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 petrochemicals and are derived from petroleum.

What does surfactant do ?

Water & Oil are mortal enemies

Surface Tension 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 at the liquid-gas interface.

adsorbing

They also reduce the interfacial tension between oil and water by adsorbing at the liquid-liquid interface.

TYPES

INTRODUCTION
Anionic (-ve) Cationic (+ve) Sodium dodecylsulfate (SDS) Zwitterionic + (Charge depends on pH) N Nonionic (No charge) Cetylpyridinium bromide Br
O O O O OCH2CH2N(CH3)3+ P OO

O S - + O Na O

Dipalmitoylphosphatidylcholine (lecithin)

OH

Polyoxyethylene(4) lauryl ether (Brij 30)

Types of Surfactants

Ionic Surfactants
Anionic Surfactants
Carboxylates
Soaps

LABS

Alkyl benzene Sulphonates

FAS

Ionic Surfactants
Surfactants
Sulfosuccinate Diester

Anionic

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+ CH3 CH2COO-

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 emulsifier

Oil in water Emulsifiers

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 Types Emulsifiers Foam Stabilizers Wetting agents Lipid Crystal Modifiers Protein Modifiers Protein Modifiers Builders Fillers Perfumery agents Detergents

Solubilizers/ Dispersing
agent Starch Complexers

Terms
Selection criteria 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 SOLVENT

Definition The medium in which soil is suspended and carried away from 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, 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.

SURFACTANTS

PENETRATING & WETTING AGENTS

By changing the chemical composition of the hydrophilic and hydrophobic ends of the surfactant molecule, different surfactants with varying degrees of effectiveness can be created. By "punching up" the penetration and wetting 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 droplets that are more easily dispersed throughout the solvent. Enable soils to be dissolved so that they are no longer solid particles, thereby making them easier to break apart. Enable the spreading of particles throughout the solvent and prevent them from 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 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 easily washed away. Give the overall solution additional strength to hold heavy soil loads. The most common builder is phosphate but, due to environmental concerns, phosphate is not used as much in modern solvents.

EMULSIFIERS

SOLUBILIZERS
DISPERSANTS

CHELATING AGENTS

SAPONIFIERS BUILDERS

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

Dil. Soln

Soln at CMC

Soln 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 Example = [M.W. hydrophilic portion / M.W. of lopophilic portion]/ 5 : 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 emulsifier

Oil in water Emulsifiers

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 non-polar compound

Reverse micelles polar compound

amphiphilic compound

Correct solubility for unique application

High Medium Low - for detergents - spreading & dispersion - invert emulsion

Examples1. 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

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Emulsifiers
Role Types :Form emulsions, Stabilize emulsions, Modify structures : 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
(surface chemistry)

Mechanical

Chemical

Liquid Soil

Roll-up Reduction in Soil Adhesion Liquefaction / Solubilization

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Solid Soil

Mechanism for Stain Removal

Liquid soil (Roll-up)
Solid soil (Emulsification)

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Anionic Surfactants
Linear Alkyl benzene sulfonate (LAS) Main Strengths

Weaknesses

Inexpensive (unless oil is expensive) Very effective at particulate soil removal Ca2+ sensitive (although not like soap) Environmental Degradation concerns (banned in the Nordic swan countries)

O S O O-

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Anionic Surfactants
Soap Advantages
Non-petroleum derived Oil particulate soil removal
O C O-

Weakness
Very Ca2+ sensitive Need to separate low and high molecular weight acids and hydrogenate for odor control

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Composition of Coconut Oil Fatty Acid

Fatty Acid Composition %

Caproic acid
Caprylic acid Capric acid Lauric acid Myristic acid Palmitic acid Palmitoleic acid

C 6:0
C 8:0 C 10:0 C 12:0 C 14:0 C 16:0 C 16.1

ND - 0.7
4.6 - 10.0 5.0 - 8.0 45.1- 53.2 16.8 - 21 7.5 - 10.2 ND

Stearic acid
Oleic acid Linoleic acid Linolenic acid

C 18:0
C 18:1 C 18:2 C 18:3

2.0 - 4.0
5.0 - 10.0 1.0 - 2.5 ND - 0.2

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

Strengths 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.

