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Rare Earth-Catalyzed Precision Copolymerization for High Performance Polymer Materials

Research Project

Project/Area Number 24350030
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypePartial Multi-year Fund
Section一般
Research Field Inorganic chemistry
Research InstitutionInstitute of Physical and Chemical Research

Principal Investigator

Nishiura Masayoshi  国立研究開発法人理化学研究所, 侯有機金属化学研究室, 専任研究員 (30332258)

Project Period (FY) 2012-04-01 – 2016-03-31
Project Status Completed (Fiscal Year 2015)
Budget Amount *help
¥18,200,000 (Direct Cost: ¥14,000,000、Indirect Cost: ¥4,200,000)
Fiscal Year 2015: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Fiscal Year 2014: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2013: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2012: ¥5,850,000 (Direct Cost: ¥4,500,000、Indirect Cost: ¥1,350,000)
Keywordsスカンジウム / 共重合 / オレフィン / C-H結合活性化 / 希土類アルキル錯体 / 触媒化学 / スチレン / 高分子化学 / イソプレン / ヘプタジエン / エチレン / アルミニウム / DFT計算
Outline of Final Research Achievements

By use of the catalyst bearing a phosphine oxide group (C5Me4SiMe2CH2P(O)Ph2)Sc(CH2SiMe3)2, the alternating copolymerizations of IP with HPD have been achieved for the first time, in which HPD is completely cyclized to the methylcyclohexane units. We found that cationic half-sandwich yttrium alkyl complexes can catalyze the addition of benzylic C-H bonds of various 2,6-dialkyl-substituted pyridines to a variety of olefins such as 1-hexene and styrenes, to afford new alkylated pyridine derivatives. By using the half-sandwich scandium diaminobenzyl complex (C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2 with borate [Ph3C][B(C6F5)4], the syndiospecific chain transfer polymerization of styrene proceeded efficiently via the ortho-C-H bond activation of anisoles, affording the corresponding end-ortho-anisyl-functionalized syndiotactic polystyrenes.

Report

(5 results)
  • 2015 Annual Research Report   Final Research Report ( PDF )
  • 2014 Annual Research Report
  • 2013 Annual Research Report
  • 2012 Annual Research Report
  • Research Products

    (56 results)

All 2016 2015 2014 2013 2012 Other

All Journal Article (16 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 16 results,  Acknowledgement Compliant: 9 results,  Open Access: 1 results) Presentation (29 results) (of which Int'l Joint Research: 3 results,  Invited: 2 results) Remarks (10 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Isolation, Structure and Reactivity of a Scandium Boryl Oxycarbene Complex2016

    • Author(s)
      B. Wang, X. Kang, M. Nishiura, Y. Luo, and Z. Hou
    • Journal Title

      Chem. Sci.

      Volume: 7 Issue: 1 Pages: 803-809

    • DOI

      10.1039/c5sc03138a

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Scandium-Catalyzed Syndiospecific Chain-Transfer Polymerization of Styrene Using Anisoles as a Chain Transfer Agent2016

    • Author(s)
      A. Yamamoto, M. Nishiura, J. Oyamada, H. Koshino, Z. Hou
    • Journal Title

      Macromolecules

      Volume: 49 Issue: 7 Pages: 2458-2466

    • DOI

      10.1021/acs.macromol.6b00083

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Catalytic C-H Bond Addition of Pyridines to Allenes by a Rare-Earth Catalyst2015

    • Author(s)
      G. Song, B. Wang, M. Nishiura, and Z. Hou
    • Journal Title

      Chem. Eur. J.

      Volume: 21 Issue: 23 Pages: 8394-8398

    • DOI

      10.1002/chem.201501121

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Half-Sandwich Rare-Earth-Catalyzed Olefin Polymerization, Carbometalation, and Hydroarylation2015

    • Author(s)
      M. Nishiura, F. Guo, and Z. Hou
    • Journal Title

      Acc. Chem. Res.

