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Influence of the degree of substitution and substituent distribution on the equilibrium properties of carboxymethylcellulose in aqueous solution

Samples of carboxymethylcellulose were prepared by the heterogeneous reaction of the soda/anthraquinone pulp obtained from sugar cane bagasse. The less substituted samples (DS<1,0) and the more substituted ones (DS> 1,0) showed different behaviors concerning to: i) the dependence of pk ap on the degree of neutralization; ii) the agreement between DS values determined by titrations and by ¹H nmr spectroscopy and iii) the agreement between the experimental values of transport coefficients (f) and the ones calculated by applying the Manning theoretical approach. All samples showed a block distribution of substituents which, in the case of the less substituted samples, are short and well separated, favoring the occurrence of associative interactions and of aggregation. Electrostatic excluded volume effects, which are more important for the more substituted samples, inhibit the aggregation and may explain the behavior of these samples.

Carboxymethylcellulose; degree of substitution; acidity constant; transport coefficient


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