-,] - , [HB(1-C6F4-2-C6F5)3] - , [HAl(1-C6F4-2-C6F5)3] - , [(CH3)B(2-C 10 F7)3] - , [(CH3)Al(2-C 10 F7)3] - , [(CH3)B(p-C6F4SiMe3)3] - , [B(p-C6F4SiMe3)4] - , [(CH3)B(p-C6F4Si(n-Bu)3)3] - , [B(p-C6F4Si(n-Bu)3)4] - , [(CH3)B(p-C6F4Si(i-Bu)3)3] - , [B(p-C6F4Si(i-Bu)3)4] - , [(CH3)B(p-C6F4Si(t-Bu)3)3] -, [B(p-C6F4Si(t-Bu)3)4] - , [(C6F5)3B-C6F4-B(C6F5)2] - , [C6F4-1,2-(B(C6F5)3)2] - , [C6F4-1,2-(Al(C6F5)3)2] - , [(C6F4)-1,2-(B(C6F5)2)2-1',2'-(C6F4)] - , [(C6F4)-1,2-(Al(C6F5)2)2-1',2'-(C6F4)] - , [(C6F5)3B-CN-B(C6F5)3] - , [(C6F5)3Al-CN-Al(C6F5)3] - , [((C6F5)3BNC)4Ni] - , [((C6F5)3AlNC)4Ni] - , [(1,1'-C 12 F8)2-2,2'-B] - , [(1,1'-C 12 F8)2-2,2'-Al] - , [B(O-C6F5)4] - , [Al(O-C6F5)4] - , [(C6F5)3Al-C6F4-Al(C6F5)2] - , [(CH3)Al(p-C6F4SiMe3)3] - , [Al(p-C6F4SiMe3)4] - , [(CH3)Al(p-C6F4Si(n-Bu)3)3] - , [Al(p-C6F4Si(n-Bu)3)4] - , [(CH3)Al(p-C6F4Si(i-Bu)3)3] - , [Al(p-C6F4Si(i-Bu)3)4] - , [(CH3)Al(p-C6F4Si(t-Bu)3)3] - , [Al(p-C6F4Si(t-Bu)3)4] - , [C5(C6H5)5] - , [C5(2,6-(CH3)2-C6H3)5] - , [C5(2,4,6-(CH3)3-C6H2)5] - , [C5(3,5-(CH3)2-C6H3)5]- 、 [C5(3,4,5-(CH3)3-C6H2)5] - 、 [C5(2,6-(CF3)2-C6H3)5] - 、 [C5(2,4,6-(CF3)3-C6H2)5] - 、 [C5(3,5-(CF3)2-C6H3)5] - 、 [C5(3,4,5-(CF3)3-C6H2)5] - 、 [C5(2,6-(CH3)2-C6F3)5] - 、 [C5(2,4,6-(CH3)3-C6F2)5] - 、 [C5(3,5-(CH3)2-C6F3)5] - 、 [C5(3,4,5-(CH3)3-C6F2)5] - 、 [C5(2,6-(CF3)2-C6F3)5] - 、 [C5(2,4,6-(CF3)3-C6F2)5] - 、 [C5(3,5-(CF3)2-C6F3)5] - 、 [C5(3,4,5-(CF3)3-C6F2)5] - 、 [C5(C6F5)5] - 、 [Li(Ta(OC6F5)4(2-OC6F5)2)2] - 、 [Nb(OC6F5)6] - 、 [PF6] - 、 [AsF6] - 、 [SbF6] - 、 [BF4]-, [ClO4]-; [C 2B9H 12 -, [CB 11 H 12 - such as carborane anions are included, but are not limited thereto.

[0108] However, the molar ratio of LA to the metallocene complex is 100 to 300.

[0109] Embodiments of the present invention relate to a method for preparing the olefin polymerization catalyst composition, which includes mixing and reacting a main catalyst, a fluorinated silica gel carrier, and a Lewis acidic substance LA in an arbitrary order in a homogeneous liquid medium. The homogeneous liquid medium includes a saturated alkane liquid medium containing pentane and its isomers, hexane and its isomers, heptane and its isomers, and octane and its isomers, and an aromatic liquid medium containing benzene, toluene, xylene and isomers, trimethylbenzene and isomers, chlorobenzene, dichlorobenzene and isomers, fluorobenzene, difluorobenzene and isomers, and polyfluorobenzene and isomers.

[0110] Here, the reaction temperature is -75°C to 150°C.

[0111] Here, the reaction time is 1 minute to 8 hours.

[0112] Furthermore, embodiments of the present invention also relate to the use of the catalyst composition in the polymerization of olefin CH2=CHR. Here, R is hydrogen or a hydrocarbon group having 1 to 12 carbon atoms.

