炭素－炭素二重結合を含むπ共役系高分子の分子量制御法の開発

2014 Fiscal Year Annual Research Report

• Project/Area Number: 24550141
• Research Institution: Kanagawa University
• Principal Investigator: 横澤 勉 神奈川大学, 工学部, 教授 (80182690)
• Co-Investigator(Kenkyū-buntansha): 太田 佳宏 神奈川大学, 工学部, 助教 (90625617)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Keywords: 触媒移動型重合 / ポリスチルベン / 連鎖縮合重合 / π共役系高分子 / Pd触媒

Outline of Annual Research Achievements

本研究では申請者が開発したポリチオフェンやポリフルオレンなどの分子量制御法（触媒移動型連鎖縮合重合）を芳香族π共役系高分子からポリフェニレンビニレンやポリアセチレンのような炭素－炭素二重結合を含むπ共役系高分子まで展開することを目的としている。これらのポリマーも触媒移動型連鎖縮合重合によって分子量制御して合成できるようになれば、ポリチオフェンとポリアセチレンとのブロック共重合体のようなこれまでにないπ共役系高分子を創製することができる。今年度の研究実績は以下のとおりである。
（１）α,ω-ジブロモポリスチルベンへの選択的両末端アリール化　　昨年度、4,4'-ジブロモスチルベンの炭素ー炭素二重結合（C=C）に結合しているフェニル基のオルト位にアルコキシ基が導入された基質では、Pd触媒がC=C上を分子内移動し、フェニルボロン酸エステルと反応して選択的に二置換体を与えることを明らかにした。今年度はさらに共役長の長いα,ω-ジブロモポリスチルベンに対してトリルボロン酸エステルを反応させて、同様に選択的にアリール二置換体が生成することを明らかにした。すなわち、C=Cを含む長い共役主鎖上もPd触媒が分子内移動することを明らかにした。
（２）スチルベンモノマーの触媒移動重合　　t-Bu3P配位子のAr-Pd-Brでは触媒のAr基がポリスチルベン末端に導入されなかったが、Ar-Pd-Iを用いるとAr基が高分子末端に導入され、触媒移動機構で重合が進行することを明らかにした。これはAr-Pd-IがAr-Pd-Brに比べて、スチルベンモノマーのC=Cによって分解しにくいためと考えられる。

Research Products

• [Journal Article] Investigation of Mizoroki-Heck Coupling Polymerization as a Catalyst-Transfer Condensation Polymerization for Synthesis of Poly(p-phenylenevinylene) (2015)
  • Author(s): Masataka Nojima, Ryosuke Saito, Yoshihiro Ohta, and Tsutomu Yokozawa
  • Journal Title: J. Polym. Sci., Part A: Polym. Chem. Volume: 53 Pages: 543-551
  • DOI: 10.1002/pola.27472
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Influence of the Boron Moiety and Water on Suzuki-Miyaura Catalyst-Transfer Condensation Polymerization (2015)
  • Author(s): Kentaro Kosaka, Yoshihiro Ohta, and Tsutomu Yokozawa
  • Journal Title: Macromol. Rapid Commun. Volume: 36 Pages: 373-377
  • DOI: 10.1002/marc.201400530
  • Peer Reviewed
• [Journal Article] Structural Requirements for Palladium Catalyst Transfer on a Carbon-Carbon Double Bond (2015)
  • Author(s): Masataka Nojima, Yoshihiro Ohta, Tsutomu Yokozawa
  • Journal Title: J. Am. Chem. Soc. Volume: 137 Pages: web released
  • DOI: 10.1021/jacs.5b03113
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Catalyst-Transfer Condensation Polymerization of Acceptor Aromatic Monomers and of Donor Carbon-Carbon Double Bond-Containing Monomers (2015)
  • Author(s): Tsutomu Yokozawa, Yutaka Nanashima, Masataka Nojima, and Yoshihiro Ohta
  • Journal Title: Macromol. Symp. Volume: 350 Pages: 22-33
  • DOI: 10.1002/masy.201400021
  • Peer Reviewed
• [Journal Article] Band Gap Tuning of Narrow-Dispersity Two-Dimensional Conductive Polymers with Electroactive Side-Chains (2014)
