Journal of the American Oil Chemists' Society

, Volume 77, Issue 3, pp 249–255 | Cite as

Long-term behavior of oil-based varnishes and paints. Fate of hydroperoxides in drying oils

  • Jacky Mallégol
  • Jean-Luc GardetteEmail author
  • Jacques Lemaire


The thermal stability of linseed oil and poppyseed oil hydroperoxides in a temperature range from ambient to 120°C has been investigated on the basis of iodometric titration. The peroxide value (PV) vs. oxidation time curves show similar developments at the six temperatures chosen for the experiments. These curves are characterized by a fast increase in the PV up to a maximal value, followed by a decrease in the PV at a lower rate. The maximal PV is higher when the curing temperature is lowered. This result indicates thermal decomposition of the hydroperoxides. The peroxy crosslink concentration in the dried oil film varies similarly to the hydroperoxide concentration. This indicates that, for dried films, the network is almost totally constituted of ether and C-C crosslinks. A comparison of the rates of peroxide decomposition under thermolytic and thermooxidative conditions has evidenced that the only homolytic scission of the O-O bonds cannot justify the decreased of the PV in thermooxidation. Another mechanism accounting for hydroperoxide decomposition, based on an induced decomposition of the hydroperoxides, has been proposed. These results have permitted completing the description of the curing mechanisms of drying oils.

Key Words

Curing mechanism hydroperoxides iodometry linseed oil peroxides peroxy bridges poppyseed oil thermal stability 


