CN120058766A - Bicarbazolyl diphenoxy ether complex and preparation method and application thereof - Google Patents

Abstract

The present invention provides a biscarbazolyl bisphenoxy ether complex and a preparation method and application thereof. The complex of the present invention has extremely high catalytic activity and high temperature resistance when used to catalyze the copolymerization of ethylene and/or alpha-olefins with cycloolefins, and the prepared copolymerization product has excellent optical properties, such as good transparency, high refractive index, high Abbe number, etc.; at the same time, it has excellent mechanical properties, such as high strength and good toughness; in addition, the copolymer has good heat resistance, such as high temperature yellowing resistance. Therefore, the complex provided by the present invention is very suitable for catalyzing the copolymerization of ethylene and/or alpha-olefins with cycloolefins, and the obtained copolymerization product has good industrialization prospects in the processing and application of the optical field.

Description

Bicarbazolyl diphenoxy ether complex and preparation method and application thereof

Technical Field

The invention relates to the field of olefin polymerization, in particular to a biscarbazolyl diphenoxy ether complex, a preparation method and application thereof, and also relates to an olefin polymerization method.

Background

COC is an amorphous engineering plastic obtained by addition copolymerization of ethylene and/or alpha-olefin and cycloolefin under the action of a coordination polymerization catalyst. Currently, the main COC in the market is Japanese Bao Liu plastics and TOPAS and APEL series commercial products developed by Mitsui chemistry.

Compared with conventional optical materials such as polymethyl methacrylate (PMMA), polycarbonate (PC), and the like, COC has comparable light transmittance, refractive index, birefringence, and the like, but the latter has excellent characteristics of low hygroscopicity, low specific gravity, and the like. In order to obtain temperature resistance comparable to or even better than PMMA and PC, it is necessary to increase the insertion rate of cyclic olefin in COC, but the brittleness of COC is increased while the temperature resistance is improved, which is disadvantageous for processing, so that development of a novel catalyst and catalytic system is required.

COC catalysts mainly include Ziegler-Natta catalysts, metallocene and non-metallocene catalysts, and the like. The Ziegler-Natta catalyst is a multi-active-center catalyst, can obtain polymers with wide molecular weight distribution, but has two polymerization modes of addition copolymerization and ring-opening metathesis polymerization when catalyzing COC polymerization, and has low catalytic activity, and the metallocene catalyst is a single-active-center catalyst, and has good catalytic activity when catalyzing polymerization reaction, but the product is generally narrower in relative molecular weight distribution, and the processability of polymer resin is reduced. To solve this problem, it is possible to achieve this by adjusting the molecular weight distribution, for example by preparing a bimodal polyolefin. For example, chinese patents CN114736321A, CN114853947a and CN105524217a respectively provide a method for preparing polymers of different molecular weight distribution. As described above, two or more catalysts are usually needed for preparing the bimodal or multimodal polyolefin, the catalyst is realized by a special process, the non-metallocene catalyst is an olefin polymerization catalyst with prospect, more catalyst framework design and modification space are provided, the occurrence of the catalyst can possibly make up for the defects of the existing catalytic system in preparing the polymer structure diversity, such as copolymerization of catalytic ethylene with alpha-olefin, diolefin, cycloolefin and even polar monomer, but the existing non-metallocene catalyst has the problems of low catalytic activity, low insertion rate of cycloolefin monomer (i.e. low glass transition temperature T _g of COC), difficult regulation and control of polymer structure, molecular weight (M _w) and distribution (PDI) and the like.

Disclosure of Invention

In order to develop a wider variety of olefin coordination polymerization catalysts and improve the catalytic performance thereof, an object of the present invention is to provide a biscarbazolyl diphenoxy ether complex, which is used as a main catalyst for catalyzing polymerization of ethylene and/or alpha-olefin and cycloolefin, can obtain COC with excellent mechanical strength and toughness and optical performance, and has good high temperature stability.

The invention also aims to provide a preparation method of the biscarbazolyl diphenoxy ether complex.

It is a further object of the present invention to provide a process for the polymerization of olefins.

The first aspect of the invention provides a biscarbazolyl diphenoxy ether complex with a structure shown as a formula (I),

Wherein M is selected from titanium, zirconium or hafnium;

R ₁～R₁₁ is independently selected from hydrogen, substituted or unsubstituted C1-C40 alkyl, C3-C40 cycloalkyl, C6-C40 aryl, heteroatom-containing group or silane group containing 1-3 Si atoms, two or more of R ₁～R₁₁ can be mutually bonded to form a hydrocarbon group 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 cyclic hydrocarbon group, a heteroatom-containing hydrocarbon group or a silane group containing 1-3 Si atoms;

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

Preferably, in the biscarbazolyl diphenoxy ether complex provided by the invention, R ₁～R₁₁ is independently selected from hydrogen, C1-C12 alkyl, C3-C16 cycloalkyl or C6-C18 aryl. In some preferred embodiments, each of the R ₁～R₁₁ is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, or (substituted) phenyl, etc., or two or more of R ₁～R₁₁ may be bonded to each other to form a hydrocarbyl ring.

Preferably, in the biscarbazolyl diphenoxy ether complex provided by the invention, X is selected from halogen, C1-C4 alkyl, benzyl or-N (C1-C4 alkyl) ₂. In some preferred embodiments, the X is selected from the group consisting of halogen, including F, cl, br, and I. In some more preferred embodiments, the X is selected from Cl.

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

The biscarbazolyl diphenoxy ether complex provided by the invention is further preferably selected from any one of the following complexes Cat.1-Cat.8:

The second aspect of the invention provides a preparation method of the biscarbazolyl diphenoxy ether complex, which comprises the following steps:

S1, synthesizing a phenoxy ether compound IV by a Williamson reaction by using the compounds II and III;

S2, dissolving the compound IV in a solvent, adding alkyl lithium at a low temperature for lithiation, adding trimethyl borate for reaction, and then adding an aqueous solution of hydrochloric acid for hydrolysis to obtain the compound V;

s3, carrying out a Suzuki coupling reaction on the compound V and a bromo (VI) of carbazole or a derivative thereof under an alkaline condition through catalysis of a palladium catalyst to obtain a ligand compound;

S4, reacting the ligand compound with alkyl lithium to obtain lithium salt of the ligand compound, and then reacting with MX ₄ (or ether complex thereof), or directly reacting the ligand compound with MR ₂X₂ (or ether complex thereof) to obtain the biscarbazolyl diphenoxy ether complex.

In a preferred embodiment, in step S1 of the present invention, II and III are added to acetone at room temperature, followed by a base-catalyzed reaction, and heated to reflux to obtain compound IV.

In the formulae (II) and (IV) according to the invention, X ₁ is selected from halogen, preferably Br.

In a preferred embodiment, in step S1 of the present invention, the base is one or more of NaOH、KOH、Ba(OH)₂、Ca(OH)₂、K₂CO₃、K₃PO₄、Na₂CO₃、Cs₂CO₃ and the like.

In a preferred embodiment, in the step S1 of the present invention, the molar ratio of the compound II to the compound III is 1 (0.5 to 10), preferably 1 (0.5 to 1).

In a preferred embodiment, in step S1 of the present invention, the molar ratio of the compound II to the base is 1 (1 to 10), preferably 1 (1 to 2).

In a preferred embodiment, in step S1 of the present invention, the amount of acetone is 0.1 to 100ml of acetone per millimole of compound II, preferably 1 to 10ml of acetone per millimole of compound II.

As a preferable scheme, in the step S1, the reaction temperature is 30-100 ℃, preferably 50-70 ℃.

As a preferable scheme, in the step S1, the reaction time is 0.1-100 h, preferably 1-10 h.

In a preferred embodiment, in the step S1 of the present invention, the reaction is performed in N ₂ or air atmosphere, and after the reaction is completed, the method further comprises post-treatment processes such as separation, refining, etc., which are not particularly required in the field of conventional operations, for example, in some specific embodiments, the method may be adopted to remove the solvent by spin evaporation or decompression, extract and separate liquid such as water, dichloromethane (DCM) or ethyl acetate, dry anhydrous Na ₂SO₄ or MgSO ₄, and purify the target product by column chromatography or recrystallization or pulping with an organic solvent.

