CN105461757B

CN105461757B - Multinuclear late transition metal olefin polymerization catalyst

Info

Publication number: CN105461757B
Application number: CN201410412200.8A
Authority: CN
Inventors: 唐勇; 季刚; 孙秀丽
Original assignee: Shanghai Institute of Organic Chemistry of CAS
Current assignee: Shanghai Institute of Organic Chemistry of CAS
Priority date: 2014-08-20
Filing date: 2014-08-20
Publication date: 2020-05-12
Anticipated expiration: 2034-08-20
Also published as: CN105461757A

Abstract

The invention relates to a bimetallic olefin polymerization catalyst, a preparation method thereof and application thereof in catalyzing olefin polymerization. The catalyst is an eighth-group transition bimetallic complex of a polydentate ligand, and the structural formula is shown as a formula I; wherein, the definition of each group is described in the specification. The catalyst of the invention has higher activity and catalytic efficiency, is suitable for olefin polymerization reaction, and is especially suitable for preparing olefin polymers with molecular weight in bimodal distribution.

Description

Multinuclear late transition metal olefin polymerization catalyst

Technical Field

The invention relates to a catalyst or a catalyst system for olefin polymerization and copolymerization, a synthesis method and application thereof in catalyzing olefin polymerization. The catalyst relates to a novel polynuclear late transition metal complex of a polydentate ligand.

Background

MgCl with high activity since the discovery of Ziegler-Natta catalysts in the fifties of the twentieth century₂Supported titanium catalysts show very good catalytic performance, (K.Ziegler, et al, Angew. chem.1995,67,424; K.Ziegler, et al, Angew. chem.1995,67,541; N.Kashiwa, et al, USP-3642746,1968) and have been used in the industry today for the production of polymers of High Density Polyethylene (HDPE), Linear Low Density Polyethylene (LLDPE), syndiotactic polypropylene (i-pp). However, the multi-active-center solid catalyst cannot control the polymer structure and performance by adjusting the catalyst structure; the discovery of group IV metallocene catalysts has better solved this problem by having a single site of activity, allowing one to obtain polymers of the desired structure by altering the structure of the catalyst as desired (W.Kaminsky et al, adv.Organomet.chem.1980,18, 99; W.Kaminsky et al, Angew.chem., int.Ed.Engl.1980,19,390; H.H.Brintzinger et al, Angew.chem.Ed.Engl.1995, 34,1143). In addition, polyolefins have low surface energies, are chemically inert, and are limited in the adhesion, dyeing, printing and blending of materials (additives, polar materials)Therefore, it is necessary to enhance the polarity of polyolefin by introducing a small amount of polar functional groups into the polyolefin polymer chain, so as to improve the compatibility of polyolefin materials with polar materials, while maintaining equivalent physical and mechanical properties. Therefore, a plurality of mild, efficient and controllable methods are searched for introducing polar functional groups into nonpolar molecular chains. However, the early transition metal catalysts, including the widely used Ziegler-Natta catalysts and metallocene catalysts, are easily poisoned and deactivated by polar groups in polar monomers, so that the copolymerization of ethylene and polar monomers is still not desirable.

In recent decades, research on a metal complex obtained by coordinating cyclopentadiene and transition metal with ligands containing coordination atoms such as N, O, P is vigorously developed, the catalyst is called as 'post-metallocene catalyst', and comprises a plurality of polynuclear catalysts, wherein the design and application of the polynuclear post-transition metal catalyst are reported, and some polynuclear catalysts show obvious synergistic effect along with the difference of complex structures, so that the catalyst activity is improved; some catalysts perform as well as the corresponding mononuclear catalysts. Representative transition metal complexes are as follows.

The post-transition metal coordinated 'post-metallocene catalyst' reported in the literature can realize the homopolymerization of olefin to obtain a polymer with narrower molecular weight distribution, but the microstructure of the polymer cannot be well regulated and controlled; copolymerization of olefins with polar monomers can also be achieved well due to the poor oxophilicity of the central metal, yielding functionalized polyolefin materials with superior properties, but with lower activity (e.g., a) the compounds provided in Johnson, L.K.et al.J.Am.chem.Soc.,1996,118(1), b) Chen, G.et al.J.Am.chem.Soc.,2003,125(22), 6697).

These problems are problematic for catalyst technology and product applications. In order to realize application, the unification of the mechanical property and the processing property of the product can be met only by a step-by-step polymerization mode or a mixed catalyst at present. In view of the foregoing, there is a need in the art for a catalyst for olefin polymerization which has high catalytic activity, can catalyze homopolymerization of ethylene and propylene and copolymerization of olefin and various comonomers, including polar monomers, and can easily obtain a polymer with adjustable molecular weight distribution.

Disclosure of Invention

The invention aims to provide a catalyst capable of efficiently catalyzing olefin polymerization and a preparation method thereof.

Another object of the present invention is to provide a novel method for controlling polymer structure to obtain unimodal or bimodal molecular weight distribution of the polymer using the catalyst technology.

In a first aspect of the invention, there is provided a compound of formula I:

in the formula:

- - - - - -is a coordinate bond;

Y₃selected from the group consisting of: hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted C3-C10 cycloalkyl; wherein, the aryl group refers to phenyl, naphthyl, fluorenyl or anthryl; by substituted is meant that one or more hydrogen atoms on the group are replaced by a group selected from the group consisting of: OR (OR)³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen, phenyl;

Z¹selected from the group consisting of: substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; wherein, the aryl group refers to phenyl, naphthyl, fluorenyl or anthryl; the heteroaryl refers to furyl, thienyl, pyrrolyl, pyridyl or pyranyl; by substituted is meant that one or more hydrogen atoms on the group are replaced by a group selected from the group consisting of: OR (OR)³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen, phenyl;

or Y₃、Z₁And adjacent N ═ C form a ring

Structure;

is a 5-12 membered heterocyclic ring containing 1-3 heteroatoms, preferably a 5-7 membered heterocyclic ring; wherein the heteroatom is selected from the group consisting of: n, S, O or P;

Y¹、Y²is composed of

One or more optional substituents on the ring, and said Y¹、Y²Each independently selected from the group consisting of: hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted C3-C10 cycloalkyl;

wherein, the aryl group refers to phenyl, naphthyl, fluorenyl or anthryl; by substituted is meant that one or more hydrogen atoms on the group are replaced by a group selected from the group consisting of: halogen, C1-C4 alkyl, OR³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²A phenyl group;

M¹、M²each independently selected from the group consisting of: fe. Co, Ni, Pd, Pt, or a combination thereof;

X¹、X²each independently selected from the group consisting of: halogen, ClO₄ ^-Substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl; wherein said substitution is one or more hydrogen atoms on the group substituted with a group selected from the group consisting of: OR (OR)³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen, phenyl, -CF₃；

Wherein, R is³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹²Each independently selected from the group consisting of: C1-C10 alkyl, phenyl, C5-C16 heteroaryl; wherein 0 to 5 hydrogen atoms of said phenyl or heteroaryl group may be substituted by a substituent selected from the group consisting of: halogen, -CF₃、OR¹³C1-C4 alkyl; r¹³Refers to C1-C4 alkyl;

and the compounds of formula I are charge balanced.

In another preferred embodiment, Y¹、Y²、Y³Each independently selected from the group consisting of: substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl; the substitution is OR³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen, phenyl. Wherein said phenyl group is an unsubstituted phenyl group or a phenyl group in which one or more hydrogen atoms on the phenyl ring are substituted with a group selected from the group consisting of: OR (OR)¹³C1-C4 alkyl, halogen, -CF₃。

In another preferred embodiment, Y¹、Y²、Y³Each independently selected from the group consisting of: substituted or unsubstituted aryl; the aryl refers to phenyl, naphthyl, fluorenyl or anthryl; the substitution is OR¹³C1-C4 alkyl, halogen, CF₃。

In another preferred embodiment, Y¹、Y²、Y³Each independently selected from the group consisting of: halogen, substituted or unsubstituted C1-C4 alkyl;

in another preferred embodiment, X¹、X²Each independently selected from the group consisting of: halogen, ClO₄ ^-Substituted or unsubstituted phenyl, substituted or unsubstituted benzyl; wherein said substitution is one or more hydrogen atoms on the phenyl ring substituted with a group selected from the group consisting of: OR (OR)¹³C1-C4 alkyl, halogen, CF₃And a phenyl group.

In another preferred embodiment, X is¹、X²Each independently selected from the group consisting of: chlorine, bromine, ClO₄ ^-。

In another preferred embodiment, Z¹Selected from the group consisting of: substituted or unsubstituted C1-C10 alkyl; the substitution is OR³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen.

