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2017 Fiscal Year Annual Research Report

Design of efficient molecular catalysis for precise olefin polymerization/oligomerization for development of new materials/green process

Research Project

Project/Area Number 15H03812
Research InstitutionTokyo Metropolitan University

Principal Investigator

野村 琴広  首都大学東京, 理工学研究科, 教授 (20304165)

Project Period (FY) 2015-04-01 – 2018-03-31
Keywords合成化学 / 錯体・有機金属 / 高機能材料 / 触媒・化学プロセス / 触媒設計・反応
Outline of Annual Research Achievements

本課題は高性能分子触媒による精密重合・多量化を基盤とした高機能新材料・革新的合成法の開発に関する研究で、具体的には(1)高性能触媒の特徴を活かした新規ポリマーの創製と特性解析、(2)高機能材料の効率精密合成や革新的合成プロセスの構築を指向した高性能触媒の設計・創製に関する。平成29年度の成果概要は以下の通りである。
当研究室で開発したチタン触媒を用いると、従来触媒では合成不可能なエチレンと置換シクロヘキセンやシクロペンテンとの共重合体が合成可能で、国際共同研究でそのミクロ構造解析(挿入形式・機構解析)に取り組んだ。入手容易かつ安価な有機Al助触媒存在下でもエチレン重合に高い触媒活性を発現するイミド配位バナジウム錯体の合成と触媒機能解析に取り組み、2-(2’-benz-imidazolyl)pyridine配位錯体やボレート含有N-ヘテロ環状カルベン(WCA-NHC)配位子を有する錯体がエチレン重合や環状オレフィンとの共重合に高性能を発現することを見出した。
環状オレフィンの開環メタセシス重合(ROMP)に高温でも高活性を示すバナジウム-アルキリデン触媒の開発に取り組み、従来の前周期遷移金属触媒では報告例が希少な、低歪み環状オレフィン(シクロオクテン)の重合を進行させる高性能触媒を開発し、高温ほど活性が向上すること、高歪みモノマーとの共重合では、ミクロブロック構造を有する耐熱性に優れた材料を与えることを明らかにした。分子量制御の揃った末端官能基化ポリマーを与え、かつ立体特異的に重合を進行させる効率触媒プロセス(連鎖移動ROMP)を確立した。

Research Progress Status

29年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

29年度が最終年度であるため、記入しない。

  • Research Products

    (46 results)

All 2018 2017 Other

All Int'l Joint Research (3 results) Journal Article (10 results) (of which Int'l Joint Research: 5 results,  Peer Reviewed: 10 results,  Open Access: 3 results) Presentation (29 results) (of which Int'l Joint Research: 9 results,  Invited: 12 results) Book (2 results) Remarks (2 results)

  • [Int'l Joint Research] ブラウンシュバイク工科大学(ドイツ)

    • Country Name
      GERMANY
    • Counterpart Institution
      ブラウンシュバイク工科大学
  • [Int'l Joint Research] CNR高分子研究所(ISMAC)(イタリア)

    • Country Name
      ITALY
    • Counterpart Institution
      CNR高分子研究所(ISMAC)
  • [Int'l Joint Research] 中国科学院化学研究所(中国)

    • Country Name
      CHINA
    • Counterpart Institution
      中国科学院化学研究所
  • [Journal Article] Ethylene copolymerization with 4-methylcyclohexene, 1-methylcyclopentene by half-titanocene catalysts: Effect of ligands and microstructural analysis of the copolymers2018

    • Author(s)
      H. Harakawa, S. Patamma, A. Boccia, L. Boggioni, D. Ferro, S. Losio, K Nomura, I. Tritto
    • Journal Title

      Macromolecules

      Volume: 51 Pages: 853-863

    • DOI

      10.1021/acs.macromol.7b02484

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Olefin metathesis polymerization: Some recent developments in the precise polymerizations for synthesis of advanced materials (by ROMP, ADMET)2018

    • Author(s)
      Y. Chen, M. M. Abdellatif, K. Nomura
    • Journal Title

      Tetrahedron (report)

