Influence of Charge Fraction on the Phase Behavior of Symmetric Single-Ion Conducting Diblock Copolymers.

A series of symmetric poly[(oligo(ethylene glycol) methyl ether methacrylate--oligo(ethylene glycol) propyl sodium sulfonate methacrylate)]--polystyrene (POEGMA-PS) diblock copolymers were synthesized as a model system to probe the effect of charge fraction on the phase behavior of charged-neutral single-ion conducting diblock copolymers. Small-angle X-ray scattering (SAXS) experiments showed that increasing the charge fraction does not alter the ordered phase morphology (lamellar) but increases the order-disorder transition temperature () significantly. Additionally, the effective Flory-Huggins interaction parameter (χ) was found to increase linearly with the charge fraction, similar to the case of conventional salt-doped diblock copolymers. This indicates that the effect of counterion solvation, attributed to the significant mismatch between the dielectric constant of each block, provides the dominant effect in tuning the phase behavior of this charged diblock copolymer. We therefore infer that electrostatic cohesion (local charge ordering induced by Coulombic interactions), which is predicted to suppress microphase separation and lead to asymmetric phase diagrams, only plays a minor role in this model system.