Polysubstituted indenyl complex as well as preparation method and application thereof

Abstract

The invention provides a polysubstituted indenyl ligand catalyst as well as a preparation method and application thereof in catalyzing olefin polymerization. The structure of the compound is shown as a formula I. The compound provided by the invention not only can improve the catalytic polymerization activity, molecular weight and comonomer reactivity rate, but also has better temperature tolerance. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of metallocene polyolefin catalysts, and particularly relates to a multi-substituted indenyl complex, a preparation method thereof, and an application in catalyzing olefin polymerization. Background Art

[0002] Due to the narrow molecular weight distribution, high comonomer reactivity ratio, and high polymerization activity of the polymerization products, constrained geometry configuration (CGC) metallocene catalysts have been widely used in the field of olefin polymerization. A large number of literatures and patents have reported the modification of indenyl ligands in the CGC catalyst structure to indirectly control the polymerization reaction rate and the comonomer reactivity ratio. The traditional view is that the introduction of heteroatoms in the ligand will have a poisoning effect on the central coordinated metal, resulting in catalyst deactivation. However, CN 117467047A found that when the 3-position of the indenyl ligand is substituted by an electron-donating heteroatom group, it shows high activity during the catalytic polymerization process and increases the molecular weight of the polymer. On the other hand, while such CGC catalysts increase the molecular weight of the polymer, they inhibit the comonomer reactivity ratio, resulting in a decrease in the α-olefin insertion rate of the polymer. Summary of the Invention

[0003] The present invention discovers that by introducing alkyl groups, bulky groups, or electron-donating heteroatom groups at multiple sites of the indenyl ligand in the catalyst structure, when the catalyst catalyzes olefin polymerization, the polymerization activity, molecular weight, and comonomer reactivity ratio can be effectively controlled simultaneously.

[0004] The technical solution of the present invention is as follows:

[0005] A compound, whose structure is shown in Formula I:

[0006]

[0007] In Formula I, R 1 is selected from any one of hydrogen and C1-C10 alkyl groups;

[0008] R 2selected from any one of C1-C10 alkyl, C1-C10 alkoxy, pyrrolidinyl, pyrrolidinyl substituted with a group selected from C1-C6 alkyl and C1-C6 alkoxy, pyrrolyl, pyrrolyl substituted with a group selected from C1-C6 alkyl and C1-C6 alkoxy, piperidinyl, piperidinyl substituted with a group selected from C1-C6 alkyl and C1-C6 alkoxy, cyclohexylimino, cyclohexylimino substituted with a group selected from C1-C6 alkyl and C1-C6 alkoxy, indolinyl, indolinyl substituted with a group selected from C1-C6 alkyl and C1-C6 alkoxy, isoindolinyl, isoindolinyl substituted with a group selected from C1-C6 alkyl and C1-C6 alkoxy, indolyl, indolyl substituted with a group selected from C1-C6 alkyl and C1-C6 alkoxy, tetrahydroquinolinyl, tetrahydroquinolinyl substituted with a group selected from C1-C6 alkyl and C1-C6 alkoxy, tetrahydroisoquinolinyl, tetrahydroisoquinolinyl substituted with a group selected from C1-C6 alkyl and C1-C6 alkoxy;

[0009] R 3 selected from any one of C1-C10 alkyl, C3-C7 cycloalkyl, C1-C10 alkoxy, phenyl, phenyl substituted with a group selected from C1-C6 alkyl and C1-C6 alkoxy, benzyl, benzyl substituted with a group selected from C1-C6 alkyl and C1-C6 alkoxy, naphthyl, naphthyl substituted with a group selected from C1-C6 alkyl and C1-C6 alkoxy;

[0010] R 4 selected from any one of hydrogen and C1-C10 alkyl;

[0011] R 5 、R 6 are the same or different and independently selected from any one of hydrogen, C1-C10 alkyl, C3-C7 cycloalkyl, phenyl, phenyl substituted with C1-C4 alkyl, phenyl substituted with C1-C4 alkoxy, benzyl, benzyl substituted with C1-C4 alkyl, naphthyl;

[0012] R 7 selected from any one of C1-C10 alkyl and C3-C7 cycloalkyl;

[0013] X 1 、X 2 are the same or different and independently selected from halogen (such as fluorine F, chlorine Cl, bromine Br, iodine I), pseudohalogen (such as cyano (-CN), thiocyanato (-SCN), selenocyanato (-SeCN), cyanato (-OCN), carbon disulfide azide group (-SCSN3)), halogenated C1-C10 alkyl (such as trifluoromethyl, difluoromethyl, monofluoromethyl), C1-C10 alkyl, C1-C10 silyl;

[0014] M is selected from Group 4 elements (such as titanium Ti, zirconium Zr, hafnium Hf), and the valence state of M is any one of +2, +3, and +4.

[0015] According to an embodiment of the present invention, in the compound shown by formula I:

[0016] R 2 is selected from any one of C1-C10 alkyl, C1-C10 alkoxy, pyrrolidinyl, C1-C4 alkyl-substituted pyrrolidinyl, pyrrolyl, C1-C4 alkyl-substituted pyrrolyl, piperidinyl, C1-C4 alkyl-substituted piperidinyl, cyclohexylimine, C1-C4 alkyl-substituted cyclohexylimine, indolinyl, C1-C4 alkyl-substituted indolinyl, isoindolinyl, and C1-C4 alkyl-substituted isoindolinyl;

[0017] R 3 is selected from any one of C1-C10 alkyl, C3-C7 cycloalkyl, C1-C10 alkoxy, phenyl, C1-C4 alkyl-substituted phenyl, C1-C4 alkoxy-substituted phenyl, benzyl, C1-C4 alkyl-substituted benzyl, C1-C4 alkoxy-substituted benzyl, and naphthyl.

[0018] According to an embodiment of the present invention, M is preferably Ti.

[0019] According to an embodiment of the present invention, R 1 is preferably hydrogen or C1-C4 alkyl.

[0020] According to an embodiment of the present invention, R 1 is preferably hydrogen, methyl, or ethyl.

[0021] According to an embodiment of the present invention, R 2 is preferably C1-C4 alkyl (such as methyl, isopropyl, tert-butyl), pyrrolidinyl, C1-C4 alkyl-substituted pyrrolidinyl (such as 2-methylpyrrolidin-1-yl, 3-methylpyrrolidin-1-yl), pyrrolyl, C1-C4 alkyl-substituted pyrrolyl, piperidinyl, C1-C4 alkyl-substituted piperidinyl, cyclohexylimine, C1-C4 alkyl-substituted cyclohexylimine, indolinyl, C1-C4 alkyl-substituted indolinyl, isoindolinyl, and C1-C4 alkyl-substituted isoindolinyl (such as 1-methylisoindolin-2-yl, 1,3-dimethylisoindolin-2-yl).

[0022] According to an embodiment of the present invention, R 2Preferably pyrrolidinyl, C1-C4 alkyl-substituted pyrrolidinyl, pyrrolyl, C1-C4 alkyl-substituted pyrrolyl, piperidinyl, C1-C4 alkyl-substituted piperidinyl, cyclohexylimino, C1-C4 alkyl-substituted cyclohexylimino, indolinyl, C1-C4 alkyl-substituted indolinyl, isoindolinyl, C1-C4 alkyl-substituted isoindolinyl, wherein pyrrolidinyl, pyrrolyl, piperidinyl, cyclohexylimino, indolinyl, isoindolinyl are linked to the indenyl group through the ring N atom or the ring carbon atom of the heterocyclic alkyl group where the N atom is located.

[0023] According to an embodiment of the present invention, R 2 Preferably pyrrolidin-1-yl, 2-methylpyrrolidin-1-yl, 3-methylpyrrolidin-1-yl, pyrrol-1-yl, piperidin-1-yl, cyclohexylimino-1-yl, indolin-1-yl, isoindolin-2-yl, 1-methylisoindolin-2-yl, 1,3-dimethylisoindolin-2-yl. According to an embodiment of the present invention, R 2 Preferably pyrrolidin-1-yl, piperidin-1-yl, cyclohexylimino-1-yl, isoindolin-2-yl.

