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Abstract

Benign polymerization routes offer new perspectives in current polymer technology. Especially for automated or continuous flow synthesis of polymers, new devices and principles have to be considered by the means of minimizing addition or separation sequences as well as the type of a polymer initiation. Near-UV and visible light-induced polymerization utilizing metal-free semiconductor polymeric carbon nitride (pCN) as heterogeneous photocatalyst was a first step into this direction. Moving from heterogeneous powder catalysis (which still requests catalyst separation) to surface photocatalysis via coating glass tubes or vials with pCN thin films is presented. Performance and effectivity of those photoactive reactors are proven by free radical photopolymerization of variety of monomers. Reusability of vials is demonstrated via reversible addition-fragmentation chain-transfer polymerization-assisted block copolymer synthesis. This strategy eliminates the necessity of adding or removing initiators, works at room temperature, and offers a platform for cheap and effective polymer synthesis at the age of automated synthesis.