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Nitroxide-Mediated Control/Living Radical Polymerization in Supercritical Carbon Dioxide

Research Project

Project/Area Number 19550125
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Polymer chemistry
Research InstitutionKobe University

Principal Investigator

PER B Zetterlund  Kobe University, 大学院・工学研究科, 准教授 (20322365)

Co-Investigator(Kenkyū-buntansha) OKUBO Masayoshi  神戸大学, 大学院・工学研究科, 教授 (30031131)
Project Period (FY) 2007 – 2008
Project Status Completed (Fiscal Year 2008)
Budget Amount *help
¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000)
Fiscal Year 2008: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2007: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywords環境適応型媒体 / 制御 / リビングラジカル重合 / 超臨界二酸化炭素 / ニトロキシル法 / リビングラジカル重合法 / ニトロキシド / 沈殿重合 / 分子量分布 / スチレン / グリーンケミストリー / 環境適応型
Research Abstract

本研究では, 超臨界二酸化炭素中における, ニトロキシド法によるスチレンの制御/リビングラジカル重合(CLRP)を行った結果, ポリマー粒子と媒体間におけるニトロキシドの分配が重合制御に悪影響を及ぼすことを明らかにした。さらに, 系内のモノマー濃度を上昇させることでニトロキシドの媒体への分配を抑制すると, 均一系である溶液重合と比較して良好な重合制御が得られることを明らかにした。この現象は, 不均一系でのCLRPが均一系より優れていることを示した最初の例であり, 不均一系でのCLRPにおいて超臨界二酸化炭素が有用であることを示すことができた。

Report

(3 results)
  • 2008 Annual Research Report   Final Research Report ( PDF )
  • 2007 Annual Research Report
  • Research Products

    (53 results)

All 2009 2008 2007 Other

All Journal Article (31 results) (of which Peer Reviewed: 30 results) Presentation (21 results) Remarks (1 results)

  • [Journal Article] Compartmentalization in atom transfer radical polymerization of styrene in dispersed systems : effects of target molecular weight and halide end group2009

    • Author(s)
      P. B. Zetterlund, Y. Kagawa, M. Okubo
    • Journal Title

      Macromolecules 42

      Pages: 2488-2488

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Network formation in nitroxide-mediated radical copolymerization of styrene and divinylbenzene in miniemulsion : effect of macroinitiator hydrophilicity2009

    • Author(s)
      Md. N. Alam, P. B. Zetterlund, M. Okubo
    • Journal Title

      Polymer 50

      Pages: 1632-1632

    • NAID

      120001460006

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] 制御/リビングラジカル重合の水媒体不均-系への適用2009

    • Author(s)
      南秀人, P. B. Zetterlund, 大久保政芳
    • Journal Title

      高分子 58

      Pages: 78-78

    • Related Report
      2008 Final Research Report
  • [Journal Article] Gelation and hollow particle formation in nitroxide-mediated radical copolymerization of styrene and divinylbenzene in miniemulsion2009

    • Author(s)
      P. B. Zetterlund, Y. Saka, M. Okubo
    • Journal Title

      Macromol. Chem. Phys 210

      Pages: 140-140

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Gelation and hollow particle formation in nitroxide-mediated radical copolymerization of styrene and divinylbenzene in miniemulsion2009

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

      Macromol. Chem. Phys. 210

      Pages: 140-149

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 制御/リビングラジカル重合の水媒体不均一系への適用2009

    • Author(s)
      南 秀人, Per B. Zetterlund, 大久保政芳
    • Journal Title

      高分子 58

      Pages: 78-81

    • NAID

      10024759080

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Controlled/Living Radical Polymerization in Dispersed Systems2008

    • Author(s)
      P. B. Zetterlund, Y. Kagawa, M. Okubo
    • Journal Title

      Chem. Rev 108(9)

      Pages: 3747-3747

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Nitroxide-mediated precipitation polymerization of styrene in supercritical carbon dioxide : Effects of monomer loading and nitroxide partitioning on control2008

    • Author(s)
      F. Aldabbagh, P. B. Zetterlund, M. Okubo
    • Journal Title

      Eur. Polym. J 44

      Pages: 4037-4037

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] TEMPO-mediated radical polymerization of styrene in aqueous miniemulsion : Macroinitiator concentration effect2008

    • Author(s)
      Md N. Alam, P. B. Zetterlund, M. Okubo
    • Journal Title

      Polymer 49

      Pages: 3428-3428

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Improved control in nitroxide-mediated radical polymerization using supercritical carbon dioxide2008

    • Author(s)
      F. Aldabbagh, P. B. Zetterlund, M. Okubo
    • Journal Title

      Macromolecules 41

      Pages: 2732-2732

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Quantification of spontaneous initiation in radical polymerization of styrene in aqueous miniemulsion at high temperature2008

