Macromolecular Research, Vol. 17, No.

6, pp 397-402 (2009)

Controlling the Size and Surface Morphology of Carboxylated Polystyrene Latex

Particles by Ammonium Hydroxide in Emulsifier-free Polymerization

Hyunbae Dong and Sang-Yup Lee*

Department of Chemical and Biomolecular Engineering, Yonsei University, Seoul 120-749, Korea

Gi-Ra Yi
Korea Basic Science Institute, Seoul 136-713, Korea

Received April 15, 2008; Revised November 15, 2008; Accepted November 30, 2008

Abstract: In emulsifier-free, emulsion polymerization with ionizable comonomer, the ionization of the comonomer
is critical in determining the size of the final polymeric particles at sub-micrometer scale. In this study, polystyrene
latex beads with carboxylates on the surface were synthesized using acrylic acid as a comonomer. Specifically,
ammonium hydroxide was added to the emulsifier-free polymerization system to promote the ionization of acrylic
acid by increasing pH. Smaller polystyrene latex particles were produced by increasing the ammonium hydroxide
concentration in the reaction system, due to the enhanced stability promoted by the ionization of acrylic acid during
the nucleation step. In addition, the surface morphology of the polystyrene latex particles was controlled by the con-
centration of acrylic acid, the dissociation of which was influenced by the ammonium hydroxide concentration.
Keywords: polystyrene, acrylic acid, ammonium hydroxide, emulsifier-free polymerization, solubility.

Introduction linker, respectively. In addition, water-soluble comonomer

and salt are used for controlling the size and surface func-
Applications of monodisperse polystyrene nanoparticles tional groups. In particular, surface functional groups were
are expanding to various engineering fields such as photo- produced from initiator and comonomer, which is of pri-
nic band gap crystals,1,2 lithographic photo masks,3 and drug mary importance because they control stability that deter-
delivery systems4 from the conventional usages of painting, mines the product size and morphology during the polym-
papers, and adhesives.5 For the advanced application of erization. In previous reports, researchers have investigated
polystyrene latex particles in electronic and photonic devices, the effects of monomer, comonomer, and initiator on the
surface-functionalized monodisperse particles with high purity particle size and degree of polymerization with feasible
are necessary. In general, the polystyrene particles are fabri- mechanisms. However, the size dependency to the initiator
cated via mini/micro-emulsion technique where the emulsi- concentration is not clarified yet specifically when addi-
fier is added in for the control of particle size and colloidal tional ions are engaged in the polymerization system.5,7 It is
stability.6 However, due to the emulsifier locating at surface, believed that the size reduction is explained not only by the
it is limited to control the surface functional groups and the promoted nucleation of polystyrene seed with increase of
emulsifier could work as a contamination source in electri- initiator concentration but by the enhanced stabilization of
cal devices. Moreover, the colloidal stability can be lost dur- polymerized particles by additional ions in the aqueous
ing purification process. Emulsifier-free emulsion polym- medium.8 From these findings, the surface electrostatic repul-
erization is a well-known synthesis method for preparing sion of particles should be controlled for the synthesis of
polystyrene latex particles precluding contamination by the stable monodisperse polystyrene particles in emulsifier-free
emulsifier. Thereby, polystyrene nanoparticles prepared emulsion polymerization. The electrostatic repulsion forces
emulsifier-free emulsion polymerization method have been between polystyrene particles are dependent to the density
used as a good model system for the advanced applications. of adsorbed ionized groups at the surfaces. The ionization of
In the general emulsifier-free emulsion polymerization, comonomer is dependent to the amount of added ammo-
the reaction system consists of styrene, potassium persul- nium hydroxide.
fate, and divinyl benzene as a monomer, initiator, and cross- In this study, the influences of ammonium hydroxide on
the average size and morphology of polystyrene latex parti-
*Corresponding Author. E-mail: [email protected] cles are investigated. Ammonium hydroxide was chosen as

397
 H. Dong et al.

additional ion source because it is expected to improve sta-

bility during the polymerization process by increasing pH.
Subsequently, the average particle size effectively will be
controlled by the addition of ammonium hydroxide solution
as well as adjustment of comonomer concentration.

