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Development of asymmetric templated polymerization systems using reversible bonds

Research Project

Project/Area Number 22K20540
Research Category

Grant-in-Aid for Research Activity Start-up

Allocation TypeMulti-year Fund
Review Section 0501:Physical chemistry, functional solid state chemistry, organic chemistry, polymers, organic materials, biomolecular chemistry, and related fields
Research InstitutionTokyo Metropolitan University

Principal Investigator

Shimoyama Daisuke  東京都立大学, 理学研究科, 助教 (00965866)

Project Period (FY) 2022-08-31 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
Fiscal Year 2023: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2022: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Keywords精密合成 / 官能基変換 / チタン触媒 / 高分子機能材料 / オレフィン重合 / 精密重合 / チタン錯体触媒 / ホウ素 / 超分子化学 / らせん
Outline of Research at the Start

生体高分子の不斉触媒機能を凌駕する触媒が求められるなか,人工高分子は次世代不斉触媒として期待されている。本研究課題では,高分子不斉触媒の実用化への更なる一歩として,精密重合された高分子から更なる不斉高分子を生成する不斉テンプレート重合法の開発を目指す。

Outline of Final Research Achievements

Construction of asymmetric templated polymerization systems requires the precise synthesis of helical polymers containing functional groups in the side chain. In this study, we developed the precise synthesis of new functionalized polyolefins through the post-modification. Olefin polymerizations of functional monomers using half-titanocene catalysts have been demonstrated, and the exclusive polymer modification (halogenation and cross-coupling reaction) of resultant polymers was able to tune the thermal and mechanical properties.

Academic Significance and Societal Importance of the Research Achievements

本研究成果では,ハーフチタンノセン触媒により精密合成した新規官能基化ポリオレフィンが,post-modificationにより様々な官能基化ポリマーに変換可能あることを示した。またポリマーの物理物性(熱物性,機械的特性等)は,変換された官能基に依存することが分かった。このポリマーの合成手法は様々な共重合体に応用が可能で汎用性が高いため,新規オレフィン系ポリマーの合成を可能とし,さらに自在に物理物性を調整できる技術となることが期待される。

Report

(3 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Research-status Report
  • Research Products

    (11 results)

All 2023 Other

All Journal Article (1 results) (of which Peer Reviewed: 1 results) Presentation (9 results) (of which Int'l Joint Research: 3 results) Remarks (1 results)

  • [Journal Article] Synthesis of ethylene/isoprene copolymers containing cyclopentane/cyclohexane units as unique elastomers by half-titanocene catalysts2023

    • Author(s)
      L. Guo, R. Makino, D. Shimoyama, J. Kadota, H. Hirano, K. Nomura
    • Journal Title

      Macromolecules

      Volume: 56 Issue: 3 Pages: 899-914

    • DOI

      10.1021/acs.macromol.2c02399

    • Related Report
      2023 Annual Research Report 2022 Research-status Report
    • Peer Reviewed
  • [Presentation] ポリフルオレンビニレンを側鎖に有する櫛型ポリマーの精密合成2023

    • Author(s)
      千野浩輝,下山大輔,野村琴広
    • Organizer
      第69回高分子研究発表会(神戸)
    • Related Report
      2023 Annual Research Report
  • [Presentation] ハーフチタノセン触媒を用いたシリルスチレンのシンジオ特異的重合2023

    • Author(s)
      Jiang Youshu,下山大輔,野村琴広
    • Organizer
      第69回高分子研究発表会(神戸)
    • Related Report
      2023 Annual Research Report
  • [Presentation] ハーフチタノセン触媒によるエチレンとα-メチルスチレンとの共重合2023

    • Author(s)
      小島輝竜, 下山大輔, 野村琴広
    • Organizer
      第132回触媒討論会
    • Related Report
      2023 Annual Research Report
  • [Presentation] 新規フェノキシ配位ハーフチタノセン触媒によるエチレンとスチレンとの共重合2023

    • Author(s)
      黄 天天, 下山大輔, 野村琴広
    • Organizer
      第53回石油・石油化学討論会
    • Related Report
      2023 Annual Research Report
  • [Presentation] Synthesis of conjugated bottlebrush polymers containing all trans-poly(fluorene-2,7-vinylene) side chains2023

    • Author(s)
      Hiroki Chino, Daisuke Shimoyama, Kotohiro Nomura
    • Organizer
      The International Symposium on Catalysis and Fine Chemicals 2023 (C&FC2023)
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Syndiospecific polymerization of trialkylsilylstyrene and the ethylene copolymerization by half-titanocene catalysts2023

    • Author(s)
      Youshu Jiang, Daisuke Shimoyama, Kotohiro Nomura
    • Organizer
      Asian Polyolefin Workshop 2023 (APO2023)
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis of new phenoxide-modified half-titanicenes for olefin polymerization2023

    • Author(s)
      Jiahao Gao, Daisuke Shimoyama, Kotohiro Nomura
    • Organizer
      Asian Polyolefin Workshop 2023 (APO2023)
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ポリフルオレンビニレンを側鎖に有する櫛型ポリマーの精密合成2023

    • Author(s)
      千野浩輝,下山大輔,野村琴広
    • Organizer
      第69回高分子研究発表会(神戸)
    • Related Report
      2022 Research-status Report
  • [Presentation] ハーフチタノセン触媒を用いたシリルスチレンのシンジオ特異的重合2023

    • Author(s)
      Jiang Youshu,下山大輔,野村琴広
    • Organizer
      第69回高分子研究発表会(神戸)
    • Related Report
      2022 Research-status Report
  • [Remarks] 東京都立大学 有機化学研究室

    • URL

      http://tmu-orgchem-lab.com/

    • Related Report
      2023 Annual Research Report

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Published: 2022-09-01   Modified: 2025-01-30  

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