Metallocene catalyst composition and preparation method therefor and application thereof

Abstract

The present invention provides a metallocene catalyst composition and a preparation method therefor and an application thereof. The metallocene catalyst composition comprises a main catalyst, a cocatalyst, an activator, and a support. The main catalyst has a structure shown in formula I: wherein M is selected from transition metal elements of third, fourth, fifth and sixth groups; n Xs are the same as or different from each other, and are each independently selected from H, halogen, -R, -OR, -SR, -OCOR, -NR2, -PR2, -OR°O-, and -OSO2CF3; n is an integer from 1 to 4; Q is a divalent free radical; and A and Z are each independently selected from formulas II-IV. The metallocene catalyst composition has high activity, and can be used for achieving the development of polypropylene having high and ultrahigh melt flow rates by means of direct hydrogen regulation.

Description

A metallocene catalyst composition and its preparation method and application Technical Field

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

[0002] High melt index polypropylene (HMI) boasts high flow rates and excellent physical properties, making it suitable for the production of large, thin-walled injection molded parts with complex structures. Currently, it is primarily used in packaging, transportation, home appliances, automotive, office equipment, consumer goods, and medical products. Ultra-high melt index polypropylene (UHIPP) generally refers to polypropylene materials with extremely high melt indexes, typically above 1200g / 10min. The higher the value, the lower the molecular weight, the better the processing flowability of the material, and the finer the meltblown fibers. It is the primary raw material for meltblown nonwovens and a core material for products such as masks, protective clothing, diapers, and automotive sound insulation. Polypropylene with an even higher melt index can be used as polypropylene wax, an important additive in inks and coatings, and has a wide range of applications.

[0003] In the prior art, two methods are generally used to obtain high melt index and ultra-high melt index polypropylene resins and polypropylene wax products with better overall performance. One method is to use a suitable controlled rheology technology, that is, to add a peroxide compound to the polypropylene resin during the extrusion granulation process to degrade the polypropylene resin, thereby improving the melt index. CN111410793A, CN111205563A, CN101153095A, etc. disclose methods for preparing high melt index polypropylene resins using peroxide degradation. In the prior art, the production of ultra-high flowability polypropylene products by adding peroxide to degrade polypropylene will result in the formation of a large amount of initiator residues and small molecule byproducts formed by free radical degradation reactions, resulting in a high volatile organic compound (VOC) content in the product and an odor level that generally exceeds industry hygiene requirements. However, with the continuous improvement of people's living standards and quality of life and the increasing awareness of health and environmental protection, the odor parameter of respiratory protective products, which are closely related to human health, has become a key indicator for judging its product quality, limiting its application in sanitary materials, household products, automotive interior parts, food packaging, etc.; secondly, a new catalyst system or an improved polymerization process is used to directly polymerize in the reactor to obtain a high melt index polypropylene resin. The high melt index polypropylene resin directly obtained by polymerization in the reactor has a low yellow index, low volatile organic compound content, and is basically odorless. It has a wide range of applications and has become a development trend in the preparation of high melt index polypropylene. CN114478880A discloses a method for producing high melt index polypropylene for meltblown fabric by an intermittent process and the high melt index meltblown fabric produced by this method. This method uses a traditional Ziegler-Natta catalyst, and the molecular weight distribution and isotacticity of the polypropylene are difficult to control. CN1206720A discloses a method for preparing polypropylene wax using an ethylene-bridged metallocene compound as a catalyst to obtain a molten polypropylene wax. 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 a granular polypropylene wax product, 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 method for preparing high melt index and ultra-high melt index polypropylene at the same time. This method is not only suitable for batch polymerization reactors but also for continuous production equipment. The polypropylene obtained by polymerization has the characteristics of low odor, narrow molecular weight distribution, and low ash content.

[0005] Summary of the Invention

[0006] In order to solve the above problems, the purpose of the present invention is to provide a metallocene catalyst composition and its preparation method and application, which has high activity and can achieve the development of high melt index and ultra-high melt index polypropylene through direct hydrogen adjustment.

[0007] In order to achieve the above object, the present invention provides a metallocene catalyst composition, which comprises a main catalyst, a co-catalyst, an activator and a carrier, wherein the main catalyst has a structure shown in Formula I:

[0008] In Formula I, M is selected from the group III transition metal elements, the group IV transition metal elements, the group V transition metal elements, and the group VI transition metal elements (including lanthanide and quinone series elements); n Xs are the same or different from each other and are independently selected from H, halogen, -R, -OR, -SR, -OCOR, -NR2, -PR2, -OR°O-, and -OSO2CF3, wherein R is independently selected from C1-C 20 Straight chain or branched alkyl, C1-C 20 Unsaturated hydrocarbon groups, C1-C 20 Halogenated alkyl, C1-C 20 hydrocarbon groups containing heteroatoms from Group 13 to Group 17 elements, C1-C 20 Silicon-based and its derivatives, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C7-C 30 Alkyl substituted aryl and its derivatives, C7-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 free radical selected from -CR'2-, -SiR'2-, -GeR'2-, -NR'-, -PR'-, -BR'-, wherein R' is independently selected from C1-C 20 Straight chain or branched alkyl, C1-C 20 Unsaturated hydrocarbon groups, C1-C 20 Halogenated alkyl, C1-C 20 hydrocarbon groups containing heteroatoms from Group 13 to Group 17 elements, C1-C 20 Silicon-based and its derivatives, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C7-C 30 Alkyl substituted aryl and its derivatives, C7-C 30 Aryl-substituted alkyl and its derivatives;

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

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

[0012] In formula II, R1 and R1' are the same or different and are independently selected from H, C1-C 20 Hydrocarbons and their derivatives, C4-C 10 Furyl and its derivatives, C4-C 10 Thienyl and its derivatives; R2 and R2' are the same or different and are independently selected from C1-C 40 Straight chain or branched alkyl, C1-C 40 Unsaturated hydrocarbon groups, C1-C 40 Halogenated alkyl, C1-C 40 hydrocarbon groups containing heteroatoms from Group 13 to Group 17 elements, C1-C 40 Silicon-based and its derivatives, C3-C 40 Cycloalkyl, C6-C 40 Aryl, C7-C 40 Alkyl substituted aryl and its derivatives, C7-C 40 Aryl-substituted alkyl and its derivatives; In Formula II, the symbol *, regardless of whether it is attached to a chemical bond, atom, or free radical, indicates that this point can form a chemical single bond with the same type of chemical bond, atom, or free radical. All symbols * hereinafter have the same meaning.

