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Macromol. Rapid Commun.

21, 57–61 (2000) 57

A correlation between morphology development and


rheology of polystyrene nanocomposites based upon orga-
nophilic layered silicates (organoclay) such as fluoromicas
was found as a function of the silicate modification. Orga-
noclay was obtained by means of ion exchange of clay
with protonated— amine-terminated polystyrenes with
molar mass of Mn = 121 and 5 800 g/mol. Only when
applying shear forces during melt compounding of orga-
noclay modified with high molar mass polystyrene (PS),
individual silicate platelets of 1 nm diameter and 600 nm
length were obtained. Dispersions of such in-situ formed
nanoparticles with aspect ratio of 600 accounted for
unique elastic properties observed in the low frequency
range of the dynamic modulus, whereas organoclay modi-
fied with low molecular PS did not exfoliate and exhibited
rheological behavior very similar to that of conventional TEM micrograph of an exfoliated PS nanocomposite.
fillers. Silicate loading: 5 wt.-%

Communication

Morphology and rheology of polystyrene


nanocomposites based upon organoclay
Botho Hoffmann, Christoph Dietricha, Ralf Thomann, Christian Friedrich*, Rolf Mülhaupt
Freiburger Materialforschungszentrum und Institut für Makromolekulare Chemie, Stefan-Meier-Str. 21,
D-79104 Freiburg i. Br., Germany
chf@fmf.uni-freiburg.de
(Received: August 18, 1999; revised: October 04, 1999)

Introduction noclay. Moet and coworkers5, 9–11) reported in-situ bulk and
solution polymerization of styrene using coreactive orga-
It is well established that effective dispersion of anisotro-
nophilic montmorillonite, obtained via ion exchange of
pic particles with high aspect ratio such as short fibers, pla-
sodium montmorillonite with vinylbenzyltrimethyl
telets and whiskers within the continuous polymer matrix
ammonium chloride, in order to achieve interfacial graft-
in combination with adequate interfacial adhesion
ing of polystyrene onto clay and to promote swelling of
between filler and polymer can account for substantially
clay in styrene and various solvents. In-situ bulk and solu-
improved reinforcement of the polymer matrix1). Pioneer-
tion styrene polymerization as well as compounding of
ing advances at Toyota research2) during the early 1990’s
organoclay in polystyrene melts12, 13), including the use of
has stimulated the development of various polymer/orga-
poly(styrene-co-vinyloxazoline)14) and polystyrene-block-
noclay nanocomposites with attractive property profiles
poly(ethylene oxide)15) as compatibilizers, afforded inter-
such as improved stiffness combined with elevated dimen-
calation but failed to achieve complete exfoliation. In aqu-
sional stability, barrier resistance, improved thermal stabi-
eous emulsion polymerization processes water swelling of
lity and inherent flame retardency3–8). Several synthetic
clays was combined with intergallery polymerization to
routes were examined to produce polystyrene/organoclay
improve exfoliation16, 17). In a recent advance Sogah and
nanocomposites, aiming at improving exfoliation of orga-
coworkers18) converted clay into initiators for TEMPO-
a
Current address: Freiburger Materialforschungszentrum und mediated controlled radical polymerization, thus improv-
Institut für Mikrosystemtechnik, ing control of polystyrene grafting onto silicates and sub-
Stefan-Meier-Str. 21; D-79104 Freiburg i. Br., Germany. stantially improving exfoliation. In the past incomplete

Macromol. Rapid Commun. 21, No. 1 i WILEY-VCH Verlag GmbH, D-69451 Weinheim 2000 1022-1336/2000/0101–0057$17.50+.50/0
58 B. Hoffmann, Ch. Dietrich, R. Thomann, Chr. Friedrich, R. Mülhaupt

