Abstract
Anionic polymerizations of t-butyl acrylate(t-BuA) were carried out in toluene with a combination of t-butyllithium(t-BuLi) and bis(2,6-di-t-butylphenoxy)methylaluminum [MeAl(ODBP)2] at low temperatures. The polymerization of t-BuA in the temperature range from −60°C to −20°C gave polymers with narrow molecular weight distribution(MWD). Anionic copolymerization of t-BuA and ethyl methacrylate(EMA) with t-BuLi/MeAl(ODBP)2 in toluene at −60°C proceeded in a monomer-selective manner. The propagating anions react selectively with t-BuA which may be activated through the preferential coordination with MeAl(ODBP)2. The copolymer showed a bimodal MWD, on-line SEC-NMR analysis of which revealed the formation of poly(t-BuA) as a lower molecular weight fraction and block-like copolymer as a higher molecular weight fraction. Increase in the polymerization temperature resulted in higher block efficiency, and the copolymers with narrow MWDs were formed at −40°C and −30°C. The 13C NMR spectra of the copolymers formed at and below −30°C indicated that the copolymers consisted of poly(t-BuA) block and poly(EMA) block. The copolymer formed at −20°C had narrow MWD and the random comonomer sequence.
Similar content being viewed by others
Article PDF
References
L. Dvorenek and P. Vlček, Macromolecules, 27, 4881 (1994).
Y. Li, D. G. Ward, S. S. Reddy, and S. Collins, Macromolecules, 30, 1875 (1997).
B. Schmitt, H. Schlaad, and A. H.E. Müller, Macromolecules, 31, 1705 (1998).
R. Fayt, R. Forte, C. Jacobs, R. Jérôme, T. Ouhadi, Ph. Teyssié, and S. K. Varshney, Macromolecules, 20, 1442 (1987).
Ph. Teyssié, R. Fayt, C. Jacobs, R. Jérôme, L. Leemans, and S. K. Varshney, Polym. Prepr., Am. Chem. Soc., Div Polym. Chem., 29/2, 52 (1988).
C. Jacobs, S. K. Varshney, J. P. Hautekeer, R. Fayt, R. Jérôme, and Ph. Teyssié, Macromolecules, 23, 4024 (1990).
P. Vlček, J. Lochmann, and J. J. Otoupalova, Macromol. Chem. Rapid Commun., 13, 163 (1992).
L. Dvoranek and P. Vlček, Polym. Bull., 31, 393 (1993).
P. Vlček, J. Otoupalova, and J. Kriz, Makromol. Chem., 194, 841 (1993).
J.-S. Wang, R. Jérôme, Ph. Bayard, L. Baylac, M. Patin, and Ph. Teyssié, Macromolecules, 27, 4615 (1994).
J.-S. Wang, R. Jérôme, Ph. Bayard, M. Patin, Ph. Teyssié, B. Vuillemin, and Ph. Heim, Macromolecules, 27, 4635 (1994).
J.-S. Wang, Ph. Bayard, R. Jérôme, S. K. Varshney, and Ph. Teyssié, Macromolecules, 27, 4890 (1994).
J.-S. Wang, R. Jérôme, Ph. Bayard, and Ph. Teyssié, Macromolecules, 27, 4908 (1994).
N. Nugay, T. Nugay, R. Jérôme, and Ph. Teyssié, J. Polym. Sci., Part A, Polym. Chem., 35, 361 (1997).
M. Kuroki, T. Watanabe, T. Aida, and S. Inoue, J. Am. Chem. Soc., 113, 5903 (1991).
D. G.H. Ballard, R. J. Bowles, D. M. Haddleton, S. N. Richards, R. Sellens, and D. L. Twose, Macromolecules, 25, 5907 (1992).
T. Kitayama, Y. Zhang, and K. Hatada, Polym. Bull., 32, 439 (1994).
T. Kitayama, Y. Zhang, and K. Hatada, Polym. J., 26, 868 (1994).
T. Kitayama, S. He, Y. Hironaka, and K. Hatada, Polym. Prepr., Jpn., 44, 153 (1995).
T. Kitayama, T. Hirano, and K. Hatada, Polym. J., 28, 61 (1996).
T. Kitayama, T. Hirano, Y. Zhang, and K. Hatada, Macromol. Symp., 107, 297 (1996).
T. Kitayama, T. Hirano, and K. Hatada, Tetrahedron, 53, 15263 (1997).
T. Hirano, T. Kitayama, and K. Hatada, Polym. J., 30, 736 (1998).
T. Hirano, H. Yamaguchi, T. Kitayama, and K. Hatada, Polym. J., 30, 767 (1998).
T. Kitayama and K. Hatada, “New Macromolecular Architecture and Functions,” M. Kamachi and A. Nakamura, Ed., Springer, Berlin, 1996, p31.
K. Hatada, K. Ute, Y. Okamoto, M. Imanari, and N. Fujii, Polym. Bull., 20, 317 (1988).
K. Hatada, K. Ute, T. Kitayama, M. Yamamoto, T. Nishimura, and M. Kashiyama, Polym. Bull., 21, 489 (1989).
K. Hatada, K. Ute, M. Kashiyama, and M. Imanari, Polym. J., 22, 218 (1990).
K. Ute, R. Niimi, S. Hongo, and K. Hatada, Polym. J., 30, 439 (1998).
S. C. Watson and J. F. Eastham, J. Organomet. Chem., 9, 195 (1965).
K. Maruoka, T. Itoh, M. Sakura, K. Nonoshita, and H. Yamamoto, J. Am. Chem. Soc., 110, 3588 (1988).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Kitayama, T., Tabuchi, M. & Hatada, K. Monomer-Selective Living Copolymerization of t-Butyl Acrylate and Ethyl Methacrylate with t-Butyllithium/Bis(2,6-di-t-butylphenoxy)methylaluminum. Polym J 32, 796–802 (2000). https://doi.org/10.1295/polymj.32.796
Issue Date:
DOI: https://doi.org/10.1295/polymj.32.796