Combinatorial Engineering of Supramolecular Waterborne Polyurethanes for Tough and Functionally Integrated Elastomer Systems

Conventional combinatorial chemistry is largely confined to single-parameter optimization and remains poorly suited for the multidimensional integration required in advanced polymer systems. Here, we introduce a combinatorial engineering strategy that integrates library synthesis, multidimensional property mapping, structure–property correlation analysis, and system-level assembly to enable predictable multifunctionality in supramolecular waterborne polyurethanes (SWPUs). By tuning supramolecular chain extenders, a 16-member SWPU elastomer library with broadly programmable mechanical and physicochemical properties is constructed, from which a mechanically robust formulation is identified. Building on this library, intrinsic integration of SWPUs with contrasting moduli or solvent responses enables stretchable electronics and solvent-driven actuators, while extrinsic integration with MXene or poly(hexamethylene guanidine) affords composites with high electromagnetic shielding or exceptional antimicrobial performance and toughness (1.0 GJ/m 3 ). Within this framework, a quantitative structure–property correlation based on mass-normalized binding energies establishes a rational metric for trend-level performance estimation, advancing combinatorial chemistry toward rational polymer system assembly.