Synthesis and Characterization of ABC-Type Asymmetric Star Polymers Comprised of Poly(3-hexylthiophene), Polystyrene, and Poly(2-vinylpyridine) Segments
Synthesis and Characterization of ABC-Type Asymmetric Star Polymers Comprised of Poly(3-hexylthiophene), Polystyrene, and Poly(2-vinylpyridine) Segments
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DOI：
10.1021/ma5023814
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发表时间：
2015-01
期刊：
影响因子：
5.5
通讯作者：
Tomoya Higashihara;Shotaro Ito;Seijiro Fukuta;T. Koganezawa;M. Ueda;Takashi Ishizone;A. Hirao
中科院分区：
文献类型：
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作者：
Tomoya Higashihara;Shotaro Ito;Seijiro Fukuta;T. Koganezawa;M. Ueda;Takashi Ishizone;A. Hirao
首次将Kumada催化转移聚合与活性阴离子聚合相结合，通过聚合物偶联/连接反应合成了含有P3 HT链段的ABC型不对称星星聚合物。合成方法包括以下三个阶段的反应：（a）ω-链端官能化的P3 HT与溴丁基部分之间的阴离子连接反应（P3 HT-C4-Br）和活性阴离子PS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（1），（B）在P3 HT和PS片段之间的连接处的3-叔丁基二甲基甲硅烷基氧基甲基苯基（TBDMS）部分转化为α-丙烯酸苯酯（PA）部分通过羟甲基苯基部分，和（c）PA链内官能化的P3 HT-b-PS和活性阴离子P2 VP之间的阴离子连接反应。实际上，其中A、B和C分别为聚（3-己基噻吩）（P3 HT）、聚苯乙烯（PS）和聚（2-乙烯基吡啶）（P2 VP）的定义明确的ABC星星聚合物，.
ABC-type asymmetric star polymers containing a P3HT segment were successfully synthesized by polymer coupling/linking reactions by combining the Kumada catalyst-transfer polymerization and living anionic polymerization for the first time. The synthetic methodology involves the following three stage reactions: (a) the anionic linking reaction between ω-chain-end-functionalized P3HT with a bromobutyl moiety (P3HT-C4-Br) and living anionic PS end-capped with 1-(3-tert-butyldimethylsilyloxymethylphenyl)-1-phenylethylene (1), (b) the transformation reaction of the 3-tert-butyldimethylsilyloxymethylphenyl (TBDMS) moiety at the junction between the P3HT and PS segments into the α-phenyl acrylate (PA) moiety through the hydroxymethylphenyl moiety, and (c) the anionic linking reaction between PA-in-chain-functionalized P3HT-b-PS and living anionic P2VP. Indeed, the well-defined ABC star polymers in which A, B and C are poly(3-hexylthiophene) (P3HT), polystyrene (PS), and poly(2-vinylpyridine) (P2VP), respectively,...