Bis-carbazolyl bis-phenoxy ether complex as well as preparation method and application thereof

Abstract

The invention provides a bis (carbazolyl) bis (phenoxy) ether complex as well as a preparation method and application of the bis (carbazolyl) bis (phenoxy) ether complex. The complex provided by the invention has extremely high catalytic activity and high temperature resistance when being used for catalyzing copolymerization of ethylene and / or alpha-olefin and cycloolefin, and the prepared copolymerization product has extremely good optical properties, such as good transparency, high refractive index, high Abbe number and the like; meanwhile, excellent mechanical properties such as high strength and good toughness are achieved; in addition, the copolymer has good heat resistance, such as high temperature yellowing resistance. Therefore, the complex provided by the invention is very suitable for catalyzing the copolymerization reaction of ethylene and / or alpha-olefin and cycloolefin, and the obtained copolymerization product has a good industrial prospect in the processing application of the optical field.

Description

Technical Field

[0001] The present invention relates to the field of olefin polymerization, and specifically relates to a bis-carbazolyl bis-phenoxy ether complex, a preparation method and a use thereof, and also relates to an olefin polymerization method. Background Art

[0002] COC is a class of amorphous engineering plastics obtained by addition copolymerization of ethylene and / or α-olefins with cycloolefins under the action of a coordination polymerization catalyst. The mainstream COCs on the market currently are commercial products of the TOPAS and APEL series launched by Polyplastics and Mitsui Chemicals in Japan.

[0003] Compared with traditional optical materials such as polymethyl methacrylate (PMMA) and polycarbonate (PC), etc., COC has comparable light transmittance, refractive index and birefringence, etc., but the latter has excellent properties such as low hygroscopicity and low specific gravity. In order to obtain heat resistance comparable to or even better than that of PMMA and PC, it is necessary to increase the insertion rate of cycloolefins in COC. However, while improving the heat resistance, the brittleness of COC is increased, which is not conducive to processing. Therefore, it is necessary to develop new catalysts and catalytic systems.

[0004] COC catalysts mainly include Ziegler-Natta catalysts, metallocene and non-metallocene catalysts, etc. Ziegler-Natta catalysts are multi-active center catalysts, which can obtain polymers with a wide molecular weight distribution, but there will be two polymerization modes, addition copolymerization and ring-opening metathesis polymerization, when catalyzing COC polymerization, and the catalytic activity is low; metallocene catalysts are single-active center catalysts. When catalyzing polymerization reactions, although they have good catalytic activity, their products usually have a relatively narrow molecular weight distribution, reducing the processing performance of polymer resins. In order to solve this problem, it can be achieved by adjusting the molecular weight distribution, such as preparing polyolefins with a bimodal distribution. For example, Chinese patents CN114736321A, CN114853947A and CN105524217A respectively provide methods for preparing polymers with different molecular weight distributions. As described above, preparing polyolefins with a bimodal or multimodal distribution usually requires two or more catalysts and is achieved through special processes; non-metallocene catalysts are a class of promising olefin polymerization catalysts with more space for catalyst skeleton design and modification. The emergence of such catalysts may make up for the deficiencies in the preparation of polymer structure diversity in the existing catalytic system, such as catalyzing the copolymerization of ethylene with α-olefins, diolefins, cycloolefins, and even with polar monomers. However, the existing non-metallocene catalysts for catalyzing COC polymerization have many problems such as low catalytic activity, low insertion rate of cycloolefin monomers (i.e., low glass transition temperature T of COC) g low), and difficulties in regulating the polymer structure, molecular weight (M w ) and its distribution (PDI). Summary of the Invention

[0005] To develop more types of olefin coordination polymerization catalysts and improve their catalytic performance, an object of the present invention is to provide a bis-carbazolyl bis-phenoxy ether complex. As a main catalyst, this complex can catalyze the polymerization of ethylene and / or α-olefins with cycloolefins to obtain a COC with excellent optical properties that has both mechanical strength and toughness. Moreover, the complex of the present invention has good high-temperature stability.

[0006] Another object of the present invention is to provide a preparation method of the bis-carbazolyl bis-phenoxy ether complex.

[0007] Still another object of the present invention is to provide an olefin polymerization method.

[0008] The first aspect of the present invention provides a bis-carbazolyl bis-phenoxy ether complex having a structure shown in formula (Ⅰ),

[0009]

[0010] wherein, M is selected from titanium, zirconium or hafnium;

[0011] R 1 ~R 11 are each independently selected from hydrogen, a substituted or unsubstituted C1-C40 hydrocarbon group, a C3-C40 cycloalkyl group, a C6-C40 aryl group, a heteroatom-containing group or a silyl group containing 1-3 Si atoms; two or more of R 1 ~R 11 can be bonded to each other to form a hydrocarbon ring;

[0012] X is selected from halogen, -NH 2 , a substituted or unsubstituted C1-C20 alkyl group, -N(C1-C20 alkyl) 2 , a C6-C20 aryl group or a benzyl group;

[0013] Y is selected from a substituted or unsubstituted C1-C20 hydrocarbon group, a C3-C20 cycloalkyl group, a heteroatom-containing hydrocarbon group or a silyl group containing 1-3 Si atoms;

[0014] When the above groups are substituted groups, the number of substituents is 1, 2, 3, 4 or 5, and are each independently selected from halogen, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C3-C10 cycloalkyl group, a C6-C20 aryl group or a benzyl group.

[0015] Preferably, in the bis-carbazolyl bis-phenoxy ether complex provided by the present invention, the R 1 ~R 11 are each independently selected from hydrogen, a C1-C12 hydrocarbon group, a C3-C16 cycloalkyl group or a C6-C18 aryl group. In some preferred embodiments, the R 1 ~R11 Each is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, or (substituted) phenyl, etc., or R 1 ~R 11 Two or more of them may be bonded to each other to form a hydrocarbon ring.

[0016] Preferably, in the bis-carbazolyl bis-phenoxy ether complex provided by the present invention, the X is selected from halogen, C1-C4 alkyl, benzyl, or -N(C1-C4 alkyl) 2 . In some preferred embodiments, the X is selected from halogen, including F, Cl, Br, and I. In some more preferred embodiments, the X is selected from Cl.

[0017] Preferably, when the Y is a substituted group, the number of substituents is 1, 2, 3, 4, or 5, and each is independently selected from C1-C10 hydrocarbon group, C1-C10 alkoxy group, C3-C10 cycloalkyl group, and silyl group containing 1-3 Si atoms. In some preferred embodiments, the Y is selected from C1-C6 alkyl group, C3-C8 cycloalkyl group, or C1-C6 alkoxy ether group, etc.

[0018] The bis-carbazolyl bis-phenoxy ether complex provided by the present invention is further preferably selected from any one of the following complexes Cat.1-Cat.8:

[0019]

[0020] The second aspect of the present invention provides a preparation method of the bis-carbazolyl bis-phenoxy ether complex, including the following steps:

[0021] S1: Synthesize a phenoxy ether compound IV from compounds II and III through a Williamson reaction;

[0022] S2: Dissolve the compound IV in a solvent, then add alkyllithium for lithiation at low temperature, then add trimethyl borate for reaction, and then add an aqueous hydrochloric acid solution for hydrolysis to obtain a compound V;

[0023] S3: Perform a Suzuki coupling reaction catalyzed by a palladium catalyst on the compound V and a bromide of carbazole or its derivative (VI) under alkaline conditions to obtain a ligand compound;

[0024] S4: React the ligand compound with alkyllithium to obtain a lithium salt of the ligand compound, and then react it with MX 4 (or its ether complex); or directly react the ligand compound with MR 2 X 2 (or its ether complex) to obtain the bis-carbazolyl bis-phenoxy ether complex.

[0025]

[0026] As a preferred embodiment, in step S1 of the present invention, II and III are added to acetone at room temperature, and then a base is added to catalyze the reaction, and the mixture is heated under reflux to obtain compound IV.

[0027] In the formulas (II) and (IV) of the present invention, X 1 is selected from halogens, preferably Br.

[0028] As a preferred embodiment, in step S1 of the present invention, the base is NaOH, KOH, Ba(OH) 2 , Ca(OH) 2 , K 2 CO 3 , K 3 PO 4 , Na 2 CO 3 , Cs 2 CO 3 or one or more of the like.

[0029] As a preferred embodiment, in step S1 of the present invention, the molar ratio of compound II to compound III is 1:(0.5 - 10), preferably 1:(0.5 - 1).

[0030] As a preferred embodiment, in step S1 of the present invention, the molar ratio of compound II to the base is 1:(1 - 10), preferably 1:(1 - 2).

[0031] As a preferred embodiment, in step S1 of the present invention, the amount of acetone used is 0.1 - 100 mL of acetone added per millimole of compound II, preferably 1 - 10 mL of acetone added per millimole of compound II.

[0032] As a preferred embodiment, in step S1 of the present invention, the reaction temperature is 30 - 100 °C, preferably 50 - 70 °C.

[0033] As a preferred embodiment, in step S1 of the present invention, the reaction time is 0.1 - 100 h, preferably 1 - 10 h.

[0034] As a preferred embodiment, in step S1 of the present invention, the reaction is carried out in an N 2 or air atmosphere; after the reaction is completed, post-treatment processes such as separation and purification are also included, which are conventional operations in the art and are not particularly required in the present invention. For example, in some specific embodiments, the methods that can be adopted include: rotary evaporation or solvent removal under reduced pressure, extraction and liquid separation using water, dichloromethane (DCM) or ethyl acetate, anhydrous Na 2 SO 4 or MgSO 4Dry it, and then purify the target product by column chromatography, recrystallization, or slurrying with an organic solvent.

