EUROPEAN

POLYMER
European Polymer Journal 42 (2006) 259–264
JOURNAL
www.elsevier.com/locate/europolj

A study of the polymerization of styrene initiated

by K–THF–GIC system
Luyi Sun a, Min Xiao b,*
, Jingjing Liu c, Kecheng Gong c

a
Polymer Technology Center, Department of Mechanical Engineering, Texas A&M University, College Station, TX 77843-3123, USA
b
School of Physics and Engineering, Sun Yat-Sen University, Guangzhou, Guangdong 510275, PR China
c
Polymer Structure and Modification Research Laboratory, South China University of Technology, Guangzhou 510640, PR China

Received 20 June 2005; received in revised form 13 July 2005; accepted 14 July 2005
Available online 31 August 2005

Abstract

In this paper, the polymerization of styrene initiated by potassium (K)-tetrahydrofuran (THF)-graphite intercalation
compound (GIC) (K–THF–GIC) was studied. The mechanism of the polymerization was determined to be anionic
polymerization according to its characteristics. The effect of the concentration of the initiator and monomer was stud-
ied. It was found that the polymerization mainly occurred on the surface and edge of the intercalated graphite. It was
also shown that the polarity of solvent has little effect on the polymerization yield in this system.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Graphite intercalation compound; Anionic polymerization; Polystyrene; GPC

1. Introduction first synthesized polyethylene by using alkali metal-GICs

Graphite intercalation compounds (GICs) are of high
interest to both chemists and physicists because of their
unique properties. In the past few decades, much atten-
tion has been paid to the preparation and properties of
GICs and their applications [1,2].
The polymerization initiated by GICs is an interest-
ing topic because GICs are a group of novel initiation
systems compared to usual initiators for polymeriza-
tions. Another reason is that delaminated graphite-poly-
mer composites can be prepared in this way and the
produced composites show excellent electrical and ther-
mal properties [3,4]. As early as in 1958, Podall, et al.
*
Corresponding author. Tel./fax: +86 20 84114113.
E-mail address: stsxm@zsu.edu.cn (M. Xiao).
as an initiator [5]. Subsequently, styrene [6–9], butadiene
[6], isoprene [6,8,10], methacrylaldehyde [8,11], crotonal-
dehyde [11], ethylene oxide [12], lactones [13], etc. were
successfully polymerized with K–GICs as an initiator.
In the past few decades, interests were mainly focused
on the polymerization mechanism and the characteriza-
tion of the synthesized polymers, while much less atten-
tion was paid to the reaction sites [3]. One research
group described that the polymerization took place on
the graphite surface [7,8], while the other group [10]
assumed that the interlayer was the reaction site. Some
recently obtained information also suggested that the
polymerization took place in the interlayer spacing of
the graphite [14,15].
In this work, the characteristics of a new GIC system
as the initiator for the polymerization of styrene were
studied. This new GIC initiation system gives some

