Aliphatic polyesters are readily degradable polymers, hydrolysis being the dominant mechanism of degradation. On one side,
this makes them extremely interesting for industrial applications in which degradability is required. On the other side, they
present considerable processing problems due to their sensitivity to process and stocking conditions. In this work, the degradation
of two aliphatic polyesters was studied in the molten state by analysing the rheological properties with the aim of defining
the significance of previous thermal history and of residence time at a given temperature. Rheological measurements were adopted
as a mean of analysis for degradation kinetics because rheological properties are strongly dependent on molecular weight.
In particular, the change in complex viscosity (at constant frequency) as a function of time at different temperatures was
measured. The experimental results show that a significant reduction of viscosity takes place during the isothermal tests
for all the materials analyzed. This reduction was ascribed to the hydrolysis reaction. Indeed, a dried sample showed only
a marginal viscosity reduction. After this initial decrease, an increase in viscosity (more pronounced at higher temperatures)
was found for all the materials and at all the temperatures investigated. This phenomenon was ascribed to the inverse reaction
(esterification) taking place in the absence of water. The dried sample showed, in fact, a much faster increase in viscosity
with respect to the undried one. The degradation kinetics was modeled considering both forward and reverse reactions. The
relative rate of the two reactions depends on the moisture content, and thus the water evaporation from the sample was kept
into account in the rate equations.