RESUMO
Commercial rayon grade cellulose was dissolved in the lithium chloride-N,N-dimethylacetamide (LiCl-DMAc) solvent system and esterified with acetic anhydride using p-toluenesulfonyl chloride (p-TsCl) and pyridine as catalysts. The reaction temperature was varied from 28 to 70 degrees C and the time of reaction from 2 to 24 h. Full substitution took place at 60 and 70 degrees C at respective reaction times of 10 and 8 h for p-TsCl, and 10 and 6 h for pyridine. Esterification of cellulose followed a second-order reaction path. The rate constants at different reaction temperatures and the activation energy for the reaction are reported. Mechanisms for these reactions using the two catalysts are also suggested. The degrees of substitution (DS) of the esters prepared using both catalysts show that pyridine is a better catalyst than p-TsCl. Molecular weights of the esters, determined viscosimetrically, show that some degradation in the cellulose chain occurred at a reaction temperature of 70 degrees C. Hence, the optimum temperature for esterification appears to be 50-60 degrees C at 10 h reaction time to obtain full degree of acetyl substitution.