International Journal of Cosmetic Science 19, 239–253 (1997)

Amphoteric surfactants: processing, product

composition and properties
H . I . L E I D R E I T E R , B . G R Ü N I N G and D . K A S E B O R N
The Goldschmidt AG, D-45116 Essen, Germany
Presented at the SCS Symposium Bristol 7–8 April 1997: ‘Surfactants, the Workhorse of the Cosmetic
Industry’

Keywords: cocamidopropyl betaine; sodium cocoamphoacetate; disodium cocoamphoacetate

Synopsis
Cocamidopropyl betaine (CAPB) has been the most important secondary surfactant for personal-cleansing
products for a long time. Its excellent toxicological profile is an important reason for its increasing use in oral-
care products. Recently it has gained interest for further applications such as household cleaners, dish-washing
liquids, and industrial and technical products. Imidazoline-derived amphoterics such as sodium cocoampho-
acetate (SCAA) or diacetate play a more minor role than CAPB. Owing to the low irritation potential of the pure
surfactant and its good toxicological properties, ampho-acetates have mainly found applications in cosmetics.
Their industrial applications have been relatively small. While CAPB has a well-defined chemical structure from
a straightforward production process, most imidazoline-derived amphoterics exhibit a complex composition of
compounds with different structures. This depends on the production parameters. Improved processing methods
have recently led to the commercial availability of well-defined SCAA with low levels of by-products. Modern
production processes and the composition of high-purity amphoterics are reviewed. Raw materials and by-
products are described, together with their analytical methods. The cosmetic performance, cleansing and
foaming power, rheological effects and mildness-enhancing properties of both CAPB and SCAA are
compared.

Résumé
La cocamidopropyl-bétaı̈ne (CAPB) est, depuis longtemps le tensio-actif secondaire le plus important pour les
produits d’hygiène personnelle. L’excellent profil toxicologique de la CAPB est certainement une raison
majeure de son usage croissant dans les produits de soin buccaux. La CAPB a suscite depuis peu un intérêt pour
des applications supplémentaires telles que les nettoyants ménagers, les liquides vaisselle, les produits
industriels et techniques. Les dérivés amphotères de l’imidazoline tels que le cocoampho-acétate de sodium
(SCAA) ou le diacétate occupent une place mineure comparée à la CAPB. En raison du faible potentiel irritant
du tensio-actif pur et même de bonne propriétés toxicologiques, les ampho-acétates trouvent principalement
leurs applications dans les cosmétiqes. Leur rôle dans les applications industrielles est relativement limité. Alors
que la CAPB a une structure chimique bien définie à partir d’un procédé de production direct, la plupart des
dérivés amphotères d’imidazoline présentent une composition complexe de composés aux structures différentes.
Ceci dépend des paramètres de production. Des procédés de production améliorés ont récemment conduit à une
disponibilité commerciale de SCAA bien définis avec de faibles teneurs en produits secondaires. Les procédés
modernes de production et la composition d’amphotères de grande pureté sont décrits. Les matières premières
et les produits secondaires sont décrits ainsi que leurs méthodes d’analyse. Le comportement cosmétique, le
pouvoir nettoyant et moussant, les effets rhéologiques et les propriétés adoucissantes sont comparés, à la fois
pour la CAPB et le SCAA.