[0035] As a preferred embodiment, in step S2 of the present invention, the solvent is one or more of benzene, toluene, xylene, chlorobenzene, n-hexane, n-heptane, dichloromethane, 1,2-dichloroethane, tetrachloroethane, tetrahydrofuran, 2-methyltetrahydrofuran, ether, n-propyl ether, isopropyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, and dioxane, preferably one or more of tetrahydrofuran, 2-methyltetrahydrofuran, ether, and methyl tert-butyl ether.

[0036] As a preferred embodiment, in step S2 of the present invention, the alkyllithium is one or more of C1-C6 alkyllithiums, preferably one or more of methyllithium, n-butyllithium, and n-hexyllithium.

[0037] As a preferred embodiment, in step S2 of the present invention, the concentration of the aqueous hydrochloric acid solution is 0.1-10N, preferably 1-2N.

[0038] As a preferred embodiment, in step S2 of the present invention, the molar ratio of compound Ⅳ, alkyllithium, trimethyl borate, and hydrochloric acid is 1:(1-3):(1-10):(1-50), preferably 1:(2-2.2):(2-4):(4-20).

[0039] As a preferred embodiment, in step S2 of the present invention, the amount of the solvent used is 0.1-100 mL of the solvent per millimole of compound Ⅳ, preferably 1-10 mL of the solvent per millimole of compound Ⅳ.

[0040] As a preferred embodiment, in step S2 of the present invention, when adding alkyllithium and trimethyl borate, the temperature of the reaction system is -80 to 40 °C, preferably -80 to 0 °C. After adding alkyllithium, the temperature of the reaction system is -80 to 40 °C, preferably -80 to -40 °C, and the reaction time is 0.1-100 h, preferably 0.1-10 h. After adding trimethyl borate, the temperature of the reaction system is -80 to 40 °C, preferably 0 to 25 °C, and the reaction time is 0.1-100 h, preferably 1-10 h.

[0041] As a preferred embodiment, in step S2 of the present invention, when adding the aqueous hydrochloric acid solution, the temperature of the reaction system is -80 to 40 °C, preferably -10 to 10 °C. After adding the aqueous hydrochloric acid solution, the temperature of the reaction system is -80 to 40 °C, preferably 0 to 25 °C, and the reaction time is 0.1-100 h, preferably 1-10 h.

[0042] As a preferred embodiment, in step S2 of the present invention, the reaction is carried out in N 2or carried out in an Ar atmosphere; after the reaction, it also includes post-treatment processes such as separation and purification, which are conventional operations in the art and are not particularly required in the present invention. For example, in some specific embodiments, the methods that can be adopted include: rotary evaporation or removal of the solvent under reduced pressure, extraction and liquid separation using water, dichloromethane (DCM), or ethyl acetate, anhydrous Na 2 SO 4 or MgSO 4 drying, and then purifying the target product by column chromatography, recrystallization, or slurrying with an organic solvent.

[0043] In the formula (V) of the present invention, Z is a boronic acid group or a boronic acid ester group, selected from -B(OH) 2 or -B(OMe) 2 .

[0044] As a preferred embodiment, in step S3 of the present invention, the base is NaOH, KOH, Ba(OH) 2 , Ca(OH) 2 , K 2 CO 3 , K 3 PO 4 , Na 2 CO 3 , Cs 2 CO 3 , TlOH, KF, CsF, Bu 4 NF, NaOCH 2 CH 3 , N(CH 2 CH 3 ) 3 and the like, preferably one or more of NaOH, KOH, K 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 .

[0045] As a preferred embodiment, in step S3 of the present invention, the palladium catalyst is Pd(PPh 3 ) 4 , Pd(dppf)Cl 2 , Pd(OAc) 2 , PdCl 2 , PdCl 2 (PPh 3 ) 2 , Pd(OAc) 2 (PPh 3 ) 2 , Pd(OAc) 2(P(Cy) 3 ) 2 、Pd(P t Bu 3 ) 2 、PdCl 2 (P(Cy) 3 ) 2 、PdCl(Bn)(PPh 3 ) 2 、Pd 2 (dba) 3 among one or more of, preferably Pd(PPh 3 ) 4 、Pd(dppf)Cl 2 、Pd(P t Bu 3 ) 2 、Pd 2 (dba) 3 among one or more of.

[0046] As a preferred embodiment, step S3 of the present invention is carried out in the presence of a solvent, and the solvent is one or more of benzene, toluene, xylene, chlorobenzene, n - hexane, n - heptane, dichloromethane, 1,2 - dichloroethane, tetrachloroethane, tetrahydrofuran, 2 - methyltetrahydrofuran, ether, n - propyl ether, isopropyl ether, methyl tert - butyl ether, ethylene glycol dimethyl ether, dioxane, water, methanol, ethanol, isopropanol, preferably one or more of toluene, xylene, dioxane, water, ethanol.

[0047] As a preferred embodiment, in step S3 of the present invention, the amount of the solvent used is 0.1 - 1000 mL of solvent added per millimole of compound V, preferably 1 - 100 mL of solvent added per millimole of compound V.

[0048] As a preferred embodiment, in step S3 of the present invention, the molar ratio of compound V, compound VI, base, and palladium catalyst is 1:(0.1 - 100):(0.1 - 100):(0.0001 - 1), preferably 1:(0.1 - 10):(0.1 - 10):(0.001 - 0.1).

[0049] As a preferred embodiment, in step S3 of the present invention, the reaction temperature is 0 - 160 °C, preferably 40 - 130 °C.

[0050] As a preferred embodiment, in step S3 of the present invention, the reaction time is 0.1 - 100 h, preferably 1 - 10 h.

[0051] As a preferred embodiment, in step S3 of the present invention, the reaction is carried out in N 2It is carried out in an Ar atmosphere; after the reaction, it also includes post-treatment processes such as separation and purification, which are conventional operations in the art and are not particularly required in the present invention. For example, in some specific embodiments, the methods that can be adopted include: rotary evaporation or reduced pressure to remove the solvent, extraction and liquid separation using water, dichloromethane (DCM), or ethyl acetate, anhydrous Na 2 SO 4 or MgSO 4 drying, and then purifying the target product by column chromatography, recrystallization, or slurrying with an organic solvent.

[0052] As a preferred embodiment, in step S4 of the present invention, the alkyllithium is one or more of C1-C6 alkyllithiums, preferably one or more of methyllithium, n-butyllithium, and n-hexyllithium.

[0053] As a preferred embodiment, in step S4 of the present invention, the ether is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, n-propyl ether, isopropyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, and dioxane, preferably one or more of tetrahydrofuran, diethyl ether, and n-propyl ether.

[0054] As a preferred embodiment, step S4 of the present invention is carried out in the presence of a solvent, and the solvent is one or more of benzene, toluene, xylene, chlorobenzene, n-hexane, n-heptane, dichloromethane, 1,2-dichloroethane, tetrachloroethane, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, n-propyl ether, isopropyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, and dioxane, preferably one or more of toluene, n-hexane, n-heptane, tetrahydrofuran, and diethyl ether.

[0055] As a preferred embodiment, in step S4 of the present invention, the solvent dosage is 0.1-1000 mL of solvent added per millimole of ligand, preferably 1-100 mL of solvent added per millimole of ligand.

[0056] In step S4 of the present invention, MX 4 is selected from one or more of TiCl 4 , ZrCl 4 , and HfCl 4 .

[0057] In step S4 of the present invention, R in MR 2 X 2 is selected from C1-C20 alkyl, aryl, or benzyl. For example, ZrBn 2 Cl 2 (Et 2 O) 2 , HfBn 2 Cl 2 (Et 2 O) 2 .

[0058] As a preferred embodiment, in step S4 of the present invention, the ligand, alkyllithium, and MX 4 (or its ether complex) have a molar ratio of 1:(0.1 - 100):(0.1 - 100), preferably 1:(1 - 3):(1 - 3).

[0059] As a preferred embodiment, in step S4 of the present invention, the ligand, MR 2 X 2 (or its ether complex) have a molar ratio of 1:(0.1 - 100), preferably 1:(1 - 3).

[0060] As a preferred embodiment, in step S4 of the present invention, the ligand, alkyllithium, and MX 4 (or its ether complex) are reacted at a temperature of -80 to 50 °C, preferably -10 to 25 °C. The reaction time of the ligand and alkyllithium is 0.1 to 100 h, preferably 0.1 to 10 h. The reaction time of the lithium salt of the ligand and MX 4 (or its ether complex) is 0.1 to 100 h, preferably 1 to 30 h.

[0061] As a preferred embodiment, in step S4 of the present invention, the ligand, MR 2 X 2 (or its ether complex) are reacted at a temperature of -20 to 150 °C, preferably 25 to 110 °C. The reaction time of the ligand and MR 2 X 2 (or its ether complex) is 0.1 to 100 h, preferably 1 to 30 h.

[0062] As a preferred embodiment, in step S4 of the present invention, the reaction is carried out in an N 2 or Ar atmosphere; after the reaction, post-treatment processes such as separation and purification are also included, which are conventional operations in the art and are not particularly required in the present invention. For example, in some specific embodiments, the methods that can be adopted include: filtering to separate the filtrate and solid residue, removing the solvent under reduced pressure, and purifying the target product by recrystallization or slurrying with an organic solvent.

[0063] The third aspect of the present invention provides the use of the described bis-carbazolyl bis-phenoxy ether complex as a main catalyst for olefin polymerization.

