[en] Poly(vinyl acetate) (PVAc) chains prepared by cobalt-mediated radical polymerization in the presence of cobalt(II) acetylacetonate (Co(acac)(2)) were quenched by radical scavengers, such as thiol compounds and nitroxides, to displace the covalently bonded Co(acac)(2) moiety and to end-cap them with a reactive group. The cobalt complex was completely removed by filtration, as confirmed by the induction coupled plasma (ICP) analysis of the polymer before and after treatment. Growing poly(vinyl acetate) chains can be end-functionalized either by addition of an appropriately functionalized nonpolymerizable olefin or by displacement of the Co(acac)(2) moiety by a functionalized nitroxide. This strategy allows PVAc to be synthesized with a predictable molecular weight, a reasonably low polydispersity (M-w/M-n similar to 1.1-1.3), and a functional omega end group, e.g., hydroxyl and epoxy.
Research center :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Debuigne, Antoine ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Caille, Jean-Raphaël; Université de Liège - ULiège > Department 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)
Language :
English
Title :
Synthesis of end-functional poly(vinyl acetate) by cobalt-mediated radical polymerization
Publication date :
28 June 2005
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
Amer Chemical Soc, Washington, United States - Washington
(a) Moad, G. H.; Solomon, D. H.; Johns, S. R.; Willing, R. I. Macromolecules 1982, 15, 1188.
(b) Georges, M. K.; Veregin, R. P. N.; Kazmaier, P. M.; Hamer, G. K. Macromolecules 1998, 26, 2987.
(c) Hawker, C. J.; Bosman, A. W.; Hart, E. Chem. Rev. 2001, 101, 3661.
(a) Kato, M.; Kamigaito, M.; Sawamoto, M.; Higashimura, T. Macromolecules 1995, 28, 1721.
(b) Wang, J. S.; Matyjaszewski, K. J. Am. Chem. Soc. 1995, 117, 5614.
(c) Kamigaito, M.; Ando, T.; Sawamoto, M. Chem. Rev. 2001, 101, 3689.
Matyjaszewski, K.; Xia, J. Chem. Rev. 2001, 101, 2921.
(a) Chiefari, J.; Chong, Y. K.; Ercole, F.; Kristina, 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.
(b) Mayadunne, R. T. A.; Rizzardo, E.; Chiefari, J.; Chong, Y. K.; Moad, G.; Thang, S. H. Macromolecules 1999, 32, 6977.
(c) 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.
Lai, J. T.; Filla, D.; Shea, R. Macromolecules 2002, 35, 6754.
(a) Rodlert, M.; Harth, E.; Rees, I.; Hawker, C. J. J. Polym. Sci., Polym. Chem. 2000, 38, 4749.
(b) Hawker, C. J.; Hedrick, J. L. Macromolecules 1995, 28, 2993.
(c) Harth, E.; Hawker, C. J.; Fan, W.; Waymouth, R. M. Macromolecules 2001, 34, 3856.
(a) Wayland, B. B.; Poszmik, G.; Mukerjee, S. L.; Fryd, M. J. Am. Chem. Soc. 1994, 116, 7943.
(b) Wayland, B. B.; Basickes, L.; Mukerjee, S. L.; Wei, M.; Fryd, M. Macromolecules 1997, 30, 8109.
(c) Lu, Z.; Fryd, M.; Wayland, B. B. Macromolecules 2004, 37, 2686.
Arvanitopoulos, L. D.; Greuel, M. P.; King, B. M.; Shim, A. K.; Harwood: H. J. ACS Symp. Ser. 1998, 685, 316-331.
Halpern, J. Science 1985, 227, 869.
Tsou, T. T.; Loots, M.; Halpern, J. J. Am. Chem. Soc. 1982, 104, 623.
Flora, T. T. Ng.; Remple, G. L.; Mancuso, C.; Halpern, J. Organometallics 1990, 9, 2762.
(a) Kemmitt, R. D. W.; Russel, D. R. In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, A., Abel, E., Eds.; Pergamon Press: Oxford, 1982; Vol. 5, pp 1-276.
(b) Sweany, R. L. In Comprehensive Organometallic Chemistry II; Wilkinson, G., Stone, A., Abel, E., Eds.; Pergamon Press: Oxford, 1995; Vol. 8, pp 1-114.
McAllister, R.; Weber, J. H. J. Organomet. Chem. 1974, 77, 91.