Journal of Materials Science

, Volume 49, Issue 7, pp 2832–2843 | Cite as

Study of the hydrophobization of TEMPO-oxidized cellulose gel through two routes: amidation and esterification process

  • A. Benkaddour
  • C. Journoux-Lapp
  • K. JradiEmail author
  • S. Robert
  • C. Daneault


In this paper, we studied the hydrophobization of TEMPO-oxidized cellulose gel (TOCgel) by covalent coupling of long carbon chains via esterification and amidation processes. In this context, amidation process was achieved by covalent coupling of stearylamine (SA) on the carboxyl moieties of TOCgel using carbodiimide and hydroxysuccimide as catalyst and amidation agent. In parallel, esterification process was realized by grafting of alkyl ketene dimer (AKD) on the hydroxyl groups of TOCgel in the presence of 1-methylimidazole as a promoter. The grafting state of the final products obtained under heterogeneous conditions was confirmed by fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), transmission and scanning electron microscopy, and contact angle measurement (CAM). The hydrophobic behavior of the obtained products was discussed based on the results of CAM and absorption rate of water drop in their film surface. FTIR and XPS results indicated the formation of amide bonding for the SA-g-TOCgel (amidation), and β-keto ester linkages for the AKD-g-TOCgel (esterification). As confirmed by CAM, the both chemical treatments enhanced the transition hydrophilic/hydrophobic behavior of the TOCgel fibers. It appeared also that CA values of grafted samples showed a slightly greater hydrophobicity of AKD-g-TOCgel (115° ± 2°) relatively to SA-g-TOCgel (102° ± 2°). However, the absorption rate of water drop seems to be relatively faster for AKD-g-TOCgel than for SA-g-TOCgel. Indeed, the water resistance of amidation product could be due to the high graft efficiency obtained (46.3 %) in comparison with that of the esterification product (30 %). In parallel, this result was confirmed by the dispersion test of modified TOCgels in hexane solvent which indicated clearly the high stable dispersion of SA-g-TOCgel obtained through the amidation process. Moreover, TGA result demonstrated that the thermal stability was found to be slightly higher for SA-g-TOCgel than for AKD-g-TOCgel. Finally, the excellent hydrophobic properties of modified TOCgel material could be suitable to be used as reinforcement for nonpolar polymer matrices in industrial applications.


Atom Transfer Radical Polymerization Contact Angle Measurement Cellulose Nanofibers Alkyl Ketene Dimer Covalent Coupling 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



The authors gratefully acknowledge the Natural Science and Engineering Research Council of Canada (NSERC) for financial support.


