Preparation of helical structure in diblock copolymer using chiral dopant and evaluation of its hierarchical structure

• Project/Area Number: 19K05590
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 35010:Polymer chemistry-related
• Research Institution: Osaka Institute of Technology
• Principal Investigator: Hirai Tomoyasu 大阪工業大学, 工学部, 准教授 (60585917)
• Project Period (FY): 2019-04-01 – 2022-03-31
• Project Status: Completed (Fiscal Year 2021)
• Budget Amount: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000); Fiscal Year 2021: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2020: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2019: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: 有機ー無機ハイブリッド材料 / キラル / シリカ / らせん / アニオン重合 / 立体規則性高分子 / ポリへドラルオリゴメリックシルセスキオキサン / らせん構造 / 立体規則性 / 有機ー無機ハイブリッド / リビングアニオン重合 / 螺旋構造 / X線回折

Outline of Research at the Start

高分子に対してキラル分子を添加することで一方巻きに制御された動的螺旋構造形成が可能になる。しかしながら、この概念は剛直な主鎖型高分子には適応できるものの、柔軟な主鎖を持つビニル系高分子への適応は困難を極める。本研究課題では、嵩高い置換基を側鎖に有し、さらに立体規則性を精密に制御したメタクリレート骨格からなるブロック共重合体を精密重合法に基づき調製し、立体規則性および置換基の嵩高さが動的螺旋構造形成ひいては動的螺旋構造が自己組織的に集合することで形成する階層的な秩序構造形成におよぼす影響を明らかにする。

Outline of Final Research Achievements

Novel stereoregular polymers with polyhedral oligomeric silsesquioxane were prepared using precise synthesis method. The polymer formed preferred-handed helical conformation when they were mixed with small amount of chiral dopants. The helical structure was kept during calcination process, leading to a chiral silica. This is the first report that chiral silica was prepared from POSS. We believe that this finding can be applied in various kinds of fields including medicine.

Academic Significance and Societal Importance of the Research Achievements

本研究課題は、これまでに煩雑なプロセスを必要とされてきたキラルシリカの簡便な調製法、さらに本手法で調製したキラルシリカは従来材料を遥かに凌駕する微細らせん空孔を有することを明確に示したものであり、学術的には極めてインパクトが大きい。また、本研究より得られるキラルシリカは、医薬品開発の要となる光学分離の機関材料として機能することが十分に期待され、研究より得られる社会的な意義は極めて大きい。

