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The Analysis of Thermo-Oxidative Degradation of Polymer Materials by CL-ST-ESR

Research Project

Project/Area Number 21K05146
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 34030:Green sustainable chemistry and environmental chemistry-related
Research InstitutionKyoto Institute of Technology

Principal Investigator

SAKAI Wataru  京都工芸繊維大学, 材料化学系, 教授 (70263176)

Project Period (FY) 2021-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2023: ¥520,000 (Direct Cost: ¥400,000、Indirect Cost: ¥120,000)
Fiscal Year 2022: ¥520,000 (Direct Cost: ¥400,000、Indirect Cost: ¥120,000)
Fiscal Year 2021: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Keywords高分子劣化 / 自動酸化反応 / ラジカル反応 / 電子スピン共鳴 / ケミルミネッセンス / ポリプロピレン / ナイロン / 自動酸化劣化 / 劣化 / 高分子材料 / ケミルミネッセンス(CL) / 電子スピン共鳴(ESR) / ラジカル
Outline of Research at the Start

本研究は、高分子材料を加熱したときに起こる酸化劣化の、これまで直接的に調べられなかった中間の反応経路をより詳しく解明することを目的として、材料の酸化状態を分析できるケミルミネッセンス(CL)測定と、短寿命ラジカル種を分析できるスピントラップ-電子スピン共鳴(ST-ESR)測定とを同時に行う手法を独自に構築し、高分子材料の加熱中に生じる過酸化物質およびラジカル反応中間体の挙動の相関性を詳しく調べるものである。本研究を通じて得られる成果は、高分子材料の寿命を原因療法的かつ能動的に制御するための重要な基礎情報であり、サステナブル社会の実現のために必要不可欠な知見となる。

Outline of Final Research Achievements

In this study, a CL-ST-ESR technique that simultaneously performs a chemiluminescence (CL) measurement to analyze peroxidation and a spin-trapping-electron spin resonance (ST-ESR) measurement to analyze short-lived radical species was developed, and the relationship of peroxidants and radical intermediates during the thermo-oxidative degradation of polymer materials was investigated in detail. As a result, a correlation between the formation of peroxidation-derived oxyradicals and carbonyl radicals and CL luminescence in polypropylene was found, and in nylon, the thermo-oxidation radical reactions in the practical temperature range and identified the sites of peroxidation were successfully measured. This method enables the analysis of thermo-oxidative degradation reactions of polymer materials that have not been directly observed before, and is expected to be applied more in the future.

Academic Significance and Societal Importance of the Research Achievements

高分子材料の劣化反応は主にラジカル反応を介して起こるとされているが、その中間体を直接観察した研究例はほとんどなく、これまでは劣化後の状態から帰納的に分析して反応経路が推測されてきた。本研究は、高分子材料の実際の使用環境下で起こる熱酸化劣化を直接的に観察することを目的として、反応途中に生じる短寿命ラジカル種および過酸化状態を同時に調べることのできる手法CL-ST-ESR法を開発し、いくつかの高分子材料の熱酸化劣化を研究対象として、この有用性を実証することができた。本手法は非常に高感度で直接的な反応解析が可能であり,従来は分析が行えなかった領域の情報を得るための手段となることが大いに期待される.

Report

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

    (26 results)

All 2024 2023 2022 2021 Other

All Journal Article (3 results) (of which Peer Reviewed: 3 results,  Open Access: 1 results) Presentation (21 results) (of which Int'l Joint Research: 5 results,  Invited: 9 results) Remarks (2 results)

  • [Journal Article] Direct observation of the thermo-oxidative degradation of PA66 by spin-trapping ESR analysis2023

    • Author(s)
      Kurima Akihiro、Nguyen Thu Anh、Kinashi Kenji、Sakai Wataru、Tsutsumi Naoto
    • Journal Title

