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Precise synthesis of new polyolefins by post metallocene type transition metal catalysis

Research Project

Project/Area Number 13555253
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field Synthetic chemistry
Research InstitutionNARA INSTITUTE OF SCIENCE AND TECHNOLOGY

Principal Investigator

NOMURA Kotohiro  Nara Institute of Science and Technology, Graduate School of Materials Science, Associate Professor, 物質創成科学研究科, 助教授 (20304165)

Co-Investigator(Kenkyū-buntansha) SHIRAI Hiroshi  Asahi Kansai Chemicals Inc., Chemicals & Plastics Research & Development Lavoratory, Manager, 化成品樹脂開発研究所, 主事(研究職)
永 直文  奈良先端科学技術大学院大学, 物質創成科学研究科, 助手 (40314538)
Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥8,000,000 (Direct Cost: ¥8,000,000)
Fiscal Year 2003: ¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 2002: ¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 2001: ¥3,600,000 (Direct Cost: ¥3,600,000)
KeywordsOlefin Polymerization / Transition Metal Complex Catalysts / Polyolefins / Precision Polymerization / Titanium Complexes / Vanadium Complexes / Controlled POlymerization / Ethylene
Research Abstract

The purpose on this research project is to create new polyolefins that possess unique properties. Olefin polymerization by homogeneous transition metal complex catalysts attracts particular attention in the field of organometallic chemistry, catalysis, and polymer chemistry. This is because the design of an efficient complex catalyst has thus been the key for the precise synthesis by controlled polymerization. We have shown that (cyclopentadienyl)(aryloxy)titanium (IV) complex of the type, Cp'Ti(OAr)X_2 (OAr=aryloxy group), exhibited remarkable catalytic activities for ethylene, α-olefin polymerization in the presence of methylaluminoxane (MAO), and monomer reactivities as well as monomer sequence distributions were directly affected by the substituents in cyclopentadienyl group. We have also shown that the catalyst of this type could be tuned to the efficient catalyst precursor for both styrene polymerization and ethylene/styrene copolymerization by the simple ligand modification. We … More have also shown that efiicient norbornene incorporation in ethylene/norbornene copolymerization can be achieved in this catalyst systems by modifying the substitutent on cyclopentadienyl group like (indenyl)TiCl_2(OAr). Based on these facts, new polyolefins that were difficult/impossible to prepare have been created by using this catalysts. We also explored the effect of ligand in olefin polymerization chemistry by Cp-anilide, Cp-amide and Cp-ketimide titanium complexes. (Anilido)(cyclopentadienyl)titanium(IV)complexes of the type, Cp'TrCl_2[N(R)(XAr)] [Cp'=Cp^*, 1,3 M_2C_5H_3,Cp ; R=SiMe_3 etc.; Ar=2,6-Me_2C_6H_3], and Cp'-amide titanium complexes of the type, Cp'TiCl_2(NMeR) have been prepared, and these complexes exhibited high catalytic activity for ethylene polymerization in the presence of MAO, and the activity increased in the order : Cp'=Cp^*>1,3-Me_2C_5H_3>Cp. The trend observed here was almost the same as that in Cp'-aryloxy titanium complexes. The efficient catalyst for symdiospecific styrene polymerization could be modified only by replacing the substituent on Cp'.
We have reported that (arylimido)(aryloxo)vanadium(V) complexes of the type, VCl_2(NAr)(OAr'), exhibited remarkable catalytic activities for ethylene polymerization in the presence of MAO, and that ring-opening metathesis polymerization (ROMP) of norbornene had been initiated by V(CH_2Ph)_2(NAr)(O-2,6Pr_2C_6H_3). Remarkably high catalytic activities for ethylene polymerization were observed if the complex was treated with Et_2AlCl. The low catalytic activity was observed if AlMe_3 was used in place of Et_2AlCl, although the use of AlMe_3 as cocatalyst was effective for the ROMP. We believe that the results observed here would be an interesting contrast among these polymerizations. Less

Report

(4 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (45 results)

All Other

All Publications (45 results)

