CN117865847A

CN117865847A - Ligand compound containing benzidine group, metal complex, metal supported catalyst and application thereof

Info

Publication number: CN117865847A
Application number: CN202410089292.4A
Authority: CN
Inventors: 潘瑶; 薛虎; 朱宁宁; 许浒
Original assignee: Hefei Zhongke Kele New Material Co ltd
Current assignee: Hefei Zhongke Kele New Material Co ltd
Priority date: 2024-01-22
Filing date: 2024-01-22
Publication date: 2024-04-12

Abstract

The invention relates to a ligand compound containing benzidine, a metal complex, a metal supported catalyst and application thereof, belonging to the technical field of catalyzing olefin polymerization and synthesizing high polymer polyolefin. The ligand compound has a structural formula shown in a formula I,wherein R is ₂ 、R ₃ 、R ₄ 、R ₅ Are independently selected from C ₁ ～C ₁₀ Any one of alkyl, substituted or unsubstituted benzhydryl, hydrogen; r is R ₁ 、R ₆ Simultaneously, any one of methoxy, hydroxy and sodium oxide substituent groups is selected; when there is a substituent on the benzhydryl group, the substituent is selected from hydroxy, C ₁ ～C ₁₀ Alkyl, C of (2) ₁ ～C ₁₀ Alkoxy, C ₂ ～C ₁₀ Any one of alkenyl groups of (a). The invention is implemented by combining R ₁ 、R ₆ Is linked to the benzil amine backbone such that on subsequent loading R ₁ 、R ₆ The group of (2) can form stronger hydrogen bond interaction with hydrogen atoms on a carrier, and cooperates with a benzidine skeleton to regulate and control the steric hindrance effect, so that the metal supported catalyst prepared later has better catalytic effect.

Description

Ligand compound containing benzidine group, metal complex, metal supported catalyst and application thereof

Technical Field

The invention relates to the technical field of catalyzing olefin polymerization and synthesizing high polymer polyolefin materials, in particular to a ligand compound containing benzidine, a metal complex, a metal supported catalyst and application thereof.

Background

Polyolefin materials have a large specific gravity in polymer composite materials, and their importance is represented in various fields of daily life. The non-functionalized polyolefin material has great advantages in solvent corrosion resistance, thermal stability and the like due to the inertia of chemical bonds of the material. However, polyolefins generally have poor adhesion, poor dyeing properties, and poor rheology and blending properties. In order to widen the application range of polyolefin materials, research on functionalized polyolefin materials has been one of the directions of attention and exploration, both in academia and in industry.

Currently, polar functional groups are introduced into polyolefin materials in the industry mainly through high-temperature high-pressure free radical polymerization, ion polymerization or post-polymerization modification and other approaches. The method is generally harsh in conditions and relatively poor in controllability, and the regulation and control of the polymer molecular level are difficult to realize.

Disclosure of Invention

Aiming at the technical problems, the invention provides a ligand compound containing benzidine, a metal complex, a metal supported catalyst and application thereof, wherein methoxy, hydroxyl or sodium oxide substituent groups are introduced to benzidine, so that oxygen atoms in the groups can form stronger hydrogen bond interaction with hydrogen atoms on a carrier when the subsequent loading is carried out, and the prepared metal supported catalyst has higher stability and activity.

According to an embodiment of one aspect of the present invention, there is provided a benzidine group-containing ligand compound of formula I, R ₁ 、R ₆ Simultaneously, any one of methoxy, hydroxy and sodium oxide substituent groups is selected; r is R ₂ 、R ₃ 、R ₄ 、R ₅ Are independently selected from C ₁ ～C ₁₀ Any one of alkyl, substituted or unsubstituted benzhydryl, hydrogen; when there is a substituent on the benzhydryl group, the substituent is selected from hydroxy, C ₁ ～C ₁₀ Alkyl, C of (2) ₁ ～C ₁₀ Alkoxy, C ₂ ～C ₁₀ Any one of alkenyl groups of (a).

According to some embodiments of the invention, R ₂ 、R ₃ 、R ₄ 、R ₅ Each independently selected from one of the following structures:

according to some embodiments of the invention, R ₂ 、R ₃ 、R ₄ 、R ₅ Are all isopropyl, R ₁ 、R ₆ And is simultaneously hydroxyl or methoxy.

