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Preparation and Application of Amphoteric Polyacrylate Containing Long

Hydrophobic Aliphatic Chain in the Presence of Poly(vinyl alcohol)
Peizhi Lia; Yiding Shena; Xiaorui Lia; Xiaowu Yanga
a
Key Laboratory of Auxiliary Chemistry & Technology for Chemical Industry, Ministry of Education,
Shaanxi University of Science & Technology, Xi'an Shaanxi, P.R.China

Online publication date: 19 January 2011

To cite this Article Li, Peizhi , Shen, Yiding , Li, Xiaorui and Yang, Xiaowu(2011) 'Preparation and Application of
Amphoteric Polyacrylate Containing Long Hydrophobic Aliphatic Chain in the Presence of Poly(vinyl alcohol)',
Polymer-Plastics Technology and Engineering, 50: 1, 29 — 35
To link to this Article: DOI: 10.1080/03602559.2010.512345
URL: http://dx.doi.org/10.1080/03602559.2010.512345

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 Polymer-Plastics Technology and Engineering, 50: 29–35, 2011
Copyright # Taylor & Francis Group, LLC
ISSN: 0360-2559 print=1525-6111 online
DOI: 10.1080/03602559.2010.512345
Preparation and Application of Amphoteric Polyacrylate
Containing Long Hydrophobic Aliphatic Chain in the
Presence of Poly(vinyl alcohol)
Peizhi Li, Yiding Shen, Xiaorui Li, and Xiaowu Yang
Key Laboratory of Auxiliary Chemistry & Technology for Chemical Industry, Ministry of Education,
Shaanxi University of Science & Technology, Xi’an Shaanxi, P.R.China
Amphoteric polyacrylate containing long hydrophobic aliphatic
chain in the presence of poly(vinyl alcohol) (PVA) was synthesized.
The influences of PVA on the properties of the emulsion and its film
were investigated in details. In addition, the emulsion and the film
were characterized by various examining methods. Furthermore,
the applied properties of paper sized by amphoteric polyacrylate
in the presence of poly (vinyl alcohol) were measured, in contrast
to acrylic polymer prepared with the conventional low molecular
Downloaded At: 08:30 28 January 2011
weight emulsifier, the physical indexes were all improved.
Keywords Amphoteric polyacrylate; Application; Hydrophobic
aliphatic chain; Poly(vinyl alcohol); Preparation
INTRODUCTION
Polyacrylate latex can be directly used without causing
pollution from organic solvents, accounting for its diverse
applications such as in coating, adhesives, paper and textile
finishes[1–4]. In emulsion polymerization, the surfactant
plays important roles in the stability, rheology, and control
of the particle size of the resulting latexes. Conventional
latex is prepared from emulsion polymerization in the
presence of low molecular weight emulsifiers, the residual
emulsifier in latexes would have negative effects on the
properties of the products, possibly cause a reduction in
water-resistance and durability of the final product, and
can even cause the environmental pollution[5–8].
There are some researches about the polymerization
using PVA as a protective colloid[9–18]. Poly(vinyl alcohol)
(PVA) plays an important role as a protective colloid in the
emulsion polymerization, the PVA will become grafted
and=or adsorbed on the latex particles providing stability
during the polymerization. An emulsion stabilized with
PVA has many advantages over surfactants, including
Newtonian fluidity, superior primary wet tackiness, high
strength and creep resistant film properties compared to
Address correspondence to Peizhi Li, Key Laboratory of
Auxiliary Chemistry & Technology for Chemical Industry, Minis-
try of Education, Shaanxi University of Science & Technology,
Xi’an Shaanxi, 710021, P.R.China. E-mail: lpz110@163.com
29
latexes stabilized with low molecular weight surfactants.
Furthermore, the polyhydric alcohol polyvinyl alcohol
(PVA) has several unique features: it is water soluble, crys-
tallizable, and capable of hydrogen bonding. Compared
with the conventional emulsion polymerization, the incor-
poration of PVA as protective colliod can endow latex with
one or more of the following advantages: no emulsifier
migration during film formation, excellent shear stability
and monodisperse particle size distribution and strong
hydrogen bonding.
In general, the stabilizer of polymer emulsions strongly
affects not only the emulsion colloidal properties but also
the film properties, and then it affects the application of the
polyacrylate. However, there are few researches about
amphoteric polymer emulsion using poly(vinyl alcohol) as
protective colloid in paper sizing agent. In this paper, PVA
was directly employed to copolymerize with acrylate mono-
mers as protective colloid by radical polymerization for pre-
paring paper sizing agent without any purification ways.
Besides, the influences of PVA on the properties of the emul-
sion and its film, such as particle size and rheology behavior of
emulsion, and mechanical properties of its film were investi-
gated in details. In addition, the emulsion and the film were
characterized respectively. Furthermore, the applied proper-
ties of amphoteric polyacrylate in paper sizing are determined.
EXPERIMENTAL
