Journal of Colloid and Interface Science 251, 78–84 (2002)
doi:10.1006/jcis.2002.8383
Emulsion Polymerization Synthesis of Cationic Polymer Latex
in an Ultrasonic Field
Melanie Bradley and Franz Grieser1
Particulate Fluids Processing Center, School of Chemistry, The University of Melbourne, Victoria, 3010, Australia
Received November 11, 2001; accepted March 23, 2002
Poly(methyl methacrylate) and poly(butyl acrylate) lattices have
been synthesized under ultrasonic irradiation in the presence of
a cationic surfactant, dodecyltrimethylammonium chloride. The
polymerization of oil-in-water emulsions of monomeric species was
carried out at 30◦ C (±5◦ C) in the absence of a chemical initiator.
The lattices were formed as stable dispersions with particle diame-
ters spanning the range of 40–150 nm and with polymer molecular
weights greater than 106 g mol−1 . The results obtained strongly sup-
port a polymerization process involving a miniemulsion system, in
which continuous nucleation of particles takes place throughout the
monomer to polymer conversion reaction. C 2002 Elsevier Science (USA)
INTRODUCTION
Synthetic latex is conventionally prepared by an emulsion
polymerization process (1). The main ingredients for conduct-
ing these polymerizations are a water-insoluble monomer, an
aqueous-phase-containing surfactant, and, commonly, a water-
soluble radical initiator. In a batch emulsion polymerization, all
ingredients are added at the beginning of the polymerization
and an oil-in-water emulsion is formed. Polymerization is usu-
ally initiated by heating the mixture, as this causes the thermal
degradation of the chemical initiator to produce free radicals that
react with monomer. Chain polymerization then leads to the for-
mation and growth of latex particles. These polymer particles
form a colloid stabilized against coalescence by surfactant that
is present on the surface of the particles.
There are some disadvantages in the use of a chemical initiator
in an emulsion polymerization in as much as it can affect the la-
tex particles formed by altering molar mass, polydispersity, and
the colloid stability of the latex. In addition, some of the prod-
ucts that are formed by aqueous phase termination of the initiator
may undergo subsequent reactions, resulting in discoloration of
the final latex or any residual initiator present after polymer-
ization may act as an undesirable contaminant. These problems
can be avoided by employing techniques that do not require a
chemical initiator. Thermal polymerization is one such process
in which monomer is converted to polymer by thermal energy
1 To whom correspondence should be addressed.
0021-9797/02 $35.00

C 2002 Elsevier Science (USA)
All rights reserved.
alone. This type of polymerization generally requires substantial
thermal energy and the radical production is restricted to specific
monomer structural functionalities. Another method of radical
initiation is by the use of ionizing radiation. Gamma radiation
or X-rays generate hydrogen and hydroxide radicals as the ini-
tiating species via the radiolysis of water. The disadvantage of
this method is largely associated with the substantial cost in the
establishment and maintenance of the radiation source.
Relatively recently, a new method for initiation of emulsion
polymerization was discovered using ultrasound (2). Insonation
is widely employed in standard emulsion polymerization prepa-
ration as a means of homogenization since sonication is an ef-
ficient method of mixing and dispersing the monomer phase
preceding the reaction being initiated by an added chemical ini-
tiator. Ostroski and Stambaugh (3) were the first to find that
sonication significantly accelerated the rate of a conventional
emulsion polymerization. It was postulated that the accelera-
tion was caused by the enhanced decomposition of the chemical
initiator in aqueous solution, as a result of faster and better emul-
sification stemming from ultrasonic induced agitation.
Insonation actually plays a duel role in liquid systems. The
first is to cause large shear gradients in the interfacial region
of the cavitation bubbles that result as a consequence of the
transmission of ultrasound through a liquid (4). The second is
the production of radicals. When the ultrasonically generated
microbubbles rapidly collapse the gas and vapor within their
core is trapped and this leads to high local temperatures of the
order of 4000 to 5000 K (5, 6) within the bubble and at least
1250 K (7) in the liquid immediately surrounding the interfacial
region. In an aqueous medium such high temperatures lead to
the homolysis of water, creating hydroxyl (OH) and hydrogen
(H) radicals and the potential for radical chemistry (8).
The synthesis of anionic and cationic lattices by the conven-
tional emulsion polymerization process using a chemical initia-
tor has been widely reported (9–11). The use of ultrasound to
initiate a free radical emulsion polymerization in the absence of
a chemical initiator is one area of research that has positive
implications for latex technology. The advantages include the
ability to conduct polymerizations at room temperature and the
elimination of problems usually associated with a chemical ini-
tiator. Research to date in the field of sonochemically induced
emulsion polymerization has resulted in the preparation of many
78
 EMULSION POLYMERIZATION SYNTHESIS OF CATIONIC POLYMER LATEX
types of anionic latex (2, 12–14). Small particle size and high
molecular weight are common features of these particles but lit-
tle is known about the mode of polymerization. In the present
study we report on the preparation and physical characteriza-
tion of poly(methyl methacrylate) and poly(butyl acrylate) latex
particles by the ultrasonic initiation of monomer emulsions sta-
bilized by a cationic surfactant.
EXPERIMENTAL SECTION
Reagents
Methyl methacrylate (MMA) and butyl acrylate (BA) (sup-
plied by Dulux Australia) were filtered through basic aluminium
oxide twice to remove the inhibitor. The sealed purified sample
was stored at 4◦ C until required. Dodecyltrimethylammonium
chloride (DTAC; TCI Chemicals) was used as supplied. Four-
stage Milli Q-filtered water was used to prepare all aqueous so-
lutions. High-purity argon (BOC Gases) was used without any
further purification.
Polymerization
All the ultrasonically initiated polymerization reactions re-
ported here were performed using a conventional 19-mm-
diameter 20-kHz horn sonifier (Branson 450); the horn was
inserted into a custom-built reaction vessel. The experimental
apparatus is shown elsewhere (2). The power generated at the
tip of the horn and adsorbed by the solution was measured by
