THERMAL HISTORY AND ENTHALPY RELAXATION OF AN INTERPENETRATING NETWORK POLYMER WITH EXCEPTIONALLY BROAD RELAXATION-TIME DISTRIBUTION

Differential scanning calorimetry (DSC) of an interpenetrating network polymer of composition 25% polyurethane-75% poly (methyl methacrylate) shows a slowly increasing heat capacity, instead of the usual glass transition endotherm, whose onset temperature is not clearly discernible. On aging of the polymer at several temperatures between 193 and 333 K, an endothermic peak is observed whose onset is in the vicinity of the respective temperature of aging. The area under these peaks increases with increasing aging time at a fixed temperature. The effects are attributed to a very broad distribution of relaxation times, which may be represented by either a sum of discrete structural relaxation times of local network arrangement or by a nonexponential relaxation function which is equivalent to a distribution of relaxation times. In either view the vitrified state of the polymer can be envisaged as containing local structures whose own T(g)s extend over a wide range of temperature. Aging decreases the enthalpy and produces an endothermic region which resembles an increase in C(p) on heating because of relaxation of that local structure. The interpretation is supported by simulation of DSC scans in which the distribution of relaxation times is assumed to be exceptionally broad and in which aging introduced at several temperatures over a wide range produces endothermic effects (or regions of DSC scans) qualitatively similar to those observed for the interpenetrating network polymer. (C) 1994 John Wiley & Sons, Inc.