References of "Debuigne, Antoine"
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See detailInfluence of the macromolecular surfactant features and reactivity on morphology and surface properties of emulsion-templated porous polymers
Mathieu, Kevin ULg; Jérôme, Christine ULg; Debuigne, Antoine ULg

in Macromolecules (2015), 48(18), 6489-6498

This work investigates key parameters of a straightfor- ward macromolecular surfactant-assisted functionalization strategy of porous polymers produced by high internal phase emulsion (HIPE) polymerization ... [more ▼]

This work investigates key parameters of a straightfor- ward macromolecular surfactant-assisted functionalization strategy of porous polymers produced by high internal phase emulsion (HIPE) polymerization. For that purpose, a series of well-defined amphiphilic poly(ethylene oxide)-b-poly(styrene) (PEO-b-PS) copolymers with various compositions and molar masses were synthesized by radical addition−fragmentation chain transfer (RAFT) polymerization and used as macromolecular surfactants for the emulsion-templated polymerization of styrene/divinylbenzene (S/DVB). The morphology of the resulting foams, referred to as polyHIPEs, was found dependent on the PS block length and concentration of the block copolymer surfactant in the emulsion. Moreover, we determined the lowest PS block length required for preserving the anchoring of the copolymer at the surface by physical entanglement within the S/DVB cross-linked matrix leading to a PEO-coated porous material. The functionalization of the porous monoliths with PEO was evidenced by sessile drop shape analyses and water uptake experiments. The chemical anchoring of the PEO-b-PS at the surface of polyHIPEs was also explored by interfacial initiation of the HIPE polymerization from a PEO-b-PS-RAFT macroinitiator leading to porous structures with permanent PEO coatings. In this case, copolymerizing DVB with acrylate instead of styrene improved the interconnectivity of the porous monoliths. [less ▲]

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See detailCobalt-mediated radical polymerization for the precision design of novel poly(ionic liquid) copolymers in aqueous media
Cordella, Daniela ULg; Kermagoret, Anthony; Debuigne, Antoine ULg et al

Poster (2015, September 11)

Poly(ionic liquid)s (PILs) have emerged as a special class of polyelectrolyte materials, featuring tunable solubility, high ionic conductivity, and a broad range of glass transition temperatures. Due to ... [more ▼]

Poly(ionic liquid)s (PILs) have emerged as a special class of polyelectrolyte materials, featuring tunable solubility, high ionic conductivity, and a broad range of glass transition temperatures. Due to their specific properties emanating from the ionic liquid (IL) units and their intrinsic polymeric nature, PILs find potential applications in various areas, such as analytical chemistry, biotechnology, gas separation, dispersants, solid ionic conductors for energy, catalysis, etc. In recent years, controlled radical polymerization (CRP) techniques have been applied to the synthesis of structurally well-defined PILs, with control attained over molar mass, dispersity, and end-group fidelity. In this poster, we will report on the implementation of cobalt-mediated radical polymerization (CMRP) technique for the precision synthesis of unprecedented PILs (co)polymers. We will discuss how an organocobalt complex can efficiently control the growth of vinyl imidazolium chains and lead to PILs with predicted molar masses and low polydispersities under mild experimental conditions, thus at low temperature and using water as a green polymerization medium. The huge potential of this system will be highlighted by describing the one-pot synthesis of all vinyl imidazolium-based block copolymers in aqueous media. This CMRP is unique for providing well-defined vinyl imidazolium based-copolymers for advanced PILs applications. [less ▲]

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See detailNovel organocobalt for the synthesis of functional polymers
Demarteau, Jérémy ULg; Kermagoret, Anthony; Jérôme, Christine ULg et al

Poster (2015, September 11)

Organocobalt(III) with acetylacetonate (acac) ligands is the most representative example of R-Co bearing a labile C-Co bond that can release alkyl radicals under mild experimental conditions without ... [more ▼]

