Kinetics and mechanisms of zwitterionic polymerizations of alkyl cyanoacrylates

Abstract

The paper reviews work in the author舗s laboratory on the polymerization of alkyl cyanoacrylates, chiefly the butyl ester, in THF, by organic bases, phosphines and amines. It presents evidence that the bases initiate by addition, thus forming zwitterionic propagating species. Polymerizations initiated by Ph3P are confirmed as 舠living polymerizations,舡 but with relatively slow initiation (e.g., equation omitted). Acid-inhibition studies of amine-initiated reactions show that rates of initiation are complex and have negative temperature dependence. This makes unnecessary an earlier postulate that these polymerizations involved a combination舑termination process. A 舠slow-initiated, non-terminated舡 kinetic scheme quantitatively describes polymerizations by pyridine, 4-vinylpyridine, 2, 6-lutidine, and benzyldimethylamine, yielding kp values (equation omitted) consistent among themselves and with that from the Ph3P-initiated kinetics. © 1980, The Society of Polymer Science, Japan. All rights reserved.