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Identification of Additives in Polypropylene and Their Degradation

under Solar Exposure Studied by Gas Chromatography−Mass
Spectrometry
Enrique Blázquez-Blázquez, María L. Cerrada, Rosario Benavente, and Ernesto Pérez*
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ABSTRACT: Additives are absolutely essential in the development of commercial

polymeric materials. Accordingly, an exhaustive control of composition and
Downloaded via 163.116.214.63 on November 20, 2024 at 05:15:31 (UTC).

evolution in these additives over time is necessary to validate their performance

and safety during their shelf life and, consequently, their ultimate applications. Gas
chromatography coupled with mass spectrometry, GC−MS, is described in the
present work to identify and analyze the content of a wide variety of additives,
commonly used in industrial polymeric materials. First, the identification under the
present experimental protocol of additives with a relatively high molecular weight
(Irganox 1330 and Irganox 1010) has been successfully attained. Second, the
evolution under solar exposure over time has been analyzed by GC−MS for 11
additives and derived substances, which have been identified in a commercial polypropylene sample, estimating the corresponding
depletion times. In addition, the resultant increase of carbonyl groups in the polymeric macrochains along the photo-oxidation has
been also determined by infrared spectroscopy. Therefore, GC−MS is found to be a reliable tool for the analysis of the evolution of
commonly used polymer additives under specific degradation conditions, which can be very useful in the formulation of improved
future additivations.

1. INTRODUCTION effort to make the decision on the appropriate and optimal

Polymers are currently one of the most commonly used ionization mode for each different additive.5
Gas chromatography−mass spectroscopy (GC−MS) has
materials. Among them, the complete hydrocarbons (poly-
been also used as a fast and simple technique to determine
ethylene (PE), polypropylene (PP), polystyrene (PS))
additives in polymers,10−15 with an optimum chromatographic
together with poly(vinyl chloride) (PVC) represent the largest
resolution power. GC−MS allows solving numerous industrial
segment of industrial polymers. This fact explains why
problems,15−19 namely, the nontargeted analysis (where the
antioxidants, lubricants, and stabilizers comprise a large part
identification of additives or components of a mixture has to be
of the organic additives since they are most frequently used in
performed), and also the migration of additives and the
polymer formulations for protection against degradation
existence of residual monomers, which may be indicative of the
during processing or during their environmental exposure to
quality of a specific product for its massive consumption.
the action of oxygen and/or ultraviolet (UV) radiation.1−3
One of the limitations of the GC−MS techniques is the
Thus, all types of commercial polymer-based materials,
analysis of substances with a relatively high molecular weight.
including thermoplastics, thermosets, and rubbers, require a
Their evaluation can be, however, performed using shorter
correct additivation, essential for optimizing their ultimate
columns with phases as thin as 0.1 μm,20,21 available for
properties and prolonging their useful life. Additives are often temperatures as high as 400 °C.
used in a dual role: on the one hand, to promote protection The main groups of additives customarily used in polymer
against external agents and, on the other hand, to contribute in formulations that can be analyzed and quantified by the GC−
the modification of the physical, chemical, and thermal MS technique are, among others, antioxidants, UV stabilizers
properties of the final material. and absorbers, thermal stabilizers, lubricants, plasticizers, and
Several works have been devoted to the evaluation of
additives in polymers,4−10 but considering the relatively high
molecular weight of some additives, many of those studies use Received: September 18, 2019
high-performance liquid chromatography (HPLC) coupled Accepted: January 23, 2020
with different types of detectors, i.e., mass spectrometry (MS) Published: April 17, 2020
or UV. The simultaneous identification of unknown complex
mixtures of additives and their degradation products is not,
however, straightforward by HPLC since it requires an extra