      Volume: 48 Issue: 8 Pages: 2209-2220

    • DOI

      10.1021/acs.accounts.5b00219

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Computational Analyses of the Effect of Lewis Bases on Styrene Polymerization Catalyzed by Cationic Scandium Half-Sandwich Complexes2015

    • Author(s)
      X. Kang, A. Yamamoto, M. Nishiura, Y. Luo, and Z. Hou
    • Journal Title

      Organometallics

      Volume: 34 Issue: 23 Pages: 5540-5548

    • DOI

      10.1021/acs.organomet.5b00719

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Cyclocopolymerization of 1,6-Heptadiene with Styrene Catalyzed by a Half-Sandwich Scandium Dialkyl Complex Bearing a Phosphine Oxide Side Arm2014

    • Author(s)
      F. Guo, M. Nishiura, Y. Li, Z. Hou
    • Journal Title

      J. Polym. Sci. Part A: Polym. Chem.

      Volume: 52 Issue: 11 Pages: 1509-1513

    • DOI

      10.1002/pola.27152

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Cyclocopolymerization of 1,6-heptadiene with ethylene by half-sandwich scandium catalysts2014

    • Author(s)
      F. Guo, M. Nishiura, Y. Li, Z. Hou
    • Journal Title

      Sci. China. Chem.

      Volume: 57 Issue: 8 Pages: 1150-1156

    • DOI

      10.1007/s11426-014-5132-9

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Substituent effect on the electroluminescence efficiency of amidinate-ligated bis(pyridylphenyl) iridium(III) complexes2014

    • Author(s)
      V. Rai Kumar, M. Nishiura, M. Takimoto Z. Hou
    • Journal Title

      J. Mater. Chem. C

      Volume: 2 Issue: 27 Pages: 5317-5326

    • DOI

      10.1039/c3tc32553a

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Half-Sandwich Scandium Boryl Complexes Bearing a Silylene-Linked Cyclopentadienyl-Amido Ligand2014

    • Author(s)
      B. Wang, M. Nishiura, J. Cheng, Z. Hou
    • Journal Title

      Dalton Trans.

      Volume: 43 Issue: 38 Pages: 14215-14218

    • DOI

      10.1039/c4dt01725k

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Copolymerization of Isoprene and Nonconjugated α,ω-Dienes by Half-Sandwich Scandium Catalysts with and without a Coordinative Side Arm2013

    • Author(s)
      F. Guo, M. Nishiura, Y. Li, and Z. Hou
    • Journal Title

      Chem. Asian J.

      Volume: 8 Issue: 10 Pages: 2471-2482

    • DOI

      10.1002/asia.201300599

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Dinitrogen Cleavage and Hydrogenation by a Trinuclear Titanium Polyhydride Complex2013

    • Author(s)
      T. Shima, S. Hu, G. Luo, X. Kang, Y. Luo, Z. Hou
    • Journal Title

      Science

      Volume: 340 Issue: 16 Pages: 1549-1552

    • DOI

      10.1002/anie.201208867

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Regio- and Stereospecific Living Polymerization and Copolymerization of (E)-1,3-Pentadiene with 1,3-Butadiene by Half-sandwich Scandium Catalysts2013

    • Author(s)
      K. Nishii, X. Kang, M. Nishiura, Y. Luo and Z. Hou
    • Journal Title

      Dalton Trans.

      Volume: 42 Issue: 25 Pages: 9030-9032

    • DOI

      10.1039/c3dt50357g

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Aluminum Effects in the Syndiospecific Copolymerization of Styrene with Ethylene by Cationic Fluorenyl Scandium Alkyl Catalysts2013

    • Author(s)
      X. Li
    • Journal Title

      Organometallics

      Volume: 32 Issue: 5 Pages: 1445-1458

    • DOI

      10.1021/om3011036

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 希土類錯体触媒を用いた高選択的分子変換反応の開発2013

    • Author(s)
      西浦正芳
    • Journal Title

      有機合成化学協会誌

      Volume: 71 Pages: 25-38

    • NAID

      10031148197

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] M4(CH2)4 Cubane-Type Rare-Earth Methylidene Complexes: Unique Reactivity toward Unsaturated C-O, C-N, and C-S Bonds2012

    • Author(s)
      T. Li
    • Journal Title

      Chem. Eur. J.

      Volume: 18 Issue: 47 Pages: 15079-15085

    • DOI

      10.1002/chem.201202796

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Binuclear Rare-Earth Polyhydride Complexes Bearing both Terminal and Bridging Hydride Ligands2012

    • Author(s)
      J. Cheng, H. Wang, M. Nishiura Z. Hou
    • Journal Title

      Chem. Sci.

