Bimetallic catalyst and preparation method thereof, and preparation method of high molecular weight olefin polymer

Abstract

The present invention discloses a bimetallic catalyst, a preparation method thereof, and a method for preparing a high-molecular-weight olefin polymer. The bimetallic catalyst has the following general structural formula. In the presence of the bimetallic catalyst, a high-molecular-weight olefin polymer can be produced, and the catalyst has good thermal stability.

Description

Technical Field

[0001] The present invention relates to a bimetallic catalyst for olefin polymerization, in particular to a bimetallic catalyst and a preparation method thereof, and a preparation method of a high molecular weight olefin polymer. Background Art

[0002] Polyolefin elastomers (POE) are a widely used class of copolymer materials composed of random copolymers of ethylene and α-olefins. As the content of α-olefin comonomers (1-butene, 1-hexene, and 1-octene) in the copolymer increases, the copolymer's crystallinity and glass transition temperature gradually decrease, transforming the product from a thermoplastic to a thermoplastic elastomer with a certain degree of elasticity. Due to the incorporation of a large amount of α-olefin comonomer into the POE backbone and the presence of the polyethylene portion, the polymer possesses a certain degree of crystallinity. Consequently, it possesses excellent physical and mechanical properties and good processing properties, making it suitable for applications in pipes, cables, films, fibers, and molding.

[0003] The production barriers to polyolefin elastomers are high, and their core technology is catalysts. Metallocene catalysts are currently the most widely used type of catalyst. Companies such as Dow Chemical, ExxonMobil, Mitsui Chemicals, and LG Chem have all entered the metallocene catalyst market and applied them to the copolymerization of ethylene / α-olefins. While they exhibit good polymerization activity, these catalysts have poor temperature resistance and produce relatively low polymer molecular weights. Furthermore, Dow Chemical has reported on the use of imine-amine transition metal catalysts for catalyzing the copolymerization of ethylene / α-olefins. While the molecular weight of the polymers is increased, isomerization of the catalyst structure occurs at high temperatures, resulting in a low insertion rate of the comonomer and insufficient thermal stability. Dow Chemical's patent CN106459286B discloses a bridged bisbiphenyl transition metal catalyst with excellent copolymerization performance and thermal stability, but the polymer molecular weight is not high.

[0004] Therefore, how to obtain catalysts with excellent thermal stability and the ability to increase polymer molecular weight remains a focus of ongoing research. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention first proposes a bimetallic catalyst, which has excellent thermal stability when catalyzing the preparation of olefin polymers and can also produce high molecular weight polyolefins.

[0006] The present invention also proposes a method for preparing a bimetallic catalyst, providing a feasible process route for industrial application.

[0007] The present invention also provides a method for preparing a high molecular weight olefin polymer, specifically an application of a bimetallic catalyst in preparing a high molecular weight olefin polymer.

[0008] To achieve the above object, the technical solutions adopted by the present invention are as follows:

[0009] According to the first aspect of the present invention, a bimetallic catalyst has the general structural formula shown in Formula I:

[0010]

[0011] Where, R1-R 12 are independently selected from hydrogen, halogen, carbazolyl, benzocarbazolyl, dibenzocarbazolyl or any of the following groups: C1-C 24 Alkyl, C1-C 24 Alkyloxy, C1-C 12 Alkylamino, C1-C 12 Alkyl halides, C6-C 30 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylamino, C6-C 30 Aryl halides, C6-C 30 Aralkyl, C6-C 30 Arylalkyl halides, C 12 -C 40 Alkyl, aryl or aralkyl substituents of the carbazolyl group;

[0012] T1 and T2 are the same or different bridging groups, each independently selected from C1-C 20 Alkyl or cycloalkyl or silyl, C1-C 20 Alkoxy, C6-C 30 an aryl or aralkyl group;

[0013] X is selected from halogen, C1-C6 alkyl or alkoxy, C2-C 10 Unsaturated hydrocarbon groups, C6-C 20 Aryl or aralkyl, C3-C 12 Silane group or siloxane group; n is 2;

[0014] M1 and M2 are the same or different and are independently selected from titanium, zirconium and hafnium.

[0015] As a preferred embodiment, in Formula I, R1-R 12 are independently selected from hydrogen, halogen, carbazolyl, benzocarbazolyl, dibenzocarbazolyl or any of the following groups: C1-C 15 Alkyl, C1-C 15 Alkyloxy, C1-C7 alkylamino, C1-C8 alkyl halide, C6-C 24 Aryl, C6-C 12 Aryloxy, C6-C 12Arylamino, C6-C 24 Aryl halides, C6-C 24 Aralkyl, C6-C 24 Arylalkyl halides, C 12 -C 24 Alkyl, aryl or aralkyl substituents of the carbazolyl group;

[0016] T1 and T2 are each independently selected from C1-C 18 Alkyl, cycloalkyl or silyl, C1-C 18 Alkoxy, C6-C 24 an aryl or aralkyl group;

[0017] X is selected from chlorine, methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, methoxy, ethoxy, n-propoxy, n-butoxy, vinyl, propenyl, butenyl, phenyl, biphenyl, 1-naphthyl, benzyl, 2-methylphenyl, 3-methylphenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 3-ethylphenyl, trimethylsilyl, ethyldimethylsilyl, methoxydimethylsilyl.

[0018] As a preferred embodiment, the bimetallic catalyst is selected from one or more compounds having the following structural expressions:

[0019]

[0020]

[0021] According to the second aspect of the present invention, a method for preparing the bimetallic catalyst as described above comprises the following steps:

[0022] In an ultra-dry organic solvent, the ligand represented by formula II is first reacted with a hydrogen extraction reagent to form a salt, and then complexed with a metal M salt to prepare a bimetallic catalyst;

[0023]

[0024] In Formula II, R1-R 12 The definitions of T1, T2 and R1-R2 in any one of claims 1-3 are the same as those in any one of claims 1-3. 12 , T1, and T2 have the same definitions;

[0025] Preferably, the ultra-dry organic solvent is one or more of toluene, xylene, pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, methylcyclohexane, octane, isooctane, tetrahydrofuran, and diethyl ether; more preferably toluene and n-hexane;

[0026] Preferably, the hydrogen extraction agent is one or more of alkyl lithium, phenyl lithium, sodium hydride, potassium hydride, lithium hydride, tetramethylethylenediamine, lithium bistrimethylsilylamide, sodium bistrimethylsilylamide, lithium diisopropylamide, and potassium carbonate, more preferably n-butyl lithium;

[0027] Preferably, the metal M salt is one or more of titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, dibenzyltitanium dichloride, dibenzylzirconium dichloride, dibenzylhafnium dichloride, trimethylsilylmethylenetitanium dichloride, trimethylsilylmethylenezirconium dichloride, and trimethylsilylmethylenehafnium dichloride;

[0028] Preferably, the molar ratio of the ligand represented by formula II to the hydrogen extraction agent is 1:(4.0-5.0); the molar ratio of the ligand represented by formula II to the metal M salt is 1:(2.0-2.5);

[0029] Preferably, the salt-forming reaction temperature is -78 to 40°C, and the salt-forming reaction time is 1 to 12 hours;

[0030] Preferably, the complexation reaction temperature is 0-180° C., and the complexation reaction time is 1-24 h.

[0031] As a preferred embodiment, the preparation method of the ligand represented by formula II is as follows:

[0032]

[0033] Among them, R1-R 12 The definitions of T1, T2 and R1-R2 in any one of claims 1-3 are the same as those in any one of claims 1-3. 12 , T1, T2 are the same as defined above; R is selected from a boric acid group, a hydroxyl group, an amino group or a carboxyl group;

[0034] 1) reacting compound a and 3,4-dihydro-2H-pyran (DHP) in the presence of pyridinium p-toluenesulfonate to produce compound b;

[0035] Preferably, the reaction conditions are: reaction temperature 25-80°C, reaction time 1-24h;

[0036] 2) reacting compound b with a lithiation reagent and triisopropyl borate to generate compound c;

[0037] Preferably, the reaction conditions are: reaction temperature -78 to 25°C, reaction time 1 to 10 h;

[0038] 3) reacting compound d and benzyl halide in the presence of a base to produce compound e;

[0039] Preferably, the reaction conditions are: reaction temperature 25-100°C, reaction time 1-8h;

[0040] 4) reacting compound e and compound c in the presence of a palladium catalyst and a base to produce compound f;

[0041] Preferably, the reaction conditions are: reaction temperature 25-150°C, reaction time 1-24h;

[0042] 5) Compound f is mixed with a bromination reagent to react to generate compound g;

[0043] Preferably, the reaction conditions are: reaction temperature -25 to 25°C, reaction time 5 to 60 min;

[0044] 6) reacting compound h and 3,4-dihydro-2H-pyran in the presence of pyridinium p-toluenesulfonate to produce compound i;

[0045] Preferably, the reaction conditions are: reaction temperature 25-80°C, reaction time 1-24h;

[0046] 7) reacting compound i with a lithiation reagent and triisopropyl borate to generate compound j;

[0047] Preferably, the reaction conditions are: reaction temperature -78 to 25°C, reaction time 1 to 10 h;

[0048] 8) reacting compound g and compound j in the presence of a palladium catalyst and a base to produce compound k;

[0049] Preferably, the reaction conditions are: reaction temperature 25-150°C, reaction time 1-24h;

[0050] 9) Compound k is mixed with a bromination reagent to react to generate compound 1;

[0051] Preferably, the reaction conditions are: reaction temperature -25 to 25°C, reaction time 5 to 60 min;

[0052] 10) reacting compound 1 with a lithiation reagent and triisopropyl borate to generate compound m;

[0053] Preferably, the reaction conditions are: reaction temperature -78 to 25°C, reaction time 1 to 10 h;

[0054] 11) reacting compound n and benzyl halide in the presence of a base to produce compound o;

[0055] Preferably, the reaction conditions are: reaction temperature 25-100°C, reaction time 1-8h;

[0056] 12) reacting compound o and compound p in the presence of a palladium catalyst and a base to produce compound q;

[0057] Preferably, the reaction conditions are: reaction temperature 25-150°C, reaction time 1-24h;

[0058] 13) Compound q is reacted with a bromination reagent to generate compound r;

[0059] Preferably, the reaction conditions are: reaction temperature -25 to 25°C, reaction time 5 to 60 min;

[0060] 14) reacting compound r and compound m in the presence of a palladium catalyst and a base, and adding hydrochloric acid after the reaction to remove the hydroxyl protecting group THP to generate compound s;

[0061] Preferably, the reaction conditions are: reaction temperature 25-150°C, reaction time 1-24h;

[0062] 15) reacting compound s and a dihalogenated hydrocarbon in the presence of a base to produce compound t;

[0063] Preferably, the reaction conditions are: reaction temperature 25-100°C, reaction time 1-4h;

[0064] 16) reacting compound t and compound s in the presence of a base to produce compound u;

[0065] Preferably, the reaction conditions are: reaction temperature 25-100°C, reaction time 1-4h;

[0066] 17) subjecting compound u to a debenzylation reaction in the presence of hydrogen and palladium on carbon to obtain a ligand represented by formula II;

[0067] Preferably, the reaction conditions are: reaction temperature 25-150° C., reaction time 1-5 h.

