杂化嵌段共聚物的无金属催化一步合成  

One-Step Synthesis of Hybrid Block Copolymers through Metal-Free Catalysis

作　　者：何冠辰 高生辉 李恒[1,3] 赵俊鹏 HE Guanchen;GAO Shenghui;LI Heng;ZHAO Junpeng(Faculty of Materials Science and Engineering,South China University of Technology,Guangzhou 510640,China;Shaanxi Yuneng Group Energy and Chemical Industry Research Institute Co.,Ltd.,Yulin 719000,China;College of Chemistry,Xiangtan University,Xiangtan 411105,China)

机构地区：[1]华南理工大学材料科学与工程学院,广东广州510640 [2]陕西榆能集团能源化工研究院有限公司,陕西榆林719000 [3]湘潭大学化学学院,湖南湘潭411105

出　　处：《中国材料进展》2023年第6期441-455,共15页Materials China

基　　金：国家自然科学基金资助项目(52022031,21734004,21971075);广东省分子聚集诱导发光重点实验室基金资助项目(2019B030301003);中国博士后科学基金资助项目(2019M662890,2020TQ0100);广州市科技计划资助项目(202102020964)。

摘　　要：杂化嵌段共聚物由两种及以上化学结构和理化性质迥异的高分子链段构成,往往具有显著的自组装和微观相分离等性能,获得了广泛的研究与应用。从异源单体(即具有不同聚合基团的单体)混合物出发,通过一步操作使之发生序列选择性的连续或同步聚合反应,是合成杂化嵌段共聚物的理想方法。然而,该方法长期以来面临着异源单体聚合反应难相容、苛刻的嵌段共聚动力学难满足等挑战。近年来,有机/无金属催化聚合发展迅猛,为实现异源单体的序列选择性共聚和杂化嵌段共聚物的“一步法”可控合成提供了一系列行之有效的新思路和新手段。综述了相关研究进展,主要包括杂环与杂环单体、杂环与乙烯基单体的一步嵌段共聚,并对关键反应机理进行简要介绍。Hybrid block copolymers,consisting of two or more polymeric segments with significantly different chemical structures and physicochemical properties,are readily prone to self-assembly and microphase separation and thus highly attractive for fundamental studies and materials applications.One-step sequence-selective block copolymerization of mixed heterogeneous monomers(with different polymerizing groups)is the ideal method for synthesizing hybrid block copolymers.However,great challenges have long been associated with this method for the incompatibility of mechanistically distinct polymerizations and the highly stringent kinetic requirements.The recent surge of organocatalytic/metal-free polymerization has heavily spurred the advancement of this area with a series of novel and effective monomer/catalyst designing strategies.The progress is reviewed for the combinations of heterocyclic monomers and heterocyclic/vinyl monomers,with the key mechanistic aspects briefly elucidated.

关 键 词：无金属催化聚合 共聚反应 开环聚合 嵌段共聚物 活性/可控聚合 

分 类 号：TQ316.3[化学工程—高聚物工业]