Tab. 1. Properties of used materials


— —
Material Abbreviation Function Mn Mw /Mn Tg
g=mol 8C

polystyrene PS100 matrix 106 000 1.07 100


amine-terminated polystyrene AT-PS8 modifier 5 800 1.33 78
2-phenylethylamine PEA modifier 121 1 –

exfoliation and formation of complex nanoparticle mix- Experimental part


tures has hampered investigation of rheological behavior
although is was well recognized that nanocomposites exhi- Materials
bit unusual rheological properties. The synthetic layered silicate SOMASIFTM ME100
The rheological properties of in-situ polymerized nano- (ME100), which represents a fluromica and was prepared by
composites with end-tethered polymer chains were at first heating talcum in the presence of Na2SiF6 , was supplied by
described by Giannelis et al.19, 20) The flow behavior of CO-OP Ltd., Japan. The negative charge of the layers is
compensated by Na+-ions in the interlayer galleries. The
poly(e-caprolactone) and polyamide-6 nanocomposites
cation exchange capacity (CEC) was in a range of 0.7 to
differed extremely from that of the neat matrices, whereas 0.8 meq/g for ME100. The interlayer spacing calculated
the thermorheological properties (Arrhenius activation from the wide angle X-ray scattering (WAXS) d001-reflection
energy of flow) of the composites were entirely deter- was 0.95 nm. The cation exchange was performed with two
mined by that behavior of the matrix20). The slope of the different swelling agents: 2-phenylethylamine (PEA,

storage modulus G9 and the loss modulus G99 versus the Mn = 121 g/mol) and amine-terminated polystyrene (AT-PS8)

frequency x in the terminal region was smaller than 2 with Mn = 5 800 g/mol and degree of polymerization of 56,
and 1, respectively. Values of 2 and 1 are expected for which was prepared by means of anionic polymerization24).
melts of linear monodisperse polymers and large devia- Polystyrene (PS100), prepared by means of anionic polymer-
tions, especially for small amounts of silicate loading in ization, was used as continuous matrix. The properties of the
the percentage range may be indicative of network forma- polystyrenes are listed in Tab. 1.
tion. However, such nanocomposites based on the in-situ
Swelling of the layered silicate
polymerization technique exhibit fairly broad molar mass
distribution of the polymer matrix which hides the struc- A mixture of 5.6 mmol/l swelling agent (AT-PS8 or PEA,
ture relevant information and impedes the interpretation respectively) and 6.7 mmol/l hydrochloric acid were sus-
pended in a THF/water (4 vol.-%/1 vol.-%) mixture at 40 8C.
of the results. Therefore, quantitative correlations
Then 8 g/l of layered silicate was added to the hot solution
between the viscoelasticity and the morphology of the
and white precipitates were obtained. The precipitates were
composites cannot be established. For a better under- filtered after 30 min and washed twice: first with a hot THF/
standing of the relationship of viscoelasticity and struc- water mixture and thereafter with hot water. The modified
ture well defined model materials are necessary. layered silicate was dried in vacuum at 45 8C for 72 h. Fluor-
From early research by Weiss21) and Vansant22) it is well omica modified with AT-PS8 will be denoted as organoclay-
known that the interlayer distance of organoclays increases PS, and fluoromica modified with 2-phenylethylamine will
with increasing chain length of alkyl groups used as substi- be denoted organoclay-PEA.
tuents of alkyl ammonium cations, which represent typical
modifiers of organoclays. Similar to observations by Compounding
Okada23), who used x-amino acids as modifiers, interlayer The composites were obtained by compounding the organo-
distance can increase from 0.95 nm up to 2 nm when using clays with PS100 at 200 8C in a DACA Microcompounder
such small molecular weight modifiers. Also high molecu- for 5 min. The compound of PS100 with organoclay-PS is
lar weight modifiers have been used. For example, an indus- called C-PS, the compound of PS100 with organoclay-PEA
trial grade difunctional amine-terminated poly(butadiene- is called C-PEA. The overall silicate loading was 5 wt.-% for
the composites.
co-acrylonitrile) with number-average molecular weight
— — —
(Mn) of 1 090 g/mol and Mw /Mn = 6.75 was applied as modi- Morphological characterization
fier5). Although intercalation was observed, all these modi-
fiers failed to afford complete exfoliation. Ultrathin sections of the composites with a thickness of
approximately 50 nm were prepared with an ultramicrotome
In our research we have used polystyrenes with narrow
(Ultracut E, Reichert & Jung) equipped with a diamond
molecular weight distributions as continuous matrix and knife. Transmission electron microscopy (TEM) was carried
as ammonium-functional modifier of organoclay in order out with a Zeiss CEM 912 transmission electron microscope
to establish correlations between morphology develop- using an acceleration voltage of 120 keV. Due to the high
ment and rheological behavior of polystyrene/organoclay electron density differences between silicate and polymer
nanocomposites. staining of the samples was not necessary.
Morphology and rheology of polystyrene nanocomposites based upon organoclay 59

