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The Complete Book on Emulsifiers with Uses,

Formulae and Processes (2nd Revised Edition)
Code: ENI201

Format: Paperback

Indian Price: 1400

US Price: 150

Pages: 428

ISBN: 9788190568531

NIIR
Publisher: PROJECT CONSULTANCY SERVICES
Emulsifier is an organic compound that encompasses in the same molecule two dissimilar structural groups
e.g. water soluble and a water insoluble moiety. It is the ingredient which binds the water and oil in a cream
or lotion together permanently. The composition, solubility properties, location and relative sizes of these
dissimilar groups in relation to the overall molecular configuration determine the surface activity of a
compound. Emulsifiers are classified on the basis of their hydrophilic or solubilizing groups in to four
categories anionic, non ionic, cationics and amphoterics. Emulsifier is utilized in various industries;
agriculture, building and construction, elastomers & plastics, food & beverages, industrial cleaning, leather,
metals, paper, textiles paints & protective coatings etc. An emulsion is an ideal formulation for the
administration. The emulsion form allows uniform application of a small amount of active ingredient on the
surface of the skin. Some of the important emulsions in different field are pharmaceutical emulsions, rosin &
rubber emulsion, textile emulsions, pesticide emulsions, food emulsions, emulsion in paint industry,
emulsion in polish industry, leather & paper treatment emulsions etc. Various cosmetics creams, such as
moisturizers, contain emulsifiers. Lighter, less greasy feeling creams are oil in water emulsions; heavier
creams used to treat rough skin are water in oil emulsions, with oil as the main ingredient. Liquid soaps,
toothpastes and other body care products also contain emulsifiers. Emulsifiers have the ability to optimize
the concentration of certain nutrients in an emulsion. For example, in hair conditioners, some conditioning
agents can damage hair if not properly diluted in the solution. Emulsifiers are among the most frequently
used types of food additives. Emulsifiers can help to make a food appealing. Emulsifiers have a big effect
on the structure and texture of many foods. Increasing demand for low fat food among health conscious
consumers is gradually driving the market for emulsifiers. Besides stabilizing emulsions, emulsifiers derived
from non hydrogenated fats help in maintaining sensory characteristics of food such as texture, flavor, and
taste that are often lost due to fat reduction. This characteristic of making healthier products similar in taste
to fat containing versions has enabled emulsifiers in gaining widespread acceptance in the market. The
global food industry is also witnessing increase in demand for multipurpose emulsifiers that perform
functions of both stabilization and emulsification. Some of the fundamentals of the book are characteristics
and application of emulsifiers, wetting and detergent structures in emulsifier, effect of surfactant on the
properties of solutions, wetting characteristics of emulsifiers, formulated emulsifiers, non surfactant
functional additives, inert fillers, functional surfactant additives, uses of emulsifiers, household and personal
products, industrial uses of emulsifier, anionic surfactants, non ionic surfactants, cationic, amphoteric and
enzyme, alkylolamides, vinylarene polymers, alkyl sulfates, ethoxylation processes, application of
emulsifiers, etc. The present book contains manufacturing processes of various types of emulsifiers which
have applications in different industries, along with photographs of machinery and equipments. This is a
resourceful book for scientists, technologists, entrepreneurs and ingredients suppliers.

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Content:
1.Characteristics and Application of Emulsifiers
Introduction, Classification of Emulsifiers,
Solubility & Surface Activity of Emulsifiers, Wetting and Detergent Structures in
Emulsifier, Effect of Surfactant on the Properties of Solutions, Wetting Characteristics of Emulsifiers,
Micellar Soluilization of Emulsifiers, Formulated Emulsifiers, Non- Surfactant Functional Additives, Inert
Fillers, Functional Surfactant Additives, Uses of Emulsifiers, Household and Personal Products, Industrial
Uses.

2. Industrial Uses of Emulsifier

Agriculture, Building and Construction, Elastomers and Plastics, Food and Beverages, Industrial Cleaning,
Leather, Metals, Paper, Paints and Protective Coatings, Petroleum Production and Products, Textiles,
Biodegradable Emulsifiers and Water Pollution, Biodegradation, Water Pollution, Re- cent Trends.

3. Anionic Surfactants
Introduction, Carboxylates, Soap, N-Acyls- arcosinates, Acylated Protein Hydrolysates, Sulfonates, Alkyl
benzene Sulfonates, Petroleum Sulfonates, Dialkyl Sulfosuccinates, Naphthalene Sulfonates, N-acyl-N-
alkyl- taurates, 2-Sulfoethyl Esters of Fatty Acids, Olefin Sulphonates, Sulfates & Sulfated fates (Sulfated
Alcohols), Sulfated Natural Fats and Oils, Sulfated Alkanolamides, Sulfated Esters, Ethoxylated and
Sulfated Alkyl
phenols, Ethoxylated and Sulfated Alcohols, Phosphate Esters.

4. Non-Ionic Surfactants
Introduction, Polyoxyethylene Surfactants,
Ethoxylated Alkyl Phenols, Ethoxylated
Aliphatic Alcohols, Carboxylic Esters, Glycerol Esters, Polyethylene Glycol Esters,
Anhydrosorbitol Esters, Ethoxylated Anhydrosorbitol Esters, Glycol Esters of Fatty
Acids, Ethoxylated Natural Fats, Oils and Waxes, Carboxylic Amides, Diethanolamine Condensates,
Monoalkanolamine Condensates, Poly- oxyethylene Fatty Acids Amides, Polyalkylene Oxide Block
Copolymers, Polyoxypropylene-Polyoxyethylene Derivatives, Organo Silicones Derivatives.

5. Cationic, Amphoteric and Enzyme Detergents

Cationic Detergents, Amines not containing Oxygen, Oxygen- Containing Amines,
Except Amides, Amine Oxides, Polyoxy ethylene Alkyl and Alicyclic Amines, 2-Alkyl- 1-(hydroxy- ethyl)-2-
imidazolines, N, N, N' N'-Tetrakis-substituted Ethylen ediamines, Other
Miscellaneous Cationic Surfactants, Amines Having Amide Linkages, Quaternary
Ammonium Salts, Amphoteric Surfactants, Enzyme Detergents.

6. Sulfonated Oils
Historical Background, Chemistry of Sulfation
and Sulfonation, Applications of Sulfonated Oils,
Manufacture of Sulfonated Oils, Sulfation, Sulfonation, Sulfation of individual Oils, Characteristics and
Analysis of Sulfonated Sulfated Oils.

7. Alkylolamides
Introduction, Alkylolamides in Shampoo Formulations, Chemistery of the Alkylola- mides, Mono-
Alkylolamides, Di-Alkylolamides, Pure Di-Alkyl olamides, Phosphoxylated Alkylolamides, Sulphated
Alkylola- mides, Foam Stabilization, Manufacture of Alkylol- amides, Coconut Fatty Acid Die thanolamide,
Lauric Acid Dieth anolamide, Oleic Acid Monoethan olamide, Stearic Acid Mono ethanolamide.

8. Vinylarene Polymers
Monomers, Anionic Polymerization, Polymer
Reactions, Stereoregular Polymerization, Cationic Polymerization, Free-Radical Polymerization, Polymer
Properties, Electrical Proper- ties, Utility and Application.

9. N-Acyl-N-Alkyltaurates
Introduction, Applications of Igepon T Products, Future of Igepons, Manufacture of Igepon T, Raw
Materials, Oleic Acid Chloride, Igepon T Gel, Igepon T Powder, Chemical Control,
Utilities, Materials of Construction.

10. Vinylamine Polymers

Preparation, Polymerization Followed by Hydrolysis, Polymerization Followed by Reduc- tion, Hofmann
Degradation of Poly(acrylamide), Polymerization Kinetics, Copolymers of Vinyl-,Amine Properties,
Chemical Reactions of Poly (vinyl-mine), Uses.

11. Alkyl Sulfates

Introduction, Manufacture of Alcohols, Properties and Performance Characteristics of Alkyl Sulfates, Krafft
Point, Critical Micelle Concentration, Surface and Interfacial Tens- ions, Wetting Time, Foam Height,
Detergency, Dishwashing Test, Emulsion Stability,
Manufacture of Alkyl Sulfates, Sulfation with Chlorosulfonic Acid, Sulfation with Sulfuric Acid, Sulfation with
Sulfur Trioxide, Manufacture of Alkyl Sulfated on Large Scale,
Formulated Products from Alkyl Sulfates.

12. N-Vinyl Amide Polymers

Monomers, Manufacture, Polymerization, Properties of Poly( vinyl Amides), Other Poly
(vinyl Amides), Uses, Cosmetics and Toiletries, Textiles and Dyes, Pharmaceuticals,
Adhesives, Beverage Clarification, Miscellaneous Uses, Specifications and Standards, Analytical and Test
Methods, Health and Safety Factors.

13. Olefin Sulfate and Sulfonates

Introduction, Olefin Sulfates, Raw Materials and Product Composition, Olefin Sulfates from Shale Oil, Olefin
Sulfate from Wax Cracked Distillates, Sulfation, Neutralization and Hydrolysis, Evaporation, Finishing,
Solvent Recovery, Olefin Sulfates, Introduction, Products of Sulfonation, Manufacture of Olefin Sulfonates
Introduction, Batch Sulfonation, Continuous
Sulfonation, Sulfonation with Dioxane- SO3 , Characteristics & Surface Active Properties of Olefin
Sulfonates, Formulated of Heavy-Duty Detergents with Ole fin Sulfonates.

14. Ethoxylation Processes

Introduction, Ethoxylated Alkyl Phenols, Laboratory Method of Preparation, Batch Ethoxylation Unit,
Properties of Ethoxylated Alkyl Phenols.

15. Ethoxylated Fatty Alcohols

Introduction, Laboratory Method of Prep- aration, Continuous Ethoxylation Unit, Properties of Ethoxylated
Fatty Alcohols, Solubility, Cloud Point, Surface and Interfacial Tension, Detergency, Wetting Properties,
Foaming Properties, Emulsifying Properties, Ethoxylated Fatty Acids, Introduction, Manufacture, Properties
of Fatty Acid Ethoxylates, Ethoxylated Fatty Amines, Formulations.

16. Alkyl Phenol Ether Sulfates

Introduction, Sulfation and Sulfonation, Man- ufacture of Alkyl Phenol Ether Sulfates, Sulfamation,
Nonylphenol 4-ethoxy Sulfate, Di- (isohexyl / isoheptyl)phenol Ether Sulfate, Do- decylphenol Ether Sulfate,
Sulfation with Sulfur Trioxide, Comparison of Sulfation with Sulfur Trioxide and Sulfamic Acid, Properties
and Performance Characteristics of Alkyl Phenol Ether Sulfates.

17. Alkyl Ether Sulfates

Introduction, Properties & Performance Characteristics of Alkyl Ether Sulfates, Individual
Alkyl Ether Sulfates, Tallow Alcohol Ether Sulfates, Manufacture of Alkyl Ether Sulfates, Process
Development, Manufacture of Alcohol Ether Sulfates, Formulated Products From Alkyl Ether Sulfates.

18. Fatty Amine Oxides

Introduction, Manufacture of Fatty Amine Oxi- des, Routes to Fatty Amines, Amine Oxidation, Commercial
Synthesis, Properties and Analysis of Fatty Amine Oxides, Amine Oxide Properties, Analytical Methods,
Formulations and Use of Fatty Amine Oxides, Light- Duty Liquids, Heavy Duty Formulations.

19. Bisquaternery and Other Cationic

Softeners
Introduction, Preparation of Bisqu- aterneries, 2- Butene-Bridged-Bisquaterneries,
Diphenyloxide- Bridged-Bisquaterneries, Diethyleneoxide-Bridged- Bisquaterneries, p-Xylylene-Bridged-
Bisquaterneries,2-Butyne-Bridged-Bisquaterneries, Performance Evaluation of Softeners, Multiwash
Softeners Evaluati- on, Softness Evaluation,
Rewettability Measurements, Performance Characteristics of Bisquaterneries and Other Cationics
Softeners, Softener Concentration, Fabric Rewettability Measurements.

20. Other Miscellaneous Emulsifiers

(i) Alkyl Naphthalene Sulfonates

Introduction, General Method of Manufacture, Nekal ‘BXG; Nekal ‘BX' Extra Strong, Dibutyl Naphthalene
Sulfonate, Diamyl Naphthalene Sulfonate.

(ii) Sulfated Alkylolamides

Introduction, Igepon ‘B' Paste, Igepon ‘C' Paste, Sodium-N-2-hydroxyethyl-hexa decanamide H Sulfate.

(iii) Sodium B-Sulfoethyl Esters of Fatty Acids

Introduction, Manufacture of Igepon A.

(iv) Polyethylene Glycol Fatty Acid Esters

Introduction, Manufacturing Process, Fatty Acid Esters of Sucrose.

(v) N-Acylsarcosinates
Introduction, Manufacture of Sodium N- Oleoylsarcosinate.

(vi) Sulfated Monoglyceride

Introduction, Manufacture.

21. Application of Emulsifiers

(i) Pharmaceutical Emulsions

Introduction, Cod Liver Oil Emulsions, Ointments, Beeler's Base, Washable Ointment Base, Greaseless
Base, Ointment Washable Type, Steroidal Emulsion, Aeriflavine Ointment, Aluminium Acetate Lotion,
Typical Antibiotic, Anesthetic and Anti-Inflammatory Ointment, O/W Type Benzyl Ointment, O/W Boric Acid
Ointment, W/O Calamine Cream, W/O Emollient Ointment, Solubilized Hexachlorophene, O/W
Oxyquinoline Sulphate Ointment, Penicillin Ointment.

(ii) Rosin and Rubber Emulsion

Rosin Emulsion, PVA Resin Emulsion, Pentaerythritol Abietate Emulsion, Methyl
Methacrylate Emulsion, Polystyrene Resin Emulsion,
Polyvinyl Ether Emulsion, Synthetic Rubber Emulsion Polymerization, Chlorinated Rubber Emulsion, Wall
Tile Adhesive, Black Industrial Cement, Reclaim Asphalt Dispersion Cement, General Purpose Cement,
Rubber Dressing.

(iii)Textile Emulsions
Antistatic Textile Dressing, Lustre Emulsion for Starching, Root proofing Emulsion, Textile Softeners,
Textile Gloss Oil, Yarn Finish, Soluble Textile Oil, Rope Preservative, Synthetic Thread Lubricant, Acetate
Rayon Oil, Screen Printing Emulsion, Mineral Oil Emulsion, Rayon Delustering.

(iv) Pesticides Emulsions

Malathion Wettable Powder, Dieldrin Formulation, Lindane Formulation, Ronnel Formulation, Butyl Ester of
2, 4-D Formulation, Fruit Coating Wax Emulsion, Cattle Dips, DDT Formulation, Chlordane Formulation,
Heptachlor Formulation, Aldrin Formulation, Endrin Emulsion Concentrate.

(v) Food Emulsion

Chocolate Milk, Stabilized, Artificial Cream, Lemon Oil Emulsion, Transparent Lemon Oil Emulsion, Orange
Emulsion, Bitter Almond Emulsion, Butter Substitute, Mayonnaise, Salad Dressings, Coffee Whitener
Liquid, Coffee Whitener (Spray Dried), Ice Cream Mix, Pickle Flavour Emulsion, Starch Paste.

(vi) Emulsions in Paint Industry

Flat Interior Paint, Semi gloss White Latex Paint, Gloss Emulsion Paint, Exterior Latex Paint, Exterior White
Paint, Interior White Paint, Resin Oil Emulsion.

(vii)Emulsions in Polish Industry

Automobile Polish, ‘Dry Bright' Floor Polish, Paste Polishes, Mineral Oil Emulsion Polishes, Silicone
Polishing Cloth, Paste Type, Automobile Cleaner Polish.

(viii)Leather and Paper Treatment Emulsions

Leather Finishes, Fat Liquors, Leather Dressing,
Shoemaker's Wax Burnishing Polish, Softner for Leather Goods, Leather Pasting, Coating for Paper, Water
Resistant Coating for Paper, Grease Resistant Paper Coating.

(ix) Cutting Oils, Soluble Oils, Miscible Oils

Napthenic Miscible Oils, Cutting Oils, Mold Release Compound.

(x) Cleaners
All Purpose Cleaners, Pine Base Cleaner,
Hand Dishwashing Detergent, Machine Dish- washing Liquid, Household Heavy Duty
Detergent, Household Light Duty Detergent, Fine Fabric Detergent, Hydrogen Peroxide Emulsions, Floor
Wax Remover, Rug Cleaner, Shoe Cleaner, Waterless Hand Cleaners, Acid Aluminium Cleaner, Copper
Cleaner, Degreaser Formulation, Light Duty Steam Cleaner, Alkaline Cleaner, Mercerization Formulation,
Powdered Caustic Bottle Washing Compound, White Wall Tire Cleaner.

22. Determination of Physical Surface

Active Characteristics of Emulsifiers
Introduction, Physical Characteristics, Density of Powdered Detergents, Apparent Bulk Density, Cup
Density, Particle Size of Powdered Detergents, Hand Sieving, Machine Sieving, pH and Alkalinity, Free
Alkalinity, Cloud Point of Non-ionic Detergents, Viscosity, Surface-Active Properties, Ring Method,
Experimental Procedure, Determination of Surface Tension, Determination of Interfacial Tension,
Calculation of Surface Tension, Calculation of Interfacial Tension, Performance Characteristics,
Dishwashing Tests, Laundry Evaluation, Split Item Tests, Bundle Test, Foam Tests, Dynamic Foam Test,
Pour Foam Test, Wetting Test, Canvas Disc Test, Skein Test.

23. Analysis of Emulsifiers

Introduction, Separation of Surfactants, Identification of Components, Anionics, Cationics, Nonionics,
Determination of Surfactants, Total Organic Active Ingredient, Procedure, Correction for Sodium Chloride
Content, Anionic Surfactants, Preliminary Estimate of Mol. Wt., Titration with Cationic Surfactants,
Preparation and Standardization of Titrant, Titration of Sample, Amine Complexation Method,
Determination of Alkylaryl
Sulfonates, Determination of Alkylaryl Sulfonates in the Presence of Short Alkyl Chain Sulfonates,
Determination of Fatty Alcohol Sulfates, Cationic Surfactants, Determination of Amine Oxides, Non-Ionic
Surfactants, Column Techniques, Batch Technique, Tooth Powders, Bath Powders, Light-Duty Liquid
Detergent.

