Off-center Mechanophore Activation in Block Copolymers

Block copolymers (BCPs) are used in numerous applications in modern materials science. Yet, like homopolymers, BCPs can undergo covalent bond scission when mechanically stressed (mechanochemistry), which could lead to unexpected consequences in such applications. BCPs' heterogeneity may affect force transduction, perhaps changing force distribution and localization. To verify this, a gem-dichlorocyclopropane (gDCC) embedded linear chain is prepared and extended with a poly(methyl methacrylate) block. When stressed in solution, the mechanochemical ring-opening of gDCC is accelerated compared to homopolymers, even though the mechanophores are at the chain ends. Moreover, a higher mechanophore activation selectivity is obtained. These results indicate that mechanochemical response outside, and even far from the chain center is quite prominent in BCPs, and that forces along the polymer chain can efficiently activate multi-mechanophores regions, even when far from the polymer midchain.