Materials
Butyl acrylate (BA), styrene (St), methacrylic acid
(MAA), methacrylatoethyl trimethyl ammonium chloride
(DMC, Fig. 1) and octadecyl acrylate (ODA) were all pur-
chased from Tianjin No. 3 Chemical Reagent Factory and
used without further purification; poly (vinyl alcohol)
(PVA), at an 88% hydrolysis degree, were bought from
Shantou XingHe Fine Chemistry Limited Company and
used without further purification; 2,2-azobis (2-amidinopro-
pane) dihydrochloride (AAPH) was purchased from
Shanghai Huarun Chemical Corporation of China; Deio-
nized water was applied for the polymerization processes.
 30 P. LI ET AL.
FIG. 1. Structural formula of DMC.
Preparation of Amphoteric Polyacrylate Emulsion
A 250-mL 3-necked round-bottom flask was equipped
with a reflux condenser, a thermometer and a mechanical
stirrer. The reactor flask charged with PVA (variable) and
deionized water were heated to 85
C in a water bath. It
was stirred at 350 rpm until the PVA was completely soluble
in water solution, the polymerization was started with 5 g of
aqueous solution of AAPH initiator (1.5 wt%) and the
mixture of St (10 g), BA (10 g), DMC (10 g), MAA (2 g)
and ODA (5 g) monomers added dropwise and finished
within 1.5 h. The reaction was kept at 85
C for 4 h. Named
as 1# acrylic resin.
For comparison, the preparation of 1# amphoteric
polyacrylate was repeated, except that PVA was not
added, and the traditional emulsifier OP-10(0.5 g) was used
Downloaded At: 08:30 28 January 2011
instead. Named as 2# acrylic resin.
Film Preparation
Films were obtained by casting the amphoteric polya-
crylate emulsion on tetrafluoroethylene (TFE) plates and
allowing them to dry at room temperature for 5 days and
then at 60
C for 12 h. After demoulding, the films were
kept into a desiccator to avoid moisture.
Performance Measurement and Characterization
Dynamic Light Scattering (DLS). The particle size of
the amphoteric polyacrylate emulsion was analyzed by a
dynamic light scattering (Zeta-plus, Brookehaven Instru-
ments Co.). All samples were redispersed by sonificator
before analyzing the particle size.
Rheology of Emulsion. The viscosity, pseudoplasticity
and thixotropy of emulsion were analyzed in an American
Brookfield DV-III Ultra Programmable Rheometer. The mea-
surements were carried out at 20
C in the rotational mode
using concentric cylinders type SC4–21. Then, 100 cm3 of
aqueous emulsion was used in the measurements. Controlled
shear rate (CSR) experiments were carried out as follows:
shear rate was increased from 10 s1 to 120 s1 and maintained
for 200 s to provide a uniform and standardized state in all the
solutions. Then, the shear rate was gradually increased from
10 s1 to 120 s1 followed by a gradual decrease from 120 s1
to 10 s1. The preceding experiments were repeated and an
excellent reproducibility was always obtained.
Mechanical Properties of the Films
The tensile strength and elongation at break of the films
were measured on a multifunctional electronic strength
tester TS2000-S (Scientific and Technological Limited
Company of High Iron in Taiwan). Tensile test bars
(5  70 mm2) were cut from films of 0.4–0.8 mm thickness.
The standard tensile test performed was an adaptation of
ASTM 412–83, D638–84 and D 882–83 methods.
Characterization
Fourier Transform Infrared (FT-IR) Spectrometry.
FT-IR spectra were obtained with a Germany Bruker
Vector 22 FT-IR Spectrometer using solution cast films
on KBr Discs.
Micromorphology Measurement of Emulsion. The mor-
phology of amphoteric polyacrylate emulsion was observed
by Hitachi (Model S570) transmission electron microscope
(TEM). The sample was diluted to the required concen-
tration with distilled water before measurement.
X-Ray Diffraction (XRD). The sample was dried at
40
C to a constant moisture content in a vacuum oven prior
to X-ray scanning with a Rigaku model D=Max-B X-ray
diffractometer (Brandt Instruments, Inc., Slidell, LA) with
a Bragg–Brentano parafocusing geometry, a diffracted
beam monochromator, and a conventional copper target
X-ray tube set to 40 kV and 30 mA. The X-ray source was
CuKa radiation. Data were collected from 3
to 70
(the
angle of diffraction) with a step width of 0.02
and a step
time of 0.4 s.
Thermogravimetric Analyzer (TGA). Thermogravi-
metric experiments were performed on a Germany Netzsch
209 TG analyzer. A film sample about 5 mg was placed in a
platinum sample pan and heated from room temperature
to 500
C, under N2 atmosphere, at a heating rate of
10
C=min.
The Application in the Paper Sizing. Sizing of the
unsized hardwood bleached paper sheets was performed
respectively by dipping the sheets into two kinds of poly-
mer aqueous solutions (1 wt%). Wet sheets were pressed
at 0.35 MPa for 5 min, then dried in an oven at 105
C for
10 min, and conditioned at 20
C and 65% relative humidity
for more than 24 hours.
Sizing degree of paper sheets were evaluated by Stockigt
method. Measurement of tensile strength was tested by ISO
1924. Measurement of folding strength was tested accord-
ing to ISO 5626. Surface strength was measured according
to ISO 3783.
RESULTS AND DISCUSSION
Effect of the Content of PVA on Particle Size
Effect of the content of PVA on particle diameter of the
emulsion is shown in Figure 2. It is found that the particle
size decreases first then increases according to the content
of incorporated PVA. When the incorporation of PVA
 AMPHOTERIC POLYACRYLATE IN THE PRESENCE OF PVA
FIG. 2. Effect of the content of PVA on particle diameter of the
emulsion.
increases from 4% to 8% (the percentage is relative to the
mass of the total monomers, the follows are as the same),
the particle size decreases with increasing amount of
PVA. However, when the incorporation of PVA is more
Downloaded At: 08:30 28 January 2011
than 8%, the particle size of the emulsion increases.
According to thermodynamic law, Equation (1) can be
used, when polymer was dispersed into water with tempera-
ture and pressure kept constant.
DG ¼ r  DA ð1Þ
where 4G represents variation in free enthalpy; r repre-
sents interfacial tension between polymer and water; 4A
represents variation in interfacial area.
In general, if the polymer can be well dispersed into
water, 4A would be positive, as well as r. And therefore
4G would be positive, as a result, the dispersion can’t pro-
cess spontaneously until in virtue of external force. In order
to increase 4A, that is, thinning down the particles, the
interfacial tension should be low enough when the external
force is the same. As to a polymer with good hydrophilicity,
r is relative small, so accordingly 4A can be bigger, and
particle size is just the opposite.
In emulsion polymerization a partially hydrolyzed PVA is
commonly used in order to exploit its hydrophobic–
hydrophilic characteristics. While at the beginning with
increasing amount of PVA, which is mainly exhibits hydro-
philic characteristics more than hydrophobic characteristics,
the interfacial tension would increase, leading to the decrease
of particle size. When the incorporation of PVA is more than
8%, the situation reverses, hydrophobic property is main
factor, which leading to the increase of particle size.
Effect of the Content of PVA on Rheology Properties
The rheological properties not only affect workability
but also have something with their stability and some other
31
properties. Rheological measurements can be a powerful
tool to investigate this aspect, since the flow behavior is
not only a fundamental property by itself, but it also car-
ries the fingerprints of the microstructure of the dispersion
and the forces acting between the particles. PVA is capable
of providing a series of desirable properties to the final
product, such as better shear resistance, and superior stab-
ility. The application conditions of paper sizing are mainly
determined by their rheological properties. Therefore, the
rheology property of amphoteric polyacrylate emulsion
has been considered in this study.
According to the Ostwald-Dewael Power-law Equation,
the rheological behavior can be described as follows:
ga ¼ k  cn1 or r ¼ k  cn ð2Þ
where r is shear stress, c is shear rate, n is flow-behavior
index (Newtonian fluid, n ¼ 1; Non-Newtonian fluid,
n<1; k is consistency coefficient (the apparent viscosity
increases with increasing k), ga is apparent viscosity.
Equation (3) can be obtained by Equation (2):
lg r ¼ lg k þ n lg c ð3Þ
Since there exists a linear relationship between lgrand
lgc, the n and k values can be calculated using a linear
regression approach.
Figure 3 shows the flow curves of latexes with different
PVA content and their flow-behavior index (n) and consist-
ency coefficient (k) were calculated from Figure 3a (as
shown in Table 1). The n value of the emulsion increased
greatly with increasing PVA content. This indicates that
these emulsions are non-Newtonian liquids, i.e., there is
great variation of viscosity by increasing the shear rate.
At the same time, addition of PVA amount produces an
increase in the apparent viscosity of emulsions. The consist-
ency coefficient (k) increased from 3.557 to 4.418 when
amount increased from 4% to 10%. The main reason is that
PVA is usually viewed as a steric stabilizer, where hydro-
phobic groups attach onto the polymer particles, while
hydrophilic moieties stretch out in the water phase to pro-
vide stability to the dispersion. PVA chains tend to extend
and associate in the water phase, creating bridges among
different particles, similar in this respect, to associative
polymers or other PVA chains, which lead to the change
of interaction force between the polymer’s latex particles.
On the one hand, due to hydrogen bond action of polymers
in water phase, the viscosity increases. On the other hand,
the increment of moieties stretching out in the water lead
to the interaction force between latex particle and water
increases, manifesting the increase of the apparent viscosity.
In addition, it is also found that ga decreased greatly at
the beginning and then become invariable with increasing
shear rate (as shown in Fig. 3b), which manifest that
 32 P. LI ET AL.

where ga is systematic apparent viscosity, Vi is particles’

interior phase volume, u is stacking coefficient, ke is shape
factor, ge is particle’s outside viscosity. Deformation took
part in particles with the action of shear stress, ke decreased
and u increased which eventually lead to the decrease of ga.
And accordingly ga keeps invariable when the particles
keep steady shape. Furthermore, due to the existence of
polar groups in polymer molecular chain, hydrogen bonds
are produced, and eventually forming hydrated layer. The
hydrated layers would be destroyed with the increase of
shear rate, which make the particles’ relative movement
more easily and therefore decreases ga; but when shear rate
increases to a certain degree, the hydrated layers would be
totally destroyed, ga would not decrease any longer. It can
be described according to a hard-sphere behavior: associ-
ation of polymer blocks from PVA chains in the water
phase, generate reversible particle flocks through bridging
mechanisms, and destroyed by shear, which make particle’s
crustaceous hydrated layer thin.

Effect of the Content of PVA on Mechanical Properties

Table 2 shows variation of mechanical properties with
Downloaded At: 08:30 28 January 2011

the dosage of PVA. The tensile strength and elongation

at break reach the peak while the dosage of PVA is 8%.
PVA is capable of forming hydrogen bonding between
polymer particles, which served as cross-linkages when
casting membranes. To a certain degree, PVA can prevent
molecules from sliding, which results in the increase of
stress and strength. However, excessive cross-linkages
make macromolecular chain hardly oriented under external
force, which leads to the decrease of tensile strength, tensile
modulus and elongation at break.

FIG. 3. Effect of PVA content on rheology curve of emulsion.
emulsions are endowed with pseudo-plasticity. Mooney
equation can explain this phenomenon, which was
described as follows:
ln ga ¼ ln ge þ ke Vi =ð1  Vi =uÞ
Characterization
The infrared spectrum of the amphoteric polyacrylate
under the incorporation of PVA is 8% is illustrated in
Figure 4. The peaks at wavenumbers of 3430 cm1 come
from the O-H groups in PVA and MAA monomer. The
one at 1731 cm1 is associated with the vibrating absorption
of carbonyl groups, and the one at 1164 cm1 is associated
ð4Þ to the C-O-C groups in acrylate monomer. The peaks at

TABLE 2
TABLE 1 Mechanical properties with variation of dosage of PVA
The n and k values with variation of dosage of
PVA for emulsion PVA Tensile Tensile Elongation at
(%) strength (MPa) modulus (MPa) break (%)
Samples PVA (%) n K
2 12 32 72.1
A 4 0.941 3.357 4 15 46 73.2
B 6 0.818 4.252 6 21 52 83.5
C 8 0.739 4.416 8 28 71 92.4
D 10 0.734 4.418 10 23 63 90.8
 AMPHOTERIC POLYACRYLATE IN THE PRESENCE OF PVA 33

FIG. 6. The particle size distribution of the amphoteric polyacrylate

emulsion.
FIG. 4. FT-IR curve of amphoteric polyacrylate.

134 nm to 203 nm, and exhibits monodisperse particle size

wave numbers of 1641 and 952 cm1 are assigned to the
distribution.
methyl groups of quaternary ammonium in the cationic
Crystallinity determines the flexibility of the molecular
monomer.
chains of polymers. XRD was used to observe the crystal-
The peaks at wave numbers of 3027, 758 and 699 cm1
Downloaded At: 08:30 28 January 2011

linity of the film. Figure 7 shows the X-ray diffraction

are associated to the C-H groups and the one at 1459 cm1
curve of the amphoteric polyacrylate. From Figure 7, it
is associated to the C¼C groups with the vibrating in
can clearly seen that there is a weak diffraction peak of
benzene ring. The peaks at wave numbers of 2952 cm1
the crystalline amphoteric polyacrylate, the crystallinity is
come from the C-H in the backbone of the copolymer.
commonly considered as ordered structure of chain seg-
The appearance of all these peaks demonstrates that ampho-
ment owing to hydrogen bonds occurring in the polymer.
teric polyacrylate has been successfully copolymerized.
The microcrystallinity is beneficial to the improvement of
The morphology of amphoteric polyacrylate emulsion is
mechanical property.
presented in Figure 5. Figure 5 demonstrates that the latex
Thermal decomposition behavior of the amphoteric
particles exhibit the regular typical spherical, the surface of
polyacrylate film was investigated by TGA. The thermo-
the particles is as clean as smooth, and uniformity distri-
gram of the amphoteric polyacrylate is shown in Figure 8.
bution. As shown in Figure 6, the average diameter of
amphoteric polyacrylate is about 172.4 nm, ranging from

FIG. 5. TEM photograph of amphoteric polyacrylate (100000). FIG. 7. X-ray diffraction spectra of the amphoteric polyacrylate.
 34 P. LI ET AL.

increased by 44.23% and the tensile strength improved

by 48.67%. Besides, the surface strength and folding
strength were improved by 38.13% and 16.28%, respect-
ively. There are two reasons for these, one is amphoteric
polyacrylate prepared by using PVA as the protective
colloid avoids the water-uptaking reaction of the small
surfactants; two is that PVA has better strength and
microcrystallinity, added PVA protective colloid can
improve the strength largely.

FIG. 8. TG curves of membrane of the amphoteric polyacrylate.
From Figure 8, it can be seen that the film remained fairly
stable because the weight loss was less than 7.1%, even
when the temperature was raised up to about 200
C, which
can meet the temperature requirement of the paper sizing
Downloaded At: 08:30 28 January 2011
CONCLUSION
Amphoteric polyacrylate containing long hydrophobic
aliphatic chain in the presence of poly(vinyl alcohol)
(PVA) as protective colloid was synthesized via radical
polymerization prepared with styrene (St), methacryla-
toethyl trimethyl ammonium chloride (DMC), butyl
acrylate (BA) and methacrylate acid (MAA). The influ-
ences of PVA on the properties of the emulsion and its film,
such as particle size and rheology behavior of the emulsion,
mechanical properties of its film, were investigated in
details.
In addition, the FT-IR spectra spectrum showed that

absolutely. the amphoteric acrylate copolymer was formed. TEM

and DLS analysis exhibited that the polymer latex particles
Application Property were uniform spheres with the diameter of about 172.4 nm,
Table 3 shows that the physical mechanical properties ranging from 134 nm to 203 nm. XRD revealed that the
of paper surface sized by amphoteric polyacrylate using microcrystallinity existed in the polymer was beneficial to
PVA as the protective colloid when the incorporation of the improvement of mechanical property. TGA concluded
PVA is 8% and by amphoteric polyacrylate using conven- that thermal decomposition behavior of the amphoteric
tional emulsifiers, respectively. In contrast to sizing by the polyacrylate film can meet the temperature requirement
polyacrylate using conventional emulsifier, the physical of the paper sizing absolutely.
mechanical properties of paper surface sized by ampho- Furthermore, in contrast to acrylic polymer prepared
teric polyacrylate using PVA as the protective colloid with the conventional low molecular weight emulsifier,
were improved evidently such as the sizing degree the applied properties of paper sized by amphoteric poly-
acrylate in the presence of poly(vinyl alcohol) were
measured: the sizing degree increased by 44.23% and the
TABLE 3 tensile strength improved by 18.67%, besides, the surface
The physical mechanical properties of paper strength and folding strength were improved by 38.13%
surface after surface sizing and 16.28%, respectively.
Sizing Tensile Surface Folding
degree strength strength strength ACKNOWLEDGMENTS
Type (s) (102 N=m) (cm=s) (n) We would like to express our great thanks to the
National Natural Science Foundation of China (Grant
Paper sizing 75 40.36 290.5 50 numbers: 20876093 and 50973057) and the Graduate
with 1# Innovation Fund of Shaanxi University of Science and
Acrylic resin Technology for financial support.
Paper sizing 52 34.01 210.3 43
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