WAXS measurements
The interlayer distance of the organoclays was studied by
means of wide angle X-ray scattering (WAXS) using a Sie-
mens D500 apparatus with CuKa radiation (k = 0.154 nm)
and a scanning rate of 0.3 8/min.

Rheological characterization
The neat PS100 and the composites C-PS and C-PEA were
dried for 48 h at 60 8C in vacuum and molten for 20 min
under vacuum at a temperature of 200 8C in a Collin PCS2
vacuum press. The samples were pressed for 10 min and sub-
sequently quenched to ambient temperature. The plates had a
diameter of 25 mm and a thickness of approximately 1 mm.
For the rheological measurements the Rheometrics
RMS 800, a strain controlled rheometer, with parallel plate Fig. 1. WAXS traces of neat ME100 (a), organoclay-PEA (b),
geometry was used. All measurements were carried out and organoclay-PS
under nitrogen. The strain region in which the material can
be regarded as linear viscoelastic was determined by ampli- nated polystyrene (AT-PS8, Tab. 1) with number average
tude sweep experiments and is in the order of 10%. Isother- molecular weight of 5 800, which corresponds to a degree
mal frequency sweeps were taken at different temperatures of polymerization of 56, and 2-phenylethylamine (PEA),
ranging from 140 8C to 220 8C. The master curves were which corresponds to a polystyrene degree of polymeriza-
shifted with the program LSSHIFT18). The temperature of
tion of 1. As illustrated in Scheme 1, the ammonium-ter-
180 8C was chosen as reference temperature.
minated polystyrene modifier was prepared by means of
anionic polymerization followed by chain termination
with dimethylchlorosilane, silylation with allyl amine and
Results and discussion protonation of the resulting amine-terminated polystyr-
The synthetic fluoromica (ME100), which represents a ene.
hectorite obtained by heating talcum with Na2SiF6 , was Fig. 1 shows the WAXS traces of neat layered silicate
rendered organophilic by means of ion exchange of the (ME100), ME100 modified with PEA (organoclay-PEA)
sodium intergallery cations for protonated amine-termi- and ME100 modified with AT-PS8 (organoclay-PS). The

