Study of secondary relaxations in poly(vinyl chloride) by phosphorescence decay: Effect of the chemical structure and the concentration of luminescent probes

The phosphorescence emission of both naphthalene and pyridine can be used to detect the secondary (β) relaxation of PVC, as this relaxation manifests by a decrease in the emission from the grafted probe at the temperatures at which the local motion at the backbone begins. In this work, an extensive study of the kinetic and spectral features of the phosphorescence of 4-mercaptopyridine, 4-methoxybenzenethiol and 4-mercaptophenol groups as a function of temperature is presented. These three luminescent probes have been grafted onto PVC, with modification levels ranging from 3% up to 46%. The phosphorescence decay from −130 °C up to 30 °C has been followed and both the intensity of the emission and the spectral features have been studied as a function of temperature. The interaction between probes as the concentration increases leads in all cases to the emission from aggregates or excimers, which have features different to those of the isolated probe. Side reactions occur when grafting the hydroxyl containing probe, what also leads to surprising phosphorescence spectral and decay rate features.