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.

Automated summary

Solid-supported organic photocatalysts offer great potential for sustainable chemical syntheses and the development of novel (super)hydrophilic materials. This study presents a hydrolysis-resistant heterogeneous photocatalysis platform based on photocatalytic polymer brushes attached to solid glass supports. The materials overcome the limitations of silane hydrolysis in aqueous conditions and enable well-controlled light-mediated radical polymerization. The addition of hydrophobic protective layers improves longevity and recyclability by mitigating silane hydrolysis and limiting water diffusion to reactive sites. The influence of this hydrophobic protective layer and the hydrophilicity of the photoactive polymer brush on the photocatalytic efficacy of the platform is investigated.