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Synthesis and characterization of silicone modified acrylic resin and its uses
in the emulsion paints

Article  in  Iranian Polymer Journal · March 2005

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 Iranian Polymer Journal
14 (3), 2005, 211-222

Synthesis and Characterization of Silicone

Modified Acrylic Resin and its Uses in the
Emulsion Paints
Hamid Javaherian Naghash*1, Shadpour Mallakpour2, and Neda Kayhan1

(1) Department of Chemistry, Shahreza Islamic Azad University, P.O. Box: 311/86145, Shahreza
Isfahan, I.R. Iran
(2) Organic Polymer Chemistry Research Laboratory, College of Chemistry, Isfahan University
of Technology, Isfahan-84156, I.R. Iran

Received 7 March 2004; accepted 18 September 2004

ABSTRACT

he acrylate-silicone emulsions were prepared by emulsion copolymerization of

T methylmethacrylate (MMA), butylacrylate (BA), methacrylic acid (MAA) with vinyl-

triethoxysilane (VTES), and auxiliary agents at 85oC in the presence of potassium
persulphate (KPS) as initiator. Alkylphenol ethersulphate and Arkupal N-300 were used
as anionic and non-ionic emulsifiers, respectively. The resulting copolymers were char-
acterized by using Fourier transform infrared spectroscopy (FTIR). Thermal properties of
the copolymers were studied by using thermogravimetric analysis (TGA) and differential
scanning calorimetry (DSC). The morphology of copolymers was also investigated by
scanning electron microscopy (SEM) and then the effects of temperature, agitation
speed, initiator and VTES concentrations on polymerization rate are discussed. The
obtained polymers had high solid content (43%) and were used in the emulsion paints as
a binder. The experimental results show that these polymers supply very useful proper-
ties such as excellent storage stability, UV light stability, washing and abrasion resistance
with good brushing in the above mentioned paints. The calculations of monomer conver-
sion versus time histories and monomer conversion to polymer indicate that by increas-
ing the VTES concentration, the polymerization rate and the number of polymer particles
Key Words: decrease, respectively.
emulsion copolymerization;
methylmethacrylate;
butylacrylate;
methacrylic acid;
vinyltriethoxysilane.

INTRODUCTION

In recent years acrylic emulsion catalyst, water with one or more

copolymerization in the presence of monomers, which are not miscible
silicone has received considerable with water and an oil in-water emul-
attention as a industrial method [1- sifier. These emulsions are generally
10]. In these processes polymeriza- opaque, milky, and viscous solution,
(*) To whom correspondence should be addressed. tions are achieved with the assistance but they can also be translucent
E-mail: [email protected] of a water or oil-soluble initiator or emulsions with particle sizes ranging
 Synthesis and Characterization of Silicone Modified ... Javaherian Naghash H. et al.

from about 8-80 nm when very high surfactant concen- EFKA-2526 was kindly supplied by EFKA, Holland.
tration is employed [11-15]. When an aqueous acrylate The dispersing agent, Disperse A was obtained from
polymer emulsion obtained by emulsion polymeriza- BASF, Germany and the softening agent dioctylphtha-
tion is dried at room temperature or under heated con- late was a commercial product. Water was double dis-
ditions, a coating is obtained which has a relatively tilled and deionized.
good durability. Therefore, aqueous acrylate polymer
emulsions have been widely used as a resin for aqueous Polymerization Procedure
paints. However, when a coating which is obtained Continuous emulsion copolymerization was carried out
from an acrylate polymer emulsion or for a paint com- using a 500-mL 5- necked round bottom flask equipped
prised of acrylate polymer emulsion with a pigment, is with a reflux condenser, stainless steel stirrer, sampling
exposed to outdoor conditions or UV light, not only is device and two separate feed streams. The first feed
the luster of the coating likely to rapidly deteriorated, stream was a solution of MMA, BA, MAA, VTES and
but also the gloss retentivity of the coating is poor. anionic surfactant. The other feed was the initiator
In order to solve these problems, it was proposed to solution 7.0 × 10-3 M. Before emulsion polymerization
add silicone to an aqueous acrylate polymer emulsion start-up, the reaction vessel was first charged with the
to increase the coating resistance to UV light, oxygen, desired amounts of water, emulsifier, NaHCO3 and ini-
permeation of water and various types of solvents. tiator solution, respectively. During polymerization
These will improve the durability of the coating [16- process the reaction mixture was stirred at a rate of
29]. Also, Yamaya and coworkers [30] emphasized that 60 rpm and the temperature was maintained at 60oC.
silicone resins, resulting from hydrolytic condensation After 5 min a small portion of the monomer mixture
of silane compounds, could be used since they are able was added to the flask at a period of 20 min. Then the
to form films having high hardness, water and heat temperature was kept at 85oC. The polymerization was
resistance. In this paper we wish to elucidate the effects performed under air atmosphere to investigate the
of VTES on the properties of acrylate emulsion poly- effect of temperature, agitation speed, initiator and
merization and emulsion paints. VTES concentration on monomer conversion. A typical
recipe for the preparation of a 43% solid product is
given in Table 1.
EXPERIMENTAL In order to determine the conversion percentage