      Volume: 3 Pages: 2230-2233

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Presentation] 希土類触媒によるピリジン類を連鎖移動剤とするスチレンのシンジオタクチック重合2016

    • Author(s)
      山本敦、西浦正芳、侯召民
    • Organizer
      日本化学会 第96春季年会 (2016)
    • Place of Presentation
      同志社大学(京都府)
    • Year and Date
      2016-03-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] Rare-Earth-Catalyzed Polymerization of Methoxyl Substituted Styrene: Step-Growth vs. Chain-Growth Polymerization2016

    • Author(s)
      Shi Xiaochao, 西浦 正芳, 侯召民
    • Organizer
      日本化学会 第96春季年会 (2016)
    • Place of Presentation
      同志社大学(京都府)
    • Year and Date
      2016-03-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] Regioselective Step-Growth Polymerization of Anisyl-Substituted Alkenes via Rare-Earth-Catalyzed C-H Alkylation2016

    • Author(s)
      Wang Haobing、西浦 正芳, 侯召民
    • Organizer
      日本化学会 第96春季年会 (2016)
    • Place of Presentation
      同志社大学(京都府)
    • Year and Date
      2016-03-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] Dinitrogen activation and transformation by a bis(phosphinophenyl)amido-ligated titanium complex2016

    • Author(s)
      Wang Baoli, 西浦 正芳, 侯召民
    • Organizer
      日本化学会 第96春季年会 (2016)
    • Place of Presentation
      同志社大学(京都府)
    • Year and Date
      2016-03-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] lsospecific-trans-1,4-polymerization of(E)-1,3-pentadiene by half-sandwich rare-earth metal catalysts2015

    • Author(s)
      Kei Nishii, Atsushi Yamamoto, Masayoshi Nishiura, Zhaomin Hou
    • Organizer
      Asian Polyolefin Workshop 2015
    • Place of Presentation
      首都大学(東京都)
    • Year and Date
      2015-11-24
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Rare-Earth-Catalyzed C−H Bond Polyaddition of 1,4-Dimethoxybenzene to α,ω-Dienes2015

    • Author(s)
      Xiaochao Shi, Atsushi Yamamoto, Masayoshi Nishiura, Zhaomin Hou
    • Organizer
      Asian Polyolefin Workshop 2015
    • Place of Presentation
      首都大学(東京都)
    • Year and Date
      2015-11-24
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Rare-Earth-Catalyzed Aromatic C-H Bond Polyaddition of Dialkoxyarenes to Unconjugated Dienes2015

    • Author(s)
      西浦正芳, Xiaochao Shi, 侯召民
    • Organizer
      第64回高分子討論会
    • Place of Presentation
      東北大学(宮城県)
    • Year and Date
      2015-09-15
    • Related Report
      2015 Annual Research Report
  • [Presentation] ハーフサンドイッチ型希土類金属触媒による(E)-1, 3-ペンタジエンのtrans1, 4-選択的重合2015

    • Author(s)
      西井圭、山本敦、西浦正芳、侯召民
    • Organizer
      第64回高分子討論会
    • Place of Presentation
      東北大学(宮城県)
    • Year and Date
      2015-09-15
    • Related Report
      2015 Annual Research Report
  • [Presentation] Rare Earth Catalyzed C-H Activation of Anisoles and Pyridines for Efficient Organic Synthesis and Polymer Functionalization2015

    • Author(s)
      西浦正芳
    • Organizer
      The 6th Japanese-Sino Symposium on Organic Chemistry for Young Scientists
    • Place of Presentation
      秋保リゾートホテルクレセント(宮城県)
    • Year and Date
      2015-09-06
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Rare-Earth-Catalyzed Aromatic C-H Bond Polyaddition of Dialkoxylbenzene to Unconjugated Dienes2015

    • Author(s)
      Xiaochao Shi, 西浦 正芳, 侯召民
    • Organizer
      第32回希土類討論会
    • Place of Presentation
      かごしま県民交流センター(鹿児島県)
    • Year and Date
      2015-05-21
    • Related Report
      2015 Annual Research Report
  • [Presentation] Rare-Earth-Catalyzed Alternating Copolymerization of 1, 4-Dimethoxybenzene and Unconjugated Dienes through Aromatic C-H Bond Activation2015

    • Author(s)
      Shi Xiaochao, Nishiura Masayoshi, Hou Zhaomin
    • Organizer
      本化学会第95春季年会
    • Place of Presentation
      日本大学(千葉県)
    • Year and Date
      2015-03-26
    • Related Report
      2014 Annual Research Report
  • [Presentation] Rare-Earth-Catalyzed Syndiotactic Polymerization of Styrene with Anisoles and Pyridines as Chain Transfer Agents2014