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flame retardants. These additives are, thus, necessary for to around 45 days), with a final deviation from that linearity
protecting the final material from degradation and/or boosting ascribed to being more at the end of the summer season.
the improvement of its properties. For instance, they are of
capital importance in polymer formulations for outdoor 3. RESULTS AND DISCUSSION
applications, as is the case of plastics in agriculture. In other 3.1. Analysis of High-Molecular-Weight Additives.
cases, however, some additives, or their degradation products, The first objective of this study has been the identification of
may involve specific health safety problems, namely, in additives with a relatively high molecular weight under the
materials with applications for drinks and food pack- present experimental protocol. Two additives found in many
aging.7,9,12,22−25 polymeric formulations have been analyzed: Irganox 1330
Studies dealing with various additives in different polymers (also named as Ethanox 330), with M = 775 g/mol, and
have been reported, including PE, PP, PVC, poly(ethylene Irganox 1010 (M = 1178 g/mol).
terephthalate),6,8,26 and also multilayer films.27 Practically all The results concluded the feasibility of detecting these two
polymer formulations include specific additives, depending compounds. Thus, although it is not possible to detect the
mainly on their precise final application. intact Irganox 1010 (since its high molecular weight prevents it
The main objective of the present research is to propose the from being volatilized at the working temperature of the
use of gas chromatography coupled to mass spectrometry injector), it is, however, recovered from the polymer by
(GC−MS) as an applicable and reliable approach for the ordinary extraction protocols.
assessment of some common additives incorporated routinely Then, its presence in a certain polymer can be easily
into polymers. The aim is twofold: first, the identification deduced from the observation of its degradation products, and
under the present experimental protocol of additives with a to get the most output of the GC−MS technique, we have
relatively high molecular weight has been tested. The second systematized the degradation path of this compound. Thus, the
objective has been the study of the effect of photo-oxidation on injection of this intact additive in the chromatographic system
a commercial sample of PP that has been exposed to natural allows observing a repetitive degradation pattern, which can be
climatic conditions. That analysis is carried out both in the seen in Figure 2.
polymer itself and in the different additives included in the
sample. Thus, the relative variations of the distinct additives
are determined as a function of solar exposure. Moreover, the
formation of oxidized species in the polymeric macrochains
along this environmental aging is examined by Fourier
transform infrared (FTIR) spectroscopy. Additionally, the
linear retention index (LRI) for commonly used additives and
their degradation products is determined.

2. SOLAR EXPOSURE PROTOCOL

Pieces of the compression-molded sheets (see Section 5 at the
end of the manuscript) were exposed to the actual weather
environment under tests ASTM G 7-99, ASTM D 1435-99,
Figure 2. Chromatogram showing the degradation products of
and ASTM D 5272-92. The photo-oxidation was carried out Irganox 1010.
during 57 days in the summer season. The weather conditions
in this period and location were characterized by rather high
temperatures (sometimes above 40 °C), with practically no It has to be considered that these compounds from Irganox
cloudy days and very low relative humidity. 1010 are degradation products obtained in the injector,
Figure 1 shows the intensity of solar energy to which the standing in contrast to the so-called nonintentionally added
samples have been exposed. The dots indicate the days when substances (NIASs), which are compounds formed during the
samples were collected for analysis. It can be observed that regular processing and useful lifetime of the polymeric
there is a linear relationship between solar energy and time (up material.9,25
The assignment of the degradation products of Irganox 1010
appearing in Figure 2 has been carried out by considering their
mass spectra (see the Supporting Information, Figure S1) and
previously reported studies, which indicate that the hydrolysis
of the ester bond is the predominant degradation mecha-
nism.28 Those authors proposed the structures of several
degrading products obtained under accelerated aging tests. In
the present GC−MS conditions, at least seven different
structures have been identified. Some of them have been
described before;28 however, it is important to keep in mind
that there were identified by HPLC.
The degradation pattern depicted in Figure 2 is, therefore,
the key characteristic to discern the presence of Irganox 1010
in a particular sample. The most abundant degradation product
Figure 1. Variation of the solar energy received by the exposed corresponds to methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-
samples as a function of time. propionate, Metilox. The tentative assignment of other
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degradation substances is depicted in Scheme S1 of the 3.2. Degradation of Additives in Polypropylene