Organocobalt(III) with acetylacetonate (acac) ligands is the most representative example of R-Co bearing a labile C-Co bond that can release alkyl radicals under mild experimental conditions without requiring a photoactivation. The unique isolated R-Co is a short oligo(vinyl acetate) end-capped by Co(acac)2. The high lability of its C-Co bond combined to the unique capacity of Co(acac)2 to reversibly trap alkyl radicals make this R-Co unique for the precision design of unprecedented polymers by Cobalt-Mediated Radical Polymerization (CMRP). The growth of unstabilized and highly reactive growing radicals formed by the addition of R• to unconjugated vinyl monomers (vinyl esters, vinyl amides, vinyl imidazolium, vinyl chloride, etc;) is controlled by the reversible formation of a weak C-Co bond at the polymer chain end. The lack of alternatives to this R-Co, especially to the structure of the alkyl group, has however placed limitations on post-functionalizations of end-chains. Other functional variants that would enable attractive chain-end derivatizations are unfortunately not available. In this poster, we will address this important challenge by describing an innovative synthetic route towards the preparation of new functional R-Co(acac)2 that are sources of halomethyl radicals under mild experimental conditions. The efficiency of these novel organocobalt complexes for the precision synthesis of end-functional and telechelic polymers will be described. Also, the solubility of these complexes in water enables the facile production of end-functionalized water soluble poly(ionic liquid)s. Further derivatizations of the halomethyl group at the chain-end of polymers produced by this system will be demonstrated by click reaction, largely broadening the range of possible functional groups. Finally, besides numerous applications in macromolecular engineering, this unexplored family of R-Co presents a high potential in radical reactions in organic synthesis by the facile production of halomethyl radicals. [less ▲]

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See detailCross-linked polymer micelles made of polyphosphate containing amphiphilic copolymers for drug delivery
Riva, Raphaël ULg; Vanslambrouck, Stéphanie ULg; Ergül, Zeynep ULg et al

Conference (2015, September 01)

In the pharmaceutical field, amphiphilic block copolymers are of great interest for the nanovectorization of active principles in Drug Delivery. Indeed, new drugs are synthesized each day but in too many ... [more ▼]

In the pharmaceutical field, amphiphilic block copolymers are of great interest for the nanovectorization of active principles in Drug Delivery. Indeed, new drugs are synthesized each day but in too many cases, their high hydrophobicity makes them useless because of the absence of an appropriated administration method. Typically, amphiphilic block copolymers present the remarkable property to self-assemble in water with formation, in most cases, of spherical micelles characterized by a hydrophobic core and a hydrophylic corona. Rapidly, their ability to encapsulate a hydrophobic drug in their hydrophiobic core was investigated to increase the solubility of the drug in aqueous media, prevent its degradation and decrease its toxicity. However, polymer micelles suffer of the main drawback to be unstable in diluted medium, leading to a premature release of the drug, when the concentration falls down the critical micellar concentration (CMC), which it is rapidly observed after intravenous injection. This work aims at reporting on the development of a drug delivery device based on a new amphiphilic block copolymers made of degradable polyphosphate and bioeliminable poly(ethylene oxide). Thanks to their biocompatibility, biodegradability and their structure similar to natural biomacromolecules, polyphosphates are appealing polymers for biomedical applications. In contrast to aliphatic polyesters, polyphosphate properties and functionality are easily tuned via the chemical nature of the lateral chains R. In order to get rid of the CMC, the crosslinking of the micelle’s core was realized by UV radiation, in order to fulfill the increasingly stringent requirements of biomedical applications. For this purpose, photo-cross-linkable groups were introduced on the polyphosphate backbone. The effect of the crosslinking rate on the drug loading and the drug release was evaluated using doxorubicin as model drug. [less ▲]

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See detailOrganometallic-mediated radical polymerization for the precision design of novel poly(ionic liquid) copolymers in water
Cordella, Daniela ULg; Kermagoret, Anthony; Debuigne, Antoine ULg et al

Conference (2015, August 18)

In recent years, poly(ionic liquid)s (PIL)s were found to take an enabling role in important fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids with the ... [more ▼]

In recent years, poly(ionic liquid)s (PIL)s were found to take an enabling role in important fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids with the flexibility and properties of macromolecular architectures giving rise to a new family of functional polymers that opens new area of applications such as polymer electrolytes in electrochemical devices, powerful dispersants and stabilizers, absorbing membranes, precursors for carbon materials, porous polymers, etc. Controlled radical polymerization techniques have recently emerged as powerful tools for the precision design of novel PILs architectures and functionalities, enabling a considerable extension of the applications of PILs with the emergence of new properties. Many efforts are devoted to tentatively control the radical polymerization of ionic liquid monomers (ILs) that directly leads to PILs without requiring further polymer derivatization. Poly(vinyl imidazolium)s belong to a class of PILs of high interest but the control radical polymerization of their corresponding monomer is touchy due to the high reactivity of their propagating radical. In this communication, we will report on the implementation of organometallic-mediated radical polymerization (OMRP) technique for the precision synthesis of unprecedented PILs (co)polymers by direct polymerization of ILs in water. We will first discuss how a commercially available cobalt complex can efficiently control the growth of poly(vinyl imidazolium) chains and lead to PILs with predicted molar masses and low dispersities under mild experimental conditions. The efficiency of the process will then be illustrated by the one-pot synthesis of vinyl imidazolium-based block copolymers in aqueous media. This OMRP technique, highly compatible to water and active under moderate temperatures (30-40°C), is unique for providing well-defined vinyl imidazolium based-copolymers and novel PILs assemblies, and open new application fields. [less ▲]

