A metallocene catalyst composition, its preparation and use

Abstract

The application discloses a metallocene catalyst composition, which comprises a main catalyst, a cocatalyst Lewis acid, a magnesium compound carrier Mg(OR I )(OR II ) and an olefin polymer; the olefin polymer is selected from a homopolymer of any one of ethylene, propylene, 1-butene, 1-hexene and 1-octene or a copolymer of at least two or more; and the main catalyst is a metallocene complex shown in formula I. The metallocene catalyst composition provided by the application can effectively reduce the fine powder content of the polymer, and can significantly improve the device plugging problem without changing the polymerization process flow and without adding new equipment when applied to the gas phase polymerization without an online prepolymerization reactor through the synergistic effect among the components. Due to the coating of a certain amount of the olefin polymer, the initial activity of the catalyst composition is inhibited, the temperature fluctuation range is reduced, and the polymerization is favorably carried out stably.

Description

Technical Field

[0001] This invention relates to the field of polyolefin catalyst technology, and more particularly to a metallocene catalyst composition, its preparation method, and its application in ethylene-propylene copolymerization. Background Technology

[0002] In the field of metallocene catalysts, in addition to the classic substituted cyclopentadienyl (Cp′), substituted indenyl (Ind′), and substituted fluorenyl (Flu′), and the large number of metallocene complexes formed by the combination of Cp′ / Ind′ / Flu′ (Metallocenes: Synthesis, Reactivity, Applications, A. Togni and R.L. Halterman Eds, Wiley, 1998), in recent years, a certain number of metallocene complexes have introduced heteroatoms such as nitrogen, phosphorus, oxygen, and sulfur into the cyclopentadienyl ring (Cp) or into the saturated or unsaturated ring adjacent to the Cp ring. Metallocene complexes containing heteroatomic rings either possess special polymerization activity toward olefins or special regio or stereoselectivity (C. DeRosa, F. Auriema, A. Di Capua, L. Resconi, S. Guidotti, I. Camurati, I. E. N. I. F. A. F. E ...

[0003] For example, US6756455 describes a class of zirconium-containing π-ligand complexes, particularly zirconium-containing complex catalysts coordinated with bridged indobenzotriazine and indobenzoindole derivatives. These zirconium-containing complex catalysts exhibit high activity, high molecular weight, and a bimodal molecular weight distribution under suitable conditions for the homopolymerization of ethylene. US6683150 discloses numerous examples of group IV transition metallocene complex catalysts using bridged indobenzoindole derivatives as ligands to catalyze the polymerization of propylene over a wide temperature range to produce high molecular weight polypropylene. WO03089485 provides a catalytic system formed by combining nitrogen-containing π-ligand group IV transition metallocene complexes with methylaluminoxane (MAO), characterized by a very low aluminum / metal ratio and high activity, capable of producing high molecular weight linear low-density polyethylene (mLLDPE) when combined with a suitable support. WO9924446 describes a class of nitrogen-containing heteroatom π-ligand complexes formed with group IV transition metals. These metallocene complexes are not only simple to synthesize and have high yields, but also excellent catalysts for olefin polymerization after activation with methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), which can be used to polymerize high molecular weight polyethylene and polypropylene respectively.

[0004] When ethylene and propylene are copolymerized using the same catalytic system, the resulting copolymers not only have lower molecular weights, but also exhibit a non-random distribution of the two monomers, tending more towards block copolymerization. Furthermore, compared to classic C2-symmetric zirconium-ceramic complexes, these zirconium-ceramic complex catalysts significantly reduce the probability of 2,1- and 1,3-misintercalation during propylene polymerization. Although heteroatom-containing π-coordinated metallocene complexes have shown remarkable performance in the homopolymerization catalysis of ethylene and α-olefins, there are very limited examples of ethylene-α-olefin copolymerization catalysis, and the resulting materials are still classified as plastics (WO03-045964, WO03-0489485).

[0005] In polymerization applications, metallocene catalysts, as homogeneous catalysts, produce polymers with poor morphology, easily causing blockages in polymerization reactors and equipment during polymerization and product transport. Their poor adaptability to industrial applications leads to difficulties in industrial use. Therefore, it is necessary to support them on solid catalysts. Since the formation of the cross-linked rubber phase in ethylene-propylene copolymerization requires a large-sized support pore, the pore size and volume distribution of silica gel supports are often insufficient to meet the requirements of high-rubber-content ethylene-propylene copolymerization. Alkoxymagnesium supports, with their large pore size and abundant internal pores, are suitable for ethylene-propylene copolymerization, facilitating the formation of large amounts of ethylene-propylene rubber within the pores, significantly increasing the ethylene-propylene rubber content in the copolymer, and improving copolymerization activity. Under normal polymerization conditions, catalyst systems supported on alkoxy magnesium support have high support particle strength and are not easily broken. However, when applied to gas-phase processes (such as the Innovene process, Novolen process, Unipol process, etc.), due to the design characteristics of these processes, there is no online prepolymerization reactor. This leads to problems such as large temperature fluctuations in the polymerization reaction, the easy generation of hot spots in the polymerization reaction, resulting in polymer agglomeration and high fine powder content in the polymer powder. These problems are more pronounced when the initial catalyst activity is high. Summary of the Invention

[0006] The purpose of this invention is to solve the problems of polymer agglomeration and high fine powder content in polymer powder when metallocene catalysts containing heteroatom rings are applied to the gas-phase synthesis of ethylene-propylene copolymers in the prior art. Therefore, this invention provides a metallocene catalyst composition, its preparation method, and its application in ethylene-propylene copolymerization.

[0007] To achieve the above objectives, the present invention provides a metallocene catalyst composition comprising a main catalyst, a co-catalyst, a magnesium compound support, and an olefin polymer; wherein the magnesium compound support is selected from Mg(OR) I (OR) II ), the R I and R II The hydrocarbon groups (such as methyl, ethyl, tert-butyl, propyl, etc.) are independently selected from C1-C8 straight-chain or branched hydrocarbon groups; the co-catalyst is a Lewis acid; the olefin polymer is selected from homopolymers or copolymers of at least two of ethylene, propylene, 1-butene, 1-hexene, and 1-octene; the main catalyst is a metallocene complex having the structure shown in Formula I.

