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Ternary catalyst for preparing aliphatic polycarbonate with high molecular weight

A three-way catalyst and polycarbonate technology, which is applied in the field of three-way catalyst preparation, can solve the problems of poor three-way copolymerization effect, the molecular weight needs to be improved, and polycarbonate separation difficulties, etc.

Inactive Publication Date: 2006-04-12
CNOOC GREEN MATERIALS
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Chinese patent applications ZL89100701.6 and ZL91109459.8 reported a polymer anion coordination bimetallic catalyst system with a catalytic efficiency of 10 4 g polymer / mol catalyst, but the resulting polycarbonate is difficult to separate due to the difficulty of removing the carrier, and the molecular weight needs to be increased
Macromolecules (1995, 28, 7577; 1999, 32, 2137) and Journal of American Chemical Society (1998, 120, 4690; 1999, 121, 107) reported that zinc salts of hindered phenols were used as catalysts to efficiently catalyze carbon dioxide and epoxy Copolymerization of cyclohexane, but poor effect on ternary copolymerization of carbon dioxide, cyclohexane oxide, and propylene oxide

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] The three-way catalyst is zinc trichloroacetate-glycerol-isopropyl zinc, and the molar ratio is 1.5:10:20. The aged catalyst and propylene oxide are added to the autoclave separately, and carbon dioxide is quickly filled into the kettle. The pressure in the kettle is maintained at 3.5 MPa. The copolymerization reaction temperature is 65°C, and the reaction time is 10 hours. The reaction solution was terminated with a calculated amount of methanol. The polymer was washed with a large amount of methanol to obtain a white polycarbonate. The catalyst efficiency is 6,600 g polymer / mol isopropyl zinc. The polycarbonate has a number average molecular weight of 160,000, a carbon dioxide fixation rate of 41% by weight, and an alternating structure content of more than 95%.

Embodiment 2

[0020] The three-way catalyst is-zinc chloroacetate-glycerol-ethyl zinc, the molar ratio is 1:10:20. The aged three-way catalyst and propylene oxide are added to the autoclave separately, and carbon dioxide is quickly filled into the kettle. , The pressure in the kettle is maintained at 3.5MPa. The copolymerization reaction temperature is 65°C, and the reaction time is 8 hours. The reaction solution was terminated with a calculated amount of methanol. The polymer was washed with a large amount of methanol to obtain a white polycarbonate. The catalyst efficiency is 4,050 g polymer / mol ethyl zinc. The polycarbonate has a number average molecular weight of 190,000, a carbon dioxide fixation rate of 41% by weight, and an alternating structure content of more than 95%.

Embodiment 3

[0022] The three-way catalyst is zinc citrate-glycerin-n-butyl zinc, the molar ratio is 1.3:10:20. The aged catalyst and propylene oxide are added to the autoclave separately, and carbon dioxide is quickly filled into the kettle. The internal pressure is maintained at 3.5 MPa. The copolymerization reaction temperature is 65°C, and the reaction time is 8 hours. The reaction solution was terminated with a calculated amount of methanol. The polymer was washed with a large amount of methanol to obtain a white polycarbonate. The catalyst efficiency is 5,200 g polymer / mol n-butyl zinc. The polycarbonate has a number average molecular weight of 80,000, a carbon dioxide fixation rate of 40% by weight, and an alternating structure content of more than 95%.

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Abstract

The ternary catalyst consists of metal salt, alkyl zinc and glycerine. Glycerine and RE salt in certain ratio are added into selected organic solvent, and under the protection of CO2 and while maintaining the reactant mixture at 25 deg.C, alkyl zinc in calculated amount is dropped. After finishing dropping alkyl zinc, the reactant product is aged in CO2 atmosphere to obtain white ternary catalyst suspension, which is used directly in the copolymerization of CO2 and epoxide to produce aliphatic polycarbonate with number-average molecular weight as high as 50,000 and CO2 fixing rate over 40 wt%.

Description

Technical field [0001] The invention belongs to a preparation method of a three-way catalyst for preparing high molecular weight aliphatic polycarbonate. Background technique [0002] Due to the burning of fossil fuels in the production processes of thermal power generation, steelmaking, oil refining, cement, etc., a large amount of carbon dioxide is emitted, and the resulting greenhouse effect has constituted increasingly serious environmental pollution. Therefore, carbon dioxide is regarded as an "environmental hazard." gas. But on the other hand, carbon dioxide is a usable resource under certain conditions. One of the main directions for using carbon dioxide is to synthesize polymer materials with it as a raw material. Carbon dioxide and epoxy compounds can be used as raw materials to synthesize a carbon dioxide copolymer (aliphatic polycarbonate) with a high alternating structure. Due to the presence of ester bonds in the main chain, the polymer is not only photodegradable, b...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G64/02C08G64/20
Inventor 赵晓江王献红王佛松闵加栋周庆海
Owner CNOOC GREEN MATERIALS