Removal of the copper catalyst from atom transfer radical polymerization mixtures by chemical reduction with zinc powder

Simple mixing of an atom transfer radical polymerization (ATRP) mixture with zinc powder was demonstrated to result in rapid decolorizing of the solution and precipitation of elemental copper, using small amounts of silica gel as seeding material. The experiments revealed that the chemical reduction of copper by wetted zinc powder (i.e., 0.325 g/mmol copper) is fast and completed within less than 5 min. UV spectra of the filtered polymer solution showed no any trace of copper. Terminal bromoalkyl groups of the polymers in the ATRP solution were determined to be unchanged by short-term contact with zinc powder at room temperature and a nearly complete reductive dehalogenation takes place only after 24 h of interaction, as evidenced by reaction of elemental zinc with a model compound, ethyl bromoacetate. Indeed, poly(methyl methacrylate) (PMMA) sample (M_n: 7900, polydispersity index: 1.09) isolated from ATRP mixture after the copper removal a by short contact with zinc powder (i.e., 15 min) was determined "still living" as confirmed by chain extension with styrene, ethyl acrylate, and t-butyl acrylate monomers to give block copolymers. The presence of acetic acid was demonstrated to accelerate reductive dehalogenation of PMMA end-groups by zinc and yields nonliving polymer within 2 h.