previously described give a slurry that, is not of acceptable quality co!orwise, it is possible to improve the color of the dekrgent slurry by t’he applicat’ion of a bleach. Laboratory work ( 3 ) has shown that chlorine gas can be satisfactorily used as a bleach. However, this process is considerably more difficult and much more corrosive to stainless steel than is the standard hypochlorite met8hod. A recommended bleaching procedure using sodium hppochlorite is as follows: The pH of a high active slurry (50 to 55% water) is adjusted to approximately 6 or 7 by addition of a highly concentrated dodec?-lbenzenesulfonic acid. A solution of sodium hypochlorite containing approximat,e!y 15% XaOCl is slo~vlyadded, and the slurry is well agitated. Agitation of the mixture is continued for approximately 15 minutes at, a temperature of 122” t o 130” F. A nearly “paper mhit’e” slurry should be obt’ained from t’his bleaching procedure, and it should have a final pH in the range 5 to 8.5. I n this bleaching process, the amount of 100% NaOCl usually equivalent to 2 to 4 pounds of hypochlorite per 100 pounds of sulfonate. The amount of bleach used, however, will depend on process conditions and the condition (color) of the sulfonate prior to bleaching. SUMWARY
The most commonly used and most thoroughly investigated method of sulfonating detergent alkylates is the process employing various concent’rations of sulfuric acids-Le., 104.5, 100.5, and 98yc sulfuric acid. Process variables are numerous and have significant effects on t,he finished sulfonates. Probably the most widely used sulfonation process is that using 20% oleum. This process gives sulfonates of good quality, cooling requirements are not excessive, and the excess acid, if properly diluted, can he shipped in tank cars.
h number of studies made on sulfonation of detergent alkylate with sulfur trioxide indicate it to be a feasible process. ACRNOWLEDGMERT
The authors wish to acknowledge the assistance of E. L. Hatlelid, J. C. Kirk, and 51.L. Sharrah in obtaining some of the data and in editing this paper. LITERATURE CITED
(1) Birch,
S. F., and associates (to Anglo-Iranian Oil Co.). Brit.
Patent 680,613 (Oct. 8, 1952). ( 2 ) Brandt, R. L. (to Colgate-Palmolive-Peet C o . ) , U.
S. Patent 2,244,512 (June 3. 1941). (3) Continental Oil Co., Houston, Tex., “Xeolene 400, Intermediate for Synthetic Detergents.” (4) Furness, R.. and Scott, A. D. (to Lever Brothers and Ijnilever, Ltd.), S.African Patent 9307 (June 19, 1950). ( 5 ) Gerhart, K. R.. and Popovac, D. O., J . Am. Oi2 Chemists’ Soe., 31, 200-3 (1954). ( 6 ) Gilbert, E. E., and associates, ISD. Esc,. CHIXI., 45, 2065-72 (1953). (7) Hoyt, L. F., U. S.Dept. of Commerce, O T 3 Report, PB 3868, Hobart Publishing Co., Washington, D. C. (8) Lemmon, N. E. (to Standard Oil Co. of Indiana), 5. S.Patent 2,448,184 (Aug. 31, 1948). (9) Mack, D. E., Chem. Eng., 58, No. 3, 9, 109-10 (1951). (10) Oronite Chemical Co., Alkane Tech. Bull., p. 9, 1950. (11) Sharrah, BI. L., and Feighner. G. C., IXD,EXG.CHEM.,46, 24854 (1954). (12) Snell, F. D., Chem. Eng. A-ews, 29, 3G-7 (1951). (13) I h i d . , 30, 30-1 (1952). (14) Ihid., 31, 38-40 (1953). (15) Ihid., 32, 36-7 (1954). (16) Snell, F. D., Allen, L. H., Sandler, R. A , , Third World Petroleum Congress Proc., 1951, See. V, pp. 109-18. (17) Snell, F. D., and Kimball, C. S.,Soap Sanii. Chemicals, 27, 27-9 (1951). RECEIVED for review March 2 5 , 1951.
ACCEPTEDJuly 10, 1954.
Nonionic Detergents Central Research Laboratory, General Aniline & F i l m Corp., Easton, Pa.
