Development of Sequence-Controlled Densely Hydroxylated Polymers via Ring-Opening Metathesis Polymerization of Cyclic Olefins and Post-Functionalization

Hydroxylated polymers are widely utilized in industrial, biomedical, pharmaceutical, and electrochemical applications owing to their biocompatibility, non-toxicity, and hydrophilicity. However, conventional synthetic approaches provide limited control over hydroxyl group density, sequence distribution, and polymer microstructure, restricting the development of materials with precisely tunable properties.

Our group previously demonstrated the ROMP of cyclohexene derivatives, a class of monomers traditionally considered difficult to polymerize because of their low ring strain energies (RSEs). Building upon this platform, we developed densely hydroxylated polymers through post-functionalization, generating polymers containing regularly distributed 1,2- and 1,3-diol motifs along the backbone, which enable systematic tuning of physical properties, particularly water solubility. Furthermore, the regularly positioned hydroxyl groups provide a versatile platform for further modification, providing a broad range of functional polymer materials.

The same post-functionalization strategy is being applied to various ROMP-derived polymers and enables the synthesis of a library of sequence-controlled hydroxylated polymers with distinct hydroxyl-group densities and distributions. By systematically varying the spacing and arrangement of hydroxyl groups, we investigate how the density and sequence of hydroxyl groups influence polymer properties. This work establishes a versatile platform for the synthesis of structurally precise hydroxylated polymers and provides fundamental insights for the rational design of next-generation functional materials.