Benzyl amino side arm-containing biphenyl half-cyclopentadienyl fourth subgroup metal complex as well as preparation method and application thereof

Abstract

The invention discloses a benzylamino side arm-containing biphenyl mono-cyclopentadienyl fourth subgroup metal complex as well as a preparation method and application thereof. The benzylamino side arm-containing biphenyl half-cyclopentadienyl fourth subgroup metal complex as shown in the formula (I) can enhance protection on an active metal center, is high and durable in catalytic activity, can tolerate higher polymerization temperature, obviously improves the thermal stability of a catalyst, greatly prolongs the service life, and is especially suitable for catalyzing olefin polymerization reaction. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of olefin polymerization catalysts, and particularly relates to a type of benzylamino-sidearm biphenyl monocyclopentadienyl fourth subgroup metal complex, a preparation method thereof and an application thereof in catalyzing olefin polymerization. Background Art

[0002] Metallocene catalysts have attracted extensive attention from academia and industry for their high catalytic activity, good polymer structure controllability, excellent comonomer insertion ability and wide comonomer applicability. Using metallocene complexes to catalyze olefin homopolymerization or copolymerization, high-performance polyolefin products such as EPDM and EPDM rubber, polyolefin elastomers, and cycloolefin copolymers (COC) can be produced. These polyolefin materials are widely used in packaging, medical devices and consumables, wires and cables, household appliances, automobiles, building materials, etc. The composition and molecular weight of these polyolefin materials mainly depend on the catalyst used in the production process.

[0003] There are many types of metallocene catalysts reported so far, but due to the difficulties faced in metallocene synthesis and polyolefin production processes, few can meet the production requirements of industrial devices. For example, the polyolefin elastomer produced by copolymerization of ethylene and 1-octene catalyzed by the constrained geometry configuration (CGC) mono-titanocenes (EP0416815A2) developed by the Dow Chemical Company has a relatively low molecular weight, with a maximum weight-average molecular weight of only 160,000, and its mechanical strength cannot meet the requirements of many high-end applications. Although the molecular weight of the copolymer produced by the copolymerization of ethylene and 1-octene catalyzed by the phenyl-bridged amino side chain monotitanocenes catalyst (Organometallics, 2008, 27, 3907) is improved, the maximum weight average molecular weight is only 250,000; WO2007 / 078134 discloses a class of mononuclear and binuclear catalysts with phenyl-bridged amino side chains of similar structure and a synthesis method thereof, the catalyst has poor copolymerization performance and obtains polymers with low molecular weight. Similarly, the biphenyl-bridged amino side chain monotitanocenes catalysts with similar structure disclosed in US9868797B2 also show poor copolymerization performance; at the same time, the synthesis process of these catalysts requires the use of palladium catalysts, resulting in high catalyst costs or the use of highly dangerous tert-butyl lithium reagents, which is not conducive to the scale-up synthesis and industrial application of the catalysts. The copolymerization of ethylene and 1-hexene catalyzed by N-arylphenyl bridged benzylamino sidearm monotitanocenes (ZL03110834.2) developed by Sumitomo Chemical Co., Ltd. of Japan can produce copolymers with high molecular weight, but the copolymerization performance of this catalyst is general; the polymer obtained by N-cyclohexylphenyl bridged benzylamino sidearm monotitanocenes catalyst (Organometallics, 2013, 32, 4185) is still difficult to be compatible with high molecular weight and high comonomer content, and cannot meet the requirements of high-end applications. CN113185545B discloses a synthesis method and application of a type of benzylamino sidearm monotitanocenes containing special structures. This type of catalyst can catalyze olefin polymerization with high activity to obtain polymers with high molecular weight and insertion rate, but this type of catalyst still needs to be further improved in terms of temperature resistance, catalytic activity and other properties, and the selectivity of the catalyst in catalyzing α-olefin homopolymerization is unclear.

[0004] In summary, although the above-mentioned known catalysts show excellent performance in some aspects, they all have the disadvantage of poor performance in some aspects. When catalyzing the copolymerization or homopolymerization of ethylene and propylene or long-chain α-olefins, there is still the problem of not being able to simultaneously obtain polymers with high comonomer content, high molecular weight and high selectivity. Therefore, in the field of polyolefin products, it is still necessary to develop catalysts with low cost, high catalytic activity, high selectivity and certain copolymerization performance, which are suitable for preparing polyolefins by high-temperature solution polymerization. Summary of the invention

[0005] In order to overcome the above-mentioned defects existing in the prior art, an object of the present invention is to provide a fourth-group metal complex of biphenyl monocyclopentadienyl containing a benzylamino sidearm. The synthesis route of this type of complex is simple and it can catalyze olefin polymerization with high activity and selectivity to obtain polymers with high molecular weight and comonomer content.

[0006] Another object of the present invention is to provide a method for preparing a fourth subgroup metal complex of biphenyl monocyclopentadienyl containing a benzylamino side arm.

[0007] Another object of the present invention is to provide a use of a benzylamino sidearm biphenyl monocyclopentadienyl group IV metal complex in catalyzing olefin polymerization.

[0008] Another object of the present invention is to provide a method for polymerizing ethylene.

[0009] Another object of the present invention is to provide a method for polymerizing propylene.

[0010] In order to achieve the above object, the present invention adopts the following technical solution:

[0011] In the first aspect, the present invention provides a benzylamino sidearm biphenyl monocyclopentadienyl group 4 metal complex having a structural formula shown in the following formula (I):

[0012]

[0013] In formula (I),

[0014] M is titanium, zirconium or hafnium;

[0015] Cp' is a substituted or unsubstituted group as follows: cyclopentadienyl, indenyl, benzoindenyl, fluorenyl;

[0016] R is a substituted or unsubstituted group as follows: C1-C30 alkyl, C3-C10 cycloalkyl, C6-C20 aryl;

[0017] Each X is independently halogen, C1-C30 alkyl, substituted C1-C30 alkyl, C1-C30 alkoxy, substituted C1-C30 alkoxy, amine, substituted amine, C6-C20 aryl, substituted C6-C20 aryl, C6-C20 arylC1-C10 alkyl, substituted C6-C20 arylC1-C10 alkyl.

[0018] In some embodiments, in formula (I):

[0019] M is titanium, zirconium or hafnium;

[0020] Cp' is cyclopentadienyl, monomethylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, methylethylcyclopentadienyl, methylpropylcyclopentadienyl, methylbutylcyclopentadienyl, dimethyldiphenylcyclopentadienyl, diphenylcyclopentadienyl, indenyl, monomethylindenyl, dimethylindenyl, benzoindenyl, 2-methylbenzoindenyl, 3-dimethylaminoindenyl, 3-diethylaminoindenyl, 3-tetrahydropyrrolylindenyl, 3-piperidinylindenyl, 2-methyl-4-phenylindenyl, 2-benzylindenyl, 2-p-methylbenzylindenyl, 2-p-fluorobenzylindenyl, fluorenyl, dimethylfluorenyl, di-tert-butylfluorenyl;

[0021] R is ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, isopentyl, tert-pentyl, n-hexyl, 2-hexyl, 3-hexyl, isohexyl, tert-hexyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, isoheptyl, tert-heptyl, n-octyl and various isomeric octyl, n-nonyl and various isomeric nonyl, n-decyl and various isomeric decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, diphenylmethyl, phenyl, o-tolyl, p-tolyl, 2,4-dimethylbenzene phenyl, 2,6-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, o-ethylphenyl, p-ethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 3,5-diethylphenyl, 2,4,6-triethylphenyl, o-isopropylphenyl, p-isopropylphenyl, 2,4-diisopropylphenyl, 3,5-diisopropylphenyl, 2,4,6-triisopropylphenyl, o-tert-butylphenyl, p-tert-butylphenyl, 2,4-di-tert-butylphenyl, 3,5-di-tert-butylphenyl, 4-methyl-2,6-di-tert-butylphenyl;

[0022] Each X is independently chlorine, bromine, iodine, methyl, neopentyl, trimethylsilyl, methoxy, ethoxy, isopropoxy, tert-butoxy, dimethylamino, diethylamino, diisopropylamino, bistrimethylsilylamino, or benzyl.

