GENERATION OF RADICALS BY THE REACTION OF OLEFINS AND BENZOQUINONE WITH C-H BONDS OF HYDROCARBONS

An analysis has been made of the question of the generation of radical s by bimolecular reactions of the type RH + CH2 = CHR --> R' + CH3CHR and RH + O = CR1R2 --> R-. + HOCR1R2. A semi-empirical method - a para bolic model of the bimolecular reaction - has been used to calculate t he activation energies and pre-exponential factors for 33 reactions of this kind. An examination has been made of the role of these reaction s in chain processes of hydrocarbon cracking, radical polymerization a nd olefin oxidation. An analysis has been made of the question of the generation of radicals by the reaction of p-benzoquinone with hydrocar bons and hydroperoxides. The rate constants have been calculated for 2 6 reactions of this kind. The role of these reactions in the phenol-in hibited oxidation of hydrocarbons is discussed. (C) 1997 Elsevier Scie nce Ltd. All rights reserved.