References of "Detrembleur, Christophe"
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See detailBio-based poly(hydroxyurethane) glues for metal substrates
Panchireddy, Satyannarayana ULiege; Grignard, Bruno ULiege; Thomassin, Jean-Michel ULiege et al

in Polymer Chemistry (in press)

Bio- and CO2-based high performance thermoset poly(hydroxyurethane)s (PHUs) glues were designed from solvent- and isocyanate-free formulations based on cyclocarbonated soybean oil, diamines (aliphatic ... [more ▼]

Bio- and CO2-based high performance thermoset poly(hydroxyurethane)s (PHUs) glues were designed from solvent- and isocyanate-free formulations based on cyclocarbonated soybean oil, diamines (aliphatic, cycloaliphatic or aromatic) and functional silica or ZnO fillers. Shear strength values and cohesive or adhesive failure of glues was correlated with the crosslinking, mechanical and thermal properties of the nanocomposite PHU thermosets. The addition of SiO2 or ZnO fillers bearing cyclic carbonate groups at their surface enabled to strongly improve the adhesion performances of the glues up to 173% compared to the unfilled PHUs. The most performant reinforced PHU adhesives showed a shear strength up to 11.3 MPa for aluminum substrate, and 10.1 MPa for stainless steel with cohesive failure. This study highlights that bio-based nanocomposite PHU thermosets are promising sustainable alternatives to conventional glues made of toxic formulations containing [less ▲]

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See detailBoosting the catalytic performance of organic salts for the fast and selective synthesis of α-alkylidene cyclic carbonates from CO2 and propargylic alcohols
Grignard, Bruno ULiege; Ngassam Tounzoua, Charlène ULiege; Gennen, Sandro ULiege et al

in ChemCatChem (in press)

The synthesis of α-alkylidene cyclic carbonates (αCCs) by carboxylative coupling of CO2 with propargylic alcohols is receiving increasing interest but requires the use of catalysts that are most often ... [more ▼]

The synthesis of α-alkylidene cyclic carbonates (αCCs) by carboxylative coupling of CO2 with propargylic alcohols is receiving increasing interest but requires the use of catalysts that are most often added in large quantity and/or are lacking of selectivity. Herein, we describe that the fine tuning of the structure of organocatalysts of the ammonium-type enables to identify the important structural parameters that dictate their catalytic performance. Tetrabutylammonium oxalate revealed to be one of the most attractive organocatalysts with a remarkable fast, complete and selective production of αCCs at low catalyst loading (2.5 mol%) under solvent free-conditions. This study clearly opens new avenues for the facile and selective synthesis of libraries of αCCs from CO2 and propargylic alcohol by using simple organocatalysts. [less ▲]

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See detailTetrabutyl ammonium salts: cheap catalysts for the facile and selective synthesis of a-alkylidene cyclic carbonates from CO2 and alkynol
Méreau, Raphaël; Grignard, Bruno ULiege; Boyaval, Amélie ULiege et al

in ChemCatChem (in press)

n-tetrabutyl ammonium organic salts are used for the first time as catalysts for the coupling of CO2 with 2-methyl-3-butyn-2-ol to form α-methylene cyclic carbonate. The final yields could reach 98% in ... [more ▼]

n-tetrabutyl ammonium organic salts are used for the first time as catalysts for the coupling of CO2 with 2-methyl-3-butyn-2-ol to form α-methylene cyclic carbonate. The final yields could reach 98% in less than 10 hours at 353K and 3MPa under solvent free conditions. A particular synergistic effect between the cation and the anion of the organocatalyst is demonstrated through catalyst screening. Online kinetic studies by ATR-IR spectroscopy correlated to DFT calculations reveal a compelling evolution of the solvation of the catalyst during the reaction that provide an understanding of the underlying reason for the observed unique kinetics and selectivity. Such in-depth fundamental mechanistic and kinetic studies enable determining and comprehending the key parameters favouring the design of novel highly active and selective catalysts for the valorisation [less ▲]

