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Effect of Polymer Characteristics on Particle Formation

and Growth in Batch Emulsion Polymerization
a a a ac a a
Shuang Liu , Baijun Liu , Zhongyu Fu , Tingting Zhou , Liang Ren , Mingyao Zhang &
ab
Huixuan Zhang
a
School of Chemical Engineering, Changchun University of Technology, Changchun, P. R.
China
b
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, P. R.
China
c
Changchun Hella Automotive Lighting Ltd, Changchun, P. R. China
Accepted author version posted online: 06 Oct 2014.
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To cite this article: Shuang Liu, Baijun Liu, Zhongyu Fu, Tingting Zhou, Liang Ren, Mingyao Zhang & Huixuan Zhang (2015)
Effect of Polymer Characteristics on Particle Formation and Growth in Batch Emulsion Polymerization, Journal of Dispersion
Science and Technology, 36:9, 1320-1326, DOI: 10.1080/01932691.2014.956364

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 Journal of Dispersion Science and Technology, 36:1320–1326, 2015
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print=1532-2351 online
DOI: 10.1080/01932691.2014.956364

Effect of Polymer Characteristics on Particle Formation

and Growth in Batch Emulsion Polymerization
Shuang Liu,1 Baijun Liu,1 Zhongyu Fu,1 Tingting Zhou,1,3 Liang Ren,1
Mingyao Zhang,1 and Huixuan Zhang1,2
1
School of Chemical Engineering, Changchun University of Technology, Changchun, P. R. China
2
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, P. R. China
3
Changchun Hella Automotive Lighting Ltd, Changchun, P. R. China

GRAPHICAL ABSTRACT
Downloaded by [ECU Libraries] at 08:37 27 April 2015

This article is an extensive investigation on particle coagulation growth in emulsion polymerization

proposed by our team (Colloid and Polymer Science, 2013, 291, 2385–2398). Monodispersed,
large-scale, high-solid content poly (butyl acrylate) latex was obtained by varying the reaction pro-
cedures in previous studies. However, the present method, which could be used in other monomer
systems such as styrene, methyl methacrylate, or the copolymerization of different monomers, has
not been reported to date. In this article, the particle formation and growth behaviors of different
monomer compositions were investigated in regard to the range of application and to clarify the
effect of monomer characteristics on particle coagulation. Experimental results indicated that
polymer characters such as hydrophilicity play an important role in particle coagulation, which
was increased with increasing monomer hydrophilicity. Moreover, particle coagulation could
improve reaction system stability and enhance the likelihood of obtaining a high solid content.
The optimal systems for styrene, methyl methacrylate, and butyl acrylate were 40, 50, and
60 wt%, respectively, due to variation in monomer hydrophilicity.
Keywords Emulsion polymerization, hydrophilicity, particle coagulation, solid content

Received 4 August 2014; accepted 17 August 2014.

Address correspondence to Mingyao Zhang, School of Chemical Engineering, Changchun University of Technology, Changchun
130012, P. R. China. E-mail: zmy@mail.ccut.edu.cn
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/ldis.

