Dynamic Diketoenamine Crosslinking Unlocks Vinyl Polymer Vitrimers From <i>β</i> ‐Triketone Chemistry

Abstract

ABSTRACT Covalent adaptable networks (CANs) offer a compelling strategy to unite the mechanical robustness of thermosets with the reprocessability of thermoplastics, yet achieving simultaneous durability, processability, and true recyclability remains challenging. We introduce diketoenamine (DKE) vitrimers derived from β ‐triketone methacrylate monomers and demonstrate how rational monomer design dictates network processability, viscoelasticity, and recyclability. By systematically varying the spacer length between the β ‐triketone (TK) moiety and the polymer backbone, we identify a key structure–property relationship that dictates vitrimer behavior. Networks bearing TK pendants minimally displaced from the backbone suppress creep but exhibit limited stress relaxation, whereas extended spacers yield lower glass transition temperatures, higher effective crosslink densities, and efficient stress dissipation, enabling optical transparency and reprocessability. Extending this platform to ultra‐high molecular‐weight prepolymers introduces physical entanglements as secondary crosslinks, further enhancing dimensional stability without compromising processability. Both mechanical and chemical recycling validate the closed‐loop circularity of these materials. These results establish TK methacrylates as a versatile platform for designing high‐performance vitrimers that integrate durability, reprocessability, and true closed‐loop recyclability.