Professional Documents
Culture Documents
FOR
CHEMICAL SPECIALTIES
OPENING REMARKS sion of the Soap Association, and other members of the Soap
Association f o r their excellent cooperation and assistance in
Mr. Chairman, Ladies and Gentlemen, the subject to be arranging this panel discussion.
discussed this morning is "Fatty Acids."
The topics to be discussed by the panel members were
For many, many years F a t t y Acids have been the main selected so t h a t fatty acids would be covered completely from
ingredients in the production of all types of soaps. The soap their basic chemistry t o their end uses i n special products.
industry is one of the oldest in America, and has been and
continues to be a very important economic factor in our The panel members were selected from the major producers
everyday living. P
of f a t t y acids and chemical specialties. They a r e all experts
in this field.
The uses of soap have become innumerable and varied.
Its largest market is in the home, where its chief uses are I would now like, to introduce the panel members. First,
as toilet soap and a s laundry soap. There are, however, very Dr. H. C. Black of Swift and Company, who will speak on
many industrial applications f o r soap because of its wetting, the "Basic Chemistry of F a t t y Acids"; Dr. H. Wittcoff of
emulsifying and cleansing powers. Soap is nqw found in many General Mills, Incorporated who will discuss the "Properties
commercial processes. of F a t t y Acids and Analytical Methods"; Dr. M. R. McCorkle
of Armour and Company, who will cover "Reaction Products
Over the past five years soap requirements, sales, and of F a t t y Acids"; Dr. George Zinzalian of E. F. Drew and
production have slowly decreased. This has also reflected a Company who will speak on "Storage and Handling of F a t t y
decreasing requirement for f a t t y acids, since they a r e the Acids"; Mr. R. D. Aylesworth of Emery Industries, Incor-
basic ingredient in soap production. porated whose subject will be "Requirements of F a t t y Acids
In view of this decline in the requirements for f a t t y acids, used in Liquid and Metallic Soaps"; and Dr. H. Lederer of
many companies have spent considerable time and effort in R. M. Hollingshead Corporation who will conclude the formal
research and market development t o develop new outlets, presentation p a r t of this program with a paper on "Re-
uses and applications for fatty acids. In this investigation quirements of F a t t y Acids used in Other Chemical Specialty
many new and interesting developments have been uncovered Products."
in regard to fatty acids. In order to keep the meeting running without any inter-
Approximately five years ago this division sponsored a ruption, the six speakers will give their papers in the order
symposium on fatty acids. I n view of the more recent develop- introduced. After the last paper has been completed, there
ments on fatty acids, it was felt worthwhile to have another will be a short recess during which we will collect the forms
panel discussion on these materials. which were handed to you a s you came in. Please write any
The purpose of this symposium, organized through the questions you wish to ask, the name of the panel member
combined efforts of the Market Development Committee of to whom you want i t directed, and your name and company.
the Fatty Acid Division of the Soap Association, and the If you do not direct i t to a n y one person, then we will t r y to
Soaps, Detergents and Sanitary Chemicals Division, is to dispose of i t a s best we can. I also want to suggest that there
convey to the members of the CSMA all the latest informa- is no rule in this panel against panel members' asking each
tion available on f a t t y acids. other questions.
We wish to thank Mr. Scott Pattison, Manager of the Now I would like to proceed with t h e more interesting
Fatty Acid Division of the Soap Association, Mr. B. W. part of the program by introducing the first speaker a t
Schroeder, Chairman CSMA Sub-committee, F a t t y Acid Divi- this time.
INTRODUCTION we have had recently. I n the past two decades, much work
has been done and. many articles and numerous good books
The basic structure of fats was established nearly a century on f a t s and f a t t y acids have been published. We know the
and one-half ago when Chevreul found that they were -com- structure of the great majority of the known f a t t y acids
posed of fatty acids and glycerol. A little later Gusserow and have information a s to how to prepare and make prac-
separated saturated from unsaturated acids by differential tical use of many of their derivatives in our expanding
solubilities of their lead salts. Even though many significant chemical era.
and ,brilliant discoveries were made during the nineteenth SOURCES
century, the fats and fatty acids were sadly neglected until
the beginning of the twentieth century. They were not attrac- F a t s a r e essential constituents of all forms of plant and
tive research materials because they were not readily crystal- animal life, and are consequently widely distributed. However,
lizable and few crystalline derivatives could be prepared. In the plants and animals that produce oils and f a t s in snffi-
spite of the lack of basic chemical knowledge during the cient quantity to constitute a significant source a r e few. The
nineteenth century, much empirical information. accumulated largest of these comprises the annual plants sucli a s flax,
permitting establishment of the consuming industries such soybean, cotton, peanut and castor bean. These grow in
as food, soap, paints and varnishes. There was no surplus a s temperate climates requiring cultivation. Production can be
varied. The second source of vegetable oils is the oil bearing UNSATURATED ACIDS
trees such a s coconut, palm, olive, and tung. These grow in
the warm o r temperate climates. These acids, particularly the highly unsaturated members,
are not a s well characterized as the saturated acids because
The commercial land animal f a t s come largely from hogs, of the difficulties in isolating them. Also, changes can occur
sheep and cattle. Milk fats are nearly all used for food. The during separation and identification.
sea contributes a considerable volume of oil. Among the most
important sources are sardine, menhaden, herring and whale, The unsaturated acids differ from one another in the
including sperm whale. number of carbon atoms, the number of double bonds, the
position of the double bonds, and the geometry of the double
bonds. All of the unsaturated acids, with the exception of
CHEMISTRY elaidic, are liquid a t room temperature.
