Olefin polymerization metallocene catalyst composition and its preparation and use

Abstract

The present invention discloses an olefin polymerization catalyst composition, characterized in that the catalyst composition comprises a main catalyst and a carrier; the carrier is fluorinated silica gel particles; the main catalyst is a metallocene complex represented by general formula (I): (I). The present invention also discloses the preparation of the composition and its application in olefin polymerization reaction. The composition provided by the present invention can reduce or avoid the use of methylaluminoxane or borate reagent, while improving the polymer morphology.

Description

TECHNICAL FIELD

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

[0002] Based on the rich substitution chemistry on the indenyl ring (Halterman, R. L. Chem. Rev. 1992, 92, 965), the infinite combination of the 1stto 7thsubstituents on the indenyl ring, and its potential scientific, technical and commercial values, the third and fourth group metallocene complexes of substituted indenyl ligands, especially the bridged fourth group transition metallocene complexes of substituted indenyl ligands, have been paid great attention in the past three decades (Luigi Resconi, Luigi Cavallo, Anna Fait, and Fabrizio Piemontesi, Chemical Reviews 2000, 100, 1253). The fourth group transition metallocene complexes of bridged substituted indenyl ligands actually constitute the mainstream of metallocene chemistry, not only providing a large number of powerful experimental basis for the development of metal organic chemistry theory, but also providing a number of catalysts with special properties for the polyolefin industry and high selectivity organic synthesis chemistry (Metallocenes in Regio-and Stereoselective Synthesis, T. Takahashi Ed, Springer, 2005). In short, the development of metallocene complex catalysts has contributed a lot to the elucidation of the mechanism of stereospecific polymerization of α-olefins, the enrichment of the variety and specifications of polyolefin materials, and the provision of new polyolefin materials with special properties (-Based Polyolefin; J. Scheirs and W. Kaminsky Eds. Wiley, 2000.).

[0003] In the development of metallocene catalysts, in addition to the classical bridged substituted cyclopentadienyl (Cp'), bridged substituted indenyl (Ind'), bridged substituted fluorenyl (Flu'), and their combinations between Cp' / Ind' / Flu' to form a large group of metallocene complexes (Metallocenes: Synthesis, Reactivity, Applications, A. Togni and R. L. Halterman Eds, Wiley, 1998), in recent years, a certain number of metallocene complexes have been introduced with heteroatoms such as nitrogen, phosphorus, oxygen, sulfur, etc. in the cyclopentadienyl ring (Cp) or in the saturated or unsaturated ring adjacent to the Cp ring. The metallocene complexes containing heteroatom-containing rings either have special activity for olefin polymerization or have special regio- or stereoselectivity (C. De Rosa, F. Auriema, A. Di Capua, L. Resconi, S. Guidotti, I. Camurati, I. E. Nifant'ev, I. P. Laishevets, J. Am. Chem. Soc. 2004, 12, 17040). For example, CA2204803 describes metallocene complexes containing phosphorus heteroatoms and their excellent activity and molecular weight distribution for catalyzing ethylene polymerization, as well as outstanding high-temperature catalytic activity. The fourth group element metallocene complex catalyst system related thereto can catalyze the polymerization of ethylene at high temperature to produce high molecular weight polyethylene. WO9822486 and EP9706297 describe a class of metallocene complexes containing oxygen or / and sulfur or / and nitrogen in the five-membered side ring adjacent to Cp. Such complexes have extremely high activity for the polymerization of propylene when combined with methylaluminoxane (MAO). WO0144318 describes metallocene complexes containing sulfur π-ligands and their process for catalyzing the copolymerization of ethylene / propylene, but the resulting ethylene / propylene copolymer has low molecular weight and is not practically useful. WO03045964 describes a process for preparing a class of dimethylsilicon-bridged substituted sulfur pentalene and substituted indene zirconocene metallocene complexes and their process for catalyzing the copolymerization of ethylene and propylene. With the process described in WO03045964, such zirconocene metallocene complexes have very high polymerization activity, and the resulting ethylene / propylene copolymer has high molecular weight, and the content of ethylene in the copolymer is between 4% and 13% by weight, and the material properties are between RCP and TPE.

[0004] US 6,756,455 describes a class of nitrogen-containing π-ligand metallocene complexes, particularly bridged indeno pyrazole derivatives and bridged indeno indole derivatives complexed to metallocene complexes catalysts. Such metallocene complex catalysts have high activity, high molecular weight, and under appropriate conditions, bimodal molecular weight distribution when used for ethylene homopolymerization. US 6,683,150 discloses fourth group transition metallocene complex catalysts with bridged indeno indole derivatives as ligands, which catalyze propylene polymerization over a wide temperature range to produce high molecular weight polypropylene in numerous examples. WO 03 / 089485 provides a class of nitrogen-containing π-ligand fourth group transition metallocene complexes in combination with methylaluminoxane (MAO) to form a catalytic system characterized by the use of very low aluminum / metal ratios and high activity to produce high molecular weight linear low density polyethylene (mLLDPE) when combined with an appropriate support. WO 99 / 24446 describes a class of nitrogen-containing heteroatom π-ligands to form metallocene complexes with fourth group transition metals. Such metallocene complexes are not only simple to synthesize and have high yield, but also are excellent olefin polymerization catalysts after activation with methylaluminoxane (MAO), modified methylaluminoxane (MMAO) or borate reagents to produce high molecular weight polyethylene and polypropylene, respectively.

[0005] In polymerization production applications, in order to obtain higher 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 more than 500 times, and sometimes even as high as several thousand times. The aluminoxane reagent or borate reagent is expensive, and the large amount used leads to high production cost of the metallocene catalyst; in addition, the metallocene catalyst is a homogeneous catalyst, and the morphology of the produced polymer product is poor, which easily causes the polymerization kettle and device to be blocked during polymerization and product transportation, and the adaptability to industrial devices is poor, which causes difficulties in industrial use. Therefore, in order to ensure the polymerization activity level of the metallocene catalyst, reduce or even avoid the use of aluminoxane reagent and borate reagent, and improve the polymer morphology, it is an urgent technical problem to be improved or solved in the industrial application process of such catalysts. SUMMARY

[0006] One of the purposes of the present application is to provide an olefin polymerization catalyst composition to reduce or avoid the use of methylaluminoxane or borate reagent while improving the polymer morphology. Another purpose of the present application is to provide a preparation method of the above-mentioned olefin polymerization catalyst composition. Still another purpose of the present application is to provide the application of the above-mentioned olefin polymerization catalyst composition in olefin polymerization.

[0007] The embodiments of the present application relate to an olefin polymerization catalyst composition, which comprises 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):

[0008]

[0009] M is a transition metal element in group 3, 4, 5 or 6 of the periodic table, including lanthanides and ruthenides;

[0010] X may be the same as or different from each other, and is selected from hydrogen, halogen, alkyl (R), alkoxy (OR), mercapto (SR), carboxyl (OCOR), amino (NR2), phosphinyl (PR2), -OR°O-, and OSO2CF3, where R is C1-C. 20 Straight-chain or branched alkyl groups, saturated or unsaturated alkyl groups, haloalkyl or non-haloalkyl groups, or alkyl groups containing heteroatoms of elements from Groups 13 to 17 of the periodic table, or C3-C 20 cycloalkyl, C6-C 30 aryl, C7-C 30 Alkyl-substituted aryl or C7-C 30 Aryl substituted alkyl; R° is a divalent radical, including C2-C 40 Alkylene, C6-C 30 The aryl, C7-C 40 alkylarylene, C7-C 40 Arylalkylene compounds; in the -OR°O- structure, the two oxygen atoms are positioned at any position on the free radical;

[0011] n is an integer from 1 to 4; the total charge of n X's is equal to the charge of M minus 2;

[0012] Q is a divalent free radical, including =CR′2, =SiR′2, =GeR′2, =NR′, =PR′, =BR′, where R′ is methyl, ethyl, isopropyl, trimethylsilyl, phenyl, or benzyl;

[0013] A is a π-ligand with a structure as shown in chemical formula (II):

[0014]

[0015] E represents a divalent free radical of an element in Group 16 or Group 15 of the periodic table, including oxygen radicals, sulfur radicals, selenium radicals, NR″, and PR″, where R″ is C1-C. 10 Straight-chain alkyl, phenyl, mono- or poly-substituted phenyl, benzyl, mono- or poly-substituted benzyl, 1-naphthyl, 2-naphthyl, 2-anthrayl, 1-phenanthyl, 2-phenanthyl or 5-phenanthyl;

