Abstract
Absolute rate constants of vinyl acetate (VAC) polymerization have been measured by using the intermittent illumination method in various aromatic solvents and ethyl acetate at 30°. It was shown that the solvent effect was mainly ascribed to the variation in propagation rate constants (kp) with solvents rather than that in termination rate constants (kt). The kp increased in the order: benzonitrile < ethyl benzoate < anisole < chlorobenzene < fluorobenzene < benzene < ethyl acetate. This order is almost the same as that for vinyl benzoate (VBZ) previously reported. There was about an eightyfold difference between the largest and the smallest values. This large variation in kp is explained neither by copolymerization through solvents nor the chain transfer to solvents, but by a reversible complex formation between the propagating radical and aromatic solvents. The kp was determined in mixed solvents of ethyl benzoate and ethyl acetate, decreasing with increasing content of ethyl benzoate. This result supports the idea of a reversible complex. The stability constants (Ks) of the complex were estimated on the assumption that the complexed radical was in a dormant state and inactive in the polymerization. The correlation between Ks or kp and the calculated delocalization stabilization energy for the complex was found, and supported the explanation for the solvent effect.
Similar content being viewed by others
Article PDF
References
W. H. Stockmayer and L. H. Peebles Jr., J. Am. Chem. Soc., 75, 2278 (1953).
L. H. Peebles, J. T. Clarke, and W. H. Stockmayer, J. Am. Chem. Soc., 82, 4780 (1960).
J. W. Breitenbach, G. Billek, G. Faltlhansl, and E. Weber, Monatsh. Chem., 92, 1100 (1961).
G. A. Mortimer and L. C. Arnold, J. Am. Chem. Soc., 84, 4986 (1962).
G. Henrici-Olive and S. Olive, Makromol. Chem., 51, 236 (1962).
H. C. Hass and H. Husek, J. Polym. Sci., A, 2, 2298 (1964).
W. H. Atkinson, C. H. Bamford, and G. C. Eastmond, Trans. Faraday Soc., 66, 1446 (1970).
G. F. Santee, R. H. Marchessault, H. G. Clark, J. J. Kearny, and V. Stannett, Makromol. Chem., 73, 177 (1964).
G. M. Burnett and H. W. Melville, Farady Discuss. Chem. Soc., 2, 327 (1947).
G. M. Burnett and L. D. Loan, Trans. Faraday Soc., 51, 219 (1955).
C. H. Bamford, Pure Appl. Chem., 12, 183 (1966).
G. Smets and A. Hertoghe, Makromol. Chem., 17, 189 (1956).
E. D. Morrison, E. H. Gleason, and V. Stannett, J. Polym. Sci., 36, 267 (1959).
A. Vrancken and G. Smets, Makromol. Chem., 30, 197 (1959).
G. M. Burnett and W. W. Wright, Trans. Faraday Soc., 49, 1108 (1953).
S. Banerjee and M. Muthana, J. Polym. Sci., 37 469 (1953).
M. Litt and V. Stannett, Makromol. Chem., 37, 19 (1960).
R. F. Mayo, J. Am. Chem. Soc., 75, 6133 (1953).
G. Hernrici-Olive and S. Olive, Makromol. Chem., 68, 219 (1963).
G. Henrici-Olive and S. Olive, Z. Phys. Chem. (Frankfurt am Main), 47, 286 (1965).
G. Herici-Olive and S. Olive, Z. Phys. Chem. (Frankfurt am Main), 48, 35 (1966).
G. Herici-Olive and S. Olive, Z. Phys. Chem. (Frankfurt am Main), 48, 51 (1966).
C. H. Bamford and S. Brumby, Makromol. Chem., 105, 122 (1967).
C. H. Bamford and S. Brumby, Chem. Ind., 1020 (1969).
C. H. Bamford and A. N. Ferrar, Proc. R. Soc. London Ser., A, 321, 425 (1971).
C. H. Bamford, “Molecular Behaviour and the Development of polymeric Materials,” A. Ledwith and A. M. North, Ed., Chapman and Hall, London, 1975, pp 51—87.
G. M. Burnett, G. G. Cameron, and B. M. Parker, Eur. Polym. J., 5, 231 (1970).
G. M. Burnett, G. G. Cameron, and M. M. Zafar, Eur. Polym. J., 6, 823 (1971).
G. M. Burnett, G. G. Cameron, and S. N. Joiner, J. Chem. Soc., Faraday Trans. 1, 69, 322 (1973).
M. Kamachi, J. Satoh, and S. Nozakura, J. Polym. Sci., Polym. Chem. Ed., 16, 1789 (1978).
M. Kamachi, D. J. Liaw, and S. Nozakura, Polym. J., 9, 307 (1977).
T. Yamamoto, T. Yamamoto, A. Mito, and M. Hirota, Nippon Kagaku Kaishi, 408 (1979).
W. I. Bengough, I. T. Brownlie, and J. Ferguson, “The Chemistry of Polymerization Process,” S.C.I. monograph 20, Society of Chemical Industry, London, 1966, pp 220—234.
S. Nozakura, Y. Morishima, and S. Murahashi, J. Polym. Sci., Polym. Chem. Ed., 10, 2853 (1972).
P. C. Deb and S. Ray, Eur. Polym. J., 13, 1015 (1977).
P. C. Deb and S. Ray, Eur. Polym. J., 14, 607 (1978).
K. Fukui, “Theory of Orientation and Stereo-selection,” Springer-Verlag, Berlin, Germany, 1975, pp 40—85.
K. Fukui, A. Imamura, T. Yonezawa, and C. Nagata, Bull. Chem. Soc. Jpn., 34, 1076 (1961).
R. S. Mulliken, Recl. Trav. Chim. Pays-Bas, 75, 845 (1956).
R. S. Mulliken and W. B. Person, “Molecular Complexes,” Wiley-Interscience, New York, N.Y., 1969.
L. J. Young, “Polymer Handbook,” 2nd ed, J. Brandrip and E. H. Immergut, Ed., John Wiley, New York, N.Y., 1975, Chapter 11, pp 387—404.
M. Kinoshita, T. Irie, and M. Imoto, Makromol. Chem., 110, 47 (1967).
K. Tsuda, S. Kobayashi, and T. Otsu, J. Polym. Sci., A-1, 6, 41 (1968).
J. Hine, “Physical Organic Chemistry,” 2nd ed, McGraw-Hill, New York, N.Y., 1962, pp 81—103.
J. T. Clarke, R. O. Howard, and W. H. Stockmayer, Makromol. Chem., 44/46, 427 (1961).
C. H. Bamford and S. U. Mullik, Polymer, 19, 948 (1978).
K. F. O’Driscoll and T. Yonezawa, Rev. Macromol. Chem., 1, 2 (1966).
N. Kawabata, T. Tsuruta and J. Furukawa, Makromol. Chem., 51, 80 (1962).
M. Kamachi, D. J. Liaw, and S. Nozakura, Polym. Prepr., Jpn., 27, 708 (1977).
L. J. Young “Polymer Hardbook,” 2nd ed, J. Brandrip and E. H. Immergut, Ed., John Wiley, New York, N.Y., 1975, Chapter 11, p 451.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Kamachi, M., Liaw, D. & Nozakura, Si. Solvent Effect on Radical Polymerization of Vinyl Acetate. Polym J 11, 921–928 (1979). https://doi.org/10.1295/polymj.11.921
Issue Date:
DOI: https://doi.org/10.1295/polymj.11.921