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See detailContinuous-porous N-doped carbon network as high-performance electrode for lithium-ion batteries
Alkarmo, Walid ULiege; Ouhib, Farid ULiege; Aqil, Abdelhafid ULiege et al

in Journal of Materials Science (2018), 53(8), 6135-6146

Hierarchical porous N-doped carbon (NPC) is prepared by pyrolysis of poly(- methyl methacrylate) (PMMA) particles decorated by graphene oxide (GO) and polypyrrole (PPy) as precursors and used as anode for ... [more ▼]

Hierarchical porous N-doped carbon (NPC) is prepared by pyrolysis of poly(- methyl methacrylate) (PMMA) particles decorated by graphene oxide (GO) and polypyrrole (PPy) as precursors and used as anode for lithium-ion batteries. The composite precursors with different diameter and composition (PMMA/GO/ PPy-A and B) were conveniently prepared by dispersion polymerization of methyl methacrylate in the presence of graphene oxide as stabilizer in aqueous medium, followed by addition of pyrrole and its oxidative polymerization. After pyrolysis, the resulting NPC composites with hierarchically structured macro- and mesopores exhibit high surface area (289–398 m2/g) and different N-doping levels (7.46 and 4.22 wt% of nitrogen content). The NPC with the highest N-doping level (7.46 wt%) shows high reversible capacities of 831 mAh/g at 74.4 mA/g (C/5) after 50 cycles and excellent rate performances. [less ▲]

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See detailControlled radical (co)polymerisation of allylic and vinylic monomers originating from renewable resources
Scholten, Philip ULiege; Demarteau, Jérémy ULiege; Gennen, Sandro ULiege et al

Conference (2018, March 22)

In light of recent efforts of applying principles of green and sustainable chemistry within macromolecular engineering, a large number of novel bio-sourced monomers are available. Especially cyclic ... [more ▼]

In light of recent efforts of applying principles of green and sustainable chemistry within macromolecular engineering, a large number of novel bio-sourced monomers are available. Especially cyclic carbonates (CCs), because of their effective polyaddition with polyamines to yield polymers such as non-isocyanate poly(urethane)s, have seen rapid progress during the past decade. Yet, very few examples exist of controlled radical polymerisations (CRP) of CCs bearing a double bond, part of the reason being that (i) up to now only some sustainable synthetic routes to such molecules are known and (ii) some interesting monomers contain reactive double bonds which are challenging to control by most radical polymerisation techniques. Herein we report on how cobalt-mediated radical polymerisation (CMRP) proves a powerful method for the (co)polymerisation of such monomers. Furthermore, the unique characteristics of the resulting (co)polymers and their value for applications in composites are highlighted. [less ▲]

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See detailInvestigation of the copolymerisation behaviour of bio-sourced vinylic and allylic cyclic carbonates
Scholten, Philip ULiege; Demarteau, Jérémy ULiege; Gennen, Sandro ULiege et al

Poster (2018, March 21)

Cyclic carbonates belong to a versatile class of compounds, that are widely used for the synthesis of non-isocyanate polyurethanes and as precursors for chiral building blocks. Their incorporation as ... [more ▼]

Cyclic carbonates belong to a versatile class of compounds, that are widely used for the synthesis of non-isocyanate polyurethanes and as precursors for chiral building blocks. Their incorporation as pendant groups in polymer chains is highly attractive for post-polymerisation functionalisation. The controlled radical polymerisation (CRP) of allylic or vinylic CCs is a route for the precision design of such type of polymers. Very few reports on the controlled copolymerisation of CCs are found in the literature part of the reason being that (i) up to now only some sustainable synthetic routes to such molecules are known and (ii) some interesting monomers contain reactive double bonds which are extremely challenging to control by most radical polymerisation techniques. Herein we report the synthesis of a new class of glycerol-based allylic cyclic carbonates and additionally report on the CRP of such and other CCs using cobalt-mediated radical polymerisation (CMRP). [less ▲]

