References of "Debuigne, Antoine"
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See detailSynthesis of thermo-responsive poly(N-vinylcaprolactam)-containing block copolymers by cobalt-mediated radical polymerization
Hurtgen, Marie ULg; Liu, Ji ULg; Debuigne, Antoine ULg et al

in Journal of Polymer Science. Part A, Polymer Chemistry (2012), 50(2), 400-408

Thermo-responsive block copolymers based on poly(N-vinylcaprolactam) (PNVCL) have been prepared by cobalt-mediated radical polymerization (CMRP) for the first time. The homopolymerization of NVCL was ... [more ▼]

Thermo-responsive block copolymers based on poly(N-vinylcaprolactam) (PNVCL) have been prepared by cobalt-mediated radical polymerization (CMRP) for the first time. The homopolymerization of NVCL was controlled by bis(acetylacetonato)cobalt(II) and a molecular weight as high as 46,000 g/mol could be reached with a low polydispersity. The polymerization of NVCL was also initiated from a poly(vinyl acetate)-Co(acac)2 (PVAc-Co(acac)2) macroinitiator to yield well-defined PVAc-b-PNVCL block copolymers with a low polydispersity (Mw/Mn = 1.1) up to high molecular weights (Mn = 87,000 g/mol), which constitutes a significant improvement over other techniques. The amphiphilic PVAc-b-PNVCL copolymers were hydrolyzed into unprecedented double hydrophilic poly(vinyl alcohol)-b-PNVCL (PVOH-b-PNVCL) copolymers and their temperature-dependent solution behavior was studied by turbidimetry and dynamic light scattering. Finally, the so-called cobalt-mediated radical coupling (CMRC) reaction was implemented to PVAc-b-PNVCL-Co(acac)2 precursors to yield novel PVAc-b-PNVCL-b-PVAc symmetrical triblock copolymers. [less ▲]

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See detailSynthesis of star and H-shape polymers via a combination of cobalt-mediated radical polymerization and nitrone mediated radical coupling reactions
Detrembleur, Christophe ULg; Debuigne, Antoine ULg; Altintas, Ozcan et al

in Polymer Chemistry (2012), 3(1), 135-147

Via consecutive cobalt-mediated radical polymerization (CMRP), nitrone-mediated radical coupling (NMRC) and copper catalyzed azide-alkyne cycloaddition (CuAAC), polymers with mikto-arm star and H-shape ... [more ▼]

Via consecutive cobalt-mediated radical polymerization (CMRP), nitrone-mediated radical coupling (NMRC) and copper catalyzed azide-alkyne cycloaddition (CuAAC), polymers with mikto-arm star and H-shape architecture were synthesized. Poly(vinyl acetate)40-block-poly(acrylonitrile)78-Co(acac)2 polymers were synthesized via CMRC and subsequently coupled using an alkyne functional nitrone. The coupling efficiency of the NMRC process was assessed employing N-tert-butyl a-phenyl nitrone (PBN), which is structurally very similar to the later employed coupling agent. Generally, coupling efficiencies of close to 90% or higher were observed in all cases. Since the coupling reaction yields triblock copolymers bearing an alkoxyamine functionality (and thus also an alkyne group) in the middle of the chain, well defined PEG conjugates could be obtained via CuAAC. Miktoarm star polymers of the structure (PVAc-b-PAN)2-PEG were generated as well as H-shaped material of the structure (PVAc-b-PAN)2-PEG-(PVAc-b-PAN)2 via conjugation with bifunctional PEG. In all cases, very narrow molecular weight material was obtained. Molecular weight analysis of the intermediate and the final products reveals that the hydrodynamic volume of the miktoarm star and the H-shaped materials is not substantially increased during the final conjugation reaction despite the fact that the absolute molecular weight increases by more than a factor of two in the latter case. Success of the conjugation reactions was confirmed via composition analysis via NMR. [less ▲]

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See detailKey role of intramolecular metal chelation and hydrogen bonding in the cobalt-mediated radical polymerization of N-vinyl amides
Debuigne, Antoine ULg; Morin, Aurélie; Kermagoret, Anthony ULg et al

in Chemistry : A European Journal (2012), 18

This work reveals the preponderance of an intramolecular metal chelation phenomenon in a controlled radical polymerization system involving the reversible trapping of the radical chains by a cobalt ... [more ▼]

This work reveals the preponderance of an intramolecular metal chelation phenomenon in a controlled radical polymerization system involving the reversible trapping of the radical chains by a cobalt complex, i.e. the bis(acetylacetonato)cobalt(II). The cobalt-mediated radical polymerization (CMRP) of a series of N-vinyl amides was considered in order to evidence the effect of the cobalt chelation by the amide moiety of the last monomer unit of the chain. The latter reinforces the cobalt-polymer bond in the order N-vinylpyrrolidone < N-vinyl caprolactam < N-methyl-N-vinyl acetamide, and is responsible for the optimal control of the polymerizations observed for the last two monomers. Such a double linkage between the controlling agent and the polymer, via a covalent bond and a dative one, is unique in the field of controlled radical polymerization and represents a powerful opportunity to fine tune the equilibrium between latent and free radicals. The possible hydrogen bond formation is also taken into account in the case of N-vinyl acetamide and N-vinyl formamide. These results are essential for understanding factors influencing a Co-C bond strength in general, and the CMRP mechanism in particular, but also for developing a powerful platform for the synthesis of new precision poly(N-vinyl amide)s, an important class of polymers which sustains numerous applications today. [less ▲]

