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1.
Billions of Dollars
Household Detergents
Commercial Soaps and Detergents
Household Soaps
Year
Figure 24.1 U.S. shipments of soaps and detergents. (Source: Annual Survey of
Manufactures)
Substrate
Figure 24.2 "Solubilizing" effect of surface active agents, (a) Greasy dirt comes into
contact with surfactant solution, (b) Hydrophobic ends of surfactant molecules dissolve
in the grease, (c) The surfactant affects the contact angle 0 between the dirt and the
substrate. If 0< 90, total removal of the grease is impossible, (d) Further agitation
displaces the greasy dirt as macroscopic particles. These form an emulsion if agitation is
sufficient. The particles form the center of micelle-like structures. Removal of grease is
seldom complete (0 < 90 as in the diagrams on the right rather than the simple
"rollback" mechanism on the left). Usually the main body of grease is removed from a
strongly adsorbed monomolecular or duplex layer of grease. Agitation is an essential part
of the process. (Source: Wittcoff and Reuben, Industrial Organic Chemicals in
Perspective. Part Two: Technology, Formulation, and Use, John Wiley & Sons, 1980.
Reprinted by permission of John Wiley & Sons, Inc.)
Type
Anionics
Linear alcohol sulfates (AS)
Linear alcohol ethoxysulfates (AES)
Linear alkylbenzenesulfonates (LAS)
Nonionics
Nonylphenol ethoxylates (NPE)
Alcohol ethoxylates (AE or AEO)
Other nonionics
Total
Source: Chemical Economics Handbook
Production
(Million Ib)
57
890
661
2%
25
19
462
1,200
244
3,514
13
34
7
100%
2.
CATIONIC SURFACTANTS
and many are quaternary nitrogen compounds such as tallow fatty acid
trimethylammonium chloride. In the more general structure R1R2R3R4N+X",
R1 is a long alkyl chain, the other R's may be alkyl or hydrogen, and X" is
halogen or sulfate.
fat or triglyceride
glycerol
(glycerin)
fatty acid
The fatty acid is then converted into the "quat" by the following sequence
of reactions.
fatty acid
amide
nitrile
primary amine
"quat"
Cationic surfactants are not very good for cleaning because most surfaces
carry a negative charge and the cationic portion adsorbs on the surface
instead of dissolving the grease. But they do have other important surfactant
applications. They inhibit the growth of bacteria, are corrosion inhibitors,
are used in ore flotation processes (separating phosphate ore from silica and
potassium chloride from sodium chloride), and are good fabric softeners and
antistatic agents. They also find use in hair conditioners and other personal
care applications.
3.
ANIONIC SURFACTANTS
This is by far the most important type of surfactant and will be discussed
under separate subtypes. In anionics the long hydrophobic alkyl chain is in
the anionic part of the molecule. The organic part is negative.
3.1
Soaps
The first type of cleansing agent, used by humankind for centuries, was
soap. Although it has now been supplemented by various synthetic
detergents in advanced countries for laundry and household use, it is still
preferred for personal hygiene. In less-developed countries it is preferred for
laundry use.
O
fats
Na H
glycerol + R-C-Q-Na+
A
Soaps are the sodium or potassium salts of certain fatty acids obtained
from the hydrolysis of triglycerides. The potassium salts form the "soft
soaps" that have become popular recently. The fats used in soap
manufacture come from diverse natural sources. Animal tallows and
coconut oil are the favored sources of the triglycerides, and quite often
mixtures from different sources are used to vary hardness, water solubility,
and cleansing action of the final product. Palm, olive, cottonseed, castor,
and tall oil are other sources. The side chains are usually Cn-Ci8 in length.
Manufacturing processes are both batch and continuous. Sometimes the
triglyceride is steam-hydrolyzed to the fatty acid without strong caustic and
then in a separate step it is converted into the sodium salt. Either way gives
a similar result. Soaps have some disadvantages compared to synthetic
detergents: they are more expensive, they compete with food uses for fats
and oils, and their calcium and magnesium salts formed in hard water are
Billions of Pounds
Synthetic Detergents
Soaps
Year
Figure 24.3 U.S. consumption of soaps vs. total synthetic detergents.
Chemical Economics Handbook)
(Source:
very insoluble and precipitate onto the clothing being washed. They also
tend to clog automatic washers. They deteriorate on storage and are unstable
in acid solutions. This is why in 1940 only 1% of cleaning agents were
detergents; in 1970 they were 85%. Fig. 24.3 shows this historical
replacement of soaps by detergents from 1940-1970. However, there will
always be that small market for soaps, presently still a significant
percentage. Advantages of soaps include greater biodegradability and less
toxicity.
