Journal of Colloid and Interface Science 230, 210212 (2000)

doi:10.1006/jcis.2000.7088, available online at http://www.idealibrary.com on

NOTE
A Simple Method for Producing Micrometer-Sized Monodisperse
Polystyrene Particles in Aqueous Media
A method was developed for producing micrometer-sized, highly
monodisperse polystyrene particles in single stage polymerization
in aqueous media. The method employs an amphoteric surfactant, dimethyldodecylbetaine, that is added to the reaction system of styrene/K2 S2 O8 /water in early stage of reaction. Polymerizations were carried out over a range of initiator concentrations
(48 mmol/dm3 H2 O). The polymerization procedure could produce particles with an average diameter of 3.4 m with a coefficient
of variation of particle size distribution of 4.0%. C 2000 Academic Press
Key Words: chemical reaction; single stage polymerization; particle size distribution; monodisperse polystyrene particles; soap-free
emulsion polymerization.

INTRODUCTION
Methods for producing micrometer-sized polymer particles have been studied by many researchers. Nonaqueous dispersion polymerization (1, 2), seeded
growth (3, 4), and two-step swelling techniques (5, 6) are typical methods that
have been proposed. Although various aspects of these techniques are successful,
they have apparent drawbacks of being multistage polymerizations or requiring
hazardous solvents.
To overcome these problems, the authors proposed a technique for singlestage polymerization in aqueous media, which was based on soap-free emulsion
polymerization (7, 8). In the previous work, monodisperse micrometer-sized
particles could be produced by adding cationic and anionic surfactants to the
system in two steps, according to the surface charge of the particles. Recently,
the authors proposed a method, which employed an amphoteric surfactant instead of cationic and anionic surfactants. In the polymerization of styrene, an
amphoteric surfactant was added at different reaction times and it was found that
this procedure could produce highly monodisperse particles with an average diameter of 2 m (9). The present work examines single-stage polymerizations of
styrene at different initiator concentrations in the presence and in the absence of
an electrolyte (KCl), with the objective of producing micrometer-sized particles
that are highly monodisperse.

EXPERIMENTAL
All chemicals were obtained from Wako Pure Chemical Industry, Ltd. (Osaka,
Japan). Styrene (99%) was used after inhibitor removal and purification by distillation at reduced pressure under a nitrogen atmosphere. Potassium persulfate (KPS) (98%) and potassium chloride (KCl) (98%) were used as received.
Dimethyldodecylbetaine (DMDB) was synthesized by the following reaction of
dimethyldodecylamine with sodium chloroacetate in water at 70 C according
to an available literature procedure (10, 11):
C12 H25 N(CH3 )2 + ClCH2 COONa C12 H25 -N+ (CH3 )2 -CH2 COO + NaCl.
0021-9797/00 $35.00

C 2000 by Academic Press

Copyright
All rights of reproduction in any form reserved.

The resulting aqueous solution contained equal moles of DMDB and NaCl and
was used in the polymerization experiments.
Polymerizations were carried out in a batch reactor (11 cm i.d., 12 cm in
height) equipped with four baffles and an agitator one-third of the reactor diameter. The reactor was charged with 700 cm3 water and 100 cm3 styrene,
and nitrogen gas was bubbled through the solution to remove oxygen from the
system. Polymerization was initiated by the addition of 50 cm3 of an aqueous
solution having a KPS concentration of 3.2 or 6.4 mmol. At a reaction time of
10 min, 50 cm3 of the resulting aqueous solution containing 0.40 mmol DMDB
was added to the system. The entire reaction was performed at 70 C in a nitrogen
atmosphere under agitation at 300 rpm.
At appropriate intervals during the reaction, small samples (less than 20 cm3 )
were withdrawn from the reactor to determine monomer-to-polymer conversion and particle size distributions. Hydroquinone was added to the samples to
terminate the polymerization. Conversions were determined from the weight
of polymer contained in reaction mixtures from the withdrawn samples. Each
particle size distribution was determined by measuring more than 200 particle
diameters with transmission electron microscopy (Hitachi H-800). From the microscopy measurements, the average diameter, dV , and coefficient of variation,
CV , were calculated from the following relationships:
dV =

n i di3

[1]

P n

CV =

1/3
ni

. P o2 1/2
n
d
i
i
i
i ni
.P
,
P
i n i di
i ni

di

[2]

where n i is the number of particles having diameter di .

RESULTS AND DISCUSSION

Figure 1 shows the dependence of monomer-to-polymer conversion on reaction time at two different initiator concentrations. The polymerization rate
increased with an increase in initiator concentration as expected. For each experiment, the polymerization rate gradually accelerated until reaction termination.
This is probably due to the gel effect and an increase in volume of reaction loci
with time.
Figure 2 shows the evolution of particle size distributions with conversion
for the experiments of Fig. 1. The size distribution at initiator concentration of
8 mmol/dm3 H2 O was unimodal throughout the reaction and attained a high
monodispersity of CV = 3.9% with dV = 1.6 m. For the polymerization at
initiator concentration of 4 mmol/dm3 H2 O, the size distribution was initially
unimodal but became bimodal as the reaction progressed. The system attained
a coefficient of variation of 2.9% for an average particle size of 2.6 m disregarding the secondary particles.
In ordinary soap-free emulsion polymerization, an increase in initiator concentration decreases particle size. It can be considered that the higher ionic
strength caused by the increase in initiator concentration reduces electrostatic

