Double metal cyanide-rare earth compound composite catalyst for CO2-epoxypropane copolymerization

A technology of double metal cyanide and rare earth complex, which is applied in the field of double metal cyanide-rare earth complex composite catalyst, can solve problems such as literature and patent reports that have not yet been studied, and achieve the effect of being beneficial to industrial development and utilization

Active Publication Date: 2010-09-15
中科应化(长春)科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] At present, the research on carbon dioxide-propylene oxide copolymerization with double metal cyanide-rare earth salt catalyst composed of double metal cyanide and rare earth complex has not been reported in literature and patents

Method used

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  • Double metal cyanide-rare earth compound composite catalyst for CO2-epoxypropane copolymerization

Examples

Experimental program
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Effect test

preparation Embodiment 1

[0021] The preparation of preparation example 1 double metal cyanide:

[0022] 40g ZnCl 2 3.32g K 3 Co(CN) 6 and 50ml of deionized water, the dropwise addition process took 2 hours. After the dropwise addition was completed, the reaction was continued to stir at 500 rpm for 2 hours at 50°C. After the reaction, the reactant was centrifuged at 5,000rpm for 30 minutes to collect the precipitate, which was continuously washed with tert-butanol / water (V / Vml)=100 / 100, 120 / 80, 140 / 60, 160 / 40, The 180 / 20 mixed solution and 200ml tert-butanol were stirred at 60-100rpm to pulp and wash 6 times. The time for each pulping and washing was 40 minutes. After each pulping and washing, it was centrifuged at 5,000rpm for 30 minutes. The obtained final product was dried in a vacuum oven at 50°C to constant weight, and the product after constant weight was divided into ampoule bottles, and treated with Ar at 50°C to 20-40Pa for 48 hours, repeatedly filled with Ar for 24 times, and finally pro...

preparation Embodiment 2

[0023] The preparation of preparation embodiment 2 rare earth complexes:

[0024] Under stirring at 80 rpm, 25 g of diyttrium trioxide was added ten times, 2.5 g each time, into a three-necked flask with 48.9 g of trichloroacetic acid and 100 ml of deionized water, and the reaction temperature was controlled at 40-45°C. After all the diyttrium trioxide was added, stirring was continued at 40-45°C for 2.5 hours. The reactant is filtered to remove unreacted diyttrium trioxide, and the clear liquid is dehydrated at 40-45°C under reduced pressure at 1.13KPa until all the water is removed. The obtained white yttrium trichloroacetate complex powder was divided into ampoules, treated with vacuum at 80°C to 20-40Pa and filled with Ar for 80 hours. After filling with Ar 40 times, it was sealed and stored under the protection of Ar.

preparation Embodiment 3

[0025] The preparation of preparation embodiment 3 rare earth complexes:

[0026] Under stirring at 80rpm, 37g of diyttrium trioxide was added to a three-necked flask with 38.7g of dichloroacetic acid and 100ml of deionized water in ten times, 3.7g each time, and the reaction temperature was controlled at 40-45°C. After all the diyttrium trioxide was added, stirring was continued at 40-45°C for 3 hours. The reactants were filtered to remove unreacted diyttrium trioxide, and the clear liquid was dehydrated under reduced pressure at 40-45°C and 1.13KPa until all the water was removed. The obtained white yttrium dichloroacetate complex powder is divided into ampoule bottles, vacuumed at 80°C to 20-40Pa and filled with N 2 Treat for 80 hours, charge N 2 After 40 times, at N 2 Store under airtight protection.

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Abstract

The invention provides a double metal cyanide-rare earth compound composite catalyst for CO2-epoxypropane copolymerization. In the catalyst, the mol ratio of the metal Co, Fe, Ni or Cr to La, Pr, Nd, Yb, Lu or Y of rare earth is 1:1-1:16. When the catalyst is used for the CO2-epoxypropane copolymerization, the weight content of cyclic carbonate ester in a reaction mixture is less than 2 percent, the polymer yield in a crude product is improved by more than 30 percent compared with the condition that only the double metal cyanide is used as the catalyst, and the maximum catalysis efficiency can reach 52kg of polymer in 1g of compound DMC (Dimethyl Carbonate). In the copolymer, the content of carbonic ester is more than 35 percent, and the content of Mn is more than 100,000g/mol.

Description

technical field [0001] The present invention belongs to CO 2 - A double metal cyanide-rare earth complex composite catalyst for the copolymerization of propylene oxide. Background technique [0002] Carbon dioxide is not only a greenhouse gas, but also an available carbon resource, and has attracted much attention. Since the advent of carbon dioxide-propylene oxide copolymer (Makromol.Chem., 130, 210, 1969), scientists from various countries have successively developed ZnEt 2 - Catalyst systems containing active hydrogen compounds, zinc salt catalysts, large hindrance zinc salt catalysts, rare earth catalyst systems and Al, Cr, Co, Mn, Mg catalyst systems, etc. [0003] The use of double metal cyanides to catalyze carbon dioxide-epoxide copolymerization originated from the research work of Kuyper et al. In 1985, the Kuyper research group first used Zn 3 [Fe(CN) 6 ] 2 Catalyzes the copolymerization of carbon dioxide and epoxides. The polymerization temperature is 35°C,...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G64/34
Inventor 王献红李志峰赵晓江闵加栋周庆海
Owner 中科应化(长春)科技有限公司
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