[0016] L is a divalent free radical and has the structure shown by the following chemical formulas (III), (IV), (V), (VI), (VII), or (VIII), where i is 2:

[0017]

[0018]

[0019] Z is a π-ligand, Z = A, or Z has the chemical structure shown by the following chemical formulas (IX), (X), (XI), (XII), or (XIII):

[0020]

[0021] Among them, R 1 R 12 It can be hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furanyl or 2-thienyl;

[0022] R 2 R 3 and R 13 These are hydrogen, fluorine, or R, respectively, where R is C1-C. 20 Straight-chain or branched alkyl groups, saturated or unsaturated alkyl groups, haloalkyl or non-haloalkyl groups, or alkyl groups containing heteroatoms of elements from Groups 13 to 17 of the periodic table, or C3-C 20 cycloalkyl, C6-C 30 aryl, C7-C 30 Alkyl-substituted aryl or C7-C 30 Aryl substituted alkyl groups;

[0023] R 4 It can be H, methyl, trifluoromethyl, isopropyl, tert-butyl, phenyl, p-tert-butylphenyl, p-trimethylsilylphenyl, p-trifluoromethylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, or 2-naphthyl;

[0024] R 5 It can be hydrogen, fluorine, or methyl;

[0025] R 6 and R 7 These are hydrogen, fluorine, or R, respectively, where R is C1-C. 20 Straight-chain or branched alkyl groups, saturated or unsaturated alkyl groups, haloalkyl or non-haloalkyl groups, or alkyl groups containing heteroatoms of elements from Groups 13 to 17 of the periodic table, or C3-C 20 cycloalkyl, C6-C 30 aryl, C7-C 30 Alkyl-substituted aryl or C7-C 30 Aryl substituted alkyl groups;

[0026] R 8 It can be methyl, ethyl, isopropyl, tert-butyl, or phenyl;

[0027] R 9 and R9’ phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, furan, thiophene, quinoline or pyrimidine, wherein the substituents in the substituted phenyl are cyano, nitro, F, methyl, ethyl, isopropyl, tert-butyl, methoxy, tert-butyl, trifluoromethoxy, Cl, trifluoromethyl, carbonyl or trimethylsilyl;

[0028] R 10 and R 10’ are hydrogen, fluorine, chlorine, methyl, ethyl or phenyl;

[0029] R 11 and R 11’ are hydrogen, fluorine, chlorine, ester, alkoxy, thiol, amine or phosphine.

[0030] In the chemical structural formula (I), the monovalent anion π-ligand of A has a chemical structure as shown in formula (II)-Li + The basic structure of the cyclopentadiene ring in the chemical formula (II) has electrophilic reactivity, and can exchange with a nucleophile to generate a compound as shown in formula (II)-Li + The basic reaction is shown in the following reaction formula:

[0031]

[0032] In the reaction formula, the nucleophile is an organic lithium reagent LiR n , wherein R n is a C1-C6 alkyl or a C6-C 12 aryl group.

[0033] In the chemical formula (II), the symbol * is connected to a chemical bond, an atom or a free radical, indicating that the point connected by * forms a chemical single bond with the same type of chemical bond, atom or free radical.

[0034] , wherein X is chlorine, bromine, C1-C 20 lower alkyl or aryl.

[0035] Specifically, in the chemical formula (I):

[0036]

[0037] M: is a transition metal element of the third, fourth, fifth or sixth group in the periodic table, including lanthanide and actinide elements. Among them, the third, fourth or lanthanide metal elements are preferred, and the fourth group zirconium, cerium and titanium are most preferred.

[0038] X are identical or different from each other and are selected from the group consisting of hydrogen, halogen, alkyl R, alkoxy OR, thio SR, carboxy OCOR, amine (NR2), phosphine (PR2), -OR°O- or OSO2CF3.

[0039] wherein R is a linear or branched alkyl, saturated or unsaturated alkyl, halogenated or non-halogenated alkyl, optionally containing heteroatoms of elements of groups 13 to 17 of the periodic table of elements, or a cycloalkyl of 3 to 8 carbon atoms, an aryl of 6 to 20 carbon atoms, an alkyl-substituted aryl of 7 to 20 carbon atoms, an aryl-substituted alkyl of 7 to 20 carbon atoms. 20 20 30 30 30 20 Examples of saturated alkyl and halogenated alkyl are, but not limited to, methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilyl, triethylsilyl, triphenylsilyl, etc. 20 Examples of unsaturated alkyl are, but not limited to, vinyl, propenyl, allyl, etc. 20 Examples of cycloalkyl are, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, etc. 30 Examples of aryl are, but not limited to, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, etc. 30 Examples of alkyl-substituted aryl are, but not limited to, 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, 2-fluoro-4-methylphenyl, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-i-propylphenyl, 2,6-di-i-propylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro-4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-i-propylphenyl, 3,5-difluoro-4-t-butylphenyl, 3,5-difluoro-4-trimethylsilylphenyl, 3-trifluoromethylphenyl, 3,5-bistrifluoromethylphenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, etc. 30 ​​​​​Examples of the aryl-substituted alkyl group are, for example, benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropylbenzyl, p-tert-butylbenzyl, p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylbenzyl, 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenethyl, p-fluorophenethyl, p-chlorophenethyl, p-isopropylphenethyl, p-tert-butylphenethyl, p-trimethylsilylphenethyl, 2,6-difluorophenethyl, 3,5-difluorophenethyl, 3,4,5-trifluorophenethyl, perfluorophenethyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like, but are not limited thereto.

[0040] R° is a divalent radical, such as C2-C 40 alkylene, C6-C 30 arylene, C7-C 40 alkylarylene, C7-C 40 arylalkylene. In the -OR°O- structure, the two oxygen atoms can be at any position of the radical, but preferably the positions of the two oxygen atoms are in the combination of adjacent (α, β-positions) and interjacent (α, γ-positions) positions of the radical. X is preferably chlorine, bromine, lower alkyl and aryl (such as methyl, phenyl, benzyl, and the like, but is not limited thereto) in the above combinations.

[0041] n is an integer from 1 to 4. The total number of charges of n X is equal to the number of charges of M minus 2.

[0042] Q is a divalent radical, such as =CR'2, =SiR'2, =GeR'2, =NR', =PR', =BR'.

[0043] wherein: R' is the same or different, and is a C1-C 20 straight-chain or branched alkyl group, saturated or unsaturated alkyl group, halogenated or non-halogenated alkyl group, alkyl group optionally containing heteroatoms of elements of Groups 13 to 17 of the Periodic Table of the Elements, or a C3-C 20 cycloalkyl group, C6-C 30 aryl group, C7-C 30 alkyl-substituted aryl group, C7-C 30 aryl-substituted alkyl group. C1-C 20 Examples of the saturated and halogenated alkyl group are, for example, methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilyl, triethylsilyl, triphenylsilyl, and the like, but are not limited thereto. C1-C 20 Examples of the unsaturated alkyl group are, for example, vinyl, propenyl, allyl, and the like, but are not limited thereto. C3-C 20Examples of cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, and the like, but are not limited thereto. C6-C 30 Examples of aryl groups are phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, and the like, but are not limited thereto. C7-C 30 Examples of alkyl-substituted aryl groups are 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, 2-fluoro-4-methylphenyl, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-isopropylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro-4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-isopropylphenyl, 3,5-difluoro-4-tert-butylphenyl, 3,5-difluoro-4-trimethylsilylphenyl, 3-trifluoromethylphenyl, 3,5-bistrifluoromethylphenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, and the like, but are not limited thereto. C7-C 30 Examples of aryl-substituted alkyl groups are benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropylbenzyl, p-tert-butylbenzyl, p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylbenzyl, 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenethyl, p-fluorophenethyl, p-chlorophenethyl, p-isopropylphenethyl, p-tert-butylphenethyl, p-trimethylsilylphenethyl, 2,6-difluorophenethyl, 3,5-difluorophenethyl, 3,4,5-trifluorophenethyl, perfluorophenethyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like, but are not limited thereto.

