Progress in Organic Coatings xxx (xxxx) xxxx

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Progress in Organic Coatings

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

Studies on synthesis and characterization of aqueous hybrid silicone-acrylic

and acrylic-silicone dispersions and coatings. Part II
Janusz Kozakiewicza,*, Joanna Trzaskowskaa, Wojciech Domanowskia, Anna Kieplinb,
Izabela Ofat-Kawaleca, Jarosław Przybylskia, Monika Woźniakb, Dariusz Witwickib,
Krystyna Sylwestrzaka
a
Industrial Chemistry Research Institute, Department of Polymer Technology and Processing, Rydygiera 8, 01-793, Warsaw, Poland
b
D&R Dispersions and Resins Sp. z o.o., Duninowska 9, 87-800, Włocławek, Poland

A R T I C LE I N FO A B S T R A C T

Keywords: Aqueous silicone-acrylic (SIL/ACR) and acrylic-silicone (ACR/SIL) dispersions with hybrid particle structure
Aqueous hybrid silicone-acrylic dispersions were synthesized, respectively, by polymerization of acrylic/styrene monomers in silicone resin dispersion (SIL)
Aqueous hybrid acrylic-silicone dispersions and of silicone monomers in two acrylic/styrene copolymer dispersions (ACR A and ACR B). A comprehensive
Silicone study of the effect of SIL/ACR or ACR/SIL (w/w) ratio, i.e. of the silicone component content in the dispersion
acrylic/styrene copolymer
solids, on the properties of such hybrid dispersions, coatings and films was conducted. It was found that in-
Silicone-containing dispersion particles
Coatings
creasing the SIL/ACR ratio from 0 to 1/9, 1/6 and 1/3 (or decreasing ACR/SIL ratio accordingly) influenced
quite significantly the appearance of hybrid dispersion particles and thus also the properties of dispersions
(particle size, MFFT, Tg of dispersion solids) as well as the properties of coatings (contact angle, surface free
energy, water resistance, water vapor permeability, hardness, impact resistance) and films (% swell in toluene, %
of toluene-soluble fraction, tensile strength, elongation at break) made from these dispersions were affected.
Based on the results of these investigations some dispersions may be selected for further testing as binders in
architectural paints.

1. Introduction
Aqueous polymer dispersions containing silicones are of great in-
terest of both researchers and industry due to advantages they can offer
if used as coating binders, especially if the dispersion particle has hy-
brid structure since it may result in synergistic effect leading to en-
hanced coating properties [1]. In the study reported in [2] we in-
vestigated the effect of method of synthesis of such dispersions on their
properties as well as on properties of coatings and films obtained from
them. In that study, dispersions with hybrid particle structure con-
taining silicones were obtained through polymerization of acrylic/
styrene monomers with different composition in aqueous dispersions of
silicone resins with different composition of starting silicone monomers
and also through polymerization of silicone monomers of the same
composition in acrylic/styrene copolymer dispersions with the same
composition of starting acrylic/styrene monomers. It was found that the
method of synthesis significantly influenced the morphology of hybrid
dispersion particles what, in consequence, affected the properties of
dispersions and corresponding coatings and films. While in all
dispersions, coatings and films obtained in that study the ratio (w/w) of
silicone component (SIL) to acrylic/styrene component (ACR) remained
at the constant level of 1/3, in this paper we present the results of in-
vestigations of the effect of SIL/ACR or ACR/SIL (w/w) ratio, i.e. of the
silicone component content in the dispersion solids on the properties of
such hybrid dispersions, coatings and films.
It is obvious that the features of any polymer system consisting of
two or more different polymers would depend on the share of in-
dividual components. The same was also proved in papers dealing with
coatings obtained from aqueous dispersions with particles consisting of
different polymers regardless of the method of dispersion synthesis –
see the reviews in [1,3] and [4]. If one of these polymers was silicone
the effect of its content on properties of dispersions and coatings could
be very significant. In the study reported in [5] hybrid dispersions and
corresponding coatings were obtained by emulsion polymerization of a
mixture of acrylic monomers (butyl acrylate, acrylic acid, acrylonitrile
and acrylamide) and silicone monomers (3-methacryloxypropyl-
trimethoxysilane, octamethylcyclotetrasiloxane (D4) and hexam-
ethyldisiloxane) applying a wide range of different silicone/acrylic

⁎
Corresponding author.
E-mail address: Janusz.kozakiewicz@ichp.pl (J. Kozakiewicz).

https://doi.org/10.1016/j.porgcoat.2019.105297
Received 30 May 2019; Received in revised form 25 July 2019; Accepted 26 August 2019
0300-9440/ © 2019 Elsevier B.V. All rights reserved.