Fatty acids a r e present in fats and oils a s glycerides o r
esters of glycerol except in sperm oil, where some of the TABLE I1
fatty acids are esterified with f a t t y alcohols, mainly cetyl
alcohol. The fatty acids a r e released by hydrolyzing ester Unsaturated Acids
linkage. This is done by chemically adding water, a process (Monoethylenic)
commonly referred to a s f a t splitting. The most common
methods are the Twitchell, autoclave, and continuous methods. Number of
In the Twitchell process a catalyst speeds up the reaction Common Name Carbon Atoms Geneva Name
a s the f a t is heated with boiling water. The autoclave method
depends on heat to speed the reaction. The continuous method Obtusilic ........................ 10 ...................... 9 :10 Decenoic
also relies on heat, and is carried out by passing water and Caproleic ....................... 10 ...................... 4:5 Decenoic
f a t countercurrently through a tower. Lauroleic...................... 12 ...................... 9:10 Dodecenoic
The fatty acids resulting from the splitting operation can 12 ...................... 4:5 Dodecenoic
be used as such o r further processed to-remove non-fatty Myristoleic ................... 14 ...................... 9 :10 Tetradecenoic
acid constituents, and fractionated by distillation or selective
solvent extraction. They may be fractionally crystallized by 14 ...................... 4:5 ~etradecenoic
chilling and pressing, o r by the use of solvents. New tech- 14 ...................... 5 :6 Tetradecenoic
niques still in the experimental stage for separation a r e Palmitoleic.................... 16 ...................... 9 :10 Hexadecenoic
molecular diffusion and the use of urea or thiourea to form Oleic............................... 18 ...................... 9 :10 Octadecenoic
complexes. Petroseleric.................. 18 ...................... 6 :7 Octadecenoic
FATTY ACIDS Elaidic ........................... 18 ............trans 9 :10 Octadecenoic
Vaccenic ........................ 18 ............trans -11:12 Octadecenoic
The natural fatty acids a r e generally aliphatic compounds
with a carboxyl group a t the end of a straight carbon chain. Gadoleic:........................ 20 ...................... 9 :10 Eicosenoie
Nearly all of them have a n even number of carbon atoms. Erucic............................ 22 ...................... 13 :14 Docosenoic
The acids differ from one another in the number of carbon
atoms and the number and position of the double or unsa-
turaljed bonds.
Table I1 shows the common fatty acids with one double
SATURATED ACIDS bond. When one double bond exists,' i t can be between any
two of the carbons except the first and second. However,
The saturated acids contain no double bonds. They vary only a few of the possible positions are found in nature.
in chain length from butyric, which contains four carbon In addition, a t any double bond, it is possible to have two
atoms, to lignoceric, which has 24. Table I shows the common geometric isomers referred to a s cis-trans isomers. Table
saturated acids. At room temperature the shorter chain length I11 represents this. Oleic acid is cis, and elaidic acid is trans.
acids are liquid. Lauric and all longer chain acids are solids
at room temperature. The most widely distributed and the
most commercially important a r e palmitic and stearic acids. TABLE I11
Commercial stearic acid in its different grades consists of
roughly equal parts of these two acids. Cis-Trans Isomers
CH,(CH ) CH CH,(CH ) CH
TABLE I
'11
HOOC (CH,) ,CH HC (CH,), COOH
Oleic - cis Elaidic - trans
Saturated Acids
~ -
Number of In the case of acids with two o r more double bonds, the
Common Name Carbon Atoms Geneva Name double bonds may have no carbon atoms o r several carbon
atoms between them. A case where no carbon atoms separate
Butyric .............................. 4 ............................Butanoic the double bonds is referred to a s a conjugated system. This
Caproic .............................. 6 ............................Hexanoic is represented in Table IV. We may have .more than two
Caprylic .............................. 8 ............................Octanoic
. Capric ................................ 10 ............................Decanoic TABLE IV
Lauric ................................ 12 ............................ Dodecanoic Position of Double Bonds
Myristic .............................. 14 ............................Tetradecanoic
Palmitic .............................. 16 ............................ Hexadecanoic H
-c=c-c=c
H H H
Stearic ................................ 18 ............................ Octadecanoic H H
Arachidic .......................... 20 ............................Eicosanoic conjugated
Behenic .............................. 22 ............................Docosanoic
Lignoceric .......................... 24 ............................ Tetracosanoic H H H H
Cerotic ................................ 26 ............................Hexacosanoic -C=C-CH,-C=C-
Non-conjugated
-
double bonds in a conjugated system. Di and poly unsatura- In the partial hydrogenation of unsaturated fatty acids,
tion imparts much faster reaction rates than one double bond. many isomers may be produced. One or more of the double
The conjugated system in fatty acids, a s in other organic bonds in any of the various positions may be hydrogenated.
