Polymer 45 (2004) 4403–4412

www.elsevier.com/locate/polymer

Irreversible structural changes during PET recycling by extrusion

R. Assadi, X. Colin*, J. Verdu
LTVP, Ecole Nationale Supérieure d’Arts et Métiers (ENSAM), 151 Bd de l’Hôpital, 75013 Paris, France
Received 30 July 2003; received in revised form 30 March 2004; accepted 1 April 2004

Abstract
Steric exclusion chromatography (SEC) and rheometry were used to study irreversible structural changes occurring during poly(ethylene
terephthalate) (PET) extrusion. It appeared that polymer gelation could occur after three successive extrusions, showing the existence of a
crosslinking process. This latter occurs only in the presence of oxygen at low oxygen pressures (typically PO2 , 9 £ 103 Pa) as a result of
coupling of alkyl radicals generated by the oxidation chain process. A kinetic model based on this assumption but taking also into account
chemical reactions occurring in nitrogen, generates kinetic curves of melt (Newtonian) viscosity changes in good agreement with
experimental ones.
q 2004 Elsevier Ltd. All rights reserved.
Keywords: Poly(ethylene terephthalate); Recycling; Crosslinking

1. Introduction theoretically given by:

1 1
Poly(ethylene terephthalate) (PET) recycling represents Mne ¼ ø
 ð1Þ
b þ b0 kH ew 1=2
one of the most successful and widespread examples of b0 þ
polymer recycling [1]. Practitioners know that, above the kR
melting point ðTm ¼ 255 8CÞ; chemical processes are
where e ¼ 10:4 mol kg21 is the ester concentration.
susceptible to modify the polymer structure in the timescale
Mne decreases rapidly with the water concentration,
of a processing operation. Hydrolysis and acid-alcohol
which explains the need for a careful polymer drying prior
condensation are, no doubt, the most important processes to processing. There is presumably a limit below which the
[2]: solid polymer will loose most of its toughness [3] and the

Let us consider, to simplify, that the acidic and
alcoholic chain ends are in equal concentration: b; the
chain ends other than acids and alcohols are in
concentration: 2b0 ; the water concentration in the
polymer is w: Then the equilibrium molar mass Mne is
* Corresponding author.
E-mail address: xavier.colin@paris.ensam.fr (X. Colin).
0032-3861/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2004.04.029
molten polymer would loose its viscoelastic character,
making impossible the blowing operation [4]. The corre-
sponding molar mass value Mnc is expected to be closely
related to the entanglement threshold (Mc ¼ 6 kg mol21)
[5]. But indeed, a hydrolytically degraded polymer can be
regenerated by heating in dry state. The maximum possible
molar mass would be then: Mn0 ¼ 1=b0 : Finally, all the
molar mass changes linked to the hydrolysis– polyconden-
sation equilibrium can be considered reversible provided that
the water concentration w is controlled. Transesterification
4404 R. Assadi et al. / Polymer 45 (2004) 4403–4412

is also expected to occur in molten state [6] but, as for

hydrolysis – polycondensation, it does not modify the
polymer structure at the molecular (monomer unit) scale
and it is characterized by an equilibrium molar weight
distribution (MWD).
Thus, neither transesterification nor hydrolysis –poly-
condensation equilibrium can be considered as unavoidable
sources of problems, at long term, in PET recycling. In other
words, in the case where there would be no other chemical
process than the above ones, it would be impossible to
differentiate, after recycling operations (each one consisting
to mix recycled and virgin polymer), between ‘new’ and
‘old’ macromolecules.
Other chemical process can be however envisaged, for
instance thermal degradation resulting from an ester
rearrangement [7]: Fig. 1. Temperature profiles for each processing operation. TC and Tm are
the respective crystallisation and melting point temperatures of PET.

This process, eventually accompanied by the acid The screw speed was set at 40 rpm and the residence time
decarboxylation, would lead to an increase of b0 in Eq. was approximately 1.30 min. Successive extrusions were
(1). Indeed, if b0 becomes higher than a critical value bc of realized under the conditions shown in Fig. 1.
the order of the reciprocal of Mc (entanglement threshold),
regenerating polycondensation treatments become unable to
restore sufficiently high molar mass values, so that recycling 2.3. Molecular weight measurements
is no longer possible. In such cases, ‘old’ macromolecules
differ from ‘new’ macromolecules by their chain ends.
Molecular weight was determined by the following
The aim of this paper is to investigate on the irreversible
methods:
processes occurring in PET during extrusion.

(i) Steric exclusion chromatography (SEC): the molecular

2. Experimental
2.1. Materials
A post-consumer adhesive-free and PVC-free PET was
obtained by milling the different French bottle trademarks.
It is supplied from the regeneration center of SOREPLA.
Scraps of post-consumer PET are characterized by an
average crystallinity of 33%, a density of 1.41, and a weight
average molar mass of 55 kg mol21.
2.2. Extrusion
Extrusion was performed with a single screw extruder.
Post-consumer PET was dried in an oven to reduce the
moisture content to less than 20 ppm [8]. For obtaining
dried samples, PET was kept at 120 8C during 2 h and at
140 8C during 4 h.
During the first cycle, the temperature profile of extruder
ranged from 240 8C (at the feeder) to 280 8C (at the die).
weight distribution was determined by SEC using a
Waters Alliance apparatus equipped with four columns
(PL Gel) (5 £ 104, 105 Å) with a multiple detection
(refractometer, UV absorption (l ¼ 270 nm) and
viscosity). The coupling of refractometry with visco-
symmetry allows the detection of chain branching in
polymers. The universal calibration curve was used to
determine molar masses. The eluant system was a
dichloromethane/hexafluoroisopropanol (95:5) mix-
ture at 30 8C.
(ii) Rheological tests: the dynamic flow properties of the
molten materials were measured with a rheometer
Rheometrics ARES, using a parallel plate geometry
(plate diameter: 50 mm, gap: 1 mm). Frequency sweep
tests (v ¼ 1 – 500 rad s21) were made at 280 8C with a
3% strain amplitude.
(iii) Infrared measurements: IR measurements were made
using an IFS 28 Brucker Infrared spectrometer. The
whole results were reported elsewhere [9]. No
significant changes were observed after extrusion.
 R. Assadi et al. / Polymer 45 (2004) 4403–4412
3. Results
The post-consumer PET was reprocessed successively
three times. SEC and rheometric measurements were
performed after each processing operation. It was imposs-
ible to perform a fourth extrusion owing to the very high
increase of polymer viscosity, presumably due to branching
and eventually crosslinking. Rheometric experiments
showed that PET behaviour is Newtonian in the low
frequency range, typically for v # 20 rad s21.
Using the classical power law:
h < KMw3:4
with Kð280 8CÞ ¼ 3:4 £ 1024 Pa s ðmol kg21 Þ3:4 ; the weight
average molar masses were calculated and compared to SEC
ones (see Fig. 2).
SEC and viscosymmetric values of Mw are identical for
non-processed samples and tend globally to decrease with
the number of extrusion cycles but there are significant
differences between both curves of Fig. 2: the viscosym-
metric curve displays a sigmoı̈dal shape whereas the SEC
curve displays a minimum at the second extrusion cycle.
Such a difference can result from drastic polydispersity
changes or from the occurrence of branching, this latter
hypothesis being confirmed by the gelation observed at the
fourth cycle. The build-up of branches on PET macromol-
ecules seems to be confirmed by viscosymmetry in solution.
The intrinsic viscosity IV was plotted against Mw ; as well
for recycled samples as for virgin linear PET samples (Fig.
3). For these latter the Mark –Houwink law was obeyed
[10]:
IV ¼ KMH Mwb with b ¼ 0:76
The points representing recycled samples are clearly
below the straight line characteristic of virgin samples and
their distance to this straight line increases with the number
of extrusion cycles. This effect of processing on the
viscosymmetric behaviour can be reasonably explained by
branching. Thus, the results of Figs. 2 and 3 indicate that
Fig. 2. Variation of the weight average molar mass, Mw ; determined by SEC
and rheometry, as a function of the number N of regeneration cycles.
4405
ð2Þ
Fig. 3. Intrinsic viscosity (IV)-weight average molar mass relationship for
virgin (S) and recycled (K) PET.
PET undergoes simultaneously chain scission and cross-
linking during its extrusion (in the chosen conditions). The
effects of crosslinking become more and more predominant
as the number of processing cycles increases. During the
fourth cycle, the number of branching sites nb approaches
presumably the gel point (schematically
nb < ð1=Mw Þ < 18 £ 1023 mol kg21 ), which explains the
dramatic viscosity increase.
Since an extrusion machine is far from an isothermal and
homogeneous reactor, it seemed interesting to study the
polymer behaviour in sharply controlled conditions. The
rheometer cavity appears to be convenient for such studies:
the temperature field is homogeneous and precisely
regulated, the atmosphere can be controlled and shear
amplitudes can be sufficiently low to insure the absence of
mechanochemical degradation. At the same time, the
ð3Þ apparatus gives direct information on molecular weight
changes with a relatively high sensitivity.
In a first approach, experiments were made in nitrogen
atmosphere since, globally, extrusion can be considered as
an almost anaerobic process. The viscosity variations during
exposure at 280 8C in nitrogen are shown in Fig. 4. The
polymer viscosity increases during the first hour of exposure
and then decreases very slowly. It appears that:
(i) There is no catastrophic crosslinking in nitrogen,
viscosity changes in the timescale of extrusion are
negligible.
(ii) Since there is no reason to suppose that a branching
process would stop after a finite time, it is reasonable to
conclude that there is no branching reaction, the initial
viscosity increase being due to the sample polycon-
densation. Polycondensation in processing conditions
or, even in solid state [11] is a well known way to
increase the molecular weight of recycled PET.
(iii) The slow viscosity decrease at long term can be
explained by a thermal degradation process involving a
random chain scission.
It can be concluded that experiments in neutral
4406 R. Assadi et al. / Polymer 45 (2004) 4403–4412

Fig. 4. Evolution of the melt Newtonian viscosity at 280 8C in nitrogen for a three times reprocessed post-consumer PET.

atmosphere cannot simulate the observed behaviour during
recycling. Since, in this latter case, PET is locally and
temporary in contact with air, at both extremities of the
extrusion machine, it seemed interesting to perform
rheometric experiments in air (all the other rheological
parameters being the same as in the preceding experiment).
The results are shown in Fig. 5. The viscosity decreases
pseudo exponentially in the first hour of exposure and then
almost linearly to reach a value about 3.5 times lower than
the initial value after about 3 h. No doubt, in air, chain
scission predominates largely over crosslinking. Here also,
there is no way to envisage a simulation of the catastrophic
crosslinking process occurring during recycling.
As it will be seen below, there are theoretical arguments
favouring the hypothesis of a crosslinking process induced
by oxidation, but at low oxygen pressures. It was tried to

Fig. 5. Evolution of the melt Newtonian viscosity at 280 8C in various oxygen partial pressures for a three times reprocessed post-consumer PET.
 R. Assadi et al. / Polymer 45 (2004) 4403–4412
Fig. 6. Evolution of the melt Newtonian viscosity at 280 8C in nitrogen but with oxygen admissions during a short interruption for a three times reprocessed
post-consumer PET.
check this hypothesis by two distinct ways:
(i) Making sequential, non-stationary experiments in
which the material is exposed in nitrogen but with
oxygen admission during a short interruption. If
crosslinking is not reversible, one should be able to
observe its consequences on the rheological behaviour.
The results are shown in Fig. 6. Each oxygen admission
is effectively followed by a viscosity increase. This
increase is stopped presumably when oxygen is totally
consumed so that viscosity reaches an asymptotic value
higher for a given step than for the preceding one. This
behaviour can be explained by the occurrence of an
‘oxidative crosslinking’ process predominating over
the oxidative chain scission at low oxygen pressures.
(ii) Making experiments at various oxygen partial press-
ures. The viscosity changes at 280 8C in oxygen –
nitrogen mixtures, the whole pressure being the
atmospheric pressure (105 Pa), are presented in Fig.
5. For the partial oxygen pressure of 9 £ 103 Pa, the
viscosity remains approximately constant, which
indicates that crosslinking effects equilibrate chain
scission ones. According to the theory [12], this would
correspond to:
dx ds
¼4
dt dt
where x and s are the respective numbers of crosslinks
and chain scissions.
For a lower partial oxygen pressure (6 £ 102 Pa),
crosslinking predominates clearly, the viscosity increases
continuously after a short initial period of decrease.
4407
4. Discussion
Our strategy of investigation can be summarised as
follows:
(1) PET undergoes significant changes of its rheological
behaviour after several extrusions.
(2) The global trends of these changes (chain scission or
crosslink) depend sharply of the presence or not of
oxygen, which is a well known characteristic of radical
chain oxidation processes.
(3) In the conversion range of interest ( p 1%), the
available methods for the characterization of the
structure at the molecular scale (formed or destroyed
groups) were not enough sensitive.
(4) Tools for the characterization of the structure at the
macromolecular scale (SEC, rheometry) are in contrast
pertinent.
(5) The link between macromolecular and molecular scale
structural changes will be hypothesized, starting from
two basic assumptions of the ‘standard’ theory of
radical chain oxidation mechanisms and kinetics:
(i) The main reactive sites are methylenes which are
considerably more reactive than aromatics CH
groups [13,14].
ð4Þ (ii) Oxidation is initiated by POOH decomposition
and propagated by P8 and PO28 radicals resulting
of methylene attack.
(6) A kinetic model will be built on the basis of these
assumptions. It will be considered reasonably
validated if it is able to predict the observed trends
