Polymer International Polym Int 51:923±930 (2002)

DOI: 10.1002/pi.917

New advances in poly(ethylene terephthalate)

polymerization and degradation†
WA MacDonald*
DuPont Teijin Films2, PO Box 2002, Wilton, Middlesbrough TS90 8JF, UK

Abstract: Poly(ethylene terephthalate) (PET) has wide acceptance for use in direct contact with food,
can be recycled and can be depolymerized to its monomer constituents. Advances are continually being
made to reduce the environmental `footprint' that the polymer leaves. This paper discusses new
advances in three speci®c areas, ie process developments, catalysis and polymer degradation, that
address this issue.
# 2002 Society of Chemical Industry

Keywords: Poly(ethylene terephthalate); polymerization catalysis; polymer degradation

1. INTRODUCTION catalyst. A phosphorus-based stabilizer is commonly

Since poly(ethylene terephthalate) (PET) was ®rst
prepared by Whin®eld and Dickson1 in 1946, it has
become one of the most important thermoplastics in
world production as a result of its balance of excellent
mechanical properties, good thermal properties and
cost. PET has been reviewed in detail elsewhere.2,3
Global production at the end of the 1990s was
approximately 24 million tonnes with the bulk of this
production being used in ®bres (67%), followed by
resin for producing blow-moulded bottles (24%).
Biaxially oriented ®lm makes up a further 5%, with
the remaining 4% being used in engineering polymer
applications. In terms of considering PET in the `living
environment', PET has wide acceptance for use in
direct contact with food, can be recycled and can be
depolymerized to its monomer constituents. However,
this is only part of the story that contributes to how
efforts are continually being made to reduce the
environmental `footprint' that the PET leaves. In this
paper three speci®c areas where advances have been
made which address this issue will be discussed. These
are, (i) the latest process developments in PET
manufacturing, (ii) alternative catalyst systems to
antimony, and (iii) polymer degradation.
2. NEXT GENERATION PET TECHNOLOGY
PET is made either via a direct esteri®cation (DE)
route from terephthalic acid and ethylene glycol
followed by a polycondensation stage (Fig 1) or by
an ester interchange (EI) process involving the
dimethyl ester of terephthalic acid and ethylene glycol
followed by polycondensation.2,3 The EI process is
commonly catalysed by manganese or zinc acetate and
the polycondensation by an antimony-oxide-based
added to complex with the catalyst to prevent colour-
forming degradation reactions during the polyconden-
sation process and subsequent polymer processing.
Polymerization is carried out in a batch process in
which the DE or EI stage is carried out in one vessel at
the end of which the esteri®ed terephthalic acid, which
is normally referred to as `monomer', is transferred to a
polycondensation vessel to carry out the polymeriza-
tion step. More commonly, PET is manufactured by
continuous polymerization (CP) which exploits econ-
omy of scale. The conventional CP process involves
three to ®ve vessels for the CP in the melt phase, a
comprehensive vacuum system, a large ®nisher and
pelletizer before the polymer chip enters a solid-state
polymerizer (SSP) (Fig 2). The chemistry is similar to
the batch process but takes place in a continuous
reaction. The esteri®cation step is carried out in the
monomer reactor which then transfers to prepolymer-
izer where the temperature is raised and the pressure
reduced, and the degree of polymerization (DP) is
raised to about 25±35. The prepolymer then enters the
high polymerizer (also called a ®nisher) operating at
higher temperatures and lower pressure to give PET
with a DP of about 100. It is often necessary to make
polymer of higher molecular weight than would be
practicable in the melt, either because the melt
viscosity would be too high or degradation reactions
would overtake the polycondensation reactions and
limit molecular weight. For this reason SSP is
commonly used. The polymer chip from the high
polymerizer is ®rst crystallized to prevent sintering and
then heated at a temperature roughly 20 °C below the
melting temperature, either in a high vacuum or in a
hot inert gas in a device that agitates the solid. The
volatile by-products of the polycondensation reaction