[0013] Ligand 2 has the structure shown in Formula III:

[0014] In formula III, R1 is selected from H, C1-C 20 Hydrocarbons and their derivatives, C4-C 10 Furyl and its derivatives, C4-C 10 Thienyl and its derivatives; R3 and R3' are the same or different, each independently selected from H, C1-C 40 Straight chain or branched alkyl, C1-C 40 Unsaturated hydrocarbon groups, C1-C 40 Halogenated alkyl, C1-C 40 hydrocarbon groups containing heteroatoms from Group 13 to Group 17 elements, C1-C 40 Silicon-based and its derivatives, C3-C 40 Cycloalkyl, C6-C 40 Aryl, C7-C 40 Alkyl substituted aryl and its derivatives, C7-C 40Aryl substituted alkyl and derivatives thereof; R4 and R4' are the same or different and are independently selected from H, halogen, C1-C 40 Straight chain or branched alkyl, C1-C 40 Unsaturated hydrocarbon groups, C1-C 40 Halogenated alkyl, C1-C 40 hydrocarbon groups containing heteroatoms from Group 13 to Group 17 elements, C1-C 40 Silicon-based and its derivatives, C3-C 40 Cycloalkyl, C6-C 40 Aryl, C7-C 40 Alkyl substituted aryl and its derivatives, C7-C 40 Aryl substituted alkyl and its derivatives; R5 is selected from H, halogen, -R, wherein R is selected from C1-C 20 Straight chain or branched alkyl, C1-C 20 Unsaturated hydrocarbon groups, C1-C 20 Halogenated alkyl, C1-C 20 hydrocarbon groups containing heteroatoms from Group 13 to Group 17 elements, C1-C 20 Silicon-based and its derivatives, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C7-C 30 Alkyl substituted aryl and its derivatives, C7-C 30 Aryl-substituted alkyl and its derivatives;

[0015] Ligand 3 has the structure shown in Formula IV:

[0016] In formula IV, R1 is selected from H, C1-C 20 Hydrocarbons and their derivatives, C4-C 10 Furyl and its derivatives, C4-C 10 Thienyl and its derivatives; R4, R4', R4" and R4"' are the same or different and are independently selected from H, halogen, C1-C 40 Straight chain or branched alkyl, C1-C 40 Unsaturated hydrocarbon groups, C1-C 40 Halogenated alkyl, C1-C 40 hydrocarbon groups containing heteroatoms from Group 13 to Group 17 elements, C1-C 40 Silicon-based and its derivatives, C3-C 40 Cycloalkyl, C6-C 40 Aryl, C7-C 40 Alkyl substituted aryl and its derivatives, C7-C 40Aryl substituted alkyl and its derivatives; R5 is selected from H, halogen, -R, wherein R is selected from C1-C 20 Straight chain or branched alkyl, C1-C 20 Unsaturated hydrocarbon groups, C1-C 20 Halogenated alkyl, C1-C 20 hydrocarbon groups containing heteroatoms from Group 13 to Group 17 elements, C1-C 20 Silicon-based and its derivatives, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C7-C 30 Alkyl substituted aryl and its derivatives, C7-C 30 Aryl substituted alkyl and its derivatives; R6 and R6' are the same or different, each independently selected from H, halogen, -OR, -SR, -OCOR, -NR2, -PR2, wherein R is independently selected from C1-C 40 Straight chain or branched alkyl, C1-C 40 Unsaturated hydrocarbon groups, C1-C 40 Halogenated alkyl, C1-C 40 hydrocarbon groups containing heteroatoms from Group 13 to Group 17 elements, C1-C 40 Silicon-based and its derivatives, C3-C 40 Cycloalkyl, C6-C 40 Aryl, C7-C 40 Alkyl substituted aryl and its derivatives, C7-C 40 Aryl-substituted alkyl and its derivatives.

[0017] 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, and more preferably selected from titanium, zirconium and hafnium.

[0018] According to a specific embodiment of the present invention, preferably, n X are the same as or different from each other and are independently selected from halogen, -R, -OR, -SR, -OCOR, -NR2, -PR2, -OR°O-, -OSO2CF3, 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, cyclopentyl, cyclopentyl, cyclohex ... Butyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, 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- Benzyl chloride, 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 are not limited thereto; X is more preferably selected from chlorine, bromine, C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 20 benzyl; R° is selected from C2-C 40 Alkylene, C6-C 30 Arylene, C7-C 40 Alkyl arylene, C7-C 40In the -OR°O- structure, the two oxygen atoms may be at any position of the free radical, but preferably the positions of the two oxygen atoms are a combination of adjacent (α, β-positions) and intervening (α, γ-positions) positions of the free radical.

[0019] According to a specific embodiment of the present invention, 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-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, 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, 2-methylenedianiline, 2-methylenedianiline, 2-methylenedianiline, 2-methylenedianiline, 2-methylenedianiline, 2-methylenedianiline, 2-methylenedianiline, 2-methylenedianiline, 2-methylenedianiline 4-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-butyl R' is independently selected from methyl, ethyl, isopropyl, trimethylsilyl, phenyl, 2,6-difluorophenethyl, 3,5-difluorophenethyl, 3,4,5-trifluorophenethyl, perfluorophenethyl, 1-naphthylmethyl, 2-naphthylmethyl and the like, but is not limited thereto; more preferably, R' is independently selected from methyl, ethyl, isopropyl, trimethylsilyl, phenyl, and benzyl.

[0020] According to a specific embodiment of the present invention, preferably, in formula II, R1 and R1' are the same or different, and are each independently selected from H, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furyl, 2-thienyl; R2 and R2' are the same or different, 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, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, 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 R2 and R2' are each independently selected from methyl, ethyl, isopropyl, tert-butyl, p-trimethylsilyl, 2,6-difluorophenethyl, 3,5-difluorophenethyl, 3,4,5-trifluorophenethyl, perfluorophenethyl, 1-naphthylmethyl, 2-naphthylmethyl, etc., but are not limited thereto; More preferably, R2 and R2' are each independently selected from methyl, ethyl, isopropyl, tert-butyl, 2,6-difluorophenethyl, 3,5-difluorophenethyl, 3,4,5-trifluorophenethyl, perfluorophenethyl, 1-naphthylmethyl, 2-naphthylmethyl, etc.

[0021] According to a specific embodiment of the present invention, preferably, in formula III, R1 is selected from H, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furyl, 2-thienyl; R3 and R3' are the same or different 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-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, 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 are not limited thereto, more preferably, R3 and R3' are each independently selected from phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, furan, thiophene, quinoline, pyrimidine, wherein the substituent in the substituted phenyl is selected from cyano, nitro, F, methyl, ethyl, isopropyl, tert-butyl, methoxy, tert-butyl, trifluoromethoxy, Cl, trifluoromethyl, carbonyl, trimethylsilyl;R4 and R4' are the same or different 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-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 are not limited thereto, more preferably, R4 and R4' are each independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, phenyl;R5 is 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 phenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, 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 phenyl, 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 are not limited thereto. ;

[0022] According to a specific embodiment of the present invention, preferably, in formula IV, R1 is selected from H, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furyl, 2-thienyl; R4, R4', R4" and R4'" are the same or different 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-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, 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-difluoro- Isopropylphenyl, 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-butyl Benzyl, 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 are not limited thereto. More preferably, R4, R4', R4" and R4'" are each independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, and phenyl;R5 is 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 phenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, 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 phenyl, 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 are not limited thereto;R6 and R6' are the same or different and are independently selected from H, halogen, -OR, -SR, -OCOR, -NR2, -PR2, 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, benzyl, 1-butyl, 1-hex ... phenyl, 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 are not limited thereto. ;

[0023] According to a specific embodiment of the present invention, preferably, the carrier is a silica-modified carrier, which is obtained by reacting a metal organic framework coordination polymer with silica gel and then heating the reacted carrier under a vacuum atmosphere.

[0024] According to a specific embodiment of the present invention, preferably, the preparation method of the silica gel modified carrier comprises the following steps: after dispersing the dehydrated silica gel in a dry organic solvent (the water content is preferably less than 15 ppm) at -30°C to 120°C, mixing and contacting with a metal organic framework coordination polymer for 0.5-10 hours, filtering and washing, vacuuming, heating at 150-200°C for 1-6 hours, and heating at 200-300°C for 1-6 hours under a protective gas atmosphere (such as argon) to obtain the silica gel modified carrier.

