CN118005828A - Transition metal catalyst and preparation and application thereof - Google Patents

Abstract

The invention discloses a transition metal catalyst and preparation and application thereof. Specifically, the invention discloses a novel zirconium and hafnium complex shown in a formula I and a catalytic system containing the complex. Under the action of a catalyst composition formed by the catalyst system and the cocatalyst, ethylene homo-polymerization or ethylene and monomer copolymerization of alpha-olefin, cyclic olefin and the like can be efficiently catalyzed, the catalytic activity is high, the thermal stability is good, and the using amount of the cocatalyst in the catalyst composition is low.

Description

Transition metal catalyst and preparation and application thereof

Technical Field

The invention relates to the technical field of polyolefin, in particular to a preparation method and application of a transition metal catalyst, and in particular relates to application in olefin polymerization.

Background

Olefin solution polymerization catalysis techniques have been commercially developed for the preparation of different types of high performance polyolefins, such as linear low density polyethylene, polyolefin elastomers, ethylene/1-octene block copolymers, and the like. Solution polymerization processes generally require higher polymerization temperatures to reduce energy consumption and optimize operating efficiency, thereby significantly reducing production costs. However, high reaction temperatures also cause problems such as deactivation of the catalyst at high temperatures, reduction of the molecular weight of the polymer, etc. Therefore, it is of great importance to develop an olefin polymerization catalyst and a polymerization reaction system which are excellent in high temperature heat stability and in which the molecular weight of the polymer is maintained at high temperature.

Currently, there are a variety of group IV metal catalysts used in the art to prepare high performance polyolefins, for example, the American Dow chemical company discloses hafnium complexes containing polyvalent aryloxy or arylthio ethers as catalysts to achieve high Wen Yixi, propylene and other olefin copolymerizations; the American Dow chemical company discloses that single negative ion dinitrogen coordinated zirconium or hafnium complex containing imine is used as a catalyst to realize the copolymerization of high Wen Yixi, propylene and other olefins; the company Symyx Technologies discloses that the pyridine ethylamine fourth group metal complex is used as a catalyst to realize high Wen Yixi, propylene homopolymerization, copolymerization with other olefins and the like. The national institute of sciences Shanghai organic chemistry discloses that ONX (X=O, N, P, S, se) tridentate ligand group IV metal complexes based on ketimines and salicylaldimines are used as catalysts to achieve copolymerization of ethylene with other olefins, and the catalysts exhibit excellent high temperature polymerization properties. However, such complexes are not effective for the preparation of polyolefin elastomers nor form stable catalysts with group IV metals.

Accordingly, there is a great need in the art to provide a class of metal complex catalysts suitable for the preparation of high performance polyolefins, particularly polyolefin elastomers.

Disclosure of Invention

The invention aims to provide an olefin polymerization catalyst which is simple to prepare, high in catalytic activity, good in thermal stability and suitable for preparing polyolefin by high-temperature solution polymerization.

The invention also provides an olefin polymerization catalyst composition, and the usage amount of the cocatalyst is low.

It is a further object of the present invention to provide a process for preparing polyolefins, in particular for ethylene polymerization, ethylene/alpha-olefin copolymerization, exhibiting very good catalytic activity and thermal stability.

In a first aspect of the present invention, there is provided a metal complex represented by formula I:

Wherein:

-is a single bond;

the → is a coordination bond;

M is selected from the group consisting of: zirconium, hafnium;

X is selected from the group consisting of: halogen, C1-C4 alkyl, C2-C6 alkenyl, allyl A benzyl group;

m is 3 or 4;

and in formula I, the absolute value of the total number of negative charges carried by all ligands is the same as the absolute value of positive charges carried by metal M in the formula (i.e., the complex is charge balanced);

Y ¹ is selected from the group consisting of: hydrogen, C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 haloalkyl, C3-C8 halocycloalkyl, unsubstituted or substituted phenyl;

Y ² is selected from the group consisting of: CR ₄R₅、NR₆, O, or S, wherein R ₄、R₅、R₆ are each independently hydrogen, C1-C4 alkyl, or haloalkyl;

Or Y ¹ and Y ², and the C-C bond to which both are attached, together form an unsubstituted or substituted 5-12 membered carbocyclic or heterocyclic ring;

Is an unsubstituted or substituted 5-7 membered monocyclic, or 8-20 membered bicyclic or tricyclic group, wherein said bicyclic or tricyclic group includes a 5-7 membered monocyclic structure (i.e., the bicyclic or tricyclic structure is formed by fusing 1-2 rings to said 5-7 membered monocyclic ring); the 5-7 membered monocyclic ring contains 1-3N, O or S atoms and contains at least one N;

Y ³ is one or more optional substituents on the 5-7 membered monocyclic or the 5-7 membered monocyclic containing bicyclic or tricyclic groups, and each Y ³ is independently selected from the group consisting of: hydrogen, C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl;

z is selected from the group consisting of: C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl;

Said substitution means that said group has 1 to 5 substituents selected from the group consisting of: C1-C4 alkyl, C1-C4 haloalkyl, halogen, nitro, cyano 、CF₃、-O-R₁、-N(R₂)₂、-Si(R₃)₃、-CH₂-O-R₈、-SR₉, or-CH ₂-S-R₁₀, wherein R ₁、R₂、R₃ is each independently C1-C4 alkyl or haloalkyl; and R ₈、R₉、R₁₀ is C1-C8 alkyl or phenyl, respectively.

In a further preferred embodiment of the present invention,Selected from the group consisting of:

Wherein Y ⁴、Y⁵、Y⁶、Y⁷、Y⁸、Y⁹、Y¹⁰ and Y ¹¹ are each independently H, halogen, C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl, -O-R ₇、-CH₂-O-R₈、-SR₉ or-CH ₂-S-R₁₀, wherein R ₇、R₈、R₉ and R ₁₀ are each independently C1-C8 alkyl, unsubstituted or substituted phenyl; y ¹² is H, C-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl; or any two groups selected from Y ⁴、Y⁵、Y⁶、Y⁷、Y⁸、Y⁹、Y¹⁰ and Y ¹¹ located on the same ring atom or on adjacent ring atoms together with the ring atoms to which they are attached form a 3-to 8-membered substituted or unsubstituted carbocyclic or heterocyclic ring.

In another preferred embodiment, the C-C bonds to which Y ¹ and Y ² are attached together form an unsubstituted or substituted C6-C8 ring, wherein "substituted" is as defined above.

In another preferred embodiment, Y ¹ is selected from the group consisting of: C1-C4 alkyl, C3-C6 cycloalkyl, C1-C8 haloalkyl, C1-C8 halocycloalkyl, unsubstituted or substituted phenyl; or Y ¹ together with Y ² and the C-C bond to which they are attached form an unsubstituted or substituted 5-to 8-membered carbocyclic or heterocyclic ring.

In another preferred embodiment, the compound has the formula:

Wherein,

Y ³ or Z is as defined above;

n is 0, 1, 2 or 3;

Is an unsubstituted or substituted 5-7 membered monocyclic ring, or a bicyclic or tricyclic group containing said 5-7 membered monocyclic ring;

g ¹、G²、G³ and G ⁴ are each H, halogen, C1-C8 alkyl, C1-C8 cycloalkyl, C1-C8 haloalkyl, silicon-based, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl, -O-R ₇、-CH₂-O-R₈、-SR₉ or-CH ₂-S-R₁₀, wherein R ₇、R₈、R₉ and R ₁₀ are each C1-C8 alkyl, unsubstituted or substituted phenyl; wherein the term "substituted" is as defined above.

In another preferred embodiment, saidHas a structure shown in the following formula:

wherein p is selected from 1,2,3 or 4;

y ² is selected from the group consisting of: NR ₆, O, or S, wherein R ₆ is hydrogen, C1-C4 alkyl, or haloalkyl;

Y ⁴ and Y ⁵ are each independently selected from the group consisting of: H. halogen, C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl; or Y ⁴、Y⁵ together with the ring atoms to which it is attached form a 3-to 8-membered, substituted or unsubstituted, carbocyclic or heterocyclic ring.

