PHOTO-OXIDATION OF POLYPROPYLENE-GRAFT-

MALEIC ANHYDRIDE- CLAY NANOCOMPOSITES

M. Diagne, A. Tidjani

LRNA, Département de Physique, Faculté des Sciences et Techniques, Université Cheikh

Anta Diop de Dakar, BP 5005, Dakar-Fann, Sénégal

ABSTRACT

Nanocomposites of PP-graft-maleic anhydride/clay were prepared by melt blending. X-ray

diffraction and transmission Electron Microscopy measurements were performed for the
structural characterization of the nanocomposites produced. The nanocomposites show
tactoid, intercalated and exfoliated structures side by side with different dominant states
depending on the clay used and on the processing conditions. Samples of nanocomposites
were exposed to UV light under accelerated and natural conditions. FTIR spectroscopy was
used to follow the degradation process. The nanocomposites showed a higher propensity
towards oxidation compared to pure polypropylene.

KEYWORDS

Polypropylene-graft-maleic anhydride; montmorillonites; nanocomposites; X-ray; photo-

oxidation; FTIR.

INTRODUCTION

Clay mineral-polymer nanocomposites that exhibit changes in composition and structure over
a nanometer scale have been extensively studied. The interest of the scientific community in
nanocomposites is due to their remarkable properties in comparison to conventional
composites. For instance enchanced mechanical property, gas barrier properties, ionic
conducticity, thermal stability and for retardancy,relative to the virgin polymer have been
observed (Green, 2000, Tidjani, 2003).
In the natural state, silicate sheets are stacked together by covalent interactions. The galleries
between these sheets are occupied by hydrated cations, such as Na+ and K+, whose charge
balances the negative charge of the layers, which arises from isomorphic substitution of
cations in the silicate. Organic cations such as alkylammonium may replace these ions in an
ion exchange reaction, thereby increasing the affinity of the surface for a variety of polymer.
The use of organoclays -through such chemical modification- as precursors to nanocomposite
production has been experienced into several polymer systems including polypropylene (PP).
Polypropylene -one of the most widely used polyolefins- is a non polar polymer, that makes
difficult the formation of PP-clay nanocomposite. Recently, a novel approach to prepare PP-
clay nanocomposite by using a functional polyolefin oligomer (e.g. maleic anhydride grafted
PP ) as compatibilizer has been reported (Kawasami et al., 1997). PP-clay nanocomposite can
be produced by direct polymer melt intercalation method. For true PP-clay nanocomposites,
the clay monolayers must be uniformly dispersed (exfoliated) in the polymer matrix, as
opposed to being aggregated as tactoids or simply intercalated.

The nanocomposites of interest in this article are made from polypropylene graft maleic
anhydride (PP-g-MA) and a current favorite nano-clay montmorillonite. They were produced
by direct melt intercalation during conventional melt blending in a extrusion machine. We
report here in their photo- and thermo-aging behaviour with the aid of IR spectroscopy.

EXPERIMENTAL

Materials

Polypropylene graft maleic anhydride from Aldrich chemical company, containing a mass
fraction of 0.6% maleic anhydride was melt blended in a Brabender mixer with organically-
modified clays. Three different organoclays were used: cloisite 30 B, closite 20A, from
Southern clay Products, containing respectively a Methyl group M, tallow, T and two
hydroxy ethyl, EtOH (MT2EtOH) and two Methyl groups M, two hydrogenated Tallow, HT
(2MHT), and Nanocor I28E from Nanocor, containing octadecyl trimethyl amine, (OD3MA)
(see Table 1). All the compounds were used as received.

TABLE 1. TYPE OF CLAYS USED; THEIR STRUCTURE AND MODIFIED CONCENTRATION

Trade Name modified clay Structure Modified concentretion

CH3
I28E
(OD3MA) C17H37 + 90 meq/100g
N CH3

CH3
HT
Closite 20A
(2M2HT) + 95 meq/100g
H3C N CH3

HT
T
Closite 30B
(MT2EtOH) + 90 meq/100g
H3C N CH2-CH2-OH

CH2-CH2-OH
The melt blending process was performed in a extruder in the presence of oxygen. The
following parameters were held constant: blending temperature of 180°C, screw speed of 50
tours/min, processing time. In all cases, PP-clay nanocomposites, with a clay mass fraction of
5%, were produced. For the X.ray, FTIR and TEM investigations, materials were pressed in a
form of thin films.

