[en] Poly(vinyl acetate)−Co(acac)2 macroinitiators, prepared by cobalt-mediated radical polymerization of vinyl acetate (VAc), were used to synthesize well-defined poly(vinyl acetate)-b-poly(acrylonitrile) (PVAc-b-PAN) block copolymers. Different solvents and temperatures were tested for the polymerization of the acrylonitrile segment by cobalt-mediated radical polymerization (CMRP), and copolymers with low polydispersity were obtained provided that dimethylformamide was used as solvent at 0 °C. The mechanism of control was assumed to change from a degenerative chain transfer mechanism for the VAc polymerization to a reversible-termination process for the AN polymerization. The hydrolysis of the ester groups of the PVAc block and the nitrile groups of the PAN sequence of the copolymer by potassium hydroxide in an ethanol/water mixture provided the double hydrophilic and pH-responsive poly(vinyl alcohol)-b-poly(acrylic acid) block copolymer. Finally, the pH responsiveness of these copolymers was demonstrated by DLS pH titration with formation of aggregates at pH < 3.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Debuigne, Antoine ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Warnant, Jérôme; Université de Liège - ULiège > Depmartment of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Robert ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Voets, Ilja; University of Wageningen, The Netherlands > Laboratory of Physical Chemistry and Colloid Science
de Keizer, Arie; University of Wageningen, The Netherlands > Laboratory of Physical Chemistry and Colloid Science
Cohen Stuart, Martien A; University of Wageningen, The Netherlands > Laboratory of Physical Chemistry and Colloid Science
Detrembleur, Christophe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
Synthesis of novel well-defined poly(vinyl acetate)-b-poly(acrylonitrile) and derivatized water-soluble poly(vinyl alcohol)-b-poly(acrylic acid) block copolymers by cobalt-mediated radical polymerization
Publication date :
08 April 2008
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
American Chemical Society, Washington, United States - Washington
Braunecker, W. A.; Matyjaszewski, K. Prog. Polym. Sci. 2007, 32, 93-146.
Hawker, C. J.; Bosman, A. W.; Harth, E. Chem. Rev. 2001, 101, 3661-3688.
Georges, M. K.; Veregin, R. P. N.; Kazmaier, P. M.; Hamer, G. K. Macromolecules 1993, 26, 2987-2988.
Kamigaito, M.; Ando, T.; Sawamoto, M. Chem. Rev. 2001, 101, 3689-3745.
Matyjaszewski, K.; Xia, J. Chem. Rev. 2001, 101, 2921-2990.
Tsarevsky, N. V.; Matyjaszewski, K. Chem. Rev. 2007, 101, 2270-2299.
Moad, G.; Rizzardo, E.; Thang, S. H. Aust. J. Chem. 2005, 58, 379-410.
Moad, G.; Chiefari, J.; Chong, Y. K.; Krstina, J.; Mayadunne, R. T. A.; Postma, A.; Rizzardo, E.; Thang, S. H. Polym. Int. 2000, 49, 993-1001.
Chiefari, J.; Chong, Y. K.; Ercole, F.; Krstina, J.; Jeffery, J.; Le, T. P. T.; Mayadunne, R. T. A.; Meijs, G. F.; Moad, C. L.; Moad, G.; Rizzardo, E.; Thang, S. H. Macromolecules 1998, 31, 5559-5562.
Lai, J. T.; Filla, D.; Shea, R. Macromolecules 2002, 35, 6754-6756.
Perrier, S.; Takolpuckdee, P.; Mars, C. A. Macromolecules 2005, 38, 2033-2036.
Charmot, D.; Corpart, P.; Adam, H.; Zard, S. Z.; Biadatti, T.; Bouhadir, G. Macromol. Symp. 2000, 150, 23-32.
