Macromolecules, Vol.29, No.21, 6907-6916, 1996
Temperature-Dependence of the Behavior of an Epoxy-Amine System Near the Gel Point Through Viscoelastic Study .1. Low-T-G Epoxy-Amine System
A flexible epoxy-amine system based on the diglycidyl ether of 1,4-butanediol (DGEBD) and 4,9-dioxa-1,12-dodecanediamine (4D) was studied between 40 and 70 degrees C by theological and viscosimetric methods near the gel point. This temperature domain is located well above the maximum glass transition temperature of the fully cured network, for which T-g infinity = -12 degrees C. At the gel point, the theoretical extent of reaction, x(gel), is equal to 0.5745, considering the reactivity ratio, n, of the secondary amines to the primary ones equal to 1.1 (equireactivity, n = 1). For the times corresponding to x(gel), the theological curves follow a classical behavior, i.e., (i) divergence of the viscosity in steady flow conditions, (ii) crossover of the tan delta curves measured as a function of time at several frequencies, and (iii) proportionality between G’ and G " and the pulsation omega(Delta)(G "(omega) and G "(omega) are proportional to omega(Delta)). Above 50 degrees C, the exponent, Delta, is constant and equal to the average value of 0.70 +/- 0.02. The width of the relaxation time spectrum is evaluated by studying the fully cured network. The highest value of Delta observed at low temperatures (40 degrees C) can be explained assuming that, in such a case, the longer relaxation times become similar to the observation times. Close to the gel point, the power laws eta proportional to to epsilon(-k) and G’ proportional to epsilon(z) (where epsilon = x - x(gel)/x(gel)), which govern the viscosity, eta, and the elastic modulus, G’, are verified within a large domain. The exponent k is constant with the temperature and is equal to 1.44 +/- 0.03. The log G " vs f(log epsilon) curves display two linear domains, at least for low temperatures and high frequencies. In the second domain, the exponent z varies with frequency, but above 50 degrees C, its value of omega = 1 rad/s remains constant with the temperature (z(0) = 2.65 +/- 0.02). The values of exponents k, to z(0) and Delta are in good agreement with those obtained from the percolation theory with molecular chains obeying the Rouse model.
Keywords:POLYCAPROLACTONE CRITICAL GELS;DYNAMIC VISCOELASTICITY;TRANSITION;NETWORKS;LINKING;GELATION;EVOLUTION;POLYMER;PDMS