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Perrin, J., Pouyet, F., Chirat, C., and Lachenal, D. (2014). "Formation of carbonyl and carboxyl groups on cellulosic pulps: Effect on alkali resistance," BioRes. 9(4), 7299-7310.


Ozone bleaching generates carbonyl groups on the cellulose polymer when applied to unbleached kraft pulps. This suggests that pulp fully bleached with a totally chlorine-free (TCF) sequence may contain more oxidized groups than standard elemental chlorine-free (ECF) bleached pulp. A fully bleached pulp was treated with sodium hypochlorite to form oxidized groups (mostly carbonyls) on the pure carbohydrates, which were investigated during subsequent alkaline treatment. Carbonyl groups had a strong impact on color development during alkaline treatment. Among the carbonyls, the keto groups were the most active. This was confirmed by the behavior of carbohydrate model compounds that contained aldehyde, keto, and/or carboxyl groups when subjected to alkaline conditions. A subsequent hydrogen peroxide (P) stage effectively decreased the carbonyl content, which reduced yellowing during alkaline treatment. However, the oxidized cellulose was severely depolymerized. The addition of magnesium sulfate (Mg) into the P stage minimized depolymerization while maintaining some of the carbonyls in the carbohydrates. It is proposed that Mg cations can hinder alkaline β-elimination, possibly by forming a complex with the carbonyl groups.
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