    • Author(s)
      Md. N. Alam, P. B. Zetterlund, M. Okubo
    • Journal Title

      Polymer 49

      Pages: 883-883

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Use of fluorescence-labeled macroinitiator to investigate nucleation mechanism in nitroxide-mediated crosslinking polymerization in aqueous miniemulsion2008

    • Author(s)
      P. B. Zetterlund, M. N. Alam, M. Okubo
    • Journal Title

      Polym. J 40

      Pages: 298-298

    • NAID

      10021116962

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Nitroxide-mediated radical polymerization in microemulsion2008

    • Author(s)
      J. Wakamatsu, M. Kawasaki, P. B. Zetterlund, M. Okubo
    • Journal Title

      Macromol. Rapid Commun 28

      Pages: 2346-2346

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Use of fluorescence-labelled macroinitiator to investigate nucleation mechanism in nitroxide-mediated crosslinking polymerization in aqueous miniemulsion2008

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

      Polym. J. 40

      Pages: 298-299

    • NAID

      10021116962

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Quantification of spontaneous initiation in radical polymerization of styrene in aqueous miniemulsion at high temperature2008

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

      Polymer 49

      Pages: 883-892

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Improved control in nitroxide-mediated radical polymerization using supercritical carbon dioxide2008

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

      Macromolecules 41

      Pages: 2732-2734

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] TEMPO-mediated radical polymerization of styrene in aqueous miniemulsion : Macroinitiator concentration effects on control/livingness2008

    • Author(s)
      Md Nur Alain, Per B. Zelterlund, Masayoshi Okubo
    • Journal Title

      J. Polym. Chem. : Part A : Polym. Chem. 48

      Pages: 3428-3435

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] TEMPO-mediated radical polymerization of slyrene in aqueous miniemulsion : Macroinitiator concentration effect2008

    • Author(s)
      Md Nur Alain, Per B. Zelterlund, Masayoshi Okubo
    • Journal Title

      Polymer 49

      Pages: 3428-3435

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Nitroxide-mediated precipitation polymerization of styrene in supercritical carbon dioxide : Effects of monomer loading and nitroxide partitioning on control2008

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

      Eur. Polym. J. 44

      Pages: 4037-4046

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Controlled/Living Radical Polymerization in Dispersed Systems2008

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

      Chem. Rev. 108

      Pages: 3747-3794

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Improved Control in Nitroxide-Mediated Radical Polymerization using Supercritical Carbon Dioxide2008

    • Author(s)
      F. Aldabbagh, P. B. Zetterlund M. Okubo
    • Journal Title

      Macromolecules 41

      Pages: 2732-2734

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Quantification of Spontaneous Initiation in Radical Polymerization of Styrene in Aqueous Miniemulsion at High Temperature2008

    • Author(s)
      Md. N. Alam, P. B. Zetterlund, M. Okubo
    • Journal Title

      Polymer 49

      Pages: 883-892

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Atom transfer radical polymerization of iso-butyl methacrylate in microemulsion with cationic and nonionic emulsifiers2007

    • Author(s)
      Y. Kagawa, M. Kawasaki, P. B. Zetterlund, H. Minami, M. Okubo
    • Journal Title

      Macromol. Rapid Commun 28

      Pages: 2354-2354

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Mechanistic investigation of particle size effects in TEMPO-mediated radical polymerization of styrene in aqueous miniemulsion2007

    • Author(s)
      P. B. Zetterlund, T. Nakamura, M. Okubo
    • Journal Title

      Macromolecules 40

      Pages: 8663-8663

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Nitroxide-mediated radical precipitation polymerization of styrene in supercritical carbon dioxide2007

    • Author(s)
      R. Mchale, F. Aldabbagh, P. B. Zetterlund, M. Okubo
    • Journal Title

      Macromol. Chemistry and Physics 28

      Pages: 1813-1822

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Compartmentalization in TEMPO-mediated radical polymerization in dispersed systems : effects of macroinitiator concentrationa2007

    • Author(s)
      P. B. Zetterlund, M. Okubo
    • Journal Title

      Macromol. Theory and Simul 16

      Pages: 221-221

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Gel formation and primary chain lengths in nitroxide-mediated radical copolymerization of styrene and divinylbenzene in miniemulsion2007

    • Author(s)
      Y. Saka, P. B. Zetterlund, M. Okubo
    • Journal Title

      Polymer 48

      Pages: 1229-1229

    • NAID

      120000943591

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Nitroxide-Mediated Radical Precipitation Polymerization of Styrene in Supercritical Carbon Dioxide2007

    • Author(s)
      R. McHale, F. Aldabbagh, P. B. Zetterlund, M. Okubo
    • Journal Title

      Macromolecular Chemistry and Physics 208

      Pages: 1813-1822

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Compartmentalization in TEMPO-Mediated Radical Polymerization in Dispersed Systems: Effects of Maeroinitiator Concentration2007

