Auto-oxidation occurs with polymers with molecular oxygen in their structure. This leads to the presence of free radicals. Hydroxide radicals are the initiation step for a multitude of of hydrolysis reactions or addition reactions, such as in aromatic compounds. Trace quantities of metals in polymers, whether impurities or minor parts or the polymer chain, can also catalyze the oxidative process. Metals are often present in the polymeric matrix as ions, which can pull a hydrogen molecule off the matrix, leaving a free radical.
Free radicals start the chain scission which leads to degredation.
This page prepared by Kimberly Farrell for Professor Sisson of WPI , for use in ME XXX, Corrosion and assorted fun times.