Synthesis of Structurally Well-defined Polymers via Microflow System Controlled Polymerization

• Project/Area Number: 20750077
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: Kyoto University
• Principal Investigator: NAGAKI Aiichiro Kyoto University, 大学院・工学研究科, 助教 (80452275)
• Project Period (FY): 2008 – 2009
• Project Status: Completed (Fiscal Year 2009)
• Budget Amount: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2009: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2008: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
• Keywords: マイクロ化学 / 有機合成化学 / 高分子化学

Research Abstract

We have developed the synthesis of structurally well-defined polymers via microflow system controlled polymerization. In this research, we have found that the use of microflow system could be effective method for (1) controlled cationic polymerization of vinyl monomer (2) controlled anionic polymerization of vinyl monomer (3) the development of the reaction based on the livingness of the polymer chain end (4)integrated and combinatorial synthesis of structurally defined block copolymers.

Research Products

• [Journal Article] Generations and Reactions of Cyano-Substituted Aryllithium Compounds Using Microreactors (2010)
  • Author(s): Nagaki, A.; Kim, H.; Matuo, C.; Yoshida, J.
  • Journal Title: Org. Biomol. Chem. 8 Pages: 1212-1217
• [Journal Article] Nitro-Substituted Aryl Lithium Compounds in Microreactor Synthesis: Switch between Kinetic and Thermodynamic Contro (2009)
  • Author(s): Nagaki, A.; Kim, H.; Yoshida, J.
  • Journal Title: Angew. Chem. Int. Ed. 48 Pages: 8063-8065
• [Journal Article] Generations and Reactions of N-t-Bus-aziridinyllithiums Using Microreactors (2009)
  • Author(s): Nagaki, A.; Takizawa, E.; Yoshida, J.
  • Journal Title: Chem. Lett. 38 Pages: 1060-1061
• [Journal Article] Allenylsilane Synthesis by Carbolithiation of Conjugated-enynes using Aryllithium in Microflow System. (2009)
  • Author(s): Tomida, Y.; Nagaki, A.; Yoshida, J.
  • Journal Title: Org. Lett. 11 Pages: 3614-1317
• [Journal Article] Microflow System Controlled Anionic Polymerization of MMA (2009)
  • Author(s): Nagaki, A.; Tomida, Y.; Miyazaki. A.; Yoshida, J.
  • Journal Title: Macromolecules 42 Pages: 4384-4387
• [Journal Article] Microflow Systems for Organic Synthesis: A New Synthetic Chemistry from Space Controlling Time. (2009)
  • Author(s): Yoshida, J.; Nagaki, A.
  • Journal Title: Kagaku 64 Pages: 22-26
• [Journal Article] Synthesis of Unsymmetrically Substituted Biaryls via Sequential Lithiation of Dibromobiaryls Using Integrated Microflow Systems. (2009)
  • Author(s): Nagaki, A.; Takabayashi, N.; Tomida, Y.; Yoshida, J.
  • Journal Title: Beilstein J. Org. Chem. 5,No16
• [Journal Article] Generation and Reactions of a-Silyl Oxiranyllithium Using Microflow System. (2009)
  • Author(s): Nagaki, A.; Takizawa, E.; Yoshida, J.
  • Journal Title: Chem. Lett. 38 Pages: 486-487
• [Journal Article] Oxiranyl Anion Methodology Using Microflow System (2009)
  • Author(s): Nagaki, A.; Takizawa. E.; Yoshida, J.
  • Journal Title: J. Am. Chem. Soc. 131 Pages: 1654-1655
• [Journal Article] Generation and Reactions of a-Silyl Oxiranyllithium Using Microflow System. (2009)
  • Author(s): Nagaki, A.; Takizawa, E.; Yoshida, J.
  • Journal Title: Chem.Lett. 38 Pages: 486-487
  • Peer Reviewed
• [Journal Article] Synthesis of Unsymmetrical Substituted Biaryls via Sequential Lithiation of Dibromobiaryls Using Integrated (2009)
  • Author(s): Nagaki, A.; Takabayashi, N.; Tomida, Y.; Yoshida, J.
