Heteroatom Substitution Strategy Modulates Thermodynamics Towards Chemically Recyclable Polyesters and Monomeric Unit Sequence by Temperature Switching

Abstract In this paper, we proposed a heteroatom substitution strategy (HSS) in the δ ‐valerolactone (VL) system to modulate thermodynamics toward chemically recyclable polyesters. Three VL‐based monomers containing different heteroatoms (M 1 (N), M 2 (S), and M 3 (O)), instead of C‐5 carbon, were designed and synthesized to verify our proposed HSS. All three monomers undergo organocatalytic living/controlled ROP and controllable depolymerization. Impressively, the resulting P(M 1 ) achieved over 99 % monomer recovery under both mild solution depolymerization and high vacuum pyrolysis conditions without any side reactions, and the recycled monomers can be polymerized again forming new polymers. The systematic study of the relationship between heteroatom substitution and recyclability shows that introducing heteroatoms does change the thermodynamics of the monomers (Δ H p o , Δ S p o and T c values), thereby adjusting the polymerizability and depolymerizability. DFT calculations found that the introduction of heteroatoms adjusts the ring strain by changing the angular strain of the monomers, and the order of their angular strain (M 2 >M 1 >M 3 ) is consistent with the order of the experimentally obtained enthalpy change. Notably, the one‐pot/one‐step copolymerization of two of each of the three monomers enables the synthesis of sequence‐controlled copolymers from gradient to random to block structures, by simply switching the copolymerization temperature.