24. Photographs of Machinery and Equipments

Vacuum emulsifying machine-lift cylinder, Vacuum emulsifying machine-lift cylinder, Vacuum emulsifying
machine-mini split, Grinding Machine, Stirrer Homogeneous Emulsifier, Corrosion- Resistant Filling
Machine, Storage Tank, Vacuum Cream Emulsifier Mixer, Vacuum Homogenizer, Meat Emulsifier,
Industrial Emulsifier, Dispersing Machine, Sigma Mixer.

Sample Chapter:
Characteristics and Application of Emulsifiers
Introduction
Emulsifier is an organic compound that encompasses in the same molecule two dissimilar structural groups
e.g. water soluble and a water insoluble moiety. The composition solubility properties location and relative
sizes of these dissimilar groups in relation to the overall molecular configuration determine the surface
activity of a compound. The water soluble moiety is generally referred to as hydrophilic lipophobic and
oleophobic and the water insoluble moiety is called hydrophobic lipophilic and oleophilic. A surfactant in
general possesses the following characteristic properties.
It must be soluble in at least one phase of a liquid system. Its molecules are composed of groups with
opposing solubility tendencies. At the interphase of a liquid system it must form oriented monolayers and its
equilibrium concentration at a phase interface is greater than its concentration in the bulk of the solution. It
forms micelles if the concentration of the solute exceeds a limiting value in the bulk of the solution.
Solutions of surfactants exhibit detergency foaming wetting emulsifying solubilizing and dispersing
properties either individually or collectively.
Classification of Emulsifiers
Emulsifiers are classified on the basis of their hydrophilic or solubilizing groups into four categories anionics
non ionics cationics and amphoterics. The anionic solubilizing groups are carboxylates sulfonates sulfates
and phosphates. Non ionics are solubilized by hydroxyl groups and polyoxyethylene chains. Primary
Secondary and tertiary amines and quaternary ammonium groups are the cationic solubilizers. Amphoteric
surfactants are solubilized by some combination of anionic and cationic moieties non ionic solubilizing
groups may also be part of amphoteric molecules. In addition to the primary solubilizing groups other
structural units c ntribute to the hydrophilic tendencies of molecules e.g. ester linkages and amide linkages.
The hydrophobic i.e. lipophilic moieties are almost invariably hydrocarbon or halogen substituted
hydrocarbon groups. Olefin linkages are less hydrophobic than carbon to carbon single bonds. Products
based on silicon containing hydrophobes are just beginning to be offered in commercial quantities.
Solubility & Surface Activity of Emulsifiers
Emulsifier solute usually displays maximum surface activity and functional effectiveness when it is near the
threshold of insolubility. Moreover the solubility of surfactants is markedly affected by temperature and
electrolyte concentrations. Thus for each set of conditions there is usually an optimum solubility balance for
each type of surfactant. Relatively small changes in the composition of a surfactant are often sufficient to
change its solubility and hence its surface activity. There are many ways to effect such changes for
example the average molecular weight of the raw material mixture i.e. hydrophobe can be increased slightly
or the degree of sulfation sulfonation or ethoxylation can be increased or decreased. Empirical solubility
tests rank with charge weights and chemical analysis as control techniques for surfactant manufacturing
processes. They make it possible to produce to tight specifications by compensating for variations in
successive lots of raw materials or to adjust a process to obtain a range of optimum performance conditions
for essentially the same product but are pointed to different uses.
Wetting and Detergent Structures in Emulsifier
Correlations of functional properties with molecular structures have been sought by numerous investigators.
One result has been the identification of strong wetting and strong detergent structures. The hydrophilic
group of strong wetting agents is located at the middle of the hydrophobic chain or at the central branching
point if the molecule contains two or more chains. Conversely the hydrophilic group in strong detergents is
located at the end of the hydro Characteristics and Application of Emulsifiers phobic chain.
Although the wetting and detersive properties of unformulated anionic and non ionic compounds follow this
structural pattern usefulness of the generalization is limited to the selection of surfactants for a few
specialized applications e.g. textile wetting agents. This limitation is due to the pronounced superiority of
formulated or built products over pure compounds for detergency emulsification etc. In formulations
detergency and wetting strength of individual components lose much of their significance. Textile wetting
efficiency is not simply related to surface tension lowering but dilute aqueous solutions of strong wetting
agents characteristically have low surface tensions.
Effect of Surfactant on the Properties of Solutions
A surfactant changes the properties of a solvent in which it is dissolved to a much greater extent than would
be expected from its concentration. This marked effect is due to (1) adsorption at the solution interfaces (2)
orientation of the adsorbed surfactant ions of molecules (3) miscelle formation in the bulk of the solution
and (4) orientation of the surfactant ions or molecules in the micelles. These effects are caused by the
amphipathic structure of a surfactant molecule and the magnitude of the effects depends to a large extent
on the solubility balance of the molecule. An efficient surfactant is usually relatively insoluble as individual
ions in the bulk of a solution.
Wetting Characteristics of Emulsifiers
Wetting of a solid by a surfactant solution may represent either the displacement of air or some other gas
from the solid surface by the solution of a liquid e.g. an oil from the solid surface. Wettability represents the
tendency of a solid to be wetted and wetting power the tendency of a liquid to wet a solid. The wetting of
one liquid by another immiscible liquid is visually apparent by the spreading of a film to create a large liquid
liquid interface and lack of wetting is evidenced by the tendency of one liquid to form droplets in the form of
a lens on the surface of the other.
The attraction between a solid or liquid to be wetted and the wetting solution determines the degree or
completeness of wetting that can be attained. In practical applications the speed of wetting may be as
important as the completeness of wetting at equillibrium.
Many investigators have pointed out that rate of migration of surfactant molecules from the bulk of the
solution to maintain the concentration of the interface is one limiting factor on the speed of wetting.
Dynamic methods for measurement of the lowering of surface free energy have been used to estimate the
significance of this factor. The effectiveness of mechanical agitation thermal agitation or capillerity in
bringing the solid or liquid to be wetted quickly into intimate contact with the wetting solution often
influences the speed of wetting more than the migration rate of the surfactant.
Micellar Solubilization of Emulsifiers
The spontaneous dissolutions of a normally insoluble substance by a relatively dilute solution of a
surfactant are called Solubilization. The substance dissolved is referred to as the solubilizate and the
surfactant as the solubilizer. There are no simple quantitative relationships between solubilizing power of a
surfactant and the micellar or surface properties of its solutions. Solubilization is primarily a phenomenon of
importance in dilute solutions. In more concentrated solutions it is sometimes difficult to distinguish between
Solubilization and cosolvency which is a term applied to a mixture of solvents that takes into solution a
higher concentration of solute than would be expected from the sum of their individual Characteristics and
Application of Emulsifiers solubilizing powers. Solubilization does not introduce another phase and
solutions containing solubilized material are thermodynamically stable. It is a reproducible phenomenon but
the rates of attainment of equilibrium differ greatly when approached from different directions.
Surfactant molecules or ions at concentrations above a minimum value characteristic of each solvent solute
system associate into aggregates called micelles. The term critical micelle concentration (CMC) is used to
denote the concentration at which micelles start to form in a system comprising solvents surfactants
possibly other solutes and a defined physical environment. The CMC of surfactants in aqueous solutions
depends on the structure of the compounds and the environment but for many anionics at low electrolyte
concentrations and room temperature it is close to 10 2 mols/litre for non ionics under comparable condition
it is less about 10 4 moles/litre. In many surfactants where the hydrophilic group is unchanged but the size
of the hydrophobic group is increased CMC values decrease with increasing size of the hydrophobe for
both ionic and nonionic types. If the hydrophobic group is held constant CMC values decrease with
decreasing ethylene oxide content of non ionic. Increasing the electrolyte concentration decreases CMC
values for both anionics and non ionics. The CMC of anionic micelles increases as the temperature
increases whereas the CMC of non ionics decreases with the increase in temperature as would be
expected from the cloud point phenomenon.
Solubilizations is a micellar phenomenon that occurs only at concentrations above the CMC. It is of
considerable importance in non aqueous applications of surfactants particularly where water is the
solubilizate. Typical applications are in dry cleaning solutions and engine lubricants. Essential oils vitamins
cosmetic emollients and textile mill processing oils are typical solubilizates in aqueous systems. Mixtures of
surfactants are generally better solubilizers than the same surfactants used individually. Ionic non ionic com
binations are especially effective.
Formulated Emulsifiers
Formulated surfactant products may be roughly divided into two major groups. One group is designed to
perform surfactant functions e.g. cleaning wetting foaming emulsifying and dispersing. The other group is
designed to convey a non surfactant functional ingredient to the point of use e.g. a herbicide or insecticide
toxicant a textile mill processing oil. In addition to primary surfactants the components of formulated
surfactant products may be classified as (1) Non surfactant functional additives (2) Inert fillers and (3)
Functional surfactant additives.
Non surfactant Functional Additives
The art of surfactant formulation is directed to finding a combination of components that will be compatible
and perform satisfactorily at the least cost to the user. Frequently a surfactant is the most expensive
component of a formulation and the mixture is designed so that less expensive inorganic additives
contribute as much as possible to the functional performance of the product. Hydrotropic agents are used to
solubilize the ingredients in concentrated liquid surfactant formulations. The most common hydrotropes are
the sodium or potassium salts of benzene cumene toluene or xylene sulfonates. These highly soluble
solutes when present at relatively high concentrations i.e. 5 15 wt percent increase the solubility of
sulfonate and sulfate surfactants in concentrated aqueous compositions. Solvents are also incorporated in
surfactant products to obtain homogeneous concentrates and also as functional additives. For example
ethanol is used as a solvent to clarify liquid shampoos. Pine oil and/or deodorized kerosene are often
functional components of industrial and consumer detergent products.
Inert Fillers
Many surfactants are viscous liquids or low melting solids that Characteristics and Application of Emulsifiers
are difficult to handle as 100 per cent active materials. Sodium sulfate clays or other inexpensive fillers are
added as diluents and carriers to the concentrated surfactants to obtain free flowing dry powders.
Sometimes a portion of the sulfonating or sulfating reagent from the manufacturing process is neutralized
and left in finished products as a filler.
Functional Surfactant Additives
Foam boosters viscosity builders and co emulsifiers are the most important functional additives to
surfactant formulations. The fatty acid alkanolamides and the alkylamine oxides are the outstanding
examples of products in this category. They are effective surfactants on the basis of their own properties
but one of their principal uses is to enhance the foaming and detergency of less expensive materials e.g.
LAS. In these applications the performance of the mixture exceeds a projection based on the sum of the
contributions of the components tested individually. The alkanolamides also increase the viscosity and
emolliency of aqueous solutions. The lipophilic emulsifiers are another group of functional surfactant
additives. Many of these materials are so hydrophobic that they have almost no utility when used alone but
in mixtures with hydrophilic emulsifiers they are exceedingly useful as co solvents solubilizers dispersants
and emulsifiers.

Industrial Uses of Emulsifier

Agriculture
Emulsifiers are used in phosphate fertilizers to shorten manufacturing cycle and prevent caking during
storage. In spray applications of herbicides insecticides and fungicides they are used in wetting dispersing
and suspending of powdered pesticides and emulsification of pesticide solutions to promote wetting
spreading and penetration of the toxicant.
Building and Construction
In paving they prevent stripping by improving the bond of asphalt to gravel and sand. Their use promote air
entrainment in concrete for control of density plasticity and insulating properties etc.
Elastomers and Plastics
In emulsion polymerization they effect the emulsification of monomers by solubilization of monomers and
catalyst which react in surfactant micelles. They also help in stabilization of latexes. In foamed polymers
they effect the introduction of air and control of cell size. In latex adhesive they promote wetting and thus
improve bond strength. In plastic articles they are used as antistatic agents and in plastic coating and
laminating they are used as wetting agents.
Food and Beverages
In food processing plants they are used for cleaning and sanitizing walls floors and process equipment.
They give improved removal of pesticide residues and aid in wax coating of fruits and vegetables. In bakery
products and ice cream they solubilize flavor oils control consistency and retard staling. In beverages they
solubilize flavor oils. In crystallization of sugar they improve washing and reduce processing time. In frying
with cooking fats and oils they prevent spattering due to superheating and sudden volatilization of water.
Industrial Cleaning
In miscellaneous cleaning janitorial supplies and clothes they are used for cleaning and sanitizing walls
floors windows vehicles engines etc. and as detergents for laundry and dry cleaning. In descaling they are
used as wetting agents and corrosion inhibitors in acid cleaning of boiler tubes and heat exchanges. In wax
strippers they are used to improve wetting and penetrations of the old finish.
Leather
In leather industry they are used as detergent and emulsifier in degreasing skins to promote wetting and
penetration in tanning as emulsifiers in fat liquoring of hides to promote wetting penetration and leveling in
dyeing.
Metals
In concentration of ores they are used for wetting and foaming i.e. collecting and frothing in ore flotation. In
cutting and forming of metals they are used for wetting emulsification lubrication and corrosion inhibition in
rolling oils drawing lubricants buffing and grinding compounds. In casting they are used as mold release
additives. In rust and scale removal they are used for wetting foaming and corrosion inhibition in pickling
and electrolytic cleaning. In electroplating they are used for wetting and foaming in electrolytic plating baths.
Paper
In pulp treatment they are used for derinsification pitch dispersion and washing. In paper machine they are
used fordefoaming felt washing colour leveling and dispersing. In calendaring they are used for wetting and
leveling in coating and colouring operations. In towels and pads they are used for wetting to improve
absorption of moisture. Industrial Uses of Emulsifier
Paints and Protective Coatings
In pigment preparation they are used for flushing i.e. promote preferential wetting by the paint vehicle
dispersing and wetting of the pigment during grinding. In latex paints they are used to emulsify the oil or
polymer disperse the pigment stabilizes the latex retard sedimentation and pigment separation modifies
wetting and rheological properties. In waxes and polishes they are used for emulsifying waxes stabilize
emulsions and wet substrates in finishes for floor and automobiles. Petroleum Production and Products
they are used in drilling fluids to emulsify oils disperse solids and modify rheological properties of drilling
and completion fluids for oil and gas wells. In mist drilling they are used to convert intrusion water to foam in
air drilling. In work over of producing wells they are used to emulsify and disperse sludge and sediment in
clean out of wells modify wetting of formation at producing zone. In producing wells they are used to
demulsify crude petroleum and inhibit corrosion of well tubing storage tanks and pipe lines. They are used
for secondary recovery in flooding operations to release crude oil from the formation surface i.e. preferential
wetting. Their application in refined petroleum products include as detergent sludge dispersant and
corrosion inhibitor in fuel oils crank case oils and turbine oils.
Textiles
In the preparation of fibres and filaments they are used as detergent and emulsifier in raw wool scouring
dispersant in viscose rayon spin baths lubricant and antistat in spinning of hydrophobic filaments. In gray
goods preparation they are used for wetting and detergency in slashing and sizing formulations wetting and
detergency in kier boiling and bleaching of cotton and carbonizing of wool detergency in scouring piece
goods emulsification of processing oils. In dyeing and printing they are used for wetting penetration
solubilization emulsification dye leveling detergency and dispersion. In finishing of textiles they are used for
wetting and emulsification in finishing formulations softening lubricating and antistatic additives to finishes.
Biodegradable Emulsifiers and Water Pollution
The Heavy duty household laundry detergents have been in use in largest amounts all over the world as
the major products of the surfactant industry for the last forty five years. The key ingredient that made this
growth possible was ABS an inexpensive alkylbenzene sulfonate in which the alkyl group was a highly
branched propylene tetramer. Its continued discharge in rivers and lakes results in formation of excessive
foams in rivers and lakes causing pollution of water. This fact became apparent for the first time in United
States in 1950. Researches carried out later soon revealed that some types of synthetic detergents were
more resistant than soap to degradation in sewage treatment plants and attempts were made in 1963 in
U.S. to replace ABS the largest volume synthetic surfactant by LAS (Linear Alkylbenzene Sulphonate) a
more biodegradable surfactant in a move to facilitate the degradation of detergent products in sewage
plants.
Research soon established that degradation of surfactants by the bacteria in sewage disposal plants is
slower and less complete if the hydrophobic chain is branched rather than linear. In the early 1950 s no
economically feasible technology was known for replacing ABS by a biodegradable substitute. The logical
approach to the problem was replacement of the propylene tetramer by an equally inexpensive linear 12
carbon alkylation feedstock from a petrochemical source. However technological breakthroughs in the early
1960 s opened up several possible routes to biodegradable alkylbenzene sulfonates.
(1) Separation of n paraffins from kerosene feedstocks in molecular sieves (or alternatively by complexing
with urea). Alkylation with the n paraffins involves only conventional processing i.e. monochlorination
followed by a Friedel Crafts reaction or dehydro Industrial Uses of Emulsifier halogenation and alkylation.
(2) Synthesis of linear 1 olefin or alcoholic detergent hydrophobes from ethylene is carried out by the
Ziegler process using an aluminium catalyst. The trialkyl aluminium intermediate in this process can be
oxidized to yield linear secondary alcohol suitable for detergent bases or catalytically decomposed to yield
1 olefins that can be used as alkylate feedstocks or hydrated to alcoholic hydrophobes.
(3) The 1 olefins obtained by cracking of petroleum waxes can also be used either as alkylation feedstocks
or hydrated to alcoholic detergent bases.
Biodegradation
Microorganisms have an inherent ability to convert organic matter including surfactants into new cell
material food and energy. The predominant mechanisms by which surfactant hydrophobes are attacked
have been described as b oxidation methyl oxidation and aromatic oxidation. In b oxidation the most
important process a linear hydrocarbon chain is oxidized at two carbons at a time a branch in the chain
interrupts the degradation. Methyl oxidation which is less well understood attacks terminal methyl groups.
Aromatic oxidation proceeds through cat echol (1 2 benzenediol) as an intermediate which is cleaved to
form an aliphatic dicarboxylic acid. The poly oxyethylene chains of non ionics are probably degraded
stepwise through a carboxylation and hydrolysis mechanism that splits glycol units from the chain. From a
practical viewpoint secondary and tertiary carbons in aliphatic chains and some phenolic nuclei slow the
biodegradation process to rates that are unacceptable in present day sewage treatment systems. Very
large polyoxyethylene chains are also degraded slowly. In terms of products carboxylic acids and salts
linear alcohol sulphates sulfated fatty acids sulfated fatty amides sulfated esters glycol esters glycerol
esters and fatty alkanolamides are most readily biodegradable. The ethoxylated and sulfated linear alcohols
linear alkylbenzene sulphonates and ethoxylated linear alcohols (upto about 70 wt per cent of
polyoxyethylene) are readily biodegradable. The residual polyoxyethylene chains from high polyethene
content non ionics are not surface active and are not a problem in sewage systems at this time. Ethoxylated
linear alkylphenols are more slowly biodegradable than aliphatic based non ionics. There is still some
question about the acceptability of these products for all uses. Unacceptable products on the basis of
biodegradability are the branched chain substituted alkylphenol derivatives branched chain substituted
alkylbenzene sulfonates and the derivatives of branched chain aliphatic alcohols i.e. sulfates or sulfated
ethyoxylates.
Development of methods to measure biodegradability of surfactants paralleled the development of
biodegradable materials. Three methods out of the many screened have received widespread acceptance.
Two of these the river die away method and shake flask methods. Biodegradation Test Methods are
suitable for quick screening and/or routine use. The third a semi continuous activated sludge method is
more time consuming but is accurate and reproducible enough to serve as a reference method The
determination of biological oxygen demand also provides useful data on biodegradation processes.

