A type of non-metallocene catalyst and its preparation method and application

Abstract

The present invention discloses a non-metallocene catalyst, preparation method, and application thereof. The catalyst has the general structural formula shown in Formula I below. This non-metallocene catalyst utilizes a bridged aryloxy backbone with a controlled geometric configuration, which enhances the catalyst's stereoselectivity. When applied to olefin polymerization, particularly ethylene and α-olefin copolymerization, it exhibits excellent high-temperature resistance and strong comonomer insertion capability.

Description

Technical Field

[0001] The present invention relates to a non-metallocene catalyst for olefin polymerization, and in particular to a non-metallocene catalyst and a preparation method and application thereof. Background Art

[0002] Polyolefins, as a major chemical product, are widely used in pipes, cables, films, fibers, and molding processes. Catalyst technology, the lifeblood of the polyolefin industry, determines its development. From the Ziegler-Natta catalyst in the 1950s to the metallocene olefin polymerization catalysts that emerged in the 1980s, the polyolefin industry has achieved significant success and remarkable advances in production technology.

[0003] Homogeneous metallocene catalysts, discovered by Kaminsky and Sinn in 1980, can efficiently catalyze the production of homogeneous polymers and copolymers. The advent of this type of catalyst revolutionized the polyolefin industry. Compared to Ziegler-Natta catalysts, metallocene catalysts offer superior solubility, a single active site, and a wide range of ligand chemical structure controllability, overcoming many of the shortcomings of traditional heterogeneous catalysts.

[0004] While research into the mechanisms of olefin polymerization catalyzed by metallocene catalysts continues to deepen, several technical challenges remain that urgently need to be addressed. Consequently, a new generation of non-metallocene catalysts has emerged. Over the past two decades, an increasing number of non-metallocene catalysts have been developed and applied, garnering widespread attention from both industry and academia. Non-metallocene catalysts are defined as organometallic complexes that contain no cyclopentadiene groups, whose coordinating atoms are heteroatoms such as oxygen, nitrogen, phosphorus, and sulfur, and whose active centers are transition metal elements. These catalysts not only retain the advantages of metallocene catalysts but also offer structural diversity and excellent stability. Therefore, continued research and development of non-metallocene catalysts holds great potential for achieving differentiated and cost-effective polyolefin products.

[0005] Patent US8372927B2 discloses an amino-imine non-metallocene catalyst with a simple synthesis method and excellent catalytic effect. However, it is prone to rearrangement reaction at high temperature to generate isomers, resulting in a low insertion rate of the comonomer and insufficient thermal stability.

[0006] Patent CN110799551B discloses a biarylphenoxy catalyst that has good catalytic performance under medium-temperature (120°C) polymerization conditions, but does not provide polymerization data at high temperatures, and its heat resistance and high-temperature performance still need to be investigated and verified. Summary of the Invention

[0007] To address the above technical issues, the present invention proposes a non-metallocene catalyst, preparation method, and application. This non-metallocene catalyst utilizes a bridged aryloxy backbone with a controlled geometry, enhancing the catalyst's stereoselectivity. When applied to olefin polymerization, particularly the copolymerization of ethylene and α-olefins, it exhibits excellent high-temperature resistance and strong comonomer insertion capabilities.

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

[0009] A type of non-metallocene catalyst has the general structural formula shown in Formula I below:

[0010]

[0011] In Formula I,

[0012] R1-R 14 are each independently selected from hydrogen, halogen or optionally the following groups: C1-C 40 Alkyl, C3-C 40 Cycloalkyl, C6-C 60 Aryl, C7-C 60 Aralkyl, and halogen-substituted C1-C 40 Alkyl, C3-C 40 Cycloalkyl, C6-C 60 Aryl, C7-C 60 Aralkyl, and C1-C 40 Alkyl, C2-C 40 Cycloalkyl, C4-C 60 Aryl, C5-C 60 Aralkyl, wherein the heteroatom is O, N, P, S, Si, or Ge;

[0013] Z is independently a heteroatom, preferably selected from O, N, P, S, Si, Ge; R0 is independently selected from C1-C 40 Alkyl or heteroatom-substituted alkyl, C6-C 40 Aryl or aralkyl, C6-C 40 a heteroatom-substituted aryl or aralkyl group;

[0014] T is selected from C1-C 40 Alkyl, C3-C 40 Cycloalkyl, C6-C 60 Aryl, C7-C 60 Aralkyl, and halogen-substituted C1-C 40 Alkyl, C3-C 40 Cycloalkyl, C6-C 60 Aryl, C7-C 60Aralkyl, and C1-C 40 Alkyl, C2-C 40 Cycloalkyl, C4-C 60 Aryl, C5-C 60 Aralkyl, wherein the heteroatom is O, N, P, S, Si, or Ge;

[0015] X is selected from halogen, C1-C 30 Alkyl, C3-C 30 Cycloalkyl, C6-C 30 Aryl, C7-C 30 Aralkyl, C2-C 20 unsaturated hydrocarbon groups, and C1-C 30 Alkyl, C2-C 30 Cycloalkyl, C4-C 30 Aryl, C5-C 30 Aralkyl, C2-C 20 An unsaturated hydrocarbon group, wherein the heteroatom is O, N, P, S, Si, or Ge;

[0016] M is selected from titanium, zirconium, and hafnium.

[0017] Preferably, in Formula I, R1-R 14 are each independently selected from hydrogen, halogen or optionally the following groups: C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C7-C 30 Aralkyl, and halogen-substituted C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C7-C 30 Aralkyl, and C1-C 20 Alkyl, C2-C 20 Cycloalkyl, C4-C 30 Aryl, C5-C 30 Aralkyl, wherein the heteroatom is O, N, P, or S;

[0018] Preferably, Z is independently a heteroatom or a C1-C 12 The heteroatom is O, N, P, S; R0 is independently selected from C1-C 15 Alkyl or heteroatom-substituted alkyl, C6-C 20 Aryl or aralkyl, C6-C 20 a heteroatom-substituted aryl or aralkyl group;

[0019] Preferably, T is selected from C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C7-C 30 Aralkyl, and halogen-substituted C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C7-C 30 Aralkyl, and C1-C 20 Alkyl, C2-C 20 Cycloalkyl, C4-C 30 Aryl, C5-C 30 Aralkyl, wherein the heteroatom is O, N, P, or S;

[0020] Preferably, X is selected from halogen, C1-C 12 Alkyl, C3-C 12 Cycloalkyl, C6-C 15 Aryl, C7-C 15 Aralkyl, C2-C 12 unsaturated hydrocarbon groups, and C1-C 12 Alkyl, C2-C 12 Cycloalkyl, C4-C 15 Aryl, C5-C 15 Aralkyl, C2-C 12 The unsaturated hydrocarbon group, wherein the heteroatom is O, N, P, or S.

[0021] Preferably, the non-metallocene catalyst is selected from one or more compounds having the following structural expressions:

[0022]

[0023]

[0024]

[0025]

[0026]

[0027] A method for preparing the non-metallocene catalyst as described above comprises the following steps:

[0028] In an ultra-dry organic solvent, the ligand of formula II is first reacted with a hydrogen extraction reagent to form a salt, and then complexed with a metal M salt to obtain a non-metallocene catalyst;

[0029]

[0030] In Formula II, R1-R 14 The definitions of R0, T, and Z are the same as those in the previous text;

[0031] 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;

[0032] 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;

[0033] 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;

[0034] Preferably, the molar ratio of the ligand of formula II to the hydrogen extraction agent is 1:(2.0-2.5); the molar ratio of the ligand of formula II to the metal M salt is 1:(1.0-1.5);

[0035] Preferably, the salt-forming reaction temperature is -78°C to 50°C, and the salt-forming reaction time is 1-15h;

[0036] Preferably, the complexation reaction temperature is 0-170° C., and the complexation reaction time is 1-15 h.

