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Oxidative crosslinking of alkyd resins studied with mass spectrometry and NMR using model compounds

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Journal of Coatings Technology

Abstract

The crosslinking of alkyd resins has been studied using ethyl linoleate and methyl ricinoate as model compounds. With quantitative13C NMR it was established that ether- and peroxy-crosslinks were formed in roughly equal amounts. Double bonds reacted to give epoxides, endoperoxides, and β-scission into aldehydes. Using SIMS it was established that dimers through pentamers were formed having included several oxygen atoms. After reduction of peroxide (crosslinks) with stannous chloride, the higher oxygen homologues decreased. In the NMR spectrum of the reduced material, peroxide and epoxide signals completely disappeared. High resolution electrospray ionization mass spectra (ESI-MS) yielded evidence regarding the crosslink mechanism. The non-conjugated linoleic acid was found to crosslink by combination of radicals: dimers were having masses 2(M-1). The conjugated linoleic acid crosslinked by addition of radicals to the double bond and disproportionation, yielding masses 2M as well. (M = mass of ethyl linoleate or methyl ricinoate, respectively, including several oxygen atoms.) EIS-MS of oligomers after isotopic exchange enabled estimation of OH and OOH groups.

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References

  1. Chang, S.S. and Kummerov, F.A.,J. Am. Oil Chem. Soc., 30, 403 (1953).

    Article  CAS  Google Scholar 

  2. Witting, L.A., Chang, S.S., and Kummerov, F.A.,J. Am. Oil Chem. Soc., 34, 470 (1957).

    Article  CAS  Google Scholar 

  3. Frankel, E.N., Garwood, R.F., Vinson, J.R., and Weedon, B.C.L.,J. Chem. Soc., Perkin I, 2707 (1982).

  4. Frankel, E.N., Evans, C.D., McConnell, D.G., and Jones, E.P.,J. Am. Oil Chem. Soc., 38, 134 (1961).

    Article  CAS  Google Scholar 

  5. Frankel, E.N., Nowakowska, J., and Evans, C.D.,J. Am. Oil Chem. Soc., 38, 161 (1961).

    Article  CAS  Google Scholar 

  6. Frankel, E.N. et al.,Lipids, 12, 908, 1055 (1977).

    Article  PubMed  CAS  Google Scholar 

  7. Neff, W.E., Frankel, E.N., and Weisleder, D.,Lipids, 16, 439 (1981).

    Article  CAS  Google Scholar 

  8. Frankel, E.N. et al.,J. Chem. Soc., Perkin I, 2233 (1984).

  9. Neff, N.W., Frankel, E.N., and Fujimoto, K.,J. Am. Oil Chem. Soc., 65, 617 (1988).

    Article  Google Scholar 

  10. Chan, H. and Levett, G.,Lipids, 12, 99 (1977).

    Article  PubMed  CAS  Google Scholar 

  11. Chan, H.,J. Am. Oil Chem. Soc., 54, 100 (1977).

    Article  CAS  Google Scholar 

  12. Muizebelt, W.J., Van Wijk, F.G.H., and Van Velde, J.,Proc. 15th Int. Conf. Org. Coat. Sci. Techn., Athens, Greece, p. 299, 1989.

