Reverse atom transfer radical polymerization of methyl methacrylate initiated by p-chlorobenzenediazonium tetrafluoroborate

The controlled polymerization of methyl methacrylate (MMA) in bulk was initiated with p-chlorobenzenediazonium tetrafluoroborate (1) and Cu(II) or Cu(I)/Cu(II)/N,N′,N″,N″-pentamethyldietylene triamine (PMDETA) complex system at various temperatures (20, 60, and 90 °C). The proposed polymerization mechanism is based on the Meerwein-type arylation reaction followed by a reverse atom transfer radical polymerization. In this mechanism, aryl radicals formed by the reaction with 1 and Cu(I) and/or PMDETA initiated the polymerization of MMA. The polymerization is controlled up to a molecular weight of 46,000 at 90 °C. Chain extension was carried out to confirm the controlled manner of the polymerization system. In all polymerization systems, the polydispersity index and initiator efficiency ranged from 1.10-1.57 to 0.10-0.21, respectively.