Instrumentation

Tne state of mixing like intercalation and for exfoliation of the blended PPgMA
nanocomposite was investigated by X-ray diffraction and TEM. The X-ray scattering
measurements of PP-nanocomposite were performed by combined small and wide angle
scatting in a kiessig pinhole camera using Mo-k-k radiation. The TEM observations were
done with a philipe CM 20 equipment at 200 KV. The ultra-thin section were cut using a
RMC ultra mikrotom : MT- 7000 at room temperature. Additional Fourier transform spectra
(FTIR) were taken using a spectrum BX instrument at a 4 cm-1 resolution to evidence the
presence of an inorganic-organic mixture;
Thin films (200-500µm) were used for the photo-oxidation study. Under accelerated
conditions, samples (in duplicate in all cases ) were UV irradiated at 60°C using the SEPAP
12.24 equipped with Xenon Lamps. The working temperature was thoughly controlled at
(60°C + 3°C) and the radiation of wave lengths shorter than 300nm were eliminated using
filters. The rate of photo oxidation of the UV degraded samples was followed by measuring
the build up in non volatile carbonyl oxidation products in the non volatile fraction of the
sample using infrared bands near 1715cm-1, 1735cm-1 and 3400cm-1.
The natural photo-aging was conducted at Dakar, Senegal. Samples were placed on a wood
frame, at the top of our building.

RESULTS AND DISCUSSION

Characterization of nanocomposites (FTIR, X-ray and TEM results)

The recorded FTIR spectra showed the presence of both the characteristic bands of
-1 -1
montmorillonite and PP-g-MA, at 1050 cm (Si-O stretching vibrations) and 1782 cm
(carbonyl of the cyclic anhydride group) for all samples produced. Further characterization is
reached with the X-ray diffraction that is one of the techniques used to prove the formation of
nanocomposite; it allows the determination of the space between structural layers of the
silicate using Bragg's law sinθ= nλ/2d. The X-ray data are collected in table 2.

TABLE 2. THE D-SPACINGS OF MODIFIED CLAYS CLOISITE 30B (MT2ETOH), CLOSITE 20A
(2MHT) AND NANOMER I28E (OD3MA) AND THEIR BLENDS WITH POLYPROPYLENE-GRAFT-
MALEIC ANHYDRIDE (PP-G-MA)

Clay d001 of clay d001 of PP-g-MA-clay /

/ nm nm
MT2EtOH 1.81± 0.05 3.32 ± 0.05/1.47 ± 0.05
OD3MA 2.45 ± 0.05 no peak
2MHT 1.85± 0.05 no peak

For P-MT2EtOH, two weak X-ray peaks appear : one towards the higher angle indicating a
decrease of the d-spacing (from 1.81 to 1.47 nm) and, the other one, towards the lower angle
corresponding to an increase of the d-spacing (from 1.81 to 3.32 nm). This result suggests a
partial intercalation of the PP-MT2EtOH nanocomposite. The disappearance of the strong
peak characterizing the undisturbed clay stacks indicates delamination or even partial
exfoliation. The TEM proves the absence of large undisturbed clay particles. Main part of the
material is exfoliated in smaller particles with length around 200 nm and stacks consisting of
1 to 8 layers. It is well known that the presence of hydroxyethyl is supposed to favour
wettability of the clay by the maleic anhydride groups grafted onto PP, facilitating the
production of nanocomposite. It can be seen that there are two X-ray peaks for the PP-
MT2EtOH composite; the first one indicated an increase of the d-spacing from 1.81 to 3.32
contrary to the second that suggested a decrease from 1.81 to 1.47. decreases from 1.81 to
1.52 nm. This decrease of the d-spacing is evidenced by a shift of the peak towards higher 2θ
angle. This suggests a partial decomposition of the alkyl ammonium modifier during the
extrusion process.

