Augmenting Polyzwitterion Permittivity via Block Polymer Self-Assembly

Polyzwitterions combine the attractive features of zwitterions (ZIs) with the mechanical support and processability of polymeric materials. Among these attractive features is a potential for superior permittivity, which is limited by the propensity of ZIs to pack into strongly associating assemblies. Block polymer (BP) self-assembly embodies a plethora of packing frustration opportunities for optimizing polyzwitterion permittivity. The capabilities of this novel approach are revealed here, where the static permittivity (ε s ) of a polyzwitterionic block is enhanced to a level comparable to that of pure liquid zwitterions near room temperature (ε s ∼ 250), but with less than a third of the ZI concentration. Structure–property mechanisms are realized deductively through a series of thermal processes and control sample experiments. Tethered ZIs within the mixed block interface are frustrated when subjected to segmental segregation under sufficient interfacial tension and packing, while noninterfacial zwitterions contribute very little to permittivity, highlighting the potential for improvement by several fold.