compounds, greatly increases the reactivity, and conjugated The double bonds may shift positions or be converted t o the
fatty acids undergo chemical reactions very similar to those trans form if not hydrogenated.
of conjugated systems in general. Table V shows some of
the di, tri and poly unsaturated acids. TABLE VI
TABLE V Fatty Acids of Unusual Structure
Unsaturated Acids Common Name
Number of
Carbon Atoms Structure
(Di & T r i & Polyethylenic)
Number of Number of
Tariric ........................ 18 Trip!e bond between 6 and 7th
Carbon Double
carbons.
Common Name Atoms Bonds Geneva Name Ricinoleic .................... 18 12-hydroxy 9 :10 Octadecenoic
Linoleic 9:10, 12:13 Licanic ........................ 18 4-keto 9 :lo, 11:12, 13 :14
Octadecadienoic Octadecatrienoic
9:10, 12:13 Hydnocarpic .............. 16 Closed 5 membered ring a t end
Docosadienoic of carbon chain.
Hiragonic 6:7, 10:11, 14:15 Chaulmoogric ............ 18 Closed 5 membered ring a t end
Hexadecatrienoic of carbon chain.
Linolenic 9:10, 12:13, 15:16
Octadecatrienoic Table V I shows several f a t t y acids of unusual structure.
Elaeostearic 9:10, 11:12, 13:14 Ricinoleic acid is the principal acid in castor oil. On dehydra-
Octadecatrienoic tion, a good portion of conjugated linoleic acid i s produced.
Parinaric 9:10, 11:12, 13:14, 15:16 This accounts for the good drying properties of dehydrated
Octadecatetraenoic castor oil. Licanic acid occurs in oiticia oil. It has three con-
Moroctic 4:15, 8:9, 12:13,-15:16 jugated double bonds and a ketone group.
Octadecatetraenoic
Arachidonic 5:6, 8:9, 11:12, 14:15 SUMMARY
Eicosatetraenoic
I n addition to their economical importance, the f a t t y acids
Clupanadonic Docasapentaenoic a r e a versatile and interesting group of organic compounds.
dustry uses a much smaller quantity of high grade acids. The textile industry is interested i n acids of good color
These find application in such products a s shaving creams, and good odor. Good oxidative stability is required together
vanishing creams and lotions, deodorants and shampoos. with low polyunsaturate contenb. Analytical procedures for
Various grades of stearic acid, oleic acid, lauric acid and determining these critical specifications have already been
coco acids a r e used by the cosmetics industry. The pub- discussed above.
lished specifications for these acids frequently do not reflect SUMMARY
the demands made b y the cosmetics industry. Such prop-
erties a s good color and low iodine value a r e important f o r his paper has outlined the specifications of several types
saturated acids. Other important properties, often not re- of f a t t y acids which a r e widely used in a number of indus-
flected in manufacturers' specifications, include crystalline tries. k n attempt has been made to explain t h e significance
structure, coefficient of shrinkage, penetration and odor. of these s~ecifications. a n d the analvtical orocedures for
Some of these properties have been discussed in a n article determining these specifications have i e e n described. It has
by Peters and Clark.19 These authors determined shrink- not been the purpose of this paper to be all-inclusive. Rather
age, for example, by melting saturated acids in a n oven a t the goal has been to point o u t the most widely used analytical
SO" C. in small. straight-sided molds. These were then al- procedures as they relate to the important uses of f a t t y acids.
lowed to cool slowly in the oven. The per cent shrinkage
was calculated by subtracting t h e diameter of the cboled REFERENCES
cake from the diameter of the mold, dividing this figure
by the diameter of the mold, and multiplying the resultant 1. American Oil Chemists' Society Official Method, Cd. 1-25.
value by 100. 2. Von Mikusch, J. D. and Fraeier, C., Idn. Eng. Chem.,
Anal. Ed., 13 782 (1941).
The degree of crystalline structure of a saturated acid 3. American .Oil Chemists' Society Official Method, Da.
or mixture of acids may be determined by inspection. As 14-48.
4. Ibid., Cd. 3-25. 15. American Oil Chemists' Society Official Method, Cd. 7-48
5. Zbid., CCB.6a-40. (Revised May, 1951).
6. Ibid., Ca. 2c-25; Ca. 2b-38; Ca. 2d-25 (1946). 16. Gardner, H. A., "Physical and Chemical Examination
7. Ibid., Cc. 12-41. of Paints, Varnishes, Lacquers and Colors", H. A. Gard-
ner Laboratory, 11th Ed., 1950, p. 343; Trusler, R. B.,
8. Ibid., Ka. 3-47. Oil and F a t Industries, 8, 51 (1931).
9. Ibid, Cc. 13b-45 (Revised Oct., 1952). 17. Wheeler, D. H., Oil and Soap, 9, 89 (1932).
10. Zbid, Cc. 138-43.
18. American Oil Chemists' Society Official Method, Ca.
11. Ibid., Cc. 13c-50 (Revised, 1952) .11-46.
12. American Society for Testing Materials, Method D1240-
52T. 19. Peters, R. M., and Clark, W. C., Jr. Am. Oil Chemists'
SOC., 27, 201 (1950).
