Mechanistic Insights into the Cobalt-Mediated Radical Polymerization (CMRP) of Vinyl Acetate with Cobalt(III) Adducts as Initiators

Over the past few years, cobalt‐mediated radical polymerization (CMRP) has proved efficient in controlling the radical polymerization of very reactive monomers, such as vinyl acetate (VAc). However, the reason for this success and the intimate mechanism remained basically speculative. Herein, two me...

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Bibliographic Details
Published in:Chemistry : a European journal Vol. 14; no. 13; pp. 4046 - 4059
Main Authors: Debuigne, Antoine, Champouret, Yohan, Jérôme, Robert, Poli, Rinaldo, Detrembleur, Christophe
Format: Journal Article
Language:English
Published: Weinheim WILEY-VCH Verlag 28.04.2008
WILEY‐VCH Verlag
Wiley
Wiley-VCH Verlag
Subjects:
Chemical Sciences
Chemistry
Chemistry, Multidisciplinary
Chimie
cobalt
cobalt-mediated radical polymerization (CMRP)
Coordination chemistry
density functional calculations
Engineering, computing & technology
Ingénierie, informatique & technologie
Materials science & engineering
Physical Sciences
Physical, chemical, mathematical & earth Sciences
Physique, chimie, mathématiques & sciences de la terre
polymerization
radical polymerization
radical reactions
Science & Technology
Science des matériaux & ingénierie
vinyl acetate
polymerization
POLY(VINYL ACETATE)
ACTIVATION
BLOCK-COPOLYMERS
FRAGMENTATION CHAIN TRANSFER
radical reactions
REACTIVITY
cobalt
ATOM
VITAMIN-B12
density functional calculations
DEGENERATIVE TRANSFER
CHEMISTRY
vinyl acetate
ACRYLATES
Polymerization
Density functional calculations
Radical reactions
Vinyl acetate
Cobalt
ISSN:0947-6539, 1521-3765, 1521-3765
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Summary:Over the past few years, cobalt‐mediated radical polymerization (CMRP) has proved efficient in controlling the radical polymerization of very reactive monomers, such as vinyl acetate (VAc). However, the reason for this success and the intimate mechanism remained basically speculative. Herein, two mechanisms are shown to coexist: the reversible termination of the growing poly(vinyl acetate) chains by the Co(acac)2 complex (acac: acetylacetonato), and a degenerative chain‐transfer process. The importance of one contribution over the other strongly depends on the polymerization conditions, including complexation of cobalt by ligands, such as water and pyridine. This significant progress in the CMRP mechanism relies on the isolation and characterization of the very first cobalt adducts formed in the polymerization medium and their use as CMRP initiators. The structure proposed for these adducts was supported by DFT calculations. Beyond the control of the VAc polymerization, which is the best ever achieved by CMRP, extension to other monomers and substantial progress in macromolecular engineering are now realistic forecasts. A radical change! Some cobalt complexes mediate the radical polymerization of vinyl monomers, and particularly the one of vinyl acetate. Polymers with well‐defined and predictable molecular parameters can thus be prepared by the so‐called Cobalt‐Mediated Radical Polymerization (CMRP) system. The synthesis and the use of cobalt(III) adduct (see graphic) as CMRP initiator revealed the intimate mechanism of this technique, as supported by kinetics data and DFT calculations.
Bibliography:ArticleID:CHEM200701867
Agence National de la Recherche - No. NT05-2 42140
Fonds National de la Recherche Scientifique
Interuniversity Attraction Poles Programme (PAI VI/27)-Functional Supramolecular Systems
Centre Interuniversitaire de Calcul de Toulouse
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istex:944FF0DBAFB067DCDE4A932A9F2FF192D654AA5A
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
scopus-id:2-s2.0-44649191888
ISSN:0947-6539
1521-3765
1521-3765
DOI:10.1002/chem.200701867