Installation of Multiple Chiral Centers in Aliphatic Polyesters Backbone Enables Unexpected Crystallinity <italic style="font-style: italic">via</italic> Asymmetric Catalytic Copolymerization

Zheng-Fei Liu; Bai-Hao Ren; Yi-Shu Fu; Jun Yang; Yong-Qiang Teng; Ye Liu; Xiao-Bing Lu

doi:10.1007/s10118-025-3266-1

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Installation of Multiple Chiral Centers in Aliphatic Polyesters Backbone Enables Unexpected Crystallinity via Asymmetric Catalytic Copolymerization

RESEARCH ARTICLE | Updated：2025-07-14

- Installation of Multiple Chiral Centers in Aliphatic Polyesters Backbone Enables Unexpected Crystallinity via Asymmetric Catalytic Copolymerization
- Chinese Journal of Polymer Science Vol. 43, Issue 6, Pages: 946-951(2025)
- Affiliations：
  
  State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China
- Author bio：
  
  liuye@dlut.edu.cn (Y.L.)
  xblu@dlut.edu.cn (X.B.L.)
- Funds：
- DOI：10.1007/s10118-025-3266-1
  CLC：
- Received：16 October 2024，
  
  Revised：2024-11-07，
  
  Accepted：12 November 2024，
  
  Online First：25 January 2025，
  
  Published：20 May 2025
- Accepted：
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Liu, Z. F.; Ren, B. H.; Fu, Y. S.; Yang, J.; Teng, Y. Q.; Liu, Y.; Lu, X. B. Installation of multiple chiral centers in aliphatic polyesters backbone enables unexpected crystallinity via asymmetric catalytic copolymerization. Chinese J. Polym. Sci. 2025, 43, 946–951

Zheng-Fei Liu, Bai-Hao Ren, Yi-Shu Fu, et al. Installation of Multiple Chiral Centers in Aliphatic Polyesters Backbone Enables Unexpected Crystallinity via Asymmetric Catalytic Copolymerization[J]. Chinese Journal of Polymer Science, 2025, 43(6): 946-951. DOI: 10.1007/s10118-025-3266-1.
Liu, Z. F.; Ren, B. H.; Fu, Y. S.; Yang, J.; Teng, Y. Q.; Liu, Y.; Lu, X. B. Installation of multiple chiral centers in aliphatic polyesters backbone enables unexpected crystallinity via asymmetric catalytic copolymerization. Chinese J. Polym. Sci. 2025, 43, 946–951 DOI： 10.1007/s10118-025-3266-1.

Zheng-Fei Liu, Bai-Hao Ren, Yi-Shu Fu, et al. Installation of Multiple Chiral Centers in Aliphatic Polyesters Backbone Enables Unexpected Crystallinity via Asymmetric Catalytic Copolymerization[J]. Chinese Journal of Polymer Science, 2025, 43(6): 946-951. DOI: 10.1007/s10118-025-3266-1. DOI：

摘要

In this study

three-carbon chiral centers were simultaneously installed in the aliphatic polyester backbone by asymmetric copolymerization of CHO with chiral MSA. The different combinations of stereochemistry in two building blocks impact the thermal properties and crystalline behaviors of the resulting polyesters considerably

and the identical configuration combination displays two Tm values of 109 and 130 °C

whereas the opposite one only exhibits a

value of 55 °C.

Abstract

The asymmetric alternating copolymerization of

meso

-epoxide and cyclic anhydrides provides an efficient access to enantiopure polyesters. Contrary to the extensive investigation of the stereochemistry resulting from epoxide building block

the chirality from anhydride and the configurational match with epoxide remain elusive. Herein

we discover that the bimetallic chromium catalysts have led to an obvious enhancement in terms of reactivity and enantioselectivity for the asymmetric copolymerization of

meso

-epoxide with various non-symmetric chiral anhydrides. Up to 97%

was obtained during the asymmetric copolymerization of cyclohexene oxide (CHO) with (

)-methylsuccinic anhydride (

-MSA)

and three- or four-carbon chiral centers were simultaneously installed in the aliphatic polyester backbone. In particular

the different combinations of stereochemistry in epoxide and anhydride building blocks considerably affect the thermal properties and crystalline behaviors of the resulting polyesters. This study uncovers an interesting method for regulating polymer crystallinity

via

matching the chirality of different monomers.

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Keywords

references

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Installation of Multiple Chiral Centers in Aliphatic Polyesters Backbone Enables Unexpected Crystallinity via Asymmetric Catalytic Copolymerization

DOI：10.1007/s10118-025-3266-1

摘要

Abstract

关键词

Keywords

references