J Surfact Deterg (2008) 11:181–186
DOI 10.1007/s11743-008-1069-3
ORIGINAL ARTICLE
Performance of U-Sulfo Fatty Methyl Ester Sulfonate Versus
Linear Alkylbenzene Sulfonate, Secondary Alkane Sulfonate
and a-Sulfo Fatty Methyl Ester Sulfonate
Leon Cohen Æ Fernando Soto Æ Ana Melgarejo Æ
David W. Roberts
Received: 22 January 2008 / Accepted: 18 March 2008 / Published online: 3 June 2008

AOCS 2008
Abstract Sulfoxidation of fatty acid methyl esters with
SO2, O2 and ultraviolet light of appropriate wavelength, has
led to the synthesis of methyl esters sulfonates or sulf-
oxylates, known as U-MES, because of the possible
random position of SO3 group in the alkyl chain. Aqueous
solutions based on the sulfoxylated methyl ester of palmitic
acid (U-MES C16) have been studied and compared to the
leading types of surfactants used today: linear alkylbenzene
sulfonate (LAS) secondary alkane sulfonate (SAS) and a-
sulfo fatty methyl ester sulfonate (a-MES) with regard to
solubility, performance and skin compatibility. The
experimental results obtained indicate that U-MES C16 can
be regarded as a potential component of detergent formu-
lations and most likely also of body care products.
Keywords Wetting
Foaming properties

Anionic surfactants
Introduction
Our research group has been working since 1993 on sulf-
oxylated fatty acid methyl esters, called here U-sulfo fatty
methyl ester sulfonates (U-MES). Sulfoxidation is the
addition of sulphur dioxide and oxygen in the presence of
UV light of appropriate wavelength to some organic
L. Cohen (&)
F. Soto
A. Melgarejo
Escuela Politécnica Superior de Algeciras.,
Universidad de Cádiz, Avda Ramon Puyol,
11202 Algeciras, Spain
e-mail: leon.cohen@uca.es
D. W. Roberts
Liverpool John Moores University, Liverpool, UK
compounds, such as aliphatic hydrocarbons or fatty acid
methyl esters.
The sulfoxidation reaction proceeds through a radicalic
mechanism unlike the a-MES traditional sulfonation,
which proceeds through an electrophilic substitution. Due
to the reaction mechanism, a characteristic of these com-
pounds is that the sulfonate group is randomly distributed
along the alkylic chain, ‘‘this being the reason they are
named U-MES’’.
U-MES exhibit [1–3] properties that make them attrac-
tive as anionic surfactants, namely:
• Good water solubility, which makes them easy to
include in liquid formulations.
• Very low viscosity of their aqueous solutions, which
makes them easy to handle and pump.
• Very good wetting power
• Excellent water hardness stability, which allows them
to be formulated in hard water regions.
• Excellent skin compatibility, which makes them poten-
tially very good for hand dishwashing formulations and
most likely for body care products.
• Expected excellent biodegradation.
• Good detergent power.
In a previous paper [2], performances of U-MES with
varying chain lengths were compared. Two main conclu-
sions were drawn: the palmitic acid U-MES (U-MES C16)
could be used as an LAS partner in detergent formulations
and the C16 alkyl chain was the optimal length. Since then,
progress has been made concerning the development of a
procedure for the separation of reaction products [4] and
analysis [5, 6]. These investigations have led to products
with fewer impurities.
It has therefore been judged worthwhile in the present
work, to present the results of standard experimental tests,
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that have allowed us to compare the performance of the

REACTOR OUTLET
most common commercial anionic surfactants such as LAS
(linear alkylbenzene sulfonate), SAS (secondary alkane
sulfonate) and a-MES (a-sulfo fatty methyl ester sulfonate)
to U-MES C16. Hot water Separation