As a preferred embodiment, in the 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, diethyl ether, n-propyl ether, isopropyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, dioxane, preferably one or more of tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether.

As a preferred embodiment, in the step S2 of the present invention, the alkyl lithium is one or more of C1-C6 alkyl lithium, preferably one or more of methyl lithium, n-butyl lithium and n-hexyl lithium.

In a preferred embodiment, in step S2 of the present invention, the concentration of the aqueous hydrochloric acid solution is 0.1 to 10n, preferably 1 to 2n.

As a preferable scheme, in the step S2, the molar ratio of the compound IV to the alkyl lithium to the trimethyl borate to the hydrochloric acid is 1 (1-3): 1-10): 1-50, preferably 1 (2-2.2): 2-4): 4-20.

In a preferred embodiment, in step S2 of the present invention, the solvent is used in an amount of 0.1 to 100ml of solvent per millimole of compound IV, preferably 1 to 10ml of solvent per millimole of compound IV.

As a preferable scheme, in the step S2, when the alkyl lithium and the trimethyl borate are added, the temperature of a reaction system is-80-40 ℃, and is preferably-80-0 ℃. The temperature of the reaction system is-80-40 ℃, preferably-80-40 ℃, and the reaction time is 0.1-100 h, preferably 0.1-10 h after the alkyl lithium is added. After trimethyl borate is added, the temperature of the reaction system is-80-40 ℃, preferably 0-25 ℃, and the reaction time is 0.1-100 h, preferably 1-10 h.

As a preferable scheme, in the step S2, the temperature of a reaction system is-80-40 ℃, preferably-10 ℃, when the aqueous hydrochloric acid solution is added. After the aqueous solution of hydrochloric acid is added, the temperature of the reaction system is-80-40 ℃, preferably 0-25 ℃, and the reaction time is 0.1-100 h, preferably 1-10 h.

In a preferred embodiment, in the step S2 of the present invention, the reaction is performed in N ₂ or Ar atmosphere, and after the reaction is completed, the method further comprises post-treatment processes such as separation, refining, etc., which are not particularly required in the field of conventional operations, for example, in some specific embodiments, the method may be adopted to remove the solvent by spin evaporation or decompression, extract and separate liquid such as water, dichloromethane (DCM) or ethyl acetate, dry anhydrous Na ₂SO₄ or MgSO ₄, and purify the target product by column chromatography or recrystallization or pulping with an organic solvent.

In the formula (V), Z is a boric acid group or a boric acid ester group, and is selected from-B (OH) ₂ or-B (OMe) ₂.

In a preferred embodiment, in step S3 of the present invention, the base is one or more of NaOH、KOH、Ba(OH)₂、Ca(OH)₂、K₂CO₃、K₃PO₄、Na₂CO₃、Cs₂CO₃、TlOH、KF、CsF、Bu₄NF、NaOCH₂CH₃、N(CH₂CH₃)₃ or the like, preferably one or more of NaOH, KOH, K ₂CO₃、Na₂CO₃、Cs₂CO₃.

As a preferred embodiment, in step S3 of the present invention, the palladium catalyst is one or more of Pd(PPh₃)₄、Pd(dppf)Cl₂、Pd(OAc)₂、PdCl₂、PdCl₂(PPh₃)₂、Pd(OAc)₂(PPh₃)₂、Pd(OAc)₂(P(Cy)₃)₂、Pd(P_tBu₃)₂、PdCl₂(P(Cy)₃)₂、PdCl(Bn)(PPh₃)₂、Pd₂(dba)₃, preferably one or more of Pd(PPh₃)₄、Pd(dppf)Cl₂、Pd(P_tBu₃)₂、Pd₂(dba)₃.

As a preferred embodiment, step S3 of the present invention is carried out in the presence of a solvent selected from 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 t-butyl ether, ethylene glycol dimethyl ether, dioxane, water, methanol, ethanol, isopropanol, preferably one or more of toluene, xylene, dioxane, water, ethanol.

In a preferred embodiment, in step S3 of the present invention, the solvent is added in an amount of 0.1 to 1000ml per millimole of the compound V, preferably 1 to 100ml per millimole of the compound V.

As a preferable scheme, in the step S3 of the invention, the molar ratio of the compound V to the compound VI to the alkali to the palladium catalyst is 1 (0.1-100): (0.0001-1), preferably 1 (0.1-10): (0.001-0.1).

As a preferable scheme, in the step S3, the reaction temperature is 0-160 ℃, preferably 40-130 ℃.

As a preferable scheme, in the step S3, the reaction time is 0.1-100 h, preferably 1-10 h.

In a preferred embodiment, in the step S3 of the present invention, the reaction is performed in N ₂ or Ar atmosphere, and after the reaction is completed, the method further comprises post-treatment processes such as separation, refining, etc., which are not particularly required in the field of conventional operations, for example, in some specific embodiments, the method may be adopted to remove the solvent by spin evaporation or decompression, extract and separate liquid such as water, dichloromethane (DCM) or ethyl acetate, dry anhydrous Na ₂SO₄ or MgSO ₄, and purify the target product by column chromatography or recrystallization or pulping with an organic solvent.

As a preferred embodiment, in the step S4 of the present invention, the alkyl lithium is one or more of C1-C6 alkyl lithium, preferably one or more of methyl lithium, n-butyl lithium and n-hexyl lithium.

In 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.

As a preferred embodiment, step S4 of the present invention is carried out in the presence of a solvent selected from 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 t-butyl ether, ethylene glycol dimethyl ether, dioxane, preferably toluene, n-hexane, n-heptane, tetrahydrofuran, diethyl ether.

In a preferred embodiment, in step S4, the solvent is added in an amount of 0.1 to 1000mL of solvent per millimole of ligand, preferably 1 to 100mL of solvent per millimole of ligand.

In step S4 of the present invention, MX ₄ is one or more selected from TiCl ₄、ZrCl₄、HfCl₄.

In the step S4, R in the MR ₂X₂ is selected from C1-C20 alkyl, aryl or benzyl. Such as ZrBn ₂Cl₂(Et₂O)₂、HfBn₂Cl₂(Et₂O)₂.

As a preferable scheme, in the step S4 of the invention, the molar ratio of the ligand to the alkyl lithium to the MX ₄ (or the ether complex thereof) is 1 (0.1-100): 0.1-100, preferably 1 (1-3): 1-3.

In a preferred embodiment, in step S4 of the present invention, the molar ratio of the ligand to MR ₂X₂ (or an ether complex thereof) is 1 (0.1 to 100), preferably 1 (1 to 3).

In a preferred embodiment, in step S4 of the present invention, the reaction temperature of the ligand, the alkyl lithium, MX ₄ (or an ether complex thereof) is-80 to 50 ℃, preferably-10 to 25 ℃. The reaction time of the ligand and the alkyl lithium is 0.1-100 h, preferably 0.1-10 h. The reaction time of the ligand lithium salt and MX ₄ (or ether complex thereof) is 0.1-100 h, preferably 1-30 h.

In a preferred embodiment, in step S4 of the present invention, the reaction temperature of the ligand and MR ₂X₂ (or its ether complex) is-20 to 150 ℃, preferably 25 to 110 ℃. The reaction time of the ligand and MR ₂X₂ (or ether complex thereof) is 0.1-100 h, preferably 1-30 h.

In a preferred embodiment, in the step S4 of the present invention, the reaction is performed in N ₂ or Ar atmosphere, and after the reaction is completed, the post-treatment processes such as separation and refining are further included, so that the present invention is not particularly limited to the conventional operation in the field, and in some specific embodiments, the method may be adopted, for example, the method includes filtering to separate filtrate and solid residues, removing solvent under reduced pressure, and obtaining the target product through recrystallization or pulping and purification with an organic solvent.

The third aspect of the invention provides the use of the biscarbazolyl diphenoxy ether complex as a main catalyst for olefin polymerization.

