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An Improved Method to Determine Epoxy Index of

Epoxy Resins
a a b b b
Shi-rong LI , Wen-chao Guan , Zhi-gao Wu , Jun-cai Lu & Jia Guo
a
Department of Material Science and Engineering , Huazhong University of Science and
Technology , Wuhan, P.R. China
b
Wuhan Institute of Technology, Hubei Key Laboratory of Novel Reactor and Green Chemical
Technology , Wuhan, P.R. China
Published online: 28 Aug 2007.

To cite this article: Shi-rong LI , Wen-chao Guan , Zhi-gao Wu , Jun-cai Lu & Jia Guo (2007) An Improved Method to Determine
Epoxy Index of Epoxy Resins, Polymer-Plastics Technology and Engineering, 46:9, 901-903, DOI: 10.1080/03602550701280315

To link to this article: http://dx.doi.org/10.1080/03602550701280315

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 Polymer-Plastics Technology and Engineering, 46: 901–903, 2007
Copyright # Taylor & Francis Group, LLC
ISSN: 0360-2559 print/1525-6111 online
DOI: 10.1080/03602550701280315

An Improved Method to Determine Epoxy Index

of Epoxy Resins
Shi-rong LI and Wen-chao Guan
Department of Material Science and Engineering, Huazhong University of Science and Technology,
Wuhan, P.R. China

Zhi-gao Wu, Jun-cai Lu, and Jia Guo

Wuhan Institute of Technology, Hubei Key Laboratory of Novel Reactor and Green Chemical
Technology, Wuhan, P.R. China
Downloaded by [McGill University Library] at 06:34 24 November 2014

may cause secondary pollution[5]. Standard spectra and

In this communication, the effects of testing conditions, i.e.,
reaction time and temperature, on the accuracy for determining
epoxy index of chloroepoxy propane were investigated, in order to
reduce errors generated by using the current Chinese Standard
GB1677-81 for determining epoxy indexes of epoxy resins. Experi-
mental results showed that, for chloroepoxy propane reacting with
hydrochloric acid-acetone for 4 h at 45
C, its epoxy index was very
close to the theoretical value. The relative error of this improved
method was ca. 0.40%, much lower than that determined by the
method defined in GB1677-81, which results in the maximum error
of 6.77%.
Keywords Chloroepoxy propane; Epoxy index; Error analysis;
Hydrochloric acid-acetone method
calibration curves are required for infrared spectrometry.
The nuclear magnetic resonance is not widely used to deter-
mine the epoxy index due to its high cost[6]. Hydrochloric
acid-acetone method is used for determining epoxy indexes
since the reagents used are relatively inexpensive and the
operation procedure is simple. However, the errors for this
method, as described in GB1677-81[7], are relatively large.
In this communication, based on hydrochloric acid-acetone
method, an improved method by changing the testing con-
ditions is proposed to accurately determine the epoxy index
of epoxy resins.

1. EXPERIMENTAL
Epoxy index, a very important parameter to evaluate the
quality of epoxy resins, is usually defined as moles of epoxy 1.1. Principle
groups per 100 g of epoxy resins. This index can be used for
calculating the amounts of cross-linking reagent needed in
the epoxy resin formula and determining the curing degree
of epoxy resins. Therefore, epoxy indexes are fundamental
data for manufacturing epoxy resins and their applications.
Currently, several methods are used to determine the epoxy
index of epoxy resins, including titration, perchloric acid-
tetriethlammonium bromide titration, infrared spectrometry,
1
H-NMR and 13C-NMR Spectrometry[1–4]. Among these
methods, the hydrochloric acid-pyridine method has some 1.2. Reagents
drawbacks, such as high poison of pyridine, strong irritation Acetone, hydrochloric acid, sodium hydroxide, and
of reagents, and relatively complicated operating procedure. chloroepoxy propane in analytical grade were provided
For perchloric acid-tetriethlammonium bromide titration, it by J & K CHEMICA1. The Hydrochloric acid-acetone
is difficult to judge the end-point and the reagents involved solution was prepared by the ratio of hydrochloric acid
to acetone (1:30). The indicator was mixed by 0.1% cresly
red solution and 0.1% thyme-penol solution with the
Address correspondence to J. Guo, Wuhan Institute of
Technology, Hubei Key Laboratory of Novel Reactor and volume ratio of 1:3. The mixture was adjusted to neutral
Green Chemical Technology, Wuhan 430073, China. E-mail: by the 0.01 mol L 1 sodium hydroxide solution and
guojia@mail.wit.edu.cn 0.01 mol L 1 hydrochloric acid.

901
 902 S. LI ET AL.

1.3. Testing Procedure

a) Place 150 mL acetone and 5 mL hydrochloric acid into a
volumetric flask;
b) Weigh 0.4 to 0.5 g chloroepoxy propane and place into
a conical bottle, and then add 25 mL hydrochloric acid.
Put it into a thermostatic bath (45
C) for 3.5 h after
mixing thoroughly;
c) Add 3 drops of indicator into 25 ml hydrochloric acid-
acetone solution. First, carry out a blank titration
within 30 s. The end-point is defined as no color change
after 5 s. The volumetric amount of NaOH consumed
is V0 ml;
d) Take the conical bottle and cool to room temperature.
Add 3 drops of indicator and carry out titration using
NaOH solution. The amount consumed is V ml.
Downloaded by [McGill University Library] at 06:34 24 November 2014

1.4. Calculation
FIG. 1. Relative errors of epoxy index versus reaction time for different
The epoxy index (EI) is calculated using the following temperatures.
equation:
ðV0  V ÞN proportional to the concentration of activation molecules.
EV ¼ ð1Þ
W  10 Therefore, the reaction rate increases with the increase of
The relative error can be calculated by the following the temperature[9]. On the other hand, considering the boil-
equation: ing temperature of acetone being 56.5
C at 1 atm, acetone
will be vaporized if the temperature is too high, resulting
EV  1:081 in the high pressure of the reaction system (vapor pressure
Er ¼  100 ð2Þ
1:081 of acetone at the boiling point is 101.33 kPa). At the same
where, N is the concentration of sodium hydroxide solution, time, HCl will also be emitted and the concentrations of
mol L 1; and W is the mass of chloroepoxy propane, g. the reactant reduce. This might affect the reaction equilib-
rium, resulting that the V 0  V value of Eq. 1 is larger than
2. RESULTS AND DISCUSSION that of the actual value. Therefore, in this test, 45
C was
chosen as the reaction temperature[10].
2.1. Conventional GB1677-81 Method
According to the method described in GB1677-81, in
2.3. Effect of Reaction Time on the Epoxy Index
order to determine the epoxy indexes, reaction of epoxy
From above two figures, it could be seen that both
and hydrochloric acid-acetone solution was all carried
reaction temperature and reaction time would affect the
out at 20
C. The testing results are shown in Fig. 1. From
Fig. 1, it could be seen that the relative error was as high as
6.77% for the reaction time of 2 h. Even the reaction time
was extended to 4 h, the relative error was about 4.49%. In
brief, the method of GB1677-81 results in a significant
experimental error.

2.2. Effect of Reaction Temperature on the Epoxy Index

For the reaction time of 2 h, the results of chloroepoxy
propane and hydrochloric acid-acetone system for different
reaction temperatures are shown in Fig. 2. With the increase
of reaction temperature, the relative errors dropped signifi-
cantly, indicating that epoxide groups were easily involved
in open chain reactions at a higher temperature. According
to Van’t Hoff empirical rule, for common reactions, the
reaction rate will increase 2 to 4 times if the reaction tem-
perature increases by 10
C[8]. On the other hand, according
to Arrhenius Law, molecules adsorb energies and are
excited to activation molecules. And the reaction rate is FIG. 2. Relative errors of epoxy index versus reaction temperature.
 DETERMINING EPOXY INDEX OF RESINS
accuracy of the testing. For example, at 45
C and the
reaction time of 2 h, the relative error was about 1.98%,
as shown in Fig. 1. For a longer reaction time, the con-
version rate of the reaction increased. However, once
the reaction reached equilibrium, the effect of reaction
time on the conversion rate was insignificant since the
conversion rate approached to a constant. With prolong-
ing the reaction time, the relative errors for epoxy index
also reduced dramatically and approached to a constant
around 0.40%. After 4 h, the relatively good testing
results are expected.
3. CONCLUSIONS
When determining the epoxy index of chloroepoxy pro-
pane using hydrochloric acid-acetone method, the relative
errors will be reduced significantly if the reaction tempera-
Downloaded by [McGill University Library] at 06:34 24 November 2014
ture is increased or the reaction time is prolonged. Experi-
mental results showed that for chloroepoxy propane
reacting with at 45
C for 4 h, its epoxy index was very close
to the theoretical value. The relative error of this improved
method was ca. 0.40%, much lower than that determined
by the method defined in GB1677-81.
ACKNOWLEDGMENT
The authors gratefully acknowledge the financial
support of this work by National Natural Science
903
Foundation of China (Grant No. 20376065) and Hubei
Educational Bureau Major Research Project (Grand
No. 2002z20004).
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