Polymer 48 (2007) 1632e1640

www.elsevier.com/locate/polymer

Evaluation of amine functionalized polypropylenes as compatibilizers

for polypropylene nanocomposites
Lili Cui, D.R. Paul*
Department of Chemical Engineering and Texas Materials Institute, The University of Texas at Austin, Austin, TX 78712-1062, USA
Received 7 November 2006; received in revised form 18 January 2007; accepted 19 January 2007
Available online 25 January 2007

Abstract

The compatibilization effects provided by amine functionalized polypropylenes versus those of a maleated polypropylene, PP-g-MA, for
forming polypropylene-based nanocomposites were compared. Amine functionalized polypropylenes were prepared by reaction of maleated
polypropylene, PP-g-MA, with 1,12-diaminododecane in the melt to form PP-g-NH2 which was subsequently protonated to form PP-g-NHþ 3.
Nanocomposites were prepared by melt processing using a DSM microcompounder (residence time of 10 min) by blending polypropylene
and these functionalized materials with sodium montmorillonite, Na-MMT, and with an organoclay. X-ray and transmission electron microscopy
plus tensile modulus tests were used to characterize those nanocomposites. Composites based on Na-MMT as the filler showed almost no im-
provement of tensile modulus compared to the polymer matrix using any of these functionalized polypropylenes, which indicated that almost no
exfoliation was achieved. All the compatibilized nanocomposites using an organoclay, based on quaternary ammonium surfactant modified
MMT, as the filler had better clay exfoliation compared to the uncompatibilized PP nanocomposites. Binary and ternary nanocomposites using
amine functionalized polypropylenes had good clay exfoliation, but no advantage over those using PP-g-MA. The PP-g-MA/organoclay and PP/
PP-g-MA/organoclay nanocomposites showed the most substantial improvements in terms of both mechanical properties and clay exfoliation.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Polypropylene; Nanocomposites; Compatibilizer

1. Introduction organoclayepolymer interaction, etc on exfoliation and prop-

erty development [1e5]. From this background, it has become
Nanocomposites formed from organoclays represent a po- clear that unmodified polyolefins lack the intrinsic thermody-
tentially attractive approach for improving some performance namic affinity with the currently available organoclays to form
characteristics (mechanical, thermal, barrier, etc) of polymers well-exfoliated nanocomposites [1,2,6,7]; yet, in principle,
without a significant increase in material mass because the materials like polypropylene, PP, would offer the greatest
high aspect ratio of the clay platelets permits significant commercial opportunity for such technology. The use of a
reinforcement at low loadings. However, the key challenge ‘‘compatibilizing’’ component has proved to be at least a
to realizing this potential is to achieve a high degree of exfo- partial solution to this problem; maleated polypropylene,
liation of the aluminosilicate layers within the polymer matrix PP-g-MA, has become the widely accepted standard for this
using a convenient and economical process, like melt com- function [8e12]. Even though PP-based nanocomposites con-
pounding. Extensive studies have been reported recently on taining PP-g-MA are not as well exfoliated as those based on
the effects of processing variables, organoclay structure, more polar polymers like nylon 6 [4,5,13], this approach has
allowed commercialization to go forward.
Clearly more extensive utilization of PP-based nanocompo-
* Corresponding author. Tel.: þ1 512 471 5392; fax: þ1 512 471 0542. sites would be possible if a more effective or less expensive
E-mail address: drp@che.utexas.edu (D.R. Paul). compatibilizer was available. The purpose of this study is to

0032-3861/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2007.01.036
 L. Cui, D.R. Paul / Polymer 48 (2007) 1632e1640 1633

