Ultrafast Synthesis of Ultrahigh Molecular Weight Degradable Semifluorinated Copolymers via Triplet‐Enhanced Photoiniferter Polymerization

The environmental persistence and ecological impact of traditional semifluorinated polymers have underscored an urgent need for sustainable alternatives that merge high performance with intrinsic degradability. Herein, we report the synthesis of degradable semifluorinated acrylate-lipoate copolymers via triplet-enhanced photoiniferter polymerization (TEPP). This platform enables oxygen-tolerant, ultrafast polymerization kinetics while maintaining exceptional end-group fidelity. Computational studies reveal high cross-reactivity between the comonomers and a distinct kinetic preference for the formation of disulfide dyads along the polymer backbone. We demonstrate the controlled synthesis of well-defined degradable copolymers across a broad range of molecular weights, chemical compositions, and monomer structures. Remarkably, low-dispersity, ultrahigh molecular weight polymers (M_n > 1400 kg mol^-1; Đ = 1.10) are achieved in less than 10 min. The resulting copolymers exhibit tunable thermal and mechanical properties without compromising their characteristic surface hydrophobicity. Post polymerization modification further diversifies the copolymer functionality and enables the facile construction of crosslinked networks that exhibit molecular-weight-dependent mechanical properties. The strategic incorporation of disulfide linkages ensures the efficient, on-demand degradation of both the linear and crosslinked architectures. This work establishes a robust and versatile platform that addresses the critical demand for high-performance, degradable semifluorinated materials, effectively bridging the gap between technical utility and environmental sustainability.