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Development of New Anionic Polymerization Initiators Based on Metal Ate Complexes

Research Project

Project/Area Number 15350071
Research Category

Grant-in-Aid for Scientific Research (B)

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

Principal Investigator

IHARA Eiji  Ehime University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (90243592)

Project Period (FY) 2003 – 2005
Project Status Completed (Fiscal Year 2005)
Budget Amount *help
¥7,100,000 (Direct Cost: ¥7,100,000)
Fiscal Year 2005: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 2004: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 2003: ¥3,300,000 (Direct Cost: ¥3,300,000)
KeywordsAte complex / Transition metal / Main group metal / Anionic polymerization / Cationic polymerization / Methyl methacrylate / t-Butyl acrylate / Isobutyl vinyl ether / 金属アート錯体 / リビング重合
Research Abstract

We have succeeded in demonstrating that ate complexes of various metals are effective as polymerization initiators.
1.Transition metal ate complexes as initiators for anionic polymerization of methyl methacrylate (MMA).
We have found that transition metal ate complexes generated by the reaction of transition metal halide with organolithium can initiate the anionic polymerization of MMA. Living polymerization of MMA was achieved by using ate complex of Fe in conjunction with an organoaluminum as an additive or by the polymerization at -78℃ using ate complexes of V and Cr. Ate complexes of Nb, Mo, and W bearing secondary amide ligands afforded highly isotactic PMMA at -78℃. Y-ate complexes with secondary amide ligands initiated the living polymerization of MMA, giving PMMAs with narrow molecular weight distributions and amino groups at chain ends.
2.Living polymerization of t-butyl acrylate (tBA) initiated with an ate complex of Al.
The Al-ate complex generated by the reaction of iBu_3Al with tBuOK initiated living polymerization of tBA. Block copolymerization of tBA with MMA was also successful using the initiating system.
3.Cationic polymerization of isobutyl vinyl ether (IBVE) initiated with ate complexes of Nb
The ate complex of Nb with trityl cation was found to be effective for the cationic polymerization of IBVE. The ate complex bearing a secondary amide ligand afforded poly(IBVE)s with narrow molecular weight distributions.

Report

(4 results)
  • 2005 Annual Research Report   Final Research Report Summary
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • Research Products

    (24 results)

All 2006 2005 2004 2003 Other

All Journal Article (19 results) Publications (5 results)

  • [Journal Article] Cationic Polymerization of Isobutyl Vinyl Ether Initiated with Transition-Metal Ate Complexes2006

    • Author(s)
      Eiji Ihara
    • Journal Title

      J. Polym. Sci., Part A., Polym.Chem 44

      Pages: 2636-2641

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Cationic Polymerization of Isobutyl Vinyl Ether Initiated with Transition-Metal Ate Complexes2006

    • Author(s)
      Eiji Ihara
    • Journal Title

      J.Polym.Sci., Part A., Polym.Chem. 44

      Pages: 2636-2641

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Cationic Polymerization of Isobutyl Vinyl Ether Initiated with Transition Metal Ate Complexes2006

    • Author(s)
      Eiji Ihara
    • Journal Title

      J.Polym.Sci., Part A, Polym.Chem. 44(印刷中)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Anionic Polymerization of Methyl Methacrylate by Initiating Systems Based on Lithium Amides of Various Secondary Amines2005

    • Author(s)
      Eiji Ihara
    • Journal Title

      J. Polym. Sci., Part A., Polym. Chem. 43

      Pages: 4405-4411

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Anionic Polymerization of Methyl Methacrylate by Initiating Systems Based on Lithium Amides of Various Secondary Amines2005

    • Author(s)
      Eiji Ihara
    • Journal Title

      J.Polym.Sci., Part A., Polym.Chem. 43

      Pages: 4405-4411

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Anionic Polymerization of Methyl Methacrylate by Initiating Systems Based on Lithium Amides of Various Secondary Amines2005

    • Author(s)
      Eiji Ihara
    • Journal Title

      J.Polym.Sci., Part A., Polym.Chem. 43・15

      Pages: 4405-4411

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Anionic Polymerization of Methyl Methacrylate Initiated with Lithium Diphenylamide(Ph_2NLi) in the Presence of Divalent Transition Metal Halide2004

