References of "Debuigne, Antoine"
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See detailCobalt-mediated radical polymerization (CMRP) of vinyl acetate initiated by redox systems: Toward the scale-up of CMRP
Bryaskova, Rayna ULg; Detrembleur, Christophe ULg; Debuigne, Antoine ULg et al

in Macromolecules (2006), 39(24), 8263-8268

A redox initiating system was developed in order to bypass 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V70) as the initiator of the cobalt-mediated radical polymerization (CMRP) of vinyl acetate ... [more ▼]

A redox initiating system was developed in order to bypass 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V70) as the initiator of the cobalt-mediated radical polymerization (CMRP) of vinyl acetate (VAc) in the presence of cobalt(II) acetylacetonate (Co(acac)(2)). It is indeed a problem to stock up with V70 because of needed storage at -20 degrees C during transportation. This paper reports on the controlled CMRP of VAc initiated by ascorbic acid combined with either lauroyl peroxide or benzoyl peroxide at 30 degrees C. Substitution of citric acid for ascorbic acid results in faster polymerization whereas the polymerization control is maintained. All these improvements facilitate the implementation of the vinyl acetate CMRP and open the door to the scale-up of the process. [less ▲]

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See detailSupported cobalt mediated radical polymerization (SCMRP) of vinyl acetate and recycling of the cobalt complex
Sciannamea, Valérie; Debuigne, Antoine ULg; Piette, Yasmine ULg et al

in Chemical Communications (2006), (40), 4180-4182

Cobalt complexes supported on silica and Merrifield resin are effective mediators for the controlled radical polymerization of vinyl acetate.

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See detailCobalt-mediated radical polymerization of vinyl acetate: a new tool for macromolecular engineering
Debuigne, Antoine ULg; Detrembleur, Christophe ULg; Bryaskova, Rayna et al

in Matyjaszewski, Krzysztof (Ed.) Controlled/living radical polymerization: from synthesis to materials (2006)

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See detailStable free radical polymerization of acrylates promoted by α-hydroxycarbonyl compounds
Debuigne, Antoine ULg; Radhakrishnan, Thottackad; Georges, Michaël K.

in Macromolecules (2006), 39(16), 5359-5363

The living-radical polymerization of n-butyl acrylate, moderated with TEMPO, is shown to proceed in a controlled fashion in the presence of a series of α-hydroxycarbonyl compounds with different organic ... [more ▼]

The living-radical polymerization of n-butyl acrylate, moderated with TEMPO, is shown to proceed in a controlled fashion in the presence of a series of α-hydroxycarbonyl compounds with different organic bases. The best results were obtained with glyceraldehyde dimer in the presence of pyridine. These results further support the suggestion that the difficulty of polymerizing acrylate monomers in the presence of TEMPO is related to the excess buildup of TEMPO due to a small amount of polymer chain termination and to a lesser extent on the higher bond dissociation energy of the TEMPO acrylate bond relative to the TEMPO styrene bond at the chain's terminus. [less ▲]

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See detailEfficient controlled radical polymerization of vinyl acetate based on cobast complexes
Debuigne, Antoine ULg; Detrembleur, Christophe ULg; Bryaskova, Rayna et al

Conference (2006, May 18)

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See detailPreparation of well-defined PVOH/C60 nanohybrids by cobalt-mediated radical polymerization of vinyl acetate
Detrembleur, Christophe ULg; Stoilova, Olya; Bryaskova, Rayna ULg et al

in Macromolecular Rapid Communications (2006), 27(7), 498-504

Poly(vinyl acetate) chains end-capped by a Co(acac)(2) complex [PVAc-Co(acac)(2)] were prepared by bulk cobalt-mediated radical polymerization (CMRP) of vinyl acetate and used for grafting fullerene (C60 ... [more ▼]

Poly(vinyl acetate) chains end-capped by a Co(acac)(2) complex [PVAc-Co(acac)(2)] were prepared by bulk cobalt-mediated radical polymerization (CMRP) of vinyl acetate and used for grafting fullerene (C60) with four PVAc arms at low temperature (30 degrees C). A photoactive water-soluble poly(vinyl alcohol)/C60 nanohybrid was then prepared by hydrolysis of the PVAc arms of the nanohybrid. Because of photoactivity and very low cytotoxicity, this type of water-soluble nanohybrid is very promising for the photodynamic cancer therapy. [less ▲]