[0025] According to a specific embodiment of the present invention, preferably, the metal organic framework coordination polymer is selected from UiO-66, UiO-66-NH2, UiO-66-MM, UiO-66-Br, UiO-66-Br2, UiO-66-CO2H, UiO-67, MIL-100 (Al), MIL-100 (Fe), MIL-53 (Al), MIL-53 (Cr), MIL-127, MIL-101-NH2 (Cr), MIL-125-NH2 (Ti), Zn-MOF-508, Zn-DMOF -A, Zn-DMOF-TM, CAU-10-H, CAU-10-CH3, CAU-10-NO2, CAU-10-NH2, CAU-10-OH, CAU-10-OCH3, 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. In the present invention, the metal organic framework coordination polymer can be obtained commercially or by synthesis.

[0026] According to a specific embodiment of the present invention, preferably, the dehydration condition of the silica gel is vacuuming at 300-600°C.

[0027] According to a specific embodiment of the present invention, preferably, the organic solvent includes one or a combination of two or more of toluene, hexane, and heptane.

[0028] 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 gel.

[0029] According to a specific embodiment of the present invention, preferably, the activator is a Lewis acidic substance (LA), more preferably comprising one or a combination of two or more of methylaluminoxane, polymethylaluminoxane, modified methylaluminoxane, and an organic boron reagent.

[0030] LA is a type of Lewis acidic material with expanded volume, electron delocalization, and poor coordination. Representative examples of this type of material are polymethylaluminoxane (PMAO), which exhibits equilibrium states of chain, ring, and cage structures in solution, and modified polymethylaluminoxane (MMAO).

[0031] There are many examples of anions with expanded volume, delocalized electrons, and poor coordination properties to choose from, such as [B(C6H5)4] - ,[(CH3)B(C6F5)3] - ,[B(C6F5)4] - ,[B(2,6-(CH3)2-C6H3)4] - ,[B(2,4,6-(CH3)3-C6H2)4] - ,[B(2,3,5,6-(CH3)4-C6H)4] - ,[B(2,6-(CF3)2-C6H3)4] - ,[B(2,4,6-(CF3)3-C6H2)4] - ,[B(2,3,5,6-(CF3)4-C6H)4] - ,[B(3,5-(CH3)2-C6H3)4] - ,[B(3,4,5-(CH3)3-C6H2)4] - ,[B(3,5-(CF3)2-C6H3)4] - ,[B(3,4,5-(CF3)3-C6H2)4] - ,[B(2,6-(CF3)2-C6F3)4] - ,[B(2,4,6-(CF3)3-C6F2)4] - ,[B(2,3,5,6-(CF3)4-C6F)4] - ,[B(3,5-(CF3)2-C6F3)4] - ,[B(3,4,5-(CF3)3-C6F2)4] - ,[Al(C6H5)4] - ,[(CH3)Al(C6F5)3] - ,[Al(C6F5)4] - ,[Al(2,6-(CH3)2-C6H3)4] - ,[Al(2,4,6-(CH3)3-C6H2)4] - ,[Al(2,3,5,6-(CH3)4-C6H)4] - ,[Al(3,5-(CH3)2-C6H3)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [Al(3,4,5-(CH3)3-C6H2)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [Al(2,6-(CH3)2-C6F3)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [Al(2,4,6-(CH3)3-C6F2)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,[Al(2,3,5,6-(CH3)4-C6F)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [Al(3,5-(CH3)2-C6F3)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [Al(3,4,5-(CH3)3-C6F2)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,[Al(2,6-(CF3)2-C6H3)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,[Al(2,4,6-(CF3)3-C6H2)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,[Al(2,3,5,6-(CF3)4-C6H)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [Al(3,5-(CF3)2-C6H3)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,[Al(3,4,5-(CF3)3-C6H2)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [Al(2,6-(CF3)2-C6F3)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [Al(2,4,6-(CF3)3-C6F2)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [Al(2,3,5,6-(CF3)4-C6F)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [Al(3,5-(CF3)2-C6F3)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [Al(3,4,5-(CF3)3-C6F2)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,{t-Bu-CH=C[B(C6F5)2]2(CH3)}<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,{Ph-CH = C[B(C6F5)2]2(CH3)}<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,{(C6F5)-CH=C[B(C6F5)2]2(CH3)}<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,{t-Bu-CH=C[Al(C6F5)2]2(CH3)}<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,{Ph-CH = C[Al(C6F5)2]2(CH3)}<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> {(C6F5)-CH = C[Al(C6F5)2]2(CH3)}<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,[1,1'-C<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> F8-2,2' = B(C6F5)2]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,[1,1'-C<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> F8-2,2' = Al(C6F5)2]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [FB(1-C6F4-2-C6F5)3]<h2 style=";text-align:left;direction:ltr"> -,[(CH3)B(1-C6F4-2-C6F5)3] - ,[(C6F5)B(1-C6F4-2-C6F5)3] - ,[(C6F5)Al(1-C6F4-2-C6F5)3] - ,[FAl(1-C6F4-2-C6F5)3]-,[(CH3)Al(1-C6F4-2-C6F5)3]-,] - ,[HB(1-C6F4-2-C6F5)3] - ,[HAl(1-C6F4-2-C6F5)3] - ,[(CH3)B(2-C 10 F7)3] - ,[(CH3)Al(2-C 10 F7)3] - ,[(CH3)B(p-C6F4SiMe3)3] - ,[B(p-C6F4SiMe3)4] - ,[(CH3)B(p-C6F4Si(n-Bu)3)3] - ,[B(p-C6F4Si(n-Bu)3)4] - ,[(CH3)B(p-C6F4Si(i-Bu)3)3] - ,[B(p-C6F4Si(i-Bu)3)4] - ,[(CH3)B(p-C6F4Si(t-Bu)3)3] - ,[B(p-C6F4Si(t-Bu)3)4] - ,[(C6F5)3B-C6F4-B(C6F5)2] - ,[C6F4-1,2-(B(C6F5)3)2] - ,[C6F4-1,2-(Al(C6F5)3)2] - ,[(C6F4)-1,2-(B(C6F5)2)2-1',2'-(C6F4)] - ,[(C6F4)-1,2-(Al(C6F5)2)2-1',2'-(C6F4)] - ,[(C6F5)3B-CN-B(C6F5)3] - ,[(C6F5)3Al-CN-Al(C6F5)3] - ,[((C6F5)3BNC)4Ni] - ,[((C6F5)3AlNC)4Ni] - ,[(1,1'-C 12<h2 style=";text-align:left;direction:ltr">F8)2-2,2'-B]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,[(1,1'-C<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> F8)2-2,2'-Al]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> , [B(O-C6F5)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,[Al(O-C6F5)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [(C6F5)3Al-C6F4-Al(C6F5)2]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [(CH3)Al(p-C6F4SiMe3)3]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [Al(p-C6F4SiMe3)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [(CH3)Al(p-C6F4Si(n-Bu)3)3]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,[Al(p-C6F4Si(n-Bu)3)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [(CH3)Al(p-C6F4Si(i-Bu)3)3]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,[Al(p-C6F4Si(i-Bu)3)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [(CH3)Al(p-C6F4Si(t-Bu)3)3]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,[Al(p-C6F4Si(t-Bu)3)4]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [C5(C6H5)5]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [C5(2,6-(CH3)2-C6H3)5]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [C5(2,4,6-(CH3)3-C6H2)5]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [C5(3,5-(CH3)2-C6H3)5]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [C5(3,4,5-(CH3)3-C6H2)5]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [C5(2,6-(CF3)2-C6H3)5]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [C5(2,4,6-(CF3)3-C6H2)5]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [C5(3,5-(CF3)2-C6H3)5]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [C5(3,4,5-(CF3)3-C6H2)5]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [C5(2,6-(CH3)2-C6F3)5]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [C5(2,4,6-(CH3)3-C6F2)5]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [C5(3,5-(CH3)2-C6F3)5]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [C5(3,4,5-(CH3)3-C6F2)5]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ,[C5(2,6-(CF3)2-C6F3)5]<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> [C5(2,4,6-(CF3)3-C6F2)5]- ,[C5(3,5-(CF3)2-C6F3)5] - ,[C5(3,4,5-(CF3)3-C6F2)5] - ,[C5(C6F5)5] - ,[Li(Ta(OC6F5)4(2-OC6F5)2)2] - ,[Nb(OC6F5)6] - ,[PF6] - ,[AsF6] - ,[SbF6] - ,[BF4] - ,[ClO4] - , carborane anions such as: [C2B9H 12 ] - ,[CB 11 H 12 ] - , but not limited to this.

