铝卟啉折叠催化剂催化二氧化碳/环氧化物共聚反应  

Aluminum Porphyrin Foldamer Catalyst Enables Efficient Copolymerization of CO_(2)/Epoxides

作　　者：周振震 刘顺杰[1,2] 郎涛涛 高凤翔 王献红[1,2] Zhen-zhen Zhou;Shun-jie Liu;Tao-tao Lang;Feng-xiang Gao;Xian-hong Wang(Key Laboratory of Polymer Ecomaterials,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022;School of Applied Chemistry and Engineering,University of Science and Technology of China,Hefei 230026)

机构地区：[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

出　　处：《高分子学报》2024年第4期396-406,共11页Acta Polymerica Sinica

基　　金：国家重点研发计划项目(项目号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(项目号2022SYHZ0004)资助。

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_(2))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_(2)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_(2)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.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 

分 类 号：O621.251[理学—有机化学]