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Precise synthesis of chain end sequence-regulated polymer and its sub10 nm microphase separation

Research Project

Project/Area Number 17K19149
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Research Field Polymer, Organic materials, and related fields
Research InstitutionTokyo Institute of Technology

Principal Investigator

Ishizone Takashi  東京工業大学, 物質理工学院, 教授 (60212883)

Project Period (FY) 2017-06-30 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000)
Fiscal Year 2018: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
Fiscal Year 2017: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
Keywords定序性高分子 / アニオン付加反応 / リビングアニオン重合 / 非重合性ビニル化合物 / 低重合性ビニル化合物 / 末端官能基化ポリマー / 鎖末端 / 1,1-ジフェニルエチレン類 / アニオン重合 / ビニル化合物 / ポリマー鎖末端 / 求電子性 / 求核性 / 高分子合成 / 末端官能基 / 相分離構造
Outline of Final Research Achievements

The anionic living polystyrene was repeatedly reacted with a series of nonpolymerizable vinyl compounds, such as 1,1-diphenylethylene derivatives having electron-donating and electron-withdrawing groups, alkyl α-phenylacrylates, and N,N-dialkyl-α-phenylacrylamides, in a sequential fashion to give chain end sequence-regulated polymers. Those resulting polymers possessed two to four regulated functional sequences at one or two polymer chain end. The nonpolymerizable vinyl compounds did not show the homopolymerizability, but they accepted a 1:1 anionic addition with the nucleophilic anionic species to form new living anions derived from those vinyl compounds. The newly formed anions could sequentially react with more electrophilic vinyl compounds in turn to construct the regulated sequences containing various reactive functional groups at the polymer chain ends.

Academic Significance and Societal Importance of the Research Achievements

酵素やDNAなどの生体高分子の中には、厳密なモノマー配列(シーケンス)を持つ定序性高分子が知られているが、高分子の合成においてシーケンスの制御は重要な課題として残されている。本研究では、1,1-ジフェニルエチレン誘導体やαーフェニルアクリル酸エステルや、α-フェニルアクリルアミド類などの非重合性ビニル化合物のリビングアニオン付加反応を用いて、鎖末端に2-4ユニットのシーケンスを制御した構造を有する高分子を合成することに成功した。連鎖重合機構でシーケンスの制御に成功したことは非常に重要であり、本研究の特徴を強く表している。

Report

(3 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Research-status Report
  • Research Products

    (21 results)

All 2019 2018 2017 Other

All Int'l Joint Research (2 results) Journal Article (12 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 12 results) Presentation (6 results) (of which Int'l Joint Research: 6 results,  Invited: 6 results) Book (1 results)

  • [Int'l Joint Research] National Tsing Hua University(台湾)

    • Related Report
      2018 Annual Research Report
  • [Int'l Joint Research] 国立清華大学/国立成功大学(台湾)

    • Related Report
      2017 Research-status Report
  • [Journal Article] Combined effects of confinement size and chain-end tethering on the crystallization of poly(ε-caprolactone) chains in nanolamellae2019

    • Author(s)
      Yuki Yoneguchi, Hiroaki Kikuchi, Shintaro Nakagawa, Hironori Marubayashi, Takashi Ishizone, Shuichi Nojima, Kazuo Yamaguchi
    • Journal Title

      Polymer

      Volume: 160 Pages: 73-81

    • DOI

      10.1016/j.polymer.2018.11.030

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Nanoscale film morphology and property characteristics of dielectric polymers bearing monomeric and dimeric adamantane units2019

    • Author(s)
      Ree Brian J.、Kobayashi Shingo、Heo Kyuyoung、Lee Taek Joon、Satoh Toshifumi、Ishizone Takashi、Ree Moonhor
    • Journal Title

      Polymer

      Volume: 169 Pages: 225-233

    • DOI

      10.1016/j.polymer.2019.02.053

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Living anionic polymerization of 1,4-divinylbenzene and its derivatives2018

    • Author(s)
      Raita Goseki, Shunsuke Tanaka, Takashi Ishizone, Akira Hirao
    • Journal Title

      React. Func. Polym.

      Volume: 127 Pages: 94-112

    • DOI

      10.1016/j.reactfunctpolym.2018.03.011

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Bioinspired structural transition of synthetic polymers through biomolecular ligand binding2018

    • Author(s)
      Suzuki Seigo、Sawada Toshiki、Ishizone Takashi、Serizawa Takeshi
    • Journal Title

      Chemical Communications

      Volume: 54 Issue: 85 Pages: 12006-12009

    • DOI

      10.1039/c8cc06232c

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A thermoresponsive dynamic polymer brush fabricated by the segregation of amphiphilic diblock copolymers2018

    • Author(s)
      Hirokazu Tanoue, Kazuma Inoue, Norifumi L. Yamada, Kohzo Ito, Syo Miyao, Takashi Ishizone, Hideaki Yokoyama
    • Journal Title

      Soft Matter

      Volume: 14 Issue: 28 Pages: 5930-5935

    • DOI

      10.1039/c8sm00891d

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of polymers carrying adamantyl substituents in side chain2018

    • Author(s)
      Takashi Ishizone, Raita Goseki
    • Journal Title

      Polym. J.

