Biorenewable Resources No.
5 / March 2008
Chemistry of Methyl Ester Sulfonates
David W. Roberts, Liverpool John Moores University, Liverpool, United Kingdom
Luigi Giusti and Alessandro Forcella, Desmet Ballestra S.p.A., Milano, Italy
Methyl ester sulfonates (MES) are anionic surfactants
with the general structure RCH(CO2Me)SO3Na. They
can be made by sulfonation of saturated fatty acid
methyl esters, RCH2CO2Me derived from natural fats
and oils (1).
Interest in MES dates back to at least the early
1960s, when there were numerous publications by
Stirton et al. from the U.S. Department of Agriculture
and numerous patents from detergent manufacturers.
Since that time interest has continued to grow,
and developments in sulfonation technology have
enabled MES to become an important part of the
formulators repertoire. Currently there is major
interest in MES because of the increasing availability
of MES feedstocks with the C 16 derivative (methyl
hexadecanoate) as the major component, as a by-
product of biodiesel production (2).
Sulfonation of methyl esters (ME) to produce MES is
a rather more complex process than sulfonation of other
major feedstocks. It is now common, with modern reactor
technology and present-day feedstock quality, to produce linear
alkylbenzene sulfonates (LAS), primary alcohol sulfates (PAS),
alcohol ethoxysulfates (AES), and alpha olefin sulfonates
(AOS) without the need for bleaching (3). In contrast,
ME sulfonation leads to very dark colored products (Klett
values well in excess of 1000) (4). Consequently all current
commercial ME sulfonation processes require a bleaching
step. Other distinguishing features of ME sulfonation are the
need for a significantly greater than stoichiometric mole ratio
of SO3 to feedstock and the need for a high-temperature aging
step.
For MES manufacture at least three stages are essential:
1. An ME/SO 3 contacting stage, in which SO 3 is
chemisorbed by the ME to give intermediate species. If
the mole ratio of SO3 to ME is significantly lower than 1.2,
full conversion of the ME cannot be achieved. This stage
is usually carried out continuously in a falling film reactor.
If the reaction mixture is neutralized at this point, much
of the ME is recovered unconverted, with conversion
of ME to sulfonated products in the range of 6075%.
The neutralized sulfonated products at this stage contain
very little MES, being mainly composed of the di-salt
RCH(CO2Na)SO3Na together with sodium methyl sulfate
(SMS) MeOSO3Na.
2. An aging stage in which the intermediate species react,
and the conversion of ME to sulfonated products goes
to completion. This aging step is much more severe
than in the aging step for linear alkylbenzene (LAB)
sulfonation, requiring temperatures of at least 80C. The
residence time required depends on the temperature, the
mole ratio of SO3 to ME, the target conversion level, and
the reactor characteristics. Thus, with a batch reactor or
an ideal plug flow reactor (PFR) and a mole ratio of 1.2,
45 minutes at 90C or 3.5 minutes at 120C should give
about 98% conversion. With an ideal continuously stirred
tank reactor (CSTR), these aging times would need to be
doubled. Usually this stage is carried out continuously in
reactors whose characteristics are intermediate between
ideal PFR and ideal CSTR.
3. A neutralization stage. If the acidic reaction mixture is
not neutralized, it deteriorates in color and, particularly
for C16 and higher ME feedstocks, becomes very viscous
and can even solidify unless heated. Neutralization on
a commercial or pilot plant scale is usually carried out
continuously in a loop reactor. It is important to avoid
extremes of pH in neutralization so as to avoid hydrolysis
of MES to di-salt. Neutralization is usually carried out to
give a ca. 60% AM paste (AM = Active Matter, in this
case consisting of MES + di-salt).
The neutralized product from a process involving
just these three stages would be a very dark colored
paste or solution with a Klett value well above 1000. The
sulfonation product would consist of a mixture of MES
and the di-salt, RCH(CO 2Na)SO 3Na, in proportions of
ca. 80:20. Sodium methyl sulfate, MeOSO 3Na, is also
present, approximately equimolar with the di-salt. The
overall reaction is shown in Scheme 1.
Depending on the formulation in which the MES is to
be used, the presence of ca. 20% of the di-salt may or may
not be acceptable. It is generally regarded as an inferior
surfactant compared with MES. Usually, therefore, two
further steps are involved:
4. Because of the high level of color produced, a bleaching
step is necessary if the product is to be used for laundry
detergents or other consumer products.
www.aocs.org / 2
 Chemistry of Methyl Ester Sulfonates
Scheme 1. Overall chemistry of methyl ester sulfonation
5. Depending on the specification required, a re-
esterification step may be included in the process,
to convert the di-salt precursor to an MES precursor.
This consists of treating the acidic reaction mixture with
methanol before neutralization, and this step can reduce
the di-salt content of the neutralized final product to well
below 10% (based on 100% active).
REACTION CHEMISTRY
Initial reactions and aging reactions
The initial reaction steps in ester sulfonation occur during the
ME/SO 3 contacting stage. Probably via complexes formed
reversibly between SO3 and the oxygen atoms of the ester, an
-sulfonated intermediate with 2:1 SO3/ME stoichiometry is
formed. This intermediate is believed to have the structure
RCH(SO 3H)COOSO 3Me (46). In the aging step, it reacts
with the remaining ME, as shown in Scheme 2. The traditional
interpretation (4) is that this is the only reaction occurring during
aging (excluding color formation, which, despite the intense
color, consumes only trace amounts of material), and that the
di-salt and SMS that are found in the neutralized material
come from residual RCH(SO3H)COOSO3Me. However, this
interpretation is inconsistent with the facts:
Scheme 2. Traditional interpretation for ME sulfonation
stoichiometry
a special supplement to inform / 3
1. If this were the only reaction, it should be possible to
achieve 100% conversion with an SO3/ME mole ratio of
1:1. This is not the case: With 1:1 mole ratio, conversion
does not increase beyond about 85% (6).
2. Kinetic plots show that there are at least two conversion-
increasing reactions taking place in the aging step, with
different rate constants (6).
Aging kinetics
A kinetic model has been developed based on the proposal
that two major intermediates are involved in aging (Scheme
3). One is RCH(SO 3H)COOSO 3Me and the other is a 3:1
adduct (or mixture of compounds with overall 3:1 SO 3/ME
stoichiometry) (6). Although this model is almost certainly
simpler than reality, it enables kinetic data to be interpreted
so as to be able to calculate aging times required for different
temperatures and different SO3/ME mole ratios.
The concentration of unconverted ME in the reaction
mixture decreases with time according to a model (6) based
on two concurrent pseudo first order reactions, one (due to
sulfonation by the 3:1 intermediate) being faster than the other
(sulfonation by the 2:1 intermediate). The rate constants kf and
ks for the faster and slower of these reactions, respectively, can
be calculated from the temperature T (K):
k = A exp (B/T)
for kf (sec1) log A = 12.10, B = 12,060
for ks (sec1) log A = 11.52, B = 12,130
The overall conversion C as a function of time t and mole ratio
M of SO3/ME is given by
C (%) = 100 M (1/M100) 0.25 exp (kst) 0.167 exp (kft)
M100 is the mole ratio that is just sufficient to give a conversion
of 100% after prolonged aging. Rounded to one decimal place,
its value is 1.2. These equations, for aging in a batch reactor
system or in a plug flow system, can be used as guidelines when
setting initial conditions before fine-tuning plant operation to
meet a required specification.
By-products
Significant levels (ca. 5% each) of two other by-products can
be detected in fresh carefully neutralized solutions of MES.
These, shown in Scheme 4, are iso-MES, RCH(CO2Na)SO3Me,
and dimethyl sulfoalkanoate (di-MES), which are easily

Scheme 3. Model for MES aging kinetics
hydrolyzed to di-salt and MES, respectively (7). Formation
of the iso-MES precursor predominates in the early part of
the aging, and the formation of di-MES predominates toward
the end of the aging period. Dimethyl sulfate also can be
detected in fresh carefully neutralized solutions of MES, at
up to 1%, but rapidly decays to undetectable levels (7). If the
acidic reaction product is treated with methanol before mild
Scheme 4. By-products of ester
sulfonation
neutralization, extra di-MES, but no iso-MES, is observed.
This suggests that the iso-MES precursor is very reactive to
methanol.