calorimetry to be between 7 and 9 W/cm2 . For all the poly-
merizations reported here the concentration of monomer was
10% (w/w) in water. The effects of different concentrations
of surfactant (DTAC) on the resultant lattices produced were
investigated.
The following description for a polymerization at the above
monomer concentration and with a DTAC concentration of 0.1 M
is typical of all the polymerizations described in this study. An
emulsion consisting of 7.5 g monomer, 2.0 g DTAC, and 67.5 g
water was thoroughly deaerated by gently purging with high-
purity argon for 45 min in the reaction vessel at room temper-
ature. Thereafter the argon gas stream was removed from the
emulsion and was allowed to pass over the surface of the liq-
uid mixture. The polymerization reaction was then initiated by
subjecting this mixture to continuous cycles of 10 min of soni-
cation with 5-min pauses between sonication periods. This pe-
riodic sonication cycle and the immersion of the reaction vessel
in an ice/water bath was sufficient to maintain the temperature at
30 ± 5◦ C. Small samples of the reaction mixture were removed
with a syringe, via the free inlet, throughout the reaction. The
samples were left to air dry overnight and then oven dried at
a moderate temperature (<80◦ C) for 3 h. The error associated
with this technique is approximately 2%. The dried samples
were used to monitor the progress of the reaction by gravimet-
ric analysis. The final lattices (10 mL) were dialyzed against
water (200 mL) for at least 7 days with regular replacement of
water.
79
Polymer Conversion
The percentage of monomer converted to polymer was de-
termined by weighing the polymer produced as a function of
sonication time. During sonication small aliquots of the emul-
sion solution were removed. These samples were dried leaving
only polymer and surfactant. Based on the assumption that the
aliquots were homogeneous, correction was made for the sur-
factant in the sample thereby giving the mass of polymer. The
“uncorrected” percentage conversion does not take into con-
sideration any coagulum formed (small amounts, <1%, of ag-
gregated latex formed around the horn) because it was only
possible to account for this at the end of the polymerization
process. With coagulum taken into account the overall conver-
sion of monomer at the end of sonication was of the order of
85–90%.
Particle Sizing
Particle size distributions and averages were determined pri-
marily using a Malvern dynamic light scattering instrument.
While capillary hydrodynamic fractionation (CHDF)–1100 par-
ticle size analysis was used for comparison.
Molecular Weight Determination
Polymer samples dissolved in HPLC grade tetrahydrofuran
(THF) were analyzed for molecular weight using gel permeation
chromatography (GPC) using a Waters HMW7 Styragel column
attached to a Waters 410 differential refractometer, and the data
was collected and processed on a Waters Millenium 32 work
station calibrated against polystyrene standards.
Latex Surface Potential
The surface potentials on the latex particles were derived
from microelectrophoresis measurements of the particles in so-
lution using a Coulter DELSA (Doppler electrophoretic light-
scattering analyzer) 440. The measured mobilities were con-
verted to zeta potential using the Helmholtz–Smoluchowski
equation (15).
Interfacial Tension
Interfacial tension (monomer/aqueous solution) measure-
ments were performed on a FTA 200 interfacial tension device
using a pendant drop of oil (monomer). The measurements were
carried out at 20◦ C and the instrument was calibrated against
high-purity octane that has an oil/water interfacial tension of
50.8 mNm−1 at 20◦ C (15).
RESULTS
The experimental conversion–time curves for the ultrasound
initiated emulsion polymerization of MMA and BA as a func-
tion of surfactant concentration are shown in Figs. 1 and 2, re-
spectively. All emulsion polymerizations were conducted above
the critical micelle concentration of DTAC (20 mM) (16). In
80 BRADLEY AND GRIESER