1320
 EFFECT OF POLYMER CHARACTERISTICS ON PARTICLE FORMATION
1. INTRODUCTION
Emulsion polymerization is among the key processes in the
production of synthetic polymers, achieving high molecular
weight and fast polymerization rate in comparison with bulk
and solution polymerization processes.[1–5] Furthermore, the
final product can be used as paper coating or starch, etc. or
directly from the beginning. In particular, latexes with high
solid content (HSC) have been given considerable attention
due to their many advantages, such as low transport and stor-
age costs and rapid drying and film formation rates.
Many studies into how to obtain HSC latexes have been
reported in recent decades. Du et al. produced HSC latexes
by thermally initiated semicontinuous emulsion poly-
merization of styrene at 75 C. Although the solid content
reached 69.1%, the reaction was prolonged (24 hours) due
to the slow generation rate of radicals in the absence of an
initiator. Finally, the particle size range of polymer latexes
is wide since the new particle continuously generated in this
system.[6] Semicontinuous emulsion polymerization is
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regarded as an efficient method in the production of HSC
latexes.[4] Emulsion copolymerization of styrene, butyl
acrylate, and methacrylic acid was carried out to produce
HSC latexes by Chu et al.[7,8] Bi- and trimodal particle size
distribution (PSD) HSC latexes were obtained by three
methods: the addition of surfactant, seed emulsion, and both
surfactant and seed. However, investigations into producing
HSC latexes by a one-step method are rare, especially those
using methyl methacrylate or styrene as monomer.
In this article, HSC latexes were synthesized by the batch
emulsion polymerization of butyl acrylate, styrene, and
methyl methacrylate based on our previous reports[9,10]
describing how to obtain large-scale HSC latex of narrow
particle size range. An interesting discovery was that the
final solid content of three polymer latexes, polystyrene
(PS), poly-(methyl methacrylate) (PMMA), and poly-(butyl
acrylate) (PBA), was different. The subject of this investi-
gation is to interpret this phenomenon and investigate the
particle coagulation mechanism; to that end, a series of
experiments using monomers of varying composition were
performed and are described below. It was assumed that
particle formation and growth by particle coagulation
represent the main procedure involved in obtaining HSC
latexes. Experiments on the emulsion copolymerization of
BA=St (butyl acrylate=styrene) and BA=MMA (butyl
acrylate=methyl methacrylate) were further carried out in
order to confirm the relation between polymer characteris-
tics and particle coagulation.
2. EXPERIMENTAL
2.1. Materials
The monomers n-butyl acrylate (BA), methyl methacry-
late (MMA), and styrene (St) were further purified by vac-
uum distillation to remove inhibitors and stored at 18 C.
1321
Sodium dodecyl sulfate (SDS), potassium carbonate
(K2CO3) and potassium persulfate (KPS) were used as
emulsifier, electrolyte, and initiator, respectively. Distilled
deionized water (DDI) was used throughout the experiment.
2.2. Latex Preparation
Polymerization was carried out in a three-necked glass
vessel equipped with a thermostatic water bath, an anchor
stirrer, and a reflux condenser. The reaction temperature
was maintained at 65 C and the stirring rate was kept
constant at 250 rpm. The monomers, emulsifier, electrolyte,
and partial DDI were all in the reactor except during the
initiation stage. Nitrogen gas was then flushed through
for 30 minutes to remove oxygen, and the initiator with
residual DDI introduced into the reactor. Reactor time zero
was set at this point. The emulsifier, electrolyte, and
initiator concentrations were maintained at 1.0, 0.6, and
0.6 wt%, respectively, of water. The variables were mono-
mer type and the ratios monomer=water and monomer1=
monomer2. The formulation procedure is shown in Table 1.
2.3. Characterization
2.3.1. Monomer Conversion
Samples (about 1–2 g) were extracted at appropriate
intervals by syringe and placed in an aluminum foil dish
for measurement of conversion. To counter the continuous
polymerization reaction, methanol with hydroquinone was
added. The sample was then dried to constant weight at
65 C. Conversion was calculated by the following formula:
weight residue=sample weight  solid fraction
X¼ ½1
monomer fraction
Solids in the sample consisted of initiator, emulsifier,
and electrolyte.
2.3.2. Particle Size and Distribution
Particle size and distribution were characterized by an
American Brookhaven 90Plus Particle Size Analyzer, with
laser light-scattering measurements performed at 90 . Sam-
ples were withdrawn from the reactor by syringe and diluted
with DDI to appropriate concentrations. Five measure-
ments were made for each sample at 10-minute intervals
and n-average size and distribution were recorded.
2.3.3. Number of Particles
Latex particle number (Np) was obtained using the
following expression:
6M0 x
Np ¼ ½2
pqp D3t
where M0 is the monomer=water ratio (g=l of water), x is the
fractional conversion, qp is the polymer density (g ¼ ml3),
 1322 S. LIU ET AL.

