Metallocene catalyst composition and preparation method and application thereof

Abstract

The invention provides a metallocene catalyst composition as well as a preparation method and application thereof. The metallocene catalyst composition comprises a main catalyst, a co-catalyst, an activator and a carrier, the main catalyst has a structure represented by formula I: # imgabs0 # M is selected from transition metal elements of the third group, the fourth group, the fifth group and the sixth group; n X is the same as or different from each other and is independently selected from H, halogen,-R,-OR,-SR,-OCOR,-NR2,-PR2,-OR degree O-and-OSO2CF3; n is an integer of 1-4; q is a divalent radical; a and Z are independently selected from # imgabs1. The metallocene catalyst composition has high activity, and development of polypropylene with high melt index and ultrahigh melt index can be completed through a direct hydrogen regulation method.

Description

Technical Field

[0001] The present invention belongs to the fields of catalyst technology and polypropylene production, and particularly relates to a metallocene catalyst composition, a preparation method thereof and an application thereof. Background Art

[0002] High melt index polypropylene has a high flow rate and good physical properties, and can be used to prepare large thin-walled injection products with complex structures. Currently, it is mainly applied in the fields of packaging, transportation, household appliances, automobiles, office, daily consumer goods, medical products, etc. Ultra-high melt index polypropylene generally refers to polypropylene materials with extremely high melt indices, generally above 1200 g / 10 min. The larger the value, the smaller the molecular weight, the better the processing fluidity of the material, and the finer the fibers extruded by melt blowing. It is the main raw material for melt-blown non-woven fabrics, and is the core material for products such as masks, protective clothing, diapers, and automotive sound insulation cotton. Polypropylene with a higher melt index can be used as polypropylene wax, which is an important additive and can be used in inks and coatings, with wide applications.

[0003] In the prior art, in order to obtain high melt index and ultra-high melt index polypropylene resins and polypropylene wax products with better comprehensive performance, generally two methods are adopted: one is to adopt a suitable controlled rheology technology, that is, in the process of extrusion granulation, peroxides are added to the polypropylene resin to cause the polypropylene resin to degrade, thereby increasing the melt index. CN111410793A, CN111205563A, CN101153095A, etc. disclose methods for preparing high melt index polypropylene resins by peroxide degradation method. In the prior art, when producing ultra-high fluidity polypropylene products by adding peroxides to degrade polypropylene, it will form more initiator residues and small molecule by-products formed by free radical degradation reactions, resulting in a higher content of volatile organic compounds (VOCs) in the product, and the odor level generally exceeds the industry's health requirements. However, with the continuous improvement of people's living standards and quality of life and the continuous enhancement of health and environmental protection awareness, as respiratory protection products closely related to human health, odor parameters have become the key indicators for evaluating the product quality, which limits its applications in medical supplies, household products, automotive interior parts, food packaging, etc.; the other is to adopt a new catalyst system or improved polymerization process to directly polymerize high melt index polypropylene resin in the reactor. The high melt index polypropylene resin directly obtained by in-reactor polymerization has a low yellowness index, a low content of volatile organic compounds, and basically no odor, and has a wide range of application fields, and has become the development trend of preparing high melt index polypropylene. CN114478880A discloses a method for producing high melt index meltblown polypropylene by batch process and the high melt index meltblown polypropylene obtained by this method. The method uses a traditional Ziegler-Natta catalyst, and it is difficult to control the molecular weight distribution and isotacticity of polypropylene; CN1206720A discloses a method for preparing polypropylene wax using an ethylidene-bridged metallocene compound as a catalyst, and a soluble polypropylene wax can be obtained. In this method, the catalyst components are added to liquid propylene in the form of a solution for reaction, and the polypropylene wax product is discharged in the form of a melt. This method is difficult to implement in actual production and has no practical application value; CN105622807B discloses a technology for preparing polypropylene wax using a supported metallocene catalyst. This method uses a supported metallocene catalyst to catalyze the bulk polymerization of propylene to directly obtain granular polypropylene wax products, but the catalyst activity is low and the industrial production cost is high.

[0004] Therefore, it is necessary for those skilled in the art to provide a preparation method that can take into account the preparation of high melt index and ultra-high melt index polypropylene at the same time. This method is not only applicable to batch polymerization reactors but also can be applied to continuous production devices. The polypropylene obtained by polymerization has characteristics such as low odor, narrow molecular weight distribution, and low ash content. Summary of the Invention

[0005] To solve the above problems, the object of the present invention is to provide a metallocene catalyst composition, a preparation method and an application thereof. The metallocene catalyst composition has high activity and can be used to develop high melt index and ultra-high melt index polypropylene through direct hydrogen regulation method.

[0006] To achieve the above object, the present invention provides a metallocene catalyst composition, which comprises a main catalyst, a cocatalyst, an activator and a carrier. Among them, the main catalyst has the structure shown in Formula I:

[0007]

[0008] In Formula I, M is selected from Group 3 transition metal elements, Group 4 transition metal elements, Group 5 transition metal elements, Group 6 transition metal elements (including lanthanide and actinide elements); n Xs are the same as or different from each other and are each independently selected from H, halogen, -R, -OR, -SR, -OCOR, -NR 2 , -PR 2 , -OR°O-, -OSO 2 CF 3 , wherein R is independently selected from straight-chain or branched alkyl groups of C 1 -C 20 , unsaturated hydrocarbon groups of C 1 -C 20 , haloalkyl groups of C 1 -C 20 , hydrocarbon groups containing heteroatoms from Group 13 elements to Group 17 elements of C 1 -C 20 , silicon-based groups and their derivatives of C 1 -C 20 , cycloalkyl groups of C 3 -C 20 , aryl groups of C 6 -C 30 , alkyl-substituted aryl groups and their derivatives of C 7 -C 30 , aryl-substituted alkyl groups and their derivatives of C 7 -C 30 ; R° is a divalent hydrocarbon group and its derivatives; n is an integer from 1 to 4, and the product of n and the charge number of X is equal to the charge number of the central metal atom M minus two;

[0009] Q is a divalent radical selected from -CR′ 2 -, -SiR′ 2 -, -GeR′ 2 -, -NR′-, -PR′-, -BR′-, wherein R′ is independently selected from straight-chain or branched alkyl groups of C 1 -C 20 ​1 -C 20 unsaturated hydrocarbon group of, C 1 -C 20 haloalkyl group of, C 1 -C 20 hydrocarbon group containing heteroatoms from Group 13 to Group 17 elements of, C 1 -C 20 silyl group and its derivatives of, C 3 -C 20 cycloalkyl group of, C 6 -C 30 aryl group of, C 7 -C 30 alkyl-substituted aryl group and its derivatives of, C 7 -C 30 aryl-substituted alkyl group and its derivatives;

[0010] A and Z are the same or different and are each independently selected from Ligand 1, Ligand 2, Ligand 3;

[0011] Ligand 1 has the structure shown in Formula II:

[0012]

[0013] In Formula II, R 1 and R 1 ' are the same or different and are each independently selected from H, C 1 -C 20 hydrocarbon group and its derivatives of, C 4 -C 10 furyl group and its derivatives of, C 4 -C 10 thienyl group and its derivatives of; R 2 and R 2 ' are the same or different and are each independently selected from C 1 -C 40 linear or branched alkyl group of, C 1 -C 40 unsaturated hydrocarbon group of, C 1 -C 40 haloalkyl group of, C 1 -C 40 hydrocarbon group containing heteroatoms from Group 13 to Group 17 elements of, C 1 -C 40 silyl group and its derivatives of, C 3 -C 40 cycloalkyl group of, C 6 -C 40 aryl group of, C 7 -C 40 alkyl-substituted aryl group and its derivatives of, C 7-C 40 aryl-substituted alkyls thereof and their derivatives; in formula II, the symbol * regardless of whether it is attached to a chemical bond, atom, or radical, indicates that this point can form a chemical single bond with the same type of chemical bond, atom, or radical. And all symbols * in the following text have the same meaning.

[0014] Ligand 2 has the structure shown in formula III:

[0015]

[0016] In formula III, R 1 is selected from H, C 1 -C 20 hydrocarbyls thereof and their derivatives, C 4 -C 10 furyls thereof and their derivatives, C 4 -C 10 thienyls thereof and their derivatives; R 3 and R 3 ' are the same or different and are each independently selected from H, C 1 -C 40 linear or branched alkyls, C 1 -C 40 unsaturated hydrocarbyls, C 1 -C 40 haloalkyls, C 1 -C 40 hydrocarbyls containing heteroatoms from Group 13 to Group 17 elements, C 1 -C 40 silyls thereof and their derivatives, C 3 -C 40 cycloalkyls, C 6 -C 40 aryls, C 7 -C 40 alkyl-substituted aryls thereof and their derivatives, C 7 -C 40 aryl-substituted alkyls thereof and their derivatives; R 4 and R 4 ' are the same or different and are each independently selected from H, halogen, C 1 -C 40 linear or branched alkyls, C 1 -C 40 unsaturated hydrocarbyls, C 1 -C 40 haloalkyls, C 1 -C 40 hydrocarbyls containing heteroatoms from Group 13 to Group 17 elements, C 1 -C 40 silyls thereof and their derivatives, C 3 -C40 The cycloalkyl group, C 6 -C 40 The aryl group, C 7 -C 40 The alkyl-substituted aryl group and its derivatives, C 7 -C 40 The aryl-substituted alkyl group and its derivatives; R 5 is selected from H, halogen, -R, wherein R is selected from C 1 -C 20 The straight-chain or branched alkyl group, C 1 -C 20 The unsaturated hydrocarbon group, C 1 -C 20 The haloalkyl group, C 1 -C 20 The hydrocarbon group containing heteroatoms from Group 13 elements to Group 17 elements, C 1 -C 20 The silyl group and its derivatives, C 3 -C 20 The cycloalkyl group, C 6 -C 30 The aryl group, C 7 -C 30 The alkyl-substituted aryl group and its derivatives, C 7 -C 30 The aryl-substituted alkyl group and its derivatives;

[0017] Ligand 3 has the structure shown in Formula IV:

[0018]

[0019] In Formula IV, R 1 is selected from H, C 1 -C 20 The hydrocarbon group and its derivatives, C 4 -C 10 The furyl group and its derivatives, C 4 -C 10 The thienyl group and its derivatives; R 4 , R 4 ’, R 4 ” and R 4 ”’ are the same or different and are each independently selected from H, halogen, C 1 -C 40 The straight-chain or branched alkyl group, C 1 -C 40 The unsaturated hydrocarbon group, C 1 -C 40 The haloalkyl group, C 1 -C 40hydrocarbyl containing a Group XIII to Group XVII heteroatom, C 1 -C 40 silanyl and its derivatives, C 3 -C 40 cycloalkyl, C 6 -C 40 aryl, C 7 -C 40 alkyl-substituted aryl and its derivatives, C 7 -C 40 aryl-substituted alkyl and its derivatives; R 5 is selected from H, halogen, -R, wherein R is selected from C 1 -C 20 linear or branched alkyl, C 1 -C 20 unsaturated hydrocarbyl, C 1 -C 20 haloalkyl, C 1 -C 20 hydrocarbyl containing a Group XIII to Group XVII heteroatom, C 1 -C 20 silanyl and its derivatives, C 3 -C 20 cycloalkyl, C 6 -C 30 aryl, C 7 -C 30 alkyl-substituted aryl and its derivatives, C 7 -C 30 aryl-substituted alkyl and its derivatives; R 6 and R 6 ’ are the same or different and are each independently selected from H, halogen, -OR, -SR, -OCOR, -NR 2 、-PR 2 ,wherein R is independently selected from C 1 -C 40 linear or branched alkyl, C 1 -C 40 unsaturated hydrocarbyl, C 1 -C 40 haloalkyl, C 1 -C 40 hydrocarbyl containing a Group XIII to Group XVII heteroatom, C 1 -C 40 silanyl and its derivatives, C 3 -C 40 cycloalkyl, C 6 -C 40 aryl, C 7 -C 40alkyl-substituted aryl and its derivatives, C 7 -C 40 aryl-substituted alkyl and its derivatives.

[0020] According to a specific embodiment of the present invention, preferably, in formula I, M is selected from Group III transition metal elements and Group IV transition metal elements, more preferably selected from titanium, zirconium, and hafnium.

[0021] According to a specific embodiment of the present invention, preferably, the n Xs are the same as or different from each other and are each independently selected from halogen, -R, -OR, -SR, -OCOR, -NR 2 , -PR 2 , -OR°O-, -OSO 2 CF 3, wherein, R is independently selected from 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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(trifluoromethyl)phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, 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-bis(trimethylsilyl)benzyl, 3,5-bis(trifluoromethyl)benzyl, 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., but not limited thereto; X is more preferably selected from chlorine, bromine, C 1 -C 20 alkyl, C 6 -C 20 aryl, C 7 -C 20 benzyl; R° is selected from C 2 -C 40 alkylene, C 6 -C 30 arylene, C 7 -C 40 alkylarylene, C 7 -C 40For the arylalkylene group, 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 a combination of adjacent (α,β-positions) and alternating (α,γ-positions) positions of the radical.

[0022] According to a specific embodiment of the present invention, preferably, Q is selected from -CR′ 2 -, -SiR′ 2 -, -GeR′ 2 -, -NR′-, -PR′-, -BR′-, where R′ is independently selected from 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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, 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., but not limited thereto; more preferably, R′ is independently selected from methyl, ethyl, isopropyl, trimethylsilyl, phenyl, benzyl.

[0023] According to a specific embodiment of the present invention, preferably, in formula II, R 1 and R 1 ' are the same or different and each independently selected from H, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furyl, 2-thienyl; R 2 and R 2 ' are the same or different and each independently selected from 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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(trifluoromethyl)phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, 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-bis(trimethylsilyl)benzyl, 3,5-bis(trifluoromethyl)benzyl, 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., but not limited thereto; more preferably, R 2 and R 2 ' are each independently selected from methyl, ethyl, isopropyl, tert-butyl, phenyl.

[0024] According to a specific embodiment of the present invention, preferably, in formula III, R 1Selected from H, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furyl, 2-thienyl; R 3 and R 3 ’ are the same or different and each independently selected from H, 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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(trifluoromethyl)phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, 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-bis(trimethylsilyl)benzyl, 3,5-bis(trifluoromethyl)benzyl, 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., but not limited thereto. More preferably, R 3 and R 3 ’ each independently selected from 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, pyrimidine, wherein the substituents in the substituted phenyl are selected from cyano, nitro, F, methyl, ethyl, isopropyl, tert-butyl, methoxy, tert-butyl, trifluoromethoxy, Cl, trifluoromethyl, carbonyl, trimethylsilyl; R 4 and R4 ' are the same or different and each independently selected from H, fluorine, chlorine, 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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(trifluoromethyl)phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, 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-bis(trimethylsilyl)benzyl, 3,5-bis(trifluoromethyl)benzyl, 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., but not limited thereto. More preferably, R 4 and R 4 ' are each independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, phenyl; R 5Selected from H, fluorine, -R, where R is selected from 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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(trifluoromethyl)phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, 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-bis(trimethylsilyl)benzyl, 3,5-bis(trifluoromethyl)benzyl, 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., but not limited thereto.

[0025] According to a specific embodiment of the present invention, preferably, in formula IV, R 1 is selected from H, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furyl, 2-thienyl; R 4 , R 4 ’, R 4 ” and R 4”’Same or different, each independently selected from H, fluorine, chlorine, 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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(trifluoromethyl)phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, 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-bis(trimethylsilyl)benzyl, 3,5-bis(trifluoromethyl)benzyl, 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., but not limited thereto. More preferably, R 4 、R 4 ’, R 4 ” and R 4 ”’ are each independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, phenyl; R 5Selected from H, fluorine, -R, wherein R is selected from 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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(trifluoromethyl)phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, 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-bis(trimethylsilyl)benzyl, 3,5-bis(trifluoromethyl)benzyl, 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., but not limited thereto; R 6 and R 6 ’ are the same or different and are each independently selected from H, halogen, -OR, -SR, -OCOR, -NR 2 , -PR 2, wherein R is independently selected from 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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(trifluoromethyl)phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, 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-bis(trimethylsilyl)benzyl, 3,5-bis(trifluoromethyl)benzyl, 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., but not limited thereto.

[0026] According to a specific embodiment of the present invention, preferably, the carrier is a silica-modified carrier, and the silica-modified carrier is obtained by reacting a metal-organic framework coordination polymer with silica and then heating in a vacuum atmosphere.

[0027] According to a specific embodiment of the present invention, preferably, the method for preparing the silica-modified support comprises the following steps: at -30°C to 120°C, dehydrated silica is dispersed in a dry organic solvent (preferably with a water content of less than 15 ppm), and then mixed and contacted with a metal-organic framework coordination polymer for 0.5 - 10 h. After filtration, washing, and vacuum pumping, it is heated at 150 - 200°C for 1 - 6 h, and then heated at 200 - 300°C for 1 - 6 h under a protective gas atmosphere (such as argon) to obtain the silica-modified support.

[0028] According to a specific embodiment of the present invention, preferably, the metal-organic framework coordination polymer is selected from one or more combinations of UiO-66, UiO-66-NH 2 、UiO-66-MM, UiO-66-Br, UiO-66-Br 2 、UiO-66-CO 2 H, UiO-67, MIL-100(Al), MIL-100(Fe), MIL-53(Al), MIL-53(Cr), MIL-127, MIL-101-NH 2 (Cr), MIL-125-NH 2 (Ti), Zn-MOF-508, Zn-DMOF-A, Zn-DMOF-TM, CAU-10-H, CAU-10-CH 3 、CAU-10-NO 2 、CAU-10-NH 2 、CAU-10-OH, CAU-10-OCH 3 、MOF-801-P, MOF-801-SC, MOF-802, MOF-804, MOF-841, DUT-51(Zr), DUT-51(Hf), DUT-67(Zr). In the present invention, the metal-organic framework coordination polymer can be obtained through commercial purchase or synthesis.

[0029] According to a specific embodiment of the present invention, preferably, the dehydration condition of silica is vacuum pumping at 300 - 600°C.

[0030] According to a specific embodiment of the present invention, preferably, the organic solvent includes one or more combinations of toluene, hexane, and heptane.

[0031] According to a specific embodiment of the present invention, preferably, 1 - 100 mg of the metal-organic framework coordination polymer is added per gram of dehydrated silica.

[0032] According to the specific embodiments of the present invention, preferably, the activator is a Lewis acidic substance (LA), more preferably including one or a combination of two or more of methylaluminoxane, polymethylaluminoxane, modified methylaluminoxane, and organoboron reagents.

[0033] LA is a class of Lewis acidic substances with a large volume, electron delocalization, and poor coordination. Representatives of such substances are polymethylaluminoxane (PMAO) that simultaneously has a chain-like, cyclic, and cage-like structure equilibrium state in solution and modified polymethylaluminoxane (MMAO) based on this.