Introduction
Presently there are many different washing and foaming surfactants in toiletries available
on the market, but there are only a handful of different products with a considerable market
share. The most important raw materials are the anionic surfactants such as lauryl sulphate
0142–5463 © 1997 International Journal of Cosmetic Science
240 Leidreiter et al.
and lauryl ether sulphate. In conjunction with these efficient and cost-effective basic
surfactants, a range of secondary surfactants has been established. In general, secondary
surfactants are used to improve the properties of base surfactants and to optimize the
performance of the final product. Since the beginning of the 1950s imidazoline-derived
amphoteric surfactants have gained increasing interest as cosmetic ingredients. The main
reasons for this are the good toxicological properties [1], its low irritation potential and
good mildness-enhancing ability. These are commonly known as cocoamphoglycinates
(INCI/CTFA name: sodium cocoamphoacetate or disodium cocoamphodiacetate). Now-
adays the most important secondary surfactant is undoubtedly coco fatty acid amidopropyl
betaine (INCI/CTFA name: cocoamidopropyl betaine) [4,5] which has an excellent toxico-
logical profile [6]. Since its introduction into the market in the 1960s this product has sur-
passed the success of SCAA and has become essential in modern surface-active formulae.
Combining primary surfactants like sodium laureth sulphate (SLES) with CAPB or
SCAA reduces irritation to skin and mucous membrane [7,8,9,10] and leads to a pleasant
feeling. Moreover the formulations are easier to thicken and develop a more pleasant foam.
CAPB is known to give a better cleansing performance [11] and to improve the
conditioning properties of hair shampoos [12,13]. The use of CAPB in very efficient,
particularly mild dish-washing agents and oral hygiene products are the latest examples of
the great interest taken in CAPB.
In spite of the widespread use of amphoteric surfactants there is little comprehensive
documentation of their synthesis, analysis and their minor components [14]. By reviewing
the routes of synthesis, we will report on composition and by-products, and analytical
determination of the components.

Production methods
The methods of production of fatty acid amidopropyl betaines and ampho-acetates
basically follow schemes which have proved valid for a long time. The first step is the
formation of the fatty acid amide and the second is carboxymethylation in aqueous
medium. For both types of amphoteric surfactants the production processes are similar.
Amide formation
Alkoylamidopropyl dimethyl amine for betaine. In the first step, 3-aminopropyldimethyla-
mine (DMPA) is reacted with fatty acids, fatty acid methyl esters or directly with natural
fats (fatty acid glycerol esters), which are predominantly used in their hydrogenated form
(Fig. 1). Factors affecting the choice of fatty raw materials are their availability and the
desired application properties of the fatty acid amidopropyl betaine.
The type of fat used, mainly hydrogenated coconut oil or occasionally hydrogenated
palm kernel oil, determines the fatty acid composition of the betaine, which thus
corresponds to that of the oil. The typical fatty acid composition of coco fatty acid betaine
is shown in Table 1.
When starting with fat, glycerol is formed as a by-product. As it has no negative effect
on most applications, and may even be desired, it can remain in the product. Thus a
glycerol content of 2–3% in commercial betaine solutions is normal. A part of the glycerol
can be removed from the amidoamine by phase separation. In this way betaine solutions
with low glycerol contents of around 1% can be obtained. The separated glycerol has to be
suitably disposed of.
Amphoteric surfactants 241

Figure 1. Betaine production: amidation R-CO- 5 fatty acid residue, R' 5 H, CH3 or
derived from glycerol.
Table I. Typical fatty acid composition of coconut oil
derived amphoterics
Fatty acid (C-atoms) Weight-% (approx values)
8 7
10 6
12 49
14 19
16 9
18 10

An excess of DMPA is used in the amidation reaction, and it can be reduced in the final
amidoamine product by distillation down to very low levels, e.g. 0.05%.
Instead of natural oils, fatty acids and fatty-acid methyl esters with fatty-acid
compositions corresponding to that of natural oils can be used for the production of
betaines. Also betaines with special fatty-acid compositions can be made. Examples are
betaines from topped fatty acids which contain no or only very few short chain
components, lauric acid amidopropyl betaine, and caprylic/capric acid amidopropyl
betaine.

1-(Hydroxyethyl)-2-alkyl imidazoline for amphocetates. Aminoethylethanol amine (AEEA)

is reacted with either fatty acids, fatty-acid methyl esters or directly with natural fats (Fig.
2).
The possible choice of fatty material for amphoacetate production is the same as for
betaine. The commercially available amphoacetates generally are based on hydrogenated
coco fatty acid, so the fatty-acid composition shown in Table 1 is typical for coco-
amphoacetates as well. When starting from fatty acid, no glycerol is formed as a by-
product.
Excess AEEA has to be used in the amidation reaction to obtain complete conversion of
the fatty acid to the amide, and it also helps avoid the formation of diamides – these are
insoluble in aqueous systems and therefore cause turbidity or precipitation of the final
product.
In the course of amidation, water is continuously removed from the reaction mix.
Finally the imidazoline compound is formed. As the last step in production, the excess of
AEEA is removed by distillation.
242 Leidreiter et al.

