European Polymer Journal 45 (2009) 714–720

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European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Preparation of ASA (acrylonitrile-styrene-acrylate) structural latexes

via seeded emulsion polymerization
Shima Tolue a, Mohammad Reza Moghbeli a,*, Seyed Mehdi Ghafelebashi b
a
School of Chemical Engineering, Iran University of Science and Technology (IUST), Maleklo St., Khavar St. Farjam St. Narmak, P.O. Box 16844-13114, Tehran, Iran
b
Petrochemical Research & Technology Company (NPC-RT), P.O. Box 14358, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Acrylonitrile-styrene-acrylate (ASA) structural latexes were synthesized in a two-stage

Received 26 August 2008 seeded emulsion polymerization. In the first-stage, partially cross-linked poly (n-butyl
Received in revised form 3 December 2008 acrylate) (PnBA) and poly (n-butyl acrylate-stat-2-ethyl hexyl acrylate) P (nBA-stat-
Accepted 5 December 2008
2EHA) (75/25 by wt) rubber cores were synthesized, and then in the second-stage, a hard
Available online 24 December 2008
poly (styrene-stat-acrylonitrile) (SAN) (70/30 by wt) shell was grafted on to the rubber
seeds. The effects of surfactant type and second-stage monomer addition mode have been
investigated on the final morphology of two-stage emulsion particles. The results indicated
Keywords:
Acrylonitrile-styrene-acrylate core–shell
that an application of anionic surfactant, that is, sodium dodecyl sulfonate (SDS), along
latex with sodium persulfate (KPS) initiator for both stages, and with first-stage tert-butyl hydro-
Non-ionic surfactant peroxide (t-BHP) and second-stage KPS initiators led to a hemisphere particle morphology.
Monomer addition mode On the other hand, raspberry and core–shell structures were observed for the structural
Seeded emulsion polymerization latexes, which were prepared using a non-ionic surfactant, that is, nonylphenol ethoxylat-
ed polyethylene glycol (Igepal CO-850), accompanying KPS initiator for both stages. It is
clear, however, that the relative surface hydrophilicity of the core phase, altered by the sur-
factant type considerably affected the type of morphology formed. For obtained structural
latexes, the gradual addition of the second-stage monomers to the core latexes resulted in
a fairly real core–shell structure with a higher shell thickness. On the contrary, a raspberry
structure in which the rubber phase was enlarged by the second-stage polymer microdo-
mains was observed for the second-stage monomer addition batch. In fact, the shell semi-
batch polymerization conditions lower the shell plasticizing effect, and increase the kinetic
barrier to prevent from further second-stage monomer diffusion and microdomain forma-
tion within the rubbery phase.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction physical and mechanical properties [3–8]. Core–shell im-

Preparation of structured latex particles with predeter-
mined complex morphologies and a variety of functions
has attracted the interest of scientists for many years
[1,2]. These polymer materials are widely used in indus-
trial applications, for example, coating, adhesives, paints,
and rubber modification of some brittle thermoplastic
polymers and thermoset resins to improve their inherent
* Corresponding author. Fax: +91 21 77240495.
E-mail address: mr_moghbeli@iust.ac.ir (M.R. Moghbeli).
pact modifiers as typical structured latex particles have
been prepared via a two-stage emulsion polymerization
process [9–15]. The rubber cores with low glass-transition
temperatures (Tg) are synthesized in the first-stage emul-
sion polymerization. In the second-stage, that is, seeded
emulsion polymerization, a glass thermoplastic polymer
is grafted onto the rubber seeds by addition across the
residual double bonds or hydrogen abstraction from the
rubber chains, to give radicals which add monomer units
to form a grafted branch.
In most cases, the resulting particle morphology in the
seeded emulation polymerization cannot result in a core–