FIGURE 1. TEM IMAGES OF PP-OD3MA

The PP-OD3MA and PP-2M2HT composites obtained present a quite different situation. The
X-ray peak disappears while strong continuous scattering of single particles occurs. The TEM
investigations of these samples reveal the absence of large undisturbed clay particles. Only a
small number of particles characterised by dimensions up to 1 µm (Figure 1) are found,
whereas the main part of the material is exfoliated in structures with length around 200 nm
consisting of stacks, that are built up by 1 to 8 layers (Figure 1). The smaller structures down
to exfoliated single layers are dominant and correspond to the continuous scattering and
vanishing Bragg peak in the X-ray investigation, which indicates isolated particles and/or
delamination of the layered structure.

Photo-oxidation under accelerated conditions

Figure 2 shows the evolution of the infrared spectrum in the carbonyl region upon UV
irradiation. All spectra were obtained by spectral subtraction of the spectrum of the
unirradiated film. At the beginning of the UV irradiation, the bands at 1715 cm-1 and at
1780cm-1 were negative indicating the disappearance of maleic anhydride group. At the same
time, a small band 1735cm-1 begins to increase. This band is much more noticeable after 40 h
of UV irradiation. The broad nature of the band at 1735cm-1 suggests a mixture of different
carbonyl species among them ester entities. The role of the anhydride groups in the photo
oxidation of nanocomposite is open to speculation. It seems that their photo decomposition
may yield ester species. However more detailed study is necessary to validate this assumption
because different mechanisms of maleic anhydride photodegradation have been proposed
(Grassie, 1980, Holland, 1991).

As the UV irradiation is increased, a progressive formation of bands at 1715 cm-1 (ascribed to

mixture of ketones and carboxylic acids) and at 1780 cm-1 (γLactones) is observed (Tidjani,
1997). At this point, the nanocomposite degrades like virgin PP giving classical products of
oxidation in both carbonyl and hydroxyl regions; figure 3 shows the IR evolution of recorded
spectra in this last region. A broad band centered at 3400 cm-1 increased regularly with UV
irradiation time. In previous work, this band was assigned to a mixture of alcohol and
hydroperoxides species ( Gilman et al., 1998).

1.48
1.4

1.2

1.0

0.8

A 0.6

0.4

0.2

0.0

-0.20
2000.0 1950 1900 1850 1800 1750 1700 1650 1600 1550 1500.0
cm-1

FIGURE 2. TYPICAL EVOLUTION OF THE INFRARED ABSORBANCE A OF NANOCOMPOSITE OVER

THE ACCELERATED PHOTO-OXIDATION IN THE CARBONYL REGION. FROM BOTTOM TO TOP, THE
IRRADIATION TIMES ARE AS FOLLOW: 10 H, 40 H, 50 H, 60 H, 70 H, 80 H AND 100 H
 0.80

0.7

0.6

0.5

0.4

0.3
A

0.2

0.1

0.0

-0.1

-0.20
3800.0 3600 3400 3200 3000.0
cm-1

FIGURE 3. TYPICAL EVOLUTION OF THE INFRARED ABSORBANCE A OF NANOCOMPOSITE OVER

THE ACCELERATED PHOTO-OXIDATION IN THE HYDROXYL. FROM BOTTOM TO TOP, THE
IRRADIATION TIMES ARE AS FOLLOW: 10 H, 40 H, 50 H, 60 H, 70 H, 80 H AND 100 H

In the unsaturation region, no noticeable changes have been observed all along the UV
irradiation process.

