SET‐LRP of vinyl chloride initiated with CHBr3 in DMSO at 25 °C

The development of Cu(0)/TREN/CuBr2‐catalyzed SET‐LRP of VC initiated with CHBr3 in DMSO at 25 °C is reported. The use of CuBr2 additive allows for the first LRP of low molecular weight VC (target DP = 100), as well as lower Cu powder loading levels, improved Ieff and control in the synthesis of higher molecular VC, targeted degree of polymerization = 350, 700, 1,000, 1,400. 1H NMR and HSQC confirm the bifunctionality of CHBr3 as an initiator and suggest that deleterious side‐reactions such as the formation of allylic chlorides occur primarily at the onset of the reaction.