日本ゴム協会誌
Print ISSN : 0029-022X
遷移金属錯体を用いたリビングラジカル重合による多重制御グラフト共重合体
佐藤 浩太郎上垣外 正己
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2008 年 81 巻 10 号 p. 424-430

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This study is directed to the synthesis of a series of well-defined graft copolymers with the controlled lengths of both the backbone and graft chains by the ruthenium-catalyzed living radical polymerization. The backbone polymer was first synthesized by the ruthenium-catalyzed living radical random copolymerization of methyl methacrylate and 2- (trimethylsilyloxy) ethyl methacrylate followed by the in-situ transformation of the silyloxyl group into the ester with a C-Br bond, which resulted in efficient multifunctional macroinitiators for living radical graft copolymerization. The methodology led to the novel controlled architectural copolymers, AxBAx-type block-graft copolymers, which can function as new building blocks for controlled nanostructures based on microphase separation and is different from that of the conventional ABA triblock copolymers. A series of well-defined AxBAx-type block-graft copolymers consisting of soft middle segments (dodecyl methacrylate) and hard outer graft chains (styrene) were synthesized by the ruthenium-catalyzed block and graft polymerizations to exhibit characteristics of a thermoplastic elastomer.
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