T h e increased consumption of nonionic surfactants is due to their use in detergent formulations. The nonionics most used in detergent €orrnulations are the ethylene oxide products of alkylphenols, the ethylene oxide products of tall oil, and the alkanolamide derivatives of fatty acids. Although unbuilt polyoxyethylated detergents are superior in cotton detergency and redeposition prevention to unbuilt anionics, the latter can be built to give detergent formulations equal i n effectiveness to the built nonionics. The built nonionic detergents are obtaining an increasingly large proportion of household laundry market, because low foaming detergents are needed in automatic rotary-drum wrashing machines. Industrial detergent uses of the nonionics include antistatic action, raw wool scouring in textile operations, germicidal cleaning in restaurants, removing wTater-soluble soils i n dry cleaning operations, metal cleaning, and washing of floors and walls. Desirable improvements of nonionics include the development of a nonionic detergent formulation of higher foam stability, and the development of a solid nonionic possessing more efficient surface active properties.
T
H E nonionic surfactants, as a class, have been relative newcomers to the American scene. Those which are used as detergents were first manufactured on a large scale basis in the early 1940’s in this country. The use of nonionics has grown considerably in the past decade, and the production of all typcs of
1930
nonionic surfactants is now estimated to he around 90,000,000 pounds per year. Since nonionics are extremely versatile surfactants, they are used for many different purposes such as detergency, wetting, emulsification, and lime soap dispersion, but the major fraction of the nonionic production goes into detergent
INDUSTRIAL A N D ENGINEERING CHEMISTRY
Vol. 46,No. 9
-Synthetic TABLE I. PREPARATION OF N o s r o ~ r cSURFACTANTS FROM ETHYLENE OXIDE Hydrophobic Portion
R-OH
Product
t
n
+
n
CH1-CHz
+R , ~ > ( O C H ~ C H ~ ) , ~ ~ H
CHr-CHz \O/
--+
!I +R-C-(OCHZCHZ)~OR
\o/
R-(OCHzCHz).'OH
0
0 'I R-C-OH
+n
CHz-CHz \ / 0
R-SH
+n
CHr-CHz \ / ---f R--S(CHZCHZO)~H 0
0
I1
R-C-XHz R-KHz
A
n
CHr-CRz \O/
/I
(CHzCHz0)aH \(cH*cH~o)~H'
CH2-CHa
+ n
0 +RC-N/
zC Hz0) a H (CHzCHz0)bH
where n +:b
, wlipre
a
=
ib = n
11
Detergents-
The alkanolamide derivatives of fatty acids are also used widely in detergent formulations. The tv-o chief general types of this class are shown in Table 111. The product obtained bv reaction of fattv acid with one mole of alkanolamine is water insoluble, while that obtained by reaction with two moles of amine is water soluble. The structure of this latter type has not been established and may not be truly nonionic. However, it is included in this discussion, since it is often referred to as a nonionic surfactant. These amides have been of particular interest in detergent formulations for their foamboosting properties. The fatty acid esters of polyhydric alcohols are another general chemical tvDe of nonionic surfactant, but thev are - * used mainly for emulsification.
HOUSEHOLD DETERGENTS applications. Only the uses of nonionics in detergency formulations arc considered in this discussion. It has been known for a long time that even unbuilt nonionic Because it is simple to vary their constitution and thus tailordetergents derived from ethylene oxide are quite effective cotton make nonionics for specific uses, there are undoubtedly more detergents. Using a wash test on cotton swatches soiled with a variations of nonionics manufactured than of the anionics or synthetic soil similar to floor sweepings, Sanders and Lambert ( 1 4 ) cationics. This paper indicates briefly the scope of these chemihave shown that an unbuilt alkylphenol-derived nonionic is an cal possibilities, shows the ones that are most important in dcterappreciably better detergent than an unbuilt alkyl aryl sulfonate. gency, disciisses their major usages in detergency, and considers Similar favorable results have been obtained with tall oil nontheir probable future. ionics. In 1982 ( 1 6 ) about 60,000,000 pounds of nonionics were preOf great importance in detergency is the ability of a material to pared by the reaction of ethylene oxide under alkaline catalysis prevent the redeposition of soil to cloth after it has been removed. with a hydrophobic material containing a reactive hydrogen as Redeposition tests have been conducted using the same synthetic ehoan in Table I. soil in a Terg-0-Tomcter containing clean white cotton