Supramolecular association of a triblock copolymer in water

Solutions of a poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) triblock copolymer, Pluronic F68, were investigated in isothermal and isopleth mode. Surface tension, σ, dynamic shear viscosity, η(ω), QELS experiments, and volumetric, colligative, and refractive index measurements characterize the system behavior in a wide range of compositions and temperatures. The thermodynamic properties associated with micelle formation, above the critical micellar temperature, were determined by different experimental methods. The large entropic contributions to the system stability are ascribed to significant dehydration of the oxypropylene portion in the copolymer, consequent to micelle formation. Temperature has a pronounced effect on the association features of F68. It gives rise to abrupt changes in QELS and rheological properties when the critical micellar temperature is approached. Such effects are explained in terms of thermally driven micellization processes and interconnection between micelles. © 2004 Published by Elsevier Inc.