Scheme 1: Synthetic route for the preparation of AT-PS8 and organoclay-PS


60 B. Hoffmann, Ch. Dietrich, R. Thomann, Chr. Friedrich, R. Mülhaupt

Fig. 3. G9 versus reduced frequency for PS100 matrix (black


line), C-PS (F), and C-PEA (9). Silicate loading: 5 wt.-%


pounding polystyrene with Mn = 106 000 in the presence
of organoclay-PEA (compound C-PEA) or organoclay-PS
(compound C-PS). The overall silicate loading was 5
wt.-% for both composites. The TEM micrographs are
displayed in Fig. 2 where the dark lines represent the sili-
cate layers in the polystyrene matrix (bright). From
Fig. 2 (a) it is apparent that in the case of compound C-
PEA the PEA modification caused intercalation but failed
to exfoliate the intercalated particles. In sharp contrast,
compound C-PS exhibited a very fine dispersion of indi-
vidual platelets being composed of individual silicate
layers. Typically such layers were 600 nm long and 1 nm
thick. From TEM tilting experiments the layers width
was estimated to be approximately 100 nm. Obviously,
the large interlayer distance in organoclay-PS (larger than
4 nm) was accompanied by weakening of the silicate
interlayer interactions and afforded complete exfoliation
Fig. 2. TEM micrographs of the melt compounds C-PEA (a) when applying shear forces during melt compounding
and C-PS (b). Silicate loading: 5 wt.-% with matrix polystyrene (Fig. 2 (b)).
Rheological properties were determined to examine the
presence of particle network formation via interparticle
interlayer distances of the organoclays were obtained interactions and self-assembly. We found that time tem-
from the peak position (d001-reflection) of WAXS traces. perature superposition (TTS) holds for all investigated
The d001-reflection for neat ME100 was found at a 2H samples. There was no influence of a silicate loading of 5
value of 9.3 8, which corresponds to an interlayer distance wt.-% on TTS because of the high compatibility between
of 0.95 nm (Fig. 1, trace a). Organoclay modification organophilic modified ME100 and PS100. Fig. 3 shows
afforded substantially increased interlayer distances. The the storage modulus (G9) versus the reduced frequency (x
reflection of organoclay-PEA (trace b in Fig. 1) was aT) for PS100 (black line), C-PS (F), and C-PEA (9).
found at 2H of 6 8, corresponding to an interlayer distance PS100 showed the normal material response of a narrow
of 1.4 nm. In contrast, organoclay-PS (trace c in Fig. 1) distributed thermoplastic polymer. The curve for C-PEA
exhibited no d001-reflection in the relevant angle region, was slightly shifted to higher moduli values, as expected
thus indicating the existence of interlayer layer distances for the filler effect. The slope in the terminal regime was
larger than 4 nm! approximately 2 for both curves. The material response
Transmission electron microscopy (TEM) was per- of C-PS was found to be very different from that of C-
formed to examine morphology development of compo- PEA. At the lowest realized frequencies, which corre-
sites, abbreviated as C, prepared by means of melt com- spond to the marked region III, strongly increased values
Morphology and rheology of polystyrene nanocomposites based upon organoclay 61