Supporting Information. under Solar Exposure. The second aim of this work has
Therefore, Irganox 1010, if present in a certain sample, been the study by GC−MS of the evolution of different
should produce the degradation pattern shown in Figure 2, i.e., additives over time in a specific commercial PP sample that has
all of the degradation peaks have to be observed simulta- been exposed to natural weathering conditions for different
neously and with the intrinsic relative areas deduced from that periods (see Figure 1 for the variation of the solar energy
figure (as explained, Metilox can also arise from the received by the samples). Figure 4 shows the chromatograms
degradation of Irganox 1076). Obviously, it can be argued
that those compounds may have been originally present in the
sample, either because they were added as additives or because
they have been produced by a former degradation product
during the processing or lifetime conditions of the material.
The first possibility is highly improbable, since those
compounds are not regular additives, and all of them have to
appear with the fingerprint in Figure 2, for the particular
column and experimental conditions employed. The second
one is also improbable, considering that the degradation
products in that figure have been obtained under the rather
rigorous conditions of the injection system (see Section 5),
with temperatures considerably higher than those employed in
the regular processing of a polymer material.
Another additive of relatively high molecular weight is
Irganox 1330, mentioned above. In this case, the intact
antioxidant can be, however, detected by GC−MS, and the Figure 4. Chromatograms of the extracts corresponding to the initial
chromatogram corresponding to the original nondegraded sample (0 days) and to that after 57 days of solar exposure.
Irganox 1330 can be observed in the upper part of Figure 3.
of the extracts corresponding to the initial sample and to that
with the maximum solar exposure analyzed (57 days). From
these chromatograms, and from the corresponding mass
spectra, 11 additives have been identified (plus the oxidized
form of Irgafos 168, labeled as Irg168ox), as shown by the
legends in Figure 4 for the chromatogram corresponding to
day 0. Figure 4 also includes 4-cyano-4′-n-oxyoctyl-biphenyl,
8OCB, added to the different extracts as an internal standard.
A more detailed report is given in Table 1, where the name
and CAS number, structure, retention time, molecular weight,
and a linear retention index of the additives are presented. As
observed, different antioxidants, UV stabilizers, plasticizers,
and lubricants were detected.
A minor amount of Metilox is also observed. This
compound is reported to be a degradation product of Irganox
Figure 3. Chromatograms of the original and degraded Irganox 1330. 1076 or Irganox 1010.17,23,25,29 Since there is no sign of other
degradation products of Irganox 1010 (compared with Figure
This additive can undergo degradation under processing or 2), this small amount of Metilox is supposed to arise from the
useful lifetime conditions; in such a case, the degraded degradation of Irganox 1076 present in the sample.
substances are, therefore, NIAS. The middle chromatogram in As mentioned in Section 5, the values of the apparent
Figure 3 shows the degradation compounds for a sample of concentration of different additives were determined from the
Irganox 1330 that has been exposed at 250 °C for 40 min, individual peak areas in relation to the area obtained for the
corresponding to around 27% degradation. It can be observed internal standard, 8OCB. The corresponding variation with
that the intact Irganox 1330 is still the most abundant exposure time is shown in Figure 5. The natural variable is the
compound (peak at 34.0 min, LRI = 4870), and the three extra solar energy received by the samples, but Figure 1 shows the
peaks arising from the NIAS are also observed (in fact, the relationship between that parameter and the time of exposure,
original sample shows already a small amount of the which is more insightful. Anyway, it can be observed in Figure
degradation product appearing at 33.7 min). 5 that the maximum intensity corresponds to Irgafos 168, while
The lower chromatogram in Figure 3 corresponds to a the initial amount of Tinuvin 770 is the lowest for the additives
sample subjected to more severe degradation conditions (80 found and analyzed.
min at 250 °C), where the intact Irganox 1330 has practically Figure 5 shows that these relative concentrations cover a
disappeared (92% degradation), and now the most abundant wide range (more than 2 orders of magnitude), and, in order to
compound is the one observed at 33.1 min. get a more intuitive picture of their variation with solar
The nature of these compounds produced from the exposure, the percentages related to the initial concentration
degradation of Irganox 1330 and their mass spectra can be are represented in Figure 6.
seen in the Supporting Information (Scheme S2 and Figure It is important to point out that although the overall peaks in
S2). the chromatograms (like those in Figure 4) may be rather
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Table 1. Name and CAS Number, Structure, Retention Time (tR), Molecular Weight (M), and Linear Retention Index (LRI)
for Different Additives Found in the Extracts

