Direct Silyl Ether Metathesis for Vitrimers with Exceptional Thermal Stability

Vitrimers are a new class of polymeric materials that simultaneously offer the desired physical properties of thermosets and malleability/reprocessability of thermoplastics. Despite significant progress being made in the field of vitrimers, there exists a critical need for the development of robust dynamic covalent chemistries for the production of strong and thermally stable vitrimers. In this work, we discovered a new silyl ether metathesis reaction and used it for the preparation of vitrimers with exceptional thermal stability. In small-molecule model studies, we observed that silyl ether motifs directly exchange under anhydrous conditions catalyzed by a Brønsted or Lewis acid catalyst. For initial vitrimer demonstration, a commodity polymer, poly(ethylene-co-vinyl alcohol) (PEOH), was silylated with trimethylsilyl (TMS) groups followed by cross-linking with a bis-silyl ether cross-linker. The resulting thermoset showed exceptional thermal stability while maintaining malleability/reprocessability at elevated temperatures. The vitrimer properties such as recyclability and stress relaxation at various temperatures were carefully investigated. The material was reprocessable at 150 °C while also exhibiting good creep resistance at temperatures below its melting transition (T_m). This work demonstrates the silyl ether metathesis reaction as a new, robust dynamic covalent chemistry to introduce plasticity, reprocessability, and recyclability to thermosets.