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See detailOrganometallic mediated radical polymerization of vinylidene fluoride
Banerjee, Sanjib; Ladmiral, Vincent; Debuigne, Antoine ULiege et al

in Angewante Chemie Intenational Edition (2018), 57(11), 2934-2937

An unprecedented level of control for the radical polymerization of vinylidene fluoride (VDF), yielding well-defined PVDF (up to 14,500 g/mol) with low dispersity (≤1.32), was achieved using ... [more ▼]

An unprecedented level of control for the radical polymerization of vinylidene fluoride (VDF), yielding well-defined PVDF (up to 14,500 g/mol) with low dispersity (≤1.32), was achieved using organometallic mediated radical polymerization (OMRP) with an organocobalt compound as initiator. The high chain-end fidelity was demonstrated by the synthesis of PVDF- and PVAc-containing di-and tri-block copolymers. DFT calculations rationalize the efficient reactivation of both head and tail chain end dormant species. [less ▲]

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See detailAnti-biofouling and antibacterial surfaces via a multicomponent coating deposited from an up-scalable atmospheric-pressure plasma-assisted CVD process
Moreno-Couranjou, Maryline; Mauchauffé, Rodolphe; Bonot, Sébastienv et al

in Journal of Materials Chemistry B (2018), 6(4), 614-623

Prevention of bacterial adhesion and biofilm formation on the surfaces of materials is a topic of major medical and societal importance. In this study, an up-scalable atmospheric-pressure plasma assisted ... [more ▼]

Prevention of bacterial adhesion and biofilm formation on the surfaces of materials is a topic of major medical and societal importance. In this study, an up-scalable atmospheric-pressure plasma assisted deposition method is introduced to produce a multicomponent coating towards the elaboration of antibacterial and anti-biofilm surfaces. Interestingly, from a single catechol-based monomer, high deposition rates of highly chemically reactive functional thin films bearing catechol as well as quinone groups are achieved. The catechol-bearing thin film allows the in situ silver nanoparticle formation, assessed by scanning electron microscopy and EDX, whilst the enriched-quinone thin film is exploited for immobilizing dispersine B, an enzyme. In vitro functional assays demonstrated the dual antibacterial and anti-biofouling resistance properties of the coatings due to the antibacterial effect of silver and the fouling resistance of grafted dispersine B, respectively. Surfaces coated only with silver provide an antibacterial effect but fail to inhibit bacterial attachment, highlighting the usefulness of such dual-action surfaces. The approach presented here provides a simple and effective chemical pathway to construct powerful antibacterial surfaces for various industrial applications. [less ▲]

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See detailEthylene/vinyl acetate-based macrocycles via organometallic-mediated radical polymerization and CuAAC ‘click’ reaction
Demarteau, Jérémy ULiege; De Winter, Julien; Detrembleur, Christophe ULiege et al

in Polymer Chemistry (2018), 9(3), 273-278

Recent advances in organometallic-mediated radical polymerization led to unique α,ω-difunctional poly(vinyl acetate) (PVAc) and ethylene/vinyl acetate copolymers (EVA). A copper- catalyzed Huisgen dipolar ... [more ▼]

Recent advances in organometallic-mediated radical polymerization led to unique α,ω-difunctional poly(vinyl acetate) (PVAc) and ethylene/vinyl acetate copolymers (EVA). A copper- catalyzed Huisgen dipolar cycloaddition ring-closure reaction was applied to these difunctional precursors paving the way to unprecedented PVAc and/or EVA macrocycles, and to their PVOH- and EVOH-counterparts after hydrolysis. [less ▲]

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See detailCatechol end-functionalized polylactide by organocatalyzed ring-opening polymerization
Sadaba, Naroa; Salsamendi, Maitane; Casado, Nerea et al

in Polymers (2018), 10(2), 155

There is a great interest in incorporating catechol moieties into polymers in a controlled manner due to their interesting properties, such as the promotion of adhesion, redox activity or bioactivity. One ... [more ▼]

