Indenyl 4-substituted metal complex, preparation method thereof and application of indenyl 4-substituted metal complex in catalysis of olefin polymerization

Abstract

The invention provides an indenyl 4-substituted metal complex, a preparation method thereof and application of the indenyl 4-substituted metal complex in catalysis of olefin polymerization. The structure of the compound is shown as a formula I. The compound provided by the invention is a novel metallocene catalyst, can improve the coordination polymerization efficiency of a comonomer in a copolymerization process, shows a higher reactivity rate of the comonomer, and further improves the comonomer insertion rate of an olefin polymer. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of metallocene polyolefin catalysts, and particularly relates to an indenyl 4-position substituted metal complex, a preparation method thereof, and an application in catalyzing olefin polymerization. Background Art

[0002] In recent years, with the rapid development of the automotive and photovoltaic industries, the demand for polyolefin products with excellent performance has been increasing, and the scale of the high-end polyolefin market has also been continuously expanding. Among them, an important class of polyolefin elastomers is the copolymer products of ethylene and α-olefins. As a single-site catalyst, metallocene catalysts are applied in the field of polyolefins, and the properties of various polymerization products can be effectively regulated from the molecular design stage, including the stereochemical configuration of polyolefins, the molecular weight and molecular weight distribution of polymers, and the copolymerization reactivity ratios of comonomers. Constrained geometry catalysts (CGCs) have shown high catalytic activity in catalyzing olefin polymerization reactions and have received great attention. Some literature reports the modification of indenyl ligands in the catalyst structure to regulate the activity of the polymerization reaction and various performance indicators of the polymer. A synthesis method and application of a class of CGC-type catalysts have been reported in the literature (CN 117467047 A). These catalysts show high polymerization activity in catalyzing olefin copolymerization. At the same time, due to the introduction of electron-donating substituents at the 3-position of the indenyl ligand, the molecular weight of the polymer is increased. However, the copolymerization reactivity ratios of comonomers during the polymerization reaction are inhibited, resulting in a low comonomer incorporation rate in the polymer.

[0003] Therefore, there is an urgent need to provide a metallocene catalyst that can improve the comonomer incorporation rate of olefin polymers. Summary of the Invention

[0004] The present invention has found through research that by introducing substituents at the 4-position of the indenyl ligand in the catalyst structure, especially introducing bulky or electron-donating groups, the comonomer incorporation rate of olefin polymers can be effectively controlled.

[0005] The technical solution of the present invention is as follows:[[]]

[0006] A compound, the structure of which is shown in Formula I:[[]]

[0007]

[0008] In Formula I, R 1 is selected from any one of hydrogen and C1-C10 alkyl;

[0009] R 2 is selected from any one of C3-C7 cycloalkyl, C1-C10 alkoxy, 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, and naphthyl;

[0010] R 3 Any one selected from hydrogen and C1-C10 alkyl;

[0011] R 4 and R 5 are the same or different and independently of each other are each selected from any one of hydrogen, C1-C10 alkyl, C3-C7 cycloalkyl, C1-C10 alkoxy, phenyl, C1-C6 alkyl-substituted phenyl, C1-C6 alkoxy-substituted phenyl, benzyl, C1-C6 alkyl-substituted benzyl, C1-C6 alkoxy-substituted benzyl, and naphthyl;

[0012] R 6 is selected from any one of C1-C10 alkyl and C3-C7 cycloalkyl;

[0013] X 1 and X 2 are the same or different and independently of each other are each selected from halogen (such as F, Cl, Br, I), halogenated C1-C10 alkyl (such as trifluoromethyl, difluoromethyl, monofluoromethyl), C1-C10 alkyl, and C1-C10 silyl;

[0014] M is selected from the elements of Group 4B (for example, titanium Ti, zirconium Zr, hafnium Hr), 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 represented by Formula I:

[0016] R 1 is selected from any one of hydrogen and C1-C10 alkyl;

[0017] R 2 is selected from any one of 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] R 3 is selected from any one of hydrogen and C1-C10 alkyl;

[0019] R 4 and R 5 are the same or different and independently of each other are each selected from any one of hydrogen, 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;

[0020] R 6Any one selected from C1-C10 alkyl groups and C3-C7 cycloalkyl groups;

[0021] X 1 and X 2 are the same or different and are each independently selected from halogen (such as F, Cl, Br, I), halo C1-C10 alkyl (such as trifluoromethyl, difluoromethyl, monofluoromethyl), C1-C10 alkyl, and C1-C10 silyl;

[0022] M is selected from the elements of Group 4B (for example, titanium Ti, zirconium Zr, hafnium Hf), and the valence state of M is any one of +2, +3, and +4.

[0023] According to an embodiment of the present invention, M is preferably Ti.

[0024] According to an embodiment of the present invention, R 1 is preferably hydrogen, C1-C4 alkyl.

[0025] According to an embodiment of the present invention, R 1 is preferably methyl, ethyl, n-propyl, isopropyl.

[0026] According to an embodiment of the present invention, R 2 is preferably C3-C7 cycloalkyl (such as cyclopentyl), C1-C10 alkoxy (such as methoxy), 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 2 is preferably wherein R 2a is selected from any one or more of C1-C6 alkyl and C1-C6 alkoxy; m is selected from 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 and C1-C4 alkoxy, preferably C1-C4 alkyl. According to an embodiment of the present invention, m is 1, and R 2a is substituted at the ortho, meta, or para position of the phenyl; or m is 2, and R 2a is substituted at the 3- and 5-positions of the phenyl; or m is 5. According to an embodiment of the present invention, R 2a is selected from methyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.

[0028] According to an embodiment of the present invention, R 2 is preferably C1-C4 alkoxy (such as methoxy), phenyl substituted with 1-5 C1-C4 alkyl groups (such as p-tolyl, pentamethylphenyl, p-tert-butylphenyl, 3,5-di-tert-butylphenyl).

[0029] According to an embodiment of the present invention, R 2 is preferably methoxy, p-tolyl, pentamethylphenyl, p-tert-butylphenyl, 3,5-di-tert-butylphenyl.

[0030] According to an embodiment of the present invention, R 3 is preferably hydrogen, C1-C4 alkyl.

[0031] According to an embodiment of the present invention, R 3 is preferably hydrogen.

[0032] According to an embodiment of the present invention, R 4 and R 5 are the same, 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).

