Professional Documents
Culture Documents
SCHEME 2
SCHEME 3
with alkyl sulfates are already employed because of the The final product has to be bleached and neutralized,
good crystallization of alkyl sulfates. Extension of the giving a yellowish paste with about 65% active matter.
application of LAS to cosmetics was suggested by the Sulfochlorination. The sulfochlorination technol-
use of the milder Mg salts [32]. ogy [37,38] is used for the conversion of paraffins or
alkanes to alkane sulfonates. In a photochemically in-
2. Aliphatic Sulfonates
duced reaction, the paraffin is contacted by dry sulfur
(a) Alkane Sulfonates. Sulfoxidation and sulfochlor- dioxide and chlorine:
ination are the core technologies for the preparation of h
alkane sulfonates. Sulfoxidation, the older process, is (>400 nm)
RH ⫹ SO2 ⫹ Cl2 → RSO Cl ⫹ HCl
more important than sulfochlorination. 20–40⬚C 2
SCHEME 5
tions, and hydrolysis, a mixture of hydroxyalkane sul- tants, showing good detergency for the C16 –C18 MES
fonates and alkene sulfonates is obtained in a ratio of event at low temperatures.
30:70. The sulfonation is quite a complex reaction (Scheme
As far as surfactant properties are concerned, the 6). Beside the desired ester sulfonate, MES contains
alkenyl sulfonate is the more desirable structure. In any methyl sulfate, ␣-sulfo fatty acids, and soap in amounts
event, bleaching of the final product is necessary be- that depend on the manufacturing process. The first
cause of oxidation side reactions. step is the insertion of SO3 into the ester linkage (Fig.
Because of the discussion of sultone intermediates 4).
[42], the use of AOS was limited. Through modern The primary reaction product, a mixed anhydride,
analytical methods, the sultones can be quantified, and can take up a second molecule of SO3 via its enol form.
the production process has been modified by adding a The anhydride carrying two SO3 units can lose one
hydrolysis step, so that sultones need not be mentioned SO3, which can react with another molecule of methyl
as a noteworthy component of AOS. The product can ester. This ‘‘storage’’ of SO3 is the reason for the nec-
be regarded as safe for the consumer and the environ- essary excess of SO3 in this sulfonation reaction. The
ment. AOS with a C14–16 alkyl chain is better foaming whole reaction sequence takes more time than is avail-
than C16–18 AOS. The sulfonate group gives high sta- able with a falling-film reactor. Therefore, in order to
bility over a wide pH range. AOS is sensitive to water achieve a high degree of sulfonation, aging is neces-
hardness. Typical applications are in detergents, sham- sary. During the subsequent neutralization, the inter-
poos, and cleansers [43–47].
␣-Sulfo fatty acid methyl esters (MESs). Starting
materials for ␣-sulfo fatty acid esters are fatty acid
methyl esters, which are available from the transester-
ification of natural oils and fats. This low refined oleo-
chemical raw material is sulfonated with SO3/air. Ester
sulfonates [48–59] are economically interesting surfac- SCHEME 6
mediate anhydride of the ␣-sulfo acid is hydrolyzed to Both mono- and diesters are obtained in a two-step
the disodium salt. To avoid this, hydrolysis of the ␣- process. In the first reaction step, maleic acid anhydride
sulfo acid anhydride with methanol is carried out. To is esterified with compounds containing hydroxyl
achieve good color, bleaching of the sulfonic acid with groups to the mono- or diester (Fig. 6). Diesters are
hydrogen peroxide is necessary. The color of MES is mainly produced with alcohols. For monoesters, many
dependent on the ester raw material. Raw materials different raw materials with hydroxyl groups are used,
with low iodine values (<0.1%) are suitable for the e.g., fatty alcohols and their ethoxylates and fatty acid
process. alkanol amides and their ethoxylates [60]. Usual ester-
The same reaction can be carried out with fatty ification catalysts such as p-toluenesulfonic acid are
acids, giving directly the disodium salt of the ␣-sulfo suitable as catalysts for diester production.
acid, which is of no industrial importance. In the second reaction step, the maleic acid ester is
Sulfosuccinates. Sulfosuccinates (sulfosuccinic sulfonated with an aqueous sodium hydrogen sulfite so-
acid esters) are anionic surfactants based on maleic acid lution to obtain the corresponding sulfosuccinate (Fig.
anhydride. One distinguishes mono- and dialkyl esters 7). In the case of the sulfosuccinic acid monoester, two
of the sulfosuccinic acid (Fig. 5). regioisomeric sulfosuccinates are possible (Fig. 8). It
was detected by 1H nuclear magnetic resonance (NMR)
analysis that the  position is preferred during sulfo-
nation. The /␣ ratio is approximately 4:1 (Henkel
KGaA, unpublished results).
Sulfosuccinates are used in many different fields of
application. Comprehensive overviews have been pub-
FIG. 5 Structure of sulfosuccinic acid esters. R1, R2 = H, lished [60,61–63]. Sulfosuccinic acid dialkyl esters are
alkyl, POE-alkyl. weakly foaming surfactants with good wetting power.
In particular, products based on n-octanol or 2-ethyl succinic acid monoalkyl esters are, for example, used
hexanol are distinguished by their outstanding wetting as emulsifiers in emulsion polymerization. Both the
properties. Therefore, they are applied as ‘‘rapid wet- mono- and dialkyl esters are readily biodegradable and
ting agents’’ in the textile industries [64]. In fiber have low toxicity [60].
technology, these products are used in spinning oils
for nylon production. Furthermore, they are used in 3. Alcohol Sulfates (ASs)/Alcohol Ether
agriculture for pesticides as well as in paint formula- Sulfates (AESs)
tions and in the leather industry. With regard to house- Through conversion of alcohol ethoxylates with sulfa-
hold products, the application of sulfosuccinic acid di- tion agents, alcohol ether sulfates [68] are obtained. On
alkyl esters is restricted to specific glass cleaners, e.g., a large technical scale, ether sulfates are produced
for spectacle lenses or glass panes, as well as carpet mainly in a continuous process through mild conver-
shampoos. sion with sulfur trioxide in a ‘‘multitube falling-film’’
In contrast to sulfosuccinic acid dialkyl esters, sul- reactor. The importance of sulfation with chlorosul-
fosuccinic acid monoalkyl esters are good-foaming sur- fonic acid has diminished considerably.
factants, especially products based on ethoxylated fatty The reaction with SO3 leads primarily to a pyro-
alcohols, e.g., lauryl or myristyl polyoxyethylene (3) sulfate:
alcohol, which exhibit outstanding skin compatibility
[65]. Because of their mildness to skin, large quantities R — (O — CH2 — CH2)n — OH ⫹ 2SO3(g)
of sulfosuccinic acid monoalkyl esters are used in per-
→ R — (O — CH2 — CH2)n — OSO2OSO3 H
sonal care products such as shower gels, shampoos, and
skin-cleaning agents. In particular, they are utilized in The pyrosulfate primarily obtained is metastable and
mild products such as baby shampoos or shampoos for decomposes very rapidly in the presence of further al-
sensitive skin. Their compatibility is very good, not cohol into the desired sulfuric acid half-ester:
only on sensitive skin but also on diseased skin [66].
Sulfosuccinic acid monoalkyl esters are very soluble in R — (O — CH2 — CH2)n — OSO2OSO3 H
water and have good hard-water resistance with a low
tendency to form calcium soaps. They exhibit high de- ⫹ R — (O — CH2 — CH2)n — OH
tergency that is synergistically enhanced in combina- → 2R — (O — CH2 — CH2)n — OSO3H
tions with other surfactants [67]. Because of the hydro-
lysis-sensitive ester bond, their application is limited to The next step is neutralization with an aqueous solution
a pH range of 6 to 8. In the industrial sector, sulfo- of the respective base, e.g., NaOH, KOH, or NH4OH,
FIG. 7 Reaction scheme to sulfosuccinates. R1, R2 = H, al- FIG. 8 Regiometric isomers of sulfosuccinic acid mono-
kyl, POE = alkyl. alkyl ester. R = alkyl.
nut or tallow-based feedstocks. A main drawback of the 1930s by the former IG-Farben and still have value as
sulfation process for alkanol amides is the high viscos- mild cosurfactants and as specialty primary surfactants.
ity of the sulfation mixture, which may be overcome
by means of cosulfation with lower molecular weight 1. Isethionates
alcohols [105], alkanol amines [106], fatty alcohols Isethionates [118] are mild cosurfactants and are es-
[107], or oxethylated fatty alcohols [108]. Because of pecially used in syndet bars. The largest market is the
a lower sulfation temperature, the products obtained by United States with about 20–30,000 tons per annum.
this route have an improved color. The choice of cati- The most common product has a C12 –C18 alkyl chain
ons comprises ammonium (including alkyl and alkanol derived from coconut oil. The most recent development
ammonium), alkali, and alkaline earth metals. in isethionates was the ammonium cocoyl isethionate
Sulfated alkanol amides are excellent foaming sur- [119], which is an alternative to the poorly soluble so-
factants with good detergency [109]. Their hydrolytic dium salt with regard to liquid formulations.
stability as well as physicochemical data have been The condensation of fatty acid with sodium isethio-
cited elsewhere [100]. Sulfated alkanol amides are used nate can be carried out in the presence of an esterifi-
almost exclusively as cosurfactants together with an- cation catalyst in a temperature range above 180–
ionic, nonionic, and sometimes cationic components. 200⬚C.