[0023] In some embodiments, in formula (I):

[0024] M is titanium, zirconium or hafnium; preferably, M is titanium or zirconium;

[0025] Cp' is cyclopentadienyl, tetramethylcyclopentadienyl, dimethyldiphenylcyclopentadienyl, indenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, 3-dimethylaminoindenyl, 3-diethylaminoindenyl, 3-tetrahydropyrrolylindenyl, 3-piperidinylindenyl, 2-methylbenzoindenyl, fluorenyl, 3,6-dimethylfluorenyl, 3,6-di-tert-butylfluorenyl; preferably, Cp' is tetramethylcyclopentadienyl, indenyl, 2-methylindenyl, fluorenyl;

[0026] R is ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, diphenylmethyl, phenyl, o-tolyl, p-tolyl, 2,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 3,5-diethylphenyl, 2,4,6-triethylphenyl, 2,4-diisopropylphenyl, 3,5-diisopropylphenyl, 2,4-di-tert-butylphenyl, 3,5-di-tert-butylphenyl; preferably, R is n-propyl, isopropyl, cyclopentyl, cyclohexyl, tert-butyl, phenyl, diphenylmethyl;

[0027] Each X is independently chlorine, bromine, methyl, trimethylsilyl, isopropoxy, tert-butoxy, dimethylamino, diethylamino, benzyl; preferably, each X is simultaneously chlorine.

[0028] In some embodiments, the benzylamino sidearm biphenyl monocyclopentadienyl group 4 metal complex represented by formula (I) is selected from the following structures:

[0029]

[0030] In a second aspect, the present invention provides a method for preparing the benzylamino sidearm biphenyl monocyclopentadienyl group 4 metal complex, the reaction scheme of which is as follows:

[0031]

[0032] Wherein, Cp', R, and M are defined as above;

[0033] X1 is selected from C1-C30 alkyl (e.g., methyl) and substituted C1-C30 alkyl; X2 is selected from halogen (e.g., Cl); X3 is selected from amine, substituted amine, C6-C20 aryl C1-C10 alkyl (e.g., benzyl) and substituted C6-C20 aryl C1-C10 alkyl (e.g., substituted benzyl);

[0034] The preparation method comprises the following steps:

[0035] (1) the compound represented by formula (II) reacts with an organic amine RNH2, and the reaction product reacts with a reducing agent (such as sodium borohydride) to obtain a ligand precursor (III);

[0036] (2) The ligand precursor (III) is synthesized according to the route selected from (b) to (d) to synthesize the fourth group metal complex containing a benzylamino side arm biphenyl monocyclopentadienyl:

[0037] (b) under an inert atmosphere, the ligand precursor (III) reacts with an alkyl lithium (e.g., n-butyl lithium) or an alkyl Grignard reagent, and the reaction product reacts with an M metal halide (e.g., MCl4) to obtain a benzylamino-sidearm biphenyl monocyclopentadienyl group 4 metal complex as shown in formula (I-1);

[0038] (c) under an inert atmosphere, the ligand precursor (III) reacts with an alkyl lithium or alkyl Grignard reagent, the reaction product reacts with trimethylsilyl chloride, and the reaction product reacts with a metal halide M to obtain a benzylamino sidearm biphenyl monocyclopentadienyl group IV metal complex as shown in formula (I-2);

[0039] (d) The ligand precursor (III) reacts with M metal amide or metal benzyl compound to obtain a benzylamino sidearm biphenyl monocyclopentadienyl group IV metal complex as shown in formula (I-3).

[0040] In a specific embodiment, the compound represented by formula (II) can be prepared according to the following method, and the reaction scheme is as follows:

[0041]

[0042] The method comprises the following steps:

[0043] When Cp' is cyclopentadienyl, indenyl or benzindenyl:

[0044] (e) reacting the compound represented by formula (III) or (IV) with alkyl lithium, substituted or unsubstituted cyclopentenone, indone or benzoindone in sequence, and then dehydrating or dehydroxylating under acidic conditions to obtain the compound represented by formula (III);

[0045] When Cp' is fluorenone or substituted fluorenone:

[0046] (f) In an inert atmosphere and in the presence of a catalytic amount of iodine, magnesium and the compound represented by formula (V) are subjected to a reflux reaction in anhydrous ether, and the generated Grignard reagent is further subjected to a reflux reaction with a substituted or unsubstituted 9-fluorenone. After the reaction is completed, hydrochloric acid is added to quench the reaction to obtain an intermediate product 1;

[0047] (g) the intermediate product 1 is reacted with dibenzoyl peroxide and N-bromosuccinimide, and the reaction product is then reacted with an excess of HI in acetic acid to obtain a compound represented by formula (VI);

[0048] (h) The compound represented by formula (VI) reacts with urotropine to obtain the compound represented by formula (II).

[0049] It should be noted that the synthesis of the benzylamino sidearm biphenyl monocyclopentadienyl group IV metal complex is not limited to the aforementioned synthesis method, and those skilled in the art can synthesize the monocyclopentadienyl group IV metal complex by different methods based on existing chemical knowledge.

[0050] In a third aspect, the present invention further provides use of the benzylamino sidearm biphenyl monocyclopentadienyl group IV metal complex described in the first aspect in catalyzing olefin polymerization.

[0051] In the use provided by the present invention, the olefin polymerization can be ethylene homopolymerization, propylene homopolymerization, copolymerization of ethylene and α-olefin, or copolymerization of propylene and α-olefin.

[0052] In the use provided by the present invention, the olefin polymerization can also be copolymerization of ethylene or propylene with cycloolefin or terpolymerization of ethylene, propylene and cycloolefin.

[0053] In a fourth aspect, the present invention further provides a method for the polymerization of ethylene, using the benzylamino side-arm biphenyl monocyclopentadienyl metal complex of the first aspect as a main catalyst, and using aluminoxane, an alkyl aluminum / organoboron compound composite system or an alkyl aluminum chloride / organoboron compound composite system as a co-catalyst to catalyze the homopolymerization of ethylene to form a homopolymer, or to catalyze the copolymerization of ethylene and α-olefins to form a copolymer, or to catalyze the copolymerization of ethylene and cycloolefins, or to catalyze the ternary copolymerization of ethylene, propylene and cycloolefins.

