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1. Vanillin-Based Epoxy Vitrimers: Looking at the Cystamine Hardener from a Different Perspective

Author

Solène Guggari, Fiona Magliozzi, Samuel Malburet, Alain Graillot, Mathias Destarac, Marc Guerre, Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), and Specific Polymers (SP)

Subjects
[CHIM.POLY]Chemical Sciences/Polymers, Renewable Energy, Sustainability and the Environment, General Chemical Engineering, Environmental Chemistry, General Chemistry
Abstract

International audience; Epoxy vitrimers encompass many advantages compared to traditional epoxy materials such as recyclability, repairability, and reprocessability. These properties are induced by the incorporation of dynamic reversible covalent bonds. Recently, the incorporation of aromatic disulfide bridges that are dynamic has expanded the development of new eco-friendly epoxy materials. Herein, we studied a bio-based aliphatic disulfide based on cystamine as a hardener with a vanillin-derived bio-sourced epoxy to prepare fully bio-based epoxy vitrimers. This article provides a comparative study between cystamine and an aromatic disulfide benchmark hardener issued from petrol resources. This work demonstrated that the presence of this aliphatic hardener has a significant influence not only on the reactivity, but most importantly on the resulting dynamic properties. An interesting yet counterintuitive accelerating effect of the dynamic exchanges was clearly demonstrated with only 2 to 20% of molar fraction of cystamine added to the aromatic disulfide formulation. A similar glass transition was obtained compared to the purely aromatic analogue, but relaxation times were decreased by an order of magnitude.

Published
2023

2. Vitrimer composites: current status and future challenges

Author

Vincent Schenk, Karine Labastie, Mathias Destarac, Philippe Olivier, Marc Guerre, Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), IRT Saint Exupéry - Institut de Recherche Technologique, Institut Clément Ader (ICA), Institut Supérieur de l'Aéronautique et de l'Espace (ISAE-SUPAERO)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-IMT École nationale supérieure des Mines d'Albi-Carmaux (IMT Mines Albi), and Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)

Subjects
[CHIM.POLY]Chemical Sciences/Polymers, Chemistry (miscellaneous), General Materials Science
Abstract

International audience; Thermosets dominate the composite industry owing to their outstanding stiffness to weight ratio and fatigue resistance. Nevertheless, the possibilities of recycling these materials are limited due to the irreversible chemical bonds created during the curing process which cause the materials to be set in their final form. The available recycling strategies generally degrade the polymer matrix either by burning off (pyrolysis) or chemically dissolving (solvolysis) the resins in order to recover the fibres. But methodologies to reprocess or fully recycle (i.e. resin + fibres) these composite materials are rare. Thus, the development of more sustainable approaches is now increasing importantly and is seen as a decisive challenge for the further development of composite materials. Vitrimer materials, which combine the mechanical resilience of thermosets with reprocessability of “glass” at high temperatures, appear as a very promising alternative towards recyclable thermoset composites. This review gathers the recent progress in the domain of vitrimer composites and points out the next future challenges to be tackled. A brief section discussing the first industrial initiatives is also presented.

Published
2022

3. Combination of Cationic and Radical RAFT Polymerizations: A Versatile Route to Well-Defined Poly(ethyl vinyl ether)

Author

Marc, Guerre, Mineto, Uchiyama, Enrique, Folgado, Mona, Semsarilar, Bruno, Améduri, Kotaro, Satoh, Masami, Kamigaito, and Vincent, Ladmiral

Abstract

Poly(vinylidene fluoride)-containing block copolymers are difficult to prepare and still very rare in spite of their potential use in high added value applications. This communication describes in detail the synthesis of unprecedented poly(ethyl vinyl ether)

Published
2022

4. Dynamic Curing Agents for Amine-Hardened Epoxy Vitrimers with Short (Re)processing Times

Author

Marc Guerre, Wim Van Paepegem, Ives De Baere, Johan M. Winne, Yann Spiesschaert, Filip Du Prez, Department of Organic and Macromolecular Chemistry, Universiteit Gent = Ghent University [Belgium] (UGENT), Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Department of Materials, Textiles and Chemical Engineering (LCT), Universiteit Gent = Ghent University (UGENT), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), and Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Polymers and Plastics, OXIRANE RINGS, curing agent, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, epoxy resin, Inorganic Chemistry, DESIGN, Materials Chemistry, vinylogous urethane, Curing (chemistry), vitrimer, RESINS, EPOXIDATION, Organic Chemistry, MECHANICAL-PROPERTIES, Epoxy, 021001 nanoscience & nanotechnology, Condensation reaction, NETWORKS, 0104 chemical sciences, Chemistry, [CHIM.POLY]Chemical Sciences/Polymers, Vitrimers, Chemical engineering, visual_art, visual_art.visual_art_medium, Amine gas treating, 0210 nano-technology
Abstract

International audience; This work presents a straightforward strategy to introduce highly dynamic and adaptable cross-links into common epoxy resin formulations. For this, an oligomeric amine-based curing agent containing vinylogous urethane (VU) bonds was developed. This novel polyfunctional amine curing agent can be used as a drop-in solution for existing epoxy resin technologies, resulting in transparent, rigid, and, at the same time, highly reprocessable catalyst-free epoxy vitrimers. The oligomeric VU-curing agents are prepolymerized via a straightforward condensation reaction between acetoacetates extended with different classical amine monomers and epoxy hardeners. It is found that vitrimer properties can be readily introduced into these epoxy formulations by converting

Published
2020

6. Fast processing of highly crosslinked, low-viscosity vitrimers

Author

Christian Michael Taplan, Marc Guerre, Johan M. Winne, and Filip Du Prez

Subjects
chemistry.chemical_classification, Work (thermodynamics), Materials science, Polymer science, Process Chemistry and Technology, Polymer, Viscoelasticity, Material flow, Vitrimers, chemistry, Mechanics of Materials, Stress relaxation, General Materials Science, Extrusion, Injection moulding, Electrical and Electronic Engineering
Abstract

Here we describe a rational approach to go beyond the current processability limits of vitrimer materials, with a demonstration of low-viscosity fast processing of highly crosslinked permanent networks. Vitrimers are a recently introduced class of polymer networks with a unique glass-like viscoelastic behavior, in which bond exchange reactions govern the macroscopic material flow. The restricted chain mobility, only enabled by chemical exchanges, typically limits the use of continuous processing techniques, such as extrusion or injection moulding. Herein, we outline a straightforward materials design approach, taking into account both the effect of minor additives on the chemistry of bond rearrangement as well as the macromolecular architecture of the vitrimeric network. These combined effects are demonstrated to work in an additive fashion, culminating in stress relaxation times below 1 s at 150 °C. The observed rapid bond exchanges in permanent networks result in an unprecedented control of the polymer material behavior, where the material flow is still dominated by chemical exchanges, but only marginally limited by the chemical exchange rate, overcoming the challenges encountered so far in continuous processing of highly crosslinked vitrimeric systems.

Published
2020

7. Vitrimers: directing chemical reactivity to control material properties

Author

Marc Guerre, Christian Michael Taplan, Johan M. Winne, Filip Du Prez, Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), Department of Organic and Macromolecular Chemistry, Universiteit Gent = Ghent University (UGENT), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), and Universiteit Gent = Ghent University [Belgium] (UGENT)

Subjects
DISULFIDE CROSS-LINKS, Nanotechnology, Context (language use), 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Lead (geology), DYNAMIC BONDS, COMPOSITES, MECHANICALLY ROBUST, EPOXY VITRIMER, POLYMER NETWORKS, chemistry.chemical_classification, CATALYST, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Circular economy, General Chemistry, Material Design, Polymer, PERFORMANCE, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Chemistry, Vitrimers, chemistry, Covalent bond, 0210 nano-technology, Material properties, COVALENT ADAPTABLE NETWORKS
Abstract

The development of more sustainable materials with a prolonged useful lifetime is a key requirement for a transition towards a more circular economy. However, polymer materials that are long-lasting and highly durable also tend to have a limited application potential for re-use. This is because such materials derive their durable properties from a high degree of chemical connectivity, resulting in rigid meshes or networks of polymer chains with a high intrinsic resistance to deformation. Once such polymers are fully synthesised, thermal (re)processing becomes hard (or impossible) to achieve without damaging the degree of chemical connectivity, and most recycling options quickly lead to a drop or even loss of material properties. In this context, both academic and industrial researchers have taken a keen interest in materials design that combines high degrees of chemical connectivity with an improved thermal (re)processability, mediated through a dynamic exchange reaction of covalent bonds. In particular vitrimer materials offer a promising concept because they completely maintain their degree of chemical connectivity at all times, yet can show a clear thermally driven plasticity and liquid behavior, enabled through rapid bond rearrangement reactions within the network. In the past decade, many suitable dynamic covalent chemistries were developed to create vitrimer materials, and are now applicable to a wide range of polymer matrices. The material properties of vitrimers, however, do not solely rely on the chemical structure of the polymer matrix, but also on the chemical reactivity of the dynamic bonds. Thus, chemical reactivity considerations become an integral part of material design, which has to take into account for example catalytic and cross-reactivity effects. This mini-review will aim to provide an overview of recent efforts aimed at understanding and controlling dynamic cross-linking reactions within vitrimers, and how directing this chemical reactivity can be used as a handle to steer material properties. Hence, it is shown how a focus on a fundamental chemical understanding can pave the way towards new sustainable materials and applications., In this minireview, we survey recent advances in the development of vitrimer materials. Focus on how to chemically control their material properties is used to highlight challenges for boosting the potential of this emerging class of polymer materials.