[0044] In the above combinations, R' is preferably methyl, ethyl, isopropyl, trimethylsilyl, phenyl, or benzyl. A is a π-ligand having the general structure of formula (II):

[0045]

[0046] In general formula (II): the symbol *, whether attached to a bond, atom or group, indicates the point of attachment of a bond to a bond, atom or group of the same designation. All symbols * have the same meaning hereinafter.

[0047] E is a divalent radical of a Group 16 or Group 15 element of the Periodic Table of the Elements, such as an oxygen radical, a sulfur radical, an arsenic radical, NR", PR".

[0048] wherein: R" is a C1-C 20 linear or branched alkyl, saturated or unsaturated alkyl, halogenated or non-halogenated alkyl, alkyl optionally containing heteroatoms of Groups 13 to 17 elements of the Periodic Table of the Elements, or a C3-C 20 cycloalkyl, C6-C 30 aryl, C7-C 30 alkyl-substituted aryl, C7-C 30 aryl-substituted alkyl. Examples of C1-C 20 saturated and halogenated alkyl groups are, for example, methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilylmethyl, triethylsilylmethyl, triphenylsilylmethyl, and the like, but are not limited thereto. Examples of C1-C 20 unsaturated alkyl groups are, for example, vinyl, propenyl, allyl, and the like, but are not limited thereto. Examples of C3-C 20 cycloalkyl groups are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, and the like, but are not limited thereto. Examples of C6-C 30 aryl groups are, for example, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, and the like, but are not limited thereto. Examples of C7-C 30 alkyl-substituted aryl groups are, for example, 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, 2-fluoro-4-methylphenyl, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-isopropylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro-4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-isopropylphenyl, 3,5-difluoro-4-t-butylphenyl, 3,5-difluoro-4-trimethylsilylphenyl, 3-trifluoromethylphenyl, 3,5-bistrifluoromethylphenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, and the like, but are not limited thereto. Examples of C7-C 30Examples of the aryl-substituted alkyl group are, for example, benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropylbenzyl, p-tert-butylbenzyl, p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylbenzyl, 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenethyl, p-fluorophenethyl, p-chlorophenethyl, p-isopropylphenethyl, p-tert-butylphenethyl, p-trimethylsilylphenethyl, 2,6-difluorophenethyl, 3,5-difluorophenethyl, 3,4,5-trifluorophenethyl, perfluorophenethyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like, but are not limited thereto.

[0049] R" is preferably C4-C 10 linear alkyl, phenyl, mono- or polysubstituted phenyl, benzyl, mono- or polysubstituted benzyl, 1-naphthyl, 2-naphthyl, 2-anthryl, 1-phenanthryl, 2-phenanthryl, 5-phenanthryl. All R" have the same meaning hereinafter.

[0050] E is preferably an element from the group consisting of sulfur, oxygen, NR" and PR". R" is defined as above.

[0051] R 1 is any one of the following: C1-C 40 saturated or unsaturated alkyl, halogenated or non-halogenated alkyl, alkyl optionally containing heteroatoms of the elements of groups 13 to 17 of the periodic table of the elements, or C3-C 40 cycloalkyl, C6-C 40 aryl, C7-C 40 alkyl-substituted aryl, C7-C 40 aryl-substituted alkyl. C1-C 40 Examples of the saturated and halogenated alkyl group are, for example, methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilylmethyl, triethylsilylmethyl, triphenylsilylmethyl, and the like, but are not limited thereto. C1-C 20 Examples of the unsaturated alkyl group are, for example, ethenyl, propenyl, allyl, and the like, but are not limited thereto. C3-C 40 Examples of the cycloalkyl group are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, and the like, but are not limited thereto. C3-C 40 Examples of the aryl group are, for example, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, and the like, but are not limited thereto. C6-C 40Examples of alkyl-substituted aryl groups are, for example, 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, 2-fluoro-4-methylphenyl, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-isopropylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro-4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-isopropylphenyl, 3,5-difluoro-4-tert-butylphenyl, 3,5-difluoro-4-trimethylsilylphenyl, 3-trifluoromethylphenyl, 3,5-bistrifluoromethylphenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, and the like, but are not limited thereto. 40 Examples of aryl-substituted alkyl groups of the formula -C7-C

[0052] R 1 Preferably, R is hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furyl, 2-thienyl. All R 1 have the same meaning.

[0053] R 2 and R 3 are hydrogen, fluorine or R. R is defined as above. R 2 and R 3 are preferably hydrogen. All R 2 and R 3 have the same meaning.

[0054] R 4 is any one of the following: C1-C 40 saturated or unsaturated alkyl, halogenated or non-halogenated alkyl, alkyl optionally containing heteroatoms of elements of groups 13 to 17 of the periodic table of the elements, or C3-C 40 cycloalkyl, C6-C 40 aryl, C7-C 40Alkyl-substituted aryl, C7-C 40 Aryl substituted alkyl groups. C1-C 40 Examples of saturated and haloalkyl groups include, but are not limited to, methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilyl, triethylsilyl, triphenylsilyl, etc. (C1-C) 20 Examples of unsaturated alkyl groups include, but are not limited to, vinyl, propenyl, and propyl groups. (C3-C) 40 Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and 1-adamantane. (C6-C) 40 Examples of aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, 9-phenanthyl, etc., but are not limited to these. C7-C 40 Examples of alkyl-substituted aryl groups include 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, 2-fluoro-4-methylphenyl, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-isopropylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3, 5-Dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro-4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-isopropylphenyl, 3,5-difluoro-4-tert-butylphenyl, 3,5-difluoro-4-trimethylsilylphenyl, 3-trifluoromethylphenyl, 3,5-bis(trifluoromethylphenyl), 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, etc., but not limited to these. C7-C 40 Examples of aryl-substituted alkyl groups include, but are not limited to, benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropylbenzyl, p-tert-butylbenzyl, p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylsilylbenzyl, 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenethyl, p-fluorophenethyl, p-chlorophenethyl, p-isopropylphenethyl, p-tert-butylphenethyl, p-trimethylsilylphenethyl, 2,6-difluorophenethyl, 3,5-difluorophenethyl, 3,4,5-trifluorophenethyl, perfluorophenethyl, 1-naphthylmethyl, 2-naphthylmethyl, etc.

[0055] R 4R is preferably H, methyl, trifluoromethyl, isopropyl, t-butyl, phenyl, p-t-butylphenyl, p-trimethylsilylphenyl, p-trifluoromethylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, 2-naphthyl. And all R 4 have the same meaning.

[0056] L is a divalent radical and has any one of the following general chemical formulae (III), (IV), (V), (VI), (VII), (VIII);

[0057]

[0058]

[0059] The symbol *, regardless of whether it is attached to a chemical bond, atom, radical, means that this point can form a single chemical bond with a like chemical bond, atom, radical. And all the symbol * below have the same meaning.

[0060] In general chemical formulae (III) and (IV) : i is an integer, i is not equal to zero, i is preferably 2.

[0061] R 5 are independently any one of the following: C1-C 40 saturated or unsaturated alkyl, halogenated or non-halogenated alkyl, alkyl optionally containing heteroatoms of elements of Groups 13 to 17 of the Periodic Table of Elements, and C3-C 40 cycloalkyl, C6-C 40 aryl, C7-C 40 alkyl-substituted aryl, C7-C 40 aryl-substituted alkyl. C1-C 40 Examples of saturated and halogenated alkyl groups are, but not limited to, methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilyl, triethylsilyl, triphenylsilyl, etc. C1-C 20 Examples of unsaturated alkyl groups are, but not limited to, ethenyl, propenyl, allyl, etc. C3-C 40 Examples of cycloalkyl groups are, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, etc. C3-C 40 Examples of aryl groups are, but not limited to, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, etc. C6-C 40Examples of alkyl-substituted aryl groups are, for example, 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, 2-fluoro-4-methylphenyl, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-isopropylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro-4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-isopropylphenyl, 3,5-difluoro-4-tert-butylphenyl, 3,5-difluoro-4-trimethylsilylphenyl, 3-trifluoromethylphenyl, 3,5-bistrifluoromethylphenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, and the like, but are not limited thereto. 40 Examples of aryl-substituted alkyl groups are, for example, benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropylbenzyl, p-tert-butylbenzyl, p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylsilylbenzyl, 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenethyl, p-fluorophenethyl, p-chlorophenethyl, p-isopropylphenethyl, p-tert-butylphenethyl, p-trimethylsilylphenethyl, 2,6-difluorophenethyl, 3,5-difluorophenethyl, 3,4,5-trifluorophenethyl, perfluorophenethyl, 1-naphtylmethyl, 2-naphtylmethyl, and the like, but are not limited thereto.