[0113] Here, the olefin is selected from ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-nonene, 1-decene, 3-methyl-1-butene and 4-methyl-1-pentene, butadiene, hexadiene, vinylcyclopentene and vinylcyclohexene.

Effects of the Invention

[0114] In embodiments of the present invention, the above metallocene catalyst composition is generally applied to the bulk slurry polymerization process of olefin polymerization. By appropriate polymerization conditions and catalyst adjustment, it can also be applied to the solvent slurry polymerization process or the gas phase polymerization process.

[0115] Using a silica fluoride carrier to support the metallocene complex described in the present invention, changing a homogeneous catalyst system to a heterogeneous catalyst system, further improving the product form of the polymer, improving the bulk density and fluidity of the product, and significantly avoiding clogging of the polymerization apparatus. Furthermore, since the fluorinated silica gel provides sufficient acidic sites, compared with the catalyst supported using ordinary silica gel, while maintaining the same activity level, the amount of activator of expensive methylaluminoxane or borate reagent can be significantly reduced. As a result, even without using an activator of methylaluminoxane or borate reagent, it has high activity, the effective life of the catalyst is prolonged, the catalyst performance is improved, the production cost is reduced, which is advantageous for the popularization of industrial applications.

[0116] As can be seen from Table 2, in Comparative Example 5, no carrier was used, so the fluidity of the polymer was poor, there was blocking, and the bulk density could not be measured. However, by using a fluorinated silica gel carrier, the morphology of the polymer can be improved and the bulk density can be increased. As can be seen from Examples 1 to 4, the polymerization activity when using a fluorinated silica gel carrier and not using methylaluminoxane (MAO) is at the same level or slightly higher compared to the activity when using an ordinary silica gel carrier in Comparative Examples 1 to 4 and using a methylaluminoxane co - agent 500 times higher. In Examples 34 to 37, only 100 times of MAO was compounded using a fluorinated silica gel carrier, and in Examples 42 to 45, only 60 times of MAO was compounded using a fluorinated silica gel carrier, and their activities are all higher than those in Comparative Examples 1 to 4. This indicates that the catalyst composition using a fluorinated silica gel carrier can significantly reduce the amount of MAO used, or can maintain high catalyst performance even by avoiding the use of MAO. As can be seen from Examples 1 to 45, the catalyst composition of the present invention has high polymerization activity within a polymerization time of less than 1 hour, can adjust the isotacticity, has a high bulk density of the polymer, and has a good morphology.

Embodiments for Carrying Out the Invention

[0117] The embodiments of the present invention will be described in detail below. These embodiments are implemented on the premise of the technical solution of the present invention and provide detailed embodiments and processes. However, the scope of the patent claims of the present invention is not limited to the following embodiments. For the process parameters not specified in the following embodiments, generally follow normal conditions.

[0118] The endpoints and any values disclosed in the scope of the present invention are not limited to the exact range or value, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint value of each range and a single point value, and between single point values, one or more new numerical ranges can be obtained by combining them with each other, and these numerical ranges should be regarded as specifically disclosed in the present invention.

Embodiment

[0119] The analysis characterization method adopted in the related technology of the present invention is as follows.

[0120] The analysis of ligands and complexes was performed using NMR and a mass spectrometer.

[0121] NMR: AV400, BRUKER, Germany.

[0122] Mass spectrometer: 5973N, Agilent, USA.

[0123] Example 1

[0124] (1) Synthesis of metallocene complex Cat-1:

[0125]

Chemical formula

[0126] In the above reaction formula, M is Zr, and the specific synthesis procedure is as described in Example 1 of CN105985368A.

[0127] (2) Preparation of fluorinated silica gel support S1: Silica gel of type number Grace 955 was evacuated at 450 °C for 3 hours and then allowed to cool to room temperature under the protection of an inert gas. 5 g of the above dehydrated silica gel was added to a 500 mL three-necked flask containing 250 mL of hexane, 15 mL of a 1 M AlEt2F toluene solution was added at room temperature, and the mixture was stirred for 2 hours. It was filtered, washed with hexane, and dried by suction. The support obtained above was heated from room temperature to 150 °C over 1 hour and held for 1 hour, then the temperature was raised to 450 °C and held for another 3 hours, and then allowed to cool to room temperature. During this temperature change process, the support was fluidized in oxygen and further fluidized in argon gas at 200 °C for 2 hours to obtain fluorinated silica gel support S1.

[0128] (3) Preparation of catalyst composition CSC-1: The metallocene complex Cat-1 was dissolved in toluene to prepare a solution with a concentration of 10 mM. 50 mg of the fluorinated silica gel support S1 was added to a 50 mL flask containing 20 mL of hexane, 3 mL of a 1 M triisobutylaluminum-hexane solution was added, and after stirring for 5 minutes, 1 mL of the Cat-1 toluene solution (10 mM) prepared as above was added, and the mixture was stirred at room temperature for 30 minutes to obtain catalyst composition CS-1.

