Cellulose Dissolution in Mixtures of Ionic Liquids and Dimethyl Sulfoxide: A Quantitative Assessment of the Relative Importance of Temperature and Composition of the Binary Solvent.

We studied the dissolution of microcrystalline cellulose (MCC) in binary mixtures of dimethyl sulfoxide (DMSO) and the ionic liquids: allylbenzyldimethylammonium acetate; 1-(2-methoxyethyl)-3-methylimidazolium acetate; 1,8-diazabicyclo [5.4.0]undec-7-ene-8-ium acetate; tetramethylguanidinium acetate. Using chemometrics, we determined the dependence of the mass fraction (in %) of dissolved cellulose (MCC-m%) on the temperature, T = 40, 60, and 80 °C, and the mole fraction of DMSO, χDMSO = 0.4, 0.6, and 0.8. We derived equations that quantified the dependence of MCC-m% on T and χDMSO. Cellulose dissolution increased as a function of increasing both variables; the contribution of χDMSO was larger than that of T in some cases. Solvent empirical polarity was qualitatively employed to rationalize the cellulose dissolution efficiency of the solvent. Using the solvatochromic probe 2,6-dichloro-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (WB), we calculated the empirical polarity ET(WB) of cellobiose (a model for MCC) in ionic liquid (IL)-DMSO mixtures. The ET(WB) correlated perfectly with T (fixed χDMSO) and with χDMSO (fixed T). These results show that there is ground for using medium empirical polarity to assess cellulose dissolution efficiency. We calculated values of MCC-m% under conditions other than those employed to generate the statistical model and determined the corresponding MCC-m% experimentally. The excellent agreement between both values shows the robustness of the statistical model and the usefulness of our approach to predict cellulose dissolution, thus saving time, labor, and material.