0014-3057/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2005.07.014
260 L. Sun et al. / European Polymer Journal 42 (2006) 259–264
new features of the polymerization. The influence of the
concentration of the initiator and monomer was studied
in detail. The results not only helped to learn more
about the characteristics of this new initiation system,
but also indicated that the polymerization mainly
occurred on the surface and edge of the graphite
intercalate.
2. Experimental
2.1. Materials
Natural flake graphite (NFG) (grain size 120 mesh,
purity 99%) was supplied by Baoding Lianxin Carbide
Co. THF and ethylene glycol dimethyl ether (DME)
were dried over potassium hydroxide, refluxed over so-
dium and naphthalene until the solution turned to be
dark green, and then distilled under nitrogen before
use. Styrene was dehydrated with molecular sieve 4
and was purified by vacuum distillation. Other chemicals
such as potassium metal (chemical grade), benzene, and
anhydrous ethyl alcohol were used as purchased.
2.2. Preparation of K–THF–GIC
Stage-1 K–THF–GIC was prepared based on previ-
ously reported approach [16] with some modifications.
Typically, 0.50 g NFG and 0.68 g potassium metal were
added to a 10.0 mL THF solution containing 2.22 g
naphthalene. The mixture was stirred in a sealed flask
at room temperature for 3 days. During the reaction in
the solution, electrons were taken from the potassium
by naphthalene because of its high electron affinity.
Thus, potassium ions were coordinated with ether mol-
ecules and paired with naphthalene anion radicals.
These ether-solvated potassium ions were intercalated
into the graphite interlayers by gradual charge transfer
from naphthalene anions to hexagonal carbon layers
[16].
The reaction products were then filtered and washed
by THF in nitrogen atmosphere. X-ray diffraction pat-
tern showed that the identity period Ic of K–THF–
GIC was 0.887 nm [17], which proves the formation of
stage-1 K–THF–GIC [18]. According to literature [19],
the stage-1 K–THF–GIC with an Ic of 0.887 nm corre-
sponds to a composition of KC24(THF)2. The concen-
tration of the initiator K–THF–GIC discussed below
was calculated based on this composition.
2.3. Synthesis of polystyrene
The prepared K–THF–GIC was quickly added to a
Pyrex flask containing freshly distilled THF. The flask
was evacuated and then sealed to maintain vacuum.
The purified styrene monomer was then injected into
the flask during stirring. The polymerization was carried
out at room temperature for 2 h. The concentrations of
monomer and initiator were regulated to study the char-
acteristics of this polymerization system and the details
will be discussed below. Finally, the reaction products
were precipitated in ethanol and then dried.
2.4. Characterization of polystyrene and polystyrene/
graphite composite
The graphite was firstly separated from the polysty-
rene using a Soxhlet extractor. Then, the molecular
weight (MW) and MW distribution of polystyrene were
determined by gel permeation chromatograph (GPC)
(Waters 991) using THF as eluent. The microstructure
of polystyrene/graphite composite was examined on a
JEOL JEM-100CXII transmission electron microscope
(TEM) operated at 100 kV. Samples were microtomed
with a diamond knife to ultrathin (about 60 nm) sections
and mounted on copper grids for TEM imaging.
3. Results and discussion
3.1. The mechanism for the polymerization of styrene
initiated by K–THF–GIC
The polystyrene was prepared by the polymerization
of styrene initiated by K–THF–GIC. When styrene
monomer was injected into the flask containing THF
solution of K–THF–GIC, the evolution of heat and
increase of viscosity was observed immediately. The
known reaction scheme for the polymerization of sty-
rene initiated by aromatic radical-anions such as potas-
sium naphthalene can be briefly described as follows: the
naphthalene anion-radical transfers an electron to sty-
rene to form the styryl radical-anion, which dimerizes
to form the dicarbanion. Then anionic propagation oc-
curs at both carbanion ends of the styryl dianion [20].
Polystyrene was obtained with a relatively narrow MW
distribution, which is the characteristic of fast initiation
and formation of ‘‘living’’ polymer (living polymeriza-
tion). As K–THF–GIC is somewhat similar in structure