Cosmetics (body, hair, and baby care) and manual
dishwashing are the main fields of application because HO — CH2 — CH2 — SO3Na ⫹ R — CO2H
catalyst
of the low skin irritancy of alkanol amide sulfates →
⫺H O
R — CO2 — CH2 — CH2 — SO3Na
2
[110], which was observed during the late 1960s [111].
Alkanol amide sulfates are good lime soap disper- An alternative route is the reaction corresponding to
sants and have thus been used in detergent composi- Schotten-Baumann with an acid chloride and sodium
tions suitable for hard-water applications [112]. isethionate:
Technical applications concerning emulsion poly-
merization of ethylenically unsaturated monomers HO — CH2 — CH2 — SO3Na ⫹ R — COCl
[113] or leather preparations [114] are related to the
favorable emulsifying properties of sulfated alkanol → R — CO2 — CH2 — CH2 — SO3Na ⫹ HCl
amides. Sulfated alkanol amides have also been used The direct esterification route is more economical than
as mold release [115] or antiadhesive reagents for the acid chloride route, but it yields a larger amount of
rubber [116]. Together with cationic surfactants, al- unreacted fatty acid.
kanol amide sulfates may serve as dehydration pro-
motion agents for the production of granular slag [117]. 2. Taurates
Taurates [120,121] also belong to the class of fatty acid
C. Fatty Acid Condensation Products
condensation products and can be prepared using the
Fatty acid condensation products have a long history. same reaction pathways as isethionates. The most com-
Most of the products were developed during the early mon preparation starts with Na-N-methyltaurate:
Protein/fatty acid condensates are used mainly as Generally applied synthesis methods are ‘‘phospha-
mild surfactants in cosmetics, in the textile industry, tions’’ by means of phosphorus pentoxide. The reaction
and in laundry or dishwashing detergents. is very complex and may occur as follows (Scheme 7).
The postulated molar ratio is obtained only if the
D. Phosphoric Acid Derivatives phosphorus pentoxide used is of a highly pure grade.
Another group of anionic surfactants with a significant Because phosphorus pentoxide always contains poly-
market potential are phosphoric acid esters. They are phosphoric acid, at best a mole ratio of 1.2:1 mono-
based on fatty alcohols as well as on oxethylated al- to diester is available. For the same reason, the final
cohols [135] and may be used for special applications products often include pyrophosphates and o-phos-
such as emulsifiers, wetting agents, antistats, lubricants, phoric acid, which are formed in subsequent steps as
flotation auxiliaries, and corrosion inhibitors. follows, where polyphosphoric acid reacts with an al-
Regarding chemical properties, partial phosphoric cohol (Scheme 8).
acid esters show marked stability to hydrolysis except The pathway just described is also suitable for the
in strongly acidic conditions. The sensitivity to hard preparation of monoalkyl phosphates, although they are
water is a real disadvantage for this surfactant class. always accompanied by o-phosphoric acid and, de-
Sometimes, compensation may be possible by appli- pending on the amount of alcohol, pyrophosphoric
cation of phosphoric acid esters based on oxethylated acid. The latter may be hydrolyzed by treatment with
alcohols. water at elevated temperatures.
Most of the practically used derivatives are mixtures Triesters based on oxethylated alcohols, which are
of mono- and diesters; triesters are present only as mi- used as cosmetic emulsifiers for ointments, creams, or
nor components (Fig. 14). lotions [136], can be produced by the reaction of al-
SCHEME 7
SCHEME 9
Technical alkylene oxide derivatives always have a (BRE = broad range ethoxylates, Fig. 16). However, it
distribution of oligomers or polymers with a mean de- should be noted that special catalysts can be applied
gree of polymerization, reflecting the mole ratio of the resulting in a narrow distribution (NRE = narrow range
reaction of alcohol and EO. The product is not uniform ethoxylates, Fig. 17).
in composition but has a distribution of homologues The difference between BRE and NRE products
that strongly depends on the type of catalyst used from an application point of view is not as great as one
[141]. Conventional alkaline catalysts such as KOH might have predicted. The problem with NRE is the
[142] or NaOMe give a relatively broad distribution higher manufacturing expenditure and costs, making
FIG. 16 Homologue distribution of broad-range ethoxy- FIG. 17 Homologue distribution of narrow-range ethoxy-
lates. lates.
