Skip to main content
SpringerLink
Log in

Synthesis and Characterization of Estolide Esters Containing Epoxy and Cyclic Carbonate Groups

  • Original Paper
  • Published:
Journal of the American Oil Chemists' Society

Abstract

The unsaturated sites in oleic 2-ethylhexyl estolide esters (containing 35 % monoenic fatty acids) were converted into epoxide and five-membered cyclic carbonate groups and the products characterized by Fourier transform infrared spectra (FTIR), 1H, and 13C nuclear magnetic resonance (NMR) spectroscopies. Epoxidation of the alkene bonds was accomplished using performic acid generated in situ from formic acid and hydrogen peroxide. Greater than 90 % alkenes were converted into their corresponding epoxide groups as determined by oxirane values and the epoxide ring structure was confirmed by 1H and 13C NMR. The estolide ester epoxide material was subsequently reacted with supercritical carbon dioxide in the presence of tetrabutylammonium bromide catalyst to produce the corresponding estolide ester containing the cyclic carbonate group. The signals at 1,807 cm−1 and δ 82 ppm in the FTIR and 13C-NMR spectra, respectively, confirmed the desired cyclic carbonate was produced. The carbonated estolide ester exhibited a dynamic viscosity, at 25 °C, of 172 mPa·s as compared to 155 mPa·s for the estolide ester starting material. The estolide ester structure of these new derivatives was shown to be consistent throughout their synthesis.

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

Fig. 1
Scheme 1
Fig. 2
Fig. 3
Scheme 2

Similar content being viewed by others

References

  1. Wagner H, Luther R, Mang T (2001) Lubricant base fluids based on renewable raw materials: their catalytic manufacture and modification. Appl Catal A 221:429–442

    Article  CAS  Google Scholar 

  2. Biermann U, Bornscheuer U, Meier MAR, Metzger JO, Schafer HJ (2011) Oils and fats as renewable raw materials in chemistry. Angew Chem Int Ed Engl 50:3854–3871

    Article  CAS  Google Scholar 

  3. Biresaw G, Adhvaryu A, Erhan SZ (2003) Friction properties of vegetable oils. J Am Oil Chem Soc 80:697–704

    Article  CAS  Google Scholar 

  4. Cermak S, Isbell T (2001) Synthesis of estolides from oleic and saturated fatty acids. J Am Oil Chem Soc 78:557–565

    Article  CAS  Google Scholar 

  5. Isbell TA, Cermak SC (2002) Synthesis of triglyceride estolides from lesquerella and castor oils. J Am Oil Chem Soc 79:1227–1233

    Article  CAS  Google Scholar 

  6. Cermak SC, Brandon KB, Isbell TA (2006) Synthesis and physical properties of estolides from lesquerella oil and castor oil fatty acid esters. Ind Crops Prod 23:54–64

    Article  CAS  Google Scholar 

  7. Isbell TA, Lowery BA, DeKeyser SS, Winchell ML, Cermak SC (2006) Physical properties of triglyceride estolides from lesquerella and castor oils. Ind Crops Prod 23:256–263

    Article  CAS  Google Scholar 

  8. Cermak SC, Isbell TA (2001) Biodegradable oleic estolide ester having saturated fatty acid end group useful as lubricant base stock. US Patent 6316649

  9. Isbell TA, Abbott TP, Asadauskas S, Lohr JE (2000) Biodegradable oleic estolide ester base stocks and lubricants. US Patent 6018063

  10. Adhvaryu A, Biresaw G, Sharma BK, Erhan SZ (2006) Friction behavior of some seed oils: biobased lubricant applications. Ind Eng Chem Res 45:3735–3740

    Article  CAS  Google Scholar 

  11. Parrish JP, Salvatore RN, Jung KW (2000) Perspectives on alkyl carbonates in organic synthesis. Tetrahedron 56:8207–8237

