Applied Catalysis A: General 204 (2000) 223227

Catalysed or uncatalysed esterication reaction of

oleic acid with 2-ethyl hexanol
Corinne Lacaze-Dufaure, Zphirin Mouloungui

Laboratoire de Chimie Agro-Industrielle/UMR 1010-INRA/INPT, cole Nationale Suprieure de Chimie de Toulouse,

118 route de Narbonne-31077, Toulouse Cedex 04, France
Received 7 December 1999; received in revised form 6 March 2000; accepted 7 March 2000
Abstract
The para-toluene sulfonic acid (p-TSA) catalysed and uncatalysed esterications between oleic acid and 2-ethylhexanol are
investigated. The reactions were carried out in the presence of the stoichiometric amount or twice the stoichiometric amount
of alcohol with respect to the fatty acid, at 140170

C. In the presence of 1% of solid p-TSA monohydrate in xylene, the

reaction is completed in 50 min at 140

C. Without xylene, a mass concentration of esters of 93% is then reached after 10 min
of reaction in the concentrated alcoholic medium containing 1% of p-TSA. Without added catalyst, the kinetic is fast and the
reaction is completed in 280 min at 170

C in the concentrated alcoholic medium. The reactive molecules and the products
of the reaction are organised in hydrophilic aggregates in the concentrated oleophobic medium. The carboxylic group of the
fatty acid is then activated and shows a high catalytic activity. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Esterication; 2-Ethylhexanol; Oleic acid; p-TSA catalysis; Reactive aggregate; Uncatalysed esterication reaction
1. Introduction
In the eld of the chemical transformations of fatty
acids to fatty esters of monoalcohols, it is esterication
of fatty acids C16C18 by various monoalcohols in-
cluding methanol, propanol, butanol, 2-ethylhexanol,
1-tridecanol, oleyl alcohol, stearyl alcohol, which
is generally described in the literature to produce
corresponding fatty esters [1]. These monoesters of
monoalcohols are uid liquids or solid waxes. They
are used as solvents in cosmetics or lubricants in
metal treatment, textile industry, plastics industry [2].
Esterication is usually catalysed by an acid catalyst
donor of protons (H
2
SO
4
, RSO
3
H, H
3
PO
4
[310]) or

Corresponding author. Tel.: +33-5-6288-5724;

fax: +33-5-6288-5730.
E-mail address: zmouloungui@ensct.fr (Z. Mouloungui).
by a metallic catalyst [11]. To shift the equilibrium
of the esterication towards the desired ester, an ex-
cess of alcohol or an additional azeotropic solvent are
often used.
In this work, according to literature, the esterica-
tion of oleic acid C18:1 (72%) with 2-ethylhexanol
was rst catalysed by para-toluene sulfonic acid
(p-TSA) with xylene as azeotropic solvent. We also
carried out the p-TSA catalysed reaction in a con-
centrated medium, without added solvent. We nally
tested the uncatalysed esterication in a free-solvent
medium.
2. Experimental
2.1. Materials
Oleic acid (OA, C18:1, 72% of purity, 11% of
linoleic acid) and 2-ethylhexanol were supplied by
0926-860X/00/$ see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S0926- 860X( 00) 00533- 0
224 C. Lacaze-Dufaure, Z. Mouloungui / Applied Catalysis A: General 204 (2000) 223227
Prolabo. Paratoluene sulfonic acid (p-TSA, 99%) was
purchased from Fluka and xylene (isomers mix, 98%,
bp=140

C) from SDS.
2.2. Esterication of oleic acid with 2-ethylhexanol
catalysed by p-TSA
A 250 ml ask is equipped with a mechanical stir-
rer (300 rpm), a thermometer and a Dean Stark trap
with a condenser. The desired amounts of oleic acid
(50 mmol), 2-ethylhexanol (50 mmol) and p-TSA (0.5,
1 or 2% with respect to the fatty acid) are introduced
in the ask. Xylene (60 ml) is then added. The mixture
is then reuxed under nitrogen for 4 h in an oil bath
regulated at 200