The complex structure provided by the invention has extremely high catalytic activity, good high temperature resistance and higher polymerization temperature resistance when being used for catalyzing polymerization reaction of ethylene and/or alpha-olefin and cycloolefin due to special coordination space and electronic effect of an active center, and better thermal stability, thereby being beneficial to prolonging service life, and on the other hand, chain segment distribution of cycloolefin bigeminy, trigeminy and above is reduced, and the ethylene and cycloolefin mainly take alternating chain segments as main, so that the distribution of cycloolefin in COC is more uniform, the stereoregularity is better, the COC transparency is improved while the high refractive index and the high Abbe number are maintained, the content of terminal double bonds of the copolymer is low, the problem of high temperature yellowing and the like is avoided, and the complex structure is more suitable for the application in the optical field. In addition, when the complex provided by the invention catalyzes the copolymerization of ethylene and/or alpha-olefin and cycloolefin, the obtained polymer has excellent toughness and is easy to process while maintaining the high mechanical strength of the polymer, and is presumed to be due to the fact that the COC has a high branching degree or has a long-chain branched structure characteristic. Therefore, the complex provided by the invention is very suitable for catalyzing the polymerization reaction of olefin, especially the copolymerization reaction of ethylene and/or alpha-olefin and cycloolefin.

In the use provided by the invention, the olefin polymerization is the copolymerization of ethylene and/or alpha-olefin with cycloolefin. In some preferred embodiments, the alpha-olefin is a C3 to C12 alpha-olefin including, but not limited to, one or more of 1-propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and the cyclic olefin is a C6 to C21 cyclic olefin including, but not limited to, one or more of cyclohexene, norbornene, tetracyclododecene.

The fourth aspect of the invention provides an olefin polymerization method, which comprises the step of carrying out polymerization reaction on ethylene and/or alpha-olefin and cycloolefin in the presence of a main catalyst and a cocatalyst to form an olefin copolymer, wherein the main catalyst is the biscarbazolyl diphenoxy ether complex.

In some preferred embodiments, the α -olefin is a C3 to C12 α -olefin, including but not limited to one or more of 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene, and the cyclic olefin is a C6 to C21 cyclic olefin, including but not limited to one or more of cyclohexene, norbornene, and tetracyclododecene.

In the polymerization method provided by the invention, the molar ratio of the main catalyst to the cocatalyst is 1:1-5000. In some preferred embodiments, the molar ratio of the procatalyst to the cocatalyst is 1:1-2000, including but not limited to molar ratio intervals of 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 procatalyst to the cocatalyst is from 1:1 to 1500.

In the polymerization process provided by the present invention, the cocatalyst may be of any kind commonly known in the art. In some preferred embodiments, the promoter is selected from one or more of an alkyl aluminum, an alkyl aluminum chloride, an aluminoxane, a boron-containing promoter. In some more preferred embodiments, the alkyl aluminum is selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, the alkyl aluminum chloride is selected from one or more of diethylaluminum chloride, ethylaluminum dichloride, diethylaluminum sesquichloride, the aluminoxane is selected from one or more of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and the boron-containing auxiliary is selected from one or two of tris (pentafluorophenyl) borane, triphenylcarbon tetrakis (pentafluorophenyl) borate.

In the polymerization method provided by the invention, as a preferable scheme, the cocatalyst is selected from Methylaluminoxane (MAO), or the cocatalyst is selected from a combination of methylaluminoxane and triisobutylaluminum in a molar ratio of 1-50:1, including but not limited to a molar ratio interval of 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 the group consisting of methylaluminoxane and triisobutylaluminum in a molar ratio of 2-30:1.

In the polymerization method provided by the invention, as a preferable scheme, the cocatalyst is selected from a combination of a boron-containing auxiliary agent and aluminum alkyl, and the cocatalyst is selected from a combination of a boron-containing auxiliary agent and aluminum alkyl in a molar ratio of 1:1-3000, including but not limited to a molar ratio interval of 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 group consisting of triphenylcarbon tetrakis (pentafluorophenyl) borate in combination with triisobutylaluminum in a molar ratio of 1:300.

In the polymerization method provided by the invention, as a preferable scheme, the cocatalyst is selected from a combination of a boron-containing auxiliary agent and MAO (or modified methylaluminoxane, MMAO), and the cocatalyst is selected from a combination of a boron-containing auxiliary agent and MAO (or MMAO) in a molar ratio of 1:1-3000, including but not limited to a molar ratio interval of 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 group consisting of triphenylcarbon tetrakis (pentafluorophenyl) borate in combination with MAO in a molar ratio of 1:500.

In the polymerization method provided by the invention, the characteristics of the prepared polymerization product, especially the cycloolefin monomer insertion rate and the polymer microstructure of the copolymer (such as the copolymer of ethylene and norbornene) can be adjusted in a wider range by adjusting the structure of the main catalyst and the polymerization process conditions. Moreover, even if the polymerization is carried out at a higher temperature (130 ℃) the polymerization activity of the catalyst is not significantly sacrificed and still can be maintained at a higher level (as shown in table 1).

In the polymerization method provided by the invention, the reaction temperature of the polymerization reaction is 50-200 ℃, and the reaction temperature can be appropriately adjusted by a person skilled in the art according to actual reaction conditions such as polymerization types, polymerization monomer types and the like. In some preferred embodiments, the reaction temperature of the polymerization reaction is 90-180 ℃. In some more preferred embodiments, the polymerization reaction is conducted at a reaction temperature greater than 110 ℃, for example 110-140 ℃.

The biscarbazolyl diphenoxy ether complex provided by the invention has good high temperature stability, can still keep higher polymerization activity at higher reaction temperature (for example, 150 ℃), and the polymerization temperature which can be tolerated by the catalyst commonly used in the field (including single or double active center metallocene or single or double active center non-metallocene catalyst) is not more than 130 ℃.

In the polymerization method provided by the invention, the reaction pressure of the polymerization reaction is 0.01-10 MPa, and the reaction pressure can be appropriately adjusted by a person skilled in the art according to actual reaction conditions such as polymerization types, polymerization monomer types and the like. In some preferred embodiments, the reaction pressure of the polymerization reaction is 0.1-3 mpa.

In the polymerization method provided by the invention, the reaction time of the polymerization reaction is 0.1-1000 min, and the reaction time can be properly adjusted by a person skilled in the art according to actual reaction conditions such as polymerization types, polymerization monomer types and the like. In some preferred embodiments, the reaction time of the polymerization reaction is 1to 100min, for example, may be 1to 30min.

The polymerization method provided by the invention can be a solution polymerization process, namely, the polymerization reaction is carried out in a solvent, and the used solvent can be any kind common in the field.

In the polymerization method provided by the invention, other process steps, post-treatment steps and the like except the process parameters can be adopted by the conventional technology in the field, or can be appropriately adjusted by the person skilled in the art according to the actual reaction conditions of the polymerization type, the polymerization monomer type and the like.

In order to overcome the defects of the existing olefin coordination polymerization catalyst, the invention optimizes the three-dimensional effect and the electronic effect of the catalytic active center by reasonably designing the catalyst skeleton structure and the modification group, thereby obtaining the excellent catalyst with high catalytic activity, high insertion rate of cycloolefin monomers, easy regulation and control of polymer microstructure, M _w and PDI and high temperature resistance. The COC obtained by taking the biscarbazolyl diphenoxy ether complex as a main catalyst has good optical performance (high transparency, yellowing resistance, refractive index and Abbe number equivalent to those of PC and PMMA, and the like), high strength, good toughness and easy processing. Can obtain more kinds of novel COC products and meet the increasingly diversified application requirements.

The technical scheme provided by the invention has the following advantages:

(1) The complex provided by the invention has extremely high catalytic activity and good high temperature resistance, and is very suitable for catalyzing the polymerization reaction of olefin, in particular to the copolymerization reaction of ethylene and/or alpha-olefin and cycloolefin.

(2) Compared with the existing metallocene and non-metallocene complex catalysts, the complex provided by the invention is used as a main catalyst to catalyze copolymerization of ethylene and/or alpha-olefin and cycloolefin, so that the chain segment distribution of the cyclic olefin in COC, i.e. the chain segment distribution of the cyclic olefin in the COC is reduced, and the ethylene and the cycloolefin mainly take alternating isotactic chain segments, so that the distribution of the cycloolefin in the COC is more uniform, the stereoregularity is better, the COC transparency is improved while the high refractive index and the low birefringence are maintained, the content of double bonds at the tail end of the copolymer is low, the problems of yellowing processing and the like are avoided, and the complex is more suitable for the application in the optical field.

(3) When the complex provided by the invention catalyzes the copolymerization of ethylene and/or alpha-olefin and cycloolefin, COC with different mechanical properties can be obtained by regulating and controlling the structure of the complex, so that the toughness of the complex is increased while the high mechanical strength of the complex is maintained, and the complex is easy to process.

