Facile Solvent- and Catalyst-Free Strategy Enabling High Creep-Resistant, Reconfigurable, and Reprocessable Shape Memory Vitrimers via Dynamic Anhydride Exchange

Developing a simple yet robust dynamic covalent network that integrates high creep resistance, excellent reconfigurability, and shape memory function without sacrificing reprocessability or increasing system complexity remains a considerable challenge. Here, we present a simple, solvent-free, and catalyst-free synthesis of a vitrimer with dynamic anhydride exchange, using commercially available monomers. This vitrimer demonstrates outstanding creep resistance, shape memory performance, shape programmability, and reprocessability. Due to its high topology-freezing temperature (Tv > 220 °C), it exhibits exceptional creep resistance, with significant creep observed only above 160 °C and a minimal creep strain of 4.6% at 140 °C. Full activation of dynamic bonds occurs above 200 °C, enabling nearly complete reprocessing (∼100% efficiency) while retaining up to 85% of the original properties after three recycling cycles. This universal strategy can be extended to enormous (methyl)acrylate-based dynamic covalent systems, offering broad potential in bulk materials, coatings, and 3D/4D printing objects.