ESR study of the molecular dynamic of peroxyradicals in the post‐irradiation oxidation of isotactic polypropylene

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AbstractBy adopting the modified Bloch equations, the analysis of the motion of macroperoxyradicals during the post‐irradiation oxidation of isotactic polypropylene at room temperature has been performed. Rotations about the chain axis and cubic jumps are the motion of prominent importance in the early stages of reaction involving mostly radicals trapped at defects or in amorphous phase; on the other hand rotations about the CO bonds at decreasing rates are dominant in the latter stages. Clear evidence of the progressive immobilization of peroxyradicals, which may be reckoned with monomolecular termination mechanism and of the trapping of peroxyradicals in the crystalline phase, have been obtained.