Metallocene compounds, catalyst compositions, olefin polymerization methods and applications

Abstract

This invention relates to the field of olefin polymerization, and discloses a metallocene compound, a catalyst composition using the metallocene compound, an olefin polymerization method using the catalyst composition, and the application of the metallocene compound or the catalyst composition in olefin polymerization. The metallocene compound has the structure shown in formula (1), where M is a tetravalent transition metal atom; X 1 and X 2 Each group is independently a halogen atom, an alkyl group with 1-10 carbon atoms, an aromatic group with 6-12 carbon atoms, or an N,N-dialkylamine group with 2-8 carbon atoms. Using the catalyst composition of the present invention provides advantages such as high catalytic activity, good copolymerization performance, and high molecular weight of the obtained polymer.

Description

Technical Field

[0001] This invention relates to the field of olefin polymerization, and more specifically, to a metallocene compound, a catalyst composition using the metallocene compound, an olefin polymerization method using the catalyst composition, and the application of the metallocene compound or the catalyst composition in olefin polymerization. Background Technology

[0002] Metallocene compounds for olefin polymerization have been a research hotspot in organometallic chemistry, catalysis, polymer chemistry, and materials science for decades. Using these catalysts, olefin polymers with highly uniform molecular weight and chemical composition distributions can be obtained, and the molecular structure and molecular weight of the polymer can be highly controlled by adjusting the catalyst structure. Metallocenes exhibit strong copolymerization capabilities in two aspects (ChemistrySelect 2020, 5, 7581-7585): firstly, under the same polymerization conditions, copolymers obtained from metallocenes contain higher levels of comonomers than those obtained from other catalysts, demonstrating their high copolymerization efficiency; secondly, some monomers that cannot be polymerized by other catalysts can also serve as comonomers in metallocene compound systems, showcasing their broad copolymerization spectrum. Due to the high efficiency and broad copolymerization spectrum of metallocene compounds, they can catalyze the formation of many novel copolymers. Compared to copolymers obtained from other catalysts, these copolymers possess new compositions and structures, potentially leading to new properties and enabling the application of polyolefin materials in new fields.

[0003] The structure of metallocene catalysts determines their catalytic performance; even small structural changes can lead to significant variations in catalytic performance. When designing metallocene catalysts, structural design aims to maximize the catalyst's polymerization activity and copolymerization performance, as well as the molecular weight of the polymer, thereby expanding the operational scope of production and improving economic efficiency.

[0004] Existing metallocene catalysts still have issues with improving catalyst activity, copolymerization performance, and polymer molecular weight. Summary of the Invention

[0005] The purpose of this invention is to provide a novel metallocene compound, a catalyst composition using the metallocene compound, an olefin polymerization method using the catalyst composition, and the application of the metallocene compound or the catalyst composition in olefin polymerization. By using the catalyst composition of this invention, the polymer has the advantages of high catalytic activity, good copolymerization performance, and high molecular weight.

[0006] To achieve the above objectives, the present invention provides a metallocene compound having the structure shown in formula (1).

[0007]

[0008] In equation (1), M is a tetravalent transition metal atom; X 1 and X 2 Each is independently a halogen atom, an alkyl group with 1-10 carbon atoms, an aromatic group with 6-12 carbon atoms, or an N,N-dialkylamine group with 2-8 carbon atoms.

[0009] Preferably, M is a titanium atom, a zirconium atom, or a hafnium atom, more preferably a titanium atom or a zirconium atom, and even more preferably a zirconium atom.

[0010] Preferably, X 1 and X 2 Each is independently a halogen atom, an alkyl group having 1-6 carbon atoms, an aromatic group having 6-10 carbon atoms, or an N,N-dialkylamino group having 2-6 carbon atoms; more preferably, X 1 and X 2 Each of the following is independently a halogen atom, an alkyl group having 1-3 carbon atoms, an aromatic group having 6-8 carbon atoms, or an N,N-dialkylamino group having 2-6 carbon atoms; more preferably, X 1 and X 2 Each of the following is independently F, Cl, Br, I, methyl, ethyl, propyl, phenyl, benzyl, N,N-dimethylamino, N,N-diethylamino, or N,N-dipropylamino; more preferably, X 1 and X 2 Each can be independently Cl, methyl, benzyl, or N,N-dimethylamino.

[0011] According to a second aspect of the present invention, a catalyst composition is provided, wherein the catalyst composition comprises the following components,

[0012] a) The metallocene compound described in the first aspect of the present invention;

[0013] b) Co-catalyst components.

[0014] Preferably, the cocatalyst component comprises alkylaluminoxane or a combination of organoboron compounds and organoaluminum compounds; more preferably, the cocatalyst component is a combination of alkylaluminoxane or organoboron compounds and organoaluminum compounds.

[0015] Preferably, the alkylaluminoxane is a compound selected from the structures shown in formula (2) and / or formula (3).

[0016]

[0017]

[0018] In formulas (2) and (3), R is selected from alkyl groups having 1-15 carbon atoms, and n represents an integer from 4 to 30; more preferably, R is selected from alkyl groups having 1-5 carbon atoms, and n represents an integer from 10 to 30.

[0019] Preferably, the alkylaluminoxane is methylaluminoxane.

[0020] Preferably, the organoboron compound is [B(C6F5)4]. - Z + Z + Having the structure shown in equation (4) or equation (5),

[0021]

[0022] Preferably, the organoaluminum compound is a compound with the general formula AlX1X2X3, where X1, X2 and X3 are halogen atoms or alkyl groups having 1-12 carbon atoms, and X1, X2 and X3 can be the same or different, and at least one of them is an alkyl group having 1-12 carbon atoms.

[0023] Preferably, the organoaluminum compound is one or a mixture of two or more of diethylaluminum chloride, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum, and is more preferably triisobutylaluminum.

[0024] Preferably, the cocatalyst component is an alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane (calculated as aluminum) is 1:(100-50000), more preferably 1:(500-10000), and even more preferably 1:(500-2000).

[0025] Preferably, the cocatalyst component is a combination of organoboron compound and organoaluminum compound, wherein the molar ratio of the metallocene compound to the organoboron compound is 1:(1-20), preferably 1:(1-5), more preferably 1:(1-2), and the molar ratio of the metallocene compound to the organoaluminum compound is 1:(10-5000), preferably 1:(50-1000), more preferably 1:(50-500).

[0026] According to a third aspect of the present invention, an olefin polymerization method is provided, wherein the method comprises contacting an olefin with a catalyst composition described in a second aspect of the present invention to induce a polymerization reaction.

[0027] Preferably, the concentration of the metallocene compound in the polymerization reaction system is 1 × 10⁻⁶. -8 mol / L ~ 1×10 -2 mol / L, preferably 1×10 -6 mol / L ~ 1×10 -3 Moles per liter.

[0028] Preferably, the olefin is ethylene or a combination of ethylene and α-olefin.

[0029] Preferably, the α-olefin is selected from one or more of propylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene.

[0030] Preferably, the partial pressure of the ethylene is 0.1-6 MPa, and more preferably 0.1-3 MPa.

[0031] Preferably, the polymerization reaction is carried out in the presence of an organic solvent, which is one or more of toluene, cyclohexane, and hexane.

[0032] Preferably, the polymerization temperature is -50 to 200°C and the polymerization time is 1 to 300 minutes; more preferably, the polymerization temperature is -20 to 150°C and the polymerization time is 5 to 60 minutes.