[0034] There are also a large number of examples to choose from for the anions with a large volume, electron delocalization, and poor coordination in the present invention, such as; [B(C 6 H 5 ) 4 -, [(CH 3 )B(C 6 F 5 ) 3 - , [B(C 6 F 5 ) 4 -, [B(2,6-(CH 3 ) 2 -C 6 H 3 ) 4 -, [B(2,4,6-(CH 3 ) 3 -C 6 H 2 ) 4 -, [B(2,3,5,6-(CH 3 ) 4 -C 6 H) 4 -, [B(2,6-(CF 3 ) 2 -C 6 H 3 ) 4 -, [B(2,4,6-(CF 3 ) 3 -C 6 H 2 ) 4 - , [B(2,3,5,6-(CF 3 ) 4 -C 6 H) 4 - , [B(3,5-(CH 3 ) 2 -C 6 H​​​3 ) 4 - ,[B(3,4,5-(CH 3 ) 3 -C 6 H 2 ) 4 - ,[B(3,5-(CF 3 ) 2 -C 6 H 3 ) 4 -,[B(3,4,5-(CF 3 ) 3 -C 6 H 2 ) 4 -,[B(2,6-(CF 3 ) 2 -C 6 F 3 ) 4 -,[B(2,4,6-(CF 3 ) 3 -C 6 F 2 ) 4 -,[B(2,3,5,6-(CF 3 ) 4 -C 6 F) 4 -,[B(3,5-(CF 3 ) 2 -C 6 F 3 ) 4 -,[B(3,4,5-(CF 3 ) 3 -C 6 F 2 ) 4 -,[Al(C 6 H 5 ) 4 - ,[(CH 3 )Al(C 6 F 5 ) 3 - ,[Al(C 6 F 5 ) 4 - ,[Al(2,6-(CH 3 ) 2 -C 6 H 3 ) 4 ​​​​​​- , [Al(2,4,6-(CH 3 ) 3 -C 6 H 2 ) 4 - , [Al(2,3,5,6-(CH 3 ) 4 -C 6 H) 4 - , [Al(3,5-(CH 3 ) 2 -C 6 H 3 ) 4 - , [Al(3,4,5-(CH 3 ) 3 -C 6 H 2 ) 4 - , [Al(2,6-(CH 3 ) 2 -C 6 F 3 ) 4 - , [Al(2,4,6-(CH 3 ) 3 -C 6 F 2 ) 4 - , [Al(2,3,5,6-(CH 3 ) 4 -C 6 F) 4 - , [Al(3,5-(CH 3 ) 2 -C 6 F 3 ) 4 - , [Al(3,4,5-(CH 3 ) 3 -C 6 F 2 ) 4 - , [Al(2,6-(CF 3 ) 2 -C 6 H 3 ) 4 - , [Al(2,4,6-(CF 3 ) 3 ​​​​​​​​​​-C 6 H 2 ) 4 - ,[Al(2,3,5,6-(CF 3 ) 4 -C 6 H 4 - ,[Al(3,5-(CF 3 ) 2 -C 6 H 3 ) 4 - ,[Al(3,4,5-(CF 3 ) 3 -C 6 H 2 ) 4 - ,[Al(2,6-(CF 3 ) 2 -C 6 F 3 ) 4 - ,[Al(2,4,6-(CF 3 ) 3 -C 6 F 2 ) 4 - ,[Al(2,3,5,6-(CF 3 ) 4 -C 6 F 4 - ,[Al(3,5-(CF 3 ) 2 -C 6 F 3 ) 4 - ,[Al(3,4,5-(CF 3 ) 3 -C 6 F 2 ) 4 -,{t-Bu-CH=C[B(C 6 F 5 ) 2 2 (CH 3 )}-,{Ph-CH=C[B(C 6 F 5 ) 2 2 (CH 3 )}-,{(C 6 F​​​​​​​​​​5 )-CH=C[B(C 6 F 5 ) 2 2 (CH 3 )} - ,{t-Bu-CH=C[Al(C 6 F 5 ) 2 2 (CH 3 )} - ,{Ph-CH=C[Al(C 6 F 5 ) 2 2 (CH 3 )} - ,{(C 6 F 5 )-CH=C[Al(C 6 F 5 ) 2 2 (CH 3 )} - ,[1,1’-C 12 F 8 -2,2’=B(C 6 F 5 ) 2 - ,[1,1’-C 12 F 8 -2,2’=Al(C 6 F 5 ) 2 - ,[FB(1-C 6 F 4 -2-C 6 F 5 ) 3 - ,[(CH 3 )B(1-C 6 F 4 -2-C 6 F 5 ) 3 - ,[(C 6 F 5 )B(1-C 6 F 4 -2-C 6 F 5 ) 3 - ,[(C 6 F 5 )Al(1-C​​​​​​​​​6 F 4 -2-C 6 F 5 ) 3 - ,[FAl(1-C 6 F 4 -2-C 6 F 5 ) 3 -,[(CH 3 )Al(1-C 6 F 4 -2-C 6 F 5 ) 3 -,] - ,[HB(1-C 6 F 4 -2-C 6 F 5 ) 3 - ,[HAl(1-C 6 F 4 -2-C 6 F 5 ) 3 - ,[(CH 3 )B(2-C 10 F 7 ) 3 - ,[(CH 3 )Al(2-C 10 F 7 ) 3 - ,[(CH 3 )B(p-C 6 F 4 SiMe 3 ) 3 - ,[B(p-C 6 F 4 SiMe 3 ) 4 - ,[(CH 3 )B(p-C 6 F 4 Si(n-Bu) 3 ) 3 - ,[B(p-C 6 F 4 Si(n-Bu) 3 ) 4 - ,[(CH​​​​​​​​​3 )B(p-C 6 F 4 Si(i-Bu) 3 ) 3 - ,[B(p-C 6 F 4 Si(i-Bu) 3 ) 4 - ,[(CH 3 )B(p-C 6 F 4 Si(t-Bu) 3 ) 3 - ,[B(p-C 6 F 4 Si(t-Bu) 3 ) 4 - ,[(C 6 F 5 ) 3 B-C 6 F 4 -B(C 6 F 5 ) 2 - ,[C 6 F 4 -1,2-(B(C 6 F 5 ) 3 ) 2 - ,[C 6 F 4 -1,2-(Al(C 6 F 5 ) 3 ) 2 - ,[(C 6 F 4 )-1,2-(B(C 6 F 5 ) 2 ) 2 -1’,2’-(C 6 F 4 )] - ,[(C 6 F 4 )-1,2-(Al(C 6 F 5 ) 2 ) 2 -1’,2’-(C 6 F 4 )]​​​​​​​- ,[(C 6 F 5 ) 3 B-CN-B(C 6 F 5 ) 3 - ,[(C 6 F 5 ) 3 Al-CN-Al(C 6 F 5 ) 3 - ,[((C 6 F 5 ) 3 BNC) 4 Ni] - ,[((C 6 F 5 ) 3 AlNC) 4 Ni] - ,[(1,1’-C 12 F 8 ) 2 -2,2’-B] - ,[(1,1’-C 12 F 8 ) 2 -2,2’-Al] - ,[B(O-C 6 F 5 ) 4 -,[Al(O-C 6 F 5 ) 4 -,[(C 6 F 5 ) 3 Al-C 6 F 4 -Al(C 6 F 5 ) 2 -,[(CH 3 )Al(p-C 6 F 4 SiMe 3 ) 3 -,[Al(p-C 6 F 4 SiMe 3 ) 4 -,[(CH 3 )Al(p-C 6 F 4 Si(n-Bu) 3 ) 3 ​​-,[Al(p-C 6 F 4 Si(n-Bu) 3 ) 4 -,[(CH 3 )Al(p-C 6 F 4 Si(i-Bu) 3 ) 3 - ,[Al(p-C 6 F 4 Si(i-Bu) 3 ) 4 - ,[(CH 3 )Al(p-C 6 F 4 Si(t-Bu) 3 ) 3 - ,[Al(p-C 6 F 4 Si(t-Bu) 3 ) 4 - ,[C 5 (C 6 H 5 ) 5 - ,[C 5 (2,6-(CH 3 ) 2 -C 6 H 3 ) 5 - ,[C 5 (2,4,6-(CH 3 ) 3 -C 6 H 2 ) 5 - ,[C 5 (3,5-(CH 3 ) 2 -C 6 H 3 ) 5 - ,[C 5 (3,4,5-(CH 3 ) 3 -C 6 H 2 ) 5 -,[C 5 (2,6-(CF 3 ) 2 -C​​​​​​​​6 H 3 ) 5 -,[C 5 (2,4,6-(CF 3 ) 3 -C 6 H 2 ) 5 - ,[C 5 (3,5-(CF 3 ) 2 -C 6 H 3 ) 5 -,[C 5 (3,4,5-(CF 3 ) 3 -C 6 H 2 ) 5 -,[C 5 (2,6-(CH 3 ) 2 -C 6 F 3 ) 5 -,[C 5 (2,4,6-(CH 3 ) 3 -C 6 F 2 ) 5 -,[C 5 (3,5-(CH 3 ) 2 -C 6 F 3 ) 5 - ,[C 5 (3,4,5-(CH 3 ) 3 -C 6 F 2 ) 5 - ,[C 5 (2,6-(CF 3 ) 2 -C 6 F 3 ) 5 - ,[C 5 (2,4,6-(CF 3 ) 3 -C 6 F 2 ) 5 - ,[C 5 (3,5-(CF​​​​​3 ) 2 -C 6 F 3 ) 5 - ,[C 5 (3,4,5-(CF 3 ) 3 -C 6 F 2 ) 5 - ,[C 5 (C 6 F 5 ) 5 - ,[Li(Ta(OC 6 F 5 ) 4 ( 2 -OC 6 F 5 ) 2 ) 2 -,[Nb(OC 6 F 5 ) 6 - ,[PF 6 - ,[AsF 6 - ,[SbF 6 - ,[BF 4 -,[ClO 4 - , carborane anions such as: [C 2 B 9 H 12 - ,[CB 11 H 12 -, but not limited to this.

[0035] According to a specific embodiment of the present invention, preferably, the cocatalyst includes one or a combination of two or more of triethylaluminum, triisobutylaluminum, tri-n-propylaluminum, trihexylaluminum, tri-n-butylaluminum, triisopropylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, ethyldi-p-tolylaluminum, diethylbenzylaluminum.

[0036] According to a specific embodiment of the present invention, preferably, 50 - 80 kg of carrier is added per mole of the main catalyst.

[0037] According to a specific embodiment of the present invention, preferably, the molar ratio of the activator to the main catalyst is 10 - 500:1. ​​​​​​​​​

[0038] According to a specific embodiment of the present invention, preferably, the molar ratio of the cocatalyst to the main catalyst is 10 - 500:1.

[0039] According to a specific embodiment of the present invention, preferably, the synthesis method of the main catalyst is as shown in the following reaction formula:

[0040]

[0041] Wherein, Ts are the same as or different from each other, and the T is a monodentate or bidentate neutral ligand; LG is a leaving group, which are 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 XIV.

