Polymer 45 (2004) 8751–8759

www.elsevier.com/locate/polymer

Water extraction and degradation of a sterically hindered phenolic

antioxidant in polypropylene films
Monica Bertoldoa,b,*, Francesco Ciardellib
a
INFM Udr Pisa, Via Risorgimento, 35 I-56126 Pisa, Italy
b
Dip. Chimica e Chim. Ind.le, Università di Pisa, Via Risorgimento, 35 I-56126 Pisa, Italy
Received 15 March 2004; received in revised form 5 October 2004; accepted 13 October 2004
Available online 5 November 2004

Abstract
Water extraction of the sterically hindered phenolic antioxidant Irganox 1010 from three polypropylene based polymeric films has been
studied in isothermal conditions at 40, 50 and 70 8C. The films made of isotactic polypropylene and two different heterophasic
polypropylene/ethylene–propylene monomers copolymers (PP/EPM copolymers) were immersed in closed water baths under nitrogen
atmosphere in order to minimise the oxidative process. The amounts of antioxidant that have left the films and are dissolved in the water bath
have been monitored over time by HPLC analysis and faster extraction kinetics were observed from the polymers than from the
homopolymer. No appreciable amounts of Irganox 1010 were found in the extraction water at any time, whereas its degradation by-products
were found by LC/MS analysis in the extraction water.
The experimental extraction kinetics from the three polymers were compared with the theoretical curves based on the Fick’s diffusion
equations solved both for a semi-infinite (degradation reaction faster than extraction) and a finite system (no degradation reaction) and
Irganox 1010 was demonstrated to be extracted by water from polypropylene based material faster than predictable only on the basis of the
values of its coefficient of diffusion in the polymers and of partition between water and polymer.
q 2004 Elsevier Ltd. All rights reserved.

Keywords: Polypropylene; Water extraction; Antioxidant hydrolysis

1. Introduction
Polyolefin based materials are widely used in many
applications where they came in direct contact with water as
in pipes, automotive parts, bottles and food packagings.
Usually polyolefins, which are made by apolar hydro-
carbonic chains, are insoluble in water and very low
permeable to water vapour so their interactions with this
solvent has often been neglected. However, when long time
contact is involved, water extraction of additives and low
molecular weight compounds can become effective thus
affecting the material properties and creating concern for the
public safety. For these reasons in the last decade an
increasing interest is arisen about possible leaching from
polypropylene products.
* Corresponding author. Address: INFM Udr Pisa, Via Risorgimento, 35
I-56126 Pisa, Italy.
E-mail address: monicab@dcci.unipi.it (M. Bertoldo).
0032-3861/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2004.10.044
Only few papers are available in the literature about the
water extraction behaviour of polyolefins [1–6], while many
data are available on the vapour permeability of derived
films [7,8]. Indeed water vapour permeability can be carried
out easily and in a relatively short time, whereas water
extraction analyses are complex and time consuming.
Moreover, the understanding of the water extraction results
requires kinetic studies already in the earlier stages of the
process and an analytical method able to detect very small
concentrations of compounds is necessary.
Materials may be subjected to water extraction
during the use either in flowing conditions like in
pipe and outdoor exposition or in static conditions,
where the equilibrium can be established between the
concentration of a specie within the material and the
extracting solvent. From a thermodynamic point of view
in the former situation all substances, also those which
are very little soluble in water could be extracted
because of the continuum washing of the surface, while
8752 M. Bertoldo, F. Ciardelli / Polymer 45 (2004) 8751–8759

in the later, only water soluble substances should be If the following conditions are realised:
extracted because of the repartition equilibrium.
The behaviour of BHT in polyethylene has been † The skin or surface layer has no different diffusion
investigated when the films are put in contact with water properties from those of the bulk.
for long time [1]. In static conditions, a continuum † The diffusion coefficient in the surrounding liquid
extraction was observed and a mechanism with reaction medium is much larger than that within the solid film.
has been proposed to explain the experimental data [2]. † The volume of the surrounding medium can be
However, no direct evidences have ever been reported on considered infinite (or the same is verified if the diffusing
the degradation of the phenolic antioxidants in water. molecules react in the surrounding medium faster than
A large number of phenols with different chemical they diffuse in the polymer).
structures were found in drinking water stored in closed
polyethylene pipes for 7 days at 23 8C [3]. The chemicals the solution of the diffusion equation corresponds to the
identified by mass spectroscopy analyse were assumed to be solution of a semi-infinite medium. In this case, the total
impurity or by-products of the phenolic additives usually amount of diffusing substance (Mt) that has entered or left
added to the polyethylene. the sheet at time t is given by Eq. (3) [9]:
In this work, a detailed investigation has been performed X N

Mt 8 Dð2n C 1Þ2 p2 t
concerning the extraction by water of the phenolic Z1K exp K (3)
MN nZ0
ð2n C 1Þ2 p2 4l2
antioxidant Irganox 1010 used as additive in films made
by three different polypropylene based materials: an where MN is the amount of diffusing substance that has
isotactic polypropylene homopolymer and two heterophasic entered or left the film after infinite time, t, the time and n,
polypropylene/ethylene–propylene monomers copolymers. an integer number.
The chosen phenolic antioxidant is widely used as If the surrounding medium is finite, the approach to the
thermal stabiliser additive in many commercial polyolefins problem is more complicated and the exact solution can be
because of its high efficiency (with respect to others found only for that case in which the system is infinitely
hindered phenol derivatives) related to its low diffusion mixed (Eq. (4)) [9].
coefficient [7].

The effects of the temperature and of the elastomer Mt XN
2að1 C aÞ Dq2n t
Z1K exp K 2 (4)
quality and quantity in PP on the extraction phenomenon MN nZ0
1 C a C a2 q2n l
have been determined and discussed. Moreover, an
analytical method allowing to detect 1 ppb of the antiox- where qns are the non-zero positive roots of Eq. (5)
idant in water has been set up and direct evidence of the tan qn Z Kaqn (5)
degradation of the Irganox 1010 by hydrolysis has been
reported. The influence of the hydrolytic mechanism on the and aZa/Kl where K is a partition factor.
migration kinetics has been discussed. MN 1
Z (6)
2lC0 1 C 1=a
1.1. Theoretical considerations

The diffusion of a molecule from a polymer film to its

surrounding medium can be described mathematically as
the case of diffusion into or out of a medium closed between
2. Experimental section
two parallel planes. This layer must be so thin that
effectively the amount of diffusing substance which does
not migrate through the plane faces can be neglected. 2.1. Materials
The process is related to the substance diffusion
coefficient D which in the case of diffusion in one direction Three polypropylene based materials manufactured with
only is defined by the Fick’s laws shown in Eqs. (1) and (2): the heterogeneous Ziegler–Natta catalyst technology were
used. Their features and characterisations were already
vC
F Z KD (1) reported elsewhere [11] and the data are summarised in
vx Table 1. The phenolic antioxidant Irganox 1010 (pentaer-
ythrityl tetrakis[3-(3,5-di-1,1dimethylethyl-4-hydroxyphe-
vC v2 C
ZD 2 (2) nyl)]propionate, CAS n. 6683-19-8), supplied by Ciba
vt vx Specialities, was added to the polymers by dry mixing. The
where F is the rate of migration per unit of section normal to resulting 0.2% (w/w) Irganox 1010/polymer mixtures were
the diffusing direction, C, the concentration of the diffusing extruded in order to obtain films with a thickness ranging
compound, x, the space co-ordinate normal to the section from 60 to 70 mm by using a laboratory heat flat extruder
and t, the time. (DR. Collin GMBH E30).
 M. Bertoldo, F. Ciardelli / Polymer 45 (2004) 8751–8759 8753

Table 1
Polymer features

Polymers Polymer features Crystallinity (a) Tm (8C)

a
HomoPP Homopolymer 0.41 159a
Heco1 Ethylene–propylene heterophasic copolymer made by polypropylene 0.26b 162b
homopolymer and 40% of EPM rubber (50/50 ethylene/propylene)
Heco 2 Ethylene–propylene heterophasic copolymer made by an ethylene/ 0.20b 142b
propylene random copolymer (2/98 ethylene/propylene) and 65% of
EPM rubber (50/50 ethylene/propylene)
a
Data taken from Ref. [10].
b
Data taken from Ref. [11].

2.2. Migration experiments
About 30 pieces of each 10!12 cm doped film were
washed with cold HPLC grade acetone by rapid immersion
and allowed to dry in a nitrogen atmosphere for about 3 days
and then placed inside a 34 mm ID and 20 cm long glass
tube (Fig. 1), previously filled with 120 ml of water. The
water was previously degassed and stored under nitrogen
atmosphere. All the water handling was carried out in a dry-
box.
Ten glass tubes for each polymer were maintained at 40,
50 and 70 8C, respectively. The tubes to be left in the oven
for more than 1 month were enclosed in 30 cm tubular films
welded at the top and bottom and filled with nitrogen.
At the appropriate time the test tubes were removed from
the oven, the films were taken out from water and stored in a
nitrogen atmosphere for 24 h or more.
2.3. Analysis of the antioxidant in the films
Each polymer film of 0.6–0.7 g was extracted by the
microwave method reported by Marcato and Vianello [12]
performing the extraction for 15 min at 125, 120 and 115 8C
for HomoPP, Heco1 and Heco2, respectively. The tempera-
tures were reduced to 120, 115, and 110 8C for films
immersed in water. The extraction solutions were concen-
trated to a few microliters and filtered through a 0.45 mm
PTFE syringe filter. The quantitative evaluations of the
antioxidant concentration were performed by HPLC using
hexadecyl 3,5-di-tert-butyl-4-hydroxy-benzoate (Aldrich
Chemical Company, CAS n. 67845-93-6) dissolved in the
extraction solvent as internal standard.
2.4. Analysis of additive in water
Each 120 ml water portion was submitted to a sequence
of four extractions with 5, 5, 3 and 2 ml of hexane,
respectively. The deriving cumulative hexane solution was
reduced to a small volume (about 0.5 ml) by flushing with
nitrogen in a lightly heated bath. Five millilitre of Irganox
1330 acetonitrile solution were added and the volume was
reduced again to about 1 ml. The determination of the
antioxidant in the resulting solution was performed by
HPLC as before.

2.5. Irganox 1010 degradation

A glass tube filled with oxygen free mixture 1/3 (v/v)

HPLC grade water/filtered-saturated solution of Irganox

Fig. 1. Assembly for migration experiments. Fig. 2. Kinetics of Irganox 1010 decrease in films at 70 8C.
8754 M. Bertoldo, F. Ciardelli / Polymer 45 (2004) 8751–8759
Fig. 3. Kinetics of Irganox 1010 decrease in films at 50 8C.
1010 prepared at 70 8C was set in an oven maintained at
70 8C and the solution concentration was monitored over the
time by HPLC analysis.
2.6. HPLC determination of antioxidants
The analysis were carried out with a HP1090 liquid
chromatograph equipped with DAD/UV detector (Agilent
Technologies, USA) and a reverse-phase column (Luna RP-
18) 15 cm length and 2.1 mm ID with 5 mm phase
(Phenomenex) that were eluted with a binary gradient
program from 5/95 to 0/100 water/acetonitrile in 1 min and
isocratically with acetonitrile for 15 min. The eluent flux
was set at a constant rate of 0.31 ml/min with column
temperature 50 8C.
Injection volume of 25 ml of the acetonitrile and water
solutions and 3 ml of ethyl acetate/hexane solution were
used. The wavelength of the UV detection was 282 nm for
the water and acetonitrile solution analysis and 274 nm for
the ethyl acetate/hexane extraction moistures analysis.
All solvents were of HPLC grade.
3. Results
The relative concentration of Irganox 1010 in HomoPP,
Heco1 and Heco2 films stored in water at 70 8C under
nitrogen atmosphere decreased with increasing the extrac-
tion time. At the beginning, an induction period was
observed which was longer for HomoPP (about 1 month)
than for the etherophasic copolymers (about 2 days). In Fig.
2, Mt indicates the amount of antioxidant in the film at t
time, and M0, the quantity of antioxidant present within the
film at zero time. Heco1 and Heco2 show similar linear with
time concentration decrease whereas a slower rate of
decrease was observed for HomoPP. The extraction of
Irganox 1010 was quite complete in both Heco1 and Heco2
after 110 days in contact with water, whereas it was half the
initial value in HomoPP films after the same period.
More complex kinetics were observed at 50 8C, (Fig. 3)
where the amount of Irganox 1010 within the films of all the
investigated polymers was constant during the early stages
of the exposure and began to decrease after some time. This
induction time was longer for the homopolymer (about 2
months) than for the hetorophasic copolymers (about 1
month).
At 40 8C, an essentially undetectable migration of the
antioxidant was observed from the homopolymer, whereas a
slow decrease of the antioxidant content began to be
observable after 230 days in Heco1 and Heco2 (Fig. 4).
The amount of Irganox 1010 in the extraction water was
very low and close to the detection limit of the method for
all the polymers and at all the temperatures investigated,
even though a different relative behaviour was detectable
with changing temperature. At 70 and 50 8C, the amount of
Irganox 1010 in water increased initially and, after having
reached a maximum value, decreased to reach a non-
detectable value after some days. As an example of this
behaviour the data relating to the extraction at 70 8C from
Heco1 are reported in Fig. 5. At 40 8C, the amount of
Irganox 1010 in water was found to be very low but constant
at any time.
In the water solutions hydrolysis products can be
detected and in particular, 3-[3,5-di-tert-butyl-4-hydroxy-
benzyl]propionic acid were found by LC/MS analysis. The
amount of these by-products increased as the time of water–
polymer contact increased. To verify the possible Irganox
1010 degradation, already postulated in literature [1], an
oxygen-free Irganox 1010 water solution kept at 70 8C
under nitrogen atmosphere was monitored over the time by
HPLC, it was observed that the antioxidant concentration
decreased to a non-detectable value in 3 days (Fig. 6).
Irganox 1010 degrades also at 50 8C even if the process is
slower with a longer induction time. As at 70 8C, the rates of
extraction–degradation of Irganox 1010 are slower for
HomoPP than for the films from copolymers.
The undetectable decrease of the antioxidant in the films
kept at 40 8C and its very low (at the first stage) or not
detectable concentration in water seems to exclude
degradative processes at this lower temperature.
A progressive yellowing over time of both the films
submitted to water extraction and of the corresponding
water solutions was also observed. In particular, the
phenomenon occurred after a short time at 70 8C, and
after somewhat longer times for the tests carried out at lower
temperatures. Moreover, no presence of CaO chromophore
in these polymer films was observed by FT-IR analysis, and
the product responsible for the yellow colour could be
extracted from the films with organic solvents. This
behaviour agrees with the observed presence of benzophe-
none derivatives found by Arvin and co-workers by GC–MS
in drinking water exposed to polyethylene pipe contact for 7
days [3]. A gel effect on the films was observed after
microwave extraction, especially in those films maintained
at 70 8C and in those which had remained for long time at 50
 M. Bertoldo, F. Ciardelli / Polymer 45 (2004) 8751–8759
and 40 8C. However, no differences were observed between
the FT-IR spectra and the DCS profiles recorded before and
after the migration tests.
4. Discussion
4.1. Irganox 1010 degradation
It is evident from the data showed in Fig. 6 that the
consumption of the antioxidant in water proceeds with a
complex mechanism.
The reaction of hydrolysis of esters in presence of water
is a well known equilibrium process which is usually
reported to require acidic or basic catalysis. The mechanism
in neutral condition should be bimolecular and involves a
nucleophile attack of a water molecule to a carbon atom of
one of the four carbonyl groups of I (Scheme 1). The
reaction product II is an organic acid, the dissociate form of
which can catalyse the hydrolysis of other Irganox 1010
molecules (I) or of further ester groups belonging to the
