High pressure dynamics of polymer/plasticizer mixtures.

Plasticizers are usually added to polymers to give them the desired flexibility and processability by changing the dynamical properties of the polymer chains. It is therefore important to give a quantitative description about how the dynamic behavior of a given polymer is modified by the incorporation of a second component. We analyze in this work, by means of dielectric spectroscopy, the dynamics of poly(vinyl acetate)/diethyl phthalate mixtures, at different concentrations, over a broad range of frequency, pressure, and temperature. The dynamics of these particular mixtures show only one main relaxation process contrarily to what is observed in athermal miscible polymer mixtures. From the dielectric spectra the maximum relaxation time as a function of pressure and temperature was obtained and analyzed. We studied the pressure dependence of the glass transition temperature as well as the fragility of both the neat components and the mixtures at different concentrations (on the rich polymer range). Finally, the experimental data were rationalized within the framework of an Adam-Gibbs (AG) based approach recently developed [G. A. Schwartz et al., J. Chem. Phys. 127, 154907 (2007)]. The model, originally developed for athermal blends, is here modified to take into account the non-negligible interaction between polymer and plasticizer. We found that the temperature-pressure dependence of the alpha-relaxation time is very well described by this AG extended model.