Assemblies of BAB triblock copolymers are prepared by PISA via aqueous RAFT dispersion polymerization. The importance of charges in the middle of the hydrophilic stabilizer loops is highlighted.

BAB triblock copolymers prepared by PISA in water self-assemble into a transient network of bridged micelles. The slowdown of the exchange of B blocks between micelles during PISA is highlighted as well as the parameters affecting the polymerization.

The incorporation of neutral hydrophilic monomer units in the hydrophobic B blocks of BAB copolymers produces transient networks exhibiting a thermoresponsive behavior with a maximum of viscosity in water.