Please cite this article as: Janusz Kozakiewicz, et al., Progress in Organic Coatings, https://doi.org/10.1016/j.porgcoat.2019.105297
J. Kozakiewicz, et al.
polymer w/w ratios. It was found that water absorption of the coatings
decreased and contact angle increased with increase in silicone/acrylic
polymer w/w ratio from 0 to 50% while in some other earlier paper [6]
it was stated that silicone content in such hybrid dispersions (also ob-
tained by direct emulsion copolymerization of acrylic and silicone
monomers) should not be higher than 20% due to “reatardation of the
polymerization and limitation of the conversion”. Similar conclusions
were made based on the results of another study [7]. Positive effect of
silicone content on water resistance and surface hydrophobicity of
coatings was also confirmed in [8] and [9] while the authors of two
other papers [10,11] reported that not total silicone content, but rather
the part of silicone grafted onto acrylic polymer is responsible for such
enhancement of properties, including also thermal stability and me-
chanical properties. As it was proved in [10], if the content of the
grafted silicone was changed the water distribution in the drying coats
was different what distinctly affected the drying time.
The effect of silicone content on the properties of hybrid disper-
sions, specifically on dispersion stability and coagulum content was
investigated in a study described in [12] where 3-methacrylox-
ypropyltrimethoxysilane was polymerized in aqueous acrylic polymer
dispersion. It was confirmed that only certain amount of silicone could
be grafted on acrylic polymer to produce core-shell particle structures
and further increase in silicone part content led to poor dispersion
stability and increased coagulum content due to formation of separate
crosslinked silicone particles. It was also proved in the other studies
[13,14] that increasing the content of silicone part in a hybrid disper-
sion led to the increase in dispersion particle size. This phenomenon
was explained by condensation of silanol groups formed during hy-
drolysis of alkoxysilane groups in silicone monomers that is more
probable at higher silicone content in the system. However, when the
hybrid dispersion was made by polymerization of acrylic monomers in
aqueous polydimethylsiloxane (PDMS) dispersion [15] the opposite
effect was observed, i.e. the particle size decreased with increase in
silicone/acrylic polymer ratio and it was explained by “shrinking of
PDMS chains in the hydrophobic core”.
The examples of studies where the effect of silicone content on
properties of silicone-containing aqueous dispersions with hybrid par-
ticle structure as well as the corresponding coatings and films show that
though some conclusions in that regard concerning specific systems
could be made there was no systematic study published were that
subject was investigated in greater detail. In this study we attempted to
fill that gap.
2. Materials and methods
2.1. Starting materials
Octamethylcyclotetrasiloxane (D4) was obtained from Momentive.
Other silicone monomers, i.e. vinyltriethoxysilane (VTES) and methyl-
triethoxysilane (MTES) were obtained from Evonic. Surfactants - do-
decylbenzenesulphonic acid (DBSA) and Rokanol T18 (non-ionic) were
obtained from PCC Exol and Emulgator E30 (anionic) was obtained
from Leuna Tenside GmbH. Other standard ingredients used in synth-
esis of dispersions (sodium acetate, sodium hydrocarbonate, potassium
persulphate and aqueous ammonia solution) were obtained from
Standard Lublin. Biocide used to protect dispersions from infestation
was Acticide MBS obtained from THOR.
Starting acrylic/styrene copolymer dispersions (ACR A and ACR B)
characterized by different glass transition temperatures (Tgs) were
supplied by Dispersions&Resins. Monomers applied in synthesis of ACR
A and ACR B dispersions were butyl acrylate (BA) obtained from ECEM,
Arkema, styrene (ST) obtained from KH Chemicals, Helm, acrylic acid
(AA) obtained from Prochema, BASF and methacrylamide (MA) ob-
tained from ECEM, Arkema. Acrylic and styrene monomers were used
as received as mixtures designated as A and B with compositions cor-
responding to compositions of monomers applied to synthesize
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Progress in Organic Coatings xxx (xxxx) xxxx
dispersions ACR A and ACR B, respectively. The compositions of
monomers were appropriately designed to get Tg of dispersion solids at
a level of ca. + 15 °C (ACR A) and at a level of ca. + 30 °C (ACR B).
Unlike in synthesis of standard aqueous acrylic/styrene polymer
dispersions ACR A and ACR B dispersions were not neutralized after
polymerization process in order to ensure low pH value (ca. 3) that was
needed to conduct subsequent polymerization of silicone monomers in
the process of synthesis of hybrid acrylic-silicone (ACR/SIL A and ACR/
SIL B) dispersions.
2.2. Synthesis of silicone resin dispersions (SIL) and hybrid silicone-acrylic
(SIL/ACR A and SIL/ACR-B) and acrylic-silicone (ACR/SIL A and ACR/
SIL B) dispersions
Synthesis of silicone resin dispersion (SIL) applied as starting dis-
persion for emulsion polymerization of acrylic monomers to obtain SIL/
ACR hybrid dispersions was conducted following the procedure de-
scribed in [16] using a mixture of silicone monomers with the following
composition : D4 - 84.0%, MTES - 9.5%, VTES - 6.5%. DBSA was acting
as both surfactant and D4 ring opening catalyst. The reactions which
proceeded during the process of synthesis of SIL dispersion comprised
ring opening polymerization of D4 and hydrolysis of ethoxysilane
groups of MTES and VTES leading to formation of silanol groups cap-
able for further condensation. The product of these reactions was
aqueous dispersion of partly crosslinked silicone resin. The process of
synthesis of silicone resin dispersion (SIL) is shown in Fig. 1.
After distillation of ethanol under vacuum no free VTES or MTES
were detected by GC in the resulting SIL dispersion, though small
amounts of D4 (ca. 0.8%) and ethanol (ca. 0.2%) were still present. The
conversion of VTES and MTES in that process was practically 100%
while the conversion of D4 was rather low due to cyclic to linear oli-
gosiloxanes thermodynamic equilibrium and varied from ca. 30% for
ACR/SIL = 3/1 to 80-90% for ACR/SIL = 9/1.
Synthesis of hybrid silicone-acrylic (SIL/ACR A and SIL/ACR B) by
polymerization of acrylic/styrene monomers in SIL dispersion and of
hybrid acrylic-silicone (ACR/SIL A and ACR/SIL B) dispersions by
