Article (Scientific journals)
Effective cobalt-mediated radical coupling (CMRC) of poly(vinylacetate) and poly(N-vinylpyrrolidone) (co)polymer precursors
Debuigne, Antoine; Poli, Rinaldo; De Winter, Julien et al.
2010In Macromolecules, 43 (6), p. 2801-2813
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Keywords :
radical polymerization; cobalt-mediated radical coupling (CMRC)
Abstract :
[en] Cobalt-mediated radical coupling (CMRC) is successfully applied to poly(vinyl acetate) (PVAc) and poly(N-vinylpyrrolidone) (PNVP) precursors for the first time. The coupling process is based on addition of isoprene onto polymer chains preformed by controlled radical polymerization with cobalt complexes (CMRP). The extents of coupling were high (>90%) to moderate (75-80%) for PVAc and PNVP precursors, respectively. Effects of the length of the polymer precursors and conditions used in the polymerization step on the coupling efficiency are discussed. Mass spectrometry (MS) and nuclear magnetic resonance (NMR) analyses conducted on the coupling products demonstrate the preferential insertion of two isoprene units in the final polymers. The CMRC mechanistic proposal, supported by DFT calculations, is based on this microstructure feature. Finally, illustration of the macromolecular engineering potential of this technique is given by the preparation of symmetrical PVAc-b-PNVP-b-PVAc triblock copolymers starting from the corresponding PVAc-b-PNVP-[Co] diblock copolymer.
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)
Poli, Rinaldo;  Université de Toulouse et Institut Universitaire de France (Paris) > Laboratoire de Chimie de Coordination (Toulouse)
De Winter, Julien;  University of Mons (UMons) > Mass Spectrometry Center > Organic Chemistry Laboratory
Laurent, Pascal ;  Université de Liège - ULiège > Chimie et bio-industries > Chimie biologique industrielle
Gerbaux, Pascal;  University of Mons (UMons) > Mass Spectrometry Center > Organic Chemistry Laboratory
Wathelet, Jean-Paul ;  Université de Liège - ULiège > Chimie et bio-industries > Chimie générale et organique
Jérôme, Christine  ;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Detrembleur, Christophe ;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
Effective cobalt-mediated radical coupling (CMRC) of poly(vinylacetate) and poly(N-vinylpyrrolidone) (co)polymer precursors
Publication date :
23 March 2010
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
American Chemical Society, Washington, United States - District of Columbia
Volume :
43
Issue :
6
Pages :
2801-2813
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique
F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE]
The french "CNRS" and the IUF
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