[0042] According to a specific embodiment of the present invention, preferably, in the synthesis method of the main catalyst, the monodentate neutral ligand is selected from ethers ROR, thioethers RSR, tertiary amines NR 3 , tertiary phosphines PR 3 , cyclic ethers, cyclic thioethers, ketones, substituted cyclohexanones, substituted pyridines, substituted pyrroles, substituted piperidines, esters, lactones, amides, lactams, wherein, R is selected from C 1 -C 20 linear or branched alkyl groups, C 1 -C 20 unsaturated hydrocarbon groups, C 1 -C 20 haloalkyl groups, C 1 -C 20 alkyl groups containing heteroatoms from Group XIII elements to Group XVII elements, C 3 -C 20 cycloalkyl groups, C 6 -C 30 aryl groups, C 7 -C 30 alkyl-substituted aryl groups, C 7 -C 30 aryl-substituted alkyl groups.

[0043] According to a specific embodiment of the present invention, preferably, in the synthesis method of the main catalyst, the bidentate neutral ligand is selected from ortho-diether classes, α,ω-diether classes, ortho-diamine classes, α,ω-diamine classes, ortho-dithioether classes, α,ω-dithioether classes, ortho-diphosphine classes, α,ω-diphosphine classes; wherein, x is 0, 1, 2 or 3.

[0044] According to a specific embodiment of the present invention, preferably, in the synthesis method of the main catalyst, the alkali metal elements include lithium, sodium and potassium; the organic radicals of the heavy elements of Group XIV include SiR 3 , GeR 3 , SnR3 , PdR 3 , ZnR, BaR, MgR and CaR, wherein R is selected from C 1 -C 20 linear or branched alkyl groups, C 1 -C 20 unsaturated hydrocarbon groups, C 1 -C 20 haloalkyl groups, C 1 -C 20 alkyl groups containing heteroatoms from Group XIII to Group XVII elements, C 3 -C 20 cycloalkyl groups, C 6 -C 30 aryl groups, C 7 -C 30 alkyl-substituted aryl groups, C 7 -C 30 aryl-substituted alkyl groups.

[0045] According to a specific embodiment of the present invention, preferably, in the synthesis method of the main catalyst, the reaction medium is C 5 -C 15 alkanes and / or cycloalkanes.

[0046] According to a specific embodiment of the present invention, preferably, in the synthesis method of the main catalyst, the reaction medium is one or a combination of two or more of hexane, heptane, octane, toluene, and xylene.

[0047] According to a specific embodiment of the present invention, preferably, in the synthesis method of the main catalyst, the reaction temperature is -100°C to 100°C, more preferably -75°C to 100°C, and further preferably -50°C to 100°C.

[0048] The present invention also provides a method for preparing the above metallocene catalyst composition, which includes the following steps: mixing the main catalyst, co-catalyst, activator, and carrier in a homogeneous liquid medium, and reacting at 5°C - 100°C for 1 - 8 h to obtain the metallocene catalyst composition.

[0049] According to a specific embodiment of the present invention, preferably, the homogeneous liquid medium includes a saturated alkane liquid medium and / or an aromatic liquid medium. The saturated alkane liquid medium includes one or a combination of two or more of pentane and its isomers, hexane and its isomers, heptane and its isomers, and octane and its isomers. The aromatic liquid medium includes one or a combination of two or more of 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. More preferably, it is one or a combination of two or more of toluene, hexane, and pentane.

[0050] The present invention also provides the application of the above metallocene catalyst composition in catalyzing olefin polymerization.

[0051] According to a specific embodiment of the present invention, preferably, the olefin polymerization process includes a bulk slurry polymerization process, a solution slurry polymerization process or a gas phase polymerization process.

[0052] According to a specific embodiment of the present invention, preferably, the olefin polymerization equipment is a batch polymerization reactor or a continuous production device.

[0053] The present invention uses a silica-modified carrier to load the metallocene complex, changing the homogeneous catalytic system into a heterogeneous catalytic system, further improving the polymer product morphology, increasing the bulk density and fluidity of the product, and can largely avoid blockage of the polymerization device; in addition, the metal-organic framework coordination polymer provides sufficient acidic sites, while increasing the specific surface area of the modified silica and improving the loading efficiency of the metal compound. Compared with the catalyst loaded with ordinary silica, the amount of expensive activators such as methylaluminoxane or borate reagents can be greatly reduced while maintaining the same activity level, and even when no activators such as methylaluminoxane or borate reagents are used, it can still have high activity, and the effective life of the catalyst is extended, reducing production costs while improving catalytic performance. The melt index of polypropylene can be adjusted only by adjusting the hydrogen concentration, and the adjustable range of the melt index is extremely wide, and the development of high melt index and ultra-high melt index polypropylene with different grades can be completed, which is conducive to industrial application and promotion. Detailed Embodiments

[0054] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solutions of the present invention are described in detail below, but it should not be construed as a limitation on the implementable scope of the present invention.

[0055] Example 1

[0056] This example provides a catalyst composition, which is prepared by the following steps:

[0057] (1) Synthesis of metallocene complex:

[0058]

[0059] In the above reaction formula, Q is a divalent radical, such as, =CR′ 2 、=SiR′ 2 、=GeR′ 2 、=NR′、=PR′、=BR′; M is Ti, Zr or Hf, and the specific synthesis steps are as follows:

[0060] Preparation of Cat-1: Dissolve the above-mentioned ligand dimethylsilylbiscyclopentadiene (0.186 g, 1 mmol) in 10 ml of dry MTBE (methyl tert-butyl ether), cool the temperature to 0 °C, add 0.8 mL of n-BuLi / hexane (2.5 M, 1.0 mmol), and stir for 2 h after naturally rising to room temperature to obtain a ligand lithium salt solution. Weigh 0.23 g of ZrCl 4 (Fw = 233.04, 1.0 mmol) into another reaction flask, add 10 mL of anhydrous MTBE under low temperature and nitrogen protection, stir for a moment in a -40 °C low-temperature cold bath, and slowly add the above-mentioned ligand lithium salt solution to the suspension of ZrCl 4 (the time used is 3 h). After the addition is completed, naturally rise to room temperature and stir overnight at room temperature. Vacuum dry the solvent to constant weight to obtain a white complex Cat-1;

[0061] (2) Preparation of metal-organic framework coordination polymer UiO-66: Add 5 mmol of zirconium chloride, 5 mmol of terephthalic acid, 1 mL of 37 wt% concentrated hydrochloric acid, and 50 mL of N,N-dimethylformamide to a 100 mL autoclave, ultrasonicate for 15 minutes, seal, heat at 120 °C for 2 days, naturally cool, and filter. Then, rinse with N,N-dimethylformamide 3 times, then soak in methanol for 2 days, during which fresh methanol needs to be replaced for soaking, then vacuum dry, and then dry and activate in vacuo at 150 °C for 12 hours to obtain a solid sample. The preparation method refers to Patent CN 116020416 A;

[0062] (3) Preparation of silica gel modified support S1:

[0063] Vacuum pump the Grace 955 type silica gel at 450 °C for 3 hours, and then naturally cool to room temperature under the protection of inert gas; add 5 g of the above dehydrated silica gel to a 500 mL three-necked flask containing 250 mL of hexane, add 0.2 g of UiO66 at room temperature, stir for 2 hours, filter and wash with hexane, vacuum pump dry, heat the above-obtained support from room temperature to 150 °C within 1 hour and keep it for 1 hour, then vacuum pump and raise the temperature to 200 °C and keep it for 3 hours, and naturally cool to room temperature, and keep the inert gas protection during the cooling process to obtain the silica gel modified support S1;

[0064] (4) Preparation of catalyst composition MPP-1:

[0065] The metallocene complex Cat-1 (20 μmol) was dissolved in toluene to prepare a solution. 1 g of the silica gel modified support S1 was added to a 50 mL flask containing 20 mL of toluene, and 3 mL of a 1 M triisobutylaluminum-hexane solution was added. After stirring for 3 hours, 5 mL of a MAO toluene solution (10 wt%, the same below) was added, the temperature was raised to 60 °C, and the reaction was heated for 2 hours, and then cooled to room temperature. The entire above-prepared Cat-1 toluene solution was added, and the mixture was stirred at room temperature for 30 minutes to obtain the catalyst composition MPP-1. The upper toluene clear solution was removed, and it was washed 3 more times with toluene, and then dried under vacuum to obtain the solid catalyst MPP-01.

[0066] Examples 2 - 6

[0067] Examples 2 to 6 respectively provided a catalyst composition MPP-2 to MPP-6, which was prepared by the following steps:

[0068] (1) Synthesis of metallocene complexes Cat-2 to Cat-6: The steps were the same as in Example 1, and the raw materials were replaced with ligand raw materials with corresponding substituents. The substituents of the metallocene complexes are shown in Table 1;

[0069] (2) Preparation of the silica gel modified support S1: The same as in Example 1.

[0070] (3) Preparation of the catalyst compositions MPP-2 to MPP-6: The same as in Example 1, except that Cat-1 was replaced with Cat-2 to Cat-6 respectively.