[0037] As a preferred embodiment of the present invention, the ligand of formula II is prepared according to the following process:

[0038]

[0039] 1) reacting compound a with a lithiation reagent and triisopropyl borate to generate compound b;

[0040] Preferably, the reaction conditions are: reaction temperature -78°C to 50°C, reaction time 1-12h;

[0041] 2) reacting compound b and compound c in the presence of a palladium catalyst and a base to produce compound d;

[0042] Preferably, the reaction conditions are: reaction temperature 25-120°C, reaction time 1-20h;

[0043] 3) Compound d is mixed with a bromination reagent to react to generate compound e;

[0044] Preferably, the reaction conditions are: reaction temperature 0-25°C, reaction time 1-60min;

[0045] 4) reacting compound e with a lithiation reagent and triisopropyl borate to generate compound f;

[0046] Preferably, the reaction conditions are: reaction temperature -78°C to 50°C, reaction time 1-12h;

[0047] 5) reacting compound g with a lithiation reagent and triisopropyl borate to generate compound h;

[0048] Preferably, the reaction conditions are: reaction temperature -78°C to 50°C, reaction time 1-12h;

[0049] 6) reacting compound h and compound i in the presence of a palladium catalyst and a base to produce compound j;

[0050] Preferably, the reaction conditions are: reaction temperature 25-120°C, reaction time 1-20h;

[0051] 7) reacting compound j with a lithiation reagent and triisopropyl borate to generate compound k;

[0052] Preferably, the reaction conditions are: reaction temperature -78°C to 50°C, reaction time 1-12h;

[0053] 8) reacting compound f, compound k, and compound 1 in the presence of a palladium catalyst and a base to generate a ligand of formula II;

[0054] Preferably, the reaction conditions are: reaction temperature 25-120° C., reaction time 1-20 h.

[0055] As a preferred embodiment of the present invention, compound a is selected from one or more of 2-bromo-4-tert-butyl-1-methoxybenzene, 2-bromo-4-fluoroanisole, 3-bromo-4-methoxytoluene, 2-bromo-4-tert-octyl-1-methoxybenzene, 1-bromo-2,5-dimethoxybenzene, 3-bromo-4-methoxytrifluorotoluene, and 2-bromoanisole;

[0056] Preferably, the compound c is selected from one or more compounds having the following structural expressions:

[0057]

[0058]

[0059] Further preferably, the compound c can be obtained by the following preparation method:

[0060]

[0061] Wherein, R is selected from boric acid group, amino group, and hydroxyl group;

[0062] The specific reaction process is to react compound C1 and compound R1-R in the presence of a palladium catalyst and a base to produce compound C2; preferably, the reaction conditions are: reaction temperature 25-120°C, reaction time 1-20 hours. Then, a bromination reagent is added to the organic phase of the reaction solution to react and produce compound C; preferably, the reaction conditions are: reaction temperature 0-25°C, reaction time 1-60 minutes.

[0063] Preferably, the compound c1 is selected from one or more of 2-bromo-4-tert-butylphenol, 2-bromo-4-fluorophenol, 2-bromo-4-methoxyphenol, 2-bromo-4-trifluoromethylphenol, 2-bromo-4-tert-octylphenol, and 2-bromophenol;

[0064] Preferably, the compound R1-R is selected from one or more of 3,5-di-tert-butylphenylboronic acid, 3,5-difluorophenylboronic acid, carbazole, 9-anthraceneboronic acid, 2,6-dimethylphenylboronic acid, 2,6-di-tert-butylphenylboronic acid, 3,6-di-tert-butylcarbazole, 3,5-dimethylphenylboronic acid, phenylboronic acid, 3,5-diphenyl-4-phenylboronic acid, and 2,3,4,5-tetramethylpyrrole.

[0065] Preferably, the compound g is selected from one or more of 2-bromo-4-tert-butyl-1-methoxybenzene, 2-bromo-4-fluoroanisole, 3-bromo-4-methoxytoluene, 2-bromo-4-tert-octyl-1-methoxybenzene, 1-bromo-2,5-dimethoxybenzene, 3-bromo-4-methoxytrifluorotoluene, and 2-bromoanisole;

[0066] Preferably, the compound i is selected from one or more of 2-bromo-4-tert-butylphenol, 2-bromo-4-fluorophenol, 2-bromo-4-methoxyphenol, 2-bromo-4-trifluoromethylphenol, 2-bromo-4-tert-octylphenol, and 2-bromophenol;

[0067] Preferably, the compound L is selected from one or more of 1,3-dibromobenzene, 1,3-dibromo-5-fluorobenzene, m-dibromobenzyl, 1,3-dibromopropane, 1,3-dibromocyclohexane, 1,3-dibromo-5-tert-butyl-benzene, 3,5-dibromoanisole, 1,4-dibromobutane, and 1,5-dibromopentane;

[0068] Preferably, the lithiation agent is selected from one or more of n-butyllithium, n-hexyllithium, cyclohexyllithium, methyllithium, ethyllithium, propyllithium, isopropyllithium, sec-butyllithium, tert-butyllithium, amyllithium, tert-octyllithium, and alkylphenyllithium;

[0069] Preferably, the palladium catalyst is selected from one or more of tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, 1,1'-bis(diphenylphosphino)ferrocenepalladium dichloride, tris(dibenzylidene-base acetone)dipalladium, palladium chloride, triphenylphosphine palladium acetate, bis(tri-tert-butylphosphine)palladium, bis(tricyclohexylphosphine)palladium, palladium acetate, and benzyl(chloro)bis(triphenylphosphine)palladium;

[0070] 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;

[0071] Preferably, the brominating agent is selected from liquid bromine and / or N-bromosuccinimide.

[0072] As a preferred embodiment of the present invention, in step 1), the molar ratio of compound a, the lithiation reagent, and triisopropyl borate is 1:(1-2):(1-2);

[0073] Preferably, in step 2), the molar ratio of compound b, compound c, palladium catalyst, and base is (1-2):1:(0.001-0.1):(1-3);

[0074] Preferably, in step 3), the molar ratio of compound d to the bromination reagent is 1:(0.8-1.2);

[0075] Preferably, in step 4), the molar ratio of compound e, the lithiation reagent, and triisopropyl borate is 1:(2-3):(1-2);

[0076] Preferably, in step 5), the molar ratio of compound g, the lithiation reagent, and triisopropyl borate is 1:(1-2):(1-2);

[0077] Preferably, in step 6), the molar ratio of compound h, compound i, palladium catalyst, and base is (1-2):1:(0.001-0.1):(1-3);

[0078] Preferably, in step 7), the molar ratio of compound j, the lithiation reagent, and triisopropyl borate is 1:(2-3):(1-2);

[0079] Preferably, in step 8), the molar ratio of compound f, compound L, compound k, palladium catalyst and base is (0.8-1.2):1:(0.8-1.2):(0.001-0.1):(2-4).

[0080] A method for preparing an ethylene and α-olefin copolymer, specifically comprising the steps of: polymerizing ethylene and α-olefin in an organic solvent in the presence of the non-metallocene catalyst described above or the non-metallocene catalyst prepared by the method described above, and then adding an organic aluminum auxiliary and an optional boronized auxiliary, to produce the ethylene and α-olefin copolymer;

[0081] Preferably, the α-olefin is one or more of propylene, styrene, 1-butene, 1-hexene, and 1-octene.

[0082] Preferably, the ratio of the organoaluminum auxiliary agent to the non-metallocene catalyst is 1-2500, preferably 2-600, calculated as the molar ratio of Al element to M element (Al / M);

[0083] Preferably, the ratio of the boronated auxiliary agent to the non-metallocene catalyst is 0-80, preferably 0-20, calculated as the molar ratio B / M of the B element to the M element.