(4) The complex provided by the invention has the advantages of simple preparation method, easy synthesis of reaction raw materials and intermediates, no need of complex process steps and high cost, and suitability for large-scale production and use.

(5) The olefin polymerization method provided by the invention has the advantages of high polymerization activity, simple and convenient process and strong operability, can be suitable for various olefin monomers, especially cycloolefin monomers with large steric hindrance, and has very important industrial value and economic value.

Detailed Description

Terminology

The term "C1-Cn" as used herein includes C1-C2, C1-C3, and. For example, the "C1-C10" group refers to a moiety having 1-10 carbon atoms, i.e., 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. Thus, for example, "C1-C4 alkyl" refers to an alkyl group containing 1-4 carbon atoms, i.e., the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Numerical ranges, such as "1-6" herein refer to each integer in the given range.

The term "alkyl" as used herein, alone or in combination, refers to an optionally substituted straight chain or optionally substituted branched saturated aliphatic hydrocarbon. The "alkyl" group herein may preferably 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 groups include methyl, ethyl, n-propyl, isopropyl, 2-methyl-l-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-l-butyl, 2-methyl-3-butyl, 2-dimethyl-1-propyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-l-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-dimethyl-l-butyl, 3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl and hexyl, and longer alkyl groups such as heptyl and octyl and the like. Where a group as defined herein, such as "alkyl" appears in a numerical range, for example, "C1-C6 alkyl" refers to an alkyl group that may be composed of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, or 6 carbon atoms, where alkyl is also inclusive of the unspecified numerical range.

"Alkyl" as used herein in combination refers to an alkyl group attached to other groups, e.g., an alkyl group in an alkoxy group, as defined above when used alone.

The term "alkoxy", as used herein, alone or in combination, refers to an alkyl ether group, denoted "alkyl-O-". Non-limiting examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy and the like.

The term "cycloalkyl", as used herein, alone or in combination, refers to a non-aromatic saturated carbocyclic ring, which may include a single carbocyclic ring (having one ring), a double carbocyclic ring (having two rings), or a multiple carbocyclic ring (having more than two rings), which may be bridged or spiro between rings. Cycloalkyl groups may preferably 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 groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.

The term "aryl" as used herein, 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-forming carbon atoms, which may be a monocyclic aryl, bicyclic aryl or more. The bicyclic aryl or more can be a monocyclic aryl fused to other independent rings, such as alicyclic, aromatic rings. Non-limiting examples of monocyclic aryl groups include phenyl groups, non-limiting examples of bicyclic aryl groups include naphthyl groups, and non-limiting examples of polycyclic aryl groups include phenanthryl, anthracyl, fluorenyl, azulenyl groups.

The term "halogen" as used herein, alone or in combination, refers to fluorine, chlorine, bromine or iodine.

The term "alpha-olefin", as used herein, alone or in combination, refers to a mono-olefin having a double bond at the end of the molecular chain, the formula being represented by R-ch=ch ₂, R representing "C1-C10 alkyl". The olefin has, but is not limited to, 3 to 12 carbon atoms, for example, 3 to 12 carbon atoms, or 3 to 10 carbon atoms, or 3 to 8 carbon atoms. The double bonds in these groups may be in either cis or trans conformation and should be understood to include both isomers. The olefins as defined herein may be a single type of olefin or may be a mixture of olefins.

The term "R ₁～R_n" as used herein, alone or in combination, refers to the group R ₁、R₂、R₃、……R_n, i.e., to all R groups within the subscripts 1 to n.

The term "hydrocarbyl", as used herein, alone or in combination, includes alkanes, alkenes, arenes, and alkynes, either linear or branched, or cyclic.

The technical scheme of the invention is further described in detail below with reference to specific embodiments.

The reagents and materials used in the examples of the present invention are all commercially available products unless otherwise specified.

The percentages used in the examples of the present invention are mass percentages unless otherwise indicated.

The test method used in the examples of the present invention is as follows:

the polymer molecular weight (M _w) and molecular weight distribution (PDI, M _w/M_n) were determined by high temperature gel permeation chromatography (PL-GPC 220), with 1,2, 4-trichlorobenzene as mobile phase, polystyrene as standard, at 150 ℃, standard concentration of 0.1mg/mL, solvent flow rate of 1.0mL/min, standard usage parameter k=59.1, α=0.69, sample parameter k=14.1, α=0.70.

The melting point (T _m) and the glass transition temperature (T _g) of the polymer were determined using a differential scanning calorimeter (METLER, DSC-1). The measurement procedure is that a 5.0-7.0mg polymer sample is taken, the temperature is raised to 250 ℃ at the rate of 30 ℃ per minute and maintained for 5 minutes to eliminate the heat history, then the temperature is lowered to 0 ℃ at the rate of 10 ℃ per minute for 3 minutes, the temperature is raised to 250 ℃ again, the crystallization peak temperature is obtained by using a temperature lowering curve, and the melting point or the vitrification temperature of the polymer is obtained by calculating the curve of the second temperature raising process.

The insertion of cyclic olefin monomers and the [ ENEN ] configuration (ethylene and norbornene alternation) content of the ethylene and/or alpha-olefin and cycloolefin copolymers were determined by ¹³ C NMR (Bruker ADVANCE III M). The polymer was dissolved in deuterated 1, 2-o-dichlorobenzene at a concentration of about 100mg/mL at 130 ℃. The instrument test parameters are that the pulse angle is 30 degrees, the whole decoupling process is carried out, the pulse delay time is 3s, and the sample scanning times are more than 3000 times. And (3) attributing the obtained high-temperature ¹³ C NMR spectrum peak to obtain the sequence distribution and comonomer insertion rate of the copolymer.

The tensile test adopts an electronic universal material tester of Instron company in the United states to test the tensile mechanical property of the polymer, and obtains a stress-strain curve and related mechanical parameters of the polymer.

The light transmittance of the sample is measured by a UV-3600Plus ultraviolet-visible spectrophotometer, the wavelength range of the test is 250-800 nm, and the test samples are all 2mmt.

The terminal double bonds of the polymer were determined by iodometry.

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

Example 1 preparation of Cat.1 Complex

The Cat.1 synthesis route is as follows:

(1) Intermediate IV-1 was prepared by adding 50mmol 2-bromo-4-tert-butylphenol and 25 mmole 1, 2-dibromoethane, respectively, to the flask, then adding 150mL acetone, after the reactants had been dissolved, adding 75mmol potassium hydroxide, refluxing at 60℃for 5h, and Thin Layer Chromatography (TLC) showed substantial completion of the reaction. After removal of the acetone solvent by rotary evaporation, 100mL DCM and 100mL water were added to the residue, respectively, the organic phase was collected by extraction, the aqueous phase was extracted with DCM (50 ml×3), all the organic phases were mixed, dried over anhydrous Na ₂SO₄, filtered, the solvent was removed by rotary evaporation from the filtrate, and the residual solid was recrystallized in acetone to give a white solid, intermediate IV-1, yield 90%.

¹H NMR(500MHz,Chloroform-d)δ7.30(d,J＝1.5Hz,2H),7.25(dd,J＝7.5,1.6Hz,2H),6.91(d,J＝7.5Hz,2H),4.40(t,J＝8.2Hz,4H),1.33(s,18H).

(2) Intermediate V-1 was prepared by adding 20mmol of intermediate IV-1 and 100mL of ultra-dry THF, respectively, dropwise at-78℃to 40mmol of N-BuLi (1.6M in hexane) under N ₂, then adding 40mmol of B (OMe) ₃, slowly rising to 25℃and reacting for 12h. After completion of the reaction, 80mL of 2N HCl was added at 0℃and stirred for 1h at 25℃and 100mL of water was added, and the mixture solution after the reaction was allowed to stand for delamination, and then the organic phase was collected and the aqueous phase was extracted with EtOAc (50 mL. Times.3). All organic phases were mixed, dried over anhydrous MgSO ₄, filtered and the solvent was removed from the filtrate by rotary evaporation to give the product as a white solid. The white solid product was further purified by washing with n-hexane (100 mL. Times.3) to give a white solid powder, intermediate V-1, in 82% yield.

