European Polymer Journal 44 (2008) 3473–3481

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European Polymer Journal

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Macromolecular Nanotechnology

Influence of nanodispersed hydrotalcite on polypropylene photooxidation

Sergio Bocchini a,b,*, Sandrine Morlat-Therias a, Jean Luc Gardette a, Giovanni Camino b
a
Laboratoire de Photochimie Moléculaire et Macromoléculaire, UMR CNRS 6505, Université Blaise Pascal (Clermont-Ferrand), F 63170 Aubière, France
b
DISMIC Politecnico di Torino sede di Alessandria, INSTM Research Unit, V. Teresa Michel 5, 15100 Alessandria, Italy

a r t i c l e i n f o a b s t r a c t

Article history: Nanocomposites containing hydrotalcite and prepared by melt compounding with poly-

MACROMOLECULAR NANOTECHNOLOGY
Received 14 February 2008 propylene were UV-light irradiated in artificial accelerated conditions representative of
Received in revised form 14 August 2008 solar irradiation (k > 300 nm) at 60 °C in air. The chemical modifications resulting from
Accepted 22 August 2008
photooxidation were followed by IR and UV–visible spectroscopies.
Available online 3 September 2008
The presence of hydrotalcite was shown to change the global rate of photooxidation of
polypropylene by reducing the oxidation induction time and increasing the oxidation rate.
Keywords:
The differences of the oxidation induction time disappeared after solvent extraction of the
Hydrotalcite
Photooxidation
antioxidant. They were attributed to a quenching of the antioxidant activity resulting from
Polypropylene a migration onto the filler surface induced by the preferential interaction with the polar
Nanocomposite hydrotalcite. Extracting the antioxidant did not change the oxidation rate at the permanent
regime. The increase of the oxidation rate was attributed to transition metal ions, present
as impurities in hydrotalcite, which can accelerate the oxidation of the polymer by various
mechanisms including a catalysed decomposition of hydroperoxides.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction Hydrotalcites are formed with layers of M(OH)6 octahe-

Nanocomposites formed by dispersion of inorganic
nanofillers in a polymer matrix are a new class of materi-
als. Introduction of quantities lower than 5 wt% of nanodi-
spersed inorganic particles offers performance similar to
conventional polymeric composites with 30–50 wt% of
reinforcing fillers. Improvements in performances such as
modulus, heat resistance, dimensional stability, barrier
properties and flame retardant performance are often ob-
tained simultaneously [1–4]. Recently, it has been shown
that the use of layered double hydroxides (LDH) [5,6] such
as microdispersed hydrotalcite [7,8] or nanodispersed
hydrotalcite-like compound [9,10] can lead to a noticeable
improvement of the fire retardance properties of polymers.
As an example using 5 wt% of an organo-modified nanodi-
spersed hydrotalcite-like compound as flame retardant for
polyethylene, reduces by half the peak of heat release rate
during polymer combustion [9].
* Corresponding author. Address: DISMIC Politecnico di Torino sede di
Alessandria, INSTM Research Unit, V. Teresa Michel 5, 15100 Alessandria,
Italy. Tel.: +39 349 8675696; fax: +39 0131 229336.
E-mail address: sergio.bocchini@polito.it (S. Bocchini).
dral sharing edges where M stands for a range of metal
cations (e.g., Mg2+, Ca2+, Al3+) and transition metals cations
(e.g., V, Fe, Co, Ni, Cu, Zn). The mineral hydrotalcite,
[Mg6Al2(OH)16]CO3
4H2O, is formed when in brucite
(Mg(OH)2), a partial substitution of Mg2+ with Al3+ takes
place. This generates a positive charge of the layers, which
is balanced by anions (e.g. carbonate [CO32 ]) located,
together with water molecules, in the interlayer region.
The resistance to UV-light is a key factor for most out-
door applications of polymeric materials. In the last few
years, the impact of light on polymer/clay nanocomposites
has been studied [11–18]. It has been shown that nano-
composites prepared with montmorillonite as a nanoclay
and polypropylene [11,14,15], polyethylene [12] and poly-
carbonate [13] as a polymer display similar behaviours
under exposure to UV-light. The nanocomposites degrade
faster than the pristine polymers, as a consequence of a
significant reduction of the oxidation induction time
(OIT). In a previous series of papers concerning the photo-
oxidation of montmorillonite/polypropylene [14,16] and
nanoboehmite/polypropylene nanocomposites [18], one
has proposed several hypotheses to explain the oxidative

