Progress in Organic Coatings 77 (2014) 1826–1833

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Progress in Organic Coatings

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

Transition behavior, surface characteristics and film formation of

functionalized poly(methyl methacrylate-co-butyl acrylate) particles
Hossein Adelnia a , Jaber Nasrollah Gavgani a,b , Hossein Riazi a ,
Hossein Cheraghi Bidsorkhi c,∗
a
Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, P.O. Box 15875-4413, Tehran, Iran
b
Department of Chemical Engineering, Amirkabir University of Technology, P.O. Box 15875-4413, Tehran, Iran
c
Department of Polymer Engineering, University Technology Malaysia (UTM), P.O. Box 07-5588166, Malaysia

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

Article history: Carboxylic functionalized poly(methyl methacrylate-co-butyl acrylate) particles were synthesized by
Received 1 November 2013 soap free emulsion polymerization using sodium salts of itaconic acid and acrylic acid. Transition behav-
Received in revised form 30 May 2014 iors of these latexes in terms of glass transition of matrix and cluster were found to be completely
Accepted 11 June 2014
different from those synthesized by solution polymerization. This disparity was attributed to the dif-
Available online 16 July 2014
ference between co-monomers sequence distribution along the chains. Distribution of functional groups
in the latexes was determined by conductometric titration. Film formation process of the latexes was
Keywords:
also examined and interpreted based on the density of surface functional groups, transition behav-
Soap free emulsion polymerization
Film formation
iors, and particle size. AFM images revealed that, as the amount of these ionic co-monomers increases,
Cluster formation more ordered films are obtained, while the particle inter-diffusion is greatly retarded. A dimensionless
Ionic co-monomer parameter indicating relative roughness of the films further supported the aforementioned findings.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction inter-diffusion [7]. In the first stage, as the medium evaporates,

Incorporation of surfactants or stabilizers into polymer latexes
is associated with several disadvantages such as desorption and
segregation of surfactants after film formation process, reduction of
mechanical strength, deterioration of optical/electrical properties,
and so on [1]. Thus, elimination of these impurities after production
is vital. Most of the processes applied to eliminate such impurities
are time-consuming and expensive [2]. Hence, synthesis of clean
particles has drawn the attention of researchers in both scientific
and industrial communities [3].
Introduction of functional groups like carboxyl into poly-
mer backbone creates chemically reactive sites which enhance
binding to various surfaces [4] and improves colloidal stabil-
ity [5]. Carboxylic functionalized particles have negative charges
on their surface, introducing them as an appropriate candidate
for monolayer adsorption on the positively charged surfaces [6].
Furthermore, they can be cast and annealed to form films with
controllable thickness even on other types of substrates.
Film formation from latex mainly consists of three various stages
including medium evaporation, particles deformation, and their
∗ Corresponding author. Tel.: +60 126064685.
E-mail address: chossein2@live.utm.my (H. Cheraghi Bidsorkhi).
the latex solid content increases and irreversible contact among
particles is obtained. It is believed that this stage ends when solid
content is around 60–75%. In the second stage, while the medium
is still evaporating, particles deform due to external forces such as
interfacial and capillary forces. This stage ends when the film is
completely dried; however, particle boundaries are still apparent.
In the last stage which occurs above glass transition temperature
of the polymer, particles are able to inter-diffuse in each other and
form a smooth, continuous, as well as mechanically stable film.
Based on the above-mentioned statements, the processing tem-
perature and its difference with Tg(s) play a key role in film
formation process. In comparison with neutral polymers (non-
ionic ones), macromolecules containing ionic co-monomer show
different thermal behaviors due to ionic interactions. Ionic groups
incorporated into the polymer chains undergo self-association to
form ionic aggregates, i.e. multiplets [8]. These regions severely
hinder the mobility of adjacent chains, resulting in an increase in
the Tg of the matrix. As the concentration of ionic co-monomer
increases, both the number and size of multiplets increase up to
a point where these regions overlap. These overlapped regions are
called clusters [9–12]. At this point, the polymer shows two distinct
Tgs; one of which, commonly the lower one, relates to the Tg of the
matrix, while the other, commonly the higher one, corresponds to
the Tg of the cluster.