Materials
Table 1. Polymerization recipe at 85oC.
The monomers MMA (Merck) and BA (Merck), were
freed from the inhibitor by shaking with 10% aqueous Initial
Compound Feed Total
NaOH, washing with water and drying over Na2SO4. charge
They were then distilled under reduced pressure before MMA (g) 4.80 43.20 48
use and stored at -15oC to avoid thermal polymeriza- n-BA (g) 2.25 20.25 22.50
tion. The MAA (Merck) was distillated directly under
MAA (g) 0.025 0.225 0.25
vacuum and stored at 0oC. VTES, (Merck) was analyt-
ical grades and used directly without further purifica- VTES (g) 10% w 90% w Variable (0-5)
tion. The initiator KPS (Merck); buffer, NaHCO3 Buffer: NaHCO3 (g) 0.75 - 0.75
(Merck); complex emulsifier alkylphenol ether sul- Initiator: K2S2O8 (g) 0.10 0.40 0.50
phate and Arkupal N-300 were purchased from Henkel,
Demineralized water (g) 126 - 126
Germany and were used as received. Sodium benzoate,
hydroxyethyl-cellulose, ammonia solution 25%, titani- No-ionic emulsifier:
um dioxide, aluminium silicate, talc (325 mesh), calci- Arkupal N-300 (g) 5.00 - 5.00
um carbonate, formaldehyde, ethylene glycol, butyl Anionic emulsifier:
glycol and mineral spirits were supplied from Fluka
Alkylphenol ethersulphate (g) 0.50 4.50 5.00
and used without further purification. The antifoam,

212 Iranian Polymer Journal / Volume 14 Number 3 (2005)

 Javaherian Naghash H. et al. Synthesis and Characterization of Silicone Modified ...

during the polymerization process, it was necessary to Where Mo is the initial monomer concentration per
withdraw samples at various intervals from the reaction mL, and ρp is the density of the polymer (g /mL) [32 -
vessel. These samples are relatively small so that the 34 ] .The volume average diameter of the latexes were
overall composition in the reactor is not seriously found to be 1500, 6000, and 7000 nm for 0.00, 0.15 and
affected. Once a sample is removed and put in a watch 0.25 molar VTES containing copolymers, respectively.
glass, polymerization is terminated by the addition of 7 Although the produced copolymers have low solubility
ppm hydroquinone. Then 2 drops of ethanol is added to in various solvents such as toluene, benzene, acetic
the sample as a coagulant agent and the contents of the acid, xylene, N,Ní-dimethylformamide (DMF),
watch glass were evaporated at room temperature, then dimethylsulphoxide (DMSO), N-methylpyrrolidone
dried to constant weight in vacuum oven. The conver- (NMP), acetone and dichloroethane which makes it dif-
sion percentage was determined gravimetrically. The ficult for their characterization, but their morphology as
purification and precipitation of the polymer were done well as their thermal properties gave important infor-
using Grassies method [31]. The number of polymer mation about their structure and property relation. On
particles per unit volume of water (NT) was calculated the other hand the appearance properties of the prod-
from the monomer conversion XM and the volume ucts such as adhesiveness, transparency of the film and
average diameter of the polymer particles, dv was elasticity are excellent and indicate the formation of
determined by a scanning electron microscope, using copolymers. Also with the prepared copolymer, we
the following equations: made some different building paints which were under
3 testing for eight months and during this time we did not
∑ nid υ
d 3υ = (1) observe any fluctuation such as decomposition, sedi-
∑ ni mentation and floating.
Furthermore, the comparison of these paints with
6M ο X M
NT = (2) their available standard samples showed a very good
πd 3υρ p maintenance time without any gelation. The repro-

Table 2. Emulsion paint recipe.

