Synthesis of polymeric topological isomers based on sequential Ugi-4CR and thiol-yne click reactions with sequence-controlled amino-functionalized polymers
Synthesis of polymeric topological isomers based on sequential Ugi-4CR and thiol-yne click reactions with sequence-controlled amino-functionalized polymers
复制标题
基于顺序 Ugi-4CR 和硫醇-炔点击反应与序列控制氨基功能化聚合物的聚合物拓扑异构体的合成
DOI：
10.1039/c9py01859j
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发表时间：
2020
影响因子：
4.6
通讯作者：
Li Yang
中科院分区：
文献类型：
--
作者：
Shen Heyu;Han Li;Ma Hongwei;Liu Pibo;Yang Lincan;Li Chao;Ma Yuting;Peng Zhixuan;Li Yang
在此，序列控制聚合和序列Ugi-4CR/巯基炔点击反应激发了一种新的合成策略，用于制备定义良好的多接枝聚合物，其中序列控制的氨基功能化骨架通过Ugi-4CR转化为单模块或双模块烷基功能化主链，并通过“接枝”方法与定义良好的巯基端功能化聚苯乙烯分支进行点击。Ugi-4CR表现出较高的转化率（91%以上），而硫醇点击反应的效率在97%以上。同时，首次提出了具有相似分子量但接枝结构不同的“聚合物拓扑异构体”的创新概念。这四种定义明确的多接枝异构体（单刷聚合物、双刷聚合物、单梳聚合物和双梳聚合物）为聚合物物理研究提供了一个高层次的平台。通过初步测量发现，随着接枝结构的变化，稀溶液的性质有明显的不同，并有规律地变化。
Herein, sequence-controlled polymerization and sequential Ugi-4CR/thiol–yne click reactions inspired a novel synthetic strategy for preparing a well-defined multigraft polymer in which the sequence-controlled amino-functionalized backbones were converted to mono- or di-modular alkynyl-functionalized main chains via an Ugi-4CR and clicked with well-defined thiol end-functionalized polystyrene branches through the “graft-onto” method. The Ugi-4CR showed high conversions (above 91%), while the efficiencies for the thiol–yne click reaction were above 97%. Meanwhile, an innovative concept of “polymeric topological isomers” that had similar molecular weights but different grafted structures was proposed for the first time. These four well-defined multigraft isomeric polymers (mono-brush polymer, double-brush polymer, mono-comb polymer and double-comb polymer) provide a high-level platform for polymer physics studies. Through preliminary measurements, the dilute solution properties were found to be significantly different and to change regularly with variations in the grafted structures.