POLYMERS FOR ADVANCED TECHNOLOGIES

Polym. Adv. Technol. 14, 733–737 (2003)

Published online in Wiley InterScience (www.interscience.wiley.com). DOI:10.1002/pat.420

Preparation of Poly(propylene)/Clay
Layered Nanocomposites by Melt
Intercalation from Pristine
Montmorillonite (MMT)
Yong Tang1, Yuan Hu1*, Shaofeng Wang1,2, Zhou Gui1, Zuyao Chen2
and Weicheng Fan1
1
State Key Lab of Fire Science, University of Science and Technology of China, Hefei, 230026, Anhui, P.R. China
2
Department of Chemistry, University of Science and Technology of China, Hefei, 230026, Anhui, P.R. China

ABSTRACT
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INTRODUCTION
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Poly(propylene)/clay nanocomposites were prepared by Polymer/clay nanocomposites have aroused peo-

melt intercalation, using pristine montmorillonite ple’s interest since Toyota group reported PA6/clay
(MMT), hexadecyl trimethyl ammonium bromide nanocomposites in situ intercalative polymerization
(C16), poly(propylene) (PP) and maleic acid (MA) [1]. Such nanocomposites have high potential for
modified PP (MAPP), The nanocomposites structure is applications as functional materials. However, there
demonstrated using X-ray diffraction (XRD) and high has been a strong restriction on the polymer used
resolution electronic microscopy (HREM). Our purpose for nanocomposites. Thus far, only polar polymers,
is to provide a general concept for manufacturing poly- such as Polyamide 6 (PA6) [2, 3], Polymethyl
mer nanocomposites by melt intercalation starting from Methacrylate (PMMA) [4, 5] have been used suc-
the pristine MMT. We found different kneaders (twin- cessfully. This is because they can intercalate
screw extruder or twin-roll mill) have influence on the between montmorillonite (MMT) layers, from
morphology of the PP/clay nanocomposites. Thermogra- which the nanocompostes is derived. But poly(pro-
vimetric analysis (TGA) shows that the thermal stability pylene) (PP), which is a non-polar polymer, has
of PP/clay nanocomposites has been improved compared never been used successfully for nanocomposites
with that of pure PP. Copyright ß 2003 John Wiley & despite a strong demand from a practical point of
Sons, Ltd. view. In order to synthesize non-polar polymer
nanocomposites, researchers usually used maleic
anhydride [6, 7], which can make a polar functional
KEYWORDS: clay; intercalated; nanocomposites; conjunct in the molecule chain of the non-polar
poly(propylene) (PP); montmorillonite (MMT) polymer and then the modified polymer can be
melt-mixed with organo-modified clay.
In this article, a novel method [8] was used to
prepare PP/clay nanocomposites by melt intercala-
*Correspondence to: Yuan Hu, State Key Lab of Fire Science, tion, using pristine clay, PP and maleic acid (MA)
University of Science and Technology of China, Hefei, 230026, modified PP (MAPP). For so doing, a cationic sur-
Anhui, P.R. China. E-mail: yuanhu@ustc.edu.cn factant such as an ammonium salt bearing long

Received 7 May 2003

Copyright ß 2003 John Wiley & Sons, Ltd. Accepted 19 June 2003
734 / Tang et al.

TABLE 1. The Compositions of the PP/Clay Hybrids

Sample MMT (wt%) C16 (wt%) Kneader Polymer (wt%) PP or PP þ MAPP

PP1 4 — Twin-roll mill PP (96%)
PP2 4 3.2 Twin-roll mill PP (92.8%)
PP3 4 3.2 Twin-roll mill PP þ MAPP (92.8%)*
PP4 4 3.2 Twin-screw extruder PP þ MAPP (92.8%)*

*As for PP3 and PP4 the weight ratio of PP/MAPP is 4.

alkyl chains (C16) has been used as a polymer/clay Thermogravimetric analysis (TGA) was deter-
reactive compatibilizer. The aim of our investiga- mined by a Netzsch STA-409c under nitrogen flow
tion is to provide a general concept for manufactur- from 25 to 600
C at the rate of 10
C/min.
ing polymer nanocomposites by direct melt
intercalation.
RESULTS AND DISCUSSION
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Figure 1 shows the XRD patterns. The d001 peak of

EXPERIMENTAL
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pristine MMT at 2 ¼ 5.8
corresponds to 1.47 nm

