Waterborne Epoxy-Acrylic Dispersions Modied by Siloxane

Kai Zhang
School of Chemical and Energy Engineering, South China University of Technology, Guangzhou, P. R. China and School of
Chemistry and Applied Chemistry, Huanggang Normal University, Huangzhou, P. R. China
He-qing Fu, Hong Huang, and Huan-qin Chen
School of Chemistry and Applied Chemistry, Huanggang Normal University, Huangzhou, P. R. China
Waterborne epoxy dispersions have been an active area of research since the early 1980s
because of legislative restrictions on the use of organic solvents in conventional solvent-
based products and also because they exhibit almost the same high performance levels as
solvent-borne epoxy. In the present study, rst the epoxy-acrylic graft copolymers (EAG)
were synthesized through grafting acrylic monomers onto the epoxy resin, and then EAG
were modied by amine-siloxane through the incorporation of the latter into the former via
ring-opening reaction. The graft copolymers act as an effective compatibilizer between the
styrene-acrylic resin phase and the epoxy matrix, which make the waterborne epoxy disper-
sions stable. The effects of methacrylic acid (MAA) content, siloxane content, neutralization
degree on the particle size and the apparent viscosity of the dispersions were investigated.
The structure of EAG, and siloxane-modied EAG copolymers (EAGS) was conrmed with
Fourier transform infrared (FTIR) spectroscopy analyses. The physical properties of the dis-
persions and the physicochemical properties of the lms show the dramatic improvement in
properties of waterborne epoxy dispersions due to epoxy-acrylic-graft-copolymer modied
by siloxane.
Keywords Waterborne coatings, epoxy-acrylic-graft-copolymers, siloxane, epoxy dispersion,
physicochemical properties
1 INTRODUCTION
Epoxy resins have been widely used as coatings, adhesives,
and sealants because of their combined properties of toughness,
exibility, adhesion, and chemical resistance.
[1,2]
However, in
order to make them tractable, it is necessary to dilute the resins
with organic solvents. Since the 1960s a substantial research
effort has been made into the development of waterborne
epoxy systems because of the limit of volatile organic com-
pounds, and some interesting methods have been proposed.
[36]
One is dependent on the external emulsier to make the resin
dispersed in water. The other is by way of chemical modi-
cation to introduce polar groups which confer water dispersi-
bility to the resin. Woo and Toman
[6,7]
synthesized the
water-reducible epoxy-acrylic composite copolymers via
grafting copolymerization, later many researchers used
similar methods to prepare the waterborne epoxy dispersions,
but the storage stability of the dispersions and the chemical
resistance of the lms is inconsistent.
[8,9]
Amine-siloxanes
are known for high reactivity, unusual exibility, high
thermal stability, excellent chemical resistance, and high cor-
rosion protective efciency.
[1014]
The conventional methods used to introduce siloxanes into
polymers involve a common blending process.
[15,16]
Blending
may increase the viscosity of the resin and a larger amount of
the solvent can be consumed in the preparation of the coatings;
the evaporation of the excess solvent, during and after curing,
may cause shrinkage and produce internal stresses in the
coatings, causing leaching after a certain time. In the case of
epoxy-siloxane blends, phase separation and bleeding of the
silicon component occur.
[15,17]
The phase separation and low
surface energy of silicone-polymer-modied epoxies hamper
their use in surface coatings.
[17]
Thus, to solve this problem, it
is mandatory to incorporate a siloxane moiety into the polymer
backbone through some chemical reaction.
[15,18]
The incorpor-
ation of siloxane into epoxy through chemical reaction
improves the aforementioned drawbacks.
[15,18]
This work was nancially supported by Science and Technology
Research Program (07BQ010), Hubei Provincial Department of
Education.
Received 18 October 2006; Accepted 29 October 2006.
Address correspondence to Kai Zhang, School of Chemical and
Energy Engineering, South China University of Technology, Guangz-
hou 510610, P. R. China. E-mail: kaizhangchem@yahoo.com.cn
Journal of Dispersion Science and Technology, 28:12091217, 2007
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print /1532-2351 online
DOI: 10.1080/01932690701527896
1209
In this study, epoxy-acrylic graft copolymers (EAG) were
modied by amine-siloxane through the incorporation of the
latter into the former via ring-opening reaction. The graft
copolymers act as an effective compatibilizer between the
styrene-acrylic resin phase and the epoxy matrix, which
make the waterborne epoxy dispersion stable. The factors inu-
encing the particle size and the apparent viscosity of epoxy
resin dispersions were discussed in detail. The physical proper-
ties of the dispersions were evaluated. The structure of EAG
and siloxane-modied EAG (EAGS) was conrmed with
Fourier transform infrared (FTIR) spectroscopy analyses. The
physicochemical analysis of EAGS was carried out by such
instrumental methods as scanning electron microscope
(SEM), thermogravimetric analysis (TGA). The chemical
resistance of the coated samples also was investigated. The
modication of EAG through siloxanes had a synergistic
effect on the properties of the EAGS paints.
2 EXPERIMENTAL
2.1 Materials
Commercially grade liquid epoxy resin diglycidyl ether of
bisphenol-A (E-44, Guangzhou Dongfeng Chemicals Ltd., Co.,
China) was used as basic material. Methacrylic acid, methyl
methacrylate, and styrene were used as grafted monomers.
Benzoyl peroxide was used as initiator. A blend of 2-butoxy-
ethanol and n-butanol was used as solvent. Monomers and
solvents used were of analytical grade and purchased from
Guangzhou Chemicals Factory, China. g-aminopropyl methyl
diethoxysilane (A-2100, Commercially grade, Guangzhou
Shuangjian Trade Ltd., Co.) was used as modier. Trimethyl-
ethanolamine (A.R., Guangzhou Chemicals Factory, China)
was used as neutralization agent. Deionized water also was used.
2.2 Synthesis of Epoxy-Acrylic Graft Copolymers (EAG)
The graft copolymers were synthesized by the copolymeri-
zation of epoxy resin with grafted monomers. The copolymer-
ization was carried out at 1101158C for 6 hours using benzoyl
peroxide and a blend of 2-butoxyethanol and n-butanol as
initiator and solvent, respectively, under a nitrogen atmos-
phere. After taking out the solvent, epoxy-acrylic graft copoly-
mers were obtained.
[7]
2.3 Preparation of Siloxane-Modied Epoxy-Acrylic-Graft-
Copolymer Dispersions
The grafted copolymers mixture was then fed into an
agitated reducing vessel with trimethyl-ethanolamine for 15
minutes at room temperature. Then calculated g-aminopropyl
methyl diethoxysilane was added dropwise through an
additional funnel. The system was reacted for 70 minutes at
508C. Siloxane-modied epoxy-acrylic-graft-copolymer dis-
persions with a solid content of 30 wt% were obtained by
adding calculated deionized water to above system, and the
dispersions were agitated for 1 hour. All the process was
agitated with stirrer.
2.4 Film Formation
Films were prepared with a dry thickness of about 0.5 mm.
After casting the dispersions onto glass plates (10 cm 5 cm),
the lms were allowed to dry for 6 hours at 1108C in the oven.
2.5 Characterization
Formation of EAG and siloxane-modied EAG was ascer-
tained from FTIR spectra. The FTIR spectra were recorded
on the Perkin-Elmer 1730 (Perkin-Elmer Co. Ltd., USA).
The fracture surface morphology of the samples was
observed using SEM (HITACHA S-510, Japan). Prior to the
examination, the surface was coated with a thin layer of gold
in order to improve the conductivity and prevent charging.
The thermal stability of the lms was assessed by TGA using
TGA-7 (Perkin-Elmer Co. Ltd., USA) at a heating rate of
108C/minutes in an inert atmosphere. The particle size of the
dispersions was measured by using dynamic light scattering
(DLS, MALVERN Autosizer Lo-C, USA). The 633.7 nm
of laser wavelength and the 908 scattering angle were used.
The transparence of lms was studied by using optical micro-
scope. Circumvolved Viscometer (BROOKFIELD DV-II
Viscometer Engineering /ABS. INC. MIDDLEBORO, MA
02346, USA) was also employed to measure the viscosity of
the dispersions.
3 RESULTS AND DISCUSSION
3.1 Evaluations of Physical Properties of the EAGS
Dispersions
3.1.1 Particle Size
The stability of dispersions is related to the size of the
particle closely, the smaller the particle size is, the steadier
the dispersion is. Research has been conducted on the factors
inuencing the particle size of the EAGS dispersions. In
summary, the particle size was mainly related to MAA
content and A-2100 content. The results were illustrated in
Tables 1 and 2.
Particle size of dispersions primary depends on hydrophili-
city which is mainly governed by the ionic group content. The
hydrophilicity of epoxy resin was greatly enhanced after
grafting because the carboxylic acid groups in MAA were
attached on epoxy resin chains. With the amount of MAA
increasing, the hydrophilicity of the modied resin was
improved, the modied resin displayed different morphology
in water, ranging from opaque cream to white-milky dispersion
and the particle size of the dispersions corresponded from large
to small. This may be due to the higher proportion of MAA,
which imparts better dispersibility of the particles of EAG
copolymer. When the amount of MAA was increased from
18 to 22.2%, the average particle size of dispersions was
K. ZHANG ET AL. 1210
decreased from 263.9 nm to 91.7 nm. Further increase of MAA
content in modied resin didnt result in further decrease of the
average particle size. Whereas, which resulted in a decrease of
the ability of chemical resistance of the lms. Therefore the
optimal amount of MAA in our system is 22.2%.
The main reason for bad stability of EAG dispersions is the
opening-ring reaction of oxirane groups with carboxylic acid
groups occurs in the presence of trimethyl-ethanolamine as cat-
alyzer during the stored process. In our experiment, the amino
groups of A-2100 reacted with oxirane groups of the EAG
copolymers, which can avoid opening-ring reaction occurring
during the stored process, and also can form new crosslinking
structure. However, the average particle size of EAGS disper-
sions was decreased in a nonlinear manner with an increase of
the A-2100 content. When more A-2100 was introduced, the
particle size of the dispersions increased, and which even
made the modied resin cant be dispersed by water. This
could be due to the possibility that certain A-2100 may
undergo hydrolysis association, resulting in entanglements
and clustering of the polymer molecules. Only when the
A-2100 content was in the range of 1 to 2.5%, the neighboring
group of EAGS copolymers can shield from A-2100 hydrolyz-
ing effectively, and the EAGS dispersions have good stability.
3.1.2 Apparent Viscosity
The rheologic properties of the dispersions not only have
effects on the construction property, but also on storage stab-
ility and lms property. It is important to study the rheologic
properties of the dispersions for valuing the qualities and mas-
tering the application of the dispersions.
[19]
Figure 1 described the curve of the apparent viscosity of dis-
persions via the MAA content at the same rate of shear. As can
be seen from Figure 1, the apparent viscosity of the dispersions
was improved greatly with the amount of MAA increasing.
From the viewpoint of thermodynamics, the total Gibbs free
energy of the polymers in the dispersions is constant.
The hydrophilicity of the modied resin was enhanced with
the amount of MAA increasing, which inevitably causes the
weakness of the boundary tension between modied resin and
water and the enlargement of the surface area of the modied
resin. The number of the absorbed hydrous layer was increased
with the increasing of the surface area of the modied resin,
TABLE 1
Effect of MAA content on the physical properties of EAGS copolymers dispersions
a
Samples
MAA content
(mass%)
Siloxane content
(mass%)
Mean diameter
(nm)
Compatibility
with water
Shelf life at
508C 1 month
Zk137 18.8 2 263.9 PC, milky PS
Zk131 22.2 2 91.7 C, White
translucent
E
Zk135 24.4 2 95.2 C, White
translucent
E
Zk136 26.6 2 71.1 C, Yellow
translucent
E
a
C compatible; CS complete separation; E excellent; IC incompatible; NS No separation; PC partially compatible; PS
partial separation.
TABLE 2
Effect of siloxane content on the physical properties of EAGS copolymers dispersions
a
Samples
Siloxane content
(mass%)
MAA content
(mass%)
Mean diameter
(nm)
Compatibility
with water
Shelf life at 508C
1 month
Zk141 0.5 22.2 Cant test IC CS
Zk139 1 22.2 257.4 PC, milky PS
Zk131 2 22.2 91.7 C, White
translucent
E
Zk140 2.5 22.2 147.2 C, White
translucent
NS
Zk142 3 22.2 Cant test IC CS
a
C compatible; CS complete separation; E excellent; IC incompatible; NS No separation; PC partially compatible; PS
partial separation.
WATERBORNE EPOXY-ACRYLIC DISPERSIONS 1211
which was equal to enlarge the volume of the disperse phase.
According the Moony theory, the larger the volume of the
disperse phase is, the greater the apparent viscosity of the disper-
sions is. In addition, the electroviscosity occurred when the dis-
persions was owing, which required external force to overcome
the interaction between the surface charge of micelle and the ion
of the inner electric double layer, then also induced the increas-
ing of the apparent viscosity.
The chain of EAGS copolymers has many carboxylic
groups, which can be neutralized with an amine such as
trimethyl-ethanolamine and diluted with water to obtain water-
borne systems. The reaction degree of carboxylic groups with
amine groups is simply called neutralization degree. Figure 2
described the curve of the apparent viscosity of dispersions
via neutralization degree at the same rate of shear. It was
shown that the dispersions were occulent and unstable when
the neutralization degree was below 80%, and the apparent vis-
cosity of the dispersions was almost kept unchanged when the
neutralization degree was in the range of 90% to 110%, while
the apparent viscosity of the dispersions was sharply increased
when the neutralization degree was above 110%. Such phenom-
ena indicated that the neutralization degree has a buffer effect on
the apparent viscosity of the dispersions. The reason for this is
that the dispersions of the waterborne epoxy are a heterogeneous
system. The pH value of the dispersive medium (water phase)
was changed with the neutralization degree, however, as the
surface of polymer micelle structured with electric double
layer, the hydrous layer of the surface of polymer micelle with
water was formed through hydrogen bond and Coulomb force.
There existed equilibriums (shown in Figure 3) for ions of the
surface of polymer micelle, and then buffer solution occurred
in hydrous layer, so the pH value of the hydrous layer
was kept little changed. Once the pH value in the water phase
was changed greatly, the buffer effect of the hydrous layer
was damaged. When the pH value was much little, ionization
of -COOH was prevented, the hydrophilicity of the modied
resin was so poor that the dispersions were occulated, while
when the pH value was much high, the hydrophilicity group
of the modied resin was almost ionized, and the hydrous
layer was thickened, then it was easy to generate particle
network, so the apparent viscosity of the dispersions was
increased greatly.
The effect of A-2100 content on the apparent viscosity of
the dispersions also was examined (shown in Figure 4). From
Figure 4 it can be observed that the apparent viscosity of the
dispersions was reduced greatly with the amount of A-2110
increasing when the content of A-2100 was low than 2%.
The main reason is the difference of structure and polarity
between A-2100 and the EAG copolymers. As we all know
that the solvation and hydrogen bond action make the increas-
ing of the dispersion viscosity. For nonpolar unit of A-2100, the
solvation and hydrogen bond action is poor. However, when
the content of A-2100 was above 2%, the hydrolysis effect of
A-2100 increased gradually, which made the increasing of
the apparent viscosity.
3.1.3 Compatibility with Water and Shelf Life
The shelf life of waterborne dispersions is a very important
characteristic, which determines their safe storage period. The
experimental sets of epoxy dispersions were kept at 508C for
one month in an incubator and any kind of phase separation
FIG. 1. Effect of the MAA content on apparent viscosity of dispersions.
FIG. 2. Effect of neutralization degree on apparent viscosity of
dispersions.
FIG. 3. Equilibrium equation for ions of the surface of polymer micelle.
K. ZHANG ET AL. 1212
was noticed. The compatibility of EAG dispersions contained
MMA content above 18.8% was quite satisfactory, but the
shelf life was less than 1 week at room temperature. When
EAG copolymers were modied by siloxane, the shelf life of
the EAGS dispersions was improved greatly when the
A-2100 content was in the range of 1 to 2.5%. The results
reported in Tables 1 and 2 also revealed that the dispersions
with small particle size showed very good performance in
terms of shelf life.
3.2 Films Characteristics
3.2.1 FTIR Analysis
The formation of EAGS proceeds in two steps and is ascer-
tained from FTIR spectra. In the rst step, the grafting of
acrylic monomers onto epoxy resin occurred in the presence
of free radical initiator. The formation of and
of epoxy at 1731 1607 cm
21
and 1582 cm
21
, respectively,
are used to ascertain the completion of the reaction
(Figure 5).
[7]
The second step involves reaction between
oxirane group of EAG copolymers and amino group of
A-2100, which is conrmed by the disappearance of epoxy at
916 cm
21
, increaseing in the intensity of hydroxyl group of
epoxy at 3420 cm
21
, and formation of Si-OCH
2
CH
3
at
1100 cm
21
and Si-CH
3
at 1256 cm
21
, but these peaks are not
obvious because of little A-2100 amount (Figure 6).
3.2.2 Optical Microscopy Observation
The miscibility of bisphenol-A epoxy resin with Styrene-
Acrylic copolymers (SA) is poor. Even when they were
mixed with the help of some solvent, the lms made from
which, however, were whitely opaque and easily peeled off.
It showed that the blends separated into two phases after
solvent evaporated at room temperature. As the components
in our system have the similar degrees of afnity to solvent,
it is difcult to separate pure EAG copolymers from the
system with common method of precipitating separation. It
was found that the lms are transparency and smooth, and
they are very difcult to be peeled off from the plates. Such
kind of phenomena indicated that the EAG copolymers inter-
connected bisphenol-A epoxy resin with Styrene-Acrylic copo-
lymer. The graft copolymers acted as an effective
compatibilizer between the styrene-acrylic resin phase and
the epoxy matrix, which leaded to the high miscibility of
FIG. 4. Effect of the siloxane content on apparent viscosity of dispersions.
FIG. 5. FTIR of EAG copolymers.
FIG. 6. FTIR of EAGS copolymers.
WATERBORNE EPOXY-ACRYLIC DISPERSIONS 1213
them. After A-2100 was introduced to EAG copolymers, trans-
parent and smooth lms also were formed. The results clearly
showed that it was through chemical reaction that the EAG
copolymers were modied by A-2100.
3.2.3 Morphological Characteristics of EAGS Copolymers
Figure 7 displays a series of SEM micrographs of EAGS
copolymers with different methods (Figure 7a by blending;
Figure 7b by grafting). The weight fraction of g-aminopropyl
methyl diethoxysilane is 1.15 wt%. The unmodied epoxy
resin is a homogeneous system, with smooth fracture
surfaces.
[14]
It can be seen that Figure 7a appeared obvious
phase separation for the poor miscibility between epoxy
resin, siloxane and styrene-acrylic blending. The size of micro-
phase region of EAGS copolymers was 0.20.5 mm, and with
relatively homogeneous distribution (Fig. 7b). Comparing the
difference between Figures 7a and 7b, we think the reason is
that the EAG copolymers modied by siloxane acted as an
effective compatibilizer between the styrene-acrylic resin
phase and the epoxy resin matrix, which reduced the gathering
rate of the dispersing phase.
[20]
Although the EAGS copoly-
mers by blending could also partly make a reaction between
epoxy resin and A-2100 during the period of depositing and
curing, the reaction degree was greatly lower than that of by
grafting, and also the reaction speed was greatly slower,
which was limited by the reaction conditions such as tempera-
ture and time. So gathering of unreacted siloxane would easily
take place. It was one of important reasons that waterborne
dispersions prepared by blending had bad storage stability.
Figure 7c described the morphological characteristics of the
fracture surfaces by grafting after curing. It was observed
that the size of microphase region had not been changed
obviously and only the margin of microphase region had
been turned blurry after curing. It indicated that the microphase
structure of EAGS copolymers had formed before curing.
Commonly, epoxy resin modied by liquid rubber takes on a
homogeneous phase before curing, while phase separation
occurs during curing because of the cross-linking of
epoxide.
[21]
The morphology of EAGS copolymers was
formed during the reaction, curing process was due to the
cross-linking of silanol, the hydrolysate of siloxane, not the
cross-linking of epoxide.
At beginning of the reaction, siloxane was dispersed in the
EAG copolymers phase for the shearing force of stirring.
When the reaction continued, the oxirane groups of EAG copo-
lymers were reacted with amido groups of siloxane, the EAGS
copolymers were formed, by which the trend of phase separ-
ation was weakened.
3.2.4 Thermal Analysis
The thermal stability of different samples was investigated
with TGA studies (Figure 8), the weight-loss percentage and
the corresponding temperature of degradation for different
samples are also given in Table 3. As can be seen from the
data, the thermal stability of plain epoxy curative systems is
good, with 5% weight loss at 2908C. Its main weight loss
range is in 3004008C, because the manner of its degradation
is mainly presented with the degradation of C-C, C-O, C-H on
the main chain. The thermal stability of SA copolymers is bad,
with 5% weight loss at 1398C, and it begins to degrade quickly
when up to 1508C. The grafting of styrene-acrylic monomers
onto epoxy resin reduces the thermal stability and decreases
the degradation temperature. This may be attributed to the
presence of thermally weak branched chain in epoxy
FIG. 7. SEM micrographs of EAGS copolymers with different methods.
FIG. 8. TG curves of different samples (1) pure epoxy, (2) SA copoly-
mers, (3) EAG copolymers, and (4) EAGS copolymers (2 wt% siloxane).
K. ZHANG ET AL. 1214
network. The incorporation of siloxane into EAG system
improves the thermal stability and enhances the degradation
temperature to an appreciable extent. The delay in degradation
caused by siloxane moiety may be attributed to its ablative
behavior imparted by partial ionic nature, high bond energy
and thermal stability of -Si-O-Si- linkage.
[22]
Although the
oxirane groups of EAG copolymers were reacted with amino
groups of siloxane, the thermal stability of EAGS copolymers
was not decreased comparing with that of EAG copolymers.
From these observations, it was concluded that lms of
EAGS copolymers showed high thermal resistivity.
3.2.5 Chemical Resistance
Films also were tested for chemical resistance by soaking of
the coated specimens in 5.0 wt% vitriol (H
2
SO
4
), 5.0 wt%
sodium hydroxide (NaOH) solutions, ethanol, ethyl acetate,
gasoline, and distilled water at room temperature (Table 4).
Table 4 showed that the chemical resistance of SA copolymers
is poor, which was quickly peeled off from the plates in
ethanol, water or 5% H
2
SO
4
, and in ethyl acetate, gasoline or
5% NaOH, it also only remained for 24 hours. The chemical
resistance of EAG copolymers is better than that of SA copo-
lymers, which is attributed to the strong adhesive force to the
glass of epoxy. When the EAG copolymers were blended
with siloxane, chemical bond on the glass surface was
formed by siloxane, which improved the adhesive force
between EAG copolymers and glass. This force would
become greater when siloxane was introduced by way of
chemical reaction, so EAGS copolymers have a good chemical
resistance after curing. But the lms contained silicon was
easily damaged under basic condition comparing with other
mediums, the reason might be that -Si-O- linkage is quite easy
to be attacked under basic condition.
3.2.6 Water Absorption
Dried lms (30 mm 30 mm; original weight designated
as W
0
) were immersed in water for 24 hours at 258C. After
the residual water was wiped from the lms using lter
paper, the weight (W
1
) was measured immediately.
[23]
It was calculated as follows: water absorption, R (%)
(W
1
2W
0
)/W
0
100 (%)
Figure 9 showed that the water absorption of EAGS copoly-
mers decreased with the increasing of siloxane weight fraction,
which is attributed to the excellent hydrophobicity of siloxane
and the cross-linking characteristics of silanol, the hydrolysate
of siloxane. The water absorption of lms decreases, which can
cause the size of hydrophilic microdomain turn small after
swelling, not enough to the half-wavelength of visual rays, at
TABLE 3
The results of TG analysis
Sample
Discompose temperature at different weight loss percent (8C)
number 5% 10% 20% 30% 40% 50% 60% 70% 80%
1 290.86 326.29 345.96 360.6 371.82 381.45 392.23 404.65 422.31
2 138.99 186.58 228.68 272.76 299.37 318.14 335.01 360.32 400.38
3 193.57 212.35 301.65 335.14 356.43 374.05 388.9 402.89 418.56
4 181.26 220.32 304.34 343.68 371.88 396.66 415.43 429.88 452.9
Note: 1: E-44; 2: SA copolymers; 3: EAG copolymers; 4: EAGS copolymers (2 wt% siloxane).
TABLE 4
The chemical resistance of different samples
a
SA
copolymers
EAG
copolymers
EAGS
copolymers
(by blending)
EAGS
copolymers
(by grafting)
Ethanol A C D E
Ethyl acetate B C D E
Gasoline B D D E
Distilled water A C D E
5% H
2
SO
4
A D D E
5% NaOH B C C D
Note: A: lms damaged after 3 hours; B: lms damaged after 24 hours; C: lms damaged after 48 hours.
a
D: unchanged after 24 hours, bubbly after 48 hours; E: unchanged after 48 hours.
WATERBORNE EPOXY-ACRYLIC DISPERSIONS 1215
the level where the lms could remain transparent. This charac-
teristic
[24]
is very important for coating materials. However,
when the weight fraction of siloxane exceeded 2.5%, the
storage stability of waterborne EAGS dispersions turned bad.
4 CONCLUSIONS
A waterborne epoxy-acrylic-graft-copolymer dispersion
modied by siloxane was synthesized. The physical properties
of the dispersions and the physicochemical properties of the
lms of the EAGS copolymers proved to be very interesting.
The following conclusions were reached:
1. The EAGS copolymers act as an effective compatibilizer
between the styrene-acrylic resin phase and the epoxy
matrix, which make the waterborne epoxy dispersions
stable.
2. When the MAA content was 22.2% and the siloxane
content was 2%, the waterborne EAGS copolymers disper-
sions were stable and the particle size was minimal.
The apparent viscosity of the dispersions increased
with the increasing of the MAA content, and decreased
with the increasing of the A-2100 content, whereas the
neutralization degree has a buffer effect on the apparent
viscosity of the dispersions.
3. The physicochemical properties of the lms showed that the
EAGS copolymers had comparatively thermal stability to
EAG copolymers, and the mass loss was 5% at 1818C.
The lms of EAGS copolymers dispersions had good
chemical and water resistance.
LIST OF ABBREVIATIONS
EAG epoxy-acrylic graft copolymers
MAA methacrylic acid
EAGS siloxane-modied EAG copolymers
FTIR Fourier transform infrared spectrometer
SEM scanning electron microscope
TGA thermogravimetric analysis
E-44 diglycidyl ether of bisphenol-A
A-2100 g-aminopropyl methyl diethoxysilone
DLS dynamic light scattering
SA Styrene-Acrylic copolymers
H
2
SO
4
vitriol
NaOH sodium hydroxide
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