Dielectric relaxation properties of poly(dimethylphenyl methacrylate)s

The dielectric relaxations of poly(dimethylphenyl methacrylate)s were studied over a wide frequency and temperature range by two methods. The α relaxation, associated with the glass transition temperature, was studied by classical dielectric measurements. Thermal peak cleaning was used to deconvolute the global thermally stimulated current spectra over the range of low temperatures, corresponding to the β relaxation. The α relaxation involves long-range, generalized and highly cooperative motions of the main chain. They are influenced by the steric hindrance and dipole-dipole interactions relative to the position of the CH₃ group of the aryl ring in the polymer repeat unit. As a first approximation it was assumed that the β process was related only to local motions of the side group, but the activation parameters are too high to be consistent with this assumption. Therefore it was concluded that intermolecular factors and local motions of the main chain could also be involved.