[0008]

[0009] M is a transition metal, selected from any element in Group IIIB, Group IVB, Group VB and Group VIB of the periodic table;

[0010] n is 1, 2, 3, or 4, and each X may be the same or different, and is independently selected from H, halogen groups, unsubstituted or Rm-substituted C1-C groups. 20 Straight-chain or branched hydrocarbon groups, unsubstituted or Rm-substituted C3-C 20 cycloalkyl, unsubstituted or Rm-substituted C6-C 30 aryl, C1-C 20 Straight-chain or branched alkoxy groups, C1-C 20 Straight-chain or branched thiol groups, C1-C 20 Carboxyl groups (straight or branched), C2-C 20 Straight-chain or branched imine groups, C2-C 20 Straight-chain or branched phosphonium group, -OR°O- or -OSO2CF3, where R° is a divalent free radical selected from C2-C. 40 Alkylene, unsubstituted or Rm-substituted C6-C 30 The arylene group (in the -OR°O- structure, the two oxygen atoms can be at any position on the free radical, but preferably the positions of the two oxygen atoms are a combination of adjacent (α, β-positions) and alternating (α, γ-positions) positions on the free radical); the charge number obtained by multiplying the charge number of n and X is equal to the charge number of the central metal atom M minus two;

[0011] Q is a divalent free radical, selected from any one of =C(R′)2, =Si(R′)2, =Ge(R′)2, =NR′, =PR′, and =BR′, wherein each R′ is independently selected from unsubstituted or Rm-substituted C1-C 20 Straight-chain or branched hydrocarbon groups, C3-C 20 cycloalkyl, unsubstituted or Rm-substituted C6-C 30 Either aryl or trimethylsilyl;

[0012] A is a π-ligand with the structure shown in Equation II:

[0013]

[0014] E is a divalent free radical of an element in Group 15 or Group 16 of the periodic table, selected from oxygen radicals, sulfur radicals, selenium radicals, =NR″, and =PR″, wherein R″ is selected from unsubstituted or Rm-substituted C1-C elements. 20 Straight-chain or branched hydrocarbon groups, unsubstituted or Rm-substituted C6-C 30 Any of the aryl groups;

[0015] L is a divalent free radical, selected from any one of the structures shown in formulas III, IV, V, VI, VII, and VIII below, where i is 2:

[0016]

[0017] Z is a π-ligand, and Z is the same as A, or is selected from any of the structures shown in Formulas IX, X, XI, XII and XIII below;

[0018]

[0019]

[0020] Among them, R 1 and each R 12 Individually selected from hydrogen, C4-C6 heteroaryl groups, unsubstituted or Rm-substituted C1-C groups. 20 Straight-chain or branched hydrocarbon groups, C3-C 20 cycloalkyl, unsubstituted or Rm-substituted C6-C 30 Any of the aryl groups;

[0021] R 2 R 3 Each R 6 Each R 7 and each R 13 Each is independently selected from hydrogen, halogen, unsubstituted or Rm-substituted C1-C 20 Straight-chain or branched hydrocarbon groups, unsubstituted or Rm-substituted C3-C 20 cycloalkyl, unsubstituted or Rm-substituted C6-C 30 Any of the aryl groups;

[0022] R 4 Selected from hydrogen, unsubstituted or Rm-substituted C1-C 20 Straight-chain or branched hydrocarbon groups, trifluoromethyl, phenyl, p-tert-butylphenyl, p-trimethylsilylphenyl, p-trifluoromethylphenyl, 3,5-dichloro-4-trimethylsilylphenyl or 2-naphthyl;

[0023] Each R 5 Each is independently selected from hydrogen, fluorine, or methyl;

[0024] Each R 8 Selected independently from unsubstituted or Rm-substituted C1-C 20 Straight-chain or branched hydrocarbon groups, phenyl groups;

[0025] R 9 and R 9’ Each is independently selected from hydrogen, unsubstituted, or Rn-substituted C6-C. 15 aryl, C3-C 10 The heteroaryl group; wherein Rn is selected from at least one of cyano, nitro, halogen, methyl, ethyl, isopropyl, methoxy, tert-butyl, trifluoromethoxy, trifluoromethyl and trimethylsilyl;

[0026] Each R 10 and R 10’ Each is independently selected from hydrogen, halogen, unsubstituted or Rm-substituted C1-C 20 Straight-chain or branched hydrocarbon groups, or unsubstituted or Rm-substituted C6-C 30 aryl;

[0027] Each R 11 and R 11’ Each group is independently selected from hydrogen, halogen, ester group, alkoxy group, thiol group, amino group or phosphine group;

[0028] In the above, Rm is selected from halogen groups, elements from groups 13 to 17 of the periodic table, and C1-C2 elements. 10 Straight-chain or branched hydrocarbon groups, C6-C 10 At least one of the aryl groups.

[0029] The symbol * in each of the above structural formulas, whether attached to a chemical bond, atom, or free radical, indicates that this point can form a single chemical bond with a similar chemical bond, atom, or free radical; and all symbols * in the following text have the same meaning.

[0030] In the above, C1-C is unsubstituted or Rm-substituted. 20 Examples of straight-chain or branched hydrocarbon groups include: 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, etc., but are not limited to these. C3-C 20 Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and 1-adamantane. Unsubstituted or Rm-substituted C6-C... 30Examples of aryl groups include: phenyl, 1-naphthyl, 2-naphthyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, 9-phenanthyl, 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-butyl Phenyl, 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, etc., p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3, 5-Difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylbenzyl, 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenethyl, p-fluorophenethyl, p-chlorophenethyl, p-isopropylphenethyl, p-tert-butylphenethyl, p-trimethylsilylphenethyl, 2,6-difluorophenethyl, 3,5-difluorophenethyl, 3,4,5-trifluorophenethyl, perfluorophenethyl, 1-naphthylmethyl, di-naphthylmethyl, etc., but not limited to these.

[0031] Optionally, in Formula I, the monovalent anion π-ligand of A is formed by the π-ligand shown in Formula II and the nucleophile LR. n It is prepared by an exchange reaction, and the reaction formula is as follows:

[0032]

[0033] Among them, R n It is a C1-C6 straight-chain alkyl or C6-C 12 aryl, the nucleophile LR n LiR is an organolithium reagent n .

[0034] Optionally, E is selected from any one of oxygen radicals, sulfur radicals, and NR″, and R″ is selected from C1-C2. 10 The radical is selected from any one of linear alkyl, phenyl, benzyl, 1-naphthyl, 2-naphthyl, 2-anthrayl, 1-phenanthyl, 2-phenanthyl, and 5-phenanthyl; preferably, E is selected from any one of oxygen radical, sulfur radical, =NPh, and =NPh.

[0035] R 1 Selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furanyl, or 2-thienyl; R 2 R 3 Each is independently selected from hydrogen, fluorine, methyl, or ethyl; R 4 It is selected from hydrogen, methyl, trifluoromethyl, isopropyl, tert-butyl, phenyl, p-tert-butylphenyl, p-trimethylsilylphenyl, p-trifluoromethylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, or 2-naphthyl.

[0036] Optionally, each X is independently selected from H, a halogen group, a C1-C5 straight-chain alkyl group, a C1-C5 straight-chain alkoxy group, and a C1-C5 straight-chain carboxyl group; preferably, in Formula I, each X is independently selected from H, Cl, methyl, methoxy, and EtCOO-.

