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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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