Random Copolymerization of Cyclohexene Oxide and Phthalic Anhydride Synergistically Catalyzed by Heterodinuclear Metal Complex

Yang-yang Xu; Tian-jun Yue; Jin-zhuo Zhao; Wei-min Ren

doi:10.11777/j.issn1000-3304.2024.24026

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Random Copolymerization of Cyclohexene Oxide and Phthalic Anhydride Synergistically Catalyzed by Heterodinuclear Metal Complex

Research Article | 更新时间：2024-08-14

- Random Copolymerization of Cyclohexene Oxide and Phthalic Anhydride Synergistically Catalyzed by Heterodinuclear Metal Complex
- Acta Polymerica Sinica Vol. 55, Issue 8, Pages: 1001-1008(2024)
- 作者机构：
  
  精细化工国家重点实验室大连理工大学化工学院大连 116024
- 作者简介：
  
  Wei-min Ren, E-mail: wmren@dlut.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2024.24026
  CLC：
- Published：20 August 2024，
  
  Published Online：30 April 2024，
  
  Received：22 January 2024，
  
  Accepted：23 February 2024
- 稿件说明：
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胥洋洋, 乐天俊, 赵金卓, 任伟民. 异核双金属协同催化环氧环己烷与邻苯二甲酸酐无规共聚. 高分子学报, 2024, 55(8), 1001-1008

Xu, Y. Y.; Yue, T. J.; Zhao, J. Z.; Ren, W. M. Random copolymerization of cyclohexene oxide and phthalic anhydride synergistically catalyzed by heterodinuclear metal complex. Acta Polymerica Sinica, 2024, 55(8), 1001-1008
胥洋洋, 乐天俊, 赵金卓, 任伟民. 异核双金属协同催化环氧环己烷与邻苯二甲酸酐无规共聚. 高分子学报, 2024, 55(8), 1001-1008 DOI： 10.11777/j.issn1000-3304.2024.24026.

Xu, Y. Y.; Yue, T. J.; Zhao, J. Z.; Ren, W. M. Random copolymerization of cyclohexene oxide and phthalic anhydride synergistically catalyzed by heterodinuclear metal complex. Acta Polymerica Sinica, 2024, 55(8), 1001-1008 DOI： 10.11777/j.issn1000-3304.2024.24026.

摘要

设计、合成了一种新型异核双金属配合物，用于催化环氧环己烷(CHO)和邻苯二甲酸酐(PA)的共聚反应，以制备聚(醚-酯)材料. 分别通过核磁共振波谱和电喷雾质谱对聚合物及其水解后产物结构进行分析，证明所得共聚物为醚酯单元呈无规分布的聚(醚-酯). 重点考察了配体结构、金属离子、反应温度和催化剂浓度对聚合反应的影响. 最后，对所得聚(醚-酯)无规共聚物热性能进行研究，表明聚醚链段的引入可以调变其玻璃化转变温度，丰富了此类聚酯材料的应用场景.

Abstract

The ring-opening copolymerization of epoxides and cyclic anhydrides constitutes a straightforward route for synthesizing polyesters. The resultant copolymers are mainly obtained with alternating structures

which might limit their application situations due to their low toughness caused by the high density of ester group. It has been demonstrated that the incorporation of ether segments into the mainchain of polyesters is an efficient strategy to tune the thermal and mechanical properties of polyesters

which is greatly limited by the lack of efficient catalyst. In response to these issues

this study proposed to achieve the random copolymerization of cyclohexene oxide (CHO) and phthalic anhydride (PA) to prepare poly(ether-ester)s

via

the hetero-bimetallic synergistic catalysis strat

egy. A series of heterodinuclear Al-K complex has been designed for catalyzing the copolymerization of CHO and PA. The structures of the resultant copolymers are confirmed as poly(ether-ester)s using nuclear magnetic resonance spectroscopy and electrospray ionization mass spectrometry. The exploration of the polymerization process further revealed the randomly structure of obtained poly(ether-ester)s

that is

ester and ether segments were randomly distributed in the polymer mainchain. Systemic studies on the effects of ligand structure

metal ions

reaction temperature and catalyst concentration on the copolymerization were explored

indicating that it is the synergistic cooperation between two metal centers that results in the formation of random copolymers. In addition

thermal property characterization of resultant copolymers indicates that the incorporation of polyether segments into polyester could effectively tune their glass transition temperatures

thus enriching the application of polyester materials.

关键词

聚(醚-酯)共聚物异核双金属配合物开环共聚无规共聚物

Keywords

Poly(ester-ether)sHeterodinuclear metal complexRing-opening copolymerizationRandom copolymer

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