polymerization of silicone monomers in acrylic/styrene polymer dis-
persions ACR A and ACR B was conducted as described in [2]. The
conversion of monomers in this process was close to 100% since the
concentration of monomers in the final dispersions was very low (below
0.01%). The ratio (w/w) of silicone polymer and acrylic polymer
components (SIL/ACR) was set at 1/9, 1/6 and 1/3 what corresponded
to 10%, 143% and 25% of silicone component in hybrid dispersions
solids. It was essential that the composition and concentration of sur-
factants remained the same in all SIL/ACR and ACR/SIL dispersions
despite the SIL/ACR or ACR/SIL ratio, so their properties (and prop-
erties of coatings obtained from them) could be compared.
2.3. Characterization of dispersions
All dispersions were characterized by:
- Solids content, wt% – percentage of sample mass remaining after
drying for 1 h at 80◦C followed by 4 h at 125 °C.
- pH – using standard indicator paper and Elmetron Pehameter CP-
411 with ERH-11S electrode
- Viscosity – using Bohlin Instruments CVO100 rheometer, cone-
plate 60 mm diameter and 1 deg measuring device, shear rate 600 s−1
- Coagulum content - after filtration of dispersion on 120 mesh net
the solids remaining on the net were dried and weighed. Coagulum
content (wt%) was calculated from equation mc/mdx100% where mc
was mass of dry coagulum remaining on the net and md was mass of
dispersion.
- Acrylic and styrene monomers, ethanol and D4 content – by GC
(HP 5890 series II apparatus, FID detector)
- Mechanical stability – lack or occurrence of separation during
rotation in Hettich Universal 32R centrifuge at 4000 r.p.m. for 90 min
J. Kozakiewicz, et al.
Fig. 1. Process of synthesis of silicone resin dispersion (SIL) by emulsion polymerization of silicone monomers.
was considered as good stability
- Average particle size (nm), particle size distribution and zeta po-
tential (mV) – light scattering method using Malvern Zeta Sizer appa-
ratus
- Particle appearance – STEM (Scanning Transmission Electron
Microscope) Hitachi 2700, dispersions were diluted 1000× with water
for taking pictures. High Angle Annular Dark Field (HAADF) mode also
called “Z-contrast” was applied for processing the images reproduced in
this paper.
- Minimum Film Forming Temperature (MFFT) – according to ISO
2115 using Coesfeld apparatus equipped with temperature gradient
plate. Temperature range : −3 °C to +50 °C.
- Glass transition temperature (Tg) of dispersion solids – by DSC (TA
Instruments Q2000 apparatus), heat–cool–heat regime, 20◦C/min
2.4. Characterization of coatings
Coatings were produced from dispersions by applying them on glass
(for testing contact angle, hardness, adhesion or water resistance),
aluminium plates (for testing elasticity) or on steel plates (for testing
impact resistance and cupping) using 120μ applicator. Drying was
carried out for 30 min at +50 °C and then the coatings were seasoned in
a climatic chamber at +23 °C and 55% R.H. for 72 h. Since no con-
tinuous coating could be obtained in this procedure for SIL/ACR B 1/3
the relevant dispersion was dried at +8 °C for 2 h and then seasoned as
above. The resulting coatings were characterized by:
- Contact angle (water) – according to EN 828:2000, using KRUSS
DSA 100E apparatus.
- Pendulum hardness (Koenig) – according to EN ISO 1522
- Adhesion to glass – according to EN ISO 2409
- Elasticity – according to EN ISO 1519
- Impact resistance (direct and reverse) – according to EN ISO 6272-
1, using Erichsen Variable Impact Tester Model 304
- Cupping – according to EN ISO 1520, using Erichsen Cupping
Tester
- Water resistance – glass Petri dishes of 50 mm diameter were filled
with distilled water and placed upside-down on the coating, so the
coating was covered with 7 mm thick layer of water. Assembles pre-
pared this way were left for 72 h and appearance of coatings was ex-
amined for the bubbles size (S0 - no bubbles, S2-S5 - low to high size of
bubbles) and density (0 - no bubbles, 2–5 low to high density of bub-
bles) according to EN ISO 4628-2. Changes of coating appearance after
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Progress in Organic Coatings xxx (xxxx) xxxx
6 days under water were also examined.
Water vapor permeability – according to ASTM F1249. TotalPerm
063 (Extra Solution) apparatus was used. Tests were conducted at 23 °C
for 0.35 mm thick film. Fomblin perfluorinated grease from Solvay
Solexis was applied to seal the test vessels.
Moreover, coatings applied on PET film were examined for surface
structure by X-ray Photoelectron Spectroscopy (XPS) using ULVAC/
PHYSICAL ELECTRONICS PHI5000 VersaProbe apparatus and by
Atomic Force Microscopy (AMF) using RHK-VHV350 apparatus
working in a “tapping mode” with PPP-RT-NCHR nanosensors.
2.5. Characterization of films
- % swell in toluene and % of toluene-soluble fraction - ca. 0.12 g
samples of 0.35 mm thick film were weighed and placed in 40 ml to-
luene contained in closed glass cups and left for 20 h at 23 °C. Then the
samples were taken out, delicately dried with filter paper and weighed.
% swell was calculated from the equation : % swell = m1-m0/
m1x100%, where m0 = mass of the sample before test and m1 = mass
of the sample after test. For determination of percentage of toluene-
soluble fraction the films were weighted before immersion in toluene
and then after complete drying at room temperature (till no weight
change was noticed). % of toluene-soluble fraction was calculated from
the equation : % of toluene soluble fraction = m1-m0/m1x100%, where
m0 = mass of the sample before test and m1 = mass of the sample after
test.
- mechanical properties (tensile strength and elongation at break) –
determined for 0.2 mm thick films using Instron 3345 testing machine
according to EN-ISO 527-1 at a speed of 50 mm/min.
3. Results and discussion
3.1. Effect of silicone content on properties of dispersions
All SIL/ACR and ACR/SIL dispersions synthesized in our study were
mechanically stable. Free acrylic/styrene monomers content in SIL/
ACR dispersions was below 0.01% while ACR/SIL dispersions contained
no free acrylic/styrene monomers. Ethanol and D4 content in both SIL/
ACR and ACR/SIL dispersions was at the level of 0.1% and 0.4% re-
spectively. The other properties of dispersions obtained using different
SIL/ACR or ACR/SIL ratio are shown in Table 1. Designation of dis-
persion in the table reflects the method of its synthesis and the
J. Kozakiewicz, et al. Progress in Organic Coatings xxx (xxxx) xxxx