Materials and Methods

Methanol Water Phase Non reacted
• ME C16 (palmitic acid methyl ester). ME C16, (CE- addition Methyl ester
1695) from Procter & Gamble Chemicals, USA, with
99 wt.% of C16:0 alkyl chain Hexane Extraction
• U-MES C16 sodium salt. This product was obtained in
our laboratory according to a modification of the
methodologies described previously [1, 4]. Methanol-Water Hexane Phase
Phase
Update. According to the water procedure described in
Ref. [4] after the separation of the non-reacted methyl
ester, a small amount of dissolved methyl ester and some Neutralization Hexane recovery
Methanol removal
fatty acid remains in the aqueous phase, and these have to
be removed in order to improve the final product quality. Scheme 1 Analytical Scheme work
An updated procedure, that we present for the first time,
has been implemented. • a-MES C16–C18. A commercial sample of C16–C18
As mentioned in Ref. [4], the reactor outlet is mixed (50/50 wt%) concentrated powder with 97% monosulf-
with an equivalent amount of water and the two phases are onate purity, from Desmet Ballestra, Italy.
left to separate at 60 C in the oven. The upper layer is
composed of unreacted methyl ester while the lower phase
is the water solution containing mono and polysulfonic
Results and Discussion
acids as well as some dissolved methyl esters and most
likely a small amount of fatty acid.
Solubility
After separation of both phases, the unreacted methyl
ester can be used for a new run and the water solution will
Turbidity points, defined as the temperature at which an
follow further treatment consisting in adding the same
aqueous solution of surfactant becomes turbid on cooling,
amount of methanol as the volume of water. The mixture is
were measured for the different surfactants as seen in
then transferred to a liquid–liquid extractor as the one
Fig. 1. Turbidity points were determined by cooling, in a
depicted in Ref. [4] and the extraction is carried out during
thermostated bath, solutions of defined surfactant concen-
8 h with a non polar solvent such as n-hexane.
tration until they became cloudy or turbid. For the same
In the hexane phase all the dissolved fatty acid and
surfactant concentration, the lower the turbidity point
methyl ester are recovered, while the water–methanol
temperature the higher the solubility in water, since the
solution is distilled under a slight vacuum and all the
surfactant solution remains clear at lower temperatures. It
methanol recovered. The remaining water solution is then
must be remembered that turbidity point is the immediate
neutralized with sodium hydroxide and concentrated as
previous step to crystallization.
desired.
In Fig. 1, the best results correspond to SAS and LAS,
As mentioned above, basically, the modification con-
while U-MESC16 has acceptable solubilities.
sisted of the use of a mixture of methanol–water 50/50 v/v
All a-MES solutions were cloudy, because these prod-
and hexane, to perform the extraction of dissolved impu-
ucts are not water soluble at laboratory temperatures
rities. The detailed analytical procedure is depicted below
(18 C). Therefore, in this case, cloud points were mea-
in Scheme 1.
sured after heating the solutions until they became clear
• LAS sodium salt. A commercial sodium sulfonate and then cooling them.
sample derived from Petresul 550 acid manufactured U-MES C16, SAS and LAS are all double chain sur-
by Petroquı́mica Española, Spain. factants, in each case consisting of mixtures of isomers,
• SAS sodium salt. A commercial cut of C14–C17 sample where the lengths of the two chains vary. In SAS and LAS
of Hostapur SAS 93 from Clariant Germany. both chains are n-alkyl, but in U-MESC16 the chains are

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Solubility (Turbidity Point) sphere of the SO3 group which is at the a carbon. Moreover
Temp. (°C)
the ester group hinders the sulfonate group and decreases
30
Surf.Conc. its interaction with water.
25 25%
20% Stability to Water Hardness
20
15%