100 TABLE 1
Polymer Molecular Weight Data as a Function of DTAC
Concentration for Poly(MMA) and Poly(BA) Latex
Uncorrected % Conversion

80
Molecular weight (g mol−1 )
60 MMA BA
[DTAC]
(mM) Mw (×10 ) Mn (×10 ) Mw /Mn Mw (×10 ) Mn (×106 ) Mw /Mn
6 6 6
40
25 2.5 0.8 3.0 1.5 0.4 3.4
50 2.8 0.9 3.1 2.3 0.7 3.3
20 75 2.8 0.9 3.1 2.8 0.7 3.9
100 3.2 1.1 2.9 2.7 0.8 3.6
0
0 10 20 30 40 50 60 70 80
Sonication Tim e / minutes
used (17). The molecular weight results obtained using GPC
FIG. 1. Ten weight percent MMA monomer conversion as a function of should only be taken as a lower limit because the technique has
sonication time in the presence of different concentrations of DTAC: 0.025 M limited sensitivity at the molecular weight magnitudes obtained.
(), 0.050 M (), 0.075 M (), and 0.100 M (). Other analytical techniques are currently being investigated
to better characterize the molecular weight of the polymers
Fig. 1 it is evident that the rate of polymerization of MMA is produced.
approximately the same over the concentration range of DTAC The final particle size of the polymer latex was examined as a
examined. However, the conversion–time profiles for BA (Fig. 2) function of surfactant concentration and the results are listed in
indicate a decreased rate of BA conversion at 0.025 M DTAC. Table 2. The particle size of poly(MMA) decreases as the surfac-
This latter observation coincides with the observed poor emul- tant concentration increases, whereas that of poly(BA) remains
sification of the BA system, particularly at this surfactant con- the same, within experimental error. The latex particle sizes
centration, in comparison with the MMA counterpart. obtained sonochemically are smaller than those obtained by con-
The molecular weight data for the number- and weight- ventional emulsion polymerization at similar surfactant concen-
average molecular weights, Mn and Mw , respectively, as well trations (18). The particle size of the latex was also measured as
as the molecular weight distribution (Mw /Mn ) for each polymer a function of sonication time at 0.1 M DTAC. For poly(MMA)
sample examined are given in Table 1. The molecular weight the particle size is constant throughout the reaction time (Fig. 3).
values for the latex obtained by ultrasonically initiated emul- However, poly(BA) synthesis proceeds with a constant particle
sion polymerization are large in magnitude compared to typ- size up to 50 min. of sonication after which a dramatic increase
ical latex prepared conventionally. However, it is possible in in size is observed (Fig. 4).
conventional emulsion polymerizations to achieve similar mag- Latex surface potentials were measured for each surfactant
nitudes in molecular weight if low initiator concentrations are concentration investigated. The samples were then dialyzed and
the zeta potentials calculated again. The results are presented
in Table 3. The results show that following dialysis the elec-
100 trostatic potential on the latex surface is greatly reduced. This
is indicative that DTAC is adsorbed at the latex interface rather
than chemically bound to the polymer and is in equilibrium with
Uncorrected % Conversion

