基于硼酸酯标签制备具有精确侧基结构的可控聚合物  

Synthesis of Controllable Polymers with Precise Side-chain Structures via Boronate-tag

作　　者：云杰 徐超然 谢志康 杜昱璇 董进 潘翔城 Jie Yun;Chao-ran Xu;Zhi-kang Xie;Yu-xuan Du;Jin Dong;Xiang-cheng Pan(State Key Laboratory of Molecular Engineering of Polymers,Department of Macromolecular Science,Fudan University,Shanghai 200438)

机构地区：[1]聚合物分子工程国家重点实验室,复旦大学高分子科学系,上海200438

出　　处：《高分子学报》2024年第7期881-890,共10页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号22322103,22271057和22201045);上海市自然科学基金(基金号22ZR1406000)资助项目。

摘　　要：结构精确的聚合物在生物医药、信息储存、分级组装等领域具有重要作用,而其制备一直是高分子合成领域的挑战之一.本工作基于N-甲基亚氨二乙酸(MIDA)硼酸酯作为液相迭代合成中的标签,制备了4种不同结构的噻吩-苯基侧基的单体,对其经可控自由基聚合制备得精确侧基结构的聚合物.聚合物的紫外可见光谱和荧光发射光谱显示了不同侧基结构聚合物具有不同的光学性质,而这些聚合物在热性质和结晶性质方面呈现相似性,这来源于其相同的主链结构和同种成分的侧基.建立了MIDA硼酸酯标签合成精确侧基单体的方法,为实现聚合物侧基的精准调控提供了思路和可行方法.Polymers with precise structures possess important roles in biomedicine,information storage,hierarchical assembly,etc.,while their preparation has always been a challenge in the field of polymer synthesis.N-Methyliminodiacetic acid(MIDA)boronates,employed as tags in liquid-phase iterative synthesis,were widely utilized in Suzuki-Miyaura coupling reactions as stable boronic acid precursors for the construction of a variety of organic molecules.In this study,four monomers with different structures of thiophene-phenyl side chains were prepared based on MIDA boronates tags.Precise aryl side-chain linkages were created through several coupling reactions between boronic acids and aryl bromides containing MIDA boronates.Further MIDA boronates can be converted into hydroxyl functional groups,allowing for further modification and introduction of vinyl functional groups to synthesize polymerizable monomers.Different monomers were employed in the controlled radical polymerization to yield polymers with precisely controlled side-chain structures.UV-Vis and fluorescence spectra of the polymers revealed distinct optical properties based on different side-chain structures,while similarities in thermal and crystalline properties were observed due to their identical main-chain structures and similar sidechain compositions.This work establishes a methodology for synthesizing precisely controlled side-chain monomers using MIDA boronate labels,providing insights and feasible approaches for the accurate modulation of polymer side chains.

关 键 词：序列精准聚合物 硼酸酯 可控/活性聚合 

分 类 号：TQ317[化学工程—高聚物工业]