[0032] According to a specific embodiment of the present invention, preferably, the co-catalyst 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, and diethylbenzylaluminum.

[0033] According to a specific embodiment of the present invention, preferably, 50-80 kg of the carrier is added per mole of the main catalyst.

[0034] According to a specific embodiment of the present invention, preferably, the molar ratio of the activator to the main catalyst is 10-500:1.

[0035] According to a specific embodiment of the present invention, preferably, the molar ratio of the co-catalyst to the main catalyst is 10-500:1.

[0036] According to a specific embodiment of the present invention, preferably, the synthesis method of the main catalyst is shown in the following reaction formula:

[0037] Wherein, T is the same as or different from each other, and is a monodentate or bidentate neutral ligand; LG is a leaving group, which is the same as or different from each other, and is an organic free radical of hydrogen, an alkali metal element, or a heavy element of Group XIV.

[0038] 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, sulfides RSR, tertiary amines NR3, tertiary phosphines PR3, cyclic ethers, cyclic sulfides, ketones, substituted cyclic ketones, substituted pyridines, substituted pyrroles, substituted piperidines, esters, lactones, amides, and lactams, wherein R is selected from C1-C 20 Straight chain or branched alkyl, C1-C 20 Unsaturated hydrocarbon groups, C1-C 20 Halogenated alkyl, C1-C 20 Alkyl groups containing heteroatoms from Group 13 to Group 17 elements, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C7-C 30 Alkyl substituted aryl, C7-C 30 An aromatic substituted alkyl group.

[0039] 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-diethers, α,ω-diethers, ortho-diamines, α,ω-diamines, ortho-disulfides, α,ω-disulfides, ortho-diphosphines, α,ω-diphosphines; wherein x is 0, 1, 2 or 3.

[0040] 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 free radicals of the fourteenth group heavy elements include SiR3, GeR3, SnR3, PdR3, ZnR, BaR, MgR and CaR, wherein R is selected from C1-C 20 Straight chain or branched alkyl, C1-C 20 Unsaturated hydrocarbon groups, C1-C 20 Halogenated alkyl, C1-C 20 Alkyl groups containing heteroatoms from Group 13 to Group 17 elements, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C7-C 30 Alkyl substituted aryl, C7-C 30 An aromatic substituted alkyl group.

[0041] According to a specific embodiment of the present invention, preferably, in the synthesis method of the main catalyst, the reaction medium is C5-C 15 Alkanes and / or cycloalkanes.

[0042] According to a specific embodiment of the present invention, preferably, in the method for synthesizing the main catalyst, the reaction medium is one or a combination of two or more of hexane, heptane, octane, toluene and xylene.

[0043] According to a specific embodiment of the present invention, preferably, in the method for synthesizing 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.

[0044] The present invention also provides a method for preparing the metallocene catalyst composition, which comprises the following steps: mixing the main catalyst, co-catalyst, activator, and carrier in a homogeneous liquid medium, reacting at 5°C-100°C for 1-8 hours to obtain the metallocene catalyst composition.

[0045] 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, 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, polyfluorobenzene and its isomers, more preferably one or a combination of two or more of toluene, hexane, and pentane.

[0046] The present invention also provides application of the metallocene catalyst composition in catalyzing olefin polymerization.

[0047] According to a specific embodiment of the present invention, preferably, the olefin polymerization process includes a bulk slurry polymerization process, a solvent slurry polymerization process or a gas phase polymerization process.

[0048] According to a specific embodiment of the present invention, preferably, the olefin polymerization equipment is a batch polymerization reactor or a continuous production device.

[0049] The present invention adopts a silica gel modified carrier to load the metallocene complex, transforming the homogeneous catalytic system into a heterogeneous catalytic system, further improving the morphology of the polymer product, increasing the bulk density and fluidity of the product, and largely avoiding clogging of the polymerization device. In addition, the metal organic framework coordination polymer provides sufficient acid sites, while increasing the specific surface area of ​​the modified silica gel and improving the metal compound loading efficiency. Compared with the catalyst supported by ordinary silica gel, the amount of expensive activators such as methylaluminoxane or borate reagents can be greatly reduced while maintaining the same activity level. Even when no activators such as methylaluminoxane or borate reagents are used, the catalyst can still have high activity, and the effective life of the catalyst is extended. The catalytic performance is improved while the production cost is reduced. The melt index of the polypropylene can be adjusted only by adjusting the hydrogen concentration. The melt index can be adjusted over a very wide range, and different brands of high melt index and ultra-high melt index polypropylene can be developed, which is conducive to industrial application and promotion. DETAILED DESCRIPTION

[0050] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be understood as limiting the scope of implementation of the present invention.

[0051] Example 1

[0052] This embodiment provides a catalyst composition, which is prepared by the following steps:

[0053] (1) Synthesis of metallocene complexes:

[0054] In the above reaction formula, Q is a divalent free 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:

[0055] Preparation of Cat-1: Dissolve the above-mentioned ligand dimethylsilyldicyclopentadiene (0.186 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), naturally warm to room temperature, and stir for 2 hours to prepare the ligand lithium salt solution. Weigh 0.23 g of ZrCl4 (Fw = 233.04, 1.0 mmol) in another reaction bottle, add 10 mL of anhydrous MTBE at low temperature and under nitrogen protection, stir for a while in a -40°C low-temperature cold bath, and slowly add the above-mentioned ligand lithium salt solution to the ZrCl4 suspension (taking 3 hours). After the addition is complete, naturally warm to room temperature and stir at room temperature overnight. Vacuum the solvent to constant weight to obtain the white complex Cat-1;

[0056] (2) Preparation of metal organic framework coordination polymer UiO-66: 5mmol zirconium chloride, 5mmol terephthalic acid, 1mL 37 wt% concentrated hydrochloric acid and 50mL N,N-dimethylformamide were added to a 100mL autoclave, ultrasonicated for 15 minutes, sealed, heated at 120℃ for 2 days, cooled naturally, and filtered. Then, rinsed with N,N-dimethylformamide 3 times, and then soaked in methanol for 2 days, during which fresh methanol needed to be replaced for soaking, and then vacuum dried. Then, dried and activated in a vacuum at 150℃ for 12 hours to obtain a solid sample. The preparation method refers to patent CN116020416A;

[0057] (3) Preparation of silica gel modified support S1:

[0058] Grace 955 silica gel was vacuumed 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 UiO 66 was added at room temperature. The mixture was stirred for 2 hours, filtered, washed with hexane, and vacuum-dried. The obtained support was heated from room temperature to 150°C within 1 hour and maintained for 1 hour, then vacuumed and heated to 200°C for another 3 hours, and naturally cooled to room temperature. Inert gas protection was maintained during the cooling process to obtain silica gel modified support S1.