[0062] R 5 is preferably hydrogen, fluorine, methyl, and all R 5 have the same meaning hereinafter.

[0063] R 6 and R 7 are equal to R 3 R 3 is as defined above. R 6 and R 7 are preferably hydrogen and fluorine, and all R 6 and R 7 have the same meaning hereinafter.

[0064] In the general formula (I), Z is a π-ligand. Z = A, A being as defined above. Or Z has the chemical structure as shown in the general formulae (IX), (X), (XI), (XII), (XIII), (XIV), (XV) below;

[0065]

[0066] The symbol *, regardless of whether it is attached to a chemical bond, atom, or radical, indicates that this point can form a single chemical bond with a like chemical bond, atom, or radical. All symbols * hereinafter have the same meaning.

[0067] In the above general chemical formulae (IX), (X), (XI), (XII), (XIII), (XIV) :

[0068] R 1 As defined previously.

[0069] R 1 Preferably, methyl, ethyl, isopropyl, t-butyl, phenyl, benzyl, 2-furyl, 2-thienyl.

[0070] R 2 is hydrogen, fluorine, R. R is as defined previously. R 2 Preferably, hydrogen.

[0071] R 8 identical or different, is any one of the following: C1-C 40 saturated or unsaturated alkyl, halogenated or non-halogenated alkyl, alkyl optionally containing heteroatoms of elements of Groups 13 to 17 of the Periodic Table of the Elements, and C3-C 40 cycloalkyl, C6-C 40 aryl, C7-C 40 alkyl-substituted aryl, C7-C 40 aryl-substituted alkyl. C1-C 40 Examples of saturated and halogenated alkyl groups are, but are not limited to, methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilyl, triethylsilyl, triphenylsilyl, and the like. C1-C 20 Examples of unsaturated alkyl groups are, but are not limited to, ethenyl, propenyl, allyl, and the like. C3-C 40 Examples of cycloalkyl groups are, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, and the like. C3-C 40 Examples of aryl groups are, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, and the like. C6-C 40Examples of the alkyl-substituted aryl group are, for example, 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, 2-fluoro-4-methylphenyl, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-isopropylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro-4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-isopropylphenyl, 3,5-difluoro-4-tert-butylphenyl, 3,5-difluoro-4-trimethylsilylphenyl, 3-trifluoromethylphenyl, 3,5-bistrifluoromethylphenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, and the like, but are not limited thereto. 40 Examples of the aryl-substituted alkyl group of the formula: -C(R

[0072] R 8 Preferably, R is a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a phenyl group. Also, all R 8 have the same meaning.

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

[0074] R 9 are preferably C1-C 20Straight-chain or branched, saturated or unsaturated, partially or fully halogenated, linear or cyclic carbon radicals. And all R radicals mentioned below... 9 They have the same meaning.

[0075] R 10 Same or different, is any one of the following: C1-C 40 Saturated or unsaturated alkyl groups, haloalkyl or non-haloalkyl groups, alkyl groups selectively containing heteroatoms of elements from Groups 13 to 17 of the periodic table, and C3-C 40 cycloalkyl, C6-C 40 aryl, C7-C 40 Alkyl-substituted aryl, C7-C 40 Aryl substituted alkyl groups. C1-C 40 Examples of saturated and haloalkyl groups include, but are not limited to, methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilyl, triethylsilyl, triphenylsilyl, etc. (C1-C) 20 Examples of unsaturated alkyl groups include vinyl, propenyl, and allyl groups, but are not limited to these. (C3-C) 40 Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and 1-adamantane. (C6-C) 40 Examples of aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, 9-phenanthyl, etc., but are not limited to these. C7-C 40 Examples of alkyl-substituted aryl groups include 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, 2-fluoro-4-methylphenyl, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-isopropylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3, 5-Dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro-4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-isopropylphenyl, 3,5-difluoro-4-tert-butylphenyl, 3,5-difluoro-4-trimethylsilylphenyl, 3-trifluoromethylphenyl, 3,5-bis(trifluoromethylphenyl), 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, etc., but not limited to these. C7-C 40Examples of aryl-substituted alkyl groups include, but are not limited to, benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropylbenzyl, p-tert-butylbenzyl, p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylsilylbenzyl, 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenethyl, p-fluorophenethyl, p-chlorophenethyl, p-isopropylphenethyl, p-tert-butylphenethyl, p-trimethylsilylphenethyl, 2,6-difluorophenethyl, 3,5-difluorophenethyl, 3,4,5-trifluorophenethyl, perfluorophenethyl, 1-naphthylmethyl, 2-naphthylmethyl, etc.

[0076] R 10 Preferably, it is hydrogen, fluorine, chlorine, methyl, ethyl, or phenyl. And all R in the following text... 10 They have the same meaning.

[0077] R 11 Same or different, meaning any of the following: hydrogen, fluorine, chlorine, bromine, OR, SR, OCOR, NR2, PR2. Where R is as defined above. Or R 11 Same or different, is any one of the following, C1-C 40 Saturated or unsaturated alkyl groups, haloalkyl or non-haloalkyl groups, alkyl groups selectively containing heteroatoms of elements from Groups 13 to 17 of the periodic table, and C3-C 40 cycloalkyl, C6-C 40 aryl, C7-C 40 Alkyl-substituted aryl, C7-C 40 Aryl substituted alkyl groups. C1-C 40 Examples of saturated and haloalkyl groups include, but are not limited to, methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilyl, triethylsilyl, triphenylsilyl, etc. (C1-C) 20 Examples of unsaturated alkyl groups include vinyl, propenyl, and allyl groups, but are not limited to these. (C3-C) 40 Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and 1-adamantane. (C6-C) 40 Examples of aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, 9-phenanthyl, etc., but are not limited to these. C7-C 40Examples of alkyl-substituted aryl groups include 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, 2-fluoro-4-methylphenyl, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-isopropylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3, 5-Dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro-4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-isopropylphenyl, 3,5-difluoro-4-tert-butylphenyl, 3,5-difluoro-4-trimethylsilylphenyl, 3-trifluoromethylphenyl, 3,5-bis(trifluoromethylphenyl), 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, etc., but not limited to these. C7-C 40 Examples of aryl-substituted alkyl groups include, but are not limited to, benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropylbenzyl, p-tert-butylbenzyl, p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylsilylbenzyl, 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenethyl, p-fluorophenethyl, p-chlorophenethyl, p-isopropylphenethyl, p-tert-butylphenethyl, p-trimethylsilylphenethyl, 2,6-difluorophenethyl, 3,5-difluorophenethyl, 3,4,5-trifluorophenethyl, perfluorophenethyl, 1-naphthylmethyl, 2-naphthylmethyl, etc.

[0078] R 11 Preferably, it is a hydrogen, fluorine, chlorine, ester, alkoxy, thiol, amino, or phosphine group. And all R groups mentioned below... 11 They have the same meaning.

[0079] In general chemical structural formula (I), A is a monovalent anionic π-ligand. Furthermore, the precursor of A is a neutral, stable organic compound with the chemical structure shown in general chemical formula (II).

[0080]

[0081] In general chemical formula (II), R 1 R 2 R 3 R 4 L and E, as previously defined. The general chemical formula (II) contains the basic structure of a cyclopentadiene ring. The active hydrogen in the cyclopentadiene structure has unique electrophilic reactivity, allowing it to undergo exchange reactions with nucleophiles such as Grignard reagents and organolithium reagents. The basic reaction is shown in the following equation:

[0082]

[0083] In the above reaction formula, the nucleophile is an organolithium reagent R. n Li is a special case, but in practice, it is not limited to using only organolithium reagents. n It is a C1-C6 alkyl group, or a C6-C 12 Aryl groups.

