In research aimed at improving the brittleness of WER (waterborne epoxy)-modified emulsified asphalt, commonly encountered issues are that the low-temperature performance of this type of asphalt becomes insufficient and the long curing time leads to low early strength. Matrix-emulsified asphalt was modified with WPU (waterborne polyurethane), WER, and DMP-30 (accelerator). Firstly, the performance changes of modified emulsified asphalt at different single-factor dosages were explored through conventional performance tests and assessments of its adhesion, tensile properties, and curing time. Secondly, based on a response surface methodology test design, the material composition of the composite-modified emulsified asphalt was optimized, and its rheological properties were analyzed by a DSR test and a force–ductility test. Finally, the modification mechanism was explored by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The results show that WER can improve the adhesion strength of modified emulsified asphalt and greatly reduce elongation at break. WPU can effectively improve the elongation at break of composite-modified emulsified asphalt, but it has a negative impact on adhesion strength. DMP-30 mainly affects the curing time of modified emulsified asphalt; EPD (composite modification) can effectively improve the high-temperature rutting resistance of matrix-emulsified asphalt, and its low-temperature performance is significantly improved compared with WER-modified emulsified asphalt. The EPD modification process mainly consists of physical blending. In the case of increasing the curing rate, it is recommended that the contents of WER and WPU be lower than 10% and 6%, respectively, to achieve excellent comprehensive performance of the composite modification.

Dynamic covalent bonds are commonly used to maintain the self-healing properties of polyurethanes and facilitate resource recycling. However, relying on a single type of dynamic covalent bond often makes it difficult to effectively regulate both mechanical and self-healing properties across a wide temperature range. In this study, a self-synthesized chain extender containing disulfide bonds was introduced into a polyurethane system, leading to the development of a novel dual-dynamic covalent bond self-healing polyurethane (SSDA-PU). Innovatively, this SSDA-PU demonstrates self-healing properties across a wide temperature range. The successful synthesis of the chain extender and the incorporation of both disulfide bonds and Diels–Alder (DA) bonds were confirmed using FTIR and Raman spectroscopy. The physical characteristics and self-healing performance were comprehensively evaluated through multi-scale testing and characterization, including thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), hardness testing, mechanical tensile tests, and self-healing experiments. The underlying synergistic self-healing mechanism was subsequently elucidated. Findings showed that a higher R-value (isocyanate index) in SSDA-PU leads to over-crosslinking, while an R-value of 1.7 achieves the best overall mechanical performance, with tensile strength and elongation at break reaching 21.1 MPa and 755.17%, respectively. Additionally, SSDA-PU demonstrated the capacity for multiple healing cycles, with an initial self-healing efficiency of 90.38%, which remained notably high at 59.21% even after three damage-healing cycles. Importantly, SSDA-PU exhibited healing capabilities even at relatively low temperatures. Cracks in SSDA-PU can be effectively repaired through the synergistic action of disulfide bond exchange, hydrogen bond dissociation, and thermally reversible DA reactions. SSDA-PU also shows excellent recyclability, offering valuable insights for the practical engineering application of functional polyurethanes.