http://dx.doi.org/10.1016/j.porgcoat.2014.06.009
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 H. Adelnia et al. / Progress in Organic Coatings 77 (2014) 1826–1833
Table 1
Particle size and polydispersity index (PDI) of synthesized particles; the left and right tables represent the results of NaAA and Na2 ita containing samples, respectively.
Sample code Particle size (nm)
Neat MBC 350
MBC-NaAA1.25 372.5
MBC-NaAA2.5 391.9
MBC-NaAA5 613.8
MBC-NaAA10 804.4
Despite the fact that extensive research has been conducted
on film formation of charged particles, there is no focused study
assessing the film formation process of sodium acrylate and sodium
itaconate functionalized particles. In the first step of this research,
such charged latexes were synthesized by soap free emulsion
polymerization (SFEP). Subsequently, the distribution of functional
groups and transition behaviors of the latexes were examined.
Finally, film formation of the synthesized latexes was evaluated
and compared with each other.
2. Experimental
2.1. Materials
Methyl methacrylate (MMA), butyl acrylate (BuA), acrylic acid
(AA), itaconic acid (Ita), ammonium persulfate (APS), sodium
hydroxide (NaOH), hydrochloric acid (HCl) and methanol were pur-
chased from Merck Co. AA and Ita were treated by excess amount
of NaOH solution to prepare fully neutralized NaAA and Na2 ita,
respectively. All of the materials were used without further purifi-
cation.
2.2. Typical soap free emulsion polymerization
MMA/BuA (6.8/1, w/w) mixture was used as stock. To synthe-
size MBC based particles, typical soap free emulsion polymerization
(SFEP) was carried out as follows: 19.76 g water was added to
10.64 g methanol as polymerization medium. In all the samples,
the monomer phase consisted of MMA, BuA and ionic co-monomer,
totally weighting 1.6 g. Moreover, 0.016 g APS (1 wt.% with respect
to total monomer weight) was added to the medium to initiate
the polymerization. The ingredients of each recipe (mixture of
methanol/water and monomer phase) were added to 50 cc glass
bottles, purged with nitrogen, capped and sealed. Each glass bot-
tle was located in a constant-temperature water bath at 75 ◦ C at
60 rpm. The reaction time for all runs was about 24 h to assure a
complete reaction. The abbreviation which will be used for syn-
thesized samples are as follows: samples containing 1.25, 2.5, 5
and 10 mol.% of sodium acrylate co-monomers in the monomer
feed were, respectively, named as MBC-NaAA1.25, MBC-NaAA2.5,
MBC-NaAA5, and MBC-NaAA10. The same approach was adopted
to abbreviate the names of samples containing sodium itaconate
co-monomer.
2.3. Characterization
Films were prepared by casting a few drops of dispersions
(5 wt.% solid content) onto 1 cm2 cleaved mica plates. The samples
were dried for a specified amount time at various temperatures
under atmospheric condition in a convection oven. The average
hydrodynamic diameter and polydispersity index (PDI) of the MBC
based particles were determined by dynamic light scattering (DLS)
(DLS, Nano ZS, Malvern Instruments). DLS was applied with an
angle of 173 by using He–Ne laser (4 mW) operated at 633 nm.
1827
PDI Sample code Particle size (nm) PDI
0.009 Neat MBC 350 0.009
