The classical division of polymeric materials into thermoplastics and thermosets based on covalent network structure often implies that these categories are distinct irreconcilable. Yet, the past two decades have seen extensive development bridge this gap through incorporation dynamic crosslinks, enabling them to behave as both robust networks moldable plastics. Although their potential utility is significant, growth adaptable (CANs) has obscured line between "thermoplastic" "thermoset"...

Cross-linked networks feature exceptional chemical and mechanical resilience but consequently lack recyclability. Vitrimers have emerged as a class of materials that the robustness thermosets recyclability thermoplastics without compromising network integrity. Most examples vitrimers involved new polymers with exchangeable bonds within their backbones. In pursuit more universal, commercially viable route, we propose method utilizing available inexpensive reagents to prepare from vinyl...

In this report, we merge block copolymers with vitrimers in an effort to realize the prospect of higher-order, nanoscale control over associative cross-link exchange and flow. We show use controlled polymerization as a vital tool understand fundamental structure–property effects through precise polymer architecture molecular weight. Vitrimers derived from self-assembling exhibit superior resistance macroscopic deformation comparison their analogs generated statistical copolymers. Our results...

Dynamic networks couple the robust nature of thermosets with shapeability and recyclability thermoplastics. Though a wealth exchange chemistries can be leveraged to fabricate dynamic networks, reversibly cross-linked systems that are comprised primarily chains nonexchangeable backbones increase network complexity render flow behavior difficult predict. Here, we report polymethacrylate-based vitrimers prepared by cross-linking β-ketoester-containing polymers multifunctional amines demonstrate...

Thermosets composed of cross-linked polymers demonstrate enhanced thermal, solvent, chemical, and dimensional stability as compared to their non-cross-linked counterparts. However, these often-desirable material properties typically come at the expense reprocessability, recyclability, healability. One solution this challenge comes from construction that are reversibly cross-linked. We relied on lessons Nature present supramolecular polymer networks comprised cooperative Janus-faced hydrogen...

In this study, we explore the distinct reactivity patterns between frontal ring-opening metathesis polymerization (FROMP) and room-temperature solventless (ROMP). Despite their shared mechanism, find that FROMP is less sensitive to inhibitor concentration than ROMP. By increasing initiator-to-monomer ratio for a fixed inhibitor/initiator quantity, reduction in ROMP background at room temperature (i.e., increased resin pot life). At elevated temperatures where dissociation prevails,...

We report a straightforward and scalable method for the generation of polystyrene-based vinylogous urethane vitrimers using conventional radical polymerization. The copolymerization commercially available inexpensive monomers styrene (2-acetoacetoxy)ethyl methacrylate produced β-ketoester-functional network precursors on multigram scale, which could be cross-linked with diamines to yield thermally robust vitrimer materials. Vitrimers were (re)processed over three destruction/compression...

Frontal ring-opening metathesis polymerization (FROMP) is a rapid, low-energy manufacturing reaction that useful for curing thermosetting materials. FROMP of dicyclopentadiene (DCPD) results in poly(dicyclopentadiene) (p(DCPD)), tough thermoset with excellent mechanical performance and chemical stability. Like most thermosets, p(DCPD) cannot be reprocessed therefore difficult to recycle. Previous work demonstrated the incorporation small quantity cleavable units strand segments networks...

Tunable molecular weight and well-defined polydispersity are the hallmarks of a controlled polymerization. This process relies on vanishingly small termination rates, minimal chain transfer, initiation rates faster than propagation rates. Ring-opening metathesis polymerization (ROMP) is well-known based opening strained cyclic olefins. The exothermic nature ROMP allows rapid conversion neat monomers to polymers through frontal (FROMP). Unlike traditional ROMP, FROMP uses heat from olefins...

We describe the application of a novel eosin Y (EY)-derived polymer photocatalyst for synthesis polymeric bioconjugates. The photocatalyst, copolymer acrylate and N-isopropylacrylamide, can induce light-mediated reversible-deactivation radical polymerization in biologically benign conditions. Heating reaction mixture to 37 °C causes precipitation hydrophilic-to-hydrophobic transition, allowing simple purification polymer–protein conjugates via filtration without compromising enzyme activity....

