Enabling controlled plastic degradation is crucial for mitigating environmental pollution and advancing a circular material economy. While significant progress has been made in developing various chemical recycling and upcycling strategies, most approaches primarily focus on material recovery while sacrificing morphological features and structural integrity due to the inevitable polymer chain deconstruction and/or depolymerization. Among diverse commodity plastics and their waste streams, styrenic thermoplastic elastomers (TPEs) represent an underexplored opportunity. These materials possess ordered nanostructures formed via self-assembly and have an annual production exceeding 600 million tons. This work introduces an efficient solid-state upcycling method for TPEs by selectively decomposing polystyrene (PS) domains through the synergistic use of acid and radical-based initiators. Specifically, incorporating a small amount of radical initiator (1 wt% dicumyl peroxide) during the TPE sulfonation reaction enables targeted cleavage of PS domains within 45 min, leading to the formation of ordered mesoporous polymers (OMP) in a simple, one-step process. These materials demonstrate exceptional performance in water remediation, attributed to their highly ordered mesoporous structure and the ionic nature of the polymer framework. Furthermore, we demonstrate that this method can be extended to crosslinked PS, enabling complete decomposition and facilitating the recovery and reuse of monomeric derivatives. Our approach provides a scalable and effective solution for transforming styrenic TPE materials into high-performance environmental remediation sorbents through selective and controlled chain degradation.