broadThe reaction products of amines with ethylene oxide are cloth and Indian Head cotton swatches. The reflectance of the cationic products, but. they are included in this table because of swatches dried after the run is a good indication of the whiteness their structural similarity to the other ethylene oxide products. retention or the ability of a product to prevent redeposition of Foil Since there are many long-chain phenols, acids, mercaptans, on the cloth. The results obtained with unbuilt nonionics and and alcohols available, and it is easy to vary the mole ratio of anionics are shown in Table IV. ethylene oxide to hydrophobic material, it is possible t o prepare The concentration of soil is much greater in this test than is an almost infinite number of polyoxyethylated nonionic surfacusually encountered in actual practice, because the test was detants. For detergent purposes, however, the products from alkylsigned to determine the soil suspending powers of surfactants phenols and from tall oil have attained the most importance under extremely severe conditions. The two nonionics are much (Table 11). better than the typical anionics tested. The best anionic in this In the case of alkylphenols, either mono- or dialkylphenols test was a sulfate of alkylphenol-ethylene oxide products. Evihave been employed, and the best alkylphenols for detergents dently, the combined oxyethylene groups possess definite soil have contained 8 to 10 carbon atoms in the alkyl groups. Products based on tall oil, which is a mixture of resin acids and CI6to suspending powers. C18 fatty acids, have also attained Fidespread usage. The et%j;ene oxide-derived surfactants TABLE 11. MA7OR POLYOXYETHYLATED DETERGEKTS are not single compounds, but are a mixture of closely related products in which Hydrophobic Reactant the mole ratio of combined ethylene oxide R ( C s t o clo)O =-,H + s t o 12 C HA\' Z - c i i z --f R \-/ /==):ocH~cH~)~-~~oH to hydrophobe differs over a fairly wide range. Mayhew and Hyatt ( 1 1 ) have " 0 0 shown by molecular distillation studies I/ I1 R-C-OH + 1.5 to 18 C H y C H z --+R-C-(OCHSCH~)I~-~BOH that the distribution of molecules of varying mole ratio in polyoxyethylated sur\O/ factants is represented by Poisson's disR = Tall Oil tribution formula. Therefore, the mole ratio of combined ethylene oxide to the base material is an average figure. Since TABLE 111. GENERAL TYPESOF ALKANOLAMIDEDERIVATIVES these ethylene oxide derived detergents 0 0 /I I/ are always mixtures, they tend to be R-C-OH + H ~ N C H Z C H Z O+ H R-C-NHCH~CHZOH + Hz0 liquids. By reaction with enough moles 0 0 of ethylene oxide, solids can be produced, 1I I1 R-C-OH + 2HN(CHzCHzOH)z e R-C-N(CH&HzOH)z . HN(CHaCHz0H)z HzO but even these are usually waxy, low melting materials.
+
September 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY
1931
TABLE Ikr.
WHITEXESS R E T E S T I O S O r U N B U I L T SURFL4CTANTS Conditions of test: 2.5 grains soil/liter 140' P. Four B X 6 inch Indian Head swatches Four 4-inch diameter broadcloth swatches Final Final Reflectance Reflectance, Broadcloth; Indian Headb Detergent, 0.05% Alkylphenol nonionic 73.1 64.1 Tall oil nonionic 72.4 64.7 Sulfate of alkyl phenox3,polyoxyptliylen~ethanol 64 2 64.1 hr-1lethy1-N-oleoyl taurate 85.7 60.2 Lauryl sulfate 58.2 53 4 Alkylbenzenesulfonate 12.4 36.7 55.4 52.5 None Initial reflectance 86.5. 5 Initial reflectance 82.5. Q
Even though the unbuilt nonionic re hetter detergents and soil suspending agents t'han alkyl aryl sulfonates, t,hey are not good enough by themselves, and must be built. As Sanders and Lambert reported ( I C ) , the alkyl aryl sulfonates are improved more by the incorporation of complex phosphates and sodium carboxymethylcellulose than are the nonionics. I n act'ual practice, equally effective formulations can be produced from t'he better nonionic or anionic deiergeiit,s by proper building with thc complex phosphates, sodium metnsilicnte, and sodium carboxymethyl cellulose. The anionic formulations have captured much of the household market because of their greater foam st,ability as compared to the nonionics. The housewife, in the presynthetic detergent daj,s, used foam as an indicator to tell her when she had added enough soap to the wash water to overcome lhe water hardness and t o provide enough extra for washing the clothes. Rather than spend the money necessary t o convince the houscwifc that high suds are not necessary for clothes-washing detergency, the major soap companies have developed high sudsing