Polymer Chain Modification via HAT Chemistry and Its Application in Graft Copolymer Synthesis

Hydrogen atom transfer (HAT) chemistry has emerged as a powerful tool for selective molecular functionalization, with significant applications in the pharmaceutical and agricultural industries. More recently, HAT has been explored in polymer chemistry as a versatile strategy for introducing targeted functional groups onto polymer chains, enabling precise control over properties such as solubility and mechanical strength. This study investigates the use of HAT to synthesize reversible addition–fragmentation chain transfer (RAFT) agents (or chain transfer agents, CTAs) by modifying various substrates, including toluene, ethyl acetate, and dioxane, in the presence of bis(dodecylsulfanylthiocarbonyl) disulfide or bis(3,5-dimethyl-1 H -pyrazol-1-ylthiocarbonyl) disulfide. The resulting CTAs were evaluated in both thermal and photoinduced electron transfer (PET)-RAFT polymerization for controlled polymerization of various monomers. This approach was then extended to functionalize polycaprolactone (PCL) and polyvinyl acetate (PVAc), enabling the synthesis of graft copolymers with various vinyl monomers. To promote HAT, a range of photocatalysts, including iron(III) chloride (FeCl 3 ), were investigated, offering advantages over conventional thermal HAT systems. Photocatalysis enables mild and efficient radical generation under light irradiation, providing a cost-effective and environmentally friendly alternative to expensive or toxic metal catalysts.