Atom transfer radical polymerization of methyl methacrylate induced by an initiator derived from an ionic liquid

An ionic liquid, 1‐(2‐bromoisobutyryloxyethyl)‐3‐methylimidazolium hexafluorophosphate, was synthesized to act as the initiator of the atom transfer radical polymerization of methyl methacrylate (MMA). By a combination with CuBr and pentamethyldiethylenetriamine, the ionic liquid initiated the free radical polymerization of MMA to proceed in a controlled way over a wide temperature range of 0 to 60 °C. The number‐average molecular weight of the poly(methyl methacrylate) (PMMA) increased with monomer conversion and the polydispersity was relatively narrow. End‐group analysis by proton NMR indicated the presence of the initiator fragments at the ends of the polymer main chain. Lowering the reaction temperature had the result of increasing the content of rr triads. The glass transition temperature was higher for PMMA obtained at lower temperature than at higher temperature. The solubility of the PMMA in methanol increased with the incorporation of imidazolium groups in the polymer. Copyright © 2006 Society of Chemical Industry