Abstract
AbstractIn this work, zero‐valent iron (Fe(0)) (powder or wire) and elemental bromine (Br2) were used as the catalysts for atom transfer radical polymerization (ATRP) of styrene (St) without any additional initiator at 110 °C. The polymerizations happened with controlled evidence at appropriate molar ratio of Fe(0) to Br2: a remarkable increase of molecular weights with St conversions, the narrow molecular weight distributions and living polymer chains end‐capped by Br. More Br2 or less Fe(0) led to a slow polymerization rate but an improved control over molecular weights. After examining the polymer chain ends by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, it was concluded that the polymerization was initiated by thermal self‐initiation, and regulated by the in situ generated FeIIIBr3. The results suggested that the Fe(0)/Br2 catalyzing polymerization was a classical ATRP process with easier operation and more economical components. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012
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