  • Journal Title: Beilstein J.Org.Chem. 5 Pages: 16-16
  • Peer Reviewed
• [Journal Article] マイクロフロー合成化学の魅力-時間を空間で制御する新しい合成化学の創製- (2009)
  • Author(s): Yoshida, J.; Nagaki, A.
  • Journal Title: 化学 64 Pages: 22-26
• [Journal Article] Microflow System Controlled Anionic Polymerization of MMA (2009)
  • Author(s): Nagaki, A.; Tomida, Y.; Miyazaki. A.; Yoshida, J.
  • Journal Title: Macromolecule 42 Pages: 4384-4387
  • Peer Reviewed
• [Journal Article] Carbolithiation of Conjugated Enynes with Aryllithiums in Microflow System and Applications to Synthesis of Allenylsilanes (2009)
  • Author(s): Tomida, Y.; Nagaki, A.; Yoshida, J.
  • Journal Title: Org.Lett. 11 Pages: 3614-3617
  • Peer Reviewed
• [Journal Article] マイクロリアクターを用いたアニオン重合の制御 (2009)
  • Author(s): Nagaki, A.; Yoshida, J.
  • Journal Title: 「マイクロリアクターによる合成技術と工業生産」サイエンス&テクノロジー Pages: 147-159
• [Journal Article] Generations and Reactions of N-Bus-aziridinyllithiums Using Microreactors (2009)
  • Author(s): Nagaki, A.; Takizawa, E.; Yoshida, J.
  • Journal Title: Chem.Lett 38 Pages: 1060-1061
  • Peer Reviewed
• [Journal Article] Nitro-Substituted Aryl Lithium Compounds in Microreactor Synthesis : Switch between Kinetic and Thermodynamic Control (2009)
  • Author(s): Nagaki, A.; Kim, H.; Yoshida, J.
  • Journal Title: Angew.Chem.Int.Ed. 48 Pages: 8063-8065
  • Peer Reviewed
• [Journal Article] Generation and Reaction of Cyano-Substituted Aryllithium Compounds Using Microreactors (2009)
  • Author(s): Nagaki, A.; Kim, H.; Usutani, H.; Matsuo, C.; Yoshida, J.
  • Journal Title: Org.Biomol.Chem. (in press.)
• [Journal Article] Oxiranyl Anion Methodology Using Microflow Systems (2009)
  • Author(s): Nagaki, A. ; Takizawa, E. ; Yoshida, J.
  • Journal Title: J. Am. Chem. Soc. 131 Pages: 1654-1655
  • Peer Reviewed
• [Journal Article] Aryllithium Compounds Bearing Alkoxycarbonyl Groups. Generation and Reactions Using a Microflow System. (2008)
  • Author(s): Nagaki, A.; Kim, H.; Yoshida, J.
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 7833-7836
• [Journal Article] Synthesis of Unsymmetrical Biaryls by Means of Mono-Selective Reaction of polyhaloarenes Using Integrated Microflow System (2008)
  • Author(s): Nagaki, A.; Takabayashi, N.; Tomida, Y.; Yoshida, J.
  • Journal Title: Org. Lett. 18 Pages: 3937-3940
• [Journal Article] Microflow System Controlled Anionic Polymerization of Styrenes. (2008)
  • Author(s): Nagaki, A.; Tomida, Y.; Yoshida, J.
  • Journal Title: Macromolecules 41 Pages: 6322-6330
• [Journal Article] Microflow System Controlled Carbocationic Polymerization of Vinyl Ethers (2008)
  • Author(s): Nagaki, A.; Iwasaki, T.; Kawamura, K.; Yamada, D.; Suga, S.; Ando, T.; Sawamoto, M.; Yoshida, J.
  • Journal Title: Chem. Asian J. 3 Pages: 1558-1567
• [Journal Article] Flash Chemistry: Fast Chemical Synthesis Using Microreactors (2008)
  • Author(s): Yoshida, J.; Nagaki, A.; Yamada, T.
  • Journal Title: Chem. Eur. J. 14 Pages: 7450-7459
• [Journal Article] Modern Strategies in Electroorganic Synthesis (2008)
  • Author(s): Yoshida, J.; Kataoka, K.; Horcajada, R.; Nagaki, A.
