A theory generalized to cage effects in radical formation for determining initiator efficiency

Abstract

The probability pB of a recombination between a radical produced at time zero and another produced subsequently by β-scission is formulated by solving diffusion equations. When the rate constant k of β-scission is so high that k>>1010 s−1, the same type as the Noyes equation is obtained from the equation for pB. When the rate of recombination is much higher than the relative diffusion rate of radicals, the same type as the Koenig equation is also obtained from pB. An equation, derived previously for the probability of recombination between radicals produced at time zero, is reestablished to explain the observed decomposition rate. On the basis of the above results, an initiator efficiency for radical polymerization is formulated. © 1985 The Society of Polymer Science, Japan.