with physically reasonable values for the rate
4408 R. Assadi et al. / Polymer 45 (2004) 4403–4412
constants. Rigorously speaking, it will be defini-
tively validated only when structural analyses at the
molecular scale (high sensitivity NMR?) will allow
to identify the oxidation products.
Radical chain oxidation propagates essentially by
hydrogen abstraction. As previously quoted, this latter is
considerably easier on CH methylenic bonds than on
aromatic CH ones, owing to the higher dissociation energy
of these latter. In saturated polymers, there are, in principle,
only two types of oxidation induced crosslinks: peroxides
(POOP) or carbon– carbon links (P – P). The former type of
bridges is highly unstable at 280 8C so that crosslinks are
expected to be essentially of the second type resulting from
the coupling of alkyl radicals:
The absence of crosslinking in neutral atmosphere
suggests that there is no significant radical production in
these conditions. Thus, radicals come essentially from
oxidation, which means that the main initiation process is
the hydroperoxide decomposition. In other words, the
oxidation process generates its own initiator: POOH. The
global trends of this system could be then explained by a
mechanistic scheme of the ‘closed-loop’ type:
Initiation lPOOH ! aP8 þ bPO2 8 þ g1 s ðk1 Þ
Propagation P8 þ O2 ! PO2 8 ðk2 Þ
Propagation PO2 8 þ PH ! POOH þ P8 ðk3 Þ ðIIIÞ
Termination P8 þ P8 ! inactive products þ g4 x ðk4 Þ
ðIVÞ
Termination P8 þ PO2 8 ! inactive products ðk5 Þ
Termination PO2 8 þ PO2 8 ! inactive products þ O2 ðk6 Þ
ðVIÞ
where PH is the methylenic group; s is a chain scission
resulting from POOH decomposition (I) with a yield g1 ; and
x is a crosslink resulting from termination (IV) with a yield
g4 :
At high temperature (typically above 200 8C), the
hydroperoxide decomposition is expected to be unimole-
cular so that l ¼ 1; a ¼ 2 and b ¼ 0:
The rates of structural changes are given by:
ds dx
¼ g1 k1 ½POOH and ¼ g4 k4 ½P82
dt dt
The melt (Newtonian) viscosity is expected to vary with
the weight average molar mass Mw according to Eq. (2) for
PET. The Mw changes are given by the Saito’s equation
[12]:
!
1 1 s
ra 2 ¼ 2 2x ð6Þ
Mw Mw0 2
where ra is the density of the amorphous phase in kg l21 if
the molar mass Mw is in kg mol21.
Using the system of differential equations derived from
the kinetic study of the set of reactions (I)– (VI), and the
Eqs. (2), (5) and (6), it is in principle possible to model the
viscosity changes due to oxidation. This model must lead to
monotonic variations of the viscosity, for instance a
continuous increase at low oxygen pressures. Experimental
results reveal, however, a non-monotonic variation of h: h
first decreases slightly and then increases (see Fig. 5). There
is no way to explain the initial decrease with the above
model.
Furthermore, experiments in neutral atmosphere confirm
the existence of this slight viscosity decrease in the early
period of exposure, but also the existence of a limited
viscosity increase attributed to polycondensation and a final
decrease presumably due to a slow thermolytic random
chain scission. All these non-radical processes have to be
taken into account in the model. The first one, responsible
for the initial viscosity decrease would merit a detailed
investigation, but in the absence of analytical data, it has
been decided to attribute it to a random chain scission linked
to the presence of structural irregularities (Irr), for instance
diethylene glycol moieties, of which the thermal instability
has been demonstrated [15]. Three reactions are thus to be
ðIÞ added to the previous mechanistic scheme:
A thermal degradation from structural irregularities:
ðIIÞ
Thermal degradation Irr ! s ðk7 Þ ðVIIÞ
A polycondensation –hydrolysis process:
Polycondensation acid þ alcohol ! Ester 2 s ðk8 Þ
ðVIIIÞ
ðVÞ And a thermal degradation (presumably according to the
mechanism seen in Section 1):
Thermal degradation PH ! inactive products þ s ðk9 Þ
ðIXÞ
Thus, the rates of structural changes are given by:
ds
¼ g1 k1 ½POOH þ k7 ½Irr 2 k8 ½Acid½Alcohol þ k9 ½PH0
dt


