Chemiluminescence from oxidation of polyamide 6,6: II. The effect of metal salts

Abstract

Chemiluminescence (CL) emission from isothermal and non-isothermal oxidation of polyamide 6,6 in the presence of Co, Ni, Cu and Zn chlorides, alone or combined with KI, demonstrates that copper salts, irrespective of the oxidation number, are the most efficient stabilizing species. They reduce CL emission of the third stage of observed kinetic runs, ascribed to the chain oxidation of polyamide, most efficiently. Cobalt chloride has pro-oxidative rather than a stabilizing action. Synergism has been observed for chlorides of Ni, Zn and Co and for KI. The kinetic analysis of chemiluminescence against temperature was based on two different pathways of initiation: 1. A fast process via either free radicals entrapped in the polymer or terminal amino groups. 2. A slower process involving the free radical chain oxidation of the polyamide. The presence of metal salts combined with KI leads to a reduction of the rate constants of the slower stage by more than two orders of magnitude whilst the rate constants of the faster stage are increased by the presence of metal salts.