The molecular mechanism of constructive remodeling of a mechanically-loaded polymer.

Large or repeated mechanical loads usually degrade polymers by accelerating fragmentation of their backbones but rarely, they can cause new backbone bonds to form. When these new bonds form faster than the original bonds break, mechanical degradation may be arrested or reversed in real time. Exploiting such constructive remodeling has proven challenging because we lack an understanding of the competition between bond-forming and bond-breaking reactions in mechanically-stressed polymers. Here we report the molecular mechanism and analysis of constructive remodeling driven by the macroradical products of mechanochemical fragmentation of a hydrocarbon backbone. By studying the changing compositions of a random copolymer of styrene and butadiene sheared at 10 °C in the presence of different additives we developed an approach to characterizing this growth/fracture competition, which is generalizable to other underlying chemistries. Our results demonstrate that constructive remodeling is achievable under practically relevant conditions, requires neither complex chemistries, elaborate macromolecular architectures or free monomers, and is amenable to detailed mechanistic interrogation and simulation. These findings constitute a quantitative framework for systematic studies of polymers capable of autonomously counteracting mechanical degradation at the molecular level.