  • Author(s): Yi-Lung Yang, Yi-Huan Lee, Yu-Ping Lee, Chi-Ju Chiang, Fong-Yu Hsu, Wei-Chun Hsu, Man-kit Leung, Leeyih Wang, Chi-An Dai, Yoshihiro Ohta, and Tsutomu Yokozawa
  • Journal Title: J. Polym. Sci., Part A: Polym. Chem. Volume: 52 Pages: 1217-1227
  • DOI: 10.1002/pola.27107
  • Peer Reviewed
• [Journal Article] Co-Crystallization Phase Transformations in All-Conjugated Block Copolymers with Different Main-Chain Moieties (2014)
  • Author(s): Yi-Huan Lee, Wei-Chih Chen, Yi-Lung Yang, Chi-Ju Chiang, Tsutomu Yokozawa, and Chi-An Dai
  • Journal Title: Nanoscale Volume: 6 Pages: 5208-5216
  • DOI: 10.1039/c3nr06037c
  • Peer Reviewed
• [Journal Article] Investigation of Catalyst-Transfer Condensation Polymerization for Synthesis of Poly(p-phenylenevinylene) (2014)
  • Author(s): Masataka Nojima, Yoshihiro Ohta, and Tsutomu Yokozawa
  • Journal Title: J. Polym. Sci., Part A: Polym. Chem. Volume: 52 Pages: 2643-2653
  • DOI: 10.1002/pola.27281
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] A New Strategy for Co-Assembling -Conjugated Polymer/Cadmium Sulfide Hybrids into Efficient Charge-Transporting Nanochannel Array by Using All-Conjugated Diblock Copolymer Motif (2014)
  • Author(s): Yi-Huan Lee, Yu-Ping Lee, Fan-Kai Wei, Chia-Hung Wu, Wei-Chih Chen, Ching Shen, Huai-An Jeng, Leeyih Wang, Ming-Wei Liu, Yi-Fan Chen, Tsutomu Yokozawa, and Chi-An Dai
  • Journal Title: J. Mater. Chem. A Volume: 2 Pages: 14600-14612
  • DOI: 10.1039/c4ta00754a
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of P3HT-P3HOT Random Copolymers with Tunable Band Gap via Grignard Metathesis Polymerization (2014)
  • Author(s): Yi-Lung Yang, Yi-Huan Lee, Yu-Ping Lee, Chi-Ju Chiang, Ching Shen , Chun-Ching Wu, Chi-An Dai, Yoshihiro Ohta, and Tsutomu Yokozawa
  • Journal Title: Polym. Int. Volume: 63 Pages: 2068-2075
  • DOI: 10.1002/pi.4744
  • Peer Reviewed
• [Presentation] Catalyst-Transfer Condensation Polymerization of Acceptor Aromatic Monomers and of Donor Carbon-Carbon Double Bond-Containing Monomers (2014)
  • Author(s): T. Yokozawa, Y. Nanashima, M. Nojima, Y. Ohta
  • Organizer: Korea-Japan Joint Polymer Symposium 2014
  • Place of Presentation: KAIST
  • Year and Date: 2014-10-29 – 2014-10-31
  • Invited
• [Presentation] 触媒移動型連鎖縮合重合における触媒の挙動 (2014)
  • Author(s): 野嶋雅貴, 太田佳宏, 横澤 勉
  • Organizer: 第 15 回リング・チューブ超分子研究会シンポジウム
  • Place of Presentation: 東京工業大学
  • Year and Date: 2014-10-27 – 2014-10-28
  • Invited
• [Presentation] 触媒移動型連鎖縮合重合における遷移金属触媒の分子内移動特性とブロック共重合挙動 (2014)
  • Author(s): 野嶋雅貴・巳上幸一郎・増本優衣・水越祥英・佐藤 玄・太田佳宏・内山真伸・横澤 勉
