Efficient Homogeneous TEMPO-mediated Oxidation of Cellulose  in Lithium Bromide Hydrates

Abstract An appropriate cellulose-dissolving solvent is critical for the homogeneous oxidation of cellulose using TEMPO (2, 2, 6, 6-tetramethylpiperidine-1-oxyl)-mediated system. Herein, TEMPO/NaClO/NaClO2 system in lithium bromide hydrates (LBHs) was developed for the homogeneous selective-oxidation of cellulose, which was two-stage protocol involving cellulose dissolution and homogeneous oxidation. Specifically, cellulose was firstly dissolved in LiBr⋅3.5H2O and offered the optimal pH (5.6) for the subsequent TEMPO/NaClO/NaClO2 oxidation without precipitation of the cellulose chains. Effect of reaction conditions on cellulose oxidation was investigated. The results showed that high degree of oxidation (DO) and evenly distributed carboxyl could be achieved. The particle size gradually decreased with DO, and oxidized cellulose with high water solubility and amorphous structure could be obtained. Furthermore, FT-IR, 13C NMR and fractionation analysis verified that cellulose was successfully converted and the carboxyl uniformly distributed onto the cellulose chains. This TEMPO-mediated system using LBHs as solvent presented an efficient method on the homogeneous selective oxidation of primary hydroxyl in cellulose.