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Chemoselective polycondensation of functional thiophene-based monomers using zincate complex

Research Project

Project/Area Number 24655097
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeSingle-year Grants
Research Field Polymer chemistry
Research InstitutionYamagata University (2013)
Tokyo Institute of Technology (2012)

Principal Investigator

HIGASHIHARA Tomoya  山形大学, 理工学研究科, 准教授 (50504528)

Project Period (FY) 2012-04-01 – 2014-03-31
Project Status Completed (Fiscal Year 2013)
Budget Amount *help
¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2013: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
Fiscal Year 2012: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Keywords半導体高分子 / 精密合成 / 亜鉛錯体 / 重縮合 / ポリチオフェン / π共役系高分子 / 精密重合 / アート錯体 / チオフェン / 根岸カップリング / 有機薄膜太陽電池
Research Abstract

Regioregular poly(3-hexylthiophene) (P3HT) has been a commonly used p-type semi-conducting material for solution processable organic electronics. To establish a living system of"Negishi-type Catalyst-Transfer Polycondensation" using zincate complex as a synthetic method for well-defined P3HT, the ligands of Ni catalyst were optimized. As a result, a ligand of 1,2-bis(dicyclohexylphosphino)ethane produced P3HTs with highly controlled number average molecular weights (1,700-33,000) and very low D values (1.03-1.17). The polymerization results were strongly influenced by steric hindrance and/or electron-donating ability of the ligands. In addition, we succeeded in the post-polymerization of P3HT and the synthesis of P3HT-b-Poly(3-octadecylthiophene), the latter of which is the first demonstration by NCTP using zincate complex. This methodology could also apply to an electron-deficient monomer containing the naphthalene bisimide group to synthesize an n-type semi-conducting material.

Report

(3 results)
  • 2013 Annual Research Report   Final Research Report ( PDF )
  • 2012 Research-status Report
  • Research Products

    (42 results)

All 2014 2013 2012 Other

All Journal Article (5 results) (of which Peer Reviewed: 5 results) Presentation (35 results) (of which Invited: 8 results) Remarks (2 results)

  • [Journal Article] Controlled synthesis of low-polydisperse regioregular poly(3-hexylthiophene) and related materials by zincate-complex metathesis polymerization2014

    • Author(s)
      T. Higashihara, E. Goto
    • Journal Title

      Polym. J.

      Volume: 46(Advance online publication) Issue: 7 Pages: 381-390

    • DOI

      10.1038/pj.2014.14

    • NAID

      40020109494

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Precision Synthesis of Tailor-made Polythiophene-based Materials and Their Application to Organic Solar Cells2013

    • Author(s)
      T. Higashihara, M. Ueda
    • Journal Title

      Macromol. Res.

      Volume: 21 Issue: 3 Pages: 257-271

    • DOI

      10.1007/s13233-013-1123-5

    • Related Report
      2013 Final Research Report 2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Characterization of All-Conjugated Graft Copolymers Comprised of n-Type or p-Type Backbones and Poly(3-hexylthiophene) Side Chains2013

    • Author(s)
      J. Wang, C. Lu, T. Mizobe, M. Ueda, W. C Chen, T. Higashihara
    • Journal Title

      Macromolecules

      Volume: 46 Issue: 5 Pages: 1783-1793

    • DOI

      10.1021/ma400043s

    • Related Report
      2013 Final Research Report 2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Postfunctionalization of Rod-Coil Diblock and Coil-Rod-Coil Triblock Copolymers Composed of Poly(3-hexylthiophene) and Poly(4-(4' -N, N-dihexylaminophenylethynyl)styre ne) Segments2012

    • Author(s)
      H. Fujita, T. Michinobu, M. Tokita, M. Ueda, T. Higashihara
    • Journal Title

      Macromolecules

      Volume: Vol.45, No.24 Issue: 24 Pages: 9643-9656

    • DOI

      10.1021/ma301692b

    • Related Report
      2013 Final Research Report 2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Thiophene-Basedπ-Conjugated Polymers Containing Oxadiazole or Thiadiazole Moieties and Their Application to Organic Photovoltaics2012

    • Author(s)
      T.Higashihara, H.C. Wu, T. Mizobe, C Lu, M. Ueda, W. C. Chen
    • Journal Title

      Macromolecules

      Volume: 45 Issue: 22 Pages: 9046-9055

    • DOI

      10.1021/ma302005j

    • Related Report
      2013 Final Research Report 2012 Research-status Report
    • Peer Reviewed
  • [Presentation] ポリチオフェン類の精密合成と有機太陽電池材料への応用2014

