Entropic Mechanism for the Lower Critical Solution Temperature of Poly(ethylene oxide) in a Room Temperature Ionic...

Polymers exhibit interesting phase behavior in room temperature ionic liquids. For example poly(ethylene oxide) (PEO) displays a lower critical solution temperature (LCST) in [BMIM][BF₄] with a critical temperature and concentration that are only weakly dependent on molecular weight, contrary to the behavior of polymers in other solvents. To shed light on the mechanism of the LCST, we study the phase behavior of PEO in [BMIM][BF₄] using molecular dynamics (MD) simulations. The simulations show the signature of a phase transition as the temperature is increased. At low temperatures, interactions similar to a hydrogen bond are found between the imidazolium hydrogen and the PEO oxygen (HI-O H-bond) and the imidazolium hydrogen and the anion fluorines (HI-F H-bond). These interactions stabilize the mixed phase. A potential of mean force (PMF) analysis shows an entropic cost associated with the HI-O H-bond, which makes the bond formation unfavorable at higher temperatures, while the HI-F H-bond does not show a significant temperature dependence: This suggests that LCST phase separation is driven by the entropic penalty of the polymer for a PEO-cation hydrogen bond. We test the effect of scaling the charges on the [BMIM][BF₄]. Interestingly, the scaled charge force-field does not predict a phase separation at any temperature, thus, emphasizing the pitfalls of charge scaling for mixtures.