Pressure-induced formation of diblock copolymer “micelles” in supercritical fluids. A combined study by small angle scattering experiments and mean-field theory. I. The critical micellization density concept

We developed a simple mean-field theory to describe polymer and AB diblock copolymer phase separation in supercritical (SC) fluids. The highly compressible SC fluid has been described by using a phenomenological hole theory, properly extended to consider the solvent/polymer/vacancy pseudoternary mixture. The model has been applied to describe the phase behavior of AB-diblock copolymers under the assumption of a strong solvent selectivity for just one copolymer chain. In our model the solvent selectivity is a strong function of the external pressure because in compressible fluids vacancies reduce the number of favorable solvent-polymer contacts. The combined effect of the pressure on the average solvent quality and selectivity for a single polymer chain makes the phase behavior of a diblock copolymer in SC fluids quite complex. Small angle neutron and x-ray scattering (SANS and SAXS) measurements have been performed on SC-CO2 solutions of different AB-diblock copolymers containing a perfluorinated chain. The data obtained over a wide range of pressure and temperature confirm our theoretical predictions.