有机催化含硫一碳单体与环氧化物共聚  

Organocatalytic Polymerization of Sulfur-containing One-carbon Monomer and Epoxides

作　　者：王莹 杨嘉良 张成建 张兴宏[1] Ying Wang;Jia-liang Yang;Cheng-jian Zhang;Xing-hong Zhang(MOE Key Laboratory of Macromolecular Synthesis and Functionalization,Department of Polymer Science and Engineering,Zhejiang University,Hangzhou 310027)

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

出　　处：《高分子学报》2020年第10期1092-1103,I0001,I0002,共14页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21774108,51973190)资助项目.

摘　　要：近几年,采用含硫一碳单体(氧硫化碳和二硫化碳)与环氧化物共聚合成含硫高分子的路线快速发展起来.有机催化剂由于底物耐受性好、对空气和水不敏感以及低毒等优势,成功用于催化含硫一碳单体与环氧化物的聚合,得到了无色无味无金属残留的含硫聚合物.结合本课题组在含硫一碳单体聚合领域的研究结果,本文讨论了有机催化氧硫化碳与环氧化物共聚的体系,阐述了两类有机路易斯(Lewis)酸碱对即三烷基硼/有机碱和硫脲/有机碱体系的种类和结构与共聚选择性及活性之间的关系,介绍了由含硫一碳单体出发合成脂肪族聚硫醚的新路线.在此基础上,总结了有机Lewis酸碱协同催化机制,归纳提出了“超分子阴离子”链末端控制聚合的策略,并介绍了体现这一策略的若干含氧单体的可控聚合反应.希望这些认识能为设计高活性高选择性的有机协同催化体系提供新的思路.The harmlessness and high-value utilization of one-carbon(C1)building blocks are the frontier issues in synthetic polymer chemistry.The copolymerization of carbonyl sulfide(COS)or carbon disulfide(CS2)with epoxides is a promising method of synthesizing sulfur-containing polymers.In recent years,organocatalysts have been successfully developed to catalyze the polymerization process of COS(CS2)owing to their low toxicity,insensitivity to air and water,and good substrate resistance,resulting in colorless,odorless,and metal-free sulfurcontaining polymers.This work comprehensively summarizes the fundamental research activities on the organocatalytic polymerization of COS(CS2)with epoxides,affording a variety of poly(thiocarbonate)s and poly(thioether)s with well-defined structures.The catalysis of several organic Lewis pairs,i.e.the trialkyl borane/organic base and(thio)urea/organic base systems,for the polymerizations of COS(CS2)with epoxides is discussed in detail.Of significance,the conceptualization of O/S ER,a unique phenomenon in the copolymerization process of COS(CS2)with epoxides,guided us to have success in synthesizing a variety of poly(thioether)s.By inhibiting O/S ER,poly(monothiocarbonate)s have been developed by the catalysis of many organocatalysts.In addition,this study proposes the“supramolecular anion”strategy for the controlled copolymerization of COS with epoxides.This strategy can be expanded to the controlled polymerization of many types of monomers with heteroatoms(e.g.,O,S,N)under the catalysis of organic Lewis pairs.The properties of the COS(CS2)-derived polymers including optical,electronic,crystalline properties are presented.Future efforts can be directed to the development of robust,versatile,highly active and stereoselective organocatalysts for the copolymerization of COS(CS2)with epoxides,as well as the synthesis of sequence-controlled sulfur-containing polymers.

关 键 词：有机催化 含硫一碳单体 环氧化物 开环共聚合 含硫聚合物 

分 类 号：TQ316.3[化学工程—高聚物工业]