Self-healing response in supramolecular polymers based on reversible zinc–histidine interactions

Enke, Marcel; Bode, Stefan; Vitz, Jürgen; Schacher, Felix H.; Harrington, Matthew J.; Hager, Martin D.; Schubert, Ulrich S.

doi:10.1016/j.polymer.2015.03.068

Cited by 67 publications

(59 citation statements)

References 58 publications

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“…Examples of metal‐ligand coordination responsible for self‐healing of supramolecular networks: A) ligands are attached to polymer backbones and reversible coordination are formed between (a) dynamic equilibrium of N‐heterocyclic carbenes (NHC) and transition metals monomeric species, (b) polymers containing 2,6‐bis(1‐methylbenzimidazolyl)pyridine (Mebip) ligands coordinated with Zn(NTf) 2 , and (c) terpyridine coordinated with (iron) Fe(II) sulfate; B) ligands are embedded within polymer backbone or as pendent groups and reversible coordination are formed between (a) 2,6‐pyridinedicarboxamide complexed with Fe(III) (B‐2), (b) triazole‐pyridine coordinated with metal salts, (c‐1) tris‐Fe(III)‐catechol complex,[2h] (c‐2) metal‐histidine complex,[42a] (c‐3) metal‐imidazole interactions, and (d) polyethylenimine–copper (II) complex A‐a) Reproduced with permission . Copyright 2007, The Royal Society.…”

Section: Metallosupramolecular Polymersmentioning

confidence: 99%

Self‐Healing of Polymers via Supramolecular Chemistry

Yang

Urban

2018

Adv Materials Inter

163

117

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rearrangements. While one challenge is to incorporate chemical modifications enabling chemical bond reformations, equally important is the coordination of chemical events with polymer network physical changes within interfacial regions resulting from mechanical damage.Recent studies suggested that two types of dynamic bonds are highly attractive to achieve self-healing in polymers: reversible covalent bonds and supramolecular chemistry. Reversible covalent bonds offer higher bonding energies, allowing the material to regain physical properties similar to conventional polymers prior to damage. Advantages and disadvantages of reversible covalent bonding were summarized in several review articles. [5] Self-healing involving dynamic dissociation/association using supramolecular chemistry offers fast reversibility under ambient conditions reaching exceptionally quickly equilibrium state, bonding directionality, and remarkable sensitivity. Since broad-range of network structures can be obtained via supramolecular interactions, applications in soft electronics, sensing, biomedical technologies, 3-4D printing, and reprocessable materials are highly attractive and may open many new technological opportunities (Figure 1). Mechanical integrity using supramolecular chemistry is achieved by the formation of multiple noncovalent interactions between multiple associative groups covalently attached to polymer side chain or chain ends of macromolecular building blocks. These interactions include H-bonding, metal-ligand complexation, hostguest, ionic interactions, π-π stacking, and hydrophobic interactions. They are depicted in Figure 1. In contrast to covalent rebonding, mechanical properties of supramolecular polymer networks are achieved by the presence of these secondary interactions forming noncovalent crosslinks, which bind liquid-like building blocks into plastic or rubbery polymers in hydrated and nonhydrated states. The dynamic nature of these noncovalent bonds provides an opportunity for self-healing attributed to reassociation of supramolecular components, similar to secondary interactions found in living systems that regulate many living functions. The rule of thumb in designing these networks is that the degree of association is determined by the equilibrium constant (K a ) values, whereas dynamics is driven by rate constants of the association-dissociation reactions, k a and k d , respectively. [6] Molecular structural and electronic features along with network heterogeneities are of particular importance in these networks. Mechanical strength and elasticity of supramolecular polymers are determined by not only the K a values, but also stacking and clustering of the associative groups which may result in heterogeneities leading to the Recent advances of supramolecular chemistry utilized in the development of self-healing polymers have revealed that the rate and equilibrium constants of bond dissociation/re-association, bonding directionality, chain relaxation time, decay rate of chain relaxation after damage, and clu...

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Section: Metallosupramolecular Polymersmentioning

confidence: 99%

Self‐Healing of Polymers via Supramolecular Chemistry

Yang

Urban

2018

Adv Materials Inter

163

117

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“…Thus, we used poly(pentafluorophenylacrylate)‐ l ‐polydimethylsiloxane (PPFPA‐ l ‐PDMS) precursor conetworks to prepare functionalized APCNs. It has been reported that non‐chelating ligands such as imidazole or histidine form kinetically more labile complexes with metal ions than chelating ligands based on terpyridine or bipyridine, thus leading to better self‐healing behavior. Therefore, pyridine and Zinc(II)‐based complexes were selected as reversible bonds within the polymer conetworks with self‐healing ability.…”

Section: Resultsmentioning

confidence: 99%

“…The last step of metallo‐supramolecular polymer conetworks synthesis consisted in loading metal ions into the APCNs. Zinc(II) was selected because Zn(II) complexes are inherently kinetic labile as demonstrated in previous works on metallo‐supramolecular self‐healing polymers . From a plethora of available Zinc(II) salts, ZnCl 2 was selected due to the high coordinating strength of chloride counter ions, in addition to the fact that they act as bridging ligand, leading to fast self‐healing .…”

Section: Resultsmentioning

confidence: 99%

Self‐Healing Metallo‐Supramolecular Amphiphilic Polymer Conetworks

Mugemana

Grysan

Dieden

et al. 2020

Macro Chemistry & Physics

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The current challenge in self‐healing materials resides in the design of materials which exhibit improved mechanical properties and self‐healing ability. The design of phase‐separated nanostructures combining hard and soft phases represents an attractive approach to overcome this limitation. Amphiphilic polymer conetworks are nanostructured materials with robust mechanical properties, which can be tailored by tuning the polymer composition and chemical functionality. This article highlights the design of phase‐separated nanostructured polymers from metallo‐supramolecular amphiphilic polymer conetworks, and their application for self‐healing surfaces. The synthesis of poly(N‐(pyridin‐4‐yl)acrylamide)‐l‐polydimethylsiloxane polymer conetworks from the poly(pentafluorophenyl acrylate)‐l‐polydimethylsiloxane activated ester is presented. Loading of ZnCl2 salt into the phase‐separated polymer conetwork strengthens the network by cross‐linking the poly(N‐(pyridin‐4‐yl)acrylamide) phases, while offering reversible interactions needed for self‐healing ability.

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“…One way to address this issue is to introduce a self-healing mechanism, which has received wide interest both from academia and industry in the last decades. [23][24][25][26][27] For polymers and polymer coatings, most reported self-healing approaches, such as encapsulation, 28,29 reversible bonds/interactions [30][31][32][33][34][35][36][37][38][39][40][41][42] or deformation recovery 43,44 aim at repairing mechanical properties or material integrity. Much less attention has been paid to self-healing mechanisms aiming to recover surface functionalities.…”

Section: -8mentioning

confidence: 99%