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Copolymerization of Styrene and n-Butyl Acrylate with Itaconic Acid:

Influence OF Carboxylic Groups Distribution on Performance of Decorative
Paints

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Effect of itaconic acid on the wet scrub
resistance of highly pigmented paints for
architectural coatings

Maurício Pinheiro de Oliveira, Caroline

Reggiani Silva & Lilia Müller Guerrini

Journal of Coatings
Technology and Research

ISSN 1547-0091
Volume 8
Number 4

J Coat Technol Res (2011)

8:439-447
DOI 10.1007/
s11998-010-9317-7

1 23
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1 23
 Author's personal copy
J. Coat. Technol. Res., 8 (4) 439–447, 2011
DOI 10.1007/s11998-010-9317-7
Effect of itaconic acid on the wet scrub resistance of highly
pigmented paints for architectural coatings
Maurı́cio Pinheiro de Oliveira, Caroline Reggiani Silva,
Lilia Müller Guerrini
Ó ACA and OCCA 2011
Abstract This study investigates the influence of
carboxylic monomers, such as itaconic acid (IA), on
the colloidal properties of the latexes made by semi-
continuous emulsion copolymerization of styrene
(STy) with n-butyl acrylate (BA). A number of
copolymerization runs were carried out with different
IA concentrations. The effect of functional monomer
on the overall conversion, the colloidal properties of
the latexes, and the distribution of the carboxylic
groups (buried, particle surface and aqueous phase)
were examined. The carboxylic groups present in the
latexes were analyzed using conductimetric and poten-
tiometric titrations. The behavior of the IA on the wet
scrub resistance of highly pigmented paints for archi-
tectural coatings was examined and correlated with the
distribution of the carboxylic groups. The results
obtained showed that the properties of highly pig-
mented paints are greatly dependent on the amount
and distribution of the carboxylic groups. The carbox-
ylic acid distributed in the aqueous phase has a strong
influence on the wet scrub resistance and on the
characteristics of the final products.
Keywords Functionalized latex, Wet scrub resistance,
Itaconic acid, Emulsion polymerization, Highly
pigmented paints
M. P. Oliveira (&), C. R. Silva
BASF S.A.-R&D, Guaratinguetá, São Paulo, Brazil
e-mail: mauricio.oliveira@basf.com
L. M. Guerrini
Department of Materials Engineering, Federal University
of São Paulo, São José dos Campos, São Paulo, Brazil
Introduction
Carboxylated latexes can be produced by performing
emulsion polymerization in the presence of monomers
that are relatively water insoluble, such as styrene
(STy), n-butyl acrylate (BA), and a small amount of
carboxylic monomers such as acrylic (AA), metha-
crylic (MAA), itaconic (IA), and fumaric (FA)
acids.1–3 These carboxylic monomers are often
employed in polymer colloid formulations to improve
the colloidal stability during and after the production of
the latexes when compared with latexes stabilized only
by physically adsorbed soaps. The enhanced colloidal
stability and freeze–thaw stability result from the
presence of carboxylic groups on the outer surface of
the latex particles, providing both steric and electro-
static stabilizations.4 These properties justify the use of
small amounts of the functional monomers in industrial
formulations used essentially as binder in paper coat-
ings, carpet backing, adhesives, bonding agents in
architectural paints, and for adjusting the latex viscosity
by varying the degree of neutralization.4–6
In decorative paints, one of the most important
properties of the carboxylic acids is the wet scrub
resistance of the dry paint film used as an indication of
the pigment binding capacity of the binder, with the
classification being according to the number of scrub
cycles. There are numerous latex and paint formulation
parameters which can influence the scrub performance
of paint. The scrub resistance results depend on the
method, type, distribution, and the amounts of carbox-
ylic acids employed to prepare the latexes.2,5 The
polymerization of the hydrophilic monomers with
hydrophobic monomers, such as STy, result in the
formation of a block copolymer anchored to the
particle.6 These carboxylic groups anchored to the latex
particle can interact directly with the pigment particle.
An additional steric barrier can be created, which can
further prevent pigment agglomeration. The ionic
439
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J. Coat. Technol. Res., 8 (4) 439–447, 2011
strength of the extent of carboxylation on the latex
particle surface changes the way the latex particles
consolidate with themselves and with the particles in
the paint formulation. Wildeson et al.2 investigated the
influence of functional acid monomers and degree of
neutralization on wet scrub resistance and their ability
to effectively disperse titanium dioxide pigment parti-
cles in flat paint applications. They showed that the
degree of acid neutralization before the emulsion
copolymerizations greatly influences the ability of
the latexes to prevent titanium dioxide particle
aggregation.
A significant generic problem for carboxylic mono-
mer is the polymerization in the aqueous phase. Some
of the factors that influence the final distribution of
carboxylic groups in latex products, such as partition-
ing of carboxylic monomer partially or totally soluble
in water between the organic phase (monomer drop-
lets and/or polymer particles) and the continuous
phase (water), are the reactivity ratios of the mono-
mers, the pH of the polymerization, and the degree of
dissociation of the functional monomer.7–11 A few
fundamental studies have been conducted on the
behavior of IA in emulsion polymerization.7,8,12 Ford-
yce and Ham8 demonstrated that a considerable
portion of IA is polymerized in the aqueous phase
on emulsion polymerization with STy. Investigations
on the nucleation and particle growth of acrylate ester
latexes containing various amounts of IA have shown
that the major effect of IA is to decrease the number
of particles formed in the earlier stages of emulsion
polymerization.12 Oliveira et al.1 demonstrated that
the kinetics of the polymerization of methyl methac-
rylate with n-butyl acrylate (MMA/BA) in the pres-
ence of IA was slower than the copolymerization of
the MMA/BA.
Given the industrial and scientific importance of
carboxylated latexes, especially concerning the use of
IA1,2,12 in latexes used for architectural coatings, the
main objective of this study was to determine the
optimal conditions regarding IA concentration and wet
scrub resistance to produce architectural coatings. IA
(methylene succinic acid) is a white, crystalline, unsat-
urated, dicarboxylated, vinyl monomer with one car-
boxyl group conjugated to the methylene group. IA is
commercially produced by the cultivation of Aspergil-
lus terreus with molasses. It can be incorporated into
polymers and may serve as a substitute for petrochem-
ical-based AA or MAA.13
In this article, the study of the emulsion copolymer-
ization of STy with BA in the presence of IA is
presented. The objective of this study was to under-
stand the effects of the amount and carboxylic acid
distribution on the wet scrub resistance of highly
pigmented paints for architectural coatings. Consider-
ing the technological importance of this carboxylic acid
and the lack of reported data about the effects of the
IA, the distribution on the wet scrub resistance of
highly pigmented paints for architectural coatings
was studied. The effects of the IA on the overall
440
conversion, colloidal properties of the latexes, as well
as on the distribution of the carboxylic groups (buried,
particle surface and aqueous phase) are discussed.
Experimental
Materials
Except for the IA, an inhibitor-free grade (99.90%),
industrial grade-inhibited monomers, STy and BA,
were received from BASF and used throughout the
reactions. The initiator, potassium persulfate (K2S2O8),
of 99% purity grade (Merck) was recrystallized before
use. The emulsifier, sodium lauryl sulfate (SLS) and
modified ethoxylated fatty alcohols POE 30 (DisponilÒ
A 3065) of commercial purity grade, were used as
received. All polymerizations and analyses of carbox-
ylic group concentration were carried out with deion-
ized water. The latex samples were cleaned using a
mixed-bed ion-exchange resin (Dowex-MR3, Dow).
To adjust the viscosity of the paints, an associative
thickener (LatekollÒ BA 978, BASF) was used. To
prepare the paints, all materials (Table 2) were used as
received.
Polymerization
The functional monomer (IA) was incorporated into
the latex particles by a semi-continuous STy/BA
emulsion copolymerization process employing a 5-L
glass reactor equipped with a mechanical stirrer and a
condenser. The temperature of the water in the cooling
jacket was kept constant by a controlled temperature
bath. Pre-emulsions (Table 1) were added at a constant
feed rate over a period of 4 h and the potassium
persulfate solution was added at a constant feed rate
over a period of 5 h. All the polymerizations were
carried out at 80°C at 50% solid content (mass of
monomers with respect to total reaction mass). The
different formulations and experimental conditions for
all syntheses of latexes are reported in Table 1. The
monomer conversion was determined by gravimetric
analyses on the samples collected from the reaction
mixture. The reaction was stopped immediately after
sampling by using a 1% w/w hydroquinone solution in
combination with an ice–water bath. The contents were
dried (at 105°C) in an oven to attain a constant weight.
The conversion was calculated according to the fol-
lowing equation:


SCðtÞ  MRðtÞ  MSðtÞ
ConversionðtÞ ¼ ð1Þ
MMðtÞ
where SC(t), MR(t), MS(t), and MM(t) are solid content,
weight of the reactor contents, weight of the solids
(emulsifier, initiator), and weight of the monomers in
the reactor at time (t), respectively.
 Author's personal copy
J. Coat. Technol. Res., 8 (4) 439–447, 2011

Table 1: Recipe for the synthesis of carboxylated latexes using a semi-continuous emulsion polymerization
Reagents (g) SBA IA-1 IA-2 IA-3 IA-4