This works reports on novel polyimine vitrimers from a bio-based and fully aromatic scaffold. The dynamic networks possess high-performance thermal stability charring behavior with facile thermomechanical viscoelastic tunability.

A photoactive eosin Y-derived monomer was developed that can induce photoelectron/energy transfer, while simultaneously partaking in the polymerization as a monomer, affording polymer catalysts with tunable Y incorporations.

Postpolymerization modification is a powerful strategy for the rapid generation of functional polymers, but availability reactions that enable fast and selective functionalization using only benign materials remains limited. We report utility condensation reaction between β-ketoesters primary amines efficient polymer at room temperature. Under Brønsted acid catalysis, polymers containing pendent could be functionalized with diverse scope various polar nonpolar groups. The formed enaminone...

Abstract Herein we introduce chalcogen squares via selenadiazole motifs as a new class of dynamic supramolecular bonding interactions for the modification and control soft matter materials. We showcase in networks varying primary chain length prepared through polymerization using tandem step‐growth/Passerini multicomponent reactions (MCRs). Compared to controls lacking motif, these display increased glass transition temperatures moduli due linkages formed between chains. These elastomeric...

The rate of frontal ring-opening metathesis polymerization (FROMP) using the Grubbs generation II catalyst is impacted by both concentration and choice monomers inhibitors, usually organophosphorus derivatives. Herein we report a data-science-driven workflow to evaluate how these factors impact FROMP long formulation mixture stable (pot life). Using this workflow, built classification model single-node decision tree determine simple phosphine structural descriptor (Vbur-near) can bin versus...

Frontal ring-opening metathesis polymerization (FROMP) involves a self-perpetuating exothermic reaction, which enables the rapid and energy-efficient manufacturing of thermoset polymers composites. Current state-of-the-art reaction-diffusion FROMP models rely on phenomenological description olefin kinetics, limiting their ability to model governing thermo-chemical processes. Furthermore, existing are unable predict variations in kinetics with changes resin composition as result limited...

We investigated intra-chain multicomponent reactions to synthesize single-chain nanoparticles (SCNP) containing sequence-defined segments at each cross-link, creating materials featuring multiple protein-inspired elements.

Two frontal polymerization (FP) mechanisms, ring-opening metathesis (FROMP) of dicyclopentadiene and radical (FRaP) benzyl acrylate hexanediol diacrylate, were combined for rapid manufacturing welded thermoset materials. Leveraging the immiscibility two different FP resins, thermosets gradient foams varying composition achieved by switching mechanisms. The adhesion strength materials differed depending on originating mechanism. Finally, porosity homogeneity generated through initiation from...

This study explores the relationship between monomer stereochemistry and materials properties of thermosets generated by frontal ring-opening metathesis polymerization (FROMP). The exo- endo-stereoisomers dicyclopentadiene (DCPD) undergo rapid FROMP to fabricate robust within seconds. exo-isomer provides significant benefits compared commonplace endo-DCPD resins; exo-DCPD supports faster fronts (≈3 times faster) than endo-analogue is an easier-to-handle liquid at room temperature. work among...

The intra-chain radical polymerization of pendant methacryloyl decorated poly(norbornene) imides is a viable route to single-chain nanoparticles, however this process complicated by adventitious molecular oxygen.

Frontal ring-opening metathesis polymerization (FROMP) presents an energy-efficient approach to produce high-performance polymers, typically utilizing norbornene derivatives from Diels-Alder reactions. This study broadens the monomer repertoire for FROMP, incorporating cycloaddition product of biosourced furan compounds and benzyne, namely 1,4-dihydro-1,4-epoxynaphthalene (HEN). We conducted a computational screening products, selecting products with resistance retro-Diels-Alder but also...

Frontal ring-opening metathesis polymerization (FROMP) involves a self-perpetuating exothermic reaction, which enables the rapid and energy-efficient manufacturing of thermoset polymers composites. Current state-of-the-art reaction-diffusion FROMP models rely on phenomenological description olefin kinetics, limiting their ability to model governing thermo-chemical processes. Furthermore, existing are unable predict variations in kinetics with changes resin composition as result limited...