Creep-Resistant Covalent Adaptable Networks with Excellent SelfHealing and Reprocessing Performance via Phase-Locked Dynamic Covalent Benzopyrazole-Urea Bonds

Covalent adaptive networks(CANs)are capable of undergoing segment rearrangement after being heated,which endows the materials with excellent self-healing and reprocessing performance,providing an efficient solution to the environment pollution caused by the plastic wastes.The main challenge remains in developing CANs with both excellent reprocessing performance and creep-resistance property.In this study,a series of CANs containing dynamic covalent benzopyrazole-urea bonds were developed based on the addition reaction between benzopyrazole and isocyanate groups.DFT calculation confirmed that relatively low dissociation energy is obtained through undergoing a five-member ring transition state,confirming excellent dynamic property of the benzopyrazole-urea bonds.As verified by the FTIR results,this nice dynamic property can be well maintained after incorporating the benzopyrazole-urea bonds into polymer networks.Excellent self-healing and reprocessing performance is observed by the 3-ABP/PDMS elastomers owing to the dynamic benzopyrazole-urea bonds.Phase separation induced by the aggregation of the hard segments locked the benzopyrazole-urea bonds,which also makes the elastomers display excellent creep-resistance performance.This hard phase locking strategy provides an efficient approach to design CANs materials with both excellent reprocessing and creep-resistance performance.

Conductive,Stretchable,and Self-healing Ionic Gel Based on Dynamic Covalent Bonds and Electrostatic Interaction

Integrating multiple functions into one gel that can be widely applied to electronic devices as well as chemical and biomedical engineering remains a big challenge.Here,a multifunctional ionic liquid/dynamic covalent bonds (ionic/DCB) type gel was designed and synthesized via one-pot polymerization.With the assistance of electrostatic interaction provided by the imidazolium cations of IL and the reversible DCB of boronic ester,as-prepared ionic/DCB gel showed good stretchable properties and high ionic conductivity at ambient conditions.In addition,the electrostatic interaction between imidazolium cations and sulfonate anions and the reversible DCB led to enhanced chain mobility and thereby excellent self-healing properties.Particularly,sulfonate anions in ionic/DCB gel could alleviate the migration of electronegative polysulfide and promote the transportation of electropositive lithium ion in lithium-sulfur battery system.Therefore,this work provides a new insight to promote the current research on self-healing gels,hopefully expanding their applications in electronic devices.

An interfacial robust and entire self-healing ionogel-elastomer hybrid for elastic electronics enables discretionary assembly and reconfiguration

Inspired by the multi-layer architecture of mammal skins,interfacial robust,stretchable,and entirely healable gel-elastomer hybrids hold great potential in diverse fields including biomedical devices,wearable electrical devices,and soft robotics.However,existing gel-elastomer hybrids have numerous limitations including low interfacial bonding toughness,complex and time-consuming preparation process,unhealable,and non-reconfiguration.Herein,we propose a simple and general chemical strategy through the interfacial dynamic bonding between gel and elastomer to simultaneously address the abovementioned obstacles.Dynamic covalent bonds readily and repeatably covalent bonding ionogel and elastomer(interfacial toughness:390 J m^(-2)),endowed the hybrids with entire self-healing features like skin and enabled discretionary assembly and reconfiguration.Moreover,this strategy resolved the troublesome contradiction between interfacial stability and reconfiguration.Taking advantage of the aforementioned features,we readily constructed a multi-module,self-healing,self-powered,and realtime monitoring of personal status integrated elastic electronics,which could simply reconfigure the output signal of elastic electronics into an input signal of the devices-braille keyboard.

3D-printed self-healing,biodegradable materials and their applications

3D printing is a versatile technology capable of rapidly fabricating intricate geometric structures and enhancing the performance of flexible devices in comparison to conventional fabrication methods.However,3D-printed devices are susceptible to failure as a result of minuscule structural impairments,thereby impacting their overall durability.The utilization of self-healing,biodegradable materials in 3D printing holds immense potential for increasing the longevity and safety of devices,thereby expanding the application prospects for such devices.Nevertheless,enhancing the self-repairing capability of devices and refining the 3D printing performance of self-healing materials are still considerable challenges that need to be addressed to achieve optimal outcomes.This paper reviews recent developments in the field of advancements in 3D printing using self-healing and biodegradable materials.First,it investigates self-healing and biodegradable materials that are compatible with 3D printing techniques,discussing their printability,material properties,and factors that influence print quality.Then,it explores practical applications of selfhealing and biodegradable 3D printing technology in depth.Finally,it critically offers practical perspectives on this topic.