Published
2020

8. Grafting from Fluoropolymers Using ATRP: What is Missing?

Author

Marc Guerre, Mona Semsarilar, Vincent Ladmiral, Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées, Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Toulouse (ICT), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), and Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM)

Subjects
PVDF, Dehydrofluorination, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Grafting-from strategy, [CHIM.POLY]Chemical Sciences/Polymers, [CHIM]Chemical Sciences, 0210 nano-technology, Fluoropolymers, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; Grafting polymers from fluoropolymer backbones is very advantageous to modify the properties of these often non-functional materials. It is particularly useful in the field of ultrafiltration membranes to tune the hydrophilicity of PVDF membranes and to add other properties such as antifouling for example. One of the main techniques used to effect such grafting is ATRP. A large number of papers are published every year on this topic. However, careful examination of this body of work reveals that the evidence provided to support the covalent bonding of polymer chains on the fluoropolymers are often limited and rather unconvincing. This is of course due to the difficult detection of the rare connecting covalent bonds. Nevertheless, this detection problem is not the only issue. Grafting from fluoropolymers using ATRP relies on the homolytic cleavage of C−F bond, notorious for their high stability and BDE. Moreover, fluoropolymers based on VDF are prone to dehydrofluorination by reaction with bases and nucleophiles, which leads to the formation of unsaturations within the polymer backbone. This reaction is often completely ignored even though ATRP ligands can trigger this elimination. These two very often overlooked reactivity features seriously question the use of ATRP as an efficient grafting technique for fluoropolymers.

Published
2021

9. Azo-Derived Symmetrical Trithiocarbonate for Unprecedented RAFT Control

Author

Oleksandr Ivanchenko, Sonia Mallet-Ladeira, Stéphane Mazières, Maksym Odnoroh, Mathias Destarac, Marc Guerre, Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), Laboratoire de chimie de coordination (LCC), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE29-0014,RAFTSWITCH,Agents de Transfert RAFT Modulables pour la Polymérisation Radicalaire Contrôlée.(2016)

Subjects
Trithiocarbonate, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Radical polymerization, Leaving group, Chain transfer, General Chemistry, Raft, Methacrylate, Biochemistry, Block copolymers, Catalysis, Polymerization, Colloid and Surface Chemistry, [CHIM.POLY]Chemical Sciences/Polymers, Polymer chemistry, Copolymer, Thiol, Thermoplastic elastomer
Abstract

International audience; Bis(2-cyanopropan-2-yl)trithiocarbonate (TTC-bCP) is a new symmetrical trithiocarbonate with the best leaving group ever reported for reversible addition–fragmentation chain transfer (RAFT) polymerization. We propose an elegant route to obtain TTC-bCP starting from 2,2′-azobis(2-methylpropionitrile) (AIBN) as a donor of the 2-cyanopropan-2-yl group. TTC-bCP allowed the preparation of a high-molar-mass (Mn ≈ 135 kg mol–1) methyl methacrylate–n-butyl acrylate–methyl methacrylate triblock copolymer with unprecedented control (D̵ = 1.04) in reversible-deactivation radical polymerization. Rheology measurements of this triblock copolymer showed a typical thermoplastic elastomer behavior with a steady rubbery plateau up to 120 °C.

Published
2021

10. Polyaddition Synthesis Using Alkyne Esters for the Design of Vinylogous Urethane Vitrimers

Author

Marc Guerre, Filip Du Prez, Jens Danneels, Johan M. Winne, Guillaume Acke, Niels Van Herck, Yann Spiesschaert, Department of Organic and Macromolecular Chemistry, Universiteit Gent = Ghent University [Belgium] (UGENT), Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Universiteit Gent = Ghent University (UGENT), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), and Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT)

Subjects
chemistry.chemical_classification, Solid-state chemistry, Materials science, Polymers and Plastics, 010405 organic chemistry, POTENT, Organic Chemistry, Alkyne, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Chemistry, Vitrimers, chemistry, TRANSESTERIFICATION, Materials Chemistry, Organic chemistry, [CHIM]Chemical Sciences, COVALENT ADAPTABLE NETWORKS, POLYMER NETWORKS, TEMPERATURE, ComputingMilieux_MISCELLANEOUS
Abstract

Vitrimers are a subclass of covalent adaptable networks which introduce reshapeability and recyclability in thermoset materials while maintaining a high degree of chemical resistance and dimensional stability. Vitrimer materials based on vinylogous urethane (VU) chemistry have drawn a lot of attention in this area. Classically, these are obtained by the polycondensation polymerization of acetoacetate and amine monomers. Unfortunately, this also releases water, often leading to porosity defects in the initially obtained non-reprocessed cross-linked materials. Here, we demonstrate that alkyne esters (AE) can be used as alternative building blocks for VU vitrimers by a polyaddition polymerization with amines, leading to water-free formulations and straightforward access to defect-free cured VU vitrimer materials. The bond formation and dynamic bond exchange was also studied by small molecule reactions, further rationalized by a computational (DFT) approach. The resulting water-free VU vitrimers display similar material properties compared to vitrimers based on acetoacetates, although also some differences are seen, which can be related to a minor amide-bond forming side reaction. Furthermore, by use of this novel AE approach, polyaddition curing of VU epoxy vitrimers can easily be prepared in a one-pot three-component method, combining AE, amine, and epoxy monomers. This study shows that AE monomers can be used as an easy drop-in method to obtain processable epoxy materials with tunable viscoelastic properties, where the viscous flow behavior can in principle be fully tuned by varying the monomers' ratios and compositions.

Published
2021

11. Solution self-assembly of fluorinated polymers, an overview

Author

Vincent Ladmiral, Gérald Lopez, Mona Semsarilar, Bruno Ameduri, Marc Guerre, Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Institut de Chimie de Toulouse (ICT-FR 2599), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM), Institut Européen des membranes (IEM), Université de Montpellier (UM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Materials science, Polymers and Plastics, Organic Chemistry, chemistry.chemical_element, Bioengineering, Nanotechnology, 02 engineering and technology, Polymer, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Ferroelectricity, 0104 chemical sciences, Electronegativity, Fluorinated monomers, chemistry, Fluorine, Copolymer, Fluorinated Polymers, [CHIM]Chemical Sciences, Self-assembly, 0210 nano-technology
Abstract

Fluoropolymers constitute an attractive family of polymer materials with remarkable properties such as high resistance to chemicals, UV and heat, ferroelectricity and piezoelectricity for semi-crystalline polymers, to name a few. The incorporation of fluorinated moieties in a polymer can confer unique properties. Due to the fluorine atom's high electronegativity and the peculiar interactions of the fluorinated group, such polymers readily self-assemble in solution and often lead to original morphologies endowed with rare properties. Thanks to advances made in organic and polymer chemistry, a large variety of fluorinated monomers and polymers have been used to design fluorinated copolymer architectures. This review gives an overview of the current state of the art of the solution self-assembly of these fluorinated copolymer architectures.

Published
2021

12. Filler reinforced polydimethylsiloxane-based vitrimers

Author

Filip Du Prez, Johan M. Winne, Marc Guerre, Lucie Imbernon, and Yann Spiesschaert

Subjects
Filler (packaging), Materials science, Polymers and Plastics, Polydimethylsiloxane, Organic Chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Elastomer, Condensation reaction, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Vitrimers, Chemical engineering, Covalent bond, Materials Chemistry, Surface modification, 0210 nano-technology, Material properties
Abstract

Vitrimers are a type of covalent adaptable networks that use an associative mechanism resulting in the ability to be thermally processed without losing their network integrity, even at elevated temperatures. Here we describe the synthesis of vinylogous urethane-based thermally stable, reinforced polydimethylsiloxane vitrimers with a special emphasis on the influence of the filler's acidic or basic functionalization on relaxation times. The vitrimer design is based on a straightforward condensation reaction between amino terminated polydimethylsiloxane and a trifunctional acetoacetate. The addition of fillers improves the mechanical properties, reduces the soluble fraction, preserves processability and, depending on the amount of filler added, maintains the ability to be recycled, without loss of properties. Furthermore, the relaxation times can be slightly tuned by using acidic or basic fillers, whilst keeping the corresponding material properties. These results show that fillers can be used as both reinforcing agents and catalysts in vinylogous urethane vitrimer systems.

