Mixed solvents for cellulose derivatization under homogeneous conditions: kinetic, spectroscopic, and theoretical studies on the acetylation of the biopolymer in binary mixtures of an ionic liquid and molecular solvents

Abstract

Rate constants for the acetylation of microcrystalline cellulose (MCC), by ethanoic anhydride in the presence of increasing concentrations of the ionic liquid (IL), 1-allyl-3-methylimidazolium chloride in dipolar aprotic solvents (DAS), N,N-dimethylacetamide (DMAC), and acetonitrile (MeCN), have been calculated from conductivity data. The third order rate constants showed a linear dependence on [IL]. We explain this result by assuming that the reacting cellulose is hydrogen-bonded to the IL. This is corroborated by kinetic data of the acetylation of cyclohexylmethanol, FTIR of the latter compound and of cellobiose in mixtures of IL/DAS, and conductivity of the binary solvent mixtures in absence, and presence of MCC. Cellulose acetylation is faster in IL/DMAC than in IL/MeCN; this difference is explained based on solvatochromic data (empirical polarity and basicity) and molecular dynamics simulations. Results of the latter indicate hydrogen-bond formation between the hydroxyl groups of the anhydroglucose unit of MCC, (Cl−) of the IL, and the dipole of the DMAC. Under identical experimental conditions, acetylation in IL/DMAC is faster than that in LiCl/DMAC (2.7–8 times), due to differences in the enthalpies and entropies of activation.