Synthesis of ladder-type polyolefins by utilizing affinity between dinuclear complexes and non-conjugated dienes

• Project/Area Number: 15H03814
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Polymer chemistry
• Research Institution: Hirosaki University (2018); Tokyo Institute of Technology (2015-2017)
• Principal Investigator: Takeuchi Daisuke 弘前大学, 理工学研究科, 教授 (90311662)
• Project Period (FY): 2015-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥13,520,000 (Direct Cost: ¥10,400,000、Indirect Cost: ¥3,120,000); Fiscal Year 2017: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2016: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2015: ¥6,110,000 (Direct Cost: ¥4,700,000、Indirect Cost: ¥1,410,000)
• Keywords: 高分子合成 / 遷移金属触媒重合 / ハシゴ型高分子 / 複核錯体 / ポリオレフィン / 共重合体 / ブロック共重合体 / ネットワークポリマー / カチオン重合 / ポリスチレン / 合成化学

Outline of Final Research Achievements

Ladder polymers have the structure containing two linear polymers cross-linked with each other. Such polymers have been synthesized by multiple cyclization of linear polymers with reactive side groups or polycondensation/polyaddition of multi-functionalized monomers. In this work, we found that double-decker type dinickel catalysts promote copolymerization of ethylene with non-conjugated dienes to give the corresponding polyolefins with ladder structure. Dipalladium catalysts are effective for copolymerization of ethylene with dienes with polar functional groups.

Academic Significance and Societal Importance of the Research Achievements

二官能性ジビニルモノマーを用いた共重合においては、通常は多数の高分子鎖同士のランダムな架橋反応が起こり、有機溶媒に不溶な架橋高分子が生成し、完全なハシゴ型高分子は得られない。本研究では二核ニッケル錯体を触媒に用いることで、選択的な架橋反応を促進し、有機溶媒に対する可溶なハシゴ型ポリオレフィンの合成を達成した。二核金属錯体触媒が、エチレンと様々なジビニルモノマーとの共重合に応用できる可能性を見出した。