15
10
5
0
Φ-M ES C16 LAS SAS αMES
-5
-10
Fig. 1 Solubility at different surfactant concentrations
different from each other, one being n-alkyl and one being
terminated by a CO2Me group. The hydrophobicity of
SAS, LAS and U-MES C16 is lower than would otherwise
be expected (water solubility higher), because of the water
sharing effect between the two chains, described and
modeled quantitatively in [7, 8]. The magnitude of the
water sharing effect is different for each isomer.
LAS is a mixture of C10–C13 homologues where each
homologue is a mixture of different isomers with a phenyl
ring attached to the alkyl chain at different positions.
SAS is a mixture of C14–C17 homologues, each
homologue being a mixture of different isomers, depending
on the position of the SO3 hydrophilic group.
Apparently SAS has a higher water solubility than LAS
and this may be due to the fact that SAS isomers are more
soluble than LAS ones because of the presence in the latter
of the six carbon atoms of the benzene ring.
U-MES C16 is less soluble than LAS and SAS, probably
because, among other factors, as it is already well known, a
pure homologue is less soluble in water than a mixture of
homologues with the same molecular weight, because of
synergic interactions between homologues and isomers in
the mixture. As mentioned above we have to bear in mind
that LAS and SAS are both mixtures of homologues with a
significantly higher number of isomers than the single U-
The determination of the stability to water hardness ions
was carried out according to UNE-55-507-72, the Spanish
standard equivalent to the widely used stability test (DIN
53905 or ISO-1063/79). In the Spanish test, five surfactant
solutions with increasing concentrations are tested for each
water hardness level. In this test, a number ranging from 1
to 5 is assigned to surfactant solutions with varying cal-
cium concentrations, depending on the apparent turbidity
and precipitate formation: five denotes clear solutions, four
opalescent, three turbid, two precipitate, one precipı̀tate
excess. According to the latter, 25 is the maximum value
for each hardness level. As seen in Fig. 2, U-MES C16
shows the highest tolerance to water hardness (numbers are
the sum of the five surfactants concentrations tested for
each water hardness level).
Due to the above depicted structure of U-MES C16,
SAS and LAS molecules, crystallization of the calcium salt
is more inhibited with U-MESC16 than it is with SAS and
LAS.
Concerning a-MES, since distilled water solutions of a-
MES are turbid even at low surfactant concentrations, we
cannot measure absolute stability but the relative one,
(meaning that, even though the stability number is neces-
sary low, its value doesn’t change when water hardness
increases) and as seen in Fig. 2, a-MES is not affected by a
water hardness increase from 150 to 650 ppm. The reason
why the single chain surfactant a-MES is reasonably
STABILITY to WATER HARDNESS
Points
25
ppm CaCO3
20 300
20 19 19
450
600
15
15 14 14

MES C16 homologue.

11 11 11 11
In order to explain the very low water solubility of a- 10
10
MES C16–C18, we have to consider that it is a mixture of 8

two linear single chain surfactants (C14 and C16)1, each

with a CH(CO2Me)SO3 head group. In this case the 5
CO2Me group does not reduce the hydrophobicity of the
carbon chain as in U-MES, being within the hydration
0
Φ- MES C16 LAS P-550 SAS αMES C16-C18
1
We don’t count the C attached to the SO3 group and we don’t count
the C’s of the CO2Me group. Fig. 2 Water hardness tolerance according to UNE-55-507-72

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hardness tolerant (at the higher hardness concentrations it WETTING POWER 1 g/l
350
is more tolerant than SAS and LAS) is because there is
15 0 300 300 300 300 300 300
some hindrance or shield effect of the CO2ME group, 300 40 0
which results in a weaker interaction with calcium ions, in 65 0
particular with 2Ca++. On the other hand, Satsuki [9] 250 ppm C aC O3 228

claims that LAS and most likely SAS, are very sensitive to

seconds
200
calcium concentration because of the production of a liquid
crystalline calcium salt which is insoluble. a and probably 150
U MES form a calcium salt that exists in a metastable state,
so that might be the reason why methyl ester sulfonates in 100

general, can be regarded as ones of the most hardness 50

50
tolerant surfactants. 21 15
12
7
0
Φ-MES C16 LAS P-550 SAS α MES C16-
Foaming Power C18

