Nitrosation of Lignosulfonates under Solid-Phase Catalysis Conditions. C. 175-187

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UDС

676.084.2:66.095.82

DOI:

10.37482/0536-1036-2024-3-175-187

Abstract

Lignosulfonates are the most common commercial lignin-based product due to their unique properties. Various methods are known for modifying lignosulfonates and lignosulfonic acids. This article presents the results of the development of a new approach to the production of nitrosated lignosulfonic acids. The method is based on a reaction catalyzed by cation exchange resins in the H-form: KU-2-8 cation exchanger and wofatite. The influence of reagent consumption and reaction duration on the course of nitrosation has been studied. The dynamics of the proposed nitrosation practically coincides with the dynamics of a similar reaction using sulfuric acid by the known method. The optimal consumption of sodium nitrite equals 15 %, and the optimal consumption of cation exchanger equals 100 % by weight of lignosulfonates. During the nitrosation of lignosulfonates, significant changes in the electronic spectra occur in the region of 280...500 nm. Two overlapping absorption bands appear with maxima at 300 and 330 nm, as well as an intense absorption band at 430 nm, due to nitroso groups conjugated with the aromatic nuclei of phenylpropane units. To analyze the ionization spectra, they have been deconvoluted. The resulting spectra are well approximated by 5 Gaussians with an error of no more than 5 %. Two options for carrying out the nitrosation reaction of lignosulfonates have been proposed: under static and dynamic conditions. It has been established that under dynamic conditions, nitroso derivatives of lignosulfonic acids are formed that do not contain metal cations, and the pH of the resulting solutions does not exceed 1.4. The elemental compositions of the isolated initial and nitrosated lignosulfonic acids have been determined. The nitrogen content of lignosulfonic acids has increased from 0.32 (initial) to 2.17 % (nitrosated). In addition, under dynamic conditions, an additional stage of separating the cation exchanger from the reaction medium by filtration is not required. New bands have appeared in the IR spectrum of nitrosated lignosulfonic acids: at 1540 cm–1, which is due to the presence of nitroso groups, and a wide absorption band at 1700...1715 cm–1, which can be caused by vibrations of the carboxyl group or the quinone monooxime tautomeric form of the guaiacyl structures of lignosulfonic acids.

Authors

Yuriy G. Khabarov*, Doctor of Chemistry, Prof.; ResearcherID: P-1802-2015, ORCID: https://orcid.org/0000-0001-8392-0985
Viacheslav A. Veshnyakov, Candidate of Chemistry; ResearcherID: E-3882-2017, ORCID: https://orcid.org/0000-0002-8278-5053
Vadim A. Plakhin, Candidate of Chemistry; ResearcherID: AAH-6544-2020, ORCID: https://orcid.org/0000-0001-9143-1663
Evgeniy A. Skripnikov, Postgraduate Student; ResearcherID: AFB-6325-2022, ORCID: https://orcid.org/0009-0007-8028-4056
Denis V. Ovchinnikov, Candidate of Chemistry; ResearcherID: B-7162-2018, ORCID: https://orcid.org/0000-0001-9313-2448

Affiliation

Northern (Arctic) Federal University named after M.V. Lomonosov, Naberezhnaya Severnoy Dviny, 17, Arkhangelsk, 163002, Russian Federation; khabarov.yu@mail.ru*, v.a.veshnyakov@narfu.ru, d.ovchinnikov@narfu.ru

Keywords

lignin, lignosulfonates, lignosulfonic acids, modification, nitrosation, solid-phase catalysis, spectrophotometry, nitrosolignosulfonic acids

For citation

Khabarov Yu.G., Veshnyakov V.A., Plakhin V.A., Skripnikov. E.A., Ovchinnikov D.V. Nitrosation of Lignosulfonates under Solid-Phase Catalysis Conditions. Lesnoy Zhurnal = Russian Forestry Journal, 2024, no. 3, pp. 175–187. (In Russ.). https://doi.org/10.37482/0536-1036-2024-3-175-187

