阅读说明：本技术 一种金属配合物及其制备方法与应用 (Metal complex and preparation method and application thereof ) 是由 刘万弼 王金强 郗朕捷 张彦雨 郭华 林小杰 刘帮明 陈冠良 于 2020-06-30 设计创作，主要内容包括：本发明提供了一种金属配合物及其制备方法与应用。一种金属配合物具有如下结构表达式；<Image he="354" wi="700" file="DDA0002562437100000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>本发明的技术优势为：提出一种基于芳氧基醚骨架的O,O,O-三齿配位催化剂,其金属活性中心与配位原子之间形成两个含柔性结构的多元环,通过脂肪醚键的旋转,表现为多个不同的空间异构体,有利于提高共单体插入率；催化剂具有较强的烯烃单体配位能力,其催化体系用于烯烃聚合反应尤其是烯烃/α-烯烃共聚时表现出优异的催化活性和热稳定性。(The invention provides a metal complex and a preparation method and application thereof. A metal complex has the following structural expression; the invention has the technical advantages that: provides an O, O, O-tridentate coordination catalyst based on an aryloxy ether skeleton, wherein two polycyclic rings containing flexible structures are formed between a metal active center and a coordination atom, and fat passes throughThe rotation of ether bond is expressed as several different space isomers, which is favorable to raising comonomer inserting rate, and the catalyst has relatively strong coordination capacity of olefin monomer, and its catalytic system is used in olefin polymerization, especially in olefin/α -olefin copolymerization, and has excellent catalytic activity and heat stability.)

1. A metal complex, wherein said metal complex has the structural formula:

wherein the content of the first and second substances,

R₁selected from hydrogen, halogen or optionally the following groups: c_1-6Alkyl radical, C_1-6Alkoxy radical, C_1-6Dihydrocarbylamino, C_3-10Cycloalkyl radical, C_3-10Cycloalkyl oxy, C_3-10Bicycloalkylamino, C_6-14Aryl radical, C_6-14Aryloxy radical, C_6-14An arylamino group;

R₂–R₆equal to or different from each other, each independently selected from hydrogen, halogen or optionally the following groups: c_1-6Alkyl radical, C_1-6Alkoxy radical, C_3-10Cycloalkyl radical, C_3-10Cycloalkyl oxy, C_6-14Aryl radical, C_6-14An aryloxy group;

F₁and F₂Identical to or different from each other, each independently selected from linear or branched aliphatic, alicyclic or derivatives thereof;

x is a monovalent ligand group having 1 to 20 atoms other than hydrogen, or a divalent ligand group having 1 to 40 atoms;

m is selected from a group IVB metal, preferably titanium, zirconium or hafnium.

2. The metal complex of claim 1, wherein R in formula I₁Selected from the following groups: dicyclohexylmethyl, benzhydryl, dibenzocycloheptyl, fluorenyl, carbazolyl, anthracenyl, bicyclohexanophenyl;

R₂–R₆each independently selected from hydrogen, halogen, C_1-6Alkyl radical, C_1-6An alkoxy group;

F₁and F₂Each independently selected from a linear or branched aliphatic group and an alicyclic group of C2-C10;

x is halogen, methyl, benzyl or dimethylamino;

m is selected from titanium, zirconium or hafnium.

3. A metal complex according to claim 1 or 2, wherein the metal complex has the following structural expression:

in the above formula, R₁Selected from the following groups: dicyclohexylmethyl, benzhydryl, dibenzocycloheptyl, fluorenyl, carbazolyl, anthracenyl, bicyclohexanophenyl;

R₂–R₆each independently selected from hydrogen, halogen, C_1-6Alkyl radical, C_1-6An alkoxy group;

x is halogen, methyl, benzyl or dimethylamino;

m is selected from titanium, zirconium or hafnium.

4. A method for preparing a metal complex, comprising the steps of:

in an ultra-dry organic solvent, reacting a compound shown as a formula II with a hydrogen extraction reagent to generate a salt, and then carrying out a complex reaction with a metal halide to obtain a complex shown as a formula I in claim 1; or the like, or, alternatively,

in an ultra-dry organic solvent, reacting a compound shown as a formula II with a hydrogen-withdrawing compound to generate a salt, then complexing with a metal halide, and adding a Grignard reagent to react to obtain a complex shown as a formula I in claim 1;

in the formula II, R₁–R₆、F₁–F₂Is as defined for formula I;

the hydrogen extraction reagent is one or more of butyl lithium, ethyl lithium, phenyl lithium, methyl lithium, sodium cyanide, sodium, potassium or a Grignard reagent;

the metal halide is one or more of a group IVB metal halide, preferably a chloride, bromide and iodide of a group IVB metal;

the Grignard reagent is one or more of methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide and ethyl magnesium chloride.

5. The method for producing a metal complex according to claim 4,

the molar ratio of the compound shown in the formula II to the hydrogen extracting reagent and the metal halide is 1: (2-2.3): (1-1.2); or the like, or, alternatively,

the mol ratio of the compound shown in the formula II to the hydrogen extracting reagent, the metal halide and the Grignard reagent is 1: (2-2.3): (1-1.2): (2-2.3).

6. The method for preparing a metal complex according to claim 4 or 5, wherein the compound represented by the formula II is prepared by the following steps:

1) reacting the compound shown in the formula III in an ultra-dry organic solvent in the presence of alkyl lithium and boric acid ester to obtain a compound shown in the formula IV; the compound shown in the formula III is preferably one or more of 1, 2-dibromobenzene, 3, 4-dibromotoluene, 1, 2-dibromo-4-tert-butyl benzene and 1, 2-dibromo-4-methoxybenzene;

preferably, the alkyl lithium is one or more of butyl lithium, ethyl lithium, phenyl lithium, methyl lithium;

preferably, the borate is one or more of triisopropyl borate, triethyl borate and trimethyl borate;

2) reacting a compound shown as a formula IV with dibromo-ether in an ultra-dry organic solvent in the presence of a palladium catalyst and an alkali metal salt to generate a compound shown as a formula V; the dibrominated ether is preferably one or more of 2, 2-dibromodiethyl ether, 1-dimethyl-2, 2-dibromoethyl ether and 1- (2-bromoethoxy) -1-bromomethylcyclohexane;

preferably, the palladium catalyst is one or more of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, bis (tri-tert-butylphosphine) palladium, triphenylphosphine palladium acetate, bis (tricyclohexylphosphorus) palladium (0), benzyl (chloro) bis (triphenylphosphine) palladium (II);

preferably, the alkali metal salt is one or more of potassium carbonate, sodium carbonate, cesium carbonate;

