Search

Hyperpolarization by dissolution dynamic nuclear polarization (dDNP) has enabled promising applications in spectroscopy and imaging, but remains poorly widespread due to experimental complexity. Broad democratization of dDNP could be realized by remote preparation and distribution of hyperpolarized samples from dedicated facilities. Here we show the synthesis of hyperpolarizing polymers (HYPOPs) that can generate radical- and contaminant-free hyperpolarized samples within minutes with lifetimes exceeding hours in the solid state. HYPOPs feature tunable macroporous porosity, with porous volumes up to 80% and concentration of nitroxide radicals grafted in the bulk matrix up to 285 μmol g−1. Analytes can be efficiently impregnated as aqueous/alcoholic solutions and hyperpolarized up to P(13C) = 25% within 8 min, through the combination of 1H spin diffusion and 1H → 13C cross polarization. Solutions of 13C-analytes of biological interest hyperpolarized in HYPOPs display a very long solid-state 13C relaxation times of 5.7 h at 3.8 K, thus prefiguring transportation over long distances., Hyperpolarization by dissolution dynamic nuclear polarization has brought highly sensitive magnetic resonance to reality but there still remains severe limitations. Here the authors show an approach relying on the generation of hyperpolarizing polymers that bear a dual function.

International audience; Polystyrene (PS) is a major commodity polymer widely used in various applications ranging from packaging to insulation thanks to its low cost, high stiffness, and transparency as well as its relatively high softening temperature. Similarly to all polymers prepared by radical polymerization, PS is constituted of a C–C backbone and thus is not degradable. To confer degradability to such materials, the copolymerization of vinyl monomers with a cyclic monomer that could undergo radical ring-opening is an efficient method to introduce purposely cleavable bonds into the polymer backbone. Dibenzo[c,e]-oxepane-5-thione (DOT) is a cyclic thionolactone monomer known for its efficient copolymerization with acrylate derivatives but so far could not be incorporated into PS backbones. From a theoretical study combining density functional theory (DFT) and kinetic models using the PREDICI software, we showed that the modification of experimental conditions could overcome these limitations and that high molar mass degradable polystyrene (Mw close to 150 000 g·mol–1) could be prepared via statistical insertion of thioester groups into the polymer backbone. This copolymerization process is compatible with conventional free radical polymerization and reversible deactivation radical polymerization (RDRP) techniques such as nitroxide mediated polymerization (NMP). Thanks to favorable reactivity ratios allowing only a few mol % of thioester units to be randomly incorporated, there was no major modification of the thermal and mechanical properties of the PS. The degradation of such PS could be performed in tetrahydrofuran (THF) at room temperature (RT) in 1 h using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a base, leading to oligomers with Mn close to 2000 g·mol–1. We successfully demonstrate further applicability of these copolymerization systems for the phototriggered decomposition of PS in solution as well as the synthesis of cross-linked PS networks degradable into soluble side products.

In addition to the traditional parameters of chi (χ) and degree of polymerization (N), we demonstrate that the segregation strength of a diblock copolymer can be increased by introduction of an ionic unit at the junction of the two blocks. Compared to neutral linking groups, the electrostatic interactions between counterions of adjacent domain junctions leads to increased enthalpy, segregation strength, and phase separation. As a result, the order disorder transition temperatures of block copolymers with a 1,2,3-triazolium ionic junction were observed to be significantly higher than the corresponding neutral block copolymers. To demonstrate the potential of block copolymers with ionic junctions for nanopatterning, block copolymers were prepared by click coupling of homopolymers and then used to fabricate well-defined sub-10 nm line features. We believe that the concept of improved thin-film assembly through the introduction of ionic junctions is a powerful tool for block copolymer lithography and compleme...

International audience; A one-pot synthesis method for various α-vinyl,ω-methoxysilyl polyethylene oligomers with well-defined lengths and high end-group functionalities and crystallinities is presented. This method relies on the combination of catalyzed chain growth of ethylene in the presence of a di(alkenyl)magnesium chain transfer agent and a neodymocene complex, followed by efficient deactivation using a variety of silane reagents: trimethoxymethylsilane, trimethoxyvinylsilane and tetramethoxysilane. Further condensation of the ω-methoxysilyl groups of these polymers in active medium (toluene/acetic acid mixture) leads to complex architectures such as comb-like structures or star-like structures that combine high vinyl functionality at extremities with a high crystallinity.