0014-3057/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2008.08.035
 3474 S. Bocchini et al. / European Polymer Journal 44 (2008) 3473–3481
degradation of these materials. The reduction of the OIT
could result of the adsorption of antioxidants onto the
nanofiller, of a catalytic effect of transition metal impuri-
ties of nanofillers, and also of additional initiation routes
due to the oxidation of the organic modifiers in the nanof-
illers. The most probable hypothesis was the interactions
between the nanofillers and the stabilizers: the antioxidant
can be adsorbed on the nanofillers thus preventing their
antioxidant action [14,18]. The photochemical behaviour
of nanocomposites PS/LDH with synthetic hybrid LDH
where M = Zn and Al has also been studied [19] and in this
case it was shown that the nanocomposites did not de-
grade faster than the PS pristine polymer.
The aim of the present study is to determine the influ-
ence of hydrotalcite and its dispersion on both the photo-
oxidation rate of polypropylene and the efficiency of
antioxidants. In order to change the dispersion of hydrotal-
cite, a polypropylene grafted maleic anhydride (PB) was
added.
2. Experimental
MACROMOLECULAR NANOTECHNOLOGY
2.1. Materials
Polypropylene highly isotactic, semi-crystalline, nucle-
ated homopolymer, HP500 N (PP), suitable for injection
moulding application (Melt flow rate (230 °C/2.16 kg)
12 g/10 min, Vicat softening temperature (50 °C/h 10 N)
153 °C), supplied by Basell S.p.A. was used. Polypropylene
functionalized with 1.2 wt% of maleic anhydride (POLY-
BOND 3200 (PB)) was supplied by Uniroyal Chemical. All
polymers were used as supplied.
The filler was a carbonate hydrotalcite (HT) [Mg6Al2
(OH)16]CO3
4H2O produced via sol-gel and supplied by
SASOL named PURAL MG63HT. The transition metals
impurities declared were Fe  20–30 ppm and Mn  30–
70 ppm.
PP or PP with 8% PB was mixed with 5 wt% of hydrotal-
cite (Table 1). Blank samples were prepared by processing
the PP with the same PP/PB proportion of composites.
2.2. Melt processing
The composites were prepared via melt-processing
with a LEISTRITZ 27 co-rotating twin screw extruder
(D = 27 mm, L/D = 40) using a low shear stress screw pro-
file (Fig. 1). Thermal profile 205-205-205-195-195-195-
190-180-195-195, throughput 6 kg/h, speed 100 rpm were
used. The residence time was about 70 s. Specimens for X-
ray diffraction and films for photooxidation were prepared
using an hydraulic press with two heated plates at 190 °C
using a pressure of 25 Bar for 1 min. The film thickness
Table 1
Composition of melt-blended samples
Sample name PP wt% POLYBOND 3200 wt% Hydrotalcite wt%
PP 100 — —
PPHT 95 — 5
PPPB 91 9 —
PPPBHT 87 8 5
Vacuum Side Feeder Polymer
40D 32D 24D 16D 8D
1 1 8
Fig. 1. LEISTRITZ 27 co-rotating twin screw extruder (d = 27 mm, L/
D = 40) profile.
were measured using a micrometer, sample thickness
was maintained below 25 lm in the range that allows to
neglect the effect of oxygen permeation on photooxidation
rate.
2.3. Irradiations
Irradiations of nanocomposite films were carried out in
air in a SEPAP 12/24 unit (ATLAS) at k > 300 nm and 60 °C.
This apparatus is equipped with four medium-pressure
mercury lamps with borosilicate envelope which filters
wavelengths below 300 nm and it is designed for the study
of accelerated artificial photodegradation, in conditions
that are relevant to natural outdoor weathering [20].
2.4. Extraction
Extractions were carried out in order to eliminate anti-
oxidant, with a solvent extractor ASE 100 DIONEX working
with supercritical solvent mixture of xylene (isomers mix-
ture)/methanol 50/50 by weight at 110 °C, 155 MPa. The
necessary time for extraction with this apparatus is quite
short, and only 25 min divided in 5 static cycles of 5 min
each were required. Extractions were continued until the
antioxidant disappeared, which was controlled by UV–vis-
ible spectrometry.
2.5. Reaction with gaseous hydrochloric acid
Reactions of films with gaseous HCl were performed in
HCl saturated atmosphere obtained under glass bell in
presence of concentrated HCl solution.
2.6. Characterization
Specimens for TEM characterizations were microtomed
at room temperature with an Ultramicrotome Leica UCT,
thickness was about 90 nm. The grid was 50 meshes,
coated with SPI-ChemTM PioloformÒ B Resin.
The analyses were performed with a Philips CM 120.
XRD-analyses were performed on compression-moulded
30  30  0.5 mm samples with a Thermo ARL diffractome-
ter X-tra 48 using Cu-Ka X-ray source (k = 1.540562 Å), step-
size 0,02° at 2 min 1 scanning rate.
Infrared spectra of films were recorded with a Nicolet
5SX-FTIR spectrometer, working with OMNIC software.
Spectra were obtained using 32 scans and a 4 cm 1
resolution.
Rates of photooxidation were followed by the absor-
bance measured at 1712 cm 1 on IR spectra which was
plotted as a function of time. In order to avoid differences
due to film thickness, the absorbance was normalized to
 S. Bocchini et al. / European Polymer Journal 44 (2008) 3473–3481
the IR absorption band at 2723 cm 1 (t(C–H) vibration
stretching band of PP).
UV–visible spectra of films were recorded on a Shima-
