Depolymerization of cellouronic acid during TEMPO-mediated oxidation

Abstract

The mechanism of partial depolymerization of cellouronic acid (β-1,4-linked polyglucuronic acid sodium salt) during 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation of cellulose was studied by treating cellouronic acid with one reagent or a combination of TEMPO-NaBr-NaClO under various conditions. Although NaClO, NaBrO and an alkali at pH 11 brought about partial depolymerization of cellouronic acid, the use of these reagents themselves did not seem to be the primary reason for depolymerization. On the other hand, when all the reagents, i.e. TEMPO-NaBr-NaClO, were applied to cellouronic acid at pH 11, a remarkable decrease in weight-average degree of polymerization (DPw) from 430 to ca. 20 was observed within the initial 10 min. Probably hydroxyl radicals formed from NaBrO and TEMPO at pH 10–11 cause the depolymerization during the oxidation. Some radical scavengers were then used for the TEMPO-mediated oxidation of cellulose in order to suppress the depolymerization. Although the addition of crotonic acid under certain conditions gave cellouronic acid having higher DPw, none of the radical scavengers examined so far could completely prevent the depolymerization. When regenerated celluloses having higher DP were used as the starting materials, cellouronic acids having DPw of more than 1000 were obtained, although they still had large low-molecular-weight fractions.