Table 1
Properties of SIL/ACR and ACR/SIL hybrid dispersions obtained using different SIL/ACR or ACR/SIL ratio.
Designation of pH Solids Coagulum Viscosity at Average Particle size Polydispersity Zeta Minimum Film- Tg (dispersion solids)
dispersions content % content % 23 °C mPas particle size distribution nm potential Forming °C
nm mV Temperature
(MFFT) °C

ACR A 6.2 51.1 < 0.1 94 105.7 74–119 0.112 −51.0 11.4 +17.17
SIL 6.3 19.3 0.00 2 121.7 104–157 0.121 −50.9 N.A. −117.33
SIL/ACR A 1/3 5.8 42.2 0.06 20 143.8 69–160 0.074 −57.7 7.3 −126.66 +17.66
SIL/ACR A 1/6 6.3 50.5 0.05 72 166.2 62-161 0.066 −51,2 10.6 −130.36 +17.24
SIL/ACR A 1/9 6.3 50.6 0.03 137 144.7 112-187 0.057 −58.3 8.1 −132.27 +16.47
ACR/SIL A 3/1 6.3 43.2 0.38 140 111.7 71–131 0.096 −55.2 −0.5 −130.54 +14.58
ACR/SIL A 6/1 6.3 50.3 0.13 148 120.4 101-134 0.059 −53.2 −0.5 +14.97
ACR/SIL A 9/1 6.3 47.7 0.02 162 105.4 95-110 0.058 −58.5 −0.2 +17.15
ACR B 6.2 51.5 < 0.1 98 112.2 108–135 0.066 −56.0 32.7 +32.36
SIL/ACR B 1/3 6.3 42.3 0.11 24 140.3 69–190 0.072 −59.5 26.2 −129.09 +30.87
SIL/ACR B 1/6 6.5 50.81 0.19 127 175.4 133-203 0.052 −56.9 25.3 −133,09;+32,25
SIL/ACR B 1/9 6.3 50.76 0.1 143 151.7 73-186 0.042 −57.6 29.4 −135,71 +35,75
ACR/SIL B 3/1 6.3 42.0 0.21 61 114.4 98–133 0.071 −55.0 16.0 −126.33 +27.98
ACR/SIL B 6/1 6.3 50.4 0.054 259 123.1 106-144 0.052 −58.8 16.0 +28.72
ACR/SIL B 9/1 6.3 48.29 5.23 346 98.7 88-118 0.058 −58.5 19.9 +30.28

composition of its solids. E.g. designation SIL/ACR A 1/9 corresponds
to hybrid dispersion synthesized by polymerization of acrylic/styrene
monomers with composition ACR A in silicone resin dispersion ap-
plying the ratio (w/w) of silicone monomers to silicone dispersion so-
lids equal to 1/9 (w/w) while designation ACR/SIL B 3/1 corresponds
to hybrid dispersion synthesized by polymerization of silicone mono-
mers in acrylic/styrene polymer dispersion ACR B applying the ratio
(w/w) of acrylic/styrene dispersion solids to silicone monomers equal
to 3/1. As it can be noted from Table 1 all hybrid dispersions had solids
content equal to ca. 50% and pH equal to ca. 6. The coagulum content
was found to be quite low, especially for SIL/ACR dispersions, as
compared to the relevant values reported for other hybrid silicone/
acrylic dispersions [17–21] and viscosity was rather low
(20–350 mPa s).
3.1.1. Particle size and particle size distribution
As it can be noted from Table 1 the particle size of hybrid disper-
sions was generally close to 100–150 nm and particle size distribution
was quite narrow. The effect of SIL/ACR or ACR/SIL ratio (i.e. silicone
content in the dispersion solids) on average particle size of SIL/ACR and
ACR/SIL hybrid dispersions is shown in Fig. 2.
The results of average particle size measurements of SIL/ACR and
ACR/SIL hybrid dispersions as compared to the corresponding acrylic/
styrene copolymer dispersions shown in Fig. 2. demonstrate that re-
gardless SIL/ACR or ACR/SIL ratio and method of hybrid dispersion
synthesis the particle size of hybrid dispersions was generally higher
Fig. 2. The effect of SIL/ACR or ACR/SIL ratio (i.e. silicone content in the
dispersion solids) on average particle size of SIL/ACR and ACR/SIL hybrid
dispersions.
than that of acrylic/styrene dispersion what suggests that indeed hybrid
particles were obtained. This finding was confirmed by TEM in-
vestigations – see 3.1.2.
It is also clear that the average particle size of SIL/ACR dispersions
was higher than that of ACR/SIL dispersions for all SIL/ACR or SIL/ACR
ratios what most probably resulted from different appearance of dis-
persion particles when dispersions were obtained by different methods -
see discussion on appearance of dispersion particles in 3.1.2 and in [2].
Another interesting finding from Fig. 2 is that the average particle size
was generally higher for higher SIL contents for both SIL/ACR and
ACR/SIL dispersions and for both ACR A - based and ACR - B based
dispersions. That finding is consistent with the results reported by the
other authors [5] who, however, obtained hybrid SIL/ACR dispersions
by different method, namely direct copolymerization of acrylic and
silicone monomers. Based on that finding it can be concluded that in-
crease in the average particle size with increase in silicone content in
hybrid SIL/ACR dispersions is a general rule. Nevertheless, in disper-
sions investigated in our study a maximum was observed for ca. 15% of
silicone in dispersion solids what could suggest that the change in ap-
pearance of dispersion particles occurred at that specific SIL/ACR (1/6)
or ACR/SIL (6/1) ratio. This assumption was confirmed by the results of
particle appearance studies described in 3.1.2.
3.1.2. Particle appearance
The particle appearance observed for different contents of silicone
in dispersion solids for both SIL/ACR and ACR/SIL dispersions is shown
in Fig. 3.
It can be noted from Fig. 3 that the appearance of dispersion par-
ticles depended very much not only on SIL/ACR or ACR/SIL ratio but
also on the method of dispersion synthesis and on type of acrylic/
styrene copolymer (A or B). The TEM images are not perfect because of
coalescence of the particles, but nevertheless certain conclusions can be
made. In the case of SIL/ACR A dispersions smaller silicone particles
were contained in bigger acrylic/styrene copolymer particles while in
the case of SIL/ACR B dispersions the single dispersion particle con-
sisted of a number of mixed tiny silicone and acrylic/styrene copolymer
particles. In both cases the increase in silicone content did not lead to
distinct changes in particle appearance. In the case of ACR/SIL dis-
persions the particle appearance changed significantly with increase in
silicone content and for ACR/SIL A 3/1 dispersion a very interesting
“embedded sphere” structure was observed where silicone part formed
a sphere trapped in the mass of acrylic/styrene copolymer. However,
such structure was not present in ACR/SIL B 3/1 dispersion.

