Expanding Soft-Segment Chemistry in Thermoplastic Polyurethane Elastomers Using Telechelic Polyacrylates

Thermoplastic polyurethanes (TPUs) derive their unique mechanical properties from the combination of flexible soft segments and physically associated hard domains. Despite their broad utility, the design of TPU soft segments has been largely confined to conventional polyether, polyester, and polycarbonate polyols. Here, we present α,ω-hydroxyl end-functionalized polyacrylates as a versatile new family of soft segments for functional TPU elastomers. Defect-minimized telechelic polyacrylates were prepared by visible-light-driven photoiniferter polymerization and incorporated into TPU architectures through conventional polyurethane chemistry. The resulting materials combine high toughness, robust elasticity, and efficient self-healing, demonstrating that polyacrylate soft segments can provide functions that are difficult to access using traditional TPU platforms. Furthermore, photo-crosslinkable acrylate units were introduced to realize photopatternable TPU elastomers without sacrificing elastomeric performance. These results establish telechelic polyacrylates as a powerful platform for expanding TPU molecular design and developing next-generation functional elastomers.