J Surfact Deterg (2011) 14:173177
DOI 10.1007/s11743-010-1218-3
ORIGINAL ARTICLE
Synthesis, IR, HPLC Analysis and Performances of Palm Fatty
Acids and Triethanolamine-Based Esterquats
Manochehr Bahmaei Flora Badiee
Hosein Kasehgari
Received: 14 September 2009 / Accepted: 8 June 2010 / Published online: 3 July 2010
AOCS 2010
Abstract Esterquats were synthesized by esterification of
palm fatty acids and triethanolamine (TEA) followed by
quaternization with dimethyl sulfate. The optimum reac-
tion conditions for the esterification of palm fatty acids and
triethanolamine were found to be 160 C under nitrogen.
The esters obtained were subjected to quaternization with
dimethyl sulfate at a 1:0.95 ratio. The maximum yield of
synthesized esterquats was 53.0 1% in isopropanol.
Instrumental techniques, viz. IR and HPLC verified the
esterification and subsequent quaternization of the ester
obtained. The performances of the esterquats produced
were evaluated by tests on towel fabric substrates. The
synthesized esterquats exhibited good softness and rewet-
tability (51 mm/6 min) for towel fabrics.
Keywords Esterquat  Cationic surfactant 
Esterification  Quaternization  Rewetting 
Surface activity
M. Bahmaei (&)  F. Badiee (&)
Islamic Azad University, North Tehran Branch,
Daftari sharghi Alley, Shariati St., Tehran, Iran
e-mail: mbahmaie@savola.com
F. Badiee
e-mail: Felora_b63@yahoo.com
M. Bahmaei
Research and Development Laboratory of Behshahr Ind. Co.,
8th Km. Fath road, Tehran, Iran
H. Kasehgari
Research and Development Laboratory of Paxan Ind. Co.,
8th Km. Fath road, Tehran, Iran
Introduction
Surfactants are chemicals, which adsorb at surfaces, and
are classified as surface-active agents. A surfactant mole-
cule consists of hydrophilic and hydrophobic parts. Anio-
nic, Nonionic, Cationic and Amphoteric-Zwitterionic are
the four main classes of surfactants [1]. Immediately after
washing, the fibers generally possess an electric charge
since the isoelectric point of the substrate is lower than the
pure water pH or because of the presence of residual
anionic surfactant; cationic softener adsorption on fibers
neutralizes natural and/or adsorbed negative charges and
leaves a layer of hydrophobic tails on the fiber surface,
ensuring a good lubricating and unraveling effects.
Esterquats are one of the varieties of cationic surfactants
used as the main ingredients of fabric softening formula-
tions used worldwide. They are quaternary ammonium
compounds, having two long (C16C18) fatty acid chains
with 2 weak ester linkages wich are produced as follows:
2RCOOH NCH2 CH2 OH3 $ RCOOCH2 CH2 2
NCH2 CH2 OH 2H2 O
RCOOCH2 CH2 2 NCH2 CH2 OH CH3 2 SO4 $
RCOOCH2 CH2 2 N CH3 CH2 CH2 OH;CH3 OSO
3:
Esterquats represent a new generation of fabric softening
agents, having replaced the dialkyldimethylammonium
salts (e.g. ditetradecyldimethylammonium chloride (DTD-
MAC) and distearyldimethylammonium chloride (DSD-
MAC)) [2]. In 1975, esterquats based on triethanol amnine
(TEA) were patented for use as fabric softeners [2, 3].
Some important features [4] of esterquats are: (1) they can
be formulated as high concentrated solutions (i.e. 25 wt%)
which are easily dispersible in water; (2) they do not cause
fabric staining and pass European environmental safety
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guidelines; (3) they have hydrolytic stability and their particle size, Philips, Pye Unicam Ltd., England),
softening can be improved by adjusting dispersion pH to a injector (E1E005) with a 20-ll stainless steel sample
maximum of 4; (4) they meet test guidelines of the Orga- loop, UVVis photodiode array detector (SPD-M 10A
nization for Economic Cooperation and Development vp) and LC Solution data software (version 1.02 sp3).
