Kinetics of polymerization of alkyl cyanoacrylates by tertiary amines and phosphines

Abstract

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 (k,) to be derived in all cases, corroborated by values derived from the simpler overall kinetics of polymerisation initiated by Ph,P. The rate constant kp shows very slight temperature dependence, less than one order of magnitude between 20 and -80 "C.

Developments and applications of cyanoacrylate adhesives

“…The failure strength or the maximum force depended on the failure energy and the cohesive energy and not on the alkyl group [88]. These alkyl cyanoacrylates form high strength adhesives for bonding glass, metals, plastics, rubber, wood, cement, paper, cloth, polyester, cellophane, and nylon to themselves or to each other [22]. The effects of moisture and sulphur dioxide on the adhesive performance of alkyl cyanoacrylates have been studied.…”

“…A Zwitterion-type species is involved in a complex initiation followed by anionic propagation [22]. Other bases such as alcohols and amines are used to speed up polymerization on porous surfaces or between surfaces having large gaps in between them.…”

An Approximate Kinetic Treatment of Slow‐Initiated Living Polymerization. I. First‐Order Initiation and Propagation

“…This problem does not have a simple solution, not even in the simple case of a polymerization process in which both initiation and propagation are first order with respect to all participants (the methods already in use do not always predict the reaction rate constants with a satisfactory precision [ 141). An accurate determination of the reaction rate constants would require knowledge of an exact analytical solution of the set of differential equations modeling the process.…”

The mechanism of polymerisation of butyl cyanoacrylate in aqueous dispersions

“…[1] Suspension stability is assisted by the incorporation of a steric stabiliser such as dextran. [2] Although the anionic polymerisation of cyanoacrylate monomers in dilute solution has been extensively studied, and detailed kinetic descriptions have been produced, [3][4][5][6] there is difficulty in relating such schemes to the more complicated situation of a dispersion polymerisation. The general assumption that initiation is anionic is clearly reasonable, but many details of the mechanism of polymerisation remain uncertain and the objective of the work described here was to obtain further information on the monomer-polymer conversion process under these special conditions.…”