[0033] According to a fourth aspect of the present invention, the use of the metallocene compound described in the first aspect of the present invention or the catalyst composition described in the second aspect of the present invention in olefin polymerization is provided.

[0034] Through the above technical solutions, the present invention provides a new metallocene compound, a catalyst composition using the metallocene compound, an olefin polymerization method using the catalyst composition, and the application of the metallocene compound or the catalyst composition in olefin polymerization. By using the catalyst composition of the present invention, it has the advantages of high catalytic activity, good copolymerization performance, and high molecular weight of the obtained polymer. Detailed Implementation

[0035] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0036] A first aspect of the present invention provides a metallocene compound having the structure shown in formula (1).

[0037]

[0038] In equation (1), M is a tetravalent transition metal atom; X 1 and X 2 Each is independently a halogen atom, an alkyl group with 1-10 carbon atoms, an aromatic group with 6-12 carbon atoms, or an N,N-dialkylamine group with 2-8 carbon atoms.

[0039] According to the metallocene compound of the present invention, in formula (1), M is a tetravalent transition metal atom, preferably, M is a titanium atom, a zirconium atom or a hafnium atom; more preferably, M is a titanium atom or a zirconium atom; particularly preferably, M is a zirconium atom.

[0040] According to the metallocene compounds of the present invention, in formula (1), X 1 and X 2 Each is independently a halogen atom, an alkyl group with 1-10 carbon atoms, an aromatic group with 6-12 carbon atoms, or an N,N-dialkylamine group with 2-8 carbon atoms.

[0041] Examples of halogen atoms include fluorine, chlorine, bromine, or iodine, with fluorine, chlorine, or bromine being preferred, chlorine or bromine being more preferred, and chlorine being particularly preferred.

[0042] Examples of alkyl groups having 1-10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl. Among these, methyl, ethyl, propyl, or isopropyl is preferred, and methyl or ethyl is more preferred.

[0043] Examples of aromatic groups with 6-12 carbon atoms include phenyl, benzyl, or phenethyl. Among these, benzyl is preferred.

[0044] In this invention, preferably, in formula (1), X 1 and X 2 Each is independently a halogen atom, an alkyl group having 1-6 carbon atoms, an aromatic group having 6-10 carbon atoms, or an N,N-dialkylamino group having 2-6 carbon atoms; more preferably, X 1 and X 2 Each of the following is independently a halogen atom, an alkyl group having 1-3 carbon atoms, an aromatic group having 6-8 carbon atoms, or an N,N-dialkylamino group having 2-6 carbon atoms; more preferably, X 1 and X 2 Each of the following is independently F, Cl, Br, I, methyl, ethyl, propyl, phenyl, benzyl, N,N-dimethylamino, N,N-diethylamino, or N,N-dipropylamino; particularly preferably, X 1 and X 2 Each can be independently Cl, methyl, benzyl, or N,N-dimethylamino.

[0045] In a particularly preferred embodiment of the invention, X 1 and X 2 Both are Cl.

[0046] In another particularly preferred embodiment of the invention, X 1 and X 2Both are methyl groups.

[0047] In another particularly preferred embodiment of the invention, X 1 and X 2 Both are benzyl groups.

[0048] In another particularly preferred embodiment of the invention, X 1 and X 2 Both are N,N-dimethylamino groups.

[0049] The following compounds are preferred examples of specific metallocene compounds.

[0050] In equation (1), M is a titanium atom, X 1 and X 2 Both are Cl;

[0051] In equation (1), M is a titanium atom, X 1 and X 2 Both are methyl groups;

[0052] In equation (1), M is a titanium atom, X 1 and X 2 Both are benzyl groups;

[0053] In equation (1), M is a titanium atom, X 1 and X 2 Both are N,N-dimethylamino groups;

[0054] In equation (1), M is a zirconium atom, X 1 and X 2 Both are Cl;

[0055] In equation (1), M is a zirconium atom, X 1 and X 2 Both are methyl groups;

[0056] In equation (1), M is a zirconium atom, X 1 and X 2 Both are benzyl groups;

[0057] In equation (1), M is a zirconium atom, X 1 and X 2 Both are N,N-dimethylamino groups;

[0058] In equation (1), M is a hafnium atom, X 1 and X 2 Both are Cl;

[0059] In equation (1), M is a hafnium atom, X 1 and X 2 Both are methyl groups;

[0060] In equation (1), M is a hafnium atom, X 1and X 2 Both are benzyl groups;

[0061] In equation (1), M is a hafnium atom, X 1 and X 2 Both are N,N-dimethylamino groups.

[0062] The metallocene compounds according to the present invention can be synthesized according to conventional methods in the art.

[0063] In this invention, X 1 and X 2 The preferred method for preparing metallocene compounds with N,N-dialkylamine groups having 2-8 carbon atoms includes the following steps:

[0064] 1) The step of allowing compound A and compound B to undergo a first contact reaction in the presence of catalyst C and a first solvent to obtain intermediate product D;

[0065] 2) The step of reacting intermediate product D with compound E in the presence of a second solvent to obtain intermediate product F;

[0066] 3) The step of reacting intermediate F with M(NA2)4 in the presence of a third solvent to obtain compound H.

[0067]

[0068] Where A is a hydrocarbon group with 1-4 atoms; n is an integer from 1 to 5; R 1 R 2 R 3 R 4 Each can be independently a hydrogen atom, methyl, ethyl, isopropyl, or tert-butyl.

[0069] The following steps will explain the process.

[0070] Step 1): In the presence of catalyst C and a first solvent, compound A and compound B are subjected to the second reaction. The initial contact reaction yields intermediate product D. .

[0071] In step 1) above, n in catalyst C is preferably 2 or 3.

[0072] Catalyst C is preferably one or more of pyrrolidine, 2-methylpyrrolidine, 2,5-dimethylpyrrolidine, 2,2,5,5-tetramethylpyrrolidine, piperidine, and 2,2,6,6-tetramethylpiperidine.

[0073] The amount of catalyst C can be selected based on the compound A. Preferably, the molar ratio of reactant A to catalyst C is 1:1-5, and more preferably 1:1.1-3.

[0074] In step 1) above, the first solvent is preferably methanol, and more preferably anhydrous methanol.

[0075] The amount of the first solvent can be selected according to the compound A. For example, relative to 1 mole of the compound A, the amount of the first solvent can be 0.5-10L, preferably 0.8-5L, and more preferably 0.8-2L.

[0076] In step 1) above, the amount of compound B can be selected based on compound A. Preferably, the molar ratio of reactant A to compound B is 1:1.2-10, more preferably 1:1.5-5, and even more preferably 1:2-4.

[0077] In step 1) above, there is no particular limitation on the contact method of the first contact reaction, as long as the intermediate product D can be obtained. Preferably, the catalyst C is mixed with the first solvent and then subjected to the first contact reaction with the compound B.

[0078] The conditions for the first contact reaction may include: a temperature of 10-25°C and a time of 8-90 hours.

[0079] After the first contact reaction, the product can be purified using conventional purification methods in the art. In a preferred embodiment of the present invention, after the first contact reaction is completed, the product of the first contact reaction is subjected to solid-liquid separation to remove the first solvent and unreacted catalyst. The solid obtained from the solid-liquid separation is then washed and dried using the first solvent to obtain intermediate product D.

