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A new electrochemical procedure is described to determine the equilibrium constant of atom transfer radical polymerization, KATRP. A rotating disk electrode (RDE) was used to monitor the concentration of the catalyst, CuIL+, during a reaction between the metal complex and an alkyl halide (RX) used as a polymerization initiator. KATRP values with errors in the range ±10% were measured. Conditions were...
Direct determination of ATRP activation rate constant, kact, is typically limited to slow or moderately fast reactions: kact<102mol−1dm3s−1 were determined by classical techniques, such as chromatography, spectrophotometry, NMR, etc. Therefore, these techniques are inadequate to study the fastest, and most useful, ATRP systems, such as the most frequently used Cu complexes with tris[2-(dimethylamino)ethyl]amine...
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