References of "Detrembleur, Christophe"
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See detailBioinspired redox-active catechol-bearing polymers as ultra-robust organic cathodes for lithium storage
Patil, Nagaraj ULiege; Aqil, Abdelhafid ULiege; Ouhib, Farid ULiege et al

in Advanced Materials (in press)

Redox-active catechols are bioinspired precursors for ortho-quinones that are characterized by higher discharge potentials than para-quinones, the latter being extensively used as organic cathode ... [more ▼]

Redox-active catechols are bioinspired precursors for ortho-quinones that are characterized by higher discharge potentials than para-quinones, the latter being extensively used as organic cathode materials for lithium ion batteries (LIBs). Here, this study demonstrates that the rational molecular design of copolymers bearing catechol- and Li+ ion-conducting anionic pendants endow redox-active polymers (RAPs) with ultrarobust electrochemical energy storage features when combined to carbon nanotubes as a flexible, binder-, and metal current collector-free buckypaper electrode. The importance of the structure and functionality of the RAPs on the battery performances in LIBs is discussed. The structure-optimized RAPs can store high-capacities of 360 mA h g−1 at 5C and 320 mA h g−1 at 30C in LIBs. The high ion and electron mobilities within the buckypaper also enable to register 96 mA h g−1 (24% capacity retention) at an extreme C-rate of 600C (6 s for total discharge). Moreover, excellent cyclability is noted with a capacity retention of 98% over 3400 cycles at 30C. The high capacity, superior active-material utilization, ultralong cyclability, and excellent rate performances of RAPs-based electrode clearly rival most of the state-of-the-art Li+ ion organic cathodes, and opens up new horizons for large-scalable fabrication of electrode materials for ultrarobust Li storage. [less ▲]

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See detailMerging supercritical carbon dioxide and organocatalysis for the precision and green synthesis of poly(lactide)-based (co)polymers
Grignard, Bruno ULiege; De Winter, Julien; Gerbaux, Pascal et al

in European Polymer Journal (in press)

Well-defined poly(lactide)-based block copolymers were synthesized by a heterogeneous solvent and metal-free green approach by using organocatalysts in supercritical carbon dioxide (scCO2). We first ... [more ▼]

Well-defined poly(lactide)-based block copolymers were synthesized by a heterogeneous solvent and metal-free green approach by using organocatalysts in supercritical carbon dioxide (scCO2). We first report on the homopolymerization of both L- and D,L- lactide by organocatalyzed Ring-Opening Polymerization (o-ROP) by using a bicomponent organocatalyst composed of a thiourea derivative and various tertiary amines as cocatalysts. Control over the molar mass and dispersity is achieved until high monomer conversion although the polylactides are insoluble in the polymerization medium. The precision synthesis of PLA-based block copolymers from various CO2-phobic hydroxyl end-capped macroinitiators such as polyethylene glycol, polycaprolactone, polybutylene succinate and polyphosphoester was then reported. Merging scCO2 with this organocatalytic system provides therefore a unique tool for the design under solvent-free conditions of poly(lactide)-based block copolymers that are insoluble in scCO2. [less ▲]

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See detailReinforced poly(hydroxyurethane) thermosets as high performance adhesives for aluminum substrates
Panchireddy, Satyannarayana ULiege; Thomassin, Jean-Michel ULiege; Grignard, Bruno ULiege et al

in Polymer Chemistry (2017), 8(38), 5897-5909

Poly(hydroxyurethane) (PHU) thermosets reinforced with (functional) nanofillers were developed to design high performance adhesives for bare aluminum. Solvent-free cyclic carbonate/amine/PDMS formulations ... [more ▼]

Poly(hydroxyurethane) (PHU) thermosets reinforced with (functional) nanofillers were developed to design high performance adhesives for bare aluminum. Solvent-free cyclic carbonate/amine/PDMS formulations loaded with native, epoxy- or cyclic carbonate-functionalized ZnO nanofillers were premixed before deposition and thermal curing onto Al. The results highlight that the addition of PDMS prevents PHUs from delamination of the Al surface by increasing the adhesive hydrophobicity and thus limiting the water uptake. The dispersion of functional fillers within PHUs improves their thermal and mechanical properties. Benchmarking of the adhesive performances of the reinforced PHU glues with existing PHU formulations attests for the benefits of dispersing functional fillers and PDMS within the resin and evidences a 270% increase of the shear strength of reinforced PHUs adhesives compared to formulations reported in the literature. [less ▲]