Hyperpolarization by dissolution dynamic nuclear polarization (dDNP) has brought highly sensitive magnetic resonance to reality and has triggered the development of a plethora of promising applications in spectroscopy and imaging. Unfortunately, some severe limitations still restrain its widespread use, amongst which the experimental complexity, the need for trained personnel, and excessive prices. Broad democratization of dDNP would require remote preparation of hyperpolarized samples in dedicated facilities and transport over long distances to the point of use. We have recently pioneered a new concept in which transport over hours was enabled by formulation of 13C-labelled molecules into micro-crystallites. However, the proposed methods lacked both versatility and biocompatibility. Here, we propose a new approach relying on a new generation of hyperpolarizing polymers (HYPOPs), extremely easy to synthesize, and that bear a dual function. Arbitrary solutions, easily impregnated into these radical-containing porous HYPOPs, can be hyperpolarized within 20 min with a polarization level exceeding P(13C) > 25% in the solid state, and further stored for hours in view of transport to a remote point of use.

International audience; Among possible routes towards isocyanate-free PUs, aminolysis of cyclic carbonates leading to polyhydroxyurethanes (PHUs) is one of the most promising pathways. Herein, we describe the solvent-free synthesis of shape memory PHU networks from diglycerol dicarbonate through reactive extrusion with varying amounts of primary and secondary triamines, Tris(2-aminoethyl)amine and Tris(2-(methyla-mino)ethyl)amine). Depending on the composition of the system, the glass transition temperature of the PHU networks can be finely tuned in the 20-40°C range and, consequently, affords shape memory recovery at body temperature. In addition, these networks revealed hydro-lysable over a few months and may find uses as bioresorbable templates for medical applications.

International audience; Epoxy-acid vitrimer particles with excellent osmotic and hydrolytic stability were synthesized by miniemulsion polymerization thanks to in situ generation of surfactants from the carboxylic acid reagent and a water-soluble base. The sulfate-free vitrimers formed in this way show greatly reduced creep viscosities.

International audience; Vitrimers, in stringent contrast to dissociative networks, involve associative covalent exchanges and remain fully cross-linked at all temperatures. However, we have previously reported on poly(1,2,3-triazolium) dynamic networks that exhibit linear rheological characterization indistinguishable from vitrimers although being based on a dissociative covalent exchange process, i.e., deN -alkylation and re-N-alkylation reactions. Herein, we highlight the main features of dissociative and associative covalent adaptable networks (CANs) and discuss their respective linear rheological behaviors. After giving a detailed overview of the extent and potential of dynamic polymer networks having 1,2,3-triazolium cross-links in particular and CANs involving trans-N-alkylation exchanges in general, we perform a detailed rheological comparative characterization of previously described aliphatic 1,2,3-triazolium-based dynamic networks and a new bicomponent thermosetting system issued from the mixing of linear polystyrene chains having complementary benzyl iodide and 1,2,3-triazole pendent groups. We propose a simple but comprehensive rheological characterization methodology that enables proper comparison between all types of CANs, i.e., vitrimers and dissociative networks. Owing to the combination of a high glass transition temperature dynamic network and fast trans-N-alkylation exchanges in this new dissociative network, it is possible to characterize both glass transition and network relaxation with single rheological experiments. We provide clear experimental evidence that although located within a narrow temperature range, the temperature dependences of these two transitions are distinct and follow WLF and Arrhenius models, respectively.

International audience; While the introduction of polymers in aerogels strongly enhances their toughness, truly elastic monolithic aerogels able to restore their dimensions upon extensive compression are still challenging to synthesize. In this context hydrophobic semi-crystalline polymers with low glass transition temperatures that combine both stiffness and flexibility have only recently gained attention. We show that polyethylene aerogels with low density combining chemical crosslinking and high crystallinity display high moduli and excellent mechanical resilience. In order to maximize the crystallinity of these aerogels while maintaining a high crosslinking density, we synthesized polyethylene networks with well-defined segments by hydrosilylation-crosslinking of telechelic, vinyl-functionalized oligomers obtained from recent advances in catalyzed chain growth polymerization. Recoverable deformations both above and below the melting temperature of polyethylene affords remarkable shape-memory properties.

