Cationic Polymerization in the Presence of π-Electron Acceptors

Abstract

Abstract The cationic polymerization of various vinyl and cyclic monomers was studied in the presence of strong electron acceptors (EA) such as tetracyanoethylene, chloranil, and syn-trinitrobenzene, added in quantities commensurate with the initiator concentrations. In all cases studied, the presence of EA brings about an increase both in the overall polymerization rate and in the molecular weights of the polymers obtained without changing the kinetic scheme of the reaction. The EA added also affects the monomer reactivities in the copolymerization reaction, the insertion of less reactive monomer being favored. The effect of EA was explained in terms of complexation with the counter-ion which causes a shift of the ionic equilibrium in the system.