Skip to main content
SpringerLink
Log in

Synthesis and characterization of some long-chain diesters with branched or bulky moieties

  • Published:
Journal of the American Oil Chemists' Society

Abstract

Several novel fatty diesters with bulky moieties were synthesized by esterification of mono- or bifunctional fatty acids or with mono- or bifunctional alcohols using p-toluenesulfonic acid as catalyst. They were characterized by 1H and 13C nuclear magnetic resonance as well as positive chemical ionization (PCl) mass spectrometry. The PCl mass spectra of the resulting diol diesters and diacid diesters are discussed and compared. The compounds were investigated as potential additives for improving the cold flow properties of vegetable oil esters used as biodiesel.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Knothe, G., R.O. Dunn, and M.O. Bagby, Biodiesel: The Use of Vegetable Oils and Their Derivatives as Alternative Diesel Fuels, in ACS Symp. Ser. 666 (Fuels and Chemicals from Biomass), American Chemical Society, Washington, DC, 1997, pp. 172–208.

    Google Scholar 

  2. Dunn, R.O., G. Knothe, and M.O. Bagby, Recent Advances in the Development of Alternative Diesel Fuel from Vegetable Oils and Animal Fats, Recent Res. Devel. Oil Chem. 1:31–56 (1997).

    CAS  Google Scholar 

  3. Lee, I., L.A. Johnson, and E.G. Hammond, Use of Branched-Chain Esters to Reduce the Crystallization Temperature of Biodiesel, J. Am. Oil Chem. Soc. 72:1155–1160 (1995).

    Article  CAS  Google Scholar 

  4. Foglia, T.A., L.A. Nelson, R.O. Dunn, and W.N. Marmer, Low-Temperature Properties of Alkyl Esters of Tallow and Grease, 74:951–955 (1997).

    CAS  Google Scholar 

  5. Wu, W.-H., T.A. Foglia, W.N. Marmer, R.O. Dunn, C.E. Goering, and T.E. Briggs, Low-Temperature Property and Engine Performance Evaluation of Ethyl and Isopropyl Esters of Tallow and Grease, 75:1173–1178 (1998).

    CAS  Google Scholar 

  6. Lee, I., L.A. Johnson, and E.G. Hammond, Reducing the Crystallization Temperature of Biodiesel by Winterizing Methyl Soyate, 73:631–636 (1996).

    Article  CAS  Google Scholar 

  7. Dunn R.O., M.W. Shockley, and M.O. Bagby, Improving the Low-Temperature Properties of Alternative Diesel Fuels: Vegetable Oil-Derived Methyl Esters, 73:1719–1728 (1996).

    Article  CAS  Google Scholar 

  8. Dunn, R.O., Effect of Winterization on Fuel Properties of Methyl Soyate, in Proceedings of the Third Commercialization of Biodiesel Conference: Producing a Quality Biodiesel Fuel, edited by C.L. Peterson, University of Idaho, Moscow, ID, 1998, pp. 164–186.

    Google Scholar 

  9. Dunn, R.O., M.W. Shockley, and M.O. Bagby, Winterized Methyl Esters from Soybean Oil: An Alternative Fuel with Improved Low-Temperature Flow Properties, SAE Techn. Pap. Ser. 971682, published in State of Alternative Fuel Technologies SP-1274, SAE, Warrendale, PA, 1997, pp. 133–142.

    Google Scholar 

  10. Fujii, K., M. Izumi, and M. Nakahara (Sanken Kako Co., Ltd.), Lubricating Oils for Refrigerators Using Tetrafluoroethane as Refrigerant, Japanese Patent 4,183,789 (1992).

  11. Cornils, B., J. Weber, P. Lappe, H. Springer, E. Preisegger, and R. Henrici (Hoechst AG), The Use of Ester Oils as Lubricants in Refrigeration Compression, Eur. Pat. Appl. EP 445,611 (1991).

    Google Scholar 

  12. Suzuki, N., J. Nishi, and Y. Ishii, Lubricants Containing Fatty Acid Esters for Processing Thermoplastic Synthetic Fibers, Japanese Patent JP 03 33,627 [91 33,267].

  13. Koch, K.H., and H. Kroke (Henkel und Cie. GmbH), Ester Lubricants and Hydraulic Fluids, German Patent 2,302,918 (1974).

  14. Goethel, H., and H. Feichtinger (Ruhrchemie AG), Lubricants Based on Aliphatic Carboxylic Acid Diesters, German Patent 1,912,486 (1970).