Block copolymers with increased Flory–Huggins interaction parameters (χ) play an essential role in the production of sub-10 nm nanopatterns in the growing field of directed self-assembly for next generation lithographic applications. A library of PDMS-b-PEO block copolymers were synthesized by click chemistry and their interaction parameters (χ) determined. The highest χ measured in our samples was 0.21 at 150 °C, which resulted in phase-separated domains with periods as small as 7.9 nm, suggesting that PDMS-b-PEO is a prime candidate for sub-10 nm nanopatterning. To suppress PEO crystallization, PDMS-b-PEO was blended with (l)-tartaric acid (LTA) which allows for tuning of the self-assembled morphologies. Additionally, it was observed that the order-disorder transition temperature (TODT) of PDMS-b-PEO increased dramatically as the amount of LTA in the blend increased, allowing for further control over self-assembly. To understand the mechanism of this phenomenon, we present a novel field-based supramolecular model, which describes the formation of copolymer-additive complexes by reversible hydrogen bonding. The mean-field phase separation behavior of the model was calculated using the random phase approximation (RPA). The RPA analysis reproduces behavior consistent with an increase of the effective χ in the PDMS-b-(PEO/LTA suprablock). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2200–2208

Nanopapers containing cellulose nanofibrils (CNFs) are an emerging and sustainable class of high performance materials. The diversification and improvement of the mechanical and functional property space critically depend on integration of CNFs with rationally designed, tailor-made polymers following bioinspired nanocomposite designs. Here we combine for the first time CNFs with colloidal dispersions of vitrimer nanoparticles (VP) into mechanically coherent nanopaper materials. Vitrimers are permanently cross-linked polymer networks that undergo temperature-induced bond shuffling through an associative mechanism and which allow welding and reshaping on the macroscale. The choice of low glass transition, hydrophobic vitrimers derived from fatty acids and polydimethylsiloxane (PDMS), and achieving dynamic reshuffling of cross-links through transesterification reactions enables excellent compatibility and covalent attachment onto the CNF surfaces. Moreover, the resulting films are ductile, stretchable and offer high water resistance. The success of imparting the vitrimeric polymeric behavior into the nanocomposite, as well as the curing mechanism of the vitrimer, is highlighted through thorough analysis of structural and mechanical properties. The dynamic exchange chemistry of the vitrimers enables efficient welding of two nanocomposite parts as characterized by good bonding strength during single lap shear tests. In the future, we expect that the dynamic character of vitrimers becomes a promising option for the design of mechanically adaptive bioinspired nanocomposites and for shaping and reshaping such materials.

International audience; While 1T′ phase-pure MX2 (M = Mo, W; X = Se, Te) have recently been reported to be superconductors, Weyl semimetals, or quantum spin Hall insulators, the electronic properties of phase-pure 1T′-WS2 samples are still lacking thorough investigation. Here, we report the study of single-layer 1T′-WS2 nanosheets prepared from lithium exfoliation of WS2. We confirmed the composition and structure of single layer 1T′-WS2 flakes using X-ray photoelectron spectroscopy, Raman spectroscopy, and aberration corrected transmission electron microscopy (STEM). The distorted octahedral structure related to the 1T′ phase with a 2a × 2a superstructure is evidenced using STEM. Photoemission and electronic measurements uncover the presence of a narrow bandgap (>120 meV) in the 1T′-WS2 nanosheets, which is completely different from semiconducting bulk or single-layer 1H-WS2. The material is found to be ambipolar with a p-type nature. At low temperatures, a slow photoresponse is also observed.

International audience; We introduce recodable surfaces solely based on reversible artificial hydrogen bonding interactions. We show that a symmetrical oligoamide (SOA) attached to poly(methyl methacrylate) (PMMA) can be repeatedly immobilized and cleaved off spatially defined surface domains photochemically functionalized with asymmetric oligoamides (AOAs). The spatially resolved recodability is imaged and quantified via ToF-SIMS.

International audience; A series of six 1,2,3-triazolium-based poly(ionic liquid)s (TPILs) having random distributions of 1,3,4- and 1,3,5-trisubstituted 3-methyl-1,2,3-triazolium units are prepared by the solvent-and catalyst-free 1,3-dipolar Huisgen cycloaddition of two alpha-azide-omega-alkyne monomers and simultaneous N-alkylation of the resulting 1,4- and 1,5-disubstituted poly(1,2,3-triazole)s by N-methyl bis(trifluoromethylsulfonyl)imide (TFSI), trimethyl phosphate or methyl methanesulfonate quaternizing agents. The physical and ion conducting properties of this series of TPILs having TFSI, dimethyl phosphate (DMP) or methanesulfonate (MSF) anions are discussed based on solubility, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), size exclusion chromatography (SEC) and broadband dielectric spectroscopy (BDS) measurements.

