CN110396116B

CN110396116B - [ N, O ] bidentate nickel and palladium complex of ketone-imidazoline-2-imine ligand, and preparation method and application thereof

Info

Publication number: CN110396116B
Application number: CN201910624163.XA
Authority: CN
Inventors: 蔡正国; 李彦青; 肖茹
Original assignee: Donghua University
Current assignee: Donghua University
Priority date: 2019-07-11
Filing date: 2019-07-11
Publication date: 2020-07-28
Anticipated expiration: 2039-07-11
Also published as: CN110396116A

Abstract

The invention relates to a ketone-imidazoline-2-imine [ N, O]The bidentate nickel and palladium complex and the preparation method and the application thereof, the preparation method is as follows: the ketone-imidazoline-2-imine ligand reacts with a hydrogen extraction reagent and a metal precursor in sequence to prepare the ketone-imidazoline-2-imine [ N, O]Bidentate nickel, palladium complexes; the structural formula of the prepared complex is one of the following formulas:

the complex and the cocatalyst form a catalyst composition; the complex or the catalyst composition is used for catalyzing homopolymerization or copolymerization of olefin monomers, and the specific process comprises the following steps: under the protection of nitrogen, firstly, the complex or the catalyst composition is dissolved in a solvent, then, an olefin monomer is added, and the mixture reacts for a period of time at a certain temperature and a certain pressure, so that the olefin polymer is prepared. The complex and the catalyst composition have high catalytic activity, high tolerance to polar monomers and low application cost.

Description

[ N, O ] bidentate nickel and palladium complex of ketone-imidazoline-2-imine ligand, and preparation method and application thereof

Technical Field

The invention belongs to the technical field of olefin catalysis, relates to an [ N, O ] bidentate nickel and palladium complex of a ketone-imidazoline-2-imine ligand, and a preparation method and application thereof, and particularly relates to an [ N, O ] bidentate nickel and palladium complex of a ketone-imidazoline-2-imine ligand, which is applied to the homopolymerization or copolymerization of ethylene and/or cycloolefin and polar/functional monomers, and a preparation method and application thereof.

Background

Polyolefin catalysts are the core and key to the industrial production process of olefin polymerization, and the variety is wide, and the current industrial catalysts mainly comprise Ziegler-Natta catalyst systems (DE Pat889229 (1953); IT Pat545332 (1956); IT Pat536899 (1956); chem.Rev., 2000,100,1169.), Phillips catalyst systems (Belg. Pat.530617 (1955); chem.Rev.,1996,96,3327.) and metallocene catalyst systems (Kaminsky. W., Berlin: Springer, 1999).

Unlike the three catalysts, the late transition metal catalyst is a catalyst using metal nickel, palladium, iron, cobalt, etc. as active centers, and the first breakthrough of the late transition metal catalyst in catalyzing olefin polymerization is α -diimine nickel and palladium catalysts containing bulky substituents reported by Brookhart et al in 1995 (Brookhart. m., j.am.chem.soc.,1995,117,6414). the development of the series of catalysts has greatly promoted the development of late transition metal olefin polymerization catalysts, and in 2000, Grubbs et al reported neutral nickel catalysts containing salicylaldehyde ligands, which can catalyze ethylene polymerization in a single component, and have good tolerance to heteroatoms such as O, S, N, which can catalyze the copolymerization of ethylene and polar monomers (grubbs.r.h., Science,2000,287,460.). from 1995 to now, the late transition metal olefin polymerization catalysts have been rapidly developed.

In addition, contains [ N, O ]]Brookhart et al have reported that a series of nickel catalysts (Brookhart, M., organometallics, 2001,20, 3217; organometallics, 2003,22, 3533; organometallics, 2003,22,250.) having 2-anilincycloheptanone as a ligand, which are five-membered chelate ring structures, can catalyze ethylene polymerization without a phosphine scavenger, and when 2, 6-diisopropylbenzene having a large steric hindrance is contained in nitrogen, they have higher catalytic activity, can obtain high molecular weight polyethylene, and have a certain tolerance to nitrogen heteroatom compounds, but have not been studied for polymerization of polar monomers₂、 B(C₆F₅)₃In the case of low activity, but via Ni (COD)₂After activation, the catalytic activity can be up to 8.0 × 10⁴g PE/mol_NiH, but the molecular weight of the obtained polymer is low, the number of branched chains is high (125 branched chains/1000C), the acidity of β -ketone monoimine ligand can be adjusted by introducing electron-donating groups or electron-withdrawing groups, the electron deficiency of the metal center of the generated metal organic complex is changed, and the regulation and control of the catalyst activity and the molecular weight of the polymer are further realized.

The structural formula of the 2-imidoimidazoline ligand is as follows:

it is analogous to cyclopentadienyl (C)₅H₅) The imidazole salt is stable, so that the 2-imidoimidazoline ligand can exist in two different meso structures, and the electron cloud density on the exocyclic N atom is high. Compared with quaternary phosphonium groups, the imidazolium ring can more effectively stabilize positive charges and increase the electronegativity of nitrogen atoms, so that the ligand alkalinity and electron donating capability are enhanced, and a stronger N-M bond can be formed when the N atom forms a bond with a metal center (M), thereby being beneficial to improving the thermal stability of the complex and further improving the catalytic activity of the complex; in addition, the ligand space and electronic effect can be easily regulated and controlled according to the property of the substituent group on the imidazoline ring. Research groups represented by Matthias Tamm and Moris S.Eisen successively develop a series of metal catalysts mainly based on 2-imino imidazoline ligands, and the metal catalysts have better catalytic activity in the olefin polymerization process.

At present, in order to achieve higher polymerization activity, a large amount of alkyl aluminoxane or expensive cocatalyst such as boron compound is still needed in most cases for the late transition metal catalyst, so that the application cost of the catalyst is increased; in order to improve the tolerance of the polar group-containing vinyl monomer, a catalyst ligand with a novel structure needs to be further developed on the basis of the existing catalyst so as to be better applied to the polymerization research of the polar monomer; the same complex can be used to obtain both high polymer and high selectivity oligomer.

Therefore, in view of the good catalytic performance of the [ N, O ] bidentate ketone-imine nickel-based catalyst and the electron supply characteristic of the 2-imidoimidazoline ligand, the research on the late transition metal catalyst based on the [ N, O ] bidentate ketone-imine nickel-based catalyst and the 2-imidoimidazoline ligand has very important significance for realizing good homopolymerization and copolymerization of ethylene/cycloolefin.

Disclosure of Invention

The invention aims to solve the problems of high application cost, poor tolerance to polar monomers and difficulty in realizing the obtainment of both high polymers and low polymers of a late transition metal catalytic system in the prior art, provides an [ N, O ] bidentate nickel and palladium complex of a ketone-imidazoline-2-imine ligand, a preparation method and application thereof, and particularly provides an [ N, O ] bidentate nickel and palladium complex of a ketone-imidazoline-2-imine ligand applied to the homopolymerization or copolymerization of ethylene and/or cycloolefins and polar/functional monomers, a preparation method and application thereof.

In view of the good catalytic performance of the [ N, O ] bidentate ketone-imine nickel-based catalyst containing anion N and the electron supply characteristic of the 2-imino imidazoline ligand, the invention designs and develops a series of novel ketone-imidazoline-2-imine ligands with the following structural general formula, and prepares the [ N, O ] bidentate nickel and palladium complex based on the ketone-imidazoline-2-imine ligand so as to realize good homopolymerization and copolymerization of ethylene/cycloolefin.

The ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex has a structural formula of one of the following formulas:

in the formula, R₁Is alkyl, aryl or aryl substituent; r₂Is H or phenyl (Ph); r₃～R₂₂Independently of one another, from hydrogen, alkyl, alkaneSubstituent of a group, alkoxy, halogen, haloalkyl, aryl or aryl, R ' is methyl, phenyl, benzyl or unsubstituted (i.e. R ' is absent and the position at which R ' is present does not have any substituent), M is nickel or palladium, L is trimethylphosphine, triphenylphosphine, pyridine, dimethylsulfoxide or allyl.

The [ N, O ] bidentate nickel and palladium complex is an [ N, O ] bidentate nickel and palladium complex which is combined by nitrogen (-N-) on an imidazoline ring with carbon oxygen (-C ═ O), sulfur oxygen (-S ═ O) and phosphorus oxygen (-P ═ O), is different from the existing [ N, O ] bidentate complex (1a, 1b, 1C and 1d) which is combined by exo-cycloimine nitrogen and carbonyl oxygen, has a more special electronegative structure of nitrogen atoms on the imidazoline ring, has better intra-ring electron delocalization property and stronger electronegativity, can well stabilize a metal center with positive charge, and is beneficial to improving and enhancing the thermal stability of a catalyst and further enhancing the catalytic activity of the catalyst, and the [ N, O ] bidentate nickel and palladium complex can catalyze ethylene polymerization with high activity even under the reaction condition of 120 ℃ without a cocatalyst, the structure is also beneficial to improving and enhancing the tolerance of the catalyst to polar monomers, and simultaneously, the complex of the structure is different from the [ N, O ] bidentate complex of a ring-shaped imine nitrogen-oxygen structure in the synthesis process, and the structural ligand is synthesized for the first time and is the [ N, O ] bidentate nickel and palladium complex of a novel ketone-imidazoline-2-imine ligand; when the [ N, O ] bidentate nickel and palladium complex is used for olefin polymerization, high polymers and low polymers can be obtained by selecting different cocatalysts.

The invention also provides a method for preparing the ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex, which comprises the steps of reacting the ketone-imidazoline-2-imine ligand with a hydrogen drawing reagent and a metal precursor in sequence to prepare the ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex;

the ketone-imidazoline-2-imine ligand is prepared by reacting N-1 substituted imidazole-2-amine with an acyl chloride compound, a benzene sulfinyl chloride compound or a phosphine chloride compound;

the acid chloride compound has the following structural formula:

the structural formula of the benzene sulfinyl chloride compound is as follows:

the structural formula of the phosphine chloride compound is as follows:

the structural formula of the N-1-substituted imidazole-2-amine is as follows:

the preparation process of the N-1-substituted imidazole-2-amine comprises the following steps: firstly, amino acetaldehyde dimethyl acetal or amino acetaldehyde dimethyl acetal reacts with O (S) -methyl isourea sulfate to prepare 2-amino-1H-imidazole hemisulfate, then the 2-amino-1H-imidazole hemisulfate reacts with alkaline substances to prepare 2-amino-1H-imidazole, and finally the 2-amino-1H-imidazole reacts with halide X-R₁Reacting to obtain N-1 substituted imidazole-2-amine;

or the following steps: firstly, 2-bromoacetophenone and 1-acetylguanidine react to prepare N- (4-phenyl-1H-imidazole-2-yl) formamide, then the N- (4-phenyl-1H-imidazole-2-yl) formamide reacts under the acidic condition to prepare 2-amino-4-phenyl-1H-imidazole hemisulfate, then the 2-amino-4-phenyl-1H-imidazole hemisulfate reacts with alkaline substances to prepare 2-amino-4-phenyl-1H-imidazole, and finally the 2-amino-4-phenyl-1H-imidazole and halide X-R₁Reacting to obtain N-1 substituted imidazole-2-amine;

the metal precursor is trans-chloro- (phenyl) bis (triphenylphosphine) nickel, trans-chloro- (methyl) bis (trimethylphosphine) nickel, allyl nickel chloride dimer, (ethylene glycol dimethyl ether) nickel bromide, chloro (cyclooctadiene) methyl palladium or allyl palladium chloride dimer;

when the metal in the metal precursor is palladium, the ketone-imidazoline-2-imine ligand reacts with the metal precursor and then also reacts with pyridine or dimethyl sulfoxide.

As a preferable scheme:

the method comprises the following specific steps:

(1) preparing a ketone-imidazoline-2-imine ligand;

(1.1) preparing hemisulfate;

(1.1.a) reacting aminoacetaldehyde dimethyl acetal or aminoacetaldehyde diethyl acetal with O (S) -methylisourea sulfate in water solution at a certain temperature and under the action of a catalyst for a period of time to prepare 2-amino-1H-imidazole hemisulfate;

(1.1.b) refluxing 2-bromoacetophenone and 1-acetylguanidine in acetonitrile to prepare N- (4-phenyl-1H-imidazol-2-yl) formamide, and reacting under the acidic condition of sulfuric acid with the pH of 2.0 (namely, sulfuric acid solution with the pH of 2.0) for a period of time to obtain 2-amino-4-phenyl-1H-imidazole hemisulfate;

(1.2) reacting 2-amino-1H-imidazole hemisulfate or 2-amino-4-phenyl-1H-imidazole hemisulfate with alkaline substances with the molar weight more than 2 times of that of the hemisulfate in an aqueous solution at a certain temperature for a period of time to prepare 2-amino-1H-imidazole or 2-amino-4-phenyl-1H-imidazole;

(1.3) reacting 2-amino-1H-imidazole or 2-amino-4-phenyl-1H-imidazole with a halide X-R₁Reacting in a solvent at a certain temperature under the action of a catalytic system for a period of time to prepare N-1 substituted imidazole-2-amine;

(1.4) reacting N-1-substituted imidazole-2-amine with an acyl chloride compound, a benzene sulfinyl chloride compound or a phosphine chloride compound in a solvent at a certain temperature under the action of a catalyst for a period of time to prepare a ketone-imidazoline-2-imine ligand;

(2) dissolving ketone-imidazoline-2-imine ligand in an organic solvent, adding a hydrogen-withdrawing reagent at a certain temperature, and reacting for a period of time to obtain a salt compound;

(3) and (3) adding a metal precursor into the system obtained in the step (2), reacting for a period of time at a certain temperature to obtain the ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex, wherein when the metal in the metal precursor is palladium, pyridine or dimethyl sulfoxide is added after the reaction for a period of time to continue the reaction for a period of time.

