Relaxation behavior of semiflexible polymers at very low frequencies

Abstract

The dielectric activity of poly(monocyclohexylmethylene itaconate) (PMCI) and poly(dicyclohexylmethylene itaconate) (PDCI) in the glassy region and in the glass–rubber transition is studied by thermostimulated discharge current (TSDC) techniques. The spectra obtained by global TSDC experiments show a prominent α-glass–rubber relaxation peak with maxima located at 97 and 55 °C for PMCI and PDCI, respectively, following in decreasing order of temperature for a well developed β absorption and a comparatively low intensity relaxation. Better resolution of the relaxation behavior of these polymers in the glassy region is obtained by calculating the components of the complex dielectric permittivity ε* at extremely low frequencies from partial TSDC experiments. The ac spectra thus obtained suggest that the β absorption is composed by two relaxations, each of them presumably associated with the motions of a side group. The differences observed in these spectra with those reported for the β mechanical relaxation reported for these polymers in the literature are interpreted in terms of the restrictions that the side groups produce in the conformational space of phase of the backbone. These restrictions also explain the small changes in enthalpy in the glass–rubber transition which preclude the possibility of obtaining the glass–rubber transition temperature of these polymers by differential scanning calorimetric techniques.