[0033] According to an embodiment of the present invention, R 4 and R 5 are the same, preferably methyl, ethyl, n-propyl, isopropyl.

[0034] According to an embodiment of the present invention, R 6 is C1-C4 alkyl, and R 6 is preferably butyl, for example, tert-butyl.

[0035] According to an embodiment of the present invention, X 1 and X 2 are the same, preferably halogen (such as Cl), C1-C4 alkyl (such as methyl).

[0036] According to an embodiment of the present invention, X 1 and X 2 are the same, preferably Cl, methyl.

[0037] According to an embodiment of the present invention, in the compound shown in formula I, R 2 is phenyl substituted by 1-5 C1-C4 alkyl groups; X 1 and X 2 are the same and are C1-C4 alkyl. More preferably, in the compound shown in formula I, R 2 is phenyl substituted by 1, 2 or 3 n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; X 1 and X 2 are the same and are methyl, ethyl. Further preferably, in the compound shown in formula I, R 2 is p-tert-butylphenyl, 3,5-di-tert-butylphenyl; X 1 and X 2 are the same and are methyl.

[0038] According to an embodiment of the present invention, the structure of the compound is shown in the following formula II:

[0039]

[0040] In formula II, R 1 , R 3 , R 4 , R 5 , R 6 , X 1 , X 2 are as described above;

[0041] R 2a is selected from any one or more of C1-C6 alkyl and C1-C6 alkoxy;

[0042] m is selected from 1, 2, 3, 4 or 5.

[0043] According to an embodiment of the present invention, R 2a is selected from any one of C1-C4 alkyl and C1-C4 alkoxy.

[0044] According to an embodiment of the present invention, m is 1, and R 2a is substituted at the ortho, meta or para position of the phenyl group; or m is 2, and R 2a is substituted at the 3-position and 5-position of the phenyl group; or m is 5.

[0045] According to an embodiment of the present invention, R 2a is selected from methyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.

[0046] According to an embodiment of the present invention, in the compound shown in formula II, R 2a is selected from C1-C4 alkyl; X 1 , X 2 are the same and are C1-C4 alkyl. More preferably, in the compound shown in formula II, R 2a is n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; X 1 , X 2 are the same and are methyl, ethyl; m is 1, 2 or 3. Further preferably, in the compound shown in formula II, (R 2a ) m is 4-tert-butyl, 3,5-di-tert-butyl; X 1 , X 2 are the same and are methyl.

[0047] According to an embodiment of the present invention, the compound is selected from at least one of the following compounds:

[0048]

[0049]

[0050] The present invention also provides a method for preparing the compound shown in the above formula I, and the preparation method includes:

[0051] (1) Using a 4-haloindenyl compound as a raw material to prepare a 4-substituted indenyl compound;

[0052] The 4-haloindenyl compound has a structure shown in formula I-1;

[0053]

[0054] In formula I-1, R 1 , R 3 have the meanings as described above, and X is selected from halogens (such as F, Cl, Br, I);

[0055] The 4-substituted indenyl compound has a structure shown in formula I-2:

[0056]

[0057] In formula I-2, R 1 , R 2 , R 3 have the meanings as described above;

[0058] (2) Reacting the 4-substituted indenyl compound prepared in step (1) with a silylamine reagent to obtain a silyl ligand compound shown in formula I-3;

[0059]

[0060] (3) Performing a coordination reaction on the silyl ligand compound prepared in step (2) with a central metal reagent to obtain the compound.

[0061] According to an exemplary embodiment of the present invention, the 4-substituted indenyl compound is, for example, 2-methyl-4-(2,3,4,5,6-pentamethylphenyl)-1H-indene, 2-methyl-4-methoxy-1H-indene, 4-phenyl-1H-indene.

[0062] According to an embodiment of the present invention, the preparation method of the 4-substituted indenyl compound in step (1) is selected from method one or method two, wherein,

[0063] Method one includes: reacting the 4-haloindenyl compound with a boric acid compound to obtain a 4-substituted indenyl compound;

[0064] Method two includes: reacting the 4-haloindenyl compound with sodium alkoxide to obtain a 4-substituted indenyl compound.

[0065] According to an embodiment of the present invention, in Method 1, a palladium complex catalyst also needs to be added, such as tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, palladium acetate, palladium chloride, (1,5-cyclooctadiene)palladium dichloride, [1,2-bis(diphenylphosphino)ethane]palladium dichloride.

[0066] According to an embodiment of the present invention, in Method 1, inorganic bases also need to be added, such as potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, potassium phosphate, potassium hydrogen phosphate, sodium hydroxide, sodium acetate, potassium acetate.

[0067] According to an embodiment of the present invention, in Method 1, quaternary ammonium salt compounds also need to be added, such as tetrabutylammonium bromide, tetrabutylammonium iodide.

[0068] According to an embodiment of the present invention, in Method 1, a mixed solvent or a high-boiling solvent needs to be added, such as a mixed solvent of 1,4-dioxane and water, PEG400, toluene.

[0069] According to an embodiment of the present invention, in Method 1, the molar ratio of the 4-haloindenyl compound to the palladium complex catalyst is 1:0.005 - 1:0.1, such as 1:0.005.

[0070] According to an embodiment of the present invention, in Method 1, the molar ratio of the 4-haloindenyl compound to the inorganic bases is 1:2 - 1:5, such as 1:3.

[0071] According to an embodiment of the present invention, in Method 1, the molar ratio of the 4-haloindenyl compound to the quaternary ammonium salt compounds is 1:1 - 1:2, such as 1:1.

[0072] According to an embodiment of the present invention, in Method 1, the boronic acid compound has the following structure:

[0073] R 2 -B(OH)2

[0074] In the formula, R 2 has the meaning as described above.

[0075] According to an embodiment of the present invention, in Method 1, the boronic acid compound preferably has the following structure:

[0076]

[0077] In the formula, R 2a , m have the meaning as described above.

[0078] According to an exemplary embodiment of the present invention, the boric acid compound is selected from at least one of 2,3,4,5,6-pentamethylphenylboronic acid, p-tert-butylphenylboronic acid, and 3,5-di-tert-butylphenylboronic acid.

[0079] According to an embodiment of the present invention, in the second method, a cuprous halide compound such as cuprous iodide needs to be added.

[0080] According to an embodiment of the present invention, in the second method, an ester compound such as ethyl acetate and methyl formate needs to be added.

