Kinetic Studies in the Chemistry of Rubber and Related Materials. II. The Kinetics of Oxidation of Unconjugated Olefins

A brief review is given of kinetic work on the oxidation of representative mono, 1,4 and 1,5 olefins. The essential process in each case is identified as a chain reaction in which hydrocarbon radicals are formed, absorb oxygen, and then react with another molecule of olefin to give a hydroperoxide and a new free radical. Three methods of chain initiation are considered: (1) direct attack of oxygen on the olefin, (2) thermal decomposition of the hydroperoxide, (3) thermal decomposition of added benzoyl peroxide. Chain termination results from interaction of two free radicals; except at low oxygen pressures, these are both peroxidic.