Dispersity Regulation in Photo-controlled Radical Polymerization by Merging Aryl Sulfonyl Chloride Initiators and Mixed Disulfide Agents

On-demand regulation of molecular weight distribution (MWD) is crucial to influence the properties of polymers. In this work, we reported an organocatalyzed photo-controlled radical polymerization (photo-CRP) from the tosyl chloride initiator by combining two disulfides as chain transfer agents. This novel synthetic protocol allows facile access toward well-defined polymers with tunable MWDs and predetermined molecular weights. Experiments including structural characterization, kinetic investigation and chain-extension polymerization exhibited good chain-growth control for polymers of different dispersities. Given the easy accessibility of the initiating site (sulfonyl chloride) on many aromatic sources, this work presents a promising avenue to modify such substances with polymers of tailored MWDs, chain lengths and repeating units under metal-free and mild conditions driven by light.