3) dissolving a compound shown as a formula VI in an ultra-dry organic solvent, then dropwise adding a hydroxyl protecting reagent, and reacting to obtain a compound shown as a formula VII; the compound shown in the formula VI is preferably one or more of 2-bromophenol, 2-bromo-4-methylphenol and 2-bromo-5-tert-butylphenol;

preferably, the hydroxyl protecting reagent is one or more of 3, 4-dihydro-2H-pyran, benzyl chloride, benzyl bromide and tert-butyldimethylchlorosilane;

4) dissolving a compound shown as a formula VII and alcohol in an ultra-dry organic solvent, adding a tin catalyst, and reacting to obtain a compound shown as a formula VIII; the alcohol is preferably one or more of benzhydryl alcohol, benzyl alcohol and phenethyl alcohol;

preferably, the tin catalyst is one or two of tin tetrabromide and tin tetrachloride;

5) dissolving the compounds shown in the formula VIII and the formula V in an organic solvent, and performing addition reaction under the action of a palladium catalyst and an alkali metal salt to generate a compound shown in the formula IX;

preferably, the palladium catalyst is one or more of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, bis (tri-tert-butylphosphine) palladium, triphenylphosphine palladium acetate, bis (tricyclohexylphosphorus) palladium (0), benzyl (chloro) bis (triphenylphosphine) palladium (II);

preferably, the alkali metal salt is one or more of potassium carbonate, sodium carbonate, cesium carbonate;

6) removing a protecting group of the compound shown in the formula IX to obtain a compound shown in the formula II;

7. the method for producing a metal complex according to claim 6,

in the step 1), the molar ratio of the compound shown in the formula III, the alkyl lithium and the boric acid ester is 1 (2-2.3) to (2-2.4);

in the step 2), the mol ratio of the compound shown in the formula IV, the dibromo-ether, the palladium catalyst and the alkali metal salt is 1 (0.4-0.6) to (0.1-1) to (0.5-2);

in the step 3), the molar ratio of the compound in the formula VI to the hydroxyl protecting reagent is 1 (1-1.3);

in the step 4), the mol ratio of the compound shown in the formula VII, the alcohol and the tin catalyst is 1 (1-1.2) to 0.1-0.5;

in the step 5), the molar ratio of the compound of the formula V, the compound of the formula VIII, the palladium catalyst and the alkali metal is 1 (1.8-2.1) to (0.1-1) to (0.5-2);

in the step 6), a specific method for removing a protecting group is as follows: dissolving the compound shown in the formula IX in a mixed solution of ethyl acetate and methanol, and reacting at room temperature under the action of concentrated hydrochloric acid to remove a protecting group.

8. A metal complex according to claims 1 to 3 or a metal complex prepared by a process according to claims 4 to 7, characterized by its use in olefin polymerisation, especially olefin/α -olefin copolymerisation.

9. The use of the metal complex of claims 1-3 or the metal complex prepared by the method of claims 4-7 in olefin polymerization, wherein the metal complex is used as a main catalyst and is used together with a cocatalyst to catalyze olefin polymerization; the cocatalyst is a composition of one or more of aluminoxane, alkyl aluminum and alkyl aluminum chloride compounds and borate in any proportion;

the polymerization temperature of the olefin is 20-250 ℃, preferably 150-200 ℃, and the polymerization pressure is 0.1-10 Mpa, preferably 1-5 Mpa;

preferably, the cocatalyst is one or two of methylaluminoxane or modified methylaluminoxane and the methyldi- (octadecyl) ammonium tetrakis (pentafluorophenyl) borate in any ratio.

10. The method of claim 9, wherein the molar ratio Al/M of the aluminum metal in the cocatalyst to the metal M in the catalyst center is 5 to 200, preferably 10 to 100.

Technical Field

The invention relates to a metal complex, in particular to a metal complex, a preparation method thereof and application of a catalyst system consisting of the metal complex in the field of olefin polymerization.

Background

The polyolefin elastomer is a copolymer of olefin and alpha-olefin catalyzed by metallocene, has plasticity and high elasticity, and can be widely applied to the fields of films, fibers, pipes, cables, mechanical tools, sealing elements, hot melt adhesives and the like. Metallocene catalysts with constrained geometry (formula 1,2, 3) are described in various publications (US5064802, EP0416815a2, US5026798, US5057475) by Dow chemical (Dow) and Exxon incorporated (Exxon), respectively, for olefin/α -olefin random copolymerization with high comonomer insertion but poor catalyst temperature resistance and low molecular weight for catalyzing olefin/α -olefin random copolymers.

Dow also reported a study of the copolymerization of ethylene/α -olefins catalyzed by group IVB metal catalysts based on imine-amine ligands (Organometallics 2011, 30, 251-262), wherein the isomerization of the complex of formula 4 occurs at higher temperatures and the insertion of the comonomer is lower. To overcome thermal instability, Dow also reported studies of imine-enamine ligand based complexes of hafnium and zirconium to catalyze ethylene/α -olefins (Organometallics 2013, 32, 2963-.

In view of the above problems in the prior art, there is a need to develop a novel high temperature resistant olefin copolymerization catalyst, which simultaneously satisfies good comonomer insertion rate.

Disclosure of Invention

The metal complex has high catalytic activity when applied to olefin polymerization, particularly olefin/alpha-olefin copolymerization, has high comonomer insertion rate and is stable under a high-temperature condition, is suitable for a high-temperature polymerization system at 150-200 ℃, can obviously improve the reaction rate, and is beneficial to obtaining a polymer product with high molecular weight.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a metal complex having the structural formula:

wherein the content of the first and second substances,

R₁selected from hydrogen, halogen or optionally the following groups: c_1-6Alkyl radical, C_1-6Alkoxy radical, C_1-6Dihydrocarbylamino, C_3-10Cycloalkyl radical, C_3-10Cycloalkyl oxy, C_3-10Bicycloalkylamino, C_6-14Aryl radical, C_6-14Aryloxy radical, C_6-14An arylamino group;

R₂–R₆equal to or different from each other, each independently selected from hydrogen, halogen or optionally the following groups: c_1-6Alkyl radical, C_1-6Alkoxy radical, C_3-10Cycloalkyl radical, C_3-10Cycloalkyl oxy, C_6-14Aryl radical, C_6-14An aryloxy group;

F₁and F₂Identical to or different from each other, each independently selected from linear or branched aliphatic, alicyclic or derivatives thereof;

x is a monovalent ligand group having 1 to 20 atoms other than hydrogen, or a divalent ligand group having 1 to 40 atoms;

m is selected from a group IVB metal, preferably titanium, zirconium or hafnium.