According to some embodiments of the invention, the ligand compound comprises formula I ₁ To formula I ₉ A compound of the structure shown in (a):

according to an embodiment of another aspect of the present invention, there is provided a metal complex of formula ii, M is nickel or palladium, X is Cl or Br; r is R ₁ 、R ₆ Simultaneously, any one of methoxy, hydroxy and sodium oxide substituent groups is selected; r is R ₂ 、R ₃ 、R ₄ 、R ₅ Are independently selected from C ₁ ～C ₁₀ Any one of alkyl, substituted or unsubstituted benzhydryl, hydrogen; when there is a substituent on the benzhydryl group, the substituent is selected from hydroxy, C ₁ ～C ₁₀ Alkyl, C of (2) ₁ ～C ₁₀ Alkoxy, C ₂ ～C ₁₀ Any one of alkenyl groups of (a).

according to some embodiments of the invention, the ligand compound includes formula II ₁ To II of ₉ A compound of the structure shown in (a):

according to an embodiment of still another aspect of the present invention, there is provided a metal supported catalyst prepared using the above metal complex and a carrier, wherein the metal complex is supported on the carrier.

According to some embodiments of the invention, the support comprises at least one of silica, magnesium chloride, and aluminum oxide.

According to an embodiment of a further aspect of the present invention, there is provided the above metal-supported catalyst for catalyzing C ₂ ～C ₁₁ Is used for the polymerization of olefin monomers.

According to some embodiments of the invention, catalyze C ₂ ～C ₁₁ The polymerization of the olefin monomers of (a) comprises:

cocatalyst and C ₂ ～C ₁₁ Adding olefin monomer into organic solvent, and then injecting metal supported catalyst to make C ₂ ～C ₁₁ Carrying out coordination polymerization reaction on olefin monomers of the catalyst; wherein the organic solvent comprises at least one of toluene, benzene and n-heptane; the cocatalyst comprises at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, tri-n-butylaluminum, alkali metal or base metal salt; c (C) ₂ ～C ₁₁ The olefin monomer of (2) comprises at least one of methacrylic acid, methyl methacrylate, ethyl methacrylate, 10-undecenol, 10-undecylenic acid, 6-chloro-1-hexene, 1-hexene and 1-octene.

Based on the technical scheme, the benzil-group-containing ligand compound, the metal complex, the metal supported catalyst and the application thereof have at least one or a part of the following beneficial effects:

the ligand compound provided by the invention has a benzidine skeleton, the ligand activity of the metal catalyst is moderate, and methoxy, hydroxyl or sodium oxide substituent groups are simultaneously introduced at the relative positions on the benzidine skeleton, so that when the subsequent loading is carried out, the oxygen atoms in the groups on the obtained metal supported catalyst have negative charges, and lone pair electrons of the oxygen atoms can form hydrogen bond interaction with atomic nuclei of hydrogen atoms on a carrier, so that the combination between the ligand compound and the carrier is more stable, a better loading effect is achieved, and the prepared metal supported catalyst has higher stability and activity relative to the homoline catalyst, and can be used for preparing polyolefin with higher molecular weight and good shape control. In addition, the heterogeneous metal supported catalyst shows higher polar monomer tolerance in the subsequent olefin polymerization, so that the olefin is easier to copolymerize with the polar monomer, and the prepared polyolefin is not sticky to the reaction kettle and is easier to industrially popularize. Meanwhile, the benzidine skeleton can form a larger steric hindrance effect, and the inserted metal is limited in a smaller space range when coordinated with nitrogen, so that uncontrollable chain walking and chain transfer behaviors of the metal center are reduced. Under the combined action of benzidine skeleton and hydrogen bond between benzidine skeleton and carrier, olefin polymerization is carried out subsequently, which is beneficial to improving the molecular weight of polyolefin and reducing branching degree.

Drawings

The present invention is described in further detail below with reference to the accompanying drawings.

FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a ligand compound 1 prepared in example 1 of the present invention;

FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the ligand compound 2 prepared in example 2 of the present invention.

