, Volume 23, Issue 2, pp 1209–1219 | Cite as

One-pot preparation of hydrophobic cellulose nanocrystals in an ionic liquid

  • Jiaojiao Miao
  • Yongqi Yu
  • Zeming Jiang
  • Liping Zhang
Original Paper


The facile one-pot preparation of hydrophobic cellulose nanocrystals (CNCs) from wood pulpboard in an ionic liquid is reported in the present paper. This process employed a so-called amorphous cellulose solvent system capable of dissolving the majority of the amorphous regions in cellulose while maintaining the crystalline domains essentially intact, and consisting of tetrabutylammonium acetate with dimethylacetamide. These solvents were mixed at a mass ratio of 1:9 in conjunction with acetic anhydride to prepare CNCs via surface acetylation. The rod-like morphology and nanometer-scale dimensions of the resulting CNCs were ascertained by atomic force microscopy and transmission electron microscopy. Successful surface acetylation while maintaining an intact crystalline core was confirmed by Fourier transform infrared, 13C CP/MAS NMR and X-ray photoelectron spectroscopy in addition to X-ray diffraction. Finally, the thermal stability and hydrophobic behavior of the hydrophobic CNCs were characterized using thermal gravimetric analysis and water contact-angle measurements, respectively.


Tetrabutylammonium acetate Hydrophobic CNC One-pot method Surface modification Amorphous cellulose solvent system 



The authors wish to acknowledge the financial support of the Fundamental Research Funds for the Central Universities (No. BJYJ 201518) and the “948” Project of the State Forestry Administration (No. 2013-4-03).

Supplementary material

10570_2016_864_MOESM1_ESM.avi (69 mb)
Supplementary material 1 (AVI 70660 kb)
10570_2016_864_MOESM2_ESM.docx (730 kb)
Supplementary material 2 (DOCX 729 kb)