80

60 TABLE 2
Number Average (dn ) and Volume Average (dv ) Particle Diam-
40 eters for Poly(MMA) and Poly(BA) Latex as a Function of DTAC
Concentration

20 Particle diameter (nm) (±15 nm)

MMA BA
[DTAC]
0
(mM) dn dv dn dv
0 10 20 30 40 50 60 70 80
Sonication Tim e / minutes 25 63 74 107 116
50 56 56 132 150
FIG. 2. Ten weight percent BA monomer conversion as a function of soni- 75 37 42 123 138
cation time in the presence of different concentrations of DTAC: 0.025 M (), 100 37 41 119 136
0.050 M (), 0.075 M (), and 0.100 M ().
 EMULSION POLYMERIZATION SYNTHESIS OF CATIONIC POLYMER LATEX 81

70 TABLE 3
Zeta Potentials of as Prepared and Dialyzed Poly(MMA) and
60 Poly(BA) Latex Particles as a Function of DTAC Concentration

Zeta potential (mV) (±10 mV)

50 [DTAC]
d / nm

(mM) MMA Dialyzed MMA BA Dialyzed BA

40
v

25 +36 +7 +25 +3
50 +29 +7 +43 +13
30
75 +43 +7 +37 +13
100 +52 +18 +50 +17
20
Note. All solutions had an ionic strength of (1.3 ± 0.3) × 10−3 mol kg−1 .
10
20 25 30 35 40 45 50 55 60
Sonication Tim e / minutes
DISCUSSION
FIG. 3. Volume average particle diameter (dv ) as a function of sonication
time for poly(MMA) latex at 0.10 M DTAC. (|) Indicates the error range that From the conversion traces shown in Figs. 1 and 2 it is evi-
applies to each data point. dent that the maximum conversion reached is consistently less
than 100% conversion. Free monomer analysis on the final latex
samples provided proof that there was no monomer left at the
that present in solution. Also, there was a marked difference in completion of the polymerizations. The possibility of monomer
the physical state of the dialyzed MMA and BA samples. Dia- evaporation during the course of the reaction was also investi-
lyzed poly(BA) latex coagulated out of solution forming a poly- gated but this proved that a negligible amount was lost by this
mer mass, whereas the dialyzed poly(MMA) latex dispersion route. Therefore, it is assumed that the missing monomer has
formed a gel. been consumed in side reactions upon sonication to produce
In addition, the interfacial tension of a monomer droplet in a water-soluble product. Apart from the missing monomer the
monomer-saturated surfactant solution was measured to gauge conversion traces show that in general the polymerization mech-
the ease with which formation of the emulsion occurs prior anism under ultrasonic initiation is independent of surfactant
to polymerization. The interfacial tension for pure MMA was concentration. The remainder of this discussion centers on the
17 mN m−1 and that of BA was 24 mN m−1 . On addition of elucidation of the ultrasonically initiated reaction mechanism.
surfactant, in the range 0.025 to 0.100 M, the interfacial tension There are three conventional heterogeneous polymerization
decreased to 4 ± 1 mN m−1 for both monomer systems. These systems all of which incorporate a water-soluble initiator and
data suggest that the ease of emulsification of monomer should are classified according to the characteristics of the oil-in-water
not be dependent on interfacial tension over the surfactant range emulsion they form: macroemulsions, miniemulsions, and mi-
used in the polymerization experiments. croemulsions.
A macroemulsion is composed of monomer droplets in the 1-
to 100-µm size range (19). Most conventional emulsion poly-
140 merizations where the surfactant concentration is at or above its
critical micelle concentration are conducted in macroemulsions.
120 Particle nucleation in macroemulsions takes place by either mi-
cellar or homogenous nucleation (20). The process of nucleation
100
results in the creation of polymer particles that take up and swell
with monomer. This monomer swollen particle phase acts as the
d / nm

