Materials Letters 161 (2015) 408–410

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Imidazole derivatives as latent curing agents for epoxy thermosetting

resins
Koji Arimitsu a,n, Sawako Fuse a, Kenji Kudo a,b, Masahiro Furutani a
a
Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
b
Central Research Laboratory, The Nippon Synthetic Chemical Industry Co. Ltd., 2-13-1 Muroyama, Ibaraki, Osaka 567-0052, Japan

art ic l e i nf o a b s t r a c t

Article history: We have developed novel liquid-type thermal latent curing agents to generate imidazoles in epoxy re-
Received 30 April 2015 sins. The latent curing agents were synthesized using a Michael addition reaction of fumarate with
Received in revised form imidazoles in 14–53% yields. The latent curing agent, having a thermally labile bulky long-chain alkyl
26 August 2015
succinate group at the nitrogen atom of the imidazole ring, underwent a thermal decomposition reaction
Accepted 29 August 2015
in the temperature range from 200 to 280 °C, which generated the corresponding imidazole by a retro-
Available online 31 August 2015
Michael addition reaction. The curing reaction of epoxy resins by thermally generated free imidazoles
Keywords: proceeded at 150 °C. Furthermore, it was demonstrated that a mixture of the latent curing agent with
Latent curing agent epoxy resins has long storage stability at room temperature, which was not accomplished with the
Imidazole
imidazoles themselves.
Epoxy resin
& 2015 Elsevier B.V. All rights reserved.
Retro-Michael addition reaction
Thermal decomposition

1. Introduction agents are powder-type agents, and there is a serious problem in

Epoxy resins have high resistance towards heat and electricity,
and they are important thermosetting resins for applications such
as adhesives, structural materials and coatings. Many kinds of
curing agents are used for epoxy resins, and they are classified into
phenols [1], acid anhydrides [1,2], carboxylic acids [1], amines [3],
imidazoles [4–7] and others [8,9]. Among them, imidazoles have
recently been paid attention because a chain polymerization of the
epoxy groups can be induced by a catalytic amount of imidazole.
Both the nucleophilic and base catalytic processes can be con-
sidered [10], and these properties can be somewhat changed by
substituted groups on the imidazole ring.
However, it is quite difficult to control the intrinsic high re-
activity of imidazoles in epoxy resins, even at room temperature.
Their liquid mixtures gradually convert into insoluble solids with
cross-linked networks, which makes it difficult to use them as
one-component industrial materials. On the other hand, latent
curing agents have been developed to overcome the storage sta-
bility problem. Hamerton et al. proposed the use of metal cation–
imidazole salt complexes as latent curing agents [11,12]. Shin et al.
prepared encapsulated imidazole derivatives in polycaprolactone
microcapsules, and achieved a long shelf life of the microcapsule-
epoxy resin system at 20 °C [13,14]. However, these latent curing
n
Corresponding author. Fax: þ81 4 7123 9890.
E-mail address: arimitsu@rs.noda.tus.ac.jp (K. Arimitsu).
that they have difficulty permeating micrometre- or submicro-
metre-sized narrow grooves of fabricated substrates in the field of
electronic industry because of their heterogeneous dispersion.
Recently, Spychaj et al. suggested long storage stability of epoxy
resins containing imidazolium salt ionic liquids as the latent cur-
ing agents, while they require a high temperature for curing [15].
Herein, we have developed novel liquid-type latent curing agents
to generate imidazoles by adding a thermally labile bulky group to
imidazole rings. The reactivity and storage stability of epoxy resins
containing these imidazole derivatives were examined.
2. Material and methods
2.1. Synthetic procedure of latent curing agents 1
2.1.1. Synthesis of bis(2-isopropyl-5-methylhexyl) fumarate (2)
Fumaryl chloride (6.64 g, 43.4 mmol) was added to tetra-
hydrolavandulol (13.8 g, 86.9 mmol) in dry tetrahydrofuran (THF,
20 mL). The mixture was stirred at room temperature for 24 h.
Purification was performed using column chromatography on si-
lica gel.
2.1.2. Synthesis of latent curing agent 1a
1,8-Diazabicyclo[5.4.0]-7-undecene (DBU, 0.12 g, 0.83 mmol)
was added to a mixture of imidazole (0.11 g, 1.7 mmol) and 2

http://dx.doi.org/10.1016/j.matlet.2015.08.141
0167-577X/& 2015 Elsevier B.V. All rights reserved.
 K. Arimitsu et al. / Materials Letters 161 (2015) 408–410 409

4H
O O 3H
O
O
O
O 2H
O N O H 1a

Pencil-hardness
R1
F
N
HB 1b
R2 2
1a (R1 = R2 = H)
B 1c
+
1b (R1 = H, R2 = Ph) R1
2B
1c (R1 = Et, R2 = Me)
N
3B
NH 4B
R2 5B
Imidazole 6B
Scheme 1. Chemical structures of liquid-type thermal latent curing agents 1a–1c,
<6B
and their thermal decomposition reaction to generate imidazoles. Liq.
80 120 150 180
Temperature / ˚C
Fig. 3. Pencil hardness of jER828 coating films prepared with 8.8 wt% of 1a–1c on
glass substrates, followed by heating at 80–180 °C for 60 min.

(1.00 g, 2.52 mmol) in dry acetonitrile (10 mL). The mixture was
stirred at room temperature for 1 h. Purification was performed
using column chromatography on silica gel.
For details, please see Supplementary data.

2.1.3. Thermal decomposition behavior of 1

For details, please see Supplementary data.

2.1.4. Evaluation of the reactivity of epoxy resin compositions con-

taining 1
Latent curing agent 1 (0.019 mmol) and jER828 (a bifunctional
epoxy resin, 0.10 g, 0.27 mmol) were dissolved in chloroform
(0.10 g), which was bar-coated on glass substrates. After curing at
80–180 °C for 60 min, the hardness of the coating films was
evaluated using the pencil-scratch method based on JIS K5400
[16].

2.1.5. Evaluation of the storage stability of epoxy resin compositions

containing 1
A liquid mixture of jER828 (0.30 g) containing 1 (0.057 mmol)
was prepared in a test tube. Each sample was stored at room
temperature in the dark until the fluidity had disappeared.

3. Results and discussion

Fig. 1. Thermal decomposition behavior of 1a itself (a), and 1a in jER828 resin (b),
measured using TG–DTA. The molecular design of latent curing agent 1, which has a
succinate moiety, is shown in Scheme 1. Three kinds of imidazoles
1.2 120 were reacted with the double bond of a fumarate via a Michael
Normalized peak intensity

addition reaction, and 1 was synthesized in two reaction steps. The

1.0 100 total yields were 36% (for 1a), 53% (for 1b) and 14% (for 1c). They
Conversion /%

were all liquid products at room temperature. The succinate

0.8 80 moiety has two 2-isopropyl-5-methylhexyl groups that were in-
troduced with a racemic starting compound (tetra-
0.6 60 hydrolavandulol), leading to the liquid states of products, which
did not crystallize. In addition, the branched long-chain alkyl
0.4 40
succinate moiety at one of the nitrogen atoms of the imidazole
0.2 20 ring would be expected to supply steric bulkiness to prevent the
other nitrogen atom reacting with the epoxy resins.
0.00 0 It is assumed that 1 would be thermally decomposed into fu-
0 10 20 30 40 marate 2 and a corresponding imidazole via a retro-Michael ad-
Heating time / h dition reaction, as shown in Scheme 1. The thermal decomposition
points (Td) evaluated using thermogravimetric–differential ther-
Fig. 2. Time courses of the generation of 2 (◆) and the consumption of 1a (■)
mal analysis (TG–DTA) measurements were 202 °C (for 1a, Fig. 1
during heating at 120 °C.
(a)), 277 °C (for 1b) and 263 °C (for 1c).
410 K. Arimitsu et al. / Materials Letters 161 (2015) 408–410

0 day 0 day 0 day 0 day

5 days 5 days 1 day 1 day

13 days 13 days 12 days 12 days

N
NH
1b N
NH
1c

Fig. 4. Observation of the fluidity for evaluating the storage stability of jER828 resins containing 4-phenylimidazole (a), 1b (b), 2-ethyl-4-methylimidazole (c) and 1c (d).