    • Author(s)
      P. B. Zetterlund, M. Okubo
    • Journal Title

      Macromolecular Theory and Simulations 16

      Pages: 221-226

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Network formation in nitroxide-mediated radical copolymerization of styrene and divinylbenzene in miniemulsion : effect of macroinitiator hydrophilicity

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

      Polymer(掲載確定) (in press)

    • NAID

      120001460006

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Compartmentalization in atom transfer radical polymerization of styrene in dispersed systems : effects of target molecular weight and halide end group

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

      Macromolecules(掲載確定) (in press)

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Presentation] Beneficial effects of supercritical carbon dioxide on control in nitroxide-mediated radical polymerization2008

    • Author(s)
      P. B. Zetterlund, F. Aldabbagh, M. Okubo
    • Organizer
      第15回高分子ミクロスフェア討論会
    • Place of Presentation
      神戸大学
    • Related Report
      2008 Annual Research Report 2008 Final Research Report
  • [Presentation] Network formation in nitroxide-mediated radical copolymerization of styrene and divinylbenzene in miniemulsion : Effect of macroinitiator hydrophilicity2008

    • Author(s)
      M. N. Alam, P. B. Zetterlund, M. Okubo
    • Organizer
      第57回高分子学会討論会
    • Place of Presentation
      大阪市立大学
    • Related Report
      2008 Annual Research Report 2008 Final Research Report
  • [Presentation] Improved control in nitroxide-mediated radical polymerization using supercritical carbon dioxide2008

    • Author(s)
      P. B. Zetterlund, F. Aldabbagh, M. Okubo
    • Organizer
      第57回高分子学会討論会
    • Place of Presentation
      大阪市立大学
    • Related Report
      2008 Annual Research Report 2008 Final Research Report
  • [Presentation] 水媒体不均一系におけるニトロキシル制御/リビングマイクロエマルション重合2007

    • Author(s)
      若松純平, P. B. Zetterlund, 香川靖之, 大久保政芳
    • Organizer
      第53回高分子研究発表会
    • Place of Presentation
      神戸
    • Year and Date
      2007-07-20
    • Related Report
      2008 Final Research Report
  • [Presentation] Kinetic features of ATRP in miniemulsion : Confined space effect and segregation effect2007

    • Author(s)
      Y. Kagawa, P. B. Zetterlund, M. Okubo
    • Organizer
      第10回環太平洋高分子国際会議(The Pacific Polymer Conference, PPC10)
    • Place of Presentation
      神戸国際会議場
    • Related Report
      2008 Final Research Report
  • [Presentation] Nitroxide-mediated precipitation polymerization of styrene in supercritical carbon dioxide using TIPNO2007

    • Author(s)
      F. Aldabbagh, P. B. Zetterlund, H. Minami, M. Okubo
    • Organizer
      第10回環太平洋高分子国際会議(The Pacific Polymer Conference, PPC10)
    • Place of Presentation
      神戸国際会議場
    • Related Report
      2008 Final Research Report
  • [Presentation] Compartmentalization, partitioning and interface effects in nitroxide-mediated polymerization in dispersed systems2007

    • Author(s)
      P. B. Zetterlund, T. Nakamura, Md. N. Alam, J. Wakamatsu, M. Okubo
    • Organizer
      第10回環太平洋高分子国際会議(The Pacific Polymer Conference, PPC10)
    • Place of Presentation
      神戸国際会議場
    • Related Report
      2008 Final Research Report
  • [Presentation] Nitroxide-mediated radical precipitation polymerization of styrene employing supercritical carbon dioxide as medium2007

    • Author(s)
      R. McHale, F. Aldabbagh, P. B. Zetterlund, M. Okubo
    • Organizer
      第56回高分子討論会
    • Place of Presentation
      名古屋
    • Related Report
      2008 Final Research Report
  • [Presentation] Nitroxide-mediated polymerization in dispersed systems : Compartmentalization, partitioning and interface effects2007

    • Author(s)
      P. B. Zetterlund, 中村 匡, M. N. Alam, 大久保政芳
    • Organizer
      第56回高分子討論会
    • Place of Presentation
      名古屋
    • Related Report
      2008 Final Research Report
  • [Presentation] Nitroxide-mediated radical polymerization in miniemulsion : Bimolecular termination in monomer-free model system2007

    • Author(s)
      M. N. Alam, P. B. Zetterlund, M. Okubo
    • Organizer
      2007 Gordon Research Conference
    • Place of Presentation
      アメリカ
    • Related Report
      2008 Final Research Report
  • [Presentation] Compartmentalization and partitioning effect in microemulsion ATRP2007

