Initialization behavior at various target molecular weight RAFT-mediated methyl acrylate polymerizations

In the reversible addition-fragmentation chain transfer (RAFT) mediated polymerization of methyl acrylate, a selective reaction is observed in the early stages of the polymerization. This initialization process was earlier observed in in situ H-1 NMR spectroscopy experiments where extremely low target molar masses were chosen (around DP = 5). Here, for the first time, the presence of the initialization process is identified as the cause of an induction period under typical conditions of a RAFT-mediated polymerization. (C) 2008 Wiley Periodicals, Inc.