, Volume 23, Issue 6, pp 3511–3520 | Cite as

Hydrophobization of phosphorylated cellulosic fibers

Original Paper


Due to their flame retardant behavior, phosphorylated cellulosic fibers could be interesting candidates for use in the composite material field. However, because of the phosphate groups, the fiber network is highly charged and hydrophilic reducing its compatibility towards synthetic resins. An effective hydrophobization method for phosphorylated cellulosic fibers was therefore developed in order to enhance their hydrophobic behavior. The best results were obtained with a straightforward addition of tosylated fatty alcohols. The influence of the carbon chain length on the reaction efficiency, the thermal degradation and the hydrophobic behavior are reported. The success of the alkylation reaction was confirmed by FTIR analyses and the degree of substitution by elemental analysis. Contact angle with water of more than 100° were obtained after alkylation. The cellulosic samples were furthermore characterized by means of SEM, fiber length distribution, NMR spectroscopy and thermo gravimetric analysis.


Cellulose Fiber Lignocellulose Kraft Phosphorylation Flame retardant Alkylation Hydrophobization Composite material 



Fourier transform infrared spectroscopy


Nuclear magnetic resonance


Phosphate mono esters


Kraft fibers




Fiber Quality Analyzer


Phosphorus content


Anhydrous Glucose Unit


Degree of substitution


Carbon content


Thermo gravimetric analysis


Author contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.


The Natural Sciences and Engineering Research Council of Canada (NSERC), Fonds de Recherche du Québec en Nature et Technologies (FRQNT).


  1. Baier RE, Shafrin EG, Zisman WA (1968) Adhesion: mechanisms that assist or impede it. Science 162(3860):1360–1368CrossRefGoogle Scholar
  2. Belgacem MN, Gandini A (2005) The surface modification of cellulose fibres for use as reinforcing elements in composite materials. Compos Interfaces 12(1–2):41–75CrossRefGoogle Scholar
  3. Belosinschi D (2014). Coating phosphate ester dispersions for release paper production. Doctoral Thesis. Trois-Rivières, Université du Québec à Trois-RivièresGoogle Scholar
  4. Blanchard EJ, Graves EE (2003) Phosphorylation of cellulose with some phosphonic acid derivatives. Text Res J 73(1):22–26CrossRefGoogle Scholar
  5. Crépy L, Chaveriat L, Banoub J, Martin P, Joly N (2009) Synthesis of cellulose fatty esters as plastics—influence of the degree of substitution and the fatty chain length on mechanical properties. ChemSusChem 2(2):165–170CrossRefGoogle Scholar
  6. Cunha AG, Gandini A (2010) Turning polysaccharides into hydrophobic materials: a critical review. Part 1. Cellulose. Cellulose 17(5):875–889CrossRefGoogle Scholar
  7. Freire CSR, Silvestre AJD, Neto CP, Belgacem MN, Gandini A (2006) Controlled heterogeneous modification of cellulose fibers with fatty acids: effect of reaction conditions on the extent of esterification and fiber properties. J Appl Polym Sci 100(2):1093–1102CrossRefGoogle Scholar
  8. Horrocks AR, Kandola BK, Davies PJ, Zhang S, Padbury SA (2005) Developments in flame retardant textiles—a review. Polym Degrad Stab 88(1):3–12CrossRefGoogle Scholar
  9. Inagaki N, Nakamura S, Asai H, Katsuura K (1976) Phosphorylation of cellulose with phosphorous acid and thermal degradation of the product. J Appl Polym Sci 20(10):2829–2836CrossRefGoogle Scholar
  10. Kazemi F, Massah AR, Javaherian M (2007) Chemoselective and scalable preparation of alkyl tosylates under solvent-free conditions. Tetrahedron 63(23):5083–5087CrossRefGoogle Scholar
  11. Kumar MSY, Galil MSA, Suresha MS, Sathish MA, Nagendrappa G (2007) A simple spectrophotometric determination of phosphate in sugarcane juices, water and detergent samples. E-J Chem 4(4):467–473CrossRefGoogle Scholar
  12. Nifant’ev EE (1965) The phosphorylation of cellulose. Russ Chem Rev 34(12):942CrossRefGoogle Scholar
  13. Pappas CS, Malovikova A, Hromadkova Z, Tarantilis PA, Ebringerova A, Polissiou MG (2004) Determination of the degree of esterification of pectinates with decyl and benzyl ester groups by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and curve-fitting deconvolution method. Carbohydr Polym 56(4):465–469CrossRefGoogle Scholar
  14. Pelletier S, Hubert P, Lapicque F, Payan E, Dellacherie E (2000) Amphiphilic derivatives of sodium alginate and hyaluronate: synthesis and physico-chemical properties of aqueous dilute solutions. Carbohydr Polym 43(4):343–349CrossRefGoogle Scholar
  15. Pieschel F, Lange E, Camacho J, Körber H (2004). Starch phosphates method for the production thereof and their use, United States PatentGoogle Scholar
  16. Pradhan, S, Pokhrel MR (2013). Spectrophotometric determination of phosphate in sugarcane juice, fertilizer, detergent and water samples by molybdenum blue method. 11(11):5Google Scholar
  17. Sakakura A, Katsukawa M, Ishihara K (2005) Selective synthesis of phosphate monoesters by dehydrative condensation of phosphoric acid and alcohols promoted by nucleophilic bases. Org Lett 7(10):1999–2002CrossRefGoogle Scholar
  18. Shi Y, Belosinschi D, Brouillette F, Belfkira A, Chabot B (2014) Phosphorylation of Kraft fibers with phosphate esters. Carbohydr Polym 106:121–127CrossRefGoogle Scholar
  19. Shi Y, Belosinschi D, Brouillette F, Belfkira A, Chabot B (2015) The properties of phosphorylated kraft fibers. Bioresources 10:4375Google Scholar
  20. Silverstein RM, Bassler GC, Morrill TC (1991) Spectrometric identification of organic compounds. Wiley, New YorkGoogle Scholar
  21. Suflet DM, Chitanu GC, Popa VI (2006) Phosphorylation of polysaccharides: new results on synthesis and characterisation of phosphorylated cellulose. React Funct Polym 66(11):1240–1249CrossRefGoogle Scholar
  22. Watanabe K, Kato Y, Masahiko Saito T, Takeo Oba H, Fukushima H, Hara T (1986) 5-fluoro-2′-deoxyduridine derivatives and a process for the preparation thereof, U.S. Patent 4,605,645Google Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2016

Authors and Affiliations

  1. 1.Centre de Recherche sur les Matériaux LignocellulosiquesUniversité du Québec à Trois-RivièresTrois-RivièresCanada
  2. 2.Laboratoire de Chimie des Substances Naturelles, Faculté des Sciences et TechniquesUniversité de LimogesLimoges CedexFrance

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