Compound Functional Amount (%) Amount (g)

Water Solvent 28 279.5

Sodium benzoate Softening agent 0.19 1.9
EFKA 2526 Antifoaming 0.36 3.58
Hydroxyethylcellulose Thickening agent 0.6 6
Ammonia solution 25% pH Adjustment 0.16 1.6
Titanium dioxide Opacifying white pigment 11.64 116.2
Aluminum silicate Extender 2.54 25.4
Talc (325 mesh) Extender 5.45 54.5
Calcium carbonate Extender 31.98 319.8
Formaldehyde Antibactericid 0.2 2
Ethylene glycol Co-solvent, antifreeze 1.07 10.7
Butyl glycol Coalescence agent 0.93 9.3
Mineral spirits Levelling agent 0.93 9.3
Disperse A Dispersing agent 0.39 3.9
Dioctylphthalate Softening agent 0.5 5
VTES Modified acrylic resin Binder 15.06 150.6

Iranian Polymer Journal / Volume 14 Number 3 (2005) 213

 Synthesis and Characterization of Silicone Modified ... Javaherian Naghash H. et al.

Table 3. Physical properties of emulsion paint.

VTES Concentration Washing and abrasion Drying time

UV resistance Brushing control
(molar) resistance (cycles) (min)

0.00 5000 Turn yellowish By painting-brush effect 60

0.05 5000 Turn yellowish By painting-brush effect 60
0.10 6000 No yellowing By painting-brush effect 60
0.15 7500 No yellowing No brush marks can be seen 75
0.20 9000 No yellowing No brush marks can be seen 75
Density: 1.35 g/mL, viscosity: 1600 cps

Table 4. Morphologies of latex particles at different VTES concentrations.

[VTES]= 0.00 XM 50 55 65 69 75 86 95 100

Dn = 1.5 × 103 nm NT × 10-13 nm 838 922 1089 1157 1257 1442 1592 1676

[VTES]= 0.15 XM 45 52 63 65 86 94 96 100

Dn = 6 × 103 nm NT × 10-13 nm 12 13.6 16.5 17 22.5 24 25 26

[VTES]= 0.25 XM 32 44 51 60 75 90 92 100

Dn = 7 × 103 nm NT × 10-13 nm 5.3 7.25 8.41 10 12.3 14.8 15.1 16.5
[M]0 = 4.0 M, ρp = 1.35 g/mL, 60 rpm, T= 85 C, [I]0 =7×10
o -3

ducibility of the kinetic data was checked by repeating using a 2000 mL round bottom metal vessel, equipped
the experiments and each monomer conversion consid- with a stainless steel stirrer. This vessel was first
ered in this paper is an average of at least four measure- charged with water, sodium benzoate, dispersing agent,
ments and the deviation between four runs was always ammonia solution, defoamer, hydroxyethyl-cellulose
less than 5%. and then the reaction mixture was stirred at a rate of
1600 rpm at room temperature. After 15 min alumini-
Polymer Characterization um silicate, talc, titanium dioxide, calcium carbonate
DSC Thermograms were taken on a Mettler TA 4000 and dispersing agent were added, respectively and it
Model apparatus at a heating rate of 10oC/min. The was stirred for another 30 min with 2000 rpm. Then it
glass transition temperature (Tg) was taken at the onset cooled to 25-30oC and silicone modified acrylic resin
of the corresponding heat capacity jump. TGA Mea- was added to the mixture. After this, mineral spirits,
surements of copolymers were carried out by a Dupont ethylene glycol, butyl glycol and formaldehyde were
TGA 951 under nitrogen atmosphere at a heating rate added and stirred for 45 min which means the whole
of 10oC/min. Scanning electron micrographs were process took 90 min and then, the pH was adjusted with
taken on a Jeol-JXA 840 A SEM. The specimens were ammonia solution between 7.5-8.0. The amount of all
prepared for SEM by freeze-fracturing in liquid nitro- ingredients [35,36] and general properties of this paint
gen and applying on a gold coating of approximately are summarized in Tables 2-4, respectively.
o
300 A on an Edwards S 150 B sputter coater. FTIR
Spectra of the copolymers were taken using a Nicolet Preparation of Paint Films
Impact 400 D Model spectrophotometer. For making paint films a four-edge applicator 125
micron has been used. In order to do this, the paints
Preparation of Emulsion Paints by the Obtained were charged in to the empty bulk of apparatus, then it
Resin was applied on the plastic surface and removed from up
The preparation of emulsion paints was carried out to down direction slowly. After coating of the glass or

214 Iranian Polymer Journal / Volume 14 Number 3 (2005)

 Javaherian Naghash H. et al. Synthesis and Characterization of Silicone Modified ...

plastic surface the evaporation of solvent (water)

resulted in the formation of paint films. In this order,
the existence of some cosolvents such as white spirits
act as a leveling agent and consequently an adequate
film was supplied. This is a short description of film
formation mechanism.

