Abstract
The polymerization of acrylonitrile(AN) initiated by a σ-complex of tetramethyltetrazene(TMT) and 1-chloro-2,4-dinitrobenzene(DNCB) was carried out in dimethylformamide(DMF). The molar ratio of TMT and DNCB in the complex was spectroscopically determined to be 1: 1. The polymerization was confirmed to proceed through a radical mechanism. The rate of polymerization was found to be 0.6-order in [TMT], approximately 0.5-order in [DNCB], and sscond-order in [AN]. The overall activation energy for the polymerization was estimated as 17.8 kcal/mol. A kinetic reaction scheme and a possible initiation mechanism for the polymerization are proposed to explain the experimental results.
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J.C. McGowan and L. Seed, Brit. Patatent 808 667 (February, 1959).
J.C. McGowan and L. Seed, Chem. Abstr., 54, 20329 (1960).
T. Nakaya, Y. Maki, and M. Imoto, Makromol. Chem., 113, 131 (1968).
T. Nakaya, Y. Maki, and M. Imoto, Makromol. Chem., 125, 161 (1969).
K. Sugiyama, T. Nakaya, and M. Imoto, Polym. J., 2, 50 (1971).
J. F. Bunnett and R. M. Conner, Org. Synth., 40, 34 (1960).
W. E. Bull, J. A. Seaton, and L. F. Audrieth, J. Am. Chem. Soc., 80, 2516 (1958).
R. C. Houts, Text. Res. J., 20, 786 (1950).
H. A. Benesi and J. H. Hildebrand, J. Am. Chem. Soc., 71, 2703 (1949).
W. M. Thomas, E. H. Gleason, and J. J. Pellon, J. Polym. Sci., 17, 275 (1955).
K. Sugiyama, T. Nakaya, and M. Imoto, submitted to J. Polym. Sci..
X. S. Bagdasaryan and Z. A. Simizina, J. Phys. Chem. (Russ.) 34, 2736 (1960).
J. F. Bunnett and J. J. Randall, J. Am. Chem. Soc., 80, 6020 (1958).
E. Buncel, A. R. Norris, and K. E. Russell, Quart. Rev., 22, 123 (1968).
G. A. Russell and E. G. Janzen, J. Am. Chem. Soc., 89, 300 (1967).
A. Ishitani, K. Kuwata, H. Tsubomura, and S. Nagakura, Bull. Chem. Soc. Jpn., 36, 1357 (1963).
C. J. Michejda and D. Romans, Tetrahedron Lett., 48, 4213 (1969).
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Sugiyama, K., Nakaya, T. & Imoto, M. Vinyl Polymerization. CCLXXI. Polymerization of Acrylonitrile Initiated by the System of Tetramethyltetrazene and 1-Chloro-2, 4-dinitrobenzene. Polym J 2, 709–716 (1971). https://doi.org/10.1295/polymj.2.709
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DOI: https://doi.org/10.1295/polymj.2.709