Recent Progress in Ring-opening Polymerizations Catalyzed by Rare Earth Catalysts

Ting Shen; Xu-feng Ni; Jun Ling

doi:10.11777/j.issn1000-3304.2020.20261

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Recent Progress in Ring-opening Polymerizations Catalyzed by Rare Earth Catalysts

Reviews | 更新时间：2021-05-07

- Recent Progress in Ring-opening Polymerizations Catalyzed by Rare Earth Catalysts
- Acta Polymerica Sinica Vol. 52, Issue 5, Pages: 445-455(2021)
- 作者机构：
  
  教育部高分子合成与功能构造重点实验室浙江大学高分子科学与工程学系　杭州 310027
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2020.20261
  CLC：
- Published：3 May 2021，
  
  Published Online：1 February 2021，
  
  Received：1 December 2020，
  
  Revised：24 December 2020，
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Ting Shen, Xu-feng Ni, Jun Ling. Recent Progress in Ring-opening Polymerizations Catalyzed by Rare Earth Catalysts. [J]. Acta Polymerica Sinica 52(5):445-455(2021)
DOI：

Ting Shen, Xu-feng Ni, Jun Ling. Recent Progress in Ring-opening Polymerizations Catalyzed by Rare Earth Catalysts. [J]. Acta Polymerica Sinica 52(5):445-455(2021) DOI： 10.11777/j.issn1000-3304.2020.20261.

摘要

稀土催化剂在开环聚合中表现出极高的催化活性，本文总结了近十年来稀土催化剂在内酯、交酯、环醚、环碳酸酯、环羧酸酐等单体开环聚合中的应用，结合催化剂结构与聚合效果总结了稀土催化剂在聚合过程可控和聚合物结构控制方面的独特优势，并介绍了稀土催化的新型开环聚合方法.

Abstract

Rare earth (RE) catalysts exhibit extremely high catalytic activity in ring-opening polymerization. This work reviews the application of rare earth catalysts in ring-opening polymerizations of lactones

lactides

cyclic ethers

cyclic carbonates and cyclic carboxyanhydrides in the past decade. Compared to other transition metals and main group elements

RE elements have larger cationic radii which allow for higher coordination numbers and more coordination modes

endowing RE catalysts with high catalytic activity. These characteristics not only fuel the widespread use of new RE catalysts in pursuing high molecular weight and polymerization rate of intensively studied monomers

such as

-caprolactone (CL)

lactide (LA) and

-butyllactone (BBL)

but also unleash the polymerization of traditionally non-polymerizable

-butyrolactone (

-BL) and its derivatives. The inherent low strain energy of the five-membered ring imparts monomer recyclability into the corresponding polymer. Furthermore

stereoselective polymerization of racemic monomers can be realized by RE catalysts containing chiral ligands with large steric hindrance. Slight modification of ligands gives rise to tailored or even inverted stereoregularity of polymers. The unique advantages of RE catalysts in the controllability of polymerization process and polymer structure are illustrated by discussing the relationship between catalyst structures and polymerization results. In addition

a novel ring-opening polymerization catalyzed by RE compounds

named Janus polymerization is introduced. This new mechanism combines cationic and anionic polymerizations at two ends of a single propagating chain and thus provides a facile methodology to synthesize polymers with sophisticated chemical structures and topologies in one step. New catalysts and mechanisms of ring-opening polymerizations have attractive potentiality in begetting new materials.

关键词

稀土催化剂开环聚合立构控制聚酯聚醚聚碳酸酯聚氨基酸两仪聚合

Keywords

Rare earth catalysisRing-opening polymerizationStereoselective polymerizationPolyestersPolyethersPolycarbonatesPoly(α-amino acid)sJanus polymerization

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Collgene of Chemical Engineering, Qingdao University of Science and Technology

Key Laboratory of Biobased Polymer Materials, Shandong Provincial Education Department, College of Polymer Science and Engineering, Qingdao University of Science and Technology

State Key Laboratory Base of Eco-Chemical Engineering, College of Chemical Engineering

Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education

College of Chemical Engineering, Qingdao University of Science and Technology

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