Topology-Accelerated and Selective Cascade Depolymerization of Architecturally Complex Polyesters.

Despite considerable recent advances already made in developing chemically circular polymers (CPs), the current framework predominantly focuses on CPs with linear-chain structures of different monomer types. As polymer properties are determined by not only composition but also topology, manipulating the topology of the single-monomer-based CP systems from linear-chain structures to architecturally complex polymers could potentially modulate the resulting polymer properties without changing the chemical composition, thereby advancing the concept of monomaterial product design. To that end, here, we introduce a chemically circular hyperbranched polyester (HBPE), synthesized by a mixed chain-growth and step-growth polymerization of a rationally designed bicyclic lactone with a pendent hydroxyl group (BiLOH ). This HBPE exhibits full chemical recyclability despite its architectural complexity, showing quantitative selectivity for regeneration of BiLOH , via a unique cascade depolymerization mechanism. Moreover, distinct differences in materials properties and performance arising from topological variations between HBPE, hb -PBiLOH , and its linear analogue, l -PBiLOH , have been revealed where generally the branched structure led to more favorable interchain interactions, and topology-amplified optical activity has also been observed for chiral (1 S , 4 S , 5 S )- hb -PBiLOH . More intriguingly, depolymerization of l -PBiLOH proceeds through an unexpected, initial topological transformation to the HBPE polymer, followed by the faster cascade depolymerization pathway adopted by hb -PBiLOH . Overall, these results demonstrate that CP design can go beyond typical linear polymers, and rationally redesigned, architecturally complex polymers for their unique properties may synergistically impart advantages in topology-augmented depolymerization acceleration and selectivity for exclusive monomer regeneration.