Published
2019

13. π-Stacking Interactions of Graphene-Coated Cobalt Magnetic Nanoparticles with Pyrene-Tagged Dendritic Poly(Vinylidene Fluoride)

Author

Vincent Collière, Anne-Marie Caminade, Enrique Folgado, Marc Guerre, Christian Bijani, Kathleen I. Moineau-Chane Ching, Bruno Ameduri, Nidhal Mimouni, Vincent Ladmiral, Armelle Ouali, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
π-stacking, magnetic nanoparticles, Dendrimers, Materials science, Stacking, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Fluorescence spectroscopy, law.invention, chemistry.chemical_compound, law, Dendrimer, Moiety, Pyrenes, Graphene, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Poly(vinylidenefluoride), [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, Pyrene, Magnetic nanoparticles, 0210 nano-technology, Cobalt
Abstract

International audience; This study investigates the non-covalent coating of cobalt magnetic nanoparticles (MNPs) involving a graphene surface with pyrene-tagged dendritic poly(vinylidene fluoride) (PVDF). Dendrimers bearing a pyrene moiety were selected to play the role of spacers between the graphene surface of the MNPs and the PVDF chains, the pyrene unit being expected to interact with the surface of the MNPs. The pyrene-tagged dendritic spacer 11 decorated with ten acetylenic units was prepared and fully characterized. Azido-functionalized PVDF chains were then grafted onto each branch of the dendrimer using Huisgen’s [3 + 2] cycloaddition reaction. Next, the association of the resulting pyrene-tagged dendritic PVDF 13 with commercially available Co/C MNPs by π -stacking interactions was studied by fluorescence spectroscopy. Evaluated were the stability of the π -stacking interactions when the temperature increased and the reversibility of the process when the temperature de- creased. Also, hybrid MNPs were prepared from pyrene-tagged dendrimers decorated either with acetylenic functions ( 11 ) or with PVDF branches ( 13 ), and they were characterized by transmission electron microscopy and comparative elemental analysis was carried out with naked MNPs.

Published
2018

14. RAFT Polymerisation of Trifluoroethylene: The importance of understanding reverse additions

Author

Rinaldo Poli, Cédric Totée, Vincent Bouad, Jean-Francois Tahon, Vincent Ladmiral, Olinda Gimello, Marc Guerre, Gilles Silly, Sophie Barrau, Bruno Ameduri, Unité Matériaux et Transformations - UMR 8207 (UMET), Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), ANR-16-CE08-0025,NanoPiC,Etude du comportement piézoélectrique multi-échelles de composites innovants micro- et nano-structurés(2016), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centrale Lille Institut (CLIL), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Polymers and Plastics, Organic Chemistry, Kinetics, Bioengineering, 02 engineering and technology, Nuclear magnetic resonance spectroscopy, Raft, Crystal structure, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, 0104 chemical sciences, chemistry.chemical_compound, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, Transfer agent, Chemical engineering, chemistry, Polymerization, 0210 nano-technology
Abstract

International audience; This article is the first report of the RAFT polymerisation of trifluoroethylene (TrFE). Trifluoroethylene is a rare but very important fluoromonomer, as it allows the preparation of materials endowed with unique electroactivity via copolymerisation with vinylidene fluoride (VDF) and other fluoromonomers. RAFT polymerisations carried out using O-ethyl-S-(1-methoxycarbonyl) ethyldithiocarbonate as a chain transfer agent and a thermal initiator were carefully examined. The polymerisation, its kinetics and the chain-end evolution were investigated by GPC, 1H{19F} and 19F{1H} NMR spectroscopy as well as MALDI-TOF mass spectrometry. Similar to the RAFT polymerisation of VDF, irreversible transfer reactions and reverse additions significantly affect the control of the polymerisation as well as the chain-end functionality. However, in contrast to VDF, unusual reverse propagation of TrFE, although limited to a few monomer units, was evidenced thanks to a combined NMR spectroscopy and DFT calculation approach. RAFT polymerisation afforded relatively well-defined PTrFE with a crystalline structure consistent with previous reports.

Published
2021

15. Surface Modification of (Non)‐Fluorinated Vitrimers through Dynamic Transamination

Author

Christian Michael Taplan, Marc Guerre, Filip Du Prez, Christopher N. Bowman, Department of Organic and Macromolecular Chemistry, Universiteit Gent = Ghent University [Belgium] (UGENT), Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Department of Chemical and Biological Engineering [Boulder], University of Colorado [Boulder], Universiteit Gent = Ghent University (UGENT), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), and Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT)

Subjects
Materials science, Polymers and Plastics, Macromolecular Substances, Polymers, Surface Properties, 02 engineering and technology, engineering.material, 010402 general chemistry, 01 natural sciences, Contact angle, chemistry.chemical_compound, Coating, Materials Chemistry, vinylogous urethane, Lithography, nano-imprint lithography, chemistry.chemical_classification, Polydimethylsiloxane, Organic Chemistry, Dynamic covalent chemistry, Polymer, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Vitrimers, Chemical engineering, vitrimers, engineering, Surface modification, Printing, covalent adaptable networks, 0210 nano-technology
Abstract

International audience; Surface modifications are typically permanent in shape and chemistry. Herein, vinylogous urethane (VU) chemistry is presented as an easily accessible and versatile platform for rapid, facile, and reworkable surface modification. It is demonstrated that both physical and chemical post-modification of permanent, yet dynamic elastic polymer networks are achieved. Surface patterns with high regularity are created, both via a straightforward replication process using a polydimethylsiloxane stamp (resolution ca. 10-100 µm) as well as using thermally activated nano-imprint lithography (NIL) to form hole, pillar, or line patterns (ca. 300 nm) in elastic VU-based vitrimers. The tunable, rapid exchange allows patterning at 130 °C in less than 15 min, resulting in an increased water contact angle and surface-structure induced light reflection. Moreover, it is also demonstrated that the use of a single dynamic covalent chemistry makes it possible to strongly adhere to fluorinated and non-fluorinated materials based on incompatible matrices, causing cohesive failure in a peel test. In a topography scan, the visibly transparent interface is shown to possess a continuous phase without a gap, while maintaining distinctively separated (non)-fluorinated domains. Finally, this approach allowed for a straightforward coating of a non-fluorinated material with a fluorinated monomer to minimize the overall fluorinated content.

Published
2021

16. NMR investigations of polytrifluoroethylene (PTrFE) synthesized by RAFT

Author

Rinaldo Poli, Cédric Totée, Vincent Bouad, Marc Guerre, Vincent Ladmiral, Sami Zeliouche, Bruno Ameduri, Gilles Silly, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), Laboratoire de chimie de coordination (LCC), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), ANR-16-CE08-0025,NanoPiC,Etude du comportement piézoélectrique multi-échelles de composites innovants micro- et nano-structurés(2016), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Polymers and Plastics, Chemical shift, Organic Chemistry, Bioengineering, 02 engineering and technology, Raft, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Ferroelectricity, 0104 chemical sciences, chemistry.chemical_compound, Monomer, Chemical engineering, chemistry, Polymerization, [CHIM]Chemical Sciences, 0210 nano-technology, Fluoride
Abstract

International audience; Trifluoroethylene (TrFE) is a relatively rare fluorinated monomer mainly used in copolymerisation with vinylidene fluoride (VDF) to prepare ferroelectric materials. While VDF homopolymerisation has been relatively well studied, that of TrFE is still poorly understood and the reversible deactivation radical polymerisation of this monomer has never been studied in depth. To better understand the RAFT polymerisation of TrFE, accurate assignments of PTrFE synthesized by RAFT polymerisation are necessary. Thus, this article reports detailed 19F, 1H and 13C 1D and 2D experiments carried out to determine and assign the different NMR chemical shifts and splitting patterns of the α- and ω-chain ends of PTrFE synthesized by RAFT polymerisation.

Published
2021

17. Covalent Adaptable Networks Using β-Amino Esters as Thermally Reversible Building Blocks

Author

Christian Michael Taplan, Filip Du Prez, Marc Guerre, Department of Organic and Macromolecular Chemistry, Universiteit Gent = Ghent University [Belgium] (UGENT), Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Universiteit Gent = Ghent University (UGENT), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), and Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT)

Subjects
010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, chemistry.chemical_compound, Colloid and Surface Chemistry, TRANSESTERIFICATION, Polymer chemistry, COMPOSITES, Moiety, EXCHANGE, POLYMER NETWORKS, TEMPERATURE, VITRIMERS, CATALYST, Acrylate, Amino esters, [CHIM.ORGA]Chemical Sciences/Organic chemistry, TRANSALKYLATION, General Chemistry, Transesterification, 0104 chemical sciences, Chemistry, Vitrimers, chemistry, Covalent bond, AZA-MICHAEL ADDITION, Glass transition
Abstract

In this study, beta-amino esters, prepared by the aza-Michael addition of an amine to an acrylate moiety, are investigated as building blocks for the formation of dynamic covalent networks. While such amino esters are usually considered as thermally nondynamic adducts, the kinetic model studies presented here show that dynamic covalent exchange occurs via both dynamic aza-Michael reaction and catalyst-free transesterification. This knowledge is transferred to create beta-amino ester-based covalent adaptable networks (CANs) with coexisting dissociative and associative covalent dynamic exchange reactions. The ease, robustness, and versatility of this chemistry are demonstrated by using a variety of readily available multifunctional acrylates and amines. The presented CANs are reprocessed via either a dynamic aza-Michael reaction or a catalyst-free transesterification in the presence of hydroxyl moieties. This results in reprocessable, densely cross-linked materials with a glass transition temperature (T-g) ranging from -60 to 90 degrees C. Moreover, even for the low T-g materials, a high creep resistance was demonstrated at elevated temperatures up to 80 degrees C. When additional beta-hydroxyl group-containing building blocks are applied during the network design, an enhanced neighboring group participation effect allows reprocessing of materials up to 10 times at 150 degrees C within 30 min while maintaining their material properties.