80
locus of further polymerization. Therefore, the particle diameter
v

60 increases during the polymerization process as a result of equi-

librium swelling to yield particles with final diameters between
40
100 and 600 nm (19).
20 Miniemulsions lie in between macro- and microemulsions
in terms of droplet size and emulsion stability. Miniemulsion
0 10 20 30 40 50 60 70 80 droplet sizes range from 50 to 500 nm and are often generated
Sonication Tim e / minutes using a high-shear device, such as a sonicator. The emulsions
are thermodynamically unstable and are often prepared with the
FIG. 4. Volume average particle diameter (dv ) as a function of sonication
time for poly(BA) latex at three different DTAC concentrations: 0.05 M (),
intent of eliminating nucleation via micellar and aqueous phase
0.10 M (), and 0.20 M (O). (|) Indicates the error range that applies to each routes (homogeneous nucleation), thereby restricting the locus
data point. of polymerization to the miniemulsion droplets. In general, final
82 BRADLEY AND GRIESER

latex particle diameters range from 60 to 200 nm in a miniemul-

sion polymerization (19).
Microemulsions are transparent solutions that are thermo-
dynamically stable, form spontaneously on mixing, and con-
tain droplet sizes varying from 10 to 100 nm. Akin to the
miniemulsion system the polymerization locus is in the preexist-
ing droplets but with the difference being that the latex formed
has a particle diameter between 20 and 60 nm (19).
Based on these conventional classifications that are commonly
used to describe an emulsion polymerization process, the one
that best fits the experimental data for latex produced through
ultrasonic initiation is the miniemulsion polymerization model.
There are several qualitative comparisons that can be made that
support this postulate. First, the emulsions produced by sonica-
tion were thermodynamically unstable—phase separation was
observed to occur when the sonicator was switched off. Second,
Sakai et al. (21) recently reported that the ultrasonic (40 kHz)
dispersion of benzene and other hydrocarbons in water produced
drops of <100 nm in diameter as measured by dynamic light
scattering and freeze-fracture electron microscopy. Finally, the
data presented in Table 2 show that the fully converted sono-
chemically produced latex particle diameters span from 40 to FIG. 5. Schematic diagram of proposed miniemulsion polymerization path-
150 nm. way induced by ultrasound. The ultrasound coming from the horn tip produces
The ultrasonic initiation of the polymerization process that cavitation bubbles that on collapse (implosion) generate the conditions that lead
forms latex particles is thought to occur through the generation to primary radical formation (·H, ·OH) and emulsification of the monomer.
of monomeric radical species in an emulsion. The individual Secondary radicals M· are formed at the surface of the collapsed bubble and
subsequently react with monomer droplets in bulk solution producing latex
steps that take place are summarized in Scheme I and shown particles.
diagrammatically in Fig. 5. The cavitation event that occurs as
ultrasound travels through a liquid medium produces microbub-
bles in solution. On collapse of the microbubble in an aqueous
solution the foremost primary radical species present are most 20 kHz. This suggests that primary organic radicals are unlikely
likely ·OH and ·H radicals. Although MMA and BA are volatile to play a major role in these cases in the ultrasonically initiated
monomers and could enter a cavitation bubble to be thermally emulsion polymerization (22).
decomposed to produce a variety of primary organic radicals, The H/OH radicals generated by the homolysis of water are
we do not believe this occurs to any significant extent at 20 kHz. intercepted before they reach the aqueous phase by the solutes
Recent work in this laboratory has shown that little pyrolysis of in the boundary layer of the bubble–solution interface. In an
methacrylic acid or MMA occurs at an acoustic frequency of emulsion these solutes are monomer and surfactant (8). The re-
sulting H/OH radicals can undergo addition to the monomer
adsorbed at the bubble solvent interface (23) (reaction (2); for
(a) Initiation simplicity this is generically denoted by M·s ). Thereafter, the
H2 O ))) · H + · OH (1) outcome is the formation of monomeric radicals (which are the
· OH(· H) + M
s → HOM· (HM· ) ≡ (M· )
s S s (2) secondary radicals referred to earlier) in bulk solution (step (3))
(b) Propagation that have three alternative pathways to initiate polymerization.
Ms· → M·b (3) They can add to a monomer molecule and undergo polymer-
Mb· + Mb → M·ib (4) ization in the bulk phase (reaction (4); the “i” refers to two or
· )+D
Mb· (Mib → D· (5)
·
Mb + micelle → M·micb (6)(a)
more monomer molecules per radical), enter a droplet (reac-
Mib· + micelle → M·micib (6)(b) tion (5)) or a micelle (reaction(6)). Reaction (7) represents a
D· → D· p (7) monomer droplet undergoing polymerization. Termination will
(c) Termination occur by reaction with another growing radical by recombina-
Dp· + Mb· (M·ib ) → L (8) tion (reactions (8) and (9)). A number of other steps could also
·
Mmicib + M·b (M·ib ) → L (9) be considered; however, Scheme I we suggest represents the
main reactions likely to be occurring in the formation of latex
SCHEME I. Mechanism for ultrasound initiated polymerization. ))) repre-
sents the applied ultrasonic field. M stands for the monomer, s for the surface
particles.
of the cavitation bubble, b for species in bulk solution, D for monomer droplet, If butyl acrylate is taken as an example, it is reasonable to
and L for a latex particle. conclude from the kinetic data presented in Table 4, which shows
 EMULSION POLYMERIZATION SYNTHESIS OF CATIONIC POLYMER LATEX 83