[0084] This invention relates to a method for synthesizing metallocene complexes represented by general formula (I), comprising:

[0085]

[0086] Wherein, T are the same or different from each other, and T is a monodentate or bidentate neutral ligand;

[0087] LG is a free radical that is the same as or different from each other, and the LG is an organic free radical of hydrogen, alkali metal, or group 14 heavy elements.

[0088] The monodentate ligands include ethers (ROR), thioethers (RSR), tertiary amines (NR3), tertiary phosphines (PR3), cyclic ethers, cyclic thioethers, ketones, substituted cyclic ketones, substituted pyridines, substituted pyrroles, substituted piperidines, esters, lactones, amides, and lactams, wherein R is C1-C. 20 Straight-chain or branched alkyl groups, saturated or unsaturated alkyl groups, haloalkyl or non-haloalkyl groups, or alkyl groups containing heteroatoms of elements from Groups 13 to 17 of the periodic table, or C3-C 20 cycloalkyl, C6-C 30 aryl, C7-C 30 Alkyl-substituted aryl or C7-C 30 Aryl substituted alkyl groups.

[0089] The bidentate ligands include ortho-diethers, α,ω-diethers, ortho-diamines, α,ω-diamines, ortho-disulfides, α,ω-disulfides, ortho-diphosphines, and α,ω-diphosphines. Where x is 0 or an integer 1, 2, or 3.

[0090] The alkali metal elements include lithium, sodium, and potassium; the organic free radicals of the group 14 heavy elements include SiR3, GeR3, SnR3, PdR3, ZnR, BaR, MgR, and CaR, where R is C1-C. 20 Straight-chain or branched alkyl groups, saturated or unsaturated alkyl groups, haloalkyl or non-haloalkyl groups, or alkyl groups containing heteroatoms of elements from Groups 13 to 17 of the periodic table, or C3-C 20 cycloalkyl, C6-C 30 aryl, C7-C30 Alkyl-substituted aryl or C7-C 30 Aryl substituted alkyl groups.

[0091] The reaction medium during the synthesis process is saturated C5-C. 15 Alkanes, cycloalkanes, or mixtures of two or more of them.

[0092] The reaction medium used in the synthesis process is hexane, heptane, octane, toluene, or xylene. The reaction temperature range is -100℃ to +300℃.

[0093] The reaction temperature range is -75℃ to +250℃.

[0094] The reaction temperature range is -50℃ to +150℃.

[0095] This invention relates to a method for preparing fluorinated silica gel carriers: fluorinated silica gel carriers are prepared by reacting silica gel with fluoride, followed by heating under an oxygen and argon atmosphere.

[0096] Alternatively, fluorinated silica gel carriers can be prepared by reacting silica gel with fluorides and fatty alcohols, followed by heating in an oxygen and argon atmosphere.

[0097] One preferred method is to prepare the fluorinated silica gel carrier by reacting silica gel with fluoride and phenol, followed by heating under an oxygen and argon atmosphere.

[0098] Specifically, the preparation method of the fluorinated silica gel carrier includes: dispersing dehydrated silica gel in an organic solvent at a dispersion temperature of -30°C to 120°C, contacting it with a fluoride (or a fluoride and a fatty alcohol) at this temperature for 0.5 to 10 hours, filtering the solid and washing and drying it with an organic solvent, then heating it at 200 to 500°C for 1 to 6 hours in an oxygen atmosphere, and then heating it at 200 to 500°C for 1 to 6 hours in an argon atmosphere to obtain the carrier.

[0099] The dehydration conditions include vacuuming at 200–700°C.

[0100] The organic solvent is toluene, hexane, or heptane.

[0101] The fluoride is dialkyl aluminum fluoride, preferably diethyl aluminum fluoride, diisopropyl aluminum fluoride or dibutyl aluminum fluoride.

[0102] The ratio of fluoride to silica gel is 1-100 mmol / g.

[0103] The weight / molar ratio of the carrier to the metallocene complex is 1–50 kg / mol.

[0104] This invention relates to a method for preparing the above-mentioned catalyst composition, comprising: mixing a main catalyst with a fluorinated silica gel support in a homogeneous liquid medium for reaction, wherein the homogeneous liquid medium includes a saturated alkane liquid medium and an aromatic liquid medium, wherein the saturated alkane includes pentane and its isomers, hexane and its isomers, heptane and its isomers, and octane and its isomers, and the aromatic liquid medium includes benzene, toluene, xylene and its isomers, trimethylbenzene and its isomers, chlorobenzene, dichlorobenzene and its isomers, fluorobenzene, difluorobenzene and its isomers, and polyfluorobenzene and its isomers.

[0105] This invention also relates to an olefin polymerization catalyst composition comprising the above-described main catalyst and the above-described fluorinated silica support, and further comprising a Lewis acidic substance LA.

[0106] Wherein, LA is a polymethylaluminoxane or modified polymethylaluminoxane or organoboron reagent that simultaneously possesses chain, cyclic and cage-like structural equilibrium states in solution.

[0107] Lewis acids (LAs) are a class of large-volume, electron-delocalized, and coordination-poor Lewis acidic substances. Representative examples include polymethylaluminoxanes (PMAO) which simultaneously possess chain, cyclic, and cage-like structures in equilibrium in solution, and modified polymethylaluminoxanes (MMAO) based on this structure.

[0108]

[0109] Numerous other examples of the volume-expanding, electron-delocalized, and coordination-poor anions described in this invention are available, such as [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] - Carborea anions, such as: [C2B9H] 12 ] - ,[CB 11 H 12 ] - However, it is not limited to this.

[0110] The molar ratio of LA to the metallocene complex is 100–300.

[0111] This invention relates to a method for preparing the above-mentioned olefin polymerization catalyst composition, comprising: mixing a main catalyst, a fluorinated silica gel support, and a Lewis acidic substance LA in a homogeneous liquid medium in any order for reaction, wherein the homogeneous liquid medium includes a saturated alkane liquid medium and an aromatic liquid medium, wherein the saturated alkanes include pentane and its isomers, hexane and its isomers, heptane and its isomers, and octane and its isomers, and the aromatic liquid medium includes benzene, toluene, xylene and its isomers, trimethylbenzene and its isomers, chlorobenzene, dichlorobenzene and its isomers, fluorobenzene, difluorobenzene and its isomers, and polyfluorobenzene and its isomers.

[0112] The reaction temperature ranges from -75℃ to 150℃.

[0113] The reaction time ranges from 1 minute to 8 hours.

[0114] The present invention also relates to the application of the above-described catalyst composition in the polymerization of olefins CH2=CHR, wherein R is hydrogen or a hydrocarbon group containing 1-12 carbon atoms.

[0115] The olefins are 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.

[0116] The metallocene catalyst composition described above in this invention is generally suitable for bulk slurry polymerization processes for olefin polymerization. With appropriate polymerization conditions and catalyst adjustments, it can also be applied to solvent slurry polymerization or gas-phase polymerization processes.

[0117] By using fluorinated silica gel as a support to support the metallocene complexes described in this invention, the homogeneous catalytic system is transformed into a heterogeneous catalytic system, further improving the polymer product morphology, increasing the product's bulk density and flowability, and greatly reducing the risk of clogging in the polymerization unit. Furthermore, fluorinated silica gel provides sufficient acidic sites, significantly reducing the amount of expensive methylaluminoxane or borate activators required while maintaining the same activity level compared to catalysts supported on ordinary silica gel. It can even achieve high activity without the use of methylaluminoxane or borate activators, and the catalyst's effective lifespan is extended. This improves catalytic performance while reducing production costs, which is beneficial for industrial application and promotion.

[0118] As shown in Table 2, Comparative Example 5, without a support, exhibited poor polymer flowability, agglomeration, and an inability to measure bulk density. Using a fluorinated silica gel support improved polymer morphology and increased bulk density. Examples 1-4 demonstrate that the polymerization activity using a fluorinated silica gel support without methylaluminoxane (MAO) was comparable to or slightly higher than that of Comparative Examples 1-4 using a conventional silica gel support with up to 500 times the amount of MAO. Examples 34-37, using a fluorinated silica gel support with only 100 times the amount of MAO, and Examples 42-45, using a fluorinated silica gel support with only 60 times the amount of MAO, all showed higher activities than Comparative Examples 1-4. This indicates that the catalyst composition using a fluorinated silica gel support can significantly reduce the amount of MAO or even eliminate the need for MAO while maintaining high catalytic performance. Examples 1-45 show that the catalyst composition of the present invention exhibits high polymerization activity, adjustable isotacticity, high polymer bulk density, and good morphology within a 1-hour polymerization time. Detailed Implementation

[0119] The following provides a detailed description of the embodiments of the present invention: These embodiments are implemented based on the technical solution of the present invention, and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Process parameters not specified in the following embodiments are generally performed under conventional conditions.

[0120] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0121] The analytical characterization methods used in the related technologies of this invention are as follows:

[0122] The analysis of ligands and coordination compounds was performed using nuclear magnetic resonance (NMR) and mass spectrometry (MS).

[0123] MRI: AV400, BRUKER, Germany.

[0124] Mass spectrometer: 5973N, Agilent Technologies, USA.

[0125] Example 1

[0126] (1) Synthesis of the metallocene complex Cat-1:

[0127]

[0128] In the above reaction formula, M is Zr. The specific synthesis steps are described in Example 1 of CN105985368A.

[0129] (2) Preparation of fluorinated silica gel carrier S1:

[0130] Grace 955 silica gel was vacuum-sealed at 450°C for 3 hours, then naturally cooled to room temperature under inert gas protection. 5g of the dehydrated silica gel was added to a 500mL three-necked flask containing 250mL hexane, and 15mL of 1M AlEt2F toluene solution was added at room temperature. The mixture was stirred for 2 hours. The mixture was filtered, washed with hexane, and dried under vacuum. The resulting support was heated from room temperature to 150°C and held for 1 hour, then heated to 450°C and held for 3 hours, and naturally cooled to room temperature. During this temperature change, the support remained fluidized in oxygen. Finally, it was fluidized in argon at 200°C for 2 hours to obtain fluorinated silica gel support S1.

[0131] (3) Preparation of catalyst composition CSC-1:

[0132] The metallocene complex Cat-1 was dissolved in toluene to prepare a 10 mM solution. 50 mg of fluorinated silica gel support S1 was added to a 50 mL flask containing 20 mL of hexane, followed by 3 mL of a 1 M triisobutylaluminum-hexane solution. After stirring for five minutes, 1 mL of the prepared Cat-1 toluene solution (10 mM) was added, and the mixture was stirred at room temperature for 30 minutes to obtain the catalyst composition CS-1.

[0133] (4) Aggregation:

[0134] The 5L reactor was evacuated and purged with nitrogen three times. Then, 1000 μmol of triisobutylaluminum and 1000 g of propylene were added to the reactor. The catalyst composition solution prepared in step (3) was then forced into the reactor using high-pressure nitrogen. The temperature was raised to 70°C, and the polymerization reaction was carried out for 1 hour, yielding 182 g of polymerized product with a catalyst activity of 1.82 × 10⁻⁶. 7 gPP / molcat.h, isotacticity 86%, bulk density 0.382 g / mL.

[0135] Examples 2-33

[0136] (1) Synthesis of metallocene complexes Cat-2 to Cat-33: The steps are the same as in Example 1, except that the raw materials are replaced with ligands with corresponding substituents. The substituents of the catalyst complexes are shown in Table 1.

[0137] (2) Preparation of fluorinated silica gel carrier S1: Same as in Example 1.

[0138] (3) Preparation of catalyst compositions CSC-2 to CSC-33: Same as in Example 1, except that Cat-1 is replaced with Cat-2 to Cat-33 respectively.

[0139] (4) Polymerization: The polymerization conditions are the same as in Example 1, and the polymerization performance is shown in Table 2.

[0140] Examples 34-37

[0141] (1) The metallocene complexes used are Cat-1 to Cat4.

[0142] (2) Preparation of fluorinated silica gel carrier S1: Same as in Example 1.

[0143] (3) Preparation of catalyst compositions CSC-34 to CSC-37:

[0144] The metallocene complex Cat-1 was dissolved in toluene to prepare a 10 mM solution. 50 mg of fluorinated silica gel support S1 was added to a 50 mL flask containing 20 mL of hexane, followed by 1000 μmol of MAO (methylaluminoxane) solution. After stirring for five minutes, 1 mL of the prepared Cat-1 to Cat-4 toluene solutions (10 mM) was added to each flask. The mixture was stirred at room temperature for 30 minutes to obtain catalyst compositions CS-34 to CSC-37.

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

[0146] Examples 38-41

[0147] (1) The metallocene complexes used are Cat-1 to Cat4.

[0148] (2) Preparation of fluorinated silica gel carrier S2:

[0149] Grace 955 silica gel was vacuum-sealed at 450°C for 3 hours, then naturally cooled to room temperature under inert gas protection. 5g of the dehydrated silica gel was added to a 500mL three-necked flask containing 250mL hexane, and 20mL of 1M AlEt2F toluene solution and 3mmol of ethanol were added at room temperature. The mixture was stirred for 2 hours. The mixture was filtered, washed with hexane, and dried under vacuum. The resulting support was heated from room temperature to 100°C and held for 1 hour, then heated to 400°C and held for 3 hours, before naturally cooling to room temperature. During this temperature change, the support remained fluidized in oxygen. Fluorinated silica gel support S2 was obtained.

[0150] (3) Preparation of catalyst compositions CSC-38 to CSC-41: Same as in Example 1, except that S2 is used instead of S1.

[0151] (4) Polymerization: The polymerization conditions are the same as in Example 1, and the polymerization performance is shown in Table 2.

[0152] Examples 42-45

[0153] (1) The metallocene complexes were Cat-1 to Cat-4 respectively.

[0154] (2) Preparation of fluorinated silica gel carrier S2: Same as in Example 38.

[0155] (3) Preparation of catalyst compositions CSC-42 to CSC-45:

[0156] Metallocene complexes Cat-1 to Cat-4 were dissolved in toluene to prepare 10 mM solutions. 50 mg of fluorinated silica gel support S2 was added to a 50 mL flask containing 20 mL of hexane, followed by the addition of 600 μmol of MAO (methylaluminoxane) solution. After stirring for five minutes, 1 mL of the prepared Cat-1 toluene solution (10 mM) was added, and the mixture was stirred at room temperature for 30 minutes to obtain catalyst compositions CSC-42 to CSC-45.

[0157] (4) Polymerization: The polymerization conditions are the same as in Example 1, and the polymerization performance is shown in Table 2.

[0158] Comparative Examples 1-4

[0159] (1) The metallocene complexes were Cat-1 to Cat-4 respectively.

[0160] (2) Activation of silica carrier S0:

[0161] After vacuuming Grace 955 silicone at 450°C for 3 hours, it was naturally cooled to room temperature under inert gas protection.

[0162] (3) Preparation of catalyst compositions D1-D4:

[0163] The metallocene complexes Cat-1 to Cat-4 were dissolved in toluene to prepare 10 mM solutions. 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, followed by 5000 μmol of MAO (methylaluminoxane) solution. After stirring for five minutes, 1 mL of the above-prepared 10 mM Cat-1 to Cat-4 toluene solution was added, and the mixture was stirred at room temperature for 30 minutes to obtain catalyst compositions D-1 to D-4.

[0164] (4) Polymerization: The polymerization conditions are the same as in Example 1, and the polymerization performance is shown in Table 2.

[0165] Comparative Example 5

[0166] (1) The metallocene complex was prepared using Cat-1.

[0167] (2) Preparation of catalyst composition D5:

[0168] The metallocene complex Cat-1 was dissolved in toluene to prepare a 10 mM solution. 1 mM of the Cat-1 toluene solution was added to 5000 μmol of MAO (methylaluminoxane) solution, and the mixture was stirred at room temperature for 30 minutes to obtain catalyst composition D5.

[0169] (3) Polymerization: The polymerization conditions are the same as in Example 1, and the polymerization performance is shown in Table 2.

[0170] As shown in Table 2, Comparative Example 5, without a support, exhibited poor polymer flowability, agglomeration, and an inability to measure bulk density. Using a fluorinated silica gel support improved polymer morphology and increased bulk density. Examples 1-4 demonstrate that the polymerization activity using a fluorinated silica gel support without methylaluminoxane (MAO) was comparable to or slightly higher than that of Comparative Examples 1-4 using a conventional silica gel support with up to 500 times the amount of MAO. Examples 34-37, using a fluorinated silica gel support with only 100 times the amount of MAO, and Examples 42-45, using a fluorinated silica gel support with only 60 times the amount of MAO, all showed higher activities than Comparative Examples 1-4. This indicates that the catalyst composition using a fluorinated silica gel support can significantly reduce the amount of MAO or even eliminate the need for MAO while maintaining high catalytic performance. Examples 1-45 show that the catalyst composition of the present invention exhibits high polymerization activity, adjustable isotacticity, high polymer bulk density, and good morphology within a 1-hour polymerization time.