SCHEME 11
SCHEME 14
the case of castor oil ethoxylated with 40 moles of
ethylene oxide, the product composition has been an-
alyzed [172]. solubilizers, and antistat additives. This application
Besides the preceding ethoxylation products, higher range varies from cleaning and detergent formulations
esters were identified in which the secondary hydroxyl to additives in gasoline and drilling fluids.
group is esterified with ricinoleic acid. Surprisingly, the
degree of ethoxylation of the secondary hydroxyl group
B. Amine Oxides
was rather low. Ethoxylated glycerol esters are used
widely in the cosmetic industry, e.g., for emulsification, A special class of surface-active substances are amine
solubilization, refatting, thickening, improvement of oxides, which belong in the class of nonionic compo-
the dermatological properties of basic surfactants, and nents. This classification is true, however, only under
improvement of skin feel [173]. Castor oil or hydro- alkaline and neutral conditions. In acid solutions they
genated castor oil ethoxylates play an important role in react weakly to form cationics.
body care applications and as solubilizers or emulsifiers The synthesis of amine oxides happens relatively
in pharmaceutical formulations. simply by the reaction of tertiary amines with hydrogen
peroxide in an aqueous medium according to Scheme
5. Ethoxylated Amines and Alkanol Amides
15. Because of the oxidizing environment, amine ox-
The synthesis of ethoxylated amines can be separated ides sometimes contain nitroso amines, which are sus-
into two reactions [174,175]. In the first step an amine pected of being carcinogenic. References [178–182]
is reacted with ethylene oxide to an amino alcohol in describe manufacturing methods to avoid these unde-
such a way that every H atom of the amine reacts with sirable by-products.
one ethylene oxide molecule (Scheme 13). The second The foaming, wetting, and cleaning properties as
step is the growth of the polyoxyethylene chain through well as the ecotoxicological aspects of C12 –C18 alkyl
reaction of more ethylene oxide with the hydroxyl dimethylamine oxides have been discussed previously
groups of the amino alcohol (Scheme 14). Whereas in [183]. Also, good thickening performance is men-
the first reaction step no catalyst is necessary, the sec- tioned.
ond step requires a catalyst such a sodium or potassium Amine oxides are very important emulsifiers for
hydroxide. many applications in which the reemulsification of ab-
The most commercially available surfactants pre- sorbed components must be prevented. Such an appli-
pared by this method are the fatty amine ethoxylates. cation is possible because of the decomposition of
Another class of ethoxylated amines are the ‘‘Jeff- amine oxides at temperatures above 100⬚C to yield ole-
amines’’ and the ‘‘Tetronics.’’ Jeffamines are prepared fins and derivatives of hydroylamine (Scheme 16). This
by first ethoxylating a short-chain alcohol or glycol. reaction is taken advantage of, for example, in the ap-
This alcohol ethoxylate is then aminated to generate an plication of waterproofing agents to textiles.
amine [176,177]. Tetronics are made by ethoxylation An interesting variety is the thermal decomposition
of low-molecular-weight diamines, e.g., ethylenedi- of amine oxides that are based on ethers of dimethyl
amine. These products are tertiary amines and often ethanolamine [184]. The vinyl ethers formed are
consist of mixtures of ethylene oxide and propylene known as reactive olefins [185]. Produced from a base
oxide adducts. of dimethyl ethanolamine esters, the preparation of vi-
Ethoxylated amines have a wide range of applica- nyl esters becomes possible (Scheme 17).
tions [178]. They are used, for example, as emulsifiers,
use of renewable resources. Whereas the derivatization source. These include sucrose from sugar beet or sugar-
of fats and oils to produce a variety of different sur- cane, glucose derived from starches, and sorbitol as the
factants for a broad range of applications has a long hydrogenated glucose derivative (Table 1). Most in-
tradition and is well established [186], the production dustrial developments in the field of sugar-based sur-
of surfactants based on fats, oils, and carbohydrates on factants have concentrated, and still concentrate, on
a larger industrial scale is relatively new. The following these carbohydrate feedstocks.