0.182 MBC-Na2 ita1.25 394 0.035
0.097 MBC-Na2 ita2.5 477 0.07
0.016 MBC-Na2 ita5 677.2 0.005
0.046 MBC-Na2 ita10 862.4 0.118
The AFM used in this research is a commercial instrument
(Nanoscope II, Digital Instruments) operated in a constant force
mode. All the measurements reported here were performed on
annealed films, using a 100 ␮m silicon nitride tip. Scanning
electron microscope (SEM) micrographs also were obtained by
High Resolution LEO 1550 FEF, working at accelerating voltage
of 10 kV.
After drying a part of the each latex, heat flow curves of the films
were collected in the temperature range of 40–220 ◦ C at 10 ◦ C/min
with a TA Instrument under nitrogen atmosphere. In all the cases,
in order to remove the thermal history, annealing was performed
at 120 ◦ C for 15 min under nitrogen atmosphere. The heat flow data
were recorded on the last heating run.
After the polymerization, a part of the latex was transferred to
a centrifuge (model Centrikon T-2060, Kontron Instrument) work-
ing at 30,000 rpm. The centrifuging process lasted 2 h to ensure
complete separation of possible impurities. The obtained serum
was separated from the coagulated particles and then was cast in
a pettry dish to examine the presence of soluble polyelectrolyte or
free copolymer chains. The coagulated particles were re-dispersed
in water by applying sound waves. The conductometric titration
was carried out on the diluted re-dispersed solution to quantify
the surface active anions. A standard solution of HCl with known
concentration (0.1 N) was used as titrant and added to the mix-
ture dropwise while the conduction of the system was measured
simultaneously.
3. Results and discussion
3.1. Particle size and particle size distribution of MBC based
particles
Poly(methyl methacrylate-co-butyl acrylate) based particles
were synthesized via SFEP in water/methanol mixture (65/35, w/w)
as the medium. Sodium salts of acrylic acid (NaAA) and itaconic
acid (Na2 ita) ranging from 1.25 to 10 mol.% were employed for
functionalization. The incorporation of both of these co-monomers
increased the average particle size and narrowed particle size dis-
tribution. Average particle size and its distribution obtained by DLS
are presented in Fig. 1a and b as well as Table 1. SEM micrographs
of the synthesized particles are also presented in supplementary
data (Fig. 1).
In direct contrast with most of the ionic co-monomers such
as sodium styrene sulfonate [13], sodium undecylenic isethion-
ate [14], and dimethyl vinyl pyridinium methyl sulfonate [15],
the incorporation of NaAA and Na2 ita progressively increased the
particle size. Particle size reduction in case of the former ionic
co-monomers has widely been attributed to the high electrostatic
repulsion between primary particles, originating from strong ionic
groups. As a result, the rate of coagulative nucleation decreases,
resulting in finer particles size.
However in case of NaAA and Na2 ita, increasing the particle
size can be ascribed to the increased chain length where grow-
ing oligomers precipitate to form nuclei. This phenomenon delays
nuclei formation which means fewer number of nuclei and higher
1828 H. Adelnia et al. / Progress in Organic Coatings 77 (2014) 1826–1833