reaction by-product III. The complete hydrolysis of I should
follow the four steps mechanism sketched and provides four
molecules of acid for each molecule of Irganox 1010.
In spite of the autocatalytic effect of the acid formed, the
reaction rate decreases as the reaction time increases (Fig. 6)
because of the equilibrium state approaching all elementary
steps. The final mixture is expected to be composed by
species I–VI at concentrations depending on the kinetic
constants of the elementary steps and on other parameters
such as the dissociation of the acid and the solubility in
waters of each specie. In particular Irganox 1010, which has
no hydroxyl groups and the highest number of condensed
groups and then it is expected to be the less soluble and
present at low concentration in the final mixture as
experimentally found.
8755
4.2. Migration kinetics
The concentration of water inside the polyolefin matrices
is very small because of the small values of its solubility
constant, thus the real probability that a molecule of Irganox
1010 may react with a water molecule is so small that the
rate of the hydrolysis reaction inside polymer can be
neglected in the discussion.
By using the diffusion coefficients of Irganox 1010
estimated for the same polymers [11] and by using the
calculated partition coefficients given in Table 2 it is
possible to simulate the kinetics given by Eqs. (3) and (4).
The former equation describes the diffusional behaviour of a
specie that moves from a finite sheet to an infinite
surrounding in which it degrades with a rate much larger
than its diffusion coefficient in the solid [2,9]. The latter
describes the diffusion from a finite sheet to a surrounding
finite medium without reaction. This equation is valid for a
solution having the same concentration as in an infinite
mixed system. Moreover, the theoretical model does not
account for the boundary layer near the surface where a
concentration gradient may exist. However, this layer
becomes negligible in infinite mixed systems or when the
rate of diffusion in the surrounding media (water) is much
higher than in the finite sheet (polymeric film). If such a
boundary layer exists linear migration kinetics is usually
observed and the curve slope depends on layer thickness. In
the migration experiments reported in this paper, the above
layer is negligible and the concentration may be assumed to
be the same in every point of the water solution. Indeed, the
diffusion coefficient of Irganox 1010 in water at 70 8C can
be estimated by using the following equation:
D Z ukT (7)
in which T is the absolute temperature, k, the Boltzman
8756 M. Bertoldo, F. Ciardelli / Polymer 45 (2004) 8751–8759
Fig. 4. Kinetics of Irganox 1010 decrease in films at 40 8C.
constant and u, the mobility of Irganox 1010 in the liquid. If
the molecule is assumed to be a spherical particle, its
mobility in a liquid may be described by the Stoke’s law:
1 effectively stirred and Eq. (4) may be used to simulate the
uZ (8)
6phr
By using the calculated radius rZ1.326!10K9 m of
Irganox 1010, its diffusion coefficient in water may be
estimated to be DZ2.97!10K6 cm2/s at 70 8C, which is
much larger than the values for the same molecule in the
polymer matrix. By using this estimated value and the
theory of Brownian motion it is possible to calculate
the average distance covered in a fixed time by a molecule
of Irganox 1010 in a water solution at 70 8C. It is evident
that (Fig. 7), in the absence of any difference of chemical
potential within the liquid, a molecule can move in only 1
day from the centre of the experimental glass tube to its
wall. If, moreover, a difference of chemical potential exists
between the polymer surface and the liquid, because of the
different concentration of the molecule, Irganox 1010 must
Fig. 5. Relative Irgano1010 amount, which was found inside water
contacted with Heco1 at 70 8C, versus time.
Fig. 6. Relative concentration of Irganox 1010 in a water solution
kept under nitrogen atmosphere at 70 8C, versus the time of
storage. The relative concentration of Irganox 1010 is given by the
ratio between its concentration in the solution at t and zero time.
move faster and then the solution can be considered as being
migration kinetics.
Some experiments were performed at 70 8C on Heco1 by
stirring the solution during the contacting time in order to
verify experimentally the absence of boundary layer effects.
It was observed that the amount of Irganox 1010 leaving the
sheets in the course of a few days and in the course of 1
month is the same as that detected under static conditions
confirming that the assumption of the absence of the
boundary layer of liquid was correct.
The partition coefficients between water and polymer of
Eq. (4) were estimated using the literature value of the
Irganox 1010 solubility in polypropylene reported by Frank
and Frenzel [13]. They gave a value of 1.5% in an atactic
amorphous polypropylene at 70 8C. Therefore, it has been
demonstrated that additives solubilise only in the amor-
phous phase of polypropylene [14] thus the values of
solubility (S) for Irganox 1010 in the three polymers under
investigation were estimated by using Eq. (9) and the value
of the amount of rubber phase (a) in each polymer (Table 1).
The solubility results in the polymers are reported in Table 2
together with the estimated partition coefficients calculated
by assuming a solubility value of 5 ppm for Irganox 1010 in
water.
S Z 1:5 !ð1 K aÞ (9)
In Fig. 8, the experimental kinetics of migration from
HomoPP into water at 70 8C was compared to the correspond-
ing simulated curves given by Eqs. (3) and (4). In the early step
of the migration the loss data are better compatible with the
model for the migration into a finite medium without reaction.
Actually the amount of Irganox 1010 in solution goes through
a maximum and later reaches a non-detectable value, which is
incompatible with the considered model. Also a kinetic model
 M. Bertoldo, F. Ciardelli / Polymer 45 (2004) 8751–8759 8757

