On the plasma polymerisation of allyl alcohol: an investigation of ion–molecule reactions using a selected ion flow tube

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Liam O'Toole, Christopher A. Mayhew and Robert D. Short


Abstract

Low power plasmas of allyl alcohol monomer (M) have been previously probed by mass spectrometry. Mechanisms describing the formation of solid-phase product, based on ion–molecule reactions, were proposed. Major mechanisms proposed initially involve the reaction of (M-H)+ ion with M, followed by a sequence of secondary ion–molecule reactions. In this paper the feasibility of these reactions has been tested using a selected ion flow tube. Parent and product ions have been monitored as a function of M concentration, providing information on the reaction rate coefficient and branching ratios, respectively. Primary and secondary products have been distinguished. The new data support the mechanism proposed for the formation of dimers and trimers in the plasma phase. However, the identity of an m/z 81 cation, previously attributed to a purely hydrocarbon containing fragment, has been revised. This ion is a primary product arising directly from reaction of (M-H)+ and M, and is most likely the pyrylium cation. This new information has resulted in a significant modification to the previously proposed scheme.


References

  1. S. Morita and S. Hattori, Plasma Deposition, Treatment, and Etching of Polymers, ed. R. d'Agostino, Academic Press, London, 1990, ch. 6 Search PubMed.
  2. A. Chilkoti, B. D. Ratner and D. Briggs, Anal. Chem., 1991, 63, 1612 CrossRef CAS.
  3. W. Gombotz and A. Hoffman, J. Appl. Polym. Sci., 1989, 37, 91 CrossRef CAS.
  4. N. Inagaki and M. Matsunga, Polym. Bull., 1986, 13, 349.
  5. M. Sanchez Urrutia, H. P. Schreiber and M. R. Wertheimer, J. Appl. Polym. Sci., Polym. Symp., 1988, 42, 305 Search PubMed.
  6. H. S. Munro, R. J. Ward, M. C. Davies and R. D. Short, Polymer, 1993, 34, 2250 CrossRef CAS.
  7. H. K. Yasuda, Plasma Polymerisation, Academic Press, London, 1985 Search PubMed.
  8. N. Morosoff, Plasma Deposition, Treatment, and Etching of Polymers, ed. R. d'Agostino, Academic Press, London, 1990, ch. 1 Search PubMed.
  9. H. Kobayashi, M. Shen and A. T. Bell, J. Macromol. Sci., Chem. Educ., 1974, A8, 1354 Search PubMed.
  10. L. O'Toole, R. D. Short, A. P. Ameen and F. R. Jones, J. Chem. Soc., Faraday Trans., 1995, 91, 1363 RSC.
  11. L. O'Toole, A. J. Beck, R. D. Short, A. P. Ameen and F. R. Jones, J. Chem. Soc., Faraday Trans., 1995, 91, 3907 RSC.
  12. L. O'Toole and R. D. Short, J. Chem. Soc., Faraday Trans., 1997, 93, 1141 RSC.
  13. H. Budzikiewicz, C. Djerassi and D. H. Williams, Interpretation of Mass Spectra of Organic Compounds, Holden-Day, San Francisco, 1964 Search PubMed.
  14. F. W. McLafferty, Interpretation of Mass Spectra, University Science Books, California, 3rd edn., 1980 Search PubMed.
  15. D. Smith and N. G. Adams, Adv. At. Mol. Phys., 1988, 24, 1 Search PubMed.
  16. T. Su and W. J. Chesnavich, J. Phys. Chem., 1982, 76, 5183 CrossRef CAS.
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