Deconvolution of the relaxations associated with local and segmental motions in poly(methacrylate)s containing dichlorinated benzyl moieties in the ester residue

Abstract

The relaxation behavior of poly(2,3-dichlorobenzyl methacrylate) is studied by broadband dielectric spectroscopy in the frequency range of 10–1–109 Hz and temperature interval of 303–423 K. The isotherms representing the dielectric loss of the glassy polymer in the frequency domain present a single absorption, called B process. At temperatures close to Tg, the dynamical (alfa) relaxation already overlaps with the (beta) process, the degree of overlapping increasing with temperature. The deconvolution of the (alfa) and (beta) relaxations is facilitated using the retardation spectra calculated from the isotherms utilizing linear programming regularization parameter techniques. The temperature dependence of the (beta) relaxation presents a crossover associated with a change in activation energy of the local processes. The distance between the (alfa) and (beta) peaks, expressed as log(fmax;/fmax;) where fmax is the frequency at the peak maximum, follows Arrhenius behavior in the temperature range of 310–384 K. Above 384 K, the distance between the peaks remains nearly constant and, as a result, the (alfa) onset temperature exhibited for many polymers is not reached in this system. The fraction of relaxation carried out through the (alfa) process, without (beta) assistance, is larger than 60% in the temperature range of 310–384 K where the so-called Williams ansatz holds.