[0129] (4) Polymerization: A 5 L reaction vessel was evacuated and replaced with nitrogen gas three times, then 1000 μmol of triisobutylaluminum and 1000 g of propylene were added to the reaction vessel, the catalyst composition solution prepared in step (3) was pressured into the reaction vessel with high-pressure nitrogen gas, the temperature was raised to 70 °C, and a polymerization reaction was carried out for 1 hour to obtain 182 g of a polymerization product. The catalyst activity was 1.82×10 7 gPP / molcat.h, the isotacticity was 86%, and the bulk density was 0.382 g / mL.

[0130] Examples 2 - 33 (1) Synthesis of metallocene complexes Cat-2 - Cat-33: The steps are the same as in Example 1, replacing the raw materials with ligand raw materials having corresponding substituents, and the substituents of the catalyst complexes are shown in Table 1.

[0131] (2) Preparation of fluorinated silica gel support S1: The same as in Example 1.

[0132] (3) Preparation of catalyst compositions CSC-2 to CSC-33: The same as in Example 1, except that Cat-1 was replaced with Cat-2 to Cat-33, respectively.

[0133] (4) Polymerization: The polymerization conditions are the same as in Example 1, and the polymerization performance is shown in Table 2.

[0134] Examples 34 to 37 (1) Metallocene complexes Cat-1 to Cat4 were used.

[0135] (2) Preparation of fluorinated silica gel support S1: The same as in Example 1.

[0136] (3) Preparation of catalyst compositions CSC-34 to CSC-37: The metallocene complex Cat-1 was dissolved in toluene to prepare a solution with a concentration of 10 mM. 50 mg of the fluorinated silica gel support S1 was added to a 50 mL flask containing 20 mL of hexane, and 1000 μmol of a MAO (methylaluminoxane) solution was added. After stirring for 5 minutes, 1 mL of the toluene solutions (10 mM) of Cat-1 to Cat-4 prepared as above was added respectively, and the mixture was stirred at room temperature for 30 minutes to obtain catalyst compositions CS-34 to CSC-37, respectively.

[0137] (4) Polymerization: The polymerization conditions are the same as in Example 1, and the polymerization performance is shown in Table 2.

[0138] Examples 38 to 41 (1) Metallocene complexes Cat-1 to Cat4 were used.

[0139] (2) Preparation of fluorinated silica gel support S2: The silica gel of model number Grace 955 was vacuum-sucked at 450 °C for 3 hours and then allowed to cool to room temperature under the protection of an inert gas. 5 g of the above dehydrated silica gel was added to a 500 mL three-necked flask containing 250 mL of hexane, 20 mL of a 1 M toluene solution of AlEt2F and 3 mmol of ethanol were added at room temperature, and the mixture was stirred for 2 hours. It was filtered, washed with hexane, and dried by vacuum suction. The carrier obtained above was heated from room temperature to 100 °C over 1 hour and held for 1 hour, then the temperature was raised to 400 °C and held for another 3 hours, and then allowed to cool to room temperature. During this temperature change process, the carrier was fluidized in oxygen to obtain a fluorinated silica gel carrier S2.

[0140] (3) Preparation of catalyst compositions CSC-38 to CSC-41: The same as in Example 1 except that S1 was replaced by S2.

[0141] (4) Polymerization: The polymerization conditions were the same as in Example 1, and the polymerization performance is shown in Table 2.

[0142] Examples 42 to 45 (1) Metallocene complexes Cat-1 to Cat-4 were used respectively.

[0143] (2) Preparation of fluorinated silica gel carrier S2: The same as in Example 38.

[0144] (3) Preparation of catalyst compositions CSC-42 to CSC-45: The metallocene complexes Cat-1 to Cat-4 were each dissolved in toluene and prepared into a solution with a concentration of 10 mM. 50 mg of the fluorinated silica gel carrier S2 was added to a 50 mL flask containing 20 mL of hexane, 600 μmol of an MAO (methylaluminoxane) solution was added, and after stirring for 5 minutes, 1 mL of the Cat-1 toluene solution (10 mM) prepared as above was added, and the mixture was stirred at room temperature for 30 minutes to obtain catalyst compositions CSC-42 to CSC-45.

[0145] (4) Polymerization: The polymerization conditions were the same as in Example 1, and the polymerization performance is shown in Table 2.

[0146] Comparative Examples 1 to 4 (1) Metallocene complexes Cat-1 to Cat-4 were used respectively.

