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Development of thc catalysts for elhylene-butadiene copolymerization and their aoolicalion for functional poly olefins

Research Project

Project/Area Number 13650930
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 高分子合成
Research InstitutionTokyo Institute of Technology

Principal Investigator

SHIONO Takeshi  Tokyo Institute of Technology, Chemical Resources Laboratory, Associate Professor, 資源化学研究所, 助教授 (10170846)

Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 2002: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 2001: ¥1,800,000 (Direct Cost: ¥1,800,000)
Keywordscoordination polymerization / half titanocene / zirconocene / ethylene / 1,3-butadiene / copolymerization / cobalt dichloride / living polymerization / チーグラー触媒 / 酸化分解
Research Abstract

A SiO_2-supported (η^5-cyclopentadienyl) titanium trichloride was prepared and applied for copolymerization of ethylene and 1,3-butadiene using the mixture of triisobutylaluminum and triphenylmethyl tetralkis (pentafluorophenyl) borate as an activator. The system was found to give copolymers with selectivities of 80 % at 40 ℃ and more than 99 % at ℃. The butadiene contents, of which structure was trans-1,4-addition, was varied from 0.5 to 2.5 mol %. The trans-1,4-addition units in the copolymer were selectively oxidized with potassium permanganate, which produced α,ω-dicarboxypolyethylene. The polydispersity of the gegradation products, M_W/M_n = 2, indicated that the butadiene units were distributed randomly in the main chain. A series of zirconocene compounds activated by the mixture of triisobutylaluminum and triphenylmethyl tetralkis (pentafluorophenyl) borate was then applied for the copolymerization of ethylene and 1,3-butadiene at 40℃. The polymerization activity strongly depend … More ed on the structure of zirconocene compounds : bridged and non-bridged C_<2v>-symmetric zirconocenes did not give polymers, whereas C_2-symmetric and C_3-symmetric bridged zirconocenes produced copolymers with more than 90 % selectivity. Among the zirconocenes used, diphenymethyl(η^5-cyclopentadienyl(η^5-cyclopentadienyl)zirconium dichloride (I) showed the highest activity and gave the copolymer with the highest butadiene content. The copolymer contained ca. 8 mol % of frans-1,4-addition unit and ca. 20 mol % of cyclopentane unit., that is, the structure of the copolymer was very similar to that of ethylene-butadiene-cyclopentene copolymer. The butadiene contents of the copolymer showed a good relation with the activity and decreased in the following order : I > other C_5-symmetric zirconocenes > C_2-symmetric zirconocenes. When the copolymerization was condacted with I at O ℃, the copolymer was selectively obtained. Copolymerization of ethylene and 1,3-butadiene was also conducted with cobalt dichloride activated by methylaluminoxane. Although the copolymerization did not proceed, cobalt dichloride-methylauminoxane was found to effective for cis-specific living polymerization of 1,3-butadiene. Less

Report

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

    (15 results)

All Other

All Publications (15 results)

  • [Publications] T.Shiono, O.Yoshino, T.Ikeda: "Copolymerization of ethene and 1,3-butadiene over a SiO_2-supported CpTiCl catalyst"Micro-Kinetics and Dynamics of Individual Active Sites in Catalytic Reactions. 131-137 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] D.C.Nath, T.Shiono, T.Ikeda: "cis-Specific living Polymerization of 1,3-butadiene Polymerization with cobalt dichloride and methylaluminoxane"Macromol. Chem. Phys.. 203・4. 756-760 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] D.C.Nath, T.Shiono, T.Ikeda: "Effect of halogen ligands on of 1,3-butadiene Polymerization with cobalt dihalides and methylaluminoxane"Macromol. Chem. Phys.. 203・9. 1171-1177 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] D.C.Nath, T.Shiono, T.Ikeda: "Copolymerization of 1,3-butadiene and isoprene with cobalt dichloride-methylaluminoxane in the presence of triphenylphosphine"J. Polym. Sci., Part A : Polym. Chem. Ed.. 40・17. 3086-3092 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] D.C.Nath, T.Shiono, T.Ikeda: "Polymerization of 1,3-butadiene by cobalt dichloride activated with various aluminoxanes"Appl. Catal. A. 238. 193-199 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] D. C. Nath, T. Shiono and T. Ikeda: "cis-Specific living polymerization of 1,3-butadiene with CoCl_2 and methylaluminoxane"Macromol. Chem. Phys.. 203[4]. 756-760 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] D. C. Nath, T. Shiono and T. Ikeda: "Effect of halogen ligands on of 1,3-butadiene polymerization with cobalt dihalides and methylaluminoxane"Macromol. Chem. Phys.. 203[9]. 1171-1177 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] D. C. Nath, T. Shiono and T. Ikeda: "Copolymerization of 1,3-buladiene and isoprene with cobalt dichloride-methylaluminoxane in the presence of triphenylphosphine"J. Polym. Sci., Part. A : Polym. Chem. Ed.. 40[7]. 3086-3092 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] D. C. Nath, T. Shiono and T. Ikeda: "Polymerization of 1,3-butadiene by cobalt dichloride activated with various aluminoxanes"Appl. Catal. A. 238. 193-199 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Shiono, O. Yoshino and T. Ikeda, ed, T. Sano, T. Uozumi, H. Nakatani, M. Terano and N. Otsuka.: "Copolymerizalion of ethene and 1, 3-butadiene over SiO_2-supported CpTiCl_3 catalyst ; "Micro-Kinetics and Dynamics of Individual Active Sites in Catalytic Reactions"T"echnology and Education Publishers. 131-137 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] D.C.Nath, T.Shiono, T.Ikeda: "cis-Specific living polymerization of 1,3-butadiene polymerization with cobalt dichioride and methylaluminoxane"Macromol.Chem.Phys.. 203・4. 756-760 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] D.C.Nath, T.Shiono, T.Ikeda: "Effect of halogen ligands on of 1,3-butadiene polymerization with cobalt dihalides and methylaluminoxane"Macromol.Chem.Phys.. 203・9. 1171-1177 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] D.C.Nath, T.Shiono, T.Ikeda: "Copolymerization of 1,3-butadiene and isoprene with cobalt dichloride-methylaluminoxane in the presence of triphenylphosphine"J.Polym.Sci., Part A : Polym.Chem.Ed.. 40・17. 3086-3092 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] D.C.Nath, T.Shiono, T.Ikeda: "Polymerization of 1,3-butadiene by cobalt dichioride activated with various aluminoxanes"Appl.Catal.A. 238. 193-199 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Shiono, O.Yoshino, T.Ikeda: "Copolymerization of ethene and 1, 3-butadiene over a SiO_2^- supported CpTiCl catalyst"Micro-Kinetics and Dynamics of Individual Active Sites in Catalytic Reactions. 131-137 (2001)

    • Related Report
      2001 Annual Research Report

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

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