Influences of monomer self‐association on the radical solution homopolymerization of N‐[3‐(dimethylamino)propyl](meth)acrylamide

The specific dependencies of the initial reduced polymerization rate on the initial monomer concentration were introduced for the radical homopolymerization of N-[3-(dimethylamino)propyl]acrylamide (DMAPA) and N-[3-(dimethylamino)propyl]methacrylamide (DMAPMA) in toluene, DMF, and water at 60 °С. The degree of the monomer self-association and the ratio of the amides constituting various types of associates were evaluated using FT-IR spectroscopy and computer simulation for the solutions of DMAPA and DMAPMA in toluene with different monomer concentrations. The hypothesis linking the type of predominant pre-reaction monomer assemblies and the revealed concentration effects was proposed for the homopolymerization of aminoamide monomers and explaining unconventional experimental data. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44412.