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Precise synthesis of dendron-like hyperbranched polymers and block copolymers by an iterative approach involving living anionic polymerization, coupling reaction, and transformation reaction

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Abstract

Dendritic hyperbranched poly(methyl methacrylate)s (PMMA)s, whose branched architectures resemble the “dendron” part(s) of dendrimer, were synthesized by an iterative methodology consisting of two reactions in each iteration process: (a) a coupling reaction of α-functionalized, living, anionic PMMA having twotert-butyldimethylsilyloxymethylphenyl (SMP) groups with benzyl bromide (BnBr)-chain-end-functionalized PMMA, and (b) a transformation reaction of the introduced SMP groups into BnBr functionalities. These two reactions, (a) and (b), were repeated three times to afford a series of dendron-like, hyperbranched (PMMA)s up to third generation. Three dendron-like, hyperbranched (PMMA)s different in branched architecture were also synthesized by the same iterative methodology using a low molecular weight, functionalized 1,1-diphenylalkyl anion prepared fromsec-BuLi and 1,1-bis(3-tert-butyldime-thylsilyloxymethylphenyl)ethylene in the reaction step (b) in each iterative process. Furthermore, structurally similar, dendron-like, hyperbranched block copolymers could be successfully synthesized by the iterative methodology using α-functionalized, living, anionic poly(2-(perfluorobutyl) ethyl methacrylate) (PRfMA) in addition to α-functionalized, living PMMA. Accordingly, the resulting block copolymers were comprised of both PMMA and PRfMA segments with different sequential orders. After the block copolymers were cast into films and annealed, their surface structures were characterized by angle-dependent XPS and contact angle measurements. All three samples showed significant segregation and enrichment of PRfMA segments at the surfaces.

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Authors and Affiliations

  1. Polymeric and Organic Materials Department, Graduate School of Science and Engineering, Tokyo Institute of Technology, H-127, 2-12-1, Ohokayama, Meguro-ku, 152-8552, Tokyo, Japan

    Akira Hirao, Yuji Tsunoda, Akira Matsuo, Kenji Sugiyama & Takumi Watanabe

Authors
  1. Akira Hirao
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  2. Yuji Tsunoda
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  3. Akira Matsuo
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  4. Kenji Sugiyama
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  5. Takumi Watanabe
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Correspondence to Akira Hirao.

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Hirao, A., Tsunoda, Y., Matsuo, A. et al. Precise synthesis of dendron-like hyperbranched polymers and block copolymers by an iterative approach involving living anionic polymerization, coupling reaction, and transformation reaction. Macromol. Res. 14, 272–286 (2006). https://doi.org/10.1007/BF03219083

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  • DOI: https://doi.org/10.1007/BF03219083

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