Abstract
AbstractThe radical polymerization of several vinyl monomers has been studied in the presence of cupric chloride. A termination reaction with CuII species leads to the formation of CuI species which can also participate significantly in termination with some, but not all, of the monomers studied. A theoretical treatment of the kinetics of such systems is presented which takes full account of initiator depletion during extended inhibition during extended inhibition periods. Specific velocity constants for reactions of polymer radicals with both CuII and CuI moieties are derived from observations on the nonstationary phase at the end of the inhibition period and from the subsequent steady state of polymerization. On the basis of the results presented here, together with the work of other authors, the patterns‐of‐reactivity approach gives α = −5.4, β = 9.0 as the parameters for copper (II) chloride. The implications of the results in relation to the mechanisms of the reactions between polymer radicals and both copper(II) chloride and copper(I) chloride are discussed. The kinetic treatment also provides an improved method for the determination of the rate of initiator decomposition and the rate of initiation form studies of the inhibition period.
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