Microphase Separation and Ionic Aggregation in Oppositely Charged End-Functionalized Polymer Blends

Abstract

We study the phase behavior of binary blends of polymers with oppositely charged termini using an ion-correlation-augmented self-consistent field theory (IC-SCFT). Under the low dielectric conditions typical for organic polymer melts, strong ion correlations drive association of multiple chain ends, leading to emergent multichain architectures that go beyond a simple ion-paired diblock copolymer picture previously used to interpret recent experiments. At moderate to strong polymer segregation, the resulting phase diagram differs considerably from this effective-diblock prediction: ion clustering broadens the lamellar and cylindrical windows while suppressing the network phases, the reverse of the trend for end-charged diblock copolymers. At weak segregation, the two polymers remain miscible even as ion clustering persists, and decreasing chain length drives the clusters themselves through a sphere-to-cylinder-to-lamella shape transition, connecting continuously to the aggregation behavior of classical terminally charged ionomers in the limit when one of the polymer species shrinks to just the charged end. These results reveal that ion clustering -- beyond simple pairwise bonding -- shapes the self-assembly of end-charged polymer blends.