Detailed Description

The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.

The endpoints and any values of the ranges invented in this invention are not limited to the precise range or value, and such range or value should be understood to include values approaching those range or value. For numerical ranges, one or more new numerical ranges may be obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point values, and are to be considered as specifically invented in the present invention.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The terms "comprises," "comprising," and/or the like, as used herein, specify the presence of stated features, steps, operations, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, or components.

All terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise defined. It should be noted that the terms used herein should be construed to have meanings consistent with the context of the present specification and should not be construed in an idealized or overly formal manner.

Similarly, in the description of exemplary embodiments of the invention above, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various inventive aspects. The description of the terms "one embodiment," "some embodiments," "example," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.

In the related art, polar functional groups are introduced by using free radical polymerization, ion polymerization or modification after polymerization, so that the conditions are harsh, the controllability of the obtained polyolefin is poor, and the morphology of the prepared polyolefin is difficult to regulate.

In the conception of the invention, it is found that the framework containing benzil amide is designed and applied to olefin polymerization, methoxy, hydroxyl or sodium oxide substituent groups are simultaneously connected at the para position of the framework of benzil amide, and the ligand compound prepared by the method has higher stability and activity after being loaded compared with the ligand compound without load through stronger hydrogen bond interaction between oxygen atoms on the groups and hydrogen atoms on a carrier, so that polyolefin with higher molecular weight and good shape control can be prepared.

According to an embodiment of one aspect of the present invention, there is provided a benzidine group-containing ligand compound of formula I, R ₂ 、R ₃ 、R ₄ 、R ₅ Are independently selected from C ₁ ～C ₁₀ Any one of alkyl, substituted or unsubstituted benzhydryl, hydrogen; r is R ₁ 、R ₆ Simultaneously, any one of methoxy, hydroxy and sodium oxide substituent groups is selected; wherein, when the benzhydryl has a substituent, the substituent is selected from hydroxy and C ₁ ～C ₁₀ Alkyl, C of (2) ₁ ～C ₁₀ Alkoxy, C ₂ ～C ₁₀ Any one of alkenyl groups of (a).

According to some embodiments of the invention, the ligand compound shown in the formula I has a benzidine skeleton, the ligand activity as a metal catalyst is moderate, methoxy, hydroxyl and sodium oxide substituents are simultaneously introduced at the para position of the benzidine skeleton, when the metal supported catalyst is formed by subsequent loading, firstly, the benzidine skeleton builds a larger steric hindrance effect, and the inserted metal is limited in a smaller space range when coordinated with nitrogen, so that uncontrollable chain walking and chain transfer behaviors of a metal center are reduced. And secondly, hydrogen bond interaction is formed between oxygen atoms in the groups and hydrogen atoms on the carrier, so that the combination between the ligand compound and the carrier is more stable, and a better loading effect is achieved. By introducing the groups at the para position of the benzil amide skeleton, the prepared metal supported catalyst has higher stability and activity, and can prepare polyolefin with higher molecular weight and good morphology control during the subsequent olefin polymerization catalysis. And the heterogeneous metal supported catalyst prepared later shows higher polar monomer tolerance when olefin polymerization is carried out later, so that the olefin is easier to copolymerize with the polar monomer, and the prepared polyolefin is not sticky to a reaction kettle and is easier to industrially popularize.

during the course of carrying out the preliminary experiments related to the invention, it was found that when R ₂ 、R ₃ 、R ₄ 、R ₅ When selected from the above groups, the subsequent preparation of olefin polymers has a lower degree of branching and a higher molecular weight.

Preferably, R ₂ 、R ₃ 、R ₄ 、R ₅ Are all isopropyl, R ₁ 、R ₆ And is simultaneously hydroxyl or methoxy.

there is also provided, in accordance with some embodiments of the present invention, a method of preparing a benzil amine group-containing ligand compound of formula I, comprising: the compound shown in the formula A, the compound shown in the formula B and the compound shown in the formula C are dissolved in a first solvent, and a formic acid catalyst is added for heating reflux. After the reaction, the reaction mixture was concentrated, and dehydrated ether was added thereto, whereby a yellowish green solid was precipitated in the reaction mixture. The yellow-green solid is separated by filtration, washed and dried in sequence to obtain the compound shown in the formula I.

