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Living Polymerization and Stereospecific Polymerization of Diazoacetates

Research Project

Project/Area Number 15K05521
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Polymer chemistry
Research InstitutionEhime University

Principal Investigator

Ihara Eiji  愛媛大学, 理工学研究科(工学系), 教授 (90243592)

Project Period (FY) 2015-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2017: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2016: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2015: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
Keywordsポリ(置換メチレン) / リビング重合 / 立体特異性重合 / ジアゾ酢酸エステル / パラジウム錯体 / ポリ(置換メチレン)
Outline of Final Research Achievements

We have established that polymerization of diazoacetates with sterically bulky substituents such as dendron and phosphazene proceeds in a living manner, affording polymers with narrow molecular weight distribution and block copolymers with a well-defined structure. A new initiating system, (naphthoquinone)Pd/borate, was revealed to be effective for controlling the polymerization of non-bulky ethyl diazoacetate.
In order to establish a method for characterizing tacticty of poly(alkoxycarbonylmethylene)s by NMR, tetramer of methyl diazoacetate was prepared and its diastereomeric separation into four isomers was successfully conducted. Two types of new initiating systems for diazoacetates were found to afford polymers with relatively controlled stereostructures.

Report

(4 results)
  • 2017 Annual Research Report   Final Research Report ( PDF )
  • 2016 Research-status Report
  • 2015 Research-status Report
  • Research Products

    (28 results)

All 2018 2017 2016 2015

All Journal Article (12 results) (of which Peer Reviewed: 12 results,  Acknowledgement Compliant: 5 results) Presentation (16 results) (of which Int'l Joint Research: 7 results,  Invited: 9 results)

  • [Journal Article] Self-Assembly of Hierarchical Structures Using Cyclotriphosphazene-Containing Poly(substituted methylene) Block Copolymers2018

    • Author(s)
      Kato Fuminobu、Chandra Alvin、Tokita Masatoshi、Asano Hironori、Shimomoto Hiroaki、Ihara Eiji、Hayakawa Teruaki
    • Journal Title

      ACS Macro Letters

      Volume: 7 Issue: 1 Pages: 37-41

    • DOI

      10.1021/acsmacrolett.7b00789

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Fluorinated Poly(substituted methylene)s Prepared by Pd-Initiated Polymerization of Fluorine-Containing Alkyl and Phenyl Diazoacetates: Their Unique Solubility and Postpolymerization Modification2018

    • Author(s)
      Shimomoto Hiroaki、Kudo Tomohiko、Tsunematsu Shogo、Itoh Tomomichi、Ihara Eiji
    • Journal Title

      Macromolecules

      Volume: 51 Issue: 2 Pages: 328-335

    • DOI

      10.1021/acs.macromol.7b01964

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Polymerization of alkyl diazoacetates initiated by the amidinate/Pd system: efficient synthesis of high molecular weight poly(alkoxycarbonylmethylene)s with moderate stereoregularity2017

    • Author(s)
      Shimomoto Hiroaki、Kawamata Junya、Murakami Hirokazu、Yamashita Kazuki、Itoh Tomomichi、Ihara Eiji
    • Journal Title

      Polymer Chemistry

      Volume: 8 Issue: 27 Pages: 4030-4037

    • DOI

      10.1039/c7py00816c

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ru-Catalyzed Polycondensation of Dialkyl 1,4-Phenylenebis(diazoacetate) with Dianiline: Synthesis of Well-Defined Aromatic Polyamines Bearing an Alkoxycarbonyl Group at the Adjacent Carbon of Each Nitrogen in the Main Chain Framework2017

    • Author(s)
      Shimomoto Hiroaki、Mukai Hiroto、Bekku Hideaki、Itoh Tomomichi、Ihara Eiji
    • Journal Title

      Macromolecules

      Volume: 50 Issue: 23 Pages: 9233-9238

    • DOI

      10.1021/acs.macromol.7b01994

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Pd-initiated Polymerization of Diazo Compounds Bearing Dialkoxyphosphinyl Group and Hydrolysis of the Resulting Polymers and Oligomers to Afford Phosphonic Acid-Containing Products2016

    • Author(s)
      Shimomoto, H.; Oda, A.; Kanayama, M.; Sako, T.; Itoh, T.; Ihara, E.; Hoshikawa, N.; Koiwai, A.; Hasegawa, N.
    • Journal Title