will discuss the most important carbohydrate-based
surfactants, such as sorbitan esters, sucrose esters, alkyl
A. Sorbitan Esters
polyglucosides, and fatty acid glucamides, with pri-
mary focus on the glucose-derived products. Sorbitan esters have been known for decades since the
Considering the amphiphilic structure of a typical first industrial processes were established for their man-
surfactant with a hydrophilic headgroup and a hydro- ufacture. One differentiates between a one-stage and a
phobic tail, it has always been a challenge to attach a two-stage process (Fig. 18). In the first process, water
carbohydrate molecule as the perfect hydrophilc group, is eliminated from sorbitol as a first step to form sor-
due to the numerous hydroxyl groups, to a fat and oil bitan, which is subsequently derivatized with fatty acid
derivative such as a fatty acid or a fatty alcohol [187]. as a second step. In the second process, both reactions
Although scientists have reported numerous ways of are carried out simultaneously [188]. Both methods
making such linkages and have also described a large have been developed for industrial scale production.
number of different carbohydrates used in such reac- Depending on the type and amount of fatty acid used,
tions, it is clear from an industrial perspective that only different types of sorbitan esters (e.g., laurates, oleates,
a few carbohydrates fulfill the criteria of price, quality, or stearates) are produced with hydrophilic-lipophilic
and availability to be an interesting raw material balance (HLB) values in a range of 1 to 8. To modify
SCHEME 16
SCHEME 17
FIG. 18 Synthesis of sorbitan esters by intramolecular dehydration of sorbitol in the presence of acid (e.g., NaH2PO3) at about
150–200⬚C and subsequent base-catalyzed (e.g., Na2CO3) esterification with fatty acids (RCOOH) at 200–250⬚C.
Production capacity,
Surfactants Manufacturers Fields of application world (t/a)a
FIG. 20 Synthesis of sucrose esters by base-catalyzed (K2CO3) transesterification with fatty acid methyl esters (R⬘COOMe),
usually carried out in solvents (e.g., dimethyl formamide at ⬃90⬚C) or microemulsions.
than the actual market potential, which is estimated to from C8 to C16. The result of the reaction is a complex
be less than 4000 tons per annum. However, demand mixture of alkyl mono-, di-, tri-, and oligoglycosides
and market volume could increase substantially if re- as a mixture of ␣- and -anomers (Fig. 24). Therefore,
action processes, especially for the synthesis of high- the industrial products are called alkyl polyglycosides.
mono products, can be further optimized. The products are characterized by the length of the al-
kyl chain and the average number of glucose units
C. Glucose-Derived Surfactants linked to it—the degree of polymerization (DP) [192].
The crucial point with regard to the development of
The first step in overcoming the problem of nonselec-
an industrial process was to establish reaction condi-
tive derivatization of carbohydrates was achieved when
tions that allowed the manufacturing of high-quality
Emil Fischer discovered the reaction of glucose with
products under safe and economically acceptable con-
alcohol to form alkyl glucosides [190]. The glucosi-
ditions. This was achieved by optimizing the reaction
dation reaction is highly selective because of the hemi-
parameters temperature, pressure, reaction time, and ra-
acetal function in the glucose molecule and the result-
tio of glucose to fatty alcohol. Of equal importance was
ing high reactivity of the hydroxyl group at C-1. The
the design of a special distillation technology to re-
same is true for the synthesis of fatty acid glucamides.
move the excess fatty alcohol as smoothly as possible,
Here the glucose molecule reacts initially with meth-
as well as appropriate bleaching and stabilization in the
ylamine, which, after hydrogenation, selectively yields
final treatment step (Fig. 25). This so-called direct syn-
the glucamine as an intermediate [191]. Further deri-
vatization with fatty acid methyl ester leads to the de- thesis of alkyl polyglycosides is the currently preferred
sired product. manufacturing mode. However, two-stage processes
have been developed as well and are used, for example,
1. Synthesis of Alkyl Polyglycosides by Hüls AG on a pilot plant scale. The breakthrough
The first syntheses of alkyl polyglycosides were carried in the production of long-chain (C12/14) alkyl polygly-
out more than 100 years ago. In the course of further coside occurred in 1992 with the inauguration of an
developments, the reaction of glucose with alcohols approximately 25,000 tons per annum production plant
was applied to long-chain alcohols with alkyl chains for APG surfactants by Henkel Corporation in the
United States and in 1995 with the opening of a second and products for industrial, institutional, and personal
plant of equal capacity by Henkel in Germany. care cleansing (Table 2).