[0080] The above solid-liquid separation is not particularly limited, and various methods commonly used in the art for solid-liquid separation can be used, such as filtration and / or centrifugation.

[0081] The above-mentioned drying can be carried out using solvent removal methods commonly used in the art. In a preferred embodiment of the present invention, the solvent is removed by vacuum at 10-25°C.

[0082] Step 2): In the presence of a second solvent, intermediate product D undergoes a second contact reaction with compound E to obtain intermediate product D. Intercalary product F .

[0083] In step 2) above, the amount of compound E can be selected according to the amount of intermediate product D. Preferably, the molar ratio of intermediate product D to compound E is 1:0.9-1.1, more preferably 1:0.95-1.05.

[0084] In step 2) above, the second solvent is one or more of aromatic hydrocarbons, ethers and haloalkanes, preferably one or more of diethyl ether, tetrahydrofuran, toluene, dichloromethane and 1,2-dichloroethane.

[0085] The amount of the second solvent can be selected according to the intermediate product D. For example, relative to 1 mole of the intermediate product D, the amount of the second solvent can be 1-30 L, preferably 5-20 L, and more preferably 12-18 L.

[0086] In step 2) above, the contact method of the second contact reaction is not particularly limited, as long as the intermediate product F can be obtained. Preferably, under an inert atmosphere (e.g., under a nitrogen atmosphere or an argon atmosphere), the compound E is dispersed in a portion of the second solvent, and then a solution in which the intermediate product D is dissolved in another portion of the solvent is added dropwise to the solution in which the compound E is dispersed to carry out the second contact reaction.

[0087] Preferably, the operation of dispersing the compound E in a portion of the second solvent is carried out at a temperature of -30 to 0°C, for example, by stirring at -20°C for about 30 minutes.

[0088] The conditions for the second contact reaction may include: a temperature of 10-40°C and a time of 8-40 hours.

[0089] After the second contact reaction, the product can be purified using conventional purification methods in the art. In a preferred embodiment of the present invention, after the second contact reaction is completed, the product of the second contact reaction is poured into a saturated aqueous solution of ammonium chloride, the organic phase is separated, the aqueous phase is extracted with, for example, diethyl ether, the organic phases are combined, dried with a drying agent (e.g., anhydrous sodium sulfate), and the organic solvent is removed (e.g., by vacuum removal of the organic solvent) to obtain intermediate product F.

[0090] Step 3): In the presence of a third solvent, intermediate product F undergoes a third contact reaction with M(NA2)4 to obtain... compound H .

[0091] In the above M(NA2)4, preferably, A is methyl, ethyl or propyl, more preferably methyl or ethyl, and particularly preferably methyl.

[0092] In the above M(NA2)4, preferably, M is a tetravalent transition metal atom, more preferably a titanium atom, a zirconium atom or a hafnium atom, even more preferably a titanium atom or a zirconium atom, and particularly preferably a zirconium atom.

[0093] In step 3) above, the amount of M(NA2)4 can be selected according to the amount of intermediate product F. Preferably, the molar ratio of intermediate product F to M(NA2)4 is 1:0.95-1.05, more preferably 1:0.98-1.02.

[0094] In step 3) above, the third solvent can be, for example, toluene.

[0095] The amount of the third solvent can be selected according to the intermediate product F. For example, relative to 1 mole of the intermediate product F, the amount of the third solvent can be 1-30 L, preferably 5-20 L, and more preferably 12-18 L.

[0096] The conditions for the third contact reaction may include reacting under reflux for 12-36 hours.

[0097] Preferably, the third contact reaction is carried out under an inert atmosphere, such as a nitrogen atmosphere or an argon atmosphere.

[0098] After the third contact reaction, the product can be purified using conventional purification methods in the art. In a preferred embodiment of the present invention, after the third contact reaction is completed, the product is cooled and subjected to solid-liquid separation, and then the solvent is removed under vacuum to obtain compound H.

[0099] The above solid-liquid separation is not particularly limited, and various methods commonly used in the art for solid-liquid separation can be used, such as filtration and / or centrifugation.

[0100] In this invention, X 1 and X 2 The preferred method for preparing metallocene compounds containing halogen atoms includes the following steps:

[0101] 4) In the presence of a fourth solvent, the intermediate product F is subjected to a fourth contact reaction with n-butyllithium, followed by a fifth contact reaction with MX4 to obtain compound I.

[0102]

[0103] In MX4 and compound I, X is a halogen atom and M is a tetravalent transition metal atom.

[0104] Examples of halogen atoms include fluorine, chlorine, bromine, or iodine, with fluorine, chlorine, or bromine being preferred, chlorine or bromine being more preferred, and chlorine being particularly preferred.

[0105] Preferably, M is a titanium atom, a zirconium atom, or a hafnium atom, more preferably a titanium atom or a zirconium atom, and particularly preferably a zirconium atom.

[0106] Specific compounds of MX4 include, for example, zirconium tetrafluoride, zirconium tetrachloride, zirconium tetrabromide, zirconium tetraiodide, titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, hafnium tetrafluoride, hafnium tetrachloride, hafnium tetrabromide or hafnium tetraiodide, preferably zirconium tetrachloride.

[0107] In step 4) above, the fourth solvent is one or more of alkanes, aromatic hydrocarbons, ethers and haloalkanes, preferably one or more of n-hexane, diethyl ether, tetrahydrofuran, toluene, dichloromethane and 1,2-dichloroethane.

[0108] In step 4) above, the amount of the fourth solvent can be selected according to the intermediate product F. For example, relative to 1 mole of the intermediate product F, the amount of the fourth solvent can be 1-30 L, preferably 5-20 L, and more preferably 12-18 L.

[0109] In step 4) above, the preferred method for the fourth contact reaction is to disperse the intermediate product F in the fourth solvent under an inert atmosphere (e.g., under a nitrogen atmosphere or an argon atmosphere), and then add a n-butyllithium solution (e.g., a n-butyllithium hexane solution) dropwise to the solution in which the intermediate product F is dispersed to carry out the fourth contact reaction.

[0110] Preferably, the operation of dispersing the intermediate product F in the fourth solvent is carried out at a temperature of -30 to 0°C, for example, by stirring at -20°C for about 30 minutes.

[0111] The conditions for the fourth contact reaction may include: a temperature of 10-40℃ and a time of 8-40h.

[0112] In step 4) above, preferably, the molar ratio of the intermediate product F to n-butyllithium is 1:2-2.4, more preferably 1:2.1-2.2.

[0113] In step 4) above, the fourth contact reaction product is subjected to a fifth contact reaction with MX4. In the fifth contact reaction, MX4 can be added directly to the fourth contact reaction product in solid form or it can be used by dispersing it in a fifth solvent.

[0114] The fifth solvent mentioned above can be any solvent that is the same as the fourth solvent mentioned above.

[0115] In step 4) above, the amount of MX4 can be selected according to the intermediate product F. Preferably, the molar ratio of the intermediate product F to MX4 is 1:0.95-1.

[0116] In step 4) above, the fifth contact method is preferably: the MX4 solution is added dropwise to the product of the fourth contact reaction under an inert atmosphere (e.g., under a nitrogen atmosphere or an argon atmosphere) at -80 to -60°C, and then the fifth contact reaction is carried out.

[0117] The conditions for the fifth contact reaction may include: a temperature of 10-40℃ and a time of 8-96h.

