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Chemistry
Materials
Journal of
A simple preparation method of epoxy resin/silica
nanocomposite for T g loss material{
Masahiro Fujiwara,*a Katsunori Kojima,b Yuko Tanakaa and Ryoki Nomurab
a
Kansai Center, National Institute of Advanced Industrial Science and Technology
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(AIST-Kansai), 1 Midorigaoka, Ikeda, Osaka 563-8577, Japan.

E-mail: m-fujiwara@aist.go.jp
b
Osaka Institute of Technology, 5 Ohmiya, Asahi-ku, Osaka 535-8585, Japan

Received 28th November 2003, Accepted 11th February 2004

First published as an Advance Article on the web 1st March 2004

Nanocomposite materials of epoxy resin and silica were prepared by a simple procedure wherein diglycidyl
ethers of bisphenol-A (DGEBA) as the pre-polymer of epoxy resin, tetraethoxysilane (TEOS) as silica source,
and hexahydrophthalic anhydride (HHPA) were mixed together and heated at 170 uC in a sealed autoclave.
HHPA played two roles in this reaction system: one role is as a well-known curing reagent of epoxy resin; the
other is as the condensation reagent of alkoxysilane, since transesterification promotes this reaction. These two
reactions occurred simultaneously in homogeneous solution, and organic–inorganic composite materials were
readily obtained. Field emission SEM/EDX images showed that silica particles of nano size (below 50 nm) were
included in the epoxy resin matrix. Some of these epoxy resin/silica nanocomposite materials displayed high
thermal stability. When DGEBA bearing about three bisphenol-A units and five molar equivalents of TEOS
were reacted, the obtained composite displayed no T g point below 300 uC in the DSC (differential scanning
calorimetry) thermogram. This high thermal stability is likely to be derived from the interaction of hydroxyl
groups of DGEBA with silica.

Introduction the preparation of these composite materials, and successfully

Nanocomposites or hybrid materials which consist of organic
and inorganic components are important research subjects in
material science and nanotechnology.1,2 In order to improve
the performances of organic polymers, mixing or hybridization
with inorganic compounds, especially with silica, has been
actively examined.3 Even the simple blending of silica micro-
particles with organic polymers often improves the compe-
tences of the materials.4 The sol–gel method is effective for
blending inorganic components at the nano level.2,3 Since
alkoxysilanes and organic compounds (monomers or poly-
mers) can form homogeneous solutions in some cases, these
mixed systems are advantageous to nanocomposite syntheses.
Epoxy resins5 are widely utilized as the basis of electronic
devices,6 coating materials,7 bone cements8 and so on. For
printed-circuit boards of micro-compact electronic devices,
more advanced specifications which are hardly accomplished
by common epoxy resins are required. In particular, thermal
deformation of materials must be avoided to prevent the
serious destruction of devices. It is well claimed that a filler
silica mixed with a cured epoxy resin enhances the thermal
stability of the corresponding material.4,9 Therefore, nano-
composite materials of epoxy resin and silica are expected to
have improved thermal and chemical resistances and mechani-
cal properties. It was reported that molecular level mixing of
epoxy resin and silica can be performed by the concurrent
reactions of pre-polymers of epoxy resins with alkoxysilanes.10
Silsesquioxanes bearing an epoxy or amino group were also
utilized for the preparation of epoxy resin/silica composite
materials.11 Partially condensed alkoxysilanes are applied to
DOI: 10.1039/b315474b
afford composites with high thermal stability. In addition,
pseudo-cubic octasiloxane derivatives are often employed to
produce epoxy resin/silica composite materials.12 Although
these novel methodologies provide excellent organic–inorganic
composite materials, some complicated preparation processes
(e.g. the partial hydrolysis of alkoxysilane)11 or some expensive
compounds (e.g. octasiloxane derivatives)12 are required.
Simpler procedures are desired for the practical applications
of these materials.
We have studied various kinds of organic–inorganic com-
posite materials.13 We recently reported that acetic anhydride
promoted the condensation of alkoxysilanes to form silica in
organic media.14 As shown in Fig. 1, transesterification is an
important step of this process. On the other hand, the common
sol–gel method proceeds by hydrolysis of alkoxysilanes by
water.15 The utilization of water as a reagent often results in the
phase separation of the organic and aqueous phases, which is
not favorable for molecular or nano level mixing of organic
and inorganic compounds. According to our experiments, the
condensation of alkoxysilanes by acid anhydride proceeded
efficiently at over 150 uC. On the other hand, cyclic acid
anhydride is also a reagent for the curing process of epoxy resin
(Fig. 2). This process is generally performed over 150 uC as
well. Thus, both the condensation of alkoxysilane and the
curing process of epoxy resin can be conducted with one acid
anhydride at the same reaction temperature. Therefore, it is