C. Samples are withdrawn at prede-

termined time intervals and cooled immediately by
immersion into cold water. The progress of the reac-
tion is followed by a thin layer chromatography/ame
ionisation detection (TLC/FID) system (Iatroscan
MK5, Iatron Laboratories). The data are acquired us-
ing Boreal software. Oleic acid and 2-ethylhexyl oleate
are quantied from calibration curves [12]. The mass
composition of the reaction medium is calculated as
follows:
Ester mass percentage (%)
= 100
mass of esters
mass of esters +mass of oleic acid
Fig. 1. Plot of the mass concentration of 2-ethylhexyl oleate in the reaction medium during the p-TSA catalysed esterication of oleic
acid by 2-ethylhexanol in xylene. Mass ratio p-TSA/OA: 02%, molar ratio 2-EH/OA=1/1; 60 ml xylene; temperature: 140170

C.
2.3. Uncatalysed esterication of oleic acid with
2-ethylhexanol
A 250 ml ask with a mechanical stirrer (300 rpm),
a thermometer and a Dean Stark trap with a condenser
is lled with 50 mmol of oleic acid and 100 mmol
of 2-ethylhexanol. The mixture is then reuxed un-
der nitrogen for 4 h in an oil bath regulated at 200

C.
Samples are withdrawn at predetermined time inter-
vals and cooled immediately by immersion into cold
water. The progress of the reaction is followed by a
TLC/FID system.
3. Results and discussion
3.1. Para-toluene sulfonic acid in xylene as catalyst
The reaction of oleic acid with 2-ethylhexanol
is rst performed by catalysis with mono hydrated
p-TSA in xylene. Under our operating conditions,
the azeotrope of the binary mixture xylene/water is
obtained at 140

C. Following the progressive and

quantitative elimination of xylene and water, the tem-
perature of the residual concentrated reaction medium
increases and reaches 170

C at the end of the reaction.

The reaction mixture is homogeneous.
Fig. 1 represents a plot of the mass concentration
of the medium during the esterication of oleic acid
C. Lacaze-Dufaure, Z. Mouloungui / Applied Catalysis A: General 204 (2000) 223227 225
Fig. 2. Hypothetical reactive structures during the p-TSA catalysed
esterication of oleic acid by 2-ethylhexanol.
with 2-ethylhexanol used in stoichiometric amount
and with various concentrations of p-TSA. Without
p-TSA, an induction period of 40 min is observed
when the reagents are diluted in xylene. An amount
of 0.5% p-TSA eliminates the induction period and
strongly accelerates the kinetic of the reaction. In
480 min, the conversion of oleic acid is complete. In
the presence of an amount of 1% p-TSA with respect
to the fatty acid, a mass concentration of 2-ethylhexyl
esters of 55% is reached in the reaction medium af-
ter 10 min of reaction. A maximum is reached after
50 min of reaction with a mass 2-ethylhexyl esters
concentration of 90%. In 120 min, all the oleic acid
is consumed. With an amount of catalyst of 2%, the
oleic acid is totally converted in 30 min. By repeating
Fig. 3. Plot of the mass concentration of 2-ethylhexyl oleate in the reaction medium during the oleic acid esterication with 2-ethylhexanol
in a concentrated medium. Mass ratio p-TSA/OA=1%; molar ratio 2-EH/OA=1/1; temperature: 170

C.
the series of experiments with various concentrations
of p-TSA, we underline the inuence of the acidity
brought by the sulfonic groups; the inuence of the
initial acid catalyst concentration in the range studied.
Even the lowest initial catalyst concentration (0.5%)
shows a great inuence on the reaction rate.
We can thus observe a synergy of heating and phys-
ical effects which is favourable to high conversion
yields. The thermal contribution causes the elimination
of xylene and water as the reaction is in progress. The
unreacted oleic acid, the 2-ethylhexanol, and p-TSA
are in a concentrated hydrophobic medium which be-
comes richer of hydrophobic 2-ethylhexyl esters as the
reaction proceeds. This has a notable incidence on the
reactivity of the carboxylic reactional centres of the
fatty acid and on the hydroxyl groups of the branched
alcohol. The molecular organisation of the reaction
medium depends on the structure of the reagents and
the products. We work with molecules, each one pre-
senting a polar head (carboxylic group of the fatty
acid, hydroxyl group of the alcohol and carboxyester
group of the 2-ethylhexyl oleate) and a long carbona-
ceous chain (six atoms of carbon for alcohol and 18
atoms of carbon for the fatty acid). We think that the
formation of some reactive structures is carried out by
the hydrophylic/hydrophylic interactions between the
polar ends and by the formation of hydrogen bonds
between the molecules of oleic acid and alcohol. The
p-TSA is integrated within these structures by solva-
tion of its acid sites and formation of reagent-catalyst
hydrogen bonds (Fig. 2). The water formed by the
reaction in the hydrophilic phase xylene, which is
226 C. Lacaze-Dufaure, Z. Mouloungui / Applied Catalysis A: General 204 (2000) 223227
Fig. 4. Plot of the mass concentration of 2-ethylhexyl oleate in the
reaction medium during the autocatalysed esterication of oleic
acid with 2-ethylhexanol. Molar ratio 2-EH/OA: 2/1, temperature:
170