[0118] After the fifth contact reaction, the product can be purified using conventional purification methods in the art. In a preferred embodiment of the present invention, after the fifth contact reaction is completed, the product of the fifth contact reaction is subjected to solid-liquid separation. The solid obtained from the solid-liquid separation is extracted 3-5 times with an organic solvent (preferably toluene). Then, the liquid phase obtained from the solid-liquid separation is combined with the extract, the solvent is removed under vacuum, and the product is washed (for example, with n-hexane). The residual solvent in the solid is then removed under vacuum to obtain compound I.

[0119] In this invention, the preparation method of compound I can also involve directly reacting the second contact reaction product obtained in step 2) with MX4 in a fifth contact reaction to obtain compound I.

[0120] In this invention, X 1 and X 2 The preparation method of metallocene compounds having an alkyl group having 1-10 carbon atoms or an aromatic group having 6-12 carbon atoms preferably includes the following steps:

[0121] 5) In the presence of a sixth solvent, react compound I with R. 0 The sixth contact reaction of MgY yields compound J.

[0122]

[0123] R 0 In MgY, R 0 It is an alkyl group with 1-10 carbon atoms or an aromatic group with 6-12 carbon atoms; Y is a chlorine atom or a bromine atom.

[0124] Alkyl groups having 1-10 carbon atoms or aromatic groups having 6-12 carbon atoms are as described above.

[0125] In step 5) above, preferably, compound I and R 0 The molar ratio of MgY is 1:2-3, preferably 1:2.2-2.5.

[0126] In step 5) above, preferably, the sixth solvent is one or more of alkanes, aromatic hydrocarbons, ethers and haloalkanes, and more preferably one or more of n-hexane, diethyl ether, tetrahydrofuran, toluene, dichloromethane and 1,2-dichloroethane.

[0127] The amount of the sixth solvent can be selected according to the compound I. For example, relative to 1 mole of the intermediate product I, the amount of the sixth solvent can be 5-60 L, preferably 10-40 L, and more preferably 25-32 L.

[0128] In step 5) above, the sixth contact method is preferably: R is placed in an inert atmosphere (e.g., under a nitrogen atmosphere or an argon atmosphere) at -30 to 0°C. 0 The sixth contact reaction is carried out after the MgY solution is added dropwise to the mixture of compound I and the sixth solvent.

[0129] The conditions for the sixth contact reaction may include: a temperature of 10-40℃ and a time of 10-30h.

[0130] After the sixth contact reaction, the product can be purified using conventional purification methods in the art. In a preferred embodiment of the present invention, after the sixth contact reaction is completed, the product of the fifth contact reaction is subjected to solid-liquid separation, and then the solvent is removed from the obtained solid under vacuum to obtain compound J.

[0131] According to a second aspect of the present invention, a catalyst composition is provided, wherein the catalyst composition comprises the following components,

[0132] a) The metallocene compound described in the first aspect of the present invention;

[0133] b) Co-catalyst components.

[0134] According to the catalyst composition of the present invention, preferably, the co-catalyst component comprises an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound; more preferably, the co-catalyst component is an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound.

[0135] The alkylaluminoxanes described above are preferably compounds selected from those shown in formula (2) and / or formula (3).

[0136]

[0137]

[0138] In formulas (2) and (3), R is selected from alkyl groups having 1-15 carbon atoms, and n represents an integer from 4 to 30; more preferably, R is selected from alkyl groups having 1-5 carbon atoms, and n represents an integer from 10 to 30.

[0139] Specific examples of the alkyl groups mentioned above include: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, isobutyl, pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl, etc.

[0140] Examples of n include: 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, etc.

[0141] Specific examples of the alkylaluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, etc., with methylaluminoxane being preferred.

[0142] According to the catalyst composition of the present invention, preferably, the organoboron compound is [B(C6F5)4]. - Z + Z + Having the structure shown in equation (4) or equation (5),

[0143]

[0144] According to the catalyst composition of the present invention, preferably, the organoaluminum compound is a compound with the general formula AlX1X2X3, wherein X1, X2 and X3 are halogen atoms or alkyl groups having 1-12 carbon atoms, and X1, X2 and X3 may be the same or different, and at least one of them is an alkyl group having 1-12 carbon atoms.

[0145] Examples of alkyl groups having 1-12 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, isobutyl, pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.

[0146] Examples of halogen atoms include fluorine, chlorine, bromine, or iodine, with fluorine, chlorine, or bromine being preferred, chlorine or bromine being more preferred, and chlorine being particularly preferred.

[0147] In this invention, specific examples of the organoaluminum compounds include, for example, one or a mixture of two or more of diethylaluminum chloride, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum, preferably triisobutylaluminum.

[0148] According to the catalyst composition of the present invention, the co-catalyst component is an alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane (calculated as aluminum) is 1:(100-50000), preferably 1:(500-10000), more preferably 1:(500-2000).

[0149] According to the catalyst composition of the present invention, when the co-catalyst component is a combination of an organoboron compound and an organoaluminum compound, the molar ratio of the metallocene compound to the organoboron compound is 1:(1-20), preferably 1:(1-5), more preferably 1:(1-2), and the molar ratio of the metallocene compound to the organoaluminum compound is 1:(10-5000), preferably 1:(50-1000), more preferably 1:(50-500).

[0150] According to a third aspect of the present invention, an olefin polymerization method is provided, wherein the method comprises contacting an olefin with a catalyst composition described in a second aspect of the present invention to induce a polymerization reaction.

[0151] According to the method of the present invention, preferably, the concentration of the metallocene compound in the polymerization reaction system is 1 × 10⁻⁶. -8 mol / L ~ 1×10 -2 mol / L, preferably 1×10 -6 mol / L ~ 1×10 -3 Moles per liter.

[0152] According to the method of the present invention, preferably, the polymerization reaction is carried out in an inert organic solvent. The inert organic solvent can be one or a mixture of several of the following: straight-chain aliphatic hydrocarbons, branched-chain aliphatic hydrocarbons, substituted or unsubstituted cyclic aliphatic hydrocarbons, and substituted or unsubstituted aromatic hydrocarbons. Specific examples of the inert organic solvent include: hexane, heptane, cyclohexane, cyclooctane, toluene, and xylene, preferably one or more of toluene, cyclohexane, and hexane. Furthermore, the amount of organic solvent can be determined according to the reactivity to ensure that the resulting polymer dissolves well in the system, or at least does not affect dispersion.

[0153] According to the method of the present invention, preferably, the olefin is ethylene or a combination of ethylene and α-olefin.

[0154] According to the method of the present invention, preferably, the α-olefin is selected from one or more of propylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene.

[0155] According to the method of the present invention, when the olefin is ethylene, the partial pressure of the ethylene is 0.1-6 MPa, preferably 0.1-3 MPa.

[0156] According to the method of the present invention, when the olefin is a combination of ethylene and α-olefin, the amounts of ethylene and the α-olefin can be those commonly used in the art for synthesizing ethylene-α-olefin copolymers. For example, the concentration of α-olefin in the polymerization reaction system is 0.001-8 mol / L, preferably 0.005-4 mol / L. Furthermore, the partial pressure of the ethylene is 0.1-6 MPa, preferably 0.1-3 MPa.

