Photooxidation of polystyrene: Irradiation at 254 and 365 nm

Abstract

AbstractStudies have been made of the near surface photooxidation of atactic polystyrene films prepared in the absence of air. The samples were photooxidized on exposure to air at two frequencies, 254 and 365 nm, using a calibrated mercury irradiation source with filters. Most studies were made at 40°C and as a function of irradition time with the reactions characterized by changes in molecular weight and composition. The former was evaluated by gel permeation chromatography and the latter by transmission Fourier transform infrared spectroscopy and by multiple‐internal‐reflectance infrared spectra using different angles and different crystals to evaluate compositions as a function of film depth. Species identified in photooxidation include the generation of hydroperoxides and the appearance of carbonyl bands with the latter identified by the spectral shift asociated with the exposure of the photooxidized polystyrene surface to ammonia. These results suggest that principal products of near‐surface oxidation of polystyrene are carboxylic acids.