, Volume 21, Issue 4, pp 2519–2527 | Cite as

Acetylation and stepwise solvent-exchange to modify hydrophilic cellulose whiskers to polychloroprene-compatible nanofiller

Original Paper


The acetylation of cellulose nanofiber (CNF) introduced hydrophobicity to the surface making it compatible with non-polar matrix, and also making it an effective nanofiller for polychloroprene (PCR) composite. The CNF was extracted from oil palm empty fruit bunches. Previously, CNF was dispersed in water, and this water was subsequently substituted with N,N-dimethylacetamide, in which CNF was acetylated by acetic anhydride with a pyridine catalyst. IR spectroscopy revealed that the acetylation extent was controllable by the reaction time. After the reaction, the DMAc was replaced by dichloromethane, and finally mixed with PCR. The CNF–PCR mixture was cast and composite film was formed at room temperature. Structural analysis and mechanical tests indicated that acetylation treatment made CNF compatible with PCR, and that nano-dispersed CNF raised the mechanical strength of the PCR–CNF nanocomposite.


Cellulose nanofiber Acetylation Nanocomposite Polychloroprene OPEFB 



This study was funded by the Japan Society for the Promotion of Science (JSPS 23-01401) through a postdoctoral fellowship for foreign researchers awarded to Farah Fahma.