[0157] According to the method of the present invention, the polymerization reaction conditions can be those commonly used in the art for the synthesis of polyolefins. Preferably, the polymerization temperature is -50 to 200°C and the polymerization time is 1 to 300 minutes; more preferably, the polymerization temperature is -20 to 150°C and the polymerization time is 5 to 60 minutes.

[0158] According to a fourth aspect of the present invention, the use of the metallocene compound described in the first aspect of the present invention or the catalyst composition described in the second aspect of the present invention in olefin polymerization is provided.

[0159] The present invention will be described in detail below through embodiments, but the present invention is not limited to the following embodiments.

[0160] Unless otherwise specified, the raw materials used in the following examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0161] In the following examples and comparative examples, the compounds synthesized were... 1 H nuclear magnetic resonance (H nuclear magnetic resonance) 1 H-NMR was performed on a Bruker AVANCE III-400MHz spectrometer using CDCl3 as solvent at 25°C.

[0162] The molecular weight of the polymer was determined by gel permeation chromatography (GPC) at 150 °C on a Waters Alliance GPCV2000 with 1,2,4-trichlorobenzene as solvent.

[0163] The content of comonomers in polymers is determined by solution. 13 C nuclear magnetic resonance (C 13 C-NMR experiments were conducted on a Bruker AVANCE III-400MHz spectrometer equipped with a 10mm PASEX 13C-1H / D Z-GRD probe. 13 The C resolution was 0.09 Hz. A sample solution was prepared by dissolving 200 mg of the polymer material in 2.5 mL of D4-o-o-dichlorobenzene (ODCB-d4) in a 10 mm test tube at 130 °C. 13 The C-NMR measurements were performed at 125 °C, a spin rate of 20 Hz, a pulse angle of 90°, continuous Waltz-16 decoupling, a spectral width of 120 ppm, an acquisition time of 5 s, and a relaxation delay of 10 s. The repeating backbone methylene peak was set to 30.0000 ppm as a chemical shift reference.

[0164] Example 1

[0165] This example illustrates the synthesis of metallocene compound H-1.

[0166] Metallocene compound H-1: In the above compound H, M is zirconium and A is dimethylamino.

[0167] 1) Synthesis of intermediate product D

[0168] At 15°C, catalyst C (pyrrolidine, 12 mmol) and 30 mL of anhydrous methanol were added to a 250 mL three-necked flask equipped with a magnetic stirrer. The mixture was stirred for 5 minutes, then compound A (1.8 g, 11.98 mmol) was added, and the mixture was stirred for another 5 minutes. Compound B (2.0 g, 30.26 mmol) was then added, and the reaction was stirred for 24 hours, maintaining the reaction temperature below 25°C. The solvent and catalyst were removed by filtration, and the resulting product was washed with anhydrous methanol. The residual solvent was removed under vacuum at room temperature to give 2.26 g of a yellow solid, with a yield of 94%.

[0169] 1 H-NMR (CDCl3): 6.62-6.55ppm (2H), 6.55-6.48ppm (2H), 3.33-3.24ppm (2H), 2.14-1.85ppm (12H).

[0170] 2) Synthesis of intermediate product F

[0171] Under a nitrogen atmosphere, 244 mg (2.0 mmol) of reactant E (indenyllithium) was dispersed in 30 mL of tetrahydrofuran and stirred at -20 °C for 30 min. 400 mg (2.0 mmol) of intermediate D was dissolved in 10 mL of tetrahydrofuran, and this solution was slowly added dropwise to the indenyllithium tetrahydrofuran solution. After the addition was complete, the mixture was slowly brought to room temperature and stirred for 24 h. The reaction mixture was poured into a saturated aqueous solution of ammonium chloride, the organic phase was separated, the aqueous phase was extracted with diethyl ether, the organic phases were combined, dried over anhydrous sodium sulfate, and the organic solvent was removed under vacuum to give 597 mg of a yellow solid, with a yield of 90%.

[0172] 3) Synthesis of metallocene compound H-1

[0173] Under a nitrogen atmosphere, 333 mg of intermediate product F (1 mmol) was dissolved in 15 mL of toluene, and 267 mg of reactant Zr(NMe2)4 (1 mmol) was added. The mixture was refluxed at 110 °C for 17 h. After cooling, the mixture was filtered, and the solvent was removed under vacuum to obtain 436 mg of orange-yellow solid, with a yield of 89%.

[0174] 1H-NMR (CDCl3): 7.49-7.46ppm (1H), 7.38-7.35ppm (1H), 7.30-7.28ppm (1H), 7.0 2-6.98ppm(1H), 6.82-6.78ppm(1H), 6.50-6.45ppm(2H), 6.11-6.08ppm(1H), 5. 74-5.71ppm(1H), 5.66-5.63ppm(1H), 3.29-3.24ppm(1H), 2.80-2.74ppm(1H), 2 .48-2.46ppm(12H), 2.36-2.29ppm(2H), 2.26-2.18ppm(2H), 2.06-1.84ppm(8H).

[0175] Example 2

[0176] Synthesis of metallocene compound I-1

[0177] Metallocene compound I-1: In compound I, M is zirconium and X is a chlorine atom.

[0178] Weigh 348.5 mg (3 mmol) of pre-distilled indene into a 250 mL three-necked flask A. After purging with nitrogen three times, dissolve the indene in 10 mL of pre-dehydrated and deoxygenated anhydrous diethyl ether. Place flask A in a -20 °C oil bath and stir for 15 minutes. At -20 °C, add n-butyllithium (1.05 equivalents, 2.5 mol / L hexane solution) dropwise to flask A. After this process, transfer flask A to room temperature and stir for 8 hours. Weigh intermediate D (631 mg, 1.05 equivalents) into another 100 mL three-necked flask B. After purging with nitrogen three times, dissolve the intermediate in 10 mL of pre-treated anhydrous diethyl ether with dried molecular sieves. Place flask A in a -20 °C oil bath and stir for 15 minutes. Add the solution from flask B dropwise to flask A. After this process, transfer flask A to room temperature and stir for 24 hours. Three-necked flask A was placed in a -20°C oil bath and stirred for 15 minutes. Butyllithium (1.05 equivalents, 2.5 mol / L hexane solution) was added dropwise to flask A. After this, flask A was transferred to room temperature and stirred for 8 hours. Flask A was then placed in a -70°C oil bath and stirred for 30 minutes. Under nitrogen protection, zirconium tetrachloride (700 mg, 3 mmol) solid was added to flask A in three portions, and the mixture was stirred at room temperature for 72 hours. The reaction mixture was transferred to a centrifuge tube and centrifuged (3500 rpm). The supernatant was collected, and the residual solid was extracted with 5 mL of anhydrous diethyl ether. The extract was centrifuged (3500 rpm) and the supernatant was collected. This extraction was repeated three times, and the residual solid was discarded. The supernatant and extract were combined, and the diethyl ether was removed under vacuum. The resulting solid was dissolved in a small amount of toluene, filtered into a sample vial, and an equal volume of hexane was added. After standing in a nitrogen chamber at room temperature for 24 hours, centrifugation yielded 326 mg of the solid compound, a yield of 23%.

[0179] 1 H-NMR (CDCl3): 7.65-7.62ppm (1H), 7.52-7.48ppm (1H), 7.36-7.32ppm (1H), 7.05-7.01ppm (1H), 6.91-6.88ppm (1H), 6.56-6.51ppm (2H), 6.15-6.12p pm(1H), 5.78-5.73ppm(1H), 5.69-5.65ppm(1H), 3.30-3.25ppm(1H), 2.83- 2.76ppm(1H), 2.37-2.29ppm(2H), 2.27-2.18ppm(2H), 2.08-1.87ppm(8H).