We report herein the modular synthesis and nanolithographic potential of poly(dimethylsiloxane-block-methyl methacrylate) (PDMS-b-PMMA) with self-assembled domains approaching sub-10 nm periods. A straightforward and modular coupling strategy, optimized for low molecular weight diblocks and using copper-catalyzed azide–alkyne “click” cycloaddition, was employed to obtain a library of PDMS-b-PMMA and poly(dimethylsiloxane-block-styrene) (PDMS-b-PS) diblock copolymers. Flory–Huggins interaction parameters, determined from small-angle X-ray scattering experiments, were high for PDMS-b-PMMA (χ ∼ 0.2 at 150 °C), suggesting this diblock copolymer system has promise for sub-10 nm lithographic applications when compared to the corresponding PDMS-b-PS diblock copolymers (χ ∼ 0.1 at 150 °C). Performance evaluation in thin film self-assembly experiments allowed domain periods as small as 12.1 nm to be obtained, which is among the smallest highly ordered nanoscale patterns reported hitherto for thermally annealed mat...

International audience; Colloidal dispersions of epoxy-acid vitrimers have been synthesized by miniemulsion polymerization. This versatile strategy enables obtaining stable cross-linked particles, even from initially incompatible precursors, while minimizing hydrolysis of the ester bonds formed during the curing. After drying of the latexes, trans-esterification exchanges occurring at high temperatures through interparticle interfaces induces an efficient sintering into homogeneous cross-linked polymer films.

International audience; Vitrimers are dynamic polymer networks with unique viscoelastic behavior combining the best attributes of thermosets and thermoplastics. Ionic vit-rimers are a recent class of dynamic materials, where 1,2,3-triazolium cross-links are reshuffled by trans-N-alkylation exchange reactions. Comparison of dynamic properties with a selection of vitrimers relying on different exchange reactions highlights the particularly high viscous flow activation energies of trans-N-alkylation reactions, thus providing an enhanced compromise between fast reprocessing at moderately high temperatures and low creep at service temperature. Varying the [monomer]/[cross-linker] ratio in the initial formulation of these 1,2,3-triazolium-based networks affords a fine tuning of their viscosity profiles. Confrontation of rheometry and X-ray photoelectron spectroscopy data allows the correlation of variations in chemical composition with changes in the covalent exchange dynamics. This unprecedented approach enables the proposition of a dissociative two-step mechanism for the trans-N-alkylation of 1,2,3-triazoliums initiated by a nucleophilic attack of the 1,2,3-triazolium cross-links by the iodide counteranion, yielding uncrosslinking by deN -alkylation. Subsequent rapid re-N-alkylation of the formed 1,2,3-triazole by surrounding iodide-functionalized dangling chains affords exchange of the cross-link position. This study highlights that strictly associative exchange reactions are not compulsory to induce vitrimer behavior, and may pave the way to a much wider variety of vitrimers relying on conventional reversible covalent reactions.

The untapped potential of radical thiol-yne mono-addition chemistry is exploited to overcome the known limitations of thiol-ene chemistry in polymer coupling and block copolymer formation. By careful choice of alkyne, the reaction can selectively lead to the mono-addition product with efficiencies surpassing those achieved by traditional thiol-ene chemistry. This improvement is illustrated by the nearly quantitative synthesis of a variety of diblock and graft copolymers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 319–326

