Biphasic liquid mixtures of ionic liquids and polyethylene glycols

We have found that 1-alkyl-3-methylimidazolium chloride ionic liquids (ILs) can form immiscible liquid mixtures with some polyethylene glycols (PEGs). Binary mixtures of 1-ethyl-3-methylimidazolium chloride with PEG of molecular weight 1500, 2000, or 3400 g mol(-1), or of 1-butyl-3-methylimidazolium chloride with PEG of molecular weight 2000 or 3400 g mol(-1), have been found to give rise to entirely liquid, stable biphasic systems over a significant temperature range (from 333.15 K to 413.15 K), while mixtures of 1-ethyl-3-methylimidazolium chloride with PEG-1000 and 1-butyl-3-methylimidazolium chloride with PEG-1000 and PEG-1500 are miscible. The mutual immiscibility of the IL and the PEG increases as the temperature increases. The evolution of the composition of the phases in equilibrium with the molecular weight of the PEG, or with the variation of the length of the alkyl substituent chain of the imidazolium cation of the IL, has been explored. The trends observed are explained through the complexity of interactions present within the binary system. A thermodynamic analysis of the liquid-liquid equilibrium data indicates negative values for the change of enthalpy and entropy of mixing. The potential application of these biphasic, entirely liquid systems, with low volatility and good solvation properties, for the dissolution and separation of cellulose and lignin at elevated temperature has been preliminarily explored, although only modest results have been achieved to date.