  1. 1.
    Azizi Samir MA, Alloin F, Dufresne A (2005) Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite field. Biomacromolecules 6:612–626CrossRefGoogle Scholar
  2. 2.
    Orts WJ, Shey J, Imam SH, Glenn GM, Guttman ME, Revol JF (2005) Application of cellulose microfibrils in polymer nanocomposites. J Polym Environ 13:301–306CrossRefGoogle Scholar
  3. 3.
    Klemm D, Heublein B, Fink HP, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Ed 44:3358CrossRefGoogle Scholar
  4. 4.
    Czaja WK, Young DJ, Kawecki M, Brown RM Jr (2007) The future prospects of microbial cellulose in biomedical applications. Biomacromolecules 8(1):1CrossRefGoogle Scholar
  5. 5.
    Siqueira G, Bras J, Dufresne A (2009) Cellulose whiskers versus microfibrils: influence of the nature of the nanoparticle and its surface functionalization on the thermal and mechanical properties of nanocomposites. Biomacromolecules 10(2):425–432CrossRefGoogle Scholar
  6. 6.
    Gradwell SE, Renneckar S, Esker AR, Heinze T, Gatenholm P, Vaca-Garcia C, Glasser W (2004) Surface modification of cellulose fibers: towards wood composites by biomimetics. CR Biol 327(9–10):945–953CrossRefGoogle Scholar
  7. 7.
    Baiardo M, Frisoni G, Scandola M, Licciardello A (2002) Surface chemical modification of natural cellulose fibers. J Appl Polym Sci 83(1):38–45CrossRefGoogle Scholar
  8. 8.
    Belgacem M, Gandini A (2005) The surface modification of cellulose fibres for use as reinforcing elements in composite materials. Compos Interfaces 12:41–75CrossRefGoogle Scholar
  9. 9.
    Bledzki AK, Gassan J (1999) Composites reinforced with cellulose based fibers. Prog Polym Sci 24:221–274CrossRefGoogle Scholar
  10. 10.
    Tingaut P, Zimmermann T, Lopez-Suevos F (2010) Synthesis and characterization of bionanocomposites with tunable properties from poly(lactic acid) and acetylated microfibrillated cellulose. Biomacromolecules 11(2):454–464CrossRefGoogle Scholar
  11. 11.
    Lonnberg H, Zhou Q, Brumer H, Teeri TT, Malmstrom E, Hult A (2006) Grafting of cellulose fibers with poly(e-caprolactone) and poly(l-lactic acid) via ring-opening polymerization. Biomacromolecules 7(7):2178–2185CrossRefGoogle Scholar
  12. 12.
    Roy D, Guthrie JT, Perrier S (2005) Graft polymerization: grafting poly(styrene) from cellulose via reversible addition-fragmentation chain transfer (RAFT) polymerization. Macromolecules 38(25):10363–10372CrossRefGoogle Scholar
  13. 13.
    Carlmark A, Malmstrom E (2003) ATRP grafting from cellulose fibers to create block-copolymer grafts. Biomacromolecules 4(6):1740–1745CrossRefGoogle Scholar
  14. 14.
    Coskun M, Temüz MM (2005) Grafting studies onto cellulose by atom-transfer radical polymerization. Polym Int 54(2):342–347CrossRefGoogle Scholar
  15. 15.
    Gaiolas C, Belgacem MN, Silva L, Thielemans W, Costa AP, Nunes M, Silva MJS (2009) Green chemicals and process to graft cellulose fiber. J Colloid Interface Sci 330(2):298–302CrossRefGoogle Scholar
  16. 16.
    Ly B, Bras J, Sadocco P, Belgacem MN, Dufresne A, Thielemans W (2010) Surface functionalization of cellulose by grafting oligoether chains. Mater Chem Phys 120(2–3):438–445CrossRefGoogle Scholar
  17. 17.
    Benkaddour A, Jradi K, Robert S, Daneault C (2013) Grafting of polycaprolactone on oxidized nanocelluloses by click chemistry. Nanomaterials 3:141–157CrossRefGoogle Scholar
  18. 18.
    Lin N, Huang J, Dufresne A (2012) Preparation, properties and applications of polysaccharide nanocrystals in advanced functional nanomaterials. Nanoscale 11(4):3274–3294CrossRefGoogle Scholar
  19. 19.
    Chanzy H (1990) Aspects of cellulose structure. In: Kennedy JF, Philips GO, William PA (eds) Cellulose sources and exploitation. Ellis Horwood Ltd, New York, p 3–12Google Scholar
  20. 20.
    Marchessault RH, Morehead FF, Walter NM (1959) Liquid crystal systems from fibrillar polysaccharides. Nature 184:632CrossRefGoogle Scholar
  21. 21.
    Kim J, Yun S, Ounaies Z (2006) Discovery of cellulose as a smart material. Macromolecules 39:4202CrossRefGoogle Scholar
  22. 22.
    Paakko M, Ankerfors M, Kosonen H, Nykanen A, Ahola S, Osterberg M, Ruokolainen J, Laine J, Larsson PT, Ikkala O, Lindstrom T (2007) Enzymatic hydrolysis combined with mechanical shearing and high-pressure homogenization for nanoscale cellulose fibrils and strong gels. Biomacromolecules 8:1934CrossRefGoogle Scholar
  23. 23.
