1. S U R F A C T A N T S “IN A NUT SHELL” By Tom Schoenberg SCHOENBERG CONSULTING

2. SURFACTANT CLASSES ANIONICSANIONICS AMPHOTERICS/BETAINESAMPHOTERICS/BETAINES CATIONICSCATIONICS NONIONICSNONIONICS

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

4. LipophilicHydrophilic LipophilicHydrophilic SODIUM LAURYL SUFATE

5. MOST COMMONLY USED ANIONICS 1.Alcohol Sulfates. 2.Ethoxylated Alcohol Sulfates. 3.Sulfosuccinates. 4.Linear Alkylbenzene Sulfonates. 5.Alpha Olefin Sulfonates.

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

7. 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.

8. ShampoosShampoos Body WashBody Wash Liquid Hand SoapLiquid Hand Soap Bath ProductsBath Products Facial CleansersFacial Cleansers Syndet BarsSyndet Bars MAJOR APPLICATIONS

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

10. LipophilicHydrophilic LipophilicHydrophilic SODIUM LAURETH SUFATE

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

12. EFFECT OF BLENDS ON IRRITATION 15% ACTIVE MEANSCORE 6.0 4.0 2.0 0 0255075100 SLES AOS SLS PERCENT DISODIUM OLEAMIDO MEA SULFOSUCCINATE

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

14. LipophilicHydrophilic LipophilicHydrophilic SODIUM DODECYLBENZENE SUFONATE

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

16. Sulfates Hydrolyze More Readily Than Sulfonates Due to the Weaker R-O-S Bond Sulfonate:Sulfate:

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

18. ALPHA OLEFIN SULFONATES Sodium 2,3 alkenylsulfonate Sodium 3-hydroxy-alkanesulfonate

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

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

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

22. TWO TYPES MONOESTER (GOOD FOAMER, MILD) DIESTER (POOR FOAMER, LOW SOLUBILITY)

23. MONOESTERS ARE FROM TWO SOURCES MONOALKANOL AMIDESMONOALKANOL AMIDES FATTY ALCOHOLS, OR ETHOXYLATED ALCOHOLSFATTY ALCOHOLS, OR ETHOXYLATED ALCOHOLS

24. GENERAL DIFFERENCES BETWEEN SULFOSUCCINATE TYPES AMIDE Mild to skin and eyes.Mild to skin and eyes. Thicken and condition.Thicken and condition. FATTY ALCOHOL Mild to skin.Mild to skin. Foams better.Foams better. Water white color.Water white color.

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

26. 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 4.7 4.0 1.5 0.90.9 100/075/2550/5025/750/100

27. EFFECT OF BLENDS ON FOAM 350 420 450 FOAMHT.(ml.) 500 400 300 200 100 0 100/025/750/100 SLES/DSLSS* *SLES: Sodium Laureth Sulfate DSLSS: Disodium Laureth Sulfosuccinate

28. AMPHOTERICS/BETAINES

29. AMPHOTERICS ARE DERIVITIVES OF FATTY IMIDAZONES

30. AMPHOTERICS Zwitter Ion (Isolectric Form) Cationic (Acid Form) Anionic (Alkaline Form)

31. PROPERTIES OF AMPHOTERICS FOR HI&I APPLICATIONS Stable in alkaline and acid conditions.Stable in alkaline and acid conditions. The propionate and dipropionate type are excellent for HI&I cleaners.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.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.A C8 will be a low foamer, whereas, a C12 is a high foamer.

32. EXAMPLES OF CAUSTIC SOLUBILITY Compound Coco Dipropionate Caprylic (C8) Dipropionate Caprylic (C8) Propionate Caprylic (C8) Diacetate Coco Propionate Octyl Betaine Sodium Xylene Sulfonate %NaOH41383028252322

33. COMPARATIVE FOAM HEIGHTS Foam Ht. 210155145503010Compound Cocamidopropyl Betaine Coco Propionate Coco Dipropionate Octyl (C8) Betaine Capryl (C8) amidopropyl Betaine Caprylic (C8) Diacetate

34. PROPERTIES OF AMPHOTERICS FOR PERSONAL CLEANSING Stable over a wide pH range.Stable over a wide pH range. Mild to skin and eye.Mild to skin and eye. Reduce irritation of ether sulfates.Reduce irritation of ether sulfates.

35. EFFECT OF BETAINE AMPHOTERIC WITH SODIUM LAURETH SULFATE ON EYE IRRITATION DRAIZE SCORE 40 30 20 10 0 100 0 75 25 50 50 25 75 0 100 SLES AMPHO/BETAINE COCAMIDOPROPYL BETAINE DISODIUM COCOAMPHODIACETATE

36. BETAINES TWO TYPES 1. Alkyl 2. Alkylamido

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

38. BETAINES Cationic (Acid Form) Zwitter Ion (Isoelectric Form)

39. BETAINES ARE BETTER VISCOSITY BUIDERS THAN AMPHOTERICS

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

41. COCAMIDOPROPYL BETAINE COMPARATIVE VISCOSITY BUILDING DISODIUM COCOAMPHODIACETATE CPS (0000) 6.0 5.0 4.0 3.0 2.0 1.0 2.03.04.05.06.0 PERCENT NaCl