[0084] As a preferred embodiment of the present invention, the organoaluminum auxiliary agent is selected from one or more of aluminoxane, alkylaluminum compound, and alkylaluminum chloride;

[0085] Preferably, the aluminoxane is one or more of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, isobutylaluminoxane, neopentylaluminoxane, n-hexylaluminoxane and n-octylaluminoxane;

[0086] 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;

[0087] 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;

[0088] Preferably, the boronization auxiliary agent is selected from one or more of tris(pentafluorophenyl)boron, trityltetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis(pentafluorophenyl)borate, triphenylformiumtetrakis(pentafluorophenyl)borate, tetrakis(pentafluorophenyl)boric acid-methyldi-(octadecyl)ammonium salt, N,N-dioctadecylmethylaminotetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, dioctadecylmethyltertiaryammoniumtetrakis(pentafluorophenyl)borate, and dihydrogenated tallow methyltertiary ammoniumtetrakis(pentafluorophenyl)borate.

[0089] As a preferred embodiment of the present invention, the polymerization reaction temperature is 40-260°C, preferably 100-230°C; the polymerization reaction gauge pressure is 0.1-60 MPa, preferably 1-10 MPa;

[0090] Preferably, the amount of the non-metallocene catalyst added is 0.02-7 μmol / L based on the molar concentration of the M element in the organic solvent.

[0091] The non-metallocene catalyst proposed in the present invention has excellent high-temperature resistance and strong comonomer insertion ability. It is suitable for catalyzing olefin polymerization under high-temperature conditions, especially the copolymerization of ethylene and α-olefins. It helps to improve production efficiency, enrich the variety of polyolefins, and has broad application prospects. DETAILED DESCRIPTION

[0092] 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.

[0093] The materials and reagents used in the following examples were purchased from commercial sources, including:

[0094] 2-Bromo-4-tert-butyl-1-methoxybenzene: AR, aladdin;

[0095] 3-Bromo-4-methoxytoluene: AR, Innochem;

[0096] 2-Bromo-4-fluoroanisole: AR, Innochem;

[0097] 2-Bromo-4-tert-butylphenol: AR, Innochem;

[0098] 3,5-di-tert-butylphenylboronic acid: AR, Innochem;

[0099] N-Bromosuccinimide: AR, Innochem;

[0100] 2-Bromo-4-fluorophenol: AR, aladdin;

[0101] 3,5-difluorophenylboronic acid: AR, aladdin;

[0102] 2-Bromo-4-methoxyphenol: AR, aladdin;

[0103] Carbazole: AR, aladdin;

[0104] 2-Bromo-4-trifluoromethylphenol: AR, aladdin;

[0105] 9-Anthraceneboronic acid: AR, aladdin;

[0106] 2,6-dimethylphenylboronic acid: AR, aladdin;

[0107] 1,3-Dibromobenzene: AR, Innochem;

[0108] 1,3-Dibromo-5-fluorobenzene: AR, aladdin;

[0109] m-Dibromobenzyl: AR, aladdin;

[0110] TiCl4: Tokyo Chemical Industry Co., Ltd.;

[0111] ZrCl4: Tokyo Chemical Industry Co., Ltd.;

[0112] HfCl4: Tokyo Chemical Industry Co., Ltd.;

[0113] ZrBn4: Tokyo Chemical Industry Co., Ltd.;

[0114] HfBn4: Tokyo Chemical Industry Co., Ltd.;

[0115] Methylaluminoxane (MAO): Albemarle;

[0116] Modified methylaluminoxane (MMAO): Albemarle;

[0117] Trimethylaluminum (Me3Al): AR, Aladdin;

[0118] Trityltetrakis(pentafluorophenyl)borate: AR, Aladdin;

[0119] Tetrakis(pentafluorophenyl)boric acid-methyldi-(octadecyl)ammonium salt: AR, Aladdin; N,N-dioctadecylmethylaminotetrakis(pentafluorophenyl)borate: AR, Aladdin; Ethylene: 99.9%, Beijing Yanshan Petrochemical Company;

[0120] 1-Hexene: 98%, Beijing Yanshan Petrochemical Company;

[0121] 1-Octene: 98%, Beijing Yanshan Petrochemical Company;

[0122] Isopar E: ExxonMobil Corporation.

[0123] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0124] Unless otherwise specified, the concentrations in the following examples are all molar concentrations.

[0125] In the following examples, "eq" means molar equivalent.

[0126] The compounds in the following examples were characterized using a nuclear magnetic resonance spectrometer (Brucker ARX-400).

[0127] 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).

[0128] In all the following examples and comparative examples, the chemical reactions involved were carried out after nitrogen substitution.

[0129] The following examples 1-10 are used to prepare different non-metallocene catalysts:

[0130] [Example 1]

[0131] The non-metallocene catalyst A was prepared as follows:

[0132]

[0133] (1) Preparation of compound b

[0134] 2-Bromo-4-tert-butyl-1-methoxybenzene (1 eq) was added to dry tetrahydrofuran and cooled to -78°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After 3 h of reaction, 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 b.

[0135] 1 H NMR (500MHz, Chloroform) δ = 7.47 (d, J = 5.0, 2H), 6.95 (s, 1H), 5.74 (s, 2H), 3.91 (s, 3H), 1.32 (s, 9H).

[0136] (2) Preparation of compound d

[0137]

[0138] 2-Bromo-4-tert-butylphenol (1 eq), 3,5-di-tert-butylphenylboronic acid (1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (2.5 eq) were added to ethylene glycol dimethyl ether and the temperature was raised to 85°C for 5 h. After the reaction solution was allowed to stand, the aqueous phase was removed, and N-bromosuccinimide (1 eq) was added to the organic phase. After stirring at room temperature for 0.5 h, the reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound c.

[0139] Compound c (1 eq), compound b (1.1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to ethylene glycol dimethyl ether and the mixture was heated to 85°C for 10 h. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound d.

[0140] 1 H NMR (500MHz, Chloroform) δ = 7.86 (d, J = 3.1, 1H), 7.86 (s, 2H), 7.73 (d, J = 3.1, 2H), 7.64 (dd, J = 15.0, 3. 1,1H),7.55(t,J=3.0,1H),7.04(d,J=15.0,1H),4.42(s,1H),3.79(s,3H),1.43(s,27H),1.32(s,9H).

[0141] (3) Preparation of compound e

[0142] Compound d (1 eq) and N-bromosuccinimide (1 eq) were added to ethanol and reacted at 0°C for 30 min. 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.

[0143] 1 H NMR (500MHz, Chloroform) δ = 7.81 (d, J = 3.1, 1H), 7.86 (s, 2H), 7.73 (d, J = 3.1, 2H), 7.64 (dd, J = 15.0 ,3.1,1H),7.04(d,J=15.0,1H),4.42(s,1H),3.79(s,3H),1.43(s,18H),1.32(s,9H),1.24(s,9H).

[0144] (4) Preparation of Compound f

[0145] Compound e (1 eq) was added to dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 2.2 eq) was slowly added dropwise. After a 3-h reaction, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction continued for another 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 f.

[0146] 1 H NMR (500MHz, Chloroform) δ = 7.87 (d, J = 2.9, 2H), 7.76 (d, J = 3.1, 2H), 7.57 (d, J = 3.1, 2H), 7.40 –7.31(m,1H),5.84(s,2H),5.57(s,1H),3.92(s,3H),1.32(s,18H),1.27(s,9H),1.22(s,9H).

[0147] (5) Preparation of compound h

[0148] Compound h is the same substance as compound b in step (1) and is synthesized by the same method.

[0149] (6) Preparation of Compound J

[0150] 2-Bromo-4-tert-butylphenol (1 eq), compound h (1.1 eq), tetrakistriphenylphosphine palladium (0.1 eq), and sodium carbonate (3 eq) were added to ethylene glycol dimethyl ether and the mixture was heated to 85°C for 10 h. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound j.

[0151] 1 H NMR (500MHz, Chloroform) δ = 7.84 (d, J = 3.1, 1H), 7.76 ( d, J = 3.1, 1H), 7.64 ( dd, J = 15.0, 3.1, 1H), 7.47 ( dd, J = 1 5.0,3.1,1H),7.04(d,J=15.0,1H),6.89(d,J=15.0,1H),5.68(s,1H),3.79(s,3H),1.43(s,9H),1.35(s,9H).

