On the propagation rate constants of cationic polymerizations

The concepts employed to explain polymerizations by ionizing radiations are used for a critical examination of the concepts involved in interpreting the kinetics of chemically initiated cationic polymerizations. It is explained how the interactions of the propagating carbenium ions with the solvent, monomer, and anion can result in the formation of up to six distinct unpaired species and several kinds of ion pairs; therefore, the consumption of the monomer can be governed simultaneously by many rate constants. Only one of these can have any general theoretical use, and suggestions are made for how it can be measured. For the first time, it is shown that the ion-pairing process must involve a ligand displacement and so resembles the amination of the Ag+ ion, for example, in an aqueous solution by NH3, rather than an association of inert ions of unchanging identity. (C) 2002 Wiley Periodicals, Inc.