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See detailAll Poly(ionic liquid)-based block copolymers by sequential controlled radical copolymerization of vinylimidazolium monomers
Cordella, Daniela ULg; Kermagoret, Anthony; Debuigne, Antoine ULg et al

in Macromolecules (2015), 48(15), 5230-5243

The organometallic-mediated radical polymerization (OMRP) of N-vinyl-3-alkylimidazolium-type monomers, featuring the bis(trifluoromethylsulfonyl)imide counteranion (Tf2N–), in the presence of Co(acac)2 as ... [more ▼]

The organometallic-mediated radical polymerization (OMRP) of N-vinyl-3-alkylimidazolium-type monomers, featuring the bis(trifluoromethylsulfonyl)imide counteranion (Tf2N–), in the presence of Co(acac)2 as controlling agent, is reported. Polymerizations of monomers with methyl, ethyl, and butyl substituents are fast, reaching high monomer conversion in ethyl acetate as solvent at 30 °C, and afford structurally well-defined hydrophobic poly(ionic liquid)s (PILs) of N-vinyl type. Block copolymer synthesis is also achieved by sequential OMRP of N-vinyl-3-alkylimidazolium salts carrying different alkyl chains and different counteranions (Tf2N– or Br–). These block copolymerizations are carried out at 30 °C, either under homogeneous solution in methanol or in a biphasic medium consisting of a mixture of ethyl acetate and water. Unprecedented PIL-b-PIL block copolymers are thus prepared under these conditions. However, anion exchange occurs at the early stage of the growth of the second block. Finally, diblock copolymers generated in the biphasic medium can be readily coupled by addition of isoprene, forming all PIL-based and symmetrical ABA-type triblock copolymers in a one-pot process. Such a direct block copolymerization method, involving vinylimidazolium monomers bearing different alkyl chains, thus opens new opportunities in the precision synthesis of all PIL-based block copolymers of tunable properties. [less ▲]

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See detailDouble hydrophilic polyphosphoester containing copolymers as efficient templating agnets for calcium carbonate microparticles
Ergül, Zeynep ULg; Debuigne, Antoine ULg; Calvignac, Brice et al

Conference (2015, June 22)

The design of drug delivery systems (DDS) often requires biodegradable and biocompatible materials that allow safe retention and controlled drug release. In this respect, CaCO3 particles are appropriate ... [more ▼]

The design of drug delivery systems (DDS) often requires biodegradable and biocompatible materials that allow safe retention and controlled drug release. In this respect, CaCO3 particles are appropriate drug carriers that have excellent properties such as low density, high specific surface areas and porosity for drugs and proteins encapsulation. Here, degradable synthetic copolymers based on polyphosphoester (PPE) were used to template CaCO3 particles. PPE is a promising candidate due to its biocompatibility, biodegradability and low toxicity of its degradation products such as phosphates. In particular, PPE copolymers with carboxylic acid pendant groups and negatively charged polyphosphodiester-based copolymers were prepared by organocatalyzed ring opening polymerization (ROP) initiated from poly(ethylene oxide). The moieties introduced along the polymer chains enhance the calcium affinity and so the ability of the copolymers to tune the morphology of the CaCO3 particles. The copolymers were tested as templating agents for the preparation of CaCO3 particles by the classical chemical pathway and the supercritical CO2 (Sc-CO2) route. The morphology of the resulting particles was then compared to the one of particles obtained using hyaluronic acid (HA) as a templating agent. The synthesis involving Sc-CO2 and the copolymer with pendant carboxylic groups was particularly interesting and led to smaller (~1.5 µm) and non-aggregated particles. In the future, the impact of the copolymer structure and of the particle size on the encapsulation and release processes will be investigated. [less ▲]

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See detailOrganometallic-mediated radical polymerization for the precision design of novel poly(ionic liquid) copolymers
Cordella, Daniela ULg; Kermagoret, Anthony; Debuigne, Antoine ULg et al

Conference (2015, June 12)

In recent years, poly(ionic liquid)s (PIL)s were found to take an enabling role in important fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids with the ... [more ▼]