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J. Kozakiewicz, et al. Progress in Organic Coatings xxx (xxxx) xxxx

Fig. 3. Particle appearance observed by TEM for SIL/ACR and ACR/SIL dispersions with different silicone content (i.e. different SIL/ACR or ACR/SIL ratio). Since the
images were taken in HAADF mode the silicone component of the particles is represented by whiter shade.

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J. Kozakiewicz, et al. Progress in Organic Coatings xxx (xxxx) xxxx

Fig. 5. The results of DSC studies conducted for SIL/ACR dispersion solids
Fig. 4. The effect of SIL/ACR or ACR/SIL ratio (i.e. silicone content in the obtained from dispersions synthesized using different SIL/ACR ratios. The re-
coating) on MMFT of SIL/ACR and ACR/SIL hybrid dispersions. sults obtained for ACR and SIL dispersion solids are also presented for com-
parison.

3.1.3. Minimum film-forming temperature (MFFT)

The results of MFFT determinations of SIL/ACR and ACR/SIL dis-
persions are shown in Fig. 4.
It is clear from Fig. 4 that modification with silicone resin resulted
in a beneficial decrease in MFFT of hybrid SIL/ACR and ACR/SIL dis-
persions as compared to the corresponding acrylic/styrene copolymer
dispersions. This finding is rather obvious assuming much lower Tg of
silicone resin than that of acrylic/styrene copolymer. It can also be
noted that the observed decrease was much more distinct for ACR/SIL
than for SIL/ACR dispersions. The reason for that difference can be the
different appearance of hybrid dispersion particles – see 3.1.2. Speci-
fically, in SIL/ACR dispersions silicone component was trapped inside
acrylic/styrene copolymer component, so its influence on MFFT could
not be very significant. Another observation form Fig. 4 is that the
MFFT values decrease only up to a certain content of silicone in dis-
Fig. 6. The results of DSC studies conducted for ACR/SIL dispersion solids
persion and further increase in SIL/ACR ratio (or decrease in ACR/SIL obtained from dispersions synthesized using different ACR/SIL ratios. The re-
ratio) does not lead to lower MFFT. sults obtained for ACR and SIL dispersion solids are also presented for com-
parison.
3.1.4. Glass transition temperature (Tg) of dispersion solids
Based on the results of Tg determinations (see Table 1) it can be
differences in dispersion particle appearance since for lower silicone
noted that Tg of silicone part of SIL/ACR hybrid dispersions solids re-
contents the uniform or “fruit-cake” type dispersion particles structures
gardless SIL/ACR ratio was significantly (almost 20 °C) lower than Tg of
were found.
starting SIL dispersion solids. This phenomenon can only be explained
by occlusion of small amounts of cyclic oligosiloxanes in hybrid dis-
persion particles. Such occlusion could occur because in these particles 3.2. Effect of silicone content on properties of coatings and films
silicone resin was, in fact, trapped in the particle (coated with a layer of
acrylic/styrene copolymer) what was confirmed by TEM investigations The properties of coatings and films made from SIL/ACR and ACR/
– see 3.1.2. Then, the occluded cyclic oligosiloxanes as well as un- SIL hybrid dispersions obtained using different SIL/ACR or ACR/SIL
reacted silanes with silanol groups that were formed by hydrolysis of ratio are shown in Table 2. Designation of dispersions is the same as
alkoxysilanes could act as plasticizers for silicone resin. The observed used in Table 1.
decrease in Tg of silicone part of hybrid dispersion solids for SIL/ACR
dispersions as compared to Tg of starting silicone dispersion solids is 3.2.1. Surface properties
further demonstrated in Fig. 5 where the results of DSC studies con- It is well known [1,2,22] that modification of aqueous acrylic/
ducted for these dispersions are presented. styrene copolymer dispersions with silicones results in significant
The explanation presented above can be assessed by the fact that for changes in surface properties of the corresponding coatings, specifically
ACR/SIL hybrid dispersions such phenomenon was observed (see in increase in contact angle and decrease in surface free energy because
Fig. 6) only for dispersion with high (ACR/SIL = 3/1) silicone content silicone component migrates to the coating surface. In our investiga-
where the particle structure was much more homogeneous than in the tions described in this paper we attempted to assess how silicone con-
case of SIL/ACR = 1/3 dispersions. In the particle structure of ACR/SIL tent in the coating affected this phenomenon. When the contact angle
= 3/1 silicone resin was “hidden” inside acrylic/styrene copolymer (CA) and surface free energy (SFE) determined for coatings made from
particle. SIL/ACR and ACR/SIL dispersions and corresponding acrylic/styrene
The same observation was made in our earlier studies of hybrid SIL/ copolymer dispersions were plotted against the silicone content in the
ACR and ACR/SIL dispersions and the corresponding coatings [2]. It is coating it became clear that the higher was silicone content the higher
interesting that while two distinct Tgs were observed for silicone part was CA and the lower was SFE – see Fig. 7 and Fig. 8, respectively.
and acrylic/styrene copolymer part of ACR/SIL dispersion solids when As it can be seen in Fig. 7 and Fig. 8 this effect was generally quite
they contained more silicone (ACR/SIL = 3/1) only a single Tg was significant (even with only 10% of silicone in the coating) and was
observed for hybrid ACR/SIL dispersions solids with lower silicone generally more distinct for coatings made from ACR/SIL dispersions
content. Explanation of this phenomenon can be also based on than from SIL/ACR dispersions, but for the latter higher CA values (or