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See detailOn the phase behaviour of oxetane-CO2 and propargylic alcohols-CO2 binary mixtures by in situ infrared micro-spectrometry
Zaky, Mohamed; Boyaval, Amélie ULiege; Grignard, Bruno ULiege et al

in Journal of Supercritical Fluids (2017), 128

The phase behaviour of carbon dioxide/propargylic alcohols and carbon dioxide/oxetanes mixtures has been investigated using in-situ FTIR microspectrometry that allows us determining the evolution of the ... [more ▼]

The phase behaviour of carbon dioxide/propargylic alcohols and carbon dioxide/oxetanes mixtures has been investigated using in-situ FTIR microspectrometry that allows us determining the evolution of the concentration of each component in the liquid phase as a function of temperature and pressure. It was at the same time possible to look inside the cell and to visualize the expansion of the liquid phase during the increase of the pressure. The measurements were performed at three different temperatures (40, 70 and 100◦C) for pressures ranging between 0.1 and 15 MPa. Propargylic alcohol (PA), 2-methyl-3-butyn-2-ol (MBOL), 3-butyn-1-ol (BOL) and trimethylene oxide (TMO) were selected as these molecules are used in the synthesis of cyclic or polycarbonates by coupling with CO2. Thus, we determined the CO2 sorption and the concentration of the substrate in the liquid phase. Thanks to these measurements, we established the pressure-composition phase diagram for the liquid phase of these substrate/CO2 binary mixtures. [less ▲]

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See detailWell-defined polyvinylamine-based copolymers: synthesis by organometallic-mediated radical polymerization and use in gene transfection
Debuigne, Antoine ULiege; Dréan, Mathilde; Detrembleur, Christophe ULiege et al

Conference (2017, August 22)

Polyvinylamine (PVAm) presents valuable properties like affinity for many supports, pH responsiveness, metal binding capacity, polyelectrolytes complexation, and is used in various applications including ... [more ▼]

Polyvinylamine (PVAm) presents valuable properties like affinity for many supports, pH responsiveness, metal binding capacity, polyelectrolytes complexation, and is used in various applications including coatings, water purification or gas membrane separation. PVAm is commonly prepared by free radical polymerization of N-vinyl monomers followed by deprotection and release of the masked amino functions. However, examples of controlled synthesis of polyvinylamine-based copolymers are scarce because of the high reactivity of the propagating radicals deriving from non-conjugated N-vinyl monomers due to the lack of resonance stabilization. The present communication aims at reporting an efficient platform for producing tailor-made PVAms via organometallic-mediated radical polymerization (OMRP) of N-vinylacetamides followed by hydrolysis of the pendent amide moieties. In this case, cobalt(II) acetylacetonate was successfully used as controlling agent. The synthesis of a series of well-defined homopolymers, statistical and block copolymers with pendent primary and/or secondary amines having low dispersities, predictable molar masses and precise compositions, will be described. Finally, we will discuss the possible use of these polyvinylamine-containing copolymers as gene transfection agents. Some of them demonstrated high DNA transfection level in combination with high cell viability. [less ▲]

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See detailCO2-sourced α-alkylidene cyclic carbonates: a Step forward in the quest for functional regioregular poly(urethane)s and poly(carbonate)s
Gennen, Sandro ULiege; Grignard, Bruno ULiege; Tassaing, Thierry et al

in Angewandte Chemie International Edition (2017), 56(35), 1039410398

We describe a robust platform for the synthesis of a large diversity of novel functional CO2 -sourced polymers by exploiting the regio-controlled and site selective ring-opening of α- alkylidene ... [more ▼]