The process as described above, in step (1.1.a), the catalyst is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid; the molar ratio of aminoacetaldehyde dimethyl acetal or aminoacetaldehyde diethyl acetal to O (S) -methylisourea sulfate is 1-3: 1-3, and the molar ratio of the catalyst to O (S) -methylisourea sulfate is 3-5: 1-2; the certain temperature is 50-90 ℃, and the certain time is 6-11 hours;

in the step (1.1.b), the molar ratio of 2-bromoacetophenone to 1-acetylguanidine is 1-2: 1-5; the temperature of the reflux reaction is 60-100 ℃, the time of the reflux reaction is 6-11 h, and the period of time is 2-6 h;

in the step (1.2), the alkaline substance is potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate or sodium bicarbonate; the certain temperature is room temperature, and the period of time is 30 min;

in step (1.3), the halide X-R₁Is methyl iodide, 2-iodopropane, iodotert-butane, iodobenzene, 1-iodopropane, 2-iodo-1, 3-dimethylbenzene, 2,4, 6-trimethyliodobenzene, 2-iodoethylbenzene, 2-bromopropane, bromotert-butane, (2-bromoethyl) benzene, benzyl bromide or 2-bromo-1, 3, 5-trimethylbenzene, the solvent is absolute ethyl alcohol, absolute isopropyl alcohol, absolute tert-butyl alcohol or absolute methyl alcohol, the catalytic system consists of a main catalyst, an auxiliary catalyst and a basic substance, the main catalyst is cuprous iodide, the auxiliary catalyst is 8-hydroxyquinoline, and the basic substance is NaO^tBu、K₃PO₄、Cs₂CO₃Or K₂CO₃；

2-amino-1H-imidazole or 2-amino-4-phenyl-1H-imidazole with a halide X-R₁The molar ratio of the main catalyst to the cocatalyst is 1: 1-1.5, the molar ratio of the main catalyst to the cocatalyst is 1: 1.0-2, the molar ratio of the main catalyst to 2-amino-1H-imidazole or 2-amino-4-phenyl-1H-imidazole is 0.05-0.2: 1, and the molar ratio of the basic substance to 2-amino-1H-imidazole or 2-amino-4-phenyl-1H-imidazole is 1-3: 1;

the certain temperature is 50-95 ℃, and the certain time is 16-36 hours;

in the step (1.4), the solvent is diethyl ether, tetrahydrofuran,Dichloromethane, chloroform, toluene, 1, 4-dioxane, n-heptane or chlorobenzene and catalyst K₂CO₃、Na₂CO₃、Cs₂CO₃、KHCO₃、NaHCO₃、NaO^tBu、KO^tBu, methyllithium, n-butyllithium, pyridine or triethylamine, the acid chloride compound is benzoyl chloride, 4-bromobenzoyl chloride, 4-bromo-3, 5-dimethoxybenzoyl chloride, 3-bromo-4-methoxybenzoyl chloride, 4-fluoro-1-adamantanoyl chloride or adamantanoyl chloride, the benzene sulfinyl chloride is 4-fluorobenzene sulfinyl chloride or 2-chloro-5-nitrobenzene sulfinyl chloride, the phosphine chloride is p- (1, 1-dimethylethyl) -p- (2,4, 6-trimethylphenyl) phosphine chloride or bis (2, 6-dimethylphenyl) phosphine chloride, the kind of the acid chloride compound of the present invention is not limited to the above, and others are 2,4, 6-trimethylbenzoyl chloride, 2, 4-diisopropylbenzoyl chloride, pyridine or triethylamine, 2, 4-di-tert-butylbenzoyl chloride, 3-ethyl-1-adamantanoyl chloride, 3, 5-dimethyl-1-adamantanoyl chloride, and the like; also, the kinds of benzenesulfinyl chloride and phosphine chloride are not limited to the above, and others such as 4-chlorobenzenesulfinyl chloride, 3-nitrobenzenesulfinyl chloride, 2,4, 5-trimethoxybenzenesulfinyl chloride, tolylphosphine chloride, p-bis [2,4, 6-tris (1, 1-dimethylethyl) phenyl]Phosphine chloride, etc.;

the molar ratio of the N-1-substituted imidazole-2-amine to the acyl chloride compound, the benzene sulfenyl chloride compound or the phosphine chloride compound is 1: 0.9-1.1, and the molar ratio of the catalyst to the N-1-substituted imidazole-2-amine is 1.0-2.0: 1;

the certain temperature is-78-50 ℃, and the certain time is 10-18 h;

in the step (2), the organic solvent is toluene, diethyl ether, tetrahydrofuran, n-heptane or 1, 4-dioxane, and the hydrogen-removing reagent is sodium hydride, potassium hydride, methyllithium, n-butyllithium, potassium tert-butoxide or sodium bis (trimethylsilyl) amide; the molar ratio of the hydrogen drawing reagent to the ketone-imidazoline-2-imine ligand is 1-2.2: 1; the certain temperature is-78-35 ℃, and the certain time is 1-8 hours;

in the step (3), the molar ratio of the addition amount of the metal precursor to the addition amount of the ketone-imidazoline-2-imine ligand in the step (2) is 0.5-1: 1, and the molar ratio of the addition amount of pyridine or dimethyl sulfoxide to the addition amount of the ketone-imidazoline-2-imine ligand in the step (2) is 1-5: 1; the certain temperature is 0-60 ℃, the reaction time is 5-26 h, and the continuous reaction time is 1-6 h.

According to the method, after the step (1.4) is finished, the product is separated and purified by adopting a column chromatography method, an organic solvent recrystallization method or an organic solvent extraction method; the elution solvent used in the column chromatography is ethyl acetate-n-hexane, ethyl acetate-dichloromethane-n-hexane, methanol-n-hexane, ethanol-n-hexane, ethyl acetate-ethanol or ethyl acetate-methanol; the organic solvent used in the organic solvent recrystallization method or organic solvent extraction method is toluene, chloroform, ethyl acetate, dichloromethane, tetrahydrofuran, diethyl ether, n-hexane, methanol or ethanol.

The invention further provides the application of the ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex, wherein the ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex is used for catalyzing homopolymerization or copolymerization of olefin monomers;

the specific process is as follows: under the protection of nitrogen, dissolving a ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex in a solvent, adding an olefin monomer, and reacting for 1-180 min at the temperature of-20-120 ℃ and the pressure of 0.1-5 MPa to prepare an olefin polymer; the process for preparing the olefin polymer herein may be carried out under an inert gas atmosphere in addition to the nitrogen atmosphere;

the solvent is toluene, chlorobenzene, n-hexane or n-heptane, the olefin monomer is more than one of ethylene, cycloolefin and polar/functional monomer, the cycloolefin is norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5-cyclopentyl-2-norbornene, dicyclopentadiene or methyl dicyclopentadiene, the polar/functional monomer is 5-norbornene-2-carboxylic acid methyl ester, the polar/functional monomer is methyl ester, 5-norbornene-2-carbaldehyde, 5-hexenyl acetate, nadic anhydride, methyl acrylate, allyl acetate, vinyl ethyl ether, allyl ethyl ether, vinyl acetate bromopropene or chloropropene;

the molar ratio of ethylene to ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex is 10000-50000: 1-2, the molar ratio of cycloolefin to ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex is 4-10000: 1-2, and the molar ratio of polar/functional monomer to ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex is 10-40000: 1;

the olefin polymer comprises olefin polymer and ethylene oligomer, wherein the number average molecular weight of the olefin polymer is 2200 to 649000g & mol^-1Molecular weight distribution index (M)_w/M_n) 1.12 to 3.90, melting point (T)_m) The temperature is 75-430 ℃, and the ethylene oligomer mainly comprises butene and hexene.

In addition, the invention also provides a catalyst composition prepared from the ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex, which mainly comprises the ketone-imidazoline-2-imine [ N, O ] bidentate nickel, palladium complex and a cocatalyst, wherein the cocatalyst is aluminoxane, an alkyl aluminum compound, an alkyl aluminum chloride compound, a boron compound or bis- (1, 5-cyclooctadiene) nickel.

As a preferable scheme:

according to the catalyst composition, the molar ratio of the ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex to aluminum in the aluminoxane, the alkyl aluminum compound or the chlorinated alkyl aluminum compound is 1: 30-5000, the aluminum compound is added in different amounts according to different polymerization systems, the polymerization activity is possibly low when the amount of the aluminum compound is small, the excessive activity cannot be continuously increased, and the raw materials are wasted, so that the molar ratio is set in the range by considering the factors of different polymers, different polymerization effects and the like; the molar ratio of the ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex to the boron compound or the bis- (1, 5-cyclooctadiene) nickel is 1: 1-10, and the molar ratio is set in the range, so that the factors such as different polymers, different polymerization effects and the like are considered.

The catalyst composition as described above, wherein the aluminoxane is Methylaluminoxane (MAO), t-butylaluminum Modified Methylaluminoxane (MMAO) or dried t-butylaluminum modified methylaluminoxane (dMMAO); the alkyl aluminum compound is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum or tri-n-octyl aluminum; the alkyl aluminum chloride compound is diethyl aluminum chloride or ethyl aluminum dichloride; the boron compound is tris (pentafluorophenyl) borane.

The invention still further provides the use of a catalyst composition as defined in any one of the preceding claims for the catalytic homo-or co-polymerisation of olefin monomers;

the specific process is as follows: under the protection of nitrogen, firstly dissolving the catalyst composition in a solvent, adding an olefin monomer, and reacting for 1-180 min at the temperature of-20-120 ℃ and the pressure of 0.1-5 MPa to prepare an olefin polymer;

the molar ratio of the ethylene to the catalyst composition is 10000-50000: 1-2, the molar ratio of the cycloolefin to the catalyst composition is 4-10000: 1-2, and the molar ratio of the polar/functional monomer to the catalyst composition is 10-40000: 1; according to the catalytic performance of the catalyst, the addition amount of the monomer is changed to change the catalytic activity, the content of functional/polar monomer in the polymer, the molecular weight of the polymer and the like, so that the content of the monomer can be adjusted as required;

the olefin polymer comprises olefin polymer and ethylene oligomer, and the number average molecular weight of the olefin polymer is 1100-620000 g & mol^-1Molecular weight distribution index (M)_w/M_n) 1.75 to 4.09, melting point (T)_m) The temperature is 83-461 ℃, and the ethylene oligomer mainly comprises butene and hexene.

Has the advantages that:

(1) the ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex contains 2-imino imidazoline and oxygen atoms with stronger 2 sigma and 4 pi electron donor characteristics, imidazoline rings can more effectively stabilize positive charges and increase electronegativity of nitrogen atoms, so that the alkalinity of a ligand and the electron donating capability are enhanced, and when the N atoms are bonded with a metal center (M), stronger N-M bonds can be formed, thereby being beneficial to improving the thermal stability of the complex and further improving the catalytic activity of the complex;

(2) the ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex forms zwitter-ion complexes with different structures when different cocatalysts act with oxygen atoms, and effectively controls the Lewis acidity of central metal, thereby effectively regulating and controlling the molecular weight and chain structure of olefin polymerization products;

(3) the ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex can have higher catalytic activity for catalyzing ethylene polymerization under the condition of no cocatalyst, can synthesize ethylene high polymer or high-selectivity ethylene oligomer under the condition of different cocatalysts, has higher polymerization activity for cycloolefins, and can obtain high molecular weight cycloolefine homopolymer and cycloolefine/ethylene copolymer;

(4) the ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex has higher tolerance to polar monomers, can be used for copolymerization of ethylene or cycloolefin and the polar monomers, and has higher molecular weight, higher activity and higher insertion rate.

Drawings

FIG. 1 is a crystal structure diagram of a ketone-imidazoline-2-imine [ N, O ] bidentate nickel complex of example 1;

FIG. 2 is a crystal structure diagram of a ketone-imidazoline-2-imine [ N, O ] bidentate nickel complex of example 2;

FIG. 3 is a crystal structure diagram of a ketone-imidazoline-2-imine [ N, O ] bidentate palladium complex of example 3;

FIG. 4 is a crystal structure diagram of a ketone-imidazoline-2-imine [ N, O ] bidentate palladium complex of example 4;

FIG. 5 is a crystal structure diagram of a ketone-imidazoline-2-imine [ N, O ] bidentate nickel complex of example 5;

FIG. 6 is a crystal structure diagram of a ketone-imidazoline-2-imine [ N, O ] bidentate nickel complex of example 6;

wherein C is a carbon atom, N is a nitrogen atom, O is an oxygen atom, P is a phosphorus atom, Ni is a nickel atom, and Pd is a palladium atom.