[0024] According to an embodiment of the present invention, R 2 Preferably wherein R 2a is selected from any one or more of C1-C6 alkyl, C1-C6 alkoxy, m1 is selected from 1, 2, 3, m2 is selected from 0, 1, 2, 3, 4, 5, n1 is selected from 1, 2, 3, n2 is selected from 0, 1, and 2 ≤ n1 + n2 ≤ 3, n3 is selected from 0, 1, 2, 3, 4 or 5. According to an embodiment of the present invention, R 2a is selected from any one of C1-C4 alkyl, C1-C4 alkoxy, preferably C1-C4 alkyl. According to an embodiment of the present invention, m1 is preferably 1. According to an embodiment of the present invention, n1 and n2 are preferably 1. According to an embodiment of the present invention, n1 is 2 and n2 is 0. According to an embodiment of the present invention, R 2a Preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.

[0025] According to an embodiment of the present invention, R 2 Preferably

[0026] According to an embodiment of the present invention, R 3 Preferably C1-C4 alkyl (such as methyl, isopropyl, tert-butyl), C3-C7 cycloalkyl (such as cyclopentyl), C1-C10 alkoxy (such as methoxy), phenyl, benzyl, C1-C4 alkyl-substituted phenyl (such as p-tolyl, pentamethylphenyl, p-tert-butylphenyl, 3,5-di-tert-butylphenyl).

[0027] According to an embodiment of the present invention, R 3 is preferably methoxy, methyl, phenyl.

[0028] According to an embodiment of the present invention, R 4 is preferably hydrogen, C1-C4 alkyl.

[0029] According to an embodiment of the present invention, R 4 is preferably hydrogen.

[0030] According to an embodiment of the present invention, R 5 and R 6 are the same, and are preferably C1-C4 alkyl (such as methyl, isopropyl), C3-C7 cycloalkyl (such as cyclopentyl), phenyl, benzyl, C1-C4 alkyl-substituted phenyl (such as p-tolyl).

[0031] According to an embodiment of the present invention, R 5 and R 6 are the same, and are preferably methyl, benzyl.

[0032] According to an embodiment of the present invention, R 7 is preferably C1-C4 alkyl, and R 7 is more preferably butyl, for example, tert-butyl.

[0033] According to an embodiment of the present invention, X 1 and X 2 are the same, and are preferably halogen (such as Cl), C1-C4 alkyl (such as methyl).

[0034] According to an embodiment of the present invention, X 1 and X 2 are the same, and are preferably Cl, methyl.

[0035] According to an embodiment of the present invention, the compound is selected from at least one of the following compounds:

[0036]

[0037] The present invention also provides a method for preparing the compound represented by the above formula I, and the preparation method includes:

[0038] (1) Using a polysubstituted indanone compound as a raw material to prepare a polysubstituted indene compound;

[0039] The polysubstituted indanone compound has a structure represented by formula I-1;

[0040]

[0041] In formula I-1, R 1 and R 3 and R 4has the meaning as described above;

[0042] The multi-substituted indene compound has the structure shown in Formula I-2:

[0043]

[0044] In Formula I-2, R 1 , R 2 , R 3 , R 4 has the meaning as described above;

[0045] (2) React the multi-substituted indene compound in step (1) with a silylamine reagent to obtain the silyl ligand compound of Formula I-3;

[0046]

[0047] (3) Perform a coordination reaction on the silyl ligand compound in step (2) with a central metal reagent to obtain the compound shown in Formula I, which is a metal complex.

[0048] According to an exemplary embodiment of the present invention, the multi-substituted indene compound of Formula I-2 in step (1) is, for example, 3-(pyrrolidin-1-yl)-4-phenyl-1H-indene, 3-(pyrrolidin-1-yl)-4-methoxy-1H-indene, 3-(pyrrolidin-1-yl)-4-methyl-1H-indene, 2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indene, 2-methyl-3-(isoindolin-N-yl)-4-phenyl-1H-indene.

[0049] According to an embodiment of the present invention, in step (1), the multi-substituted indene ketone compound shown in Formula I-1 is reacted with an azacyclic compound to obtain the multi-substituted indene compound shown in Formula I-2.

[0050] According to an embodiment of the present invention, in step (1), the multi-substituted indene ketone compound is, for example, 7-phenyl-1-indanone, 7-methoxy-1-indanone, 7-methyl-1-indanone, 2-methyl-7-phenyl-1-indanone.

[0051] According to an embodiment of the present invention, in step (1), the azacyclic reagent preferably has the structure shown below:

[0052] R 2 H

[0053] In the formula, R 2 has the meaning of a nitrogen-containing heterocyclic group in the definition of R 2 described above.

[0054] According to an embodiment of the present invention, in step (1), the molar ratio of the polysubstituted indanone compound to the azacyclic reagent is 1:1 - 1:5, for example, 1:1.

[0055] According to an embodiment of the present invention, in step (1), a Lewis acid reagent also needs to be added, such as titanium tetrachloride, titanium trichloride tetrahydrofuran complex, phosphorus pentoxide, aluminum trichloride.

[0056] According to an embodiment of the present invention, in step (1), the molar ratio of the polysubstituted indanone compound to the Lewis acid reagent is 1:0.1 - 1:1, for example, 1:0.1.

[0057] According to an embodiment of the present invention, in step (2), the silyl ligand compound of formula I-3 is, for example, N-(tert-butyl)-1-(3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)-1,1-dimethylsilylamine, N-(tert-butyl)-1-(3-(pyrrolidin-1-yl)-4-methoxy-1H-indenyl)-1,1-dimethylsilylamine, N-(tert-butyl)-1-(3-(pyrrolidin-1-yl)-4-methyl-1H-indenyl)-1,1-dimethylsilylamine, N-(tert-butyl)-1-(2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)-1,1-dimethylsilylamine, N-(tert-butyl)-1-(2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)-1,1-dibenzylsilylamine, N-(tert-butyl)-1-(2-methyl-3-(isoindolinyl-N)-4-phenyl-1H-indenyl)-1,1-dimethylsilylamine.

[0058] According to an embodiment of the present invention, in step (2), the silylamine reagent has the structure shown below:

[0059]

[0060] In the formula, R 5 , R 6 , R 7 have the meanings as described above.

[0061] According to an embodiment of the present invention, in step (2), the silylamine reagent is selected from at least one of N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine, N-(tert-butyl)-N-(1-chloro-1,1-dibenzylsilyl)amine, N-(tert-butyl)-N-(1-chloro-1,1-dimethylphenylsilyl)amine.

[0062] According to an embodiment of the present invention, in step (2), an alkyllithium also needs to be added, such as n-butyllithium.

[0063] According to an embodiment of the present invention, in the step (2), the molar ratio of the polysubstituted indene compound represented by formula I-2 to the silylamine reagent is 1:0.8 - 1.2, for example, 1:1.

[0064] According to an embodiment of the present invention, in the step (2), the molar ratio of the polysubstituted indene compound represented by formula I-2 to the alkyllithium is 1:1 - 1.2, for example, 1:1.

[0065] According to an embodiment of the present invention, in the step (3), the silyl ligand compound reacts with the central metal reagent to form the metal complex represented by formula I. Examples of the metal complex represented by formula I include dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)amino)titanium, dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(pyrrolidin-1-yl)-4-methoxy-1H-indenyl)amino)titanium, dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(pyrrolidin-1-yl)-4-methyl-1H-indenyl)amino)titanium, dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)amino)titanium, dichloro(N-(tert-butyl)-1,1-dibenzylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)amino)titanium, dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-3-(isoindolinyl-N)-4-phenyl-1H-indenyl)amino)titanium.

[0066] According to an embodiment of the present invention, in the step (3), the central metal reagent is selected from metal compounds containing M, where M represents a fourth subgroup element, for example, titanium Ti, zirconium Zr, hafnium Hf.

[0067] According to an embodiment of the present invention, in the step (3), the metal compound containing M has the following structure:

[0068] MCl n (THF) m

[0069] In the formula, M has the meaning as described above, n is selected from 2, 3 or 4, and m is selected from 0, 1, 2 or 3.

[0070] According to an embodiment of the present invention, in step (3), the molar ratio of the silicon-based ligand compound to the central metal reagent is 1:0.5 - 1.2, for example, 1:1.

[0071] According to an exemplary embodiment of the present invention, the central metal reagent is, for example, titanium trichloride, titanium tetrachloride.

[0072] According to an embodiment of the present invention, in step (3), lead chloride needs to be further added. Preferably, the molar ratio of the central metal reagent to lead chloride is 10:0 - 10, for example, 10:7.5.

[0073] According to an embodiment of the present invention, in step (3), dichloromethane is optionally added or not added. Preferably, the molar ratio of the silicon-based ligand compound to dichloromethane is 1:4 - 1:10, for example, 1:5.