[0064] Due to the special coordination space and electronic effects of the active center in the complex structure provided by the present invention, when used to catalyze the polymerization reaction of ethylene and / or α-olefin with cycloolefin, on the one hand, it has extremely high catalytic activity and good high-temperature resistance, can withstand higher polymerization temperatures, thus having better thermal stability and being conducive to extending the service life; on the other hand, it reduces the distribution of cycloolefin segments with two, three or more linkages, and ethylene and cycloolefin mainly consist of alternating segments, making the distribution of cycloolefin in COC more uniform and the stereoregularity better, improving the transparency of COC while maintaining high refractive index and high Abbe number, and the content of terminal double bonds in the copolymer is low, avoiding problems such as yellowing at high temperatures, and being more suitable for applications in the optical field. In addition, when the complex provided by the present invention catalyzes the copolymerization of ethylene and / or α-olefin with cycloolefin, the resulting polymer has excellent toughness while maintaining its own high mechanical strength and is easy to process, presumably because the COC of the present invention has a relatively high degree of branching or a structure feature of long-chain branching. Therefore, the complex provided by the present invention is very suitable for catalyzing the polymerization reaction of olefins, especially the copolymerization reaction of ethylene and / or α-olefin with cycloolefin.

[0065] In the use provided by the present invention, the olefin polymerization is the copolymerization of ethylene and / or α-olefin with cycloolefin. In some preferred embodiments, the α-olefin is an α-olefin having 3 to 12 carbon atoms, including but not limited to one or more of 1-propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and the cycloolefin is a cycloolefin having 6 to 21 carbon atoms, including but not limited to one or more of cyclohexene, norbornene, tetracyclododecene.

[0066] The fourth aspect of the present invention provides a method for olefin polymerization. The polymerization method is: in the presence of a main catalyst and a cocatalyst, ethylene and / or α-olefin and cycloolefin carry out a polymerization reaction to form a copolymer of olefins; wherein, the main catalyst is the bis-carbazolyl bis-phenoxy ether complex described above.

[0067] In the polymerization method provided by the present invention, in some preferred embodiments, the α-olefin is an α-olefin having 3 to 12 carbon atoms, including but not limited to one or more of 1-propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and the cycloolefin is a cycloolefin having 6 to 21 carbon atoms, including but not limited to one or more of cyclohexene, norbornene, tetracyclododecene.

[0068] In the polymerization method provided by the present invention, the molar ratio of the main catalyst to the cocatalyst is 1:1 to 5000. In some preferred embodiments, the molar ratio of the main catalyst to the cocatalyst is 1:1 to 2000, including but not limited to molar ratio ranges such as about 1:1, about 1:2, about 1:4, about 1:6, about 1:8, about 1:10, about 1:20, about 1:40, about 1:60, about 1:80, about 1:100, about 1:200, about 1:400, about 1:600, about 1:800, about 1:1000, about 1:1200, about 1:1500, about 1:1800, about 1:2000, or any combination. In some more preferred embodiments, the molar ratio of the main catalyst to the cocatalyst is 1:1 to 1500.

[0069] In the polymerization method provided by the present invention, the cocatalyst can be any common type in the art. In some preferred embodiments, the cocatalyst is selected from one or more of alkylaluminum, alkylaluminum chloride, aluminoxane, and boron-containing additives. In some more preferred embodiments, the alkylaluminum is selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-hexylaluminum; the alkylaluminum chloride is selected from one or more of diethylaluminum chloride, dichloroethylaluminum, and sesqui-diethylaluminum chloride; the aluminoxane is selected from one or more of methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane; the boron-containing additive is selected from one or two of tris(pentafluorophenyl)borane and triphenylcarbenium tetrakis(pentafluorophenyl)borate.

[0070] In the polymerization method provided by the present invention, as a preferred scheme, the cocatalyst is selected from methylaluminoxane (MAO); or the cocatalyst is selected from a combination of methylaluminoxane and triisobutylaluminum with a molar ratio of 1 to 50:1, including but not limited to molar ratio ranges such as about 1:1, about 2:1, about 5:1, about 10:1, about 15:1, about 20:1, about 25:1, about 30:1, about 35:1, about 40:1, about 45:1, about 50:1, or any combination. In some preferred embodiments, the cocatalyst is selected from a combination of methylaluminoxane and triisobutylaluminum with a molar ratio of 2 to 30:1.

[0071] In the polymerization method provided by the present invention, as a preferred embodiment, the cocatalyst is selected from the combination of a boron-containing additive and an alkylaluminum; the cocatalyst is selected from the combination of a boron-containing additive and an alkylaluminum with a molar ratio of 1:1 to 3000, including but not limited to molar ratio ranges such as about 1:10, about 1:20, about 1:50, about 1:100, about 1:150, about 1:200, about 1:250, about 1:300, about 1:350, about 1:400, about 1:450, about 1:500, or any combination. In some preferred embodiments, the cocatalyst is selected from the combination of triphenylcarbenium tetrakis(pentafluorophenyl)borate and triisobutylaluminum with a molar ratio of 1:300.

[0072] In the polymerization method provided by the present invention, as a preferred embodiment, the cocatalyst is selected from the combination of a boron-containing additive and MAO (or modified methylaluminoxane, MMAO); the cocatalyst is selected from the combination of a boron-containing additive and MAO (or MMAO) with a molar ratio of 1:1 to 3000, including but not limited to molar ratio ranges such as about 1:10, about 1:20, about 1:50, about 1:100, about 1:150, about 1:200, about 1:250, about 1:300, about 1:350, about 1:400, about 1:450, about 1:500, or any combination. In some preferred embodiments, the cocatalyst is selected from the combination of triphenylcarbenium tetrakis(pentafluorophenyl)borate and MAO with a molar ratio of 1:500.

[0073] In the polymerization method provided by the present invention, by adjusting the main catalyst structure and polymerization process conditions, the characteristics of the prepared polymerization products can be adjusted within a relatively wide range, especially the cycloolefin monomer insertion rate and polymer microstructure of copolymers (such as copolymers of ethylene and norbornene). Moreover, even when the polymerization is carried out at a relatively high temperature (130 °C), the polymerization activity of the catalyst will not be significantly sacrificed and can still be maintained at a relatively high level (as shown in Table 1).

[0074] In the polymerization method provided by the present invention, the reaction temperature of the polymerization reaction is 50 to 200 °C, and within this range, those skilled in the art can make appropriate adjustments according to the actual reaction conditions such as the type of polymerization and the type of polymerization monomers. In some preferred embodiments, the reaction temperature of the polymerization reaction is 90 to 180 °C. In some more preferred embodiments, the reaction temperature of the polymerization reaction is higher than 110 °C, such as 110 to 140 °C.

[0075] The bis-carbazolyl bis-phenoxy ether complex provided by the present invention has good high-temperature stability and can still maintain a relatively high polymerization activity at a relatively high reaction temperature (such as at 150 °C), while the polymerization temperatures that the commonly used catalysts in the art (including single- or double-active center metallocenes or single- or double-active center non-metallocene catalysts) can tolerate do not exceed 130 °C.

[0076] In the polymerization method provided by the present invention, the reaction pressure of the polymerization reaction is 0.01 to 10 MPa, and within this range, those skilled in the art can make appropriate adjustments according to the actual reaction conditions such as the polymerization type and the type of polymerization monomer. In some preferred embodiments, the reaction pressure of the polymerization reaction is 0.1 to 3 MPa.

[0077] In the polymerization method provided by the present invention, the reaction time of the polymerization reaction is 0.1 to 1000 min, and within this range, those skilled in the art can make appropriate adjustments according to the actual reaction conditions such as the polymerization type and the type of polymerization monomer. In some preferred embodiments, the reaction time of the polymerization reaction is 1 to 100 min, for example, it can be 1 to 30 min.

[0078] The polymerization method provided by the present invention can be a solution polymerization process, that is, the polymerization reaction is carried out in a solvent, and the solvent used can be any common type in the art.

[0079] In the polymerization method provided by the present invention, other process steps, post-treatment steps, etc. except the above process parameters can all adopt conventional techniques in the art, or can be appropriately adjusted by those skilled in the art according to the actual reaction conditions such as the polymerization type and the type of polymerization monomer.

[0080] In order to improve the disadvantages of existing olefin coordination polymerization catalysts, the present invention optimizes the steric effect and electronic effect of the catalytic active center by reasonably designing the catalyst skeleton structure and modifying groups, thereby obtaining an excellent catalyst with high catalytic activity, high cycloolefin monomer insertion rate, easy regulation of polymer microstructure, M w and PDI, and high temperature resistance. The COC obtained by using the bis-carbazolyl bis-phenoxy ether complex described in the present invention as the main catalyst has good optical properties (high transparency, yellowing resistance, refractive index and Abbe number comparable to those of PC and PMMA, etc.), high strength, good toughness, and is easy to process. More types of new COC products can be obtained to meet the increasingly diversified application requirements.

[0081] The technical solution provided by the present invention has the following advantages:

[0082] (1) The complex provided by the present invention has extremely high catalytic activity and good high temperature resistance, and is very suitable for catalyzing the polymerization reaction of olefins, especially the copolymerization reaction of ethylene and / or α-olefin with cycloolefin.

[0083] (2) Compared with the existing metallocene and non-metallocene complex catalysts, the complex provided by the present invention, as the main catalyst, reduces the distribution of cycloolefin di-block, tri-block and above chain segments in the COC obtained by the copolymerization of ethylene and / or α-olefin with cycloolefin. Ethylene and cycloolefin mainly consist of alternating isotactic segments, making the distribution of cycloolefin in the COC more uniform and the stereoregularity better. While maintaining high refractive index and low birefringence, the transparency of the COC is improved, and the content of terminal double bonds in the copolymer is low, avoiding problems such as yellowing during processing, and is more suitable for applications in the optical field.