¹H NMR(500MHz,Chloroform-d)δ7.35(d,J＝1.7Hz,2H),7.28(dd,J＝7.5,1.5Hz,2H),7.06(d,J＝7.5Hz,2H),6.29(s,4H),4.34(t,J＝8.2Hz,4H),1.34(s,18H).

(3) Cat.1 ligand preparation 20mmol 1-bromo-9H-carbazole, 10mmol of intermediate V-1 and 100mmol of Na ₂CO₃ are added respectively in a 500mL Schlenk bottle, 90mL toluene, 30mL ethanol and 30mL water are then added respectively, after freezing and degassing for 3 times, 1mmol Pd (PPh ₃)₄) is added into the mixed solution under N ₂ atmosphere, the temperature is raised to 80 ℃ and stirring is carried out for 12H, after standing and layering the mixed solution after reaction, the organic phase is collected, the aqueous phase is extracted with dichloromethane (30 mL×3), all the organic phases are mixed and then dried with anhydrous MgSO ₄, then the organic phase filtrate is obtained after the filtrate is removed by spin evaporation, and the product is separated and purified by column chromatography (petroleum ether: ethyl acetate=20:1) to obtain a white solid product, namely the Cat.1 ligand, the yield is 75%.

¹H NMR(500MHz,Chloroform-d)δ8.13–8.08(m,4H),8.03(dd,J＝7.6,1.7Hz,2H),7.72(dd,J＝7.5,1.5Hz,2H),7.49–7.43(m,4H),7.41(dd,J＝7.4,1.6Hz,2H),7.35–7.25(m,4H),7.20(td,J＝7.4,1.6Hz,2H),6.95(d,J＝7.5Hz,2H),4.40(s,4H),1.36(s,18H).

(4) Cat.1 complex is prepared by adding 5mmol of Cat.1 ligand and 5mmol HfBn ₂Cl₂(Et₂O)₂ to 60mL of toluene in a 200mL Schlenk flask under N ₂ atmosphere, reacting for 12h at 80 ℃ in the dark, filtering, collecting filtrate, concentrating, and standing at-18 ℃ to precipitate to obtain white crystalline solid, namely Cat.1 complex with a yield of 66%.

¹H NMR(400MHz,C₆D₆):δ8.15–8.09(m,2H),8.01–7.96(m,2H),7.56–7.49(m,4H),7.44(ddd,J＝7.3,6.1,1.3Hz,2H),7.37–7.30(m,6H),7.21(dd,J＝6.5,2.2Hz,2H),6.94(d,J＝6.5Hz,2H),4.24(s,4H),1.32(s,18H).

Example 2 preparation of Cat.2 Complex

The Cat.2 synthesis route is as follows:

(1) Cat.2 ligand preparation 20mmol of 8-bromo-7H-benzoc carbazole, 10mmol of intermediate V-1 and 100mmol of Na ₂CO₃ are added respectively in a 500mL Schlenk bottle, 90mL of toluene, 30mL of ethanol and 30mL of water are then added respectively, the mixture is frozen and degassed 3 times, 1mmol of Pd (PPh ₃)₄) is added into the mixture under an atmosphere of N ₂, the temperature is raised to 80 ℃ and stirred for reaction for 12H, the mixture after the reaction is left to stand for delamination, the organic phase is collected, the aqueous phase is extracted with dichloromethane (30 mL×3), all the organic phases are mixed and dried with anhydrous MgSO ₄, then the organic phase filtrate is obtained after the solvent is removed by spin evaporation, and the product is purified by column chromatography (petroleum ether: ethyl acetate=15:1) to obtain a white solid product, namely the Cat.2 ligand, the yield is 69%.

¹H NMR(500MHz,Chloroform-d)δ8.58–8.51(m,4H),7.98(dd,J＝7.4,1.5Hz,2H),7.94–7.87(m,2H),7.72(dd,J＝7.5,1.5Hz,2H),7.52–7.43(m,8H),7.42(d,J＝7.5Hz,2H),7.36(dd,J＝7.6,1.5Hz,2H),7.28(dd,J＝7.5,1.5Hz,2H),6.95(d,J＝7.5Hz,2H),4.40(s,4H),1.36(s,18H).

(2) Cat.2 complex is prepared by adding 5mmol of Cat.2 ligand and 5mmol HfBn ₂Cl₂(Et₂O)₂ respectively into 60mL of toluene in a 200mL Schlenk bottle under N ₂ atmosphere, carrying out light-proof reaction for 12h at 80 ℃, filtering and collecting filtrate, concentrating, and standing at-18 ℃ to precipitate to obtain white crystalline solid, namely Cat.2 complex with the yield of 60%.

¹H NMR(400MHz,C₆D₆):δ7.94–7.87(m,4H),7.84(dt,J＝7.5,1.2Hz,4H),7.58–7.51(m,4H),7.46(ddd,J＝8.0,6.8,1.3Hz,2H),7.42–7.32(m,6H),7.25(dd,J＝6.5,2.3Hz,2H),6.84(d,J＝6.5Hz,2H),4.14(s,4H),1.38(s,18H).

Example 3 preparation of Cat.3 Complex

The Cat.3 synthesis route is as follows:

(1) Cat.3 ligand preparation 20mmol of 1-bromo-3,6-di-tert-butyl-9H-carbazole, 10mmol of intermediate V-1 and 100mmol of Na ₂CO₃ are added respectively in a 500mL Schlenk bottle, 90mL of toluene, 30mL of ethanol and 30mL of water are then added respectively, the mixture is frozen and degassed 3 times, 1mmol of Pd (PPh ₃)₄) is added into the mixed solution under an atmosphere of N ₂, the temperature is raised to 80 ℃ and stirred for 12H, the organic phase is collected after standing and layering the reacted mixed solution, the aqueous phase is extracted with dichloromethane (30 mL×3), all the organic phases are mixed and dried with anhydrous MgSO ₄, then the filtrate is filtered to obtain an organic phase filtrate, the solvent is removed by spin evaporation, and the product is separated and purified by column chromatography (petroleum ether: ethyl acetate=25:1), so that a white solid product is obtained, namely the Cat.2 ligand, the yield is 83%.

¹H NMR(500MHz,Chloroform-d)δ8.25(d,J＝1.5Hz,2H),8.16(d,J＝1.4Hz,2H),7.47(d,J＝1.5Hz,2H),7.44–7.35(m,6H),7.32–7.26(m,4H),7.01(d,J＝7.5Hz,2H),4.40(s,4H),1.41(s,18H),1.36(s,18H),1.32(s,18H).

(2) Cat.3 complex preparation, namely, under the atmosphere of N ₂, 5mmol of Cat.3 ligand and 5mmol HfBn ₂Cl₂(Et₂O)₂ are respectively added into 60mL of toluene in a 200mL Schlenk bottle, and are reacted for 12 hours at 80 ℃ in a dark place, filtered and collected, concentrated and placed at-18 ℃ to separate out, so that white crystalline solid is obtained, namely, the Cat.3 complex, and the yield is 76%.

¹H NMR(400MHz,C₆D₆):δ8.01–7.97(m,2H),7.85(d,J＝2.2Hz,2H),7.54(d,J＝2.1Hz,2H),7.38–7.30(m,6H),7.22(dd,J＝6.6,2.2Hz,2H),7.02(d,J＝6.6Hz,2H),4.08(s,4H),1.36–1.30(m,54H).

Example 4 preparation of Cat.4 Complex

The Cat.4 synthesis route is as follows:

(1) Intermediate VI-1 was prepared by adding 15mmol 1-bromo-3,6-diiodo-9H-carbazole, 30mmol (3, 5-di-tert-butylphenyl) of boronic acid and 200mmol Na ₂CO₃, respectively, to a 500mL Schlenk flask, then adding 90mL toluene, 30mL ethanol and 30mL water, freezing and degassing 3 times, adding 1mmol Pd (PPh ₃)₄) to the mixed solution under N ₂ atmosphere, raising the temperature to 80 ℃ and stirring for 13H, standing the reacted mixed solution for delamination, collecting the organic phase, extracting the aqueous phase with dichloromethane (30 mL. Times.3), mixing all the organic phases, drying with anhydrous MgSO ₄, filtering to obtain an organic phase filtrate, separating and purifying the filtrate by column chromatography (petroleum ether: ethyl acetate=40:1) to obtain a white solid product, namely intermediate VI-1, with a yield of 73%.

