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

polymer w/w ratios. It was found that water absorption of the coatings dispersions ACR A and ACR B, respectively. The compositions of
decreased and contact angle increased with increase in silicone/acrylic monomers were appropriately designed to get Tg of dispersion solids at
polymer w/w ratio from 0 to 50% while in some other earlier paper [6] a level of ca. + 15 °C (ACR A) and at a level of ca. + 30 °C (ACR B).
it was stated that silicone content in such hybrid dispersions (also ob- Unlike in synthesis of standard aqueous acrylic/styrene polymer
tained by direct emulsion copolymerization of acrylic and silicone dispersions ACR A and ACR B dispersions were not neutralized after
monomers) should not be higher than 20% due to “reatardation of the polymerization process in order to ensure low pH value (ca. 3) that was
polymerization and limitation of the conversion”. Similar conclusions needed to conduct subsequent polymerization of silicone monomers in
were made based on the results of another study [7]. Positive effect of the process of synthesis of hybrid acrylic-silicone (ACR/SIL A and ACR/
silicone content on water resistance and surface hydrophobicity of SIL B) dispersions.
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 2.2. Synthesis of silicone resin dispersions (SIL) and hybrid silicone-acrylic
the part of silicone grafted onto acrylic polymer is responsible for such (SIL/ACR A and SIL/ACR-B) and acrylic-silicone (ACR/SIL A and ACR/
enhancement of properties, including also thermal stability and me- SIL B) dispersions
chanical properties. As it was proved in [10], if the content of the
grafted silicone was changed the water distribution in the drying coats Synthesis of silicone resin dispersion (SIL) applied as starting dis-
was different what distinctly affected the drying time. persion for emulsion polymerization of acrylic monomers to obtain SIL/
The effect of silicone content on the properties of hybrid disper- ACR hybrid dispersions was conducted following the procedure de-
sions, specifically on dispersion stability and coagulum content was scribed in [16] using a mixture of silicone monomers with the following
investigated in a study described in [12] where 3-methacrylox- composition : D4 - 84.0%, MTES - 9.5%, VTES - 6.5%. DBSA was acting
ypropyltrimethoxysilane was polymerized in aqueous acrylic polymer as both surfactant and D4 ring opening catalyst. The reactions which
dispersion. It was confirmed that only certain amount of silicone could proceeded during the process of synthesis of SIL dispersion comprised
be grafted on acrylic polymer to produce core-shell particle structures ring opening polymerization of D4 and hydrolysis of ethoxysilane
and further increase in silicone part content led to poor dispersion groups of MTES and VTES leading to formation of silanol groups cap-
stability and increased coagulum content due to formation of separate able for further condensation. The product of these reactions was
crosslinked silicone particles. It was also proved in the other studies aqueous dispersion of partly crosslinked silicone resin. The process of
[13,14] that increasing the content of silicone part in a hybrid disper- synthesis of silicone resin dispersion (SIL) is shown in Fig. 1.
sion led to the increase in dispersion particle size. This phenomenon After distillation of ethanol under vacuum no free VTES or MTES
was explained by condensation of silanol groups formed during hy- were detected by GC in the resulting SIL dispersion, though small
drolysis of alkoxysilane groups in silicone monomers that is more amounts of D4 (ca. 0.8%) and ethanol (ca. 0.2%) were still present. The
probable at higher silicone content in the system. However, when the conversion of VTES and MTES in that process was practically 100%