[0059] (4) Preparation of catalyst composition MPP-1:

[0060] The metallocene complex Cat-1 (20 μmol) was dissolved in toluene to prepare a solution. 1 g of the silica-modified support S1 was added to a 50 mL flask containing 20 mL of toluene. 3 mL of a 1 M triisobutylaluminum-hexane solution was added, and after stirring for 3 hours, 5 mL of a 10 wt% MAO toluene solution (the same below) was added. The temperature was raised to 60°C, heated for a reaction for 2 hours, and then cooled to room temperature. The entire Cat-1 toluene solution prepared above was added, and the mixture was stirred at room temperature for 30 minutes to obtain the catalyst composition MPP-1. The upper layer of the clear toluene solution was removed, and the mixture was washed with toluene three times. Then, the mixture was vacuum-dried to obtain the solid catalyst MPP-01.

[0061] Example 2-Example 6

[0062] Examples 2 to 6 provide a catalyst composition MPP-2 to MPP-6, respectively, which are prepared by the following steps:

[0063] (1) Synthesis of metallocene complexes Cat-2 to Cat-6: The steps were the same as in Example 1, except that the raw materials were replaced with ligand raw materials having corresponding substituents. The substituents of the metallocene complexes are shown in Table 1.

[0064] (2) Preparation of silica gel modified support S1: same as Example 1.

[0065] (3) Preparation of catalyst compositions MPP-2 to MPP-6: Same as Example 1, except that Cat-1 was replaced by Cat-2 to Cat-6, respectively.

[0066] Example 7

[0067] This embodiment provides a catalyst composition, which is prepared by the following steps:

[0068] (1) Synthesis of metallocene complexes:

[0069] In the above reaction formula, Q is a divalent free 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:

[0070] Preparation of Cat-7: Dissolve the aforementioned 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), naturally warm to room temperature, and stir for 2 h to prepare the ligand lithium salt solution. Weigh 0.23 g of ZrCl4 (Fw = 233.04, 1.0 mmol) into another reaction flask, add 10 mL of anhydrous MTBE at low temperature under nitrogen protection, and stir for a while in a -40°C cold bath. Slowly add the aforementioned ligand lithium salt solution to the ZrCl4 suspension (over 3 h), naturally warm to room temperature after the addition is complete, and stir at room temperature overnight. Vacuum the solvent to constant weight to obtain the yellow complex Cat-7.

[0071] (2) Preparation of silica gel modified support S2:

[0072] Grace 955 silica gel was vacuumed 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 MIL-53(Al) was added at room temperature. The mixture was stirred for 2 hours, filtered, washed with hexane, and vacuum-dried. The obtained support was heated from room temperature to 150°C within 1 hour and maintained for 1 hour. The mixture was then vacuumed and heated to 200°C and maintained for 3 hours. The support was naturally cooled to room temperature, and inert gas protection was maintained during the cooling process to obtain silica gel modified support S2.

[0073] (3) Preparation of catalyst composition MPP-07:

[0074] The metallocene complex Cat-7 (20 μmol) was dissolved in toluene to prepare a solution. 1 g of the silica-modified support S2 was added to a 50 mL flask containing 20 mL of toluene. 3 mL of a 1 M triisobutylaluminum-hexane solution was added, and after stirring for 3 hours, 5 mL of a toluene solution of MAO was added. The temperature was raised to 60°C, heated for a reaction of 2 hours, and then cooled to room temperature. The entire Cat-7 toluene solution prepared above was added, and the mixture was stirred at room temperature for 30 minutes to obtain the catalyst composition MPP-7. The upper layer of the clear toluene solution was removed, and the mixture was washed with toluene three times. The mixture was then vacuum-dried to obtain the solid catalyst MPP-07.

[0075] Example 8 to Example 16

[0076] Examples 8 to 16 provide a catalyst composition MPP-8 to MPP-16, respectively, which are prepared by the following steps:

[0077] (1) Synthesis of metallocene complexes Cat-8 to Cat-16: The steps were the same as in Example 7, except that the raw materials were replaced with ligand raw materials having corresponding substituents. The substituents of the metallocene complexes are shown in Table 1.

[0078] (2) Preparation of silica gel modified support S2: same as Example 7;

[0079] (3) Preparation of catalyst compositions MPP-8 to MPP-16: Same as Example 7, except that Cat-7 was replaced by Cat-8 to Cat-16, respectively.

[0080] Example 17

[0081] This embodiment provides a catalyst composition, which is prepared by the following steps:

[0082] (1) Synthesis of metallocene complexes:

[0083] In the above reaction formula, Q is a divalent free 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:

[0084] Preparation of Cat-17: Dissolve the aforementioned ligand, dimethylsilylbis(4,5-benzindenyl)zirconium chloride (0.62 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), naturally warm to room temperature, and stir for 2 h to prepare the ligand lithium salt solution. Weigh 0.23 g of ZrCl4 (Fw = 233.04, 1.0 mmol) into another reaction flask, add 10 mL of anhydrous MTBE at low temperature under nitrogen protection, and stir for a while in a -40°C cold bath. Slowly add the aforementioned ligand lithium salt solution to the ZrCl4 suspension (over 3 h), naturally warm to room temperature after the addition is complete, and stir at room temperature overnight. Vacuum the solvent to constant weight to obtain the purple complex Cat-17.

[0085] (2) Preparation of silica gel modified support S3:

[0086] Grace 955 silica gel was vacuumed at 450°C for 3 hours and then cooled naturally to room temperature under an inert gas atmosphere. 5g of the dehydrated silica gel was added to a 500mL three-necked flask containing 250mL of hexane, and 0.2g of DUT-51 was added at room temperature and stirred for 2 hours. The mixture was filtered, washed with hexane, and vacuumed to dryness. The resulting support was heated from room temperature to 150°C within 1 hour and held for 1 hour. The temperature was then vacuumed and raised to 200°C for another 3 hours. The support was then cooled naturally to room temperature, maintaining an inert gas atmosphere during the cooling process, to obtain silica-modified support S3.

[0087] (3) Preparation of catalyst composition MPP-17:

[0088] The metallocene complex Cat-17 (20 μmol) was dissolved in toluene to prepare a solution. 1 g of the silica-modified support S3 was added to a 50 mL flask containing 20 mL of toluene. 3 mL of a 1 M triisobutylaluminum-hexane solution was added, and after stirring for 3 hours, 4 mL of a toluene solution of MAO was added. The temperature was raised to 60°C, heated for a reaction of 2 hours, and then cooled to room temperature. The entire Cat-17 toluene solution prepared above was added, and the mixture was stirred at room temperature for 30 minutes to obtain the catalyst composition MPP-17. The upper layer of the clear toluene solution was removed, and the mixture was washed three times with toluene. The mixture was then vacuum-dried to obtain the solid catalyst MPP-017.

