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Importance of reversible reaction for the selective synthesis of telechelic polymer by means of polycondensation

Research Project

Project/Area Number 21H01989
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 35010:Polymer chemistry-related
Research InstitutionKanagawa University

Principal Investigator

Yokozawa Tsutomu  神奈川大学, 化学生命学部, 教授 (80182690)

Project Period (FY) 2021-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥17,810,000 (Direct Cost: ¥13,700,000、Indirect Cost: ¥4,110,000)
Fiscal Year 2023: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000)
Fiscal Year 2022: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000)
Fiscal Year 2021: ¥10,270,000 (Direct Cost: ¥7,900,000、Indirect Cost: ¥2,370,000)
Keywords重縮合 / テレケリックポリマー / 可逆反応 / 平衡重合 / 末端官能基化 / ポリエステル / ポリカーボネート / ポリエーテルスルホン / 環状ポリカーボネート / 開環重合
Outline of Research at the Start

重縮合でどちらかのモノマーを過剰に用いると、過剰に用いたモノマーがポリマー両末端に結合したテレケリックポリマーが生成すると一般的に考えられているが、実際は環状ポリマーが混入する。本研究では同様な重縮合で選択的にテレケリックポリマーだけが生成する合成手法の開発を目的とした。注目したのは可逆的結合生成反応の重縮合である。可逆反応であれば重合途中に生成した環状ポリマーは、過剰に加えたモノマーと反応してテレケリックポリマーが選択的に得られると期待される。

Outline of Final Research Achievements

Quantitative end-functionalization in the polycondensation of difunctional nucleophilic monomer and difunctional electrophilic monomer (A2 + B2 polycondensation) is not necessarily easy, because the polymer ends A and B undergo cyclization in competition with propagation even when any of the two monomers is used in excess. In this research, we investigated a simpler approach to end-functionalized polymer by means of unstoichiometric reversible polycondensation of two monomers. The use of an excess of one monomer resulted in the formation of linear polymer end-capped with the excess monomer at both ends without formation of cyclic polymer. Furthermore, the reversible polycondensation of equimolar monomers in the presence of a small molecule, having the same functional group as that of the main chain, afforded a variety of telechelic polymers with the functional groups derived from the small molecule at both ends.

Academic Significance and Societal Importance of the Research Achievements

重縮合において環状ポリマーを含まずに選択的にテレケリックポリマーを合成するための手法を開発するという問題提起がこれまで行われていなかった。さらにはこれまで常識的に良く行われていた、どちらかのモノマーを過剰に用いる重縮合において不可逆反応を用いると環状ポリマーが混ざるが、可逆反応にすれば選択的にテレケリックポリマーが生成するという可逆反応の重要性を明らかにした。この手法によって純度の高いテレケリックポリマーを社会に提供できるようになった。

Report

(4 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Annual Research Report
  • 2021 Annual Research Report
  • Research Products

    (25 results)

All 2023 2022 2021 Other

All Journal Article (7 results) (of which Peer Reviewed: 7 results) Presentation (16 results) (of which Int'l Joint Research: 8 results,  Invited: 6 results) Remarks (2 results)

  • [Journal Article] Introduction of end groups into cyclic poly(ether sulfone) by means of transetherification with bis(aryloxyphenyl) sulfone2023

    • Author(s)
      Okabayashi Ryouichi、Shirai Ken‐ichiro、Ohba Ryo、Katoh Takayoshi、Ohta Yoshihiro、Yokozawa Tsutomu
    • Journal Title

      Journal of Polymer Science

      Volume: 62 Issue: 7 Pages: 1323-1330

    • DOI

      10.1002/pol.20230779

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of polycarbonates and polycarbonate/polyester copolymers through an ester-carbonate exchange reaction2022

    • Author(s)
      Katoh Takayoshi、Saso Maai、Ohta Yoshihiro、Yokozawa Tsutomu
    • Journal Title

      Polymer Journal

      Volume: 54 Issue: 9 Pages: 1063-1069

    • DOI

      10.1038/s41428-022-00663-7

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Functionalization of poly(methyl acrylate) with formate esters and polyester through ester‐ester exchange reaction2022

    • Author(s)
      Katoh Takayoshi、Ohta Yoshihiro、Yokozawa Tsutomu
    • Journal Title

      Journal of Polymer Science

      Volume: 60 Issue: 17 Pages: 2591-2596

    • DOI

      10.1002/pol.20220013

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 重縮合における最近の進歩2022

    • Author(s)
      横澤勉, 岡林龍一, 加藤顕禎, 太田佳宏
    • Journal Title

      日本接着学会誌

      Volume: 58 Pages: 322-330

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Control of Polycondensation2022