Experimental

Chemicals and Equipments. Styrene monomer (99%),

divinyl benzene (ACS technical grade, 80%), potassium
persulfate (ACS grade, 99%) were purchased from Aldrich
and used without further purification. Acrylic acid (Aldrich
99%) was chosen as a comonomer that is soluble in water.
Ammonium hydroxide solution (Duksan Chemical, 30 wt%)
was used for pH control. Polymerization was carried out in
a jacketed cylindrical glass reaction vessel which equipped Figure 1. Average diameter of polystyrene latex particles pre-
with a reflux condenser and a teflon stirrer. The stirrer with pared without acrylic acid (solid line is guide for eye).
anchor type baffle was positioned 1 cm from the bottom.
Stirring rate was maintained at 400 rpm during the reaction. keeping the reaction concentrations of initiator, styrene
Temperature of the reactor was kept constant at 70 oC with monomer, and crosslinker constant, emulsifier-free emul-
the use of a circulating temperature bath. The reaction ves- sion polymerization was carried out with variance of ammo-
sel was purged with nitrogen to remove dissolved oxygen in nium hydroxide concentration. In Figure 1, the average
the reaction solution at the initial stage and then the nitrogen diameter of polystyrene particles was plotted against the
environment was kept during the whole reaction process. concentration of ammonium hydroxide. Under the ammo-
Synthesis of Polystyrene Latex Particles. Emulsifier- nium hydroxide concentration of 0.28 M, the average diam-
free emulsion polymerization was carried out in a batch eter increased almost linearly. This size increment is similar
reactor. A volume of 12 mL styrene and 0.12 mL divinyl to the size increase driven by salting out effect.9-11 In con-
benzene were injected in reaction vessel containing 400 mL trast, over the ammonium hydroxide concentrations of 0.28 M,
deionized water and various amounts of ammonia solution. particle size increased with small slope and saturated. This
The temperature was increased to 70 oC for the decomposi- saturation of particle size at high ammonium concentration
tion of initiator, potassium persulfate. In order to remove is likely due to the saturated salting out effect where the sol-
oxygen inside, nitrogen gas was purged in the reactor for ubility of styrene changes little by the addition of ammo-
30 min and then various amount of acrylic acid and 25 mL nium hydroxide. The crucial concentration of 0.28 M was
of 37 mM potassium persulfate solution were injected. The determined from the cross point where two different slope
reaction was left to reflux for 8 h. Nitrogen purge and stir- of size increment meets.
ring at a rate of 400 rpm were maintained throughout the With the observation of particle size, conversion was
polymerization. monitored during the polymerization. In order to observe
Characterization. Size distribution of polystyrene latex the ammonium hydroxide effect clearly, two conditions were
particles was determined using a dynamic light scattering chosen from Figure 1 where the product particle sizes are
equipment (ELS-Z, Otsuka electronics). The hydrodynamic different obviously. In Figure 2, plots of conversion and size
radii were measured five times for each sample, then the change are present. The first interval of the reaction
average and standard deviations were calculated. The mor- increased with the increase of ammonium hydroxide con-
phologies of polystyrene nanoparticles were observed using tents as present in Figure 2(a). This behavior is similar to
scanning electron microscopy (SEM, S4700, Hitachi, 10 the commonly observed salt addition effect that reduces sol-
kV) and field-emission transmission electron microscopy ubility of monomer.12
(FE-TEM, FEI Co., 300 kV). From the plot of particle sizes against conversion, the size
difference was clearly observed with increment of conver-
Results and Discussion sion. In Figure 2(b), the size variation with the conversion is
present where larger product particles were obtained at high
Effects of Ammonium Hydroxide Concentration on ammonium hydroxide concentration. In a condition of low
Polystyrene Particle Size in the Absence of Acrylic Acid. ammonium hydroxide concentration, particle grows large
Firstly, the effects of ammonium hydroxide concentration even at a low conversion. These particles grew up slowly
on the average size of polystyrene nanoparticles were exam- with progress of polymerization. In contrast, when large
ined in the absence of comonomer, acrylic acid. While amount of ammonium hydroxide was added, relatively

398 Macromol. Res., Vol. 17, No. 6, 2009

 Size Control of PS Particle by Ammonium Hydroxide

Figure 3. SEM images of polystyrene latex particles synthesized

without acrylic acid with variation of ammonium hydroxide con-
centrations. (a) 0.0 M, (b) 0.18 M, (c) 0.24 M, (d) 0.75 M of
ammonium hydroxide.

