Skip to content
Licensed Unlicensed Requires Authentication Published by De Gruyter January 6, 2016

Monitoring of free phenol content in lignosulfonates by ClO2 titration and UV difference spectroscopy

  • Orianne Broussard , Morgane Petit , Nicolas Elie , Stéphanie Baumberger , Alix Arnaud , Paul-Henri Ducrot EMAIL logo and Florent Allais EMAIL logo
From the journal Holzforschung

Abstract

Lignosulfonates (LS) are water-soluble polyphenolic macromolecules derived from lignins and common industrial additives in plasticizers and dispersants. A key feature for a more efficient utilization of modified LS is the monitoring of their free phenol (OHphen) content during various reactions as these phenols govern a large part of their chemical reactivity. Against this background, the UV difference spectroscopy (Δεi method) and ClO2 titration have been revisited. Synthetic LS model compounds with a SO3H group on their benzylic position and H, G, and S aromatic rings were synthesized and used to assess the suitability of both the ClO2 titration and the Δεi method on LS. The methodology combining the two analytical methods was then used to determine the molar extinction coefficient of a given LS allowing the calibration of the Δεi method for a convenient and rapid monitoring of OHphen in the course of LS reactions involving the OHphen groups.


Corresponding authors: Paul-Henri Ducrot and Florent Allais, Institut Jean-Pierre Bourgin, INRA, AgroParisTech, CNRS, Université Paris-Saclay, RD10, 78026 Versailles Cedex, France, e-mail: (P.-H. Ducrot); , (F. Allais)

Acknowledgments

The authors thank Saint-Gobain Recherche for financial support. The authors are also grateful to Dr. Serge Ratton for fruitfull discussions.

References

Allan, G.G. Process for the partial substitution of ammonium lignosulfonate for phenol in phenolic-aldehyde resin adhesives. Patent US 4172544. 10-11-1975.Search in Google Scholar

Alonso, M., Rodríguez, J., Oliet, M., Rodríguez, F., Garcia, J., Gilarranz, M. (2001) Characterization and structural modification of ammonic lignosulfonate by methylolation. J. Appl. Polym. Sci. 82:2661–2668.10.1002/app.2119Search in Google Scholar

Argyropoulos, D.S. (1995) 31P NMR in wood chemistry: a review of recent progress. Res. Chem. Intermed. 21:373–395.10.1007/BF03052265Search in Google Scholar

Aulin-Erdman, G. (1954) Phenolic Groups in Spruce Lignin. Svensk Papperstidn. 57:745–760.Search in Google Scholar

Aulin-Erdtman, G., Sanden, R. (1968) Spectrographic contributions to lignin chemistry. Acta Chem. Scand. 22:1187–1209.10.3891/acta.chem.scand.22-1187Search in Google Scholar

Ba, K., Tine, E., Destain, J., Cissé, N., Thonart, P. (2010) Etude comparative des composés phénoliques, du pouvoir antioxydant de différentes variétés de sorgho sénégalais et des enzymes amylolytiques de leur malt. Biotechnology, Agronomy, Society and Environment 14:131–139.Search in Google Scholar

Behrooz Eshkiki, R., Mortha, G., Lachenal, D. (2007) A new method for the titration of free phenolic groups in pulps. Holzforschung 61:242–246.10.1515/HF.2007.039Search in Google Scholar

Biermann, C.J. Kraft spent liquor recovery. In: Handbook of Pulping and Papermaking. Academic Press, San Diego, 1996. pp. 101–122.10.1016/B978-012097362-0/50008-XSearch in Google Scholar

Bornstein, L.F. Lignin-based composition board binder comprising a copolymer of a lignosulfonate, melamine and an aldehyde. Patent US4130515. 06-30-1977.Search in Google Scholar

Cole, B., Kwon, H. (1995) The periodate oxidation method: does it really measure phenolic hydroxyl content. 8th International symposium, Wood and pulping chemistry Finland. 1:541–548.Search in Google Scholar

Delmas, D. Dosage des groupements phénoliques et quinoniques dans les pâtes cellulosiques. Thesis Laboratoire de Génie des Procédés Papetiers de Grenoble INP-Pagora. Grenoble. Institut Polytechnique de Grenoble. 2009a. pp. 225.Search in Google Scholar