    • Author(s)
      東原知哉
    • Organizer
      野口遵助成金講演会
    • Place of Presentation
      野口研究所、東京・竹橋・如水会館
    • Year and Date
      2014-03-11
    • Related Report
      2013 Final Research Report
  • [Presentation] Precision Synthesis of Tailor-made Polythiophene-based Materials and Their Application to Organic Solar Cells2014

    • Author(s)
      T. Higashihara
    • Organizer
      The 3rd International Symposium of Green Map Institute and Life 3D-Printing Innovation Center at Yamagata University
    • Place of Presentation
      Yonezawa, Yamagata, Japan
    • Related Report
      2013 Final Research Report
  • [Presentation] Precision Synthesis of Tailor-made Polythiophene-based Materials and Their Application to Organic Solar Cells2014

    • Author(s)
      Tomoya Higashihara
    • Organizer
      The 3rd International Symposium of Green Map Institute and Life 3D-Printing Innovation Center at Yamagata University
    • Place of Presentation
      山形大学
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] ポリチオフェンの精密合成と有機薄膜太陽電池材料への応用2013

    • Author(s)
      東原知哉
    • Organizer
      第49回茨城地区活動講演会
    • Place of Presentation
      住友化学(株)
    • Year and Date
      2013-11-27
    • Related Report
      2013 Annual Research Report 2013 Final Research Report
  • [Presentation] Precision Synthesis of Regioregular Poly(3-hexylthiophene) Using Zincate Complex2013

    • Author(s)
      T. Higashihara
    • Organizer
      The 13th Pacific Polymer Conference (PPC2013)
    • Place of Presentation
      Kaohsiung, Taiwan
    • Related Report
      2013 Final Research Report
  • [Presentation] Precision Synthesis of Regioregular Poly(3-hexylthiophene) Using Zincate Complex2013

    • Author(s)
      T. Higashihara
    • Organizer
      10th IUPAC International Conference on Advanced Polymers via Maclomolecular Engineering (APME2013)
    • Place of Presentation
      Durham University, Durham, UK.
    • Related Report
      2013 Final Research Report
  • [Presentation] Synthesis of New Thiadiazole-Containing Polythiophene Derivatives and Their Application to Organic Solar Cells2013

    • Author(s)
      T. Higashihara, T. Mizobe, W. C. Chen, M. Ueda
    • Organizer
      The 30th International Conference of Photopolymer Science and Technology, Materials & Process for Advanced Microlithography and Nanotechnology
    • Place of Presentation
      Chiba, Japan
    • Related Report
      2013 Final Research Report
  • [Presentation] Precision Synthesis of Tailor-made Polythiophene-based Materials and Their Application to Organic Solar Cells2013

    • Author(s)
      T. Higashihara
    • Organizer
      第93春季年会Asian International Symposium-Polymer-
    • Place of Presentation
      立命館大学, 滋賀
    • Related Report
      2013 Final Research Report
  • [Presentation] Synthesis of Block Copolymers and Their Application to Organic Photovoltaics2013

    • Author(s)
      T. Higashihara
    • Organizer
      4th International Symposium for Young Organic Chemists (ISYOC)
    • Place of Presentation
      NIMS, Tsukuba
    • Related Report
      2013 Final Research Report
  • [Presentation] Synthesis of New Thiadiazole-Containing Polythiophene Derivatives and Their Application to Organic Solar Cells2013

    • Author(s)
      Tomoya Higashihara, Tetsunari Mizobe, We-Chang Chen and Mitsuru Ueda
    • Organizer
      The 30th International Conference of Photopolymer Science and Technology, Materials & Process for Advanced Microlithography and Nanotechnology
    • Place of Presentation
      千葉大学
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Precision Synthesis of Regioregular Poly(3-hexylthiophene) Using Zincate Complex2013

    • Author(s)
      Tomoya Higashihara
    • Organizer
      The 13th Pacific Polymer Conference (PPC2013)
    • Place of Presentation
      Grand Hi-Lai Arena, Kaohsiung, Taiwan
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Precision Synthesis of Regioregular Poly(3-hexylthiophene) Using Zincate Complex2013

    • Author(s)
      Tomoya Higashihara
    • Organizer
      10th IUPAC International Conference on Advanced Polymers via Maclomolecular Engineering (APME2013)
    • Place of Presentation
      Durham University, Durham, UK
    • Related Report
      2013 Annual Research Report
  • [Presentation] Synthesis of Block Copolymers and Their Application to Organic Photovoltaics2013