Fig. 1. Size distribution of functionalized particles synthesized by SFEP using NaAA (a) and Na2 ita (b) as anionic co-monomers.

final particle size [16]. Apart from that, it seems that there exists
a competition between ionic co-monomer concentration and ionic
strength of the medium [17,18]. The former contributes to stabilize
nuclei, prevent homo-coagulation, and reduce the size of parti-
cles while the latter results in an increase in the average particle
size. Here, ionic strength of the medium overcomes co-monomer
concentration which can be considered as another factor of the
increased average particle size.
Particle size distribution, the other important feature of the latex
was increased by the addition of co-monomer and subsequently
decreased. Broadening of particle size distribution can be attributed
to secondary nucleation. However, at higher co-monomer
concentration, particle size distribution was narrowed. Yamamoto
[19] described heterocoagulation between the primary and sec-
ondary particles as the main reason of narrowing particle size
distribution. He mentioned that the media with high ionic strength
destabilize the primary and secondary particles to coagulate. This
hypothesis can also be applied to the case of co-monomer incor-
poration. In fact, since the addition of more ionic co-monomer
contributes to an increase in the ionic strength, it can be concluded
that the increase of ionic co-monomer itself is responsible for nar-
rowing particle size distribution.
More details about particle size, particle size distribution, and
their differences with each other were discussed in our previous
work [18].
3.2. Functional group distribution of MBC based particles
Practically, carboxylic groups can be found in three different
places including: (i) inside the final particles as buried groups,
(ii) on the surface of the particles as stabilizing groups, and (iii)
in the medium as soluble carboxylic groups. Since no polymer
was gained after casting the serum, it can be concluded that
neither free polyelectrolytes nor soluble copolymer chains were
synthesized during the course of polymerization. This phenomenon
is attributed to the addition of methanol to the polymerization
medium [20]. So, the remaining carboxylic groups incorporated
into the chains are either buried inside the particles or located at
the particle surface. Therefore, conductometric titration was per-
formed on re-dispersed latexes to measure the ratio of buried to
surface carboxylic groups. Conductometric titration curves of the
latexes are shown in Fig. 2. The appearance of two distinct break-
ing points in the titration curves of sodium acrylate based latexes
signifies the presence of both weak and strong base groups on
the surface of the polymer particles [21]. The former is generated
from initiator fragment (SO4 − ) while the latter is obtained from
the functional co-monomer, NaAA. On the other hand, three break-
ing points were observed in the conductometric titration curves
of sodium itaconate based latexes. Two of them are related to car-
boxylic groups of itaconic molecules which possess unequal pKa
(3.5 and 5.5) [22]. The third breaking point is ascribed to initiator

Fig. 2. Conductometric titration curves of MBC based latexes containing (a) NaAA and (b) Na2 ita.
 H. Adelnia et al. / Progress in Organic Coatings 77 (2014) 1826–1833 1829

Table 2
population of charged species on particle surface (microequivalent/g polymer).

NaAA functionalized latexes Population of charged species Na2 ita functionalized latexes Population of charged species

MBC-NaAA1.25 106 MBC-Na2 ita1.25 138

MBC-NaAA2.5 155 MBC-Na2 ita2.5 200
MBC-NaAA5 221 MBC-Na2 ita5 262
MBC-NaAA10 335 MBC-Na2 ita10 395

fragment that has stronger acid strength as compared to itaconic
acid. The titration curves revealed that almost 60% of the loaded
sodium acrylate groups are located on the surface of the MBC-
NaAA1.25 particles while this number decreased to 30% in the case
of MBC-NaAA10 particles. Burial percentage in Na2 ita samples is
greater as compared with NaAA ones due to significant increase in
ionic strength of the medium. Chang and Chen [23] showed that by
increasing ionic strength of the polymerization medium, average
particle size of sulfonate functionalized polystyrene increases. This
phenomenon implicitly shows more burial of functional groups as
a result of ionic strength increment. Andersson and Backfolk [24]
also reported similar results where they detected that 18% of initial
carboxyl groups in styrene/butyl acrylate copolymer were buried
inside the particles. Table 2 shows population of charged groups on
the surface of synthesized particles.
Competition between ionic strength of the medium and co-
monomer concentration determines burial extent of carboxylic
groups. Addition of salt to the latex media (i.e. higher ionic strength)
leads to screening effect which increases average particle size in the
early stages and results in catastrophic coagulation of the latex [25].
On the contrary, the addition of ionic co-monomers causes parti-
cle size reduction [26]. Indeed, in case of these two co-monomers,
it seems that the effect of ionic strength induced by sodium ions
overcomes the effect of increased co-monomer concentration and
as a result, burial percentage increases.
monomer mixture are rMMA =2.07 and rBuA = 0.35 [32]. This indi-
cates that MMA reacts much faster than BuA; consequently, the
monomers distribution (MMA and BuA) within samples becomes
nonuniform. In fact, preforming polymerization in batch condi-
tion and the difference in reactivity ratios of co-monomers both
contribute to the synthesis of nonuniform chains consisting of
MMA-rich and BuA-rich regions.
When either Na2 ita or NaAA was introduced, two distinct peaks
were resolved. What’s more, the threshold for aggregation of ionic
groups was too low (≤1.25 mol.%) as compared to the literature
results [28]. Comparing these results with previous investigations
performed on poly (methyl methacrylate-co-sodium acrylate)
synthesized by solution polymerization, one can realizes a great
disparity in the Tg of the matrix and cluster. This can be attributed
to the more uniform distribution of ionic co-monomer sequence in
the polymers synthesized by solution polymerization as compared
to SFEP. Generally, distribution of co-monomer along the polymer
chains can be affected by the difference in monomers reactivity
ratio and their thermodynamic affinity to the medium. Regardless
of the difference in reactivity ratio, ionic co-monomers in emulsion

