Conversion among photo-oxidative products of polypropylene in solid, liquid and gaseous states

During aging of polymers, oxidized species on macromolecular chains in solid state, volatile degradation products in liquid state and gaseous degradation products in gaseous state are often investigated separately. The conversion among these products is not especially concerned and biased results may be obtained based on the products in a single state. In this paper, photo-oxidative products of commercial polypropylene (PP) and unstabilized PP in solid, liquid and gaseous states were investigated by using Fourier transform infrared spectroscopy (FTIR), pyrolysis–gas chromatography/mass spectrometry (Py-GC/MS) and gas chromatography (GC). By comparing the formation profiles, conversion among the photo-oxidative products in three states was traced. During photo-oxidative aging, the main chains of PP were first oxidized to form carbonyl species in solid state, or fractured to form volatile alkenes as liquid. With the proceeding of aging, the oxidized main chains fractured to form small molecules, resulting in the conversion of oxidized species from solid state to liquid and gaseous states. When the aging degree was extremely high, the accumulation of liquid oxidized products was limited due to migration and condensation. Therefore, both the carbonyl index (CI) and the concentrations of volatile oxidized products were increased first and then decreased, while the concentrations of gaseous products kept increasing all along.