6
 J. Kozakiewicz, et al.

Table 2
Properties of coatings and films made from SIL/ACR and ACR/SIL hybrid dispersions obtained using different SIL/ACR or ACR/SIL ratio.
Designation of Water vapor Water Hardness Swell in Toluene-soluble Contact Impact Impact Cupping mm Elasticity (rod Adhesion to Tensile Elongation at
dispersions permeability g/ resistance (Koenig) toluene % fraction% angle Resistance Resistance diameter2 mm) glass strength break %
m2/24 h after 72 h % (H2O) ° (direct) J (reverse) J MPa

ACR A 28.1 > 5(S5) 0.08 1156 21.5 30,1 2 19,6 10,7 passed 5 4,23 999,95
SIL/ACR A 1/3 56.5 5(S2)Medium 0,04 591 15.6 82,7 9,8 19,6 11,6 passed 3 2,13 773,28
whitening
SIL/ACR A 1/6 40.1 4(S3) Large 0,04 703 17.7 80,6 11,8 19,6 11,1 passed 2 1,11 765,35
whitening
SIL/ACR A 1/9 31.4 4(S2) Large 0,02 707 14.9 73,8 5.0 19,6 10,8 passed 5 2,22 966,07
whitening
ACR/SIL A 3/1 45.0 0(S0)Light 0,02 1050 58.6 95,2 15.7 19,6 11,0 passed 2 0,75 1851,15
whitening
ACR/SIL A 6/1 37.8 2(S5)Medium 0,023 1037 43.4 93,3 2.0 19,6 10,9 passed 5 1,02 1410,79

7
whitening
ACR/SIL A 9/1 35.1 0(S0)Medium 0,023 1228 24.3 45,8 2.0 19,6 10,4 passed 2 1,05 1039,82
whitening
ACR B 15.6 5(S2)Medium 0,458 1547 31.2 34,5 2 0 10,7 failed 5 12,00 340,49
whitening
SIL/ACR B 1/3 64.5 5(S2) Light 0,085 561 25.9 81,1 0 0 10,9 passed 5 4,33 11,01
whitening
SIL/ACR B 1/6 28.4 5(S4) Medium 0,156 643 17.0 68,6 0 2 10,8 passed 4 8,21 62,08
whitening
SIL/ACR B 1/9 25.3 4(S3) Medium 0,154 723 17.3 72,3 3,9 0 10,5 passed 5 1011 244,41
whitening
ACR/SIL B 3/1 34.6 0(S0) Medium 0,050 905 39.6 91,5 5,9 19,6 10,9 passed 5 3,05 1015,22
whitening
ACR/SIL B 6/1 31.3 0(S0)Medium 0,127 1440 39.2 58,0 1 1 10,4 passed 5 4,74 808,52
whitening
ACR/SIL B 9/1 27.0 3(S2)Large 0,185 Sample Sample 45,9 2 0 9,6 passed 4 7,83 333,75
whitening deteriorated deteriorated
Progress in Organic Coatings xxx (xxxx) xxxx
J. Kozakiewicz, et al.
Fig. 7. The effect of silicone content on CA (water) of coatings made from
hybrid SIL/ACR and ACR/SIL dispersions.
Fig. 8. The effect of silicone content on SFE of coatings made from hybrid SIL/
ACR and ACR/SIL dispersions.
Fig. 9. Differences in Si content on the surface of coatings made from hybrid
SIL/ACR dispersions obtained using different SIL/ACR ratio.
lower SFE values) are observed at lower SIL/ACR ratios. These results
suggested that the surfaces of coatings which contained more silicone
were more enriched with silicone what was proved by XPS studies – see
Fig. 9.
The apparent differences in the structure of coating surface de-
pending on SIL/ACR ratio can be seen on AFM images presented in
Fig. 10. While the surface of coating made from unmodified ACR B
dispersion (c) seem to be rather smooth the round-shaped structures
with ca. 100 nm size are emerging from the surface of coatings made
from SIL/ACR B dispersions modified with silicone (a) and (b) and are
much more abundant for the coating that contains more silicone (a).
3.2.2. Water resistance
The effect of silicone content on water resistance of coatings made
8
Progress in Organic Coatings xxx (xxxx) xxxx
from SIL/ACR and ACR/SIL dispersions is shown in Figs. 11 and 12. It is
clear from Fig. 11 that water resistance was significantly enhanced in
coatings produced from hybrid dispersions containing silicone as
compared to unmodified acrylic/styrene copolymer (ACR) dispersions
even if silicone content in the coating was very low (10%). This effect
was much more distinct for coatings obtained from ACR/SIL dispersions
than for coatings obtained from SIL/ACR dispersions what can be ex-
plained by the fact that in the latter coatings silicone that could stop
water penetration was much more “hidden” inside the acrylic/styrene
copolymer particles – see 3.1.2. It can also be noted that water re-
sistance was generally much better for coatings obtained from SIL/ACR
A and ACR/SIL A dispersions than for coatings obtained from SIL/ACR
B and ACR/SIL B dispersions.
3.2.3. Percentage of swell in toluene and percentage of toluene-soluble
fraction
The percentage of swell of the polymer film in a solvent may be used
for estimation of the level of crosslinking density of the polymer. In our
studies toluene was selected since it is good solvent for both polymers
that constituted the hybrid dispersion particle, i.e. acrylic/styrene co-
polymer and silicone resin. The results shown in Fig. 13 indicate that
the hybrid polymer material that was formed in synthesis of SIL/ACR
dispersions by emulsion polymerization of acrylic/styrene monomers in
starting SIL dispersion was apparently more resistant to solvent than the
acrylic/styrene copolymers of ACR dispersions even for quite low sili-
cone content. This finding may suggest that some grafting of acrylic/
styrene monomers on starting SIL dispersion particles has occurred. In
the case of synthesis of ACR/SIL dispersions by emulsion polymeriza-
tion of silicone monomers in starting ACR dispersions this effect was
observed only when silicone content was quite high what indicated that
it resulted rather from the fact that silicone resin itself was much more
resistant to solvent than silicone-acrylic hybrid. These assumptions
were confirmed by the results of determination of percentage of to-
luene-soluble fraction -see Table 2. For SIL/ACR dispersions values of
that parameter were lower than for ACR dispersions what conformed
that some grafting of acrylic/styrene monomers on silicone resin oc-
curred during polymerization process. For ACR/SIL dispersions values
of that parameter were higher than for ACR dispersions what suggested
that no grafting was present.
3.2.4. Water vapor permeability
Expected improvement of water vapor permeability of the coating is
one of the key reasons why the modification of acrylic/styrene copo-
lymer dispersions used as binders architectural paints with silicone is
recommended. In our study described in [2] we proved that for 25%
silicone content in the particles of hybrid ACR/SIL or SIL/ACR disper-
sions water vapor permeability of the coatings increased significantly. It
was therefore interesting to see whether lower silicone contents (10%
and ca. 15%) would also influence this parameter to large extent. The
results presented in Fig. 14 show that for both coatings made SIL/ACR
and ACR/SIL dispersions water vapor permeability increased distinctly
with increase in silicone content reaching the maximum value for 25%
of silicone in the coating. Specifically, for the coating obtained from
SIL/ACR B dispersion the increase was quite spectacular. In this case
water vapor permeability increased from ca. 15 g/m2/24 h measured
for the coating obtained from unmodified acrylic/styrene copolymer
dispersion up to ca. 25 g/m2/24 h and ca. 65 g/m2/24 h for coatings
containing 10% and 25% silicone, respectively. These results suggest
that even relatively low silicone content in coatings produced from si-
licone/acrylic dispersions with hybrid particle structure will be enough
to achieve distinct increase in water vapor permeability. These results
are, however, quite different from findings of other study [23] where
hybrid dispersions were synthesized by polymerization of acrylic
monomers in PDMS dispersion modified with methacryloyloxypropyl
trimethoxysilane (MATS). The authors of that paper found that in-
creasing the amount of MATS resulted in decrease of water vapor
J. Kozakiewicz, et al. Progress in Organic Coatings xxx (xxxx) xxxx

