Viscoelastic Properties of Unentangled Multicyclic Polystyrenes

We report on the viscoelastic properties of linear, monocyclic, and multicyclic polystyrenes with the same low molecular weight. All polymers investigated were found to exhibit unentangled dynamics. For monocyclic polymers without inner loops, a cyclic-Rouse model complemented by the contribution of unlinked chains (whose fraction was determined experimentally) captured the observed rheological response. On the other hand, multicyclic polymers with inner loops were shown to follow a hierarchical cyclic-Rouse relaxation with the outer loops relaxing first, followed by the inner loop relaxation. The influence of unlinked linear chains was less significant in multicyclic polymers with inner loops. The isofrictional zero-shear viscosity decreased with increasing number of constrained segments on the coupling sites, which was attributed to the decreasing loop size and the dilution effect due to the hierarchical relaxation.