Pre-emulsiona
H2O 689.6 689.6 689.6 689.6 689.6
STy 980.0 960.0 940.0 920.0 900.0
BA 980.0 980.0 980.0 980.0 960.0
IA – 20.0 40.0 60.0 80.0
SLS 21.6 21.6 21.6 21.6 21.6
A 3065b 13.0 13.0 13.0 13.0 13.0
Reactor initial charge
H2O 1000.0 1000.0 1000.0 1000.0 1000.0
SLS 12.0 12.0 12.0 12.0 12.0
Initiator
H2O 300.0 300.0 300.0 300.0 300.0
K2S2O8 3.8 3.8 3.8 3.8 3.8
a
Was added over 4.0 h
b
Modified ethoxylated fatty alcohols POE 30

Composition and paint formulation

Table 2: Paint formulation used in this study
The highly pigmented paints were formulated using a Reagents (g)
standard recipe (Table 2) with TiO2 as pigment and
precipitated calcium carbonate as filler. In all the Grind at high speed for 20 min
paints, the total amount of the materials was kept Water 72.80
constant. The pigment volume concentration (PVC) Tetrapotassium pyrophosphate 0.15
was set to 90% with 8% of carboxylated latexes. To UltradispersÒ MD-21 1.20
prepare a white base, both pigment and filler were DisponilÒ 15B 0.15
dispersed using a typical lab high-speed disperser Ammonium hydroxide (25%) 0.30
(700 rpm) having a double-bottom container water- Defoamer 0.30
cooled at 30°C. The sodium salt of a copolymer of Butylglycol 1.20
maleic acid and diisobutene (UltradispersÒ MD-21) Precipitated calcium carbonate 113.00
were used as dispersing agents. The fineness of the Titanium dioxide (rutile) 12.00
grinding was measured using a BYK Gardner grin- Mix for 10 min at 200 rpm
dometer. The size of the dispersed phase was observed Water 58.00
to be less than 10 lm in diameter. The latex was finally Butylglycol 4.60
added to the pigment slurry followed by viscosity Defoamer 0.40
adjustment using an associative thickener. To investi- Dispersion (50% solids)a 30.0
gate the influence of water-soluble polymer, the Ammonium hydroxide (25%) 0.30
dialyzed latex was used in the paint formulation. In Preservative 0.20
this procedure, surfactant and oligomers were removed Associative thickener (25%) 5.40
from the sample. After 24-h period, the paint was then a
Dispersions obtained in this study (SBA, IA-1, IA-2, IA-3
drawn down onto a PVC foil (Leneta) with a dry and IA-4)
thickness of 175 lm. The sample was allowed to dry for
7 days at 23°C and 55–65% relative humidity. The
materials and white-base formulation are given in Viscosity and pH
Table 2.
The viscosity was measured in a Brookfield viscosim-
eter at 25°C (method LVT with spindle number 1 at
Characterizations 60 rpm). The pH was measured in a Metrohm pH
meter at 25°C.
Particle size analysis

The latexes were characterized in terms of average Coagulum formation

particle diameter by the light scattering technique,
using the Mastersizer 2000G instrument (Malvern) at The amount of coagulum after the polymerizations was
25°C. All measurements were performed in triplicate measured by screening out the coagulum using a
on highly diluted aqueous dispersions. stainless steel screen (125 mesh). An aliquot of 50 g

441
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J. Coat. Technol. Res., 8 (4) 439–447, 2011

of original latex was diluted with approximately 500 g
water, stirred for 10 min at room temperature, filtered,
and the residual amount calculated by means of
gravimetric analyses.
Freeze–thaw stability
The freeze–thaw stability of the polymer latexes was
determined by placing the latex in a freezer at 18°C
for 24 h and then removing it and leaving it at room
temperature for another 24 h. This completes one
freeze–thaw cycle.
foil with a dry film thickness of 175 ± 5 lm. The
coating thickness has to be checked carefully. After
drying for 7 days, the test was performed wet, since
during the test a soap solution drops onto the coating.
The final scrub resistance was reached when the first
spot of Leneta foil appeared indicating that the paint
layer had been removed, and so a higher number of
cycles show a more scrub-resistant paint. Three panels
were tested, and the average of the four most similar
panels was rated.
Optical property