RESULTS AND DISCUSSION

Agitation Effect
In heterogeneous reaction systems, mass transfer is one
of the important factor that affects polymerization rate. Figure 2. The effect of agitation speed on monomer conver-
In order to investigate the mass transfer effect on the sion vs. impeller speed at ( ) 15; ( ) 60; and (*) 90 min. Min
polymerization rate, experiments were carried out [M]0 = 4.0 M, [VTES] = 0.05 M, T = 85oC, [I]0 = 7.0 × 10-3 M.
under conditions of different impeller speeds [37].
Experimental results are presented in Figures 1 and 2 emulsion polymerization. However, a reduction in
where the conversion of monomer to polymer are plot- impeller speed to 60 rpm leads to earlier attainment of
ted against reaction time and impeller speeds at differ- an acceleration in the polymerization rate. According-
ent agitation speeds. In these experiments, initiator ly, the reaction time required to attain high conversion
concentration, was 7.0 × 10-3 M in H2O and the con- is shorter at 60 rpm than at the other impeller speeds.
centration of total monomer added per unit volume of Arai and coworkers [39] observed a similar tendency
aqueous phase, M0 was 4.0 M in H2O. In Figure 1 agi- for emulsion polymerization in the absence of a solid
tation speeds show the highest polymerization rate at phase and were explained by a consideration of
60 rpm and lowest polymerization rate at 300 rpm. Fig- monomer mass transfer from monomer droplets to the
ure 2 confirms a decrease in the polymerization rate by polymer particles formed in the aqueous phase.
increasing the agitation speed and also the experimen-
tal results at agitation speeds between 72 and 100 rpm Effect of Initiator Concentration
do not show any difference in polymerization rate. It is Figure 3 shows the results of different initiator concen-
worth to be mentioned that Peng et al. [38] have report- trations on the polymerization reaction rate. Upon
ed the same variation in the organosilicon composite increase in initiator concentrations at both the initial

Figure 1. The effect of agitation speed on monomer conver- Figure 3. The effect of initial initiator concentration on
sion vs. polymerization time at ( ) 100; (*) 200; and ( ) 300 monomer conversion vs. time at [K2S2O8] × 10-3 = ( ) 3;
rpm . [M]0 = 4.0 M, [ VTES ] = 0.05 M, T = 85oC, [I]0 = 7.0 ( ) 7; and (*) 14 M; [M]0 = 4.0 M, [VTES] = 0.05 M, 60 rpm,
× 10-3 M. T = 85oC.

Iranian Polymer Journal / Volume 14 Number 3 (2005) 215

Synthesis and Characterization of Silicone Modified ... Javaherian Naghash H. et al.

and intermediate stages of reaction leads to an enhance-

ment of the polymerization rate. The rate increase at the
intermediate stage suggests the existence of more than
one radical in a polymerization locus. Thus the poly-
merization mechanism is different from that of an ideal
emulsion polymerization, [40, 41], in which only one
radical can exist and no gel effect appears.

Effect of Temperature
The effects of temperature of maximum conversion and
the initial rate of emulsion copolymerization of silicone
modified acrylic are represented in Figure 4. The tem-
perature range studied at fixed concentration of Figure 5. The effect of initial VTES concentration on
monomers and initiator was between 60 to 90oC. It was monomer conversion vs. time at ( ) 0.05; ( ) 0.20; and ( )
observed that both initial rate of polymerization and 0.25 M. [M]0 = 4.0 M, 60 rpm, [I]0 = 7.0 × 10-3 M, T = 85oC.
maximum conversion increased with increasing tem-
perature. Figure 4 also shows that there is no any poly- agent and softener [42] and it is enriched on surface of
merization onset at 75oC. After this temperature it has the film [27]. On the other hand You et al. [28] demon-
been observed that there is an increase in the polymer- strated that silanes can be bonded with hydroxyl groups
ization rate by increasing temperature. The tempera- on the surface of substrate to increase the adhesion and
tures 85 and 90oC are suitable for these systems but at also FTIR analysis indicated that organic functional
85oC the highest conversion percentage is noticed silanes can be polymerized with other monomers. Fig-
others. Actually very high temperature such as 90oC ure 5 shows the effect of VTES concentration on the
and more is dangerous for these systems, because the conversion versus time histories where the initial initia-
polymer may turn to gel point. tor and total monomer concentrations were constant at
[I]0 = 7.0 × 10-3 M and [M]0 = 4.0 M. It has been
Effects of the VTES Concentration observed that the rate of reaction decreases with
Addition of VTES in acrylic emulsion provides benefi- increase the amount of VTES. Figure 6 confirms a
cial effects by improving various mechanical properties decreasing in the reaction rate with increasing VTES
such as water and weatherability and good acid and concentration. Kan et al. [44] also observed the same
alkali resistance [24,27,43]. In addition to this, the
incorporation of silicone plays the roles of coupling

Figure 6. The effect of initial VTES concentration on

Figure 4. The effect of reaction temperature on monomer monomer conversion vs. silicone percent at ( ) 15; ( ) 30;
conversion vs. time at ( ) 60; ( ) 70; ( ) 85 and (×) 90oC [M] ( ) 45; ( ) 90 and (*) 120 min. [M]0 = 4.0 M, 60 rpm, [I]0 =
0 = 4.0 M, [VTES] = 0.05 M, 60 rpm, [I]0 = 7.0 × 10-3 M. 7.0 ×10 -3 M, T = 85oC.