C.
a non-dissociating solvent, does not break these in-
termolecular weak interactions. 2-Ethylhexanol has
a structure which develop co-surfactant properties.
Indeed we showed that its interfacial surface tension
with water at 25

C is 13.5 mNm
1
[13]. During
the reaction, the formation of 2-ethylhexyl esters al-
lows to stabilise the structure of the medium because
2-ethylhexyl oleate has surface-active properties, its
Fig. 5. Hypothetical reactive structures during the uncatalysed esterication of oleic acid by 2-ethylhexanol.
interfacial tension with water being of 5.8 mNm
1
at 25

C [13]. We think that the esters formed leave

easily the reactive structures in the reaction medium
while being directed to the surface of the hydrophilic
aggregates.
3.2. Para-toluene sulfonic acid as catalyst in
concentrated medium
We carried out an assay without xylene with a con-
centration in p-TSA of 1% with respect to the fatty
acid. The oleic acid is mixed to the 2-ethylhexanol
in a molar ratio 1/1 (Fig. 3). The temperature raised
170

C in the ask within the rst minutes of reaction

and part of the water produced by the reaction is thus
eliminated from reaction medium and condensed in
the Dean Stark trap. As soon as the co-reagents are
concentrated, the reaction of esterication is sponta-
neous. A mass percentage of esters (75%) is obtained
after 5 min of reaction. After 10 min of reaction, the
2-ethylhexyl ester concentration reaches a maximum
value of 93%. One notes a benecial effect due to
the concentration of the reagents and the contribu-
tion of temperature. For these reversible reactions of
C. Lacaze-Dufaure, Z. Mouloungui / Applied Catalysis A: General 204 (2000) 223227 227
esterication, temperatures higher than 200

C are usu-
ally required. We then underline the performance of
our catalytic system of hydrophilic aggregates in a
concentrated alcoholic for a fast and total reaction at
170

C.
3.3. Uncatalysed esterication in concentrated
oleophobic medium
We demonstrated the dominating inuence of the
reactive structures in the reaction medium on the
kinetics of the reaction. We carried out an experi-
ment without catalyst being at 170

C. To obtain high
conversion yields, we used twice the stoichiometric
amount of 2-ethylhexanol to force the reaction to
completion. The results show that the condensation
of oleic acid with 2-ethylhexanol took place without
added catalyst (Fig. 4). In the absence of a third sol-
vent, the concentrated oleophobic medium constituted
by oleic acid/2-ethylhexanol in a molar ratio 1/2 en-
hanced the velocity of the uncatalysed esterication
reaction. The reaction begins quickly and a content
of esters of 90% is reached after 130 min of reaction.
In 280 min of reaction, one obtains a reactional crude
product containing 99% of esters. The temperature
helps to break the hydrogen bonds between the fatty
acid molecules and to insert the alcohol molecules and
fatty ester molecules in the active aggregates (Fig. 5).
The carboxylic group of the fatty acid, the hydroxyl
group of the alcohol and the carboxyester group of
the fatty ester develop hydrogen bonds. Optimisation
of the reaction conditions will need to be based on
this medium structuration.
4. Conclusion
Oleic acid was esteried by 2-ethylhexanol under
the following conditions: (i) in presence of p-TSA in
xylene to achieve high yield of conversion of the fatty
acid with small duration times; (ii) with p-TSA in a
concentrated solvent free mediumand (iii) without any
added catalyst in the concentrated medium. All the
experiments were conducted under equimolar amounts
of the chosen reactants or of twice the stoichiometric
amount of alcohol with respect to the fatty acid at
140170

C.
High esterication yields occurred without added
catalyst, the kinetic is fast and the reaction is com-
pleted in 280 min at 170

C in the concentrated alco-

holic medium. The carboxylic group of the fatty acid
is activated by aggregation. The esterication of fatty
acids with a high weight alcohol can be carried out in
concentrated free solvent. This is due to the formation
of hydrophilic aggregates in the oleophobic medium.
The reactional conditions are on investigation.
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