In a preferred embodiment, in said formula I, R₁Selected from the following groups: dicyclohexylmethyl, benzhydryl, dibenzocycloheptyl, fluorenyl, carbazolyl, anthracenyl, bicyclohexanophenyl;

at the same time, R₂–R₆Each independently selected from hydrogen, halogen, C_1-6Alkyl radical, C_1-6An alkoxy group;

at the same time, F₁And F₂Each independently selected from a linear or branched aliphatic group and an alicyclic group of C2-C10;

meanwhile, X is halogen, methyl, benzyl or dimethylamino;

and M is selected from titanium, zirconium or hafnium.

In a further preferred embodiment, the metal complex has the following structural expression:

in the above formula, R₁Selected from the following groups: dicyclohexylmethyl, benzhydryl, dibenzocycloheptyl, fluorenyl, carbazolyl, anthracenyl, bicyclohexanophenyl;

R₂–R₆each independently selected from hydrogen, halogen, C_1-6Alkyl radical, C_1-6An alkoxy group;

x is halogen, methyl, benzyl or dimethylamino;

m is selected from titanium, zirconium or hafnium.

A preparation method of the metal complex comprises the following steps:

in an ultra-dry organic solvent, reacting a compound shown as a formula II with a hydrogen extraction reagent to generate a salt, and then carrying out a complex reaction with a metal halide to obtain a complex shown as a formula I in claim 1;

or the like, or, alternatively,

in an ultra-dry organic solvent, reacting a compound shown as a formula II with a hydrogen-withdrawing compound to generate a salt, then complexing with a metal halide, and adding a Grignard reagent to react to obtain a complex shown as a formula I in claim 1;

wherein the temperature of the salt forming reaction is-90 ℃ to 35 ℃, such as-90 ℃, 80 ℃, 35 ℃ and 25 ℃, and the reaction time is 0.5 to 6 hours, such as 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours and 6 hours; the temperature of the complex reaction is 100-180 ℃, such as 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, and the reaction time is 1-8h, if the Grignard reagent is added, the reaction is continued for 1-3h, such as 1h, 2h, and 3h, and the metal complex is obtained.

In the formula II, R₁–R₆、F₁–F₂Is as defined for formula I;

in the above embodiments, the organic solvent is one or more of benzene, toluene, xylene, chlorobenzene, diethyl ether, tetrahydrofuran, n-hexane, and heptane; the hydrogen extraction reagent is one or more of butyl lithium, ethyl lithium, phenyl lithium, methyl lithium, sodium cyanide, sodium, potassium or a Grignard reagent; the metal halide is one or more of a group IVB metal halide, preferably a chloride, bromide and iodide of a group IVB metal; the Grignard reagent is one or more of methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide and ethyl magnesium chloride.

Further, the molar ratio of the compound shown in the formula II to the hydrogen extracting reagent and the metal halide is 1: (2-2.3): (1-1.2), e.g., 1:2:1, 1:2.2:1, 1:2.3:1.2, 1:2:1.1, etc.;

or the like, or, alternatively,

the mol ratio of the compound shown in the formula II to the hydrogen extracting reagent, the metal halide and the Grignard reagent is 1: (2-2.3): (1-1.2): (2-2.3), for example 1:2: 1:2.1: 2.2:1:2.2, 1:2.3:1.2:2.3, 1:2:1.1:2.1, etc.;

further, the compound shown in the formula II is prepared by the following steps:

1) reacting the compound shown in the formula III in an ultra-dry organic solvent in the presence of alkyl lithium and boric acid ester to obtain a compound shown in the formula IV; the compound shown in the formula III is preferably one or more of 1, 2-dibromobenzene, 3, 4-dibromotoluene, 1, 2-dibromo-4-tert-butyl benzene and 1, 2-dibromo-4-methoxybenzene;

preferably, the alkyl lithium is one or more of butyl lithium, ethyl lithium, phenyl lithium, methyl lithium;

preferably, the borate is one or more of triisopropyl borate, triethyl borate and trimethyl borate;

preferably, the molar ratio of the compound of formula III, alkyl lithium, borate is 1 (2-2.3) to (2-2.4), e.g., 1:2:2.4, 1:2.3:2.2, 1:2.1:2.2, 1:2:2, etc.;

preferred reaction conditions are: the reaction temperature is-80 ℃ to 0 ℃, such as-80 ℃, 60 ℃, 40 ℃, 20 ℃, 10 ℃ and 0 ℃, and the reaction time is 0.5 to 5 hours, such as 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours and 5 hours.

2) Reacting a compound shown as a formula IV with dibromo-ether in an ultra-dry organic solvent in the presence of a palladium catalyst and an alkali metal salt to generate a compound shown as a formula V; the dibrominated ether is preferably one or more of 2, 2-dibromodiethyl ether, 1-dimethyl-2, 2-dibromoethyl ether and 1- (2-bromoethoxy) -1-bromomethylcyclohexane;

preferably, the palladium catalyst is one or more of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, bis (tri-tert-butylphosphine) palladium, triphenylphosphine palladium acetate, bis (tricyclohexylphosphorus) palladium (0), benzyl (chloro) bis (triphenylphosphine) palladium (II);

preferably, the alkali metal salt is one or more of potassium carbonate, sodium carbonate, cesium carbonate;

preferably, the molar ratio of the compound of formula IV, dibromo-ether, palladium catalyst, alkali metal salt is 1 (0.4-0.6) to (0.1-1) to (0.5-2), such as 1:0.5:0.1:0.4, 1:0.6:1:2, 1:0.5:0.5:1, 1:0.4:0.6:1.5, etc.;

preferred reaction conditions are: the reaction temperature is 50-120 deg.C, such as 50 deg.C, 60 deg.C, 80 deg.C, 100 deg.C, 120 deg.C, and the reaction time is 1-10h, such as 1h, 3h, 5h, 7h, 9h, 10 h.