Detailed Description

The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

Example 1

The preparation method of the ketone-imidazoline-2-imine [ N, O ] bidentate nickel complex comprises the following specific steps:

(1) preparing a ketone-imidazoline-2-imine ligand;

(1.1) dissolving aminoacetaldehyde dimethyl acetal and O-methylisourea sulfate in water at a molar ratio of 1.5:1, and reacting for 6 hours at 60 ℃ under the action of catalyst hydrochloric acid to obtain a colorless solution, wherein the molar ratio of the hydrochloric acid to the O-methylisourea sulfate is 3: 1; namely 2-amino-1H-imidazole hemisulfate with the yield of 75 percent,¹H NMR(D₂O,,ppm):7.80(s,2H,＝CH)；

(1.2) reacting 2-amino-1H-imidazole hemisulfate with sodium carbonate with the molar weight 2 times that of the hemisulfate in an aqueous solution at room temperature for 3 hours to prepare a water-insoluble yellow brown oily matter 2-amino-1H-imidazole;

(1.3) dissolving 2-amino-1H-imidazole and iodobenzene in absolute ethyl alcohol, reacting for 16H at 80 ℃ under the action of a catalytic system, cooling to 50 ℃, drying the reaction solvent under vacuum condition, extracting with dichloromethane for multiple times, centrifuging to obtain a green dichloromethane extract, collecting the extract after sufficient extraction, drying under vacuum to obtain a crude product, recrystallizing in a toluene/n-hexane mixed solution to obtain a light green crystal product 1-phenyl-1H-imidazole-2-amineThe yield is 72 percent,¹H NMR(CDCl₃,,ppm):7.49(t,2H,＝CH),7.37-7.41(m,3H,＝CH),6.71 (d,2H,＝CH),4.48(s,2H,-NH₂) Wherein the catalytic system consists of cuprous iodide, 8-hydroxyquinoline and Cs₂CO₃The composition is that the molar ratio of 2-amino-1H-imidazole to iodobenzene is 1:1.1, the molar ratio of cuprous iodide to 8-hydroxyquinoline is 1:1.5, the molar ratio of cuprous iodide to 2-amino-1H-imidazole is 0.12:1, and Cs₂CO₃The molar ratio of the 2-amino-1H-imidazole to the compound is 3: 1;

(1.4) dissolving 1-phenyl-1H-imidazole-2-amine and benzoyl chloride in a molar ratio of 1:0.9 in toluene, reacting for 10 hours at 30 ℃ under the action of catalyst pyridine, wherein the molar ratio of pyridine to 1-phenyl-1H-imidazole-2-amine is 1.5:1, draining the reaction solvent, adding a proper amount of 5% KOH solution by mass, fully stirring, adding 50m L of extraction liquid dichloromethane, separating the extraction liquid by a separating funnel, collecting the extraction liquid after 3 times of extraction, adding anhydrous magnesium sulfate to remove water, reacting overnight, centrifuging and filtering to obtain yellow clear solution, draining to obtain a light yellow product N- (1-phenyl-1H-imidazole-2-yl) benzamide with the yield of 77%,¹H NMR(CDCl₃,,ppm):12.61(brs,1H,-NH),8.22(d,2H, ＝CH),7.71(d,2H,＝CH),7.54(t,2H,＝CH),7.46(t,1H,＝CH),7.40(q,4H,＝CH),6.88(d,2H,＝CH)。¹³C NMR(CDCl₃,,ppm):174.57,149.75,137.85,136.60,130.90,129.18,128.87,127.92,127.61,124.59,114.87, 113.16；

(2) dissolving N- (1-phenyl-1H-imidazole-2-yl) benzamide in tetrahydrofuran, adding N-butyllithium at the temperature of-78 ℃, slowly heating to room temperature, and reacting for 4 hours to obtain a salt compound, wherein the molar ratio of the N-butyllithium to the N- (1-phenyl-1H-imidazole-2-yl) benzamide is 1.2: 1;

(3) adding trans-chloro- (phenyl) bis (triphenylphosphine) nickel into the system in the step (2), wherein the molar ratio of the addition amount to the addition amount of the ketone-imidazoline-2-imine ligand in the step (2) is 1:1, reacting at 30 ℃ for 9H, draining, washing with 30m L anhydrous N-hexane for 2 times, and obtaining a yellow green crystal in dichloromethane/N-hexane, namely the ketone-imidazoline-2-imine with the N- (1-phenyl-1H-imidazole-2-yl) benzamide as a ligand structureN,O]The corresponding crystal structure schematic diagram of the bidentate nickel complex is shown in figure 1;¹H NMR(C₄D₈O,600MHz):7.71(d, 2H,Ar-H),7.61-7.64(m,6H,Ar-H),7.49(t,2H,Ar-H)，7.41(t,3H,Ar-H)，7.28-7.41(m,10H,Ar-H), 7.11-7.14(m,3H,Ar-H)，6.91(t,2H,Ar-H),6.80(s,1H,＝CH),6.61-6.66(m,3H,Ar-H,＝CH)。³¹P NMR (C₄D₈O,600MHz):31.53(s,P)。Anal.Calcd.for C₄₀H₃₂N₃NiOP:C,72.75；H,4.88；N,6.36.Found:C,72.56； H,4.85；N,6.23。

the structural formula of the prepared nickel complex is as follows:

wherein R is₁R' is phenyl, R₂～R₇Is hydrogen, M is nickel, L is triphenylphosphine.

Example 2

(1) preparing a ketone-imidazoline-2-imine ligand;

(1.1) dissolving aminoacetaldehyde dimethyl acetal and O-methylisourea sulfate in water at a molar ratio of 1.5:1, and reacting for 6 hours at 60 ℃ under the action of catalyst sulfuric acid to obtain a colorless solution, wherein the molar ratio of the sulfuric acid to the O-methylisourea sulfate is 3: 2; namely 2-amino-1H-imidazole hemisulfate with a yield of 75%.¹H NMR(D₂O,,ppm):7.80(s,2H,＝CH)；

(1.2) reacting 2-amino-1H-imidazole hemisulfate with sodium carbonate with the molar weight of 2.5 times of that of the sodium carbonate in an aqueous solution at room temperature for 3 hours to prepare 2-amino-1H-imidazole;

(1.3) dissolving 2-amino-1H-imidazole and iodobenzene in anhydrous isopropanol, reacting for 16H at 80 ℃ under the action of a catalytic system, cooling to 50 ℃, drying the reaction solvent under vacuum, extracting with dichloromethane for multiple times, centrifuging to obtain green dichloromethane extract, collecting the extract after sufficient extraction, drying under vacuum to obtain a crude product, and purifying with toluene/n-hexaneRecrystallizing in the mixed solution to obtain a light green crystal product 1-phenyl-1H-imidazole-2-amine with the yield of 72 percent,¹H NMR(CDCl₃,,ppm):7.49(t,2H,＝CH),7.37-7.41(m,3H,＝CH), 6.71(d,2H,＝CH),4.48(s,2H,-NH₂) Wherein the catalytic system consists of cuprous iodide, 8-hydroxyquinoline and Cs₂CO₃The composition is that the molar ratio of 2-amino-1H-imidazole to iodobenzene is 1:1.1, the molar ratio of cuprous iodide to 8-hydroxyquinoline is 1:1.5, the molar ratio of cuprous iodide to 2-amino-1H-imidazole is 0.12:1, and Cs₂CO₃The molar ratio of the 2-amino-1H-imidazole to the compound is 3: 1;

(1.4) dissolving 1-phenyl-1H-imidazole-2-amine and adamantane chloride with a molar ratio of 1:0.9 in toluene, reacting for 10 hours at 30 ℃ under the action of catalyst pyridine, wherein the molar ratio of pyridine to 1-phenyl-1H-imidazole-2-amine is 1.5:1, draining the reaction solvent, adding a proper amount of 5% KOH solution by mass, fully stirring, adding 50m L of extraction liquid dichloromethane, separating the extraction liquid by a separating funnel, extracting for 3 times, collecting the extraction liquid, adding anhydrous magnesium sulfate to remove water, reacting overnight, centrifuging and filtering to obtain yellow clear solution, draining to obtain a light yellow product N- (1-phenyl-1H-imidazole-2-yl) adamantane formamide with a yield of 71%,¹H NMR(DMSO,,ppm):9.44(s,1H,-NH),7.48(t, 2H,＝CH),7.36-7.40(m,4H,＝CH),6.99(s,1H,＝CH),1.94(s,3H,-CH₂),1.70(s,6H,-CH),1.65(q,6H, -CH₂).¹³C NMR(DMSO,,ppm):178.06,138.44,137.23,129.53,128.08,126.85,124.75,121.00,40.67, 38.70,36.43,27.96；

(2) dissolving N- (1-phenyl-1H-imidazole-2-yl) adamantane carboxamide ligand in tetrahydrofuran, adding N-butyl lithium at the temperature of-78 ℃, slowly heating to room temperature, and reacting for 4H to obtain a salt compound, wherein the molar ratio of the N-butyl lithium to the N- (1-phenyl-1H-imidazole-2-yl) adamantane carboxamide ligand is 1.2: 1;

(3) adding trans-chloro- (phenyl) bis (triphenylphosphine) nickel into the system in the step (2), wherein the molar ratio of the addition amount of the trans-chloro- (phenyl) bis (triphenylphosphine) nickel to the addition amount of the ketone-imidazoline-2-imine ligand in the step (2) is 1:1, reacting for 9h at 30 ℃, draining, washing for 2 times by 30m L anhydrous n-hexane, and obtaining yellow needle-like n-hexane in dichloromethane/n-hexaneCrystal, namely the ketone-imidazoline-2-imine [ N, O ] taking N- (1-phenyl-1H-imidazole-2-yl) adamantane formamide as a ligand structure]The corresponding crystal structure schematic diagram of the bidentate nickel complex is shown in FIG. 2;¹H NMR(C₄D₈O,600MHz): 7.69(d,2H,Ar-H),7.57-7.60(m,6H,Ar-H),7.49(s,1H,Ar-H)，7.39-7.42(m,5H,Ar-H),7.30-7.33(m,6H, Ar-H)，7.24-7.27(m,3H,Ar-H)，6.73(s,1H,＝CH)，6.58(m,3H,Ar-H,＝CH)，1.65(s,3H,-CH),1.52(d,3H, -CH),1.41(d,3H,-CH),1.31-1.33(m,6H,-CH)。³¹P NMR(C₄D₈O,600MHz):31.94(s,P)。Anal.Calcd.forC₄₄H₄₂N₃NiOP:C,73.55；H,5.89；N,5.85.Found:C,73.46；H,5.84；N,5.81。

the structural formula of the prepared nickel complex is as follows:

wherein R is₁R' is phenyl, R₂、R₈-R₁₁Is hydrogen, M is nickel, L is triphenylphosphine.

Example 3

The preparation method of the ketone-imidazoline-2-imine [ N, O ] bidentate palladium complex comprises the following specific steps:

(1) preparing a ketone-imidazoline-2-imine ligand;

(1.1) dissolving aminoacetaldehyde dimethyl acetal and O-methylisourea sulfate in water at a molar ratio of 1.5:1, and reacting for 6 hours at 60 ℃ under the action of catalyst nitric acid to obtain a colorless solution, wherein the molar ratio of the nitric acid to the O-methylisourea sulfate is 3: 2; namely 2-amino-1H-imidazole hemisulfate with a yield of 75%.¹H NMR(D₂O,,ppm):7.80(s,2H,＝CH)；

(1.2) reacting 2-amino-1H-imidazole hemisulfate with sodium carbonate with the molar weight being 3 times of that of the hemisulfate in an aqueous solution at room temperature for 3 hours to prepare 2-amino-1H-imidazole;

(1.3) dissolving 2-amino-1H-imidazole and iodobenzene in anhydrous isopropanol, reacting for 16H at 80 ℃ under the action of a catalytic system, cooling to 50 ℃, and pumping out the reaction solvent under the vacuum conditionExtracting with dichloromethane for multiple times, centrifuging to obtain green dichloromethane extractive solution, collecting the extractive solution after extraction, vacuum drying to obtain crude product, recrystallizing in toluene/n-hexane mixed solution to obtain light green crystal product 1-phenyl-1H-imidazole-2-amine with yield of 72%,¹H NMR(CDCl₃,,ppm):7.49(t,2H,＝CH),7.37-7.41(m,3H,＝CH), 6.71(d,2H,＝CH),4.48(s,2H,-NH₂) Wherein the catalytic system consists of cuprous iodide, 8-hydroxyquinoline and Cs₂CO₃The composition is that the molar ratio of 2-amino-1H-imidazole to iodobenzene is 1:1.1, the molar ratio of cuprous iodide to 8-hydroxyquinoline is 1:1.5, the molar ratio of cuprous iodide to 2-amino-1H-imidazole is 0.12:1, and Cs₂CO₃The molar ratio of the 2-amino-1H-imidazole to the compound is 3: 1;

