Synthesis of Surfactants
Amphoteric Surfactants
CUHCHE215
Amphoteric surfactants
• Introduction
• Aminopropionates and Iminodipropionates
• Imidazoline-based amphoteric surfactants
• Betaine surfactants
• Other amphoteric surfactants
Amphoteric Surfactants
• Depending on pH, the hydrophilic head of amphoteric surfactants in
water has a positive, negative or both positive and negative charges
• They are cations in acidic solutions, anions in alkaline solutions and
zwitterions (both ionic groups show equal ionisation and behave
uncharged) in an intermediate pH range.
• Commonly used in toiletries, baby shampoos, daily cleaners and
detergents
• Use of C16-C18 carbon chains improves product mildness, C12-C14
carbon chains boost product viscosity in presence of additional salt,
enhance foam volume, stability and quality
Amphoteric Surfactants
• Amphoacetates, are anionic, cationic or zwitterionic at various
points in the pH spectrum.
• Betaines, sultaines and sulfonated amphoterics are common
examples
• Amphoteric surfactants are generally milder to the skin and
eyes than anionic, cationic and some nonionic surfactants
• Have the ability to modify micellar structure because of their
large ‘head groups’
Amphoteric Surfactants
• Used in formulations with anionic or nonionic surfactants to modify the:
– solubility,
– micelle size,
– foam stability,
– detergency and
– viscosity of various cleansing systems and emulsions.
• Minimal impact on the biocidal activity of quaternary ammonium salts
due to their being internally neutralised
• Betaines have high thermal stability, caustic and hypochlorite
compatibility (esp. drain cleaning)
• Betaines have high thermal stability, caustic and hypochlorite
compatibility (esp. drain cleaning)
Iminodipropionates
• Produced when a primary amine and either acrylic acid, an ester of
acrylic acid such as methyl acrylate, ethyl acrylate or crotonic acid
react
• If 1 mol acrylate used = N-alkyl β-alanine, if 2 mol acrylate used = N-
carboxyethyl β-alanine derivative
• Monopropionates (N-alkyl β-alanine derivatives) have distinct
isoelectric points than most other amphoteric surfactants
Iminodipropionates
• Isoelectric point is the pH at which the molecule is internally neutralized,
existing as a zwitterion.
• Aqueous solubility and the propensity to foam are lowest at the isoelectric
point
• Both alkyl primary amines and ‘ether amines’ are used to produce this
group of surfactants
• Ether amine derived products have branched alkyl chains as they are
produced from fatty alcohols such as 2-ethylhexanol, isodecyl and tridecyl
alcohol.
• Those from alkyl amines have linear hydrocarbon chains since they are
produced from naturally derived fatty acids except when made from 2-
ethylhexylamine
Iminodipropionates
• Dipropionates, produced with 2 mol of acrylate per mole of amine,
include 2-ethylhexyliminodipropionate, lauriminodipropionate,
isodecyloxypropyliminodipropionate and tallowiminodipropionate
• If from an acrylic acid ester, they are sold as disodium salt and contain
2 moles of either methanol or ethanol as a by-product
• Alkyliminodipropionates are used in highly alkaline ‘built’ detergent
formulations and strong acid cleaners
• Sodium lauriminodipropionate finds use in personal care applications
because of high foaming and conditioning properties at slightly acidic
pH
– Also used in firefighting foam (generates heavy and wet quality foam)
Imidazoline-based amphoteric surfactants
• Synthesis of hydroxyethyl alkyl imidazolines
+ →
Heat and vacuum
Fatty acids reacted with aminoethylethanolamine to
produce an amido-functional alkanolamine, which then
cyclizes to an alkyl hydroxyethyl imidazoline H2O +
an alkyl hydroxyethyl imidazoline
OH
• Imidazolines act as intermediates to amphoteric surfactants
• Alkyliminodipropionates are hydrolytically stable and more soluble in
fairly concentrated solutions of electrolytes, they find use in highly
alkaline ‘built’ detergent formulations and strong acid cleaners
Imidazoline-based amphoteric surfactants
• Amphoacetates
– ‘amphoacetates’ or ‘amphodiacetates’, are based on alkyl hydroxyethyl
imidazolines from either a whole coconut fatty acid distribution or a lauric cut.
– Either 1 or 2 mol of sodium chloroacetate is added to each mole of fatty
imidazoline.
• Exceptional mildness to the skin and eyes makes them candidates for
use in:
– baby shampoos, geriatric cleansing products, hand wash for medical facilities
– skin cleansers and body washes
– Causes less ‘defatting’ of the skin and perceived conditioning effect to the
skin.