  • [Publications] 野村琴広, 他: "Olefin polymerization and ring-opening metathesis polymerization(ROMP) of norbornene by (arylimido)(aryloxo)vanadium(V) complexes of the type, VX_2(NAr)(OAr'). -Remarkable effect of aluminum cocatalyst for the coordination insertion and ring-opening metathesis polymerization-"Macromolecules. 35. 1583-1591 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 若林保武, 宮下晃, 野村琴広, 野平博之: "Me_2Si(indenyl)(N^tBu)]TiX_2(X=Cl,Me)錯体触媒によるエチレン重合及びエチレンとスチレンとの共重合"高分子論文集特集号「遷移金属触媒重合の新展開」. 59. 393-401 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 野村琴広, 他: "Ethylene/styrene copolymerization by various (cyclopentadienyl)(aryloxy)titanium(IV) complexes-MAO catalyst system"Macromolecules. 34. 5388-5395 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 野村琴広, 他: "Effect of ligand in ethylene/styrene copolymerization by [Me_2Si(C_5Me_4)(NR)]TiCl_2(R=tert-Bu,cyclohexyl) and (1,3-Me_2C_5H_3)TiCl_2(O-2,6-^iPr_2C_6H_3)-MAO catalyst systems"J.Mol.Catal.A. 190. 225-234 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 野村琴広, 他: "A study concerning the effect of organoboron compounds in 1-hexene polymerization catalyzed by Cp^*TiMe_2(O-2,6-^iPr_2C_6H_3)"Inorg.Chim.Acta.. 345. 37-43 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 野村琴広, 他: "Effect of cyclopentadienyl and amide fragment in olefin polymerization by nonbridged (amide)-(cyclopentadienyl)titanium(IV) complexes of the type, Cp'TiCl_2[N(R^1)R^2],-methylaluminoxane (MAO) catalyst systems"Macromolecules. 36. 2633-2641 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 野村琴広, 他: "Some reactions of Cp^*TiMe_2(OAr) and Cp^*TiMe(CF_3SO_3)(OAr) with 5-hexen-1-ol and 3-buten-1-ol, structural analysis for Cp^*Ti(CF_3SO_3)[OCH_2(CH_2)_3CH=CH_2](OAr) (OAr=O-2,6-^iPr_2C_6H_3)"Inorg.Chem.Commun.. 6. 517-522 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 野村琴広, 他: "Effect of aryloxo ligand for ethylene polymerization by (arylimido)(aryloxo)vanadium(V) complexes-MAO catalyst systems. Attempt for polymerization of styrene"Catal.Commun.. 4. 159-164 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 野村琴広, 他: "Efficient ethylene/norbornene copolymerization by (aryloxo)(indenyl)titanium(IV) complexes-MAO catalyst system"Macromolecules. 36. 3797-3799 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 野村琴広, 他: "Syndiospecific styrene polymerization by (tert-BuC_5H_4)TiCl_2(O-2,6-^iPr_2C_6H_3)-Borate Catalyst System"Catal.Commun.. 4. 269-274 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 野村琴広, 他: "Efficient living polymerization of 1-hexene by Cp^*TiMe_2(O-2,6-^iPr_2C_6H_3)-borate catalyst system at low temperature"J.Mol.Catal.A. 209. 9-17 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 野村琴広, 他: "Polymerization of 1,5-Hexadiene by Nonbridged Half-Titanocene Complex-MAO Catalyst System : Remarkable Difference in the Selectivity of Repeated 1,2-Insertion"Macromolecules. 37. 1693-1695 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 野村琴広, 他: "Effects of Cyclopentadienyl Fragment in Ethylene, 1-Hexene, and Styrene Polymerizations Catalyzed by Half-Titanocenes Containing Ketimide Ligand of the Type, Cp'TiCl_2(N=C^tBu_2)"Catal.Comun.. (in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 野村琴広, 他: "Ethylene polymerization catalyzed by various (aryloimido)(aryloxo)vanadium(V) complexes-MAO catalyst systems, and attempted styrene (co)polymerization"Symposium special issue of 3rd International Workshop on Heterogeneous Ziegler-Natta Catalysts (JAIST,2003). (accepted).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 野村琴広, 他: "Effect of Cyclopentadienyl and Anionic Ancillary Ligand in Syndiospecific Styrene Polymerization Catalyzed by Nonbridged Half-Titanocenes Containing Aryloxo, Amide,and Anilide Ligands-Cocatalyst Systems"Macromolecules. (accepted).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 野村琴広(著者分担): "「触媒活用事典」重合触媒の将来展望,"シングルサイト触媒"(第13章)(触媒学会(編))"(株)工業調査会(掲載予定).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Nomura, A.Sagara, Y.Imanishi: "Olefin polymerization and ring-opening metathesis polymerization (ROMP) of norbornene by (arylimido)-(aryloxo)vanadium(V) complexes of the type, VX_2(NAr)(OAr'). -Remarkable effect of aluminum cocatalyst for the coordination insertion and ring-opening metathesis polymerization -"Macromolecules. 