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Stereospecific radical and anionic polymerization utilizing hydrogen bonding and characterization by statistical 2D NMR

Research Project

Project/Area Number 23750130
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Polymer chemistry
Research InstitutionThe University of Tokushima

Principal Investigator

HIRANO Tomohiro  徳島大学, ソシオテクノサイエンス研究部, 准教授 (80314839)

Project Period (FY) 2011 – 2013
Project Status Completed (Fiscal Year 2013)
Budget Amount *help
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2013: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2012: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2011: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
Keywords水素結合 / ラジカル重合 / アニオン重合 / 立体規則性 / NMR / 主成分分析 / 部分最小二乗回帰 / 帰属 / 不斉誘導ラジカル環化重合
Research Abstract

Stereospecificities were successfully induced not only in radical polymerization but also in anionic polymerization, with the aid of formation of hydrogen-bond-assisted complexes of amide-containing monomers, such as N-allyl-N-tert-butylacrylamide, N-vinyl-2-pyrrolidone, N-n-propyl-alpha-fluoroacrylamide, and N-isopropylacrylamide. In particular, chirality was also induced in the polymerization of N-allyl-N-tert-butylacrylamide in the presence of chiral tartrates.
Statistical 2D NMR, in which principle component analysis was applied, successfully interpreted assignments of NMR spectra of synthetic polymers in terms of stereoregularities. In addition, tacticities distributions were precisely predicted by partial least squares regression.

Report

(4 results)
  • 2013 Annual Research Report   Final Research Report ( PDF )
  • 2012 Research-status Report
  • 2011 Research-status Report
  • Research Products

    (41 results)

All 2013 2012 2011 Other

All Journal Article (3 results) (of which Peer Reviewed: 3 results) Presentation (36 results) Remarks (2 results)

  • [Journal Article] Isotactic-specific anionic polymerization of N-isopropylacrylamide with dilithium tetra-tert-butylzincate in the presence of a fluorinated alcohol or Lewis acid2012

    • Author(s)
      T. Hirano, T. Furutani, T. Saito, T. Segata, M. Oshimura, K. Ute
    • Journal Title

      Polymer

      Volume: 53 Issue: 22 Pages: 4961-4966

    • DOI

      10.1016/j.polymer.2012.09.004

    • NAID

      120006884842

    • Related Report
      2013 Final Research Report 2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Syndiotactic- and heterotactic-specific radical polymerizations of N-n-propyl-α-fluoroacrylamide and phase-transition behaviors of aqueous solutions of poly(N-n-propyl-α-fluoroacrylamide)2012

    • Author(s)
      T. Hirano, T. Furutani, M. Oshimura, K. Ute
    • Journal Title

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

      Volume: 50 Issue: 12 Pages: 2471-2483

    • DOI

      10.1002/pola.26024

    • NAID

      120006884844

    • Related Report
      2013 Final Research Report 2011 Research-status Report
    • Peer Reviewed
  • [Journal Article] Application of multivariate analysis of NMR spectra of poly(N-isopropylacrylamide) to assignment of stereostructures and prediction of tacticity distribution2012

    • Author(s)
      T. Hirano, T. Anmoto, N. Umezawa, H. Momose, Y. Katsumoto, M. Oshimura, K. Ute
    • Journal Title

      Polym. J

      Volume: 44 Issue: 8 Pages: 815-820

    • DOI

      10.1038/pj.2012.61

    • NAID

      10030931436

    • Related Report
      2013 Final Research Report 2011 Research-status Report
    • Peer Reviewed
  • [Presentation] poly(N,N-ジメチルアクリルアミド) のNMR スペクトルにおける多変量解析2013

    • Author(s)
      松本 大志,押村 美幸,平野 朋広,右手 浩一
    • Organizer
      第59回高分子研究発表会(神戸)
    • Place of Presentation
      兵庫県民会館(兵庫県)
    • Year and Date
      2013-07-12
    • Related Report
      2013 Final Research Report
  • [Presentation] Ute Multivariate analysis of NMR spectra of poly(lactic acid)2013

    • Author(s)
      T. Hirano, R. Yahata, K. Suganuma, T. Asakura, M. Oshimura, K
    • Organizer
      The 13th Pacific Polymer Conference (PPC-13)
    • Place of Presentation
      Grand Hi-Lai Arena (Kaohsiung, Taiwan)
    • Related Report
      2013 Final Research Report
  • [Presentation] Tacticity analysis of poly(lactic acid) by multivariate analysis of NMR spectra2013