[0074] According to an embodiment of the present invention, the preparation method further includes: step (4): when M in the metal complex prepared in step (3) is connected to a halogen, it can further undergo a substitution reaction with an organomagnesium salt or an organolithium salt to obtain X 1 、X 2 Metal complexes in which X and X are each independently selected from halogenated C1 - C10 alkyl groups, C1 - C10 alkyl groups, and C1 - C10 silyl groups.

[0075] According to an embodiment of the present invention, in step (4), the metal complex is, for example, dimethyl(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)amino)titanium, dimethyl(N-(tert-butyl)-1,1-dibenzylsilyl-1-((1,2,3,3a,7a-η)-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)amino)titanium.

[0076] According to an embodiment of the present invention, preferably, the organomagnesium salt is X'-Mg-X, where X' is selected from halogenated C1 - C10 alkyl groups (such as trifluoromethyl, difluoromethyl, monofluoromethyl), C1 - C10 alkyl groups, C1 - C10 silyl groups; X is selected from halogens (such as Cl); X'-Mg-X is, for example, methylmagnesium chloride.

[0077] According to an embodiment of the present invention, preferably, the organolithium salt is X'-Li, where X' is selected from halogenated C1 - C10 alkyl groups (such as trifluoromethyl, difluoromethyl, monofluoromethyl), C1 - C10 alkyl groups, C1 - C10 silyl groups; X'-Li is, for example, at least one of trimethylsilylmethyllithium and methyllithium.

[0078] The present invention also provides the use of the compound shown in the above formula I as an olefin polymerization catalyst.

[0079] According to an embodiment of the present invention, the olefin polymerization includes but is not limited to homopolymerization of ethylene, copolymerization of ethylene and α-olefin, and copolymerization of ethylene and cyclic olefin.

[0080] The present invention also provides a catalytic system comprising the compound shown in the above formula I.

[0081] According to an embodiment of the present invention, the catalytic system further includes borate, such as including but not limited to at least one of trityl tetrakis(pentafluorophenyl)borate, N,N-dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, etc.

[0082] The present invention also provides the use of the compound shown in the above formula I or the catalytic system in olefin polymerization, and the olefin polymerization includes but is not limited to homopolymerization of ethylene, copolymerization of ethylene and α-olefin, and copolymerization of ethylene and cyclic olefin.

[0083] The present invention also provides an olefin polymerization method, which includes: carrying out an olefin polymerization reaction in the presence of the compound shown in the above formula I or the catalytic system.

[0084] The present invention also provides an olefin copolymerization method, which includes: carrying out a copolymerization reaction of ethylene and α-olefin in the presence of the compound shown in the above formula I or the catalytic system to obtain a copolymer of ethylene and α-olefin.

[0085] According to an embodiment of the present invention, the molecular formula of the α-olefin is R-CH=CH2, where R is an alkyl group with 4 or more carbon atoms, preferably an alkyl group with 6 carbon atoms; the α-olefin is, for example, 1-octene.

[0086] According to an embodiment of the present invention, in the copolymer of ethylene and α-olefin, the mass content of the α-olefin unit is 15-50%, such as 20%, 30%, 40%, 50%, 60%.

[0087] According to an embodiment of the present invention, the copolymer of ethylene and α-olefin is an ethylene-1-octene copolymer. Preferably, in the ethylene-1-octene copolymer, the mass content of the 1-octene unit is 15-50%, such as 20%, 30%, 40%, 50%, 60%.

[0088] Beneficial effects

[0089] Compared with traditional CGC catalysts, the present invention provides a class of multi-substituted indenyl ligand catalysts. Substituting the indenyl group with an alkyl group, a bulky group or an electron-donating heteroatom group can not only improve the catalytic polymerization activity, molecular weight and monomer reactivity ratios of copolymerization, thereby improving the polymer properties, but also, the catalyst has good temperature tolerance, and the polymerization reaction can be carried out under relatively high temperature conditions, which is very important for increasing the polymer production capacity and the molecular weight of the polymer at relatively high temperatures.

[0090] The present invention uses multi-substituted indanone compounds as starting materials, and then introduces electron-donating, heteroatom or nitrogen-containing heterocyclic groups at the 3- and 4-positions to form multi-substituted indenyl ligands. By reacting with silylamine reagents and then coordinating with metal reagents, a variety of novel metal complexes are synthesized. It is found that introducing an electron-donating substituent at the 3-position of the indenyl group can improve the catalytic polymerization activity of the metal complex, resulting in an increase in the molecular weight of the copolymer. However, the insertion rate of the comonomer in the polymer will decrease accordingly. For the novel metal complexes provided by the present invention, since the 3- and 4-positions of the indenyl ligand are substituted by a variety of optimized groups, when catalyzing olefin copolymerization, not only can the polymerization reaction activity be improved, but even at relatively high polymerization reaction temperatures, the polymer still shows a relatively high molecular weight, and the reactivity ratios of the comonomers are significantly improved compared with the catalysts in the prior art (such as the catalysts disclosed in CN117467047A). Such metal complexes have extremely high application value for improving the performance indicators of olefin polymers.

[0091] Definitions and explanations:

[0092] C 1-10 is selected from C1, C2, C3, C4, C5, C6, C7, C8, C9 and C 10 ; C 3-8 is selected from C3, C4, C5, C6, C 7、 C8.

[0093] As used herein, the term "halogen" means fluorine, chlorine, bromine and iodine.

[0094] As used herein, the term "alkyl" should be understood to mean a saturated aliphatic hydrocarbon group having a straight or branched chain. For example, "C 1-10 alkyl" means a straight and branched chain alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, "C 1-6 alkyl" means a straight and branched chain alkyl group having 1, 2, 3, 4, 5 or 6 carbon atoms, "C 1-4"Alkyl" means straight-chain and branched-chain alkyl groups having 1, 2, 3, or 4 carbon atoms. The alkyl groups are, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, etc., or their isomers.

[0095] The term "alkoxy" is "alkyloxy", and "alkyl" is defined as above.

[0096] The term "cycloalkyl" should be understood to represent saturated monocyclic, bicyclic hydrocarbon rings or tricyclic alkanes, where the bicyclic or tricyclic can be fused rings, bridged rings, spiro rings, such as "C 3-8 cycloalkyl", preferably "C 3-6 cycloalkyl". The term "C 3-8 cycloalkyl" should be understood to represent saturated monocyclic, bicyclic hydrocarbon rings or bridged alkanes having 3, 4, 5, 6, 7, or 8 carbon atoms. The C 3-8 cycloalkyl can be a monocyclic hydrocarbon group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

[0097] As used herein, the term "substituted with …… " means substituted with more than 1 group, for example, 1, 2, 3, 4, 5, or more groups. "Substituted with 1 to 5 …… " means that it can be substituted with 1, 2, 3, 4, or 5 groups. Detailed Description of the Embodiments

[0098] The technical solutions of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only for illustrative explanation of the present invention and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0099] Unless otherwise specified, the raw materials and reagents used in the following embodiments are commercially available products or can be prepared by known methods.

[0100] Catalyst Preparation

[0101] Example 1: Preparation of Dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)amino)titanium (Compound 1)

[0102]

[0103] (1) Preparation of 3-(Pyrrolidin-1-yl)-4-phenyl-1H-indene (Compound 1-1)

[0104] Prepare a dry and clean 250 mL reaction flask, connect it to a Schlenk line, and displace the nitrogen. Weigh 7-phenyl-1-indanone (6.2 g, 30 mmol) into the reaction flask, dissolve it in 60 mL of toluene, start stirring, and slowly add titanium tetrachloride (0.6 g, 3 mmol) to the reaction flask at low temperature. After reacting for 2 hours, add pyrrolidine (2.1 g, 30 mmol) dropwise to the system, and stir the reaction overnight. Filter the system in the reaction flask under reduced pressure, collect the filtrate, and concentrate the filtrate under reduced pressure to obtain an oily product (7.4 g, 94%), which is Compound 1-1. 1 H NMR (500 MHz, CDCl3, rt): δ 7.57–7.52 (m, 2H), 7.41–7.38 (m, 1H), 7.34 (ddt, J = 8.1, 6.5, 1.1 Hz, 2H), 7.31–7.28 (m, 1H), 7.26–7.23 (m, 2H), 5.60 (t, J = 2.6 Hz, 1H), 3.37 (d, J = 2.5 Hz, 2H), 2.53–2.43 (m, 4H), 1.49–1.38 (m, 4H).