[0068] As a preferred embodiment, compound a is selected from one or more of 3-bromo-4-methylphenol, 3-bromo-4-fluorophenol, 3-bromo-5-methylphenol, 3-bromo-4-ethylphenol, m-bromophenol, 3-bromo-4-(trifluoromethyl)phenol, 3-bromo-4-chlorophenol, 3-bromo-4-methoxyphenol, and 3-bromo-5-methoxyphenol;

[0069] Preferably, the compound d is selected from one or more of 3-bromo-4-methylphenol, 3-bromo-4-fluorophenol, 3-bromo-5-methylphenol, 3-bromo-4-ethylphenol, m-bromophenol, 3-bromo-4-(trifluoromethyl)phenol, 3-bromo-4-chlorophenol, 3-bromo-4-methoxyphenol, and 3-bromo-5-methoxyphenol;

[0070] Preferably, the compound h is selected from one or more of 2-bromo-4-tert-butylphenol, 2-bromo-4-methylphenol, 2-bromo-4-fluorophenol, 2-bromophenol, 2-bromo-4,5-dimethylphenol, 2-bromo-4-ethylphenol, 3-bromo-4-hydroxybiphenyl, 2-bromo-4,6-dimethylphenol, 2-bromo-4-trifluoromethylphenol, and 2-bromo-6-(trifluoromethyl)phenol;

[0071] Preferably, the compound n is selected from one or more of 2-bromo-4-tert-butylphenol, 2-bromo-4-methylphenol, 2-bromo-4-fluorophenol, 2-bromo-5-methylphenol, 2-bromo-3-methylphenol, 2-bromo-4,5-dimethylphenol, 2-bromo-3,5-dimethylphenol, 2-bromo-5-fluorophenol, 2-bromo-4,5-difluorophenol, 2-bromo-3,5-difluorophenol, and 2-bromo-4-trifluoromethylphenol;

[0072] Preferably, the compound p is selected from one or more of 3,5-di-tert-butylphenylboronic acid, benzylboronic acid, 2-naphthaleneboronic acid, 1-naphthaleneboronic acid, 3-(trifluoromethyl)phenylboronic acid, 9-phenanthreneboronic acid, 2-triphenylboronic acid, 2-anthraceneboronic acid, 9-anthraceneboronic acid, 7H-dibenzocarbazole, 2,7-di-tert-butylcarbazole, carbazole, 11H-benzo[C]carbazole, and indole;

[0073] Preferably, the dihalogenated hydrocarbon is selected from one or more of 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,2-dibromocyclohexane, and bis(dichloromethyl)dimethylsilane;

[0074] Preferably, the lithiation agent is selected from n-butyllithium and / or n-hexyllithium;

[0075] Preferably, the benzyl halide is selected from benzyl bromide and / or benzyl chloride;

[0076] Preferably, the palladium catalyst is selected from one or more of tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, 1,1'-bis(diphenylphosphino)ferrocenepalladium dichloride(II), tris(dibenzylidene-baseacetone)dipalladium(0), palladium chloride, triphenylphosphinepalladium acetate, bis(tri-tert-butylphosphine)palladium, bis(tricyclohexylphosphine)palladium(0), palladium acetate, and benzyl(chloro)bis(triphenylphosphine)palladium(II);

[0077] Preferably, the base is selected from one or more of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, potassium phosphate, cesium fluoride, sodium bicarbonate, rubidium carbonate, cesium carbonate, francium carbonate, and barium hydroxide;

[0078] Preferably, the brominating agent is selected from liquid bromine and / or N-bromosuccinimide.

[0079] As a preferred embodiment, in step 1), the molar ratio of compound a, 3,4-dihydro-2H-pyran, and pyridinium p-toluenesulfonate is 1:(1-5):(0.1-1);

[0080] Preferably, in step 2), the molar ratio of compound b, the lithiation reagent, and triisopropyl borate is 1:(1-2):(1-2);

[0081] Preferably, in step 3), the molar ratio of compound d, benzyl halide, and base is 1:(1-2):(1-2);

[0082] Preferably, in step 4), the molar ratio of compound e, compound c, palladium catalyst, and base is 1:(1-2):(0.001-0.1):(1-3);

[0083] Preferably, in step 5), the molar ratio of compound f and bromination reagent is 1:(0.8-1.2);

[0084] Preferably, in step 6), the molar ratio of compound h, 3,4-dihydro-2H-pyran, and pyridinium p-toluenesulfonate is 1:(1-5):(0.1-1);

[0085] Preferably, in step 7), the molar ratio of compound i, the lithiation reagent, and triisopropyl borate is 1:(1-2):(1-2);

[0086] Preferably, in step 8), the molar ratio of compound g, compound j, palladium catalyst, and base is 1:(1-2):(0.001-0.1):(1-3);

[0087] Preferably, in step 9), the molar ratio of compound k to the bromination reagent is 1:(0.8-1.2);

[0088] Preferably, in step 10), the molar ratio of compound 1, the lithiation reagent, and triisopropyl borate is 1:(1-2):(1-2);

[0089] Preferably, in step 11), the molar ratio of compound n, benzyl halide, and base is 1:(1-2):(1-2);

[0090] Preferably, in step 12), the molar ratio of compound o, compound p, palladium catalyst, and base is 1:(1-2):(0.001-0.1):(1-3);

[0091] Preferably, in step 13), the molar ratio of compound q to the bromination reagent is 1:(0.8-1.2);

[0092] Preferably, in step 14), the molar ratio of compound r, compound m, palladium catalyst, base, and hydrochloric acid is 1:(1-2):(0.001-0.1):(1-3):(1-2);

[0093] Preferably, in step 15), the molar ratio of compound s, dihalogenated hydrocarbon, and base is 1:(2-8):(1-2);

[0094] Preferably, in step 16), the molar ratio of compound t, compound s, and base is 1:(0.8-1.2):(1-2);

[0095] Preferably, in step 17), the molar ratio of compound u, hydrogen, and palladium on carbon is 1:(4-10):(0.1-1).

[0096] According to a third aspect of the present invention, a method for preparing a high molecular weight olefin polymer comprises the following steps: in the presence of the bimetallic catalyst described above or the bimetallic catalyst prepared by the method described above, an organoaluminum auxiliary and an optional boronized auxiliary are simultaneously added to polymerize ethylene and an α-olefin in an organic solvent to produce a high molecular weight olefin polymer;

[0097] Preferably, the ratio of the organoaluminum adjuvant to the bimetallic catalyst is 1-2000, preferably 2-800, calculated as a metal molar ratio;

[0098] Preferably, the ratio of the boronization auxiliary agent to the bimetallic catalyst is 0-60, preferably 0-10, calculated as the molar ratio of boron element to metal element.

[0099] As a preferred embodiment, the organoaluminum auxiliary agent is selected from one or more of aluminoxane, alkyl aluminum compound, and alkyl aluminum chloride;

[0100] Preferably, the aluminoxane is one or more of methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, isobutylaluminoxane, neopentylaluminoxane, n-hexylaluminoxane and n-octylaluminoxane;

[0101] Preferably, the alkyl aluminum compound is one or more of triethylaluminum, triisobutylaluminum, trioctylaluminum, trimethylaluminum, triisohexylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-hexylaluminum, tri-n-butylaluminum, triisobutylaluminum and tri-n-octylaluminum;

[0102] Preferably, the alkylaluminum chloride is one or more of methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum monochloride, diethylaluminum monochloride, di-n-butylaluminum monochloride, diisobutylaluminum monochloride, n-butylaluminum dichloride, isobutylaluminum dichloride, n-butylaluminum sesquichloride, ethylaluminum sesquichloride, methylaluminum sesquichloride and isobutylaluminum sesquichloride;

[0103] Preferably, the boronization auxiliary agent is selected from one or more of tetrakis(pentafluorophenyl)boric acid-methyldi-(octadecyl)ammonium salt, trityltetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)boron, N,N-dioctadecylmethylaminotetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, dioctadecylmethyltertiaryaminetetrakis(pentafluorophenyl)borate, and dihydrogenated tallow methyltertiaryaminetetrakis(pentafluorophenyl)borate.

[0104] As a preferred embodiment, the polymerization reaction temperature is 30-260°C, preferably 100-220°C; the polymerization reaction pressure is 0.1-50 MPa, preferably 1-12 MPa;

[0105] Preferably, the amount of the bimetallic catalyst added is 0.05-6 μmol / L based on the molar concentration of the metal element in the organic solvent.

[0106] The positive effects of the present invention are:

[0107] The bimetallic catalyst proposed in the present invention has very excellent high-temperature resistance and can be used to catalyze olefin polymerization, especially ethylene / α-olefin copolymerization. The molecular weight of the resulting polymer is between 10,000 and 600,000 g / mol, which can meet different performance requirements and has good industrial application prospects. DETAILED DESCRIPTION

[0108] The present invention will be further described below through specific examples. The examples of the present invention are only for illustration of the present invention and do not limit the scope of the present invention.