  • Journal Title: Chem. Rev. 108 Pages: 2265-2299
• [Journal Article] Flash Chemistry : Fast Chemical Synthesis by Using Microreactors. (2008)
  • Author(s): Yoshida, J. ; Nagaki, A. ; Yamada, T.
  • Journal Title: Chem. Eur. J. 14 Pages: 7450-7459
  • Peer Reviewed
• [Journal Article] Modern Strategies in Electroorganic Synthesis (2008)
  • Author(s): Yoshida, J. ; Kataoka, K. Horcajada, R. ; Nagaki, A.
  • Journal Title: Chem. Rev. 108 Pages: 2265-2299
  • Peer Reviewed
• [Journal Article] Microflow System Controlled Carbocationic Polymerization of Vinyl Ethers (2008)
  • Author(s): Nagaki, A. ; Iwasaki, T. ; Kawamura, K. ; Yamada, D. ; Suga
  • Journal Title: Chem. As J. 3 Pages: 1558-1567
  • Peer Reviewed
• [Journal Article] Microflow System Controlled Anionic Polymerization of Styrenes (2008)
  • Author(s): Nagaki, A. ; Tomida, Y. ; Yoshida, J.
  • Journal Title: Macromolecules 41 Pages: 6322-6330
  • Peer Reviewed
• [Journal Article] Synthesis of Unsymmetrical Biaryls by Means of Mono-Selective Reaction of polyhaloarenes Using Integrated (2008)
  • Author(s): Nagaki, A. ; Takabayashi, N. Tomida, Y. ; Yoshida, J.
  • Journal Title: Org. Lett. 10 Pages: 3937-3940
  • Peer Reviewed
• [Journal Article] Aryllithium Compounds Bearing Alkoxycarbonyl Groups. Generation and Reactions Using a Microflow System (2008)
  • Author(s): Nagaki, A. ; Kim, H. ; Yoshida, J.
  • Journal Title: Angew. Chem., Int. Ed. 47 Pages: 7833-7836
  • Peer Reviewed
• [Presentation] Unstable Aryllithiums Using Integrated Microflow Systems (2010)
  • Author(s): A. Nagaki, H Kim, Y. Tomida, N. Takabayashi, H. Usutani, J. Yoshida
  • Organizer: The 11nd International Conference on Microreaction Technology, Kyoto Research Park
  • Place of Presentation: Kyoto, Japan
• [Presentation] Generation and Reactions of Unstable Aryllithiums Using Integrated Microflow Systems (2010)
  • Author(s): 永木愛一郎
  • Organizer: The 11nd International Conference on Microreaction Technology
  • Place of Presentation: Kyoto Research Park, Kyoto, Japan
• [Presentation] Flash Chemistry: Fast Chemical Synthesis in Microflow Systems (2009)
  • Author(s): A. Nagaki, J. Yoshida
  • Organizer: Proceedings of the Seventh International ASME Conference on Nanochannels, Microchannels and Minichannels (ICNMM2009) Pohang
  • Place of Presentation: South Korea(invited)
• [Presentation] マイクロフローシステムを用いた不安定アリールリチウム種の発生・反応 (2009)
  • Author(s): 永木愛一郎、金ヒジン、高林尚史、富田裕、吉田潤一
  • Organizer: 第56回有機金属化学討論会
  • Place of Presentation: 京都
• [Presentation] アルキルメタクリルレート類のマイクロフロー精密アニオン重合反応 (2009)
  • Author(s): 永木愛一郎、宮崎豊生、富田裕、吉田潤一
  • Organizer: 第58回高分子討論会
  • Place of Presentation: 熊本
• [Presentation] マイクロフロー精密アニオン重合反応によるスチレン-アルキルメタクリルレート類のブロックポリマー合成 (2009)
  • Author(s): 永木愛一郎、宮崎豊生、吉田潤一
  • Organizer: 第58回高分子討論会
  • Place of Presentation: 熊本
• [Presentation] スチレン類のマイクロフロー精密アニオン重合反応による精密構造制御ポリマー合成 (2009)
  • Author(s): 永木愛一郎、富田裕、吉田潤一
  • Organizer: 第58回高分子討論会
  • Place of Presentation: 熊本
• [Presentation] 有機合成反応へのマイクロリアクターの利用 (2009)