[0054] The present invention also provides a method for polymerizing propylene, using the benzylamino sidearm biphenyl monocyclopentadienyl group 4 metal complex as a main catalyst, and using aluminoxane, an alkyl aluminum / organoboron compound composite system or an alkyl aluminum chloride / organoboron compound composite system as a co-catalyst to catalyze the homopolymerization of propylene to form a homopolymer, or to catalyze the copolymerization of propylene and α-olefin to form a copolymer.

[0055] In some embodiments, the α-olefin used as a comonomer may be a common type in the art, and may be a C3 to C12 α-olefin. In some preferred embodiments, the d-olefin may be 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene or 1-octene.

[0056] In some embodiments, the cycloolefin used as a comonomer may be a common type in the art, and the cycloolefin may be a cycloolefin such as cyclopentadiene, norbornene, ethylidene norbornene, dicyclopentadiene, etc.

[0057] In the polymerization method provided by the present invention, the aluminoxane used as a co-catalyst can be a common type in the art. In some preferred embodiments, the alkyl aluminum includes but is not limited to methyl aluminoxane (MAO) and the like.

[0058] In the polymerization method provided by the present invention, the alkyl aluminum used as a co-catalyst can be any common type in the art. In some preferred embodiments, the alkyl aluminum includes but is not limited to trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, etc.

[0059] In the polymerization method provided by the present invention, the alkylaluminum chloride used as a co-catalyst can be a common type in the art. In some preferred embodiments, the alkylaluminum chloride includes but is not limited to diethylaluminum chloride, sesquiethylaluminum chloride, and the like.

[0060] In the polymerization method provided by the present invention, the organic boron compound used as a co-catalyst can be a common type in the art. In some preferred embodiments, the organic boron compound includes but is not limited to Ph3CB(C6F5)4, B(C6F5)3, Me3OB(C6F5)4, Ph3CB[C6H3(CF3)2]4, B[C6H3(CF3)2]3, Me3OB[C6H3(CF3)2]4, and PhR a 2HNB(C6F5)4 and PhR a 2HNB[C6H3(CF3)2]4, where R a In some more preferred embodiments, the organic boron compound may be Ph3CB(C6F5)4 or PhMe2HNB(C6F5)4.

[0061] In the polymerization method provided by the present invention, when the co-catalyst is methylaluminoxane (MAO), the molar ratio of aluminum in the co-catalyst to the metal in the main catalyst is 5-10000: 1. In some preferred embodiments, the molar ratio of Al to metal M can be 100-2000: 1; in some more preferred embodiments, the molar ratio of Al to metal M can be 1000-1500: 1.

[0062] In the polymerization method provided by the present invention, when the co-catalyst is an alkyl aluminum / organoboron compound composite system or an alkyl aluminum chloride / organoboron compound composite system, the molar ratio of aluminum in the co-catalyst to the metal in the main catalyst is 5-10000:1, and the molar ratio of boron in the co-catalyst to the metal in the main catalyst is 1-2:1. In some preferred embodiments, the molar ratio of Al to metal M can be 50-150:1; in some more preferred embodiments, the molar ratio of Al to metal M can be 50-75:1.

[0063] In the polymerization method provided by the present invention, the polymerization temperature (including homopolymerization and copolymerization) in the polymerization reaction can be 0 to 200° C. In some preferred embodiments, the polymerization temperature can be 100 to 180° C. In some more preferred embodiments, the polymerization temperature can be 120 to 180° C., for example, 120° C., 130° C., 140° C., 150° C., 160° C., 170° C., 180° C.

[0064] In the polymerization method provided by the present invention, the pressure of the ethylene monomer in the polymerization reaction can be 0.05 to 5 MPa. In some preferred embodiments, the pressure of the ethylene monomer can be 0.1 to 1 MPa.

[0065] In the polymerization method provided by the present invention, other process conditions except the above process parameters may be conventional process parameters, or may be appropriately adjusted by those skilled in the art according to actual reaction conditions such as polymerization type.

[0066] The benzylamino sidearm biphenyl monocyclopentadienyl group 4 metal complex and the ethylene polymerization method using the same as a polymerization catalyst provided by the present invention have the following advantages:

[0067] (1) The structure of the fourth group metal complex of the biphenyl monocyclopentadienyl containing benzylamino sidearm of the present invention can enhance the protection of the active metal center, and the catalytic activity is high and long-lasting, and can withstand higher polymerization temperatures. The thermal stability of the catalyst is significantly improved, and the service life is also greatly extended.

[0068] (2) The fourth group metal complex containing benzylamino sidearm biphenyl monocyclopentene of the present invention can not only catalyze the homopolymerization of ethylene, but also can catalyze the copolymerization of ethylene with α-olefins such as propylene, 1-butene, 1-hexene, 1-octene, 1-decene, and cycloolefins such as norbornene, ethylidene norbornene, dicyclopentadiene, etc. with high activity to generate corresponding high comonomer content and high molecular weight copolymers, which can be used to produce high-performance di- and terpolymers of ethylene propylene diene rubber, polyolefin elastomers, cycloolefin copolymers, and other polyolefin products. The substrate applicability is wider, the types of polymerization products are more, and thus the application field is also wider.

[0069] (3) The preparation method of the benzylamino-containing sidearm biphenyl monocyclopentadienyl group IV metal complex of the present invention is simple, does not require complicated process steps and high costs, and can be adapted to large-scale production and use.

[0070] In conclusion, the benzylamino sidearm biphenyl monocyclopentadienyl group IV metal complex and ethylene polymerization method of the present invention can significantly improve the catalytic activity and service life of the catalyst, and are suitable for a variety of polymerization processes, can improve the production efficiency and product quality of ethylene polymers, and have a large-scale industrial application prospect. DETAILED DESCRIPTION

[0071] The present invention will be further described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several variations and improvements may be made without departing from the concept of the present invention. These all fall within the scope of protection of the present invention.

[0072] The experimental methods used in the following examples of compounds are conventional methods unless otherwise specified. Most of the chemical reagents and materials used are commercially available, and some chemical reagents are synthesized according to literature methods. The ligands used in each example were synthesized according to literature methods (Organometallics, 2013, 32, 4185-4191; Bull. Chem. Soc. Jpn., 1989, 62, 2093-2095).

[0073] Example 1: Synthesis of intermediate product 2′-Cp′-1,1′-biphenyl-formaldehyde

[0074] Synthesis of 2′-(Substituted) Cyclopentadienyl-1,1′-Biphenyl-2-Carboxaldehyde / 2′-(Substituted) Indenyl-1,1′-Biphenyl-2-Carboxaldehyde

[0075]

[0076] Under an inert atmosphere, 2-bromo-2′-(1,3-dioxolane)-1,1′-biphenyl (9.15 g, 30.0 mmol) or 2-bromo-2′-(dimethoxymethyl)-1,1′-biphenyl (9.21 g, 30.0 mmol) was dissolved in 100 mL of anhydrous ether, and n-butyl lithium (13.2 mL, 2.5 mol / L) was added at -40°C and stirred for 30 minutes. (Substituted) cyclopentenone or (substituted) indanone (33 mmol) was slowly added to the reaction system, and then the reaction solution was allowed to naturally rise to room temperature and continued to react for 5 hours, and 50 mL of water was added to quench the reaction, and the organic phase was washed twice with a saturated sodium bicarbonate aqueous solution and once with distilled water, and then dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The obtained oily substance was dissolved in 200 mL of tetrahydrofuran, and 20 mL of acetone and 100 mL of 3% dilute hydrochloric acid solution were added, and stirred at room temperature for 5 hours. 80 mL of ethyl acetate was added, and the liquid was separated. The organic phase was washed once with 80 mL of saturated salt water, washed three times with 80 mL of distilled water, and dried over anhydrous sodium sulfate. Filtered, the solvent was evaporated under reduced pressure to obtain an orange crude product, and the corresponding intermediate product was separated by column chromatography to obtain a pure product.

