SURFACTANTS

IN A NUT SHELL

By Tom Schoenberg SCHOENBERG CONSULTING

SURFACTANT CLASSES
ANIONICS

AMPHOTERICS/BETAINES
CATIONICS NONIONICS

ANIONICS
Definition: The anion portion of the molecule is lipophilic. Example: Sodium Lauryl Sulfate: Cation: Sodium (hydrophilic) Anion: Laurylsulfate (lipophilic)

SODIUM LAURYL SUFATE

Lipophilic

Hydrophilic

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. 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.

4.
5. 6. 7.

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

4.7
2.0

4.0

1.0

1.5

0.9
0 100/0 75/25 50/50 25/75

0.9
0/100

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 30 20 10 0
SLES AMPHO/BETAINE COCAMIDOPROPYL 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 5.0 6.0

PERCENT NaCl

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 Mild to Eyes Foam Boosting Viscosity Building Amphoterics

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. 4. 5. 6.

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.

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 40

75

4
Isostearamidopropyl Morpholine Lactate Distearyldimethylammonium Chloride Stearalkonium Chloride 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