Scalable design of uniform oligourethanes for impact study of chain length, sequence and end groups on thermal properties†

The full potential of sequence-defined macromolecules remains unexplored, hindered by the difficulty of synthesizing sufficient amounts for the investigation of the properties of such uniform structures and their derived materials. Herein, we report the bidirectional synthesis and thermal behavior analysis of sequence-defined oligourethanes. The synthesis was conducted on a large scale (up to 50 grams) using a straightforward protocol, yielding uniform macromolecules as validated by NMR, ESI-MS and SEC. With this approach, a library of uniform oligourethanes (up to the octamers) was produced using two structural units: a hydrogen-bonding carbamate and a methyl-substituted alternative structure. By varying the chain length, monomer sequence and functionality, we were able to perform a systematic study of the impact of hydrogen bonding on the thermal properties of polyurethanes. Thermal analysis of the discrete oligomers using DSC revealed that both the molecular weight and microstructure significantly affect the glass transition and melting temperatures. TGA measurements also revealed differences in the thermal stability of the oligomers, underscoring the significance of the primary structure of polyurethanes. Additionally, the influence of the terminal groups on the degradation pathway was assessed via pyrolysis-GC-MS, which specifically highlighted the increased thermal stability in the absence of hydroxyl end groups. This work shows the interest of using sequence-defined synthetic macromolecules for the elucidation of structure–property relationships and thereby facilitates their fine-tuning towards specific material applications.