Microsoft Word - 409-418 _20110207_ 021 Synthesis fo~_Hamid Javaheri…409
Introduction
application because of their excellent properties including
good mechanical properties, abrasion, and chemical resis-
tance.1-3 However, poor water resistance and thermal stability
limit their applications in some fields. On the other hand,
siloxane materials have high thermal and oxidative stability,
weatherability, low surface energy and a wide service tem-
perature range (glass transition temperature (Tg, -123 )),
but lower mechanical property and abrasion resistance.4 It is
possible to prepare polyurethane/silicone/acrylic (PU/Si/A) or
polyurethane/silicone/vinyl acetate (PU/Si/VAc) copolymers
polyurethane (PU), while the mechanical and abrasion charac-
teristics are little damaged.5 Landfester and coworkers6 have
explored different synthetic pathways to synthesize siloxane
-modified polyurethane/acrylic (PU/A) hybrid latexes with
small particle sizes narrowly distributed and using the specific
advantages of the miniemulsion approach. It was demonstrated
by Youssef et al.7 that the introduction of functional silane
improves some physical and chemical properties, i.e. very
low surface energy, excellent gas and moisture permeability,
good heat stability, low temperature flexibility and biocom-
patibility. Jung et al.8 illustrated that high siloxane content
PU/A hybrid nanocomposite film show a decrease of tensile
strength, elastic modulus and Tg an increase in water
resistance as well as friction resistance. Webster et al.9
showed PU/A hybrid coatings went from a hydrophilic
surface to a hydrophobic surface when the siloxane was
incorporated into the polyurethane formulation. Zhang and
coworkers10 pointed out that the Si modified PU/A emulsion
resin can improve the physical and chemical properties of
the building paints. According to Wu et al.11 modification
with organosilicone is one of the ideal methods available for
improving the hydrophobicity of the surfaces of thermoplastic
PUs coats. Zhang12 and Lee et al.13 indicated that the chain
structure and the particle size of siloxane modified PU/A
hybrid emulsion were confirmed by FTIR and TEM analysis.
Additionally, the emulsion particle size was uniform and around

Polyurethane-Veova/Vinyl Acetate
Hamid Javaherian Naghash Elham Kasaeian Naeni
Department of Chemistry, Islamic Azad University
(2011 2 7 , 2011 4 12 , 2011 4 26 )
Synthesis of Novel Silicone Containing Vinylic Monomer and Its Uses in the Waterborne Polyurethane-Veova/Vinyl Acetate Hybrid Emulsion Copolymers
Hamid Javaherian Naghash and Elham Kasaeian Naeni
Department of Chemistry, Islamic Azad University,
Shahreza Branch, P.O. Box 311-86145, Shahreza, Isfahan, I. R. Iran
(Received February 7, 2011; Revised April 12, 2011; Accepted April 26, 2011)
Abstract: A novel silicone (Si) containing vinylic monomer, N-(3-(triethoxysilyl)propyl) methacrylamide
(TESPMA), based on 3-aminopropyltriethoxysilane (APTES) and methacryloyl chloride (MCl) has been
synthesized for formulation of waterborne polyurethane (WPU). Two types of vinyl group containing
Si, methacryloxypropyltriethoxysilane (MPTES) and triethoxyvinylsilane (TEVS), have been used as
coupling reagents for comparison of the effects of Si kinds with TESPMA on the WPU. A series of new
siliconized WPU, vinyl acetate/vinyl ester of versatic acid (VAc-Veova), TESPMA, MPTES and TEVS
hybrid latexes have been successfully prepared by emulsion polymerization in the presence of WPU
dispersion. Keywords: N-(3-(triethoxysilyl)propyl) methacrylamide, silicones, polyurethanes, polymer synthesis
and characterization, glass transition, coatings.
†To whom correspondence should be addressed. E-mail: hsbyun@kmu.ac.kr
†To whom correspondence should be addressed. E-mail: Javaherian @ iaush.ac.ir
410 Hamid Javaherian Naghash and Elham Kasaeian Naeni
,  35 5, 2011
45 nm, which ensures better performance of the formed film.
