Many studies of the polymerization of vinyl monomers initiated by molecules which decompose with the formation of free radicals have indicated that the rate of the initiation step may be a function of the monomer concentration. The present paper examines the mechanisms previously proposed to account for this behavior in the light of data on a variety of catalyst‐monomer‐solvent systems. It is shown that the rate and efficiency of initiation may, on the basis of the “cage‐effect,” vary with monomer concentration in various ways according to the relative rates of the processes involved and that, in some circumstance, the efficiency of initiation may appear to exceed unity.
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A. D. Jenkins (1958) studied this question.
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