[0109] The main sources of the main materials and reagents used in the following examples are as follows:

[0110] 3-Bromo-4-methylphenol: AR, Innochem;

[0111] 3-Bromo-4-fluorophenol: AR, Innochem;

[0112] 2-Bromo-4-tert-butylphenol: AR, Innochem;

[0113] 2-Bromo-4-fluorophenol: AR, Innochem;

[0114] 3,5-di-tert-butylphenylboronic acid: AR, Innochem; benzylboronic acid: AR, Innochem;

[0115] 3-(Trifluoromethyl)phenylboronic acid: AR, Innochem; 7H-dibenzocarbazole: AR, Innochem;

[0116] 2,7-di-tert-butylcarbazole: AR, Innochem;

[0117] 1,2-Dibromoethane: AR, Innochem;

[0118] 1,3-Dibromopropane: AR, Innochem;

[0119] 1,2-Dibromocyclohexane: AR, Innochem;

[0120] Bis(dichloromethyl)dimethylsilane: AR, Innochem; Benzyl bromide: AR, Innochem;

[0121] Potassium carbonate: AR, Innochem;

[0122] Cesium carbonate: AR, Innochem;

[0123] Tetrakis(triphenylphosphine)palladium: AR, Innochem;

[0124] Sodium carbonate: AR, Innochem;

[0125] N-bromosuccinimide: AR, Innochem; pyridinium p-toluenesulfonate: AR, Innochem; 3,4-dihydro-2H-pyran: AR, Innochem;

[0126] n-Butyllithium: AR, Innochem;

[0127] Triisopropyl borate: AR, Innochem;

[0128] Ethylene glycol dimethyl ether: AR, Aladdin;

[0129] Acetonitrile: AR, Innochem;

[0130] Ethanol: AR, Innochem;

[0131] Petroleum ether: AR, Innochem;

[0132] Ethyl acetate: AR, Innochem;

[0133] Tetrahydrofuran: AR, Innochem;

[0134] Hydrochloric acid: AR, aladdin;

[0135] Toluene: AR, Innochem;

[0136] Hydrogen: Yantai Mingju Gas Co., Ltd.;

[0137] Palladium carbon: Hangzhou Kangna New Materials Co., Ltd.;

[0138] TiCl4: Tokyo Chemical Industry Co., Ltd.;

[0139] ZrCl4: Tokyo Chemical Industry Co., Ltd.;

[0140] HfCl4: Tokyo Chemical Industry Co., Ltd.;

[0141] Methylaluminoxane (MAO): Albemarle;

[0142] Modified methylaluminoxane (MMAO): Albemarle;

[0143] Trityltetrakis(pentafluorophenyl)borate: AR, Aladdin;

[0144] Tetrakis(pentafluorophenyl)boric acid-methyldi-(octadecyl)ammonium salt: AR, Aladdin; N,N-dioctadecylmethylaminotetrakis(pentafluorophenyl)borate: AR, Aladdin; Ethylene: 99.9%, Beijing Yanshan Petrochemical Company;

[0145] 1-Hexene: 98%, Beijing Yanshan Petrochemical Company;

[0146] 1-Octene: 98%, Beijing Yanshan Petrochemical Company;

[0147] Isopar E: ExxonMobil Corporation.

[0148] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0149] Unless otherwise specified, the concentrations in the following examples are all molar concentrations.

[0150] In the following examples, "eq" means molar equivalent.

[0151] The compounds in the following examples were characterized using a nuclear magnetic resonance spectrometer (Brucker ARX-400).

[0152] The polymerization activities of the polymers described in the following examples were calculated according to the following formula: Polymerization activity = polymer mass / (metal content in catalyst × polymerization time). The melting points of the polymers were determined using conventional DSC (Q2000) methods. The weight-average molecular weight (Mw) of the polymers was determined using a PL-GPC220 at 160°C. The comonomer insertion rate was calculated using the reference (Macromolecules 1999, 32, 3817).

[0153] In all the following examples and comparative examples, the chemical reactions involved were carried out after nitrogen substitution.

[0154] The following examples 1-10 are used to prepare different bimetallic catalysts:

[0155] [Example 1]

[0156] The bimetallic catalyst A was prepared as follows:

[0157]

[0158] (1) 3-Bromo-4-fluorophenol (1 eq), 3,4-dihydro-2H-pyran (2 eq), and pyridinium p-toluenesulfonate (1 eq) were added to 500 ml of acetonitrile and the mixture was heated to 80°C for 1 h. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound b.

[0159] (2) Compound b (1 eq) was added to 500 ml of dry tetrahydrofuran, cooled to -78°C, and n-butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After reacting for 3 h, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was continued for 3 h. An appropriate amount of water was added to quench the residual n-butyl lithium. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 150:1 (v / v)) to obtain compound c.

[0160] (3) 3-Bromo-4-fluorophenol (1 eq), benzyl bromide (1.1 eq), and potassium carbonate (2 eq) were added to 500 ml of acetonitrile and heated to 60°C for 3 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound e.

[0161] (4) Compound e (1 eq), compound c (1.1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to 500 ml of ethylene glycol dimethyl ether and the temperature was raised to 80°C for 10 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound f.

[0162] 1H NMR (C6D6, 400MHz, TMS): δ7.37(m,4H),7.28(m,2H),7.05-7.10(m,5H),6.34(s,1H),5.57(s,2H),3.71(m,2H),1.67-1.86(m,6H).

[0163] (5) Compound f (1 eq) and N-bromosuccinimide (1 eq) were added to 500 ml of ethanol and reacted at 0°C for 30 min. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound g.

[0164] (6) 2-Bromo-4-fluorophenol (1 eq), 3,4-dihydro-2H-pyran (4 eq), and pyridinium p-toluenesulfonate (0.5 eq) were added to 500 ml of acetonitrile and the mixture was heated to 60°C for 15 h. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound i.

[0165] (7) Compound i (1 eq) was added to 500 ml of dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After reacting for 3 h, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was continued for 3 h. An appropriate amount of water was added to quench the residual n-Butyl lithium. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 150:1 (v / v)) to obtain compound j.

[0166] (8) Compound g (1 eq), compound j (1.2 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to 500 ml of ethylene glycol dimethyl ether and the temperature was raised to 80°C for 10 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound k.

[0167] 1H NMR (C6D6, 400MHz, TMS): δ7.35-7.43(m,6H),7.26(m,2H),7.04-7.10(m,5H),6.41(d,2H),5.58(s,2H),3.68(m,4H),1.62-1.81(m,12H).

[0168] (9) Compound k (1 eq) and N-bromosuccinimide (1 eq) were added to 500 ml of ethanol and reacted at -25°C for 60 min. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound l.

[0169] 1H NMR (C6D6, 400MHz, TMS): δ7.31-7.42(m,6H),7.25(d,1H),7.02-7.09(m,5H),6.43(d,2H),5.60(s,2H),3.71(m,4H),1.60-1.78(m,12H).

[0170] (10) Compound 1 (1 eq) was added to 500 ml of dry tetrahydrofuran and cooled to -20°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After reacting for 3 h, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was continued for 5 h. An appropriate amount of water was added to quench the residual n-Butyl lithium. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 150:1 (v / v)) to obtain compound m.

[0171] (11) 2-Bromo-4-fluorophenol (1 eq), benzyl bromide (1.2 eq), and potassium carbonate (2.5 eq) were added to 500 ml of acetonitrile and heated to 100°C for 1 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound o.

[0172] (12) Compound o (1 eq), 3,5-di-tert-butylphenylboronic acid (1.2 eq), tetrakis(triphenylphosphine)palladium (0.05 eq), and sodium carbonate (2 eq) were added to 500 ml of ethylene glycol dimethyl ether and the temperature was raised to 60°C for 15 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound q.

[0173] 1H NMR (C6D6, 400MHz, TMS): δ7.48(s,2H),7.41(s,1H),7.32-7.36(m,2H),7.28(s,1H),7.05-7.11(m,5H),5.60(s,2H),1.24(s,18H).

[0174] (13) Compound q (1 eq) and N-bromosuccinimide (1.05 eq) were added to 500 ml of ethanol and reacted at 0°C for 40 min. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound r.

[0175] 1H NMR (C6D6, 400MHz, TMS): δ7.48(s,2H),7.41(s,1H),7.33(s,1H),7.27(s,1H),7.05-7.10(m,5H),5.65(s,2H),1.23(s,18H).

[0176] (14) Compound r (1 eq), compound m (1.3 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (2.5 eq) were added to 500 ml of ethylene glycol dimethyl ether, and the temperature was raised to 70°C for reaction for 15 h. Then, hydrochloric acid (3 eq) was added to the reaction solution, and the reaction was continued for 1 h. The raw material disappeared completely after TLC spot plate monitoring. After extraction, concentration, and purification by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)), compound s was obtained.

[0177] 1H NMR (C6D6, 400MHz, TMS): δ7.57(d,2H),7.48(s,2H),7.41(s,1H),7.18-7.36(m,9H),7.02-7.10(m,10H),5.65(s,2H),5.61(s,2H),1.24(s,18H).

[0178] (15) Compound s (1 eq), 1,3-dibromopropane (2 eq), and cesium carbonate (2.5 eq) were added to 500 ml of acetonitrile and heated to 80°C for 2 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound t.

[0179] 1H NMR (C6D6, 400MHz, TMS): δ7.48(s,2H),7.41(s,1H),7.18 -7.36(m,9H),7.02-7.10(m,10H),5.65(s,2H),5.61(s,2H),4.26 -4.28(m,4H),3.63 -3.66(m,4H),2.35 -2.39(m,4H),1.23(s,18H).

[0180] (16) Compound t (1 eq), compound s (1 eq), and cesium carbonate (2.5 eq) were added to 500 ml of acetonitrile and heated to 80°C for 2 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound u.

[0181] 1H NMR(C6D6,400MHz,TMS): δ7.48-7.60(m,4H),7.44(s,1H),7.42(s,1H),7. 40(d,4H),7.17-7.38(m,18H),7.01-7.09(m,20H),5.64-5.68(m,8H),4.35 -4.41(m,8H),3.46-3.49(m,4H),1.31(s,18H),1.23(s,18H).

[0182] (17) Compound u (1 eq), palladium on carbon (0.01 eq), and 500 ml of ethanol were added to a 1 L pressure reactor. The atmosphere was replaced with nitrogen five times, and 0.6 MPa of hydrogen was introduced. The temperature was raised to 100°C and the reaction was carried out for 4 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain ligand v.

[0183] 1H NMR(C6D6,400MHz,TMS): δ7.48-7.60(m,4H),7.44(s,1H),7.42(s,1H),7.40(d,4H),7 .17-7.38(m,18H),4.35-4.41(m,8H),3.46-3.49(m,4H),1.31(s,18H),1.24(s,18H).

[0184] (18) Ligand v (1 eq) was dissolved in 500 ml of dry toluene, cooled to -40 °C, and n-butyl lithium (4.0 eq) was slowly added dropwise. The reaction was continued for 6 h, and then zirconium tetrachloride (2.0 eq) was added. The temperature was raised to 25 °C and the reaction was continued for 10 h. The reaction solution was filtered, concentrated, and crystallized from n-hexane to obtain bimetallic catalyst A.

[0185] [Example 2]

[0186] The bimetallic catalyst B was prepared as follows:

[0187]

[0188] (1) 3-Bromo-4-methylphenol (1 eq), 3,4-dihydro-2H-pyran (1 eq), and pyridinium p-toluenesulfonate (0.1 eq) were added to 500 ml of acetonitrile and the mixture was heated to 60°C for 10 h. The starting material disappeared completely after TLC monitoring. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound b.

[0189] (2) Compound b (1 eq) was added to 500 ml of dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After the reaction was allowed to proceed for 3 h, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was continued for 5 h. An appropriate amount of water was added to quench the residual n-Butyl lithium. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 150:1 (v / v)) to obtain compound c.