In another preferred embodiment, Z¹Selected from the group consisting of: substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; the aryl group refers to phenyl, naphthyl, fluorenyl or anthracenyl, and the heteroaryl group refers to furyl, thienyl, pyrrolyl, pyridyl or pyranyl. The substitution is OR³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen, phenyl. Wherein said phenyl group comprises a substituted or unsubstituted phenyl group, said substitution being such that one or more hydrogen atoms on the phenyl ring are substituted by a group selected from the group consisting of: OR (OR)¹³C1-C4 alkyl, halogen, CF₃(ii) a Wherein, R is³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²Each independently selected from the group consisting of: C1-C10 alkyl, phenyl, C5-C16 heteroaryl; wherein 0 to 5 hydrogen atoms of said phenyl or heteroaryl group may be substituted by a substituent selected from the group consisting of: halogen, CF₃、OR¹³C1-C4 alkyl; r¹³Refers to C1-C4 alkyl.

The halogen refers to fluorine, chlorine, bromine or iodine.

In another preferred embodiment, Z is¹The heteroatom(s) may optionally be substituted with M²Forming a coordination bond.

In another preferred embodiment, M is¹And M²Each independently selected from the group consisting of: fe. Co, Ni, Pd.

In another preferred embodiment, M is¹、M²Each independently selected from the group consisting of: fe (II), Co (II), Ni (II), Pd (II).

In a second aspect of the invention, there is provided a process for the preparation of a compound according to the first aspect of the invention, said process comprising the steps of:

reacting a compound of formula III with a reagent selected from the group consisting of or a hydrate thereof in an inert solvent to obtain a compound of formula I; m¹X¹、M¹X¹·B、M²X²、M²X²B, or a combination thereof;

wherein, M is₁X₁B or M₂X₂B is each M₁X₁Or M₂X₂A metal compound formed with a coordinating solvent B; preferably, the coordinating solvent B is selected from the group consisting of: DME (ethylene glycol dimethyl ether), THF (tetrahydrofuran), acetonitrile, ethanol, ethylene glycol, methanol, AcAc (acetylacetonyl), DMF, or a combination thereof;

the remaining groups are as defined in the first aspect of the invention.

In another preferred example, the steps include: with compounds of the formula III first with M¹X¹Or M¹X¹B reaction with M²X²Or M²X²B reaction.

In another preferred embodiment, said complex of formula I may also be present in the form of a stable structure by interaction with a ligand selected from the group consisting of: triphenylphosphine, acetonitrile, tetrahydrofuran, and C4-C16 heteroarene.

In another preferred embodiment, the C4-C16 heteroarene is pyridine.

In another preferred embodiment, M is selected from the group consisting of: fe. Co, Ni, Pd; preferably selected from the group consisting of: fe (II), Co (II), Ni (II), Pd (II).

In another preferred embodiment, the oxidizing agent is selected from the group consisting of: benzoyl peroxide, ozone, air, oxygen, hydrogen peroxide, or a combination thereof.

In another preferred embodiment, the inert solvent is a weakly polar solvent.

In another preferred embodiment, the weakly polar solvent is selected from the group consisting of: tetrahydrofuran, diethyl ether, toluene, hexane, acetonitrile, dichloromethane, or combinations thereof.

In another preferred embodiment, the reaction is carried out in oxygen, air.

In another preferred embodiment, the reaction is carried out at-78 ℃ to 150 ℃.

In another preferred embodiment, the reaction is carried out at 0 ℃ to 100 ℃.

In another preferred embodiment, the reaction is carried out at a temperature of 0 ℃ to 75 ℃.

In another preferred embodiment, the reaction is carried out at 20 ℃ to 80 ℃.

In another preferred embodiment, the reaction time is 2h to 15 days.

In another preferred example, the reaction time is 3 to 10 days.

In another preferred embodiment, the reaction is carried out under 0.01-10 MPa.

In another preferred embodiment, the reaction is carried out at 0.1 to 5 MPa.

In a third aspect of the present invention, there is provided a compound having the structure of formula III:

wherein each group is as defined in the second aspect of the invention.

In a further preferred embodiment of the method,

is a multi-substituted or unsubstituted five-or six-membered ring containing 1-3N, S, O or P atoms thereinAt least one N.

In another preferred embodiment, the multi-substituted or unsubstituted five-or six-membered ring is selected from the group consisting of:

wherein, Y⁴、Y⁵、Y⁶、Y⁷、Y⁸Each independently selected from the group consisting of: hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted C3-C10 cycloalkyl;

wherein, the aryl group refers to phenyl, naphthyl, fluorenyl or anthryl; by substituted is meant that one or more hydrogen atoms on the group are replaced by a group selected from the group consisting of: OR (OR)³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen, phenyl;

wherein, R is³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹²Each independently selected from the group consisting of: C1-C10 alkyl, phenyl, C5-C16 heteroaryl; wherein 0 to 5 hydrogen atoms of said phenyl or heteroaryl group may be substituted by a substituent selected from the group consisting of: halogen, -CF₃、OR¹³、C1-C4 alkyl; r¹³Refers to C1-C4 alkyl;

in another preferred embodiment, Y⁴、Y⁵、Y⁶、Y⁷、Y⁸Each independently selected from the group consisting of: substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl; the substitution is OR³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen, phenyl. Wherein said phenyl group is an unsubstituted phenyl group or a phenyl group in which one or more hydrogen atoms on the phenyl ring are substituted with a group selected from the group consisting of: OR (OR)¹³C1-C4 alkyl, halogen, -CF₃。

In another preferred embodiment, Y⁴、Y⁵、Y⁶、Y⁷、Y⁸Each independently selected from the group consisting of: substituted or unsubstituted aryl; the aryl refers to phenyl, naphthyl, fluorenyl or anthryl; the substitution is OR¹³C1-C4 alkyl, halogen, CF₃。

In another preferred embodiment, Y⁴、Y⁵、Y⁶、Y⁷、Y⁸Together form a substituted or unsubstituted C1-C4 alkylene group.

In another preferred embodiment, Y⁴、Y⁵、Y⁶、Y⁷、Y⁸Each independently selected from the group consisting of: halogen, substituted or unsubstituted C1-C4 alkyl;

The halogen refers to fluorine, chlorine, bromine or iodine.

In a fourth aspect of the invention, there is provided a process for the preparation of a compound of formula III as described in the third aspect of the invention, said process comprising the steps of:

reacting a compound of formula II with an oxidizing agent in an inert solvent in the presence of a base to provide a compound of formula III.

In another preferred embodiment, the oxidizing agent is selected from the group consisting of: oxygen, benzoyl peroxide, ozone, air, hydrogen peroxide, or a combination thereof.

In another preferred embodiment, the base is selected from the group consisting of: n-butyllithium, lithium diisopropylamide, potassium diisopropylamide, sodium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, Et₃N, pyridine, or a combination thereof.

In another preferred embodiment, the inert solvent is a weakly polar solvent.

In another preferred embodiment, the base is selected from the group consisting of: KH. NaH, BuLi, Et₃N, pyridine, or a combination thereof.

In a fifth aspect of the present invention, there is provided a compound having the structure of formula II:

wherein each group is as defined in the third aspect of the invention.

In a sixth aspect of the present invention, there is provided a process for the preparation of a compound of formula II as described in the fifth aspect of the present invention, said process comprising the steps of:

(a1) reacting a compound of formula IIc with a compound of formula IIb in an inert solvent to provide a compound of formula IIa;

(a2) reacting a compound of formula IIa in an inert solvent to obtain a compound of formula IIf;

and step (a3) using the compound of formula IIf to prepare a compound of formula II;

or the method comprises the steps of:

(b1) reacting a compound of formula IId with a compound of formula IIb in an inert solvent to obtain a compound of formula IIe;

(b2) reacting with a compound of formula IIe to give a compound of formula IIg;

and step (b3) using the compound of formula IIg to prepare a compound of formula II;

in the formula, D₁、D₂、D₃、D₄Each independently selected from the group consisting of: n, S, O, P, NH, PH;

Y₄、Y₅each independently selected from the group consisting of: substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; wherein, the aryl group refers to phenyl, naphthyl, fluorenyl or anthryl; the heteroaryl refers to furyl, thienyl, pyrrolyl, pyridyl or pyranyl; by substituted is meant that one or more hydrogen atoms on the group are replaced by a group selected from the group consisting of: OR (OR)³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen, phenyl;

or Y₄、Y₅And two carbon atoms connected with the substituted or unsubstituted benzene ring; or together form a substituted or unsubstituted 5-to 12-membered heteroaromatic ring, preferably a 5-to 7-membered heteroaromatic ring; wherein said substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of: hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted C3-C10 cycloalkyl;

the remaining groups are as defined in the third aspect of the invention.

In another preferred embodiment, the asymmetric substituted compound precursor II is prepared as follows:

polysubstituted pyridine and substituted β -amino alcohol take condensation reaction to obtain intermediate, the intermediate takes dichloromethane as solvent, TsCl and DMAP are condensed to form ring, and the final product is obtained.

β -carboxylic ester substituted ketone and substituted β -amino alcohol are subjected to condensation reaction to obtain an intermediate 1, the intermediate 1 is subjected to condensation cyclization by using dichloromethane as a solvent and TsCl and DMAP to obtain an intermediate 2, and the intermediate 2 is subjected to condensation with substituted amine under Lewis acid catalysis to obtain a final product.