[0105]

[0106] (2) Preparation of N-(tert-Butyl)-1-(3-(pyrrolidin-1-yl)-4-phenyl-1H-inden-1-yl)-1,1-dimethylsilylamine (Compound 1-2)

[0107] Prepare a dry and clean 250 mL reaction flask and place it in a glove box. Weigh 3-(pyrrolidin-1-yl)-4-phenyl-1H-indene (3.1 g, 15 mmol) into the reaction flask, dissolve it in 100 mL of n-hexane at low temperature, start stirring, and then add n-butyllithium n-hexane solution (6.6 mL, 16.5 mmol) dropwise to the reaction flask. A large amount of precipitate precipitates, and the reaction is carried out at room temperature overnight. Filter the reaction system, dissolve the filter cake in tetrahydrofuran (50 mL) to obtain an indenyllithium salt tetrahydrofuran solution. Weigh N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine (2.5 g, 15 mol) and slowly add it dropwise to the above indenyllithium salt tetrahydrofuran solution. Stir the reaction system at room temperature overnight. Concentrate the system in the reaction flask under reduced pressure to remove the solvent. Then add 20 mL of n-hexane to the residue in the reaction flask twice for extraction twice, filter and collect the filtrate, and concentrate it under reduced pressure to obtain an oily product (4.6 g, 79%), which is Compound 1-2. 11H NMR (500 MHz, CDCl3, rt): δ 7.55–7.49 (m, 2H), 7.46 (t, J = 4.3 Hz, 1H), 7.32 (dd, J = 8.0, 6.3 Hz, 2H), 7.27 (d, J = 7.2 Hz, 1H), 7.20 (d, J = 4.4 Hz, 2H), 5.77 (d, J = 2.4 Hz, 1H), 3.44 (d, J = 2.3 Hz, 1H), 2.50–2.43 (m, 4H), 1.48–1.36 (m, 4H), 1.19 (s, 9H), 0.00 (s, 3H), -0.10 (s, 3H).

[0108]

[0109] (3) Preparation of dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)amido)titanium (Compound 1)

[0110] Prepare a dry and clean 250 mL reaction flask and place it in the glove box. Weigh N-(tert-butyl)-1-(3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)-1,1-dimethylsilylamine (4.6 g, 11.8 mmol) into the reaction flask and dissolve it in 100 mL of n-hexane. Under low temperature conditions, add n-butyllithium n-hexane solution (9.7 mL, 24 mmol) dropwise to the reaction flask. After the system is transferred to room temperature and stirred overnight, filter to collect the filter cake, and add 100 mL of tetrahydrofuran to the filter cake and stir to dissolve. Weigh titanium(III) chloride tetrahydrofuran complex (1:3) (4.0 g, 11 mmol) and add it to the tetrahydrofuran solution. After stirring for 2 h, add lead(II) chloride (1.7 g, 6.3 mmol) and react at room temperature overnight. Concentrate the system in the reaction flask under reduced pressure to remove the solvent. Then add 30 mL of toluene to the residue in the reaction flask for extraction, filter to collect the filtrate and concentrate it under reduced pressure to remove toluene. Then add 30 mL of n-hexane to the residue in the reaction flask for pulping, and filter to obtain 0.6 g of a black powder product, which is Compound 1. 1 1H NMR (500 MHz, CDCl3, rt): δ 7.63 (d, J = 7.9 Hz, 1H), 7.39–7.34 (m, 3H), 7.32–7.22 (m, 3H), 7.19–7.14 (m, 1H), 5.97 (s, 1H), 2.99–2.74 (m, 4H), 1.66–1.56 (m, 4H), 1.34 (s, 9H), 0.91 (s, 3H), 0.67 (s, 3H).

[0111] Example 2: Preparation of Dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(pyrrolidin-1-yl)-4-methoxy-1H-indenyl)amido)titanium (Compound 2)

[0112]

[0113] (1) Preparation of 3-(pyrrolidin-1-yl)-4-methoxy-1H-indene (Compound 2-1):

[0114] Prepare a dry and clean 100 mL reaction flask, connect it to a Schlenk line, and displace the nitrogen. Weigh 7-methoxy-1-indanone (3.2 g, 20 mmol) into the reaction flask, dissolve it in 50 mL of toluene, start stirring, and slowly add titanium tetrachloride (0.4 g, 2 mmol) to the reaction flask at low temperature. After reacting for 2 hours, add pyrrolidine (1.4 g, 20 mmol) dropwise to the system, and stir the reaction overnight. Filter the system in the reaction flask under reduced pressure, collect the filtrate, and concentrate the filtrate under reduced pressure to obtain an oily product (4.3 g, 99%). 1 H NMR (500 MHz, CDCl3, rt): δ 7.16 (t, J = 7.8 Hz, 1H), 7.05 (d, J = 7.3 Hz, 1H), 6.82 (d, J = 8.2 Hz, 1H), 5.38 (t, J = 2.5 Hz, 1H), 3.90 (s, 3H), 3.30 (d, J = 2.5 Hz, 2H), 3.19 (td, J = 5.3, 3.1 Hz, 4H), 1.94 (td, J = 2.8 Hz, 4H).

[0115]

[0116] (2) Preparation of N-(tert-butyl)-1-(3-(pyrrolidin-1-yl)-4-methoxy-1H-indenyl)-1,1-dimethylsilylamine (Compound 2-2)

[0117] Place a dry and clean 250 mL reaction flask in the glove box. Weigh 3-(pyrrolidin-1-yl)-4-methoxy-1H-indene (2.1 g, 10 mmol) into the reaction flask, dissolve it in a mixed solvent of 120 mL of toluene and n-hexane (7:5), and place it at low temperature. Start stirring, and then add n-butyllithium n-hexane solution (4.4 mL, 11 mmol) dropwise to the reaction flask. A large amount of precipitate precipitates, and the reaction is carried out at room temperature overnight. Filter the reaction system, dissolve the filter cake in tetrahydrofuran (30 mL) to obtain a tetrahydrofuran solution of indenyl lithium salt. Weigh N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine (1.5 g, 10 mol) and slowly add it dropwise to the above-mentioned tetrahydrofuran solution of indenyl lithium salt. Stir the reaction system at room temperature overnight. Concentrate the system in the reaction flask under reduced pressure to remove the solvent. Then add 20 mL of n-hexane to the residue in the reaction flask twice for extraction twice, filter and collect the filtrate, and concentrate it under reduced pressure to obtain an oily product (1.6 g, 48%), which is compound 2-2. 1 H NMR(500MHz,CDCl3,rt):δ7.07–7.04(m,2H),6.67(t,J=4.5Hz,1H),5.52(d,J=2.4Hz,1H),3.83(d,J=2.1Hz,3H),3.31(d,J=2.4Hz,1H),3.17–3.03(m,4H),1.91–1.83(m,4H),1.13(s,9H),-0.10(s,3H),-0.21(s,3H).

[0118]

[0119] (3) Preparation of dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(pyrrolidin-1-yl)-4-methoxy-1H-indenyl)amino)titanium (Compound 2)

[0120] Place a dry and clean 250 mL reaction flask in a glove box. Weigh N-(tert-butyl)-1-(3-(pyrrolidin-1-yl)-4-methoxy-1H-indenyl)-1,1-dimethylsilylamine (2.4 g, 7 mmol) into the reaction flask and dissolve it in 70 mL of n-hexane. Dropwise add a n-butyllithium n-hexane solution (5.8 mL, 14 mmol) to the reaction flask under low temperature conditions. After the system is transferred to room temperature and stirred overnight, filter and collect the filter cake, and add 40 mL of tetrahydrofuran to the filter cake and stir to dissolve. Weigh titanium(III) chloride tetrahydrofuran complex (1:3) (1.5 g, 4 mmol) and add it to the tetrahydrofuran solution. After stirring for 2 h, add lead(II) chloride (0.6 g, 2.4 mmol) and 5 mL of dichloromethane, and react at room temperature overnight. Concentrate the system in the reaction flask under reduced pressure to remove the solvent. Then add 30 mL of toluene to the residue in the reaction flask for extraction, filter and collect the filtrate, and concentrate it under reduced pressure to remove toluene. Then add 30 mL of n-hexane to the residue in the reaction flask for pulping, and filter to obtain 0.5 g of a black powder product, which is compound 2. 1 H NMR(500MHz,CDCl3,rt):δ7.14(t,J=4.5Hz,1H),6.89–6.62(m,2H),5.22(s,1H),3.82(s,3H),3.16–2.96(m,4H),1.97–1.90(m,4H),1.20(s,9H),0.81(s,3H),0.31(s,3H).