[0147] (2) Activation of silica gel support S0: Silica gel of model number Grace 955 was vacuum aspirated at 450 °C for 3 hours and then allowed to cool to room temperature under the protection of an inert gas.

[0148] (3) Preparation of catalyst compositions D1 - D4: Metallocene complexes Cat-1 to Cat-4 were respectively dissolved in toluene to prepare solutions with a concentration of 10 mM. 50 mg of the Grace-955 silica gel support activated in step (2) was added to a 50 mL flask containing 20 mL of hexane, and 5000 μmol of MAO (methylaluminoxane) solution was added. After stirring for 5 minutes, 1 mL of the Cat-1 to Cat-4 toluene solution (10 mM) prepared as above was added, and the mixture was stirred at room temperature for 30 minutes to obtain catalyst compositions D-1 to D-4.

[0149] (4) Polymerization: The polymerization conditions were the same as in Example 1, and the polymerization performance is shown in Table 2.

[0150] Comparative Example 5 (1) Metallocene complex Cat-1 was used.

[0151] (2) Preparation of catalyst composition D5: Metallocene complex Cat-1 was dissolved in toluene to prepare a solution with a concentration of 10 mM. 5000 μmol of MAO (methylaluminoxane) solution was added to 1 mL of the toluene solution of Cat-1, and the mixture was stirred at room temperature for 30 minutes to obtain catalyst composition D5.

[0152] (3) Polymerization: The polymerization conditions were the same as in Example 1, and the polymerization performance is shown in Table 2. As can be seen from Table 2, in Comparative Example 5, since no carrier was used, the fluidity of the polymer was poor, there was blocking, and the bulk density could not be measured. However, by using a fluorinated silica gel carrier, the morphology of the polymer can be improved and the bulk density can be increased. As can be seen from Examples 1 to 4, when a fluorinated silica gel carrier is used and methylaluminoxane (MAO) is not used, the polymerization activity is at the same level or slightly higher compared to the activity when using a normal silica gel carrier in Comparative Examples 1 to 4 and using a methylaluminoxane auxiliary agent 500 times as much. In Examples 34 to 37, only 100 times of MAO was blended using a fluorinated silica gel carrier, and in Examples 42 to 45, only 60 times of MAO was blended using a fluorinated silica gel carrier, and their activities were all higher than those in Comparative Examples 1 to 4. This indicates that the catalyst composition using a fluorinated silica gel carrier can significantly reduce the amount of MAO used, or can maintain high catalytic performance even by avoiding the use of MAO. As can be seen from Examples 1 to 45, the catalyst composition of the present invention has high polymerization activity within a polymerization time of 1 hour or less, can adjust the isotacticity, has a high bulk density of the polymer, and has a good morphology.

[0153]

Table 1

[0154]

Table 2-1

[0155]

Table 2-2

[0156] The above content is only a preferred embodiment of the present invention and does not limit the scope of the claims of the present invention. All various modifications or applications made according to the above embodiments are within the scope of the claims of this technical solution.

[0157] Although specific embodiments of the present invention have been described in detail, it will be apparent to those skilled in the art that various modifications and substitutions can be made to those details based on all the disclosed teachings, and all such changes are within the scope of the claims of the present invention. The full scope of the present invention is given by the appended claims and their equivalents.