[0190] (3) 3-Bromo-4-methylphenol (1 eq), benzyl bromide (1.2 eq), and potassium carbonate (2 eq) were added to 500 ml of acetonitrile and the temperature was raised to 80°C for 3 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound e.

[0191] (4) Compound e (1 eq), compound c (1.1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to 500 ml of ethylene glycol dimethyl ether and the temperature was raised to 80°C for 10 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound f.

[0192] 1H NMR(C6D6,400MHz,TMS): δ7.36(m,4H),7.28(m,2H),7.04-7.10(m,5H),6.34( s,1H),5.56(s,2H),3.71(m,2H),1.67-1.85(m,6H),1.31(s,3H),1.25(s,3H).

[0193] (5) Compound f (1 eq) and N-bromosuccinimide (1 eq) were added to 500 ml of ethanol and reacted at 0°C for 30 min. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound g.

[0194] (6) 2-Bromo-4-tert-butylphenol (1 eq), 3,4-dihydro-2H-pyran (2.5 eq), and pyridinium p-toluenesulfonate (0.5 eq) were added to 500 ml of acetonitrile and the mixture was heated to 60°C for 15 h. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound i.

[0195] (7) Compound i (1 eq) was added to 500 ml of dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After reacting for 3 h, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was continued for 3 h. An appropriate amount of water was added to quench the residual n-Butyl lithium. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 150:1 (v / v)) to obtain compound j.

[0196] (8) Compound g (1 eq), compound j (1.2 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to 500 ml of ethylene glycol dimethyl ether and the temperature was raised to 80°C for 10 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound k.

[0197] 1H NMR(C6D6,400MHz,TMS): δ7.35-7.42(m,6H),7.27(m,2H),7.04-7.10(m,5H),6.42(d,2H) ),5.57(s,2H),3.68(m,4H),1.62-1.82(m,12H),1.29(s,3H),1.26(s,3H),1.20(s,9H).

[0198] (9) Compound k (1 eq) and N-bromosuccinimide (1 eq) were added to 500 ml of ethanol and reacted at -25°C for 60 min. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound l.

[0199] 1H NMR (C6D6, 400MHz, TMS): δ7.36-7.42(m,6H),7.27(m,1H),7.04-7.11(m,5H),6.42(d,2H) ),5.56(s,2H),3.67(m,4H),1.62-1.81(m,12H),1.29(s,3H),1.25(s,3H),1.20(s,9H).

[0200] (10) Compound 1 (1 eq) was added to 500 ml of dry tetrahydrofuran and cooled to -20°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After reacting for 3 h, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was continued for 5 h. An appropriate amount of water was added to quench the residual n-Butyl lithium. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 150:1 (v / v)) to obtain compound m.

[0201] (11) 2-Bromo-4-tert-butylphenol (1 eq), benzyl bromide (1.2 eq), and potassium carbonate (2.5 eq) were added to 500 ml of acetonitrile and heated to 100°C for 1 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound o.

[0202] (12) Compound o (1 eq), 3-(trifluoromethyl)phenylboronic acid (1.2 eq), tetrakis(triphenylphosphine)palladium (0.05 eq), and sodium carbonate (2 eq) were added to 500 ml of ethylene glycol dimethyl ether and the temperature was raised to 60°C for 15 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound q.

[0203] 1H NMR (C6D6, 400MHz, TMS): δ7.42-7.47(m,4H),7.33-7.36(m,2H),7.28(s,1H),7.05-7.11(m,5H),5.60(s,2H),1.25(s,9H).

[0204] (13) Compound q (1 eq) and N-bromosuccinimide (1.05 eq) were added to 500 ml of ethanol and reacted at 0°C for 40 min. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound r.

[0205] 1H NMR (C6D6, 400MHz, TMS): δ7.43-7.47(m,4H),7.34(s,1H),7.27(s,1H),7.04-7.11(m,5H),5.61(s,2H),1.24(s,9H).

[0206] (14) Compound r (1 eq), compound m (1.3 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (2.5 eq) were added to 500 ml of ethylene glycol dimethyl ether, and the temperature was raised to 70°C for reaction for 15 h. Then, hydrochloric acid (3 eq) was added to the reaction solution, and the reaction was continued for 1 h. The raw material disappeared completely after TLC spot plate monitoring. After extraction, concentration, and purification by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)), compound s was obtained.

[0207] 1H NMR(C6D6,400MHz,TMS): δ7.31-7.45(m,6H),7.19-7.27(m,4H),7.04-7.11(m,10H),6.92-6.98(m,3H), 6.87(s,1H),6.74(s,1H),5.84(s,2H),5.68(s,2H),2.57(s,3H),2.42(s,3H),1.29(s,9H),1.22(s,9H).

[0208] (15) Compound s (1 eq), bis(dichloromethyl)dimethylsilane (2 eq), and cesium carbonate (2.5 eq) were added to 500 ml of acetonitrile and heated to 80°C for 2 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound t.

[0209] 1H NMR (C6D6, 400MHz, TMS): δ7.28-7.38(m,6H),7.17-7.25(m,4H),7.04-7.10(m,10H),6.95-6.98(m,3H),5.84(s,2H),5. 66(s,2H),3.50-3.55(m,4H),3.01-3.15(m,4H),2.56(s,3H),2.44(s,3H),1.29(s,9H),1.24(s,9H),0.1-0.2(m,12H).

[0210] (16) Compound t (1 eq), compound s (1 eq), and cesium carbonate (2.5 eq) were added to 500 ml of acetonitrile and heated to 80°C for 2 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound u.

[0211] 1H NMR (C6D6, 400MHz, TMS): δ7.32-7.41(m,12H),7.18-7.22(m,8H),7.03-7.12(m,20H),6.94-6.98(m,6H),5.85(s,4H),5. 67(s,4H),3.51-3.55(m,4H),3.06-3.15(m,4H),2.57(s,6H),2.46(s,6H),1.27(s,18H),1.23(s,18H),0.1-0.2(m,12H).

[0212] (17) Compound u (1 eq), palladium on carbon (0.01 eq), and 500 ml of ethanol were added to a 1 L pressure reactor. The atmosphere was replaced with nitrogen five times, and 0.6 MPa of hydrogen was introduced. The temperature was raised to 100°C and the reaction was carried out for 4 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain ligand v.

[0213] 1H NMR(C6D6,400MHz,TMS): δ7.33-7.40(m,12H),7.18-7.23(m,8H),6.91-6.97(m,6H),3.52-3.57(m ,4H),3.06-3.14(m,4H),2.57(s,6H),2.45(s,6H),1.27(s,18H),1.22(s,18H),0.1-0.2(m,12H).

[0214] (18) The ligand v (1 eq) was dissolved in 500 ml of dry toluene, cooled to -40 °C, and n-butyl lithium (4.0 eq) was slowly added dropwise. The mixture was reacted for 6 h, and then hafnium tetrachloride (2.0 eq) was added. The temperature was raised to 100 °C and the reaction was continued for 10 h. The reaction solution was filtered, concentrated, and crystallized from n-hexane to obtain the bimetallic catalyst B.

[0215] [Example 3]

[0216] Catalyst C was prepared as follows:

[0217]

[0218] (1) 3-Bromo-4-fluorophenol (1 eq), 3,4-dihydro-2H-pyran (5 eq), and pyridinium p-toluenesulfonate (1 eq) were added to 500 ml of acetonitrile and the mixture was heated to 60°C for 10 h. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound b.

[0219] (2) Compound b (1 eq) was added to 500 ml of dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After the reaction was allowed to proceed for 3 h, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was continued for 5 h. An appropriate amount of water was added to quench the residual n-Butyl lithium. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 150:1 (v / v)) to obtain compound c.

[0220] (3) 3-Bromo-4-fluorophenol (1 eq), benzyl bromide (1.2 eq), and potassium carbonate (2 eq) were added to 500 ml of acetonitrile and the temperature was raised to 80°C for 3 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound e.

[0221] (4) Compound e (1 eq), compound c (1.1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to 500 ml of ethylene glycol dimethyl ether and the temperature was raised to 80°C for 10 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound f.

[0222] 1H NMR (C6D6, 400MHz, TMS): δ7.36(m,4H),7.28(m,2H),7.05-7.11(m,5H),6.33(s,1H),5.57(s,2H),3.71(m,2H),1.68-1.82(m,6H).

[0223] (5) Compound f (1 eq) and N-bromosuccinimide (1 eq) were added to 500 ml of ethanol and reacted at 0°C for 30 min. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound g.

[0224] (6) 2-Bromo-4-tert-butylphenol (1 eq), 3,4-dihydro-2H-pyran (3.5 eq), and pyridinium p-toluenesulfonate (0.8 eq) were added to 500 ml of acetonitrile and the mixture was heated to 60°C for 15 h. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound i.

[0225] (7) Compound i (1 eq) was added to 500 ml of dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After reacting for 3 h, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was continued for 3 h. An appropriate amount of water was added to quench the residual n-Butyl lithium. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 150:1 (v / v)) to obtain compound j.

[0226] (8) Compound g (1 eq), compound j (1.2 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to 500 ml of ethylene glycol dimethyl ether and the temperature was raised to 80°C for 10 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound k.

[0227] 1H NMR(C6D6,400MHz,TMS): δ7.36-7.43(m,6H),7.27(m,2H),7.04-7.09(m,5H ),6.41(d,2H),5.57(s,2H),3.68(m,4H),1.62-1.80(m,12H),1.24(s,9H).

[0228] (9) Compound k (1 eq) and N-bromosuccinimide (1 eq) were added to 500 ml of ethanol and reacted at -25°C for 60 min. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound l.

[0229] 1H NMR(C6D6,400MHz,TMS): δ7.30-7.42(m,6H),7.25(d,1H),7.04-7.09(m,5H) ),6.44(d,2H),5.61(s,2H),3.73(m,4H),1.60-1.78(m,12H),1.25(s,9H).

[0230] (10) Compound 1 (1 eq) was added to 500 ml of dry tetrahydrofuran and cooled to -20°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After reacting for 3 h, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was continued for 5 h. An appropriate amount of water was added to quench the residual n-Butyl lithium. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 150:1 (v / v)) to obtain compound m.

[0231] (11) 2-Bromo-4-tert-butylphenol (1 eq), benzyl bromide (1.2 eq), and potassium carbonate (2.5 eq) were added to 500 ml of acetonitrile and heated to 100°C for 1 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound o.

