Macromol. Rapid Commun.

2003, 24, 585–588 585

Communication: Poly(methyl methacrylate) nanosize par-

ticles were synthesized by a differential microemulsion
polymerization process. Sodium dodecylsulfate and ammo-
nium persulfate were used as the surfactant and initiator,
respectively. The effects of reaction conditions on the particle
size have been investigated. A particle size of less than 20 nm
in diameter has been achieved with surfactant/monomer and
surfactant/water weight ratios of 1:18 and 1:120, i.e. much
milder conditions than those previously reported in the
literature.

TEM image of nanoparticles prepared via differential

microemulsion polymerization.

Synthesis of Poly(methyl methacrylate) Nanosize

Particles by Differential Microemulsion Polymerization
Guangwei He, Qinmin Pan,* Garry L. Rempel*
Department of Chemical Engineering, University of Waterloo, 200 University Ave. West, Waterloo, Ontario, N2L 3G1, Canada
E-mail: qpan@cape.uwaterloo.ca, grempel@cape.uwaterloo.ca

Keywords: differential microemulsion polymerization; nanoparticles; polymer particles; poly(methyl methacrylate)

Introduction polymerization methods. Miniemulsion and microemulsion

Nanosize particles have attractive characteristics, which
have been receiving a great amount of attention in the last
decade. Owing to the very small size, the surface area is
very large, and the percentage of molecules or atoms on the
surface is greatly increased, which is expected to have wide
applications in various fields such as medical, semicon-
ductor, catalyst, agriculture and environment.[1] Polymer
nanoparticles have especially important uses, for example,
as drug delivery carriers,[2,3] impact modifiers for plastics[4]
and so on. However, making polymer nanoparticles remains
a challenging topic.
The methods for making inorganic nanoparticles, con-
sisting of ceramic, metal, semiconductors, and other mate-
rials, such as metal oxides, have been the subject of
extensive investigation, including methods of gas phase,[5]
sol-gel,[6] and laser irradiation,[7] etc. However, they are not
suitable for making polymer nanoparticles, as polymers
cannot endure high temperature or other extreme conditions,
which are involved in the methods mentioned above. Poly-
mer nanoparticles are at present prepared mainly by
polymerization methods are the representative methods.
The microemulsion method requires a much higher
amount of surfactant compared with conventional emulsion
polymerization, which raises concerns with cost required
for materials and post-treatment to remove the surfactants
after polymerization. One of the reasons that microemul-
sion polymerization has not been widely used in industry is
the requirement of large amounts of surfactant. These
surfactants are expensive and have significantly negative
impact on the properties of the polymers. Jones and Fu[8,9]
and Ming et al.[10] used this method to synthesize
poly(methyl methacrylate) (PMMA) nanoparticles, termed
modified microemulsion polymerization. A small amount
of monomer was added into the reactor first, and then the
remaining monomer was added dropwise. Reaction tem-
perature was reduced to 40 8C by adopting a redox initiation
system. The stirrer speed was 600 rpm. The surfactant used
was 98% sodium dodecylsulfate.[8] The PMMA particles
obtained were larger than 13 nm with a surfactant/monomer
ratio higher than 1:10. In another paper,[9] dodecyltri-
methylammonium bromide was used as the surfactant and

Macromol. Rapid Commun. 2003, 24, No. 9 ß WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2003 1022-1336/2003/0906–585$17.50þ.50/0
586 G. He, Q. Pan, G. L. Rempel