dzu UV-2101 PC spectrometer equipped with an integrat-
ing sphere.
3. Results
3.1. PP/hydrotalcite nanocomposites
3.1.1. Morphological characterization
From X-ray diffraction d001, the commonly named
‘‘interlayer-spacing”, is calculated using the Bragg’s law.
In (Fig. 2) the hydrotalcite presents a diffraction peak at
2h 11.7° equivalent to d001 = 0.76 nm. The X-ray diffrac-
togramms of nanocomposites show the diffraction peaks
of PP and hydrotalcite without any expansion of the inter-
layer spacing. On dispersion in PP, intercalation of the
polymer between the layers of the hydrotalcite does not
take place for both nanocomposites.
TEM images (Fig. 3) of the nanocomposites with and
without PB show a better dispersion in the case of the sam-
ple containing pure PP. One can observe, in the case of the
PPHT samples, the presence of aggregates with 200–
500 nm dimension formed by 3–4 layers of double hydrox-
ide. Micrometric aggregates are still present in PPPBHT as
can be observed in Fig. 3c.
On the basis of X-ray and TEM characterisations it is
possible to conclude that the dispersion of hydrotalcite in
polyolefins is completely different from what is usually ob-
tained with cationic clays. For cationic clays, exfoliation or
intercalation is usually synonymous of good dispersion
with individual platelets being well dispersed in the poly-
mer. The hydrotalcite dispersion is due to shear forces that
disaggregates the micrometric hydrotalcite particles but
without exfoliation (Fig. 4). The poor dispersion of hydro-
talcite in presence of compatibiliser can be explained sup-
posing the phase separation between PP and PB due to the
high concentration of compatibiliser and favoured by the
different polarity. The hydrotalcite is so accumulated in
Fig. 2. X-ray diffraction of melt-blended samples: PPHT (PP containing
5 wt% of HT) and PPPBHT (PP containing 8 wt% of PB and 5 wt% of HT)
compared with blank samples PP, PPPB (PP containing 9.1 wt% of PB) and
carbonate hydrotalcite (HT).
3475
the PB phase, more polar, pillaring and forming micromet-
ric aggregates.
3.1.2. Spectroscopic characterization
The IR spectrum of hydrotalcite (Fig. 5) corresponds to
those reported in the literature for carbonated hydrotalcite
[21]. The OH-stretching bands are recognisable at 3456
and 3065 cm 1, the bending vibration band of interlayer
water is at 1582 cm 1. The presence of carbonate anions
is indicated by the stretching band at 1369 and
943 cm 1, while the metal hydroxide stretching bands
are at 782 and 673 cm 1. The IR spectra of PP/hydrotalcite
nanocomposites show the bands of hydrotalcite in addition
to those of PP (Fig. 6). The most intense hydrotalcite bands
can be easily observed (OH-stretching at 3456 cm 1 and
metal hydroxide deformation at 673 cm 1), indicating no
evident alteration of the chemical structure of hydrotalcite
due to the specimen preparation.
The UV spectra of polypropylene and PP/hydrotalcite
nanocomposites (Fig. 7) clearly show the presence of a
residual processing phenolic antioxidant with the two typ-
MACROMOLECULAR NANOTECHNOLOGY
ical absorption bands at 227 and 277 nm. The overall
absorbance is increased for the sample containing PB as a
consequence of the presence of anhydride which absorbs
in the UV range.
3.2. Photooxidation of PP/hydrotalcite nanocomposites
3.2.1. Polypropylene films
The photooxidation mechanism of isotactic PP has
been extensively reported in the literature [18,22,23]. The
main primary product of the combined action of UV-radia-
tion and oxygen is a tertiary hydroperoxide (II) (Fig. 8)
which prevails on the secondary hydroperoxide by a ratio
around 9–1. Tertiary hydroperoxides decompose to pro-
duce alkoxy radicals (III) and hydroxy radical HO. These
radicals can abstract hydrogen from the polymer backbone
and propagate the chain oxidation reaction. The alkoxy
radicals (III) can also undergo b-scissions with scission of
the carbon–carbon bond either in the polymer backbone
or between backbone-methylbond. The successive oxida-
tion of the various products which are formed continues
up to the production of carboxylic acids, esters, peresters
lactones as evidenced by the presence of a broad carbonyl
band around 1800–1600 cm 1. These chemical modifica-
tions that result from photooxidation can be easily fol-
lowed by IR spectroscopy. The infrared analysis shows
the formation of an absorption band with a maximum at
1712 cm 1 and shoulders at 1735 and 1780 cm 1 (Fig. 9)
indicating the formation of carboxylic acids, ketones, es-
ters, peresters, and lactones. In the hydroxyl region, a
broad absorption band is observed with a maximum at
3400 cm 1 that corresponds to products such as hydroper-
oxides and alcohols.
The UV analysis (Fig. 10) of irradiated specimens shows
that a dramatic consumption of the antioxidant occurs, as
indicated by the progressive decrease of the bands at 227
and 277 nm with increasing oxidation time. It can also be
observed that after 40–44 h, the oxidation of PP results in
a progressive shift of absorbance toward the long wave-
lengths, but no defined maximum can be observed.
 3476 S. Bocchini et al. / European Polymer Journal 44 (2008) 3473–3481
MACROMOLECULAR NANOTECHNOLOGY