216 Iranian Polymer Journal / Volume 14 Number 3 (2005)

 Javaherian Naghash H. et al. Synthesis and Characterization of Silicone Modified ...

behaviour in the acrylate-silicone emulsion. 0.10, 0.15 and 0.20 molar VTES can be clearly
It is known that the rate of propagation and conse- observed. In this relation it is worth mentioning that the
quently the rate of copolymerization in a radical washing and abrasion resistance tests were done by
copolymerization reaction is inversely related to the making films on a plastic surface of 10 cm width and
termination rate constant. As the amount of VTES 30 cm length with an applicator 125 micron. Then they
increases it can act as a chain transfer agent and were settled on the tester apparatus for 48 h. The veloc-
decreases the rate of polymerization reaction. ity of this apparatus is 37±1 rpm and it works until no
abrasion is seen in the films. The measure of washing
Studies of Paints Properties apparatus is the round of brush on the film of paint.
The obtained paints have acceptable results such as Generally it has been measured around 1000 round for
excellent storage stability, great surface coating, good the paints which their binder is a homopolymer and
brushing, UV light stability, washing and abrasion 5000-7000 round for copolymers, respectively. Table 3
resistance. Among these properties, the surface coating, shows the stabilities of these paints until 9000 round
washing and UV resistance have been shown in Figures that it is belong to the existence of VTES and Figure 8
7-9, respectively. Figure 7 shows that excellent surface shows that by increasing the VTES concentration the
coating by using white paints by considering Table 2 washing and abrasion resistance increase as well. The
recipe of emulsion paint on the dark background, and UV resistance of these paints has been shown in Figure
the disappearance of the black fraction after coating 9 (A with 0.25 molar and B without VTES). The com-
could be obtained. As Figure 8 (A-D) reveals some dif- parison of two film samples shows that the colour of B
ferences between the samples which contained 0.00, has a tendency to become yellowish while A is stable

Figure 7. The photograph of surface coating of sample paints with (A) 0.15, (B) 0.20 and (C) 0.25 M VTES.

Iranian Polymer Journal / Volume 14 Number 3 (2005) 217

Synthesis and Characterization of Silicone Modified ... Javaherian Naghash H. et al.

painting brush at low VTES concentration is being

observed but it is improved by increasing the VTES
concentration.

Solubility and FTIR Studies

The emulsion copolymers basically have low solubility
or show no solubility in any solvents at all.
These copolymers which have been synthesized
from MMA, BA and MAA with or without VTES are
not exceptions. They are not soluble even in aprotic
polar solvents such as NMP, DMSO, DMF or dimethy-
lacetamide (DMAC). This insolubility could be due to
conversion of the polymer samples to gelation immedi-
ately during drying under atmospheric air or vacuum.
Different procedures for the preparation, purification
and drying of the polymer samples were carried out.
For example, the product was isolated by filtration after
precipitation with a large amount of methanol and dried
under vacuum at 60oC. After 48 h it was observed that
it is insoluble in all of the above mentioned solvents. It
is worth to mention that these copolymers will turn to
Figure 8. The picture of washing and abrasion resistance of gel in ethanol after dissolving in little water. Anyway,
sample paints with (A) 0.00, (B) 0.15, (C) 0.20 and (D) 0.25 the characterization of these copolymers is very diffi-
M VTES. cult with the aim of their solubilities. For example
NMR study of these copolymers is nearly impossible to
and this is another important improvement because of perform, but FTIR spectra in the region from 4000 to
the presence of VTES. Brushing control studies have 500 cm-1 were recorded with a sample prepared by
been done by dissolving the paint in the determined making a film of the latex on the surface of a glass and,
amount of water, then it has been applied on the surface drying it, then removing the film from the glass. Figure
of chalk by a painting brush. Basically no painting 10 shows the FTIR spectra of (A) MMA, BA, MAA,
brush effect must be observed during the painting.
According to the results of brushing control which is
shown in Table 3, it has been observed that the effect of

Figure 10. FTIR Spectra of (A) MMA, BA, MAA copolymer

Figure 9. The picture of UV resistance of sample paints with (B) with 0.15 and (C) with 0.25 molar VTES [M]0 = 4.0 M, 60
(A) 0.00 and (B) 0.25 M VTES. rpm, [I] = 7.0× 10-3 M, T = 85oC.

