Micellization of Sliding Polymer Surfactants

Following up a recent paper on grafted sliding polymer layers [Macromolecules 2005, 38, 1434−1441], we investigated the influence of the sliding degree of freedom on the self-assembly of sliding polymeric surfactants that can be obtained by complexation of polymers with cyclodextrins. In contrast to the micelles of quenched block copolymer surfactants, the free energy of micelles of sliding surfactants can exhibit two minima:  the first corresponding to small micelles with symmetric arm lengths and the second corresponding to large micelles with asymmetric arm lengths. The relative sizes and concentrations of small and large micelles in the solution depend on the molecular parameters of the system. The appearance of small micelles drastically reduces the kinetic barrier, allowing for the fast formation of equilibrium micelles.