Figure 2. Conversion and particle size changes with the progress

of reaction (a) conversion changes with time, (b) particle size
change against conversion (lines are guides for eye).

small particles were formed at the low conversion and they

grew up continuously with the polymerization. This particle
growth behavior is reported to be due to the monomer solu- Figure 4. Polystyrene latex particle size dependence to the ion
bility change, and larger particle would be harvested when concentration. The experimental data were fitted with Goodwin’s
the solubility is low.13 Since the solubility of monomer is model.
dependent to the ammonium hydroxide concentration in this
system, it can be inferred that the ammonium hydroxide might logD = 0.0795logC + 2.581 (at 70 oC)
have caused salting out effect during the polymerization.
SEM images of polystyrene particles prepared with dif- where, D is the diameter of particle and C is the ionic strength
ferent concentrations of ammonium hydroxide are present dissolved in. This experimental trend of increasing particle
in Figure 3. The particles keep their spherical shape with size with ammonium hydroxide concentration agrees with
smooth surface in all cases. This spherical shapes indicate Goodwin’s model, though the slope of the fitted equation was
that the coagulation of styrene oligomers were done at lowered around one-third of the original Goodwin’s equation.
the initial stage of polymerization due to the salting out This small value of slope suggests that the particle size
effect.14 change is less dependent to the ammonium concentration
The size dependency of polystyrene nanoparticles to the comparing to other salts used in Goodwin’s experiments.
ionic concentration could be predicted with a model equa- Effects of Ammonium Hydroxide Concentration on
tion proposed by Goodwin et al..15 In Figure 4, by compar- the Polymerization of Polystyrene Particles with Acrylic
ing our experimental data with model equation, all data was Acid. When comonomer of acrylic acid was added to the
fitted well into the following equation; above polymerization system, the average particle size was

Macromol. Res., Vol. 17, No. 6, 2009 399

 H. Dong et al.

ammonium hydroxide is added in. The addition of ammo-

nium hydroxide makes reaction medium basic from acidic,
which promotes the dissociation of carboxyl group of
acrylic acid to form carboxylate anion. The ionized acrylic
acid form more oligomers and these charged oligomers with
carboxylates would diffuse to the particle surface. By the
association of charged oligomer, the nanoparticles were sta-
bilized at the early stage of reaction. The rich carboxyl
groups from acrylic acid provide sufficient electrical repul-
sive force that stabilizes polystyrene particle.16,17 In the
same fashion, the particle sizes were reduced with increase
of ammonium hydroxide concentration at the same acrylic
acid concentration. The addition of ammonium hydroxide
resulted in increase of pH promoting the acrylic acid disso-
Figure 5. Average diameter of polystyrene latex particles pre- ciation. A similar behavior is reported for the well-known
pared with different concentrations of acrylic acid with and with- comonomer of methacrylic acid. The promoted dissociation
out ammonium hydroxide (lines are guide for eye). of methacrylic acid is observed with pH increase.18,19 The
enhanced dissociation of methacrylic acid resulted in reduc-
tion of reaction rate suggesting reduction of product particle
reduced with both increases of acrylic acid and ammonium size.20
hydroxide concentrations. The average particle sizes are All of these observations consistently indicate that the
shown in Figure 5 with the both changes of acrylic acid and polystyrene particle size can be adjusted by controlling the
ammonium hydroxide concentrations. In most of cases, par- ionization of comonomer of acrylic acid, which can be pro-
ticle sizes were reduced comparing to the sizes of particles moted by addition of ammonium hydroxide. By adjusting
that were prepared without acrylic acid. In the absence of the pH above the pKa of carboxylate, more acrylic acid
ammonium hydroxide, the particle size was not changed would dissociate to stabilize the polystyrene particles at the
much even when the concentration of acrylic acid was early stage of formation. This dissociation also explains well
increased to 0.17 M. This slight change of particle size is the decrease of particle diameter with increase of acrylic
because of the acidity of acrylic acid. As noted in Table I, acid concentration at high ammonium hydroxide concentration.
the pH of reaction system was maintained lower than 3.0 in Particle Morphology Dependence to Ammonium Hy-
the absence of ammonium hydroxide. Since acrylic acid droxide and Acrylic Acid Concentrations. Morphologies
would not fully dissociate at such a low pH, under the pKa of polystyrene nanoparticles were strongly affected by the
of carboxylate, acrylic acid would contribute little to stabi- comonomer and ammonium hydroxide concentrations. As
lize the polystyrene particle at the early stage. Subsequently, shown in images of scanning electron microscopy of Figure
the polystyrene particle size would not be influenced by the 6, wrinkled surfaces of polystyrene particle are observed
increase of acrylic acid. On the while, pH of the reaction with the increase of acrylic acid concentration. In addition,
system changes when the amounts of ammonium hydroxide increment of acrylic acid concentration resulted in size re-
and acrylic acid are balanced. Changes of pH resulted in duction with broadening of the size distribution. The rough-
particle size variation as present in Figure 5. In each experi- ened surface of polystyrene particle is clearly observed in
ment, changes of the pH during the polymerization were the TEM picture present in Figure 7. As observed in Figure
negligible as far as the pH maintained above pKa of acrylic 6, the higher concentration of acrylic acid would result in
acid, around 4.3. In the pH range above pKa, over 90% of rough surface with irregular surface morphology.
acrylic acid would be dissociated and affected little by the As described in the reference cited, such non-smooth sur-
slight pH change during the polymerization. face of particles might be from deposition of polymeric
The average particle size dramatically decreased when materials such as oligomers and tiny nanoparticles in the