The reaction process is as follows:

according to some embodiments of the invention, the reaction conditions for preparing the compound of formula I are: under the condition of 70 to 90 ℃, for example, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, preferably 80 ℃. The heating reflux time is 10 to 14 hours, and may be, for example, 10 hours, 11 hours, 12 hours, 13 hours or 14 hours, preferably 12 hours.

According to some embodiments of the invention, the first solvent comprises methanol or toluene.

According to some embodiments of the invention, the compound of formula a, the compound of formula B, the compound of formula C are added in a molar ratio of 1:1:1.

According to some embodiments of the invention, the compound of formula a, the compound of formula B, the compound of formula C may be purchased and used directly.

According to an embodiment of the present invention, there is also provided a metal complex of formula ii, wherein M is nickel or palladium and X is Cl or Br; r is R ₁ 、R ₆ Simultaneously, any one of methoxy, hydroxy and sodium oxide substituent groups is selected; r is R ₂ 、R ₃ 、R ₄ 、R ₅ Are independently selected from C ₁ ～C ₁₀ Any one of alkyl, substituted or unsubstituted benzhydryl, hydrogen; when there is a substituent on the benzhydryl group, the substituent is selected from hydroxy, C ₁ ～C ₁₀ Alkyl, C of (2) ₁ ～C ₁₀ Alkoxy, C ₂ ～C ₁₀ Any one of alkenyl groups of (a).

According to some embodiments of the present invention, the formation of metal complexes reduces the uncontrolled chain walking and chain transfer of the metal center by using benzidine backbones to build greater steric hindrance to inhibit the spatial extent of metal to nitrogen coordination. The method is beneficial to improving the molecular weight of polyolefin and reducing the branching degree when olefin polymerization is carried out subsequently.

According to some embodiments of the invention, the nickel complex comprises formula II ₁ To II of ₉ A compound of the structure shown in (a):

according to some embodiments of the present invention, there is also provided a method of preparing a metal complex of formula ii, comprising: under anhydrous and anaerobic conditions, reacting a compound of formula I with (DME) NiBr ₂ Adding (DME is 1, 2-dimethoxyethane) into a first organic solvent, mixing and stirring, and sequentially filtering, recrystallizing, filtering and drying to obtain the metal complex shown in the formula II.

The reaction change process is as follows:

according to some embodiments of the invention, the compound of formula I and (DME) NiBr ₂ The addition molar ratio of (2) is 1:1.

According to some embodiments of the invention, the reaction conditions for preparing the compound of formula ii are: under the condition of 5 to 25 ℃, for example, 5 ℃, 10 ℃, 15 ℃, 20 ℃ or 25 ℃ can be used. The mixing and stirring time is 10 to 14 hours, for example, 10 hours, 11 hours, 12 hours, 13 hours or 14 hours, preferably 12 hours.

According to some embodiments of the present invention, there is also provided a metal supported catalyst comprising a metal complex as described above and a support, wherein the metal complex is supported on the support.

According to some embodiments of the invention, the oxygen atoms in methoxy, hydroxyl and sodium oxide substituents are simultaneously introduced to para positions of the benzidine skeleton, so that stronger hydrogen bond interaction can be formed with the hydrogen atoms on the carrier, and the active sites on the surface of the carrier are improved, so that the metal supported catalyst can be more tightly contacted with the carrier, has a better supporting effect, and forms a heterogeneous supported catalyst with excellent catalytic performance.

According to some embodiments of the invention, the support comprises at least one of silica, magnesium chloride or aluminum oxide, preferably silica.

There is also provided, in accordance with some embodiments of the present invention, a method of preparing a metal supported catalyst, comprising: and (3) under the room temperature condition, adding the metal complex shown in the formula II and the carrier into a second solvent, stirring for 8-16 hours, and then sequentially filtering and drying to obtain the metal supported catalyst.

According to some embodiments of the invention, the second solvent comprises dichloromethane or tetrahydrofuran.

According to some embodiments of the present invention, there is also provided a metal supported catalyst as described above for catalyzing C ₂ ～C ₁₁ Is used for the polymerization of olefin monomers.

