Effective cobalt-mediated radical coupling (CMRC) of poly(vinylacetate) and poly(N-vinylpyrrolidone) (co)polymer precursors

Debuigne, Antoine; Poli, Rinaldo; De Winter, Julien; Laurent, Pascal; Gerbaux, Pascal; Wathelet, Jean-Paul; Jérôme, Christine; Detrembleur, Christophe

doi:10.1021/ma902610m

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.

2010 • In Macromolecules, 43 (6), p. 2801-2813

Peer Reviewed verified by ORBi

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https://hdl.handle.net/2268/26799

DOI
10.1021/ma902610m

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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/Unit :

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 :

Issue :

Pages :

2801-2813

Peer reviewed :

Peer Reviewed verified by ORBi

Additional URL :

http://pubs.acs.org/doi/pdf/10.1021/ma902610m

Funders :

BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique
F.R.S.-FNRS - Fonds de la Recherche Scientifique
The french "CNRS" and the IUF

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