Micellization of monomeric and poly-ω-methacryloyloxyundecyltrimethylammonium surfactants

We have used small-angle neutron scattering to study how micelle morphology of the tail-polymerizable surfactants MUTAB and MUTAC (ω-methacryloyloxyundecyltrimethylammonium bromide and chloride) is affected by classic self-assembly modifiers such as temperature changes, salt addition, and counterion exchange, as a function of their conversion from monomer into polymer amphiphile in aqueous solution. Contrary to common assumptions about polymerized surfactants, these systems remain in dynamic equilibrium under all conditions examined and at all conversions (except for a small amount of high-molecular-weight precipitation by MUTAC). Counterintuitively, the polymerized methacrylate backbone has little influence on aggregate morphology, except for the formation of rod-like mixed micelles of polymerized and unpolymerized surfactant at intermediate conversions. The addition of salt produces a transition to rod-like micelles at all conversions except in the unpolymerized surfactant, which has some characteristics of an asymmetric bolaform surfactant and retains its spheroidal geometry under almost all conditions.