13. Norris, F. A. and Terry, D. E., Oil and Soap, 22, 41
(1945) ; Toilet Goods Association Method # 61. 20. American Society for Testing Materials. Method D-5-52.
14. Earle, F. R. 'and Milner, R. T., Oil and Soap, 17, 106 21. Worth, H. A,, "The Chemistry and Technology of
- "(1940). Waxes", Reinhold Publishing Co., 1947, pp. 338-343.
The most $remising, new markets f o r fatty acids probably mono-, di-, and triethanolamines, isopanolamine, morpholine,
lie in the direction of derivative formation. The fatty acids ctc. The compounds formed by such reactions a r e simple
themselves are well known and their applications well ex- neutralization products, prepared in solvent usually, but
ploited. The variety and versatility of their derivatives, how- rarely isolated a s such.
ever, constitute a challenge to the research and manufactur- 0
ing chemist.
II
I should like to discuss just one phase-a still-developing RC-OH + R'NH, j - RCOO [R'NH,]
phase--of the attack on this problem. Acid Primary Amine Salt or "Soap"
Leaving aside consideration of the simple, inorganic neu- They are, generally, prepared in situ, where needed, by a low
tralization products of the fatty acids, the metallic soaps, temperature reaction in a one-to-one molar ratio of acid to
the largest volume derivatives a r e the alcohols, the esters and amine. Their largest areas of application a r e a s lubricating
the nitrogen-containing compounds. The alcohols probably agents in rayon filament cone-winding or in wool spinning
constitute the largest single group of products, in their func- and weaving, a s emulsifying agents in preparing resin emul-
tion as base materials for synthetic detergents, although sions, and in the cosmetic field, where they are characterized
much of this is captive production. The mono-and poly-esters by the high-stability emulsions and soft creams they give
of the fatty acids a r e probably next in tonnage produced, in hair waving lotions, shampoos, etc. Their ability to be
and a r e largely found a s plasticizers, a s surface-active removed easily, by water rinsing usually, after serving their
agents, or a s protective coating ingredients- The nitrogen- prescribed function is p a r t of their value a s emulsifiers, too.
containing derivatives, those under discussion here, a r e next.
Totalling about 60 million pounds of product in 1953, for
surface-active uses alone, they more than doubled their
The substituted amides are, a t present, the largest repre-
sentative class of nitrogen-containing compounds. The sim-
plest approach to these derivatives is through certain of the
.
production rate of 1948.
organic amines just mentioned. Low temperature reaction
Although f a r from the leading volume consumer of fatty gives neutralization, or salt formation. Elevated reaction
acids, this latter group does constitute one of the most ver- temperatures, say 140-200" C., with the primary or secondary
satile and interesting groupings-at least from a chemical amines gives the mono- o r di-substituted amides, respectively,
standpoint. with the resultant loss of a mol of water.
The nitrogen is usually added t o the molecule by reaction 0
with, or by replacement of the carboxylic function. The re- A II H
sulting compounds a r e usually surface-active, combining the RCOO [R'NH,] + RCNR'
balance of a long-chain, hydrocarbon, hydrophobic "tail" with Salt or "Soap" Mono Substituted Amide
a polar, hydrophilic "head." They can be diversified a s to s i x to seven hours of heating time is necessary to drop the
mode of ionization. They can be classified a s non-ionics, for free acid to the few per cent level.
example the ethylene oxide addition products of the unsub-
stituted amides; a s anionics, by sulfation of the ethanol- The simplest substituted amides a r e those prepared from a
ilmides; or a s cationics, characterized by the highly adsorbent one-to-one molar ratio of acid to, e.g., mono- or diethano]-
amines and quaternary ammonium salts. amine. These a r e well defined compounds, essentially non-
ionic, useful in their own right or a s chemical intermedi-
The nitrogen-containing derivatives may be divided, on the ates. Their major application is as additi jes to the better
basis of commercial significance, into five major groups; the know alky] sulfates or alkyl-aryl sulfonates. ~h~~ function,
organic soaps, the amides, nitrilest amines and quaternary here, a s suds boosters and stabilizers, enhancing the effect
amonium compounds. I should like to examine each of these
in turn, particularly from the standpoint of preparation and sf the base detergent. Tailor-making of these compounds,
by balancing the hydrophobic 'dtailn (the length and unsat-
application. uration of the chain) and the hydrophillic "head" (the na-
The fatty acids, a s acidic compounds, can of course be ture of the hydroxyl grouping around the amide function)
neutralized by basic materials. The most common of the will give a wide area of activity. Direction toward synergism
organic amines t h a t have been used for this purpose a r e the with a specific detergent formulation can be arranged.
