References of "Debuigne, Antoine"
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See detailSINGLE-MOLECULE AFM STUDY OF ADHESIVE POLYMERS PREPARED BY COBALT-MEDIATED RADICAL POLYMERIZATION AND NITRONE-MEDIATED RADICAL COUPLING
Willet, Nicolas ULg; Sluysmans, Damien ULg; Delvaux, Cédric ULg et al

Scientific conference (2012, September 10)

Well-defined poly(vinyl acetate) (PVAc) chains prepared by CMRP (cobalt-mediated radical polymerization) were coupled using an alkyne-functional nitrone via NMRC (nitrone-mediated radical coupling).1 In ... [more ▼]

Well-defined poly(vinyl acetate) (PVAc) chains prepared by CMRP (cobalt-mediated radical polymerization) were coupled using an alkyne-functional nitrone via NMRC (nitrone-mediated radical coupling).1 In all the cases, the coupling efficiencies were close to 90% or higher. The polymers mid-chain functionalized with an alkyne group were then reacted with azide-functionalized atomic force microscopy (AFM) tips via copper-catalyzed azide-alkyne cycloaddition (CuAAC). As a result, polymers having a double-branch architecture were linked to AFM tips via a short linker. The structure and the molecular parameters of the polymers were determined by NMR and GPC, whereas the ‘click’ step onto AFM tips was assessed by performing the same CuAAC reaction onto macroscopic surfaces and characterizing them by ATR FT-IR. The adhesive properties of these double-branched polymers were studied by AFM single-molecule force spectroscopy. By performing approach-retraction cycles in solution upon a glass surface, the interaction between single PVAc chains and the surface was investigated. The effect of the double-branch architecture on the adhesion forces was under focus. Setting a residence time of the tip on the surface before retraction was found to have a beneficial influence on the adhesion forces. Signs of multiple interactions acting in parallel were detected in the experimental force-distance traces. [less ▲]

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See detailOrganometallic-mediated radical polymerization of vinyl amides: Effect of metal coordination
Kermagoret, Anthony ULg; Morin, A.; Hurtgen, Marie ULg et al

Poster (2012, September 04)

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See detailOrganometallic-mediated radical polymerization of vinyl amides: Effect of metal coordination
Kermagoret, Anthony ULg; Morin, A.; Hurtgen, Marie ULg et al

Conference (2012, September 04)

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See detailSynthesis of microsphere-loaded porous polymers by combining emulsion and dispersion polymerisations in supercritical carbon dioxide
Boyère, Cédric ULg; Léonard, Alexandre ULg; Grignard, Bruno ULg et al

in Chemical Communications (2012), 48(67), 8356-8358

Highly porous materials were produced by acrylamide polymerisation templated by supercritical CO2-in-water emulsions using new fluorinated glycosurfactants. Properties of the resulting polymer scaffolds ... [more ▼]

Highly porous materials were produced by acrylamide polymerisation templated by supercritical CO2-in-water emulsions using new fluorinated glycosurfactants. Properties of the resulting polymer scaffolds were tuned by performing dispersion polymerisations within their cavities filled with supercritical CO2. [less ▲]

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See detailSynthetic and mechanistic inputs of photochemistry into the bisacetylacetonatocobalt- mediated radical polymerization of n-butyl acrylate and vinyl acetate
Detrembleur, Christophe ULg; Versace, Davy-Louis; Piette, Yasmine et al

in Polymer Chemistry (2012), 3(7), 1856-1866

The input of photochemistry to the Co(acac)2 mediated radical polymerization (CMRP) of n-butyl acrylate and vinyl acetate is investigated for the first time. Upon UV irradiation, photoinitiators are able ... [more ▼]

The input of photochemistry to the Co(acac)2 mediated radical polymerization (CMRP) of n-butyl acrylate and vinyl acetate is investigated for the first time. Upon UV irradiation, photoinitiators are able to initiate the n-butyl acrylate polymerization that remains controlled up to very high molar masses (>4 × 106 g mol−1) with low polydispersities. The photoinitiator as well as the irradiation time must be appropriately chosen to reach acceptable initiator efficiencies while maintaining an optimal control over the polymerization. Laser flash photolysis experiments were then carried out to evidence the addition of alkyl and phosphonyl radicals onto Co(acac)2 and to determine the rate constants (kdeact) of these addition reactions that were still lacking. Finally, both kinetics of polymerization and spin-trapping experiments have evidenced that the C–Co bond at the extremity of the dormant polymer chains can be easily photocleaved. UV irradiation can therefore be considered as an additional lever for tuning the reactivity of the CMRP process mediated by Co(acac)2. [less ▲]