Claims

1. An olefin polymerization catalyst composition comprising a main catalyst and a carrier, wherein the carrier is fluorinated silica gel particles and the main catalyst is a metallocene complex represented by the general formula (I). 【Chemical 1】 [Here, M is a Group 3, 4, 5 or 6 transition metal element in the periodic table, including lanthanoid elements and actinide elements. X may be the same as or different from each other, and is a hydrogen element, a halogen, an alkyl group R, an alkoxy group OR, a mercapto group SR, a carboxyl group OCOR, an amine group NR 2 , a phosphino group PR 2 , -OR°O- and OSO 2 CF 3 and is selected from, where R is a linear or branched alkyl group of C 1 -C 20 , a saturated or unsaturated alkyl group of C 1 -C 20 , a halogenated or non-halogenated alkyl group of C 1 -C 20 , an alkyl group containing a heteroatom of Group 13 to Group 17 elements in the periodic table of C 1 -C 20 , a cycloalkyl group of C 3 -C 20 , an aryl group of C 6 -C 30 , an alkyl-substituted aryl group of C 7 -C 30 or an aryl-substituted alkyl group of C 7 -C 30 . R° is a divalent radical, and the divalent radical is an alkylene group of C 2 -C 40 , an arylene group of C 6 -C 30 , an alkyl-substituted arylene group of C 7 -C 40 , an aryl-substituted alkylene group of C 7 -C 40 . In the -OR°O- structure, the two oxygen atoms are at either position of the radical. n is an integer from 1 to 4. The total charge number of n Xs is the charge number of M - 2. Q is a divalent radical, and the divalent radical is =CR' 2 , =SiR' 2 , =GeR' 2 , =NR', =PR', =BR', where R' is a methyl group, an ethyl group, an isopropyl group, a trimethylsilyl group, a phenyl group or a benzyl group. A is a π-ligand and has a structure represented by the chemical formula (II). 【Chemical 2】 E is a divalent radical of a Group 16 or Group 15 element in the periodic table, and the divalent radical includes an oxygen radical, a sulfur radical, a selenium radical, NR", and PR", where R" is C 1 -C 10 a linear alkyl group, a phenyl group, a mono-substituted phenyl group, a poly-substituted phenyl group, a benzyl group, a mono-substituted benzyl group, a poly-substituted benzyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, or a 5-phenanthryl group. L is a divalent radical and has a structure represented by the following chemical formula (III), (IV), (V), (VI), (VII) or (VIII), where i is 2. 【Chemical 3】 Z is a π-ligand, Z = A, or Z has a chemical structure represented by the following chemical formula (IX), (X), (XI), (XII) or (XIII). [Chemical Formula 4] Here, R 1 and R 12 are hydrogen, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a phenyl group, a benzyl group, a 2-furyl group or a 2-thienyl group. R 2 、 R 3 and R 13 are each hydrogen, fluorine or R, where R is a C 1 -C 20 linear or branched alkyl group, a C 1 -C 20 saturated or unsaturated alkyl group, a C 1 -C 20 halogenated or non-halogenated alkyl group, a C 1 -C 20 alkyl group containing a heteroatom of Group 13 to Group 17 elements in the periodic table, a C 3 -C 20 cycloalkyl group, a C 6 -C 30 aryl group, a C 7 -C 30 alkyl-substituted aryl group or a C 7 -C 30 aryl-substituted alkyl group. R 4 is H, a methyl group, a trifluoromethyl group, an isopropyl group, a tert-butyl group, a phenyl group, a p-tert-butylphenyl group, a p-trimethylsilylphenyl group, a p-trifluoromethylphenyl group, a 3,5-dichloro-4-trimethylsilylphenyl group or a 2-naphthyl group. R 5 is a hydrogen, fluorine or methyl group. R 6 and R 7 is each hydrogen, fluorine or R, where R is C 1 -C 20 a linear or branched alkyl group of 1 -C 20 a saturated or unsaturated alkyl group of 1 -C 20 a halogenated or non-halogenated alkyl group of 1 -C 20 an alkyl group containing a heteroatom of Group 13 to Group 17 elements in the periodic table of 3 -C 20 a cycloalkyl group of 6 -C 30 an aryl group of 7 -C 30 an alkyl-substituted aryl group or C 7 -C 30 an aryl-substituted alkyl group of. R 8 is a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or a phenyl group. R 9 and R 9' are a phenyl group, a substituted phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, furan, thiophene, quinoline or pyrimidine, where the substituent in the substituted phenyl group is a cyano group, a nitro group, F, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a methoxy group, a tert-butyl group, a trifluoromethoxy group, Cl, a trifluoromethyl group, a carbonyl group or a trimethylsilyl group. R 10 and R 10' is a hydrogen, fluorine, chlorine, methyl group, ethyl group or phenyl group. R 11 and R 11' is hydrogen, fluorine, chlorine, an ester group, an alkoxy group, a thiol group, an amine group or a phosphino group.

2. The monovalent anionic π-ligand as A has a chemical structure represented by the chemical formula (II)-Li + and the chemical formula (II) includes a basic structure having a cyclopentadiene ring. The active hydrogen in the cyclopentadiene structure has electrophilic reactivity and can undergo an exchange reaction with a nucleophile to form a compound represented by the chemical formula (II)-Li + The olefin polymerization catalyst composition according to claim 1, wherein the basic reaction is as shown in the following reaction formula. [Chemical Formula 5] [Here, the nucleophile in the reaction formula is an organolithium reagent LiR n where R n is an alkyl group of C 1 -C 6 or an aryl group of C 6 -C 12 where the symbol * is linked to a chemical bond, atom or radical, and indicates that the same kind of chemical bond, atom or radical as the point linked to * forms one chemical single bond.]

3. X is chlorine, bromine, C 1 -C 20 The olefin polymerization catalyst composition according to claim 2, which is a low-carbon alkyl group or aryl group.

