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

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 which are not friends between two phases

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.

 Surfactants are molecules that preferentially adsorb at an interface, i.e.

Solid/liquid Liquid/gas Liquid/liquid (froth flotation) (foams) (emulsions)

Water: surface tension = 72 dynes/cm Water + 1.0% Surfactant: Surface tension = 20 40 dynes/cm Significantly alter interfacial free energy (work needed to create or expand interface/unit area). Surface free energy of interface minimized by reducing interfacial area.

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)

Anionic Surfactants
Carboxylates
Soaps

LABS

Alkyl benzene Sulphonates

FAS

Sulfosuccinate Diester

Sulfosuccinate

Monoester

Uses

: Anionic Surfactants

Cleansing Formulation Shampoo Hand wash Bath gels Tooth Paste Soaps & Detergents

Cationic Surfactants

Important Property Substantivity

Cationic 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

MOST COMMONLY USED ANIONICS

1. 2. 3. 4. 5. Alcohol Sulfates. Ethoxylated Alcohol Sulfates. Sulfosuccinates. Linear Alkylbenzene Sulfonates. Alpha Olefin Sulfonates.

ALCOHOL SULFATES
History: Commercial usage began in the mid 1940s. Made by the reaction of a fatty alcohol (C8-C18) with sulfur trioxide. The alcohol sulfuric acid is neutralized with sodium or ammonium hydroxide, or an amine.

CHARACTERISTICS OF ALCOHOL SULFATES

1. 2. 3. 4. 5. 6. 7. C12 (Lauryl) provides the highest foam. Hydrolyzes at pH < 4.5. Can be readily thickened when combined with alkanolamides, betaines, amine oxides etc. Thickening can be greatly enhanced by the addition of electrolytes (NaCl, KCl etc.). Light color. Bland odor.

MAJOR APPLICATIONS
Shampoos Body Wash Liquid Hand Soap Bath Products Facial Cleansers Syndet Bars

ETHOXYLATED ALCOHOL SULFATES

History: Commercial usage began in the early 1950s. Made by the sulfation of an ethoxylated fatty alcohol. Typically, the alcohol is lauryl (C12) and ethylene oxide is in the range of 2-3 moles. The salts are typically sodium or ammonium.

SODIUM LAURETH SUFATE

Lipophilic

Hydrophilic

PROPERTIES OF ETHER SULFATES

More soluble than alcohol sulfates. Hydrolyze at pH < 4.5. Enhance foam stability of LAS (Linear Alkylbenzene Sulfonates). More mild than alcohol sulfates. Mildness is significantly improved when blended with a sulfosuccinate.

MEAN SCORE 6.0

EFFECT OF BLENDS ON IRRITATION 15% ACTIVE

SLS 4.0 AOS

2.0

SLES 0 0 25 50 75 100

PERCENT DISODIUM OLEAMIDO MEA SULFOSUCCINATE

LINEAR ALKYLBENZENE SULFONATE (LAS)

Prepared by the sulfonation of alkyl (typically C12) benzene with sulfur trioxide. Salts are typically sodium, ammonium or amines.

SODIUM DODECYLBENZENE SUFONATE

Lipophilic

Hydrophilic

APPLICATIONS OF LAS
Primary surfactant used in household and industrial products: liquid dish wash, car wash, laundry, etc. Rarely used in personal care. Stable in acidic products.

Sulfates Hydrolyze More Readily Than Sulfonates Due to the Weaker R-O-S Bond

Sulfonate: Sulfate:

ALPHA OLEFIN SULFONATES

Made by the sulfonation of C14-16 alpha olefin. Product is actually a mixture of Na 2,3 alkenylsulfonate and Na 3hydroxy-alkanesulfonate.

ALPHA OLEFIN SULFONATES

Sodium 2,3 alkenylsulfonate

Sodium 3-hydroxy-alkanesulfonate

PROPERTIES
Excellent foamer. Difficult to thicken. Stable in acid. Used in both personal care and house hold cleansers. More mild than LAS.

APPLICATIONS
Liquid dish wash. Acid cleaners. Car wash. Liquid hand soap. Sulfate free cleansers.

SULFOSUCCINATES
Monoesters are primarily used in personal care cleansers. Diester (sodium dioctylsulfosuccinate) is the most cost effective wetting agent available.

TWO TYPES
MONOESTER
(GOOD FOAMER, MILD)

DIESTER
(POOR FOAMER, LOW SOLUBILITY)

MONOESTERS ARE FROM TWO SOURCES

MONOALKANOL AMIDES

FATTY ALCOHOLS, OR ETHOXYLATED ALCOHOLS

GENERAL DIFFERENCES BETWEEN SULFOSUCCINATE TYPES AMIDE

Mild to skin and eyes. Thicken and condition.

FATTY ALCOHOL
Mild to skin. Foams better. Water white color.