  • Organizer: 第 63 回高分子討論会
  • Place of Presentation: 長崎大学
  • Year and Date: 2014-09-24 – 2014-09-26
• [Presentation] DFT 計算を用いた触媒移動型連鎖縮合重合の素反応解析 (2014)
  • Author(s): 巳上 幸一郎・増本 優衣・水越 祥英・佐藤 玄・野嶋 雅貴・横澤 勉・内山 真伸
  • Organizer: 第 63 回高分子討論会
  • Place of Presentation: 長崎大学
  • Year and Date: 2014-09-24 – 2014-09-26
• [Presentation] Pd 触媒前駆体を用いた鈴木-宮浦カップリング触媒移動型連鎖縮合重合に適した配位子の検討 (2014)
  • Author(s): 小坂 研太郎・太田佳宏・横澤 勉
  • Organizer: 第 63 回高分子討論会
  • Place of Presentation: 長崎大学
  • Year and Date: 2014-09-24 – 2014-09-26
• [Presentation] Investigation of Catalyst-Transfer Condensation Polymerization of Pyridine-Thiophene Monomer By Means of Model Reactions (2014)
  • Author(s): M. Katoh, Y. Ohta, T. Yokozawa
  • Organizer: Polycondensation 2014
  • Place of Presentation: Tokyo Institute of Technology
  • Year and Date: 2014-09-08 – 2014-09-11
• [Presentation] Band Gap Tuning of Narrow-Polydispersity Two-Dimensional Conductive Polymers with Electroactive Side-Chains (2014)
  • Author(s): Y.-L. Yang, Y.-H. Lee, Y.-P. Lee, C.-J. Chiang, F-Y. Hsu, W.-C. Hsu, L. Wang, C.-A. Dai, Y. Ohta, T. Yokozawa
  • Organizer: Polycondensation 2014
  • Place of Presentation: Tokyo Institute of Technology
  • Year and Date: 2014-09-08 – 2014-09-11
• [Presentation] Investigation of Ni-Catalyzed Suzuki-Miyaura Cross-Coupling Polymerization for the Synthesis of Well-Defined Poly(3-hexylthiophene) (2014)
  • Author(s): K. Kosaka, Y. Ohta, T. Yokozawa
  • Organizer: Polycondensation 2014
  • Place of Presentation: Tokyo Institute of Technology
  • Year and Date: 2014-09-08 – 2014-09-11
• [Presentation] Intramolecular Transfer Properties of Transition Metal Catalysts and Block Copolymerization Behavior in Catalyst-Transfer Condensation Polymerization (2014)
  • Author(s): M. Nojima, K. Mikami, Y. Masumoto, Y. Mizukoshi, H. Sato, Y. Ohta, M. Uchiyama, T. Yokozawa
  • Organizer: Polycondensation 2014
  • Place of Presentation: Tokyo Institute of Technology
  • Year and Date: 2014-09-08 – 2014-09-11
• [Presentation] 縮合系高分子やπ共役系高分子の精密合成 (2014)
  • Author(s): 横澤 勉
  • Organizer: 高分子夏季大学
  • Place of Presentation: 東京
  • Year and Date: 2014-07-16 – 2014-07-18
  • Invited
• [Presentation] Intramolecular Transfer of Catalyst on Carbon-Carbon Double Bond and Aryl Group for the Synthesis of Well-Defined π-Conjugated Polymers Containing Vinylene Group (2014)
  • Author(s): T. Yokozawa, M. Nojima, Y. Ohta
  • Organizer: 8th International Symposium on High-Tech Polymer Materials
  • Place of Presentation: Beijing
  • Year and Date: 2014-07-01 – 2014-07-05
  • Invited
• [Presentation] Similar and Different Behavior of Catalyst-Transfer Condensation Polymerization with Several Catalysts (2014)