Fig. 3. TEM analyses of (a and b) PPHT (Polypropylene with 5 wt% of carbonate hydrotalcite) and (c and d) PPPBHT (Polypropylene with 8 wt% of maleic
anhydride grafted polypropylene and 5 wt% of carbonate hydrotalcite).

1712 cm 1 as a function of irradiation time. The time

Dispersion dependence of the rate of oxidation is typical of polypro-
pylene containing a phenolic antioxidant: after an initial
induction time (OIT around 40 h), where no oxidation is
Particles detected, the photooxidation rate progressively increases
and then reaches a constant value (PP t > 50 h) (Fig. 11).
Platelets The rate of oxidation as measured by the slope of the
linear part of the curves together with oxidation induc-
Exfoliation tion time (OIT) is reported in Table 2. The rates of pho-
tooxidation at the permanent regime are identical for PP
and PPPB. Only a slight difference can be observed be-
Fig. 4. The hydrotalcite dispersion is due to disaggregation of small tween the OIT, the one of PPPB being shorter. The de-
particles of not-exfoliated particles.
crease of oxidation induction time is due to the
presence of PB that dilutes the phenolic antioxidant pres-
The rate of photooxidation of PP is characterized in ent in the PP decreasing the overall percentage of antiox-
Fig. 11 by plotting the increase of absorbance at idant in the sample.
 S. Bocchini et al. / European Polymer Journal 44 (2008) 3473–3481 3477

