Abstract
With the use of two classes of reversible addition-fragmentation chain-transfer agents—dithiobenzoates and trithiocarbonates—multiblock copolymers based on styrene and n-butyl acrylate, which are the best-studied monomers in these processes, are synthesized. It is shown that the polymers containing dithiobenzoate and trithiocarbonate groups are highly efficient for the synthesis of block copolymers, which is independent of the number of stages at which the polymeric RAFT agents are used in polymerization: In all cases, the polymeric RAFT agent is fully consumed in the polymerization of the “alien” monomer. The mechanism governing chain formation during the synthesis of multiblock copolymers, that is, the character of monomer insertion into the polymer chain, via one or both ends, is studied. It is found that the order of monomer loading determines the ratio of chains growing through one or two ends. The thermal stability of amphiphilic multiblock copolymers, their solubility in various solvents, and self-organizing ability are investigated.
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References
N. Hadjichristidis, S. Pispas, and G. Floudas, Block Copolymers: Synthesis Strategies, Physical Properties, and Applications (Wiley, Hoboken, 2003).
C. Sadron and A. Gallot, Makromol. Chem. 164, 301 (1973).
L. Z. Rogovina and G. A. Slonimskii, Usp. Khim. 46, 1871 (1977).
A. Noshay and J. McGrath, Block Copolymers (Academic, New York, 1977; Mir, Moscow, 1980).
Developments in Block Copolymer Science and Technology, Ed. by I. W. Hamley (Wiley, Hoboken, 2004).
Y. K. Chong, J. Kristina, T. P. T. Le, G. Moad, A. Postma, E. Rizzardo, and S. H. Thang, Macromolecules 36, 2256 (2003).
E. V. Chernikova, Doctoral Dissertation in Chemistry (Moscow State Univ., Moscow, 2010).
J. Chiefari, Y. K. Chong, F. Ecrole, J. Kristina, J. Jeffery, T. P. T. Le, R. T. Mayadunne, G. F. Meijs, C. L. Moad, G. Moad, E. Rizzardo, and S. H. Thang, Macromolecules 31, 5559 (1998).
G. Moad, E. Rizzardo, and S. H. Thang, Polymer 49, 1079 (2008).
S. Perrier and P. Takolpuckdee, J. Polym. Sci., Part A: Polym. Chem. 43, 5347 (2005).
A. Goto, K. Sato, Y. Tsujii, T. Fukuda, G. Moad, and E. Rizzardo, Macromolecules 34, 402 (2001).
E. V. Chernikova, A. V. Tarasenko, V. V. Yulusov, E. S. Garina, V. B. Golubev, Polymer Science, Ser. A 51, 667 (2009) [Vysokomol. Soedin., Ser. A 51, 992 (2009)].
J.-J. Yuan, R. Ma, Q. Gao, Y.-F. Wang, S.-Y. Cheng, L. Feng, Z.-Q. Fan, and L. Jiang, J. Appl. Polym. Sci. 89, 1017 (2003).
E. V. Sivtsov, E. V. Chernikova, P. S. Terpugova, and O. G. Yasnogorodskaya, Zh. Prikl. Khim. (S.-Peterburg) 82, 630 (2009).
Y. T. Li, B. S. Lokitz, and C. L. McCormick, Macromolecules 39, 81 (2006).
E. V. Bryuzgin and A. V. Navrotskii, in Proceedings of VII International Russia-Kazakhstan-Japan Scientific Conference, Moscow, 2009, p. 797.
W. Zhang, N. Zhou, Z. Cheng, J. Zhu, and X. Zhu, Polymer 49, 4569 (2008).
C. Barner-Kowollik and S. Perrier, J. Polym. Sci., Part A: Polym. Chem. 46, 5715 (2008).
M. Eberhardt and P. Theato, Macromolecules 26, 1488 (2005).
T. Krasia, R. Soula, H. G. Borner, and H. Schlaad, Chem. Commun., 538 (2003).
J. Xu, W. Zhang, N. Zhou, J. Zhu, Z. Cheng, Y. Xu, and X. Zhu, J. Polym. Sci., Part A: Polym. Chem. 46, 5652 (2008).
J. Wang, W. Xu, Z. Cheng, X. Zhu, Z. Zhang, and J. Zhu, J. Polym. Sci., Part A: Polym. Chem. 46, 7690 (2008).
Y. Q. Hu, M. S. Kim, and D. S. Lee, J. Polym. Sci., Part A: Polym. Chem. 46, 3740 (2008).
V. B. Golubev, E. V. Chernikova, E. A. Leonova, and A. V. Morozov, Polymer Science, Ser. A 47, 678 (2005) [Vysokomol. Soedin., Ser. A 47, 1115 (2005)].
E. V. Chernikova, A. V. Tarasenko, E. S. Garina, and V. B. Golubev, Polymer Science, Ser. A 48, 1046 (2006) [Vysokomol. Soedin., Ser. A 48, 1787 (2006)].
E. V. Chernikova, P. S. Terpugova, E. S. Garina, and V. B. Golubev, Polymer Science, Ser. A 49, 108 (2007) [Vysokomol. Soedin., Ser. A 49, 208 (2007)].
E. V. Chernikova, P. S. Terpugova, M. Yu. Trifilov, E. S. Garina, V. B. Golubev, E. V. Sivtsov, Polymer Science, Ser. A 51, 658 (2009) [Vysokomol. Soedin., Ser. A 51, 983 (2009)].
P. S. Terpugova, Candidate’s Dissertation in Chemistry (Moscow State Univ., Moscow, 2009).
A. V. Tarasenko, Candidate’s Dissertation in Chemistry (Moscow State Univ., Moscow, 2008).
E. Chernikova, A. Morozov, E. Leonova, E. Garina, V. Golubev, Ch. Bui, and B. Charleux, Macromolecules 37, 6329 (2004).
E. V. Chernikova, P. S. Terpugova, A. N. Filippov, E. S. Garina, V. B. Golubev, A. I. Gostev, and E. V. Sivtsov, Zh. Prikl. Khim. (S.-Peterburg) 82, 1730 (2009).
Infrared Absorption Spectra of Polymers and Individual Compounds, Ed. by V. M. Chulanovskii (Khimiya, Moscow, 1969) [in Russian].
Handbook of RAFT Polymerization, Ed. by C. Barner-Kowollik (Wiley-VCH, Weinheim, 2008).
Encyclopedia of Polymers (Sovetskaya Entsiklopediya, Moscow, 1972), Vol. 1 [in Russian].
Chemical Encyclopedia (Bol’shaya Rossiiskaya Entsiklopediya, Moscow, 1992), Vol. 3 [in Russian].
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Original Russian Text © E.V. Chernikova, D.V. Vishnevetskii, E.S. Garina, A.V. Plutalova, E.A. Litmanovich, B.A. Korolev, A.V. Shlyakhtin, Yu.V. Kostina, G.N. Bondarenko, 2012, published in Russian in Vysokomolekulyarnye Soedineniya, Ser. B, 2012, Vol. 54, No. 3, pp. 455–470.
This work was supported by the Russian Foundation for Basic Research, project nos. 11-03-00640 and 11-03-00232.
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Chernikova, E.V., Vishnevetskii, D.V., Garina, E.S. et al. Controlled synthesis of multiblock copolymers by pseudoliving radical polymerization via the reversible addition-fragmentation chain-transfer mechanism. Polym. Sci. Ser. B 54, 127–141 (2012). https://doi.org/10.1134/S1560090412030025
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DOI: https://doi.org/10.1134/S1560090412030025