These hydroxy-substituted amides may also be further The polyamines (ethylene diamine, diethyl ethylene di-
reacted to give anionic, sulfated products. amine, etc.) also contribute to a distinctive class of arnide
derivatives, the so-called "Sapamine~.~' These a r e prepared
0 0
by reacting a mol of fatty acid with one amine of a polyamine
II H II H
RCNCHzCHzOH + H,SO, -+ RC NCH,CH,OSO,H
molecule, leaving a free substituted or unsubstituted amine
- grouping in the final product.
Monoethanolamide Sulfated Amide
This can be carried out by low temperature reactions (with
or without solvent) with sulphuric acid, oleum o r chlorsul- II
RCOH +
H,NCH,CH,NH, -,R NCH,CH,NH,
JH
fonic acid. These are excellent heavy-duty detergents in Ethylene Diamine N-Aminoethyl ~ l k ~ l a m i d e
themselves, with good hard-water foaming characteristics
and good sudsing properties. They a r e quite mild to the These ,are now cationic agents, ionizing so t h a t the long alkyl
skin, compatible with soaps, and a r e used by the cosmetic chain bears the positive charge. They a r e often used in the
chemist in shampoo formulations. form of their salts, the neutralization products of the.free
By varying the ratio of hydroxy-containing amine to fatty amine function. Besides their general classification a s emulsi-
acid, the nature of the product is radically changed, from an fying agents and detergents, they have found use a s fabric
essentially water insoluble product to a soluble one. A two- softeners, levelling agents for dyes, in formulating shampoos,
to-one ratio of diethanolamine to fatty acid, e.g., gives a acid creams, etc.
mixture, of unknown chemical structure, that is a n excellent Carried further, the polyamines contribute two other
primary detergent itself. This phenomenon will occur with classes of nitrogen derivatives. Those with more than one
several compounds of this type, giving rise to a class of primary or secondary amine can give polyamides with excess
products collectively called by the trade name "Ninols." fatty acids. Those amido amines still with a free amino
Diethanolamine "NinolJJ@
They find rather wide application in liquid detergents, as grouping can undergo thermal dehydration and ring closure
emulsifying agents (in horticultural sprays, e.g.), a s dye to the corresponding cyclic imidazoline derivative.
Diethylene Triamine
1"
I
CH,CH,NH,
"Imidazoline"
solvents in lipsticks, a s pigment dispersing agents, a s thick- These are finding application as asphalt anti-stripping addi-
ening agents for synthetic detergents or liquid soaps, a s tives, a s emulsifiers (cationic), in ore flotation, and a s inter-
viscosity increasers in paste or cream preparation, a s vat mediates in quaternary ammonium salt formation.
dye suspenders in textile dyeing and a s shampoo ingredients.
The simplest of the amides, and most promising from a
Another major group of amide derivatives centers around chemical intermediate standpoint, a r e those derived from
the sulfonated amines typified by the "IgeponJJ type of com- fatty acids and ammonia. Under the proper conditions, about
pound. This involves the reaction between the fatty acid 200°C. under a slightly vented ammonia atmosphere, the in-
(usually in the form of the acid chloride) and a primary or termediate ammonium soap decomposes, loses a mol of water
secondary amine containing a sulfonic acid grouping in the and is converted to the unsubstituted amide. These are, gen-
molecule. erally, neutral, waxy, high-melting solids, of low water solu-
bility. They are useful, in themselves, a s anti-tack and anti-
0 blocking agents, a s foam boosters and stabilizers for the
II
RC-CI + HNCH,Cfi,SO,Na NaOH
----+ C N CH2CH2S03Na
synthetic anionic detergents, as mutual solvents f o r blending
I I
waxes and plastics, a s ink additives, etc. One of their largest
I uses, however, depends upon further reaction with formal-
Acid Chloride h ~ , CH3 dehyde. Alone, with a n acid catalyst, the diamides a r e formed,
Sodium N Methyl Taurine "1gepon7'@ potential wax extenders and substitutes.
The resultant sulfonated amide, atypically anionic compound, 0 0
can be varied in properties, again by balancing the polar HCHO
and non-polar functions in the molecule. These compounds,
in general, have excellent emulsifying, wetting and detergent
+
H+
properties, and a r e resistant to acid, base, hard water, and
hydrolysis in neutral solution. Their uses include admixture Unsubstituted Diamide
with soaps to prevent lime soap deposition, a s a levelling Amide
agent in dyeing textile fibers, in the kier boiling of cotton, in
bleaching heavy cotton fabrics, in electroplating, in sham- I n conjunction with pyridine and HCl, the resulting quater-
poos, a s a detergent or detergent additive, etc. nary is a fabric softener and water repellent.
C
Water Repellent Film
Applied in solution and decomposed by heat, t h e so-called cently available compounds, their potential markets a r e quite
Zelan process, a water repellent film deposits on the fabric. substantial.