[0077] The structures of the intermediates a, b and c are as follows:

[0078]

[0079] a: Cp′=2,3,4,5-tetramethylcyclopentadienyl; yield, 81.1%. 1 H NMR (400MHz, CDCl3): δ9.91 (1H, s), 8.02 (1H, dd, J=8.5, 2.0, 0.5Hz), 7.31-7.80 (7H, m), 4 .18(1H,s), 3.39-3.13(1H,m), 1.89(3H,s), 1.81(3H,s), 1.64(3H,s), 0.90(3H,d,J=7.8).

[0080] b: Cp′ = indenyl; yield, 84.3%. 1 H NMR (400MHz, CDCl3): δ9.98 (1H, s), 7.97-7.02 (12H, m), 6.63 (1H, s), 3.35 (2H, d, J = 10.5Hz).

[0081] c: Cp′=2-methylindenyl; yield, 79.5%. 1 H NMR (400MHz, CDCl3): δ10.10 (1H, s), 8.11-7.05 (12H, m), 6.71 (1H, s), 4.29 (1H, s), 1.90 (3H, s).

[0082] Synthesis of 2′-(Substituted)fluorenyl-1,1′-biphenyl-2-carboxaldehyde

[0083]

[0084] Under an inert atmosphere, magnesium stick (1.25g, 52mmol) and a catalytic amount of iodine were added to a round-bottom flask containing 100mL of anhydrous ether, stirred and heated until the ether began to reflux, and then the heating was stopped. 2-bromo-2'-methyl-1,1'-biphenyl (12.36g, 50mmol) in 100mL of anhydrous ether solution was added dropwise to the above system, and the system was kept in a reflux state. After the system refluxed itself, it was continued to heat and reflux for 3h. (Substituted) 9-fluorenone (50mmol) was slowly added thereto, and reflux was continued for 2h. 60mL of hydrochloric acid (1mol / L) was added to the reaction system to quench the reaction, and the organic phase obtained after separation was dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to obtain a solid.

[0085] The solid obtained above was dissolved in 100 mL of carbon tetrachloride, and catalytic amounts of dibenzoyl peroxide (BPO) and N-bromosuccinimide (NBS) (9.00 g, 50 mmol) were added successively under stirring, and the reaction system was heated to reflux for 2 h, and insoluble matter was filtered out while hot. The filtrate was distilled under reduced pressure to remove the solvent. HI acetic acid solution (19.19 g, 150 mmol) and 60 mL of acetic acid were added to the obtained residue, and refluxed for 5 h. After the reaction system was cooled to room temperature, the reaction was quenched with a saturated sodium bisulfite solution, and the organic phase was separated and the solvent was removed by distillation under reduced pressure.

[0086] The obtained solid was dissolved in 60 mL of chloroform, and urotropine (21.03 g, 150 mmol) was added thereto, and the mixture was heated under reflux for 2 h, cooled to room temperature, and filtered. The obtained white solid was dissolved in 80 mL of 50% acetic acid aqueous solution, heated at 100° C. for a period of time, and the organic matter was separated, and the corresponding intermediate product was obtained by column chromatography.

[0087] Among them, the structure of the intermediate product d is as follows:

[0088]

[0089] d: Yield, 69.5%. 1 H NMR (400MHz, CDCl3): δ10.46 (1H, s), 7.89-6.80 (16H, m), 6.48 (1H, s).

[0090] Example 2: Synthesis of ligand precursor

[0091]

[0092] Under an inert atmosphere, add 2′-Cp′-1,1′-biphenyl-2-carboxaldehyde (10 mmol), organic amine RNH2 (10 mmol), 5 g molecular sieve and 2 drops of formic acid to 100 mL of anhydrous methanol, stir at room temperature, and monitor the reaction by NMR until the aldehyde signal disappears. Add sodium borohydride (0.567 g, 15 mmol) to the above reaction system in batches, and continue stirring for half an hour after completion. Add saturated ammonium chloride solution to the reaction system, separate the liquid to obtain the organic phase. The organic phase is dried over anhydrous magnesium sulfate, filtered, distilled under reduced pressure, and separated by column chromatography to obtain the corresponding pure ligand precursor.

[0093] Among them, the structures of ligands L1-L10 are as follows:

[0094]

[0095]

[0096] L1: Cp′=2,3,4,5-tetramethylcyclopentadienyl, R=n-propyl; yield, 69.1%. 1 H NMR (CDCl3, 400MHz): δ7.55-7.26 (6H, m), 7.87-7.73 (2H, m), 3.66 (1H, d, J = 13.2Hz), 3.61 (1H, d, J = 13.2Hz), 2.78-2.67 (1H, m), 2.70-7 .74 (2H, t, J = 6.0Hz), 1.90 (3H, s), 1.77 (3H, s), 1.64 (3H, s), 1.48-1.35 (2H, m), 1.26 (3H, d, J = 6.9Hz), 0.97-0.92 (3H, t, J = 7.5Hz) ppm.

[0097] L2: Cp′=2,3,4,5-tetramethylcyclopentadienyl, R=isopropyl; yield, 62.3%. 1 H NMR (CDCl3, 400MHz): δ7.89-7.73 (2H, m), 7.43-7.20 (5H, m), 7.56 (1H, m), 3.76 (1H, d, J = 13.2Hz), 3.71 (1H, d, J = 13.2Hz), 2. 75-2.67 (1H, m), 2.61-2.54 (1H, m), 1.91 (3H, s), 1.78 (3H, s), 1.65 (3H, s), 1.27 (3H, d, J = 7.3Hz), 0.96 (6H, d, J = 6.9Hz) ppm.

[0098] L3: Cp′=2,3,4,5-tetramethylcyclopentadienyl, R=cyclopentyl; yield, 67.6%. 1 H NMR (CDCl3, 400MHz): δ7.86-7.73 (2H, m), 7.56 (1H, m), 7.43-7.20 (5H, m), 3.7 9-3.57(2H,m), 3.25-3.04(1H,m), 2.93-2.65(1H,m), 1.88-0.93(20H,m)ppm.

[0099] L4: Cp′=2,3,4,5-tetramethylcyclopentadienyl, R=cyclohexyl; yield, 61.0%. 1 H NMR (CDCl3, 400MHz): δ7.83-7.72 (2H, m), 7.53 (1H, m), 7.40-7.20 (5H, m), 3.7 6-3.55(2H,m), 3.21-3.02(1H,m), 2.91-2.63(1H,m), 1.86-0.91(22H,m)ppm.

[0100] L5: Cp′=2,3,4,5-tetramethylcyclopentadienyl, R=tert-butyl; yield, 65.7%. 1 H NMR (CDCl3, 400MHz): δ7.86-7.73 (2H, m), 7.56 (1H, m), 7.44-7.20 (5H, m), 3.81 (1H, d, J = 12.0Hz), 3. 74 (1H, d, J = 12.0Hz), 1.85 (3H, s), 1.71 (3H, s), 1.55 (3H, s), 1.27 (9H, s), 1.18 (3H, d, J = 7.1Hz) ppm.

