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Periodically Sequenced Polymers via Iterative Vinyl Monomer Additions and Subsequent Efficient Polymerizations

Research Project

Project/Area Number 18H03917
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Review Section Medium-sized Section 35:Polymers, organic materials, and related fields
Research InstitutionNagoya University

Principal Investigator

Kamigaito Masami  名古屋大学, 工学研究科, 教授 (00273475)

Project Period (FY) 2018-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥44,330,000 (Direct Cost: ¥34,100,000、Indirect Cost: ¥10,230,000)
Fiscal Year 2020: ¥14,300,000 (Direct Cost: ¥11,000,000、Indirect Cost: ¥3,300,000)
Fiscal Year 2019: ¥14,300,000 (Direct Cost: ¥11,000,000、Indirect Cost: ¥3,300,000)
Fiscal Year 2018: ¥15,730,000 (Direct Cost: ¥12,100,000、Indirect Cost: ¥3,630,000)
Keywordsビニルモノマー / モノマー配列 / シークエンス / ラジカル付加 / 一分子付加 / メタセシス / チオール・エン / 異性化重合 / 高分子合成 / 高分子構造・物性 / 合成化学 / 有機工業化学 / 精密重合
Outline of Final Research Achievements

Monomer sequence control in synthetic polymers is one of the most challenging topics in polymer chemistry, in particular, for vinyl polymers, which are usually prepared by chain-growth addition polymerizations. In this research, sequence-regulated oligomers were first prepared by iterative atom-transfer radical additions of vinyl monomers. After introduction of reactive groups such as vinyl groups at the chain ends, the end-functionalized sequence-regulated oligomers were linked by precision polymerizations, such as olefin metathesis polymerization, thiol-ene polymerization, and radical isomerization polymerization, to produce sequence-regulated polymers with periodic vinyl monomer sequences in the main chain. Furthermore, simultaneous control of stereostructures and molecular weights as well as introduction of polar functional groups was achieved. Finally, effects of monomer sequences on polymer properties were evaluated.

Academic Significance and Societal Importance of the Research Achievements

ビニルモノマー配列が1分子単位で精密に制御された周期配列高分子の合成が初めて可能となり、高分子化学における究極の課題の解決策を示したことは学術的に意義深い。さらに周期配列高分子に対して分子量と立体構造の制御も可能も可能となり、究極のビニルポリマーにさらに近づいたとして高く評価される。また、1分子単位でのビニルモノマー配列がポリマー物性に及ぼす影響がわかりつつあり、高分子構造と物性の研究にも波及効果が期待される。このような超精密制御ビニルポリマーの合成が可能となることで、高性能・高機能な次世代ビニルポリマーの発展につながり、工業的および社会的意義も大きいと考えられる。

Report

(4 results)
  • 2021 Final Research Report ( PDF )
  • 2020 Annual Research Report
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • Research Products

    (63 results)

All 2022 2021 2020 2019 2018

All Journal Article (13 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 13 results,  Open Access: 10 results) Presentation (50 results) (of which Int'l Joint Research: 18 results,  Invited: 16 results)

  • [Journal Article] Periodically Functionalized Sequence‐Regulated Vinyl Polymers via Iterative Atom Transfer Radical Additions and Acyclic Diene Metathesis Polymerization2022

    • Author(s)
      Miyajima Masato、Satoh Kotaro、Kamigaito Masami
    • Journal Title

      Macromolecular Chemistry and Physics

      Volume: 223 Issue: 12 Pages: 2100426-2100426

    • DOI

      10.1002/macp.202100426

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Sequence-regulated vinyl polymers <i>via</i> iterative atom transfer radical additions and acyclic diene metathesis polymerization2021

    • Author(s)
      Miyajima Masato、Satoh Kotaro、Kamigaito Masami
    • Journal Title

      Polymer Chemistry

      Volume: 12 Issue: 3 Pages: 423-431

    • DOI

      10.1039/d0py01564d

    • NAID

      120007163657

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Progress and Perspectives Beyond Traditional RAFT Polymerization2020