Today, the main producers of alkyl polyglycosides
are Cognis, Seppic, ICI, Kao, Union Carbide, and 2. Fatty Acid Glucamides
BASF with an estimated total production capacity of The synthesis to produce fatty acid glucamides in-
approximately 80,000 tons per annum. The main ap- volves the reaction of glucose with methylamine, under
plications for the C12/14 alkyl polyglycosides are liquid reductive conditions, to form the corresponding N-
dishwashing agents and detergents and personal care methylglucamine. In a subsequent reaction step, this
products. For the C8/10 (or branched C8) alkyl polygly- intermediate is converted with fatty acid methyl ester
cosides, there are hard surface cleaners, agrochemicals, to the corresponding fatty acid amide. Compared with
the alkyl polyglycosides, fatty acid glucamides are cant amounts of unreacted N-methylglucamine, which
composed of only a single carbohydrate molecule at- could be considered as potential precursors for nitro-
tached to the fatty acid chain (Fig. 26). This is one samines, Procter & Gamble has developed an optional
reason why fatty acid glucamides are less soluble and reaction with acetic anhydride in the finished product.
tend to crystallize more easily from aqueous solutions. Free secondary amines can be acetylated in this step,
Figure 26 shows the manufacturing scheme for the and the resulting acetates can remain in the final prod-
production of fatty acid glucamides. To avoid signifi- uct [193].
The existing production capacity is estimated to be ferences in specific product formulations. If, for ex-
30,000 to 50,000 tons per annum active substance ac- ample, the stability of concentrated manual dishwash-
cording to a study by Colin A. Houston & Associates ing detergents is investigated, as in the case of a paste
[194]. Producers are Pfizer, Hatco in the United States, based on alkyl ether sulfate and alkyl polyethylene gly-
and Clariant (formerly Hoechst) in Germany (Table 2). col ether, it is found that best results are obtained when
alkyl polyglycosides are used as cosurfactants (Table
3. Properties of Alkyl Polyglycosides and 3) [196]. In general, glucose-derived surfactants have
Fatty Acid Glucamides shown to be very efficient components in manual dish-
With regard to their basic physicochemical properties, washing detergents and liquid and powder detergents
such as surface and interfacial tension and critical mi- [196]. In contrast to alkyl polyglycosides, fatty acid
celle concentration, alkyl polyglycosides and fatty acid glucamides are thus far not known in applications other
glucamides (C12/14) are very comparable. There are than detergents.
slight differences in the basic foam behavior for the In personal care products, alkyl polyglycosides rep-
pure sugar-based surfactants as well as binary combi- resent a new concept in compatibility and care. They
nations. With regard to their ecological, toxicological, may be combined with conventional components and
and dermatological properties, alkyl polyglycosides as can even replace them in new types of formulations,
well as fatty acid glucamides can be considered as sur- leading to a broad spectrum of supplementary effects.
factants with extraordinary product safety characteris- With regard to foam, they are comparable to betaines
tics. This has been proved for both products in a series and sulfosuccinates but do not match the foam volume
of detailed investigations. The results are published in of alkyl ether sulfates. On the other hand, alkyl poly-
several papers, mainly by Henkel and Procter & Gam- glycosides can stabilize the foam of anionics in hard
ble but also by independent research institutes [195]. water and in the presence of sebum. The alkyl poly-
Although it can be concluded that alkyl polygly- glycoside foam consists of finer bubbles and is more
cosides and fatty acid glucamides are more or less creamy than in the case of SLES (Fig. 27) [197a].
comparable with regard to their basic performance in To demonstrate the large performance spectrum of
detergents and dishwashing agents, there might be dif- alkyl polyglycosides, one more application should
be mentioned briefly. Alkyl polyglycosides (C8/10 and Because alkyl polyglycosides are available in suffi-
C12/14) have been shown to be substitutes for alkyl phe- cient quantities and at competitive costs at present,
nol ethoxylates in agrochemical formulations. They their use as a raw material for the development of spe-
lead to higher salt tolerances and show good results as cialty surfactants has generated considerable interest.
adjuvants in several post applied herbicides, such as The derivatization of alkyl polyglycosides is currently
control of giant foxtail in soybeans with Assure II being pursued with a goal to modify the surfactant
(DuPont) and control of common lambsquarters in soy- properties of alkyl polyglycosides [192b,199]. A broad
bean with Pursuit (American Cyanamid). Currently, the range of alkyl polyglycoside derivatives can be ob-
short-chain products (C8/10 and C9–11) are approved as tained by using relatively simple methods, for example,
inert ingredients by the U.S. Environmental Protection nucleophilic substitution. In addition to the reaction to
Agency (USEPA) [198]. esters or ethoxylates, ionic alkyl polyglycoside deriv-
atives, such as sulfates and phosphates, can be synthe-
D. Derivatives of Alkyl Polyglycosides sized. However, only a few products are established in
the market: methylglucoside esters and a series of spe-
In principle, two different approaches exist to combine cial esters based on alkyl polyglycosides.
