Abstract
The copolymerization of 1-phenylbutadiene with olefinic monomers was performed by using isobutene, styrene, and α-methylstyrene as comonomers catalyzed by BF3OEt2 or SnCl4-trichloroacetic acid. From the monomer reactivity ratios in these copolymerizations in methylene chloride, the following order of the reactivities of the monomers is indicated: α-methylstyrene>1-phenylbutadiene>isobutene>styrene>isoprene>butadiene. This order of the reactivities will be explained by the stability of the cations formed from the monomers and by the nucleophilicity of the monomers. In the copolymerization of 1-phenylbutadiene with styrene catalyzed by BF3OEt2, the reactivity of 1-phenylbutadiene increased with increasing the polarity of the solvent in the order of nitroethane>methylene chloride>toluene. The temperature effect on the copolymerization was also recognized in such polar solvent as nitroethane. These results and the block character in the copolymerization of 1-phenylbutadiene with isobutene were interpreted on the basis of the two-step theory of propagation.
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R. Asami, K. Hasegawa, and T. Onoe, Polym. J., 8, 43 (1976).
R. Asami and H. Hasegawa, Polym. J., 8, 67 (1976).
J. P. Kennedy and N. H. Canter, J. Polym. Sci., Part A-1, 5, 2455 (1967).
R. M. Thomas and W. J. Sparks, U.S. Patent 2356128 (1944).
Y. Imanishi, T. Yamane, Z. Momiyama, and T. Higashimura, Kobunshi Kagaku (Chem. High Polymers), 23, 152 (1966).
Y. Imanishi, T. Higashimura, and S. Okamura, J. Polym. Sci., Part A, 3, 2455 (1965).
S. Okamura, T. Higashimura, and K. Takeda, Kobunshi Kagaku (Chem. High Polymers), 18, 389 (1961).
C. G. Overberger and W. G. Kamath, J. Am. Chem. Soc., 85, 466 (1963).
T. Yonezawa, T. Higashimura, K. Katagiri, K. Hayashi, S. Okamura, and K. Fukui, J. Polym. Sci., 26, 311 (1957).
J. P. Kennedy and R. G. Squires, J. Macromol. Chem., 1, 861 (1967).
V. I. Anosov and A. A. Kortkov, Vysokomol. Soedin., 2, 354 (1960).
R. Asami and K. Hasegawa, Polym. J., 8, 53 (1976).
J. Rehner, Jr., R. L. Zapp, and W. J. Sparks, J. Polym. Sci., 11, 21 (1953).
G. R. Brown and D. C. Pepper, J. Chem. Soc., 1963, 5930.
T. Masuda, M. Otsuki, and T. Higashimura, J. Polym. Sci., Polym. Chem. Ed., 12, 1385 (1974).
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Asami, R., Hasegawa, Ki., Asai, N. et al. Cationic Polymerization of Phenylbutadienes. IV. Cationic Copolymerization of trans-1-Phenyl-1,3-butadiene with Olefinic Monomers. Polym J 8, 74–80 (1976). https://doi.org/10.1295/polymj.8.74
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DOI: https://doi.org/10.1295/polymj.8.74