References of "Mathieu, Kevin"
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See detailMacroporous poly(ionic liquid)/ionic liquid gels via CO2-based emulsion-templating polymerization
Mathieu, Kevin ULiege; Jérôme, Christine ULiege; Debuigne, Antoine ULiege

in Polymer Chemistry (2018), 9(4), 428-437

Structuring poly(ionic liquid)s (PILs) into porous materials or swelling PILs with free ionic liquids (ILs) has received specific attention recently and contributed to improve the performances of these ... [more ▼]

Structuring poly(ionic liquid)s (PILs) into porous materials or swelling PILs with free ionic liquids (ILs) has received specific attention recently and contributed to improve the performances of these materials used in a wide range of applications. The present work aims to take benefit of both approaches and produce macroporous PIL/IL gels in a single step through an innovative emulsion-templated polymerization method based on supercritical carbon dioxide (scCO2). More precisely, ILs vinyl monomers and crosslinkers were polymerized in the presence of non polymerizable ILs within the outer phase of a CO2-in-ILs high internal phase emulsion (HIPE). Specific macromolecular surfactants were synthesized by controlled radical polymerization techniques and tested for the stabilization of the CO2-in-ILs emulsions. While optimizing the polymerization conditions, we found that adding a limited amount of water in the medium was beneficial for the emulsion stability. Overall, this straightforward process gave access to macroporous polyHIPEs composed of poly(vinyl imidazolium) networks swollen by ‘free’ vinyl imidazolium-based ILs having interesting properties such as switchable polarity upon simple anion exchange reaction. [less ▲]

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See detailAdvanced emulsion-templated porous polymers through controlled radical polymerization
Mathieu, Kevin ULiege

Doctoral thesis (2017)

Macroporous polymer monoliths are remarkable materials used in several applications such as supported catalysis, chromatography, water purification, gas capture, to name but a few. The emulsion-templated ... [more ▼]

Macroporous polymer monoliths are remarkable materials used in several applications such as supported catalysis, chromatography, water purification, gas capture, to name but a few. The emulsion-templated polymerization method, often based on conventional radical polymerization, is a very popular and straightforward approach for preparing such porous polymers. Nevertheless, the demand for more and more sophisticated porous supports with controlled porosity, good mechanical properties and specific surface properties, is increasing and requires the development of innovative synthesis strategies. The present thesis aims to explore the possible benefits of controlled radical polymerization (CRP) for the design of advanced macroporous monoliths via emulsion templated polymerization. In a general approach, copolymers with precise architecture, composition and chain-end functionality, were synthesized by CRP and used as macromolecular surfactants for stabilizing various types of high and medium internal phase emulsion polymerizations. A clear effect of the nature and concentration of the surfactants on the porous structures was emphasized. The physical and chemical anchoring of the macromolecular surfactants at the surface of the porous monoliths was also achieved allowing the functionalization of porous supports while preserving their openness. Finally, specific surfactants were designed by CRP for stabilizing CO2-in-ionic liquid (IL) emulsions which paved the way to the single step synthesis of unique and valuable macroporous poly(ionic liquid)s/ILs gels. Overall, the present work highlights the great potential of CRP for the emulsion-templated polymerization and the production of advanced functional macroporous monoliths. [less ▲]

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See detailFunctional emulsion-templated porous polymers by macromolecular surfactant anchoring strategies
Mathieu, Kevin ULiege; Jérôme, Christine ULiege; Debuigne, Antoine ULiege

Poster (2017, May 22)

Macroporous polymer monoliths with interconnected structures have attracted considerable interest in the fields of supported catalysis, chromatography, water purification, etc. A popular and ... [more ▼]

Macroporous polymer monoliths with interconnected structures have attracted considerable interest in the fields of supported catalysis, chromatography, water purification, etc. A popular and straightforward synthesis approach for such open-cell polymers is based on the polymerization of high internal phase emulsion (HIPE). Advanced functional polyHIPEs were also produced via different post-modification strategies but the latter often consists in tedious multi-step processes. This communication aims at reporting an efficient one-pot macromolecular surfactant-assisted method for the simultaneous synthesis and chemical functionalization of macroporous polyHIPEs. Briefly, amphiphilic block copolymers prepared by nitroxide-mediated radical polymerization (NMP) or reversible addition-fragmentation chain transfer (RAFT) were used as HIPE stabilizers and grafted at the surface of the walls of polyHIPE during the polymerization process. The impact of the controlled radical polymerization mechanism on the porous structure, openness and functionalization of the monoliths will be discussed. This strategy was also implemented with alkyne-terminated copolymers in order to decorate the surface of the polyHIPE’s cavities with “clickable” moieties which broadens the scope of functional macroporous polymers. [less ▲]