In another preferred embodiment, said step (a1) comprises condensation reaction of diethyl malonate with substituted β -amino alcohol to obtain intermediate IIa by recrystallization;

in another preferred example, the step (a2) includes: and (3) condensing the intermediate IIa in dichloromethane by using TsCl and DMAP to form a ring to obtain a final product.

In another preferred embodiment, step (b1) comprises the condensation of a polysubstituted pyridine with a substituted β -amino alcohol to provide intermediate IIe.

In another preferred embodiment, the step (b2) includes: the intermediate is condensed into a ring by using TsCl and DMAP in dichloromethane as a solvent to obtain a final product.

In another preferred embodiment, step (b1) comprises the condensation of a β -carboxylate substituted ketone with a substituted β -amino alcohol to provide intermediate IIe.

And (3) condensing the intermediate 1 into a ring by using dichloromethane as a solvent and using TsCl and DMAP to obtain an intermediate 2, and condensing the intermediate 2 with substituted amine under the catalysis of Lewis acid to obtain a final product.

In a seventh aspect of the invention, there is provided the use of a compound according to the third or fifth aspect of the invention as (a) an olefin polymerisation catalyst; (b) preparing an olefin polymerization catalyst composition; or (c) for the preparation of a compound of formula I as described in the first aspect of the invention.

In an eighth aspect of the present invention, there is provided the use of a compound according to the first aspect of the present invention, wherein the compound (a) is used as a catalyst for catalyzing the polymerization of olefins; or (b) for the preparation of an olefin polymerization catalyst composition.

In another preferred embodiment, the catalyst composition further comprises an effective amount of a cocatalyst.

In another preferred embodiment, the cocatalyst is selected from the group consisting of: an alkylaluminum compound, an alkylaluminoxane, a weakly coordinating anion, or a combination thereof.

In another preferred embodiment, the molar ratio of the catalyst to the cocatalyst is 1: 1-10000.

In another preferred embodiment, the alkyl aluminum compound is selected from the group consisting of: AlEt₃、AlEt₂Cl、AlEtCl₂、AlMe₂Cl、AlMe₃、Al(i-Bu)₃Or a combination thereof.

In another preferred embodiment, the alkylaluminoxane is methylaluminoxane.

In another preferred embodiment, the weakly coordinating anion is selected from the group consisting of: [ B (3,5- (CF) ]₃)₂C₆H₃)₄]^-、^-OSO₂CF₃、((3,5-(CF₃)₂)C₆H₃)₄B^-Or a combination thereof.

In a ninth aspect of the present invention there is provided an olefin polymerisation catalyst composition comprising a catalytically effective amount of a compound of formula I as described in the first aspect of the present invention and/or a compound of formula II as described in the third aspect of the present invention or a complex thereof.

In another preferred embodimentWherein the alkyl aluminum compound is selected from the group consisting of: AlEt₃、AlEt₂Cl、AlEtCl₂、AlMe₂Cl、AlMe₃、Al(i-Bu)₃Or a combination thereof.

In another preferred embodiment, the alkylaluminoxane is methylaluminoxane.

In a tenth aspect of the present invention, there is provided a process for producing an olefin polymer, characterized in that the process comprises: subjecting an olefin to an olefin polymerization reaction in the presence of a catalytically effective amount of a catalyst to obtain an olefin polymer;

wherein the catalyst is selected from the group consisting of: a compound according to the first aspect of the present invention, a compound according to the third aspect of the present invention or a complex thereof, a catalyst composition according to the ninth aspect of the present invention, or a combination thereof.

In another preferred embodiment, the olefin is a substituted or unsubstituted C2-C30 olefin.

In another preferred embodiment, the olefin is a substituted or unsubstituted α -olefin having from C3 to C30.

In another preferred embodiment, the olefin is a substituted or unsubstituted α -olefin having from C6 to C30.

In another preferred embodiment, the olefin is a substituted or unsubstituted C5-C30 cyclic olefin.

In another preferred embodiment, the olefin is C containing polar groups₃～C₅₀And 1-olefin derivatives and cyclic olefin derivatives.

In another preferred embodiment, the olefin is C containing polar groups₃～C₃₀1-olefin derivatives and cyclic olefin derivatives. In another preferred embodiment, the olefin polymer has a molecular weight selected from the group consisting ofOne or more characteristics of the group:

(a) molecular weight is 1000 to 5,000,000 g/mol;

(b) the molecular weight distribution of the olefin polymer is unimodal, bimodal or multimodal.

In another preferred embodiment, the compound of formula I is used as a catalyst when preparing olefin polymers having a bimodal molecular weight distribution.

In another preferred embodiment, the olefin polymer is a copolymer of a C2-C4 olefin and a polar monomer.

In another preferred embodiment, the polar monomer is protected with a functional group protecting agent prior to polymerization.

In another preferred embodiment, the functional group protecting agent is TBS, TES, TBDPS, TMS, Et₃Al、i-Bu₃Al, methylaluminoxane, ethylaluminoxane, butylaluminoxane, modified methylaluminoxane, or a combination thereof.

In another preferred embodiment, the polar monomer is C containing polar groups₃～C₅₀And a cyclic olefin derivative containing a polar group selected from the group consisting of: carbonyl, hydroxy, carboxyl, COOR³²Ester group of (A), OR³³Alkoxy group of (2), NR³⁴R³⁵Amino group of (A), CONR³⁴R³⁵Amide group of (2), SR³⁶Of thioethers or SeR³⁷Selenoethers of (a); wherein R is³²Or R³³Is C_1-10A hydrocarbon group of (a); r³⁴、R³⁵、R³⁶Or R³⁷Is hydrogen or C_1-10A hydrocarbon group of (1).

In another preferred embodiment, the polar monomer has a structure represented by the following formula a:

wherein n is an integer of 0 to 48;

ra, Rb, Rc are each independently selected from the group consisting of: H. or two or three of Ra, Rb, Rc taken together with the adjacent double bond form an unsaturated C3-C50 monocyclic, polycyclic or bridged ring structure;

FG is a polar group, which means an oxygen-, nitrogen-, sulfur-, and/or selenium-containing organic functional group including a carbonyl group (C ═ O), a hydroxyl group (OH), a carboxyl group (COOH), an ester group (COOR)³²) Alkoxy (OR)³³) Amino group (NR)³⁴R³⁵) Amide group (CONR)³⁴R³⁵) Thioether (SR)³⁶) Selenium ether (SeR)³⁷) Or a combination thereof; wherein R is³²Or R³³Is C_1-10A hydrocarbon group of (a); r³⁴、R³⁵、R³⁶Or R³⁷Is hydrogen or C_1-10A hydrocarbon group of (a);

or one, two or three of Ra, Rb, Rc and- (CH)₂)_n-and adjacent double bonds together form an unsaturated C3-C50 monocyclic, polycyclic or bridged ring structure.

In another preferred embodiment, the monocyclic, polycyclic or bridged ring structure has polar groups and optionally non-polar groups.

In another preferred embodiment, the polar monomer has a structure represented by the following formula:

wherein, in the 1-olefin derivative, n and m are each independently an integer of 0 to 48.

In another preferred embodiment, in the formula a2, the cyclic moiety may be a monocyclic structure or a bridged cyclic structure.

FG is a polar group, which means an oxygen-, nitrogen-, sulfur-, and/or selenium-containing organic functional group including a carbonyl group (C ═ O), a hydroxyl group (OH), a carboxyl group (COOH), an ester group (COOR)³²) Alkoxy (OR)³³) Amino group (NR)³⁴R³⁵) Amide group (CONR)³⁴R³⁵) Thioether (SR)³⁶) Selenium ether (SeR)³⁷) (ii) a Wherein R is³²Or R³³Is C_1-10A hydrocarbon group of (a); r³⁴、R³⁵、R³⁶Or R³⁷Is hydrogen orC_1-10A hydrocarbon group of (1).

In another preferred embodiment, the polar monomer is selected from the group consisting of:

in an eleventh aspect of the present invention, there is provided an olefin polymer characterized in that the olefin polymer is produced by the method according to the tenth aspect of the present invention.

The present invention provides an olefin polymerisation reaction catalysed by a compound according to the first or second aspects of the invention, or by a catalyst composition according to the ninth aspect of the invention.

In another preferred embodiment, the polymerization pressure of the polymerization reaction is 0.01 to 10MPa, preferably 0.1 to 10 MPa.

In another preferred embodiment, the polymerization temperature range of the polymerization reaction is-50 to 150 ℃.