TABLE 1
Fundamental recipe for preparation of various monomer latexesa
Emulsifier (g) Initiator (g) Electrolyte (g)

Monomer Monomer=water Monomer ratio SDS KPS K2CO3

Set1 BA 60=40 100=0 0.67 0.402 0.402

Set2 St 40=60 100=0 1.50 0.90 0.90
Set3 St 50=50 100=0 1.00 0.60 0.60
Set4 MMA 40=60 100=0 1.50 0.90 0.90
Set5 MMA 50=50 100=0 1.00 0.60 0.60
Set6 MMA 60=40 100=0 0.67 0.402 0.402
Set7 BA=St 60=40 90=10 0.67 0.402 0.402
Set8 BA=St 60=40 80=20 0.67 0.402 0.402
Set9 BA=St 60=40 70=30 0.67 0.402 0.402
Set10 BA=MMA 60=40 90=10 0.67 0.402 0.402
Set11 BA=MMA 60=40 80=20 0.67 0.402 0.402
Set12 BA=MMA 60=40 70=30 0.67 0.402 0.402
a
Emulsifier concentration, initiation concentration, and electrolyte concentration is 1 wt%, 0.6 wt%, and 0.6 wt% for water,
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respectively.

and Dn is particle n-average size, which is the increased size
calculated using a previous method.[11]
2.3.4. Contact Angle
The contact angle between the polymer and aqueous
phase was measured by a Contact Angle Measuring Instru-
ment DSA-30 (KRÜSS, Germany). The detailed character-
ization procedure followed was from our previous report.[12]
2.3.5. Glass Transition Temperature
The glass transition temperature (Tg) of the polymer was
measured with a TA Instruments differential scanning
calorimeter (DSC) Q20 with a Universal Analysis 2000.
Measurement was carried out at a heating rate of 3 C=
min. Thermograms were obtained via a second heating.
demulsification occurred with a higher solid content for
St (St=water ¼ 50=50) and MMA (MMA=water ¼ 60=40).
These findings are meaningful in regard to investigating
how to obtain HSC latex and understanding the particle
coagulation mechanism. It is well known that tracking
the evolution of particle size and number as a function of
monomer conversion is an effective approach to confirm-
ing the process of particle formation and growth, and to
determining the reaction mechanisms for emulsion poly-
merization. Thus the following section discusses the evol-
ution of particle size and number.

