Backbone Degradation of Polymethacrylates via Metal-Free Ambient-Temperature Photoinduced Single-Electron Transfer.

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Polymeric materials comprised of all-carbon backbones are ubiquitous to modern society due to their low cost, impressive robustness, and unparalleled physical properties. It is well-known that these materials often persist long beyond their intended usage lifetime, resulting in environmental accumulation of plastic waste. A substantial barrier to the breakdown of these polymers is the relative chemical inertness of carbon-carbon bonds within their backbone. Herein, we describe a photocatalytic strategy for cleaving carbon-based polymer backbones. Inclusion of a low mole percent of a redox-active comonomer allows for a dramatic reduction in polymer molecular weight upon exposure to light. The N-(acyloxy)phthalimide comonomer, upon reception of an electron from a single-electron transfer (SET) donor, undergoes decarboxylation to yield a backbone-centered radical. Depending on the nature of this backbone radical, as well as the substitution on neighboring monomer repeat units, a β-scission pathway is thermodynamically favored, resulting in backbone cleavage. In this way, polymers with an all-carbon backbone may be degraded at ambient temperature under metal-free conditions.