Progress in Organic Coatings 77 (2014) 10631068

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Progress in Organic Coatings
j our nal homepage: www. el sevi er . com/ l ocat e/ por gcoat
Synthesis and characterization of polystyrene-acrylate/polysiloxane
(PSA/PSi) core shell polymers and evaluation of their properties for
high durable exterior coatings
Kamakshi. R. Christopher

, Amarjeet Pal, Girish Mirchandani, Tapan Dhar

Asian Paints Research & Technology Centre, Plot No C-3B/1 TTC Industrial Area, MIDC Pawane, Thane Belapur Road, Navi Mumbai 400703, India
a r t i c l e i n f o
Article history:
Received 3 January 2013
Received in revised form23 January 2014
Accepted 14 March 2014
Keywords:
Coreshell latex
Morphology
Acrylic siloxane hybrids
Exterior coatings
Emulsion polymerization
a b s t r a c t
Poly acrylic siloxane coatings are generating a lot of interest due to their high durability and superior
performance properties in different applications. However, synthesis of high siloxane containing acrylic
binder through emulsion polymerization is a challenge. Herein, we present a study on the synthesis and
characterization of polystyrene-acrylate/polysiloxane core shell latex systems through regular seeded
emulsion polymerization. Hybrid polymers have been characterized for their physical, chemical, thermal
and surface properties using different characterizing techniques like FTIR, DSC, DMA, SEM, TEM, DLS
and contact angle measurements. Incorporation of polysiloxane in the shell of the polymer particle was
found to improve hydrophobicity and mechanical properties. Exterior paints prepared using the hybrid
polymers as binders exhibited superior performance properties like weather ability and dirt pick up
resistance.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Coatings that exhibit high durability are of enormous relevance
today [15]. Acrylic polymers are widely used in architectural coat-
ings because of their high durability and aesthetic appeal. Acrylic
copolymers provide good water and alkali resistance, elasticity and
adhesive properties [6]. They are broadly classied into styrene
containing latexes and styrene-free latexes and both are widely
used in coatings, paints and adhesives so far by virtue of their
excellent lm-forming property, cohesiveness and drying ability.
Styrenewhenusedas amonomer provides goodhardness, strength,
adhesion and water resistance to the latex lms and therefore
nds application in many architectural coatings. However, styrene
basedpolymers are prone toyellowing under ultra-violet (UV) light
leading to the loss in aesthetic appeal of coatings [7]. Styrene-free
latexes are generally used for outdoor coatings but these are also
plagued by failure to sustain their gloss, hardness and weathering
properties and hence the surface needs to be recoated [8]. There-
fore, there exists a scope for improvement latex systems that can
yield better performance for outdoor applications.

Corresponding author. Tel.: +91 22 39153434.

