Self-Assembly in a Polymer Matrix and Its Impact on Phase Separation

Molecular self-assembly often occurs in the presence of long chain polymers, and we develop a theory to describe the competition between self-assembly and phase separation that generally occurs in these complex fluid mixtures. The theory includes a description of the particularly interesting situation where the associating monomeric species form high molecular mass polymeric structures and where the assembly process transforms the phase boundary from a form typical of a polymer solution to one that more resembles a polymer blend. We consider both self-assembly upon cooling and upon heating, but the van der Waals interactions are chosen so that phase separation occurs only upon cooling in the absence of association. Systems that associate upon heating prove to be particularly rich, and closed loop and ordinary (upper solution critical) phase boundaries are found to coexist over a wide range of interaction parameter values. Each critical temperature in the limit of a large polymerization index for the matrix polymers approaches its respective theta temperature. The calculations elucidate basic physical principles governing the phase behavior of these complex mixtures.