In another preferred embodiment, the olefin polymerization is copolymerization of ethylene and an olefin selected from the group consisting of substituted or unsubstituted C3-C30 α -olefin, substituted or unsubstituted C6-C30 α -olefin, and substituted or unsubstituted C5-C30 cyclic olefin, wherein the substitution is alkyl substitution or polar functional group substitution of the polar functional group-substituted olefin, i.e., polar monomers, including polar group-containing C3-C50 1-olefin derivatives and cyclic olefin derivatives, etc.

wherein n is an integer of 0 to 48;

FG is a polar group, saidThe polar group refers to an organic functional group containing oxygen, nitrogen, sulfur, and/or selenium, and includes a carbonyl group (C ═ O), a hydroxyl group (OH), a carboxyl group (COOH), an ester group (COOR)³²) Alkoxy (OR)³³) Amino group (NR)³⁴R³⁵) Amide group (CONR)³⁴R³⁵) Thioether (SR)³⁶) Selenium ether (SeR)³⁷) Or a combination thereof; wherein R is³²Or R³³Is C_1-10A hydrocarbon group of (a); r³⁴、R³⁵、R³⁶Or R³⁷Is hydrogen or C_1-10A hydrocarbon group of (a);

FG is a polar group, which means an oxygen-, nitrogen-, sulfur-, and/or selenium-containing organic functional group including a carbonyl group (C ═ O), a hydroxyl group (OH), a carboxyl group (COOH), an ester group (COOR)³²) Alkoxy (OR)³³) Amino group (NR)³⁴R³⁵) Amide group (CONR)³⁴R³⁵) Thioether (SR)³⁶) Selenium ether (SeR)³⁷) (ii) a Wherein R is³²Or R³³Is C_1-10A hydrocarbon group of (a); r³⁴、R³⁵、R³⁶Or R³⁷Is hydrogen or C_1-10A hydrocarbon group of (1).

the present invention also provides a process for producing an olefin polymer, the process comprising: subjecting an olefin to an olefin polymerization reaction in the presence of a catalytically effective amount of a catalyst to obtain an olefin polymer;

It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.

Detailed Description

The present inventors have conducted extensive and intensive studies and, as a result, have unexpectedly found that a class of compounds having a bimetallic active center can be used as catalysts for olefin polymerization. The catalyst is used for catalyzing olefin polymerization reaction, can obviously improve the catalytic efficiency, and is particularly suitable for olefin polymers with molecular weight in bimodal distribution. Based on the above findings, the inventors have completed the present invention.

Term(s) for

As used herein, the terms "olefin polymer" and "polyolefin" are used interchangeably and refer to olefin polymers.

The term "catalytic system" as used herein refers to the catalyst (I) described above, or the system formed by catalyst (I) and cocatalyst W:

as used herein, "co-catalyst" refers to a substance that can be used with the catalyst of the present invention to catalyze olefin polymerization reactions and improve the reactions. In the present invention, a preferred cocatalyst may be a neutral Lewis acid (Lewis acid).

The term "weakly coordinating anion" means relatively non-coordinatingCoordinating anions whose coordination can be found in the literature (W.Beck., et al., chem.Rev., vol.88, p 1405-1421(1988), and S.H.Stares, chem.Rev., vol.93, p927-942(1993)) and references thereto, for example (R.Beck., et al., chem.Rev., vol.93, p927-942(1993))¹⁴)₃AlX^-、(R¹⁴)₂AlX₂ ^-、(R¹⁴)AlX₃ ^-、SbF₆ ^-、PF₆ ^-、BF₄ ^-、(C₆F₅)₄B^-、(R_fSO₂)₂,N^-、CF₃SO₃ ^-、((3,5-(CF₃)₂)C₆H₃)₄B^-；

The term "substituted" means that one or more hydrogen atoms on a group are replaced with a substituent selected from the group consisting of: means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of: C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkoxy, halogen, hydroxyl, C1-C10 aldehyde group, C2-C10 acyl, C2-C10 ester group, amino, C6-C30 aryl and C5-C30 heteroaryl; OR (OR)³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰Or SeR¹¹、SiR¹²；

Wherein R is³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²Each independently selected from the group consisting of: C1-C10 alkyl, phenyl, C5-C16 heteroaryl; wherein 0 to 5 hydrogen atoms of said phenyl or heteroaryl group may be substituted by a substituent selected from the group consisting of: halogen, CF₃、OR¹³C1-C4 alkyl; r¹³Refers to C1-C4 alkyl.

The aryl and heteroaryl groups include unsubstituted aryl and heteroaryl groups, or substituted aryl or heteroaryl groups having 1 to 3 substituents selected from the group consisting of: halogen, C1-C10 alkyl, cyano, OH, nitro, C3-C10 cycloalkyl, C1-C10 alkoxy and amino.

In particular, in the present invention, unless otherwise specified, all of the substituents are inert substituents, that is, substituents which are difficult to coordinate with a metal. Preferred substituents of the present invention are selected from the group consisting of: C1-C30 alkyl, C3-C30 cycloalkyl, C6-C30 aryl and C5-C30 heteroaryl.

The term "C1-C30 alkyl" refers to a straight or branched chain alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, or the like.

The term "C3-C30 cycloalkyl" refers to a cycloalkyl group having 3 to 30 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, or the like.

The term "C6-C30 aryl" refers to aryl groups having 6 to 30 carbon atoms, including monocyclic or bicyclic aryl groups, such as phenyl, naphthyl, or the like.

The term "C5-C30 heteroaryl" refers to a heteroaryl group having 5-30 carbon atoms, such as pyrrolyl, pyridyl, furyl, or the like.

The term "C1-C10 acyl" refers to a group having the structure "-CO-alkyl", preferably having the structure "-CO-C1-C10 alkyl", such as methyl acyl, ethyl acyl, propyl acyl, isopropyl acyl, butyl acyl, isobutyl acyl, sec-butyl acyl, tert-butyl acyl, or the like.

The term "halogen" refers to F, Cl, Br and I.

As used herein, the term "inert functional group" refers to other carbon-containing functional groups other than hydrocarbyl and substituted hydrocarbyl groups that do not substantially interfere with reactions that may be involved in the substituted compound and that do not coordinate to the metal more strongly than oxygen, nitrogen, Z groups containing a coordinating atom when the inert functional group is in close proximity to the metal atom, i.e., the functional groups should not replace the desired coordinating group.

In each compound structural formula, "→" represents a coordinate bond.

The term "coordinating solvent" means a solvent which can form a coordinate bond with the group VIII metal M, and in the present invention, preferred coordinating solvents are solvents selected from the group consisting of: ethanol, methanol, glycol dimethyl ether, pyridine, acetonitrile, tetrahydrofuran and water.

The "ligand containing a group selected from the group consisting of: OR (OR)³、SR⁴、NR⁵R⁶、PR⁷R⁸Or a combination thereof "may be selected from the group consisting of: methanol, ethanol and ethylamine.

Compounds of formula I and their preparation

The invention provides a compound with a structure shown as a formula I:

in the formula:

- - - - - -is a coordinate bond;

Z¹selected from the group consisting of: substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; wherein, the aryl group refers to phenyl, naphthyl, fluorenyl or anthryl; the heteroaryl refers to furyl, thienyl, pyrrolyl, pyridyl or pyranyl; by substituted is meant that one or more hydrogen atoms on the group are replaced by a group selected from the group consisting of: OR (OR)³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halophenyl

Or Y3, Z1 and adjacent N ═ C together form a ring

Structure;

Y¹、Y²is composed of

X¹、X²each independently selected from the group consisting of: halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl; wherein said substitution is one or more hydrogen atoms on the group substituted with a group selected from the group consisting of: OR (OR)³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen, phenyl, -CF₃；

Wherein, R is³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹²Each independently selected from the group: C1-C10 alkyl, phenyl, C5-C16 heteroaryl; wherein 0 to 5 hydrogen atoms of said phenyl or heteroaryl group may be substituted by a substituent selected from the group consisting of: halogen, -CF₃、OR¹³C1-C4 alkyl; r¹³Refers to C1-C4 alkyl;

and the compounds of formula I are charge balanced.

In another preferred embodiment, Y¹、Y²、Y³Each independently selected from the group consisting of: substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl; the substitution is OR³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen, phenyl. Wherein said phenyl group is an unsubstituted phenyl group or a phenyl group in which one or more hydrogen atoms on the phenyl ring are substituted with a group selected from the group consisting of: OR (OR)¹³C1-C4 alkyl, halogen, CF₃。

in another preferred embodiment, X¹、X²Each independently selected from the group consisting of: halogen, substituted or unsubstituted C1-C4 alkyl;

in another preferred embodiment, X¹、X²Each independently selected from the group consisting of: halogen, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl; wherein said substitution is one or more hydrogen atoms on the phenyl ring substituted with a group selected from the group consisting of: OR (OR)¹³C1-C4 alkyl, halogen, CF₃And a phenyl group.

In another preferred embodiment, X is¹、X²Each independently selected from the group consisting of: chlorineAnd bromine.

The halogen refers to fluorine, chlorine, bromine or iodine.

In another preferred embodiment, M is¹And M²Each independently selected from the group consisting of: fe. Co, Ni, Pd, or combinations thereof.

In another preferred embodiment, M is¹、M²Each independently selected from the group consisting of: fe (II), Co (II), Ni (II), Pd (II), or combinations thereof.

