Skip to main content

Official Journal of the Japan Wood Research Society

  • Original Article
  • Published:

Oxidation of bleached wood pulp by TEMPO/NaClO/NaClO2 system: effect of the oxidation conditions on carboxylate content and degree of polymerization

Abstract

Oxidation of bleached wood pulp by the TEMPO/NaClO/NaClO2 system was carried out at pH 3.5–6.8 and 25°–60°C with different amounts of NaClO, and investigated in terms of effects of the reaction conditions on carboxylate content and degree of polymerization (DP) of the oxidized pulp. Oxidation was accelerated by the addition of NaClO, when carried out at pH 6.8 and 40°–60°C. Addition of NaClO of more than 0.5 mmol per gram of the pulp was effective to accelerate the oxidation. Carboxylate content of pulp oxidized under such conditions increased to approximately 0.6 mmol/g within 6 h. Although DP of the oxidized pulp gradually decreased with oxidation time, no significant differences in DP of oxidized pulps were found at oxidation temperatures between 25° and 60°C, and DP values of more than 900 were maintained after oxidation for 54 h at 60°C.

References

  1. Heinze T (1998) New ionic polymers by cellulose functionalization. Macromol Chem Phys 199:2341–2364

    Article  CAS  Google Scholar 

  2. Yackel EC, Kenyon WO (1942) The oxidation of cellulose by nitrogen dioxide. J Am Chem Soc 64:121–127

    Article  CAS  Google Scholar 

  3. Painter TJ (1977) Preparation and periodate oxidation of C-6-oxycellulose: conformational interpretation of hemiacetal stability. Carbohydr Res 55:95–103

    Article  CAS  Google Scholar 

  4. Jackson EL, Hudson CS (1937) Application of the cleavage type of oxidation by periodic acid to starch and cellulose. J Am Chem Soc 59:2049–2050

    Article  CAS  Google Scholar 

  5. Kim UJ, Kuga S, Wada M, Okano T, Kondo T (2000) Periodate oxidation of crystalline cellulose. Biomacromolecules 1:488–492

    Article  CAS  PubMed  Google Scholar 

  6. Lewin M (1997) Oxidation and aging of cellulose. Macromol Symp 118:715–724

    CAS  Google Scholar 

  7. Varela O (2003) Oxidative reactions and degradations of sugars and polysaccharides. Adv Carbohydr Chem Biochem 58:307–369

    Article  CAS  PubMed  Google Scholar 

  8. Nevell TP (1951) Oxidation of cotton cellulose by nitrogen dioxide. J Textile Inst 42:T91–T129

    CAS  Google Scholar 

  9. Head FSH, Hughes G (1954) The oxidation of cellobiose by periodate. J Chem Soc 603–606

  10. Isogai A, Kato Y (1998) Preparation of polyuronic acid from cellulose by TEMPO-mediated oxidation. Cellulose 5:153–164

    Article  CAS  Google Scholar 

  11. Tahiri C, Vignon M (2000) TEMPO-oxidation of cellulose: synthesis and characterisation of polyglucuronans. Cellulose 7:177–188

    Article  CAS  Google Scholar 

  12. Kitaoka T, Isogai A, Onabe F (1999) Chemical modification of pulp fibers by TEMPO-mediated oxidation. Nordic Pulp Paper Res J 14:274–279

    Article  Google Scholar 

  13. de Nooy AEJ, Besemer AC, van Bekkum H (1995) Highly selective nitroxyl radical-mediated oxidation of primary alcohol groups in water-soluble glucans. Carbohydr Res 269:89–98

    Article  Google Scholar 

  14. Anelli PL, Biffi C, Montanari F, Quiciet SJ (1987) Fast and selective oxidation of primary alcohols to aldehydes or to carboxylic acids and of secondary alcohols to ketones mediated by oxoammonium salts under two-phase conditions. J Org Chem 52:2559–2562

    Article  Google Scholar 

  15. Saito T, Isogai A (2004) TEMPO-mediated oxidation of native cellulose. The effect of oxidation conditions on chemical and crystal structures of the water-insoluble fractions. Biomacromolecules 5:1983–1989

    Article  CAS  PubMed  Google Scholar 

  16. Saito T, Shibata I, Isogai A, Suguri N, Sumikawa N (2005) Distribution of carboxylate groups introduced into cotton linters by the TEMPO-mediated oxidation. Carbohydr Polym 61:414–419

    Article  CAS  Google Scholar 

  17. Saito T, Okita Y, Nge TT, Sugiyama J, Isogai A (2006) TEMPO-mediated oxidation of native cellulose. Microscopic analysis of fibrous fractions in the oxidized products. Carbohydr Polym 65:435–440

    Article  CAS  Google Scholar 

  18. Montanari S, Roumani M, Heux L, Vignon M (2005) Topochemistry of carboxylated cellulose nanocrystals resulting from TEMPO-mediated oxidation. Macromolecules 38:1665–1671

    Article  CAS  Google Scholar 

  19. Saito T, Isogai A (2005) Novel method to improve wet strength of paper. Tappi J 4:3–8

    CAS  Google Scholar 

  20. Saito T, Isogai A (2006) Introduction of aldehyde groups on surfaces of native cellulose fibers by TEMPO-mediated oxidation. Colloids Surfaces A 289:219–225