of storage modulus were found and the slope of the curve Acknowledgement: The authors gratefully acknowledge finan-
approached zero. Such a behavior is an indication of net- cial support by the Sonderforschungsbereich SFB 428 of the
Deutsche Forschungsgemeinschaft, and thank K. Crämer for the
work formation involving assembly of individual plate-
synthesis of At-758.
lets being composed of silicate layers. In the regime of
intermediate frequencies (region II in Fig. 3) the moduli
values were reduced in comparison of that of the neat
1) H. S. Katz, J. V. Milewski, Eds., Handbook of Fillers for
matrix. This might be a dilution effect caused by the
amine-terminated polystyrene having a molecular weight Plastics, Van Nostrand Reinhold Publ., New York 1987
2) G. Lagaly, “Smectic Clays as Ionic Macromolecules” in:
lower than the entanglement molecular weight of poly- Developments in Ionic Polymers, A. D. Wilson, H. T. Posser,
styrene. A validation of the thinning effect will be Eds., Applied Science Publishers, London 1986, p. 77 ff.
described elsewhere25). At high frequencies (region I) an 3) A. Okada, Y. Kojima, M. Kawasumi, Y. Fukushima, T. Kur-
increase in the storage modulus was detected with respect auchi, O. Kamigaito, J. Mater. Res. 8, 1179 (1993)
4) A. Akelah, Polymers and Other Advanced Materials, P. N.
to that of the neat matrix. This modulus increase in this
Prasad, J. E. Mark, T. J. Fai, Eds., Plenum Press, New York
frequency range was independent of the state of disper- 1995, p. 625 ff.
sion and represents the combination of elasticity of both 5) A. Akelah, N. Salahuddin, A. Hiltner, E. Baer, A. Moet,
components, the matrix and the silicate. Nanostruct. Mater. 4, 965 (1994)
6) E. P. Giannelis, Adv. Mater. 8, 29 (1996)
7) E. P. Giannelis, Appl. Organomet. Chem. 3(5), 490 (1998)
8) C. Zilg, P. Reichert, F. Dietsche, T. Engelhardt, R. Mülhaupt,
Conclusions
Kunststoffe 88, 1812 (1998)
Organophilic modification of clay with amine-terminated 9) A. Moet, A. Akelah, Mater. Lett. 18, 97 (1993)
10) A. Moet, A. Akelah, A. Hiltner, E. Baer, Molecularly
polystyrene, obtained by means of anionic polymerization,
affords completely exfoliated polystyrene nanocomposites Designed Ultrafine/Nanostructured Materials, K. E. Gon-
salves, G. M. Chow, T. D. Xiao, R. C. Cammarata, Eds.,
containing silicate nanoparticles with an aspect ratio MRS Symp. Proc. 351, 91 (1994)
exceeding 600, when such organoclays were melt com- 11) A. Akelah, A. Moet, J. Mater. Sci. 31(13), 3589 (1996)
pounded together with polystyrene. In contrast, small 12) R. A. Vaia, K. D. Jandt, E. J. Kramer, E. P. Giannelis, Macro-
molecular weight modifiers, such as 2-phenylethylamine, molecules 28, 8080 (1995)
13) M. Sikka, L. N. Cerini, S. S. Ghosh, K. I. Winey, J. Polym.
only promoted intercalation and failed to exfoliate the sili-
Sci., Part B: Polym. Phys. 34(8), 1443 (1996)
cate particles during melt compounding. Since both the 14) N. Hasegawa, H. Okamoto, M. Kawasumi, A. Usuki, Polym.
polystyrene continuous matrix and the ammonium-termi- Mater. Sci Eng. 80, 353 (1999)
nated polystyrene attached to the silicate nanoparticle sur- 15) H. R. Fischer, L. H. Gielgens, T. P. M. Koster, Acta Polym.
face exhibited very narrow molecular weight distributions 50, 122 (1999)
16) M. Laus, M. Camerani, M. Lelli, K. Sparnacci, F. Sandrolini,
it became possible to examine rheological behavior and to
F. Francesangeli, J. Mater. Sci. 33(11), 2883 (1998)
correlate superstructure formation with rheological prop- 17) M. W. Noh, D. C. Lee, Polym. Bull. (Berlin) 42, 619 (1999)
erties. Only when high molecular weight polystyrene was 18) M. W. Weimer, H. Chen, E. P., Giannelis, D. Y. Sogah, J. Am.
grafted onto the dispersed silicate layers, rheological Chem. Soc. 121, 1615 (1999)
19) R. Krishnamoorti, E. P. Giannelis, Macromolecules 30, 4097
investigation revealed the formation of networks via
assembly of in-situ formed silicate nanoparticles. (1997)
20) E. P. Giannelis, R. Krishnamoorti, E. Manias, Adv. Polym.
It should be possible to control silicate/polymer inter- Sci. 138, 107 (1999)
action of such “hairy” silicate nanoparticles by varying 21) A. Weiss, Clays Clay Min. 10, 191 (1963)
the chain length of polystyrenes which are attached to the 22) E. F. Vansant, J. B. Uytterhoeven, Clays Clay Min. 20, 47
silicate nanoparticles surface via their ammonium end (1972)
23) A. Okada, A. Usuki, T. Kurauchi, O. Kamigaito, Hybrid Or-
group. Fully exfoliated nanocomposites based upon orga-
ganic-Inorganic Composites, J. E. Mark, C. Y. Lee, P. A.
noclay and polystyrene represent very effective model Bianci, Eds., ACS Symp. Ser. 585, 55 (1995)
systems to achieve better understanding of morphology 24) K. Crämer, H. A. Schneider, New Polymeric Mater 4, 153
development, processing and structure/property correla- (1994)
25) B. Hoffmann, C. Dietrich, Ch. Friedrich, J. Rheol., submitted
tions of nanocomposites based upon layered silicates.

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