{ Electronic supplementary information (ESI) available: infrared spec-

trum of silica directly obtained from TEOS and acetic anhydride in
autoclave, SEM image of Sample 3-5, 1H NMR spectra of DGEBA-1,
DGEBA-3, allyl-DGEBA-3, Si-DGEBA-3, hydridodimethylsilyloxy-
POSS and POSS-DGEBA-3. See http://www.rsc.org/suppdata/jm/b3/ Fig. 1 Reaction scheme of tetraethoxysilane and acetic anhydride to
b315474b/ silica.

This journal is ß The Royal Society of Chemistry 2004 J. Mater. Chem., 2004, 14, 1195–1202 1195

Fig. 2 Reaction scheme of the cure process of DGEBA with cyclic
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acid anhydride.
expected that these two reactions occur simultaneously to
produce both silica, by condensation, and epoxy resin, by the
cure process, in one homogeneous solution system. Finally,
the silica and epoxy resin thus produced will be blended at the
molecular or nano level by this simple method using three
common and cheap starting compounds. This system is
regarded as a novel variation of the hybrid material production
method ‘Type III’ noted by Novak.1 We attempted this
reaction system, and eventually succeeded in the preparation of
nanocomposite materials of epoxy resin/silica. Furthermore,
some of these composites were found to be T g loss materials. In
this paper, we wish to report this simple preparation process
for the nanocomposite synthesis of epoxy resin/silica and their
thermal performances.
Experimental
Materials
Diglycidyl ethers of bisphenol-A (DGEBA) as pre-polymers
of epoxy resins were purchased from Aldrich. DGEBA
bearing approximately one or three bisphenol-A units are
named as DGEBA-1 and DGEBA-3 in this paper, respectively.
Average molecular numbers of DGEBA-1 and DGEBA-3
are 355 and 1075, respectively. 1-(Hydridodimethylsilyloxy)-
3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.13,9.15,15.17,13]-
octasiloxane (hydridodimethylsilyloxy-POSS) was also
obtained from Aldrich. The toluene solution (2 mM) of the
platinum complex catalyst was obtained from the xylene
solution of the platinum-1,3-divinyl-1,1,3,3-tetramethyldisilox-
ane complex (Aldrich). TEOS (tetraethoxysilane; from Kanto
Chemical), HHPA (hexahydrophthalic anhydride, 1,2-cyclo-
hexanedicarboxylic anhydride; from Tokyo Kasei) and other
common chemicals were also commercial available ones.
Measurement
DSC and TGA thermograms were recorded using a Shimadzu
DSC-60 or Shimadzu TGA 50M instrument, respectively. DSC
measurement was carried out under nitrogen flow conditions
with 10 uC min21 temperature increase. TGA measurement was
performed under air with 10 uC min21 temperature increase.
Infrared spectra were obtained using a Perkin Elmer Spectrum
One spectrometer using KBr pellets. 1H NMR spectra
(400 MHz) were measured by a JEOL AL-400 spectrometer.{
FE-SEM (field emission SEM) images were measured using a
Hitachi S-5000 microscope apparatus, and EDX images were
obtained using a Horiba EMAX-5770W instrument.
Preparation of the epoxy resin/silica composite
Required amounts of DGEBA, TEOS and HHPA were mixed
in a glass vessel and the resulting homogeneous solutions were
reacted statically in an autoclave. A typical reaction procedure
is described by taking Sample 3-5 (see Table 1), which is well
characterized in this paper, as an example. 2.15 g (about
2 mmol) of DGEBA-3, 2.09 g (10.0 mmol) of TEOS and 3.70 g
(24.0 mmol) of HHPA were mixed in a 50 mL glass vessel and
heated at 90 uC for 2 h, forming a homogeneous, high viscous
solution. This vessel was placed in a stainless autoclave of
1196 J. Mater. Chem., 2004, 14, 1195–1202
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Table 1 Profiles and T g points of various epoxy resin/silica compo-
site materials
DGEBA-1 DGEBA-3