1 1 1 1
Fig. 5. FTIR spectrum of carbonated hydrotalcite (Pural MG 63HT). 3456 and 3065 cm tOH, 1582 cm dH2O, 1369 and 943 cm tCO3, 782 and 673 cm
tM OH.

1.0
3456
Absorbance

673
0.5

MACROMOLECULAR NANOTECHNOLOGY
3500 3000 2500 2000 1500 1000 500
-1
Wavenumber (cm )
1
Fig. 6. FT-IR spectra of Polypropylene (PP) (Gray line) and polypropylene with 5 wt% of carbonated hydrotalcite (PPHT) (Black line) 3456 cm tOH,
673 cm 1 tM OH.

1.2 PP
1.0 PPPB
227 PPHT
Adsorbance

0.8
PPPBHT
0.6 277
0.4

0.2

0.0
200 300 400
λ (nm)

Fig. 7. UV spectra: Polypropylene (PP), Polypropylene with Polybond (PPPB), Polypropylene with 5 wt% of carbonated hydrotalcite (PPHT) and
Polypropylene with Polybond and 5 wt% of carbonated hydrotalcite (PPPBHT).

3.2.2. Polypropylene–hydrotalcite films
In the case of the samples containing hydrotalcite, one
can observe a drastic reduction of the OIT. This means that
the antioxidant disappears much more quickly than in PP
films, which indicates that it is less efficient. Moreover dif-
ferences are observed between the two nanocomposites.
PPHT has an OIT of 12 h whereas PPPBHT has an OIT of
about 16 h, which can be regarded as significant: the pres-
ence of PB leads to a stabilizing effect in presence of hydro-
talcite. Parallely, the rates of oxidation are remarkably
higher than those of PP and PPPB films.
During photooxidation, the modifications of the IR spec-
tra of a PP film containing nanodispersed hydrotalcite are
different from those of PP (Fig. 12). Indeed in presence of
hydrotalcite, a band around 1600 cm 1 appears and in-
creases with the time of exposure (Fig. 13). This result
could indicate the presence of carboxylic acid salts pro-
duced by reaction of the carboxylic acids coming from pho-
tooxidation of PP with hydrotalcite, which is made of basic
hydroxides. In order to confirm the formation of salts, the
films were exposed to gaseous HCl for 24 h. The reaction
with HCl results in a shift of the carboxylic acid/salt equi-
librium forming thus the carboxylic acid. As shown in
Fig. 14, after exposure to HCl, the carboxylic salt band dis-
appears (1600 cm 1) and a small increase of the absor-
bance of the carboxylic acid band (1712 cm 1) is noticed
(it is recalled that the molar absorption coefficient of car-
boxylate at 1600 cm 1 is 14 times higher than carboxylic
 3478 S. Bocchini et al. / European Polymer Journal 44 (2008) 3473–3481

O2 OOH
CH2 CH CH2 C CH2
CH3 hν CH3 CH3
(II)
90 % hν
H2O + (I)
(I) CH2 CH
CH3
CH2 CH
O
CH3
CH2 + OH
Alcohols
CH
(III) 3
scission

O O
+ CH CH2 CH2 + CH3
CH3
CH3

O2 hν O2 hν
MACROMOLECULAR NANOTECHNOLOGY

Acid, Esters, Peresters, Lactones

Fig. 8. The photooxidation mechanism of polypropylene.

1 1
Fig. 9. FTIR spectra of a PP film versus photo-oxidation time at k > 300 nm, 60 °C (a) 4000–3000 cm (b) 2000–1500 cm .

