Mechanochemical Diversity in Block Copolymers

Covalent polymer chains are known to undergo mechanochemical events when subjected to mechanical forces. Such force-coupled reactions, like C-C bond scission in homopolymers, typically occur in a non-selective manner but with a higher probability at the mid-chain. In contrast, block copolymers (BCPs), composed of two or more chemically distinct chains linked by covalent bonds, have recently been shown to exhibit significantly different mechanochemical reactivities and selectivities. These differences may be attributable to the atypical conformations adopted by their chains, compared to the regular random coil. Beyond individual molecules, when BCPs self-assemble into ordered aggregates in solution, the non-covalent interactions between the chains lead to meaningful acceleration in the activation of embedded force-sensitive motifs. Furthermore, the microphase segregation of BCPs in bulk creates periodically dispersed polydomains, locking the blocks in specific conformations which have also been shown to affect their mechanochemical reactivity, with different morphologies influencing reactivity to varying extents. This review summarizes the studies of mechanochemistry in BCPs over the past two decades, from the molecular level to assemblies, and up to bulk materials.