Base-free trifluoroacetylation: From methyl glucopyranoside to cellulose nanofibers

Trifluoroacetic anhydride (TFAA) reacts smoothly with low molecular weight carbohydrates and cellulose nanofibers (CNFs) under base-free conditions. Methyl α- and β-d-glucopyranoside were used as model compounds to optimize reaction conditions, which were then applied to lyophilized CNFs for surface modification. ATR-IR spectroscopy and powder X-ray diffraction were employed to characterize the modified CNFs. Trifluoroacetylation for 4 h yields a degree of substitution (DS) of 0.4 acyl groups per anhydroglucose unit while maintaining a crystallinity index near 50 %. DS values were quantified by gravimetry, acid–base titration after saponification, and a novel approach utilizing solution 19F NMR spectroscopy which offers greater accuracy than the other techniques. This study presents an efficient, base-free method for derivatizing carbohydrates as well as surface functionalization of CNFs with trifluoroacetyl groups, potentially expanding their application in fiber-reinforced thermoplastic composites. [Display omitted] •Trifluoroacetylation of sugars and cellulose nanofibers (CNFs) without added base.•Complete characterization of methyl α-and β-glucopyransoide tetratrifluoroacetate.•Degree of substitution (DS) quantified by 19F NMR spectroscopy.•Retention of crystallinity in CNFs after several hours of treatment.