0.5
Adsorbance

8h 44 h
48 h
4h 52 h

0h
200 300
λ (nm)

Fig. 10. PP film photo-oxidation at k > 300 nm, 60 °C. UV–visible absorption spectra of a PP film versus time.
 S. Bocchini et al. / European Polymer Journal 44 (2008) 3473–3481 3479

3.2.3. Polypropylene–hydrotalcite extracted films

Fig. 15 shows the oxidation curves after extraction of
the antioxidant. One can observe for all the samples a de-
crease of the OITs reaching a common value which is
around 12 h for the four samples. At opposite the slopes
of the oxidation curves are not affected by extraction and
are similar to those observed in the case of the unextracted
samples. Once again it is observed that the oxidation rate
of the nanocomposites is higher than that of the PP
samples.

4. Discussion

During the induction period, when no oxidation of the

Fig. 11. Photo-oxidation at k > 300 nm, 60 °C of film of PP containing
hydrotalcite (normalised absorption at 1712 cm 1 versus time).
Table 2
polymer is observed, the remaining processing antioxidant
plays its stabilizing role being consumed as a sacrificial
additive [25]. The OIT is thus directly linked to the concen-
tration of the antioxidant. The OIT in the presence of
hydrotalcite (PPHT and PPPBHT) is significantly lower than
for PP and PPPB. The differences between the samples with
and without hydrotalcite disappear after extraction of the

MACROMOLECULAR NANOTECHNOLOGY
Oxidation induction time (OIT) and oxidation rate (Slope) obtained from
normalised absorption at 1712 cm 1 of PP/hydrotalcite films before and antioxidant. This behaviour is a strong evidence of a direct
after extraction
correlation between the presence of hydrotalcite and the
Sample Before extraction After extraction quenching of the efficiency of the antioxidant.
OIT Slope 10 2 OIT Slope 10 2 The decrease of OIT in the presence of nanofillers has al-
h(±2) (h 1)(±0.4) h(±2) (h 1)(±0.4) ready been discussed for nanocomposites containing
PP 40 6.0 12 5.7 organically modified montmorillonite [14–17] and, more
PPHT 12 9.6 12 8.4 recently, with boehmite [18]. A number of explanations
PPPB 32 6.1 12 6.3 were proposed in literature [14–16]: catalytic effect of me-
PPPBHT 16 8.9 12 9.3
tal transition impurities in montmorillonite, decomposi-
tion of the organic modifier of the filler and antioxidant
adsorption on the filler surface because of the preferential
interactions with the polar filler [18]. It was concluded that
[18], especially in absence of organic modifier and transi-
1712 cm-1
tion metal impurities, antioxidant can be trapped on the
PP
0.28 surface of the filler because of preferential interactions
PP5HT 1600 cm-1 with the polar centres. This is likely to decrease the effi-
ciency of the antioxidant since the labile hydrogen of the
Absorbance

0.22 phenolic group participates in the interactions with the fil-

0.16
0.10
1850 1800 1750 1700 1650
Wavenumbers cm -1
Fig. 12. FTIR spectra in the domain 1900–1500 cm
PPHT (Gray) after photo-oxidation.
acid at 1712 cm 1 [24]). One also observes two new
absorption bands at 1646 and 1618 cm 1 identified as
hydrogen carbonate bands, due to the reaction of the
hydrotalcite carbonate with hydrochloric acid. The hypoth-
esis about the hydrogen carbonate bands has been
confirmed by exposure of the original PPHT (not photoox-
idized) films to hydrochloric acid: the bands at 1646 and
1618 cm 1 were formed without further modification of
the IR spectrum.
ler. Adsorption of antioxidant onto hydrophilic hydrotal-
cite can explain these results, as observed previously
with smectite clays.
The sample PPHT shows a shorter OIT than PPPBHT.
This behaviour confirms the hypothesis of interactions be-
tween hydrotalcite and antioxidant and the influence of
1600 1550 1500 dispersion of HT. Establishing interactions requires a good
dispersion at a nanometric level, leading to an increase of
1
interfaces which enhances the adsorption of the antioxi-
of PP (Black) and
dant onto hydrotalcite. The sample PPPBHT, prepared
using maleic anhydride grafted polypropylene, presents a
poorer dispersion of hydrotalcite than PPHT and aggre-
gates of hydrotalcite particles can be indeed observed by
TEM. The smaller surface of interface thus reduces antiox-
idant migration onto hydrotalcite particles in the case of
PPPBHT and the OIT is less reduced.
In presence of hydrotalcite the oxidation rate of poly-
propylene increases, in literature it was proposed that
some organic modifiers can increases the oxidation rate
producing, under UV-irradiation, radical initiating centres
which can accelerate photooxidation of the matrix [18].
 3480 S. Bocchini et al. / European Polymer Journal 44 (2008) 3473–3481

