双功能卟啉铝催化二氧化碳与长链末端环氧化物共聚  

Bifunctional Porphyrin Aluminum Catalyzed Copolymerization of Carbon Dioxide and Long Chain Terminal Epoxide

作　　者：刘克共 刘顺杰[1,2] 范培鑫 张若禹 陈学思 王献红[1,2] Ke-gong Liu;Shun-jie Liu;Pei-xin Fan;Ruo-yu Zhang;Xue-si Chen;Xian-hong Wang(Key Laboratory of Polymer Ecomaterials,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022)

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》2025年第2期242-252,共11页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号51988102)资助.

摘　　要：长链末端环氧化物(LCTE)由于大位阻侧基的存在,难以高选择性地与二氧化碳(CO_(2))共聚并得到高碳酸酯单元含量的聚合物.本研究通过在卟啉meso苯环不同位置引入大位阻有机碱1,5,7-三叠氮双环[4.4.0]癸-5-烯(TBD),设计了一系列双功能卟啉铝催化剂,旨在调控TBD基团与铝中心的空间协同作用.其中TBD连接在meso苯环间位上的催化剂m-4展现出最佳的催化效果,可高选择性(99%)催化1,2-环氧丁烷或1,2-环氧己烷与CO_(2)完全交替共聚,制备得到分子量大于32 kg/mol的聚碳酸酯.通过原位红外光谱对反应进行动力学研究证明该催化剂分子内协同的催化特征.本文工作探究了双功能催化剂分子内催化位点的空间分布与所产生协同作用的关系,为LCTE/CO_(2)高效交替共聚合成聚碳酸酯提供了一种新思路.Long chain terminal epoxide(LCTE),due to the existence of large steric hindrance side groups,is more difficult to achieve high selectivity in obtaining polymers with high carbonate unit content through copolymerization with carbon dioxide(CO_(2)).This work reported bifunctional catalysts with large steric hindrance organic base 1,5,7-triazo bicyclic[4.4.0]decane-5-ene(TBD)introduced into the meso-benzene ring of porphyrin,aiming to regulate the spatial synergistic effect between the anchored TBD and aluminum centers.Among them,the catalyst m-4 with TBD anchored at the meso-benzene ring’s meso-position exhibited the best catalytic activity,which could selectively(99%)catalyze the alternating copolymerization of 1,2-epoxybutane or 1,2-epoxyhexane with CO_(2).Catalyst m-4 could prepare polymers with molecular weight higher than 32 kg/mol.The obtained polymer’s glass transition temperature was lower than room temperature.In situ FTIR kinetic studies demonstrated the intramolecular synergistic effect in the designed catalysts.In summary,this work probed differences in the spatial distribution of intramolecular catalytic sites in bifunctional catalysts and the resulting synergistic effect,providing a way of efficiently synthesizing polycarbonate for LCTE/CO_(2) copolymerization.

关 键 词：双功能卟啉铝 二氧化碳 长链末端环氧化物 有机碱 开环共聚 

分 类 号：TQ316.314[化学工程—高聚物工业]