[0121] Example 3: Preparation of dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(pyrrolidin-1-yl)-4-methyl-1H-indenyl)amido)titanium (Compound 3)

[0122]

[0123] (1) Preparation of 3-(pyrrolidin-1-yl)-4-methyl-1H-indene (Compound 3-1):

[0124] Prepare a dry and clean 250 mL reaction flask connected to a Schlenk line and displace nitrogen. Weigh 7-methyl-1-indanone (4.4 g, 30 mmol) into the reaction flask and dissolve it in 100 mL of n-hexane. Start stirring, and slowly add titanium(IV) chloride (0.6 g, 3 mmol) to the reaction flask under low temperature. After reacting for 2 h, add pyrrolidine (2.1 g, 30 mmol) dropwise to the system, and stir the reaction overnight. Filter the system in the reaction flask under reduced pressure, collect the filtrate, and concentrate the filtrate under reduced pressure to obtain an oily product (5.4 g, 90%), which is Compound 3-1. 11H NMR (500 MHz, CDCl3, rt): δ 7.23 (d, J = 7.1 Hz, 1H), 7.11–7.03 (m, 2H), 5.69 (t, J = 2.4 Hz, 1H), 3.27 (d, J = 2.5 Hz, 2H), 3.03–2.95 (m, 4H), 2.66 (s, 3H), 1.95–1.84 (m, 4H).

[0125]

[0126] (2) Preparation of N-(tert-butyl)-1-(3-(pyrrolidin-1-yl)-4-methyl-1H-inden-1-yl)-1,1-dimethylsilylamine (Compound 2-2):

[0127] Prepare a dry and clean 250 mL reaction flask and place it in the glove box. Weigh 3-(pyrrolidin-1-yl)-4-methyl-1H-indene (3.0 g, 15 mmol) into the reaction flask, dissolve it in 50 mL of n-hexane, and place it at low temperature. Start stirring, and then add a n-hexane solution of n-butyllithium (6.6 mL, 16 mmol) dropwise to the reaction flask. A large amount of precipitate forms, and the reaction is carried out at room temperature overnight. The reaction system is filtered, and the filter cake is dissolved in tetrahydrofuran (60 mL) to obtain a tetrahydrofuran solution of indenyl lithium salt. Weigh N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine (2.4 g, 14 mmol) and slowly add it dropwise to the above tetrahydrofuran solution of indenyl lithium salt. The reaction system is stirred at room temperature overnight. The solvent in the reaction flask is concentrated under reduced pressure. Then, 20 mL of n-hexane is added to the residue in the reaction flask twice for extraction, and the filtrate is collected by filtration and concentrated under reduced pressure to obtain an oily product (4 g, 81%), which is Compound 3-2. 1 1H NMR (500 MHz, CDCl3, rt): δ 7.33–7.29 (m, 1H), 7.07 (t, J = 7.5 Hz, 1H), 7.01 (d, J = 7.4 Hz, 1H), 5.89 (d, J = 2.3 Hz, 1H), 3.34 (d, J = 2.3 Hz, 1H), 3.06–3.04 (m, 2H), 2.98–2.89 (m, 2H), 2.69 (s, 3H), 1.93–1.88 (m, 4H), 1.20 (s, 9H), -0.03 (s, 3H), -0.11 (s, 3H).

[0128]

[0129] (3) Preparation of dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(pyrrolidin-1-yl)-4-methyl-1H-inden-1-yl)amino)titanium (Compound 3)

[0130] Place a dry and clean 250 mL reaction flask in the glove box. Weigh N-(tert-butyl)-1-(3-(pyrrolidin-1-yl)-4-methyl-1H-indenyl)-1,1-dimethylsilylamine (2.0 g, 6.1 mmol) into the reaction flask and dissolve it in 60 mL of n-hexane. Dropwise add a n-hexane solution of n-butyllithium (5.0 mL, 12.5 mmol) to the reaction flask under low temperature conditions. After the system is transferred to room temperature and stirred overnight, filter to collect the filter cake, and add 60 mL of tetrahydrofuran to the filter cake and stir to dissolve. Weigh titanium(III) chloride tetrahydrofuran complex (1:3) (2.7 g, 7.3 mmol) and add it to the tetrahydrofuran solution. After stirring for 2 h, add lead(II) chloride (1.2 g, 4.3 mmol), and react at room temperature overnight. Concentrate the system in the reaction flask under reduced pressure to remove the solvent. Then add 30 mL of toluene to extract the residue in the reaction flask, filter to collect the filtrate, and concentrate it under reduced pressure to remove toluene. Then add 30 mL of n-hexane to the residue in the reaction flask for pulping, and filter to obtain 1.0 g of a black powder product (37%), which is compound 3. 1 H NMR (500 MHz, CDCl3, rt): δ 7.49 (d, J = 7.9 Hz, 1H), 7.17–7.10 (s, 2H), 6.09 (s, 1H), 3.85 (s, 2H), 3.42 (s, 2H), 2.67 (s, 3H), 2.03–1.99 (s, 4H), 1.32 (s, 9H), 0.87 (s, 3H), 0.63 (s, 3H).

[0131] Example 4: Preparation of dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)amido)titanium (Compound 4)

[0132]

[0133] (1) Preparation of 2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indene (Compound 4-1): Connect a Schlenk line to a dry and clean 1 L reaction flask and displace the nitrogen. Weigh 2-methyl-7-phenyl-1-indanone (23 g, 0.1 mol) into the reaction flask and dissolve it in 500 mL of toluene. Start stirring, and slowly add titanium(IV) chloride (1.9 g, 10 mmol) to the reaction flask at low temperature. After reacting for 2 h, add pyrrolidine (7.1 g, 0.1 mol) dropwise to the system, and stir the reaction overnight. Filter the system in the reaction flask under reduced pressure, collect the filtrate, and concentrate the filtrate under reduced pressure to obtain a black solid product (26 g, 94%), which is compound 4-1. 11H NMR (500 MHz, CDCl3, rt): δ 7.42–7.38 (m, 2H), 7.32–7.22 (m, 4H), 7.15–7.09 (m, 2H), 3.28 (s, 2H), 2.81–2.74 (m, 4H), 2.07 (s, 3H), 1.41–1.28 (m, 4H).

[0134]

[0135] (2) Preparation of N-(tert-butyl)-1-(2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-inden-1-yl)-1,1-dimethylsilylamine (Compound 4-2):

[0136] Prepare a dry and clean 100 mL reaction flask and place it in a glove box. Weigh 2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indene (2.8 g, 10 mmol) into the reaction flask, dissolve it in a mixed solvent of toluene and n-hexane (1:1, 40 mL), and place it at low temperature. Start stirring, and then add a n-butyllithium n-hexane solution (4.2 mL, 10.5 mmol) dropwise to the reaction flask. A large amount of precipitate forms, and the reaction is carried out at room temperature overnight. The reaction system is filtered, and the filter cake is dissolved in tetrahydrofuran (40 mL) to obtain an indenyllithium salt tetrahydrofuran solution. Weigh N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine (1.6 g, 10 mmol) and slowly add it dropwise to the above indenyllithium salt tetrahydrofuran solution. The reaction system is stirred at room temperature overnight. The solvent in the reaction flask is concentrated under reduced pressure to remove the solvent. Then, add 20 mL of n-hexane to the residue in the reaction flask twice for extraction, and filter to collect the filtrate. Concentrate it under reduced pressure to obtain an oily product (3.3 g, 82%), which is Compound 4-2. 1 1H NMR (500 MHz, CDCl3, rt): δ 7.37–7.33 (m, 4H), 7.31–7.27 (m, 2H), 7.09–7.06 (m, 2H), 3.31 (s, 1H), 2.83–2.74 (m, 4H), 2.10 (s, 3H), 1.47–1.38 (m, 2H), 1.29–1.26 (m, 2H), 1.17 (s, 9H), 0.08 (s, 3H), 0.04 (s, 3H).