Molar SiO2/ T g/ SiO2/ T g/
ratioa Sample wt%b uCc Sample wt%b uCc
0 Sample 1-0 0.0 113 Sample 3-0 0.0 124
1 Sample 1-1 8.3 50 Sample 3-1 4.2 75
2 Sample 1-2 15.3 44 Sample 3-2 8.0 84
d
3 Sample 1-3 21.4 uncl. Sample 3-3 11.5 80
5 Sample 1-5 31.2 uncl.d Sample 3-5 17.8 losse
a
Molar ratio of TEOS:DGEBA in staring compounds. b Weight per-
cent estimated from the molar ratio of starting compounds. c Deter-
mined from DSC thermograms. d T g points were unclear from DSC
thermograms. e DSC thermogram showed no T g point.
suitable size. After being sealed tightly, the autoclave was
heated with a thermostat at 170 uC for 20 h. After cooling to
room temperature, the autoclave was opened and the glass
vessel was taken out. For the post-cure process, the vessel was
heated directly again with a thermostat at 250 uC for 20 h (not
in the autoclave). Samples thus prepared are denominated as
Sample X-Y by both the kinds of DGEBA and the molar ratio
of silica to DGEBA. The label X is 1 or 3 in Samples obtained
from DGEBA-1 or DGEBA-3, respectively. The label Y is the
number of the molar ratio (silica:DGEBA) in the starting
mixtures. For example, a composite material obtained from
DGEBA-3 with ‘five’ molar equivalents of TEOS was named as
Sample 3-5.
Preparation of allyl-DGEBA-3
An allylated derivative of DGEBA-3 at hydroxyl groups
between bisphenol-A units (allyl-DGEBA-3) was prepared as
follows. To a dry THF solution (140 mL) of DGEBA-3
(23.04 g, 21.43 mmol), 3.22 g (60 wt%, 80.5 mmol as sodium
hydride) of oily sodium hydride was added at room
temperature over 1 h. After gas generation (hydrogen) was
complete, 14.00 g (115.72 mmol) of allyl bromide was added
and the resulting solution was reacted at 60 uC for 3 h. The
reaction was quenched by the addition of water and the organic
components were extracted by diethyl ether. After drying the
ether phase with anhydrous magnesium sulfate, the volatiles
were removed by evaporation. The obtained oil was subjected
to silica-gel column chromatography to afford the desired
allylated compound in chloroform effluent (9.89 g; 10.88 mmol,
yield 39%). This compound was successfully identified as the
desired compound by 1H NMR measurement.{
Preparation of Si-DGEBA-3
A triethoxysilylpropyl ether derivative of DGEBA-3 at
hydroxyl groups (Si-DGEBA-3) was prepared as follows. To
a dry toluene solution (15 mL) of allyl-DGEBA-3 (1.404 g,
3.083 mmol), 1 mL of the toluene solution of the platinum-1,3-
divinyl-1,1,3,3-tetramethyldisiloxane complex was added, and
dry nitrogen was bubbled into the solution for 10 min to
remove dissolved oxygen. Finally, 0.544 g (3.311 mmol) of
triethoxysilane was added and stirred for 18 h at room
temperature. After removing the volatiles in vacuo, the crude
product was obtained (1.771 g; yield 96%). This compound
was also successfully identified as the desired compound by 1H
NMR measurement.{
Preparation of POSS-DGEBA-3
A POSS-dimethylsilyloxypropyl ether derivative of DGEBA-3
at hydroxyl groups (POSS-DGEBA-3) was prepared as
follows. To a dry toluene solution (20 mL) of allyl-DGEBA-
3 (0.107 g, 0.108 mmol) and hydridodimethylsilyloxy-POSS
 View Article Online

(0.214 g, 0.219 mmol), dry nitrogen was bubbled into the

solution for 10 min to remove dissolved oxygen. 0.4 mL of
the toluene solution of the platinum complex was added, and
stirred for 18 h at room temperature. After removing the
volatiles in vacuo, the crude product was yielded. This solid was
recrystallized from a benzene–hexane solution and a purified
compound was obtained (0.283 g; yield 90%). This compound
was also successfully identified as the desired compound by 1H
NMR measurement.{
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Results and discussion

We selected tetraethoxysilane (TEOS) as the alkoxysilane
because it is the commonest and the cheapest one suitable
for practical use. As mentioned in our previous paper,14 the
resulting solution from TEOS and acetic anhydride after
heating afforded a gel after allowing the mixture to stand under
ambient atmosphere conditions for several days. However, Fig. 3 DSC thermograms of epoxy resin/silica composite materials
allowing the mixture to stand is not essential for this silica obtained from DGEBA-1: (a) Sample 1-0, (b) Sample 1-1, (c) Sample
synthesis. When the reaction process was carried out at 170 uC 1-2, (d) Sample 1-3, (e) Sample 1-5.
in a sealed stainless autoclave in order to prevent the
evaporation of TEOS (boiling point: 168 uC), silica solid was
directly obtained without the gelation process (allowing to
stand) after several days. After drying this transparent
yellowish bulk silica at 80 uC, the solid broke into several
pieces. The infrared spectrum of this silica solid (see ESI{)
indicated that silica was directly formed, and intermediates like
silane acetate species did not remain. Even when HHPA
(hexahydrophthalic anhydride) was employed instead of acetic
anhydride, the silica solid including the ethyl ester of HHPA as
a by-product of this condensation reaction was yielded. Epoxy
resin cured by HHPA is also prepared under approximately
similar conditions. These results indicated that both the con-
densation reaction of TEOS and the cure process of epoxy resin
occur concurrently under these conditions.
Pre-polymers (not cured) of epoxy resins used in this study
were diglycidyl ethers of bisphenol-A (DGEBA), which have
been satisfactorily employed in practical resins bearing approxi-
mately one or three bisphenol-A units (called DGEBA-1 or
DGEBA-3 in this paper, respectively). The reaction of DGEBA Fig. 4 DSC thermograms of epoxy resin/silica composite materials
with HHPA is a typical process for the production of epoxy obtained from DGEBA-3: (a) Sample 3-0, (b) Sample 3-1, (c) Sample
3-2, (d) Sample 3-3, (e) Sample 3-5.
resins. Then, the synthesis of composite materials comprised of
epoxy resin and silica was attempted. The mixture of TEOS,
DGEBA and HHPA afforded their homogeneous solution by the materials.16 For example, T g points of Sample 1-0
heating at 90 uC. This mixed solution was heated at 170 uC for [Fig. 3(a)] and Sample 3-0 [Fig. 4(a)] were estimated to be
20 h in a sealed autoclave to prevent the evaporation of approximately 113 and 124 uC from the shoulder temperatures
TEOS. The stoichiometric amounts of HHPA were added for of their thermograms, respectively. When one or two molar
this reaction system. Two equivalents of HHPA are required equivalents of TEOS were mixed with DGEBA, T g points
for TEOS and DGEBA, respectively, according to the reaction became lower (in the range 44–84 uC) than the samples without
scheme (Fig. 1 and 2). Various ratios of TEOS and DGEBA silica. No shoulders of thermograms were observed in Sample
were examined for this reaction process. Solid samples were 1-3 and Sample 1-5 as shown in Fig. 3(d,e). However, the
obtained in all reactions. These solids contained ethyl esters of continuous endothermic courses of these samples do not
HHPA as by-product. Therefore, further heating at 250 uC for suggest that they are T g loss materials. As described later, T g
20 h was carried out. This treatment was expected to be loss materials have no clear endothermic courses with tem-
effective not only for the evaporation of those esters but also peratures like those in Sample 3-5. In the case of DGEBA-3
for a post-cure process well performed in epoxy resin samples (Fig. 4), the loading of TEOS up to three molar
synthesis.9,10 equivalents of DGEBA (Sample 3-1, Sample 3-2 and Sample
Table 1 summarizes the profiles of various epoxy resin/silica 3-3) afforded composites with lower T g points than the
composite materials and their T g (glass transition temperature) material without silica (Sample 3-0). However, a composite
point data estimated from DSC thermograms. As mentioned in material obtained from five molar equivalents of TEOS
the Introduction, thermal deformation of materials causes (Sample 3-5) displayed no shoulder part in the DSC thermo-
serious problems in various practical uses. This property is gram and the endothermic course with temperature was slight.
evaluated by T g points of materials. Especially for compact These observations suggested that this composite material,
electronic devices, some materials are required to be T g loss Sample 3-5, had no T g point below 300 uC as observed by DSC
(no T g point). DSC analysis is a common and reliable method measurement.
to determine T g points of materials.16 Fig. 3 and 4 show Fig. 5 shows the infrared spectra of Sample 3-0 and Sample
DSC thermograms of epoxy resin/silica composite materials 3-5. In Sample 3-5, the strong absorption at about 1100 cm21
obtained from DGEBA-1 or DGEBA-3, respectively. The was observed, while it is absent in Sample 3-0. This absorption
shoulder parts of the thermograms are regarded as T g points of is well known as an infrared band of the Si–O–Si bond which

J. Mater. Chem., 2004, 14, 1195–1202 1197

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Fig. 5 Infrared spectra of (a) Sample 3-0 and (b) Sample 3-5.
indicated the presence of silica in Sample 3-5. Furthermore,
the intensities of the carbonyl absorption at approximately
1740 cm21 derived from esters of HHPA were different
between Sample 3-0 and Sample 3-5. The absorption of Sample
3-5 was obviously stronger than that of Sample 3-0. Although
this absorption might include the absorption from the ethyl
ester of HHPA as by-product of the reaction with TEOS, TGA
analysis of Sample 3-5 (this analysis will be discussed later)
revealed that most of the ethyl ester was removed by the post-
cure process at 250 uC. The formation of ester groups from
epoxide and acid anhydride was promoted by TEOS in the
curing reaction of DGEBA with HHPA. It is reported that
the cure process of acid anhydride without catalyst forms ether
Fig. 7 TGA profiles of epoxy resin/silica composite materials: (A) Sample 3-5, (B) Sample 3-0, (C) Sample 1-5, and (D) Sample 1-0.
1198 J. Mater. Chem., 2004, 14, 1195–1202
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Fig. 6 DSC thermograms of epoxy resin/silica composite materials
related to Sample 3-5: (a) without a post-cure process, (b) after the post-
cure process at 200 uC for 20 h, and (c) after the post-cure process at
250 uC for 20 h (Sample 3-5).
bonds from alcohol and epoxide.17,18 On the other hand, amine
catalyst promotes the formation of esters by anionic reaction of
carboxylate with epoxide.18 It seems that the increase of ester
groups observed in the infrared spectrum of Sample 3-5 was
caused by the nucleophilic reaction of TEOS or by the action of
silane carboxylate as an intermediate of the condensation of
TEOS with acid anhydride.2a,14 The influence of the post-cure
process on the thermal properties of Sample 3-5 was significant.
As shown in Fig. 6, DSC thermograms of three samples related
to Sample 3-5 were different. Without the post-cure process
[Fig. 6(a)], endothermic phenomena were observed at around

120 and 220 uC. Some volatiles were evaporated during this
DSC experiment. As these endotherms were complete below
250 uC, the post-cure process at 250 uC for the evaporation of
esters as by-products was appropriate. In the sample after a
post-cure process at 200 uC, an endothermic phenomenon was
continuously found [Fig. 6(b)]. However, the sample after post-
cure at 250 uC [Fig. 6(c); i.e. Sample 3-5] had no T g point and
no remarkable endothermic course. Therefore, the post-cure
process at 250 uC was essential for producing epoxy resin/
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silica composites with high thermal stability as well as the
evaporation of by-products.
TGA analysis of Sample 3-5 is shown in Fig. 7A. The weight
decrease occurred mainly over 350 uC and was completed
below 700 uC. The weight loss below 800 uC was approximately
81.0% and the incombustible part of this material derived from
silica was estimated to be 19.0 wt%. The calculated silica
content of Sample 3-5 from the starting materials was about
17.8 wt% (Table 1). This value was in good agreement with the
TGA result. This observation indicated that the material after
the post-cure process at 250 uC predominantly consisted of
cured epoxy resin and condensed silica, and that no other
volatile compounds such as the ethyl ester of HHPA as a
by-product were included. The thermal stability was compared
with other analogous materials as shown in Fig. 7. The weight
decreases started at around 350 uC in all materials. No clear
enhancement of the thermal decomposition temperature in
going from silica-free materials (Sample 1-0 and Sample 3-0) to
composite materials (Sample 1-5 and Sample 3-5) was found.
The TGA profile of Sample 1-5 showed approximately 67.2%
weight loss in good accord with the expected value from the
starting ratio (68.8 wt%). The starting compounds were
Fig. 8 TGA profile (A) and DSC thermogram (B) of an epoxy resin/
silica composite material obtained by reaction in an open glass vessel.
The content of the starting compounds was similar to Sample 3-5.
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apparently converted into the corresponding cured resin and
silica completely. However, when the reaction was not per-
formed in a sealed autoclave but in an open glass vessel using
similar starting compounds to Sample 3-5, 96.0% of the weight
loss was observed in the obtained sample (Fig. 8A). This
material had a T g point at about 112 uC (Fig. 8B). These
differences resulted from the removal of TEOS by evaporation
during the reaction. Therefore, the indispensable utilization of
the sealed autoclave was verified for the effective synthesis of
epoxy resin/silica composite materials.
It is thought that the T g loss character found in Sample 3-5
is derived from the composition manner of epoxy resin and
silica. Our procedure in this paper is characterized by the
simultaneous formations of epoxy resin and silica from their
monomers. This process is expected to result in molecular or
nano level mixing of these two material components. Fig. 9
shows the FE-SEM image and EDX image of the same place in
Sample 3-5 (see also ESI{). The white dot points in the EDX
image are parts where the silicon atom is included. These parts
could be regarded as silica particles. The dot size of these silica
particles is approximately below 50 nm. They are dispersed in
all parts of the material, and no island part of silica was found.
It is evidenced that small silica particles below 50 nm were
distributed homogeneously in the samples. It seems that the T g
loss character of Sample 3-5 resulted from this nano level
dispersion of silica particles in the epoxy resin matrix.
We employed two kinds of DGEBA (DGEBA-1 and
DGEBA-3) for the preparation of these composite materials.
It is well claimed that T g points of epoxy resin become lower
with an increase of the number of bisphenol-A units in
DGEBA, especially in the case of the diamine cure process.19
On the other hand, our results observed here were generally the
reverse. T g points of epoxy resin/silica composites from
DGEBA-3 were higher than those from DGEBA-1. Even in
the absence of the silica component, T g points of cured epoxy
resins showed no clear difference (Sample 1-0: 113 uC; and
Sample 3-0: 124 uC). Although silica contents of Sample 1-2
(15.3 wt%) and Sample 3-5 (17.8 wt%) were approximately
similar, their T g points were drastically different. Sample 3-5
had no T g point, whereas the T g point of Sample 1-2 was
observed at about 44 uC. A difference in molecular structure
between DGEBA-1 and DGEBA-3 is the hydroxyl group
between the bisphenol-A units.20 DGEBA-1 has few hydroxyl
groups, whereas DGEBA-3 has mostly two hydroxyl groups.
In general, the T g point of the cured resin increases with the
number of cross-linked parts in the polymer matrix. When the
cross-linked part is only an epoxy group, DGEBA-1 is more
advantageous for the production of higher T g material than
DGEBA-3.19 However, if the hydroxyl groups between
bisphenol-A units participate in the cross-linking of DGEBA
as well as the epoxy groups, DGEBA-3 will be more suitable
for high T g material preparation. DGEBA-3 can be cross-
linked by the ester formation through the hydroxyl groups with
Fig. 9 FE-SEM image (A) and EDX image (B) of the same place in
Sample 3-5. White dots in the EDX image indicate parts containing
silicon atoms.
J. Mater. Chem., 2004, 14, 1195–1202 1199
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Fig. 10 Scheme of syntheses of allyl-DGEBA-3, Si-DGEBA-3 and POSS-DGEBA-3.
HHPA, which does not occur in the case of the diamine cure
process. The high T g point of Sample 3-0 is probably caused
from this effect. Furthermore, these hydroxyl groups have
some interactions and/or chemical bonds with silica during the
reaction. The hydroxyl groups in the DGEBA parts are
reported to be significant for the preparation of epoxy resin/
silica nanocomposites.10 In the paper,10 DGEBA-1-type
compounds are mainly employed and the effects of hydroxyl
groups formed from the ring opening of epoxy groups on the
structures of composites are discussed. Similarly, hydroxyl
groups between bisphenol-A units in DGEBA-3 also partici-
pate in the properties of epoxy resin/silica nanocomposites.
Fig. 11 DSC thermograms of cured materials obtained from (a) allyl-
DGEBA-3, (b) Si-DGEBA-3 and (c) Si-DGEBA-3 with three molar
equivalents of TEOS.
1200 J. Mater. Chem., 2004, 14, 1195–1202
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To investigate the effects of these hydroxyl groups on the T g
point, we prepared three kinds of derivatives wherein hydroxyl
groups of DGEBA-3 were modified to other substituents.
An O-allylated DGEBA-3 was prepared from DGEBA-3
and allyl bromide (allyl-DGEBA-3). This allyl-DGEBA-3
was hydrosilylated using triethoxysilane [H–Si(OEt)3] or
(hydridodimethylsilyloxy-POSS) [1-(hydridodimethylsilyloxy)-
3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.13,9.15,15.17,13]-
octasiloxane] to form the corresponding 3-silylpropyl ether
derivatives, Si-DGEBA-3 and POSS-DGEBA-3, respectively,
as shown in Fig. 10. The POSS unit is often utilized to improve
the thermal properties of polymers.12,21 These three compounds
Fig. 12 DSC thermogram of a product after the reaction of POSS-
DGEBA-3 with HHPA.
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Fig. 13 An expected scheme of interaction between DGEBA and silica nano-particle in the epoxy resin/silica nanocomposites.
were also reacted with HHPA under the same conditions as
other samples. The T g point of the composite material from
allyl-DGEBA-3 was observed at 41 uC by DSC thermogram
(Fig. 11). In the case of Si-DGEBA-3, the reaction of the epoxy
group and ethoxysilane in one molecule is expected to occur
concurrently as in the above-mentioned samples. However, the
obtained composite from HHPA had a low T g point (82 uC).
Even when three molar equivalents of TEOS were added to
adjust the molar ratio of silicon to DGEBA to five, similar to
Sample 3-5, the T g point of the obtained material was still
low (89 uC) as shown in Fig. 11. On the other hand, Fig. 12
shows the DSC thermogram of the obtained solid after the
reaction of POSS-DGEBA-3 with HHPA at 170 uC for 20 h.
The thermogram had an endothermic peak around 220 uC.
However, this type of profile generally indicated melting point
temperature (T m). The obtained solid sample was powdery and
was readily soluble in organic solvents such as chloroform. The
1
H NMR spectrum of this product in CDCl3 solution clearly
showed the peaks of the epoxy groups of DGEBA. The peak
areas of the epoxy groups in this 1H NMR spectrum showed
that the cure process by HHPA hardly proceeded (below 20%).
A longer reaction time was not effective and an approximately
similar product was obtained. The bulky POSS unit bearing
seven cyclopentyl groups probably prevented the reaction of
the epoxy groups with HHPA, and consequently the cured
epoxy resin was scarcely formed. Thus, all our attempts to
modify the hydroxyl groups of DGEBA-3 between bisphenol-
A units were not successful for the preparation of high T g
material. On the other hand, the drastic decrease of the T g
point of Allyl-DGEBA-3 indicated the importance of free
hydroxyl groups between the bisphenol-A units for high T g
material preparation. It seems that T g loss character of Sample
3-5 was caused by the direct interaction between hydroxyl
groups in DGEBA-3 and silica particles. The covalent bond
and/or hydrogen bond between them are expected in this nano-
composite system. Allyl-DGEBA-3 has no hydroxyl group to
interact with silica. In the case of the propylsilane-modified
DGEBA (Si-DGEBA-3), the silica particle formed is combined
with DGEBA-3 through the propylsilane group. The free move-
ment of this propyl group in cured materials is unfavorable for
high T g materials. The direct and strong bonding between
DGEBA and silica nano-particles through the hydroxyl groups
results in the suitable packing effect of silica in the epoxy resin
matrix, that restricts free movement of the epoxy resin part.
Finally, when a suitable amount of silica is mixed, the
composite material had no T g point below 300 uC (Fig. 13).
View Article Online
Conclusions
Epoxy resin/silica nanocomposite materials were prepared by a
simple procedure in which DGEBA, TEOS and HHPA were
mixed and heated at 170 uC in a sealed autoclave. The curing
reaction of the epoxy resin and the condensation of TEOS
occurred simultaneously to form nanocomposite materials of
the resulting corresponding polymers, i.e. cured epoxy resin
and silica. Some of these materials had no T g point below
300 uC. No thermal decomposition occurred until 350 uC. In
these nanocomposite materials, silica particles below 50 nm
were dispersed homogeneously in all matrices of the epoxy
resin. For the production of T g loss material, hydroxyl groups
between bisphenol-A units are important because of the
interaction with the silica particles, which restricts the free
movement of the epoxy resin part. These high T g point
materials will be advantageous to be used in printed-circuit
boards of compact electronic devices and other applications.
Acknowledgements
The authors acknowledge the support of Dr Satoshi Ichikawa
and his co-workers (in AIST-Kansai) for FE-SEM/EDX
measurement.
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