Intrinsically Self-Healing Polymers: From Mechanistic Insight to Current Challenges

Chemical Reviews, Journal Year: 2022, Volume and Issue: 123(2), P. 701 - 735

Published: Dec. 28, 2022

Self-healing materials open new prospects for more sustainable technologies with improved material performance and devices' longevity. We present an overview of the recent developments in field intrinsically self-healing polymers, broad class based mostly on polymers dynamic covalent noncovalent bonds. describe current models mechanisms discuss several examples systems different types bonds, from various hydrogen bonds to The advances indicate that most intriguing results are obtained have combined These demonstrate high toughness along a relatively fast rate. There is clear trade-off relationship between rate mechanical modulus materials, we propose design principles toward surpassing this trade-off. also applications summarize challenges field. This review intends provide guidance intrinsic required properties.

Language: Английский

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A Highly Dynamic Covalent Polymer Network without Creep: Mission Impossible?

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(48)

Published: Sept. 26, 2022

Dynamic covalent polymer networks provide an interesting solution to the challenging recyclability of thermosets and elastomers. One remaining design constraints, however, is balancing thermal reprocessability in form material flow with dimensional stability during use. As a result, many chemistries are being investigated order improve bond reactivity control robustness. This Minireview highlights number promising concepts, particular emphasis on disconnecting chemical low high temperature regimes obtain creep resistant, yet highly dynamic networks. In addition, we will highlight impact sharp changes when applying extrapolation-based approaches rheological analysis. confident that abandoning myth "permanent" aid development sustainable polymeric materials can truly combine benefits thermoplastic thermoset behaviour.

Language: Английский

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Self-compliant ionic skin by leveraging hierarchical hydrogen bond association

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 30, 2024

Abstract Robust interfacial compliance is essential for long-term physiological monitoring via skin-mountable ionic materials. Unfortunately, existing epidermal skins are not compliant and durable enough to accommodate the time-varying deformations of convoluted skin surface, due an imbalance in viscosity elasticity. Here we introduce a self-compliant that consistently works at critical gel point state with almost equal elasticity over super-wide frequency range. The material designed by leveraging hierarchical hydrogen bond association, allowing continuous release polymer strands create topological entanglements as complementary crosslinks. By embodying properties rapid stress relaxation, softness, conductivity, self-healability, flaw-insensitivity, self-adhesion, water-resistance, this fosters excellent cyclically deforming substrates, facilitates acquisition high-fidelity electrophysiological signals alleviated motion artifacts. presented strategy generalizable could expand applicability more complex service conditions.

Language: Английский

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A tutorial review of linear rheology for polymer chemists: basics and best practices for covalent adaptable networks

Polymer Chemistry, Journal Year: 2024, Volume and Issue: 15(9), P. 815 - 846

Published: Jan. 1, 2024

This tutorial review of linear viscoelasticity is targeted at polymer chemists working with covalent adaptable networks. It provides an overview concepts, analysis, misconceptions, and best practices for rheological experiments.

Language: Английский

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Entropy-Driven Design of Highly Impact-Stiffening Supramolecular Polymer Networks with Salt-Bridge Hydrogen Bonds

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7533 - 7542

Published: March 7, 2024

Impact-stiffening materials that undergo a strain rate-induced soft-to-rigid transition hold great promise as soft armors in the protection of human body and equipment. However, current impact-stiffening materials, such polyborosiloxanes shear-thickening fluids, often exhibit limited response. Herein, we propose design strategy for fabricating highly supramolecular polymer networks by leveraging high-entropy-penalty physical interactions. We synthesized fully biobased comprising poly(α-thioctic acid) arginine clusters, whose chain dynamics are governed specific guanidinium-carboxylate salt-bridge hydrogen bonds. The resulting material exhibits an exceptional response ∼2100 times, transitioning from dissipating state (21 kPa, 0.1 Hz) to stiffened glassy (45.3 MPa, 100 with increasing rates. Moreover, material's high energy-dissipating hot-melting properties bring excellent damping performance easy hybridization other scaffolds. This entropy-driven approach paves way development next-generation soft, sustainable, impact-resistant materials.

