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Development of Stereospecific Living Radical Polymerization

Research Project

Project/Area Number 26620084
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeMulti-year Fund
Research Field Synthetic chemistry
Research InstitutionKyoto University

Principal Investigator

Shigeru Yamago  京都大学, 化学研究所, 教授 (30222368)

Project Period (FY) 2014-04-01 – 2016-03-31
Project Status Completed (Fiscal Year 2015)
Budget Amount *help
¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2015: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2014: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Keywords立体規則的重合 / ラジカル重合 / 立体選択的反応 / ルイス酸 / イソタクチックポリアクリレート / リビングラジカル重合 / 立体規則性重合
Outline of Final Research Achievements

A new stereospecific radical polymerization reaction has been developed. While the conventional methods use on the penultimate effect, the current method relies on the auxiliary control at the propagating polymer-chain end. Lewis acid (MgBr2)-catalyzed radical polymerization of acrylimides bearing chiral oxazolidinones gave highly isotactic polyacrylimides with up to >99% meso tetrad (mmm) selectivity. Polymerization in the absence of Lewis acid gave atactic polymers with 80% racemo diad (r) selectivity; the selectivity was deliberately tuned from 80% r to >99% mmm by varying the polymerization conditions. The polyacrylimide was quantitatively converted to corresponding polyacrylates while preserving the stereoregularity, thus providing a general method for the synthesis of atactic to isotactic polyacrylates.

Report

(3 results)
  • 2015 Annual Research Report   Final Research Report ( PDF )
  • 2014 Research-status Report
  • Research Products

    (7 results)

All 2015 2014

All Journal Article (2 results) (of which Peer Reviewed: 2 results,  Acknowledgement Compliant: 1 results) Presentation (5 results) (of which Int'l Joint Research: 1 results,  Invited: 2 results)

  • [Journal Article] Lewis-acid-mediated Stereospecific Radical Polymerization of Acrylimides bearing Chiral Oxazolidinones2015

    • Author(s)
      Fujita, T.; Yamago, S.
    • Journal Title

      Chem. Eur. J.

      Volume: 21 Issue: 51 Pages: 18547-18550

    • DOI

      10.1002/chem.201504184

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Expanding the scope of controlled radical polymerization via cobalt-tellurium radical exchange reaction2014

    • Author(s)
      Kermagoret, A.; Nakamura, Y.; Bourguignon, M.; Detrembleur, C.; Jerome, C.; Yamago, S.; Debuigne, A.
    • Journal Title

      ACS Macro Lett.

      Volume: 3 Issue: 1 Pages: 114-118

    • DOI

      10.1021/mz400635h

    • Related Report
      2014 Research-status Report
    • Peer Reviewed
  • [Presentation] 立体規則的ラジカル重合の開発2015

    • Author(s)
      山子茂, 藤田健弘
    • Organizer
      財団法人日本化学繊維研究所第73回講演会
    • Place of Presentation
      京都
    • Year and Date
      2015-11-10
    • Related Report
      2015 Annual Research Report
    • Invited
  • [Presentation] Stereospecific radical polymerization of acrylimides bearing chiral oxazolidinones2015

    • Author(s)
      Fujita, T.; Yamago, S.
    • Organizer
      International Science & Nature Congress (ISNaC) 2015
    • Place of Presentation
      Kuala Lumpur, Malaysia
    • Year and Date
      2015-09-22
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ラジカル-ラジカル反応の選択性における溶媒ケージ効果2015

    • Author(s)
      荻原祐、中村泰之、山子茂
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      船橋
    • Year and Date
      2015-03-28
    • Related Report
      2014 Research-status Report
  • [Presentation] Photo-Induced Organotellurium-Mediated Living Radical Polymerization (TERP) and Radical Coupling Reaction2015

    • Author(s)
      山子茂
    • Organizer
      MACRO2015, International Symposium on Polymer Science and Technology
    • Place of Presentation
      Kolkata, India
    • Year and Date
      2015-01-26
    • Related Report
      2014 Research-status Report
  • [Presentation] Recent Developments in Organotellurium-Mediated Living Radical Polymerization (TERP)2014

    • Author(s)
      山子茂
    • Organizer
      EUChem Conference on Organic Free Radicals
    • Place of Presentation
      Prag, Czech Republic
    • Year and Date
      2014-07-02
    • Related Report
      2014 Research-status Report
    • Invited

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Published: 2014-04-04   Modified: 2017-05-10  

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