[0081] According to an embodiment of the present invention, in the second method, the molar ratio of the 4-haloindenyl compound to the cuprous halide compound is 1:0.1 - 1:1, for example, 1:0.2.

[0082] According to an embodiment of the present invention, in the second method, the molar ratio of the 4-haloindenyl compound to the ester compound is 1:0.5 - 1:2, for example, 1:1.

[0083] According to an exemplary embodiment of the present invention, the sodium alkoxide is selected from at least one of sodium methoxide and sodium ethoxide.

[0084] According to an embodiment of the present invention, the silyl ligand compound is, for example, N-(tert-butyl)-1-(2-methyl-4-(2,3,4,5,6-pentamethylphenyl)-1H-indenyl)-1,1-dimethylsilylamine, N-(tert-butyl)-1-(2-methyl-4-methoxy-1H-indenyl)-1,1-dimethylsilylamine, N-(tert-butyl)-1-(2-methyl-4-phenyl-1H-indenyl)-1,1-dimethylsilylamine, N-(tert-butyl)-1-(2-methyl-4-p-tert-butylphenyl-1H-indenyl)-1,1-dimethylsilylamine, N-(tert-butyl)-1-(2-methyl-4-(3,5-di-tert-butylphenyl)-1H-indenyl)-1,1-dimethylsilylamine, N-(tert-butyl)-1-(4-phenyl-1H-indenyl)-1,1-dimethylsilylamine.

[0085] According to an embodiment of the present invention, in step (2), the silylamine reagent has the structure shown below:

[0086]

[0087] In the formula, R 4 , R 5 , R 6 have the meanings as described above.

[0088] According to an exemplary embodiment of the present invention, the silylamine reagent is selected from at least one of N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine.

[0089] According to an embodiment of the present invention, in step (2), the 4-substituted indenyl compound reacts with a silylamine reagent to form a silyl ligand compound, and 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, and N-(tert-butyl)-N-(1-chloro-1,1-dimethylphenylsilyl)amine.

[0090] According to an embodiment of the present invention, in the method for preparing the silyl ligand compound in step (2), an alkyllithium, such as n-butyllithium, also needs to be added.

[0091] According to an embodiment of the present invention, in the method for preparing the silyl ligand compound in step (2), the molar ratio of the 4-substituted indenyl compound to the silylamine reagent is 1:0.8 - 1.2, for example, 1:1.

[0092] According to an embodiment of the present invention, in the method for preparing the silyl ligand compound in step (2), the molar ratio of the 4-substituted indenyl compound to the alkyllithium is 1:1 - 1.2, for example, 1:1.

[0093] According to an embodiment of the present invention, in step (3), the silyl ligand compound reacts with a central metal reagent to form a compound of formula I (the compound of formula I is a metal complex), and the compound of formula I is, for example, dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-(2,3,4,5,6-pentamethylphenyl)-1H-indenyl)amido)titanium, dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-methoxy-1H-indenyl)amido)titanium, dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-indenyl)amido)titanium, dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-p-tert-butylphenyl-1H-indenyl)amido)titanium, dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-(3,5-di-tert-butylphenyl)-1H-indenyl)amido)titanium, dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-4-phenyl-1H-indenyl)amido)titanium.

[0094] According to an embodiment of the present invention, in 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.

[0095] According to an embodiment of the present invention, in step (3), the metal compound containing M has the following structure:

[0096] MCl n

[0097] In the formula, M has the meaning as described above, and n is selected from 2, 3 or 4.

[0098] 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.

[0099] According to an exemplary embodiment of the present invention, the central metal reagent is, for example, titanium trichloride, titanium tetrachloride.

[0100] According to an embodiment of the present invention, in step (3), lead chloride needs to be further added, and the molar ratio of the central metal reagent to lead chloride is 10:0 - 10, for example, 10:7.5.

[0101] According to an embodiment of the present invention, in step (3), dichloromethane is optionally added or not added, and the molar ratio of the silicon-based ligand compound to dichloromethane is 1:4 - 1:10, for example, 1:5.

[0102] 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 The metal complexes are each independently selected from halogenated C1 - C10 alkyl groups (such as trifluoromethyl, difluoromethyl, monofluoromethyl), C1 - C10 alkyl groups, C1 - C10 silyl groups.

[0103] 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)-2-methyl-4-phenyl-1H-indenyl)amino)titanium, dimethyl(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-p-tert-butylphenyl-1H-indenyl)amino)titanium, dimethyl(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-(3,5-di-tert-butylphenyl)-1H-indenyl)amino)titanium.

[0104] Preferably, the organic magnesium 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.

[0105] Preferably, the organic lithium 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.

[0106] The present invention also provides the use of the complex shown in the above formula I as an olefin polymerization catalyst.

[0107] According to the embodiments of the present invention, the olefin polymerization includes but is not limited to ethylene homopolymerization, copolymerization of ethylene and α-olefins, and copolymerization of ethylene and cyclic olefins.

[0108] The present invention also provides a catalytic system comprising the compound shown in the above formula I.

[0109] According to the embodiments of the present invention, the catalytic system further includes borate salts, for example, including but not limited to at least one of trityl tetrakis(pentafluorophenyl)borate, N,N-dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, etc.

[0110] The present invention also provides the use of the compound or catalytic system shown in the above formula I in olefin polymerization, and the olefin polymerization includes but is not limited to ethylene homopolymerization, copolymerization of ethylene and α-olefins, and copolymerization of ethylene and cyclic olefins.

[0111] The present invention also provides an olefin polymerization method, which includes: carrying out an olefin polymerization reaction in the presence of the compound or catalytic system shown in the above formula I.

[0112] The present invention also provides an olefin copolymerization method, which includes: carrying out a copolymerization reaction of ethylene and α-olefins in the presence of the metal complex or catalytic system shown in the above formula I to obtain a copolymer of ethylene and α-olefins.

[0113] According to the embodiments 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.

[0114] 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 15-80%, preferably 15-70%, for example 20%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%.

[0115] 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 15-80%, preferably 15-70%, for example 20%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%.

[0116] Beneficial effects

[0117] The present invention provides a novel CGC type metallocene catalyst by introducing a substituent (such as a bulky or electron-donating group) at the 4-position of the indenyl ligand in the catalyst structure. The catalyst can improve the coordination polymerization efficiency of the comonomer in the catalytic copolymerization process, thereby increasing the comonomer insertion rate of the olefin polymer.