small and involve huge uncertainty, the relative variation of Finally, there is a third group with a much higher rate of
some additives has been evaluated (see Section 5) under SIM depletion: less than 10 days for t0.5, including three additives:
mode (selected ion monitoring) from the analysis of the more isopropyl myristate, erucamide, and Irgafos 168.
representative m/z peak in the corresponding mass spectrum. It follows, therefore, that under solar exposure most of these
Coming back to Figure 6, the relative variations of additives additives are considerably degraded and consumed, and it is
can be categorized into three groups. In the first one, important to mention that the depletion of these additives
(with the exception of adipate) follows an exponential
corresponding only to bis(2-ethylhexyl) adipate, shows a
behavior, inside the experimental error. Thus, the time
practical constancy with exposure time, indicating that it does dependence of these processes can be expressed by an
not exhibit significant degradation over the analyzed exposure. exponential function of the type
The reason may be the presence of less labile groups in this
compound. I = I0 exp( −t /τ ) (1)
The second group (the more numerous one, which includes were I0 and I are the initial concentration and that at time t,
seven compounds) shows an “intermediate” rate of depletion. respectively, and τ is the characteristic time of depletion so that
If the time necessary for 50% depletion, t0.5, is taken as a simple 1/τ represents a kind of rate for the degradation process.
parameter, this group presents values for this parameter from Obviously, the time for 50% depletion, t0.5, mentioned above,
around 15 to 40 days. corresponds to I/I0 = 0.5, so that from eq 1 it follows that τ =
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Regarding this additive, it is important to mention that its

decomposition involves the formation of an oxidized form
(structure represented in the last file of Table 1). The
concentration of Irgafos 168 in the extract for the highest solar
exposure is diminished very much (see upper chromatogram in
Figure 4), with the corresponding increase of the signal for the
oxidized form of Irgafos 168. However, the initial chromato-
gram shows also a very important proportion of oxidized
Irgafos 168. In fact, the corresponding quantification gives a
value of around 40% in the oxidized structure for the day
labeled as 0. It means that a considerable degradation has
occurred prior to these experiments (including the initial
pelletization of the polymer, its posterior exposure to ambient
conditions, and the compression-molding into sheets for these
analyses). That percentage of 40% means that the initial state
Figure 5. Variation of the apparent concentrations of different corresponds to around 5 days of solar exposure when
additives with exposure time. considering the results in Figure 6.
It is important to consider that the relevance of the observed
degradation rates will depend mainly on the purpose intended
for a particular additive. Thus, certain additives may be used
only as lubricants for facilitating polymer processing, so it does
not matter if that additive degrades more rapidly. The opposite
case corresponds to antioxidants, where it is essential that they
last as much as possible in the polymer system. In Figure 7, we
focus our attention on the additives with the fastest
degradation rates isopropyl myristate, erucamide, and Irgafos
168; among these, the first two are lubricants, mostly intended
for processing, so that their formulations may be appropriate.
In the case of Irgafos 168, however, a more convenient
formulation has about twice the initial concentration found in
the studied polymer sample.
The effect of photo-oxidation in the PP sample itself has also
been studied by monitoring the evolution of carbonyl groups.
Figure 6. Variation with exposure time of the percentage in relation to This analysis has been performed by FTIR-attenuated total
the initial concentration for the different additives. For simplicity, only reflectance (ATR) both in the initial polymer and in the
error bars of selected compounds have been included. samples after solar exposure. Additionally, a small amount of
polymer without additives (they were extracted as detailed in
Experimental Section) has been also exposed to solar
irradiation (up to 29 days).
t0.5/0.693. Therefore, either τ or t0.5 can be used for
It has to be considered that only when the concentration of
characterizing the process, although t0.5 is slightly more
antioxidants has been reduced very much, then the polymer
intuitive.
begins to degrade appreciably.14
Figure 7 shows the values of time τ0.5 for different additives.
The results in the carbonyl region (plus those associated
Irgafos 168 presents the highest degradation rate, as deduced
with the band at 1460 cm−1 taken as reference) are displayed
from this figure; precisely, its own degradation is supposed to
protect the entire system (polymer and also the other in Figure 8 for some selected samples (with and without
additives).30,31 additives). The band at 1460 cm−1 is ascribed to the
asymmetric deformation vibration of the methylene group, as
an internal standard.32,33
It can be clearly observed in Figure 8 that the original PP
sample exhibits already a small number of carbonyl groups,
mainly centered at 1735 cm−1, attributed to ester groups,34−37
with a much smaller proportion of the band at 1712 cm−1,
assigned to acid groups.34,36−39 The total amount of carbonyl
groups rises with solar exposure, and this increase is
considerably higher, as expected, for the PP sample without
additives. Moreover, there is a clear inversion of the relative
intensities between the bands at 1735 (ester groups) and 1712
cm−1 (acid groups), so that the latter species become dominant
at high exposure times. A third component of the oxidation
species appears at 1780 cm−1, attributed to lactones.36,37,40
This behavior differs somewhat from those of other
findings,36 where initially the band at 1712 cm−1 is dominant
Figure 7. Values of degradation time τ0.5 for different additives. and the band at 1735 cm−1 becomes dominant only after more
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amount of carbonyl species were detected in the aforemen-