[0180] Example 3

[0181] Synthesis of metallocene compound I-1

[0182] Metallocene compound I-1: In compound I, M is zirconium and X is a chlorine atom.

[0183] Under a nitrogen atmosphere, 333 mg of intermediate F (1 mmol) was dissolved in 15 mL of toluene. At -20 °C, 0.84 mL of n-butyllithium (2.5 mol / L hexane solution) was added dropwise. After completion, three-necked flask A was transferred to room temperature and stirred for 8 hours. Three-necked flask A was then placed in a -70 °C oil bath and stirred for 30 minutes. Under nitrogen protection, 233 mg (1 mmol) of zirconium tetrachloride solid was added to three portions of flask A, and the mixture was stirred at room temperature for 72 hours. The reaction mixture was transferred to a centrifuge tube and centrifuged (3500 rpm). The supernatant was collected, and the residual solid was extracted with 5 mL of anhydrous diethyl ether. The extraction was repeated three times, and the residual solid was discarded. The supernatant and extract were combined, and the diethyl ether was removed under vacuum. The resulting solid was dissolved in a small amount of toluene, filtered into a sample vial, and an equal volume of ultra-dry n-hexane was added. After standing in a nitrogen chamber at room temperature for 24 hours, the sample was centrifuged to obtain 259 mg of solid compound, with a yield of 55%.

[0184] The solid compound obtained was confirmed by nuclear magnetic resonance (NMR) analysis to be metallocene compound I-1.

[0185] Example 4

[0186] Synthesis of metallocene compound J-1

[0187] Metallocene compound J-1: M is zirconium, R 0 It is benzyl.

[0188] Under a nitrogen atmosphere, 474 mg of metallocene compound I-1 (1 mmol) was dissolved in 30 mL of toluene. The mixture was stirred in an oil bath at -70°C for 30 minutes, and 2.2 mL of benzyl magnesium chloride solution (1 mol / L tetrahydrofuran solution) was added dropwise. The mixture was slowly heated to room temperature and reacted for 24 hours. After filtration, the solvent was removed under vacuum to give 502 mg of an orange-yellow solid, with a yield of 85%.

[0189] 1H-NMR(CDCl3): 7.61-7.58ppm(1H), 7.50-7.47ppm(1H), 7.42-7.38ppm(4H), 7.36-7.32ppm(1H) ), 7.12-7.10ppm(4H), 7.04-7.00ppm(1H), 6.95-6.88ppm(2H), 6.92-6.88ppm(1H), 6.55-6.51 ppm(2H), 6.16-6.11ppm(1H), 5.78-5.73ppm(1H), 5.68-5.64ppm(1H), 3.30-3.25ppm(1H), 2.8 3-2.74ppm(1H), 2.67-2.61(4H), 2.36-2.27ppm(2H), 2.24-2.13ppm(2H), 2.08-1.190ppm(8H).

[0190] Example 5

[0191] Synthesis of metallocene compound J-2

[0192] Metallocene compound J-2: M is zirconium, R 0 It is a methyl group.

[0193] Under a nitrogen atmosphere, 472 mg of metallocene compound I (1 mmol) was dissolved in 30 mL of toluene and stirred in an oil bath at -70°C for 30 minutes. 2 mL of methyl magnesium bromide solution (1 mol / L tetrahydrofuran solution) was added dropwise, and the mixture was slowly heated to room temperature. The reaction was allowed to proceed for 24 hours. After filtration, the solvent was removed under vacuum to obtain 311 mg of an orange-yellow solid, with a yield of 72%.

[0194] 1 H-NMR (CDCl3): 7.64-7.60ppm (1H), 7.50-7.47ppm (1H), 7.35-7.32ppm (1H), 7. 05-7.00ppm(1H), 6.91-6.88ppm(1H), 6.56-6.51ppm(2H), 6.15-6.11ppm(1H), 5.76-5.71ppm(1H), 5.68-5.65ppm(1H), 3.30-3.24ppm(1H), 2.83-2.76ppm(1H) ), 2.37-2.29ppm (2H), 2.27-2.18ppm (2H), 2.08-1.87ppm (8H), -0.99ppm (6H).

[0195] Example 6

[0196] This example illustrates the homopolymerization of ethylene.

[0197] A thoroughly dried 250 mL glass polymerization flask was evacuated and rinsed with nitrogen three times. Evacuation was then performed, followed by the introduction of ethylene. The flask was heated in an oil bath to 70°C to maintain an ethylene pressure of 1 atmosphere. 25 mL of toluene, 1 mL of triisobutylaluminum toluene solution (containing 1.0 mmol / L triisobutylaluminum), and 2 mL of catalyst toluene solution (containing 5 μmol / L compound I-1) were added sequentially. After the temperature stabilized at 70°C, 2 mL of triphenylcarbazone (pentafluorophenyl)borate toluene solution (containing 6.0 μmol / L triphenylcarbazone (pentafluorophenyl)borate) was added, and timing was started. During the reaction, ethylene was replenished as needed to maintain an ethylene pressure of 1 atmosphere in the polymerization flask. After 20 minutes, the ethylene supply was shut off, the reaction solution was poured into a beaker, 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added, and the mixture was stirred for at least 6 hours. The polymer was obtained by filtration and vacuum drying at 60°C for 24 hours, yielding 0.72 g of polymer. The activity was 432 kg polymer / molar catalyst / hour. Gel permeation chromatography determined the polymer's weight-average molecular weight (Mw) to be 6.5 × 10⁻⁶. 4 The molecular weight distribution MWD is 1.98.

[0198] Example 7

[0199] This example illustrates the homopolymerization of ethylene.

[0200] A thoroughly dried 250 mL glass polymerization flask was evacuated and rinsed with nitrogen three times. Vacuuming was then initiated, controlled by a solenoid valve, and ethylene was introduced. The flask was heated in an oil bath to 70°C to maintain an ethylene pressure of 1 atmosphere. 25 mL of toluene, 1 mL of triisobutylaluminum toluene solution (containing 1.0 mmol / L triisobutylaluminum), and 2 mL of catalyst toluene solution (containing 5 μmol / L compound I-1) were added sequentially. After the temperature stabilized at 70°C, 2 mL of N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate toluene solution (containing 6.0 μmol / L N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate) was added, and timing was started. During the reaction, ethylene was replenished as needed to maintain an ethylene pressure of 1 atmosphere in the polymerization flask. After 20 minutes, the ethylene supply was shut off, the reaction solution was poured into a beaker, 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added, and the mixture was stirred for at least 6 hours. The polymer was obtained by filtration and vacuum drying at 60 °C for 24 hours, yielding 0.81 g of polymer. The activity was 486 kg polymer / molar catalyst / hour. Gel permeation chromatography determined the polymer's weight-average molecular weight (Mw) to be 7.2 × 10⁻⁶. 4 The molecular weight distribution (MWD) is 2.03.

[0201] Example 8

[0202] This example illustrates the homopolymerization of ethylene.

