Mussel byssal threads are well-known due to their self-healing ability after the mechanical stress caused by waves. The proposed mechanism demonstrates the importance of reversible histidine-metal interactions as well as the block copolymer-like hierarchical architecture of the underlying protein structure. Taking these two aspects as inspiration for the design of synthetic analogs, different histidine-rich block copolymers were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. The hard domain was mimicked using polystyrene and the soft domain consists of n-butyl acrylate (BA) as well as histidine moieties as ligands. The block copolymers were crosslinked using different zinc(ii) salts and the resulting metallopolymers were investigated with respect to their self-healing abilities. The observed two-step mechanism of the self-healing process was studied in detail. Furthermore, the mechanical properties were determined by nanoindentation and were correlated with other results.

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The main aim of this work is to study the respective contribution of the hard and soft blocks of a metal-ligand containing block copolymer to the self-healing behavior. To this aim, different block copolymers containing terpyridine were synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization. These block copolymers consisted of polystyrene as the hard block, n-butyl acrylate (BA) as soft block and terpyridine units as the ligand moiety placed at different locations in the soft block. These block copolymers were complexed with manganese(II) chloride to introduce transient crosslinks and, thus, self-healing behavior. Homopolymers with the hard and soft block only were also synthesized and tested. A quasi-irreversible crosslinking, i.e. by using nickel(II) nitrate, was performed in order to study the dynamics of the permanently (strongly) crosslinked network. Rheological master curves were generated enabling the determination of the terminal flow in these networks and the reversibility of the supramolecular interactions. Additionally, the macroscopic scratch healing behavior and the molecular mobility of the polymer chains in these supramolecular networks were investigated. A kinetic study of the scratch healing was performed to determine the similarities in temperature dependence for rheological relaxations and macroscopic scratch healing. In our previous work, we have explored the effect of strength of the reversible metal-ligand interaction and the effect of changing the ratio of hard to soft block. This work goes further in separating the individual contributions of the hard and soft blocks as well as the reversible interactions and to reveal their relative importance in the complex phenomenon of scratch healing.

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In order to accelerate the progress of the development of new self-healing ionomers, a new pathway toward fully organic ionomers containing methacrylic acid and phosphate-based functional groups, respectively, as well as butyl methacrylate as comonomer is presented in the current study. The well-defined copolymer structures are synthesized using the reversible addition-fragmentation chain transfer polymerization and further characterized by NMR, size exclusion chromatography as well as titration. Two different metal-free ionomers as well as one reference K+ based ionomer are created and tested. The results of the detailed investigation by NMR, thermal analysis, and rheology are correlated with the scratch-healing performance in order to identify trends and dependencies leading to preconditions for further improvements.@en

Different block copolymers containing terpyridine were synthesized applying the reversible addition-fragmentation chain transfer (RAFT) polymerization. The block copolymers contain polystyrene as hard block, and the soft block consists of n-butyl acrylate (BA) as well as terpyridine units as ligand. These block copolymers were further cross-linked with several metal salts in order to tune the self-healing behavior. Metallopolymers cross-linked with manganese(II) chloride featured the best self-healing behavior. Furthermore, a two-step mechanism behind the self-healing process of these metallopolymers could be attributed to each block of the copolymer and was studied extensively. In addition, rheological parameters were determined and correlated with the other results.@en

A new polymeric material utilizing a highly efficient as well as reversible thiol-ene click reaction is presented. For this purpose, a trithiol is reacted with a bisbenzylcyanoacetamide derivative resulting in the formation of a dynamic polymer network. The self-healing ability of this novel material is tested by scratch healing experiments. Healing is found to take place from 60 °C onward. The underlying healing mechanism is studied in detail using temperature-dependent Raman spectroscopy confirming the reversible opening of the thiol-ene adducts. Additionally, the thermal and mechanical properties are investigated by differential scanning calorimetry, thermogravimetric analysis, and rheological measurements proving the network formation as well as its reversibility during the thermal treatment. (Figure presented.).

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