Dielectric relaxation of polystyrene with side-chain- and chain-end-labels

Polystyrenes with different concentrations of side groups with cyano groups were prepared and complex dielectric constants were measured in the range of the glass transition temperature and the frequency range of 10^–2–10⁷ Hz.The GPC and DSC measurements showed that the molecular weight of these polystyrenes was about 10500 g/mole and the glass transition temperatures were 89.5°C for all samples.The dielectric relaxation spectra obtained for the side group polystyrene labels and also the chain-end polystyrene labels prepared before 9] were analyzed to find out the degree of coupling of the chain-end and side-group labels with the cooperative reorientation of the polymeric matrix. The analysis of the spectra was carried out using the analysis method developed by Mansour and Stoll 6].The results obtained showed that both end- and side-group labels are strongly coupled with the segmental reorientation and relax with relaxation times longer than that of the segments.The value of logf _m = (logf _m(label)) – logf _m(matrix)) was obtained from the recently designed comparison diagram suggested by Mansour and Stoll 6, 14]. The value of logf _m depends on the label length in the case of chain-end labels.It was surprising to find that the side groups relax slower than the segments by only 0.9 decades. These results obtained implied that the label relaxes through a multistep relaxation mechanism of the side and end groups and not through a diffusion mechanism of the whole chain. In addition, the effective lengths of the relaxing units were determined using the empirical equation obtained before in the case of rodlike molecules in polyisoprene 7].