“Living”/Controlled Free Radical Polymerization Usingbis(Thionaphthoyl) Disulfide as a Source of RAFT Agent

The reversible addition fragmentation chain transfer (RAFT) bulk polymerization of styrene has been studied using bis(thionaphthoyl) disulfide (BTNDS) and 2,2′‐azobis(isobutyronitrile) (AIBN) to generate RAFT agent (2‐cyanoprop‐2‐yl 1‐dithionaphthalate, CPDN) in situ at 80°C. The results show that the polymerization displays living free radical polymerization characteristics: controlled molecular weight with low polydispersity (PDI = 1.14–1.26) and first order kinetics. The extension polymerization using obtained polystyrene as a macro‐RAFT agent displays controlled polymerization behavior. The RAFT polymerizations of methyl methacrylate (MMA), methacrylate (MA), butyl methacrylate (BMA), and octyl acrylate (OA) were successfully carried out using the same polymerization system.