0014-3057/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2008.12.014
 S. Tolue et al. / European Polymer Journal 45 (2009) 714–720 715

shell structure with completely separated core and shell 2.2. Core and core–shell synthesis
phases [16,17]. Varying some polymerization parameters,
such as emulsifier and initiator types, the amount of The ASA core–shell latexes were synthesized via a two-
cross-linker, core-to-shell phase ratio, monomer composi- stage seeded emulsion polymerization. Acrylate rubber core
tion, and monomer addition mode at different polymeriza- and core–shell polymers were prepared in a 150-ml three-
tion stages provide various composite particle neck glass reactor equipped with a reflux, inlet nitrogen,
morphologies [17–25]. In many cases, the observed particle and a magnetic stirrer. The reactor was held in a bath with
morphology that deviates from the ideal core–shell struc- thermostatic control. Firstly, PnBA and P(nBA-stat-2EHA)
ture including morphologies are described simply as hemi- core latexes were synthesized at 80 °C and 250 rpm for
spherical, raspberry, mushroom, and confetti in the 3.5 h according to the emulsion recipes listed in Table 1. Var-
literatures [16,17]. In fact, the diversity in composite parti- ious types of aforementioned initiators and emulsifiers were
cle morphologies can be attributed to the phenomenologi- utilized to make the rubber cores with different surface
cal thermodynamic/kinetic behaviors which control the polarities. In the second-stage polymerization, the St/AN
phase distribution within particles in the seeded emulsion (70/30) monomer mixture was added to form the shell layer
polymerization [17,26]. over the rubber cores at 80 °C and 250 rpm for 3.5 h in batch
Commercialized core–shell structured latex particles as and semi-batch seeded emulsion polymerization processes
impact modifiers are composed of traditional grafted rub- (Table 2). Synthesized ASA emulsion particles were desig-
ber–thermoplastic materials, such as methacrylte-butadi- nated with a common name CS, a recipe number correspond-
ene-styrene (MBS), all-acrylics impact modifier (AIM), ing to a core recipe listed in Table 1, and an abbreviation B or
and acrylonitrile-butadiene-styrene (ABS). Commercial SB which is a representative of the shell batch (B) or semi-
acrylonitrile-styrene-acrylate (ASA) core–shell latexes, batch (SB) emulsion polymerization process.
with obvious similarities to ABS latexes, have also been
developed for the toughening of rigid SAN copolymers by 2.3. Characterization
a few industrial manufacturers [27]. Although the graft
shell in both ABS and ASA modifiers is similar, the hydro- 2.3.1. Gel content of the seed latex
phobic poly (butadiene) (PB) rubber core within the ABS The gel content of rubber seed particles was measured
particles is substituted by the less hydrophobic PnBA rub- via solvent extraction method. Three samples of dried
ber core in the ASA particles. Thus, the difference in the PnBA and P(nBA-stat-2EHA) film, 0.25 g each were added
interfacial tension of various rubber cores against water, to 25 ml THF, and stirred at 300 rpm and room tempera-
and in their compatibilities to the shell polymer units ture for 48 h. Then samples were centrifuged at 5000 rpm
may lead to some significant complexities in their manu- for 1 h. The sediment gel phase was separated from the
facturing process. sol phase and dried in a vacuum oven at 50 °C. The gel frac-
Although more research investigations have been car- tion was determined gravimetrically, based on the total
ried out in the preparation of ABS latexes, less attention weight of the sample.
has been paid to the preparation of ASA latexes [27]. In
the present research work, the effects of surfactant type 2.3.2. Grafting degree
and second-stage monomer addition mode on the final In order to determine the grafting degree, the compos-
morphology of the ASA emulsion particles have been ite latexes were freeze-dried to a fine powder, and placed
investigated. in a vacuum oven at 40 °C for 3 h to remove the trace
amount of water. Then, three samples of powder, 1 g each,
were dispersed in 25 ml toluene and were stirred at room
2. Experiments temperature and 300 rpm for 8 h. The dispersions were
centrifuged at 5000 rpm for 2 h at 4 °C. The gel phase at
2.1. Materials the bottom of the cell was separated from supernatant
phase, and both fractions were dried to remove solvents
All reagents were prepared from Merck Co., unless under vacuum at 40 °C for 24 h. The grafting degree, the
otherwise stated. Styrene (St), n-Butyl acrylate (nBA), weight ratio of grafted SAN to rubber seed particles, Gd,
and acrylonitrile (AN) were distillated under vacuum to was measured gravimetrically.
remove their inhibitors. Allyl methacrylate (ALMA) from
Aldrich and tertiary dodecyl mercaptan (TDM) from Fluka Table 1
were purchased as cross-linking agent and chain-transfer Recipes for the preparation of acrylate seed latexes.
agent, respectively. Sodium dodecyl sulfonate (SDS) as an-
Ingredientsa C1 C2 C3 C4
ionic surfactant and nonylphenol ethoxylated polyethyl-
BA 24 24 24 18
ene glycol (Igepal CO-850) as non-ionic surfactant from
2EHA 0 0 0 6
Rhodia, potassium persulfate (KPS) and water soluble DDI 72 72 72 72
tert-butyl hydroperoxide (t-BHP) both as initiators were KPS 0.06 – 0.06 0.06
used directly without any further purification. Tetrahy- t-BHP – 0.06 – –
drofuran (THF) and toluene, both analytical grades, were ALMA 0.09 0.09 0.09 0.09
SDS 0.12 0.12 – –
purchased for solvent extraction experiments. Distillated
Igepal CO-850 – – 0.33 0.33
deionized water (DDI) was prepared in the laboratory of
a
the author. Quantities are in weight parts.
716 S. Tolue et al. / European Polymer Journal 45 (2009) 714–720