E-mail address: kamakshi.christopher@asianpaints.com
(Kamakshi.R. Christopher).
Approaches to enhance exterior durability include the use of
uoro monomers or siloxane-acrylates as co-monomers or post
polymerization additives in the latex. While the uoro monomers
are prohibitively expensive, organo-siloxane monomers or inter-
mediates present a system that can provide good cost to benet
performance. Polysiloxane is endowed with excellent thermal sta-
bility, low surface energy, weather resistance, high exibility and
good biological compatibility owing to its unique structure [911].
Therefore, a systemthat is synthesized through emulsion polymer-
ization route that properties of both acrylates and polysiloxanes
would be highly preferred as binders for paints. In the past decade,
research on silicone or polysiloxane modied polyacrylate and
poly (acrylate-styrene) systems have been extensively studied.
Silicone-acrylic resin composed of 30wt% 3-methacryloxypropyl
trimethoxysilane (MPTS) was noted to be a super-weatherable
coating that showed improved properties like gloss retention,
yellowing index difference, color difference, and lightness index
differences [12,13].
Synthesis of siloxane modied acrylics is relatively easy in
non aqueous medium but poses a challenge through traditional
emulsion polymerization technique. This is due to the inher-
ent vulnerability of alkoxy silane group to undergo hydrolysis
that may affect processing and cause a loss in mechanical prop-
erties. Alternate methods including use of hydrolysis resistant
monomers, barrier techniques and mini-emulsion processing are
being attempted to control this adverse reaction [14,15]. However,
http://dx.doi.org/10.1016/j.porgcoat.2014.03.008
0300-9440/ 2014 Elsevier B.V. All rights reserved.
1064 Kamakshi.R. Christopher et al. / Progress in Organic Coatings 77 (2014) 10631068
Fig. 1. Schematic representation of the synthesis of core shell polymer.
these procedures involve newreactor designs and longer process-
ing times that may not be commercially feasible.
An area of recent advancement in developing hybrid polymers
is in modifying the morphology of latex particles while process-
ing through regular seeded emulsion polymerization. Structured
particles such as core shell, raspberry type, and gradient phase
polymers showadvanced performance properties due to their spe-
cial morphological structure [16]. Core shell particles containing
polyacrylate core and polysiloxane shell are the most favored type
owing to their superiority in performance [17]. Recently, Fei and
co-workers [2] have discussed incorporation of siloxane shell up
to 8% in polystyrene acrylate using polymerisable surfactant and
studied its effects in paper sizing. The characterization of the core
shell particles presents a challenge in itself [18]. Most researchers
have relied on transmission electron microscopy (TEM) that shows
a typical contrast difference as per morphology. In certain struc-
tures wherein the chemistry of the core and shell are similar, other
analytical techniques like scanning electron microscopy (SEM),
dynamic light scattering (DLS), solid state nuclear magnetic reso-
nance (NMR), atomic force microscopy (AFM), differential scanning
calorimetry (DSC) and dynamic mechanical analysis (DMA) have
also been used to identify such morphology in latexes [1923].
In this study we present a simple methodology to synthe-
size core shell latexes with polystyrene-acrylate (PSA) core and
polysiloxane (PSi) shell using conventional seeded emulsion poly-
merization. In this method, the polystyrene-acrylate core is cross
linked with the organosiloxane intermediate to give hybrid poly-
mer (Fig. 1). The process helps to incorporate siloxane in the shell
ranging from 5% to 30%. Morphology of the PSA/PSi hybrid poly-
mers has beencharacterizedby TEM, DLS andDMA andshows clear
phase separated regions in the latex. The surface properties show
an increase in water repellency with increased siloxane content.
White paints formulated using the hybrid binders show superior
weatherability and mechanical properties.
2. Experimental
2.1. Materials and methods
All monomers were of commercial grade and used as such.
Siloxane intermediate was purchased from Dow Corning. Anionic
Table 2
Formulation of the white paint for testing the hybrid lattices.
Material used Weight %
Cellulose thickener 0.5
Surfactant (anionic) 0.5
Defoamer 0.1
Antifungal 1.0
Rutile TiO
2
21
Marble powder (10 micron) 7
Calcined clay 6
Coalescent 1
Binder 40
In-can preservative 1.0
Water 21.9
surfactant (Galaxy), persulfate initiator, oxidant, reductant and
buffer were of commercial grade and were used as such.
Fourier TransformInfra Red spectroscopy (FTIR) measurements
were carried out on Perkin-Elmer Spectrum 1. X-Ray orescence
characterization was performed in BRUKER AXS INC. S
2
RANGER
XRF instrument. Particle size of the synthesized emulsions (diluted
1:50 withwater) was measuredonZeta Potential Analyzer Zetatrac
Model NPA152 (Microtrac Inc). DSC analyses were carried out on
48h dried lms using a TA Instruments Q10 under nitrogen atmo-
sphere at a ramp of 10

C within the temperature range of 50

C to
100

C. Dynamic mechanical analysis was performed on paint lms

using dynamic mechanical analyzer (TA Q800). Contact angle of
emulsion lms was evaluated using the sessile drop method, mea-
sured on a glass plate using 3S surface tensiometer. Whiteness and
color change were measured in spectrophotometer.
2.2. Experimental method of styrene-acrylic latex synthesis
Polymerization was performed in a one liter, three-neck ask
equipped with a mechanical stirrer, a temperature control system,
an inlet for a monomer emulsion fed by a peristaltic pump, and
a reux condenser. Emulsion latex was prepared through seeded
semi continuous emulsion polymerization at 75

