, Volume 18, Issue 2, pp 393–404

Heterogeneous modification of various celluloses with fatty acids

  • Pirita Uschanov
  • Leena-Sisko Johansson
  • Sirkka Liisa Maunu
  • Janne Laine


Heterogeneous modification of various types of cellulose (microcrystalline cellulose, cellulose whiskers and regenerated cellulose) was performed with long-chain fatty acids by an esterification reaction. The differences in reactivity between the celluloses were studied as well as the influences of the chain length and double bond content of the fatty acids. The success of the modification reaction and the structure of modified samples were studied with diverse characterization methods. Surface modification changed the thermal stability of cellulose by decreasing the degradation temperature but also made the pyrolysis curve two-stepped due to the double bonds in the fatty acid chain. It was observed that the nature of the fatty acid affected the degree of substitution (DS). The longer the fatty acid chain was, the lower was the DS. Fatty acids with increased double bond content gave decreased DS. Regenerated cellulose seemed to have the highest surface reactivity due to the distinct morphological structure, which also led to a much lower quantity of fatty acids attached to the structure than for other modified cellulose particles. The mixture of tall oil fatty acids behaved in the same manner as the commercial fatty acids, proving to be an excellent “green” choice for this kind of application.


Microcrystalline cellulose Whisker Fatty acid Surface modification Esterification 