Solvent-Free Synthesis of Self-Healable and Recyclable Crosslinked Polyurethane Based on Dynamic Oxime-Urethane Bonds

Polyurethane is widely used for its versatility in design and range of performance.Self-healing and recyclable dynamic polyurethane networks have attracted extensive attention due to their potential to extend service life and ensure safety in use,as well as to promote sustainable use of resources.Developing green and environment-friendly methods to obtain this material is an interesting and challenging task,as the majority of current dynamic polyurethane networks utilize the solution polymerization method.The use of solvents makes the processes complicated,harmful to environment,and increase the cost.Poly(oxime-urethanes)(POUs)are emerging dynamic polyurethanes and show great potential in diverse fields,such as biomaterials,hot melt adhesives,and flexible electronics.In this study,we utilized the solubility properties of dimethylglyoxime in raw material poly(ethylene glycol)to prepare POUs through bulk polymerization for the first time.This method is simple,convenient and cost-efficient.Simultaneously,copper ion coordination improves POUs strength and dynamic properties,with mechanical strength up from 0.54 MPa to 1.03 MPa and self-healing recovery rate up from 85.5%to 91.8%,and activation energy down from 119.6 k J/mol to 95.4 k J/mol.To demonstrate the application of this technology,self-healing and stretchable circuits are constructed from this dynamic polyurethane network.

Dynamic Oxime-Urethane Bonds, a Versatile Unit of High Performance Self-healing Polymers for Diverse Applications

Oxime-urethane bond featuring with high reversibility even at room temperature and multiple reactivity is an emerging dynamic covalent bond,and has shown great potential for self-healing polymers,which are one of the most attractive development directions for next generation of polymeric materials.In this review,recent progresses on the oxime-urethane-based self-healing polymers,including their designs and applications in diverse fields such as biomedicine,flexible electronics,soft robots,3D printing,protective materials,and adhesives,are summarized,and outlooks on the future development of this field are discussed.

Functional polymer materials based on dynamic covalent chemistry

In the past two decades,dynamic covalent chemistry has been greatly developed,which is mainly reflected in two aspects:1.new dynamic covalent bonds(DCBs)are continuously discovered;2.various DCBs have been introduced into polymer materials for different functions.These functional polymer materials have brought new opportunities for sustainable development.In this review,we provide an overview of various functions endowed by DCBs in polymer materials,including self-healing,chemical recycling,and shape controlling.Particularly,we pay much attention to the three-dimensional(3D)shape reconfiguration/programming,surface patterning,and reversible actuation.In addition,we also give the current issues,challenges,and opportunities on DCBs-containing materials and point out its developing directions in the future.

Self-healing Hydrogelsand Underlying Reversible Intermolecular Interactions

Self-healing hydrogels have attracted growing attention over the past decade due to their biomimetic structure,biocompatibility,as well as enhanced lifespan and reliability,thereby have been widely used in various biomedical,electrical and environmental engineering applications.This feature article has reviewed our recent progress in self-healing hydrogels derived from mussel-inspired interactions,multiple hydrogen-bonding functional groups such as 2-ureido-4[1H]-pyrimidinohe(UPy),dynamic covalent bonds(eg,Schiff base reactions and boronic ester bonds).The underlying molecular basics of these interactions,hydrogel preparation principles,and corresponding performances and applications are introduced.The underlying reversible intermolecular interaction mechanisms in these hydrogels were investigated using nanomechanical techniques such as surface forces apparatus(SFA)and atomic force microscopy(AFM),providing fundamental insights into the self-healing mechanisms of the hydrogels.The remaining challenging issues and perspectives in this rapidly developing research area are also discussed.

A Strong and Rigid Coordination Adaptable Network that Can Be Reprocessed and Recycled at Mild Conditions

The investigation of covalent adaptable networks(CANs)is expanding rapidly due to the growing demand for sustainable materials,as CANs show thermoset-like behavior and yet can be reprocessed,recycled,and healed.However,most of the CANs reported so far have a trade-off between mechanical strength and reversible properties and often show performance reduction after reprocessing and/or recycling.Herein,we designed and synthesized a coordination adaptable network(CoAN)by crosslinking low-molecular-weight monomers with abundant coordination bonds.Owning to its excellent variable-stiffness property,leading to high stiffness at ambient conditions and low viscosity at elevated temperature,the as-prepared CoAN showed high mechanical rigidity but could be reprocessed rapidly and recycled at mild conditions.After reprocessing or recycling,the mechanical properties of the samples showed no performance reduction,compared with a pristine sample.Density functional theory calculations showed that free thiol ligands played a key role in reducing the activation energy for bond exchange.When used as binders for composites,the embedded carbon fibers could be recycled rapidly and still maintain the original microstructure.The material also showed temperature-sensitive dielectric and conductive properties due to the release of metal ions upon heating.Overall,such performances are superior among the CANs reported previously.