3. RESULTS AND DISCUSSION

3.1. Evolution of Monomer Conversion
Evolution of monomer conversion as a function of time
at varying monomer=water ratios is shown in Figure 1. As
expected, monomer conversion increased with reaction
time for all reaction systems. It was observed from the
conversion versus time curves for the same monomer with
different monomer=water ratios that polymerization rate
decreased with increase in monomer content, which is
contradictory to the theory of Smith–Ewart.[13–15] More-
over, monomer polymerization rate varied significantly
for different monomers although the procedure for all
systems, as shown in Table 1, was identical. It was noted FIG. 1. Monomer conversion versus reaction time for emulsion
that the stability of reaction systems was reduced because polymerization of different monomers at varying monomer=water ratios.
 EFFECT OF POLYMER CHARACTERISTICS ON PARTICLE FORMATION
3.2. Evolution of Particle Size and Number
Figures 2 and 3 illustrate the evolution of particle size and
number versus monomer conversion curves. It will be seen
from Figure 2 that particle size slightly increased as mono-
mer conversion increased for St systems. However, particle
size with PMMA rapidly increased from the initial reac-
tions, especially between 0 and 0.3 monomer conversions.
The corresponding curves of particle number evolution are
shown in Figure 3. The trends in particle number evolution
are similar, namely, initial increase with monomer conver-
sion increase then decrease to a constant value.
The emulsion polymerization reaction can be divided
into three phases based on conventional Smith–Ewart
theory.[15] In the first phase (nucleation), new particles are
created by the micellar nucleation mechanism and particle
number increases with increase in monomer conversion; in
the second phase (particle growth), particles grow by
consuming the monomer origin from monomer droplets,
with latex particle number maintaining a constant value.
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When the monomer droplets are consumed completely,
latex particles will consume the monomer and the third
stage commences, finishing when polymerization is
complete. Based on this, particle number should increase
with increased monomer conversion to reach the constant
value reported by Brooks,[16,17] which is not in agreement
with the evolution of particle number in this study. On
the other hand, homogeneous nucleation can occur in
reaction systems, especially in MMA systems.[15] The
number of particles will increase if homogeneous nucleation
occurs in the reaction process, but why did particle number
decrease with increase in monomer conversion?
Taken together with our previous reports,[9,10,12,18] it can
be concluded that in the process of latex particle formation
FIG. 2. Curves of particle size versus monomer conversion for
emulsion polymerization of different monomers at varying monomer=
water ratios.
1323
FIG. 3. Curves of particle number versus monomer conversion for
emulsion polymerization of different monomers at varying monomer=
water ratios.
and growth, particle coagulation will take place leading
to increase in particle size at a faster rate and decrease in par-
ticle number, as shown in Figures 2 and 3. Chern and Lin
investigated the stability of carboxylated poly-(butyl acry-
late) lattices during semi-batch emulsion polymerization,
and were of the opinion that emulsion polymer particles
can expand by mild aggregation of a few particles to main-
tain colloid stability.[19] Hansen and Ugelstad claimed that
when particles formed they might start to coagulate with
each other.[20] Indeed, particle coagulation commences with
the formation of primary particles from micellar or homo-
geneous nucleation, with increased particle size resulting
from initial consumption of the monomer and the stability
of polymer particles, thus decreasing the ratio of surface
emulsifier molecules covered. Particle coagulation can
reduce total particle surface, thereby improving this ratio
and enhancing particle stability.
3.3. The Extent of Particle Coagulation
Another important aspect that will be seen from Figure 3
is that the extent of particle coagulation varied for different
monomer composition or content. The effect of monomer
characteristics on the extent of particle coagulation, defined
as the ratio of actual particle number divided by maximum
particle number, is shown in Figure 4. Particle number
for conventional batch emulsion polymerization was
found not to be dependent on the monomer=water (M=W)
ratio,[21] and hence the maximum particle number for emul-
sion polymerization of different monomers was obtained
using a M=W ratio of 20=80 in the absence of electrolytes.
The lower the ratio of Np=Nmax (Nmax ¼ the particle number
without the particle coagulation occurred), the greater the
extent of particle coagulation. From Figure 4, the order of
 1324
FIG. 4. The extent of particle coagulation versus monomer conversion
for different monomer compositions and content.
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particle coagulation will be seen as PMMA > PBA > PS,
which is an agreement with the order of polymer
hydrophilicity. In general, polymer hydrophilicity can be
characterized by the contact angle. Figure 5 shows images
of the contact angle between different homopolymer films
and water. The contact angle for PMMA, PBA, and PS film
with water was 67.3 , 76.3 , and 81.8 , respectively.
Piirma and Chen studied the adsorption of ionic
emulsifiers on latex particles and claimed that saturation
adsorption depends on both the orientation of emulsifier
molecules on polymer surface and the latex adsorption equi-
librium. In regard to PS, when emulsifier molecules were
tightly packed on the polymer surface, the stability of latex
particles improved; however, for PMMA latex particles, the
emulsifier molecules were loosely packed on particle sur-
faces, reducing their stability in the aqueous phase.[22]
Yamamoto considered that the pi electron cloud of
benzene in the styrene is favor of polymer particle stability
improved.[23] In this regard, particle coagulation would be
enhanced by an increase in polymer hydrophilicity. How-
ever, for the same monomer, the extent of particle coagu-
lation was also determined by collision of latex particles
FIG. 5. Images of contact angle for different homopolymerization films with water.
S. LIU ET AL.
in the aqueous phase. The greater the frequency of particle
collision, the greater the extent of particle coagulation. It is
well known that the frequency of particle collision is pro-
portional to the density of polymer particles in the aqueous
phase. Mayer et al. modified the Smoluchowski equation by
adding the collision frequency of different particle sizes to
simulate limited particle coagulation in emulsion polymeri-
zation, which was calculated by the following equation:[24]
 3
Bði; jÞ ¼ f ðcÞNðiÞNðjÞ dp ðiÞ þ dp ðjÞ ½3
where B (i, j) and f (c) denote, respectively, the number of
collisions between particles in size classes i and j, and a con-
stant that depends on shear rate; N (i) and (j) denote the
density of latex particles in size classes i and j, respectively.
Thus particle coagulation will increase with increase in
monomer content due to particle size being proportional
to monomer content. As monomer content increases, the
stability of latex particles will decrease due to reduction in
the emulsifier covered ratio on the particle surface, which
was reported in our previous study. That is the reason
why demulsification took place when the monomer reached
a critical value.
3.4. Control of Particle Coagulation
In previous studies, the effect of the procedure compo-
sition (i.e., initiator, emulsifier, and electrolytes) on particle
coagulation has been widely investigated.[9,10] However, to
our knowledge there are few reports on the control of particle
coagulation using copolymerization of different monomers
of varying hydrophilicity. Thus, in this section, the copoly-
merization of BA and MMA or St was carried out at a
monomer=water ratio of 60=40 in order to control particle
coagulation and improve the solid content of the final latex.
Table 2 shows polymer glass temperatures as measured
by DSC, including both theoretical and experimental
values. The theoretical value of the glass transition tem-
perature of the polymer was calculated using the following
equation:[25]
1 W1 W2
¼ þ ½4
Tg Tg1 Tg2
 EFFECT OF POLYMER CHARACTERISTICS ON PARTICLE FORMATION 1325