[0203] A thoroughly dried 250 mL glass polymerization flask was evacuated, rinsed with nitrogen, and repeated three times. Vacuuming was then initiated using a solenoid valve, and ethylene was introduced. The flask was heated in an oil bath to 70°C to maintain an ethylene pressure of 1 atmosphere. 25 mL of toluene and 3 mL of a methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) were added sequentially. After the temperature stabilized at 70°C, 2 mL of a catalyst toluene solution (containing 5 μmol of compound I-1) was added, and timing began. During the reaction, ethylene was replenished as needed to maintain an ethylene pressure of 1 atmosphere in the polymerization flask. After 20 minutes, the ethylene supply was shut off, the reaction mixture was poured into a beaker, and 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added. The mixture was stirred for at least 6 hours, filtered to obtain the polymer, and vacuum-dried at 60°C for 24 hours to obtain 0.68 g of polymer. The activity was 408 kg polymer / molar catalyst / hour. Gel permeation chromatography determined the polymer's weight-average molecular weight (Mw) to be 6.7 × 10⁻⁶. 4 The molecular weight distribution MWD is 2.11.

[0204] Example 9

[0205] This example illustrates the homopolymerization of ethylene.

[0206] A thoroughly dried 100 mL stainless steel polymerization reactor was evacuated, purged with nitrogen three times, and finally filled with ethylene. The heating was set to 75 °C. During heating, 50 mL of toluene and 1 mL of triisobutylaluminum toluene solution (containing 1.0 mmol of triisobutylaluminum) were added sequentially. After the temperature stabilized at 75 °C, 2 mL of catalyst toluene solution (containing 2 μmol of compound I-1) was added. After 5 minutes, 2 mL of triphenylcarbazone (pentafluorophenyl)borate toluene solution (containing 2.4 μmol of triphenylcarbazone (pentafluorophenyl)borate) was added. The ethylene was rapidly pressurized to 6 atmospheres, and the heating was set to 80 °C. Timing was started. During the reaction, ethylene was replenished as needed to maintain the total pressure in the polymerization flask at 6 atmospheres. After 30 minutes, the ethylene supply was shut off, the reaction solution was poured into a beaker, 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added, and the mixture was stirred for at least 6 hours. The mixture was then filtered to obtain the polymer, which was vacuum dried at 60°C for 24 hours to yield 5.70 g of polymer. The activity was 5700 kg polymer / molar catalyst / hour. Gel permeation chromatography determined the polymer's weight-average molecular weight (Mw) to be 14.7 × 10⁻⁶. 4 The molecular weight distribution (MWD) is 2.25.

[0207] Example 10

[0208] This example illustrates the homopolymerization of ethylene.

[0209] The procedure was carried out according to Example 8, except that compound I-1 was replaced with the same molar amount of compound H-1. The same result yielded 0.65 g of polymer with an activity of 3890 catties polymer / molar catalyst / hour. Gel permeation chromatography analysis showed that the polymer's weight-average molecular weight Mw = 6.9 × 10⁻⁶. 4 The molecular weight distribution (MWD) is 2.16.

[0210] Example 11

[0211] This example illustrates the homopolymerization of ethylene.

[0212] The procedure was carried out according to Example 8, except that compound I-1 was replaced with the same molar amount of compound J-1. The same result yielded 0.93 g of polymer with an activity of 558 kg polymer / molar catalyst / hour. Gel permeation chromatography analysis showed that the polymer's weight-average molecular weight Mw = 9.6 × 10⁻⁶. 4 The molecular weight distribution (MWD) is 2.25.

[0213] Example 12

[0214] This example illustrates the homopolymerization of ethylene.

[0215] The procedure was carried out according to Example 8, except that compound I-1 was replaced with the same molar amount of compound J-2. The same result yielded 0.99 g of polymer with an activity of 594 kg polymer / molar catalyst / hour. Gel permeation chromatography determined the polymer's weight-average molecular weight (Mw) to be 8.2 × 10⁻⁶. 4 The molecular weight distribution (MWD) is 2.19.

[0216] Comparative Example 1

[0217] A thoroughly dried 250 mL glass polymerization flask was evacuated, rinsed with nitrogen, and repeated three times. Vacuuming was then initiated using a solenoid valve, and ethylene was introduced. The flask was heated in an oil bath to 70°C to maintain an ethylene pressure of 1 atmosphere. 25 mL of toluene and 3 mL of a methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) were added sequentially. After the temperature stabilized at 70°C, 2 mL of a catalyst toluene solution (containing 5 μmol of zirconium dichloroethylene) was added, and timing began. During the reaction, ethylene was replenished as needed to maintain an ethylene pressure of 1 atmosphere in the polymerization flask. After 20 minutes, the ethylene supply was shut off, the reaction mixture was poured into a beaker, and 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added. The mixture was stirred for at least 6 hours, filtered to obtain the polymer, and vacuum-dried at 60°C for 24 hours to obtain 0.47 g of polymer. The activity was 282 kg polymer / molar catalyst / hour. Gel permeation chromatography determined the polymer's weight-average molecular weight (Mw) to be 2.6 × 10⁻⁶. 4 The molecular weight distribution (MWD) is 1.99.

[0218] Example 13

[0219] This example illustrates the copolymerization of ethylene and 1-hexene.

[0220] A thoroughly dried 250 mL glass polymerization flask was evacuated, rinsed with nitrogen, and repeated three times. Vacuuming was then initiated using a solenoid valve, and ethylene was introduced. The flask was heated in an oil bath to 70°C to maintain an ethylene pressure of 1 atmosphere. 24 mL of toluene, 1 mL of 1-hexene, and 3 mL of a methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) were added sequentially. After the temperature stabilized at 70°C, 2 mL of a catalyst toluene solution (containing 5 μmol of compound I-1) was added, and timing began. During the reaction, ethylene was replenished as needed to maintain an ethylene pressure of 1 atmosphere in the polymerization flask. After 20 minutes, the ethylene supply was shut off, the reaction mixture was poured into a beaker, and 300 mL of ethanol and 5 mL of concentrated hydrochloric acid were added. The mixture was stirred for at least 6 hours, filtered to obtain the polymer, and vacuum-dried at 60°C for 24 hours to obtain 1.82 g of polymer. The activity was 1092 kg polymer / molar catalyst / hour. Gel permeation chromatography determined the polymer's weight-average molecular weight (Mw) to be 3.7 × 10⁻⁶. 4 The molecular weight distribution (MWD) was 1.88, and the 1-hexene unit content in the polymer was 8.7 mol as determined by carbon-13 NMR spectroscopy.

[0221] Example 14

[0222] This example illustrates the copolymerization of ethylene and 1-hexene.

[0223] The procedure was carried out according to Example 13, except that compound I-1 was replaced with the same molar amount of compound H-1. The same result yielded 1.52 g of polymer with an activity of 912 kg polymer / molar catalyst / hour. Gel permeation chromatography analysis showed that the polymer's weight-average molecular weight Mw = 3.1 × 10⁻⁶. 4 The molecular weight distribution (MWD) was 1.91, and the 1-hexene unit content in the polymer was 9.1 mol as determined by NMR carbon-13 spectroscopy.

[0224] Example 15

[0225] This example illustrates the copolymerization of ethylene and 1-hexene.

[0226] The procedure was carried out according to Example 13, except that compound I-1 was replaced with the same molar amount of compound J-1, yielding polymer 2.01 with an activity of 1206 kg polymer / molar catalyst / hour. Gel permeation chromatography analysis showed that the polymer's weight-average molecular weight Mw = 4.1 × 10⁻⁶. 4 The molecular weight distribution (MWD) was 1.90, and the 1-hexene unit content in the polymer was 8.9 mol% as determined by NMR carbon-13 spectroscopy.

