SURFACTANTS

INTRODUCTION
Are surfactants of natural or synthetic origin
?

They can be either. Surfactants from natural origin

(vegetable or animal) are known as oleo-chemicals and
are derived from sources such as palm oil or tallow.
Surfactants from synthetic origin are known as petro-
chemicals and are derived from petroleum.
 What does surfactant do ?

Water & Oil

Surface
are mortal
Tension –
enemies
Force
between
two liquids

Surfactants
acts as clamp
binding Water
& Oil are
together
How does surfactant work?
Cleaning/Detergency
How does cleaning take place ?

Real Soil Composition

Required Effects when Cleaning
How Surfactants Work
Surfactant
Definition
Surface Active Agent
 Substance which reduces surface/interfacial tension between
two phases
 Compounds having tendency to gather around
the interface between two different materials by
altering the properties of interface remarkably
 Serves as good mediator to settle dispute between
two phases which are not friends
• Water: surface tension = 72 dynes/cm
• Water + 1.0% Surfactant: Surface tension = 20 – 40 dynes/cm

 Surfactants reduce the surface tension of water by adsorbing

at the liquid-gas interface.
 They also reduce the interfacial tension between oil and water by
adsorbing at the liquid-liquid interface.
TYPES
 INTRODUCTION
O
• Anionic (-ve) S - +
O Na
• Cationic (+ve) O
Sodium dodecylsulfate (SDS)
• Zwitterionic
+
(Charge depends on pH) N
-
• Nonionic (No charge) Cetylpyridinium bromide Br
O
O
O OCH2CH2N(CH3)3+
P O-
O
O
Dipalmitoylphosphatidylcholine (lecithin)

O O OH
O O
Polyoxyethylene(4) lauryl ether (Brij 30)
Types of Surfactants
 Ionic Surfactants
Anionic Surfactants

Carboxylates
Soaps

Alkyl benzene Sulphonates

LABS

FAS
Ionic Surfactants Anionic
Surfactants

Sulfosuccinate
Diester

Sulfosuccinate
Monoester
 Ionic Surfactants: Uses
Anionic Surfactants

• Cleansing Formulation
– Shampoo
– Hand wash
– Bath gels
– Tooth Paste
– Soaps & Detergents
Cationic Surfactants(1)
Cationic Surfactants(2)
Important Property
Substantivity
Cationic Surfactants
Ionic Surfactants
Amphoteric Surfactants

Cocobetaine (CB)
CH3

N+ CH2COO-

CH3
Cocoamidopropylbetaine ( CAPB)
CH3

CONH(CH2)3 N+ CH2COO-

CH3
 Uses : Amphoteric Surfactants

• Betaines are used in personal care products e.g.

hair shampoos, liquid soaps, and cleansing
lotions.
• All-purpose cleaning agents, hand dishwashing
agents, and special textile detergents..
Nonionic Surfactants
Nonionic Surfactants
Water Solubility of Nonionics
Reason
Cloud Point
Effect of moles of EO on Cloud Points
of Nonionic
Influence of Cloud Point on Soil
Removal
HLB –Hydrophilic Lipophilic
Balance

HLB is a means of expressing the hydrophilic property

of surfactants in figures
HLB Value
Significance

HLB Value 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Water in oil
Oil in water Emulsifiers
emulsifier

Use
Wetting Agents Detergents

Solubilizer
HLB According to Griffin
(only for PEG types)

substantive to skin and hair

HLB According to Griffin
(only for polyhydric alcohol types)

HLB = 20 ( 1 – SV / AV )
Where S V = Sap value of ester of polyhydric alcohol
AV = Acid value of fatty acid used

Calculation of HLB value of PEG-7-glyceryl-cocoate

AV of cocofatty acid = 265 mg KOH/g

SV of PEG-7-glyceryl-cocoate = 95

HLB = 20 ( 1 – 95 / 265 )
= 12.8
 HLB According to Davis
HLB = 7 + m * Hh + n * Hl
where
• m - number of hydrophilic groups in the molecule
• Hh - Value of the hydrophilic groups
• n - Number of lipophilic groups in the molecule
• Hl - Value of the lipophilic groups