We describe a robust platform for the synthesis of a large diversity of novel functional CO2 -sourced polymers by exploiting the regio-controlled and site selective ring-opening of α- alkylidene carbonates by various nucleophiles. The remarkable reactivity of α-alkylidene carbonates is dictated by the exocyclic olefinic group that selectively orients the cyclic carbonate ring- opening with the formation of an enol species. The polyaddition of CO2 -sourced bis-α-alkylidene carbonates (bis-αCCs) with primary and secondary diamines provides novel regioregular functional poly(urethane)s. The reactivity of bis-αCCs is also exploited for producing new poly(β-oxo-carbonate)s by organocatalyzed polyaddition with a diol. All polyadditions were feasible under ambient conditions. This synthesis platform provides new functional variants of world-class leading polymers families (polyurethanes, polycarbonates) and valorises CO2 as a chemical feedstock. [less ▲]

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See detailOrganometallic-mediated alternating radical copolymerization of tert-butyl-2- trifluoromethacrylate with vinyl acetate and synthesis of block copolymers thereof
Banerjee, Sanjib; Ladmiral, Vincent; Debuigne, Antoine ULiege et al

in Macromolecular Rapid Communications (2017), 38(15), 1700203

Organometallic-mediated radical polymerization (OMRP) has given access to well-defined poly(vinyl acetate-alt-tert-butyl-2-trifluoromethacrylate)-b-poly(vinyl acetate) and poly (VAc- alt-MAF-TBE ... [more ▼]

Organometallic-mediated radical polymerization (OMRP) has given access to well-defined poly(vinyl acetate-alt-tert-butyl-2-trifluoromethacrylate)-b-poly(vinyl acetate) and poly (VAc- alt-MAF-TBE) copolymers composed of two electronically distinct monomers: vinyl acetate (VAc, donor, D) and tert-butyl-2-trifluoromethacrylate (MAF-TBE, acceptor, A), with low dispersity (≤1.24) and molar masses up to 57 000 g mol−1. These copolymers have a precise 1:1 alternating structure over a wide range of comonomer feed compositions. The reactivity ratios are determined as rVAc = 0.01 ± 0.01 and rMAF-TBE = 0 at 40 °C. Remarkably, from a feed containing >50% molar VAc content, poly(VAc-alt-MAF-TBE)-b- PVAc block copolymers are produced via a one- pot synthesis. Such diblock copolymers exhibit two glass transition temperatures attributed to the alternating and homopolymer sequences. The OMRP of this fluorine-containing alter- nating monomer system may provide access to a wide range of new polymer materials. [less ▲]

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See detailInnovative polyelectrolytes/poly(ionic liquid)s for energy and environment
Ajjan, Fátima N.; Ambrogi, Martina; Tiruye, Girum Ayalneh et al

in Polymer International (2017), 66(8), 1119-1126

This manuscript presents the work carried out within the European Project RENAISSANCE-ITN, which was dedicated to the development of innovative polyelectrolytes for energy and environmental applications ... [more ▼]

This manuscript presents the work carried out within the European Project RENAISSANCE-ITN, which was dedicated to the development of innovative polyelectrolytes for energy and environmental applications. Within the project different types of innovative polyelectrolytes were synthesized such as poly(ionic liquid)s coming from renewable or natural ions, thiazolium cations, cathechol functionalities or from a new generation of cheap deep-eutectic monomers. Further, macromolecular architectures such as new poly(ionic liquid) block copolymers and new (semi)conducting polymer/polyelectrolyte complexes were also developed. As the final goal, the application of these innovative polymers in energy and environment was investigated. Important advances in energy storage technologies included the development of new carbonaceous materials, new lignin/conducting polymer biopolymer electrodes, new iongels and single-ion conducting polymer electrolytes for supercapacitors and batteries and new poly(ionic liquid) binders for batteries. On the other hand, the use of the innovative polyelectrolytes into sustainable environmental technologies led to the development of new liquid and dry water, new materials for water cleaning technologies such as floculants, oil absorbers, new recyclable organocatalysts platform and multifunctional polymer coatings with antifouling and antimicrobial properties. All in all this article demonstrates the potential of the poly(ionic liquid)s for high-value applications in Energy & Enviromental areas. [less ▲]

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See detailBio- and CO2-sourced polyhydroxyurethanes for hydrogels coatings, foams and high performance adhesives
Gennen, Sandro ULiege; Panchireddy, Satyannarayana ULiege; Grignard, Bruno ULiege et al

Poster (2017, June 09)