[0071] Example 7

[0072] This example provided a catalyst composition, which was prepared by the following steps:

[0073] (1) Synthesis of metallocene complex:

[0074]

[0075] In the above reaction formula, Q is a divalent radical, such as, =CR′ 2 、=SiR′ 2 、=GeR′ 2 、=NR′、=PR′、=BR′; M is Ti, Zr or Hf. The specific synthesis steps are as follows:

[0076] Preparation of Cat-7: Dissolve the above ligand dimethylsilylbis(2-methylindenyl)zirconium dichloride (0.47 g, 1 mmol) in 10 ml of dry MTBE (methyl tert-butyl ether), cool to 0 °C, add 0.8 mL of n-BuLi / hexane (2.5 M, 1.0 mmol), and stir for 2 h after naturally rising to room temperature to obtain a ligand lithium salt solution. Weigh 0.23 g of ZrCl 4 (Fw = 233.04, 1.0 mmol) into another reaction flask, add 10 mL of anhydrous MTBE under low temperature and nitrogen protection, stir briefly in a -40 °C low-temperature cold bath, and slowly add the above ligand lithium salt solution to the suspension of ZrCl 4 (over 3 h). After the addition is complete, naturally rise to room temperature and stir overnight at room temperature. Vacuum dry the solvent to constant weight to obtain a yellow complex Cat-7;

[0077] (2) Preparation of silica-modified support S2:

[0078] Vacuum the Grace 955 type silica at 450 °C for 3 hours, and then naturally cool to room temperature under inert gas protection; add 5 g of the above dehydrated silica to a 500 mL three-necked flask containing 250 mL of hexane, add 0.2 g of MIL-53(Al) at room temperature, stir for 2 hours, filter and wash with hexane, vacuum dry, heat the above-obtained support from room temperature to 150 °C within 1 hour and hold for 1 hour, then vacuum and heat up to 200 °C and hold for another 3 hours, and naturally cool to room temperature, maintaining inert gas protection during the cooling process to obtain the silica-modified support S2;

[0079] (3) Preparation of catalyst composition MPP-07:

[0080] Dissolve the metallocene complex Cat-7 (20 umol) in toluene to prepare a solution. Add 1 g of the silica-modified support S2 to a 50 mL flask containing 20 mL of toluene, add 3 mL of a 1 M triisobutylaluminum-hexane solution, stir for 3 hours, then add 5 ml of a MAO toluene solution, heat up to 60 °C, heat and react for 2 hours, and then cool to room temperature. Add all of the above-prepared Cat-7 toluene solution, stir at room temperature for 30 minutes to obtain the catalyst composition MPP-7. Remove the upper toluene clear solution, continue to wash with toluene 3 times, and then vacuum dry to obtain the solid catalyst MPP-07.

[0081] Examples 8 to 16

[0082] Examples 8 to 16 respectively provide a catalyst composition MPP-8 to MPP-16, which is prepared by the following steps:

[0083] (1) Synthesis of metallocene complexes Cat-8 to Cat-16: The steps are the same as in Example 7, with the ligand raw materials replaced by those with corresponding substituents. The substituents of the metallocene complexes are shown in Table 1;

[0084] (2) Preparation of silica-modified support S2: The same as in Example 7;

[0085] (3) Preparation of catalyst compositions MPP-8 to MPP-16: The same as in Example 7, except that Cat-7 is replaced by Cat-8 to Cat-16 respectively.

[0086] Example 17

[0087] This example provides a catalyst composition, which is prepared by the following steps:

[0088] (1) Synthesis of metallocene complex:

[0089]

[0090] In the above reaction formula, Q is a divalent radical, such as, =CR′ 2 , =SiR′ 2 , =GeR′ 2 , =NR′, =PR′, =BR′; M is Ti, Zr or Hf. The specific synthesis steps are as follows:

[0091] Preparation of Cat-17: Dissolve the above ligand dimethylsilylbis(4,5-benzoindenyl)zirconium chloride (0.62 g, 1 mmol) in 10 ml of dry MTBE (methyl tert-butyl ether), cool down to 0 °C, add 0.8 mL of n-BuLi / hexane (2.5 M, 1.0 mmol), and stir for 2 h after naturally rising to room temperature to obtain a ligand lithium salt solution. Weigh 0.23 g of ZrCl 4 (Fw = 233.04, 1.0 mmol) into another reaction flask, add 10 mL of anhydrous MTBE under low temperature and nitrogen protection, stir briefly in a -40 °C low-temperature cold bath, and slowly add the above ligand lithium salt solution to the suspension of ZrCl 4 (it takes 3 h), and after the addition is completed, naturally rise to room temperature and stir overnight at room temperature. Vacuum dry the solvent to constant weight to obtain the purple complex Cat-17;

[0092] (2) Preparation of silica-modified support S3:

[0093] The Grace 955 type silica gel was evacuated at 450 °C for 3 hours and then naturally cooled to room temperature under inert gas protection; 5 g of the above dehydrated silica gel was added to a 500 mL three-necked flask containing 250 mL of hexane, and 0.2 g of DUT-51 was added at room temperature, followed by stirring for 2 hours. It was filtered, washed with hexane, and dried under vacuum. The obtained support was heated from room temperature to 150 °C within 1 hour and maintained for 1 hour, then evacuated and heated to 200 °C and maintained for another 3 hours, and naturally cooled to room temperature while maintaining inert gas protection during the cooling process to obtain the silica gel modified support S3;

[0094] (3) Preparation of catalyst composition MPP-17:

[0095] The metallocene complex Cat-17 (20 μmol) was dissolved in toluene to prepare a solution. 1 g of the silica gel modified support S3 was added to a 50 mL flask containing 20 mL of toluene, and 3 mL of a 1 M triisobutylaluminum-hexane solution was added. After stirring for 3 hours, 4 mL of a MAO toluene solution was added, the temperature was raised to 60 °C, and the reaction was heated for 2 hours, and then cooled to room temperature. The entire above-prepared Cat-17 toluene solution was added, and the mixture was stirred at room temperature for 30 minutes to obtain the catalyst composition MPP-17. The upper toluene clear solution was removed, and it was washed 3 more times with toluene, and then dried under vacuum to obtain the solid catalyst MPP-017.

[0096] Examples 18 to 25

[0097] Examples 18 to 25 respectively provided a catalyst composition MPP-18 to MPP-25, which was prepared by the following steps:

[0098] (1) Synthesis of metallocene complexes Cat-18 to Cat-25: The steps were the same as in Example 17, and the raw materials were replaced with ligand raw materials with corresponding substituents. The substituents of the metallocene complexes are shown in Table 1;

[0099] (2) Preparation of silica gel modified support S3: The same as in Example 17;

[0100] (3) Preparation of catalyst composition MPP-18 to MPP-25: The same as in Example 17, except that Cat-17 was replaced with Cat-18 to Cat-25 respectively.

[0101] Examples 26 to 30

[0102] (1) Synthesis of metallocene complexes Cat-26 to Cat-30: The steps were the same as in Example 1, and the raw materials were replaced with ligand raw materials with corresponding substituents. The substituents of the metallocene complexes are shown in Table 1;

[0103] (2) Preparation of silica-modified support S3: The same as in Example 17;

[0104] (3) Preparation of catalyst compositions MPP-26 to MPP-30: The same as in Example 17, except that Cat-17 was replaced with Cat-26 to Cat-30 respectively.

[0105] Table 1: Metallocene complex structure

[0106]

[0107]

[0108] Example 31

[0109] This example provides a catalyst composition, which is prepared by the following steps:

[0110] Dissolve the metallocene complex Cat-1 (20 μmol) in toluene to prepare a solution. Add 1 g of silica-modified support S1 to a 50 mL flask containing 20 mL of toluene, add 3 mL of a 1 M triisobutylaluminum-hexane solution, stir for 3 hours, then add 5 mL of an isobutyl-modified MAO (MMAO) toluene solution (10 wt%), heat up to 50 °C, heat and react for 2 hours, and then cool down to room temperature. Add all the above-prepared Cat-1 toluene solution, stir at room temperature for 30 minutes to obtain the catalyst composition MPP-31. Remove the upper toluene clear solution, continue to wash with toluene 3 times, and then vacuum dry to obtain the solid catalyst MPP-031.

[0111] Example 32

[0112] This example provides a catalyst composition, which is prepared by the following steps:

[0113] Dissolve the metallocene complex Cat-1 (20 μmol) in toluene to prepare a solution. Add 1 g of silica-modified support S1 to a 50 mL flask containing 20 mL of toluene, add 1 mL of a 1 M triethylaluminum hexane solution, stir for 3 hours, dissolve 10 mg of [PhMe 2 NH][B(C 6 F 5 ) 4 in 5 mL of toluene, slowly add it dropwise to the above reaction solution, heat up to 50 °C, heat and react for 2 hours, and then cool down to room temperature. Add all the above-prepared Cat-1 toluene solution, stir at room temperature for 30 minutes to obtain the catalyst composition MPP-32. Remove the upper toluene clear solution, continue to wash with toluene 3 times, and then vacuum dry to obtain the solid catalyst MPP-032.

[0114] Example 33

[0115] This example provides a catalyst composition, which is prepared by the following steps:

[0116] (1) Preparation of silica-modified support S4:

[0117] After evacuating Grace 955 type silica gel at 450 °C for 3 hours, it is naturally cooled to room temperature under inert gas protection; 5 g of the above dehydrated silica gel is added to a 500 mL three-necked flask containing 250 mL of hexane, 0.5 g of MIL-53(Al) is added at room temperature, stirred for 2 hours, heated to 50 °C, reacted for 2 h, then cooled to room temperature, filtered and washed with hexane, and dried under vacuum. The support obtained above is heated from room temperature to 150 °C within 1 hour and maintained for 1 hour, then evacuated and heated to 200 °C and maintained for 3 hours, and naturally cooled to room temperature. During the cooling process, inert gas protection is maintained to obtain silica-modified support S4;

[0118] (2) Preparation of catalyst composition MPP-33:

[0119] The metallocene complex Cat-7 (20 μmol) is dissolved in toluene to prepare a solution. 1 g of silica-modified support S4 is added to a 50 mL flask containing 20 mL of toluene, 10 mL of a 1 M triethylaluminum hexane solution is added, heated to 60 °C, and reacted for 3 hours, then cooled to room temperature. 0.47 g of the toluene solution of Cat-7 is added, stirred at room temperature for 30 minutes to obtain catalyst composition MPP-33. The upper toluene clear solution is removed, and it is washed 3 times with toluene, and then dried under vacuum to obtain solid catalyst MPP-033.