The compound of formula I may be prepared by a process comprising the steps of:

in an inert solvent, introducing oxygen into the compound shown in the formula II under a strong alkali condition to prepare a compound III; reacting a compound of formula III with M, respectively, in an inert solvent₁X₁(or M)₁X₁·B)、M₂X₂(or M)₂X₂Reaction of the hydrate of B) to obtain the compound of formula I; wherein, M is₁X₁B or M₂X₂B is each M₁X₁Or M₂X₂A metal compound formed with a coordinating solvent B.

B is a coordinating solvent, such as DME (ethylene glycol dimethyl ether), THF (tetrahydrofuran), acetonitrile, ethanol, ethylene glycol, methanol, AcAc (acetylacetonato), DMF;

in the above formulas, M is selected from the following group: fe. Co, Ni, Pd, Pt, or a combination thereof;

base is an english abbreviation for strong Base selected from the group consisting of: n-butyllithium, lithium diisopropylamide, potassium diisopropylamide, sodium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, Et₃N, pyridine, or a combination thereof.

X is selected from the group consisting of: halogen, C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl;

the remaining groups are as defined above.

In another preferred embodiment, said complex of formula I may also be associated with a ligand selected from the group consisting of: triphenylphosphine, acetonitrile, tetrahydrofuran and C4-C16 heteroarene act to form a stable structure which exists in a solution or exists in a single solid state. After the complex is formed with the ligand, the function of the compound shown in the formula I as a catalyst is not influenced.

In another preferred embodiment, the C4-C16 heteroarene is pyridine.

In another preferred embodiment, the complex of the compound of formula II is formed by coordination of the M atom to a heteroatom in the ligand.

In another preferred embodiment, the oxidizing agent is selected from the group consisting of: benzoyl peroxide, air, ozone, oxygen, hydrogen peroxide, or a combination thereof. More preferably, oxygen or air is used as the oxidizing agent, which is effective.

In another preferred embodiment, the inert solvent is a weakly polar solvent.

In another preferred embodiment, the reaction is carried out in oxygen, air.

In another preferred embodiment, the reaction time is 2h to 15 days.

In another preferred example, the reaction time is 3 to 10 days.

In another preferred embodiment, the reaction is carried out under 0.01-10 MPa.

In another preferred embodiment, the reaction is carried out at 0.1 to 5 MPa.

In another preferred embodiment, the compound of formula I may be combined with a cocatalyst to prepare a catalyst composition. In another preferred embodiment, the cocatalyst is selected from the group consisting of: an alkylaluminum compound, an alkylaluminoxane, a weakly coordinating anion, or a combination thereof.

In another preferred embodiment, the alkylaluminoxane is methylaluminoxane.

Compounds of formula II and their preparation

The present invention also provides a compound having the structure of formula II:

Y₃selected from the group consisting of: hydrogen, substituted or unsubstituted C_1-C₁₀Substituted or unsubstituted aryl, substituted or unsubstituted C3-C10 cycloalkyl; wherein, the aryl group refers to phenyl, naphthyl, fluorenyl or anthryl; by substituted is meant that one or more hydrogen atoms on the group are replaced by a group selected from the group consisting of: OR (OR)³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen, phenyl;

Z¹selected from the group consisting of: substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; wherein, the aryl group refers to phenyl, naphthyl, fluorenyl or anthryl; the above-mentioned impuritiesAryl means furyl, thienyl, pyrrolyl, pyridyl or pyranyl; by substituted is meant that one or more hydrogen atoms on the group are replaced by a group selected from the group consisting of: OR (OR)³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen, phenyl;

or Y3, Z1 and adjacent N ═ C together form a ring

Structure;

Y¹、Y²is composed of

X¹、X²each independently selected from the group consisting of: halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl; wherein the content of the first and second substances,by substituted is meant that one or more hydrogen atoms on the group are replaced by a group selected from the group consisting of: OR (OR)³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen, phenyl, -CF₃；

in another preferred embodiment, the compound of formula II

Is a multi-substituted or unsubstituted five-membered or six-membered ring containing 1 to 3N, S, O or P atoms containing at least one N;

In another preferred embodiment, Z¹Selected from the group consisting of: substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; the aryl group is phenyl, naphthyl, fluorenyl or anthracenyl, and the heteroaryl group is furyl, thienyl, pyrrolyl, pyridyl or pyraneAnd (4) a base. The substitution is OR³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen, phenyl. Wherein said phenyl group comprises a substituted or unsubstituted phenyl group, said substitution being such that one or more hydrogen atoms on the phenyl ring are substituted by a group selected from the group consisting of: OR (OR)¹³C1-C4 alkyl, halogen, CF₃(ii) a Wherein, R is³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²Each independently selected from the group consisting of: C1-C10 alkyl, phenyl, C5-C16 heteroaryl; wherein 0 to 5 hydrogen atoms of said phenyl or heteroaryl group may be substituted by a substituent selected from the group consisting of: halogen, CF₃、OR¹³C1-C4 alkyl; r¹³Refers to C1-C4 alkyl.

The compound II of the invention can be prepared by the following routes:

preparation of symmetrically or asymmetrically substituted compound precursor II method 1 is shown below:

diethyl malonate and substituted β -amino alcohol are subjected to condensation reaction, an intermediate is obtained through recrystallization, and the intermediate is subjected to condensation cyclization by using TsCl and DMAP in dichloromethane as a solvent to obtain a final product.

Preparation of unsymmetrically substituted compound precursor II method 2 is shown below:

Preparation of symmetrically or asymmetrically substituted compound precursor II method 3 is shown below:

Compounds of formula III and their preparation

The invention provides a preparation method of a compound shown in formula III:

reacting a compound shown in a formula II with strong base in an inert solvent, and then introducing an oxidant to obtain a compound shown in a formula III;

in the above formulae, each group is as defined in the first aspect of the present invention.

In another preferred embodiment, the inert solvent is a weakly polar solvent.

In another preferred embodiment, the reaction is carried out in the presence of a base.

Co-catalyst

As used herein, the term "cocatalyst" refers to a substance that can be used with the catalyst of the present invention to catalyze olefin polymerization reactions and improve the reaction.

In the present invention, the preferred cocatalyst may be a neutral Lewis acid (Lewis acid) which abstracts X-from the metal M to form (WX)^-(ii) a When (WX)^-Is a weakly coordinating anion, W can transfer alkyl or hydrogen to the metal M, such as an alkylaluminum compound, especially Methylaluminoxane (MAO) or Modified Methylaluminoxane (MMAO); alternatively, a combination of two compounds can be used, one of which can transfer an alkyl or hydrogen to the metal M, such as an alkylaluminum compound, especially AlEt₃，AlMe₃，Al(i-Bu)₃The other can abstract X-from the metal M to form a weakly coordinating anion, such as a sodium or silver salt: na [ B (3,5- (CF)₃)₂C₆H₃)₄]、AgOSO₂CF₃Alkyl aluminum compounds or boranes B (C)₆F₅)₃。

Olefin polymerization catalyst

The invention provides a catalyst for catalyzing olefin polymerization reaction, which comprises an effective amount of a compound shown as a formula I or a complex thereof; and/or a compound shown as formula II, or a complex thereof. Or the catalyst is a compound of formula I or a complex thereof, and/or a compound of formula II or a complex thereof.

In another preferred embodiment, the catalyst can also be combined with an effective amount of a cocatalyst to form a catalyst composition for catalysis.

In another preferred embodiment, the alkylaluminoxane is methylaluminoxane.

In another preferred embodimentSaid weakly coordinating anion is selected from the group consisting of: [ B (3,5- (CF) ]₃)₂C₆H₃)₄]^-、^-OSO₂CF₃、((3,5-(CF₃)₂)C₆H₃)₄B^-Or a combination thereof.

Olefin polymerization

The present invention also provides an olefin polymerization reaction comprising: the above-described catalysts of the present invention are used alone or in the presence of a cocatalyst to catalyze the polymerization of olefins. The kind of the olefin is not limited, and the olefin may be ethylene, propylene, butylene, and other olefins commonly used in polymerization reactions, and may also be some olefins with large steric hindrance, higher 1-olefins (such as olefins with carbon number > 8), cyclic olefins, and the like.

In a preferred embodiment of the present invention, the polymerization reaction comprises: catalyzing the reaction with a compound of formula I or formula II of the present invention, or with a catalyst composition of the present invention; or in the presence of a catalytically effective amount of a catalyst selected from the group consisting of: a compound of formula I or a compound of formula II, a catalyst composition of the present invention, or a combination thereof.

In a preferred embodiment of the present invention, the olefin polymerization is a copolymerization of an olefin selected from the group consisting of a substituted or unsubstituted C2-C30- α -olefin, a substituted or unsubstituted C6-C30- α -olefin, a substituted or unsubstituted C5-C30-cyclic olefin, and the like.

Wherein the α -olefin is C3-C30 olefin with double bond at the end of molecular chain, preferably C3-C18 olefin, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-decene, 1-dodecene, 1-octadecene and their mixture.