The optical property was studied by evaluating con-

Carboxylic group distribution
The latexes were purified using the method described in
the literature using a mixed-bed ion-exchange resin.1
They were diluted to 2.0% solid content (by mass) using
deionized water of conductivity 1.8 lS cm1. In this
study, two methods were used for determining the
carboxylic group’s distribution: conductometry to eval-
uate the number of carboxylic groups on the surface of
the latex particles, and titration with NaOH in meth-
anol solution to determine the number of carboxylic
groups inside and on the surface of the latex parti-
cles.1,8,14,15 The concentration of carboxylic groups in
the serum (water phase) was determined by centrifu-
gation and conductometric titration by means of a mass
balance, i.e., deduced from the initial amount of
carboxylic monomer introduced and the determined
amounts of carboxylic groups inside and at the surface
of the latex particles. The number of carboxylic groups
on the particle surface was determined by titration of a
cleaned latex solution against a 0.05 N NaOH. The
degree of incorporation of acid groups inside and on the
surface of the latex particles was evaluated by poten-
tiometric analysis in an organic medium. The purified
polymer was dissolved in 100 mL of tetrahydrofuran to
obtain solutions with three different concentrations and
titrated using a 0.05 N NaOH solution in methanol.1
Because all the methods involving acid base chemistry
are very sensitive to the presence of CO2, every
experiment was performed under nitrogen atmosphere.
trast ratio value.17 The instrument used was spectro-
photometer, Datacolor International, model Spectra
Flash SF 6000.
Results and discussion
Overall conversion and particle size
Figure 1 shows the conversion–time curves for semi-
continuous emulsion polymerization of STy with BA.
The presence of IA had a negative influence on the
rate of copolymerization as well as the copolymer
conversion. The polymerizations performed by increas-
ing the carboxylic monomer concentration from 0.5%
to 2.0% show a successively stronger reduction in the
polymerization rate (Fig. 1). In this study, a water-
soluble initiator was used to form radicals. These
radicals react with monomer dissolved in the aqueous
phase to form soluble oligomeric radicals. It is postu-
lated that a radical of IA can terminate the propaga-
tion step in a homopolymerization reaction. It is also
100
90
80
70
Conversion (%)

For each series of analysis, a blank was carried out to 60

determine the acidity of the solvent. The carboxylic 50
groups located in the interior of the particles could be
computed by the difference between the conductomet- 40
SBA (0%)
ric and potentiometric titrations. 30 IA-1 (0.5%)
IA-2 (1.0%)
20
IA-3 (1.5%)
Wet scrub test 10 IA-4 (2.0%)
0
Wet scrub resistance was evaluated quantitatively as
0 30 60 90 120 150 180 210 240 270 300
the number of cycles required to scrub off a paint film Time (min)
with a brush.16 During the test, a soap solution was
poured drop wise on the coating. The experiments Fig. 1: Overall conversions vs time for the emulsion
were carried out in typical relative humidity of a copolymerizations of STy and BA in the presence of
laboratory (50–65%). The paint was coated on Leneta different IA concentrations

442
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J. Coat. Technol. Res., 8 (4) 439–447, 2011

known that the use of water-soluble carboxylic acids in
emulsion polymerization reactions normally leads to
the formation of water-soluble species. The polarity of
an acid monomer radical formed in the core of the
particles by a chain transfer mechanism can cause their
migration to the aqueous phase, resulting in the
reduction of the average number of radicals per
particle, n, and consequently, in the reduction of the
overall rate of polymerization.18 In spite of the low
concentration of IA used in the present study, the
assumption mentioned above would explain the lower
polymerization rate observed for the reaction per-
formed in the presence of this functional monomer
(Fig. 1).
The effect of IA on the rate of copolymerization has
been discussed in the literature.1,12,19 It is proposed
that IA forms a sterically hindered propagating radical
and that this radical is unlikely to react with another IA
unit. Václavová et al.19 demonstrated that the IA has a
negative influence on the rates of the copolymerization
of BA/IA and STy/IA. According to those authors, this
influence increased significantly with increasing the
amount of IA in the monomer feed. A similar behavior
180
170
160
150
Particle diameter (nm)
was observed by Ceska20 in the STy/butadiene copo-
lymerization performed in the presence of IA. Egusa
and Makauuchi21 demonstrated that the copolymeri-
zation rate of STy and carboxylic acid increases with an
increase in the acid monomer content for AA and
MAA, whereas for IA, the rate decreases. Oliveira
et al.1 demonstrated that the kinetics of the polymer-
ization of MMA/BA in the presence of IA and AA was
slower than the copolymerization of the MMA with
BA.
Figure 2 shows the average particle diameter–time
curves for the STy/BA copolymerizations using differ-
ent IA concentrations. The particle diameter increased
significantly with increasing IA content. These results
show that a major effect of IA is to decrease the
number of particles nucleated. Further, the presence of
this carboxylated monomer causes flocculation of the
primary particles by some destabilization process, such
as the polymerization (IA-4) with 2.0% of IA. The
increase in the average particle diameters was also
observed in the copolymerization of methyl acrylate
with BA using different concentrations of IA.12 The
incorporation of IA into the polymer chain occurs on
the surface of the polymer particles during the copo-
lymerization of STy and BA by a homogeneous
nucleation and coagulation. The particle size formed
increased significantly as the amount of IA was
increased. During the course of copolymerization,
significant change in the particle diameter occurs,
indicating the flocculation of existing particles. The
analysis of the particles by the light scattering tech-

