A polymer shows thermoset-like stability while displaying melt processability like that of a thermopolymer.

Catalytic control of bond exchange reactions enables healing cross-linked polymer materials under a wide range conditions. The capability at high temperatures is demonstrated for epoxy-acid and epoxy-anhydride thermoset networks in the presence transesterification catalysts. At lower temperatures, are very sluggish, have properties classical epoxy thermosets. Studies model molecules confirmed that kinetics controlled by reaction rate. possibility varying catalyst concentration brings...

Exploiting exchangeable covalent bonds as dynamic cross-links recently afforded a new class of polymer materials coined vitrimers. These permanent networks are insoluble and infusible, but the network topology can be reshuffled at high temperatures, thus enabling glasslike plastic deformation reprocessing without depolymerization. We disclose herein development functional high-value ion-conducting vitrimers that take inspiration from poly(ionic liquid)s. Tunable with ionic content obtained...

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 a exchange process, i.e., de-N-alkylation re-N-alkylation reactions. Herein, highlight the main features of adaptable (CANs) discuss their respective behaviors....

Abstract Vitrimers are dynamic polymer networks with unique viscoelastic behavior combining the best attributes of thermosets and thermoplastics. Ionic vitrimers a recent class materials, where 1,2,3‐triazolium cross‐links reshuffled by trans‐ N ‐alkylation exchange reactions. Comparison properties selection relying on different reactions highlights particularly high viscous flow activation energies reactions, thus providing an enhanced compromise between fast reprocessing at moderately...

We propose a strategy to obtain through facile one-pot synthesis large variety of supramolecular materials that can behave as differently associating low-viscosity liquids, semicrystalline or amorphous thermoplastics, viscoelastic melts rubbers. Such versatility is achieved thanks simultaneous branched backbones and grafting units. This contrasts with usual synthetic pathways rely on functional groups preprepared backbones. use oligocondensation fatty di- triacids diethylenetriamine finely...

Abstract 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 but do not flow relies on use a wide molecular distribution randomly branched oligomers equipped with self‐complementary complementary hydrogen bonding groups. prepared such two steps procedure. In first step, triamine was condensed dimer acids. second obtained were allowed react The molecules...

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 coupling strategy, optimized for low molecular weight diblocks using copper-catalyzed azide–alkyne "click" cycloaddition, was employed to obtain a library PDMS-b-PMMA poly(dimethylsiloxane-block-styrene) (PDMS-b-PS) diblock copolymers. Flory–Huggins interaction parameters,...

Nanopapers containing cellulose nanofibrils (CNFs) are an emerging and sustainable class of high performance materials. The diversification improvement the mechanical functional property space critically depend on integration CNFs with rationally designed, tailor-made polymers following bioinspired nanocomposite designs. Here we combine for first time colloidal dispersions vitrimer nanoparticles (VP) into mechanically coherent nanopaper Vitrimers permanently cross-linked polymer networks...

Polystyrene (PS) is a major commodity polymer widely used in various applications ranging from packaging to insulation thanks its low cost, high stiffness, and transparency as well relatively softening temperature. Similarly all polymers prepared by radical polymerization, PS constituted of C–C backbone thus not degradable. To confer degradability such materials, the copolymerization vinyl monomers with cyclic monomer that could undergo ring-opening an efficient method introduce purposely...

A remarkable self-healing property has been achieved recently with rubbers formed by a supramolecular network of oligomers. Here we explore this through tack-like experiment where two parts rubber are simply brought into contact and then taken apart. These experiments reveal that the self-adhesive strength surfaces is significantly enhanced fracture or other damaging processes. The mechanical energy required to separate were back about one order magnitude larger than for close thermodynamic...

Thermoplastic elastomers (TPEs) are designed by embedding discrete glassy or semicrystalline domains in an elastomeric matrix. Typical styrenic-based amorphous TPEs made of linear ABA-type triblock copolymers, where the volume fraction f A is typically less than 0.3. This limitation ultimately restricts range mechanical strength attainable with these materials. We had previously predicted using self-consistent field theory (SCFT) that A(BA′)n miktoarm block copolymers approximately 8:1 ratio...

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 remote preparation distribution hyperpolarized samples from dedicated facilities. Here we show the synthesis hyperpolarizing polymers (HYPOPs) that can generate radical- contaminant-free within minutes with lifetimes exceeding hours solid state. HYPOPs...

