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Depelopment of supported catalysts for living polymerization of olefins and its application to gas-phse polymerization

Research Project

Project/Area Number 15360419
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Reaction engineering/Process system
Research InstitutionHIROSHIMA UNIVERSITY (2004-2005)
Tokyo Institute of Technology (2003)

Principal Investigator

SHIONO Takeshi  Hiroshima University, Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (10170846)

Project Period (FY) 2003 – 2005
Project Status Completed (Fiscal Year 2005)
Budget Amount *help
¥10,400,000 (Direct Cost: ¥10,400,000)
Fiscal Year 2005: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 2004: ¥2,400,000 (Direct Cost: ¥2,400,000)
Fiscal Year 2003: ¥5,300,000 (Direct Cost: ¥5,300,000)
Keywordsolefin / living polymerization / Ziegler-Natta catalyst / supported catalyst / single-site catalyst / propylene / methylaluminoxane / gas-phase polymerization / 1-ヘキセン / チグラー-ナッタ触媒 / 担特触媒
Research Abstract

The living polymerization, therefore, has attracted much attention and several papers have reported on the living polymerization of propene by homogeneous catalytic systems. There are, however, few examples for living polymerization of propene by supported single-site catalytic systems, which should be very important from the practical point of view. We have previously found that living polymerization of propene proceeded in heptane at 0℃ by a chelating (diamide) dimethyltitaniumcomplex (1) activated with trialkylaluminum-free modified methylaluminoxane (dMMAO), which is easily soluble in hydrocarbons.
We prepared supported dMMAOs using silica gel, alumina and magnesia by the reaction of the support and dMMAO in heptane and conducted propene polymerization with 1 to clarify the supporting effects of dried MMAO. The supported systems conducted living polymerization of propene at 0℃ without any induction period regardless of the metal oxides for dried MMAO. The propagation rate constants (k_p) of these systems and the molecular weight distribution (M_w/M_n) of the produced polymer depended on the metal oxide employed. The k_p value increased with the increase in Lewis acidity of MMAO on the support and the broadening (M_w/M_n) was ascribed to the distribution of Lewis acidity caused by the heterogeneity of the supported cocatalyst. The systems gave atactic polypropylene regardless of the metal oxides for dried MMAO.
We also conducted propene polymerization with ansa-fluorenylamidodimethyltitanium (2), which conducts living polymerization of propene when activated with dMMAO, in place of 1. Although the 2-supported dMMAO systems of silica-gel and alumina showed very high initial activity, the system deactivated and chain transfer also occurred. The results indicated that the combination of the complex and the supported activator was very important for the living polymerization with supported catalytic systems.

Report

(4 results)
  • 2005 Annual Research Report   Final Research Report Summary
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • Research Products

    (16 results)

All 2006 2005 2004

All Journal Article (16 results)

  • [Journal Article] Effects of Solvent in Syndiospecific Living Polymerization of Propylene with [t-BuNSiMe_2(3,6-t-Bu_2Flu)]TiMe_2-MMAO Catalyst2006

    • Author(s)
      Z.Cai
    • Journal Title

      Stud. Surf. Sci. Catal. 160

      Pages: 189-192

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Propene Polymerization by ansa-Fluorenylamidodimethyltitanium Activated with SiO_2-Supported Modified Methylalminoxane2006

    • Author(s)
      T.Shiono
    • Journal Title

      Stud. Surf. Sci. Catal. 160

      Pages: 241-144

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Effects of Solvent in Syndiospecific Living Polymerization of Propylene with [t-BuNSiMe_2(3,6-t-Bu_2Flu)]TiMe_2-MMAO Catalyst.2006

    • Author(s)
      CAI, Zengguo
    • Journal Title

      Stud.Surf.Sci.Catal. 160

      Pages: 189-192

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Propene Polymerization by ansa-Fluorenylamidodimethyltitanium Activated with SiO_2-Supported Modified Methylalminoxane.2006