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See detailSynthesis of macrocyclic poly(epsilon-caprolactone) by intramolecular cross-linking of unsaturated end groups of chains precyclic by the initiation
Li, Haiying; Debuigne, Antoine ULg; Jérôme, Robert ULg et al

in Angewandte Chemie (International ed. in English) (2006), 45(14), 2264-2267

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See detailQuinone transfer radical polymerization of styrene: Synthesis of the actual initiator
Debuigne, Antoine ULg; Caille, Jean-Raphaël; Jérôme, Robert ULg

in Journal of Polymer Science. Part A, Polymer Chemistry (2006), 44(3), 1233-1244

ortho-Quinones, such as phenanthrenequinone and 3,6-dimethoxyphenanthrenequinone, added with a catalytic amount of metal complexes, impart control to styrene polymerization via the previously reported ... [more ▼]

ortho-Quinones, such as phenanthrenequinone and 3,6-dimethoxyphenanthrenequinone, added with a catalytic amount of metal complexes, impart control to styrene polymerization via the previously reported quinone transfer radical polymerization (QTRP) process. In this study, compounds that mimic the dormant species proposed in the QTRP mechanism have been synthesized and tested as initiators in the presence of cobalt(II) acetylacetonate. These compounds, and particularly 3,6-dimethoxy-10-hydroxy-10-(l-phenyl-ethyl)-phenanthren-9-one, are effective control agents for the radical polymerization of styrene, in agreement with the recently proposed mechanism. Moreover, the induction period, which has been systematically reported in the presence of ortho-quinones, is no longer observed. The end capping of the polystyrene chains by the control agent has been confirmed by H-1 NMR analysis. [less ▲]

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See detailCobalt-mediated radical polymerization of vinyl acetate in miniemulsion: Very fast formation of stable poly(vinyl acetate) latexes at low temperature
Detrembleur, Christophe ULg; Debuigne, Antoine ULg; Bryaskova, Rayna ULg et al

in Macromolecular Rapid Communications (2006), 27(1), 37-41

Poly(vinyl acetate) macroinitiators end-capped by a Co(acac)(2) complex (PVAc-Co(acac)(2)), prepared in bulk by cobalt-mediated radical polymerization (CMRP), are used for the controlled radical ... [more ▼]

Poly(vinyl acetate) macroinitiators end-capped by a Co(acac)(2) complex (PVAc-Co(acac)(2)), prepared in bulk by cobalt-mediated radical polymerization (CMRP), are used for the controlled radical polymerization of vinyl acetate in miniemulsion to give high-molecular-weight polymers and high monomer conversion. Stable poly(vinyl acetate) latexes with solid contents ranging from 25 to 30 wt.-% are prepared within unusually short reaction times (similar to 1 h) at low temperatures (0-30 degrees C). [less ▲]

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See detailVinyl acetate: a challenge for living radical polymerisation
Debuigne, Antoine ULg

Scientific conference (2005, December 01)

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See detailSynthesis of poly(vinyl acetate) and poly(vinyl alcohol) containing block copolymers by combination of cobalt-mediated radical polymerization and ATRP
Debuigne, Antoine ULg; Caille, Jean-Raphaël; Willet, Nicolas ULg et al

in Macromolecules (2005), 38(23), 9488-9496

Poly(vinyl acetate) (PVAc) chains of a low polydispersity (Mw/Mn similar to 1.1-1.2) have been prepared by cobalt-mediated radical polymerization of vinyl acetate (VAc). They have been end-capped by an ... [more ▼]

Poly(vinyl acetate) (PVAc) chains of a low polydispersity (Mw/Mn similar to 1.1-1.2) have been prepared by cobalt-mediated radical polymerization of vinyl acetate (VAc). They have been end-capped by an activated bromide by addition of an alpha-bromoester or an alpha-bromoketone containing nitroxide and converted into effective macroinitiators for the atom transfer radical polymerization of styrene (Sty), ethyl acrylate, and methyl methacrylate. Because each block is formed by a controlled process, well-defined PVAc containing diblock copolymers are easily prepared. The PVAc-b-PS copolymers synthesized from alpha-bromoketone end-capped PVAc can be converted into well-defined poly(vinyl alcohol)-b-polystyrene amphiphiles by methanolysis of the poly(vinyl acetate) block. Self-association of an amphiphilic poly(vinyl alcohol)(3500)-b-polystyrene(16 600) in a (4/1) water/tetrahydrofuran mixture results in the formation of vesicles as observed by transmission electron microscopy. [less ▲]

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See detailVinyl acetate: a challenge for living radical polymerisation
Debuigne, Antoine ULg

Scientific conference (2005, September 11)

