The curing reaction of stoichiometric mixtures of the diglycidyl ether
of bisphenol-A with difunctional diamino diphenyl methane and monofun
ctional aniline was studied using isothermal differential scanning cal
orimetry over a range of temperatures. High temperature data, beyond t
he diffusion controlled range, was used to fit the kinetics to an auto
catalytic rate equation to determine the chemically-controlled rate co
nstants. In order to model the effect of diffusion on reaction rate, t
he Couchman-Karasz equation was used to fit the glass transition tempe
rature (T-g) of partially cured samples to the degree of conversion. T
his T-g/conversion relationship was used in the Williams-Landel-Ferry
(WLF) equation to calculate the diffusional rate constant during cure.
The chemical and diffusional rate constants were combined in the Rabi
nowitch equation to model the overall rate constant for the reaction.
This model predicts rate/ conversion data and has reasonable agreement
with the experimental curves. Differences between theory and experime
nt were discussed in terms of the dependence of the diffusion coeffici
ent on molecular size and the non-universality of the WLF constants. (
C) 1997 Elsevier Science Ltd.