Figure 2. SCAA production: amidation.

Carboxymethylation
All amidoamines (fatty acid ester or fatty acid derived) contain small amounts of non-
amidated fatty acids which are then carried over into the final product. The carbox-
ymethylation is carried out in aqueous medium with chloroacetic acid (MCA) or its
sodium salt.

Betaine
The reaction of alkoylamidopropyl amine with MCA (Fig. 3) directly leads to the betaine
which is normally obtained as a 30% aqueous solution. Sodium chloride, formed as a by-
product, is present in most betaine solutions at a level of approximately 5%. Apart from
the reaction with the tertiary nitrogen atom, chloroacetic acid can also be hydrolysed in a
side reaction which leads to the formation of glycolic acid. The glycolic acid content can
reach levels of over 1% in the betaine solution, but normally considerably lower (e.g.
0.1%).
During the last few years, research on the production of betaines has mainly
concentrated on the improvement of production processes. These efforts have focused
predominantly on manufacturing purer products, i.e. minimizing by-products. Other efforts
have focused on increasing the concentration or reducing the water content in betaine

Figure 3. Betain production: 2. carboxymethylation, R-CO- 5 fatty acid residue.

Amphoteric surfactants 243
solutions. This means that all these efforts essentially refer to the carboxymethylation
step.
As the tertiary amines are consumed during the carboxymethylation the pH value is
reduced considerably during the reaction. The reaction rate slows down proportionally
because the free amine is removed from the reaction medium not only by carboxymethyla-
tion but also by protonation. By maintaining an alkaline pH value through the whole
reaction the carboxymethylation can be carried out faster and more completely so that less
amidoamine remains in the final product [15]. In this way an amidoamine content of less
than 0.3% in betaine can be obtained. Some types of CAPB have higher amidoamine
contents of up to 3% for special application reasons.
Chloroacetic acid and dichloroacetic acid, which is present in chloroacetic acid in small
amounts, are unwanted by-products in betaine – and of course also in other zwitterionic or
amphoteric surfactants like amphoglycinates – because of their negative toxicological
properties. Whereas chloroacetic acid is used up almost completely during the smoothly
proceeding carboxymethylation reaction, dichloroacetic acid is almost inert under the
typical reaction conditions. If betaine is submitted to further post-treatment steps the
residual chloroacetic acids can further be reduced. This can be achieved either by reaction
at alkaline pH or by additional treatment with ammonia or amino acids [16] which will
predominately reduce the amount of monochloroacetic acid. Another possibility is the use
of sulphonating reagents [17]. Finally both mono- and dichloroacetic acid can be
hydrolytically decomposed simply by treatment at higher temperatures (.120°C) [18].
Thus levels of mono- and dichloroacetic acid of ,5 ppm or ,10 ppm respectively can be
realized. There are, however, only very few products on the market which fulfil the purity
requirements for modern CAPBs, namely amidoamine content ,0.3%, monochloroacetic
acid ,5 ppm and dichloroacetic acid ,10 ppm.
Based on weight, the most important components of the commercial aqueous coco fatty
acid amidopropyl betaine solutions are the betaine itself and sodium chloride. In general
sodium chloride is left in the solution since it does not interfere with most applications. In
fact it is even desired for the build-up of viscosity in ready-to-use preparations such as
shampoos. For special applications there are also betaine types with reduced salt contents.
This can be achieved by using solvents or separation processes by membranes.
Most commercial CAPB solutions contain approximately 30% active matter. This is due
to the fact that aqueous betaine solutions form non-flowable, gel-like phases at slightly
higher concentrations. In contrast to surfactants like lauryl ether sulphate, at higher
concentrations fluid mesophases consisting of CAPB, sodium chloride and water do not
exist. The critical concentration above which non-flowable gel phases are formed depends
partly on the length of the alkyl chains of the fatty acid. This is shown in Fig. 4 in which
this relationship is demonstrated using the example of solutions composed of stoichio-
metric amounts of fatty acid amidopropyl betaine and sodium chloride.
Numerous attempts have been made to obtain flowable betaine solutions with increased
active matter [14]. In some of these other surfactants have been added. Other ways of
acheiving higher concentrated betaines are the use of solvents or additional salts which
normally are not contained in betaine solutions, e.g. sodium citrate, trimethylglycine [19]
or nitrilotriacetate.
There is a relatively simple way of obtaining higher concentrated betaine solutions – by
adjusting to a specific content of free, not covalently bound, fatty acid [20]. As small
amounts of fatty acid are brought into the betaine with the amidoamine, this opens an
244 Leidreiter et al.