    Article  CAS  Google Scholar 

  12. Shaikh AAG, Sivaram S (1996) Organic carbonates. Chem Rev 96:951–976

    Article  CAS  Google Scholar 

  13. Gryglewicz S, Oko FA, Gryglewicz G (2003) Synthesis of modern synthetic oils based on dialkyl carbonates. Ind Eng Chem Res 42:5007–5010

    Article  CAS  Google Scholar 

  14. Kenar JA, Tevis ID (2005) Convenient preparation of fatty ester cyclic carbonates. Eur J Lipid Sci Technol 107:135–137

    Article  CAS  Google Scholar 

  15. Kenar JA, Knothe G, Copes AL, Kenar JA (2004) Synthesis and characterization of dialkyl carbonates prepared from mid-, long-chain, and Guerbet alcohols. J Am Oil Chem Soc 81:285–291

    Article  CAS  Google Scholar 

  16. Holser RA (2007) Carbonation of epoxy methyl soyate at atmospheric pressure. J Oleo Sci 56:629–632

    Article  CAS  Google Scholar 

  17. Doll KM, Erhan SZ (2005) Synthesis of carbonated fatty methyl esters using supercritical carbon dioxide. J Agric Food Chem 53:9608–9614

    Article  CAS  Google Scholar 

  18. Doll KM, Erhan SZ (2005) The improved synthesis of carbonated soybean oil using supercritical carbon dioxide at a reduced reaction time. Green Chem 7:849–854

    Article  CAS  Google Scholar 

  19. Li Z, Zhao Y, Yan S, Wang X, Kang M, Wang J, Xiang H (2008) Catalytic synthesis of carbonated soybean oil. Catal Lett 123:246–251

    Article  CAS  Google Scholar 

  20. Tamami B, Sohn S, Wilkes GL, Tamami B (2004) Incorporation of carbon dioxide into soybean oil and subsequent preparation and studies of nonisocyanate polyurethane networks. J Appl Polym Sci 92:883–891

    Article  CAS  Google Scholar 

  21. Wilkes GL, Sohn S, Tamami B (2006) Preparations of nonisocyanate polyurethane materials from epoxidized soybean oils and related epoxidized vegetable oils. US Patent 7045577

  22. Mann N, Mendon SK, Rawlins JW, Thames SF (2008) Synthesis of carbonated vernonia oil. J Am Oil Chem Soc 85:791–796

    Article  CAS  Google Scholar 

  23. Zhang L, Luo Y, Hou Z, He Z, Eli W (2014) Synthesis of carbonated cotton seed oil and its application as lubricating base oil. J Am Oil Chem Soc 91:143–150

    Article  CAS  Google Scholar 

  24. Moser BR, Erhan SZ (2006) Synthesis and evaluation of a series of α-hydroxy ethers derived from isopropyl oleate. J Am Oil Chem Soc 83:959–963

    Article  CAS  Google Scholar 

  25. Findley TW, Swern D, Scanlan JT (1945) Epoxidation of unsaturated fatty materials with peracetic acid in glacial acetic acid solution. J Am Chem Soc 67:412–414

    Article  CAS  Google Scholar 

  26. Schmitz WR, Wallace JG (1954) Epoxidation of methyl oleate with hydrogen peroxide. J Am Oil Chem Soc 31:363–365

    Article  CAS  Google Scholar 

  27. La Scala J, Wool RP (2002) Effect of FA composition on epoxidation kinetics of TAG. J Am Oil Chem Soc 79:373–378

    Article  Google Scholar 

  28. Isbell TA, Kleiman R (1996) Mineral acid-catalyzed condensation of meadowfoam fatty acids into estolides. J Am Oil Chem Soc 73:1097–1107

    Article  CAS  Google Scholar 

  29. Litchfield C, Lord JE, Isbell AF, Reiser R (1963) Cis–trans isomerization of oleic, linoleic and linolenic acids. J Am Oil Chem Soc 40:553–557