Foam height. The Ross–Miles test was conducted at 49 C.
and 1 g/l of surfactant at three different levels of water
hardness expressed as ppm of CaCO3. Experimental results
are represented in Fig. 3.
U-MESC16 gives the best results together with LAS. A
water hardness increase has less effect on both U-MESC16
and a-MES than on LAS and SAS. This can be explained
based on stability to water hardness of U-MESC16 and a-
MES (which reaches a maximum at 1 g/l and 400 ppm),
compared to SAS and LAS.
Foam stability. According to the Ross–Miles test, foam
stability is given by the foam height variation after 5 min.
The results show that all the surfactants show a similar
variation after 5 min.
Fig. 4 Wetting time (Draves Test) at 20 8C as a function of water
hardness
Wetting Power
The Draves test was conducted and 1 g/l of surfactant
concentration used at three water hardness levels.
According to the experimental results plotted in Fig. 4, U-
MES C16 is by far the best wetting agent, specially at a
higher water hardness. According to Rosen, since the rate
of wetting is a function of the surface tension of the wetting
front, the wetting power of a surfactant is a function of the
concentration of molecularly dispersed material at the
front, so we can utilize the same argument used for dish-
washing, in the sense that more monomers exist in solution.

Dishwashing
Initial Foam Height 1 g/l
80 The method used gives a stability index for foam generated
72 using a certain type of soil, in our case a mixture of olive
70
70 150 ppm oil 75% and lard 25%, at a definite surfactant concentration
64
400 ppm [10] and 49 C. A correlation exists between the stability
60 index and a hypothetical number of dishes washed
56 56 650 ppm
53 53
ppm CaCO3 according to the typical dishwashing manual test. A choice
50
has been made so that the value 50 is an indication when
the number of dishes washed is above 50. The results
mm

40
plotted in Fig. 5, show that the best performance is reached
31 with U-MES C16 at medium water hardness. This probably
30
23 23
reflects the higher CMC of U-MES C16 due to the lower
22
micellar radius (particularly compared to a-MES), which
20
means that more monomer is in solution to replenish the
12
10
foam.

0 Skin Compatibility
Φ-MES C16 LAS P-550 SAS α MES C16-
C18
Zein test. The Zein test, a widespread screening in vitro test
Fig. 3 Foam height (t = 0) at 49 8C as a function of water hardness for the evaluation of skin irritancy of surfactants, was used.

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DISHWASHING TEST 0.5 g/l ZEIN TEST

600 564
60
526

500
50 50 50 50 50
50 Surf.
400 Conc.

mgN2/100ml
0,50%
40 300 288
1%
N° Dishes

255
2,50%
150 ppm
200
30 400 ppm 190 164
136
650 ppm 109 169 108
22 100
ppm CaCO3 63
85
20
14 0
13
12 Φ -MES C16 LAS P-550 SAS α MES C16-
C18
10
6
5 5
Fig. 6 Zein test versus surfactant concentration. Zein protein
concentration : 2 g/40 mL
0
Φ MES C16 LAS P-550 SAS α MES C16-C18