¹H NMR(500MHz,Chloroform-d)δ7.86(dd,J＝13.3,1.5Hz,2H),7.73(d,J＝1.4Hz,1H),7.54(dd,J＝7.5,1.5Hz,1H),7.45(d,J＝7.5Hz,1H),6.91(d,J＝1.4Hz,2H),6.89–6.84(m,5H),2.26(m,36H).

(2) Cat.4 ligand preparation 20mmol of intermediate VI-1, 10mmol of intermediate V-1 and 100mmol of Na ₂CO₃ were added respectively in 500mL Schlenk flask, then 90mL toluene, 30mL ethanol and 30mL water were added respectively, after freeze-degassing 3 times, 1mmol of Pd (PPh ₃)₄ was added to the mixed solution under N ₂ atmosphere, the temperature was raised to 80 ℃ to stir and react for 12h.

¹H NMR(500MHz,Chloroform-d)δ7.79(d,J＝1.5Hz,2H),7.72(d,J＝1.7Hz,2H),7.57–7.44(m,8H),7.34(d,J＝1.8Hz,2H),7.16(dt,J＝7.4,1.2Hz,2H),6.95(d,J＝7.5Hz,2H),6.91–6.82(m,12H),4.40(s,4H),2.46(s,18H),2.27(m,72H).

(3) Cat.4 complex is prepared by adding 5mmol of Cat.4 ligand and 5mmol HfBn ₂Cl₂(Et₂O)₂ respectively into 60mL of toluene in a 200mL Schlenk bottle under N ₂ atmosphere, carrying out light-proof reaction for 12h at 80 ℃, filtering and collecting filtrate, concentrating, and standing at-18 ℃ to precipitate to obtain white crystalline solid, namely Cat.4 complex with the yield of 56%.

¹H NMR(400MHz,C₆D₆):δ8.07(dd,J＝15.0,2.0Hz,4H),7.72–7.64(m,4H),7.60(d,J＝6.3Hz,2H),7.56(d,J＝2.1Hz,2H),7.43(dd,J＝12.9,2.2Hz,8H),7.35(dt,J＝4.6,2.2Hz,4H),7.22(dd,J＝6.5,2.2Hz,2H),6.97(d,J＝6.6Hz,2H),4.34(s,4H),1.40–1.28(m,90H).

Example 5 preparation of Cat.5 Complex

The Cat.5 synthesis route is as follows:

(1) Intermediate IV-2 was prepared by adding 50mmol 2-bromo-4-tert-butylphenol and 25mmol 1, 3-dibromopropane, respectively, to a 500mL round bottom flask, then adding 150mL acetone, adding 75mmol potassium hydroxide after the reactants had dissolved, refluxing at 60℃for 5h, and Thin Layer Chromatography (TLC) showed substantial completion of the reaction. After removal of the acetone solvent by rotary evaporation, 100mL of DCM and 100mL of water were added to the residue, respectively, the organic phase was collected by extraction, the aqueous phase was extracted with DCM (50 ml×3), all the organic phases were mixed, dried over anhydrous Na ₂SO₄, filtered, the solvent was removed by rotary evaporation from the filtrate, and the residual solid was recrystallized in acetone to give a white solid, intermediate IV-2, yield 93%.

¹H NMR(500MHz,Chloroform-d)δ7.31–7.24(m,4H),6.95(d,J＝7.5Hz,2H),4.18(t,J＝7.1Hz,4H),2.32(p,J＝7.1Hz,2H),1.33(s,18H).

(2) Intermediate V-2 was prepared by adding 20mmol of intermediate IV-2 and 100mL of ultra-dry THF, respectively, dropwise at-78℃to 40mmol of N-BuLi (1.6M in hexane) under N ₂, then adding 40mmol of B (OMe) ₃, slowly rising to 25℃and reacting for 12h. After completion of the reaction, 80mL of 2N HCl was added at 0℃and stirred for 1h at 25℃and 100mL of water was added, and the mixture solution after the reaction was allowed to stand for delamination, and then the organic phase was collected and the aqueous phase was extracted with EtOAc (50 mL. Times.3). All organic phases were mixed, dried over anhydrous MgSO ₄, filtered and the solvent was removed from the filtrate by rotary evaporation to give the product as a white solid. The white solid product was further purified by washing with n-hexane (100 mL. Times.3) to give a white solid powder, intermediate V-2, in 85% yield.

¹H NMR(500MHz,Chloroform-d)δ7.36(d,J＝1.4Hz,2H),7.28(dd,J＝7.5,1.5Hz,2H),7.06(d,J＝7.5Hz,2H),6.06(s,4H),4.11(t,J＝7.1Hz,4H),2.30(p,J＝7.1Hz,2H),1.34(s,18H).

(3) Cat.5 ligand preparation 20mmol 1-bromo-9H-carbazole, 10mmol of intermediate V-2 and 100mmol of Na ₂CO₃ are added respectively in a 500mL Schlenk bottle, 90mL toluene, 30mL ethanol and 30mL water are then added respectively, after freezing and degassing for 3 times, 1mmol Pd (PPh ₃)₄) is added into the mixed solution under N ₂ atmosphere, the temperature is raised to 80 ℃ and stirring is carried out for 12H, after standing and layering the mixed solution after reaction, the organic phase is collected, the aqueous phase is extracted with dichloromethane (30 mL×3), all the organic phases are mixed and then dried with anhydrous MgSO ₄, then the organic phase filtrate is obtained after the filtrate is removed by spin evaporation, and the product is separated and purified by column chromatography (petroleum ether: ethyl acetate=20:1) to obtain a white solid product, namely the Cat.4 ligand, the yield is 79%.

¹H NMR(500MHz,Chloroform-d)δ8.13–8.08(m,2H),8.03(dd,J＝7.6,1.7Hz,2H),7.73(dd,J＝7.4,1.5Hz,2H),7.49(d,J＝1.5Hz,2H),7.46(t,J＝7.5Hz,2H),7.41(dd,J＝7.4,1.6Hz,2H),7.35–7.27(m,6H),7.20(td,J＝7.4,1.6Hz,2H),6.95(d,J＝7.4Hz,2H),4.13(t,J＝7.1Hz,4H),2.29(p,J＝7.1Hz,2H),1.36(s,18H).

(4) Cat.5 complex is prepared by adding 5mmol of Cat.5 ligand and 5mmol HfBn ₂Cl₂(Et₂O)₂ respectively into 60mL of toluene in a 200mL Schlenk bottle under N ₂ atmosphere, carrying out light-proof reaction for 12h at 80 ℃, filtering and collecting filtrate, concentrating, and standing at-18 ℃ to precipitate to obtain white crystalline solid, namely Cat.5 complex, with the yield of 71%.

¹H NMR(400MHz,C₆D₆):δ8.11(dt,J＝7.5,1.0Hz,2H),8.00–7.94(m,2H),7.54–7.45(m,4H),7.40(ddd,J＝7.2,5.8,1.2Hz,2H),7.35–7.28(m,6H),7.19(dd,J＝6.5,2.2Hz,2H),6.93(d,J＝6.5Hz,2H),4.12(t,J＝8.4Hz,4H),2.36(p,J＝8.4Hz,2H),1.27(s,18H).

Example 6 preparation of Cat.6 Complex

The Cat.6 synthesis route is as follows:

(1) Cat.6 ligand preparation 20mmol of 8-bromo-7H-benzoc carbazole, 10mmol of intermediate V-2 and 100mmol of Na ₂CO₃ are added respectively in a 500mL Schlenk bottle, 90mL of toluene, 30mL of ethanol and 30mL of water are then added respectively, the mixture is frozen and degassed 3 times, 1mmol of Pd (PPh ₃)₄) is added into the mixture solution under an atmosphere of N ₂, the temperature is raised to 80 ℃ and stirred for reaction for 12H, the mixture solution after the reaction is left to stand for delamination, the organic phase is collected, the aqueous phase is extracted with dichloromethane (30 mL×3), all the organic phases are mixed and dried with anhydrous MgSO ₄, then the organic phase filtrate is obtained after the solvent is removed by spin evaporation, and the product is purified by column chromatography (petroleum ether: ethyl acetate=15:1) to obtain a white solid product, namely the Cat.6 ligand, the yield is 70%.