Figure 4. Flowability of aqueous betaine solutions, liquid and gel phase, T 5 25°C.

elegant way – avoiding extreneous additional components – to produce higher concen-

trated betaines with betaine contents of 34–36% and contents of wash-active substance
including the fatty acid of 36–38%. The increase in concentration has an importannt
positive side effect: such betaine solutions are microbiologically stable and do not require
preservatives.
By spray-drying aqueous betaine solutions, betaine products of highest concentration are
obtained, typically consisting of 80–85% fatty acid aminopropyl betaine, 13–15% sodium
chloride and 0.3–3.0% water.
The route of production of betaine means that commercial solutions contain by-products
in the CAPB, whose determination is important for the characterization of the betaine
quality. We will review the determination of the components in the following sections.

Amphoacetates. The imidazoline compound is carboxymethylated in alkaline aqueous

medium with chloracetic acid or its sodium salt. The reaction leads to sodium alklyampho-
acetate, which is normally obtained as a 30% aqueous solution. Sodium chloride, formed
as a by-product, is present at a level of approximately 6%. In Fig. 5 the reaction is split
into two steps to show possible intermediates arising from splitting the imadazoline ring.
In modern production processes of SCAA two important measures are taken to obtain a
high-purity final product: a small excess of MCA, and the continuous monitoring and
adjusting of the pH value during the reaction process. In this way it is possible to obtain
a concentration of amido hydroxyethyl amine below 1% in the final product.
Under the conditions of the carboxymethlation reaction the imidazoline ring is opened
forming mainly the primary amido derivative as final product. A secondary amido
derivative, shown without final carboxymethylation in Fig. 5 is of minor importance. This
Amphoteric surfactants 245

Figure 5. Amphoacetate production: 2. carboxymethylation.

compound occurs only in small ratios of about 10% of the total active compounds. A true
disodium cocoamphodiacetate cannot be obtained by this process. Only the secondary
amido derivative can be carboxymethylated by a second equivalent of MCA. This reaction
step is obtained already by the small excess of MCA in the production of a high-purity
monoacetate. The only relevant difference between commercial disodium cocoamphodi-
acetates and sodium cocoamphoacetates are the higher amounts of sodium chloride and
glycolic acid, both being the products of alkaline hydrolysis of excess MCA.

Analytical methods
Most analytical methods characterizing cocamidopropyl betaine and sodium cocoampho-
acetate are quite similar. All methods reviewed here are evaluated for application to
CAPB. Only small adaptions are necessary for most methods to be applied to SCAA.

Water determination
Karl Fischer titration, as described in several standard methods [21], is still the preferred
method for a quick and exact determination of the water content, and with modern titrators
and reagents it can be carried out in a few minutes. Other methods, such as for example
oven drying at 105°C or water determination by extraction [22], are generally more time
consuming and show a greater standard deviation than Karl Fischer titration. In some
cases, a quick method to determine the water content can be carried out with (sugar)
refractometers, but these instruments must be calibrated on products with known water
content (determined by Karl Fischer titration).
246 Leidreiter et al.
Surfactant actives content
For a long time the content of actives in solutions could only be determined reliably by
subtraction methods. Many attempts have been made [23] to determine amphoterics by
direct titration methods. Yet all methods proposed have led to inaccurate results according
to our investigations. Thus the results are falsified by other protonable substances, such as
free amidoamines, glycolic acid, citric acid, or trimethylglycine, during the titration with,
for example, perchloric acid in acetic acid [23]. Other methods, such as the method
according to Platinga et al. [24], lead to too low values as short-chain fatty-acid
amidopropyl betaines are only partially measured because of an extraction step.
Recently, a modified titration method has been proposed which allows a differentiating
titration of fatty-acid amidopropyl betaines and alkoylamphoacetates by the choice of a
proper solvent. The basic approach and results are described in detail in a separate
publication [25]. The titration is carried out with a perchloric acid solution in 1,4-dioxane.
A mixture of methanol and ethylene glycol monomethyl ether serves as the solvent for the
amphoteric.
The amphoteric is adjusted to its pure zwitterionic form with a sodium hydroxide/
sodium acetate buffer. Titration with perchloric acid transforms the amphoteric into its
cationic form. The choice of the special solvent mixture methanol/ethylene glycol
monomethyl ether allows an almost selective titration. The titration curves obtained shown
in Fig. 6 [25], can be evaluated by modern titrators without problems. According to our
experience there is a relative standard deviation of approximately 0.6% by this method.

