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Development of Metal-Free Click Reactions and Their Application to Polymeric Materials

Research Project

Project/Area Number 15H03863
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Polymer/Textile materials
Research InstitutionTokyo Institute of Technology

Principal Investigator

Michinobu Tsuyoshi  東京工業大学, 物質理工学院, 准教授 (80421410)

Project Period (FY) 2015-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥16,770,000 (Direct Cost: ¥12,900,000、Indirect Cost: ¥3,870,000)
Fiscal Year 2018: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Fiscal Year 2017: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Fiscal Year 2016: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000)
Fiscal Year 2015: ¥6,890,000 (Direct Cost: ¥5,300,000、Indirect Cost: ¥1,590,000)
Keywords高分子合成 / 合成化学 / 環境材料 / 構造・機能材料 / クリックケミストリー
Outline of Final Research Achievements

It was found that dehydrobenzo[12]annulene derivatives undergo cycloaddition reactions with 2 equivalents of organic azides under mild conditions without metal catalysts, yielding emissive triazole products. This reaction was applied to polyaddition to produce linear polymers. In addition, when dehydrobenzo[12]annulene derivatives were used as a crosslinker of partially azidated polymers, mechanically tough crosslinked polymer films were formed. Since the emissive sites were fixed as crosslinking points in the polymer films, the crosslinked polymer films showed excellent oxygen sensitivities.

Academic Significance and Societal Importance of the Research Achievements

高価な金属触媒を使用せずに機能性材料を創製することができればコスト削減に繋がるため非常に意義深い。本研究では、環境負荷が低い効率的な反応を金属触媒無しで実施する方法を確立した。また、この方法を用いると様々な機能性高分子材料を製造することができた。特に強調すべきポイントは、高価な発光性色素を添加しないでも十分に強く光る高分子膜を製造できた点である。光る高分子膜は酸素に応答して発光強度が減少するため、航空機の風洞試験や構造物のひび割れ検出などに利用できる可能性がある。

Report

(5 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Annual Research Report
  • 2016 Annual Research Report
  • 2015 Annual Research Report
  • Research Products

    (38 results)

All 2019 2018 2017 2016 2015 Other

All Journal Article (13 results) (of which Int'l Joint Research: 3 results,  Peer Reviewed: 11 results,  Open Access: 3 results,  Acknowledgement Compliant: 3 results) Presentation (21 results) (of which Int'l Joint Research: 4 results,  Invited: 3 results) Book (2 results) Remarks (2 results)

  • [Journal Article] Strain-Promoted Double Azide Addition to Octadehydrodibenzo[12]annulene Derivatives2019

    • Author(s)
      S. Fukushima, M. Ashizawa, S. Kawauchi, T. Michinobu
    • Journal Title

      Helv. Chim. Acta

      Volume: 102 Issue: 4

    • DOI

      10.1002/hlca.201900016

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Functional Covalent Layer-by-Layer Thin Films by [2+2] Cycloaddition-Retroelectrocyclization2018

    • Author(s)
      H. Fujita,T. Michinobu
    • Journal Title

      ACS Macro Lett.

      Volume: 7 Issue: 6 Pages: 716-719

    • DOI

      10.1021/acsmacrolett.8b00365

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Antibacterial Polymeric Films Fabricated by [2+2] Cycloaddition-Retroelectrocyclization and Ag+ Ion Coordination2018

    • Author(s)
      H. Fujita, N. Nihei, M. Bito, T. Michinobu
    • Journal Title

      Macromol. Biosci.