      Volume: 74 Pages: 619-643

    • DOI

      10.1016/j.tet.2017.12.041

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] 高性能分子触媒が先導する新規オレフィン系高分子機能材料の創製2018

    • Author(s)
      野村琴広
    • Journal Title

      ペトロテック

      Volume: 41 Pages: 20-23

    • Peer Reviewed
  • [Journal Article] Ring opening metathesis polymerization of norbornene or tetracyclododecene with cyclooctene by using (arylmido)vanadium(V)-alkylidene catalyst2017

    • Author(s)
      S. Chaimongkolkunasin, X. Hou, K. Nomura
    • Journal Title

      J. Polym. Sci.: Part A: Polym. Chem. (special issue)

      Volume: 55 Pages: 3067-3074

    • DOI

      10.1002/pola.28622

    • Peer Reviewed
  • [Journal Article] Effect of Al cocatalyst in ethylene and ethylene/norbornene (Co)polymerization by (imido)vanadium dichloride complexes containing anionic N-heterocyclic carbenes having weakly coordinating borate moiety2017

    • Author(s)
      G. Nagai, T. Mitsudome, K. Tsutsumi, S. Sueki, T. Ina, M. Tamm, K. Nomura
    • Journal Title

      J. Jpn. Petrol. Inst. (special issue)

      Volume: 60 Pages: 256-262

    • DOI

      10.1627/jpi.60.256

    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Synthesis and structural analysis of aryloxo-modified trinuclear half-titanocenes, and their use as catalyst precursors for ethylene polymerisation2017

    • Author(s)
      Q. Yan, K. Tsutsumi, K. Nomura
    • Journal Title

      RSC Adv.

      Volume: 7 Pages: 41345-41358

    • DOI

      10.1039/C7RA07581B

    • Peer Reviewed / Open Access
  • [Journal Article] Cis Specific chain transfer ring-opening metathesis polymerization using a vanadium(V)-alkylidene catalyst for efficient synthesis of end-functionalized polymers2017

    • Author(s)
      K. Nomura, X. Hou
    • Journal Title

      Organometallics

      Volume: 36 Pages: 4103-4106

    • DOI

      10.1021/acs.organomet.7b00675

    • Peer Reviewed
  • [Journal Article] Synthesis, structural analysis of (imido)vanadium dichloride complexes containing 2-(2’-benz-imidazolyl)pyridine ligands: Effect of Al cocatalyst for efficient ethylene (co)polymerization2017

    • Author(s)
      K. Nomura, M. Oshima, T. Mitsudome, H. Harakawa, P. Hao, K. Tsutsumi, G. Nagai, T. Ina, H. Takaya, W.-H. Sun, S. Yamazoe
    • Journal Title

      ACS Omega

      Volume: 2 Pages: 8660-8673

    • DOI

      10.1021/acsomega.7b01225

    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Synthesis and reaction chemistry of alkylidene complexes with titanium, zirconium, vanadium, and niobium: Effective catalysts for olefin metathesis polymerization and the other organic transformations2017

    • Author(s)
      S. Zhang, W. Zhang, K. Nomura
    • Journal Title

      Adv. Organomet. Chem

      Volume: 68 Pages: 93-136

    • DOI

      10.1016/bs.adomc.2017.08.001

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] オレフィンメタセシス化学の最近の進展ーより高活性かつ緻密な反応制御を可能とする触媒開発2017

    • Author(s)
      野村琴広
    • Journal Title

      化学

      Volume: 72 Pages: 70-71

    • Peer Reviewed
  • [Presentation] 高性能分子触媒が先導する新しいオレフィン系高分子機能材料の研究開発2018

    • Author(s)
      野村琴広
    • Organizer
      日本化学会第98年会  アドバンスト・テクノロジー・プログラム(ATP)-触媒元素戦略で拓く未来社会-
    • Invited
  • [Presentation] Synthesis of (imido)niobium(V) complexes and some reactions2017

