Anionic polymerization of butyl cyanoacrylate by tetrabutylammonium salts, 1. Initiation processes

Anionic polymerizations of butyl cyanoacrylate by tetrabutylammonium salts (acetate, cyano‐ and chloroacetates, and bromide) in tetrahydrofuran and 1,2‐dimethoxyethane show definite ‘retardation periods’ in presence of strong acids. The back‐extrapolated ‘retardation times’ are proportional to [Acid] and inversely proportional to [Salt] and to [Monomer]1,5. The deduced rate of chain‐initiation increases with temperature, in contrast to the negative temperature dependence of initiation by covalent amines. A stationary‐state theory of the retardation is proposed, having a composite initiation process, involving a reversible precursor stage.