Abstract
Intimate relationship between the thermal behavior and the structural change has been clarified for the first time by an organized combination of isothermal DSC thermogram and FT/IR spectra measured for the stabilization reaction of an acrylonitrile (AN)/methacrylic acid (MAA) copolymer. In an early stage of the isothermal exothermic thermogram measured by DSC under air, a flat region or the induction period of the cyclic structure formation was found to exist, which is immediately followed by the two stages of steep heat evolution and the slow heat release. Based on the IR spectral changes observed during this thermal reaction, the induction stage was found to be associated with the reaction of methacrylic acid groups with the adjacent nitrile groups and the steep heat evolution region with the propagation of the cyclic structure and dehydrogenation of the polyacrylonitrile (PAN) chain sequences to give an unsaturated ladder structure. An activation energy for this initiation reaction of the cyclic structure formation was evaluated to be ca. 26 kcal/mol by an Arrhenius plot.
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Kakida, H., Tashiro, K. & Kobayashi, M. Mechanism and Kinetics of Stabilization Reaction of Polyacrylonitrile and Related Copolymers I. Relationship between Isothermal DSC Thermogram and FT/IR Spectral Change of an Acrylonitrile/Methacrylic Acid Copolymer. Polym J 28, 30–34 (1996). https://doi.org/10.1295/polymj.28.30
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DOI: https://doi.org/10.1295/polymj.28.30
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