[0171]

[0172] Table 2

[0173]

[0174] The above are merely preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. All modifications or applications made in accordance with the above embodiments are within the scope of protection of this technical solution.

[0175] Although specific embodiments of the invention have been described in detail, those skilled in the art will understand that various modifications and substitutions can be made to those details based on all the teachings disclosed, and all such changes are within the scope of protection of this invention. The full scope of this invention is given by the appended claims and any equivalents thereof.

Claims

1. An olefin polymerization catalyst composition, characterized in that, The catalyst composition comprises a main catalyst and a support; the support is fluorinated silica gel particles; the main catalyst is a metallocene complex of general formula (I): ； Where M represents the lanthanides and ruthenes; X may be the same as or different from each other, and is selected from hydrogen, halogen, alkyl (R), alkoxy (OR), mercapto (SR), carboxyl (OCOR), amino (NR2), phosphinyl (PR2), -OR°O-, and OSO2CF3, where R is C1-C. 20 Straight-chain or branched alkyl, saturated or unsaturated alkyl, halo- or non-halogenated alkyl, or C3-C 20 cycloalkyl, C6-C 30 aryl, C7-C 30 Alkyl-substituted aryl or C7-C 30 aryl-substituted alkyl; R° is a divalent radical, including C2-C 40 Alkylene, C6-C 30 The aryl, C7-C 40 alkylarylene, C7-C 40 Arylalkylene compounds; in the -OR°O- structure, the two oxygen atoms are positioned at any position on the free radical; n is an integer from 1 to 4; the total charge of n X's is equal to the charge of M minus 2; Q is a divalent free radical, including =CR′2, =SiR′2, =GeR′2, =NR′, =PR′, =BR′, where R′ is methyl, ethyl, isopropyl, trimethylsilyl, phenyl, or benzyl; A is a π-ligand with a structure as shown in chemical formula (II): ； E represents a divalent free radical of an element in Group 16 or Group 15 of the periodic table, including oxygen radicals, sulfur radicals, selenium radicals, NR″, and PR″, where R″ is C1-C. 10 Straight-chain alkyl, phenyl, mono- or poly-substituted phenyl, benzyl, mono- or poly-substituted benzyl, 1-naphthyl, 2-naphthyl, 2-anthrayl, 1-phenanthyl, 2-phenanthyl or 5-phenanthyl; L is a divalent free radical and has the structure shown by the following chemical formulas (III), (IV), (V), (VI), (VII), or (VIII), where i is 2: ； Z is a π-ligand, Z = A, or Z has the chemical structure shown by the following chemical formulas (IX), (X), (XI), (XII), or (XIII): ； Among them, R 1 R 12 It can be hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furanyl or 2-thienyl; R 2 R 3 and R 13 These are hydrogen, fluorine, or R, respectively, where R is C1-C. 20 Straight-chain or branched alkyl, saturated or unsaturated alkyl, halo- or non-halogenated alkyl, or C3-C 20 cycloalkyl, C6-C 30 aryl, C7-C 30 Alkyl-substituted aryl or C7-C 30 aryl-substituted alkyl groups; R 4 It can be H, methyl, trifluoromethyl, isopropyl, tert-butyl, phenyl, p-tert-butylphenyl, p-trimethylsilylphenyl, p-trifluoromethylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, or 2-naphthyl; R 5 It can be hydrogen, fluorine, or methyl; R 6 and R 7 These are hydrogen, fluorine, or R, respectively, where R is C1-C. 20 Straight-chain or branched alkyl, saturated or unsaturated alkyl, halo- or non-halogenated alkyl, or C3-C 20 cycloalkyl, C6-C 30 aryl, C7-C 30 Alkyl-substituted aryl or C7-C 30 aryl-substituted alkyl groups; R 8 It can be methyl, ethyl, isopropyl, tert-butyl, or phenyl; R 9 and R 9’ It is phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, 9-phenanthyl, furan, thiophene, quinoline or pyrimidine, wherein the substituent in the substituted phenyl is cyano, nitro, F, methyl, ethyl, isopropyl, tert-butyl, methoxy, tert-butyl, trifluoromethoxy, Cl, trifluoromethyl, carbonyl or trimethylsilyl; R 10 and R 10’ It can be hydrogen, fluorine, chlorine, methyl, ethyl, or phenyl; R 11 and R 11’ It can be hydrogen, fluorine, chlorine, ester, alkoxy, thiol, amino, or phosphine. The fluorinated silica gel carrier is prepared by the following method: dehydrated silica gel is dispersed in an organic solvent at a dispersion temperature of -30°C to 120°C, and then contacted with a fluoride, or a combination of a fluoride and a fatty alcohol, at this temperature for 0.5 to 10 hours. The solid is filtered, washed with an organic solvent, dried, and then heated at 200 to 500°C for 1 to 6 hours in an oxygen atmosphere, followed by heating at 200 to 500°C for 1 to 6 hours in an argon atmosphere to obtain the carrier. The fluoride is dialkyl aluminum fluoride.

2. The olefin polymerization catalyst composition of claim 1, characterized in that, The monovalent anion π-ligand of A has the chemical formula (II)-Li + The chemical structure shown; chemical formula (II) contains the basic structure of a cyclopentadiene ring. The active hydrogen in the cyclopentadiene structure is electrophilic and can undergo an exchange reaction with a nucleophile to form chemical formula (II)-Li. + The basic reaction of the compound shown is shown in the following reaction equation: ； In the reaction formula, the nucleophile is an organolithium reagent, LiR. n , where R n It is a C1-C6 alkyl or C6-C 12 The aryl group, where the symbol * is attached to a chemical bond, atom, or free radical, indicates that the point where * is attached forms a single chemical bond with a similar chemical bond, atom, or free radical.

3. The olefin polymerization catalyst composition of claim 2, characterized in that, X represents chlorine, bromine, or Cl-C. 20 Low carbon alkyl or aryl.

4. The olefin polymerization catalyst composition of claim 1, characterized in that, M is a lanthanide metal element; X may be the same or different from each other, and is selected from hydrogen, halogen, alkyl R, alkoxy OR, mercapto SR, carboxyl OCOR, amino (NR2), phosphin (PR2), -OR°O- or OSO2CF3; Where R is C1-C 20 Straight-chain or branched alkyl, saturated or unsaturated alkyl, halo- or non-halogenated alkyl, or C3-C 20 cycloalkyl, C6-C 30 aryl, C7-C 30 Alkyl-substituted aryl, C7-C 30 aryl-substituted alkyl groups; R° is a divalent free radical; In the -OR°O- structure, the two oxygen atoms can be located at any position on the free radical; Q is a divalent free radical; Where R′ is the same or different, it is C1-C 20 Straight-chain or branched alkyl, saturated or unsaturated alkyl, halo- or non-halogenated alkyl, or C3-C 20 cycloalkyl, C6-C 30 aryl, C7-C 30 Alkyl-substituted aryl, C7-C 30 Aryl-substituted alkyl groups.

5. The olefin polymerization catalyst composition of claim 4, characterized in that, M is selected from zirconium, iron, and titanium; X is selected from halogens such as chlorine and bromine, as well as low-carbon alkyl and aryl groups; R° is selected from C2-C 40 Alkylene, C6-C 30 The aryl, C7-C 40 alkyl arylene or C7-C 40 Aranediene; In the -OR°O- structure, the positions of the two oxygen atoms are a combination of adjacent and alternating positions in the free radical; Q is selected from =CR′2, =SiR′2, =GeR′2, =NR′, =PR′ or =BR′.