  1. Abe K, Yano H (2009) Cellulose nanofiber-based hydrogels with high mechanical strength. Cellulose 16:1017–1023CrossRefGoogle Scholar
  2. Alemdar A, Sain M (2008) Isolation and characterization of nanofibers from agricultural residues—wheat straw and soy hulls. Bioresour Technol 99:1664–1671CrossRefGoogle Scholar
  3. Beck-Candanedo S, Roman M, Gray DG (2005) Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions. Biomacromolecules 6:1048–1054CrossRefGoogle Scholar
  4. Bhattacharya D, Germinario LT, Winter WT (2008) Isolation, preparation and characterization of cellulose microfibers obtained from bagasse. Carbohydr Polym 73:371–377CrossRefGoogle Scholar
  5. Cavaille JY, Chanzy H, Fleury E, Sassi JF (1997) Surface modified cellulose microfibrils, method for making the same, and use thereof as a filler in composite materials. US Patent 6,117.545Google Scholar
  6. Cetin NH, Taingaut P, Ozmen N, Henry N, Harper D, Dadmun M, Sebe G (2009) Acetylation of cellulose nanowhiskers with vinyl acetate under moderate conditions. Macromol Biosci 9:997–1003CrossRefGoogle Scholar
  7. Chen Y, Liu C, Chang PR, Cao X, Anderson DP (2009) Bionanocomposites based on pea starch and cellulose nanowhiskers hydrolyzed from pea hull fibre: effect of hydrolysis time. Carbohydr Polym 76:607–615CrossRefGoogle Scholar
  8. Cherian BM, Pothan LA, Nguyen-Chung T, Mennig G, Kottaisamy M, Thomas S (2008) A novel method for the synthesis of cellulose nanofibril whiskers from banana fibers and characterization. J Agric Food Chem 56:5617–5627CrossRefGoogle Scholar
  9. de Rodriguez NLG, Thielemans W, Dufresne A (2006) Sisal cellulose whiskers reinforced polyvinyl acetate nanocomposites. Cellulose 13:261–270CrossRefGoogle Scholar
  10. Eichhorn SJ, Dufresne A, Aranguren M, Marcovich NE, Capadona JR, Rowan SJ, Weder C, Thielemans W, Roman M, Renneckar S, Gindl W, Veigel S, Keckes J, Yano H, Abe K, Nogi M, Nakagaito AN, Mangalam A, Simonsen J, Benight AS, Bismarck A, Berglund LA, Peijs T (2010) Review: current international research into cellulose nanofibres and nanocomposites. J Mater Sci 45:1–33CrossRefGoogle Scholar
  11. Fahma F, Iwamoto S, Hori N, Iwata T, Takemura A (2010) Isolation, preparation, and characterization of nanofibers from oil palm empty-fruit-bunch (OPEFB). Cellulose 17:977–985CrossRefGoogle Scholar
  12. Fahma F, Iwamoto S, Hori N, Iwata T, Takemura A (2011) Effect of pre-acid-hydrolysis treatment on morphology and properties of cellulose nanowhiskers from coconut husk. Cellulose 18:443–450CrossRefGoogle Scholar
  13. Fahma F, Hori N, Iwata T, Takemura A (2013) The morphology and properties of poly(methyl methacrylate)-cellulose nanocomposites prepared by immersion precipitation method. J Appl Polym Sci 128:1563–1568Google Scholar
  14. Favier V, Chanzy H, Cavaille JY (1995) Polymer nanocomposites reinfordced by cellulose whiskers. Macromolecules 28:6365–6367CrossRefGoogle Scholar
  15. Frisoni G, Baiardo M, Scandola M (2001) Natural cellulose fibers: heterogeneous acetylation kinetics and biodegradation behavior. Biomacromolecules 2:476–482CrossRefGoogle Scholar
  16. Gañán P, Cruz J, Garbizu S, Arbelaiz A, Mondragon M (2004) Stem and bunch banana fibers from cultivation wastes: effect of treatments on physico-chemical behavior. J Appl Polym Sci 94:1489–1495CrossRefGoogle Scholar
  17. Gousse C, Chanzy H, Cerradab ML, Fleury E (2004) Surface silylation of cellulose microfibrils: preparation and rheological properties. Polymer 45(5):1569–1575CrossRefGoogle Scholar
  18. Grunert M, Winter WT (2002) Nanocomposites of cellulose acetate butyrate reinforced with cellulose nanocrystals. J Polym Environ 10:27–30CrossRefGoogle Scholar
  19. Hanley SJ, Giasson J, Revol JF, Gray DG (1992) Atomic force microscopy of cellulose microfibrils—comparison with transmission electron-microscopy. Polymer 33:4639–4642CrossRefGoogle Scholar
  20. Ifuku S, Morooka S, Morimoto M, Saimoto H (2010) Acetylation of chitin nanofibers and their transparent nanocomposite films. Biomacromolecules 11:1326–1330CrossRefGoogle Scholar
  21. Isogai A, Usuda M (1990) Crystallinity indexes of cellulosic materials. Sen’I Gakkaishi 46:324–329CrossRefGoogle Scholar
  22. Ladouce L, Fleury, E, Gousse C, Cantiani R, Chanzy H, Excoffier G (2000) Cellulose microfibrils with modified surface, preparation method and use thereof. US Patent 6,703,497Google Scholar
  23. Moran JI, Alvarez VA, Cyras VP, Vazquez A (2008) Extraction of cellulose and preparation of nanocellulose from sisal fibers. Cellulose 15:149–159CrossRefGoogle Scholar
  24. Oksman K, Etang JA, Mathew AP, Jonoobi M (2011) Cellulose nanowhiskers separated from a bio-residue from wood bioethanol production. Biomass Bioenergy 35:146–152CrossRefGoogle Scholar
  25. Rosa MF, Medeiros ES, Malmonge JA, Gregorski KS, Wood DF, Mattoso LHC, Glenn G, Orts WJ, Imam SH (2010) Cellulose nanowhiskers from coconut husk fibers: effect of preparation conditions on their thermal and morphological behavior. Carbohydr Polym 81:83–92CrossRefGoogle Scholar
  26. Sassi JF, Chanzy H (1995) Ultrastructural aspects of the acetylation of cellulose. Cellulose 2:111–127CrossRefGoogle Scholar
  27. Teixeira ED, Pasquini D, Curvelo AAS, Corradini E, Belgacem MN, Dufresne A (2009) Cassava bagasse cellulose nanofibrils reinforced thermoplastic cassava starch. Carbohydr Polym 78:422–431CrossRefGoogle Scholar
  28. Terech P, Chazeau L, Cavaille JY (1999) A small-angle scattering study of cellulose whiskers in aqueous suspensions. Macromolecules 32:1872–1875CrossRefGoogle Scholar
  29. Tingaut P, Zimmermann T, Lopez-Suevos F (2010) Synthesis and characterization of bionanocomposites with tunable properties from poly (lactic acid) and acetylated micro-brillated cellulose. Biomacromolecules 11(2):454–464CrossRefGoogle Scholar
  30. Wada M, Okano T, Sugiyama J (1997) Synchrotron-radiated X-ray and neutron diffraction study of native cellulose. Cellulose 4:221–232CrossRefGoogle Scholar
  31. Wang B, Sain M (2007) Dispersion of soybean stock-based nanofiber in a plastic matrix. Polym Int 56:538–546CrossRefGoogle Scholar
  32. Wu J, Zhang J, Zhang H, He J, Ren Q, Guo M (2004) Homogeneous acetylation of cellulose in a new ionic liquid. Biomacromolecules 5:266–268CrossRefGoogle Scholar
  33. Zimmermann T, Bordeanu N, Strub E (2010) Properties of nanofibrillated cellulose from different raw materials and its reinforcement potential. Carbohydr Polym 79:1086–1093CrossRefGoogle Scholar
  34. Zini E, Scandola M (2003) Heterogeneous acylation of flax fibers. reaction kinetics and surface properties. Biomacromolecules 4:821–827CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2014

Authors and Affiliations

  1. 1.Graduate School of Agricultural and Life SciencesThe University of TokyoTokyoJapan
  2. 2.Department of Agroindustrial TechnologyBogor Agricultural UniversityBogorIndonesia

Personalised recommendations