Polylactide‐polydimethylsiloxane copolymers enabled by one‐pot chain‐shuttling ring‐opening copolymerization: Synthesis, properties and chemical recycling

The development of degradable and incompatible copolymers with tunable material properties has garnered significant attention. Direct copolymerization of lactide (LA) and hexamethylcyclotrisiloxane (D 3 ) faces severe technical barriers due to their significant structural and reactivity differences. In this study, one‐pot chain shuttling ring‐opening polymerization process for the copolymerization of LA and D 3 is reported using the Zn‐Co double metal cyanide as heterogeneous catalyst and propylene oxide (PO) as bridging intermediate. Copolymerization kinetic study shows that the polymerization of LA is dominant in the early stage, and the average molecular weight of the copolymer unimodally increases with monomer conversion. Mechanistic investigations based on experimental and computational studies support a dual‐cycle chain‐shuttling pathway, in which PO acts as an intermediate in the chain shuttling process between the LA‐PO and D 3 ‐PO copolymerization cycles. The as‐prepared copolymers with different chemical compositions exhibit tunable thermal properties. Moreover, the resulting copolymers can be depolymerized to regenerate LA and silicone oil, demonstrating their potential for chemical recyclability. This study presents a practical and versatile approach for the synthesis of degradable and incompatible copolymers.