Ex : Calculation of HLB of SLES

Formula of SLES : CH3(CH2)11O (CH2CH2O)2SO3Na

HLB = 7 + (1 x 1.3 + 2 x 0.33 + 38.7)+(12 x - 0.475)

= 42
Nonionic Surfactants
Properties
Nonionic Surfactants
Applications

• Cleansing agent in detergents

• Emulsifying agents household & I & I

formulations

• Wetting agents in textile processing,

agrochemical formulations
CONTENTS
 CONTENTS
• Selection criteria • Protein Modifiers
• Types • Protein Modifiers
• Emulsifiers • Builders
• Foam Stabilizers • Fillers
• Wetting agents • Perfumery agents
• Lipid Crystal Modifiers • Detergents
• Solubilizers/ Dispersing • Terms
agent • Selection criteria
• Starch Complexers • Thickening
SELECTION CRITERIA
 Selection criteria
• Type selection : Anionic, cationic…..
• Correct solubility for unique application
TERMS
 TERMS
• CMC
• Solid Fat Index (SFI) & SFC
• Span 60/ Span 80
• Tween 60/ Tween 80
Term Definition
The medium in which soil is suspended and carried away from
SOLVENT the surface. The customer adds most of the solvent to Simple
Green Products- I.E. water
Abbreviation for “Surface Active Agent”,surfactants work at the
boundary layer (the interface) between the soil and the solvent.
Each molecule of surfactant has a hydrophilic end which is
attracted to water, and a hydrophobia end which is attracted to
soil. In an effective cleaner/degreaser such as Simple Green,
SURFACTANTS many surfactant molecules attack the soil with their
hydrophobic ends, breaking it up into small bits and
surrounding it. Their hydrophilic ends then allow
the soil to be lifted, suspended, and washed away.
 By changing the chemical composition of the hydrophilic and hydrophobic ends
of the surfactant molecule, different surfactants with varying degrees of
PENETRATING &
effectiveness can be created. By "punching up" the penetration and wetting
WETTING AGENTS ability of the surfactant, more water is able to surround soil particles that would
otherwise repel water.
Enable surfactants to break up soils (particularly petroleum soils) into smaller
EMULSIFIERS
droplets that are more easily dispersed throughout the solvent.
Enable soils to be dissolved so that they are no longer solid particles, thereby
SOLUBILIZERS
making them easier to break apart.
Enable the spreading of particles throughout the solvent and prevent them from
DISPERSANTS
re-adhering to the cleaned surface.
Chelators [ “key-laters” ] “bind up” hardness minerals found in water, enabling
the other active ingredients to more effectively attack the soils. Chelators can
CHELATING AGENTS
also pull minerals and metals into solution and, in some extreme precision
applications, this is not always desirable.
Are strong alkaline chemicals that make animal fats soluble in water and more
SAPONIFIERS
easily washed away.
Give the overall solution additional strength to hold heavy soil loads. The most
BUILDERS common builder is phosphate –but, due to environmental concerns, phosphate is
not used as much in modern solvents.
 Critical Micelle Concentration

CMC

• Minimum concentration at which surfactants

molecules begin to form micelles
• Determined by surface tension measurements
• < Below CMC = Surfactant adsorbs on the surface
decreases surface tension
• > Above CMC the micelles are formed
Important Property
Small Micelle
Micelle

Extremely Dil. Soln Soln at Soln

Dil. Soln CMC above
CMC
 Specific Interactions: Chain-Chain
• As surface concentration of ionic surfactant increases, if
attractive hydrophobic interactions between alkyl chains
can compensate for ionic head group repulsion,
hemimicelles can form.

• At low coverages, patches can form on the surface.

