Partners in Epoxide Copolymerization Catalysis: Approach to High Activity and Selectivity

Xiao-Bing Lu; Bai-Hao Ren

doi:10.1007/s10118-022-2744-y

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Partners in Epoxide Copolymerization Catalysis: Approach to High Activity and Selectivity

FEATURE ARTICLE | Updated：2022-10-25

- Partners in Epoxide Copolymerization Catalysis: Approach to High Activity and Selectivity
- Partners in Epoxide Copolymerization Catalysis: Approach to High Activity and Selectivity
- 高分子科学（英文版） 2022年40卷第11期页码：1331-1348
- Affiliations：
  
  State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China
- Author bio：
  
  xblu@dlut.edu.cn
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 21920102006).
- DOI：10.1007/s10118-022-2744-y
  中图分类号：
- 收稿：2022-03-04，
  
  修回：2022-3-26，
  
  录用：2022-3-28，
  
  网络首发：2022-06-17，
  
  纸质出版：2022-11-01
- Accepted：
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Lu, X. B.; Ren, B. H. Partners in epoxide copolymerization catalysis: approach to high activity and selectivity. Chinese J. Polym. Sci. 2022, 40, 1331–1348

Xiao-Bing Lu, Bai-Hao Ren. Partners in Epoxide Copolymerization Catalysis: Approach to High Activity and Selectivity[J]. Chinese Journal of Polymer Science, 2022, 40(11): 1331-1348.
Lu, X. B.; Ren, B. H. Partners in epoxide copolymerization catalysis: approach to high activity and selectivity. Chinese J. Polym. Sci. 2022, 40, 1331–1348 DOI： 10.1007/s10118-022-2744-y.

Xiao-Bing Lu, Bai-Hao Ren. Partners in Epoxide Copolymerization Catalysis: Approach to High Activity and Selectivity[J]. Chinese Journal of Polymer Science, 2022, 40(11): 1331-1348. DOI： 10.1007/s10118-022-2744-y.

摘要

The unprecedented activities and selectivities were achieved in epoxide copolymerization reactions with CO

COS or anhydrides

via

inter- or/and intra-molecular synergistic catalysis

affording the completely alternating copolymers with low dispersities. In some cases

highly enantioselective epoxide copolymerization was realized in a controllable manner to generate isotactic copolymers with main-chain chirality.

Abstract

The ring-opening alternating copolymerization processes of epoxides with small-molecule monomers

such as carbon dioxide (CO

)

carbonyl sulfide (COS) and cyclic anhydrides

are powerful strategies for preparing polymeric materials with degradable carbonate/ester/thiocarbonate main-chain backbone units. The catalysts selected for copolymerization processes play crucial roles in determining their reaction rates and productivities

as well as the selectivity

regio- and stereochemistry

compositions

and the molecular weights of their resultant copolymers. These processes often generate undesirable byproducts such as polyether or ether linkages dispersed randomly within the copolymer’s chain

and/or more thermodynamically stable cyclic products. In this account

we outline our efforts of over a dozen years on developing highly active well-defined metal catalysts based on inter- and intra-molecular synergistic strategies to selectively produce completely alternating copolymers from epoxides and various small-molecule monomers. Much attention was paid to the enantioselective resolution copolymerization processes of

racemic

epoxides

via

regioselective ring-openings

and the asymmetric copolymerization processes of

meso

-epoxides with CO

COS

or cyclic anhydrides

via

dissymmetrical ring-openings using multichiral catalytic systems

and affording isotactic copolymers with main-chain chirality. In addition

this account provides a thorough mechanistic understanding of the high reactivities

excellent selectivity

and unprecedented stereochemical controls of these copolymerization systems

mediated by inter- and intramolecular synergistic catalysis.

关键词

Keywords

references

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