OECD [5]. Out of the various existing cationic molecules A gas chromatography system model 17-A (Shimadzu,
for fabric softening, esterquats are becoming favored Japan) with a capillary injection system, fused silica
because of their eco-friendly nature and excellent biode- capillary column (60 m 9 0.25 mm) coated with SP-
gradability [6]. By definition, the ultra or compact fabric 2,340 (Supleco, USA) and a flame-ionization detector
softeners are 2030 wt.% concentrates with advanced for- (FID).
mulas that can be added directly to cool rinse water without
fear of fabric staining, and ultra softener formulations are
Chemical Analysis
certainly more convenient for the consumers. They need to
reduce and to recycle plastic packaging; however, it is the
Acid Value: Free fatty acids were determined according to
primary strategic influence supporting this product trend
AOCS official method Ca 5a-40 [9].
[4]. Concentrate and ultra product lines are two popular
Saponification Value: Saponification value was mea-
fabric softening formulations existing in rinse cycle soft-
surement according to AOCS official method Cd 325 [9].
ener [7] technology. The concentrate contains 5% cationic
Iodine Value: Iodine value was determined according to
base and the ultra 25% as well as some other ingredients
AOCS official method Tg 1a-64 [9].
[8].
Titer Index: Titer test was done according to AOCS
The aim of this work was to synthesize esterquats by
official method Tr 1a-64 [9].
esterification of the palm fatty acids and TEA followed by
Determination of the cationic content in the esterquats.
a quaternization reaction using dimethyl sulfoxide (DMS).
Cationic content was determined according to ISO 2,871
The synthesized esterquats were analyzed through reversed
(1998) [10, 11] with slight modifications, i.e., using
phase high performance liquid chromatography (RP-
methylene blue instead of dimidium bromide and disulfine
HPLC) and its effectiveness was estimated on specific
blue.
fabric substrates.
Instrumental Analysis
Experimental
IR Spectrum
Materials
Infrared spectra of the synthesized diester and esterquats
were recorded between 4,000400 cm-1.
The palm fatty acids were obtained from Paxan Ind. Co.
(Tehran, IRAN). Triethanol amine (98% purity) was
GC Analysis
purchased from Arak petrochemicals (Arak, Iran). All of
other components and solvents were analytical grade and
The fatty acids methyl esters were prepared according to
purchased from Merck (Germany). The esterquat refer-
the Welcher method [12] and were analyzed according to
ence came from CECA, (France) and the Softener Sepid
AOCS official method Ce 1c-89 [9].
and Softlan brands, from Iran. Towel fabrics were
obtained from the market. All solvents used in HPLC
HPLC Analysis
analysis were HPLC grade and obtained from Merck
(Germany).
The reversed phase high performance liquid chromatogra-
phy (RP-HPLC) on a CN-column was used for separation
Instruments
and analysis of the reaction mixture [13]. The mobile phase
consisted of a 10-3 M solution of the tetraphenyl phos-
The analytical instruments used were:
phonium bromide in water and isopropanol in a ratio of
An infrared spectrophotometer model 470 (Shimadzu, 70:30 with a flow rate of 1 ml/min. The solvents were
Japan). mixed and filtered with a clarifier system before use. The
A liquid chromatography system model 10A vp column effluent was monitored by a UV-absorption mea-
(Shimadzu, Japan) equipped with a degasser (DGU- surement at 254 nm. The procedures were performed at
14AM), pump (LC-10AD vp), column oven (CTO-10A 50 C. The area normalization method was used for
vp), Spherisorb5Nitrile column (250 9 4.6 mm, 5 lm quantitative analysis.