Conjugated polyrotaxanes jacketed with hole-transport groups have been synthesized from water-soluble polyrotaxanes consisting of a polyfluorene-alt-biphenylene (PFBP) conjugated polymer threaded through β-cyclodextrin macrocycles. The hydroxyl groups of the oligosaccharides were efficiently functionalized with triphenylamine (TPA) so that every polyrotaxane molecule carries a coat of about 200 TPA units, forming a supramolecular coaxial structure. This architecture was characterized using a range of techniques, including small-angle X-ray scattering. Absorption of light by the TPA units results in excitation energy transfer (EET) and photoinduced electron transfer (ET) to the inner conjugated polymer core. These energy- and charge-transfer processes were explored by steady-state and time-resolved fluorescence spectroscopy, femtosecond transient absorption spectroscopy, and molecular modeling. The time-resolved measurements yielded insights into the heterogeneity of the TPA coat: those TPA units which are close to the central polymer core tend to undergo ET, whereas those on the outer surface of the polyrotaxane, far from the core, undergo EET. Sections of the backbone that are excited indirectly via EET tend to be more remote from the TPA units and thus are less susceptible to electron-transfer quenching. The rate of EET from the TPA units to the PFBP core was effectively modeled by taking account of the heterogeneity in the TPA-PFBP distance, using a distributed monopole approach. This work represents a new strategy for building and studying well-defined arrays of >100 covalently linked chromophores. © 2014 American Chemical Society.

We combine the supramolecular chemistry of heterocyclic ureas with the chemistry of epoxides to synthesize new crosslinked materials incorporating both chemical and supramolecular hydrogen-bonded links. A two-step facile and solvent-free procedure is used to obtain chemically and thermally stable networks from widely available ingredients: epoxy resins and fatty acids. The density of both chemical and physical crosslinks is controlled by the stoichiometry of the reactants and the use of a proper catalyst to limit side reactions. Depending on the stoichiometry, a wide range of thermomechanical properties can be attained. The method can be used to produce elastomeric objects of complex shapes. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1133–1141, 2010

We describe the synthesis of supramolecular self-healing elastomers from vegetable oil fatty acid derivatives, diethylene triamine, and urea. Our strategy to obtain materials that are self-healing but do not flow relies on the use of a wide molecular distribution of randomly branched oligomers equipped with self-complementary and complementary hydrogen bonding groups. We prepared such oligomers with a two steps procedure. In the first step, diethylene triamine was condensed with dimer acids. In the second step, the oligomers obtained were allowed to react with urea. The molecules were characterized by NMR and IR spectroscopies and Monte-Carlo simulations were used to analyze the molecular size distribution. The sensitivity to small variations of the experimental conditions has been examined and the robustness of the synthetic procedure optimized. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7925–7936, 2008

International audience; We designed efficient precursors that combine complementary associative groups with exceptional binding affinities and thiocarbonylthio moieties enabling precise RAFT polymerization. Well defined PS and PMMA supramolecular polymers with molecular weights up to 30 kgmol(-1) are synthesized and shown to form highly stable supramolecular diblock copolymers (BCPs) when mixed, in non-polar solvents or in the bulk. Hierarchical self-assembly of such supramolecular BCPs by thermal annealing affords morphologies with excellent lateral order, comparable to features expected from covalent diblock copolymer analogues. Simple washing of the resulting materials with protic solvents disrupts the supramolecular association and selectively dissolves one polymer, affording a straightforward process for preparing well-ordered nanoporous materials without resorting to crosslinking or invasive chemical degradations.

International audience; Exploiting exchangeable covalent bonds as dynamic cross-links recently afforded a new class of polymer materials coined as vitrimers. These permanent networks are insoluble and infusible, but the network topology can be reshuffled at high temperatures, thus enabling glasslike plastic deformation and reprocessing without depolymerization. We disclose herein the development of functional and high-value ion-conducting vitrimers that take inspiration from poly(ionic liquid)s. Tunable networks with high ionic content are obtained by the solvent- and catalyst-free polyaddition of an alpha-azide-omega-alkyne monomer and simultaneous alkylation of the resulting poly(1,2,3-triazole)s with a series of difunctional cross-linking agents. Temperature-induced transalkylation exchanges of C-N bonds between 1,2,3-triazolium cross-links and halide-functionalized dangling chains enable recycling and reprocessing of these highly cross-linked permanent networks. They can also be recycled by depolymerization with specific solvents able to displace the transalkylation equilibrium, and they display a great potential for applications that require solid electrolytes with excellent mechanical performances and facile processing such as supercapacitors, batteries, fuel cells, and separation membranes.