explore the possibility of other functional PPs that might serve Sodium montmorillonite and an organoclay (Cloisite 20A)
as a better compatibilizer than PP-g-MA. It has been reported based on dimethyl, dihydrogenated tallow quaternary ammo-
[14] that an ammonium terminated PP (PP-t-NHþ 3 ) forms nium, M2(HT)2, were provided by Southern Clay Products
a very well-exfoliated nanocomposite when combined with Inc. The exchange ratio of the organic ammonium ion on
clay using a static melt intercalation technique; this chemical MMT was 95 meq/100 g clay (MER). The organic loading
approach seems promising. Inspired by this idea, we explore was determined by the mass loss on ignition (LOI) to be
here a practical way to produce amine funtionalized PP mate- 38 wt%. These two clays were selected for the following rea-
rials and test their effectiveness as compatibilizers for PP sons. Wang et al. [14] speculated that the cations of the proton-
nanocomposites using conventional melt processing tech- ated amine grafted to PP might exchange with the sodium ions
niques. Wang et al. [14] also proposed a possible cation of Na-MMT which would separate the clay platelets from each
exchange reaction between PP-t-NHþ 3 and the sodium cations other and facilitate exfoliation. Recent studies have shown that
at the MMT surfaces during the formation of nanocomposites, for each polymer matrix there is an optimum structure of the
which would exfoliate the clay platelets. To test this idea, we surfactant on the organoclay for achieving exfoliation or dis-
used both sodium montmorillonite and an ammonium surfac- persion [22,23]; Cloisite 20A has been shown to be a good
tant modified montmorillonite organoclay as the nanofillers choice for polyolefins, which was the basis for including it
for the nanocomposites. in this study.

2.2. Preparation of nanocomposites

2. Experimental
All the nanocomposites were prepared using a DSM Micro
2.1. Materials 5 melt compounder, which has a net barrel capacity of 5 cm3,
using a screw speed of 100 rpm and a barrel temperature of
The materials used in this study are described in Table 1. 190  C, with all the components added at the same time. All
The PP matrix polymer is of commercial injection molding the materials were dried in a vacuum oven at 80  C overnight
grade from Basell with a melt index of 37. prior to use.
The PP-g-MA selected for this work was PB3200, supplied Test bars were formed using a DSM micro-injection mold-
by Crompton, which contains 1 wt% maleic anhydride groups; ing machine with the barrel temperature set at 195  C and the
this material has been shown by other studies to be effective mold temperature at 35  C. The dimensions of the molded
for promoting exfoliation of organoclays in polypropylene specimen were 0.32  1.00  7.10 cm3. The injection molding
nanocomposites [15e19]. It has a high melt index because pressure and holding pressure were both set at 40 bar. The data
of the chain scission that accompanies grafting. Such materials below are reported in terms of the weight percent montmoril-
are made by reactive extrusion of PP with maleic anhydride lonite (MMT) in the composites rather than the amount of
and a peroxide [20,21]. The free radicals produced by the organoclay, since the silicate is the reinforcing component.
peroxide abstract hydrogens from the carbon backbone of
PP. These sites allow grafting of maleic anhydride, typically 2.3. Characterization
only one unit is added at each site; however, the hydrogen ab-
straction also leads to chain scission of the PP backbone at this Mechanical property tests were performed on an Instron
point. Thus, there is a tendency for the maleic anhydride units model 1137 upgraded for computerized data acquisition.
to exist at the end of the broken PP chain; such chains would Modulus values were determined using an extensometer at a
approximate an end functionalized polypropylene, i.e., PP-t- crosshead speed of 0.51 cm/min. Because dumb-bell shaped
MA. Of course, this is an over simplification of the structure specimens could not be prepared by the available molds for
of PP-g-MA, and some chains may contain more MA units the micro-injection molding machine, failure properties were
than the single one envisioned by the above scenario; thus, not measured.
some PP-g-MA may be multifunctional. The amine function- X-ray diffraction scans were obtained using a Scintag XDS
alized compatibilizer was prepared from this PP-g-MA in 2000 diffractometer in the reflection mode, with an incident
our laboratory by procedures explained later. X-ray wavelength of 1.541 Å at a scan rate of 1.0 deg/min