218 Iranian Polymer Journal / Volume 14 Number 3 (2005)

 Javaherian Naghash H. et al. Synthesis and Characterization of Silicone Modified ...

(B) with 0.15 and (C) with 0.25 molar VTES-added

copolymers, respectively. The comparison of A spectra
with B or C has not shown any differences between two
different samples of copolymers. The same analyses were
repeated for each sample three times and from the FTIR
data it was concluded that this method is not able to show
the presence of VTES moiety in these copolymers.

Morphologies of Latex Particles at Different VTES

Concentrations
The particle morphologies of the VTES modified
acrylic copolymers were examined by SEM, and the
data are given in Table 4. Figure 11A-11C are electron
micrographs of the latex particles of samples that con- (a)
tain 0,00, 0.15 and 0.25 molar VTES and the number
average particle diameters were found to be 1500, 6000
and 7000 nm, respectively. According to these micro-
graphs the acrylic copolymers have very low particle
size compared to VTES modified samples and by
increasing the VTES concentration the particle size
increases and their size distributions become narrower.
On the other hand from the date of the Table 4 it is
observed that the number of polymer particles decreas-
es by increasing the VTES concentration. In addition it
is obvious that the number of polymer particles for the
emulsions obtained increases by increasing the time
and conversion monomers to copolymers. These results
suggest that MMA, BA, and MAA monomers were
completely polymerized in the presence VTES. (b)

Thermal Properties
The thermal properties of acrylic and VTES modified
acrylic copolymers were evaluated by means of TGA/
DTG and DSC under nitrogen atmosphere and are
shown in Figures 12 and 13. The acrylic emulsion of
Figure 12a shows some weight loss between 50-130oC
which is due to loss of solvent. Then it is stable up to
280oC. The chemical decomposition will start after this
temperature and the maximum decomposition is
around 370oC. On the other hand VTES modified
acrylic copolymers exhibited thermal decomposition
similar to the above, but the maximum decomposition
was around 380oC. The results are represented in Fig-
(c)
ures 12b and c for 0.15 and 0.25 molar VTES, respec-
tively. According to these results it is concluded that the Figure 11. SEM Pictures of (a) MMA, BA, MAA copolymer,
existence of VTES moiety in the copolymers causes (b) with 0.15 and (c) 0.25 molar VTES [M]0 = 4.0 M, 60 rpm
some thermal stability and by increasing the amount of [I] = 7.0 × 10-3 M, T = 85oC.

Iranian Polymer Journal / Volume 14 Number 3 (2005) 219

Synthesis and Characterization of Silicone Modified ... Javaherian Naghash H. et al.

(a)

Figure 13. DSC Thermograms of (A) MMA,BA,MA, copoly-

mer, (B) with 0.15 and (C) with 0.25 molar VTES, [M]0 = 4.M,
60rpm, [I] = 7.0 × 10-3 M, T= 85oC.

silicone thermal stability increases. The DSC curve of

the copolymers is shown in Figure 13A-C for 0.00, 0.15
(b) and 0.25 molar ratio VTES, respectively. Curve A in
Figure 13 reveals an endothermic shift around 50oC
which corresponds to Tg without VTES. The Tg is
around -85 and -100oC for (B) and (C), respectively. On
the other hand all of these copolymers (A-C) show very
sharp endothermic peak with a maximum of 380oC
which corresponds to the Tm. From these data it is very
interesting to mention that without VTES the resulting
copolymer is thermoplastic, while by addition of VTES
the Tg of copolymer will be drastically lowered and it
shifts to the elastomeric materials while its Tm remains
unchanged. According to these results it is found that
the presence of VTES moiety causes the change in ther-
mal behaviour and it particularly affects Tg.

(c)

CONCLUSION
Figure 12. TGA/ DTG Thermograms of (a) MMA, BA, MAA
copolymer, (b) with 0.15 and (c) with 0.25 molar VTES in N2 Continuous emulsion copolymerization of VTES modi-
atmosphere. [M]0 = 4.0 M, 60 rpm, [I] = 7.0 × 10-3 M , T= 85oC. fied acrylic resin, initiated by K2S2O8, was evaluated.

220 Iranian Polymer Journal / Volume 14 Number 3 (2005)

 Javaherian Naghash H. et al. Synthesis and Characterization of Silicone Modified ...