Table 2 and non-ionic surfactants, and anionic and non-ionic first-

Recipes for the preparation of ASA latexes. stage initiators were used to synthesis the ASA latexes
Ingredientsa CS1-Bb CS2-B CS3-B/CS3-SBc CS4-B/CS4-SB (Table 2). In all cases, the second-stage initiator was the
Seed latex 50 50 50 50 anionic type, and the relative amount of the shell phase
St 8.60 8.60 8.60 8.60 to rubber core was selected to 50/50 (wt/wt). For the ASA
AN 3.72 3.72 3.72 3.72 latexes prepared using the non-ionic surfactant, the sec-
KPS 0.03 0.03 0.03 0.03 ond-stage monomer mixture was added at the beginning
SDS 0.005 0.005 – –
Igepal CO-850 – – 0.01 0.01
of polymerization in a preswelling batch process condition
NaHCO3 0.1 0.1 0.1 0.1 or during the polymerization reaction in a semi-batch pro-
TDM 0.012 0.012 0.012 0.012 cess with a constant feeding rate (Table 2).
a
Quantities are in weight parts.
b
The second-stage monomer mixture was added at the beginning of 3.2. ASA particle properties
the polymerization, batch operation (B).
c
The monomer mixture feeding rate in the semi-batch (SB) second- The characteristics of the prepared rubber cores and ASA
stage polymerization was 0.2 ml/min.
latex particles are indicated in Table 3. As shown, changing
the emulsifier type from anionic to non-ionic one in the
2.3.3. Particle size and size distribution first-stage polymerization caused the rubber particle size
The size and size distribution of the latex particles were to increase considerably, while the gel content was approx-
measured via dynamic laser light scattering (DLLS) with a imately constant, except for the rubber particles synthe-
wavelength of 632.8 nm and laser-source light He and Ne sized using t-BHP first-stage initiator (Table 3). Thus, the
gas. Light-scattering measurements were performed using initiator type seems to play an important role in determin-
a Sematech SEM-633 stepper-motor-driven goniometer. ing the gel content of the acrylate cores for a given cross-
The particle size and polydispersity index (PDI), the linking agent level. In fact, the success of the various initia-
ratio of the weight-to-number average diameter, Dw/Dn, tors in the preparation of gel particles and graft copolymers
which is a representative of latex particle size distribution, depends critically on the kinetics and mechanism of radical
were also determined by transmission electron micros- production, initiator efficiency, and the relative stability of
copy, TEM, technique based on 300 particles for each the various radical generating functions [29].
sample [28]. On the other hand, applying a special kind of cross-link-
ing/compatibilizing agent in the first-stage emulsion poly-
2.3.4. Glass-transition temperature (Tg) merization, that is, allyl methacrylate (ALMA), resulted in
The Tg values of the graft copolymers were determined preparing structural core–shell particles with a rather high
with a differential scanning calorimeter, Mettler Toledo grafting degree, even for the high gel-containing acrylate
DSC 822 system. The temperature scanning range was rubber particles. Nevertheless, the grafting degree of the
150 to 150 °C at a heating rate of 10 °C/min under a composite particles prepared using the non-ionic surfac-
nitrogen atmosphere. tant was higher than that of the particles synthesized using
the anionic surfactant (Table 3). This is due to the higher
2.3.5. Contact-angle measurement grafting density of the SAN copolymer chains tethered to
Contact angle of a water drop on a dried latex film was the rubber chains and more interfacial area exists between
used to estimate the hydrophilicity of the core and shell two incompatible phases. Unexpectedly, the grafting de-
latex polymers prepared by using various surfactants. The gree of the ASA composite particles prepared in the shell
dried PBA latex film and the compression-molded SAN semi-batch polymerization process was found to be lower
latex powder were annealed at 40 °C and 120 °C under than that of the particles synthesized in the shell batch
vacuum for 2 h, respectively, before measurement. polymerization process. This behavior can be attributed
to the resulting composite particle morphology formed in
2.3.6. Morphology of latex particles the batch polymerization process, compared to the mor-
Transmission Electron Microscopy, TEM, Zeiss CEM phology resulted in the shell semi-batch polymerization.
902A, was used to observe the morphology of structural la- Two glass-transition temperatures were observed for all
tex particles. The latexes were further diluted with distillat- the ASA structured latex particles. The lower glass-transi-
ed water, and then diluted droplets was transferred onto the tion temperature corresponds with the Tg of the rubbery
copper grids, mesh 200, and dried in open air. Then the sam- core and the upper temperature belongs to the SAN shell
ples were stained by osmium tetroxide vapor (OsO4) and polymer. The glass-transition temperatures of the compos-
phosphotungstic acid (PTA) solution 1% before microscopy, ite particles are summarized in Table 3. As one can expect,
in order to distinguish the core and shell regions. the ASA composite particles based on P(nBA-stat-2EHA)
rubber core showed a lower Tg in comparison with those
3. Results and discussion that were based on the PnBA rubber core.