[0137]

[0138] (3) Preparation of dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-inden-1-yl)amino)titanium (Compound 4)

[0139] Place a dry and clean 250 mL reaction flask in the glove box. Weigh N-(tert-butyl)-1-(2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)-1,1-dimethylsilylamine (1.7 g, 4.3 mmol) into the reaction flask and dissolve it in 50 mL of n-hexane. Dropwise add n-butyllithium n-hexane solution (3.6 mL, 9 mmol) to the reaction flask under low temperature conditions. After the system is transferred to room temperature and stirred overnight, filter to collect the filter cake, and add 100 mL of tetrahydrofuran to the filter cake and stir to dissolve. Weigh titanium(III) chloride tetrahydrofuran complex (1:3) (1.9 g, 5.2 mmol) and add it to the tetrahydrofuran solution. After stirring for 2 h, add lead(II) chloride (1.2 g, 4.3 mmol) and 10 mL of dichloromethane, and react overnight at room temperature. Concentrate the system in the reaction flask under reduced pressure to remove the solvent. Then add 50 mL of toluene to the residue in the reaction flask for extraction, filter to collect the filtrate, and concentrate it under reduced pressure to remove toluene. Then add 30 mL of n-hexane to the residue in the reaction flask for pulping, and filter to obtain 1.3 g of a black powder product (58%), which is compound 4. 1 H NMR(500MHz,CDCl3,rt):δ7.72(d,J=8.5Hz,1H),7.53–7.43(m,2H),7.35(dt,J=14.9,7.2Hz,3H),7.28(d,J=7.0Hz,1H),7.22(d,J=7.9Hz,1H),3.17–(m,2H),3.07–2.99(m,2H),2.42(s,3H),1.43–1.38(m,4H),1.37(s,8H),0.95(s,3H),0.79(s,3H).

[0140] Example 5: Preparation of Dimethyl(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)amino)titanium (Compound 5)

[0141]

[0142] Place a dry and clean 100 mL reaction tube in the glove box. Weigh dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)amido)titanium (0.26 g, 0.5 mmol) into the reaction flask and dissolve it in 25 mL of toluene. Dropwise add methyllithium ether solution (1.0 mL, 1.5 mmol) to the reaction flask under low temperature conditions. After the system is transferred to room temperature and stirred overnight, concentrate the system in the reaction flask under reduced pressure to remove the solvent. Then add 30 mL of n-hexane to extract the residue in the reaction flask, filter and collect the filtrate, and concentrate it under reduced pressure to obtain a black solid product (0.21 g, 88%) and store it at low temperature in the glove box. 1 H NMR (500 MHz, CDCl3, rt): δ 7.52–7.48 (m, 2H), 7.45 (dd, J = 8.5, 1.0 Hz, 1H), 7.39–7.32 (m, 3H), 7.12 (dd, J = 6.9, 1.0 Hz, 1H), 7.00 (dd, J = 8.6, 6.9 Hz, 1H), 2.12 (s, 3H), 1.51 (s, 9H), 0.75 (s, 3H), 0.71 (s, 3H), 0.59 (s, 3H), -0.39 (s, 3H).

[0143] Example 6: Preparation of dichloro(N-(tert-butyl)-1,1-dibenzylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)amido)titanium (Compound 6)

[0144]

[0145] (1) Preparation of N-(tert-butyl)-1-(2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)-1,1-dibenzylsilylamine (Compound 6-1)

[0146] Place a dry and clean 100 mL reaction flask in a glove box. Weigh 2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indene (2.8 g, 10 mmol) into the reaction flask, dissolve it in a mixed solvent of 40 mL of toluene and n-hexane (1:1), and place it at low temperature. Start stirring, and then add a n-hexane solution of n-butyllithium (4.2 mL, 10.5 mmol) dropwise to the reaction flask. A large amount of precipitate forms, and the reaction is carried out at room temperature overnight. Filter the reaction system, dissolve the filter cake in tetrahydrofuran (40 mL) to obtain a tetrahydrofuran solution of indenyl lithium salt. Weigh N-(tert-butyl)-N-(1-chloro-1,1-dibenzylsilyl)amine (3.2 g, 10 mol) and slowly add it dropwise to the above tetrahydrofuran solution of indenyl lithium salt. Stir the reaction system at room temperature overnight. Concentrate the system in the reaction flask under reduced pressure to remove the solvent. Then add 30 mL of n-hexane to the residue in the reaction flask twice for extraction twice, filter and collect the filtrate, and concentrate it under reduced pressure to obtain an oily product (5.2 g, 93%), which is Compound 6-1. 1 H NMR (500 MHz, CDCl3, rt): δ 7.47–7.43 (m, 1H), 7.40 (dt, J = 6.4, 1.6 Hz, 2H), 7.32–7.25 (m, 4H), 7.21–7.09 (m, 4H), 7.05 (dd, J = 7.5, 1.6 Hz, 2H), 6.91–6.88 (m, 1H), 6.88–6.84 (m, 4H), 3.54 (s, 1H), 2.92 (s, 2H), 2.83–2.73 (m, 4H), 2.14 (s, 3H), 1.48–1.41 (m, 2H), 1.33–1.23 (m, 2H), 1.12 (s, 2H), 1.07 (s, 9H).

[0147]

[0148] (2) Preparation of Dichloro(N-(tert-butyl)-1,1-dibenzylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)amido)titanium (Compound 6)

[0149] Place a dry and clean 250 mL reaction flask in the glove box. Weigh N-(tert-butyl)-1-(2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)-1,1-dibenzylsilylamine (2.2 g, 4.0 mmol) into the reaction flask and dissolve it in 50 mL of n-hexane. Dropwise add n-butyllithium n-hexane solution (3.3 mL, 8.2 mmol) to the reaction flask under low temperature conditions. After the system is transferred to room temperature and stirred overnight, filter to collect the filter cake, and add 50 mL of tetrahydrofuran to the filter cake and stir to dissolve. Weigh titanium(III) chloride tetrahydrofuran complex (1:3) (1.91 g, 2.8 mmol) and add it to the tetrahydrofuran solution. After stirring for 2 h, add lead(II) chloride (0.5 g, 1.6 mmol) and 5 mL of dichloromethane, and react at room temperature overnight. Concentrate the system in the reaction flask under reduced pressure to remove the solvent. Then add 50 mL of toluene to extract the residue in the reaction flask, filter to collect the filtrate and concentrate it under reduced pressure to remove toluene. Then add 30 mL of n-hexane to the residue in the reaction flask for pulping, and filter to obtain 1.0 g of a black-green powder product (37%), which is Compound 6. 1 HNMR(500MHz,CDCl3,rt):δ7.84(dd,J=8.6,0.9Hz,1H),7.42–7.30(m,4H),7.24–7.19(m,4H),7.19–7.11(m,2H),7.10–7.08(m,5H),7.06–7.03(m,2H),3.17–3.08(m,4H),3.03(td,J=7.0,3.2Hz,2H),2.92(d,J=15.6Hz,1H),2.84(d,J=15.5Hz,2H),2.76(d,J=15.6Hz,1H),2.38(s,3H),2.35(s,2H),1.39(s,9H).

[0150] Example 7: Preparation of dimethyl(N-(tert-butyl)-1,1-dibenzylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)amino)titanium (Compound 7)

[0151]

[0152] Place a dry and clean 100 mL reaction tube in the glove box. Weigh dichloro(N-(tert-butyl)-1,1-dibenzylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-3-(pyrrolidin-1-yl)-4-phenyl-1H-indenyl)amido)titanium (0.34 g, 0.5 mmol) into the reaction flask and dissolve it in 25 mL of toluene. Under low temperature conditions, slowly add methyllithium ether solution (1.0 mL, 1.5 mmol) dropwise to the reaction flask. After the system is transferred to room temperature and stirred overnight, concentrate the system in the reaction flask under reduced pressure to remove the solvent. Then, add 30 mL of n-hexane to extract the residue in the reaction flask, filter and collect the filtrate, and concentrate it under reduced pressure to obtain a black solid product (0.2 g, 63%), which is compound 7, and store it at low temperature in the glove box. 1 H NMR (500 MHz, CDCl3, rt): δ 7.59 (d, J = 8.6 Hz, 1H), 7.53–7.49 (m, 2H), 7.41–7.33 (m, 3H), 7.21 (d, J = 7.7 Hz, 2H), 7.16 (dd, J = 10.2, 6.9 Hz, 2H), 7.10 (t, J = 7.6 Hz, 2H), 7.07 (d, J = 4.3 Hz, 4H), 7.05–6.99 (m, 2H), 3.03 (d, J = 6.6 Hz, 2H), 2.92–2.89 (m, 4H), 2.70 (d, J = 15.4 Hz, 2H), 2.58 (d, J = 15.4 Hz, 2H), 2.35 (s, 2H), 2.06 (s, 3H), 1.52 (s, 9H), 0.78 (s, 3H), -0.30 (s, 3H).