Figure 6. Titration of CAPB in methanol/ethylene glycol monomethyl ether with

perchloro acetic acid in dioxane.
Amphoteric surfactants 247
This method does not allow determination of CAPB and SCAA separately in one
sample.
In the publication of Gerhards et al. [25] other methods of the quantitative determination
of CAPB such as titration with ion-sensitive electrodes are discussed.

Sodium chloride determination

The determination of chloride by potentiometric titration in dilute nitric acid with silver
nitrate is one of the most reliable of all analytical methods applied to aqueous amphoterics
[26]. This precipitation titration can be carried out reliably with a relative standard
deviation of 0.4%. From the chloride content the sodium chloride content is calculated.

Glycerol
As previously mentioned, glycerol is formed as a by-product during the production of
amidoamine starting from trigylcerides. It is most convenient to determine the glycerol in
the final products by iodometric titration [27].
Compounds with vicinal OH-groups are cleaved by periodate, then the periodate is
reduced to iodate. By the addition of iodide, iodine is formed which is titrated with sodium
thiosulphate using starch as indicator:

CH2OH-CHOH-CH2OH 1 2 NaIO4 → 2HCHO 1 HCOOH 1 2 NaIO3 1 H2O

Fatty acid
A gas chromatography (GC) method [23] has been proposed to extract the fatty acids from
the dried betaine using diethyl ether. After elution through a silica gel cartridge the eluate
is neutralized with tetramethylammonium hydroxide in the presence of phenolphthalein
and directly injected into a gas chromatograph. The formation of fatty-acid methyl esters
takes place in the injector of the gas chromatograph. Pentadecanoic acid is used as the
internal standard. Apart from problems with the time-consuming preparation of samples
this procedure has also inexplicable problems with the reproducibility.
A modern newly developed method is the determination of fatty-acid derivatives by
HPLC. In this method no extraction is needed. The fatty acid is derivatized in situ with
naphthacyl bromide. The derivatives can directly be analysed by HPLC on reversed-phase
material with a UV detector at 254 nm. The sum of free fatty acids can also be determined
with nuclear magnetic resonance (NMR) spectroscopy.

Fatty acid amidoamine

A variety of methods have also been discussed to determine residual amounts of free fatty-
acid amidopropyl amines [23,28,29]. Until now mainly titration and chromatographic
methods have been investigated. Käseborn [23] explains in detail why existing titration
methods cannot be satisfactorily applied to alkylamidopropyl betaines.
Thin-layer chromatography has proved to be a successful method for the semi-
quantitative determination of free amidopropyl dimethyl amine or amidoethyl ethanol
amine. The silica-gel plate can be developed in a solvent mixture of chloroform, ethanol
and ammonia (30/50/2), and the amido compounds are detected by bromophenol dye
solution.
248 Leidreiter et al.

Figure 7. Determination of amidoamine (7.73 min) by HPLC, all alkoyl chain length are
detected together in one single peak.

The amidopropyl dimethyl amine can be quantitatively determined by HPLC without

problems. A special ion-exchange column (ProTens, Artificial Sensing Instruments,
Switzerland) is used. A 0.02 M phosphate-buffer solution serves as eluent. Under these
conditions the amidoamine can be detected as a single peak and is not separated according
to the fatty acid composition. Figure 7 shows an example of such a determination. This
method is currently being discussed by different committees. A quantitative HPLC method
comparable to the above for the determination of amidoethyl ethanol amine is under
evaluation.