[0118] The present invention unexpectedly finds that when the substituent at the 4-position of the indenyl ligand in the catalyst structure is a phenyl group substituted by a bulky group (such as tert-butyl), the comonomer insertion rate increases most significantly.

[0119] The present invention uses 4-haloindenyl compounds as starting materials, introduces different types of substituent groups at the 4-position, and synthesizes a variety of novel metallocene catalysts by reacting with silylamine reagents and then coordinating with metal reagents. In the application of olefin polymerization, the metallocene catalysts provided by the present invention show a higher comonomer (such as α-olefin) reactivity ratio compared with traditional CGC type catalysts, and have extremely high application value for improving the performance indexes of olefin polymers.

[0120] The novel metallocene catalyst provided by the present invention can not only improve the comonomer reactivity ratio, thereby increasing the comonomer insertion rate, but also has high catalytic activity, and important indexes such as the comonomer insertion rate and product molecular weight of the prepared polymer are controllable.

[0121] Definitions and explanations:

[0122] C 1-10 selected from C1, C2, C3, C4, C5, C6, C7, C8, C9 and C 10 ; C 3-8 selected from C3, C4, C5, C6, C 7、 C8.

[0123] As used herein, the term "alkyl" should be understood to represent a saturated aliphatic hydrocarbon group having a straight or branched chain. For example, "C 1-10 alkyl" represents straight and branched chain alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, "C 1-6 alkyl" represents straight and branched chain alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms, "C 1-4 alkyl" represents straight 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.

[0124] The term "alkoxy" is "alkyloxy", and "alkyl" is defined as above.

[0125] The term "cycloalkyl" should be understood to represent a saturated monocyclic, bicyclic hydrocarbon ring or tricyclic alkane, where the bicyclic or tricyclic can be a fused ring, bridged ring, spiro ring, for example, "C 3-8 cycloalkyl", preferably "C 3-6 cycloalkyl". The term "C 3-8 cycloalkyl" should be understood to represent a saturated monocyclic, bicyclic hydrocarbon ring or bridged alkane 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.

[0126] As used herein, the term "substituted by..." means substituted by more than 1, for example, 1, 2, 3, 4, 5 or more groups. "Substituted by 1 to 5..." means that it can be substituted by 1, 2, 3, 4 or 5 groups. Detailed Description of the Invention

[0127] 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.

[0128] Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

[0129] Catalyst Preparation

[0130] Synthesis Example 1: Preparation of Dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-(2,3,4,5,6-pentamethylphenyl)-1H-indenyl)amido)titanium (Compound 1)

[0131]

[0132] (1) Preparation of 2-Methyl-4-(2,3,4,5,6-pentamethylphenyl)-1H-indene (Compound 1-1)

[0133] Prepare a dry and clean 250 mL reaction flask, connect it to a Schlenk line, and displace the nitrogen. Weigh 2-methyl-4-bromo-1H-indene (8.3 g, 40 mmol) into the reaction flask, dissolve it in 100 mL of PEG400, start stirring, and then add 2,3,4,5,6-pentamethylphenylboronic acid (8.1 g, 42 mmol), tetrakis(triphenylphosphine)palladium (2.3 g, 2 mmol), tetrabutylammonium bromide (12.9 g, 40 mmol), and potassium carbonate (11.1 g, 80 mmol) to the reaction flask. Heat the system to 110 °C and react overnight. After TLC detection shows that the raw materials are completely converted, add 100 mL of water to quench the reaction, extract the reaction mixture with ethyl acetate (50 mL × 2), combine the organic phases, and then rotary evaporate the organic solvents. The concentrated organic phase is separated by silica gel column chromatography to obtain a pale yellow target product (3.8 g, 35%), which is Compound 1-1. 1 1H NMR (500 MHz, CDCl3, rt): δ 7.32 (d, J = 7.4 Hz, 1H), 7.27–7.19 (m, 1H), 6.93 (dd, J = 7.6, 1.0 Hz, 1H), 6.04–6.01 (m, 1H), 3.36 (s, 2H), 2.07 (d, J = 1.7 Hz, 6H), 1.91 (s, 12H).

[0134]

[0135] (2) Preparation of N-(tert-butyl)-1-(2-methyl-4-(2,3,4,5,6-pentamethylphenyl)-1H-indenyl)-1,1-dimethylsilylamine (Compound 1-2)

[0136] Place a dry and clean 100 mL reaction flask in the glove box. Weigh 2-methyl-4-(2,3,4,5,6-pentamethylphenyl)-1H-indene (1.4 g, 5 mmol) into the reaction flask, dissolve it in 50 mL of n-hexane, place it at low temperature, start stirring, and then add n-butyllithium n-hexane solution (2.1 mL, 5.2 mmol) dropwise to the reaction flask. A large amount of yellow precipitate precipitates, and the reaction is carried out overnight at room temperature. Filter the reaction system, dissolve the filter cake in tetrahydrofuran (50 mL) to obtain a tetrahydrofuran solution of indenyl lithium salt. Weigh N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine (0.8 g, 5 mol) and slowly add it dropwise to the above-mentioned tetrahydrofuran solution of indenyl lithium salt. Stir the reaction system overnight at room temperature. 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 a pale yellow oily product (1.8 g, 89%), which is compound 1-2. 1 HNMR(500MHz,CDCl3,rt):δ7.40(d,J=7.6Hz,1H),7.11(t,J=7.5Hz,1H),6.91(d,J=7.4Hz,1H),6.07(dd,J=2.2,1.2Hz,1H),3.47(s,1H),2.32(s,3H),2.27(d,J=6.4Hz,6H),2.18(d,J=1.4Hz,3H),1.94(s,3H),1.87(s,3H),1.19(s,9H),0.14(s,3H),-0.02(s,3H).