* Correspondence to: WA MacDonald, DuPont Teijin Films, PO Box 2002, Wilton, Middlesbrough TS90 8JF, UK
†
Keynote lecture – Session A: Paper presented at the Polymers in the Third Millennium Conference, 2–6 September 2001, Montpellier,
France
(Received 27 July 2001; revised version received 21 November 2001; accepted 22 January 2002)

# 2002 Society of Chemical Industry. Polym Int 0959±8103/2002/$30.00 923

WA MacDonald
Figure 1. Direct esterification and
polycondensation route to PET.
escape by vapour diffusion from the solid chip and are
rapidly removed from the surface of the chip instead of
being limited by viscous diffusion through a bulk melt.
SSP commonly raises the DP from about 100 to 140
repeat units.4
A new technology has recently been developed by
DuPont and is a signi®cant departure from conven-
tional CP technology.5±9 This technology, designated
NG3 (from `Next Generation version 3') eliminates
several vessels in the melt plant and instead uses a two-
vessel continuous process (Fig 3). In addition to this,
the NG3 process eliminates the need for extensive
overhead condensing and vacuum systems, and
inherent dif®culties linked with handling high-viscos-
ity polymer. Instead the NG3 process produces a low
molecular weight intermediate in the melt phase with a
DP of around 20±30. These pastilles are then
conveyed to the solid-state polymerizer where the bulk
of the polycondensation is carried out to reach the
required degree of polymerization. For this technology
to be viable the low molecular weight pastilles must be
robust enough to withstand the solid-state polymer-
ization. DuPont scientists have developed a novel and
proprietary technology whereby the particle formation
technology imparts a unique crystal structure to the
pellets providing the required strength for solid stating.
The crystal structure is the basis for composition of
Figure 2. Schematic diagram of
continuous polymerization process.
924
matter patents that are currently being ®led for the
NG3 intermediate and ®nal products.
The signi®cant process simpli®cation with NG3 and
resulting elimination of several unit operation steps,
makes the NG3 process less capital-intensive, and as a
result has lower maintenance and energy costs.
Compared to conventional technologies, NG3 offers
signi®cant economy-of-scale advantages. In conven-
tional technologies, the size of the ®nisher or high
polymerizer restricts the ultimate capacity of a single
melt plant line. Because the NG3 process eliminates
the ®nisher, the size of an NG3 plant is not constrained
like that of conventional technologies. In addition, the
elimination of several steps required in the conven-
tional process enables a signi®cant reduction in both
the initial plant investment and the ongoing operating
cost. Not only does NG3 have capital cost advantages
over competitor technologies, it also offers savings in
operating cost, eg less operating labour, reduced
maintenance and insulation costs due to reduction in
equipment, fewer motors and lower total electrical
demand. In terms of the impact on the living
environment the signi®cant bene®t of all this is that
the NG3 process technology leaves a smaller environ-
mental `footprint'.
In addition to its technical and investment advan-
tages, DuPont claim that the NG3 process technology
Polym Int 51:923±930 (2002)