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See detailInterpolymer radical coupling: A toolbox complementary to controlled radical polymerization
Debuigne, Antoine ULg; Hurtgen, Marie ULg; Detrembleur, Christophe ULg et al

in Progress in Polymer Science (2012), 37(7), 1004-1030

The current review focuses on the relevance and practical benefit of interpolymer radical coupling methods. The latter are developing rapidly and constitute a perfectly complementary macromolecular ... [more ▼]

The current review focuses on the relevance and practical benefit of interpolymer radical coupling methods. The latter are developing rapidly and constitute a perfectly complementary macromolecular engineering toolbox to the controlled radical polymerization techniques (CRP). Indeed, all structures formed by CRP are likely to be prone to radical coupling reactions, which multiply the available synthetic possibilities. Basically, the coupling systems can be divided in two main categories. The first one, including the atom transfer radical coupling (ATRC), silane radical atom abstraction (SRAA) and cobalt-mediated radical coupling (CMRC), relies on the recombination of macroradicals produced from a dormant species. The second one, including atom transfer nitroxide radical coupling (ATNRC), single electron transfer nitroxide radical coupling (SETNRC), enhanced spin capturing polymerization (ESCP) and nitrone/nitroso mediated radical coupling (NMRC), makes use of a radical scavenger in order to promote the conjugation of the polymer chains. More than a compilation of macromolecular engineering achievements, the present review additionally aims to emphasize the particularities, synthetic potential and present limitations of each system. [less ▲]

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See detailControlled radical polymerization of halogenated monomers
Bodart, Vincent; Piette, Yasmine; Detrembleur, Christophe ULg et al

Patent (2012)

Process for the preparation of a halogenated polymer comprising a controlled radical polymerization step of at least one monomer containing at least one halogen-carbon bond performed in the presence of an ... [more ▼]

Process for the preparation of a halogenated polymer comprising a controlled radical polymerization step of at least one monomer containing at least one halogen-carbon bond performed in the presence of an organo-cobalt complex, said polymerization step being further carried out in the presence of at least one ligand. [less ▲]

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See detailControlled radical polymerization of halogenated monomers
Bodart, Vincent; Piette, Yasmine; Detrembleur, Christophe ULg et al

Patent (2012)

Process for the preparation of a halogenated polymer comprising a controlled radical polymerization step of at least one monomer containing at least one halogen-carbon bond, performed in the presence of ... [more ▼]

Process for the preparation of a halogenated polymer comprising a controlled radical polymerization step of at least one monomer containing at least one halogen-carbon bond, performed in the presence of an organo-cobalt complex, said polymerization step being further carried out in non-isotherm conditions. [less ▲]

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See detailSynthèse de copolymères amphiphiles originaux par polymérisation radicalaire contrôlée via des complexes de cobalt
Debuigne, Antoine ULg; Hurtgen, Marie ULg; Liu, Ji ULg et al

Conference (2012, June 05)

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See detailUse of glycosurfactants for the synthesis of polyHIPES in supercritical carbon dioxide
Boyère, Cédric ULg; Favrelle, Audrey; Léonard, Alexandre ULg et al

Poster (2012, June 04)

The abstract is available as a pdf file.

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See detailDesign of sugar-based surface active agents for emulsion polymerization in supercritical carbon dioxide
Boyère, Cédric ULg; Favrelle, Audrey; Broze, Guy ULg et al

Conference (2012, May 10)

