Supported rare earth ternary catalyst for combined polymerization of carbonic anhydride and epoxide and preparing method therefor

A three-way catalyst and epoxide technology, applied in the field of supported rare earth three-way catalysts, can solve the problems of complicated preparation process, no rare earth three-way catalyst, etc., and achieve the effect of increasing catalytic activity and improving yield

Active Publication Date: 2009-04-08
中科应化(长春)科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although US 6,844,287 B2 claims that the supported zinc glutarate catalyst improves the catalytic efficiency of zinc glutarate, the preparation process of the loaded zinc glutarate is cumbersome, the catalyst needs

Method used

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  • Supported rare earth ternary catalyst for combined polymerization of carbonic anhydride and epoxide and preparing method therefor

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Embodiment 1 is used for the preparation of the supported rare earth three-way catalyst of carbon dioxide and epoxide copolymerization

[0022] in 99.98% pure CO 2 Under protection, add 30ml 1,3-dioxolane in the catalyst preparation bottle, then add 0.000975mol rare earth complex yttrium trichloroacetate (Y(CCl 3 COO) 3 ) and 0.00975mol glycerol, to be Y (CCl 3 COO) 3 After all dissolved, slowly drop ZnEt into the bottle 2 , ZnEt 2 It is advisable to control the reaction temperature at 35-45°C for the dropping speed; after the dropping is completed, after no gas is released, the prepared rare earth three-way catalyst is aged at 60°C for 3 hours with shaking. in CO 2 Under protection, add γ-Al activated at 600°C for 10 hours to the aged rare earth three-way catalyst 2 o 3 (50-100 nm) 0.0244 mol and 15 g of glass beads with a particle diameter of 4-6 mm, and additionally add 10 ml of 1,3-dioxa-pentane. The prepared bottle was placed in a constant temperature bath...

Embodiment 2

[0023] Embodiment 2 is used for the preparation of the supported rare earth three-way catalyst of carbon dioxide and epoxide copolymerization

[0024] in CO 2 Under protection, add γ-Al activated at 600°C for 10 hours to the aged rare earth three-way catalyst in the preparation bottle 2 o 3 (50~100nm)0.0122mol, La 2 o 3 (100-250 nm) 0.0122 mol and 15 g of glass beads with a particle diameter of 4-6 mm, and 10 ml of 1,3-dioxa-pentane was added. The prepared bottle was placed in a constant temperature bath at 60±2°C for mechanical vibration grinding for 8 hours, the vibration frequency was 180 times / min, and the amplitude was 45 mm. Other conditions are as in Example 1.

Embodiment 3

[0025] Embodiment 3 is used for the preparation of the supported rare earth three-way catalyst of carbon dioxide and epoxide copolymerization

[0026] in CO 2 Under protection, add SiO activated at 650°C for 8 hours to the aged rare earth three-way catalyst in the preparation bottle 2 (150-250 nm) 0.0244 mol and 15 g of glass beads with a particle diameter of 4-6 mm, and 10 ml of 1,3-dioxa-pentane was added. The preparation bottle was placed in a constant temperature bath at 60±2° C. for 8 hours with sealed magnetic stirring and grinding, and the magnetic stirring speed was 500 rpm. Other conditions are as in Example 1.

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Abstract

The invention provides a loaded rare-earth three-way catalyst used for the copolymerization of carbon dioxide and epoxide, which is prepared through constant-temperature sealed magnetic stirring grinding or mechanical oscillating grinding of a rare-earth three-way catalyst and a carrier. The load ratio between the mol of Zn in the rare-earth three-way catalyst and the mol of the carrier is 1:0.5 to 1:7. Catalytic activity is more than 7000g of polymer per mol of Zn, which is increased by more than 30 percent to 48 percent compared with the catalytic activity of the rare-earth three-way catalyst which is not supported used for the copolymerization of CO2 and propylene oxide. The number average molecular weight of the polymer produced is more than 100,000 and the alternating structure of the carbon dioxide and the epoxide is more than 95 percent.

Description

technical field [0001] The invention belongs to a supported rare earth three-way catalyst for copolymerization of carbon dioxide and epoxide and a preparation method. Background technique [0002] The aliphatic polycarbonate with high molecular weight and high alternating structure synthesized from carbon dioxide and epoxide has full biodegradation and excellent oxygen permeation barrier performance, and is expected to be widely used in food preservation, medicine, food packaging and other fields. [0003] Adoption of ZnEt from Inoue 2 -H 2 Since O(1:1) catalytic system realized the copolymerization of carbon dioxide and propylene oxide (Makrom.Chem., 130, 210, 1969), there have been some related use of diethylzinc / active hydrogen compound catalytic system and carboxylic acid Patents and papers on the copolymerization of carbon dioxide and epoxides catalyzed by salt catalysts (US Patents US 3,585,168, US 3,900,424 and US 3,953,383; J. Polym. J.Polym.Sci., Polym.Chem.Ed., ...

Claims

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Application Information

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IPC IPC(8): C08G64/34
Inventor 王献红路宏伟赵晓江王佛松
Owner 中科应化(长春)科技有限公司
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