Facile Synthesis of Polyhydroperoxides from Ethylene and Carbon Monoxide

A synthetic strategy for preparing on-chain polyhydroperoxides is reported, utilizing the postpolymerization functionalization of polyketone. Alternating polyketones, derived from the copolymerization of ethylene and carbon monoxide, were quantitatively and selectively transformed into solid polyperoxides using aqueous hydrogen peroxide at room temperature. The complete conversion of carbonyl into peroxy groups made the resulting polyperoxide ideal for free radical graft copolymerization. As a functional polymer, polyperoxide was employed as a macroinitiator to prepare densely grafted copolymers, polyethylene-g-poly(4-methylstyrene) and polyethylene-g-poly(methyl methacrylate). Moreover, the degradability of the graft copolymer was demonstrated, further highlighting the sustainability of polyperoxide from production to application.