potassium persulfate as the initiator. Reaction temperature
was 60 8C and magnet stirring was applied to the system.
The diameters of the resulting PMMA particles were within
the range of 33–46 nm.
Miniemulsion polymerization is a method that uses
highly water-insoluble monomers or water-insoluble
reagents to make fine particles. The number of monomer
droplets is the same as that of the polymer particles
obtained. The particle sizes are usually in the range of 50–
500 nm,[11,12] which is larger than those obtained by
microemulsion polymerization. However, it is advanta-
geous that less surfactant is needed compared with
microemulsion polymerization.
It is very desirable to improve microemulsion polymer-
ization so that much less surfactant is required. This
Communication presents an attempt to significantly reduce
the amount of surfactant in microemulsion polymerization
for the preparation of polymer nanoparticles.
Experimental Part
PMMA nanoparticles were synthesized through differential
microemulsion polymerization by a semi-batch operation.
Ammonium persulfate (APS) was used as the initiator and
sodium dodecyl sulfate (SDS) as the surfactant. APS, SDS and
deionized water were put into a three-neck round-bottom flask
(250 ml) equipped with magnetic stirrer, reflux condenser and
thermometer. After the temperature was raised to 75 8C, the
monomer was added in a differential manner (continuously
addition in very small drops) for about 1 h. Afterwards, the
reaction temperature was kept at 80–85 8C for an additional
hour before a cooling operation was applied. Pure PMMA was
obtained by precipitating with 10 wt.-% calcium chloride,
washing with deionized water and drying under vacuum at
40–50 8C.
The solid content (S%) of the polymer emulsion was
determined by the weighing method and calculated by
S% ¼ W1 =W2
100% ð1Þ
where W1 and W2 are the weights of dried polymer and polymer
latex, respectively. Particle mean size and its polydispersity
(PD) were determined by means of dynamic light scatting with
a 90Plus particle size analyzer of Brookhaven Instrument
Corporation with software of ver. 3.37. The PD was defined as
PD ¼ m=G2 ð2Þ
where m is proportional to the variance of the intensity-
weighted diffusion coefficient distribution and G is related to
the relaxation of the intensity fluctuations of the scattered light.
A small PD means a narrow distribution. Molecular weights
and molecular weight distributions (MWD) were measured
by gel permeation chromatography (GPC) equipped with
DAWN1DSP-F laser photomer and Waters 2410 refractive
index detector. Polystyrene standards were used for calibra-
tion. Tetrahydrofuran (THF) was used as the eluent.
Results and Discussion
The effect of the solid content on particle sizes is shown
in Table 1. At lower solid content, for example, run 1
(S% ¼ 13%), the average particle size is 16.1 nm in
diameter. As the water/monomer ratio was relatively high,
the probability that one particle collides with another
particle was lower, and hence the size of the particles was
smaller than for other samples obtained at higher solid
content even though the surfactant/monomer ratio was the
same. Besides the changes in the sizes of the PMMA
particles, the appearance changed from translucent dilute
liquid to a translucent viscous one with increasing solid
content.
The types and amounts of surfactant have a great
influence on particle sizes. With the increase in the amount
of surfactant, the particle sizes become smaller (Figure 1).
However, beyond a certain level, the amount of surfactant
had little effect on particle size. The particle size of run
1 was less than 20 nm (16.1 nm) at an SDS/water weight
ratio of 1:120 (ca. 0.84 wt.-% of water phase) and an SDS/
MMA weight ratio of 1:18 (ca. 5.5 wt.-% of monomer
phase). These ratios are much lower than those reported in
the literature.[8–10,13] In these experiments, nucleation is
mainly in the water phase because MMA is slightly water-
soluble (ca. 2 wt.-%). When the initiator decomposes into
free radicals in the water phase, these free radicals first
attack MMA in the water phase to form monomer radicals.
These monomer radicals will grow in the water phase to a
certain chain length and then precipitate. These precipitates
are surrounded by the surfactant to become polymer
precursors. The polymer radical in the small newly formed
particle will continue to grow by accepting monomers from
the water phase until termination. These particles are small
if the amounts of surfactant are adequately sufficient to

Table 1. Effect of the solid content on particle sizes of PMMA (MMA containing 1-pentanol was added in a differential manner and
stirring speed was set at 4th level by using a magnetic stirrer).

Run MMA 1-Pentanol SDS APS Water Solid content Appearance Particle size PD
ml ml g g ml % nm
1 14 0.2 0.7 0.08 84 13.7 translucent 16.1 0.167
2 14 0.2 0.7 0.08 60 16.6 translucent 18.2 0.149
3 28 0.4 1.4 0.16 60 29.6 viscous translucent 32.4 0.121
4 28 0.4 1.4 0.16 45 35.9 viscous translucent 40.2 0.169
Synthesis of Poly(methyl methacrylate) Nanosize Particles . . . 587