35. 1583-1591 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Nomura, H.Okumura, T.Komatsu, N.Naga: "Ethylene/styrene copolymerization by various (cyclopentadienyl)-(aryloxy)titanium(IV) complexes -MAO catalyst system"Macromolecules. 34. 5388 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Nomura, H.Okumura, T.Komatsu, Y.Imanishi: "Effect of ligand in ethylene/styrene copolymerization by [Me_2Si(C_5Me_4)-(NR)]TiCl_2 (R=tert-Bu, cyclohexyl) and (1,3-Me_2C_5H_3)TiCl_2(O-2,6-^iPr_2C_6H_3)-MAO catalyst systems"J.Mol.Catal.A(Invited paper for a special issue of 14th international symposium on olefin metathesis and related chemistry, ISOMXIV). 190. 225-234 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Nomura, A.Fudo: "A study concerning the effect of organoboron compounds in 1-hexene polymerization catalyzed by Cp^*TiMe_2(O-2,6-^iPr_2C_6H_3). -Structural analysis for Cp^*TiMe_2(O-2,6-^iPr_2C_6H_3) and Cp^*TiMe(CF_3SO_3)(O-2,6-^iPr_2C_6H_3)-"Inorg.Chim.Acta(Special issue dedicated to Prof.R.R.Schrock). 345. 37-43 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Nomura, K.Fujii: "Effect of cyclopentadienyl and amide fragment in olefin polymerization by nonbridged (amide)-(cyclopentadienyl)titanium(IV) complexes of the type, Cp'TiCl_2[N(R^1)R^2], -methylaluminoxane (MAO) catalyst systems"Macromolecules. 36. 2633-2641 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Nomura, Y.Hatanaka: "Some reactions of Cp^*TiMe_2(OAr) and Cp^*TiMe(CF_3SO_3)(OAr) with 5-hexen-1-ol and 3-buten-1-ol, structural analysis for Cp^*Ti(CF_3SO_3)-[OCH_2(CH_2)3CH=CH_2](OAr) (OAr=O-2,6-^iPr_2C_6H_3)"Inorg.Chem.Commun. 6. 517-522 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] W.Wang, J.Yamada, M.Fujiki, K.Nomura: "Effect of aryloxo ligand for ethylene polymerization by(arylimido)(aryloxo)vanadium(V) complexes -MAO catalyst systems. Attempt for polymerization of styrene"Catal.Commun. 4. 159-164 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Nomura, M.Tsubota, M.Fujiki: "Efficient ethylene/norbornene copolymerization by (aryloxo)(indenyl)-titanium(IV) complexes -MAO catalyst system"Macromolecules. 36. 3797-3799 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Nomura, A.Fudo: "Syndiospecific styrene polymerization by (tert-BuC_5H_4)TiCl_2(O-2,6--iPr_2C_6H_3) -borate catalyst system"Catal.Commun. 4. 269-274 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Nomura, A.Fudo: "Efficient living polymerization of 1-hexene by Cp^*TiMe_2(O-2,6-^iPr_2C_6H_3) -borate catalyst system at low temperature"J.Mol.Catal.A. 209. 9-17 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Nomura, Y.Hatanaka, H.Okumura, M.Fujiki, K.Hasegawa: "Polymerization of 1,5-hexadiene by nonbridged half-titanocene complex -MAO catalyst system : Remarkable difference in the selectivity of repeated 1,2-insertion"Macromolecules. 37. 1693-1695 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Nomura, K.Fujita, M.Fujiki: "Effects of cyclopentadienyl fragment in ethylene, 1-hexene, and styrene polymerizations catalyzed by half-titanocenes containing ketimide ligand of the type, Cp'TiCl_2(N=C^tBu_2)"Catal.Commun.. (accepted.).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] W.Wang, J.Yamada, M.Fujiki, K.Nomura: "Ethylene polymerization catalyzed by various(aryloimido)(aryloxo)vanadium(V) complexes -MAO catalyst systems, and attempted styrene (co)polymerization"Symposium special issue of 3rd international Workshop on Heterogeneous Ziegler-Natta Catalysts(JAIST 2003). (accepted.).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 野村琴広他: "Efficient ethylene/norbornene copolymerization by (aryloxo)(indenyl)titanium(IV) complexes - MAO catalyst system"Macromolecules. 36. 3797-3799 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 野村琴広他: "Syndiospecific styrene polymerization by (tert-BuC_5H_4)TiCl_2(O-2,6-^iPr_2C_6H_3)-borate catalyst system"Catalysis Communications. 4. 269-274 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 野村琴広他: "Efficient living polymerization of 1-hexene by Cp^*TiMe_2(O-2,6-^iPr_2C_6H_3)-borate catalyst system at low temperature"Journal of Molecular Catalysis A : Chemical. 209. 9-17 (2000)