In another preferred embodiment, saidIs a spiro or fused ring, preferably having any one of the structures:

Wherein,

Each n is 1, 2, 3 or 4, respectively;

y ¹、Y², and Z are as defined in the first aspect of the invention;

Y ⁴、Y⁵ is independently H, halogen, C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl, -O-R ₇、-CH₂-O-R₈、-SR₉, or-CH ₂-S-R₁₀, wherein R ₇、R₈、R₉ and R ₁₀ are independently C1-C8 alkyl, unsubstituted or substituted phenyl; wherein Y ⁴ and Y ⁵ cannot be both halogen, -O-R ₇ or-SR ₉.

In another preferred embodiment, Z is unsubstituted or substituted phenyl, wherein the substituted phenyl has 1 to 5 substituents selected from the group consisting of: C1-C4 alkyl and C1-C4 haloalkyl, halogen, nitro, cyano 、CF₃、-O-R₁、-N(R₂)₂、-Si(R₃)₃、-CH₂-O-R₈、-SR₉ or-CH ₂-S-R₁₀, wherein R ₁、R₂、R₃ is each independently C1-C4 alkyl or haloalkyl; and R ₈、R₉ and R ₁₀ are each C1-C8 alkyl or phenyl;

and up to one nitro or cyano group on the substituted phenyl group;

Preferably, Z is selected from the group consisting of:

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

In a second aspect, the invention provides a method for synthesizing a metal complex of formula I according to the first aspect of the invention, which is characterized in that ligand II of the following structural formula and a metal compound react for 5-30 hours in a molar ratio of 1-3:1 in an organic solvent at a temperature of 50-100 ℃ to obtain the complex of the first aspect of the invention;

The ligand has the structural formula as follows:

wherein: y ¹、Y²、Y³, Z are the same as described in the first aspect above;

The metal compound refers to MX _m or MX _(m-1); wherein M and X are the same as described above; m is 3 or 4.

In a third aspect of the invention there is provided the use of an olefin polymerisation catalyst according to the first aspect of the invention, for catalysing the polymerisation of olefins by the action of an optional cocatalyst.

In another preferred embodiment, the catalytic olefin polymerization is olefin homo-or co-polymerization, wherein the homo-polymerization is ethylene, alpha-olefin, or C3-C20 cycloolefin homo-polymerization; the copolymerization refers to the copolymerization of ethylene and alpha-olefin; the alpha-olefin refers to C3-C18 alpha-olefin.

In another preferred embodiment, the cocatalyst is selected from the group consisting of: boron compounds, alkylaluminum compounds, alkylaluminoxane.

In another preferred embodiment, the boron compound is selected from triphenylcarbon tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-bishexadecylammonium tetrakis (pentafluorophenyl) borate or tris (pentafluorophenyl) borane; the alkyl aluminum compound is selected from AlMe ₃,AlEt₃ or Al (i-Bu) ₃; said; the alkylaluminoxane is selected from Methylaluminoxane (MAO) and Modified Methylaluminoxane (MMAO).

In a fourth aspect of the present invention, there is provided a process for the polymerisation of olefins, said process comprising step (a) or step (b):

step (a): catalyzing the homo-or copolymerization of olefins in the presence of a catalyst according to the first aspect of the invention and optionally a cocatalyst;

step (b): catalyzing olefin to carry out homopolymerization or copolymerization in the presence of ligand and metal compound as shown in formula II;

wherein: y ¹、Y²、Y³, Z are the same as described in the first aspect above;

The metal compound refers to MX _m or MX _(m-1); wherein M and X are the same as described above; m is 3 or 4;

The homo-polymerization is ethylene, alpha-olefin or C3-C20 cycloolefin homo-polymerization; the copolymerization refers to the copolymerization of ethylene and alpha-olefin; the alpha-olefin refers to C3-C18 alpha-olefin.

In another preferred embodiment, when m is 4, the method is performed using step (b).

In a fifth aspect of the present invention, there is provided a metal ligand having a structure represented by formula II:

Y ¹ is selected from the group consisting of: hydrogen, C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 haloalkyl, C3-C8 halocycloalkyl, unsubstituted or substituted phenyl;

Y ² is selected from the group consisting of: CR ₄R₅、NR₆, O, or S, wherein R ₄、R₅、R₆ are each independently hydrogen, C1-C4 alkyl, or haloalkyl;

Or Y ¹ and Y ², and the C-C bond to which both are attached, together form an unsubstituted or substituted 5-12 membered carbocyclic or heterocyclic ring;

Is an unsubstituted or substituted 5-7 membered monocyclic, or 8-20 membered bicyclic or tricyclic group, wherein said bicyclic or tricyclic group includes a 5-7 membered monocyclic structure (i.e., the bicyclic or tricyclic structure is formed by fusing 1-2 rings to said 5-7 membered monocyclic ring); the 5-7 membered monocyclic ring contains 1-3N, O or S atoms and contains at least one N;

Y ³ is one or more optional substituents on the 5-7 membered monocyclic or the 5-7 membered monocyclic containing bicyclic or tricyclic groups, and each Y ³ is independently selected from the group consisting of: hydrogen, C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl;

z is selected from the group consisting of: C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl;

Said substitution means that said group has 1 to 5 substituents selected from the group consisting of: C1-C4 alkyl, C1-C4 haloalkyl, halogen, nitro, cyano 、CF₃、-O-R₁、-N(R₂)₂、-Si(R₃)₃、-CH₂-O-R₈、-SR₉, or-CH ₂-S-R₁₀, wherein R ₁、R₂、R₃ is each independently C1-C4 alkyl or haloalkyl; and R ₈、R₉、R₁₀ is C1-C8 alkyl or phenyl, respectively.

In another preferred embodiment, the metal ligand has a structure selected from the group consisting of:

It is understood that within the scope of the present invention, the above-described technical features of the present invention and technical features specifically described below (e.g., in the examples) may be combined with each other to constitute new or preferred technical solutions. And are limited to a space, and are not described in detail herein.

Drawings

FIG. 1 is a diagram of the structure of a single crystal of complex C2;

FIG. 2 is a diagram showing the structure of single crystals of complex C3.

Detailed Description

The present inventors have conducted extensive studies to provide a complex suitable as a catalyst for producing polyolefin elastomers. The complex is formed by an amine-imine compound and trivalent or tetravalent metal salt and metal alkyl compound, wherein the metal salt or metal alkyl compound contains metal selected from the following groups: zirconium, hafnium, or a combination thereof.

In a first aspect of the present invention, there is provided an olefin polymerization catalyst I having the general formula shown below:

Wherein the arrow represents an optional electron donating bond between the nitrogen atom and M;

m is a metal selected from the fourth subgroup of the periodic Table of the elements, in particular zirconium, hafnium or a combination thereof;

X is independently halogen, C1-C4 alkyl, C2-C6 alkenyl, allyl Or benzyl; m is 3 or 4; preferably, X is benzyl.

Y ¹ is independently hydrogen, C1-C8 alkyl or C1-C8 haloalkyl, unsubstituted or substituted phenyl;

Y ² is CR ₄R₅、NR₆, O or S, R ₄、R₅、R₆ is each independently H, C-C4 alkyl or haloalkyl;

Or Y ¹ and Y ², together with the C-C bond to which they are attached, form together an unsubstituted or substituted 5-12 membered ring (e.g., together forming a ring Wherein the dashed line represents a chemical bond or no);

Is an unsubstituted or substituted 5-7 membered monocyclic ring, or a bicyclic or tricyclic group containing said 5-7 membered monocyclic ring, which is co-formed with Y ², wherein the 5-7 membered monocyclic ring contains 1-3N, O or S atoms and contains at least one N;

Y ³ is one or more optional substituents on the 5-7 membered monocyclic or the 5-7 membered monocyclic-containing bicyclic or tricyclic groups, each Y ³ is independently hydrogen, C1-C8 alkyl or C1-C8 haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl;

z is C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl;

Wherein, unless otherwise specified, "substituted" as defined in the above definitions means that the group has 1 to 5 substituents selected from the group consisting of: C1-C4 alkyl and C1-C4 haloalkyl, halogen, nitro, cyano 、CF₃、-O-R₁、-N(R₂)₂、-Si(R₃)₃、-CH₂-O-R₈、-SR₉ or-CH ₂-S-R₁₀, wherein R ₁、R₂、R₃ is each independently C1-C4 alkyl or haloalkyl; and R ₈、R₉ and R ₁₀ are each C1-C8 alkyl or phenyl.