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  1. 1.
    Mallégol, J., J.L. Gardette, and J. Lemaire, Long-Term Behavior of Oil-Based Varnishes and Paints. 1. Spectroscopic Analysis of Curing Drying Oils, J. Am. Oil Chem. Soc. 76:967–976 (1999).Google Scholar
  2. 2.
    Gladovic, N., L. Zupancic-Kralj, and J. Plavec, Determination of Primary Oxidation Products of Linoleic Acid and Triacylglycerols, J. Chromatogr. A. 767:63–68 (1997).CrossRefGoogle Scholar
  3. 3.
    Chan, H.W.S., The Mechanism of Oxidation, in Autoxidation of Unsaturated Lipids, edited by H.W.S. Chan, Academic Press, London, 1987, pp. 1–16.Google Scholar
  4. 4.
    Lercker, G., R. Bortolomeazzi, and L. Pizzale, Thermal Degradation of Single Methyl Oleate Hydroperoxides Obtained by Photosensitized Oxidation, J. Am. Oil Chem. Soc. 75:1115–1120 (1998).Google Scholar
  5. 5.
    Frankel, E.N., Lipid Oxidation, Prog. Lipid Res. 19:1–22 (1980).CrossRefGoogle Scholar
  6. 6.
    Schieberle, P., W. Grosch, and J. Firl, Photolysis of Unsaturated Fatty Acid Hydroperoxides, in Proceedings of the Third International Conference on Oxygen Radicals in Chemistry and Biology, edited by W. Bors, M. Saran, and D. Tait, De Gruyter, Berlin, 1984, pp. 257–265.Google Scholar
  7. 7.
    Neff, W.E., and E. Selke, Volatile Compounds from the Triacylglycerol of cis-cis 9,15-Linoleic Acid, J. Am. Oil Chem. Soc. 70:157–161 (1993).Google Scholar
  8. 8.
    Schieberle, P., and W. Grosch, Model Experiments About the Formation of Volatile Carbonyl Compounds,——Ibid. 58:602–607 (1981).Google Scholar
  9. 9.
    Bourgeois, G., N. Vivas, Y. Glories, and C. Vutry, Identification by Gas Chromatography/Mass Spectrometry of Degradation Products from Linoleic Acid Hydroperoxides, Sci. Aliments 15:625–630 (1995).Google Scholar
  10. 10.
    Toschi, T.G., A. Costa, and G. Lercker, Gas Chromatographic Study on High-Temperature Thermal Degradation Products of Methyl Linoleate Hydroperoxides, J. Am. Oil Chem. Soc. 74:387–391 (1997).Google Scholar
  11. 11.
    Kamal-Eldin, A., G. Marquez-Ruiz, M.C. Dobarganes, and L.Å. Appelqvist, Characterization of Aldehydic Acids in Used and Unused Frying Oils, J. Chromatogr. A 776:245–254 (1997).CrossRefGoogle Scholar
  12. 12.
    Privett, O.S., Autoxidation and Autoxidative Polymerization, J. Am. Oil Chem. Soc. 36:507–512 (1959).Google Scholar
  13. 13.
    Carlsson, D.J., R. Brousseau, C. Zhang, and D.M. Wiles, Polyolefin Oxidation: Quantification of Alcohol and Hydroperoxide Products by Nitric Oxide Reactions, Polym. Degrad. Stab. 17:303–318 (1987).CrossRefGoogle Scholar
  14. 14.
    Lacoste, J., D. Vaillant, and D.J. Carlsson, Gamma-, Photo-, and Thermally-Initiated Oxidation of Isotactic Polypropylene, J. Polym. Sci.: Polym. Chem. 31:715–722 (1993).CrossRefGoogle Scholar
  15. 15.
    Gallon, A.A., and W.A. Pryor, The Identification of the Allylic Nitrite and Nitro Derivatives of Methyl Linoleate and Methyl Linolenate by Negative Chemical Ionization Mass Spectroscopy, Lipids 28:125–133 (1993).Google Scholar
  16. 16.
    Kolthoff, I.M., and A.I. Medalia, Determination of Organic Peroxides by Reaction with Ferrous Iron, Anal. Chem. 23:595–603 (1951).CrossRefGoogle Scholar
  17. 17.
    Ma, K., F.R. van de Voort, A.A. Ismail, and J. Sedman, Quantitative Determination of Hydroperoxides by Fourier Transform Infrared Spectroscopy with a Disposable Infrared Card, J. Am. Oil Chem. Soc. 75:1095–1101 (1998).Google Scholar
  18. 18.
    Miyazawa, T., K. Fujimoto, M. Kinoshita, and R. Usuki, Rapid Estimation of Peroxide Content of Soybean Oil by Measuring Thermoluminescence,——Ibid. 71:343–345 (1994).Google Scholar
  19. 19.
    Scheirs, J., D.J. Carlsson, and S.W. Bigger, A Review of the Methods for Detecting and Characterizing Hydroperoxide Groups in Oxidized Polyolefins, Polym. Plast. Technol. Eng. 34:97–116 (1995).Google Scholar
  20. 20.
    Hicks, M., and J.M. Gebicki, A Spectrophotometric Method for the Determination of Lipid Hydroperoxides, Anal. Biochem. 99:249–253 (1979).CrossRefGoogle Scholar