3.2
3.3
or triethanolamine
The linear alcohols can be made from other long-chain linear materials,
but a new process with a triethylaluminum catalyst allows their formation
directly from ethylene and oxygen.
3.4
They have high foam for shampoos and are "kind to the skin." They are
also used in light duty products such as dishwashing detergents. It is the
least sensitive of the anionics to water hardness and therefore has benefited
in the trend away from phosphates. They have 25% of the production for the
major household surfactant market.
3.5
Originally the cheap tetramer of propylene was used as the source of the
alkyl group in alkylbenzenesulfonates. This tetramer is not a single
compound but a mixture. However, they are all highly branched. For
example:
nonlinear C 12^4
This nonlinear alkylbenzenesulfonate formed the basis for the heavy duty
household washing powders of the 1950s and early 1960s with excellent
cleaning ability. But rivers and lakes soon began foaming since enzymes
present in bacteria could not degrade these "hard" detergents because of the
highly branched side chain. They were banned in 1965.
Thus /7-alkanes (Ci0-Ci4) separated from the kerosene fraction of
petroleum (by urea complexation or absorption with molecular sieves) are
now used as one source of the alkyl group. Chlorination takes place
anywhere along the chain at any secondary carbon. Friedel-Crafts alkylation
followed by sulfonation and caustic treatment gives a more linear
alkylbenzenesulfonate (LAS) which is "soft" or biodegradable. The
chlorination process is now the source of about 40% of the alkyl group used
for the manufacture of LAS detergent.
linear C\2^26
C10-C14; 2, 3, 4, 5, 6-isomers; o +p
The other 60% of the alkyl groups for LAS detergents are made through
linear a-olefins. w-Alkanes can be dehydrogenated to a-olefins, which then
can undergo a Friedel-Crafts reaction with benzene as described above for
the nonlinear olefins. Sulfonation and basification gives the LAS detergent.
LAS detergents made from the chlorination route have lower amounts of
2-phenyl product. Use of the a-olefins gives greater 2-phenyl content,
which in turn changes the surfactant action somewhat. LAS detergents for
many years had the highest percentage of the market, but now they own 19%
of production for the major household surfactant market.
4.
NONIONICS
4.1
4.2
linear
5.
AMPHOTERICS
the pH. They are derivatives of amino acids and may have one of two
general formulas, where R is linear Ci2-Ci8. Amphoterics are used in
shampoos. Near pH = 7 they are less irritating and "milder." They can be
used with alkalies for greasy surfaces as well as in acids for rusty surfaces.
6.
DETERGENT BUILDERS
trisodium nitrilotriacetate
sodium poly-a-hydroxyacrylate
sodium aluminosilicate
(zeolite)
sodium silicate
sodium carbonate
sodium citrate
sodium sulfate
benzene polycarboxylates
the states have banned their use. Currently nearly all laundry detergents do
not use phosphates. Phosphate use in laundry detergents declined from 2
billion Ib in 1970 to almost zero in 1995. Figure 24.4 lists some of the
compounds tried as phosphate substitutes.
Ethylenediaminetetracetic acid (EDTA) is a good sequestering agent but
its cost is excessive. Nitrilotriacetate is effective but has been suggested to
be teratogenic and carcinogenic so it is not used in the U.S. Sodium citrate
is harmless but does not work well. Benzene polycarboxylates are expensive
and are not biodegradable. Sodium carbonate is successful except in hard
water areas. Commercial use of zeolites and poly-a-hydroxyacrylate has
begun. Sodium sulfate occurs as a by-product of any sulfate or sulfonate
detergent, but has limited use as a builder, as does sodium silicate.
Phosphates have been replaced largely with zeolites and sodium carbonate,
with the aid of newer antideposition aids like acrylic polymers. Only about
50% of phosphate came from detergents, with 33% from household wastes
and 17% from fertilizer runoff contributing to eutrophication, so we must be
watchful of pollution from other sources. The search for phosphate
substitutes will probably continue.
Suggested Readings
Chemical and Engineering News, an annual product report entitled "Soaps
and Detergents," usually published in a January issue.
Kent, Riegel's Handbook of Industrial Chemistry, pp. 1012-1049.
Wittcoff and Reuben, Industrial Organic Chemicals in Perspective. Part
Two: Technology, Formulation, and Use, pp. 182-212.