Table I. pH of the Polystyrene System Present in Figure 4

Acrylic acid (mL)
*pH of the Reaction System
0.03 M (1.0 mL) 0.06 M (2.0 mL) 0.09 M (3.0 mL) 0.17 M (5.0 mL)
0.0 M (0 mL) 2.8 2.8 2.8 2.9
Ammonium Hydroxide 0.24 M (3.2 mL) 9.3 9.4 7.5 5.8
Concentration (added volume)
0.75 M (10.0 mL) 10.1 10.0 9.9 9.6
* pH was measured after completing the reaction.

400 Macromol. Res., Vol. 17, No. 6, 2009

 Size Control of PS Particle by Ammonium Hydroxide

Figure 6. Surface morphology changes with respect to the comonomer and ammonium hydroxide concentrations. The acrylic acid con-
centrations were set 0.0, 0.06, and 0.17 M for each ammonium hydroxide concentration. The acrylic acid concentration increases from
left to right. (a~c) particles prepared without ammonium hydroxide, (d~f) particles prepared with 0.24 M ammonium hydroxide, (g~i)
particles prepared with 0.75 M ammonium hydroxide. SEM pictures were taken at 50,000 times magnification.

polymeric materials.21 This kind of polymeric material dep-

osition can be thought as the heterocoagulation between
core latex particle and polymeric materials are taking place.
The size reduction of the product latex particle is known
due to the promoted formation of nuclei at the early stage of
polymerization.21 It is reasonable that the increased acrylic
acid concentration promotes hydrophilic oligomer forma-
tion working as nuclei. Therefore, the product latex particle
size would decrease with the acrylic acid concentration.

Figure 7. TEM images of polystyrene latex particles prepared Conclusions

different comonomer and ammonium hydroxide concentrations.
(a) a smooth surface: 0.0 M of acrylic acid and 0.24 M of The addition of ammonium hydroxide to the emulsifier-
NH4OH, (b) a rough surface: 0.06 M of acrylic acid and 0.24 M free polystyrene synthesis system was an effective way to
of NH4OH (Scale bar: 200 nm). control the average particle sizes. In the absence of acrylic
acid, increased ammonium hydroxide concentration pro-
moted salting out of styrene monomer resulting in particle
bulk to the larger polystyrene particle surface and further size growth. On the contrary, the average particle size was
polymerization was stopped due to the depletion of mono- reduced with a rise of ammonium and acrylic acid concen-
mer.14 Formation of the hydrophilic oligomers were pro- trations. The ionization of acrylic acid is the key factor lead-
moted with increase of acrylic acid at high pH working ing particle size reduction, which was influenced by the

Macromol. Res., Vol. 17, No. 6, 2009 401

 H. Dong et al.

addition of ammonium hydroxide to the reacting solution. (7) P. J. Feeney, D. H. Napper, and R. G. Gilbert, Macromole-
In addition, the surface morphology of nanoparticles was cules, 20, 2922 (1987).
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402 Macromol. Res., Vol. 17, No. 6, 2009