detergent formulations. The anionic detergents, such as the lauryl sulfates and dodecj-lhenxenesulfonates, not only produre higher foam t,han the nonionics, but also lend themselves hetter to foam boosting and stahilization. The proper proportion of derivatives s1ion.n in Table 111 will increase the foam stability of thcse anionim against, the defoaming action of mechanical agitation and soil. -4s s h o m by Sanders and Knaggs ( I S ) the best result's are obtained with approximately equal amounts of anionic and allranolamide derivatives. It is impossible t o know the total amount of alkanolamides used for this purpose, but it is certainly measured in tens of millions of pounds per year. The low foaming action of nonionics which is a drawback for use in agitator-type machines has proved beneficial in the automatic rotary-drum machines, where use of t,he ordinary high foaming detergents may cause an overflow of foam out of the machine. Escessive foam may also interfere with the proper mechanicrrl agitation with resultant loss in cleaning efficiency. One of the products t,hat has obtained widespread acceptancc as a "cont,rolled-sudsing" detergrnt is based on a polyoxyethylated tall oil that has been forinulated with complex phosphati,s, metasilicates, and carboxymethylcellulose (CMC) ( 7 , 9). Similar products have been made from the alkylphenol-derived nonionics (31,but so far they have not attained the commercial importance of the tall oil-derived products. Since both of the above nonionic types are liquid, some dificiilty was originally encountered in preparing free-flowing p o a ders from them. Because of their high detergent and white retention efficiency, however, t,he detergent formulations require only 10 to 15% of the nonionic itself, and the other ingredients such as complex phosphat,es and CMC sorb the nonionic well enough t o prepare powdered products. Until very recently, the commercially built nonionic detergent products have been high density products and have met with some sales resistance for this reason. It is pofisible to prepare low density nonionic products
1932
however, and the introduction of these should increase the sale of built nonionic formulations. Two other materials xhich have been used for absorbing the liquid nonionics are fluffed borax ( 1 2 ) and urea ( 1 ) . Thrso formulations have been used particularly in the manufact,ure of the mobile laundry detergent for the Quartermaster Corps which must be effective for laundering in soft, hard, or sea water. T t has been necessary to find the proper sorbing agents and drying equipment for the nonionic detergcnts that are liquid. For some time a need existed for a solid nonionic that could be dr5- mixed with other ingredients in any type of equipment. Recently, Vaughn, Jackson, and Lundstcd ( 17 ) reported that polypropylene glycols wit,h molecular weights above approximately 900 functioned as hydrophobic, materials, and that a solid nonionic could be made from such a mat'erial by reaction with ethylene oxide. The general formula of this solid nonionic is
CH3
I
HL-OCH,. CII,-)c-(-O-CH-CH?
-)~---(--OCH2CI12)aOII
This product does not exhibit a really high degree of wetting and surface tension 10s-ering, but satiskwtory low foaming detergent' formulations can be huilt with it ( 1 8 ) . It is still too early to determine the impact of this product in t,he field of detergency, but its solid form and Ion- foam has made it of interest for consideration in low foaming formulations. Another household application for detergents is that of a neutral product for washing dishes and fine fabrics. The most interesting development in this field since Korld K a r 11 has been the introduction of liquid products, The original detergent used for a liquid light-duty detergent was a nonionic derived from an alkylphenol, but thie has been supplemented hy higher foaming anionic formulations, I n recent years, antistatic action of fine fabrics detergents has at,tained importance because of the static encountered with clothing made from the hydrophobic fibers. One approach to the alleviation of this static problem is t,he use of an antistatic fine fabrics detergent t,hat can also be employed in the final rinse by the housewife. Studies were carried out in this laboratory, in nhich swatches of various fibers were rinsed in solutions of a polyosyethylated nonylphenol, dried, and examined for tendency t o generate static electricity in an apparatus that is a modification of that, described by Lehmiclte ( 1 0 ) .