  15. Aylesworth, R.D., and R.H. Boehringer (Emery Industries, Inc.), Blends of Ester Lubricants, U.S. Patent 3,309,918 (1967).

  16. Nanu, I., and R.F. Pape, Weichmachereigenschaften von Diestern mit Neoalkylstruktur, Plaste Kautsch. 26:301–306 (1979).

    CAS  Google Scholar 

  17. Nanu, L., and R.F. Pape, Diesters of Neopentyl Glycol. Evaluation of Plasticizing. Properties, Mater. Plast. (Bucharest) 16:218–220 (1979). Chem. Abstr. 92:164673x.

    CAS  Google Scholar 

  18. Uehara, K., and H. Katsura (Shiseido Co., Ltd.), Cosmetic Neopentyl Glycol Esters, Japanese Patent 80 02,648 (1980).

  19. Finley, J.W., and A. Scimone (Nabisco, Inc.), Diol Lipid Analogs as Edible Fat Replacers, U.S. Patent 5,286,512 (1994).

  20. Givens, P.S., Jr., E.L. Wheeler, R.P. D'Amelia, M.S. Otterburn, G.A. Leveille, J.W. Finley, and L.P. Klemann (Nabisco Brands, Inc.), Cyclohexyl Diol Diesters as Low-Calorie Fat Mimetics, U.S. Patent 5,006,351 (1989).

  21. Isa, H., T. Inagaki, Y. Shimizu, and M. Nagayama (Lion Fat and Oil Co., Ltd.), Esters of Polyhydric Alcohols, Japanese Patent 75 62,925 (1975).

  22. Shinei Kagaku, K.K., and K.K. Shinko Kagaku, C22-Dihydric Alcohol Mixture, Japanese Patent 80,167234 (1980).

    Google Scholar 

  23. Bhatnagar, A.K., and K.K. Bhattacharyya, Synthetic Ester Lubricants: Pt. I—Synthesis and Properties of 2,2,-Dialkyl-1,3-propanediol Esters, J. Indian Chem. Soc. 58:594–596 (1981).

    CAS  Google Scholar 

  24. Bochkova, V.A., V.A. Proskuryakov, K.V. Puzitskii, S.D. Pirozhkov, and Y.T. Eidus, Synthesis and Properties of Esters of α,α-Dimethylalkanoic Acids and Polyhydric Alcohols, Zh. Prikl. Khim. (Leningrad) 46:1818–1822 (1973) Chem. Abstr. 79:125776v.

    CAS  Google Scholar 

  25. Volkova, I.A., V.A. Proskuryakov, and V.V. Gromova, Esters of Dodecanedioic Acid with Monohydric Alcohols, Okislenie Uglevodorodov, Ikh Proizvod. Bitumov: 15–19 (1971), from Rfe. Zh., Khim. 1972, Abstract No. 24Zh181. Chem. Abstr. 79:4962u.

  26. Ucciani, E., M. Schmitt-Rozieres, A. Debai, and L.C. Comeau, Enzymatic Synthesis of Some Wax Esters, Fett/Lipid 98:206–210 (1996).

    Article  CAS  Google Scholar 

  27. Zeman, A., P. Bartl, and A. Schaaff, Die massenspektrometrische Fragmentierung von Neopentylpolyolestern. III Neopentylglycoldifettsäureester, Fette Seifen Anstrichm. 80:388–392 (1978).

    Article  CAS  Google Scholar 

  28. Zeman, A., P. Bartl, and A. Schaaff, Die massenspektrometrische Fragmentierung von Neopentylpolyolestern. I. Pentaerythrittetrafettsäureester, Org. Mass Spectrom. 13:248–253 (1978).

    Article  CAS  Google Scholar 

  29. Zeman, A., P. Bartl, and A. Schaaff, Die massenspektrometrische Fragmentierung von Neopentylpolyolestern. II. Trimethylolpropanfettsäureester, Fette Seifen Anstrichm. 80:278–282 (1978).

    Article  CAS  Google Scholar 

  30. Zeman, A., P. Bartl, and A. Schaaff, Die massenspektrometrische Fragmentierung von Neopentylpolyolestern. IV. Di- und Tripentaerythritfettsäureester, 80:262–267 (1980).