Due to concerns about global warming combined with the decrease of fossil resources, the chemical transformation of carbon dioxide (CO2) into added-value products has gained interest in both academic and ... [more ▼]

Due to concerns about global warming combined with the decrease of fossil resources, the chemical transformation of carbon dioxide (CO2) into added-value products has gained interest in both academic and industrial fields. Indeed, CO2 can be viewed as a cheap, non-toxic and renewable C1 building block precursor of sophisticated organic molecules and polymers. One representative example of CO2 transformation includes the synthesis of various (bis)cyclic carbonates via CO2/epoxide coupling.1-3 Bis-cyclic carbonates were then valorized as monomers for the synthesis of series of novel low carbon footprint poly(hydroxyurethane)s (PHUs). These polymers are now exploited to produce sustainable materials including foams for thermal insulation,4 hydrogels (for potential biomedical use)5 and high performance adhesives and glues (for metal, glass and wood). [less ▲]

Detailed reference viewed: 33 (1 ULiège)
See detailMultifunctional poly(ionic liquid)s: from synthesis to applications in energy and environment
Detrembleur, Christophe ULiege; Patil, Nagaraj ULiege; Debuigne, Antoine ULiege et al

Conference (2017, May 24)

Poly(ionic liquid)s (PILs) are a subclass of polyelectrolytes that gained an enabling role in many fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids ... [more ▼]

Poly(ionic liquid)s (PILs) are a subclass of polyelectrolytes that gained an enabling role in many fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids with the flexibility and properties of macromolecules, and provide novel attractive functions. Recently, the precision design of novel PILs by controlled/living polymerization (CLP) techniques was intensively searched for developing emerging applications. This talk will first discuss recent routes for the precision synthesis of all vinyl-imidazolium based (co)polymers in water or in organic media under non-demanding experimental conditions. We will then describe the preparation of innovative redox and surface active PILs, and show the potential of these PILs in battery applications and for multifunctional coatings. More specifically, we will show how macromolecular engineering can be exploited for designing innovative polymer cathodes for ultra-high performance Li storage with unprecedented performances (high capacities and ultra-long life-span over more than 3000 cycles at an extreme current-rate). This innovative and effective molecular design for polymer cathodes opens up new horizons in developing an economical and environmentally benign platform for large-scalable fabrication of high performance batteries. [less ▲]

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See detailControlled synthesis of fluorinated copolymers via cobalt-mediated radical copolymerization of perfluorohexylethylene and vinyl acetate
Demarteau, Jérémy ULiege; Améduri, Bruno; Ladmiral, Vincent et al

in Macromolecules (2017), 50(10), 3750-3760

Designing novel polyfluoropolymer architectures is attractive for the development of new applications, such as advanced coatings, purification membranes, or materials for energy. Nevertheless, controlling ... [more ▼]

Designing novel polyfluoropolymer architectures is attractive for the development of new applications, such as advanced coatings, purification membranes, or materials for energy. Nevertheless, controlling the radical polymerization of fluoroalkenes is very challenging due to the high reactivity of the propagating fluorinated macroradicals. This study aims at exploring the controlled copolymerization of perfluoro- hexylethylene (PFHE) and vinyl acetate (VAc) in order to prepare a range of well-defined statistical poly(PFHE-stat-VAc) copolymers with different compositions. Cobalt-mediated radical polymerization demonstrated to be active at 40 °C starting from an alkylcobalt(III) initiator, and copolymers with a fluorinated monomer content as high as ca. 80 wt % were successfully prepared. Reactivity ratios were determined to be rVAc = 0.18 and rPFHE = 0 at 40 °C and emphasized a clear tendency for alternation. Unprecedented PFHE/VAc containing block copolymers were also prepared via a single-step approach or through sequential copolymerizations. Finally, hydrolysis of the pendant ester groups of these copolymers led to the corresponding fluorinated copolymers bearing vinyl alcohol (VOH). A preliminary solution behavior study, carried out by dynamic light scattering and transmission electron microscopy on block copolymers composed of PFHE and VAc or VOH units, evidenced a marked amphiphilicity of the copolymer composed of an extremely hydrophobic PFHE block associated with a highly hydrophilic PVOH segment. [less ▲]

