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Novel benzobarrelene pentiptycene ligand, transition metal catalyst, preparation method and application in ethylene polymerization

A technology of pentaptycene and transition metal, applied in the fields of catalyst synthesis and polymer synthesis, can solve the problems of low branching degree, remain unchanged, rarely show active polymerization characteristics, catalyst temperature tolerance, etc. The effect of reduced branching degree, high activity and high temperature resistance

Active Publication Date: 2020-06-05
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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  • Abstract
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Problems solved by technology

[0003] At present, α-diimine palladium catalysts can be used to catalyze ethylene polymerization, although high molecular weight (up to millions) polymers can be obtained by regulating the steric and electronic effects of the ligands, but the degree of branching is generally not high (< 130 / 1000C), the degree of branching generally remains almost unchanged with the change of reaction conditions (temperature, pressure), and rarely exhibits the characteristics of active polymerization, and the temperature tolerance of the catalyst is generally below 110°C
thus limiting the scope of application of the polymer to some extent

Method used

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  • Novel benzobarrelene pentiptycene ligand, transition metal catalyst, preparation method and application in ethylene polymerization
  • Novel benzobarrelene pentiptycene ligand, transition metal catalyst, preparation method and application in ethylene polymerization
  • Novel benzobarrelene pentiptycene ligand, transition metal catalyst, preparation method and application in ethylene polymerization

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preparation example Construction

[0035] The present invention also provides a preparation method of a novel benzobarrelene pentadecyl ligand, comprising:

[0036] The diketone compound with the structure (a) and the aniline compound with the structure (b) are dissolved in an organic solvent, and the organic solvent is preferably toluene, xylene, chlorobenzene, methylene chloride, chloroform or acetonitrile, and then add Stir the catalyst at 25-150°C for 6h-7 days, preferably 2-5 days, cool to room temperature, evaporate the solvent by rotary evaporation until a yellow solid appears, add excess methanol or ethanol to precipitate the product, separate the yellow solid by filtration, and use methanol or Wash with ethanol three times and dry under vacuum to obtain a class of novel benzobarrelene pentadecyl ligands described by the general formula (I). The molar ratio of the diketone compound with the structure (a) to the aniline compound with the structure (b) is 1:N, where N≥2, more preferably 1:1-100; most pref...

Embodiment 1

[0051] Embodiment 1 Synthesis of benzobarrelene pentadecyl ligand

[0052]

[0053] 1. Synthesis of 4-methoxypentyl aniline

[0054]

[0055] 4-Hydroxypentylene aniline (3g, 6.50mmol) was dissolved in 100mL of dimethylformamide, sodium hydride (468mg, 19.5mmol) was added under a nitrogen atmosphere, stirred until no bubbles were generated, then methyl iodide ( 0.6mL, 9.75mmol). Stir under nitrogen atmosphere for 1-10 days. Pour into 200mL water, extract 3-20 times with 100mL dichloromethane, separate the organic layer, dry over anhydrous magnesium sulfate for 10min-3h, filter the liquid, evaporate the solvent by rotary evaporation until a yellow solid appears, separate the yellow solid by filtration and put it in Drying under vacuum gave the product as a yellow solid (2.60 g, 84.10% yield).

[0056] 1 H NMR (500MHz, 298K, CDCl 3 ,7.26ppm): δ=7.27-7.36(m,8H,aryl-H), 6.98-6.88(m,8H,aryl-H),5.67(s,2H,CHPh 2 ),5.39(s,2H,CHPh 2 ),3.85 (s,3H,OCH 3 ) ppm.

[0057] 2. S...

Embodiment 2

[0060] Synthesis of embodiment 2 tert-butylbenzobarrelene pentadecyl ligand

[0061]

[0062] A solution of 4-methoxypentetylaniline (6.5g, 13.67mmol), tert-butylbenzobarrelene (1.9g, 5.50mmol) and p-toluenesulfonic acid (10mg) in toluene (250mL) was stirred at 145°C Reflux and maintain for 72 hours, cool to room temperature, evaporate the solvent until a yellow solid appears, add excess ethanol to precipitate the product, separate the yellow solid by filtration, wash three times with ethanol and dry under vacuum to obtain a yellow solid product (4.31g, 62.15% yield).

[0063] 1 H NMR (500MHz, 298K, DMSO-d6, 2.50ppm): δ=7.59-7.53(d, 2H, aryl-H), 7.47-7.41(d, 4H, aryl-H), 7.38-7.31(m, 10H , aryl-H), 7.16-7.11 (m, 4H, aryl-H), 7.07-6.98 (m, 4H, aryl-H), 6.91-6.80 (m, 10H, aryl-H), 6.77-6.70 (d, 2H, aryl-H), 5.88 (d, 4H, CHPh 2 ),5.34(s,2H,CHPh 2 ),5.06 (d,2H,CHPh 2 ),4.07(s,3H,OCH 3 ),1.41(d,2H,C(CH 3 ) 3 )ppm.

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Abstract

The invention provides a novel benzobarrelene pentiptycene ligand, a transition metal catalyst, a preparation method and an application in ethylene polymerization, and belongs to the technical field of catalyst synthesis. The structural formula of the novel ligand is shown as a general formula (I). The structural formula of the transition metal catalyst is shown as a general formula (II). The invention also provides a preparation method of the transition metal catalyst. The method comprises the following steps: dissolving the novel benzobarrelene pentiptycene ligand shown in the general formula (I) and (COD)PdMeCl in a solvent, and reacting to obtain the transition metal catalyst. The invention also provides the application of the transition metal catalyst in ethylene polymerization. According to the catalyst disclosed by the invention, on the basis of ensuring the thermal stability of the catalyst, the polymer with the characteristics that the maximum Mw can reach 2 million and the maximum branching degree can reach 250 / 1000C can be obtained by catalyzing ethylene polymerization.

Description

technical field [0001] The invention belongs to the technical field of catalyst synthesis and the field of polymer synthesis, and specifically relates to a novel benzobarrelene pentadecyl ligand, a transition metal catalyst, a preparation method and an application in ethylene polymerization. Background technique [0002] Since 1995, α-diimine post-transition metal (palladium) catalysts (J. Am. Chem. Soc. 1995, 117, 6414) have been developed as a class of very useful ethylene catalysts due to the unique chain walking mechanism. polymerization catalyst. However, there are still some problems in this system that have not been resolved, such as the easy thermal deactivation of the catalyst and the difficulty in regulating the microstructure of the polymer. In order to solve these problems, the current common means is to adjust the axial steric hindrance of the catalyst, or to adjust the electronic effect of the ligand. [0003] At present, α-diimine palladium catalysts can be ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C251/20C07C249/02C07F15/00C08F110/02C08F4/70
CPCC07C251/20C07F15/0093C08F110/02C07C2603/90C08F4/7006C08F2500/01
Inventor 简忠保张宇星
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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