  • Author(s): 永木愛一郎、吉田潤一
  • Organizer: INCHEM TOKYO 2009
  • Place of Presentation: 東京
• [Presentation] Flash Chemistry : Fast Chemical Synthesis in Microflow Systems (2009)
  • Author(s): 永木愛一郎
  • Organizer: Proceedings of the Seventh International ASME Conference on Nanochannels, Microchannels and Minichannels (ICNMM2009)
  • Place of Presentation: Pohang, South Korea
• [Presentation] Generation and Reactions of ortho-Bromophenyllithium without Benzyne Formation Using Microflow System (2008)
  • Author(s): Nagaki, A
  • Organizer: 2008 AIChE Spring Meeting
  • Place of Presentation: USA New Jersey
  • Year and Date: 2008-04-03
• [Presentation] Generation and Reactions of ortho-Bromophenyllithium without Benzyne Formation Using Microflow System. (2008)
  • Author(s): A. Nagaki, Y. Usutani, H. Tomida, H Kim, N. Takabayashi, T. Nokami, H. Okamoto, J. Yoshida
  • Organizer: The 10nd International Conference on Microreaction Technology
  • Place of Presentation: New Orleans, US
• [Book] マイクロリアクターによる合成技術と工業生産(マイクロリアクターを用いたアニオン重合の制御) (2009)
  • Author(s): Nagaki, A.; Yoshida, J.
  • Publisher: サイエンス&テクノロジー
• [Book] Polymerization: Cationic Living Polymeriation(Micro Process Engineering, Volume 2: Devices, Reactions and Applications., Chapter 14) (2009)
  • Author(s): Yoshida, J.; Nagaki, A.
  • Publisher: Wiley-VCH
• [Book] Gas Phase and Gas/Liquid Phase Reactions: Substitution(Micro Process Engineering, Volume 2: Devices, Reactions and Applications., Chapter 8) (2009)
  • Author(s): Yoshida, J.; Nagaki, A.
  • Publisher: Wiley-VCH
• [Book] Liquid Phase and Liquid/Liquid Phase Reactions: Oxidations and reductions(Micro Process Engineering, Volume 2: Devices, Reactions and Applications., Chapter 7) (2009)
  • Author(s): Yoshida, J.; Nagaki, A.
  • Publisher: Wiley-VCH
• [Book] Liquid Phase and Liquid/Liquid Phase Reactions: Addition and elimination reactions(Micro Process Engineering, Volume 2: Devices, Reactions and Applications., Chapter 5.) (2009)
  • Author(s): Yoshida, J.; Nagaki, A.
  • Publisher: Wiley-VCH
• [Book] Handbook of micro reactors : Devices, Reactions and Applications. Volume 2 (Liquid Phase and Liquid/Liquid Phase Reactions : Addition and elimination reactions) (2009)
  • Author(s): Yoshida, J. ; Nagaki, A.
  • Total Pages: 15
  • Publisher: Wiley -VCH
• [Book] Handbook of micro reactors : Devices, Reactions and Applications. Volume 2(Liquid Phase and Liquid/Liquid Phase Reactions : Oxidations and reductions) (2009)
  • Author(s): Yoshida, J. ; Nagaki, A.
  • Total Pages: 16
  • Publisher: Wiley-VCH
• [Book] Handbook of micro reactors : Devices, Reactions and Applications. Volume 2(Gas Phase and Gas/Liquid Phase Reactions : Substitution) (2009)
  • Author(s): Yoshida, J. ; Nagaki, A.
  • Total Pages: 9
  • Publisher: Wiley-VCH
• [Book] Handbook of micro reactors : Devices, Reactions and Applications. Volume 2(Polymerization : Cationic Living Polymeriation) (2009)
  • Author(s): Yoshida, J. ; Nagaki, A.
  • Total Pages: 13
  • Publisher: Wiley-VCH