Research Products

• [Int'l Joint Research] ストラスブール大学(フランス)
• [Journal Article] Ethylene polymerization catalyzed by dinickel complexes with a double-decker structure (2017)
  • Author(s): Daisuke Takeuchi, Yuriko Chiba, Shigenaga Takano, Hideo Kurihara, Minoru Kobayashi, Kohtaro Osakada
  • Journal Title: Polymer Chemistry Volume: 印刷中 Issue: 34 Pages: 5112-5119
  • DOI: 10.1039/c7py00333a
  • Peer Reviewed
• [Journal Article] Synthesis of Optically Active Polystyrene Catalyzed by Monophosphine Pd Complexes (2016)
  • Author(s): Matthieu Jouffroy, Dominique Armspach, Dominique Matt, Kohtaro Osakada, Daisuke Takeuchi
  • Journal Title: Angew. Chem. Int. Ed. Volume: 55 Pages: 8367-8370
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Controlled isomerization polymerization of olefins, cycloolefins, and dienes (2016)
  • Author(s): Daisuke Takeuchi, Kohtaro Osakada
  • Journal Title: Polymer Volume: 82 Pages: 392-405
  • DOI: 10.1016/j.polymer.2015.09.077
  • Peer Reviewed
• [Journal Article] Synthesis of Optically Active Polystyrene using Monophosphine Pd Complexes (2016)
  • Author(s): Matthieu Jouffroy, Dominique Armspach, Dominique Matt, Kohtaro Osakada, Daisuke Takeuchi
  • Journal Title: Angewandte Chemie, International Edition Volume: 55
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Double cyclizative polymerization of trienes catalyzed by Pd complexes. Combined ring-forming and chain-walking reactions of the growing end (2015)
  • Author(s): Kenya Motokuni, Daisuke Takeuchi, Kohtaro Osakada
  • Journal Title: Polymer Chemistry Volume: 6 Issue: 8 Pages: 1248-1254
  • DOI: 10.1039/c4py01555j
  • Peer Reviewed
• [Journal Article] Cyclopolymerization of 1,6-heptadienes and 1,6,11-dodecatrienes having acyclic substituents catalyzed by Pd-diimine complexes (2015)
  • Author(s): Kenya Motokuni, Daisuke Takeuchi, Kohtaro Osakada
  • Journal Title: Polymer Bulletin Volume: 72 Issue: 3 Pages: 583-597
  • DOI: 10.1007/s00289-014-1293-0
  • Peer Reviewed
• [Journal Article] Polymerization of Methylenecyclohexanes Catalyzed by Diimine-Pd Complex. Polymers Having trans- or cis-1,4- and trans-1,3-Cyclohexylene Groups (2015)
  • Author(s): Daisuke Takeuchi, Keisuke Watanabe, Kenji Sogo, Kohtaro Osakada
  • Journal Title: Organometallics Volume: 34 Issue: 12 Pages: 3007-3011
  • DOI: 10.1021/acs.organomet.5b00313
  • Peer Reviewed
• [Journal Article] Synthesis of Polyketones Containing substituted Six-Membered Rings via Pd-Catalyzed Copolymerization of Methylenecyclohexanes with Carbon Monoxide (2015)
  • Author(s): Daisuke Takeuchi, Keisuke Watanabe, Kohtaro Osakada
  • Journal Title: Macromolecules Volume: 48 Issue: 18 Pages: 5745-6749
  • DOI: 10.1021/acs.macromol.5b01458
  • Peer Reviewed
• [Journal Article] Olefin Polymerization Catalyzed by Double-Decker Dipalladium Complexes: Low Branched Poly(a-Olefin)s by Selective Insertion of the Monomer Molecule (2015)
  • Author(s): Shigenaga Takano, Daisuke Takeuchi, Kohtaro Osakada
  • Journal Title: Chemistry - A European Journal Volume: 21 Issue: 45 Pages: 16209-16218
  • DOI: 10.1002/chem.201501991
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] 単核および二核パラジウム錯体触媒による新しいオレフィン重合 (2018)
  • Author(s): 竹内大介
  • Organizer: 重合触媒設計研究会セミナー
  • Invited
• [Presentation] 二層型二核パラジウム錯体によるエチレンとスチレン誘導体との共重合 (2017)
  • Author(s): 岩澤 孝，竹内 大介，小坂田 耕太郎
  • Organizer: 第66回高分子討論会
• [Presentation] ジヒドロキシビピリジンコバルト錯体を用いたブタジエンの重合 (2017)
  • Author(s): 山川 進二，竹内 大介，小坂田 耕太郎
  • Organizer: 第66回高分子討論会
• [Presentation] ビピリジン配位子を有するニッケル錯体を用いたブタジエンとノルボルネン類の共重合 (2017)
  • Author(s): 山川 進二，竹内 大介，小坂田 耕太郎
  • Organizer: 第66回高分子討論会
• [Presentation] Synthesis of poly(arylene alkylene) utilizing Pd-catalyzed polycondensation (2017)
  • Author(s): Liyi TAN, Daisuke TAKEUCHI, Kohtaro OSAKADA
  • Organizer: 第66回高分子討論会
• [Presentation] 位置選択的かつ立体選択的にメチル分岐の導入されたポリアルケニルシクロヘキサンの合成と物性 (2017)
  • Author(s): 佐藤 圭，竹内 大介，小坂田 耕太郎
  • Organizer: 第66回高分子年次大会
• [Presentation] Heck Polycondensation of Diiodo Arenes with N,N'-Dialkenyl Diimides by Pd Catalysts (2017)
  • Author(s): Liyi TAN, Daisuke TAKEUCHI, Kohtaro OSAKADA
  • Organizer: 第66回高分子年次大会
• [Presentation] 二層型二核パラジウム錯体によるエチレンと種々のコモノマーとの共重合 (2017)
  • Author(s): 竹内大介・岩澤孝・高野重永・小坂田耕太郎
  • Organizer: 第66回高分子年次大会
• [Presentation] Controlled Polymerization and Copolymerization of Olefins by Diimine Pd Catalysts (2016)