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See detailCobalt-mediated radical polymerization
Debuigne, Antoine ULg; Jérôme, Robert ULg; Jérôme, Christine ULg et al

in Schlüter, Dieter A.; Hawker, Craig; Sakamoto, Junji (Eds.) Synthesis of polymers: new structures and methods (2012)

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See detailCombination of lipase catalysis and thiol-Michael addition for the synthesis of carbohydrate esters used as stabilizers in supercritical carbon dioxide emulsions
Boyère, Cédric ULg; Favrelle, Audrey; Broze, Guy ULg et al

Poster (2011, November 21)

The use of aqueous dispersed media, such as emulsions and miniemulsions, has many advantages over solution processes for chemical transformations and polymerization reactions, i.e. limited environmental ... [more ▼]

The use of aqueous dispersed media, such as emulsions and miniemulsions, has many advantages over solution processes for chemical transformations and polymerization reactions, i.e. limited environmental impact, ease of products recovery and increased reaction rate. Although, dispersed media are usually implemented from water/solvent mixtures, supercritical carbon dioxide (scCO2) (Pc =74 bars; Tc = 31°C) constitutes an interesting alternative to the traditional organic solvents because it is inexpensive, non-toxic, non-flammable and environmentally friendlier. In this context, we develop a novel class of surface active compounds able to stabilize water/scCO2 emulsions, i.e. fluorinated modified carbohydrates. The hydrophilic head of the surfactant consists in a sugar moiety whereas the fluorinated tail has a strong affinity for the scCO2 phase. These carbohydrate esters are prepared by a two-step strategy which takes advantage of the selectivity of enzymatic catalysis and the versatility of the thiol-Michael addition reaction. The new thiolated mannose intermediate is a useful building block for the incorporation of unprotected sugar moieties into complex molecules. The surface active properties of the fluorinated derivatives have been evaluated as well as their use as stabilizers for the preparation of microparticles and highly porous polymer materials in scCO2. [less ▲]

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See detailNew functional poly(N-vinylpyrrolidone) based (co)polymers via photoinitiated cobalt-mediated radical polymerization
Debuigne, Antoine ULg; Schoumacher, Matthieu ULg; Willet, Nicolas ULg et al

in Chemical Communications (2011), 47(47), 12703-12705

The photoinitiated cobalt-mediated radical polymerization enables the synthesis of novel alpha-functional and alpha,omega-telechelic polymers. In combination with ring-opening polymerization, it also ... [more ▼]

The photoinitiated cobalt-mediated radical polymerization enables the synthesis of novel alpha-functional and alpha,omega-telechelic polymers. In combination with ring-opening polymerization, it also produces new amphiphilic copolymers which self-assemble into flower-like vesicles in water. [less ▲]

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See detailLipase catalysis and thiol-Michael addition: a relevant association for the synthesis of new surface active carbohydrate esters
Boyère, Cédric ULg; Favrelle, Audrey ULg; Broze, Guy ULg et al

in Carbohydrate Research (2011), 346(14), 2121-2125

A novel class of surface-active carbohydrate esters is prepared by a two-step strategy that takes advantage of the selectivity of enzymatic catalysis and the versatility of the thiol-Michael addition ... [more ▼]

A novel class of surface-active carbohydrate esters is prepared by a two-step strategy that takes advantage of the selectivity of enzymatic catalysis and the versatility of the thiol-Michael addition reaction. The surfactant performance of the produced aliphatic, fluorinated and silicon based sugar esters are evaluated by surface tension measurements. The novel thiolated mannose, made available in this work, appears as a powerful building block for the incorporation of unprotected sugar moieties into complex molecules. [less ▲]

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See detailSynthesis of 1-vinyl-3-ethylimidazolium-based ionic liquid (co)polymers by cobalt-mediated radical polymerization
Detrembleur, Christophe ULg; Debuigne, Antoine ULg; Hurtgen, Marie ULg et al

in Macromolecules (2011), 44(16), 6397-6404

The cobalt-mediated radical polymerization (CMRP) of 1-vinyl-3-ethylimidazolium bromide (VEtImBr) is described. Polymerizations were performed at 30 °C in solution either in dimethylformamide (DMF) or in ... [more ▼]

