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Catalyst loaded with alpha-diimine metal complex and application of catalyst to olefin polymerization

A technology of metal complexes and diimine compounds, which is applied in the field of catalysts loaded with α-diimine metal complexes, can solve the problems of high cost, general high temperature resistance of catalysts, complex ligand synthesis steps, etc., and achieve the goal of preparing The effect of low cost, good heat resistance and high temperature catalytic activity

Inactive Publication Date: 2019-01-29
HEBEI UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the supported catalyst has good catalytic activity, the high temperature resistance of the catalyst reported by them is average, and the synthesis steps of the ligand are relatively complicated and the cost is relatively high

Method used

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  • Catalyst loaded with alpha-diimine metal complex and application of catalyst to olefin polymerization
  • Catalyst loaded with alpha-diimine metal complex and application of catalyst to olefin polymerization
  • Catalyst loaded with alpha-diimine metal complex and application of catalyst to olefin polymerization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Synthesis of 5-(4-hydroxymethylphenyl)acenaphthenequinone bis(2,6-diisopropyl)benimide nickel bromide(NiI1)

[0038] Ligand 5-(4-hydroxymethylphenyl)acenaphthenequinone bis(2,6-diisopropyl)phenylimine (I1) (i.e. the structure of compound I, wherein Ar=p-methylphenyl, R = (2,6-diisopropyl) phenyl) the preparation route is as follows:

[0039]

[0040] Synthesis of 5-dibromoacenaphthoquinone bis(2,6-diisopropyl)phenylimine a1:

[0041] Add 5-bromoacenaphthenequinone (2.09g, 8mmol), 2,6-diisopropylaniline (3.36g, 19mmol) and 150mL of anhydrous methanol into a 250mL reaction flask, and add 10 drops of anhydrous formic acid , and the mixture was refluxed for 48 hours. The reaction was tracked by chromatography until the raw materials were completely reacted. After the reaction mixture was cooled, a brown-red solid was obtained by suction filtration. The solid was purified by silica gel chromatography to obtain 4.27 g of a yellow solid a1 with a yield of 92%. 1 H NMR (4...

Embodiment 2

[0047] Synthesis of 5-(4-hydroxyphenyl)acenaphthenequinone bis[2,4-dimethyl-6-bis(4-fluorophenyl)methyl]phenylimide nickel bromide (NiI2)

[0048] Ligand 5-(4-hydroxyphenyl)acenaphthenequinone bis[2,4-dimethyl-6-bis(4-fluorophenyl)methyl]phenylimine (I2) (i.e. the structure of compound I, Wherein Ar=p-phenyl, R=[2,4-dimethyl-6-bis(4-fluorophenyl)methyl]phenyl) The preparation route is as follows:

[0049]

[0050] The preparation of compound I2 is the same as that of compound I1 in Example 1, wherein 2,4-dimethyl-6-bis(4-fluorophenyl)methylaniline is used instead of 2,6-diiso Propylaniline, toluene instead of methylene chloride in Example 1, p-toluenesulfonic acid instead of formic acid in Example 1, 4-hydroxybenzopinacol borate instead of 4-hydroxymethyl in Example 1 Phenylboronic acid, bis(dibenzylideneacetone) palladium replaces tetrakis(triphenylphosphine) palladium in embodiment 1, and anhydrous sodium carbonate replaces anhydrous potassium carbonate in embodiment 1. ...

Embodiment 3

[0053] Synthesis of 5-(4-hydroxymethylphenyl)acenaphthenequinone bis[2,6-bis(benzhydryl)-4-methoxy]phenylimide nickel bromide (NiI3)

[0054] Ligand 5-(4-hydroxymethylphenyl) acenaphthoquinone bis[2,6-bis(benzhydryl)-4-methoxyl group] phenylimine (I3) (i.e., the structure of compound I, wherein Ar=p-methylphenyl, R=[2,6-bis(benzhydryl)-4-methoxy]phenyl) The preparation route is as follows:

[0055]

[0056] The preparation of compound I3 is the same as that of compound I1 in Example 1, wherein 2,6-benzhydryl-6-methoxyaniline is used instead of 2,6-diisopropylaniline in Example 1, and toluene is used instead Dichloromethane in Example 1, p-toluenesulfonic acid replaces the formic acid in Example 1, and anhydrous cesium carbonate replaces the anhydrous potassium carbonate in Example 1. The yield of compound I3 was 79%. 1 H NMR (400MHz, CDCl 3): δ7.66(d, J=8.4Hz, 1H), 7.57(d, J=7.9Hz, 2H), 7.41(d, J=7.9Hz, 2H), 7.21-7.12(m, 20H), 6.96 -6.91(m,9H),6.76-6.61(m,17H),6.34(d,J=...

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Abstract

The invention relates to application of a catalyst loaded with alpha-diimine metal complex to olefin polymerization. Hydroxyl at a diimine ligand can react with reactive groups on a chemically modified carrier to form covalent bonds, so that the alpha-diimine compound is firmly supported on the carrier by chemical bonding and is prevented from being detached from the carrier. The alpha-diimine exhibits high-temperature-resistant catalytic activity in the presence of a small steric hindrance group. Meanwhile, an aromatic group on an imine group in the alpha-diimine compound can be arbitrarily changed as needed. Moreover, the preparation of the alpha-diimine ligand is simple, thereby facilitating application of the alpha-diimine metal complex to polymerization of olefins. The load of the alpha-diimine metal complex can improve the problems of adherence to a kettle, control difficulty on polymer morphology, large usage amount of a co-catalyst, bad thermal stability and the like of a homogeneous alpha-diimine late transition metal catalyst in actual application in the prior art.

Description

technical field [0001] The invention relates to the field of olefin catalysis, in particular to a catalyst loaded with α-diimine metal complex and its application in olefin polymerization. Background technique [0002] Although Brookhart et al. (J Am Chem Soc, 1995, 117:6414) found in 1995 that the late transition metal catalysts of α-diimine nickel and palladium catalyzed the polymerization of ethylene into high molecular weight polymers under normal pressure. However, they also found that this type of catalyst has poor high temperature resistance and cannot be industrialized. Subsequent further studies have found that if the volume of the α-diimine ligand substituent becomes larger, its high temperature resistance will be further improved. Long et al. reported α-diimine nickel (ACS Catal. 2014, 4, 2501-2504) with the following structure. The catalyst still has good catalytic activity for ethylene polymerization at 90°C and can meet the requirements of industrialization. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F4/02C08F4/70C08F110/02C08F110/06C08F210/16C08F232/08C08F210/14
CPCC08F4/025C08F4/7006C08F110/02C08F110/06C08F210/16C08F232/08C08F210/14
Inventor 杨敏赵丁丁侯彦辉张锐芳崔咪咪宋小雪
Owner HEBEI UNIV OF TECH
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