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DEVELOPMENT AND APPLICATIONS OF HIGH-SPEED LIVING AND IMMORTAL POLYMERIZATIONS

Research Project

Project/Area Number 07555672
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section試験
Research Field 高分子合成
Research InstitutionTHE UNIVERSITY OF TOKYO

Principal Investigator

AIDA Takuzo  THE UNIVERSITY OF TOKYO,GRADUATE SCHOOL OF ENGINEERING,PROFESSOR, 大学院・工学系研究科, 教授 (00167769)

Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1996: ¥1,400,000 (Direct Cost: ¥1,400,000)
KeywordsLIVING POLYMERIZATION / ORGANOALUMINUM / ATE COMPLEX / LEWIS ACID / OXETANE / EPOXIDE / エボキシド / 合成高分子 / 金属ポルフィリン錯体 / アニオン重合
Research Abstract

Synthesis of polymers with uniform, controlled molecular weight is one of the important subjects in the field of polymer chemistry. We have found that some metalloporphyrins serve as excellent initiators for the living and immortal anionic polymerizations of a variety of monomers.
High-speed living polymerization is realized by, e.g., aluminum porphyrins (1) as nucleophiric initiators in conjunction with bulky Lewis acids (2), which function as monomer activators through coordinative interaction. In such a nucleophile-electrophile coexisting system, a degradative neutralization between these two species, leading to termination of polymerization, is very likely to occur. However, this undesired reaction is suppressed by the steric repulsion between the porphyrin ligand in the initiator and the bulky phenolate ligands in the Lewis acids. This is the principle of the high-speed living polymerization.
The high-speed living polymerization can be applied to monomers such as methacrylic esters … More and nitrile, epoxides, lactones, and cyclic carbonates. By changing the monomer-to-initiator mole ratio, molecular weight of the produced polymer is nicely controlled, where a narrow MWD polymer with a molecular weight >10^6 can be obtained under optimized conditions. The high-speed living polymerization of racemic alpha-methylbenzyl methacrylate by an aluminum porphyrin in the presence of a chiral Lewis acid proceeds enantioselectively as a result of the stereoselective monomer activation. Oxetane, which has been understood to polymerize only cationically, is also polymerizable by the present binary system, affording a narrow MWD polyether. Sequential high-speed living polymerization of methyl methacrylate followed by oxetane is successful to give a novel polyvinyl-polyether block copolymer with a narrow MWD.Immortal polymerization of epoxides by aluminum porphyrin/alcohol systems is also accelerated by bulky Lewis acids, and, under suitable conditions, more than 1000 polymer molecules with narrow MWD can be obtained per one initiator molecule. Less

Report

(3 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • Research Products

    (7 results)

All Other

All Publications (7 results)

  • [Publications] Takuzo Aida: "Metalloporphyrins as Initiators for Living and Immartal Pdymerizations" Aceounts of Chemical Research. 29. 39-48 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Daisuke Takeuchi,Takuzo Aida: "Controlled Coordnate Anionic Polymerization of Oxetane by Novel Initiating Systems.Onium Salf/Bulky Organsalnminum Diphenslates." Macromolecules. 29,25. 8096-8100 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Aida, T. ; Inoue, S.: "Metalloporphyrins as Initiators for Living and Immortal Polymerizations" Acc.Chem.Res.29. 39-48 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Takeuchi, D. ; Aida, T.: "Controlled Coordinate Anionic Polymerization of Oxetane by Novel Initiating Systems : Onium Salts-Bulky Organoaluminum Diphenolates" Macromolecules. 29. 8096-8100 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Takuzo Aida,: "Metalkprplynins as Initiators for Living and Immontal Polymerizations" Acconts of Chemical Research. 29. 39-48 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Daisuke Takeuchi: "Controlled Coordinate Anionic Polymerization of Oxetane by Novel Initiating Systems:Onium Salt/Bulky Organoaluminum Diphenolates" Macromolecules. 29・25. 8096-8100 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Takuzo Aida: "Living polymerization of methacrylic esters with aluminum porpuyrin initiators Axial ligand exchange activities of alkyl-and euolate-aluminum porphgrius" Journal of physical Organic Chemistry. 8. 249-257 (1995)

    • Related Report
      1995 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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