Hydrolysis-resistant heterogeneous photocatalysts for PET-RAFT polymerization in aqueous environments

Solid-supported organic photocatalysts for radical polymerization are promising materials towards more sustainable chemical syntheses and may also open the pathway towards novel (super)hydrophilic materials. This contribution reports on the development of a hydrolysis-resistant heterogeneous photocatalysis platform based on photocatalytic polymer brushes tethered to solid glass supports. The obtained materials circumvent limitations of silane hydrolysis in aqueous conditions and provide well-controlled light-mediated radical polymerization. Moreover, significantly improved longevity and recyclability can be accomplished by adding hydrophobic protective layers that mitigate silane hydrolysis by limiting water-diffusion to reactive sites. We interrogate both the influence of this hydrophobic protective layer and the influence of the hydrophilicity of the photoactive polymer brush on photocatalytic efficacy of the described platform.