Cationic polymerization of glycidol: coexistence of the activated monomer and active chain end mechanism

Abstract

Cationic polymerization of glycidol ((hydroxymethyl)oxirane) may involve two competing propagation mechanisms: active chain end (ACE) mechanism (nucleophilic attack of the monomer on the tertiary oxonium ion active species) and activated monomer (AM) mechanism (an attack of the hydroxyl group of the polymer on the protonated monomer). The first mechanism should lead to polymers containing exclusively primary hydroxyl groups. Propagation by the AM mechanism leads on the other hand to polymers containing both primary and secondary (mostly) hydroxyl groups, depending on the detection of the opening of the protonated oxirane ring