[0089] Example 18 to Example 25

[0090] Examples 18 to 25 provide catalyst compositions MPP-18 to MPP-25, respectively, which are prepared by the following steps:

[0091] (1) Synthesis of metallocene complexes Cat-18 to Cat-25: The steps were the same as in Example 17, except that the raw materials were replaced with ligand raw materials having corresponding substituents. The substituents of the metallocene complexes are shown in Table 1.

[0092] (2) Preparation of silica gel modified support S3: same as Example 17;

[0093] (3) Preparation of catalyst compositions MPP-18 to MPP-25: Same as Example 17, except that Cat-17 was replaced by Cat-18 to Cat-25, respectively.

[0094] Example 26 to Example 30

[0095] (1) Synthesis of metallocene complexes Cat-26 to Cat-30: The steps were the same as in Example 1, except that the raw materials were replaced with ligand raw materials having corresponding substituents. The substituents of the metallocene complexes are shown in Table 1.

[0096] (2) Preparation of silica gel modified support S3: same as Example 17;

[0097] (3) Preparation of catalyst compositions MPP-26 to MPP-30: Same as Example 17, except that Cat-17 was replaced by Cat-26 to Cat-30, respectively.

[0098] Table 1: Metallocene complex structures

[0099] Example 31

[0100] This embodiment provides a catalyst composition, which is prepared by the following steps:

[0101] The metallocene complex Cat-1 (20 μmol) was dissolved in toluene to prepare a solution. 1 g of the silica-modified support S1 was added to a 50 mL flask containing 20 mL of toluene. 3 mL of a 1 M triisobutylaluminum-hexane solution was added, and after stirring for 3 hours, 5 mL of a 10 wt% toluene solution of isobutyl-modified MAO (MMAO) was added. The temperature was raised to 50°C, heated for a reaction for 2 hours, and then cooled to room temperature. The entire Cat-1 toluene solution prepared above was added, and the mixture was stirred at room temperature for 30 minutes to obtain the catalyst composition MPP-31. The upper layer of the clear toluene solution was removed, and the mixture was washed with toluene three times, followed by vacuum drying to obtain the solid catalyst MPP-031.

[0102] Example 32

[0103] This embodiment provides a catalyst composition, which is prepared by the following steps:

[0104] The metallocene complex Cat-1 (20 μmol) was dissolved in toluene to prepare a solution. 1 g of the silica-modified support S1 was added to a 50 mL flask containing 20 mL of toluene. 1 mL of a 1 M triethylaluminum hexane solution was added and stirred for 3 hours. 10 mg of [PhMe2NH][B(C6F5)4] was dissolved in 5 mL of toluene and slowly added dropwise to the reaction solution. The temperature was raised to 50°C, heated for 2 hours, and then cooled to room temperature. The entire Cat-1 toluene solution prepared above was added and stirred at room temperature for 30 minutes to obtain the catalyst composition MPP-32. The upper layer of the clear toluene solution was removed, and the solution was washed three times with toluene before being vacuum dried to obtain the solid catalyst MPP-032.

[0105] Example 33

[0106] This embodiment provides a catalyst composition, which is prepared by the following steps:

[0107] (1) Preparation of silica gel modified support S4:

[0108] Grace 955 silica gel was vacuumed 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 0.5 g of MIL-53 (Al) was added at room temperature. The mixture was stirred for 2 hours, heated to 50°C, reacted for 2 hours, and then cooled to room temperature. The mixture was filtered and washed with hexane and vacuum-dried. The obtained support was heated from room temperature to 150°C within 1 hour and maintained for 1 hour. The mixture was then vacuumed and heated to 200°C and maintained for 3 hours. The mixture was naturally cooled to room temperature. Inert gas protection was maintained during the cooling process to obtain silica gel modified support S4.

[0109] (2) Preparation of catalyst composition MPP-33:

[0110] The metallocene complex Cat-7 (20 μmol) was dissolved in toluene to prepare a solution. 1 g of the silica-modified support S4 was added to a 50 mL flask containing 20 mL of toluene. 10 mL of a 1 M triethylaluminum hexane solution was added. The temperature was raised to 60°C and heated for 3 hours before cooling to room temperature. 0.47 g of the Cat-7 toluene solution was added and stirred at room temperature for 30 minutes to obtain the catalyst composition MPP-33. The upper clear toluene solution was removed, and the mixture was washed three times with toluene before vacuum drying to obtain the solid catalyst MPP-033.

[0111] Example 34 Propylene bulk polymerization

[0112] The polymerization was carried out in a 5L autoclave. The polymerization autoclave was first purged and replaced with dry nitrogen, and then 0.05MPa of hydrogen was introduced. 55mg of the catalyst MPP-01 prepared in Example 1 was suspended in 5ml of n-hexane to make a slurry and added to the catalyst feeder. Subsequently, 3.5ml of a 1mol / L triisobutylaluminum hexane solution was added, stirring was started, and the catalyst and triisobutylaluminum were flushed into the reactor with 2.3L of liquid propylene. The temperature was raised to 70°C and the reaction was carried out for 1 hour to obtain 240g of powdered polypropylene. The polymerization reaction activity was 4356gPP / gcat, the polypropylene melt index was 35g / 10min, the molecular weight distribution was 3.3, and the polymer bulk density was 0.39g / cm 3 .

[0113] Example 35 Propylene bulk polymerization

[0114] The polymerization was carried out in a 5L autoclave. The polymerization autoclave was first purged and replaced with dry nitrogen, and then 0.07MPa of hydrogen was introduced. 54mg of the catalyst MPP-01 prepared in Example 1 was suspended in 5ml of n-hexane to make a slurry and added to the catalyst feeder. Subsequently, 3.5ml of a 1mol / L triisobutylaluminum hexane solution was added, stirring was started, and the catalyst and triisobutylaluminum were flushed into the reactor with 2.3L of liquid propylene. The temperature was raised to 70°C and the reaction was carried out for 1 hour to obtain 278g of powdered polypropylene. The polymerization reaction activity was 5148gPP / gcat, the polypropylene melt index was 78g / 10min, the molecular weight distribution was 3.3, and the polymer bulk density was 0.38g / cm 3 .

[0115] Example 36 Propylene Bulk Polymerization

[0116] The polymerization was carried out in a 5L autoclave. The polymerization autoclave was first purged and replaced with dry nitrogen, and then 0.09MPa of hydrogen was introduced. 50mg of the catalyst MPP-01 prepared in Example 1 was suspended in 5ml of n-hexane to make a slurry and added to the catalyst feeder. Subsequently, 3.5ml of a 1mol / L triisobutylaluminum hexane solution was added, stirring was started, and the catalyst and triisobutylaluminum were flushed into the reactor with 2.3L of liquid propylene. The temperature was raised to 70°C and the reaction was carried out for 1 hour to obtain 312g of powdered polypropylene. The polymerization reaction activity was 6240gPP / gcat, the polypropylene melt index was 248g / 10min, the molecular weight distribution was 3.4, and the polymer bulk density was 0.39g / cm 3 .

[0117] Example 37 Propylene Bulk Polymerization

[0118] The polymerization was carried out in a 5L autoclave. The polymerization autoclave was first purged and replaced with dry nitrogen, and then 0.12MPa of hydrogen was introduced. 50mg of the catalyst MPP-01 prepared in Example 1 was suspended in 5ml of n-hexane to make a slurry and added to the catalyst feeder. Subsequently, 3.5ml of a 1mol / L triisobutylaluminum hexane solution was added, stirring was started, and the catalyst and triisobutylaluminum were flushed into the reactor with 2.3L of liquid propylene. The temperature was raised to 70°C and the reaction was carried out for 1 hour to obtain 336g of powdered polypropylene. The polymerization reaction activity was 6720gPP / gcat, the polypropylene melt index was 820g / 10min, the molecular weight distribution was 3.4, and the polymer bulk density was 0.39g / cm 3 .