[0232] (12) Compound o (1 eq), 2,7-di-tert-butylcarbazole (1.2 eq), tetrakis(triphenylphosphine)palladium (0.05 eq), and sodium carbonate (2 eq) were added to 500 ml of ethylene glycol dimethyl ether and the temperature was raised to 60°C for 15 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound q.

[0233] 1H NMR (C6D6, 400MHz, TMS): δ7.45(d,2H),7.43(d,2H),7.36(d,2H),7-26-7.31(m,3H),7.02-7.10(m,5H),5.55(s,2H),1.32(s,18H),1.27(s,9H).

[0234] (13) Compound q (1 eq) and N-bromosuccinimide (1.05 eq) were added to 500 ml of ethanol and reacted at 0°C for 40 min. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound r.

[0235] 1H NMR (C6D6, 400MHz, TMS): δ7.51(m,2H),7.42(m,2H),7.36(m,2H),7.24-7.30(m,2H),7.01-7.11(m,5H),5.71(s,2H),1.37(s,18H),1.23(s,9H).

[0236] (14) Compound r (1 eq), compound m (1.3 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (2.5 eq) were added to 500 ml of ethylene glycol dimethyl ether, and the temperature was raised to 70°C for reaction for 15 h. Then, hydrochloric acid (3 eq) was added to the reaction solution, and the reaction was continued for 1 h. The raw material disappeared completely after TLC spot plate monitoring. After extraction, concentration, and purification by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)), compound s was obtained.

[0237] 1H NMR(C6D6,400MHz,TMS): δ7.34-7.49(m,6H),7.17-7.28(m,6H),7.04-7.10(m,10H),6.90-6.94(m ,3H),6.86(s,1H),6.75(s,1H),5.80(s,2H),5.67(s,2H),1.54(s,18H),1.26(s,9H),1.23(s,9H).

[0238] (15) Compound s (1 eq), 1,3-dibromopropane (2 eq), and cesium carbonate (2.5 eq) were added to 500 ml of acetonitrile and heated to 80°C for 2 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound t.

[0239] 1H NMR(C6D6,400MHz,TMS): δ7.31-7.45(m,6H),7.18-7.25(m,6H),7.03-7.10(m,10H),6.91-6.97(m,3H), 5.78(s,2H),5.64(s,2H),4.21-4.48(m,8H),3.46-3.63(m,4H),1.58(s,18H),1.27(s,9H),1.22(s,9H).

[0240] (16) Compound t (1 eq), compound s (1 eq), and cesium carbonate (2.5 eq) were added to 500 ml of acetonitrile and heated to 80°C for 2 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound u.

[0241] 1H NMR(C6D6,400MHz,TMS): δ7.32-7.44(m,12H),7.19-7.26(m,12H),7.03-7.10(m,20H),6.95-6.97(m,6H), 5.82(s,4H),5.64(s,4H),4.35-4.46(m,8H),3.54-3.65(m,4H),1.54(s,36H),1.24(s,18H),1.20(s,18H).

[0242] (17) Compound u (1 eq), palladium on carbon (0.01 eq), and 500 ml of ethanol were added to a 1 L pressure reactor. The atmosphere was replaced with nitrogen five times, and 0.6 MPa of hydrogen was introduced. The temperature was raised to 100°C and the reaction was carried out for 4 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain ligand v.

[0243] 1H NMR(C6D6,400MHz,TMS): δ7.32-7.43(m,12H),7.19-7.25(m,12H),6.94-6.96(m,6H ),4.36-4.46(m,8H),3.54-3.63(m,4H),1.55(s,36H),1.24(s,18H),1.23(s,18H).

[0244] (18) The ligand v (1 eq) was dissolved in 500 ml of dry toluene, cooled to -40 °C, and n-butyl lithium (4.0 eq) was slowly added dropwise. The reaction was continued for 6 h, and then zirconium tetrachloride (2.0 eq) was added. The temperature was raised to 60 °C and the reaction was continued for 10 h. The reaction solution was filtered, concentrated, and crystallized from n-hexane to obtain bimetallic catalyst C.

[0245] [Example 4]

[0246] Catalyst D was prepared as follows:

[0247]

[0248] (1) 3-Bromo-4-methylphenol (1 eq), 3,4-dihydro-2H-pyran (2 eq), and pyridinium p-toluenesulfonate (1 eq) were added to 500 ml of acetonitrile and the mixture was heated to 60°C for 10 h. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound b.

[0249] (2) Compound b (1 eq) was added to 500 ml of dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After the reaction was allowed to proceed for 3 h, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was continued for 5 h. An appropriate amount of water was added to quench the residual n-Butyl lithium. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 150:1 (v / v)) to obtain compound c.

[0250] (3) 3-Bromo-4-methylphenol (1 eq), benzyl bromide (1.2 eq), and potassium carbonate (2 eq) were added to 500 ml of acetonitrile and the temperature was raised to 80°C for 3 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound e.

[0251] (4) Compound e (1 eq), compound c (1.1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to 500 ml of ethylene glycol dimethyl ether and the temperature was raised to 80°C for 10 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound f.

[0252] 1H NMR(C6D6,400MHz,TMS): δ7.36(m,4H),7.28(m,2H),7.04-7.10(m,5H),6.34( s,1H),5.55(s,2H),3.71(m,2H),1.67-1.85(m,6H),1.31(s,3H),1.25(s,3H).

[0253] (5) Compound f (1 eq) and N-bromosuccinimide (1 eq) were added to 500 ml of ethanol and reacted at 0°C for 30 min. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound g.

[0254] (6) 2-Bromo-4-tert-butylphenol (1 eq), 3,4-dihydro-2H-pyran (2.5 eq), and pyridinium p-toluenesulfonate (0.5 eq) were added to 500 ml of acetonitrile and the mixture was heated to 60°C for 15 h. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound i.

[0255] (7) Compound i (1 eq) was added to 500 ml of dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After reacting for 3 h, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was continued for 3 h. An appropriate amount of water was added to quench the residual n-Butyl lithium. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 150:1 (v / v)) to obtain compound j.

[0256] (8) Compound g (1 eq), compound j (1.2 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to 500 ml of ethylene glycol dimethyl ether and the temperature was raised to 80°C for 10 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound k.

[0257] 1H NMR(C6D6,400MHz,TMS): δ7.35-7.42(m,6H),7.27(m,2H),7.05-7.10(m,5H),6.42(d,2H) ),5.57(s,2H),3.68(m,4H),1.62-1.82(m,12H),1.29(s,3H),1.26(s,3H),1.20(s,9H).

[0258] (9) Compound k (1 eq) and N-bromosuccinimide (1 eq) were added to 500 ml of ethanol and reacted at -25°C for 60 min. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound l.

[0259] 1H NMR(C6D6,400MHz,TMS): δ7.36-7.43(m,6H),7.27(m,1H),7.04-7.11(m,5H),6.42(d,2H) ),5.56(s,2H),3.67(m,4H),1.62-1.81(m,12H),1.29(s,3H),1.25(s,3H),1.20(s,9H).

[0260] (10) Compound 1 (1 eq) was added to 500 ml of dry tetrahydrofuran and cooled to -20°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After reacting for 3 h, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was continued for 5 h. An appropriate amount of water was added to quench the residual n-Butyl lithium. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 150:1 (v / v)) to obtain compound m.

[0261] (11) 2-Bromo-4-tert-butylphenol (1 eq), benzyl bromide (1.2 eq), and potassium carbonate (2.5 eq) were added to 500 ml of acetonitrile and heated to 100°C for 1 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound o.

[0262] (12) Compound o (1 eq), benzylboronic acid (1.2 eq), tetrakis(triphenylphosphine)palladium (0.05 eq), and sodium carbonate (2 eq) were added to 500 ml of ethylene glycol dimethyl ether and the temperature was raised to 60°C for 15 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound q.

[0263] 1H NMR (C6D6, 400MHz, TMS): δ7.31-7.35(m,2H),7.26(s,1H),6.98-7.10(m,10H),5.60(s,2H),3.60(s,2H),1.25(s,9H).

[0264] (13) Compound q (1 eq) and N-bromosuccinimide (1.05 eq) were added to 500 ml of ethanol and reacted at 0°C for 40 min. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound r.

[0265] 1H NMR(C6D6,400MHz,TMS):7.18-7.26(m,2H),7.04-7.11(m,10H),5.78(s,2H),4.67(s,2H),1.23(s,9H).

[0266] (14) Compound r (1 eq), compound m (1.3 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (2.5 eq) were added to 500 ml of ethylene glycol dimethyl ether, and the temperature was raised to 70°C for reaction for 15 h. Then, hydrochloric acid (3 eq) was added to the reaction solution, and the reaction was continued for 1 h. The raw material disappeared completely after TLC spot plate monitoring. After extraction, concentration, and purification by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)), compound s was obtained.

[0267] 1H NMR(C6D6,400MHz,TMS):7.22-7.41(m,6H),7.04-7.11(m,15H),6.90-7.00(m,3H),6.87(s,1H),6.7 2(s,1H),5.78(s,2H),5.65(s,2H),4.13(s,2H),2.56(s,3H),2.47(s,3H),1.26(s,9H),1.22(s,9H).

[0268] (15) Compound s (1 eq), 1,2-dibromocyclohexane (2 eq), and cesium carbonate (2.5 eq) were added to 500 ml of acetonitrile and heated to 80°C for 2 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound t.

[0269] 1H NMR(C6D6,400MHz,TMS):7.25-7.41(m,6H),7.03-7.12(m,15H),6.90-7.01(m,3H),5.75(s,2H),5.67(s,2H),4.67(m,2 H),4.43(m,2H),4.14(s,2H),2.56(s,3H),2.45(s,3H),1.71-1.84(m,8H),1.41-1.66(m,8H),1.25(s,9H),1.22(s,9H).

[0270] (16) Compound t (1 eq), compound s (1 eq), and cesium carbonate (2.5 eq) were added to 500 ml of acetonitrile and heated to 80°C for 2 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound u.

[0271] 1H NMR(C6D6,400MHz,TMS):7.27-7.41(m,12H),7.04-7.12(m,30H),6.90-7.03(m,6H),5.76(s,4H),5.68(s,4H),4.70(m,2H) ),4.45(m,2H),4.14(s,4H),2.58(s,6H),2.44(s,6H),1.71-1.85(m,8H),1.41-1.67(m,8H),1.26(s,18H),1.23(s,18H).

[0272] (17) Compound u (1 eq), palladium on carbon (0.01 eq), and 500 ml of ethanol were added to a 1 L pressure reactor. The atmosphere was replaced with nitrogen five times, and 0.6 MPa of hydrogen was introduced. The temperature was raised to 100°C and the reaction was carried out for 4 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain ligand v.

