Abstract
A kinetic scheme for controlled radical polymerization in the presence of copper is developed, first neglecting comproportionation or disproportionation reactions, then taking them into account. Experimental results on the kinetics of the elementary reactions of comproportionation, activation by copper(0) and biradical termination are presented, showing solvent effects on activation and comproportionation reactions and chain length dependence of activation and termination. Unusually high rates of termination are observed in controlled radical polymerizations in the presence of copper; around an order of magnitude faster than in conventional or RAFT polymerizations.
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