3.3. Transition behavior of MBC based particles

As discussed in previous studies [27,28], the matrix and cluster

Tgs progressively increase with increasing the content of ionic co-
monomer. However, the increasing rates of the Tgs and the extent of
divergence between the Tgs of the matrix and cluster are different
for each matrix/ionomer pair. As the polarity of the matrix increases
(higher dielectric constant), cluster formation is inhibited thanks
to the higher tendency of the ions for dissolution in the host poly-
mer [28]. Commonly, the increasing rate is introduced by the slope
of first order polynomial equation which can be obtained by fit-
ting the DSC results. Fig. 3a and b, respectively, show a typical heat
flow first-derivative curve of MBC-NaAA5, and the glass transition
temperatures of the matrix and cluster regions as a function of co-
monomer content. All the samples containing ionic co-monomer
showed two distinct peaks except Neat MBC which exhibited just
one peak. The first and second peaks appeared at lower and higher
temperatures are attributed to the Tgs of matrix and cluster regions,
respectively. The Tgs of the matrix and cluster regions remained
nearly constant as the ion content increased.
The Tg of the matrix for all the samples was about 89 ◦ C which
is much higher than the calculated Tg obtained by Fox equation
[29] (when methyl metharylate weight fraction is around 82%, esti-
mated Tg value is 72.86 ◦ C).

1 wMMA wBuA wMMA wBua

= + = + (1)
Tg(copolymer) Tg,MMA Tg,MMA 378 219

Such a great difference in the calculated and experimental Tg

of copolymers has widely been discussed so far [30,31]. In brief,
the Fox equation assumes that monomers in copolymer chains are
distributed randomly, while reactivity ratios for MMA/BuA
Fig. 3. (a) DSC curves of Neat MBC, and MBC-NaAA5 particles, (b) glass transition
temperatures of the cluster regions as a function of co-monomer content for differ-
ent amounts of NaAA and Na2 ita (dashed circle in DSC curve represents the cluster
region).
1830 H. Adelnia et al. / Progress in Organic Coatings 77 (2014) 1826–1833

Fig. 4. Schematic representation parameters used in Eq. (2) for  value.

polymerization tend to be located and/or polymerized at the inter-
face due to the lack of thermodynamic affinity between monomer
pairs. This leads to an intense segregation of NaAA-rich domains
from MMA/BuA ones in case of SFEP, as compared to the solution
polymerization. Doubtlessly, segregation of the matrix from ionic
co-monomer was so intense that the mobility of matrix chains
was not affected. In other words, segregated domains were large
enough to form completely separated regions of matrix and cluster,
consequently leading to a core–shell like structure. In order to
further verify these statements, MBC-NaAA2.5, and MBC-Na2 ita2.5
were solution-polymerized in ethanol/water (90/10, w/w), and Tgs
of matrix and cluster were measured and compared with those of
synthesized by SFEP (see Fig. 2 in supplementary data). As can be
seen, no cluster was formed for samples synthesized by solution

