Rheological Control of Aqueous Dispersions by Thermoresponsive BAB* Copolymers of Different Architectures

Temperature control of rheological properties of aqueous solutions can be achieved by the addition of amphiphilic polymers that show temperature-dependent self-assembly. For this purpose, we explored three sets of acrylamide-based block copolymers with BAB*-, B2AB*-, and B(AB*)2-type architectures, where “B” represents a permanently hydrophobic unit, “A” is a permanently hydrophilic block, and “B*” is a thermoswitchable block, which undergoes a phase transition of the lower critical solution temperature (LCST) type. Depending on the specific polymer architecture and choice of the thermoresponsive block, the viscosity of their aqueous solutions can augment substantially with increasing temperature. The macroscopic rheological changes were correlated with the results of static and dynamic light scattering (SLS, DLS) and small-angle neutron scattering (SANS) experiments, showing a clear correlation with the mesoscopic organization of the respective systems. Complementary studies with the fluorescence probe Prodan also revealed a clear correlation of the enhanced viscosity to the formation of hydrophobic domains of the thermoresponsive block. Accordingly, the appropriate design of such “smart” copolymer thickeners enables the tuning of the viscoelastic properties of aqueous solutions.