We examine the role of molecular architecture on the phase diagram of the PS/PVME (poly[styrenel /poly[vinyl methyl ether]) blend, a mixture which in previous studies with linear chains exhibited a lower critical solution temperature, (LCST) i.e. it phase separated on heating. In this investigation, two blends with components exceeding the critical molecular weight for entanglement were compared: one consisting of linear PS and PVME and a second with cyclic PS and linear PVME. Cloud point experiments over a broad composition range reveal that the blend containing cyclic PS undergoes phase separation at temperatures 7-8 °C higher than the analogous linear blend. In other words, the mixture of cycles and linear chains is more thermodynamically stable than the mixture of two linear chains.
The LCST nature of the system facilitates examining chain mobility by considering the phase separation kinetics. Time-resolved light scattering studies of blends near their critical compositions tracked the spinodal decomposition following a rapid temperature jump from the one-phase to the two-phase region. An analysis of the scattering intensity growth ultimately led to mutual diffusion coefficients whose temperature dependence confirmed the observed cloud points. An approximation of the second derivative of the free energy function based on SANS studies of the linear PS/PVME blend allowed us to estimate mutual mobilities. The values determined for the cycle-containing blend were considerably lower than those for the blend of linear chains at these molecular weights.