    Article  CAS  Google Scholar 

  30. Frost DJ, Gunstone FD (1975) The PMR analysis of non-conjugated alkenoic and alkynoic acids and esters. Chem Phys Lipids 15:53–85

    Article  CAS  Google Scholar 

  31. Bueno-Ferrer C, Jiménez A, Garrigós MC (2010) Migration analysis of epoxidized soybean oil and other plasticizers in commercial lids for food packaging by gas chromatography-mass spectrometry. Food Addit Contam Part A Chem Anal Control Expo Risk Assess 27:1469–1477

    Article  CAS  Google Scholar 

  32. Bueno-Ferrer C, Garrigós MC, Jiménez A (2010) Characterization and thermal stability of poly(vinyl chloride) plasticized with epoxidized soybean oil for food packaging. Polym Degrad Stab 95:2207–2212

    Article  CAS  Google Scholar 

  33. Forest J, Bredsguard J (2012) Epoxidized estolides and methods of making and using the same. US Patent 8258326

  34. Kenar JA (2007) Functionalization of oleyl carbonate by epoxidation. J Am Oil Chem Soc 84:457–461

    Article  CAS  Google Scholar 

  35. Whiteoak CJ, Martin E, Martínez Belmonte M, Benet-Buchholz J, Kleij AW (2012) An efficient iron catalyst for the synthesis of five- and six-membered organic carbonates under mild conditions. Adv Synth Catal 354:469–476

    Article  CAS  Google Scholar 

  36. Clements JH (2003) Reactive applications of cyclic alkylene carbonates. Ind Eng Chem Res 42:663–674

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors acknowledge Erin L. Walter and Amber L. Durham for synthesis and spectroscopy, Andrew J. Thomas for rheology measurements and interpretation, and Karl E. Vermillion for NMR spectroscopy used in this work. This work was a part of the in-house research of the Agricultural Research Service of the United States Department of Agriculture.

Author information

Authors and Affiliations

  1. Bio-Oils Research Unit, National Center for Agricultural Utilization Research, ARS, USDA, 1815 N. University St, Peoria, IL, 61604, USA

    Kenneth M. Doll, Steven C. Cermak & Terry A. Isbell

  2. Functional Foods Research Unit, National Center for Agricultural Utilization Research, ARS, USDA, 1815 N. University St, Peoria, IL, 61604, USA

    James A. Kenar

Authors
  1. Kenneth M. Doll
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Steven C. Cermak
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. James A. Kenar
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Terry A. Isbell
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Kenneth M. Doll.

Additional information

Mention of trade names or commercial products in this publication is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the U.S. Department of Agriculture. USDA is an equal opportunity provider and employer. The U.S. Department of Agriculture (USDA) prohibits discrimination in all its programs and activities on the basis of race, color, national origin, age, disability, and where applicable, sex, marital status, familial status, parental status, religion, sexual orientation, genetic information, political beliefs, reprisal, or because all or part of an individual’s income is derived from any public assistance program. (Not all prohibited bases apply to all programs.) Persons with disabilities who require alternative means for communication of program information (Braille, large print, audiotape, etc.) should contact USDA’s TARGET Center at (202) 720-2600 (voice and TDD). To file a complaint of discrimination, write to USDA, Director, Office of Civil Rights, 1400 Independence Avenue, S.W., Washington, D.C. 20250-9410, or call (800) 795-3272 (voice) or (202) 720-6382 (TDD). USDA is an equal opportunity provider and employer.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material (DOCX 849 kb)

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Doll, K.M., Cermak, S.C., Kenar, J.A. et al. Synthesis and Characterization of Estolide Esters Containing Epoxy and Cyclic Carbonate Groups. J Am Oil Chem Soc 93, 1149–1155 (2016). https://doi.org/10.1007/s11746-016-2857-y

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11746-016-2857-y

Keywords

Search

Navigation