TABLE v.
hSTIGT4TIC *4CTION O F
SOSYLPHENOL
0
WITH
10 M O L E S
REACTION k'RODUCT OF OF ETHYLENE OXIDE
Charge Developed (Units of 2.7 X 10-10 Coulombs') Rinsed, 1$& Solution Rinsed, 0.25% Solution of Agent of Agent NO 1-wk. 9-ivk. 1-wk, 4-wk Fabric Agent storage storage storage storage Dacron 500 12 15 18 30 500 24 30 a4 100 Orlon 400 15 70 72 150 h-iylon Acetate 600 18 90 BO 120 27 30 48 130 Dyne1 5.50 Xcrilan 500 45 30 80 l8 48 90 195 x-51 650 48 Ileterinined at 405% relative humidity, 80° F.
The results obtained in Table VI show that the use of 0.1 to of this nonionic detergent in the final rinse would alleviate many of the static problems encountered with a wide variety of fabrics by the consumer (8). Since Il-orld K a r 11, mechanical dishwashing machines have become a common household appliance. A very low-foaming formulation must be used because of the violent agitation in these machines. There are two general classes of detergent dishwa-hing machine formulations: Those that are essentially polyphosphate-alkali mixtures and those that are built synthetic deter-
O.%%
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 46, No. 9
-Synthetic gents. The polyphosphate-alkali mixtures often contain a very small amount of a low foaming nonionic to promote uniform drainage of the water. I n regard to the synthetic detergent mixtures, the regular heavy-duty detergent formulations based on the tall oil or alkylphenol-based nonionics are used for mechanical dishwashing, but these foam a little too much for optimum results. I n addition, as Sanders and Peager (16)have reported, certain nonionic-phosphate combinations permit film formation on the glassware more than similar combinations based on a low foaming anionic taurate detergent. INDUSTRIAL DETERGENTS
Thus far, household detergent products have been discussed, because they represent the greatest portion of the market for detergent uses. However, there are many industrial uses for detergents. The textile industry, for example, was probably the first large scale consumer of synthetic detergents and today uses them in many of its operations. Some of the important general characteristics that have led to the widespread usage of nonionics in the textile industry are: 1. 2. 3. 4. 5. 6.
High detergency and whiteness retention Liquid form Lack of substantivitg High wetting, emulsification, and lime soap dispersion Stability Compatibility
I n some of the textile operations, the high detergent and whiteness retention powers of the unbuilt nonionics are important, since the common built formulations cannot always be used bemuse of pH limitations and compatibility problems. The nonionic detergents shown in Table I1 are usually liquid in their 100% active form, and are therefore advantageous in many textile operations because rapid rate of solution is required in the modern high speed textile scouring operations and in addition many mills prefer a nondusting product. The nonionics, because of their lack of strongly sorptive groups, have less substantivity to most fibers than the cationics or anionics, and thus rinse faster. This makes their use advantageous in high speed textile processing steps. I n contrast to the soil enrountered in laundering, which probably contains only about 10% of oils, the soil to be removed in textile processing very often contains a high percentage of naturally occurring fats and waxes, or of oily material added during processing. Thus, the emulsifying properties of a detergent are of greater importance in textile processing than in laundering. Likewise, the detergent sometimes must function as a limesoap dispersant because of the formation of fatty acids by saponification of the naturally occurring fats. I n addition, it must very often be a fast wetting agent. The nonionics derived from alkylphenols, in particular, are efficient in all of the above surface active performance characteristics. The ethylene oxide product of lert-dodecyl niercaptan also is a highly effective all-round surfactant, but suffers from its instability to the oxidizing conditions, and tendency to form odors in the acid conditions that may be encountered. Finally, the nonionics are of particular use in cases where cationic dyestuffs or finishing agents must be removed, since they ai e compatible with cationic materials, whereas the anionics form insoluble precipitates
R-SO,-Na+
+ R?N+Cl-+ R-SOaNRa
J
+ Na+ + C1-
.4 few specific detergency uscs for thr nonionics in the textile industry are: 1. Raw wool scouring, where the dirt, sand, suint, and grease are removed from the shorn wool. Both anionics and nonionics are employed for this use. The nonionics have one advantage in
September 1954
Detergents-