    • Author(s)
      R. Yahata, K. Suganuma, T. Asakura, M. Oshimura, T. Hirano, K. Ute
    • Organizer
      IUPAC International Symposium on Ionic Polymerization 2013 (IP2013)
    • Place of Presentation
      Awaji Yumebutai International Conference Center (Awaji Island, Hyogo)
    • Related Report
      2013 Final Research Report
  • [Presentation] NMR スペクトルの多変量解析によるポリ乳酸の立体規則性解析(3)2013

    • Author(s)
      八幡 莉紗,菅沼 こと,朝倉 哲郎,押村 美幸,平野 朋広,右手 浩一
    • Organizer
      第18回高分子分析討論会
    • Place of Presentation
      明治大学(東京都)
    • Related Report
      2013 Final Research Report
  • [Presentation] PTBMAから変換したMMA-TBMA共重合体とPMMAの13C NMRスペクトルの多変量解析2013

    • Author(s)
      菅野 夏基,押村 美幸,平野 朋広,右手 浩一
    • Organizer
      第18回高分子分析討論会
    • Place of Presentation
      明治大学(東京都)
    • Related Report
      2013 Final Research Report
  • [Presentation] NMR スペクトルの多変量解析によるポリN,N-ジメチルアクリルアミドの立体規則性の解析2013

    • Author(s)
      松本 大志,押村 美幸,平野 朋広,右手 浩一
    • Organizer
      第62回高分子討論会
    • Place of Presentation
      金沢大学(石川県)
    • Related Report
      2013 Final Research Report
  • [Presentation] NMR スペクトルの多変量解析を用いたポリ乳酸の立体規則性解析(2)2013

    • Author(s)
      八幡 莉紗,菅沼 こと,朝倉 哲郎,押村 美幸,平野 朋広,右手 浩一
    • Organizer
      第62回高分子学会年次大会
    • Place of Presentation
      京都国際会館(京都府)
    • Related Report
      2013 Final Research Report
  • [Presentation] Multivariate Analysis of NMR Spectra of Poly(Lactic Acid)2013

    • Author(s)
      Tomohiro Hirano, Risa Yahata, Koto Suganuma, Tetsuo Asakura, Miyuki Oshimura, Koichi Ute
    • Organizer
      The 13th Pacific Polymer Conference (PPC-13)
    • Place of Presentation
      Grand Hi-Lai Arena ( Kaohsiung, Taiwan)
    • Related Report
      2013 Annual Research Report
  • [Presentation] Tacticity analysis of poly(lactic acid) by multivariate analysis of NMR spectra2013

    • Author(s)
      Risa Yahata, Koto Suganuma, Tetsuo Asakura, Miyuki Oshimura, Tomohiro Hirano, Koichi Ute
    • Organizer
      IUPAC International Symposium on Ionic Polymerization 2013 (IP2013)
    • Place of Presentation
      Awaji Yumebutai International Conference Center (Awaji Island, Japan)
    • Related Report
      2013 Annual Research Report
  • [Presentation] NMRスペクトルの多変量解析によるポリ乳酸の立体規則性解析(3)2013

    • Author(s)
      八幡 莉紗,菅沼 こと,朝倉 哲郎,押村 美幸,平野 朋広,右手 浩一
    • Organizer
      第18回高分子分析討論会
    • Place of Presentation
      明治大学(東京都)
    • Related Report
      2013 Annual Research Report
  • [Presentation] PTBMAから変換したMMA-TBMA共重合体とPMMAの13C NMRスペクトルの多変量解析2013

    • Author(s)
      菅野 夏基,押村 美幸,平野 朋広,右手 浩一
    • Organizer
      第18回高分子分析討論会
    • Place of Presentation
      明治大学(東京都)
    • Related Report
      2013 Annual Research Report
  • [Presentation] NMRスペクトルの多変量解析によるポリN,N-ジメチルアクリルアミドの立体規則性の解析2013

    • Author(s)
      松本 大志,押村 美幸,平野 朋広,右手 浩一
    • Organizer
      第62回高分子討論会
    • Place of Presentation
      金沢大学(石川県金沢市)
    • Related Report
      2013 Annual Research Report
  • [Presentation] poly(N,N-ジメチルアクリルアミド)のNMRスペクトルにおける多変量解析2013

