Rapid and Controlled Polymerization of Bio‐sourced δ‐Caprolactone toward Fully Recyclable Polyesters and Thermoplastic Elastomers

The development of chemically recyclable polymers presents the most appealing solution to address the plastics' end-of-use problem. Despite the recent advancements, it is highly desirable to develop chemically recyclable polymers from commercially available monomers to avoid the costly and time-consuming commercialization. In this contribution, we achieve the controlled ring-opening polymerization (ROP) of bio-sourced δ-caprolactone (δCL) using strong base/urea binary catalysts. The obtained PδCL is capable of chemical recycling to δCL in an almost quantitative yield by thermolysis. Sequential ROP of δCL and l-lactide (l-LA) affords well-defined PLLA-b-PδCL-b-PLLA triblock copolymers, which behave as thermoplastic elastomers with excellent elastic recovery, tensile strength and ultimate elongation. The upcycling of PLLA-b-PδCL-b-PLLA to recover ethyl lactate and δCL with high yields is achieved by refluxing with ethanol and then distillation under reduced pressure.