    • Author(s)
      Tomoya Higashihara
    • Organizer
      4th International Symposium for Young Organic Chemists (ISYOC)
    • Place of Presentation
      物材機構、筑波
    • Related Report
      2012 Research-status Report
    • Invited
  • [Presentation] Precision Synthesis of Tailor-made Polythiophene-based Materials Precision Synthesis of Tailor-made Polythiophene-based Materials and Their Application to Organic Solar Cells2013

    • Author(s)
      Tomoya Higashihara
    • Organizer
      第93春季年会Asian International Symposium-Polymer-
    • Place of Presentation
      立命館大学、滋賀
    • Related Report
      2012 Research-status Report
    • Invited
  • [Presentation] 含ポリチオフェン鎖共重合体の合成と有機薄膜太陽電池への応用2012

    • Author(s)
      東原知哉
    • Organizer
      グループ研究セミナー「先端光科学技術と光機能性材料開発の最前線」
    • Place of Presentation
      横浜国立大学
    • Year and Date
      2012-12-21
    • Related Report
      2013 Final Research Report 2012 Research-status Report
  • [Presentation] All-conjugated Graft Copolymers with P3HT Brushes via Grafting-From Process2012

    • Author(s)
      J. Wang, T. Higashihara, M. Ueda
    • Organizer
      The 9th SPSJ International Polymer Conference (IPC 2012)
    • Place of Presentation
      Kobe, Japan
    • Related Report
      2013 Final Research Report
  • [Presentation] Synthesis of Block Copolymers with Poly(3-hexylthiophene) Segments and Their Application to Organic Photovoltaics2012

    • Author(s)
      T. Higashihara, M. Ueda, and M. Ree
    • Organizer
      The 9th SPSJ International Polymer Conference (IPC 2012)
    • Place of Presentation
      Kobe, Japan
    • Related Report
      2013 Final Research Report
  • [Presentation] 半導体ブロック共重合体の合成と有機薄膜太陽電池への応用2012

    • Author(s)
      東原知哉、Ryo Yecheol、Ree Moonhor、上田充
    • Organizer
      第61回高分子討論会
    • Place of Presentation
      名古屋工業大学
    • Related Report
      2013 Final Research Report
  • [Presentation] 深HOMO化ポリチオフェン誘導体の合成と有機薄膜太陽電池への応用2012

    • Author(s)
      チョンミンアン、東原知哉、上田充
    • Organizer
      第61回高分子討論会
    • Place of Presentation
      名古屋工業大学
    • Related Report
      2013 Final Research Report
  • [Presentation] Protection-free Synthesis of Functionalized Polythiophene Derivatives by Using Zincate Complex2012

    • Author(s)
      E. Goto, T. Higashihara, M. Ueda
    • Organizer
      Polycondensation2012 Meeting
    • Place of Presentation
      San Francisco,CA, USA
    • Related Report
      2013 Final Research Report
  • [Presentation]2012

    • Author(s)
      T. Mizobe, T. Higashihara, H. C. Wu, C. Lu, W. C. Chen, M. Ueda
    • Organizer
      Polycondensation2012 Meeting
    • Place of Presentation
      San Francisco,CA, USA
    • Related Report
      2013 Final Research Report
  • [Presentation] Enhancement of P3HT/PCBM photovoltaic efficiency and stability based on surfactant approach2012

    • Author(s)
      T. Higashihara, Y. C. Lai, J. H. Tsai, W. C. Chen, and M. Ueda
    • Organizer
      244th ACS National Meeting
    • Place of Presentation
      Philadelphia, PA, USA
    • Related Report
      2013 Final Research Report
  • [Presentation] Purification-free and Regioregular Poly(3-hexylthiophene)2012

    • Author(s)
      T. Higashihara
    • Organizer
      Poly International Symposium on Polymer Chemistry (PC2012)
    • Place of Presentation
      Changchun, China
    • Related Report
      2013 Final Research Report
  • [Presentation] 両親媒性ブロックコポリチオフェンの合成と相分離観察2012

    • Author(s)
      東原知哉、大清水薫、Yecheol Ryo、高橋歩、Moonhor Ree、上田充
    • Organizer
      第61回高分子年次大会
    • Place of Presentation
      横浜
    • Related Report
      2013 Final Research Report 2012 Research-status Report
  • [Presentation] 亜鉛アート錯体を用いたポリ(3-(6-ヒドロキシ)ヘキシルチオフェン)の合成2012