PROPERTIES
Will hydrolyze in acid or alkaline conditions. Should be formulated in a pH range of 5.0-7.0. Are mild to skin and eyes. The most cost/effective mild surfactants available.

EFFECT OF BLENDS ON SKIN IRRITATION

5.0

4.0

3.0

2.0

4.7

4.0
1.5 0.9 0.9
0/100

1.0

0 100/0 75/25 50/50 25/75

SLES/DSLSS*
*SLES: Sodium Laureth Sulfate DSLSS: Disodium Laureth Sulfosuccinate

EFFECT OF BLENDS ON FOAM

500

400 FOAM HT. 300 (ml.)

450
200

420

350

100

0 100/0 25/75 0/100

SLES/DSLSS*
*SLES: Sodium Laureth Sulfate DSLSS: Disodium Laureth Sulfosuccinate

AMPHOTERICS/BETAINES

AMPHOTERICS ARE DERIVITIVES OF FATTY IMIDAZONES

AMPHOTERICS

Zwitter Ion (Isolectric Form)

Cationic (Acid Form)

Anionic (Alkaline Form)

PROPERTIES OF AMPHOTERICS FOR HI&I APPLICATIONS

Stable in alkaline and acid conditions. The propionate and dipropionate type are excellent for HI&I cleaners. Low and high foaming is dependant on the molecular weight of the fatty moiety. A C8 will be a low foamer, whereas, a C12 is a high foamer.

EXAMPLES OF CAUSTIC SOLUBILITY

Compound Coco Dipropionate Caprylic (C8) Dipropionate Caprylic (C8) Propionate Caprylic (C8) Diacetate Coco Propionate Octyl Betaine Sodium Xylene Sulfonate %NaOH 41 38 30 28 25 23 22

COMPARATIVE FOAM HEIGHTS

Compound Cocamidopropyl Betaine Coco Propionate Coco Dipropionate Octyl (C8) Betaine Capryl (C8) amidopropyl Betaine Caprylic (C8) Diacetate Foam Ht. 210 155 145 50 30 10

PROPERTIES OF AMPHOTERICS FOR PERSONAL CLEANSING Stable over a wide pH range. Mild to skin and eye.

Reduce irritation of ether sulfates.

EFFECT OF BETAINE AMPHOTERIC WITH SODIUM LAURETH SULFATE ON EYE IRRITATION

DRAIZE SCORE 40
COCAMIDOPROPYL BETAINE

30
20 10 0
SLES AMPHO/BETAINE DISODIUM COCOAMPHODIACETATE

100 0

75 25

50 50

25 75

0 100

BETAINES
TWO TYPES 1. Alkyl 2. Alkylamido

REASONS FOR BETAINE GROWTH

1. Formulators Became Familiar With the Advantages. 2. Recently Used In Household and Institutional Cleaners. 3. Favored Replacement for Diethanolamides

BETAINES

Cationic (Acid Form)

Zwitter Ion (Isoelectric Form)

BETAINES ARE BETTER VISCOSITY BUIDERS THAN AMPHOTERICS

MODEL FORMULA
Sodium Lauryl Sulfate Amphoteric or Betaine Water pH=7.0 Wt.% 8.0 2.0 90.0

COMPARATIVE VISCOSITY BUILDING

CPS (0000)
6.0
COCAMIDOPROPYL BETAINE

5.0

4.0

3.0

DISODIUM COCOAMPHODIACETATE

2.0

1.0 2.0 3.0 4.0 PERCENT NaCl 5.0 6.0

AMPHOTERICS ARE MORE MILD THAN BETAINES

EFFECT OF FREE AMINE ON EYE IRRITATION: BETAINE VS. AMPHOTERIC DRAIZE

SCORE

50
COCAMIDOPROPYL BETAINE

ACTIVES: pH:

15.0% 7.0

40 30 20 10 0 1.0
DISODIUM COCOAMPHODIACETATE

2.0

3.0

4.0

5.0

PERCENT FREE AMINE

EFFECT OF BLENDING BETAINE WITH AMPHOTERIC ON EYE IRRITATION:

DRAIZE SCORE

ACTIVES: pH:

15.0% 7.0

40 30

20
10 0
COCAMIDOPROPYL BETAINE DISODIUM COCOAMPHODIACETATE

100 0

75 25

50 50
PERCENT

25 75

0 100

GENERAL DIFFERENCES
Betaines Mild to Skin Amphoterics

Mild to Eyes
Foam Boosting

Viscosity Building

CATIONIC SURFACTANTS

Definition: The cation is the lipophilic portion of the molecule. Types: Quaternary Ammonium Compounds Amine Salts

CATIONICS
Amine Salt:

Lipophilic

Hydrophilic

Quaternary:

Lipophilic

Hydrophilic

PROPERTIES OF QUATERNARY AMMONIUM COMPOUNDS

Lower molecular weight are typically used as biocides. Higher molecular weight (C18) are excellent hair conditioners. Most are incompatible with anionic surfactants. Low foaming. Extremely sensitive to hard water and usually require a chelant.

