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1992 Fiscal Year Final Research Report Summary

Synthesls and Characterization of Block Copolymers consisting of Conjugated Monomers and Ethylene by Means of Active Site Modification

Research Project

Project/Area Number 03650751
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field 高分子合成
Research InstitutionOsaka City University

Principal Investigator

ENDO Kiyoshi  Osaka City University, Fac. of Engineering, Associate Professor, 工学部, 助教授 (10047409)

Co-Investigator(Kenkyū-buntansha) MATSUMOTO Akikazu  Osaka City University, Fac. of Engineering, Research Associate, 工学部, 助手 (00183616)
YAMADA Bunichiro  Osaka City University, Fac. of Engineering, Associate Professor, 工学部, 助教授 (50047198)
OTSU Takayuki  Osaka City University, Fac. of Engineering, Professor, 工学部, 教授 (00046864)
Project Period (FY) 1991 – 1992
KeywordsActive Species / Active Site Modification / Conjugated Monomer / Ethylene / Styrene / Isoprene / tert-Diamines / Block Copolymers
Research Abstract

The following results were obtained from the study on synthesis and characterization of block copolymers by means of active site modification. First, block copolymer consisting of styrene and ethylene bearing narrow molecular weight distribution has been synthesized by means of active site modification performed by the addition of t-diamines to living poly(styrene). Similarly, block copolymer consisting of isoprene and ethylene segments has been synthesized by means of "active site modification" performed by adding appropriate t-diamines such as N,N,N,N-tetramethylethylenediamine (TMEDA) and sparteine to the living polymer initiated with alkyllithium. Block copolymers formed have a relative narrow molecular weight distribution and retained the mainly 1,4-units in the microstructure of IP segment. Such block copolymerization with ethylene could not be admitted in the absence of the t-diamines and only homopolymer of isoprene was recovered. Block copolymer of ethylene and methyl methacrylate with alkyllithium complexed with tert-diamines by means of chain end modification by diphenyl ethylene was synthesized. These were applied to homopolymerization of ethylene and isoprene. The polymerization of ethylene initiated with alkyllithiums complexed by TMEDAN was studied by using ^<13>C NMR spectroscopy and GPC. In the cases of s-butyllithium and t-butyllithium, both initiation and termination chain end were determined by ^<13>C NMR spectra, and GPC elution curves of the polymers shifted to higher molecular weight side with reaction time. This suggests that the polymerization of ethylene initiated with alkylgroups in alkyllithiums and propagating species have a living nature. In the case of isoprene, the microstructure of the polymers could be controlled by the activesite modification.

  • Research Products

    (4 results)

All Other

All Publications (4 results)

  • [Publications] Kiyoshi Endo and Takayuki Otsu: "A novel method for the syn thesis of block copolymers of isoprene and ethylene by means of active site modification" Makromol.Chem.,Rapid Communs. 13. 135-139 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kiyoshi Endo and Takayuki Otsu: "Polymerization of Ethylene with alkyl lithium compounds in the presence of tertiary diamines studied by ^<13>CNMR spectroscopy and gel permeation chromato graphy" Makromol.Chem.,Rapid Communs. 14. 1-3 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kiyoshi Endo and Takayuki Otsu: "Novel Method for the Synthesis of Block Copolymers of Isoprene of Isoprene and Ethylene by Means of Active Site Modification" Makromol. Chcm., Rapid Communs. 13. 135-139 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kiyoshi Endo and Takayuki Otsu: "Polymerization of Ethylene with Alkyllithium Compounds in the Presence of tertiary Diamines studied by 13C NMR Spectroscopy and Gel-permeation Chromatography" Makromol. Chem., Rapid Communs. 14. 1-3 (1993)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1994-03-24  

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