Sensitive luminescence techniques to study the early stages of polymer oxidation

This paper describes recent developments in the use of chemiluminescence (CL) and profluorescent nitroxides (PFNs) in probing the “induction period” of polymer oxidation. CL measures the instantaneous rate of reaction of hydroperoxides responsible for initiating degradation and the spreading of oxidation, while PFNs can be used to measure the concentration of alkyl radicals produced in oxidation events and thus provide an integrating sensor for the extent of cumulative damage. The PFN additive acts as an oxidation retarder by competing with oxygen to scavenge the alkyl radicals that generate chain carrying peroxy radicals and so mirrors the performance of hindered amine stabilisers (HAS) in one part of their stabilisation cycle. Using the example of polypropylene (PP) and cis-polyisoprene (PIP) as substrates which can rapidly spread oxidative damage, the factors controlling the reaction of PFNs can be determined from CL and fluorescence as well as infra-red (IR) spectroscopy through the detection of oxidation products as measured by the carbonyl index. Matrix effects on the reactivity are demonstrated using a polyethylene-norbornene copolymer (TOPAS) as carrier for both PIP and the PFN and it is seen that the PFN is a radical scavenger only above T_g of the carrier. When PIP alone is oxidized, the PFN is an integrating sensor for free radical production under ambient conditions for up to twelve months while also stabilizing the polymer. Critically, it is thus able to determine the underlying rate of radical production in the oxidation induction period.