Abstract
The radical telomerization of 2-fluorenyl (2-FMA) and 9-fluorenyl (9-FMA) methacrylates was carried out using bromotrichloromethane as a telogen at 50, 70, and 90°C. Despite no significant difference in the apparent rate of telomerization, the average degree of telomerization of 9-FMA was lower than that of 2-FMA regardless of the reaction temperature. Moreover, the telomerization of 9-FMA preferentially gave lactones with formation of 9-bromofluorene. On the other hand, the telomerization of 2-FMA gave both the syndiotactic (st) and the isotactic dimeric telomers in a similar tacticity as that of most reseached monomers, but that of 9-FMA gave only st one. The 2-FMA telomers had a higher melting point than the 9-FMA homologues. The lactonization of dimeric and trimeric telomers was induced by the catalytic action of silica gel or heating. The 9-FMA telomers were greatly subject to lactonization in comparison with the 2-FMA ones, and the reactions of 2- and 9-FMA telomers, respectively, gave 2-hydroxy- and 9-bromo-fluorenes as by-products.
Similar content being viewed by others
Article PDF
References
C. A. Barson, R. R. Mather, and J. C. Robb, Trans. Faraday Soc., 66, 2585 (1970).
D. A. J. Harker, R. A. M. Thomson, and I. R. Walters, Trans. Faraday Soc., 67, 3057 (1971).
C. A. Barson, A. R. Luxton, and J. C. Robb, J. Chem. Soc., Faraday Trans. 1, 68, 1666 (1972).
C. A. Barson, R. A. Batten, and J. C. Robb, Eur. Polym. J., 10, 97 (1974).
C. A. Barson and R. Ensor, Eur. Polym. J., 13, 53 (1977).
T. Kimura, T. Kodaira, and M. Hamashima, Polym. J., 15, 293 (1983).
T. Kimura and M. Hamashima, Polym. J., 18, 21 (1986).
T. Kimura, I. Nakanishi, and M. Hamashima, Polym. J., 18, 689 (1986).
T. Kimura, H. Tasaka, and M. Hamashima, Polym. J., 19, 305 (1987).
W. E. Kuhn, Org. Synth., Coll. Vol. II, 447 (1943).
F. E. Ray and C. F. Hull, J. Org. Chem., 14, 349 (1949).
N. Ishikawa and T. Ozawa, “Yukikagoubutsu Gouseihou,” Vol. 11, The Society of Synthetic Organic Chemistry, Japan, Ed., Gihoudou, Tokyo, 1959, pp 93–96.
K. Suzuki, “Yukikagoubutsu Gouseihou,” Vol. 11, The Society of Synthetic Organic Chemistry, Japan, Ed., Gihoudou, Tokyo, 1959, pp 18–20.
C. I. Simionescu and V. Percec, Polym. Bull., 2, 51 (1980).
J. Nishino, H. Nakahata, and Y. Sakaguchi, Polym. J., 2, 555 (1971).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Kimura, T., Yoshimura, T., Morimoto, H. et al. Study on Radical Telomerization of Esters of Methacrylic Acid Using Bromotrichloromethane and Characteristics of the Resulting Telomers V. Fluorenyl Methacrylates. Polym J 19, 1165–1172 (1987). https://doi.org/10.1295/polymj.19.1165
Issue Date:
DOI: https://doi.org/10.1295/polymj.19.1165