[0037] M is selected from any one of zirconium, titanium, yttrium, hafnium, vanadium, and chromium;

[0038] Q is selected from any one of =C(R′)2, =Si(R′)2, =Ge(R′)2, =NR′, =PR′ and =BR′, and each R′ is independently selected from any one of methyl, ethyl, isopropyl, benzyl and phenyl; preferably, Q is selected from any one of =C(Me)2, =Si(Me)2, =NPh and =PPh.

[0039] Optionally, each R 5 Each R 7 Each is independently selected from hydrogen, fluorine, or methyl;

[0040] Each R 8 Each R is independently selected from C1-C5 straight-chain or branched alkyl or phenyl groups, preferably, each R 8 Each of the following is independently selected from methyl, ethyl, isopropyl, tert-butyl, n-butyl, or phenyl;

[0041] Each R 9 and R 9’ Each of the following is independently selected from hydrogen, phenyl, 1-naphthyl, 2-naphthyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, 9-phenanthyl, furanyl, thiophene, quinolinyl, imidazolyl, pyrimidinyl, or Rn-substituted phenyl, wherein Rn is selected from at least one of cyano, nitro, halogen (F, Cl, Br, etc.), methyl, ethyl, isopropyl, tert-butyl, methoxy, tert-butyl, trifluoromethoxy, trifluoromethyl, and trimethylsilyl; each R 10 and R 10’ Each R is independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, or phenyl; 11 and R11’ Each R is independently selected from hydrogen, fluorine, chlorine, ester, alkoxy, thiol, amino, or phosphine groups; 12 Each R is independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furanyl, or 2-thiopheneyl; 13 Each is independently selected from hydrogen, fluorine, or chlorine.

[0042] The content of each component in the catalyst composition provided by the present invention can be adjusted according to actual needs.

[0043] Optionally, the content of the olefin polymer in the metallocene catalyst composition is 5% to 95% by mass percentage; preferably, the content of the olefin polymer in the metallocene catalyst composition is 10% to 90%; more preferably, the content of the olefin polymer in the metallocene catalyst composition is 15% to 85%.

[0044] Optionally, the olefin polymer is selected from polyethylene, polypropylene, or ethylene-propylene copolymer; the magnesium compound carrier is at least one of dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium; and the Lewis acid is selected from polymethylaluminoxane, modified polymethylaluminoxane, or organoboron reagent that simultaneously possesses chain, cyclic, and cage-like structural equilibrium states in solution.

[0045] Specifically, Lewis acids are a class of Lewis acidic substances that are bulky, electron-delocalized, and poorly coordinated. Representative examples of this class are polymethylaluminoxane (PMAO), which simultaneously possesses chain, cyclic, and cage-like structural equilibrium states in solution, and modified polymethylaluminoxane (MMAO).

[0046]

[0047] Numerous other examples of the volume-expanding, electron-delocalized, and coordination-poor anions described in this invention are available, such as [B(C6H5)4]. - ,[(CH3)B(C6F5)3] - [B(C6F5)4] - [B(2,6-(CH3)2-C6H3)4] - [B(2,4,6-(CH3)3-C6H2)4] - ,[B(2,3,5,6-(CH3)4-C6H)4] - ,[B(2,6-(CF3)2-C6H3)4] - ,[B(2,4,6-(CF3)3-C6H2)4] -[B(2,3,5,6-(CF3)4-C6H)4] - [B(3,5-(CH3)2-C6H3)4] - [B(3,4,5-(CH3)3-C6H2)4] - [B(3,5-(CF3)2-C6H3)4] - ,[B(3,4,5-(CF3)3-C6H2)4]-,[B(2,6-(CF3)2-C6F3)4]-,[B(2,4,6-(CF3)3-C6F2)4] - [B(2,3,5,6-(CF3)4-C6F)4] - [B(3,5-(CF3)2-C6F3)4] - [B(3,4,5-(CF3)3-C6F2)4] - [Al(C6H5)4] - [(CH3)Al(C6F5)3] - [Al(C6F5)4] - [Al(2,6-(CH3)2-C6H3)4] - ,[Al(2,4,6-(CH3)3-C6H2)4] - [Al(2,3,5,6-(CH3)4-C6H)4] - [Al(3,5-(CH3)2-C6H3)4] - [Al(3,4,5-(CH3)3-C6H2)4] - [Al(2,6-(CH3)2-C6F3)4] - ,[Al(2,4,6-(CH3)3-C6F2)4] - [Al(2,3,5,6-(CH3)4-C6F)4] - [Al(3,5-(CH3)2-C6F3)4] - [Al(3,4,5-(CH3)3-C6F2)4] - [Al(2,6-(CF3)2-C6H3)4] - ,[Al(2,4,6-(CF3)3-C6H2)4] - [Al(2,3,5,6-(CF3)4-C6H)4] - [Al(3,5-(CF3)2-C6H3)4] - [Al(3,4,5-(CF3)3-C6H2)4] -,[Al(2,6-(CF3)2-C6F3)4] - ,[Al(2,4,6-(CF3)3-C6F2)4] - ,[Al(2,3,5,6-(CF3)4-C6F)4] - ,[Al(3,5-(CF3)2-C6F3)4] - ,[Al(3,4,5-(CF3)3-C6F2)4] - ,{t-Bu-CH=C[B(C6F5)2]2(CH3)} - ,{Ph-CH=C[B(C6F5)2]2(CH3)} - ,{(C6F5)-CH=C[B(C6F5)2]2(CH3)} - ,{t-Bu-CH=C[Al(C6F5)2]2(CH3)} - ,{Ph-CH=C[Al(C6F5)2]2(CH3)} - ,{(C6F5)-CH=C[Al(C6F5)2]2(CH3)} - ,[1,1’-C 12 F8-2,2’=B(C6F5)2] - ,[1,1’-C 12 F8-2,2’=Al(C6F5)2] - ,[FB(1-C6F4-2-C6F5)3] - ,[(CH3)B(1-C6F4-2-C6F5)3] - ,[(C6F5)B(1-C6F4-2-C6F5)3] - ,[(C6F5)Al(1-C6F4-2-C6F5)3] - ,[FAl(1-C6F4-2-C6F5)3]-,[(CH3)Al(1-C6F4-2-C6F5)3]-,] - ,[HB(1-C6F4-2-C6F5)3] - ,[HAl(1-C6F4-2-C6F5)3] - ,[(CH3)B(2-C 10 F7)3] - ,[(CH3)Al(2-C 10 F7)3] - ,[(CH3)B(p-C6F4SiMe3)3] - ,[B(p-C6F4SiMe3)4] -[(CH3)B(p-C6F4Si(n-Bu)3)3] - [B(p-C6F4Si(n-Bu)3)4] - [(CH3)B(p-C6F4Si(i-Bu)3)3] - [B(p-C6F4Si(i-Bu)3)4] - ,[(CH3)B(p-C6F4Si(t-Bu)3)3]-,[B(p-C6F4Si(t-Bu)3)4]-,[(C6F5)3B-C6F4-B(C6F5)2] - [C6F4-1,2-(B(C6F5)3)2] - [C6F4-1,2-(Al(C6F5)3)2] - ,[(C6F4)-1,2-(B(C6F5)2)2-1',2'-(C6F4)] - ,[(C6F4)-1,2-(Al(C6F5)2)2-1',2'-(C6F4)] - [(C6F5)3B-CN-B(C6F5)3] - [(C6F5)3Al-CN-Al(C6F5)3] - [((C6F5)3BNC)4Ni] - [((C6F5)3AlNC)4Ni] - ,[(1,1'-C 12 F8)2-2,2'-B] - ,[(1,1'-C 12 F8)2-2,2'-Al] - [B(O-C6F5)4] - [Al(O-C6F5)4] - [(C6F5)3Al-C6F4-Al(C6F5)2] - [(CH3)Al(p-C6F4SiMe3)3] - [Al(p-C6F4SiMe3)4] - [(CH3)Al(p-C6F4Si(n-Bu)3)3] - [Al(p-C6F4Si(n-Bu)3)4] - [(CH3)Al(p-C6F4Si(i-Bu)3)3] - [Al(p-C6F4Si(i-Bu)3)4] - [(CH3)Al(p-C6F4Si(t-Bu)3)3]- [Al(p-C6F4Si(t-Bu)3)4] - [C5(C6H5)5] - [C5(2,6-(CH3)2-C6H3)5] - [C5(2,4,6-(CH3)3-C6H2)5] - [C5(3,5-(CH3)2-C6H3)5] - [C5(3,4,5-(CH3)3-C6H2)5] - [C5(2,6-(CF3)2-C6H3)5] - [C5(2,4,6-(CF3)3-C6H2)5] - [C5(3,5-(CF3)2-C6H3)5] - [C5(3,4,5-(CF3)3-C6H2)5] - ,[C5(2,6-(CH3)2-C6F3)5]-,[C5(2,4,6-(CH3)3-C6F2)5]-,[C5(3,5-(CH3)2-C6F3)5] - [C5(3,4,5-(CH3)3-C6F2)5] - [C5(2,6-(CF3)2-C6F3)5] - ,[C5(2,4,6-(CF3)3-C6F2)5] - ,[C5(3,5-(CF3)2-C6F3)5] - ,[C5(3,4,5-(CF3)3-C6F2)5] - [C5(C6F5)5] - ,[Li(Ta(OC6F5)4(2-OC6F5)2)2] - [Nb(OC6F5)6] - [PF6] - [AsF6] - [SbF6] - [BF4] - [ClO4] - Carborea anions, such as: [C2B9H] 12 ] - ,[CB 11 H 12 ] - However, it is not limited to this.