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See detailFunctional emulsion-templated macroporous polymers via controlled radical polymerization
Mathieu, Kevin ULiege; Jérôme, Christine ULiege; Debuigne, Antoine ULiege

Conference (2017, May 05)

Macroporous polymer monoliths with interconnected structures have attracted considerable interest in the fields of supported catalysis, chromatography, water purification, etc. A popular and ... [more ▼]

Macroporous polymer monoliths with interconnected structures have attracted considerable interest in the fields of supported catalysis, chromatography, water purification, etc. A popular and straightforward synthesis approach for such open-cell polymers is based on the emulsion-templated polymerization. In this strategy, a major phase is dispersed in a minor continuous phase containing monomers, cross-linker, initiator and surfactant. The curing of the continuous phase followed by the removal of the dispersed phase leads to a monolith with voids interconnected by pores. Size and number of the latters are influenced by several parameters and especially by the nature of the surfactant. Consequently, we prepared by controlled radical polymerization a series of well-defined amphiphilic copolymers having different hydrophilic-lipophilic balance (HLB) and chain-ends, used it as stabilizers for the emulsion-templated polymerizations and demonstrated the crucial effect of the macromolecular features as well as the concentration on the foam morphology. Secondly, the physical and the chemical anchoring of the macromolecular surfactants at the surface of the pores were also considered for tuning the surface properties of the porous monoliths in one step. This strategy was also implemented with alkyne-terminated copolymers in order to decorate the surface of the cavities with “clickable” moieties which broadens the scope of functional macroporous polymers. [less ▲]

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See detailSimultaneous synthesis and chemical functionalization of emulsion-templated porous polymers using nitroxide-terminated macromolecular surfactants
Mathieu, Kevin ULiege; De Winter, Julien; Jérôme, Christine ULiege et al

in Polymer Chemistry (2017), 8(11), 1850-1861

The design of functional 3D macroporous monoliths has become a necessity for a wide range of applications. Traditional post-modification strategies of porous materials are efficient but often consist in ... [more ▼]

The design of functional 3D macroporous monoliths has become a necessity for a wide range of applications. Traditional post-modification strategies of porous materials are efficient but often consist in tedious multi-steps processes. This work describes a straightforward macromolecular surfactant-assisted method for producing chemically functionalized macroporous polyHIPEs with interconnected structures. Accordingly, high internal phase emulsion-templated polymerizations were implemented in the presence of SG1-terminated amphiphilic copolymers prepared by nitroxide- mediated radical polymerization (NMP). The latter served as both stabilizers and functionalizing agents upon thermal activation of its terminal alkoxyamine and covalent anchoring of the released radical copolymer onto the walls of the scaffold. The effect of the polymerization temperature on the functionalization and openness of the final porous materials was explored. As a result, a range of open-cell styrene and acrylate-based polyHIPEs chemically grafted with PEO were obtained. Moreover, polyHIPEs were also decorated with alkyne-bearing PEO and subsequently modified via CuAAc click chemistry in order to demonstrate the potential of this macromolecular surfactants-assisted functionalization method. [less ▲]

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See detailMacro- and near-mesoporous monoliths by medium internal phase emulsion polymerization: a systematic study
Mathieu, Kevin ULiege; Jérôme, Christine ULiege; Debuigne, Antoine ULiege

in Polymer (2016), 99

The synthesis of a series of poly(ethylene oxide)-b-polystyrene copolymers with different block lengths was performed by radical addition fragmentation chain transfer. These amphiphilic copolymers were ... [more ▼]

The synthesis of a series of poly(ethylene oxide)-b-polystyrene copolymers with different block lengths was performed by radical addition fragmentation chain transfer. These amphiphilic copolymers were tested as stabilizers for water-in-oil medium internal phase emulsion (MIPE) templating polymerization and the formation of polyMIPEs with controlled morphology. Aside from the structure of the emulsion stabilizer, several parameters susceptible to influence the size of the cavities and the interconnectivity of the porous monoliths were probed including the choice of the comonomers, treatment of the emulsion by ultrasound, the use of controlled radical polymerization method for the network formation as well as interfacial initiation. Interconnected cellular monoliths were produced. The polymerization of the ultrasonicated water-in-ethylhexylacrylate/divinylbenzene MIPE notably led to near-mesoporous open-cell material. Mechanical properties and specific surface areas of the polyMIPEs were also investigated and discussed. [less ▲]

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See detailTuning morphology and surface properties of emulsion-templated porous polymers by controlled radical polymerization
Mathieu, Kevin ULiege; Jérôme, Christine ULiege; Debuigne, Antoine ULiege

Poster (2016, May 23)