[0273] 1H NMR(C6D6,400MHz,TMS):7.25-7.41(m,12H),6.91-7.04(m,6H),6.81-86(m,2H),6.70-75(m,2H),4.71(m,2H),4.4 2(m,2H),4.13(s,4H),2.60(s,6H),2.45(s,6H),1.71-1.79(m,8H),1.41-1.65(m,8H),1.27(s,18H),1.22(s,18H).

[0274] (18) The ligand v (1 eq) was dissolved in 500 ml of dry toluene, cooled to -40 °C, and n-butyl lithium (4.0 eq) was slowly added dropwise. The reaction was continued for 6 h, and then zirconium tetrachloride (2.0 eq) was added. The temperature was raised to 80 °C and the reaction was continued for 10 h. The reaction solution was filtered, concentrated, and crystallized from n-hexane to obtain the bimetallic catalyst D.

[0275] [Example 5]

[0276] Catalyst E was prepared as follows:

[0277]

[0278] (1) 3-Bromo-4-fluorophenol (1 eq), 3,4-dihydro-2H-pyran (1 eq), and pyridinium p-toluenesulfonate (1 eq) were added to 500 ml of acetonitrile and the mixture was heated to 60°C for 10 h. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound b.

[0279] (2) Compound b (1 eq) was added to 500 ml of dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After the reaction was allowed to proceed for 3 h, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was continued for 5 h. An appropriate amount of water was added to quench the residual n-Butyl lithium. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 150:1 (v / v)) to obtain compound c.

[0280] (3) 3-Bromo-4-fluorophenol (1 eq), benzyl bromide (1.2 eq), and potassium carbonate (2 eq) were added to 500 ml of acetonitrile and the temperature was raised to 80°C for 3 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound e.

[0281] (4) Compound e (1 eq), compound c (1.1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to 500 ml of ethylene glycol dimethyl ether and the temperature was raised to 80°C for 10 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound f.

[0282] 1H NMR (C6D6, 400MHz, TMS): δ7.36(m,4H),7.28(m,2H),7.05-7.10(m,5H),6.34(s,1H),5.57(s,2H),3.71(m,2H),1.67-1.86(m,6H).

[0283] (5) Compound f (1 eq) and N-bromosuccinimide (1 eq) were added to 500 ml of ethanol and reacted at 0°C for 30 min. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound g.

[0284] (6) 2-Bromo-4-tert-butylphenol (1 eq), 3,4-dihydro-2H-pyran (1 eq), and pyridinium p-toluenesulfonate (0.5 eq) were added to 500 ml of acetonitrile and the mixture was heated to 60°C for 15 h. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound i.

[0285] (7) Compound i (1 eq) was added to 500 ml of dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After reacting for 3 h, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was continued for 3 h. An appropriate amount of water was added to quench the residual n-Butyl lithium. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 150:1 (v / v)) to obtain compound j.

[0286] (8) Compound g (1 eq), compound j (1.2 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to 500 ml of ethylene glycol dimethyl ether and the temperature was raised to 80°C for 10 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound k.

[0287] 1H NMR(C6D6,400MHz,TMS): δ7.35-7.43(m,6H),7.26(m,2H),7.04-7.10(m,5H ),6.41(d,2H),5.58(s,2H),3.68(m,4H),1.62-1.81(m,12H),1.24(s,9H).

[0288] (9) Compound k (1 eq) and N-bromosuccinimide (1 eq) were added to 500 ml of ethanol and reacted at -25°C for 60 min. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound l.

[0289] 1H NMR(C6D6,400MHz,TMS): δ7.31-7.42(m,6H),7.25(d,1H),7.02-7.09(m,5H) ),6.43(d,2H),5.60(s,2H),3.71(m,4H),1.60-1.78(m,12H),1.21(s,9H).

[0290] (10) Compound 1 (1 eq) was added to 500 ml of dry tetrahydrofuran and cooled to -20°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After reacting for 3 h, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was continued for 5 h. An appropriate amount of water was added to quench the residual n-Butyl lithium. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 150:1 (v / v)) to obtain compound m.

[0291] (11) 2-Bromo-4-tert-butylphenol (1 eq), benzyl bromide (1.2 eq), and potassium carbonate (2.5 eq) were added to 500 ml of acetonitrile and heated to 100°C for 1 h. TLC was monitored for complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound o.

[0292] (12) Compound o (1 eq), 7H-dibenzocarbazole (1.2 eq), tetrakis(triphenylphosphine)palladium (0.05 eq), and sodium carbonate (2 eq) were added to 500 ml of ethylene glycol dimethyl ether and the temperature was raised to 60°C for 15 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound q.

[0293] 1H NMR (C6D6, 400MHz, TMS): δ7.42-7.46(m,6H),7.35(m,4H),7.23-7.31(m,4H),7.02-7.09(m,5H),5.62(s,2H),1.23(s,9H).

[0294] (13) Compound q (1 eq) and N-bromosuccinimide (1.05 eq) were added to 500 ml of ethanol and reacted at 0°C for 40 min. TLC was performed to monitor the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound r.

[0295] 1H NMR(C6D6,400MHz,TMS):7.36-7.54(m,6H),7.19-7.29(m,6H),7.02-7.10(m,5H),6.85-6.90(m,2H),5.65(s,2H)1.22(s,9H).

[0296] (14) Compound r (1 eq), compound m (1.3 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (2.5 eq) were added to 500 ml of ethylene glycol dimethyl ether, and the temperature was raised to 70°C for reaction for 15 h. Then, hydrochloric acid (3 eq) was added to the reaction solution, and the reaction was continued for 1 h. The raw material disappeared completely after TLC spot plate monitoring. After extraction, concentration, and purification by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)), compound s was obtained.

[0297] 1H NMR(C6D6,400MHz,TMS):7.43-7.58(m,6H),7.35-7.43(m,4H),7.18-7.31(m,4H),6.98-7.10(m,10H ),6.87-6.96(m,7H),6.84(s,1H),6.68(s,1H),5.78(s,2H),5.65(s,2H),1.26(s,9H),1.22(s,9H).

[0298] (15) Compound s (1 eq), 1,2-dibromoethane (2 eq), and cesium carbonate (2.5 eq) were added to 500 ml of acetonitrile and heated to 80°C for 2 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound t.

[0299] 1H NMR(C6D6,400MHz,TMS):7.45-7.54(m,6H),7.36-7.44(m,4H),7.18-7.32(m,4H),6.99-7.10(m,10H),6.87-6.91 (m,7H),5.80(s,2H),5.67(s,2H),4.83(t,2H),4.67(t,2H),3.64(t,2H),3.43(t,2H),1.34(s,9H),1.22(s,9H).

[0300] (16) Compound t (1 eq), compound s (1 eq), and cesium carbonate (2.5 eq) were added to 500 ml of acetonitrile and heated to 80°C for 2 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound u.

[0301] 1H NMR(C6D6,400MHz,TMS):7.41-7.55(m,12H),7.37-7.41(m,8H),7.19-7.35(m,8H),7.01-7.11(m,20H),6.82-6.90 (m,14H),5.81(s,4H),5.75(s,4H),4.64(m,4H),3.57(m,4H),1.45(s,9H),1.33(s,9H),1.28(s,9H),1.22(s,9H).

[0302] (17) Compound u (1 eq), palladium on carbon (0.01 eq), and 500 ml of ethanol were added to a 1 L pressure reactor. The atmosphere was replaced with nitrogen five times, and 0.6 MPa of hydrogen was introduced. The temperature was raised to 100°C and the reaction was carried out for 4 h. TLC monitoring indicated the complete disappearance of the starting material. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain ligand v.

[0303] 1H NMR(C6D6,400MHz,TMS):7.41-7.55(m,12H),7.37-7.41(m,8H),7.19-7.35(m,8H),6.75-6 .90(m,18H),4.64(m,4H),3.57(m,4H),1.45(s,9H),1.33(s,9H),1.28(s,9H),1.22(s,9H).

[0304] (18) The ligand v (1 eq) was dissolved in 500 ml of dry toluene, cooled to -40 °C, and n-butyl lithium (4.0 eq) was slowly added dropwise. The reaction was continued for 6 h, and then titanium tetrachloride (2.0 eq) was added. The temperature was raised to 80 °C and the reaction was continued for 10 h. The reaction solution was filtered, concentrated, and crystallized from n-hexane to obtain the bimetallic catalyst E.

[0305] [Example 6]

[0306] Bimetallic catalyst F was prepared by a method substantially the same as that in Example 1, except that zirconium tetrachloride in step (18) was replaced by titanium tetrachloride.

[0307] [Example 7]

[0308] The bimetallic catalyst G was prepared by a method substantially the same as that in Example 1, except that the zirconium tetrachloride in step (18) was replaced by hafnium tetrachloride.

[0309] [Example 8]

[0310] The bimetallic catalyst H was prepared by a method substantially the same as that in Example 2, except that the hafnium tetrachloride in step (18) was replaced by zirconium tetrachloride.

[0311] [Example 9]

[0312] The bimetallic catalyst I was prepared by a method substantially the same as that in Example 3, except that the zirconium tetrachloride in step (18) was replaced by hafnium tetrachloride.

[0313] [Example 10]

[0314] Bimetallic catalyst J was prepared by a method substantially the same as that of Example 4, except that the zirconium tetrachloride in step (18) was replaced by hafnium tetrachloride.

[0315] The following Examples 11-28 were used to prepare olefin polymers:

[0316] [Example 11]

[0317] A 1L autoclave containing a weighed amount of bimetallic catalyst A (1 μmol), a temperature sensor, a cooling reflux device, and a mechanical stirrer was dried continuously at 130°C for 2 hours, then evacuated and gradually cooled to 25°C. 300mL of Isopar E, 80mL of 1-octene (an α-olefin), and a predetermined amount of MMAO (a molar ratio of Al to Zr) were added to the autoclave. The temperature was raised to the desired polymerization temperature of 150°C, and ethylene gas was introduced at 5.0 MPa. The ampoule was then broken to initiate the polymerization reaction. Throughout the polymerization, the stirring rate, polymerization temperature, and ethylene pressure were maintained constant. After 10 minutes, the autoclave was vented, and the reaction mixture was neutralized with a 5% hydrochloric acid-containing industrial alcohol solution. The polymer precipitate was washed several times, dried under vacuum to a constant weight, and sampled for analysis.

[0318] [Examples 12-28]

[0319] Olefin polymers were prepared according to the raw materials, feed ratios, reaction conditions, etc. in Table 1. The molar ratio of Al in the organoaluminum adjuvant to the metal in the bimetallic catalyst is denoted as "Ratio 1," and the molar ratio of B in the boronated adjuvant to the metal in the bimetallic catalyst is denoted as "Ratio 2."