[0084] (3) When the complex provided by the present invention catalyzes the copolymerization of ethylene and / or α-olefin with cycloolefin, COCs with different mechanical properties can be obtained by regulating the structure of the complex, thereby increasing its toughness while maintaining its high mechanical strength, and being easy to process.

[0085] (4) The preparation method of the complex provided by the present invention is simple, and the reaction raw materials and intermediates are also easy to synthesize, without complex process steps and high costs, and can adapt to large-scale production and use.

[0086] (5) The olefin polymerization method provided by the present invention has high polymerization activity, simple process and strong operability, can adapt to a variety of olefin monomers, especially cycloolefin monomers with large steric hindrance, and has very important industrial value and economic value. Detailed Embodiments

[0087] Terms

[0088] As used herein, "C1-Cn" includes C1-C2, C1-C3, …… C1-Cn. For example, the group of "C1-C10" means that this part has 1 to 10 carbon atoms, that is, the group contains 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms or 10 carbon atoms. Therefore, for example, "C1-C4 alkyl" means an alkyl containing 1 to 4 carbon atoms, that is, the alkyl is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. The numerical ranges in this article, such as "1-6", refer to each integer within the given range.

[0089] As used herein, the term "alkyl", alone or in combination, refers to an optionally substituted straight-chain or optionally substituted branched-chain saturated aliphatic hydrocarbon. The "alkyl" herein preferably may have 1 to 10 carbon atoms, for example, 1 to 8 carbon atoms, or 1 to 6 carbon atoms, or 1 to 5 carbon atoms, or 1 to 4 carbon atoms, or 1 to 3 carbon atoms. Non-limiting examples of alkyl include methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl and hexyl, as well as longer alkyl groups such as heptyl and octyl. When a group defined herein, such as "alkyl", appears with a numerical range, for example, "C1-C6 alkyl" refers to an alkyl that may be composed of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms or 6 carbon atoms. The alkyl herein also includes cases where no numerical range is specified.

[0090] As used herein in combination, "alkyl" refers to an alkyl group linked to other groups, for example, the alkyl in an alkoxy group, and its definition is the same as when used alone.

[0091] As used herein, the term "alkoxy", alone or in combination, refers to an alkyl ether group, represented as "alkyl-O-". Non-limiting examples of alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, etc.

[0092] As used herein, the term "cycloalkyl", alone or in combination, refers to a non-aromatic saturated carbocyclic ring, which may include a monocyclic ring (having one ring), a bicyclic ring (having two rings) or a polycyclic ring (having more than two rings), and the rings may be bridged or spiro. The cycloalkyl preferably may have 3 to 10 ring-forming carbon atoms, for example, 3 to 8 ring-forming carbon atoms, or 3 to 6 ring-forming carbon atoms. Non-limiting examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.

[0093] As used herein, the term "aryl" used alone or in combination refers to an optionally substituted aromatic hydrocarbon group which preferably may have 6 to 20, such as 6 to 12 or 6 to 10 ring carbon atoms, and which may be a monocyclic aryl group, a bicyclic aryl group or a polycyclic aryl group. The bicyclic aryl group or the polycyclic aryl group may be a monocyclic aryl group fused with other independent rings, such as an alicyclic ring or an aromatic ring. Non-limiting examples of the monocyclic aryl group include phenyl; non-limiting examples of the bicyclic aryl group include naphthyl; non-limiting examples of the polycyclic aryl group include phenanthryl, anthryl, fluorenyl, azulyl.

[0094] As used herein, the term "halogen" used alone or in combination refers to fluorine, chlorine, bromine or iodine.

[0095] As used herein, the term "α-olefin" used alone or in combination refers to a monoolefin with a double bond at the end of the molecular chain, and its molecular formula can be represented as R-CH=CH 2 , where R represents "C1-C10 alkyl". The olefin has but is not limited to 3 to 12 carbon atoms. For example, it has 3 to 12 carbon atoms, or has 3 to 10 carbon atoms, or has 3 to 8 carbon atoms. The double bond in these groups can be in a cis or trans conformation and should be understood to include both of these isomers. The olefin defined herein can be a single type of olefin or a mixture of multiple olefins.

[0096] As used herein, the term "R 1 ~R n " refers to the groups R 1 , R 2 , R 3 , ……R n , that is, it refers to all R groups within the range of subscripts 1 to n.

[0097] As used herein, the term "hydrocarbyl" used alone or in combination includes alkanes, alkenes, arenes and alkynes, and can be a straight-chain or branched-chain group or a cyclic group.

[0098] The technical solutions of the present invention will be further described in detail below in conjunction with specific embodiments.

[0099] Unless otherwise specified, the reagents or raw materials used in the embodiments of the present invention are all commercially available products.

[0100] Unless otherwise specified, the percentages used in the embodiments of the present invention are all mass percentages.

[0101] The test methods used in the embodiments of the present invention are as follows:

[0102] Polymer molecular weight (M w ) and molecular weight distribution (PDI, M w / M n)Determined by high-temperature gel permeation chromatography (PL-GPC220), using 1,2,4-trichlorobenzene as the mobile phase, polystyrene as the standard sample, and measuring at 150 °C. The concentration of the standard sample is 0.1 mg / mL, the solvent flow rate is 1.0 mL / min, the parameters of the standard sample are K = 59.1 and α = 0.69, and the parameters of the sample are K = 14.1 and α = 0.70.

[0103] The melting point (T m ) and glass transition temperature (T g ) of the polymer were determined by differential scanning calorimetry (METTLER, DSC-1). The determination procedure is as follows: Take 5.0 - 7.0 mg of the polymer sample, heat it to 250 °C at a rate of 30 °C / min and maintain for 5 min to eliminate the thermal history, then cool it to 0 °C at a rate of 10 °C / min and keep it constant for 3 min, and then heat it to 250 °C again. The crystallization peak temperature is obtained from the cooling curve, and the melting point or glass transition temperature of the polymer is calculated from the curve of the second heating process.

[0104] The insertion rate of cycloolefin monomers and the content of [ENEN] configuration (ethylene and norbornene alternation) in the copolymer of ethylene and / or α-olefin and cycloolefin were determined by 13 13C NMR (Bruker ADVANCE III 400M). The polymer was dissolved in deuterated 1,2-o-dichlorobenzene at 130 °C, and the concentration was about 100 mg / mL. Instrument test parameters: The pulse angle is 30 degrees, full decoupling, the pulse delay time is 3 s, and the number of sample scans is more than 3000 times. After the peaks of the obtained high-temperature 13 13C NMR spectrum were assigned, the sequence distribution and copolymer monomer insertion rate of the copolymer were obtained.

[0105] The tensile experiment was used to test the tensile mechanical properties of the polymer by an electronic universal material testing machine of Instron Company in the United States, and the stress-strain curve and related mechanical parameters of the polymer were obtained.

[0106] The light transmittance of the sample was measured by a UV-3600Plus ultraviolet-visible spectrophotometer, and the test wavelength range was 250 - 800 nm. All test samples were 2 mm thick.

[0107] The terminal double bonds of the polymer were measured according to the iodometric method.

[0108] The refractive index and Abbe number of the polymer were measured by an Abbe refractometer (DR-M4, ATAGO), and the test was carried out at room temperature (25 °C).

[0109] Preparation of the Cat.1 complex in Example 1

[0110]

[0111] The synthetic route of Cat.1 is as follows:

[0112]

[0113]

[0114] (1) Preparation of Intermediate Ⅳ-1: Add 50 mmol of 2-bromo-4-tert-butylphenol and 25 mmol of 1,2-dibromoethane to a flask, then add 150 mL of acetone. After the reactants are dissolved, add 75 mmol of potassium hydroxide, and reflux at 60 °C for 5 h. Thin-layer chromatography (TLC) shows that the reaction is basically complete. After removing the acetone solvent by rotary evaporation, add 100 mL of DCM and 100 mL of water to the residue, extract and collect the organic phase. The aqueous phase is extracted with DCM (50 mL × 3). After mixing all the organic phases, dry with anhydrous Na 2 SO 4 Dry, filter, and then remove the solvent from the filtrate by rotary evaporation. The residual solid is recrystallized from acetone to obtain a white solid, which is Intermediate Ⅳ-1, with a yield of 90%.

[0115] 1 1H NMR (500 MHz, Chloroform-d) δ 7.30 (d, J = 1.5 Hz, 2H), 7.25 (dd, J = 7.5, 1.6 Hz, 2H), 6.91 (d, J = 7.5 Hz, 2H), 4.40 (t, J = 8.2 Hz, 4H), 1.33 (s, 18H).

[0116] (2) Preparation of Intermediate Ⅴ-1: Under a N 2 atmosphere, add 20 mmol of Intermediate Ⅳ-1 and 100 mL of ultra-dry THF to a 500 mL Schlenk flask. Dropwise add 40 mmol of n-BuLi (1.6 M hexane solution) at -78 °C and react for 30 min, then add 40 mmol of B(OMe) 3 , slowly warm to 25 °C and react for 12 h. After the reaction is completed, add 80 mL of 2N HCl at 0 °C, stir at 25 °C for 1 h, add 100 mL of water. After the reaction mixture stands and separates into layers, collect the organic phase. The aqueous phase is extracted with EtOAc (50 mL × 3). After mixing all the organic phases, dry with anhydrous MgSO 4 Dry, filter, and then remove the solvent from the filtrate by rotary evaporation to obtain a white solid product. The white solid product is further purified by washing with n-hexane (100 mL × 3) to obtain a white solid powder, which is Intermediate Ⅴ-1, with a yield of 82%.

[0117] 11H NMR (500 MHz, Chloroform-d) δ 7.35 (d, J = 1.7 Hz, 2H), 7.28 (dd, J = 7.5, 1.5 Hz, 2H), 7.06 (d, J = 7.5 Hz, 2H), 6.29 (s, 4H), 4.34 (t, J = 8.2 Hz, 4H), 1.34 (s, 18H).

