Successive Synthesis of Well-Defined Star-Branched Polymers by a New Iterative Approach Involving Coupling and Transformation Reactions
Successive Synthesis of Well-Defined Star-Branched Polymers by a New Iterative Approach Involving Coupling and Transformation Reactions
复制标题
DOI：
10.1021/ma050248e
复制
发表时间：
2005-04
期刊：
影响因子：
5.5
通讯作者：
Tomoya Higashihara;M. Nagura;Kyoichi Inoue;N. Haraguchi;A. Hirao
中科院分区：
文献类型：
--
作者：
Tomoya Higashihara;M. Nagura;Kyoichi Inoue;N. Haraguchi;A. Hirao
基于活性阴离子聚合的新迭代方法成功地合成了结构明确的星形支化聚合物。该方法仅涉及用于整个迭代反应序列的两组反应条件：（a）苄基溴官能化的聚合物与聚（取代的苯乙烯基）锂封端的1-（3-叔丁基二甲基甲硅烷基氧基甲基苯基）-1-苯乙烯连接两个聚合物链并引入苄基溴前体的3-叔丁基二甲基甲硅烷基氧基甲基苯基，和（B）通过用（CH 3）3SiCl−LiBr处理，引入的前体转化为苄基溴官能团。通过重复这两个反应，连续合成了一系列不对称星形支化聚合物。它们包括3臂ABC、4臂ABCD和A2 B2以及6臂A2 B2 C2星，其A、B、C和D片段分别为聚苯乙烯、聚α-甲基苯乙烯、聚4-甲基苯乙烯、聚甲基丙烯酸甲酯和聚苯乙烯。
Successive synthesis of well-defined star-branched polymers has been successfully achieved by a new iterative methodology based on living anionic polymerization. The methodology involves only two sets of reaction conditions for the entire iterative reaction sequence: (a) a coupling reaction of the benzyl bromide-functionalized polymer with poly(substituted styryl)lithium end-capped with 1-(3-tert-butyldimethylsilyloxymethylphenyl)-1-phenylethylene to link two polymer chains and introduce 3-tert-butyldimethylsilyoxymethylphenyl group(s) of benzyl bromide precursor(s) and (b) a transformation reaction of the introduced precursor(s) into benzyl bromide functionality (functionalities) by treatment with (CH3)3SiCl−LiBr. By repeating these two reactions, an array of asymmetric star-branched polymers were successively synthesized. They involved 3-arm ABC, 4-arm ABCD and A2B2, and 6-arm A2B2C2 stars whose A, B, C, and D segments are polystyrene, poly(α-methylstyrene), poly(4-methylstyrene), poly(methyl methacryla...