Research Products

• [Int'l Joint Research] 国立陽明交通大学 （台湾）(その他の国・地域)
• [Int'l Joint Research] National Chiao Tung University(その他の国・地域 台湾)
• [Journal Article] Preferred-handed helical conformation in organic-inorganic hybrid block copolymers with well-controlled stereoregularity (2022)
  • Author(s): Satoshi Kometani, Tomoki Kato, Kei Manabe, Tamio Seko, Yu-Ning Chang, Huai-Rou Luo, Yoshihiro Agata, Noboru Ohta, Teruaki Hayakawa, Syuji Fujii, Yoshinobu Nakamura, Ming-Chia Li, Tomoyasu Hirai
  • Journal Title: Journal of Polymer Science Volume: 60 Issue: 5 Pages: 766-773
  • DOI: 10.1002/pol.20210761
• [Journal Article] Chiral Silica with Preferred-Handed Helical Structure via Chiral Transfer (2021)
  • Author(s): Kei Manabe, Sung-Yu Tsai, Satoshi Kuretani, Satoshi Kometani, Katsuyuki Ando, Yoshihiro Agata, Noboru Ohta, Yeo-Wan Chiang, I-Ming Lin, Syuji Fujii, Yoshinobu Nakamura, Yu-Ning Chang, Yuta Nabae, Teruaki Hayakawa, Chien-Lung Wang, Ming-Chia Li, and Tomoyasu Hirai
  • Journal Title: JACS Au Volume: 1 Issue: 4 Pages: 375-379
  • DOI: 10.1021/jacsau.1c00098
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Hairy Particles Synthesized by Living Anionic Polymerization-induced Self-assembly and Evaluation of Their Nanostructure (2021)
  • Author(s): Toshiki Terao, Hibiki Shiraishi, Mikito Yamazaki, Teruaki Hayakawa, Noboru Ohta, Syuji Fujii, Yoshinobu Nakamura, and Tomoyasu Hirai
  • Journal Title: Chemistry Letters Volume: 50 Issue: 5 Pages: 920-923
  • DOI: 10.1246/cl.200957
  • NAID: 130008040433
  • Peer Reviewed
• [Journal Article] Preparation of polymethyl methacrylate with well-controlled stereoregularity using anionic polymerization in ionic liquid (2020)
  • Author(s): Nobuyuki Otozawa, Rio Hamajima, Masataka Yoshioka, Raito Kato, Arisa Tanaka, Hiroto Fukuma, Toshiki Terao, Kei Manabe, Syuhu Fujii, Yoshnobu Nakamura, Atsushi Takahara, Tomoyasu Hirai
  • Journal Title: Journal of Polymer Science Volume: 58 Issue: 14 Pages: 1960-1964
  • DOI: 10.1002/pol.20200244
  • Peer Reviewed
• [Journal Article] Anionic Polymerization of Methacrylate-Functionalized Ionic Monomers in Ionic Liquid (2020)
  • Author(s): Nobuyuki Otozawa, Masataka Yoshioka,Daiki Ihara, Rio Hamajima, Raito Kato, Toshiki Terao, Hiroto Fukuma, Satoshi Kuretani, Tamio Seko, Syuji Fujii, Yoshinobu Nakamura, Motoyasu Kobayashi, Atsushi Takahara, Tomoyasu Hirai
  • Journal Title: Chemistry Letters Volume: 49 Issue: 12 Pages: 1459-1461
  • DOI: 10.1246/cl.200546
  • NAID: 130007956008
  • Peer Reviewed
• [Journal Article] Preparation of Polyhedral Oligomeric Silsesquioxane-Containing Block Copolymer with Well-Controlled Stereoregularity (2019)
  • Author(s): Sung-Yu Tsai, Satoshi Kuretani, Kei Manabe, Toshiki Terao, Takahiro Komamura, Yoshihiro Agata, Noboru Ohta, Syuji Fujii, Yoshunobu Nakamura, Chien-Lung Wang, Teruaki Hayakawa, Tomoyasu Hirai
  • Journal Title: Journal of Polymer Science Polymer Chemistry Volume: 57 Issue: 21 Pages: 2181-2189
  • DOI: 10.1002/pola.29498
  • Peer Reviewed / Int'l Joint Research
• [Presentation] Controlling of One-Handed Helical Conformation and Memory of Helicity in Poly(Methacrylate-Functionalized Polyhedral Oligomeric Silsesquioxane) with Well-Controlled Stereoregularity (2021)
  • Author(s): Tomoyasu Hirai, Kei Manabe, Syuji Fujii, Yoshinobu Nakamura
  • Organizer: Pacifichem
  • Int'l Joint Research / Invited
• [Presentation] 精密合成法に基づく立体規則性高分子の調製とその分子鎖凝集構造評価 (2021)
  • Author(s): 平井智康
  • Organizer: 第70回高分子学会年次大会
  • Invited
• [Presentation] Preparation of novel polymers with well-controlled stereoregularity and evaluation of its molecular aggregation state (2020)
  • Author(s): Tomoyasu Hirai
  • Organizer: PACCON2020
  • Int'l Joint Research / Invited
• [Presentation] 精密重合法に基づく立体規則性高分子の調製とその構造・物性評価 (2020)
  • Author(s): 平井智康
  • Organizer: 第69回高分子学会年次大会係
  • Invited
• [Presentation] Precise synthesis of stereoregular polymer with polyhedral oligomeric silsesquioxane side chain (2019)
  • Author(s): Tomoyasu Hirai, Sung-Yu Tsai, Satoshi Kuretani, Kei Manabe, Shuji Fujii, Yoshinobu Nakamura, Chien-Lung Wang, Teruaki Hayakawa
  • Organizer: 第68回高分子年次大会
• [Presentation] 新規立体規則性有機―無機ブロック共重合体の調製とその分子鎖凝集構造評価 (2019)
  • Author(s): 平井智康、榑谷仁志、真鍋圭、藤井秀司、中村吉伸、早川晃鏡
  • Organizer: 第38回無機高分子研究討論会
• [Presentation] Precise synthesis of novel polymer with well-controlled stereoregularity (2019)
  • Author(s): Tomoyasu Hirai, Sung-Yu Tsai, Satoshi Kuretani, Kei Manabe, Syuji Fujii, Yoshinobu Nakamura, Chien-Lung Wang, Teruaki Hayakawa
  • Organizer: 第30回エラストマー討論会
• [Presentation] 精密重合法に基づく高分子の立体規則性の制御とその分子鎖凝集構造 (2019)
  • Author(s): 平井智康
  • Organizer: 第169回東海高分子研究会講演会
  • Invited
• [Remarks] 機能性材料として注目の人工らせん高分子
  • URL: https://www.u-presscenter.jp/article/post-45784.html
• [Remarks] 機能性材料として注目の人工らせん高分子_らせん構造キラルシリカを簡便調製
  • URL: http://www.oit.ac.jp/japanese/pressrelease/show.php?id=7558