[0118] (3) Preparation of Cat.1 ligand: In a 500 mL Schlenk flask, add 20 mmol of 1-bromo-9H-carbazole, 10 mmol of intermediate V-1 and 100 mmol of Na 2 CO 3 , then add 90 mL of toluene, 30 mL of ethanol and 30 mL of water respectively. After freezing and degassing 3 times, under the atmosphere of N 2 , add 1 mmol of Pd(PPh 3 ) 4 to the mixed solution, raise the temperature to 80 °C and stir for 12 h. After the reaction mixture is allowed to stand and separate into layers, collect the organic phase. The aqueous phase is extracted with dichloromethane (30 mL × 3). After mixing all the organic phases, dry with anhydrous MgSO 4 , then filter to obtain the filtrate of the organic phase. After removing the solvent by rotary evaporation, the product is separated and purified by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain a white solid product, which is the Cat.1 ligand with a yield of 75%.

[0119] 1 1H NMR (500 MHz, Chloroform-d) δ 8.13–8.08 (m, 4H), 8.03 (dd, J = 7.6, 1.7 Hz, 2H), 7.72 (dd, J = 7.5, 1.5 Hz, 2H), 7.49–7.43 (m, 4H), 7.41 (dd, J = 7.4, 1.6 Hz, 2H), 7.35–7.25 (m, 4H), 7.20 (td, J = 7.4, 1.6 Hz, 2H), 6.95 (d, J = 7.5 Hz, 2H), 4.40 (s, 4H), 1.36 (s, 18H).

[0120] (4) Preparation of Cat.1 complex: Under the atmosphere of N 2 , in a 200 mL Schlenk flask, add 5 mmol of Cat.1 ligand and 5 mmol of HfBn 2 Cl 2 (Et 2 O) 2It was added to 60 mL of toluene and reacted under dark at 80 °C for 12 h. After filtration, the filtrate was collected, concentrated, and then precipitated at -18 °C to obtain a white crystalline solid, which was the Cat.1 complex with a yield of 66%.

[0121] 1 H NMR (400 MHz, C 6 D 6 ): δ 8.15–8.09 (m, 2H), 8.01–7.96 (m, 2H), 7.56–7.49 (m, 4H), 7.44 (ddd, J = 7.3, 6.1, 1.3 Hz, 2H), 7.37–7.30 (m, 6H), 7.21 (dd, J = 6.5, 2.2 Hz, 2H), 6.94 (d, J = 6.5 Hz, 2H), 4.24 (s, 4H), 1.32 (s, 18H).

[0122] Example 2 Preparation of Cat.2 Complex

[0123]

[0124] The synthetic route of Cat.2 is as follows:

[0125]

[0126] (1) Preparation of Cat.2 ligand: In a 500 mL Schlenk flask, 20 mmol of 8-bromo-7H-benzo[c]carbazole, 10 mmol of intermediate V-1 and 100 mmol of Na 2 CO 3 were added respectively. Then, 90 mL of toluene, 30 mL of ethanol and 30 mL of water were added respectively. After freezing and degassing three times, under N 2 atmosphere, 1 mmol of Pd(PPh 3 ) 4 was added to the mixed solution, and the temperature was raised to 80 °C and stirred for 12 h. After the reaction, the mixed solution was allowed to stand and separate into layers, and the organic phase was collected. The aqueous phase was extracted with dichloromethane (30 mL × 3). After mixing all the organic phases, they were dried with anhydrous MgSO 4 , and then filtered to obtain the organic phase filtrate. After removing the solvent by rotary evaporation, the product was separated and purified by column chromatography (petroleum ether:ethyl acetate = 15:1) to obtain a white solid product, which was the Cat.2 ligand with a yield of 69%.

[0127] 11H NMR (500 MHz, Chloroform-d) δ 8.58–8.51 (m, 4H), 7.98 (dd, J = 7.4, 1.5 Hz, 2H), 7.94–7.87 (m, 2H), 7.72 (dd, J = 7.5, 1.5 Hz, 2H), 7.52–7.43 (m, 8H), 7.42 (d, J = 7.5 Hz, 2H), 7.36 (dd, J = 7.6, 1.5 Hz, 2H), 7.28 (dd, J = 7.5, 1.5 Hz, 2H), 6.95 (d, J = 7.5 Hz, 2H), 4.40 (s, 4H), 1.36 (s, 18H).

[0128] (2) Preparation of Cat.2 complex: Under N 2 atmosphere, in a 200 mL Schlenk flask, 5 mmol of Cat.2 ligand and 5 mmol of HfBn 2 Cl 2 (Et 2 O) 2 were added to 60 mL of toluene, and the mixture was reacted at 80 °C in the dark for 12 h. The filtrate was filtered and collected, concentrated, and then precipitated at -18 °C to obtain a white crystalline solid, which was the Cat.2 complex with a yield of 60%.

[0129] 1 1H NMR (400 MHz, C 6 D 6 ): δ 7.94–7.87 (m, 4H), 7.84 (dt, J = 7.5, 1.2 Hz, 4H), 7.58–7.51 (m, 4H), 7.46 (ddd, J = 8.0, 6.8, 1.3 Hz, 2H), 7.42–7.32 (m, 6H), 7.25 (dd, J = 6.5, 2.3 Hz, 2H), 6.84 (d, J = 6.5 Hz, 2H), 4.14 (s, 4H), 1.38 (s, 18H).

[0130] Example 3 Preparation of Cat.3 complex

[0131]

[0132] The synthetic route of Cat.3 is as follows:

[0133]

[0134] (1) Preparation of Cat.3 Ligand: In a 500 mL Schlenk flask, add 20 mmol of 1-bromo-3,6-di-tert-butyl-9H-carbazole, 10 mmol of Intermediate V-1, and 100 mmol of Na 2 CO 3 , then add 90 mL of toluene, 30 mL of ethanol, and 30 mL of water respectively. After freezing and degassing three times, under a N 2 atmosphere, add 1 mmol of Pd(PPh 3 ) 4 to the mixed solution, raise the temperature to 80 °C and stir for 12 h. After the reaction mixture is allowed to stand and separate into layers, collect the organic phase. The aqueous phase is extracted with dichloromethane (30 mL × 3). After mixing all the organic phases, dry over anhydrous MgSO 4 , then filter to obtain the organic phase filtrate. After removing the solvent by rotary evaporation, the product is separated and purified by column chromatography (petroleum ether: ethyl acetate = 25:1) to obtain a white solid product, which is the Cat.2 ligand with a yield of 83%.

[0135] 1 1H NMR (500 MHz, Chloroform-d) δ 8.25 (d, J = 1.5 Hz, 2H), 8.16 (d, J = 1.4 Hz, 2H), 7.47 (d, J = 1.5 Hz, 2H), 7.44–7.35 (m, 6H), 7.32–7.26 (m, 4H), 7.01 (d, J = 7.5 Hz, 2H), 4.40 (s, 4H), 1.41 (s, 18H), 1.36 (s, 18H), 1.32 (s, 18H).

[0136] (2) Preparation of Cat.3 Complex: Under a N 2 atmosphere, in a 200 mL Schlenk flask, add 5 mmol of Cat.3 ligand and 5 mmol of HfBn 2 Cl 2 (Et 2 O) 2 to 60 mL of toluene, and react under dark conditions at 80 °C for 12 h. Filter and collect the filtrate, concentrate it, and precipitate at -18 °C to obtain a white crystalline solid, which is the Cat.3 complex with a yield of 76%.

[0137] 1 1H NMR (400 MHz, C 6 D 6): δ 8.01–7.97 (m, 2H), 7.85 (d, J = 2.2 Hz, 2H), 7.54 (d, J = 2.1 Hz, 2H), 7.38–7.30 (m, 6H), 7.22 (dd, J = 6.6, 2.2 Hz, 2H), 7.02 (d, J = 6.6 Hz, 2H), 4.08 (s, 4H), 1.36–1.30 (m, 54H).

[0138] Example 4 Preparation of Cat.4 Complex

[0139]

[0140] The synthetic route of Cat.4 is as follows:

[0141]

[0142]

[0143] (1) Preparation of Intermediate VI-1: In a 500 mL Schlenk flask, add 15 mmol of 1-bromo-3,6-diiodo-9H-carbazole, 30 mmol of (3,5-di-tert-butylphenyl)boronic acid, and 200 mmol of Na 2 CO 3 , then add 90 mL of toluene, 30 mL of ethanol, and 30 mL of water respectively. After freezing and degassing 3 times, under a N 2 atmosphere, add 1 mmol of Pd(PPh 3 ) 4 to the mixed solution, raise the temperature to 80 °C and stir the reaction for 13 h. After the reaction mixture is allowed to stand and separate into layers, collect the organic phase. The aqueous phase is extracted with dichloromethane (30 mL × 3). After mixing all the organic phases, dry with anhydrous MgSO 4 , then filter to obtain the filtrate of the organic phase. After removing the solvent by rotary evaporation, the product is separated and purified by column chromatography (petroleum ether: ethyl acetate = 40:1) to obtain a white solid product, which is Intermediate VI-1 with a yield of 73%.

[0144] 1 1H NMR (500 MHz, Chloroform-d) δ 7.86 (dd, J = 13.3, 1.5 Hz, 2H), 7.73 (d, J = 1.4 Hz, 1H), 7.54 (dd, J = 7.5, 1.5 Hz, 1H), 7.45 (d, J = 7.5 Hz, 1H), 6.91 (d, J = 1.4 Hz, 2H), 6.89–6.84 (m, 5H), 2.26 (m, 36H).