Published
2021

18. Internal catalysis on the opposite side of the fence in non-isocyanate polyurethane covalent adaptable networks

Author

Aitor Hernández, Hannes A. Houck, Fermin Elizalde, Marc Guerre, Haritz Sardon, Filip E. Du Prez, Department of Organic and Macromolecular Chemistry, Universiteit Gent = Ghent University (UGENT), Departamento de Ciencia y Tecnologıa de Polımeros e Instituto de Materiales Polimericos (POLYMAT), Universidad del Pais Vasco / Euskal Herriko Unibertsitatea [Espagne] (UPV/EHU), Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), and Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT)

Subjects
ORGANOCATALYSIS, Polymers and Plastics, Organic Chemistry, RUBBER, General Physics and Astronomy, [CHIM.CATA]Chemical Sciences/Catalysis, RECOVERY, Non-isocyanate polyurethane, Polyhydroxyurethane, Chemistry, [CHIM.POLY]Chemical Sciences/Polymers, Materials Chemistry, TRANSCARBAMOYLATION, CO2, Internal catalysis, EXCHANGE, POLYMER NETWORKS, Covalent adaptable network, CARBONATES
Abstract

International audience; Within the context of covalent adaptable networks (CANs), we developed in this study a novel methodology to provide non-isocyanate polyurethane-based CANs with embedded tertiary amines that serve as internal catalytic moieties for the dynamic bond exchange processes. For the CAN design, we made use of multifunctional N-substituted 8-membered cyclic carbonates that are ring-opened by macromolecular amines. Several model reactions were conducted to investigate transcarbamoylation bond exchange reactions at elevated temperatures and assess the influence of catalytic moieties within the urethane structure. This led us to design a non-isocyanate polyurethane CAN wherein the position of the internal catalyst was changed with respect to previous reported polyhydroxyurethane CANs, while maintaining close proximity to the dynamic carbamate linkages. It is shown that this positioning change of the tertiary amines still resulted in an internal catalytic effect on the dynamic exchange reactions, hence providing a better understanding of the role of tertiary amines as internal catalysts during the reprocessing of polyurethane networks. Moreover, the model experiments and thermomechanical investigations of the (re)processed networks allowed to identify the occurrence of competing reactions, involving a dissociative mechanism giving rise to urea formation, which significantly impacts the materials’ reprocessability and properties.

Published
2022

19. An Agent-Based Data Acquisition Pipeline for Image Data

Author

Benjamin Acar, Martin Berger, Marc Guerreiro Augusto, Tobias Kuster, Fikret Sivrikaya, and Sahin Albayrak

Subjects
Data pipelines, agents, data processing, streaming, autonomous driving, Electrical engineering. Electronics. Nuclear engineering, TK1-9971
Abstract

The efficient processing of information plays a critical role in data-driven domains. Data acquisition pipelines, which act as the interface between data collection and subsequent processing, are central to this. Traditional software engineering methods form the foundation for the development of robust data acquisition pipelines, but agent-based systems hold great potential for realizing such pipelines, and this study presents an innovative architecture that uses agent-based components. This modular approach makes it possible to use specialized agents for individual tasks and to increase the effectiveness of the pipelines. The applicability and effectiveness of this architecture are demonstrated using a system for autonomous driving that collects and processes data from edge computers along roads. Our results are on GitHub (https://github.com/BenjaminAcar/Agent-based-Data-Acquisition-Pipeline).

Published
2024
Full Text
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20. Driving into the future: a cross-cutting analysis of distributed artificial intelligence, CCAM and the platform economy

Author

Marc Guerreiro Augusto, Benjamin Acar, Andrea Carolina Soto, Fikret Sivrikaya, and Sahin Albayrak

Subjects
Autonomous Mobility, Cooperative Connected and Automated Mobility, Distributed Artificial Intelligence, Intelligent Infrastructure, Platform Development, Platform Economy, Electronic computers. Computer science, QA75.5-76.95, Computer engineering. Computer hardware, TK7885-7895
Abstract

Abstract The future of driving is autonomous. It requires a comprehensive stack of embedded software components, enabled by open-source and proprietary platforms at different abstraction layers, and then operating within a larger ecosystem. Autonomous driving demands connectivity, cooperation and automation to form the cornerstone of autonomous mobility solutions. Platform economy principles have revolutionized the way we produce, deliver and consume products and services worldwide. More and more businesses in the field of mobility and transport appear to implement transaction, innovation, and integration platforms as core enablers for Mobility-as-a-Service and transport applications. Artificial intelligence approaches, especially those dealing with distributed systems, enable new mobility solutions, such as autonomous driving. This paper contributes to understanding the intertwining role between distributed artificial intelligence, autonomous mobility and the resulting platform ecosystem. A systematic literature review is applied, in order to identify the intersection between those aspects. Furthermore, the research project BeIntelli is considered as a hands-on application of our findings. Taking into account our analysis and the aforementioned research project, we pose a blueprint architecture for autonomous mobility. This architecture is the subject of further research. Our conclusions facilitate the development and implementation of future urban transportation systems and resulting mobility ecosystems in practice.

Published
2024
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21. OPACA: Toward an Open, Language- and Platform-Independent API for Containerized Agents

Author

Benjamin Acar, Tobias Kuster, Oskar F. Kupke, Robert K. Strehlow, Marc Guerreiro Augusto, Fikret Sivrikaya, and Sahin Albayrak

Subjects
Multi-agent systems, microservices, Kubernetes, Docker, API, Electrical engineering. Electronics. Nuclear engineering, TK1-9971
Abstract

While multi-agent frameworks can provide many advanced features, they often suffer from not being able to seamlessly interact with the outside world, e.g., with web-services or other multi-agent frameworks. This may be one factor that hinders a broader application of multi-agent systems in production systems. A possible solution to this problem is the combination of multi-agent systems with the concepts of micro-services and containerization, providing language-agnostic open interfaces, as well as encapsulation and modularity. In this paper, we propose an API and reference implementation that can be employed by multi-agent systems based on different languages and frameworks. Each agent component is encapsulated in a container and is accessed through its parent runtime platform, which takes care of aspects such as authentication, input validation, monitoring and other infrastructure tasks. Multiple runtime platforms can then be connected to form systems of distributed, heterogeneous multi-agent societies.

Published
2024
Full Text
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22. 'One-pot' aminolysis/thia-Michael addition preparation of well-defined amphiphilic PVDF- b -PEG- b -PVDF triblock copolymers: self-assembly behaviour in mixed solvents

Author

Vincent Ladmiral, Anthony Ferri, Marc Guerre, Mona Semsarilar, Enrique Folgado, Ahmed Addad, Antonio Da Costa, Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), UCCS Équipe Couches Minces & Nanomatériaux, Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Unité Matériaux et Transformations - UMR 8207 (UMET), Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Institut Européen des membranes (IEM), ANR-16-CE08-0025,NanoPiC,Etude du comportement piézoélectrique multi-échelles de composites innovants micro- et nano-structurés(2016), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Unité de Catalyse et de Chimie du Solide - Site Artois (UCCS Artois), Université d'Artois (UA)-Université de Lille, Sciences et Technologies-Ecole Centrale de Lille-Ecole Nationale Supérieure de Chimie de Lille (ENSCL)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Ecole Nationale Supérieure de Chimie de Lille (ENSCL)-Institut National de la Recherche Agronomique (INRA), Université de Montpellier (UM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille-Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centrale Lille Institut (CLIL), and Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)

Subjects
Materials science, Polymers and Plastics, Organic Chemistry, Bioengineering, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Polyvinylidene fluoride, Micelle, 0104 chemical sciences, Solvent, chemistry.chemical_compound, Aminolysis, chemistry, Amphiphile, Polymer chemistry, Copolymer, [CHIM]Chemical Sciences, Self-assembly, 0210 nano-technology, Ethylene glycol, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; Polyvinylidene fluoride-(PVDF) containing block copolymers are scarce and difficult to prepare. Amphiphilic block copolymers containing PVDF have been rarely reported. In consequence, few studies of the self-assembly of PVDF-based block copolymers exist. Here a new synthetic route to prepare poly(vinylidene fluoride)-block-poly(ethylene glycol)-block-poly(vinylidene fluoride) (PVDF-b-PEG-b-PVDF) ABA triblock copolymer is presented. The synthesis relies on the efficient coupling of a PVDF prepared by RAFT and a PEG diacrylate in one pot via aminolysis of the xanthate moiety and subsequent thia-Michael addition. The novel amphiphilic triblock copolymer was fully characterized by 1 H and 19 F NMR spectroscopies, GPC, TGA, DSC and XRD; and its self-assembly in water and ethanol was studied. Micellization (addition of a selective solvent for PVDF to a solution of the triblock) and nanoprecipitation (addition of a solution of the triblock into a non solvent of PVDF) protocols led to the formation of micelles and vesicles. Surprisingly, under nanoprecipitation conditions (in THF/ ethanol), well-defined crystalline micrometric structures were obtained.