    • Author(s)
      松本 大志,押村 美幸,平野 朋広,右手 浩一
    • Organizer
      第59回高分子研究発表会(神戸)
    • Place of Presentation
      兵庫県民会館(兵庫県神戸市)
    • Related Report
      2013 Annual Research Report
  • [Presentation] NMRスペクトルの多変量解析を用いたポリ乳酸の立体規則性解析(2)2013

    • Author(s)
      八幡 莉紗,菅沼 こと,朝倉 哲郎,押村 美幸,平野 朋広,右手 浩一
    • Organizer
      第62回高分子学会年次大会
    • Place of Presentation
      京都国際会館(京都府京都市)
    • Related Report
      2013 Annual Research Report
  • [Presentation] Tacticity analysis of poly(lactic acid) by multivariate analysis of NMR spectra2012

    • Author(s)
      R. Yahata, T. Hirano, M. Oshimura, K. Ute, K. Suganuma, T. Asakura
    • Organizer
      The 9th International Polymer Conference (IPC 2012)
    • Place of Presentation
      Kobe International Conference Center (Kobe, Hyogo)
    • Related Report
      2013 Final Research Report
  • [Presentation] NMR スペクトルの多変量解析によるポリ乳酸の立体規則性解析2012

    • Author(s)
      八幡 莉紗,平野 朋広,押村 美幸,右手 浩一,菅沼 こと,朝倉 哲郎
    • Organizer
      第61回高分子討論会
    • Place of Presentation
      名古屋工業大学(愛知県)
    • Related Report
      2013 Final Research Report
  • [Presentation] MMA-TBMA 共重合体から変換した PMMA の13C NMR スペクトルの多変量解析2012

    • Author(s)
      菅野 夏基,平野 朋広,押村 美幸,右手 浩一
    • Organizer
      第61回高分子討論会
    • Place of Presentation
      名古屋工業大学(愛知県)
    • Related Report
      2013 Final Research Report
  • [Presentation] Tacticity analysis of poly(lactic acid) by multivariate analysis of NMR spectra2012

    • Author(s)
      Risa Yahata, et al
    • Organizer
      The 9th International Polymer Conference (IPC 2012)
    • Place of Presentation
      Kobe International Conference Center(兵庫県)
    • Related Report
      2012 Research-status Report
  • [Presentation] MMA-TBMA共重合体から変換したPMMAの13C NMRスペクトルの多変量解析2012

    • Author(s)
      菅野 夏基,他
    • Organizer
      第61回高分子討論会
    • Place of Presentation
      名古屋工業大学(愛知県)
    • Related Report
      2012 Research-status Report
  • [Presentation] NMRスペクトルの多変量解析によるポリ乳酸の立体規則性解析2012

    • Author(s)
      八幡 莉紗,他
    • Organizer
      第61回高分子討論会
    • Place of Presentation
      名古屋工業大学(愛知県)
    • Related Report
      2012 Research-status Report
  • [Presentation] NMR Assignment of poly(1-vinylpyrrolidone) by statistical 2D NMR2011

    • Author(s)
      T. Anmoto, N. Umezawa, T. Hirano, H. Momose, Y. Katsumoto, M. Oshimura, K. Ute
    • Organizer
      The 12th Pacific Polymer Conference
    • Place of Presentation
      The Shilla Hotel (Jeju Island, Korea)
    • Related Report
      2013 Final Research Report
  • [Presentation] Anionic Polymerization of N-Isopropylacrylamide with t-Bu_4ZnLi_2 in the Presence of Alcohols2011

    • Author(s)
      T. Furutani, E. Kaji, T. Kaneko, M. Oshimura, T. Hirano, Koichi Ute
    • Organizer
      The 12th Pacific Polymer Conference
    • Place of Presentation
      The Shilla Hotel (Jeju Island, Korea)
    • Related Report
      2013 Final Research Report
  • [Presentation] フッ素化アルコール存在下N-n-プロピル-α-フルオロアクリルアミドの立体特異性重合2011

    • Author(s)
      古谷 喬大,加地 栄一,金子 俊幸,押村 美幸,平野 朋広,右手 浩一
    • Organizer
      2011年日本化学会西日本大会
    • Place of Presentation
      徳島大学(徳島県)
    • Related Report
      2013 Final Research Report
  • [Presentation] 立体規則性の異なるポリマーのNMRスペクトルの多変量解析 ― 立体規則性による帰属2011

