Influence of a strong polyelectrolyte block on the formation and properties of polymer micelles with a mixed corona

Joint micellization of two amphiphilic diblock copolymers is studied by velocity sedimentation, transmission electron microscopy, electrophoretic mobility measurements, and static light scattering. One of the diblock copolymers is a strong polyelectrolyte (polystyrene-block-poly(N-ethyl-4-vinylpyridinium bromide)), while the second one is a weakly charged or uncharged copolymer (polystyrene-block-poly(acrylic acid) or polystyrene-block-poly(4-vinylpyridine)). It is shown that the mixing of the diblock copolymers in a selective aqueous-organic solvent (DMF-methanol-water) leads to the formation of joint (hybrid) micelles and that the composition of these micelles is close to the composition of the polymer mixture. Micelles consist of an insoluble polystyrene core and a mixed corona composed of blocks of a strong polyelectrolyte and a weakly charged or uncharged copolymer. Aqueous dispersions of mixed micelles are obtained with the use of the dialysis technique, the spherical morphology of the micelles is ascertained, and their three-layered structure is proposed. The nonlinear dependence of the molecular mass of micelles on their composition is found. The decisive effect of electrostatic repulsion between strong polyelectrolyte units on the thermodynamics of micellization and the dispersion stability and molecular-mass characteristics of the mixed micelles is demonstrated.