    • Author(s)
      後藤栄祐、東原知哉、上田充
    • Organizer
      第61回高分子年次大会
    • Place of Presentation
      横浜
    • Related Report
      2013 Final Research Report 2012 Research-status Report
  • [Presentation] オキサジアゾールまたはチアジアゾールを主鎖に有する新規共役系高分子の合成2012

    • Author(s)
      溝邉哲成、東原知哉、上田充
    • Organizer
      第61回高分子年次大会
    • Place of Presentation
      横浜
    • Related Report
      2013 Final Research Report 2012 Research-status Report
  • [Presentation] PURIFICATION-FREE AND PROTECTION-FREE SYNTHESIS OF REGIOREGULAR POLY(3-HEXYLTHIOPHENE) AND POLY(3-(6-HYDROXYHEXYL)THIOPHENE) USING A ZINCATE COMPLEX2012

    • Author(s)
      Tomoya Higashihara
    • Organizer
      The 5th International Symposium on Polymer Chemistry (PC2012)
    • Place of Presentation
      長春、中国
    • Related Report
      2012 Research-status Report
    • Invited
  • [Presentation] Enhancement of P3HT/PCBM photovoltaic efficiency and stability based on surfactant approach2012

    • Author(s)
      Tomoya Higashihara, Yi-Cang Lai, Jung-Hsun Tsai, Wen-Chang Chen, and Mitsuru Ueda
    • Organizer
      244th ACS National Meeting
    • Place of Presentation
      フィラデルフィア、米国
    • Related Report
      2012 Research-status Report
  • [Presentation] 深HOMO化ポリチオフェン誘導体の合成と有機薄膜太陽電池への応用2012

    • Author(s)
      チョン ミンアン、東原 知哉、上田 充
    • Organizer
      第61回高分子討論会
    • Place of Presentation
      名古屋
    • Related Report
      2012 Research-status Report
  • [Presentation] 半導体ブロック共重合体の合成と有機薄膜太陽電池への応用2012

    • Author(s)
      東原 知哉、Ryo Yecheol、Ree Moonhor、上田 充
    • Organizer
      第61回高分子討論会
    • Place of Presentation
      名古屋
    • Related Report
      2012 Research-status Report
    • Invited
  • [Presentation] Synthesis of Polythiophene Derivatives Having Oxadiazole or Thiadiazole Units and Their Application to Polymer Solar Cells2012

    • Author(s)
      Tetsunari Mizobe, Tomoya Higashihara, Hung-Chin Wu, Chien Lu, Wen-Chang Chen, and Mitsuru Ueda
    • Organizer
      Polycondensation2012 Meeting
    • Place of Presentation
      サンフランシスコ、米国
    • Related Report
      2012 Research-status Report
  • [Presentation] Protection-free Synthesis of Functionalized Polythiophene Derivatives by Using Zincate Complex2012

    • Author(s)
      Eisuke Goto, Tomoya Higashihara, and Mitsuru Ueda
    • Organizer
      Polycondensation2012 Meeting
    • Place of Presentation
      サンフランシスコ、米国
    • Related Report
      2012 Research-status Report
  • [Presentation] Synthesis of Block Copolymers with Poly(3-hexylthiophene) Segments and Their Application to Organic Photovoltaics2012

    • Author(s)
      Tomoya Higashihara, Mitsuru Ueda, and Moonhor Ree
    • Organizer
      The 9th SPSJ International Polymer Conference (IPC 2012)
    • Place of Presentation
      神戸
    • Related Report
      2012 Research-status Report
  • [Presentation] All-conjugated Graft Copolymers with P3HT Brushes via Grafting-From Process2012

    • Author(s)
      Jin Wang, Tomoya Higashihara, and Mitsuru Ueda
    • Organizer
      The 9th SPSJ International Polymer Conference (IPC 2012)
    • Place of Presentation
      神戸
    • Related Report
      2012 Research-status Report
  • [Presentation] ポリチオフェン類の精密合成と有機太陽電池材料への応用

    • Author(s)
      東原知哉
    • Organizer
      野口遵助成金講演会
    • Place of Presentation
      東京・竹橋・如水会館
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Remarks] 東原研究室URL

    • URL

      http://higashihara-lab.yz.yamagata-u.ac.jp/

    • Related Report
      2013 Final Research Report
  • [Remarks] 東原研究室ホームページ

    • URL

      http://higashihara-lab.yz.yamagata-u.ac.jp/

    • Related Report
      2013 Annual Research Report

URL: 

Published: 2013-05-31   Modified: 2019-07-29  

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