Atom transfer radical polymerization (ATRP) is dictated by a dynamic reversible equilibrium which is strongly influenced by the transition metal catalyst.  For ATRP correlations between catalyst activity, ligand denticity, type of N-donor atoms, etc. have been established.  A useful tool for assessing catalytic activity is cyclic voltammetry which provides a convenient method for assessing the ATRP equilibrium constant via the half wave potential of the coordination complex.  More reducing complexes were observed to be better catalysts in ATRP for a wide range of metal centers including Cu, Fe, and Ru.  Based on these concepts we have developed novel ligands for copper complexes based on the tris(2-pyridylmethyl)amine (TPMA) scaffold.  After electrochemical characterization was performed, the catalytic activity was estimated to be up to 1000 times larger in comparison to previous catalysts. Finally, the performance of these complexes was evaluated for various ATRP processes.Basic Concept for ATRP.

Designing active catalysts for Atom Transfer Radical Polymerization (ATRP)

244th National Meeting (2012)

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