  1. Adebajo MO, Frost RL, Kloprogge JT, Kokot S (2006) Raman spectroscopic investigation of acetylation of raw cotton. Spectrochim Acta A Mol Biomol Spectrosc 64:448–453CrossRefGoogle Scholar
  2. Andresen M, Johansson L-S, Tanem BS, Stenius P (2006) Properties and characterization of hydrophobized microfibrillated cellulose. Cellulose 13:665–677CrossRefGoogle Scholar
  3. Braun B, Dorgan JR (2008) Single-step method for the isolation and surface functionalization of cellulosic nanowhiskers. Biomacromolecules 10:334–341CrossRefGoogle Scholar
  4. Buchanan CM, Edgar KJ, Hyatt JA, Wilson AK (1991) Preparation of cellulose [1-carbon-13] acetates and determination of monomer composition by NMR spectroscopy. Macromolecules 24:3050–3059CrossRefGoogle Scholar
  5. Cetin NS, Tingaut P, Özmen N, Henry N, Harper D, Dadmun M, Sèbe G (2009) Acetylation of cellulose nanowhiskers with vinyl acetate under moderate conditions. Macromol Biosci 9:997–1003CrossRefGoogle Scholar
  6. Chen L, Wang Q, Hirth K, Baez C, Agarwal UP, Zhu J (2015) Tailoring the yield and characteristics of wood cellulose nanocrystals (CNC) using concentrated acid hydrolysis. Cellulose 22:1753–1762CrossRefGoogle Scholar
  7. Elazzouzi-Hafraoui S, Nishiyama Y, Putaux J-L, Heux L, Dubreuil F, Rochas C (2007) The shape and size distribution of crystalline nanoparticles prepared by acid hydrolysis of native cellulose. Biomacromolecules 9:57–65CrossRefGoogle Scholar
  8. Espino-Pérez E, Domenek S, Belgacem N, Sillard C, Bras J (2014) Green process for chemical functionalization of nanocellulose with carboxylic acids. Biomacromolecules 15:4551–4560CrossRefGoogle Scholar
  9. French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896CrossRefGoogle Scholar
  10. Habibi Y (2014) Key advances in the chemical modification of nanocelluloses. Chem Soc Rev 43:1519–1542CrossRefGoogle Scholar
  11. Habibi Y, Lucia LA, Rojas OJ (2010) Cellulose nanocrystals: chemistry, self-assembly, and applications. Chem Rev 110:3479–3500CrossRefGoogle Scholar
  12. Ifuku S, Nogi M, Abe K, Handa K, Nakatsubo F, Yano H (2007) Surface modification of bacterial cellulose nanofibers for property enhancement of optically transparent composites: dependence on acetyl-group DS. Biomacromolecules 8:1973–1978CrossRefGoogle Scholar
  13. Jonoobi M, Niska KO, Harun J, Misra M (2009) Chemical composition, crystallinity, and thermal degradation of bleached and unbleached kenaf bast (Hibiscus cannabinus) pulp and nanofibers. BioResources 4:626–639Google Scholar
  14. Jonoobi M, Harun J, Mathew AP, Hussein MZB, Oksman K (2010) Preparation of cellulose nanofibers with hydrophobic surface characteristics. Cellulose 17:299–307CrossRefGoogle Scholar
  15. Kim D-Y, Nishiyama Y, Kuga S (2002) Surface acetylation of bacterial cellulose. Cellulose 9:361–367CrossRefGoogle Scholar
  16. Klemm D, Kramer F, Moritz S, Lindström T, Ankerfors M, Gray D, Dorris A (2011) Nanocelluloses: a new family of nature-based materials. Angew Chem Int Ed Engl 50:5438–5466CrossRefGoogle Scholar
  17. Miao J, Sun H, Yu Y, Song X, Zhang L (2014) Quaternary ammonium acetate: an efficient ionic liquid for the dissolution and regeneration of cellulose. RSC Adv 4:36721–36724CrossRefGoogle Scholar
  18. Missoum K, Belgacem MN, Barnes J-P, Brochier-Salon M-C, Bras J (2012) Nanofibrillated cellulose surface grafting in ionic liquid. Soft Matter 8:8338–8349CrossRefGoogle Scholar
  19. Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994CrossRefGoogle Scholar
  20. Salajková M, Berglund LA, Zhou Q (2012) Hydrophobic cellulose nanocrystals modified with quaternary ammonium salts. J Mater Chem 22:19798–19805CrossRefGoogle Scholar
  21. Samir MASA, Alloin F, Sanchez J-Y, Dufresne A (2005) Nanocomposite polymer electrolytes based on poly (oxyethylene) and cellulose whiskers. Polímeros 15:109–113CrossRefGoogle Scholar
  22. Sassi J-F, Chanzy H (1995) Ultrastructural aspects of the acetylation of cellulose. Cellulose 2:111–127CrossRefGoogle Scholar
  23. Siqueira G, Bras J, Dufresne A (2010) Cellulosic bionanocomposites: a review of preparation, properties and applications. Polymers 2:728–765CrossRefGoogle Scholar
  24. Sun XF, Sun R (2002) Comparative study of acetylation of rice straw fiber with or without catalysts. Wood Fiber Sci 34:306–317Google Scholar
  25. Tserki V, Zafeiropoulos N, Simon F, Panayiotou C (2005) A study of the effect of acetylation and propionylation surface treatments on natural fibres. Compos A 36:1110–1118CrossRefGoogle Scholar
  26. Xiang Q, Lee Y, Pettersson PO, Torget RW (2003) Heterogeneous aspects of acid hydrolysis of α-cellulose. In: Biotechnology for fuels and chemicals. Springer, pp 505–514Google Scholar
  27. Zafeiropoulos N, Baillie C (2007) A study of the effect of surface treatments on the tensile strength of flax fibres—part II: application of Weibull statistics. Compos A 38:629–638CrossRefGoogle Scholar
  28. Zhang H, Wu J, Zhang J, He J (2005) 1-Allyl-3-methylimidazolium chloride room temperature ionic liquid: a new and powerful nonderivatizing solvent for cellulose. Macromolecules 38:8272–8277CrossRefGoogle Scholar
  29. Zhao Y, Liu X, Wang J, Zhang S (2013) Insight into the cosolvent effect of cellulose dissolution in imidazolium-based ionic liquid systems. J Phys Chem B 117:9042–9049CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2016

Authors and Affiliations

  • Jiaojiao Miao
    • 1
  • Yongqi Yu
    • 1
  • Zeming Jiang
    • 1
  • Liping Zhang
    • 1
  1. 1.Beijing Key Laboratory of Lignocellulosic Chemistry, MOE Engineering Research Center of Forestry Biomass Materials and Bioenergy, College of Materials Science and TechnologyBeijing Forestry UniversityBeijingPeople’s Republic of China

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