Polymer Degradation and Stability 44 (1994) 9-15
~ %/I
ELSEVIER
Effect of some current antioxidants on the
thermo-oxidative stability of poly(ethylene
terephthalate)
George P. Karayannidis, Irini D. Sideridou, Demetris X. Zamboulis, George A. Stalidis,
Demetris N. Bikiaris
Department of Chemistry, Aristotle University of Thessaloniki, GR-54006 Thessaloniki, Greece
&
Aioyse Wilmes
Du Pont de Nemours (Luxembourg) S.A., L-2984 Luxembourg
(Received 6 July 1993; accepted 8 October 1993)
Four current commercial antioxidants (Naugard 445, Ethanox 330, Irganox
1098 and a blend of Irganox 1098 and 1019) were added during synthesis of
poly(ethylene terephthalate) in order to test their thermo-oxidative stability
and eventually to obtain more thermostable products during synthesis and
processing. Their stabilization effect was evaluated by DSC analysis in
nitrogen and air, using as criteria the stabilization coefficient and the induction
period of oxidation. At low concentrations (0.03% and 0.10%), under the
conditions used, better results were obtained with Naugard 445 and Ethanox
330, while at higher concentrations (0.5% and 1-0%) Irganox 1098 and the
blend of Irganox 1098 and 1019 were better than the others.
1 INTRODUCTION
Poly(ethylene terephthalate) (PET) is one of the
most widely used polymers for the manufacture
of films (supports for magnetic tapes or insulation
layers for capacitors), textile fibres and soft drink
bottles. It is usually prepared in two stages from
dimethyl terephthalate (DMT) and ethylene
glycol (EG). In the first stage (transesterifica-
tion), the diglycol ester of terephthalic acid is
mainly formed with a certain amount of
oligomers. Transesterification is catalyzed by
metallic ions such as Zn 2+, Mn 2+, Mg 2+, etc. In
the second stage, the above precondensate is
polycondensed to PET by heating at high
temperature under high vacuum. Polycondensa-
tion is catalyzed by a heavy metal compound,
Polymer Degradation and Stability 0141-3910/94/$07.00
© 1994 Elsevier Science Limited.
usually antimony trioxide. However, during
transesterification and mainly polycondensation I 3
degradation reactions occur simultaneously, le-
ading to the formation of various side products
such as acetaldehyde4 and diethylene glycol. 5.6
The carboxy end group content of PET also
increases by these reactions and strongly affects
the thermal and hydrolytic stability of the
polymer. 7 Moreover, as PET degrades its colour
changes from white to yellow, then to brown and
finally to black; 8 this is a serious problem since
the consumer of white polyester goods demands
a brilliant white colour.
PET also degrades during its melt processing in
the presence of air (thermo-oxidative
degradation), 8~ but in comparison with other
polymers, e.g. polyolefins, is more stable against
auto-oxidation. In general, in order to prevent
the thermo-oxidative degradation, antioxidants
are added during polycondensation or process-