Kinetics of polymerization of alkyl cyanoacrylates by tertiary amines and phosphines

A theory of the overall rates and molecular weights in slowly‐initiated, non‐terminated polymerizations is developed for cases of complex initiation of alkyl cyanoacrylates by tertiary amines. Results with butyl cyanoacrylate (BCA) in the solvent THF, and five different amines (chiefly pyridine and derivatives) show widely differing overall rates. The theory, with the aid of previously determined initiation rate constants, permits the same value for the propagation rate constant (kp) to be derived in all cases, corroborated by values derived from the simpler overall kinetics of polymerisation initiated by Ph3P. The rate constant kp shows very slight temperature dependence, less than one order of magnitude between 20 and −80°C.