ABSTRACT

Kinetic studies of the decomposition of the polymer hydroperoxides in an inert atmosphere are expected to give a clear answer to the question of initiation molecularity, but here also, a doubt remains. As a matter of fact, Chien and Jabloner (44) and, more recently, Gijsman et al. (22), by chemical titration obtained POOH decay curves interpretable in terms of superposition of two first-order processes, corresponding to the coexistence of fast-and slow-decomposing hydroperoxides. Billingham et al. (46) used chemiluminescence and obtained decay curves well fitted, in the whole conversion range, by the second-order model. However, here, the mechanism of light emission remains unknown, and the intensity is not necessarily proportional to the POOH decomposition rate, especially if chemiluminescence results from the PO; bimolecular combination, as frequently proposed.