    • Author(s)
      Y. Kagawa, P. B. Zetterlund, H. Minami, M. Okubo
    • Organizer
      2007 Gordon Research Conference
    • Place of Presentation
      アメリカ
    • Related Report
      2008 Final Research Report
  • [Presentation] "Confined space effect" on deactivation in nitroxide-mediated polymerization in aqueous dispersed systems2007

    • Author(s)
      P. B. Zetterlund, Y. Kagawa, J. Wakamatsu, M. Okubo
    • Organizer
      2007 Gordon Research Conference
    • Place of Presentation
      アメリカ
    • Related Report
      2008 Final Research Report
  • [Presentation] Effects of compartmentalization and partitioning in nitroxide-mediated radical polymerization in dispersed systems2007

    • Author(s)
      P. B. Zetterlund, M. Okubo
    • Organizer
      第56回高分子学会年次大会
    • Place of Presentation
      京都国際会議場
    • Related Report
      2008 Final Research Report
  • [Presentation] Nitroxide-mediated radical precipitation polymerization of styrene in supercritical carbon dioxide2007

    • Author(s)
      R. McHale, F. Aldabbagh, P. B. Zetterlund, M. Okubo
    • Organizer
      第56回高分子学会年次大会
    • Place of Presentation
      京都国際会議場
    • Related Report
      2008 Final Research Report
  • [Presentation] Nitroxide-mediated radical polymerization in miniemulsion : Bimolecular termination in monomer-free model systems2007

    • Author(s)
      M. N. Alam, P. B. Zetterlund, M. Okubo
    • Organizer
      第56回高分子学会年次大会
    • Place of Presentation
      京都国際会議場
    • Related Report
      2008 Final Research Report
  • [Presentation] ニトロキシル制御/リビングラジカルミニエマルション重合における粒子径がニトロキシル濃度に与える影響2007

    • Author(s)
      中村匡, P. B. Zetterlund, 香川 靖之, 大久保政芳
    • Organizer
      第56回高分子学会年次大会
    • Place of Presentation
      京都国際会議場
    • Related Report
      2008 Final Research Report
  • [Presentation] ミニエマルション系での原子移動ラジカル重合における銅触媒の分配及びコンパートメンタリゼーション効果2007

    • Author(s)
      香川靖之, 南秀人, P. B. Zetterlund, 大久保政芳
    • Organizer
      第56回高分子学会年次大会
    • Place of Presentation
      京都国際会議場
    • Related Report
      2008 Final Research Report
  • [Presentation] Nitroxide-Mediated Radical Precipitation Polymerization of Styrene Employing Supercritical Carbon Dioxide as Medium2007

    • Author(s)
      R. MeHale, F. Aldabbagh, P. B. Zetterlund, M. Okubo
    • Organizer
      Society of Polymer Science, Japan, 56th Symposium on Macromolecules
    • Place of Presentation
      Nagoya Institute of Technology,
    • Related Report
      2007 Annual Research Report
  • [Presentation] Nitroxide-Mediated Precipitation Polymerization of Styrene in Supercritical Carbon Dioxide2007

    • Author(s)
      F. Aldabbagh, P. B. Zetterlund, H. Minami, M. Okubo
    • Organizer
      10th Pacific Polymer Conference (PPC 10)
    • Place of Presentation
      Kobe, Japan
    • Related Report
      2007 Annual Research Report
  • [Presentation] Nitroxide-Mediated Polymerization in Dispersed Systems: Compartmentalization, Partitioning and Interface Effects2007

    • Author(s)
      P. B. Zetterlund, T. Nakamura, Md. N. Alam, M. Okubo
    • Organizer
      Society of Polymer Science, Japan, 56th Symposium on Macromolecules
    • Place of Presentation
      Nagoya Institute of Technology,
    • Related Report
      2007 Annual Research Report
  • [Presentation] Miniemulsion Polymerization of Styrene by Spontaneous Initiation at High Temperature2007

    • Author(s)
      Md. Nur Alam, P. B. Zetterlund, M. Okubo
    • Organizer
      10th Pacific Polymer Conference (PPC 10)
    • Place of Presentation
      Kobe, Japan
    • Related Report
      2007 Annual Research Report
  • [Remarks] 本研究成果は19年度のゴードン研究会議でのポスター発表「"Confined Space Effect"on Deactivation in Nitroxide-Mediated Polymerization in Aqueous Dispersed Systems」に対してPoster Prize (third prize)を授与されるなど, 世界最高峰の研究者が集まる会議においてもそのレベルの高さが認められた。さらに, 化学分野において世界最高の総説誌と位置づけられるChemical Reviews誌(Impact Factor : 22.76)に「水媒体不均一系でのリビングラジカル重合」と題する総説(48項, 引用文献数507)が受理され, すでに掲載されている。

    • Related Report
      2008 Final Research Report

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Published: 2007-04-01   Modified: 2016-04-21  

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