[0152] (7) Preparation of Compound K

[0153] Compound j (1 eq) was added to dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 2.2 eq) was slowly added dropwise. After 3 h of reaction, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction 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 k.

[0154] 1 H NMR(500MHz,Chloroform)δ=7.82(d,J=3.1,1H),7.72–7.60(m,2H),7.40(d,J=2.9,1H) ,7.04(d,J=15.0,1H),5.52(s,2H),5.29(s,1H),3.79(s,3H),1.43(s,9H),1.32(s,9H).

[0155] (8) Preparation of Compound II-1

[0156] 1,3-Dibromobenzene (1 eq), compound f (1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (4 eq) were added to ethylene glycol dimethyl ether and heated to 85°C for 5 h. Compound k (1 eq) was then added to the reaction solution and the reaction continued for 5 h. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound II-1.

[0157] 1 H NMR (500MHz, Chloroform) δ=7.85(d,J=3.1,1H),7.89-7.86(m,4H),7.76–7.59(m,6H),7.49–7.31(m,4H),7.04(d,J= 15.0,1H),5.57(s,1H),5.13(s,1H),3.92(s,3H),3.79(s,3H),1.43(s,9H),1.32(s,27H),1.27(s,9H),1.22(s,9H).

[0158] (9) Preparation of non-metallocene catalyst A

[0159] Compound II-1 (1 eq) was dissolved in dry toluene, cooled to -40°C, and n-butyllithium (2.2 eq) was slowly added dropwise. The reaction was allowed to proceed for 6 hours. Zirconium tetrachloride (1.00 eq) was then added, the temperature was raised to 100°C, and the reaction was continued for 10 hours. The solution was then cooled to 0°C, and MgMeBr solution (4 eq) was added. The reaction was continued for 2 hours, and the reaction was completed. The reaction solution was filtered, concentrated, and crystallized from n-hexane to obtain non-metallocene catalyst A.

[0160] 1 H NMR(500MHz,Chloroform)δ=7.84(d,J=3.1,1H),7.89-7.86(m,4H),7.76–7.59(m,6H),7.49–7.31(m,4H),7.04 (d,J=15.0,1H),3.92(s,3H),3.79(s,3H),1.43(s,9H),1.32(s,27H),1.27(s,9H),1.22(s,9H),-0.22(s,9H).

[0161] [Example 2]

[0162] The non-metallocene catalyst B was prepared as follows:

[0163]

[0164] (1) Preparation of compound b

[0165] 2-Bromo-4-fluoroanisole (1 eq) was added to dry tetrahydrofuran and cooled to -78°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After 3 h of reaction, 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 b.

[0166] 1 H NMR (500MHz, Chloroform) δ = 7.38 (dd, J = 8.0, 1.5, 1H), 7.13 (td, J = 7.9, 1.4, 1H), 6.80 (dd, J = 7.5, 5.1, 1H), 5.74 (s, 2H), 3.91 (s, 3H).

[0167] (2) Preparation of compound d

[0168]

[0169] 2-Bromo-4-fluorophenol (1 eq), 3,5-difluorophenylboronic acid (1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (2.5 eq) were added to ethylene glycol dimethyl ether and heated to 85°C for 5 h. The reaction solution was allowed to stand for 5 h, and the aqueous phase was removed. N-bromosuccinimide (1 eq) was added to the organic phase, and the mixture was stirred at room temperature for 0.5 h. The reaction solution was then extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound c.

[0170] Compound c (1 eq), compound b (1.1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to ethylene glycol dimethyl ether and the mixture was heated to 85°C for 10 h. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound d.

[0171] 1 H NMR(500MHz,Chloroform)δ=7.56–7.41(m,3H),7.29(dddd,J=8.4,7.0,5.9,3.1,3H ),7.10(dd,J=15.0,10.0,1H),6.96(tt,J=15.9,3.0,1H),5.32(s,1H),3.79(s,3H).

[0172] (3) Preparation of compound e

[0173] Compound d (1 eq) and N-bromosuccinimide (1 eq) were added to ethanol and reacted at 0°C for 30 min. 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.

[0174] 1 H NMR (500MHz, Chloroform) δ = 7.52–7.41 (m, 4H), 7.29 (ddt, J = 16.3, 3.0, 1.6, 2H), 6.96 (tt, J = 16.1, 3.1, 1H), 5.53 (s, 1H), 3.92 (s, 3H).

[0175] (4) Preparation of Compound f

[0176] Compound e (1 eq) was added to dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 2.2 eq) was slowly added dropwise. After a 3-h reaction, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction continued for another 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 f.

[0177] (5) Preparation of compound h

[0178] Compound h is the same substance as compound b in step (1) and is synthesized by the same method.

[0179] (6) Preparation of Compound J

[0180] 2-Bromo-4-fluorophenol (1 eq), compound h (1.1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to ethylene glycol dimethyl ether and the mixture was heated to 85°C for 10 h. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound j.

[0181] 1 H NMR (500MHz, Chloroform) δ=7.52(dd,J=16.1,3.0,1H),7.39–7.24(m,2H),7.18–7.05(m,2H),6.95(dd,J=15.0,10.0,1H),5.16(s,1H),3.79(s,3H).

[0182] (7) Preparation of Compound K

[0183] Compound j (1 eq) was added to dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 2.2 eq) was slowly added dropwise. After 3 h of reaction, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction 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 k.

[0184] (8) Preparation of Compound II-2

[0185] 1,3-Dibromo-5-fluorobenzene (1 eq), compound f (1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (4 eq) were added to ethylene glycol dimethyl ether and the reaction temperature was raised to 85°C for 5 h. Compound k (1 eq) was then added to the reaction solution and the reaction continued for 5 h. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound II-2.

[0186] 1 H NMR (500MHz, Chloroform) δ = 7.88 (t, J = 3.0, 1H), 7.62 (dt, J = 15.9, 1.4, 4H), 7.56–7.41 (m, 5H), 7.34–7.23 (m, 3 H),7.10(dd,J=15.0,9.9,1H),6.97(tt,J=16.1,3.1,1H),6.11(s,1H),5.15(s,1H),4.16(s,3H),3.79(s,3H).

[0187] (9) Preparation of non-metallocene catalyst B

[0188] Compound II-2 (1 eq) was dissolved in dry toluene, cooled to -40°C, and n-butyllithium (2.2 eq) was slowly added dropwise. The reaction was allowed to proceed for 6 hours. Zirconium tetrachloride (1.1 eq) was then added, the temperature was raised to 100°C, and the reaction was continued for 10 hours. The reaction solution was filtered, concentrated, and crystallized from n-hexane to obtain non-metallocene catalyst B.

[0189] 1 H NMR (500MHz, Chloroform) δ = 7.62 (d, J = 8.1, 8H), 7.52 (dd, J = 8.1, 1.4, 1H), 7.40 (t, J = 1.5, 1H), 7.29 (qd,J=4.5,1.5,3H),7.10(dd,J=7.5,5.0,1H),6.99(tt,J=7.8,1.4,1H),4.16(s,3H),3.79(s,3H).

[0190] [Example 3]

[0191] The non-metallocene catalyst C was prepared as follows:

[0192]

[0193] (1) Preparation of compound b

[0194] 2-Bromo-4-tert-butyl-1-methoxybenzene (1 eq) was added to dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 1.4 eq) was slowly added dropwise. After 3 h of reaction, triisopropyl borate (1.4 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 40°C and the reaction 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 b.

[0195] (2) Preparation of compound d

[0196]

[0197] 2-Bromo-4-methoxyphenol (1 eq), carbazole (1 eq), cuprous iodide (0.2 eq), potassium carbonate (2.5 eq), and N,N'-dimethylethylenediamine (0.4 eq) were added to a toluene solvent and heated to 85°C for 24 h. The reaction solution was cooled to 0°C, and then N-bromosuccinimide (1 eq) was added. After stirring at room temperature for 0.5 h, the reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound c.