Anionic Surfactants
Introduction
The hydrophilic moiety in anionic surfactants is a polar group that is negatively charged in aqueous
solutions or dispersions. In commercial products it is either a carboxylate sulphonate sulfate or phosphate
group. In dilute alkaline solutions in soft water the solubilizing power of the sodium salts of the four anionic
radicals is approximately equal and strong enough to balance the hydrophobic tendency of a 12 carbon
saturated hydrocarbon group the sulfate is actually a somewhat stronger solubilizer than the sulphonate. In
neutral or acidic media or in the presence of heavy metal ions the solubilizing power of the carboxylate is
markedly less than that of the other groups.
The ionic environment associated with anionic surfactants influences the properties of their solutions.
Sodium and potassium salts are generally more soluble in water and less soluble in hydrocarbons.
Conversely the calcium barium and magnesium salts are more compatible with hydrocarbon solvents and
less so with water. Ammonium and amine salts e.g. triethanolamine improve the compatibility of anionics
with water and hydrocarbons and are widely used in emulsification and detergent applications. Higher total
ionic strengths are usually associated with lower solubilities of anionic surfactants. To offset this effect the
molecular weight of the hydrophobe is lower in products designed for use at high electrolyte concentrations.
Micellar solubilization by anionics is markedly affected by total ionic strength and also by the identity of the
associated cations. The anionic surfactants can be divided into four groups according to their anionic
groups (1) Carboxylates (2) Sulfonates (3) Sulfates and Sulfated Products (4) Phosphate Esters.
Carboxylates
Soaps and a small volume of aminocarboxylates are the only Anionic Surfactants commercial products in
the carboxylate class of surfactants. Two types of aminocarboxylate surfactants N acy lsarcosinates and
acylated protein hydrolysates are produced in small quantities as specialties.
Both series of products are fatty acyl derivatives of aminocraboxylates. As compared to the corresponding
soaps the hydrophilic tendency of the amide linkages in these molecules is strong enough to significantly
lessen inactivation of the carboxylate ions by the calcium and magnesium ions that are present in hard
water.
Soap
For many years soap was the only surfactant produced commercially. Inspite of the development of many
new surfactant types it may be noted that soap possesses some desirable properties which are not found in
many other surfactants. The sodium and potassium cocofatty acid soaps are unexcelled as lathering and
cleansing agents in bar detergents for personal use in soft to medium hard water. The C14 to C18 fatty acid
sodium soaps are effective laundry and industrial detergents in soft to medium hard hot water. Soaps
especially amine salts are excellent emulsifiers dispersants and solubilizing agents with a wide range of
industrial uses. Soaps have an emollient action in contact with the skin and leave a soft feel on textile
fabrics.
N Acylsarcosinates
Sodium N lauroylsarcosinate and the sodium N acylsarcosinate derived from coconut fatty acids are soap
like detergents with good lathering properties. They are principally used in dentifrices where it is claimed
they also inactivate the enzymes that convert glucose to lactic acid in the mouth. N Oleoy1 sarcosinate is
used as a textile auxiliary and detergent. The N acylsarcosinates are prepared by the condensation of a
fatty acid chloride with sarcosine (i.e. N methylglycine obtained from the reaction of methylamine formal
dehyde and sodium cyanide) in alkaline aqueous solution.
Acylated Protein Hydrolysates
Fatty acyl aminocarboxylates are prepared from protein hydrolysates by acylation with fatty acid chlorides
or by direct condensation with fatty acids. The commercial products are mixtures that vary in composition
from acyl derivatives of polypeptides from incompletely hydrolyzed protein to mixtures of acylated amino
acids derived from completely hydrolyzed protein. Collagen from leather scraps and low grade hide glues is
used as a source of protein. Derivatives of the incompletely hydrolyzed peptides have a great tolerance for
hard water but their effective ness as surfactants is lower.
Sulfonates
The most effective structure for an anionic surfactant is a sulfonate of the general formula RSO3Na where
R is a biodegradable hydrocarbon group in the surfactant molecular weight range. The R group can be alkyl
or alkylarylene and the product can be a random mixture of isomers as long as it does not contain chain
branching that interferes with biodegradability. The surface activity of the SO3 group is not oversensitive to
variations in the pH or to heavy metal ions and the C S linkage is not susceptible to hydrolysis or oxidation
under normal conditions of use.
Sulfonation processes on surfactant raw materials can usually be adjusted to increase or decrease slightly
the degree of substitution of the solubilizing group on the hydrophobe. The average molecular weight of the
hydrophobic bases can also be increased or decreased slightly. Minor adjustments in these two variables
produce significant differences in performance. Sulfonates are usually obtained in the production process
as free acids that can be neutralized to form alkali metal salts alkaline earth metal salts or amine salts thus
neutralization is another parameter for modification of properties. Manipulation of these variables leads to
products with a multiplicity of combinations of properties from the same raw materials and production
equipment.
The surfactants of commercial importance in this group are alkylbenzene sulfonates petroleum sulfonates
di alkyl sulfosuccinates naphthalene sulfonates N acyl N alkyltaurates 2 sulfo ethyl esters of fatty acids and
olefin sulfonates.
Alkylbenzene Sulfonates
Linear dodecylbenzene sulfonates rank next to soaps in total usage. The sodium salt of linear
dodecylbenzene sulfonate is commonly referred to as LAS . Linear dodecylbenzene sulfonic acid is called
LAS acid and salts other than sodium are named in an analogous manner e.g. LAS salt. Commercial
dodecylbenzene sulfonic acid is a light coloured viscous liquid that is used almost entirely as an
intermediate for the manufacture of alkalimetal alkaline earth metal and amine salts.
In comparisons of the performance of alkylbenzene sulfonates to that of aliphatic sulfonates the effect of
the benzene ring is often considered as approximately equivalent to three carbon atoms in an aliphatic
chain.
Alkylbenzene sulfonic acids are strong organic acids and form essentially neutral alkalimetal salts that have
a good solubility in aqueous solutions at use concentrations over the entire pH range.
These acids are not sensitive to precipitation by the natural hardness of the surface waters but the alkaline
earth metal salts are less water soluble than the alkali metal and amine salts. The calcium salts are
sufficiently soluble in hydrocarbons for use in these media. The alkylbenzene sulfonates are one of the
most chemically stable types of surfactants. The sulfonic group is not susceptible to acidic or ammonium
alkaline hydrolysis under normal conditions of storage or use. The compounds are stable to strong oxidising
agents is aqueous solutions at use concentrations and are stable in carefully formulated products
containing oxidizing agents.
The surface activity of unformulated unbuilt dodecyl benzene sulfonates is sufficiently strong for the salts to
be useful for their detersive wetting emulsifying dispersing and foaming properties but they are not
outstanding surfactants. The widespread usage of LAS stems from other factors which include their low
cost reproducible quality adequate supply light colour low odour and excellent response to formulation and
builders. For example LAS solutions are only average foamers but mixtures of LAS with alkanolamine or
alkylamine oxide foam boasters have excellent foaming properties. Similarly LAS performs well in built
heavy duty cleaning products where the wetting foaming emulsifying and dispersing properties of the
surfactant component are as important as the detergency power. Amine salts of LAS & ABS acids are used
in blends with other emulsifiers particularly the non ionic types in emulsifiable concentrates of pesticides.
Petroleum Sulfonates
The petroleum sulfonates are the only large volume class of surfactants that are used predominantly in non
aqueous systems. They are available as co products of the refining of certain petroleum fractions. They are
usually grouped into two broad classes water soluble types called green soaps and oil soluble types called
mahogany soaps (which may also be soluble in water).
The green soaps are of little use. The mahogany soaps are valuable for their properties of solubilization
detergency dispersion emulsification and corrosion inhibition. Their principal use is in lubricating oils for
sludge dispersion detergency micellar solubilization of water and corrosion inhibition. They are also widely
used in other products for corrosion inhibition and emulsification. Alkylaromatic hydrocarbon sulfonates are
the surfactant components in both product types. The green soaps contain a higher proportion of
disulfonates than the mahogany sulfonates which are principally monosul fonates.
Dialkyl Sulfosuccinates
Sodium di (2 ethyl hexyl) sulfosuccinate is the largest volume product of this group. It is now a widely used
specialty surfactant.These sulfosuccinates as sodium salts are available as white waxy odourless solids or
as concentrated colourless solutions. The di C8 esters have the optimum solubility balance for use in tap
water or aqueous solution with low inorganic salt content lower alkyl esters are more effective in saline
solutions. Sodium dialkyl sulfosuccinates are highly surface active but the susceptibility of the ester linkage
to acidic or alkaline hydrolysis limits their usefulness. The products have strong wetting rewetting
penetration and solubilization properties. The symmetrical diesters are produced by esterification of maleic
anhydride using conventional technology followed by addition of sodium bisulfite across the olefin linkage.
Naphthalene Sulfonates
Four series of specialty surfactants make up the widely used but relatively low volume group naphthalene
sulfonate products viz. salts of alkylnaph thalene sulfonates salts of sulfonated formaldehyde naphthalene
condensates salts of naphthalene sulfonates and salts of tetrahydronaphalene sulfonates.
In the concentrated dry form most of the salts are almost odourless light grey solids. They are readily and
highly soluble in water. In fact except for the nonyl derivatives the naphthalene sulfonates are generally too
soluble to be strongly surface active in soft water. The naphthalene sulfonates are stable to hydrolysis in
acidic or alkaline media and are not sensitive to oxidation by strong oxidizing agents under use conditions.
The naphthalene sulfonates are used in many different applications as wetting and dispersing agents.
Several members of the series are effective as stabilizing and suspending agents in disperse systems.
Some of the products are useful for their solubilizing properties. Hard water does not adversely affect the
surface activity of typical members of the series.
N acyl N alkyl taurates
The taurates are technically interesting as the only class of anionic surfactants with the combination of
many advantages. They are stable against hydrolysis by acidic or alkaline media at use concentrations.
They show no loss of performance in hard water. They have soap like biodegradability and residual feel on
washed fabrics and they have a molecular structure capable of yielding either strong wetting or strong
detergent configurations. For example the products RCON (R`) CH2CH2SO3Na are strong detergents
when R = C11 C17 and R` = CH3 or C2H5 but are strong wetters when R = R` = C6 9. Relatively high raw
material costs have held usage of the presently available N acyl N alkyl taurates in the specialty category
and have precluded the introduction of additional products with markedly different properties.
The commercial product N Oleoyl N methyltaurate is marketed as a light yellow solid at about 70 per cent
assay or at lower concentrations in water as a light coloured slurry solution or gel. It is principally used in
detergent applications with out builders. Foaming of the N methyl derivatives is only moderate and is not
readily improved by the usual foam builders the N cyclohexyl derivatives are low foaming detergents with
good wetting power.
The production of sodium N oleoyl N methyltaurate involves three chemical steps and yields average 95
percent or higher in each step.
2 Sulfoethyl Esters of Fatty Acids
These products known commercially as b sulfoesters resemble closely in properties the fatty acids from
which they are derived but they have the advantage that hard water does not impair their performance.
Only the sensitivity of the ester linkage to hydrolysis has prevented their widespread usage in consumer
detergents. Hydrolysis is not a problem with detergents for personal use and the sodium salt of the 2
sulfoethyl ester of lauric acid or similar coconut acid mixture has found acceptance as the foaming and
cleansing ingredient in synthetic detergent bars. The oleic acid analog is less foaming but is a good
detergent with specialty uses in neutral or mildly alkaline systems.
The esters can be produced commercially from isethionate (obtained by the reaction of ethylene oxide with
a concentrated solution of sodium bisulfite) and the fatty acid or acyl chloride. The reaction between the
acyl chloride which is a viscous liquid and the powdered anhydrous sodium isethionate is carried out in the
absence of water or solvent under vacuum in a heavy duty mixer. After the total charge is added to the
reactor and brought to temperature HCL is rapidly evolved leaving the finally divided light coloured product
as the sodium salt.
Olefin Sulphonates
The increasing availability of relatively low cost linear 1 olefins in the C14 to C18 range has spurred
research and commercial development of their sulfonate derivatives.
The 3 and 4 hydroxysulfonates which may amount to as much as half of the yield of sulfonated products
are not very water soluble but they are solubilized in the presence of the more soluble olefin sulfonate. The
sulfonation mixture which is referred to as a olefin sulfonate or AOS has detergency and foaming properties
similar to C11 14 LAS. It is superior in performance to similar products made from internal straight chain
olefins. Biodegradability of the AOS is slightly better than LAS toxicity and skin irritation are slightly less.
Sulfates & Sulfated Products
The hydrophilic group in the surfactants falling in this group is SO3 attached through an oxygen atom to a
carbon atom in the hydrophobic moiety. The additional oxygen makes the sulfate a stronger solubilizing
group than the sulfonate but the C O S linkage of the sulfates is more easily hydrolyzed than the C S
linkage of the sulfonates. This susceptibility to hydrolysis especially in acidic media limits the utility of the
sulfates. Solubilization of hydrophobes through the combination of ethoxylation and sulfation is frequently
used to obtain the optimum solubility balance and also to utilize less expensive raw materials that cannot
be solubilized sufficiently by sulfation alone e.g. derived from tallow alcohols. The shift of the detergent
industry to more biodegradable products has started a trend away from ethoxylated and sulfated alkyl
phenols and towards ethoxylated and sulfated aliphatic alcohols. The principal sub groups of this class of
surfactants are discussed below.
Alkyl Sulfates (Sulfated Alcohols)
The hydrophobes of this class of surfactants are obtained by reduction of fatty acids or esters of C12 to
C20 hydrocarbon groups.
Secondary olefins sulfates are prepared by the addition of sulfuric acid to an olefin. These products have
been marketed under the Teepol trademark of shell Oil Company. Sulfates obtained from the normal
primary alcohols are similar in performance properties and in feel or emollient characteristics to the soaps
of corresponding molecular weight. The branched chain alkyl sulfates are strong wetters. As the carbon
chain length increases the temperature needed to attain maximum detergent and wetting effects also
increases. The stability of alkyl sulfates to hard water is excellent. In fact magnesium lauryl sulfate forms
voluminous foams with a low water content that is useful in rug shampoos where the soil is removed by
vacuum pick up of the foam that is generated by vigorous brushing with a minimum volume of detergent
solution. Sensitivity to hydrolysis in hot alkaline or acidic media is one of the principal disadvantages of the
alkyl sulfates. Alkyl sulfates are high foaming detergents and strong wetters as well as effective emulsifiers
and dispersants. Some of the products are used as leathering and cleansing agents in shampoos and
dentifrices. Others are detergent and wetting agents for textile processing. Another use of the alkyl sulfates
is as emulsifiers and dispersents in emulsion polymerization.
Lauryl sulfates can be prepared as the ammonium sodium potassium magnesium diethanolamine and
triethanolamine salts which is indicative of the marked influence of the cations on the performance
properties of this series of anionic surfactants.
Sulfated Natural Fats and Oils
The sulfated surfactants from natural fats and oils are obtained by the reaction of sulfuric acid which either
CH = CH or OH groups in natural fats and oils. The sulfate half esters so obtained are neutralized with
caustic soda in a later step.
Olive oil was the first oil to be sulfated to obtain a commercial surfactant other than soap. Later on almost
every potentially available animal vegetable and fish oil was tried and it was found that ricinoleic acid which
contains one hydroxyl group and one double bond is a desirable constituent of an oil for sulfation. Oleic
acid is also satisfactory. Esters of these acids can usually be sulfated with a minimum of hydrolysis.
Polyunsaturated fatty acid moieties are undesirable components of glycerides for sulfation since the
resulting surfactants are usually dark in colour and sensitive to oxidation.