tioned study43 and in other works.36 Here, the results in Figure
9 show a continuous increase of the carbonyl signals, without
the “induction” period. The reason might be associated with
the fact, mentioned above, that the initial PP sample previous
to its solar exposure already shows a significant amount of the
oxidized form of Irgafos 168, corresponding to about 5 days of
irradiation.
An important feature is the evolution of the two main
components of the carbonyl signal. The component at 1735
cm−1 (related to ester groups) is dominant in the initial stages
of the photo-oxidation, as observed in Figure 8. The rate of
formation of species appearing at 1712 cm−1 (acid groups) is,
Figure 8. FTIR spectra in the carbonyl region expanded down to the
however, considerably higher than that related to the band at
band at 1460 cm−1, taken as reference, for the indicated PP samples: 1735 cm−1 (by a factor of around 1.5 in both additivated and
additivated (Addit) at different times of exposure and nonadditivated nonadditivated samples). This is the reason why the
(NAddi) at 29 days. The spectra have been shifted vertically for component at 1712 cm−1 becomes dominant at high exposure
clarity. times.
As a final aspect, the effect of photo-oxidation is clearly
than 80 h of thermo-oxidation. Moreover, the relative noticed from the progressive whitening of the samples (see
proportion of lactones (band at 1780 cm−1) is much more Figure S3 in the Supporting Information).
relevant in that work. This trend was also found in isotactic
metallocene iPP irradiated by different doses of the electron 4. CONCLUSIONS
beam.41 It should be indicated, however, that the additivation
of those PP samples is rather different from that in the present Gas chromatography coupled with mass spectrometry, GC−
case. Furthermore, the electron beam irradiated specimens MS, has been proved to identify and analyze the content of a
were synthesized with a metallocene catalyst instead of using a wide variety of common additives used in polymeric materials
Ziegler−Natta one and, consequently, important micro- (antioxidants, UV stabilizers, lubricants, plasticizers), including
structural variations exist.41 It has to be considered that the the evaluation of additives with relatively high molecular
amount of thermo-oxidation, in addition to the presence of weights and their degradation compounds.
stabilizers, depends on details of both chemical and physical Thus, the identification under the present experimental
structures of the polymer.42 protocol has been successfully attained in the case of two
Quantification of the carbonyl groups has been made by additives of relatively high molecular weights found in many
integrating all of the signals involved in this region, from 1640 polymeric formulations: Irganox 1330 (also named as Ethanox
to 1820 cm−1, considering that the carbonyl species include 330), with M = 775 g/mol, and Irganox 1010 (M = 1178 g/
those various components and that their relative intensity mol).
changes considerably with oxidation degree. The results are Moreover, GC−MS has been also effectively tested for
shown in Figure 9. analyzing the evolution of 11 additives identified in a
commercial PP sample as a function of solar exposure time,
and the corresponding depletion times have been determined.
The effect of photo-oxidation in the PP sample itself, studied
by FTIR−ATR, indicates that the amount of carbonyl groups
in the sample with additives is, as expected, considerably lower,
by a factor of around 5, than that found in a nonadditivated
sample.
There is also a clear inversion of the relative intensities
between the bands at 1735 cm−1 (ester groups) and 1712 cm−1
(acid groups). The latter species become dominant at high
exposure times since their rate of formation is higher than that
for the ester groups by a factor of around 1.5.
In conclusion, GC−MS under the present experimental
protocol is found to be a powerful and reliable tool for the
Figure 9. Variation of the total amount of carbonyl groups as a analysis of the commonly used polymer additives and their
function of solar exposure time for the additivated and nonadditivated evolution under specific degradation conditions, which can be
PP samples. very useful in the formulation of improved future additivations.
As expected, the amount of carbonyl groups in the
5. EXPERIMENTAL SECTION
nonadditivated sample is considerably higher, by a factor of
around 5, than that found in the sample with additives. A A commercial Ziegler−Natta isotactic PP has been used for
rather similar value has been reported before,43 where the this study, with the following characteristics: melt flow index of
factor between nonadditivated and additivated PP sample was 4.2 g/min (at 230 °C, load 2.16 kg); Mw = 395 000 g/mol;
