Modular Synthesis of Mid-Chain Functionalized Polymers by Photoinduced Diene- and Styrene-Assisted Radical Coupling Reaction of Polymer-End Radicals
Modular Synthesis of Mid-Chain Functionalized Polymers by Photoinduced Diene- and Styrene-Assisted Radical Coupling Reaction of Polymer-End Radicals
复制标题
光诱导二烯和苯乙烯辅助聚合物末端自由基偶联反应模块化合成中链功能化聚合物
作者：
Nakamura;Y.; Arima;T.; Yamago;S.
在二烯或苯乙烯存在下，通过有机碲介导的活性自由基聚合制备的结构明确的“活性”聚合物的光照射诱导选择性聚合物末端偶联反应，伴随着二烯或苯乙烯的插入，偶联效率>90%。当使用丙烯酸类聚合物时，插入的二烯或苯乙烯的数目可以高度控制为两个分子。因此，通过使用官能化的二烯或苯乙烯，成功地合成了各种中链官能化的聚合物，其在分子量、分子量分布、官能度和位置方面具有良好控制的分子和大分子结构。该方法被应用于中链官能化的遥爪聚合物和具有良好控制的结构的4-杂臂星星聚合物的简易合成。
Photoirradiation of structurally well-defined “living” polymers prepared by organotellurium-mediated living radical polymerization in the presence of dienes or styrenes induced selective polymer-end coupling reaction with the concomitant insertion of the dienes or styrenes with >90% coupling efficiency. The number of inserted dienes or styrenes could be highly controlled to two molecules when acrylic polymers were used. Therefore, various mid-chain-functionalized polymers with well-controlled molecular and macromolecular structure in terms of their molecular weight, molecular weight distribution, functionality, and position were successfully synthesized by employing functionalized dienes or styrenes. The method was applied to the facile synthesis of mid-chain-functionalized telechelic polymers and a 4-miktoarm star polymer with a well-controlled structure.