Figure 3. Schematic diagram of NG3
process.
will bring product advantages to the market in terms of
productivity with respect to bottle blowing, product
quality (clarity and gloss) and properties (lower
residual acetaldehyde levels which lead to lower
¯avour taint, and improved strength).
3. ADVANCES IN PET CATALYSIS
A large number of main group and transition metals
have been shown to have catalytic activity for the
polycondensation of PET.10±14 Antimony oxide (and
derivatives thereof) historically emerged as the catalyst
of choice because it demonstrates a good balance of
catalytic activity in the presence of the phosphorus-
based stabilizer, colour and cost. Germanium oxide is
also used; although it is a more active catalyst than
antimony, the high cost of the germanium precludes its
common use in commercial production of PET. In
addition to increasing output through process design
as discussed above, increased rates through improve-
ments in catalysts offer a further route to improving
plant ef®ciencies. Furthermore, the use of antimony-
based catalysts in the preparation of PET used in
packaging applications have come under increasing
scrutiny within Europe and Asia and this, together
with the desire to increase output, has led to PET
manufacturers researching potential alternatives to
antimony which offer a balance of compliance with
food contact regulations, activity, cost and colour. By
far the front runner as an alternative to antimony that
meets the above criteria is titanium.
Titanium-based catalysts are very active relative to
antimony, and the ®rst generation of titanium catalysts
were either alkoxides or simple chelates. Although they
were found to enhance reaction rates, they were prone
to hydrolysis to form oxoalkoxides which have reduced
activity and give rise to haze in the polymer, yielded
polymers of poor colour and were sensitive to
deactivation in the presence of phosphorus-based
stabilizers. Several companies are now developing
titanium-based catalyst systems: Synetix,15,16 Du-
Pont17±23 Lurgi Zimmer and Sachtleben,24 Akzo
Nobel,25 Atochem26 and Hoechst27 are several who
have patented in this area. These latest catalysts are
designed to be stable and have been formulated to give
Polym Int 51:923±930 (2002)
Poly(ethylene terephthalate) polymerization and degradation
a balance of good activity and good colour. This results
in polymers with excellent clarity and also improve-
ments in reaction rates, so offering the potential of
extra capacity on existing assets.
One route taken to achieve this has been to form
titanium chelates with, for example, 2-hydroxy car-
boxylic acids such as citric, malic or lactic.15 Catalysts
of this type are less active than the alkoxides, but can
be more ef®cient as they are water-stable and less
titanium is knocked out as inactive oxoalkoxides.
Catalysts of this type are also soluble in ethylene glycol
at room temperature, making them easy to handle on a
manufacturing plant and meeting regulatory require-
ments for use in contact with food. With careful
control of the balance of titanium to phosphorus and
with the incorporation of a blueing agent, such as
cobalt acetate or red/blue dyes, good polymerization
rates can be achieved and the inherent yellow colour of
the titanium-catalysed polymers can be minimized or
masked. The optimum titanium content can be as low
as 10±30 ppm compared with 250±300 ppm elemental
antimony for an antimony-oxide-catalysed polycon-
densations.3 A further development has been to
incorporate an organophosphorus-based compound
into the catalyst. This allows catalysts to be developed
that are optimized to have a balance of good reaction
rate and yet yield polymers of good colour.16
Despite the importance of catalysis to PET manu-
facture, the mechanism of catalysis in the polycon-
densation reaction is poorly understood; yet an
increased understanding of how the metal centre
interacts with the polymerizing PET chain is impor-
tant for facilitating further developments in catalyst
design. Two different mechanisms have been pro-
posed: (i) coordination to the carboxyl group and (ii)
coordination to the hydroxyl group.
The mechanism proposed by Ravindranath28 in-
volves a hexacoordinate metal catalyst molecule. It was
proposed that the primary step involved coordination
of the metal ion to the ester carbonyl bond. The
coordination of the ester carbonyl group lowers the
electron density of the carbonyl carbon atom and
facilitates nucleophilic attack. It was proposed that the
reaction then proceeded via the activation of the