Detailed reference viewed: 41 (6 ULiège)
See detailPrecision synthesis and characterization of novel functional polymers
Scholten, Philip ULiege; Debuigne, Antoine ULiege; Demarteau, Jérémy ULiege et al

Poster (2017, May 23)

Among controlled radical polymerisation techniques, cobalt-mediated radical polymerisation (CMRP) has proven to be a valuable alternative in polymerising unreactive and unconjugated monomers of many ... [more ▼]

Among controlled radical polymerisation techniques, cobalt-mediated radical polymerisation (CMRP) has proven to be a valuable alternative in polymerising unreactive and unconjugated monomers of many different monomer classes under mild conditions, including α-olefins. In a reversible deactivation mechanism, a cobalt complex reversibly traps the active growing chains and converts them into dormant species, avoiding side reactions and allowing for a controlled polymerisation. A fine control over the architecture is possible and allows to synthesise a large diversity of unprecedented block and alternating copolymers. Furthermore, functionalisation of the α- and ω-chain ends is now also possible. In this poster, the polymerization of different vinyl monomers using CMRP has been investigated to design highly functional materials under mild experimental conditions. The copolymerisation behaviour of these novel monomers was examined, and the structure and thermal properties of the new copolymers were investigated. [less ▲]

Detailed reference viewed: 31 (9 ULiège)
See detailMerging CO2 transformation and utilization with renewable bio-resources: a step forward to a double vision of sustainable chemistry
Grignard, Bruno ULiege; Poussard, Loïc; Raquez, Jean-Marie et al

Conference (2017, May 22)

Valorizing waste CO2 as a cheap, inexhaustible and renewable C1 feedstock is an early stage technology with strong innovation potential that imposes itself as a strategic driver for developing future low ... [more ▼]

Valorizing waste CO2 as a cheap, inexhaustible and renewable C1 feedstock is an early stage technology with strong innovation potential that imposes itself as a strategic driver for developing future low carbon footprints materials. Beside its use as raw chemical, the “physical” valorization of CO2 in a series of industrial cost-efficient processes will also accelerate the development of a low carbon economy and support the elaboration of a global low carbon vision scheme. The synergistic and paradigm-transforming holistic project we propose perfectly illustrates these concepts by encompassing a “cradle” to “grave” vision, i.e. from the products conception from CO2 and bio-resources to their production and processing through sustainable processes compatible with existing industrial relevant infrastructures. It focuses on the elaboration of sustainable isocyanate-free polyurethane foams with promising thermal insulation properties. By its objectives, this study also proposes an ideal alternative to the conventional synthesis of PUs and a practical answer to the challenge the PU sector is facing due to changes in the REACH regulations limiting the use of isocyanates. The success of the project relies on 3 key steps involving: i) The synthesis of bio- and CO2-sourced cyclic carbonates monomers: Due to the low reactivity of CO2 versus epoxides, addition of catalysts is necessary. To overcome this limitation, we developed a new highly-efficient bicomponent homogeneous organocatalyst that showed unexpected activity for the fast (within a few minutes) and selective addition of CO2 onto model epoxides and epoxidized vegetable oil under solvent-free and mild experimental conditions at the multiKg scale. The use of this powerful dual organocatalyst was further extended to the first organocatalytic coupling of CO2 with less reactive oxetanes to produce hydroxyl telechelic oligocarbonate entering the synthesis of CO2-sourced conventional PUs. - The synthesis of sustainable bio- and CO2- sourced isocyanates-free polyurethanes (NIPU): Sustainable NIPUs were produced by step-growth polymerization between the so-produced bio- and CO2-sourced cyclic carbonates and biosourced amino-telechelic comonomers derived from linseed fatty acids according to a process compatible with existing industrial infrastructures (extrusion). - The foaming of NIPUs: Sustainable foams with thermal insulation were produced by the supercritical CO2 assisted foaming technology. Due to its solubility in polymers, CO2 can replace conventional flammable VOCs and ozone depletion physical blowing agents as hydro- or fluorocarbons exhibiting long atmospheric life-time and/or mean global warming potential 2800 higher than CO2. By finely choosing the CO2 impregnation and the foaming conditions, low density microcellular NIPU foams with a thermal conductivity as low as 0.050 Wm-1K-1 were produced. Our study shows that CO2 is not only sequestered in the material for long-term application, but is also valorized as a blowing agent in the production of sustainable thermally insulating NIPU foams. Such low carbon footprints materials will contribute to energy conservation and savings by reducing CO2 emissions. [less ▲]