[0153] Example 8: Preparation of dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-3-(isoindolinyl-N)-4-phenyl-1H-indenyl)amido)titanium (Compound 8)

[0154]

[0155] (1) Preparation of 2-methyl-3-(isoindolinyl-N)-4-phenyl-1H-indene (Compound 8-1): Prepare a dry and clean 100 mL reaction flask connected to a Schlenk line and displace the nitrogen. Weigh 2-methyl-7-phenyl-1-indanone (1.1 g, 5 mmol) into the reaction flask and dissolve it in 20 mL of toluene. Start stirring, and slowly add titanium tetrachloride (0.1 g, 0.5 mmol) dropwise to the reaction flask at low temperature. After reacting for 2 hours, add isoindoline (0.6 g, 5 mmol) dropwise to the system, and stir the reaction overnight. Filter the system in the reaction flask under reduced pressure, collect the filtrate, and concentrate the filtrate under reduced pressure to obtain a black solid product (1.5 g, 92%). 11H NMR (500 MHz, CDCl3, rt): δ 7.34 (d, J = 7.5 Hz, 3H), 7.17–7.14 (m, 3H), 7.09 (dd, J = 5.6, 3.1 Hz, 2H), 7.00–6.93 (m, 4H), 4.13 (s, 4H), 3.32 (s, 2H), 2.02 (s, 3H).

[0156]

[0157] (2) Preparation of N-(tert-butyl)-1-(2-methyl-3-(isoindolinyl-N)-4-phenyl-1H-indenyl)-1,1-dimethylsilylamine (Compound 8-2):

[0158] Prepare a dry and clean 250 mL reaction flask and place it in a glove box. Weigh 2-methyl-3-(isoindolinyl-N)-4-phenyl-1H-indene (4.1 g, 12.6 mmol) into the reaction flask, dissolve it in a mixed solvent of 140 mL of toluene and n-hexane (4:3), and place it at low temperature. Start stirring, and then add a n-butyllithium n-hexane solution (5.3 mL, 13.2 mmol) dropwise to the reaction flask. React at room temperature overnight. The solvent in the reaction system is removed by distillation under reduced pressure. Then, add 60 mL of tetrahydrofuran to the residue after distillation and stir to dissolve it to obtain an indenyl lithium salt tetrahydrofuran solution. Weigh N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine (2.1 g, 12.6 mol) and slowly add it dropwise to the above indenyl lithium salt tetrahydrofuran solution. The reaction system is stirred at room temperature overnight. The solvent in the reaction flask is concentrated under reduced pressure to remove the solvent. Then, add 30 mL of n-hexane to the residue in the reaction flask twice for extraction twice, filter and collect the filtrate, and concentrate it under reduced pressure to obtain an oily product (4.9 g, 86%). 1 1H NMR (500 MHz, CDCl3, rt): δ 7.41–7.37 (m, 1H), 7.35–7.30 (m, 2H), 7.14–7.08 (m, 4H), 7.00–6.95 (m, 4H), 6.88–6.84 (m, 1H), 4.21–4.10 (m, 4H), 3.38 (s, 1H), 2.09 (s, 3H), 1.19 (s, 9H), 0.13 (s, 3H), 0.05 (s, 3H).

[0159]

[0160] (3) Preparation of dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-3-(isoindolinyl-N)-4-phenyl-1H-indenyl)amino)titanium (Compound 8)

[0161] Place a dry and clean 250 mL reaction flask in a glove box. Weigh N-(tert-butyl)-1-(2-methyl-3-(isoindolinyl-N)-4-phenyl-1H-indenyl)-1,1-dimethylsilylamine (4.9 g, 10.8 mmol) into the reaction flask and dissolve it in 100 mL of n-hexane. Dropwise add a n-butyllithium n-hexane solution (8.8 mL, 22.2 mmol) to the reaction flask under low temperature conditions. After the system is transferred to room temperature and stirred overnight, filter to collect the filter cake, and add 30 mL of tetrahydrofuran to the filter cake and stir to dissolve. Weigh titanium(III) chloride tetrahydrofuran complex (1:3) (1.2 g, 3.4 mmol) and add it to the tetrahydrofuran solution. After stirring for 2 h, add lead(II) chloride (0.6 g, 2 mmol) and 5 mL of dichloromethane, and react at room temperature overnight. Concentrate the system in the reaction flask under reduced pressure to remove the solvent. Then add 50 mL of toluene to the residue in the reaction flask for extraction, filter to collect the filtrate, and concentrate it under reduced pressure to remove toluene. Then add 30 mL of n-hexane to the residue in the reaction flask for pulping, and filter to obtain 720 mg of a black powder product, which is Compound 8. 1 H NMR(500MHz,CDCl3,rt):δ7.32(d,J=7.4Hz,2H),7.27–7.24(m,2H),7.19–7.07(m,3H),7.01–6.91(m,4H),6.89–6.87(m,1H),4.17(s,4H),2.17(s,3H),1.28(s,9H),0.22(s,3H),0.08(s,3H).

[0162] Polymerization application example

[0163] Introduce 750 mL of n-hexane, 410 mL of 1-octene, and triisobutylaluminum (the molar ratio to the metal complex in the example is 600:1) into the polymerization kettle at room temperature. Heat the polymerization kettle to 120 °C, and at the same time raise the ethylene pressure in the polymerization kettle to 3.7 MPa and add 0.25 MPa of hydrogen. Dissolve the metal complex (1.5 μmol) in the example and triphenylcarbenium tetrakis(pentafluorophenyl)borate (the molar ratio to the metal complex is 2:1) fully in 20 mL of n-hexane to form an activated catalyst solution (the total volume of the polymerization system is 1200 mL, and the concentration of 1-octene is 2.17 mol / L). Subsequently, quickly inject the activated catalyst solution into the polymerization kettle to initiate polymerization, and open the ethylene gas switch to supplement ethylene at any time so that the pressure in the polymerization kettle is maintained at 3.7 MPa. Set the polymerization temperature to 120 °C. After reacting for 30 minutes, close the ethylene inlet switch and the kettle heating switch, then cool down to room temperature, and then release the pressure in the polymerization kettle to atmospheric pressure and open the kettle. Take out the polymer and terminate it with an acid-alcohol solution (ethanol:hydrochloric acid = 9:1). After filtration, dry the polymer to a constant weight, which is the obtained product.

[0164] The physical and chemical properties of the polymers prepared by the catalyst of the present invention and the comparative catalyst were tested, including polymer output, weight-average molecular weight, octene content, melt index, and density. The results are shown in Table 1.

[0165] Table 1 Physical and Chemical Properties of Polymers Prepared by the Catalyst of the Present Invention and the Comparative Catalyst

[0166]

[0167] The metal complex used in Comparative Example 1 in Table 1 is dimethylsilyl(tert-butylamido)tetramethylcyclopentadienyltitanium dichloride.

[0168] The metal complex used in Comparative Example 2 in Table 1 is dimethyl(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(pyrrolidin-1-yl)-1H-inden-1-yl)amido)titanium.

[0169] The above is an exemplary description of the implementation manner of the technical solution of the present invention. It should be understood that the protection scope of the present invention is not limited to the above implementation manner. Any modification, equivalent replacement, improvement, etc. made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the claims of this application.

Claims

1. A compound, characterized in that, The structure of the said compound is shown in Formula I: In formula I, R 1 is selected from any one of hydrogen and C1-C10 alkyl; R 2 selected from any one of C1-C10 alkyl, C1-C10 alkoxy, pyrrolidinyl, pyrrolidinyl substituted by a group selected from C1-C6 alkyl and C1-C6 alkoxy, pyrrolyl, pyrrolyl substituted by a group selected from C1-C6 alkyl and C1-C6 alkoxy, piperidinyl, piperidinyl substituted by a group selected from C1-C6 alkyl and C1-C6 alkoxy, cyclohexylimine group, cyclohexylimine group substituted by a group selected from C1-C6 alkyl and C1-C6 alkoxy, indolinyl, indolinyl substituted by a group selected from C1-C6 alkyl and C1-C6 alkoxy, isoindolinyl, isoindolinyl substituted by a group selected from C1-C6 alkyl and C1-C6 alkoxy, indolyl, indolyl substituted by a group selected from C1-C6 alkyl and C1-C6 alkoxy, tetrahydroquinolinyl, tetrahydroquinolinyl substituted by a group selected from C1-C6 alkyl and C1-C6 alkoxy, tetrahydroisoquinolinyl, and tetrahydroisoquinolinyl substituted by a group selected from C1-C6 alkyl and C1-C6 alkoxy; R 3 selected from any one of C1-C10 alkyl, C3-C7 cycloalkyl, C1-C10 alkoxy, phenyl, phenyl substituted by a group selected from C1-C6 alkyl and C1-C6 alkoxy, benzyl, benzyl substituted by a group selected from C1-C6 alkyl and C1-C6 alkoxy, naphthyl, and naphthyl substituted by a group selected from C1-C6 alkyl and C1-C6 alkoxy; R 4 Any one selected from hydrogen and C1-C10 alkyl groups; R 5 and R 6 are the same or different and each independently selected from any one of hydrogen, C1-C10 alkyl, C3-C7 cycloalkyl, phenyl, C1-C4 alkyl-substituted phenyl, C1-C4 alkoxy-substituted phenyl, benzyl, C1-C4 alkyl-substituted benzyl, and naphthyl; R 7 Selected from any one of C1-C10 alkyl groups and C3-C7 cycloalkyl groups; X 1 、X 2 are the same or different and are each independently selected from halogen, pseudohalogen, halogenated C1-C10 alkyl, C1-C10 alkyl, C1-C10 silyl; M is selected from the elements of Group 4B, and the valence state of M is any one of +2, +3, and +4.

