Kinetic study of radical polymerization of dialkyl fumarates using electron spin resonance spectroscopy
Corresponding Author
Akikazu Matsumoto
Department of Applied Chemistry, Faculty of Engineering, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558, Japan
Department of Applied Chemistry, Faculty of Engineering, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558, JapanSearch for more papers by this authorYoshinori Sano
Department of Applied Chemistry, Faculty of Engineering, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558, Japan
Search for more papers by this authorMasahiro Yoshioka
Department of Applied Chemistry, Faculty of Engineering, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558, Japan
Search for more papers by this authorTakayuki Otsu
Faculty of Biology-Oriented Science and Technology, Kinki University, Uchita-cho, Naga-gun, Wakayama 649-64, Japan
Search for more papers by this authorCorresponding Author
Akikazu Matsumoto
Department of Applied Chemistry, Faculty of Engineering, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558, Japan
Department of Applied Chemistry, Faculty of Engineering, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558, JapanSearch for more papers by this authorYoshinori Sano
Department of Applied Chemistry, Faculty of Engineering, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558, Japan
Search for more papers by this authorMasahiro Yoshioka
Department of Applied Chemistry, Faculty of Engineering, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558, Japan
Search for more papers by this authorTakayuki Otsu
Faculty of Biology-Oriented Science and Technology, Kinki University, Uchita-cho, Naga-gun, Wakayama 649-64, Japan
Search for more papers by this authorAbstract
The radical polymerization of dialkyl fumarates (DRF) bearing various ester alkyl groups was kinetically studied. The propagation and termination rate constants were determined using electron spin resonance (ESR) spectroscopy. The introduction of the bulky ester alkyl groups such as a tert-butyl group decreased the termination rate constant as expected. However, it has also been revealed that the bulky groups promote propagation despite the steric repulsion. The propagation rate and mechanism are discussed in relation to the propagation manner, i.e., tacticity of the polymer. © 1996 John Wiley & Sons, Inc.
References and Notes
- 1 T. Otsu, T. Yasuhara, and A. Matsumoto, J. Macromol. Sci. Chem., A25, 537 (1988).
- 2
T. Otsu,
A. Matsumoto, and
M. Yoshioka,
Progress in Pacific Polymer Science,
Vol. 2,
Y. Imanishi, Ed.,
Springer,
Berlin,
1992,
p. 59.
10.1007/978-3-642-77636-6_6 Google Scholar
- 3 A. Matsumoto and T. Otsu, Macromol. Chem. Phys., Macromol. Symp., 98, 139 (1995).
- 4 T. Otsu, T. Yasuhara, K. Shiraishi, and S. Mori, Polym. Bull., 12, 449 (1984).
- 5 M. Kamachi, Adv. Polym. Sci., 82, 207 (1987).
- 6 A. Matsumoto, K. Mizuta, and T. Otsu, Macromolecules, 27, 5863 (1994), and references cited therein.
- 7 T. Otsu, B. Yamada, and T. Ishikawa, Macromolecules, 24, 415 (1991).
- 8 M. Yoshioka and T. Otsu, Macromolecules, 25, 559, 2599 (1992).
- 9 A. Matsumoto and T. Otsu, Proc. Jpn. Acad., B, 70, 43 (1994).
- 10 T. G. Carswell, D. J. T. Hill, D. S. Hunter, P. J. Pomery, J. H. O'Donnell, and C. L. Winzor, Eur. Polym. J., 26, 541 (1990).
- 11 Kh. S. Bagdasaryan, Theory of Radical Polymerization, Moscow, 1959; translated in Japanese by M. Imoto and T. Futami, Asakura,
- 12 G. Ordian, Principles of Polymerization, 3rd ed., Wiley New York, 1991.
- 13 A. Matsumoto, Y. Sano, M. Yoshioka, and T. Otsu, Eur. Polym. J., to appear.
- 14 M. Yoshika, A. Matsumoto, and T. Otsu, Polym. J., 23, 1249 (1991).
- 15 C. Hansh and A. Leo, Substituent Constants for Corelation Analysis in Chemistry and Biology, Wiley, New York, 1979.
- 16 T. Otsu, A. Matsumoto, K. Shiraishi, N. Amaya, and Y. Koinuma, J. Polym. Sci., Part A: Polym. Chem., 30, 1559 (1992).
- 17 T. Otsu, K. Shiraishi, and A. Matsumoto, J. Polym. Sci., Part A: Polym. Chem., 31, 2523 (1993).
- 18 X. Wang, T. Komoto, I. Ando, and T. Otsu, Makromol. Chem., 189, 1845 (1988).
- 19 M. Yoshioka, A. Matsumoto, T. Otsu, and I. Ando, Polymer, 32, 2741 (1991).
- 20 M. Yoshioka, A. Matsumoto, and T. Otsu, Polym. J., 23, 1191 (1991).
- 21 M. Yoshioka, A. Matsumoto, and T. Otsu, Macromolecules, 25, 2837 (1992).
- 22 B. Giese, W. Damm, F. Wetterich, and H.-G. Zeitz, Tetrahedron Lett., 33, 1863 (1992).
- 23 P. D. Bartlett and T. Funahashi, J. Am. Chem. Soc., 84, 2596 (1962).
- 24 T. Otsu and B. Yamada, J. Macromol. Sci.-Chem., A3, 187 (1969).
- 25 A. Matsumoto, T. Tarui, and T. Otsu, Macromolecules, 23, 5102 (1990).
- 26 A. Matsumoto and K. Mizuta, Macromolecules, 27, 1657, 5863 (1994).
- 27 A. Matsumoto, K. Mizuta, and T. Otsu, J. Polym. Sci., Part A: Polym. Chem., 31, 2539 (1993).
- 28 A. Matsumoto and K. Mizuta, Polym. Bull., 33, 141 (1994).
- 29 A. Matsumoto, K. Shimizu, K. Mizuta, and T. Otsu, J. Polym. Sci., Part A: Polym. Chem., 32, 1957 (1994).
- 30 T. Otsu, K. Yamagishi, and M. Yoshioka, Macromolecules, 25, 2713 (1992).
- 31 T. Otsu, K. Yamagishi, A. Matsumoto, M. Yoshioka, and H. Watanabe, Macromolecules, 26, 3026 (1993).
- 32 A. Matsumoto, K. Yamagishi, and T. Otsu, Eur. Polym. J., 31, 121 (1995).
- 33 T. Otsu and M. Yoshioka, Macromolecules, 25, 1615 (1992).