In a further preferred embodiment of the present invention,May be optically active or racemic.

In another preferred embodiment, inWherein N is ortho to the C-carbon atom and the C-atom has one or two non-hydrogen substituents.

In another preferred embodiment, the non-hydrogen substituents are selected from the group consisting of: C3-C8 alkyl (preferably branched alkyl) or C3-C8 haloalkyl (preferably halo branched alkyl), unsubstituted or substituted phenyl, unsubstituted or substituted benzyl.

In another preferred embodiment, the term "co-formed with Y ²" includes co-formed with the entire Y ² or with a portion (mole) of Y ².

In a further preferred embodiment of the present invention,Selected from the group consisting of:

Wherein Y ⁴、Y⁵、Y⁶、Y⁷、Y⁸、Y⁹、Y¹⁰ and Y ¹¹ are each independently H, halogen, C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl, -O-R ₇、-CH₂-O-R₈、-SR₉ or-CH ₂-S-R₁₀, wherein R ₇、R₈、R₉ and R ₁₀ are each independently C1-C8 alkyl, unsubstituted or substituted phenyl; y ¹² is H, C-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl.

In a further preferred embodiment of the present invention,For/>Wherein 1-3 substituents in Y ⁴、Y⁵、Y⁶ and Y ⁷ are H, C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl, and 1-3 substituents are H, halogen, C1-C4 alkyl and C1-C4 haloalkyl.

In a further preferred embodiment of the present invention,For/>Wherein 1-3 substituents in Y ⁴、Y⁵、Y⁶、Y⁷ and Y ¹² are H, C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl, and 1-3 substituents are H, halogen, C1-C4 alkyl and C1-C4 haloalkyl.

In another preferred embodiment, Y ¹² is not halogen.

In another preferred embodiment, Y ¹ and Y ² may form together with the C-C bond to which they are attached an unsubstituted or substituted C6-C8 ring, wherein "substituted" is as defined above.

In another preferred embodiment, the compound has the formula:

Wherein Y ³ or Z is as defined in the first aspect of the invention;

n is 0, 1, 2 or 3;

is an unsubstituted or substituted 5-7 membered monocyclic ring, or a bicyclic or tricyclic group containing said 5-7 membered monocyclic ring; /(I)

G ¹、G²、G³ and G ⁴ are each H, halogen, C1-C8 alkyl, C1-C8 haloalkyl, silicon-based, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl, -O-R ₇、-CH₂-O-R₈、-SR₉ or-CH ₂-S-R₁₀, wherein R ₇、R₈、R₉ and R ₁₀ are each C1-C8 alkyl, unsubstituted or substituted phenyl; wherein the term "substituted" is as defined above.

In another preferred embodiment, the bicyclic ring containing the 5-7 membered monocyclic ring is a spiro ring or a fused ring, preferably the compound has any one of the structures:

Wherein,

Each n is 1, 2, 3 or 4, respectively;

y ¹、Y² and Z are as defined in the first aspect of the invention;

Y ⁴、Y⁵ is independently H, halogen, C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl, -O-R ₇、-CH₂-O-R₈、-SR₉, or-CH ₂-S-R₁₀, wherein R ₇、R₈、R₉ and R ₁₀ are independently C1-C8 alkyl, unsubstituted or substituted phenyl; wherein Y ⁴ and Y ⁵ cannot be both halogen, -O-R ₇ or-SR ₉.

In another preferred embodiment, each chiral center (preferably C carbon) in the compounds of formula I is of the R and/or S type.

In another preferred embodiment, wherein the C atom on the 5-7 membered monocyclic ring attached to Y ⁴ and/or Y ⁵ is in the R and/or S form.

In another preferred embodiment, Z is unsubstituted or substituted phenyl, wherein the substituted phenyl has 1 to 5 substituents selected from the group consisting of: C1-C4 alkyl and C1-C4 haloalkyl, halogen, nitro, cyano 、CF₃、-O-R₁、-N(R₂)₂、-Si(R₃)₃、-CH₂-O-R₈、-SR₉ or-CH ₂-S-R₁₀, wherein R ₁、R₂、R₃ is each independently C1-C4 alkyl or haloalkyl; and R ₈、R₉ and R ₁₀ are each C1-C8 alkyl or phenyl; and at most one nitro or cyano group can be present on the substituted phenyl group.

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

in another preferred embodiment, any one of ,Y¹、Y²、Y³、Y⁴、Y⁵、Y⁶、Y⁷、Y⁸、Y⁹、Y¹⁰、Y¹¹、Y¹²、Z、R₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉ and R ₁₀ in the compounds is a group corresponding to the particular compound of the invention.

Preparation of complexes of formula I

Complexing a trivalent or tetravalent metal salt or metal alkyl compound (e.g. ZrCl ₄、ZrBn₄、HfCl₄ or HfBn ₄) in an inert solvent to obtain, after purification, a complex of formula i according to the first aspect of the invention:

the trivalent or tetravalent metal salt or metal alkyl compound has a structure shown in MX _m or MX _(m-1),

Wherein when each X is independently C1-C4 alkyl, C2-C6 alkenyl, allylWhen benzyl (i.e., is a metal alkyl compound), the conditions for preparing the complex of formula I satisfy the following conditions: /(I)

The reaction temperature in the step can be 50-100 ℃; the reaction time can be 5-30 h; the molar ratio of the compound of formula II to the metal alkyl is preferably 1-3:1.

Preferably, the reaction is carried out under an inert atmosphere (e.g., nitrogen, argon, helium atmosphere); more preferably, the reaction is carried out under anhydrous and anaerobic conditions (e.g., water content. Ltoreq.0.1%).

In another preferred embodiment, X may also independently be halogen, and the preparation of the complex of formula I more specifically comprises the steps of:

(a) Reacting a compound shown in a formula II with sodium hydride to generate sodium salt by taking tetrahydrofuran as a solvent;

(b) And then carrying out a complex reaction between the sodium salt and the metal salt, and purifying after the reaction is finished to obtain the complex of the formula I.

Preferably, the step reaction is carried out under almost anhydrous conditions (e.g., water content. Ltoreq.0.1%); in another preferred embodiment, the step reaction is carried out under an inert atmosphere (e.g., nitrogen).

In the method, the molar ratio of the compound of the formula II to sodium hydride is 1: (2-3); in the step (a), the reaction temperature may be-78℃to 25 ℃.

In the process according to the invention for preparing the complexes of the formula I, in step (a), the reaction time is from 6 to 24 hours, preferably from 8 to 12 hours, for example 8, 10 or 12 hours.

In the process, the molar ratio of the compound of formula II to the metal salt is most preferably 1:1, a step of; the temperature of the reaction in step (b) may be from-78℃to 25℃and the time may be from 6 to 24 hours, preferably from 8 to 12 hours, for example 8 hours, 10 hours or 12 hours.

In a preferred embodiment, the compounds of the formula II as starting materials can be prepared by the following process:

And (3) using absolute methanol as a solvent to hydrogenate the compound A to obtain the formula II.

Wherein the reaction temperature of the step is preferably 20-50 ℃, and the reaction time can be 10 min-2 h. In a preferred embodiment, after the step is finished, the method further comprises the step of separating and purifying the product by using a silica gel short column; the eluent can be diethyl ether.

The preparation method of the compound A required in the preparation process of the complex of the formula II is shown in Chinese patent: CN105503763a/PCT patent: disclosed in WO 2016/058559.