    • Author(s)
      Nishiura Masayoshi,Yamamoto Atsushi, Hou Zhaomin
    • Organizer
      The 10th SPSJ International Polymer Conference(IPC2014)
    • Place of Presentation
      つくば国際会議場(茨城県)
    • Year and Date
      2014-12-05
    • Related Report
      2014 Annual Research Report
  • [Presentation] ハーフサンドイッチ型希土類触媒による(E)-1,3-ペンタジエンの重合2014

    • Author(s)
      西井 圭, 手島 章太, 西浦 正芳, 侯 召民
    • Organizer
      第114回触媒討論会
    • Place of Presentation
      広島大学(広島県)
    • Year and Date
      2014-09-27
    • Related Report
      2014 Annual Research Report
  • [Presentation] イットリウム触媒によるイソプレンとミルセンのアイソタクチックブロック共重合2014

    • Author(s)
      張 立新, 西浦 正, Shi Xiaochao, 侯 召民
    • Organizer
      第63回高分子討論会
    • Place of Presentation
      長崎大学(長崎県)
    • Year and Date
      2014-09-26
    • Related Report
      2014 Annual Research Report
  • [Presentation] 希土類触媒によるメタクリル酸メチルのヘテロタクチック重合2014

    • Author(s)
      戸田 智之, 西浦 正芳, 侯 召民
    • Organizer
      第63回高分子討論会
    • Place of Presentation
      長崎大学(長崎県)
    • Year and Date
      2014-09-24
    • Related Report
      2014 Annual Research Report
  • [Presentation] Half-Sandwich Scandium Boryl Oxy Carbene Complex: Synthesis, Structure and Reactivity2014

    • Author(s)
      Wang Baoli, Nishiura Masayoshi, Hou Zhaomin
    • Organizer
      The XXVI International Conference on Organometallic Chemistry
    • Place of Presentation
      ロイトン札幌(北海道)
    • Year and Date
      2014-07-17
    • Related Report
      2014 Annual Research Report
  • [Presentation] Terpolymerization of Styrene with Ethylene and α-Olefins by Scandium Catalysts2014

    • Author(s)
      Zhang Hongxia, Nishiura Masayoshi, Hou Zhaomin
    • Organizer
      The XXVI International Conference on Organometallic Chemistry
    • Place of Presentation
      ロイトン札幌(北海道)
    • Year and Date
      2014-07-17
    • Related Report
      2014 Annual Research Report
  • [Presentation] Rare-Earth-Catalyzed Syndiospecific Polymerization of Styrene with Anisoles and Pyridines as Chain Transfer Agents2014

    • Author(s)
      Yamamoto Atsushi, Oyamada Juzo, Nishiura Masayoshi, Hou Zhaomin
    • Organizer
      The XXVI International Conference on Organometallic Chemistry
    • Place of Presentation
      ロイトン札幌(北海道)
    • Year and Date
      2014-07-15
    • Related Report
      2014 Annual Research Report
  • [Presentation] Synthesis, Structure and Reactivity of a Half-Sandwich Scandium Boryl Oxy Carbene Complex2014

    • Author(s)
      王 保力, 西浦 正芳, 侯 召民
    • Organizer
      第31回希土類討論会
    • Place of Presentation
      タワーホール船堀(東京都)
    • Year and Date
      2014-05-23
    • Related Report
      2014 Annual Research Report
  • [Presentation] 高機能性希土類錯体触媒の開発と精密分子変換反応への応用2013

    • Author(s)
      西浦正芳
    • Organizer
      第30回希土類討論会
    • Place of Presentation
      北九州
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Synthesis, Structure and Reactivity of Scandium Boryl Complex2013

    • Author(s)
      王 保力、西浦 正芳、侯 召民
    • Organizer
      第30回希土類討論会
    • Place of Presentation
      北九州
    • Related Report
      2013 Annual Research Report
  • [Presentation] スカンジウム触媒を用いたアニソール類を連鎖移動剤とするスチレンのシンジオタクチック重合 宋2013

    • Author(s)
      山本 敦、西浦正芳、侯召民
    • Organizer
      第93春季年会
    • Place of Presentation
      立命館大学(滋賀)
    • Related Report
      2012 Annual Research Report
  • [Presentation] ハーフサンドイッチ型スカンジウムボリル錯体の合成と構造および反応性2013

