Addition-Fragmentation Chain Transfer Reactivities of .ALPHA.-Methylstyrene Unsaturated Dimer

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  • YAMADA Bunichiro
    Department of Applied and Bioapplied Chemistry, Graduate School of Engineering, Osaka City University
  • INOUE Kentarou
    Department of Applied and Bioapplied Chemistry, Graduate School of Engineering, Osaka City University

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Other Title
  • α－メチルスチレン不飽和二量体の付加開裂連鎖移動反応性
  • アルファ メチルスチレン フホウワ 2リョウタイ ノ フカカイレツレンサ イドウ ハンノウセイ

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Description

The α-methylstyrene unsaturated dimer (2, 4-diphenyl-4-methyl-1-pentene, MSD) was used for photosensitized styrene (St) polymerization at 30-130°C. The adduct radical formed from MSD was detected by ESR spectroscopy to monitor the after effect. The rate constants (kt) for mutual reaction of the adduct radical were calculated from the decay curves. The kt values at 100°C or above deviated from the linear relationship obtained by the Arrhenius plot at lower temperatures. The adduct radical was considered to react mutually and to undergo β-fragmentation. The chain transfer constant of MSD at 100 and 130°C were 0.26 and 0.46, respectively. A kinetic equation consisting of the terms of bimolecular reaction and β-fragmentation was derived and the rate constants for these reactions were estimated at different temperatures. Chain transfer constants of MSD were calculated from the Mayo equation: 0.26 and 0.46 at 100 and 130°C, respectively. It was predicted that MSD acts as an effective chain transfer agent in styrene polymerization to reduce molecular weight and to introduce the 2-phenyl-2-propenyl end group competing with addition of the adduct radical to styrene over the temperature range examined. More significant acceleration of the β-fragmentation with increasing temperature than the mutual reaction results in higher chain transfer reactivity of MSD at higher temperatures. MSD also act as an effective AFCT agent in methyl methacrylate polymerization

Journal

  • KOBUNSHI RONBUNSHU

    KOBUNSHI RONBUNSHU 61 (4), 275-281, 2004

    The Society of Polymer Science, Japan

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