hydroxyl end-group of a different incoming polymer
925
WA MacDonald
chain which attacked the positively polarized carbonyl
carbon. This was followed by subsequent intramol-
ecular rearrangement to generate a new ester bond and
a metal glycolate species (Fig 4).
An alternative mechanism proposed by Parshall and
Ittel29 involves a pentacoordinate metal centre. In this
mechanism the hydroxyl end-groups of two different
incoming polymer chain ends coordinate to the metal
centre in the form of alkoxide ligands. Intramolecular
rearrangement within the coordination sphere then
results in the formation of a new ester linkage which
couples the two growing polymer chains, thereby
generating a new metal glycolate species (Fig 5).
One reason for the poor understanding of the
reaction mechanism involved in the polycondensation
process is that it is dif®cult to follow spectroscopically
what is happening at the elevated temperatures of
polymerization (270±300 °C). The catalysed polycon-
densation process was investigated recently by Kelly at
the University of Newcastle30 with model systems that
allowed application of lower temperatures. Metal
alkoxides of the type shown in Table 1 were reacted
in a 1:1 reaction at room temperature in solvent with
the monofunctional ethylene glycol monobenzoate
(EGBD) which was used as a model for the end-
group functionality in the monomer bis(hydroxyethyl)
terephthalate. The infra red spectra of the isolated
compounds were recorded as nujol mulls between CsI
plates on a Perkin Elmer 598 spectrometer. In all the
isolated compounds there appeared to be no signi®-
cant shift in the carbonyl region, suggesting that the
carbonyl bond remained unchanged on coordination
and was not coordinated to the metal centre as
postulated in the `Ravindranath' mechanism.28 This
can be compared to shifts of 60±70 wavenumbers
when titanium coordinates to aldehydes and ke-
tones.31 Instead it suggests that exchange of the
monohydroxyethyl benzoate with the metal centre
occurs primarily through the hydroxyl end-group.
This supports the mechanism proposed by Parshall
and Ittel.29 An intermediate of type I is postulated.
4. RECENT ADVANCES IN PET DEGRADATION
There has been considerable activity in developing
routes to recovery of monomer from PET via
methanolysis, glycolysis and hydrolysis. However,
Figure 4. ‘Ravindranath’ mechanism.
926
Figure 5. ‘Parshall and Ittel’ mechanism.
one other recycle route is via the reuse of PET through
multiple extrusion; for this to be viable it is essential
that the PET retains suf®cient rheological and mech-
anical properties to be reused in extrusion and
injection moulding applications, ie molecular weight
fall-off and gel formation should be minimized. In
addition to this, however, it is also important to
minimize discolouration that can negate use in all but
low-grade material. A considerable amount of research
was undertaken in the 1960s and early 1970s on PET
degradation in different environments, but much of
the published work was of a fundamental nature based
on studies carried out on model compounds or at
temperatures that did not re¯ect real operating
conditions. (This work has been reviewed by Zimmer-
man32 and detailed references can be found therein.)
In more recent years there has been much activity
within our own laboratories to make this link between
theory and application.
4.1 The role of DEG
PET contains diethylene glycol (DEG) at a level from
1 to 3.6 mol%. DEG is a naturally occurring by-
product of PET manufacture and, depending upon the
polymerization route, the level of DEG in the ®nal
polymer will vary. Commercially made PET, therefore
is never a true homopolymer but contains ether links.
These labile ether links are potentially a site of
degradation weakness in PET, yet never appear in
the proposed degradation mechanisms for PET. To
ascertain the role of DEG in PET degradation, a series
of PET chips were passed four times through a ZSK 30
extruder at an extrusion rate of 20 kg/hr and an
extrusion temperature of 290 °C in our laboratory.
The experiment was also carried out at 10 kg/hr. In
both series, the chips were dried for several hours at
160 °C before each pass through the extruder. After
four passes the the DEG content (as measured by
NMR) had decreased from 2.8 mol% to about
2.1 mol% (Table 2). These results strongly indicate
that thermooxidative degradation occurs preferentially
at the ether link in DEG.
4.2 Colour formation
The published view for colour formation in PET is
Polym Int 51:923±930 (2002)
 Poly(ethylene terephthalate) polymerization and degradation