C using persul-
fate as the initiator and a pre-emulsion made of anionic/nonionic
combination surfactants with styrene and butyl acryate as co-
monomers. The addition was carried out for a period of 4h and
then cooled after a hold period of 1h.
To the styrene-acrylate core, organosiloxane intermediate
that contains methoxy linkages was added drop-wise into
kettle by using peristaltic pump and the reactions were pro-
cessed at room temperature until homogenous emulsions were
obtained. Finally the emulsion latex was ltered and polystyrene-
acrylate/polysiloxane hybridlatexwas obtained. Sevenexperimen-
tal sets wereprocessedusingtheabovemethodas showninTable1.
2.3. Preparation of white paints
White paints were made by stirring the millbase and polymer in
a 60:40 ratio as given in Table 2. The mill base was prepared using a
dispersion of pigments and extenders with a thickener and surfac-
tant. Paints were made with all the binders with different amounts
Table 1
Comparisons of synthesized binders and their physico-chemical properties.
Exp no. % Core % Siloxane Coagulum pH Solids MFFT (

C) Particle size (nm)

I 100 0 Negligible 10.2 40.0 15.08 73.4
II 95 5 Negligible 10.4 41.8 15.6 77.5
III 90 10 Negligible 9.9 42.7 16.08 80.8
IV 85 15 <1% 10.3 43.2 16.28 91.8
V 80 20 <1% 10.18 44.5 17.08 95.6
VI 75 25 <1% 10.26 45.8 17.26 99.3
VII 70 30 <1% 10.1 47.7 17.9 115.6
Kamakshi.R. Christopher et al. / Progress in Organic Coatings 77 (2014) 10631068 1065
Fig. 2. FTIR spectra of (a) organo siloxane (b) PSA core & (c) PSA/PSi hybrid polymer.
of siloxanes and their properties compared. The paint lms were
cast in silicone release papers for studying their mechanical prop-
erties.
3. Results and discussion
3.1. Fourier transforminfrared (FTIR) spectra of the polymers
FTIR spectra of organosiloxane, styrene acrylic core, and PSA/PSi
hybrid polymer (system VII) are shown in Fig. 2ac respectively.
The organosiloxane is a phenylmethyl methoxy functional inter-
mediate. The Si O Si bending is observed at 482cm
1
in the
neat intermediate while the same is observed at 495cm
1
. The
Si C linkage at 809cm
1
was observed in organosiloxane and at
801cm
1
in PSA/PSi hybrid polymer. The sharp peaks at 1191cm
1
and2840cm
1
inthe neat intermediate correspondtothe methoxy
group and these are absent in the hybrid polymer indicating a pos-
sible reaction having occurred. Additional peak corresponding to
Si O Si bending at 1129cm
1
was observed in the intermediate
and as a shoulder in hybrid while the same was absent in styrene
acrylic core emulsion.
3.2. X-ray uorescence (XRF) of
polystyrene-acrylate/polysiloxane hybrid latex
X-ray uorescence analysis of the hybrid polymers showed that
the silicon content in the hybrids to be increasing linearly as may
be observed by the R
2
denoted by 0.99. The results of the various
hybrid samples are given in Fig. 3.
3.3. Dynamic light scattering of styrene acrylic siloxane hybrid
latex
The dynamic light scattering analyses (Figs. 4a and b) were
performed on latexes which were diluted to 1:50 with deminer-
alised water. The polystyrene-acrylate core particles showed a
mean particle diameter of 73.4nm while the PSA/PSi hybrid (Exp.
VII) displayed a mean diameter of 115.6nm, an increase of 42.2nm
with the same polydispersity index. The particle size was found
to increase progressively with increasing siloxane content in the
latex containing the different ratios.(Table 1) This demonstrated
that the organo siloxane intermediate is forming the shell on the
Fig. 3. Determination of silicon content by XRF in the polymer latex.
1066 Kamakshi.R. Christopher et al. / Progress in Organic Coatings 77 (2014) 10631068
Fig. 4. Mean particle size of (a) styrene acrylic core (b) PSA/PSi core shell latex (VII).
Fig. 5. DSC graphs of (a) styrene acrylic core emulsion (b) PSA/PSi core shell latex (V).
the surface of the core latex and not creating secondary species
in the latex system. Thus there is an inference of the existence of
coreshell morphology in the hybrid emulsions.
3.4. Differential scanning calorimetry
Differential scanning calorimetry (DSC) analysis of the lms
were carried out from 50

