Synthesis of surfactants

Cationic Surfactants
 Cationic surfactants
• Introduction and background
– Surfactants in the class are dominated by a positively charged nitrogen as the
core hydrophile

– Other positively charged hydrophiles are possible, such as sulfonium and

phosphonium

– Largest market for cationic surfactants is as the active ingredient in fabric

softeners, Used as hydrophobation agents in organoclays

– Surfactant molecules with hydrocarbon chains >16 carbons have high lubricity,
Unsaturated carbon chains have less lubrication
 Cationic surfactants
• Introduction and background
– Due to the positive charge of the head group, cationic surfactants strongly
adsorb onto negatively charged surfaces such as fabric, hair and cell
membrane of bacteria

– Used as fabric softeners, hair conditioners and antibacterial agents

– In the dying process: cationic surfactants form highly insoluble complexes with
anionic dye molecules, affixing the dyes and preventing their loss

– On metal surfaces, cationic surfactants impart corrosion inhibition and

lubricity
 Synthesis of Cationic Surfactants
• Biocidal properties: surfactant molecules interact with the negatively
charged surfaces of simple biological systems, thus disrupting cell wall
structures of single celled organisms and inactivate viruses

• Cationic surfactants are synthesised via:

– Conversion of a carboxylic acid –containing group into a nitrile, then hydrogenation
to an amine
– Condensation products based on fatty acids and their derivatives but without
nitrile intermediates
– From α-olefins or fatty alcohols
 Cationic Surfactants - Manufacturing
processes
• Fatty acid (from triglyceride splitting) is reacted with ammonia and
converted to fatty nitrile under high pressure and temperature
forming an alkylated amine

• Nitrile is then hydrogenated to a primary amine (n = 8-20)

 Cationic Surfactants - Manufacturing
processes
• Another route is reacting phosphorus trichloride and fatty alcohol
to give fatty chloride

• The fatty chloride is reacted with dimethylamine to give the alkyl

dimethylamine
 Cationic Surfactants - Manufacturing
processes
• Another route involves reacting an α-olefin derived from ethylene
with HBr and a free radical initiator giving an alkyl bromide

• Alkyl bromide then reacts with dimethylamine

• Alcohols can be directly converted to amines under hydrogenation

conditions in the presence of ammonia

• Aldehydes are prereacted to form imine followed by hydrogenation

 Cationic Surfactants - Manufacturing
processes
• Novel structural surfactants (not attainable from natural sources)
molecules can be obtained from alcohols and aldehydes

• Hydrogenated tallow-2-ethyl hexyl amine is prepared by reacting

hydrogenated tallow amine with 2-ethyl hexanal

• Intermediate imine is hydrogenated giving the secondary amine

 Cationic Surfactants - Manufacturing
processes
• Difunctional small molecule amines can be used to prepare nitrogen
cationic surfactants

• After formation of an amide or ester bond, an amine residue,

suitable for quarternization, remains in the structure
 Cationic Surfactants - Manufacturing
processes
• Quaternization in cationic surfactants is achieved through reaction of
a tertiary amine with an alkylating agent such as dimethyl sulfate,
methyl-, benzyl-, or ethyl chloride

• Describe the quaternisation of tertiary amines using methyl chloride

and dimethyl sulfate in the production of cationic surfactants. [10]

• A surfactant molecule useful for fabric softening must have two alkyl
groups each with 12–18 carbon atoms and

• At least one positively charged hydrophile which, in commercial

fabric softeners, is exclusively nitrogen
• Positively charged nitrogen aids in the deposition of the surfactant
onto the fabric and the ‘twin tails’ provide the lubricity and hand-
feel desired by consumers

• Cationic surfactant softener molecules are required to be highly

biodegradable
 Cationic surfactant biodegradation

• New, more biodegradable, cleavable structures have the

hydrophobe connected to the positively charged nitrogen
hydrophile via an ester linkage

• Increasing the degree of unsaturation of the tallow backbone of the

cationic surfactant increases the concentration at which these
materials can be formulated (to 17–26%)
 Formulation
• Carbon number for fabric softener structures is 17.5, a lower carbon
number decreases softening and reduces the deposition onto the
fabric

• Increasing the carbon number leads to difficulty in formulation due

to the formation of gels @ concs > 5%.

• Carbon atom numbers closer to an average of 16 are common for

hair conditioners

• Manipulation of these properties and the hydrophile structure will

influence the properties of the final product
 Fabric Softeners
• Ethoxylated alcohol can stabilise cationic surfactants which do not
readily form stable vesicular structures

• High degree of unsaturation gives higher liquidity and a higher

aqueous concentration of a softener dispersion than can be
achieved

• Products with high or even modest degrees of unsaturation

frequently require the addition of an antioxidant, like butylated
hydroxy toluene

• For concentrated fabric softeners, high cis/trans ratios are preferred

to reduce the likelihood of gel formation in the final product or
during processing
 Dryer Softeners
• To control the buildup of static charge in the tumble clothes dryer,
dryer softeners are used.

• Counter ion for the dryer softeners cationic surfactants is methyl

sulfate and not Cl- which causes corrosion of the interior parts of
the dryer

• Softergents: best softening is found using products high in diester,

and low in monoester and triester
 Hair Conditioning
• Conditioners restore the hair to its original condition by providing a
synthetic oil to repair the damaged hair fibers

• 2% of a hydrophobic cationic surfactant is used in formulations

• Dihydrogenated tallow dimethyl ammonium chloride gives a high

level of conditioning, while dipalmityl-dimethyl ammonium chloride
gives a lower level of conditioning
 Cationic surfactants
• Ester-based cationics are drawing attention: conditioning
performance is excellent and, additionally, improved static control is
demonstrated

• There is improved hydration of the hair follicle as a consequence of

the more polar nature of the ester-based cationics

• Cationic surfactants are also employed in detergent formulation to

enhance the activity of anionic surfactants

• Also used as thickeners

 Cationic Surfactants
• Thickeners
– cationic surfactants are frequently employed as the primary surfactants to thicken
high salt formulas
– Used to maintain solutions of sodium hypochlorite (not easily diluted) at a higher
concentration for the purpose of oxidizing clogs of human hair which form in drains

• Hard surface cleaning

– are attracted to many surfaces altering the surface and changing the force required
for cleaning.
– Cationic surfactants modify surface energy which raises the contact angle of the soil
subsequently deposited on the surface

• Organoclays
– quaternary ammonium salts are used in the production of organoclays through ion-
exchange
– As non-aqueous fluids rheology modifiers, they give greases, solvent-based paints and
drilling fluids
Effect of cationic surfactants on effort
required for cleaning