有机小分子催化环醚与环状酸酐共聚研究进展  

Recent Progress in the Copolymerization of Cyclic Ethers and Cyclic Anhydrides via Organocatalysts

作　　者：胡岚方 张兴宏[1] HU Lanfang;ZHANG Xinghong(MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department ofPolymer Science and Engineering, Zhejiang University, Hangzhou 310027, China)

机构地区：[1]浙江大学高分子科学与工程学系高分子合成与功能构造教育部重点实验室,杭州310027

出　　处：《功能高分子学报》2019年第3期259-270,共12页Journal of Functional Polymers

基　　金：国家自然科学基金(21474083);浙江省杰出青年基金(LR16B040001)

摘　　要：有机小分子催化聚合反应是合成化学领域新的研究方向。有机催化环醚(主要为环氧化物)与环状酸酐共聚制备聚酯的合成路线,由于单体具有来源广泛、有机催化剂低毒、对水和空气不敏感等特点,因而应用前景广阔。本文按有机小分子催化剂、环醚与环状酸酐的种类综述了近年来出现的有机催化共聚合成聚酯的反应,并详细讨论了该共聚反应及其机理,尤其是高催化活性和聚合可控性的Lewis酸碱对催化共聚的机理;提出了利用Lewis酸为增长链阴离子提供结构因素(如基团和电子结构效应)来调控聚合的方法。今后,催化环氧化物与环状酸酐共聚研究的中心任务仍然是发展新的高活性有机催化剂,并实现"活性"的全交替共聚反应,进一步提高共聚物的分子量,并实现共聚反应的化学选择性、区域和立体选择性的精确控制。It is an emerging method to synthesize polymers via organocatalysts in very recent years. More attention has been paid to the organocatalytic ring-opening copolymerization of cyclic ethers (epoxides) with cyclic anhydrides since that these monomers are abundant and most of organocatalysts are low toxic and non-sensitive to oxygen and moisture. Thus, the organocatalytic copolymerization of epoxides with cyclic anhydrides is very promising and has a wide application prospect. In this review, the types of organocatalysts, cyclic ethers (epoxides) and anhydrides are systematically presented with detail discussion. The typical copolymerization and related mechanism are intensively discussed. Of special, the activity of the Lewis pairs consisted of the organoboron compounds and onium salts are comparable to the counterparts of metal organic catalysts, which means that the organocatalysts have a great potential in synthesizing polyesters. A synthetic strategy is proposed to utilize neutral organic molecules (i.e., Lewis acids) to introduce the steric and electronic effect for the growing anions for controlled copolymerization of epoxides and cyclic anhydrides. The future mission in this field is to develop highly active organocatalysts for the living copolymerization of epoxides with cyclic anhydrides for making polyesters with perfect selectivity (including chemoselectivity, regioselectivity and stereoselectivity).

关 键 词：有机小分子催化 环醚 环氧化物 环状酸酐 开环共聚 

分 类 号：O63[理学—高分子化学]