1712

1600

Time
Absorbance

1850 1800 1750 1700 1650 1600 1550

-1
Wavenumbers (cm )
1
Fig. 13. FTIR spectra of a PPHT film versus photo-oxidation time at k > 300 nm, 60 °C 1900–1500 cm .
MACROMOLECULAR NANOTECHNOLOGY

In our case hydrotalcite was not organically modified and

1712 1646 1618 there are no report about aluminium or magnesium
oxide/hydroxides nor carbonate accelerating polypropyl-
1600 ene photooxydation, moreover such effect was not
Absorbance

founded for polystyrene/hydrotalcite nanocomposites

without transition metal impurities [19]. The IR spectra
of nanocomposites after UV-irradiation differ from those
of PP. This indicates that PP/hydrotalcite nanocomposites
and pristine PP form different products in photooxidative
conditions. From reaction with gaseous HCl, the presence
of carboxylate salts was proved in presence of hydrotalcite.
By reaction of hydroxides from hydrotalcite with the car-
1850 1750 1650 1550 boxylic acids photoproducts, some of hydrotalcite lamellas
Wavelength cm-1 could be disrupted, which could in turn favour a releasing
of the transition metal impurities (iron and manganese) in
Fig. 14. FTIR spectra of a PPHT film after photo-oxidation time before
(black) and after (gray) exposition to gaseous HCl for 24 h.
the polymer. The catalytic effect of metallic compounds
has been largely reviewed and can be considered as well
admitted [26]. It has been proposed that metal ions could
cause an acceleration of the oxidation of polymers by var-
ious processes including the decomposition of POOH
(Scheme 1). However, such an effect was not observed in
the case of montmorillonite [15], which is a natural clay
that contains iron impurities. This could reflect a difference
of accessibility of the metallic cations in both cases. The
localisation of iron in montmorillonite would make more
difficult the contact between the macromolecular chains
and the metallic cations. Another hypothesis is the role
played by manganese, which is only present in the case
of the hydrotalcite used in the present study.

R OOH + M n+ RO + Mn+1+ + OH (1)

+
R OOH + M n+1+ RO + Mn+ + H (2)

Scheme 1. Photocatalytic decomposition of hydroperoxides by transition

Fig. 15. Photo-oxidation at k > 300 nm, 60 °C of extracted film containing metal ions: Transition metal ion catalyses of hydroperoxide
hydrotalcite (normalised absorption at 1712 cm 1 versus time). decomposition.
 S. Bocchini et al. / European Polymer Journal 44 (2008) 3473–3481
5. Conclusions
The OITs are sensibly shorter in samples containing
hydrotalcite as compared to virgin polymer, whereas this
effect is completely erased after extraction of the antioxi-
dant. The OIT shortening can be attributed to adsorption
of antioxidant onto hydrotalcite which prevents its protec-
tive action towards oxidation of polymer. Furthermore,
hydrotalcite increases the rate of polypropylene photooxi-
dation owing to the transition metal ions present in hydro-
talcite as impurities. The influence of hydrotalcite must be
taken into account for outdoor applications of these nano-
composites and these results show that a well-adapted
strategy of stabilization is required.
Acknowledgments
The authors would thank Mr. Olaf Torno of Sasol com-
pany for supply with hydrotalcite and Mr. Angelo Ferraro
of BASELL for supply of polypropylene. The EU supports
this work by the FP6 Project: NMP3-CT-2005-516972
‘‘NANOHYBRID”.
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