A designed library of covalent adaptable networks (CANs) having 1,2,3-triazolium dynamic cross-links are obtained through the combination solvent- and catalyst-free thermally induced azide–alkyne cycloaddition N-alkylation reactions. The use rigid heterocyclic or aromatic segments affords CANs with a greatly extended range thermomechanical profiles, Tgs up to 146 °C, dramatic changes in relaxation times (from 1.5 h less than 2 min at 150 °C) depending on chemical structure N-substituents...

Abstract We combine the supramolecular chemistry of heterocyclic ureas with epoxides to synthesize new crosslinked materials incorporating both chemical and hydrogen‐bonded links. A two‐step facile solvent‐free procedure is used obtain chemically thermally stable networks from widely available ingredients: epoxy resins fatty acids. The density physical crosslinks controlled by stoichiometry reactants use a proper catalyst limit side reactions. Depending on stoichiometry, wide range...

Abstract 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 viscosity modifier of interface compatibilizer yields well‐dispersed phases with fractions up to 75 wt.% in phase. These can be easily reprocessed by multiple shredding‐injection cycles processed high‐shear conditions capillary rheometry. Rheological analyses...

The activity of various additives promoting siloxane equilibration reactions is examined and quantified on model compounds. We found in particular that the "superbase" phosphazene derivative P4 -t Bu can promote very fast exchanges (a few seconds at 90 °C) even low concentration (<0.1 wt %). demonstrate permanent silicone networks be transformed into reprocessable recyclable dynamic by mere introduction such additives. Annealing high temperature degrades deactivates features networks,...

Abstract This work investigates the correlation between formulation of waterborne acrylic pressure‐sensitive adhesives (PSAs) and their resulting adhesive performance. A library n ‐butyl acrylate‐based latexes is synthesized via miniemulsion polymerization. Controlled variations in composition these polyacrylates – such as inclusion rigid comonomers, latent crosslinkers chain transfer agents enabled precise control over key network structures particles leading then to a range physical...

A modular and robust method for preparing end-functionalized donor–acceptor (D–A) narrow bandgap conjugated polymers is reported that avoids multistep reactions postpolymerization modification. The strategy well-controlled affords functional materials with predictable molecular weight high end-group fidelity. To exemplify this synthetic strategy, based on PDPP2FT were prepared contain perylene diimide (PDI) units at the chain-ends. Monte Carlo simulations confirm degree of chain-end...

A straightforward and expeditious monotopic approach for the preparation of 1,2,3‐triazolium‐based poly(ionic liquids) (TPILs) is reported. It based on solvent‐ catalyst‐free polyaddition an α‐azide‐ω‐alkyne monomer in presence methyl iodide or N ‐methyl bis[(trifluoromethyl)sulfonyl]imide alkylating agents. Poly(1,2,3‐triazole)s generated bulk by thermal azide–alkyne cycloaddition (AAC) are quaternized in‐situ to afford TPILs composed 1,3,4‐ 1,3,5‐trisubstituted 1,2,3‐triazolium units. The...

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 the ester bonds formed during curing. After drying latexes, trans-esterification exchanges occurring at high temperatures through interparticle interfaces induces an efficient sintering into homogeneous polymer films.

We designed efficient precursors that combine complementary associative groups with exceptional binding affinities and thiocarbonylthio moieties enabling precise RAFT polymerization. Well defined PS PMMA supramolecular polymers molecular weights up to 30 kg mol(-1) are synthesized shown form highly stable diblock copolymers (BCPs) when mixed, in non-polar solvents or the bulk. Hierarchical self-assembly of such BCPs by thermal annealing affords morphologies excellent lateral order,...

In addition to the traditional parameters of chi (χ) and degree polymerization (N), we demonstrate that segregation strength a diblock copolymer can be increased by introduction an ionic unit at junction two blocks. Compared neutral linking groups, electrostatic interactions between counterions adjacent domain junctions leads enthalpy, strength, phase separation. As result, order disorder transition temperatures block copolymers with 1,2,3-triazolium were observed significantly higher than...

Among possible routes toward isocyanate-free polyurethanes, aminolysis of cyclic carbonates leading to polyhydroxyurethanes (PHUs) is one the most promising pathways. Herein, we describe solvent-free synthesis shape memory PHU networks from diglycerol dicarbonate through reactive extrusion with varying amounts primary and secondary triamines, tris(2-aminoethyl)amine tris(2-(methylamino)ethyl)amine). Depending on composition system, glass transition temperature can be finely tuned in 20–40 °C...