6. The olefin polymerization catalyst composition according to any one of claims 1-5, characterized in that, R′ is methyl, ethyl, isopropyl, trimethylsilyl, phenyl, or benzyl; E is a divalent radical of an element in Group 16 or Group 15 of the periodic table; Where: R″ is C1-C 20 Straight-chain or branched alkyl, saturated or unsaturated alkyl, halo- or non-halo-alkyl, C3-C 20 cycloalkyl, C6-C 30 aryl, C7-C 30 Alkyl-substituted aryl, C7-C 30 Aryl-substituted alkyl groups.

7. The olefin polymerization catalyst composition of claim 6, characterized in that, The E is selected from oxygen free radical, sulfur free radical, arsenic free radical, NR″, PR″, and the E is selected from elemental sulfur, oxygen, NR″ and PR″. The R″ is selected from C4-C. 10 Straight-chain alkyl, phenyl, mono- or poly-substituted phenyl, benzyl, mono- or poly-substituted benzyl, 1-naphthyl, 2-naphthyl, 2-anthrayl, 1-phenanthyl, 2-phenanthyl, 5-phenanthyl.

8. The olefin polymerization catalyst composition of claim 1, characterized in that, R 1 It is any one of the following: C1-C 40 Saturated or unsaturated alkyl groups, haloalkyl or non-haloalkyl groups, C3-C 40 cycloalkyl, C6-C 40 aryl, C7-C 40 Alkyl-substituted aryl, C7-C 40 Aryl-substituted alkyl groups.

9. The olefin polymerization catalyst composition of claim 8, characterized in that, R 1 The radicals selected are hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furanyl, and 2-thienyl.

10. The olefin polymerization catalyst composition of claim 1, characterized in that, R 2 and R 3 It can be hydrogen, fluorine, or R.

11. The olefin polymerization catalyst composition of claim 10, characterized in that, R 2 and R 3 It is hydrogen.

12. The olefin polymerization catalyst composition of claim 1, characterized in that, R 4 It is any one of the following: C1-C 40 Saturated or unsaturated alkyl groups, haloalkyl or non-haloalkyl groups, C3-C 40 cycloalkyl, C6-C 40 aryl, C7-C 40 Alkyl-substituted aryl, C7-C 40 Aryl-substituted alkyl groups.

13. The olefin polymerization catalyst composition of claim 12, characterized in that, R 4 The derivatives are selected from H, methyl, trifluoromethyl, isopropyl, tert-butyl, phenyl, p-tert-butylphenyl, p-trimethylsilylphenyl, p-trifluoromethylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, and 2-naphthyl.

14. The olefin polymerization catalyst composition of claim 1, characterized in that, R 5 Same or different, is any one of the following: C1-C 40 Saturated or unsaturated alkyl groups, haloalkyl or non-haloalkyl groups, C3-C 40 cycloalkyl, C6-C 40 aryl, C7-C 40 Alkyl-substituted aryl groups, C7-C 40 Aryl-substituted alkyl groups.

15. The olefin polymerization catalyst composition of claim 14, characterized in that, R 5 The components are selected from hydrogen, fluorine, and methyl.

16. The olefin polymerization catalyst composition of claim 1, characterized in that, In chemical formulas (V), (VI), (VII), and (VIII), R 6 and R 7 Equal to R 3 .

17. The olefin polymerization catalyst composition of claim 16, characterized in that, R 6 and R 7 It consists of hydrogen and fluorine elements.

18. The olefin polymerization catalyst composition of claim 1, characterized in that, In chemical formula (I), Z is a π-ligand, Z = A; or Z has the chemical structure shown in the following general chemical formulas (IX), (X), (XI), (XII), (XIII), (XIV), (XV); ； In the above equations (IX), (X), (XI), (XII), and (XIII): R 1 The compounds are methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furanyl, and 2-thienyl. R 2 It is hydrogen; R 8 Same or different, is any one of the following: C1-C 40 Saturated or unsaturated alkyl groups, haloalkyl or non-haloalkyl groups, C3-C 40 cycloalkyl, C6-C 40 aryl, C7-C 40 Alkyl-substituted aryl, C7-C 40 aryl-substituted alkyl groups; R 9 Same or different, is any one of the following: C1-C 40 Saturated or unsaturated alkyl groups, haloalkyl or non-haloalkyl groups, alkyl groups selectively containing heteroatoms of elements from Groups 13 to 17 of the periodic table, and C3-C 40 cycloalkyl, C6-C 40 aryl, C7-C 40 Alkyl-substituted aryl, C7-C 40 aryl-substituted alkyl groups; R 10 Same or different, is any one of the following: C1-C 40 Saturated or unsaturated alkyl groups, haloalkyl or non-haloalkyl groups, alkyl groups selectively containing heteroatoms of elements from Groups 13 to 17 of the periodic table, and C3-C 40 cycloalkyl, C6-C 40 aryl, C7-C 40 Alkyl-substituted aryl, C7-C 40 aryl-substituted alkyl groups; R 11 Same or different is any of the following: hydrogen, fluorine, chlorine, bromine, OR, SR, OCOR, NR2, PR2; or R 11 Same or different, is any one of the following, C1-C 40 Saturated or unsaturated alkyl groups, haloalkyl or non-haloalkyl groups, C3-C 40 cycloalkyl, C6-C 40 aryl, C7-C 40 Alkyl-substituted aryl, C7-C 40 Aryl-substituted alkyl groups.

19. The olefin polymerization catalyst composition of claim 18, characterized in that, R 8 Selected from methyl, ethyl, isopropyl, tert-butyl, and phenyl; R 9 Selected from C1-C 20 Straight-chain or branched, saturated or unsaturated, partially or fully halogenated, linear or cyclic carbon radicals; R 10 Selected from hydrogen, fluorine, chlorine, methyl, ethyl, or phenyl; R 11 Selected from hydrogen, fluorine, chlorine, ester, alkoxy, thiol, amino, and phosphine groups.

20. The composition according to claim 1, characterized in that, The dehydration conditions are vacuum at 200~700℃; the organic solvent is toluene, hexane or heptane; the fluoride is dialkyl aluminum fluoride; the feeding ratio of fluoride to silica gel is 1-100 mmol / g.

21. The composition according to claim 20, characterized in that, The fluoride is selected from diethylaluminum fluoride, diisopropylaluminum fluoride or dibutylaluminum fluoride; the feeding ratio of the fluoride to silica gel is 1~50 kg / mol.

22. A method for preparing the catalyst composition according to any one of claims 1-21, characterized in that, include: The main catalyst is mixed with a fluorinated silica gel support in a homogeneous liquid medium for reaction. The homogeneous liquid medium includes a saturated alkane liquid medium and an aromatic liquid medium. The saturated alkanes include pentane and its isomers, hexane and its isomers, heptane and its isomers, and octane and its isomers. The aromatic liquid medium includes benzene, toluene, xylene and its isomers, trimethylbenzene and its isomers, chlorobenzene, dichlorobenzene and its isomers, fluorobenzene, difluorobenzene and its isomers, and polyfluorobenzene and its isomers.

23. An olefin polymerization catalyst composition, characterized in that, The catalyst composition comprises any one of the compositions of claims 1-21, and further comprises a Lewis acidic substance LA; wherein LA is a polymethylaluminoxane or modified polymethylaluminoxane or organoboron reagent having a chain, cyclic and cage-like structure in equilibrium in solution.

24. The composition of claim 23, characterized in that, The molar ratio of LA to the metallocene complex is 100~300.

25. A method for preparing the composition according to any one of claims 23-24, characterized in that, include: The main catalyst, fluorinated silica gel support, and Lewis acidic substance LA are mixed in any order in a homogeneous liquid medium for reaction. The homogeneous liquid medium includes saturated alkane liquid medium and aromatic liquid medium. The saturated alkanes include pentane and its isomers, hexane and its isomers, heptane and its isomers, and octane and its isomers. The aromatic liquid medium includes benzene, toluene, xylene and its isomers, trimethylbenzene and its isomers, chlorobenzene, dichlorobenzene and its isomers, fluorobenzene, difluorobenzene and its isomers, and polyfluorobenzene and its isomers.

26. The method of claim 25, characterized in that, The reaction temperature is between -75℃ and 150℃; the reaction time is between 1 minute and 8 hours.

27. The use of any composition according to claims 1-21 or any composition according to claims 23-24 in the polymerization of olefins CH2=CHR, wherein, R is hydrogen or a hydrocarbon group containing 1-12 carbon atoms.

28. The application according to claim 27, characterized in that, The olefins are 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.

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