Elsevier

Polymer

Volume 37, Issue 9, April 1996, Pages 1583-1587
Polymer

Polymer paper
Thermal degradation and melt viscosity of ultra-high-molecular-weight poly(ethylene terephthalate)

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Abstract

The thermal degradation and melt viscosity of ultra-high-molecular-weight poly(ethylene terephthalate) (UHMW-PET) with an intrinsic viscosity exceeding 2 dl g−1 were studied in the melt phase under a nitrogen atmosphere. The degradation rate increased with the molecular weight of the polymer. The high degradation rate of UHMW-PET could be interpreted by the differences in the terminal-end-group concentrations. The activation energy for the degradation of UHMW-PET with an intrinsic viscosity (IV) of 2.3 dl g−1 was 41 kcal mol−1. The effect of molecular-weight change on the thermal degradation of UHMW-PET could be simulated by an empirical formula. The melt viscosity of UHMW-PET with Mw = 2.3 × 105 at 300°C under zero shear was 8 × 105 P and the empirical formula for calculation of the melt viscosity was η0 = 1.45 × 10−17 Mw4.23.

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    In addition, it is possible to notice two interesting behaviors from the Cole-Cole curve: (i) there is a greater contribution of G' at higher frequencies for the more degraded samples, as at this frequency the relaxation process is associated with smaller molecules and segments of larger molecules [39] and (ii) for the samples submitted to a SSP process there is a narrowing in the Mw/Mn, since the curve format of these samples are slightly closer to the equimoduli line. Most studies on the rheological properties of polymers are based on the results of zero-shear viscosity (η0) [15,40]. However, the η0 value was not reached in the present study, since PET is a polymer which presents a short relaxation time as a consequence of its relative low molar mass.

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