Electrochemical Modification and Degradation of Macromolecules

Electrochemistry is a powerful tool to break and form challenging chemical functionality. We demonstrate that electrochemical-induced decarboxylation enables reliable post-polymerization modification and degradation of polymers. Polymers containing N-(acryloxy)phthalimides were subjected to electrochemical decarboxylation under mild conditions, which led to the formation of transient alkyl radicals. This enables the production of poly(ethylene-co-methyl acrylate) and poly(propylene-co-methyl acrylate) copolymers, which are difficult to synthesize by direct polymerization. Spectroscopic and chromatographic techniques reveal these transformations are near-quantitative on several polymer systems. Electrochemical decarboxylation also enables the degradation of all-methacrylate poly(N-(methacryloxy)phthalimide-co-methyl methacrylate) copolymers with a degradation efficiency of >95 %. A deep understanding of the radical processes at place in this chemistry also inspired new approaches to polymerizing ultra-high molecular weight polymers. Taken together, this mechanistic exploration reveals how controlled radical processes are an important tool to generate and post-synthetically modify macromolecules.

Biography