Photocatalytic Decarboxylative Heck-Type Postpolymerization Modification of Polyacrylates

Postpolymerization modification of commodity polymers has emerged as a powerful strategy for synthesizing functional polymers that are challenging to obtain via direct polymerization. Moreover, it offers opportunities to upcycle existing polymers and enhance their material properties. In this work, we introduce a photocatalytic decarboxylative Heck-type approach to upcycle polyacrylates. By employing an acridine-based photocatalyst in combination with a cobaloxime catalyst, hydrolyzed polyacrylates with varying carboxylic acid contents were efficiently converted into polymers bearing olefin functionalities. The degree of olefin incorporation notably influenced the thermal properties of the resulting materials. Importantly, this protocol is applicable to a broad range of vinyl comonomers, yielding 1,3-diene copolymers with exclusive 1,2-insertion selectivity. Furthermore, a variety of terminal alkenes can be utilized to functionalize the acrylate copolymers, and subsequent thiol-ene click reactions further expand the versatility of the accessible polymers.