Indefinitely active aqueous cationic polymerizations, part I: Low cost, recyclable initiator systems

This article describes the first example of an aqueous cationic polymerization that utilizes a low cost, safe, and highly recyclable initiator system (phosphotungstic acid) that retains its activity indefinitely. Quantitative yields of low to medium molecular weight polymers of p ‐methoxystyrene and N ‐vinylcarbazole are obtained within minutes to hours. Polymerization is first order in both monomer and phosphotungstic acid. Negatively charged surfactants suppress polymerization; whereas, nonionic soaps increase the reaction rate and reduce both polymer molecular weight and polydispersity index. Herein, the discovery of a new form of aqueous cationic polymerization involving the condensation of the alcoholic derivative of p ‐methoxystyrene, 1‐(4‐methoxyphenyl)ethanol, is also disclosed.