Rheokinetics of crosslinkable poly(vinyl acetate) emulsion and diethylene triamine

The study of the rheological behavior associated with the crosslinking process of epoxy‐functionalized poly(vinyl acetate) emulsion and diethylene triamine showed that the system was reactive and very sensitive to temperature. Gelation times and gelation temperatures were determined from the abrupt changes of the viscoelastic material functions G′, G″, and η* in time sweeps and temperature sweeps. Isothermal kinetics models of the crosslinking process based on the isoconversional method predicted the relationship of curing rate, degree of conversion, reaction nature and kinetic parameters, and temperature. The temperature dependence of the rate constants was found to be described by the Arrhenius relationship. The temperature dependencies of G′, G″, and η* were found to be frequency independent at the gel point, Tgel, providing a fingerprint for determining Tgel of the crosslinkable systems. The variation of G′ and G″ with frequency followed the power laws showing G′ = A′ωb and G″ = A″ωc through the frequency sweep. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012