_ _
_ _ _ _ _ _
+ + + + +
+
Surfactant Behavior
 Solid Fat Index (SFI) & Solid Fat
Content (SFC)
Solid Fat Index (SFI)
• Ratio of solid fat to total fat
• Based on dilatometry
(change in volume – liquid fat has a greater volume
than solid fat)
• Common among US suppliers. They converts SFI to SFC
based on empirical equation

Solid Fat Content (SFC)

• Ratio of solid fat to total fat (same as SFI)
• determined by NMR
 Hydrophillic-Lipophillic Balance (HLB)
• Invented by Willam Graffin (55 yrs ago)
• Ratio of oil loving portion to water loving portion
• Made for easier use of nonionics (end use appln.)
• Intended as a large scale use of emulsion
performance
• concept for choosing emulsifiers
• Ranges = 1-20
• Low HLB emulsifiers = lipophilic/ soluble in oil
• high HLB = hydrophilic/ emulsifiers are soluble
in water
HLB –Hydrophilic Lipophilic
Balance

HLB is a means of expressing the hydrophilic property

of surfactants in figures
 HLB determination
• HLB = [M.W. hydrophilic portion / M.W. of lopophilic portion]/ 5

• Example : 20 mole ethoxylate of oleyl alcohol

M.W. 20 moles of ethylene oxide ( one mole ETO =44 )=

20 x 44 = 880
M.W. (oleyl alcohol)= 270
880+ 270 = 1150 ( M.W. of whole compound)
What percentage of 1150 is 880 ?
880/1150 = 76.5%

76.5% divided by 5 = 15.3

15.3 is the HLB value of (20 mole ethoxylate of oleyl alcohol)
HLB According to Griffin
(only for polyhydric alcohol types)

HLB = 20 ( 1 – SV / AV )
Where S V = Sap value of ester of polyhydric alcohol
AV = Acid value of fatty acid used

Calculation of HLB value of PEG-7-glyceryl-cocoate

AV of cocofatty acid = 265 mg KOH/g

SV of PEG-7-glyceryl-cocoate = 95

HLB = 20 ( 1 – 95 / 265 )
= 12.8
HLB Value
Significance

HLB Value 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Water in oil
Oil in water Emulsifiers
emulsifier

Use
Wetting Agents Detergents

Solubilizer
 HLB and Use of Surfactants

Solubility HLB Range

• Antifoam 1-3.5 (Reverse micelle)
• W/O emulsifiers 3.5-8
• Wetting & spreading agents
powder (in oils) 7-9
• O/W emulsifiers 8-16
• Detergent solution 13-15
• Solubilizers 15-40
PROPERTIES
 Solubilization
• Spontaneous transfer of a compound insoluble in
the bulk solvent into solution due to incorporation
into the surfactant micelles

Normal micelles Reverse micelles

non-polar compound polar compound

amphiphilic compound
• Correct solubility for unique application
– High - for detergents
– Medium - spreading & dispersion
– Low - invert emulsion
• Examples-
1. Soaps - Medium to high in water - Low in oils/fats.
2. Anionics (SLS) - Very High in water, low in oil
3. Cationics & amphoterics- Very High in water
4. Nonionics - predicted by HLB

5. .

• \
Wetting effect
Paraffin or new cotton cloth barely wetted by water
But
When surfactant is added to water their surface
easily becomes wet

Surfactant in floor cleaner as a wetting agent

Wetting
Contact Angle and Wetting

59
 Emulsifiers
• Role :Form emulsions, Stabilize emulsions, Modify structures
• Types : Water In Oil - Low Hlb
Oil In Water - High Hlb
• Examples :
1. Mono & diglycerides: HLB = 1 to 10 (Highly lipophilic) :
produced by transesterification of glycerol and triacylcerides
2. Polysorbates: Polyoxyenthyene esters of sorbitan monoesters
3. Lecithin: A mixture of phospholipids including phosphatidyl
cholines, phosphatidyl ethanolamines, inositol phosphatides, etc

Example 1. Glycerol Monostearate : HLB value of 3.6~4.2

Dissolves in hot grease, paraffine, ethanol, chloroform, acetone
and aether, the material is widely used when producing of chocolate,
margarine, ice cream, skin care balsam, cold cream, hair oil and drug
ointment, also lubricant for plastic processing
Emulsions
Emulsification

Examples of Emulsions
Foaming effect
Foam consist of gas covered with thin liquid film.
Surfactant molecule absorbed to interface between
gas and liquid
 Substantivity
• Adsorptive property of Cationics & related
nitrogen compounds
• Adsorption, particularly into solid surfaces
• Attraction between +ve charge on nitrogen
atom & -ve charge surfaces
 cloud point & pour point