[0101] L6: Cp′=2,3,4,5-tetramethylcyclopentadienyl, R=phenyl; yield, 69.2%. 1 H NMR (CDCl3, 400MHz): δ7.86-7.73 (2H, m), 7.56 (1H, m), 7.44-7.17 (7H, m), 6.93-6.72 (3H, m), 3.75 (1H, d, J=11.5Hz), 3.69 (1H, d, J=1 1.5Hz), 1.79(3H,s), 1.65(3H,s), 1.58(3H,s), 1.03(3H,d,J=6.9Hz)ppm.

[0102] L7: Cp′=2,3,4,5-tetramethylcyclopentadienyl, R=diphenylmethyl; yield, 60.0%. 1 H NMR: δ7.86-7.73 (2H, m), 7.62-7.20 (16H, m), 3.83 (2H, s), 5.84 (1H, s), 1.76 (3H, s), 1.61 (3H, s), 1.50 (3H, s), 1.03 (3H, d, J = 7.2Hz) ppm.

[0103] L8: Cp′ = indenyl, R = cyclohexyl; yield, 66.1%. 1 H NMR (CDCl3, 400MHz): δ7.86-7.73 (2H, m), 7.57-6.94 (10H, m), 6.82 (1H, d, J=8.2Hz), 3 .85(1H,s), 3.75(1H,s), 3.24-3.12(1H,m), 2.46-2.51(1H,m), 1.81-0.99(22H,m)ppm.

[0104] L9: Cp′=2-methylindenyl, R=cyclohexyl; yield, 61.8%. 1H NMR (CDCl3, 400MHz): δ7.86-7.73 (2H, m), 7.58-7.08 (10H, m), 6.66 (1H, s), 3.78 (1H, s), 3.83 ( 1H, s), 3.21-3.10 (1H, m), 2.40-2.48 (1H, m), 1.89 (3H, s), 1.73 (3H, s), 1.29-1.62 (19H, m)ppm.

[0105] L10: Cp′ = fluorenyl, R = cyclohexyl; yield, 63.7%. 1 H NMR (CDCl3, 400MHz): δ7.87-7.73 (4H, m), 7.66-7.53 (3H, m), 7.50-7.28 (9H, m), 5.3 8(1H,s), 4.22(2H,s), 3.19(1H,t,J=12.1Hz), 2.51(1H,s), 1.99-0.96(10H,m)ppm.

[0106] Example 3: Synthesis of complex

[0107]

[0108] Under an inert atmosphere, weigh the ligand precursor (20.00mmol) in a 250mL Schlenk bottle, add 100mL of anhydrous tetrahydrofuran, add n-BuLi (16mL, 40.00mmol, 2.50mol / L) in n-hexane at -30°C, then warm to room temperature and continue stirring for 1h. Add Me3SiCl (5.1mL, 40.00mmok) to the obtained ligand lithium salt solution and react at 50°C for 6h. Remove the reaction solvent under reduced pressure, extract the residue with toluene (50mL), and filter to remove the lithium chloride precipitate. The resulting filtrate is slowly added to a toluene (30mL) solution of titanium tetrachloride (3.79g, 20.00mmol) or a toluene (30mL) suspension of zirconium tetrachloride (4.66g, 20.00mmol) at room temperature. The reaction mixture is stirred at room temperature for 1h, and then reacted at 70°C overnight. The generated precipitate is filtered off, and the solvent in the filtrate is removed in vacuo to obtain a crude product. The crude product is recrystallized from a mixed solvent of dichloromethane / n-hexane to obtain an orange-red, orange-yellow or orange solid.

[0109] Under an inert atmosphere, titanium dichloride (10 mmol) was weighed into a 250 mL Schlenk bottle, 50 mL of anhydrous ether was added, and methylmagnesium chloride (6.67 mL, 20 mmol, 3 mol / L THF) was added thereto. The system was reacted at 23 °C for 12 h, the solvent was removed in vacuo, the residue was extracted and filtered with pentane, and the filtrate was concentrated and recrystallized to obtain the corresponding methylated complex.

[0110] The corresponding relationship between the complex and the ligand is as follows:

[0111] C1: L1; yield, 46.1%; 1 H NMR (CDCl3, 400MHz): δ7.91-7.56 (8H, m), 4.64 (s, 2H), 4.27 (2H, t, J = 7.5Hz), 2.26 (6H, s), 1.85 (6H, s), 1.68-1.56 (2H, m), 1.01 (3H, t, J = 7.5Hz) ppm.

[0112] C2: L2; yield, 56.7%; 1 H NMR (CDCl3, 400MHz): δ7.80-7.55 (8H, m), 5.89 (1H, m), 4.56 (s, 2H), 4.27 (2H, t, J = 7.5Hz), 2.26 (6H, s), 1.85 (6H, s), 1.23 (6H, d, J = 6.1Hz) ppm.

[0113] C3: L3; yield, 66.0%; 1 H NMR (CDCl3, 400MHz): δ7.94-7.75 (8H, m), 6.16 (1H, q, J = 7.9Hz), 4.59 (2H, s), 2.25 (6H, s), 1.71 (6H, s), 2.11-1.24 (8H, m)ppm.

[0114] C4: L4; yield, 61.3%; 1 H NMR (CDCl3, 400MHz): δ7.94-7.70 (8H, m), 5.92 (1H, q, J=7.2Hz), 4.59 (2H, s), 2.26 (6H, s), 1.77 (6H, s), 1.95-1.26 (10H, m)ppm.

[0115] C5: L5; yield, 64.9%; 1 H NMR (CDCl3, 400MHz): δ7.93-7.72 (8H, m), 4.61 (2H, s), 2.23 (6H, s), 1.70 (6H, s), 1.56 (9H, s)ppm.

[0116] C6:L6; yield, 59.8%; 1 H NMR (CDCl3, 400MHz): δ8.02-7.77 (13H, m), 4.68 (2H, s), 2.29 (6H, s), 2.07 (6H, s) ppm.

[0117] C7:L7; yield, 62.7%; 1 H NMR (CDCl3, 400MHz): δ8.19 (1H, s), 8.05-7.71 (18H, m), 4.46 (2H, s), 2.25 (6H, s), 1.97 (6H, s)ppm.

[0118] C8: L8; yield, 56.4%; 1 H NMR (CDCl3, 400MHz): δ7.74-7.48 (12H, m), 4.62 (2H, s), 4.18 (1H, s), 1.99-1.27 (11H, m)ppm.

[0119] C9:L9; yield, 65.4%; 1 H NMR (CDCl3, 400MHz): δ7.74-7.48 (12H, m), 4.62 (2H, s), 4.18 (1H, s), 1.92-1.27 (13H, m)ppm.

[0120] C10: L9; yield, 65.4%; 1 H NMR (CDCl3, 400MHz): δ7.71-7.43 (12H, m), 4.48 (2H, s), 4.17 (1H, s), 1.90-1.28 (13H, m)ppm.

[0121] C11: L10; yield, 70.0%; 1 H NMR (CDCl3, 400MHz): δ8.22-7.43 (16H, m), 4.78 (2H, s), 4.64 (1H, t, J=5.5Hz), 1.78-1.18 (10H, m).