C to 100

C with a ramp of 10

C per
min and the transitions of the styrene acrylic core emulsion and
PSA/PSi hybrid core shell polymer hybrid polymers are given in
Table 3. DSC analyses of styrene acrylic siloxane hybrid polymer
show that the T
g
of the polymer showing two transitions indica-
tive of heterogeneity in the hybrid (Fig. 5a and b). The major T
g
is
found to raise corresponding to increasing siloxane content while
the opposite is true for the minor T
g
. This is due to a more differ-
entiated structure in the polymer [22]. An increase in minimum
lmformation temperature (MFFT as in Table 1) is also attributed
this phase separation. The pure core particle does not showdouble
transition as expected.
Table 3
Glass transition temperatures of the PSA core and core shell polymers by DSC.
Latex Tg (major) Tg (Minor)
Pure SA core 17.8
Core shell (90:10) 22.6 2.6
Core shell (80:20) 25.4 3.6
Core shell (75:25) 26.8 8.2
3.5. Dynamic mechanical analysis
Dynamic mechanical analysis (DMA) was carried out on cured
paint lms (14 days) using a DMA Q800 (TA Instruments), which
can obtain the storage modulus E

, the loss modulus E

, and the
loss factor (tan) over a temperature range from 50 to 100

C.
The isochronal tan curve at 1Hz as a function of temperature
is recorded using DMA. The DMA curves (Fig. 6) clearly show a
change inthe tan values of the polystyrene acrylic core andhybrid
latex particles (systems I & VII). There is a decrease in the storage
Fig. 6. DMA curves of PSA core (systemI)and PSA/Si (systemVII) depicting storage,
loss moduli and tan.
Kamakshi.R. Christopher et al. / Progress in Organic Coatings 77 (2014) 10631068 1067
Fig. 7. SEM-EDXS image of the hybrid polymer lm showing uniform presence of
silicon.
modulus of the hybrid polymer compared to the pure polystyrene-
acrylate whereas the tan has decreased from2.0 to 1.5. This may
be attributed to the T
g
difference between core and shell of the
hybrid latex. However, the effective tan (>0.5) of the core (from
15