      Volume: 18 Issue: 12 Pages: 1800336-1800336

    • DOI

      10.1002/mabi.201800336

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Covalent Layer-by-Layer Thin Films with Charge-Transfer Chromophores: Side Chain Engineering for the Efficient Ag+ Ion Recognition from Aqueous Solutions2018

    • Author(s)
      H. Fujita,T. Michinobu
    • Journal Title

      Soft Matter

      Volume: 14 Issue: 44 Pages: 9055-9060

    • DOI

      10.1039/c8sm01986j

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] クリックケミストリーによる新高分子材料合成2018

    • Author(s)
      道信 剛志
    • Journal Title

      機能材料

      Volume: 38 Pages: 12-20

    • Related Report
      2018 Annual Research Report
  • [Journal Article] Temperature Compensation of Pressure-Sensitive Luminescent Polymer Sensors2018

    • Author(s)
      S. Sano, T. Yuuki, T. Hyakutake, K. Morita, H. Sakaue, S. Arai, H. Matsumoto, T. Michinobu
    • Journal Title

      Sens. Actuator B-Chem.

      Volume: 255 Pages: 1960-1966

    • DOI

      10.1016/j.snb.2017.08.221

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] The [2+2] Cycloaddition-Retroelectrocyclization (CA-RE) Click Reaction: Facile Access to Molecular and Polymeric Push-Pull Chromophores2018

    • Author(s)
      T. Michinobu, F. Diederich
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 57 Issue: 14 Pages: 3552-3557

    • DOI

      10.1002/anie.201711605

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Polymeric Chemosensors: A Conventional Platform with New Click Chemistry2017

    • Author(s)
      Y. Wang, T. Michinobu
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 90 Issue: 12 Pages: 1388-1400

    • DOI

      10.1246/bcsj.20170294

    • NAID

      130006250393

    • ISSN
      0009-2673, 1348-0634
    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Colorimetric Ion Sensors Based on Polystyrenes Bearing Side Chain Triazole and Donor–Acceptor Chromophores2017

    • Author(s)
      Y. Li, Y. Washino, T. Hyakutake, T. Michinobu
    • Journal Title

      Analytical Sciences

      Volume: 33 Issue: 5 Pages: 599-604

    • DOI

      10.2116/analsci.33.599

    • NAID

      130006777383

    • ISSN
      0910-6340, 1348-2246
    • Related Report
      2017 Annual Research Report 2016 Annual Research Report
    • Peer Reviewed
  • [Journal Article] クリックケミストリーを用いた高分子合成2017

    • Author(s)
      道信 剛志
    • Journal Title

      CHEMISTRY & EDUCATION

      Volume: 65 Issue: 9 Pages: 444-445

    • DOI

      10.20665/kakyoshi.65.9_444

    • NAID

      130006413321

    • ISSN
      0386-2151, 2424-1830
    • Related Report
      2017 Annual Research Report
  • [Journal Article] Side-Chain Engineering of Polyphenylacetylene Derivatives for Tuning the Self-Assembly and Gas Permeability Properties2017

    • Author(s)
      Y. Li, H. Fujita, T. Hyakutake, T. Michinobu
    • Journal Title

      Journal of Fiber Science and Technology

      Volume: 73 Issue: 4 Pages: 82-86

    • DOI

      10.2115/fiberst.2017-0011

    • NAID

      130005562233

    • ISSN
      2189-7654
    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Cross-Linking and Postfunctionalization of Polymer Films by Utilizing the Orthogonal Reactivity of 7,7,8,8-Tetracyanoquinodimethane2016

    • Author(s)
      Y. Washino, T. Michinobu
    • Journal Title

      Phys. Chem. Chem. Phys.

      Volume: 18 Issue: 4 Pages: 2288-2291

    • DOI

      10.1039/c5cp05180k

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] High Performacne Triazole-Containing Brush Polymers via Azide-Alkyne Click Chemistry: A New Functional Polymer Platform for Electrical Memory Devices2015

    • Author(s)
      S. Song, Y.-G. Ko, H. Lee, D. Wi, B. J. Ree, Y. Li, T. Michinobu, M. Ree
    • Journal Title

      NPG Asia Mater.

