How to Predict the Order of Phase Separation of Polyelectrolyte Complexes and Their Miscibility.

Abstract

The mixture of two oppositely charged polyelectrolyte solutions results in complexation that may lead to an associative phase separation, forming a highly concentrated phase in both polyelectrolytes in equilibrium with a dilute phase. In this work, we aim to investigate what controls the order of complexation when more polyelectrolytes of the same charge are present. For this, the effect of the addition of a third oppositely charged polyelectrolyte in a mixture of two polyelectrolytes with the same charge was studied. Our results show that, under certain conditions, the electrostatic complexation takes place selectively, where one polyanion (or polycation) phase separates first, followed by the other phase separation, with both complexes at their 1:1 charge stoichiometry. Infrared analyses of the phase-separated complexes confirmed that, in a mixture of polyanions, poly(styrenesulfonate) is complexed first, followed by poly(acrylate). For polycations, these analyses showed that poly(diallyldimethylammonium) is preferentially complexed over poly(allylamine). These results suggest that electrostatic complexation occurs following the sequence predicted as in an acid/base titration, where the acidic/basic strength of the involved polyions dictates which one is complexed first. In this respect, the order of complexation can be associated with the equivalence pH for each pair, which we propose can be used as a parameter to predict phase separation in polyelectrolyte mixtures. In addition, we have investigated the miscibility of these complex mixtures, confirming that multiphasic complexes are formed whenever the polyions display ionizable groups with different acid/basic strengths and that this can also be related to their equivalence pH.