The obtained PU/Si/A proved to possess higher contact
angle and better water resistance when siloxane content
was higher than 6.5% and also the mechanical property has
great change when siloxane content is above 6.5%. Finally,
Larock et al.14 showed that the acrylics play an important
role in enhancing the thermal stability of the PU/Si/A hybrid
latexes. The improved thermal stability of the hybrid latexes
can be explained by the occurrence of extensive grafting,
cross-linking, and interpenetration.
In this work, we make modifications of the PU/P (VAc-
Veova) hybrid emulsion by TESPMA, using the solvent-free
method. We used TESPMA to incorporate the siloxane into
the soft segment of PU chains and obtained a new material
of TESPMA modified WPU/P (VAc-Veova). Then, two types
of vinyl group containing Si, the MPTES and TEVS were
used as coupling reagents for comparison of the effects of
Si kinds on the WPU. The preparation technology was di-
scussed systematically and the effect of TESPMA content on
PU/Si/(VAc-Veova) was investigated.
Materials and Equipment. Reagent grade VAc (Fisher Sci-
entific Co) was further purified by distillation in a rotary eva-
porator at reduced pressure of 30 mmHg to remove inhibitor.
The Veova provided by Achema (Lithuania) was also di-
stillated under vacuum and stored at 0 to avoid thermal poly-
merization. Dibutyltin dilaurate (DBTDL, Aldrich, Gillingham,
UK) was analytical grade and used directly without further
purification. Polypropylene glycol 1000 (PPG-1000, Korea
Polyol Ltd., Korea) was dried and degassed at 65 under
vacuum. APTES and MCl (Fluka) were used as received.
Hexamethylene diisocyanate (HMDI), dimethylol propionic
acid (DMPA), potassium persulfate (KPS), hydroxyethyl
cellulose (HEC), sodium bicarbonate (NaHCO3), sodium
chloride (NaCl), MPTES, TEVS and tetrahydrofuran (THF)
were supplied by Merck, Hohenbrunn, Germany, and were
used as received. Triethylamine (TEA, Junsei) was used
without further purification. Double-distilled water (D.D.W)
was used throughout. Fourier-transform infrared (FTIR)
spectroscopy analysis was performed with a Nicolet Impact
400D Model spectrophotometer (Nicolet Impact, Madison,
USA) using KBr pellets. The spectra were obtained over
the wavenumber range 4000∼400 cm-1 at a resolution of 2
cm-1 using an MCT detector with co-addition of 64 scans.
Scanning electron micrographs were taken on a JEOL-JXA
840 A SEM (JEOL, Boston, USA). The specimens were
prepared for SEM by freeze-fracturing in liquid nitrogen
and the application of a gold coating of approximately 300
with an Edwards S 150 B sputter coater. Transmission
electron microscope (TEM) analysis was performed with a
Hitachi H-600, Hitachi Corporation, Japan.
Preparation of Polyurethane Dispersion (PUD). A 500 mL,
round bottom, 4-necked-flask, separable glass reactor with
mechanical stirrer, thermometer, condenser and nitrogen purge
was used. Basic recipe for the synthesis of PUD is presented
in Table 1. Polyaddition reaction was carried out in a N2
atmosphere in a constant-temperature water bath. HMDI
and PPG were first charged into the reactor and heated to
80 under stirring, and then DBTDL was dropped into the
reactor while keeping the temperature at 80 . The reaction
proceeded over approximately 1 hr, DMPA was subsequently
charged and reaction proceeded for another 4 hrs at the same
temperature, upon which the theoretical NCO/OH value of
1.2. was determined by the dibutylamine back titration. This
PU was then neutralized by the addition of TEA at 25 ,
followed by dispersion at high speed (1200 rpm) with D.D.W.
which was added drop-wise to produce a WPUD.
Semi-Continuous Emulsion Polymerization Using PUD. Semi-
continuous emulsion copolymerization was carried out using
a 500 mL four-necked round-bottom flask equipped with a
reflux condenser, a stainless-steel stirrer, a sampling device,
and one feed stream. The feed stream was a solution of VAc
and Veova, by adding, TESPMA, MPTES and TEVS, each one
through emulsion copolymerization. Before emulsion poly-
merization start-up, the reaction vessel was first charged
with the desired amounts of water, PUD, HEC, NaHCO3, and
initiator solution (2.8×10-3 molL-1), respectively. During
polymerization, the reaction mixture was stirred at a rate of
100 rpm, and the temperature was maintained at 65 . After
5 min, 10 w% of total amount of the monomer mixture was
added to the flask in a period of 20 min. Then, the tem-
perature was kept at 80 until the end of polymerization
(4 hrs). The polymerization was performed with feeding
rate of 1.0 mL/min under N2 atmosphere to investigate the
effect of TESPMA, MPTES or TEVS concentrations and also
PU/P (VAc-Veova) ratios on monomer conversion. A typical
recipe for the preparation of a product is given in Table 2.