  1. Battista OA, Armstrong AT, Radchenko SS (1978) Novel derivatives of cellulose microcrystals. Polym Prepr Am Chem Soc Div Polym Chem 19:567–571Google Scholar
  2. Belgacem MN, Gandini A (2005) The surface modification of cellulose fibres for use as reinforcing elements in composite materials. Compos Interfaces 12:41–75CrossRefGoogle Scholar
  3. Belgacem MN, Gandini A (2008) Surface modification of cellulose fibers. In: Belgacem MN, Gandini A (eds) Monomers, polymers and composites from renewable resources, 1st edn. Elsevier, Oxford, pp 385–400CrossRefGoogle Scholar
  4. Bondeson D, Oksman K (2007) Dispersion and characteristics of surfactant modified cellulose whiskers nanocomposites. Compos Interfaces 14:617–630CrossRefGoogle Scholar
  5. Bondeson D, Mathew A, Oksman K (2006) Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis. Cellulose 13:171–180CrossRefGoogle Scholar
  6. Braun B, Dorgan JR (2009) Single-step method for the isolation and surface functionalization of cellulosic nanowhiskers. Biomacromolecules 10:334–341CrossRefGoogle Scholar
  7. Fink H-P, Walenta E, Kunze J (1999) The structure of natural cellulosic fibers. Part 2: the supermolecular structure of bast fibers and their changes by mercerization as revealed by x-ray diffraction and 13C-NMR spectroscopy. Papier 53:534–542Google Scholar
  8. Fink H-P, Weigel P, Purz HJ, Ganster J (2001) Structure formation of regenerated cellulose materials from NMMO-solutions. Prog Polym Sci 26:1473–1524CrossRefGoogle Scholar
  9. Freire CSR, Silvestre AJD, Pascoal Neto C, Belgacem MN, Gandini A (2006a) 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 100:1093–1102CrossRefGoogle Scholar
  10. Freire CSR, Silvestre AJD, Pascoal Neto C, Gandini A, Fardim P, Holmbom B (2006b) Surface characterization by XPS, contact angle measurements and ToF-SIMS of cellulose fibers partially esterified with fatty acids. J Colloid Interf Sci 301:205–209CrossRefGoogle Scholar
  11. Freire CSR, Silvestre AJD, Pascoal Neto C, Gandini A, Martin L, Mondragon I (2008) Composites based on acylated cellulose fibers and low-density polyethylene: effect of the fiber content, degree of substitution and fatty acid chain length on final properties. Compos Sci Technol 68:3358–3364CrossRefGoogle Scholar
  12. Goetz L, Mathew A, Oksman K, Gatenholm P, Ragauskas AJ (2009) A novel nanocomposite film prepared from crosslinked cellulosic whiskers. Carbohydr Polym 75:85–89CrossRefGoogle Scholar
  13. Goussé C, Chanzy H, Cerrada ML, Fleury E (2004) Surface silylation of cellulose microfibrils: preparation and rheological properties. Polymer 45:1569–1575CrossRefGoogle Scholar
  14. Grun A, Wittka F (1921) Representation and esterification of cellulose esters: stearic and lauric acids of cellulose. Z Angew Chem 34:645–648CrossRefGoogle Scholar
  15. Heinze T, Petzold K (2008) Cellulose chemistry: novel products and synthesis paths. In: Belgacem MN, Gandini A (eds) Monomers, polymers and composites from renewable resources, 1st edn. Elsevier, Oxford, pp 343–368CrossRefGoogle Scholar
  16. Hubbe MA, Rojas OJ, Lucia LA, Sain M (2008) Cellulosic nanocomposites: a review. BioResources 3:929–980Google Scholar
  17. Jandura P, Kokta BV, Riedl B (2000a) Fibrous long-chain organic acid cellulose esters and their characterization by diffuse reflectance FTIR spectroscopy, solid-state CP/MAS carbon-13 NMR, and x-ray diffraction. J Appl Polym Sci 78:1354–1365CrossRefGoogle Scholar
  18. Jandura P, Riedl B, Kokta BV (2000b) Thermal degradation behavior of cellulose fibers partially esterified with some long chain organic acids. Polym Degrad Stab 70:387–394CrossRefGoogle Scholar
  19. Johansson L, Campbell JM (2004) Reproducible XPS on biopolymers: cellulose studies. Surf Interface Anal 36:1018–1022CrossRefGoogle Scholar
  20. Johansson L, Campbell JM, Koljonen K, Stenius P (1999) Evaluation of surface lignin on cellulose fibers with XPS. Appl Surf Sci 144–145:92–95CrossRefGoogle Scholar
  21. Katz S, Beatson RP, Scallan AM (1984) The determination of strong and weak acidic groups in sulfite pulps. Sven Papperstidn 6:48–53Google Scholar
  22. Klemm D, Heublein B, Fink H, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Ed 44:3358–3393CrossRefGoogle Scholar
  23. Kvien I, Tanem BS, Oksman K (2005) Characterization of cellulose whiskers and their nanocomposites by atomic force and electron microscopy. Biomacromolecules 6:3160–3165CrossRefGoogle Scholar
  24. Malm CJ, Mench JW, Kendall DL, Hiatt GD (1951) Aliphatic acid esters of cellulose. Ind Eng Chem 43:688–691CrossRefGoogle Scholar
  25. Matsumura H, Sugiyama J, Glasser WG (2000) Cellulosic nanocomposites. I. Thermally deformable cellulose hexanoates from heterogeneous reaction. J Appl Polym Sci 78:2242–2253CrossRefGoogle Scholar
  26. Maunu SL (2002) NMR studies of wood and wood products. Prog Nucl Magn Reson Spectrosc 40:151–174CrossRefGoogle Scholar
  27. Pasquini D, Belgacem MN, Gandini A, Curvelo AAdS (2006) Surface esterification of cellulose fibers: characterization by DRIFT and contact angle measurements. J Colloid Interf Sci 295:79–83CrossRefGoogle Scholar
  28. Petzold K, Koschella A, Klemm D, Heublein B (2003) Silylation of cellulose and starch—selectivity, structure analysis, and subsequent reactions. Cellulose 10:251–269CrossRefGoogle Scholar
  29. Sealey JE, Samaranayake G, Todd JG, Glasser WG (1996) Novel cellulose derivatives. IV. Preparation and thermal analysis of waxy esters of cellulose. J Polym Sci B 34:1613–1620CrossRefGoogle Scholar
  30. Shimzu YI, Hayashi J (1989) Acylation of cellulose with carboxylic acids. Cell Chem Technol 23:661–670Google Scholar
  31. Szczesniak L, Rachocki A, Tritt-Goc J (2008) Glass transition temperature and thermal decomposition of cellulose powder. Cellulose 15:445–451CrossRefGoogle Scholar
  32. Vittadini E, Dickinson LC, Chinachoti P (2001) 1H and 2H NMR mobility in cellulose. Carbohydr Polym 46:49–57CrossRefGoogle Scholar
  33. Yuan H, Nishiyama Y, Wada M, Kuga S (2006) Surface acylation of cellulose whiskers by drying aqueous emulsion. Biomacromolecules 7:696–700CrossRefGoogle Scholar
  34. Zhao H, Kwak JH, Wang Y, Franz JA, White JM, Holladay JE (2007) Interactions between cellulose and N-methylmorpholine-N-oxide. Carbohydr Polym 67:97–103CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2010

Authors and Affiliations

  • Pirita Uschanov
    • 1
  • Leena-Sisko Johansson
    • 2
  • Sirkka Liisa Maunu
    • 1
  • Janne Laine
    • 2
  1. 1.Laboratory of Polymer ChemistryUniversity of HelsinkiHelsinkiFinland
  2. 2.Department of Forest Products Technology, School of Science and TechnologyAalto UniversityAaltoFinland

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