through this process is stable, and even after a month,

Figure 1. Effect of amounts of surfactants on particle size
(MMA: 14 ml, 1-pentanol: 0.2 ml, APS: 0.08 g, water: 84 ml,
addition method: differential).
allow the generation of other particle precursors and cove-
rage of the newly formed surfaces. Therefore, in differential
microemulsion polymerization, there is a critical amount of
surfactant in order to generate small particles. If the amount
of surfactant is smaller than the critical amount, the number
of particle precursors is lower, and therefore, the probabi-
lity of polymer radicals in the water phase penetrating into
the already formed dead particle is higher. That is why the
particle size increases very fast when low amounts of
surfactant are used. If the amount of surfactant is higher
than the critical amount, the particle size does not change
much. It was reported that the average number of polymer
chains per particle is little more than just one macro-
molecule.[13] Therefore, the particle size does not change
much when the amount of surfactant used is increased by
3 times, from 0.7 g to 2.1 g. The microemulsion obtained
particle size did not change. The amount of surfactant used
in the present study is much lower than the usual levels
reported in the literature described above.
The method of monomer addition also affects particle
size (Table 2). When MMAwas added in one single portion,
the particle size was very large (run 5 in Table 2). Addition
of MMA in several portions results in decreasing particle
size, with increasing the number of portions. The mono-
mers in the reaction system form monomer droplets when
the monomer amount added in the beginning is high. When
polymerization starts, there is monomer transfer between
the water phase and the oil phase. Therefore, the particle
size will increase during polymerization.[11,12] To make
smaller particles, monomer transfer should be prevented
during polymerization. One method to solve this problem is
miniemulsion polymerization where water-insoluble che-
micals are used to prevent particle agglomeration. Another
method to overcome this problem is to ‘‘starve’’ the feed. In
the starving feed method, monomer droplets cannot exist.
The monomer added to the reaction system is quickly con-
sumed by the growing chains or used to generate polymer
radical particles. The differential addition of monomer gave
the smallest polymer particles applying all these addition
methods.
The number of polymer chains per particle (N) can be
calculated by Equation (3)
4
N ¼ pðD=2Þ3 rNA =M w ð3Þ
3
where D is the diameter of the particle, and r is the density
of the particle, assuming that all monomers in the particles
have been polymerized. For PMMA the density is

Table 2. Effect of monomer addition methods on particle sizes.

Run Addition method Particle size PD Notes

nm
5 one portion 45 0.163 paddle stirrer
6 2 þ 8 þ 6 ml 36 0.197 MMA: 16 ml, 1-pentanol: 0.2 ml, SDS: 1.4 g, APS: 0.14 g, water: 84 ml
7 2 þ 3 þ 5 þ 6 ml 27.9 0.188 –
8 differential 14.5 0.156 magnetic stirrer
9 2 ml MMA first 17.5 0.092 MMA: 14 ml, 1-pentanol: 0.2 ml, SDS: 1.4 g, APS: 0.08 g, water: 84 ml
10 3 ml MMA first 20.9 0.135 –

Table 3. Molecular weight of some samples (MMA: 16 ml, 1-pentanol: 0.2 ml, water: 84 ml).

Run SDS APS Particle size PD M n
105 M w
105 M z
105 M w/M n M z/M n N
g g nm
11 0.7 0.08 18.9 0.137 0.8702 1.572 19.18 1.8 22 15.9
12 0.36 0.08 28.3 0.148 0.7153 1.492 8.256 2.1 11.5 56.5
13a) 0.7 0.04 18.4 0.187 – – – – – –
14 1.4 0.08 14 0.157 0.848 1.532 2.224 1.8 26.2 6.7
a)
PMMA could not be dissolved thoroughly into THF. There are a lot of insoluble flocculants in THF.
588
Figure 2. Transmission electron microscopy image of run 8
nanoparticles.
1.18 g  cm3. NA is 6.02
1023/mol and M w is the weight-
average molecular weight. The number of polymer chains
per particle could give us an idea of whether we can make
the particles even smaller at a certain molecular weight.
Molecular weights and number of polymer chains per
particle of some samples are given in Table 3.
The diameter obtained from the light scanning method in
the present study is the hydrodynamic diameter, i.e. the
z-average diameter, which is higher than the number-
average diameter. The z-average diameter of run 8 (Table 2)
is 14.5 nm. The particles of run 8 were also checked by
means of TEM, and the corresponding image is shown in
Figure 2, indicating that the number-average diameter of
the run 8 particles is less than 10 nm. This number-average
diameter is even less than the level we presented in the
tables and in Figure 1 and the average number of polymer
chains per particle is lower than that obtained from
Equation (3). The number of polymer chains per particle
changes with the amount of initiator used if other conditions
were kept unchanged. For example, in the case of runs 11
and 13, the only difference is that for run 13 half the amount
of APS was used compared with run 11. The average
particle sizes were similar, however, the average number of
polymer chains per particle in run 13 must be much lower
G. He, Q. Pan, G. L. Rempel
due to the presence of a THF-insoluble, higher-molecular-
weight fraction.
In summary, PMMA particles of less than 20 nm i.d. can
be obtained by differential microemulsion polymerization.
As soon as the reaction temperature reached the decom-
position temperature of the initiator (between 80 8C and
85 8C) monomer was added in a differential manner. With
low weight ratios of SDS/water and SDS/MMA of 1:120
and 1:18, respectively, this process provides a new method
for preparing nanosize polymer particles.
Acknowledgement: Support from the Natural Science and
Engineering Research Council of Canada (NSERC) is gratefully
acknowledged.
Received: March 22, 2003
Revised: May 18, 2003
Accepted: May 22, 2003
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