卟啉铝高选择性催化聚碳酸环己烯酯解聚

刘永思; 于艳; 李宸; 刘野; 吕小兵

doi:10.11777/j.issn1000-3304.2026.26116

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卟啉铝高选择性催化聚碳酸环己烯酯解聚

研究论文 | 更新时间：2026-07-24

- 卟啉铝高选择性催化聚碳酸环己烯酯解聚
- Highly Selective Depolymerization of Poly(cyclohexene carbonate) Using Aluminum Porphyrin Catalysts
- 高分子学报 2026年57卷第8期页码：1680-1688
- 作者机构：
  
  大连理工大学精细化工全国重点实验室大连 116024
- 作者简介：
  
  E-mail: xblu@dlut.edu.cn
- 基金信息：
  
  国家重点研发计划(2021YFA1501700)
- DOI：10.11777/j.issn1000-3304.2026.26116
  中图分类号：
- CSTR：32057.14.GFZXB.2026.7617
- 收稿：2026-04-13，
  
  录用：2026-05-06，
  
  网络首发：2026-07-03，
  
  纸质出版：2026-08-20
- 稿件说明：
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刘永思, 于艳, 李宸, 刘野, 吕小兵. 卟啉铝高选择性催化聚碳酸环己烯酯解聚. 高分子学报, 2026, 57(8), 1680-1688.

Liu, Y. S.; Yu, Y.; Li, C.; Liu, Y.; Lu, X. B. Highly selective depolymerization of poly(cyclohexene carbonate) using aluminum porphyrin catalysts. Acta Polymerica Sinica (in Chinese), 2026, 57(8), 1680-1688.
刘永思, 于艳, 李宸, 刘野, 吕小兵. 卟啉铝高选择性催化聚碳酸环己烯酯解聚. 高分子学报, 2026, 57(8), 1680-1688. DOI： 10.11777/j.issn1000-3304.2026.26116. CSTR： 32057.14.GFZXB.2026.7617.

Liu, Y. S.; Yu, Y.; Li, C.; Liu, Y.; Lu, X. B. Highly selective depolymerization of poly(cyclohexene carbonate) using aluminum porphyrin catalysts. Acta Polymerica Sinica (in Chinese), 2026, 57(8), 1680-1688. DOI： 10.11777/j.issn1000-3304.2026.26116. CSTR： 32057.14.GFZXB.2026.7617.

摘要

设计开发了金属卟啉配合物和有机碱组成的二元催化体系，以聚乙二醇500 (PEG500)作溶剂催化热解具有代表性的CO

基聚碳酸酯——聚碳酸环己烯酯(PCHC)，实现了环氧环己烷(CHO)单体的高选择性回收. 通过催化剂筛选研究，发现以三氟乙酸根为轴向负离子的四苯基铝配合物和1

7-三氮杂二环[4.4.0

]

癸-5-烯(TBD)的催化体系活性最高，在200 ℃、铝配合物/TBD/PCHC = 1/2/1000 (摩尔比)的条件下反应1小时，PCHC完全解聚，CHO的选择性达到97%. 机理性研究确定PCHC通过随机断链和链端回咬结合的方式解聚，并经过反式碳酸环己烯酯(

trans

-CHC)中间体，再进一步分解形成CHO单体.

Abstract

A series of binary catalytic systems composed of metal porphyrin complexes and organic bases were designed and developed to catalyze the pyrolysis of the representative CO

-based polycarbonate

polycyclohexene carbonate (PCHC)

using poly(ethylene glycol) 500 (PEG 500) as the reaction solvent. This strateg enabled the highly selective recovery of cyclohexene oxide (CHO)

the corresponding epoxide monomer

from PCHC depolymerization Systematic catalyst screening was performed to evaluate the in

fluence of the metal center

axial anion

and organic base on the catalytic activity and product selectivity. The results showed that the catalytic system of aluminum tetraphenylporphyrin complex with trifluoroacetate as the axial ion and 1

7-triazabicyclo[4.4.0

]

dec-5-ene (TBD) exhibited the highest activity. Under optimized reaction conditions

namely a temperature TBD/PCHC=1/2/1000

PCHC was completely depolymerized within 1 h

affording CHO with a selectivity as high as 97%. Mechanistic studies confirmed that PCHC depolymerized through a combination of random chain scission and chain-end back-biting

through the intermediate

trans

-cyclohexene carbonate (

trans

-CHC)

which was further decomposed to form CHO monomer. These results demonstrate that the metal porphyrin/organic base binary catalytic system provides an efficient approach for the selective chemical recycling of CO

-based polycarbonates into value-added monomers.

关键词

Keywords

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