Abstract
Free-radical polymerization of N,N-dimethylacrylamide (DMAA) and N,N-dephenylacrylamide (DPAA) were carried out under various conditions. DMAA gave an isotactic-rich polymer in most cases, whereas DPAA gave a syndiotactic polymer. The polymerization stereochemistry was also affected by reaction solvents including toluene, tetrahydrofuran, and fluoroalcohols. It is notable that the stereochemistry of the polymerization depended on monomer concentration: a lower monomer concentration led to a higher isotacticity for DMAA polymerization and a higher syndiotacticity for DPAA polymerization. This effect was explained by assuming that there exist two types of growing radicals having different stereoselectivities. By optimizing the aforementioned reaction conditions, poly(DMAA) with dial isotacticity (m) of 77% (polymerization in toluene at −78°C at [M]0=0.1M) and poly(DPAA) with diad syndiotacticity (r) of 93% (polymerization in THF at -98°C at [M]0=0.22M) were obtained. Stereoregular poly(methyl acrylate)s were derived from the poly(DPAA)s. Thermal property of the poly(methyl acrylate)s with different tacticities was studied by DSC.
Similar content being viewed by others
Article PDF
References
For a review,see: T. Nakano and Y. Okamoto, in “Controlled Radical Polymerization,” K. Matyjazsewski, Ed., ACS Symposium Series 685, American Chemical Society, Washington, D.C., 1998, pp451—462.
T. Nakano, A. Matsuda, and Y. Okamoto, Polym. J., 28, 556 (1996).
Y. Isobe, K. Yamada, T. Nakano, and Y. Okamoto, macromolecules, 32, 5979 (1999).
W. Liu, T. Nakano, and Y. Okamoto, J. Polym. Sci., Polym. Chem., in press.
K. Shiohara, S. Habaue, and Y. Okamoto, Polym. J., 28, 682 (1996).
S. Habaue, K. Shiohara, T. Uno, and Y. Okamoto, Enantiomer, 1, 55 (1996).
K. Shiohara, S. Habaue, and Y. Okamoto, Polym. J., 30, 249 (1998).
T. Uno, K. Shiohara, S. Habaue, and Y. Okamoto, Polym. J., 30, 352 (1998).
N. A. Porter, T. R. Allen, and R. A. Breyer, J. Am. Chem. Soc., 114, 7676 (1992).
K. Yamada, T. Nakano, and Y. Okamoto, Macromolecules, 31, 7598 (1998).
K. Yamada, T. Nakano, and Y. Okamoto, J. Polym. Sci., Polym. Chem., 37, 2677 (1999).
K. Matsuzaki, T. Uryu, and A. Ishida, J. Polym. Sci., Part A-1, 5, 2167 (1967).
H. Gia and J. E. McGrath, Polym. Prepr., Am. Chem. Soc., Div. Polym. Chem., 21 (1), 74 (1980).
H. Gia and J. E. McGrath, Polym. Bull., 2, 837 (1980).
S. S. Huang and J. E. McGrath, Polym. Prepr., Am. Chem. Soc., Div. Polym. Chem., 24 (2), 138 (1983).
X. Xie and T. E. Hogen-Esch, Macromolecules, 29, 1746 (1996).
T. Uryu, H. Shiroki, M. Okada, K. Hosonuma, and K. Matsuzaki, J. Polym. Sci., Part A-1, 9, 2335 (1971).
M. Kobayashi, S. Okuyama, T. Ishizone, and S. Nakahama, Macromolecules, 32, 6466 (1999).
S. Nakahama, M. Kobayashi, T. Ishizone, and A. Hirao, J. Macromol. Sci.-Pure Appl. Chem., A34, 1845 (1997).
A. Bulai, M. L. Jimeno, A. A.D. Queiroz, A. Gallardo, and J. S. Roman, Macromolecules, 29, 3240 (1996).
For an example: W. Liu, T. Nakano, and Y. Okamoto, Polym. J., 31, 479 (1999).
J. W. L. Fordham, J. Polym. Sci., 39, 321 (1959).
T. Kitayama, T. Kawauchi, M. Tabuchi, and K. Hatada, Polym. Prepr., Jpn., 48, 1289 (1999).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Liu, W., Nakano, T. & Okamoto, Y. Stereocontrol in Radical Polymerization of N,N-Dimethylacrylamide and N,N-Diphenylacrylamide and Thermal Properties of Syndiotactic Poly(methyl acrylate)s Derived from the Obtained Polymers. Polym J 32, 771–777 (2000). https://doi.org/10.1295/polymj.32.771
Issue Date:
DOI: https://doi.org/10.1295/polymj.32.771