[0119] Example 38 Propylene Bulk Polymerization

[0120] The polymerization was carried out in a 5L autoclave. The polymerization autoclave was first purged and replaced with dry nitrogen, and then 0.15MPa of hydrogen was introduced. 51mg of the catalyst MPP-01 prepared in Example 1 was suspended in 5ml of n-hexane to make a slurry and added to the catalyst feeder. Subsequently, 3.5ml of a 1mol / L triisobutylaluminum hexane solution was added, stirring was started, and the catalyst and triisobutylaluminum were flushed into the reactor with 2.3L of liquid propylene. The temperature was raised to 70°C and the reaction was carried out for 1 hour to obtain 371g of powdered polypropylene. The polymerization reaction activity was 7274gPP / gcat, the polypropylene melt index was 1650g / 10min, the molecular weight distribution was 3.3, and the polymer bulk density was 0.41g / cm 3 .

[0121] Example 39 Propylene Bulk Polymerization

[0122] The polymerization was carried out in a 5L autoclave. The polymerization autoclave was first purged and replaced with dry nitrogen, and then 0.18MPa of hydrogen was introduced. 52mg of the catalyst MPP-01 prepared in Example 1 was suspended in 5ml of n-hexane to make a slurry and added to the catalyst feeder. Subsequently, 3.5ml of a 1mol / L triisobutylaluminum hexane solution was added, stirring was started, and the catalyst and triisobutylaluminum were flushed into the reactor with 2.3L of liquid propylene. The temperature was raised to 70°C and the reaction was carried out for 1 hour to obtain 352g of powdered polypropylene. The polymerization reaction activity was 6769gPP / gcat, the polypropylene melt index was 3450g / 10min, the molecular weight distribution was 3.3, and the polymer bulk density was 0.40g / cm 3 .

[0123] Example 40 Propylene bulk polymerization

[0124] The polymerization was carried out in a 5L autoclave. The polymerization autoclave was first purged and replaced with dry nitrogen, and then 0.23MPa of hydrogen was introduced. 51mg of the catalyst MPP-01 prepared in Example 1 was suspended in 5ml of n-hexane to make a slurry and added to the catalyst feeder. Subsequently, 3.5ml of a 1mol / L triisobutylaluminum hexane solution was added, stirring was started, and the catalyst and triisobutylaluminum were flushed into the reactor with 2.3L of liquid propylene. The temperature was raised to 70°C and the reaction was carried out for 1 hour to obtain 345g of powdered polypropylene. The polymerization reaction activity was 6764gPP / gcat, the polypropylene melt index was 8950g / 10min, the molecular weight distribution was 3.5, and the polymer bulk density was 0.39g / cm 3 .

[0125] Propylene Bulk Polymerization of Examples 41 to 72

[0126] (1) Metallocene complexes range from Cat-2 to Cat-30;

[0127] (2) Metallocene catalysts used are MPP-02 to MPP-033;

[0128] (3) The polymerization process was the same as in Example 38. The catalyst activity, polymerization reaction conditions and polymer properties are shown in Table 2.

[0129] Example 73

[0130] The metallocene catalyst prepared by the present invention is also suitable for continuous production, particularly the Spheripol continuous loop production unit, a double-loop polypropylene production unit. When used for metallocene product production, the unit comprises: 1. a catalyst storage tank; 2. a prepolymerization reactor; 3. a first loop polymerization reactor; 4. a second loop polymerization reactor; 5. a flash tank; 6. a filter; 7. a steamer and dryer. The prepolymerization reactor can be a small single-loop reactor or a tank reactor. The tank reactor used in this experiment is the prepolymerization unit.

[0131] The specific steps are as follows:

[0132] (1) Catalyst MPP-01 was first added to a catalyst preparation tank, and then a mixture of vaseline and white oil (mass ratio 7:3) was added to prepare a slurry with a catalyst mass fraction of 20%. The catalyst was then fed into a prepolymerization reactor under the combined action of triethylaluminum and propylene. 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 feed propylene was 1:5000, the reaction temperature was 25°C, the reaction pressure was 3.4 MPa, and the reaction time was 8 minutes.

[0133] (2) The prepolymer obtained in step (1) is fed into a first loop reactor with fresh propylene and hydrogen to continue polymerization reaction. The mass ratio of hydrogen to propylene entering the first loop reactor is 1:5000 (200 ppm). The reaction temperature is 70° C., the reaction pressure is 3.8 MPa, and the reaction time is 40 minutes.

[0134] (3) The polymer obtained in step (2) and fresh propylene and hydrogen are fed into a second loop reactor to continue the reaction. The mass ratio of hydrogen to propylene entering the second loop reactor is 1:5000 (200 ppm). The reaction temperature is 70° C., the reaction pressure is 3.8 MPa, and the reaction time is 40 minutes. The material at the outlet of the second loop is passed through a flash kettle, a dryer, and other devices to obtain a polypropylene powder, i.e., a high melt index polypropylene resin, with a polypropylene melt index of 1750 g / 10 min and a polymer bulk density of 0.41 g / cm 3 , molecular weight distribution 2.9; the calculated catalyst activity is 10025gPP / gcat.

[0135] Example 74

[0136] The process of Example 74 was similar to that of Example 73, except for the catalyst used and the amount of components added in each polymerization stage. Specifically, the catalyst used in this example was MPP-08. In the prepolymerization stage, the catalyst feed rate was 0.18 mL / min, the hydrogen concentration in the loop reactor was 220 ppm, and the reaction temperature was 70°C. The resulting polypropylene had a melt index of 1680 g / 10 min and a polymer bulk density of 0.41 g / cm 3 , molecular weight distribution 2.8; the calculated catalyst activity is 9825gPP / gcat.

[0137] Example 75

[0138] The process of Example 75 is similar to that of Example 73, except for the catalyst used and the amount of components added in each polymerization stage. Specifically, the catalyst used in this example is the 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 resulting polypropylene has a melt index of 7880 g / 10 min and a polymer bulk density of 0.41 g / cm 3 , molecular weight distribution 2.8; the calculated catalyst activity is 11825gPP / gcat.

[0139] Comparative Examples 1 to 3

[0140] (1) Metallocene complexes are Cat-1 to Cat-3 respectively;

[0141] (2) Activation of silica gel carrier S0:

[0142] Grace 955 silica gel was vacuumed at 450°C for 3 hours and then naturally cooled to room temperature under inert gas protection.

[0143] (3) Preparation of catalyst compositions D1 to D3:

[0144] Metallocene complexes Cat-1 to Cat-3 (20 μmol) were dissolved in toluene to prepare 10 mM solutions. 5 g of activated Grace-955 silica gel support was added to a 50 mL flask containing 20 mL of toluene. 3 mL of a 1 M triisobutylaluminum-hexane solution was added, and after stirring for 3 hours, 15 mL of a 10 wt% MAO toluene solution was added. The mixture was heated to 60° C. and heated to react for 2 hours. The mixture was then cooled to room temperature, and all of the above-prepared toluene solutions of Cat-1 to Cat-3 were added. The mixture was stirred at room temperature for 30 minutes to obtain a catalyst composition. The upper layer of the clear toluene solution was removed, and the mixture was washed with toluene three times. The mixture was then vacuum-dried to obtain solid catalysts D-1 to D-3.

