铝卟啉折叠催化剂催化二氧化碳/环氧化物共聚反应

周振震; 刘顺杰; 郎涛涛; 高凤翔; 王献红

doi:10.11777/j.issn1000-3304.2023.23282

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铝卟啉折叠催化剂催化二氧化碳/环氧化物共聚反应

研究论文 | 更新时间：2024-04-16

- 铝卟啉折叠催化剂催化二氧化碳/环氧化物共聚反应
  增强出版
- AluminumPorphyrin Foldamer Catalyst Enables Efficient Copolymerization of CO₂/Epoxides
- 高分子学报 2024年55卷第4期页码：396-406
- 作者机构：
  
  1.中国科学院长春应用化学研究所生态环境高分子材料重点实验室长春 130022
  2.中国科学技术大学应用化学与工程学院合肥 230026
- 作者简介：
  
  E-mail: sjliu@ciac.ac.cn
  xhwang@ciac.ac.cn
- 基金信息：
  
  国家重点研发计划项目(2021YFD1700700);吉林省与中国科学院科技合作高技术产业化专项资金项目(2022SYHZ0004)
- DOI：10.11777/j.issn1000-3304.2023.23282
  中图分类号：
- 纸质出版日期：2024-04-20，
  
  网络出版日期：2024-02-09，
  
  收稿日期：2023-12-12，
  
  录用日期：2023-12-26
- 稿件说明：
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周振震, 刘顺杰, 郎涛涛, 高凤翔, 王献红. 铝卟啉折叠催化剂催化二氧化碳/环氧化物共聚反应. 高分子学报, 2024, 55(4), 396-406

Zhou, Z. Z.; Liu, S. J.; Lang, T. T.; Gao, F. X.; Wang, X. H. Aluminum porphyrin foldamer catalyst enables efficient copolymerization of CO₂/epoxides. Acta Polymerica Sinica, 2024, 55(4), 396-406
周振震, 刘顺杰, 郎涛涛, 高凤翔, 王献红. 铝卟啉折叠催化剂催化二氧化碳/环氧化物共聚反应. 高分子学报, 2024, 55(4), 396-406 DOI： 10.11777/j.issn1000-3304.2023.23282.

Zhou, Z. Z.; Liu, S. J.; Lang, T. T.; Gao, F. X.; Wang, X. H. Aluminum porphyrin foldamer catalyst enables efficient copolymerization of CO₂/epoxides. Acta Polymerica Sinica, 2024, 55(4), 396-406 DOI： 10.11777/j.issn1000-3304.2023.23282.

摘要

折叠催化剂因具有“类酶”的二级结构，被广泛应用于小分子化合物合成，然而其在高分子合成中的应用却鲜有报道. 基于双氨基功能化的铝卟啉与2

5-吡啶二甲酰氯的缩聚反应，本文报道了一种铝卟啉芳香酰胺折叠体催化剂，有效(300~1250 h

-1

)、高选择性(99%)地催化了二氧化碳(CO

)与环氧化物的共聚反应. 值得一提的是，该催化剂可以实现无助催化剂条件下CO

和环氧丙烷的共聚，催化活性可达525 h

-1

，同时聚合物选择性在95%以上，并且在80 ℃下表现出“类酶”的最佳温度特性. 在催化CO

与环氧环己烷共聚时，催化活性与二氧化碳压力(1~7 MPa)呈线性正相关关系，催化活性最高可达1250 h

-1

，聚合物选择性和碳酸酯单元含量保持在99%以上. 本文报道的铝卟啉折叠体催化剂为芳香酰胺折叠体在催化领域的发展提供了借鉴，同时也进一步拓展了折叠催化在高分子合成中的应用.

Abstract

Foldamer catalysts have been extensively applied in the synthesis of small molecules due to the "enzyme-like" secondary structure

while their contributions in polymer synthesis were rarely reported. Based on the polycondensation reaction of aluminum bis-aminoporphyrin and 2

‍5-diacylchloropyridine

we reported an aluminum porphyrin aromatic amide foldamer catalyst (AAF)

and its foldamer structure was verified by the circular dichroism spectrum. The foldamer catalyst AAF effectively (turnover frequency

TOF=300‍‒‍1250 h

-1

) catalyzed the copolymerization of carbon dioxide and epoxides with high polymer selectivity (99%). It is worth mentioning that

this catalyst can realize the copolymerization of carbon dioxide and propylene oxide even in the absence of cocatalyst with a TOF of 525 h

-1

and polymer selectivity of 95%

which also exhibits an enzyme-like optimum temperature of 80 ℃. Additionally

it could also catalyze the copolymerization of carbon dioxide and cyclohexane oxide

the catalytic activity (TOF=550‍‒‍1250 h

-1

) was linearly positively correlated with carbon dioxide pressure (1‍‒‍7 MPa)

and the polymer selectivity and carbonate units were all over 99%. Herein

we reported an aluminum porphyrin based aromatic amide foldamer catalyst

which broadens the application of foldamer catalysis in polymers and opens up new avenues for the study of aromatic amide foldamers in the field of catalysis.

关键词

铝卟啉芳香酰胺折叠体二氧化碳环氧化物协同催化

Keywords

Aluminum porphyrinAromatic amide foldamerCarbon dioxideEpoxidesCooperative catalysis

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