Poly(β-Cyclodextrin) Prepared by Ring-Opening Metathesis Polymerization Enables Creation of Supramolecular Polymeric Networks.

The controlled synthesis of polymers containing densely grafted cyclodextrin units has proven challenging due to the steric hindrance of these cyclic oligosaccharides. In this study, we report the controlled synthesis of poly(β-cyclodextrin) [poly(β-CD)] through ring-opening metathesis polymerization (ROMP) using Grubbs third-generation catalyst. Molecular weights of >10 g/mol were obtained with dispersity values () of ≤1.2. In aqueous solution, β-cyclodextrin forms a host-guest complex with adamantyl groups (Ad). These interactions were utilized to prepare supramolecular polymer networks (SPNs) made by adding poly(β-CD) to α,ω-adamantyl-functionalized poly(2-hydroxyethyl acrylate) (Ad-PHEA-Ad). These poly(β-CD)/Ad-PHEA-Ad SPNs were prepared in aqueous solution and then dried to make homogeneous, transparent films. Varying the ratios of the two components enabled structure-property studies via tensile measurements.