• The Cloud point of a fluid is the temperature at

which dissolved solids are no longer completely
soluble, precipitating as a second phase giving
the fluid a cloudy appearance.
• The highest temp at which a nonionic surfactant
solution is clear.
• The pour point of a liquid is the lowest
temperature at which it will pour or flow under
prescribed conditions.
 What causes cloud points?
• The solution becomes cloudy at & above the CPt
temperature as the solution splits in to two
phases
– Phase1 : Very dilute surfactant solution
– Phase2 : Surfactant-rich micellar phase
• The cloudiness you see comes from the micelles
growing large enough to scatter light
• Cloud points are reversible, and upon cooling, the
solution will return to the original clear state.
cloud point & pour point
Fabric softener

(also called Fabric Conditioner)

*is used to prevent static cling and makes the fabric
softer.
An emulsifier
*(also known as an
emulgent or
surfactant) is a
substance which
stabilizes an emulsion.
An adhesive

*is a compound that adheres or bonds two items

together.
An ink

*is a liquid containing various pigments and/or dyes

used for colouring a surface to render an image or
text. Ink is used for drawing or writing with a pen or
brush.
A laxative

*is a preparation used for encouraging defecation, or

the expulsion of feces. Laxatives are most often taken
to treat constipation.
DETERGENTS
Detergent

*is a compound, or a mixture of

compounds, intended to assist
cleaning. The term is often used to
differentiate between soap and
other chemical surfactants used for
cleaning purposes.
 Soil Removal Mechanisms

Detergency Mechanical Chemical

(surface chemistry)

Liquid Soil
Roll-up

Reduction in Soil Adhesion

Solid Soil

Liquefaction / Solubilization

75
Mechanism for Stain Removal
Liquid soil Solid soil
(Roll-up) (Emulsification)

76
 Anionic Surfactants
Linear Alkyl benzene sulfonate (LAS)

• Main Strengths
– Inexpensive (unless oil is expensive) O

– Very effective at particulate soil removal S O-

• Weaknesses O

– Ca2+ sensitive (although not like soap)

– Environmental Degradation concerns (banned in
the Nordic swan countries)

77
 Anionic Surfactants
O
Soap
C
• Advantages O-

– Non-petroleum derived
– Oil particulate soil removal
• Weakness
– Very Ca2+ sensitive
– Need to separate low and high molecular weight
acids and hydrogenate for odor control

78
Composition of Coconut Oil Fatty Acid
Fatty Acid Composition %
Caproic acid C 6:0 ND - 0.7
Caprylic acid C 8:0 4.6 - 10.0
Capric acid C 10:0 5.0 - 8.0
Lauric acid C 12:0 45.1- 53.2
Myristic acid C 14:0 16.8 - 21
Palmitic acid C 16:0 7.5 - 10.2
Palmitoleic acid C 16.1 ND
Stearic acid C 18:0 2.0 - 4.0
Oleic acid C 18:1 5.0 - 10.0
Linoleic acid C 18:2 1.0 - 2.5
Linolenic acid C 18:3 ND - 0.2

79
 Anionic Surfactants
O
• Alcohol ether sulfate
C12 -C15 O CH2CH2O - CH2CH2O - CH 2CH2O S O - Na+

• Strengths Alcohol ethoxy sulfate O

– Milder to the skin than alkyl benzene sulfonate

– Less effected by water hardness than other anionic surfactants
– High foaming
– Both the hydrophile and hydrophobe can be modified to give a
range of chemical and physical properties
– Improved proteinaceous soil removal
• Weaknesses
– More expensive of than alkyl benzene sulfonate.

80
 Nonionic Surfactants
Alcohol Ethoxylate
• Strengths R= C 11 - C 16 Alkyl and n = 7 - 9
RO CH CH O n H
– Ca2+ insensitive 2 2

– Decrease critical micelle concentration (CMC)

– Good for oil soil removal
• Weakness
– Very harsh towards hands (lipid extraction)
– Forms a gel phase on dilution with H2O and needs to be processed at T > 125
oF (52 oC) or utilize significant amounts of mechanical energy

– Higher levels of ethoxylation are solids and need to be melted and / or

transported and stored hot
– Alkyl phenol ethoxylates are less expensive than linear ethoxylates but are
possible endocrine disruptors.

