Abstract
The ruthenium-catalyzed living radical polymerization was first applied to the synthesis of a series of well-defined graft polymers with the controlled lengths of both the backbone and graft chains. The synthetic method was based on the ruthenium-catalyzed “grafting-from” polymerization of various monomers, such as methacrylate, acrylate, and styrene, from the backbone polymers also obtained via the ruthenium-catalyzed living radical polymerization. The backbone polymer was first synthesized by the ruthenium-catalyzed living radical random copolymerization of methyl methacrylate (MMA) and 2-(trimethylsilyloxy)ethyl methacrylate (TMSHEMA) followed by the in situ transformation of the silyloxyl group into the ester with a C–Br bond via direct reaction with the acid bromide (2-bromoisobutyryl bromide). The obtained multifunctional macroinitiator was employed for the ruthenium-catalyzed “grafting-from” radical polymerization of MMA, n-butyl acrylate, styrene, and TMSHEMA to afford a series of the graft polymers (Mw/Mn∼1.1) with controlled lengths of the backbone and graft chains.
Similar content being viewed by others
Article PDF
References
M. K. Georges, R. P. N. Veregin, P. M. Kazmaier, and G. K. Hamer, Macromolecules, 26, 2987 (1993).
M. K. Georges, R. P. N. Veregin, P. M. Kazmaier, and G. K. Hamer, Trends. Polym. Sci., 2, 66 (1994).
C. J. Hawker, J. Am. Chem. Soc., 116, 11185 (1994).
C. J. Hawker, A. W. Bosman, and E. Harth, Chem. Rev., 101, 3661 (2001).
M. Kato, M. Kamigaito, M. Sawamoto, and T. Higashimura, Macromolecules, 28, 1721 (1995).
M. Kamigaito, T. Ando, and M. Sawamoto, Chem. Rev., 101, 3689 (2001).
M. Kamigaito, T. Ando, and M. Sawamoto, Chem. Rec., 4, 3661 (2004).
J.-S. Wang and K. Matyjaszewski, J. Am. Chem. Soc., 117, 5614 (1995).
K. Matyjaszewski and J. Xia, Chem. Rev., 101, 2921 (2001).
J. Chiefari, Y. K. (B.) Chong, F. Ercole, J. Krstina, J. Jeffery, T. P. T. Le, R. T. A. Mayadunne, G. F. Meijs, C. L. Moad, G. Moad, E. Rizzardo, and S. H. Thang, Macromolecules, 31, 5559 (1998).
For reviews, see: 11–13. K. A. Davis and K. Matyjaszewski, Adv. Polym. Sci., 159, 1 (2002).