[0198] Compound c (1 eq), compound b (1.1 eq), tetrakis(triphenylphosphine)palladium (0.05 eq), and sodium carbonate (2 eq) were added to ethylene glycol dimethyl ether and the mixture was heated to 75°C and reacted for 15 h. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound d.

[0199] 1 H NMR(500MHz,Chloroform)δ=7.62–7.49(m,1H),7.47–7.43(m,1H),7.41(d,J=3.1,1H),7.37 –7.30(m,4H),7.27–7.00(m,5H),6.45(d,J=2.9,1H),5.05(s,1H),3.79(s,6H),1.43(s,9H).

[0200] (3) Preparation of compound e

[0201] Compound d (1 eq) and N-bromosuccinimide (1 eq) were added to ethanol and reacted at 25°C for 60 min. 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.

[0202] 1H NMR (500MHz, Chloroform) δ=7.62–7.52(m,1H),7.45–7.42(m,1H),7.41(d,J=2.9,1H),7.36–7.31(m,3H),7. 30(d,J=2.9,1H),7.27–7.05(m,4H),6.45(d,J=2.9,1H),5.06(s,1H),3.92(s,3H),3.79(s,3H),1.32(s,9H).

[0203] (4) Preparation of Compound f

[0204] Compound e (1 eq) was added to dry tetrahydrofuran and cooled to -20°C. n-Butyl lithium (1.6 mol / L, 2.5 eq) was slowly added dropwise. After 3 h of reaction, triisopropyl borate (1.5 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was continued for 6 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 f.

[0205] (5) Preparation of compound h

[0206] Compound h is the same substance as compound b in step (1) and is synthesized by the same method.

[0207] (6) Preparation of Compound J

[0208] 2-Bromo-4-methoxyphenol (1 eq), compound h (1.5 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to ethylene glycol dimethyl ether and the reaction temperature was raised to 85°C for 10 h. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound j.

[0209] 1 H NMR(500MHz,Chloroform)δ=7.81(d,J=3.1,1H),7.64(dd,J=15.0,3.1,1H),7.86–6.83(m,2H),7.28(ddd,J= 138.3,69.1,9.1,3H),7.86–6.51(m,4H),6.49(d,J=2.8,1H),4.92(s,1H),3.80(d,J=9.9,6H),1.43(s,9H).

[0210] (7) Preparation of Compound K

[0211] Compound j (1 eq) was added to dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 2.2 eq) was slowly added dropwise. After 3 h of reaction, triisopropyl borate (1.2 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction 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 k.

[0212] (8) Preparation of Compound II-3

[0213] 1,3-Dibromobenzene (1 eq), compound f (1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (4 eq) were added to ethylene glycol dimethyl ether and heated to 85°C for 5 h. Compound k (1 eq) was then added to the reaction solution and the reaction continued for 5 h. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound II-3.

[0214] 1 H NMR(500MHz,Chloroform)δ=7.74–7.45(m,2H),7.38(d,J=4.3,3H),7.36(d,J=3.1,1H),7.33–7.27(m,7H),7.25–7.00( m,5H),6.59(s,2H),6.45(d,J=2.9,1H),5.05(s,1H),4.97(s,1H),4.16(s,3H),3.79(s,9H),1.43(s,9H),1.32(s,9H).

[0215] (9) Preparation of non-metallocene catalyst C

[0216] Compound II-3 (1 eq) was dissolved in dry toluene, cooled to -40°C, and n-butyllithium (2.2 eq) was slowly added dropwise. The reaction was allowed to proceed for 6 hours. Tetrabenzylzirconium (1.00 eq) was then added, the temperature was raised to 100°C, and the reaction was continued for 5 hours. The reaction solution was filtered, concentrated, and crystallized from n-hexane to obtain non-metallocene catalyst C.

[0217] 1H NMR (500MHz, Chloroform) δ=7.66–7.47(m,1H),7.45–7.43(m,1H),7.42(d,J=4.5,3H),7.39(d,J=3.0,1H),7.37–7.31(m, 7H),7.26–7.00(m,15H),6.59(s,2H),6.45(d,J=2.9,1H),5.74(m,4H)4.16(s,3H),3.79(s,9H),1.43(s,9H),1.32(s,9H).

[0218] [Example 4]

[0219] The non-metallocene catalyst D was prepared as follows:

[0220]

[0221] (1) Preparation of compound b

[0222] 3-Bromo-4-methoxytoluene (1 eq) was added to dry tetrahydrofuran and cooled to -60°C. n-Butyl lithium (1.6 mol / L, 1.3 eq) was slowly added dropwise. After 3 h of reaction, triisopropyl borate (1.4 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 40°C and the reaction 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 b.

[0223] (2) Preparation of compound d

[0224]

[0225] 2-Bromo-4-trifluoromethylphenol (1 eq), 9-anthraceneboronic acid (1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (2.5 eq) were added to ethylene glycol dimethyl ether and heated to 85°C for 5 h. After the reaction solution was allowed to stand, the aqueous phase was removed, and N-bromosuccinimide (1 eq) was added to the organic phase. After stirring at room temperature for 0.5 h, the reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound c.

[0226] Compound c (1 eq), compound b (1.1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to ethylene glycol dimethyl ether and the mixture was heated to 85°C for 10 h. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound d.

[0227] 1H NMR (500MHz, Chloroform) δ = 7.83 (t, J = 3.0, 1H), 7.61–7.56 (m, 6H), 7.55 (d, J = 2.9, 1H), 7.51–7.4 0(m,4H),7.27(dd,J=15.0,2.9,1H),7.07(d,J=15.0,1H),4.94(s,1H),3.79(s,3H),2.50(s,3H).

[0228] (3) Preparation of compound e

[0229] Compound d (1 eq) and N-bromosuccinimide (1.2 eq) were added to ethanol and reacted at 0°C for 60 min. 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.

[0230] 1 H NMR (500MHz, Chloroform) δ = 7.83 (t, J = 3.0, 1H), 7.65–7.57 (m, 6H), 7.54 (d, J = 2.9, 1H), 7.51–7.42 (m, 5H), 4.77 (s, 1H), 3.92 (s, 3H), 2.31 (s, 3H).

[0231] (4) Preparation of Compound f

[0232] Compound e (1 eq) was added to dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 2.5 eq) was slowly added dropwise. After 3 h of reaction, triisopropyl borate (1.6 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 f.

[0233] (5) Preparation of compound h

[0234] Compound h is the same substance as compound b in step (1) and is synthesized by the same method.

[0235] (6) Preparation of Compound J

[0236] 2-Bromo-4-trifluoromethylphenol (1 eq), compound h (1.1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to ethylene glycol dimethyl ether and the reaction temperature was raised to 85°C for 10 h. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound j.

[0237] 1 H NMR (500MHz, Chloroform) δ = 7.61 (d, J = 2.9, 1H), 7.54 ( d, J = 2.9, 1H), 7.46 ( dd, J = 15.0, 2.9, 1H), 7.27 ( dd,J=15.0,2.9,1H),7.07(d,J=15.0,1H),6.90(d,J=15.0,1H),5.80(s,1H),3.79(s,3H),2.50(s,3H).

[0238] (7) Preparation of Compound K

[0239] Compound j (1 eq) was added to dry tetrahydrofuran and cooled to -40°C. n-Butyl lithium (1.6 mol / L, 2.3 eq) was slowly added dropwise. After a 3-h reaction, triisopropyl borate (1.5 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction continued for another 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 k.

[0240] (8) Preparation of Compound II-4

[0241] 1,3-Dibromobenzene (1 eq), compound f (1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (4 eq) were added to ethylene glycol dimethyl ether and heated to 85°C for 6 h. Compound k (1 eq) was then added to the reaction solution and the reaction continued for 10 h. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound II-4.

[0242] 1 H NMR (500MHz, Chloroform) δ = 7.74 (t, J = 3.0, 1H), 7.60–7.51 (m, 9H), 7.48 (s, 2H), 7.47 (d, J = 2.9, 1H), 7.45 (dd, J = 17.1, 12.2, 1H), 7.42–7.34 (m, 2H) ,7.32–7.27(m,4H),7.25(dd,J=15.0,2.9,1H),7.07(d,J=15.0,1H),5.25 (s,1H),4.78(s,1H),4.16(s,3H),3.79(s,3H),2.50(s,3H),2.31(s,3H).