[0137]

[0138] (3) Preparation of dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-(2,3,4,5,6-pentamethylphenyl)-1H-indenyl)amino)titanium (Compound 1)

[0139] Prepare a dry and clean 100 mL reaction flask and place it in a glove box. Weigh N-(tert-butyl)-1-(2-methyl-4-(2,3,4,5,6-pentamethylphenyl)-1H-indenyl)-1,1-dimethylsilylamine (1.3 g, 3.3 mmol) into the reaction flask and dissolve it in 30 mL of n-hexane. Dropwise add a n-hexane solution of n-butyllithium (2.8 mL, 6.8 mmol) to the reaction flask under low temperature conditions. After the system is transferred to room temperature and stirred overnight, the reaction suspension is filtered and the filter cake is added to another dry and clean 100 mL reaction flask. Then add 30 mL of tetrahydrofuran and stir to dissolve. Weigh titanium(III) chloride tetrahydrofuran complex (1:3) (1.3 g, 3.5 mmol) and add it to the system. After stirring for 2 h, add lead(II) chloride (0.6 g, 2.0 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 extract the residue in the reaction flask, filter and collect the filtrate, and concentrate it under reduced pressure to remove toluene. Filter the residue in the reaction flask and wash it with 30 mL of n-hexane to obtain a black solid product (0.55 g, 32%), which is Compound 1. 1 H NMR(500MHz,CDCl3,rt):δ7.42(d,J=7.6Hz,1H),7.16(t,J=7.5Hz,1H),7.06(d,J=7.4Hz,1H),6.14(s,1H),2.19(s,3H),2.24(m,6H),1.92(s,3H),1.81(s,3H),1.41(s,3H),1.05(s,9H),0.31(s,3H),0.22(s,3H).

[0140] Synthesis Example 2: Preparation of dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-methoxy-1H-indenyl)amino)titanium (Compound 2)

[0141]

[0142] (1) Preparation of 2-methyl-4-methoxy-1H-indene (Compound 2-1)

[0143] Prepare a dry and clean 250 mL reaction flask, connect it to a Schlenk line, and displace the nitrogen. Weigh 2-methyl-4-bromo-1H-indene (10.5 g, 50 mmol) into the reaction flask, dissolve it in 50 mL of methanol, start stirring, and then add sodium methoxide (6 g, 100 mmol), copper(I) iodide (1.9 g, 10 mmol), and 5 mL of ethyl acetate to the reaction flask. Heat the system to reflux and react overnight. Add 100 mL of water to quench the system, extract the reaction mixture with ethyl acetate (50 mL×2), combine the organic phases, and then rotary evaporate the organic solvents. The concentrated organic phase is separated by silica gel column chromatography to obtain the target product as a pale yellow oil (3.2 g, 40%), which is compound 2-1. 1 H NMR (500 MHz, CDCl3, rt): δ 7.19 (t, J = 7.8 Hz, 1H), 6.90 (d, J = 7.4 Hz, 1H), 6.65 (d, J = 8.2 Hz, 1H), 6.44 (m, 1H), 3.86 (s, 3H), 3.25 (s, 2H), 2.14 (d, J = 1.5 Hz, 3H).

[0144]

[0145] (2) Preparation of N-(tert-butyl)-1-(2-methyl-4-methoxy-1H-indenyl)-1,1-dimethylsilylamine (Compound 2-2)

[0146] Prepare a dry and clean 100 mL reaction flask and place it in a glove box. Weigh 2-methyl-4-methoxy-1H-indene (1.6 g, 10 mmol) into the reaction flask, dissolve it in 70 mL of n-hexane, place it at low temperature, start stirring, and then slowly add n-butyllithium n-hexane solution (4.2 mL, 10.5 mmol) dropwise to the reaction flask. A large amount of white precipitate precipitates, and react at room temperature overnight. Filter the reaction system, dissolve the filter cake in tetrahydrofuran (50 mL) to obtain an indenyl lithium salt tetrahydrofuran solution. Weigh N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine (1.4 g, 8.4 mmol) and slowly add it dropwise to the above indenyl lithium 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 a pale oil product (2.6 g, 90%), which is compound 2-2. 1 H NMR (500 MHz, CDCl3, rt): δ 7.08 (d, J = 7.5 Hz, 1H), 7.02 (t, J = 7.7 Hz, 1H), 6.72–6.67 (m, 2H), 3.88 (s, 3H), 3.42 (s, 1H), 2.26 (d, J = 1.5 Hz, 3H), 1.19 (s, 9H), 0.11 (s, 3H), -0.08 (s, 3H).

[0147]

[0148] (3) Preparation of Dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-methoxy-1H-indenyl)amino)titanium (Compound 2)

[0149] Prepare a dry and clean 250 mL reaction flask and place it in a glove box. Weigh N-(tert-butyl)-1-(2-methyl-4-methoxy-1H-indenyl)-1,1-dimethylsilylamine (2.6 g, 9 mmol) into the reaction flask and dissolve it in 80 mL of n-hexane. Dropwise add n-butyllithium n-hexane solution (7.4 mL, 18.4 mmol) into the reaction flask under low temperature conditions. After the system is transferred to room temperature and stirred overnight, the reaction suspension is filtered and the filter cake is added to another dry and clean 250 mL reaction flask. Then add 90 mL of tetrahydrofuran and stir to dissolve. Weigh titanium(III) chloride tetrahydrofuran complex (1:3) (4.0 g, 10.8 mmol) and add it to the system. 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 and collect the filtrate, and concentrate it under reduced pressure to remove toluene. Filter the residue in the reaction flask and wash it with 30 mL of n-hexane to obtain a brown solid product (1.2 g, 33%), which is Compound 2. 1 H NMR(500MHz,CDCl3,rt): 1 H NMR(500MHz,CDCl3,rt):δ7.19(d,J=7.5Hz,1H),7.16(t,J=7.5Hz,1H),7.06(t,J=7.7Hz,1H),6.57(s,1H),3.93(s,3H),2.37(s,3H),1.38(s,9H),0.87(s,3H),0.76(s,3H).

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

[0151]

[0152] (1) Preparation of N-(tert-butyl)-1-(2-methyl-4-phenyl-1H-indenyl)-1,1-dimethylsilylamine (Compound 3-1):

[0153] Place a dry and clean 250 mL reaction flask in the glove box. Weigh 2-methyl-4-phenyl-1H-indene (10.3 g, 50 mmol) into the reaction flask, dissolve it in 150 mL of n-hexane, place it at low temperature, start stirring, and then dropwise add n-butyllithium n-hexane solution (22 mL, 55 mmol) into 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 (100 mL) to obtain a tetrahydrofuran solution of indenyl lithium salt. Weigh N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine (8.3 g, 50 mol) and slowly drop it into 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 40 mL of n-hexane to the residue in the reaction flask twice for extraction, filter and collect the filtrate, and concentrate it under reduced pressure to obtain a light oil product (15.4 g, 92%), which is compound 3-1. 1 H NMR(500MHz,CDCl3,rt):δ7.61–7.56(m,2H),7.51–7.44(m,4H),7.40–7.36(m,1H),7.18(t,J=7.5Hz,1H),6.77(q,J=1.2Hz,1H),3.52(s,1H),2.31(s,3H),1.24(s,9H),0.20(s,3H),0.02(s,3H).