According to some embodiments of the invention, the polymerization reaction includes C ₂ ～C ₁₁ Homo-and/or co-polymerization of olefin monomers of (a).

Specifically, when the polymerization reaction is C ₂ ～C ₄ During the homopolymerization of olefin monomers, C is added into a reaction vessel ₂ ～C ₄ The olefin monomer, the cocatalyst and the organic solvent are uniformly mixed, a metal supported catalyst is added, the homopolymerization reaction is carried out under the condition of 1-50 atmospheres, and quenching is carried out after the reaction is finished.

When the polymerization is C ₅ The above long-chain olefin homopolymerization is carried out under the same conditions as in the above homopolymerization, except that the long-chain olefin homopolymerization is carried out under an inert gas atmosphere.

When the polymerization is C ₂ ～C ₄ During the copolymerization of olefin monomers, C is added into the reaction vessel ₂ ～C ₄ The comonomer of the olefin, the cocatalyst and the organic solvent are uniformly mixed, a metal supported catalyst is added, the copolymerization reaction is carried out under the condition of 1-50 atmospheres, and quenching is carried out after the reaction is finished.

According to some embodiments of the invention, the reagent used in quenching comprises methanol.

According to some embodiments of the invention, catalyze C ₂ ～C ₁₁ The polymerization of the olefin monomers of (a) comprises: cocatalyst and C ₂ ～C ₁₁ Adding the olefin monomer into the organic solvent, and then introducing the metal supported catalyst to lead C ₂ ～C ₁₁ Is subjected to coordination polymerization. Wherein the organic solvent comprises at least one of toluene, benzene and n-heptane. The cocatalyst comprises at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, tri-n-butylaluminum, alkali metal and alkali metal salt. C (C) ₂ ～C ₁₁ The olefin monomer of (C) comprises methacrylic acid, methyl methacrylate, ethyl methacrylate, 10-undecylenic alcohol, 10-undecylenic acid and 6-chlorine-at least one of 1-hexene, 1-octene. In the process of screening the organic solvent, the cocatalyst and the olefin monomer, the obtained polymerization product has higher molecular weight, stronger activity and lower branching degree when the organic solvent, the cocatalyst and the olefin monomer are respectively selected from the specific compounds.

In a typical experiment, taking ethylene homo-polymerization as an example, the specific preparation steps are as follows:

into a 350mL glass thick-wall pressure vessel in a glove box was charged 500eq of ethylaluminum dichloride (AlEt) ₂ Cl), 18mL of n-hexane and a magnetic stirring bar, and the pressure vessel was connected to a high-pressure line and the solution was degassed. The vessel was heated to 20-40 ℃ using an oil bath and allowed to equilibrate for 15 minutes. 2mL of CH was injected by syringe ₂ Cl ₂ 5. Mu. Mol of the metal complex or 5. Mu. Mol of the metal-supported catalyst were injected into the polymerization system, respectively. The reactor was pressurized and maintained at 8.0atm of ethylene with rapid agitation. After the desired time, the pressure vessel was vented and the polymer was precipitated in acidified methanol (methanol/hcl=50/1) and dried under vacuum at 50 ℃ for 24 hours.

In a typical experiment, for example, the undecylenic acid was copolymerized, and the specific preparation steps were as follows:

a350 mL glass thick-walled pressure vessel was charged with a total of 18mL of 500eq AlEt in a glove box ₂ Cl, n-hexane and undecylenic acid, and a magnetic stirring bar. The pressure vessel was then connected to a high pressure line and the solution was degassed. The vessel was heated to 20-40 ℃ using an oil bath and allowed to equilibrate for 15 minutes. 2mL of CH was injected by syringe ₂ Cl ₂ 15. Mu. Mol of the metal complex or 15. Mu. Mol of the metal-supported catalyst were injected into the polymerization system. The reactor was pressurized and maintained at 8.0atm of ethylene with rapid agitation. After a duration of 30min, the solvent was evaporated and the polymer was dried under vacuum at 50 ℃ for 24 hours.