[0122] Example 4: Ethylene Homopolymerization

[0123] The polymerization reaction was carried out in a 250 mL stainless steel autoclave. The autoclave was heated to 120°C and vacuum-evacuated for 1 h. The system was adjusted to the required temperature for polymerization. Ethylene gas at 0.1 MPa was introduced. iThe 60mL toluene solution of Bu3 after drying and purification was kept warm for a period of time until the temperature was constant, and 0.5MPa ethylene gas was introduced, and then the main catalyst and CPh3B(C6F5)4 were added and stirred for a period of time. After the polymerization reaction was completed, the residual ethylene gas was released, the reactor was opened, and the obtained polymerization reaction mixture was poured into a mixed solution of 3M hydrochloric acid and ethanol in a volume ratio of 1:1, stirred for 5 minutes, and then filtered. The polyethylene product was dried in a vacuum oven, weighed, and its molecular weight was measured. The results are shown in Table 1.

[0124] Table 1. Results of ethylene homopolymerization catalyzed by C1-C11 as the main catalyst

[0125]

[0126]

[0127] aPolymerization conditions: The amount of the main catalyst is 2 μmol; the co-catalyst is Al i Bu3 / CPh3B(C6F5)4, CPh3B(C6F5)4 / primary catalyst = 1.5; b unit is 10 6 g(molM) -1 h -1 ;cM w It is measured by GPC at 135℃ with trichlorobenzene as solvent, and the unit is 10 4 g mol -1 .

[0128] Example 5: Propylene Homopolymerization

[0129] The polymerization reaction was carried out in a 250 mL stainless steel autoclave. The autoclave was heated to 120°C and vacuum-evacuated for 1 h. The system was adjusted to the required temperature for polymerization. 0.1 MPa of propylene gas was introduced. i The 60mL toluene solution of Bu3 after drying and purification was kept warm for a period of time until the temperature was constant, and 0.5Mpa propylene gas was introduced, and then the main catalyst and CPh3B(C6F5)4 were added and stirred for a period of time. After the polymerization reaction was completed, the residual propylene gas was released, the reactor was opened, and the obtained polymerization reaction mixture was poured into a mixed solution of 3M hydrochloric acid and ethanol in a volume ratio of 1:1. After stirring for 5 minutes, the mixture was collected by hand, and the polypropylene product was dried in a vacuum oven, weighed, and its molecular weight and isotacticity were measured. The results are shown in Table 2.

[0130] Table 2. Results of propylene homopolymerization catalyzed by C1-C11 as the main catalyst a

[0131]

[0132]

[0133] aPolymerization conditions: polymerization temperature is 70℃; polymerization time is 10min; the amount of main catalyst is 2μmol; co-catalyst is Al i Bu3 / CPh3B(C6F5)4,Al i Bu3 / CPh3B(C6F5)4 / main catalyst = 75 / 1.5 / 1; b unit is 10 6 g(mol M) -1 h -1 ; c Isotacticity is determined by the n-heptane extraction method (extraction with boiling n-heptane for 6 hours): 2 g of the dried polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. The residue is dried to constant weight. The ratio of the polymer weight (g) to 2 g is the isotacticity; d M w It is measured by GPC at 40°C with tetrahydrofuran as solvent, and the unit is 10 4 g mol -1 .

[0134] Example 6: Copolymerization of ethylene and α-olefin (1-hexene or 1-octene)

[0135] The polymerization reaction was carried out in a 250 mL stainless steel autoclave. The autoclave was heated to 120°C and vacuum-evacuated for 1 h. 0.1 MPa of ethylene gas was introduced. The system was adjusted to the required temperature for polymerization. A certain amount of Al was added to the autoclave. i A mixed solution of Bu3 and a certain concentration of α-olefin (1-hexene or 1-octene) in 60 mL toluene was kept warm for a period of time until the temperature was constant, 0.5 MPa of ethylene gas was introduced, and then the main catalyst and CPh3B(C6F5)4 were added and stirred for a period of time. After the polymerization reaction was completed, the residual ethylene gas was released, the reactor was opened, and the obtained polymerization reaction mixture was poured into a mixed solution of 3M hydrochloric acid and ethanol in a volume ratio of 1:1, stirred for 5 minutes, filtered, dried in a vacuum oven, weighed, and its molecular weight and molecular weight distribution were measured. The comonomer insertion rate was measured by carbon spectrum, and the results are shown in Tables 3 and 4.

[0136] Table 3. Results of copolymerization of ethylene and 1-hexene

[0137]

[0138]

[0139] aPolymerization conditions: polymerization temperature is 150℃; polymerization time is 5min; the amount of main catalyst C1-C11 is 1μmol, and the co-catalyst is Al i Bu3 / CPh3B(C6F5)4,Ali Bu3 / CPh3B(C6F5)4 / main catalyst = 75 / 1.5 / 1; b unit is 10 7 g(molM) -1 h -1 ;c M w It is measured by GPC at 135℃ with trichlorobenzene as solvent, and the unit is 10 4 g mol -1 ;d by 13 C NMR was measured, refer to J. Macromol. Sci. Rev. Macromo. Chem. Phys., 1989, C29(2&3): 201-317.

[0140] Table 4. Results of copolymerization of ethylene and 1-octene a

[0141]

[0142]

[0143] aPolymerization conditions: polymerization temperature is 150℃; polymerization time is 5min; the amount of main catalyst C1-C11 is 1μmol, and the co-catalyst is Al i Bu3 / CPh3B(C6F5)4,Al i Bu3 / CPh3B(C6F5)4 / main catalyst = 75 / 1.5 / 1; b unit is 10 7 gmol -1 h -1 ;c Molecular weight is measured and calculated by GPC at 135°C using trichlorobenzene as solvent, and the unit is 10 4 g mol -1 ;d by 13 CNMR was measured, refer to J. Macromol. Sci. Rev. Macromo. Chem. Phys., 1989, C29(2&3): 201-317.

[0144] Example 7: Ethylene / norbornene copolymerization

[0145] The polymerization reaction was carried out in a 250 mL stainless steel autoclave. The autoclave was heated to 120°C and vacuum-evacuated for 1 h. 0.1 MPa of ethylene gas was introduced. The system was adjusted to the required temperature for polymerization. A certain amount of Al was added to the autoclave. iA mixed solution of Bu3 and a certain concentration of norbornene in 60 mL toluene was kept warm for a period of time until the temperature was constant, 0.5 MPa of ethylene gas was introduced, and then the main catalyst and CPh3B(C6F5)4 were added and stirred for a period of time. After the polymerization reaction was completed, the residual ethylene gas was released, the reactor was opened, and the obtained polymerization reaction mixture was poured into a mixed solution of 3M hydrochloric acid and ethanol in a volume ratio of 1:1, stirred for 5 minutes, filtered, dried in a vacuum oven, weighed, and its molecular weight and molecular weight distribution were measured. The comonomer insertion rate was measured by carbon spectrum, and the results are shown in Table 5.