  21. 21.
    Abrahamson, E.W., and H. Linschitz, Determination of Organic Peroxides, Anal. Chem. 24:1355–1356 (1952).CrossRefGoogle Scholar
  22. 22.
    Banerjee, D.K., and C.C. Budke, Spectrophotometric Determination of Traces of Peroxides in Organic Solvents,——Ibid. 36:792–796 (1964).CrossRefGoogle Scholar
  23. 23.
    Dahle, L.K., and R.T. Holman, Modified Iodometric Method for Semi-Microdetermination of Lipid Peroxides,——Ibid. 33:1960–1961 (1961).CrossRefGoogle Scholar
  24. 24.
    Hartman, L., and M.D.L. White, Reagents for Iodometric Determination of Peroxides in Fats,——Ibid. 24:527–529 (1952).CrossRefGoogle Scholar
  25. 25.
    Mair, R.D., and A.J. Graupner, Determination of Organic Peroxides by Iodine Liberation Procedures,——Ibid. 36:194–204 (1964).CrossRefGoogle Scholar
  26. 26.
    Lovass, E., A Sensitive Spectrophotometric Method for Lipid Hydroperoxide Determination, J. Am. Oil Chem. Soc. 69:777–783 (1992).Google Scholar
  27. 27.
    Wagner, C.D., R.H. Smith, and E.D. Peters, Determination of Organic Peroxides—Evaluation of a Modified Iodometric Method, Anal. Chem. 19:976–979 (1947).CrossRefGoogle Scholar
  28. 28.
    Carlsson, D.J., and J. Lacoste, A Critical Comparison of Methods for Hydroperoxide Measurement in Oxidized Polyolefins, Polym. Degrad. Stab. 32:377–386 (1991).CrossRefGoogle Scholar
  29. 29.
    Gardette, J.L., and J. Lemaire, Advantages and Limits of Hydroperoxide Titration Methods in Solid Polymers, Polym. Photochem. 7:409–416 (1986).CrossRefGoogle Scholar
  30. 30.
    Hiatt, R., T. Mill, K.C. Irwin, and J.K. Castleman, Homolytic Decompositions of Hydroperoxides. II. Radical-Induced Decompositions of t-Bytyl Hydroperoxide, J. Org. Chem. 33:1421–1428 (1968).CrossRefGoogle Scholar
  31. 31.
    Gardner, H.W., Reactions of Hydroperoxides—Products of High Molecular Weight, in Autoxidation of Unsaturated Lipids, edited by H.W.S. Chan, Academic Press, London, 1987, pp. 51–93.Google Scholar
  32. 32.
    Hess, P.S., and G.A. O'Hare, Oxidation of Linseed Oil—Temperature Effects, Ind. Eng. Chem. 42:1424–1431 (1950).CrossRefGoogle Scholar
  33. 33.
    Muizebelt, W.J., J.C. Hubert, and R.A.M. Venderbosch, Mechanistic Study of Drying of Alkyd Resins Using Ethyl Linoleate as a Model Substance, Prog. Org. Coat. 24:263–279 (1994).CrossRefGoogle Scholar
  34. 34.
    Frankel, E.N., W.E. Neff, and E. Selke, Analysis of Autoxidized Fats by Gas Chromatography-Mass Spectrometry. IX. Homolytic vs. Heterolytic Cleavage of Primary and Secondary Oxidation Products, Lipids:19:790–800 (1984).Google Scholar
  35. 35.
    Chan, H.W.S., G. Levett, and J.A. Matthew, Thermal Isomerisation of Methyl Linoleate Hydroperoxides. Evidence of Molecular Oxygen Leaving Group in a Radical Rearrangement, J. Chem. Soc. Chem. Comm.: 756–757 (1978).Google Scholar
  36. 36.
    Porter, N.A., B.A. Weber, H. Weenent and J.A. Khan, Autoxidation of Polyunsaturated Lipids. Factors Controlling the Stereochemistry of Product Hydroperoxides, J. Am. Chem. Soc. 102:5597–5601 (1980).CrossRefGoogle Scholar
  37. 37.
    Chan, H.W.S., F.A.A. Prescott, and P.A.T. Swoboda, Thermal Decomposition of Individual Positional Isomers of Methyl Linoleate Hydroperoxide: Evidence of Carbon-Oxygen Bond Scission, J. Am. Oil Chem. Soc. 53:572–576 (1976).Google Scholar
  38. 38.
    Teisseidre, G., J.F. Pilichowski, S. Schmela, and J. Lacoste, Ageing of EPDM-I: Photo and Thermal Stability of EPDM Hydroperoxides, Polym. Degrad. Stab. 53:207–215 (1996).CrossRefGoogle Scholar

Copyright information

© AOCS Press 2000

Authors and Affiliations

  • Jacky Mallégol
    • 1
  • Jean-Luc Gardette
    • 1
    Email author
  • Jacques Lemaire
    • 1
  1. 1.Laboratoire de Photochimie Moléculaire et Macromoléculaire, UMR CNRS 6505Université Blaise Pascal (Clermont II), Ensemble Scientifique des CézeauxAubière CedexFrance

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