4. M is a Group 3, 4 or lanthanoid metal element, X may be the same as or different from each other, and is a hydrogen element, halogen, alkyl group R, alkoxy group OR, mercapto group SR, carboxyl group OCOR, amine group (NR 2 ), phosphino group (PR 2 ), -OR°O-, OSO 2 CF 3 and is selected from Here, R is C 1 -C 20 a linear or branched alkyl group, C 1 -C 20 a saturated or unsaturated alkyl group, C 1 -C 20 a halogenated or non-halogenated alkyl group, C 1 -C 20 an alkyl group selectively containing a heteroatom of Group 13 to Group 17 elements in the periodic table, C 3 -C 20 a cycloalkyl group, C 6 -C 30 an aryl group, C 7 -C 30 an alkyl-substituted aryl group or C 7 -C 30 an aryl-substituted alkyl group, and R° is a divalent radical, In the -OR°O- structure, the two oxygen atoms may be at any position of the radical, Q is a divalent radical, Here, R' is the same or different and is C 1 -C 20 a linear or branched alkyl group of, C 1 -C 20 a saturated or unsaturated alkyl group of, C 1 -C 20 a halogenated or non-halogenated alkyl group of, C 1 -C 20 an alkyl group selectively containing a heteroatom of Group 13 to Group 17 elements in the periodic table of, C 3 -C 20 a cycloalkyl group of, C 6 -C 30 an aryl group of, C 7 -C 30 an alkyl-substituted aryl group or C 7 -C 30 an aryl-substituted alkyl group, The olefin polymerization catalyst composition according to claim 1.

5. The olefin polymerization catalyst composition according to claim 4, wherein M is zirconium, hafnium or titanium of Group 4.

6. The olefin polymerization catalyst composition according to claim 4, wherein X is selected from halogens such as chlorine and bromine, and lower carbon alkyl groups and aryl groups.

7. R° is C 2 -C 40 an alkylene group of, C 6 -C 30 an arylene group of, C 7 -C 40 an alkyl-substituted arylene group of or C 7 -C 40 an aryl-substituted alkylene group of, the olefin polymerization catalyst composition according to claim 4.

8. The olefin polymerization catalyst composition according to claim 4, wherein in the -OR°O- structure, the positions of the two oxygen atoms are a combination of adjacent (α, β-position) and alternating (α, γ-position) positions of the radical.

9. Q is =CR' 2 , =SiR' 2 , =GeR' 2 , =NR', =PR' or =BR', and the olefin polymerization catalyst composition according to claim 4.

10. R' is a methyl group, an ethyl group, an isopropyl group, a trimethylsilyl group, a phenyl group or a benzyl group, and E is a divalent radical of a Group 16 or Group 15 element in the periodic table. The olefin polymerization catalyst composition according to claim 1.

11. E is an oxygen radical, a sulfur radical, an arsenic radical, NR” or PR”, Here, R” is C 1 -C 20 a linear or branched alkyl group, C 1 -C 20 a saturated or unsaturated alkyl group, C 1 -C 20 a halogenated or non-halogenated alkyl group, C 1 -C 20 an alkyl group selectively containing a heteroatom of Group 13 to Group 17 elements in the periodic table, C 3 -C 20 a cycloalkyl group, C 6 -C 30 an aryl group, C 7 -C 30 an alkyl-substituted aryl group or C 7 -C 30 an aryl-substituted alkyl group, and the olefin polymerization catalyst composition according to claim 10.

12. The olefin polymerization catalyst composition according to claim 11, wherein E is a sulfur element, an oxygen element, NR” or PR”.

13. "R” is C 4 -C 10 a linear alkyl group, phenyl group, monosubstituted phenyl group, polysubstituted phenyl group, benzyl group, monosubstituted benzyl group, polysubstituted benzyl group, 1-naphthyl group, 2-naphthyl group, 2-anthryl group, 1-phenanthryl group, 2-phenanthryl group or 5-phenanthryl group, and the olefin polymerization catalyst composition according to claim 12.

14. R 1 is a saturated or unsaturated alkyl group of C 1 -C 40 , a halogenated or non-halogenated alkyl group of C 1 -C 40 , an alkyl group selectively containing a heteroatom of Group 13 to Group 17 elements in the periodic table of C 1 -C 40 , a cycloalkyl group of C 3 -C 40 , an aryl group of C 6 -C 40 , an alkyl-substituted aryl group of C 7 -C 40 , an aryl-substituted alkyl group of C 7 -C 40 The olefin polymerization catalyst composition according to claim 1, which is any one of them.

15. R 1 is the olefin polymerization catalyst composition according to claim 14, which is selected from a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a phenyl group, a benzyl group, a 2-furyl group, and a 2-thienyl group.

16. R 2 and R 3 The olefin polymerization catalyst composition according to claim 1, wherein R and R are hydrogen, fluorine or R.