In order to determine the conversion percent during the
Table 1. Recipe for Synthesis of PUD
Ingredients Charge(g)
PPG(M.W.: 1000) 60.00 HMDI 20.00 DMPA 1.60 TEA 1.50 D.D.W 80.00
  Synthesis of Novel Silicone Containing Vinylic Monomer and Its Uses in the WPU–Veova/VA Hybrid Emulsion Copolymers 411
Polymer(Korea), Vol. 35, No. 5, 2011
polymerization process, it was necessary to withdraw samples
at various intervals from the reaction vessel. These samples
are relatively small so that the overall composition in the
reactor is not seriously affected; once a sample is removed
and put in a watch glass, polymerization is terminated by the
addition of 7 ppm hydroquinone. Then, two drops of ethanol
was added to the sample as a coagulant and the contents of
the watch glass were evaporated at room temperature and
then dried to a constant weight in a vacuum oven. The con-
version percent was determined gravimetrically. The purifi-
cation and precipitation of the polymer were done using a
reported method.15 The number of polymer particles per unit
volume of water (NT) was calculated from the monomer
conversion XM and the volume average diameter of the poly-
mer particles, dυ was determined by a scanning electron
microscope, using the following equations:
∑ ∑=
where M0 is the initial monomer concentration per mL, and
ρp is the density of the polymer (g/cm3).16-18 The volume
average diameter )( 3 υd of the latexes was found to be 3.8
×10-12, 4.9×10-12, and 1.7×10-12 mL for P(VAc-Veova),
PU/P(VAc-Veova) and PU/P(VAc-Veova)/TESPMA, res-
S. Chen et al.19 and is illustrated in Scheme 1.
Particle Size and Distribution of PU/P (VAc-Veova)/TESPMA.
The morphology and particle sizes of emulsions were mea-
sured by using SEM (JEOL-JXA 840 A) and TEM (Hitachi
H-600). The samples of emulsions were diluted with deionized
water to adjust the solid content to around 1 w% and directly
placed in the cell. The temperature of the cell was kept at
around 25 and the measuring time was 300 s.
Film Formation. Films were prepared with a dry thickness
of about 0.5 mm. After casting the emulsion onto glass plates
(20 cm×20 cm), the films were allowed to dry for 1 week at
ambient temperature (25 ).
Water Absorption. Dried films (30 mm×30 mm; original
weight designated as W0) were immersed in water for 24 hrs
at 25 . After the residual water was wiped from the films
using filter paper, the weight (W1) was measured imme-
diately.20 It was calculated as follows:
Water Absorption, R(%)=((W1−W0)/W0)×100
Results and Discussion
50 mL three–necked round bottom flask which was dried,
purged with nitrogen, equipped with a reflux condenser, a
dropping funnel and nitrogen inlet, 2.6 g (25 mmol) MCl, 20
mL, THF and 2 g (20 mmol) TEA were taken. To this, 5.5
g (25 mmol) APTES was added drop-wise maintaining tem-
perature at 0 under nitrogen atmosphere. After complete
addition, the reaction mixture was maintained at room tem-
perature for 1 hr and then 2 hrs under stirring at reflux tem-
perature (65 ). Use of TEA promotes the desirable con-
Table 2. Recipe for Semi-continuous Emulsion Polymerization of PU/P(VAc-Veova)/Si
Ingredients Charge(g)
PUDs(20 wt% solid) 30.00 D.D.W 100.00 HEC 0.60 NaCl 0.20 NaHCO3 0.20 Initiator: K2S2O8 0.20 VAc 48.00 Veova 21.00 TESPMA, TEVS or MPTES 0.00∼4.00
R*=OH and SO4 - I= K2S2O8
I 2R*
O
CH3
O
CH3
SiO O
O CH2CH2
CH3 CH3CH2
,  35 5, 2011
propyltriethoxysilane -H. Then, the pall yellow by product
salt was filtered off quickly to minimize contamination of the
product by hydrolysis when the salt is exposed to moisture.
