Effect of Accelerated Thermal Degradation of Poly(Vinyl Chloride): The Case of Unplasticized PVC

Abstract: The thermal degradation of unplasticized poly(vinyl chloride), PVC, was comprehensively investigated through the application of spectroscopic techniques, as well as contact angle measurements (CA), dynamic mechanical analysis (DMA), and size-exclusion chromatography (SEC). To study the effect of relative humidity (RH) on the deterioration of unplasticized PVC, two regimes of accelerated degradation experiments were selected: low RH (max. 30% RH) and high RH = 60% levels, which corresponds to usually the highest RH in heritage institutions equipped with an HVAC system. Nuclear magnetic resonance (NMR) and infrared spectroscopy (FTIR) did not reveal any significant changes in the material during its degradation up to 20 weeks at temperatures ranging from 60{\deg}C to 80{\deg}C. Notable changes were observed in the Raman and UV-Vis spectra, indicative of the formation of conjugated carbon-carbon double bonds. The formation of polyenes was responsible for the yellowing of samples. Notwithstanding, the aforementioned changes did not lead to a notable decline in the mechanical properties, as evidenced by DMA and SEC measurements. EPR measurements demonstrated the formation of 2 radicals at 60{\deg}C, and in the sample degraded at 80{\deg}C the presence of radicals was evident. This indicates that a radical degradation mechanism cannot be excluded even at such low temperatures.