Compound n(OÐH) n(CÐH) n(C=O) n(C=C) n(CÐO) n(OÐM)

EGMB 3500 3000 1700 1600 1100 ±
Ti(OPr1)3(EGBD)a ± 3021 1710 1600 1000±1150 600
Sb(OEt)2(EGBD) ± 3019 1710 1600 1000±1100 575
Table 1. Main bands of Ti and Sb complexes with
a
ethylene glycol monobenzoate Microanalysis was consistent with the formula C6H5CO2C2H4O Ti(OPr1)3.

that under conditions of thermal degradation, PET
undergoes a b scission reaction resulting in the
formation of a vinyl ester end-group and a carboxyl
end-group (Fig 6). These vinyl ends can undergo
further reactions, one of which leads to polymerization
of the vinyl group ultimately to yield polyenes.24
However, experimental evidence for this in the
literature is minimal and studies were carried out
within our own laboratory by N Everall to look for
evidence of polyenes. Measurement of the conjugated
Ð(C=C)nÐ stretching frequency using resonance
Raman spectroscopy gives precise information on the
value and polydispersity of the conjugation length `n',
and allows detection of the polyenes at very low levels.
This is because polyene bands are very strong when
the laser wavelength falls within the electronic
absorption pro®le, even dominating the spectrum at
levels as low as 0.5 ppm. The classical examples of this
occur in elimination reactions of vinyl polymers, such
as dehydrochlorination of PVC, or dehydration of
poly(vinyl alcohol).33 If polyenes were present in
degraded PET then they should be readily apparent
in the Raman spectrum. However, no evidence was
found for the presence of polyenes in any of the
degraded PET samples studied, even when the
samples were highly coloured. This strongly suggests
that classical polyenes are not responsible for the
degraded in air at 300 °C closely matched that of II.
Further oxidation of these degraded PET samples with
lead oxide led to further changes in the ¯uorescence
and phosphorescence spectra that were proposed to be
associated with further degradation of the hydroxy-
lated species.
A possible pathway for colour formation in PET is
shown in Fig 7. Peroxidation of the PET occurs at the
ether link in DEG incorporated into PET. The
peroxides break down to give hydroxy radicals which
attack the phenyl ring and ultimately lead to quinone-
type structures incorporated into the PET backbone.
These compounds have only to be present in ppm
amounts for the PET to be discoloured. The pathways
are deliberately left as dotted lines as the intermediates
can only be guessed at.
4.3 Heterogeneity of degradation
Pellets of PET were dried and then annealed at 235 °C
for 1 and 3 h in air. The samples were then cooled and
a 30±35 mm section microtomed along as close as
possible the long axis of the chip. End-group measure-
ments were undertaken within our own laboratory
using transmission IR microscopy (N Everall, PJ Mills
Table 2. Change in DEG level after repeated passes through an extruder

colour formation in PET. In further studies carried out Number of Mol% DEG Mol% DEG
by Edge et al 34,35 at The Manchester Metropolitan passes (extrusion rate 10 kg/h) (extrusion rate 20 kg/h)
University, changes in the ¯uorescence and phosphor-
0 2.8 2.8
escence spectra of PET degraded in the absence and 4 2.2 2.1
presence of oxygen at melt temperatures were com-
pared relative to model compounds such as 2,5-
dihydroxydiethylterephthalate (II) and 2,2,6,6'-tetra
(test-butyl)stilbenequinone (III).

This work has already been published and will not

be discussed in detail, but the conclusions drawn from
this study were that the luminescence spectra of PET Figure 6. Proposed pathway leading to polyenes.

Polym Int 51:923±930 (2002) 927

WA MacDonald
Figure 7. Proposed pathway to colour formation in PET.
and J Chalmers). The microscope apertures were set to
give a sampling area of about 200 mm by 25 mm. The
intensity of the vibrations due to COOH (3255 cm 1)
and OH (3542 cm 1) were internally referenced to the
1950 cm 1 band to normalize for thickness variations.
Values plotted were normalized to a control sample.
The depth over which degradation was measured was
small compared to the chip dimensions. As the
polyester degraded the concentration of COOH
increased relative to OH. It can seen from Fig 8 that
the proportion of COOH was highest at the surface
and decreased into the bulk. With further time this
became more pronounced. This indicates that oxygen
diffusion is controlling the thermo-oxidative degrada-
tion, but also demonstrates that the degradation of
Figure 8. Degradation profile of PET aged in air.
928
Figure 9. Chemiluminescence intensity versus temperature for virgin PET
film.
polymer can be inhomogeneous. Confocal Raman
microscopy can also been used on these materials to
measure crystallinity pro®les over the same region of
the chips; one normally ®nds correlations between
crystallinity and end-group balance. This has been
useful in understanding solid-phase polymerization
processes and the in¯uence on chip `sintering'.
Chemiluminescence (CL) has gained recognition as
a technique for studying the degradative processes in a
variety of polymers.36 In the presence of air, when
polymers oxidize they emit small quantites of light and
this CL can be used to track the rate of oxidation.
Recently, Fredrikssen37 has investigated the degrada-
tion of PET using CL: this is the ®rst time this
technique has been used to study the thermo-oxidative
degradation process in PET.37 The CL detecting
Figure 10. Variation of maximum chemiluminescence intensity with film
thickness.
Polym Int 51:923±930 (2002)

