Dielectric and dynamic mechanical behavior of poly(vinyl acetate) containing small concentrations of cholesteryl additives

Abstract

AbstractDielectric loss measurements at four temperatures and as a function of frequency are presented for the poly(vinyl acetate) (PVAc) systems containing small concentrations of cholesterol, cholesteryl acetate, cholesteryl oleate, cholesteryl nonanoate, cholesteryl benzoate, cholesteryl oleyl carbonate, p‐methoxy benzilidine‐p‐n‐butyl aniline, diphenyl ether, and cetyl acetate. For the first five systems, the α‐relaxation temperature for sure PVAc was found to be increased in the presence of the said additives. The results of the dielectric depolarization spectroscopy at 1 kHz and the dynamic mechanical analysis also conform with these observations. It is inferred that the segmental motion in PVAc is hindered by these first five additive molecules through a specific dipolar interaction. These additives are therefore described as antiplasticizers to PVAc as they extend the glassy region over a wider temperature interval. The analysis of the dielectric data to give the dielectric decay function and the β parameter reveals that the two types of the additives, viz., plasticizers and antiplasticizers, can be distinguished by the opposite signs obtained for the ratio Δβ/ΔC, where C is the concentration. The analysis based on the WLF theory shows that the WLF reference temperature T0 is higher than that for pure polymer if the additive is an antiplasticizer while the same is lower for the plasticizing additives. The apparent enthalpy of activation for the dielectric relaxation process is found to be higher in the case of additives which show antiplasticization of PVAc.