    • Author(s)
      Yokozawa Tsutomu、Ohta Yoshihiro
    • Journal Title

      Macromolecular Engineering, 2nd Edition

      Volume: 2 Pages: 1-71

    • DOI

      10.1002/9783527815562.mme0013

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Importance of a reversible reaction for the synthesis of telechelic polymers by means of polycondensation using an excess of one monomer2022

    • Author(s)
      Katoh Takayoshi、Suzuki Tomoya、Ohta Yoshihiro、Yokozawa Tsutomu
    • Journal Title

      Polymer Chemistry

      Volume: 13 Issue: 6 Pages: 794-800

    • DOI

      10.1039/d1py01498f

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of polyester by means of polycondensation of diol ester and dicarboxylic acid ester through ester?ester exchange reaction2021

    • Author(s)
      Katoh Takayoshi、Ogawa Yukiko、Ohta Yoshihiro、Yokozawa Tsutomu
    • Journal Title

      Journal of Polymer Science

      Volume: 59 Issue: 9 Pages: 787-797

    • DOI

      10.1002/pol.20210032

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Presentation] エステル-カーボネート交換反応を利用した可逆的非等モル下重縮合による選択的鎖状ポリカーボネートの合成2023

    • Author(s)
      小林菜緒
    • Organizer
      第72回高分子学会年次大会
    • Related Report
      2023 Annual Research Report
  • [Presentation] エーテル-エーテル交換反応を利用した可逆的非等モル下重縮合による選択的鎖状ポリエーテルスルホンの合成2023

    • Author(s)
      大和怜央
    • Organizer
      第72回高分子学会年次大会
    • Related Report
      2023 Annual Research Report
  • [Presentation] Polymer reaction of poly(methyl acrylate) with various esters via ester-ester exchange reaction2023

    • Author(s)
      T. Katoh
    • Organizer
      The 13th SPSJ International Polymer Conference
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Selective synthesis of linear polycarbonate by reversible unstoichimetric polycondensation through ester-carbonate exchange reaction2023

    • Author(s)
      N. Kobayashi
    • Organizer
      The 13th SPSJ International Polymer Conference
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] エステル-カーボネート交換反応を利用したポリカーボネートの末端官能基化2023

    • Author(s)
      小林菜緒
    • Organizer
      第72回高分子討論会
    • Related Report
      2023 Annual Research Report
  • [Presentation] Synthesis of telechelic polymer free from cyclic polymer2022

    • Author(s)
      T. Yokozawa
    • Organizer
      Polycondensation 2022
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis of telechelic polymer free from cyclic polymer in polycondensation2022

    • Author(s)
      T. Yokozawa
    • Organizer
      15th Japan-Belgium Symposium on Polymer Science
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Importance of reversible reaction for the synthesis of telechelic polymer free from cyclic polymer in polycondensation2022

    • Author(s)
      T. Yokozawa
    • Organizer
      17th Pacific Polymer Conference (PPC 17)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ジオールエステルとジアルキルカーボネートの重縮合によるポリカーボネートの合成2022

    • Author(s)
      加藤顕禎
    • Organizer
      第71回高分子学会年次大会
    • Related Report
      2022 Annual Research Report
  • [Presentation] アルコキシ交換反応に基づく高分子合成及び高分子反応2022

    • Author(s)
      加藤顕禎
    • Organizer
      第71回高分子討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Importance of Reversible Reaction for the Synthesis of Telechelic Polymer in Polycondensation2021

    • Author(s)
      T. Yokozawa
    • Organizer
      IUPAC-MACRO2020+
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Importance of Reversible Reaction in Polycondensation2021

    • Author(s)
      T. Yokozawa
    • Organizer
      Taiwan-Japan Bilateral Polymer Symposium
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 縮合系高分子を用いる接着剤の耐熱化・高強度化2021

    • Author(s)
      横澤勉
    • Organizer
      接着学会西部支部令和3年度第二回講演会
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] エステル-エステル交換反応によるポリアクリレート側鎖の修飾2021

    • Author(s)
      加藤顕禎
    • Organizer
      第70回高分子学会年次大会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 種々のエステルとポリ(メチルアクリレート)とのエステル-エステル交換反応による高分子反応2021

    • Author(s)
      加藤顕禎
    • Organizer
      第70回高分子討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Synthesis of Telechelic Polyester through Unstoichiometric Polycondensation2021

    • Author(s)
      T. Katoh
    • Organizer
      Pacifichem 2021
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Remarks] 当研究室の業績と論文

    • URL

      http://apchem2.kanagawa-u.ac.jp/yokozawalab/frame.html

    • Related Report
      2023 Annual Research Report 2022 Annual Research Report 2021 Annual Research Report
  • [Remarks] 研究室・教職員の紹介 分子アーキテクチャー研究室

    • URL

      http://www.apchem.kanagawa-u.ac.jp/staff/012.html

    • Related Report
      2023 Annual Research Report 2022 Annual Research Report 2021 Annual Research Report

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Published: 2021-04-28   Modified: 2025-01-30  

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