The thermal oxidation of non-stabilized isotactic polypropylene was st
udied in air at 80, 90, 100 and 150 degrees C using gravimetric and IR
spectrophotometric determinations (hydroxyls and carbonyls). A kineti
c model in which radical production results only from unimolecular hyd
roperoxide decomposition was developed. This model predicts that: the
induction time depends only on the rate constant of hydroperoxide deco
mposition. It must be almost independent of the polypropylene source (
for low content of catalytic impurities and low initial hydroperoxide
concentration) and its apparent activation energy must be about 100 kJ
mol(-1); the induction times relative to, respectively, weight, carbo
nyl and hydroxyl gain must be in the ratio 2:3:3; 'the steady state' o
xidation rate must be independent of initiation rate constant. The exp
erimental data on oxidation kinetics in the temperature range under st
udy confirm all these predictions. (C) 1997 Elsevier Science Limited.