Ionic and covalent species in the cationic polymerization – equilibria and reactivities

Abstract

AbstractStructure and reactivities in the cationic polymerization of the heterocyclic monomers is reviewed. Particularly the equilibria between major kinds of active species, including the kinetics of interconversions between the covalent species and the corresponding macroion‐pairs are discussed. Reason for the higher reactivity of the ionic species than of the covalent ones in the chain growth, observed in the majority of studied systems, is confronted with the recently observed similarity in reactivities, found for oxepane. Further evidence is discussed, supporting the earlier formulated opinion that ion‐pairs and ions propagate with similar rate constants. These features of the cationic ring‐opening polymerizations were compared with the cationic vinyl polymerization. In the former process the covalent and ionic active species have separately been observed by NMR and the covalent propagation clearly demonstrated, whereas there is only a secondary and weak support for the covalent growth of vinyl monomers.