  • Author(s): M. Nojima, Y. Ohta, T. Yokozawa
  • Organizer: NIMS CONFERENCE 2014
  • Place of Presentation: Tsukuba
  • Year and Date: 2014-07-01 – 2014-07-03
• [Presentation] Intramolecular Transfer of Catalyst on Carbon-Carbon Double Bond for the Synthesis of Well-Defined Conjugated Polymers (2014)
  • Author(s): T. Yokozawa, M. Nojima, Y. Ohta
  • Organizer: NIMS CONFERENCE 2014
  • Place of Presentation: Tsukuba
  • Year and Date: 2014-07-01 – 2014-07-03
  • Invited
• [Presentation] DFT 計算を用いた触媒移動型連鎖縮合重合の理論解析 (2014)
  • Author(s): 巳上 幸一郎・増本 優衣・水越 祥英・佐藤 玄・野嶋 雅貴・横澤 勉・内山 真伸
  • Organizer: 第 63 回高分子学会年次大会
  • Place of Presentation: 名古屋国際会議場
  • Year and Date: 2014-05-28 – 2014-05-30
• [Presentation] 高分子末端 Pd 開始剤化法によるポリフェニレンビニレンとポリチオフェンとのブロック共重合体の合成 (2014)
  • Author(s): 佐野 武志・野嶋 雅貴・太田佳宏・横澤 勉
  • Organizer: 第 63 回高分子学会年次大会
  • Place of Presentation: 名古屋国際会議場
  • Year and Date: 2014-05-28 – 2014-05-30
• [Presentation] 置換基効果型連鎖縮合重合によるシアノ基置換ポリフェニレンビニレンの合成 (2014)
  • Author(s): 高辻 孝信・信田 恭平・野嶋 雅貴・太田佳宏・横澤 勉
  • Organizer: 第 63 回高分子学会年次大会
  • Place of Presentation: 名古屋国際会議場
  • Year and Date: 2014-05-28 – 2014-05-30
• [Presentation] INVESTIGATION OF Ni-CATALYST-TRANSFER SUZUKI-MIYAURA COUPLING POLYMERIZATION FOR THE SYNTHESIS OF POLY(3-HEXYLTHIOPHENE) (2014)
  • Author(s): K. Kosaka, Y. Ohta, T. Yokozawa
  • Organizer: 3rd International Symposium on Controlled/Living Polymerization
  • Place of Presentation: Antalya
  • Year and Date: 2014-05-01 – 2014-05-04
• [Presentation] COMPARATIVE STUDY OF CATALYSTS FOR CATALYST-TRANSFER CONDENSATION POLYMERIZATION (2014)
  • Author(s): M. Nojima, Y. Ohta, T. Yokozawa
  • Organizer: 3rd International Symposium on Controlled/Living Polymerization
  • Place of Presentation: Antalya
  • Year and Date: 2014-05-01 – 2014-05-04
• [Presentation] INVESTIGATION OF CATALYST-TRANSFER CONDENSATION POLYMERIZATION OF DONOR-ACCEPTOR BIARYL MONOMERS BY MEANS OF MODEL REACTIONS (2014)
  • Author(s): M. Katoh, Y. Ohta, T. Yokozawa
  • Organizer: 3rd International Symposium on Controlled/Living Polymerization
  • Place of Presentation: Antalya
  • Year and Date: 2014-05-01 – 2014-05-04
• [Presentation] CATALYST-TRANSFER CONDENSATION POLYMEIZATION OF MONOMERS CONTAINING CARBON-CARBON DOUBLE BOND (2014)
  • Author(s): T. Yokozawa, M. Nojima, Y. Ohta
  • Organizer: 3rd International Symposium on Controlled/Living Polymerization
  • Place of Presentation: Antalya
  • Year and Date: 2014-05-01 – 2014-05-04
  • Invited
• [Remarks] 横澤研究室の業績と論文
  • URL: http://apchem2.kanagawa-u.ac.jp/~yokozawalab/frame.html