Polymerization in a system of discrete particles

It has been shown that subdivision of certain homogeneous polymerizing systems into droplets of diameter 10−4 to 10−5 cm. will entail a probability of finding only one active chain in each particle if the kinetics of the reaction remained otherwise unaffected. Some cases of polymerization in compartmentalized systems have been considered, and it has been shown that, where active centers are generated singly within completely isolated drops, the effect of increasing subdivision would be to increase the rate of reaction and chain length. On the other hand, with the formation of active chains in pairs, the opposite effect is to be anticipated, namely a decreasing rate of reaction with increasing subdivision. These conclusions are briefly considered in relation to the problem of dispersion polymerization, and it is shown that the theory of compartmentalization could account for the occurrence of high rates of reaction and chain lengths in the emulsion process, as compared with a bulk system. On the other hand, there is no evidence showing that the reaction rate is ever reduced in finely dispersed systems.