三中心卟啉铝配合物催化二氧化碳/环氧丙烷共聚反应

张聪聪; 邱天豪; 曲瑞; 秦玉升

doi:10.11777/j.issn1000-3304.2026.26036

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三中心卟啉铝配合物催化二氧化碳/环氧丙烷共聚反应

研究论文 | 更新时间：2026-06-02

- 三中心卟啉铝配合物催化二氧化碳/环氧丙烷共聚反应
- Copolymerization of Carbon Dioxide and Propylene Oxide Catalyzed by Tri-centered Aluminum Porphyrin Complexes
- 高分子学报 2026年57卷第6期页码：1364-1374
- 作者机构：
  
  1.烟台大学化学化工学院烟台 264005
  2.烟台大学高分子材料研究所烟台 264005
- 作者简介：
  
  E-mail: qurui@ytu.edu.cn
  E-mail: ysqin@ytu.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 ┣52473010;U25A20250);52203128┫;山东省自然科学基金(基金号 ZR2025ZD23)
- DOI：10.11777/j.issn1000-3304.2026.26036
  中图分类号：
- CSTR：32057.14.GFZXB.2026.7581
- 收稿：2026-02-04，
  
  录用：2026-03-19，
  
  网络首发：2026-05-15，
  
  纸质出版：2026-06-20
- 稿件说明：
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张聪聪, 邱天豪, 曲瑞, 秦玉升. 三中心卟啉铝配合物催化二氧化碳/环氧丙烷共聚反应. 高分子学报, 2026, 57(6), 1364-1374.

Zhang, C. C.; Qiu, T. H.; Qu, R.; Qin, Y. S. Copolymerization of carbon dioxide and propylene oxide catalyzed by tri-centered aluminum porphyrin complexes. Acta Polymerica Sinica (in Chinese), 2026, 57(6), 1364-1374.
张聪聪, 邱天豪, 曲瑞, 秦玉升. 三中心卟啉铝配合物催化二氧化碳/环氧丙烷共聚反应. 高分子学报, 2026, 57(6), 1364-1374. DOI： 10.11777/j.issn1000-3304.2026.26036. CSTR： 32057.14.GFZXB.2026.7581.

Zhang, C. C.; Qiu, T. H.; Qu, R.; Qin, Y. S. Copolymerization of carbon dioxide and propylene oxide catalyzed by tri-centered aluminum porphyrin complexes. Acta Polymerica Sinica (in Chinese), 2026, 57(6), 1364-1374. DOI： 10.11777/j.issn1000-3304.2026.26036. CSTR： 32057.14.GFZXB.2026.7581.

摘要

面对全球碳排放持续攀升、塑料污染日益严峻的双重挑战，开发高效催化体系实现CO

与环氧化物的开环共聚反应(ROCOP)已成为绿色高分子合成领域的研究热点. 本研究设计并合成了一类新型三中心卟啉铝配合物(T-TPPAl)，通过一步酰化反应构建具有刚性共轭骨架的配体，显著增强了活性中心之间的协同效应. 该催化剂在CO

与环氧丙烷(PO)共聚反应中表现出优异的催化性能，最高聚碳酸酯选择性达98.4%，碳酸酯单元含量超过96.4%. 研究结果表明，催化性能对CO

压力具有显著依赖性：在中等压力(3~7 MPa)下可获得高选择性与高碳酸酯含量；在超临界CO

条件下，活性中心协同作用增强，显著加速环氧化物的活化与连续开环插入，使聚醚链段比例上升、碳酸酯单元含量下降，但聚碳酸酯选择性仍保持较高水平. 本研究成功开发出一种性能优异的多中心卟啉铝催化剂，为调控反应产物结构、优化反应工艺提供了理论支撑，同时为绿色高分子材料的工业化合成路径开拓了新思路与新方向.

Abstract

To address the growing global carbon emissions and rising plastic pollution crisis

developing efficient catalytic systems for the ring-opening copolymerization (ROCOP) of CO

and epoxides has emerged as a critical frontier in green polymer synthesis. Herein

we report the design and synthesis of a novel class of tri-centered aluminum porphyrin complexes (T-TPPAl). By constructing a ligand with a rigid conjugated backbone

via

a one-step acylation reaction

the synergistic effect among the active centers was significantly enhanced. This catalyst demonstrated superior efficacy in the copolymerization of CO

and propylene oxide (PO)

achieving a maximum polymer selectivity of 98.4% and a carbonate unit content exceeding 96.4%. Systematic studies revealed a significant dependence of catalytic performance on CO

pressure. High selectivity and high carbonate content were obtained at moderate pressures (3-7 MPa). Notably

under supercritical CO

conditions

the enhanced synergistic effect of active sites significantly accelerated the activation and consecutive ring-opening insertion of epoxides

leading to an increased proportion of polyether segments and decreased carbonate unit content

while the polymer selectivity remains high. The successful development of this high-performance multi-centered aluminum porphyrin catalyst provides robust theoretical support for structural regulation and process optimization. Furthermore

it opens new avenues and perspectives for the industrial synthesis pathways of green polymeric materials.

关键词

Keywords

references

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