140
130 nique reveals that the latex with 2.0% of IA shows a
120 bimodal mode.
110 Table 3 shows that the pH values for the latexes that
100
contained IA ranged from 4.0 to 3.0, whereas that for
90
the latex made without IA was 5.7. The pH is
SBA (0%) important since the rate of consumption of the IA
80 IA-1 (0.5%) depends on the pH of the reaction medium, and it will
70 IA-2 (1.0%)
define the ionic nature that will, in turn, influence
60 IA-3 (1.5%)
IA-4 (2.0%) directly the reactivity ratios as well as the Kp of the
50
IA.1 Table 3 shows that the viscosity of the latexes
40 decreased with increased IA concentration at low pH
0 30 60 90 120 150 180 210 240 270 300
Time (min)
values. The decrease in viscosity is connected with an
increase of the particle size and an increased proba-
Fig. 2: Particle diameter vs time for the emulsion copoly- bility of an IA reaction with a propagating radical. In
merizations of STy and BA in the presence of different IA this case, shorter polymer chains with an IA unit are
concentrations formed.

Table 3: Properties of the final latexes

Properties Latexes
SBA IA-1 IA-2 IA-3 IA-4

Viscosity (mPaÆs) 1100 900 850 150 75

Dp (nm) 110 119 126 135 152
pH 5.7 4.0 3.8 3.4 3.0
Coagulum (ppm) 190 300 420 570 2430

