Characterization of Non-Derivatized Cellulose Samples by Size Exclusion Chromatography in Tetrabutylammonium Fluoride/Dimethylsulfoxide (TBAF/DMSO).

This paper deals with the use of tetrabutylammonium fluoride/dimethylsulfoxide (TBAF/DMSO) to characterize the molar mass distribution of non-derivatized cellulosic samples by size exclusion chromatography (SEC). Different cellulose samples with various average degree of polymerization (DP) were first solubilized in this solvent system, with increasing TBAF rates, and then analyzed by SEC coupled to a refractive index detector (RID), using DMSO as mobile phase. The Molar Masses (MM) obtained by conventional calibration were then discussed and compared with suppliers' data and MM determined by viscosimetry measurements. By this non-classic method, molar mass of low DP samples (Avicel® and cotton fibers) have been determined. For high DP samples (α-cellulose and Vitacel®), dissolution with TBAF concentration of 10 mg/mL involved elution of cellulose aggregates in the exclusion volume, related to an incomplete dissolution or the dilution of TBAF molecules in elution solvent, preventing the correct evaluation of their molar mass.

Structural modifications of cellulose samples after dissolution into various solvent systems.

This work deals with the modifications resulting from the dissolution of four commercial cellulosic samples, with different crystallinity rates and degrees of polymerization (DPs), in four solvent systems, known and used to dissolve cellulose. The dissolution conditions were optimized for the 16 various systems and followed by turbidity measurements. After regeneration, the samples were analyzed by thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), and X-ray diffractometry (XRD) to study their modification. Viscosimetry measurements were used to evaluate the potential decrease of the DP after dissolution. The observed structural modifications established that, for low DP, all the solvent systems were efficient in dissolving the cellulose without altering the DP, except BMIM [Cl], which provoked a decrease of up to 40 % and a decrease of around 20 % of the degradation temperature (onset temperature, T o). For high molecular weight (MW) celluloses, DMSO/TBAF was the only system to allow a complete dissolution without any molar mass loss and degradation temperature modification.