Functional Thermoplastic Polyurethane Elastomers with α, ω‐Hydroxyl End‐Functionalized Polyacrylates

Abstract Thermoplastic polyurethane (TPU) is an essential class of materials for demanding applications, from soft robotics and electronics to medical devices and batteries. However, traditional TPU development is primarily relied on specific soft segments, such as polyether, polyester, and polycarbonate polyols. Here, a novel method is introduced for developing TPU elastomers with enhanced performance and superior functionalities compared to conventional TPUs, achieved through the use of α,ω‐hydroxyl end‐functionalized polyacrylates. This approach involves a defect‐free synthesis of α,ω‐hydroxyl end‐functionalized polyacrylates through visible‐light‐driven photoiniferter polymerization. By strategically blending these functionalized polyacrylates with conventional polyols, TPUs that exhibit exceptional toughness and notable self‐healing capabilities, traits rarely found in existing TPUs are engineered. Furthermore, incorporating photo‐crosslinkable acrylic monomers has enabled the creation of the first TPU with superior elastomeric properties and photopatterning capabilities. This approach paves the way for a new direction in polyurethane engineering, introducing a novel class of soft segments and unlocking the potential for a wide range of advanced applications.