Partial degrees of substitution in cellulose nitrates determined by means of 13C magnetic resonance studies

High resolution ¹³C n.m.r. proton noise decoupled (75.5 MHz) spectra have been recorded for a series of nitrated celluloses and denitrated cellulose nitrates. From the detailed spectral assignments an analysis of the partial degrees of substitution and distribution of nitrate groups in the β-D-glucopyranose residues is presented. The data are compared with the predictions of a model based on the constancy of ratio of three equilibrium constants for nitration—denitration at the C2, C3 and C6 positions for differently substituted β-D-glucopyranose residues and it is shown that the situation is considerably more complex than provided for by the model. Analysis of the anomeric ¹³C carbon region produces some sequence information which indicates non-random distribution of nitrate ester groups.