a hydrophobic alkyl chain with the hydrophilic glucose
molecule. These are glycosylation, the reaction of glu- 1. Methyl Glucoside Esters
cose with an alcohol as described earlier, and acylation, Esterification of methyl glucoside with methyl esters of
the esterification or amidation of a suitable glucose de- stearic or oleic acid enhances the lipophilic character
rivative, such as the alkyl polyglycosides. (Fig. 28). Methyl glucoside esters are, in contrast to
SCHEME 20
SCHEME 21
[212]. Inorganic as well as organic acids with a weak As per the following, a further interesting route for
or strong character and even partial esters of polyvalent the preparation of polyquaternary compounds should
acids are suitable. The optimal reaction temperature is be mentioned. Oxethylated fatty amines are polycon-
approximately 80⬚C. It should be mentioned that no densed with dicarboxylic acids, i.e., adipic acid [213],
strong acids force the formation of dioxane as a by- and afterward quaternized with ethylene oxide [214]
product if ethylene oxide was applied. Also, alkylene (Scheme 25).
glycols are always present. Because of hydrolysis re- Most of the quaternization reactions here are per-
actions, ester amines are unsuitable for this preparation formed with ethylene oxide or propylene oxide as well.
method. Analogous works with long-chain epoxides normally
failed because of the heterogeneity of the aqueous
mixtures with the tertiary amine salts. This problem,
however, has been solved [215] by the use of a phase
transfer catalyst (PTC) such as dimethyl distearyl am-
monium chloride. Because of its versatility, many other
reaction systems are conceivable (Scheme 26).
Another class with minor technological importance
are the so-called betaine esters. The somewhat mis-
FIG. 31 Cationic protein derivative. leading name can be traced back to the property that
SCHEME 23
SCHEME 24
SCHEME 25
SCHEME 26
SCHEME 27
of the latter types [220] describes a pathway in which i.e., C12 –C18, or pure C12 are prominent. Because of
amine oxides are formed as intermediates. difficult handling, long-chain betaines play only a sub-
Because of the variety of cationic surfactant types, ordinate role.
it is impossible to make generally binding statements The synthesis proceeds relatively simply according
about toxicity within the scope of a short review. Only to the following reaction (Scheme 28). In principle, the
a few aspects should be highlighted. reaction must be understood as a quaternization reac-
Sometimes, the alkyl chain length may be respon- tion of a tertiary amine with monochloroacetate as an
sible for toxicological effects. A comparison between alkylating reagent. A high degree of conversion occurs
behenyl and stearyl derivatives regarding eye and skin only under the assumption that during the alkylation
irritation showed that the behenyl chain dramatically process, the salt form of chloroacetic acid is present
lowers irritation potential [221]. because the free acid would block the amine function.
Because of their excellent biodegradability, ester Therefore, weakly alkaline conditions, analogous to the
quats show moderate aquatoxicity (Biological Labora- dissociation degree of chloroacetic acid, are recom-
tories of Henkel KGaA, private communications, mended. Also, a slight excess of chloroacetate, usually
1988). Also, human toxicity with regard to skin and the sodium salt, increases the yield. Depending on the
mucous membrane irritation, acute toxicity (oral/der- type of tertiary amine used, a reaction temperature of
mal), mutagenicity, and sensitization has been evalu- 70–95⬚C is required. Normally, the reaction is carried
ated as very low for ester quats with long alkyl chains. out in an aqueous solution resulting in a final concen-
Medium-chain (C8 –C12) ester quats, however, may act tration of 30% betaine. Because of a tendency to ge-
as biocides, as may other quaternary ammonium salts latinize, slightly higher betaine concentrations may be
with a comparable alkyl chain length range. possible only by adding special hydrotropes, such as
polyols or fatty acids [223,224].
