Collision between polymeric radicals for termination rate constants

Abstract

AbstractThe motion of each polymeric radical during a collision between the polymeric radicals with the same radius is treated as completely random motion. The result obtained is: kt = 0.250ks (where kt is the chain‐termination rate constant and ks is the reaction rate constant between radical chain ends). On taking the motion of the primary radical during a collision between a primary radical and a large polymeric radical to be completely random, the result obtained is: kti = 0.250ksi (where kti is the primary radical termination rate constant and ksi is the reaction rate constant between primary radical and radical chain end). On substituting ks for ksi in the second equation, the rate constant obtained becomes the chain termination rate constant between the very small polymeric radical and the very large polymeric radical, and identical to the former equation. This identity indicates that the effect of the difference of the size of the polymeric radicals on the collision process relating to the chain termination rate constant should not be large.