Abstract
To obtain information about the transition state for the cationic polymerization of monophenylbutadienes, the ring-substituent and the temperature effects on the copolymerizability were investigated. Judging from the magnitude of the ρ+ values for the copolymerizations of styrene with ring-substituted 1- and 2-phenylbutadienes, it is suggested that the propagation of monophenylbutadiene proceeds through the transition state which involves an cyclic carbonium ion intermediate. The same interpretation could be applied for the attack of a cinnamyl-type cation onto monophenylbutadiene. The reactivity of monomers toward a styryl cation decreased according to the following order: 1-phenylbutadiene>styrene>2-phenylbutadiene. The lower reactivity of 2-phenylbutadiene in comparison with styrene may be ascribed to the enthalpy increase which overweighs the entropy increase in the transition state.
Similar content being viewed by others
Article PDF
References
R. Asami, K. Hasegawa, N. Asai, I. Moribe, and A. Doi, Polym. J., 8, 74 (1976).
R. Asami, K. Hasegawa, and T. Onoe, Polym. J., 8, 43 (1976).
R. Asami and K. Hasegawa, Polym. J., 8, 67 (1976).
“Organic Syntheses” Coll. IV, N. Rabjohn Ed., John Wiley & Sons, Inc., New York, N.Y., 1963, p 727.
A. I. Ezrielev, E. L. Brokhina, and E. S. Roskin, Vysokomol. Soedin., 11, 1670 (1969).
K. Izawa, T. Okuyama, T. Sakagami, and T. Fueno, J. Am. Chem. Soc., 95, 6752 (1973).
J. P. Kennedy in “Copolymerization,” G. E. Ham, Ed,, Interscience, New York, N.Y., 1964, p 308.
W. M. Schubert, B. Lamm, and J. R. Keefe, J. Am. Chem. Soc., 86, 4272 (1964).
J. H. Polston and K. Yates, J. Am. Chem. Soc., 91, 1483 (1969).
W. L. Orr and R. Kharash, J. Am. Chem. Soc., 78, 1201 (1956).
T. Okuyama, N. Asami, and T. Fueno, Bull. Chem. Soc. Jpn., 43, 3553 (1970).
T. Masuda, M. Otsuki, and T. Higashimura, J. Polym. Sci., Polym. Chem. Ed., 12, 1385 (1974).
H. Ishida and I. Yamaji, Kobunshi Ronbunshu, 32, 357 (1975).
K. Hasegawa and R. Asami, to be published.
A. Mizote, T. Tanaka, T. Higashimura, and S. Okamura, J. Polym. Sci., Part A, 3, 2567 (1965).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Hasegawa, Ki., Asami, R. Cationic Polymerization of Phenylbutadienes. V. Cationic Copolymerization of Monophenyl-1,3-butadienes. Polym J 8, 276–280 (1976). https://doi.org/10.1295/polymj.8.276
Issue Date:
DOI: https://doi.org/10.1295/polymj.8.276