Reprocessable and Chemically Recyclable Hard Vitrimers Based on Liquid-Crystalline Epoxides.

The rapid increase in demand for recyclable and reusable thermosets has necessitated the development of materials with chemical structures that exhibit these features. Thus, functional mesogenic epoxide monomers bearing both ester and imine groups that can be vitrimerized and recycled are reported herein. The compounds show mesophase characteristics at 100-200 °C and can be converted into hard epoxides by a common curing reaction. The obtained hard epoxides have high isotropic thermal conductivity (≈0.64 W m -1 K -1 ), which is derived from their highly ordered microstructures. The cured products can be easily reprocessed through imine metathesis and transesterification, and decomposed products can be obtained through imine hydrolysis under acidic or basic conditions and subsequently be re-cured. Surprisingly, recycled materials can be repeatedly reprocessed or chemically decomposed. The reprocessed materials retain the properties of their pristine counterparts, and the recycled products preserve the advantages of the hard thermosets without alteration to any of their unique properties. A dehydration reaction occurs between the residual hydroxyl groups during the re-hardening, which dramatically increases the glass transition temperature by ≈60 °C. These reprocessable and recyclable vitrimers demonstrate the effectiveness and environmental friendliness of the molecular design strategy reported herein.