Nitroxide-Mediated Radical Polymerization of N-tert-Butylacrylamide

The nitroxide-mediated polymerization of N-tert-butylacrylamide (TBAM) in DMF at 120 degrees C using SG1/DEPN and AIBN has been investigated. Linear growth in number-average molecular weight ((M) over bar (n)) versus conversion and narrow molecular weight distributions (MWDs) with high livingness were obtained up to approximate to 8 000 g . mol(-1). For higher molecular weights, the MWDs gradually became broader with low molecular weight tailing, and (M) over bar (n) deviated downwards from theoretical values. Quantitative analyses of MWDs, along with specifically designed conventional radical polymerizations at 120 degrees C, were consistent with chain transfer to monomer limiting the attainable (M) over bar (n). This finding can be equally applied to existing literature polymerizations of TBAM.