[0145] (2) Preparation of Cat.4 Ligand: In a 500 mL Schlenk flask, add 20 mmol of intermediate VI-1, 10 mmol of intermediate V-1, and 100 mmol of Na 2 CO 3 , then add 90 mL of toluene, 30 mL of ethanol, and 30 mL of water respectively. After freezing and degassing three times, under an N 2 atmosphere, add 1 mmol of Pd(PPh 3 ) 4 to the mixed solution, raise the temperature to 80 °C and stir for 12 h. After the reaction mixture is allowed to stand and separate into layers, collect the organic phase. The aqueous phase is extracted with dichloromethane (30 mL × 3). After mixing all the organic phases, dry with anhydrous MgSO 4 , then filter to obtain the filtrate of the organic phase. After removing the solvent by rotary evaporation, the product is separated and purified by column chromatography (petroleum ether:ethyl acetate = 10:1) to obtain a white solid product, which is the Cat.4 ligand with a yield of 66%.

[0146] 1 1H NMR (500 MHz, Chloroform-d) δ 7.79 (d, J = 1.5 Hz, 2H), 7.72 (d, J = 1.7 Hz, 2H), 7.57–7.44 (m, 8H), 7.34 (d, J = 1.8 Hz, 2H), 7.16 (dt, J = 7.4, 1.2 Hz, 2H), 6.95 (d, J = 7.5 Hz, 2H), 6.91–6.82 (m, 12H), 4.40 (s, 4H), 2.46 (s, 18H), 2.27 (m, 72H).

[0147] (3) Preparation of Cat.4 Complex: Under an N 2 atmosphere, in a 200 mL Schlenk flask, add 5 mmol of Cat.4 ligand and 5 mmol of HfBn 2 Cl 2 (Et 2 O) 2 to 60 mL of toluene, and react in the dark at 80 °C for 12 h. Filter and collect the filtrate, concentrate it, and precipitate it at -18 °C to obtain a white crystalline solid, which is the Cat.4 complex with a yield of 56%.

[0148] 1 1H NMR (400 MHz, C 6 D 6): δ 8.07 (dd, J = 15.0, 2.0 Hz, 4H), 7.72–7.64 (m, 4H), 7.60 (d, J = 6.3 Hz, 2H), 7.56 (d, J = 2.1 Hz, 2H), 7.43 (dd, J = 12.9, 2.2 Hz, 8H), 7.35 (dt, J = 4.6, 2.2 Hz, 4H), 7.22 (dd, J = 6.5, 2.2 Hz, 2H), 6.97 (d, J = 6.6 Hz, 2H), 4.34 (s, 4H), 1.40–1.28 (m, 90H).

[0149] Preparation of Example 5 Cat.5 Complex

[0150]

[0151] The synthetic route of Cat.5 is as follows:

[0152]

[0153]

[0154] (1) Preparation of Intermediate Ⅳ-2: Add 50 mmol of 2-bromo-4-tert-butylphenol and 25 mmol of 1,3-dibromopropane to a 500 mL round-bottom flask, then add 150 mL of acetone. After the reactants are dissolved, add 75 mmol of potassium hydroxide and reflux at 60 °C for 5 h. Thin layer chromatography (TLC) shows that the reaction is basically complete. After removing the acetone solvent by rotary evaporation, add 100 mL of DCM and 100 mL of water to the residue, extract and collect the organic phase. The aqueous phase is extracted with DCM (50 mL × 3). After mixing all the organic phases, dry with anhydrous Na 2 SO 4 , filter, and then remove the solvent from the filtrate by rotary evaporation. The residual solid is recrystallized from acetone to obtain a white solid, which is Intermediate Ⅳ-2 with a yield of 93%.

[0155] 1 1H NMR (500 MHz, Chloroform-d) δ 7.31–7.24 (m, 4H), 6.95 (d, J = 7.5 Hz, 2H), 4.18 (t, J = 7.1 Hz, 4H), 2.32 (p, J = 7.1 Hz, 2H), 1.33 (s, 18H).

[0156] (2) Preparation of Intermediate Ⅴ-2: In N 2Under this atmosphere, 20 mmol of intermediate Ⅳ-2 and 100 mL of ultra-dry THF were added to a 500 mL Schlenk flask. 40 mmol of n-BuLi (1.6 M hexane solution) was added dropwise at -78 °C and the mixture was reacted for 30 min. Then 40 mmol of B(OMe) 3 was added. After slowly warming up to 25 °C, the reaction was carried out for 12 h. After the reaction was completed, 80 mL of 2N HCl was added at 0 °C, and the mixture was stirred at 25 °C for 1 h. 100 mL of water was added. After the reaction mixture was allowed to stand and layer, the organic phase was collected, and the aqueous phase was extracted with EtOAc (50 mL×3). After all the organic phases were combined, they were dried over anhydrous MgSO 4 . After filtration, the solvent in the filtrate was removed by rotary evaporation to obtain a white solid product. The white solid product was further purified by washing with n-hexane (100 mL×3) to obtain a white solid powder, which was intermediate Ⅴ-2 with a yield of 85%.

[0157] 1 1H NMR (500 MHz, Chloroform-d) δ 7.36 (d, J = 1.4 Hz, 2H), 7.28 (dd, J = 7.5, 1.5 Hz, 2H), 7.06 (d, J = 7.5 Hz, 2H), 6.06 (s, 4H), 4.11 (t, J = 7.1 Hz, 4H), 2.30 (p, J = 7.1 Hz, 2H), 1.34 (s, 18H).

[0158] (3) Preparation of Cat.5 ligand: In a 500 mL Schlenk flask, 20 mmol of 1-bromo-9H-carbazole, 10 mmol of intermediate Ⅴ-2 and 100 mmol of Na 2 CO 3 were added respectively. Then 90 mL of toluene, 30 mL of ethanol and 30 mL of water were added respectively. After freezing and degassing three times, under N 2 atmosphere, 1 mmol of Pd(PPh 3 ) 4 was added to the mixed solution. The temperature was raised to 80 °C and the mixture was stirred and reacted for 12 h. After the reaction mixture was allowed to stand and layer, the organic phase was collected, and the aqueous phase was extracted with dichloromethane (30 mL×3). After all the organic phases were combined, they were dried over anhydrous MgSO 4 . Then the organic phase filtrate was obtained by filtration. After the solvent in the filtrate was removed by rotary evaporation, the product was separated and purified by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain a white solid product, which was Cat.4 ligand with a yield of 79%.

[0159] 11H NMR (500 MHz, Chloroform-d) δ 8.13–8.08 (m, 2H), 8.03 (dd, J = 7.6, 1.7 Hz, 2H), 7.73 (dd, J = 7.4, 1.5 Hz, 2H), 7.49 (d, J = 1.5 Hz, 2H), 7.46 (t, J = 7.5 Hz, 2H), 7.41 (dd, J = 7.4, 1.6 Hz, 2H), 7.35–7.27 (m, 6H), 7.20 (td, J = 7.4, 1.6 Hz, 2H), 6.95 (d, J = 7.4 Hz, 2H), 4.13 (t, J = 7.1 Hz, 4H), 2.29 (p, J = 7.1 Hz, 2H), 1.36 (s, 18H).

[0160] (4) Preparation of Cat.5 Complex: Under N 2 atmosphere, in a 200 mL Schlenk flask, 5 mmol of Cat.5 ligand and 5 mmol of HfBn 2 Cl 2 (Et 2 O) 2 were added to 60 mL of toluene, and the mixture was reacted under dark at 80 °C for 12 h. After filtration and collection of the filtrate, it was concentrated and then precipitated at -18 °C to obtain a white crystalline solid, which was the Cat.5 complex with a yield of 71%.

[0161] 1 1H NMR (400 MHz, C 6 D 6 ): δ 8.11 (dt, J = 7.5, 1.0 Hz, 2H), 8.00–7.94 (m, 2H), 7.54–7.45 (m, 4H), 7.40 (ddd, J = 7.2, 5.8, 1.2 Hz, 2H), 7.35–7.28 (m, 6H), 7.19 (dd, J = 6.5, 2.2 Hz, 2H), 6.93 (d, J = 6.5 Hz, 2H), 4.12 (t, J = 8.4 Hz, 4H), 2.36 (p, J = 8.4 Hz, 2H), 1.27 (s, 18H).

[0162] Example 6 Preparation of Cat.6 Complex

[0163]

[0164]

[0165] The synthetic route of Cat.6 is as follows:

[0166]

[0167] (1) Preparation of Cat.6 Ligand: In a 500 mL Schlenk flask, 20 mmol of 8-bromo-7H-benzo[c]carbazole, 10 mmol of intermediate V-2 and 100 mmol of Na 2 CO 3 were added respectively. Then, 90 mL of toluene, 30 mL of ethanol and 30 mL of water were added respectively. After freezing and degassing three times, under a N 2 atmosphere, 1 mmol of Pd(PPh 3 ) 4 was added to the mixed solution. The temperature was raised to 80 °C and stirred for 12 h. After the reaction, the mixed solution was allowed to stand and separate into layers. The organic phase was collected, and the aqueous phase was extracted with dichloromethane (30 mL × 3). After mixing all the organic phases, they were dried with anhydrous MgSO 4 . Then, the organic phase filtrate was obtained by filtration. After removing the solvent by rotary evaporation, the product was separated and purified by column chromatography (petroleum ether: ethyl acetate = 15:1) to obtain a white solid product, which was the Cat.6 ligand with a yield of 70%.