  13. Muizebelt, W.J., Hubert, J.C., and Venderbosch, R.A.M.,Progr. Org. Coat., 24, 263 (1994).

    Article  CAS  Google Scholar 

  14. Muizebelt, W.J. and Nielen, M.W.F.,J. Mass Spectrom., 31, 545 (1996).

    Article  Google Scholar 

  15. Terao, J. and Matsushita, S.,Agric. Biol. Chem., 39, 2027 (1975).

    CAS  Google Scholar 

  16. Terao, J. and Matsushita, S.,J. Am. Oil Chem. Soc., 54, 234 (1977).

    Article  CAS  Google Scholar 

  17. Terao, J., Inoue, T., Yamagata, S., Murakami, H., and Matsushita, S.,Agric. Biol. Chem., 48, 1735 (1984).

    CAS  Google Scholar 

  18. Yamamoto, Y., Niki, E., and Kamiya, Y.,Lipids, 17, 870 (1982).

    Article  CAS  Google Scholar 

  19. Yamamota, Y., Saeki, N., Haga, S., Niki, E., and Kamiya, Y.,Bull. Chem. Soc. Jap., 57, 3177 (1984).

    Article  Google Scholar 

  20. Horvat, R.J. et al.,J. Am. Oil Chem., 46, 94 (1969).

    Article  CAS  Google Scholar 

  21. Miyashita, K., Fujimoto, K., and Kaneda, T.,Agric. Biol. Chem., 46, 751, 2293 (1982).

    CAS  Google Scholar 

  22. Niyashita, K., Fujimoto, K., and Kaneda, T.,Agric. Biol. Chem., 48, 2511 (1984).

    Google Scholar 

  23. Miyashita, K., Hara, N., Fujimoto, K., and Kaneda, T.,Agric. Biol. Chem., 49, 2633 (1985).

    CAS  Google Scholar 

  24. Miyashita, K., Hara, N., Fujimoto, K., and Kaneda, T.,Lipids, 20, 578 (1985).

    Article  CAS  Google Scholar 

  25. Morita, M.,Agric. Biol. Chem., 45, 2403 (1981).

    CAS  Google Scholar 

  26. O’Connor, D.E., Michelich, E.D., and Coleman, M.C.,J. Am. Chem. Soc., 103, 223 (1981).

    Article  Google Scholar 

  27. Kennedy, R.J., FATIPEC, 237 (1988).

  28. Falla, N.A.R., “Linoleic Based Coatings: A Study of the Dry Film Structure,”Journal of Coatings Technology,64, 815, 55 (1992).

    Google Scholar 

  29. Carless, H.A.J. and Batten, R.J.,J. Chem. Soc., Perkin I, 1999 (1987).

  30. Hubert, J.C., Venderbosch, R.A.M., Muizebelt, W.J., Klaasen, R.P., and Zabel, K.H.,Progr. Org. Coat., to be published.

  31. Porter, N.A., Lehman, L.S., Weber, B.A., and Smith, K.J.,J. Am. Chem. Soc., 103, 6447 (1981).

    Article  CAS  Google Scholar 

  32. Porter, N.A. and Wujek, D.G.,J. Am. Chem. Soc., 106, 2626 (1984).

    Article  CAS  Google Scholar 

  33. Frankel, E.N., Nowakowska, J., and Evans, C.D.,J. Am. Oil. Chem. Soc., 38, 161 (1961).

    Article  CAS  Google Scholar 

  34. ASTM Test Method D 2075-89, p. 316.

  35. Mair, R.D. and Graupner, A.J.,Anal. Chem., 36, 194 (1964).

    Article  CAS  Google Scholar 

  36. Bletsos, I.V., Hercules, D.M., Greifendorf, D., and Benninghoven, A.,Anal. Chem., 57, 2384 (1985).

    Article  CAS  Google Scholar 

  37. Mizuno, G.R. and Chipault, J.R.,J. Am. Oil Chem. Soc., 42, 839 (1965).

    Article  CAS  Google Scholar 

  38. Bulsing, J.M., Brooks, W.M., Field, J., and Doddrell, D.M.,J. Magn. Reson., 56, 167 (1984). The POMMIE (Phase Oscillations to MaxiMIze Editing) NMR technique yields spectra with separate methyl, methylene and methine carbon signals. The latter are relevant for double bonds and crosslinks.

    CAS  Google Scholar 

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Authors and Affiliations

  1. Akzo Nobel Central Research, The Netherlands

    W. J. Muizebelt, J. J. Donkerbroek, M. W. F. Nielen, J. B. Hussem & M. E. F. Biemond

  2. Akzo Nobel Coatings Research, The Netherlands

    R. P. Klaasen & K. H. Zabel

Authors
  1. W. J. Muizebelt
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  2. J. J. Donkerbroek
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  3. M. W. F. Nielen
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  4. J. B. Hussem
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  5. M. E. F. Biemond
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  6. R. P. Klaasen
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  7. K. H. Zabel
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General Analytical and Environmental Chemistry Dept., P.O. Box 9300, 6800 SB Arnhem, The Netherlands.

P.O. Box 3, 2157 BA Sassenheim, The Netherlands.

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Muizebelt, W.J., Donkerbroek, J.J., Nielen, M.W.F. et al. Oxidative crosslinking of alkyd resins studied with mass spectrometry and NMR using model compounds. Journal of Coatings Technology 70, 83–93 (1998). https://doi.org/10.1007/BF02720501

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