TABLE 4 particle number per milliliter of solution increases throughout

Kinetic Data for the Possible Pathways of Polymer Initiation the conversion. This is interpreted as continuous nucleation of
monomer droplets occurring to form latex particles. Indeed, this
Rate Relative
Concentration constant initial
is what would be expected in a miniemulsion process if the num-
No. Reaction (mol L−1 ) (L mol−1 s−1 ) rate ber of latex particles increase with a decrease in the number of
droplets.
1 M·b ·
+ Mb . . . → Mib a 10 × 10−3 d 5 × 102 1 For the BA system not all the experimental observations, at
2 Mb· (M·ib ) + D → D· b 5.6 × 10−6 e 2 × 1011 2 × 105 first glance, appear to be consistent with a miniemulsion poly-
Mb· + micelle → M·micb c0 f 7 × 109
3 0 merization process. For example, the 0.1 M DTAC data in Fig. 4
M· ib + micelle → M· micib
indicate that with longer sonication times a rapid particle growth
Note. Where the monomer (M) is BA, D is a monomer droplet and Mmic is occurs after about 50 min of sonication (60% conversion to
the BA swollen micelle. The superscript ( · ) represents a radical. polymer). This observation is inconsistent with the arguments
a The water solubility of BA is 10 mmol L−1 (24).
b Assuming that 10 wt% monomer is dispersed as emulsion droplets 40 nm
that support a polymerization process involving a miniemulsion.
in diameter.
However, on a closer inspection of this figure it can be noticed
c If 10 wt% BA and 0.05 M DTAC produces droplets 40 nm in diameter and that the particle size of poly(BA) latex prior to 50 min of son-
DTAC adsorbs to the surface of the droplets (60 A2 /molecule (25)), the amount ication is constant with an average particle diameter of about
of free DTAC will be less than the cmc (20 mM) and therefore no micelles will 30 nm ± 15 nm. This is comparable, within experimental er-
be present in the emulsion. ror, to the average particle diameter determined for poly(MMA)
d The propagation rate coefficient for BA (24).
e Calculated (26, 27) using k = 4π DRN with the monomer diffusion coeffi- latex (30 ± 15 nm; shown in Fig. 3). This particle growth, which
cient D of 1 × 10−5 cm2 s−1 (28) and assuming a droplet radius (R) of 20 nm; results from prolonged sonication time, need not be due to a
N is Avogadro’s constant. change in the mechanism of polymerization.
f Entry rate constant of low-molecular-weight hydrocarbon molecules into a
One important difference between poly(BA) and poly(MMA)
micelle (26, 27). is the glass transition of the polymer, (−)55◦ C and (+)105◦ C,
respectively. Under the given reaction conditions poly(MMA)
latex particles would be glassy, whereas poly(BA) latex particles
the three main steps in monomer polymerization, that droplet
would be soft and deformable. Hence, at longer sonication times
nucleation is the dominant pathway for latex formation.
where latex particle numbers are high and the rate of particle–
The results on particle diameters as a function of monomer
particle collisions increases, it is then probable that for a soft
conversion provide additional insight into the polymeriza-
polymer latex particle coalescence/fusion occurs. Further evi-
tion process. The particle diameter during monomer conver-
dence that particle coalescence is occurring in the BA system
sion/sonication was observed to remain approximately constant
comes from the effects on particle size associated with chang-
during the synthesis of poly(MMA) latex and is consistent with
ing the surfactant concentration. It can be seen in Fig. 4 that on
a miniemulsion polymerization process. A knowledge of the
reducing the DTAC concentration, and consequently reducing
amount of monomer reacted and the particle diameter makes it
particle stability, the particle size increases at shorter sonication
possible to calculate the number of particles produced through-
times. In essence, it is reasonable to conclude that BA latex par-
out the reaction. The results presented in Table 5 show that
ticles are formed in the same way as MMA particles with an
added reaction step involving particle–particle fusion at longer
sonication times.
TABLE 5
Particle Number (Nc ) per Milliliter as a Function
of Monomer Conversion CONCLUSIONS
MMA BA
The ultrasonically initiated emulsion polymerization of MMA
Percentage Percentage and BA in the presence of DTAC produces cationic lattices in the
conversion of conversion of
monomer dn (nm) Nc (×1015 ) monomer dn (nm) Nc (×1015 )
size range of 30–100 nm. Collectively, the results obtained are
consistent with a miniemulsion polymerization process that in-
25 35 0.9 18 28 1.5 volves the direct polymerization of the small monomer droplets
30 35 1.1 26 28 2.1 that are formed by the effects of ultrasound in mixing monomer
34 35 1.3 29 28 2.4
and water to produce an emulsion. For the case of BA latex,
36 35 1.3 34 28 2.8
40 35 1.5 36 28 3.0 there is some evidence that suggests that prolonged sonication
41 35 1.6 45 28 3.7 leads to particle–particle fusion resulting in the growth of larger
44 35 1.6 53 28 4.3 diameter latex. Overall it has been found that emulsion polymer-
49 35 1.9 60 28 4.9 ization using ultrasound as the initiator is readily achieved and
60 35 2.3 70 46 1.1
is a convenient method for producing nanosized cationic latex
67 35 2.5 74 130 0.05
particles.
84 BRADLEY AND GRIESER
ACKNOWLEDGMENTS
M.B. acknowledges the receipt of an Australian Postgraduate Award. The
project funding is in part supported by Dulux Australia Pty. Ltd. and the ARC
Particulate Fluids Processing Centre. We are also grateful for the contributions
to the program made by Michelle Carey and Chris Such of Dulux, Australia.
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