Synthesis of Well-Defined Poly(methyl methacrylate) by Radical Polymerization with a New Initiation System TPED/FeCl₃/PPh₃

Well-defined poly(methyl methacrylate) (PMMA) with an α-hydrogen atom and an ω-chlorine atom as the end groups has been synthesized by bulk polymerization of MMA at 95 °C using a new initiation system, 1,1,2,2-tetraphenyl-1,2-ethanediol (TPED)/FeCl3/PPh3. The conversion of polymerization reached to ∼100%. The molecular weight of PMMA obtained was high and the polydispersity index was quite narrow (e.g., Mn = 171 800; Mw/Mn = 1.13). The polymerization of MMA exhibited some “living”/controlled radical polymerization characteristics. The mechanism of polymerization was proposed as a reverse atom transfer radical polymerization (ATRP). The presence of the hydrogen and the chlorine atoms as end groups of the PMMA obtained was determined by 1H NMR spectroscopy.