H. G. Börner and K. Matyjaszewski, Macromol. Symp., 177, 1 (2002).
A. Bhattacharya and B. N. Misra, Prog. Polym. Sci., 29, 767 (2004).
H. Mori and A. H. E. Müller, Prog. Polym. Sci., 28, 1403 (2003).
Y. Cai, M. Hartenstein, and A. H. E. Müller, Macromolecules, 37, 7484 (2004).
S. G. Roos, A. H. E. Müller, and K. Matyjaszewski, Macromolecules, 32, 8331 (1999).
H. Shinoda, K. Matyjaszewski, L. Okrasa, M. Mierzwa, and T. Pakula, Macromolecules, 36, 4772 (2003).
D. Neugebauer, Y. Zhang, T. Pakula, S. S. Sheiko, and K. Matyjaszewski, Macromolecules, 36, 6746 (2003).
D. Neugebauer, M. Theis, T. Pakula, G. Wegner, and K. Matyjaszewski, Macromolecules, 39, 584 (2006).
D. M. Haddleton, S. Perrier, and S. A. F. Bon, Macromolecules, 33, 8246 (2000).
K. Yamada, M. Miyazaki, K. Ohno, T. Fukuda, and M. Minoda, Macromolecules, 32, 290 (1999).
G. Cheng, A. Böker, M. Zhang, G. Krausch, and A. H. E. Müller, Macromolecules, 34, 6883 (2001).
C. Li, N. Gunari, K. Fischer, A. Janshoff, and M. Schmidt, Angew. Chem., Int. Ed., 43, 1101 (2004).
K. L. Beers, S. G. Gaynor, K. Matyjaszewski, S. S. Sheiko, and M. Möller, Macromolecules, 31, 9413 (1998).
H. G. Börner, K. L. Beers, K. Matyjaszewski, S. S. Sheiko, and M. Möller, Macromolecules, 34, 4375 (2001).
H. G. Börner, D. Duran, K. Matyjaszewski, M. da Silva, and S. S. Sheiko, Macromolecules, 35, 3387 (2002).
S. Qin, K. Matyjaszewski, H. Xu, and S. S. Sheiko, Macromolecules, 36, 605 (2003).
S. J. Lord, S. S. Sheiko, I. LaRue, H.-I. Lee, and K. Matyjaszewski, Macromolecules, 37, 4235 (2004).
B. S. Sumerlin, D. Neugebauer, and K. Matyjaszewski, Macromolecules, 38, 702 (2005).
H. Lee, K. Matyjaszewski, S. Yu, and S. S. Sheiko, Macromolecules, 38, 8264 (2005).
Y. Miura, Y. Isobe, T. Nakamura, M. Sugiura, and Y. Okamoto, Polym. J., 37, 617 (2005).
R. B. Grubbs, C. J. Hawker, J. Dao, and J. M. J. Fréchet, Angew. Chem., Int. Ed., 36, 270 (1997).
R. Venkatesh, L. Yajjou, C. E. Koning, and B. Klumperman, Macromol. Chem. Phys., 205, 2161 (2004).
N. Khelfallah, N. Gunari, K. Fischer, G. Gkogkas, N. Hadjichristidis, and M. Schmidt, Macromol. Rapid Commun., 26, 1693 (2005).
For reviews, see: 35–37. J. Pyun and K. Matyjaszewski, Chem. Mater., 13, 3436 (2001).
J. Pyun, T. Kowalewski, and K. Matyjaszewski, Macromol. Rapid Commun., 24, 1043 (2003).
S. Edmondson, V. L. Osborne, and W. T. S. Huck, Chem. Soc. Rev., 33, 14 (2004).
M. Ejaz, S. Yamamoto, K. Ohno, Y. Tsujii, and T. Fukuda, Macromolecules, 31, 5934 (1998).
S. Yamamoto, M. Ejaz, Y. Tsujii, M. Matsumoto, and T. Fukuda, Macromolecules, 33, 5602 (2000).
S. Yamamoto, M. Ejaz, Y. Tsujii, and T. Fukuda, Macromolecules, 33, 5608 (2000).
S. Yamamoto, Y. Tsujii, and T. Fukuda, Macromolecules, 33, 5995 (2000).
H. Sakata, M. Kobayashi, H. Otsuka, and A. Takahara, Polym. J., 37, 767 (2005).
K.-Y. Beak, Kamigaito, and M. Sawamoto, J. Polym. Sci., Part A: Polym. Chem., 40, 1937 (2002).
T. Ando, M. Kamigaito, and M. Sawamoto, Macromolecules, 31, 6708 (1998).
Y. Kotani, M. Kato, M. Kamigaito, and M. Sawamoto, Macromolecules, 29, 6979 (1996).
J. Ueda, M. Matsuyama, M. Kamigaito, and M. Sawamoto, Macromolecules, 31, 557 (1998).
J. Ueda, M. Kamigaito, and M. Sawamoto, Macromolecules, 31, 6762 (1998).
K.-Y. Beak, Kamigaito, and M. Sawamoto, Macromolecules, 34, 215 (2001).
T. Terashima, M. Kamigaito, K.-Y. Beak, T. Ando, and M. Sawamoto, J. Am. Chem. Soc., 125, 5288 (2003).
T. Ando, M. Kamigaito, and M. Sawamoto, Macromolecules, 33, 2819 (2000).
H. Takahashi, T. Ando, M. Kamigaito, and M. Sawamoto, Macromolecules, 32, 3820 (1999).
S. Hamasaki, M. Kamigaito, and M. Sawamoto, Macromolecules, 35, 2934 (2002).
T. Ando, M. Kamigaito, and M. Sawamoto, Macromolecules, 33, 5825 (2000).
Y. Watanabe, T. Ando, M. Kamigaito, and M. Sawamoto, Macromolecules, 34, 4370 (2001).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Miura, Y., Satoh, K., Kamigaito, M. et al. Well-Defined Graft Copolymers of Methacrylate, Acrylate, and Styrene via Ruthenium-Catalyzed Living Radical Polymerization. Polym J 38, 930–939 (2006). https://doi.org/10.1295/polymj.PJ2006031
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1295/polymj.PJ2006031
Keywords
This article is cited by
-
Controlled/living polymerization of renewable vinyl monomers into bio-based polymers
Polymer Journal (2015)
-
Synthesis and characterization of poly(2-ethylhexyl acrylate) prepared via atom transfer radical polymerization, reverse atom transfer radical polymerization and radical polymerization
Journal of Chemical Sciences (2013)
-
Recent developments in metal-catalyzed living radical polymerization
Polymer Journal (2011)