[0048] The present invention also provides a method for preparing the above-mentioned metallocene catalyst composition, comprising the following steps:

[0049] (1) A mixture is obtained by contacting a metallocene complex, a magnesium compound support and a co-catalyst in an organic solvent at -75°C to 120°C.

[0050] (2) After cooling the mixture to -20℃ to 50℃, olefins are introduced to obtain a crude metallocene catalyst composition;

[0051] (3) The crude product of the metallocene catalyst composition is washed, separated and dried to obtain the metallocene catalyst composition;

[0052] In step (2), the olefin is selected from at least one of ethylene, propylene, 1-butene, 1-hexene and 1-octene.

[0053] Optionally, in step (1), the contact time is 5s to 1h, the molar ratio of M in the co-catalyst and the main catalyst is 50 to 500, and the molar ratio of Mg in the magnesium compound support to M in the main catalyst is 100 to 1000.

[0054] Optionally, in step (2), the olefin is introduced at a rate of 0.1 g to 50 g / g magnesium compound carrier per hour, and the introduction time is 5 s to 2 h.

[0055] Optionally, in step (2), hydrogen (an activator) is introduced at the same time as the olefin, and the molar ratio of the olefin to the hydrogen is ≤100; preferably, the molar ratio of the olefin to the hydrogen is ≤50; more preferably, the molar ratio of the olefin to the hydrogen is ≤30.

[0056] Optionally, in step (3), the crude metallocene catalyst composition is washed with an organic solvent.

[0057] Optionally, the organic solvent is hexane, heptane, octane, decane, or toluene.

[0058] The present invention can control the content of olefin polymer in catalyst components by adjusting the amount of olefins entering the reactor per unit time, reaction time, reaction temperature, hydrogen usage and the molar ratio of metal elements in metallocene complex in step (2).

[0059] Optionally, the preparation method of the magnesium compound support includes the following steps:

[0060] alcohol R I OH and alcohol R II OH reacts with metallic magnesium powder in the presence of halogen. After the reaction is complete (heated until no more hydrogen gas is produced), the magnesium compound carrier Mg(OR) is obtained by washing. I (OR) II ).

[0061] Optionally, the preparation method of the metallocene complex includes the following steps:

[0062]

[0063] The compound of formula XIV was reacted with the compound of formula XV to prepare the compound shown in formula I;

[0064] Wherein, T is selected from monodentate or dipordentate ligands, and each T may be the same or different;

[0065] LG is a free radical, and each LG may be the same or different. The LG is selected from organic free radicals of hydrogen, alkali metal elements or group 14 heavy elements.

[0066] x is 0, 1, 2 or 3.

[0067] Optionally, the monodentate ligand includes ethers (ROR), thioethers (RSR), tertiary amines (N(R)3), tertiary phosphines (P(R)3), cyclic ethers, cyclic thioethers, ketones, Rm-substituted cyclic ketones, Rm-substituted pyridines, Rm-substituted pyrroles, Rm-substituted piperidines, esters, lactones, amides, and lactams, wherein R is selected from C1-C1. 20 Straight-chain or branched hydrocarbon groups, alkyl groups containing heteroatoms of elements from groups 13 to 17 of the periodic table, C3-C 20 cycloalkyl, unsubstituted or Rm-substituted C6-C 30 aryl groups, where Rm is defined as described above.

[0068] Optionally, the bidentate ligands include ortho-diethers, α,ω-diethers, ortho-diamines, α,ω-diamines, ortho-disulfides, α,ω-disulfides, ortho-diphosphines, and α,ω-diphosphines.