3) Dissolving a compound shown as a formula VI in an ultra-dry organic solvent, then dropwise adding a hydroxyl protecting reagent, and reacting to obtain a compound shown as a formula VII; the compound shown in the formula VI is preferably one or more of 2-bromophenol, 2-bromo-4-methylphenol and 2-bromo-5-tert-butylphenol;

preferably, the hydroxyl protecting reagent is one or more of 3, 4-dihydro-2H-pyran, benzyl chloride, benzyl bromide and tert-butyldimethylchlorosilane;

preferably, the molar ratio of the compound of formula VI to the hydroxy protecting agent is 1 (1-1.3), e.g., 1:1, 1:1.3, 1:1.2, 1:1.1, etc.

Preferred reaction conditions are: the reaction temperature is 15-100 deg.C, such as 15 deg.C, 25 deg.C, 40 deg.C, 60 deg.C, 80 deg.C, 100 deg.C, and the reaction time is 1-6h, such as 1h, 2h, 3h, 4h, 5h, 6 h;

4) dissolving a compound shown as a formula VII and alcohol in an ultra-dry organic solvent, adding a tin catalyst, and reacting to obtain a compound shown as a formula VIII; the alcohol is preferably one or more of benzhydryl alcohol, benzyl alcohol and phenethyl alcohol;

preferably, the tin catalyst is one or two of tin tetrabromide and tin tetrachloride;

preferably, the molar ratio of the compound of formula VII, alcohol, tin catalyst is 1 (1-1.2) to (0.1-0.5), such as 1:1:0.5, 1:1.2:0.3, 1:1.1:0.1, 1:1:0.2, etc.;

preferred reaction conditions are: the reaction temperature is 50-130 deg.C, such as 50 deg.C, 60 deg.C, 80 deg.C, 100 deg.C, 120 deg.C, 130 deg.C, and the reaction time is 1-5h, such as 1h, 2h, 3h, 4h, 5 h.

5) Dissolving the compounds shown in the formula VIII and the formula V in an organic solvent, and performing addition reaction under the action of a palladium catalyst and an alkali metal salt to generate a compound shown in the formula IX;

preferably, the palladium catalyst is one or more of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, bis (tri-tert-butylphosphine) palladium, triphenylphosphine palladium acetate, bis (tricyclohexylphosphorus) palladium (0), benzyl (chloro) bis (triphenylphosphine) palladium (II);

preferably, the alkali metal salt is one or more of potassium carbonate, sodium carbonate, cesium carbonate;

preferably, the molar ratio of the compound of formula V, the compound of formula VIII, the palladium catalyst, the alkali metal is 1 (1.8-2.1): 0.1-1: 0.5-2, for example 1: 2:0.1: 0.5, 1:2.1:1:2, 1:1.8:0.5:0.5, 1:1.9: 0.4: 1.1: 2:0.8:1.5, etc.;

preferred reaction conditions are: the reaction temperature is 50-120 deg.C, such as 50 deg.C, 60 deg.C, 80 deg.C, 100 deg.C, 120 deg.C, and the reaction time is 1-10h, such as 1h, 3h, 5h, 8h, 10 h.

6) Dissolving the compound shown in the formula IX in a mixed solution of ethyl acetate and methanol, reacting at room temperature under the action of concentrated hydrochloric acid, and removing a protecting group to obtain a compound shown in the formula II;

preferred reaction conditions are: dissolving the compound shown in the formula IX in a mixed solution of ethyl acetate and methanol with a volume ratio of 1 (0.5-1.5), reacting at room temperature for 0.5-5h under the action of 12mol/L concentrated hydrochloric acid, concentrating the reaction solution by rotary evaporation, extracting, and then carrying out rotary evaporation to obtain the compound shown in the formula II. The addition amount of the concentrated hydrochloric acid is 2-4 times of that of the compound shown in the formula IX by mol.

The above reaction process can be shown by the following reaction expression:

the invention also provides an application of the metal complex in olefin polymerization, especially olefin/alpha-olefin copolymerization.

The application method of the metal complex in olefin polymerization reaction is characterized in that the metal complex is used as a main catalyst and is used together with a cocatalyst for catalyzing the olefin polymerization reaction; the cocatalyst is a composition of one or more of aluminoxane, alkyl aluminum and alkyl aluminum chloride compounds and borate in any proportion;

the aluminoxane compound is selected from methylaluminoxane, ethylaluminoxane and the like, preferably ethylaluminoxane;

the alkyl aluminum compound is selected from trimethyl aluminum, triethyl aluminum, tributyl aluminum and the like, and trimethyl aluminum and triethyl aluminum are preferred;

the alkylaluminum chloride compound is selected from dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, dibutylaluminum chloride, etc., and dimethylaluminum chloride and diethylaluminum chloride are preferable.

The olefin polymerization temperature is 20 to 250 ℃, for example 20 ℃, 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃, 180 ℃, 200 ℃, 220 ℃, 250 ℃, preferably 150 to 250 ℃, more preferably 180 to 200 ℃, and the polymerization pressure is 0.1 to 10Mpa, for example 0.1Mpa, 0.5Mpa, 2Mpa, 3Mpa, 5Mpa, 7Mpa, 8Mpa, 10Mpa, preferably 1 to 5 Mpa;

preferably, the cocatalyst is one or two of methylaluminoxane or modified methylaluminoxane and the methyldi- (octadecyl) ammonium tetrakis (pentafluorophenyl) borate in any ratio.

Further, the molar ratio Al/M of the metal aluminum in the cocatalyst to the catalyst central metal M is 5 to 200, for example, 5, 10, 20, 50, 80, 100, 120, 150, 170, 200, preferably 10 to 100.

Compared with the prior art, the invention has the following technical advantages:

1) an O, O, O-tridentate coordination catalyst based on an aryloxyether framework is provided, two polycyclic rings containing flexible structures are formed between a metal active center and coordination atoms, and the polycyclic rings are expressed as a plurality of different space isomers through the rotation of a fatty ether bond, so that the insertion rate of a comonomer is improved;

2) the catalyst has stronger coordination capacity of olefin monomers, and the catalytic system of the catalyst shows excellent catalytic activity and thermal stability when being used for olefin polymerization reaction, particularly olefin/alpha-olefin copolymerization.

Detailed Description

The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.

The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.

The concentrations in the following examples are molar concentrations unless otherwise specified.

