单质硫、异腈和硫醇的多组分串联聚合合成聚二硫代氨基甲酸酯  

Multicomponent Tandem Polymerizations of Sulfur, Diisocyanides and Dithiols toward Polydithiocarbamates

作　　者：于冰 霍金磊 胡蓉蓉[1] 唐本忠 Bing Yu;Jin-lei Huo;Rong-rong Hu;Ben Zhong Tang(State Key Laboratory of Luminescent Materials and Devices,Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates,South China University of Technology,Guangzhou 510640;School of Science and Engineering,The Chinese University of Hong Kong,Shenzhen City,Shenzhen 518172;AIE Institute,Guangzhou 510530)

机构地区：[1]华南理工大学发光材料与器件国家重点实验室、广东省分子聚集发光重点实验室,广州510640 [2]香港中文大学(深圳)理工学院,深圳518172 [3]聚集诱导发光高等研究院,广州510530

出　　处：《高分子学报》2023年第10期1509-1520,共12页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号52173005);科技部重点研发项目(项目号2021YFA1501600);广东省基础与应用基础研究基金(基金号2023B1515040003);中央高校基本科研业务费(项目号2022ZYGXZR107)资助项目.

摘　　要：聚二硫代氨基甲酸酯具有优异的力学性质和动态可逆性,是一类富有前景的功能高分子材料,然而其合成方法较为有限,限制了其结构和功能的拓展.在本文中,我们针对单质硫、异腈和硫醇的反应中存在副反应、效率低等问题,通过设计分步投料的方式、有机碱的种类和反应温度,提高了反应效率和选择性,并成功发展为有机碱催化的单质硫、异腈和硫醇的多组分串联聚合,以N,N-二异丙基乙胺为碱,在二甲亚砜溶剂中分步反应,得到数均分子量可达1.77×104 g/mol的聚二硫代氨基甲酸酯.该聚合条件温和、操作便捷,可适用于苄基异腈和芳香异腈单体,用于合成结构多样的聚二硫代氨基甲酸酯.这类聚合物具有较好的热稳定性,并可在硫醇存在下高效降解为低聚物.该多组分串联聚合为聚二硫代氨基甲酸酯材料提供了温和便捷的合成方法,有望促进这类新型可降解高分子材料的发展.Polydithiocarbamates are a group of promising functional polymer materials with unique mechanical property and dynamic reversible property,however,the exploration of structures and functionalities of these polymers are limited by the synthetic approaches.In this work,considering the problems regarding the side reactions and low efficiency in the reaction of elemental sulfur,isocyanide,and thiol,one-pot two-step tandem strategy,organic bases,and reaction temperature were carefully designed to improve the efficiency and selectivity of the reaction.The organic base-catalyzed multicomponent tandem polymerizations of elemental sulfur,diisocyanides and dithiols were developed,with N,N-diisopropylethylamine as the base in DMSO,affording polydithiocarbamates with Mns of up to 1.77×104 g/mol.The polymerization was mild and convenient,which could be applied to both aliphatic and aromatic isocyanides,to synthesize polydithiocarbamates with different structures.These polymers possessed good thermal stability,and could be degraded to oligomers in the presence of thiol.The multicomponent tandem polymerizations could provide a mild and convenient synthetic approach for polydithiocarbamates,which may accelerate the development of these sulfur-containing degradable polymer materials.

关 键 词：单质硫 多组分串联聚合 聚二硫代氨基甲酸酯 可降解高分子 

分 类 号：O633.14[理学—高分子化学]