Chemical Recycling of Polycaprolactones via Reactive Melt Processing

Chemical recycling is a promising technology for the deconstruction of waste plastics into monomers or other chemical intermediates, which can be converted into other value-added products or repolymerized into polymers. In this work, polycaprolactone and poly(4-propylcaprolactone) were chemically recycled by exploiting ring-closing depolymerization (RCD). To demonstrate the utility of this approach, reactive distillation experiments were initially conducted in a heated round-bottom flask with a distillation head to explore the effect of temperature and catalyst loading on RCD. Inspired by industrial devolatilization equipment, analogous experiments were conducted using a twin-screw melt compounder that was modified to simultaneously heat and mix polymer in the presence of a catalyst while continuously removing the evolved monomer vapors with a vacuum system and collecting them in a cold trap. Yield and selectivity of the recovered monomer were characterized by 1H nuclear magnetic resonance spectroscopy and gas chromatography-mass spectrometry. Importantly, the more scalable twin-screw melt compounder approach produced values of monomer selectivity (∼90%) and yield (∼80%) similar to those of the round-bottom flask experiments. The recovered monomers were also successfully repolymerized into the same neat polymer with comparable molar masses without purification steps or adding initiator. The results of this study promote the use of reactive devolatilization extrusion as a scalable approach to polyester depolymerization.