EFFECT OF EXCLUDED VOLUME ON SPECIFIC RATE OF COMBINATION REACTIONS BETWEEN POLYMER RADICALS

The specific rate k//D for reaction between polymer radicals is formulated when the potential of average force on the basis of the excluded volume affects the motion of the polymer radicals. An equation is derived in which k//D is given as a function of k//S, alpha and F. In this equation k//S is specific rate of reaction between radical chain ends and alpha is the average expansion of the polymer arising from the long-range effects. The effect of the excluded volume reduces k//D. F depends on the degree of polymerization of the polymer radical when alpha is not equal to 1. These results are discussed in terms of the experimental data for very low polymer concentrations.