Reaction with ethylene oxide gives a series of water dis- I n terms of strictly chemical approaches to the amines,
persible o r soluble products, useful a s dispersing agents, in many avenues of derivative rsearch and reaction a r e avail-
waterless hand cleaners, in buffing sticks and liquids and a s able. Some have already successfully reached volume produc-
silicone and wax emulsifiers. tion. The amines, since they contain active hydrogen atoms,
will undergo reaction with ethylene oxide, giving rise to a
series of basic, cationic derivatives containing the derived
ethoxy units in the molecule.
H
I
RN - H + (x + y) CH, - H z -, R N
/ (CH,CH,O)x H
Ethylene Oxide "Ethomidl'@
However, the most versatile outlet for the unsubstituted 0' - 9 \(CH,CH,O) y H
"EthomeenW@
amides is a s their decomposition products, the nitriles. These
a r e formed by the loss of a mol of water from the amide, They a r e useful as emulsifjring agents, in soluble cutting
under essentially vapor-phase, catalytic, dehydration con- oils, as anti-static ,agents, in dry-cleaning detergents, etc.
ditions. The amines will form carbamates with CO,, a n easily re-
versible reaction;
I
R OH + 'I:
NH, + R 0 [NH,] II
+ RCNH, + RC - N
L
H
2 R -H +
CO, +
0
H II
RNC- 0 [NH,Rl
Ammonia Soap Amide Nitrile
Their uses, per se, a r e limited, a s plasticizers and yarn spin- Carbon
ning lubricants. Their most important reaction, however, Dioxide Carbamate
is reduction to the primary or symmetrical secondary amines, they can be converted to the isocyanates, useful a s toxicants,
source materials f o r a score of versatile and interesting with phosgene;
derivatives.
H
RC = N + H, RCH,NH, Primary Amine I
Hydrogen
cll'talyst RN - H +
COCI, -+ RNCO 2HC1 +
(RCH,),
- - NH +NH,
Phosgene Isocyanate
I -H H [HI H
RN + CH, = CHCN -+ RN - CH,CH,CN + R N - CH,,CH,CH,NH,
Acrylonitrile Diamine
and they will react with acrylates and crotonates to give (those derived from the secondary amines a r e oil-soluble)
alkyl substituted amino acids, o r Zwitterions, valuable deter- a s inhibitors for sulfate-reducing organisms; they are used
gents and surface-active agents. a s wetting and finishing agents in the textile industry; as
anti-static agents in the plastic and fiber industries; as
H after-rinses in laundry washing, for their germicidal and
RN
I - H + CH, H
= CHCOOH + RN - CH,CH,COOH
very noticeable cloth-softening effects; a s flotation agents;
a s ingredients i n Bentone grease formulations - particularly
Acrylic Acid Amino Acid the di long-alkyl-chain derivatives; etc. On the debit side
However, the largest class of amine derivatives is that en- they are not particularly good detergents themselves and are
compassing the quaternary ammonium compounds. These a r e incompatible with anionics. Their advantages f a r outweigh
prepared by the exhaustive alkylation of the amines, giving their disadvantages, however.
a positively charged long chain a s the-cation and containing
a pentavalent nitrogen atom with four co-valent carbon sub- In general, the nitrogen-containing fatty-acid-derivatives
stituents and an electrovalent-bonded anion. These com- field is a promising one. Its fundamental assets a r e the sur-
pounds a r e extremely valuable surface-active agents, and are face activity of its members, tailor-made by varying the
obviously capable of great structural variation. The primary molecular elements; its many avenues for derivative varia-
and secondary amines are alkylated with methyl chloride, tion, its chemical versatility and functional group varia-
dimethyl sulfate, etc., in solvent and in the presence of a n bility; and a potentially cheap and plentiful source of supply.
inorganic alkali;
n,n-Dimethyl Benzyl
Alkylamine Chloride
I. FA'ITY ACIDS FOR METALLIC SOAPS dures and end-uses f o r metallic soaps. Licata4 has related
f a t t y acid composition a n d the common manufacturing pro-
INTRODUCTION cedures f o r metallic soaps. A n excellent summary of lubricat-
ing grease applications for metallic soaps may be found
The purpose of this paper is to review briefly the com- in Boner's Manufacture and Application of Lubricating
mercially f a t t y acids used in t h e manufacture of metallic Greases.1
soaps. Elliott3 defines metallic soaps a s the alkali, alkaline-
earth, o r heavy-metal salts of monobasic, complex organic One important source of information relative to metallic
salts. The more commonly accepted industrial connotation soaps might be overlooked: the manufacturers of metallic
excludes the water soluble sodium and potassium soaps. Tal- soaps. The industry stresses application research t o a high
lates, resinates, a n d naphthenates a r e not considered in this degree. Most manufacturers of metallic soaps have well-
presentation. qualified technical personnel who specialize i n application
research and are available for discussion of specific applica-
LITERATURE tion problems.
