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Licensed Unlicensed Requires Authentication Published by De Gruyter July 18, 2006

The formation of aromatic end group structures in O-alkyl substituted celluloses under alkaline pulping conditions

Anne Vikkula and Tapani Vuorinen
From the journal


UV resonance Raman (UVRR) spectroscopy was used to study changes in the structure of reducing end groups of O-alkyl substituted celluloses under conditions simulating the initial phase of soda pulping. The derivatives studied were carboxymethyl cellulose (CMC) with a degree of substitution (DS) of 0.58 and methyl cellulose (MC) with DS of 1.64–1.95. Hot alkaline treatments were carried out in solutions of sodium hydroxide (0.1–1 M) at 95°C in the presence of creosol as a lignin model compound. Alkali-stable aromatic end groups were generated in both cellulose ethers. Moreover, the end groups of methyl cellulose were extensively condensed with creosol. The results demonstrate that aromatisation and condensation depend on the pH and reaction time.


Corresponding author: Laboratory of Forest Products Chemistry, Department of Forest Products Technology, Helsinki University of Technology, P.O. Box 6400, FIN-02150 Espoo, Finland Fax +358-9-4514259


Enström, N., Vikkula, A., Teleman, A., Vuorinen, T. (1995) Structure of hemicelluloses in pine kraft cooking liquors. In: Proceedings of the 8th International Symposium on Wood and Pulping Chemistry, Helsinki, Vol. III. pp. 195–200.Search in Google Scholar

Forsskåhl, I., Popoff, T., Theander, O. (1976) Reactions of d-xylose and d-glucose in alkaline, aqueous solutions. Carbohydr. Res.48:13–21.10.1016/S0008-6215(00)83510-7Search in Google Scholar

Fullerton, T.J., Wilkins, A.L. (1985) The mechanism of cleavage of β-ether bonds in lignin model compounds by reducing sugars. J. Wood Chem. Technol.5:189–201.10.1080/02773818508085187Search in Google Scholar

Gierer, J., Wännström, S. (1984) Formation of alkali-stable C-C bonds between wood polymers during kraft pulping. Holzforschung38:181–184.10.1515/hfsg.1984.38.4.181Search in Google Scholar

Halttunen, M., Vyörykkä, J., Hortling, B., Tamminen, T., Batchelder, D., Zimmermann, A., Vuorinen, T. (2001) Study of residual lignin in pulp by UV resonance Raman spectroscopy. Holzforschung55:631–638.10.1515/HF.2001.103Search in Google Scholar

Iversen, T., Wännström, S. (1986) Lignin-carbohydrate bonds in a residual lignin isolated from kraft pulp. Holzforschung40:19–22.10.1515/hfsg.1986.40.1.19Search in Google Scholar

Iversen, T., Westermark, U. (1985) Lignin-carbohydrate bonds in pine lignins dissolved during kraft pulping. Cellulose Chem. Technol.19:531–536.Search in Google Scholar

Johansson, M.H., Samuelson, O. (1977) Alkaline destruction of birch xylan in the light of recent investigations of its structure. Svensk Papperstidn.16:519–524.Search in Google Scholar

Johnson, K.G., Overend, R.P. (1991) Lignin-carbohydrate complexes from Populus deltoides I. Purification and characterization. Holzforschung4:469–475.Search in Google Scholar

Karlsson, O. (1997) Studies on the extent of bonding between lignin and polysaccharides in pulps. Doctoral dissertation. Royal Institute of Technology (KTH), Stockholm. pp. 1–44.Search in Google Scholar

Létumier, F., Ämmänlahti, E., Sipilä, J., Vuorinen, T. (2003) A facile route of formation of lignin-carbohydrate complexes during alkaline pulping. J. Pulp Pap. Sci.29(2):42–47.Search in Google Scholar

Minor, J.L. (1983) Chemical linkage of polysaccharides to residual lignin in pine kraft pulps. In: Proceedings of the International Symposium on Wood and Pulping Chemistry, Japan. pp. 2153–2158.Search in Google Scholar

Ohara, S., Hosoya, S., Nakano, J. (1980) Studies on the formation of lignin-carbohydrate complex during alkaline pulping processes. Mokuzai Gakkaishi26:408–413.Search in Google Scholar

Ragnar, M., Lindgren, C.T., Nilvebrandt, N.-O. (2000) pKa values of guaiacyl and syringyl phenols related to lignin. J. Wood Chem. Technol.20:277–305.10.1080/02773810009349637Search in Google Scholar

Saariaho, A.-M., Jääskeläinen, A-.S., Nuopponen, M., Vuorinen, T. (2003) Ultraviolet resonance Raman spectroscopy in lignin analysis: Determination of characteristic vibrations of p-hydroxyphenyl, guaiacyl and syringyl lignin structures. Appl. Spectrosc.57:58–66.10.1366/000370203321165214Search in Google Scholar

Sjöström, E. (1993) Wood Chemistry. Fundamentals and Applications. 2nd ed. Academic Press. pp. 136–137.Search in Google Scholar

Valkama, J.-P. (2002) Model compound studies of the formation of C-C bonds between lignin and polysaccharide under kraft pulping conditions. Master's thesis, Helsinki University of Technology, Espoo.Search in Google Scholar

Vikkula, A. (1999). Hemicelluloses in kraft cooking liquors. Licentiate's thesis, Helsinki University of Technology, Espoo. pp. 68–71.Search in Google Scholar

Vikkula, A., Létumier, F., Tenkanen, M., Sipilä, J., Vuorinen, T. (2001) Generation of phenol-xylan complexes in kraft pulping conditions. In: Proceedings of the 11th International Symposium on Wood and Pulping Chemistry (ISWPC), Nice, Vol. 1. pp. 51–54.Search in Google Scholar

Vikkula, A., Valkama, J., Vuorinen, T. (2006) Formation of aromatic and other unsaturated end groups in carboxymethyl cellulose during hot alkaline treatment. Cellulose, in press.10.1007/s10570-005-9024-1Search in Google Scholar

Yamasaki, T., Hosoya, S., Chen, C.-T., Gratzl, J.S., Chang, H. (1981) Characterization of residual lignin in kraft pulp. In: Proceedings of the International Symposium On Wood and Pulping Chemistry, Stockholm, Vol. II. pp. 34–42.Search in Google Scholar

Published Online: 2006-07-18
Published in Print: 2006-07-01

©2006 by Walter de Gruyter Berlin New York