In recent years, poly(ionic liquid)s (PIL)s were found to take an enabling role in important fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids with the flexibility and properties of macromolecular architectures giving rise to a new family of functional polymers that opens new area of applications such as polymer electrolytes in electrochemical devices, powerful dispersants and stabilizers, absorbing membranes, precursors for carbon materials, porous polymers, etc. In this communication, we will report on the implementation of organometallic-mediated radical polymerization (OMRP) technique for the precision synthesis of unprecedented PILs (co)polymers. We will discuss how an organocobalt complex can efficiently control the growth of vinyl imidazolium chains and lead to PILs with predicted molar masses and low polydispersities under mild experimental conditions, which provide low temperatures (compared to the conventional radical polymerization techniques) and also the use of water as green polymerization medium. The huge potential of this system will be also highlighted by describing the one-pot synthesis of vinyl imidazolium-based block copolymers in heterogeneous conditions. This OMRP is unique for providing well-defined vinyl imidazolium based-copolymers opening for advanced PILs applications. [less ▲]

Detailed reference viewed: 7 (2 ULg)
See detailOrganometallic-mediated radical synthesis of well-defined ethylene-vinyl acetate statistical and block copolymers
Demarteau, Jérémy ULg; Kermagoret, Anthony; Jérôme, Christine ULg et al

Poster (2015, May 18)

The copolymerization of ethylene (E) and vinyl acetate (VAc) is of high interest for polymer industry. Nevertheless, the control of the macromolecular parameters of ethylene-vinyl acetate copolymers (EVAs ... [more ▼]

The copolymerization of ethylene (E) and vinyl acetate (VAc) is of high interest for polymer industry. Nevertheless, the control of the macromolecular parameters of ethylene-vinyl acetate copolymers (EVAs) is difficult to achieve. Herein, we report the controlled radical copolymerization of these monomers by organometallic-mediated radical polymerization (OMRP) using Co(acac)2 as controlling agent. The ethylene pressure is varied from 10 to 100 bar and we discuss the effect of this parameter on kinetics, level of control and copolymer composition. EVAs are synthetized accordingly with low dispersities and ethylene content reaches up to 57 mol%. The precision design of EVA-containing block copolymers, i.e. PVAc-block-EVA, is also addressed. [less ▲]

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See detailA tool for the precision synthesis of poly(ionic liquid)s in water
Cordella, Daniela ULg; Kermagoret, Anthony; Debuigne, Antoine ULg et al

Conference (2015, May 18)

In recent years, poly(ionic liquid)s (PIL)s were found to take an enabling role in important fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids with the ... [more ▼]

In recent years, poly(ionic liquid)s (PIL)s were found to take an enabling role in important fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids with the flexibility and properties of macromolecular architectures giving rise to a new family of functional polymers that opens new area of applications such as polymer electrolytes in electrochemical devices, powerful dispersants and stabilizers, absorbing membranes, precursors for carbon materials, porous polymers, etc. In this communication, we will report on the implementation of organometallic-mediated radical polymerization (OMRP) technique for the precision synthesis of unprecedented PILs (co)polymers. We will discuss how an organocobalt complex can efficiently control the growth of vinyl imidazolium chains and lead to PILs with predicted molar masses and low polydispersities under mild experimental conditions, which provide low temperatures (compared to the conventional radical polymerization techniques) and also the use of water as green polymerization medium. The huge potential of this system will be also highlighted by describing the one-pot synthesis of vinyl imidazolium-based block copolymers in heterogeneous conditions. This OMRP is unique for providing well-defined vinyl imidazolium based-copolymers opening for advanced PILs applications. [less ▲]

Detailed reference viewed: 59 (7 ULg)
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See detailControlled synthesis of ethylene-vinyl acetate based copolymers by organometallic mediated radical polymerization
Demarteau, Jérémy ULg; Kermagoret, Anthony ULg; Jérôme, Christine ULg et al

in Matyjaszewski, Krzysztof; Sumerlin, Brent S.; Tsarevsky, Nicolay V. (Eds.) et al Controlled Radical Polymerization: Materials (2015)

The controlled radical copolymerization of ethylene (E) and vinyl acetate (VAc) is further investigated by organometallic- mediated radical polymerization (OMRP) using Co(acac)2 as controlling agent at ... [more ▼]

The controlled radical copolymerization of ethylene (E) and vinyl acetate (VAc) is further investigated by organometallic- mediated radical polymerization (OMRP) using Co(acac)2 as controlling agent at ethylene pressure up to 100 bar. The effect of ethylene pressure on kinetics, level of control and copolymer composition, is discussed. Ethylene-Vinyl Acetate copolymers (EVAs) with low dispersities and ethylene content reaching 57 mol% are notably reported. This work also successfully addresses the precision design of EVA-containing block copolymers, i.e. PVAc-block-EVA. In this case, the order of the synthesis of the blocks is a key parameter. The “PVAc-first” strategy is by far more practical and efficient. [less ▲]