The invention is further illustrated by the following examples. In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough explanation of the embodiments of the invention. It may be evident, however, that one or more embodiments may be practiced without these specific details. Moreover, the details of the various embodiments below may be arbitrarily combined into other viable embodiments without conflict.

It should be noted that the following examples illustrate the details of the present invention and the data presented include ligand synthesis, metal compound synthesis, ethylene polymerization or copolymerization processes, wherein the complex synthesis is carried out in the absence of water and oxygen, all sensitive materials are stored in a glove box, all solvents are strictly dried to remove water, and ethylene gas is purified by a water removal oxygen removal column. All materials are used as they are after being purchased, unless otherwise specified. Methods such as immunofluorescent staining are well known in the art and may be performed by textbooks or descriptions of related documents, and are not described in detail.

The nuclear magnetic detection of the embodiment of the invention uses a Bruker 400MHz nuclear magnetic instrument, the element analysis is measured by China science and technology center of theory, the molecular weight and the molecular weight distribution are measured by high-temperature GPC, and the mass spectrum is measured by Thermo LTQ Orbitrap XL.

Example 1:

synthesis of ligand compound 1:

2mmol of aniline and 2mmol of methylbenzoyl (2 mmol) with a few drops of formic acid (1 mL) were added to a solution of 20mL of methanol and refluxed at 80 ℃ for 12 hours until a new product spot formed on a thin layer chromatography plate (TLC), and the remaining mixture was diluted in 30mL of diethyl ether and stirred for 1 hour. The pale yellow solid was isolated by filtration to give ligand compound 1 in 73% yield. FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a ligand compound 1 prepared in example 1 of the present invention, and the structure of the prepared product can be determined as shown in FIG. 1. ¹ H NMR(400MHz,CDCl3)δ7.45,7.04,6.99,6.97,6.95,6.93,6.92,6.91,6.89,6.88,6.87,6.86,6.85,6.55,6.53,6.52,6.45,6.44,6.43,3.86,3.66,3.14,3.12,3.10,3.09,3.07,2.50,2.48,2.46,2.45,2.43,2.22,2.20,2.20,2.18,2.17,2.15,2.14,2.12,2.10,2.08,1.30,1.28,1.26,1.22,1.08,1.07,1.06,1.04,1.02,1.00,0.92,0.91,0.90,0.89,0.88,0.87,0.61,0.60。

The reaction change process is as follows:

synthesis of nickel complex Ni 1:

under nitrogen atmosphere, 1mmol of ligand compound 1, 1mmol of (DME) NiBr was poured into a 50mL Schlenk flask ₂ And 10mL of methylene chloride. After stirring at room temperature for 12 hours, the resulting product was precipitated with n-hexane, separated by filtration and dried under vacuum to give a yellowish solid nickel complex Ni1 in 78% yield.

The reaction change process is as follows:

example 2:

synthesis of ligand compound 2:

under nitrogen atmosphere, 10.00mmol of ligand compound 1 was dissolved in 30mL of dried dichloromethane, and placed in an ice-water bath at-30℃to react for 4 hours with the addition of 20.00mmol of boron tribromide, 10mL of water was added, and then the reaction was carried out at room temperature overnight. And (3) draining the solvent after the reaction is finished, extracting with water and ethyl acetate, drying and filtering the organic phase, taking filtrate, spin-drying the filtrate, and recrystallizing with petroleum ether to obtain gray yellow solid powder which is the ligand compound 2. FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the ligand compound 2 prepared in example 2 of the present invention, and the structure of the prepared product can be determined as shown in FIG. 2. ¹ H NMR(400MHz,MeOD)δ8.10–8.05,7.86,7.48,7.39–7.22,6.81,6.68,3.05–2.95,1.25,1.02。

The reaction change process is as follows:

synthesis of nickel complex Ni 2:

under nitrogen atmosphere, 1mmol of ligand compound 2 and 1mmol of (DME) NiBr were added to a 50mL Schlenk flask ₂ And 10mL of methylene chloride. After stirring at room temperature for 8 hours, the resulting product was precipitated with n-hexane, separated by filtration and dried under vacuum to give a red solid nickel complex Ni2 in 84% yield.