[0168] 1 H NMR (500 MHz, Chloroform-d) δ 8.58–8.51 (m, 2H), 7.98 (dd, J = 7.4, 1.5 Hz, 2H), 7.94–7.87 (m, 4H), 7.72 (dd, J = 7.5, 1.5 Hz, 2H), 7.52–7.39 (m, 10H), 7.36 (dd, J = 7.5, 1.4 Hz, 2H), 7.30 (dd, J = 7.5, 1.6 Hz, 2H), 6.94 (d, J = 7.5 Hz, 2H), 4.13 (t, J = 7.1 Hz, 4H), 2.29 (p, J = 7.1 Hz, 2H), 1.36 (s, 18H).

[0169] (2) Preparation of Cat.6 Complex: Under a N 2 atmosphere, in a 200 mL Schlenk flask, 5 mmol of Cat.6 ligand and 5 mmol of HfBn 2 Cl 2 (Et 2 O) 2 were added to 60 mL of toluene respectively. The reaction was carried out in the dark at 80 °C for 12 h. The filtrate was filtered and collected, concentrated and then precipitated at -18 °C to obtain a white crystalline solid, which was the Cat.6 complex with a yield of 68%.

[0170] 1 H NMR (400 MHz, C 6 D 6): δ 7.96–7.88 (m, 4H), 7.81 (dt, J = 7.4, 1.1 Hz, 4H), 7.63–7.57 (m, 4H), 7.45 (ddd, J = 8.2, 7.2, 1.5 Hz, 2H), 7.44–7.31 (m, 6H), 7.19 (dd, J = 6.5, 2.2 Hz, 2H), 6.93 (d, J = 6.5 Hz, 2H), 4.15 (t, J = 8.4 Hz, 4H), 2.37 (p, J = 8.4 Hz, 2H), 1.29 (s, 18H).

[0171] Preparation of Example 7 Cat.7 Complex

[0172]

[0173] The synthetic route of Cat.7 is as follows:

[0174]

[0175] (1) Preparation of Cat.7 Ligand: In a 500 mL Schlenk flask, add 20 mmol of 1-bromo-3,6-di-tert-butyl-9H-carbazole, 10 mmol of intermediate V-2 and 100 mmol of Na 2 CO 3 , then add 90 mL of toluene, 30 mL of ethanol and 30 mL of water respectively. After freezing and degassing 3 times, under the atmosphere of N 2 , add 1 mmol of Pd(PPh 3 ) 4 to the mixed solution, raise the temperature to 80 °C and stir the reaction for 12 h. After the reaction mixture is allowed to stand and separate into layers, collect the organic phase. The aqueous phase is extracted with dichloromethane (30 mL × 3). After mixing all the organic phases, dry with anhydrous MgSO 4 , then filter to obtain the filtrate of the organic phase. After removing the solvent by rotary evaporation of the filtrate, the product is separated and purified by column chromatography (petroleum ether: ethyl acetate = 25:1) to obtain a white solid product, which is the Cat.7 ligand with a yield of 81%.

[0176] 11H NMR (500 MHz, Chloroform-d) δ 8.25 (d, J = 1.5 Hz, 2H), 8.16 (d, J = 1.4 Hz, 2H), 7.49 (d, J = 1.5 Hz, 2H), 7.43–7.35 (m, 4H), 7.34–7.27 (m, 6H), 7.01 (d, J = 7.5 Hz, 2H), 4.13 (t, J = 7.1 Hz, 4H), 2.30 (p, J = 7.1 Hz, 2H), 1.41 (s, 18H), 1.36 (s, 18H), 1.32 (s, 18H).

[0177] (2) Preparation of Cat.7 Complex: Under N 2 atmosphere, in a 200 mL Schlenk flask, 5 mmol of Cat.7 ligand and 5 mmol of HfBn 2 Cl 2 (Et 2 O) 2 were added to 60 mL of toluene, and the mixture was reacted under dark at 80 °C for 12 h. After filtration and collection of the filtrate, it was concentrated and precipitated at -18 °C to obtain a white crystalline solid, which was the Cat.7 complex with a yield of 73%.

[0178] 1 1H NMR (400 MHz, C 6 D 6 ): δ 8.03–7.98 (m, 2H), 7.83 (d, J = 2.2 Hz, 2H), 7.52 (d, J = 2.1 Hz, 2H), 7.39–7.29 (m, 6H), 7.20 (dd, J = 6.5, 2.1 Hz, 2H), 7.00 (d, J = 6.6 Hz, 2H), 4.16 (t, J = 8.4 Hz, 4H), 2.33 (p, J = 8.4 Hz, 2H), 1.38–1.28 (m, 54H).

[0179] Example 8 Preparation of Cat.8 Complex

[0180]

[0181] The synthetic route of Cat.8 is as follows:

[0182]

[0183] (1) Preparation of Cat.8 Ligand: In a Schlenk flask, 20 mmol of Intermediate VI-1, 10 mmol of Intermediate V-2 and 100 mmol of Na 2 CO 3, then add 90 mL of toluene, 30 mL of ethanol, and 30 mL of water respectively. After freeze-degassing 3 times, under N 2 atmosphere, add 1 mmol of Pd(PPh 3 ) 4 to the mixed solution, raise the temperature to 80 °C, and stir the reaction for 12 h. After the reaction mixture is allowed to stand and layer, collect the organic phase. The aqueous phase is extracted with dichloromethane (30 mL × 3). After mixing all the organic phases, dry with anhydrous MgSO 4 , then filter to obtain the organic phase filtrate. After removing the solvent by rotary evaporation of the filtrate, the product is separated and purified by column chromatography (petroleum ether: ethyl acetate = 10:1) to obtain a white solid product, which is the Cat.8 ligand with a yield of 67%.

[0184] 1 H NMR (500 MHz, Chloroform-d) δ 7.79 (d, J = 1.4 Hz, 2H), 7.72 (d, J = 1.7 Hz, 2H), 7.55 (d, J = 1.4 Hz, 2H), 7.51 (d, J = 7.5 Hz, 2H), 7.46 (dd, J = 7.5, 1.5 Hz, 2H), 7.34 (d, J = 1.5 Hz, 2H), 7.18–7.13 (m, 4H), 6.95 (d, J = 7.5 Hz, 2H), 6.88 (dd, J = 8.6, 1.5 Hz, 8H), 6.84 (q, J = 1.8 Hz, 4H), 4.13 (t, J = 7.1 Hz, 4H), 2.46 (m, 2H), 2.35–2.25 (m, 90H).

[0185] (2) Preparation of Cat.8 complex: Under N 2 atmosphere, in a 200 mL Schlenk flask, add 5 mmol of Cat.8 ligand and 5 mmol of HfBn 2 Cl 2 (Et 2 O) 2 to 60 mL of toluene, and react under light protection at 80 °C for 12 h. Filter and collect the filtrate. Concentrate and precipitate at -18 °C to obtain a white crystalline solid, which is the Cat.8 complex with a yield of 51%.

[0186] 1 H NMR (400 MHz, C 6 D 6): δ 8.05 (dd, J = 15.0, 2.0 Hz, 4H), 7.75–7.66 (m, 4H), 7.61 (d, J = 6.3 Hz, 2H), 7.54 (d, J = 2.1 Hz, 2H), 7.41 (dd, J = 12.9, 2.2 Hz, 8H), 7.32 (dt, J = 4.6, 2.2 Hz, 4H), 7.19 (dd, J = 6.6, 2.2 Hz, 2H), 6.96 (d, J = 6.6 Hz, 2H), 4.11 (t, J = 8.4 Hz, 4H), 2.35 (p, J = 8.4 Hz, 2H), 1.39–1.27 (m, 90H).

[0187] Example 9 Copolymerization of Ethylene and Norbornene Catalyzed by Bis(carbazolyl)biphenoxy Ether Complex

[0188] A 250 mL stainless steel reactor equipped with a magnetic stir bar was dried at 100 °C for more than 2 h. While it was still hot, it was evacuated to ~2.5 mbar, and then N 2 and replaced with vacuum-N 2 three times, and then replaced with vacuum-ethylene gas three times. While maintaining a slightly positive pressure inside the reactor and a stirring speed of 500 rpm, 100 mL of 3 M norbornene / toluene solution and 1.7 mL of MAO (1.5 M toluene solution) were successively added to the reactor. Then the reaction temperature was raised to 130 °C, and the pressure inside the reactor (polymerization reaction pressure) was maintained at 0.4 MPa by ethylene gas. After the reaction system was stable, 5.0 mL of bis(carbazolyl)biphenoxy ether complex solution (0.001 M toluene solution) was pressured into the reaction system through ethylene gas to start the polymerization reaction. After 2 min of polymerization reaction, the ethylene gas was stopped. After the reactor was cooled to 100 °C, the unreacted ethylene was depressurized and discharged, and the reaction solution was drained into 500 mL of ethanol. The polymerization product was washed three times with ethanol and then dried to a constant weight in a vacuum oven at 50 °C. The polymerization reaction activity and copolymer characterization results are shown in Tables 1, 2, and 3.

[0189] Comparative Example 1 rac-SiMe 2 (Ind) 2 ZrCl 2 Complex Catalyzed Copolymerization of Ethylene and Norbornene

[0190] A 250 mL stainless steel reactor equipped with a magnetic stir bar was dried at 100 °C for more than 2 h. While it was still hot, it was evacuated to ~2.5 mbar, and then N 2 and replaced with vacuum-N 2Replace three times, and then replace with vacuum-ethylene gas three times. While maintaining a slightly positive pressure inside the reaction kettle and a stirring speed of 500 rpm, sequentially add 100 mL of 3M norbornene / toluene solution and 1.7 mL of MAO (1.5M toluene solution) into the reaction kettle, then raise the temperature to the reaction temperature of 130 °C, and maintain the pressure inside the kettle (polymerization reaction pressure) at 0.4 MPa through ethylene gas. After the reaction system is stable, press 5.0 mL of the rac-SiMe 2 (Ind) 2 ZrCl 2 complex solution (0.001M toluene solution) into the reaction system to start the polymerization reaction. After 2 minutes of the polymerization reaction, stop passing ethylene gas. After the reaction kettle is cooled to 100 °C, release the pressure to discharge the unreacted ethylene, and drain the reaction solution into 500 mL of ethanol. Wash the polymerization product three times with ethanol, and then place it in a vacuum oven at 50 °C to dry to a constant weight. The results of the polymerization reaction activity and copolymer characterization are shown in Tables 1, 2, and 3.