Detailed reference viewed: 69 (6 ULiège)
See detailUnprecendeted fluoroalkene-based copolymers through cobalt-mediated radical polymerization
Demarteau, Jérémy ULiege; Ameduri, Bruno; Ladmiral, Vincent et al

Poster (2017, May 22)

The precision design of fluorinated copolymers is challenging but also attractive for future developments in a wide range of applications involving fluoropolymers, such as advanced coatings or ... [more ▼]

The precision design of fluorinated copolymers is challenging but also attractive for future developments in a wide range of applications involving fluoropolymers, such as advanced coatings or purification membranes. In particular, controlling the radical polymerization of fluoroalkenes remains extremely difficult because of the high reactivity of these monomers due to the lack of resonance stabilizing group on their double bond. Herein, Cobalt-Mediated Radical Polymerization (CMRP) was used to efficiently control the bulk copolymerization of perfluorohexylethylene (PFHE) and vinyl acetate (VAc). Well-defined statistical poly(PFHE-stat-VAc) copolymers with different compositions (0 < FPFHE < 0.5) were obtained accordingly. In some cases, fluorinated monomer content as high as 80 % by weight were achieved. Reactivity ratios were determined (rVAc = 0.18 and rPFHE = 0) and emphasized a clear tendency for alternation. Single step approach and sequential polymerization were assessed for the synthesis of novel PFHE/VAc block copolymers. Finally, the acidic hydrolysis of the pendant ester groups of these block copolymers led to the formation of novel highly amphiphilic macromolecules bearing a PVOH hydrophilic segment and a hydrophobic PFHE-based block. [less ▲]

Detailed reference viewed: 39 (3 ULiège)
See detailSimple, cheap but highly efficient organo catalysts for the fixation of CO2 on propargylic alcohols
Ngassam Tounzoua, Charlene Gabriela ULiege; Gilbert, Bernard ULiege; Detrembleur, Christophe ULiege et al

Poster (2017, May 04)

In the last years, many efforts have been devoted to the valorisation of CO2 as an abundant and renewable C1 building block for cyclic carbonate synthesis. Many synthetic routes have been proposed to ... [more ▼]

In the last years, many efforts have been devoted to the valorisation of CO2 as an abundant and renewable C1 building block for cyclic carbonate synthesis. Many synthetic routes have been proposed to convert CO2 into five or six-membered cyclic carbonates finding applications as green solvent, electrolytes for Li-ion batteries, intermediates for organic synthesis, monomers for the production of polycarbonates or isocyanate-free synthesis of poly(hydroxyrethane)s, etc. Although the 100% atom economy synthesis of 5-membered cyclic carbonates from CO2 and epoxides/oxetanes has been widely reported in the literature, the carboxylative coupling of CO2 with alkynols remains unexplored. Transition metal-based complexes, organic bases (guanidine, amidine, phosphine), N-heterocyclic carbenes or olefins, and K2CO3 have been proposed as catalysts. However they generally present sufficient activity at high pressure and/or temperature or require a high catalyst loading. Additionally some of them are toxic and/or sensitive to hydrolysis or oxidation. In this work, we designed novel, cheap, easily customizable and highly efficient organocatalysts for the synthesis of cyclic α-methylene carbonates from CO2 and alkynols. Kinetics of the CO2/alkynol coupling reaction were followed by Raman spectroscopy with organocatalysts of different structures, and the best candidate was identified. The main parameters that influenced the system reactivity and selectivity have been identified and will be presented in this poster. [less ▲]

Detailed reference viewed: 55 (8 ULiège)
See detailSynthesis of hierarchical N-doped porous carbon structure/nanospheres Fe2O3 composites and its application in lithium-ion battery as lithium-ion anodes
Alkarmo, Walid ULiege; Ouhib, Farid ULiege; Aqil, Abdelhafid ULiege et al

Poster (2017, May 04)