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

The use of aqueous dispersed media, such as emulsions, 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. Emulsions are usually implemented from a water/organic solvent mixture in the presence of a surfactant. However, supercritical carbon dioxide (scCO2) (Pc =74 bars; Tc = 31°C) constitutes an interesting alternative to the traditional organic solvents in these heterogeneous systems because it is inexpensive, non-toxic, non-inflammable and environmentally friendlier. In this context, we developed a novel class of surfactants for the stabilization of H2O/scCO2 emulsions, i.e. fluorinated modified carbohydrates. The hydrophilic head of the surfactant consists in a sugar moiety whereas a fluorinated tail is specifically located in the scCO2 phase. The strategies for the synthesis of these carbohydrates esters rely on selective lipase-catalyzed modifications of sugars and on the versatile thiol-Michael addition reaction. The ability of these molecules to decrease the H2O/scCO2 interfacial tension and to stabilize such emulsions will be presented. Finally, high internal phase scCO2-in-water emulsion (HIPE) were prepared with these new surfactants and used as template for the acrylamide polymerization. The monomer is polymerized in the continuous aqueous phase before removing the CO2 droplets (at least 70 % of the total volume). The resulting permeable porous polymers, called polyHIPEs, exhibit highly interconnected voids (cfr SEM picture) and should be valuable in many applications including support for catalyst, filtration process, immobilization of proteins, etc. [less ▲]

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See detailSynthesis of novel poly(N-vinyl amide)s containing copolymers by cobalt-mediated radical polymerization
Kermagoret, Anthony ULg; Hurtgen, Marie ULg; Liu, Ji ULg et al

Poster (2012, May 10)

Poly(N-vinyl amide)s are found in many applications due to their valued properties including water solubility, biocompatibility, metal-coordination ability, etc. Although N-vinyl amides are easily ... [more ▼]

Poly(N-vinyl amide)s are found in many applications due to their valued properties including water solubility, biocompatibility, metal-coordination ability, etc. Although N-vinyl amides are easily polymerized via radical pathways, their growing radicals are quite reactive due to the lack of stabilizing group, rendering the synthesis of well-defined poly(N-vinyl amide)s challenging. Thus, we explored the organometallic-mediated radical polymerization (OMRP) of a series of N-vinyl amides using bis(acetylacetonato)cobalt(II) as controlling agent in order to develop a platform for the precision synthesis of poly(N-vinyl amide)s. [less ▲]

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See detailUse of ionic liquids for biocatalytic synthesis of sugar derivatives
Galonde, Nadine ULg; Nott, Katherine ULg; Debuigne, Antoine ULg et al

in Journal of Chemical Technology & Biotechnology (2012), 87(4), 451-471

Sugar-based compounds are widely used in pharmaceuticals, cosmetics, detergents and food. They are mainly produced by chemical methods, but the use of enzymes as ‘a greener alternative’ to organic ... [more ▼]

Sugar-based compounds are widely used in pharmaceuticals, cosmetics, detergents and food. They are mainly produced by chemical methods, but the use of enzymes as ‘a greener alternative’ to organic synthesis has been investigated for more than 20 years. Due to the low polar substrate solubility in organic solvents compatible with enzymes, research has focused on the application of substitutes for biocatalysis, especially ionic liquids (ILs). After introducing the main properties of ILs and especially their ability to solubilize sugars, this review focuses on one of their applications, the biocatalytic synthesis of carbohydrate derivatives. In this context, they can be used in pure IL systems, in IL/IL systems or in IL/organic solvent systems. Finally, this review provides an update on the environmental fate of ILs. Their exploitation in ‘green’ processes is still limited due to their low degradability but research is currently under way to design new more ‘eco-friendly’ ILs. [less ▲]

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See detailRadical coupling of polymers formed by cobalt-mediated radical polymerization
Debuigne, Antoine ULg; Hurtgen, Marie ULg; Jérôme, Christine ULg et al

in Matyjaszewski, Krzysztof; Sumerlin, Brent; Tsarevsky, Nicolas V. (Eds.) Progress in controlled radical polymerization: mechanisms and techniques (2012)

Considerable progress has been recently made in cobalt-mediated radical polymerization (CMRP), a controlled radical polymerization system based on the temporary deactivation of the polymer chains by a ... [more ▼]

Considerable progress has been recently made in cobalt-mediated radical polymerization (CMRP), a controlled radical polymerization system based on the temporary deactivation of the polymer chains by a cobalt complex, like the improvement of the mechanistic understanding, the extension to a range of monomers and the preparation of novel architectures. However, the real breakthrough in this field concerns the development of efficient radical coupling methods for polymer precursors preformed by CMRP. This book chapter aims to describe the general principle and main characteristics of such radical coupling techniques involving dienes, nitrones, fullerenes or carbon nanotubes. Well-defined and complex architectures obtained by these techniques are provided in order to illustrate their potential for macromolecular engineering. [less ▲]

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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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