Abstract
The kinetics of the TEMPO-mediated oxidation of regenerated celluloses has been studied. It is revealed that the oxidation reaction of the regenerated celluloses by the 2,2,6,6-tetramethyl-piperidine-1-oxyl radical (TEMPO)–NaBr–NaOCl system can be approximately described by first-order kinetics with respect to substrate. In the concentration range used the rate constant k is directly proportional to the concentration of TEMPO, while it is proportional to the concentration of NaBr in a relatively lower range and tends to level off at higher concentration. The effect of temperature on the rate constant can be well described by the Arrhenius equation, the apparent activation energy measured is about 66.2 kJ/mol. The effect of the pH of the reaction solution, the crystallinity and morphology of the substrates on the oxidation rate is also discussed.
Similar content being viewed by others
References
P.S. Chang J.F. Robyt (1996) ArticleTitleOxidation of primary alcohol groups of naturally occurring polysaccharides with 2,2,6,6-tetramethyl-1-piperidine oxoammonium ion J. Carbohydr. Chem. 15 819–830
P.S. Chang J.F. Robyt (1998) ArticleTitleOxidation of the primary alcohol groups of cyclomaltodextrins with 2,2,6,6-tetramethyl-1-piperidine oxoammonium ion Carbohydr. Lett. 3 31–38
A.E. De Nooy A.C. Besemer H. van Bekkum (1994) ArticleTitleHighly selective TEMPO-mediated oxidation of primary alcohol groups in polysaccharides Recl. Trav. Chim. Pays-Bas 113 165–166
A.E. De Nooy A.C. Besemer H. van Bekkum (1995a) ArticleTitleHighly selective nitroxyl radical-mediated oxidation of primary alcohol groups in water-soluble glucans Carbohydr. Res. 269 89–98
A.E. De Nooy A.C. Besemer H. van Bekkum (1995b) ArticleTitleSelective oxidation of primary alcohols mediated by nitroxyl radical in aqueous solution. Kinetics and mechanism Tetrahedron 51 8023–8032
A.E. De Nooy A.C. Besemer H. van Bekkum J.A.P.P. van Dijk J.A.M. Smit (1996) ArticleTitleTEMPO-mediated oxidation of pullulan and influence of ionic strength and linear charge density on the dimensions of the obtained polyelectrolyte chains Macromolecules 29 6541–6547
L. Farkas M. Lewin R. Bloch (1949) ArticleTitleThe reaction between hypochlorite and bromides J. Am. Chem. Soc. 71 1988–1991
B.I. Friedlander A.S. Dutt W.H. Rapson (1966) ArticleTitleThe infrared spectra of oxidized cellulosepart III, sodium hypochlorite oxidation Tappi 49 IssueID10 468–472
M. Ibert F. Marsais N. Merbouh et al. (2002) ArticleTitleDetermination of the side-products formed during the nitro-mediated bleach oxidation of glucose to glucaric acid Carbohydr. Res. 337 1059–1063
A. Isogai Y. Kato (1998) ArticleTitlePreparation of polyuronic acid from cellulose by TEMPO-mediated oxidation Cellulose 5 153–164
J. Lenz J. Schurz E. Wrentachur (1993) ArticleTitleProperties and structure of solvent-spun and viscose-type fibers in the swollen state Colloid Polym. Sci. 271 IssueID5 460–468
Y. Kato R. Matsuo A. Isogai (2003) ArticleTitleOxidation process of water-soluble starch in TEMPO-mediated system Carbohydr. Polym. 51 69–75
K. Kumar D.W. Margerum (1987) ArticleTitleKinetics and mechanism of general-acid-assisted oxidation of bromide by hypochlorite and hypochlorous acid Inorg. Chem. 26 2706–2711
T.P. Nevell (1951) ArticleTitleOxidation of cotton cellulose by nitrogen dioxide J. Textile Inst. 42 T91–T129
T.J. Painter (1977) ArticleTitlePreparation and periodate oxidation of C-6-oxycellulose: conformational interpretation of hemiacetal stability Carbohydr. Res. 55 95–103
T.J. Painter (1985) ArticleTitleNew glucuronoglucans obtained by oxidation of amylose at position 6 Carbohydr. Res. 140 61–68
K. Rahn T. Heinze (1998) ArticleTitleNew cellulosic polymers by subsequent modification of 2,3-dialdehyde cellulose Cell. Chem. Technol. 32 173–183
I. Shibata A. Isogai (2003) ArticleTitleDepolymerization of celluronic acid during TEMPO-mediated oxidation Cellulose 10 151–158
C. Tahiri M.R. Vignon (2000) ArticleTitleTEMPO-oxidation of cellulose: synthesis and characterization of polyglucuronans Cellulose 7 177–188
C.C. Unruh W.O. Kenyon (1942) ArticleTitleInvestigation of the properties of cellulose oxidized by nitrogen dioxide J. Am. Chem. Soc. 64 127–131
A.J. Varma V.B. Chavan (1995) ArticleTitleSome preliminary studies on polyelectrolyte and rheological properties of sodium 2,3-dicarboxy-cellulose Carbohydr. Polym. 27 63–67
E.C. Yackel W.O. Kenyon (1942) ArticleTitleOxidation of cellulose by nitrogen dioxide J. Am. Chem. Soc. 64 121–127
M. Yalpani (1985) ArticleTitleA survey of recent advances in selective chemical and enzymic polysaccharide modifications Tetrahedron 41 2957–3020
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Sun, B., Gu, C., Ma, J. et al. Kinetic study on TEMPO-mediated selective oxidation of regenerated cellulose. Cellulose 12, 59–66 (2005). https://doi.org/10.1007/s10570-004-0343-4
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/s10570-004-0343-4