    • Related Report
      2003 Annual Research Report
  • [Publications] 野村琴広他: "Polymerization of 1,5-hexadiene by nonbridged half-titanocene complex - MAO catalyst system : Remarkable difference in the selectivity of repeated 1,2-insertion"Macromolecules. 37. 1693-1695 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] 野村琴広他: "Ethylene polymerization catalyzed by various (aryloimido)(aryloxo)vanadium(V) complexes - MAO catalyst systems, and attempted styrene (co)polymerization"Symposium special issue of 3rd International Workshop on Heterogeneous Ziegler-Natta Catalysts (JAIST, 2003). (掲載予定).

    • Related Report
      2003 Annual Research Report
  • [Publications] 野村琴広他: "Effects of cyclopentadienyl fragment in ethylene, 1-hexene, and styrene polymerizations catalyzed by haif-titanocenes containing ketimide ligand of the type, Cp'TiCl_2(N=C^tBu_2)"Catalysis Communication. (掲載予定).

    • Related Report
      2003 Annual Research Report
  • [Publications] 野村琴広(著書分担): "「触媒活用辞典」重合触媒の将来展望,"シングルサイト触媒"(第13章)"触媒学会(編),(株)工業調査会(掲載予定).

    • Related Report
      2003 Annual Research Report
  • [Publications] 野村琴広他: "Ethylene/styrene copolymerization by various (cyclopentadienyl)(aryloxy)titanium (IV) complexes -MAO catalyst system"Macromolecules. 34. 5388-5395 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 野村琴広他: "A study concerning the effect of organoboron compounds in 1-hexene polymerization catalyzed by Cp^*TiMe_2(O-2,6-^iPr_2C_6H_3). -Structural analysis for Cp^*TiMe_2(O-2,6-^iPr_2C_6H_3) and Cp^*TiMe(CF_3SO_3)(O-2,6-^iPr_2C_6H_3)-"Inorg. Chim. Acta (Special issue dedicated to Prof R.R. Schrock). 345. 37-43 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] 野村琴広他: "Effect of ligand in ethylene/styrene copolymerization by [Me_2Si(C_5Me_4)(NR)]TiCl_2 (R=tert-Bu, cyclohexyl) and (1,3-Me_2C_5H_3)TiCl_2(O-2,6-^iPr_2C_6H_3)-MAO catalyst systems"J. Mol. Catal. A. (Invited paper for a special issue of 14^<th> international symposium on olefin metathesis and related chemistry). 130. 225-234 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 野村琴広他: "Effect of cyclopentadienyl and amide fragment in olefin polymerization by nonbridged(amide)(cyclopentadienyl)titanium(IV) complexes of the type, Cp'TiCl_2[N(R^1)R^2], -methylaluminoxane (MAO) catalyst systems"Macromolecules, in press (Web release on March 5, 2003)..

    • Related Report
      2002 Annual Research Report
  • [Publications] 野村琴広他: "Some reactions of Cp^*TiMe_2(OAr) and Cp^*TiMe(CF_3SO_3)(OAr) with 5-hexen-1-ol and 3-buten-1-ol, structural analysis for Cp^*Ti(CF_3SO_3)[OCH_2(CH_2)_3CH=CH_2](OAr)(OAr=O-2,6-^iPr_2C_6H_3)"Inorg. Chem. Commun.. 5/6. 517-522 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] 野村琴広他: "Effect of aryloxo ligand for ethylene polymerization by (arylimido)(aryloxo)vanadium(V) complexes -MAO catalyst systems. Attempt for polymerization of styrene"Catal. Commun.. (掲載予定).

    • Related Report
      2002 Annual Research Report
  • [Publications] 野村琴広他: "Effect of ligand in ethylene/styrene copolymerization by [Me_2Si(C_5Me_4)(NR)]TiCl_2(R=tert-Bu, cyclohexyl)and(1,3-Me_2C_5H_3)TiCl_2(O-2, 6-^iPr_2C_6H_3)-MAO catalyst"J. Mol. Catal. A(Symposium Special Issue for 14^<th> International Symposium on Olefin Metathesis and Related Chemistry). (in press). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] 野村琴広他: "Olefin polymerization and ring-opening metathesis polymerization(ROMP)of norbornene by(arylimido)(aryloxo)vanadium(V)complexes of the type, VX_2(NAr)(OAr')-Remarkable effect of aluminum cocatalyst for the coordination insertion and ring-opening metathesis polymerization-"Macromolecules. 35. 1583-1591 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] 野村琴広他: "[Me_2Si(indenyl)(N^tBu)]TiX_2(X=Cl, Me)錯体触媒によるエチレン重合及びエチレンとスチレンとの共重合"高分子論文集特集号. (掲載予定). (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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