the presence of the ester linkage in the hydrophobe portion

Fig. 5 Number of washed dishes at 49 8C as a function of water
hardness
The test is based on the solubilization of the water-insol-
uble zein protein by surfactants. Solubilization of zein is
measured through the determination of nitrogen content of
the solubilized protein, giving the so-called Zein number.
According to Kaestner and Frosch [11], the ability of a
surfactant to dissolve the water-insoluble zein protein
correlates very well with in vitro test data. Irritation of
human skin is due to the formation of a complex between
the protein present in the skin and the surfactant. Accord-
ing to Seibert and Bolsterdorf [12] the extent to which a
combination of anionic surfactant and protein takes place
depends on many factors. Only surfactant monomers or
submicellar species penetrate membranes, whereas
micelles would presumably be too large to penetrate.
Apparently a reduction of critical micelle concentration
(CMC) results in lower levels of free monomers; therefore,
surfactants with high CMC penetrate faster.
The nitrogen content of the solubilized protein gives the
so-called Zein number which classifies anionic surfactants
into: \200 mg N/100 ml: nonirritant; 200–400 mg N/
100 ml: moderate irritant; [400 mg N/100 ml: strong
irritant.
The results plotted in Fig. 6, show that U-MES C16
sodium salt is nonirritant up to 2.5 wt% and can be com-
pared favorably to LAS, SAS and a-MES and gives similar
results to AES [1].
We see that a-MES is much less irritant than LAS and
SAS, which can be explained by the shield effect of the
CO2Me group as mentioned earlier. Even if U-MES C16
has a higher CMC than a-MES, its lower Zein number may
reflect weaker hydrophobic binding to the protein, due to
of U-MES C16. In a-MES, the ester linkage is within the
hydration sphere of the sulfonate group and leaves intact
the hydrophobic binding of the chain.
References
1. Cohen L, Trujillo F (1998) Synthesis, characterization and sur-
face properties of sulfoxylated methyl esters. J Surfactants
Detergents 1:335–341
2. Cohen L, Trujillo F (1999) Performance of sulfoxylated fatty acid
methyl esters. J Surfactants Detergents 2:363–365
3. Cohen L, Soto F, Luna MS (2001) Sulfoxylated methyl esters as
potential components for liquid formulations. J Surfactants
Detergents 4:147–150
4. Cohen L, Soto F, Luna MS (2001) Separation and extraction of
U-methyl ester sulfoxylate: new features. J Surfactants Deter-
gents 4:73–74
5. Cohen L, Soto F, Luna MS, Roberts DW, Saul CD, Lee K,
Williams E, Bravo JE (2002) Derivatization GC-MS, LSIMS and
NMR analysis of sulfoxylated methyl esters. Tenside Surfactants
Detergents 39:78–83
6. Cohen L, Soto F, Luna MS, Pratesi CR, Cassani G, Faccetti L
(2003) Analysis of sulfoxylated methyl esters: sulfonic acid
composition and isomers identification. J Surfactants Detergents
6:151–154
7. Roberts DW (2000) Aquatic toxicity—are surfactant properties
relevant? J Surfactants Detergents 3:309–315
8. Roberts DW (2004) Environmental risk assessment of surfac-
tants: quantitative structure activity relationships for aquatic
toxicity. In: Zoller U (ed) Handbook of detergents: part B envi-
ronmental impact. Dekker, New York, pp 271–298
9. Satsuki T et al (1998) Effect of calcium ions on detergency.
Tenside Surfactants Detergents 35:112–117
10. Soler J (1984) Proceedings of the XV Jornadas del Comité Es-
pañol de la Detergencia. Barcelona, Spain, pp 139–169
11. Kaestner W, Frosch PJ (1981) Fette-Seiffen und Anstrichmittel
83:33
12. Seibert K, Bolsterdorf D (1988) Magnesium surfactants—as
contribution to mildness, Proceedings of the 2nd CESIO World
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Author Biographies
Dr. Leon Cohen received his Ph.D. in chemistry at Sevilla Univer-
sity. In 1994, he earned the EURCHEM designation. He worked for
PETRESA from 1970 to 1996. Since 1989 he has been a Professor of
Chemical Engineering at the University of Cadiz, where he has led
the research group on ‘‘Surface Activity and Detergency’’ since 1993.
He is the author of more than 25 papers, more than 40 contributions to
Congresses, and has four patents related to detergency.
Dr. Fernando Soto received his M.Sc. in chemistry at the Sevilla
University and his Ph.D. in Chemical Engineering in 2001 at Cadiz
University. He has been a Professor of Chemical Engineering at the
University of Cadiz, since 1979. He has been a member of the
research group on ‘‘Surface Activity and Detergency’’ since 1994.
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J Surfact Deterg (2008) 11:181–186
Ana Melgarejo received her B.Sc. in Chemical Engineering at Cadiz
University in 2007.
Dr. David W Roberts received his Ph.D. in Chemistry from Man-
chester University, UK, in 1965. He is a Fellow of the Royal Society
of Chemistry and has the EURCHEM designation. He worked for
Unilever Research from 1967 to 2003. Since 2003 he has been a
consultant in Manufacturing and Toxicological Chemistry and is an
honorary researcher at John Moores University in Liverpool. He is the
author of more than 100 papers in the fields of surfactant science and
toxicology.