210

211

NOTE

FIG. 1. Conversion versus reaction time during polymerization at initiator

concentrations of 4 mmol/dm3 H2 O (d) and 8 mmol/dm3 H2 O (m); monomer
concentrations: 1.1 mol/dm3 H2 O; stirring speed: 300 rpm; DMDB concentration: 0.5 mmol/dm3 H2 O; DMDB addition time: 10 min.

repulsion between particles and promotes particle aggregation. A similar effect can be expected in the present polymerizations and is possibly the reason for the appearance of the larger particles at the lower initiator concentrations.
The appearance of the secondary particles in Fig. 2a can be attributed to an
increase in electric surface potential of particles during the reaction. As the
reaction proceeds, ionic groups, originating from ionic radicals, accumulate on
the particle surface. From the measurements, the number of particles formed
in the early stage of the reaction in Fig. 2a is less than one-fourth of that in
Fig. 2b. Therefore, even though the generation rate of ionic radicals for Fig. 2a
is half of that for Fig. 2b, the particles in the reaction of Fig. 2a can have
higher surface density of ionic groups. The higher surface charge density and
the lower ionic strength induce stronger electrostatic repulsion between particles
and ionic radicals. If the stronger electrostatic repulsion is an important factor

FIG. 3. Particle size distributions and TEM photograph of final particles

at a KCl concentration of 20 mmol/dm3 H2 O and an initiator concentration of
4 mmol/dm3 H2 O before the decantation (a) and after decantation (b), (c).

for the generation of the secondary particles, the generation may be suppressed
by the addition of electrolytes to the solution.
Figure 3a shows final size distribution in a polymerization in which KCl
was added to the system after 1 h reaction time. The concentration of KCl was
20 mmol/dm3 H2 O. In this reaction, only a few secondary particles were generated, as can be seen in Fig. 2a. Thus, the addition of the electrolyte seemed to
be effective for suppressing the generation of the secondary particles. A trace
of the secondary particles was removed from the reactant mixture by decantation. As shown in Figs. 3b and 3c, the secondary particles were completely
removed. The dV and CV values of these particles were 3.4 m and 4.0%,
respectively.
The dV value for the case of electrolyte addition was more than six times
larger than that in ordinary soap-free emulsion polymerization in corresponding
reaction conditions without any surfactants. It is difficult to explain the strong
effect that the addition of the amphoteric surfactant has on the particle sizes.
One reason may be the incorporation of the amphoteric surfactant into particles,
which would increase the osmotic pressure of monomer in the particles. The
expansion of particle volume due to the osmotic pressure might give rise to
the rapid capture of radicals, and reduce the precipitation of new particles. The
total volume of particles in early reaction stage is so small that the formation of
particles is strongly affected by the adsorption or incorporation of small amounts
of surfactant.

CONCLUSIONS
A method that used amphoteric surfactant for polymerization of styrene over
a range of initiator concentrations was examined. At low initiator concentration, secondary particles were generated in an intermediate stage of the reaction, which resulted in a bimodal particle size distribution. Generation of secondary particles was greatly suppressed by the addition of KCl to the reaction
system.
FIG. 2. Evolution of the particle size distributions with conversion for the
experiments of Fig. 1 at initiator concentrations of 4 mmol/dm3 H2 O (a) and
8 mmol/dm3 H2 O (b).

REFERENCES
1. Almog, Y., Reich, S., and Levy, M., Br. Polym. J. 14, 131 (1982).

212

NOTE

2. Horak, D., J. Polym. Sci. A 37, 3785 (1999).

3. Vanderhoff, J. W., Vitkuske, J. F., Bradford, E. B., and Alfrey, T., Jr.,
J. Polym. Sci. 20, 225 (1956).
4. Kim, J. H., Sudol, E. D., El-Aaser, M. S., Vanderhoff, J. W., and Kornfelt,
D. M., Chem. Eng. Sci. 43, 2025 (1988).
5. Ugelstad, J., and Mork, P. C., Adv. Colloid Interface Sci. 13, 101
(1980).
6. Ugelstad, J., Muftakhamba, H. R., and Mork, P. C., J. Polym. Sci. Polym.
Symp. 22, 225 (1985).
7. Gu, S., and Konno, M., J. Chem. Eng. Japan 30, 742 (1997).
8. Gu, S., Mogi, T., and Konno, M., J. Colloid Interface Sci. 207, 113
(1998).
9. Konno, M., and Orihara, S., J. Chem. Eng. Japan 33, (2000) in press.
10. Schwartz, A. M., and Perry, J. W., in Surface Active Agents, p. 162.
Interscience, New York, 1949.

11. Fujimoto, T., in Shin Kaimenkasseizai Nyumori, p. 87. Sanyo Kasei

Kogyo, Tokyo, 1992.
Shinya Orihara
Mikio Konno1
Department of Chemical Engineering
Tohoku University
Sendai 980-8579, Japan
Received March 20, 2000; accepted July 5, 2000

1 To whom correspondence should be addressed. E-mail: Konno@mickey.

che.tohoku.ac.jp.