C4 -C10 Alkyl O CH2CH2O n H n=7-9

81
Commercial Routes for Production of
Linear Alkylbenzenesulfonate

Blend of C10 to C14 olefins Catalyst

AlCl3 or HF
+
linear alkylbenzene

SO3

NaOH

O O

S O - Na+ S OH

O O
sodium linear alkylbenzene sulfonate linear alkylbenzene sulfonic acid

82
Synthesis of Fatty Acids and Alcohols from
O
Plants & Animals
R C O
O CH2 O CH2OH
H 2O
R C O CH R C OH + H C OH
O
CH2 CH2OH
R C O
Triglyceride Fatty Acid Glycerine

transesterification hydrogenation
CH3OH H2

O
hydrogenation
R C OCH3 R CH2OH
H2
Methyl ester
+
Glycerine 83
Synthesis of Alcohol Ethoxylate &
Alcohol Ether Sulfate

O
catalyst
R OH + H2C CH2 RO CH2CH2O n H

alcohol ethylene alcohol ethoxylate

oxide

SO 3

NaOH
RO CH2CH2O n SO3- Na + RO CH2CH2O n SO3H

alcohol ether sulfate alkyl ether sulfuric acid

84
Laundry Detergent Formulations
Raw Materials Percentage
Surfactants 10 – 30 %
Wt. ratio of anion : nonionic ~ 2:1
Buffer 1–3%
Chelating Agent 0–5%
Polymers 0 – 1%
Enzymes 0–1%
Optical Brightener 0 – 0.20 %
Fragrance 0 – 0.50 %
Water (or Powder Filler) 90 – 50 %

85
 Detergent Evaluations
• Evaluations normally done in washing
machines or on tergotometers.

86
 Evaluation
• Need to acquire or make stains
– Laborious and time consuming process
– Reproducibility is major concern
• For consumer stained garments, need to match stain intensity.
• Laboratory made stains, need to weigh and apply stain reproducibly.
– For example, to evaluate 4 products on 10 stain sets requires: (4
clothes/stain)*10 stains*4 products * 2 repeats = 320 stain clothes
• Evaluation either by instrumental reading or panelists
– Reflectance Colorimeter shades of color calibrated with black (0)
and white (100).

Reflectance Colorimeter 87
Challenges Facing the Detergent Industry

• Increasing cost of raw materials

• Cost of transportation
• Changing demographics
– Manufacturing sector of the economy in decline means that few
consumers get clothes really dirty
– Nintendo effect leads to less youth participation in organized sports
• Wal-Mart effect
• Wall Street effect
– Emphasis of reduction in capital expenditures
– Leads to downsizing and outsourcing of manufacturing requirements

88
 Structure of a Personal Care Corporation
CEO
CFO

Marketing Finance Supplier Chain

Advertising
Focus Groups Purchasing
R&D
Raw Material
Customers Manufacturing
Suppliers
Retailers
Wal-Mart
Drug / Food
Stores

Consumers
89
DETERGENTS INGREDIENTS
 Buffers
Importance of buffers
• Maintaining an alkalinity reserve
• Ease of obtaining the target pH during manufacturing
Common Detergent Buffers pKa
Sodium Citrate pKa3 = 6.3
Phosphates pKa2 = 7.2
pKa3 =12.67
Borate (Borax, Na2B4O7·10H2O) pKa = 9.24
Sodium Carbonate (Soda Ash) pKa2 = 10.33
Sodium Silicate (Sand + NaOH) pKa ~ 10 -11.2

91
 Chelating Agents
Chelating agents complex Ca2+ and Mg2+ which
allows for better surfactant efficiency.

Detergent Chelating Agents Comments

EDTA Impacts bioavailability of Ca2+. Not
normally used in laundry applications.
Phosphates Eutrophication
Zeolites Solid particles, Increases septic tank
burden
Sodium Carbonate Precipitation of CaCO3 (used in powders)
Polymers of polycarboxylic acids Very Expensive
Sodium Citrate Most commonly used in liquid laundry
detergents.
92
 Enzymes
Biological macromolecules which have a high affinity for a select
subset of stains

