Knowledge of the equilibrium constant KATRP and the rate constants kact and kdeact is crucial for designing a successfully controlled atom transfer radical polymerization (ATRP). These reaction parameters not only depend on the monomer, the temperature, the transition metal, and the ligand, but also on the solvent. The present investigation analyzed the solvent effects on KATRP and kact of an atom transfer reaction. For this purpose, time-resolved UV-vis spectrometry was employed to follow the evolution of the CuIIspecies.The results indicate that solvents providing higher values of KATRP are characterized by larger kact and smaller kdeact. No linear correlation between the obtained data and any common single solvent property, such as the dielectric constant, exists. However, the linear solvation energy relationship by Kamlet and Taft could be applied by excluding protic solvents. It is therefore possible to estimate KATRP and kact in non-protic solvents when the corresponding solvent parameters are known.

Solvent effects on the activation/deactivation step in ATRP

245th National Meeting (2013)

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