Published
2020

23. Influence of the polymer matrix on the viscoelastic behaviour of vitrimers

Author

Marc Guerre, Filip Du Prez, Johan M. Winne, Yann Spiesschaert, Lucas Stricker, Christian Michael Taplan, Department of Organic and Macromolecular Chemistry, Universiteit Gent = Ghent University (UGENT), Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), Universiteit Gent = Ghent University [Belgium] (UGENT), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)

Subjects
chemistry.chemical_classification, Work (thermodynamics), Materials science, Polymers and Plastics, Organic Chemistry, Thermodynamics, Bioengineering, 02 engineering and technology, Polymer, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Viscoelasticity, 0104 chemical sciences, Matrix (chemical analysis), [PHYS.MECA.MEMA]Physics [physics]/Mechanics [physics]/Mechanics of materials [physics.class-ph], [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Vitrimers, Covalent bond, Relaxation (physics), Solvent effects, 0210 nano-technology
Abstract

International audience; Vitrimer materials are a rapidly growing field of research, in which still many fundamental aspects of material design remain to be explored. In this study, we report a systematic study about the effect of the choice of the matrix on a dynamic covalent bond exchange reaction in a polymer network. In some way, this investigation follows the logic of a ‘solvent effect’ study that is typical for the development of an organic reaction or synthetic method in solution. Thus, this work constitutes a study of matrix effects on the viscoelastic properties of vitrimers, in particular with regard to their stress-relaxation behaviour. For that purpose, the dynamic transamination within vinylogous urethanes (VU) vitrimers, derived from a wide range of different commercially available diols, was chosen as vitrimer chemistry reaction platform. Additionally, the influence of the molecular weight, and thus the cross-link density, was also investigated using two oligomeric diols of different molecular weights. It was found that changing the molecular weight resulted in vitrimers with significantly different activation energies (from 68 to 149 kJ mol−1) and relaxation times (from 7 to 230 min at 140 °C). These remarkable results suggest that both the molecular weight and the nature of the polymer matrix have a large influence on the resulting viscoelastic properties. However, no straightforward prediction of relaxation times or activation energies is possible at this stage, and it becomes clear that many more structure–reactivity studies will be required to arrive at a more general understanding of the factors that underly vitrimer properties

Published
2020

24. Covalent Adaptable Networks with Tunable Exchange Rates Based on Reversible Thiol-yne Cross-Linking

Author

Diederick Maes, Filip Du Prez, Niels Van Herck, Kamil Unal, Marc Guerre, Johan M. Winne, Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), Polymer Research Group, State Univ Ghent, Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Thioacetal, Alkyne, Dynamic covalent chemistry, General Chemistry, Polymer, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Small molecule, Catalysis, 0104 chemical sciences, Covalent bond, Michael reaction, Click chemistry, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

The design of covalent adaptable networks (CANs) relies on the ability to trigger the rearrangement of bonds within a polymer network. Simple activated alkynes are now used as versatile reversible cross-linkers for thiols. The click-like thiol-yne cross-linking reaction readily enables network synthesis from polythiols through a double Michael addition with a reversible and tunable second addition step. The resulting thioacetal cross-linking moieties are robust but dynamic linkages. A series of different activated alkynes have been synthesized and systematically probed for their ability to produce dynamic thioacetal linkages, both in kinetic studies of small molecule models, as well as in stress relaxation and creep measurements on thiol-yne-based CANs. The results are further rationalized by DFT calculations, showing that the bond exchange rates can be significantly influenced by the choice of the activated alkyne cross-linker.

Published
2019

25. Syntheses of 2-(trifluoromethyl)acrylate-containing block copolymers via RAFT polymerization using a universal chain transfer agent

Author

Sanjib Banerjee, Marc Guerre, Vincent Ladmiral, Bruno Ameduri, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Acrylate, Polymers and Plastics, Organic Chemistry, Dispersity, Bioengineering, Chain transfer, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, 0104 chemical sciences, Styrene, chemistry.chemical_compound, chemistry, Polymer chemistry, Copolymer, Vinyl acetate, [CHIM]Chemical Sciences, Reversible addition−fragmentation chain-transfer polymerization, Methyl methacrylate, 0210 nano-technology
Abstract

International audience; This article describes the synthesis and characterization of a series of well-defined block copolymers (BCPs) comprising a poly(vinyl acetate-alt-tert-butyl-2-trifluoromethacrylate) (poly(VAc-alt-MAF-TBE)) alternating copolymer segment and a homopolymer segment (PVAc, polystyrene, poly(meth)acrylate, polyacrylamide, or poly(N-vinylpyrrolidone)) using RAFT polymerization under mild conditions (at 40 °C). The abilities of four chain transfer agents (CTAs) to copolymerize VAc and MAF-TBE were compared. Recently reported as a universal RAFT CTA, cyanomethyl 3,5-dimethyl-1H-pyrazole-1-carbodithioate (CDPCD) afforded better-defined BCPs compared to O-ethyl-S-(1-methoxycarbonyl)ethyldithiocarbonate (CTA-XA), 2-cyano-2-propyl benzodithioate (CPDB), and 4-cyano-4-(2-phenylethanesulfanylthiocarbonyl)sulfanyl pentanoic acid (PETTC). While the chain extension of poly(VAc-alt-MAF-TBE)-DPCD with vinyl acetate (VAc), styrene (St), n-butyl acrylate (nBA), and dimethyl acrylamide (DMA) led to well-defined poly(VAc-alt-MAF-TBE)-b-poly(M) BCPs with acceptable dispersity values (Đ ≤ 1.36), high Đ values were observed when methyl methacrylate (MMA) and N-vinylpyrrolidone (NVP) were used to form the second block. An attempt to synthesize poly(M)-b-poly(VAc-alt-MAF-TBE) block copolymers using poly(M)-DPCD as the macroCTA led to copolymers with high Đ values (1.53–2.0).Graphical abstract: Syntheses of 2-(trifluoromethyl)acrylate-containing block copolymers via RAFT polymerization using a universal chain transfer agent

Published
2018

26. Photocrosslinked PVDF-based star polymer coatings: an all-in-one alternative to PVDF/PMMA blends for outdoor applications

Author

Gérald Lopez, Jean-Pierre Habas, Bruno Ameduri, Marc Guerre, Vincent Ladmiral, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Polymers and Plastics, potocrosslinking, Bioengineering, 02 engineering and technology, tetraxanthate, engineering.material, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Biochemistry, Contact angle, Coating, Polymer chemistry, Composite material, PVDF, Organic Chemistry, 4-arm star, Adhesion, 021001 nanoscience & nanotechnology, Surface energy, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Star polymer, surface energy, engineering, blends, 0210 nano-technology
Abstract

International audience; A 4-arm star PVDF was synthesized as an appealing alternative to PVDF/PMMA blends since it provides crosslinked PVDF transparentcoatings via photocrosslinking. The process is very fast and versatile, the resulting coating displays very good adhesion propertiesto a metal surface, and the surface energy and the water contact angle are easily tunable.

Published
2017

27. Polymerization-induced self-assembly of PVAc-b-PVDF block copolymers via RAFT dispersion polymerization of vinylidene fluoride in dimethyl carbonate

Author

Bruno Ameduri, Franck Godiard, Vincent Ladmiral, Marc Guerre, Mona Semsarilar, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Université de Montpellier (UM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Polymers and Plastics, Bioengineering, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biochemistry, law.invention, chemistry.chemical_compound, law, Polymer chemistry, Copolymer, Reversible addition−fragmentation chain-transfer polymerization, Crystallization, Fluoropolymers, Dispersion polymerization, RAFT polymerization, Organic Chemistry, PISA, Chain transfer, self-assembly, Raft, 021001 nanoscience & nanotechnology, Block copolymers, PVAc-b-PVDF, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, Dimethyl carbonate, 0210 nano-technology
Abstract

International audience; Polymerization-induced self-assembly of PVAc-b-PVDF block copolymers (BCPs) in dimethyl carbonate (DMC) was performed and studied using vinylidene fluoride (VDF) RAFT dispersion polymerization protocols in DMC in the presence of PVAc macromolecular chain transfer agents (macro-CTAs). The polymerizations were conducted at 73 °C in DMC using three PVAc macro-CTAs of different molar masses and targeting various DPPVDF. The relatively high frequency of head-to-head (HH) additions in VAc polymerization and the much lower reactivity of the resulting PVAc chains terminated with a–CH(OAc)–CH2–SC(S) OCH2CH3group (PVAcT–XA, where XA stands for the xanthate end-group) compared to their regularly terminated analogs (PVAcH–XA) leads to an accumulation of PVAcT–XA chains during polymerization. These PVAcT–XA reactivate slower than PVAcH–XA in the presence of PVDF• radicals. In addition, RAFT polymerization of VDF is prone to the same chain defect problem and to non-negligible transfer to DMC. In consequence, RAFT dispersion polymerization of VDF in the presence of PVAc macro-CTAs afforded PVAc-b-PVDF BCPs (contaminated with starting unreacted PVAc and PVDF homopolymers formed viatransfer to DMC). These phenomena were studied using 1H and 19F NMR spectroscopy and size exclusion chromatography. Nevertheless, the VDF RAFT dispersion polymerization in DMC experiments resulted in self-assembled BCP morphologies in the form of crystalline (1–5μm) ovoidal flakes.These flakes stack on top of each other and form star-like structures. The structures are thought to formby epitaxial growth of the PVDF crystals and interparticle interpenetration crystallization. Although they are formed under polymerization-induced self-assembly conditions, the morphologies of these BCP structures are governed by the crystallization of PVDF.