(1.4) dissolving 1-phenyl-1H-imidazole-2-amine and benzoyl chloride in a molar ratio of 1:0.9 in toluene, reacting for 10 hours at 30 ℃ under the action of catalyst pyridine, wherein the molar ratio of pyridine to 1-phenyl-1H-imidazole-2-amine is 1.5:1, draining the reaction solvent, adding a proper amount of 5% KOH solution by mass, fully stirring, adding 50m L of extraction liquid dichloromethane, separating the extraction liquid by a separating funnel, collecting the extraction liquid after 3 times of extraction, adding anhydrous magnesium sulfate to remove water, reacting overnight, centrifugally filtering to obtain yellow clear solution, draining to obtain a light yellow product N- (1-phenyl-1H-imidazole-2-yl) benzamide with the yield of 77%,¹H NMR(CDCl₃,,ppm):12.61(brs,1H,-NH),8.22(d,2H, ＝CH),7.71(d,2H,＝CH),7.54(t,2H,＝CH),7.46(t,1H,＝CH),7.40(q,4H,＝CH),6.88(d,2H,＝CH)。¹³C NMR(CDCl₃,,ppm):174.57,149.75,137.85,136.60,130.90,129.18,128.87,127.92,127.61,124.59,114.87, 113.16；

(2) dissolving an N- (1-phenyl-1H-imidazole-2-yl) benzamide ligand in tetrahydrofuran, adding N-butyllithium at the temperature of-78 ℃, slowly heating to room temperature, and reacting for 4 hours to obtain a salt compound, wherein the molar ratio of the N-butyllithium to the N- (1-phenyl-1H-imidazole-2-yl) benzamide ligand is 1.2: 1;

(3) adding chlorine (cyclooctadiene) methyl palladium into the system in the step (2) in the same amount as that of the N- (1-phenyl-1H-imidazole in the step (2)The molar ratio of the adding amount of the (E) -2-yl) benzamide ligand is 0.5:1, the reaction is carried out for 9H at the temperature of 30 ℃, then pyridine is added, the molar ratio of the adding amount of the pyridine to the adding amount of the N- (1-phenyl-1H-imidazole-2-yl) benzamide ligand in the step (2) is 1:1, the reaction is continued for 1H, the pumping is carried out, 30m L anhydrous N-hexane is used for washing for 2 times, yellow crystals, namely the ketone-imidazoline-2-imine [ N, O ] are obtained in dichloromethane/N-hexane]The corresponding crystal structure schematic diagram of the bidentate palladium complex is shown in FIG. 3;¹H NMR(CDCl₃,600MHz):8.13(d,4H,Ar-H),7.71(d,4H,Ar-H), 7.56(t,4H,Ar-H)，7.44-7.45(m,4H,Ar-H)，7.40(t,6H,Ar-H),7.36(d,2H,-C＝H)，7.02(d,2H,-C＝H)。Anal. Calcd.forC₃₂H₂₄N₆O₂Pd:C,60.91；H,3.83；N,13.32.Found:C,60.73；H,3.90；N,13.21。

the structural formula of the prepared [ N, O ] bidentate palladium complex is as follows:

wherein R is₁、R₂～R₇Is hydrogen and M is palladium.

Example 4

(1) preparing a ketone-imidazoline-2-imine ligand;

(1.1) dissolving aminoacetaldehyde dimethyl acetal and O-methyl isourea sulfate in water at a molar ratio of 1.5:1, and reacting for 6 hours at 60 ℃ under the action of catalyst phosphoric acid to obtain a colorless solution, wherein the molar ratio of the phosphoric acid to the O-methyl isourea sulfate is 3: 2; namely 2-amino-1H-imidazole hemisulfate with a yield of 75%.¹H NMR(D₂O,,ppm):7.80(s,2H,＝CH)；

(1.2) reacting 2-amino-1H-imidazole hemisulfate with sodium carbonate with the molar weight 5 times that of the sodium carbonate in an aqueous solution at room temperature for 3 hours to prepare 2-amino-1H-imidazole;

(1.3) dissolving 2-amino-1H-imidazole and iodobenzene in anhydrous isopropanol, reacting for 16H at 80 ℃ under the action of a catalytic system, cooling to 50 ℃, and carrying out vacuum stripPumping the reaction solvent off the components, extracting with dichloromethane for multiple times, centrifuging to obtain green dichloromethane extract, collecting the extract after sufficient extraction, vacuum-pumping to obtain crude product, recrystallizing in toluene/n-hexane mixed solution to obtain light green crystal product 1-phenyl-1H-imidazole-2-amine with yield of 72%,¹H NMR(CDCl₃,,ppm):7.49(t,2H,＝CH),7.37-7.41(m,3H,＝CH), 6.71(d,2H,＝CH),4.48(s,2H,-NH₂) Wherein the catalytic system consists of cuprous iodide, 8-hydroxyquinoline and Cs₂CO₃The composition is that the molar ratio of 2-amino-1H-imidazole to iodobenzene is 1:1.1, the molar ratio of cuprous iodide to 8-hydroxyquinoline is 1:1.5, the molar ratio of cuprous iodide to 2-amino-1H-imidazole is 0.12:1, and Cs₂CO₃The molar ratio of the 2-amino-1H-imidazole to the compound is 3: 1;

(1.4) dissolving 1-phenyl-1H-imidazole-2-amine and adamantane chloride with a molar ratio of 1:0.9 in toluene, reacting for 10 hours at 30 ℃ under the action of catalyst pyridine, wherein the molar ratio of pyridine to 1-phenyl-1H-imidazole-2-amine is 1.5:1, draining the reaction solvent, adding a proper amount of 5% KOH solution by mass, fully stirring, adding 50m L of extraction liquid dichloromethane, separating the extraction liquid by a separating funnel, extracting for 3 times, collecting the extraction liquid, adding anhydrous magnesium sulfate to remove water, reacting overnight, centrifuging and filtering to obtain yellow clear solution, draining to obtain a light yellow product N- (1-phenyl-1H-imidazole-2-yl) adamantane formamide with a yield of 71%,¹H NMR(DMSO,,ppm):9.44(s,1H,-NH),7.48(t,2H, ＝CH),7.36-7.40(m,4H,＝CH),6.99(s,1H,＝CH),1.94(s,3H,-CH₂),1.70(s,6H,-CH),1.65(q,6H,-CH₂).¹³C NMR(DMSO,,ppm):178.06,138.44,137.23,129.53,128.08,126.85,124.75,121.00,40.67,38.70,36.43,27.96；

(3) adding chloro (cyclooctadiene) methyl palladium into the system in the step (2) in the amount ofThe molar ratio of the addition amount of the ketone-imidazoline-2-imine ligand in the step (2) is 0.5:1, the reaction is carried out for 9 hours at the temperature of 30 ℃, then dimethyl sulfoxide is added, the molar ratio of the addition amount of the dimethyl sulfoxide to the addition amount of the N- (1-phenyl-1H-imidazole-2-yl) adamantane formamide ligand in the step (2) is 2:1, the reaction is continued for 3 hours, the pumping is carried out, the washing is carried out for 2 times by 30m L anhydrous N-hexane, and yellow needle-shaped crystals are obtained in dichloromethane/N-hexane, namely the ketone-imidazoline-2-imine [ N, O]The corresponding crystal structure schematic diagram of the bidentate palladium complex is shown in FIG. 4;¹H NMR(CDCl₃,600MHz):7.67(d,4H,Ar-H),7.48(t,4H,Ar-H), 7.35(t,2H,Ar-H)，7.12(d,2H,-C＝H),6.91(d,2H,-C＝H)，2.02(s,6H,-CH)，1.94(d,12H,-CH₂)，1.72(d,12H, -CH₂)。Anal.Calcd.for C₄₀H₄₄N₆O₂Pd:C,64.29；H,5.94；N,11.25.Found:C,63.83；H,5.92；N,11.15。

wherein R is₁Is phenyl, R₂、R₈～R₁₁Is hydrogen and M is palladium.

Example 5

(1) preparing a ketone-imidazoline-2-imine ligand;

(1.1) refluxing 2-bromoacetophenone and 1-acetylguanidine in a molar ratio of 1:2 in acetonitrile at 80 ℃ for 9H to prepare N- (4-phenyl-1H-imidazol-2-yl) formamide, reacting for 4H under the acidic condition of sulfuric acid with the pH of 2.0 to obtain 2-amino-4-phenyl-1H-imidazole hemisulfate with the yield of 16%,¹H NMR(DMSO,,ppm):12.68(s,H,-OH),12.06(s,H,-NH),7.64(d,2H,＝CH),7.54(s,2H, -NH₂),7.45(t,H,＝CH),7.43(s,H,＝CH),7.34(t,H,＝CH)；

(1.2) reacting 2-amino-4-phenyl-1H-imidazole hemisulfate with sodium carbonate with the molar weight 5 times that of the sodium carbonate in an aqueous solution at room temperature for 3 hours to prepare 2-amino-4-phenyl-1H-imidazole;

(1.3) dissolving 2-amino-4-phenyl-1H-imidazole and iodobenzene in anhydrous tert-butyl alcohol, reacting for 16H at 80 ℃ under the action of a catalytic system, cooling to 50 ℃, draining the reaction solvent under vacuum condition, extracting with dichloromethane for multiple times, centrifuging to obtain a green dichloromethane extract, collecting the extract after sufficient extraction, draining under vacuum to obtain a crude product, recrystallizing in a toluene/n-hexane mixed solution to obtain a light green crystal product 1, 4-diphenyl-1H-imidazole-2-amine with a yield of 61%,¹HNMR(CDCl₃,,ppm):7.73(d,2H,＝CH),7.54(t,2H, ＝CH),7.48(d,2H,＝CH),7.43(t,H,＝CH),7.38(t,2H,＝CH),7.24(t,H,＝CH),7.05(s,H,＝CH),4.44(s,H, -NH₂) Wherein the catalytic system consists of cuprous iodide, 8-hydroxyquinoline and Cs₂CO₃The composition is that the molar ratio of 2-amino-4-phenyl-1H-imidazole to iodobenzene is 1:1.1, the molar ratio of cuprous iodide to hydroxyquinoline is 1:1.5, the molar ratio of cuprous iodide 2-amino-4-phenyl-1H-imidazole is 0.12:1, and Cs₂CO₃The molar ratio to 2-amino-4-phenyl-1H-imidazole is 3: 1;

(1.4) dissolving 1, 4-diphenyl-1H-imidazole-2-amine and benzoyl chloride with a molar ratio of 1:0.9 in toluene, reacting for 10 hours at 30 ℃ under the action of catalyst pyridine, wherein the molar ratio of pyridine to 1-phenyl-1H-imidazole-2-amine is 1.5:1, pumping out the reaction solvent, adding a proper amount of 5% by mass KOH solution, fully stirring, adding 50m L dichloromethane extract, separating the extract by using a separating funnel, collecting the extract after 3 times of extraction, adding anhydrous magnesium sulfate to remove water, reacting overnight, centrifuging and filtering to obtain yellow clear solution, pumping out to obtain a light yellow product N- (1, 4-diphenyl-1H-imidazole-2-yl) benzamide with a yield of 67%,¹H NMR(CDCl₃,,ppm):7.83(d,2H,＝CH),7.67(d, 4H,＝CH),7.47(t,2H,＝CH),7.42(t,2H,＝CH),7.39(d,2H,＝CH),7.33(m,3H,＝CH,-NH),7.19(d,2H, ＝CH)。¹³C NMR(CDCl₃,,ppm):171.95,141.13,138.95,135.55,133.58,133.46,132.80,129.60,129.29,128.91,128.61,128.40,127.31,125.08,125.02,116.23；

(2) dissolving an N- (1, 4-diphenyl-1H-imidazol-2-yl) benzamide ligand in tetrahydrofuran, adding N-butyl lithium at the temperature of-78 ℃, slowly heating to room temperature, and reacting for 4 hours to obtain a salt compound, wherein the molar ratio of the N-butyl lithium to the ketone-imidazoline-2-imine N- (1, 4-diphenyl-1H-imidazol-2-yl) benzamide ligand is 1.2: 1;

(3) adding (ethylene glycol dimethyl ether) nickel bromide into the system in the step (2), wherein the molar ratio of the addition amount of the nickel bromide to the addition amount of the N- (1, 4-diphenyl-1H-imidazole-2-yl) benzamide ligand in the step (2) is 0.5:1, reacting for 9H at 30 ℃, draining, washing for 2 times by 30m L anhydrous N-hexane, and obtaining a reddish brown crystal in dichloromethane/N-hexane, namely the ketone-imidazoline-2-imine [ N, O ] with the N- (1, 4-diphenyl-1H-imidazole-2-yl) benzamide ligand as the structure]The corresponding crystal structure schematic diagram of the bidentate nickel complex is shown in FIG. 5;¹H NMR(C₄D₈O,600 MHz):7.90(d,4H,Ar-H),7.49(t,2H,Ar-H),7.42(m,5H,Ar-H,＝CH)，7.33(m,6H,Ar-H)，7.28(s,1H, ＝CH),6.78(br,4H,Ar-H)。Anal.Calcd.for C₄₃H₃₁N₆NiO₂:C,71.49；H,4.33；N,11.63.Found:C,71.44；H, 4.35；N,11.43。

the structural formula of the prepared [ N, O ] bidentate nickel complex is as follows:

wherein R is₁、R₂And R' is phenyl, R₃～R₇Is hydrogen and M is nickel.