Any reasonably complete summary of references to the
use of fatty acids f o r metallic soaps is beyond the scope of MAJOR FATTY ACID PRODUCTS
this paper. However, the listing of several general sources of USED FOR METALLIC SOAPS
information may be of value to technical personnel who a r e I n various degrees of purity o r grade, the following fatty
not intimately acquainted with the field. acid products account f o r the major volume of sales to manu-
Elliott's American Chemical Society monograph The Al- facturers of metallic soaps:
kaline-Ewth and Heavy-Metal Soaps3 affords a standard Stearic acid
textbook treatment of metallic soaps. The Texas Company h a s Hydrogenated Tallow acids
published a compilation of Properties of the Principal Pats,
Fatty Oils, Waxes, and Fatty Acids and Their Salts2 includ-
Hydrogenated Fish acids
Oleic acid
-
ing a bibliography of more than 600 references. Wendt a n d Vegetable F a t y acids (high iodine value)
Wagner6 have provided a summary of manufacturing proce- Coconut acids
TABLE I APPLICATIONS FOR METALLIC SOAPS
Composition of Major Commercial Fatty Acids Typical applications f o r metallic soaps of several . fatty
Used in the Manufacture of Metallic S o a ~ s acids a r e indicated in Table 111. The number of commercially
available metallic soaps of f a t t y acids is, of course, much
unsaturated larger. Obviously, the potential number that could be pro-
Commercial Product Saturated bid Composition Acids duced by different methods of manufacture from various com-
. binations of the scores of commercial f a t t y acids and 40-45
Stearic Acid ....................91-99.5% (55 parts C,,) 0.6-9% readily available metals is astronomical.
(45 parts C,,)
TABLE I11
Hydrogenated Tallow 91-99.5% (70 parts C,,) 0.5-9%
Fatty Acids ................ (30 parts C16) Typical Applications for Several Metallic Soaps
Hydrogenated Fish of Fatty Acids
. Acids ......................... -95-99% (mixture-C,,-C,,) 1-6%
Fatty Acid Metal Typical Application
Oleic Acid ........................ 5-10% (Cl,-C16) 90-95%
Stearic Acid Calcium Cosmetic Formulation
Vegetable Fatty Acids 5-30% (C,,-C,,) 70-95%
Hydrogenated Tallow
Coconut Acids ................90-99% (mixture C,-C,,) 1-10% Acids Zinc Rubber compounding
Hydrogenated Fish
Table I is a summary of the compositions of the major Acids Aluminum Flattening Agent
commercial fatty acids used in the manufacture of metallic Oleic Acid Copper Mildew Prevention
soaps. Of the individual component f a t t y acids found in these Vegetable Acids Manganese Paint Drier
products eight account for' an overwhelmingly large propor-
tion of the total fatty acid usage by metallic soap producers: Lauric Acid Cadmium- Vinyl Stabilizer
These are stearic (C,, saturated), palmitic (C,, saturated), Barium
arachidic (C,, saturated), behenic (C,, saturated), lauric 12-Hydroxystearic Lithium Lubricating Greases
(C,, saturated), oleic (C,, monounsaturated), linoleic (C,, Acid
diunsaturated) , and linolenic (C,, triunsaturated) .
SPECIALTY FA'ITY PRODUCTS CONCLUSIONS AND SUMMARY
USED FOR METALLIC SOAPS The major sales volume of f a t t y acids to producers of
Table I1 is a listing of a number of specialty f a t t y acid and metallic soaps is accounted for by a restricted group of
fatty derived products used for manufacture of metallic products and component acids. There are, however, many
soaps. Some of these specialty products are used a s modifiers additional f a t t y .acid and f a t t y derived products t h a t meet
for standard metallic soaps. Others are used as the total special requirements of the metallic soap industry.
organic components. All offer the manufacturer of metallic Tremendous technological progress during the past two
soaps and his customers the opportunity of attaining optimum decades has been a characteristic of the f a t t y acid industry.
answers to specific industrial requirements. The primary benefits to manufacturers of metallic soaps and
their customers have been threefold (1) standardization of
TABLE I1 commodity f a t t y acids (2) availability of f a t t y acids of
Specialty Fatty Acid and Fatty Derived Products higher purity, and (3) development of new and unique fatty
Used in the Manufacture of Metallic Soaps acid and f a t t y derived chemicals.
10 1. I* I2 26 10 S* Y
10 14 11 22 26 30 14 J 42
C R E A L SOAP
C R E A L SOAP
The effect on liquid soap viscosity of 2%, 5, 10 and 20 per tallow acids, and other C,,-C,, f a t t y acids is in the range
cent modification of potassium oleate solutions with saturated of 18-22 per cent soap concentration.' The level will vary
acids is shown in Table V. Concentrations of the various somewhat depending on f a t t y acid composition, unsaponifi-
soaps required to achieve viscosities of 20 centipoises and 80 able content, and state of oxidation.l.2 That saponification
centipoises a t 25°C. are given. The data for Table V were number, titre, iodine value, etc., a r e of limited value in pre-
derived by determining soap concentration-viscosity relation- dicting viscosities of liquid soap solutions is demonstrated
ships a t 25°C. for potash liquid soaps of oleic acid and oleic by the data in Table VI.
