Kannapiran Rajendrakumar and R. Dhamodharan
Isobornyl methacrylate (IBMA), a bulky hydrophobic methacrylate, undergoes a spontaneous initiator-free polymerization with Cu(I)Br/N,N,N′,N″,N″-pentamethyldiethylenetriamine/ethyl-2-bromoisobutyrate catalytic system in dimethyl sulfoxide–water mixtures, at ambient temperature. The rate of polymerization increases with increasing water content up to 80 mol % and then decreases. The active Cu(0) formed with the disproportionation of Cu(I) species, in aqueous medium, probably plays a vital role for a possible air-initiation of IBMA via single electron transfer-living radical polymerization mechanism. Poly(IBMA) samples of narrow molecular weight distribution (1.1–1.3) are obtained. This observation is specific only to bulky hydrophobic methacrylates, isobornyl methacrylate, and 1-adamantyl methacrylate.