Example 6

(1) preparing a ketone-imidazoline-2-imine ligand;

(1.4) dissolving 1, 4-diphenyl-1H-imidazole-2-amine and adamantane chloride in toluene, reacting for 10H at 30 ℃ under the action of catalyst pyridine, wherein the molar ratio of the pyridine to the 1-phenyl-1H-imidazole-2-amine is 1.5:1, pumping out the reaction solvent, adding a proper amount of 5% KOH solution, fully stirring, adding 50m L dichloromethane extract, separating the extract by a separating funnel, extracting for 3 times, collecting the extract, adding anhydrous magnesium sulfate to remove water, reacting overnight, centrifugally filtering to obtain yellow clear solution, pumping out to obtain a light yellow product N- (1, 4-diphenyl-1H-imidazole-2-yl) adamantane formamide with the yield of 36%,¹HNMR(CDCl₃,,ppm):11.04(s,H,-NH),7.90(d,2H,＝CH), 7.28-7.49(m,7H,＝CH),6.78(s,2H,＝CH),1.97(s,3H,-CH),1.77(s,6H,-CH),1.63-1.70(m,6H,-CH)。¹³C NMR(CDCl₃,,ppm):193.67,169.85,158.54,130.73,130.53,129.77,128.51,128.39,127.18,126.76,102.17,99.37,43.94,38.90,36.69,28.17；

(2) dissolving an N- (1, 4-diphenyl-1H-imidazol-2-yl) adamantane carboxamide ligand in tetrahydrofuran, adding N-butyl lithium at the temperature of-78 ℃, slowly heating to room temperature, and reacting for 4H to obtain a salt compound, wherein the molar ratio of the N-butyl lithium to the N- (1, 4-diphenyl-1H-imidazol-2-yl) adamantane carboxamide ligand is 1.2: 1;

(3) adding (ethylene glycol dimethyl ether) nickel bromide into the system in the step (2), wherein the molar ratio of the addition amount of the nickel bromide to the addition amount of the N- (1, 4-diphenyl-1H-imidazole-2-yl) adamantane carboxamide ligand in the step (2) is 0.5:1, reacting for 9H at 30 ℃, draining, washing for 2 times by 30m L anhydrous N-hexane, and obtaining a reddish brown crystal in dichloromethane/N-hexane, namely the ketone-imidazoline-2-imine [ N, O ] with the N- (1, 4-diphenyl-1H-imidazole-2-yl) adamantane carboxamide ligand as the structure]The corresponding crystal structure schematic diagram of the bidentate nickel complex is shown in FIG. 6;¹H NMR (C₄D₈O,600MHz):7.90(d,4H,＝CH),7.41-7.50(m,7H,＝CH),7.28-7.34(m,7H,＝CH)，6.78(s,4H,＝CH), 1.97(s,6H,-CH)，1.79(s,12H,-CH)，1.62-1.70(m,12H,-CH)。Anal.Calcd.for C₅₂H₅₂N₆NiO₂:C,73.33；H, 6.15；N,9.87.Found:C,73.03；H,6.23；N,9.47。

wherein R is₁、R₂R' is phenyl, R₈～R₁₁Is hydrogen and M is nickel.

Example 7

(1) preparing a ketone-imidazoline-2-imine ligand;

(1.1) dissolving aminoacetaldehyde diethyl acetal and S-methylisourea sulfate in water in a molar ratio of 1:3, and reacting for 11 hours at 50 ℃ under the action of catalyst hydrochloric acid to prepare 2-amino-1H-imidazole hemisulfate, wherein the molar ratio of the hydrochloric acid to the S-methylisourea sulfate is 5: 1;

(1.2) reacting 2-amino-1H-imidazole hemisulfate with potassium hydroxide with the molar weight being 10 times of that of the hemisulfate in an aqueous solution at room temperature for 3 hours to prepare 2-amino-1H-imidazole;

(1.3) dissolving 2-amino-1H-imidazole and methyl iodide in absolute methanol, and reacting for 36H at 50 ℃ under the action of a catalytic system to prepare 1-methyl-1H-imidazole-2-amine, wherein the catalytic system is mainly cuprous iodide, 8-hydroxyquinoline and NaO^tBu, the molar ratio of 2-amino-1H-imidazole to methyl iodide is 1:1, the molar ratio of cuprous iodide to 8-hydroxyquinoline is 1:1, the molar ratio of cuprous iodide to 2-amino-1H-imidazole is 0.05:1, and NaO^tThe molar ratio of Bu to 2-amino-1H-imidazole is 1: 1;

(1.4) 1-methyl-1H-imidazol-2-amine and 4-bromobenzoyl chloride in a molar ratio of 1:1 were dissolved in ethanol at 50 ℃ with KHCO as catalyst₃Reacting for 12H under the action of the catalyst to obtain 4-bromo-N- (1-methyl-1H-imidazole-2-yl) benzoylimine ligand, wherein KHCO is₃The molar ratio of the bromobenzoyl chloride to the 4-bromobenzoyl chloride is 4: 1;

separating and purifying the product by column chromatography; the elution solvent used in the column chromatography is ethyl acetate-n-hexane;

(2) dissolving 4-bromo-N- (1-methyl-1H-imidazole-2-yl) benzoylimine ligand in toluene, and adding sodium hydride to react for 1H at the temperature of 35 ℃ to prepare a salt compound, wherein the molar ratio of the sodium hydride to the ketone-imidazoline-2-imine ligand is 1.2: 1;

(3) adding trans-chloro- (methyl) bis (trimethylphosphine) nickel into the system in the step (2), wherein the molar ratio of the addition amount to the addition amount of the 4-bromo-N- (1-methyl-1H-imidazol-2-yl) benzoylimine ligand in the step (2) is 0.5:1, and reacting for 26H at 25 ℃ to obtain the ketone-imidazoline-2-imine [ N, O ] bidentate nickel complex taking the 4-bromo-N- (1-methyl-1H-imidazol-2-yl) benzoylimine ligand as the structure.

example 8

(1) preparing a ketone-imidazoline-2-imine ligand;

(1.1) dissolving aminoacetaldehyde dimethyl acetal and S-methylisourea sulfate in water at a molar ratio of 3:1, and reacting for 7 hours at 90 ℃ under the action of catalyst phosphoric acid to prepare 2-amino-1H-imidazole hemisulfate, wherein the molar ratio of phosphoric acid to S-methylisourea sulfate is 3: 2;

(1.2) reacting 2-amino-1H-imidazole hemisulfate with sodium hydroxide with the molar weight being 2 times of that of the hemisulfate in an aqueous solution at room temperature for 3 hours to prepare 2-amino-1H-imidazole;

(1.3) dissolving 2-amino-1H-imidazole and 2-iodopropane in anhydrous tert-butyl alcohol, reacting for 18H at 95 ℃ under the action of a catalytic system, and cooling to 50 ℃ to obtain 1-propyl-1H-imidazole-2-amine, wherein the catalytic system comprises cuprous iodide, 8-hydroxyquinoline and K₃PO₄The composition is that the molar ratio of 2-amino-1H-imidazole to 2-iodopropane is 1:1.5, the molar ratio of cuprous iodide to 8-hydroxyquinoline is 1:2, the molar ratio of cuprous iodide to 2-amino-1H-imidazole is 0.2:1, K₃PO₄The molar ratio of the 2-amino-1H-imidazole to the compound is 3: 1;

(1.4) dissolving 1-propyl-1H-imidazole-2-amine and 4-bromo-3, 5-dimethoxybenzoyl chloride in a molar ratio of 1.2:1 in dichloromethane, and reacting for 18H at-78 ℃ under the action of a catalyst triethylamine to obtain 4-bromo-3, 5-dimethoxy-N- (1-propyl-1H-imidazole-2-yl) benzoylimine ligand, wherein the molar ratio of triethylamine to 4-bromo-3, 5-dimethoxybenzoyl chloride is 3: 1;

separating and purifying the product by an organic solvent recrystallization method; the organic solvent used in the organic solvent recrystallization method is toluene;

(2) dissolving 4-bromo-3, 5-dimethoxy-N- (1-propyl-1H-imidazol-2-yl) benzoylimine ligand in diethyl ether, adding potassium hydride at the temperature of 5 ℃ to react for 8 hours to prepare a salt compound, wherein the molar ratio of the potassium hydride to the 4-bromo-3, 5-dimethoxy-N- (1-propyl-1H-imidazol-2-yl) benzoylimine ligand is 2.2: 1;

(3) adding allyl nickel chloride dimer into the system in the step (2), wherein the molar ratio of the addition amount to the addition amount of the ketone-imidazoline-2-imine ligand in the step (2) is 0.8:1, and reacting for 5 hours at 30 ℃ to obtain the ketone-imidazoline-2-imine [ N, O ] bidentate nickel complex with the 4-bromo-3, 5-dimethoxy-N- (1-propyl-1H-imidazole-2-yl) benzoylimine ligand as the structure.

example 9

(1) preparing a ketone-imidazoline-2-imine ligand;

(1.1) refluxing 2-bromoacetophenone and 1-acetylguanidine in a molar ratio of 1:5 in acetonitrile at 60 ℃ for 11H to prepare N- (4-phenyl-1H-imidazole-2-yl) formamide, and then reacting for 2H under the acidic condition of sulfuric acid with the pH value of 2.0 to obtain 2-amino-4-phenyl-1H-imidazole hemisulfate;

(1.2) reacting 2-amino-4-phenyl-1H-imidazole hemisulfate with potassium carbonate with the molar weight 5 times that of the hemisulfate in an aqueous solution at room temperature for 3 hours to prepare 2-amino-4-phenyl-1H-imidazole;

(1.3) dissolving 2-amino-4-phenyl-1H-imidazole and iodo-tert-butane in absolute ethanol, reacting for 16H at 90 ℃ under the action of a catalytic system, and cooling to 50 ℃ to obtain 1-tert-butyl-4-phenyl-1H-imidazole-2-amine, wherein the catalytic system comprises cuprous iodide, 8-hydroxyquinoline and K₂CO₃Comprises 2-amino-4-phenyl-1H-imidazole and iodo-tert-butane at a molar ratio of 1:1.2, cuprous iodide at a molar ratio of 1:1.5 to 8-hydroxyquinoline at a molar ratio of 0.1:1, and K₂CO₃The molar ratio to 2-amino-4-phenyl-1H-imidazole is 2: 1;

(1.4) 1-tert-butyl-4-phenyl-1H-imidazol-2-amine and 3-bromo-4-methoxybenzoyl chloride in a molar ratio of 1.2:1 were dissolved in 1, 4-dioxane at 50 ℃ and catalyst Cs₂CO₃Reacting for 15 hours under the action of the catalyst to obtain 3-bromo-4-methoxy-N- (1-tert-butyl-4-phenyl-1H-imidazole-2-yl) benzoylimine ligand, wherein Cs is₂CO₃The molar ratio of the acyl chloride compound to the acyl chloride compound is 2: 1;

separating and purifying the product by an organic solvent extraction method; the organic solvent used in the organic solvent recrystallization method or the organic solvent extraction method is n-hexane;

(2) dissolving ketone-imidazoline-2-imine ligand in N-heptane, and adding methyllithium to react for 8H at the temperature of 5 ℃ to prepare a salt compound, wherein the molar ratio of methyllithium to 3-bromo-4-methoxy-N- (1-tert-butyl-4-phenyl-1H-imidazol-2-yl) benzoylimine ligand is 1.2: 1;

(3) adding allyl palladium chloride dimer into the system in the step (2), wherein the molar ratio of the addition amount of allyl palladium chloride dimer to the addition amount of the ketone-imidazoline-2-imine ligand in the step (2) is 0.5:1, reacting at 60 ℃ for 5 hours, then adding dimethyl sulfoxide, wherein the molar ratio of the addition amount of the dimethyl sulfoxide to the addition amount of the ketone-imidazoline-2-imine ligand in the step (2) is 5:1, and continuing to react for 6 hours to obtain the ketone-imidazoline-2-imine [ N, O ] bidentate palladium complex with the 3-bromo-4-methoxy-N- (1-tert-butyl-4-phenyl-1H-imidazole-2-yl) benzoyl imine ligand as the structure.

example 10

(1) preparing a ketone-imidazoline-2-imine ligand;

(1.1) refluxing 2-bromoacetophenone and 1-acetylguanidine in a molar ratio of 2:1 in acetonitrile at 100 ℃ for 6H to prepare N- (4-phenyl-1H-imidazole-2-yl) formamide, and then reacting for 2H under the acidic condition of sulfuric acid with the pH value of 2.0 to obtain 2-amino-4-phenyl-1H-imidazole hemisulfate;

(1.2) respectively reacting 2-amino-4-phenyl-1H-imidazole hemisulfate with sodium bicarbonate with the molar weight being 6 times of that of the hemisulfate in an aqueous solution at room temperature for 3 hours to prepare 2-amino-4-phenyl-1H-imidazole;

(1.3) dissolving 2-amino-4-phenyl-1H-imidazole and 1-iodopropane in absolute ethyl alcohol, reacting for 20H at 80 ℃ under the action of a catalytic system, and cooling to 50 ℃ to obtain 1-propyl-4-phenyl-1H-imidazole-2-amine, wherein the catalytic system comprises cuprous iodide, 8-hydroxyquinoline and K₃PO₄Comprises 2-amino-4-phenyl-1H-imidazole and 1-iodopropane in a molar ratio of 1:1.5, cuprous iodide and 8-hydroxyquinoline in a molar ratio of 1:1.7, cuprous iodide and 2-amino-4-phenyl-1H-imidazole in a molar ratio of 0.15:1, and K₃PO₄The molar ratio to 2-amino-4-phenyl-1H-imidazole is 2.4: 1;