Language: Английский

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Taking dynamic covalent chemistry out of the lab and into reprocessable industrial thermosets

Nature Reviews Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 31, 2025

Language: Английский

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Influence of theα-Methyl Group on Elastic-To-Glassy Transition of Supramolecular Hydrogels with Hydrogen-Bond Associations

Macromolecules, Journal Year: 2022, Volume and Issue: 55(17), P. 7512 - 7525

Published: Sept. 1, 2022

The molecular chemical structure has a decisive influence on physicochemical properties of polymer materials, which becomes more complex for hydrogels with dense associative interactions. Recently, we have developed series tough supramolecular robust hydrogen-bond associations, and the gels severely depend composition copolymers. Here, examine mechanical viscoelastic behaviors these synthesized from copolymerization acrylamide/methacrylamide acrylic acid/methacrylic acid varied α-methyl group basic unit. obtained four kinds as-prepared exhibit distinct performances dynamics, evolving elastic to glassy state increase in number groups. Rheological dynamic spectra follow time–temperature superposition principle, are used elucidate correlation between dynamics gel materials. incorporation hydrophobic effectively improves chain rigidity enhances associations. Furthermore, methyl carboxylic unit strengthens significantly than that acrylamide unit, also results stability water. This comparative study discloses effect copolymers hydrogels, should be informative understand structure–property relationship other soft materials

Language: Английский

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Controlling Dynamics of Associative Networks through Primary Chain Length

Macromolecules, Journal Year: 2022, Volume and Issue: 55(22), P. 10052 - 10061

Published: Nov. 2, 2022

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 molecular weight dispersity primary tuned actively tailor dynamics resulting networks. Vitrimers similar composition cross-link density made from below well above entanglement exhibited distinct viscoelastic properties energies activation ranging 93 264 kJ/mol. Resistance creep increased dramatically increasing chain length. Finally, blending prepolymers skew Mn above/below Me was demonstrated, showing distinguishable effect prepolymer breadth skewness on vitrimer flow. Our results suggest tailoring chain-length distribution is viable strategy design materials predictable customizable behavior.

Language: Английский

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Viscoelasticity of Polymers with Dynamic Covalent Bonds: Concepts and Misconceptions

Macromolecules, Journal Year: 2023, Volume and Issue: 56(21), P. 8688 - 8696

Published: Nov. 3, 2023

Polymers with dynamic covalent bonds are an exciting class of materials properties and potential applications that rapidly gain significant attention from diverse scientific communities. While the number publications on this emerging topic increases exponentially, navigating through literature reveals a series physical inconsistencies in previously established concepts some misconceptions data analysis interpretation. The current paper presents practices often applied to characterization systems emphasizes particular may lead critical divergences misinterpretations results. We particularly focus should be avoided interpretation stress–relaxation viscoelastic estimates bond dissociation energy. Instead, we suggest using traditional approaches have been polymer for decades. Lastly, emphasize challenges full understanding microscopic behavior vitrimers.

Language: Английский

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Synthesis and characterization of polyolefin thermoplastic elastomers: A review

The Canadian Journal of Chemical Engineering, Journal Year: 2023, Volume and Issue: 101(9), P. 4886 - 4906

Published: Jan. 4, 2023

Abstract Polyolefin thermoplastic elastomers (TPE‐Os) are high‐performance polyolefins consisting of both plastic and rubber phases. Compared with other elastomers, the TPE‐Os possess better chemical stability, transparency, re‐processability, electrical insulation, which renders their broad applications possible. By manipulating chain structures topologies TPE‐Os, differently structured improved thermal mechanical properties have been developed, including ethylene α‐olefin random copolymers (POEs), olefin block (OBCs), comb‐shaped polyolefin (CPOEs), dynamically cross‐linked elastomers. Herein, we review synthesis POE, OBC, CPOE, dynamical elastomer, catalyst systems, polymerization techniques, processes, kinetic modelling. The characterization relationships between TPE‐O structure, aggregated state, product performance discussed. future development higher‐performance is envisaged.

Language: Английский

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