The reaction change process is as follows:

example 3:

synthesis of ligand compound 3:

under nitrogen atmosphere, 10.00mmol of ligand compound 2 is dissolved in 30mL of dry tetrahydrofuran, and placed in an ice water bath at the temperature of minus 10 ℃, 20.00mmol of sodium hydride is added for reaction for 1 hour, and the solvent is pumped out at room temperature after the reaction is finished, so as to obtain the ligand compound 3.

The reaction change process is as follows:

synthesis of nickel complex Ni 3:

under nitrogen atmosphere, 1mmol of ligand compound 3 and 1mmol of (DME) NiBr were added to a 50mL Schlenk flask ₂ And 10mL of tetrahydrofuran. After stirring at room temperature for 8 hours, the resulting product was precipitated with n-hexane, separated by filtration and dried under vacuum to give a blue solid nickel complex Ni3 in 78% yield.

The reaction change process is as follows:

example 4:

supported nickel catalyst Ni2@SiO ₂ Is synthesized by the following steps:

stirring 2 mu mol of nickel complex Ni2 prepared in the embodiment 2, 100mg of silicon dioxide and 15ml of dichloromethane in a glove box at 20 ℃ for 12 hours, filtering and drying filter residues to obtain pale yellow solid Ni2@SiO ₂ 。

Example 5:

supported nickel catalyst Ni3@SiO ₂ Is synthesized by the following steps:

stirring 5 mu mol of nickel complex Ni3 prepared in example 3, 100mg of silicon dioxide and 15ml of dichloromethane in a glove box at 20 ℃ for 12 hours, filtering and drying filter residues to obtain light orange solid Ni3@SiO ₂ 。

The effect of the nickel benzidine catalyst before and after loading prepared in examples 1 to 5 was tested for ethylene homopolymerization.

Into a 350mL glass thick-wall pressure vessel in a glove box was charged 500eq of AlEt ₂ Cl, 18mL of n-hexane and a magnetic stirring bar. The pressure vessel was connected to a high pressure line and the solution was degassed. The vessel was heated to the desired temperature using an oil bath and allowed to equilibrate for 15 minutes. 2mL of CH was injected by syringe ₂ Cl ₂ The nickel benzidine catalysts before and after loading prepared in examples 1 to 5 above were injected into the polymerization system, respectively. The reactor was pressurized and maintained at 8.0atm of ethylene with rapid agitation. After 30min, the pressure vessel was vented and the polymer was precipitated in acidified methanol (methanol/hcl=50/1) and dried under vacuum at 50 ℃ for 24 hours. The data obtained for the ethylene homo-polymerization products catalysed by the different catalysts are shown in table 1 below.

TABLE 1 ethylene homo-polymerization Table ^a

^a Polymerization conditions: ni-AlEt ₂ Cl (500 eq), 8atm ethylene pressure, 30min. ^b Activity at 10 ⁶ gmol ^-1 h ^-1 In units of. ^c Molecular weight of 10 ⁴ gmol ^-1 In units of. Determined by Gel Permeation Chromatography (GPC) in trichlorobenzene with polystyrene standards at a temperature of 150 ℃. ^d The degree of branching is given per 1000 carbon atoms. Count per 1000 c= (CH ₃ /3)/[(CH+CH ₂ +CH ₃ )/2]*1000。 ^e As determined by differential scanning calorimetry (DSC, reheat).

The effect of the nickel catalyst containing benzil amine before and after loading, prepared in examples 1 to 5, on catalyzing the copolymerization reaction of ethylene and polar monomer was tested.

A350 mL glass thick-walled pressure vessel was charged with a total of 18mL of 1500eq of AlEt in a glove box ₂ Cl, n-hexane and undecylenic acid, and a magnetic stirring bar. The pressure vessel was connected to a high pressure line and the solution was degassed. The vessel was heated to the desired temperature using an oil bath and allowed to equilibrate for 15 minutes. 2mL of CH was injected by syringe ₂ Cl ₂ 15. Mu. Mol of the metal complex or 15. Mu. Mol of the metal-supported catalyst were injected into the polymerization system. The reactor was pressurized and maintained at 2.0atm of ethylene with rapid agitation. After a duration of 30min, the solvent was evaporated and the polymer was dried under vacuum at 50 ℃ for 24 hours. The copolymerization data obtained for ethylene and undecylenic acid catalyzed by the different catalysts are shown in table 2 below.