(1.4) 1-propyl-4-phenyl-1H-imidazol-2-amine and 4-fluorophenylsulfinyl chloride in a molar ratio of 1.2:1 were dissolved in chlorobenzene solvent at 50 ℃ with KHCO as catalyst₃Reacting for 15 hours under the action to prepare a 4-fluorine-N- (1-propyl-4-phenyl-1H-imidazole-2-yl) benzene sulfenimide ligand, wherein the molar ratio of the catalyst to the 4-fluorobenzene sulfenyl chloride is 2: 1;

separating and purifying the product by an organic solvent extraction method; the organic solvent used in the organic solvent extraction method is chloroform;

(2) dissolving a 4-fluoro-N- (1-propyl-4-phenyl-1H-imidazole-2-yl) benzene sulfinimide ligand in 1, 4-dioxane, and adding bis (trimethylsilyl) sodium amide to react for 6 hours at the temperature of 5 ℃ to prepare a salt compound, wherein the molar ratio of the bis (trimethylsilyl) sodium amide to the ketone-imidazoline-2-imine ligand is 2: 1;

(3) adding trans-chloro- (phenyl) bis (triphenylphosphine) nickel into the system in the step (2), wherein the molar ratio of the addition amount to the addition amount of the 4-fluoro-N- (1-propyl-4-phenyl-1H-imidazole-2-yl) benzene sulfenimide ligand in the step (2) is 1:1, and reacting for 17 hours at 30 ℃ to obtain the ketone-imidazoline-2-imine [ N, O ] bidentate nickel complex taking the 4-fluoro-N- (1-propyl-4-phenyl-1H-imidazole-2-yl) benzene sulfenimide ligand as the structure.

examples 11 to 13

A process for producing a ketone-imidazoline-2-imine [ N, O ] bidentate nickel complex, which is substantially the same as in example 10, except that 1-iodopropane in step (1.3) is replaced with 2-iodo-1, 3-dimethylbenzene, 2,4, 6-trimethyliodobenzene, 2-iodoethylbenzene, wherein 4-fluorobenzene sulfinyl chloride in the step (1.4) is replaced by 2-chloro-5-nitrobenzene sulfinyl chloride, p- (1, 1-dimethylethyl) -p- (2,4, 6-trimethylphenyl) phosphine chloride and bis (2, 6-dimethylphenyl) phosphine chloride respectively, and the finally prepared [ N, O ] bidentate nickel complex of the ketone-imidazoline-2-imine ligand has the following structural formula:

examples 14 to 18

The preparation method of the ketone-imidazoline-2-imine [ N, O ] bidentate nickel complex is basically the same as that in example 10, except that 1-iodopropane in the step (1.3) is replaced by 2-bromopropane, bromo-tert-butane, (2-bromoethyl) benzene, benzyl bromide and 2-bromo-1, 3, 5-trimethylbenzene, the structure of the finally prepared [ N, O ] bidentate nickel complex of the ketone-imidazoline-2-imine ligand is basically the same as that in example 10, and the difference is that the structure of the obtained N-1 substituted imidazole-2-amine is different, namely the N-1 substituted imidazole-2-amine is replaced by isopropyl, tert-butyl, phenethyl, benzyl and 1,3, 5-trimethylphenyl, and the synthesized N-1 substituted imidazole-2-amine is 1-isopropyl-4-phenyl respectively -1H-imidazol-2-amine, 1-tert-butyl-4-phenyl-1H-imidazol-2-amine, 1-phenethyl-4-phenyl-1H-imidazol-2-amine, 1-benzyl-4-phenyl-1H-imidazol-2-amine, and 1- (1,3, 5-trimethyl) phenyl-4-phenyl-1H-imidazol-2-amine.

Examples 19 to 24

Ketone-imidazoline-2-imines [ N, O ]]Process for the preparation of bidentate nickel complexes, based onThe same as example 10, except that the catalyst reacted in the step (1.4) was replaced with NaHCO respectively₃、NaO^tBu、KO^tBu, methyllithium, N-butyllithium and triethylamine to finally prepare [ N, O ] of ketone-imidazoline-2-imine ligand]The structural formula of the bidentate nickel complex is the same as in example 10.

Example 25

The keto-imidazoline-2-imine [ N, O ] prepared in example 1]The bidentate nickel complex is used for catalyzing homopolymerization of ethylene monomers: after a reaction kettle containing a polytetrafluoroethylene lining is installed, the temperature is raised to 120 ℃, the reaction kettle is kept at a constant temperature for heating for 2 hours, then the reaction kettle is cooled to a set polymerization temperature of 60 ℃, gas exchange is carried out for 3 times by high-purity nitrogen, and toluene and ketone-imidazoline-2-imine [ N, O ] are sequentially added]The method comprises the steps of adding 25M L of bidentate nickel complex toluene solution in total, sealing a reaction system, introducing 3.0MPa ethylene, starting a mechanical rotating device with the rotating speed of 400r/min, keeping the ethylene constant pressure for reaction for 10min, after the reaction is finished, decompressing the reaction kettle to normal pressure, pouring the reaction solution into a 500M L beaker added with 200M L ethanol, adding a certain amount of hydrochloric acid ethanol solution with the mass fraction of 10% to terminate the reaction, stirring overnight, filtering, washing to obtain white solid, and performing vacuum drying at 60 ℃ to constant weight to obtain the number-average molecular weight M_n＝6.13×10³g·mol^-1、M_w/M_nPolyethylene with a melting point of 102 ℃ of 1.96.

Example 26

The keto-imidazoline-2-imine [ N, O ] prepared in example 2]The bidentate nickel complex is used for catalyzing homopolymerization of ethylene monomers: after a reaction kettle containing a polytetrafluoroethylene lining is installed, the temperature is raised to 120 ℃, the reaction kettle is kept at a constant temperature and heated for 2 hours, during the process, high-purity nitrogen is used for ventilation for 3 times, and toluene and ketone-imidazoline-2-imine [ N, O ] are sequentially added]The method comprises the steps of adding 25m L of bidentate nickel complex toluene solution in total, sealing a reaction system, introducing 3.0MPa ethylene, starting a mechanical rotating device with the rotating speed of 400r/min, keeping the ethylene constant pressure for reaction for 10min, after the reaction is finished, decompressing a reaction kettle to normal pressure, pouring the reaction solution into a 500m L beaker added with 200m L ethanolAdding a certain amount of hydrochloric acid ethanol solution with the mass fraction of 10% to terminate the reaction; stirring overnight, filtering, washing to obtain white solid, vacuum drying at 60 deg.C to constant weight to obtain M_n＝3.61×10³g·mol^-1、M_w/M_n2.36 polyethylene with a melting point of 92 ℃.

Example 27

The keto-imidazoline-2-imine [ N, O ] prepared in example 3]The bidentate palladium complex is used for catalyzing homopolymerization of ethylene monomers: after a reaction kettle containing a polytetrafluoroethylene lining is installed, the temperature is raised to 120 ℃, the reaction kettle is kept at a constant temperature for heating for 2 hours, then the reaction kettle is cooled to a set polymerization temperature of 60 ℃, gas exchange is carried out for 3 times by high-purity nitrogen, and toluene and ketone-imidazoline-2-imine [ N, O ] are sequentially added]The method comprises the steps of adding 25M L of bidentate palladium complex toluene solution in total, sealing a reaction system, introducing 3.0MPa ethylene, starting a mechanical rotating device with the rotating speed of 400r/min, keeping the ethylene constant pressure for reaction for 10min, after the reaction is finished, decompressing the reaction kettle to normal pressure, pouring the reaction solution into a 500M L beaker added with 200M L ethanol, adding a certain amount of hydrochloric acid ethanol solution with the mass fraction of 10% to terminate the reaction, stirring overnight, filtering, washing to obtain white solid, and performing vacuum drying at 60 ℃ to constant weight to obtain the number-average molecular weight M_n＝7.6×10³g·mol^-1、M_w/M_nPolyethylene with a melting point of 112 ℃ of 1.78.

Example 28

The keto-imidazoline-2-imine [ N, O ] prepared in example 4]The bidentate palladium complex is used for catalyzing homopolymerization of ethylene monomers: after a reaction kettle with a polytetrafluoroethylene lining is installed, the temperature is raised to 120 ℃, the reaction kettle is kept at a constant temperature for heating for 2 hours, then the reaction kettle is cooled to the set polymerization temperature of 40 ℃, gas exchange is carried out for 3 times by high-purity nitrogen, and toluene and phosphine scavenging agent Ni (COD) are sequentially added₂Toluene solution and ketone-imidazoline-2-imine [ N, O ]]The bidentate palladium complex toluene solution is 25m L in total, wherein the adding amount of the complex is 10 mu mol, then the reaction system is sealed, 1.0MPa ethylene is introduced, a mechanical rotating device with the rotating speed of 400r/min is started, and the ethylene constant pressure is maintained to be reversely rotatedReacting for 10min, releasing pressure of the reaction kettle to normal pressure after the reaction is finished, pouring the reaction solution into a 500M L beaker added with 200M L ethanol, adding a certain amount of hydrochloric acid ethanol solution with the mass fraction of 10% to stop the reaction, stirring overnight, filtering and washing to obtain white solid, and drying in vacuum at 60 ℃ to constant weight to obtain the molecular weight M_n＝5.11×10³g·mol^-1、M_w/M_n2.26 polyethylene with a melting point of 98 ℃.

Example 29

The keto-imidazoline-2-imine [ N, O ] prepared in example 5]The bidentate nickel complex is used for catalyzing homopolymerization of ethylene monomers: after a reaction kettle with a polytetrafluoroethylene lining is installed, the temperature is raised to 120 ℃, the reaction kettle is kept at a constant temperature for heating for 2 hours, then the reaction kettle is cooled to the set polymerization temperature of 40 ℃, gas exchange is carried out for 3 times by high-purity nitrogen, and toluene and phosphine scavenging agent Ni (COD) are sequentially added₂Toluene solution and ketone-imidazoline-2-imine [ N, O ]]The method comprises the steps of adding 25M L of bidentate nickel complex toluene solution in total, sealing a reaction system, introducing 1.0MPa ethylene, starting a mechanical rotating device with the rotating speed of 400r/min, keeping the ethylene constant pressure for reaction for 10min, after the reaction is finished, decompressing the reaction kettle to normal pressure, pouring the reaction solution into a 500M L beaker added with 200M L ethanol, adding a certain amount of hydrochloric acid ethanol solution with the mass fraction of 10% to terminate the reaction, stirring overnight, filtering, washing to obtain white solid, and performing vacuum drying at 60 ℃ to constant weight to obtain the number-average molecular weight M_n＝4.30×10³g·mol^-1、M_w/M_nPolyethylene with a melting point of 97 ℃ of 1.93.

Example 30

The keto-imidazoline-2-imine [ N, O ] prepared in example 6]The bidentate nickel complex is used for catalyzing copolymerization of ethylene and norbornene monomer, namely, after a reaction kettle containing a polytetrafluoroethylene lining is installed, the temperature is raised to 120 ℃, the reaction kettle is kept at a constant temperature and heated for 2 hours, then the reaction kettle is cooled to a set polymerization reaction temperature of 40 ℃, gas exchange is carried out for 3 times by high-purity nitrogen, toluene, a cocatalyst MAO (Al/Ni-2500) and a norbornene solution (7 mol/L toluene solution) are sequentially added under the nitrogen atmosphere, and the rotation speed is atFully dissolving ethylene under the condition of 400r/min to obtain ethylene saturated solution, and then quickly adding ketone-imidazoline-2-imine [ N, O ]]The method comprises the steps of adding 25M L of bidentate nickel complex toluene solution in total, sealing a reaction system, introducing 1.0MPa ethylene, starting a mechanical rotating device with the rotating speed of 400r/min, keeping the ethylene constant pressure for reaction for 30min, after the reaction is finished, decompressing the reaction kettle to normal pressure, pouring the reaction solution into a 500M L beaker added with 200M L ethanol, adding a certain amount of hydrochloric acid ethanol solution with the mass fraction of 10% to terminate the reaction, stirring overnight, filtering, washing to obtain white solid, and performing vacuum drying at 60 ℃ to constant weight to obtain the number-average molecular weight M_n＝5.0×10³g·mol^-1、M_w/M_n3.90, melting point 75 ℃.

Example 31

The keto-imidazoline-2-imine [ N, O ] prepared in example 7]The bidentate nickel complex is used for catalyzing copolymerization of ethylene and 5-hexenyl acetate monomer: after a reaction kettle with a polytetrafluoroethylene lining is installed, the temperature is raised to 120 ℃, the reaction kettle is kept at a constant temperature for heating for 2 hours, then the reaction kettle is cooled to a set polymerization temperature of 60 ℃, gas exchange is carried out for 3 times by high-purity nitrogen, and toluene, 30mmol of 5-hexyl acetate and ketone-imidazoline-2-imine [ N, O ] are sequentially added]The method comprises the steps of adding 25M L of bidentate nickel complex toluene solution in total, sealing a reaction system, introducing 3.0MPa ethylene, starting a mechanical rotating device with the rotating speed of 400r/min, keeping the ethylene constant pressure for reaction for 15min, after the reaction is finished, decompressing the reaction kettle to normal pressure, pouring the reaction solution into a 500M L beaker added with 200M L ethanol, adding a certain amount of hydrochloric acid ethanol solution with the mass fraction of 10% to terminate the reaction, stirring overnight, filtering, washing to obtain white solid, and performing vacuum drying at 60 ℃ to constant weight to obtain the number-average molecular weight M_n＝2.2×10³g·mol^-1、M_w/M_n1.88, melting point 101 ℃, and the polar monomer 5-hexenyl acetate insertion of 0.76 mol%.