[0069] Optionally, the alkali metal element includes lithium, sodium, and potassium; the organic radicals of the group 14 heavy elements include Si(R)3, Ge(R)3, Sn(R)3, Pd(R)3, ZnR, BaR, MgR, and CaR, wherein each R is independently selected from C1-C. 20 Straight-chain or branched hydrocarbon groups, containing halogens or heteroatoms of elements from groups 13 to 17 of the periodic table, C1-C 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, unsubstituted or Rm-substituted C6-C 30 Aryl groups, etc., where Rm is defined as described above.

[0070] Optionally, the metallocene complex is prepared using a C5-C reaction medium. 15 Saturated alkanes, C5-C 15At least one of the cycloalkanes; preferably, the reaction medium is hexane, heptane, octane, toluene, or xylene.

[0071] Optionally, the reaction temperature between compound XIV and compound XV is -100℃ to +300℃; preferably, the reaction temperature is -75℃ to +250℃; more preferably, the reaction temperature is -50℃ to +150℃.

[0072] The present invention also provides the application of the above-described metallocene catalyst composition in olefin polymerization, preferably in ethylene-propylene copolymerization; more preferably in ethylene-propylene gas-phase copolymerization.

[0073] The metallocene catalyst composition provided by this invention can be used in known olefin polymerization processes, including slurry and gas-phase polymerization. The polymerization conditions can be selected from those commonly used in the art, and are particularly suitable for gas-phase polymerization. It can be applied to gas-phase fluidized beds, vertical gas-phase stirred tanks, or horizontal gas-phase stirred tanks. In any polymerization method used, the catalyst composition can be pre-contacted with an alkylaluminum compound before being introduced into the polymerization reactor. This pre-contact step can be carried out in the absence of polymerizable olefins.

[0074] Optionally, when the metallocene catalyst composition is used to catalyze olefin polymerization, the polymerization temperature is 0–120°C, preferably 20–90°C.

[0075] Optionally, when the metallocene catalyst composition is used to catalyze olefin polymerization, a Lewis acid is added during the polymerization process; preferably, the molar ratio of the added Lewis acid to the metallocene complex is 50 to 2000.

[0076] Optionally, when the metallocene catalyst composition is used to catalyze olefin polymerization, hydrogen gas can be introduced during the polymerization process.

[0077] Compared with the prior art, the present invention has the following advantages:

[0078] The metallocene catalyst composition provided by this invention, through the synergistic effect of its components, can effectively reduce the fine powder content of the polymer when applied to the gas-phase synthesis of ethylene-propylene copolymers, significantly improving the problem of equipment blockage. Furthermore, the initial activity of the catalyst composition is relatively suppressed, reducing temperature fluctuations and promoting stable polymerization. Specifically, the alkoxymagnesium support in this metallocene catalyst composition has a large pore size and abundant internal pores, making it suitable for ethylene-propylene copolymerization. This facilitates the generation of a large amount of ethylene-propylene rubber within the pores, significantly increasing the ethylene-propylene rubber content in the copolymer and enhancing copolymerization activity. By using offline prepolymerization to coat a solid catalyst with a certain amount of olefin polymer, the metallocene catalyst composition further increases the strength of the support particles. When applied to gas-phase polymerization units without an online prepolymerization reactor, this effectively reduces the fine powder content of the polymer, significantly improving equipment blockage without altering the polymerization process or adding new equipment. The coating of a certain amount of polyolefin suppresses the initial activity of the catalyst, reducing temperature fluctuations and promoting stable polymerization. Detailed Implementation

[0079] The present invention will now be described in detail through embodiments. It should be noted that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description.

[0080] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0081] In all examples, the preparation of the catalyst compositions was carried out under high-purity nitrogen protection. Specific examples are as follows.

[0082] The analytical characterization methods used in the related technologies of this invention are as follows:

[0083] MRI: AV400, BRUKER, Germany.

[0084] Determination of polymer content in catalyst component: Accurately weigh approximately 2g (weight recorded as m1) of solid catalyst component, soak it in 100mL of 1mol / L sulfuric acid solution, sonicate and vibrate for 30 minutes, filter, then wash three times with 100mL of distilled water, and dry the hollow solid powder (weight recorded as m2). Calculate the polymer content as: m2 / m1X100%.

[0085] Determination of the actual ethylene propylene rubber content (Ru) in polymer products: The percentage of the weight of the xylene soluble portion at room temperature relative to the sample weight is the rubber content.

[0086] Determination of fine powder content: According to ASTM E1187, particles below 80 mesh (equivalent to a particle size of less than 180 μm) are defined as fine powder.

[0087] Example 1

[0088] (1) Synthesis of the metallocene complex Cat-1:

[0089]

[0090] In the above reaction formula, M is Zr, and the specific synthesis steps are the same as those in Example 1 of Chinese Patent Document CN105985368A.

[0091] (2) Alkoxymagnesium support S mg Preparation of 1:

[0092] In a four-necked flask equipped with a stirrer, a reflux condenser was installed and a flow meter was connected to the reflux condenser. 60 ml of anhydrous ethanol and 1 g of iodine were added and dissolved. 5 g of magnesium was added, and the mixture was heated to 80°C with stirring. Starting from reflux, 45 ml of anhydrous ethanol and 5 g of magnesium were added every 10 minutes, for a total of three additions. After the third addition, when the viscosity of the liquid began to rise sharply (approximately 1 hour), 220 ml of toluene was added, and the reaction continued until no more hydrogen gas was produced. The entire reaction took approximately 6 hours. The remaining liquid was then filtered thoroughly, and the resulting solid was washed three times with 600 ml of toluene to obtain support S. mg 1.

[0093] (3) Preparation of catalyst composition CM-1:

[0094] The metallocene complex Cat-1 obtained in step (1) was dissolved in toluene to prepare a solution with a concentration of 10 mM.

[0095] 0.20 g of ethoxymagnesium carrier S mg 1. Add the solution to a 500 mL flask containing 200 mL of hexane, add 4 mL of the Cat-1 toluene solution (10 mM) prepared above, stir at room temperature for 30 minutes, then add 5 mmol of MAO (methylaluminoxane) solution, control the temperature at 10 °C, and hold at this temperature for 5 minutes; propylene is introduced through a mass flow meter at a rate of 20 g / h, and the propylene introduction is stopped after 60 minutes. After washing with n-hexane, filtering, and vacuum drying, 0.38 g of solid (catalyst composition) is obtained, in which the propylene polymer content is 40.5 (wt)%.

[0096] (4) Polymerization: The polymerization reaction was carried out in a horizontal gas phase polypropylene pilot plant with a capacity of 4 kg / hr, with two horizontal reactors connected in series.

[0097] The catalyst composition obtained in step (3) is continuously fed into the first reactor through the reactor inlet under the transport of liquid propylene. In this reactor, the homopolymerization of propylene is completed. MAO (Al / M molar ratio of 500) is added, the polymerization temperature is 70℃, and the pressure is 2.0 MPa. A certain amount of hydrogen is added to the reactor to control the molecular weight of the homopolymerized polypropylene. The molar ratio of hydrogen to propylene is 2.5*10. -3 The stay time is 80 minutes.