[0320] [Comparative Example 1]

[0321] A catalyst having the following structure was prepared according to the method in patent CN106459286B (see patent Example 4), recorded as catalyst D1, and olefin polymer was prepared using this catalyst under the same reaction conditions as in Example 19.

[0322]

[0323] [Comparative Example 2]

[0324] A commercially available catalyst SC-5899, manufactured by Jiangsu Xinnok (referred to as catalyst D2), was used to prepare an olefin polymer under the same reaction conditions as in Example 19.

[0325]

[0326] Table 1, Reaction Conditions in Examples 11-28 and Comparative Examples 1-2

[0327]

[0328] Note: B1 represents tetrakis(pentafluorophenyl)boric acid-methyldi-(octadecyl)ammonium salt, B2 represents trityl tetrakis(pentafluorophenyl)borate, and B3 represents N,N-dioctadecylmethylamino tetrakis(pentafluorophenyl)borate.

[0329] The olefin polymers obtained in the Examples and Comparative Examples were subjected to the performance tests shown in Table 2, and the results were as follows:

[0330] Table 2. Performance test results

[0331]

[0332] The above is only a preferred embodiment of the present invention. It should be pointed out that ordinary technicians in this field can make several improvements and supplements without departing from the method of the present invention. These improvements and supplements should also be considered within the scope of protection of the present invention.

Claims

1. A bimetallic catalyst, characterized in that: It has the general structural formula shown in Formula I: Where, R1-R 12 are independently selected from hydrogen, halogen, carbazolyl, benzocarbazolyl, dibenzocarbazolyl or any of the following groups: C1-C 24 Alkyl, C6-C 30 Aralkyl, C6-C 30 Arylalkyl halides, C 12 -C 40 The alkyl group of the carbazolyl group; T1 and T2 are the same or different bridging groups, each independently selected from C1-C 20 an alkyl group, a cycloalkyl group, or a silyl group; X is selected from halogen, C1-C6 alkyl or alkoxy, C6-C 20 Aryl or aralkyl, C3-C 12 Silane group or siloxane group; n is 2; M1 and M2 are the same or different and are independently selected from titanium, zirconium and hafnium.

2. The bimetallic catalyst according to claim 1, characterized in that In Formula I, R1-R 12 are independently selected from hydrogen, halogen, carbazolyl, benzocarbazolyl, dibenzocarbazolyl or any of the following groups: C1-C 15 Alkyl, C6-C 24 Aralkyl, C6-C 24 Arylalkyl halides, C 12 -C 24 The alkyl group of the carbazolyl group; T1 and T2 are each independently selected from C1-C 18 an alkyl group, a cycloalkyl group, or a silyl group; X is selected from chlorine, methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, methoxy, ethoxy, n-propoxy, n-butoxy, vinyl, propenyl, butenyl, phenyl, biphenyl, 1-naphthyl, benzyl, 2-methylphenyl, 3-methylphenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 3-ethylphenyl, trimethylsilyl, ethyldimethylsilyl, methoxydimethylsilyl.

3. The bimetallic catalyst according to claim 2, characterized in that The bimetallic catalyst is selected from one or more compounds having the following structural expressions:

4. A method for preparing a bimetallic catalyst according to any one of claims 1 to 3, characterized in that: The following steps are involved: In an ultra-dry organic solvent, the ligand represented by formula II is first reacted with a hydrogen extraction reagent to form a salt, and then complexed with a metal M salt to prepare a bimetallic catalyst; In Formula II, R1-R 12 The definitions of T1, T2 and R1-R2 in any one of claims 1-3 are the same as those in any one of claims 1-3. 12 , T1, and T2 have the same definitions.

5. The method for preparing a bimetallic catalyst according to claim 4, characterized in that: The ultra-dry organic solvent is one or more of toluene, xylene, pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, methylcyclohexane, octane, isooctane, tetrahydrofuran, and ether.

6. The method for preparing a bimetallic catalyst according to claim 5, characterized in that: The ultra-dry organic solvent is toluene or n-hexane.

7. The method for preparing a bimetallic catalyst according to claim 4, characterized in that: The hydrogen extraction reagent is one or more of alkyl lithium, phenyl lithium, sodium hydride, potassium hydride, lithium hydride, tetramethylethylenediamine, lithium bistrimethylsilylamide, sodium bistrimethylsilylamide, lithium diisopropylamide, and potassium carbonate.

8. The method for preparing a bimetallic catalyst according to claim 7, characterized in that: The hydrogen extraction reagent is n-butyl lithium.

9. The method for preparing a bimetallic catalyst according to claim 4, characterized in that: The metal M salt is one or more of titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, dibenzyltitanium dichloride, dibenzylzirconium dichloride, dibenzylhafnium dichloride, trimethylsilylmethylenetitanium dichloride, trimethylsilylmethylenezirconium dichloride, and trimethylsilylmethylenehafnium dichloride.

10. The method for preparing a bimetallic catalyst according to claim 4, characterized in that: The molar ratio of the ligand represented by formula II to the hydrogen extraction agent is 1:(4.0-5.0); the molar ratio of the ligand represented by formula II to the metal M salt is 1:(2.0-2.5).

11. The method for preparing a bimetallic catalyst according to claim 4, characterized in that: The salt-forming reaction temperature is -78 to 40° C., and the salt-forming reaction time is 1 to 12 hours.

12. The method for preparing a bimetallic catalyst according to claim 4, characterized in that: The complexation reaction temperature is 0-180° C., and the complexation reaction time is 1-24 hours.

13. The method for preparing a bimetallic catalyst according to claim 4, characterized in that: The preparation method of the ligand shown in formula II is as follows: Among them, R1-R 12 The definitions of T1, T2 and R1-R2 in any one of claims 1-3 are the same as those in any one of claims 1-3. 12 , T1, T2 are the same as defined above; R is selected from a boric acid group, a hydroxyl group, an amino group or a carboxyl group; 1) reacting compound a and 3,4-dihydro-2H-pyran (DHP) in the presence of pyridinium p-toluenesulfonate to produce compound b; 2) reacting compound b with a lithiation reagent and triisopropyl borate to generate compound c; 3) reacting compound d and benzyl halide in the presence of a base to produce compound e; 4) reacting compound e and compound c in the presence of a palladium catalyst and a base to produce compound f; 5) Compound f is mixed with a bromination reagent to react to generate compound g; 6) reacting compound h and 3,4-dihydro-2H-pyran in the presence of pyridinium p-toluenesulfonate to produce compound i; 7) reacting compound i with a lithiation reagent and triisopropyl borate to generate compound j; 8) reacting compound g and compound j in the presence of a palladium catalyst and a base to produce compound k; 9) Compound k is mixed with a bromination reagent to react to generate compound 1; 10) reacting compound 1 with a lithiation reagent and triisopropyl borate to generate compound m; 11) reacting compound n and benzyl halide in the presence of a base to produce compound o; 12) reacting compound o and compound p in the presence of a palladium catalyst and a base to produce compound q; 13) Compound q is reacted with a bromination reagent to generate compound r; 14) reacting compound r and compound m in the presence of a palladium catalyst and a base, and adding hydrochloric acid after the reaction to remove the hydroxyl protecting group THP to generate compound s; 15) reacting compound s and a dihalogenated hydrocarbon in the presence of a base to produce compound t; 16) reacting compound t and compound s in the presence of a base to produce compound u; 17) Compound u is subjected to a debenzylation reaction in the presence of hydrogen and palladium on carbon to obtain a ligand represented by formula II.

14. The method for preparing a bimetallic catalyst according to claim 13, characterized in that: In step 1), the reaction conditions are: reaction temperature 25-80° C., reaction time 1-24 h.

15. The method for preparing a bimetallic catalyst according to claim 13, characterized in that: In step 2), the reaction conditions are: reaction temperature -78 to 25° C., and reaction time 1 to 10 h.

16. The method for preparing a bimetallic catalyst according to claim 13, characterized in that: In step 3), the reaction conditions are: reaction temperature 25-100° C., reaction time 1-8 h.

17. The method for preparing a bimetallic catalyst according to claim 13, characterized in that: In step 4), the reaction conditions are: reaction temperature 25-150° C., reaction time 1-24 h.

18. The method for preparing a bimetallic catalyst according to claim 13, characterized in that: In step 5), the reaction conditions are: reaction temperature -25 to 25° C., and reaction time 5 to 60 min.

19. The method for preparing a bimetallic catalyst according to claim 13, wherein: In step 6), the reaction conditions are: reaction temperature 25-80° C., reaction time 1-24 h.

20. The method for preparing a bimetallic catalyst according to claim 13, characterized in that: In step 7), the reaction conditions are: reaction temperature -78 to 25° C., and reaction time 1 to 10 h.

21. The method for preparing a bimetallic catalyst according to claim 13, wherein: In step 8), the reaction conditions are: reaction temperature 25-150° C., reaction time 1-24 h.

22. The method for preparing a bimetallic catalyst according to claim 13, wherein: In step 9), the reaction conditions are: reaction temperature -25 to 25° C., and reaction time 5 to 60 min.

23. The method for preparing a bimetallic catalyst according to claim 13, characterized in that: In step 10), the reaction conditions are: reaction temperature -78 to 25° C., and reaction time 1 to 10 h.

24. The method for preparing a bimetallic catalyst according to claim 13, wherein: In step 11), the reaction conditions are: reaction temperature 25-100° C., reaction time 1-8 h.

25. The method for preparing a bimetallic catalyst according to claim 13, wherein: In step 12), the reaction conditions are: reaction temperature 25-150° C., reaction time 1-24 h.

26. The method for preparing a bimetallic catalyst according to claim 13, wherein: In step 13), the reaction conditions are: reaction temperature -25 to 25° C., and reaction time 5 to 60 min.

27. The method for preparing a bimetallic catalyst according to claim 13, wherein: In step 14), the reaction conditions are: reaction temperature 25-150° C., reaction time 1-24 h.

28. The method for preparing a bimetallic catalyst according to claim 13, characterized in that: In step 15), the reaction conditions are: reaction temperature 25-100° C., reaction time 1-4 h.

29. The method for preparing a bimetallic catalyst according to claim 13, wherein: In step 16), the reaction conditions are: reaction temperature 25-100° C., reaction time 1-4 h.

30. The method for preparing a bimetallic catalyst according to claim 13, wherein: In step 17), the reaction conditions are: reaction temperature 25-150° C., reaction time 1-5 h.