Alcohol ethoxy sulfate

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Nonionic Surfactants
Alcohol Ethoxylate Strengths
2 2 n Ca2+ insensitive Decrease critical micelle concentration (CMC) Good for oil soil removal

RO

CH CH O

R= C 11 - C 16 Alkyl and n = 7 - 9

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.
CH2CH2O n H n=7-9

C4 -C10 Alkyl

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Commercial Routes for Production of Linear Alkylbenzenesulfonate

Blend of C10 to C14 olefins
+

Catalyst AlCl3 or HF

linear alkylbenzene

SO3

NaOH
O S O - Na+ O S O OH

sodium linear alkylbenzene sulfonate

linear alkylbenzene sulfonic acid

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Synthesis of Fatty Acids and Alcohols from Plants & Animals O

R R R C O C O C O CH2 O O CH CH2

H 2O

O R C OH

CH2OH

OH

CH2OH

Triglyceride transesterification CH3OH

Fatty Acid hydrogenation H2

Glycerine

O R C OCH3

hydrogenation H2
R CH2OH

Methyl ester + Glycerine

83

Synthesis of Alcohol Ethoxylate & Alcohol Ether Sulfate

O R OH

H2C

CH2

catalyst

RO

CH2CH2O n H

alcohol

ethylene oxide

alcohol ethoxylate SO 3

RO

CH2CH2O n SO3- Na +

NaOH

RO

CH2CH2O n SO3H

alcohol ether sulfate

alkyl ether sulfuric acid

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Laundry Detergent Formulations

Raw Materials Surfactants Wt. ratio of anion : nonionic Buffer Chelating Agent Polymers Enzymes Optical Brightener Percentage 10 30 % ~ 2:1 13% 05% 0 1% 01% 0 0.20 %

Fragrance
Water (or Powder Filler)

0 0.50 %
90 50 %
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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

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Structure of a Personal Care Corporation

CEO CFO

Marketing
Advertising Focus Groups

Finance

Supplier Chain

R&D Customers Retailers Wal-Mart Drug / Food Stores Consumers

Purchasing
Manufacturing Raw Material Suppliers

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DETERGENTS INGREDIENTS

Buffers
Importance of buffers Maintaining an alkalinity reserve Ease of obtaining the target pH during manufacturing Common Detergent Buffers pKa

Sodium Citrate Phosphates

Borate (Borax, Na2B4O710H2O) Sodium Carbonate (Soda Ash) Sodium Silicate (Sand + NaOH)

pKa3 = 6.3 pKa2 = 7.2 pKa3 =12.67 pKa = 9.24 pKa2 = 10.33 pKa ~ 10 -11.2
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Chelating Agents
Chelating agents complex Ca2+ and Mg2+ which allows for better surfactant efficiency.
Detergent Chelating Agents EDTA Phosphates Zeolites Comments Impacts bioavailability of Ca2+. Not normally used in laundry applications. Eutrophication Solid particles, Increases septic tank burden

Sodium Carbonate
Polymers of polycarboxylic acids Sodium Citrate

Precipitation of CaCO3 (used in powders)

Very Expensive Most commonly used in liquid laundry detergents.
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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

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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 N N N N
+

H C N N SO3 Na
+

H N Na - O3S C

N N

H N

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)
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Fragrances
Top Notes

Middle Notes

Bottom Notes

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

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Surfactant applications
Oral Skin Sodium Lauryl Sulfate Ammonium Lauryl Sulfate Sodium Lauryl Ether Sulfate Ammonium Lauryl Ether Sulfate Alcohol ethoxylates Sulfosuccinate Ethanolamides Amine oxide Hair Soap Bath Sun Disinfectant/ protection Bleaching

Surfactant applications
Oral Skin Hair Soap Bath Disinfectant/ Bleaching Benzalkonium chloride

CAPB CAPB - DC PEG -7 Glyceryl Cocoate

Surfactant based Soap noodles & flakes