[0145] (4) Polymerization: The polymerization conditions were the same as in Example 34. The polymerization results are shown in Table 2.

[0146] Comparative Example 4

[0147] (1) The metallocene complex uses Cat-1;

[0148] (2) Preparation of catalyst composition D4:

[0149] Dissolve the metallocene complex Cat-1 in toluene to prepare a 10 mM solution. Add 5000 μmol of MAO (methylaluminoxane) solution to 1 mL of the toluene solution and stir at room temperature for 30 minutes to obtain catalyst composition D4.

[0150] (3) Polymerization: The polymerization conditions were the same as in Example 34. The polymerization results are shown in Table 2.

[0151] Table 2: Catalyst and polymerization performance

[0152] Test standards: Melt index, GB / T3682; Bulk density, ASTM D1895A; Molecular weight distribution, GB / T 36214.2-2018.

[0153] As can be seen from Table 2, Comparative Example 4 does not use a carrier, the polymer has poor fluidity, there are agglomerates, and the bulk density cannot be measured. The present invention proposes a new structure of metallocene complex and uses silica gel to modify the carrier to optimize the final catalyst. It can improve the polymer morphology, increase the bulk density, enhance the catalyst activity, and reduce the polymer molecular weight distribution. It can also 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 equipment and exhibit high activity and high hydrogen adjustment sensitivity.

[0154] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art may make various corresponding changes and modifications based on the present invention, but these corresponding changes and modifications should all fall within the scope of protection 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 the 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 linear or branched alkyl of C 1 -C 20 , unsaturated hydrocarbon group of C 1 -C 20 , haloalkyl of C 1 -C 20 , hydrocarbon group containing heteroatoms from Group 13 elements to Group 17 elements of C 1 -C 20 , silyl and its derivatives of C 1 -C 20 , cycloalkyl of C 3 -C 20 , aryl of C 6 -C 30 , alkyl-substituted aryl and its derivatives of C 7 -C 30 , aryl-substituted alkyl and its derivatives of C 7 -C 30 ; 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′-, wherein 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 are each independently selected from Ligand 1, Ligand 2, Ligand 3; Ligand 1 has the 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; The ligand 2 has the 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 XIII to Group XVII 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 XIII to Group XVII 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 elements 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; The ligand 3 has the 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 each independently selected from H, halogen, C 1 -C 40 linear or branched alkyl, C 1 -C 40 unsaturated hydrocarbyl, C 1 -C 40 haloalkyl, C 1 -C 40 hydrocarbyl groups containing heteroatoms from Group XIII to Group XVII elements, C 1 -C 40 silyl groups and their 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 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; 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 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.

3. The metallocene catalyst composition according to claim 1, wherein, In Formula I, M is selected from titanium, zirconium, hafnium.

4. The metallocene catalyst composition according to claim 1, wherein, In formula I, 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 , 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-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 4, wherein, In Formula I, X is 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 40 arylalkylene.

6. The metallocene catalyst composition according to claim 1, wherein, In Formula I, 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.

7. The metallocene catalyst composition according to claim 6, wherein, R′ is independently selected from methyl, ethyl, isopropyl, trimethylsilyl, phenyl, benzyl.

8. 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 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.

9. The metallocene catalyst composition according to claim 8, wherein, R 2 and R 2 ' are each independently selected from methyl, ethyl, isopropyl, tert-butyl, phenyl.

10. 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 or different 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; 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; 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.

11. The metallocene catalyst composition according to claim 10, wherein, 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-butyl, trifluoromethoxy, Cl, trifluoromethyl, carbonyl, trimethylsilyl.

12. The metallocene catalyst composition according to claim 10, wherein, R 4 and R 4 ' are each independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, phenyl.

13. 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; R 5 selected 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; 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.

14. The metallocene catalyst composition according to claim 13, wherein, R 4 、R 4 ’, R 4 ” and R 4 ”’ are each independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, phenyl.

15. The metallocene catalyst composition according to claim 1, wherein, The support is a silica modified support, and the silica modified support is obtained by heating after reacting a metal-organic framework coordination polymer with silica.

16. The metallocene catalyst composition according to claim 15, wherein, 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.

17. The metallocene catalyst composition according to claim 15, 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.

18. The metallocene catalyst composition according to claim 16, wherein, The dehydration condition of silica is to evacuate at 300 - 600°C.

19. The metallocene catalyst composition according to claim 16, wherein, The organic solvent includes one or a combination of two or more of toluene, hexane, heptane.

20. The metallocene catalyst composition according to claim 16, wherein, 1 - 100 mg of the metal-organic framework coordination polymer is added per gram of dehydrated silica.

21. The metallocene catalyst composition according to claim 1, wherein, The activator is a Lewis acidic substance.

22. The metallocene catalyst composition according to claim 1, wherein, The activator includes one or a combination of two or more of methylaluminoxane, polymethylaluminoxane, modified methylaluminoxane, and organoboron reagents.

23. 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, and diethylbenzylaluminum.

24. The metallocene catalyst composition according to claim 1, wherein, 50 - 80 kg of carrier is added per mole of the main catalyst.

25. The metallocene catalyst composition according to claim 1, wherein, the molar ratio of the activator to the main catalyst is 10 - 500:

1.

26. The metallocene catalyst composition according to claim 1, wherein, the molar ratio of the cocatalyst to the main catalyst is 10 - 500:

1.

27. The metallocene catalyst composition according to claim 1, wherein, The synthesis method of the main catalyst is shown by the following reaction formula: wherein, Ts are the same or different from each other, and the T is a monodentate or bidentate neutral ligand; LG is a leaving group, which are 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.

28. The metallocene catalyst composition according to claim 27, 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 13 to Group 17 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.

29. The metallocene catalyst composition according to claim 27, wherein, in the synthesis method of the main catalyst, the bidentate neutral ligand is selected from ortho-diether compounds, α,ω-diether compounds, ortho-diamine compounds, α,ω-diamine compounds, ortho-dithioether compounds, α,ω-dithioether compounds, ortho-diphosphine compounds, and α,ω-diphosphine compounds; wherein, x is 0, 1, 2, or 3.

30. The metallocene catalyst composition according to claim 27, 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 .

31. The metallocene catalyst composition according to claim 27, wherein, In the synthesis method of the main catalyst, the reaction medium is C 5 -C 15 alkane and / or cycloalkane.

32. The metallocene catalyst composition according to claim 27, 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.

33. The metallocene catalyst composition according to claim 27, wherein, in the synthesis method of the main catalyst, the reaction temperature is -100 °C to 100 °C.

34. The metallocene catalyst composition according to claim 33, wherein, in the synthesis method of the main catalyst, the reaction temperature is -75 °C to 100 °C.

35. The metallocene catalyst composition according to claim 33, wherein, in the synthesis method of the main catalyst, the reaction temperature is -50 °C to 100 °C.

36. The preparation method of the metallocene catalyst composition according to any one of claims 1 - 35, 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.

37. The preparation method according to claim 36, 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.

38. Use of the metallocene catalyst composition according to any one of claims 1-35 in the catalytic polymerization of olefins.

39. The use according to claim 38, wherein, the process of olefin polymerization includes a bulk slurry polymerization process, a solution slurry polymerization process or a gas phase polymerization process.

40. The use according to claim 38, wherein, the equipment for olefin polymerization is a batch polymerization reactor or a continuous production device.

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