    • Author(s)
      Eiji Ihara
    • Journal Title

      J. Polym. Sci., Part A., Polym. Chem. 42

      Pages: 31-37

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] tBuOK/iBu_3AI as New Initiating System for Controlled Anionic Polymerization of tert-Butyl Acrylate and Methyl Methacrylate2004

    • Author(s)
      Eiji Ihara
    • Journal Title

      Macromolecules 37

      Pages: 4048-4054

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Anionic Polymerization of Methyl Methacrylate Initiated with Lithium Diphenylamide(Ph_2NLi) in the Presence of Divalent Transition Metal Halide2004

    • Author(s)
      Eiji Ihara
    • Journal Title

      J.Polym.Sci., Part A., Polym.Chem. 42

      Pages: 31-37

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] tBuOK/iBu_3Al as New Initiating System for Controlled Anionic Polymerization of tert-Butyl Acrylate and Methyl Methacrylate2004

    • Author(s)
      Eiji Ihara
    • Journal Title

      Macromolecules 37

      Pages: 4048-4054

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] tBuOK/iBu_3Al as New Initiating System for Controlled Anionic Polymerization of tert-Butyl Acrylate and Methyl Methacrylate2004

    • Author(s)
      Eiji Ihara
    • Journal Title

      Macromolecules 37・11

      Pages: 4048-4054

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Anionic Polymerization of Methyl Methacrylate Initiated with Late Transition-Metal Halides/Organolithium/Triisobutylaluminum Systems2003

    • Author(s)
      Eiji Ihara
    • Journal Title

      J. Polym. Sci., Part A., Polym. Chem. 41

      Pages: 1962-1977

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Anionic polymerization of methyl methacrylate in the presence of chromium carbonyl[Cr(CO)_6]2003

    • Author(s)
      Eiji Ihara
    • Journal Title

      Polym. Bull. 50

      Pages: 213-218

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] 遷移金属アート錯体を開始剤とするアクリレート類の重合2003

    • Author(s)
      井原栄治
    • Journal Title

      接着 47

      Pages: 225-229

    • NAID

      40005761565

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Anionic Polymerization of Methyl Methacrylate Initiated with Chromium and Vanadium Ate Complexes Incorporating Diisopropylamide Ligand2003

    • Author(s)
      Eiji Ihara
    • Journal Title

      Polym. J. 35

      Pages: 972-977

    • NAID

      10011839469

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Anionic Polymerization of Methyl Methacrylate Initiated with Late Transition-Metal Halides/Organolithium/Triisobutylaluminum Systems2003

    • Author(s)
      Eiji Ihara
    • Journal Title

      J.Polym.Sci., Part A., Polym.Chem. 41

      Pages: 1962-1977

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Anionic polymerization of methyl methacrylate in the presence of chromium carbonyl [Cr(CO)_6]2003

    • Author(s)
      Eiji Ihara
    • Journal Title

      Polym.Bull. 50

      Pages: 213-218

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Polymerization of Acrylates Initiated with Transition-metal Ate Complexes2003

    • Author(s)
      Eiji Ihara
    • Journal Title

      Adhesion and Sealing 47

      Pages: 225-229

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Anionic Polymerization of Methyl Methacrylate Initiated with Chromium and Vanadium Ate Complexes Incorporating Diisopropylamide Ligand2003

    • Author(s)
      Eiji Ihara
    • Journal Title

      Polym.J. 35

      Pages: 972-977

    • NAID

      10011839469

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Publications] Eiji IHARA: "Anionic Polymerization of Methyl Methacrylate Initiated with Late Transition-Metal Halides/Organolithium/Trilsobutylaluminum Systems"J.Polym.Sci., Part A., Polym.Chem.. 41・13. 1962-1977 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 井原 栄治: "遷移金属アート錯体を開始剤とするアクリレート類の重合"接着. 47・5. 225-229 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Eiji IHARA: "Anionic polymerization of methyl methacrylate in the presence of chromium carbonyl [Cr(CO)_6]"Polym.Bull.. 50・4. 213-218 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Eiji IHARA: "Anionic Polymerization of Methyl Methacrylate Initiated with Chromium and Vanadium Ate Complexes Incorporating Diisopropylamide Ligand"Polymer J.. 35・12. 972-977 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Eiji IHARA: "Anionic Polymerization of Methyl Methacrylate Initiated with Lithium Diphenylamide (Ph_2NLi) in the Presence of Divalent Transition Metal Halide"J Polym.Sci., Part A., Polym.Chem.. 42・1. 31-37 (2004)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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