Synthesis of network polymers composed of well-defined silyl ether macrocycles

Abstract

We report a straightforward synthetic route to silyl ether-based network polymers, enabled by efficient macrocyclization of diols with dichlorosilacyclobutane (DCSB) followed by thermal ring-opening of the silacyclobutane units. This strategy allows well-defined macrocyclic motifs composed of silyl ether linkages to be embedded directly into the polymer backbone. The resulting films are optically transparent and exhibit excellent thermal stability. Mechanical characterization reveals relatively low hardness, reflecting the intrinsic flexibility of the silyl ether framework. Despite the hydrolytic sensitivity of the macrocyclic precursors, the resulting network films demonstrate high acid resistance, which is attributed to their hydrophobic surface properties.