Activation of TEMPO by ClO2 for oxidation of cellulose by hypochlorite—Fundamental and practical aspects of the catalytic system

• Published in: Carbohydrate polymers 2017-10, Vol.174, p.524-530
• Main Authors: Pääkkönen, Timo, Pönni, Raili, Dou, Jinze, Nuopponen, Markus, Vuorinen, Tapani
• Format: Article
• Language: English
• Subjects: Birch pulp; Bromide-free; Carboxylates; Cellulose; ClO2 activated TEMPO-mediated oxidation; UV–vis spectrometry
• ISSN: 0144-8617; 1879-1344
• DOI: 10.1016/j.carbpol.2017.06.117

•TEMPO can be rapidly activated with ClO2 without bromide addition.•Oxidation of primary alcohols is not dependent on the activation method of TEMPO.•Oxidation of secondary alcohols can be avoided with exclusion of bromide. Bromide-free TEMPO-catalyzed oxidation of the primary alcohols by sodium hypochlorite (NaOCl) does not proceed without a prior activation of the catalyst. Here were demonstrate an immediate in situ activation of the catalyst with an equimolar addition of chlorine dioxide (ClO2) relative to TEMPO. Sodium bromide (NaBr) had a similar role in activating the catalyst although NaBr was needed in excess and the activation took several minutes depending on the dosage of NaBr. The activation method, or the concentration of NaBr, did not affect the bulk oxidation rate. The selectivity of the ClO2 initiated oxidation remained high up to NaOCl addition of 3mol/kg bleached birch kraft pulp after which additional loss in yield and depolymerization of cellulose were emphasized with negligible increase in carboxylate content. A carboxylate content of 0.8–1mol/kg, sufficient for easy mechanical fibrillation of the pulp, was achieved under mild conditions with NaOCl addition of 2-2.5mol/kg pulp.