around 6. The difference observed with the present results is Mw/Mn = 6.5; melting temperature: 161 °C. This particular
that a certain induction period took place before a significant polymer is intended for use under weathering conditions.
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Sheets around 500 μm thick were obtained by compression The relative variation of some additives appearing in a small
molding in a Collin press at 210 °C for 4 min and at a nominal concentration has been evaluated under SIM mode from the
pressure of 25 bar, followed by fast cooling to room analysis of the more representative m/z peak in the
temperature at the same pressure. corresponding mass spectrum. This is the case of Tinuvin
The samples were exposed to the actual weather environ- 770, which presents a rather prominent peak for m/z = 124,
ment for 57 days in the summer season (see Section 2). For and also for Irganox 1076, which appears to coelute with the
this purpose, a self-made aluminum sample rack was used, much more prominent signal of oxidized Irgafos 168 (see
placed on the roof of our institute located in Madrid Figure 4). In this case, the selected m/z values were 515 and
(coordinates 40°25′ N, 3°41′ W). As recommended by the 530, which are distinctive of Irganox 1076 and not present in
standard, the rack is positioned with an inclination of 45° on the mass spectra of oxidized Irgafos 168 (see Figure S4).
the horizontal base, oriented toward the south, and at more Identification of compounds was carried out, first, by
than 1 m above ground level. The amount of solar energy was matching their mass spectra vs NIST08 (US National Institute
measured using a KIMP and ZONEN radiometer model of Standards and Technology, Gaithersburg, MD) commercial
Solarimeter Integrator CC2 located next to the sample rack. library, with a probability above 90%. The identification was
This equipment measures the accumulated solar energy further ascertained by comparison with the corresponding pure
between 300 and 3000 nm. compounds when these were available.
The evolution of additives was analyzed periodically, taking The studied compounds cannot always be found in the mass
the solar energy received as a variable. These samples were spectrometer software libraries (especially when the peaks
extracted in a Soxhlet with dichloromethane for 8 h by taking correspond to degradation products identified from high-
1.2 g of each exposed sheet and using 70 mL of organic molecular-weight additives). In such cases, the assignment is
solvent. Once the programmed extraction period was finished, made by comparing the expected fragmentation path from the
the solvent was concentrated in a rotary evaporator. The most probable degradation products with that observed in the
obtained residue was transferred to a chromatographic vial and chromatogram.
dried with a nitrogen stream. Then, it was redissolved in a In addition, the use of a linear retention index (LRI) turns
known volume of chloroform containing 0.35 mg/mL 4-cyano- out of practical importance.44,45 This approach is obtained
4′-n-oxyoctyl-biphenyl (8OCB) employed as an internal from the elution times and is calculated taking into account the
standard. The volume of solvent used was 1 mL for all the retention times of the unknown compound and those of the
samples. The 8OCB is one of the components of the well- corresponding anterior and posterior eluating n-alkanes. The
known Merck E7 mixture of liquid crystal compounds, which is evaluation of the results of a hydrocarbon standard comprising
stable at high temperatures, and it is not present in polymer between C12 and C49 has allowed establishing retention times
from which it was possible to estimate the LRI for different
formulations.
compounds of interest found in the sample under analysis.
The use of other solvents, such as diethyl ether or ethyl
These values, together with those of other many common
acetate, and the increase of the extraction times did not show
additives and their degradation compounds, are collected in
higher recoveries for the studied additives.
Figure S5 of the Supporting Information; also, their structures
The analytical determination was carried out using a Hewlett
are given in Table S1.
Packard 6890 GC gas chromatograph equipped with an
The effect of photo-oxidation in the PP sample has been also
Agilent Technologies mass spectrometry detector model 5973.
studied by analyzing the evolution of carbonyl groups. For that,
The separation of the compounds was performed on a DB5- Fourier transform infrared spectra with attenuated total
HT capillary column (15 m length × 250 μm internal diameter reflectance (FTIR−ATR) were recorded on a PerkinElmer
and 0.1 μm film thickness). The carrier gas used was helium Spectrum One spectrophotometer (PerkinElmer, Waltham,
with a flow rate of 1 mL/min. A volume of 1 μL of the MA) with a resolution of 4 cm−1.