      J. Polym. Sci., Part A: Polym. Chem.

      Volume: 54 Issue: 12 Pages: 1742-1751

    • DOI

      10.1002/pola.28030

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Lithium Ion Conductivity of Polymers Containing N-Phenyl-2,6-dimethoxybenzamide Framework in Their Side Chains: Possible Role of Bond Rotation in Polymer Side Chain Substituents for Efficient Ion Transport2016

    • Author(s)
      Shimomoto, H.; Uegaito, T.; Yabuki, S.; Teratani, S; Itoh, T.; Ihara, E.; Hoshikawa, N.; Koiwai, A.; Hasegawa, N.
    • Journal Title

      Solid State Ionics

      Volume: 292 Pages: 1-7

    • DOI

      10.1016/j.ssi.2016.05.001

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Cyclopolymerization of Bis(diazocarbonyl) Compounds Leading to Well-defined Polymers Essentially Consisting of Cyclic Constitutional Units2016

    • Author(s)
      Shimomoto, H.; Kikuchi, M.; Aoyama, J.; Sakayoshi, D.; Itoh, T.; Ihara, E.
    • Journal Title

      Macromolecules

      Volume: 49 Issue: 22 Pages: 8459-8465

    • DOI

      10.1021/acs.macromol.6b01809

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] ジアゾ酢酸エステルの重合によるポリ(置換メチレン)合成2016

    • Author(s)
      井原栄治,下元浩晃
    • Journal Title

      日本接着学会誌

      Volume: 52 Pages: 348-356

    • NAID

      130007431809

    • Related Report
      2016 Research-status Report
    • Peer Reviewed
  • [Journal Article] Pd-initiated Controlled Polymerization of Diazoacetates with a Bulky Substituent: Synthesis of Well-defined Homopolymers and Block Copolymers with Narrow Molecular Weight Distribution from Cyclophosphazene-containing Diazoacetates2015

    • Author(s)
      Shimomoto, H.; Asano, H.; Itoh, T.; Ihara, E.
    • Journal Title

      Polymer Chemistry

      Volume: 6 Issue: 26 Pages: 4709-4714

    • DOI

      10.1039/c5py00532a

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis of Polymers with Densely-grafted Oligo(ethylene glycol)s by Pd-initiated Polymerization of Oxyethylene-containing Diazoacetates2015

    • Author(s)
      Shimomoto, H.; Shimizu, K.; Takeda, C.; Kikuchi, M.; Kudo, T.; Mukai, H.; Itoh, T.; Ihara, E.; Hoshikawa, N.; Koiwai, A.; Hasegawa, N.
    • Journal Title

      Polymer Chemistry

      Volume: 6 Issue: 47 Pages: 8124-8131

    • DOI

      10.1039/c5py01378j

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Polymerization of Alkyl Diazoacetates Initiated with Pd Complexes2015

    • Author(s)
      *Ihara, E.; Itoh, T.; Shimomoto, H.
    • Journal Title

      Macromolecular Symposia

      Volume: 349 Issue: 1 Pages: 57-64

    • DOI

      10.1002/masy.201400007

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Journal Article] Polymerization of Diazocarbonyl Compounds Initiated with Pd Complexes2015

    • Author(s)
      井原栄治,伊藤大道,下元浩晃
    • Journal Title

      KOBUNSHI RONBUNSHU

      Volume: 72 Issue: 7 Pages: 375-384

    • DOI

      10.1295/koron.2014-0100

    • NAID

      130005088929

    • ISSN
      0386-2186, 1881-5685
    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Presentation] Pd錯体を開始剤とするジアゾ酢酸エステルの重合:精密重合の実現と機能性高分子合成の試み2018

    • Author(s)
      井原 栄治
    • Organizer
      九州大学先導研特別講演会
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] Advances in Pd-initiated polymerization of diazoacetates: From variety of functional groups, living polymerization system, to high stereoregularity2017

    • Author(s)
      Hiroaki Shimomoto and Eiji Ihara
    • Organizer
      253rd American Chemical Society National Meeting & Exposition
    • Related Report
      2017 Annual Research Report
  • [Presentation] Pd-initiated Polymerization of Diazoacetates: New Synthetic Strategy for C-C Main Chain Polymers2017

    • Author(s)
      Eiji Ihara
    • Organizer
      InternationalSymposium on Advanced Polymeric Materials 2017 (ISAPM 2017)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 元素ブロックを有するジアゾ酢酸エステルの精密重合2017