The viscous crude product was recovered after removing
the solvent using an evaporator and the residue was finally
dried in a vacuum at 25 . The final product was viscous
yellow oil. Yield7.225 g, 83%. The reaction path is pre-
sented in Scheme 2.
FTIR Spectrum of TESPMA. Figure 1 shows the typical
FTIR spectra of (a) MCl, (b) APTES and (c) TESPMA. It
can be seen from Figure 1(a) that there are absorption
peaks at 2990, 2929, 2855 and 1787 cm-1 which are
ascribed to the vibration of -CH2, and C=O respectively.
Figure 1(b) indicates strong absorption peaks at 3369,
2974, 2925, 2888 and 1092 cm-1, which are ascribed to the
vibration of -NH2, -CH2, and Si-O-R, respectively. As
shown in Figure 1(c) a new sharp peak appeared at
3335 cm-1, which was attributed to N-H absorption. Also,
the absorption peak at 1528 cm-1 was attributed to N-H
bond vibration and C-N symmetry stretch vibration, and the
sharp and strong peak at 790 cm-1 was absorption due to
C-N bond vibration. The peak at 1099 cm-1 was protected
which is attributed to the Si-O-R, stretch vibration and a
peak appeared at 1448 cm-1 which was attributed to vinyl
group in the Si containing vinylic monomer.
NMR Analysis of TESPMA. 1H NMR is the most useful instru-
ment for the measurement of hydrogen chemical environ-
ment because of its high sensitivity to hydrogen bond strength,
while the area of apex also evidently reflects the abundance
of hydrogen in different chemical shift.21 The 1H NMR of
TESPMA is shown in Figure 2. It could be seen that all the
relevant peaks of monomer could be found in this figure.
The peak at 0.68, 1.8 and 3.4 ppm results from the group of
-CH2 in the chain of Si-CH2 in the molecule of TESPMA.
A small signal has been shown at 3.8 ppm belonging to
-NH bond. Also two small peaks were observed at 5.3 and
5.7 ppm which belong to vinyl group (CH2=CH-) in the
molecule of TESPMA. Figure 3 indicates the 13C NMR spec-
trum of TESPMA. The number of carbons in the TESPMA
is compatible with the number of peaks in the 13C NMR
spectrum.
Veova)/TESPMA. Figure 4 illustrates the FTIR spectra of
(a) PU, (b) PU/P(VAc-Veova) and (c) PU/P(VAc-Veova)/
TESPMA, respectively. It can be seen from Figure 4(a)
that there are strong absorption peaks at 3426, 2968, 2874
and 1705 cm-1, which are ascribed to the vibration of -OH,
-CH3, -CH2 and C=O, respectively. After cross-linking
Figure 2. 1H NMR spectrum of TESPMA. ppm 8 6 4 2 0
a
b
d
c
g
b c d
C C
CH3 Scheme 2. Preparation of TESPMA.
Figure 1. FTIR spectra of (a) MCl; (b) APTES; (c) TESPMA.
4000 3500 3000 2500 2000 1500 1000 500
Wavenumbers(cm-1)
Tr an
sm itt
an ce
(% )
  Synthesis of Novel Silicone Containing Vinylic Monomer and Its Uses in the WPU–Veova/VA Hybrid Emulsion Copolymers 413
Polymer(Korea), Vol. 35, No. 5, 2011
(see Figure 4(b)), the wide and strong -OH absorption 3426
cm-1 disappeared and two new peaks appeared between
3439 and 3345 cm-1, which were attributed to N–H ab-
sorption. The NCO absorption peak at 2273 cm-1 did not
appear, perhaps indicating that the -NCO group had reacted
completely. The absorption peak at 1544 cm-1 was attributed
to N-H bond vibration and C-N symmetry stretch vibration,
and the sharp and strong peak at 776 cm-1 was absorption
due to C-N bond vibration. These indicated the presence
of urethane bond and urea bond formation. A new peak
appeared at 1028 cm-1 Figure 4(c) that was attributed to
the Si-O-R.