[0120] Example 34 Propylene bulk polymerization reaction

[0121] The polymerization is carried out in a 5 L autoclave. The autoclave is first purged and replaced with dry nitrogen, and then hydrogen at 0.05 MPa is introduced. 55 mg of the catalyst MPP-01 prepared in Example 1 is suspended in 5 ml of n-hexane to form a slurry and added to the catalyst feeder. Subsequently, 3.5 ml of a 1 mol / L triisobutylaluminum hexane solution is added, the stirring is started, and 2.3 L of liquid propylene is used to flush the catalyst and triisobutylaluminum into the reaction kettle, heated to 70 °C and reacted for 1 hour to obtain 240 g of powdery polypropylene. The polymerization activity is 4356 gPP / gcat, the melt index of polypropylene is 35 g / 10 min, the molecular weight distribution is 3.3, and the bulk density of the polymer is 0.39 g / cm 3 .

[0122] Example 35 Propylene bulk polymerization reaction

[0123] The polymerization was carried out in a 5 L autoclave. The autoclave was first purged and replaced with dry nitrogen, and then hydrogen gas at 0.07 MPa was introduced. 54 mg of the catalyst MPP-01 prepared in Example 1 was suspended in 5 ml of n-hexane to form a slurry, which was added to the catalyst feeder. Subsequently, 3.5 ml of a 1 mol / L solution of triisobutylaluminum in hexane was added. Stirring was started, and the catalyst and triisobutylaluminum were flushed into the reaction kettle with 2.3 L of liquid propylene. The temperature was raised to 70 °C and the reaction was carried out for 1 hour to obtain 278 g of powdery polypropylene. The polymerization activity was 5148 g PP / g cat, the melt index of polypropylene was 78 g / 10 min, the molecular weight distribution was 3.3, and the bulk density of the polymer was 0.38 g / cm 3 。

[0124] Example 36 Bulk Polymerization of Propylene

[0125] The polymerization was carried out in a 5 L autoclave. The autoclave was first purged and replaced with dry nitrogen, and then hydrogen gas at 0.09 MPa was introduced. 50 mg of the catalyst MPP-01 prepared in Example 1 was suspended in 5 ml of n-hexane to form a slurry, which was added to the catalyst feeder. Subsequently, 3.5 ml of a 1 mol / L solution of triisobutylaluminum in hexane was added. Stirring was started, and the catalyst and triisobutylaluminum were flushed into the reaction kettle with 2.3 L of liquid propylene. The temperature was raised to 70 °C and the reaction was carried out for 1 hour to obtain 312 g of powdery polypropylene. The polymerization activity was 6240 g PP / g cat, the melt index of polypropylene was 248 g / 10 min, the molecular weight distribution was 3.4, and the bulk density of the polymer was 0.39 g / cm 3 。

[0126] Example 37 Bulk Polymerization of Propylene

[0127] The polymerization was carried out in a 5 L autoclave. The autoclave was first purged and replaced with dry nitrogen, and then hydrogen gas at 0.12 MPa was introduced. 50 mg of the catalyst MPP-01 prepared in Example 1 was suspended in 5 ml of n-hexane to form a slurry, which was added to the catalyst feeder. Subsequently, 3.5 ml of a 1 mol / L solution of triisobutylaluminum in hexane was added. Stirring was started, and the catalyst and triisobutylaluminum were flushed into the reaction kettle with 2.3 L of liquid propylene. The temperature was raised to 70 °C and the reaction was carried out for 1 hour to obtain 336 g of powdery polypropylene. The polymerization activity was 6720 g PP / g cat, the melt index of polypropylene was 820 g / 10 min, the molecular weight distribution was 3.4, and the bulk density of the polymer was 0.39 g / cm 3 。

[0128] Example 38 Bulk Polymerization of Propylene

[0129] The polymerization was carried out in a 5L autoclave. The autoclave was first purged and replaced with dry nitrogen, and then hydrogen gas at 0.15 MPa was introduced. 51 mg of the catalyst MPP-01 prepared in Example 1 was suspended in 5 ml of n-hexane to form a slurry, which was added to the catalyst feeder. Subsequently, 3.5 ml of a 1 mol / L solution of triisobutylaluminum in hexane was added. Stirring was started, and the catalyst and triisobutylaluminum were flushed into the reaction kettle with 2.3 L of liquid propylene. The temperature was raised to 70 °C and reacted for 1 hour to obtain 371 g of powdery polypropylene. The polymerization activity was 7274 gPP / gcat, the melt index of polypropylene was 1650 g / 10 min, the molecular weight distribution was 3.3, and the bulk density of the polymer was 0.41 g / cm 3 。

[0130] Example 39 Propylene Bulk Polymerization Reaction

[0131] The polymerization was carried out in a 5L autoclave. The autoclave was first purged and replaced with dry nitrogen, and then hydrogen gas at 0.18 MPa was introduced. 52 mg of the catalyst MPP-01 prepared in Example 1 was suspended in 5 ml of n-hexane to form a slurry, which was added to the catalyst feeder. Subsequently, 3.5 ml of a 1 mol / L solution of triisobutylaluminum in hexane was added. Stirring was started, and the catalyst and triisobutylaluminum were flushed into the reaction kettle with 2.3 L of liquid propylene. The temperature was raised to 70 °C and reacted for 1 hour to obtain 352 g of powdery polypropylene. The polymerization activity was 6769 gPP / gcat, the melt index of polypropylene was 3450 g / 10 min, the molecular weight distribution was 3.3, and the bulk density of the polymer was 0.40 g / cm 3 。

[0132] Example 40 Propylene Bulk Polymerization Reaction

[0133] The polymerization was carried out in a 5L autoclave. The autoclave was first purged and replaced with dry nitrogen, and then hydrogen gas at 0.23 MPa was introduced. 51 mg of the catalyst MPP-01 prepared in Example 1 was suspended in 5 ml of n-hexane to form a slurry, which was added to the catalyst feeder. Subsequently, 3.5 ml of a 1 mol / L solution of triisobutylaluminum in hexane was added. Stirring was started, and the catalyst and triisobutylaluminum were flushed into the reaction kettle with 2.3 L of liquid propylene. The temperature was raised to 70 °C and reacted for 1 hour to obtain 345 g of powdery polypropylene. The polymerization activity was 6764 gPP / gcat, the melt index of polypropylene was 8950 g / 10 min, the molecular weight distribution was 3.5, and the bulk density of the polymer was 0.39 g / cm 3 。

[0134] Example 41 to Example 72 Propylene Bulk Polymerization Reaction

[0135] (1) The metallocene complexes used were Cat-2 to Cat-30 respectively;

[0136] (2) The metallocene catalysts used were MPP-02 to MPP-033 respectively;

[0137] (3) The polymerization process was the same as that in Example 38. The catalyst activity, polymerization reaction conditions and polymer properties are shown in Table 2.

[0138] Example 73

[0139] The metallocene catalyst prepared by the present invention is also applicable to continuous devices, especially applicable to the Spheripol continuous loop reactor device, which is a double-loop polypropylene production device. When used for the production of metallocene products, the device includes: 1. Catalyst storage tank; 2. Prepolymerization reactor; 3. First loop reactor; 4. Second loop reactor; 5. Flash tank; 6. Filter; 7. Steam stripping tank and dryer. The prepolymerization reactor is a small single-loop reactor or a kettle reactor. The prepolymerization used in this experiment is a kettle reactor.

[0140] The specific steps are as follows:

[0141] (1) The catalyst MPP-01 was first added to the catalyst preparation tank, and then a mixed solution of vaseline and white oil (mass ratio 7:3) was added to prepare a slurry with a catalyst mass fraction of 20%. Then, under the combined action of triethylaluminum and propylene, the catalyst entered the prepolymerization reactor. The main catalyst feed rate was 0.2 ml / min, the propylene feed rate was 30 kg / h, the mass ratio of triethylaluminum to all fed propylene was 1:5000, the reaction temperature was 25 °C, the reaction pressure was 3.4 MPa, and the reaction time was 8 minutes;

[0142] (2) The prepolymer obtained in step (1) and fresh propylene and hydrogen entered the first loop reactor to continue the polymerization reaction. The mass ratio of hydrogen to propylene entering the first loop reactor was 1:5000 (200 ppm), the reaction temperature was 70 °C, the reaction pressure was 3.8 MPa, and the reaction time was 40 minutes;

[0143] (3) The polymer obtained in step (2) and fresh propylene and hydrogen entered the second loop reactor to continue the reaction. The mass ratio of hydrogen to propylene entering the second loop reactor was 1:5000 (200 ppm), the reaction temperature was 70 °C, the reaction pressure was 3.8 MPa, and the reaction time was 40 minutes; The material at the outlet of the second loop passed through devices such as a flash tank and a dryer to obtain polypropylene powder, which was high melt index polypropylene resin. The melt index of polypropylene was 1750 g / 10 min, the bulk density of the polymer was 0.41 g / cm 3 , and the molecular weight distribution was 2.9; After calculation, the catalyst activity was 10025 gPP / gcat.

[0144] Example 74

[0145] Example 74 is similar to Example 73, except for the catalyst used and the addition amounts of components in each polymerization stage. Specifically, the catalyst used in this example is catalyst MPP-08. In the prepolymerization stage, the catalyst feed rate is 0.18 mL / min, the hydrogen concentration in the loop reactor is 220 ppm, and the reaction temperature is 70°C. The obtained polypropylene has a melt index of 1680 g / 10 min and a polymer bulk density of 0.41 g / cm 3 , and a molecular weight distribution of 2.8; the catalyst activity is calculated to be 9825 gPP / gcat.

[0146] Example 75

[0147] Example 75 is similar to Example 73, except for the catalyst used and the addition amounts of components in each polymerization stage. Specifically, the catalyst used in this example is supported catalyst MPP-020. In the prepolymerization stage, the catalyst feed rate is 0.21 mL / min, the hydrogen concentration in the loop reactor is 330 ppm, and the reaction temperature is 70°C. The obtained polypropylene has a melt index of 7880 g / 10 min and a polymer bulk density of 0.41 g / cm 3 , and a molecular weight distribution of 2.8; the catalyst activity is calculated to be 11825 gPP / gcat.

[0148] Comparative Examples 1 to 3

[0149] (1) Metallocene complexes Cat-1 to Cat-3 are used respectively;

[0150] (2) Activation of silica gel support S0:

[0151] Silica gel of Grace 955 type is evacuated at 450°C for 3 hours and then naturally cooled to room temperature under inert gas protection.

