Large-steric-hindrance ketimine nickel catalyst as well as ligand compound, preparation method and application thereof

A technology of ketimine nickel and complexes, which is applied in the field of preparation of large sterically hindered ketimine nickel catalysts and ligand compounds thereof, can solve the problems of low activity and low molecular weight of polyethylene products, and achieves increased molecular weight and improved thermal conductivity. Effects of stability and chemical activity

Active Publication Date: 2019-11-22
UNIV OF SCI & TECH OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] However, such catalyst 6 has very low activity in ethylene polymerization (only 6.4×10 4 g·mol -1 h -1 ), and the molecular weight of the resulting polyethylene product is not high (the number average molecular weight is less than 80000)

Method used

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  • Large-steric-hindrance ketimine nickel catalyst as well as ligand compound, preparation method and application thereof
  • Large-steric-hindrance ketimine nickel catalyst as well as ligand compound, preparation method and application thereof
  • Large-steric-hindrance ketimine nickel catalyst as well as ligand compound, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0068] Example 1: 3-((2,4-bis(xylylmethyl)-8-(p-tolyl)naphthalen-1-yl)imino)butan-2-one (II 1 ) preparation

[0069]

[0070] Under nitrogen protection, 2,4-benzhydryl-8-(p-tolyl)naphthalene-1-amine (1.13 g, 2 mmol), 2,3-butanedione (344 mg, 4 mmol) and p-toluenesulfonic acid (20 mg) in toluene (20 ml) were stirred at 80°C for 24 hours and passed through a thin The reaction was monitored by layer chromatography (TLC). The reaction was terminated after showing a major product spot on the TLC plate. The solvent was evaporated under reduced pressure, and the remaining mixture was diluted in methanol (30 mL) and stirred for 1 hour. A yellow solid (887 mg, 70% yield) was isolated by vacuum filtration. The obtained product was detected and analyzed, and the results confirmed that it was the title compound.

[0071] 1 H NMR (400MHz, CDCl 3 )δ8.00(d, J=8.3Hz, 1H), 7.38-7.32(m, 1H), 7.24-6.97(m, 21H), 6.90-6.82(m, 2H), 6.76(d, J=6.6Hz , 2H), 6.65(s, 1H), 6.21(s, 1H, CHPh 2 ...

Embodiment 2

[0074] Example 2: 4-((2,4-bis(xylylmethyl)-8-(p-tolyl)naphthalene-1-yl)imino)-2,2-dimethylpenta-3- Ketone (II 2 ) preparation

[0075]

[0076] Under nitrogen protection, in a 250 ml round bottom flask equipped with reflux condenser, magnetic stirring device and oil bath, at 30 °C, 1-tert-butyl-1-propyne (960 mg, 10 mmol) , 0.01 equivalent of ruthenium trichloride (20.7 mg, 0.1 mmol) and 3 equivalents of iodobenzenediacetic acid (9660 mg, 30 mmol) in dichloromethane (40 ml) and water (10 ml) mixed solution was stirred for 5 Hour. The mixture was then separated using a separatory funnel, the dichloromethane phase was dried over anhydrous sodium sulfate, filtered and the solvent was removed in vacuo. The crude product was purified by standard silica gel chromatography using hexane / ethyl acetate as eluent to afford 4,4-dimethylpentane-2,3-dione. Since 4,4-dimethylpentane-2,3-dione has a low boiling point, it can be used directly in the next step.

[0077] Next, 2,4-benzhy...

Embodiment 3

[0081] Example 3: 2-((2,6-bis(xylylmethyl)-4-methylphenyl)imino)-1-(4-methoxyphenyl)propan-1-one ( II 3 ) preparation

[0082]

[0083] Under nitrogen protection, 2,6-bis(diphenylmethyl)-4-methylaniline (879 mg, 2 mmol), 1-(4-methoxyphenyl)propane-1,2-dione (712 mg, 4 mmol) and p-toluenesulfonic acid (20 mg) in toluene (20 ml) in Stir at 120° C. for 48 hours until there is a main product spot on the TLC plate, then the reaction is terminated. The solvent was evaporated under reduced pressure, and the remaining mixture was diluted in methanol (30 mL) and stirred for 1 hour. A yellow solid (720 mg, 60% yield) was isolated by vacuum filtration. The obtained product was detected and analyzed, and the results confirmed that it was the title compound.

[0084] 1 H NMR (400MHz, CDCl 3 )δ7.90(d, J=8.8Hz, 2H), 7.32-7.16(m, 13H), 7.04(dd, J=10.9, 7.7Hz, 8H), 6.74(d, J=8.8Hz, 2H), 6.67(s, 2H), 5.31(s, 2H, CHPh 2 ), 3.84(s, 3H, OMe), 2.15(s, 3H, aryl-CH 3 ), 1.08 (s, 3H, N=CM...

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Abstract

The invention relates to a large-steric-hindrance ketimine nickel complex shown as a formula (I) and a ligand compound, a preparation method and application thereof. R1, R2, Ar and BAF- are defined inthe specification. The large-steric-hindrance ketimine nickel complex can be used as a catalyst for catalyzing polymerization reaction of lower olefins such as ethylene; the catalyst has high catalytic activity (the activity can reach 1.06*10<8> g.mol<-1>.H<-1>) and high thermal stability, and polyethylene with high molecular weight (the number-average molecular weight can reach 1.23*10<6> g / mol)can be obtained. The large-steric-hindrance nickel catalyst can also be used for copolymerization reaction of ethylene and other polymerizable monomers such as methyl undecylenate and the like to obtain a copolymer with high molecular weight and polar monomer units, and with a relatively high insertion ratio.

Description

technical field [0001] The invention relates to the field of catalysis and the field of synthetic polymer polyolefin materials, in particular to a large sterically hindered ketimine nickel catalyst and its ligand compound, preparation method and application. Background technique [0002] For more than half a century, late-transition metal-catalyzed olefin polymerization has been a global research hotspot. Nickel metal entered this field as a "poison". Ziegler and his colleagues demonstrated the well-known "nickel effect" in which aluminum alkyls in the presence of nickel salts lead to complete conversion of ethylene to 1-butene. This discovery became the starting point for the development of Ziegler catalysts. Now, there are many nickel metals reported to produce high molecular weight polyethylene. An important work of Brookhart in 1995 was to show that nickel diimide can prepare high molecular weight polyethylene, and its activity is comparable to that of early transitio...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/04C07C249/02C07C251/16C08F110/02C08F210/02C08F4/70
CPCC07C251/16C07F15/04C08F110/02C08F210/02C08F4/7008
Inventor 陈昶乐梁涛
Owner UNIV OF SCI & TECH OF CHINA
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