Industrial Crops and Products 15 (2002) 139– 144

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Studies on the epoxidation of rubber seed oil

F.E. Okieimen a,*, O.I. Bakare a, C.O. Okieimen b
a
Department of Chemistry, Faculty of Science, Industrial Agriculture Products Research Laboratory, Uni6ersity of Benin,
P.M.B. 1154, Benin City, Nigeria
b
Department of Chemical Engineering, Uni6ersity of Benin, Benin City, Nigeria

Accepted 20 July 2001

Abstract

The kinetics epoxidation of rubber seed oil (RSO) by peroxyacetic acid generated in situ were studied at various
temperatures. It was found that epoxidation with almost complete conversion of unsaturated carbon and negligible
oxirane cleavage can be attained by the in situ technique. The rate constant for epoxidation of RSO was found to be
of the order of 10 − 6 l mol − 1 s − 1 and activation energy of epoxidation of 15.7 kcal mol − 1 was determined. Some
thermodynamic parameters: enthalpy, entropy and free energy activation of 15.2, − 31.94 and 25.44 kcal mol − 1,
respectively were obtained for the epoxidation of RSO. The kinetic and thermodynamic parameters of epoxidation
obtained from this study indicate that an increase in the process temperature would increase the rate of epoxide
formation. © 2002 Elsevier Science B.V. All rights reserved.

Keywords: Epoxidation; Kinetics; Rubber seed oil; Peroxyacetic acid

1. Introduction esters used as plasticizers has ranged from

Epoxidation is the formation of an oxirane
group (epoxide) by the reaction of peroxyacids
(peracids) and olefinic and aromatic double
bonds. Epoxides are valuable commercial prod-
ucts. Epoxides of long chain olefins and of prod-
ucts based on limonene are useful detergent and
flavour precursors, respectively (Lutz, 1978).
Epoxidised vegetable oils and esters derived from
them have found important applications as plasti-
cizers and additives for polyvinyl chloride (Gan et
al., 1995). The annual production of epoxidised
* Corresponding author.
E-mail address: okiemen@uniben.edu (F.E. Okieimen).
30,000 –73,000 ton (USTIC, 1983). Epoxidised
soybean oil accounted for about the total epoxi-
dised ester production (Rangaraja et al., 1995;
Carlson et al., 1981). Other epoxidised oils used as
plasticizers are prepared from linseed, rapeseed,
olive, corn safflower, melon seed and cotton seed
(Khuddus et al., 1965; Milliahi et al., 1960). How-
ever, reports on similar studies using rubber seed
oil as starting material are scanty (Milliahi et al.,
1960; Vijayagopalan and Gopalakrishna, 1971;
Okieimen et al., in press). RSO is obtained from
the seeds of the plant He6ea brasilienses Muell.
Agr., an economic tree widely cultivated in the
southern parts of Nigeria. The physico-chemical
characteristics and the fatty acid composition of
the RSO are similar to those of the seed oils

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140 F.E. Okieimen et al. / Industrial Crops and Products 15 (2002) 139–144

currently used in the commercial production of from BDH Ltd., hydrogen peroxide (30%) from
epoxy esters (Table 1). At present RSO has no MERCK and sulphuric acid (Analar) from May
commercial value in this country. In our previ- and Baker Ltd. They were used without further
ous studies, we reported on the utilization of purification.
RSO in the preparation of alkyd resins (Okiei-
men and Aigbodion, 1997, 1998) and of epoxi- 2.2. Epoxidation of rubber seed oil
dised rubber seed oil and its metal soaps as
thermal stabilizer for polyvinyl chloride (Okiei- Epoxidation of RSO was carried out by using
men, 2000; Okieimen and Ebhoaye, 1992; Ok- peroxyacetic acid prepared in situ by reacting
ieiemen and Ebhoaye, 1993). The overall various mixtures of acetic acid and hydrogen
purpose of these studies is the development of peroxide in the presence of small quantities of
value-added products from locally available re- concentrated sulphuric acid. In a typical experi-
newable resources. The kinetics of epoxidation ment, a known amount of RSO was placed in a
of rubber seed oil by peroxyacetic acid generated 500 ml flask containing the required amounts of
in situ are examined in the present study. the acids (acetic acid and sulphuric acid), con-
denser, thermometer and stirrer. The flask was
allowed to attain the reaction temperature in a
2. Experimental thermostat bath (controlled to better than 9
2 °C) and hydrogen peroxide previously equilib-
2.1. Materials erated at the reaction temperature was added.
The stirring rate was controlled so that the oil
Rubber seed oil was soxhlet-extracted with n- in the mixture was finely dispersed. The reaction
hexane from ground and oven-dried (40 °C) was monitored by withdrawing aliquots of the
seeds. Glacial acetic acid (99.5%) was obtained reaction mixture at various time intervals into a
large excess of cold water in a separatory funnel.
The aqueous layer was drawn off and the oil
Table 1 layer was washed successively with warm water
Physico-chemical characteristics and fatty acid profile of rub-
until it was acid free. The level of epoxidation in
ber seed oil and soybean oil
the oil was determined using the method de-
Parameters Rubber seed oila Soybean oilb scribed by Pagout and Hautfenne (1987). Epoxi-
dation was carried out at various temperatures
Physico-chemical characteristics (30, 50, 60 and 70 °C) and using various initial
Specific gravity (30 °C) 0.926 0.918
amounts of acetic acid and hydrogen peroxide.
Acid value (MgKOH/g) 23.00 –
Free fatty acid (% oleic 11.29 0.7
acid)
Peroxide value 0.40 3. Results and discussion
(meq/kg)
Iodine value (gl2/100 g) 155.56 120
Saponification value 192.93 189
3.1. Dependence of extent of epoxidation on
(MgKOH/g) initial amounts of acetic acid and hydrogen
peroxide
Fatty acid composition (%)
Myristic C14:0 2.2 0.1
Palmitic C16:0 7.6 12.0 The effect of acetic acid concentration on the
Stearic C18:1 10.7 4.0 level of epoxidation of RSO is shown in Table
Oleic C18:1 20.0 24.0 2. The results show that an increase in the acetic
Linoleic C18:2 36.0 52.0 acid content of the reaction mixture is accom-
Linolenic C18:3 23.5 8.0
panied by an increase in the level of epoxidation
a
Okieimen, 2000. (measured in % oxirane). Table 3 shows
b
Kildiran et al., 1996. similar increase in the extent of epoxidation
 F.E. Okieimen et al. / Industrial Crops and Products 15 (2002) 139–144 141

Table 2
Effect of acetic acid concentration on the extent of epoxida-
tion of RSO at 30 °C

Amount of acetic acid Extent of epoxidation

(mmol) (% oxirane)

17.0 1.76
35.0 3.17
52.0 3.52
70.0 3.40
80.0 3.49
140.0 3.64

Amount of H2O2 = 0.24 mol.

with increase in the hydrogen peroxide content

of the reaction mixture. The formation of per-
oxyacetic acid from acetic acid and hydrogen
peroxide is a reversible reaction (CH3COOH + Fig. 1. Rate of oxidation of rubber seed oil by peroxyacetic
H2O2 X CH3COOOH +H2O). Therefore, an in- acid at various temperatures.
crease in the concentration of acetic acid would
lead to an increaser in the equilibrium concentra-
tion of the peroxyacid in the reaction mixture and portant. However, since the reagents involved in
consequently to an increase in the level of epoxi- the cleavage reactions are mainly in the aqueous
dation. This may, however, not be the case. In phase, oxirane cleavage reactions may be consid-
situ epoxidation of RSO is inherently a heteroge- ered insignificant compared with epoxide forma-
neous reaction process. The peroxyacetic acid is tion. The results in Tables 2 and 3 suggest that
generated in the aqueous phase and must be acetic acid is the more critical reagent in epoxida-
transferred to the oil phase to effect epoxidation. tion reaction.
The mass transfer process may be diffusion-con-
trolled. For a reaction mixture containing a fixed
3.2. Effect of temperature on epoxidation
amount of vegetable oil (double bonds), there
may be a concentration of acetic acid required for
The rates of epoxidation of RSO by peroxy-
optimum epoxidation, beyond which oxirane
acetic acid generated in situ at various tempera-
cleavage (epoxide degradation) may become im-
tures are shown in Fig. 1. The results show that
the initial increase in the extent of epoxidation
Table 3
Effect of hydrogen peroxide concentration on the extent of
with reaction time reached maximum values (for
epoxidation of RSO at 30 °C epoxidation at 50, 60 and 70 °C) and decreased
with further increase in reaction time. The time
Amount of hydrogen Extent of epoxidation (% required for epoxidation to attain maximum val-
peroxide (mol) oxirane) ues and the maximum levels of epoxidation at-
0.05 0.45
tained at the different temperatures are shown in
0.10 0.69 Table 4. The reductions in the levels of epoxida-
0.20 1.54 tion observed for reaction at 50, 60 and 70 °C)
0.29 3.20 are low (generally less than 12%) and was highest
0.39 3.40 at 70 °C. These results suggest that optimum
0.44 3.65
0.49 3.60
levels of epoxidation could be attained at moder-
ate reaction temperatures (50–60 °C) at which
Amount of acetic acid 0.087 mol. epoxide degradation would be minimal.
142 F.E. Okieimen et al. / Industrial Crops and Products 15 (2002) 139–144

Table 4
Levels of epoxidation and rate constant of epoxidation of RSO at various temperatures

Temperature Maximum oxirane Time for maximum oxirane to be Rate constant of epoxidation 106 k
attained (%) obtained (h) (l mol−1 s−1)

30 – – 0.20
50 3.0 8.50 1.34
60 3.8 3.25 3.32
70 3.7 2.0 5.01

4. Kinetics of epoxidation tions of the plots. The rate constants obtained

for the in situ epoxidation of RSO by peroxy-
The chemistry of in situ epoxidation may be acetic acid (Table 4) are of the order of 10 − 6 l
explained in terms of the following reaction pro- mol − 1 s − 1 and are comparable with the values
cesses, (Rangaraja et al., 1995): reported for soybean oil (Zaher et al., 1989;
(a) Formation of peroxyacid Princen, 1979). The values of the rate constant
RCOOH + H2O2 X RCOOOH +H2O showed the expected dependence on temperature
as an increase in the reaction temperature from
(b) Epoxidation 30 to 70 °C was accompanied by about 25-fold
increase in the value of the rate constant of
RCOOOH +R1CH =CHR2 epoxidation. The kinetic data for the in situ
“ R1CHOCHR2 epoxidation of RSO by peroxyacetic acid gave
good Arrhenius plot (Fig. 3) from which the
+RCOOH
activation energy, Ea of epoxidation was deter-

If the formation of peroxy acid is considered

to be the rate-determining step and the concen-
tration of this acid is assumed to be constant
throughout the reaction, the rate of epoxidation
will be given by expression (Gan et al., 1992),
d[EP]
=k{[H2O2]o − [EP]} [RCOOH]o. (1)
dt
Here EP denotes the epoxide, and the subscript
o initial concentration.
It follows that:
ln{[H2O2]o − [EP]} =k[RCOOH]ot +ln[H2O2].
(2)
The plot of ln{[H2O2]o −[EP]} vs reaction
time (t) according to Eq. (2) should yield
straight line from which the rate constant for
epoxidation can be determined. Fig. 2 shows the
plots of ln{[H2O2]o −[EP]} vs t for the in situ
epoxidation of RSO at different temperatures.
The deviations from linearity were considered to
be due to epoxide degradation and rate con- Fig. 2. Kinetics of epoxidation of rubber seed oil by peroxy-
stants were obtained from the initial linear por- acetic acid.
 F.E. Okieimen et al. / Industrial Crops and Products 15 (2002) 139–144
Fig. 3. Activation energy, Ea for the epoxidation of RSO by
peroxyacetic acid.
mined to be 15.7 kcal mol − 1. This value com-
pares favourably with the values of 15.12 and 18.3
kcal mol − 1 reported for the epoxidation of
methyl esters of palm olein (Gan et al., 1992) and
soybean oil (Zaher et al., 1989), respectively.
5. Thermodynamics of epoxidation of rubber seed
oil
The enthalpy of activation, DH, was calculated,
using the equation (Frost and Pearson 1961; Za-
her et al., 1989),
DH =Ea −RT, (3)
to be 15.12 kcal mol − 1.
The average entropy of activation, DS, and free
energy of activation, DF, were obtained using the
relationship (Frost and Pearson, 1961):
RT DS/R − E/RT
k= e e . (4)
Nh
Here k, rate constant; R, gas constant; T, absolute
temperature; N, Avogadro constant; and h,
Planck constant.
The average values of the thermodynamic
parameters were found to be DS = −31.94 cal
mol − 1 K − 1 and DF =25.44 kcal mol − 1.
143
6. Conclusion
The results from this study show that the epox-
idation of RSO by peroxyacetic acid generated in
situ can be carried out at moderate temperatures
with minimum epoxide degradation. The kinetic
and thermodynamic parameters of epoxidation
obtained indicate that an increase in the process
temperature would increase the rate of epoxide
formation and useful for the scale-up production
of epoxidised RSO using the in situ technique.
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