Catalyst composition

The catalyst composition of the invention comprises a main catalyst and a cocatalyst. The main catalyst is shown as a formula I; the promoter is a reagent capable of promoting the catalytic reaction and can be an alkyl aluminum compound, alkyl aluminoxane or boron compound.

The alkyl aluminum compound described in the present invention includes any compound containing a carbon-aluminum bond, including Methylaluminoxane (MAO), MMAO, triethylaluminum, tripropylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, etc. Wherein the molar ratio of aluminum in the cocatalyst to metal in the catalyst is 1: 2-1000: 1.

The boron compound of the present invention may include any of carbon-boron bond-containing compounds, including tri-substituted ammonium salts, such as: n, N-dimethylanilinium tetrakis (pentafluorophenyl) borate; boron-based compounds containing carbonium ions, such as: triphenylcarbon tetrakis (pentafluorophenyl) borate; boron-based compounds comprising lewis acids, such as: tris (pentafluorophenyl) borane.

Process for the preparation of polyolefins

The present invention also provides a process for the preparation of polyolefins, generally described as polymerization under coordination polymerization conditions in the presence of a combination of the foregoing catalysts, using the catalysts and compounds of the present invention in solution, high pressure polymerization processes which may be carried out in batch, semi-batch, or continuous mode, to polymerize one or more monomers, particularly ethylene and alpha-olefins, to produce polyolefins.

In a preferred embodiment of the invention, the polyolefin preparation may also be carried out in the presence of a ligand of formula II together with a trivalent or tetravalent metal salt or metal alkyl compound, which react in situ during the reaction to form a complex of formula I, which then acts as a catalyst to catalyze the olefin polymerization.

In the method for preparing polyolefin, the polymerization reaction temperature is 30-110 ℃, specifically can be 70 ℃, 80 ℃, 90 ℃, the time is 1 min-2.5 h, and the pressure is 0.1-10 MPa.

The pressure is absolute pressure.

In the process for preparing polyolefins according to the invention, the catalyst/cocatalyst molar ratio used is preferably in the range 1: in the range of 10000 to 100:1, more preferably in the range of 1:5000 to 10:1, and most preferably in the molar ratio of 1:1000 to 1:1. When aluminoxane is used as cocatalyst, it is generally used in large amounts, generally at least 100 times the amount of metal complex used; when boron-based compounds or alkyl aluminum compounds are used as cocatalysts, they are generally used in a molar ratio of 0.5:1 to 10:1, more preferably 1:1 to 6:1, most preferably 1:1 to 5:1 relative to the metal complex.

In the process for preparing polyolefins described in the present invention, a suitable solvent for solution polymerization is an inert liquid. Examples include, but are not limited to, toluene, n-hexane, methylene chloride, 1, 2-dichloroethane, chlorobenzene, tetrahydrofuran, or combinations thereof.

In another preferred embodiment, the olefin polymerization is carried out under homogeneous conditions.

In another preferred embodiment, the polyolefin product is a solid powdered polymer.

In another preferred embodiment, the polyolefin product has a molecular weight of: 1-400kg/mol.

Compared with the prior art, the invention has the main advantages that:

The invention uses the hydrogenation of the monodentate ligand of the diimine as a basic framework, and the electronic effect and the steric effect of the ligand can be conveniently regulated and controlled through the change of substituent groups on the imine and the aniline, so that different catalytic performances are realized. By selecting the appropriate ligands and metals, compositions and/or complexes can be obtained to provide the desired properties of the resulting product. The novel transition metal catalyst has the characteristics of simple preparation, high catalytic activity, good thermal stability and certain copolymerization performance, and is suitable for high-temperature solution polymerization preparation.

The olefin polymerization catalyst provided by the invention is used for catalyzing ethylene homopolymerization and ethylene and alpha-olefin copolymerization, and has good catalytic activity and thermal stability. Wherein the ethylene polymerization activity can reach up to 1700 kg/(mol h atm).

The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise indicated.

Typically: all air-sensitive and moisture-sensitive operations or steps were performed under high purity N ₂ or Ar using standard Schlenk techniques or in a Vigor glove box equipped with a high capacity recycler (< 1ppm O ₂). According to known techniques, all glassware was dried in a vacuum oven at 110 ℃ for at least 48 hours. The polymer grade ethylene was purified by an ethylene purification system (developed by the institute of chemical and physical of the university of academy of sciences of China).

According to known methods, all solvents are purified anhydrous and oxygen-free. The hydrocarbon solvents used (e.g., toluene, n-hexane, C ₆D₆) and the olefin monomer 1-octene were distilled with sodium/benzophenone and then vacuum transferred to the sodium/potassium alloy for more rigorous deoxygenation by dehydration. All ligands and metal precursors were prepared or purchased according to the procedures of the public function of the person skilled in the art. The ¹H NMR、¹³ C NMR, DEPT 135 spectra of the following examples were recorded on a Agilent Technologies MHz spectrometer, a Varian400MHz spectrometer, a Bruker 400MHz spectrometer, a JEOL 600MHz spectrometer or a Agilent Technologies 600MHz spectrometer. Internal solvent resonance was used to reference chemical shifts of ¹ H and ¹³ C spectra and reported relative to Tetramethylsilane (TMS). NMR experiments on air sensitive samples were performed in a polytetrafluoro valve sealed sample tube (J-Young). ¹³ C NMR analysis and DEPT 135 analysis of the polymer microstructure were measured using deuterated 1, 2-tetrachloroethane as solvent at 120 ℃ using Agilent Technologies 600MHz, relaxation time (d ₁) =10 seconds. Attribution was done for these polymer signals according to literature. Elemental analysis was performed by the Shanghai institute of organic chemistry, analytical laboratory, national academy of sciences. The M _n、M_w and molecular weight distribution (PDI) of the Polymer were determined by Polymer Char CFC at 150℃with 1, 2-dichlorobenzene as solvent and a solvent flow rate of 1.0mL/min at 150 ℃. The melting points of the polymers were determined by conventional DSC methods. X-ray crystallography data were collected using Bruker AXSD X-ray diffractometer.

Examples 1 to 14 illustrate the synthesis of a portion of the ligands used for the catalyst, examples 15 to 18 illustrate the synthesis of a portion of the catalyst, and examples 19 to 20 illustrate the results of a portion of ethylene homo-and co-polymerization with other alpha-olefins.

EXAMPLE 1 Synthesis of ligand L1

To a 100mL reaction flask, 309.1mg of iminooxazoline ligand P1 (0.926 mmol) was added, 15mL of anhydrous methanol, and the mixture was hydrogenated at 40℃for 15 minutes. The reaction mixture was concentrated under reduced pressure, followed by passing through a short column of silica gel with anhydrous diethyl ether, concentrating under reduced pressure, and drying under vacuum to give L1 as a pale yellow solid (307.8 mg, yield 99%).

Anal.Calcd.For C₂₂H₂₈N₂O:C,78.53；H,8.39；N,8.33；O,4.75

Found:C,78.33；H,8.19；N,8.31；O,4.65

¹H NMR(400MHz,Chloroform-d):δ＝7.37(d,J＝8.0Hz,2H,Ar-H),7.35–7.27(m,3H,Ar-H),7.07-6.97(m,3H,Ar-H),4.77(s,1H,CH),4.37–4.20(m,2H,CH₂),4.13(s,1H,NH),3.91(t,J＝8Hz,2H,CH₂),3.14(p,J＝8Hz,2H,CH),1.18(d,J＝8.0Hz,6H,CH₃),1.04(d,J＝8.0Hz,6H,CH₃).

EXAMPLE 2 Synthesis of ligand L2

Hydrogenation of 1g of the iminooxazoline ligand P2 (2.758 mmol) gave L2 as a pale yellow solid, 0.98g (98% yield) according to a similar synthetic method to ligand L1.