Fig. 5. AFM images of films prepared from MBC-NaAA0 (a), NaAA1.25 (b), NaAA5 (c), and NaAA10 (d) latexes at 100 ◦ C for 30 min.
 H. Adelnia et al. / Progress in Organic Coatings 77 (2014) 1826–1833 1831

Fig. 6. AFM images of films prepared from NaAA5 latex annealed at 70 ◦ C (a), 100 ◦ C (b), 140 ◦ C (c) and Na2 ita5 latex a annealed at 70 ◦ C (d), 100 ◦ C (e), 140 ◦ C (f) for 30 min.
1832 H. Adelnia et al. / Progress in Organic Coatings 77 (2014) 1826–1833
polymerization even at 2.5 mol.% of co-monomer. However, the Tgs
of matrix are ca. 13–15 ◦ C higher than those of synthesized by SFEP.
3.4. Film formation stages of MBC based particles
Before discussing the film formation process and how it is
affected by a change in the processing temperature and co-
monomer content, a dimensionless roughness mean value was
introduced as follows to eliminate the effect of initial particle size
on the surface roughness of films:
Ra
= (2)
Rb
where , Rb and Ra are relative roughness, roughness before and
after annealing, respectively (see Fig. 4). The relative roughness can
vary from zero to unity.  values close to zero imply the presence
of a smooth film, while those close to unity signify the presence of
intact particles and lack of proceeding in film formation process.
Since the dimensions of particles do not change before anneal-
ing, Rb can roughly be estimated to be half of particle size measured
by DLS or SEM. Here, diameters measured by DLS are used as an
indicator of Rb .
Fig. 5 shows AFM images of films formed from the latexes with
various amounts of NaAA, after being kept at 100 ◦ C for 30 min. As
the concentration of NaAA increases, more distinguishable particle
boundaries are observable. However, in the films without any NaAA
(Neat MBC), no particles were seen as an effect of complete inter-
diffusion of particles. In fact, since there exists no cluster region in
this sample and since the annealing temperature is slightly higher
than the Tg, copolymer chains were enough mobile to readily inter-
diffuse in each other in annealing time as short as 30 min. Moreover,
in this case it seems that ionic groups arising from initiator at the
particle surface were not adequately able to hinder inter-diffusion.
It also seems that more amount of time was needed to obtain a
more perfect film with the least roughness and the most extent of
inter-diffusion, since  value of this film is not very close to zero
yet ( = 0.1057).
In contrast to Neat MBC sample, distinguishable spherical
particles are detected in AFM images of films formed from NaAA
containing latexes (Fig. 5b–d). This indicates that higher tem-
perature and/or more time is needed for particle contours to
disappear, as well as for particles to inter-diffuse in each other.
As the amount of NaAA incorporated in the latexes increases, 
values also increase, indicating that NaAA domains strongly retard
the inter-diffusion (Table 3). As DSC results showed, ionic clusters
are formed even at low amount of ionic co-monomer. So, it can
be concluded that these clusters were strong enough to make a
suppressive pathways (i.e. polyelectrolyte membrane) which sub-
sequently lead to inter-diffusion hindrance. Fig. 5 also shows that
as weight fraction of ionic co-monomer increases in the polymer,
more ordered films are obtained. Formation of more ordered films
in MBC-NaAA5 and MBC-NaAA10 can be ascribed to the presence of
more charged species on the particle surface. In fact, more repulsive
interactions between particles during drying process arrange them
into a more ordered films [33]. Narrower particle size distribution
Table 3
 values of films prepared from the latexes containing various amounts of NaAA as
anionic co-monomer.
Sample code  values (dimensionless)
Neat MBC 0.1057
MBC-NaAA1.25 0.2578
MBC-NaAA5 0.2337
MBC-NaAA10 0.4950
Table 4
 values of films prepared from MBC-NaAA5 and MBC-Na2 ita5 at three different
temperatures.
Annealing temperature (◦ C) Sample code  values (dimensionless)
MBC-NaAA5 0.1608
70
MBC-Na2 ita5 0.02038
MBC-NaAA5 0.1095
100
MBC-Na2 ita5 0.1244
MBC-NaAA5 0.0522
140
MBC-Na2 ita5 0.0561
of the MBC-NaAA5 and MBC-NaAA10 can also be considered as
