Dynamic Disulfide Chemistry for Functional Polymers: Self‐Healing, Vitrimer Behavior, and Biochemical/Electronic Applications

Dynamic covalent disulfide bonds offer a powerful strategy for engineering polymeric materials with self-healing, recyclability, and programable degradation. Unlike traditional polymers with static covalent networks, disulfide-based systems respond to mild stimuli, such as heat, UV irradiation, or pH changes, through reversible bond dissociation and exchange. This allows structural rearrangement without compromising integrity, supporting repeated reuse and extended service life. Owing to their relatively low bond dissociation energy, disulfide bonds can undergo rapid exchange even at ambient temperatures. Their associative [2 + 2] metathesis pathway enables efficient bond reshuffling without molecular fragmentation, offering thermodynamically favorable reconfigurability compared to dissociative mechanisms. This review critically examines recent advances in disulfide-exchange chemistry and its integration into functional polymer platforms, including elastomers, vitrimers, and degradable networks. Particular emphasis is placed on how disulfide linkages contribute to long-term performance and circularity, by enabling on-demand reprocessing, localized repair, and environmentally responsive disassembly. From biomedical materials to soft electronics and smart coatings, disulfide chemistry is proving instrumental in aligning polymer design with sustainability goals. We conclude with key challenges and future directions for translating disulfide-based dynamic networks into scalable, high-performance materials for a circular materials economy.