    • Author(s)
      庵本 卓矢,梅澤 奈央,平野 朋広,百瀬 陽,勝本 之晶,押村 美幸,右手 浩一
    • Organizer
      2011年日本化学会西日本大会
    • Place of Presentation
      徳島大学(徳島県)
    • Related Report
      2013 Final Research Report
  • [Presentation] 酒石酸エステル存在下でのN-アリル-N-tert-ブチルアクリルアミドの不斉ラジカル環化重合2011

    • Author(s)
      四宮 未来,森上 晃弘,平野 朋広,右手 浩一
    • Organizer
      2011年日本化学会西日本大会
    • Place of Presentation
      徳島大学(徳島県)
    • Related Report
      2013 Final Research Report
  • [Presentation] Statistical two-dimensional NMR : Assignment of complicated resonances due to the carbonyl carbons of methacrylate copolymers2011

    • Author(s)
      T. Hirano, H. Momose, T. Maeda, T. Naono, S. Asakawa, Y. Katsumoto, K. Ute
    • Organizer
      24th International Symposium on Polymer Analysis and Characterization
    • Place of Presentation
      Villa Gualino (Torino, Italy)
    • Related Report
      2013 Final Research Report
  • [Presentation] フッ素化アルコール存在下t-Bu_4ZnLi_2 によるアクリルアミド誘導体のアニオン重合2011

    • Author(s)
      古谷 喬大,加地 栄一,金子 俊幸,平野 朋広,右手 浩一
    • Organizer
      第60回高分子学会年次大会
    • Place of Presentation
      大阪国際会議場(大阪府)
    • Related Report
      2013 Final Research Report
  • [Presentation] ポリ(N-イソプロピルアクリルアミド)のNMRスペクトルの多変量解析による帰属2011

    • Author(s)
      平野 朋広,梅澤 奈央,庵本 卓矢,百瀬 陽,右手 浩一
    • Organizer
      第60回高分子学会年次大会
    • Place of Presentation
      大阪国際会議場(大阪府)
    • Related Report
      2013 Final Research Report
  • [Presentation] NMRスペクトルの多変量解析の研究2011

    • Author(s)
      Takuya Anmoto
    • Organizer
      The 12th Pacific Polymer Conference
    • Place of Presentation
      The Shilla Hotel (Jeju Island, Korea)
    • Related Report
      2011 Research-status Report
  • [Presentation] 立体特異性アニオン重合の研究2011

    • Author(s)
      Takahiro Furutani
    • Organizer
      The 12th Pacific Polymer Conference
    • Place of Presentation
      The Shilla Hotel (Jeju Island, Korea)
    • Related Report
      2011 Research-status Report
  • [Presentation] 立体特異性ラジカルおよびアニオン重合の研究2011

    • Author(s)
      古谷喬大
    • Organizer
      2011年日本化学会西日本大会
    • Place of Presentation
      徳島大学(徳島市)
    • Related Report
      2011 Research-status Report
  • [Presentation] NMRスペクトルの多変量解析の研究2011

    • Author(s)
      庵本卓矢
    • Organizer
      2011年日本化学会西日本大会
    • Place of Presentation
      徳島大学(徳島市)
    • Related Report
      2011 Research-status Report
  • [Presentation] 不斉誘導ラジカル重合の研究2011

    • Author(s)
      四宮未来
    • Organizer
      2011年日本化学会西日本大会
    • Place of Presentation
      徳島大学(徳島市)
    • Related Report
      2011 Research-status Report
  • [Presentation] NMRスペクトルの多変量解析の研究2011

    • Author(s)
      Tomohiro Hirano
    • Organizer
      24th ISPAC
    • Place of Presentation
      Villa Gualino (Torino, Italy)
    • Related Report
      2011 Research-status Report
  • [Presentation] 立体特異性アニオン重合の研究2011

    • Author(s)
      古谷喬大
    • Organizer
      第60回高分子学会年次大会
    • Place of Presentation
      大阪国際会議場(大阪市)
    • Related Report
      2011 Research-status Report
  • [Presentation] NMRスペクトルの多変量解析の研究2011

    • Author(s)
      庵本卓矢
    • Organizer
      第60回高分子学会年次大会
    • Place of Presentation
      大阪国際会議場(大阪市)
    • Related Report
      2011 Research-status Report
  • [Remarks]

    • URL

      http://poly.chem.tokushima-u.ac.jp

    • Related Report
      2013 Final Research Report
  • [Remarks] Ute Lab - HOME

    • URL

      http://poly.chem.tokushima-u.ac.jp

    • Related Report
      2013 Annual Research Report

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Published: 2011-08-05   Modified: 2019-07-29  

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