The experimental conditions of impeller speed, initiator 7. Matsui F., Uotani N., Murakami M., Itoh Y., Poly-
concentration, temperature, and VTES concentration organosiloxane and process for producing the same, U.S.
were varied and the following results were obtained: Patent 5,491,203 (1996).
- The obtained copolymers have high solid content 8. Lee I., Acrylic emulsion coatings for formed articles, U.S.
(43%) and are used in the emulsion paints as a binder. Patent 5,700,585 (1997).
- An increase in VTES concentration causes an 9. Lee I., Acrylic emulsion coatings, U.S. Patent 5,712,346
increase in heat stability and particle size, while the Tg, (1998).
number of polymer particles and polymerization rate 10. Czech A., Koczo K., Hydrophilic siloxane latex emul-
decrease and also particle size distributions became sion, U.S. Patent 6,207,782 (2001).
narrower. 11. Gornowicz G.A., kennan L.D., Saxena A.k., Tselepis
- The presence of VTES moiety in the copolymers A.J., Homopolymerization of acrylate or methacrylate end
causes conversion of thermoplastic structure to elas- blocked polydiorganosiloxanes, U.S. Patent 5,840,813
tomeric property. (1998).
- An increase in initiator concentration at both ini- 12. Graiver D., Tanaka O., Methods for making poly-
tial and intermediate stages of polymerization resulted diorganosiloxane microemulsions, U.S. Patent 5,817,714
in an increase in polymerization rate. (1998).
- In the region of relatively low impeller speed, a 13. Yang H.W., Pacansky T.J., Inverse emulsion process for
reduction in impeller speed shortens the reaction time preparing hydrophobe-containing polymers., U.S. Patent
required to attain high conversion. 4,918,123 (1990).
- It is observed that both initial rate of polymeriza- 14. Liles D.T., Murray D.L., Functional polyorganosiloxane
tion and maximum conversion are increased by emulsions from monohydrolyzable silanes and photocur-
increasing the temperature. able compositions therefrom, U.S. Patent 5,480,919
(1996).
15. Share P.E., Pippin W.H., Aqueous compositions contain-
REFERENCES ing polymerizable surfactant compounds, U.S. Patent
5,563,214 (1996).
1. Kondo H., Koshii T., Silicone water-based emulsion com- 16. Yamauchi T. Kamiyama Y., Aqueous, silicone-modified
position, U.S. Patent 4,782,112 (1998). acrylate polymer emulsion, U.S. Patent 5,852,095
2. Liles D.T., Murray D.l., Weyenberg D.R., Tselepis A.J., (1998).
Revis A. Silicone/organic copolymer emulsion from pre- 17. Walker J.L., Foreman P.B., Removable pressure sensitive
formed organic emulsions, U.S. Patent 5,482,994 (1996). adhesive, U.S. Patent 4,716,194 (1987).
3. Yamaya M., kizaki H., Furuya M., Yamamoto A., Silicone 18. Pons D.A., Van Hout J.B., Sep W.J., Composition based
resin-containing emulsion composition, method for mak- on an aqueous dispersion of an addition polymer, U.S.
ing same, and article having a cured film of same, U.S. Patent 5,100,955 (1992).
Patent 5,973,068 (1999). 19. Werner J.R., Ervin R., Konsza E.E., Waterbased acrylic
4. Okibe J., Inoue M., Haruna M., Yasuda A., Sundag T., silane and polyurethane containing coating composition,
Iwabuchi Y., Sato N., Coating resin composition contain- U.S. Patent 5,204,404 (1993).
ing hydrolyzable organosilane, acrylic resin and poly- 20. Asanaka Y., Takeuchi H., Ohiwa M., Nakatsuka T.,
organosiloxane, U.S. Patent 6,329,456 ( 2001). Yamoto S., Reactive particulate resin, method for produc-
5. Oochi. I., Miki D., Tanaka S., Sawai T., Resin composi- ing the same, and resin composition for thermoforming,
tion, processes for their production and their uses, U.S. U.S. Patent 5,459,179 (1995).
Patent 6,287,701 (2001). 21. Tahara S., Hashimoto T., Kanayama T., Process for pro-
6. Campbell J.D., Debling J.A., Deyoung D.J., Giannakitsas ducing water-base resin dispersion, U.S.Patent 5,489,645
I., Hellwig D.R., Schatz D.D., Teymour F., Villalobos (1996).
M.A., Process for producing polymers by free radical poly- 22. Asanaka Y., Takeuchi H., Ohiwa M., Nakatsuka T.,
merization and condensation reactions and apparatus and Yamoto S., Reactive particulate resin and method for its
products related thereto, U.S. Patent 6, 346, 590, (2002). production, U.S. Patent 5,494,974 (1996).

