A Cleavable Crosslinking Strategy for Commodity Polymer Functionalization and Generation of Reprocessable Thermosets

Abstract

Covalently crosslinked polymeric materials, known as thermosets, possess enhanced mechanical strength and thermal stability relative to the corresponding uncrosslinked thermoplastics. However, the presence of covalent inter-chain crosslinks that makes thermosets so attractive is precisely what makes them so difficult to reprocess and recycle. Here, we demonstrate the introduction of chemically cleavable groups into a bis-diazirine crosslinker. Application of this cleavable crosslinker reagent to commercial low-functionality polyolefins (or to a small-molecule model) results in the rapid, efficient introduction of molecular crosslinks that can be uncoupled by specific chemical inputs. These proof-of-concept findings provide one potential strategy for circularization of the thermoplastic/thermoset plastics economy, and may allow crosslinked polyolefins to be manufactured, used, reprocessed, and re-used without losing value. As an added benefit, the method allows the ready introduction of functionality into non-functionalized commodity polymers.