r 2
¼ g1 k1 ½POOH þ k7 ½Irr 2 k8 a þk9 ½PH0
Mn
and
ð5Þ
dx
¼ g4 k4 ½P82 ð5bisÞ
dt
An example of application is given in the case of a post-
consumer PET reprocessed three times ðN ¼ 3Þ using the
 R. Assadi et al. / Polymer 45 (2004) 4403–4412 4409

Table 1
Parameter values for kinetic modelling at 280 8C

Initial conditions for N ¼ 3 [POOH]0 (mol l21) 1024 a

[PH]0 (mol l21) 14 b

[Irr]0 (mol l21) (1.5– 2.1) £ 1023 a

Mn0 (kg mol21) 21.2 c

Mw0 (kg mol21) 45 c

c
Volume fraction of crystalline phase xC (%) 33%
Density of amorphous phase ra (kg l21) 1.33 b

Transport properties of O2 Smelt (mol l21 Pa21) 4.6 £ 1025 b

Rate constants k1 (s21) 1.6 b

k2 (l mol21 s21) 5 £ 108 b

k3 (l mol21 s21) 1.8 £ 103 b

k4 (l mol21 s21) 8.1 £ 1012 a

k5 (l mol21 s21) 2.8 £ 109 a

k6 (l mol21 s21) 2.2 £ 109 b

k7 (s21) (0.9– 1.7) £ 1023 a

k8 (l mol21 s21) 9.3 £ 1023 a

k9 (s21) 2.7 £ 1028 a

a
Yields of macromolecular changes g1 80%
a
g4 20%
Bueche’s constant K (Pa s (mol kg21)3.4) 3.4 £ 1024 b

a
Parameters determined using the model as an inverse method.
b
Parameters determined from a literature survey.
c
Parameters determined experimentally.

parameter values of Table 1 (at 280 8C). The initial

s¼x¼0
conditions were:
Mn ¼ Mn0
½P8 ¼ ½PO2 8 ¼ 0
and
½POOH ¼ ½POOH0
Mw ¼ Mw0
½PH ¼ ½PH0
Examples of simulation runs corresponding to neutral
½Irr ¼ ½Irr0 atmosphere and oxygen partial pressures of 9 £ 103 and

Fig. 7. Simulation of the melt Newtonian viscosity changes at 280 8C in nitrogen for a three times reprocessed post-consumer PET. Comparison to
experimental data.
4410 R. Assadi et al. / Polymer 45 (2004) 4403–4412

Fig. 8. Simulation of the melt Newtonian viscosity changes at 280 8C for two oxygen partial pressures for a three times reprocessed post-consumer PET.
Comparison to experimental data.

6 £ 102 Pa were superposed to experimental curves in Figs.
7 and 8. The agreement between model and experimental
data is satisfactory.
The parameter values of Table 1 call for several
comments:
(i) The substrate concentration was determined from the
theoretical PET structure:
½PH0 ¼ m2 where m, mass molar of the monomer ¼ 192
g mol21
e.g. [PH]0 ¼ 10.4 mol kg21
e.g. [PH]0 < 14 mol l21 if the density of amorphous phase
is ra ¼ 1:33 [5].
Since the PET samples were dried prior to testing, the
water concentration was neglected during all the exposure
[H2O] ¼ 0.
The initial content of irregular structures (about 1 per
4000 monomer units, e.g. about 1 per 17 chains) seems to be
reasonable.
(ii) The oxygen solubility, Smelt ; in the melt PET (at
280 8C) was predicted from the oxygen solubility, Srubber ; in
semi-crystalline PET above its glass transition temperature
[16] knowing its crystallinity ratio, xC ; but neglecting the
temperature effect on the solubility:
Assuming that oxidation is homogeneous within the
whole sample during the rheometer experiment, the oxygen
concentration at any time, in any place, is given by:
½O2  ¼ Smelt PO2
where PO2 is the oxygen partial pressure.
(iii) In a first approach, the values of k1 ; k2 ; k3 and k6 ;
were considered equal to those of polyethylene [17] or
model compounds having non-conjugated methylenic units
[18]. At the opposite, the values of k4 and k5 were adjusted
from experimental viscosity curves, using the model
through an inverse method. The following trends can be
observed:
k4 q k5 < k6 ð7Þ
as logically expected at high temperature (at 280 8C) where
the ‘primary’ products of coupling reactions such as
peroxides (PO-OP) cannot survive:

Smelt ¼ Srubber ð1 2 xC Þ

with Srubber ¼ 3:1 £ 1028 mol l21 Pa21 [16] and xC ¼ 33%:
 R. Assadi et al. / Polymer 45 (2004) 4403–4412 4411

(iv) The stoichiometric ratio values giving the better fit of
experimental results are:
g4 ¼ 0:2 for crosslinking (the competitive reaction is
presumably disproportionation):
What lacks now, to confirm the validity of this model, is
an evidence of the formation of oxidation products of
methylene groups, obtained from analytical investigations
on the molecular scale structure (IR, NMR). This is, no
doubt, a challenge, owing to the very low conversion range

g1 ¼ 0:8 for chain scission (the competitive reaction is under consideration. For instance, gelation occurs at a
presumably hydrogen abstraction): crosslink density of the order of 18 £ 1023 mol kg21, i.e.
involving only 0.35% of the initially present methylene

The effect of oxygen pressure on average molecular weight
changes is well illustrated by Fig. 9 in which the changes of
average molecular weight with exposure time have been
plotted for many values of the oxygen partial pressure. For a
best visualisation of this effect, one can plot the molecular
weight, at a given time of exposure, versus oxygen partial
pressure. Then, it appears clearly that there is a catastrophic
crosslinking up to polymer gelation ðMw ! 1Þ for a relatively
low oxygen partial pressure of typically 6 £ 103 Pa.
groups. Carbon – carbon bonds are practically undetectable
by IR and probably accessible only by sophisticated NMR
methods.
5. Conclusions
During its recycling by extrusion, PET can undergo
reversible structural changes resulting of hydrolysis –

Fig. 9. Weight average molar mass changes for various oxygen partial pressures.
4412 R. Assadi et al. / Polymer 45 (2004) 4403–4412
polycondensation or from transesterification process. But
irreversible degradation processes can also take place.
According to our experimental results two distinct processes
can be observed in absence of oxygen: the random
degradation presumably linked to a rearrangement of the
ester group into acid and vinyl groups and a chain scission
occurring at randomly distributed unstable structural
irregularities (for instance of the diethylene glycol type).
Both processes have very limited consequences in practice:
the first one, because it is the result of a very slow reaction in
processing conditions, the second one, because the pre-
cursor concentration is very low (typically 1 per 4000
monomer units).
In the presence of oxygen, however, radicals are formed
and, at low oxygen concentrations, these latter can lead to
crosslinking by radical coupling whereas at high oxygen
concentration, they lead to fast chain scission. This
behaviour can be well simulated using a kinetic model
based on the classical mechanistic scheme for polymer
autoxidation of the ‘closed-loop’ type. The model can be
validated on the basis of experiments made at controlled
temperature and oxygen partial pressure in a rheometer
cavity. In the case of extrusion, the problem is considerably
more complex for many reasons:
(i) Oxygen is in contact with the polymer only at both
extremities of the machine. Oxidation is thus diffusion
controlled.
(ii) The spatial distribution of oxygen concentrations in the
polymer must take into account not only the oxygen
diffusion into the melt, but also the mechanical
transport of oxygenated polymer particles through the
extrusion machine.
(iii) Thermal fields are non-homogeneous.
There is no doubt, however, that there is a part of the
polymer particle trajectory into the extrusion machine,
where the conditions are favourable to crosslinking by
radical coupling, the source of (alkyl) radicals being the
oxidation process. In principle, the corresponding structural
changes are expected to be limited owing to the relatively
low extent of polymer oxygenation during processing.
However, there changes are cumulative and could lead, at
long term, in unfavourable conditions, to catastrophic
crosslinking.
A systematic characterisation of the degree of branching
in recycled PET could be then recommended. Stabilisation
by antioxidants working at high temperature, such as
phosphites, must improve significantly the long term
stability of PET in the processing conditions.
Acknowledgements
The Agence de l’Environnement et de la Maitrise de
l’Energie (ADEME) and the company ECO-EMBAL-
LAGES are gratefully acknowledged for their financial
support.
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