CLOSE LOOP MECHANISTIC SCHEMES FOR HYDROCARBON POLYMER OXIDATION

Mechanistic schemes of radical oxidation of hydrocarbon polymers in wh ich initiation is only due to unimolecular or bimolecular hydroperoxid e decomposition have been studied. The results of their kinetic analys is have been compared with literature data relative to the thermal oxi dation of polypropylene in solid state (60-160 degrees C). These data are in remarkably good agreement with the ''unimolecular'' scheme whos e main characteristics are: (1) the quasi-independence of the kinetic behavior with initial conditions (for low initial content of thermolab ile structures), and (2) the fact that an arbitrarily defined inductio n period depends only on the rate constant of unimolecular hydroperoxi de decomposition. (C) 1995 John Wiley and Sons, Inc.