[0152] (3) Preparation of catalyst compositions D1 to D3:

[0153] Metallocene complexes Cat-1 to Cat-3 (20 umol) are respectively dissolved in toluene to prepare solutions with a concentration of 10 mM. 5 g of the activated Grace-955 silica gel support is added to a 50 mL flask containing 20 mL of toluene, 3 mL of a 1 M triisobutylaluminum-hexane solution is added, and after stirring for 3 hours, 15 ml of a MAO toluene solution (10 wt%) is added. The temperature is raised to 60°C and heated for 2 hours, then cooled to room temperature. The above-prepared Cat-1 to Cat-3 toluene solutions are added respectively, and stirred at room temperature for 30 minutes to obtain catalyst compositions. The upper toluene clear solution is removed, and the catalyst compositions are washed with toluene 3 more times, and then dried under vacuum to obtain solid catalysts D-1 to D-3.

[0154] (4) Polymerization: The polymerization conditions are the same as in Example 34, and the polymerization results are shown in Table 2.

[0155] Comparative Example 4

[0156] (1) The metallocene complex used is Cat-1;

[0157] (2) Preparation of catalyst composition D4:

[0158] Dissolve the metallocene complex Cat-1 in toluene to prepare a solution with a concentration of 10 mM. Take 1 mL of the toluene solution of Cat-1 and add 5000 μmol of MAO (methylaluminoxane) solution, and stir at room temperature for 30 minutes to obtain catalyst composition D4;

[0159] (3) Polymerization: The polymerization conditions are the same as in Example 34, and the polymerization results are shown in Table 2.

[0160] Table 2: Catalysts and Polymerization Performance

[0161]

[0162]

[0163] Test standards: Melt index, GB / T3682; Bulk density, ASTM D1895A; Molecular weight distribution, GB / T36214.2 - 2018.

[0164] It can be seen from Table 2 that in Comparative Example 4, no carrier was used, the polymer had poor fluidity and caking, and the bulk density could not be measured. The present invention proposes a novel structure of the metallocene complex and uses a silica-modified carrier to optimize the final catalyst, which can improve the polymer morphology, increase the bulk density, enhance the catalyst activity, reduce the polymer molecular weight distribution, and can simultaneously achieve the development of high melt index and ultra-high melt index polypropylene. In particular, this series of catalysts can be used in continuous production devices and exhibit the characteristics of high activity and high hydrogen response sensitivity.

[0165] Certainly, the present invention may also have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and deformations according to the present invention, but these corresponding changes and deformations should all fall within the protection scope of the claims of the present invention.

Claims

1. A metallocene catalyst composition, the composition of which comprises a main catalyst, a cocatalyst, an activator and a support, wherein, the main catalyst has a structure shown in Formula I: In Formula I, M is selected from Group 3 transition metal elements, Group 4 transition metal elements, Group 5 transition metal elements, and Group 6 transition metal elements; the n Xs are the same as or different from each other and are each independently selected from H, halogen, -R, -OR, -SR, -OCOR, -NR 2 , -PR 2 , -OR°O-, -OSO 2 CF 3 , where R is independently selected from C 1 -C 20 linear or branched alkyl, C 1 -C 20 unsaturated hydrocarbon group, C 1 -C 20 haloalkyl, C 1 -C 20 hydrocarbon group containing heteroatoms from Group 13 elements to Group 17 elements, C 1 -C 20 silyl and its derivatives, C 3 -C 20 cycloalkyl, C 6 -C 30 aryl, C 7 -C 30 alkyl-substituted aryl and its derivatives, C 7 -C 30 aryl-substituted alkyl and its derivatives; R° is a divalent hydrocarbon group and its derivatives; n is an integer from 1 to 4; Q is selected from -CR′ 2 -, -SiR′ 2 -, -GeR′ 2 -, -NR′-, -PR′-, -BR′-, where R′ is independently selected from C 1 -C 20 linear or branched alkyl, C 1 -C 20 unsaturated hydrocarbon group, C 1 -C 20 haloalkyl, C 1 -C 20 hydrocarbon group containing heteroatoms from Group 13 to Group 17 elements, C 1 -C 20 silyl and its derivatives, C 3 -C 20 cycloalkyl, C 6 -C 30 aryl, C 7 -C 30 alkyl-substituted aryl and its derivatives, C 7 -C 30 aryl-substituted alkyl and its derivatives; A and Z are the same or different, and each independently selected from Ligand 1, Ligand 2, Ligand 3; Ligand 1 has a structure shown in Formula II: In formula II, R 1 and R 1 ’ are the same or different and each independently selected from H, a hydrocarbon group of C 1 -C 20 and its derivatives, a furyl group of C 4 -C 10 and its derivatives, a thienyl group of C 4 -C 10 and its derivatives; R 2 and R 2 ’ are the same or different and each independently selected from a linear or branched alkyl group of C 1 -C 40 , an unsaturated hydrocarbon group of C 1 -C 40 , a haloalkyl group of C 1 -C 40 , a hydrocarbon group containing a heteroatom from Group 13 to Group 17 elements of C 1 -C 40 , a silyl group of C 1 -C 40 and its derivatives, 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 and its derivatives, an aryl-substituted alkyl group of C 7 -C 40 and its derivatives; Ligand 2 has a structure shown in Formula III: In formula III, R 1 is selected from H, C 1 -C 20 hydrocarbyl groups and their derivatives, C 4 -C 10 furyl groups and their derivatives, C 4 -C 10 thienyl groups and their derivatives; R 3 and R 3 ' are the same or different and each independently selected from H, C 1 -C 40 linear or branched alkyl groups, C 1 -C 40 unsaturated hydrocarbyl groups, C 1 -C 40 haloalkyl groups, C 1 -C 40 hydrocarbyl groups containing heteroatoms from Group 13 to Group 17 elements, C 1 -C 40 silyl groups and their derivatives, C 3 -C 40 cycloalkyl groups, C 6 -C 40 aryl groups, C 7 -C 40 alkyl-substituted aryl groups and their derivatives, C 7 -C 40 aryl-substituted alkyl groups and their derivatives; R 4 and R 4 ' are the same or different and each independently selected from H, halogen, C 1 -C 40 linear or branched alkyl groups, C 1 -C 40 unsaturated hydrocarbyl groups, C 1 -C 40 haloalkyl groups, C 1 -C 40 hydrocarbyl groups containing heteroatoms from Group 13 to Group 17 elements, C 1 -C 40 silyl groups and their derivatives, C 3 -C 40 cycloalkyl groups, C 6 -C 40 aryl groups, C 7 -C 40 alkyl-substituted aryl groups and their derivatives, C 7 -C 40 aryl-substituted alkyl groups and their derivatives; R 5 is selected from H, halogen, -R, where R is selected from C 1 -C 20 linear or branched alkyl, C 1 -C 20 unsaturated hydrocarbon group, C 1 -C 20 haloalkyl, C 1 -C 20 hydrocarbon group containing heteroatoms from Group 13 to Group 17 elements, C 1 -C 20 silyl group and its derivatives, C 3 -C 20 cycloalkyl, C 6 -C 30 aryl, C 7 -C 30 alkyl-substituted aryl and its derivatives, C 7 -C 30 aryl-substituted alkyl and its derivatives; Ligand 3 has a structure shown in Formula IV: In formula IV, R 1 is selected from H, C 1 -C 20 hydrocarbyl groups and their derivatives, C 4 -C 10 furyl groups and their derivatives, C 4 -C 10 thienyl groups and their derivatives; R 4 , R 4 ’, R 4 ” and R 4 ”’ are the same or different and are each independently selected from H, halogen, C 1 -C 40 linear or branched alkyl groups, C 1 -C 40 unsaturated hydrocarbyl groups, C 1 -C 40 haloalkyl groups, C 1 -C 40 hydrocarbyl groups containing heteroatoms from Group 13 to Group 17 elements, C 1 -C 40 silyl groups and their derivatives, C 3 -C 40 cycloalkyl groups, C 6 -C 40 aryl groups, C 7 -C 40 alkyl-substituted aryl groups and their derivatives, C 7 -C 40 aryl-substituted alkyl groups and their derivatives; R 5 is selected from H, halogen, -R, where R is selected from C 1 -C 20 linear or branched alkyl groups, C 1 -C 20 unsaturated hydrocarbyl groups, C 1 -C 20 haloalkyl groups, C 1 -C 20 hydrocarbyl groups containing heteroatoms from Group 13 to Group 17 elements, C 1 -C 20 silyl groups and their derivatives, C 3 -C 20 cycloalkyl groups, C 6 -C 30 aryl groups, C 7 -C 30 alkyl-substituted aryl groups and their derivatives, C 7 -C 30 aryl-substituted alkyl groups and their derivatives; R 6 and R 6 'Same or different, each independently selected from H, halogen, -OR, -SR, -OCOR, -NR 2 , -PR 2 , wherein R is independently selected from C 1 -C 40 linear or branched alkyl, C 1 -C 40 unsaturated hydrocarbon group, C 1 -C 40 haloalkyl, C 1 -C 40 hydrocarbon group containing heteroatoms from Group 13 to Group 17 elements, C 1 -C 40 silyl and its derivatives, C 3 -C 40 cycloalkyl, C 6 -C 40 aryl, C 7 -C 40 alkyl-substituted aryl and its derivatives, C 7 -C 40 aryl-substituted alkyl and its derivatives.