[0154]

[0155] (2) Preparation of dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-indenyl)amino)titanium (Compound 3)

[0156] : Place a dry and clean 250 mL reaction flask in the glove box. Weigh N-(tert-butyl)-1-(2-methyl-4-phenyl-1H-indenyl)-1,1-dimethylsilylamine (6.7 g, 20 mmol) into the reaction flask and dissolve it in 50 mL of n-hexane. Dropwise add n-butyllithium n-hexane solution (17.6 mL, 44 mmol) to the reaction flask under low temperature conditions. After the system is transferred to room temperature and stirred overnight, the reaction suspension is filtered and the filter cake is added to another dry and clean 250 mL reaction flask. Then add 100 mL of tetrahydrofuran and stir to dissolve. Weigh titanium(III) chloride tetrahydrofuran complex (1:3) (8.9 g, 24 mmol) and add it to the system. After stirring for 2 h, add lead(II) chloride (3.9 g, 14 mmol) 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 and collect the filtrate, and concentrate it under reduced pressure to remove toluene. Then add 50 mL of diethyl ether to the residue in the reaction flask and stir for overnight. Filter and collect the filter cake, and dry it to obtain 1.1 g of pink solid product, which is Compound 3. 1 H NMR(500MHz,CDCl3,rt):δ7.73(d,J=8.0Hz,1H),7.61–7.56(m,2H),7.48(t,J=7.6Hz,2H),7.41(dd,J=8.4,6.3Hz,1H),7.37–7.29(m,2H),7.19(s,1H),2.38(s,3H),1.41(s,9H),0.95(s,3H),0.80(s,3H).

[0157] Synthesis Example 4: Preparation of dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-p-tert-butylphenyl-1H-indenyl)amido)titanium (Compound 4)

[0158]

[0159] (1) Preparation of N-(tert-butyl)-1-(2-methyl-4-p-tert-butylphenyl-1H-indenyl)-1,1-dimethylsilylamine (Compound 4-1)

[0160] Place a dry and clean 250 mL reaction flask in the glove box. Weigh 2-methyl-4-(4-tert-butylphenyl)-1H-indene (13 g, 50 mmol) into the reaction flask, dissolve it in 150 mL of n-hexane, and place it at low temperature. Start stirring, and then slowly add n-butyllithium n-hexane solution (22 mL, 55 mmol) dropwise to the reaction flask. A large amount of precipitate will form, and the reaction will proceed overnight at room temperature. Filter the reaction system, dissolve the filter cake in tetrahydrofuran (100 mL) to obtain a solution of indenyl lithium salt in tetrahydrofuran. Weigh N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine (8.3 g, 50 mmol) and slowly add it dropwise to the above solution of indenyl lithium salt in tetrahydrofuran. Stir the reaction system overnight at room temperature. Concentrate the reaction system in the reaction flask under reduced pressure to remove the solvent. Then, add 40 mL of n-hexane to the residue in the reaction flask twice for extraction, filter to collect the filtrate, and concentrate it under reduced pressure to obtain a light oily product (18.3 g, 94%), which is compound 4-1. 1 H NMR(500MHz,CDCl3,rt):δ7.39(d,J=2.8Hz,4H),7.31(d,J=7.5Hz,1H),7.13(d,J=7.5Hz,1H),7.04(t,J=7.5Hz,1H),6.67(s,1H),3.38(s,1H),2.17(d,J=1.5Hz,3H),1.30(s,9H),1.10(s,9H),0.07(s,3H),-0.12(s,3H).

[0161]

[0162] (2) Preparation of Dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-(4-tert-butylphenyl)-1H-indenyl)amido)titanium (Compound 4)

[0163] Place a dry and clean 250 mL reaction flask in the glove box. Weigh N-(tert-butyl)-1-(2-methyl-4-p-tert-butylphenyl-1H-indenyl)-1,1-dimethylsilylamine (7.8 g, 20 mmol) into the reaction flask and dissolve it in 50 mL of n-hexane. Dropwise add n-butyllithium n-hexane solution (17.6 mL, 44 mmol) to the reaction flask under low temperature conditions. After the system is transferred to room temperature and stirred overnight, the solvent of the reaction system is removed by distillation under reduced pressure. The residue is dissolved in 100 mL of tetrahydrofuran. Weigh titanium(III) chloride tetrahydrofuran complex (1:3) (8.9 g, 24 mmol) and add it to the system. After stirring for 2 h, add lead(II) chloride (3.9 g, 14 mmol), and react at room temperature overnight. Concentrate the system in the reaction flask under reduced pressure to remove the solvent. Add 50 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. Add 50 mL of n-hexane to the residue in the reaction flask and slurry overnight, filter and collect the filter cake, and dry to obtain 1.0 g of a red solid product, which is compound 4. 1 H NMR(500MHz,CDCl3,rt):δ7.71(d,J=8.3Hz,1H),7.56–7.48(m,4H),7.36–7.27(m,2H),7.24(s,1H),2.38(s,3H),1.41(s,9H),1.38(s,9H),0.95(s,3H),0.80(s,3H).

[0164] Synthesis Example 5: Preparation of dimethyl(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-p-tert-butylphenyl-1H-indenyl)amino)titanium (Compound 5)

[0165]

[0166] Dimethyl(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-p-tert-butylphenyl-1H-indenyl)amino)titanium: 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-4-p-tert-butylphenyl-1H-indenyl)amino)titanium (0.5 g, 1 mmol) into the reaction flask and dissolve it in 20 mL of diethyl ether. Dropwise add methylmagnesium chloride tetrahydrofuran solution (0.8 mL, 2.2 mmol) to the reaction flask under low temperature conditions. After the system is transferred to room temperature and stirred overnight, the system in the reaction flask is concentrated under reduced pressure to remove the solvent. Add 30 mL of n-hexane to the residue in the reaction flask for extraction, filter and collect the filtrate, and concentrate it under reduced pressure to obtain a yellow powder product (0.36 g, 77%), which is compound 5, and store it at low temperature in the glove box.1 1H NMR (500 MHz, CDCl3, rt): δ 7.71 (d, J = 8.4 Hz, 1H), 7.54 (d, J = 8.5 Hz, 1H), 7.43 (d, J = 8.4 Hz, 1H), 7.30–7.23 (m, 2H), 7.15–7.11 (m, 1H), 7.04–6.98 (m, 2H), 2.11 (s, 3H), 1.50 (s, 9H), 1.29 (s, 9H), 0.90 (s, 3H), 0.62 (s, 3H), 0.49 (s, 3H), 0.07 (s, 3H).