Table 1
Materials used in this study
Materials Commercial designation Supplier Properties
Polypropylene Pro-Fax PH020 Basell MI ¼ 37; density ¼ 0.902 g/cm3
PP-g-MA PB3200 Crompton MI ¼ 105; density ¼ 0.91 g/cm3; MA content ¼ 1.0 wt%; M w ¼ 90;000, MWDz2:7
Sodium MMT Cloisite NAþ Southern Clay Product Percent loss on ignition ¼ 7; d001 ¼ 1.17 nm
(Na-MMT)
Organoclay Cloisite 20A Southern Clay Product Surfactant: Dimethyl, dihydrogenated tallow quaternary ammonium; surfactant
concentration ¼ 95 meq/100 g clay; percent loss on ignition ¼ 38; d001 ¼ 2.42 nm
Diamine 1,12-Diaminododecane SigmaeAldrich Melting point ¼ 69  C; boiling point ¼ 304  C
1634 L. Cui, D.R. Paul / Polymer 48 (2007) 1632e1640

over the range of 2q ¼ 1e12 . The skin areas of the injection 3.2. Reaction scheme
molded rectangular bars were scanned while the clay was
analyzed in powder form. The reaction between an amine and an anhydride unit,
TEM images were obtained using a JEOL 2010F transmis- shown in Fig. 1, first leads to an amide and a carboxylic
sion electron microscope operating under an accelerating volt- acid or amic acid; this is a very fast reaction and can happen
age of 120 kV. Ultra-thin sections (w50 nm) were cut from even at room temperature. The subsequent cyclization step is
the central part of the injection molded bars parallel to the comparatively much slower and is reversible [24] but can be
flow direction under cryogenic conditions using a RMC effectively completed at melt processing temperatures.
PowerTome XL microtome. During the reactive blending, the torque values were
recorded. Fig. 2 compares the torque evolution for different
reactant ratios (x ¼ the molar ratio of amine groups to maleic
3. Preparation of amine functionalized polypropylene
anhydride groups). For pure PP-g-MA, the torque stabilizes af-
(PP-g-NH2 and PP-g-NHD 3 )
ter 3e4 min. After adding the diamine, the torque increased
immediately and dramatically, which means at 195  C the re-
3.1. Reactive blending
actions suggested in Fig. 1 occur very fast. The torque increase
is due to the increase in molecular weight and possible cross-
The amine functionalized polypropylene was prepared by re-
linking when one amine of the diamine reacts with one PP-g-
active blending of PP-g-MA with 1,12-diaminododecane from
MA molecule while the other amine reacts with a different
Aldrich. Two factors guided the choice of this diamine. The re-
PP-g-MA molecule as suggested in Fig. 1. If each PP-g-MA
actions of aliphatic amines with anhydrides have been reported
[24] to be faster than aromatic amines and can lead to higher re-
action extents. A diamine with high molecular weight, which
tends to have high melting and boiling points, is a requirement 10

for the current melt reactive blending technique at high temper-

atures to prevent diamine loss by evaporation. 8
Approximately 45 g of PP-g-MA was first introduced into
Torque (N m)

the mixing chamber of a Brabender mixer at 195  C and 6 x = NH2/MA ratio =

50 rpm. After PP-g-MA was melted and the torque stabilized,
1
1,12-diaminododecane was added in an amount to give a spec- Addition
4 of diamine
ified molar ratio of amine groups to maleic anhydride groups.
After mixing for another 5.5 min, samples were taken from the 2
mixing chamber, solidified and ground to form a powder 2
4
which was purified by soxhlet extraction, using xylene as
0
the solvent, for 24 h to remove the excess diamine. 0
0 5 10 15 20 25 30
Some of the purified PP-g-NH2 was further treated with acid
Time (min)
to form PP-g-NHþ 3 . The protonation was done in a reflux of HCl
solution in toluene at 70  C for 7 h under N2 protection [14]. Fig. 2. Brabender torque evolution during reaction of PP-g-MA with diamine.

PP PP PP
-H2O O
O O O
H2N R NH2 + C C
NH-R-NH2 N
O OH
NH2 R
O O

Possible crosslinking:
PP

O O
C C
HN OH O
R N PP R=(CH2)12
HN R
O
C NH
O C
O

PP

Fig. 1. Reaction of 1,12-diaminododecane with maleic anhydride grafted polypropylene.