17. R 2 and R 3 is hydrogen, the olefin polymerization catalyst composition according to claim 16.

18. R 4 is a saturated or unsaturated alkyl group of C 1 -C 40 , a halogenated or non-halogenated alkyl group of C 1 -C 40 , an alkyl group selectively containing a heteroatom of Group 13 to Group 17 elements in the periodic table of C 1 -C 40 , a cycloalkyl group of C 3 -C 40 , an aryl group of C 6 -C 40 , an alkyl-substituted aryl group of C 7 -C 40 , an aryl-substituted alkyl group of C 7 -C 40 The olefin polymerization catalyst composition according to claim 1, which is any one of

19. R 4 is the olefin polymerization catalyst composition according to claim 18, which is selected from H, a methyl group, a trifluoromethyl group, an isopropyl group, a tert-butyl group, a phenyl group, a p-tert-butylphenyl group, a p-trimethylsilylphenyl group, a p-trifluoromethylphenyl group, a 3,5-dichloro-4-trimethylsilylphenyl group, and a 2-naphthyl group.

20. R 5 is the same as or different from, C 1 -C 40 saturated or unsaturated alkyl group, C 1 -C 40 halogenated or non-halogenated alkyl group, C 1 -C 40 alkyl group selectively containing a heteroatom of Group 13 to Group 17 elements in the periodic table and C 3 -C 40 cycloalkyl group, C 6 -C 40 aryl group, C 7 -C 40 alkyl-substituted aryl group, C 7 -C 40 The olefin polymerization catalyst composition according to claim 1, which is any one of aryl-substituted alkyl groups.

21. R 5 is the olefin polymerization catalyst composition according to claim 20, selected from hydrogen, fluorine, and methyl groups. Claim 22 In Chemical Formulas (V), (VI), (VII), and (VIII), R 6 and R 7 are R 3 The olefin polymerization catalyst composition according to claim 1, wherein Claim 23 R 6 and R 7 is an olefin polymerization catalyst composition according to claim 22, selected from hydrogen and fluorine elements. Claim 24 In the chemical formula (I), Z is a π-ligand, Z = A, or Z has a chemical structure represented by the following general formulas (IX), (X), (XI), (XII), (XIII), (XIV), (XV). The olefin polymerization catalyst composition according to claim 1. 【Chemical Formula 6】 [In the above formulas (IX), (X), (XI), (XII), (XIII), R 1 is a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a phenyl group, a benzyl group, a 2-furyl group or a 2-thienyl group, R 2 is hydrogen, and R 8 is the same or different and is a C 1 -C 40 saturated or unsaturated alkyl group, a C 1 -C 40 halogenated or non-halogenated alkyl group, a C 1 -C 40 alkyl group selectively containing a heteroatom of Group 13 to Group 17 elements in the periodic table and a C 3 -C 40 cycloalkyl group, a C 6 -C 40 aryl group, a C 7 -C 40 alkyl-substituted aryl group, a C 7 -C 40 aryl-substituted alkyl group, and is any of them, R 9 is the same as or different from, C 1 -C 40 a saturated or unsaturated alkyl group of C 1 -C 40 a halogenated or non-halogenated alkyl group of C 1 -C 40 an alkyl group selectively containing a heteroatom of Group 13 to Group 17 elements in the periodic table of C 3 -C 40 a cycloalkyl group of C 6 -C 40 an aryl group of C 7 -C 40 an alkyl-substituted aryl group of C 7 -C 40 any of an aryl-substituted alkyl group of C, and R 10 is the same or different and is a C 1 -C 40 saturated or unsaturated alkyl group, a C 1 -C 40 halogenated or non-halogenated alkyl group, a C 1 -C 40 alkyl group selectively containing a heteroatom of an element from Group 13 to Group 17 in the periodic table and a C 3 -C 40 cycloalkyl group, a C 6 -C 40 aryl group, a C 7 -C 40 alkyl-substituted aryl group, a C 7 -C 40 aryl-substituted alkyl group, and is any of them, R 11 are the same or different and are each hydrogen, fluorine, chlorine, bromine, OR, SR, OCOR, NR 2 , PR 2 ; or R 11 are the same or different and are each a saturated or unsaturated alkyl group of C 1 -C 40 , a halogenated or non-halogenated alkyl group of C 1 -C 40 , an alkyl group selectively containing a heteroatom of a Group 13 to Group 17 element in the periodic table of C 1 -C 40 , a cycloalkyl group of C 3 -C 40 , an aryl group of C 6 -C 40 , an alkyl-substituted aryl group of C 7 -C 40 , an aryl-substituted alkyl group of C 7 -C 40 ; or any of the foregoing.] Claim 25 R 8 is the olefin polymerization catalyst composition according to claim 24, selected from a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a phenyl group. Claim 26 R 9 is a linear or branched carbon radical of C 1 -C 20 , a saturated or unsaturated carbon radical of C 1 -C 20 , a carbon radical in which part or all of C 1 -C 20 is halogenated, or a linear or cyclic carbon radical of C 1 -C 20 The olefin polymerization catalyst composition according to claim 24, selected from Claim 27 R 10 is the olefin polymerization catalyst composition according to claim 24, selected from hydrogen, fluorine, chlorine, methyl group, ethyl group, and phenyl group. Claim 28 R 11 is the olefin polymerization catalyst composition according to claim 24, selected from hydrogen, fluorine, chlorine, an ester group, an alkoxy group, a thiol group, an amine group, and a phosphino group. Claim 29 The fluorinated silica gel carrier is obtained by reacting silica gel with a fluoride and then heating it in an oxygen and argon atmosphere, or the fluorinated silica gel carrier is obtained by reacting silica gel with a fluoride and a fatty alcohol and then heating it in an oxygen and argon atmosphere. The olefin polymerization catalyst composition according to claim 1. Claim 30 The fluorinated silica gel carrier is obtained by reacting silica gel with a fluoride and phenol and then heating it in an oxygen and argon atmosphere. The olefin polymerization catalyst composition according to claim 29. Claim 31 The fluorinated silica gel carrier is prepared by dispersing silica gel dehydrated at a dispersion temperature of -30°C to 120°C in an organic solvent, contacting it with a fluoride (or a fluoride and a fatty alcohol) at this temperature for 0.5 to 10 hours, filtering the solid, washing it with an organic solvent, drying it, heating it in an oxygen atmosphere at 200 to 500°C for 1 to 6 hours, and further heating it in an argon atmosphere at 200 to 500°C for 1 to 6 hours to obtain the carrier. The olefin polymerization catalyst composition according to claim 29. Claim 32 The dehydration is carried out under the conditions of 200 to 700°C and vacuum suction. The organic solvent is toluene, hexane or heptane. The fluoride is dialkylaluminum fluoride. The charging ratio of the fluoride to silica gel is 1 to 100 mmol / g. The olefin polymerization catalyst composition according to claim 31. Claim 33 The organic solvent is diethylaluminum fluoride, diisopropylaluminum fluoride or dibutylaluminum fluoride. The olefin polymerization catalyst composition according to claim 32. Claim 34 The charging ratio of the fluoride to silica gel is 1 to 50 kg / mol. The olefin polymerization catalyst composition according to claim 32. Claim 35 A method comprising mixing and reacting a main catalyst and a fluorinated silica gel carrier in a homogeneous liquid medium, wherein the homogeneous liquid medium comprises a saturated alkane liquid medium containing pentane and its isomers, hexane and its isomers, heptane and its isomers, and octane and its isomers, and an aromatic liquid medium containing benzene, toluene, xylene and isomers, trimethylbenzene and isomers, chlorobenzene, dichlorobenzene and isomers, fluorobenzene, difluorobenzene and isomers, and polyfluorobenzene and isomers, for preparing an olefin polymerization catalyst composition according to any one of claims 1 to 34.