There is a great interest in incorporating catechol moieties into polymers in a controlled manner due to their interesting properties, such as the promotion of adhesion, redox activity or bioactivity. One possibility is to incorporate the catechol as end-group in a polymer chain using a functional initiator by means of controlled polymerization strategies. Nevertheless, the instability of catechol moieties under oxygen and basic pH requires tedious protection and deprotection steps to perform the polymerization in a controlled fashion. In the present work, we explore the organocatalyzed synthesis of catechol end-functional, semi-telechelic polylactide (PLLA) using non-protected dopamine, catechol molecule containing a primary amine, as initiator. NMR and SEC-IR results showed that in the presence of a weak organic base such as triethylamine, the ring-opening polymerization (ROP) of lactide takes place in a controlled manner without need of protecting the cathechol units. To further confirm the end-group fidelity the catechol containing PLLA was characterized by Cyclic Voltammetry and MALDI-TOF confirming the absence of side reaction during the polymerization. In order to exploit the potential of catechol moieties, catechol end-group of PLLA was oxidized to quinone and further reacted with aliphatic amines. In addition, we also confirmed the ability of catechol functionalized PLLA to reduce metal ions to metal nanoparticles to obtain well distributed silver nanoparticles. It is expected that this new route of preparing catechol-PLLA polymers without protection will increase the accessibility of catechol containing biodegradable polymers by ROP. [less ▲]

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See detailBis(formylphenolato)cobalt(II)-mediated alternating radical copolymerization of tert-butyl 2-trifluoromethylacrylate with vinyl acetate
Banerjee, Sanjib; Bellan, Ekaterina V.; Gayet, Florence et al

in Polymers (2017), 9(12), 705

The organometallic-mediated radical polymerization (OMRP) of vinyl acetate (VAc) and its OMR copolymerization (OMRcoP) with tert-butyl 2-trifluoromethylacrylate (MAF-TBE) mediated by Co(SAL)2 (SAL = 2 ... [more ▼]

The organometallic-mediated radical polymerization (OMRP) of vinyl acetate (VAc) and its OMR copolymerization (OMRcoP) with tert-butyl 2-trifluoromethylacrylate (MAF-TBE) mediated by Co(SAL)2 (SAL = 2-formylphenolato or deprotonated salicylaldehyde) produced relatively well-defined PVAc and poly(VAc-alt-MAF-TBE) copolymers at moderate temperature (<40 ◦C) in bulk. The resulting alternating copolymer was characterized by 1H-, 13C- and 19F-nuclear magnetic resonance (NMR) spectroscopies, and by size exclusion chromatography. The linear first-order kinetic plot, the linear evolutions of the molar mass with total monomer conversion, and the relatively low dispersity (Đ~1.55) of the resulting copolymers suggest that this cobalt complex provides some degree of control over the copolymerization of VAc and MAF-TBE. Compared to the previously investigated cobalt complex OMRP mediators having a fully oxygen-based first coordination sphere, this study emphasizes a few peculiarities of Co(SAL)2: a lower ability to trap radical chains as compared to Co(acac)2 and the absence of catalytic chain transfer reactions, which dominates polymerizations carried in the presence of 9-oxyphenalenone cobalt derivative. [less ▲]

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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 (2017), 29(40), 1703373

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 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 detailPolyvinyl alcohol and method for producing same
Takayama, Takumi; Amano, Yusuke; Maekawa, Kazuko et al

Patent (2017)

According to the present invention a polyvinyl alcohol is produced by performing: a polymerization step wherein a polymer solution containing a polyvinyl ester is obtained by polymerizing a vinyl ester ... [more ▼]

According to the present invention a polyvinyl alcohol is produced by performing: a polymerization step wherein a polymer solution containing a polyvinyl ester is obtained by polymerizing a vinyl ester monomer by means of controlled radical polymerization in the presence of a radical initiator and an organic cobalt complex; an extraction step wherein a cobalt complex is extracted from the polymer solution by bringing the polymer solution into contact with an aqueous solution containing a water-soluble ligand; and a saponification step wherein a polyvinyl alcohol is obtained by saponifying the polyvinyl ester after the extraction step. Consequently, the present invention provides a method for producing a polyvinyl alcohol which has narrow molecular weight distribution, high number average molecular weight and good hue, while exhibiting good solubility in water. [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 (2017), 95

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 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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