to potassium naphthalene, it is assumed that the poly-
merization of styrene initiated by K–THF–GIC pro-
ceeds through an anionic mechanism similar to that
initiated by potassium naphthalene. The increase of
the MW of the polystyrene on introducing additional
amount of styrene supports above assumption (Fig. 1).
However, Fig. 1 shows that the MW distribution
of the polystyrene initiated by K–THF–GIC is not as
narrow as that of polystyrene initiated by aromatic rad-
ical-anions. In curve I, there is a small tail in the low
molecular weight range, while in curve I, there appear
two peaks. These results can be explained by the hetero-
geneous characteristic of the initiator. The anions on the
 L. Sun et al. / European Polymer Journal 42 (2006) 259–264
Fig. 1. GPC curves of polystyrenes initiated by K–THF–GIC.
(I) 0.06 mol styrene was injected to a pre-evacuated flask
containing 0.04 mol/L K–THF–GIC in 40.0 mL THF. The
reaction lasted for 2 h with stirring. (II) 0.06 mol styrene was
injected to a pre-evacuated flask containing 0.04 mol/L K–
THF–GIC in 40.0 mL THF. After 2 h of reaction with stirring,
an additional 0.06 mol styrene was injected and reacted for
another 2 h with stirring.
surface or on the edge of the graphite layers could initi-
ate styrene once the styrene monomer was injected into
the flask. Due to steric hindrance, it took some time for
the styrene to be intercalated into the interlayer space of
the graphite and to be initiated by the anions contained
within. This delay resulted in a small tail in the low MW
range in curve I. As for the double peaks in curve II, it is
certain that the left peak is because of the resumed prop-
agation of the polymer chain induced by the secondly
introduced styrene at the end of the original polystyrene
living chains. While the right peak is due to the initiation
of the secondly introduced styrene by the unreacted an-
ions deep inside of the layer of the graphite and the ori-
ginal polystyrene chains which did not propagate or
only slightly propagated.
3.2. The effect of the concentration of initiator and
monomer
Usually, anionic polymerizations have the character-
istic of fast initiation and propagation, and narrow MW
distribution. The degree of polymerization of living
anionic polymerization is given by the ratio of the con-
centrations of monomer ([M]) and living ends ([I]). For
the usual situation where all of the initiator is converted
into propagating living anionic ends, the degree of
polymerization
DPn ¼ 2½M
=½I
ðaÞ
261
or
DPn ¼ ½M
=½I
ðbÞ
depending on the mode of initiation. Eq. (a) applies to
polymerizations initiated by electron transfer since each
final polymer molecule originates from two initiator
molecules. Initiation processes other than electron trans-
fer involve one polymer molecule per initiator molecule
and Eq. (b) is applicable [20].
For both of the above two cases, the higher monomer
concentration and/or the lower initiator concentration,
the higher MW can be achieved. Therefore, the experi-
ments were designed by changing monomer concentra-
tion while fixing the initiator concentration, and
changing initiator concentration while fixing monomer
concentration, respectively. The mole concentration of
K–THF–GIC, which has a composition of KC24(THF)2,
was used as the initiator concentration here. The MW
determined by GPC is shown in Figs. 2 and 3, respec-
tively. It is clear that the MW increases with the increase
of the monomer concentration and the decrease of the
initiator concentration.
However, the MW determined by GPC is much
higher than the value from the theoretical calculation.
It is believed that this is mainly because of the heteroge-
neous initiator system used here. The living anions on
the surface and edge of the graphite can initiate the poly-
merization of styrene very quickly. However, it would
take some time for styrene monomers to reach the anion
in the graphite layers, especially the ones deep inside of
the layers. Because the initiation and propagation was so
fast that this delay resulted in the fact that all the mono-
mers had been polymerized before they could reach the
Fig. 2. The influence of monomer concentration on the MW of
polystyrene [I] = 0.04 mol/L: (I) [M] = 3.0 mol/L, (II) [M] =
2.0 mol/L and (III) [M] = 1.5 mol/L.
262 L. Sun et al. / European Polymer Journal 42 (2006) 259–264