3.1. ASA latex synthesis 3.3. ASA particle morphology

The ASA latex particles with a soft PnBA and P(nBA-stat- 3.3.1. Effect of surfactant type
2EHA) cores, and a hard SAN shell were synthesized via a As well-known, the morphology of composite latex par-
two-stage emulsion polymerization. Two different anionic ticles is crucial for achieving the desired properties of these
 S. Tolue et al. / European Polymer Journal 45 (2009) 714–720
Table 3
The characteristics of the synthesized core and core–shell particles.
Code Da (nm) Dnb (nm) Dwb (nm)
CS1-B 177.1 177.0 198.1
CS2-B 149.7 149.0 162.5
CS3-B 475.6 522.0 564.4
CS3-SB 446.2 529.0 653.6
CS4-B 591.0 502.4 516.1
CS4-SB 584.7 519.5 526.8
a
The mean diameter of the ASA latex particles is measured by means of DLLS apparatus.
b
The weight and number-average particles diameters, Dw and Dn, respectively, and PDI were determined by TEM.
c
The glass-transition temperatures (Tg) of the PnBA and P(nBA-stat-2EHA) rubber seeds measured by DSC experiment were
respectively.
structural polymer materials, which depend on many
parameters in the two-stage emulsion polymerization.
The particle morphology of the ASA latexes was studied
by means of transmission electron microscopy (TEM). This
conventional characterization method gives clearer infor-
mation on the particle morphology, but contains some dif-
ficulties in sample preparation method especially for the
ASA and AIM core–shell emulsion particles which have
chemical similarities amongst their intrinsic constituents.
Fig. 1 shows the morphology of the ASA particles consisted
of a soft PnBA or P(nBA-stat-2EHA) core which is partially
or completely engulfed by a hard SAN shell. As indicated in
the TEM micrographs, the dark and bright regions of the
composite particles represent the soft rubber and hard
shell polymer phases, respectively. For the ASA latexes,
the existence of residual and entrapped double bonds of
the ALMA comonomer within the rubber core microgels
caused OsO4 to stain the acrylic core phase preferentially
allowing one to distinguish it from the SAN shell. For the
ASA latexes prepared using anionic surfactant, a complete
phase-separated-type particle with hemisphere and cham-
pignon morphologies was observed (Fig. 1a and b). On the
contrary, using PnBA or P(nBA-stat-2EHA) rubber seeds
prepared with the non-ionic surfactant in both shell batch
and semi-batch polymerization resulted in ASA core–shell-
type morphologies (Fig. 1c–f). These different composite
morphologies that appeared to be arising from using dif-
ferent surfactant types can be ascribed to the thermody-
namic/kinetic control limitations that determine the final
morphology based on getting the minimum possible Gibbs
free energy of the system. From a thermodynamic point of
view, it was shown that only small differences in Gibbs free
energy arise from changing the interfacial tensions are re-
quired to vary composite particle morphology from core–
shell to partially engulfed structure [17]. In fact, one of
the most direct approaches to change the composite parti-
cle morphology is to use various surfactants and initiators