      Polymer Degradation and Stability

      Volume: 215 Pages: 110429-110429

    • DOI

      10.1016/j.polymdegradstab.2023.110429

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Spin Trapping Analysis of Radical Intermediates on the Thermo-Oxidative Degradation of Polypropylene2022

    • Author(s)
      Nguyen Thu Anh、Lim Hui Ming、Kinashi Kenji、Sakai Wataru、Tsutsumi Naoto、Okubayashi Satoko、Hosoda Satoru、Sato Tetsu
    • Journal Title

      Polymers

      Volume: 15 Issue: 1 Pages: 200-200

    • DOI

      10.3390/polym15010200

    • Related Report
      2022 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Spin trapping analysis of the thermal degradation of polypropylene2022

    • Author(s)
      Thu Anh Nguyen, Shota Ichise, Kenji Kinashi, Wataru Sakai, Naoto Tsutsumi, Satoko Okubayashi
    • Journal Title

      Polymer Degradation and Stability

      Volume: 197 Pages: 109871-109871

    • DOI

      10.1016/j.polymdegradstab.2022.109871

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Presentation] Radical Reaction Analysis of Polymer Materials by Electron Spin Resonance2024

    • Author(s)
      Wataru SAKAI
    • Organizer
      KIT-ASEAN Joint Symposium 2024
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] CL-ESR分析によるポリプロピレンの熱酸化劣化反応の解析2023

    • Author(s)
      坂井 亙, Nguyen Anh Thu,木梨 憲司,細田 覚,佐藤 哲
    • Organizer
      マテリアルライフ学会,第34回研究発表会
    • Related Report
      2023 Annual Research Report
  • [Presentation] スピントラップ法による高分子材料の劣化反応のラジカル解析2023

    • Author(s)
      坂井 亙
    • Organizer
      第26回ESRフォーラム研究会
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] 高分子材料の劣化反応とラジカル反応解析2023

    • Author(s)
      坂井 亙
    • Organizer
      東京工業大学特別講演会
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] スピントラップ法による高分子材料の劣化反応のラジカル解析2023

    • Author(s)
      坂井 亙
    • Organizer
      高分子学会,高分子計算機科学研究会
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] 高分子材料の劣化とラジカル反応解析2023

    • Author(s)
      坂井 亙
    • Organizer
      クラレ,くらしき研究センター特別講演
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] ゴム材料におけるラジカル反応解析2023

    • Author(s)
      坂井 亙
    • Organizer
      日本ゴム協会,令和5年度広島高分子材料研修会(広島ゴム技術員会2月例会講演会)
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] SPIN TRAPPING & CHEMILUMINESCENCE ANALYSIS OF THERMO-OXIDATION OF POLYPROPYLENE2023

    • Author(s)
      Thu Anh Nguyen, Yutaro Muramatsu, Kenji Kinashi, and Wataru Sakai
    • Organizer
      マテリアルライフ学会主催:第15回ケミルミネッセンス研究会
    • Related Report
      2022 Research-status Report
    • Invited
  • [Presentation] Investigation of Thermo-Oxidative Degradation of Polypropylene using ESR and CL2022

    • Author(s)
      Thu Anh NGUYEN, Kenji KINASHI, Wataru SAKAI*, Naoto TSUSTUMI
    • Organizer
      日本ゴム協会2022年年次大会
    • Related Report
      2022 Research-status Report
  • [Presentation] Oxidation Degradation of Polymer Materials2022

    • Author(s)
      NGUYEN Anh Thu, KINASHI Kenji, SAKAI Wataru
    • Organizer
      第25回ESRフォーラム研究会
    • Related Report
      2022 Research-status Report
  • [Presentation] Investigation of Thermo-Oxidative Degradation of Polypropylene Using Simultaneous CL-ESR Measurement2022

    • Author(s)
      Thu Anh Nguyen, Yutaro Muramatsu, Kenji Kinashi, Wataru Sakai, and Naoto Tsustumi
    • Organizer
      第61回電子スピンサイエンス学会年会
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research
  • [Presentation] Investigation of Thermo-Oxidative Degradation of Polypropylene Using Simultaneous CL-ESR Measurement2022