[0167] Synthesis Example 6: Preparation of Dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-(3,5-di-tert-butylphenyl)-1H-indenyl)amino)titanium (Compound 6)

[0168]

[0169] (1) Preparation of N-(tert-butyl)-1-(2-methyl-4-(3,5-di-tert-butylphenyl)-1H-indenyl)-1,1-dimethylsilylamine (Compound 6-1)

[0170] Prepare a dry and clean 250 mL reaction flask and place it in the glove box. Weigh 2-methyl-4-(3,5-di-tert-butylphenyl)-1H-indene (9.5 g, 30 mmol) into the reaction flask, dissolve it in 100 mL of n-hexane, place it at low temperature, start stirring, and then add n-butyllithium n-hexane solution (13 mL, 33 mmol) dropwise to the reaction flask. React at room temperature overnight. Distill off the solvent from the system under reduced pressure, and then add 60 mL of tetrahydrofuran to the residue of the reaction system and stir to dissolve to obtain an indenyllithium salt tetrahydrofuran solution. Weigh N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine (5.0 g, 30 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 40 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 a light oil-like product (13 g, 98%). 1 1H NMR (500 MHz, CDCl3, rt): δ 7.41–7.35 (m, 3H), 7.26–7.22 (m, 2H), 7.13 (t, J = 7.5 Hz, 1H), 6.71 (s, 1H), 3.46 (s, 1H), 2.25 (s, 3H), 1.38 (s, 18H), 1.17 (s, 9H), 0.17 (s, 3H), -0.01 (s, 3H).

[0171]

[0172] (2) Preparation of dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-(3,5-di-tert-butylphenyl)-1H-indenyl)amino)titanium (Compound 6)

[0173] Prepare a dry and clean 100 mL reaction flask and place it in a glove box. Weigh N-(tert-butyl)-1-(2-methyl-4-(3,5-di-tert-butylphenyl)-1H-indenyl)-1,1-dimethylsilylamine (7.5 g, 16 mmol) into the reaction flask and dissolve it in 30 mL of n-hexane. Dropwise add n-butyllithium n-hexane solution (14.7 mL, 36 mmol) to the reaction flask under low temperature conditions. After the system is transferred to room temperature and stirred overnight, the solvent of the reaction system is removed by vacuum distillation. The residue is dissolved in 100 mL of tetrahydrofuran. Weigh titanium trichloride tetrahydrofuran complex (1:3) (7.4 g, 20 mmol) and add it to the system. After stirring for 2 h, add lead chloride (3.2 g, 12 mmol) and react at room temperature overnight. Concentrate the system in the reaction flask under reduced pressure to remove the solvent. Add 50 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. Add 50 mL of ether to the residue in the reaction flask and slurry overnight, filter and collect the filter cake, and dry to obtain 0.7 g of a red solid product, which is Compound 6. 1 H NMR(500MHz,CDCl3,rt):δ7.71(d,J=8.5Hz,1H),7.48(t,J=1.9Hz,1H),7.44(d,J=1.8Hz,2H),7.39–7.30(m,2H),7.19(s,1H),2.38(s,3H),1.42(s,9H),1.39(s,18H),0.95(s,3H),0.80(s,3H).

[0174] Synthesis Example 7: Preparation of dimethyl(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-2-methyl-4-(3,5-di-tert-butylphenyl)-1H-indenyl)amino)titanium (Compound 7)

[0175]

[0176] 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-4-(3,5-di-tert-butylphenyl)-1H-indenyl)amido)titanium (0.56 g, 1 mmol) into the reaction flask and dissolve it in 35 mL of diethyl ether. Dropwise add methylmagnesium chloride tetrahydrofuran solution (1.0 mL, 3 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 40 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 yellow powder product (0.35 g, 67%), which is compound 7, and store it at low temperature in the glove box. 1 H NMR(500MHz,CDCl3,rt):δ7.48–7.35(m,4H),7.19(dd,J=13.1,7.4Hz,2H),7.11(d,J=5.1Hz,1H),7.06(t,J=7.4Hz,1H),2.08(s,3H),1.46(s,9H),1.32(s,18H),0.65(s,3H),0.59(s,3H),0.53(s,3H),-0.49(s,3H).

[0177] Polymerization application example

[0178] 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 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 turn on the ethylene gas switch to supplement ethylene at any time, so as to maintain the pressure in the polymerization kettle at 3.7 MPa. Set the polymerization temperature to 120 °C. After reacting for 30 minutes, turn off the ethylene inlet switch and the kettle body heating switch, then cool down to room temperature, and then relieve 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 to obtain the product.

[0179] Test the physical and chemical properties of the polymers prepared by different catalysts, including weight-average molecular weight, octene content, and density. The results are shown in Table 1.

[0180] Table 1 Physical and chemical properties of polymers prepared by different catalysts

[0181]

[0182] The metal complex used in the comparative example in Table 1 is dimethyl(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(pyrrolidin-1-yl)-1H-indenyl)amido)titanium.

[0183] The experimental results of the application examples show that the compounds of the present invention can significantly improve the comonomer insertion rate of olefin polymers.

