Substituent effects in surface-initiated ATRP of substituted styrenes

•Suitably substituted styrenes can lead to rapid synthesis of uniform and thick polystyrene brushes (>100nm in 1h) from gold surface via surface initiated ATRP.•High growth rates were observed for styrenes substituted with electron withdrawing groups in meta/para positions.•Electron donors at meta sites show surprisingly fast growth rates, which may be due to steric inhibition of termination.•Surface polymerization rates for substituted styrenes followed the Hammett relation with ρ=0.51, similar to conventional radical polymerization in solution. Surface initiated atom transfer radical polymerization (ATRP) of substituted styrenes leads to rapid synthesis of uniform and thick substituted polystyrene brushes (>100nm in 1h) from gold surface. High growth rates were observed for styrenes substituted with electron withdrawing groups in meta/para positions. The effects seen in surface and solution polymerizations are similar for styrenes with electron withdrawing groups, and for electron donors in ortho and para positions. However, electron donors at meta sites have surprisingly fast growth rates, which may be due to steric inhibition of termination. The overall surface polymerization rates for substituted styrenes was analyzed and found to follow the Hammett relation with ρ=0.51. The ratio of kp to kt, is as an indicator of the likelihood that a reaction will reach high degrees of polymerization before termination.