Benzaldehyde-mediated selective aerobic polyethylene functionalisation with isolated backbone ketones

Post-synthetic functionalisation of commodity polymers such as polyethylene (PE) is an increasingly important strategy for giving waste plastics new 'lease-of-lives' as functional polymers. In particular, installing oxygenated functional groups such as alcohols and ketones is valuable due to their chemical versatility for further chemical modifications. However, this is especially challenging for PE due to its unreactive nature, and often requires hazardous and environmentally damaging chlorinated solvents owing to PE's excellent solvent resistance. Herein, we demonstrate a highly selective method to install isolated carbonyl groups on PE using only benzaldehyde and O 2 as a terminal oxidant, without the need for stoichiometric organic oxidants or any hazardous organic solvents. This process relies on the aerobic auto-oxidation of benzaldehyde to benzoic acid, generating reactive radical intermediates in the process that are responsible for both C-H activation and exclusive carbonyl formation. Our method is compatible with copper( ii ) oxidation catalysts to enhance the extent of PE oxidation, and can also minimise the waste produced as the benzoic acid side product can be easily isolated and reused for different applications. The versatility of carbonyl-containing PEs for further chemical derivatisation offers many exciting options for transforming waste PE into diverse polymeric materials for a materials circular economy. A solvent-free approach for the post-synthetic functionalisation of polyethylene with carbonyl groups exclusively is described using oxygen as the oxidant, with industrially-relevant benzoic acid being the sole organic side product of the reaction.