(Fig. 1a). PP1 exhibits only a weak peak corre-
Materials sponding to an interlayer distance of 1.4 nm
PP (F401, homopolymer, melt flow rate: 2.5 g/ (Fig. 1b), which indicates that PP can not intercalate
10 min) was supplied as pellets by Yangzi Petro- into the interlayer without C16. But there are dif-
chemical Company, China. The pristine MMT ferent results when reactive compatibilizer C16 is
(with a cation exchange capacity of 97 meq/100 g, used in PP3. Figure 1(c) shows the intercalated
average size 20 mm) was kindly provided by KeYan morphology characterized by a main diffraction
Company. MAPP was supplied by Chemical Mate- peak (d001) corresponding to an interlayer distance
rial Co. Ltd. The acid value of MAPP is 52 mg of 4.0 nm. PP2 microstructure has been observed by
KOH/g and its Mw measured by gel permeation HREM and the HREM image (Fig. 2a) shows a
chromatography (GPC) is 30 000. Hexadecyl tri- more complex situation. The distance of the inter-
methyl ammonium bromide (C16) was brought layer distance is from 2.5 to 4.0 nm. In Fig. 2(a) the
from Shanghai Chemistry Company. position marked A shows the distance of the clay is
4.0 nm while the position marked B shows the
distance is 2.5 nm. This may be that at position
Preparation of PP/MMT Nanocomposite marked A the PP with C16 is intercalated into the
Different kneaders were used to prepare the PP/clay clay interlayer and at position marked B only
nanocomposites in this work. Firstly, the pristine the C16 is intercalated into the clay interlayer, but
MMT (dried powder) and hexadecyl trimethyl am- the ratio of the two different ingredients can not be
monium bromide (C16) were mixed and ground measured in the compound. As for PP3, MAPP was
together in a pestle and mortar, then the mixed pow- added into the matrix. The d001 peak of PP3 (Fig. 1c)
der (MMT þ C16) and PP with (or without) MAPP
were added into a twin-roll mill (XK-160, JiangShu,
China) or a twin-screw extruder (TE-35, JiangShu,
China). The screw speed and roll speed were main-
tained at 220 and 50 rpm, respectively. The tempera-
ture was maintained at about 210
C. Table 1 shows
the mixing weight ratio of the samples.

Characterization
The dispersion of the MMT was evaluated by
means of X-ray diffraction (XRD) and high resolu-
tion electronic microscopy (HREM). XRD analysis
has been carried out (Cu,  ¼ 1.54178 Å, between
2 ¼ 1.5–10
) on the samples and pristine MMT.
HREM specimens were cut from an epoxy block
with embedded films of compounds at room tem-
perature using an ultramicrotome (Ultracut-1, UK)
with a diamond knife. HREM images were
obtained with a JEOL2010 microscope at an accel- FIGURE 1. XRD patterns for MMT and PP/clay hybrids: (a)
eration voltage of 200 kV. MMT; (b) PP1; (c) PP2; (d) PP3; (e) PP4.

Copyright ß 2003 John Wiley & Sons, Ltd. Polym. Adv. Technol., 14, 733–737 (2003)