    • Author(s)
      N. Srisupap, K. Wised, K. Nomura
    • Organizer
      16th Korea-Japan Symposium on Catalysis & 3rd International Symposium of Institute for Catalysis
    • Int'l Joint Research
  • [Presentation] Imido Vanadium(V)-Alkylidene Complexes for Olefin Metathesis Polymerization2017

    • Author(s)
      S. Chaimongkolkunasin, X. Hou, K. Nomura
    • Organizer
      16th Korea-Japan Symposium on Catalysis & 3rd International Symposium of Institute for Catalysis
    • Int'l Joint Research
  • [Presentation] Synthesis of ultrahigh molecular weight Poly(α-olefin)s by half titanocene catalysts2017

    • Author(s)
      S. Pengoubol, K. Nomura
    • Organizer
      16th Korea-Japan Symposium on Catalysis & 3rd International Symposium of Institute for Catalysis
    • Int'l Joint Research
  • [Presentation] Synthesis of (imido)niobium(V) complexes and some reactions2017

    • Author(s)
      M. Kuboki, K. Nomura
    • Organizer
      The 19th IUPAC International Symposia on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS19)
    • Int'l Joint Research
  • [Presentation] Copolymerzation of ethylene with methylcyclohexenes, 1-methylcyclopentene using half-titanocene catalysts2017

    • Author(s)
      H. Harakawa, S. Patamma, I. Tritto, K. Nomura
    • Organizer
      The 19th IUPAC International Symposia on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS19)
    • Int'l Joint Research
  • [Presentation] Synthesis of (imido)Vanadium(V)-alkylidene complexes: Highly-active thermally robust olefin metathesis catalysts2017

    • Author(s)
      S. Chaimongkolkunasin, X. Hou, K. Nomura
    • Organizer
      The 22nd International Symposium on Olefin Metathesis and Related Chemistry (ISOM XXII)
    • Int'l Joint Research
  • [Presentation] イミド配位バナジウム錯体によるエチレンの重合・二量化と溶液XAFS手法を活用した触媒活性種解析2017

    • Author(s)
      野村琴広, 満留敬人, 永井 豪, 五十嵐 淳, 堤 健, 末木俊輔, 高谷 光, M. Tamm, 山添誠司
    • Organizer
      第64回有機金属化学討論会
  • [Presentation] キレート多座配位二オブ錯体の合成と反応性に関する研究2017

    • Author(s)
      大宮拓也, 堤 健, 野村琴広
    • Organizer
      第64回有機金属化学討論会
  • [Presentation] キレートアニオン性配位子を有するイミド配位ニオブ錯体の合成と反応性2017

    • Author(s)
      久保木勝晴, 堤 健, 野村琴広
    • Organizer
      第64回有機金属化学討論会
  • [Presentation] Reaction chemistry of (arylimido)niobium(V) tris(ketimide) complex with various phenol/alcohols2017

    • Author(s)
      N. Srisupap, K. Wised, 堤 健, 野村琴広
    • Organizer
      第120回触媒討論会
  • [Presentation] イミド配位バナジウム-アルキル錯体とフェノールとの配位子交換反応の解析, 及び簡便な触媒スクリーニング手法への適用2017

    • Author(s)
      林原 瞳, X. Hou, 野村琴広
    • Organizer
      第120回触媒討論会
  • [Presentation] ハーフチタノセン触媒を用いるエチレンと置換シクロへキセンや置換シクロペンテンとの共重合2017

    • Author(s)
      原川仁志, S. Patamma, I. Tritto, 野村琴広
    • Organizer
      第120回触媒討論会
  • [Presentation] Imido vanadium(V)-alkylidene complexes for olefin metathesis polymerization2017

    • Author(s)
      S. Chaimongkolkunasin, X. Hou, 野村琴広
    • Organizer
      第66回高分子討論会
  • [Presentation] Olefin metathesis: Design of efficient catalysts for synthesis of advanced materials2017

    • Author(s)
      K. Nomura
    • Organizer
      Inner Mongolia University
    • Invited
  • [Presentation] Design of efficient molecular catalysts for development of advanced polymeric materials2017