42. AMPHOTERICS ARE MORE MILD THAN BETAINES

43. EFFECT OF FREE AMINE ON EYE IRRITATION: BETAINE VS. AMPHOTERIC DRAIZE SCORE 40 30 20 10 0 1.0 2.03.0 4.05.0 PERCENT FREE AMINE COCAMIDOPROPYL BETAINE DISODIUM COCOAMPHODIACETATE 50 ACTIVES:15.0% pH: 7.0

44. EFFECT OF BLENDING BETAINE WITH AMPHOTERIC ON EYE IRRITATION: DRAIZE SCORE 40 30 20 10 0 100 0 25 75 0 100 PERCENT COCAMIDOPROPYL BETAINE DISODIUM COCOAMPHODIACETATE ACTIVES:15.0% pH: 7.0 75 25 50 50

45. GENERAL DIFFERENCES Mild to Skin Mild to Eyes Foam Boosting Viscosity Building BetainesAmphoterics

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

47. CATIONICS Amine Salt: LipophilicHydrophilic Quaternary:

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

49. MAJOR USES OF “QUATS” Biocides.Biocides. Fabric Softeners.Fabric Softeners. Hair Conditioners.Hair Conditioners. Antistatic Agents.Antistatic Agents. “Cheater” Wax.“Cheater” Wax. Corrosion Inhibitors.Corrosion Inhibitors. Leather Softening.Leather Softening. Pigment Dispersants.Pigment Dispersants. Sewage Flocculants.Sewage Flocculants.

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

51. BIOCIDAL “QUATS” MODE OF ACTION 1.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.

52. FABRIC SOFTENERS Most widely used Distearyl dimethyl ammonium chloride.Distearyl dimethyl ammonium chloride. Dialkyl imidazolinium methyl methoslfate.Dialkyl imidazolinium methyl methoslfate.

53. MOST WIDELY USED “QUATS” USED IN HAIR CONDITIONERS Cetrimonium ChlorideCetrimonium Chloride Stearalkonium ChlorideStearalkonium Chloride Distearyldimonium ChlorideDistearyldimonium Chloride

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

55. MOST COMMONLY USED Alkyamidopropyl Dimethylamine Alkyamidopropyl Dimethylamine Alkyamidopropyl Morpholine Alkyamidopropyl Morpholine

56. COMPARATIVE EYE IRRITATION Isostearamidopropyl Morpholine Lactate DistearyldimethylammoniumChloride StearalkoniumChlorideCetrimoniumChloride 4 40 58 75 0 20 40 60 80 100

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

58. 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).

59. REACTION (DEA Amide) Diethanolamine + Fatty Acid Fatty Diethanolamide + Water

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

61. MONOETHANOL AND MONOISOPROPANOL AMIDES Both are solid at room temperature.Both are solid at room temperature. Both are used as replacements for diethanol amides.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.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.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.

62. AMINE OXIDES Prepared by the oxidation of a fatty tertiary amine with hydrogen peroxide.Prepared by the oxidation of a fatty tertiary amine with hydrogen peroxide. They are weakly cationic on the acid side.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.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.Not widely used in personal care.

63. REACTION (Amine Oxide) Fatty Tertiary + Amine HydrogenPeroxide Fatty Amine + OxideWater

64. ETHOXYLATED ALCOHOLS AND NONYL PHENOLS CHARACTERISTICS Fatty end of molecule is lipophilic and ethoxylatated end is hydrophilic.Fatty end of molecule is lipophilic and ethoxylatated end is hydrophilic. Excellent detergent and wetting properties.Excellent detergent and wetting properties. Poor foamers.Poor foamers. Can not be thickened with other surfactants.Can not be thickened with other surfactants.

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

66. REACTION (Ethoxylated Alcohol) Ethoxylated Alcohol FattyAlcoholEthyleneOxide+

67. REGULATORY STATUS OF ETHOXYLATED NONYL PHENOLS Banned in Europe.Banned in Europe. Banned in some states.Banned in some states. Will eventually be banned in the U.S. and Canada.Will eventually be banned in the U.S. and Canada.

68. H I & I APPLICATIONS OF NONIONICS Commercial Dishwash.Commercial Dishwash. Home Floor Carpet Care.Home Floor Carpet Care. Dairy and Food.Dairy and Food. Hard Surface Cleaning.Hard Surface Cleaning.

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

70. SOME NEW GUYS ON THE BLOCK “NATURAL SURFACTANTS” Decylglucoside: Derived from sugar and coconut oil.Decylglucoside: Derived from sugar and coconut oil. Cocoyl Glutamate: Derived from glutamic acid (amino acid) and coconut oil.Cocoyl Glutamate: Derived from glutamic acid (amino acid) and coconut oil. Cocosulfate: Derived from coconut oil.Cocosulfate: Derived from coconut oil.

71. CURRENT TRENDS AND LIMITATIONS Natural.Natural. Certified Organic.Certified Organic. Animal friendly.Animal friendly. DEA Free.DEA Free. Formaldehyde Free.Formaldehyde Free. Nitrosamine Free.Nitrosamine Free. Sulfate Free.Sulfate Free. Low Dioxane.Low Dioxane.

72. THAT’S IT “IN A NUTSHELL”