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Kinetics and thermal properties of epoxy resins based on bisphenol

uorene structure
Zhen Dai, Yanfang Li, Shuguang Yang, Ning Zhao, Xiaoli Zhang, Jian Xu
*
Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, The Chinese Academy of Sciences, Box 50, Zhongguancun North First Street 2,
Beijing 100190, PR China
a r t i c l e i n f o
Article history:
Received 5 September 2008
Received in revised form 2 April 2009
Accepted 10 April 2009
Available online 22 April 2009
Keywords:
Epoxy resins
Fluorene
Thermal properties
Kinetics
a b s t r a c t
The uorene-containing epoxy, diglycidyl ether of 9,9-bis(4-hydroxyphenyl) uorene
(DGEBF) was synthesized by a two-step reaction procedure. In order to investigate the rela-
tionship between uorene structure and material properties, DGEBF and a commonly used
diglycidyl ether of bisphenol A (DGEBA) were cured with 4,4-diaminodiphenyl methane
(DDM) and 4,4-(9-uorenylidene)-dianiline (FDA). The curing kinetics, thermal properties
and decomposition kinetics of these four systems (DGEBA/DDM, DGEBF/DDM, DGEBA/FDA,
and DGEBF/FDA) were studied in detail. The curing reactivity of uorene epoxy resins was
lower, but the thermal stability was higher than bisphenol A resins. The onset decomposi-
tion temperature of cured epoxy resins was not signicantly affected by uorene structure,
but the char yield and T
g
value were increased with that of uorene content. Our results
indicated that the addition of uorene structure to epoxy resin is an effective method to
improve the thermal properties of resins, but excess uorene ring in the chain backbone
can depress the curing efciency of the resin.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Epoxy resins are widely used in the industry eld as
coatings, adhesives, insulating and substrate materials
due to their superior electrical and mechanical properties,
excellent moisture and chemical resistance, low shrinkage
and good cohesiveness compared to many materials [13].
With the development of advanced technology, many at-
tempts have been made to prepare for high-performance
epoxy resins, especially to improve their thermal proper-
ties [47]. An effective approach to enhance thermal prop-
erties of epoxy resins is introducing various aromatic ring
structures into the skeleton of epoxy or curing agent, such
as biphenyl, naphthalene, uorene, heterocyclic ring, etc.
[812].
The compound that contains uorene ring usually has
excellent heat resistance, high refractive index, high trans-
parency and low linear expansion coefcient [1315].
Diglycidyl ether of 9,9-bis(4-hydroxyphenyl) uorene
(DGEBF) as a resin containing uorene structure was rst
prepared by Korshak et al. [16]. They found that polymers
with a uorene or anthrone group between the two phenyl
groups show a better thermal property. At present, the u-
orene-containing epoxy resins are widely used for produc-
ing molded product, forming interlayer insulation lm, and
the binder composition for soldering resist in printed wir-
ing board manufacture and so on [1719]. However, the
study on the basic theories of epoxy resins which contains
uorene structure either in epoxy or in curing agent has
less been reported.
We have previously studied the curing kinetics and
thermal properties of DGEBF cured with DDM [11]. In or-
der to study the specic relationship between polymer
structures and properties of the epoxy resins based on
bisphenol uorene, DGEBF was then cured with 4,4-(9-u-
orenylidene)-dianiline (FDA), which also contains uorene
structure. Meanwhile, a commercially available epoxy re-
sin, diglycidyl ether of bisphenol A (DGEBA) was also cured
with the same curing agents for comparison. The curing
0014-3057/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2009.04.012
* Corresponding author. Tel./fax: +86 10 82619667.
E-mail address: jxu@iccas.ac.cn (J. Xu).
European Polymer Journal 45 (2009) 19411948
Contents lists available at ScienceDirect
European Polymer Journal
j our nal homepage: www. el sevi er . com/ l ocat e/ eur opol j
kinetics, thermal properties and decomposition kinetics of
these epoxy resins (DGEBA/DDM, DGEBF/DDM, DGEBA/
FDA, and DGEBF/FDA) were studied in detail.
2. Experimental
2.1. Materials
9,9-Bis(4-hydroxyphenyl) uorene was purchased from
Suqian Ever-Galaxy Pharmacy & Chem. Co., China. Epichlo-
rohydrin (ECH), tetraethyl ammonium bromide (TEAB),
1,4-dioxane, sodium hydroxide (NaOH), acetone and etha-
nol were obtained from Beijing Chemical Reagents Co.,
Chinaandwereusedwithout further purication. Diglycidyl
ether of bisphenol A (DGEBA, EEW = 196 g/mol) and 4,4
0
-