In Figure 4, the kinetic evolution of the major band at 1735 cm-1 was plot. One can observe a
lower induction period for polypropylene comparatively to its counterpart nanocomposites.
Remind that the induction period is the time in which the material does not undergo any
noticeable oxidation. This time is around 30 hours for polypropylene against an average of 15
hours for the other samples. For all samples, after the oxidation has commenced, an
autoacceleration of the plot was observed. This one continued for polypropylene but not for
the other samples that displayed a tendancy to a plateau in the long run. This result suggests
that the presence of the silicate layers does not delay the oxidation to happen but can slow
down this process when it takes place. An explanantion can be given by the decrease mobility
of chains, products of oxidation and reduced permeability of oxygene gas due to the presence
of silicate layers that impose a tortuous path (Tidjani et al., in press).
 0,4

0,35
PPgMA
PPgMA +I28E

0,3
PPgMA +20A
Absorbance à 3400cm-1

PPgMA +30B

0,25

0,2

0,15

0,1

0,05

0
0 20 40 60 80 100 120

Temps d'irradiation (heures)

FIGURE 4. KINETIC EVOLUTION AT 1735 CM-1 OF THE INVESTIGATED SAMPLES UNDER

ACCELERATED PHOTO-OXIDATION

0,4

0,35 PPgMA
PPgMA +I28E
PPgMA +20A
0,3
PPgMA +30B
Absorbance à 3400cm-1

0,25

0,2

0,15

0,1

0,05

0
0 20 40 60 80 100 120

Temps d'irradiation (heures)

FIGURE 5. KINETIC EVOLUTION AT 3400 CM-1 OF THE INVESTIGATED SAMPLES UNDER

ACCELERATED PHOTO-OXIDATION
Photo-oxidation under natural conditions

0.6 PPgMA
PPgMA+I28E
0.5 PPgMA+20A
-1
Absorbance at 1735cm

PPgMA+30B
0.4

0.3

0.2

0.1

0.0
0 500 1000 1500 2000 2500
Solar exposure time (hours)

FIGURE 6. KINETIC EVOLUTION AT 1735 CM-1 OF THE INVESTIGATED SAMPLES UNDER NATURAL
PHOTO-OXIDATION

1.2
1.1 PPgMA
1.0 PPgMA+I28E
0.9 PPgMA+20A
-1
Absorbance at 3400 cm

0.8 PPgMA+30B
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0 500 1000 1500 2000 2500
Solar exposure time (hours)

FIGURE 7. KINETIC EVOLUTION AT 3400 CM-1 OF THE INVESTIGATED SAMPLES UNDER NATURAL
PHOTO-OXIDATION
The FTIR spectral evolution did not display any fundamental differences with the ones
obtained under accelerated conditions. Figure 5 & 6 that show the kinetic evolution obtained
called for some comments.
In the following table, the acceleration factor for each formulation has been listed. This factor
is calculated by divided the time corresponding to 0.1 absorbance at 1735 cm-1 obtained under
natural conditions by the one obtained un der accelerated conditions.

TABLE 3. ACCELARATION FACTOR (AF)OF EACH FORMULATION TESTED. IT IS CALCULATED BY

DIVIDED THE TIME CORRESPONDING TO 0.1 ABSORBANCE AT 1735 CM-1 OBTAINED UNDER
NATURAL CONDITIONS BY THE ONE OBTAINED UNDER ACCELARATED CONDITIONS

Samples PP PP-g-MA PP-I28E PP-20A PP-30B

AF 19.7 18.46 40.08 37.94 22.90

A surprising disparity of the acceleration factor is noticed here for the nanocomposites tested
here in. One can suspect the type of modified clay used to prepare nanocomposite to be responsible for this
disparity. Our result brings another piece of evidence to avoid any attempt to extrapolate from
one sample the prediction for other sample of the same class. Study is in progress in our
laboratory to understand the chemistry behind such differences. For that, SF4 and NO
chemical derivatzations are in use to be able to identify and quantify the products of
oxidation.

CONCLUSION

In this work, the photo-aging of nanocomposites blended with polypropylene-graft-

nanocomposites and modified clay was investigated with the FTIR technique. The
nanocomposites obtained, characterized by X-ray and TEM techniques displayed mostly an
exfoliated structure. These nanocomposites showed a higher propensity towards initiation of
oxidation compared to pure polypropylene. In the long run of oxidation process, the silicate
layers present in the nanocomposites seem to slow down the oxidation process; the reduced
mobility and permeability of gases and oxidation products could be the reason. Comparison of
the natural and accelerated photo-aging allowed us to determine an acceleration factor that is
characteristic to each sample.

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