Polydisperse polymer fractionation between phases.

Polymer mixtures fractionate between phases depending on their molecular weight. Consequently, by varying solvent conditions, a polydisperse polymer sample can be separated between phases to achieve a particular molecular weight distribution in each phase. In principle, predictive physics-based theories can help guide separation design and interpret experimental phase-diagram and fractionation measurements. Even so, applying the standard Flory-Huggins model can require numerical computations that hamper the predictions considering the full molecular weight distribution. Here, we apply a recently derived exact analytical solution of multicomponent Flory-Huggins theory for polydisperse homopolymers to understand the principles of polymer fractionation for common molecular weight distributions. Consistent with previous studies, the method highlights the sensitivity of polymer fractionation to the shape, and in particular the tails, of this distribution. Our results provide a systematic approach to evaluate the full molecular weight distribution in phase coexistence calculations over the possible composition space.