    • Author(s)
      K. Nomura
    • Organizer
      Institute of Process Engineering, CAS
    • Invited
  • [Presentation] Design of efficient molecular catalysts for development of advanced polymeric materials2017

    • Author(s)
      K. Nomura
    • Organizer
      Beijing Institute of Technology
    • Invited
  • [Presentation] ポリオレフィンの精密合成のための触媒設計2017

    • Author(s)
      野村琴広
    • Organizer
      2017年度高分子学会Webinar講演
    • Invited
  • [Presentation] Design of (arylimido)vanadium(V) alkylidene complex catalysts for ring-opening metathesis polymerization of cyclic olefins2017

    • Author(s)
      S. Chaimongkolkunasin, X. Hou, K. Nomura
    • Organizer
      Asian Polyolefin Workshop 2017 (APO2017)
    • Int'l Joint Research / Invited
  • [Presentation] Copolymerzation of ethylene with methylcyclohexenes, 1-methylcyclopentene using half-titanocene catalysts2017

    • Author(s)
      H. Harakawa, S. Patamma, I. Tritto, K. Nomura
    • Organizer
      Asian Polyolefin Workshop 2017 (APO2017)
    • Int'l Joint Research
  • [Presentation] Synthesis of ultrahigh molecular weight poly(α-olefin)s and their functionalization by half-titanocene catalysts2017

    • Author(s)
      S. Pengoubol, K. Nomura
    • Organizer
      Asian Polyolefin Workshop 2017 (APO2017)
    • Int'l Joint Research
  • [Presentation] Design of efficient molecular catalysts for development of polymeric functional materials2017

    • Author(s)
      K. Nomura
    • Organizer
      Solvay Colloquium, Universite libre de Bruxelles
    • Invited
  • [Presentation] Olefin metathesis: Design of efficient catalysts and synthesis of advanced conjugated materials2017

    • Author(s)
      K. Nomura
    • Organizer
      University of Mons
    • Invited
  • [Presentation] ボレート含有N-ヘテロ環状カルベン(WCA-NHC)配位子を有するバナジウム及びチタン錯体の合成とエチレン重合2017

    • Author(s)
      永井 豪,M. Tamm, 野村琴広
    • Organizer
      第47回石油・石油化学討論会
  • [Presentation] イミド配位ニオブ錯体の合成とエチレンとの反応2017

    • Author(s)
      久保木勝晴,堤 健,野村琴広
    • Organizer
      第47回石油・石油化学討論会
  • [Presentation] Olefin metathesis: efficient methods for synthesis of advanced materials2017

    • Author(s)
      K. Nomura
    • Organizer
      University of Liege
    • Invited
  • [Presentation] (Imido)vanadium complex catalysts for olefin polymerization/dimerization2017

    • Author(s)
      K. Nomura
    • Organizer
      University of Lille
    • Invited
  • [Presentation] Precise synthesis of cyclic olefin polymers by olefin insertion/metathesis polymerization2017

    • Author(s)
      K. Nomura
    • Organizer
      Beijing University of Chemical Technology
    • Invited
  • [Presentation] (Imido)vanadium complex catalysts for olefin polymerization/oligomerization2017

    • Author(s)
      K. Nomura
    • Organizer
      University of Science and Technology of China
    • Invited
  • [Book] Handbook of Transition Metal Polymerization Catalysts, 2nd Edition: Olefin polymerization by vanadium complex catalysts2018

    • Author(s)
      K. Nomura, X. Hou
    • Total Pages
      26
    • Publisher
      Wiley
    • ISBN
      978-1-119-24213-0
  • [Book] 触媒技術の動向と展望2018: バナジウム錯体触媒によるオレフィン重合・二量化反応 高性能分子触媒の創製と活性種解析2018

    • Author(s)
      野村琴広、林原 瞳
    • Total Pages
      13
    • Publisher
      触媒学会(編)
  • [Remarks] 首都大学東京 有機化学研究室

    • URL

      http://tmu-orgchem-lab.com

  • [Remarks] Kotohiro Nomura

    • URL

      http://kotohiro-nomura.com/

URL: 

Published: 2018-12-17  

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