The materials, reagents, etc. used in the following examples are commercially available from the following sources:

1, 2-dibromobenzene: AR, Innochem

N-butyl lithium: AR, Innochem

Ultra-dry tetrahydrofuran: AR, Innochem

Triisopropyl borate: AR, Innochem

2, 2-dibromodiethyl ether: AR, Innochem

1, 1-dimethyl-2, 2-dibromoethyl ether: AR, Innochem

Ethylene glycol dimethyl ether: AR, Innochem

Palladium tetratriphenylphosphine: AR, Innochem

Anhydrous sodium carbonate: AR, Innochem

2-bromophenol: AR, Innochem

3, 4-dihydro-2H-pyran: AR, Innochem

Pyridinium p-toluenesulfonate: AR, Aladdin

Dichloromethane: AR, Innochem

Benzhydrol: AR, Innochem

Tin tetrabromide: AR, Aldrich

Anhydrous methanol: AR, Innochem

Ethyl acetate: AR, Innochem

Concentrated hydrochloric acid: AR, Innochem

Ultra-dry toluene: AR, Innochem

Ultra-dry n-hexane: AR, Innochem

Petroleum ether: 60-90 ℃ from Beijing chemical reagent company

Silica gel: chemical reagents of 200-300 mesh, Shanghai Wusi, AR

Deuterated chloroform: AR, Acros

Industrial alcohol: 95% of Beijing chemical reagent Co

TiCl₄(THF)₂: tokyo chemical industry Co Ltd

ZrCl₄(THF)₂: tokyo chemical industry Co Ltd

HfCl₄(THF)₂: tokyo chemical industry Co Ltd

Tetrakis (pentafluorophenyl) borate-methyldi- (octadecyl) ammonium salt: AR, Aladdin

Dimethylsilyldiindenyl zirconium dichloride: strem Corp

MAO (alkylaluminoxane), MMAO (modified alkylaluminoxane): 10% by weight toluene solution, Albemarle

Ethylene: 99.9% Beijing Yanshan chemical Co., Ltd

1-octene: 98% of Beijing YinuoKai science and technology

High-purity nitrogen gas: beijing Shunqanqite gas Co Ltd

Liquid nitrogen: beijing Shunqanqite gas Co Ltd

Isopar E: exxon Mobil Co Ltd

Other raw materials and reagents were obtained from commercial sources unless otherwise specified.

The molecular weight and molecular weight distribution of the polymers obtained in the following examples of ethylene polymerization were measured by PL-GPC220 at 150 ℃ using three PLgel 10 μm MIXED-B separation columns in series, 1,2, 4-trichlorobenzene as a solvent. The melting points of the polymers were measured by a conventional DSC (Q2000) method, and the polymerization activities of the polymers were calculated according to the following formulas: polymerization activity is the polymer mass/(metal content in catalyst polymerization time). Reference is made to the method for calculating the insertion rate of 1-octene (Macromolecules 1999, 32, 3817). The compounds in the following examples were characterized by means of nuclear magnetic resonance apparatus (Brucker ARX-400). The polymer high-temperature nuclear magnetism is obtained by using deuterated 1,1,2, 2-tetrachloroethane as a solvent and adopting Bruker DMX300MHz test at the temperature of 120 ℃.

The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.

Description of the drawings: in the examples eq represents a molar equivalent, for example, 1eq represents 1 molar equivalent.

The synthesis of the complex in the following examples was carried out according to the following reaction equation:

synthetic route of complex A

Synthetic route of complex B

[ example 1 ] Synthesis of Complex 7A, where M is Ti, preparation according to "synthetic route for Complex A

(1) Preparation of compound 1:

under nitrogen atmosphere, 21.23g of 1, 2-dibromobenzene (0.09mol, 1eq) is dissolved in 150mL of ultra-dry tetrahydrofuran, the temperature of the system is reduced to-78 ℃, 99.0mL of 2mol/L n-butyllithium (0.198mol, 2.2eq) hexane solution is slowly dropped for reaction for 30min at-78 ℃, 35.55g of triisopropyl borate (0.189mol, 2.1eq) is slowly dropped, 10.0mL of water is added for quenching after the room temperature is slowly recovered, the reaction solution is concentrated by rotary evaporation, the ethyl acetate is extracted and then is rotary evaporated, the n-hexane is recrystallized and washed, 12.4g of white solid is obtained, and the yield is 83.1%.

The nuclear magnetic structure confirmation data of compound 1 is shown below:

¹H NMR(CDCl₃,400MHz,TMS):7.44(s,2H),7.31～7.28(s,2H),4.07(s,4H).

¹³C NMR(CDCl₃,100MHz,TMS):137.5,132.6,128.1。

(2) preparation of compound 2:

11.6g of Compound 1(0.07mol, 1eq) was dissolved in 200mL of ethylene glycol dimethyl ether, 47mL of a 3mol/L aqueous solution of sodium carbonate (0.14mol, 2eq) was added, the mixture was frozen in liquid nitrogen, evacuated to remove oxygen, 16.16g of tetrakistriphenylphosphine palladium (0.014mol, 0.2eq) was added under nitrogen protection, and 8.12g of 2, 2-dibromodiethyl ether (0.035mol, 0.5eq) was slowly added dropwise while heating and refluxing were started, followed by reaction for 8 hours. The reaction solution was concentrated by rotary evaporation, extracted with ethyl acetate, and the filtrate was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate: 200: 1(v/v)) to obtain 9.7g of a white solid with a yield of 88.5%.

The nuclear magnetic structure confirmation data for compound 2 is shown below:

¹H NMR(CDCl₃,400MHz,TMS):7.37(s,2H),7.29～7.25(s,6H),4.07(s,4H),3.81(t,J＝8.0Hz,4H),1.91～1.85(m,4H).

¹³C NMR(CDCl₃,100MHz,TMS):148.3,143.1,132.5,131.5,126.3,122.4,66.3,26.1。

(3) preparation of compound 3:

under a nitrogen atmosphere, 17.30g of 2-bromophenol (0.1mol, 1eq) was diluted in 150mL of super-dry dichloromethane, and then 10.94g of 3, 4-dihydro-2H-pyran (0.13mol, 1.3eq) and 2.51g of pyridinium p-toluenesulfonate (0.01mol, 0.1eq) were added and reacted at room temperature for 6 hours. After extraction with dichloromethane, the filtrate was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate: 200: 1(v/v)) to give 21.44g of a colorless oil in 83.4% yield.