Anal.Calcd.For C₂₄H₃₂N₂O:C,79.08；H,8.85；N,7.68；O,4.39

Found:C,78.76；H,8.65；N,7.45；O,4.38

¹H NMR(400MHz,Chloroform-d):δ＝7.38(d,J＝8.0Hz,2H,Ar-H),7.35–7.27(m,3H,Ar-H),7.07–6.97(m,3H,Ar-H),4.68(s,1H,CH),4.08(s,1H,NH),3.97(d,J＝8.0Hz,1H,CH₂),3.90(d,J＝8.0Hz,1H,CH₂),3.12(p,J＝8.0Hz,2H,CH),1.29(d,J＝12.0Hz,6H,CH₃),1.17(d,J＝8.0Hz,6H,CH₃),1.02(d,J＝8.0Hz,6H,CH₃).

EXAMPLE 3 Synthesis of ligand L3

Hydrogenation of 1g of the iminooxazoline ligand P3 (2.484 mmol) gave L3 as a pale yellow solid, 0.99g (yield 98.5%) according to a similar synthetic method to ligand L1.

Anal.Calcd.For C₂₇H₃₆N₂O:C,80.15；H,8.97；N,6.92；O,3.95

Found:C,80.35；H,8.89；N,6.97；O,3.90

¹H NMR(400MHz,Chloroform-d):δ＝7.40(d,J＝4.0Hz,2H,Ar-H),7.36–7.26(m,3H,Ar-H),7.02(m,3H,Ar-H),4.67(s,1H,CH),4.16(s,1H,NH),4.00(d,J＝8.0Hz,1H,CH₂),3.92(d,J＝8.0Hz,1H,CH₂),3.15(p,J＝8.0Hz,2H,CH),1.85–1.66(m,4H,CH₂),1.52(m,3H,CH₂),1.31(m,4H,CH₂),1.16(d,J＝8.0Hz,6H,CH₃),1.03(d,J＝4.0Hz,6H,CH₃).

EXAMPLE 4 Synthesis of ligand L4

Hydrogenation of 0.5g of the iminooxazoline ligand P4 (1.280 mmol) gave L4 as a pale yellow solid, 0.49g (97% yield) according to a similar synthetic method to ligand L1.

Anal.Calcd.For C₂₆H₃₆N₂O:C,79.55；H,9.24；N,7.14；O,4.08

Found:C,79.49；H,8.91；N,7.20；O,4.15

EXAMPLE 5 Synthesis of ligand L5

Hydrogenation of 0.5g of the iminooxazoline ligand P5 (1.280 mmol) gave L5 as a pale yellow solid, 0.49g (98% yield) according to a similar synthetic method to ligand L1.

Anal.Calcd.For C₂₆H₃₆N₂O:C,79.55；H,9.24；N,7.14；O,4.08

Found:C,80.04；H,8.96；N,7.07；O,4.55

EXAMPLE 6 Synthesis of ligand L6

Hydrogenation of 0.5g of the iminooxazoline ligand P6 (1.522 mmol) gave L6 as a pale yellow solid, 0.48g (yield 96%) according to a similar synthetic method to ligand L1.

Anal.Calcd.For C₂₁H₃₄N₂O:C,76.31；H,10.37；N,8.48；O,4.84

Found:C,76.38；H,10.02；N,8.45；O,4.68

EXAMPLE 7 Synthesis of ligand L7

Hydrogenation of 0.5g of the iminooxazoline ligand P7 (1.189 mmol) gave L7 as a pale yellow solid, 0.48g (yield 96%) according to a similar synthetic method to ligand L1.

Anal.Calcd.For C₂₇H₃₈N₂O₂:C,76.74；H,9.06；N,6.63；O,7.57

Found:C,77.32；H,8.90；N,6.46；O,7.55

EXAMPLE 8 Synthesis of ligand L8

Hydrogenation of 0.5g of the iminooxazoline ligand P8 (1.383 mmol) gave L8 as a pale yellow solid, 0.49g (98% yield) according to a similar synthetic method to ligand L1.

Anal.Calcd.For C₂₄H₃₃N₃:C,79.29；H,9.15；N,11.56

Found:C,79.43；H,8.84；N,11.62

EXAMPLE 9 Synthesis of ligand L9

Hydrogenation of 0.5g of the iminooxazoline ligand P9 (1.230 mmol) gave L9 as a pale yellow solid, 0.49g (97% yield) according to a similar synthetic method to ligand L1.

Anal.Calcd.For C₂₆H₃₆N₂S:C,76.42；H,8.88；N,6.86；S,7.85

Found:C,76.30；H,8.92；N,6.85；S,7.66

EXAMPLE 10 Synthesis of ligand L10

Hydrogenation of 0.5g of the iminooxazoline ligand P10 (1.236 mmol) gave L10 as a pale yellow solid, 0.49g (97% yield) according to a similar synthetic method to ligand L1.

Anal.Calcd.For C₂₇H₃₈N₂O:C,79.76；H,9.42；N,6.89；O,3.93

Found:C,79.45；H,9.32；N,6.91；O,3.88

EXAMPLE 11 Synthesis of ligand L11

Hydrogenation of 0.5g of the iminooxazoline ligand P11 (1.189 mmol) gave L11 as a pale yellow solid, 0.48g (yield 96%) according to a similar synthetic method to ligand L1.

Anal.Calcd.For C₂₇H₃₈N₂S:C,76.72；H,9.06；N,6.63；S,7.59

Found:C,76.67；H,9.25；N,6.54；S,7.67

EXAMPLE 12 Synthesis of ligand L12

Hydrogenation of 0.5g of the iminooxazoline ligand P12 (1.194 mmol) gave L12 as a pale yellow solid, 0.48g (yield 96%) according to a similar synthetic method to ligand L1.

Anal.Calcd.For C₂₈H₄₀N₂O:C,79.95；H,9.59；N,6.66；O,3.80

Found:C,79.76；H,9.61；N,6.38；O,3.45

EXAMPLE 13 Synthesis of ligand L13

Hydrogenation of 0.5g of the iminooxazoline ligand P13 (1.414 mmol) gave L13 as a pale yellow solid, 0.49g (97% yield) according to a similar synthetic method to ligand L1.

Anal.Calcd.For C₂₃H₃₇N₃:C,77.69；H,10.49；N,11.82

Found:C,77.71；H,10.35；N,11.61

EXAMPLE 14 Synthesis of ligand L14

Hydrogenation of 0.5g of the iminooxazoline ligand P14 (1.356 mmol) gave L14 as a pale yellow solid, 0.49g (98% yield) according to a similar synthetic method to ligand L1.

EXAMPLE 15 Synthesis of ligand L15

Hydrogenation of 0.5g of the iminooxazoline ligand P15 (1.280 mmol) gave L15 as a pale yellow solid, 0.48g (yield 96%) according to a similar synthetic method to ligand L1.

EXAMPLE 16 Synthesis of ligand L16

Hydrogenation of 0.5g of the iminooxazoline ligand P16 (1.379 mmol) gave L16 as a pale yellow solid, 0.49g (97% yield) according to a similar synthetic method to ligand L1.

EXAMPLE 17 Synthesis of ligand L17

Hydrogenation of 0.5g of the iminooxazoline ligand P17 (1.499 mmol) gave L17 as a pale yellow solid, 0.48g (yield 96%) according to a similar synthetic method to ligand L1.

EXAMPLE 18 Synthesis of ligand L18

Hydrogenation of 0.5g of the iminooxazoline ligand P18 (1.439 mmol) gave L18 as a pale yellow solid, 0.49g (97% yield) according to a similar synthetic method to ligand L1.

EXAMPLE 19 Synthesis of ligand L19

Hydrogenation of 0.5g of the iminooxazoline ligand P19 (1.142 mmol) gave L19 as a pale yellow solid, 0.49g (97% yield) according to a similar synthetic method to ligand L1.

EXAMPLE 20 Synthesis of ligand L20

Hydrogenation of 0.5g of the iminooxazoline ligand P20 (1.221 mmol) gave L20 as a pale yellow solid, 0.49g (98% yield) according to a similar synthetic method to ligand L1.