TABLE 2 copolymerization of ethylene and undecylenic acid ^a

^a Polymerization conditions: ni catalyst (15. Mu. Mol), alEt ₂ Cl (1500 eq), undecylenic acid (1M), n-hexane (20 mL), 2atm ethylene pressure, 30min. ^b The activity unit is 10 ⁵ gmol ^-1 h ^-1 。 ^c Calculated from the ratio of the polymer obtained and the raw 1-undecylenic acid feed, use is made of ¹ H NMR measurement. ^d Molecular weight of 10 ⁴ gmol ^-1 In units of. Gel Permeation Chromatography (GPC) was performed at 150℃in trichlorobenzene using polystyrene standards. ^e As determined by differential scanning calorimetry (DSC, reheat).

From the results of tables 1 and 2 above, it is found that the use of heterogeneous supported catalysts exhibits higher catalytic activity relative to homogeneous catalysts, resulting in higher molecular weights and lower branching of the polyethylene and ethylene-undecylenic acid produced. In addition, the supported catalyst prepared by the method is less prone to being stuck to a kettle compared with a homogeneous catalyst.

The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.

Claims

1. A benzil group-containing ligand compound having a structural formula shown in formula (I):

wherein R is ₂ 、R ₃ 、R ₄ 、R ₅ Are independently selected from C ₁ ～C ₁₀ Any one of alkyl, substituted or unsubstituted benzhydryl, hydrogen;

R ₁ 、R ₆ simultaneously, any one of methoxy, hydroxy and sodium oxide substituent groups is selected;

wherein when the benzhydryl has a substituent, the substituent is selected from the group consisting of hydroxy, C ₁ ～C ₁₀ Alkyl, C of (2) ₁ ～C ₁₀ Alkoxy, C ₂ ～C ₁₀ Any one of alkenyl groups of (a).

2. The ligand compound of claim 1, wherein R ₂ 、R ₃ 、R ₄ 、R ₅ Each independently selected from one of the following structures:

3. the ligand compound of claim 1, wherein said ligand compound has formula (I ₁ ) Of formula (I) ₉ ) Any one of the structures shown in:

4. a metal complex having a structural formula represented by formula (ii):

wherein M is nickel or palladium, and X is Cl or Br;

R ₂ 、R ₃ 、R ₄ 、R ₅ are independently selected from C ₁ ～C ₁₀ Any one of alkyl, substituted or unsubstituted benzhydryl, hydrogen;

5. The metal complex according to claim 4, wherein R ₂ 、R ₃ 、R ₄ 、R ₅ Each independently selected from one of the following structures:

6. the metal complex according to claim 4, wherein the metal complex has the formula (II) ₁ ) To formula (II) ₉ ) Any one of the structures shown in:

7. a metal-supported catalyst comprising the metal complex according to any one of claims 4 to 6 and a carrier, wherein the metal complex is supported on the carrier.

8. The metal supported catalyst of claim 7, wherein the support comprises at least one of silica, magnesium chloride, and aluminum oxide.

9. A metal supported catalyst as claimed in claim 7 or 8 for catalyzing C ₂ ～C ₁₁ Is used for the polymerization of olefin monomers.

10. The use according to claim 9, wherein the catalyst C ₂ ～C ₁₁ The polymerization of the olefin monomers of (a) comprises:

cocatalyst and C ₂ ～C ₁₁ Is added into an organic solvent, and then the metal negative is injectedSupported catalyst such that C ₂ ～C ₁₁ Carrying out coordination polymerization reaction on olefin monomers of the catalyst;

wherein the organic solvent comprises at least one of toluene, benzene and n-heptane;

the cocatalyst comprises at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, tri-n-butylaluminum, alkali metal or base metal salt;

the C is ₂ ～C ₁₁ The olefin monomer of (2) comprises at least one of methacrylic acid, methyl methacrylate, ethyl methacrylate, 10-undecenol, 10-undecylenic acid, 6-chloro-1-hexene, 1-hexene and 1-octene.