Electrochemical C–H Functionalization and Defunctionalization of Polystyrene

Abstract

Covalent modification of simple commodity polymers by C–H functionalization is an efficient way to access new structure–property characteristics and a promising strategy for repurposing plastic waste. We developed an electrochemical method for preparing sulfonium polyelectrolytes by C–H functionalization of polystyrene (PS) from simple thianthrenes. This methodology affords access to structurally diverse polysulfonium products with a controllable degree of functionalization and tunable properties. Modular access to new thianthrenium-functionalized PS materials in this fashion enabled detailed structure–property studies, which revealed that the thianthrenium polymers exhibit high thermal stability, multiphase behavior, and photochemical reactivity that introduces photoacid generator functionality and the ability to undergo defunctionalization.