[0184] The above has given an exemplary description of the implementation manners 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 manners. Any modifications, equivalent substitutions, improvements, 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: Wherein: R 1 Any one selected from hydrogen and C1-C10 alkyl groups; R 2 selected from any one of C3-C7 cycloalkyl, C1-C10 alkoxy, 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, and naphthyl; R 3 Any one selected from hydrogen and C1-C10 alkyl groups; R 4 、R 5 are the same or different and are each independently selected from any one of hydrogen, C1-C10 alkyl, C3-C7 cycloalkyl, C1-C10 alkoxy, phenyl, C1-C6 alkyl-substituted phenyl, C1-C6 alkoxy-substituted phenyl, benzyl, C1-C6 alkyl-substituted benzyl, C1-C6 alkoxy-substituted benzyl, naphthyl; R 6 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 the fourth subgroup, 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 C3-C7 cycloalkyl, C1-C10 alkoxy, C1-C4 alkyl-substituted phenyl, C1-C4 alkoxy-substituted phenyl, benzyl, C1-C4 alkyl-substituted benzyl, C1-C4 alkoxy-substituted benzyl, naphthyl; R 4 and R 5 are the same or different and each independently selected from any one of hydrogen, 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 is hydrogen, C1-C4 alkyl; preferably, R 1 is methyl, ethyl, n-propyl, or isopropyl; (3)R 2 is a C3-C7 cycloalkyl group, a C1-C10 alkoxy group, a benzyl group, or a C1-C4 alkyl-substituted phenyl group; preferably, R 2 is a C1-C4 alkoxy group, a phenyl group, or a phenyl group substituted with 1-5 C1-C4 alkyl groups; preferably, R 2 is a methoxy group, a phenyl group, a p-tolyl group, a pentamethylphenyl group, a p-tert-butylphenyl group, or a 3,5-di-tert-butylphenyl group; (4)R 3 is hydrogen, C1-C4 alkyl; preferably, R 3 is hydrogen; (5)R 4 and R 5 are the same and are C1-C4 alkyl, C3-C7 cycloalkyl, phenyl, benzyl, C1-C4 alkyl-substituted phenyl; preferably, R 4 and R 5 are the same and are methyl, ethyl, n-propyl, isopropyl; (6)R 6 is a C1-C4 alkyl group; preferably, R 6 is butyl, such as tert-butyl; (7)X 1 and X 2 are the same and are halogen, C1-C4 alkyl; preferably, X 1 and X 2 are Cl and methyl; (8)R 2 is a phenyl group substituted by 1 to 3 n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl groups; X 1 , X 2 are the same and are methyl or ethyl; Further preferably, R 2 is p-tert-butylphenyl or 3,5-di-tert-butylphenyl; X 1 , X 2 are the same and are methyl; (9) The structure of the said compound is shown in the following Formula II: In formula II, R 2a is selected from any one or more of C1-C6 alkyl and C1-C6 alkoxy; m is selected from 1, 2, 3, 4 or 5; preferably, R 2a is selected from any one of C1-C4 alkyl and C1-C4 alkoxy; preferably, R 2a is selected from methyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; preferably, in the compound represented by formula II, R 2a is n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; X 1 , X 2 are the same and are methyl, ethyl; m is 1, 2 or 3; further preferably, in the compound represented by formula II, (R 2a ) m is 4-tert-butyl, 3,5-di-tert-butyl; X 1 , X 2 are the same and are methyl; (10) The said compound is selected from at least one of the following compounds:

4. A process for preparing the compound according to any one of claims 1-3, characterized in that, The said preparation method includes: (1) Using a 4-haloindenyl compound as a raw material to prepare a 4-substituted indenyl compound; The said 4-haloindenyl compound has a structure shown in Formula I-1; In formula I-1, R 1 , R 3 has the meaning as described in any one of claims 1-3, and X is selected from halogen; The said 4-substituted indenyl compound has a structure shown in Formula I-2: In Formula I-2, R 1 , R 2 , R 3 has the meaning as described in any one of Claims 1-3; (2) Reacting the 4-substituted indenyl compound prepared in step (1) with a silylamine reagent to obtain a silyl ligand compound shown in Formula I-3; In Formula I-3, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 has the meaning as described in any one of Claims 1-3; (3) Performing a coordination reaction on the silyl ligand compound prepared in step (2) with a central metal reagent to obtain the said compound.

5. The preparation method according to claim 4, characterized in that, The preparation method of the 4-substituted indenyl compound in step (1) is selected from Method 1 or Method 2, wherein Method 1 includes: Reacting the said 4-haloindenyl compound with a boric acid compound to obtain a 4-substituted indenyl compound; Method 2 includes: Reacting the said 4-haloindenyl compound with sodium alkoxide to obtain a 4-substituted indenyl compound; Preferably, in Method 1, a palladium complex catalyst needs to be added; preferably, in Method 1, the molar ratio of the 4-haloindenyl compound to the palladium complex catalyst is 1:0.005 - 1:0.1; Preferably, in Method 1, inorganic bases need to be added; preferably, in Method 1, the molar ratio of the 4-haloindenyl compound to the inorganic bases is 1:2 - 1:5; Preferably, in Method 1, quaternary ammonium salt compounds need to be added; preferably, in Method 1, the molar ratio of the 4-haloindenyl compound to the quaternary ammonium salt compounds is 1:1 - 1:2; Preferably, in Method 1, a mixed solvent or a high-boiling solvent needs to be added; Preferably, in Method 1, the boric acid compound has the following structure: R 2 -B(OH)2 Preferably, in Method 1, the boric acid compound has the following structure: Preferably, in Method 2, cuprous halide compounds need to be added; preferably, in Method 2, the molar ratio of the 4-haloindenyl compound to the cuprous halide compounds is 1:0.1 - 1:1; Preferably, in Method 2, ester compounds need to be added; preferably, in Method 2, the molar ratio of the 4-haloindenyl compound to the ester compounds is 1:0.5 - 1:2; and / or Preferably, in step (2), the said silylamine reagent has the following structure: Preferably, in step (2), an alkyllithium needs to be added; preferably, in step (2), the molar ratio of the 4-substituted indenyl compound to the alkyllithium is 1:1 - 1.2; Preferably, in step (2), the molar ratio of the 4-substituted indenyl compound to the silylamine reagent is 1:0.8 - 1.2; and / or Preferably, in step (3), the central metal reagent is selected from metal compounds containing M, where M represents an element of Group 4B; preferably, the metal compound containing M has the structure shown below: MCl n 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 metal complexes independently selected from halogenated C1-C10 alkyl groups, C1-C10 alkyl groups, and C1-C10 silyl groups; Preferably, in step (4), the organic magnesium salt is X’-Mg-X, where X’ is selected from halogenated C1-C10 alkyl groups, C1-C10 alkyl groups, C1-C10 silyl groups; X is selected from halogens; Preferably, in step (4), the organic lithium salt is X’-Li, where X’ is selected from halogenated C1-C10 alkyl groups, C1-C10 alkyl groups, C1-C10 silyl groups.

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 method for olefin copolymerization, 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.

Images