, Volume 12, Issue 4, pp 435–444 | Cite as

Starch Derivatives of High Degree of Functionalization 11: Studies on Alternative Acylation of Starch with Long-chain Fatty Acids Homogeneously in N,N-dimethyl acetamide/LiCl



Starch materials of different amylose content were allowed to react with saturated and unsaturated fatty acids of varying chain length from C14 to C18 under homogeneous conditions applying the solvent N,N-dimethyl acetamide in combination with LiCl. As reagent the corresponding acid chlorides and, alternatively, carboxylic acids in situ activated with toluene-4-sulfonyl chloride and N,N′-carbonyldiimidazole (CDI) were studied. Using fatty acid chlorides (FACl) and toluene-4-sulfonyl chloride-activated acids an almost complete substitution of the starch occurs. By in situ activation of the fatty acids with CDI, products with a degree of substitution up to 2 were obtained, which, in particular, represents a simple and very mild procedure.

Key words

N,N′-Carbonyldiimidazole N,N-Dimethyl acetamide/LiCl Esterification Long-chain fatty acid Polysaccharide Starch Toluene-4-sulfonyl chloride 


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  1. Aburto, J., Alric, I., Borrredon, E. 1999bPreparation of long chain esters of starch using fatty acid chlorides in the absence of an organic solventStarch/Stärke51132135CrossRefGoogle Scholar
  2. Aburto, J., Hamaili, H., Mousset-Baziard, G., Senocq, F., Alric, I., Borredon, E. 1999cFree-solvent synthesis and properties of higher fatty esters of starch – Part 2Starch/Stärke51302307CrossRefGoogle Scholar
  3. Aburto, J., Thiebaud, S., Alric, I., Borredon, E., Bikiaris, D., Prinos, J., Panayiotou, C. 1997Properties of octanoated starch and blends with polyethyleneCarbohydr. Polym.34101112CrossRefGoogle Scholar
  4. Aburto, J., Thiebaud, S., Alric, I., Borredon, E., Bikiaris, D., Prinos, J., Panayiotou, C. 1999aSynthesis, characterization and biodegradability of fatty-acid esters of amylose and starchJ. Appl. Polym. Sci.7414401451CrossRefGoogle Scholar
  5. Bader H., Rafler G., Lang J., Lindhauer M., Klaas M.R., Funke U. and Warwel S. inventors 1997. EP 0859012 A2: Verfahren zur Herstellung von bioabbaubaren Werkstoffen. Fraunhofer-Gesellschaft zur Förderung der Angewandten Forschung e. V. Chem. Abstr. 1998 129: 204–389.Google Scholar
  6. Becker, H.G.O., Berger, W., Domschke, G., Fanghänel, E., Faust, J., Fischer, M., Gentz, F., Gewald, K., Gluch, R., Mayer, R., Müller, K., Pavel, D., Schwedtlick, K., Seiler, E., Zeppenfeld, G. 1981Organikum. 2. Reprint15. EditionVEB Deutscher Verlag der WissenschaftenBerlin504505Google Scholar
  7. Bikiaris, D., Aburto, J., Alric, I., Borrredon, E., Botev, M., Betchev, C., Panayiotou, C. 1999Mechanical properties and biodegradability of LDPE blends with fatty-acid esters of amylose and starchJ. Appl. Polym. Sci.7110891100CrossRefGoogle Scholar
  8. Brewster, J.H., Ciotti, C.J.,,Jr. 1955Dehydrations with aromatic sulfonyl halides in pyridine. A convenient method for the preparation of estersJ. Am. Chem. Soc.7762146215CrossRefGoogle Scholar
  9. Dicke, R., Rahn, K., Haack, V., Heinze, Th. 2001Starch derivatives of high degree of functionalization Part 2. Determination of the functionalization pattern of p-toluenesulfonyl starch by peracetylation and NMR spectroscopyCarbohydr. Polym.454351CrossRefGoogle Scholar
  10. Fang, J.M., Fowler, P.A., Tomkinson, J., Hill, C.A.S. 2002The preparation and characterization of a series of chemically modified potato starchesCarbohydr. Polym.47245252CrossRefGoogle Scholar
  11. Frigant, C., Rinaudo, M., Foray, M.F., Bardet, M. 1998Preparation of mixed esters of starch or use of an external plasticizer: two different ways to change the properties of starch acetate filmsCarbohydr. Polym.3597106CrossRefGoogle Scholar
  12. Glasser, W.G., Becker, U., Todd, J.G. 2000Novel cellulose derivatives. Part VI. Preparation and thermal analysis of two novel cellulose esters with fluorine-containing substituentsCarbohydr. Polym.42393400CrossRefGoogle Scholar
  13. Gräbner, D., Liebert, T., Heinze, T. 2002Synthesis of novel adamantoyl cellulose using differently activated carboxylic acid derivativesCellulose9193201CrossRefGoogle Scholar
