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