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See detailDouble thermo-responsive hydrogels from poly(vinylcaprolactam) containing diblock and triblock copolymers
Thomassin, Jean-Michel ULg; Mathieu, Kevin ULg; Kermagoret, Anthony ULg et al

in Polymer Chemistry (2015), 6(10), 1856-1864

The thermally-induced gelation and gel properties of concentrated aqueous solutions of double thermoresponsive poly(N-vinylamide)-based di- and triblock copolymers are studied by rheology. The copolymers ... [more ▼]

The thermally-induced gelation and gel properties of concentrated aqueous solutions of double thermoresponsive poly(N-vinylamide)-based di- and triblock copolymers are studied by rheology. The copolymers under investigation, prepared by cobalt-mediated radical polymerization and coupling reactions, are composed of poly(vinylcaprolactam) (PNVCL) blocks and of a statistical poly(vinylcaprolactam-stat-vinylpyrrolidone) segment with a cloud point temperature (TCP) higher than that of PNVCL. Heating the di- and triblock solutions beyond the first phase transition temperature favors gel formation while heating above the second TCP leads to opaque gels without macroscopic demixing. Moduli of the triblock hydrogels are systematically higher than those of the corresponding diblocks, even above the second transition. Rheological data suggest distinct micellar structures for each copolymer architecture: densely packed micelles of diblocks and 3-D networks of bridged micelles for triblocks. Strain sweep experiments also emphasize the positive effect of the micelle bridging on the elasticity and stability of the hydrogels. The formation and properties of the obtained gels are also shown to depend on the copolymer concentration, block length, and composition. Addition of salt also allows us to tune the phase transition temperatures of these double thermoresponsive hydrogels. [less ▲]

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See detailPoly(vinyl ester 1,2,3-triazolium)s: a new member of the poly(ionic liquid)s family
Obadia, M. M.; Colliat-Dangus, G.; Debuigne, Antoine ULg et al

in Chemical Communications (2015), 51(16), 3332-3335

A vinyl ester monomer carrying a pendant 1,2,3-triazole group is synthesized in two steps and polymerized by cobalt-mediated radical polymerization. Subsequent alkylation with N-methyl bis ... [more ▼]

A vinyl ester monomer carrying a pendant 1,2,3-triazole group is synthesized in two steps and polymerized by cobalt-mediated radical polymerization. Subsequent alkylation with N-methyl bis[(trifluoromethyl)sulfonyl]imide affords the corresponding poly(vinyl ester 1,2,3-triazolium). This unprecedented example of poly(vinyl ester ionic liquid) exhibits an ionic conductivity of 9.2 × 10(-7) S cm(-1) at 30 °C [less ▲]

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See detailStimuli-responsive behavior of micelles prepared from a poly(vinyl alcohol)-block-poly(acrylic acid)-block-poly(4-vinylpyridine) triblock terpolymer
Poggi, Elio; Guerlain, Claire; Debuigne, Antoine ULg et al

in European Polymer Journal (2015), 62

A poly(vinyl alcohol)-block-poly(acrylic acid)-block-poly(4-vinylpyridine) triblock terpolymer (PVOH-b-PAA-b-P4VP) is prepared by hydrolyzing a poly(vinyl acetate)-block-poly(acrylonitrile)-block-poly(4 ... [more ▼]

A poly(vinyl alcohol)-block-poly(acrylic acid)-block-poly(4-vinylpyridine) triblock terpolymer (PVOH-b-PAA-b-P4VP) is prepared by hydrolyzing a poly(vinyl acetate)-block-poly(acrylonitrile)-block-poly(4-vinylpyridine) precursor (PVAc-b-PAN-b-P4VP) synthesized by a combination of cobalt-mediated radical polymerization (CMRP) and nitroxide mediated polymerization (NMP). The PVOH-b-PAA-b-P4VP terpolymer is further micellized in water and the accordingly obtained micellar structures are characterized by a combination of dynamic light scattering (DLS) and cryo-transmission electron microscopy (cryo-TEM) as a function of pH. Well-defined micelles are observed in the whole pH range except for pH values below 4.5 where non-aggregated chains (unimers) are present. The formation of micelles can be rationalized by the formation of insoluble PAA/P4VP inter-polyelectrolyte complexes in the 4.5–6 pH range while hydrophobic P4VP cores are observed at pH values above 6. Finally, the effect of the addition of different salts on the micellar characteristic features is investigated. [less ▲]

Detailed reference viewed: 74 (4 ULg)