The cyclic olefin refers to an olefin having a cyclic carbon skeleton in its structure and a double bond in the ring, such as cyclopentene, cyclohexene, norbornene, and cyclopentadiene diene, and a mixture thereof and the like.

In the present invention, a particularly preferred olefin polymerization is the copolymerization of a C2-C4 olefin with a polar monomer, wherein in another preferred embodiment, the polar monomer has the structure shown in formula a below:

wherein n is an integer of 0 to 48;

in another preferred embodiment, the olefin is a substituted or unsubstituted C3-C30 olefin.

In another preferred embodiment, the olefin is C containing polar groups₃～C₃₀1-olefin derivatives and cyclic olefin derivatives.

The polymerization comprises homopolymerization and copolymerization including oligomerization of the monomers.

The polymerization process of the present invention is not particularly limited, and any conventional technique in the art, such as slurry polymerization, loop polymerization, gas phase polymerization, or other forms of conventional polymerization processes, may be employed.

The polymerization is generally carried out in an inert solvent, such as a hydrocarbon, cyclic hydrocarbon or aromatic hydrocarbon. To facilitate reactor operation and polymerization product, the inert solvent is not particularly limited in kind, and hydrocarbons of less than 12 carbons may be used, such as solvents including (but not limited to) those selected from the group consisting of: propane, isobutane, n-pentane, 2-methylbutane, hexane, toluene, chlorobenzene, or combinations thereof.

The polymerization temperature is not particularly limited and is selected depending on the kind of polymerization, the apparatus, and the desired product. Preferably, the polymerization temperature may be maintained at-50 to 150 ℃ and 0 to 120 ℃ for good catalytic activity and productivity.

The pressure of the polymerization reaction is also not particularly limited, and may be varied from 0.01 to 10MPa, preferably from 0.1 to 10MPa, depending on the kind of the polymerization reaction, the equipment and the desired product. In a preferred embodiment of the invention, better reactor operating parameters and polymers are obtained by operating in the range of 0.1 to 3 MPa.

In the catalytic reaction of the present invention, a co-catalyst may also be added to further improve the catalyst efficiency. The cocatalyst can be an alkylaluminum compound, alkylaluminoxane or a weakly coordinating anion.

In another preferred embodiment, the alkyl aluminum compound is preferably AlEt₃，AlMe₃，Et₂AlCl or Al (i-Bu)₃。

In another preferred embodiment, the alkylaluminoxane is preferably Methylaluminoxane (MAO), MMAO (modified methylaluminoxane), MAO or MMAO is preferably selected from the products of akzo nobel.

In another preferred embodiment, the weakly coordinating anion is preferably [ B (3,5- (CF)₃)₂C₆H₃)₄]^-、^-OSO₂CF₃Or ((3,5- (CF)₃)₂)C₆H₃)₄B^-。

The catalyst and cocatalyst may be added to the system in any order to allow the polymerization to proceed. The ratio of catalyst to cocatalyst used for the polymerization can vary. The molar ratio of catalyst to cocatalyst is generally in the range of 1:1 to 10000, and can generally be in the range of 1:10 to 2000 in order to maintain the catalytic activity, polymer properties and production costs in a good range.

Olefin polymers

The invention also provides an olefin polymer prepared by the olefin polymerization reaction method.

In another preferred embodiment, the olefin polymer has one or more characteristics selected from the group consisting of:

(a) molecular weight is 1000 to 5,000,000 g/mol;

Preferably, the olefin polymer is a product of homopolymerization or copolymerization of a monomer selected from the group consisting of substituted or unsubstituted C2-C30 olefin, substituted or unsubstituted C6-C30 α -olefin, substituted or unsubstituted C5-C30 cyclic olefin, substituted or unsubstituted C with polar group₃～C₃₀And cyclic olefin derivatives of (a) or combinations thereof.

The main advantages of the invention include:

(1) the present invention provides a new kind of olefin polymerization catalyst and its preparation process. The olefin polymerization catalyst can be used for preparing olefin polymers with molecular weight in bimodal or multimodal distribution.

(2) The catalyst provided by the invention can be used for catalyzing homopolymerization and copolymerization of ethylene, α -olefin, cyclic olefin and the like including oligomerization independently or under the action of a cocatalyst, the catalytic efficiency is improved by 2-8 times at most compared with the general level of the prior art, and the catalytic activity is high.

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.

General procedure

All manipulations (including reaction, preparation and storage) were carried out under a dry inert atmosphere using standard Schlenk procedures.

Molecular weight M of the Polymer_wThe determination was carried out using a Waters Alliance GPC2000 in 1,2,4 trichlorobenzene (stream 1.0mL/min) at 135 ℃ using polystyrene standards.

The measurement of the melting point of the polymer is carried out on a Perkin-Elmer Pyris 1 type Differential Scanning Calorimetry (DSC), the temperature rise rate is 5 ℃/min, the temperature range is 20-200 ℃, and the melting point data of a second temperature rise curve is recorded.

Polymer and method of making same¹H-NMR spectra on a Varian XL-400MHz NMR spectrometer with D₄-o-dichlorobenzene as solvent, measured at 110 ℃. Comonomer insertion rate of¹The information provided by the H-NMR spectrum is calculated.

Polar monomer treatment method 1 (hereinafter referred to as T1)

In a Shlenck flask evacuated by baking at high temperature and replaced with argon, 96mmol of alkylaluminum (AlEt) were initially charged₃、AlMe₃、AlⁱBu₃Or AlEt₂Cl, both of which are products of Akzo Chemical company) or alkylaluminoxane (MMAO (1.9M in toluene) or MAO (1.6M in toluene), both of which are products of Akzo Chemical company) and 20mL of toluene, then 80mmol of polar monomer is slowly added dropwise to the solution at-78 ℃, after 2 hours of reaction, the solution is heated to room temperature for 12 hours of reaction, and a certain amount of toluene is added to prepare a toluene solution with the molar concentration of the polar monomer of 1.0mol/L for later use. The polar monomer M03 in the following examples was treated using this method.

Polar monomer treatment method 2 (hereinafter referred to as T2)

In the copolymerization of ethylene and polar monomer, the cocatalyst and the polar monomer are used for on-site reaction for 3 hours in a polymerization reaction kettle before the main catalyst is added.

Copolymerization process

50mL of toluene, a polar monomer treated or not by the methods T1 and T2, and MMAO (Akzo Chemical Co., 1.88mol/L heptane solution, hereinafter referred to as MMAO)) were sequentially added to a 250mL dry two-necked flask which was baked at a high temperature and evacuated and replaced with ethylene gas at room temperature, and the mixture was heated to a polymerization temperature and stirred for 10min, and a main catalyst was added to start copolymerization while maintaining the ethylene pressure at 0.1 MPa. After 10min of reaction, the ethylene air inlet valve is closed, the temperature is reduced to room temperature, the copolymer is precipitated in 300mL 5% (volume ratio) hydrochloric acid solvent, the mixture is stirred for 2h of reaction and then filtered, and then the pure solvent (100mL multiplied by 3) is used for washing and filtering, and the copolymer is obtained after vacuum drying at 50 ℃ until the weight is constant.

In example 1, the compound precursors II are all compounds of the following formula:

EXAMPLE 1 Synthesis of Compounds II-1-II-20

The other compound II-1 was obtained by the same preparation method as above (yield 62%); II-2 (yield 87%); II-3 (yield 72%); II-4 (89% yield); II-5 (yield 79%); II-6 (81% yield); II-7 (91% yield); II-8 (61% yield); II-9 (66% yield); II-10 (yield 54%); II-11 (yield 76%); II-12 (61% yield); II-13 (yield 57%); II-14 (yield 87%); II-15 (yield 76%); II-16 (68% yield); II-17 (81% yield); II-18 (56% yield); II-19 (64% yield); II-20 (yield 76%);

in example 2, the compound precursors III are all compounds of the following formula:

In another preferred embodiment, the inert solvent is a weakly polar solvent.

A preparation method of the compound III-1 comprises the following steps:

after compound II-10.182g (1mmol) was added to 10mL of a toluene solution and stirred together for 10min, the mixture was slowly added dropwise to a 1.2N-butyllithium toluene solution in a dry ice-acetone bath, and after completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. And introducing oxygen after 2h, oxidizing to obtain a product which is a yellow oily substance, and separating by column chromatography to obtain a compound III-1.

EXAMPLE 2 Synthesis of Compound III-2-III-20

The other compound II-2 was obtained in the same manner as in the above preparation of the compound III-1 (yield 54%); II-3 (43% yield); II-4 (yield 51%); II-5 (yield 36%); II-6 (43% yield); II-7 (56% yield); II-8 (yield 60%); II-9 (55% yield); II-10 (48% yield); II-11 (56% yield); II-12 (yield 51%); II-13 (yield 45%); II-14 (yield 51%); II-15 (44% yield); II-16 (yield 46%); II-17 (41% yield); II-18 (39% yield); II-19 (55% yield); II-20 (yield 57%);

EXAMPLE 3 Synthesis of Metal Compound I-1

To 20mL of toluene solvent were added 0.2g (1mmol) of the III-1 compound and 1.2 equivalents of Ni (ClO)₄)₂·6H₂O reaction to obtain 0.11g of the compound of formula I-1 with a yield of 22%;

elemental analysis, actually measured (calculated) C:20.25 (20.45); h:2.10 (2.29); n:5.43 (5.30).

