Chin. J. Chem. Eng.

, 15(6) 899905 (2007)

Synthesis and Characterization of Waterborne Epoxy Curing Agent

Modified by Silane
LU Guangqi(), SUN Jianzhong()* and ZHOU Qiyun()
State Key Laboratory of Chemical Engineering, Department of Chemical and Biochemical Engineering, Zhejiang
University, Hangzhou 310027, China
Abstract A novel waterborne epoxy curing agent was prepared using 3-glycidoxypropyl trimethoxysilane
(GPTMS) as a termination agent of adduct, which was synthesized by triethylene tetramine (TETA) and liquid epoxy resin (E-51). The effects of the reaction temperature and time on the synthesis process were investigated experimentally. The particle size and the distribution of water dispersion of the curing agent were measured by dynamic light scattering (DLS). The structure of the products was characterized by Fourier transform infrared spectrometer (FTIR) and 1H-nuclear magnetic resonance (1H NMR). The properties of the synthesized curing agent and
the epoxy resin film cured by it were also measured. The results showed that the appropriate temperature for the
synthesis of adduct was at 6575 and the reaction time was 45h, and that the suitable reaction temperature of
curing agent synthesis was 7585 and the reaction time was 34h. When the mass ratios of GPTMS and acetic
acid were 3%5% and 5%10% respectively, the hardness, water resistance and adhesion of the cured film were
improved significantly.
Keywords waterborne epoxy curing agent, silane, modification

INTRODUCTION
Epoxy resins are widely applied in protective
coatings, structural adhesives, and electronic industry
because of their heat, solvent, moisture and chemical
resistance, good mechanical and electrical properties,
and great adherence to many substrates[1]. Recently,
more attentions have been paid to the water dispersion
of epoxy curing agent in consideration of the environmental protection[2]. The curing agent plays an
important role in the performances of epoxy resin
cured film. The organic acids are commonly used in
epoxy-polyamine curing agents to make them distributed in water[3]. However, the performances of cured
film are not satisfactory due to the acid neutralization,
besides the flexibility and chemical resistance of the
cured film should be improved[4]. Lately, silane is
often used in coatings as modification agent and additive to improve the flexibility, chemical resistance and
thermal stability of the film[5].
A waterborne curing agent was prepared using
liquid epoxy resin and polyamine by Waler et al.[6],
which had poor intermiscibility with epoxy resin, so
the performance of cured film is not perfect. An
epoxy-polyamine curing agent incorporated with a
surface active agent was synthesized by Tao et al.[7].
In their study the surface active agent was used as
both emulsifying agent and curing agent. An amidoamine curing agent was prepared using carboxyl
terminal polyether alcohol as termination agent for
epoxy-polyamine adduct by Elmore et al.[8]. A
self-emulsified waterborne epoxy curing agent of the
nonionic type was synthesized by Zhou et al.[9] using
diglycidyl ether of polyglycol (DGEPG), triethylene
tetramine (TETA) and liquid epoxy resin (EPON828)
as raw materials, which has good property of emulsifying liquid epoxy resin. A series of epoxy silane as
active additives for reactive polymer emulsions have

been evaluated in both one-pack and two-pack systems by Chen et al.[10]. A novel amine terminated
elastomeric siloxane modifier (siloxane amide, SA)
for solvent epoxy networks was synthesized and the
dual role of SA amine, not only as a curing agent and
but also as a toughener, was studied by Marimuthu et
al.[11].
In this work, a novel waterborne epoxy curing
agent modified by silane was prepared using
3-glycidoxypropyltrimethoxysilane (GPTMS) and C12
acyclic glycidyl ether (AGE) as a termination agent of
adduct, which was synthesized by triethylene tetramine (TETA) and liquid epoxy resin (E-51). The
structure of the curing agent was characterized. The
synthetic process and the effects of the amount of
GPTMS on the properties of curing agent and performances of cured film were studied.
2 EXPERIMENTAL
2.1 Materials
Diglycidyl ether of bisphenol A (DGEBA, E-51, epoxy equivalent mass 196) was purchased from Shanghai
Resin Co. (China). 3-Glycidoxypropyltrimethoxysilane
(GPTMS) was supplied by Shanghai Junjiang Tech.
(China). C12 acyclic glycidyl ether (AGE) was obtained from Shanghai Yinsheng Chemical Co. Ltd.,
(China). Triethylene tetramine (TETA), propylene
glycol methyl ether (PM) and acetic acid (HAc) were
purchased from Sinopharm Chemical Reagent Co.
(China). Waterborne epoxy resin emulsion (AB-EP-20,
solid diglycidyl ether of bisphenol A, 50% solids content, epoxy equivalent mass 417556) was supplied
by Zhejiang Anbang New Material Development Co.
(China). All chemicals were used as received. All solvents and other chemicals were reagent grade or better.

Received 2007-01-25, accepted 2007-08-27.

* To whom correspondence should be addressed. E-mail: bigwig@zju.edu.cn

900

Chin. J. Ch. E. (Vol. 15, No. 6)

2.2 Synthesis of waterborne epoxy curing agent

modified by silane
Into a 250ml four-necked round-bottom flask
equipped with a heating water bath, stirrer and reflux
condenser, were charged with 15.53g TETA and 20g
PM. The mixture was heated to 75 to let TETA
dissolved in PM. Under nitrogen atmosphere, 18.64g
of E-51 was added gradually over a period of 1.5h.
The reaction was maintained for another 2.5h. The
chemical reaction is shown in Fig.1 (Reaction 1). After the reaction completed, the reactant mixture was
distilled to remove excess TETA and most PM. Then
PM solution of AGE and/or GPTMS (66.30%, by
mass) was added dropwise evenly in 1h. The reaction
was maintained for 2h at 80. The reaction is shown
in Fig.1 (Reaction 2). The reactant mixture was cooled
to 60. 2.55g of HAc was added dropwise for neutralization. After most solvent was distilled out, the
water dispersion of epoxy curing agent modified by
silane with solid content of 40% was obtained by
adding deionized water dropwise with stirring. In the
reaction system mentioned above, the mass ratio of
TETA to E-51 was 2.231. The molar ratio of epoxy
group in terminator to NH2 is 11. The molar ratios of GPTMS to AGE were 0100, 397, 595,
and 1090. The molar ratios of HAc to N H were
0%, 5%, and 25%.
2.3

Curing of waterborne epoxy resin

The curing agent synthesized was mixed with
waterborne epoxy resin emulsion (AB-EP-20) by molar ratio (N H to epoxy group) of 11. The mixture

was coated on tinplate, and placed at ambient temperature for 24h. The sample was put into an oven at
60 for 2h, and maintained at 90 for 1h. Then the
sample was cooled slowly to room temperature.
2.4

Measurement and characterization

The epoxy group conversions were measured by
non-aqueous titration with HBr/glacial acetic acid[12].
FTIR spectra were recorded on a Nicolet 5700 FTIR
spectrometer. 1H NMR characterizations were carried
out by Bruker AC-80 NMR spectrometer using
tetramethylsilane (TMS) as internal standard. The particle size was determined by Malvern Zetasizer
3000HSA Zeta laser nanometer particle size analyzer.
The viscosity of waterborne curing agent was obtained
on HAAKE VT550 Viscometer. The performances of
cured film, such as water resistance, adhesion, surface
dry time, and pencil hardness were measured by Chinese standard GB 1733/79, GB/T 9286-1998, GB/T
1728-79, and GB/T 6739-1996, respectively.
3 RESULTS AND DISCUSSION
3.1 Effects of reaction time and temperature on
epoxy group conversion of E-51
The effects of reaction time and temperature on
the conversion of epoxy group of E-51 are shown in
Fig.2. It can be seen from Fig.2(a) that the conversion
of epoxy group of E-51 increases with the reaction
time. The conversion reaches about 97% in 4h, which
is considered as the proper reaction time.
The effect of reaction temperature on the epoxy
group conversion of E-51 is shown in Fig.2(b). It can

Figure 1 Addition reaction between E-51 and TETA (Reaction 1) and

termination reaction by AGE and/or GPTMS (Reaction 2)
December, 2007

Synthesis and Characterization of Waterborne Epoxy Curing Agent Modified by Silane

(a) Effect of reaction time

(b) Effect of reaction temperature

Figure 2 Epoxy group conversion of E-51
(Molar ratio of TETA/E-51 is 2.231)

901

(a) Effect of reaction time

(b) Effect of reaction temperature

Figure 3 Epoxy group conversion of AGE and/or
GPTMS (Molar ratio of epoxy group of AGE and/or
GPTMS/N-H is 11)

be seen that the conversion of epoxy group increases

with the reaction temperature. However, gel phenomenon may occur in the reaction system due to a
high reactive activity of secondary amine as TETA to
the epoxy group of E-51 when the reaction temperature is too high. So the proper reaction temperature
should be 6575.
3.2 Effects of reaction time and temperature on
termination reaction of the adduct by AGE and
GPTMS
The effects of reaction time and temperature on
the conversion of epoxy group of AGE and/or
GPTMS are shown in Fig.3. The conversion of epoxy
group increases with the reaction time, and the conversion of epoxy group reached 97% when the reaction was continued for 2h with stirring after AGE
and/or GPTMS were added dropwise. Fig.3(b) suggests that the appropriate temperature is 7585.
The yield is 95% under the following condition:
the addition reaction between TETA and E-51 should
be accomplished at 75 for 4h, the mass ratio of
TETA to E-51 was 1 1.2, and the adduct of
TETA-E-51 was terminated by AGE and/or GPTMS
at 75 for 34h, the molar ratio of the epoxy group
of terminator to -NH2 group was 11.
3.3 Characterization
3.3.1 FTIR
Figure 4 shows FTIR spectra of E-51, adduct of
TETA-T-51, GPTMS, and products terminated by
AGE and/or GPTMS.
In Fig.4, diagnostic peaks of diglycidyl ether of

bisphenol A can be seen at 1247cm 1, 2980cm 1,

1
1
1300cm , 830cm [13] in spectra (a), (b) and (d).

The band at around at 910cm 1[14] in spectra (a) and

Figure 4 FTIR spectra of (a) E-51, (b) TETA-E-51

adduct, (c) pure GPTMS, (d) product
terminated by AGE and/or GPTMS

(c) is the diagnostic peak of epoxy group. In spectra (b)

and (d), there is no diagnostic peak of epoxy group,
which means the addition reaction between epoxy
group and N H2. It also can be proved by the appear
ance of Fermi resonance double-hump at 3300cm 1
1
and 3360cm in spectra (b) and disappearance in

spectra (d). The band at around 1070cm 1 in spectra

(c) is assigned to Si O band. And in spectra d, a

strong peak can be seen at 1110cm 1 but not at

1

1070cm . The peak height of 11101120cm 1 rela1

tive to aromatic ring (830cm ) in spectra (b) is
smaller than that in spectra (d), although there are

peaks in 11101120cm 1 range in spectra (b) origi

nally. So, Si O bond at 1070cm 1 in spectra (d)
1
has made an excursion to 1110cm and superposes upon
the peaks in this range. So, it can be reasoned out that
the reaction between silane and polyamine happened.
3.3.2 1H NMR
1
H NMR spectra of E-51 is shown in Fig.5. Aromatic protons was shown at : 6.57.5(a), protons on
Chin. J. Ch. E. 15(6) 899 (2007)

Chin. J. Ch. E. (Vol. 15, No. 6)

902

CH3 of diglycidyl ether of bisphenol A at : 1.72 (b),

protons of epoxy group at : 2.73.0(c), protons of
carbon which is combined with oxygen in diglycidyl
ether of bisphenol A at : 3.64.4[15] (d). All the

Figure 5

Figure 6
December, 2007

integral areas are normalized by integral area of aromatic protons, and the same normalization is conduct
in Figs.6 and 7. Integral area ratio of (a) to (b) is
10.77 which is approximate 1.3. And Integral area

H NMR spectra of E-51

H NMR spectrogram of TETA-E-51 adduct

Synthesis and Characterization of Waterborne Epoxy Curing Agent Modified by Silane

Figure 7

903

H NMR spectra of the product terminated by AGE

ratio of (c) to a is 0.491 which is approximate 0.49,

which is supposed as x. Integral area of (d) is 0.56.
1
H NMR spectrogram of TETA-E-51 adduct is
shown in Fig.6. Aromatic protons can be seen at :
6.57.5 (a), protons of CH3 of diglycidyl ether of
bisphenol A at : 1.5 (b), protons of carbon which is
combined with nitrogen at : 2.32.8 (c), protons of
carbon which is combined with oxygen in diglycidyl
ether of bisphenol A at : 34. Integral area ratio of
(c) to (a) is 3.73 which is supposed as y. As the quantity relation referred before, number ratio of protons of
epoxy group to aromatic protons is x: 0.49. And y/x is
approximate 7.5. Since the amount of aromatic protons keeps constant through the whole reaction process and there are two epoxy groups in each molecule,
it can be deduced that the number of C combined with
N is 14. So it proved that addition reaction happened
between TETA and E-51.
1
H NMR spectra of the product terminated by
AGE is shown in Fig.7. Aromatic protons can be seen
at : 7 (a), protons of carbon which is combined with
nitrogen at : 23 (b), saturated aliphatic protons in
AGE at : 11.6 (c). Integral area ratio of (b) to (a) is
4, which is supposed as z. The ratio of z to x is 4
0.49, which is approximate 8. So, with the quantity
relation mentioned before, it is can be gained that the
number of C combined with N increase from 14 to 16
in one molecule. And the ratio of (c) to (b) is 5.904
which is equal to 2316 approximately. It is almost
the ratio of saturated aliphatic protons of AGE to protons of carbon which is combined with nitrogen. So,
the structure of the product terminated by AGE in
Fig.7 could be confirmed.

3.4

Effects of amount of silane

The influences of oxygen, water vapor and CO2
were eliminated by nitrogen atmosphere. The performance of cured film is improved by silane, but the
amount of silane using in this system has restrictions.
If the amount of silane is more than 10% of all termination agents used in the reaction system, the silane in
curing agent will cure with each other to become
blocks and gels when the curing agent is distributed in
the water. The effects of amount of GPTMS on the
appearance, mean particle size and viscosity of curing
agent water dispersion with 40% solid content are
shown in Table 1. With increasing of the amount of
GPTMS using in the system, the mean particle size of
curing agent water dispersion modified by silane with
different amount of GPTMS is about 5nm, and the
dispersion of distribution is narrow, about 3nm. So the
biggest diameter of curing agent is less than 10nm.
The result measured after 90d shows that the particle
size and the dispersion of distribution of curing agent
are hardly changed. As a result, the stability of the
waterborne epoxy curing agent is perfect.
The color of water dispersion darkens and the
viscosity increases as it stands. A major cause is that
GPTMS contains hydrolysable alkoxy group
(Si OCH3). The alkoxy group will hydrolyze and
yield silanols (Si OH) when curing agent is dispersed
in water[16]. The hydrogen bond action strengthens
with increasing amount of Si O in the system[17].
And another reason could be that the molecular chain
may be lengthened by crosslink between some
Si OH with each other. Therefore, the viscosity increases with increasing amount of GPTMS, and so
Chin. J. Ch. E. 15(6) 899 (2007)

Chin. J. Ch. E. (Vol. 15, No. 6)

904
Table 1

Properties of water dispersions of curing agent with different contents of silane (solid content of 40%)

Content of Mean parti- Dispersion of Mean particle Dispersion of

Viscosity, Pas
GPTMS, % cle size, nm distribution, nm
size, nm
distribution, nm

Theoretic amine

value, mgg 1

Appearance
(visualizing)

4.1

2.3

4.7

3.3

23

135.24

light yellow

4.4

2.7

5.1

2.7

24.5

129.42

light yellow

5.2

4.1

4.5

3.5

34

129.53

light yellow

10
5.0
Measured after 90d.

3.6

3.7

2.6

50

130.53

yellow

does the color. The theoretic amine value of waterborne epoxy curing agent is about 130mg KOH per
gram when the solid content is 40%.
The effects of amount of GPTMS on the performances of cued film are shown in Table 2. It can be
seen from Table 2 that the hardness and adhesion to
metal are improved by using GPTMS as termination
agent. Without using GPTMS in curing agent, the
pencil hardness of the cured film is 5 H, and the adhesion is 1. With curing agent modified by GPTMS, the
adhesion of cured film is 0 and pencil hardness is
harder than 6 H. The reason is that Si O transforms to Si OH by hydrolyzing in water. Si OH
bonds can cure with each other, and also can react
with epoxy group to become cross-linking network.
The energy of Si O bond is more than that of C C
and C O bonds. The stability of Si O bond is better
because it needs more energy to be broken[18]. Besides degree of the cross-linking increasing, the water
resistance of cured film is perfected by using silane in
curing agent due to hydrophobic property of silane. It
can be seen from Table 2 that the surface dry time decreases and curing temperature declines, and that the
water resistance of cured film is improved with increasing of the amount of GPTMS. However, the
more silane is not the better always. The smoothness
of cured film gets worse if the amount of GPTMS is
over 10% of total termination agents. A possible reason is that silane cross-links and conglomerates rapidly with evaporation of water if amount of GPTMS is
excessive.
Table 2

3.5

Effects of HAc
The effects of the amount of HAc using as neutralization agent on performances of cured film are
shown in Table 3. The hardness, adhesion, and
smoothness of cured film become worse, and that the
color becomes darker with increasing amount of HAc.
It can be seen from Table 3 that the pencil hardness
drops from 6 H to 4 H and the adhesion turns into 1
from 0 with increasing amount of HAc. The primary
reason is that the ionicity of the curing agent enhances
with increasing amount of HAc. The intermiscibility
of the curing agent to epoxy emulsion decreases, although the water-solubility is enhanced[19]. As a result, the system of epoxy emulsion and waterborne
curing agent can not be crosslink completely since the
diffusion of curing agent into epoxy emulsion particle
becomes more difficult. And color of the film is darkened because of the oxidation occurring on the unreacting N H during the curing process[20]. So the
amount of HAc using as neutralization agent should
be under 10%.
4

CONCLUSIONS
A waterborne epoxy curing agent modified by
silane was prepared. The performances of epoxy
coating film cured by the waterborne epoxy curing
agent modified by silane, such as the degree of
cross-linking, the hardness, the adhesion, and the water resistance, are improved significantly. The addition
reaction between TETA and E-51 could be accom-

Performances of films cured by the synthesized curing agent with different contents of silane
Surface dry time,
Water resistance
h

Starting curing
temperature,

Content of
GPTMS, %

Smoothness

Adhesion

Pencil hardness

smooth

5H

smooth

6H

7d

80

smooth

6H

10d

60

10

not smooth

 6H

3.5

15d

50

Table 3

1d

90

Performances of films cured by the synthesized curing agent with different amounts of HAc

HAc/N H, %

Smoothness

Adhesion

Pencil hardness

Appearance

smooth

6H

slight yellow

10

smooth

6H

yellow

25

not smooth

4H

yellow heavier

December, 2007

Synthesis and Characterization of Waterborne Epoxy Curing Agent Modified by Silane

plished at 75 for 4h, the mass ratio of TETA to

E-51 was 11.2. The appropriate conditions of the
termination reaction of the adduct of TETA-E-51 by
AGE and/or GPTMS were as follows: reaction temperature was 7585, reaction time was 34h,
molar ratio of epoxy group of terminator to NH2
group was 11, amount of GPTMS was 3%5%,
and amount of HAc was 5%. The yield coefficient is
95%. The particle size is round 5nm, and the theoretic
amine value is about 130mg KOH per gram.
REFERENCES
1

2
3

4
5

6
7

Ren, H., Sun, J.Z., Wu, B.J., Zhou, Q.Y., Synthesis and
curing properties of a novel Novolac curing agent containing naphthyl and dicyclopentadiene moieties, Chin.
J. Chem. Eng., 15(1), 127131(2007).
Elisabete, A., Dulcinea, S., Jorge U., Corrosion performance of waterborne coatings for structural steel,
Prog. Org. Coat., 37, 131140(1999).
Hawkins, C.A., Sheppard, A.C., Wood, T.G., Recent
advances in aqueous two-component systems for
heavy-duty metal protection, Prog. Org. Coat., 32,
253261(1997).
Schneider, W., Ambient temperature curing waterborne
epoxy systems, Mater. Performance, 30(1), 28
31(1991).
Ren, H., Qu, Y., Zhao, S., Reinforcement of styrene-butadiene rubber with silica modified by silane
coupling agents: Experimental and theoretical chemistry
study, Chin. J. Chem. Eng., 14(1), 9398(2006).
Waler, F.H., Amide-containing self-emulsifying epoxy
curing agent, U.S. Pat., 5596030 (1997).
Tao, Y.Z., Chen T., Gu G.F., Synthesis and property of
type I waterborne epoxy coating, Chin. J. Colloid
Polymer, 19(6), 1922(2001). (in Chinese)

8
9

10
11

12
13
14

15
16
17
18
19
20

905

Elmore, J.D., Maksymowski, V.J., Henning, Jr.R.W.,

Galgoci, Jr.E.W., Process to prepare aqueous dispersions of epoxy resins, U.S. Pat., 6143809 (2000).
Zhou, J.L., Tu, W.P., Synthesis of nonionic type
self-emulsified waterborne epoxy curing agent and its
properties, J. Chem. Eng. Chin. Univ., 20(1), 94
99(2006). (in Chinese)
Chen, M.J., Fred, D.O., Antonio, C., Philbert,
E.R., Bruce, A.W., Epoxy silanes in reactive polymer
emulsions, J. Coat. Technol., 69, 4955(1997).
Marimuthu, S., Madurai, S.L., Boreddy, S.R.R., Chemistry of siloxane amide as a new curing agent for epoxy
resins: Material characterization and properties, Macromol. Chem. Phys., 206, 25012511(2005).
Li, G.L., Epoxy Resins and Epoxy Coatings, Chemical
Industry Press, Beijing (2003). (in Chinese)
Shen, D.Y., Application of Infrared Spectroscopy in
Macromolecule Research, Science Press, Beijing (1982).
(in Chinese)
Ren, H., Sun, J.Z., Wu, B.J., Zhou, Q.Y., Synthesis and
characterization of a novel epoxy resin containing
naphthyl/dicyclopentadiene moieties and its cured polymer , Polymer, 47(25), 83098316(2006).
Gong, W.M., Analytical Chemistry, Dalian University of
Technology Press, Beijing (2000). (in Chinese)
Ji, W.G., Hu, J.M., Zhang, J.Q., Cao, C.N., Reducing the
water absorption in epoxy coatings by silane monomer
incorporation, Corros. Sci., 48, 37313739(2006).
Liu, W.Y., Study on systhesis and properties of silane-graft-epoxy dispersion, M.S. Thesis, Zhejiang
Univ., China (2006). (in Chinese)
Ebsworth, E.A.V., MacDiarmid, A.G., The Bond to Carbon, Marcel Dekker, New York (1968).
Liu, G.J., Aqueous Dispersoid Coating, China Light Industry Press, Beijing (2004). (in Chinese)
Xu, S.C., Organic Chemistry, Higher Education Press,
Beijing (2000). (in Chinese)

Chin. J. Ch. E. 15(6) 899 (2007)