Carboxyalkylation of chitosan in the gel state

This study presents a new approach for direct carboxyalkylation of chitosan in the gel state by using aza-Michael addition and substitution reactions. Various reagents were applied including acrylic and crotonic acids, and α-, β-, γ-, δ-, and ɛ-halocarboxylic acids. The reaction of chitosan with γ- and δ-halocarboxylic acids showed no target product formation either in solution or in the gel state. In the case of acrylic, crotonic, α- and β-halocarboxylic acids, the reaction performed in the gel state (concentration of chitosan 20–40%) shows higher degree of substitution at lower reaction time and temperature than in diluted solutions (concentration of chitosan 0.5–2%). The results were discussed in terms of kinetics of the target and side reactions. 1H and 13C NMR confirmed that in all cases the carboxyalkylation of chitosan proceeds exclusively at the amino groups.