The nuclear magnetic structure confirmation data for compound 3 is shown below:

¹H NMR(CDCl₃,400MHz,TMS):7.41(d,J＝8.0Hz,1H),7.12(t,J＝8.0Hz,1H),6.80(t,J＝8.0Hz,1H),6.71(d,J＝8.0Hz,1H),5.62(t,J＝8.0Hz,1H),3.64–3.51(m,2H),1.95–1.82(m,2H),1.69–1.65(m,2H),1.61–1.55(m,2H).

¹³C NMR(CDCl₃,100MHz,TMS):160.3,130.2,126.8,120.4,111.2,111.4,101.6,63.1,28.4,24.3,18.8。

(4) preparation of compound 4:

under a nitrogen atmosphere, 20.57g of Compound 3(0.08mol, 1eq) and 14.74g of benzhydrol (0.08mol, 1.0eq) were dissolved in 150mL of ultra-dry methylene chloride, 7.01g of tin tetrabromide (0.016mol, 0.2eq) was added slowly, and the mixture was stirred at 60 ℃ for 5 hours. The reaction was quenched by the addition of 10mL of saturated aqueous sodium bicarbonate solution, extracted with dichloromethane, and the filtrate was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate: 200: 1(v/v)) to obtain 29.02g of a white solid with a yield of 85.7%.

The nuclear magnetic structure confirmation data for compound 4 is shown below:

¹H NMR(CDCl₃,400MHz,TMS):7.46(d,J＝8.0Hz,1H),7.29(t,J＝8.0Hz,4H),7.21(t,J＝8.0Hz,2H),7.13(d,J＝8.0Hz,4H),7.10(d,J＝8.0Hz,1H),6.90(t,J＝8.0Hz,1H),5.66(t,J＝8.0Hz,1H),5.55(s,1H),3.66–3.57(m,2H),1.93–1.86(m,2H),1.68–1.64(m,2H),1.58–1.54(m,2H).

¹³C NMR(CDCl₃,100MHz,TMS):149.8,141.0,131.2,129.7,127.1,127.8,126.2,120.7,111.4,110.6,101.2,62.8,48.7,28.7,24.1,19.3.

(5) preparation of compound 5:

9.42g of compound 2(0.03mol, 1eq) and 26.67g of compound 4(0.063mol, 2.1eq) are respectively dissolved in 200mL of ethylene glycol dimethyl ether, 20mL of 3mol/L sodium carbonate aqueous solution (0.06mol, 2eq) is added, liquid nitrogen is frozen, vacuum is conducted to remove oxygen, 13.86g of tetrakistriphenylphosphine palladium (0.012mol, 0.4eq) is added under the protection of nitrogen, and heating reflux reaction is carried out for 8 hours. The reaction solution was concentrated, extracted with ethyl acetate, and the filtrate was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate: 200: 1(v/v)) to obtain 18.78g of a white solid with a yield of 68.7%.

The nuclear magnetic structure confirmation data for compound 5 is shown below:

¹H NMR(CDCl₃,400MHz,TMS):7.86(s,2H),7.59(d,J＝8.0Hz,6H),7.48(t,J＝8.0Hz,10H),7.35(d,J＝8.0Hz,12H),7.13(d,J＝8.0Hz,2H),7.04(d,J＝8.0Hz,2H),5.86(t,J＝8.0Hz,2H),5.38(s,2H),3.75(t,J＝8.0Hz,4H),3.67–3.55(m,4H),2.73(m,4H),1.94–1.88(m,4H),1.65–1.62(m,8H).

¹³C NMR(CDCl₃,100MHz,TMS):157.4,143.4,139.1,137.2,129.2,128.6,128.1,127.9,126.3,125.6,122.3,121.3,104.7,74.5,63.4,38.6,35.2,29.5,29.0,24.6.

(6) preparation of compound 6:

18.22g of Compound 5(0.02mol, 1eq) was dissolved in a mixed solution of 50mL of ethyl acetate and 50mL of methanol, and 5mL of 12mol/L concentrated hydrochloric acid (0.06mol, 3eq) was added to the solution to react at room temperature for 2 hours. The solvent was dried, extracted and rotary evaporated to give 14.43g of a white solid in 97.1% yield.

The nuclear magnetic structure confirmation data for compound 6 is shown below:

¹H NMR(CDCl₃,400MHz,TMS):9.35(s,2H),7.83(s,2H),7.55(d,J＝8.0Hz,6H),7.46(t,J＝8.0Hz,10H),7.36(d,J＝8.0Hz,12H),7.17(d,J＝8.0Hz,2H),7.10(d,J＝8.0Hz,2H),5.35(s,2H),3.71(t,J＝8.0Hz,4H),2.74(m,4H).

¹³C NMR(CDCl₃,100MHz,TMS):157.1,143.2,138.7,137.3,129.3,128.5,127.6,126.4,125.3,122.1,121.3,74.6,38.8,29.1.

(7) preparation of Complex 7A:

in a glove box, 7.43g of Compound 6(0.01mol, 1eq) was dissolved in 40mL of dry toluene, 11mL of 2mol/L n-butyllithium (0.022mol, 2.2eq) was slowly added dropwise, after reaction at 25 ℃ for 1 hour, toluene was drained, 15mL of dry n-hexane was added, stirred for 15min, left to stand, filtered and washed with dry n-hexane, the residue was dissolved in 40mL of dry toluene, and 3.32g of TiCl was added₄(THF)₂(0.01mol, 1.0eq), heating to 120 ℃, refluxing for reaction for 8h, draining the toluene after the reaction is finished, adding 15mL of dry n-hexane, stirring for 15min, standing, filtering, washing with the dry n-hexane, draining the filtrate, adding 20mL of dry toluene, filtering, collecting the filtrate, draining the solvent to obtain 5.63g of light red solid with the yield of 65.5%.

The nuclear magnetic structure confirmation data of complex 7A is as follows:

¹H NMR(CDCl₃,400MHz,TMS):7.82(s,2H),7.52(d,J＝8.0Hz,6H),7.45(t,J＝8.0Hz,10H),7.36(d,J＝8.0Hz,12H),7.17(d,J＝8.0Hz,2H),7.11(d,J＝8.0Hz,2H),5.34(s,2H),3.71(t,J＝8.0Hz,4H),2.73(m,4H).