2. The metallocene catalyst composition according to claim 1, wherein, in Formula I, M is selected from Group 3 transition metal elements and Group 4 transition metal elements, preferably selected from titanium, zirconium, hafnium; Preferably, the n Xs are the same as or different from each other and are each independently selected from halogen, -R, -OR, -SR, -OCOR, -NR 2 , -PR 2 , -OR°O-, -OSO 2 CF 3 , wherein R is independently selected from 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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(trifluoromethyl)phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, 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-bis(trimethylsilyl)benzyl, 3,5-bis(trifluoromethyl)benzyl, 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; X is more preferably selected from chlorine, bromine, C 1 -C 20 alkyl of, C 6 -C 20 aryl of, C 7 -C 20 benzyl of; R° is selected from C 2 -C 40 alkylene of, C 6 -C 30 arylene of, C 7 -C 40 alkylated arylene of, C 7 -C 40 arylated alkylene of; Preferably, Q is selected from -CR′ 2 -, -SiR′ 2 -, -GeR′ 2 -, -NR′-, -PR′-, -BR′-, wherein R′ is independently selected from 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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(trifluoromethyl)phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, 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-bis(trimethylsilyl)benzyl, 3,5-bis(trifluoromethyl)benzyl, 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; more preferably, R′ is independently selected from methyl, ethyl, isopropyl, trimethylsilyl, phenyl, benzyl.

3. The metallocene catalyst composition according to claim 1, wherein, In formula II, R 1 and R 1 ' are the same or different and each independently selected from H, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furyl, 2-thienyl; R 2 and R 2 ’ are the same as or different from each other and are each independently selected from 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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(trifluoromethyl)phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, 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-bis(trimethylsilyl)benzyl, 3,5-bis(trifluoromethyl)benzyl, 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; preferably, R 2 and R 2 ’ are each independently selected from methyl, ethyl, isopropyl, tert-butyl, phenyl.

4. The metallocene catalyst composition according to claim 1, wherein, In formula III, R 1 is selected from H, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furyl, 2-thienyl; R 3 and R 3 ’ are the same as or different from each other and are each independently selected from H, 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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(trifluoromethyl)phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, 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-bis(trimethylsilyl)benzyl, 3,5-bis(trifluoromethyl)benzyl, 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. Preferably, R 3 and R 3 ’ are each independently selected from 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, pyrimidine, wherein the substituents in the substituted phenyl are selected from cyano, nitro, F, methyl, ethyl, isopropyl, tert-butyl, methoxy, tert-butoxy, trifluoromethoxy, Cl, trifluoromethyl, carbonyl, trimethylsilyl; R 4 and R 4 ’ are the same as or different from each other and are each independently selected from H, fluorine, chlorine, 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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(trifluoromethyl)phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, 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-bis(trimethylsilyl)benzyl, 3,5-bis(trifluoromethyl)benzyl, 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. Preferably, R 4 and R 4 ’ are each independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, phenyl; R 5 selected from H, fluorine, -R, wherein R is selected from 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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(trifluoromethyl)phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, 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-bis(trimethylsilyl)benzyl, 3,5-bis(trifluoromethyl)benzyl, 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.

5. The metallocene catalyst composition according to claim 1, wherein, In formula IV, R 1 is selected from H, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furyl, 2-thienyl; R 4 、R 4 ’, R 4 ” and R 4 ”’ are the same as or different from each other, and are each independently selected from H, fluorine, chlorine, 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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(trifluoromethyl)phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, 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-bis(trimethylsilyl)benzyl, 3,5-bis(trifluoromethyl)benzyl, 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. Preferably, R 4 、R 4 ’, R 4 ” and R 4 ”’ are each independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, and phenyl; R 5 selected from H, fluorine, -R, wherein R is selected from 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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, 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; R 6 and R 6 ’ are the same or different and each independently selected from H, halogen, -OR, -SR, -OCOR, -NR 2 , -PR 2 , wherein R is independently selected from 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, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 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(trifluoromethyl)phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-trimethylsilylphenyl, 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-bis(trimethylsilyl)benzyl, 3,5-bis(trifluoromethyl)benzyl, 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.

6. The metallocene catalyst composition according to claim 1, wherein, the support is a silica modified support, and the silica modified support is obtained by reacting a metal-organic framework coordination polymer with silica and then heating; Preferably, the preparation method of the silica modified support comprises the following steps: At -30°C to 120°C, dehydrated silica is dispersed in an organic solvent, and then mixed and contacted with a metal-organic framework coordination polymer for 0.5 - 10 h, filtered and washed, evacuated, heated at 150 - 200°C for 1 - 6 h, and heated at 200 - 300°C for 1 - 6 h under a protective gas atmosphere to obtain the silica modified support.

7. The metallocene catalyst composition according to claim 6, wherein, The metal-organic framework coordination polymer is selected from UiO-66, UiO-66-NH 2 , UiO-66-MM, UiO-66-Br, UiO-66-Br 2 , UiO-66-CO 2 H, UiO-67, MIL-100(Al), MIL-100(Fe), MIL-53(Al), MIL-53(Cr), MIL-127, MIL-101-NH 2 (Cr), MIL-125-NH 2 (Ti), Zn-MOF-508, Zn-DMOF-A, Zn-DMOF-TM, CAU-10-H, CAU-10-CH 3 , CAU-10-NO 2 , CAU-10-NH 2 , CAU-10-OH, CAU-10-OCH 3 , MOF-801-P, MOF-801-SC, MOF-802, MOF-804, MOF-841, DUT-51(Zr), DUT-51(Hf), DUT-67(Zr), or a combination of two or more thereof; Preferably, the dehydration condition of silica is to evacuate at 300 - 600°C; Preferably, the organic solvent includes one or a combination of two or more of toluene, hexane, heptane; Preferably, 1 - 100 mg of the metal-organic framework coordination polymer is added per gram of dehydrated silica.

8. The metallocene catalyst composition according to claim 1, wherein, the activator is a Lewis acidic substance, preferably including one or a combination of two or more of methylaluminoxane, polymethylaluminoxane, modified methylaluminoxane, organic boron reagent.

9. The metallocene catalyst composition according to claim 1, wherein, the cocatalyst includes one or a combination of two or more of triethylaluminum, triisobutylaluminum, tri-n-propylaluminum, trihexylaluminum, tri-n-butylaluminum, triisopropylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, ethyldi-p-tolylaluminum, diethylbenzylaluminum.

10. The metallocene catalyst composition according to claim 1, wherein, 50 - 80 kg of support is added per mole of the main catalyst; Preferably, the molar ratio of the activator to the main catalyst is 10 - 500:1; Preferably, the molar ratio of the cocatalyst to the main catalyst is 10 - 500:

1.

11. The metallocene catalyst composition according to claim 1, wherein, the synthesis method of the main catalyst is shown by the following reaction formula: wherein, T are the same or different from each other, and the T is a monodentate or bidentate neutral ligand; LG is a leaving group, which may be the same or different from each other, and the LG is hydrogen, an alkali metal element or an organic radical of a Group XIV heavy element.

12. The metallocene catalyst composition according to claim 11, wherein, In the synthesis method of the main catalyst, the monodentate neutral ligand is selected from ethers ROR, thioethers RSR, tertiary amines NR 3 , tertiary phosphines PR 3 , cyclic ethers, cyclic thioethers, ketones, substituted cyclohexanones, substituted pyridines, substituted pyrroles, substituted piperidines, esters, lactones, amides, lactams, wherein R is selected from C 1 -C 20 linear or branched alkyl groups, C 1 -C 20 unsaturated hydrocarbon groups, C 1 -C 20 haloalkyl groups, C 1 -C 20 alkyl groups containing heteroatoms from Group XIII to Group XVII elements, C 3 -C 20 cycloalkyl groups, C 6 -C 30 aryl groups, C 7 -C 30 alkyl-substituted aryl groups, C 7 -C 30 aryl-substituted alkyl groups.

13. The metallocene catalyst composition according to claim 11, wherein, In the synthesis method of the main catalyst, the bidentate neutral ligand is selected from ortho-diether, α,ω-diether, ortho-diamine, α,ω-diamine, ortho-dithioether, α,ω-dithioether, ortho-diphosphine, α,ω-diphosphine; wherein, x is 0, 1, 2 or 3.

14. The metallocene catalyst composition according to claim 11, wherein, In the synthesis method of the main catalyst, the alkali metal elements include lithium, sodium and potassium; the organic radicals of the Group XIV heavy elements include SiR 3 、GeR 3 、SnR 3 、PdR 3 、ZnR, BaR, MgR and CaR, where R is selected from straight-chain or branched alkyl groups of C 1 -C 20 , unsaturated hydrocarbon groups of C 1 -C 20 , haloalkyl groups of C 1 -C 20 , alkyl groups containing heteroatoms of Group XIII elements to Group XVII elements of C 1 -C 20 , cycloalkyl groups of C 3 -C 20 , aryl groups of C 6 -C 30 , alkyl-substituted aryl groups of C 7 -C 30 , aryl-substituted alkyl groups of C 7 -C 30 .

15. The metallocene catalyst composition according to claim 11, wherein, In the synthesis method of the main catalyst, the reaction medium is C 5 -C 15 alkane and / or cycloalkane.

16. The metallocene catalyst composition according to claim 11, wherein, In the synthesis method of the main catalyst, the reaction medium is one or a combination of two or more of hexane, heptane, octane, toluene, and xylene.

17. The metallocene catalyst composition according to claim 11, wherein, In the synthesis method of the main catalyst, the reaction temperature is -100°C to 100°C, preferably -75°C to 100°C, more preferably -50°C to 100°C.

18. The preparation method of the metallocene catalyst composition according to any one of claims 1-17, which comprises the following steps: Mix the main catalyst, cocatalyst, activator, and carrier in a homogeneous liquid medium, and react at 5°C - 100°C for 1 - 8 h to obtain the metallocene catalyst composition.

19. The preparation method according to claim 18, wherein, The homogeneous liquid medium includes a saturated alkane liquid medium and / or an aromatic liquid medium. The saturated alkane liquid medium includes one or a combination of two or more of pentane and its isomers, hexane and its isomers, heptane and its isomers, and octane and its isomers. The aromatic liquid medium includes one or a combination of two or more of 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.

20. The application of the metallocene catalyst composition according to any one of claims 1-17 in the catalytic polymerization of olefins.

21. The application according to claim 20, wherein, The process of olefin polymerization includes bulk slurry polymerization process, solution slurry polymerization process or gas phase polymerization process.

22. The application according to claim 20, wherein, The equipment for olefin polymerization is a batch polymerization reactor or a continuous production device.

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