Macromolecular Research

The Polymer Society of Korea (한국고분자학회)
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Successive Synthesis of Well-Defined Star-Branched Polymers by an Iterative Approach Based on Living Anionic Polymerization

  • Higashihara Tomoya (Polymeric and Organic Materials Department, Graduate School of science and Engineering, Tokyo Institute of Technology) ;
  • Inoue Kyoichi (Polymeric and Organic Materials Department, Graduate School of science and Engineering, Tokyo Institute of Technology) ;
  • Nagura Masato (Polymeric and Organic Materials Department, Graduate School of science and Engineering, Tokyo Institute of Technology) ;
  • Hirao Akira (Polymeric and Organic Materials Department, Graduate School of science and Engineering, Tokyo Institute of Technology)
  • Published : 2006.06.01
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Abstract

To successively synthesize star-branched polymers, we developed a new iterative methodology which involves only two sets of the reactions in each iterative process: (a) an addition reaction of DPE or DPE-functionalized polymer to a living anionic polymer, and (b) an in-situ reaction of 1-(4-(4-bromobutyl)phenyl)-1-phenylethylene with the generated 1,1-diphenylalkyl anion to introduce one DPE functionality. With this methodology, 3-, 4-, and 5-arm, regular star-branched polystyrenes, as well as 3-arm ABC, 4-arm ABCD, and a new 5-arm ABCDE, asymmetric star-branched polymers, were successively synthesized. The A, B, C, D, and E arm segments were poly(4-trimethylsilylstyrene), poly(4-methoxystyrene), poly(4-methylstyrene), polystyrene, and poly(4-tert-butyldimethylsilyloxystyrene), respectively. All of the resulting star-branched polymers were well-defined in architecture and precisely controlled in chain length, as confirmed by SEC, $^1H$ NMR, VPO, and SLS analyses. Furthermore, we extended the iterative methodology by the use of a new functionalized DPE derivative, 1-(3-chloromethylphenyl)-1-((3-(1-phonyletheny1)phenyl) ethylene, capable of introducing two DPE functionalities via one DPE anion reaction site in the reaction (b). The number of arm segments of the star-branched polymer synthesized by the methodology could be dramatically increased to 2, 6, and up to 14 by repeating the iterative process.

Keywords

References

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