to modify the surface character of the products of first and
subsequent stage polymerization [20].
As shown in Table 4, the PBA latex particles prepared
using both the ionic initiator and surfactant have a higher
contact angle and surface hydrophilicity than the shell
polymer prepared with the same ionic initiator and surfac-
tant ones. As well-known, a system with a hydrophilic core
and a hydrophobic shell would be inherently difficult to
717
PDIb Gel (%) Gd (%) Tgc (°C)
Core Shell
1.12 76.8 36.7 – –
1.09 41.4 34.2 – –
1.08 72.6 66.4 46.5 106.3
1.23 72.6 57.3 47.6 107.1
1.03 68.5 54.7 51.1 103.7
1.01 68.5 45.9 50.9 104.2
49.7 and 58.7 °C,
achieve because of the thermodynamic constrains [30].
Nevertheless, using the non-ionic surfactant in such a com-
plicated system varying the core surface character resulted
in ASA composite emulsion particles with core–shell
morphology.
3.3.2. Effect of second-stage monomer addition mode
Interestingly, the core–shell-type morphologies ob-
served for the ASA latexes using non-ionic surfactant were
different, dependent upon the type of monomer addition
mode applied in the second-stage polymerization. Obvi-
ously, a fairly real core–shell structure with a bright thick
shell rings around the rubber seeds was observed for the
ASA latex particles, which were synthesized under the
starved monomer feed in the second-stage polymerization
(Fig. 1d and f). In contrast, particle morphology similar to
like that is between the raspberry and core–shell struc-
tures was observed for the shell batch polymerization con-
ditions (Fig. 1c and e). This inhomogeneous raspberry-like
morphology with a non-uniform size of SAN microbeads
on the rubber core surface could suggest an initiation of
the second-stage polymerization by a homogenous nucle-
ation mechanism as previously discussed in other seeded
emulsion polymerization systems [31,32]. It was shown
that the primary particles collide with the first-stage core,
adhere, and grow and then coagulate to form the shell [32].
On the other hand, swelling the partially cross-linked rub-
ber cores by all the shell monomer units at the beginning
of the reaction in the batch process cannot provide the de-
sired condition in which the second-stage polymer was
completely placed on the outside of the final particles. In
this case, the probable formation of second-stage polymer
microdomains within the core region of the core–shell par-
ticles seems to enlarge intensively the rubber phase as
compared with the particles prepared in the shell semi-
batch polymerization process. Thus, the final latex parti-
cles may display an internal phase-separated granular
structure [33]. Inversely, for the structured particles pre-
pared under shell semi-batch or starved-feed polymeriza-
tion condition, a core–shell structure with a smaller
rubber phase and higher shell thickness was observed
(Fig. 1d and f). In the shell semi-batch polymerization, a
gradual monomer addition prevents from further plastisiz-
ing effect of the second-stage monomers in the first-stage
polymer, the conditions which cause the particle morphol-
718 S. Tolue et al. / European Polymer Journal 45 (2009) 714–720

