Self-assembly of amphiphilic di and triblock copolymers of styrene and quaternized 5-(N,N-diethylamino) isoprene in selective solvents

Self-association of highly asymmetric block copolymers of styrene and quaternized 5-(N,N-diethylamino)isoprene was studied. After quaternization with dimethyl sulfate, the di and triblock copolymers consisted of a long block of polystyrene (PS) with a short poly[5-(N,N,N-diethylmethylammonium)isoprene][methyl sulfate](PAI) block at one or both chain ends, respectively. The aggregates were prepared by first dissolving the copolymers in an organic solvent and then adding water to induce the segregation of the PS chains. Pure DMF, THF or dioxane was used as the organic solvent, as well as DMF/THF mixtures. The critical water content (cwc) and the morphologies were studied as a function of the common solvent, initial copolymer concentration and architecture (di or triblock) by static light scattering and by Transmission Electron Microscopy (TEM), respectively. It was found that both, the cwc and the morphologies of the aggregates are most strongly affected by the nature of the common solvent. Some unexpected behaviors were found for the triblock copolymer. Morphologies of a triblock copolymer in various mixtures of DMF and THF, quenched at determined water contents, were investigated in order to study the degree of morphological control that can be achieved solely as function of the organic solvent composition. Multiple morphologies have been found including equilibrium morphologies and kinetically trapped ones. Finally, the stability of primary micelles prepared in DMF was studied by DLS, upon dilution with DMF and water, and a possible mechanism for the destabilization of the aggregates is proposed.