NON IONIC Surfactants

Introduction
A non ionic surfactant as the name implies bears essentially no charge when dissolved or dispersed in
aqueous media. The hydrophilic tendency in a non ionic is due primarily to oxygen in the molecule which
hydrates by hydrogen bonding to water molecules. The strongest hydrophilic moieties in non ionics are
ether linkages and hydroxyl groups but ester and amide linkages which are also hydrophilic are present in
many non ionics. The contribution of each oxygen to solubilization is weak and non ionic molecules must
contain a multiplicity of them in order to be water soluble. Nearly all of the unmodified polyol surfactants are
lipophilic and they are frequently used as coemulsifiers in combinations with more hydrophilic surfactants.
One advantage of the non ionics is that they are compatible with ionic and amphoteric surfactants.
Polyoxyethylene solubilization is the key to the substantial and continuing growth of the non ionics. Since
the polyoxyethylene group can be introduced into almost any organic compound that has reactive hydrogen
a wide range of organic substances can be solubilized by ethoxylation. Sub division of the non ionics into
classes in accordance with the composition of the solubilizing groups is not as straight forward as with the
ionic surfactants.
Polyoxyethylene Surfactants
The polyoxyethylene solubilized non ionics are mainly used as textile auxiliaries. The solubility of these
products depends on recurring ether linkages in a polyoxyethylene chain. A solubilized molecule contains
many such chains and its hydrophilic tendency increases with the polyoxyethylene content of the molecule
and 60 70 per cent by weight is required on most surfactant hydrophobes for complete miscibility with water
at room temperature. A rule of thumb is that the hydrophilic strength of one ethylene oxide unit is
approximately equal to the hydrophobic strength of one methylene unit. The water solubility of
polyoxyethylene compounds decreases as the temperature increases which is attributed to a decrease in
the degree of hydration or to an increase in the size of the micelles. The temperature at which a second
phase appears is called the cloud point a practical solubility test that is not sensitive to concentration
differences in the range between 0.5 to 10 per cent by weight. A minor proportion of anionic mixed with a
non ionic will often raise the cloud point to several degrees. Surface activity and performance efficiency of
polyoxyethylene non ionics is not adversely affected by hard water. High electrolyte concentrations in which
sodium ions are the predominant component decrease the solubility of polyoxyethylene compounds by a
salting out effect whereas hydrochloric acid and calcium ions increase their solubility. Non ionic surfactants
solubilize iodine in aqueous solutions and lessen its toxicity to humans but do not weaken its biocidal
activity to the lower forms of life. The polyoxyethylene surfactants are moderate foamers and do not
respond to the conventional foam boosters. They exhibit a foam maximum as a function of polyoxyethylene
content. Low foaming non ionics are prepared by terminating the polyoxyethylene chain with a less soluble
group e.g. polypropylene oxide. A significant advantage of solubilization by means of polyoxyethylene is the
capacity of attaining almost any hydrophilic/hydrophobic balance. A shortcoming is that the polyoxyethylene
non ionics tends to be liquids or low melting waxes that are difficult to incorporate into dry free flowing
powders. Flaked solid products containing a high ratio of polyoxyethylene are manufactured but their
surface activity is low because they are too hydrophilic.
The conversion of an aliphatic alcohol alkyl phenol or fatty acid into a polyoxyethylene derivative can be
divided into two steps addition of ethylene oxide to the hydrophobe to form a monoadduct and subsequent
additions of ethylene oxide in a polymerization reaction. Ethoxylations of these hydrophobes are catalyzed
by bases. Ethoxylation is normally carried out as a batch re action although continuous reactors have been
designed and operated. The hydrophobe and a solution of catalyst are charged into a reactor. Air and
solvent for the catalyst are removed by agitating and heating under a vacuum or purging with nitrogen or
both. When the hydropbobe is at the reaction temperature addition of ethylene oxide is started. The
polymerization is exothermic (20 kcal/mole of ethylene oxide reacted) and the rate of ethylene oxide
addition should not exceed the cooling capacity of the reactor since careful maintenance of the reaction
temperature is essential for reproducible manufacture of products to specifications. The end point of
ethylene oxide addition is often determined by testing the solubility of a sample for its cloud point in water a
salt solution or a water solvent mixture. After the reaction is complete the catalyst is neutralized and the
product is discharged to storage or packaged. Polyoxyethylene solubilized non ionics are poly disperse
mixtures of compounds that differ principally in the distribution of the polymer chain lengths. Their
properties usually approximate those of the pure isomer represented by their average composition.
Ethoxylated Alkyl Phenols
Undiluted polyoxyethylated C8 to C12 alkyl phenols have a slight aromatic odour and vary from pale yellow
to almost colourless. Products with low polyoxyethylene content are liquids and their viscosity increases
with the content of combined ethylene oxide. High ratios of polyoxyethylene to hydrophobe are waxes. The
specific gravity at room temperature increases with polyoxyethylene content from less than 1 to 1.2
Physical properties of the polyoxyethylated higher alkyl phenols e.g. dinonylphenol and hexadecylphenol
are similar to those of the C8 to C12 derivatives with the same wt. percentage of combined ethylene oxide.
The solubility in water of the ethoxylated alkyl phenols increases with the polyoxyethylene content. About
60 per cent by weight of polyoxyethylene is required for complete miscibility in cold water and at above 75
per cent of polyoxyethylene the products do not cloud out at the boiling point. Water hardness does not
adversely affect the surface activity of the products. The solubility of polyoxyethylene alkyl phenols in highly
aliphatic mineral oils decreases faster with increasing polyoxyethylene content than the corresponding
increase in solubility in water. Solubility in aromatic solvents and unsaturated triglycerides persists at higher
mole ratios of combined ethylene oxide to hydrophobe. The excellent stability of the polyoxyethylene alkyl
phenols against decomposition is demonstrated by their uses in formulations for acid cleaning of metals in
hot alkaline detergent systems and in oil well drilling fluids for use at high bottom hole temperatures.
The maximum surface activity of the unformulated polyoxyethylene alkyl phenols in water hardness of 0
300 ppm is associated with polyoxyethylene proportions in the range of 50 75. per cent by wt. The optimum
composition varies somewhat within this range depending upon the property. Typical commercial products
of polyoxyethylene alkyl phenols include nonyl octyl and doceyl phenoxy polyethylene oxy ethanols. Uses
of polyxyethylene alkyl phenols as a function of polyoxyethylene content can be summarized as follows
Alkyl phenols containing 20 40 per cent polyoxyethylene are used as defbamers in surfactant
solutions detergent and/or dispersing agents in petroleum oils coemulsifiers intermediates for sulfation.
Alkyl phenols containing 40 60 percent polyoxyethylene are used for oil soluble detergents dispersants and
emulsifiers emulsifiers in emulsifiable concentrates of insecticides and herbicides intermediates for
sulfation.
Alkyl phenols containing 60 70 per cent polyoxyethylene are used for textile detergents and
processing auxiliaries pitch control in manufacture of paper pulp rewetting agents in paper towels
processing assistants in leather manufacture detergents in industrial and consumer cleaning products
wetting agents in acid and alkaline cleaners emulsifiers in emulsifiable concentrates of insecticides and
herbicides.
Alkyl phenols containing 70 80 per cent poly oxyethylene are used for detergents and wetters at high
temperature and/or electrolyte concentrations emulsifiers for fats oils and waxes stabilizers for synthetic
latexes wetting and penetrating agents in caustic solutions.
Alkyl phenols containing 80 95 per cent poly oxyethylene are used as stabilizers synthetic latexes
emulsifiers for vinyl acetate and acrylate emulsion polymerization dyeing and leveling assistants lime soap
dispersants.
Commercial ethoxylations of Alkyl phenols are always alkali catalyzed but the reaction conditions catalyst
and catalyst concentration are chosen to obtain optimum properties for the intended use. All of the Alkyl
phenol combines with one molecule of ethylene oxide to form the monoadduct before the build up of linear
polyoxyethylene chains start but by relatively minor variations in reaction conditions it is possible to obtain
either a broad or narrow distribution of isomers at the same percentage content of polyoxyethylene. These
differences are reflected in the properties of the products particularly the solubilities. Another variant at
constant gross composition is the percentage of polyglycol in the product i.e. ethylene oxide polymer not
combined with the Alkyl phenol.
Ethoxylated Aliphatic Alcohols
The ethoxylated aliphatic alcohols are costlier than the ethoxylated Alkyl phenols but due to recent change
over to biodegradable products in the ensuing reformulation of industrial and consumer products a shift in
non ionic types appears to be taking place with polyoxyethylene alcohols instead of polyoxyethylene linear
Alkyl phenols replacing the branched chain Alkyl phenol derivatives in a significant fraction of the newer
formulations. In the products of commerce which include oleyl cetyl stearyl lauryl tridecyl myristyl and
tallow polyethylene oxy ethanols the hydrophobes are generally mixtures of straight chain alcohols in the
range from C12 to C18 and contain combined ethylene oxide in more ratios varying from 1 to 50 to
hydrophobe. The undiluted products vary in physical form from liquids to many solids viscosity in each
homologous series increases as the polyoxyethylene content increases. The products have a slight odour
characteristic of the hydrophobe that decreases as the polyethelene content increases. The liquids vary
from pale yellow to almost colourless and the solids from yellow to white waxes the products become lighter
coloured as the polyoxyethylene content increases. Within each homologous series the specific gravity at
room temperature increases with the polyoxyethylene content from slightly less than 1 until it levels off a
little under 1.2. Solubility of the alkylpoly (ethyleneoxy) ethanols in water increases with the ethylene oxide
content about 65 70 vol percent of polyethylene is required for complete miscibility at room temperature.
The solubility of the polyoxyethylene derivatives of straight chain alcohols in aliphatic solvents is slightly
greater than for the Alkyl phenols of comparable polyoxyethylene content. The water hardness does not
impair the surface activity of the alkylpoly (ethyleneoxy) ethanols.
The functional properties and uses of the polyoxyethylene alcohols parallel very closely those of the
polyoxyethylene Alkyl phenols. The usage of alkylpoly (ethyleneoxy) ethanols is divided more evenly
among the available hydrophobes than with Alkyl phenols. This makes available a wider range of
solubilities in water insoluble liquids and contributes to the widespread use of the products as special
purpose emulsifiers. The Alkyl polyethyleneoxy ethanols have certain uses such as textile fibre lubrication
that are due to properties of the hydrophobe and for which the comparable polyoxyethylene Alkyl phenols
are not applicable.
Ethoxylation processes and equipment for manufacture of the alkylpoly (ethyleneoxy) ethanols are similar
to those described for the Alkyl phenols. However the rate of reaction of primary alcohols with ethylene
oxide is much faster than it is with Alkyl phenols it is much closer to the rate at which the polyoxyethylene
chains grows. Thus the build up of polyoxyethylene polymer chain starts before all of the hydrophobe has
reacted with one unit of ethylene oxide. The reactivity of alcohols with ethylene oxide varies in the order
primary > secondary > tertiary. It is difficult to prepare polyoxyethylene derivatives of tertiary alcohols by
direct reaction of the alcohol with ethylene oxide.
Carboxylic Esters
The carboxylic esters may be polyolsolubilized or poly oxyethylene solubilized or both for surfactant use.
They are based on several different types of hydrophobes and accordingly they are classified as glycerol
esters polyethylene glycol esters anhydrosorbitol esters ethoxylated nhydrosorbitol esters ethylene a and
diethylene glycol esters propanediol esters ethoxylated natural fats and oils carboxylic acid esters silicone
compounds etc.
Glycerol Esters
These are partial fatty acid esters either mono or diglycerides of fatty acids. The products of commerce are
almost invariably mixtures of mono and diglycerides that also differ in respect to the positions of the
hydroxyl group that are esterified. Typical products in the series include the mono and diglycerides of
stearic lauric oleic and ricinoleic acids and coconut tallow lard cottonseed and safflower oils.
Mono and di glycerol esters of the saturated fatty acids are light coloured solids with melting points between
25 and 85°C. The 1 monoglycerides have higher melting points than the corresponding 2 monoglycerides.
The glycerides of the unsaturated fatty acids are liquids at room temperature. The partial glycerol fatty
esters have the characteristic odour of the fats from which they are derived. The polyol group of a
monoglyceride is not strong enough as a hydrophilic moiety to carry even an easily solubilized acid like
oleic into aqueous solution. Despite their lack of water solubility the partial glycerol esters have
commercially important and technically interesting surfactant uses.
The uses of mono and diglycerides centre around applications involving emulsification dispersion
suspension solubilization and lubrication. One important use is as additives to foods and pharmaceuticals.
Products intended for ingestion are prepared from edible fats. Mono and di glycerides are widely used in
bread cakes and other bakery products for their emulsifying dispersing and lubricating properties. They are
also used in candies ice creams yeasts butter whipped tappings and icings. Flavour oils for carbonated
beverages as well as bakery products are emulsified or solubilized by surfactant mixtures that include
blends of mono and diglycerides. Glycerol mono stearate is used as an emulsifier and opacifier in cosmetic
formulations. The partial glycerol esters are used as compounds of textile mill processing and in lubricants
and softener formulations. The products also find application as emulsifiers lubricants and corrosion
inhibitors in cutting drawing and finishing of metal products. In the manufacture of paints and polymers the
mono and diglycerides are used as emulsifiers dispersants suspending agents and grinding oils.
Alcoholysis of fats with glycerol is the most important industrial method for the preparation of the partial
fatty acid esters of glycerol. In this reaction the fatty acid groups are redistributed between the original
combined glycerol and the added glycerol without weight loss by heating at 180 250°C in the presence of
an alkaline catalyst.
Polyethylene Glycol Esters
The polyoxy ethylene esters of fatty acids and of aliphatic carboxylic acids related to abietic acid comprise
the polyethylene glycol series of surfactants. Properties and uses of these two groups of products differ
markedly. Commercial polyoxyethylene fatty acid esters are mixtures that contain varying proportions of
mono esters di esters and polyglycol. The composition of the mixture can be forced toward the mono or di
ester by the ratio of reactants and process of manufacture. The polyoxyethylene esters of fatty acids range
in consistency from free flowing liquids to slurries to firm waxes.
Within a homologous series the products change from liquids to waxes as the polyethylene content
increases. Only low mole ratios of polyoxyethylene to unsaturated fatty acids or lower molecular weight
acids yield liquid products. The odour of the products is characteristic of the fatty acid hydrophobe and
decreases as the polyoxyethylene content increases. Odour and odour stability are important
characteristics of these products because of their use in textile finishing. Colour stability is also important
for the same reason. The oleates for example have good softening and lubricating properties but are
precluded from some uses because of yellowing on exposure to air and heat.
The ester linkage is slightly hydrophilic and only about 60 wt. per cent of polyoxyethylene is required to
solubilize the saturated fatty acids in water at room temperature. The surface activity of the fatty acid
polyglycol esters e.g. wetting and surface tension lowering is in the useful range but less than for
ethoxylated Alkyl phenols or aliphatic alcohols. The products are low foamers in aqueous solutions which is
advantageous for certain uses. Emulsification is a key property of this series of compounds and its
importance is reflected in the wide range of lipophilic solubilities that are available in commercial products.
Susceptibility to hydrolysis in hot acidic or alkaline solutions is their principal limitation. The fatty acid that is
formed by acidic hydrolysis either separates as oil or forms an insoluble precipitate with the heavy metal
ions in hard water.
The Polyoxyethylene fatty acids are used extensively in the textile industry as emulsifiers for processing oils
antistatic agents softeners fibre lubricants and detergents for neutral scouring operations. The products are
also used as emulsifiers in cosmetic preparations pesticide formulations etc.
Two methods are used commercially for manufacture of the polyoxyethylene acids. One is the alkali
catalyst reaction of a fatty acid with ethylene oxide. The other is esterification of a fatty acid with a
preformed polyethylene glycol in the presence of an acid catalyst. Some manufacturers claim that the
properties are different for products of the same gross composition as prepared by the two methods.
However the ethoxylation catalysts also catalyze trans esterification and the products of direct ethoxylation
approach closely those obtained by esterification if the manufacturing process is directed to this end.
Deodourization and decolorization treatments are commonly incorporated in manufacturing processes.
The polyoxyethylene derivatives of the rosin acids are generally similar to the corresponding
polyoxyethylene fatty acids in surfactant properties and processes of manufacture except that they are
stable towards hydrolysis. The chemical stability of the polyoxyethylene tallates together with their
characteristic low foam generation at use concentrations makes themuseful as components of consumer
deter include the mono and diglycerides of stearic lauric oleic and ricinoleic acids and coconut tallow lard
cottonseed and safflower oils.
Mono and di glycerol esters of the saturated fatty acids are light coloured solids with melting points between
25 and 85°C. The 1 monoglycerides have higher melting points than the corresponding 2 monoglycerides.
The glycerides of the unsaturated fatty acids are liquids at room temperature. The partial glycerol fatty
esters have the characteristic odour of the fats from which they are derived. The polyol group of a
monoglyceride is not strong enough as a hydrophilic moiety to carry even an easily solubilized acid like
oleic into aqueous solution. Despite their lack of water solubility the partial glycerol esters have
commercially important and technically interesting surfactant uses. The uses of mono and diglycerides
centre around applications involving emulsification dispersion suspension solubilization and lubrication.
One important use is as additives to foods and pharmaceuticals. Products intended for ingestion are
prepared from edible fats. Mono and di glycerides are widely used in bread cakes and other bakery
products for their emulsifying dispersing and lubricating properties. They are also used in candies ice
creams yeasts butter whipped tapings and icings. Flavour oils for carbonated beverages as well as bakery
products are emulsified or solubilized by surfactant mixtures that include blends of mono and diglycerides.
Glycerol mono stearate is used as an emulsifier and opacifier in cosmetic formulations. The partial glycerol
esters are used as compounds of textile mill processing and in lubricants and softener formulations. The
products also find application as emulsifiers lubricants and corrosion inhibitors in cutting drawing and
finishing of metal products. In the manufacture of paints and polymers the mono and diglycerides are used
as emulsifiers dispersants suspending agents and grinding oils.
Alcoholysis of fats with glycerol is the most important industrial method for the preparation of the partial
fatty acid esters of glycerol. In this reaction the fatty acid groups are redistributed between the original
combined glycerol and the added glycerol without weight loss by heating at 180 250°C in the presence of
an alkaline catalyst.
Anhydrosorbitol Esters
Fatty acid esters of anhydrosorbitol are the second largest class of polyol solubilized surfactants. The
important commercial products in the group are mono di or triesters of sorbitan and fatty acids. Sorbitan is
a mixture of anhydrosorbitols with the principal isomers being 1 4 sorbitan and isosorbide.
The sorbitan oleates and the monolaurate are pale yellow liquids. The palmitates and stearates are light tan
solids. Sorbitan is not a strong hydrophilic group and its derivatives are not water soluble but they are
soluble in a wide range of mineral and vegetable oils. The sorbitan esters are lipophilic emulsifiers
solubilizers softeners and fibre lubricants. Many of the products have been approved for human ingestion
and are widely used as emulsifiers and solubilizers in foods beverages and pharmaceuticals. Another
important application is in synthetic fibre manufacture and textile processing as antistats fibre lubricants
softeners and emulsifiers of textile mill processing oils. The sorbitan esters are also widely used as
emulsifiers in cosmetic products.
The anhydrosorbitol esters are prepared commercially by direct esterification of sorbitol with a fatty acid in
the presence of an acidic catalyst at temperatures in the range 225 250 °C. Internal ether formation as well
as esterification takes place under these conditions. The commercial products of importance in this group
include the mono and trilaurates oleates stearates and palmitates.
Ethoxylated Anhydrosorbitol Esters
Ethoxylation of the sorbitan fatty acid esters leads to a series of more hydrophilic surfactants. They are
widely used as emulsifiers antistats softeners fibre lubricants and solubilizers. The ethoxylated sorbitan
esters are often used as co emulsifiers with the unethoxylated sorbitan fatty acid esters or the glycerol
partial fatty acid esters. Sorbitan fatty acid esters can be reacted with ethylene oxide in the presence of an
alkaline catalyst at temperatures from 130 to 170°C to produce the ethoxylated derivatives.
Glycol Esters of Fatty Acids
The ethylene glycol diethylene glycol and 1 2 propanediol esters of fatty acids are widely used surfactants.
The commercial products are mixtures of mono and diesters even though the stated composition usually
refers only to the principal component. The mono and dilaurates and oleates of ethyleneglycol diethylene
glycol and propylene glycol are liquids. Stearates of these glycols are solids. The glycol esters are strongly
lipophilic emulsifiers opacifiers and plasticizers that are normally formulated in combination with hydrophilic
emulsifiers. They are used as components of cosmetic preparations. The monoesters of glycols can be
manufactured by the alkali catalyzed reaction of ethylene or propylene oxide with fatty acids. Mono and
diesters are also prepared by esterification of a fatty acid with a glycol.
Ethoxylated Natural Fats Oils and Waxes
The products of commercial importance in this group of surfactants are chiefly ethoxylated castor oil and
ethoxylated lanolin derivatives.
Castor oil is a triglyceride with a high content of esterified ricinoleic acid. Its ethoxylation in the presence of
an alkaline catalyst to a polyoxyethylene content of 60 70 wt. per cent yields water soluble surfactants. The
composition of the ethoxylated derivatives is more complex than might be expected. The ethoxylates are
yellow to amber viscous liquids with specific gravities slightly greater than 1.0 at room temperature.
Ethoxylated castor oils are hydrophilic emulsifiers dispersants and lubricants. They are used as processing
assistants and finishing agents in the manufacture of paper leather and textile products. Other uses are in
emulsion polymerizations paints polishes and cosmetic products. Skin irritation and phytotoxicity are usually
low.
Lanolin alcohols are derived from the fat that is stripped from raw wool. They are a mixture of cholesterol
isocholesterol and other higher alcohols. Lanolin alcohols purified by bleaching solvent extraction
crystallization or molecular distillations are ethoxylated to yield non ionic emulsifiers. The mole ratios of
ethylene oxide to alcohols that are offered commercially represent a full series of lipophilic and hydrophilic
products. Their largest use is as emulsifiers in cosmetic preparations.