Fig. 1. TEM micrographs of ASA structured latex particles prepared using different surfactants, first-stage initiators, and second-stage monomer addition
modes: (a) CS1-B, (b) CS2-B, (c) CS3-B, (d) CS3-SB, (e) CS4-B, and (f) CS4-SB. (The structured latex particles were positively stained by OsO4 vapor and
magnification is 30,000.)

ogy to deviate from the ideal core–shell structure. It can be
assumed that the formation and growth of an initial rigid
shell layer formed around the soft rubber phase raised a ki-
netic barrier to prevent forming further monomer diffusion
into the rubber seeds.
Fig. 2 shows the DSC curves of a rubber core, a SAN
copolymer with 30 wt% AN, and an ASA graft rubber mate-
rial which was synthesized via shell semi-batch polymeri-
zation for comparison purposes. An enhancement in the Tg
of the rubber phase from 49.7 °C for the PnBA seeds to
46.6 °C for the PnBA rubber phase of the ASA latex parti-
cles was observed. This temperature enhancement can be
attributed to the existence of second-stage polymer micro-
domains within the rubber phase of the ASA composite
 S. Tolue et al. / European Polymer Journal 45 (2009) 714–720 719

Table 4
Measured contact angles on various latex films.
a b c
Sample Initiator type Surfactant type Contact angle (°)
C1 Ionic Ionic 102.2
C3 Ionic Non-ionic 89.2
SANa Ionic Ionic 97.0
SANa Ionic Non-ionic 93.7
a
The SAN latexes were synthesized with the same recipes and poly-
merization conditions which were applied to the core latexes. Fig. 4. Schematic ASA latex particle morphologies which were prepared:
(a) hemisphere; (b) and (c) interphase and microdomain morphology
models deviating from the ideal core–shell structure.

C1
CS3-B
Nevertheless, the DSC results indicate two Tg for all the ASA
SAN latex samples prepared by both shell batch and semi-batch
-0.5
polymerization processes, corresponding to the acrylate
core and shell polymers, respectively (Fig. 3).
Heat flow (mW)

-1 4. Conclusion

Acrylonitrile-styrene-acrylate (ASA) latexes were pre-

-1.5 pared via seeded emulsion polymerization to overcoat an
acrylate PnBA and P(nBA-stat-2EHA) seed polymers with
a glassy SAN copolymer shell. For the ASA latexes, using
-2
anionic surfactant in the two-stage emulsion polymeriza-
tion resulted in a complete phase-separated-type particle
with a hemisphere or champignon morphologies. Decreas-
ing the surface hydrophilicity of the rubber seeds using
-2.5
non-ionic surfactant caused a raspberry and core–shell
-100 -50 0 50 100 150
particle structures dependent upon the mode of monomer
Temp. (C) addition was observed. When the St/AN shell monomer
mixture was added gradually to the rubber seed latex,
Fig. 2. DSC results for C3 rubber seeds, CS1-B structural particles, and
SAN latex particles (St/AN: 70/30 by wt).
semi-batch or starved-feed condition, a real ASA core–shell
particles consisting of completely separated rubber core
and shell phases was obtained (Fig. 4). On the contrary,
particles. In fact, to some extent, the occluded rigid poly- the results showed that a raspberry structure with sec-
mer units within the swollen rubbery phase seem to influ- ond-stage polymer inclusion and thicker core and shell
ence slightly the mobility and Tg of the soft rubber chains. interphase layer was observed for the ASA composite la-
texes which were prepared via shell batch emulation
polymerization.
-0.5

CS3-B Acknowledgments
CS3-SB
CS4-B
-1 CS4-SB
The authors gratefully thank the Petrochemical Re-
search and Technology Company of Iran for partial finan-
cial support of this work.
Heat flow (mW)

-1.5
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