VI. AMPHOTERIC SURFACTANTS Besides the alkyl betaines already shown, alkyl-
amidopropyl betaines (Fig. 33) are the predominant
A. Betaines commercialized types. The preparation is a two-step
It was approximately 1969 when betaines were pro- process. First, fatty acids or their esters (glycerides or
posed as cosurfactants for shampoo formulations [222]. methyl esters) are condensed with, usually, dimethyl-
The mildness to skin and eyes has been the decisive aminopropyl amine, followed by reaction with sodium
reason. choroacetate [225] (Scheme 29). For a quantitative
Regarding the chemistry, betaines are homologues yield of intermediate, a redistillable excess of amine
of trimethyl glycinate, which was discovered more than should be applied. The reaction temperature is limited
a century ago in sugar beet (Beta vulgaris) juice. The by the amine boiling point of approximately 140⬚C.
general structure is depicted in Fig. 32. The residue R The following betainization reaction takes place under
normally represents an alkyl or an alkylamido popyl conditions similar to those described before.
group based on coconut or palm kernel oil. The main Usually, the sodium chloride generated remains in
carbon chain distribution includes the C8 –C18 range. the betaine solution. Sometimes, however, special ap-
Sometimes products with a narrower chain distribution, plications require salt-free products. For this reason, the
SCHEME 28
SCHEME 30
SCHEME 31
reaction is carried out in an alcoholic solution with sub- Another commercial betaine type is the sulfobetaines,
sequent filtration of the precipitated salt [226,227] or also called sultaines. They are prepared similarly to the
by means of ultrafiltration methods [228] (N. Kühne common types with chlorosulfonates instead of chloro-
and G. Uphues, unpublished results, Henkel KGaA, acetate, usually 1-chloro-2-hydroxypropane sulfonate
1991). [230], as alkylating reagents (Scheme 30). In earlier
With regard to other by-products and trace impuri- times, propane sultone was the agent used for the man-
ties, environmental and product safety is becoming ufacture of sulfobetaines. The high carcinogenic poten-
more and more relevant. A partial hydrolysis of mono- tial of sultones, however, prohibited the use of such
chloroacetate is responsible for a small content of substances more than 20 years ago (Scheme 31).
harmless glycolic acid. Careful control of reaction con- Of somewhat academic interest may be a synthesis
ditions limits the amount. Concerning the removal of route described for the preparation of sulfato betaines
critical impurities, i.e., free amines and monochloro- [231]. According to this method, a tertiary amine is
and dichloroacetic acid, some hints are given in Ref. reacted with sulfur trioxide followed by an insertion
229. reaction of ethylene oxide. Ethylene or propylene car-
bonate is used as an inert solvent (Scheme 32).
SCHEME 34
SCHEME 35
SCHEME 36
1. Physicochemical Behavior
The particular properties of amphoteric surfactants are
related to their zwitterionic character. That means that
both anionic and cationic structures are found in one
molecule. Differences between betaines and true am-
photerics are caused by changing behavior at several
SCHEME 37 pH values.
Regardless of the pH value, betaines permanently
represent a four-bonded nitrogen atom. Only at a very
The methyl ester groups are hydrolyzed under pressure low pH value can the anionic group be protonated to
with various quantities of caustic in an autoclave, pro- take on a cationic character.
ducing only sodium salts or mixtures of both salt and Unlike betaines, true amphoterics form salts at pH
acid groups (Scheme 38). values higher than the isoelectric point. At lower pH
Unfortunately, the methanol generated cannot be re- values, the basic nitrogen is protonated and the mole-
moved completely by less expensive methods. As mod- cule behaves like a cationic surfactant. So it is under-
ern cosmetic products require methanol-free ingredi- standable that true amphoterics show the best applica-
ents, the so-called propionates are prepared by the tion results outside the isoelectric range.
addition of acrylic acid. This alternative procedure is The amphoterics are mainly used as cosurfactants
restricted by the fact that only diadducts can be ob- for cosmetic shampoo or dishwashing formulations,
tained. Usually, the reaction is carried out in a neutral where they provide mildness to skin and hair, espe-
aqueous solution forming the monosodium salt cially in blends with alkyl and alkyl ether sulfates. An-
(Scheme 39). other advantage is compatibility with most ionic sur-
Another route for the manufacture of salt-free true factants. In addition, the general surfactant properties,
amphoterics is the addition of acrylic acid to ring- i.e., wetting power, cleansing ability, foaming power,
opened imidazolines. As the addition reaction runs hard-water tolerance, and lime soap dispersibility, are
slower than the shift of the acyl group just mentioned, excellent.
essentially mono adducts are obtained (Scheme 40).
The specialized literature shows numerous other 2. Ecological and Toxicological Behavior
types and synthesis methods for amphoterics, but they A coco betaine, a cocoamidopropyl betaine, and a co-
have found only small or no commercial interest. coamphoacetate were extensively tested with regard to
SCHEME 38
SCHEME 39
SCHEME 40
Sensitization
Type of amphoteric Acute toxicity Irritation to Irritation to (Magnusson- Gene mutation NOAELb
surfactant (rat) skina (rabbit) eyea (rabbit) Kligman test) (Ames test) (mg/kg)