Chemically Recyclable Dithioacetal Polymers via Reversible Entropy‐Driven Ring‐Opening Polymerization**

In a sustainable circular economy, polymers capable of chemical recycling to monomers are highly desirable. We report an efficient monomer-polymer recycling of polydithioacetal (PDTA). Pristine PDTAs were readily synthesized from 3,4,5-trimethoxybenzaldehyde and alkyl dithiols. They then exhibited depolymerizability via ring-closing depolymerization into macrocycles, followed by entropy-driven ring-opening polymerization (ED-ROP) to reform the virgin polymers. High conversions were obtained for both the forward and reverse reactions. Once crosslinked, the network exhibited thermal reprocessability enabled by acid-catalyzed dithioacetal exchange. The network retained the recyclability into macrocyclic monomers in solvent which can repolymerize to regenerate the crosslinked network. These results demonstrated PDTA as a new molecular platform for the design of recyclable polymers and the advantages of ED-ROP for which polymerization is favored at higher temperatures.