2. The compound according to claim 1, wherein R 2 selected from any one of C1-C10 alkyl, C1-C10 alkoxy, pyrrolidinyl, C1-C4 alkyl-substituted pyrrolidinyl, pyrrolyl, C1-C4 alkyl-substituted pyrrolyl, piperidinyl, C1-C4 alkyl-substituted piperidinyl, cyclohexylimine, C1-C4 alkyl-substituted cyclohexylimine, indolinyl, C1-C4 alkyl-substituted indolinyl, isoindolinyl, and C1-C4 alkyl-substituted isoindolinyl; R 3 Selected from any one of C1-C10 alkyl, C3-C7 cycloalkyl, C1-C10 alkoxy, phenyl, C1-C4 alkyl-substituted phenyl, C1-C4 alkoxy-substituted phenyl, benzyl, C1-C4 alkyl-substituted benzyl, C1-C4 alkoxy-substituted benzyl, naphthyl.

3. The compound according to claim 1 or 2, characterized in that, it satisfies one or more of the following: (1) M is Ti; (2)R 1 selected from hydrogen, C1-C4 alkyl, R 1 preferably hydrogen, methyl, ethyl; (3)R 2 is a C1-C4 alkyl group, pyrrolidinyl group, C1-C4 alkyl-substituted pyrrolidinyl group, pyrrolyl group, C1-C4 alkyl-substituted pyrrolyl group, piperidinyl group, C1-C4 alkyl-substituted piperidinyl group, cyclohexylimino group, C1-C4 alkyl-substituted cyclohexylimino group, indolinyl group, C1-C4 alkyl-substituted indolinyl group, isoindolinyl group, C1-C4 alkyl-substituted isoindolinyl group; R 2 is preferably pyrrolidin-1-yl, 2-methylpyrrolidin-1-yl, 3-methylpyrrolidin-1-yl, pyrrol-1-yl, piperidin-1-yl, cyclohexylimino-1-yl, indolin-1-yl, isoindolin-2-yl, 1-methylisoindolin-2-yl, 1,3-dimethylisoindolin-2-yl; R 2 is preferably pyrrolidin-1-yl, piperidin-1-yl, cyclohexylimino-1-yl, isoindolin-2-yl; (4)R 2 is wherein R 2a is selected from any one or more of C1-C6 alkyl and C1-C6 alkoxy, m1 is selected from 1, 2, 3, m2 is selected from 0, 1, 2, 3, 4, 5, n1 is selected from 1, 2, 3, n2 is selected from 0, 1, and 2 ≤ n1 + n2 ≤ 3, n3 is selected from 0, 1, 2, 3, 4 or 5; R 2 is preferably (5)R 3 is a C1-C4 alkyl group, a C3-C7 cycloalkyl group, a C1-C10 alkoxy group, a phenyl group, a benzyl group, or a C1-C4 alkyl-substituted phenyl group; R 3 is preferably a methoxy group, a methyl group, or a phenyl group; (6)R 4 is hydrogen, C1-C4 alkyl; R 4 is preferably hydrogen; (7)R 5 and R 6 are the same and are C1-C4 alkyl, C3-C7 cycloalkyl, phenyl, benzyl, C1-C4 alkyl-substituted phenyl; R 5 and R 6 are the same and are preferably methyl or benzyl. (8)R 7 Preferably a C1-C4 alkyl group, more preferably butyl, such as tert-butyl; (9)X 1 and X 2 are the same, preferably halogen, C1-C4 alkyl; X 1 and X 2 are the same, preferably Cl, methyl. (10) The said metal compound is selected from at least one of the following compounds:

4. A method for preparing the compound according to any one of claims 1-3, characterized in that, The said preparation method comprises: (1) Using a polysubstituted indanone compound as a raw material to prepare a polysubstituted indene compound; The said polysubstituted indanone compound has a structure shown in Formula Ⅰ-1; In Formula I-1, R 1 , R 3 , R 4 have the meanings as described above; The said polysubstituted indene compound has a structure shown in Formula I-2: In Formula I-2, R 1 , R 2 , R 3 , R 4 has the meanings as described above; (2) Reacting the polysubstituted indene compound obtained in step (1) with a silylamine reagent to obtain the silyl ligand compound of Formula Ⅰ-3; (3) Performing a coordination reaction on the silyl ligand compound obtained in step (2) with a central metal reagent to obtain the compound shown in Formula I.

5. The preparation method according to claim 4, wherein in step (1), reacting the polysubstituted indanone compound shown in Formula I-1 with a nitrogen heterocyclic compound to obtain the polysubstituted indene compound shown in Formula I-2; Preferably, in step (1), the nitrogen heterocyclic compound has the following structure: R 2 H In the formula, R 2 has the meaning of R 2 defined as a nitrogen-containing heterocyclic group; Preferably, in step (1), the molar ratio of the polysubstituted indanone compound to the nitrogen heterocyclic reagent is 1:1 - 1:5; Preferably, in step (1), a Lewis acid reagent needs to be added; preferably, in step (1), the molar ratio of the polysubstituted indanone compound to the Lewis acid reagent is 1:0.1 - 1:1; and / or in step (2), the said silylamine reagent has the following structure: Preferably, in step (2), the molar ratio of the polysubstituted indene compound shown in Formula I-2 to the silylamine reagent is 1:0.8 - 1.2; Preferably, in step (2), an alkyllithium needs to be added; preferably, the molar ratio of the polysubstituted indene compound shown in Formula I-2 to the alkyllithium is 1:1 - 1.2; and / or in step (3), the said central metal reagent is selected from metal compounds containing M, where M represents an element of Group 4B; preferably, in step (3), the said metal compound containing M has the following structure: MCl n (THF) m wherein, n is selected from 2, 3, or 4, and m is selected from 0, 1, 2, or 3; Preferably, in step (3), the molar ratio of the silyl ligand compound to the central metal reagent is 1:0.5 - 1.2; Preferably, in step (3), lead chloride needs to be added; preferably, the molar ratio of the central metal reagent to lead chloride is 10:0 - 10; Preferably, in step (3), dichloromethane is optionally added or not added; preferably, the molar ratio of the silyl ligand compound to dichloromethane is 1:4 - 1:10; and / or The preparation method further includes step (4): when M in the metal complex prepared in step (3) is connected to a halogen, it can further undergo a substitution reaction with an organomagnesium salt or an organolithium salt to obtain X 1 and X 2 are each independently a metal complex selected from a halogenated C1-C10 alkyl group, a C1-C10 alkyl group, and a C1-C10 silyl group; Preferably, the said organic magnesium salt is X’-Mg-X, where X’ is selected from halogenated C1-C10 alkyl, C1-C10 alkyl, C1-C10 silyl; X is selected from halogen; Preferably, the said organic lithium salt is X’-Li, where X’ is selected from halogenated C1-C10 alkyl, C1-C10 alkyl, C1-C10 silyl.

6. Use of the compound according to any one of claims 1-3 as an olefin polymerization catalyst.

7. A catalytic system, characterized in that, The catalytic system comprises the compound according to any one of claims 1-3.

8. Use of the compound according to any one of claims 1-3 or the catalytic system according to claim 7 in olefin polymerization.

9. A process for olefin polymerization, characterized in that, The olefin polymerization method comprises: carrying out an olefin polymerization reaction in the presence of the compound according to any one of claims 1-3 or the catalytic system according to claim 7.

10. A process for copolymerizing olefins, characterized in that, The olefin copolymerization method comprises: carrying out a copolymerization reaction of ethylene and an α-olefin in the presence of the compound according to any one of claims 1-3 or the catalytic system according to claim 7 to obtain a copolymer of ethylene and an α-olefin.

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