• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Studies of Radical Polymerization by Using Long-lived Propagating Polymer Radicals

Research Project

Project/Area Number 02453108
Research Category

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

Allocation TypeSingle-year Grants
Research Field 高分子合成
Research InstitutionThe University of Tokushima

Principal Investigator

SATO Tsuneyuki  The University of Tokushima, Faculty of Engineering, Professor, 工学部, 教授 (20047187)

Co-Investigator(Kenkyū-buntansha) TANAKA Hitoshi  The University of Tokushima, Faculty of Engineerig, Associate Professor, 工学部, 助教授 (40127840)
Project Period (FY) 1990 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥5,200,000 (Direct Cost: ¥5,200,000)
Fiscal Year 1991: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1990: ¥4,500,000 (Direct Cost: ¥4,500,000)
KeywordsRadical Polymerization / Propagating Polymer Radical / ESR Spectrum / Rate Constant of Propagation / Rate Constant of Termination / Lewis Acid Effect / Solvent Effect / キャプトデイティブ置換
Research Abstract

Itaconic acid derivatives and some related monomers were found to be easily polymerized by radical initiators in spite of their two bulky alpha -substituents. The polymerization systems were observed to involve ESR-detectable propagating polymer radicals under the actual polymerization conditions. Using the polymer radical concentration determined by ESR, we succeeded in estimating the rate constants of propagation (k_p) and termination (k_t) of these monomers. The k_p and k_t values of dialkyl itaconates decrease as the alkyl chain becomes longer. The steric effect due to the alkyl group suppresses much more termination than propagation, leading to the fact that the monomer with longer alkyl group shows a higher polymerization rate. The k_p value of dioctyl itaconate is smaller in a more polar solvent. The considerable solvent effect is explicable in terms of affinity of the propagating polymer radical for the solvent used. The presence of SnCl_4 reduces both the k_p and k_t values of diethyl itaconate, which seems to be due to an entropy factor. k_p (990 l/mols, 60゚C) of ethyl alpha -benzoyloxymethylacrylate (EBMA) is much larger (about two factors) than those of itaconates, and k_t (2.9x10^6 l/mol s) of EBMA is ten times those of itaconates. Methyl N-phenylitaconamate shows the k_p (8.2 l/mol s) and k_t (1.9-4.2 l/mol s) values 55゚C similar to those of itaconates. k_p (24-27 l/mol s) of N- (2.6-dimethylphenyl) itaconimide at 50゚C is almost independent of the monomer concentration, while kt (3.8x10^4-2.0x10^5l/mols) decreases with the monomer concentration which is ascribable to dependence of k_t on the polymer chai n length. ESR spectroscopic and kinetic evidences for penultimate effect were obtained in the radical copolymerization of dibutyl itaconate with N-cyclohexylmaleimide.

Report

(3 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • Research Products

    (19 results)

All Other

All Publications (19 results)

  • [Publications] Tsuneyuki Sato: "An ESR study on the radical copolymerization of N-cyclohexylmaleimide and di-n-butyl itaconate in benzene" Macromolecules. 24. 2330-2333 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Tsuneyuki Sato: "Radical Polymerization of ethyl α-benzoyloxymethyl-acrylate in benzene" European Polymer Journal. 27. 1087-1092 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Tsuneyuki Sato: "Kinetic and ESR studies on the radical-initiated polymerization of N-(2,6-dimethylphenyl)itaconimide" Makromolekulare Chemie. 192. 2231-2241 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Tsuneyuki Sato: "Effect of SnCl_4 on the radical-initiated polymerization of diethyl itaconate:Kinetical and ESR studies" Makromolekulare Chemie. 192. 2659-2668 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Tsuneyuki Sato: "Effect of alkyl group on the rate constants of propagation and termination in the radical polymerization of dialkyl itaconate" Makromolekulare Chemie. 192. 2909-2914 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Tsuneyuki Sato: "Solvent effect on the propagation rate constant in the radical polymerization of di-2-ethylhexyl itaconate" Makromolekulare Chemie,.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Tsuneyuki Sato: "An ESR study on the radical copolymerization of N-cyclohexylmaleimide and di-n-butyl itaconate in benzene" Macromolec.24. 2330-2333 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Tsuneyuki Sato: "Radical polymerizatin of ethyl alpha-benzoyloxymethylacrylate in benzene" Eur., Polym. J.27. 1087-1092 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Tsuneyuki Sato: "Kinetic and ESR studies on the radical-initiated polymerization of n- (2, 6-dimethylphenyl) itaconimide" Macromol. Chem.192. 2231-2241 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Tsuneyuki Sato: "Effect of SuCl_4 on the radical-initiated polymerization of diethyl itaconate : kinetical and ESR studies" Macromol. Chem.192. 2909-2668 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Tsuneyuki Sato: "Effect of alkyl group on the rate constants of propagation and termination in the radical polymerization of dialkyl itaconates" Macromol. Chem.192. 2909-2914 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Tsuneyuki Sato: "Solvent effect on the propagation rate constant in the radical polymerization of di-2-ethylhexyl itaconate" Macromol. Chem.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Tsuneyuki Sato: "An ESR study on the radical copolymerization of Nーcyclohexylmaleimide and diーnーbutyl itaconate in benzene" Macromolecules. 24. 2330-2333 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Tsuneyuki Sato: "Effect of SnCl_4 on the radicalーinitiated polymerization of diethyl itaconate:Kinetical and ESR studies" Makromol.Chem.192. 2659-2668 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Tsuneyuki Sato: "Effect of alkyl group on the rate constants of propagation and termination in the radical polymerizations of dialkyl itaconates" Makromol.Chem.

    • Related Report
      1991 Annual Research Report
  • [Publications] Tsuneyuki Sato: "Solvent effect on the propagation rate constant in the radical polymerization of diー2ーethylhexyl itaconate" Makromol.Chem.

    • Related Report
      1991 Annual Research Report
  • [Publications] Tsuneyuki Sato: "Radical polymerization of ethyl αーbenzoyloxymethylacrylate in benzene" Eur.Polym.J.

    • Related Report
      1990 Annual Research Report
  • [Publications] Tsuneyuki Sato: "Kinetic and ESR studies on theradical polymerization of Nー(2,6ーdimethylphenyl)itaconimide" Makromol.Chem.

    • Related Report
      1990 Annual Research Report
  • [Publications] Hitoshi Tanaka: "Radical and spontaneous thermal polymrtization of some captodative substituted acrylates" Makromol.Chem.

    • Related Report
      1990 Annual Research Report

URL: 

Published: 1990-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi