Influence of the Fine Structure on the Response of Polymer Chains to Perturbation Fields

The relaxation behavior of poly(3-methylbenzyl methacrylate), poly(3-fluorobenzyl methacrylate), and poly(3-chlorobenzyl methacrylate) was thoroughly studied by broadband dielectric spectroscopy with the aim of investigating the influence of slight differences in chemical structure on the response of polymers to electric perturbation fields. Retardation spectra calculated from dielectric isotherms utilizing linear programming regularization parameter techniques were used to facilitate the deconvolution of strongly overlapped absorptions. Above the glass transition temperature, the spectra of the two halogenated polymers present a secondary γ process well separated from a prominent peak resulting from the overlapping of the α and β relaxations. The spectra of poly(3-methylbenzyl methacrylate) exhibit at long times a well-developed α absorption followed in decreasing order of time by two weak absorptions, named β and γ, whose intensities increase with temperature. The temperature dependence of the distance of the α peak from the β and γ peaks, expressed in terms of log(f max, β/f max, α) and log(f max, γ/f max, α), respectively, is studied. The Williams ansatz and the extended ansatz give a fairly good account of the relaxation behavior of the polymers. The stretch exponent associated with the α relaxation increases with temperature from ca. 0.2 at low temperatures to the vicinity of 0.5 at high temperatures. At low temperatures, the α relaxation is described by a Vogel-type equation, but at high temperature the β and α processes are roughly described by the same Arrhenius equation. In the whole temperature range, the activation energy o the γ relaxation is significantly lower than that of the β absorption. The mechanisms involved in the development of the secondary relaxations are qualitatively discussed.