Electron spin resonance study of monomeric, dimeric, and polymeric acrylate radicals prepared using the atom transfer radical polymerization technique-direct detection of penultimate-unit effects

Model radicals generated through the reaction of organotin compounds with radical precursors prepared by atom transfer radical addition (ATRA) or atom transfer radical polymerization (ATRP) were studied by electron spin resonance (ESR). Dimers of various (meth)acrylate units, methyl acrylate (MA), tert-butyl acrylate (tBA), and methyl methacrylate (MMA), MA-MA-Br, MA-tBA-Br, tBA-tBA-Br, MMA-tBA-Br, and MA-MMA-Br, were prepared by ATRA. These dimers provided radicals mimicking the active species in a radical copolymerization of MA, MMA, and tBA. Well-resolved ESR spectra of the dimeric radicals confirm electronic and steric effects of the penultimate unit on the propagating radical. Hyperfine splitting constants observed for monomeric, dimeric, oligomeric, and polymeric tert-butyl acrylate radicals depend on the polymer chain length. The variation of ESR spectra with the chain length and penultimate unit was compared with the rate constants of activation in an ATRP using a CuBr/bpy catalyst system.