The cobalt-mediated radical polymerization (CMRP) of 1-vinyl-3-ethylimidazolium bromide (VEtImBr) is described. Polymerizations were performed at 30 °C in solution either in dimethylformamide (DMF) or in methanol (MeOH) or in a mixture of both solvents, using a preformed alkyl–cobalt(III) adduct, CH3OC(CH3)2CH2–C(CH3)(CN)–(CH2–CHOAc)<4–Co(acac)2, as the mediating agent. Excellent control over molecular weights and dispersities (Mw/Mn 1.05–1.06) was achieved in MeOH, with a linear increase of experimental molecular weights with the monomer conversion. Substituting methanol for DMF induced much faster polymerization process, even under quite high diluted conditions: for instance, about 80% monomer conversion was reached in 30 min in DMF, compared to 10 h in MeOH. However, size exclusion chromatography (SEC) traces of PVEtImBr samples synthesized in DMF revealed a side population in the high molecular weight region, presumably due to the occurrence of irreversible coupling reactions of a small proportion of growing chains. Well-defined diblock copolymers featuring both a poly(vinyl acetate) (PVAc) block and a PVEtImBr-based poly(ionic liquid) block, PVAc-b-PVEtImBr, were next obtained by sequential CMRP of VAc and VEtImBr. To this end, a PVAc-Co(acac)2 was first prepared by CMRP and employed as a macroinitiator for the polymerization of VEtImBr either in methanol or in a mixture of DMF and MeOH (2/1: v/v) at 30 °C. Finally, cobalt-mediated radical coupling (CMRC) of the aforementioned PVAc-b-PVEtImBr diblock copolymers, using isoprene as a simple coupling agent, led to unprecedented and structurally well-defined PVAc-b-PVEtImBr-b-PVAc triblock copolymers. [less ▲]

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See detailEnzymatic synthesis and surface active properties of novel hemifluorinated mannose esters
Favrelle, Audrey ULg; Boyère, Cédric ULg; Laurent, Pascal ULg et al

in Carbohydrate Research (2011), 346(9), 1161-1164

The lipase-catalysed esterification of sugars with hemifluorinated acid derivatives is reported for the first time. A series of mannose modified derivatives having fluorinated chains with different length ... [more ▼]

The lipase-catalysed esterification of sugars with hemifluorinated acid derivatives is reported for the first time. A series of mannose modified derivatives having fluorinated chains with different length have been prepared accordingly in moderate yield. A preliminary evaluation of the surface active properties of these hemifluorinated mannose esters revealed their ability to reduce the surface tension of water much more efficiently than their aliphatic counterparts. [less ▲]

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See detailOrganometallic-mediated radical polymerization: unusual route toward (quasi-) diblock graft copolymers starting from a mixture of monomers of opposed reactivity
Hurtgen, Marie ULg; Debuigne, Antoine ULg; Fustin, Charles-André et al

in Macromolecules (2011), 44(12), 4623-4631

Graft copolymers have been prepared by one-step organometallic-mediated radical polymerization (OMRP) for the first time. Poly(ethylene glycol) acrylate (PEGA) was copolymerized with vinyl acetate (VAc ... [more ▼]

Graft copolymers have been prepared by one-step organometallic-mediated radical polymerization (OMRP) for the first time. Poly(ethylene glycol) acrylate (PEGA) was copolymerized with vinyl acetate (VAc) to yield well-defined P(PEGA-grad-VAc) gradient graft copolymers using bis(acetylacetonato)cobalt(II) as the control agent. The influence of experimental parameters such as the PEGA/VAc molar ratio, the nature of the initiator, and the temperature on the control of the copolymerization was discussed. The use of an excess of cobalt complex appeared as a key parameter to maintain a good level of control when higher contents of acrylate were used in the comonomer feed. The reactivity ratios were estimated and revealed that PEGA was added around 30 times faster than VAc, which gave access to a gradient P(PEGA-grad-VAc) copolymer or to a P(PEGA-grad-VAc)-b-PVAc diblock copolymer when the VAc polymerization was pursued after the full consumption of PEGA. The amphiphilic character of the copolymers makes them prone to self-assemble into micelles in water, as evidenced by dynamic light scattering. [less ▲]

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See detailProgress in cobalt-mediated radical polymerization
Debuigne, Antoine ULg; Hurtgen, Marie ULg; Piette, Yasmine ULg et al

Poster (2011, May 12)

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See detailInsight into organometallic-mediated radical polymerization
Hurtgen, Marie ULg; Detrembleur, Christophe ULg; Jérôme, Christine ULg et al

in Polymer Reviews (2011), 51(2), 188-213

This review focuses on an emerging class of controlled radical polymerization named Organometallic-Mediated Radical Polymerization (OMRP). The latter is based on the temporary deactivation of the growing ... [more ▼]

This review focuses on an emerging class of controlled radical polymerization named Organometallic-Mediated Radical Polymerization (OMRP). The latter is based on the temporary deactivation of the growing radical species by a transition metal complex and the reversible formation of a carbon-metal covalent bond. Initially developed with cobalt complexes, OMRP has extended to several metals today. As highlighted here, the choice of the metal, the structure of ligands, temperature, and additives deeply affect the course of the polymerization and its mechanism. Macromolecular engineering opportunities offered by OMRP are also described, as well as practical applications sustained by the resulting polymer materials. [less ▲]

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