Nitrogen-doped porous carbons are of special interest, because their unique physical properties such as high surface area, multidimensional electron transport pathways and good mechanical strength, and ... [more ▼]

Nitrogen-doped porous carbons are of special interest, because their unique physical properties such as high surface area, multidimensional electron transport pathways and good mechanical strength, and are thus very important for applications in the fields of catalysis, environment techniques and energy generation and storage. Moreover, nitrogen-doping can be further amplified in a porous structure that bears a high surface area to increases their materials performance in electrochemical devices, such as double layer capacitors and lithium-ion batteries. In addition, nitrogen-doping can enhance the lithium insertion, between the nitrogen-doped carbon material and lithium. And it can create a large number of defects in the porous configuration and offer more active sites for lithium insertion. Toward this goal, a hierarchically structured macro- and mesoporous N-doped carbon with dispersed Fe2O3 nanoparticles (NDC@Fe2O3) is prepared by thermal treatment of a novel composite composed by PMMA particles decorated by graphene oxide (GO), PPy and iron salts. The NDC@Fe2O3 composite exhibited high surface area with a hierarchical pores structure. Integrated as a lithium ion battery anode, NDC@Fe2O3 exhibited high reversible capacity of 930 mA h/g over 200 cycles. The combination of Fe2O3 nanoparticles with nitrogen-doped porous carbons to form hybrid anode has been an efficient way to maintain the electronic integrity of the whole electrode since the carbon acts as a buffer layer to accommodate the volume variation and to provide multidimensional electron transport pathways during the charge/discharge process. [less ▲]

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See detailReinforced poly(hydroxyurethane) coatings and high performance adhesive
Panchireddy, Satyannarayana ULiege; Grignard, Bruno ULiege; Thomassin, Jean-Michel ULiege et al

Poster (2017, May 04)

Polyurethane (PU) is one of the most widely used polymeric materials and largely valorised in coating applications as paints or as adhesives. Because toxicity issues of isocyanates and changes in the ... [more ▼]

Polyurethane (PU) is one of the most widely used polymeric materials and largely valorised in coating applications as paints or as adhesives. Because toxicity issues of isocyanates and changes in the environmental and REACH regulations, there is a need today to develop new greener and safer alternatives to produce PU. One of the most promising way relies on the synthesis of polyurethane by a non-isocyanate route (NIPU) by copolymerization between a bicyclic carbonate monomers and a diamine. This study reports on the synthesis of new sustainable NIPU coatings for Al anti-corrosion protection and for metal adhesion. In a first step, (bio- and) CO2-sourced cyclic carbonates will be synthesized by coupling of multifunctional epoxides with CO2 using a new efficient bicomponent organocatalyst. In a second step, various cyclic carbonates/amines formulations were developed and cured in presence of fillers to produce reinforced NIPUs thermosets which anti-corrosion and adhesive properties are evaluated and benchmarked with existing formulations. Some formulations present outstanding adhesions to various substrates. [less ▲]

Detailed reference viewed: 57 (5 ULiège)
See detailAll poly(ionic) liquid-based block copolymers incorporating fluorinated and triethyleneglycol units: direct synthesis in water and investigation as single-ion conductive solids
Ouhib, Farid ULiege; Cordella, Daniela; Aqil, Abdelhafid ULiege et al

Poster (2017, May 04)

Poly(ionic liquid)s (PILs) have attracted a considerable attention as innovative single-ion solid polyelectrolytes (SPEs) in substitution to the more conventional electrolytes for a variety of ... [more ▼]

Poly(ionic liquid)s (PILs) have attracted a considerable attention as innovative single-ion solid polyelectrolytes (SPEs) in substitution to the more conventional electrolytes for a variety of electrochemical devices. Imidazolium-based PILs are amongst the most investigated, because they are easy to synthesize and some of them have shown a good combination between high ionic conductivity, wide chemical and electrochemical stability, and good mechanical properties. Herein, we report the precise synthesis, characterization, and use as single-ion SPE of a novel double PIL-based amphiphilic diblock copolymer (BCP), i.e. where all monomer units are of N-vinyl-imidazolium-type, with triethylene glycol pendant groups in the first block, and a statistical distribution of N-vinyl-3-ethyl- and N-vinyl-3-perfluorooctyl-imidazolium bromides in the second block. BCP synthesis is achieved directly in water by a one-pot process, following the principle of the cobalt-mediated radical polymerization-induced self-assembly (CMR-PISA). A subsequent anion exchange reaction substituting bis(trifluoromethylsulfonyl)imide (Tf2N-) for bromide (Br-) counter-anions leads to the targeted PIL BCPs with two different lengths of the first block. They demonstrate ionic conductivity σDC = 1-3 10-7 S cm-1, as determined by broadband dielectric spectroscopy at 30 °C (under anhydrous conditions), and form free standing films with mechanical properties suited for SPE applications with Young’s modulus of 3.8 MPa and elongation at break of 250 % as determined by stress/strain experiments. [less ▲]

