Photochemical degradation of poly(ethylene terephthalate). III. Determination of decomposition products and reaction mechanism



The vacuum photolysis and air photo-oxidation of poly(ethylene terephthalate) were studied using light in the wavelength ranges of 225–420 nm and 300–420 nm. The volatile photodegradation products were determined by mass-spectrometric and gas-chromatographic analysis; CO and CO2 were found to be the predominant products. In addition, the rates of formation of carboxylic acid endgroups and the net weight losses of the film samples were determined as a function of irradiation time. Quantum yields for the initial rates of formation of CO and CO2 and of [BOND]COOH within the film were calculated. On the basis of the results obtained, in this and the preceding papers in this series, reaction mechanisms have been proposed for the photochemical degradation of the polymer. The production of CO and [BOND]COOH in both vacuum and air have been attributed mainly to a Norrish type I cleavage and a Norrish type II photorearrangement, respectively. It has also been concluded that, in the presence of air, an oxidative reaction sequence occurs whereby alkyl radicals produced on photolysis react with oxygen to form ROO. radicals. These subsequently react further to produce CO2 as the main volatile product of photooxidation.