Chloroacetic acid/dichloroacetic acid/glycolic acid

Initiated by discussions about the toxicological effects of chloroacetic aids, new analytical
methods had to be elaborated with detection limits lower than the known applied methods
(mainly ion chromatography with suppressor techniques or capillary zone electrophoresis).
This discussion focuses mainly on two methods: (a) GC methods according to Cetinkaya
[30] and Arens and Spilker [31]; and (b) HPLC methods with ion-exchange columns.
For the GC methods the organic acids are converted into the methyl esters and are
detected using an electron-capture detector (ECD).
The HPLC method can be carried out directly with little sample preparation (only
dilution) on an anion-exchange column (Aminex HPX-87 H). The elution is achieved with
0.01 M sulphuric acid, and detection is by a UV detector at 205 nm. Another advantage of
the HPLC method is that glycolic acid can be measured at the same time. Figure 8 shows
a corresponding chromatogram.
Whereas the GC method has proved more reliable in interlaboratory tests, the HPLC
method turns out to be considerably less time-consuming and more universal since all the
organic acids mentioned above are detected simultaneously.
In the HPLC method the detection limit for monochloroacetic acid is approximately 5
ppm and 10 ppm for dichloroacetic acid.
Amphoteric surfactants 249

Figure 8. Determination of monochloroacetic acid (18.18 min.), dichloroacetic acid (10.52 min.)
and glycolic acid (13.77 min.) by HPLC.

Dimethyl aminopropyl amine (DMPA)

Residual DMPA is normally determined in the amidoamine before it is used for the betaine
production, but with a recently developed method [32] it is also possible to detect free
DMPA in the final betaine. In both amidoamine and betaine, DMPA is analysed by
reversed-phase HPLC with UV-detection after derivatizing with phenyl isothiocyanate.
This sensitive method is especially suitable for the detection of very low concentrations
of DMPA. In betaines, DMPA occurs only in the lower ppm-level, typically from ,5 to
20 ppm.

Aminoethylethanol amine (AEEA)

The determination of residual AEEA has to be monitored in the imidazoline intermediate.
In the final SCAA a quantitative method is currently not available. The valuation of a
method on the basis of the DMPA determination procedure will be finished soon.

Fatty acid composition

With the help of the analytical methods discussed above it is possible to characterize the
quality of the production of amphoterics. Fatty-acid composition is, however, a
characteristic of the fatty raw material, which is therefore normally analysed rather than
the final product. Nevertheless methods are available to determine the fatty-acid
composition. The free fatty acids can be obtained after cleavage of the amide bond by
heating in concentrated hydrochloric acid. After their conversion into methyl esters by
known methods (e.g. with methanol/sulphuric acid) the fatty acids can be analysed by gas
chromatography.
250 Leidreiter et al.
For CAPB, these sample preparations can be avoided with two other HPLC methods
[23,25]. Using these methods alkyl distributions can be obtained directly after separation
on a reversed-phase column (RP 18/7 mm) with methanol/water (detection by UV at 215
nm) or on an ion-exchange column (Nucleosil SA) with a buffer solution (detection with
RI detector). In ion-exchange chromatography the order of elution is reversed compared to
the RP chromatography – the longest chain betaine is eluted first followed by shorter chain
derivatives.

Application characteristics
Typical analytical data for CAPB and SCAA are shown in Table II. CAPB is available in
a somewhat higher active concentration than SCAA. As mentioned above, only high-purity
CAPB types with a water content below approximately 55% are stable against
microbiological attack. The SCAA types show sufficient microbiological stability even at
a water content of about 60%. One has to assume, that the amphoacetate moiety provides
a microbicidal activity, while the betaine moiety does not.
The mildness of amphoteric surfactants is one of the most important issues. The
availability of reliable in-vitro methods for the determination of mucous membrane
irritation allows an interesting comparison. The data in Fig. 9 are generated by the red
blood cell (RBC) method introduced by Pape et al. [33]. The data show that pure SCAA
is milder than CAPB. Due to a synergistic effect in the SLES/CAPB system no significant
difference in mildness is observed between both amphoterics at ratios of 90% amphoteric
and below. In common surfactant systems with high ratios of SLES, the mildness-
enhancing effect of both CAPB and SCAA is very similar. Amphoteric surfactants
contribute strongly to the viscosity build-up in cosmetic cleansing formulations. This is
surely due to the sodium chloride content but also to synergistic interaction between the
anionic primary surfactant and the neutral or positive charged amphoteric. Therefore, the
viscosity of an SLES/amphoteric solution is strongly pH dependent.
Figure 10 shows the viscosity profile of an SLES/amphoteric surfactant solution. CAPB
and SCAA show very similar behaviour in this example. Both amphoteric surfactants
provide a strong thickening effect. The sodium chloride content of the surfactant solutions
compared in Fig. 10 is adjusted to the same level at each SLES/amphoteric ratio. Owing