    • Author(s)
      Nothling Mitchell D.、Fu Qiang、Reyhani Amin、Allison‐Logan Stephanie、Jung Kenward、Zhu Jian、Kamigaito Masami、Boyer Cyrille、Qiao Greg G.
    • Journal Title

      Advanced Science

      Volume: 7 Issue: 20 Pages: 2001656-2001656

    • DOI

      10.1002/advs.202001656

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Synergistic Advances in Living Cationic and Radical Polymerizations2020

    • Author(s)
      Kamigaito Masami、Sawamoto Mitsuo
    • Journal Title

      Macromolecules

      Volume: 53 Issue: 16 Pages: 6749-6753

    • DOI

      10.1021/acs.macromol.0c01392

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Multifactor Control of Vinyl Monomer Sequence, Molecular Weight, and Tacticity via Iterative Radical Additions and Olefin Metathesis Reactions2020

    • Author(s)
      Miyajima Masato、Satoh Kotaro、Horibe Takahiro、Ishihara Kazuaki、Kamigaito Masami
    • Journal Title

      Journal of the American Chemical Society

      Volume: 142 Issue: 44 Pages: 18955-18962

    • DOI

      10.1021/jacs.0c09289

    • NAID

      120007147364

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cooperative reduction of various RAFT polymer terminals using hydrosilane and thiol via polarity reversal catalysis2019

    • Author(s)
      Uchiyama Mineto、Satoh Kotaro、Kamigaito Masami
    • Journal Title

      Chemical Communications

      Volume: 55 Issue: 37 Pages: 5327-5330

    • DOI

      10.1039/c9cc00900k

    • NAID

      120006723421

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Cationic Polymerization via Activation of Alkoxyamines Using Photoredox Catalysts2019

    • Author(s)
      Konya Masato、Uchiyama Mineto、Satoh Kotaro、Kamigaito Masami
    • Journal Title

      ChemPhotoChem

      Volume: 3 Issue: 11 Pages: 1100-1108

    • DOI

      10.1002/cptc.201900148

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] 1:3 ABAA sequence-regulated substituted polymethylenes via alternating radical copolymerization of methyl cinnamate and maleic anhydride followed by post-polymerization reactions2019

    • Author(s)
      Terao Yuya、Sugihara Shizuka、Satoh Kotaro、Kamigaito Masami
    • Journal Title

      European Polymer Journal

      Volume: 120 Pages: 109225-109225

    • DOI

      10.1016/j.eurpolymj.2019.109225

    • NAID

      120006840785

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Valencene as a naturally occurring sesquiterpene monomer for radical copolymerization with maleimide to induce concurrent 1:1 and 1:2 propagation2019

    • Author(s)
      Hashimoto Hiroaki、Takeshima Hisaaki、Nagai Tomonari、Uchiyama Mineto、Satoh Kotaro、Kamigaito Masami
    • Journal Title

      Polymer Degradation and Stability

      Volume: 161 Pages: 183-190

    • DOI

      10.1016/j.polymdegradstab.2019.01.025

    • NAID

      120006650165

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Construction of Sequence-Regulated Vinyl Copolymers via Iterative Single Vinyl Monomer Additions and Subsequent Metal-Catalyzed Step-Growth Radical Polymerization2019

    • Author(s)
      Satoh Kotaro、Ishizuka Kenta、Hamada Tsuyoshi、Handa Masato、Abe Tomohiro、Ozawa Satoshi、Miyajima Masato、Kamigaito Masami
    • Journal Title

      Macromolecules

      Volume: 印刷中 Issue: 9 Pages: 3327-3341

    • DOI

      10.1021/acs.macromol.9b00676

    • NAID

      120006723422

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Discrete and Stereospecific Oligomers Prepared by Sequential and Alternating Single Unit Monomer Insertion2018

    • Author(s)
      Huang Zixuan、Noble Benjamin B.、Corrigan Nathaniel、Chu Yingying、Satoh Kotaro、Thomas Donald S.、Hawker Craig J.、Moad Graeme、Kamigaito Masami、Coote Michelle L.、Boyer Cyrille、Xu Jiangtao
    • Journal Title