      Volume: 50 Issue: 9 Pages: 805-819

    • DOI

      10.1038/s41428-018-0081-3

    • NAID

      40021648011

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Effects of Bulky End-Groups on the Crystallization Kinetics of Poly(ε-caprolactone) Homopolymers Confined in a Cylindrical Nanodomain2017

    • Author(s)
      Kawazu Koshun、Nakagawa Shintaro、Ishizone Takashi、Nojima Shuichi、Arai Daiki、Yamaguchi Kazuo、Nakahama Seiichi
    • Journal Title

      Macromolecules

      Volume: 50 Issue: 18 Pages: 7202-7210

    • DOI

      10.1021/acs.macromol.7b01536

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Tunable magneto-responsive mesoporous block copolymer membranes2017

    • Author(s)
      Tang Yanchun、Lin Xi、Ito Kohzo、Hong Ling、Ishizone Takashi、Yokoyama Hideaki、Ulbricht Mathias
    • Journal Title

      Journal of Membrane Science

      Volume: 544 Pages: 406-415

    • DOI

      10.1016/j.memsci.2017.08.069

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] A Segregation and Deprotection Approach for Hydrophilic Surfaces Using Amphiphilic Block Copolymers Possessing Polystyrene and Poly[(tri(ethylene glycol) methacrylate)] Segments2017

    • Author(s)
      Seki Akiko、Ishizone Takashi、Oyane Ayako、Yokoyama Hideaki
    • Journal Title

      Macromolecular Chemistry and Physics

      Volume: 218 Issue: 12 Pages: 1700048-1700048

    • DOI

      10.1002/macp.201700048

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Living Anionic Polymerization of 1-Adamantyl 4-vinylphenyl ketone2017

    • Author(s)
      Matsuoka Daigo、Goseki Raita、Uchida Satoshi、Ishizone Takashi
    • Journal Title

      Macromolecular Chemistry and Physics

      Volume: 218 Issue: 12 Pages: 1700015-1700015

    • DOI

      10.1002/macp.201700015

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Anionic Polymerization of Divinylbenzenes Possessing Methoxy Group2017

    • Author(s)
      Otake Kohei、Matsumoto Masayoshi、Tanaka Shunsuke、Uchida Satoshi、Goseki Raita、Hirao Akira、Ishizone Takashi
    • Journal Title

      Macromolecular Chemistry and Physics

      Volume: 218 Issue: 12 Pages: 1600550-1600550

    • DOI

      10.1002/macp.201600550

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis and surface characterization of well-defined amphiphilic block copolymers composed of polydimethylsiloxane and poly[oligo(ethylene glycol) methacrylate]2017

    • Author(s)
      Goseki Raita、Hong Ling、Inutsuka Manabu、Yokoyama Hideaki、Ito Kohzo、Ishizone Takashi
    • Journal Title

      RSC Advances

      Volume: 7 Issue: 41 Pages: 25199-25207

    • DOI

      10.1039/c7ra02569f

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Presentation] Anionic polymerization of benzofulvene derivatives2018

    • Author(s)
      Takashi Ishizone
    • Organizer
      Japan Korea Joint Symposium on Polymer 2018 (JKJS2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Anionic Polymerization of Monomers Possessing Adamantyl Groups2018

    • Author(s)
      Takashi Ishizone
    • Organizer
      Taiwan Japan Bilateral Polymer Symposium 2018 (TJBPS2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Living Anionic Polymerization of Functional Monomers2018

    • Author(s)
      Takashi Ishizone
    • Organizer
      2nd International Conference of Molecular Engineering of Polymers (MEP2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Anionic Polymerization of Monomers Possessing Adamantyl Groups2018

    • Author(s)
      Takashi Ishizone
    • Organizer
      he 12th SPSJ International Polymer Conference (IPC2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Anionic Polymerization of Styrene Derivatives Possessing Adamantyl Groups2017

    • Author(s)
      Takashi Ishizone
    • Organizer
      International Symposium on Ionic Polymerization-IP2017
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Anionic Polymerization of p-Divinylbenzene Derivatives Carrying Adamantyl Groups2017

    • Author(s)
      Takashi Ishizone
    • Organizer
      Japan-Taiwan Bilateral Polymer Symposium 2017
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Book] リビングラジカル重合-機能性高分子の合成と応用展開2018

    • Author(s)
      後関頼太、石曽根隆
    • Total Pages
      10
    • Publisher
      シーエムシー出版
    • ISBN
      9784781313368
    • Related Report
      2018 Annual Research Report

URL: 

Published: 2017-07-21   Modified: 2022-08-19  

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