Example 32

The keto-imidazoline-2-imine obtained in example 8[N,O]The bidentate nickel complex is used for catalyzing homopolymerization of norbornene monomer, namely a 50m L single-mouth round bottom reaction bottle containing a magnetic stirrer is dried in a drying oven at the constant temperature of 120 ℃ for 2 hours, the flask is vacuumized for 30 minutes, gas replacement is carried out in a high-purity nitrogen atmosphere by utilizing a standard Schlenk technology for 4 times, then the flask is placed on a reactor with the functions of magnetic stirring, heating and temperature control, then the temperature is adjusted to be 0 ℃ which is preset as the polymerization temperature, and chlorobenzene and 2 mu mol of ketone-imidazoline-2-imine [ N, O ] are sequentially added]Stirring at 300r/min, adding 40mmol of norbornene (7 mol/L toluene solution) after the catalyst is fully activated, adding 40mmol of norbornene (7 mol/L toluene solution), pouring the reaction solution into a 500M L beaker with 200M L ethanol after the polymerization reaction time reaches 30s, adding a certain amount of 10% hydrochloric acid ethanol solution to terminate the reaction, stirring overnight, filtering, washing to obtain a white solid, and vacuum drying at 60 ℃ to constant weight to obtain the M-Ni complex with the number average molecular weight of M (aluminum/nickel) (-) M (1000)_n＝6.49×10⁵g·mol^-1、M_w/M_nPolynorbornene with melting point 430 deg.c 2.11.

Example 33

The keto-imidazoline-2-imine [ N, O ] prepared in example 9]The bidentate palladium complex is used for catalyzing the copolymerization of norborneol and hexene monomers, namely drying a 50m L single-mouth round-bottom reaction bottle containing a magnetic stirrer in a drying oven at the constant temperature of 120 ℃ for 2h, vacuumizing the flask for 30min, performing gas replacement in a high-purity nitrogen atmosphere by using a standard Schlenk technology for 4 times, then placing the flask on a reactor with the functions of magnetic stirring, heating and temperature control, adjusting the temperature to 40 ℃ which is preset as a polymerization temperature, and sequentially adding chlorobenzene and 10 mu mol of ketone-imidazoline-2-imine [ N, O ] into the flask]Stirring the bidentate palladium complex chlorobenzene solution and a cocatalyst MMAO (Al/Ni ═ 1000) at 300r/min, adding a mixed solution of 24mmol of norbornene (7 mol/L toluene solution) and 16mmol of hexene after the catalyst is fully activated, wherein the total volume of the reaction system is 20m L, pouring the reaction solution after the polymerization reaction time reaches a preset reaction time of 1hAdding into 500M L beaker containing 200M L ethanol, adding a certain amount of 10% hydrochloric acid ethanol solution to terminate reaction, stirring overnight, filtering, washing to obtain white solid, vacuum drying at 60 deg.C to constant weight to obtain M_n＝3.11×10⁴g·mol^-1、M_w/M_n2.68, melting point 186 ℃.

Example 34

The keto-imidazoline-2-imine [ N, O ] prepared in example 10]The bidentate nickel complex is used for catalyzing the copolymerization of the norborneol and methyl acrylate monomers, namely drying a 50m L single-mouth round-bottom reaction bottle containing a magnetic stirrer in a drying oven at the constant temperature of 120 ℃ for 2h, vacuumizing the flask for 30min, performing gas replacement in a high-purity nitrogen atmosphere by using a standard Schlenk technology for 4 times, then placing the flask on a reactor with the functions of magnetic stirring, heating and temperature control, adjusting the temperature to 40 ℃ which is preset as a polymerization temperature, and sequentially adding toluene and 10 mu mol of ketone-imidazoline-2-imine [ N, O ] into the flask]The toluene solution of bidentate nickel complex and cocatalyst are 40 mu mol B (C)₆F₅)₃Stirring toluene solution at 300r/min, adding mixed solution of 36mmol norbornene (7 mol/L toluene solution) and 10mmol methyl acrylate after the catalyst is fully activated, wherein the total volume of the reaction system is 20M L, pouring the reaction solution into a 500M L beaker added with 200M L ethanol after the polymerization reaction time reaches the preset reaction time of 30min, adding a certain amount of hydrochloric acid ethanol solution with the mass fraction of 10% to terminate the reaction, stirring overnight, filtering, washing to obtain white solid, and vacuum drying at 60 ℃ to constant weight to obtain the M with the number average molecular weight_n＝1.20×10⁴g·mol^-1、 M_w/M_nThe insertion rate of methyl acrylate was 2.14 mol% for a copolymer having a melting point of 355 ℃ of 1.12.

Example 35

The keto-imidazoline-2-imine [ N, O ] prepared in example 11]The bidentate nickel complex is used for catalyzing homopolymerization of ethylene monomers: after a reaction kettle containing a polytetrafluoroethylene lining is installed, the temperature is raised to 120 ℃, the constant temperature is kept for heating for 2 hours, and then the temperature is lowered to the set temperatureSetting the polymerization temperature at 60 deg.C, ventilating with high-purity nitrogen for 3 times, and sequentially adding toluene and ketone-imidazoline-2-imine [ N, O ]]The method comprises the steps of adding 25M L of bidentate nickel complex toluene solution in total, sealing a reaction system, introducing 3.0MPa ethylene, starting a mechanical rotating device with the rotating speed of 400r/min, keeping the ethylene constant pressure for reaction for 10min, after the reaction is finished, decompressing the reaction kettle to normal pressure, pouring the reaction solution into a 500M L beaker added with 200M L ethanol, adding a certain amount of hydrochloric acid ethanol solution with the mass fraction of 10% to terminate the reaction, stirring overnight, filtering, washing to obtain white solid, and performing vacuum drying at 60 ℃ to constant weight to obtain the number-average molecular weight M_n＝7.25×10³g·mol^-1、 M_w/M_nPolyethylene with a melting point of 115 ℃ of 1.87.

Example 36

The keto-imidazoline-2-imine [ N, O ] prepared in example 12]The bidentate nickel complex is used for catalyzing homopolymerization of ethylene monomers: after a reaction kettle containing a polytetrafluoroethylene lining is installed, the temperature is raised to 120 ℃, the reaction kettle is kept at a constant temperature for heating for 2 hours, then the reaction kettle is cooled to a set polymerization temperature of 60 ℃, gas exchange is carried out for 3 times by high-purity nitrogen, and toluene and ketone-imidazoline-2-imine [ N, O ] are sequentially added]The method comprises the steps of adding 25M L of bidentate nickel complex toluene solution in total, sealing a reaction system, introducing 3.0MPa ethylene, starting a mechanical rotating device with the rotating speed of 400r/min, keeping the ethylene constant pressure for reaction for 10min, after the reaction is finished, decompressing the reaction kettle to normal pressure, pouring the reaction solution into a 500M L beaker added with 200M L ethanol, adding a certain amount of hydrochloric acid ethanol solution with the mass fraction of 10% to terminate the reaction, stirring overnight, filtering, washing to obtain white solid, and performing vacuum drying at 60 ℃ to constant weight to obtain the number-average molecular weight M_n＝5.76×10³g·mol^-1、 M_w/M_n2.18 polyethylene with a melting point of 96 ℃.

Example 37

The keto-imidazoline-2-imine [ N, O ] prepared in example 13]The bidentate nickel complex is used for catalyzing homopolymerization of ethylene monomers: will contain reation kettle of polytetrafluoroethylene inside liningAfter the installation, the temperature is raised to 120 ℃, the constant temperature is kept for heating for 2 hours, then the temperature is reduced to the set polymerization temperature of 60 ℃, gas exchange is carried out for 3 times by high-purity nitrogen, and toluene and ketone-imidazoline-2-imine [ N, O ] are sequentially added]The method comprises the steps of adding 25M L of bidentate nickel complex toluene solution in total, sealing a reaction system, introducing 3.0MPa ethylene, starting a mechanical rotating device with the rotating speed of 400r/min, keeping the ethylene constant pressure for reaction for 10min, after the reaction is finished, decompressing the reaction kettle to normal pressure, pouring the reaction solution into a 500M L beaker added with 200M L ethanol, adding a certain amount of hydrochloric acid ethanol solution with the mass fraction of 10% to terminate the reaction, stirring overnight, filtering, washing to obtain white solid, and performing vacuum drying at 60 ℃ to constant weight to obtain the number-average molecular weight M_n＝8.12×10³g·mol^-1、 M_w/M_nPolyethylene with a melting point of 122 ℃ of 1.76.

Example 38

A catalyst composition was prepared from the ketone-imidazoline-2-imine [ N, O ] bidentate nickel complex prepared in example 1 and methylaluminoxane as a cocatalyst in a molar ratio of 1: 30.

The catalyst composition is used for catalyzing homopolymerization of ethylene monomer, and the specific process comprises the steps of dissolving the catalyst composition in toluene under the protection of nitrogen, adding the ethylene monomer, and reacting for 60min under the conditions that the temperature is minus 20 ℃ and the pressure is 5MPa to obtain the catalyst composition with the number average molecular weight of 1.6 × 10³g·mol^-1Polyethylene having a molecular weight distribution index of 1.75 and a melting point of 93 ℃.

Example 39

A catalyst composition comprises the ketone-imidazoline-2-imine [ N, O ] bidentate nickel complex prepared in the example 2 and methylaluminoxane modified by cocatalyst tert-butyl aluminum, wherein the molar ratio of the ketone-imidazoline-2-imine [ N, O ] bidentate nickel complex to the cocatalyst is 1: 50.

The catalyst composition is used for catalyzing homopolymerization of ethylene monomer, and the specific process comprises the steps of dissolving the catalyst composition in toluene under the protection of nitrogen, adding the ethylene monomer, and reacting for 60min under the conditions that the temperature is 60 ℃ and the pressure is 2MPa to obtain the catalyst composition with the number average molecular weight of 2.3 × 10³g·mol^-1A polyethylene having a molecular weight distribution index of 2.37 and a melting point of 101 ℃.

Example 40

A catalyst composition comprised of the keto-imidazoline-2-imine [ N, O ] bidentate palladium complex prepared in example 3 and tri-N-hexylaluminum cocatalyst in a molar ratio of 1: 5000.

The catalyst composition is used for catalyzing homopolymerization of olefin monomers, and the specific process comprises the steps of dissolving the catalyst composition in chlorobenzene under the protection of nitrogen, adding norbornene monomers, and reacting for 1min at 85 ℃ to obtain the catalyst composition with the number average molecular weight of 6.2 × 10⁵g·mol^-1And a polymer having a molecular weight distribution index of 2.11 and a melting point of 461 ℃, wherein the molar ratio of norbornene to catalyst composition is 10000: 1.

EXAMPLE 41

A catalyst composition comprised of the keto-imidazoline-2-imine [ N, O ] bidentate palladium complex prepared in example 4 and trimethylaluminum cocatalyst in a molar ratio of 1: 860.

The catalyst composition is used for catalyzing homopolymerization of olefin monomers, and the specific process is that under the protection of nitrogen, the catalyst composition is firstly dissolved in toluene, 4-acetoxystyrene is added, and then the reaction is carried out for 60min at the temperature of 40 ℃ to obtain the catalyst composition with the number average molecular weight of 1.5 × 10³g·mol^-1And a molecular weight distribution index of 1.88, a melting point of 98 ℃, wherein the molar ratio of 4-acetoxystyrene to the catalyst composition is 4000: 1.

Example 42

A catalyst composition comprised of the keto-imidazoline-2-imine [ N, O ] bidentate nickel complex prepared in example 5 and triethylaluminum as cocatalyst in a molar ratio of 1: 5000.

The catalyst composition is used for catalyzing the copolymerization of olefin monomers, and the specific process comprises the steps of dissolving the catalyst composition in n-heptane under the protection of nitrogen, adding norbornene and hexene monomers, and reacting for 60min at 40 ℃ to obtain the catalyst with the number average molecular weight of 5.2 × 10³g·mol^-1Is divided intoThe polymer has a molecular weight distribution index of 2.61 and a melting point of 186 ℃, wherein the molar ratio of norbornene, hexene to catalyst is 2400:1600: 1.

Example 43

A catalyst composition comprised of the keto-imidazoline-2-imine [ N, O ] bidentate nickel complex prepared in example 6 and triisobutylaluminum cocatalyst in a molar ratio of 1: 2800.

The catalyst composition is used for catalyzing the copolymerization of olefin monomers, and the specific process comprises the steps of dissolving the catalyst composition in toluene under the protection of nitrogen, adding norbornene and styrene monomers, and reacting for 15min at the temperature of 60 ℃ to obtain the catalyst composition with the number average molecular weight of 5.0 × 10³g·mol^-1And the polymer has a molecular weight distribution index of 4.09 and a melting point of 268 ℃, wherein the molar ratio of the norbornene, the styrene and the catalyst is 2400:1600: 1.