      Journal of the American Chemical Society

      Volume: 140 Issue: 41 Pages: 13392-13406

    • DOI

      10.1021/jacs.8b08386

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Controlled Radical Copolymerization of Cinnamic Derivatives as Renewable Vinyl Monomers with Both Acrylic and Styrenic Substituents: Reactivity, Regioselectivity, Properties, and Functions2018

    • Author(s)
      Terao Yuya、Satoh Kotaro、Kamigaito Masami
    • Journal Title

      Biomacromolecules

      Volume: 20 Issue: 1 Pages: 192-203

    • DOI

      10.1021/acs.biomac.8b01298

    • NAID

      120006635884

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Degenerative chain-transfer process: Controlling all chain-growth polymerizations and enabling novel monomer sequences2018

    • Author(s)
      Kamigaito Masami、Satoh Kotaro、Uchiyama Mineto
    • Journal Title

      Journal of Polymer Science Part A: Polymer Chemistry

      Volume: 57 Issue: 3 Pages: 243-254

    • DOI

      10.1002/pola.29257

    • NAID

      120006635881

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Presentation] Synergistic Developments in Living Cationic and Radical Polymerizations for Sustainability2022

    • Author(s)
      M. Kamigaito
    • Organizer
      ACS Spring 2022 Meeting
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Sequence-Regulated Vinyl Polymers by Controlled Radical Additions and Precision Polymerizations2021

    • Author(s)
      M. Kamigaito
    • Organizer
      IUPAC-MACRO2020+
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synergistic Advances in Living Cationic and Radical Polymerizations and Sustainable Developments2021

    • Author(s)
      M. Kamigaito
    • Organizer
      IUPAC-MACRO2020+
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Multiple Controls of Vinyl Monomer Sequence, Molecular Weight, and Stereoregularity via Iterative Single Unit Monomer Additions and Controlled Polymerizations2021

    • Author(s)
      M. Kamigaito
    • Organizer
      The 2021 International Chemical Congress of Pacific Basin Societies (Pacifichem 2021)
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ラジカル重合における多重制御重合系の開発2021

    • Author(s)
      上垣外正己
    • Organizer
      第70回高分子学会年次大会
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] ラジカル反応に基づく配列制御ビニルポリマーの合成2021

    • Author(s)
      上垣外正己
    • Organizer
      第56回北海道支部研究発表会
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] 1分子ラジカル付加とメタセシス反応によるスチレン系配列制御高分子の合成2021

    • Author(s)
      相馬健太, 藤原直生, 山田勇介, 宮島雅斗, 内山峰人, 上垣外正己
    • Organizer
      第70回高分子学会年次大会
    • Related Report
      2020 Annual Research Report
  • [Presentation] リビングラジカル重合とチオール・エン反応によるマルチブロック共重合体の合成2021

    • Author(s)
      森川元喜, 谷元貴幸, YOO Dasom, 宮島雅斗, 内山峰人, 上垣外正己
    • Organizer
      第70回高分子学会年次大会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 1分子ラジカル付加とメタセシス反応による配列制御スチレン―エチレン共重合体の合成2021

    • Author(s)
      相馬健太, 内山峰人, 上垣外正己
    • Organizer
      第70回高分子討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 1分子ラジカル付加とメタセシス反応を駆使した配列制御スチレン―エチレン共重合体の合成2021

    • Author(s)
      相馬健太, 内山峰人, 上垣外正己
    • Organizer
      2021年度東海高分子研究会学生発表会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 1分子ラジカル付加とチオール-エン重付加によるカテコールやアミノ基を有する配列制御高分子の合成2020

    • Author(s)
      山田勇介, 宮島雅斗, 内山峰人, 上垣外正己
    • Organizer
      第69回高分子学会年次大会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 1分子ラジカル付加とチオール-エン重付加による官能基が組み込まれた配列制御高分子の合成2020