¹³C NMR(CDCl₃,100MHz,TMS):157.3,143.3,138.7,137.2,129.3,128.6,127.9,127.1,126.4,125.3,122.2,121.3,74.5,38.8,29.2.

[ example 2 ] preparation of Complex 8A, M is Ti, and X is-CH₃Preparation according to the "synthetic route for Complex A

The earlier stage of the experiment in this example is basically the same as that in example 1, except that methyl magnesium bromide is used to further modify complex 7A, the specific modification process is as follows: in a glove box, 5.16g of complex 7A (0.006mol, 1.0eq) is dissolved in 40mL of dry toluene, 4mL of 3mol/L toluene solution of methyl magnesium bromide (0.012mol, 2.0eq) is slowly added dropwise, after reaction for 3h at 25 ℃, the filtrate is filtered and collected, and after the solvent is drained, 4.1g of light red solid, namely complex 8A, is obtained, wherein the yield is 83.5%.

The nuclear magnetic structure confirmation data for complex 8A is shown below:

¹H NMR(CDCl₃,400MHz,TMS):7.83(s,2H),7.52(d,J＝8.0Hz,6H),7.44(t,J＝8.0Hz,10H),7.38(d,J＝8.0Hz,12H),7.17(d,J＝8.0Hz,2H),7.12(d,J＝8.0Hz,2H),5.34(s,2H),3.71(t,J＝8.0Hz,4H),2.74(m,4H)，1.23(s,6H)

¹³C NMR(CDCl₃,100MHz,TMS):156.8,143.3,138.8,137.2,129.3,128.7,127.9,127.2,126.4,125.3,122.1,121.3,74.5,38.9,29.2，23.1。

[ example 3 ] preparation of Complex 9A, M is Zr, X is-CH₃Preparation according to the "synthetic route for Complex A

The experimental procedure of this example is substantially the same as that of example 2, except that ZrCl was used as the material₄(THF)₂(3.75g, 0.01mol, 1.0eq) preparing a metal complex, and further modifying the metal complex by adopting methyl magnesium bromide, wherein the specific modification process comprises the following steps: 5.42g of the metal complex (0.006mol, 1.0eq) was dissolved in 40mL of dry toluene, 4mL of a 3mol/L toluene solution of methylmagnesium bromide (0.012mol, 2.0eq) was slowly added dropwise, and after reaction at 25 ℃ for 3h, the filtrate was filtered and collected to obtain 3.63g of an off-white solid with a yield of 70.2% after draining off the solvent.

The nuclear magnetic structure confirmation data for complex 9A is shown below:

¹H NMR(CDCl₃,400MHz,TMS):7.82(s,2H),7.53(d,J＝8.0Hz,6H),7.45(t,J＝8.0Hz,10H),7.36(d,J＝8.0Hz,12H),7.17(d,J＝8.0Hz,2H),7.12(d,J＝8.0Hz,2H),5.34(s,2H),3.70(t,J＝8.0Hz,4H),2.73(m,4H).

¹³C NMR(CDCl₃,100MHz,TMS):157.3,143.3,138.7,137.2,129.3,128.7,127.8,127.2,126.4,125.3,122.2,121.3,74.5,38.9,29.2.

EXAMPLE 4 preparation of Complex 10A, M is Hf, and X is-CH₂CH₃Preparation according to the "synthetic route for Complex A

The experimental procedure of this example is substantially the same as that of example 2, except that HfCl is selected for use in this example₄(THF)₂(4.63g, 0.01mol, 1.0eq) preparing a metal complex, and further modifying the metal complex by adopting ethyl magnesium bromide, wherein the specific modification process comprises the following steps: 5.94g of the metal complex (0.006mol, 1.0eq) was dissolved in 40mL of dry toluene, 4mL of a 3mol/L solution of ethylmagnesium bromide in toluene (0.012mol, 2.0eq) was slowly added dropwise, and after reaction at 25 ℃ for 3h, the filtrate was filtered and collected to obtain 3.14g of an off-white solid in 53.6% yield after draining off the solvent.

The nuclear magnetic structure confirmation data for complex 10A is shown below:

¹H NMR(CDCl₃,400MHz,TMS):7.80(s,2H),7.54(d,J＝8.0Hz,6H),7.45(t,J＝8.0Hz,10H),7.36(d,J＝8.0Hz,12H),7.16(d,J＝8.0Hz,2H),7.10(d,J＝8.0Hz,2H),5.34(s,2H),3.71(t,J＝8.0Hz,4H),2.72(m,4H)，2.02(m,4H)，1.1(m,6H).

¹³C NMR(CDCl₃,100MHz,TMS):157.5,143.3,138.7,137.3,129.3,128.5,127.7,127.1,126.4,125.3,122.2,121.3,74.5,38.9,29.3，23.1.

[ example 5 ] preparation of Complex 7B, M is Ti and X is Cl, according to "synthetic route for Complex B

The experimental procedure of this example is essentially the same as in example 1, except that in this example, 1-dimethyl-2, 2-dibromoethyl ether (9.1g, 0.035mol, 0.5eq) is used as the starting material to prepare compound 2, and then the final product is prepared by the method of example 1 using compound 2 as the starting material, to obtain 5.96g of light red solid with a yield of 67.1%.

The nuclear magnetic structure confirmation data of complex 7B is as follows:

¹H NMR(CDCl₃,400MHz,TMS):7.82(s,2H),7.51(d,J＝8.0Hz,6H),7.46(t,J＝8.0Hz,10H),7.36(d,J＝8.0Hz,12H),7.15(d,J＝8.0Hz,2H),7.11(d,J＝8.0Hz,2H),5.35(s,2H),3.72(t,J＝8.0Hz,2H),2.73(m,4H),1.17(m,6H).

¹³C NMR(CDCl₃,100MHz,TMS):157.6,143.3,138.8,137.5,129.3,128.6,127.8,127.1,126.8,125.3,122.5,121.3,74.6,38.8,29.3,21.5.