 L. Cui, D.R. Paul / Polymer 48 (2007) 1632e1640 1635

molecule contained only one maleic anhydride unit, these re- through cyclization of the acid and amide can also be identi-
actions with the diamine should lead only to chain extension. fied by the new absorption band at 1770 cm1. Imide units
However, to the extent that the PP-g-MA material contains have been reported to have carbonyl absorption at
molecules with more than one maleic anhydride unit, this 1770 cm1 (asymmetrical stretching) and 1700e1720 cm1
reaction can lead to crosslinking [24]. An excess of diamine (symmetrical stretching) [25,26]. The absorption due to sym-
would tend to reduce the possibility of coupling two PP-g- metrical carbonyl stretching of imide groups superimposed
MA molecules or crosslinking and would favor the desired re- on the strong absorption at 1710 cm1 due to carbonyl stretch-
sult of only one of the amines on the diamine reacting with an ing of the carboxylic acid.
anhydride leaving the other amine unreacted. The results show
that as the value of x increases beyond unity, the maximum 4. Results
value of the torque decreases and the time needed to reach
the maximum becomes shorter. This indicates that excess di- 4.1. Force recordings via DSM microcompounder
amine tends to diminish the extent of chain coupling or cross-
linking as would be expected. In this study, x ¼ 4 was chosen The force measurement capability of the DSM micro-
for preparation of the amine functionalized PP, since the extent compounder provides similar rheological information as the
of chain coupling or crosslinking is minimized. The progres- torque measurement does in the Brabender mixer. Thus, force
sive decrease of the torque after the maximum in this case evolution versus time traces on the DSM microcompounder
might be attributed in part to the excess diamine acting as were recorded and are shown in Fig. 4 for virgin PP, PP-g-
a plasticizer; however, reduced molecular weight build up is MA, and PP-g-NH2. The force for PP-g-NH2 is about three
likely the dominant effect. times higher than that for PP-g-MA while PP falls in between.
This observation is consistent with the equilibrium torque
recordings from the Brabender during the reaction used to
3.3. FTIR characterization of PP-g-NH2 make the amine functionalized PP. This suggests that even at
the amine to anhydride ratio of 4 used to make the PP-g-
FTIR was used to characterize the product structure, see NH2, some chain coupling or crosslinking still occurs. Note
Fig. 3 and Table 2 [25,26]. The disappearance of the anhydride that owing to the purification scheme used, no free diamine
carbonyl stretching absorption at 1780 cm1 indicates a con- should be present in these materials during processing in the
siderable extent of reaction. Formation of the imide groups DSM microcompounder.

4 4.2. Mechanical properties

PP-g-MA
PP-g-NH2
The moduli of binary nanocomposites formed from neat
3
polypropylene and the various functionalized polypropylenes
1706 cm-1 and sodium montmorillonite or M2(HT)2 organoclay are com-
2 pared in Table 3. The absolute moduli for the neat polymers
Intensity

1650 cm-1
1550 cm-1 and their composites containing w5 wt% MMT are listed
1770 cm -1
along with the ratio of the composite modulus to that of the
1
matrix which indicates the extent of reinforcement by the
nanofiller and is a rough indicator of the extent of exfoliation.
0
1712 cm-1
1780 cm-1
1200

-1
2000 1900 1800 1700 1600 1500
1000
Wavenumbers (cm-1)

Fig. 3. FTIR spectra of PP-g-MA and PP-g-NH2. 800

Force (N)

PP-g-NH2
600

Table 2 PP
Infrared peak assignments 400

Peak location (cm1) Group assignment

200
1550 Secondary amide groups PP-g-MA
1650 Secondary amide groups
1706 Carboxylic acid carbonyl stretching 0
0 2 4 6 8 10 12 14
1712 Imide carbonyl symmetrical stretching
1770 Imide carbonyl asymmetrical stretching Time (min)
1780 Anhydride carbonyl stretching
Fig. 4. Force versus time relationships during DSM compounding.
1636 L. Cui, D.R. Paul / Polymer 48 (2007) 1632e1640