diaminodiphenylmethane (DDM) were received from
Shanghai Chemical Co., China. 4,4-(9-Fluorenylidene)-dian-
iline(FDA) was purchased from Aldrich.
2.2. Synthesis of diglycidyl ether of 9,9-bis(4-hydroxyphenyl)
uorene
9,9-Bis(4-hydroxyphenyl) uorene (175.21 g, 0.5 mol),
TEAB (21.02 g, 0.1 mol), ECH (470.25 ml, 6.0 mol), and
1,4-dioxane (96.71 ml, 1.1 mol) were added to a three-
necked ask. The reaction mixture was stirred at 65 C
for 1 h, and then 120 ml of 50 wt.% NaOH aqueous solution
was added drop wise over a period of 1 h. The reactants
was stirred for another 2 h at 65 C, and then distilled to re-
move excess ECH and other solvent. The crude products
were ltered to remove the residual sodium chloride, and
the organic phase was washed several times with deion-
ized water. After precipitated from its cold water, the prod-
uct was puried through recrystallization in an acetone/
ethanol (5:1, volume ratio) solution. Then the white crys-
talline powers of DGEBF were obtained [11].
2.3. Preparation of the cured epoxy resins
The chemical structures of epoxies and curing agents
are shown in Table 1. The epoxies were initially heated
to be melting and then a stoichiometric ratio of curing
agent according to epoxy equivalent weight was mixed
homogeneously, which form four reactions of DGEBA/
DDM, DGEBF/DDM, DGEBA/FDA and DGEBF/FDA. Then
the mixtures were cured in their respective optimal curing
condition, decided by dynamic DSC tracing of epoxy and
curing agent compositions. The curing cycles are listed in
Table 2.
2.4. Characterization
Differential scanning calorimetry (DSC) was performed
on a Mettler Toledo 822
e
with a constant nitrogen ow
of 20 mL/min. The dynamic scanning experiments were
ranged from 25 to 300 C at heating rates of 5, 10, 15 and
25 C/min, respectively. Thermogravimetric analysis
(TGA) was performed using a PerkinElmer Pyris1 at the
heating rates of 10, 20, 30, 40 C/min in a nitrogen atmo-
sphere from 25 to 750 C and the thermal stable residue
was formed. FT-IR spectra were performed on a Bruker
Equinox55 spectrometer in the range from 4000 to
400 cm
1
. The cured epoxy resin was ground with potas-
sium bromide for FT-IR measurement. Dynamic mechani-
cal analysis (DMA) was carried out on a Rheometric
Scientic instrument in air at a heating rate of 5 C/min.
The specimen of 8 5 1.5 mm was loaded in a single
cantilever mode with a frequency of 1 Hz.
Table 1
Chemical structure of epoxies and curing agents.
Component Chemical structure
Epoxy
DGEBA O CH
2
CH CH
2
O
O CH
2 H
2
C
O
CH C
CH
3
CH3
DGEBF
O CH
2
CH CH
2
O
O CH
2
H
2
C
O
CH
Curing agent
DDM
H
2
N
H
2
C NH
2
FDA
H
2
N NH
2
1942 Z. Dai et al. / European Polymer Journal 45 (2009) 19411948
3. Results and discussion
3.1. Curing kinetics of epoxy resins
The curing behavior and kinetics of the epoxies and
curing agents were studied by dynamic DSC. The reactivity
of epoxies and curing agents can be directly obtained from
the DSC curves. Fig. 1 shows the DSC curves of these four
epoxy resins with a heat rate of 5 C/min. The exothermic
peak temperature (T
p
) refers to the curing temperature,
and the T
p
of DGEBA/DDM, DGEBF/DDM, DGEBA/FDA and
DGEBF/FDA were 148, 156, 165 and 175 C, respectively.
The T
p
shifts to a higher temperature with the increasing
of uorene ring in the reaction systems, and the inuence
was quite obvious by using a uorene-containing curing
agent. This is because the curing mechanism of epoxy
and amine curing agent is the primary amine changed into
secondary amine, then into tertiary amine which has
catalysis function and the process is critical to curing reac-
tion. When uorene structure was in curing agents, the
steric hindrance of this process was more obvious, while
epoxies with uorene group have no inuence on this
course.
The curing kinetics of these four resins was studied by a
non-isothermal DSC method. The curing activation ener-
gies E were simulated by the method of Kissinger and Oza-
wa, and the order of reaction n and the reaction rate
constant k were deduced from Crane and Arrhenius equa-
tion [2022]. Fig. 2 shows the DSC curves of these four
epoxy resins at different heat rates.
Kissingers method is based on the fact that T
p
varies
with the heating rates and that it assumes the maximum
reaction rate (da/dt) occurs at the peak temperatures. The
equation can be expressed as Eq. (1). So the E
k
values of
curing can be determined from a plot of lnb=T
2
p
vs. 1/T
p
.
For Ozawas method, its on the assumption that the degree
of conversion at peak temperatures for different heating
rates is constant, as shown in Eq. (2). The E
o
values of cur-
ing can be obtained by plotting ln b vs. 1/T
p
.
E
k
R
dlnb=T
2
p

d1=T
p

1
E
o

R
1:052
d ln b
d1=T
p

2
where E
k
and E
o
are the curing activation energy simu-
lated by Kissinger and Ozawas method. b is the heating
rate and T
p
is the maximum peak temperature, and R is
the ideal gas constant. All the obtained results are sum-
marized in Table 3.
The E values calculated from the Ozawa method were
slightly higher than that of the Kissinger method, but the
trend of E values determined by both of methods was con-
sistent with each other. The E values were increased with
the uorene content in epoxy resins, and also the inuence
was much obvious when uorene structures were in cur-
ing agents. This can also attribute to the steric hindrance
in curing process; which leading to a higher curing temper-
ature was required. The reaction type of these systems was
all the same as the order of reaction n were very close to
each other. The reaction rate constant k at three different
temperatures was also calculated. The reaction rate con-
stant also decreased with the increase of uorene content,
which was corresponding to the increase of E values of dif-
ferent systems.
3.2. Thermal properties and decomposition kinetics of cured
epoxy resins
The TG and DTG thermograms of the cured epoxy resins
at a heat rate of 10 C/min are shown in Fig. 3. The degrada-
tion temperature at 5% weight loss and the residual char
yield at 750 C for DGEBA/DDMand DGEBA/FDA epoxy res-
ins wereat 384 C, 375 Cand17.1%, 17.9%, respectively, and
for DGEBF/DDM and DGEBF/FDA epoxy resins that were
376 C, 360 C and 24.3%, 27.2%, respectively. DGEBA based
epoxy resins showed slightly higher initial decomposition
temperature, which due to the higher crosslink density of
DGEBA matrix resins. The crosslink density is important
for deciding the initial decomposition temperature, because
the chain breakage mainly occurs between intermolecular
in the beginning of decomposition. The curing reaction
was dependent not only on the reactivity of the functional
group but also on the molecular mobility. It is well-known
that a molecular unit with a higher aromatic ring content
has a higher rigidity and a higher steric hindrance to molec-
ular motion. The melt viscosity activation energies for DGE-
BA and DGEBF were 23.84 and 56.90 kJ/mol, respectively
Table 2
Optimal curing conditions of epoxy resins.
System Curing
temperature
(C)
Curing
time
(h)
Post-curing
temperature
(C)
Post-curing
time (h)
DGEBA/DDM 140 4 180 4
DGEBF/DDM 155 4 185 4
DGEBA/FDA 160 4 190 3
DGEBF/FDA 170 3 200 4
140 160 180 200
H
e
a
t

F
l
o
w
Temperature /
o
C
e

x

o
a b c d
Fig. 1. DSC curves of curing process of epoxy resins: (a) DGEBA/DDM; (b)
DGEBF/DDM; (c) DGEBA/FDA and (d) DGEBF/FDA. (Heat rate: 5 C/min).
Z. Dai et al. / European Polymer Journal 45 (2009) 19411948 1943
[23]. Because of the much higher viscosity of DGEBF com-
pared with DGEBA resin, it shifts to diffusion control with
a slower rate of reaction during curing process. Fig. 4 shows
the FT-IR spectrum of cured epoxy resins, DGEBF based
epoxy resins still have characteristic absorption of epoxy
group even at the end of the cure process. The results indi-
cated that the curing reaction of uorene-containing epox-
ies was incomplete, which leads to a lower crosslink
density of epoxy resins. Therefore, the onset decomposition
temperature was not improved by uorene. But at the later
stage of decomposition, molecular internal interaction is
critical in chain breaking reaction. So the char yield of cured
bisphenol uorene epoxy resins were higher than that of
bisphenol A epoxy resins, which corresponds to molecular
internal aromatization and cyclization of uorene ring.
The thermal decomposition kinetics of cured resins was
studied by dynamic method [2426]. Fig. 5 shows the TGA
curves of cured epoxy resins at four different heating rates.
The values of decomposition activation energy E
d
, accord-
ing to the non-isothermal kinetic theory, can be written
as follows:
ln b 1:105
E
d
RT
ln
0:0048AE
f a

3
75 100 125 150 175 200 225 250 275 300
1. 5
o
C/min
2. 10
o
C/min
3. 15
o
C/min
4. 25
o
C/min
1. 5
o
C/min
2. 10
o
C/min
3. 15
o
C/min
4. 25
o
C/min
1. 5
o
C/min
2. 10
o
C/min
3. 15
o
C/min
4. 25
o
C/min
1. 5
o
C/min
2. 10
o
C/min
3. 15
o
C/min
4. 25
o
C/min
H
e
a
t


F
l
o
w
Temperature (
o
C )
exo
1
2
3
4
(a)
100 125 150 175 200 225 250 275 300
H
e
a
t


F
l
o
w
Temperature (
o
C )
exo
1
2
3
4
(c)
150 175 200 225 250 275 300
H
e
a
t


F
l
o
w
Temperature (
o
C )
exo
1
2
3
4
(d)
125 150 175 200 225 250 275
H
e
a
t


F
l
o
w
Temperature (
o
C )
exo
1
2
3
4
(b)
Fig. 2. DSC curves of curing epoxy resins at four different heating rates: (a) DGEBA/DDM; (b) DGEBF/DDM; (c) DGEBA/FDA and (d) DGEBF/FDA.
Table 3
The curing kinetic parameters of curing resins.
Epoxy resins DGEBA/DDM DGEBF/DDM DGEBA/FDA DGEBF/FDA
Kissingers method E
k
(kJ/mol) 49.20 51.65 54.36 61.44
Ozawas method E
o
(kJ/mol) 53.81 56.26 58.95 65.99
n 0.87 0.87 0.88 0.88
(T
1
= 373 K) 0.02752 0.01907 0.01306 0.00716
k (T
2
= 423 K) 0.1795 0.1366 0.1037 0.07445
(T
3
= 473 K) 0.7876 0.6450 0.5314 0.4720
1944 Z. Dai et al. / European Polymer Journal 45 (2009) 19411948
here b is the heating rate, f(a) is the differential expression
of a kinetic model function, a is the conversion of thermal
decomposition, A and R are pre-exponential factor and
ideal gas constant [27].
A single step decomposition were observed in these
four kinds of cured epoxy resins, implied that the thermal
decomposition was controlled by a single activation en-
ergy. The E
d
for these four cured epoxy resins were calcu-
lated by ln b versus 1/T plots at several decomposition
conversions, which are summarized in Fig. 6. We investi-
gated the process when a were 040%, because the re-
search object were not the original resin at the latter
stage of decomposition. The E
d
of DGEBF/FDA resin were
highest at any conversions due to the highest content of
uorene in these systems, and that of DGEBA/DDM resin
were lowest since no uorene group in resin. The average
decomposition activation energy of DGEBA/DDM, DGEBF/
DDM, DGEBA/FDA and DGEBF/FDA were 149.58, 176.40,
181.97 and 249.40 kJ/mol. The decomposition activation
energy of resins were increased as uorene increased, this
is also because of a higher rigidity and of a higher resis-
tance to molecular motion of uorene. Therefore, the ther-
mal stability of epoxy resins was elevated by introducing
uorene to the backbone of the resins.
3.3. DMA analysis of cured epoxy resins
The DMA curves of these four cured resins are shown in
Fig. 7. Because of the higher crosslink density, the storage
modulus values (E
0
) of DGEBA based epoxy resins are high-
er than that of DGEBF in the glassy region. But the DGEBF
based resins have better retention of E
0
at elevated temper-
ature due to their higher rigidity of uorene skeleton in the
chain backbone. The T
g
of DGEBA/DDM, DGEBF/DDM, DGE-
BA/FDA and DGEBF/FDA were 168, 260, 224 and 300 C,
respectively, which determined by the peak temperature
250 300 350 400 450 500 550
-15
-10
-5
0
b
d
c
D
e
r
i
v
a
t
i
v
e

W
e
i
g
h
t


(
%

/

m
i
n
)
Temperature (
o
C)
a
100 200 300 400 500 600 700
0
20
40
60
80
100
W
e
i
g
h
t


(
%
)
Temperature (
o
C)
a
b
c
d
Fig. 3. TG and DTG thermograms of cured epoxy resins: (a) DGEBA/DDM; (b) DGEBF/DDM; (c) DGEBA/FDA and (d) DGEBF/FDA. (Heat rate: 10 C/min).
4000 3500 3000 2500 2000 1500 1000 500
(d)
(b)
(c)
T
r
a
n
s
m
i
t
t
a
n
c
e

(
%
)
Wavenumber ( cm
-1
)
(a)
940 920 900 880 860
(d)
(b)
(c)
(a)
Fig. 4. FT-IR spectrum of cured epoxy resins: (a) DGEBA/DDM; (b) DGEBF/DDM; (c) DGEBA/FDA and (d) DGEBF/FDA.
Z. Dai et al. / European Polymer Journal 45 (2009) 19411948 1945
of the tan d curve. The T
g
values of these resins were en-
hanced with the increase of uorene, which is related to
the stiffness of molecular chain and a low degree of free
conformational rotation. Moreover, the enhancement was
more obvious when uorene comes from the epoxy unit.
This is because the stoichiometric ratio of bisphenol epoxy
and diamine curing agent was 2:1, the DGEBF/DDM system
have more uorene content in the main chain. In addition,
it is worthwhile to mention that the cured DGEBF/FDA re-
sin shows a very broad glass transition, and a secondary
transition appeared in the range of 180200 C. The reason
is that the low crosslink density caused by the stiff of u-
orene skeleton, which would restrain the internal rotation
and motion of molecular segments in curing reaction. Fur-
thermore, the molecular chains of resin begin to move and
the resin continues to post-curing with the temperature
increase, and this enhanced interaction lead to a very
broad glass transition of resin. When its used in real appli-
cations, this phenomenon deserves attention greatly in
that it would seriously affect the performance of resins.
Therefore, the T
g
of cured resin can be elevated drastically
by introducing some rigid groups into main molecular
chain, but the excessive aromatic ring may have negative
effect on the performance of resins.
4. Conclusions
A uorene epoxy compound DGEBF was successfully
synthesized, and then DGEBF and a commonly used epoxy
DGEBA were cured with DDM and uorene contained dia-
mine FDA. The DSC analyses indicated uorene contained
100 200 300 400 500 600 700
100 200 300 400 500 600 700 100 200 300 400 500 600 700
0
20
40
60
80
100
W
e
i
g
h
t


(
%
)
Temperature (
o
C)
10
o
C/min
20
o
C/min
30
o
C/min
40
o
C/min
(a)
100 200 300 400 500 600 700
0
20
40
60
80
100
W
e
i
g
h
t


(
%
)
Temperature (
o
C)
10
o
C/min
20
o
C/min
30
o
C/min
40
o
C/min
(b)
0
20
40
60
80
100
W
e
i
g
h
t


(
%
)
Temperature (
o
C)
10
o
C/min
20
o
C/min
30
o
C/min
40
o
C/min
(c)
0
20
40
60
80
100
W
e
i
g
h
t


(
%
)
Temperature (
o
C)
10
o
C/min
20
o
C/min
30
o
C/min
40
o
C/min
(d)
Fig. 5. TGA curves of cured epoxy resins at four different heating rates: (a) DGEBA/DDM; (b) DGEBF/DDM; (c) DGEBA/FDA and (d) DGEBF/FDA.
10 15 20 25 30 35 40
120
140
160
180
200
220
240
260
280
300
E
d


(
k
J
/
m
o
l
)
(%)
Fig. 6. E
d
curves at different conversions of cured epoxy resins: (d)
DGEBA/DDM; (j) DGEBF/DDM; (.) DGEBA/FDA; (N) DGEBF/FDA.
1946 Z. Dai et al. / European Polymer Journal 45 (2009) 19411948
epoxy resin needs higher curing temperature; especially
when a uorene group comes from curing agents. The
curing kinetics was studied, and the results indicated that
the reactivity of epoxy resin was depressed with the u-
orene structure. The onset decomposition temperature
of cured epoxy resins were decreased with the increase
of uorene content, which is affected by a lower crosslink
density of epoxy resins. The char yield and the decompo-
sition activation energy E
d
of resins were increased due to
aromatization and cyclization of uorene ring. The T
g
of
these cured epoxy resins were improved by introducing
uorene, and the elevation was quite obvious when uo-
rene structure were in epoxies. In DGEBF/FDA systems,
which have too much uorene ring in main chain, will af-
fect the properties of resins. Therefore, the presence of
uorene in resin skeleton is an effective way to enhance
the thermal properties of materials and to base on com-
prehensive consideration of polymer properties, the addi-
tion of the uorene group into one component of epoxy
resin is a better way to improve the performance of
resins.
Acknowledgements
The authors thank the National Science Foundation of
China (Nos. 50425312, 50373049, 50521302) and Chinese
Academy of Sciences Innovation Project for nancial
support.
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75 100 125 150 175 200 225
10
6
10
7
10
8
10
9
Temperature (
o
C)
E'
E''
(a)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
t
a
n

(Pa)
100 150 200 250 300
10
7
10
8
10
9 E'
E''
(b)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
t
a
n

(Pa)
50 100 150 200 250
10
6
10
7
10
8
10
9
E''
E'
Temperature (
o
C)
(c)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
t
a
n

(Pa)
100 150 200 250 300 350
10
7
10
8
10
9
E''
E'
Temperature (
o
C)
(Pa)
(d)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
t
a
n

Fig. 7. DMA curves of the cured epoxy resins: (a) DGEBA/DDM; (b) DGEBF/DDM; (c) DGEBA/FDA and (d) DGEBF/FDA.
Z. Dai et al. / European Polymer Journal 45 (2009) 19411948 1947
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