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Preparation of Diesteramine of Palm Fatty Acids
and TEA
Palm fatty acids were mixed with TEA at a ratio of 2:1.
The reaction was carried out at 160 C in a silicon bath for
5 h under nitrogen sparge gas and a moderate vacuum for
removing the produced water.
allowed individually to feel the sets of test fabrics and rate
their softness on a scale of 1 through 5 with 1 being the
harshest and 5 being the softest. The average of the softness
rating adjudged by individual members was calculated and
is depicted by integral values 1, 2, 3, 4, 5 as per well set
assumptions.

Esterquat Synthesis Results and Discussion

The synthesized diester solution was prepared in isopro-
panol as 10 wt% solution, as the reaction medium after
cooling down to 40 C under nitrogen. Then, the mixture
was heated up to 60 C under constant stirring and DMS
was added drop-wise to the reaction mixture at a desired
molar ratio and at the desired temperature. The reaction
mixture was stirred for 3 h.
Analytical Characteristics of Palm Fatty Acids
The acid value, saponification value, iodine value, titer
index and fatty acid composition of palm fatty acids are
shown in Table 1.
Synthesis of the Diester of Palm Fatty Acids and TEA

Preparation of the Softener Formulation
Esterquat formulations were prepared at concentrations of 7
and 10 wt%. The specified amounts of esterquats were added
2 g MgCl2 (as electrolyte), 0.05 g hydrol (as preservative
and antibacterial) agent, 0.4 g Fragrance and 0.0025 g dye.
Finally, water was added up to 100 g of solution.
Performance Evaluation
Softness Evaluation
The towel fabric was cut into 10 9 10 cm2 size swatches
that were boiled with distilled water for 30 min to remove
water-soluble impurities and unreacted finishing compo-
nents. The fabric samples were dried in a drying oven at
105 C for 2 h and stored in a desiccator. They were
weighed and the appropriate volume formulation dilutions
were put into beakers, with a liquid to cloth ratio of 30:1.
The samples used to evaluate fabric properties were treated
for 20 min at 35 C [14]. After treatment, they were
removed from the beaker and were allowed to dry.
The properties of diester synthesized under different reac-
tion temperatures are shown in Table 2. The lowest acid
value diester was obtained at 160 C and was observed as
4.6. It was concluded that 160 C is the best temperature
for reaction completion, as the lowest possible acid value
was achieved at this temperature (Table 2).
Esterquats Synthesis
The quaternization of the lowest acid value diester of palm
fatty acids and TEA was carried out for 3 h. During the
quaternization, the molar ratio of the diester:DMS and the
temperature were studied as well. The diester was reacted
with varying molar ratios of DMS, i.e., 0.7, 0.95, 1.2 at 50,
60 and 70 C and the esterquats were obtained. As shown
in Table 3, the best result (53.0 1% cationic content)
was obtained at 60 C using a 1:0.95 diester:DMS molar
ratio.
Table 1 Analytical characteristic of palm fatty acids
Characteristica Value

Acid value (mg KOH/g) 201.3

Rewettability Evaluation
Iodine value (wijs) 39.8
Soaponification value (mg KOH/g) 227.9
The rewettability of the dried fabrics was evaluated
Titer index 50.0 C
according to standard methods and compared with others
Fatty acid composition wt%
and with the control [15]. The control which was a towel
C 12:0
fabric which had been treated only with water under the
C 14:0 0.84
same conditions.
C 16:0 45.58
C 18:0 5.04
Panel Feel Test for Softness of Fabric
C 18:1 40.01
C 18:2 8.53
A panel consisting of at least twenty people was asked to
a
rate the softness of the test fabric. The panel members were Average of two determinations

