B. Ryan et G. Mccann, NOVEL SUB-CEILING TEMPERATURE RAPID DEPOLYMERIZATION-REPOLYMERIZATIONREACTIONS OF CYANOACRYLATE POLYMERS, Macromolecular rapid communications, 17(4), 1996, pp. 217-227
Dilute solutions of unimodal high-molecular-weight poly(butyl cyanoacr
ylate) (''parent'' polymer) in tetrahydrofuran (THF) at 21 degrees C u
nderwent rapid depolymerization accompanied by simultaneous repolymeri
zation of the unzipped monomer to yield lower-molecular-weight ''daugh
ter'' polymer following addition of tetrabutylammonium hydroxide (TBAO
H), a slow initiator of butyl cyanoacrylate (BCA) monomer. The rate-de
termining step for the reaction was tentatively identified as abstract
ion of the terminal chain proton. Similarly, addition of TBAOH to a TH
F solution of BCA monomer resulted in initial formation of high-molecu
lar-weight (MW) polymer that subsequently rapidly depolymerized with s
imultaneous formation of TBAOH initiated, low-MW daughter polymer. The
depolymerization-repolymerization reaction is the relaxation process
that occurs following perturbation of the monomer/high-MW parent polym
er equilibrium by low-MW daughter polymer and proceeds at least 100 de
grees C below the ceiling temperature of the parent polymer.