Published
2017

28. Self-assembly of poly(vinylidene fluoride)-block-poly(2-(dimethylamino)ethylmethacrylate) block copolymers prepared by CuAAC click coupling

Author

Vincent Ladmiral, Cédric Totée, Marc Guerre, Mona Semsarilar, Bruno Ameduri, Gilles Silly, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut Européen des membranes (IEM), and Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)

Subjects
Materials science, Polymers and Plastics, fluoropolymer, micelles, click coupling, Bioengineering, ATRP, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biochemistry, Micelle, chemistry.chemical_compound, poly(vinylidene fluoride), Polymer chemistry, Copolymer, Reversible addition−fragmentation chain-transfer polymerization, reversible deactivation radical polymerization, Reversible-deactivation radical polymerization, RAFT polymerization, Organic Chemistry, Raft, 021001 nanoscience & nanotechnology, 0104 chemical sciences, block copolymers, [CHIM.POLY]Chemical Sciences/Polymers, Polymerization, chemistry, Fluoropolymer, Self-assembly, 0210 nano-technology, RAFT
Abstract

International audience; Poly(vinylidene fluoride) (PVDF) is a very important fluoropolymer which possesses remarkable physicochemicalproperties such as high thermal and chemical resistances as well as ferroelectricity, for example.To date, only iodine transfer polymerization and RAFT polymerization have enabled the preparation ofwell-defined PVDF and of some PVDF-based block copolymers (BCPs). However, these reversible deactivationradical polymerization techniques suffer from undesired reactions which impair the synthesis ofa wide range of PVDF-containing BCPs. Here, unprecedented poly(vinylidene fluoride)-block-poly(2-(dimethylamino)ethylmethacrylate)(PVDF-b-PDMAEMA) BCPs were prepared by CuAAC click coupling ofazide-functionalized PVDF synthesized by RAFT polymerization and alkyne-functionalized PDMAEMAsynthesized by ATRP. This strategy was quite efficient and afforded three relatively well-defined BCPs(PVDF40-b-PDMAEMA23, PVDF40-b-PDMAEMA69, PVDF40-b-PDMAEMA162, Đ < 1.55). These amphiphilicBCPs were self-assembled in water at pH 2, 8 (native pH) and 10. The morphologies obtained were mainlypolydisperse (20–500 nm), roughly spherical aggregates. However, at pH 8, PVDF40-b-PDMAEMA69 alsoformed micrometer-long rigid cylindrical micelles. These morphologies are likely the first examples ofPVDF-containing BCP nanostructures produced by crystallization-driven self-assembly

Published
2017

29. Limits of Vinylidene Fluoride RAFT Polymerization

Author

Vincent Ladmiral, Rinaldo Poli, S. M. Wahidur Rahaman, Marc Guerre, Bruno Ameduri, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), ANR-14-CE07-0012,FLUPOL,Meilleurs polymères fluorés par la polymérisation radicalaire par voie organométallique(2014), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Kinetic chain length, Polymers and Plastics, Bulk polymerization, Reversible deactivation radical polymerization, DFT calculations, 010402 general chemistry, 01 natural sciences, Vinylidene fluoride, Inorganic Chemistry, Chain-growth polymerization, Radical polymerization, Polymer chemistry, Activation energy, Materials Chemistry, Reversible addition−fragmentation chain-transfer polymerization, Reversed addition, Xanthate, 010405 organic chemistry, Chemistry, Organic Chemistry, Chain transfer, NMR, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Polymerization, Living polymerization, Mechanism, Ionic polymerization, RAFT
Abstract

International audience; The investigations reported in this article probe the behavior of the RAFT polymerization of vinylidene fluoride (VDF) when degrees of polymerization higher than 50 are targeted: they demonstrate that higher molar mass PVDF (11 000 g mol–1) can indeed be prepared by RAFT polymerization, but only at rather low monomer conversions (

Published
2016

30. Kufast: A tool for multi-tenancy in autonomous driving testbeds

Author

Benjamin Acar and Marc Guerreiro Augusto

Subjects
Multi tenancy, Autonomous driving, Third party deployments, Computer software, QA76.75-76.765
Abstract

For the development and testing of autonomous driving technologies, there is a need for a robust and reliable testbed infrastructure that can support the deployment and testing of multiple applications from different tenants’s in parallel. We propose a multi-tenancy approach for autonomous driving testbeds to address this issue. In our approach, multiple users are able to deploy and test their applications on a shared infrastructure without interfering with each other. We have developed a tool called Kufast for the automation of the deployment process and the isolation of each tenants resources. This tool allows users to deploy their applications quickly and easily without advanced technical skills, and provides a user-friendly Command Line Interface.

Published
2023
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31. Fluorinated vitrimer elastomers with a dual temperature response

Author

Marc Guerre, Christian Michael Taplan, Johan M. Winne, Filip Du Prez, Renaud Nicolaÿ, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Laboratoire Matière Molle et Chimie (MMC), Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Polymer Research Group, and State Univ Ghent

Subjects
FABRICATION, 02 engineering and technology, Electrolyte, Activation energy, 010402 general chemistry, Elastomer, 01 natural sciences, Biochemistry, Catalysis, OLEFIN METATHESIS, Colloid and Surface Chemistry, Rheology, GLYCOL), [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, [PHYS]Physics [physics], Chemistry, ELECTROLYTES, Drop (liquid), POLY(ETHYLENE, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, VINYLOGOUS URETHANE VITRIMERS, NETWORKS, BONDS, Vitrimers, Chemical bond, Chemical physics, CROSS-LINKED POLYMERS, 0210 nano-technology, PERFLUOROPOLYETHER, PHOTOPOLYMERIZATION
Abstract

Vitrimers are an emerging new class of permanently cross-linked polymeric materials that show a liquid behavior upon heating wherein the macroscopic deformation is controlled by the rate of internal chemical bond exchange reactions. Thus, quite uniquely among polymeric materials, flow rates and material viscosities can be enhanced or controlled by the addition of catalysts and additives. We now report a catalyst-free vitrimer system, prepared from mixing two simple components, wherein two competing bond exchange mechanisms coexist, each showing a strikingly different temperature dependence, related to the large difference in activation energy for the different exchange pathways (60 vs 130-170 kJ/mol). The low barrier process is predominant at lower temperatures, but is outcompeted by the high barrier process that becomes dominant at higher temperatures because of its much more pronounced temperature dependence. The result is an interesting and highly unusual dual viscosity profile for this new class of vitrimer materials: a very gradual decrease in viscosity at lower temperatures, intercepted by a much sharper drop in viscosity at higher temperatures. The highly counterintuitive effect where a higher barrier pathway is dominant over a much lower barrier process can be rationalized by the exchange mechanisms that involve different reactive species, but lead to the overall same exchange. We observed this unusual but highly promising behavior first for fluorinated vitrimer elastomers, aimed at high performance materials, but the effect was also shown to hold in related nonfluorinated elastomers. A new way to control and design the rheological behavior of vitrimers toward finely tuned and precisely controlled processing applications has thus been provided.

Published
2018

32. Thermal and photo-RAFT polymerization of 2,2,2-trifluoroethyl α-fluoroacrylate

Author

Bruno Ameduri, Marc Guerre, Qizhi Yang, Vincent Ladmiral, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), European Project: 647857,H2020,ERC-2014-CoG,SENSOILS(2015), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Molar mass, Polymers and Plastics, Chemistry, Organic Chemistry, Bioengineering, Chain transfer, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, Polymerization, Thermal, Polymer chemistry, Propionate, Reversible addition−fragmentation chain-transfer polymerization, 0210 nano-technology
Abstract

International audience; The RAFT polymerization of 2,2,2-trifluoroethyl α-fluoroacrylate (FATRIFE) was investigated under thermal conditions and light irradiation. The performances of 4 different chain transfer agents (3,5-dimethyl-1H-pyrazole-1-carbodithioate (CTA 1), 4-cyano-4-(2-phenylethanesulfanylthiocarbonyl)sulfanylpentanoic acid (CTA 2), dibenzyl trithiocarbonate (CTA 3), and Ethyl 2-(phenylcarbonothioylthio) propionate (CTA 4)) were compared under thermal conditions. CTA 2 afforded relatively good control of the polymerization with relatively low dispersities (apparent molar mass M n,SEC ~ 37.8 kg/mol vs. PMMA, Đ < 1.10). Pseudo-first-order polymerization kinetics and a linear increase of the molar masses versus monomer conversions were observed. The RAFT polymerization of FATRIFE was further explored under photoirradiation using CTA 2 as chain transfer agent and white LED lamps (14 W × 2) irradiation. In the absence of exogenous radical sources or catalysts, controlled polymerization was observed at room temperature. Linear increase of molar masses (up to 25.3 kg/mol) with monomer conversions and low dispersities (Đ < 1.10) were successfully obtained. Temporal control of the polymerization was also observed using light ON/OFF experiments. Poly(FATRIFE) based macroCTA synthesized by photoRAFT was also extended with 1,1,1,3,3,3-hexafluoropropan-2-yl 2-fluoroacrylate and tert-butyl-2-trifluoromethacrylate/FATRIFE.