    • Author(s)
      王保力・西浦正芳・侯召民
    • Organizer
      第93春季年会
    • Place of Presentation
      立命館大学(滋賀)
    • Related Report
      2012 Annual Research Report
  • [Presentation] 希土類アルキル錯体触媒による高選択的分子変換反応の開発2012

    • Author(s)
      西浦正芳
    • Organizer
      第29回有機合成化学セミナー
    • Place of Presentation
      グランシップ(静岡)(招待講演)
    • Related Report
      2012 Annual Research Report
  • [Presentation] 4核希土類メチリデン錯体の合成と反応2012

    • Author(s)
      Tingting Li, 西浦正芳, 程建華, 侯召民
    • Organizer
      錯体化学討論会
    • Place of Presentation
      富山大学(富山)
    • Related Report
      2012 Annual Research Report
  • [Presentation] Synthesis and Reactivity Studies of Tetranuclear Rare Earth Methylidene Complexes2012

    • Author(s)
      T. Li, M. Nishiura, J. Cheng, Z. Hou
    • Organizer
      International Symposium on Rare Earths in 2012
    • Place of Presentation
      沖縄ハーバービューホテルクラウンプラザ(沖縄)
    • Related Report
      2012 Annual Research Report
  • [Presentation] Chain-Shuttling Polymerization by Mixed Scandium and Zirconium Catalysts : The First Regio- and Stereoselective Block Copolymerization of Propylene and Butadiene ,2012

    • Author(s)
      H. Zhang, L. Pan, M. Nishiura, Z. Hou
    • Organizer
      The 9th SPSJ International Polymer Conference (IPC2012)
    • Place of Presentation
      神戸国際会議場(神戸)
    • Related Report
      2012 Annual Research Report
  • [Presentation] Scandium-Catalyzed Polymerization of Styrene and Isoprene with Anisoles as Chain Transfer Agents

    • Author(s)
      山本 敦、小山田 重蔵、西浦 正芳、侯 召民
    • Organizer
      第62回高分子学会年次大会
    • Place of Presentation
      京都
    • Related Report
      2013 Annual Research Report
  • [Presentation] Scandium-catalyzed copolymerization of styrene with ethylene and α-olefins

    • Author(s)
      Nishiura Masayoshi、Hou Zhaomin
    • Organizer
      第62回高分子討論会
    • Place of Presentation
      金沢
    • Related Report
      2013 Annual Research Report
  • [Remarks] 理研研究室ホームページ

    • URL

      http://www.riken.jp/lab-www/organometallic/index.html

    • Related Report
      2015 Annual Research Report 2014 Annual Research Report
  • [Remarks] RIKEN public website-english

    • URL

      http://www.riken.jp/en/research/labs/chief/organometal_chem/

    • Related Report
      2015 Annual Research Report
  • [Remarks] 理研研究室ホームページ

    • URL

      http://www.riken.jp/research/labs/chief/organometal_chem/

    • Related Report
      2013 Annual Research Report
  • [Remarks] 理研研究室ホームページ英語

    • URL

      http://www.riken.jp/en/research/labs/chief/organometal_chem/

    • Related Report
      2013 Annual Research Report
  • [Remarks] 研究室

    • URL

      http://www.riken.jp/lab-www/organometallic/index.html

    • Related Report
      2013 Annual Research Report
  • [Remarks] 環境資源科学センターホームページ

    • URL

      http://www.csrs.riken.jp/jp/labs/acrg/index.html

    • Related Report
      2013 Annual Research Report
  • [Remarks]

    • URL

      http://www.riken.jp/r-world/research/lab/wako/organometallic/index.html

    • Related Report
      2012 Annual Research Report
  • [Remarks]

    • URL

      http://www.riken.jp/engn/r-world/research/lab/wako/organometallic/index.html

    • Related Report
      2012 Annual Research Report
  • [Remarks]

    • URL

      http://www.riken.jp/lab-www/organometallic/index.html

    • Related Report
      2012 Annual Research Report
  • [Remarks]

    • URL

      http://www.riken.jp/lab-www/organometallic/engl/index_e.html

    • Related Report
      2012 Annual Research Report
  • [Patent(Industrial Property Rights)] 高分子化合物及び高分子化合物の製造方法2015

    • Inventor(s)
      西浦正芳、石暁超、侯召民
    • Industrial Property Rights Holder
      理研
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2015-040111
    • Filing Date
      2015-03-02
    • Related Report
      2014 Annual Research Report

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Published: 2012-04-24   Modified: 2019-07-29  

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