Segmental Dynamics in Multicyclic Polystyrenes

The segmental dynamics and the corresponding glass temperature, T-g, were investigated in a monocyclic and in the corresponding linear polystyrene as well as in a series of multicyclic polystyrenes, all with the same total molecular weight, with dielectric spectroscopy and DSC. There is a strong reduction of T-g with decreasing molecular weight for linear chains but only a moderate reduction for cyclic chains and this below a certain critical molecular weight (M-n similar to 18 000 g/mol). These data contradict the Gibbs-Di Marzio lattice model predicting an increasing glass temperature with decreasing molecular weight of cyclic polymers. In multicyclic polystyrenes the results emphasize the role of constrained segments at the coupling sites (linkers) on determining practically all features of segmental dynamics: the exact temperature dependence of relaxation times and associated T-g, the dielectric strength, the distribution of relaxation times, and fragility. A nearly linear increase of T-g was found with increasing number of intramolecular constraints. Furthermore, the total molecular weight is an irrelevant parameter in discussing the dynamics of multicyclic polymers. An alternative approach that is based on the concept of free volume emphasizes intermolecular contributions and predicts the same amount of fractional free volume for multicyclic polystyrenes at their respective glass temperature (3.3%) but differences in the respective thermal expansion coefficient of free volume.