Sulfonated Oils
Historical Background
In the early days of textile industry soap in one form or the other was the only cleansing wetting emulsifying
and dispersing agent available. Its inability to stand hard water and acid led to the development of a product
possessing the valuable properties of soap without its defects. The first successful attempt towards this was
of Fremy a Frenchman who studied the effect of concentrated sulfuric acid on olive oil but it was A. Runge
who first prepared sulfated olive oil by first reacting the olive oil with concentrated sulfuric acid and then
neutralized the reaction product with cold caustic potash solution. The product was an oily water dispersible
substance. A British patent was granted to Mercer in 1847 for sulfonating olive oil which was to be used in
dyeing madder Turkey Reds. Since then many different oils have been sulfated e.g. rapeseed oil
cottonseed oil castor oil groundnut oil and corn oil etc and neutralized with alkalies. The term Turkey Red
Oil has since been used for sulfonated castor oil.
The reaction between any oil and sulfuric acid takes place in several ways depending on the temperature
the intimacy with which the materials are brought into contact and the time. The major reaction results in a
sulfated rather than a sulfonated product. With ordinary oils sulfation occurs at the double bonds of the fatty
acids resulting in triolein hydrogen sulfate. Sulfuric acid reacts with the hydroxyl group of the ricinoleyl (12
hydroxy 9 octadecenoic acid) radical of castor oil to form the sulfate.
These products when used in the last stage of wet processing of textiles impart the fabric a desirable
softness or fullness and thus by the end of the 19th century the use of sulfated oils as an important textile
auxiliary chemical and finishing agent became well established. The sulfated oils of the late nineteenth
century were usually only partially sulfated and thus contained a proportion of unchanged fatty glycerides.
Sulfated oils in which a large part of the glycerides had been hydrolysed to the fatty acids possessed all the
faults of the fatty acids themselves particularly their sensitivity to hard water and to acidic conditions. These
defects led to the production (in the 1920 35 period) of so called highly sulfonated oils.
Chemistry of Sulfation and Sulfonation
In sulfonated oils the strongly polar sulfo group appears in the centre or thereabouts of a C18 alkyl chain
and the specific properties of the products although useful are not so highly developed as in compounds in
which the polar group terminates a long alkyl or acyl carbon chain. Hence for many purposes the sulfonated
oils are being replaced by one or other of the more recent preparations.
The oils have therefore not been sulfonated but sulfated and the term sulfonated oil does not convey an
accurate picture of the process. Other side reactions proceed concurrently during either of the above two
main actions. The sulfate group is fairly easily removed in an acid medium in presence of moisture and
consequently the final product contains a certain proportion of hydroxy acids. Further estolides and
possibly other anhydride like compounds are produced during the reaction by elimination of water between
the alcoholic group of one molecule of sulfated fatty acid and the carboxyl (or possibly sulfate) groups of
another. Finally in the case of sulfation of oils the sulfated derivatives have the typical constitution of fat
splitting (hydrolytic) agents and considerable production of free fatty acid sulfated or otherwise from neutral
oil usually takes place during their manufacture.
On the other hand production of true sulfonic derivatives in place of or accompanying the sulfated products
may occur if the action is allowed to take place under strongly dehydrating conditions and especially if
fuming sulfuric acid (oleum) sulfur trioxide or chlorosulfonic acid is used in place of sulfuric acid as the
sulfonating agent. In these cases the reaction probably takes a course such as the acid sulfate group in the
complex formed is comparatively easily hydrolyzed during subsequent washing of the product with water
and true (hydroxy) sulfonic acids CH (SO3H) CH (OH) and their condensation products are present in the
material finally obtained. These compounds will of course be completely stable in so far as the direct
attachment of the sulfonic group SO3H to a carbon atom is concerned whereas the hydrogen sulfate
groups of turkey red and the ordinary sulfonated oils and oleins are liable to hydrolyse in presence of water
of dilute acid yielding free sulfuric acid and a neutral hydroxy fatty compound as between the true fatty
(hydroxy) sulfonates and the unhydrolysed sulfate derivatives of the type of turkey red oil there is probably
little to choose on the score of relative efficiency. Claims that the true sulfonates are more effective textile
assistants may in reality be based upon their greater stability which is due to their incapacity to loose the
polar sulfo acid group by hydrolytic action.
Applications of Sulfonated Oils
Sulfonated oils and fats fulfill many vital needs in the textile processing industry. Their earliest use as
assistants in the dyeing of fabrics still remains one of their dominant functions in this field. They are
characterized by their dispersing properties surface activity and colloidal nature. These characteristics suit
them admirably to the dyeing process. Sulfated castor oil is used in dyeing cotton and rayon fabrics with
direct dyeing colours to facilitate penetration and ensure level dyeing. It is also used as dispersing and
penetrating agent in the application of vat and naphthol colours. Sulfated oil containing high organically
combined sulfate contents (5 to 7 percent) is most suitable for these uses as they generally possess
greater penetrating power and exhibit high tolerance to electrolyte. Excessive sulfation however reduces
the softening properties of sulfated oils and destroys the natural antioxidant which helps to prevent
rancidity. For this reason finishing oils should be prepared to contain a minimum amount of organically
combined sulfate consistent with good solubility and stability.
Sulfated oils and fats are probably consumed in greater quantities in finishing operation. Here they are
incorporated into the fabric in the final wet process for the purpose of enhancing its appearance and feel.
Sulfated olive oil is now almost universally used as a softener on cotton and rayon fabrics where extreme
silkiness and drape are desired. Sulfated olive and castor oils are used as lubricants for soaping and as
tinting oil ingredients for natural silk and rayon. In both cases the sulfated oil is generally combined with
gelatin and dispersed in water as is the case when they are used in warp sizing formulation. Sulfated oils
are sometimes combined with highly purified mineral oils to impart added surface lubrication and sleekness
to the fabric.
Sulfated tallow is commonly used for moderate softening effects and to add body or apparent weight to the
fabric. For additional body and firmness the sulfated tallows are sometimes combined with gums and
starches. They may also be combined with polyoxyethylene condensate and salt or an alkylolamide
condensate and alkali for the dual purpose of scouring and fulling of woollen fabrics. Sulfated tallow has
proved to be an excellent emulsifying agent with all types of waxes and thus it has been possible to
formulate many types of wax emulsions based on sulfated tallow. These wax emulsions are applied to
cotton and rayon to produce an effect of fullness and body enhancing the lustre of calendared fabric s
surface.
One of the greatest uses of sulfated tallow is in the warp sizing of cotton yarns where it is generally used in
conjunction with gums or starches. Here it serves the dual function of plasticizing the size film and
lubricating the yarn to reduce the frictional resistance in the loom. Mixtures of sulfated oils with white
mineral oils impart excellent softness and lubrication and are quite commonly used on high quality cotton
rayon fabrics. The presence of high grade mineral oils improves materially the heat and ageing stability of
sulfated finishing oils.
Pine oil xylol and cresylic acid are mixed with sulfated oils to improve their penetrating and detergency
power. They are then used as kier boiling assistants general scouring agents and agents for removal of
grease and tar stains.
Manufacture of Sulfonated Oils
Fatty oils are sulfated with concentrated sulfuric acid and sulfonated with sulfur trioxide. Both processes are
of semi batch type and the sulfur trioxide process gives a product containing a much higher combined SO3.
Sulfation
The sulfation is carried out in a lead lined vessel jacketed or fitted with cooling coils and agitator. The
reactor is fed with appropriate amounts of the oil and about 25 to 50 per cent on the basis of the amount of
oil charged cold and concentrated sulfuric acid is added to the oil with constant stirring. The circulation of
cooling water is started simultaneously. The rate of addition of acid must be so adjusted that the
temperature does not exceed 35°C. With olive or rapeseed a some what lower temperature is safer and the
less saturated oil e.g. fish linseed soyabean etc are better treated at or below 10°C to avoid undesirable
results. After the addition of all the acid cooling and agitation are continued for some more time in order to
complete the reaction. The mixture is left overnight and again stirred next day. The reaction is considered
complete when a sample of the product completely solubilizes in a given amount of water depending upon
the degree of sulfation desired.
The free sulfuric acid is removed by adding a quantity of cold water equal in weight to the reaction mixture
and allowing it to settle overnight. The aqueous acid layer is then drawn off and the oil is either washed
several times with sodium chloride solution or treated with dilute caustic soda solution until the mixture is
neutral to Congo red paper. Exacting control during washing and neutralizing step is essential. Conditions
occur during this operation which tends to promote desulfation and hydrolysis resulting in an end product
low in organic sulfur trioxide and high in free fatty acids. When it is desired to prevent splitting to the
greatest possible extent washing is done with sodium sulfate solution instead of salt solution. Washing and
neutralization temperature are kept low time of reaction short and pH adjustment accurate. After
neutralization the oil is allowed to settle out from the excess of the solution of inorganic salts. The finished
product usually contains about 35 per cent water. Optimum conditions for individual oil should be
determined by experiments. Monel and nickel clad steel are excellent materials of construction for the
reactor but since they are costly lead lined steel is most often used.
Sulfonation
The process development work for sulfonation with SO3 was Sulfonated Oils carried out by flask
sulfonation. In a typical laboratory batch reaction castor oil is charged to a reaction flask and SO3 diluted to
4 per cent by volume with dry air is introduced below the surface while agitating vigorously. The reaction
temperature is maintained between 45 50°C and the reaction time is between 20 25 minutes. After all of the
SO3 has been added the reaction mass is drowned in 15 per cent sodium hydroxide. The resulting product
contains about 25 percent water and has 8 per cent organically combined SO3 based on 100 per cent
solids. It also displays excellent water solubility at all concentrations.
Results obtained in the laboratory sulfonation can generally be duplicated in the pilot plant and product
quality is often improved because of better heat removal and SO3 distribution in the continuous reactor.
The continuous reactor used for this work consists of a set of vertically mounted water jacketed stainless
steel concentric cylinders divided into three sections the distribution section the reaction section and the
separation section. The main function of the distribution section is to direct flow so as to deposit
continuously an even film of oil to the inner and outer walls of the reaction section. This is accomplished by
pumping the castor oil through small peripheral shots in the distributor.
The SO3/air mixture is introduced above the distributor and passes through the annular space between the
concentric cylinders in such a way that contact is made with the castor oil just at the point where the film is
developed. In the upper part of the reaction section the gas stream containing the initial concentration of
SO3 contacts the unreacted castor oil. As the gas stream and the organic film continue to move together
down the reactor waIls SO3 is absorbed by the liquid organic phase reacting with it so that at the end of the
reaction section SO3 remaining in the gas phase approaches zero concentration. Virtually all the SO3 in
the entering gas stream is absorbed by the organic film and converted to organic sulfate or sulfonate. The
film is in intimate contact with the water jacketed reactor walls and movement in the liquid film generated by
differential velocity of the gas stream provides an efficient heat removal and excellent temperature control.
It also minimizes localized overheating. The reaction mass then passes into the separation section where
acid product is withdrawn for subsequent processing and spent gas is separated and exhausted to
atmosphere through a suitable mist filter.
A batch SO3/air system on the other hand would operate in a manner similar to that used in the continuous
system except that the continuous reactor would be replaced by a stainless steel reaction vessel equipped
with a turbine agitator and circulating pump and a heat exchanger.
In India sulfuric acid is generally used for sulfation of oils and thus most of the products marketed are
sulfated oils rather than sulfonated oils although they are marketed under the latter name. They contain
about 30 50 and 75 percent sulfated organic matter and free oil the rest is mainly water.
Sulfation of Individual Oils
This product was at one time manufactured according to a German process as practiced by M/s. Bohme
Felt Chemie. The product was marketed as A Virol K M. In this process 200 kg. sulfuric acid is slowly added
into 1600 kg. castor oil with continuous stirring in about four and a half hours. The temperature of the
mixture is maintained between 25 30°C by circulating water in cooling coils and/or jacket. After stirring for
1½ hour further 130 kg. of sulfuric acid is added slowly and With continuous stirring in over 3 hours and the
batch is allowed to stand for 13 hours without stirring. Finally a further quantity 50 kg. of sulfuric acid is
added in about 1 hour and stirring is continued for another hour. The batch is then neutralized as quickly as
possible by stirring with 40°Be caustic soda (860 kg.). The temperature rises 90 to 100°C. The product
should now show an acid reaction to phenolphthalein. Live steam is now passed in for 1/2 hour. After
standing overnight the aqueous salt layer is run off. The product is settled for 2 weeks the aqueous layer is
run off and it is then standardized by addition of requisite quantity of water.
Alkylolamides
Introduction
Alkylolamides are condensates of alkylolamines and fatty acids and are generally referred to as foam
boosters or additives. Their use in detergent formulation goes a long way towards solving the problems of
stabilization improvement and creaming of lather which are so important to the success of compounded
detergents. They can be used as detergents in their own right but probably their main outlet is as
ingredients in shampoo and liquid and powder detergent production.
The condensates of commercial interest can be divided into three classes
Products from the reaction of one mole of a monoalkylolamine and one mole of fatty acid.
Products of reaction of one mole of a dialkylolamine with one mole of fatty acid.
Condensation products of more than one mole of a dialkylolamine with one mole of fatty acid.
The products of the class (1) with free fatty acid contents in the range of 5 10 per cent are oily light
brown liquids which are soluble in water and are quite good detergents particularly for cleaning hard
surfaces walls tiles floors etc. These products can be used in the formulation of liquid cleaners and the
following formula has been suggested.
This type of formulation is advocated for packing in mild steel drums for sale to hospitals institutions
bakeries etc.
The products of the class (2) with low free fatty acid contents are used as foam boosters particularly in the
formulation of liquid cleaners. They also act as solubilizing agents for alkyaryl sulfonates and sodium lauryl
sulfates depressing the cloud points of mixtures and helping to ensure that no separation of active matter
occurs at low temperatures. These products are also used to a more limited extent as additives for powder
detergents they are incorporated by spraying in the molten state on to spray dried or physically mixed
powders.
The monoalkylolamine derivatives find their major outlet as builders for all purpose spray dried powder
detergents where they are normally used at the level of 1 3 per cent. The range of useful additives is wide
but can be limited to some extent by economic considerations. In the choice of additive for any particular
formulation the following points must be considered
Does the additive have the desired foam boosting properties when added at the desired economic
level ?
Are the raw materials available at a reasonable and stable price?
Can the additive be made consistently or does it suffer batch to batch variation which impairs its properties.
(d) Is it compatible with other ingredients in formula e.g. if used with a liquid product can it be sufficiently
solubilized together with the other solution ?