    • Author(s)
      Thu Anh Nguyen, Yutaro Muramatsu, Kenji Kinashi, and Wataru Sakai
    • Organizer
      日本ゴム協会第33 回エラストマー討論会
    • Related Report
      2022 Research-status Report
  • [Presentation] スピントラップ法によるゴム材料の劣化反応のラジカル解析2022

    • Author(s)
      坂井 亙
    • Organizer
      日本ゴム協会・第160回環境劣化研究分科会
    • Related Report
      2022 Research-status Report
    • Invited
  • [Presentation] スピントラップ法によるゴム材料の劣化反応のラジカル解析2022

    • Author(s)
      坂井 亙
    • Organizer
      日本ゴム協会・第282回ゴム技術シンポジウム
    • Related Report
      2022 Research-status Report
    • Invited
  • [Presentation] スピントラップ法による高分子材料の劣化反応のラジカル解析2022

    • Author(s)
      坂井 亙
    • Organizer
      高分子学会主催・高分子同友会・高分子に関する最新の技術および市場を勉強する会
    • Related Report
      2022 Research-status Report
    • Invited
  • [Presentation] Spin-Trapping Analysis for Thermal Degradation Polypropylene Fabric Using Supercritical Carbon Dioxide2022

    • Author(s)
      Thu Anh Nguyen, Kenji Kinashi, Wataru Sakai, Naoto Tsutsumi, and Satoko Okubayashi
    • Organizer
      3rd JAPAN-ASEAN Seminar 2022
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research
  • [Presentation] 高分子材料の酸化劣化とラジカル2022

    • Author(s)
      Nguyen Anh Thu,Lim Ming Hui,木梨 憲司,坂井 亙,佐藤 哲
    • Organizer
      マテリアルライフ学会第26回春季年次大会
    • Related Report
      2021 Research-status Report
  • [Presentation] Spin-Trapping Analysis for Thermal Degradation Polypropylene Fiber Using Supercritical Carbon Dioxide2021

    • Author(s)
      Thu Anh Nguyen, Kenji Kinashi, Wataru Sakai, Naoto Tsutsumi, and Satoko Okubayashi
    • Organizer
      日本ゴム協会2021年年次大会
    • Related Report
      2021 Research-status Report
  • [Presentation] Spin-Trapping Analysis for Thermal Degradation Polypropylene Fiber Using Supercritical Carbon Dioxide2021

    • Author(s)
      Thu Anh Nguyen, Kenji Kinashi, Wataru Sakai, Naoto Tsutsumi, and Satoko Okubayashi
    • Organizer
      高分子学会第70回年次大会
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research
  • [Presentation] Spin-Trapping Analysis for Thermo-Oxidative Degradation of Polypropylene2021

    • Author(s)
      Thu Anh Nguyen, Kenji Kinashi, Wataru Sakai, Naoto Tsutsumi, and Satoko Okubayashi
    • Organizer
      ISMAR-APNMR-NMRSJ-SEST2021
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research
  • [Presentation] Spin-Trapping Analysis for Thermo-Oxidative Degradation of Polypropylene2021

    • Author(s)
      Thu Anh Nguyen, Kenji Kinashi, Wataru Sakai
    • Organizer
      第24回ESRフォーラム研究会
    • Related Report
      2021 Research-status Report
  • [Remarks] Functional Polymer Design Laboratory

    • URL

      http://www.cis.kit.ac.jp/~fpd/

    • Related Report
      2021 Research-status Report
  • [Remarks] 京都工芸繊維大学・研究者総覧・坂井 亙

    • URL

      https://www.hyokadb.jim.kit.ac.jp/profile/ja.2f965ca8f50ea3fc4fdbfb781cece39a.html

    • Related Report
      2021 Research-status Report

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

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