Chemiluminescence studies of the low temperature thermooxidation of poly(phenylene sulfide)

Chemiluminescence has been used to study the thermooxidation of poly(phenylene sulfide) film at 85–110°C in oxygen. To identify reaction products, the degraded surfaces were immediately analyzed by x‐ray photoelectron spectroscopy, then exposed to light and reanalyzed. In the proposed reaction sequence, thiyl radicals generated by oxidation of thiol end groups undergo chain transfer with polymer and bimolecular termination giving thiones, emitters that account for part of the chemiluminescence spectrum. Reaction is extensive at the surface, and subsequent exposure of the thermooxidized surface to light results in considerable loss of sulfur as well as carbon. The role of the thione products in subsequent degradation and chemiluminescence is discussed.