Structure–Reactivity–Property Relationships in Covalent Adaptable Networks

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(49), P. 22358 - 22377

Published: Nov. 29, 2022

Polymer networks built out of dynamic covalent bonds offer the potential to translate control and tunability chemical reactions macroscopic physical properties. Under conditions at which these occur, topology adaptable (CANs) can rearrange, meaning that they flow, self-heal, be remolded, respond stimuli. Materials with properties are necessary fields ranging from sustainability tissue engineering; thus time scale network rearrangement must compatible intended use. The mechanical CANs based on thermodynamics kinetics their constituent bonds. Therefore, strategies needed connect molecular worlds. In this Perspective, we analyze structure-reactivity-property relationships for several classes CANs, illustrating both general design principles predictive linear free energy (LFERs) applied CANs. We discuss opportunities in field develop quantitative open challenges.

Language: Английский

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Introducing Dynamic Bonds in Light‐based 3D Printing

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(20)

Published: April 23, 2023

Abstract Light‐based 3D printing has received significant attention due to several advantages including high speed and resolution. Along with the development of new technologies, material design is key for next generation light‐based printing. Conventional printable polymeric materials, also known as photopolymers or photoresins, often lead thermosets–polymer networks cross‐linked by permanent covalent bonds which bring limited adaptability restricted reprocessability. Dynamic that can reversibly break reform enable network rearrangement, thereby offering unprecedented properties materials such adaptability, self‐healing, recycling capabilities. Hence, introducing dynamic into a promising strategy further expand meet diverse application scenarios printed multi‐functional moreover more demanding sustainable nature‐inspired considerations (e.g., self‐healing). Herein, an overview recent advances in printing, aiming bridge these two research fields presented. Importantly, current challenges are analyzed perspectives developing their potential applications provided.

Language: Английский

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High-Performance Recyclable and Malleable Epoxy Resin with Vanillin-Based Hyperbranched Epoxy Resin Containing Dual Dynamic Bonds

ACS Sustainable Chemistry & Engineering, Journal Year: 2023, Volume and Issue: 11(30), P. 11077 - 11087

Published: July 18, 2023

Dynamic covalent polymer networks represent new opportunities in the design of sustainable epoxy resins due to their excellent malleability and reprocessability; however, adaptable network is usually accompanied by low glass transition temperature, poor creep resistance, mechanical brittleness. Herein, we demonstrate a vanillin-based hyperbranched resin (VEHBP) containing disulfide imine dynamic bonds for recyclable malleable with high temperature (Tg), significantly improved properties. The 5%VEHBP exhibited 175 °C 130 34.1, 19.7, 173.3% increase tensile strength, storage modulus, toughness respectively, compared neat resin. Meanwhile, topological structure VEHBP complemented dual endowed these materials self-healing ability, reprocessability, degradability, which represents an important step toward fabrication high-performance networks.

Language: Английский

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Epoxy Adhesives with Reversible Hardeners: Controllable Thermal Debonding in Bulk and at Interfaces

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(31)

Published: May 18, 2023

Abstract On‐demand adhesive dismantling has the potential to improve multimaterial product recycling, but its implementation been hampered by a critical trade‐off between strong bonding and easy debonding. As result, temperature range in which these temporary adhesives can be used is relatively limited. Here, new class of dynamic epoxy resins reported that significantly extends this upper limit still achieves fast Specifically, two types polyamidoamine curing agents for hardening are developed, being polysuccinamides (PSA) polyglutaramides (PGA). debonding/rebonding process PSA especially PGA linkages more thermally demanding at same time robust than previously covalent systems, resulting materials triggered high temperatures, remain bonded over wide range. The versatility system demonstrated classical bulk formulations, as well linking PSA‐ or PGA‐functionalized surface. an attractive drop‐in strategy achieved producing debondable rebondable adhesives, with complementarity existing resin technologies applicable industrially relevant window.

Language: Английский

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Circularity in polymers: addressing performance and sustainability challenges using dynamic covalent chemistries

Chemical Science, Journal Year: 2023, Volume and Issue: 14(20), P. 5243 - 5265

Published: Jan. 1, 2023

This review provides a multidisciplinary overview of the challenges and opportunities for dynamic covalent chemistry-based macromolecules towards design new, sustainable, recyclable materials circular economy.

