Disproportionation or Combination? the Termination of Acrylate Radicals in ATRP

The termination of acrylate radicals in atom transfer radical polymerization (ATRP) can involve either conventional bimolecular radical termination (RT) or catalytic radical termination (CRT). These processes were investigated using a poly(methyl acrylate)-Br macroinitiator under different initial conditions tuned to change the RT/CRT ratio. The polymers, obtained from alkyl halide chain-end activation by [CuI(L)]+ (L = tris[2-(dimethylamino)ethyl]amine (Me6TREN), tris(2-pyridylmethyl)amine (TPMA), or tris(3,5-dimethyl-4-methoxy-2-pyridylmethyl)amine (TPMA∗3)) in the absence of monomer, were analyzed by size exclusion chromatography (SEC). RT-promoting conditions resulted in the increase of a shoulder with double molecular weight (MW) relative to the macroinitiator distribution, indicating that RT occurred predominantly via radical combination. Conversely, when CRT was promoted, the macroinitiator distribution did not shift, indicating a disproportionation-like pathway. The termination reactions for the TPMA system were further analyzed via PREDICI simulations, which showed the significant impact of midchain radicals, arising from backbiting, on the overall termination profile. In all cases, CRT and cross-termination between secondary chain-end and tertiary midchain radicals contributed the most to the overall amount of terminated chains.