Asymmetric alpha-diimine nickel catalysts as well as preparation method and application thereof

A nickel diimide, asymmetric technology, applied in the field of asymmetric α-diimine nickel catalyst and its preparation, can solve the problem of low degree of polymer branching and the like, achieve wide processing methods, reduce processing costs, and facilitate processing Effect

Active Publication Date: 2019-12-20
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The purpose of the present invention is to solve the problem in the prior art that the degree of branching of the polymer obtained by catalyst catalyzing ethylene polymerization is not high on the basis of ensuring the thermal stability of the catalyst and the catalytic performance of the catalyst that can catalyze and obtain high molecular weight polymers Problem, provide a class of asymmetric α-diimine nickel catalyst and its preparation method and application

Method used

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  • Asymmetric alpha-diimine nickel catalysts as well as preparation method and application thereof
  • Asymmetric alpha-diimine nickel catalysts as well as preparation method and application thereof
  • Asymmetric alpha-diimine nickel catalysts as well as preparation method and application thereof

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preparation example Construction

[0056] The preparation method of asymmetric α-diimine nickel catalyst of the present invention, the steps are as follows:

[0057] Step 1, dissolving the aniline represented by formula (a) and the diketone represented by formula (b) in an organic solvent according to the ratio of substances being 1:N, adding a catalyst amount of catalyst, and stirring at 25-80° C. for more than 6 h, Cool to room temperature, evaporate the organic solvent until a yellow solid appears, precipitate the yellow solid, filter, wash, and vacuum-dry to obtain the monoimine product represented by formula (d), and the yield can reach more than 90%;

[0058] Among them, N≥1, the larger N is, the shorter the reaction time is, and the product conversion can be improved;

[0059] Step 2, dissolving the monoimine product prepared in step 1 and the aniline represented by formula (c) in an organic solvent according to the ratio of the substances of 1:1, adding a catalyst amount of catalyst, stirring and reacti...

Embodiment 1

[0075] Step 1, 2,6-diphenylmethyl-4-hydroxyaniline (6.00g, 13.59mmol), 2,3-butanedione (5.85g, 67.95mmol) and p-toluenesulfonic acid monohydrate (20mg ) was dissolved in toluene (200mL), stirred at 80°C and maintained for 24h, cooled to room temperature, and evaporated toluene by rotary evaporation until a yellow solid appeared, and an excess of methanol was added to precipitate the product, the yellow solid was separated by filtration, washed three times with methanol, and Dry to obtain a yellow solid product (5.23g, 75.5% yield), namely 2-(2,6-benzhydryl-4-hydroxyphenylimino) butanone, the structural formula is as follows:

[0076]

[0077] Step 2, 2-(2,6-diphenylmethyl-4-hydroxyphenylimino) butanone (2.00g, 3.92mmol), 4-hydroxypentadecene aniline (1.81g) obtained in step 1 , 3.92mmol) and p-toluenesulfonic acid monohydrate (20mg) were dissolved in toluene (250mL), heated to reflux at 120°C for 3 days, cooled to room temperature, and evaporated methanol until a yellow sol...

Embodiment 2～19

[0084] Steps 1 to 4 are the same as in Example 1, except that the R of the asymmetric α-diimine nickel catalyst is 1 =CH 3 , R 2 =H,R 3 =OCH 3 ,R 4 and R 5 As shown in Table 1. The properties of the obtained polyethylene were tested, and the results are shown in Table 1.

[0085] (R 4 , R 5 ) The structure of the asymmetric α-diimine nickel catalyst and the performance of the catalyzed polyethylene

[0086]

[0087]

[0088] In Table 1, activity: take 10 6 gmol -1 h -1 as the unit. m w is the weight average molecular weight, M w / M n is the polymer dispersibility index, determined by GPC in 1,2,4-trichlorobenzene at 150°C, relative to polystyrene standards. Branching degree = the number of branches per 1000 carbons, determined by proton nuclear magnetic resonance spectroscopy. All data in Table 1 are based on at least two parallel experiments (unless otherwise stated).

[0089] As can be seen from Table 1, when controlling the catalyst substituent R 1 ...

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Abstract

The invention relates to asymmetric alpha-diimine nickel catalysts as well as a preparation method and application thereof, and belongs to the technical field of catalysts. On the basis of ensuring the thermal stability of the catalysts and the catalytic performance of the catalysts capable of obtaining a polymer with a high molecular weight through catslysis, the catalysts solve the technical problem of a low degree of branching of a polymer obtained by catalyst-catalyzed ethylene polymerization in the prior art. The asymmetric alpha-diimine nickel catalysts have a structural formula represented by a formula (I) shown in the specification, on one hand, the catalysts adopt large steric hindrance skeletons of 2,6-bis(diphenylmethyl)phenyl and derivatives of the 2,6-bis(diphenylmethyl)phenylwhich can rotate freely, the electronic and steric effects of the large steric hindrance are changed, on the other hand, the catalysts adopt skeletons of pentiptycene and derivatives of the pentiptycene which can limit geometric rotation, and the electronic and steric effects of the pentiptycene are changed, so that the target that the polymer with the high molecular weight and a branching degreecapable of being regulated and controlled in a large scale is obtained at high temperature can be realized.

Description

technical field [0001] The invention belongs to the technical field of catalysts, and in particular relates to a class of asymmetric α-diimine nickel catalysts and a preparation method and application thereof. Background technique [0002] The α-diimine nickel catalyst can efficiently catalyze ethylene polymerization to obtain polyethylene with high relative molecular weight and different topological structures, but its heat resistance is poor, and it will decompose rapidly when the temperature is not higher than 60 ° C, and with the polymerization As the temperature increases, the relative molecular weight of polyethylene usually decreases, and the branching degree of polyethylene obtained by ethylene polymerization catalyzed by α-diimine nickel catalyst is not easy to control. [0003] In the prior art, in order to improve the thermal stability of the catalyst and obtain polymers with high molecular weight and controllable branching degree, common means are to increase the...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F110/02C08F4/70C07F15/04
CPCC07F15/045C08F110/02C08F4/7006
Inventor 简忠保胡小强
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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