  • Author(s): Daisuke Takeuchi, Yuki Tokura, Keisuke Ito, Kohtaro Osakada
  • Organizer: The International Rubber Conference 2016
  • Place of Presentation: 北九州国際会議場
  • Year and Date: 2016-10-24
  • Int'l Joint Research
• [Presentation] Polymerization of 1,3-Butadiene by Iron Catalysts with Tridentate Ligands (2016)
  • Author(s): Fukutaro Iijima, Ho Chee Tuck, Daisuke Takeuchi, Kohtaro Osakada
  • Organizer: The International Rubber Conference 2016
  • Place of Presentation: 北九州国際会議場
  • Year and Date: 2016-10-24
  • Int'l Joint Research
• [Presentation] HUGPHOS配位子を有するパラジウム錯体によるスチレンの不斉重合 (2016)
  • Author(s): Daisuke Takeuchi・Matthieu Jouffroy, Dominique Armspach, Dominique Matt, Kohtaro Osakada
  • Organizer: 第６５回高分子討論会
  • Place of Presentation: 神奈川大学
  • Year and Date: 2016-09-14
• [Presentation] Palladium-catalyzed polycondensation utilizing chain-walking of non-conjugated dienes (2016)
  • Author(s): Liyi Tan, Daisuke Takeuchi, Kohtaro Osakada
  • Organizer: 第６５回高分子討論会
  • Place of Presentation: 神奈川大学
  • Year and Date: 2016-09-14
• [Presentation] 二層型複核金属錯体によるオレフィン重合および共重合 (2016)
  • Author(s): 岩澤孝・竹内大介・小坂田耕太郎
  • Organizer: 第５回JACI/GSCシンポジウム
  • Place of Presentation: ANAクラウンプラザホテル神戸
  • Year and Date: 2016-06-02
• [Presentation] Polycondensation accompanying chain-walking of non-conjugated dienes by Pd catalyst (2016)
  • Author(s): Liyi Tan, Daisuke Takeuchi, Kohtaro Osakada
  • Organizer: 第６５回高分子学会年次大会
  • Place of Presentation: 神戸国際会議場
  • Year and Date: 2016-05-25
• [Presentation] ジイミンパラジウム錯体によるオレフィンとアクリル酸無水物との共重合 (2016)
  • Author(s): 岩澤孝・竹内大介・小坂田耕太郎
  • Organizer: 第６５回高分子学会年次大会
  • Place of Presentation: 神戸国際会議場
  • Year and Date: 2016-05-25
• [Presentation] パラジウム錯体によるイミンと一酸化炭素の共重合によるポリアミドの合成 (2016)
  • Author(s): 中丸裕一朗・竹内大介・小坂田耕太郎
  • Organizer: 第６５回高分子学会年次大会
  • Place of Presentation: 神戸国際会議場
  • Year and Date: 2016-05-25
• [Presentation] Polymerization of 3,3-dimethyl-1-butene by Diimine Pd Complexes (2015)
  • Author(s): Keisuke Ito, Daisuke Takeuchi, Kohtaro Osakada
  • Organizer: Asian Polyolefin Workshop 2015
  • Place of Presentation: 首都大学東京
  • Year and Date: 2015-11-23
  • Int'l Joint Research
• [Presentation] Stereoselective Polymerization of Chiral Olefins by Diimine Pd Complexes (2015)
  • Author(s): Yuki Tokura，Daisuke Takeuchi, Kohtaro Osakada
  • Organizer: Asian Polyolefin Workshop 2015
  • Place of Presentation: 首都大学東京
  • Year and Date: 2015-11-23
  • Int'l Joint Research
• [Presentation] Polymerization of 3,3-dimethyl-1-butene by Diimine Pd Complexes (2015)
  • Author(s): Keisuke Ito, Daisuke Takeuchi, Kohtaro Osakada
  • Organizer: The 8th International Forum on Chemistry of Functional Organic Chemicals
  • Place of Presentation: 東京大学
  • Year and Date: 2015-11-15
  • Int'l Joint Research
• [Presentation] Isomerization Polymerization of Alkenylcycloalkanes by Diimine Pd Complexes (2015)
  • Author(s): Daisuke Takeuchi
  • Organizer: The 11th International Conference on Advanced Polymers via Macromolecular Engineering
  • Place of Presentation: パシフィコ横浜
  • Year and Date: 2015-10-18
  • Int'l Joint Research
• [Presentation] Polymerization of 3,3-dimethyl-1-butene by Diimine Pd Complexes (2015)
  • Author(s): Keisuke Ito, Daisuke Takeuchi, Kohtaro Osakada
  • Organizer: The 11th International Conference on Advanced Polymers via Macromolecular Engineering
  • Place of Presentation: パシフィコ横浜
  • Year and Date: 2015-10-18
  • Int'l Joint Research
• [Presentation] パラジウム触媒を用いた異性化重合による官能基配列の精密に制御されたポリオレフィンの合成 (2015)
  • Author(s): 竹内大介、渡邉恵介、元国献也、小坂田耕太郎
  • Organizer: 第６４回高分子討論会
  • Place of Presentation: 東北大学
  • Year and Date: 2015-09-15
• [Presentation] ジイミンパラジウム錯体による４級炭素をもつオレフィン類の重合 (2015)
  • Author(s): 伊藤敬佑、竹内大介、小坂田耕太郎
  • Organizer: 第６４回高分子討論会
  • Place of Presentation: 東北大学
  • Year and Date: 2015-09-15
• [Presentation] ジイミンパラジウム錯体によるキラルオレフィンの重合 (2015)
  • Author(s): 徳良雄貴、竹内大介、小坂田耕太郎
  • Organizer: 第６４回高分子討論会
  • Place of Presentation: 東北大学
  • Year and Date: 2015-09-15
• [Presentation] パラジウム触媒による異性化重合を活用した新構造高分子の創製 (2015)
  • Author(s): 竹内大介
  • Organizer: 平成２７年度繊維学会年次大会
  • Place of Presentation: タワーホール船堀
  • Year and Date: 2015-06-10
  • Invited
• [Presentation] トリスピラゾリルメタン配位子を有する鉄錯体によるブタジエンの重合 (2015)
  • Author(s): Ho Chee Tuck、竹内大介、小坂田耕太郎
  • Organizer: 第６４高分子学会年次大会
  • Place of Presentation: 札幌コンベンションセンター
  • Year and Date: 2015-05-27