[0098] The material discharged from the first gas-phase reactor enters the second gas-phase reactor, where propylene and ethylene copolymerize to obtain an ethylene-propylene copolymer. The gas-phase reaction temperature is 75℃, the pressure is 2.1MPa, and the ethylene / propylene ratio is 1 (volume ratio). A certain amount of hydrogen is added to the feed to the gas-phase reactor, with a hydrogen / (ethylene + propylene) ratio of 0.001 (molar ratio). Low-purity nitrogen (oxygen content of 6000ppm) is introduced, and the residence time is 50min. The polymerization performance is shown in Table 2.

[0099] Examples 2-33

[0100] (1) Synthesis of metallocene complexes Cat-2 to Cat-33: The steps are the same as in Example 1, except that the raw materials are replaced with ligands with corresponding substituents. The substituents of the catalyst complexes are shown in Table 1.

[0101] (2) Alkoxymagnesium support S mg Preparation of 1: Same as in Example 1.

[0102] (3) Preparation of catalyst compositions CM-2 to CM-33: Same as in Example 1, except that Cat-1 is replaced with Cat-2 to Cat-33 respectively.

[0103] (4) Polymerization: The polymerization conditions are the same as in Example 1, and the polymerization performance is shown in Table 2.

[0104] Example 34

[0105] (1) The metallocene complex was Cat-4;

[0106] (2) Alkoxymagnesium support S mg Preparation of 1: Same as in Example 1.

[0107] (3) Preparation of catalyst composition CM-34:

[0108] The metallocene complex Cat-1 was dissolved in toluene to prepare a 10 mM solution.

[0109] 0.20 g of ethoxymagnesium carrier Smg 1. Add the solution to a 500 mL flask containing 200 mL of hexane, add 4 mL of the prepared Cat-1 toluene solution (10 mM), stir at room temperature for 30 minutes, then add 5 mmol of MAO (methylaluminoxane) solution, maintain the temperature at 10 °C, and hold for 5 minutes. Then, introduce propylene through a mass flow meter at a rate of 40 g / h, and react for 60 minutes. Stop the propylene flow, wash with n-hexane, filter, and dry under vacuum to obtain 0.57 g of solid with a propylene polymer content of 60.4% (wt)%.

[0110] (4) Polymerization: The polymerization conditions are the same as in Example 1, and the polymerization performance is shown in Table 2.

[0111] Example 35

[0112] (1) The metallocene complex was Cat-4;

[0113] (2) Alkoxymagnesium support S mg Preparation of 1: Same as in Example 1.

[0114] (3) Preparation of catalyst composition CM-35:

[0115] The metallocene complex Cat-4 was dissolved in toluene to prepare a 10 mM solution.

[0116] 0.20 g of ethoxymagnesium carrier S mg 1. Add the solution to a 500 mL flask containing 200 mL of hexane, add 4 mL of the prepared Cat-4 toluene solution (10 mM), stir at room temperature for 30 minutes, then add 5 mmol of MAO (methylaluminoxane) solution, maintain the temperature at 20 °C, and hold for 5 minutes. Then, introduce propylene through a mass flow meter at a rate of 20 g / h, and react for 60 minutes. Stop the propylene flow, wash with n-hexane, filter, and dry under vacuum to obtain 0.46 g of solid with a polymer content of 50.9% (wt)%.

[0117] (4) Polymerization: The polymerization conditions are the same as in Example 1, and the polymerization performance is shown in Table 2.

[0118] Example 36

[0119] (1) The metallocene complex was Cat-4;

[0120] (2) Alkoxymagnesium support S mg Preparation of 2:

[0121] In a four-necked flask equipped with a stirrer, a reflux condenser was installed and a flow meter was connected to it. 30 mL of anhydrous ethanol, 40 mL of anhydrous butanol, and 1 g of iodine were added and dissolved. 5 g of magnesium was added, and the mixture was heated to 80°C with stirring. Starting from reflux, 45 mL of anhydrous ethanol and 5 g of magnesium were added every 10 minutes, for a total of three additions. After the third addition, when the viscosity of the liquid began to rise sharply (approximately one hour), 220 mL of toluene was added, and the reaction continued until no more hydrogen gas was produced. The entire reaction took approximately 8 hours. The remaining liquid was then filtered thoroughly, and the resulting solid was washed three times with 600 mL of toluene to obtain support S. mg 2.

[0122] (3) Preparation of catalyst composition CM-36:

[0123] The metallocene complex Cat-4 was dissolved in toluene to prepare a 10 mM solution.

[0124] 0.20 g of ethoxybutoxymagnesium carrier S mg 2. Add the solution to a 500 mL flask containing 200 mL of hexane, add 4 mL of the prepared Cat-4 toluene solution (10 mM), stir at room temperature for 30 minutes, then add 5 mmol of MAO (methylaluminoxane) solution, maintain the temperature at 10 °C, and hold for 5 minutes. Plutonium is then introduced through a mass flow meter at a rate of 20 g / h, and the reaction is allowed to proceed for 60 minutes. The propylene flow is then stopped, and the mixture is washed with n-hexane, filtered, and dried under vacuum to obtain a solid with a polymer content of 30.6% (wt)%.

[0125] (4) Polymerization: The polymerization conditions are the same as in Example 1, and the polymerization performance is shown in Table 2.

[0126] Example 37

[0127] (1) The metallocene complex was Cat-4;

[0128] (2) Alkoxymagnesium support S mg Preparation of 1: Same as in Example 1.

[0129] (3) Preparation of catalyst composition CM-37:

[0130] The metallocene complex Cat-1 was dissolved in toluene to prepare a 10 mM solution.

[0131] 0.20 g of ethoxymagnesium carrier S mg1. Add the solution to a 500 mL flask containing 200 mL of hexane, add 4 mL of the prepared Cat-1 toluene solution (10 mM), stir at room temperature for 30 minutes, then add 1 mmol of MAO (methylaluminoxane) solution, maintain the temperature at 10 °C, and hold for 5 minutes. Then, introduce ethylene through a mass flow meter at a rate of 20 g / h, and react for 30 minutes. Stop the ethylene flow, wash with n-hexane, filter, and dry under vacuum to obtain a solid with an ethylene polymer content of 32.5% (wt)%.

[0132] (4) Polymerization: The polymerization conditions are the same as in Example 1, and the polymerization performance is shown in Table 2.

[0133] Comparative Example 1

[0134] (1) The metallocene complex was Cat-4.

[0135] (2) Activation of silica carrier S0:

[0136] After evacuating the Grace 955 silicone at 450°C for 3 hours, it was naturally cooled to room temperature under the protection of inert nitrogen gas.

