Copolymerization of amine-containing monomers and dodecyl (meth)acrylate in toluene: controlling compositional heterogeneity

The radical copolymerizations of N-[(3-dimethylamino)propyl]methacrylamide (DMAPMA) with n-dodecyl acrylate (DA) or n-dodecyl methacrylate (DMA) in toluene (70 °C) were shown to have a peculiar nature: the total initial concentration of monomers significantly influences the composition and compositional heterogeneity of copolymers. Such processes can not be adequately described using the comonomer reactivity ratios. No concentration effects were found in the copolymerization of 2-(dimethylamino)ethyl methacrylate (DMAEMA) and n-dodecyl methacrylate in toluene; the calculated comonomer reactivity ratios were respectively 1.57 ± 0.20 and 0.83 ± 0.02. The differences in the behavior of systems involving amine monomers are related to the ability of DMAPMA to form assemblies with different reactivity due to the hydrogen bonding.