EXAMPLE 4 Synthesis of complexes I-2 to I-20

The experimental procedure is essentially identical to that of example 3, except that I-1 is replaced by compounds III-2 to III-20, giving the other complex I-2 (yield 33%); i-3 (yield 26%); i-4 (yield 34%); i-5 (yield 45%); i-6 (41% yield); i-7 (yield 34%); i-8 (yield 57%); i-9 (47% yield); i-10 (yield 32%); i-11 (50% yield); i-12 (48% yield); i-13 (52% yield); i-14 (yield 46%); i-15 (yield 45%); i-16 (47% yield); i-17 (41% yield); i-18 (53% yield); i-19 (44% yield); i-20 (yield 51%).

The correspondence between the various starting materials and the products is shown in the following table.

Raw materials	Product of	Yield%
			II-2	I-2	33
II-3	I-3	26
			II-4	I-4	34

II-5	I-5	41
			II-6	I-6	34
II-7	I-7	45
			II-8	I-8	57
II-9	I-9	47
			II-10	I-10	32
II-11	I-11	50
			II-12	I-12	48
II-13	I-13	52
			II-14	I-14	46
II-15	I-15	45
			II-16	I-16	47
II-17	I-17	41
			II-18	I-18	53
II-19	I-19	44
			II-20	I-20	51

Part of the analytical data is as follows:

i-2 elemental analysis-measured (calculated) C:28.81 (28.62); h:3.55 (3.70); n:5.12 (5.14).

I-3 elemental analysis-measured (calculated) C:31.20 (31.41); h:4.01 (4.22); n:4.53 (4.88).

I-4 elemental analysis-measured (calculated) C:26.91 (37.05); h:2.87 (2.96); n:4.10 (4.12).

I-5 elemental analysis, actually measured (calculated) C:34.30 (34.33); h:4.12 (4.25); n:4.11 (4.21).

I-6 elemental analysis-measured (calculated) C:30.55 (30.56); h:1.52 (1.37); n:4.88 (4.75).

I-7 elemental analysis-measured (calculated) C:31.53 (31.41); h:4.20 (4.22); n:4.78 (4.88).

I-8 elemental analysis-measured (calculated) C:37.30 (37.29); h:5.56 (5.42); n:11.55 (11.60).

I-9 elemental analysis-measured (calculated) C:37.00 (36.89); h:2.21 (2.19); n:5.24 (5.06).

I-10 elemental analysis-measured (calculated) C:46.90 (46.55); h:4.23 (4.08); n:4.67 (4.72).

I-11 elemental analysis-measured (calculated) C:34.21 (34.22); h:2.56 (2.70); n:4.56 (4.70).

I-12 elemental analysis-measured (calculated) C:42.89 (42.78); h:5.12 (5.00); n:4.14(4.34)

I-13 elemental analysis-measured (calculated) C:46.10 (35.85); h:2.34 (2.53); n:4.41 (4.40).

I-14 elemental analysis-measured (calculated) C:37.03 (37.38); h:4.55 (4.48); n:4.11 (4.15).

I-15 elemental analysis-measured (calculated) C:33.29 (33.62); h:2.00 (1.76); n:4.89 (4.90).

I-16 elemental analysis, actually measured (calculated) C:39.77 (39.68); h:4.78 (4.76); n:4.55 (4.41).

I-17 elemental analysis, actually measured (calculated) C:40.71 (40.70); h:3.68 (3.69); n:4.00 (3.80).

I-18 elemental analysis-measured (calculated) C:39.12 (39.19); h:3.56 (3.45); n:4.55 (4.35).

I-19 elemental analysis-measured (calculated) C:47.23 (47.11); h:5.55 (5.65); n:4.12 (3.92).

I-20 elemental analysis, measured (calculated) C:47.57 (47.38); h:5.23 (5.11); n:4.10 (3.95).

Example 5 part of the catalyst catalyzed ethylene polymerization experiment

Under the ethylene atmosphere of 0.1Mpa, 100ml of toluene and MMAO (the molar ratio of MMAO to the catalyst is 1500) are sequentially added into a pumped and baked 250ml polymerization bottle, stirred vigorously, then placed in an oil bath at 30 ℃ and kept at a constant temperature for a certain time, the toluene solution of the catalysts I-1-I-2, I-6-I-7, I-10-I-13 and I-17-I-19 (5 mu mol) is added, and after the reaction is carried out for 10 minutes, the reaction is stopped by ethanol containing 5 percent of hydrochloric acid. The polymer is precipitated, filtered, washed and dried in vacuum at 50 ℃ to constant weight to obtain the polyethylene. The ethylene homopolymerization results are shown in table 1 below.

TABLE 1 results of ethylene polymerization catalyzed by catalysts I-1 to I-11

Note: a Cat: a catalyst; w: weight of polyethylene; activity: activity; m_w: a weight average molecular weight; m_w/M_n: molecular weight distribution.

The result shows that the catalyst system can catalyze the ethylene polymerization under normal pressure, and the activity can reach 10⁵g/mol. h, molecular weight 10⁵g/mol, and the branching degree is 19-28/1000C.

EXAMPLE 6 part of the catalyst experiments in the polymerization of ethylene catalyzed at high pressure

Under the ethylene atmosphere of 1.0Mpa, 100ml of toluene and MMAO (the molar ratio of MMAO to the catalyst is 1500) are sequentially added into a baked 350ml autoclave, stirred vigorously, then placed in an oil bath at 30 ℃, kept at a constant temperature for a certain time, added with toluene solutions (5 mu mol each) of the catalysts I-1, I-2, I-7, I-10 and I-18, reacted for 10 minutes, and then stopped by ethanol containing 5% hydrochloric acid. The polymer is precipitated, filtered, washed and dried in vacuum at 50 ℃ to constant weight to obtain the ethylene polymer. The ethylene polymerization results are shown in table 2 below.

TABLE 2 results of catalytic ethylene polymerization at high pressure for a portion of the catalysts

Note: a Cat: a catalyst; w: copolymer weight; activity: activity; m_w: a weight average molecular weight; m_w/M_n: molecular weight distribution.

The results show that the molecular weight of the obtained polymer can reach 10 relative to the normal pressure polymerization⁶g/mol, the degree of branching decreases.

Example 7 partial catalyst catalyzed propylene polymerization example

100mL of toluene and MMAO (the molar ratio of MMAO to the catalyst is 1500) are sequentially added into a 250mL polymerization bottle which is baked under the atmosphere of propylene of 0.1Mpa, stirred vigorously, then placed in an oil bath at 30 ℃, kept at a constant temperature for a certain time, catalysts I-1-I-2, I-10-I-12 and I-16-I-20(5 mu mol) of toluene solution are added, and after reaction for 10 minutes, the reaction is stopped by ethanol containing 5 percent of hydrochloric acid. The polymer is precipitated, filtered, washed and dried in vacuum at 50 ℃ to constant weight to obtain the polypropylene. The propylene homopolymerization results are shown in Table 3 below.

TABLE 3 partial catalyst catalyzed propylene polymerization results

The result shows that the catalyst system can catalyze propylene polymerization with higher activity.

EXAMPLE 8 partial catalysis of hexene polymerization experiments

100mL of toluene, 10mL of 1-hexene and MMAO (the molar ratio of MMAO to the catalyst is 1500) are added into a 250mL polymerization bottle which is roasted by pumping, the mixture is stirred vigorously, then the mixture is placed into an oil bath at the temperature of 30 ℃, the temperature is kept constant for a certain time, the toluene solutions of the catalysts I-2-I-3, I-9-12 and I-16-I-17(5 mu mol) are added, and after the reaction is carried out for 10 minutes, the reaction is stopped by ethanol containing 5 percent of hydrochloric acid. After washing, the mixture is dried in vacuum at 50 ℃ to constant weight to obtain the polyhexene. Results of hexene homopolymerization are given in table 4 below.

TABLE 4 results of hexene polymerization catalyzed by part of the catalysts

The results show that the catalyst system can well catalyze hexene polymerization.

Example 9I-2 catalysis of ethylene copolymerization with olefin experiments

100ml of toluene, 10mmol of olefin and MMAO (the molar ratio of MMAO to the catalyst is 1500) are added into a pumped and baked 250ml polymerization bottle under the ethylene atmosphere of 0.1Mpa, stirred vigorously, then placed in an oil bath at 30 ℃ and kept at a constant temperature for a certain time, a toluene solution of catalyst I-2(5 mu mol) is added, and after reaction for 10 minutes, the reaction is stopped by ethanol containing 5% hydrochloric acid. After washing, the polymer was obtained by vacuum drying at 50 ℃ to constant weight. The results of the copolymerization of ethylene with olefins are shown in Table 5 below.