It was found that 1a is decomposed at a lower temperature in
the presence of epoxy resins (Fig. 1(b)). In this case, the exothermic
peaks of the DTA curves were observed in the lower temperature
region (around 150 °C). Such a shift was also observed in the TG
curves. A peak shoulder was observed at around 120 °C in the DTA
curve, which would indicate a curing reaction associated with the
thermal decomposition of 1a.
To confirm the thermal decomposition products, 1a was heated
with butyl glycidyl ether in 1,4-dioxane-d8, monitored by 1H-NMR
spectroscopy (see Supplementary data). After heating in a sealed
tube at 120 °C for 34 h, a peak assigned to two olefin protons of
fumarate 2 appeared at 6.8 ppm, while the intensity of the peak
assigned to a methine proton of 1a was slightly decreased at
5.3 ppm. The generation of 2 was consistent with the consumption
of 1a, which indicated that the decomposition reaction of 1 would
occur without any side reactions (Fig. 2).
As an application for thermosetting resins, jER828 coating films
containing 8.8 wt% of 1a–1c were cured at 80–180 °C for 60 min.
The hardness of the coating films on glass substrates was eval-
uated using the pencil-scratch method based on JIS K5400. The
hardness of the pencils is arranged as follows: 6B (softest), 5B, 4B,
3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H (hardest). The
results are shown in Fig. 3. Films containing 1a were not ade-
quately cured below 120 °C. The maximum value of 3H was re-
corded with 1a and 1b at 180 °C. Well-cured films were obtained
with 1b at 120 °C (2H) or 150 °C (H), for a reason that is under
investigation. In the case of 1c, the hardness value of the cured
films was 6B even with heating at 180 °C. Nevertheless, all mix-
tures retained their liquid state after heating at 80 °C for 60 min,
and it was found that 1a–1c work as thermal latent curing agents.
We also examined the storage stability. A liquid mixture of
jER828 (0.30 g) containing 8.8 wt% of 1b or 1c was prepared in a
test tube, as shown in Fig. 4. As a control, a mixture of the resin
containing the same molar amount of 4-phenylimidazole or
2-ethyl-4-methylimidazole was also prepared. These samples
were stored at room temperature until the fluidity of each sample
disappeared. In the case of 4-phenylimidazole, the mixed resin
was set and colored within 13 days (Fig. 4(a)). On the other hand,
the corresponding mixture of 1b was not set even after 13 days
(Fig. 4(b)). Such a clear difference was also observed between
samples of 2-ethyl-4-methylimidazole and of 1c (Fig. 4(c) and (d)).
The sample of 1c showed fluidity even after 12 days. These results
would indicate that the nucleophilicity of these imidazoles is well
restrained by their branched long-chain alkyl succinate group.
4. Conclusions
In conclusion, we have designed novel liquid-type latent curing
agent 1 that are thermally decomposed without any side reactions.
We confirmed that 1 has a high active curability towards epoxy
resins at 120 °C, and that well-cured films are obtained at this
temperature by using 1b as a latent curing agent. The epoxy
compositions containing of 1b or 1c have long storage stability at
room temperature for more than 12 days. These results show a
unique strategy for fabricating a one-component epoxy thermo-
setting resin.
Appendix A. Supplementary material
Supplementary data associated with this article can be found in
the online version at doi:10.1016/j.bios.2014.05.063.
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