References

1. Bellamy L. The Infra-Red Spectra of Complex Molecules. Moscow, Inostrannaya literatura Publ., 1963. 590 p. (In Russ.).
2. Gogotov A.F. Nitrite Treatments of Unbleached Pulps Followed by Oxygen-Alkaline Delignification. Khimija Rastitel’nogo Syr’ja, 1999, no. 1, pp. 89–97. (In Russ.).
3. Gogotov A.F., Zakazov A.N., Babkin V.A. Nitrite Method for Analyzing Paper Compositions. Khimija Rastitel’nogo Syr’ja, 2001, no. 2, pp. 39–46. (In Russ.).
4. Zakis G.F., Mozheiko L.N., Telysheva G.M. Methods for Determining Functional Groups of Lignin. Riga, Zinatne Publ., 1975. 174 p. (In Russ.).
5. Sykes P. A Guidebook to Mechanism in Organic Chemistry. Moscow, Khimiya Publ., 1991. 448 p. (In Russ.).
6. Khabarov Yu.G., Koshutina N.N. Changing of Complexing Properties of Lignosulfonates by Nitrosing. Lesnoy Zhurnal = Russian Forestry Journal, 2001, no. 5-6, pp. 134–139. (In Russ.).
7. Khabarov Yu.G., Pes’yakova L.A., Kolygin A.V. Nitrosation of Lignosulfonic Acids for Their Colorimetric Determination. Russian Journal of Applied Chemistry, 2006, vol. 79, iss. 9, pp. 1555–1558. (In Russ.). https://doi.org/10.1134/S1070427206090333
8. The Chemistry of the Nitro and Nitroso Groups. Vol. 1. Ed. by H. Feuer. Moscow, Mir Publ., 1972. 536 p. (In Russ.).
9. The Chemistry of the Nitro and Nitroso Groups. Vol. 2. Ed. by H. Feuer. Moscow, Mir Publ., 1973. 301 p. (In Russ.).
10. Berlin A., Balakshin M. Chapter 18 – Industrial Lignins: Analysis, Properties, and Applications. Bioenergy Research: Advances and Applications, 2014, pp. 315–336. https://doi.org/10.1016/B978-0-444-59561-4.00018-8
11. Duval A., Lawoko M. A Review on Lignin-Based Polymeric, Micro- and NanoStructured Materials. Reactive and Functional Polymers, 2014, vol. 85, pp. 78–96. https://doi.org/10.1016/j.reactfunctpolym.2014.09.017
12. Graupner N. Application of Lignin as Natural Adhesion Promoter in Cotton Fibre-Reinforced Poly(Lactic Acid) (PLA) Composites. Journal of Materials Science, 2008, vol. 43, pp. 5222–5229. https://doi.org/10.1007/s10853-008-2762-3
13. Housecroft C.E., Sharpe A.G. Inorganic Chemistry. 4th ed. London, Pearson Education Limited, 2012. 1213 p.
14. Kazzaz A.E., Fatehi P. Technical Lignin and its Potential Modification Routes: A Mini-Review. Industrial Crops and Products, 2020, vol. 154, art. no. 112732. https://doi.org/10.1016/j.indcrop.2020.112732
15. Laurichesse S., Avérous L. Chemical Modification of Lignins: Towards Biobased Polymers. Progress in Polymer Science, 2014, vol. 39, iss. 7, pp. 1266–1290. https://doi.org/10.1016/j.progpolymsci.2013.11.004
16. Liu Y. Tert-Butyl Nitrite. Synlett, 2011, iss. 8, pp. 1184–1185. https://doi.org/10.1055/s-0030-1259948
17. Mimini V., Kabrelian V., Fackler K., Hettegger H., Potthast A., Rosenau T. Lignin-Based Foams as Insulation Materials: a Review. Holzforschung, 2019, vol. 73, no. 1, pp. 117–130. https://doi.org/10.1515/hf-2018-0111
18. Miyahara M., Kamiya S., Nakadate M. Nitrosation of 1,3-Diarylureas with Nitrosyl Chloride, Dinitrogen Trioxide and Dinitrogen Tetroxide in Dimethylformamide. Chemical and Pharmaceutical Bulletin, 1983, vol. 31, iss. 1, pp. 41–44. https://doi.org/10.1248/cpb.31.41
19. Pearl I.A., Benson H.K. A Nitrosolignin Colorimetric Test for Sulfite Waste Liquor in Sea Water. Paper Trade Journal, 1940, vol. 111, pp. 235–236.
20. Shchavlev A.E., Pankratov A.N., Enchev V. Intramolecular Hydrogen-Bonding Interactions in 2-Nitrosophenol and Nitrosonaphthols: Ab Initio, Density Functional, and Nuclear Magnetic Resonance Theoretical Study. The Journal of Physical Chemistry A, 2007, vol. 111, iss. 30, pp. 7112–7123. https://doi.org/10.1021/jp068540r
21. Strassberger Z., Tanase S., Rothenberg G. The Pros and Cons of Lignin Valorisation in an Integrated Biorefinery. RSC Advances, 2014, vol. 4, iss. 48, pp. 25310–25318. https://doi.org/10.1039/C4RA04747H