TABLE 5I-2 results of the catalyst catalyzed copolymerization of ethylene and olefins

The results show that the catalyst system can well catalyze the copolymerization of olefin.

EXAMPLE 10 partial catalysis of ethylene with AlⁱBu₃Protected polar monomer copolymerization experiments

The comonomers used are all polar monomers M03, using AlⁱBu₃The treatment was carried out according to method T1 described in the general rules of the examples.

The copolymerization was carried out as described in the general rules of the examples, after completion of the polymerization, the copolymer was precipitated in 5% by volume ethanol hydrochloride and washed with ethanol (100 mL. times.3).

Other polymerization conditions, polymerization results, and copolymer characterization results are detailed in table 6.

TABLE 6 ethylene/M03 copolymerization data

From the above table data it can be concluded that: the catalyst can catalyze ethylene and Al under normal pressureⁱBu₃The activity of the protected monomer M03 can reach 10⁵g/mol. h, molecular weight 10⁵g/mol, polar monomer insertion rate of 1.8-4.1 mol%.

EXAMPLE 11 partial catalysis of the copolymerization of ethylene with TBS or TMS protected polar monomers experiment

The comonomers used are all polar monomers M18, 19, 20, 21, 22, 23.

The copolymerization was carried out as described in the general rules of the examples, with 5. mu. mol of catalyst, MMAO as cocatalyst and a polymerization time of 10min, after completion of the polymerization, the copolymer was precipitated in 5% by volume of ethanol hydrochloride and washed with ethanol (100 mL. times.3).

Other polymerization conditions, polymerization results, and copolymer characterization results are detailed in table 7.

TABLE 7 ethylene/polar monomer copolymerization data

From the above table data it can be concluded that: the catalyst can well catalyze the copolymerization of ethylene and TBS or TMS protected monomers under normal pressure, and the activity can reach 10⁵g/mol. h, molecular weight 10⁵g/mol, polar monomer insertion rate of 1.3-5.1 mol%.

EXAMPLE 12 partial catalysis of the catalyst for copolymerization of ethylene with Co-catalyst protected polar monomers

The polar monomer was treated according to method T2 described in the general rules of the examples.

The copolymerization was carried out as described in the general rules of the examples, with 5. mu. mol of procatalyst, MMAO as cocatalyst, 10mmol of polar monomer, cocatalyst and polar monomer mixed and stirred for 3h before polymerization, at 30 ℃ for 10min, after completion of polymerization, the copolymer was precipitated in 5% (volume ratio) ethanol hydrochloride, and washed with ethanol (100 mL. times.3).

Other polymerization conditions, polymerization results, and copolymer characterization results are detailed in table 8.

TABLE 8 ethylene/polar monomer copolymerization data

From the above table data it can be concluded that: after the polar monomer and MMAO are pretreated, the catalyst can well catalyze the copolymerization of ethylene and various monomers under normal pressure.

EXAMPLE 13 partial catalysis of copolymerization of ethylene with unprotected polar monomers

The comonomer is directly copolymerized with ethylene without protection.

The copolymerization was carried out as described in the general rules of the examples, MMAO as cocatalyst, at a polymerization temperature of 30 ℃ in 50mL of solvent, 5min later in addition of polar monomer, stirring for 10min, then in addition of the catalyst solution dissolved beforehand, polymerization for 10min, after completion of the polymerization, precipitation of the copolymer in 5% (by volume) ethanol hydrochloride, and washing with ethanol (100 mL. times.3).

Other polymerization conditions, polymerization results, and copolymer characterization results are detailed in table 9.

TABLE 9 ethylene/polar monomer copolymerization data

From the above table data it can be concluded that: the catalyst can well catalyze the copolymerization of ethylene and unprotected monomers under normal pressure, and the activity of the catalyst is slightly reduced compared with that of the protected polar monomer; the insertion of some monomers which are difficult to copolymerize under normal conditions, such as M01, can also be achieved.

EXAMPLE 14 partial catalysis of copolymerization of propylene with polar monomers experiment

The comonomer is directly copolymerized with propylene without protection.

Other polymerization conditions, polymerization results, and copolymer characterization results are detailed in table 10.

TABLE 10 copolymerization data of propylene/polar monomer

The result shows that the catalyst can catalyze the copolymerization of propylene and unprotected monomers under normal pressure.

EXAMPLE 15 partial catalysis of copolymerization of 1-butene with polar monomers experiment

The comonomer is directly copolymerized with 1-butene without protection.

Other polymerization conditions, polymerization results, and copolymer characterization results are detailed in table 11.

TABLE 11.1 butene/polar monomer copolymerization data

The result shows that the catalyst can well catalyze the copolymerization of 1-butene and unprotected monomers under normal pressure.

EXAMPLE 16 partial catalysis of polymerization of ethylene with polar monomers under high pressure

Under the ethylene atmosphere of 1.0Mpa, 100ml of toluene and MMAO (the molar ratio of MMAO to the catalyst is 3000) are sequentially added into a baked 350ml autoclave, the mixture is vigorously stirred, then the autoclave is placed in an oil bath at 30 ℃, the temperature is kept constant for a certain time, 10 mu m of protected polar monomer is added, toluene solutions (5 mu mol each) of catalysts I-2, I-3, I-10, I-13 and I-20 are added, and after the reaction is carried out for 10 minutes, the reaction is stopped by ethanol containing 5 percent of hydrochloric acid. The polymer is precipitated, filtered, washed and dried in vacuum at 50 ℃ to constant weight to obtain the ethylene polymer. The ethylene polymerization results are shown in the table below.

TABLE 12 results of catalytic ethylene polymerization at high pressure for a portion of the catalysts

The results show that the molecular weight of the obtained polymer can reach 10 relative to the normal pressure polymerization⁶g/mol, the insertion rate is obviously reduced.

All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.

Claims

1. A compound of formula I:

in the formula:

is a coordinate bond;

Z₁selected from the group consisting of: substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; wherein, the aryl group refers to phenyl, naphthyl, fluorenyl or anthryl; the heteroaryl refers to furyl, thienyl, pyrrolyl, pyridyl or pyranyl; by substituted is meant that one or more hydrogen atoms on the group are replaced by a group selected from the group consisting of: OR (OR)³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen, phenyl;

or Y₃、Z₁And adjacent N ═ C form a ring

Structure;

is a 5-12 membered heterocyclic ring containing 1-3 heteroatoms; wherein the heteroatom is selected from the group consisting of: n, S, O or P;

Y₁、Y₂is composed of

One or more optional substituents on the ring, and said Y₁、Y₂Each independently selected from the group consisting of: hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted C3-C10 cycloalkyl;

M¹、M²each independently selected from the group consisting of: ni;

X¹、X²each independently selected from the group consisting of: halogen, ClO₄ ^-Substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted phenyl; wherein said substitution is one or more hydrogen atoms on the group substituted with a group selected from the group consisting of: OR (OR)³、SR⁴、NR⁵R⁶，PR⁷R⁸Or P (O) R⁹R¹⁰、SiR¹²C1-C4 alkyl, halogen, phenyl, -CF₃；

and the compounds of formula I are charge balanced.

2. The compound of claim 1,

is a 5-7 membered heterocyclic ring containing 1-3 heteroatoms.

3. A method of making a compound of claim 1, comprising the steps of:

wherein, M is¹X¹B or M²X²B is each M¹X¹Or M²X²A metal compound formed with a coordinating solvent B; the definition of each group is as defined in claim 1.

4. The method according to claim 3, wherein the coordinating solvent B is selected from the group consisting of: DME (ethylene glycol dimethyl ether), THF (tetrahydrofuran), acetonitrile, ethanol, ethylene glycol, methanol, AcAc (acetylacetonato), DMF, or a combination thereof.

5. A method according to claim 3, characterized in that the method comprises the steps of:

6. The method of claim 5, wherein the method comprises the steps of:

or the method comprises the steps of:

(b2) reacting with a compound of formula IIe to give a compound of formula IIg;

or Y₄、Y₅And two carbon atoms connected with the substituted or unsubstituted benzene ring; or together form a substituted or unsubstituted 5-12 membered heteroaromatic ring; wherein said substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of: hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted C3-C10 cycloalkyl;

the remaining groups are as defined in claim 3.

7. The method of claim 6, wherein Y is₄、Y₅And two carbon atoms connected with the same form a substituted or unsubstituted 5-7 membered heteroaromatic ring.

8. Use of a compound according to claim 1, wherein the compound (a) is used as a catalyst for catalyzing the polymerization of olefins; or (b) for the preparation of an olefin polymerization catalyst composition.

9. An olefin polymerization catalyst composition comprising a catalytically effective amount of a compound of formula I as described in claim 1.

10. A process for preparing an olefin polymer, comprising: subjecting an olefin to an olefin polymerization reaction in the presence of a catalytically effective amount of a catalyst to obtain an olefin polymer;

wherein the catalyst is selected from the group consisting of: the compound of claim 1, the catalyst composition of claim 9, or a combination thereof.