Morphological Transitions in Solutions of Macromolecules with Solvophilic Backbone and Orientationally Mobile Solvophobic Side Groups

A theoretical model describing the self-assembly in dilute solutions of amphiphilic macromolecules containing the backbone built of the solvophilic units (the P groups) and the solvophobic side chains (the H groups) possessing orientational mobility relative to the backbone units has been elaborated. In the framework of strong segregation limit (The size of the insoluble regions of the formed micelles is on the order of the hydrophobic side chains), state diagrams of the solution have been calculated with and without accounting for the orientational entropy contribution of the side groups to the total free energy of the solution at different thermodynamic qualities of solvent for the macromolecules and the grafting density of the H groups; the regions of stability of spherical and cylindrical micelles as well as planar bilayers (vesicles) have been revealed. It has been found that the contribution of the orientational entropy significantly affects the view of the state diagrams. In the case of considering the orientational mobility, the conditions of the cylindrical micelle stability are very sensitive to the change in the grafting density of the side groups. This sensitivity can be the reason why the formation of long cylindrical (wormlike) micelles is not observed in experiments and computer simulations. As earlier demonstrated at a qualitative level, the orientational mobility of the side groups can lead to the emergence of the orientation-induced attraction between the polymer micelles (A. I. Buglakov, D. E. Larin, and V. V. Vasilevskaya, Polymer 232, 124160 (2021)). In this study, exact analytical calculations of the energy of orientation-induced attraction for the case of the interaction between two planar bilayer micelles has been performed. At distances being of the order of the size of the side H group, the orientation-induced attraction forces are much stronger than the van der Waals forces and, hence, the orientation-induced attraction can be decisive in the formation of large aggregates observed in experiments.