Damien Montarnal

• PhD
• Institut National des Sciences Appliquées de Lyon

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 withou...

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 grafti...

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 kg mol(-1) are synthesized and shown to form highly stable supramolecular diblock copo...

This work investigates the correlation between the formulation of waterborne acrylic pressure‐sensitive adhesives (PSAs) and their resulting adhesive performance. A library of n ‐butyl acrylate‐based latexes is synthesized via miniemulsion polymerization. Controlled variations in the composition of these polyacrylates – such as the inclusion of rig...

Olefin triblock copolymers based on glassy polystyrene (PS), ethylene butadiene rubber (EBR) and highly crystalline polyethylene (PE) segments were prepared for the first time using a switch strategy from anionic polymerization to coordinative chain transfer (co)polymerization (CCT(co)P). PS chains obtained by anionic polymerization were transmetal...

Olefin triblock copolymers based on glassy polystyrene (PS), ethylene butadiene rubber (EBR) and highly crystalline polyethylene (PE) segments were prepared for the first time using a switch strategy from anionic polymerization to coordinative chain transfer (co)polymerization (CCT(co)P). PS chains obtained by anionic polymerization were transmetal...

Cerium dioxide (CeO2) has huge potential in many applications ranging from biochemical engineering to the coating industry. Here, the first example of visible light photo‐mediated Pickering emulsion polymerization of (meth)acrylate monomers is reported using CeO2 nanoparticles (NPs) as solid stabilizer. A ω,ω′−dicarboxylic acid diphenyl disulfide p...

The low sensitivity of liquid‐state nuclear magnetic resonance (NMR) can be overcome by hyperpolarizing nuclear spins by dissolution dynamic nuclear polarization (dDNP). It consists of transferring the near‐unity polarization of unpaired electron spins of stable radicals to the nuclear spins of interest at liquid helium temperatures, below 2 K, bef...

The low sensitivity of liquid‐state nuclear magnetic resonance (NMR) can be overcome by hyperpolarizing nuclear spins by dissolution dynamic nuclear polarization (dDNP). It consists of transferring the near‐unity polarization of unpaired electron spins of stable radicals to the nuclear spins of interest at liquid helium temperatures, below 2 K, bef...

A cationic poly(ionic liquid) (PIL) with pendent butyl imidazolium cations and free bis(trifluoromethylsulfonyl)imide (TFSI) anions and an anionic PIL with pendent TFSI anions and free 1-butyl-3-methylimidazolium cations are synthesized by postpolymerization chemical modification and reversible addition–fragmentation chain-transfer radical copolyme...

The low sensitivity of liquid-state nuclear magnetic resonance (NMR) can be overcome by hyperpolarizing nuclear spins by dissolution dynamic nuclear polarization (dDNP). It consists of transferring the near-unity polarization of unpaired electron spins of stable radicals to the nuclear spins of interest at liquid helium temperatures, below 2 K, bef...

1,3,4‐Trisubstituted 1,2,3‐triazolium salts having either aliphatic or benzylic substituents at the N‐1 and N‐3 positions were synthesized in two steps involving: i) copper(I) catalyzed azide‐alkyne 1,3‐dipolar cycloaddition (CuAAC), and ii) N‐alkylation of the 1,2,3‐triazole intermediates. Trans‐N‐alkylation reactions in bulk and in the presence o...

Phase‐separated polymer blends including a transesterification vitrimer and polypropylene are synthesized from widely available precursors through reactive processing. It is shown that proper formulation during the process including a viscosity modifier of the vitrimer precursors and a reactive interface compatibilizer yields well‐dispersed vitrime...

Block copolymers based on polyethylene (PE) and ethylene butadiene rubber (EBR) were obtained by successive controlled coordinative chain transfer polymerization (CCTP) of a mixture of ethylene and butadiene (80/20) and pure ethylene. EBR‐b‐PE diblock copolymers were synthesized using the {Me2Si(C13H8)2Nd(BH4)2Li(THF)}2 complex in combination with...

Block copolymers based on polyethylene (PE) and ethylene butadiene rubber (EBR) were obtained by successive controlled coordinative chain transfer polymerization (CCTP) of a mixture of ethylene and butadiene (80/20) and pure ethylene. EBR‐b‐PE diblock copolymers were synthesized using {Me2Si(C13H8)2Nd(BH4)2Li(THF)}2 complex in combination with n‐bu...

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 temper-ature. Similarly to all polymers prepared by radical polymerization, PS is constituted of a C-C backbone and thus is not degra...

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 th...