EXAMPLE 21 Synthesis of ligand L21

Hydrogenation of 0.5g of the iminooxazoline ligand P21 (1.310 mmol) gave L21 as a pale yellow solid, 0.48g (yield 96%) according to a similar synthetic method to ligand L1.

EXAMPLE 22 Synthesis of Complex C1

Ligand L1 (487.9 mg,1.45 mmol) was weighed into a 50mL Schlenk reaction tube in a glove box, zrBn ₄ (628.9 mg,1.38 mmol) was added, and 20mL toluene solution was added. Heating at 75deg.C for 3h. The solvent was removed under reduced pressure, and after addition of n-hexane, stirring was continued until a yellow solid precipitated, which was filtered, washed with n-hexane several more times, collected and dried under vacuum to give C1 (pale yellow solid) in 71.2% yield.

Anal.Calcd.For C₄₃H₄₈N₂OZr:C,73.77；H,6.91；N,4.00；O,2.29；Zr,13.03

Found:C,73.55；H,6.73；N,3.84；O,2.29；Zr,13.23

¹H NMR(400MHz,C₆D₆):δ＝7.24–7.06(m,10H,Ar-H),7.03–6.90(m,7H,Ar-H),6.86(d,J＝8.0Hz,6H,Ar-H),6.80(s,2H,Ar-H),5.30(s,1H,CH),3.60–3.40(m,2H,CH₂),3.30(q,J＝1.2Hz,2H,CH₂),2.75(m,2H,CH),2.41(d,J＝12.0Hz,3H,CH₂),2.25(d,J＝12.0Hz,3H,CH₂),1.40(dd,J＝8.0,8.0Hz,6H,CH₃),1.34(d,J＝4.0Hz,3H,CH₃),0.14(d,J＝8.0Hz,3H,CH₃).

EXAMPLE 23 Synthesis of Complex C2

Ligand L2 (528.6 mg,1.45 mmol) was weighed into a 50mL Schlenk reaction tube in a glove box, zrBn ₄ (628.9 mg,1.38 mmol) was added, and 20mL toluene solution was added. Heating at 75deg.C for 14h. The solvent was removed under reduced pressure, and after addition of n-hexane, stirring was continued until a yellow solid precipitated out, which was filtered, washed with n-hexane several more times, collected and dried under vacuum to give C2 (yellow solid) in 64.7% yield.

Anal.Calcd.For C₄₅H₅₂N₂OZr:C,74.23；H,7.20；N,3.85；O,2.20；Zr,12.53

Found:C,74.12；H,7.11；N,3.75；O,2.31；Zr,12.64

¹H NMR(400MHz,C₆D₆):δ＝7.21(t,J＝8.0Hz,6H,Ar-H),7.12–7.05(m,2H,Ar-H),7.01(d,J＝8.0Hz,6H,Ar-H),6.98–6.87(m,9H,Ar-H),5.25(s,1H,CH),3.53(p,J＝8.0Hz,1H,CH),3.37–3.23(m,2H,CH₂),3.16(d,J＝8.0Hz,1H,CH),2.65(s,6H,CH₂),1.41(d,J＝8.0Hz,3H,CH₃),1.34(d,J＝8.0Hz,3H,CH₃),1.19(d,J＝8.0Hz,3H,CH₃),0.92(s,3H,CH₃),0.88(s,3H,CH₃),0.21(d,J＝4.0Hz,3H,CH₃).

EXAMPLE 24 Synthesis of Complex C3

Ligand L3 (554.3 mg,1.37 mmol) was weighed into a 50mL Schlenk reaction tube in a glove box, zrBn ₄ (591.8 mg,1.30 mmol) was added, and 20mL toluene solution was added. Heating at 75deg.C for 20h. The solvent was removed under reduced pressure, and after addition of n-hexane, stirring was continued until a yellow solid precipitated, which was filtered, washed with n-hexane several more times, collected and dried under vacuum to give C3 (earthy yellow solid) in 46.4% yield.

Anal.Calcd.For C₄₈H₅₆N₂OZr:C,75.05；H,7.35；N,3.65；O,2.08；Zr,11.87

Found:C,75.13；H,7.16；N,3.39；O,2.08；Zr,11.65

¹H NMR(400MHz,C₆D₆):δ＝7.30(t,J＝8.0Hz,6H,Ar-H),7.24(s,4H,Ar-H),7.14(s,3H,Ar-H),7.03(t,J＝8.0Hz,10H,Ar-H),5.38(s,1H,CH),3.72–3.62(m,1H,CH),3.60(s,2H,CH₂),3.31(m,1H,CH),2.77(s,6H,CH₂),1.76–1.56(m,3H,CH₂),1.50(d,J＝8.0Hz,3H,CH₃),1.43(d,J＝4.0Hz,3H,CH₃),1.27(d,J＝8.0Hz,4H,CH₃),1.13–0.91(m,3H,CH₂),0.69–0.36(m,3H,CH₂),0.33(d,J＝8.0Hz,3H,CH₃).

EXAMPLE 25 Synthesis of Complex C4-C23

Similar experimental methods for Complex C1 gave other complexes C4(48.5％);C5(51.2％);C6(54.1％);C7(48.5％);C8(65.3％);C9(71.4％);C10(61.2％);C11(58.5％);C12(53.2％);C13(55.6％);C14(54.2％);C15(51.3％);C16(50.4％);C17(49.5％);C18(61.2％);C19(62.2％);C20(44.5％);C21(43.7％).

The partial analysis data are as follows:

C4

Anal.Calcd.For C₄₇H₅₆N₂OZr:C,74.65；H,7.46；N,3.70；O,2.12；Zr,12.06

Found:C,74.35；H,7.28；N,3.86；O,2.14；Zr,12.02

C5

Anal.Calcd.For C₄₇H₅₆N₂OZr:C,74.65；H,7.46；N,3.70；O,2.12；Zr,12.06

Found:C,74.22；H,7.18；N,3.62；O,2.43；Zr,12.16

C6

Anal.Calcd.For C₄₂H₅₆N₂OZr:C,72.46；H,8.11；N,4.02；O,2.30；Zr,13.10

Found:C,72.19；H,8.44；N,4.34；O,2.18；Zr,13.21

C7

Anal.Calcd.For C₄₈H₅₈N₂O₂Zr:C,73.33；H,7.44；N,3.56；O,4.07；Zr,11.60

Found:C,73.21；H,7.23；N,3.21；O,4.14；Zr,11.76

C8

Anal.Calcd.For C₄₇H₅₆N₂SZr:C,73.10；H,7.31；N,3.63；S,4.15；Zr,11.81

Found:C,73.25；H,7.16；N,3.34；S,4.08；Zr,11.76

C9

Anal.Calcd.For C₄₈H₅₈N₂OZr:C,74.85；H,7.59；N,3.64；O,2.08；Zr,11.84

Found:C,74.62；H,7.37；N,3.45；O,2.16；Zr,11.75

C10

Anal.Calcd.For C₄₈H₅₈N₂SZr:C,73.32；H,7.44；N,3.56；S,4.08；Zr,11.60

Found:C,73.15；H,7.27；N,3.43；S,4.11；Zr,11.75

C11

Anal.Calcd.For C₄₉H₆₀N₂OZr:C,75.04；H,7.71；N,3.57；O,2.04；Zr,11.63

Found:C,75.15；H,7.62；N,3.43；O,2.16；Zr,11.39

C12

Anal.Calcd.For C₄₄H₅₇N₃Zr:C,73.48；H,7.99；N,5.84；Zr,12.68

Found:C,73.23；H,7.65；N,5.78；Zr,12.59

C13

Anal.Calcd.For C₄₅H₅₈N₂OZr:C,73.62；H,7.84；N,3.82；O,2.18；Zr,12.44

Found:C,73.45；H,7.66；N,3.89；O,2.34；Zr,12.27

C14

Anal.Calcd.For C₄₇H₅₆HfN₂O:C,66.93；H,6.69；Hf,21.16；N,3.32；O,1.90

Found:C,66.92；H,6.28；Hf,21.32；N,3.26；O,1.78

C15

Anal.Calcd.For C₄₅H₅₂HfN₂O:C,66.28；H,6.43；Hf,21.89；N,3.44；O,1.96

Found:C,66.24；H,6.15；Hf,21.44；N,3.21；O,1.67

C16

Anal.Calcd.For C₂₆H₃₅Cl₃N₂OZr:C,53.01;H,5.99;Cl,18.05;N,4.75;O,2.72;Zr,15.48

Found:C,53.31；H,5.95；Cl,18.32；N,4.42；O,2.51；Zr,15.82

C17

Anal.Calcd.For C₂₆H₃₅Cl₃HfN₂O:C,46.17;H,5.22;Cl,15.72;Hf,26.39;N,4.14;O,2.37

Found:C,46.16；H,5.25；Cl,15.52；Hf,26.58；N,4.12；O,2.30

C18

Anal.Calcd.For C₄₄H₅₁HfN₃:C,66.03；H,6.42；Hf,22.30；N,5.25

Found:C,65.98；H,6.54；Hf,22.43；N,5.61

C19

Anal.Calcd.For C₅₁H₅₇N₃Zr:C,76.26；H,7.15；N,5.23；Zr,11.36

Found:C,76.6；H,7.15；N,5.23；Zr,11.36

C20

Anal.Calcd.For C₄₉H₅₃HfN₃:C,68.24；H,6.19；Hf,20.70；N,4.87

Found:C,68.53；H,6.21；Hf,20.29；N,4.66

C21

Anal.Calcd.For C₄₇H₄₉HfN₃:C,67.65；H,5.92；Hf,21.39；N,5.04

Found:C,67.23；H,5.76；Hf,21.01；N,5.00

Example 26 catalyst homopolymerization experiment

Preparation of the catalyst solution: the catalyst solution is prepared just prior to use. The catalyst/cocatalyst ratio was 1/1.2. In a glove box, 10. Mu. Mol of catalyst and 12. Mu. Mol of cocatalyst were weighed into a 30mL clear glass vial, 5mL toluene was added and rapidly shaken to give a catalyst solution, which was transferred to a syringe, removed from the glove box, and immediately injected into a polymerization flask to initiate polymerization.

Ethylene homopolymerization step: in a glove box, 45mL of anhydrous anaerobic toluene was placed in a 350mL glass pressure bottle (dried in an oven at 110 ℃ for two days prior to use). In all cases, the total volume was kept at 50mL. A large magnetic stirrer was added to the vessel, which was removed from the glove box in a sealed manner and connected to an N ₂/high vacuum line. The mixture was degassed and then 1atm of ethylene was continuously and stably introduced. The solution was magnetically stirred under ethylene and externally heated to the desired temperature with a water/oil bath and kept at constant temperature for a certain period of time, and the bath temperature was monitored by a thermocouple. The required amount of 5mL of catalyst/cocatalyst solution was rapidly injected to start the polymerization. The reaction system was maintained at the desired atmospheric ethylene pressure of 1 atm. Adding 1-2 mL of deoxidized ethanol after the polymerization reaction is finished, and quenching the reaction; ethanol containing 10% hydrochloric acid was poured into the polymerization mixture to precipitate a product. Stirring was maintained overnight, filtration, washing with ethanol, collecting the polymerization product and drying to constant weight under vacuum at 50 ℃. Selected ethylene homomeric effects are shown in the following table:

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^a Conditions 1atm ethylene, 10.0. Mu. Mol of metal complex .12.0μmol Ph₃C⁺B^-(C₆F₅)₄,1min,50mL toluene.^b 10⁶g/mol·h·atm.^c, 1,2, 4-trichlorobenzene, 150℃as determined by GPC. ^d 3min.^e Ph₃C⁺B^-(C₆F₅)₄ +mmao as cocatalyst. ^f Ph₃C⁺B^-(C₆F₅)₄ +MAO as cocatalyst.

Example 27 catalyst copolymerization experiments

Preparation of the catalyst solution: the catalyst solution is prepared just prior to use. The catalyst/cocatalyst ratio was 1/1.2. In a glove box, 10. Mu. Mol of catalyst and 12. Mu. Mol of cocatalyst were weighed into a 30mL clear glass vial, 5mL toluene was added and rapidly shaken to give a catalyst solution, which was transferred to a syringe, removed from the glove box, and immediately injected into a polymerization flask to initiate polymerization.

Ethylene/1-octene atmospheric copolymerization step:

In a glove box, a 350mL glass pressure bottle (dried in an oven at 110 ℃ C. For two days before use) was filled with 45mL of anhydrous anaerobic toluene and a specified amount of 1-octene monomer. In all cases, the total volume was kept at 50mL. A large magnetic stirrer was added to the vessel, which was removed from the glove box in a sealed manner and connected to an N ₂/high vacuum line. The mixture was degassed and then 1atm of ethylene was continuously and stably introduced. The solution was magnetically stirred under ethylene and externally heated to the desired temperature with a water/oil bath and kept at constant temperature for a certain period of time, and the bath temperature was monitored by a thermocouple. The required amount of 5mL of catalyst/cocatalyst solution was rapidly injected to start the polymerization. The reaction system was maintained at the desired atmospheric ethylene pressure of 1 atm. Adding 1-2 mL of deoxidized ethanol after the polymerization reaction is finished, and quenching the reaction; ethanol containing 10% hydrochloric acid was poured into the polymerization mixture to precipitate a product. Stirring was maintained overnight, filtration, washing with ethanol, collecting the polymerization product and drying to constant weight under vacuum at 50 ℃. Selected ethylene and 1-octene copolymerization results are shown in the following table:

^a Conditions 1atm ethylene, 10.0. Mu. Mol of metal complex .12.0μmol Ph₃C⁺B^-(C₆F₅)₄,3min,50mL toluene.^b 10⁶g/mol·h·atm.^c, 1,2, 4-trichlorobenzene, 150℃as determined by GPC. ^{d 13} C-NMR.

Ethylene/1-octene high pressure copolymerization step:

Drying under reduced pressure for four hours in a 1L autoclave at 110 ℃, cooling the autoclave to a set temperature, pumping nitrogen for 3 times, sucking a mixed solution of aluminum alkyl and boron salt into the autoclave under negative pressure, stirring for 5min, blowing catalyst into the autoclave with ethylene under the protection of nitrogen, closing a valve on the autoclave, continuously introducing ethylene gas at the set pressure until the reaction is finished, rapidly cutting off the ethylene gas, emptying the unreacted ethylene gas in the autoclave, and pouring a polymer solution in the reaction system into ethanol containing 5% hydrochloric acid to precipitate a precipitated product. Stirring was maintained overnight, filtration, washing with ethanol, collecting the polymerization product and drying to constant weight under vacuum at 50 ℃.

^a Under the conditions of 1atm ethylene, 10.0. Mu. Mol of the metal complex. 12.0. Mu. Mol Ph ₃C⁺B^-(C₆F₅)₄, 10min,50mL toluene. ^b 10⁶g/mol·h·atm.^c 1,2, 4-trichlorobenzene, 150℃as determined by GPC. ^d 1000 carbon atoms correspond to the degree of branching, determined by ¹ H NMR (corrected for saturated end groups). ^e atm ethylene, 20.0. Mu. Mol of metal complex .i-Bu₃Al+Ph(C₁₆H₃₃)₂NH⁺B^-(C₆F₅)₄ as cocatalyst, 15min,450mL hexene.

All documents mentioned in this disclosure are incorporated by reference in this disclosure as if each were individually incorporated by reference. Further, it will be appreciated that various changes and modifications may be made by those skilled in the art after reading the above teachings, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.

