Soft-Hard Phase Microinfiltration Enables Tunable Hydrogen-Bond Network in High-Performance Bio-Based Polyurethanes

Sustainable bio-based polyurethanes (PUs) combining high strength, high toughness, fatigue resistance, and stimuli-responsive properties are highly desirable for flexible electronics, biomedical engineering, and anticounterfeiting applications. However, overcoming the conventional trade-off between strength and toughness through hydrogen-bond network engineering remains a formidable challenge. Herein, we report a soft-hard phase microinfiltration strategy by introducing varying amounts of poly(hexamethylene 2,5-furandicarboxylate) (PHF) into the PUs matrix. The ester groups of PHF gradually infiltrate from the soft-hard interface to the hard domain through competitive interactions with the inherent hydrogen-bond network. The hydrogen‑bond network restructuring induced by this microinfiltration process enables the BFPU‑10 elastomer to achieve its optimal mechanical performance: a tensile strength of 12.49 ± 0.81 MPa, an elongation at break of 1410 ± 41.74%, and a toughness of 71.83 ± 4.75 MJ m^-3. In addition, spatial confinement imposed by tertiary amine groups and the rigid furan skeleton give the BFPU-x elastomers intrinsic blue aggregation-induced emission and reversible optical responses to temperature and mechanical strain. This research presents a molecular design strategy for restructuring the hydrogen-bond network in sustainable PUs and provides a new pathway for the development of elastomers with high mechanical robustness and sensitive optical responsiveness.