    Article  Google Scholar 

  31. Zeman, A., P. Bartl, A. Schaaff, and V. Christ, Analyse synthetischer Flugturbinenöle durch Gas Chromatographie-Massenspektrometrie. Teil I. Pentaerythritesteröle, Fresenius Z. Anal. Chem. 290:21–28 (1978).

    Article  CAS  Google Scholar 

  32. Zeman, A., P. Bartl, and A. Schaaff, Analyse synthetischer Flugturbinenöle durch Gas Chromatographie-Massenspektrometrie. Teil II. Trimethylolpropan-Dipentaerythritesteröle, 293:4–10 (1978).

    Article  CAS  Google Scholar 

  33. Zeman, A., Analyse synthetischer Schmieröle auf Esterbasis durch Gas Chromatographie-Cl(NH3)-Massenspektrometrie, 310:243–249 (1982).

    Article  CAS  Google Scholar 

  34. Kiiko, V.M., V.V. Gromova, and V.A. Proskuryakov, Study of the Composition of Products of the Thermal Decomposition of Neopentyl Glycol Ester by a Chromato-Mass Spectrometric Method, Zh. Prikl. Khim. (Leningrad) 53:2554–2556 (1980). Chem. Abstr. 94:174253r.

    CAS  Google Scholar 

  35. LeTellier, P.R., and W.W. Nawar, Mass Spectrometry of Some Ethane- and Propanediol Diesters, J. Agric. Food Chem. 23:642–645 (1975).

    Article  CAS  Google Scholar 

  36. Baumann, W.J., J. Seufert, H.W. Hayes, and R.T. Holman, Mass Spectrometric Analysis of Long-Chain Esters of Diols, J. Lipid Res. 10:703–709 (1969).

    CAS  Google Scholar 

  37. Knothe, G., and K.D. Carlson, Synthesis, Mass Spectrometry and Nuclear Magnetic Resonance Characterization of Di-Guerbet Esters, J. Am. Oil Chem. Soc. 75:1861–1866 (1998).

    CAS  Google Scholar 

  38. Murphy, R.C., Fatty Acids, in Mass Spectrometry of Lipids, Handbook of Lipid Research 7, Plenum Press, New York, 1993, pp. 71–130.

    Google Scholar 

  39. Breitmaier, E., and W. Voelter, Carbon-13 NMR Spectroscopy, 3rd edn., VCH, Weinheim, 1989.

    Google Scholar 

  40. Gunstone, F.D., High Resolution 13C NMR Spectroscopy of Lipids, in Advances in Lipid Methodology—Two, edited by W.W. Christie, The Oily Press, Dundee, 1993, pp. 1–68.

    Google Scholar 

  41. Chandler, J.E., F.G. Horneck, and G.I. Brown, The Effect of Cold Flow Additives on Low Temperature Operability of Diesel Fuels, in SAE Tech. Paper Ser., Paper No. 922186, Society of Automotive Engineers, Warrendale, PA, 1992.

    Google Scholar 

  42. Lewtas, K., R.D. Tack, D.H.M. Beiney, and J.W. Mullin, Wax Crystallisation in Diesel Fuel: Habit Modification and the Growth of n-Alkane Crystals, in Advances in Industrial Crystallisation, edited by J. Garside, R.J. Davey, and A.G. Jones, Butterworth-Heineman, Oxford, 1991, pp. 166–179.

    Google Scholar 

  43. The Lipid Handbook, edited by F.D. Gunstone, J.L. Harwood, and F.B. Padley, Chapman and Hall, London, 1994, p. 1.

    Google Scholar 

  44. , 1994, p. 428.

    Google Scholar 

Download references

Author information

Author notes

  1. Michael W. Shockley

    Present address: Caterpillar, Inc., Tech Center-E, P.O. Box 1875, 61656-1875, Peoria, IL

Authors and Affiliations

  1. USDA, ARS, NCAUR, 1815 N. University St., 61604, Peoria, IL

    Gerhard Knothe, Robert O. Dunn, Michael W. Shockley & Marvin O. Bagby

Authors
  1. Gerhard Knothe
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Robert O. Dunn
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Michael W. Shockley
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Marvin O. Bagby
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Gerhard Knothe.

Additional information

Retired.

About this article

Cite this article

Knothe, G., Dunn, R.O., Shockley, M.W. et al. Synthesis and characterization of some long-chain diesters with branched or bulky moieties. J Amer Oil Chem Soc 77, 865–871 (2000). https://doi.org/10.1007/s11746-000-0138-x

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11746-000-0138-x

Key Words

Search

Navigation