hybrid dispersion was made by polymerization of acrylic monomers in while the conversion of D4 was rather low due to cyclic to linear oli-
aqueous polydimethylsiloxane (PDMS) dispersion [15] the opposite gosiloxanes thermodynamic equilibrium and varied from ca. 30% for
effect was observed, i.e. the particle size decreased with increase in ACR/SIL = 3/1 to 80-90% for ACR/SIL = 9/1.
silicone/acrylic polymer ratio and it was explained by “shrinking of Synthesis of hybrid silicone-acrylic (SIL/ACR A and SIL/ACR B) by
PDMS chains in the hydrophobic core”. polymerization of acrylic/styrene monomers in SIL dispersion and of
The examples of studies where the effect of silicone content on hybrid acrylic-silicone (ACR/SIL A and ACR/SIL B) dispersions by
properties of silicone-containing aqueous dispersions with hybrid par- polymerization of silicone monomers in acrylic/styrene polymer dis-
ticle structure as well as the corresponding coatings and films show that persions ACR A and ACR B was conducted as described in [2]. The
though some conclusions in that regard concerning specific systems conversion of monomers in this process was close to 100% since the
could be made there was no systematic study published were that concentration of monomers in the final dispersions was very low (below
subject was investigated in greater detail. In this study we attempted to 0.01%). The ratio (w/w) of silicone polymer and acrylic polymer
fill that gap. 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
2. Materials and methods solids. It was essential that the composition and concentration of sur-
factants remained the same in all SIL/ACR and ACR/SIL dispersions
2.1. Starting materials despite the SIL/ACR or ACR/SIL ratio, so their properties (and prop-
erties of coatings obtained from them) could be compared.
Octamethylcyclotetrasiloxane (D4) was obtained from Momentive.
Other silicone monomers, i.e. vinyltriethoxysilane (VTES) and methyl- 2.3. Characterization of dispersions
triethoxysilane (MTES) were obtained from Evonic. Surfactants - do-
decylbenzenesulphonic acid (DBSA) and Rokanol T18 (non-ionic) were All dispersions were characterized by:
obtained from PCC Exol and Emulgator E30 (anionic) was obtained - Solids content, wt% – percentage of sample mass remaining after
from Leuna Tenside GmbH. Other standard ingredients used in synth- drying for 1 h at 80◦C followed by 4 h at 125 °C.
esis of dispersions (sodium acetate, sodium hydrocarbonate, potassium - pH – using standard indicator paper and Elmetron Pehameter CP-
persulphate and aqueous ammonia solution) were obtained from 411 with ERH-11S electrode
Standard Lublin. Biocide used to protect dispersions from infestation - Viscosity – using Bohlin Instruments CVO100 rheometer, cone-
was Acticide MBS obtained from THOR. plate 60 mm diameter and 1 deg measuring device, shear rate 600 s−1
Starting acrylic/styrene copolymer dispersions (ACR A and ACR B) - Coagulum content - after filtration of dispersion on 120 mesh net
characterized by different glass transition temperatures (Tgs) were the solids remaining on the net were dried and weighed. Coagulum
supplied by Dispersions&Resins. Monomers applied in synthesis of ACR content (wt%) was calculated from equation mc/mdx100% where mc
A and ACR B dispersions were butyl acrylate (BA) obtained from ECEM, was mass of dry coagulum remaining on the net and md was mass of
Arkema, styrene (ST) obtained from KH Chemicals, Helm, acrylic acid dispersion.
(AA) obtained from Prochema, BASF and methacrylamide (MA) ob- - Acrylic and styrene monomers, ethanol and D4 content – by GC
tained from ECEM, Arkema. Acrylic and styrene monomers were used (HP 5890 series II apparatus, FID detector)
as received as mixtures designated as A and B with compositions cor- - Mechanical stability – lack or occurrence of separation during
responding to compositions of monomers applied to synthesize rotation in Hettich Universal 32R centrifuge at 4000 r.p.m. for 90 min