36. An olefin polymerization catalyst composition, other than the olefin polymerization catalyst composition according to any one of claims 1 to 34, further comprising a Lewis acidic substance LA, wherein the LA is polymethylaluminoxane or modified polymethylaluminoxane or an organoboron reagent having simultaneously an equilibrium state of linear, cyclic and cage structures in solution.

37. The olefin polymerization catalyst composition according to claim 36, wherein the molar ratio of the LA to the metallocene complex is 100 to 300.

38. A method comprising mixing and reacting a main catalyst, a fluorinated silica gel carrier and a Lewis acidic substance LA in a homogeneous liquid medium in any order, wherein the homogeneous liquid medium comprises a saturated alkane liquid medium containing pentane and its isomers, hexane and its isomers, heptane and its isomers, and octane and its isomers, and an aromatic liquid medium containing benzene, toluene, xylene and isomers, trimethylbenzene and isomers, chlorobenzene, dichlorobenzene and isomers, fluorobenzene, difluorobenzene and isomers, and polyfluorobenzene and isomers, for preparing an olefin polymerization catalyst composition according to claim 36.

39. The method according to claim 38, wherein the reaction temperature is -75°C to 150°C and the reaction time is 1 minute to 8 hours.

40. Use of the olefin polymerization catalyst composition according to any one of claims 1 to 34 or the olefin polymerization catalyst composition according to claim 36 or 37 in the polymerization of an olefin CH2=CHR (R is hydrogen or a hydrocarbon group having 1 to 12 carbon atoms).

41. The olefin is selected from ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-nonene, 1-decene, 3-methyl-1-butene and 4-methyl-1-pentene, butadiene, hexadiene, vinylcyclopentene and vinylcyclohexene, the use according to claim 40.

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