Table II. Typical values af amphoteric surfactants: commercial high purity quality
Commercial name TEGO® Betain F50 TEGO® Glycinate 818 M
INCI/CTFA Cocamidopropyl betaine Sodium cocoamphoacetate
Pure active surfactant ca. 35% ca. 30%
Water ca. 54% ca. 59%
Amidoamine ,0.3% ,0.5%
Fatty acid ca. 1.5–2.0% ,1%
Diamide Not possible ,0.6%
Glycerol ca. 2–3% –
Glycolic acid ca. 0.2–0.5% ca. 1–2%
NaCl ca. 7% ca. 7%
MCA/DCA ,5 ppm/,10 ppm ,5 ppm/,10 ppm
pH ca. 5 ca. 8.5
Amphoteric surfactants 251

Figure 9. Mildness in in vitro RBC-test of SLES/amphoteric mixtures as a function of

amphoteric ratio. High values correspond to best mildness, e.g. lowest mucous membrane
irritation. s, CAPB; n, SCAA.

Figure 10. Viscosity of an aqueous solution of a SLES/amphoteric mixture as a function of the

amphoteric ratio: 12% active, pH6, total NaCl: 4.5% 3 amphoteric ratio (e.g. 50% amphoteric corr.
2.25% NaCl)
252 Leidreiter et al.
to the high sodium chloride content in SCAA and the need to neutralize the SCAA-
containing solutions, the sodium chloride content of the CAPB-containing solutions had to
be adapted to the same level to achieve comparable results. The sodium chloride content
of each mixture quoted in Fig. 10 is calculated by multiplying 4.5% with the respective
ratio of amphoteric.

Conclusion
The production of coco fatty acid amidopropyl betaine or sodium cocoamphoacetates and
their related commercial forms can be carried out in a controlled manner to ensure a
consistent high quality and reduced level of by-products.
The analytical methods described to determine the main components water and
surfactant actives, the side components sodium chloride, glycerol and fatty acid, and trace
components such as fatty acid amidoamine, diamide, glycolic acid, mono- and di-
chloroacetic acid are reliable and can be routinely applied. If required, these analytical
methods can be supplemented by modern HPLC methods to determine fatty acid
composition or by spectroscopic methods like 1H- and 13C-NMR spectroscopy. The NMR
methods repeatedly prove to be a helpful tool to recognize unexpected additional
components; trace components however cannot be detected by NMR spectroscopy.
The further development of analytical methods is an essential requirement for the
continual improvement of amphoterics production and the quality of its forms of supply.
Thus the cosmetic and detergent industries can be offered amphoteric surfactants to satisfy
their highest demands of quality and technical properties.
CAPB and SCAA of comparable high quality and purity provide similar basic technical
performance as viscosity response, foam behaviour and mildness-enhancing effectivity.
The choice between both types has to be made on detailed formulation optimization and
sensory evaluation.

References
1. Final report on the safety assessment of cocoamphoacetate, cocoamphopropionate, cocoampho-
diacetate and cocoamphodipropionate. J. Am. Coll. Tox. 9, 121 (1990).
2. Rieger, M.M. Cosmet. Toiletries 99, 61 (1984).
3. Denan, P.J., Ricca, J.M., Marcenac, F., Vukov, R., Tracy, D. and Dahanayake, M. SÖFW-J.
121, 399 (1995).
4. Hoffmann, K. Jahrbuch f.d. Praktiker Verlag f. chem. Industrie H. Ziolkowsky (1973).
5. Hüttinger, R. Goldschmidt informiert . . . 32, 39 (1975).
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