    Article  CAS  Google Scholar 

  21. Saito T, Isogai A (2007) Wet strength improvement of TEMPO-oxidized cellulose sheets prepared with cationic polymers. Ind Eng Chem Res 46:773–780

    Article  CAS  Google Scholar 

  22. Saito T, Isogai A (2007) Ion-exchange behavior of carboxylate groups in fibrous cellulose oxidized by the TEMPO-mediated system. Carbohydr Polym 61:183–190

    Article  CAS  Google Scholar 

  23. Saito T, Nishiyama Y, Putaux JL, Vignon M, Isogai A (2006) Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose. Biomacromolecules 7:1687–1691

    Article  CAS  PubMed  Google Scholar 

  24. Saito T, Kimura S, Nishiyama Y, Isogai A (2007) Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules 8:2485–2491

    Article  CAS  PubMed  Google Scholar 

  25. Fukuzumi H, Saito T, Iwata T, Kumamoto Y, Isogai A (2009) Transparent and high gas barrier films of cellulose nanofibers prepared by TEMPO-mediated oxidation. Biomacromolecules 10:162–165

    Article  CAS  PubMed  Google Scholar 

  26. Shibata I, Yanagisawa M, Saito T, Isogai A (2006) SEC-MALS analysis of cellouronic acid prepared from regenerated cellulose by TEMPO-mediated oxidation. Cellulose 13:73–80

    Article  CAS  Google Scholar 

  27. Isogai T, Yanagisawa M, Isogai A (2009) Degrees of polymerization (DP) and DP distribution of cellouronic acids prepared from alkali-treated celluloses and ball-milled native celluloses by TEMPO-mediated oxidation. Cellulose 16:117–127

    Article  CAS  Google Scholar 

  28. de Nooy AEJ, Besemer AC, van Bekkum H, van Dijk JAPP, Smit JAM (1996) TEMPO-mediated oxidation of pullulan and influence of ionic strength and linear charge density on the dimensions of obtained polyelectrolyte chains. Macromolecules 29:6541–6547

    Article  Google Scholar 

  29. Shibata I, Isogai A (2003). Depolymerization of cellouronic acid during TEMPO-mediated oxidation. Cellulose 10:151–158

    Article  CAS  Google Scholar 

  30. Saito T, Hirota M, Tamura N, Fukuzumi H, Kimura S, Heux L, Isogai A (2009) Individualization of nano-sized plant cellulose fibrils by direct surface carboxylation using TEMPO catalyst under neutral conditions. Biomacromolecules 10:1992–1996

    Article  CAS  Google Scholar 

  31. Hirota M, Tamura N, Saito T, Isogai A (2009) Oxidation of regenerated cellulose with NaClO2 catalyzed by TEMPO and NaClO under acid-neutral conditions. Carbohydr Polym 78:330–335

    Article  CAS  Google Scholar 

  32. Zhao M, Li J, Mano E, Song Z, Tschaen DM, Grabowski EJJ, Reider PJ (1999) Oxidation of primary alcohols to carboxylic acids with sodium chlorite catalyzed by TEMPO and bleach. J Org Chem 64:2564–2566

    Article  CAS  Google Scholar 

  33. Sihtola H, Kyrklund B, Laamanen L, Palenlus I (1963) Comparison and conversion of viscosity and DP values determined by different methods. Paperi Ja Puu 45:225–323

    Google Scholar 

  34. Deshwal BR, Jo HD, Lee HK (2004) Reaction kinetics of decomposition of acidic sodium chlorite. Can J Chem Eng 82:619–623

    Article  CAS  Google Scholar 

  35. Abdel-Hafiz SA (1995) Accelerated oxidation of maize starch using the sodium chlorite/thiourea system. Polym Deg Stab 47:275–281

    Article  CAS  Google Scholar 

  36. Hebeish A, Ragheb AA, Haggag K, El-Rahman AAA (1997) Oxidation of moghat mucilage with sodium chlorite. Polym Deg Stab 58:33–40

    Article  CAS  Google Scholar 

  37. Bailey WF, Bobbitt JM, Wiberg KB (2007) Mechanism of the oxidation of alcohols by oxoammonium cations. J Org Chem 72:4504–4509

    Article  CAS  PubMed  Google Scholar 

  38. de Nooy AEJ, Besemer AC, van Bekkum H (1996) On the use of stable organic nitroxyl radicals for the oxidation of primary and secondary alcohols. Synthesis 10:1153–1174

    Article  Google Scholar 

  39. Bragd FL, Besemer AC, van Bekkum H (2001) TEMPO-derivatives as catalysts in the oxidation of primary alcohol groups in carbohydrates. J Mol Catal A Chem 170:35–42

    Article  CAS  Google Scholar 

  40. Whistler RL, Schweiger R (1957) Oxidation of amylopectin with hypochlorite at different hydrogen ion concentration. J Am Chem Soc 79:6460–6464

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Tsuguyuki Saito.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Saito, T., Hirota, M., Tamura, N. et al. Oxidation of bleached wood pulp by TEMPO/NaClO/NaClO2 system: effect of the oxidation conditions on carboxylate content and degree of polymerization. J Wood Sci 56, 227–232 (2010). https://doi.org/10.1007/s10086-009-1092-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10086-009-1092-7

Keywords