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

Lijsebetten, Filip Van; Debsharma, Tapas; Winne, Johan M.; Prez, Filip E. Du

doi:10.1002/ange.202210405

Cited by 6 publications

(6 citation statements)

References 116 publications

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“…To our knowledge, the kinetics of self-healing in CANs have not been directly measured and quantitatively compared to k a or k ex . 74 In the supramolecular network literature, Scherman has demonstrated this quantitative relationship for a host−guest system using cucurbit [8]uril ternary complexes. 13 2.3.…”

Section: Theories and Established Relationshipsmentioning

confidence: 92%

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Structure–Reactivity–Property Relationships in Covalent Adaptable Networks

et al. 2022

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

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Section: Theories and Established Relationshipsmentioning

confidence: 92%

“…For example, a plastic with improved recyclability should exhibit flow at elevated temperatures but undergo minimal rearrangement at room temperature. 8 Similarly, a dynamic hydrogel for biomimetic cell culture should match the mechanics of the native tissue of interest at 37 °C and cannot employ cytotoxic catalysts.…”

Section: Introductionmentioning

confidence: 99%

Structure–Reactivity–Property Relationships in Covalent Adaptable Networks

et al. 2022

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“…20 nm) by using a plasma sputter coater. All samples were analyzed at an acceleration of 15 A time sweep experiment was performed in parallel plate geometry using 20 mm smooth disks with a strain of 1% and an applied frequency of 10 rad.s −1 for a duration of 400 min at 30 °C. The storage modulus (G′) and loss modulus (G″) were recorded over time.…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

Aza-Michael Chemistry for PDMS-Based Covalent Adaptable Elastomers: Design and Dual Role of the Silica Filler

Nguyen,

Mertens,

Du Prez

2024

Macromolecules

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In this study, polydimethylsiloxane (PDMS)-based covalent adaptable networks have been prepared in a one-pot, catalyst-free way in which dynamic β-amino esters (BAEs) are introduced via aza-Michael addition between available acrylate/amine-terminated PDMS-compounds. The straightforward introduction of those BAE-groups in such high-value elastomers provides the ability to relax the applied stress at elevated temperatures and hence the capability of reshaping the networks by compression molding at least 5 times without significant changes in properties. Moreover, the mechanical and dynamic properties are tunable by varying the cross-linker and/or filler content. Interestingly, the utilization of silica fillers not only enhances the network formation and mechanical properties but also accelerates the exchange reactions, resulting in twice faster stress relaxation at elevated temperatures while maintaining creep resistance at service temperatures.

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“…The drawback is that the dimension stability cannot be guaranteed due to the automatic bond exchange reaction at room temperature. 54 To fabricate room-temperature recycled wearable electronic devices with excellent sensitivity and service stability, we propose to use the elastomer with CANs structure containing a room-temperature dynamic covalent bond that can be locked in the separate phase as the substrate. Our strategy to prepare the PDMS elastomer is shown in Figure 1.…”

Section: Introductionmentioning

confidence: 99%

“…In this case, CANs containing room-temperature dynamic covalent bonds could be a choice. The drawback is that the dimension stability cannot be guaranteed due to the automatic bond exchange reaction at room temperature …”

Section: Introductionmentioning

confidence: 99%

Room-Temperature Dynamic and Creep-Resistant Covalent Adaptive Networks via Phase-Locked Benzimidazole Urea Bonds: Toward Recyclable Elastomers for Wearable Electronic Devices

Xie,

Wang,

Lai

et al. 2023

ACS Sustainable Chem. Eng.

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The rapid development of flexible electronic devices has resulted in serious electronic pollution, which has aroused great attention in recent years. This study focuses on the development of dynamic cross-linking poly(dimethylsiloxane) (PDMS) elastomers with covalent adaptive network structures that can be recycled by a solvolytic approach to address this challenge. The elastomer is prepared through the addition reaction between amine-terminated PDMS, isophorone diisocyanate, and 2-aminobenzimidazole followed by cross-linking with hexamethylene diisocyanate trimer. The secondary ureidobenzimidazole (SUBI) moieties formed by benzimidazole and isocyanate groups can undergo a six-memberedring transition state, enabling automatic dissociation and reformation character at room temperature. Hydrogen-bonded aggregates formed by SUBI moieties work as physical cross-linking units to protect urea bonds from dissociation, which endows the materials with excellent creep-resistant performance. Decomposition of the aggregates by solvation, releasing the SUBI moieties, is mainly responsible for the recycling process. Wearable electronic devices with a microcrack structure for vibratory monitoring are assembled through 3D printing nanosilver paste onto the elastomer with predesigned structure. The excellent recycling performance can be transferred from the PDMS substrate to the devices, which enables the separation of PDMS and nanosilver, providing promising principles to develop facile degradable materials at room temperature for fabricating recyclable wearable electronic devices.

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

Cited by 6 publications

References 116 publications

Structure–Reactivity–Property Relationships in Covalent Adaptable Networks

Structure–Reactivity–Property Relationships in Covalent Adaptable Networks

Aza-Michael Chemistry for PDMS-Based Covalent Adaptable Elastomers: Design and Dual Role of the Silica Filler

Room-Temperature Dynamic and Creep-Resistant Covalent Adaptive Networks via Phase-Locked Benzimidazole Urea Bonds: Toward Recyclable Elastomers for Wearable Electronic Devices

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