system was a bialkali type photomultiplier tube
capable of detecting light between 180 and 650 nm.
This was coupled to a heating stage in which the
atmosphere could be controlled. It was shown that
PET emits light very strongly above its melting point
(Tm) in oxygen, whereas under a nitrogen atmosphere
it was shown that there was little or no CL up to
temperatures of 360 °C when there was a sharp
increase due to the infrared glow from the instrument
itself (Fig 9). Under oxygen, PET chemiluminesces
very weakly with very little change in intensity until
some point before the Tm where the rate of change in
the CL signal dramatically increases. This indicates
that the oxidation of PET is profoundly affected by the
melting of the polymer. To investigate this phenom-
enon further, the effect of thickness on oxidation was
investigated by stacking biaxially-oriented 23 mm thick
PET ®lm and studying the variation in CL with
thickness at different temperatures (Fig 10). At
temperatures below Tm (about 255 °C), it was found
that the CL intensity was independent of thickness,
and it was only above the Tm that there was some
increase in intensity with ®lm thickness. This indicates
that oxidation is very surface limited at temperatures
below Tm and con®rms the observation made above
using transmission IR microscopy.
The rate of oxidation of a polymer depends not only
on the kinetics of the reaction itself, but also on the rate
at which oxygen diffuses into the polymer via its
surface, and diffusion-limited effects are observed
when the rate of oxygen consumption in the polymer
exceeds the rate of oxygen diffusion. With PET, the
depth to which oxidation occurs increases with
increasing temperature and is more pronounced above
Tm. This implies that below the melting point the rate
of oxidation is greater than rate of oxygen diffusion,
but above the Tm the oxygen is then able to penetrate
to greater depths. This is the opposite to what is found
with polymers such as polypropylene where, as the
temperature increases, the rate of oxidation increases
much faster than the rate of diffusion and the depth to
which oxidation occurs will be smaller at high
temperatures than low temperatures. The implications
of this are that PET is stable to oxidation below the Tm
by virtue of the low rate of oxygen diffusion rather than
inherent chemical stability. However, it may also imply
that the surface layer of a PET chip may be more
heavily degraded than the bulk, the implications of
which are not properly understood.
4.4 Summary
On the basis of the above it is proposed that: DEG is
the weak link in PET (the ether link is preferentially
attacked by oxidation); colour formers in PET result
from attack on the phenyl group by hydroxyl radicals;
oxidation is heterogeneous below the Tm. Knowledge
of this type will help develop process routes that will
minimize the impact of oxygen and hence colour and
molecular weight loss.
Polym Int 51:923±930 (2002)
Poly(ethylene terephthalate) polymerization and degradation
5. CONCLUDING REMARKS
PET is only one member of the polyester family, but it
is by far the dominant member and for this reason it
has been chosen to illustrate advances being made in
the ®eld of polyester research. Poly(butylene ter-
ephthalate) is well established as an engineering
polymer, poly(ethylene naphthalate) is ®nding a niche
market in ®lms (Kaladex1 and Teonex1 (DuPont
Teijin Films2)), and poly(propylene terephthalate),
which has recently become commercially available
(Corterra (Shell) and Sorona1 (DuPont)) is generat-
ing interest in the market place at present. Although
PET is a mature polymer there are still large aspects of
its chemistry that are only poorly understood, as has
been shown above. The chemistry of the other
polyesters is even less well delineated. However,
research of the type described above will lead to new
process and product opportunities for these polymers
and a major component in this will be the desire to
reduce the environmental `footprint' that these poly-
mers leave.
ACKNOWLEDGEMENTS
I would like to acknowledge contributions from L
Farnos (DuPont), J Ridland (Synetix), J Errington
(University of Newcastle), N Billingham (University
of Sussex), N Everall (ICI) and Peter Mills (UCB).
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Polym Int 51:923±930 (2002)