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Report on Surfactants market
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S U R F A C T A N T S
“IN A NUT SHELL”
By Tom SchoenbergSCHOENBERG CONSULTING
SURFACTANT CLASSES
• ANIONICS
• AMPHOTERICS/BETAINES
• CATIONICS
• NONIONICS
Definition: The anion portion of the
molecule is lipophilic.
Example: Sodium Lauryl Sulfate: Cation: Sodium
(hydrophilic) Anion: Laurylsulfate (lipophilic)
ANIONICS
Lipophilic Hydrophilic
SODIUM LAURYL SUFATE
MOST COMMONLY USED ANIONICS
1. Alcohol Sulfates.2. Ethoxylated Alcohol Sulfates.3. Sulfosuccinates.4. Linear Alkylbenzene
Sulfonates.5. Alpha Olefin Sulfonates.
ALCOHOL SULFATES
• History: Commercial usage began in the mid 1940’s.
• 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. C12 (Lauryl) provides the highest foam.
2. Hydrolyzes at pH < 4.5.3. Can be readily thickened when
combined with alkanolamides, betaines, amine oxides etc.
4. Thickening can be greatly enhanced by the addition of electrolytes
5. (NaCl, KCl etc.).6. Light color.7. Bland odor.
• Shampoos• Body Wash• Liquid Hand
Soap• Bath Products• Facial Cleansers• Syndet Bars
MAJOR APPLICATIONS
ETHOXYLATED ALCOHOL SULFATES
• History: Commercial usage began in the early 1950’s.
• 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.
Lipophilic Hydrophilic
SODIUM LAURETH SUFATE
• 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.
PROPERTIES OF ETHER SULFATES
EFFECT OF BLENDS ON IRRITATION15% ACTIVE
MEANSCORE
6.0
4.0
2.0
0
0 25 50 75 100
SLES
AOS
SLS
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.
Lipophilic Hydrophilic
SODIUM DODECYLBENZENE SUFONATE
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 3-hydroxy-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
SLES/DSLSS**SLES: Sodium Laureth Sulfate
DSLSS: Disodium Laureth Sulfosuccinate
5.0
4.0
3.0
2.0
1.0
0
4.74.0
1.50.9 0.9
100/0 75/25 50/50 25/75 0/100
EFFECT OF BLENDS ON FOAM
350420450
FOAM HT. (ml.)
500
400
300
200
100
0100/0 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 AMPHOTERICSFOR 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
CompoundCoco Dipropionate Caprylic (C8) Dipropionate Caprylic (C8) Propionate Caprylic (C8) Diacetate Coco Propionate
Octyl Betaine Sodium Xylene Sulfonate
%NaOH41383028252322
COMPARATIVE FOAM HEIGHTS
Foam Ht. 210155145503010
Compound Cocamidopropyl BetaineCoco PropionateCoco DipropionateOctyl (C8) Betaine Capryl (C8) amidopropyl Betaine Caprylic (C8) Diacetate
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
DRAIZESCORE
40
30
20
10
0
1000
7525
5050
2575
0100
SLES
AMPHO/BETAINE
COCAMIDOPROPYLBETAINE
DISODIUMCOCOAMPHODIACETATE
BETAINES
TWO TYPES
1. Alkyl2. 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 SulfateAmphoteric or BetaineWater
pH=7.0
Wt.% 8.0 2.090.0
COCAMIDOPROPYL BETAINE
COMPARATIVE VISCOSITY BUILDING
DISODIUMCOCOAMPHODIACETATE
CPS(0000)
6.0
5.0
4.0
3.0
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. AMPHOTERICDRAIZE
SCORE
40
30
20
10
0
1.0 2.0 3.0 4.0 5.0
PERCENT FREE AMINE
COCAMIDOPROPYLBETAINE
DISODIUMCOCOAMPHODIACETATE
50 ACTIVES: 15.0%
pH: 7.0
EFFECT OF BLENDING BETAINE WITH AMPHOTERIC ON EYE IRRITATION:
DRAIZESCORE
40
30
20
10
0
1000
2575
0100
PERCENT
COCAMIDOPROPYL BETAINE
DISODIUM COCOAMPHODIACETATE
ACTIVES: 15.0%
pH: 7.0
7525
5050
GENERAL DIFFERENCES
Mild to Skin
Mild to Eyes
Foam Boosting
Viscosity Building
Betaines 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”
MODE OF ACTION1. Reduce surface tension at
interface.2. Attracted to negatively charged
surfaces, including microorganisms.
3. Denature protein of bacterial or fungi cells.
4. Affect the metabolic reactions of the cell.
5. Vital substances leak out.6. 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
Isostearamidopropyl Morpholine Lactate
Distearyldimethylammonium Chloride
Stearalkonium Chloride
Cetrimonium Chloride
4
4058
75
0
20
40
60
80
100
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 1940’s.
• 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
HydrogenPeroxide
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)
Ethoxylated AlcoholFatty Alcohol
Ethylene Oxide
+
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.
THAT’S IT “IN A NUTSHELL”