fication with organosilicone is one of the ideal methods
available for improving the hydrophobicity of the surfaces
of thermoplastic PU coats. The most widely used organo-
silicone is polydimethylsiloxane (PDMS).22-27 For example,
Wynne et al.28 synthesized PDMS-urea-urethane copoly-
mers by two-step polymerization method. Rochery et al.29
also incorporated PDMS into polytetramethyleneoxide
(PTMO) based PUs by using both hydroxyl-terminated PDMS
and isophorone diisocyanate (IPDI). All of the above pre-
pared Si-containing PUs showed a reduction in surface-
free energy. In addition, for a long product life, strong adhesion
between Si and the target matrix is required. The inherently
hydrophobic nature of Si compounds coupled with their ability
to segregate to the surface facilitates their use as a surface
modifier for other materials. This property has been exploited
in the preparation of Si-modified U/A emulsion copolymers.
Although copolymerization of Si/U/A has been well esta-
blished,30-33 their copolymerization in the presence of
TESPMA has not been reported. The TESPMA is compatible
with acrylic chains due to carry on functional group double
bond of vinylic linkage. During copolymerization process,
this monomer makes part of the copolymer chain. However,
the extent of its incorporation in the polymer chain has not
measured. Figure 5 shows the effect of TESPMA on the
monomer conversion versus time, where the initial initiator
and total monomer concentrations were fixed. This figure
shows that the rate of reaction changes with the Si concen-
tration. As shown in Figure 5, the reaction rate decreases
by increasing TESPMA and the same results were obtained
for the other silane compounds.34-38 It is known that the
rates of propagation and consequently copolymerization in
a radical copolymerization reaction are inversely related to
the termination rate constant. As the amount of Si increased,
it acted as a chain transfer agent and the rate of polymeri-
zation decreased. Although chain transfer generally does
not decrease the polymerization rate, this matter has been
observed by the authors for many times and it can be justified
as follows, the radicals obtained from vinyl silanes are more
stable in comparison with other radicals which exist in the
Si containing emulsion copolymers. This stability could be
due to the π-bonds and resonance effects of double bonds,
Figure 4. FTIR spectra of (a) PU; (b) PU/P(VAc-Veova); (c) PU/P(VAc-Veova)/TESPMA.
4000 3500 3000 2500 2000 1500 1000 500
Wavenumbers(cm-1)
100 80 60 40 20 0
100
50
0
(% )
Figure 5. Effect of initial Si concentration on monomer con- version versus time at () 0.25 and () 1.00 molL-1 for TESPMA; () 0.25 and () 1.00 molL-1 for TEVS. T=80 , 100 rpm, [I ]o=2.2×10-3 molL-1.
0 20 40 60 80 100 120 140 160 180 200
Time(min)
100
90
80
70
60
50
40
30
20
10
0
TESPMA=0.25 M
TESPMA=1.00 M
TEVS=0.25 M
TEVS=1.00 M
Figure 6. Effects of TESPMA () and TEVS () content seed latex to water absorption ratio of the latex films.
0.25 0.5 0.75 1 1.25
Silicone(molL-1)
0.048 0.046 0.044 0.042 0.04
0.038 0.036 0.034 0.032 0.03
0.028 0.026 0.024 0.022 0.02
0.018 0.016
W at
er a
bs or
pt io
n ra
,  35 5, 2011
observed.
water absorption ratio of the PU/P(VAc-Veova)/TESPMA
or PU/P(VAc-Veova)/TEVS films is an important evidence
of hydrophobicity. As shown in Figure 6, the absorption ratio
was greatly influenced by TESPMA or TEVS concentrations.
With the increase of the Si content, the water absorption
ratio of the PU/P(VAc-Veova)/TESPMA or PU/P(VAc-
Veova)/TEVS films decreased, which can be contributed
to the excellent hydrophobicity of the TESPMA and TEVS
monomers. When the Si content increased from 0.25 to
1.25 molL-1, the water absorption of the films decreased
sharply from 0.06 to 0.018%. According to this figure, we
conclude that an increase in TESPMA concentration would
give better water resistance than TEVS.
Effects of PU Content on the Reaction Rate of PU/P (VAc-
Veova)/TESPMA Hybrid Emulsion. PU/P(VAc-Veova)/
a mixture of (VAc-Veova) monomers and TESPMA in the
presence of PU dispersion. The weight ratio between PU
component and P(VAc-Veova) component was varied by
changing the amount of both PU and P(VAc-Veova) while
Figure 8. SEM pictures of (a) P(VAc-Veova); (b) PU/P(VAc-Veova); (c) PU/P(VAc-Veova)/TESPMA; (d) PU/P(VAc-Veova)/ TEVS at 80 , 100 rpm, [I ]o=2.2×10-3 molL-1.