Table 3
Modulus comparisons for two component nanocomposites
Matrix polymer Filler Modulus of pure Modulus of nanocomposites with Modulus ratio of nanocomposite
polymer (GPa) 5 wt% MMT (GPa) to polymer matrix
Std. Dev Std. Dev
PP Na-MMT 1.58 0.047 1.57 0.021 0.99
PP-g-NH2 Na-MMT 1.72 0.028 1.90 0.021 1.10
PP-g-NHþ
3 Na-MMT 1.80 0.042 1.74 0.127 0.97
PP-g-MA Na-MMT 1.49 0.035 1.49 0.042 1.00
PP Cloisite 20A 1.58 0.047 1.74 0.036 1.10
PP-g-NH2 Cloisite 20A 1.72 0.028 1.91 0.049 1.11
PP-g-NHþ
3 Cloisite 20A 1.80 0.042 2.34 0.078 1.30
PP-g-MA Cloisite 20A 1.49 0.035 2.14 0.165 1.44

When using sodium MMT as the filler, the improvements in the property determinations discussed earlier. Fig. 7 compares
modulus are quite small for each composite; whereas, when the WAXS scans for pure sodium montmorillonite and binary
the organoclay, Cloisite 20A, is the nanofiller, all the compos- composites containing w5 wt% MMT. The scan for the pure
ites show greater improvements in modulus. However, PP-g- Na-MMT reveals an intense peak around 2q ¼ 7.3 , which
MA nanocomposites show the most substantial improvement, indicates the basal spacing of the as received Na-MMT
while the composites based on unmodified PP have the least (d001 ¼ 1.21 nm). All the composites showed corresponding
improvement. The composites based on PP-g-NHþ 3 and PP- peaks, but these peaks are largely shifted to higher angles
g-NH2 fall in between. (d001 ¼ 0.98 nm). This shifting is probably due to the loss of
Ternary nanocomposites based on PP/functionalized PP/ water in clay galleries during the melt processing; dry Na-
clay were prepared at several MMT loadings to obtain MMT has a basal spacing of 0.96 nm [27,28], which is close
a more complete picture of the relative benefit of each func- to the values shown by the composites formed here. In
tionalized PP as a compatibilizer for nanocomposites formed Fig. 8, similar behavior is seen for ternary composites based
by melt processing. The ratio of functionalized PP to clay on Na-MMT.
was set at 1; this ratio has been shown by several studies in Fig. 9 compares the WAXS scans for pure Cloisite 20A
our laboratory [15e17] to be an optimum level of PP-g-MA organoclay and binary nanocomposites containing w5 wt%
for compatibilization of PP/organoclay mixtures. Higher ratios MMT. The scan for the pure organoclay reveals an intense
lead to very little additional benefit. Since PP-g-MA is rela-
tively expensive compared to PP, there is an incentive to use
no more than necessary to achieve effective dispersion of the 2.4
organoclay or property improvement. Filler = Na-MMT
For the composites using sodium MMT as the filler, Fig. 5 Matrix = PP
shows almost no modulus improvement at any loading. Appar- 2.2 Compatibilizer = PP
ently, the dispersion of the sodium MMT is very poor with PP/PP-g-MA
almost no exfoliation achieved; slight property improvements PP/PP-g-NH2
could only be realized at high filler loadings as in composites 2.0 PP/PP-g-NH3+
with conventional fillers [15].
Modulus (GPa)

Fig. 6 shows the effect of montmorillonite content on the Ratio of functionalized PP to Na-MMT = 1
modulus for four different systems based on the organoclay 1.8

Cloisite 20A. The addition of organoclay to the polymer ma-

trix produces significant increases in the modulus in all cases.
1.6
Each system containing a compatibilizer shows a higher mod-
ulus increase than the uncompatibilized system, and this
difference becomes larger with increasing MMT loading. 1.4
Among the three compatibilized systems, those based on PP-
g-MA show the highest modulus, the one based on PP-g-
NHþ 3 show the second highest modulus improvement, while 1.2
those based on PP-g-NH2 rank third. These results agree
with the TEM and WAXS observations discussed below.
1.0
0 2 4 6 8
4.3. Wide angle X-ray scattering MMT Loading (wt%)

Fig. 5. Effect of MMT content on the tensile modulus of PP/Na-MMT and

The morphology of the composites determined by WAXS PP/functionalized PP/Na-MMT (ratio of functionalized PP to clay ¼ 1)
and TEM described in this and the next section complement composites.
 L. Cui, D.R. Paul / Polymer 48 (2007) 1632e1640 1637