443
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J. Coat. Technol. Res., 8 (4) 439–447, 2011
Distribution of carboxyl groups
Understanding the latex morphology and especially
the location of the hydrophilic monomer (IA) in the
polymer particles would provide information about the
mechanisms of wet scrub resistance. The distribution of
IA groups in our latexes was investigated by conduc-
tometric and potentiometric titration. In accordance
with Fig. 3, one can observe that the IA is differently
distributed in the three phases of the system (buried/
surface/water phase). The acid groups were predomi-
nantly located in the aqueous phase and on the particle
surface, with only a small proportion located and
buried in the latex particles. At a concentration of
0.5% w/w of IA, the final pH was 4.0 (latex IA-1), and
the concentration of carboxylic acid buried in the latex
particles was less when compared with the fraction of
carboxylic groups for the other latexes. In the case of
the latex with 2.0% w/w of IA (latex IA-4), the analysis
indicated a very large amount of IA in the aqueous
phase (59% w/w) and the particle surface (32% w/w).
The results shown in Fig. 3 demonstrate that the
distribution of the carboxyl groups present in the final
latex is greatly dependent on the water solubility of the
carboxylic monomer (IA), the hydrophilic nature of IA
under acidic conditions, and the amount of IA in the
monomer feed. In this study, the final latexes had a pH
from 4.0 to 3.0. At low pH, IA is in the un-ionized form
and, therefore, less hydrophilic form, which is less
polar than the dissociated form found at higher pH
values. Moreover, under certain conditions, the car-
boxylic groups tend to be located in the water phase
forming hydrosoluble compounds or generating new
particles by homogeneous nucleation. The IA copoly-
merizes with other monomers, i.e., STy or BA and
tends to make random copolymers. In this case,
we could expect the formation of particles with a
80
Buried
70 Surface
Aqueous phase
60
COOH groups (%)
50
40
30
20
10
0
0.5 1.0 1.5
Itaconic acid (% w/w)
Fig. 3: Amounts of acid groups at different phases of the
emulsion system (buried, surface of particles and aqueous
phase) as a function of the IA in the monomer feed
444
hairy-layer-like morphology, depending, of course, on
the amount of IA used in the monomer feed. The
distribution of the carboxyl groups has been previously
exploited in the literature.1,7,12 It is proposed that IA
forms a sterically hindered propagating radical and
that this radical is unlikely to react with another IA
unit.
The results from this study are useful because they
allow us to better understand the different profiles of
the carboxylic groups distributions for the latexes
obtained in this study. The data reveal that most of
the acid resides in the aqueous phase and that different
concentrations of carboxylic acid in the aqueous phase
have a larger influence on the wet scrub resistance and
the viscosity of the latexes (Table 3). These results
showed that IA was insufficient to produce a stable
emulsion, even when its concentration was increased
from 0.5% to 2.0% w/w of the monomer (Table 3). In
this case, the latex stability decreased in the reactions
with a higher IA concentration. Increasing the con-
centration of functional monomer (2.0% w/w) leads to
the increase of the coagulum formation. Coagulum is
formed as a consequence of colloidal instability of the
latex particles as well as of higher kinetic energy of the
particles.22 In this study, the variables that affected
the coagulum formation were the amount of IA added
in the formulation and the pH of the reaction medium.
For the same copolymerization process and tempera-
ture, the coagulation rate depends only on the number
of latex particles and, therefore, the coagulum amount
in the latex was increased with the concentration of IA.
The freeze–thaw stability of polymer latexes is of
considerable industrial importance, because of the
need to store and transport these products within cold
areas. The results showed that all the latexes coagu-
lated completely in the third cycle (Fig. 4). There was
no improvement in the latex stability with increasing
IA concentration. No changes were observed between
carboxylated latexes and noncarboxylated latex
(SBA). At a low pH (high IA content), the latexes
3
Stability (cycles)
1
2.0
0
SBA IA-1 IA-2 IA-3 IA-4
Latexes
Fig. 4: Freeze–thaw stability of functionalized latexes
 Author's personal copy
were even less stable than the latex without IA (latex
SBA), indicating that the addition of IA did not
improve the colloidal stability. The steric stabilization
effect is lowered at lower pH because the solubility of
water-soluble polymer is less than that at high pH.
Increasing the pH leads first of all to an increase in the
ionic strength of the latex and contributes to a
contraction of the electronic double layer, which has
a certain influence on the stability. In accordance with
Blackley,23 the freezing process started with the
reduction of temperature, which led, to the appearance
of a third phase (ice crystals), resulting in rapid particle
aggregation and interparticle coalescence.
Scrub resistance of dried paint film
The primary objective of this study was to investigate
the effect of functional monomer (IA) on the wet scrub
resistance of highly pigmented paints. The influence of