  14. Gros, A.T., Feuge, R.O. 1962Properties of fatty acid esters of amyloseJ. Am. Oil Chem. Soc.391924Google Scholar
  15. Heinze, T., Liebert, T. 2001Unconventional methods in cellulose functionalizationProgr. Polym. Sci.2616891762CrossRefGoogle Scholar
  16. Heinze, T., Schaller, J. 2000New water-soluble cellulose esters synthesized by an effective acylation procedureMacromol. Chem. Phys.20112141218CrossRefGoogle Scholar
  17. Heinze, T., Talaba, P., Heinze, U. 2000Starch derivatives of high degree of functionalization. 1. Effectivehomogeneous synthesis of p-toluenesulfonyl (tosyl) starch with a new functionalization patternCarbohydr. Polym.42411420CrossRefGoogle Scholar
  18. Hussain, M.A., Liebert, T., Heinze, Th. 2004Acylation of cellulose with NN′-carbonyldiimidazole-activated acids in the novel solvent dimethyl sulfoxide/tetrabutylammonium fluorideMacromol. Rapid Commun.25916920CrossRefGoogle Scholar
  19. Jonker, E.H. 1991EP 0486092 A1: fatty esters of starch method of preparing and use. AKZO NVChem. Abstr.1992117133259Google Scholar
  20. Koschella, A., Hauke, G., Heinze, T. 1997New fluorescence active cellulosics prepared by a convenient acylation procedurePolym. Bull.39597604CrossRefGoogle Scholar
  21. Lower, E.S. 1996Starchfatty, organic and inorganic acid estersLa Rivista Italiana Delle Sostanza Grasse73159163Google Scholar
  22. Neumann, U., Wiege, B., Warwel, S. 2002Synthesis of hydrophobic starch esters by reaction of starch with various carboxylic acid imidazolidesStarch/Stärke54449453CrossRefGoogle Scholar
  23. Peltonen S. and Harju K. inventors 1994. WO 94/22919: fatty acid esters of polysaccharides, their preparation and use in adhesive coatings. Oy Alko Ab. Chem. Abstr. 1995 123: 86469.Google Scholar
  24. Rooney, M.L. 1976Interesterification of starch with methyl palmitatePolymer17555558CrossRefGoogle Scholar
  25. Sagar, A.D., Merrill, E.W. 1995Properties of fatty acid esters of starchJ. Appl. Polym. Sci.5816471656CrossRefGoogle Scholar
  26. Samaranayake, G., Glasser, W.G. 1993Cellulose derivatives with low DS – I: A novel acylation systemCarbohydr. Polym.2217CrossRefGoogle Scholar
  27. Sealey, J.E., Samaranayake, G., Glasser, W.G. 2000Novel cellulose derivatives. V. Synthesis and thermal properties of esters with trifluoroethoxy acetic acidJ. Polym. Sci.38486494Google Scholar
  28. Sealey, J.E., Samaranayake, G., Todd, J.G., Glasser, W.G. 1996Novel cellulose derivatives. IV. Preparation and thermal analysis of waxy esters of celluloseJ. Polym. Sci. Part B: Polym. Phys.3416131620CrossRefGoogle Scholar
  29. Shimizu, Y., Hayashi, J. 1988A new method for cellulose acetylation with acetic acidSen-I Gakkaishi44451456Google Scholar
  30. Staab, H.A. 1962Synthesen mit heterocyclischen Amiden (Azoliden)Angew. Chem.74407423Google Scholar
  31. Teng J. and Rha C. inventors 1970. US 3,666,492: chewing gum. Anheuser Busch Inc. Chem. Abstr. 1972 77: 60348.Google Scholar
  32. Tessler M.M. inventors 1972. DE 2230884: Verfahren zur Herstellung von Stärkeestern. National Starch and Chemical Corp. Chem. Abstr. 1973 78: 99447.Google Scholar
  33. Thiebaud, S., Aburto, J., Alric, I., Borrredon, E., Bikiaris, D., Prinos, J., Panayiotou, C. 1997Properties of fatty-acid esters of starch and their blends with LDPEJ. Appl. Polym. Sci.65705721CrossRefGoogle Scholar
  34. Vaca-Garcia, C., Borredon, M. E. 1999Solvent-free fatty acylation of cellulose and lignocellulosic wastes. Part 2: Reactions with fatty acidsBiores. Technol.70135142CrossRefGoogle Scholar
  35. Vaca-Garcia, C., Thiebaud, S., Borredon, M.E., Gozzelino, G. 1998Cellulose esterification with fatty acids and acetic anhydride in lithium chloride/NN-dimethylacetamide mediumJ. Am. Chem. Soc.75315319Google Scholar
  36. Whistler, R.L., Madson, M.A., Zhao, L., Daniel, J.R. 1988Surface derivatization of corn starch granulesCereal Chem.757274Google Scholar

Copyright information

© Springer 2005

Authors and Affiliations

  1. 1.Kompetenzzentrum PolysaccharidforschungFriedrich-Schiller-Universität JenaJenaGermany

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