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 ternary copolymerization effect, the need to improve the molecular weight, and the difficulty of separation of polycarbonate.

Inactive Publication Date: 2003-08-20
CNOOC GREEN MATERIALS
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  • Application Information

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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

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] The three-way catalyst is yttrium trichloroacetate-glycerol-ethyl zinc, molar ratio: 1:10:20, add the aged catalyst and propylene oxide into the autoclave respectively, and quickly fill the autoclave with carbon dioxide, and the autoclave The internal pressure is maintained at 3.5MPa. The copolymerization reaction temperature was 65° C., and the reaction time was 10 hours. The reaction was quenched with the calculated amount of methanol. The polymer was washed with copious amounts of methanol to obtain a white polycarbonate. Catalyst efficiency 6,500 g polymer / mol ethylzinc. The number-average molecular weight of the polycarbonate is 180,000, the carbon dioxide fixation rate is greater than 40 wt%, and the alternating structure content exceeds 95%.

Embodiment 2

[0025] The three-way catalyst is zinc trichloroacetate-glycerin-isopropyl zinc, the molar ratio is 1.5:10:20, the aged catalyst and propylene oxide are respectively added to the autoclave, and carbon dioxide is quickly charged into the autoclave. The pressure in the kettle was maintained at 3.5MPa. The copolymerization reaction temperature was 65° C., and the reaction time was 10 hours. The reaction was quenched with the calculated amount of methanol. The polymer was washed with copious amounts of methanol to obtain a white polycarbonate. Catalyst efficiency 6,600 g polymer / mol zinc isopropyl. The polycarbonate has a number-average molecular weight of 160,000, a carbon dioxide fixation rate of 41 wt%, and an alternating structure content of over 95%.

Embodiment 3

[0027] The three-way catalyst is -zinc chloroacetate-glycerol-ethyl zinc, molar ratio: 1:10:20, add the aged three-way catalyst and propylene oxide into the autoclave respectively, and quickly fill the autoclave with carbon dioxide , The pressure in the kettle was maintained at 3.5MPa. The copolymerization reaction temperature was 65° C., and the reaction time was 8 hours. The reaction was quenched with the calculated amount of methanol. The polymer was washed with copious amounts of methanol to obtain a white polycarbonate. Catalyst efficiency 4,050 g polymer / mol ethylzinc. The polycarbonate has a number-average molecular weight of 190,000, a carbon dioxide fixation rate of 41 wt%, and an alternating structure content of over 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 process 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 considered an "environmental hazard". gas. But on the other hand, carbon dioxide is a resource that can be used under certain conditions. One of the main directions of using carbon dioxide is to synthesize polymer materials from it. Carbon dioxide copolymers (aliphatic polycarbonates) with highly alternating structures can be synthesized from carbon dioxide and epoxy compounds. Due to the presence of ester bonds in the main chain, the polymer is not only photodegradable, but also a fully biodeg...

Claims

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Application Information

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