Fig. 10. AFM images of the surface of coatings made from hybrid SIL/ACR B dispersions obtained using different SIL/ACR ratio (a) 1/3 and (b) 1/9 as compared to
the surface of coating made from unmodified ACR B dispersion (c).

Fig. 11. The effect of silicone content on water resistance of coatings made
from hybrid SIL/ACR A and ACR/SIL A dispersions.

permeability and explained that phenomenon by formation of more
crosslinked polymer structures with increase in MATS content. In our
study the probability of formation of crosslinked structures was quite
low and therefore we observed better water vapor permeability for
coatings containing more silicone.
3.2.5. Mechanical properties
3.2.5.1. Hardness. The effect of silicone content on hardness (Koenig)
of the coatings made from SIL/ACR and ACR/SIL dispersions is
Fig. 12. The effect of silicone content on water resistance of coatings made
from hybrid SIL/ACR B and ACR/SIL B dispersions.
presented in Fig. 15.
It is obvious from the results shown in Fig. 15 that coating hardness
was much affected by modification of coatings with silicone. For
coatings made from SIL/ACR A and ACR/SIL A hybrid dispersions this
effect was not so clear because hardness of coating made from un-
modified acrylic/styrene copolymer dispersion (ACR A) was very low.

9
J. Kozakiewicz, et al.
Fig. 13. The effect of silicone content on % swell in toluene determined for
films made from hybrid SIL/ACR and ACR/SIL dispersions. Swell in toluene
determined for SIL dispersion solids was 202%. Since ACR/SIL B sample con-
taining 10% silicone was completely deteriorated after soaking in toluene (see
Table 2) that experimental point could not be represented on the graph.
Fig. 14. The effect of silicone content on water vapor permeability of coatings
made from hybrid SIL/ACR and ACR/SIL dispersions.
Fig. 15. The effect of silicone content on hardness of films made from hybrid
SIL/ACR and ACR/SIL dispersions.
In the same time it was very significant for coatings made from SIL/ACR
B and ACR/SIL B hybrid dispersions – a drop from 0.5 to ca. 0.2 was
observed even with only 10% silicone in the coating. Such distinct ef-
fect could have been expected taking into account that silicone resin is
quite soft and even small amount of such soft modifier in the coating
may soften the whole body of coating significantly. However, since SIL/
ACR and ACR/SIL hybrid dispersions are foreseen to be applied as
binders for architectural paints the lower hardness of the binder may
not necessarily result in worse performance of the pigmented paint.
3.2.5.2. Adhesion to glass. As it can be seen in Table 1 adhesion to glass
determined for coatings made from both ACR A and ACR B dispersions
was rather poor (according to ENISO 2409 value of 5 means the worst
10
Progress in Organic Coatings xxx (xxxx) xxxx
Fig. 16. The effect of silicone content on impact resistance (direct) of films
made from hybrid SIL/ACR and ACR/SIL dispersions.
adhesion) and generally improved for coatings made from ACR/SIL or
SIL/ACR dispersions, but no clear distinct effect of silicone content in
the coating on adhesion to glass could be observed.
3.2.5.3. Impact resistance and cupping. As it can be noted from Table 2
both direct and reverse impact resistance of coatings made from SIL/
ACR and ACR/SIL dispersions was determined. Based on these results it
can be anticipated that modification with silicone did not affect the
impact resistance (reverse) of coating made from ACR A dispersion
simply because already for that unmodified coating the maximum value
of impact resistance (reverse) was measured. However, in the case of
coating made from ACR B dispersion that was quite brittle, i.e. zero
impact resistance (reverse) was measured, modification with silicone
could help much, but only when silicone content in the coating was
quite high (25%). As it can be noted from the results presented in
Fig. 16 the effect of silicone content on impact resistance (direct) was
quite distinct.
For coatings made from SIL/ACR A and ACR/SIL A dispersions
impact resistance (direct) started to increase really significantly above
10–15% of silicone content in the coating. However, for coatings based
on silicone-modified ACR B this increase was observed only for coatings
made from ACR/SIL B dispersions while for coatings made from SIL/
ACR B dispersions and more silicone resulted in lower impact resistance
(direct). This phenomenon could result from distinct phase segregation
that might occur in these coatings when silicone content was high. The
phase segregation (i.e. silicone particles were mostly separated from
acrylic/styrene copolymer particles) occurred in SIL/ACR B = 1/3 and
SIL/ACR B = 1/6 samples and did not occur in SIL/ACR A = 1/3 and
SIL/ACR A = 1/6 samples. The reason for that phenomenon most
probably was that the composition of monomers in ACR part was dif-
ferent. Actually, for ACR B there was more styrene in the monomers
mixture what resulted in higher Tg (ca. 30 °C as compared to ca. 15 °C
for ACR A).
As it can also be noted from Table 2 the cupping test did not reveal
any differences between coatings made from unmodified acrylic/
