Uncoupling Short-Range Bond Exchange From Long-Range Viscoelastic Flow in Circular Polydiketoenamine Elastomers

Here, we show how to architect dynamic covalent polydiketoenamine (PDK) elastomers prepared from polyetheramine and triketone monomers, not only for energy-efficient circularity, but also outstanding creep resistance at high temperature. By appending polytopic crosslinking functionality at the chain ends of flexible polyetheramines, we reduced creep from >200% to less than 1%, relative to monotopic controls, producing mechanically robust and stable elastomers and carbon-reinforced rubbers that are readily depolymerized to pure monomer in high yield. We also found that the multivalent chain end was essential for ensuring complete PDK deconstruction.