[0191] Comparative Example 2 Me 2 Si(C 5 Me 4 )(N-tBu)TiCl 2 Copolymerization of ethylene and norbornene catalyzed by the complex

[0192] Dry a 250 mL stainless steel reaction kettle equipped with a magnetic stirrer at 100 °C for more than 2 h. While it is still hot, evacuate to ~2.5 mbar, and then introduce N 2 and replace with vacuum-N 2 three times, and then replace with vacuum-ethylene gas three times. While maintaining a slightly positive pressure inside the reaction kettle and a stirring speed of 500 rpm, sequentially add 100 mL of 3M norbornene / toluene solution and 1.7 mL of MAO (1.5M toluene solution) into the reaction kettle, then raise the temperature to the reaction temperature of 130 °C, and maintain the pressure inside the kettle (polymerization reaction pressure) at 0.4 MPa through ethylene gas. After the reaction system is stable, press 5.0 mL of the Me 2 Si(C 5 Me 4 )(N-tBu)TiCl 2 complex solution (0.001M toluene solution) into the reaction system to start the polymerization reaction. After 2 minutes of the polymerization reaction, stop passing ethylene gas. After the reaction kettle is cooled to 100 °C, release the pressure to discharge the unreacted ethylene, and drain the reaction solution into 500 mL of ethanol. Wash the polymerization product three times with ethanol, and then place it in a vacuum oven at 50 °C to dry to a constant weight. The results of the polymerization reaction activity and copolymer characterization are shown in Tables 1, 2, and 3.

[0193] Table 1 Test results of the copolymerization reaction activity of ethylene and norbornene and the polymer indexes

[0194]

[0195] Table 2 Characterization Results of Polymer Structure and Optical Properties

[0196]

[0197] Table 3 Characterization Results of Polymer Mechanical Properties

[0198]

[0199]

[0200] The results in Table 1 show that the bis-carbazolyl bis-phenoxy ether complex described in the present invention has excellent catalytic activity for copolymerization of ethylene and norbornene, a high cycloolefin monomer insertion rate, a relatively large molecular weight, and a wide range for regulating its distribution.

[0201] The results in Table 2 show that the COC prepared by the method described in the present invention has excellent optical properties, such as good transparency (light transmittance > 91%), a high refractive index (> 1.50), a high Abbe number (> 50), etc.

[0202] The results in Table 3 show that the COC prepared by the method described in the present invention has excellent mechanical properties, and has excellent toughness while maintaining high mechanical strength.

[0203] In addition, the bis-carbazolyl bis-phenoxy ether complex described in the present invention also has excellent high-temperature stability, and can still maintain a relatively high polymerization activity and cycloolefin monomer insertion rate at a high reaction temperature of 130 °C.

[0204] Unless otherwise specified, the terms used in the present invention have the meanings commonly understood by those skilled in the art.

[0205] The embodiments described in the present invention are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. Those skilled in the art can make various other substitutions, changes, and improvements within the scope of the present invention. Therefore, the present invention is not limited to the above embodiments and is only defined by the claims.

Claims

1. A bis-carbazolyl bis-phenoxy ether complex having a structure shown in formula (Ⅰ), wherein, M is selected from titanium, zirconium or hafnium; R 1 ~R 11 Each independently selected from hydrogen, a substituted or unsubstituted C1-C40 hydrocarbon group, a C3-C40 cycloalkyl group, a C6-C40 aryl group, a heteroatom-containing group, or a silyl group containing 1 to 3 Si atoms; R 1 ~R 11 Two or more of them may be bonded to each other to form a hydrocarbon ring; X is selected from halogen, -NH 2 , substituted or unsubstituted C1-C20 alkyl, -N(C1-C20 alkyl) 2 , C6-C20 aryl or benzyl; Y is selected from a substituted or unsubstituted C1-C20 hydrocarbon group, a C3-C20 cycloalkyl group, a heteroatom-containing hydrocarbon group or a silyl group containing 1-3 Si atoms.

2. The bis-carbazolyl bis-phenoxy ether complex according to claim 1, characterized in that, In the bis-carbazolyl bis-phenoxy ether complex, the R 1 ~R 11 are each independently selected from hydrogen, a C1-C12 hydrocarbon group, a C3-C16 cycloalkyl group or a C6-C18 aryl group. Preferably, the R 1 ~R 11 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, a substituted phenyl, or two or more of R 1 ~R 11 can bond to each other to form a hydrocarbon ring; X is selected from halogen, C1-C4 alkyl, benzyl or -N(C1-C4 alkyl). 2 Preferably, X is selected from halogen, including F, Cl, Br and I.

3. The bis-carbazolyl bis-phenoxy ether complex according to claim 1 or 2, characterized in that, the bis-carbazolyl bis-phenoxy ether complex is selected from any one of the following complexes Cat.1-Cat.8: Cat.1 Cat.2 Cat.3 Cat.4 Cat.5 Cat.6 Cat.7 Cat.8 4. A method for preparing the bis-carbazolyl bis-phenoxy ether complex according to any one of claims 1-3, characterized in that, comprises the following steps: S1: Synthesize a phenoxy ether compound Ⅳ from compounds Ⅱ and Ⅲ through a Williamson reaction; S2: Dissolve the compound Ⅳ in a solvent, then add an alkyllithium for lithiation at a low temperature, then add trimethyl borate for reaction, and then add an aqueous hydrochloric acid solution for hydrolysis to obtain a compound Ⅴ; S3: Carry out a Suzuki coupling reaction catalyzed by a palladium catalyst between the compound Ⅴ and a bromide Ⅵ of carbazole or its derivative under alkaline conditions to obtain a ligand compound; S4: React the ligand compound with alkyllithium to obtain the lithium salt of the ligand compound, and then react it with MX 4 or its ether complex; alternatively, directly react the ligand compound with MR 2 X 2 or its ether complex to obtain the bis(carbazolyl)diphenoxy ether complex 5. The method according to claim 4, characterized in that, In the formulas II and IV, X 1 is selected from halogens, preferably Br; in the step S2, the alkyllithium is one or more of C1-C6 alkyllithiums, preferably one or more of methyllithium, n-butyllithium, and n-hexyllithium; in the formula (V), Z is a boronic acid group or a boronic acid ester group, preferably selected from -B(OH) 2 or -B(OMe) 2 ; in the step S4, the alkyllithium is one or more of C1-C6 alkyllithiums, preferably one or more of methyllithium, n-butyllithium, and n-hexyllithium; MX 4 is selected from one or more of TiCl 4 , ZrCl 4 , HfCl 4 ; in the step S4, R in MR 2 X 2 is selected from C1-C20 alkyl, aryl or benzyl, preferably ZrBn 2 Cl 2 (Et 2 O) 2 , HfBn 2 Cl 2 (Et 2 O) 2 .

6. Use of the bis-carbazolyl bis-phenoxy ether complex according to any one of claims 1-3 as a main catalyst for olefin polymerization.

7. The use according to claim 6, characterized in that, the olefin polymerization is a copolymerization of ethylene and / or an α-olefin with a cycloolefin; Preferably, the α-olefin is a C3-C12 α-olefin, preferably selected from one or more of 1-propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and the cycloolefin is a C6-C21 cycloolefin, preferably selected from one or more of cyclohexene, norbornene, tetracyclododecene.

8. An olefin polymerization method, comprising the following steps, in the presence of a main catalyst and a cocatalyst, ethylene and / or an α-olefin and a cycloolefin are polymerized to form an olefin copolymer; wherein, the main catalyst is the bis-carbazolyl bis-phenoxy ether complex according to any one of claims 1-3; Preferably, the α-olefin is a C3-C12 α-olefin, preferably selected from one or more of 1-propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and the cycloolefin is a C6-C21 cycloolefin, preferably selected from one or more of cyclohexene, norbornene, tetracyclododecene.

9. The olefin polymerization method according to claim 8, characterized in that, the molar ratio of the main catalyst to the cocatalyst is 1:1-5000, preferably 1:1-2000; and / or, The cocatalyst is selected from one or more of alkylaluminum, alkylaluminum chloride, aluminoxane, and boron-containing additives; preferably, the alkylaluminum is selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-hexylaluminum, and the alkylaluminum chloride is selected from one or more of diethylaluminum monochloride, diethylaluminum dichloride, and sesqui-diethylaluminum monochloride; the aluminoxane is selected from one or more of methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane; the boron-containing additive is selected from one or two of tris(pentafluorophenyl)borane and triphenylcarbenium tetrakis(pentafluorophenyl)borate; More preferably, the cocatalyst is selected from methylaluminoxane or a combination of methylaluminoxane and triisobutylaluminum in a molar ratio of 1 to 50:1, preferably 2 to 30:

1.

10. The olefin polymerization process according to claim 8 or 9, characterized in that the reaction temperature of the polymerization reaction is 50 to 200 °C, preferably 90 to 180 °C; and / or, the reaction pressure of the polymerization reaction is 0.01 to 10 MPa, preferably 0.1 to 3 MPa; and / or, the reaction time of the polymerization reaction is 0.1 to 1000 min, preferably 1 to 100 min.

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