Comparative study of homogeneous solvents for the esterification crosslinking of cellulose with 1,2,3,4‐butanetetracarboxylic dianhydride and water absorbency of the reaction products

Superabsorbent hydrogels were prepared via esterification crosslinking of cellulose with 1,2,3,4‐butanetetracarboxylic dianhydride (BTCA) in three solvent systems: lithium chloride (LiCl)/N‐methyl‐2‐pyrrolidinone (NMP), LiCl/N,N‐dimethylacetamide (DMAc), and tetrabutylammonium fluoride/dimethyl sulfoxide (TBAF/DMSO). The absorbency of the hydrogels was strongly dependent on the BTCA feed to cellulose ratio as well as the nature of the solvent system used. The rate of cellulose esterification was enhanced in TBAF/DMSO relative to the other systems, and the highest water absorbency of the hydrogels (987 g g^?1 polymer) was also achieved using this system. The hydrogels obtained in the TBAF/DMSO system had a similar degree of both crosslinking and grafting, indicating that both reactions were promoted to the same extent in this solvent, whereas crosslinking was preferentially enhanced over grafting in the LiCl/NMP and LiCl/DMAc systems. The difference in the composition of the hydrogels was attributed to the difference in the electronegativity of the fluoride and chloride anions in these solvents. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013