Table 2
Influence of initiator concentration on the yield, molecular
weight and initiator efficiency
[I] (mol/L) Y (%) DPn PDI [LE] (mol/L) IE (%)
0.02 98.1 875.3 2.93 0.0045 22.5
0.04 94.5 730.6 2.25 0.0052 13.0
0.08 97.0 697.8 1.49 0.0056 7.0
Note: [M] = 2.0 mol/L, reaction time = 2 h.

lay on the surface or on the edge of the graphite layers.

Fig. 3. The influence of initiator concentration on the MW of
polystyrene [M] = 2.0 mol/L: (I) [I] = 0.02 mol/L, (II) [I] =
0.04 mol/L and (III) [I] = 0.08 mol/L.
anions deep inside of the layers. Therefore, in fact, only
a part of the anions participated in the initiation of the
polymerization of the styrene. This is the reason why the
actual MW is much higher than the theoretical value.
Tables 1 and 2 list the influence of monomer concen-
tration and initiator concentration on the yield, MW
and initiator efficiency. Y, DPn, PDI, [LE], IE represents
yield, degree of polymerization, polydispersity index, liv-
ing ends concentration, and initiator efficiency, respec-
tively. Here, [LE] = 2[M] Æ Y/DPn; IE = [LE]/[I].
Table 1 shows that when the initiator concentration
was kept constant, with the increase of the monomer
concentration, both yield and MW increased, but the
change of the MW distribution did not show any regu-
larity. Both [LE] and IE exhibited low values and both
also increased slightly with the increasing monomer con-
centration. This likely due to the fat that anions that
took part in the initiation of the polymerization mainly
With the increase of the monomer concentration, more
monomers have a chance to enter the graphite layers
to be initiated by anions contained within. Therefore,
more anions between the graphite layers had a chance
to take part in the initiation. However, because it took
time for the monomers to enter the interlayers of graph-
ite, and due to the fast initiation and propagation of the
whole reaction, most of the monomers were consumed
before they could enter the layers. Therefore, generally,
the number of anionic ends which took part in the initi-
ation only increased slightly, which results in the small
increase of the initiator efficiency.
Table 2 shows when monomer concentration was
kept constant, PDI and IE changed remarkably with
the increase of the initiator concentration. The higher
initiator concentration resulted in lower MW, narrower
MW distribution and lower initiator efficiency. This is
because when the concentration of the initiator in-
creased, there were relatively more living anions on the
surface or edge of the graphite. In such a case, less living
anions in the layer had a chance to take part in the poly-
merization. Therefore, most of the monomers were
quickly polymerized on the surface or on the edge of
the graphite. This resulted in the narrower MW distribu-
tion and lower initiator efficiency. However, when the
initiator concentration was low, the number of the living
anions on the surface or the edge of the graphite was
limited. When these anions were initiating the polymeri-
zation and the propagation was going on, other mono-
mers can enter the graphite layers to be initiated by
the living anions within the interlayer. Therefore, it
resulted in higher initiator efficiency. But such polymer
chains formed in the layers were usually shorter. This
gave rise to the wide MW distribution.