Published
2018
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33. Deeper Insight into the MADIX Polymerization of Vinylidene Fluoride

Author

Vincent Ladmiral, Olinda Gimello, Benjamin Campagne, Marc Guerre, Bruno Ameduri, Karine Parra, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)

Subjects
chemistry.chemical_classification, Materials science, Polymers and Plastics, Organic Chemistry, Radical polymerization, technology, industry, and agriculture, Solution polymerization, macromolecular substances, Fluorine-19 NMR, Polymer, Raft, Inorganic Chemistry, Solvent, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, Polymerization, Polymer chemistry, Materials Chemistry, Fluoride, ComputingMilieux_MISCELLANEOUS
Abstract

Controlled radical polymerization protocols for vinylidene fluoride (VDF) are still very elusive. MADIX polymerization of VDF has very rarely been reported. The synthesis of PVDF using MADIX solution polymerization was thus investigated in detail. More efficient protocols for solution polymerization were developed and afforded relatively well-defined PVDF. Careful polymer chain-end monitoring using MALDI-TOF as well as 1H, 19F, and HETCOR 1H–19F NMR revealed that VDF reverse additions and transfer to solvent reactions severely affect the control of the polymerization. Indeed, these unwanted reactions are responsible for a non-negligible loss of CTA and for the accumulation of nonreactive polymer chains in the reaction medium. MADIX polymerization lead to the synthesis of PVDF with high chain-end functionality. However, these PVDF chains cannot reinitiate the polymerization of VDF. This work is the first comprehensive study of the MADIX solution polymerization of VDF.

Published
2015

34. An amphiphilic poly(vinylidenefluoride)-bpoly(vinyl alcohol) block copolymer: synthesis and self-assembly in water

Author

Vincent Ladmiral, Judith Schmidt, Yeshayahu Talmon, Bruno Ameduri, Marc Guerre, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), and Technion - Israel Institute of Technology [Haifa]

Subjects
Vinyl alcohol, Materials science, Polymers and Plastics, Bioengineering, block copolymer, macromolecular substances, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biochemistry, chemistry.chemical_compound, amphiphilic, Amphiphile, Polymer chemistry, Copolymer, Reversible addition−fragmentation chain-transfer polymerization, Fourier transform infrared spectroscopy, RAFT polymerization, Organic Chemistry, PVDF, PVAc, technology, industry, and agriculture, Self-assembly, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, 0210 nano-technology, Fluoride, Saponification
Abstract

International audience; This study is thefirst report of the synthesis and self-assembly in water of an amphiphilic PVDF-b-PVA block copolymer. The blockcopolymer was prepared by sequential RAFT polymerization of VDF and VAc followed by saponification of the PVAc block and wascharacterized by 1H NMR and FTIR. The self-assembled nanoparticles were characterized by DLS and cryo-TEM.

Published
2017

35. A Survey on the Use of Container Technologies in Autonomous Driving and the Case of BeIntelli

Author

Benjamin Acar, Marc Guerreiro Augusto, Marius Sterling, Fikret Sivrikaya, and Sahin Albayrak

Subjects
Docker, containerization, automotive, CCAM, autonomous driving, Transportation engineering, TA1001-1280, Transportation and communications, HE1-9990
Abstract

The application of containerization technology has seen a significant increase in popularity in recent years, both in the business and scientific sectors. In particular, the ability to create portable applications that can be deployed on different machines has become a valuable asset. Autonomous driving has embraced this technology, as it offers a wide range of potential applications, including the operation of autonomous vehicles and the digitization of infrastructure for the development of Cooperative, Connected, and Automated Mobility (CCAM) services. This paper provides a comprehensive analysis of containerization in autonomous driving, emphasizing its application, utility, benefits, and limitations.

Published
2023
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36. RAFT synthesis of well-defined PVDF-b-PVAc block copolymers

Author

Marc Guerre, S. M. Wahidur Rahaman, Bruno Ameduri, Vincent Ladmiral, Rinaldo Poli, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), ANR-14-CE07-0012,FLUPOL,Meilleurs polymères fluorés par la polymérisation radicalaire par voie organométallique(2014), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)

Subjects
RDRP, Polymers and Plastics, Radical, Bioengineering, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biochemistry, chemistry.chemical_compound, Polymer chemistry, Vinyl acetate, Copolymer, Moiety, Reversible addition−fragmentation chain-transfer polymerization, Organic Chemistry, PVAc, PVDF, Raft, 021001 nanoscience & nanotechnology, 0104 chemical sciences, fluoroplymers, defects of chaning, block copolymers, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, controlled radical polymerization, Xanthate, 0210 nano-technology
Abstract

International audience; RAFT polymerization of vinylidene fluoride (VDF), leading to relatively well defined poly(vinylidenefluoride) (PVDF), is negatively affected by chain inversion resulting in less easily reactivatable PVDFT-XAdormant chains (terminated with the tail end of an inversely added VDF unit; XA = xanthate moiety).Although slow reactivation of these chains by PVDF• radicals (in contrast to general belief) was recentlydemonstrated, slow radical exchange leads to progressive loss of chain growth control. This article dealswith the possibility of synthesizing block copolymers from PVDF-XA macroCTAs by sequential addition.The investigations show that only PVDFH-XA (chains terminated with the head end of regularly addedVDF) can be reactivated by PNVP• (poly(N-vinylpyrrolidone)) radicals and that PVDFT-XA chains are completelyunreactive in the presence of PNVP•, PB• (poly(butylacrylate)) or PDM• (poly(N,N’-dimethylacrylamide)).However, both PVDFH-XA and PVDFT-XA can be reactivated by PVAc• (poly(vinyl acetate))radicals. The reactivation of the PVDFT-XA, albeit slower than that of the PVDFH-XA, is sufficiently fast toallow the synthesis of unprecedented well-defined PVDF-b-PVAc block copolymers with relatively highend-group fidelity. DFT calculations rationalize this behavior on the basis of faster radical exchange in theorder PVDFH-XA/VAc > PVDFH-XA/NVP > PVDFT-XA/VAc ≫ PVDFT-XA/NVP. The success of the chainextension also relies on faster activation relative to homopropagation of the chain extending monomer, aswell as fast addition of the released PVDF•H and PVDF•T to the monomer.

Published
2016

37. Well-defined poly(vinylidene fluoride) (PVDF) based-dendrimers synthesized by click chemistry: enhanced crystallinity of PVDF and increased hydrophobicity of PVDF films

Author

Marc Guerre, Bruno Ameduri, Armelle Ouali, Anne-Marie Caminade, Vincent Ladmiral, Christian Bijani, Enrique Folgado, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Fédérale Toulouse Midi-Pyrénées, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Polymers and Plastics, Organic Chemistry, Bioengineering, 02 engineering and technology, Fluorine-19 NMR, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, 0104 chemical sciences, Contact angle, chemistry.chemical_compound, Crystallinity, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Dendrimer, Polymer chemistry, Click chemistry, [CHIM]Chemical Sciences, Well-defined, 0210 nano-technology, High-resolution transmission electron microscopy, Fluoride, ComputingMilieux_MISCELLANEOUS
Abstract

This study reports the preparation by click chemistry of a novel fluorinated dendrimer bearing PVDF branches and its characterization by several analytical methods including 1H, 13C, 31P and 19F NMR, diffusional NMR, SEC, DLS, ATG, DSC and HRTEM. As remarkable properties, this dendritic PVDF displayed crystallinity (HRTEM highlighted crystalline disc-like zones of ca. 5 nm) and a much higher hydrophobicity than both its precursors with the water contact angle (WCA) reaching 108°.