[0146] Table 5. Results of copolymerization of ethylene and bornene

[0147]

[0148]

[0149] aPolymerization conditions: polymerization temperature is 150℃; polymerization time is 3min; the dosage of main catalyst C1-C11 is 1μmol, and the co-catalyst is AI i Bu3 / CPh3B(C6F5)4,AI i Bu3 / CPh3B(C6F5)4 / main catalyst=75 / 1.5 / 1; b M w It is measured and calculated by GPC at 135°C using trichlorobenzene as solvent. The unit is 10 4 g mol -1 ;c 13 C NMR was measured, refer to J. Macromol. Sci. Rev. Macromo. Chem. Phys., 1989, C29(2&3): 201-317.

[0150] Comparative Example 1

[0151] The polymerization reaction was carried out in a 250 mL stainless steel autoclave. The autoclave was heated to 120°C and vacuum-evacuated for 1 h. 0.1 MPa of ethylene gas was introduced and the temperature was adjusted to 150°C. A certain amount of Al iA mixed solution of Bu3 and 1mol / L 1-octene in 60mL toluene was kept warm for a period of time until the temperature was constant, 0.5MPa ethylene gas was introduced, and then the catalyst shown in the following formula (self-made with reference to CN105408338A) and CPh3B(C6F5)4 were added and stirred for a period of time. After the polymerization reaction was completed, the residual ethylene gas was released, the reactor was opened, and the obtained polymerization reaction mixture was poured into a mixed solution of 3M hydrochloric acid and ethanol in a volume ratio of 1:1, stirred for 5min, filtered, dried in a vacuum oven, and weighed. The remaining reaction conditions were consistent with the reaction conditions of No. 2 in Table 3 in Example 6. The molecular weight and molecular weight distribution were measured according to the method of Example 6, and the comonomer insertion rate was measured by carbon spectrum. The polymer yield was 0.5g, and the molecular weight Mw was 14.5×10 4 g / mol, and the 1-octene insertion rate was 8.9mol%. Comparison of the data in this comparative example with the data of No. 2 in Table 3 shows that, under the same polymerization conditions, the catalyst having the same substituent in the embodiment of the present invention has higher activity than that in the comparative example, and the obtained polymer has higher molecular weight and comonomer content, and has better copolymerization performance.

[0152]

[0153] Comparative Example 2

[0154] The polymerization reaction was carried out in a 250 mL stainless steel autoclave. The autoclave was heated to 120°C and vacuum-evacuated for 1 h. The system was adjusted to the required temperature for polymerization. Ethylene gas at 0.1 MPa was introduced. i The 60mL toluene solution of Bu3 after drying and purification was kept warm for a period of time until the temperature was constant, and 0.5MPa ethylene gas was introduced, and then the main catalyst and CPh3B(C6F5)4 shown in the following formula were added and stirred for a period of time. After the polymerization reaction was completed, the residual ethylene gas was released, the reactor was opened, and the obtained polymerization reaction mixture was poured into a mixed solution of 3M hydrochloric acid and ethanol in a volume ratio of 1:1, stirred for 5 minutes, and then filtered. The polyethylene product was dried in a vacuum oven and its mass was weighed. The results are shown in Table 6.

[0155]

[0156] Table 6. Comparative Example 2 Catalytic Ethylene Polymerization Results a

[0157] Serial number Temperature(℃) Yield (g) Polymerization time (min) <![CDATA[Active b > 1 90 0.58 10 1.74 2 120 0.66 10 1.98 3 150 0.46 10 1.38 4 120 1.98 30 1.79 5 120 1.79 60 1.61 6 120 1.61 120 1.54 7 120 1.54 180 1.27 8 120 1.27 240 1.00

[0158] aPolymerization conditions: The amount of the main catalyst is 2 μmol; the co-catalyst is Al i Bu3 / CPh3B(C6F5)4,Al iBu3 / CPh3B(C6F5)4 / main catalyst = 75 / 1.5 / 1; b unit is 10 6 g(mol M) -1 h -1 .

[0159] From the comparison of the data of Table 6 and No. 11 to 18 in Table 1, it can be seen that, under the same polymerization conditions, the catalysts with the same substituents have a more obvious decrease in activity with increasing temperature, and a lower temperature at which the highest activity is achieved; and the activity of the catalysts with the same substituents has a more obvious decrease with increasing polymerization time. This shows that the catalysts with the same substituents in the present invention have higher stability and activity, and longer catalytic life than the comparative examples.

Claims

1. A benzylamino sidearm biphenyl monocyclopentadienyl group 4 metal complex having a structural formula as shown in the following formula (I): In formula (I), M is titanium, zirconium or hafnium; Cp' is a substituted or unsubstituted group as follows: cyclopentadienyl, indenyl, benzoindenyl, fluorenyl; R is a substituted or unsubstituted group as follows: C1-C30 alkyl, C3-C10 cycloalkyl, C6-C20 aryl; Each X is independently halogen, C1-C30 alkyl, substituted C1-C30 alkyl, C1-C30 alkoxy, substituted C1-C30 alkoxy, amine, substituted amine, C6-C20 aryl, substituted C6-C20 aryl, C6-C20 arylC1-C10 alkyl, substituted C6-C20 arylC1-C10 alkyl.

2. The fourth group metal complex of biphenyl monocyclopentadienyl containing benzylamino sidearm according to claim 1, characterized in that: In formula (I): M is titanium or zirconium; and / or Cp' is cyclopentadienyl, monomethylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, methylethylcyclopentadienyl, methylpropylcyclopentadienyl, methylbutylcyclopentadienyl, dimethyldiphenylcyclopentadienyl, diphenylcyclopentadienyl, indenyl, monomethylindenyl, dimethylindenyl, benzoindenyl, 2-methylbenzoindenyl, 3-dimethylaminoindenyl, 3-diethylaminoindenyl, 3-tetrahydropyrrolylindenyl, 3-piperidinylindenyl, 2-methyl-4-phenylindenyl, 2-benzylindenyl, 2-p-methylbenzylindenyl, Preferably, Cp' is cyclopentadienyl, tetramethylcyclopentadienyl, dimethyldiphenylcyclopentadienyl, indenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, 3-dimethylaminoindenyl, 3-diethylaminoindenyl, 3-tetrahydropyrrolylindenyl, 3-piperidinylindenyl, 2-methylbenzoindenyl, fluorenyl, 3,6-dimethylfluorenyl, 3,6-di-tert-butylfluorenyl; further preferably, Cp' is tetramethylcyclopentadienyl, indenyl, 2-methylindenyl, fluorenyl; and / or R is ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, isopentyl, tert-pentyl, n-hexyl, 2-hexyl, 3-hexyl, isohexyl, tert-hexyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, isoheptyl, tert-heptyl, n-octyl and various isomeric octyl, n-nonyl and various isomeric nonyl, n-decyl and various isomeric decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, o-tolyl, p-tolyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, o-ethylphenyl, p-ethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 3,5-diethylphenyl, 2,4,6-triethylphenyl, o-isopropylphenyl, p-isopropylphenyl, 2,4-diisopropylphenyl, 3,5-diisopropylphenyl , 2,4,6-triisopropylphenyl, o-tert-butylphenyl, p-tert-butylphenyl, 2,4-di-tert-butylphenyl, 3,5-di-tert-butylphenyl, 4-methyl-2,6-di-tert-butylphenyl; preferably, R is ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, benzhydryl, phenyl, o-tolyl, p-tolyl, 2, 4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 3,5-diethylphenyl, 2,4,6-triethylphenyl, 2,4-diisopropylphenyl, 3,5-diisopropylphenyl, 2,4-di-tert-butylphenyl, 3,5-di-tert-butylphenyl; further preferably, R is n-propyl, isopropyl, cyclopentyl, cyclohexyl, tert-butyl, phenyl, diphenylmethyl; and / or Each X is independently chlorine, bromine, iodine, methyl, neopentyl, trimethylsilyl, methoxy, ethoxy, isopropoxy, tert-butoxy, dimethylamino, diethylamino, diisopropylamino, bistrimethylsilylamino, or benzyl; preferably, each X is independently chlorine, bromine, methyl, trimethylsilyl, isopropoxy, tert-butoxy, dimethylamino, diethylamino, or benzyl; more preferably, each X is simultaneously chlorine.