another reason for the formation of highly ordered films.
The effect of annealing temperature on morphology of films
obtained from MBC-NaAA5 and MBC-Na2 ita5 was depicted in Fig. 6,
and its results are listed in Table 4. It is widely reported that ionic
species on the particle surface self-assemble to form ionomer mem-
branes during film formation process. These ionomer membranes
are formed when the concentration of functional groups exceeds
a minimum, causing a great hindrance in particle inter-diffusion.
In other words, the presence of ionic groups on the particle sur-
face retards film formation process and causes a sharp decrease
in inter-diffusion coefficient of the particles. Although the forma-
tion of ionomer regions before neutralization of acidic groups is
possible, their neutralized forms create denser ionomer regions. It
means that particles face more severe inter-diffusion hindrance if
functional groups are neutralized [34]. However, such hindrance
can be obviated at the higher processing temperatures, especially
if the annealing temperature is higher than the Tg of cluster.
In fact, the aforementioned system including matrix and
ionomer regions can be compared with a latex blend system made
from hard and soft particles. When the annealing temperature
exceeds the Tg of soft particle, they flow between hard ones like
glue. If the annealing temperature exceeds the Tg of hard particles,
the harder ones also have the chance of flow [35]. Based on this
analogy, it can be deduced how ionomers and adjacent polymeric
chains inter-diffuse in each other to form a continuous film. This
hypothesis is fully supported in Fig. 6 where inter-diffusion of par-
ticles and the formation of smooth films gradually occurs as the
annealing temperature increases from 70 to 140 ◦ C. More impor-
tantly, as disused in DSC section, the formation of ionomers and
their extent in MBC-Na2 ita samples are more intense than those
of MBC-NaAA ones. This is due to the presence of two functional
groups in each co-monomer molecule; and this is why at a specific
annealing temperature the  values of Na2 ita samples are higher
than those of NaAA ones.
4. Conclusion
Functionalized poly(methyl methacrylaye-co-butyl acrylate)
latexes were synthesized by SFEP. Sodium acrylate and sodium
itaconate were used for functionalization. As the amount of
co-monomer increases, particle size and particle size distri-
bution are, respectively, increased and narrowed. The former
was attributed to the fact that ionic strength overcomes ionic
co-monomer concentration, while the latter was assigned to het-
erocoagulation between the primary and the secondary particles
induced by increased ionic strength. Moreover, conductometric
titration revealed that a fraction incorporated carboxylic groups
are buried inside the particles. This phenomenon is more severe
in case of sodium itaconate due to the presence of two functional
groups in each molecule of the co-monomer. In addition, the clus-
ter formation threshold was found to be completely different from
the results of other research done on MBC based polymer syn-
thesized by solution polymerization. The relative roughness value
was defined as a measure of film formation proceeding. This value
 H. Adelnia et al. / Progress in Organic Coatings 77 (2014) 1826–1833
increases as the amount of co-monomer concentration increases,
indicating the retardation effect of ionic co-monomer on inter-
diffusion. However, as the annealing temperature increases, the
relative roughness value decreases. This reduction was more sig-
nificant in samples containing NaAA, implying more retardation
strength of Na2 ita than that of NaAA in inter-diffusion.
Acknowledgments
This work was fully supported financially by PooyaFaraz NikAn-
dish (Tehran, Iran) Co. Besides, our special thanks are due to Ferdos
Taleb for her kind patience to read this work and providing us with
her valuable remarks.
Appendix A. Supplementary data
Supplementary material related to this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.porgcoat.
2014.06.009.
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