– disodium cocoamphodiacetate, sodium lauroamphoacetate or sodium
cocoamphoacetate are commonly used
Imidazoline-based amphoteric surfactants
• Amphoacetates
– Glycolic acid irritates the skin and produce a kerotolytic effect at pH values below 4.5
Imidazoline-based amphoteric surfactants
• Amphoacetates
– Glycolic acid irritate the skin and produce a kerotolytic effect at pH values below 4.5
Imidazoline-based amphoteric surfactants
• Amphopropionates
– Derived from imidazolines but, rather than being alkylated with sodium
chloroacetate, they are ‘carboxylated’ with an acrylate via the Michael reaction.
– A primary or secondary amine is added across the double bond of the acrylate to
yield the beta-alanine derivative
– Amphopropionates find most utility in hard surface cleansing.
• Disodium cocoamphodipropionate is a fairly good detergent for liquid
cleaners
• Highly soluble in electrolyte solutions such as the metasilicate and
pyrophosphate builders
Imidazoline-based amphoteric surfactants
• Disodium cocoamphodipropionate
– couples nonionic surfactants into strong electrolytes efficiently
– Exhibit modest corrosion inhibition properties
• In personal care products, they are used for coupling high amounts
of conditioning polymers into ‘neutralizing shampoos,’ applied after
the use of alkali-based hair relaxers
• Conditioning is accomplished with cationic polymers that are
rendered compatible with sodium laureth sulfate by the use of
disodium cocoamphodipropionate.
– Methanol and NaCl are not desirable
– disodium cocoamphodipropionate is synthesised from Na-
acrylate
Synthesis of amphopropionates
+
+
2 NaOH
Disodium alkylampodiacetate
Synthesis of Amphopropionates
• Most of amphopropionate surfactants produced are of the
amphodipropionate type, 2 mol of methyl acrylate or sodium
acrylate added per mole of imidazoline
• 1 mol of acrylate can add to the fatty R group at the alpha carbon
• Upon hydrolysis of the imidazoline, the 2nd mol of acrylate reacts
with the liberated secondary amine to produce the beta alanine
derivative.
• If methyl acrylate is used, the methyl ester of the amphoteric
surfactant is formed
Synthesis of amphopropionates
Hydrolysis +
H2O OR
+ NaOH
Amphohydroxypropylsulfonates
• Derived from hydrolyzed alkyl hydroxyethyl imidazolines.
• Products have good hard water tolerance and have applications
including metal cleaning as well as personal cleansing
• Amidofunctional alkanolamine hydrolysis product is alkylated with
sodium 1-chloro-2-hydroxypropane sulfonic acid
Synthesis of ‘sulfonated’ amphoterics
NaHSO3 +
NaOH
Betaines
• Betaine, or trimethyl glycine, is a naturally occurring zwitterionic nutrient
found in beets
• Most simple surfactant betaines are alkyl betaines where one of the
methyl groups of trimethyl glycine is replaced with a fatty alkyl moiety
• Made by condensing 1 mol of sodium chloroacetate with an
alkyldimethylamine to yield the surfactant and 1 mol of sodium chloride
by-product
• Betaine surfactants form mixed micelles with anionic surfactants and the
large hydrophilic group (of betaines) affects the packing, altering micelle
shape
Betaines
+ NaCl
+
• Affects the detergency, foaming and the viscosity of formulations based on
betaines
• Cocamide DEA (CDEA) no longer in use since free diethanolamine forms
carcinogenic nitrosodiethanolamine, DEA itself shows carcinogenic activity in
laboratory animals
• Alkylamidopropyl betaines enhance detergency; stabilize foam and aid in
viscosity building of formulated products so they are the preferred replacements
for CDEA in many applications
Synthesis of Alkylamidopropyl Betaines
• +
Betaines
• Betaine surfactants are relatively mild to the skin
• Low foam and mildness to the skin makes these candidates in
personal care products
• Free dimethylaminopropylamine (DMAPA) and cocamidopropyl
dimethylamine are sensitisers,
• Betaine surfactants produced today have less than 10 ppm of free
DMAPA and less than 0.5% of cocamidopropyl dimethylamine
• Sodium dihydroxyethyl tallow glycinate is a thickener and surfactant
Hydroxysultaines
• Assignment 2
• Describe the synthesis of hydroxysultaines.
[10]
• Hydroxysultaines find use in personal care
products, Propane sultone is a known human
carcinogen