Example 44

A catalyst composition comprised of the keto-imidazoline-2-imine [ N, O ] bidentate nickel complex prepared in example 7 and tri-N-octylaluminum co-catalyst in a molar ratio of 1: 300.

The catalyst composition is used for catalyzing the copolymerization of olefin monomers, and the specific process comprises the steps of dissolving the catalyst composition in toluene under the protection of nitrogen, adding norbornene and hexene monomers, and reacting for 70min at the temperature of 60 ℃ to obtain the catalyst composition with the number average molecular weight of 5.3 × 10³g·mol^-1And the polymer has a molecular weight distribution index of 2.73 and a melting point of 230 ℃, wherein the molar ratio of the norbornene, the hexene to the catalyst is 1600:2400: 1.

Example 45

A catalyst composition comprised of the keto-imidazoline-2-imine [ N, O ] bidentate nickel complex prepared in example 8 and diethylaluminum chloride as the cocatalyst in a molar ratio of 1: 1480.

The catalyst composition is used for catalyzing homopolymerization of ethylene monomers, and the specific process comprises the following steps: under the protection of nitrogen, firstly dissolving the catalyst composition in toluene, then adding ethylene monomer, and reacting at the temperature of 60 ℃ and the pressure of 2MPa for 75min to obtain a number average molecular weight of 1.1 × 10³g·mol^-1Polyethylene having a molecular weight distribution index of 2.61 and a melting point of 65 ℃.

Example 46

A catalyst composition comprised of the keto-imidazoline-2-imine [ N, O ] bidentate palladium complex prepared in example 9 and ethyl aluminum dichloride as a cocatalyst in a molar ratio of 1: 3000.

The catalyst composition is used for catalyzing homopolymerization of ethylene monomer, and the specific process comprises the steps of dissolving the catalyst composition in toluene under the protection of nitrogen, adding the ethylene monomer, and reacting for 30min under the conditions that the temperature is 70 ℃ and the pressure is 2MPa to obtain the catalyst composition with the number average molecular weight of 1.7 × 10³g·mol^-1A polyethylene having a molecular weight distribution index of 2.83 and a melting point of 83 ℃.

Example 47

A catalyst composition comprised of the keto-imidazoline-2-imine [ N, O ] bidentate nickel complex prepared in example 10 and tris (pentafluorophenyl) borane as the cocatalyst was prepared at a molar ratio of 1:1.

The catalyst composition is used for catalyzing homopolymerization of ethylene monomer, and the specific process comprises the steps of dissolving the catalyst composition in toluene under the protection of nitrogen, adding the ethylene monomer, and reacting for 30min under the conditions that the temperature is 70 ℃ and the pressure is 2MPa to obtain the catalyst composition with the number average molecular weight of 6.6 × 10³g·mol^-1Polyethylene having a molecular weight distribution index of 2.76 and a melting point of 98 ℃.

Example 48

A catalyst composition comprised of the keto-imidazoline-2-imine [ N, O ] bidentate nickel complex prepared in example 11 and the cocatalyst bis- (1, 5-cyclooctadiene) nickel in a molar ratio of 1: 10.

The catalyst composition is used for catalyzing the copolymerization of olefin monomers, and the specific process comprises the steps of dissolving the catalyst composition in chlorobenzene under the protection of nitrogen, adding ethylene and hexene monomers, and reacting for 60min under the conditions of temperature of 30 ℃ and pressure of 2.6MPa to obtain the catalyst composition with the number average molecular weight of 3.3 × 10³g·mol^-1A molecular weight distribution index of 2.66 and a melting point of115 ℃ polymer, wherein the molar ratio of hexene to catalyst is 1000: 1.

Example 49

A catalyst composition comprised of the keto-imidazoline-2-imine [ N, O ] bidentate nickel complex prepared in example 12 and the cocatalyst bis- (1, 5-cyclooctadiene) nickel in a molar ratio of 1: 7.

The catalyst composition is used for catalyzing the copolymerization of olefin monomers, and the specific process comprises the steps of dissolving the catalyst composition in chlorobenzene under the protection of nitrogen, adding ethylene and hexene monomers, and reacting for 60min under the conditions of temperature of 30 ℃ and pressure of 2.6MPa to obtain the catalyst composition with the number average molecular weight of 3.8 × 10³g·mol^-1And the molecular weight distribution index is 2.51, the melting point is 125 ℃, wherein, the mol ratio of the hexene to the catalyst is 1000: 1.

Example 50

A catalyst composition comprised of the keto-imidazoline-2-imine [ N, O ] bidentate nickel complex prepared in example 13 and the cocatalyst bis- (1, 5-cyclooctadiene) nickel in a molar ratio of 1: 4.

The catalyst composition is used for catalyzing the copolymerization of olefin monomers, and the specific process comprises the steps of dissolving the catalyst composition in chlorobenzene under the protection of nitrogen, adding ethylene and hexene monomers, and reacting for 60min under the conditions of temperature of 30 ℃ and pressure of 2.6MPa to obtain the catalyst composition with the number average molecular weight of 2.6 × 10³g·mol^-1And the molecular weight distribution index is 2.23, the melting point is 102 ℃, wherein, the mol ratio of the hexene to the catalyst is 1000: 1.

Claims

1. The ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex is characterized in that the structural formula is one of the following formulas:

in the formula, R₁Is alkyl, aryl or aryl substituent; r₂Is H or phenyl; r₃～R₂₂Independently of one another, from hydrogen, alkyl,Alkyl, alkoxy, halogen, halogenated alkyl, aryl or aryl substituent, R' is methyl, phenyl, benzyl or no substituent, M is nickel or palladium, L is trimethyl phosphine, triphenyl phosphine, pyridine, dimethyl sulfoxide or allyl.

2. A process for preparing a ketone-imidazoline-2-imine [ N, O ] bidentate nickel, palladium complex according to claim 1, characterized in that: reacting the ketone-imidazoline-2-imine ligand with a hydrogen extraction reagent and a metal precursor in sequence to prepare a ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex;

the acid chloride compound has the following structural formula:

the structural formula of the benzene sulfinyl chloride compound is as follows:

the structural formula of the phosphine chloride compound is as follows:

the structural formula of the N-1-substituted imidazole-2-amine is as follows:

the preparation process of the N-1-substituted imidazole-2-amine comprises the following steps: firstly, amino acetaldehyde dimethyl acetal or amino acetaldehyde dimethyl acetal reacts with O (S) -methyl isourea sulfate to prepare 2-amino-1H-imidazole hemisulfate, and then the 2-amino-1H-imidazole hemisulfate reacts with alkaline substances to prepare 2-amino-1H-Imidazole, finally 2-amino-1H-imidazole with a halide X-R₁Reacting to obtain N-1 substituted imidazole-2-amine;

3. The method according to claim 2, characterized by the following specific steps:

(1) preparing a ketone-imidazoline-2-imine ligand;

(1.1) preparing hemisulfate;

(1.1.b) carrying out reflux reaction on 2-bromoacetophenone and 1-acetylguanidine in acetonitrile to prepare N- (4-phenyl-1H-imidazole-2-yl) formamide, and then carrying out reaction for a period of time under the acidic condition of sulfuric acid with the pH value of 2.0 to obtain 2-amino-4-phenyl-1H-imidazole hemisulfate;

4. A process according to claim 3, wherein in step (1.1.a), the catalyst is hydrochloric acid, sulphuric acid, nitric acid or phosphoric acid; the molar ratio of aminoacetaldehyde dimethyl acetal or aminoacetaldehyde diethyl acetal to O (S) -methylisourea sulfate is 1-3: 1-3, and the molar ratio of the catalyst to O (S) -methylisourea sulfate is 3-5: 1-2; the certain temperature is 50-90 ℃, and the certain time is 6-11 hours;

in the step (1.2), the alkaline substance is potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate or sodium bicarbonate; the certain temperature is room temperature, and the period of time is 3 hours;

in step (1.3), the halide X-R₁Is methyl iodide, 2-iodopropane, iodotert-butane, iodobenzene, 1-iodopropane, 2-iodo-1, 3-dimethylbenzene, 2,4, 6-trimethyliodobenzene, 2-iodoethylbenzene, 2-bromopropane, bromotert-butane, iodobenzene, iodopropane, iodobutane,(2-bromoethyl) benzene, benzyl bromide or 2-bromo-1, 3, 5-trimethylbenzene, the solvent is absolute ethyl alcohol, absolute isopropanol, absolute tert-butyl alcohol or absolute methanol, the catalytic system consists of a main catalyst, an auxiliary catalyst and an alkaline substance, the main catalyst is cuprous iodide, the auxiliary catalyst is 8-hydroxyquinoline, and the alkaline substance is NaO^tBu、K₃PO₄、Cs₂CO₃Or K₂CO₃；

the certain temperature is 50-95 ℃, and the certain time is 16-36 hours;

in the step (1.4), the solvent is diethyl ether, tetrahydrofuran, dichloromethane, chloroform, toluene, 1, 4-dioxane, n-heptane or chlorobenzene, and the catalyst is K₂CO₃、Na₂CO₃、Cs₂CO₃、KHCO₃、NaHCO₃、NaO^tBu、KO^tBu, methyllithium, n-butyllithium, pyridine or triethylamine, wherein the acyl chloride compound is benzoyl chloride, 4-bromobenzoyl chloride, 4-bromo-3, 5-dimethoxybenzoyl chloride, 3-bromo-4-methoxybenzoyl chloride or adamantane acyl chloride, the benzene sulfinyl chloride compound is 4-fluorobenzene sulfinyl chloride or 2-chloro-5-nitrobenzene sulfinyl chloride, and the phosphine chloride compound is p- (1, 1-dimethylethyl) -p- (2,4, 6-trimethylphenyl) phosphine chloride or bis (2, 6-dimethylphenyl) phosphine chloride;

the certain temperature is-78-50 ℃, and the certain time is 10-18 h;

5. The method as claimed in claim 3, wherein after the step (1.4) is finished, the product is further separated and purified by column chromatography, organic solvent recrystallization or organic solvent extraction; the elution solvent used in the column chromatography is ethyl acetate-n-hexane, ethyl acetate-dichloromethane-n-hexane, methanol-n-hexane, ethanol-n-hexane, ethyl acetate-ethanol or ethyl acetate-methanol; the organic solvent used in the organic solvent recrystallization method or organic solvent extraction method is toluene, chloroform, ethyl acetate, dichloromethane, tetrahydrofuran, diethyl ether, n-hexane, methanol or ethanol.

6. The use of a [ N, O ] bidentate [ N, O ] nickel, palladium complex of a ketone-imidazoline-2-imine as claimed in claim 1, characterized in that: the ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex is used for catalyzing homopolymerization or copolymerization of olefin monomers;

the specific process is as follows: under the protection of nitrogen, dissolving a ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex in a solvent, adding an olefin monomer, and reacting for 1-180 min at the temperature of-20-120 ℃ and the pressure of 0.1-5 MPa to prepare an olefin polymer;

the solvent is toluene, chlorobenzene, n-hexane or n-heptane, and the olefin monomer is more than one of ethylene, cycloolefin and polar/functional monomer;

the olefin polymer comprises olefin polymer and ethylene oligomer, wherein the number average molecular weight of the olefin polymer is 2200 to 649000g & mol^-1The molecular weight distribution index is 1.12-3.90, the melting point is 75-430 ℃, and the ethylene oligomer mainly comprises butene and hexene.

7. A catalyst composition prepared from the ketone-imidazoline-2-imine [ N, O ] bidentate nickel, palladium complex of claim 1, characterized by: mainly consists of ketone-imidazoline-2-imine [ N, O ] bidentate nickel, a palladium complex and a cocatalyst, wherein the cocatalyst is aluminoxane, an alkyl aluminum compound, an alkyl aluminum chloride compound, a boron compound or bis- (1, 5-cyclooctadiene) nickel.

8. The catalyst composition of claim 7, wherein the molar ratio of the keto-imidazoline-2-imine [ N, O ] bidentate nickel, palladium complex to aluminum in the aluminoxane, alkyl aluminum compound, or alkyl aluminum chloride compound is 1:30 to 5000; the molar ratio of the ketone-imidazoline-2-imine [ N, O ] bidentate nickel and palladium complex to the boron compound or bis- (1, 5-cyclooctadiene) nickel is 1: 1-10.

9. The catalyst composition of claim 7, wherein the aluminoxane is methylaluminoxane or t-butylaluminum modified methylaluminoxane; the alkyl aluminum compound is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum or tri-n-octyl aluminum; the alkyl aluminum chloride compound is diethyl aluminum chloride or ethyl aluminum dichloride; the boron compound is tris (pentafluorophenyl) borane.

10. Use of a catalyst composition according to any one of claims 7 to 9, characterized in that: the catalyst composition is used for catalyzing homopolymerization or copolymerization of olefin monomers;

the molar ratio of the ethylene to the catalyst composition is 10000-50000: 1-2, the molar ratio of the cycloolefin to the catalyst composition is 4-10000: 1-2, and the molar ratio of the polar/functional monomer to the catalyst composition is 10-40000: 1;

the olefin polymer comprises olefin polymer and ethylene oligomer, and the number average molecular weight of the olefin polymer is 1100-620000 g & mol^-1The molecular weight distribution index is 1.75-4.09, the melting point is 83-461 ℃, and the ethylene oligomer mainly comprises butene and hexene.