Thermoplastic elastomers (TPEs) are designed by embedding discrete glassy or semicrystalline domains in an elastomeric matrix. Typical styrenic-based amorphous TPEs are made of linear ABA-type triblock copolymers, where the volume fraction f of the glassy domains A is typically less than 0.3. This limitation ultimately restricts the range of mechanical strength attainable with these materials. We had previously predicted using self-consistent field theory (SCFT) that A(BA′)n miktoarm block copolymers with an approximately 8:1 ratio of the A to A′ block molecular weights and n ≥ 3 should exhibit discrete A domains at considerably larger f and offer potential for the combination of high modulus, high recoverable elasticity, and high strength and toughness. Using transmission electron microscopy and small-angle X-ray scattering on model polystyrene-b-polyisoprene (PS–PI) miktoarm copolymers, we show that such polymers indeed possess discrete PS domains for f values considerably higher than 0.3. The hexagonal...

International audience; The patterning of solid electrolytes that builds upon traditional fabrication of semiconductors is described. An azide-, functionalized poly(1,2,3-triazolium ionic liquid) is used as an ion conducting negative tone photoresist. After UV-irradiation through an optical mask, micron-scaled, patterned, solid polyelectrolyte layers with controlled sizes and shapes are obtained. Furthermore, alkylation of poly(1,2,3-triazole)s can be generalized to the synthesis of poly(ionic liquid)s with a tunable amount of pendant functionalities.

A modular and robust method for preparing end-functionalized donor–acceptor (D–A) narrow bandgap conjugated polymers is reported that avoids multistep reactions and postpolymerization modification. The strategy is well-controlled and affords functional materials with predictable molecular weight and high end-group fidelity. To exemplify this synthetic strategy, narrow bandgap conjugated polymers based on PDPP2FT were prepared that contain perylene diimide (PDI) units at the chain-ends. Monte Carlo simulations confirm the high degree of chain-end functionalization while photoluminescence studies reveal the unique photophysical properties of the end-functional polymers with efficient charge transfer occurring between the main polymer chain and PDI end-groups that results exclusively from their covalent linkage.

International audience; A remarkable self-healing property has been achieved recently with rubbers formed by a supramolecular network of oligomers. Here we explore this property through a tack-like experiment where two parts of supramolecular rubber are simply brought into contact and then taken apart. These experiments reveal that the self-adhesive strength of rubber surfaces is significantly enhanced by fracture or other damaging processes. The mechanical energy required to separate two fracture surfaces that were brought back into contact is about one order of magnitude larger than that for surfaces close to thermodynamic equilibrium. Moreover, we find that fracture faces stored apart at room temperature still self-heal after 12 h but that this self-healing can be fully deactivated within a couple of hours by annealing around 90 °C. More generally, these results provide useful quantitative data to investigate the intensity and kinetics of self-healing in these soft rubbers.

Catalytic control of bond exchange reactions enables healing of cross-linked polymer materials under a wide range of conditions. The healing capability at high temperatures is demonstrated for epoxy–acid and epoxy–anhydride thermoset networks in the presence of transesterification catalysts. At lower temperatures, the exchange reactions are very sluggish, and the materials have properties of classical epoxy thermosets. Studies of model molecules confirmed that the healing kinetics is controlled by the transesterification reaction rate. The possibility of varying the catalyst concentration brings control and flexibility of welding and assembling of epoxy thermosets that do not exist for thermoplastics.

Permanently cross-linked materials have outstanding mechanical properties and solvent resistance, but they cannot be processed and reshaped once synthesized. Non–cross-linked polymers and those with reversible cross-links are processable, but they are soluble. We designed epoxy networks that can rearrange their topology by exchange reactions without depolymerization and showed that they are insoluble and processable. Unlike organic compounds and polymers whose viscosity varies abruptly near the glass transition, these networks show Arrhenius-like gradual viscosity variations like those of vitreous silica. Like silica, the materials can be wrought and welded to make complex objects by local heating without the use of molds. The concept of a glass made by reversible topology freezing in epoxy networks can be readily scaled up for applications and generalized to other chemistries.

We have demonstrated recently [1] that an assembly of molecules, connected to each other by strong, but thermally reversible, hydrogen bonds, is able to show rubber elasticity and, in striking contrast to conventional rubbers, is able to self-heal when cut or torn into pieces. Self-repair is achieved by simply bringing the broken pieces into contact with no chemical reactions, no heat nor strong pressure applied. In this paper, we briefly review the design principles, synthesis and physical properties of such materials.