¹H NMR(500MHz,Chloroform-d)δ8.58–8.51(m,2H),7.98(dd,J＝7.4,1.5Hz,2H),7.94–7.87(m,4H),7.72(dd,J＝7.5,1.5Hz,2H),7.52–7.39(m,10H),7.36(dd,J＝7.5,1.4Hz,2H),7.30(dd,J＝7.5,1.6Hz,2H),6.94(d,J＝7.5Hz,2H),4.13(t,J＝7.1Hz,4H),2.29(p,J＝7.1Hz,2H),1.36(s,18H).

(2) Cat.6 complex is prepared by adding 5mmol of Cat.6 ligand and 5mmol HfBn ₂Cl₂(Et₂O)₂ respectively into 60mL of toluene in a 200mL Schlenk bottle under N ₂ atmosphere, carrying out light-proof reaction for 12h at 80 ℃, filtering and collecting filtrate, concentrating, and standing at-18 ℃ to precipitate to obtain white crystalline solid, namely Cat.6 complex with the yield of 68%.

¹H NMR(400MHz,C₆D₆):δ7.96–7.88(m,4H),7.81(dt,J＝7.4,1.1Hz,4H),7.63–7.57(m,4H),7.45(ddd,J＝8.2,7.2,1.5Hz,2H),7.44–7.31(m,6H),7.19(dd,J＝6.5,2.2Hz,2H),6.93(d,J＝6.5Hz,2H),4.15(t,J＝8.4Hz,4H),2.37(p,J＝8.4Hz,2H),1.29(s,18H).

EXAMPLE 7 preparation of Cat.7 Complex

The Cat.7 synthesis route is as follows:

(1) Cat.7 ligand preparation 20mmol of 1-bromo-3,6-di-tert-butyl-9H-carbazole, 10mmol of intermediate V-2 and 100mmol of Na ₂CO₃ are added respectively in a 500mL Schlenk bottle, 90mL of toluene, 30mL of ethanol and 30mL of water are then added respectively, the mixture is frozen and degassed 3 times, 1mmol of Pd (PPh ₃)₄) is added into the mixed solution under an atmosphere of N ₂, the temperature is raised to 80 ℃ and stirred for 12H, the mixed solution after the reaction is allowed to stand for delamination, an organic phase is collected, the aqueous phase is extracted with dichloromethane (30 mL×3), all the organic phases are mixed and dried with anhydrous MgSO ₄, then the filtrate is filtered to obtain an organic phase filtrate, the solvent is removed by spin evaporation, and the product is separated and purified by column chromatography (petroleum ether: ethyl acetate=25:1), so that a white solid product is obtained, namely the Cat.7 ligand, the yield is 81%.

¹H NMR(500MHz,Chloroform-d)δ8.25(d,J＝1.5Hz,2H),8.16(d,J＝1.4Hz,2H),7.49(d,J＝1.5Hz,2H),7.43–7.35(m,4H),7.34–7.27(m,6H),7.01(d,J＝7.5Hz,2H),4.13(t,J＝7.1Hz,4H),2.30(p,J＝7.1Hz,2H),1.41(s,18H),1.36(s,18H),1.32(s,18H).

(2) Cat.7 complex is prepared by adding 5mmol of Cat.7 ligand and 5mmol HfBn ₂Cl₂(Et₂O)₂ to 60mL of toluene in a 200mL Schlenk flask under N ₂ atmosphere, reacting for 12h at 80 ℃ in the dark, filtering and collecting filtrate, concentrating, and standing at-18 ℃ to precipitate to obtain white crystalline solid, namely Cat.7 complex with the yield of 73%.

¹H NMR(400MHz,C₆D₆):δ8.03–7.98(m,2H),7.83(d,J＝2.2Hz,2H),7.52(d,J＝2.1Hz,2H),7.39–7.29(m,6H),7.20(dd,J＝6.5,2.1Hz,2H),7.00(d,J＝6.6Hz,2H),4.16(t,J＝8.4Hz,4H),2.33(p,J＝8.4Hz,2H),1.38–1.28(m,54H).

Example 8 preparation of Cat.8 Complex

The Cat.8 synthetic route is as follows:

(1) Cat.8 ligand preparation 20mmol of intermediate VI-1, 10mmol of intermediate V-2 and 100mmol of Na ₂CO₃ were added respectively in Schlenk flask, then 90mL of toluene, 30mL of ethanol and 30mL of water were added respectively, after freeze-degassing 3 times, 1mmol of Pd (PPh ₃)₄) was added to the mixed solution under N ₂ atmosphere, the temperature was raised to 80 ℃ to stir and react for 12h.

¹H NMR(500MHz,Chloroform-d)δ7.79(d,J＝1.4Hz,2H),7.72(d,J＝1.7Hz,2H),7.55(d,J＝1.4Hz,2H),7.51(d,J＝7.5Hz,2H),7.46(dd,J＝7.5,1.5Hz,2H),7.34(d,J＝1.5Hz,2H),7.18–7.13(m,4H),6.95(d,J＝7.5Hz,2H),6.88(dd,J＝8.6,1.5Hz,8H),6.84(q,J＝1.8Hz,4H),4.13(t,J＝7.1Hz,4H),2.46(m,2H),2.35–2.25(m,90H).

(2) Cat.8 complex preparation, namely, under the atmosphere of N ₂, 5mmol of Cat.8 ligand and 5mmol HfBn ₂Cl₂(Et₂O)₂ are respectively added into 60mL of toluene in a 200mL Schlenk bottle, and are reacted for 12 hours at 80 ℃ in a dark place, filtered and collected, concentrated and placed at-18 ℃ to separate out, so that white crystalline solid is obtained, namely, the Cat.8 complex, and the yield is 51%.

¹H NMR(400MHz,C₆D₆):δ8.05(dd,J＝15.0,2.0Hz,4H),7.75–7.66(m,4H),7.61(d,J＝6.3Hz,2H),7.54(d,J＝2.1Hz,2H),7.41(dd,J＝12.9,2.2Hz,8H),7.32(dt,J＝4.6,2.2Hz,4H),7.19(dd,J＝6.6,2.2Hz,2H),6.96(d,J＝6.6Hz,2H),4.11(t,J＝8.4Hz,4H),2.35(p,J＝8.4Hz,2H),1.39–1.27(m,90H).

EXAMPLE 9 bis-carbazolyl diphenoxyether Complex catalyzed ethylene and norbornene copolymerization

A250 mL stainless steel reaction kettle with a magnetic stirrer is dried for more than 2 hours at 100 ℃, vacuumized to 2.5mbar when the reaction kettle is hot, then N ₂ is introduced and replaced by vacuum-N ₂ for 3 times, and then vacuum-ethylene gas is used for 3 times. 100mL of 3M norbornene/toluene solution and 1.7mL of MAO (1.5M toluene solution) are sequentially added into the reaction kettle under the condition of keeping micro positive pressure and stirring speed of 500rpm in the reaction kettle, then the reaction temperature is raised to 130 ℃, the pressure (polymerization pressure) in the kettle is kept to be 0.4MPa through ethylene gas, and after the reaction system is stable, 5.0mL (0.001M toluene solution) of biscarbazolyl diphenoxy ether complex solution is pressed into the reaction system through ethylene gas, so that polymerization reaction is started. After 2min of polymerization, stopping introducing ethylene gas, cooling the reaction kettle to 100 ℃, discharging unreacted ethylene by decompression, discharging the reaction liquid into 500mL of ethanol, washing the polymerization product with ethanol for 3 times, and drying in a vacuum oven at 50 ℃ to constant weight. The polymerization activity and copolymer characterization results are shown in tables 1,2 and 3.