FIGURE 2. The HREM image of PP/clay nanocomposites: (a) PP2; (b) PP3; (c) PP4.
is observed at lower angle (2 ¼ 2.33
) than that of
pristine clay, this indicates the average of basal
spacing increase from 1.4 to 3.79 nm. Figure 1
shows that when MAPP was added into the matrix,
the d001 peak of PP3 is observed at higher angle
(2 ¼ 2.33
) compared with that of PP2 (2 ¼ 2.20
).
In the literature it is reported that organoclay has
three types of structure, which depend on the
charge density of clay and the onium ion surfactant
[9]. When MAPP intercalated into the interlayer,
different arrangements of the onium ions are pos-
sible, so the d001 peak of PP3 is observed at higher
angle. The HREM image of PP3 shows that the
distance of interlayer is about 3.7 nm (marked B),
which may be PP and MAPP with C16 intercalated
into the interlayer. Moreover, the individual lamel-
lae (marked A) can be seen in the image of PP3. The
probable reasons for marked A and marked B in the
Copyright ß 2003 John Wiley & Sons, Ltd.
Poly(propylene)/Clay Nanocomposites / 735
images of Fig. 2 may be that: in the reactive process,
modification and intercalation are both occurring.
In the process of modification, the surfactant (C16)
does not diffuse into the interlayer at the same time,
there is little surfactant staying at the polymer
matrix (PP or PP þ MAPP), which may enhance
the compatibility when the polymer matrix is inter-
calated into the interlayer (see discussion of
mechanism). During the intercalation process, the
polymer matrix (PP or PP þ MAPP) with surfactant
intercalated into the in situ-formed modified MMT
expanded the space of interlayer. However, the
modification of MMT is mainly by the diffusion
of C16 and the extent of the modification of MMT is
different, which also has an influence on the nano-
morphologies. So in some place, PP or PP þ MAPP
intercalated into the interlayer formed the interca-
lated or exfoliated structure (Fig. 2b or marked A in
Polym. Adv. Technol., 14, 733–737 (2003)
736 / Tang et al.
FIGURE 3. The TGA curves for pure PP and PP/clay nanocomposites: (a)
pure PP; (b) PP2; (c) PP3; (d) PP4.
Fig. 2a). At the same time, due to the extent of the
modification of the MMT in the molten system, the
polymer matrix hardly intercalated into the inter-
layer, so there may only be C16 (or little polymer)
intercalated into the interlayer (marked B in Fig. 2b).
As for PP4, Fig. 1(d) indicates the absence of diffrac-
tion peaks, which clearly reveals that the MMT is
delaminated. However, XRD shows a very weak
and broad peak corresponding to 1.3 nm at 2 ¼ 6.8
.
This may be due to interlayer water residing
between the aluminosilicate layers which evolve
between 100–400
C [10]. The HREM image of the
PP4 showes that the PP nanocomposite has a mixed
nanomorphology. Individual silicate layer, along
with two or three layer stacks, are observed to be
well-dispersed (exfoliated) in the polymer matrix.
The silicates dispersed in a regular manner, which
may be the shear flow in melt extrusion.
Thermal stability is an important property for
which the nanocomposite morphology plays an
important role. Pure PP and these samples were
analyzed by thermogravimetric analysis (TGA).
The TGA curves are shown in Fig. 3. Both the 5%
loss temperature (T5%) and the maximum weight
loss temperatures (Tmax) and char residue at 600
C
TABLE 2. Thermal Properties of PP and PP/Clay Nano-
composite
Sample T5% (
C) Tmax (
C) Char residue at
600
C (wt%)
Pure PP 336.4 440.8 2.4
PP2 349.3 451.9 3.2*
PP3 378.6 457.4 4.0*
PP4 390.5 458.6 4.9*
* The char for MMT and C16 at 600
C has already
been subtracted.
Copyright ß 2003 John Wiley & Sons, Ltd.
are listed in Table 2. The results of the thermal
analysis further confirm the nano-structure in PP/
clay hybrids.
DISCUSSION OF MECHANISM
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In this work, we use pristine MMT to prepare PP/
clay nanocomposites by melt intercalation. The
probable mechanism may be that: this system is a
reactive process during melt-mixed. The prominent
interaction will arise between the three components
[11] of the system—the silicate surface, the surfac-
tant chains (C16), and the polymer matrix. At first,
some surfactant chains diffuse into the interlayer
under physical absorb and shear. Because the
negative charge originates in the silicate layer, the
cationic head group of the surfactant will preferen-
tially reside at the layer surface and the aliphatic
tail will radiate away from the surface [12]. In fact,
this course just makes the MMT organophilic,
which will reduce the interfacial energies. How-
ever, there is some difference in this system
because the surfactant does not diffuse into the
interlayer at the same time, that is to say there is
some surfactant left at the polymer matrix (PP or
PP þ MAPP), which may enhance the compatibility
when the polymer matrix intercalated into the
interlayer. In fact, there is an interaction between
the polymer matrix and the surfactant, just like the
interaction between the surfactant and the silicates.
However, the MAPP in this system may be divided
into two portions (If MAPP was used in the matrix).
There may be a little MAPP intercalated into the
interlayer of MMT after the surfactant make the
silicates organophilic enough, which also increases
the compatibility when the polymer intercalated
into the interlayer. When the packing density in the
interlayer increases to an appropriate value, inter-
calation of the main polymer matrix molecular
chains begins with the help of shear force until
Polym. Adv. Technol., 14, 733–737 (2003)
 Poly(propylene)/Clay Nanocomposites / 737

(C16) able to compatibilize the clay platelets with

PP and MAPP. The nanocomposite structure is
evidenced by the XRD and HREM, and moreover,
TGA shows that thermal stability of PP/clay nano-
composites has been improved. The probable
mechanism of intercalation has been discussed.
This approach has been successfully used in other
polymer matrices such as nylons, acrylonitrile-
butadiene-styrene (ABS), polyethylene (PE), ethy-
lene-vinyl acetate copolymer (EVA) in our labora-
tory.

ACKNOWLEDGMENTS
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The work was financially supported by the

National Natural Science Foundation of China
(No. 50003008), the China NKBRSF project (No.
2001CB409600), Anhui ‘the tenth five years’ tackle
key problems project.

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CONCLUSIONS
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Copyright ß 2003 John Wiley & Sons, Ltd. Polym. Adv. Technol., 14, 733–737 (2003)