      Volume: 7 Issue: 12 Pages: e228-e228

    • DOI

      10.1038/am.2015.130

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Presentation] [2+2]付加環化反応を用いたマルチカラー高分子の合成2018

    • Author(s)
      道信 剛志
    • Organizer
      第67回高分子討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] クリック反応を利用した新しい高窒素含有エネルギーポリマーの合成研究2017

    • Author(s)
      道信 剛志
    • Organizer
      火薬学会2017年度春季研究発表会
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] ポリエチレングリコール鎖が付加したデヒドロベンゾ[12]アヌレン誘導体のクリック合成と蛍光特性2017

    • Author(s)
      兼平 航至、道信 剛志
    • Organizer
      第66回高分子年次大会
    • Related Report
      2017 Annual Research Report 2016 Annual Research Report
  • [Presentation] 新規ビストリアゾール環状分子の発光特性と金属イオンおよびアクセプター分子の認識に関する研究2017

    • Author(s)
      永井 良樹、道信 剛志
    • Organizer
      平成29年度繊維学会年次大会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Chiral Induction from Troeger’s Base into Twisted 1,1,4,4-Tetracyanobuta-1,3-dienes (TCBDs)2017

    • Author(s)
      W. Li, T. Michinobu
    • Organizer
      Chirality 2017
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Supramolecular Materials by Macromolecular Silver Ion Complexes2017

    • Author(s)
      T. Michinobu
    • Organizer
      IUPAC 17th International Symposium on MacroMolecular Complexes (MMC-17)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Improvement and New Application of Pressure-Sensitive Paints2017

    • Author(s)
      T. Michinobu, S. Sano, A. Hamasaki, T. Hyakutake, H. Nitta
    • Organizer
      第66回高分子討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] ポリ(1,8-カルバゾール)誘導体のクリック合成とイオン認識能の評価2016

    • Author(s)
      多根 静香、道信 剛志
    • Organizer
      第65回高分子討論会
    • Place of Presentation
      神奈川大学
    • Year and Date
      2016-09-14
    • Related Report
      2016 Annual Research Report
  • [Presentation] 歪んだアルキンとアジドのクリック反応を利用したネットワークポリマーの作製と蛍光特性の評価2016

    • Author(s)
      福島 智美、道信 剛志
    • Organizer
      第65回高分子討論会
    • Place of Presentation
      神奈川大学
    • Year and Date
      2016-09-14
    • Related Report
      2016 Annual Research Report
  • [Presentation] 発光型ひび割れ検出塗膜の気体透過性と検出感度に関する検討2016

    • Author(s)
      百武 壮、西崎 到、新田 弘之、道信 剛志
    • Organizer
      土木学会平成28年度全国大会第71回年次学術講演会
    • Place of Presentation
      東北大学
    • Year and Date
      2016-09-07
    • Related Report
      2016 Annual Research Report
  • [Presentation] 電子求引性基を持つデヒドロベンゾアヌレン化合物の合成とクリック反応による高分子架橋への応用2016

    • Author(s)
      武田 直樹、道信 剛志
    • Organizer
      平成28年度繊維学会年次大会
    • Place of Presentation
      タワーホール船堀
    • Year and Date
      2016-06-08
    • Related Report
      2016 Annual Research Report 2015 Annual Research Report
  • [Presentation] 新規ビストリアゾール環状分子の発光特性と金属イオンおよびアクセプター分子の認識に関する研究2016

    • Author(s)
      永井 良樹、道信 剛志
    • Organizer
      平成29年度繊維学会年次大会
    • Place of Presentation
      タワーホール船堀
    • Year and Date
      2016-06-07
    • Related Report
      2016 Annual Research Report
  • [Presentation] 1,8-位連結カルバゾールを主鎖に含む高分子のクリック合成と金属イオン認識能の評価2015

    • Author(s)
      多根 静香、道信 剛志
    • Organizer
      繊維学会関東支部平成27年度学生論文発表会
    • Place of Presentation
      東京農工大学
    • Year and Date
      2015-12-19
    • Related Report
      2015 Annual Research Report
  • [Presentation] 電子求引型デヒドロベンゾアヌレン化合物の合成とクリック反応による蛍光特性の調査2015

