Coherent States Field Theory for Supramolecular Miktoarm Star Polymer Networks

The conformational asymmetry of AB_n mitoarm star polymers results in deflected phase boundaries that favor discrete A domains and non-conventional (Frank-Kasper) spherical packings. The stabilization of discrete A domains to extreme volume fractions offers potential for unique property combinations in dry and wet networks that utilize the AB_n motif. In this study, we explore the use of miktoarm stars as supramolecular building blocks to form reversible dry networks that retain the unique morphologies of non-reactive polymers, but with thermally tunable mechanical properties. To study such systems, we apply the coherent states (CS) field-theoretic representation in tandem with a mean-field approximation. The CS framework is highly advantaged over the conventional “auxiliary field” (AF) representation because it eliminates the need for explicit enumeration of all reaction products. We show how the phase behavior is influenced by the placement of reactive groups, their binding strength, and their self vs. hetero-complementary character. In particular, the relative stability of Frank-Kasper phases was explored and compared with non-reactive miktoarm stars.