■
obtained extract was injected in split mode with a split ratio of
20:1, at 270 °C. An Agilent glass liner, containing glass wool,
was employed. ASSOCIATED CONTENT
The chosen chromatographic method lasted 37.5 min. The *
sı Supporting Information
initial test temperature was 80 °C, which was increased up to The Supporting Information is available free of charge at
340 °C at a controlled rate of 8 °C/min. It was maintained at https://pubs.acs.org/doi/10.1021/acsomega.9b03058.
that temperature for 5 min. This method is suitable for
optimum separation of a wide range of compounds found Mass spectra and assignment of the degradation
frequently in polymers, and also of linear hydrocarbons products of Irganox 1010 and Irganox 1330; whitening
between around C12 (dodecane) and C49 (nonatetracon- of the sample by the effect of photo-oxidation; mass
tane). The electron impact (70 eV) was the selected type of spectra of oxidized Irgafos 168 and Irganox 1076; and
ionization for the mass spectrometer. values of the linear retention index for various additives
The values of apparent concentration for the diverse and degradation products (PDF)

■
additives were determined from the individual peak areas in
the total ion chromatogram of each additive in relation to the
AUTHOR INFORMATION
area obtained for the internal standard, 8OCB. Absolute
concentrations may be somewhat different since variations in Corresponding Author
response factors among the studied substances are expected. Ernesto Pérez − Instituto de Ciencia y Tecnologiá de Polimeros
́
Anyway, the most relevant issue is the relative change of the (ICTP-CSIC), 28006 Madrid, Spain; orcid.org/0000-
different additives with degradation time, and that shall remain 0002-5144-9268; Phone: 34-912587577; Email: ernestop@
unaffected by considering or not the response factors. ictp.csic.es
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ACS Omega http://pubs.acs.org/journal/acsodf Article

Authors (13) Lv, G.; Wang, L. B.; Liu, J.; Li, S. F. Method for determination
Enrique Blázquez-Blázquez − Instituto de Ciencia y Tecnologiá of fatty acid amides in polyethylene packaging materials-Gas
́
de Polimeros (ICTP-CSIC), 28006 Madrid, Spain chromatography/mass spectrometry. J. Chromatogr. A 2009, 1216,
María L. Cerrada − Instituto de Ciencia y Tecnologiá de 8545−8548.
́
Polimeros (ICTP-CSIC), 28006 Madrid, Spain; orcid.org/ (14) Blázquez-Blázquez, E.; Barranco-Garcia, R.; Cerrada, M. L.;
Perez, E. Effect of thermo-oxidation on loss of plasticizers, on
0000-0003-4261-0627 crystalline features and on properties in a metallocene isotactic
Rosario Benavente − Instituto de Ciencia y Tecnologiá de polypropylene. Polymer 2019, 181, No. 121749.
́
Polimeros (ICTP-CSIC), 28006 Madrid, Spain (15) Yang, Y. P.; Hu, C. Y.; Zhong, H. N.; Chen, X.; Chen, R. J.;
Complete contact information is available at: Yam, K. L. Effects of Ultraviolet (UV) on Degradation of Irgafos 168
https://pubs.acs.org/10.1021/acsomega.9b03058 and Migration of Its Degradation Products from Polypropylene Films.
J. Agric. Food Chem. 2016, 64, 7866−7873.
Notes (16) Salafranca, J.; Pezo, D.; Nerin, C. Assessment of specific
migration to aqueous simulants of a new active food packaging
The authors declare no competing financial interest.

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containing essential oils by means of an automatic multiple dynamic
hollow fibre liquid phase microextraction system. J. Chromatogr. A
ACKNOWLEDGMENTS 2009, 1216, 3731−3739.
This work was funded by project MAT2016-79869-C2-1-P (17) Onghena, M.; van Hoeck, E.; Vervliet, P.; Scippo, M. L.; Simon,
(AEI/FEDER, UE). C.; van Loco, J.; Covaci, A. Development and application of a non-

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