Abstract
Two monomers of 6-membered cyclic imino ethers having 2-perfluoroalkyl substituent, i.e., 2-(pentafluoroethyl)-5,6-dihydro-4H-1,3-oxazine (1a) and 2-(heptafluoropropyl)-5,6-dihydro-4H-1,3-oxazine (1b), were prepared for the first time, whose ring-opening polymerization initiated by sulfonate esters were examined. With methyl p-toluenesulfonate as initiator, the polymerization of 1 proceeded via a covalent propagating species. On the other hand, with methyl trifluoromethanesulfonate, the propagating species was of the structure of 1,3-oxazinium cation. The above mechanisms were confirmed by the in situ 1H and 19F NMR spectra of the polymerization systems as well as the isolation of the 1:1 adducts of 1 with each of the initiators. The polymerizability of 1 was discussed on the basis of the results of an equimolar reaction between the adducts and some cyclic imino ether monomers. The surface energies of the resulting polymers were evaluated by the measurement of contact angles of the polymer film against water and methylene iodide, which were found to be quite low.
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References
M. Miyamoto, K. Aoi, and T. Saegusa, Macromolecules, 21, 1880 (1988).
M. Miyamoto, K. Aoi, and T. Saegusa, Macromolecules, 24, 11 (1991).
S. Kobayashi and T. Saegusa, “Ring-Opening Polymerization,” Vol. 2, Elsevier Applied Science Publishers, New York, N.Y., 1985, Chapter 11.
M. H. Litt, A. J. Levy, and T. G. Bassiri, Belgian Patent 666,831 (1965).
M. Miyamoto, K. Aoi, and T. Saegusa, Macromolecules, 22, 3540 (1989).
M. S. Morgan and L. H. Cretcher, J. Am. Chem. Soc., 70, 375 (1948).
K. J. Ivin, L. C. Kuan-Essig, E. D. Lillie, and L. Watt, Polymer, 17, 656 (1976).
S. Kobayashi, K. Morikawa, N. Shimizu, and T. Saegusa, Polym. Bull., 11, 253 (1984).
T. Saegusa, S. Kobayashi, and A. Yamada, Macromol. Chem., 177, 2271 (1976).
T. Saegusa, S. Kobayashi, and Y. Nagura, Macromolecules, 7, 265 (1974).
T. Saegusa, S. Kobayashi, and Y. Nagura, Macromolecules, 7, 272 (1974).
D. K. Owens and R. C. Wendet, J. Appl. Polym. Sci., 13, 1741 (1969).
R. Ramharack and T. H, Nguyen, J. Polym. Sci., Polym. Lett., 25, 93 (1987).
Two examples for the equilibrium between an ionic species and a covalent one has been actually known: see ref. 7.
For a review of carbonyl group functions as neighboring groups, H. Perst, “Oxonium Ions in Organic Chemistry,” Verlag Chemie, Weinheim/Bergstrasse, 1971, pp 105–127.
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Miyamoto, M., Aoi, K. & Saegusa, T. Preparation of 2-(Perfluoroalkyl)-5,6-dihydro-4H-1,3-oxazines and Their Ring-Opening Polymerization Initiated by Sulfonates. Polym J 24, 383–394 (1992). https://doi.org/10.1295/polymj.24.383
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DOI: https://doi.org/10.1295/polymj.24.383