IA on the wet scrub resistance is shown in Fig. 5. The
results indicate that, generally, the IA gives better wet
scrub resistances for lower IA concentrations when
compared with high IA concentrations. It can be seen
that lower IA monomer contents (0.5–1.0% w/w)
resulted in a higher scrub resistance than the higher
level (2.0% w/w). The oligomeric radicals with a very
high IA content remained in the aqueous phase,
presumably became terminated, and formed a water-
soluble polymer. Their solubility increased with
increasing IA content in the monomer feed. However,
these water-soluble polymers lead to low wet scrub
resistance which has a negative effect on end-use
properties, such as the water resistance of the coating.
The abrasion test (Fig. 5) was performed under wet
conditions, and so the main factors affecting the results
will be the pigment binding ability of the latex and the
hydrophilicity of the latex. The differences in the
latexes, which could account for the abrasion results,
may be because of the varying hydrophilicities of the
200
180
160
140
Scrub cycles
120
100
80
60
Original latexes
40 Dialyzed latexes
20
0.0 0.5 1.0 1.5
Itaconic acid (% w/w)
Fig. 5: Effect of the amount of itaconic acid on the wet
scrub resistance of dried paint film
J. Coat. Technol. Res., 8 (4) 439–447, 2011
latex caused by modifying the particle surface. After
latex purification, the paints obtained gave rise to
better performance for all IA concentrations.
In contrast to the behavior observed in this study,
Kirsch et al.24 showed that there was no difference
between the original and dialyzed latexes. This result
was attributed to a strong adsorption of the water-
soluble polymer onto the surface of the latex particle.
In such a case, we could expect that the formation of
particles with a hairy-layer-like morphology is more
favorable than that formed in the aqueous phase. In
other words, these water-soluble polymers give rise to
improved wetting properties and are effective in
breaking up filler and pigment (CaCO3 and TiO2)
agglomeration.2 Khorassani et al.,5 suggest that the
higher polarity of carboxylic acid led to increased
water permeability of the dried paint film. The pres-
ence of carboxylic groups increases the wetting and
adhesion properties of the pigment–latex and filler–
latex systems.
The effect of latex particle size on the wet scrub
resistance was examined, and the general trend
observed was the decreased value of the scrub resis-
tance of the paint as the latex particle size increases
(see Fig. 5 and Table 3). In this case, there are
differences in the effectiveness of film formation
quality, which have the greatest influence over wet
scrub resistance of the dried film and their ability to
disperse pigment or filler. From the results shown in
Fig. 5 and considering the effect of latex particle size
on the wet scrub resistance, we could confirm the
assumptions made by Wildeson et al.2 and Khorassani
et al.5
The hiding power of paint is evaluated by measuring
the opacity of the highly pigmented paint. The effect of
IA in hiding power was not quite clear. No appropriate
tests were available for determining reproducible
hiding power values of the paint formulations. The
results show (Table 4) that the contrast ratio of the
highly pigmented paint with auxiliary monomers, such
as IA, give rise to better performance compared to the
one without IA. Latexes with 0.5% and 1.5% of IA
show the best result in this regard. During the mill-
grinding stage, the pigment-particle agglomerates are
broken down and stabilized by the dispersant and the
water-soluble polymers on the particle surface. Vari-
ations in surface roughness between paint films were
immediately observed onto a glass substrate. Latexes
Table 4: Opacity of the paints with different IA compo-
sitions
Paint IA (% w/w) Opacity (contrast ratio)
1 0 90.26
2.0 2 0.5 93.25
3 1.0 93.84
4 1.5 94.07
5 2.0 91.72
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J. Coat. Technol. Res., 8 (4) 439–447, 2011
with high IA concentration on the particle surface are
the most effective at achieving even dispersal of the
pigment and filler particles than that low IA concen-
tration. A similar behavior was observed by Wildeson
et al.2 in the acrylic latexes performed in the presence
of different carboxylic acids. Thus, these latexes
potentially can be applied as an alternative to reduce
pigment in paints.
Conclusions
The kinetics of the semi-continuous emulsion poly-
merization of STy with BA is affected by the presence
of IA. The presence of IA has a negative influence on
the rate of copolymerization as well as the copolymer
conversion. The difference observed in the kinetics in
the presence of IA was very significant. The particle
diameter increased significantly with increasing IA
content. The ionizing comonomer was responsible for
the increase of the average particle diameter. This fact
was attributed to the formation of a higher number of
particles due to the more accentuated ability of IA to
induce particle formation by a homogeneous nucle-
ation mechanism.
The IA is distributed differently in the three phases of
the emulsion system (particle buried, particle surface,
and aqueous phase). A small fraction of this acid was
found buried inside the particles, and the remaining was
distributed between the particle surface and in higher
concentration, in the aqueous phase. The water-soluble