3.3. Reaction sites

Table 1
When explaining the mechanism of the polymeriza-
Influence of monomer concentration on the yield, molecular
weight and initiator efficiency tion and the influence of the concentration of monomer
and initiator on the polymerization, it is assumed that
[M] (mol/L) Y (%) DPn PDI [LE] (mol/L) IE (%)
the polymerization mainly occurred at the surface and
1.5 92.3 610.9 2.61 0.0045 11.3 edge of the graphite, but some of the monomer still en-
2.0 94.5 730.6 2.25 0.0052 13.0 tered the interlayer of the graphite and were polymerized
3.0 99.2 1077.4 2.52 0.0055 13.8 between the layers. The characterization of the micro-
Note: [I] = 0.04 mol/L, reaction time = 2 h. structure of the produced polymer composite further
 L. Sun et al. / European Polymer Journal 42 (2006) 259–264
Fig. 4. TEM image of polystyrene/graphite nanocomposite
containing 2.8 wt% graphite.
confirms our assumption. Fig. 4 shows the TEM image
of polystyrene/graphite composite containing 2.8 wt%
graphite. The dark bands shown in the figure correspond
to graphite layers. The graphite layers dispersed in the
polystyrene matrix with thickness less than 100 nm.
The orientation of the graphite layers reflects the initial
stacking arrangement of the layers of pristine NFG. It is
shown that in this K–THF–GIC initiated styrene poly-
merization system, styrene can intercalate into the inter-
layer space of the graphite and be initiated by the anions
in the interlayer space. However, due to the high activity
of the anions on the surface and edge of graphite layers,
most styrene was polymerized there. Some styrene
monomers entered some of the interlayer space of
the graphite and were polymerized, caused the graphite
to be exfoliated into lamellae with thickness of less
than 100 nm. Further more, some other good properties
of this graphite/polystyrene nanocomposite also indi-
cated that there must be some interfacial interaction
between the graphite layers and the polymer working
here [21].
3.4. The effect of solvent on the polymerization yield
Although anionic polymerization is mainly deter-
mined by the characteristic of the initiator and the
monomer, solvent polarity also plays an important role.
Usually, the higher polarity of the solvent, the higher
reaction rate [20].
In the previous studies, Panaiotov, etc. found that
with the decrease of the polarity of the solvents, the yield
of the polymerization decreased when they studied the
polymerization of styrene initiated by K–GIC system
in different solvents [8]. The effect of solvents on yield
was also studied here, but the result was not consistent
with the previous report.
Table 3 shows that there is no significant change in
yield with the decrease of the polarity of the solvents
when K–THF–GIC was used as an initiator. It has been
reported that when K–GIC was used to initiate the poly-
263
Table 3
Yield of polystyrene synthesized in different solvents
Solvent THF DME Benzene
Yield (%) (initiated by K–GIC; 98 53 30
data from Ref. [7])
Yield (%) (initiated by 99 94 97
K–THF–GIC)
merization, solvents may be co-intercalated into the
graphite layers depending on the affinity of the solvents
for the monomers and graphene layers [22]. Thus, the
polymerization may be seriously affected by the selection
of solvents. While for the K–THF–GIC system, THF al-
ready exists within the graphene layers. Therefore, no
matter what solvent is selected, the yield of the polymer-
ization of styrene can maintain almost constant.
Compared with K–GIC, K–THF–GIC initiator sys-
tem shows some advantages. K–THF–GIC is easier to
prepare, and when it is used to polymerize styrene, some
nonpolar solvents, which are cheaper and easier to be
separated from water, can be used.
4. Conclusions
Polystyrene was successfully synthesized using K–
THF–GIC as the initiator system. The polymerization
was determined to be living anionic polymerization
based on its characteristics. The polymerization mainly
occurred at the surface and edge of the graphite, but
some of the monomer also entered the interlayer of the
graphite and were polymerized between the layers. It
was also found that the polarity of the solvent has little
effect on the polymerization yield. This K–THF–GIC
initiation system may find applications for the prepara-
tion of polymer/graphite nanocomposites.
Acknowledgement
Financial Support from the National Natural Science
Foundation of China (No. 59836230 and No. 50203016)
is gratefully acknowledged.
References
[1] Inagaki M. J Mater Res 1989;4:1560.
[2] Kagan HB. CHEMTECH 1976;6:510.
[3] Shioyama H. Synth Met 2000;114:1.
[4] Rashkov IB. Mater Sci Forum 1992;91–93:829.
[5] Podall H, Foster WE, Giraitis AP. J Org Chem 1958;23:82.
[6] Parrod J, Beinert G. J Polym Sci 1961;53:99.
[7] Panayotov IM, Rashkov IB. J Polym Sci 1972;10:1267.
[8] Panayotov IM, Rashkov IB. J Polym Sci 1973;11:2615.
264 L. Sun et al. / European Polymer Journal 42 (2006) 259–264
[9] Panayotov IM, Rashkov IB. Makromol Chem 1974;175:
3305.
[10] Gole J. Mater Sci Eng 1977;31:309.
[11] Rashkov IB, Spassov SL, Panayotov IM. Makromol Chem
1973;170:39.
[12] Panayotov IM, Berlinova IV, Rashkov IB. J Polym Sci
1975;13:2043.
[13] Rashkov I, Panayotov I, Gitsov I. Polym Bull 1981;4:97.
[14] Shioyama H. Carbon 1997;35:1664.
[15] Shioyama H, Tatsumi K, Iwashita N, Fujita K, Sawada Y.
Synth Met 1998;96:229.
[16] Tanaike O, Inagaki M. Carbon 1997;35:831.
[17] Xiao M, Liu JJ, Li Y, Gong KC. New Carbon Mater 2003;
18:53.
[18] Inagaki M, Tanaike O. Synth Met 1995;73:77.
[19] Beguin F, Setton R, Hamwi A, Touzain P. Mater Sci Eng
1979;40:167.
[20] Odian G. Principles of polymerization, third ed. New
York: John Wiley & Sons; 1991 [chapter 5].
[21] Xiao M, Sun LY, Liu JJ, Li Y, Gong KC. Polymer 2002;
43:2245.
[22] Shioyama H. J Mater Chem 2001;11:3307.