    • Author(s)
      山田勇介, 宮島雅斗, 内山峰人, 上垣外正己
    • Organizer
      第69回高分子討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 一分子ラジカル付加とオレフィンメタセシスを駆使した立体規則性配列制御ビニルポリマーの合成2020

    • Author(s)
      宮島雅斗, 内山峰人, 佐藤浩太郎, 堀部貴大, 石原一彰, 上垣外正己
    • Organizer
      第69回高分子討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 1分子ラジカル付加とチオール-エン重付加による官能基が組み込まれた配列制御高分子の合成2020

    • Author(s)
      山田勇介, 宮島雅斗, 内山峰人, 上垣外正己
    • Organizer
      2020年度東海高分子研究会学生発表会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 遷移金属触媒によるラジカル付加反応を用いた精密重合2020

    • Author(s)
      上垣外正己
    • Organizer
      19-2高分子学会講演会「高分子合成~意のままに合成する技術と秘訣~」
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] Vinyl Monomer Sequence Control via Precision Polymerization2019

    • Author(s)
      M. Kamigaito
    • Organizer
      2019 Japan-USA Symposium on Polymer Chemistry: Macromolecules: - Challenges and Opportunities for the 21st Century -
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Vinyl Monomer Sequence Control via Precision Polymerization2019

    • Author(s)
      M. Kamigaito
    • Organizer
      Precision Synthesis and Thin Film Self-Assembly of Polymers
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Vinyl Monomer Sequence Control via Precision Polymerization2019

    • Author(s)
      M. Kamigaito
    • Organizer
      he 16th Pacific Polymer Conference (PPC16)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis of Sequence-Regulated Vinyl Polymer by 1,5-Shift Radical Polymerization2019

    • Author(s)
      M. Goto, M. Miyajima, M. Uchiyama, K. Satoh, M. Kamigaito
    • Organizer
      13th IUPAC International Symposium on Ionic Polymerization (IP’19)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis of Sequence-Regulated Vinyl Polymers by Entropy-Driven Ring-Opening Metathesis Polymerization2019

    • Author(s)
      M. Miyajima, K. Satoh, M. Kamigaito
    • Organizer
      The 16th Pacific Polymer Conference (PPC16)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis of Sequence-Regulated Vinyl Polymer by 1,5-Shift Radical Polymerization2019

    • Author(s)
      M. Goto, M. Miyajima, M. Uchiyama, K. Satoh, M. Kamigaito
    • Organizer
      The 16th Pacific Polymer Conference (PPC16)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 精密重合における最近の進展2019

    • Author(s)
      上垣外正己
    • Organizer
      第68回高分子学会年次大会
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] 1,5-シフトを伴う種々の定序配列ビニルモノマーのラジカル重合2019

    • Author(s)
      後藤美咲, 宮島雅斗, 内山峰人, 佐藤浩太郎, 上垣外正己
    • Organizer
      第68回高分子学会年次大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 18員環定序配列ビニルオリゴマーのエントロピー駆動型開環メタセシス重合および共重合2019

    • Author(s)
      宮島雅斗, 佐藤浩太郎, 上垣外正己
    • Organizer
      第68回高分子学会年次大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 1,5-シフトを伴うラジカル異性化重合による配列制御ビニルポリマーの合成2019

    • Author(s)
      後藤美咲, 宮島雅斗, 内山峰人, 佐藤浩太郎, 上垣外正己
    • Organizer
      第169回東海高分子研究会講演会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 1,5-シフトを伴うラジカル異性化重合による配列制御ビニルポリマーの合成2019

    • Author(s)
      後藤美咲, 宮島雅斗, 内山峰人, 佐藤浩太郎, 上垣外正己
    • Organizer
      第68回高分子討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 1分子ラジカル付加とチオール-エン重付加による種々の官能基を有する配列制御高分子の合成2019

    • Author(s)
      山田勇介, 宮島雅斗, 内山峰人, 上垣外正己
    • Organizer
      第68回高分子討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] エントロピー駆動型開環メタセシス重合による配列制御ビニルポリマーの合成2019