acid modified with varying proportions of saturated acids. Coconut fatty acids a r e unique among the commonly avail-
The liquid soap concentrations exhibiting viscosities of 20 dble commercial fatty acids in allowing preparation of a 35-36
centipoises and 80 centipoises were obtained from the in- per cent free-flowing potash soap.&The less frequently used
dividual viscosity-soap concentration curves. babassu and palm kernel f a t t y acids are, of course, similar
TABLE V
Real Soap Concentrations for Potassium Oleate Soaps
Exhibiting Viscosities of 20 Centipoises and 80 Centipoises at 25' C. When
24/20Jo-2070Saturated Fatty Acids Are Substituted for Oleic Acid
% Modifying Real Soap Exhibiting 20 Centipoises 70 Real Soap Exhibiting 80 C e n t i p o i s e s
Acid Content 2% 5 10 20 2% 5 10 20
>Iodifying F a t t y Acid
Stearic .................... 17.1 17.4 17.2 17.2 19.0 19.2 19.1 19.0
Palmitic ................. 17.4 17.4 17.5 17.2 19.4 19.4 -19.4 19.3
Myristic ................. 17.7 18.6 18.6 19.8 19.7 20.6 28.6 21.8
Lauric.................... 17.8 18.7 19.9 24.5 20.0 21.2 ' 23.5 27.5
.Capric.................... 18.4 20.0 23.7 28.4 21.1 22.9 27.0 31.6
Pelargonic ............. 18.6 20.8 26.2 30.5 21.2 23.4 29.1 36.8
Caprylic ................. 18.9 20.9 26.3 32.1 21.3 23.8 31.9 38.8
. 17.0% Potassium Oleate Solution 19.1 % Potaspiurn Oleate Solution
has a viscosrty of 20 C e n t ~ p o ~ s e s has a v r s c o s ~ t y of 80 C e n t i p o l s e s
PANEL DISCUSSION
MR. TERRY:If there are no more questions to be turned DR. WITTCOFF:I suspect t h a t I had better yield the floor
in, we will proceed with the question and answer period. to Mr. Ayelsworth on-this question as he seems to be a spe-
If there are any additional thoughts from the audience cialist in that area. Therefore, I will pass the buck.
please do not hesitate to raise any questions and we will MR. AYLESWORTH : There a r e a . number of other perform-
recognize you. Also, a s I mentioned earlier, I would like to ance factors that a r e influenced by variations in fatty acid
have the panel members ask each other questions if they composition in liquid soaps. That is a very interesting
so desire. subject. Some information is available in the literature and
The first question is directed to Mr. Aylesworth. I t is a s there are some references given in the printed version of the
follows: "What ratios of low molecular weight acids and talk on liquid soaps. Sudsing, foam stability, cold test, color,
vegetable acid would replace coconut relative to high viscosity and odor a r e important in potash liquid soaps and all of these
soaps?" a r e influenced by variations in fatty acid composition.
MR. AYLESWORTH: The particular fatty acid we used a s MR. TERRY:The next question is directed to Dr. McCorkle.
a standard is a low linoleic oleic acid. The maximum soap con- "Can the fatty amines be satisfactorily alkylated with for-
tent for a free-flowing soap of this acid is approximately 18 maldehyde and formic acid?"
per cent. Commercial fatty acids high in linoleic acid will go DR. MCCORKLE:The answer is "Yes", in good yields. Dur-
somewhat higher in viscosity before reaching the breaking ing the war there were some people making tertiary amines
point, and thus require a somewhat lower proportion of low by this method. It is not necessarily t h e cheapest way to
molecular weight acids to match the liquid soap viscosity riake tertiary amines, but i t can be done very satisfactorily
of coconut. a s to yields and quality.
MR. TERRY: The next question is also directed to Mr. MR. TERRY:The next question is directed to Dr. Wittcoff.
Aylesworth. "Has any work been done on use of Ricinoleic "Would you recommend a reference on color stability deter-
Acid in decreasing viscosity of oleic and potash soap?" mination?"
DR. WITTCOFF:There a r e a number of references and I
MR. AYLESWORTH: That is a very good question. We have have them in my briefcase. I cannot quote them offhand, but
done a limited amount of work on the effect of ricinoleic acid if the gentleman who asked the question will see me later, I
in liquid soap viscosity and I know of little in the literature shall be glad to give him the references.
on this subject. Generally, ricinoleic acid and oxidizied acids MR. TERRY:The next question is also directed to Dr. Witt-
will reduce liquid soap viscosity. As you know, the soaps coff. "What differences, if any, exist between vegetable
of ricinoleic acid a r e rather a special case. They do not fatty acids and animal fatty acids of like compositions? Can
suds. They are used in sudsless shampoos and products of they be substituted for each other?"
that type.
DR. W I ~ C O F FThere
: a r e marked differences but in some
MR
. TERRY:The next question is directed to Dr. Wittcoff instances, especially after appropriate processing, they can
or Mr. Aylesworth. "What other factors in liquid soap per- be interchanged. Hydrogenated vegetable acids, for example,
formance a r e influenced by variations in the fatty acids?" can frequently replace animal acids in certain applications.