We propose a strategy to obtain through a facile one-pot synthesis a large variety of supramolecular materials that can behave as differently as associating low-viscosity liquids, semicrystalline or amorphous thermoplastics, viscoelastic melts or rubbers. Such versatility is achieved thanks to simultaneous synthesis of branched backbones and grafting of associating units. This contrasts with usual synthetic pathways that rely on grafting functional groups on preprepared backbones. We use oligocondensation of fatty di- and triacids with diethylenetriamine and finely tune the molecular weight and degree of branching by end-capping some acid groups before condensation by reaction with aminoethylimidazolidone. Supramolecular assembly is formed thanks to complementary and self-complementary associations of amide, imidazolidone, and dialkylurea groups, and the stoichiometry directly controls the mesoscopic structure and properties.

This thesis work deals with the application of reactive extrusion to the bulk synthesis of polyhydroxyurethanes (PHUs). On the one hand, thermoplastic PHUs have been synthesized from three biobased 5-membered biscyclic carbonates, two of them being ester- or ether- chemically ‘activated’. The complete conversion of reactive functions has been reached in most cases, in relatively short reaction times (few hours), despite very cohesive systems, specifically in the case of one biscyclic carbonate bearing amide moieties. On the other hand, thermosets PHUs with shape memory capacity and reprocessability have been synthesized through this process. Simultaneously, a study was performed on model reactions in order to determine the experimental conditions that limit urea formation during the aminolysis of biscyclic carbonates. Finally, a purification protocol was developed in order to separate the two enantiomers of DGDC biscyclic carbonate. The polymerization of these two separated enantiomers with diamines demonstrated that the stereochemistry of biscyclic carbonate monomers plays a crucial role in the final polymer size and properties., Cette thèse porte sur l’application du procédé d’extrusion réactive à la synthèse, sans solvant, de polyhydroxyuréthanes (PHUs). D’une part, des PHUs thermoplastiques ont été synthétisés à partir de trois biscarbonates cycliques à 5 chaînons, activés ou non par des fonctions ester ou éther en béta du cycle, et différentes diamines. La conversion totale des fonctions réactives a été atteinte dans la majorité des cas en des temps courts (quelques heures), malgré le caractère très cohésif des substrats biscarbonates employés et notamment ceux comportant un lien amide. D’autre part, via ce même procédé d’extrusion réactive, différents PHUs réticulés qui présentent des propriétés de mémoire de forme ou encore de reprocessabilité ont été synthétisés. En parallèle, une étude via des réactions modèles menées hors extrudeuse a permis de mettre en évidence les conditions expérimentales permettant de fortement limiter la formation d’un produit secondaire de type urée. Dans le cas particulier du dicarbonate de diglycerol (DGDC), un protocole de purification par recristallisation a été mis au point de façon à séparer ses deux formes énantiomères. La polymérisation des deux énantiomères séparés, avec différentes diamines, a révélé que la stéréochimie du monomère biscarbonate joue un rôle déterminant sur les dimensions et les caractéristiques thermomécaniques des PHUs finaux.

