Abstract
Anionic polymerization of α-(aminomethyl)acrylates (2—8) having an unprotected amino proton was carried out using lithium reagents at −78°C. Acrylates except for 4 and 8 afforded the polymers in good yields. The polymerization of ethyl α-[N-(diphenylmethyl)aminomethyl]acrylate (3) with n-BuLi or the Ph2NLi-N,N,N′,N′-tetramethylethylene-diamine (TMEDA) complex in toluene afforded a polymer with a normal vinyl polymer structure and high isotacticity. Hydrogen-transfer of the amino proton hardly occurred in the polymerization process. The anionic polymerizations of ethyl α-[N-(1-phenylethyl)aminomethyl]acrylate (2) using lithium reagents in toluene and tetrahydrofuran (THF) proceeded with hydrogen-transfer reaction. CH carbon generated by hydrogen-transfer in the main chain was detected by DEPT NMR measurement of poly(2). The CH-containing unit in the polymer increased up to nearly 40% when THF was used as a solvent. Monomers 4 and 8 showed low polymerizability.
Similar content being viewed by others
Article PDF
References
B. Yamada and S. Kobatake, Prog. Polym. Sci., 19, 1089 (1994).
S. Habaue, H. Yamada, and Y. Okamoto, Macromolecules, 29, 3326 (1996).
S. Habaue, H. Yamada, T. Uno, and Y. Okamoto, J. Polym. Sci., Part A, Polym. Chem., 35, 721 (1997).
S. Habaue, T. Uno, and Y. Okamoto, Macromolecules, 30, 3125 (1997).
S. Habaue, T. Uno, H. Baraki, and Y. Okamoto, Polym. J., 29, 983 (1997).
S. Habaue, H. Baraki, and Y. Okamoto, Polym. J., 29, 872 (1997).
D. S. Breslow, G. E. Hulse, and A. S. Matlack, J. Am. Chem. Soc., 79, 3760 (1957).
S. Okamura, Y. Oishi, T. Higashimura, and T. Senoo, Kobunshi Kagaku, 19, 323 (1962).
H. Wexler, Makromol. Chem., 115, 262 (1968).
T. Tsunetsugu, T. Matsuo, and J. Furukawa, Makromol. Chem., 107, 222 (1967).
M. Guaita, G. Camino, and L. Trossarelli, Makromol. Chem., 131, 309 (1970).
S. Negishi and Y. Tamura, J. Polym. Sci., Part A-1, 5, 2911 (1967).
K. Kojima, N. Yoda, and C. S. Marvel, J. Polym. Sci., Part A-1, 4, 1121, (1966).
J. Villieras and M. Rambaud, Synthesis, 924 (1982).
T. Tsuruta, J. Polym Sci., Part D, 6, 179 (1972).
Y. Okamoto, K. Ohta, and H. Yuki, Chem. Lett., 617 (1977).
Y. Okamoto, K. Urakawa, K. Ohta, and H. Yuki, Macromolecules, 11, 719 (1978).
Y. Okamoto and E. Yashima, Prog. Polym. Sci., 15, 263 (1990).
T. Uno, S. Habaue, and Y. Okamoto, Chirality, 10, 711 (1998).
G. Wulff and Y. Wu, Makromol. Chem., 191, 3005 (1990).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Baraki, H., Habaue, S. & Okamoto, Y. Stereospecific Anionic Polymerization and Novel Hydrogen-Transfer Polymerization of α-(Aminomethyl)acrylates Having Unprotected Amino Group. Polym J 31, 1260–1266 (1999). https://doi.org/10.1295/polymj.31.1260
Issue Date:
DOI: https://doi.org/10.1295/polymj.31.1260