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

Fig. 1. Process of synthesis of silicone resin dispersion (SIL) by emulsion polymerization of silicone monomers.

was considered as good stability 6 days under water were also examined.
- Average particle size (nm), particle size distribution and zeta po- Water vapor permeability – according to ASTM F1249. TotalPerm
tential (mV) – light scattering method using Malvern Zeta Sizer appa- 063 (Extra Solution) apparatus was used. Tests were conducted at 23 °C
ratus for 0.35 mm thick film. Fomblin perfluorinated grease from Solvay
- Particle appearance – STEM (Scanning Transmission Electron Solexis was applied to seal the test vessels.
Microscope) Hitachi 2700, dispersions were diluted 1000× with water Moreover, coatings applied on PET film were examined for surface
for taking pictures. High Angle Annular Dark Field (HAADF) mode also structure by X-ray Photoelectron Spectroscopy (XPS) using ULVAC/
called “Z-contrast” was applied for processing the images reproduced in PHYSICAL ELECTRONICS PHI5000 VersaProbe apparatus and by
this paper. Atomic Force Microscopy (AMF) using RHK-VHV350 apparatus
- Minimum Film Forming Temperature (MFFT) – according to ISO working in a “tapping mode” with PPP-RT-NCHR nanosensors.
2115 using Coesfeld apparatus equipped with temperature gradient
plate. Temperature range : −3 °C to +50 °C. 2.5. Characterization of films
- Glass transition temperature (Tg) of dispersion solids – by DSC (TA
Instruments Q2000 apparatus), heat–cool–heat regime, 20◦C/min - % 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-
2.4. Characterization of coatings 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.
Coatings were produced from dispersions by applying them on glass % swell was calculated from the equation : % swell = m1-m0/
(for testing contact angle, hardness, adhesion or water resistance), m1x100%, where m0 = mass of the sample before test and m1 = mass
aluminium plates (for testing elasticity) or on steel plates (for testing of the sample after test. For determination of percentage of toluene-
impact resistance and cupping) using 120μ applicator. Drying was soluble fraction the films were weighted before immersion in toluene
carried out for 30 min at +50 °C and then the coatings were seasoned in and then after complete drying at room temperature (till no weight
a climatic chamber at +23 °C and 55% R.H. for 72 h. Since no con- change was noticed). % of toluene-soluble fraction was calculated from
tinuous coating could be obtained in this procedure for SIL/ACR B 1/3 the equation : % of toluene soluble fraction = m1-m0/m1x100%, where
the relevant dispersion was dried at +8 °C for 2 h and then seasoned as m0 = mass of the sample before test and m1 = mass of the sample after
above. The resulting coatings were characterized by: test.
- Contact angle (water) – according to EN 828:2000, using KRUSS - mechanical properties (tensile strength and elongation at break) –
DSA 100E apparatus. determined for 0.2 mm thick films using Instron 3345 testing machine
- Pendulum hardness (Koenig) – according to EN ISO 1522 according to EN-ISO 527-1 at a speed of 50 mm/min.
- Adhesion to glass – according to EN ISO 2409
- Elasticity – according to EN ISO 1519 3. Results and discussion
- Impact resistance (direct and reverse) – according to EN ISO 6272-
1, using Erichsen Variable Impact Tester Model 304 3.1. Effect of silicone content on properties of dispersions
- Cupping – according to EN ISO 1520, using Erichsen Cupping
Tester All SIL/ACR and ACR/SIL dispersions synthesized in our study were
- Water resistance – glass Petri dishes of 50 mm diameter were filled mechanically stable. Free acrylic/styrene monomers content in SIL/
with distilled water and placed upside-down on the coating, so the ACR dispersions was below 0.01% while ACR/SIL dispersions contained
coating was covered with 7 mm thick layer of water. Assembles pre- no free acrylic/styrene monomers. Ethanol and D4 content in both SIL/
pared this way were left for 72 h and appearance of coatings was ex- ACR and ACR/SIL dispersions was at the level of 0.1% and 0.4% re-
amined for the bubbles size (S0 - no bubbles, S2-S5 - low to high size of spectively. The other properties of dispersions obtained using different
bubbles) and density (0 - no bubbles, 2–5 low to high density of bub- SIL/ACR or ACR/SIL ratio are shown in Table 1. Designation of dis-
bles) according to EN ISO 4628-2. Changes of coating appearance after persion in the table reflects the method of its synthesis and the