[0243] (9) Preparation of non-metallocene catalyst D

[0244] Compound II-4 (1 eq) was dissolved in dry toluene, cooled to -40°C, and n-butyllithium (2.2 eq) was slowly added dropwise. The reaction was allowed to proceed for 6 hours. Tetrabenzylzirconium (1.00 eq) was then added, the temperature was raised to 100°C, and the reaction was continued for 10 hours. The reaction solution was filtered, concentrated, and crystallized from n-hexane to obtain non-metallocene catalyst D.

[0245] 1 H NMR (500MHz, Chloroform) δ = 7.81 (t, J = 3.0, 1H), 7.63–7.55 (m, 9H), 7.50 (s, 2H), 7.46 (d, J = 2.9, 1H), 7.43 (dd, J = 17.1, 12.2, 1H), 7.42–7.37 (m, 2H) ),7.35–7.32(m,4H),7.27(dd,J=15.0,2.9,1H),7.11-7.07(m,11H),5.42 (s,2H),5.25(s,2H),4.16(s,3H),3.79(s,3H),2.50(s,3H),2.31(s,3H).

[0246] [Example 5]

[0247] The non-metallocene catalyst E was prepared as follows:

[0248]

[0249] (1) Preparation of compound b

[0250] 2-Bromo-4-fluoroanisole (1 eq) was added to dry tetrahydrofuran and cooled to -78°C. n-Butyl lithium (1.6 mol / L, 1.2 eq) was slowly added dropwise. After 3 h of reaction, triisopropyl borate (1.4 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 40°C and the reaction 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 b.

[0251] (2) Preparation of compound d

[0252]

[0253] 2-Bromo-4-trifluoromethylphenol (1 eq), 2,6-dimethylphenylboronic acid (1.1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (2.5 eq) were added to ethylene glycol dimethyl ether and heated to 85°C for 5 h. The reaction mixture was allowed to stand for 5 h, and the aqueous phase was removed. N-bromosuccinimide (1 eq) was added to the organic phase. After stirring at room temperature for 0.5 h, the reaction mixture was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound c.

[0254] Compound c (1 eq), compound b (1.1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to ethylene glycol dimethyl ether and heated to 75°C for 8 h. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound d.

[0255] 1 H NMR (500MHz, Chloroform) δ = 7.58–7.41 (m, 4H), 7.34–7.24 (m, 3H), 7.10 (dd, J = 15.0, 10.0, 1H), 4.49 (s, 1H), 3.79 (s, 3H), 2.58 (s, 6H).

[0256] (3) Preparation of compound e

[0257] Compound d (1 eq) and N-bromosuccinimide (1.2 eq) were added to ethanol and reacted at 0°C for 60 min. 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.

[0258] 1 H NMR (500MHz, Chloroform) δ = 7.52–7.40 (m, 4H), 7.32–7.21 (m, 2H), 7.11 (dd, J = 15.0, 10.0, 1H), 4.45 (s, 1H), 3.82 (s, 3H), 2.61 (s, 6H).

[0259] (4) Preparation of Compound f

[0260] Compound e (1 eq) was added to dry tetrahydrofuran and cooled to -60°C. n-Butyl lithium (1.6 mol / L, 2.5 eq) was slowly added dropwise. After 3 h of reaction, triisopropyl borate (1.6 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 f.

[0261] (5) Preparation of compound h

[0262] Compound h is the same substance as compound b in step (1) and is synthesized by the same method.

[0263] (6) Preparation of Compound J

[0264] 2-Bromo-4-fluorophenol (1 eq), compound h (1.1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (3 eq) were added to ethylene glycol dimethyl ether and the mixture was heated to 85°C for 10 h. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound j.

[0265] 1 H NMR (500MHz, Chloroform) δ=7.52(dd,J=16.1,3.0,1H),7.39–7.24(m,2H),7.18–7.05(m,2H),6.95(dd,J=15.0,10.0,1H),5.16(s,1H),3.79(s,3H).

[0266] (7) Preparation of Compound K

[0267] Compound j (1 eq) was added to dry tetrahydrofuran and cooled to -50°C. n-Butyl lithium (1.6 mol / L, 2.3 eq) was slowly added dropwise. After a 3-h reaction, triisopropyl borate (1.5 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction continued for another 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 k.

[0268] (8) Preparation of Compound II-5

[0269] Benzyl m-dibromide (1 eq), compound f (1 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), and sodium carbonate (4 eq) were added to ethylene glycol dimethyl ether and the reaction temperature was raised to 75°C for 10 h. Compound k (1 eq) was then added to the reaction solution and the reaction continued for 10 h. The reaction solution was extracted, concentrated, and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 200:1 (v / v)) to obtain compound II-5.

[0270] 1H NMR (500MHz, Chloroform) δ=7.57–7.37(m,6H),7.34–7.20(m,5H),7.11(ddd,J=18.8,13.3,6.4,3H),7.00(dd,J= 16.0,3.0,1H),6.85(t,J=3.0,1H),5.42(s,1H),4.87(s,1H),3.99(s,4H),3.92(s,3H),3.79(s,3H),2.58(s,6H).

[0271] (9) Preparation of non-metallocene catalyst E

[0272] Compound II-5 (1 eq) was dissolved in dry toluene, cooled to -40°C, and n-butyllithium (2.2 eq) was slowly added dropwise. The reaction was allowed to proceed for 4 hours. Tetrabenzylzirconium (1.00 eq) was then added, the temperature was raised to 100°C, and the reaction was continued for 6 hours. The reaction solution was filtered, concentrated, and crystallized from n-hexane to obtain non-metallocene catalyst E.

[0273] 1 H NMR(500MHz,Chloroform)δ=7.57–7.37(m,6H),7.34–7.20(m,5H),7.11-7.00(m,14H),6.85( t,J=3.0,1H),4.87(s,2H),4.54(s,2H),3.99(s,4H),3.92(s,3H),3.79(s,3H),2.58(s,6H).

[0274] [Example 6]

[0275] The non-metallocene catalyst F was prepared by a method substantially the same as that in Example 1, except that the zirconium tetrachloride in step (9) was replaced by hafnium tetrachloride.

[0276] [Example 7]

[0277] The non-metallocene catalyst G was prepared by a method substantially the same as that in Example 1, except that the zirconium tetrachloride in step (9) was replaced by titanium tetrachloride.

[0278] [Example 8]

[0279] The non-metallocene catalyst H was prepared by a method substantially the same as that in Example 2, except that the zirconium tetrachloride in step (9) was replaced by hafnium tetrachloride.

[0280] [Example 9]

[0281] The non-metallocene catalyst I was prepared by a method substantially the same as that in Example 3, except that tetrabenzyl zirconium in step (9) was replaced by tetrabenzyl hafnium.

[0282] [Example 10]

[0283] The non-metallocene catalyst J was prepared by a method substantially the same as that in Example 4, except that tetrabenzyl zirconium in step (9) was replaced by tetrabenzyl hafnium.

[0284] The following Examples 11-32 are used to prepare copolymers of ethylene and α-olefins:

[0285] [Example 11]

[0286] A 2L autoclave containing a weighed amount of non-metallocene catalyst A (2 μmol), a temperature sensor, a cooling reflux device, and a mechanical stirrer was dried continuously at 140°C for 3 hours, then evacuated and gradually cooled to 25°C. 600mL of Isopar E, 200mL of 1-octene, 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 200°C, and ethylene gas was introduced at 4.0 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.

[0287] [Example 12-32]

[0288] Polyolefin products were prepared according to the raw materials, feed ratios, reaction conditions, etc. in Table 1. The molar ratio of Al in the organoaluminum additive to the metal M in the non-metallocene catalyst is denoted as "Al / M," and the molar ratio of B in the boronated additive to the metal M in the non-metallocene catalyst is denoted as "B / M."