3. The fourth subgroup metal complex of biphenyl monocyclopentadienyl containing benzylamino sidearm according to claim 1 or 2, characterized in that: The benzylamino sidearm biphenyl monocyclopentadienyl group 4 metal complex shown in formula (I) is selected from the following structures:

4. A method for preparing the fourth group metal complex of biphenyl monocyclopentadienyl containing benzylamino sidearm according to any one of claims 1 to 3, wherein the reaction scheme is as follows: in, Cp', R, M are defined as in claims 1-3; X1 is selected from C1-C30 alkyl, substituted C1-C30 alkyl; X2 is selected from halogen; X3 is selected from amine, substituted amine, C6-C20 aryl C1-C10 alkyl, substituted C6-C20 aryl C1-C10 alkyl; The preparation method comprises the following steps: (1) The compound represented by formula (II) reacts with an organic amine RNH2, and the reaction product reacts with a reducing agent to obtain a ligand precursor (III); (2) The ligand precursor (III) is synthesized according to the route selected from (b) to (d) to synthesize the fourth group metal complex containing a benzylamino side arm biphenyl monocyclopentadienyl: (b) under an inert atmosphere, the ligand precursor (III) reacts with an alkyl lithium (e.g., n-butyl lithium) or an alkyl Grignard reagent, and the reaction product reacts with an M metal halide (e.g., MCl4) to obtain a benzylamino-sidearm biphenyl monocyclopentadienyl group 4 metal complex as shown in formula (I-1); (c) under an inert atmosphere, the ligand precursor (III) reacts with an alkyl lithium or alkyl Grignard reagent, the reaction product reacts with trimethylsilyl chloride, and the reaction product reacts with a metal halide M to obtain a benzylamino sidearm biphenyl monocyclopentadienyl group IV metal complex as shown in formula (I-2); (d) reacting the ligand precursor (III) with a metal amide or a metal benzyl compound M to obtain a benzylamino-sidearm biphenyl monocyclopentadienyl group IV metal complex as shown in formula (I-3); Preferably, the compound represented by formula (II) is prepared according to the following method, and the reaction scheme is as follows: The method comprises the following steps: When CD' is cyclopentadienyl, indenyl or benzindenyl: (e) reacting the compound represented by formula (III) or (IV) with alkyl lithium, substituted or unsubstituted cyclopentenone, indone or benzoindone in sequence, and then dehydrating or dehydroxylating under acidic conditions to obtain the compound represented by formula (III); When CD' is fluorenone or substituted fluorenone: (f) In an inert atmosphere and in the presence of a catalytic amount of iodine, magnesium and the compound represented by formula (V) are subjected to a reflux reaction in anhydrous ether, and the generated Grignard reagent is further subjected to a reflux reaction with a substituted or unsubstituted 9-fluorenone. After the reaction is completed, hydrochloric acid is added to quench the reaction to obtain an intermediate product 1; (g) the intermediate product 1 is reacted with dibenzoyl peroxide and N-bromosuccinimide, and the reaction product is then reacted with an excess of HI in acetic acid to obtain a compound represented by formula (VI); (h) The compound represented by formula (VI) reacts with urotropine to obtain the compound represented by formula (II).

5. Use of the benzylamino sidearm biphenyl monocyclopentadienyl group 4 metal complex according to any one of claims 1 to 3 in catalyzing olefin polymerization; Preferably, the olefin polymerization is ethylene homopolymerization, propylene homopolymerization, copolymerization of ethylene and α-olefin, copolymerization of propylene and α-olefin, or copolymerization of ethylene or propylene and cycloolefin, or terpolymerization of ethylene, propylene and cycloolefin.

6. A method for the polymerization of ethylene, which uses the benzylamino sidearm biphenyl monocyclopentadienyl group 4 metal complex as a main catalyst, and uses aluminoxane, an alkyl aluminum / organoboron compound composite system or an alkyl aluminum chloride / organoboron compound composite system as a co-catalyst to catalyze the homopolymerization of ethylene to form a homopolymer, or catalyzes the copolymerization of ethylene and α-olefins to form a copolymer, or catalyzes the copolymerization of ethylene and cycloolefins, or catalyzes the ternary copolymerization of ethylene, propylene and cycloolefins.

7. A method for polymerizing propylene, which comprises using the benzylamino sidearm biphenyl monocyclopentadienyl group 4 metal complex as a main catalyst, and using aluminoxane, an alkyl aluminum / organoboron compound composite system or an alkyl aluminum chloride / organoboron compound composite system as a co-catalyst to catalyze the homopolymerization of propylene to form a homopolymer, or to catalyze the copolymerization of propylene and α-olefin to form a copolymer.

8. The polymerization method according to claim 6 or 7, characterized in that The α-olefin is a C3-C12 α-olefin, preferably 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene or 1-octene; and / or The cycloolefin is cyclopentadiene, norbornene, ethylidene norbornene, dicyclopentadiene; and / or The alkylaluminum comprises methylaluminoxane; and / or The alkylaluminum includes trimethylaluminum, triethylaluminum, triisobutylaluminum; and / or The alkylaluminum chloride includes diethylaluminum chloride, sesquiethylaluminum chloride; and / or The organic boron compounds include Ph3CB(C6F5)4, B(C6F5)3, Me3OB(C6F5)4, Ph3CB[C6H3(CF3)2]4, B[C6H3(CF3)2]3, Me3OB[C6H3(CF3)2]4, and PhR a 2HNB(C6F5)4 and PhR a 2HNB[C6H3(CF3)2]4, where R a It is a C1-C18 alkyl group; preferably, the organic boron compound is Ph3CB(C6F5)4 or PhMe2HNB(C6F5)4.

9. The polymerization method according to claim 6 or 7, characterized in that When the co-catalyst is methylaluminoxane, the molar ratio of aluminum in the co-catalyst to the metal in the main catalyst is 5-10000:1, preferably 100-2000:1, more preferably 1000-1500:1; and / or When the co-catalyst is an alkylaluminum / organoboron compound composite system or an alkylaluminum chloride / organoboron compound composite system, the molar ratio of aluminum in the co-catalyst to the metal in the main catalyst is 5-10000:1, preferably 50-150:1, and further preferably 50-75:1; the molar ratio of boron in the co-catalyst to the metal in the main catalyst is 1-2:

1.

10. The polymerization method according to claim 6 or 7, characterized in that The polymerization temperature in the polymerization reaction is 0 to 200° C., preferably 100 to 180° C., more preferably 120 to 180° C.; and / or The pressure of the ethylene monomer during the polymerization reaction is 0.05 to 5 MPa, preferably 0.1 to 1 MPa.

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