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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 than that of acrylic/styrene dispersion what suggests that indeed hybrid
to hybrid dispersion synthesized by polymerization of acrylic/styrene particles were obtained. This finding was confirmed by TEM in-
monomers with composition ACR A in silicone resin dispersion ap- vestigations – see 3.1.2.
plying the ratio (w/w) of silicone monomers to silicone dispersion so- It is also clear that the average particle size of SIL/ACR dispersions
lids equal to 1/9 (w/w) while designation ACR/SIL B 3/1 corresponds was higher than that of ACR/SIL dispersions for all SIL/ACR or SIL/ACR
to hybrid dispersion synthesized by polymerization of silicone mono- ratios what most probably resulted from different appearance of dis-
mers in acrylic/styrene polymer dispersion ACR B applying the ratio persion particles when dispersions were obtained by different methods -
(w/w) of acrylic/styrene dispersion solids to silicone monomers equal see discussion on appearance of dispersion particles in 3.1.2 and in [2].
to 3/1. As it can be noted from Table 1 all hybrid dispersions had solids Another interesting finding from Fig. 2 is that the average particle size
content equal to ca. 50% and pH equal to ca. 6. The coagulum content was generally higher for higher SIL contents for both SIL/ACR and
was found to be quite low, especially for SIL/ACR dispersions, as ACR/SIL dispersions and for both ACR A - based and ACR - B based
compared to the relevant values reported for other hybrid silicone/ dispersions. That finding is consistent with the results reported by the
acrylic dispersions [17–21] and viscosity was rather low other authors [5] who, however, obtained hybrid SIL/ACR dispersions
(20–350 mPa s). 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
3.1.1. Particle size and particle size distribution hybrid SIL/ACR dispersions is a general rule. Nevertheless, in disper-
As it can be noted from Table 1 the particle size of hybrid disper- sions investigated in our study a maximum was observed for ca. 15% of
sions was generally close to 100–150 nm and particle size distribution silicone in dispersion solids what could suggest that the change in ap-
was quite narrow. The effect of SIL/ACR or ACR/SIL ratio (i.e. silicone pearance of dispersion particles occurred at that specific SIL/ACR (1/6)
content in the dispersion solids) on average particle size of SIL/ACR and or ACR/SIL (6/1) ratio. This assumption was confirmed by the results of
ACR/SIL hybrid dispersions is shown in Fig. 2. particle appearance studies described in 3.1.2.
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- 3.1.2. Particle appearance
gardless SIL/ACR or ACR/SIL ratio and method of hybrid dispersion The particle appearance observed for different contents of silicone
synthesis the particle size of hybrid dispersions was generally higher 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
Fig. 2. The effect of SIL/ACR or ACR/SIL ratio (i.e. silicone content in the a sphere trapped in the mass of acrylic/styrene copolymer. However,
dispersion solids) on average particle size of SIL/ACR and ACR/SIL hybrid such structure was not present in ACR/SIL B 3/1 dispersion.
dispersions.

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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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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

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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. 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.

Fig. 7. The effect of silicone content on CA (water) of coatings made from 3.2.3. Percentage of swell in toluene and percentage of toluene-soluble
hybrid SIL/ACR and ACR/SIL dispersions. 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
Fig. 8. The effect of silicone content on SFE of coatings made from hybrid SIL/ resistant to solvent than silicone-acrylic hybrid. These assumptions
ACR and ACR/SIL dispersions. 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
Fig. 9. Differences in Si content on the surface of coatings made from hybrid results presented in Fig. 14 show that for both coatings made SIL/ACR
SIL/ACR dispersions obtained using different SIL/ACR ratio. and ACR/SIL dispersions water vapor permeability increased distinctly
with increase in silicone content reaching the maximum value for 25%
lower SFE values) are observed at lower SIL/ACR ratios. These results of silicone in the coating. Specifically, for the coating obtained from
suggested that the surfaces of coatings which contained more silicone SIL/ACR B dispersion the increase was quite spectacular. In this case
were more enriched with silicone what was proved by XPS studies – see water vapor permeability increased from ca. 15 g/m2/24 h measured
Fig. 9. for the coating obtained from unmodified acrylic/styrene copolymer
The apparent differences in the structure of coating surface de- dispersion up to ca. 25 g/m2/24 h and ca. 65 g/m2/24 h for coatings
pending on SIL/ACR ratio can be seen on AFM images presented in containing 10% and 25% silicone, respectively. These results suggest
Fig. 10. While the surface of coating made from unmodified ACR B that even relatively low silicone content in coatings produced from si-
dispersion (c) seem to be rather smooth the round-shaped structures licone/acrylic dispersions with hybrid particle structure will be enough
with ca. 100 nm size are emerging from the surface of coatings made to achieve distinct increase in water vapor permeability. These results
from SIL/ACR B dispersions modified with silicone (a) and (b) and are are, however, quite different from findings of other study [23] where
much more abundant for the coating that contains more silicone (a). hybrid dispersions were synthesized by polymerization of acrylic
monomers in PDMS dispersion modified with methacryloyloxypropyl
3.2.2. Water resistance trimethoxysilane (MATS). The authors of that paper found that in-
The effect of silicone content on water resistance of coatings made creasing the amount of MATS resulted in decrease of water vapor

