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
- Chinese Journal of Polymer Science Vol. 40, Issue 11, Pages: 1331-1348(2022)
- Affiliations：
  
  1.State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China
- Author bio：
  
  xblu@dlut.edu.cn
- Funds：
- DOI：10.1007/s10118-022-2744-y
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Xiao-Bing Lu, Bai-Hao Ren. Partners in Epoxide Copolymerization Catalysis: Approach to High Activity and Selectivity. [J]. Chinese Journal of Polymer Science 40(11):1331-1348(2022)
DOI：

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

摘要

The unprecedented activities and selectivities were achieved in epoxide copolymerization reactions with CO,2, 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,2,), 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,2, 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

EpoxideRing-opening copolymerizationSynergistic catalysisCO2Stereochemistry control

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