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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Mechanically Robust, Recyclable, and Self‐Healing Polyimine Networks

Advanced Science, Journal Year: 2023, Volume and Issue: 10(19)

Published: April 23, 2023

To achieve energy saving and emission reduction goals, recyclable healable thermoset materials are highly attractive. Polymer copolymerization has been proven to be a critical strategy for preparing high-performance polymeric materials. However, it remains huge challenge develop Here, polyimine dynamic networks based on two monomers with bulky pendant groups, which not only displayed mechanical properties higher than the strong tough polymers, e.g., polycarbonate, but also excellent self-repairing capability recyclability as thermosets developed. Owing stability of conjugation effect by aromatic benzene rings, final far more stable reported counterparts, exhibiting hydrolysis resistance under both alkaline condition most organic solvents. These structure can completely depolymerized into recovery in an acidic aqueous solution at ambient temperature. Resulting from units, this method allows exchange reactions vitrimer easily within minutes self-healing function. Moreover, introduction trifluoromethyl diphenoxybenzene backbones significantly increases tensile This work provides effective fabricating polymer multiple functions.

Language: Английский

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Chemically Recyclable and Upcyclable Epoxy Resins Derived from Vanillin

ACS Sustainable Chemistry & Engineering, Journal Year: 2023, Volume and Issue: 11(22), P. 8308 - 8316

Published: May 22, 2023

Epoxy resins constitute a very significant portion of all high-performance plastics due to their excellent thermal and mechanical properties that appear in wide range applications. Nevertheless, traditional epoxy networks show limitations regarding chemical recycling covalently crosslinked structures. The current methods recycle are not indeed through sustainable ways, but this issue could be solved by developing smart monomers with functional groups, which can switched between polymerized depolymerized states. Herein, we developed two bio-based liquid based on vanillin structures containing aldehyde, acetal, oxirane-ring functionalities. These were solvent-free conditions using commercially available diamines, resulting double-dynamic imine-acetal-containing thermosets. combine the systems dynamic polymers. Most importantly, such thermosets fully into vanillin, reused for preparation original monomers, mixture well-defined polyols, was upcycled polyurethane.

Language: Английский

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Thermally Latent Bases in Dynamic Covalent Polymer Networks and their Emerging Applications

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(24)

Published: March 14, 2023

A novel strategy allowing temporal control of dynamic bond exchange in covalently crosslinked polymer networks via latent transesterification catalysts is introduced. Obtained by a straightforward air- and water-tolerant synthesis, the catalyst designed for an irreversible temperature-mediated release strong organic base. Its long-term inactivity at temperatures below 50 °C provides unique opportunity to equip covalent with creep resistance high bond-exchange rates, once activated. The presented thermally base conveniently introducible readily available building blocks and, as proof concept, applied radically polymerized thiol-ene network. Light-mediated curing used 3D-printing functional objects, on which possibility spatially controlled reshaping welding based illustrated. Since activated, limitations regarding sample geometry optical transparency do not apply, facilitates transfer well-established industrial technologies. Consequently, fiber-reinforced highly filled magneto-active composites are fabricated thermal approach. on-demand activation demonstrated (magneto-assisted) experiments, highlighting wide range potential future applications offered concept.

Language: Английский

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β-Triketones as Reactive Handles for Polymer Diversification via Dynamic Catalyst-Free Diketoenamine Click Chemistry

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 16257 - 16267

Published: June 4, 2024

The spontaneous condensation of amines with β-triketones (TK), forming β,β′-diketoenamines (DKE) and releasing water as the sole byproduct, exhibits many hallmarks "click" reactions. Such characteristics render TKs a highly advantageous platform for efficient polymer diversification, even in biological contexts. Leveraging reversible addition–fragmentation chain transfer (RAFT) photoiniferter polymerization novel TK-containing vinylic monomers, we synthesized polymers containing pendent excellent control molecular weights, excess 106 g mol–1. Under mild, catalyst-free conditions, poly(β-triketone methacrylate) could be modified diverse scope plethora functional groups. high efficiency this functionalization approach was further emphasized when grafting-to poly(ethylene glycol)-amine resulting bottlebrushes weights reaching 2.0 × 107 Critically, while formed DKE linkages are stable under ambient they undergo catalyst-free, dynamic transamination at elevated temperatures, paving way associative covalent adaptable networks. Overall, introduce triketone moieties into methacrylate acrylamide polymers, establishing postpolymerization modification technique that facilitates ligation permissible conditions.

Language: Английский

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