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See detailA new system for the controlled radical polymerization of vinyl acetate
Debuigne, Antoine ULg; Detrembleur, Christophe ULg; Bryaskova, Rayna ULg et al

in Polymer Preprints (2005), 46(2), 313-314

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See detailQuinone transfer radical polymerization of styrene catalyzed by metal complexes in the presence of various o-quinones
Debuigne, Antoine ULg; Caille, Jean-Raphaël; Jérôme, Robert ULg

in Macromolecules (2005), 38(15), 6310-6315

Several o-quinones have been tested as control agents for the quinone transfer radical polymerization (QTRP) of styrene in the presence of cobalt(II) acetylacetonate. In contrast to the commercially ... [more ▼]

Several o-quinones have been tested as control agents for the quinone transfer radical polymerization (QTRP) of styrene in the presence of cobalt(II) acetylacetonate. In contrast to the commercially available 3,5-di-tert-butyl-o-benzoquinone (3,5-DtBBQ) and tetrachloro-1,2-benzoquinone (tetrachloro-1,2-BQ), 3,6-dimethoxy-9,10-phenanthrenequinone (3,6-DMPhQ) imparts a better control to the radical polymerization of styrene compared to 9,10-phenanthrenequinone (PhQ) used as a reference. Indeed, whenever 3,6-DMPhQ is added with a catalytic amount of metal complexes (Co(acac)(2) or Al(acac)(3)), the evolution of the molar mass with the monomer conversion is linear, and low polydispersity (M-w/M-n similar to 1.1-1.2) is observed until very high monomer conversion (similar to 90%). Finally, the methoxy protons of 3,6-DMPhQ have been detected by H-1 NMR analysis of the polystyrene end groups, which is important mechanistic information. [less ▲]

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See detailLiving radical polymerization under emulsion conditions
Szkurhan, K.; Chan-Seng, D.; Kasahara, T. et al

Poster (2005, July 03)

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See detailQuinone transfer radical polymerization (QTRP) of styrene: Catalysis by different metal complexes
Caille, Jean-Raphaël; Debuigne, Antoine ULg; Jérôme, Robert ULg

in Journal of Polymer Science. Part A, Polymer Chemistry (2005), 43(13), 2723-2733

Styrene has been polymerized by a Quinone Transfer Radical Polymerization (QTRP) based on the redox reaction of an ortho-quinone and a metal catalyst. Several metal acetylacetonates have been tested in ... [more ▼]

Styrene has been polymerized by a Quinone Transfer Radical Polymerization (QTRP) based on the redox reaction of an ortho-quinone and a metal catalyst. Several metal acetylacetonates have been tested in this work. The radical polymerization of styrene is largely controlled when phenanthrenequinone (PhQ) is used with catalytic amounts of Co(acac)(2), Ni(acac)(2), Mn(acac)2 or 3, and Al(acac)(3). As a rule, in the presence of all these metallic complexes, the polystyrene molar mass increases with the monomer conversion, and polydispersity (M-w/M-n) is in the 1.3-1.6 range (at least until 40% monomer conversion). Styrene polymerization has also been resumed by polystyrene chains prepared by QTRP. In the specific case of manganese acetylacetonates, an amine or phosphine ligand has to be added for the control to be effective. Finally, two mechanistic hypotheses have been proposed, depending on whether the oxidation state of the metal can be easily changed or not. [less ▲]

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See detailSynthesis of end-functional poly(vinyl acetate) by cobalt-mediated radical polymerization
Debuigne, Antoine ULg; Caille, Jean-Raphaël; Jérôme, Robert ULg

in Macromolecules (2005), 38(13), 5452-5458

Poly(vinyl acetate) (PVAc) chains prepared by cobalt-mediated radical polymerization in the presence of cobalt(II) acetylacetonate (Co(acac)(2)) were quenched by radical scavengers, such as thiol ... [more ▼]

Poly(vinyl acetate) (PVAc) chains prepared by cobalt-mediated radical polymerization in the presence of cobalt(II) acetylacetonate (Co(acac)(2)) were quenched by radical scavengers, such as thiol compounds and nitroxides, to displace the covalently bonded Co(acac)(2) moiety and to end-cap them with a reactive group. The cobalt complex was completely removed by filtration, as confirmed by the induction coupled plasma (ICP) analysis of the polymer before and after treatment. Growing poly(vinyl acetate) chains can be end-functionalized either by addition of an appropriately functionalized nonpolymerizable olefin or by displacement of the Co(acac)(2) moiety by a functionalized nitroxide. This strategy allows PVAc to be synthesized with a predictable molecular weight, a reasonably low polydispersity (M-w/M-n similar to 1.1-1.3), and a functional omega end group, e.g., hydroxyl and epoxy. [less ▲]

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See detailEffective cobalt mediation of the radical polymerization of vinyl acetate in suspension
Debuigne, Antoine ULg; Caille, Jean-Raphaël; Detrembleur, Christophe ULg et al

in Angewandte Chemie (International ed. in English) (2005), 44(22), 3439-3442

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