Macroporous polymer monoliths with interconnected structures have attracted considerable interests in the last decades and sustain many applications in the fields of supported catalysis, chromatography ... [more ▼]

Macroporous polymer monoliths with interconnected structures have attracted considerable interests in the last decades and sustain many applications in the fields of supported catalysis, chromatography, microfluidic, water purification, membrane separation, tissue engineering, to name but a few. A very popular and straightforward synthetic approach for such open-cell polymers is the High Internal Phase Emulsion (HIPE) polymerization method. The latter consists in three steps: (i) stabilization of an emulsion in which an internal phase with a volume fraction higher than 74% is dispersed within a minor continuous phase containing a polymer network precursor, (ii) curing of the polymer phase by polymerization or crosslinking reactions, (iii) removal of the internal phase to release the porosity. The surface properties and morphology of the polyHIPEs are important features that must be controlled and adjusted for each applications. In this context, we prepared by controlled radical polymerization a series of well-defined amphiphilic copolymers having different hydrophilic-lipophilic balance (HLB) and chain-ends, used it as stabilizers for the emulsion-templated polymerizations and demonstrated the crucial effect of the structure of the macromolecular surfactant on the morphology of the polyHIPEs. Finally, the physical and chemical anchoring of the macromolecular surfactants at the surface pores were also considered for tuning the surface properties of the porous monoliths. [less ▲]

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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 ULiege; Jérôme, Christine ULiege; Debuigne, Antoine ULiege

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 detailDouble thermo-responsive hydrogels from poly(vinylcaprolactam) containing diblock and triblock copolymers
Thomassin, Jean-Michel ULiege; Mathieu, Kevin ULiege; Kermagoret, Anthony ULiege 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 detailDouble thermoresponsive di- and triblock copolymers based on N-vinylcaprolactam and N-vinylpyrrolidone: synthesis and comparative study of solution behaviour
Kermagoret, Anthony ULiege; Mathieu, Kevin ULiege; Thomassin, Jean-Michel ULiege et al

in Polymer Chemistry (2014), 5(22), 6534-6544

Poly(N-vinylcaprolactam) (PNVCL) and poly(N-vinylpyrrolidone) (PNVP) are water soluble polymers of interest especially in the biomedical field. Moreover, PNVCL is characterized by a lower critical ... [more ▼]

Poly(N-vinylcaprolactam) (PNVCL) and poly(N-vinylpyrrolidone) (PNVP) are water soluble polymers of interest especially in the biomedical field. Moreover, PNVCL is characterized by a lower critical solution temperature close to 36 °C in water, which makes it useful for the design of thermoresponsive systems. In this context, we used the cobalt-mediated radical polymerization (CMRP) and reaction coupling (CMRC) for synthesizing a series of well-defined NVCL and NVP-based copolymers, including statistical copolymers as well as double thermoresponsive diblocks and triblocks. Dynamic light scattering and turbidimetry analyses highlighted the crucial impact of the copolymer composition and architecture on the cloud point temperature (TCP) of each segment and also their influence on the multistep assembly behaviour of block copolymers. Addition of NaCl enabled us to adjust the inter-TCP range of the di- and triblock in which selective precipitation of one block and self-assembly of the copolymer were favoured. Overall, data presented here provide a basis for the synthesis of a broad range of NVCL/NVP based copolymer architectures with a tunable thermal response in water. [less ▲]

Detailed reference viewed: 54 (17 ULiège)
See detailRheological characterization of double thermo-responsive block copolymer hydrogels
Thomassin, Jean-Michel ULiege; Mathieu, Kevin ULiege; Kermagoret, Anthony ULiege et al

Poster (2013, November 20)

The ability of double thermoresponsive block copolymers to form hydrogels has been thoroughly studied by rheology. These copolymers having two discrete LCSTs were synthesized following a one-pot strategy ... [more ▼]

The ability of double thermoresponsive block copolymers to form hydrogels has been thoroughly studied by rheology. These copolymers having two discrete LCSTs were synthesized following a one-pot strategy based on the sequential cobalt mediated radical polymeryzation of N-vinylcaprolactam (NVCL) followed by the copolymerization of N-vinylpyrrolidone (NVP) with the residual NVCL.Moreover, the very efficient cobalt mediated radical coupling of the growing chains was advantageously used to design triblock copolymers with similar morphological characteristics than the diblock copolymers (same external block length, copolymer ratio…) allowing direct comparison between their respective gels to be established. Different parameters have been compared such as the block length and the copolymer concentration. Temperature ramps were first performed to distinguish the different states, i.e., solubilized copolymers (below the two LCSTs), micelles (between the two LCSTs) and precipitated polymers (above the two LCSTs). [less ▲]

Detailed reference viewed: 53 (12 ULiège)