(e) Can it be easily incorporated at the right concentration in the powder e.g. can it be sprayed evenly on to
the powder will it be stable at spray drying temperatures or will it result in a sticky powder and tend to bleed
out ?
(/) Is it stable under long term storage conditions or will it turn rancid or affect the perfume in anyway ?
(g) Has it any disadvantages in use e.g. does it leave streaks on glasses washed in the detergent solution?
The time taken between laboratory trials and launching a detergent powder on a commercial scale may be
anything from six months to three years depending on time taken for consumer trials necessary plant
alterations stability testing etc. When asked to recommend an additive for any particular proposed formula
the additive manufacturer must weigh all these points carefully and if necessary carry out extensive tests.
There is no one additive which will perform satisfactorily with all formulae and the additive makers have
constantly to be searching for new and improved products particularly in view of such developments as the
increasing use of primary alkyl sulfates in all purpose formulae.
Alkylolamides in Shampoo Formulations
The mono and dialkylolamides are widely used in liquid and liquid cream shampoo formulations. They
exhibit additive powers so far as volume of foam goes and also help to ensure the creamy thick lather
desired by the customer. They are of great assistance in thickening liquid shampoos and by their addition to
alkylolamine neutralized lauryl sulfate practically any desired viscosity can be achieved.
They may be looked upon as amides derived by condensing an aliphatic acid of moderate or long chain
length with an amino alcohol.
However it does not necessarily follow that amides actu ally used are produced by direct condensation. The
RCO will be derived from any of the natural fatty acids in the range of capric caprylic to oleic and stearic
and behenic.
Mono Alkylolamides
The substance in class I are waxy materials and on their own are substantially insoluble in water. The
members of this class derived from the fatty acids of moderate chain length such as lauric and myristic can
however be soluble in water when they form part of a composition with other synthetic detergents which are
themselves water soluble. These particular alkylolamides have the power of improving the soil removal
efficiency of other detergents particularly sulfated and sulfonated detergents such as sodium lauryl sulfate
and sodium dodecyl benzene sulfonate. They also have the power of enhancing the foaming powers of
detergents particularly those just named under the appropriate conditions.
Alkylolamide falling in class (1) but derived from higher fatty acids are practically insoluble in water and do
not improve the lathering power or soil removal efficiency of detergents but they are valuable emulsifying
agents and in some cases they serve to render translucent detergent compositions opaque or pearly in
appearance. It is also stated in the literature that certain alkylolamides derived from higher unsaturated fatty
acids are useful as conditioning agents for the hair when incorporated in shampoos. The alkylolamides
derived from lauric and myristic acids which are probably the most used in this class are generally chosen
to enhance the foaming or detergent power of other surface active agents in preparations which are to be
marketed as powders. Generally speaking these alkylolamides even in the presence of substantial
quantities of sulfated anionic detergents are not sufficiently soluble to enable clear or translucent liquid
preparations to be formulated. However under some conditions in the presence of other materials which act
as coupling agents clear liquid products can be produced. The coupling agents may be aliphatic alcohols or
may even be alkylolamides derived from other fatty acids. As an example of the latter it may be noted that
the mono ethanolamide derived from coconut oil fatty acids which will contain approximately 65 per cent of
the lauric and myristic ethanolamides is much more soluble in liquid detergents concentrates than an
alkylolamide derived from pure lauric or myristic acid.
Di Alkylolamides
The alkylolamides falling in class (2) are more soluble than those in the previous class. Until recently the
alkylolamides in this class were most frequently made not as the pure amides represented by the formula
given but in the form of a complex composed of genuine amide free amino alcohol and some soap. There is
considerable evidence that the complex does not function as simple mixture and in this form many
alkylolamides of class (2) are readily soluble in water although they may be salted out by electrolytes under
certain conditions.
On account of their solubility in water di alkylolamides derived from lauric or myristic acid and
diethanolamine in the form of the complex containing excess diethanolamine have found extensive
application in the formulations of liquid detergent preparations. These alkylolamides have the power to
augment the foaming power of other surface active agents under certain conditions and at the same time
they have a thickening effect upon liquid detergent preparations generally. Unlike the products in class (1)
which are purely effective as improvers for other detergents the alkylolamides in this class possess in the
form of the complex very considerable detergent power in their own right and are frequently used without
the admixture of other surface active agents in the formulation of the general cleaning and so called
sanitizing detergent preparations.
The alkylolamides represented by formula (3) are interesting in that the balance may be altered by varying
the number of molecules of ethylene oxide in the two radicals attached to the nitrogen atom. Compounds in
this group show reason able wetting properties and the precise wetting power depends upon the balance of
the molecule. Thus if RCO is derived from short chain fatty acids such as lauric or myristic the wetting
power is at its highest when the side chains contain not more than five molecules of ethylene oxide (in other
words when m+n in the formula does not exceed 5). Whether RCO is derived from a longer fatty acid such
as stearic or oleic it is necessary for the hydrophilic properties of the molecule to be increased to achieve
optimum wetting power. In this case the best results are obtained when the number of molecules of
ethylene oxide is about 10 (that is where m+n = 10). The alkylolamides however in this class have never
become as extensive in use as the alkylolamides in the other two groups. They are principally of interest for
their value as emulsifiers. The products from coconut oil fatty acids and containing 10/50 molecules of
ethylene oxide are good oil in water emulsifiers for carnauba wax.
Pure Di Alkylolamides
Until recently the alkylolamides in class (2) have generally been available and used in the form of a
complex. This was in many ways convenient as the complexes were more soluble and possessed better
wetting and detergent power than the pure amides and also because it is simpler and therefore cheaper to
manufacture this type of product free from undesirable by products if an excess of alkylolamine is present.
Where however these products are used in conjunction with sulfated detergents to enhance the foam of the
latter the effective material is the true amide while excess diethanolamine contained in the complex does
not contribute towards the effect. In cases such as these the di alkylolamides can normally be adequately
solubilized by the sulfated detergent and therefore the excess diethanolamine serves no useful purpose.
For the majority of applications however the whole issue would seem to hinge on the price one is paying for
100 per cent active amide when one buys it in the nearly pure state as compared with the conventional
complex. It cannot of course be overemphasized that where di alkylolamide is being used as a detergent in
its own right alone or with only minor amounts of other detergents the complex will of course be preferred
on account of its allround greater solubility and wetting and detergent power.
Phosphoxylated Alkylolamides
Recently interest has been taken in the production of phosphoric acid esters of the alkylolamides. These
have been claimed to have an anti static effect when used in the washing of synthetic fibres such as nylon.
Other phosphoric acid esters of alkylolamides have found application to produce a pearly effect in some
types of cream shampoos.
Sulphated Alkylolamides
The product so far described where they have been soluble in water and possessed surface active
properties have been essentially non ionic in their behaviour. It is possible by preparing the acid esters of
sulfuric acid or phosphoric acid of these alkylolamides to produce detergents which are anionic in their
behaviour. In general the mono alkylolamides falling in class (1) are preferred for sulfation or
phosphorylation. The sulfated mono alkylol amides of coconut oil fatty acids have excellent lathering power
comparable with that possessed by sodium or triethanolamine lauryl sulfate. They show a superior
detergency to the latter materials and also greater ability when in dilute solution to retain dirt particles in
suspension.
The sulfated alkylolamides however are not one of the big volume detergents and they have never equaled
the alkyl sulfates in popularity. Probably one of the reasons for this is that it is extremely difficult to control
the sulfation procedure to ensure that the finished product is free from undesirable by products which impair
efficiency. The fact that on paper the preparation of sulfated alkylolamide detergents appeared relatively
easy at one time tempted some firms to try and produce these materials without adequate research. The
earlier products however were very variable and frequently contained substantial amounts of undesirable
side products. Properly prepared however the sulfated alkylolamides are excellent products. Probably the
best known of this type of detergent is the sulfated monoethanol amide or isopropanolamide derived from
coconut oil fatty acids. Detergents have been prepared however from higher unsaturated fatty acids and
though under some conditions they lack the lathering power of the products from coconut oil they do
possess exceptionally good detergency and also incidentally exceptional power to disperse lime soaps.
Whereas the sulfated fatty alcohols are generally processed so as to ensure the maximum degree of
sulfation and the minimum residual amount of unsulfated fatty alcohols it is not usual in the case of such
materials as coconut oil fatty acids monoethanolamide to secure such a high degree of sulfation. Frequently
75 percent to 85 percent sulfation is the maximum desired. The reason for this is that unsulfated and
unsulfated material is vary effective in use. Products containing as much as 50 percent unsulfated material
(provided always that they are free from undesirable side reaction products) have excellent lathering and
cleaning power.
Foam Stabilization
The original patents which referred to the use of alkylolamides in detergent compositions were mainly
concerned with the improving effect that the alkylolamides exerted upon the soil removal efficiency of other
detergents.However alkylolamides today are most frequently added to detergent compositions in order to
improve the lathering power under the conditions of use. When we come to consider how to estimate
quantitatively the effect of the alkylolamides the position is by no means simple. Many compositions in
practical use are improved by the presence of an alkylolamide. However it is not always easy to measure
this improvement quantitatively under laboratory conditions. For example it is often quite useless attempting
to infer how a shampoo composition will behave in use of the hair by measuring the foam obtained by
shaking solutions of the detergent preparation in measuring cylinders in the laboratory.
One satisfactory way consists in devising a laboratory test which simulates the actual conditions under
which a detergent product is to be used. The effect that an alkylolamide exerts upon the foam of a
preparation when the foam is created in narrow capillary in a relatively narrow foam cylinder is quite
different from that exerted when the foam is produced on a wide surface area such as one has in a sink
during dishwashing operation. The conditions which apply during a shampooing operation on the hair are
different again. It is further most important that in tests designed to evaluate detergent preparations in the
laboratory soil such as would be expected in actual practice should be present. It is also important that the
tests should be carried out at the same active detergent concentration as would apply in practice.
The effect of concentrations on lathering power is readily illustrated by an example concerning the sulfated
alkylolamides. Salts of sulfated lauric acid mono ethanolamide possess excellent lathering power at high
concentrations such as might be employed in shampooing or for the washing of clothes under domestic
conditions but if a solution of the detergent is excessively diluted once the detergent concentration falls
below a certain critical level the foaming power disappears. Sulfated alkylolamides derived from C19
unsaturated acids however behave quite differently. These give however at a similar concentration level to
that at which the sulfated lauric mono ethanolamide would have ceased to lather these produce extremely
stable foam. The detergent concentration in a washing machine in a commercial laundry would be at a low
level.
Another interesting method for testing a shampoo product under pratical conditions has recently been
described in the literature. The effect of alkylolamides on sulfated and sulfonated anionic detergents is not
normally to improve the lathering power of the detergent in plain water. Alkylolamides offset the deleterious
action of oily or fatty soiling matter on the foam of these detergents. Many anionic detergents though they
lather well in plain water tend to lose their lather to an astonishing extent in the presence of oil and fatty
soiling matter and this effect is prevented by the use of suitable alkylolamides. The effect however is not
quite true at all concentrations and the effectiveness of the alkylolamide only takes place above a certain
threshold concentration of active detergent in solution. Fortunately this threshold concentration where lauric
or myristic monoalkylolamides or dialkylolamides used in conjunction with such detergents as the alkylaryl
sulfonates or alkyl sulfates is below the concentration at which most domestic washing operations are
carried out.
An alkylolamide of much higher threshold concentration is capable of improving the lather of anionic
detergents at high concentrations (e.g. 3 per cent and over) such as would be used when shampooing the
hair. Where however the dilution becomes much greater the lathering power rapidly diminishes. Thus using
this particular alkylolamide it is possible to prepare a composition which yields rich stable foam on the hair
but immediately the rising operation commences the foam disappears. This effect would notappeal to
consumers who like to judge the lathering power of a shampoo by the amount of lather to be seen in the
washbowl after rinsing. However it would appeal to those who find stable detergent foams difficult to rinse
away down the sink and to the sewage authorities who find stable detergent foams so difficult to handle.
The most commonly used alkylolamides for the purpose of stabilizing foam are the monoalkylolamides
which fall in class (1) and the alkylolamides which fall in class (2) derived from either lauric or myristic
acids. Products derived from mixed fatty acids containing substantial proportions of lauric or myristic acid
such as coconut oil or palm kernal fatty acids are also used. In general however when one comes to
measure effective foam stabilization as such it is generally found that the products derived from mixed fatty
acids associated with them behave virtually as no more than inert diluents although in the case of the
monoalkylolamides products from mixed fatty acids sometimes have the advantage of greater solubility in
liquid detergent preparations. Therefore it is frequently a better economic proposition to buy what is initially
a more expensive product devised from a fractionated lauric acid than to use a mixed product which has a
lower market price.
These observations apply to the stabilization of foam and there are of course other aspects of the use of
alkylolamides where the mixed products may be more worthwhile. Generally the lauric monoalkylolamides
are preferred for use in powder compositions. Frequently they are here associated with polyphosphates
and in the case of some alkylolamides particularly isopropanolamides the presence of polyphosphates
seems to be necessary for the maximum stabilising effect to be produced. The monoalkylolamides are
generally dispersed in detergent slurry at an elevated temperature before it is mixed with the phosphates or
other builders and fed to the spray drier. Mono alkylolamides are now available in powder form which
greatly facilitates the operation of dispersing them in a detergent slurry. Lauric diethanolamides either in the
form of complex previously referred to or in the pure state are used in the formulation of liquid detergents
since they do not impair the cloud point of these products. In actual fact diethanolamides in the form of the
complex frequently effectively lower the point at which alkylaryl sulfonate and other compositions cloud.
However there is no hard and fast rule concerning the use of the different types of alkylolamides.
Dialkylolamides may be incor porated into powders in quite significant amounts and on the other hand
mono alkylolamides may be included in liquid composition either in restricted amounts alone or solubilized
by the addition of alcohol.

