Second-virial theory for shape-persistent living polymers templated by disks.

Abstract

Living polymers composed of noncovalently bonded building blocks with weak backbone flexibility may self-assemble into thermoresponsive lyotropic liquid crystals. We demonstrate that the reversible polymer assembly and phase behavior can be controlled by the addition of (nonadsorbing) rigid colloidal disks which act as an entropic reorienting "template" onto the supramolecular polymers. Using a particle-based second-virial theory that correlates the various entropies associated with the polymers and disks, we demonstrate that small fractions of discotic additives promote the formation of a polymer nematic phase. At larger disk concentrations, however, the phase is disrupted by collective disk alignment in favor of a discotic nematic fluid in which the polymers are dispersed antinematically. We show that the antinematic arrangement of the polymers generates a nonexponential molecular-weight distribution and stimulates the formation of oligomeric species. At sufficient concentrations the disks facilitate a liquid-liquid phase separation which can be brought into simultaneously coexistence with the two fractionated nematic phases, providing evidence for a four-fluid coexistence in reversible shape-dissimilar hard-core mixtures without cohesive interparticle forces. We stipulate the conditions under which such a phenomenon could be found in experiment.