[0289] [Comparative Example 1]

[0290] The olefin polymerization reaction was carried out using the catalyst provided by the method in Examples 1-7 of patent CN110799551B (denoted as Catalyst X). The reaction method was similar to that in Example 15 above, with the only difference being the catalyst.

[0291]

[0292] Table 1, Reaction Conditions in Examples 11-32 and Comparative Example 1

[0293]

[0294] Note: B1 represents trityltetrakis(pentafluorophenyl)borate, B2 represents N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, and B3 represents N,N-dioctadecylmethylammoniumtetrakis(pentafluorophenyl)borate.

[0295] The copolymers obtained in the embodiments and comparative examples were subjected to the performance tests shown in Table 2, and the results are as follows:

[0296] Table 2. Performance test results

[0297]

[0298] 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 non-metallocene catalyst, characterized in that It has the general structural formula shown in the following formula I: In Formula I, R1-R 14 are each independently selected from hydrogen, halogen or optionally the following groups: C1-C 40 Alkyl, C3-C 40 Cycloalkyl, C6-C 60 Aryl, C7-C 60 Aralkyl, and halogen-substituted C1-C 40 Alkyl, C3-C 40 Cycloalkyl, C6-C 60 Aryl, C7-C 60 Aralkyl, and C1-C 40 Alkyl, C2-C 40 Cycloalkyl, C4-C 60 Aryl, C5-C 60 Aralkyl, wherein the heteroatom is O, N, P, S, Si, or Ge; Z is independently a heteroatom; R0 is independently selected from C1-C 40 Alkyl or heteroatom-substituted alkyl, C6-C 40 Aryl or aralkyl, C6-C 40 a heteroatom-substituted aryl or aralkyl group; T is selected from C6-C 60 Aryl, C7-C 60 Aralkyl, and halogen-substituted C6-C 60 Aryl, C7-C 60 Aralkyl, and C4-C 60 Aryl, C5-C 60 Aralkyl, wherein the heteroatom is O, N, P, S, Si, or Ge; X is selected from halogen, C1-C 30 Alkyl, C3-C 30 Cycloalkyl, C6-C 30 Aryl, C7-C 30 Aralkyl, C2-C 20 unsaturated hydrocarbon groups, and C1-C 30 Alkyl, C2-C 30 Cycloalkyl, C4-C 30 Aryl, C5-C 30 Aralkyl, C2-C 20 An unsaturated hydrocarbon group, wherein the heteroatom is O, N, P, S, Si, or Ge; M is selected from titanium, zirconium, and hafnium.

2. The non-metallocene catalyst according to claim 1, characterized in that Z is independently selected from O, N, P, S, Si, and Ge.

3. The non-metallocene catalyst according to claim 1, characterized in that In Formula I, R1-R 14 are each independently selected from hydrogen, halogen or optionally the following groups: C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C7-C 30 Aralkyl, and halogen-substituted C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C7-C 30 Aralkyl, and C1-C 20 Alkyl, C2-C 20 Cycloalkyl, C4-C 30 Aryl, C5-C 30 The heteroatom is O, N, P, or S.

4. The non-metallocene catalyst according to claim 3, characterized in that In formula I, Z is independently a heteroatom, wherein the heteroatom is O, N, P, or S; R0 is independently selected from C1-C 15 Alkyl or heteroatom-substituted alkyl, C6-C 20 Aryl or aralkyl, C6-C 20 The aryl or aralkyl group is substituted with a heteroatom.

5. The non-metallocene catalyst according to claim 3, characterized in that In Formula I, T is selected from C6-C 30 Aryl, C7-C 30 Aralkyl, and halogen-substituted C6-C 30 Aryl, C7-C 30 Aralkyl, and C4-C 30 Aryl, C5-C 30 The heteroatom is O, N, P, or S.

6. The non-metallocene catalyst according to claim 3, characterized in that In formula I, X is selected from halogen, C1-C 12 Alkyl, C3-C 12 Cycloalkyl, C6-C 15 Aryl, C7-C 15 Aralkyl, C2-C 12 unsaturated hydrocarbon groups, and C1-C 12 Alkyl, C2-C 12 Cycloalkyl, C4-C 15 Aryl, C5-C 15 Aralkyl, C2-C 12 The unsaturated hydrocarbon group, wherein the heteroatom is O, N, P, or S.

7. The non-metallocene catalyst according to any one of claims 1 to 6, characterized in that One or more compounds selected from the group consisting of:

8. A method for preparing the non-metallocene catalyst according to any one of claims 1 to 6, characterized in that: The following steps are involved: In an ultra-dry organic solvent, the ligand of formula II is first reacted with a hydrogen extraction reagent to form a salt, and then complexed with a metal M salt to obtain a non-metallocene catalyst; In Formula II, R1-R 14 , R0, T, and Z are defined as R1-R 14 , R0, T, and Z have the same definitions.

9. The method for preparing a non-metallocene catalyst according to claim 8, wherein: 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.

10. The method for preparing a non-metallocene catalyst according to claim 9, wherein: The ultra-dry organic solvent is toluene or n-hexane.

11. The method for preparing a non-metallocene catalyst according to claim 8, wherein: 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.

12. The method for preparing a non-metallocene catalyst according to claim 11, characterized in that: The hydrogen extraction reagent is n-butyl lithium.

13. The method for preparing a non-metallocene catalyst according to claim 8, wherein: 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.

14. The method for preparing a non-metallocene catalyst according to claim 8, wherein: The molar ratio of the ligand of formula II to the hydrogen extraction agent is 1:(2.0-2.5); the molar ratio of the ligand of formula II to the metal M salt is 1:(1.0-1.5).

15. The method for preparing a non-metallocene catalyst according to claim 8, characterized in that: The salt-forming reaction temperature is -78°C to 50°C, and the salt-forming reaction time is 1-15h.

16. The method for preparing a non-metallocene catalyst according to claim 8, characterized in that: The complexation reaction temperature is 0-170° C., and the complexation reaction time is 1-15 hours.

17. The method for preparing a non-metallocene catalyst according to any one of claims 8 to 16, characterized in that: The ligand of formula II is prepared according to the following process: 1) reacting compound a with a lithiation reagent and triisopropyl borate to generate compound b; 2) reacting compound b and compound c in the presence of a palladium catalyst and a base to produce compound d; 3) Compound d is mixed with a bromination reagent to react to generate compound e; 4) reacting compound e with a lithiation reagent and triisopropyl borate to generate compound f; 5) reacting compound g with a lithiation reagent and triisopropyl borate to generate compound h; 6) reacting compound h and compound i in the presence of a palladium catalyst and a base to produce compound j; 7) reacting compound j with a lithiation reagent and triisopropyl borate to generate compound k; 8) Compound f, compound k, and compound L are reacted in the presence of a palladium catalyst and a base to generate a ligand of formula II.

18. The method for preparing a non-metallocene catalyst according to claim 17, characterized in that: In step 1), the reaction conditions are: reaction temperature -78°C to 50°C, and reaction time 1-12h.

19. The method for preparing a non-metallocene catalyst according to claim 17, wherein: In step 2), the reaction conditions are: reaction temperature 25-120° C., reaction time 1-20 h.

20. The method for preparing a non-metallocene catalyst according to claim 17, wherein: In step 3), the reaction conditions are: reaction temperature 0-25° C., reaction time 1-60 min.

21. The method for preparing a non-metallocene catalyst according to claim 17, wherein: In step 4), the reaction conditions are: reaction temperature -78°C to 50°C, and reaction time 1-12h.

22. The method for preparing a non-metallocene catalyst according to claim 17, wherein: In step 5), the reaction conditions are: reaction temperature -78°C to 50°C, and reaction time 1-12h.

23. The method for preparing a non-metallocene catalyst according to claim 17, wherein: In step 6), the reaction conditions are: reaction temperature 25-120° C., reaction time 1-20 h.