    Elazzouzi-Hafraoui S, Nishiyama Y, Putaux JL, Heux L, Dubreuil F, Rochas C (2008) The shape and size distribution of crystalline nanoparticles prepared by acid hydrolysis of native cellulose. Biomacromolecules 9:57CrossRefGoogle Scholar
  24. 24.
    Saito T, Nishiyama Y, Putaux JL, Vignon M, Isogai A (2006) Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose. Biomacromolecules 7:1687CrossRefGoogle Scholar
  25. 25.
    Loranger E, Piché AO, Daneault C (2012) Influence of high shear dispersion on the production of cellulose nanofibers by ultrasound-assisted TEMPO-oxidation of kraft pulp. Nanomaterials 2(3):286–297CrossRefGoogle Scholar
  26. 26.
    Loranger E, Paquin M, Daneault C, Chabot B (2011) Comparative study of sonochemical effects in an ultrasonic bath and in a large-scale flow-through sonoreactor. Chem Eng J 178:359–365CrossRefGoogle Scholar
  27. 27.
    Okita Y, Saito T, Isogai A (2010) Entire surface oxidation of various cellulose microfibrils by TEMPO-mediated oxidation. Biomacromolecules 11:1696CrossRefGoogle Scholar
  28. 28.
    Lasseuguette E (2008) Grafting onto cellulose microfibrils. Cellulose 15:571–580CrossRefGoogle Scholar
  29. 29.
    Araki J, Wada M, Kuga S (2001) Steric stabilization of a cellulose microcrystal suspension by poly(ethylene glycol) grafting. Langmuir 17:21CrossRefGoogle Scholar
  30. 30.
    Johnson RK, Zink-Sharp A, Glasser WG (2011) Preparation and characterization of hydrophobic derivatives of TEMPO-oxidized nanocellulose. Cellulose 18:1599–1609CrossRefGoogle Scholar
  31. 31.
    Oh SY, Yoo DI, Shin Y, Seo G (2005) FTIR analysis of cellulose treated with sodium hydroxide and carbon dioxide. Carbohydr Res 340:417–428CrossRefGoogle Scholar
  32. 32.
    Barazzouk S, Daneault C (2012) Tryptophan-based peptides grafted onto oxidized nanocellulose. Cellulose 19:481–493CrossRefGoogle Scholar
  33. 33.
    Missoum K, Bras J, Belgacem MN (2012) Organization of aliphatic chains grafted on nanofibrillated cellulose and influence on final properties. Cellulose 19:1957–1973CrossRefGoogle Scholar
  34. 34.
    Kamdem DP, Zhang J, Adnot A (2001) Identification of cupric and cuprous copper in copper naphthenate-treated wood by X-ray photoelectron spectroscopy. Holzforschung 55:16–20CrossRefGoogle Scholar
  35. 35.
    Johansson LS, Campbell JM (2004) Reproducible XPS on biopolymers: cellulose studies. Surf Interface Anal 36:1018–1022CrossRefGoogle Scholar
  36. 36.
    Ahmed A, Adnot A, Grandmaison JL, Kaliaguine S, Doucet J (1987) ESCA analysis of cellulosic materials. Cellulose Chem Technol 21(5):483–492Google Scholar
  37. 37.
    Song X, Chen F, Liu F (2012) Preparation and characterization of alkyl ketene dimer (AKD) modified cellulose composite membrane. Carbohydr Polym 88:417–421CrossRefGoogle Scholar
  38. 38.
    Matuana LM, Balatinecz JJ, Sodhi RNS, Park CB (2001) Surface characterization of esterified cellulosic fibers by XPS and FTIR Spectroscopy. Wood Sci Technol 35:191–201CrossRefGoogle Scholar
  39. 39.
    Habibi Y, Goffin AL, Schiltz N, Duquesne E, Dubois P, Dufresne A (2008) Bionanocomposites based on poly(3-caprolactone)-grafted cellulose nanocrystals by ring-opening polymerization. J Mater Chem 18:5002–5010CrossRefGoogle Scholar
  40. 40.
    Littunen K, Hippi U, Johansson LS, Österberg M, Tammelin T, Liane J, SeppäläJ (2011) Free radical graft copolymerization of nanofibrillated cellulose with acrylic monomers. Carbohydr Polym 84:1039–14047CrossRefGoogle Scholar
  41. 41.
    Rambo CR, Recouvreux DOS, Carminatti CA, Pitlovanciv AK, Antonio RV, Porto LM (2008) Template assisted synthesis of porous nanofibrous cellulose membranes for tissue engineering. Mater Sci Eng C 28:549CrossRefGoogle Scholar
  42. 42.
    Cunha AG, Freire CSR, Silvestre AJD, Neto CP, Gandini A, Orblin E, Fardim P (2007) Highly hydrophobic bio- polymers prepared by the surface pentafluorobenzoylation of cellulose substrates. Biomacromolecules 8:1347–1352CrossRefGoogle Scholar
  43. 43.
    Cassie ABD, Baxter S (1944) Wettability of porous surfaces. Trans Faraday Soc 40:546–551CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2014

Authors and Affiliations

  • A. Benkaddour
    • 1
  • C. Journoux-Lapp
    • 1
  • K. Jradi
    • 1
    Email author
  • S. Robert
    • 1
  • C. Daneault
    • 2
  1. 1.Lignocellulosic Material Research CentreUniversité du Québec à Trois-RivièresTrois-RivièresCanada
  2. 2.Canada Research Chair in Value-Added PaperUniversité du Québec à Trois RivièresTrois-RivièresCanada

Personalised recommendations