2.8 2500

2.6 2000
Compatibilizers = Na-MMT

Intensity (CPS)
2.4 1500
PP-g-MA PP/PP-g-MA/Na-MMT

2.2 PP/PP-g-NH2/Na-MMT
1000
Modulus (GPa)

PP-g-NH3+
PP/PP-g-NH3+/Na-MMT
2.0 PP-g-NH2 500
PP/Na-MMT
1.8 No compatibilizer 0
0 2 4 6 8 10 12 14
2 (degrees)
1.6
Fig. 8. X-ray scans for pure Na-MMT, PP/Na-MMT, and PP/functionalized
PP/Na-MMT nanocomposites containing w5 wt% MMT. The curves are
1.4 Filler = M2(HT)2 Organoclay vertically offset for clarity.
Matrix = PP

1.2 6000
0 2 4 6 8 10
MMT Loading (wt%)
5000
Fig. 6. Effect of MMT content on the tensile modulus of PP/functionalized PP/
organoclay (ratio of functionalized PP to organoclay ¼ 1) nanocomposites.
Intensity (CPS)

4000

C20A Organoclay
peak around 2q ¼ 3.6 , which is characteristic of the basal 3000
spacing of the modified layered silicate; nanocomposites,
PP-g-MA/C20A
except for unmodified PP, do not show a distinctive basal
2000 PP-g-NH3+/C20A
reflection which is consistent with a more well dispersed or
exfoliated structure. However, there are slight hints of curva- PP-g-NH2/C20A
1000
ture that could be interpreted as an extremely broad peak sug-
gesting these three systems could be almost but not completely PP/C20A

exfoliated; this extremely broad peak is shifted largely to 0

0 2 4 6 8 10 12 14
lower angles suggesting some intercalation into the organoclay 2 (degrees)
galleries [7,29].
Fig. 10 shows the WAXS scans of pure organoclay and Fig. 9. X-ray scans for pure C20A organoclay and polymer/organoclay
nanocomposites containing w5 wt% MMT. The curves are vertically offset
ternary PP/functionalized PP/organoclay nanocomposites with for clarity.
5 wt% MMT. The ratio of functionalized PP to organoclay
6000
2500

5000

2000
Intensity (CPS)

Na-MMT 4000
Intensity (CPS)

1500 C20A Organoclay

PP-g-MA/Na-MMT 3000

PP-g-NH3+/Na-MMT
1000 2000 PP/PP-g-MA/C20A

PP-g-NH2/Na-MMT PP/PP-g-NH2/C20A
1000
500 PP/PP-g-NH3+/C20A
PP/Na-MMT PP/C20A
0
0 2 4 6 8 10 12 14
0
0 2 4 6 8 10 12 14 2 (degrees)
2 (degrees)
Fig. 10. X-ray scans for pure C20A organoclay, PP/C20A, and PP/functional-
Fig. 7. X-ray scans for pure Na-MMT and polymer/Na-MMT nanocomposites ized PP/organoclay nanocomposites containing w5 wt% MMT. The curves
containing w5 wt% MMT. The curves are vertically offset for clarity. are vertically offset for clarity.
1638 L. Cui, D.R. Paul / Polymer 48 (2007) 1632e1640