[0137] (3) Preparation of catalyst composition D1:

[0138] The metallocene complex Cat-4 was dissolved in toluene to prepare a 10 mM solution. 50 mg of the Grace-955 silica support activated in step (2) was added to a 50 mL flask containing 20 mL of hexane, followed by 5000 μmol of MAO (methylaluminoxane) solution. After stirring for five minutes, 1 mL of the Cat-4 toluene solution (10 mM) prepared above was added, and the mixture was stirred at room temperature for 30 minutes to obtain catalyst composition D1.

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

[0140] Comparative Example 2

[0141] (1) The metallocene complex was Cat-4;

[0142] (2) Alkoxymagnesium support S mg Preparation of 1: Same as in Example 1.

[0143] (3) Preparation of catalyst composition D2:

[0144] The metallocene complex Cat-4 was dissolved in toluene to prepare a 10 mM solution.

[0145] 0.20 g of ethoxymagnesium carrier S mg1. Add to a 500 mL flask containing 200 mL hexane, add 4 mL of the Cat-1 toluene solution (10 mM) prepared above, stir at room temperature for 30 minutes to obtain catalyst composition D2.

[0146] (4) Polymerization: The polymerization conditions are the same as in Example 1, and the polymerization performance is shown in Table 2.

[0147] Comparative Example 3

[0148] (1) The metallocene complex was Cat-4.

[0149] (2) Activation of silica carrier S0:

[0150] After evacuating the Grace 955 silicone at 450°C for 3 hours, it was naturally cooled to room temperature under the protection of inert nitrogen gas.

[0151] (3) Preparation of catalyst composition D3:

[0152] 0.20 g of silica gel support SO was added to a 500 mL flask containing 200 mL of hexane, followed by 4 mL of Cat-4 toluene solution (10 mM). The mixture was stirred at room temperature for 30 minutes, then 5 mmol of MAO (methylaluminoxane) solution was added. The temperature was maintained at 10 °C for 5 minutes. Propylene was introduced through a mass flow meter at a rate of 20 g / h. After 60 minutes, the propylene introduction was stopped. The mixture was washed with n-hexane, filtered, and dried under vacuum to obtain 0.38 g of solid (catalyst composition), of which the propylene polymer content was 53.1% (wt).

[0153] (4) Polymerization: The polymerization conditions are the same as in Example 1, and the polymerization performance is shown in Table 2.

[0154] Table 1

[0155]

[0156]

[0157] Table 2

[0158]

[0159]

[0160] As shown in Table 2 above, compared with Comparative Example 1, which uses silica gel as a carrier and does not contain olefin polymer components, Example 4 exhibits a significantly increased ethylene propylene rubber content, a significantly reduced fine powder content, no agglomeration in the feed line, and smaller temperature fluctuations. Compared with Comparative Example 2, which uses alkoxymagnesium as a carrier and does not contain polyolefin components, Example 4 exhibits a significantly reduced fine powder content, no agglomeration in the feed line, and smaller temperature fluctuations. Compared with Comparative Example 3, Example 4 shows a significantly increased rubber content. The experimental results of Examples 1-36 demonstrate that the catalyst composition provided by this invention possesses the aforementioned technical effects, indicating that coating a certain amount of polyolefin onto the metallocene catalyst supported by alkoxymagnesium through offline prepolymerization can increase catalyst particle strength, reduce breakage, decrease fine powder content, and reduce reactor scaling.

[0161] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A metallocene catalyst composition, characterized in that, It includes a main catalyst, a co-catalyst, a magnesium compound support, and an olefin polymer; wherein the magnesium compound support is selected from Mg(OR) I (OR) II ), the R I and R II The hydrocarbon groups are independently selected from C1-C8 straight-chain or branched hydrocarbon groups; the co-catalyst is a Lewis acid; the olefin polymer is selected from homopolymers or copolymers of any one of ethylene, propylene, 1-butene, 1-hexene, and 1-octene; the main catalyst is a metallocene complex having the structure shown in Formula I. M is a transition metal, selected from any element in Group IIIB, Group IVB, Group VB and Group VIB of the periodic table; n is 1, 2, 3, or 4, and each X may be the same or different, and is independently selected from H, halogen groups, unsubstituted or Rm-substituted C1-C groups. 20 Straight-chain or branched hydrocarbon groups, unsubstituted or Rm-substituted C3-C 20 cycloalkyl, unsubstituted or Rm-substituted C6-C 30 aryl, C1-C 20 Straight-chain or branched alkoxy groups, C1-C 20 Straight-chain or branched thiol groups, C1-C 20 Carboxyl groups (straight or branched), C2-C 20 Straight-chain or branched imine groups, C2-C 20 Straight-chain or branched phosphonium group, -OR°O- or -OSO2CF3, where R° is a divalent free radical selected from C2-C 40 Alkylene, unsubstituted or Rm-substituted C6-C 30 The product of the charges of n and X is equal to the charge of the central metal atom M minus two. Q is a divalent free radical, selected from any one of =C(R′)2, =Si(R′)2, =Ge(R′)2, =NR′, =PR′, and =BR′, wherein each R′ is independently selected from unsubstituted or Rm-substituted C1-C 20 Straight-chain or branched hydrocarbon groups, C3-C 20 cycloalkyl, unsubstituted or Rm-substituted C6-C 30 Either aryl or trimethylsilyl; A is a π-ligand with the structure shown in Equation II: E is a divalent free radical of an element in Group 15 or Group 16 of the periodic table, selected from oxygen radicals, sulfur radicals, selenium radicals, =NR″, and =PR″, wherein R″ is selected from unsubstituted or Rm-substituted C1-C elements. 20 Straight-chain or branched hydrocarbon groups, unsubstituted or Rm-substituted C6-C 30 Any of the aryl groups; L is a divalent free radical, selected from any one of the structures shown in formulas III, IV, V, VI, VII, and VIII below, where i is 2: Z is a π-ligand, and Z is the same as A, or is selected from any of the structures shown in Formulas IX, X, XI, XII and XIII below; Among them, R 1 and each R 12 Individually selected from hydrogen, C4-C6 heteroaryl groups, unsubstituted or Rm-substituted C1-C groups. 20 Straight-chain or branched hydrocarbon groups, C3-C 20 cycloalkyl, unsubstituted or Rm-substituted C6-C 30 Any of the aryl groups; R 2 R 3 Each R 6 Each R 7 and each R 13 Each is independently selected from hydrogen, halogen, unsubstituted or Rm-substituted C1-C 20 Straight-chain or branched hydrocarbon groups, unsubstituted or Rm-substituted C3-C 20 cycloalkyl, unsubstituted or Rm-substituted C6-C 30 Any of the aryl groups; R 4 Selected from hydrogen, unsubstituted or Rm-substituted C1-C 20 Straight-chain or branched hydrocarbon groups, trifluoromethyl, phenyl, p-tert-butylphenyl, p-trimethylsilylphenyl, p-trifluoromethylphenyl, 3,5-dichloro-4-trimethylsilylphenyl or 2-naphthyl; Each R 5 Each is independently selected from hydrogen, fluorine, or methyl; Each R 8 Selected independently from unsubstituted or Rm-substituted C1-C 20 Straight-chain or branched hydrocarbon groups or phenyl groups; R 9 and R 9’ Selected independently from unsubstituted or Rn-substituted C6-C 15 aryl, C3-C 10 The heteroaryl group; wherein Rn is selected from at least one of cyano, nitro, halogen, methyl, ethyl, isopropyl, methoxy, tert-butyl, trifluoromethoxy, trifluoromethyl and trimethylsilyl; Each R 10 and R 10’ Each is independently selected from hydrogen, halogen, unsubstituted or Rm-substituted C1-C 20 Straight-chain or branched hydrocarbon groups, or unsubstituted or Rm-substituted C6-C 30 aryl; Each R 11 and R 11’ Each group is independently selected from hydrogen, halogen, ester group, alkoxy group, thiol group, amino group or phosphine group; In the above, Rm is selected from halogen groups, C1-C 10 Straight-chain or branched hydrocarbon groups, C6-C 10 At least one of the aryl groups; The preparation method of the metallocene catalyst composition includes the following steps: (1) A mixture is obtained by contacting a metallocene complex, a magnesium compound support, and a co-catalyst in an organic solvent at -75°C to 120°C. (2) After cooling the mixture to -20℃~50℃, olefins are introduced to obtain a crude metallocene catalyst composition; (3) The crude metallocene catalyst composition is washed, separated and dried to obtain the metallocene catalyst composition.