(a) (b)
(c) (d)
Figure 9. TEM pictures of (a) PU/P(VAc-Veova); (b) PU/P(VAc-Veova)/TESPMA at 80 , 100 rpm, [I ]o=2.2×10-3 molL-1.
(a) (b)
Figure 7. Effects of PU content on reaction rate of PU/P(VAc- Veova)/TESPMA hybrid emulsion.
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200
Time(min)
100
% )
  Synthesis of Novel Silicone Containing Vinylic Monomer and Its Uses in the WPU–Veova/VA Hybrid Emulsion Copolymers 415
Polymer(Korea), Vol. 35, No. 5, 2011
keeping the amount of Si constant (0.50 molL-1). Figure 7
shows the effect of weight ratio between PU component
and P(VAc-Veova) component versus time. According to
this figure, 30% PU and 70%(2050) VAc-Veova shows
the maximum conversion percent. This result suggests that
the best ratio of PU/P(VAc-Veova) is 30/70, a phenomenon
observed by many researchers.39,40
Veova), and PU/P(VAc-Veova)/Si. The particle morphologies
of the P(VAc-Veova), PU/P(VAc-Veova), PU/P(VAc-
Veova)/TESPMA and PU/P(VAc-Veova)/TEVS were examined
by SEM and TEM, respectively. The micrographs are shown
in Figure 8(a-d), and Figure 9(a-d) and data for TESPMA
are given in Table 3. According to Figure 8(a-d) the P(VAc-
Veova) and PU/P(VAc-Veova) copolymers have very low
particle size compared to PU/P(VAc-Veova)/Si samples. By
increasing the Si concentration the particle size increases in a
linear manner and their size distributions get narrower. On
the other hand, by comparison of the SEM micrographs of
Figure 8(c) and 8(d), it can be seen that the particles of
Figure 8(d) are not spherical. This may result from the
procedure used for the sample preparation. It seems that
there are two different types of particles in Figure 8(a-c).
They actually are one type and the other is air bubbles. From
the data in Table 3, it could be inferred that the number of
polymer particles increase by increasing the TESPMA
concentration. In addition, it is obvious that the number of
polymer particles for the emulsions obtained increase by
Figure 10. TGA/DTG thermograms of (a) P(VAc-Veova); (b) PU/P(VAc-Veova); (c) PU/P(VAc-Veova)/TESPMA; (d) PU/P (VAc-Veova)/TEVS in N2 atmosphere, T80 , 100 rpm, [I ]o =2.2×10-3 molL-1.
-1 100 200 300 400 500 600 657
Temperature()
110
100
90
80
70
60
50
Temperature()
110
100
90
80
Temperature()
110
Table 3. Morphologies of Latex Particles of P(VAc-Veova), PU/P(VAc-Veova) and PU/P(VAc-Veova)/TESPMA
P(VAc/Veova) 3 υd =3.8×10-12
XM NT×1012
XM NT×1012
XM NT×1012
Mo=0.50 g/mL, P(VAc-Veova)(ρp=1.24 g/mL), PU/P(VAc-Veova)(ρp=1.21 g/mL) and PU/P(VAc-Veova)/TESPMA(ρp=1.19 g/mL), T=80 , [I ]o =2.2×10-3 molL-1.
-1 100 200 300 400 500 600 657
Temperature()
,  35 5, 2011
mers. Also Figure 8(a) and 8(b) show very smaller particle
sizes compared to 8(c). It could be clearly observed in
Figures 8(c) that some Si containing PU/P(VAc-Veova)
particles agglomerate together. The results obtained from
the TEM micrographs are displayed in Figure 9(a) and 9(b),
the white section and the dark points were PU/P(VAc-
Veova) and PU/(VAc-Veova)/TESPMA respectively, are
in accordance with the expected result. The PU prepoly-
mer could act as a macromolecular emulsifier for its hydro-
philic carboxy group. The hydrophobic (VAc-Veova)/Si
monomers could migrate into the PU particle adequately
before the radical polymerization to achieve the homoge-
neous particle size. It may be concluded that the outer
component is mostly PU while the inner component is mostly
hydrophobic P(VAc-Veova)/Si. It could further be inferred
from Figure 9(a) and (b) that there is little influence to
particle configuration when Si is introduced into PU/(VAc-
Veova).
were completely polymerized in the presence TESPMA.
