Dielectric and mechanical relaxation processes in methyl acrylate/tri-ethyleneglycol dimethacrylate copolymer networks

The dielectric properties of methylacrylate (MA)/tri-ethyleneglycol dimethacrylate (TrEGDMA) copolymers at different compositions, ranging from 0 to 100, were measured between −120 and 150 °C over the frequency range 0.1 Hz–1 MHz. In the given frequency range, three relaxation processes were detected by dielectric relaxation spectroscopy in homo poly-TrEGDMA and copolymers: the α process associated with the glass transition, and two secondary processes due to localized mobility. In PMA only one secondary process was observed besides the alpha relaxation process. The influence of copolymerization going from PMA, monofunctional softer component with a glass transition determined calorimetrically as 284 K, to poly-TrEGDMA, higher glass transition component, bifunctional, that also forms a dense network due to cross linking, reflects mainly in the alpha process that shifts to higher temperatures and becomes broader. The raise and broadening in the glass transition with TrEGDMA increase was also observed by dynamic mechanical thermal analysis and differential scanning calorimetry. The glass transition temperature of poly-TrEGDMA was not detected calorimetrically but a value of 429 K was estimated from the best fit of the Fox equation. In what concerns the secondary relaxation process detected in poly-TrEGDMA and copolymers at the lowest temperatures, it is related with local twisting motions of ethyleneglycol moieties, being designated as γ relaxation, while the process detected in the medium temperature range is associated with the rotation of the carboxylic groups as in poly(alkyl methacrylates), designated as β relaxation. This process is detected at much lower temperatures in homo PMA in the same temperature region than the above mentioned γ relaxation. The copolymerization influences mainly the α process while the γ process remains almost unaffected in copolymers relative to homo poly-TrEGDMA. The β process is largely determined by the presence o the tri-ethylene glycol dimethacrylate monomeric units even in copolymers with the lowest TrEGDMA content.