Claims (12)

1. A metal complex of formula I:

Wherein:

-is a single bond;

the → is a coordination bond;

M is selected from the group consisting of: zirconium, hafnium;

X is selected from the group consisting of: halogen, C1-C4 alkyl, C2-C6 alkenyl, allyl A benzyl group;

m is 3 or 4;

and in formula I, the absolute value of the total number of negative charges carried by all ligands is the same as the absolute value of positive charges carried by metal M in the formula (i.e., the complex is charge balanced);

Y ¹ is selected from the group consisting of: hydrogen, C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 haloalkyl, C3-C8 halocycloalkyl, unsubstituted or substituted phenyl;

Y ² is selected from the group consisting of: CR ₄R₅、NR₆, O, or S, wherein R ₄、R₅、R₆ are each independently hydrogen, C1-C4 alkyl, or haloalkyl;

Or Y ¹ and Y ², and the C-C bond to which both are attached, together form an unsubstituted or substituted 5-12 membered carbocyclic or heterocyclic ring;

Is an unsubstituted or substituted 5-7 membered monocyclic, or 8-20 membered bicyclic or tricyclic group, wherein said bicyclic or tricyclic group includes a 5-7 membered monocyclic structure (i.e., the bicyclic or tricyclic structure is formed by fusing 1-2 rings to said 5-7 membered monocyclic ring); the 5-7 membered monocyclic ring contains 1-3N, O or S atoms and contains at least one N;

Y ³ is one or more optional substituents on the 5-7 membered monocyclic or the 5-7 membered monocyclic containing bicyclic or tricyclic groups, and each Y ³ is independently selected from the group consisting of: hydrogen, C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl;

z is selected from the group consisting of: C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl;

Said substitution means that said group has 1 to 5 substituents selected from the group consisting of: C1-C4 alkyl, C1-C4 haloalkyl, halogen, nitro, cyano 、CF₃、-O-R₁、-N(R₂)₂、-Si(R₃)₃、-CH₂-O-R₈、-SR₉, or-CH ₂-S-R₁₀, wherein R ₁、R₂、R₃ is each independently C1-C4 alkyl or haloalkyl; and R ₈、R₉、R₁₀ is C1-C8 alkyl or phenyl, respectively.

2. A compound according to claim 1 wherein,Selected from the group consisting of:

Wherein Y ⁴、Y⁵、Y⁶、Y⁷、Y⁸、Y⁹、Y¹⁰ and Y ¹¹ are each independently H, halogen, C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl, -O-R ₇、-CH₂-O-R₈、-SR₉ or-CH ₂-S-R₁₀, wherein R ₇、R₈、R₉ and R ₁₀ are each independently C1-C8 alkyl, unsubstituted or substituted phenyl; y ¹² is H, C-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl; or any two groups selected from Y ⁴、Y⁵、Y⁶、Y⁷、Y⁸、Y⁹、Y¹⁰ and Y ¹¹ located on the same ring atom or on adjacent ring atoms together with the ring atoms to which they are attached form a 3-to 8-membered substituted or unsubstituted carbocyclic or heterocyclic ring.

3. The complex of claim 1, wherein Y ¹ is selected from the group consisting of: C1-C4 alkyl, C3-C6 cycloalkyl, C1-C8 haloalkyl, C1-C8 halocycloalkyl, unsubstituted or substituted phenyl; or Y ¹ together with Y ² and the C-C bond to which they are attached form an unsubstituted or substituted 5-to 8-membered carbocyclic or heterocyclic ring.

4. The complex of claim 1, wherein said complex comprisesHas a structure shown in the following formula:

wherein p is selected from 1,2,3 or 4;

y ² is selected from the group consisting of: NR ₆, O, or S, wherein R ₆ is hydrogen, C1-C4 alkyl, or haloalkyl;

Y ⁴ and Y ⁵ are each independently selected from the group consisting of: H. halogen, C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl; or Y ⁴、Y⁵ together with the ring atoms to which it is attached form a 3-to 8-membered, substituted or unsubstituted, carbocyclic or heterocyclic ring.

5. The complex of claim 1, wherein Z is unsubstituted or substituted phenyl, wherein the substituted phenyl has 1 to 5 substituents selected from the group consisting of: C1-C4 alkyl and C1-C4 haloalkyl, halogen, nitro, cyano 、CF₃、-O-R₁、-N(R₂)₂、-Si(R₃)₃、-CH₂-O-R₈、-SR₉ or-CH ₂-S-R₁₀, wherein R ₁、R₂、R₃ is each independently C1-C4 alkyl or haloalkyl; and R ₈、R₉ and R ₁₀ are each C1-C8 alkyl or phenyl;

and up to one nitro or cyano group on the substituted phenyl group;

Preferably, Z is selected from the group consisting of:

6. the compound of claim 1, wherein said complex is selected from the group consisting of:

7. A process for the synthesis of a metal complex of formula i according to claim 1, characterized in that a ligand ii of the formula is reacted with a metal compound in a molar ratio of 1 to 3:1 in an organic solvent at a temperature of 50-100 ℃ for 5-30 hours, thereby obtaining the complex of claim 1;

The ligand has the structural formula as follows:

wherein: y ¹、Y²、Y³, Z are the same as described in the preceding claim 1;

The metal compound refers to MX _m or MX _(m-1); wherein M and X are the same as described in the preceding claim 1; m is 3 or 4.

8. Use of an olefin polymerization catalyst according to claim 1 for catalyzing olefin polymerization with an optional cocatalyst.

9. The use according to claim 8, wherein in another preferred embodiment the cocatalyst is selected from the group consisting of: boron compounds, alkylaluminum compounds, alkylaluminoxane.

10. A process for the polymerization of olefins, said process comprising step (a) or step (b):

Step (a): catalyzing the homo-or copolymerization of olefins in the presence of the catalyst according to any of claims 1 to 6 and optionally a cocatalyst;

step (b): catalyzing olefin to carry out homopolymerization or copolymerization in the presence of ligand and metal compound as shown in formula II;

wherein: y ¹、Y²、Y³, Z are the same as described in the preceding claim 1;

The metal compound refers to MX _m or MX _(m-1); wherein M and X are the same as described in the preceding claim 1; m is 3 or 4;

The homo-polymerization is ethylene, alpha-olefin or C3-C20 cycloolefin homo-polymerization; the copolymerization refers to the copolymerization of ethylene and alpha-olefin; the alpha-olefin refers to C3-C18 alpha-olefin.

11. A metal ligand, characterized in that the metal ligand has a structure as shown in the following formula II:

Y ¹ is selected from the group consisting of: hydrogen, C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 haloalkyl, C3-C8 halocycloalkyl, unsubstituted or substituted phenyl;

Y ² is selected from the group consisting of: CR ₄R₅、NR₆, O, or S, wherein R ₄、R₅、R₆ are each independently hydrogen, C1-C4 alkyl, or haloalkyl;

Or Y ¹ and Y ², and the C-C bond to which both are attached, together form an unsubstituted or substituted 5-12 membered carbocyclic or heterocyclic ring;

Is an unsubstituted or substituted 5-7 membered monocyclic, or 8-20 membered bicyclic or tricyclic group, wherein said bicyclic or tricyclic group includes a 5-7 membered monocyclic structure (i.e., the bicyclic or tricyclic structure is formed by fusing 1-2 rings to said 5-7 membered monocyclic ring); the 5-7 membered monocyclic ring contains 1-3N, O or S atoms and contains at least one N;

Y ³ is one or more optional substituents on the 5-7 membered monocyclic or the 5-7 membered monocyclic containing bicyclic or tricyclic groups, and each Y ³ is independently selected from the group consisting of: hydrogen, C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl;

z is selected from the group consisting of: C1-C8 alkyl, C1-C8 haloalkyl, unsubstituted or substituted phenyl;

Said substitution means that said group has 1 to 5 substituents selected from the group consisting of: C1-C4 alkyl, C1-C4 haloalkyl, halogen, nitro, cyano 、CF₃、-O-R₁、-N(R₂)₂、-Si(R₃)₃、-CH₂-O-R₈、-SR₉, or-CH ₂-S-R₁₀, wherein R ₁、R₂、R₃ is each independently C1-C4 alkyl or haloalkyl; and R ₈、R₉、R₁₀ is C1-C8 alkyl or phenyl, respectively.

12. The ligand of claim 11, wherein said metal ligand has a structure selected from the group consisting of: