The hydroxylation reaction was carried out in 9
hours at 70 oC temperature, 2000 rpm stirring speed,
the molar ratio of ESO:H2O and the concentration of
catalyst H2SO4 were fixed at 1:15 and 8 wt.%
respectively. The progress of reaction was monitored
by measuring the oxirane and the hydroxyl content
of the product. The results are shown in Fig. 9.
As can be seen from Fig. 9, the oxirane content
of polyol dropped strongly from 6.68 to 2.12 % for
the reaction in one hour and continued to go down
1.05 % for that of five hours but decreased very
slowly to 0.77 % when further extending the
reaction up to 9 hours. However, the hydroxyl
content of polyol raised to 358.51 mg KOH/g at five
hours and increased gradually to 372.96 mg KOH/g
when further prolonging the time to nine hours.
These results indicated that after five hours both the
epoxide ring-opening and the hydroxyl group
forming reactions took place very slowly.
The correlation P/E reached 0.8 in one hour
reaction and incresaed to 0.91 in three hours but
went down 0.86 in five hours and remained
unchanged up to nine hours.
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Vietnam Journal of Chemistry, International Edition, 55(4): 411-416, 2017
DOI: 10.15625/2525-2321.2017-00482
411
Synthesis of bio-polyols by epoxide ring opening reaction
with H2O as a reagent
Nguyen Thi Thuy
*
, Vu Minh Duc, Nguyen Thanh Liem
Polymer Center, Hanoi University of Science and Technology
Received 13 December 2016; Accepted for publication 28 August 2017
Abstract
The different nucleophilic reagents have been using in epoxide ring opening reactions among which water is the
most preferable. At first, the epoxide group must be protonated by water in the presence of H2SO4 as catalyst. The
successful epoxide ring opening reaction of epoxidized soybean oil (ESO) by water in the H2SO4 environment was
verified by FTIR and H-NMR spectroscopy. The effect of reaction parameters like the amount of reagents, catalyst,
temperature and time of a polyol synthesis were studied through the hydroxyl and oxirane oxygen content of product.
Moreover, the impact of the parameters on the correlation P/E was determined by comparing a hydroxyl group
formation to an epoxide group consumption. When the hydroxylation reaction was carried out with ESO:H2O mole ratio
of 1:15; in 8 wt.% H2SO4; at temperature of 70
o
C and in 5 hours, the hydroxyl content of 358.51 mgKOH/g of the
obtained product was achieved.
Keywords. Epoxidized vegetable oil, biopolyol, epoxide ring-opening, epoxidized soybean oil.
1. INTRODUCTION
There are many methods to synthesize polyols from a
epoxidized vegetable oil (EVO). These methods can
be divided into two groups. Group 1 (indirect
method) - polyols are synthesized from the
epoxidized vegetable oil through the formation of
intermediate compounds. This group has two
methods: method 1-the epoxidized vegetable oils
were first performed by ring-opening polymerization
catalyst HBF4, then reduced by catalytic LiH4;
method 2 – the epoxidized vegetable oil was initially
carbonized by CO2 and catalyst, then ring opened by
agent of HR forms such as HN[R'OH]2. Group 2
(direct method) – polyol is synthesized directly from
the epoxidized vegetable oil without going through
intermediate compounds. This group has also two
methods: method 1 - polyol is synthesized by the
hydrogenation of epoxidized vegetable oil with
catalyst of Ni; method 2 - polyol is synthesized by
epoxide ring opening reaction in the presence of ring-
opening agent of HXR form such as HR, H2O [1].
Biobased polyols were synthesized from reaction
between epoxidized soybean oil and lactic, glycolic,
or acetic acids by Sylvain Caillol and the average
hydroxyl functionality of polyol were between 4 and
5 [2]. According to Zlatanić, the polyols were
synthesized from six epoxidized oils by epoxide ring
opening reaction with boiling methanol in the
presence of a tetrafluoroboric acid catalyst and the
hydroxyl value of these polyols ranges from 163.5
mgKOH/g to 247.8 mgKOH/g [3]. A.A. Beltrán and
L.A. Boyacá studied epoxide ring-opening reaction
of epoxidized soybean oil with ethylene glycol and
ethanol by using catalyst of H2SO4 in the period from
2 to 6 hours and found the optimal temperature is 70
°C with ethanol and 80 °C with ethylene glycol [4].
This work studied the influence of reaction
parameters like the amount of reagents (H2O),
catalyst (H2SO4), temperature and time on the
hydroxylation reaction in order to find the optimal
conditions for synthesis of the bio-polyol with high
hydroxyl content.
2. EXPERIMENTAL
2.1. Materials
Vietnam soybean oil with iodine value of 131 cgI2/g.
Sodium tungstate dehydrate and Wijs solution are
from Merck, Germany. Hydrogen bromide solution
(33 wt.%) is of Sigma-Aldrich, USA. Phosphoric
acid H3PO4 (85 wt.%) and hydrogen peroxide (30
wt.%), sulfuric acid H2SO4 (98 wt.%), glacial acetic
acid are from Xilong Chemical, China.
VJC, 55(4), 2017 Nguyen Thi Thuy et al.
412
2.2. Methods
2.2.1. Epoxidation procedure
The reaction was performed in a 500 ml four neck
flask equipped with a stirrer, thermometer, dropping
funnel and reflux cooler. The Vietnam soybean oil
and catalyst were added to the flask and then the
30wt.% hydrogen peroxide was dropped. After
charging H2O2 was completed, the reaction was
continued mixing for another hour. After that, the
mixture was cooled down and treated with water.
The final product (ESO) was dried out by heating
about 60
o
C in a vacuum oven.
2.2.2. Hydroxylation procedure
The reaction was carried out in the 500 ml three
neck flask equipped with a stirrer, thermometer and
reflux cooler. The ESO, reagent of H2O and catalyst
of H2SO4 were added to the flask. After charging,
the reaction was continued mixing at certain
temperature for a further time. After that, the
mixture was cooled down and treated with water.
The final product was dried out by heating at about
60
o
C in the vacuum oven.
2.2.3. Analytical techniques
Fourier transform infrared spectroscopic analysis
and nuclear magnetic resonance spectroscopic
analysis were performed on the IRAffiniti-1S,
Shimadzu (Japan) and Bruker Avance 500 (USA).
Iodine value is determined according to standard
ASTM D5768: sample was dissolved in the solvent
in the presence of Wijs solution and titrated with
0,1N Na2S2O3 solution. Oxirane content is
determined according to standard ASTM D1652:
sample was dissolved in the solvent and titrated
directly with HBr solution 0,1N. Hydroxyl content is
determined according to standard ASTM D1957:
sample was first acetylated and then titrated by KOH
solution 0,5N. The density and viscosity are
determined by using pycnometer 25ml (China) and
Brookfield Model RVT (Germany) respectively.
3. RESULTS AND DISCUSSION
3.1. Synthesis and characteristics of ESO
Epoxidized soybean oil was synthesized according
to a published procedure [5]. The characteristics of
ESO are shown in table 1.
Table 1: Characteristics of ESO and biopolyol
Characteristics ESO Biopolyol
Hydroxyl content, mgKOH/g 18.02 358.51
Oxirane content, % 6.68 0.73
Iodine value, cgI2/g 7.5 2.87
Density 20 °C, g/ml
1.02 1.02
Viscosity 20 °C, cP 375 1920
3.2. Evaluating the result of epoxide ring opening
reaction
The success of the hydroxylation reaction associated
with the formation of hydroxyl groups on
macromolecule of the product. The FTIR
spectroscopic analysis of obtained polyol and
epoxidized soybean oil was studied to confirm the
presence of hydroxyl groups on macromolecules.
FTIR spectra of epoxidized soybean oil and
polyol are shown in figure 1. The disappearance of
the band at 821.67 cm
-1
in the spectra of polyol
indicated that the epoxide group had been used up.
The appearance of the band at 3406.29 cm
-1
, which
was not seen in spectra of epoxidized soybean oil
(ESO), was the characteristic of the hydroxyl group
that connected with carbon atom. This analysis
confirmed that the hydroxylation reaction had taken
place.
Polyol was synthesized with ESO:H2O molar ratio of
1:10; H2SO4 8 wt.%; 70
o
C; 2000 rpm
Figure 1: FTIR spectrum of ESO and polyol
In parallel with the FTIR spectroscopic analysis,
nuclear magnetic resonance spectroscopy was used
as well. The
1
H-NMR spectra of epoxidized soybean
oil and polyol are shown in Fig. 2.
It is found that the peaks at 2.9÷3.3 ppm which
are the characteristic of epoxide group protons
821,67
epoxide
ESO
Polyol 3406,29
OH
40
70
100
130
160
500150025003500
T
ra
n
s
m
it
a
n
c
e
,
%
Wavenumber, cm-1
VJC, 55(4), 2017 Synthesis of bio-polyols by epoxide
413
existed clearly on the
1
H-NMR spectra of the ESO
but these peaks did not appear in the
1
H-NMR
spectra of the polyol. Also the peaks at 3.4÷4.1 ppm
were assigned to the protons of methine -CH- and
hydroxyl groups connected to carbon atom (HC-OH)
were absent from the
1
H-NMR spectra of ESO but
appeared on the
1
H-NMR spectra of the polyol. This
proves the epoxide groups in the ESO were
converted to hydroxyl groups in the polyol. The
results of the nuclear magnetic resonance
spectroscopic analysis once again confirmed the
success of hydroxylation reaction.
Polyol was synthesized with ESO:H2O molar ratio of
1:20; 8 wt.% H2SO4; 70
o
C; 2000 rpm
Figure 2:
1
H-NMR spectrum of ESO and polyol
3.3. The impact of reaction parameters on the
hydroxylation reaction
3.3.1. The effect of reagent content
A series of hydroxylation reactions were carried out
at 70
o
C temperature, 2000 rpm stirring speed, the
molar ratio of the epoxide group of ESO to water
(ESO:H2O) in the range of 1:10 to 1:20 and the
concentration of H2SO4 was fixed at 8 wt.%. The
progress of reaction was monitored by measuring the
oxirane and hydroxyl content of products.
As can be seen from Fig. 3, prolonging reaction
time decreased the oxirane content of polyol while
increased the hydroxyl content. When raising the
amount of H2O from molar ratio of 1:10 to 1:15, the
oxirane content of polyol declined remarkably,
indicating that the ability to open epoxide ring
increased strongly and consequently the hydroxyl
content of polyol grew remarkably as well.
Increasing further the amount of H2O to 1:20,
the oxirane content of polyol had greater value than
the reaction with molar ratio of 1:15 but smaller
value than the one with molar ratio of 1:10. This
demonstrated the ability to open the epoxide ring in
this case was lower than the case of 1:15, but higher
than the one of 1:10. The inevitable result of the
hydroxyl content of the polyol in this case also
followed the same trend. The ESO:H2O ratio of 1:15
has the highest ability to either open the epoxide ring
or form the hydroxyl group.
Hy: hydroxyl content, Ox: oxirane content
Figure 3: The effect of H2O content on the oxirane
and hydroxyl contents of polyol
The correlation between hydroxyl group
formation (P) and the epoxide group consumption
(E) (it was called correlation P/E) allows to evaluate
the presence of site reaction, in which:
(exp: experiment; th: theory)
From the oxirane content of ESO (6.68%), it is
easy to calculate theoretical hydroxyl content of the
polyol (468.435 mgKOH/g). The effect of H2O
content on the correlation P/E is presented in Fig. 4.
Figure 4: The effect of H2O content on
the correlation P/E
0
2
4
6
8
0
100
200
300
400
0 2 4 6
O
x
ir
a
n
e
c
o
n
te
n
t,
%
H
y
d
ro
x
y
l
v
a
lu
e
,
m
g
K
O
H
/g
Time, hrs
Hy 1:10 Hy 1:15 Hy 1:20
Ox 1:10 Ox 1:15 Ox 1:20
0.61
0.91
0.86 0.81
0
0.25
0.5
0.75
1
0 2 4 6
C
o
rr
e
la
ti
o
n
P
/E
Time, hrs
1:10 1:15 1:20
VJC, 55(4), 2017 Nguyen Thi Thuy et al.
414
As can be noticed from Fig. 4, when the amount
of H2O was small (1:10 and 1:15), along with the
prolongation of reaction time, the correlation P/E
increased and reached the maximum value (for three
hours) and then decreased with further increase in
reaction time. When the amount of H2O increased
from 1:10 to 1:15 molar ratio, the correlation P/E
increased from 0.61 to 0.81 (for one hour) and from
0.81 to 0.91 (for three hours).
Increasing the amount of H2O to the molar ratio
of 1:20, the correlation P/E for one hour reaction
(0.81) showed the same value with that of the molar
ratio of 1:15. However, the correlation P/E in three
or five hours declined obviously to the same value
with that of the molar ratio of 1:10.
Therefore, the ESO:H2O ratio of 1:15 showed
the highest in either the hydroxyl group or the
correlation P/E, indicating that this reaction had the
lowest degree of side reactions.
3.3.2. The effect of catalyst content
Three hydroxylation reactions were carried out at 70
o
C temperature, 2000 rpm stirring speed, the molar
ratio of ESO:H2O was fixed at 1:15 and the
concentration of catalyst H2SO4 changed from 6
wt.% to 10 wt.%. The progress of reaction was
monitored by determining the oxirane and hydroxyl
contents of products. The results are shown in Fig. 5.
Hy: hydroxyl content, Ox: oxirane content
Figure 5: The effect of H2SO4 content on the
oxirane and the hydroxyl content of polyol
The oxirane content declined and the hydroxyl
content of polyol increased along with the
prolongation of reaction time. When the content of
catalyst increased from 6 wt.% to 10 wt.%, the
oxirane content had trend of slightly increasing,
suggesting that the ability to open epoxide ring
reduced gently (Fig. 5).
Unlike the oxirane content, the hydroxyl content
of polyol seems to depend noticeably on the content
of catalyst. The results indicated that increasing the
catalytic content from 6 wt.% to 8 wt.%, the
hydroxyl content of polyol increased sharply (from
31.33 mgKOH/g to 273.12 mgKOH/g in one hour
and from 206.05 mgKOH/g to 358.51 mgKOH/g in
five hours). Further increasing the amount of
catalyst to 10 wt.%, the hydroxyl content of polyol
was greater than that of 6 wt.% catalyst but much
smaller than that of 8 wt.% catalyst (Fig. 5). These
results demonstrated that the catalyst of 8 wt.% is
optimum content for hydroxylation reaction.
With different catalyst contents, the ability to
open ring of epoxide group was not much different
but the ability to form hydroxyl group was greatly
different so that the correlation P/E was also large
different. The effect of H2SO4 content on the
correlation P/E is described in Fig. 6.
Figure 6: The effect of H2SO4 content on
the correlation P/E
When the amount of catalyst was 6 wt.%, the
ability to open ring of epoxide group was the highest
but the ability to form hydroxyl group was the
lowest (Fig. 5). Thus, the correlation P/E was the
lowest (Fig. 6). This illustrated that when the
amount of catalyst was small, many side reactions
took place. The oxirane content of polyols decreased
sharply within the first hour of the reaction and
slightly in the following hours. However, the
hydroxyl content of polyol increased marginally
within the first hour of the reaction and remarkably
in the next hours (Fig. 5). These results suggested
that the correlation P/E also increased in parallel
with the increase of the reaction time (Fig. 6).
When the amount of catalysts was at 8 wt.% and
10 wt.%, the oxirane content of polyol also
decreased exceptionally within the first hour of the
reaction and gently in the next hours. However, the
hydroxyl content of polyol increased strongly within
273,12
322,47
358,51
0
2
4
6
8
0
100
200
300
400
0 2 4 6
O
x
ir
a
n
e
c
o
n
te
n
t,
%
H
y
d
ro
x
y
l
v
a
lu
e
,
m
g
K
O
H
/g
Time, hrs
Hy 10 Hy 8 Hy 6
Ox 10 Ox 8 Ox 6
0.40
0.56
0.54
0.80
0.91
0.86
0
0.25
0.5
0.75
1
0 2 4 6
C
o
rr
e
la
ti
o
n
P
/E
Time, hrs
10 8 6
VJC, 55(4), 2017 Synthesis of bio-polyols by epoxide
415
the first hour of the reaction and lightly in the
following hours (Fig. 5). So the correlation P/E
increased and reached the maximum value for the
reaction in three hours. The correlation P/E
decreased with the elongation of the reaction time to
five hours. It was indicated that the highest
correlation P/E was 0.91 for the reaction in three
hours when the amount of catalyst was in 8 wt.%
(fig.6).
3.3.3. The effect of temperature reaction
A series of hydroxylation reactions were carried out
at 60, 70 and 80
o
C temperature, 2000 rpm stirring
speed, the molar ratio of ESO:H2O and the
concentration of catalyst H2SO4 were fixed at 1:15
and 8 wt.% respectively. The progress of reaction
was monitored by measuring the oxirane and
hydroxyl contents of products. The results are shown
in Fig. 7.