Vinylarene Polymers
This article covers polymers derived from monomers that have a vinyl group attached to an aromatic ring
(1). It does not cover aromatic monomers having a heteroatom in the ring styrenes or except for 4
vinylbiphenyl Substituted styrenes.
Monomers
Vinylarene monomers are general1y prepared by dehydration of the corresponding carbinol which can
usually be obtained by the acetylation of the corresponding hydrocarbon and reduction of the ketone. The
carbinol can also be obtained by the reaction of the aryl Grignard reagent with acetaldehyde (eq.1)
In Table 1 are listed some vinylarene monomers and their physical properties.
Anionic Polymerization
Kinetics of the anionic homopolymerization of 1 vinylnaphthalene 2 vinylnaphthalene and 9 vinylanthracene
in tetrahydrofuran at 25°C have been determined and propagation rate constants of 500 300 and 0.2 l mole
1 sec 1 found. The greater reactivity of 1 and 2 vinylnaphthalene as compared with that of styrene has been
attributed to their lower localization energies.
The anionic polymerization of 9 vinylanthracene produces only low molecular weight polymer and initation
by naphthalene or biphenyl radical anions or by butyllithium yields oligomers having a DP of 4 12. A study
of the reaction has shown that although the concentration of the living ends remains unchanged during the
reaction the degree of polymerization does not correspond to the concentration of initiator indicating an
efficient chain transfer reaction. When additional monomer is supplied to the polymerized system more
polymer forms without affecting its molecular weight thus indicating that no chain transfer to polymer takes
place.
It has been shown that 9 vinylanthracene can polymerize both along the vinyl group and across the central
ring of the anthracene system and structural analysis has shown that material polymerized in the presence
of lithium potassium and sodium contains a lower percentage of anthracene rings than material
polymerized with cesium.
The polymerization mechanism shown in equations 2 4 has been proposed. Accumulated physical and
chemical evidence indicates that the predominant structure for the polymer is that resulting from a 1 6
across the ring addition. To account for the low molecular weight of the polymer the chain transfer reaction
shown in equation 5 has been proposed.
A kinetic study of the anionic polymerization of acenaphthylene has shown that the reaction follows pseudo
first order kinetics and that a chain transfer reaction to monomer similar to that observed for 9
vinylanthracene takes place. The highest molecular weight that could be obtained by anionic polymerization
was 8000 although thermal polymerization in bulk produced polymers having very high molecular weight
(ca 2 000 000). Although the chain transfer mechanism has not been established it probably involves
electron transfer to monomer coupled with hydrogen abstraction from solvent. The copolymerization of 1
vinylnaphthalene with 2 vinylpyridine and with styrene has been investigated in both sequential and
simultaneous polymerizations and good yields of copolymers were obtained when 1 vinylnaphthalene was
initiated with a polystyrene anion. Interesting results are reported when styrene is initiated with a poly(l
vinylnaphthalene) anion addition of two or three equivalents of styrene to living poly(l vinylnaphthalene)
leads to the disappearance of the characteristic 558 mm absorption maximum of the poly(1
vinylnaphthalene) anion but the expected 340 mm maximum of the polystyrene anion does not appear.
Instead a new absorption peak at 440 mm appears but on standing for 24 hr the original 558 mm peak of
poly(l vinylnaphthalene) reappears. When a large excess of styrene twentyfold or more is added the
characteristic spectrum of polystyrene appears permanently.
The observations were explained by assuming that the reaction involves three steps (eqs. 6 8).
The addition of the first styrene molecule produces a benzyl type anion that froms a bond with the
preceding naphthalene group. The product resembles the adduct of living Polystyrene and thracene and
the product very slowly adds a second molecule of styrene. The addition of the second molecule destroys
the complexing with naphthalene and the resulting polymer propagates as ordinary polystyrene does.
The complex formed on addition of a small excess of styrene to living poly(l vinylnaphthalene) must be
unstable because the spectrum of the poly(l vinylnaphthalene) reappears within 24 hr. It has been
concluded that the formation of the complex is reversible and that the equilibrium concentration of styrene
is given by the reaction shown in equation 9. The reaction mixture must however contain some living
polystyrene anions since some segments have added two or more styrene units. Hence another equilibrium
is established (eq. 10). These three equilibria are coupled in the overall process and the equilibrium of the
overall process favors the right side (eq. 11). This scheme has been tested with a methylstyrene the
propagation of which is thermodynamically unfavorable and a stable complex was formed when this
monomer was added to living poly(l vinylnaphthalene).
ABA block copolymers of 4 vinylbiphenyl and isoprene have been prepared using living polymer techniques
Because of difficulties in achieving a rigorous purification of 4 vinylbiphenyl a coupling technique was used
whereby the A monomer was polymerized first the B monomer was then added and the AB anion was next
coupled with a reactive dihalide. Using this technique the residual impurities in the A monomer only destroy
some initiator by estimating the degree of purity it is easy to use a slight excess of initiator to compensate
for the amount destroyed by the impurities Coupling of the AB anions was achieved by using phosgene
which was allowed to diffuse very slowly into a vigorously agitated polymer solution.
The block copolymers were characterized by gel permeation chromatography and from knowledge of the
ratio of the refractive index increments of the two homopolymers and the overall composition a quantitative
analysis was carried out.
Polymer Reactions
The transfer of an electron from alkali metals to an aromatic hydrocarbon such as naphthalene or biphenyl
is well known. The same reaction occurs when the vinylarene group is attached to a polymer chain. The
products have been referred to as polyradical anions and are formed experimentally in all glass
highvacuum systems by the reaction of the polymer in tetrahydrofuran with a sodium mirror at temperatures
ranging from 80 to 30°C.
The reaction products have been characterized by viscometric spectrophotometric and electron spin
resonance measurements. It was found that the viscosity of the solution decreases with time and that the
final viscosity depends essentially on the alkali metal concentration. Spectrophotometric data have shown
that with time the spectrum becomes almost identical to living polymer dianions and electron spin
resonance studies have indicated the presence of unpaired electrons in concentrations proportional to the
sodium content. The disappearance of the signal to practically zero the formation of anions and the
decrease in viscosity with time are consistent with a cleavage mechanism in which an electron migrates
from the aromatic ring to the a carbon of the aliphatic chain with formation of a negatively charged end (eq.
12). The same mechanism has been proposed for poly (N vinylcarbazole) poly (l vinylnaphthalene) poly (2
vinylnaphthalene) and poly (4 vinylbiphenyl). Poly (acenaphthylene) degrades so fast that it is not possible
to follow changes in viscosity as a function of time. It has also been found that monomeric fragments are
produced (eq. 13).
Polyradical anions have been used to initiate graft polymerization reactions. The reaction is not applicable
to monomers that polymerize by an electrontransfer mechanism where only homopolymerization is
achieved. However monomers such as cyclic ethers that cannot polymerize by an electron transfer process
but do polymerize anionically do form graft copolymers. The mechanism of the polymerization is similar to
that proposed for the carbonation of the naphthalene radical anion (eqs. 14 16).
Poly (2 vinylfluorene) has been metalated with metallic sodium or lithium or with the corresponding
naphthalene radical anions (eq. 17) and graft copolymers with a variety of vinyl monomers such as styrene
methyl methacrylate or vinylpyridine in addition to ethylene oxide have been prepared.
Metalation of 2 vinylnaphthalene units incorporated into a copolymer has also been used to provide sites for
anionic grafting reactions. Thus a copolymer of butadiene containing small proportions of 2
vinylnaphthalene has been prepared by free radical copolymerization techniques the resulting copolymer
metalated with butyllithium and styrene or 2 vinylnaphthalene graft copolymerized on the anionic sites. The
resulting materials exhibited elastomeric properties similar to those of styrene butadiene ABA block
copolymers provided the number of grafts per backbone was small.
Stereoregular Polymerization
Although the stereoregular polymerization of styrene and substituted styrenes has received considerable
attention other vinylarene monomers have been studied much less extensively. Natta and co workers have
surveyed the stereoregular polymerization of over 20 vinyl aromatic monomers among these were1
vinylnaphthalene 2 vinylnaphthalene 1 vinyl 4 chloronaphth alene 1 2 3 4 tetrahydro 6 viny1 naphthalene 4
vinylbiphenyl 9 vinylphenanthrene and 9 vinylanthracene. This study established that Ziegler Natta
polymerizations are very sensitive to steric hindrance about the double bond and when the steric hindrance
is excessive such as in 9 vinylanthracene no polymerization takes place. Although one study does report a
polymerization of 9 vinylanthracene in yields from 20 to 90% depending on the Al/Ti ratio with an Al
(C2H5)3 TiCl4 catalyst system the results indicate a cationic polymerization.
Stereoregular polymers of 1 vinylnaphthalene 2 vinylna phthalene and 4 vinylbiphenyl have been prepared
using a (C2H5)3Al TiCl4 (C2H5)2AlCl TiCl3 or (C2H5)3 AI TiCl3 catalyst system . The latter catalyst gave
polymers in 75 95% conversion that were at least 90% isotactic. The atactic fraction could be separated
from the isotactic ones by extraction with methyl ethyl ketone. The isotactic polymers were also
characterized by infrared and nuclear magnetic resonance spectroscopy (35).
Not all stereoregular polymers could be crystallized. In polymers in which steric factors lead to a crystalline
phaseNot all stereoregular polymers could be crystallized. In polymers in which steric factors lead to a
crystalline phase that would have a lower density than the amorphous phase no crystallization took place.
Thus only 1 vinylnaphthalene produced a crystallizable polymer .An x ray diffraction study on this polymer
has been carried out. The Bragg distances in the unit cell are a = b = 21.20 Å and c = 8.12 Å and the
specific gravity is 1.12.
The stereoregular ionic polymerization of acenaphthylene has been investigated in some detail. Although
four stereoisomers can be written eg cis and trans isotactic and cis and trans syndiotactic a study of
molecular models has shown that only the trans isotactic and trans syndiotactic conformations can exist in
polymers. The trans isotactic poly(acenaphthylene) forms a helix and the trans syndiotactic poly
(acenaphthylene) forms a stair stepped rigid rod. These stereoisomers were obtained by n butyllithium or
boron trifluoride polymerizations and characterized by infrared and nuclear magnetic resonance
spectroscopy.
Acenaphthylene has also been polymerized with an Al(C2H5)3 Ti(OC3H7)4 catalyst system but no mention
of stereoregularity was made.
Cationic Polymerization
The cationic polymerization of vinylarene monomers other than styrene is not well understood and little
reliable quantitative information is available. Acenaphthylene readily forms polymers of high molecular
weight although a dimer can be obtained when a solution of acenaphthylene in glacial acetic acid is treated
with a small quantity of concentrated hydrochloric acid. The kinetics of the cationic polymerization catalyzed
by boron trifluoride and iodine has also been studied. In the first case a second order reaction with respect
to boron trifluoride was observed and in the second case a high order reaction with respect to iodine
concentration and cocatalysis by hydrogen iodide was noted.
Unlike free radical polymerization the cationic polymerization of 9 polymerization rates. Early studies
assumed a normal vinyl polymerization but it was later shown that the normal addition takes place to only a
very minor extent and that polymerization across the ring similar to that already discussed in the anionic
polymerization takes place. A wide variety of catalyst systems and solvents was also investigated.Very little
information is available on the cationic polymerization of other vinylarene monomers. l Vinylnaphthalene
apparently can be polymerized to a high molecular weight product but monomers substituted in the a or b
position of the vinyl group yield mainly dimers. The polymerization of 4 vinylbiphenyl with Friedel Crafts
catalysts has been reported and l vinylpyrene and 2 vinylfluorene have also been polymerized with BF3.
Stable carbonium ions such as tropylium hexachloro antimonate (C7H7 SbC16 ) and tetrafluoroborate
(C7H7 BF4 ) have been used to initiate the polymerization of acenaphthylene and 1 and 2
vinylnaphthalene.
Free Radical Polymerization
The kinetics of the 2 2 azobisisobutyronitrile initiated bulk polymerization of 1 vinylnaphthalene have been
reported. The polymerization rate is proportional to the 1/2 power of the initiator concentration and the first
power of the monomer concentration. The molecular weight of the polymer was shown to be controlled by a
chain transfer reaction with the monomer and a chain transfer constant of 0.03 about 300 times that for
styrene was found. As a consequence only low molecular weight polymers (2000 6000) were obtained. The
bulk polymerization of 2 vinylnaphthalene leads to a product having a molecular weight of about 66 000.
Emulsion polymerization techniques yielded a poly(l vinylnaphthalene) having a molecular weight of 25 000
and a poly (2 vinylnaphthalene) having a molecular weight of 115 000.
The relative ease of bulk polymerization of 1 vinylnaphthalene 2 vinylnaphthalene 6 vinyl 1 2 3 4
tetrahydronaphthalene and vinyldecahydronaphthalene has been compared 1 and 2 vinylnaphthal enes
were the easiest to polymerize 6vinyl 1 2 3 4 tetrahydronaphthalene had polymerization rates comparable
with those of unsubstituted styrene and vinyldecahydronaphthalene did not polymerize during 30 days at
100°C.
The solid state postpolymerization of 60Co g irradiated 2 vinylnaphthalene has been studied. The monomer
was irradiated at 78°C and then postpolymerized at temperatures ranging from 20 to 41°C. A limiting
conversion of about 40% was obtained. The soild state polymerization under pressure has also been
investigated.
The polymerization rates of 1 and 9 vinylanthracene and 9 vinylphenanthrene have also been compared.
The highest reactivity was shown by 9 vinylphenanthrene and the lowest by 9 vinylanthracenc. The
reactivities were explained on the basis of steric hindrance to conjugation between the ring system and the
vinyl group and the nonaromatic character of the 9 10 double bond in phenanthrene. The free radical
polymerization of 9 vinylanthracene proceeds so slowly that it holds little promise as an acceptable
polymerization technique. No studies have been reported in which the structure of this polymer has been
examined.
Acenaphthylene can be polymerized to a high molecular weight polymer using free radical initiators and a
molecular weight of over 150 000 has been reported. The kinetics of the thermal polymerization of a highly
purified sample have been studied dilatometrically and a high activation energy for both initiation and
propagation was found.
The effect of high pressure on the free radical polymerization of acenaphthylene has also been
investigated. It was found that the rate of polymerization is not increased as much by pressure as is that of
other olefinic monomers such as styrene. The effect of pressure on molecular weight was also less than for
polystyrene and the molecular weight of the polymer increased by a factor of 2.6 between 1 and 2880 atm.
The solid state polymerization of acenaphthylene initiated by x rays has been studied in air in nitrogen and
under vacuum. The results indicate that the molecular weight is essentially independent of the total dose
rate and the rate of polymerization is proportional to the first power of the dose rate. The polymer was
amorphous as indicated by x ray diffraction.
The polymerization rates of a series of substituted vinylbiphenyls have been found to be first order in
monomer and they were claimed to increase with increased conjugation and polarity of the substituents.
Reactivity ratios for various vinylarene monomers are shown in Table 2.
As indicated by the 1/r1 values all vinylarene monomers shown with the exception of 9 vinylanthracene are
more reactive in copolymerization than is monomer M1.
A series of copolymers of 4 vinylbiphenyl with styrene and vinylchlorobiphenyl and vinylfluorobiphenyl each
with a methylstyrene or a p dimethylstyrene have been prepared by mass and emulsion copolymerization.
The 4 vinylbiphenyl styrene copolymer was claimed to have improved resistance to heat distortion.
The effect of styrene on bulk polymerization rates and molecular weights of copolymers with various vinyl
naphthalenes has received considerable attention. Thus the bulk polymerization rateof 1 vinylnaphthalene
is decreased by the addition of styrene and the rate reaches a minimum with 60 mole % styrene in the feed.
In general the addition of styrene to vinylnaphthalene increases the molecular weight of the copolymer.
With 1 vinylnaphthalene addition of styrene had little effect until about 60% had been added and then the
molecular weight increased almost linearly from 20 000 to 110 000. The increase in molecular weight of
poly(2vinylnaphthalene) by addition of styrene was in general more gradual but was more rapid at low
styrene concentration. The same effect was also noted in methyl methacrylate 2 vinylnaphthalene
copolymerization. As in homopoly merization emulsion copolymerizations produce copolymers having
higher molecular weights relative to those prepared by bulk polymerization.
Addition of styrene to 6 chloro 2 vinylnaphthalene leads to increasing rates with increasing styrene content
in the feed whereas the opposite is true with 4 chloro 1 vinylnaphthalene. The addition of methyl
methacrylate has little or no effect on 4 chloro l vinylnaphthalene but decreases the rate of copolymerization
of 6 chloro 2vinylnaphthalene.
The copolymerization behavior of anthracene and phenanthrene derivatives with styrene has been
investigated. The same order of decreasing activity (9 vinylphenanthrene> l vinylanthracene > 9
vinylanthracene) as in homopoly merization is also noted in copolymerization. Although the rate of
copolymerization of 9 vinylanthracene with styrene is faster than that of 9 vinylanthracene alone 9
vinylanthracene feeds greater than 25% by weight inhibit the polymerization of styrene 2 And 3
vinylphenanthrenes have been copolymerized with methyl acrylate. Even though both monomers are more
reactive than styrene toward methyl acrylate radicals the addition of methyl acrylate to either of the
phenanthrenes reduced both the molecular weight of the polymer and the rate of copolymerization.
Various copolymers of 1 vinylpyrene have been prepared and their softening points determined.
The copolymerization of acenaphthylene with other vinyl monomers has been described. Of these the most
extensively investigated was the copolymerization of styrene with acenaphthylene. Mass polymerizations
using peroxide initiators or thermal polymerizations at 120 125°C for as long as 10 days yielded only low
molecular weight copolymers. However emulsion polymerization at 30°C with redox catalyst systems gave
excellent yields and high molecular weight products. Terpolymers of acenaphthylene styrene and butadiene
have also been prepared. Acenaphthylene has been copolymerized with divinylbenzene and the
crosslinked network sulfonated. Strongly acidic ion exchange series were thus produced.
Solid state g radiation induced copolymerization studies of acenaphthylene with acrylamide and maleic
anhydride have been carried out. Only polyacrylamide homopolymers could be obtained in attempted
copolymerizations of eutectic mixtures with acenaphthylene. Solid state copolymerizations of maleic
anhydride with acenaphthylene produced 1 1 copolymers.The same alternating copolymer was also
obtained in free radical solution copolymerization.
Graft copolymers of acenaphthylene onto polyethylene have been prepared by roll mixing polyethylene
acenaphthylene and benzoyl peroxide in air at 100°C. Maximum grafting was obtained at 30 min and
thereafter the amount grafted decreased because the grafted branches were selectively masticated. No
grafting was obtained in the absence of benzoyl peroxide.
Polymer Properties
Characterization. In Table 3 are collected the parameters for the Mark Houwink equation for some
vinylarene polymers correlating intrinsic viscosity with molecular weight.
Light scattering studies have shown that the coil size of poly (2 vinylnaphthalene) exceeds that of
polystyrene by a factor of 1.4 indicating that substitution of benzene by a naphthalene ring increases the
thermodynamic stiffness of the polymer. However another study has shown that even though considerable
hindrance to rotational motion of chain segments should be expected in poly (acenaphthylene) its dilute
solution behavior indicates that it has a hydrodynamic volume comparable with that of polystyrene. It has
also been shown that poly (4 vinylbiphenyl) poly (l vinylnaphthalene) and poly(2 vinylnaphthalene) can be
represented by a common plot of intrinsic viscosity times the molecular weight of the repeat unit versus
weight average degree of polymerization and that they also exhibit a common gel permeation
chromatography calibration plot. These results lead to the some what surprising conclusion that all these
vinylarene polymers have similar hydrodynamic volumes. Poly (acenaphthylene) could not be included in
these studies be cause it has been found to be unstable in solution and to degrade by a free radical
mechanism that is at least partially an unzipping process.
Electrical Properties.
A number of charge transfer complexes have been prepared in which the electron donor is a vinylarene
polymer. They are of interest because the complexes are known to show semi conductive properties in the
solid state.