Thermal Properties. The thermal properties of P(VAc-
Veova), PU/P(VAc-Veova), PU/P(VAc-Veova)/TESPMA
under nitrogen atmosphere. The TGA/DTG curve of the
copolymers is shown in Figure 10(a) for P(VAc-Veova), 10(b)
for PU/P(VAc-Veova), 10(c) for PU/P(VAc-Veova)/TESPMA
and 10(d) for PU/P(VAc-Veova)/TEVS, respectively. The
P(VAc-Veova) emulsion (Figure 10(a)) shows a stable
situation up to 340 . The chemical decomposition will start
after this temperature and the maximum decomposition is
around 400 . The PU/P(VAc-Veova) emulsion(Figure 10(b))
shows a stable situation up to 350 and the chemical de-
composition starts after this temperature and the maximum
decomposition is around 400 . In addition, the PU/P(VAc-
Veova)/TESPMA(Figure 10(c)) and PU/P(VAc-Veova)/
TEVS, (Figure 10(d)) show stable situations up to 200 and
the maximum decompositions are around 400 . From a
comparison of the TGA thermograms of Figure 10(c) and
(d), it could be concluded that the synthesized monomer
(TESPMA) is more effective than TEVS as the char yield
weight of polymer with TESPMA at 614 was about 10.82%
while in the case of polymer with TEVS it was about 9.98%.
Based on these results, it could be concluded that the
existence of TESPMA or TEVS moieties in the copolymers
causes some thermal stability.
Veova), PU/P(VAc-Veova), PU/P(VAc-Veova)/TESPMA
Temperature()
0.800
0.700
0.600
0.500
0.400
0.300
0.200
Temperature()
Tan delta
Dynamic properties vs temperature 1.800 1.600 1.400 1.200 1.000 0.800 0.600 0.400 0.200 0.000 -0.200
Ta n δ
Temperature()
1.00E+09
1.00E+08
1.00E+07
1.00E+06
1.00E+05
1.00E+04
M od
ul us
(P a)
(a) 1.800 1.600 1.400 1.200 1.000 0.800 0.600 0.400 0.200 0.000 -0.200
Ta n δ
Temperature()
Tan delta
Dynamic properties vs temperature 1.800 1.600 1.400 1.200 1.000 0.800 0.600 0.400 0.200 0.000
Ta n δ
(b)
Figure 11. DMTA thermograms of (a) P(VAc-Veova); (b) PU/P VAc-Veova); (c) PU/P(VAc-Veova)/TESPMA; (d) PU/P VAc- Veova)/TEVS in N2 atmosphere, T80 , 100 rpm, [I ]o =2.2×10-3 molL-1.
  Synthesis of Novel Silicone Containing Vinylic Monomer and Its Uses in the WPU–Veova/VA Hybrid Emulsion Copolymers 417
Polymer(Korea), Vol. 35, No. 5, 2011
and PU/P(VAc-Veova)/TEVS copolymers is shown in Figure
11(a-d), respectively. From the DMTA curves, the plateau
of the elastic modulus in the rubbery state can be used to
make qualitative comparisons of the level of cross-linking
and Tg among the various polymers. This figure also shows
that the storage modulus change with temperature. The
storage modulus of the Si adducts based urethane prepoly-
mer above room temperature showed lower values than any
other copolymers. The peak position related to the Tg was
higher in the order P(VAc-Veova)>PU/P(VAc-Veova)>
PU/P(VAc-Veova)/TESPMA>PU/P(VAc-Veova)/TEVS.
The higher Tg for P(VAc-Veova) or PU/P(VAc-Veova)
was interpreted as being due to the effect of the more
difficult micro Brownian motion of the stiffer chains rather
than Si containing polymer chains. The Tg values estimated
from the maximum peak of tan δ are given as 42.3, 41.0,
35.5 and 26.2 , for the P(VAc-Veova), PU/P(VAc-Veova),
PU/P(VAc-Veova)/TESPMA and PU/P(VAc-Veova)/TEVS,
behavior and it particularly affects Tg.