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Table 2 Properties of diesters of palm fatty acids and TEA synthe- Instrumental Data of Diester and Esterquats
sized at different temperature
Temperature Acid value Soaponification value IR (cm-1)
(C) (mg KOH/g) (mg KOH/g)
For diester: A peak observed at 3,370 cm-1 is due to free
140 15.7 210
-OH gp of the diester. The stretching vibration of meth-
150 7.9 200
ylene (CH2) is indicated by the peak at 2,925 and
160 4.6 199
2,850 cm-1. The peak obtained at 1,735 and 1,171 cm-1
170 12.5 203
are due to C=O ester and CO gp. of ester present in the
diester [16, 17].
Table 3 Quaternization of diester of palm fatty acids and TEA by For esterquats: IR spectra of the esterquats indicated the
DMS for 3 h similar type of peaks as in the spectra of the diester except
Temperature Molar ratio Cationic contenta the peaks at 1,223, 1,212 and 1,060 cm-1. These peaks are
(C) (DMS:Diesteramine) (%wt/wt) (2-phase titration) due to the S=O stretching vibration present in the esterquats.
50 0.7:1 29.2
Further, the presence of N? was confirmed by a peak
0.95:1 49.0
obtained at 1,005 cm-1 [18, 19]. The peak which is observed
at 3,148 cm-1 in the diester spectrum, was not obtained for
1.2:1 30.3
the esterquats. Also, the wider peak appeared at 3,370 cm-1.
60 0.7:1 30.0
0.95:1 53.0
HPLC
1.2:1 30.5
70 0.7:1 21.6
Chromatograms of diesteramines and esterquats under
0.95:1 42.1
the mentioned conditions are shown in Fig. 1. Mono, di
1.2:1 24.7
and tri basic ester amines and tri, di and mono-esterquats
a
Average of three determinations were eluted at 4.0, 5.2, 5.6, 17.2, 20.5 and 22.3 min,

Fig. 1 Chromatograms of basic

esteramines a and esterquats b

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Table 4 Performance evaluation of formulated softeners on towel
fabric
Sample Softnessa Rewettabilityb
Control 0 40
0.05% (wt/wt)
Reference 2 39
Synthesized 3 51
Sepid 3 35
Softlan 3 25
0.07% (wt/wt)
Synthesized 4 41
a
Average ranking by twenty panelists assuming 0 for the harshest
and 5 for the softest fabric samples
b cation-active matter, ISO 2871-1
Dye migration after 6 min (in mm)
respectively. The cationic content of synthesized esterquats
was determined as 52.5 1 wt% via HPLC analysis and
was comparable with data obtained by conventional
2-phase titration method (53.0 1%wt). The same samples
were used in two methods.
Performance Evaluation of the Softener
The prepared softener formulation was diluted to 0.05 wt%
and was compared with softener made by the reference
esterquat and two market samples at the same concentra-
tion. Softness and rewettability of samples on the towel
fabric were evaluated as described above. As it shown in
Table 4, the softness achieved by the synthesized softener
(0.05 wt%) was close to the market samples, but it had a
higher rewettability. A higher concentration of this softener
(0.07 wt%) gave the best softness and good rewettability.
Conclusion
The lowest acid value diester of palm fatty acid with TEA
was obtained at 160 C. The quaternization of the above
diester was carried out at 60 C for 3 h using a 1:0.95
diester:DMS molar ratio and resulted in an esterquats of
maximum cationic content, i.e. 53 1%.
The RP-HPLC analysis showed results similar to those
achieved by the conventional two-phase titration method
(T-test = 95%). The synthesized esterquats produced good
softness and rewettability in the towel fabric.
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Author Biographies
Manochehr Bahmaei earned a B.Sc. and an M.Sc. in chemistry, and
a Ph.D. (1997) in analytical chemistry from Islamic Azad University,
Tehran, Iran. In the last ten years, he has worked in chemical and
pharmaceutical research at Daroupakhsh and KianKaveb and was an
assistant profesor in Islamic Azad University. He is currently Quality
Control and Research & Development manager at Savola Behshahr
Co. His interests in research deal with oil and fats, as well as
pharmaceutical analysis, particularly chromatography.
Flora Badiee earned an M.Sc. degree (2009) in analytical chemistry
working on esterquat surfactants. Her research interest is in analytical
chemistry, particularly chromatography, related to oils, surfactants
and detergents.
Hossein Kasehgari earned a Ph.D. degree in analytical chemistry
from France in 1992. He worked at Golsan Co. and Kimia Co., and is
now Research & Development manager at Paxan Co., Iran. His
research has dealt with powder without phosphate and heavy
hydrocarbons in the past, and he is now involved in surfactants and
detergents.
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