References of "Debuigne, Antoine"
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See detailIsoprene-assisted radical coupling of (co)polymers prepared by cobalt-mediated radical polymerization
Debuigne, Antoine ULg; Jérôme, Christine ULg; Detrembleur, Christophe ULg

in Angewandte Chemie (International ed. in English) (2009), 48(8), 1422-1424

The isoprene-assisted radical coupling (I-ARC) of polymers prepared by cobalt-mediated radical polymerization (see picture) is the first efficient radical coupling method that is not restricted to short ... [more ▼]

The isoprene-assisted radical coupling (I-ARC) of polymers prepared by cobalt-mediated radical polymerization (see picture) is the first efficient radical coupling method that is not restricted to short chains. When applied to AB diblock copolymers, I-ARC constitutes a straightforward approach to the preparation of novel symmetrical ABA triblock copolymers [less ▲]

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See detailCobalt-assisted synthesis of novel block copolymers
Debuigne, Antoine ULg

Scientific conference (2009, February 05)

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See detailCobalt-mediated radical polymerization of acrylonitrile: Kinetics investigations and DFT calculations
Debuigne, Antoine ULg; Michaux, Catherine; Jérôme, Christine ULg et al

in Chemistry : A European Journal (2008), 14(25), 7623-7637

The successful controlled homopolymerization of acrylonitrile (AN) by cobalt-mediated radical polymerization (CMRP) is reported for the first time. As a rule, initiation of the polymerization was carried ... [more ▼]

The successful controlled homopolymerization of acrylonitrile (AN) by cobalt-mediated radical polymerization (CMRP) is reported for the first time. As a rule, initiation of the polymerization was carried out starting from a conventional azo-initiator (V-70) in the presence of bis(acetylacetonato)cobalt(II) ([Co(acac)2]) but also by using organocobalt(III) adducts. Molar concentration ratios of the reactants, the temperature, and the solvent were tuned, and the effect of these parameters on the course of the polymerization is discussed in detail. The best level of control was observed when the AN polymerization was initiated by an organocobalt(III) adduct at 0 °C in dimethyl sulfoxide. Under these conditions, poly(acrylonitrile) with a predictable molar mass and molar mass distribution as low as 1.1 was prepared. A combination of kinetic data, X-ray analyses, and DFT calculations were used to rationalize the results and to draw conclusions on the key role played by the solvent molecules in the process. These important mechanistic insights also permit an explanation of the unexpected solvent effect that allows the preparation of well-defined poly(vinyl acetate)-b-poly(acrylonitrile) by CMRP. [less ▲]

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See detailKey role of metal-coordination in cobalt mediated radical polymerization
Debuigne, Antoine ULg; Poli, Rinaldo; Jérôme, Christine ULg et al

Poster (2008, May 22)

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See detailSynthesis 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
Debuigne, Antoine ULg; Warnant, Jérôme; Jérôme, Robert ULg et al

in Macromolecules (2008), 41(7), 2353-2360

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 ... [more ▼]

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. [less ▲]

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See detailMechanistic Insights into the Cobalt-Mediated Radical Polymerization (CMRP) of Vinyl Acetate with Cobalt(Iii) Adducts as Initiators
Debuigne, Antoine ULg; Champouret, Yohan; Jérôme, Robert ULg et al

in Chemistry : A European Journal (2008), 14(13), 4046-4059

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 ... [more ▼]

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. [less ▲]

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See detailMetal-coordination: an effective lever for cobalt-mediated radical polymerization
Debuigne, Antoine ULg; Jérôme, Christine ULg; Jérôme, Robert ULg et al

in Polymer Preprints (2008), 49(27), 193-194

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See detailAmphiphilic poly(vinyl acetate)-b-poly(N-vinylpyrrolidone) and novel double hydrophilic poly(vinyl alcohol)-b-poly(N-vinylpyrrolidone) block copolymers prepared by cobalt-mediated radical polymerization
Debuigne, Antoine ULg; Willet, Nicolas ULg; Jérôme, Robert ULg et al

in Macromolecules (2007), 40(20), 7111-7118

Well-defined amphiphilic block copolymers of poly(vinyl acetate) (PVAc) and poly(N-vinylpyrrolidone) (PNVP) were synthesized by cobalt-mediated radical polymerization (CMRP). The NVP polymerization ... [more ▼]

Well-defined amphiphilic block copolymers of poly(vinyl acetate) (PVAc) and poly(N-vinylpyrrolidone) (PNVP) were synthesized by cobalt-mediated radical polymerization (CMRP). The NVP polymerization initiated by poly(vinyl acetate) end-capped by the cobalt(II)acetylacetonate complex met the criteria of controlled polymerization, i.e., first-order kinetic in NVP, increase of the molar mass with the NVP conversion, and narrow molar mass distribution. Therefore, the length of the two blocks can be tuned by the [VAc]/[Co(acac)(2)] and the [NVP]/[PVAc] ratios for the synthesis of the macroinitiator and the polymerization of the second monomer, respectively. These amphiphilic PVAc-b-PNVP block copolymers were easily converted into the double hydrophilic PVOH-b-PNVP counterparts by selective methanolysis of the PVAc block. These two types of copolymers were prone to self-association into micelles in appropriate solvents. [less ▲]

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See detailCobalt(II) complexes as controlling agents for the radical polymerization of vinyl monomers
Debuigne, Antoine ULg; Sciannaméa, Valérie; Piette, Yasmine ULg et al

Poster (2007, August 31)

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See detailSynthesis and evaluation of sterically hindered 1,1-diamantyl nitroxide as a low-temperature mediator for the stable free radical polymerization process
Debuigne, Antoine ULg; Chan-Seng, Delphine; Li, Lichun et al

in Macromolecules (2007), 40(17), 6224-6232

An efficient procedure for the oxidation of 1,1-diadamantylamine with m-chloroperbenzoic acid (m-CPBA) to the corresponding sterically hindered nitroxide in high yield (72%) is reported. The corresponding ... [more ▼]

An efficient procedure for the oxidation of 1,1-diadamantylamine with m-chloroperbenzoic acid (m-CPBA) to the corresponding sterically hindered nitroxide in high yield (72%) is reported. The corresponding styrene-based alkoxyamine was synthesized by an atom transfer radical addition (ATRA) reaction. Because of the bulkiness of the adamantyl substituents, the cleavage of the C−ON bond of the alkoxyamine occurred readily at temperatures below 100 °C. However, in spite of the low bond dissociation temperature of the alkoxyamine, the (co)polymerizations of styrene and n-butyl acrylate proceeded poorly. The results in this paper support the argument that the most important determinant in a nitroxide-mediated polymerization of styrene and acrylate is the ability to control the excess concentration of nitroxide in solution either by an inherent instability of the nitroxide or by the use of additives that destroy the excess nitroxide. Thus, for the 1,1-diadamantyl nitroxide case, and maybe more generally, while a lower C−O bond dissociation energy of an alkoxyamine moiety at the end of the chain may allow lower polymerization temperatures and faster reactions rates, it does not enable polymerizations to proceed to high conversions if the excess nitroxide is not controlled in some manner. [less ▲]

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See detailAdvances in cobalt mediated radical polymerization (CMRP) of vinyl monomers
Debuigne, Antoine ULg; Detrembleur, Christophe ULg; Bryaskova, Rayna et al

Conference (2007, July 11)

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