Phase Behavior of Double Zwitterionic Block Copolymers in Water: Morphology Transition through Concentration Dependent Selectivity of Water Partitioning

Phase behavior of double zwitterionic diblock copolymers composed of a poly(carboxybetaine methacrylate) (PCB2) and a poly(sulfobetaine methacrylate) (PSB4) (PCB2n‐b‐PSB4m) has been mapped out in aqueous solutions. Phase diagrams are constructed with polymer concentration, ϕ, ranging from 0.08 to 0.80 and PSB4 volume fraction in the PCB2n‐b‐PSB4ms, fPSB4, ranging from 0.23 to 0.93 at 25 °C. PCB2n‐b‐PSB4m aqueous solutions show symmetric phase diagram above ϕ = 0.55, indicating that water is nearly neutral with respect to PCB2 and PSB4. The morphology transforms from columnar with PCB2 cylinders to lamellar to columnar with PSB4 cylinders with decreasing ϕ, and the phase boundaries exhibit a negative slope below ϕ = 0.45. The morphology transition is rationalized in terms of interfacial curvature modulation through the volume expansion of the PCB2 phase due to the selective water partitioning. The lyotropic mesophase of double hydrophilic block copolymers is a unique molecular compartment for hydrophilic molecules with low interfacial tension. Aqueous solutions of double zwitterionic diblock copolymers composed of a poly(carboxybetaine methacrylate) and a poly(sulfobetaine methacrylate) exhibit unique phase behavior depending on the composition and concentration. The morphology transforms depending on the polymer concentration below the threshold due to the selective partitioning of water to exhibit phase boundaries with negative slope in the phase diagrams.