The simplest interpretation for these by-products is that
they are formed as a result of disproportionation reactions in
which the major intermediate, the mixed anhydride, acts as a
methylating agent toward sulfonate groups. In the early stages
of aging, the major species with a sulfonate group is the mixed
anhydride itself, and toward the end of the aging process, the
major sulfonate species is MES in its acid form. Scheme 5
represents the overall stoichiometry of the disproportionation
reactions. It is likely that the detailed mechanisms are more
complex than shown, involving dimethyl sulfate as the
Biorenewable Resources No. 5 / March 2008
methylating species. Dimethyl sulfate could be formed by
attack of ionized MeOSO3H on the methyl group of the mixed
anhydride.
The proposed precursor of iso-MES is the methylated
mixed anhydride (MMA). Since iso-MES is hydrolyzed to
di-salt, MMA can be regarded as a precursor of the di-salt.
The di-acid shown in Scheme 5 is also a precursor of the di-
salt. It is important to note that, since MMA does not have an
ionizable sulfonate group, it cannot undergo the reversible
intramolecular reaction to a cyclic mixed anhydride, which is
proposed as a key step in the release of SO3 during aging (see
Scheme 6). Thus, the SO3 in the form of the OSO3Me group in
MMA is not available as a sulfonating agent. The formation of
MMA explains why a 1:1 mole ratio of SO3/ME is not enough
to give complete conversion. MMA, di-acid, and di-MES are
all final products in the aging process.
Color formation
As mentioned earlier, severe color formation is a characteristic
of ester sulfonation. ME feedstocks containing unsaturated
fatty acid ME yield particularly severe colors, and these have
been attributed to the formation of poylsulfonated impurities
with conjugated double bonds (8). An unsaturated ME is an
internal olefin with a carboxymethyl group at one end of
the hydrocarbon chain. Olefins are very readily sulfonated
by SO3, much more so than saturated esters, so if a mixture
of saturated and unsaturated ME is sulfonated under MES
conditions, the unsaturated ester tends to react first, at the
double bond, and subsequently oversulfonation and oxidation
of the resulting carboxymethyl internal olefin sulfonate
compete with sulfonation of the saturated ester. In practice it
is very difficult to produce MES of good color quality, even
www.aocs.org / 4
 Chemistry of Methyl Ester Sulfonates
Scheme 5. Disproportionation reactions of the mixed anhydride
after bleaching, from an ME with an iodine value (IV) greater
than 1. Generally, the lower the IV the better, and feedstocks
hydrogenated to IV values of ca. 0.1 are preferred (1).
The foregoing should not be taken to mean that unsaturated
impurities in the feedstock are the only cause of the color
produced in saturated ME sulfonation. Even with laboratory
feedstocks having undetectable levels of unsaturation, color
formation is very severe compared with what is experienced
in, for example, LAB sulfonation. However, the color can
be removed by bleaching much more easily than when the
feedstock has IV > 1.
The following explanation for color formation from
saturated ME has been proposed (9). The major reaction
in the aging step is the conversion of the intermediate
RCH(SO 3H)COOSO 2OMe to RCH(SO 3H)CO 2Me and SO 3,
which reacts with more of the ester. The proposed mechanism
is via reversible formation of a cyclic -anhydride and
MeOSO3H, as shown in Scheme 6. As a minor side reaction,
this -anhydride may undergo reversible unimolecular ring
a special supplement to inform / 5
opening to a zwitterion, which could lose carbon monoxide to
give an alkene sulfonic acid (Scheme 6). Alkene sulfonic acids
are formed as major products in alpha olefin sulfonation, and
alpha olefin sulfonates are very susceptible to color formation
if aged in the acid form.
To suppress the unimolecular ring opening of the cyclic
-anhydride, and hence to suppress color formation, an
extra competing reaction leading to release of SO 3 should be
provided. Inorganic sulfates should serve this purpose (Scheme
6) and indeed have been shown to reduce the extent of color
formation (10, 11).
Bleaching
All MES processes require a bleaching step. Usually hydrogen
peroxide is used as the bleaching agent, and it can give good
results when used either before or after neutralization.
Acid bleaching can be carried out on the acid after the
re-esterification step, or simultaneously with re-esterification
by addition of methanol at the same time. Hydrogen peroxide,

Scheme 6. Main aging reaction mechanism, proposed color formation mechanism
usually added at 23%, is used as an aqueous solution (35 or
50%). The water introduced at this stage tends to hydrolyze the
MES acid, which would lead to substantially increased levels
of di-salt after neutralization. Residual methanol from the re-
esterification, or methanol added at the bleaching stage, can
suppress this hydrolysis and also reduces the viscosity of the
reaction mixture (1). Without addition of methanol, the di-salt
level would be too high for many applications.