31. The method for preparing a bimetallic catalyst according to any one of claims 13 to 30, characterized in that: Compound a is selected from one or more of 3-bromo-4-methylphenol, 3-bromo-4-fluorophenol, 3-bromo-5-methylphenol, 3-bromo-4-ethylphenol, m-bromophenol, 3-bromo-4-(trifluoromethyl)phenol, 3-bromo-4-chlorophenol, 3-bromo-4-methoxyphenol, and 3-bromo-5-methoxyphenol.

32. The method for preparing a bimetallic catalyst according to claim 31, characterized in that: The compound d is selected from one or more of 3-bromo-4-methylphenol, 3-bromo-4-fluorophenol, 3-bromo-5-methylphenol, 3-bromo-4-ethylphenol, m-bromophenol, 3-bromo-4-(trifluoromethyl)phenol, 3-bromo-4-chlorophenol, 3-bromo-4-methoxyphenol, and 3-bromo-5-methoxyphenol.

33. The method for preparing a bimetallic catalyst according to claim 31, wherein: The compound h is selected from one or more of 2-bromo-4-tert-butylphenol, 2-bromo-4-methylphenol, 2-bromo-4-fluorophenol, 2-bromophenol, 2-bromo-4,5-dimethylphenol, 2-bromo-4-ethylphenol, 3-bromo-4-hydroxybiphenyl, 2-bromo-4,6-dimethylphenol, 2-bromo-4-trifluoromethylphenol, and 2-bromo-6-(trifluoromethyl)phenol.

34. The method for preparing a bimetallic catalyst according to claim 31, wherein: The compound n is selected from one or more of 2-bromo-4-tert-butylphenol, 2-bromo-4-methylphenol, 2-bromo-4-fluorophenol, 2-bromo-5-methylphenol, 2-bromo-3-methylphenol, 2-bromo-4,5-dimethylphenol, 2-bromo-3,5-dimethylphenol, 2-bromo-5-fluorophenol, 2-bromo-4,5-difluorophenol, 2-bromo-3,5-difluorophenol, and 2-bromo-4-trifluoromethylphenol.

35. The method for preparing a bimetallic catalyst according to claim 31, wherein: The compound p is selected from one or more of 3,5-di-tert-butylphenylboronic acid, benzylboronic acid, 2-naphthaleneboronic acid, 1-naphthaleneboronic acid, 3-(trifluoromethyl)phenylboronic acid, 9-phenanthreneboric acid, 2-triphenylboronic acid, 2-anthraceneboric acid, 9-anthraceneboric acid, 7H-dibenzocarbazole, 2,7-di-tert-butylcarbazole, carbazole, 11H-benzo[C]carbazole, and indole.

36. The method for preparing a bimetallic catalyst according to claim 31, wherein: The dihalogenated hydrocarbon is selected from one or more of 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,2-dibromocyclohexane, and bis(dichloromethyl)dimethylsilane.

37. The method for preparing a bimetallic catalyst according to claim 31, wherein: The lithiation agent is selected from n-butyllithium and / or n-hexyllithium.

38. The method for preparing a bimetallic catalyst according to claim 31, wherein: The benzyl halide is selected from benzyl bromide and / or benzyl chloride.

39. The method for preparing a bimetallic catalyst according to claim 31, wherein: The palladium catalyst is selected from one or more of tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, 1,1'-bis(diphenylphosphino)ferrocenepalladium dichloride(II), tris(dibenzylidene-base acetone)dipalladium(0), palladium chloride, triphenylphosphine palladium acetate, bis(tri-tert-butylphosphine)palladium, bis(tricyclohexylphosphine)palladium(0), palladium acetate, and benzyl(chloro)bis(triphenylphosphine)palladium(II).

40. The method for preparing a bimetallic catalyst according to claim 31, wherein: The base is selected from one or more of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, potassium phosphate, cesium fluoride, sodium bicarbonate, rubidium carbonate, cesium carbonate, francium carbonate, and barium hydroxide.

41. The method for preparing a bimetallic catalyst according to claim 31, wherein: The brominating agent is selected from liquid bromine and / or N-bromosuccinimide.

42. The method for preparing a bimetallic catalyst according to any one of claims 13 to 30, characterized in that: In step 1), the molar ratio of compound a, 3,4-dihydro-2H-pyran, and pyridinium p-toluenesulfonate is 1:(1-5):(0.1-1).

43. The method for preparing a bimetallic catalyst according to claim 42, wherein: In step 2), the molar ratio of compound b, the lithiation reagent, and triisopropyl borate is 1:(1-2):(1-2).

44. The method for preparing a bimetallic catalyst according to claim 42, wherein: In step 3), the molar ratio of compound d, benzyl halide and base is 1:(1-2):(1-2).

45. The method for preparing a bimetallic catalyst according to claim 42, wherein: In step 4), the molar ratio of compound e, compound c, palladium catalyst and base is 1:(1-2):(0.001-0.1):(1-3).

46. ​​The method for preparing a bimetallic catalyst according to claim 42, wherein: In step 5), the molar ratio of compound f and bromination reagent is 1:(0.8-1.2).

47. The method for preparing a bimetallic catalyst according to claim 42, wherein: In step 6), the molar ratio of compound h, 3,4-dihydro-2H-pyran, and pyridinium p-toluenesulfonate is 1:(1-5):(0.1-1).

48. The method for preparing a bimetallic catalyst according to claim 42, wherein: In step 7), the molar ratio of compound i, the lithiation reagent, and triisopropyl borate is 1:(1-2):(1-2).

49. The method for preparing a bimetallic catalyst according to claim 42, wherein: In step 8), the molar ratio of compound g, compound j, palladium catalyst and base is 1:(1-2):(0.001-0.1):(1-3).

50. The method for preparing a bimetallic catalyst according to claim 42, wherein: In step 9), the molar ratio of compound k to the bromination reagent is 1:(0.8-1.2).

51. The method for preparing a bimetallic catalyst according to claim 42, wherein: In step 10), the molar ratio of compound 1, the lithiation reagent, and triisopropyl borate is 1:(1-2):(1-2).

52. The method for preparing the bimetallic catalyst according to claim 42, wherein: In step 11), the molar ratio of compound n, benzyl halide and base is 1:(1-2):(1-2).

53. The method for preparing the bimetallic catalyst according to claim 42, wherein: In step 12), the molar ratio of compound o, compound p, palladium catalyst and base is 1:(1-2):(0.001-0.1):(1-3).

54. The method for preparing a bimetallic catalyst according to claim 42, wherein: In step 13), the molar ratio of compound q to the bromination reagent is 1:(0.8-1.2).

55. The method for preparing a bimetallic catalyst according to claim 42, wherein: In step 14), the molar ratio of compound r, compound m, palladium catalyst, base and hydrochloric acid is 1:(1-2):(0.001-0.1):(1-3):(1-2).

56. The method for preparing a bimetallic catalyst according to claim 42, wherein: In step 15), the molar ratio of compound s, dihalogenated hydrocarbon, and base is 1:(2-8):(1-2).

57. The method for preparing a bimetallic catalyst according to claim 42, wherein: In step 16), the molar ratio of compound t, compound s, and base is 1:(0.8-1.2):(1-2).

58. The method for preparing a bimetallic catalyst according to claim 42, wherein: In step 17), the molar ratio of compound u, hydrogen, and palladium carbon is 1:(4-10):(0.1-1).

59. A method for preparing a high molecular weight olefin polymer, characterized in that: In the presence of the bimetallic catalyst described in any one of claims 1 to 3 or the bimetallic catalyst prepared by the method described in any one of claims 4 to 58, an organic aluminum auxiliary and an optional boronated auxiliary are added simultaneously to allow ethylene and α-olefin to undergo polymerization in an organic solvent to produce a high molecular weight olefin polymer.

60. The method for preparing a high molecular weight olefin polymer according to claim 59, wherein: The ratio of the organoaluminum auxiliary agent to the bimetallic catalyst is 1-2000 based on the metal molar ratio.

61. The method for preparing a high molecular weight olefin polymer according to claim 60, wherein: The ratio of the organoaluminum auxiliary agent to the bimetallic catalyst is 2-800 based on the metal molar ratio.

62. The method for preparing a high molecular weight olefin polymer according to claim 59, wherein: The ratio of the boronization auxiliary agent to the bimetallic catalyst is 0-60 based on the molar ratio of the boron element to the metal element.

63. The method for preparing a high molecular weight olefin polymer according to claim 62, wherein: The ratio of the boronization auxiliary agent to the bimetallic catalyst is 0-10 based on the molar ratio of the boron element to the metal element.

64. The method for preparing a high molecular weight olefin polymer according to claim 59, wherein: The organoaluminum auxiliary agent is selected from one or more of aluminoxane, alkylaluminum compound, and alkylaluminum chloride.

65. The method for preparing a high molecular weight olefin polymer according to claim 64, wherein: The aluminoxane is one or more of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, isobutylaluminoxane, neopentylaluminoxane, n-hexylaluminoxane and n-octylaluminoxane.

66. The method for preparing a high molecular weight olefin polymer according to claim 64, wherein: The alkyl aluminum compound is one or more of triethylaluminum, triisobutylaluminum, trioctylaluminum, trimethylaluminum, triisohexylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-hexylaluminum, tri-n-butylaluminum, triisobutylaluminum and tri-n-octylaluminum.

67. The method for preparing a high molecular weight olefin polymer according to claim 64, wherein: The alkylaluminum chloride is one or more of methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum monochloride, diethylaluminum monochloride, di-n-butylaluminum monochloride, diisobutylaluminum monochloride, n-butylaluminum dichloride, isobutylaluminum dichloride, n-butylaluminum sesquichloride, ethylaluminum sesquichloride, methylaluminum sesquichloride and isobutylaluminum sesquichloride.

68. The method for preparing a high molecular weight olefin polymer according to claim 64, wherein: The boronization auxiliary agent is selected from one or more of tetrakis(pentafluorophenyl)boric acid-methyldi-(octadecyl)ammonium salt, trityltetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)boron, N,N-dioctadecylmethylaminotetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, dioctadecylmethyltertiaryaminetetrakis(pentafluorophenyl)borate, and dihydrogenated tallow methyltertiaryaminetetrakis(pentafluorophenyl)borate.

69. The method for preparing a high molecular weight olefin polymer according to any one of claims 59 to 68, characterized in that: The polymerization reaction temperature is 30-260° C.; the polymerization reaction pressure is 0.1-50 MPa.

70. The method for preparing a high molecular weight olefin polymer according to claim 69, wherein: The polymerization reaction temperature is 100-220°C; the polymerization reaction pressure is 1-12 MPa.

71. The method for preparing a high molecular weight olefin polymer according to claim 69, wherein: The amount of the bimetallic catalyst added is 0.05-6 μmol / L based on the molar concentration of the metal element in the organic solvent.

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