Photocatalytic Metal‐Free Radical Hydrosilylation for Polymer Functionalization^†

Comprehensive Summary Post‐modification of polymers offers a route to prepare functionalized polymers through efficient chemical reactions, and hydrosilylation is one of the most effective strategies. Silane‐functionalized polymers have found a wide range of potential applications, such as adhesives, rubbers, and drug delivery agents. For decades, the hydrosilylation for the post‐modification of polymers has typically used transition metals as catalysts. Metal‐free hydrosilylation strategies that can avoid metal residues in polymers are largely lacking in this field. Herein, we report the photocatalytic metal‐free radical hydrosilylation strategy for the post‐modification of polymers bearing pendant vinyl groups using the organic photocatalyst and hydrogen atom transfer (HAT) catalyst under blue light irradiation. We used monofunctional silanes to functionalize polymers and the bis(silane)s as crosslinkers to prepare crosslinked polymers.