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4-vinylpyridine homopolymerized and ethylene copolymerized acenaphthenyl diimido nickel catalyst and the prepn process

A vinylpyridine and acenaphthylene diimide technology is applied in the field of acenaphthylene diimide nickel supported catalyst and its preparation, which can solve the problems of complex preparation, performance and application limitations of the catalyst.

Inactive Publication Date: 2005-07-13
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the preparation of this catalyst is complicated, and high-valence MAO or boron compounds need to be used as cocatalysts. The obtained product ester is mainly located at the end group, and its performance and application are limited.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] 1. Preparation of supported catalyst

[0020] 1-1 1.624g nickel complex NiL 1 Cl 2 Dissolve in 20ml of dichloromethane to obtain a homogeneous solution;

[0021] 1-2. Mix 2 g of MgCl 2 Dissolve in the mixed solution of ethanol and THF, and stir evenly to obtain the mother liquor; the dosage is MgCl in molar ratio 2 : Alcohol = 3:1, MgCl 2 :THF=1:(24~40);

[0022] 1-3. In N 2 Under protection, add 4g of SiO pretreated by activation at 400-600°C for 4-6 hours to the mother liquor obtained in 1-2 2 , stirred and reacted for 3 hours, heated and drained the liquid; that is, SiO 2 -MgCl 2 Composite carrier;

[0023] 1-4. Add 8ml of hexane to the product of 1-3, raise the temperature to 50-60°C, and add the nickel complex NiL prepared in 1-1 under stirring condition 1 Cl 2 solution, reacted for 1.5h, filtered, washed three times with dichloromethane, and vacuum-dried to obtain a solid-loaded procatalyst; the amount of dichloromethane was per gram of SiO 2 Add 5-12m...

Embodiment 2

[0031] In embodiment 1 step 1-1 " 1.624g nickel complex NiL 1 Cl 2 Dissolved in 20ml of dichloromethane "change" to "1.486gNiL 2 Cl 2 Dissolved in 20ml of dichloromethane"; all the other conditions and operations are the same as in Example 1. The prepared catalyst is used for the polymerization reaction under the same conditions as in Example 1.

[0032]Under the above conditions, P4-VP was prepared by homopolymerization, the catalytic efficiency was 43.4kg P4-VP / mol Ni·h, and the conversion rate of 4-VP was 75.7%. P(E-4-VP) was prepared by copolymerization reaction, the catalytic efficiency was 32.5kg P(E-4-VP) / mol Ni·h, and the 4-VP content in the copolymer was 3.3%.

Embodiment 3

[0034] In embodiment 1 step 1-1 " 1.624g nickel complex NiL 1 Cl 2 Dissolved in 20ml of dichloromethane "change" to "1.486gNiL 3 Cl 2 Dissolved in 20ml of dichloromethane"; all the other conditions and operations are the same as in Example 1. The prepared catalyst is used for the polymerization reaction under the same conditions as in Example 1.

[0035] Under the above conditions, P4-VP was prepared by homopolymerization, the catalyst efficiency was 45.4kg P4-VP / mol Ni·h, and the conversion rate of 4-VP was 70.5%. P(E-4-VP) was prepared by copolymerization reaction, the catalytic efficiency was 28.5kg P(E-4-VP) / mol Ni·h, and the 4-VP content in the copolymer was 4.1%.

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Abstract

The present invention relates to supported acenaphthenyl diimido nickel catalyst for the homopolymerization of 4-vinyl pyridine to prepare poly(4-vinyl pyridine) and the copolymerization of 4-vinyl pyridine and ethylene to prepare ethylene-4-vinyl pyridine copolymer and its preparation process. The catalyst includes main catalyst component and co-catalyst component, the main catalyst component is acenaphthenyl diimido nickel compound supported on composite MgCl2-SiO2 carrier, and the co-catalyst component is AlEt2Cl. The catalyst is prepared through soaking reaction process and the catalyst is spherical grain. The present invention makes it possible to catalyze the homopolymerization of 4-vinyl pyridine to prepare homopolymer and the copolymerization of 4-vinyl pyridine and ethylene to prepare copolymer without using MAO catalyst.

Description

technical field [0001] The invention relates to an acenaphthylenediimide nickel-supported catalyst used for homopolymerization of 4-vinylpyridine and copolymerization with ethylene to prepare polyvinylpyridine (P4-VP) and ethylene / 4-7 alkenylpyridine copolymer and its preparation method. Background technique [0002] It is well known that it is difficult to polymerize and copolymerize polar monomers to obtain homopolymers and copolymers using traditional Ziegler-Natta (Z-N) catalysts. It is reported in the literature that the double imine complexes of late transition metal Pd and methyl Aluminoxane (MAO) catalyzes the copolymerization of methyl acrylate to produce random copolymers, which has attracted widespread attention (Johnsom L.K., Mecking, S, Brookhart M., J.Am.Chem.Soc, 1996, 118:267.). However, the preparation of this catalyst is complicated, and high-valence MAO or boron compounds need to be used as cocatalysts, and the obtained product ester is mainly located at ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F4/70C08F26/06
Inventor 王海华胡扬剑江洪流
Owner SUN YAT SEN UNIV