• Advantages
– Very efficient catalysts

• Disadvantages
– Difficult to stabilize (lifetime of a laundry detergent may last more
than 6 months to 1 year
• Sensitive to high pH (pH > 9)
• Some surfactants denature proteins
– Very expensive

93
 Classes of Enzymes
• Protease
– Protein sensitive stains include: milk (casein), grass, meats, blood
– Most widely used enzyme
– Proteases will destroy other enzymes (enzymes are proteins)
• Amylase
– Degrade starch based foods
• Cellulase
– Reduces pilling by cleaving cellulose linkages
• Lipase
– Breaks down triglycerides (natural oils)
– Works slowly and most effectively after the wash cycle is complete.
Results in potential odor issues from the release of low molecular
weight fatty acids.

94
 Anti-Redeposition
Keep suspended soils from redepositing on garments.
• Modified cellulosics
– Sacrificial layer provides a multi-wash benefit.
• Cellulose deposits on cotton. Soil/stain deposits on cellulose.
Cellulose (with soil) removed by detergent.
– Benefit is only for cotton
• Combination of anionic polymer (polyacrylate) with
partially cationic polymer (polyvinylpyrolidone, PVP).
– Mechanism is likely entrapment of particulates.
– PVP also effective at reducing dye transfer

PVP

Lauryl methacrylate Acrylic acid copolymer, z/y > 10

95
 Bleach
• Normally added to laundry process as a separate product.
– Tide with Bleach powder is exception
• Most common bleaches are chlorine bleach (¯OCl and
peroxides) O
R C O O H
Peroxy Acid

– Difficult or expensive to stabilize the bleach or other raw materials

(from bleach) in the formulation.
– Reacts with conjugated carbon double bonds to decolorize
chromophores.

-Carotene
– Denatures proteins by oxidizing the S-H bonds.
96
 Optical Brighteners
• Fluorescent Whitening Agents
• Generate a bluish hue that most people associate with a
more satisfying white.
• Worldwide consumers recognize about 2500 different
shade of white.
• Increases the brightness by converting UV light into visible
light.
• Emitted blue light hides yellow and brown tones making
treated textiles (or paper appear whiter).
• Generate a strong purple color when exposed to UV light.

97
 How Do Optical Brighteners Work?
H
H H
H H N
N C N N
N N C N N
N N H - +
SO3 Na
+
Na - O3S H N
N H

Optical Brightner

• Highly strained system (steric hindrance)

• Can control wavelength of light emission by
changing steric and/or electron donating
characteristics
• Can alter solubility and deposition by changing
the substituents (more hydrophobic or
hydrophilic)
98
 Fragrances

• Important factor in consumer

Top
acceptance or rejection of product.
Notes • Top notes: Fragrance out of bottle.
• Middle notes: Fragrance while doing
laundry (smell on wet clothes).
Middle Notes • Bottom notes: Fragrance on dry
garments (need to with stand heat of
dryer).
• Target: Elusive “fresh and clean” smell.
Bottom Notes • Different cultures have different
preferences, e.g., Gain targeted
towards Hispanic market.

99
 Surfactant applications
Oral Skin Hair Soap Bath Sun Disinfectant/
protection Bleaching
Sodium Lauryl √ √ √ √ √
Sulfate

Ammonium Lauryl √ √
Sulfate

Sodium Lauryl √ √ √ √
Ether Sulfate

Ammonium Lauryl √ √ √
Ether Sulfate

Alcohol ethoxylates √
Sulfosuccinate √ √ √ √
Ethanolamides √ √ √ √
Amine oxide √
 Surfactant applications
Oral Skin Hair Soap Bath Disinfectant/
Bleaching

Benzalkonium chloride √ √

CAPB √ √ √ √

CAPB - DC √

PEG -7 Glyceryl Cocoate √ √ √

Surfactant based Soap √

noodles & flakes