Abstract
This paper describes the catalyst character of copper (I) tert-butoxide (t-BuOCu) for vinyl polymerization. At the low temperature of 0°C, t-BuOCu initiated the anionic polymerization of acrylonitrile (AN) in the presence of a coordinating compound such as tert-butyl isocyanide (t-BuNC), trimethyl phosphite, triphenylphosphine, and hexamethylphosphoric triamide (HMPT). The mechanism of the anionic polymerization was shown by the reaction of AN monomer with t-BuOCu—t-BuNC in the presence of a protic solvent of tert-BuOH and by copolymerization experiments. Without any coordinating compound, t-BuOCu caused the polymerization of styrene (ST), methylaerylate (MA), methyl methacrylate (MMA), and AN at the higher temperature of 80°C, where a radical mechanism was assumed.
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T. Saegusa, S. Horiguchi, and T. Tsuda, Macromolecules, 8, 112 (1975).
T. Tsuda, T. Hashimoto, and T. Saegusa, J. Am. Chem. Soc., 94, 658 (1972).
T. Tsuda, H. Habu, S. Horiguchi, and T. Saegusa, J. Am. Chem. Soc., 96, 5930 (1974).
R. G. Pearson, J. Am. Chem. Soc., 85, 3533 (1963).
R. G. Pearson, Science, 151, 172 (1966).
J. Trekoval and D. Lim, J. Polym. Sci., Part C, 4, 333 (1964).
J. F. Normant, Synthesis, 1972, 63.
T. Ikariya, and A. Yamamoto, J. Organometal. Chem., 72, 145 (1974).
S. Inoue, “Structure and Mechanism in Vinyl Polymerization”, T. Tsuruta, Ed., Marcel Dekker, New York, N.Y., 1969, p 125.
The monomer reactivity ratios for the radical copolymerization: γAN=1.5, γMA=0.84 (by BPO at 60°C).
C. S. Marvel and R. Schwen, J. Am. Chem. Soc., 79, 6003 (1957).
M. Tomoi and H. Kakiuchi, Kogyo Kagaku Zasshi (J. Chem. Soc. Japan, Ind. Chem. Sect.), 73, 2367 (1970). A Grignard reagent—coordinating compound system polymerizes ST.
F. Dawans and G. Smets, Makromol. Chem., 59, 163 (1963).
T. Saegusa and S. Horiguchi, Polym. J., 6, 419 (1974).
N. L. Zutty and F. J. Welch, J. Polym. Sci., 43, 445 (1960).
I. Ugi and R. Meyr, Chem. Ber., 93, 239 (1960).
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Saegusa, T., Horiguchi, S. & Tsuda, T. Vinyl Polymerization by Copper (I) tert-Butoxide. Polym J 8, 302–306 (1976). https://doi.org/10.1295/polymj.8.302
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DOI: https://doi.org/10.1295/polymj.8.302