Paste bleaching is in many ways simpler than acid
bleachingfor example, hydrolysis during bleaching is
not a major issuebut has sometimes been considered to
be less reliable. This is probably because the implications
of the chemistry of the by-product di-MES have not been
fully appreciated. As discussed earlier, di-MES, which has
Biorenewable Resources No. 5 / March 2008
both the sulfonate and the carboxylate groups as their methyl
esters (Scheme 4), is formed at about 5% level during the
acid aging process, and a further 5% is formed from the iso-
MES precursor if methanol is added in a re-esterification step.
Although di-MES is easily hydrolyzed, the MES neutralization
step is carried out under mild conditions, to avoid hydrolysis
of the MES, and consequently some di-MES can survive.
Di-MES is electrophilic and reacts with the nucleophilic
hydroperoxide anion, leading to depletion of the bleach. To
eliminate this source of inconsistency, the neutralized paste
can be aged before bleaching (11) to allow the residual di-
MES to be hydrolyzed. After paste aging the bleaching step
gives consistently good results that are comparable with acid
bleaching.
www.aocs.org / 6
 Chemistry of Methyl Ester Sulfonates
OCCUPATIONAL AND CONSUMER SAFETY
ISSUES FOR MES
Like all sulfonate and sulfate surfactants in their acid forms,
MES acid is corrosive. This in itself is no more of a problem
than with well-established surfactants such as LAS acid.
However, there are some special features uniquely associated
with ester sulfonates.
Firstly, the methanol injected for re-esterification and/
or acid bleaching is flammable, having a flash point of 10C
and being explosive in the range of 544% in air. Appropriate
safety procedures for storage and handling therefore need
to be followed when methanol addition is a part of the MES
process.
Secondly, if methanol recovery is part of the process,
precautions must be taken against explosions in the recovery
step, which can happen if peroxides formed in the bleaching
step build up. This is potentially more of a problem with acid
bleaching than with paste bleaching.
Thirdly, the by-products in MES acid are hazardous by
skin contact and, in the case of dimethyl sulfate, by inhalation.
Dimethyl sulfate, detectable at 1% (100% AM basis) in fresh
carefully neutralized MES solutions, penetrates skin readily
and is a carcinogen in rats. However, it does not survive long
after neutralization and is not a cause for concern regarding
consumer safety. Di-MES, present in MES acid at ca. 510%,
is a strong skin sensitizer in guinea pigs, but at levels below
100 ppm is not considered to give cause for concern on
consumer safety grounds. The 100 ppm level may be exceeded
in the freshly neutralized paste, but not in bleached paste or
in dried MES.
HYDROLYIC STABILITY
The CO2Me group of MES can undergo hydrolysis to CO2H
(acid hydrolyis) or CO2Na (alkaline hydrolysis). Thus, MES
can be hydrolyzed to di-salt or the corresponding acid.
However, due to a combination of steric and electronic
effects of the -sulfo group, the hydrolysis is slower than for
nonsulfonated esters. In the pH range 39.5 the hydrolysis
is very slow (12). Under conditions of acid bleaching with
aqueous hydrogen peroxide the pH will be below this range,
which explains why hydrolysis during acid bleaching can be
quite extensive if methanol is not added. In a neutralization
loop the pH can be controlled below 9.5 so hydrolysis can be
minimized at that stage.
Laundry powders have traditionally been made by spray
drying an aqueous slurry of the surfactants and the inorganic
salts in a spray drying tower to form the bulk of the formulated
powder. Spray drying is still widely used, but nontower routes
are now also used. Under spray-drying conditions MES
undergoes partial hydrolysis to di-salt. Thus, MES is not
suitable for formulation by spray drying. However, it can be
used as the dried solid for nontower production of powders.
a special supplement to inform / 7
SURFACTANT PROPERTIES AND APPLICATIONS
OF MES
In Table 1 critical micelle concentrations (CMC) and
Krafft points (T K) are tabulated for MES homologs and the
corresponding PAS homologs. For the sodium salts and the
calcium salts, the CMC values of the two surfactants are
similar when the same carbon numbers (excluding the methyl
carbon of the ester group in MES) are compared. However,
the TK values for sodium PAS are much higher (by over 20C)
than for the corresponding sodium MES. The difference is
even greater (by over 40C) when TK values of the calcium
salts are compared. The di-salt that can result from hydrolysis
of MES has a much higher T K value than the corresponding
MES, as illustrated in Table 1 for the C 16 homolog.