Conclusions
APTES and MCl, has been synthesized for formulation of WPU.
MPTES and TEVS were used for comparison of the effects
of Si kinds on the WPU. A series of new siliconized WPU,
(VAc-Veova), TESPMA, MPTES, and TEVS hybrid latexes
have been successfully prepared by the emulsion poly-
merization in the presence of a WPU dispersion by using
KPS as an initiator. The WPU dispersion has been prepared
by a polyaddition reaction of HMDI, on PPG-1000 and DMPA
as chain extender.
containing monomer with one functional group, double bond
of vinyl. 13C NMR, 1H NMR and FTIR analysis showed that
TESPMA segments are present in the structures of mo-
nomer and copolymer. PU/P(VAc-Veova)/TESPMA improves
the water resistance of PU latex. The presence of TESPMA in
the PU/P(VAc-Veova) copolymer caused an increase in
the heat stability while the Tg decreased. The reaction rate
decreases by increasing TESPMA. The obtained results
show that 30% PU and 70%(2050) VAc-Veova is the best
ratio of PU/P (VAc-Veova) in the TESPMA containing co-
polymer. In addition, MPTES containing copolymers did not
show good results due to its incompatibility with this polymer
system but TEVS was a compatible monomer. The above
results suggest that TESPMA containing copolymer is better
than TEVS.
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adatti per visualizzare e stampare documenti aziendali in modo affidabile. I documenti PDF creati possono essere aperti con Acrobat e Adobe Reader 5.0 e versioni successive.) /JPN <FEFF30d330b830cd30b9658766f8306e8868793a304a3088307353705237306b90693057305f002000410064006f0062006500200050004400460020658766f8306e4f5c6210306b4f7f75283057307e305930023053306e8a2d5b9a30674f5c62103055308c305f0020005000440046002030d530a130a430eb306f3001004100630072006f0062006100740020304a30883073002000410064006f00620065002000520065006100640065007200200035002e003000204ee5964d3067958b304f30533068304c3067304d307e305930023053306e8a2d5b9a3067306f30d530a930f330c8306e57cb30818fbc307f3092884c3044307e30593002> /NLD (Gebruik deze instellingen om Adobe PDF-documenten te maken waarmee zakelijke documenten betrouwbaar kunnen worden weergegeven en afgedrukt. De gemaakte PDF-documenten kunnen worden geopend met Acrobat en Adobe Reader 5.0 en hoger.) /NOR <FEFF004200720075006b00200064006900730073006500200069006e006e007300740069006c006c0069006e00670065006e0065002000740069006c002000e50020006f0070007000720065007400740065002000410064006f006200650020005000440046002d0064006f006b0075006d0065006e00740065007200200073006f006d002000650072002000650067006e0065007400200066006f00720020007000e5006c006900740065006c006900670020007600690073006e0069006e00670020006f00670020007500740073006b007200690066007400200061007600200066006f0072007200650074006e0069006e006700730064006f006b0075006d0065006e007400650072002e0020005000440046002d0064006f006b0075006d0065006e00740065006e00650020006b0061006e002000e50070006e00650073002000690020004100630072006f00620061007400200065006c006c00650072002000410064006f00620065002000520065006100640065007200200035002e003000200065006c006c00650072002e> /PTB <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> /SUO <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> /SVE <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> /ENU (Use these settings to create Adobe PDF documents suitable for reliable viewing and printing of business documents. Created PDF documents can be opened with Acrobat and Adobe Reader 5.0 and later.) /KOR <FEFFc7740020c124c815c7440020c0acc6a9d558c5ec0020be44c988b2c8c2a40020bb38c11cb97c0020c548c815c801c73cb85c0020bcf4ace00020c778c1c4d558b2940020b3700020ac00c7a50020c801d569d55c002000410064006f0062006500200050004400460020bb38c11cb97c0020c791c131d569b2c8b2e4002e0020c774b807ac8c0020c791c131b41c00200050004400460020bb38c11cb2940020004100630072006f0062006100740020bc0f002000410064006f00620065002000520065006100640065007200200035002e00300020c774c0c1c5d0c11c0020c5f40020c2180020c788c2b5b2c8b2e4002e> >> >> setdistillerparams << /HWResolution [1200 1200] /PageSize [595.276 793.701] >> setpagedevice