Photothermal Polymerization of Epoxides and Carbon Dioxide Catalyzed by Polymeric Aluminum Porphyrin

Hao Zhou; Shun-jie Liu; Pei Chen; Han Cao; Chun-wei Zhuo; Xian-hong Wang

doi:10.11777/j.issn1000-3304.2025.25143

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Photothermal Polymerization of Epoxides and Carbon Dioxide Catalyzed by Polymeric Aluminum Porphyrin

Research Article | 更新时间：2026-05-11

- Photothermal Polymerization of Epoxides and Carbon Dioxide Catalyzed by Polymeric Aluminum Porphyrin
  增强出版
- Acta Polymerica Sinica Vol. 56, Issue 11, Pages: 1954-1964(2025)
- 作者机构：
  
  1.中国科学技术大学应用化学与工程学院合肥 230026
  2.中国科学院长春应用化学研究所高分子科学与技术全国重点实验室长春 130022
- 作者简介：
  
  Shun-jie Liu, E-mail: sjliu@ciac.ac.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25143
  CLC：
- CSTR：32057.14.GFZXB.2025.7446
- Received：10 June 2025，
  
  Accepted：04 July 2025，
  
  Online First：11 September 2025，
  
  Published：20 November 2025
- 稿件说明：
移动端阅览
周浩, 刘顺杰, 陈佩, 曹瀚, 卓春伟, 王献红. 高分子铝卟啉催化下环氧化物与二氧化碳的光热聚合. 高分子学报, 2025, 56(11), 1954-1964

Zhou, H.; Liu, S. J.; Chen, P.; Cao, H.; Zhuo, C. W.; Wang, X. H. Photothermal polymerization of epoxides and carbon dioxide catalyzed by polymeric aluminum porphyrin. Acta Polymerica Sinica, 2025, 56(11), 1954-1964
周浩, 刘顺杰, 陈佩, 曹瀚, 卓春伟, 王献红. 高分子铝卟啉催化下环氧化物与二氧化碳的光热聚合. 高分子学报, 2025, 56(11), 1954-1964 DOI： 10.11777/j.issn1000-3304.2025.25143. CSTR： 32057.14.GFZXB.2025.7446.

Zhou, H.; Liu, S. J.; Chen, P.; Cao, H.; Zhuo, C. W.; Wang, X. H. Photothermal polymerization of epoxides and carbon dioxide catalyzed by polymeric aluminum porphyrin. Acta Polymerica Sinica, 2025, 56(11), 1954-1964 DOI： 10.11777/j.issn1000-3304.2025.25143. CSTR： 32057.14.GFZXB.2025.7446.

摘要

光热聚合兼备光响应的时空可控性与热聚合的高效性，具有广阔的应用前景. 本研究设计开发了铝卟啉主链型高分子催化剂(P

(

-Cat)用于催化环氧化物与CO

的高效光热聚合. P

(

-Cat采用模块化合成策略，为系统研究其结构与性能关系提供了基础. 研究表明，随着活性中心间距的增大(

10)，P

(

-Cat的分子内协同效应减弱，而光热效率保持稳定(

≈23.8%). 随着卟啉meso位苯环对位取代基吸电子能力增强(R=

Br)，催化剂的协同效应增强，但光热效率依次下降(30.9%、23.8%、15.8%). 综合催化剂的协同效应与光热转换能力，P

-Cat在催化环氧丙烷(PO)与CO

光热聚合时具有最佳的性能(turnover frequency，TOF=660 h

-1

，聚合物选择性

99%). 此外，多活性中心的局部富集效应使其在极低催化剂用量下([PO

]

/[Al

]

=20000/1)仍能保持催化性能. 本研究不仅优化了光热聚合体系，也为催化剂的模块化设计提供了新思路.

Abstract

Photothermal polymerization offers both the spatiotemporal controllability of light-responsive processes and the high efficiency of thermal polymerization

making it highly promising for practical applications. In this work

an aluminum porphyrin backbone polymeric catalyst (P

(

-Cat) was developed for the efficient photothermal copolymerization of epoxides and CO

. The modular synthesis strategy provides a basis for systematically studying the structure-performance relationship of P

(

-Cat. The study showed that increasing the spatial distance

of the active centers (

10) impaired the synergistic effect of P

(

-Cat

but the photothermal efficiency remained stable (

≈23.8%). Meanwhile

as the electron-withdrawing ability of the

para

-substituent of porphyrin meso-benzene increases (R =

Br)

the synergistic effect of the catalyst increases

but the

decreases (30.9%

23.8%

15.8%). Taking into account both synergistic catalysis and photothermal performance

-Cat exhibited the best catalytic activity in the photothermal copolymerization of propylene oxide (PO) and CO

(TOF=660 h⁻

polymer selectivity

99%). Moreover

due to the local enrichment of multiple active centers

-Cat maintained catalytic performance even at extremely low loadings ([PO

]

/[Al

]

=20000/1). This study not only optimizes photothermal polymerization systems but also offers a new perspective on the modular design of polymer catalysts.

关键词

Keywords

references

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