| Abstract: | The photodegradation of polyesters prepared by the reaction of o-phthalic, adipic, and “dimer” acids with ethylene glycol has been studied. The polyesters softened at temperatures in the range of 25–50°C. Polymer films were irradiated in air by means of a medium pressure mercury lamp and the extent of formation of COOH groups determined by infrared spectroscopy. The films were also irradiated in vacuo and in air by means of a high-pressure mercury lamp, and the volatile products, consisting mainly of carbon monoxide and carbon dioxide, were determined by gas chromatography. The results are interpreted in terms of simultaneous Norrish type I and type II decompositions of the polyesters. The type I process accounts for the formation of carbon monoxide and carbon dioxide in the absence of air. The enhanced yield of carbon dioxide in irradiations performed in air is ascribed to the formation of hydroperoxide which undergoes further photolysis. The type II process accounts for the formation of COOH groups. The photodegradation of these glassy polyesters parallels that of crystalline poly(ethylene terephthalate) and is relatively unaffected by changes in composition of the aromatic polyester. |