Published
2016

38. A Journey into the Microstructure of PVDF Made by RAFT

Author

Gérald Lopez, Marc Guerre, Thibaut Soulestin, Vincent Ladmiral, Bruno Ameduri, Gilles Silly, Cédric Totée, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Polymers and Plastics, reversible-deactivation radical polymerization, Radical polymerization, 02 engineering and technology, 010402 general chemistry, Poly(vinylidene fluoride), 01 natural sciences, chemistry.chemical_compound, Polymer chemistry, Materials Chemistry, Reversible addition−fragmentation chain-transfer polymerization, 19F NMR, Physical and Theoretical Chemistry, Reversible-deactivation radical polymerization, Organic Chemistry, 1H NMR, Chain transfer, Raft, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, End-group, [CHIM.POLY]Chemical Sciences/Polymers, Polymerization, chemistry, Fluoropolymer, 0210 nano-technology, RAFT, MADIX
Abstract

International audience; Poly(vinylidene fluoride) (PVDF) is a very important fluoropolymer. It possesses high resistances to weathering or ageing and to chemical and thermal aggressions, as well as unique electroactive properties. The reversible-deactivation radical polymerization (RDRP) of VDFcan, so far, only be achieved via degenerative transfer using ITP (iodine transfer polymerization) or RAFT (reversible addition–fragmentation chain transfer). However, due to chain defects, and transfer to solvents, the RAFT polymerization of VDF produces PVDF chains with different chain ends. This article presents the results obtained from advanced 1H, 13C, and 19F NMR spectroscopy experiments using decoupling strategies, to ascertain unequivocally the microstructure of the PVDF chains synthesized using RAFT polymerization. This article provides a very detailed description of the different α- and ω-chain ends of PVDF 51-XA and reveals an uncommon NMR heteronuclear coupling between the proton of the stereocenterof the CTA R-group and the fluorine atoms of the CF2 moiety of the first added VDF unit.

Published
2016

39. An amphiphilic PEG-b-PFPE-b-PEG triblock copolymer: synthesis by CuAAC click chemistry and self-assembly in water

Author

Gérald Lopez, Vincent Ladmiral, Yeshayahu Talmon, Bruno Ameduri, Jean-Pierre Habas, Judith Schmidt, Marc Guerre, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), and Technion - Israel Institute of Technology [Haifa]

Subjects
Materials science, Polymers and Plastics, DLS, Bioengineering, 02 engineering and technology, 010402 general chemistry, catalyzed alkyne–azide cycloaddition, 01 natural sciences, Biochemistry, Micelle, Dynamic light scattering, PEG ratio, Amphiphile, Polymer chemistry, Copolymer, triblock copolymers, tehrmalstability, Organic Chemistry, Nuclear magnetic resonance spectroscopy, Diffusion-ordered spectroscopy, 021001 nanoscience & nanotechnology, NMR, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Critical micelle concentration, Click chemistry, fluoropolymers, 0210 nano-technology
Abstract

International audience; A new PEG2000-b-PFPE1200-b-PEG2000 amphiphilic triblock copolymer was synthesized by copper(I)-catalyzed alkyne–azide cycloaddition (CuAAC). The microstructure of this ABA triblock copolymer wasunequivocally characterized by NMR spectroscopy. Diffusion-ordered spectroscopy (DOSY) NMR experimentrevealed that 1H resonances belonging to PEG and PFPE are aligned on the same horizontal line,thus implying that all these signals are due to the same macromolecule whose diffusion coefficient islower than that of PEG and PFPE homopolymers. Thanks to its semi-fluorinated backbone bearing robusttriazole rings, the PEG2000-b-PFPE1200-b-PEG2000 triblock copolymer exhibits good thermal stability withno significant weight loss until 275 °C under air. This triblock copolymer undergoes self-assembly intomicelles (D = 10–20 nm) in aqueous solution as confirmed from cryogenic-temperature transmissionelectron microscopy, DOSY experiment in D2O, and dynamic light scattering. The critical micelle concentrationwas determined by pyrene fluorescence assay, and was found to be 0.1 mg mL−1.

Published
2016

40. One-pot synthesis of poly(vinylidene fluoride) methacrylate macromonomers via thia-Michael addition

Author

Vincent Ladmiral, Marc Guerre, Bruno Ameduri, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Acrylate, Polymers and Plastics, Organic Chemistry, One-pot synthesis, Bioengineering, 02 engineering and technology, Raft, 010402 general chemistry, 021001 nanoscience & nanotechnology, Methacrylate, 01 natural sciences, Biochemistry, 0104 chemical sciences, chemistry.chemical_compound, Aminolysis, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, Polymer chemistry, Copolymer, Organic chemistry, [CHIM]Chemical Sciences, Xanthate, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

This study presents a new synthetic route to prepare original PVDF macromonomers and PVDF-based architectures. A poly(vinylidene fluoride), PVDF, synthesized using MADIX controlled polymerization in the presence of O-ethyl-S-(1-methoxycarbonyl)ethyldithiocarbonate was chemically modified via two strategies and fully characterized. Using a one-pot procedure, the xanthate end-groups of the PVDF were converted into thiols which were immediately added onto the acrylate moieties of 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHPMA) via regioselective thia-Michael addition to form new PVDF-MA macromonomers. Two methods of elimination of the thiocarbonylthio group were tested and compared: aminolysis, and elimination using sodium azide. These reactions were thoroughly examined via1H and 19F NMR spectroscopy and SEC-HPLC. The aminolysis procedure was shown to give better coupling efficiency and better-defined macromonomers. The PVDF-MA macromonomers with the highest functionality were further polymerized by RAFT. The RAFT homopolymerization of PVDF-MA revealed that a non-negligible amount of macromonomers did not react. In contrast RAFT copolymerization of PVDF-MA and MMA resulted in the total conversion of the macromonomers and allowed the synthesis of novel methacrylic copolymers and block copolymers.

Published
2015

41. Growth of high quality single crystals of strontium doped (Nd,Pr)-nickelates, Nd$_{2−x}$Sr$_x$NiO$_{4+δ}$ and Pr$_{2−x}$SrxNiO$_{4+δ}$

Author

Alain Cousson, Jean-Marc Bassat, Antoine Villesuzanne, Isabelle Weill, Marc Guerre, Werner Paulus, Martin Meven, Monica Ceretti, François Weill, Olivia Wahyudi, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universität Munchen - Université Technique de Munich [Munich, Allemagne] (TUM), Rheinisch-Westfälische Technische Hochschule Aachen University (RWTH), IREET, University of Bolton, ANR-08-BLAN-0069,FuSTOM,Fundamental Study of Oxygen Mobility at Moderate Temperature in Solid Oxides(2008), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Université de Bordeaux (UB), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, and Rheinisch-Westfälische Technische Hochschule Aachen (RWTH)

Subjects
Thermogravimetric analysis, Chemistry, Doping, Non-blocking I/O, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Crystal, Crystallinity, Crystallography, Transmission electron microscopy, General Materials Science, Crystallite, 0210 nano-technology, Stoichiometry
Abstract

International audience; Large size and high quality single crystals of Nd$_{2−x}$Sr$_x$NiO$_{4+δ}$ and Pr$_{2−x}$SrxNiO$_{4+δ}$, with selected composition (x = 0.0, 0.1 and 0.5), were grown by a floating-zone technique using an image furnace. We found that even small deviations from the ideal cation stoichiometry led to either NiO segregation or formation of Ni-poor Pr$_4$Ni$_3$O$_{10−x}$, or RE$_x$O$_y$ intergrowth phases, rendering the title compounds unstable even under ambient conditions. Related to potential applications as membranes in SOFC, we importantly found Nd$_{2−x}$Sr$_x$NiO$_{4+δ}$ and Pr$_{2−x}$SrxNiO$_{4+δ}$ powders, obtained from ground stoichiometric single crystals, to be stable in air at high temperature (1000 °C), contrary to the partial decomposition observed when synthesized as polycrystalline powders by classical solid state synthesis. The presence of NiO/Pr$_4$Ni$_3$O$_{10−x}$ or RE$_x$O$_y$ intergrowth phases are discussed as a drawback limiting high temperature stability for Pr$_2$NiO$_{4+δ}$. Grown single crystals were characterised by neutron and X-ray diffraction as well as by electron microscopy (SEM/EDS), revealing their excellent quality in terms of composition, homogeneity and crystallinity. For each crystal, the oxygen content was determined by thermogravimetric analysis in a reductive atmosphere. Transmission electron microscopy highlighted a complex incommensurate structure for Pr$_2$NiO$_{4.25}$ and Nd$_2$NiO$_{4.25}$ with a 2D modulation vector related to oxygen ordering.

Published
2015

42. Towards Dependable IoT via Interface Selection: Predicting Packet Delivery at the End Node in LoRaWAN Networks

Author

Marc Guerrero, Cristina Cano, Xavier Vilajosana, and Pascal Thubert

Subjects
IoT, LoRaWAN, dual-band, dependable, estimation, Chemical technology, TP1-1185
Abstract

Estimating channel conditions to predict packet delivery can be exploited as a powerful tool to ensure wireless networks dependability. In this article we explore the practical application of this idea from the end-device perspective, using the LoRaWAN protocol stack. We aim to understand if packet delivery can be estimated considering different levels of feedback at the end-device. For that, an extensive data collection campaign is carried out. Through an analysis of the obtained traces, we establish correlations between connectivity metrics at the end node and the fact that a packet is received at the gateway. The study is complemented considering different levels of feedback: (i) No feedback, (ii) enabling acknowledgements frames, and (iii) considering application/control plane data about the channel status at the gateway side. The results show that it is possible to estimate packet delivery in all the evaluated cases.

Published
2021
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