    • Author(s)
      SHIONO, Takeshi
    • Journal Title

      Stud.Surf.Sci.Catal. 160

      Pages: 241-245

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Effects of Solvent in Syndiospecific Living Polymerization of Propylene with [t-BuNSiMe_2(3,6-t-Bu_2Flu)]TiMe_2-MMAO Catalyst2006

    • Author(s)
      T.Shiono, Z.Cai, Y.Nakayama
    • Journal Title

      Stud.Surf.Sci.Catal. (in press.)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] シンプルプロセスによるポリオレフィンの高性能化・高機能化は可能か?2005

    • Author(s)
      塩野 毅
    • Journal Title

      化学工業 56・10

      Pages: 189-192

    • NAID

      40006913990

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] A challenge for the synthesis of high-performance polyolefins with simple process. (Japanese)2005

    • Author(s)
      SHIONO, Takeshi
    • Journal Title

      Kagakukogyo 160

      Pages: 189-192

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] シングルサイト触媒によるオレフィンのリビング重合2005

    • Author(s)
      塩野 毅
    • Journal Title

      化学 60・10

      Pages: 74-75

    • Related Report
      2005 Annual Research Report
  • [Journal Article] シンプルプロセスによるポリオレフィンの高性能化・高機能化は可能か?2005

    • Author(s)
      塩野 毅, 石原 毅
    • Journal Title

      化学工業 56・10

      Pages: 801-805

    • NAID

      40006913990

    • Related Report
      2005 Annual Research Report
  • [Journal Article] アルキルチタン錯体と担持型活性化剤によるプロピレンのリビング重合2004

    • Author(s)
      塩野 毅
    • Journal Title

      触媒 46・8

      Pages: 644-649

    • NAID

      10014157644

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary 2004 Annual Research Report
  • [Journal Article] Effect of Aluminoxanes on Kinetic Feature of 1-Hexene Polymerization with ansa-(Fluorenylamido)dimetnyltitanium2004

    • Author(s)
      T.Shiono
    • Journal Title

      Proceedigs of the 3rd International Workshop on "Heterogeneous Ziegler-Natta Polymerization", (Sankeisha Co. Ltd.)

      Pages: 65-70

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Supporting effects of methylaluminoxane on living polymerization of propylene with a chelating (diamide)dimethyltitanium complex2004

    • Author(s)
      H.Hagimoto
    • Journal Title

      Macromol. Chem. Phys 205・1

      Pages: 16-26

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Living polymerization of propene with alkyltitanium complexes activated with supported methylaluminoaxane. (Japanese)2004

    • Author(s)
      SHIONO, Takeshi
    • Journal Title

      Shokubai 46

      Pages: 644-649

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Effect of Aluminoxanes on Kinetic Feature of 1-Hexene Polymerization with ansa-(Fluorenylamido) dimetnyltitanium.2004

    • Author(s)
      SHIONO, Takeshi
    • Journal Title

      Proceedings of the 3rd International Workshop on "Heterogeneous Ziegler-Natta Polymerization" (Sankeisha Co.Ltd.)

      Pages: 65-70

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Supporting effects of methylaluminoxane on living polymerization of propylene with a chelating (diamide) dimethyltitanium complex2004

    • Author(s)
      HAGIMOTO, Hitoshi
    • Journal Title

      Macromol.Chem.Phys. 205

      Pages: 19-26

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Effect of Aluminoxanes on Kinetic Feature of 1-Hexene Polymerization with ansa-(Fluorenylamido)dimetnyltitanium2004

    • Author(s)
      T.Shiono, T.Matsumae, K.Nishii, T.Ikeda
    • Journal Title

      Proceedigs of the 3rd International Workshop on "Heterogeneous Ziegler-Natta Polymerization", Sankeisha Co.Ltd.

      Pages: 65-70

    • Related Report
      2004 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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