24. The method for preparing a non-metallocene catalyst according to claim 17, wherein: In step 7), the reaction conditions are: reaction temperature -78°C to 50°C, and reaction time 1-12h.

25. The method for preparing a non-metallocene catalyst according to claim 17, wherein: In step 8), the reaction conditions are: reaction temperature 25-120° C., reaction time 1-20 h.

26. The method for preparing a non-metallocene catalyst according to claim 17, wherein: The compound a is selected from one or more of 2-bromo-4-tert-butyl-1-methoxybenzene, 2-bromo-4-fluoroanisole, 3-bromo-4-methoxytoluene, 2-bromo-4-tert-octyl-1-methoxybenzene, 1-bromo-2,5-dimethoxybenzene, 3-bromo-4-methoxytrifluorotoluene, and 2-bromoanisole.

27. The method for preparing a non-metallocene catalyst according to claim 26, wherein: The compound c is selected from one or more compounds having the following structural expressions:

28. The method for preparing a non-metallocene catalyst according to claim 26, wherein: The compound g is selected from one or more of 2-bromo-4-tert-butyl-1-methoxybenzene, 2-bromo-4-fluoroanisole, 3-bromo-4-methoxytoluene, 2-bromo-4-tert-octyl-1-methoxybenzene, 1-bromo-2,5-dimethoxybenzene, 3-bromo-4-methoxytrifluorotoluene, and 2-bromoanisole.

29. The method for preparing a non-metallocene catalyst according to claim 26, wherein: The compound i is selected from one or more of 2-bromo-4-tert-butylphenol, 2-bromo-4-fluorophenol, 2-bromo-4-methoxyphenol, 2-bromo-4-trifluoromethylphenol, 2-bromo-4-tert-octylphenol, and 2-bromophenol.

30. The method for preparing a non-metallocene catalyst according to claim 26, wherein: The compound L is selected from one or more of 1,3-dibromobenzene, 1,3-dibromo-5-fluorobenzene, m-dibromobenzyl, 1,3-dibromopropane, 1,3-dibromocyclohexane, 1,3-dibromo-5-tert-butyl-benzene, 3,5-dibromoanisole, 1,4-dibromobutane, and 1,5-dibromopentane.

31. The method for preparing a non-metallocene catalyst according to claim 26, wherein: The lithium reagent is selected from one or more of n-butyllithium, n-hexyllithium, cyclohexyllithium, methyllithium, ethyllithium, propyllithium, isopropyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, tert-octyllithium, and alkylphenyllithium.

32. The method for preparing a non-metallocene catalyst according to claim 26, wherein: The palladium catalyst is selected from one or more of tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, 1,1'-bis(diphenylphosphino)ferrocenepalladium dichloride, tris(dibenzylidene-base acetone)dipalladium, palladium chloride, triphenylphosphine palladium acetate, bis(tri-tert-butylphosphine)palladium, bis(tricyclohexylphosphine)palladium, palladium acetate, and benzyl(chloro)bis(triphenylphosphine)palladium.

33. The method for preparing a non-metallocene catalyst according to claim 26, 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.

34. The method for preparing a non-metallocene catalyst according to claim 26, wherein: The brominating agent is selected from liquid bromine and / or N-bromosuccinimide.

35. The method for preparing a non-metallocene catalyst according to claim 17, wherein: In step 1), the molar ratio of compound a, the lithiation reagent, and triisopropyl borate is 1:(1-2):(1-2).

36. The method for preparing a non-metallocene catalyst according to claim 35, wherein: In step 2), the molar ratio of compound b, compound c, palladium catalyst and base is (1-2):1:(0.001-0.1):(1-3).

37. The method for preparing a non-metallocene catalyst according to claim 35, wherein: In step 3), the molar ratio of compound d to the bromination reagent is 1:(0.8-1.2).

38. The method for preparing a non-metallocene catalyst according to claim 35, wherein: In step 4), the molar ratio of compound e, the lithiation reagent, and triisopropyl borate is 1:(2-3):(1-2).

39. The method for preparing a non-metallocene catalyst according to claim 35, wherein: In step 5), the molar ratio of compound g, the lithiation reagent, and triisopropyl borate is 1:(1-2):(1-2).

40. The method for preparing a non-metallocene catalyst according to claim 35, wherein: In step 6), the molar ratio of compound h, compound i, palladium catalyst and base is (1-2):1:(0.001-0.1):(1-3).

41. The method for preparing a non-metallocene catalyst according to claim 35, wherein: In step 7), the molar ratio of compound j, the lithiation reagent, and triisopropyl borate is 1:(2-3):(1-2).

42. The method for preparing the non-metallocene catalyst according to claim 35, wherein: In step 8), the molar ratio of compound f, compound L, compound k, palladium catalyst and base is (0.8-1.2):1:(0.8-1.2):(0.001-0.1):(2-4).

43. A method for preparing a copolymer of ethylene and α-olefin, characterized in that: In the presence of the non-metallocene catalyst according to any one of claims 1 to 7 or the non-metallocene catalyst prepared by the method according to any one of claims 8 to 42, an organic aluminum auxiliary and an optional boronated auxiliary are added to allow ethylene and α-olefin to undergo polymerization in an organic solvent to produce an ethylene and α-olefin copolymer.

44. The method for preparing a copolymer of ethylene and α-olefin according to claim 43, wherein: The ratio of the organoaluminum auxiliary agent to the non-metallocene catalyst is 1-2500, calculated as the molar ratio of Al element to M element (Al / M).

45. The method for preparing a copolymer of ethylene and α-olefin according to claim 44, wherein: The ratio of the organoaluminum auxiliary agent to the non-metallocene catalyst is 2-600, calculated as the molar ratio of Al element to M element (Al / M).

46. ​​The method for preparing a copolymer of ethylene and α-olefin according to claim 43, wherein: The ratio of the boronized auxiliary agent to the non-metallocene catalyst is 0-80, calculated as the molar ratio B / M of the B element to the M element.

47. The method for preparing a copolymer of ethylene and α-olefin according to claim 46, wherein: The ratio of the boronized auxiliary agent to the non-metallocene catalyst is 0-20, calculated as the molar ratio B / M of the B element to the M element.

48. The method for preparing a copolymer of ethylene and α-olefin according to claim 43, wherein: The organoaluminum auxiliary agent is selected from one or more of aluminoxane, alkylaluminum compound, and alkylaluminum chloride.

49. The method for preparing a copolymer of ethylene and α-olefin according to claim 48, wherein: The aluminoxane is one or more of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, isobutylaluminoxane, neopentylaluminoxane, n-hexylaluminoxane and n-octylaluminoxane.

50. The method for preparing a copolymer of ethylene and α-olefin according to claim 48, 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.

51. The method for preparing a copolymer of ethylene and α-olefin according to claim 48, 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.

52. The method for preparing a copolymer of ethylene and α-olefin according to claim 48, wherein: The boronization auxiliary agent is selected from one or more of tris(pentafluorophenyl)boron, trityltetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis(pentafluorophenyl)borate, triphenylformiumtetrakis(pentafluorophenyl)borate, tetrakis(pentafluorophenyl)boric acid-methyldi-(octadecyl)ammonium salt, N,N-dioctadecylmethylaminotetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, dioctadecylmethyltertiaryammoniumtetrakis(pentafluorophenyl)borate, and dihydrogenated tallow methyltertiaryammoniumtetrakis(pentafluorophenyl)borate.

53. The method for preparing a copolymer of ethylene and α-olefin according to any one of claims 43 to 52, characterized in that: The polymerization reaction temperature is 40-260° C.; the polymerization reaction gauge pressure is 0.1-60 MPa.

54. The method for preparing a copolymer of ethylene and α-olefin according to claim 53, wherein: The polymerization reaction temperature is 100-230°C; the polymerization reaction gauge pressure is 1-10Mpa.

55. The method for preparing a copolymer of ethylene and α-olefin according to claim 53, wherein: The amount of the non-metallocene catalyst added is 0.02-7 μmol / L based on the molar concentration of the M element in the organic solvent.

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