Detailed reference viewed: 79 (3 ULiège)
See detailHow to exploit bio- and CO2-based isocyanates-free polyurethanes for environmental and biomedical applications?
Gennen, Sandro ULiege; Grignard, Bruno ULiege; Alves, Margot et al

Poster (2017, May 04)

Polyurethane (PU) is one of the most important family of polymers that is largely used in coatings, foams, elastomers, sealants/adhesives in the building, automotive, household and biomedical sectors ... [more ▼]

Polyurethane (PU) is one of the most important family of polymers that is largely used in coatings, foams, elastomers, sealants/adhesives in the building, automotive, household and biomedical sectors. Classically, PU is produced by a step-growth polymerization between di- or polyols and di- or polyisocyanates. However, isocyanates are toxic and produced from even more toxic phosgene. To avoid the use of isocyanates, different synthetic alternatives for PUs have been developed. One of the most studied approaches relies on the step-growth polymerization between di- or polyamines and CO2-sourced di- or polycyclic carbonates, affording poly(β-hydroxyurethane)s (PHUs) that showed improved thermal, chemical and mechanical properties compared to conventional PUs. In this study, we would like to show how PHUs can be exploited to design (bio- and) CO2-based foams for thermal insulation as well as novel reinforced hydrogels for potential biomedical applications. First, we developed a highly efficient binary organocatalyst for the fast and selective synthesis of cyclic carbonates under very mild conditions from CO2 and various epoxides, including bio-based ones. Secondly, these cyclic carbonates were valorised as monomers for the preparation of foams and hydrogels based on PHUs. In this poster, we will describe the preparation and characterization of these PHU foams and hydrogels, and highlight their huge potential as thermal insulating materials (PHU foams) or as biomaterials for shock absorption properties (PHU hydrogels). [less ▲]

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See detailControlled synthesis of α-olefins-based copolymers by organocobalt(III) complexes
Demarteau, Jérémy ULiege; Debuigne, Antoine ULiege; Detrembleur, Christophe ULiege

Conference (2017, May 04)

Polyolefins, and ethylene-vinyl acetate (EVA) copolymers in particular, are highly attractive materials that are industrially synthesized by a free radical process for large range of applications from ... [more ▼]

Polyolefins, and ethylene-vinyl acetate (EVA) copolymers in particular, are highly attractive materials that are industrially synthesized by a free radical process for large range of applications from food packaging to coatings. Their production requires drastic synthesis conditions (high pressure and high temperature) and the resulting polymers are generally ill-defined. Controlling the polymerization of these unconjugated monomers remains however extremely difficult because of the lack of stabilizing group on their double bond. Moreover, the preparation of chain-end functionalized polyolefins is actually impossible under these conditions. This communication aims at reporting an efficient platform for the precision design of alpha-olefin-based copolymers through a controlled radical polymerization technique called Cobalt-Mediated Radical Polymerization (CMRP). The latter is based on the reversible deactivation of the radical chains by a cobalt complex bearing acetylacetonate (acac) ligands, which is very efficient under mild experimental conditions. The presentation will focus on three main axes: (i) the synthesis of a novel organocobalt(III) complex useful for the functionalization of the polymer chains, (ii) the preparation of various EVA architectures, (iii) the controlled copolymerization of vinyl acetate with a perfluorinated alkene, i.e. perfluorohexylethylene. The hydrolysis of the pendent esters moieties of these fluorinated copolymers paved the way to their polyvinylalcohol counterparts with a marked amphiphilicity. [less ▲]

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