This thesis focuses on the development and study of thermomechanical properties of dynamic polymers incorporating borylated derivatives. While applying this concept to a variety of macromolecular architectures: functional copolymers, di- and tri-functional bricks, two distinct reactivities of boron have been explored. A wide range of characterization methods has been used to carry out this project: FTIR and NMR spectroscopies under numerous stimuli, as well as many thermal and mechanical analyses. In a first step, we considered the formation of Frustrated Lewis Pairs between Lewis acids (organoboranes) and Lewis bases (amines and phosphines) sterically hindered, as this interaction can be strongly modulated by the participation of a third compound such as gas molecules. Thus, we have been able to form dynamic networks reversibly crosslinkable with carbon dioxide. In a second step, we demonstrated a new reactivity in cyclic boronic esters involving a ring-opening at high temperature, assisted by the presence of nucleophiles. This reaction has been used to form dynamically crosslinked polymers, which can reach glass transition temperatures up to 220°C and de-crosslinkable by dilution in a good (apolar) polymer solvent. This reactivity has been applied to a variety of polymers accessible by radical copolymerization (styrene, ethylene, vinyl acetate, butyl acrylate) or by post-functionalization of commercial polymers (polybutadiene), Ces travaux de thèse portent sur l’élaboration et l’étude des propriétés thermomécaniques de polymères dynamiques incorporant des dérivés borés. Tout en appliquant ce concept sur une variété d’architectures macromoléculaires : copolymères fonctionnels, briques di- et tri-fonctionelles, deux réactivités distinctes du bore ont été étudiées et exploitées. Une large gamme de méthodes de caractérisation a été utilisée pour mener à bien ce projet : spectroscopies FTIR et RMN sous différents stimuli, ainsi que de nombreuses analyses thermiques et mécaniques. Dans un premier temps, nous avons considéré la formation de paires de Lewis frustrées entre des acides de Lewis (organoboranes) et des bases de Lewis (amines et phosphines) stériquement encombrés, cette interaction pouvant être fortement modulée par la participation d’un troisième composé tels que des molécules de gaz. Ainsi, nous avons été capables de former des réseaux dynamiques réticulables de façon réversible avec le dioxyde de carbone. Dans un second temps, nous avons mis en évidence une nouvelle réactivité dans les esters boroniques cycliques impliquant une ouverture de cycle à haute température, assistée par la présence de nucléophiles. Cette réaction a été mise à profit pour former des polymères réticulés dynamiquement, pouvant atteindre des températures de transition vitreuse jusqu’à 220°C et dé-réticulables par dilution avec un bon solvant du polymère (apolaire). Cette réactivité a été appliquée à une variété de polymères accessibles par copolymérisation radicalaire (styrène, éthylène, acétate de vinyle, acrylate de butyle) ou par post-fonctionnalisation de polymères commerciaux (polybutadiène)

This PhD thesis tackles the development of monotopic (or single step) processes enabling the accelerated synthesis of ion conducting polymer materials. A bibliographic study on 1,2,3-triazolium-based poly(ionic liquid)s (TPILs) have demonstrated their unequaled structural and functional richness. However, their syntheses require several synthetic steps and the use of catalysts, solvents and polymerization mediators.A first part is devoted to the development of an accelerated synthetic approach enabling in a single step to access TPILs with broad structural variety without solvent nor catalyst. Indeed the chemical structure of the spacer, the counter-anion and the N-3 substituent of the 1,2,3-triazolium group can be readily tuned from a broad library of a-azide-?-alkyne monomers and alkylating agents.A second part is devoted to the extension of this original synthetic approach to the formation of a series of ion conducting polymer networks, thus demonstrating the flexibility of the process and the broad capacity in structural design. These networks possess the unique properties of vitrimer materials based on dynamic exchanges of the cross-linking points by transalkylation reactions of C-N bonds under strain and temperature. They can thus be reshaped and recycled without significant loss of their properties, which constitute the first example of functional vitrimer.The properties of these materials, as well as the rapidity, the versatility and the flexibility of their syntheses constitute a major breakthrough in the field of ion conducting polymer materials and their applications, Cette thèse s'intéresse au développement de procédés monotopes (en une seule étape) permettant la synthèse accélérée de polymères conducteurs ioniques.Une étude bibliographique sur les poly(liquides ioniques) à base 1,2,3-triazolium (TPILs) a démontré leurs richesses structurale et fonctionnelle inégalées. Leur synthèse requière cependant plusieurs étapes nécessitant l'emploi de catalyseurs, de solvants et d'agents de polymérisation.Une première partie est consacrée au développement d'une voie de synthèse accélérée permettant d'accéder en une seule étape, sans solvant, ni catalyseur à des TPILs de structures variées. Il est en effet aisément possible de moduler les structures chimiques de l'espaceur, du contre-anion et du substituant en position N-3 du groupe 1,2,3-triazolium à partir d'un large choix de monomères a-azoture-?-alcyne et d'agents alkylants.Une seconde partie est consacrée à l'extension de cette voie de synthèse originale à l'élaboration d'une série de réseaux conducteurs ioniques, démontrant ainsi la souplesse du procédé et l'immense possibilité de variation structurale. Ces réseaux possèdent les propriétés uniques des matériaux vitrimères sur la base d'échanges dynamiques des points de réticulation par des réactions de transalkylation des liaisons C-N sous contrainte et température. Ils peuvent ainsi être remis en forme et recyclés sans pertes majeures de leurs propriétés et constituent donc le premier exemple de vitrimère fonctionnel. L'ensemble de ces matériaux de par leurs propriétés ainsi que leur rapidité et leur facilité de synthèse constituent donc une avancée majeure dans le domaine des polymères conducteurs ioniques et leurs applications