有机催化CO_(2)/环氧/酸酐交替共聚合成聚碳酸酯/聚酯及其共聚物  

Organocatalytic Alternating Copolymerization of CO_(2)/Epoxide/Anhydride for Synthesis of Polycarbonate/Polyester Copolymers

作　　者：马钰琨 刘绍峰 李志波[1,2] Yu-kun Ma;Shao-feng Liu;Zhi-bo Li(Key Laboratory of Biobased Polymer Materials,Shandong Provincial Education Department,College of Polymer Science and Engineering,Qingdao 266042;Collgene of Chemical Engineering,Qingdao University of Science and Technology,Qingdao 266042)

机构地区：[1]青岛科技大学,高分子科学与工程学院,山东省教育厅生物基高分子材料重点实验室,青岛266042 [2]青岛科技大学化工学院,青岛266042

出　　处：《高分子学报》2022年第9期1041-1056,共16页Acta Polymerica Sinica

基　　金：国家重点研究计划(项目号2021YFA1500095);国家自然科学基金(基金号22031005)资助项目。

摘　　要：发展环境友好高分子材料符合当代绿色及可持续发展的理念,同时也是解决目前环境问题的有效途径之一.二氧化碳(CO_(2))来源广泛且无毒,却是造成温室效应的主要气体.利用CO_(2)和环氧交替共聚可以制备聚碳酸酯材料,而环氧和酸酐交替共聚则可以制备聚酯材料.聚碳酸酯/聚酯高分子材料在人们生活的诸多方面(食品包装和生物医药等)有着广泛的应用.有机催化剂作为一种新兴的“无金属”催化剂,在近20年中发展迅速且独具特色.近年来,我们课题组开发了一系列有机磷腈催化剂,其碱性和分子结构可调控,能够高效地催化各类环状单体的开环聚合,制备聚酯、聚醚、聚硅氧烷、聚碳酸酯等多种高分子材料.此外,有机磷腈催化剂与路易斯酸等相结合,能够方便地构筑组成多样化的二元有机催化体系,通过协同催化效应实现独特的催化性能.本专论主要包括CO_(2)/环氧交替共聚制备聚碳酸酯、环氧/酸酐交替共聚制备聚酯、混合单体三元共聚制备聚碳酸酯/聚酯共聚物3个部分.根据催化体系的不同,分别介绍了近年来有机催化CO_(2)/环氧/酸酐交替共聚合成聚碳酸酯/聚酯及其共聚物的研究进展,对聚合机理进行了适当的解释和讨论,并展望了该领域未来的发展,包括新型高效高选择性有机催化剂、新型单体和可持续高分子材料等方向.The synthesis of environment-friendly polymer materials,including polycarbonates and polyesters,supports the strategy of sustainable development,and it is also one of the feasible ways to solve the current environmental stress(greenhouse effect and white pollution,etc.).Carbon dioxide(CO_(2))has a wide range of sources and is non-toxic,but it could cause the greenhouse effect.Therefore,developing efficient techniques to transform CO_(2)into value-added chemicals is a promising solution for our sustainable society.CO_(2)-based polycarbonate materials can be prepared by ring-opening alternating copolymerization(ROCO_(2)P)of CO_(2)and epoxide,while polyester materials can be prepared by ROCO_(2)P of epoxide and anhydride.Organocatalysts,as a type of emerging“metal-free”catalysts,have developed rapidly in the past 20 years and exhibited unique properties and exceptional promises for various polymerization reactions.Recently,our group have developed a series of organic phosphazenes,which are a family of extremely strong,non-nucleophilic,and uncharged auxiliary bases and show remarkable potential as organocatalysts for ring-opening polymerization(ROP)of cyclic monomers.On the other hand,phosphazenes in combination with a Lewis acid,such as triethyleborane(TEB),can easily construct diverse binary organocatalysts that exhibite excellent catalytic performances.Apparently,organocatalytic synthesis of polymer materials has become an important and hot research topic.This feature article reviews the recent progress in the field of ROCO_(2)P of CO_(2)/epoxide/anhydride catalysed by organocatalysts followed by a proper discussion of respective polymerization mechanisms.The review includes three sub-topics,i.e.,ROCO_(2)P of CO_(2)/epoxide,ROCO_(2)P of epoxide/anhydride,and terpolymerization of CO_(2)/epoxide/anhydride.A short perspective viewpoint is provided at the end for readers who are interested in this area.

关 键 词：有机催化剂 开环聚合 交替共聚 聚碳酸酯 聚酯 

分 类 号：TQ317[化学工程—高聚物工业] TQ426