Abstract
A general kinetic model for the substitution of cellulose was developed. The model assesses the differences in the reactivity of the cellulose hydroxyl groups and a decrease in the reactivity as the substitution proceeds. The model predicts the detailed distribution of the different mono (2, 3, 6)-, di (23, 26, 36) – and trisubstituted (236) units as a function of the reaction time. The classical Spurlin distribution is obtained as a special case of the general model. Numerical strategies were developed for the solution and computer simulation of the model. Simulation results were shown to be valid for various reactivity ratios of the hydroxyl groups. The modelling concept was verified with experimental data obtained for carboxymethylation of cellulose in a slurry reactor. The detailed data, which revealed the non-uniform reactivities of the different hydroxyl groups and the decline of the substitution rate with time, were successfully described by the mathematical model.
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