Rheological characterization of degradation and polycondensation of poly(ethylene terephthalate) melt in air and in nitrogen

Abstract

Three different poly(ethylene terephthalate) (PET) samples based on dimethyl terephthalate or terephthalic acid, were studied in terms of alterations and mutations caused by thermal exposure during rheological characterization. Thermal stability and frequency sweep experiments were performed in the melt state at a temperature of 280°C, and the influence of the atmosphere (air or nitrogen) as well as the effect of sample preparation (pellets molten directly between the plates of the rheometer vs. samples cut from compression molded sheets) were studied. Thermal stability tests reveal a fundamentally different behavior of the storage (G′) and the loss (G″) modulus for measurements in air compared to measurements in a pure nitrogen atmosphere. Samples measured in air show a decrease of both moduli due to thermal degradation, while an unexpected strong increase was observed in nitrogen due to polycondensation. The loading time of the samples caused already a significant change of the rheological properties, which could be reconstructed by extrapolation to zero loading time. Frequency sweep test were significantly affected by the rapid changes of the molecular structure. Frequency sweeps were conducted bidirectional, i.e. by first increasing the angular frequency from 0.05 rad.s−1 to 500 rad.s−1, which was then followed by a decrease from 500 rad.s−1 to 0.05 rad.s−1, and vice versa. These tests confirm the effects of the atmosphere applied, air or nitrogen, causing degradation and condensation, respectively. However, besides these dominating alterations, i.e. reduction of the molecular weight due to chain scission in air and increase of the molecular weight due to condensation reactions in nitrogen, also the opposite effects were detected. This indicates clearly the formation of a bimodal molecular weight distribution whose existence was supported by the rheological characterization of compression molded plates, which were found to show more degradation but also enhanced bimodality.