MAJOR USES OF QUATS

Biocides. Fabric Softeners. Hair Conditioners. Antistatic Agents. Cheater Wax. Corrosion Inhibitors. Leather Softening. Pigment Dispersants. Sewage Flocculants.

BIOCIDES
The most commonly used for household and industrial applications: Lauryl Dimethyl Benzyl Ammonium Chloride

BIOCIDAL QUATS
1. 2. 3. MODE OF ACTION Reduce surface tension at interface. Attracted to negatively charged surfaces, including microorganisms. Denature protein of bacterial or fungi cells. Affect the metabolic reactions of the cell. Vital substances leak out. Causes death.

4. 5. 6.

FABRIC SOFTENERS
Most widely used

Distearyl dimethyl ammonium chloride. Dialkyl imidazolinium methyl methoslfate.

MOST WIDELY USED QUATS USED IN HAIR CONDITIONERS

Cetrimonium Chloride Stearalkonium Chloride Distearyldimonium Chloride

FATTY AMINE SALTS

Compatible with anionic surfactants. Do not depress foam. Excellent thickeners. Insoluble in alkaline media. Some are very mild to skin and eyes.

MOST COMMONLY USED

Alkyamidopropyl Dimethylamine

Alkyamidopropyl Morpholine

COMPARATIVE EYE IRRITATION

100 80

60

40 58 20 4
Isostearamidopropyl Morpholine Lactate Distearyldimethylammonium Chloride Stearalkonium Chloride

75

40

Cetrimonium Chloride

NONIONICS
Alkanol Amides.
Amine Oxides. Ethoxylated Nonyl Phenol or Alcohols.

PREPARATION OF ALKANOL AMIDES

Made by the reaction of a mono or diethanol amine with a fatty acid, methylester or fatty glyceride, (e.g., coconut oil).

REACTION
(DEA Amide)

Diethanolamine + Fatty Acid

Fatty Diethanolamide + Water

ALKANOL AMIDES
Most cost/effective thickener and foam stablizer available. History: Commercially available in the mid 1940s. Diethanolamides are being phased out of formulas due to reported cancer link. They are being replaced by: Betaines, Amine Oxides, Monoethanolamides and Monoisopropanolamides.

MONOETHANOL AND MONOISOPROPANOL AMIDES

Both are solid at room temperature. Both are used as replacements for diethanol amides. For clear products the level should be low, or the product can haze due to the low solubility of the amides. The monoethanol amides have trace amounts of DEA which is not accepted by some customers. The MIPA is a better choice since DEA does not exist in MIPA.

AMINE OXIDES
Prepared by the oxidation of a fatty tertiary amine with hydrogen peroxide. They are weakly cationic on the acid side. The alkyl amine oxides are stable in the presence of sodium hypochlorite and are excellent surfactants for bleach cleaners. Not widely used in personal care.

REACTION
(Amine Oxide)

Fatty Tertiary + Amine

Hydrogen Peroxide

Fatty Amine Oxide

Water

ETHOXYLATED ALCOHOLS AND NONYL PHENOLS

CHARACTERISTICS
Fatty end of molecule is lipophilic and ethoxylatated end is hydrophilic.

Excellent detergent and wetting properties.

Poor foamers. Can not be thickened with other surfactants.

MANUFACTURED BY:
Ethoxylation of a natural derived straight chain fatty alcohol. Ethoxylation of synthetic branched chain alcohol. Ethoxylation of nonyl phenol.

REACTION
(Ethoxylated Alcohol)

Fatty Alcohol

Ethylene Oxide

Ethoxylated Alcohol

REGULATORY STATUS OF ETHOXYLATED NONYL PHENOLS

Banned in Europe. Banned in some states.

Will eventually be banned in the U.S. and Canada.

H I & I APPLICATIONS OF NONIONICS

Commercial Dishwash. Home Floor Carpet Care.

Dairy and Food.

Hard Surface Cleaning.

OTHER INDUSTRIES
Paints and Coatings. Agrochemicals. Electroplating. Textiles. Pulp and Paper. Oil Field. Metal Working.

SOME NEW GUYS ON THE BLOCK NATURAL SURFACTANTS

Decylglucoside: Derived from sugar and coconut oil. Cocoyl Glutamate: Derived from glutamic acid (amino acid) and coconut oil. Cocosulfate: Derived from coconut oil.

CURRENT TRENDS AND LIMITATIONS

Natural. Certified Organic. Animal friendly. DEA Free. Formaldehyde Free. Nitrosamine Free. Sulfate Free. Low Dioxane.

THATS IT IN A NUTSHELL