polymers present in higher concentration in the aqueous
phase led to low wet scrub resistance. Paints prepared
with latexes with a lower proportion of IA were more
resistant to abrasion than those with the higher IA
concentration. After latex purification, the paints
obtained with low IA concentration give rise to better
performance compared with high IA concentration.
The amount of IA used in emulsion polymerization
affects numerous factors, including particle size,
freeze–thaw stability, kinetics, coagulum formation,
wet scrub resistance, hiding power, and water sensitiv-
ity. It may be concluded that to obtain latexes with a
high wet scrub resistance, information about the
distribution of carboxylic groups is generally needed
to tune the synthesis procedure, and that for this
system, a concentration of 0.5% w/w in recipe was
found to be the best.
References
1. Oliveira, MP, Giordani, DS, Santos, AM, ‘‘The Role of
Itaconic and Fumaric Acid in the Emulsion Copolymeriza-
tion of Methyl Methacrylate and n-Butyl Acrylate.’’ Eur.
Polym. J., 42 1196–1205 (2006)
2. Wildeson, J, Smith, A, Gong, X, Davis, HT, Scriven, LE,
‘‘Understanding and Improvement of TiO2 Efficiency in
Waterborne Paints Through Latex Design.’’ JCT Coatings-
Tech, 5 32–39 (2008)
446
3. Fukuhara, D, Sundberg, D, ‘‘Latex Produced with Carbox-
ylic Acid Comonomer for Waterborne Coatings: Particle
Morphology Variations with Changing pH.’’ J. Coat. Tech-
nol. Res., 2 509–516 (2005)
4. Vorwerg, L, Gilbert, RG, ‘‘Electrosteric Stabilization with
Poly(acrylic acid) in Emulsion Polymerization: Effect on
Kinetics and Secondary Particle Formation.’’ Macromole-
cules, 33 6693–6703 (2000)
5. Khorassani, M, Afshar-Taromi, F, Mohseni, M, Pourmahdian,
S, ‘‘The Role of Auxiliary Monomers and Emulsifiers on Wet
Scrub Resistance of Various Latex Paints at Different Pigment
Volume Concentrations.’’ J. Appl. Polym. Sci., 113 3264–3268
(2009)
6. Koh, AYC, Mange, S, Bothe, M, Leyrer, RJ, Gilbert, RG,
‘‘The Influence of Copolymerization with Methacrylic Acid
on Poly(butyl acrylate) Film Properties.’’ Polymer, 47
1159–1165 (2006)
7. Vijayendran, BR, ‘‘Effect of Carboxylic Monomers on Acid
Distribution in Carboxylated Polystyrene Lattices.’’ J. Appl.
Polym. Sci., 23 839–901 (1979)
8. Fordyce, RG, Ham, GE, ‘‘Copolymerization. II. The Mech-
anism of Emulsion Copolymerization of Styrene and Itaconic
Acid.’’ J. Am. Chem. Soc., 69 695–696 (1947)
9. Santos, AM, McKenna, TF, Guillot, J, ‘‘Emulsion Copoly-
merization of Styrene and n-Butyl Acrylate in Presence of
Acrylic and Methacrylic Acids: Effect of pH on Kinetics and
Carboxyl Group Distribution.’’ J. Appl. Polym. Sci., 65
2343–2355 (1997)
10. Santos, AM, Guillot, J, McKenna, TF, ‘‘Partitioning of
Styrene, Butyl Acrylate and Methacrylic Acid in Emulsion
Systems.’’ Chem. Eng. Sci., 53 2143–2151 (1998)
11. Reynhout, XEE, Beckers, M, Meuldijk, J, Drinkenburg,
BAH, ‘‘Electrosteric Stability of Styrene/Acrylic Acid
Copolymer Latices Under Emulsion Polymerization Reac-
tion Conditions.’’ J. Polym. Sc., Part A: Polym. Chem., 43
726–732 (2005)
12. Lock, MR, El-Aasser, MS, Klein, A, Vanderhoff, JW, ‘‘Role
of Itaconic Acid in Latex Particle Nucleation.’’ J. Appl.
Polym. Sci., 42 1065–1072 (1992)
13. Willke, Th, Vorlop, KD, ‘‘Biotechnological Production of
Itaconic Acid.’’ Appl. Microb. Biotechnol., 56 289–295 (2001)
14. Slawinski, M, Schellekens, MAJ, Meuldijk, J, van Herk, AM,
German, AL, ‘‘Seeded Emulsion Polymerization of Styrene:
Influence of Acrylic Acid on the Particle Growth Process.’’
J. Appl. Polym. Sci., 76 1186–1196 (2000)
15. Araújo, PHH, Sayer, C, Caldas, E, Santos, AF, Fortuny, M,
‘‘Investigation of Stabilization and Kinetics in the Semi-
Continuous Emulsion Copolymerization of Vinyl Acetate
and Butyl Acrylate Using Carboxylic Monomers.’’ Macro-
mol. Symp., 245–246 61–67 (2006)
16. ABNT, NBR 15078 ‘‘Método para avaliação do desempenho
de tintas para edificações não industriais—Determinação da
resistência à abrasão úmida sem pasta abrasiva,’’ Rio de
Janeiro, 2006
17. Khan, AK, Roy, BC, Dolui, SK, ‘‘Preparation of Core–Shell
Emulsion Polymer and Optimization of Shell Composition
with Respect to Opacity of Paint Film.’’ Prog. Org. Coat., 62
65–70 (2008)
18. Bajaj, P, Meenakshi, G, Chavan, RB, ‘‘Synthesis and
Characterization of Methacrylic Acid-Ethyl Acrylate
Copolymers.’’ J. Appl. Polym. Sci., 53 1771–1783 (1994)
19. Václavová, E, Hrivı́k, A, Chrástová, V, ‘‘Emulsion Copoly-
merization of Styrene and Butyl Acrylate with Itaconic
Acid.’’ Makrom. Chem., 193 2243–2250 (1992)
20. Ceska, GW, ‘‘Carboxyl-Stabilized Emulsion Polymers.’’
J. Appl. Polym. Sci., 18 2493–2499 (1974)
 Author's personal copy
21. Egusa, S, Makauuchi, K, ‘‘Radiation-Initiated Emulsion
Copolymerization of Styrene and Carboxylic Acid Mono-
mers.’’ J. Polym. Sci. Polym. Chem., 20 863–874 (1982)
22. Vanderhoff, JW, ‘‘The Making of a Polymer Colloid.’’ In:
Poehlein, GW, Ottewill, RH, Goodwin, JW (eds.) Science
and Technology of Polymer Colloid, p. 167. Martinus Nijhoff,
The Hague, The Netherlands, 1983
View publication stats
J. Coat. Technol. Res., 8 (4) 439–447, 2011
23. Blackley, DC, Polymer Latices—Science and Technology,
Vol. 1. Chapman & Hall, London, 1997
24. Kirsch, S, Pfau, A, Frechen, T, Schrof, W, Pföhler, P,
Francke, D, ‘‘Scrub Resistance of Highly Pigmented
Paints. A Study on Abrasion Mechanisms of Dif-
ferent Scrub Techniques.’’ Prog. Org. Coat., 43 99–110
(2001)
447