to 60

C) has increased considerably for the hybird polymer

(from 20

to 100

C). It has been reported that the particles hav-

ing a multi layer particles have a broad tan peak which is also
observed in the hybrid polymers [19].
3.6. SEM-EDXS
The hybrid lms were characterized using scanning electron
microscopy (SEM) coupled with elemental analysis. Fig. 6 shows
the SEMimage of PSA/PSi hybrid polymer (systemVII) with the ele-
mental silicon composition in the surface. It may be observed that
silicon is distributed uniformly across the lmstructure as denoted
by the dots in Fig. 7. There is no disparity in the concentration of
silicon throughout the surface of the sample. Siloxane chains when
present in the surface would protect the styrene groups that are
prone to damage under UV light.
3.7. Morphology studies by TEM
Transmission electron microscopy (TEM) micrographs (Fig. 8)
showaclear differenceincontrast betweentheouter andinner por-
tion of the particle (systemVII). The dark shade in the TEMimages
of the coreshell particles refer to higher concentration of styrene
in the core. The phase separation indicates presence of siloxane in
the shell of the latex particle.
Fig. 9. Water contact angle (WCA) on the PSA/PSi hybrid lms with varying shell
ratios.
Table 4
Mechanical properties of the paint lms after 7 days.
Siloxane (wt%) % Elongation Tensile strength (MPa)
0 116 2.1
5 135 2.5
10 180 2.4
20 150 2.4
25 113 2.7
30 61.5 2.8
3.8. Contact angle of the emulsion polymers
The contact angle of the latex lms was measured after seven
days of casting the lms on a glass plate. The increase in siloxane
content was found to enhance the contact angle of the emulsion
lmwith respect to water (Fig. 9). This might be due to the fact that
organo-siloxane groups inthe shell being moderately hydrophobic,
tend to accumulate on the surface. However, there is not a great
augumentation of the contact angle beyond a certain content of
siloxane. It may be speculated that at this siloxane content there is
a saturation of the groups in the surface and hence further increase
does not lead to improvement in hydrophobicity.
3.9. Evaluation of mechanical properties of paint lms
Films of white paints were casted on release papers using 625
micronmultiple lmapplicator andallowedtodry for 7days. These
were tested as per procedures described in test method ASTM
D4708. The PSA/PSi hybrid coatings show good elongation with
high tensile strength (Table 4). There is a need for coatings that
showimproved hardness along with exibility. It may be observed
Fig. 8. TEMmicrographs of the core shell hybrid polymer latex showing distinct PSA/PSi domains.
1068 Kamakshi.R. Christopher et al. / Progress in Organic Coatings 77 (2014) 10631068
Fig. 10. Color change (dE*) after 650h of QUV-A exposure.
Fig. 11. Dirt pickupresistanceafter 6months of exposureof of whitepaintedsurface
(a) PSA/PSi hybrid polymer (b) PSA core polymer.
that there is a decrease in elongation after 10% of siloxane content
which may be attributed to extensive crosslinking in the lms after
coalescence.
3.10. Weatherability tests
3.10.1. QUV results
The panels were coatedwithwhite paints made usingthe exper-
imental binders. The initial reectance readings for all the samples
were found to be comparable. The coated panels were exposed
to the UV A radiation for 600h. Paint lm made of polystyrene-
acrylate binder was found to undergo chalking and yellowing on
exposure to UV light. Incorporation of merely 5% siloxane into the
system reduced the yellowing considerably. The Si O Si bonds
resist degradation and thus protect the paint lms from UV radi-
ation. The color change (measured as dE*) on UV exposure and is
foundto decrease considerably withincreasing siloxane content up
to 20% (Fig. 10). This is due to the fact that the siloxane shell is able
to coat the surface completely thus shielding the styrene backbone.
3.10.2. Dirt pickup resistance
Dirt pickup resistance refers to a coatings ability to maintain
its original appearance with respect to soiling of the surface due
to exterior environmental conditions. The painted panels were
exposed for a period of 6 months at 45

facing south and evalu-

ated visually by their appearance. It may be observed that the paint
lmwith the core shell polymer (systemVII) shows less soiling to
the polymer with styrene-acrylate polymer (Fig. 11).
4. Conclusion
Polystyrene-acryate/polysiloxane hybridlatexes have beensyn-
thesized using regular seeded emulsion polymerization. It was
noted that siloxane groups could be incorporated upto to 30%
using this technique. The synthesizedpolymers were characterized
through multiple techniques like DLS, DSC DMA & TEM and were
found to have the polystyrene-acrylate core and polyorganosilox-
ane shell morphology. The siloxane groups are found to be present
in the surface which leads to a a signiant improvement in the
surface properties. White paints made from the core shell poly-
mers werefoundtodisplaysuperior mechanical andweatherability
properties that may be exploited for high durable exterior paints.
The methodoffers aneasy route tostructuredlatex that canbe used
in paints to improve performance properties.
Acknowledgements
Authors wish to thank members (Imtiyaz, Sonali, Sushma &
Latheish) of Instruments Lab, Asian Paints for their support in char-
acterization. Authors thank Dr. Mosongo Moukwa, Dr. Mohan Rao,
Dr. Randhirsinh Parmar & Dr. Subhramanya Shreepathi for their
help in reviewing the manuscript. Thanks are due to Dr. B.P. Mallik
and Asian Paints Management for their continuous support.
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