Delmas, D., Lachenal, D., Mortha, G., Marlin, N., Calais, C. (2009b) Titration of free phenolic groups in pulps 10th EWLP, Stockholm, Sweden, August 25–28, 2008. Holzforschung 63:705–710.10.1515/HF.2009.101Search in Google Scholar

El Mansouri, N.E., Salvadó, J. (2006) Structural characterization of technical lignins for the production of adhesives: application to lignosulfonate, kraft, soda-anthraquinone, organosolv and ethanol process lignins. Ind. Crop. Prod. 24:8–16.10.1016/j.indcrop.2005.10.002Search in Google Scholar

El Mansouri, N.E., Farriol, X., Salvadó, J. (2006) Structural modification and characterization of lignosulfonate by a reaction in an alkaline medium for its incorporation into phenolic resins. J. Appl. Polym. Sci. 102:3286–3292.10.1002/app.24744Search in Google Scholar

Gärtner, A., Gellerstedt, G., Tamminen, T. (1999) Determination of phenolic hydroxyl groups in residual lignin using a modified UV-method Nord. Pulp Pap. Res. J. 14:163–170.10.3183/npprj-1999-14-02-p163-170Search in Google Scholar

Glennie, D.W. (1971) Reactions in sufite pulping. Chap. 15. In: Lignins – occurrence, formation, structure and reactions. Eds. Sarkanen, K.V., Ludwig, C.H. Wiley-Interscience, New York. pp. 597–632.Search in Google Scholar

Hamzeh, Y. Evaluation de Nouveaux Procédés de Delignification et Blanchiment en Reacteur a Deplacement de Liqueur, et Comparaison avec les Procédés Traditionnels. Thesis Laboratoire de Génie des Procédés Papetiers. Grenoble. Ecole Française de Papeterie et des Industries Graphiques de Grenoble, 2005. pp. 222.Search in Google Scholar

Janiga, E.R. Lignosulfonate-phenol-formaldehyde resin binder in sheet material and method of making said sheet material. Patent US4701383. 12-16-1985.Search in Google Scholar

Lin, S.Y. Method for polymerization of lignosulfonates. Patent US4332589. 11-24-1980.Search in Google Scholar

Lin, S.Y., Dence, C.W. Methods in lignin chemistry. Science, W. Springer-Verlag, 1992.10.1007/978-3-642-74065-7Search in Google Scholar

Lora, J.H., Glasser, W.G. (2002) Recent industrial applications of lignin: A sustainable alternative to nonrenewable materials. J. Polym. Environ. 10:39–48.10.1023/A:1021070006895Search in Google Scholar

Lutnaes, B.F., Myrvold, B.O., Lauten, R.A., Endeshaw, M.M. (2008) 1H and 13C NMR data of benzylsulfonic acids – model compounds for lignosulfonate. Magn. Reson. Chem. 46: 299–305.10.1002/mrc.2184Search in Google Scholar

Månsson, P. (1983) Quantitative determination of phenolic and total hydroxyl groups in lignins. Holzforschung 37: 143–146.10.1515/hfsg.1983.37.3.143Search in Google Scholar

Sen, S., Sadeghifar, H., Argyropoulos, D.S. (2013) Kraft lignin chain extension chemistry via propargylation, oxidative coupling, and claisen rearrangement. Biomacromolecules 14:3399–3408.10.1021/bm4010172Search in Google Scholar

Singleton, V.L., Orthofer, R., Lamuela-Raventos, R.M. (1999) Analysis of total phenols and other oxidation substrates and antioxidants by means of folin-ciocalteu reagent. Methods Enzymol 299:152–178.10.1016/S0076-6879(99)99017-1Search in Google Scholar

Sixta, H. Chemical pulping process. In: Handbook of Pulp, Vol. 1. Ed. Sixta, H. Wiley-VCH, Weinheim, Germany, 2006. pp. 109–510.10.1002/9783527619887.ch4aSearch in Google Scholar

Wexler, A.S. (1964) Characterization of lignosulfonates by ultraviolet spectrometry. Direct and difference spectrograms. Anal. Chem. 36:1829–1831.10.1021/ac60207a066Search in Google Scholar

Received: 2015-5-11
Accepted: 2015-11-24
Published Online: 2016-1-6
Published in Print: 2016-8-1

©2016 Walter de Gruyter GmbH, Berlin/Boston

Downloaded on 5.6.2023 from https://www.degruyter.com/document/doi/10.1515/hf-2015-0111/html
Scroll to top button