基于炔类单体的点击聚合制备超支化聚合物  

Hyperbranched Polymers Prepared by Alkyne-based Click Polymerization

作　　者：黄蝶[1] 秦安军[1] 唐本忠[1,2] Die Huang An-jun Qin Ben Zhong Tang(State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640 Department of Chemistry, Hong Kong Branch of National Engineering Research Center for Tissue Restoration ＆ Reconstruction, The Hong Kong University of Science ＆ Technology, Hong Kong)

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,广州510640 [2]香港科技大学化学系国家人体组织功能重建工程技术研究中心香港分中心

出　　处：《高分子学报》2017年第2期178-199,共22页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21525417;21490571);国家重点基础研究发展规划(973计划;项目号2013CB834702);中组部青年拔尖人才支持计划;中央高校基本科研业务费(项目号2015ZY013);广东省引进创新科研团队(项目号201101C0105067115)资助

摘　　要：超支化聚合物由于其独特的树枝状结构和物理化学性质,已经得到了广泛关注及应用.而基于炔类单体的点击聚合作为一类简单、高效的聚合反应已被广泛用于超支化聚合物的制备.本文对近5年利用叠氮-炔和巯基-炔点击聚合制备超支化聚合物的工作进行了简要综述.其中,Cu(I)催化的叠氮-炔点击聚合可制备1?4-立构规整的超支化聚三唑;Ru(II)催化的叠氮-炔点击聚合可制备1?5-立构规整的超支化聚三唑;活化的炔类单体和叠氮单体的无金属催化点击聚合可得到1?4-异构体含量高(高达91.7%)的超支化聚合物;而光引发?热引发及自发的巯基-炔点击聚合可制备含硫的超支化聚合物.此外,对所制备的超支化聚合物的功能和应用进行了简单介绍,最后还简单讨论了点击聚合制备超支化聚合物方面的可能发展方向.Hyperbranched polymers, as one kind of three dimensional macromolecules with globular and dendritic architectures, have unique properties of good solubility, low viscosity, topological structure, a lot of functional groups, etc. Over the past decades, the hyperbranched polymers have attracted more and more attention and been widely applied in diverse areas including coatings, additives, biomaterials, supramolecular chemistry,nanoscience and technology, photoelectricmaterials, and so on. Click polymerization with the advantages of facile monomers accessibility, mild reaction conditions and high reaction efficiency has been developed into a sort of powerful polymerization tool for the synthesis of polymers with well-defined molecular structures and advanced functional properties. This method has also been extensively used in the synthesis of hyperbranched polymers. This review mainly summarizes the progress on the synthesis of the hyperbranched polymers via alkyne-based click polymerizations in the last 5 years. The Cu（I）-catalyzed azide-alkyne click polymerization could readily produce 1,4-regioregular hyperbranched polytriazoles, whereas the Ru（II）-catalyzed azide-alkyne click polymerization could generate 1,5-regioregular hyperbranched polytriazoles. Meanwhile, the azide-alkyne click polymerizations under metal-free conditions were also developed through the ingenious design of monomers. Metal-free click polymerization of activated alkyne and azide monomers could efficiently produce hyperbranched polytriazoles with fraction of 1,4-isomers up to 91.7%. The obtained polytriazoles are thermally stable and well soluble in most common solvents, such as tetrahydrofuran, dichloromethane, N,N-dimethyl formamide, dimethyl sulfoxide. Moreover, the photo- and thermo-initiated as well as spontaneous thiol-yne click polymerizations could be used to facilely prepare sulfur-containing hyperbranched polymers. The thiol-yne addition process could be fine-tuned by the control of the polymerization condition, and hyperbran

关 键 词：超支化聚合物 点击聚合 区域选择性 功能化 

分 类 号：O631.5[理学—高分子化学]