Aqueous metal-catalyzed living radical polymerization : highly active water-assisted catalysis

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Catalytic aqueous living radical polymerization was achieved through a ligand design for a ruthenium-based catalyst. A phenolic phosphine ligand [PPh2(pPhOH)] was combined with a pentamethylcyclopentadienyl (Cp*)-based tetrameric ruthenium precursor, and the resulting complex showed a high catalytic activity for aqueous living radical polymerizations of hydrophilic methacrylates (for example, poly(ethylene glycol) methacrylate and 2-hydroxyethyl methacrylate) in conjunction with a chlorine initiator [H–(MMA)2–Cl]. The catalytic system allowed very fast living polymerizations, block copolymerizations and syntheses of high-molecular-weight polymers (DPn~1000) with narrow-molecular-weight distributions. Importantly, the activity was high enough to control the polymerization using a catalytic amount of the complex, even though the polymerizations were performed at low temperature (40 °C). Such advanced catalysis was achieved by not only simple hydrophilicity of the ligand but also by a water-assisted dynamic transformation from the original coordinatively saturated form [Cp*RuCl(PR3)2; 18e; PR3=phosphine] into an unsaturated and active form [Cp*RuCl(PR3); 16e]. Water molecule(s) may also coordinate for further stabilization as demonstrated by 31P NMR analyses.

収録刊行物

  • Polymer journal

    Polymer journal 44(1), 51-58, 2012-01-15

    Nature Publishing Group

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各種コード

  • NII論文ID(NAID)
    10030168044
  • NII書誌ID(NCID)
    AA00777013
  • 本文言語コード
    ENG
  • 資料種別
    ART
  • ISSN
    00323896
  • NDL 記事登録ID
    023389248
  • NDL 請求記号
    Z53-R487
  • データ提供元
    CJP書誌  CJP引用  NDL  IR 
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