Linking Molecular Sequence to Material Performance: Model Networks and Volumetric 3D Printing of Sequence-Defined Oligourethanes

Sequence-defined macromolecules provide uniform chain composition and precise control over monomer order, yet their implementation in materials science has been constrained by challenges in achieving their scalable synthesis. Here, we report the multigram-scale (i.e., 120 g) preparation of telechelic sequence-defined oligourethanes incorporating distinct hydrogen-bonding motifs and their subsequent cross-linking into structurally well-defined model networks. This scalable access to such uniform structures enables comprehensive structural, thermal, and mechanical characterization, including precise analysis of network integrity through network-disassembly spectrometry. This in-depth analysis revealed clear correlations between the molecular design of the cross-linker and bulk network properties, including swelling behavior, hydrophilicity, and Young’s modulus. Importantly, the scalability of these macromolecules also allowed integration with volumetric 3D printing as a representative high-volume fabrication method, demonstrating that molecular-level sequence control can be reliably translated into advanced manufacturing applications.