Influence of counterions on the thermal and solution properties of strong polyelectrolytes

Strong polyelectrolytes (i.e., macromolecules whose charge density is independent of the medium's pH) are invaluable assets in the soft matter toolbox, as they can readily disperse in aqueous media, complex to oppositely charged species - polymers and small molecules alike - and can be implemented in a plethora of applications, ranging from surface modification to chelating agents and lubricants. However, the direct synthesis of strong polyelectrolytes in a controlled fashion remains a challenging endeavour, and their in-depth characterisation is often limited. Additionally, producing a set of charged macromolecules with the same chain length but varying counterions would open doors towards a fine control of the polymer's chemistry and physical properties. Unfortunately, this either necessitates the direct polymerisation of several monomers with potentially varying reactivities, or a time-consuming ion exchange from a single batch. Herein we explore the facile and efficient production of strong polyanions through the deprotection of a poly(3-isobutoxysulphopropyl methacrylate) using a range of inorganic and organic iodide-containing salts. Owing to the contrasting nature of their counterions, the resulting polyanions exhibit a wide range of glass transition temperatures, which follow a non-monotonic trend with increasing counterion size. While all polymers readily dissolve in water, some can also be dissolved in non-aqueous media as well. This strategy, applied to block copolymers, permits the production of a library of amphiphilic macromolecules with consistent hydrophilic and hydrophobic blocks, yet varying nature of their polyanionic segments. All amphiphiles, regardless of their counterions, readily disperse in aqueous media and form well-defined micelles featuring a hydrophobic core and a charged hydrophilic shell, as evidenced by dynamic light scattering, ζ-potential and transmission electron microscopy. Additionally, a handful of block copolymers are capable of yielding polymer micelles in organic solvents, opening an avenue to the build-up of nanostructured soft matter in non-aqueous media.