Scheme 1.

Table 2
Thermodynamic data of Irganox 1010 at 70 8C

Polymer S (%) K (!104)a ab D (!101l)c (cm2/d)

HomoPP 0.885 5.6 0.087 1.87
Heco 1 1.11 4.5 0.068 87.0
Heco 2 1.20 4.2 0.059 311.0
a
Partition coefficient between water and polymer estimated by assuming the experimentally estimated value of 5 ppm for Irganox 1010 in water and the
values given for the solubilities within the polymers.
b
aZK(Vwater/Vpolymer).
c
Data taken from Ref. [11].
8758 M. Bertoldo, F. Ciardelli / Polymer 45 (2004) 8751–8759
pffiffiffiffiffiffiffiffi
 Z 2DtÞ
Fig. 7. Time depending of average migration distance ðDr
of a molecule of Irganox 1010 in water at 70 8C.
Fig. 8. Comparison between the experimental kinetics of migration of Irganox 1010 from HomoPP into water at 70 8C and the corresponding
simulated curves given by Eqs. (3) and (4).
as those proposed by Gandek and co-workers [1] controlled by
the degradation reaction does not agree with the experimental
data because in this case a constant concentration of Irganox
1010, corresponding to the steady state value, must be present.
If the degradation reaction is the rate determining step
following a first-order kinetics, a straight line is expected
with positive intercept [2]. On the contrary the extrapolation of
the experimental curve to timeZ0 shows an apparent negative
value which indicates a more complex mechanism than that
described by the model.
5. Conclusion
A direct evidence of the degradation of Irganox 1010 by
hydrolysis of the ester groups in deionised water was
demonstrated while effect by the polymer or its by-products
is excluded. As the consequence the migration of Irganox
1010 into water from polypropylene polymers was found to
be a complex process probably because of the degradation
reaction and the small affinity for water. The amount of
Irganox 1010 found in water was below the detection limit
at any times indicating its rapid hydrolysis. The hydrolysis
in water is responsible for the continuous decrease of the
antioxidant concentration in the films and the rate at which
the additive leaves the films was higher than predictable
only on the basis of the values of its coefficient of diffusion
in the polymers and of partition between water and polymer.
From a practical view point, the present study confirms
and suggests that the contact with water may reduce the
lifetime of polypropylene products. On the other hand, the
necessity was evident of investigating the nature of
the Irganox 1010 degradation products and their possible
toxicological effects.
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