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Evidence Contrary to the Accepted Diels–Alder Mechanism in the Thermal Modification of Vegetable Oil

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Journal of the American Oil Chemists' Society

Abstract

A fatty methyl ester product has been made using two routes. Soybean oil was thermally polymerized anaerobically without a catalyst at 330 °C and the material was then transesterified using base catalyst and methanol. Alternatively, a similar product can be obtained by heating methyl linoleate to the same temperature in a pressure reactor. The product structure was studied by NMR spectroscopy, gel permeation chromatography and mass spectrometry. It is a dimeric product which does not contain substituted cyclohexane structures. This evidence shows that the Diels–Alder reaction has not occurred under these conditions. This is in contradiction to many literature reports, but in agreement with a neglected paper from 1971. This correction has implications in both biodiesel and industrial oil products.

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Acknowledgments

Karl E. Vermillion is acknowledged for NMR analysis and discussion. This research was part of a joint effort by the Agricultural Research Service of the United States Department of Agriculture, Oil Products Group, Peoria, IL and the Tribology Group, Chemical Engineering Department of the Pennsylvania State University, University Park, PA.

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Authors and Affiliations

  1. USDA/NCAUR/ARS, Bio-Oils Research, 1815 N. University Street, Peoria, IL, 61604, USA

    Mert Arca & Kenneth M. Doll

  2. Renewable Processing Technology, 1815 N. University Street, Peoria, IL, 61604, USA

    Neil P. J. Price

  3. Department of Chemical Engineering, Pennsylvania State University, University Park, PA, 16802, USA

    Mert Arca & Joseph M. Perez

  4. Illinois Sustainable Technology Center, University of Illinois, Urbana-Champaign, 1 Hazelwood Drive, Champaign, IL, 61820, USA

    Brajendra K. Sharma

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  1. Mert Arca
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  2. Brajendra K. Sharma
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  3. Neil P. J. Price
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  4. Joseph M. Perez
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  5. Kenneth M. Doll
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Corresponding author

Correspondence to Kenneth M. Doll.

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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 US Department of Agriculture. USDA is an equal opportunity provider and employer.

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Arca, M., Sharma, B.K., Price, N.P.J. et al. Evidence Contrary to the Accepted Diels–Alder Mechanism in the Thermal Modification of Vegetable Oil. J Am Oil Chem Soc 89, 987–994 (2012). https://doi.org/10.1007/s11746-011-2002-x

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  • DOI: https://doi.org/10.1007/s11746-011-2002-x

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