Iranian Polymer Journal / Volume 14 Number 3 (2005) 221

Synthesis and Characterization of Silicone Modified ... Javaherian Naghash H. et al.

23. Yang M., Liu H., Zhang H., Chen D., Wang J., Wang C., 37. Peng H., Huang G.F., Lu W., li X.B., Huang S.Q., Kinet-
Silicone acrylic emulsion coatings., Tuliao Gongye, 30, ics and nucleation mechanism of organosilicon composite
12 -15 (2000). emulsion polymerization., Gongneng Gaofenzi xuebao,
24. Maeda O., Kobayashi H., Kageishi K., Acrylic silicone 13, 173-176 (2000).
emulsion compositions for coatings with good resistance 38. Song Z., Poehlein G.W., Kinetics of emulsifier free emul-
to water and weather, Japan Patent, 26,691 (2000). sion polymerization of styrene, J. Polym. Sci. Part A,
25. Liu D., Nie Z., Xu W., Sun L., Chen G., Acrylic poly- Polym. Chem. 28, 2359-2392 (1990).
siloxane coatings for building materials and their manu- 39. Arai K., Arai M., Iwasaki S., Saito S., J. Polym. Sci,
facture., Faming zhuanli shenqing Gongkai shuomingshu Polym. Chem., 20, 1203- (1982).
CN, China Patent 97,105,779 (1997). 40. Harkins W.D., General theory of mechanism of emulsion
26. Wang Y., Zhang B., Zhu K., Study on process of acrylate- polymerization., J. Am. Chem. Soc., 69, 1428-1444
silicone emulsion copolymerization., Tuliao Gongye, 30, (1947).
1-2 (2000). 41. Smith W.V., Ewart R.H., Kinetics of emulsion polymer-
27. Qiao Y., Yu J., Song D., Wang D., Hou Z., Synthesis of ization, J. Chem. Phys., 16, 592-599 (1948).
silicone modified acrylic emulsion and its film structure., 42. Kumar K., Rana K.S., Mechanical properties and aging
Tuliao Gongye, 31, 3-6 (2001). behaviour of styrene-butadiene-vinyltriethoxysilane cou-
28. You B., Chen X., Li D., Feng Q., Wu L., Study on emul- pled carbon black vulcanizates., Iran. Polym. J., 11, 287-
sion polymerization of silanes / acrylate., Zhanjie, 21, 21- 293 (2002).
23 (2000). 43. Sun Z., Ding W., Liu J., Li J., High weather-resistant sil-
29. Chen Z., Synthesis and properties of silicone modified icone-modified acrylic resin and its coating., Shanghai
styrene-acrylic emulsion,. Tuliao Gongye, 29, 15-16 Tuliao, 4, 201-204 (1998).
(1999). 44. Kan C.Y., Zhu X.L., Yuan Q., Kong X.Z., Graft emulsion
30. Yamaya M., Furuya M., Kizaki H., Yamamoto A., Sili- copolymerization of acrylates and siloxane., Polym. Adv.
cone resin-containing emulsion composition, making Technol., 8, 631-633 (1997).
method, and article having cured film of the composition,
U.S. Patent 6,147,156 (2000).
31. Shaffie A., Moustafa, A.B., Mohamed E.S., Badran A.S.,
The course of emulsion polymerization of vinyl acetate
using redox systems of different oxidizing agents, J.
Polym. Sci. Part A: Polym. Chem., 35, 3141-3149 (1997).
32. Naveen Kumar P., Paresh Sanghvi G.S., Shah D.O.,
Surekha D., Kinetics and behaviour of copolymerization
in emulsion and microemulsion systems, Langmuir, 16,
5864-5870 (2000).
33. Badran A.S., Moustafa A.B., Yehia A.A. Shendy S.M.M.,
Emulsion polymerization of vinyl acetate initiated by
potassium persulfate cyclohexanone sodium bisulfite
redoxe pair system, J. Polym. Sci. Part A: Polym. Chem.,
28, 411-424 (1990).
34. Lambourne R., Paint and Surface Coatings Theory and
Practice, Edited by Ellis Horwood Market Cross House,
Chichester, West Sussex, England Ch. 9, pp. 359-363
(1987).
35. Swaraj P. Surface Coatings Science and Technology,
John Wiley, Ch. 8, pp. 559-594 (1986).
36. Konno M., Shimizu K., Arai K., Saito S., J. Polym. Sci.
Part A, Polym. Chem., 25, 223-230 (1987).

222 Iranian Polymer Journal / Volume 14 Number 3 (2005)

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