styrene copolymer (ACR) dispersions and the coatings made from SIL/
ACR or ACR/SIL dispersions. The reason may be the relatively high
values of cupping resistance obtained in this test for unmodified coat-
ings, so modification with silicone did not result in increase of these
values.
3.2.5.4. Tensile strength and elongation at break. The effect of silicone
content on tensile strength and elongation at break of the films made
from SIL/ACR and ACR/SIL dispersions is presented in Figs. 17 and 18
respectively.
It can be noted from Fig. 17 that tensile strength of the films ob-
tained from SIL/ACR and ACR/SIL dispersions decreased very much
with increase in silicone content. This phenomenon can be explained by
the presence of rigid and tough part (acrylic/styrene copolymer) and
J. Kozakiewicz, et al.
Fig. 17. The effect of silicone content on tensile strength of films made from
hybrid SIL/ACR and ACR/SIL dispersions.
Fig. 18. The effect of silicone content on elongation at break of films made from
hybrid SIL/ACR and ACR/SIL dispersions.
much more soft and elastic part (silicone resin) in the hybrid structure
of the dispersion particles which coalesced to form the films in the
process of drying of the dispersions. It could be then expected that
elongation at break of the films would increase with increase in silicone
content. However, it is interesting that such assumption appeared to be
true only with regard to the films produced from ACR/SIL dispersions
while for the films produced from SIL/ACR dispersions elongation at
break (see Fig. 18) remained at approximately the same level up to 10%
of silicone and after started to decrease slightly with increase in silicone
content. This phenomenon can only be explained by specific structure
of the film made from SIL/ACR dispersions where silicone part was
totally covered by acrylic/styrene copolymer part because of such hy-
brid particles structure - see 3.1.2. If the silicone content was low, si-
licone did not influence the elongation at break at all while for higher
silicone contents the presence of mechanically weak silicone part could
lead to faster break during testing. For films made from ACR/SIL dis-
persions elongation at break increased with increase in silicone content
most probably because silicone and acrylic/styrene copolymer parts
were mixed up well in hybrid dispersion particles.
4. Conclusions
The results of investigations of the effect of silicone content on
properties of aqueous hybrid SIL/ACR and ACR/SIL dispersions syn-
thesized, respectively, by emulsion polymerization of acrylic/styrene
monomers in silicone resin dispersion and by emulsion polymerization
of silicone monomers in acrylic/styrene copolymer dispersion as well as
on properties of coatings and films made from such dispersions proved
that modification with silicone positively influenced several important
features of these dispersions, coatings and films. The substantial con-
clusion is that the properties which are most important from the point
of view of application of these hybrid dispersions as binders for archi-
tectural paints, namely MFFT, surface hydrophobicity, water vapor
permeability and water resistance of coatings could be significantly
improved even for relatively low silicone content (10%) while me-
chanical properties of coatings and films were not much deteriorated.
11
Progress in Organic Coatings xxx (xxxx) xxxx
Hybrid dispersions synthesized in our study were mechanically stable
and have solids content around 50%, small particle size (100–180 nm),
narrow particle size distribution and very low coagulate content.
Differences in dispersion particle appearance for dispersions synthe-
sized with different silicone content or using different method were
identified and it was anticipated that properties of coatings and films
could be influenced by these differences. Detailed investigations of
coating surface properties by XPS and AFM revealed that silicone mi-
grated to coating surface what was reflected in increased surface hy-
drophobicity. Based on the results of the study described in this paper
certain hybrid dispersions can be selected for further examination as
binders in architectural paints. Since the performance of paints was
found to be very good even when hybrid dispersions containing only
10% of silicone part were used as binders we believe that there would
be no techno-economic obstacles in their commercialization.
Data availability
The raw/processed data required to reproduce these findings cannot
be shared at this time due to legal or ethical reasons.
Acknowledgments
This research was funded by Polish State R&D Centre (NCBiR), grant
number PBS/B1/8/2015. The Authors wish to thank dr Piotr Bazarnik
from Warsaw University for conducting TEM studies, dr Janusz Sobczak
and dr Konstantin Nikiforow from Polish Academy of Sciences for
conducting XPS and AFM studies, respectively. The assistance of
Colleagues from Industrial Chemistry Research Institute in testing me-
chanical properties of films, water vapor permeability and dispersion
particle size distribution is also acknowledged.
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