Hy: hydroxyl content, Ox: oxirane content
Figure 7: The effect of temperature on the oxirane
and the hydroxyl content of polyol product
Figure 8: The effect of temperature on
the correlation P/E
It was found that when the reaction was carried
out at 60 °C, the oxirane content of polyol product
remained quite high and the hydroxyl group was
low. Raising the temperature to 70 °C, the ability to
open epoxide group increased. Moreover, the
oxirane contents of polyol product of reaction at 70
o
C and 80
o
C gave almost the same. However, the
hydroxyl group of the product at one hour and 80
o
C
(292.98 mgKOH/g) was higher than that at 70
o
C
(273.21 mgKOH/g). Therefore the correlation P/E at
one hour and at 80
o
C (0.84) was also higher that at
70
o
C (0.8 %) (Fig. 8). For the reaction in three
hours and five hours, the hydroxyl group of the
polyol product at 70 °C was higher than that of at 80
°C. As the result the correlation P/E at 70 °C (0.91
in three hours) was higher than that at 80 °C (0.81 in
three hours) (Fig. 8).
With the temperature of 60 °C, the correlation
P/E was likely to increase from one hour to five
hours but at 70
o
C the correlation P/E increased and
reached the maximum value for the reaction in three
hours then decreased if further extending the
reaction time up to 5 hours. However, when the
reaction was carried out at 80 °C, the correlation P/E
dropped immediately after the first hour reaction
(Fig. 8). That result indicated that prolonging
reaction time led to more side reactions.
3.3.4. The effect of reaction time
The hydroxylation reaction was carried out in 9
hours at 70
o
C temperature, 2000 rpm stirring speed,
the molar ratio of ESO:H2O and the concentration of
catalyst H2SO4 were fixed at 1:15 and 8 wt.%
respectively. The progress of reaction was monitored
by measuring the oxirane and the hydroxyl content
of the product. The results are shown in Fig. 9.
As can be seen from Fig. 9, the oxirane content
of polyol dropped strongly from 6.68 to 2.12 % for
the reaction in one hour and continued to go down
1.05 % for that of five hours but decreased very
slowly to 0.77 % when further extending the
reaction up to 9 hours. However, the hydroxyl
content of polyol raised to 358.51 mg KOH/g at five
hours and increased gradually to 372.96 mg KOH/g
when further prolonging the time to nine hours.
These results indicated that after five hours both the
epoxide ring-opening and the hydroxyl group
forming reactions took place very slowly.
The correlation P/E reached 0.8 in one hour
reaction and incresaed to 0.91 in three hours but
went down 0.86 in five hours and remained
unchanged up to nine hours.
273,21
292,98
0
2
4
6
8
0
100
200
300
400
0 2 4 6
O
x
ir
a
n
e
c
o
n
te
n
t,
%
H
y
d
ro
x
y
l
v
a
lu
e
,
m
g
K
O
H
/g
Time, hrs
Hy 60 Hy 70 Hy80
Ox 60 Ox 70 Ox 80
0.80
0.91 0.84
0.79
0
0.25
0.5
0.75
1
0 2 4 6
C
o
rr
e
la
ti
o
n
P
/E
Time, hrs
60 70 80
VJC, 55(4), 2017 Nguyen Thi Thuy et al.
416
Hy: hydroxyl content, Ox: oxirane content
P/E: correlation P/E
Figure 9: The effect of time on the oxirane and the
hydroxyl content of polyol and the correlation P/E
4. CONCLUSIONS
The success of hydroxylation reaction of epoxidized
soybean oil was confirmed by FTIR and H-NMR
spectrum.
The optimal conditions for the hydroxylation
reaction of epoxidized soybean oil was found: the
ESO:H2O molar ratio of 1:15, the H2SO4 of 8 wt.%,
at temperature of 70 °C. The hydroxyl content of
bio-polyol which received after 5 hours reached to
358.51 mgKOH/g and other characteristics of this
bio-polyol have been determined.
Acknowledgement. This work was supported by
National Key Laboratory for Polymer & Composite
Materials, Hanoi University of Science and
Technology, Project T2016-PC-011.
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5. Nguyen Thi Thuy, Vu Minh Duc, Nguyen Thanh
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Corresponding author: Nguyen Thi Thuy
Hanoi University of Science and Technology
No. 1, Dai Co Viet Road, Hai Ba Trung Dist., Hanoi
E-mail: thuy.nguyenthi1@.hust.edu.vn; Telephone: 0904505335.
273,21
358,51 372,96
6,68
2,12
1,91
1,05 0,77
0.8
0,91 0.86 0.83
0
2
4
6
8
0
100
200
300
400
0 2 4 6 8 10
C
o
rr
e
la
ti
o
n
P
/E
O
x
ir
a
n
e
c
o
n
te
n
t,
%
H
y
d
ro
x
y
l
v
a
lu
e
,
m
g
K
O
H
/g
Time, hrs
Hy 70 Ox 70 P/E
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