    • Author(s)
      武田 直樹、道信 剛志
    • Organizer
      繊維学会関東支部平成27年度学生論文発表会
    • Place of Presentation
      東京農工大学
    • Year and Date
      2015-12-19
    • Related Report
      2015 Annual Research Report
  • [Presentation] New Redox-Active Multilayer Thin Films and Their Silver Complexes by Alkyne-Acceptor Click Chemistry2015

    • Author(s)
      T. Michinobu
    • Organizer
      The International Chemical Congress of Pacific Basin Societies (Pacifichem 2015)
    • Place of Presentation
      Hawaii, USA
    • Year and Date
      2015-12-15
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] A New Metal-Free Azide-Alkyne Click Reaction for Self-Healing Polymer Films2015

    • Author(s)
      S. Fukushima, T. Michinobu
    • Organizer
      The International Chemical Congress of Pacific Basin Societies (Pacifichem 2015)
    • Place of Presentation
      Hawaii, USA
    • Year and Date
      2015-12-15
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] デヒドロベンゾアヌレン化合物のクリック反応による蛍光特性の発現と架橋剤への応用2015

    • Author(s)
      福島 智美、道信 剛志
    • Organizer
      平成27年度繊維学会秋季研究発表会
    • Place of Presentation
      京都工芸繊維大学
    • Year and Date
      2015-10-22
    • Related Report
      2015 Annual Research Report
  • [Presentation] 1,8-位連結カルバゾールを主鎖に含む高分子のクリック合成と金属イオン認識能の評価2015

    • Author(s)
      多根 静香、道信 剛志
    • Organizer
      平成27年度繊維学会秋季研究発表会
    • Place of Presentation
      京都工芸繊維大学
    • Year and Date
      2015-10-22
    • Related Report
      2015 Annual Research Report
  • [Presentation] デヒドロベンゾアヌレン化合物のクリック反応による位置選択性と二官能性モノマーへの展開2015

    • Author(s)
      福島 智美、道信 剛志
    • Organizer
      平成27年度繊維学会年次大会
    • Place of Presentation
      タワーホール船堀
    • Year and Date
      2015-06-10
    • Related Report
      2015 Annual Research Report
  • [Presentation] 1,8-ジエチニルカルバゾール誘導体のクリック重合とイオンセンサーへの応用2015

    • Author(s)
      多根 静香、道信 剛志
    • Organizer
      平成27年度繊維学会年次大会
    • Place of Presentation
      タワーホール船堀
    • Year and Date
      2015-06-10
    • Related Report
      2015 Annual Research Report
  • [Presentation] 電荷移動部位への銀イオン認識に基づくメカノクロミック材料の開発2015

    • Author(s)
      佐野 祥子、道信 剛志
    • Organizer
      平成27年度繊維学会年次大会
    • Place of Presentation
      タワーホール船堀
    • Year and Date
      2015-06-10
    • Related Report
      2015 Annual Research Report
  • [Book] Encyclopedia of Polymer Applications2018

    • Author(s)
      T. Michinobu, Y. Wang
    • Total Pages
      2954
    • Publisher
      Taylor & Francis
    • Related Report
      2018 Annual Research Report 2017 Annual Research Report
  • [Book] Organometallics and Related Molecules for Energy Conversion2015

    • Author(s)
      T. Michinobu
    • Publisher
      Springer
    • Related Report
      2015 Annual Research Report
  • [Remarks] 東京工業大学 道信研究室

    • URL

      http://www.op.titech.ac.jp/lab/michinobu/jp/index.html

    • Related Report
      2018 Annual Research Report 2017 Annual Research Report 2016 Annual Research Report
  • [Remarks] 東京工業大学 道信研究室

    • URL

      http://www.op.titech.ac.jp/lab/michinobu/jp/index.html

    • Related Report
      2015 Annual Research Report

URL: 

Published: 2015-04-16   Modified: 2020-03-30  

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