Comparative example 1 rac-SiMe ₂(Ind)₂ZrCl₂ Complex catalyzed copolymerization of ethylene and norbornene

A250 mL stainless steel reaction kettle with a magnetic stirrer is dried for more than 2 hours at 100 ℃, vacuumized to 2.5mbar when the reaction kettle is hot, then N ₂ is introduced and replaced by vacuum-N ₂ for 3 times, and then vacuum-ethylene gas is used for 3 times. 100mL of 3M norbornene/toluene solution and 1.7mL of MAO (1.5M toluene solution) are sequentially added into the reaction kettle under the condition of keeping micro positive pressure and stirring speed of 500rpm in the reaction kettle, then the reaction temperature is raised to 130 ℃, the pressure (polymerization pressure) in the kettle is kept to be 0.4MPa through ethylene gas, and after the reaction system is stable, 5.0mL (0.001M toluene solution) of rac-SiMe ₂(Ind)₂ZrCl₂ complex solution is pressed into the reaction system through ethylene gas, so that polymerization reaction is started. After 2min of polymerization, stopping introducing ethylene gas, cooling the reaction kettle to 100 ℃, discharging unreacted ethylene by decompression, discharging the reaction liquid into 500mL of ethanol, washing the polymerization product with ethanol for 3 times, and drying in a vacuum oven at 50 ℃ to constant weight. The polymerization activity and copolymer characterization results are shown in tables 1,2 and 3.

Comparative example 2 Me ₂Si(C₅Me₄)(N-tBu)TiCl₂ Complex catalyzed copolymerization of ethylene and norbornene

A250 mL stainless steel reaction kettle with a magnetic stirrer is dried for more than 2 hours at 100 ℃, vacuumized to 2.5mbar when the reaction kettle is hot, then N ₂ is introduced and replaced by vacuum-N ₂ for 3 times, and then vacuum-ethylene gas is used for 3 times. 100mL of 3M norbornene/toluene solution and 1.7mL of MAO (1.5M toluene solution) are sequentially added into the reaction kettle under the condition of keeping micro positive pressure and stirring speed of 500rpm in the reaction kettle, then the reaction temperature is raised to 130 ℃, the pressure (polymerization pressure) in the kettle is kept to be 0.4MPa through ethylene gas, and after the reaction system is stable, 5.0mL (0.001M toluene solution) of Me ₂Si(C₅Me₄)(N-tBu)TiCl₂ complex solution is pressed into the reaction system through ethylene gas, so that polymerization reaction is started. After 2min of polymerization, stopping introducing ethylene gas, cooling the reaction kettle to 100 ℃, discharging unreacted ethylene by decompression, discharging the reaction liquid into 500mL of ethanol, washing the polymerization product with ethanol for 3 times, and drying in a vacuum oven at 50 ℃ to constant weight. The polymerization activity and copolymer characterization results are shown in tables 1,2 and 3.

TABLE 1 copolymerization Activity of ethylene and norbornene and Polymer index test results

TABLE 2 characterization of Polymer Structure and optical Properties results

TABLE 3 characterization of Polymer mechanical Properties results

The results in Table 1 show that the biscarbazolyl diphenoxy ether complex of the invention has excellent ethylene and norbornene copolymerization catalytic activity, high cycloolefin monomer insertion rate, larger molecular weight and distribution regulation and control interval.

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

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

In addition, the biscarbazolyl diphenoxy ether complex of the invention has excellent high temperature stability, and can still keep higher polymerization activity and cycloolefin monomer insertion rate at a high reaction temperature of 130 ℃.

Unless otherwise defined, all terms used herein are intended to have the meanings commonly understood by those skilled in the art.

The described embodiments of the present invention are intended to be illustrative only and not to limit the scope of the invention, and various other alternatives, modifications, and improvements may be made by those skilled in the art within the scope of the invention, and therefore the invention is not limited to the above embodiments but only by the claims.

Claims (10)

1. A biscarbazolyl bisphenoxy ether complex having a structure as shown in formula (I), wherein M is selected from titanium, zirconium or hafnium; R ₁ to R ₁₁ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C40 hydrocarbon group, a C3 to C40 cycloalkyl group, a C6 to C40 aryl group, a heteroatom-containing group or a silyl group containing 1 to 3 Si atoms; two or more of R ₁ to R ₁₁ 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 hydrocarbon group containing a heteroatom, or a silyl group containing 1 to 3 Si atoms. 2. The biscarbazolyl bisphenoxy ether complex according to claim 1, characterized in that, in the biscarbazolyl bisphenoxy ether complex, the R ₁ to R ₁₁ are each independently selected from hydrogen, C1 to C12 hydrocarbon groups, C3 to C16 cycloalkyl groups or C6 to C18 aryl groups, preferably, the R ₁ to R ₁₁ are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, substituted phenyl, or two or more of R ₁ to R ₁₁ can be bonded to each other to form a hydrocarbon ring; The X is selected from halogen, C1-C4 alkyl, benzyl or -N(C1-C4 alkyl) ₂ . Preferably, the X is selected from halogen, including F, Cl, Br and I. 3. The biscarbazolyl bisphenoxy ether complex according to claim 1 or 2, characterized in that the biscarbazolyl bisphenoxy ether complex is selected from any one of the following complexes Cat. 1 to Cat. 8: Cat.1 Cat.2 Cat.3 Cat.4 Cat.5 Cat.6 Cat.7 Cat.8 4. A method for preparing the biscarbazolyl bisphenoxy ether complex according to any one of claims 1 to 3, characterized in that it comprises the following steps: S1: Synthesize phenoxy ether compound IV from compounds II and III via Williamson reaction; S2: Compound IV is dissolved in a solvent, and then alkyl lithium is added at low temperature for lithiation, trimethyl borate is added for reaction, and then aqueous hydrochloric acid is added for hydrolysis to obtain compound V; S3: subjecting the compound V to a Suzuki coupling reaction with a bromide VI of carbazole or a derivative thereof under alkaline conditions using a palladium catalyst to obtain a ligand compound; S4: reacting the ligand compound with alkyl lithium to obtain a lithium salt of the ligand compound, and then reacting the ligand compound with MX ₄ or its ether complex; or directly reacting the ligand compound with MR ₂ X ₂ or its ether complex to obtain the biscarbazolyl bisphenoxy ether complex. 5. The method according to claim 4, characterized in that, in the formula II and IV, X ₁ is selected from halogen, preferably Br; in the step S2, the alkyl lithium is one or more of C1-C6 alkyl lithiums, preferably one or more of methyl lithium, n-butyl lithium, and n-hexyl lithium; in the formula (V), Z is a boronic acid group or a boric acid ester group, preferably -B(OH) ₂ or -B(OMe) ₂ ; in the step S4, the alkyl lithium is one or more of C1-C6 alkyl lithiums, preferably one or more of methyl lithium, n-butyl lithium, and n-hexyl lithium; MX ₄ is selected from one or more of TiCl ₄ , ZrCl ₄ , and 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 biscarbazolyl bisphenoxy ether complex according to any one of claims 1 to 3 as a main catalyst for olefin polymerization. 7. The use according to claim 6, characterized in that the olefin polymerization is copolymerization of ethylene and/or α-olefin and cycloolefin; Preferably, the α-olefin is a C3 to C12 α-olefin, preferably selected from one or more of 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene; the cycloolefin is a C6 to C21 cycloolefin, preferably selected from one or more of cyclohexene, norbornene, and tetracyclododecene. 8. An olefin polymerization method, comprising the following steps: in the presence of a main catalyst and a co-catalyst, ethylene and/or α-olefin and a cycloolefin are polymerized to form an olefin copolymer; wherein the main catalyst is the biscarbazolyl bisphenoxy ether complex according to any one of claims 1 to 3; Preferably, the α-olefin is a C3 to C12 α-olefin, preferably selected from one or more of 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene; the cycloolefin is a C6 to C21 cycloolefin, preferably selected from one or more of cyclohexene, norbornene, and tetracyclododecene. 9. The olefin polymerization method according to claim 8, characterized in that the molar ratio of the main catalyst to the co-catalyst is 1:1 to 5000, preferably 1:1 to 2000; and/or, The co-catalyst is selected from one or more of alkyl aluminum, alkyl aluminum chloride, aluminoxane, and boron-containing auxiliary agent; preferably, the alkyl aluminum is selected from one or more of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, and tri-n-hexyl aluminum; the alkyl aluminum chloride is selected from one or more of diethyl aluminum chloride, ethyl aluminum dichloride, and diethyl aluminum sesquichloride; the aluminoxane is selected from one or more of methyl aluminoxane, ethyl aluminoxane, and isobutyl aluminoxane; the boron-containing auxiliary agent is selected from one or two of tris(pentafluorophenyl) borane and triphenyl carbon tetrakis(pentafluorophenyl) borate; More preferably, the co-catalyst 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 method 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.