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Metal hydrides coordination catalyst and preparation and application thereof

A coordination catalyst and double metal cyanide technology, which is applied in the preparation of metal cyanide coordination catalysts and the preparation of new metal cyanide coordination catalysts, can solve problems that do not involve the chemical modification of the active center of the catalyst. , to achieve the effect of improving the degradation performance and reducing the degree of reaction

Active Publication Date: 2016-08-03
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The preparation methods of these catalysts do not involve the chemical modification of the active center of the catalytic capitalization agent, thus cannot solve the above-mentioned problems

Method used

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  • Metal hydrides coordination catalyst and preparation and application thereof
  • Metal hydrides coordination catalyst and preparation and application thereof
  • Metal hydrides coordination catalyst and preparation and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] First, 1.00 g of Zn-Co(III) DMCC described in formula (2) was dried at a temperature of 130° C. under vacuum for 20 hours. TGA results showed that water and tert-butanol in the catalyst could be removed, and the structural formula was Zn 2 [Co(CN) 6 ](OH) 0.6 Cl 0.4 . Then add 309mL acetic acid to the dry complex under a dry argon atmosphere, and react with magnetic stirring at 20°C for 200 hours. Dry in a vacuum oven to constant weight to obtain 0.92 g of a white solid, which is sealed and stored.

Embodiment 2

[0046] First, 0.50 g of Zn-Co(III) DMCC described in formula (2) was dried at a temperature of 190° C. under vacuum for 8 hours. TGA results showed that the water and tert-butanol in the catalyst were completely removed, and the structural formula was Zn 2 [Co(CN) 6 ](OH) 0.6 Cl 0.4 . Then 22.06 g of trichloroacetic acid was added, dissolved in n-hexane and reacted with magnetic stirring at 70° C. for 100 hours. After the reaction, filter with suction, wash the filter cake three times with 300 mL of n-hexane, and dry the solid filter cake in a vacuum oven at 60°C until constant weight to obtain 0.41 g of white solid, which is sealed and stored.

Embodiment 3

[0048] First, 0.20 g of Zn-Co(III) DMCC described in formula (2) was dried at a temperature of 250° C. under vacuum for 2 hours. TGA results showed that the water and tert-butanol in the catalyst were completely removed, and the structural formula was Zn 2 [Co(CN) 6 ](OH) 0.6 Cl 0.4 . Then 7.7g of propiolic acid was added, dissolved in cyclohexane and reacted with magnetic stirring at 120°C for 0.5 hours. After the reaction, filter with suction, wash the filter cake three times with 300 mL of cyclohexane, and dry the solid filter cake in a vacuum oven at 60°C to constant weight to obtain 0.16 g of white solid, which is sealed and stored.

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Abstract

The invention relates to a catalyst preparation technology and aims at providing a metal hydrides coordination catalyst and preparation and application thereof. The structural formula of an active component of the catalyst is Zn2[Co(CN)6](OR)mXn, wherein R is alkyl, aryl or acyl, X is a single valence anion, m and n are positive numbers, and m plus n is 1. The divalent Zn ions in the activated component are coordinated with inner metal trivalent cobalt ions through cyanide ions and surrounding anions OR and X at the same time to form a Co-CN-Zn-OR structure and a Zn-X structure. The activated triggering center structure of the catalyst is a definite Zn-OR bond; when the catalyst catalyzes a reaction in which epoxyalkane takes participate, due to the fact that one end of the generated polymer is an R group, the chain transfer reaction degree is reduced, and the degradation property of a product is improved; one end of the obtained polymerisate is an OR group, due to the diversity of the R group, functionalization of the end group of the polymer is achieved, and only polymer with the two ends being hydroxyls can be obtained through reported DMCC containing the Zn-OH bond.

Description

technical field [0001] The invention relates to catalyst preparation technology, in particular to the invention about the preparation and application of a novel metal cyanide coordination catalyst. It specifically relates to the preparation technology and application of a metal cyanide coordination catalyst whose catalytic active center is Zn-OR (R is an alkyl group, an aryl group and an acyl group), and which can catalyze a series of copolymerization reactions in which epoxides participate. Background technique [0002] Double metal cyanide complex (DMCC) was first reported by the General Tire Rubber Company of the United States in the 1960s, and was originally used to catalyze the ring-opening polymerization of epoxides to prepare polyether polyols. The polyether polyol prepared by DMCC has the characteristics of low unsaturation, high molecular weight and narrow distribution, so it has been widely studied and applied at home and abroad. In recent years, modified DMCC cat...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G65/06C08G63/83C08G64/34C08G63/64C07F19/00
CPCC07F15/065C08G63/64C08G63/83C08G64/34C08G65/06C08G2650/24
Inventor 张兴宏张滢滢魏人建
Owner ZHEJIANG UNIV
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