    • Author(s)
      宮島雅斗, 佐藤浩太郎, 上垣外正己
    • Organizer
      第68回高分子討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 1分子ラジカル付加とチオール-エン重付加による種々の官能基を有する配列制御高分子2019

    • Author(s)
      山田勇介, 宮島雅斗, 内山峰人, 上垣外正己
    • Organizer
      第9回CSJ化学フェスタ2019
    • Related Report
      2019 Annual Research Report
  • [Presentation] 1,5-シフトを伴うラジカル異性化重合による配列制御ビニルポリマーの合成2019

    • Author(s)
      後藤美咲, 宮島雅斗, 内山峰人, 佐藤浩太郎, 上垣外正己
    • Organizer
      第50回中部化学関係協会支部連合秋季大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 1,5-シフトを伴う種々の定序配列ビニルモノマーのラジカル重合2019

    • Author(s)
      後藤美咲, 宮島雅斗, 内山峰人, 佐藤浩太郎, 上垣外正己
    • Organizer
      第28回ポリマー材料フォーラム
    • Related Report
      2019 Annual Research Report
  • [Presentation] Synthesis of Sequence-Regulated Vinyl Polymers by Combining Atom Transfer Radical Addition and Metathesis Polymerization2019

    • Author(s)
      宮島雅斗, 佐藤浩太郎, 上垣外正己
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Sequence-Regulated Polymers via Iterative Single Monomer Addition and Controlled Polymerization2018

    • Author(s)
      M. Kamigaito, K. Satoh, T. Soejima, M. Miyajima, Y. Tanaka
    • Organizer
      Bordeaux Polymer Conference 2018 (BPC2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Vinyl Monomer Sequence Regulation via Controlled Addition and Polymerization2018

    • Author(s)
      M. Kamigaito, K. Satoh,
    • Organizer
      The IUPAC World Polymer Congress (MACRO2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Monomer Sequence Regulation via Controlled Additions and Polymerizations2018

    • Author(s)
      M. Kamigaito
    • Organizer
      Japan-Korea Joint Symposium on Polymer Science 2018
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Monomer Sequence Regulation via Controlled Additions and Polymerizations2018

    • Author(s)
      M. Kamigaito, K. Satoh
    • Organizer
      2nd International Conference of Molecular Engineering of Polymers (MEP-2018, MEP-2)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis of Sequence-Regulated Vinyl Polymers via Combination of Atom Transfer Radical Additions and Olefin Metathesis Reactions2018

    • Author(s)
      M. Miyajima, K. Satoh, M. Kamigaito
    • Organizer
      Japan-Korea Joint Symposium on Polymer Science 2018
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 1,5-Hydorgen Transfer Radical Polymerization for Synthesis of Sequence-Regulated Vinyl Polymers2018

    • Author(s)
      M. Goto, M. Uchiyama, K. Satoh, M. Kamigaito
    • Organizer
      The 12th SPSJ International Polymer Conference (IPC2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Entropy-Driven Ring-Opening Metathesis Polymerization of Sequence-Regulated Cyclic Vinyl Oligomers2018

    • Author(s)
      M. Miyajima, K. Satoh, M. Kamigaito
    • Organizer
      The 12th SPSJ International Polymer Conference (IPC2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis of Sequence-Regulated Polymers via Atom Transfer Radical Addition and Thiol-Ene Polymerization2018

    • Author(s)
      Y. Tanaka, M. Uchiyama, K. Satoh, M. Kamigaito
    • Organizer
      nternational Conference on Advanced and Applied Petroleum, Petrochemicals, and, Polymers (ICAPPP2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ビニルポリマーでモノマーが並ぶ反応開発2018

    • Author(s)
      上垣外正己
    • Organizer
      第8回CSJ化学フェスタ2018
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] 一分子ラジカル付加とチオール―エン重付加による定序配列ポリマーの合成:ビニルモノマー配列の効果2018

    • Author(s)
      田中良樹, 内山峰人, 佐藤浩太郎, 上垣外正己
    • Organizer
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Published: 2018-04-23   Modified: 2023-01-30  

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