8
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 Fig. 12. The effect of silicone content on water resistance of coatings made
crosslinked polymer structures with increase in MATS content. In our from hybrid SIL/ACR B and ACR/SIL B dispersions.
study the probability of formation of crosslinked structures was quite
low and therefore we observed better water vapor permeability for presented in Fig. 15.
coatings containing more silicone. 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
3.2.5. Mechanical properties effect was not so clear because hardness of coating made from un-
3.2.5.1. Hardness. The effect of silicone content on hardness (Koenig) modified acrylic/styrene copolymer dispersion (ACR A) was very low.
of the coatings made from SIL/ACR and ACR/SIL dispersions is

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

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- Fig. 16. The effect of silicone content on impact resistance (direct) of films
taining 10% silicone was completely deteriorated after soaking in toluene (see made from hybrid SIL/ACR and ACR/SIL dispersions.
Table 2) that experimental point could not be represented on the graph.

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. 14. The effect of silicone content on water vapor permeability of coatings Fig. 16 the effect of silicone content on impact resistance (direct) was
made from hybrid SIL/ACR and ACR/SIL dispersions. 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
Fig. 15. The effect of silicone content on hardness of films made from hybrid
for ACR A).
SIL/ACR and ACR/SIL dispersions. 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/
In the same time it was very significant for coatings made from SIL/ACR
ACR or ACR/SIL dispersions. The reason may be the relatively high
B and ACR/SIL B hybrid dispersions – a drop from 0.5 to ca. 0.2 was
values of cupping resistance obtained in this test for unmodified coat-
observed even with only 10% silicone in the coating. Such distinct ef-
ings, so modification with silicone did not result in increase of these
fect could have been expected taking into account that silicone resin is
values.
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 3.2.5.4. Tensile strength and elongation at break. The effect of silicone
binders for architectural paints the lower hardness of the binder may content on tensile strength and elongation at break of the films made
not necessarily result in worse performance of the pigmented paint. 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-
3.2.5.2. Adhesion to glass. As it can be seen in Table 1 adhesion to glass tained from SIL/ACR and ACR/SIL dispersions decreased very much
determined for coatings made from both ACR A and ACR B dispersions with increase in silicone content. This phenomenon can be explained by
was rather poor (according to ENISO 2409 value of 5 means the worst the presence of rigid and tough part (acrylic/styrene copolymer) and

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J. Kozakiewicz, et al. 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
Fig. 17. The effect of silicone content on tensile strength of films made from binders in architectural paints. Since the performance of paints was
hybrid SIL/ACR and ACR/SIL dispersions. 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
Fig. 18. The effect of silicone content on elongation at break of films made from and dr Konstantin Nikiforow from Polish Academy of Sciences for
hybrid SIL/ACR and ACR/SIL dispersions. conducting XPS and AFM studies, respectively. The assistance of
Colleagues from Industrial Chemistry Research Institute in testing me-
much more soft and elastic part (silicone resin) in the hybrid structure chanical properties of films, water vapor permeability and dispersion
of the dispersion particles which coalesced to form the films in the particle size distribution is also acknowledged.
process of drying of the dispersions. It could be then expected that
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