Development of Stereospecific Cationic Polymerizationthrough Intramolecular Participation at Polymer-end

• Project/Area Number: 23655039
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Kyoto University
• Principal Investigator: YAMAGO Shigeru 京都大学, 化学研究所, 教授 (30222368)
• Project Period (FY): 2011 – 2012
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2012: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2011: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
• Keywords: 立体規則性重合 / 立体選択的反応 / カチオン重合 / ラジカル重合 / 立体選択的重合 / ルイス酸 / カチオン反応 / 分子内関与 / ブロック共重合体

Research Abstract

New monomers for the stereospecific cationic polymerization were designed and synthesized, and model reactions for the polymerization reaction were investigated. The monomer was designed to utilize intramolecular participation of the olefin-pendant group to the polymer-end cation, which would regulate the direction of an incoming monomer. The model reaction proceeded in good yield with >90% diastereoselectivity by an appropriate choice of the pendant group and Lewis acid used as an activator. The results suggest a new possibility for the control of stereoselectivity by using the polymer-end group, while the conventional method so far utilized steric effects of the penultimate group. The same concept was applied to the monomer design for the stereospecific radical polymerization, and a conditions for the extremely high (>99%) stereospecific radical polymerization was developed.

Research Products

• [Journal Article] Highly Controlled Random and Alternating Copolymerization of (Meth)acrylates, Acrylonitrile, and (Meth)acrylamides with Vinyl Ethers by Organotellurium, Organostibine, and Organobismuthine Mediated Living Radical Polymerization Reactions (2012)
  • Author(s): Mishima, E.; Yamago, S
  • Journal Title: J. Polym. Sci. Part A: Polym. Chem Volume: 50 Issue: 11 Pages: 2254-2264
  • DOI: 10.1002/pola.26004
  • Peer Reviewed
• [Journal Article] Precision Synthesis of Hybrid Block Copolymers by Organotellurium-Mediated Successive Living Radical and Cationic Polymerizations (2011)
  • Author(s): Mishima, E.; Yamada, T.; Watanabe, H.; Yamago, S.
  • Journal Title: Chem. Asian J. Volume: 6 Issue: 2 Pages: 445-451
  • DOI: 10.1002/asia.201000402
  • Peer Reviewed
• [Journal Article] Controlled Alternating Copolymerization of (Meth)acrylates and Vinyl Ethers by Organoheteroatom-Mediated Living Radical Polymerization (2011)
  • Author(s): Mishima, E.; Yamago, S.
  • Journal Title: Macromol. Rapid Commun. Volume: 22 Issue: 3-4 Pages: 307-315
  • DOI: 10.1002/hc.20681
  • Peer Reviewed
• [Presentation] 光学活性オキサゾリジノンを持つアクリルイミドのルイス酸存在下における立体特異的ラジカル重合 (2013)
  • Author(s): 藤田健弘, 山子茂
  • Organizer: 第62回高分子学会年次大会
  • Place of Presentation: 京都
• [Presentation] 有機合成を基盤とした高分子の精密合成 (2012)
  • Author(s): 山子茂
  • Organizer: 日本化学会第92春季年会(招待講演)
  • Place of Presentation: 慶応義塾大学（横浜市）
• [Presentation] 有機合成に先導される新材料の創製 (2011)
  • Author(s): 山子茂
  • Organizer: 第21回万有福岡シンポジウム(招待講演)
  • Place of Presentation: 九州大学医学部（福岡市）
• [Presentation] ヘテロ元素の特徴を生かした高分子の精密合成 (2011)
  • Author(s): 山子茂
  • Organizer: 第38回有機典型元素化学討論会(招待講演)
  • Place of Presentation: 石川県立音楽堂邦楽ホール（金沢市）
• [Presentation] Precision Polymer Synthesis Based on Organoheteroatom-Mediated Controlled/Living Radical Polymerization (2011)
  • Author(s): S. Yamago
  • Organizer: 43rd IUPAC World Chemistry Congress(招待講演)
  • Place of Presentation: Pueruto Rico Convention Center (San Juan, Puerto Rico)
• [Presentation] Controlled Radical Polymerization and Radical Coupling Reactions Mediated by Organotellurium Compounds (2011)
  • Author(s): S. Yamago
  • Organizer: 242nd ACS National Meeting International Year of Chemistry Symposium: Controlled Radical Polymerization(招待講演)
  • Place of Presentation: Colorado Convention Center (Denver, USA)
• [Presentation] 高周期ヘテロ元素連鎖移動剤を用いたアクリレートとα,α-ジアルキルエチレンおよびα-アルキルエチレンとのリビングラジカル共重合 (2011)
  • Author(s): 三島絵里, 田村友樹, 山子茂
  • 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）
• [Presentation] Controlled Random Copolymerization of (Meth)acrylates and Nonconjugated Monomers by Organoheteroatom-mediated Living Radical polymerization (2011)
  • Author(s): E. Mishima, S. Yamago
  • Organizer: 5th Pacific Symposium on Radical Chemistry
  • Place of Presentation: HOTEL SEAMORE (Shirahama, Japan)
• [Book] 有機テルル化合物を用いるリビングラジカル重合法 TERP の最近の進歩 (2013)
  • Author(s): 山子茂
  • Publisher: 触媒
• [Book] 有機テルル化合物を用いるリビングラジカル重合法 TERP の開発と応用 (2013)
  • Author(s): 山子茂
  • Publisher: 未来材料
• [Book] 触媒 (2013)
  • Author(s): 山子茂
  • Total Pages: 6
  • Publisher: 触媒学会
• [Book] Organotellurium compounds as chain transfer agents for living radical polymerization (2012)
  • Author(s): Yamago, S.; Nakamura, Y.
  • Total Pages: 2012
  • Publisher: Patai' s Chemistry of Functional Groups, Organic Selenium and Tellurium Compounds, Vol. 3. Rappoport, Z., Marek, I.; Liebman, J. F. Eds, John Wiley & Sons Ltd, Chichester, UK