[ example 6 ] preparation of Complex 9B, M is Zr, X is-CH₃Preparation according to the "synthetic route for Complex B

The experimental procedure of this example is substantially the same as that of example 5, except that ZrCl was used as the material₄(THF)₂(3.75g, 0.01mol, 1.0eq) preparing a metal complex, and further modifying the metal complex by adopting methyl magnesium bromide, wherein the specific modification process comprises the following steps: in a glove box, 5.59g of the metal complex (0.006mol, 1.0eq) was dissolved in 40mL of dry toluene, 4mL of a 3mol/L toluene solution of methylmagnesium bromide (0.012mol, 2.0eq) was slowly added dropwise, and after 3 hours of reaction at room temperature, the filtrate was filtered and collected to obtain 3.66g of an off-white solid in 68.5% yield after draining off the solvent.

The nuclear magnetic structure confirmation data for complex 9B is shown below:

¹H NMR(CDCl₃,400MHz,TMS):7.81(s,2H),7.51(d,J＝8.0Hz,6H),7.47(t,J＝8.0Hz,10H),7.35(d,J＝8.0Hz,12H),7.15(d,J＝8.0Hz,2H),7.10(d,J＝8.0Hz,2H),5.35(s,2H),3.73(t,J＝8.0Hz,2H),2.73(m,4H),1.16(m,6H).

¹³C NMR(CDCl₃,100MHz,TMS):157.6,143.4,138.8,137.8,129.1,128.6,127.7,127.1,126.8,125.8,122.5,121.4,74.5,38.8,29.3,21.0.

[ example 7 ] ethylene/1-octene copolymerization catalyzed by Complex 7A/MAO

An ampere bottle filled with weighed complex 7A (1 mu mol), a temperature sensor, a cooling reflux device and a mechanically stirred 1L high-pressure reaction kettle are continuously dried for 1 hour at 120 ℃, vacuumized and gradually cooled to 25 ℃. 400mL of Isopar E solution of tetrakis (pentafluorophenyl) borate-methyldioctadecyl ammonium salt (2. mu. mol), 100mL of Isopar E diluted solution of 0.002mol/L MAO (0.2mmol) and 100mL of 1-octene were sequentially added, the temperature was further raised to 150 ℃, 3.0MPa of ethylene monomer was introduced, an ampoule was broken, and polymerization was started. The stirring rate, the polymerization temperature andkeeping the ethylene pressure unchanged for 15min, evacuating the kettle, neutralizing the reaction solution with 5% hydrochloric acid acidified industrial alcohol solution to obtain polymer precipitate, washing several times, vacuum drying to constant weight to obtain 35g polymer with Al/Ti ratio of 200 and catalytic activity of 1.4 × 10⁸gmol^-1(Ti)h^-1，M_w＝1.42×10⁵g mol^-1，PDI＝2.7，T_mThe insertion rate of 1-octene was 53.5 wt% at 77.8 ℃. Wherein PDI represents a molecular weight distribution coefficient, M_wRepresents a weight average molecular weight.

Example 8 copolymerization of ethylene/1-octene with Complex 8A/MAO

The polymerization process was substantially the same as in example 7 except that the main catalyst was replaced with Complex 8A to prepare 46.23g of a polymer having a catalytic activity of 1.85 × 10⁸g mol^-1(Ti)h^-1，M_w＝1.79×10⁵g mol^-1，PDI＝2.9，T_mThe 1-octene insertion rate was 60.1 wt% at 70.8 ℃.

[ example 9 ] ethylene/1-octene copolymerization catalyzed by Complex 9A/MAO

The polymerization process was substantially the same as in example 7 except that the main catalyst was changed to the complex 9A, the polymerization time was 30min, the polymerization pressure was 1MPa, 79g of a polymer was obtained, and the catalytic activity was 1.58 × 10⁸g mol^-1(Zr)h^-1，M_w＝1.53×10⁵g mol^-1，PDI＝2.9，T_mThe 1-octene insertion rate was 56.4 wt% at 73.4 ℃.

[ example 10 ] ethylene/1-octene copolymerization catalyzed by Complex 10A/MMAO

The polymerization process was substantially the same as in example 7 except that the main catalyst was replaced with the complex 10A and the cocatalyst was replaced with 0.002mol/L of MMAO (100mL), the polymerization temperature was 200 ℃ and the polymerization pressure was 5MPa, 32.1g of the polymer was obtained, and the catalytic activity was 1.28 × 10⁸g mol^-1(Hf)h^-1，M_w＝1.35×10⁵g mol^-1，PDI＝3.3，T_mThe 1-octene insertion rate was 57.1 wt% at 73.1 ℃.

[ example 11 ] ethylene/1-octene copolymerization catalyzed by Complex 7B/MAO

The polymerization process was substantially the same as in example 7 except that the main catalyst was changed to complex 7B and the amount of 0.002mol/L of MAO solution was changed to 50mL, the reaction temperature was 180 ℃ and the polymerization time was 5min, whereby 17.67g of a polymer having a catalytic activity of 2.12 × 10 was obtained⁸g mol^-1(Ti)h^-1，M_w＝1.56×10⁵g mol^-1，PDI＝3.1，T_mThe 1-octene insertion rate was 58.5 wt% at 71.4 ℃.

[ example 12 ] ethylene/1-octene copolymerization catalyzed by Complex 9B/MMAO

The polymerization process was substantially the same as in example 10 except that the main catalyst was changed to 9B, the amount of 0.002mol/L of MMAO solution was changed to 25mL, the polymerization temperature was 180 ℃ and the polymerization pressure was 5MPa, 58.2g of the polymer was obtained, and the catalytic activity was 2.33 × 10⁸g mol^-1(Zr)h^-1，M_w＝1.74×10⁵g mol^-1，PDI＝2.6，T_mThe 1-octene insertion rate was 57.9 wt% at 71.6 ℃.

[ COMPARATIVE EXAMPLES ]

The copolymerization of ethylene/1-octene was catalyzed with commercially available dimethylsilyldiindenyl zirconium dichloride as the main catalyst:

the polymerization process was substantially the same as in example 12 except that the main catalyst was replaced with dimethylsilyldiindenyl zirconium dichloride to obtain 7.78g of a polymer having a catalytic activity of 0.31 × 10⁸g mol^-1(Zr)h^-1，M_w＝0.43×10⁵g mol^-1，PDI＝3.2，T_mThe 1-octene insertion rate was 18.1 wt% at 110 ℃.

TABLE 1 results of ethylene/1-octene copolymerization Performance test

As can be seen from the above examples and comparative examples, the polymerization catalyst system of the complex and the cocatalyst has good synergistic effect, and shows higher comonomer insertion rate, thermal stability and copolymerization activity.

The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.