FT-IR and FT-Raman spectroscopy study of the cyclic anhydride intermediates for the esterification of cellulose: III. Cyclic anhydrides formed by the isomers of cyclohexanedicarboxylic acid

Multifunctional carboxylic acids have been used as crosslinking agents for cotton and wood pulp cellulose. In our previous research, we found that a polycarboxylic acid esterifies cellulose through the formation of a 5-membered cyclic anhydride intermediate by the dehydration of two carboxyl groups. In this research, we studied the formation of cyclic anhydride intermediates by different isomers of cyclohexanedicarboxylic acid (CHA) so that we can elucidate the effects of molecular structure on the formation of the anhydride intermediates. We found that both cis- and trans-1,2-CHA form 5-membered anhydride intermediates when temperature reaches their melting points and that cis-1,2-CHA forms the cyclic anhydride at temperatures lower than does trans-1,2-CHA. 1,3-CHA forms 6-membered cyclic anhydride at temperatures much higher than its melting point. The formation of a 5-membered cyclic anhydride intermediates takes place at temperatures lower than that of a 6-membered anhydride. This is probably the main reason why those polycarboxylic acids with their carboxylic acid groups bonded to the adjacent carbons of the molecular backbones are more effective crosslinking agents for cellulose than those with their carboxylic groups bonded to the alternative carbons. No formation of cyclic anhydride was found for 1,4-CHA. The formation of a five-membered cyclic anhydride was accelerated by monosodium phosphate, which is used as a catalyst for the esterification of cotton cellulose by polycarboxylic acids.