    • Author(s)
      下元 浩晃・井原 栄治
    • Organizer
      第66回高分子討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] ジアゾ酢酸エステルの重合による柔らかな合成高分子系の構築2017

    • Author(s)
      井原 栄治・下元 浩晃
    • Organizer
      第66回高分子討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Pd-initiated Polymerization of Diazoacetates: New Synthetic Strategy for C-C Main Chain Polymers2016

    • Author(s)
      Ihara, E.
    • Organizer
      The 11th SPSJ International Polymer Conference (IPC2016)
    • Place of Presentation
      福岡国際会議場(福岡県・福岡市)
    • Year and Date
      2016-12-13
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Pd-mediated Controlled Polymerization of Diazoacetates Bearing a Dendron Unit2016

    • Author(s)
      Hohsaki, R.; Shimomoto, H.; Itoh, T.; Ihara, E.
    • Organizer
      The 11th SPSJ International Polymer Conference (IPC2016)
    • Place of Presentation
      福岡国際会議場(福岡県・福岡市)
    • Year and Date
      2016-12-13
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] Controlled Polymerization of Diazoacetates to Afford Well-defined Poly(alkoxycarbonylmethylene)s2016

    • Author(s)
      Ihara, E.
    • Organizer
      10th Korea-Japan Joint Symposium on Polymer Science 2016 (KJJS2016)
    • Place of Presentation
      Gwangju (Korea)
    • Year and Date
      2016-08-31
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] ジアゾ酢酸エステルの重合による官能基集積型機能性高分子の開発2016

    • Author(s)
      井原栄治
    • Organizer
      第65回高分子年次大会
    • Place of Presentation
      神戸国際会議場(兵庫県・神戸市)
    • Year and Date
      2016-05-25
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] オリゴエチレングリコール鎖で置換されたシクロトリホスファゼンを有するジアゾ酢酸エステルの重合2016

    • Author(s)
      山田智弘,下元浩晃,伊藤大道,井原栄治
    • Organizer
      第65回高分子年次大会
    • Place of Presentation
      神戸国際会議場(兵庫県・神戸市)
    • Year and Date
      2016-05-25
    • Related Report
      2016 Research-status Report
  • [Presentation] ポリ(アルコキシカルボニルメチレン)の立体規則性解析手法確立の試み:連鎖移動剤を用いたオリゴマーの合成およびそのジアステレオマーへの分離2016

    • Author(s)
      寄本佳孝,下元浩晃,伊藤大道,井原栄治,岡村 岳,右手 浩一
    • Organizer
      第65回高分子年次大会
    • Place of Presentation
      神戸国際会議場(兵庫県・神戸市)
    • Year and Date
      2016-05-25
    • Related Report
      2016 Research-status Report
  • [Presentation] Pd-Initiated Controlled Polymerization of Diazoacetates2016

    • Author(s)
      Ihara, E.
    • Organizer
      The 251th American Chemical Society National Meeting
    • Place of Presentation
      San Diego(USA)
    • Year and Date
      2016-03-13
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] ジアゾ酢酸エステルの精密重合:ポリ(置換メチレン)合成の新展開2016

    • Author(s)
      井原栄治
    • Organizer
      2016年度中国四国地区高分子講演会
    • Place of Presentation
      広島大学(広島県・東広島市)
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] Controlled Polymerization of Diazoacetates by Pd-based Initiating Systems2015

    • Author(s)
      Ihara, E.
    • Organizer
      IUPAC 11th International Conference on Advanced Polymers via Macromolecular Engineering (APME 2015)
    • Place of Presentation
      パシフィコ横浜(神奈川県横浜市)
    • Year and Date
      2015-10-18
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] ジアゾ酢酸エステルの精密重合:構造の明確な官能基集積型高分子の合成2015

    • Author(s)
      下元浩晃,浅野宏徳,法崎凌,伊藤大道,井原栄治
    • Organizer
      第64回高分子討論会
    • Place of Presentation
      東北大学川内キャンパス(宮城県仙台市)
    • Year and Date
      2015-09-15
    • Related Report
      2015 Research-status Report
  • [Presentation] Pd-Initiated Controlled Polymerization of Diazoacetates2015

    • Author(s)
      Ihara, E.
    • Organizer
      The 10th East Asian Symposium on Polymers for Advanced Technology (EASPAT 2015)
    • Place of Presentation
      淡路夢舞台国際会議場(兵庫県淡路市)
    • Year and Date
      2015-07-27
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research / Invited

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Published: 2015-04-16   Modified: 2019-03-29  

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