[0227] Example 16

[0228] This example illustrates the copolymerization of ethylene and 1-hexene.

[0229] The procedure was carried out according to Example 13, except that compound I-1 was replaced with the same molar amount of compound J-2, and polymer 2.11 was obtained in the same manner, with an activity of 1266 kg polymer / molar catalyst / hour. The weight-average molecular weight of the polymer, Mw, was determined by gel permeation chromatography to be 4.0 × 10⁻⁶. 4 The molecular weight distribution (MWD) was 1.86, and the 1-hexene unit content in the polymer was 9.4 mol as determined by NMR carbon-13 spectroscopy.

[0230] Comparative Example 2

[0231] The procedure was carried out according to Example 13, except that the same molar amount of zirconium dichlorocerocene was used to replace compound I-1, yielding the same 1.01 g of polymer with an activity of 606 kg polymer / molar catalyst / hour. Gel permeation chromatography analysis showed that the polymer's weight-average molecular weight Mw = 0.97 × 10⁻⁶. 4 The molecular weight distribution (MWD) was 1.94, and the 1-hexene unit content in the polymer was 7.8 mol as determined by NMR carbon-13 spectroscopy.

[0232] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A metallocene compound, characterized in that, The metallocene compound has the structure shown in formula (1). Equation (1) In formula (1), M is a titanium atom, a zirconium atom, or a hafnium atom; X 1 and X 2 Each is independently a halogen atom, an alkyl group with 1-10 carbon atoms, an aromatic group with 6-12 carbon atoms, or an N,N-dialkylamine group with 2-8 carbon atoms.

2. The metallocene compound according to claim 1, wherein, M represents a titanium atom or a zirconium atom.

3. The metallocene compound according to claim 2, wherein, M represents a zirconium atom.

4. The metallocene compound according to claim 1, wherein, X 1 and X 2 Each is independently a halogen atom, an alkyl group with 1-6 carbon atoms, an aromatic group with 6-10 carbon atoms, or an N,N-dialkylamine group with 2-6 carbon atoms.

5. The metallocene compound according to claim 1, wherein, X 1 and X 2 Each is independently a halogen atom, an alkyl group with 1-3 carbon atoms, an aromatic group with 6-8 carbon atoms, or an N,N-dialkylamine group with 2-6 carbon atoms.

6. The metallocene compound according to claim 1, wherein, X 1 and X 2 Each of them independently represents F, Cl, Br, I, methyl, ethyl, propyl, phenyl, benzyl, N,N-dimethylamino, N,N-diethylamino, or N,N-dipropylamino.

7. The metallocene compound according to claim 1, wherein, X 1 and X 2 Each can be independently Cl, methyl, benzyl, or N,N-dimethylamino.

8. A catalyst composition, characterized in that, The catalyst composition comprises the following components. a) The metallocene compound according to any one of claims 1-7; b) Co-catalyst components.

9. The catalyst composition according to claim 8, wherein, The cocatalyst component includes alkylaluminoxanes or a combination of organoboron compounds and organoaluminum compounds.

10. The catalyst composition according to claim 9, wherein, The cocatalyst component is an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound.

11. The catalyst composition according to claim 9, wherein, The alkylaluminoxane is a compound selected from the structures shown in formula (2) and / or formula (3). Equation (2) Equation (3) In formulas (2) and (3), R is selected from alkyl groups with 1-15 carbon atoms, and n represents an integer from 4 to 30.

12. The catalyst composition according to claim 11, wherein, R is selected from alkyl groups with 1-5 carbon atoms, and n represents an integer from 10 to 30.

13. The catalyst composition according to claim 12, wherein, The alkylaluminoxane is methylaluminoxane.

14. The catalyst composition according to claim 9, wherein, The organoboron compound is [B(C6F5)4]. - Z + Z + Having the structure shown in equation (4) or equation (5), Equation (4) Equation (5).

15. The catalyst composition according to claim 9, wherein, The organoaluminum compound is a compound with the general formula AlX1X2X3, where X1, X2 and X3 are halogen atoms or alkyl groups having 1-12 carbon atoms, respectively. X1, X2 and X3 can be the same or different, and at least one of them is an alkyl group having 1-12 carbon atoms.

16. The catalyst composition according to claim 15, wherein, The organoaluminum compound is one or a mixture of two or more of diethylaluminum chloride, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum.

17. The catalyst composition according to claim 16, wherein, The organoaluminum compound is triisobutylaluminum.

18. The catalyst composition according to claim 9, wherein, The cocatalyst component is an alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane (calculated as aluminum) is 1:(100-50000).

19. The catalyst composition according to claim 18, wherein, The cocatalyst component is an alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane (calculated as aluminum) is 1:(500-10000).

20. The catalyst composition according to claim 19, wherein, The cocatalyst component is an alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane (calculated as aluminum) is 1:(500-2000).

21. The catalyst composition according to claim 9, wherein, The cocatalyst component is a combination of organoboron compounds and organoaluminum compounds, wherein the molar ratio of the metallocene compound to the organoboron compound is 1:(1-20), and the molar ratio of the metallocene compound to the organoaluminum compound is 1:(10-5000).

22. The catalyst composition according to claim 21, wherein, The cocatalyst component is a combination of organoboron compounds and organoaluminum compounds, wherein the molar ratio of the metallocene compound to the organoboron compound is 1:(1-5), and the molar ratio of the metallocene compound to the organoaluminum compound is 1:(50-1000).

23. The catalyst composition according to claim 22, wherein, The cocatalyst component is a combination of organoboron compounds and organoaluminum compounds, wherein the molar ratio of the metallocene compound to the organoboron compound is 1:(1-2), and the molar ratio of the metallocene compound to the organoaluminum compound is 1:(50-500).

24. A method for olefin polymerization, characterized in that, The method includes contacting an olefin with the catalyst composition of any one of claims 8-23 to induce a polymerization reaction.

25. The method according to claim 24, wherein, The concentration of the metallocene compound in the polymerization reaction system is 1 × 10⁻⁶. -8 mol / L ~ 1×10 -2 Moles per liter.

26. The method of claim 25, wherein, The concentration of the metallocene compound in the polymerization reaction system is 1 × 10⁻⁶. -6 mol / L ~ 1×10 -3 Moles per liter.

27. The method according to claim 24, wherein, The olefin is ethylene or a combination of ethylene and α-olefin.

28. The method according to claim 27, wherein, The α-olefin is selected from one or more of propylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene.

29. The method according to claim 27, wherein, The partial pressure of the ethylene is 0.1-6 MPa.

30. The method according to claim 29, wherein, The partial pressure of the ethylene is 0.1-3 MPa.

31. The method according to claim 24, wherein, The polymerization reaction is carried out in the presence of an organic solvent, which is one or more of toluene, cyclohexane, and hexane.

32. The method according to any one of claims 24-31, wherein, The polymerization reaction temperature is -50~200℃, and the polymerization reaction time is 1-300 minutes.

33. The method according to claim 32, wherein, The polymerization reaction temperature is -20~150℃, and the polymerization reaction time is 5-60 minutes.

34. The use of the metallocene compound according to any one of claims 1-7 or the catalyst composition according to any one of claims 8-23 in olefin polymerization.

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