A designed library of covalent adaptable networks (CANs) having 1,2,3-triazolium dynamic cross-links are obtained through the combination of solvent- and catalyst-free thermally induced azide-alkyne cycloaddition and N-alkylation reactions. The use of rigid heterocyclic or aromatic segments affords CANs with a greatly extended range of thermomechan...

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, th...

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, foll...

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...

While the introduction of polymers into aerogels strongly enhances their toughness, truly elastic monolithic aerogels which restore their dimensions upon extensive compression are still challenging to synthesize. In this context hydrophobic semi‐crystalline polymers with low glass transition temperatures, and combined stiffness and flexibility, hav...

Form annehmen: Polyethylen‐Aerogele mit niedriger Dichte und ausgezeichneter mechanischer Belastbarkeit wurden durch Kombination und Maximierung der physikalischen Vernetzung durch Kristallisation sowie der chemischen Vernetzung durch Hydrosilylierungsreaktionen erhalten. Die Materialien weisen bemerkenswerte Formgedächtniseigenschaften auf. Abstr...

Differential scanning calorimetry of high molar mass poly(4‐vinylphenylboronic acid, pinacol ester)s evidenced unusual reactive events above 120 °C, resulting in a high glass‐transition temperature of 220 °C. A reversible ring‐opening reactivity of pinacol boronates is proposed, involving a nucleophilic attack on the sp² boron and subsequent bridgi...

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....

Differential scanning calorimetry of high molar mass poly(4‐vinylphenylboronic acid, pinacol ester)s evidenced unusual reactive events above 120°C, resulting in a high glass‐transition temperature of 220°C. We hypothesize a reversible ring‐opening reactivity of pinacol boronates involving a nucleophilic attack on the sp2 boron and subsequent bridgi...

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...

Nanopapers formed from 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 comb...

Vitrimers are dynamic polymer networks with unique viscoelastic behavior combining the best attributes of thermosets and thermoplastics. Ionic vitrimers 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 r...

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...

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) de...

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 junc...

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 α-azide-ω-alkyne monomers and simultaneous N-alkylation of the resulting 1,4- and 1,5-disubstituted...

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,...

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 glass-like plastic deformation and reprocessing without depolymerization. We disclos...

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...

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 a...

A straightforward and expeditious monotopic approach for the preparation of 1,2,3-triazolium-based poly(ionic liquids) (TPILs) is reported. It is based on the solvent- and catalyst-free polyaddition of an α-azide-ω-alkyne monomer in the presence of methyl iodide or N-methyl bis[(trifluoromethyl)sulfonyl]imide alkylating agents. Poly(1,2,3-triazole)...

Front Cover: 1,2,3-Triazolium-based poly(ionic liquid)s are prepared by a solvent- and catalyst-free monotopic approach based on thermal polyaddition of an α-azide-ω-alkyne and in-situ quaternization of the resulting 1,4-/1,5-disubstituted poly(1,2,3-triazole) s. While a significant reduction in time, number of synthetic and purification steps is a...

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 po...

The present invention relates to a method for synthesizing a supramolecular material comprising: 1—the reaction of at least one carboxylic diacid, or ester or chloride of such a diacid, with, on the one hand, at least one modifier compound bearing both reactive functional groups capable of reacting with the carboxylic acid, ester or acid chloride f...

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 synthe...

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 sl...

Silicon containing block copolymers, such as Poly(styrene-b-dimethylsiloxane) (PS-PDMS), have recently received significant attention for nanolithographic applications [Jung et al., Nano Letters 2010, 10, 1000]. PDMS provides indeed a robust and highly selective mask to oxygen reactive ion etching. In addition, the high Flory-Huggins χPS-PDMS param...

Self-healing materials have the ability to restore autonomously their structural integrity after damage. Such a remarkable property was obtained recently in supramolecular rubbers formed by a network of small molecules associated via hydrogen bonds [1]. Here we explore this self-healing through an original tack experiment where two parts of supramo...

Incorporating reversible bonds in polymer materials is an attractive method for obtaining crosslinked networks, that can still be reshaped or recycled after use. In the scope of this thesis, we synthesized and studied polymer networks maintained through two distinct types of reversible bonds: non-covalent hydrogen bonds and covalent ester bonds abl...

Supramolecular chemistry teaches us to control non-covalent interactions between organic molecules, particularly through the use of optimized building blocks able to establish several hydrogen bonds in parallel as in DNA. This discipline is emerging as a powerful tool in the design of new materials through the concept of supramolecular polymers. Ho...

We have demonstrated recently1 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 w...

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 re...

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 hydr...