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超臨界二酸化炭素媒体におけるニトロキシド制御/リビングラジカル重合

Research Project

Project/Area Number 17750109
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeSingle-year Grants
Research Field Polymer chemistry
Research InstitutionKobe University

Principal Investigator

PERB. Zetterlund (ZETTERLUND Per B.)  神戸大学, 自然科学研究科, 助手 (20322365)

Project Period (FY) 2005 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥2,400,000 (Direct Cost: ¥2,400,000)
Fiscal Year 2006: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 2005: ¥1,300,000 (Direct Cost: ¥1,300,000)
Keywords臨界CO_2流体 / ニトロキシド制御 / リビングラジカル重合 / 分子量分布 / 不均一系 / 沈殿重合 / 超臨界CO_2流体 / 分散重合
Research Abstract

本研究は,リビングラジカル重合法のひとつであるニトロキシド制御/リビングラジカル重合(NMP)を超臨界二酸化炭素媒体(scCO_2)系に適用する世界でも初めての取り組みである。昨年度は,超臨界系ではNMPを不均一系で行うという難しさや,scCO_2流体系における分散安定剤の選定も必要であることから,各種重合因子の詳細な検討を行い,分散重合系における最適な重合条件を見出すことができた。本研究は特に,重合処方が最もシンプルな沈殿重合系でスチレンの重合を行った。開始剤としてはAIBN,安定ラジカルとしてはthe nitroxideN-tert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl)(SGI)を用いた。SGIや開始剤濃度などの重合処方・条件の検討を詳細に行ない,110℃,approx.42Mpaのもと72時間の重合を行った結果,固形分温度40%という高濃度の系でも,SGIを大過剰量用いることにより,重合率92%に達し,真っ白い粉末としてポリスチレンを得ることができた。その分子量は重合の進行に伴い増大したが,分子量分布は比較的狭いまま(M_w/M_n<.33)を維持し,リビング性を持って重合は進行した。重合条件の更なる最適化を目指したところ,30%過剰なSGIを用いることにより,48hの重合で重合率が60wt%に達成できることを明らかにした。高重合率を達成するためには,従来のNMP-SG1重合系よりも高温で重合を行わないといけないが,scCO_2流体中での重合においては,非リビング重合系の沈殿重合において報告されている,重合率が上昇しないという問題点と対照的であり,scCO_2流体中のリビング重合系特有の大きなアピールポイントである。今後の更なるNMP系の発展において,重要となる指針を得ることができた。

Report

(2 results)
  • 2006 Annual Research Report
  • 2005 Annual Research Report
  • Research Products

    (11 results)

All 2007 2006 2005

All Journal Article (11 results)

  • [Journal Article] Gel formation and primary chain lengths in nitroxide-mediated radical copolymerization of styrene and divinylhenzene in miniemulsion2007

    • Author(s)
      Yuichi Saka, Per B.Zetterlund, Masayoshi Okubo
    • Journal Title

      Polymer 48

      Pages: 1229-1236

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Compartmentalization in Nitroxide-Mediated Radical Polymerization in Dispersed Systems2006

    • Author(s)
      Per B.Zetterlund, Masayoshi Okubo
    • Journal Title

      Macromolecules 39

      Pages: 8959-8967

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Particle Size Effects in TEMPO-Mediated Radical Polymerization of Styrene in Aqueous Miniemulsion2006

    • Author(s)
      Tadashi Nakamura, Per B.Zetterlund, Masayoshi Okubo
    • Journal Title

      Macroml. Rapid Commun 27

      Pages: 2014-2018

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Nitroxide-mediated radical polymerization of styrene : Experimental evidence of chain transfer to monomter2006

    • Author(s)
      Per B.Zetterlund, Yuichi Saka, Ronan McHlale, Tadashi Nakamura, Fawaz Aldabbagh, Masayoshi Okubo
    • Journal Title

      Polymer 47

      Pages: 7900-7908

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Effects of Laplace Pressure on Propagation and Termination in Aqueous Heterogeneous Free Radical Polymerization2006

    • Author(s)
      Pcr B.Zetterlund, Masayoshi Okubo
    • Journal Title

      Macromol. Theory and Simul. 15

      Pages: 40-45

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Nitroxide-Mediated Radical Dispersion Polymerization of Styrene in Supercritical Carbon Dioxide Using a Poly(dimtehyllsiloxane-block-styrene) Alkoxyamine as Initiator and Stabilizer2006

    • Author(s)
      Ronan McHale, Fawaz Aldabbagh, Per B. Zetterlund, Masayoshi Okubo
    • Journal Title

      Macroml. Rapid Commun. 27

      Pages: 1465-1471

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Comartmentalization in Atom Transfer Radical Polymieriztion (ATRP) in Dispersed Systems2006

    • Author(s)
      Yasuyuki Kagawa, Per B.Zetterlund, Hideto Minami, Masayoshi Okubo
    • Journal Title

      Macromol. Theory Simul. 15

      Pages: 608-613

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Network Formation in Nitroxide-Mediated Radical Copolymerization of Styrene and Divinylbenzene in Miniemulsion2006

    • Author(s)
      Md.Nur Alam, Per B.Zetterlund, Masayoshi Okubo
    • Journal Title

      Macromol. Chemistry and Physics 207

      Pages: 1732-1741

    • NAID

      120002055760

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Nitroxide-Mediated Radical Dispersion Polymerization of Styrene in Supercritical Carbon Dioxide using a Poly(dimethylsiloxane-b-methyl methacrylate) Stabilizer2006

    • Author(s)
      Ronan McHale, Fawaz Aldabbagh, Per B.Zetterlund, Hideto Minami, Masayoshi Okubo
    • Journal Title

      Macromolecules 39

      Pages: 6853-6860

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Nitroxide-Mediated Radical Polymerization in Miniemulsion at Stationary State : Rationale for Independence of Polymerization Rate on Nitroxide Partitioning Using Oil-Phase Initiation2005

    • Author(s)
      Syuji Fujii, Hideto Minami, Masayoshi Okubo
    • Journal Title

      Macromol.Theory Simul. 14

      Pages: 415-420

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Nitroxede-Mediated Controlled/Living Free Radical Copolymerization of Styrene and Divinylbenzene in Aqueous Miniemulsion2005

    • Author(s)
      Per B.Zetterlund, Md.Nur Alam, Hideto Minami, Masayoshi Okubo
    • Journal Title

      Macroml.Rapid Commun. 26

      Pages: 955-960

    • Related Report
      2005 Annual Research Report

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Published: 2005-04-01   Modified: 2016-04-21  

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