used was set at 1. The nanocomposites show very similar better exfoliation of the organoclay; most of the particles are
distinctive peaks as the pure organoclay indicative of the individual platelets. The nanocomposites formed from PP-g-
presence of clay tactoids in these composites [7,29]. These NH2 and PP-g-NHþ 3 also have very small particles indicating
results agree well with the morphologies seen by TEM. good, but not complete, exfoliation of the organoclay.
Fig. 12 shows the morphology of the nanocomposites
4.4. Transmission electron microscopy formed from ternary nanocomposites based on PP, organoclay,
and the functionalized PPs, acting as the compatibilizer at
Fig. 11 shows TEM images of nanocomposites formed MMT loadings of w5 wt%. The ratio of functionalized PP
from the different polymer matrices and the organoclay, i.e., to organoclay was set at 1. Comparing these images for the
PP/organoclay, PP-g-MA/organoclay, PP-g-NH2/organoclay three compatibilized nanocomposites, it is apparent that the
and PP-g-NHþ 3 /organoclay; the MMT loadings in all cases one based on PP-g-MA gives the best exfoliation of the orga-
are w5 wt%. The PP/organoclay composite contains many noclay, while the other two nanocomposites based on amine
large aggregates of micro-sized particles, which means the functionalized PP do not show good exfoliation. Protonation
non-polar polypropylene matrix does not exfoliate the organo- seems to improve the exfoliation; the nanocomposite based
clay. The PP-g-MA/organoclay nanocomposite shows much on PP-g-NHþ 3 has somewhat better organoclay exfoliation

500 nm 200 nm
PP/organoclay PP-g-MA/organoclay

200 nm 200 nm
PP-g-NH2/organoclay PP-g-NH3+/organoclay

Fig. 11. TEM micrographs for PP and functionalized PP/organoclay nanocomposites containing w5 wt% MMT. Images were taken from the core of injection
molded specimens and viewed perpendicular to the flow direction within the molded bars.
 L. Cui, D.R. Paul / Polymer 48 (2007) 1632e1640 1639

500 nm 500 nm

PP/organoclay PP/PP-g-MA/organoclay

500 nm 500 nm

PP/PP-g-NH2/organoclay PP/PP-g-NH3+/organoclay

Fig. 12. TEM micrographs of PP/organoclay and PP/functionalized PP/organoclay nanocomposites containing w5 wt% MMT and a functionalized PP/organoclay
ratio of 1. Images were taken from the core of injection molded specimens and viewed perpendicular to the flow direction within the molded bars.

than the one based on PP-g-NH2, which is consistent with the Thus, preparation of nanocomposites from both Na-MMT
modulus results. and an organoclay, Cloisite 20A, using our amine functional-
ized polypropylenes, PP-g-NH2 and PP-g-NHþ 3 , as the matrix
5. Discussion and as a compatibilizer with polypropylene was explored us-
ing a melt compounding approach. Very little exfoliation
Maleic anhydride grafted polypropylenes, PP-g-MA, typi- was achieved with Na-MMT while better exfoliation was
cally have one anhydride unit located at the chain end owing observed with the organoclay. PP-g-NHþ 3 led to better exfolia-
to the chain scission that accompanies grafting. A simple tion than PP-g-NH2; however, neither amine functionalized
scheme was used here to form amine terminated polypropyl- polypropylene is superior to PP-g-MA as a matrix nor as
ene analogous to similar materials, PP-t-NH2 and PP-t-NHþ 3, a compatibilizer for formation of polypropylene-based
described previously using a different approach [14]. Wang nanocomposites.
et al. [14] claimed that a molten mixture of PP-t-NHþ 3 with Clearly, kinetic factors may explain the differences between
Na-MMT held in a static condition for 2 h led to a high level the observations reported here versus the claims by Wang et al.
of exfoliation perhaps due to an ion exchange mechanism. The [14]. In their static melt process, the polymer and clay mixture
purpose of the current work is to determine if this concept can were heated at 190  C for 2 h, while under the current melt
be implemented in a practical melt processing scheme to make processing conditions, the mixture only stays in the DSM mi-
high performance polypropylene-based nanocomposites. crocompounder for 10 min, which is a longer time than typical
1640 L. Cui, D.R. Paul / Polymer 48 (2007) 1632e1640

for conventional melt processing but may not be enough time [4] Fornes TD, Hunter DL, Paul DR. Macromolecules 2004;37(5):1793e8.
for the proposed ion exchange to happen. Another possible [5] Shah RK, Paul DR. Polymer 2004;45(9):2991e3000.
[6] Ellis TS, D’Angelo JS. Journal of Applied Polymer Science
factor may be that the molecular structures and molecular 2003;90(6):1639e47.
weights of the PP-g-NH2 and PP-g-NHþ 3 formed via the [7] Shah RK, Paul DR. Polymer 2006;47(11):4075e84.
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