Initiation processes in polymerizations of alkyl cyanoacrylates by tertiary amines: Inhibition by strong acids

Abstract

Abstract Polymerizations of butyl and ethyl cyanoacrylates, in the solvent THF, initiated by pyridine and other tertiary amines, are inhibited by strong acids, which cause well‐defined inhibition periods ( t i ) proportional to the concentration of acid added, but irrespective of its nature. The temperature and monomer concentration dependence of t i indicate that chain‐initiation is a composite sequence involving two or three successive additions of monomer. A detailed theory is proposed and used to evaluate the composite initiation rate constants over the temperature range 20°C to −80°C. The influence of steric factors on the initiation by pyridine, picolines and lutidine is exemplified and discussed.