2. The metallocene catalyst composition according to claim 1, characterized in that, E is selected from any one of oxygen free radicals, sulfur free radicals, =PR″ and =NR″, wherein R″ is selected from C1-C 10 Any one of straight-chain alkyl, phenyl, benzyl, 1-naphthyl, 2-naphthyl, 2-anthrayl, 1-phenanthyl, 2-phenanthyl and 5-phenanthyl; R 1 Selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furanyl, or 2-thienyl; R 2 R 3 Each is independently selected from hydrogen, methyl, ethyl, or fluorine; R 4 It is selected from hydrogen, methyl, trifluoromethyl, isopropyl, tert-butyl, phenyl, p-tert-butylphenyl, p-trimethylsilylphenyl, p-trifluoromethylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, or 2-naphthyl.

3. The metallocene catalyst composition according to claim 1, characterized in that, Each X is independently selected from H, halogen groups, C1-C5 straight-chain alkyl groups, C1-C5 straight-chain alkoxy groups, and C1-C5 straight-chain carboxyl groups; M is selected from any one of zirconium, titanium, yttrium, hafnium, vanadium, and chromium; Q is selected from any one of =C(R′)2, =Si(R′)2, =Ge(R′)2, =NR′, =PR′ and =BR′, and R′ is selected from any one of methyl, ethyl, isopropyl and phenyl.

4. The metallocene catalyst composition according to claim 1, characterized in that, Each R 5 Each R is independently selected from hydrogen, fluorine, or methyl; 7 Each is independently selected from hydrogen, fluorine, or methyl; Each R 8 Alkyl or phenyl groups, each independently selected from C1-C5 straight-chain or branched-chain groups; Each R 9 and R 9’ Each of the following is independently selected from phenyl, 1-naphthyl, 2-naphthyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, 9-phenanthyl, furanyl, thiophene, quinolinyl, imidazolyl, pyrimidinyl, or Rn-substituted phenyl, wherein Rn is selected from at least one of cyano, nitro, halogen, methyl, ethyl, isopropyl, methoxy, tert-butyl, trifluoromethoxy, trifluoromethyl, and trimethylsilyl; each R 10 and R 10 Each R is independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, or phenyl; 11 and R 11’ Each R is independently selected from hydrogen, fluorine, chlorine, ester, alkoxy, thiol, amino, or phosphine groups; 12 Each R is independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furanyl, or 2-thiopheneyl; 13 Each is independently selected from hydrogen, fluorine, or chlorine.

5. The metallocene catalyst composition according to claim 1, characterized in that, The content of the olefin polymer in the metallocene catalyst composition is 5% to 95% by mass percentage.

6. The metallocene catalyst composition according to claim 1, characterized in that, The olefin polymer is selected from polyethylene, polypropylene, or ethylene-propylene copolymer; and / or The magnesium compound support is at least one selected from dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium; and / or The Lewis acid is selected from polymethylaluminoxane, modified polymethylaluminoxane, or organoboron reagent.

7. The metallocene catalyst composition according to claim 2, characterized in that, The E is selected from any one of oxygen free radicals, sulfur free radicals, =PPh, and =NPh.

8. The metallocene catalyst composition according to claim 1, characterized in that, In step (2), hydrogen gas is introduced at the same time as olefin, and the molar ratio of olefin to hydrogen gas is ≤100.

9. The metallocene catalyst composition according to claim 1, characterized in that, The preparation method of the magnesium compound support includes the following steps: alcohol R I OH and alcohol R II OH reacts with metallic magnesium powder in the presence of halogen. After the reaction is complete, the mixture is washed to obtain the magnesium compound support Mg(OR). I (OR) II ).

10. The metallocene catalyst composition according to claim 3, characterized in that, Each X is independently selected from H, Cl, methyl, methoxy, and EtCOO-.

11. The metallocene catalyst composition according to claim 3, characterized in that, Q is selected from any one of =C(Me)2, =Si(Me)2, =NPh, and =PPh.

12. The metallocene catalyst composition according to claim 4, characterized in that, Each R 8 Each of the following is independently selected from methyl, ethyl, isopropyl, n-butyl, tert-butyl, or phenyl.

13. The metallocene catalyst composition according to claim 5, characterized in that, The content of the olefin polymer in the metallocene catalyst composition is 10% to 90%.

14. The metallocene catalyst composition according to claim 13, characterized in that, The content of the olefin polymer in the metallocene catalyst composition is 15% to 85%.

15. The metallocene catalyst composition according to claim 8, characterized in that, In step (2), the molar ratio of the olefin to hydrogen is ≤50.

16. The metallocene catalyst composition according to claim 15, characterized in that, In step (2), the molar ratio of the olefin to hydrogen is ≤30.

17. The use of the metallocene catalyst composition according to any one of claims 1-16 in olefin polymerization.

18. The application according to claim 17, characterized in that, Applications in ethylene-propylene copolymerization.

19. The application according to claim 18, characterized in that, Application in ethylene-propylene vapor-phase copolymerization.

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