Table 1. CMC and TK for MES and linear PASa
Surfactant CMC (mmolar) TK (C) Reference
Sodium salts
C12 MES 5.3 <0 4,12
C12 PAS 8 8 14
C14 MES 2.8 6 4,12
C14 PAS 2 30 14
C16 MES 0.4 17 4,12
C16 PAS 0.40.6 45 14
C18 MES 0.080.16 30 4,12
C18 PAS 0.2 56 14
C16 Di-salt 65 4
Calcium salts
C14 MES 0.66 28 12
C14 PAS 0.68 71 12
C16 MES 0.19 41 12
C16 PAS 85 12
C18 MES 0.04 49 12
a
Abbreviations: CMC, critical micelle concentration; TK, Krafft
temperature; MES, methyl ester sulfonate; PAS, primary alcohol sulfates.
The figures in Table 1 demonstrate that for MES the
higher homologs, which are more abundant in vegetable oils
and have better detergency, are sufficiently water soluble to
be useful in low-temperature laundry products. For PAS the
higher homologs are too insoluble and the less abundant lower
homologs (C 12C 14) are more suitable for low-temperature
laundry products. It is also clear that MES is much more
calcium tolerant than PAS. The di-salt, however, is less water
soluble and less calcium tolerant.
Various detergency measurements comparing different
homologs of MES against each other and against other
surfactants have been reported (e.g., 4, 13). Such comparisons do
not always translate well into realistic consumer use situations,
but the following general conclusions can be drawn:

1. The optimal detergency with MES is for the C16 homolog
(whose parent ME will be the most abundant if the
feedstock is sourced as a by-product from biodiesel).
2. MES detergency is more resistant to water hardness than
detergency of other anionic surfactants.
3. In enzyme detergent formulations, enzyme activity is less
affected by MES than by other surfactants.
4. MES is a good lime-soap dispersant, i.e., when used as
a co-surfactant with soap in hard water it prevents the
precipitation of calcium soap.
These surfactant properties of MES are all consistent with
the concept that the polar but uncharged ester linkage, being
in close proximity to the negatively charged sulfonate group,
reduces the charge density of the latter so that electrostatic
binding to cations is weaker than in simple sulfonates and
sulfates. A similar effect, in this case the interaction between
the ether linkage and the sulfate group, underlies the differences
between PAS and AES.
Because of these properties and because of the perceived
potential for cheap availability of the feedstocks, interest
has grown in using MES, in combination with other anionic
surfactants, in laundry powders and, in markets where soap-
based products are extensively used, in combination with
soap (4). For these applications a carbon number distribution
with C 16 dominant is the optimum. Because of its mildness
to skin and mucous membranes, MES is also of interest for
dishwashing and shampoo applications, the C12/C 14 carbon
numbers being preferred (4).
ENVIRONMENTAL CHARACTERISTICS
In aquatic toxicity studies, MES has been shown to behave,
like other anionic surfactants, as a polar narcotic (15). Table
2 shows EC 50 values to Daphnia for C 12 to C 16 homologs.
C 18 MES is too insoluble to be tested alone. Intrinsically
its toxicity is greater than that of the C 16 homolog, and for
Scheme 7. MES biodegradation
Biorenewable Resources No. 5 / March 2008
tallow-based MES (C16/C18) fish toxicity EC50 values of 0.40.9
have been reported (16). However, the primary degradation
of ester sulfonates (see below) is fast and would prevent an
accumulation of toxicity.
Table 2. Daphnia toxicity of MES
MES EC50a (mg/L)
C12 184
C14 28
C16 7
a
EC50, effective concentration at which a 50% response is observed.