N Acyl N Alkyltaurates
Introduction
N acyl N alkyltaurates have a general formula RR`NCH2 CH2SO3Na where R may be oleoyl cocoacyl taIl
oil or taIlow group and R may be a methyl or cyclohexyl group. However the most commonly used and
produced product in this group of compounds is sodium N Oleoyl N methyltaurate. It is sold throughout the
world under various trade names most common among them being IGEPON T.
Igepon T was first introduced by I.G. Farben industries in Germany and is still in the market in its original
form. It is sufficiently stable for most textile processing work except the carbonizing of wool where a strong
sulfuric acid bath is encountered. Igepon T has enjoyed a steady expansion of market upto the present time
in U.S.A. and Germany and most other developed countries inspite of the advent of alkyl benzene
sulfonates. In India however most of its requirements are met through imports.
In a more general formula of N acyl N alkyltaurates
R1 represents hydrocarbon radicals of the fatty acid series which for economic reasons may contain twelve
to eighteen carbon atoms. R2 represents an alkyl or cycloaliphatic group which should range from one to
eight carbon atoms. Total carbons in Rl and R2 preferably should not be less than twelve nor more than
twenty one. Beyond these limits the quality of the product falls off sharply in one of several properties. R3
may be a metal or an organic base or hydrogen. A computation of the number of possible products under
the above stated limits might reach 1000.
The effect of changes in structure is fairly well defined. Little detergency is obtained unless Rl and R2
combined contain at least twelve carbon atoms. Detergency is increased by increasing the length of either
Rl or R2 or both. The limit is reached at approximately sixteen carbon atoms for Rl if the chain is straight
and saturated. If unsaturated then maximum detergency occurs at approximately eighteen carbons and it is
believed that with more unsaturation the maximum length of carbons is further increased Departures from
straight chain in R1 by branching or by introduction of a solubilizing group will de crease detergency but
increase the wetting power. A decrease in the length of Rl increases both solubility and wetting power. If Rl
is kept within twelve to sixteen carbon atoms and if the size of the R2 group is increased from a methyl to a
higher homolog such as the butyl or amyl group the resulting Igepon becomes more soluble inspite of the
molecular weight increase. If Rl is twelve carbons the solubility of the Igepon passes through a maximum
when R2 is a four carbon straight chain. Wetting increases with increase in the lengths of R2 until Rl and
R2 combined contain approximately eighteen carbons. Further increase in R2 brings on a decrease in
wetting. R2 may be hydrogen but when a taurine is used a substitution of at least one carbon group
enhances the properties of the resulting product tremendously. The choice of a metal for R3 may affect
foaming and the power to emulsify and disperse other substances. There is little difference in solubility
between the sodium and potassium salts in the Igepon compounds investigated. The calcium salts are
much less soluble. The representative types of Igepon T currently manufactured in developed countries
such as U.S.A. and Germany are given in Table 1.
Although one primary factor in determining which Igepon type compounds will be commercially important is
the cost of raw materials the economic limitations stilI permit a relatively wide area of investigation. The
product derived from oleic acid and N methyl taurine provides the optimum combination of desirable proper
ties. This compound is further recommended by the relatively low price of its raw materials.
Applications of Igepon T Products
Igepon T finds its greatest use today in the textile field where it was first introduced. It finds its way into
almost every phase of textile wet processing. The list of uses include scouring wetting out degumming kier
boiling dye leveling dye pasting chlorine and peroxide bleaching fulling lime soap dispersing and finishing. It
also finds application in agriculture paper leather and metal cleaning and also to a small extent in
household products including dentrifices shampoos cosmetics and pharmaceutical preparations. It is also
used in the scouring of feathers in electrolytic plating baths in the washing of automobiles airplanes rail
road coaches and locomotives rugs floors buildings and for cleaning streets and roads and in the dairy food
and for industries.
Igepon T can be prepared in a variety of forms. One is a clear liquid suitable for incorporation into
consumer products. It looks much like a conventional liquid soap and is available with 15 and 25 per cent
active ingredients. Another form is a slurry or an opaque heavy liquid. This material contains 28 per cent
active ingredients and is essentially the product as it comes from the condensation kettles it contains no
added chemicals. It may be used by formulators who will process it further by adding it to other ingredients
or drying it to a powder. It can be shipped in tank cars and is the least expensive of the various Igepons.
Future of Igepons
The future of Igepon T its analogs and homologs is bright. The economic existence of this type of product is
assured by the fact that the biggest weight in its molecule is a fatty acid. The principal fatty acid used is
oleic acid which is found abundantly in vegetable and animal oils. As synthetic detergents derived from non
fatty soures encroach on the soap market the fats and particularly tallow from which oleic acid is largely
derived will tend to become more a surplus product.
Another advantage enjoyed by the taurine type Igepon (N acyl N alkyltaurates) is the fact that the Igepon T
gel largest seller in the group today is not the best wetter in the series nor is it the best emulsifier or
dispersant. It is not the best foamer the best textile softening agent or lime soap dispersant nor is it the
most soluble member of the group. It has a good high average on all counts which led its developers to call
it the universal soap. The taurine type Igepon can be modified to well over 100 varieties. Any one of the
various surfactant properties may be obtained to a high degree by making changes in the structure of the
1gepon molecule. Consequently it is predicted that the 1gepon type surfactants will have an important
future in the development of special purpose products where price is not the primary consideration.
Manufacture of Igepon T
Raw materials
The major materials required for the production of sodium N oleoyl N methy ltaurine are oleic acid
phosphorous trichloride N methyltaurine and caustic soda. It is extremely important that a high quality of
oleic acid be used in the process. If an excessive amount of esters or unsaponifiable material is present the
resultant Igepon will have an excess of free fat which tends to make the gels cloudy.
The N methyItaurine may be used as a 25 to 30 percent filtered aqueous solution. The 30 and 50 per cent
caustic soda solutions and the hydrochloric acid used to control the pH of the batch at various points in the
processes can be the standard commercial products.
Oleic Acid Chloride
The first step in manufacturing Igepon T gel or Igepon T powder is the production of oleic acid chloride
(oleoylchloride) from oleic acid and phosphorous trichloride. Acid chlorides other than oleic may be used to
make special Igepon compounds.
The reaction takes place in a jacketted lead lined kettle equipped with both cooling water and low pressure
steam connections. A horse shoe type agitator stirrs the charge. A 1.5 lead vent to the roof of the building
removes volatile acid fumes and decomposition products of phosphorous trichloride from the kettle. It is
essential that the kettle be dry before charging is begun to prevent hydrolysis of the phosphorous
trichloride. If any condensation accumulates on the kettle due to extended inactivity it is driven off by
introducing steam into the jacket while the kettle is empty.
To begin the operation oleic acid is blown by air from a feed tank to a steel weigh tank phosphorous
trichloride is similarly blown into a lead lined weigh tank. A 400 kg. charge of acid is drawn from the weigh
tank and dropped by gravity into the kettle. Phosphorous trichloride (103 kg.) at room temperature is
introduced from the weigh tank over a period of one hour while cooling water is circulated through the
jacket of the kettle. A sight glass in the lead line through which the phosphorous trichloride is charged
permits the operator to judge the flow rate of this stream. After the kettle has been completely charged the
temperature is raised. to 50°C to 52oC and is held there for 6 hours by introducing 15 kg. steam into the
jacket. At the end of this period the temperature is raised to 60°C for an additional 15 minutes to ensure
completion of reaction.
About 60 per cent of excess phosphorous trichloride is used in the process. This excess about 38 kg. is
partially retained in solution in the fatty acid chloride and appears in the final product as phosphite salt.
The finished product is blown by air pressure into two lead lined cone shaped tanks and allowed to stand
over night settle out the by product phosphorous acid. The bases of the cones are heated with extended
1.5`` lead steam coils to thin down the heavy acid sludge and aid in the separation. After drawing off the
first waste acid the contents of the cone tanks are agitated and then a second separation of acid is drawn
off. The point of separation is determined by observation through sight classes in the draw off lines. The
spent acid is piped direct to the sewer through lead pipes traced with 1.5 outside diameter pipes carrying
low pressure steam.
Oleic acid achloride will descompose on standing if exposed to atmospheric moisture consequently it is
made up only as needed and is piped through steam traced lead lines direct from the cone tanks to the
weigh tanks of the Igepon unit.
This product is made in a brick lined kettle equipped with a four fingered stainless steel agitator. A stainless
steel submerged coil provides temperature control. The kettle has stainless steel feed lines for oleic acid
chloride and hydrochloric acid and caustic solution a stainless steel thermometer well and a lead vent pipe.
Air for forcing the charge out of the kettle is introduced into the vent pipe.
A stainless steel kettle equipped with an anchor type agitator is also available. Process temperatures in this
kettle are controlled by a steel jacket connected to both steam and cooling water lines. Inlets and vents are
arranged similarly to those in the larger kettle.
To begin the batch 25 to 30 percent aqueous solution of N methyl taurine is blown over from the storage
tanks until an amount of solution equal to 89.25 kg. of N methyltaurine has entered the weigh tank. The
correct gross weight of this charge based on the N methyltaurine analysis of the storage tank is supplied to
the operator by the analytical laboratory. This charge is then dropped by gravity into the reaction kettle and
the flow of cooling water is started in the jacket to bring the temperature of the charge down to 22° to 25°C.
Water weighed in the same weigh tank is then added to bring the total weight of the charge at that point to
1296 kg. Addition of 30 per cent aqueous caustic solution is begun and when the equivalent of 14.25kg. of
sodium hydroxide has been weighed in oleic acid chloride is introduced from a lead lined weigh tank.
The caustic and acid chloride enters the kettle through separate perforated stainless steel pipes below the
level of the initial taurine charge. This practice minimizes the liberation of noxious fumes reduces the
corrosive effect of the acid chloride above the liquid level and safeguards against side reaction between
sodium hydroxide and oleic acid chloride.
Simultaneous addition of the two reactants is continued for 4 to 6 hours until a total of 43.5 kg. of sodium
hydroxide and 214.2 kg. of about 92 per cent oleic acid and chloride have been charged. The rate of
addition of these two solutions is adjusted to maintain a slight stoichiometeric excess of sodium hydroxide
in the kettle at all time as determined by spot tests on triazine paper 2 (4 nitro O tolyldiazoamino 4
sulfobenzoic acid).
After all the reagents have been added the charge is agitated for an additional hour to ensure completion of
reaction. Cooling water is circulated through the coils at maximum flow rate during the entire reaction
period. During the winter months the temperature of the charge is about 22°C at the beginning of the
reaction and rises to 27°C. However in the summer time the final temprature may go as high as 40°C.
After the reaction has been completed a sample is taken and the percentage of excess N methyItaurine is
determined by coupling with diazotized mnitraniline. It is desirable to have a slight excess of N
methyltaurine in theproduct to ensure that the reaction has gone to completion. After completion of the
reaction hydrochloric acid is added to the kettle through a glass and rubber siphon from a carbon mounted
on a platform scale. Acid is added until the charge gives a slightly red spot test with brilIiant yellow paper
(pH 6 to 8). This neutralization usually requires about 15.3 kg. of acid. In making some of the special
Igepon products additional hydrochloric acid may be needed at this point.
In making the standard T gel the neutralized batch is diluted to 1734 kg. with water and 0.725 kg. of a light
floral liquid perfume. The charge is then heated to 55°C and held there for 1.5 hours. The charge is blown
into white oak gum or ash wood barrels. Air used to blow out the batch passes through a trap to remove
rust particles which would tend to darken the finished product. As a further precaution against
contamination a 0.007 opening stainless steel filter on the product discharge line removes all solid particles
from the liquid product before it enters the shipping containers. The barrels are allowed to cool on the
shipping platform and when the Igepon reaches a temperature of about 40°C it sets up as a firm opalescent
gel.
Igepon T gel may be shipped in polyethylene lined fibre board drums or wooden barrels. The batch
yields about 1090 kgs. gel having a composition of 15.3 to 16.3 per cent Sodium N oleoyl N methyltaurine
0.8 to 1.0 per cent sodium oleate 0.14 per cent N methyltaurine 4.0 per cent sodium chloride and 78 per
cent water. This represents approximately the theoretical yield.
Igepon T Powder
In manufacturing this product the initial charge of 30 per cent N methyltaurine solution contains 95 kg. of
100 per cent N methyltaurine and when diluted with water to 1224 kg. it gives a slightly more concentrated
solution than that used in the gel process. As a 30 per cent solution 17.6 kg. of sodium hydroxide are added
to this intial charge to keep the reaction mixture on the alkaline side. Then 226.5 kg. of technical oleic acid
ehloride are added simultaneously with 30 kgs. of sodium hydroxide as a 30 per cent solution over a period
of 4 to 6 hours as in gel production.
The batch is stirred for 1 hour after charging is completed and any excess of N methyltaurine is reactcd with
additional acid chloride and caustic soda as in the production of gel. The completely reacted charge is then
heated to 50°C by the steam coils and neutralized to the brilliant yellow and point with hydrochloride acid.
Immediately after neutralization 530 kgs. of common salt are dumped into the batch from bags and water is
added to bring the total weight of the batch to about 2652 kgs. At this concentration about 36 percent solids
the saIt is completely dissolved. It is important that no suspended solid material remains in the charge
because it would plug up the nozzles of the spray drier. If the pH of the batch after the addition of the salt
does not fall between 7.1 and 7.3 sodium hydroxide or hydrochloric acid is added to adjust the pH within
these limits.
The salt loaded mixture is blown from the reaction kettles into a 3/8 lead lined sted feed tank. The charge is
heated to 50°C by lead steam coils in the feed tank and then is pumped to the three 10 gauon feed pots of
the spray dryer. The dryer atomizers use air at 80 Ibs/in2 pressure heated to maintain 501bs. pressure at
the injection nozzles to ensure adequate atomization in the tower. Air supplied to top of the dryer is
preheated to about 225°C by an oil fired furnace and forced into the dryer by a centrifugal fan at a rate of
about 250 cubic feet per minute. The major part of the dried powder is discharged from the bottom of the
dryer tower and carried along by the added cold air into the primary cyclone separator from which it drops
directly into a transfer drum. About 10 per cent of the product however is carried through the cyclone and is
reintroduced into the dryer chamber. A second take off from the dryer chamber is located just above the
bottom taper. This duct carries a more dilute stream of air borne powder into a larger secondary cyclone
separator. The solids which fall out in this separator are refluidized by more cold air and returned to the top
of the primary cyclone. The overhead from the secondary cyclone containing 7 to 10 percent of the product
is introduced into a water scrubber. One water spray above the inlet and three below remove all but about 2
per cent of the product from the dryer exhaust. The scrubbed air is vented to the atmosphere. The liquor is
drawn from the bottom of the tower into a storage tank. Make up water is added to this tank by an
automatic level control. A high silicon iron pump drawing from the tank recycles water to the spray nozzles
and supplies process water to the condensation kettle.
If a kettle batch is made each day the dryer feed pots can be kept full and provide an uninterrupted feed to
the dryer. Under these circumstances the dryer can handle as much as 180 to 200 kg. Igepon per hour as it
has a rated capacity of 335 kg. water per hour. The product comes from the dryer as low density granules
which are lightly milled in a paddle mixer to break up the larger lumps and to mix in 500 grams of a light
floral perfume per ton of Igepon. From the mill the powder is dropped directly into the open top steel drums
in which it will be shipped. Yields of powdered product run about 836.4 kg. per batch and analyze about
30.5 to 32.5 per cent oleoylmethyltaurine 1.5 to 3.0 per cent sodium oleate and 0.14 to 0.8 per cent N
methyItaurine the remainder of the powder comprises inorganic salts. Chief among these is sodium chloride
and a trace of sodium sulfate. However phosphite salts (about 3 per cent) are also present these are
formed from the excess phosphorous trichloride dissolved in the oleic acid chloride. The yield is about 91
per cent of theory.
Chemical Control
Chemical control on the Igepon T operation is relatively simple. By experience rule of thumb knowledge can
be accumulated which tells the operators whether the reaction is going properly. At some points analytical
samples are taken merely as a precaution and only analyzed if trouble develops later in the operation.
The phosphorous trichloride oleic acid and N methyItaurine are checked for rigid spacifications each time a
shippment of materials arrive at the factory. The acid chloride charged to the reaction kettle is analyzed the
oleic acid chloride phosphorous trichloride and free fatty acid. After the condensation is complete the batch
is checked for pH and residual N methyltaurine. The pH is checked by a standard calomel cell pH meter
and is then adjusted as explained in the operation procedure.
After the pH has been adjusted it is checked again and the final shipping sample is sent to the laboratory.
This final sample is examined for clarity viscosity and alkalinity. A 10 percent water solution of this sample
must be perfectly clean and must have a pH between 7.2 and 7.5 at this point.
The Igepon T powder undergoes an almost identical analysis routine. If the content of oleoylmethyltaurine
falls outside of the permissible limits it is blended into the subsequent batches at the ribbon blender.
Utilities
In the Igepon process steam is used only for process heating. Since the temperatures required are all
reasonably low steam at 100 psi is adequate for this operation. Compressed air is used in the plant for
forcing liquids from one vessel to another the 45 psi air is sufficient. The air used for transfering
phosphorous tricoloride is passed through a dryer and filter to present hydrolysis and contamination. The
purifying unit consists of a liquid trap a steel chamber 12 in diameter and 6 long filled with quick lime to dry
the steam and a similar tank 4 long containing a cloth bag filler to remove any particles of lime or other
solids that might be carried over into the phosphorous trichloride tanks.
The spray drier may have a separate compressor which provides 90 Ib/in2 air for atomization.
Materials of Construction
The corrosion problem is not critical in the operations as described but some special materials must
be used. Carbon steel is suitable for most vessels. However those which must contain phosphorous
trichloride or oleic acid chloride are homogeneously lead bonded. This type of lining is applied by tinning
the entire inner surface of the steel vessel and then soldering the lead lining plates to the whole steel
surface. This technique eliminates the problem of buckling and blistering. It also means that in the event of
failure of the lining only the steel directly behind the gap in the lining is attacked. In the so called loose lining
technique in which the lead sheets are tacked to the shell only along with seams a failure at any point
usually means that the corrosive contents of the vessel will shortly enter the entire space between the lining
and the vessel wall. The spray drier feed tank may be lined in this fashion but only moderate temperature
are encountered in this tank and the agitation is never violent.
In general the lead linings in the Igepon process equipment last 7 to 9 years before they must be
replaced. The reaction kettles may be of stainles steel. If however it is brick lined construction it may require
re lining after about each two years. All equipment which comes in contact with finished liquid Igepon is
made of stainless steel. since the detergent will exchange cations with ordinary steel to form iron salt which
has an undesirable dark colour.
Submerged steam lines in the brick lined kettle are stainless steel in the spray dryer feed tank these are
lead. The other kettles are equipped with external jackets. Agitators are either lead cov N Acyl N
Alkyltaurates ered stainless steel or in the case of the spray drier feed tank wooden.Neither stainless steel
nor lead will stand up in the duct which carries the moist exhaust from the spray drier. Nickel or high nickel
alloy serves well. The spray drier itself is made of carbon steel.
Tanks which must with stand static pressure such as those employing air pressure transfer are
entered and inspected and subjected to hydraulic testing every 2 years. Unpressurized steel tanks which
store corrosive liquids are on a similar inspection schedule. Storage tanks in non corrosive service are
inspected every 5 years. Kettles are also inspected at 5 years intervals. Jacketed kettles are lifted out of
their jackets and the surfaces are cleaned and inspected for pits. Pits usually occur in the welded seams. If
the welds are badly pitted below the surface of the adjacent plates the bead is chipped off and the seam
rewelded.
Since most of the materials involved in the process are transferred through the plant by air pressure
pumps present only a limited corrosion problem. Where pumps are used they are of motor driven
centrifugal type. Where pure oleic acid must be pumped a high alloy steel pump is used. All other pumps
are of carbon steel.
Stainless steel valves are used on all lines which transfer finished liquid Igepon T. Pipe lines which
carry liquid Igepon T also are of stainless steel. Those which transfer oleic acid chloride are lead lined and
steam traced. The steam tracing is only used in the winter when the acid chloride has a tendency to thicken
and move sluggishly.

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