TABLE 2 Table 2 that the copolymer has only one glass temperature;
Glass temperatures of polymers of varying composition moreover, the experimental value is similar to the
theoretical, indicating that the polymer is a kind of random
Tg (theoretical Tg (experimental copolymerization and that consistency among the chain
value,  C) value,  C) segments is fairly good.[26]
BA –54.0[27] –47.3 As shown in Figure 6, particle size increased with
St 107.3[12] 105.5 increase in MMA content from 221 to 267 nm due to the
MMA 127.2[12] 127.7 level of particle coagulation enhancement. It was noted that
BA=St 70=30 –19.9 –16.8 demulsification occurred when the MMA proportion of
BA=St 80=20 –31.4 –35.4 total monomer content was 30 wt%. With increase in
BA=St 90=10 –42.0 –40.2 MMA content, the hydrophilicity of copolymer increased.
BA=MMA 90=10 –41.3 –41.9 (The contact angle of the copolymer composition
responded to MMA=BA ¼ 10=90 and 20=80 and was
70.1 and 72.6 , respectively.) Further, the stability of latex
Tg denotes the glass transition temperature of the poly-
particles was reduced and particle coagulation improved.
mer, K; Tg1 is the glass transition temperature of polymer1
When the MMA=BA ratio was 30=70, particle stability
obtained by batch emulsion polymerization of monomer1,
due to particle coagulation could not balance the instability
K; Tg2 is the glass transition temperature of polymer2
originating from particle growth by the consuming mono-
obtained by batch emulsion polymerization of monomer2,
mer, leading to demulsification. However, by using the
K; W1 is the mass fraction of monomer1; and W2 is the mass
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inclusion of MMA in the procedure, it was not possible to

fraction of monomer2 (W1 þ W2 ¼ 1). It will be seen from
obtain a polymer latex of greater particle size. With this
method, copolymerization of St and BA can be used to
reduce the extent of particle coagulation, further reducing
latex particle size. The final latex particle size was around
240 nm with a St=BA ratio of 30=70.

4. CONCLUSIONS
A series of emulsion polymerizations were performed
under the same reaction conditions to investigate the effect
of the monomer or polymer on particle coagulation. The
highest latex polymer content for different monomer
compositions varied, corresponding to 40, 50, and 60 wt%
for St, MMA, and BA, respectively. Variation in polymer
hydrophilicity was considered the main factor determining
particle coagulation: the higher the hydrophilicity, the more
loosely the emulsifier molecules on the polymer particle
surface were packed; furthermore, particle stability was
decreased and particle extent enhanced. By copolymeriza-
tion of monomers of varying hydrophilicity, the extent of
particle coagulation can be controlled.

FUNDING
The authors appreciate financial support from the
National Natural Scientific Foundation of China (Grant
Number 51273026).

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