The biodegradation characteristics of MES are rather
similar to those of LAS. Although it is resistant to anaerobic
biodegradation, in aerobic systems MES undergoes rapid
biodegradation of the alkyl chain to a slower-degrading
residue, which is ultimately completely mineralized (16). The
biodegradation pathway is shown in Scheme 7. The initial
-oxidation step at the end of the alkyl chain is followed by
a sequence of -oxidation cycles to arrive at monomethyl
-sulfosuccinate. This undergoes desulfonation to succinic
acid, which features naturally in cell metabolism.
ESTER SULFONATES OTHER THAN METHYL
So far only ME sulfonates have been developed to the stage of
production on a manufacturing scale and for use in consumer
products. It is conceivable that a future economic situation
could arise, for example government incentives to combine
bioethanol technology with biodiesel technology to produce
ethyl ester biodiesel, where ethyl esters become attractive
as sulfonation feedstocks. The sulfonation characteristics of
ethyl esters are very similar to those of ME, although higher
temperatures or longer reaction times are required for the aging
and transesterification stages. It should be quite straightforward
to adapt an MES production operation to produce ethyl ester
sulfonates.
www.aocs.org / 8
 Chemistry of Methyl Ester Sulfonates
REFERENCES
1. Roberts, D.W., Manufacture of Anionic Surfactants, in
F.D. Gunstone and R.J. Hamilton, eds., Oleochemical
Manufacture and Applications, Sheffield Academic Press,
Sheffield, U.K., 2001, pp. 5573.
2. Ahmad, S., P. Siwayanan, Z. Abd Murad, H. Abd Aziz,
and H. Seng Soi, Beyond Biodiesel. Methyl Esters as the
Route for the Production of Surfactants Feedstock, inform
18:216220, 2007.
3. Roberts, D.W., Sulfonation Technology for Anionic
Surfactant Manufacture, Org. Proc. Res. Devel. 2:194202,
1998.
4. Schwuger, M.J., and H. Lewandowski, -Sulfomono-
carboxylic Esters, in H.W. Stache, ed., Anionic Surfactants,
Organic Chemistry, Vol. 56 in Surfactant Science Series,
Marcel Dekker, New York, 1995, pp. 461500.
5. Schmid, K., H. Baumann, W. Stein, and H. Dolhaine,
Proc. 1st World Surfactants Congress, Munich, Vol. II,
105, 1984.
6. Roberts, D.W., P.S. Jackson, C.D. Saul, C.J. Clemett, and
K. Jones, A Kinetic and Mechanistic Investigation of Ester
Sulphonation, Proc. 2nd World Surfactants Congress,
Paris, Vol. II, 3841, 1988.
7. Roberts, D.W., C.J. Clemett, C.D. Saul, A. Allan, and
R.A. Hodge, Intermediate By-products in Methyl Ester
Sulphonation, Jorn. Com. Esp. Deterg. 26:2733, 1995.
a special supplement to inform / 9
8. Yamada, K., and S. Matsutani, Analysis of the Dark
Colored Impurities in Sulfonated Fatty Acid Methyl Ester,
J. Am. Oil Chem. Soc. 73:121125, 1996.
9. Roberts, D.W., The Origin of Colour Formation in Methyl
Ester Sulphonation, Jorn. Com. Esp. Deterg., 37:153159,
2007.
10. United States Patent 6,657,071, to Lion Corporation.
December 2, 2003.
11. United States Patent Application USSN61/026,174,
Desmet Ballestra S.p.A., February 8, 2008.
12. Stein, W., and H. Baumann, -Sulfonated Fatty Acids
and Esters: Manufacturing Process, Properties, and
Applications, J. Am. Oil Chem. Soc. 52:323329, 1975.
13. Satsuki, T., Applications of MES in Detergents, inform 3:
10991108, 1992.
14. Domingo, X., Alcohol and Alcohol Ether Sulfates, in H.W.
Stache, ed., Anionic Surfactants, Organic Chemistry, Vol.
56 in Surfactant Science Series, Marcel Dekker, New
York, 1995, pp. 223312.
15. Roberts, D.W., S.J. Marshall, and G. Hodges, Quantitative
Structure-Activity Relationships for Acute Aquatic
Toxicity of Surfactants, World Surfact. Congr., 4th, 4:
340351, 1996.
16. Gode, P., W. Guhl, and J. Steber, kologische Bewurtung
von -Sulfofettsauremethylestern, Fat Sci. Technol.
89:548552, 1987.