that they are much less substantive to the wool and therefore do not require as frequent replenishment. 2. Scouring naturally occurring fats and waxes, mineral oil, sizing agents, dirt before dyeing. 3. Scouring loose colors and print gums after dyeing. There are many other industrial detergent applications for nonionic surfactants. Because of their compatibility with cationic materials, nonionics are used with quaternary germicides in restaurants, dairieq, and other places where control of germs is of especial importaucca. In such formulations, the nonionic functions as a detergent, while the quaternary functions as a sanitizer. Surfactants are used in the dry cleaning industry to emulsify water in the dry cleaning solvent, aid the water in the removal of watei-soluble soil, and suspend insoluble materiale. The anionic petroleum sulfonates are probably the most widely used surfactant type for this application, but nonionics have also been used. According to Barker and Ranauto (2) a blend of a predominantly hydrophilic and a predominantly hydrophobic noriionic surfactant is often used to combine the detergency properties of the former with the ability to form water-in-oil emulsions of the latter. Heavy-duty hard surface detergents that are used for washing floors and walls usually contain alkaline inorganic materials a s well as a surfactant, Both the alkyl arylsulfonates and nonionics are used in such formulations. Extended laboratory woilc has shown (6, 6) that the alkylphenol-derived nonionics ale superior to the anionics for cleaning soil from a wide variety of substrates. Nevertheless, the sulfonate has been employed to n greater extent because of its lower cost and greater ease of formulation in a solid product. Recently, there has been some interest in a liquid type product containing a nonionic because of absencr of caking and troublesome dusting, and higher speed of solution. The various needs for metal cleaners are manifold, depentling on the metal to be cleaned, type of soil to be removed, cleanliness required, and subsequent handling of the metal. The nonionics and anionics are used in metal cleaning, and the choice of material to be used for a specific purpose must be based on the relative efficiencies of the detergent formulations under the particular conditions to be met. One example where the nonionics are preferable to anionics is as an assistant in pickling, where the oxide scale is removed from ferrous metals by treatment in a dilute acid bath. These baths usually contain a cationic corrosion inhibitor. The acid-stable alkylphenol-ethylene oxide products aid in the penetration of the scaIe by the acid, disperse acid-insoluble materials, and in some cases increase the effectiveness of the cationic inhibitors. Anionics cannot be used in this system, because they would precipitate the cationic inhibitor. Another case where the nonionics have been found advantageous is in cIeaning under conditions of high agitation, such as spray cleaning, where high foaming is deleterious to the cleaning action. FUTURE O F NONIORIC DETERGENTS
Some important improvements remain to be achieved in the nonionic field. Two worthy of mention are the development of a nonionic detergent formulation of higher foam stability, and the devrlopment of a solid nonionic possessing more efficient surfactant properties such as wetting. The formulation of a high foaming nonionic detergent is one of the classic problems in the surfactant field, and many companies have been unsuccessful in finding a satisfactory foam stabilizer for the nonionics. This problem, however, will probably be solved as additional information is obtained on foam formation and stabilization. Finding a solid nonionic with high surface active properties will probably also be difficult. Thus far, the solid nonionics have been materials of comparatively high molecular weight. As Cross ( 4 ) has indicated, nonionic products possessing good all-
INDUSTRIAL AND ENGINEERING CHEMISTRY
1933
round surface active properties have had a fairiy critical hydrophobic niolccular weight and a fairly definite hydrophobic-hydrophilic balance. The present solid nonionics possess too high a molecular n-eight and do not have the proper hydrophobic-hydrophilic balance. The development of a highly surface active solid nonionic may very n d l require a different approach from using a hydrophobic base of high molecular weight. As for future marli-et developments, the alkylbenzenesulfonates are versatile products also and because of their lower cost they have in many inst,ances been used instead of the ethylene oxide products. However, the alkylbenzenesulfonates are mass production chemicals. As t,he ethylene oxide-derived nonionics attain larger volume production, their prices should fali in relation to the sulfonates. If t'hese scientific goals for the nonionics can be reached, their use in the next decade will increase to a marked extent. RCKNOWLEDGIIEYT
The a,uthors n-ish to thank J. 11. Cloney, G. 11. Gantz, and C. E. Stevens of the Antara Chemicals Division, General *hiline & Film Corp., for their helpful suggcslions i n t,he prepamtion of this paper. LITER-iTURE CITED
(1) Barker, G. E. (to the Atlas Powder Co.), U. S.Patent 2,559,583 (July 10, 1951). ( 2 ) Barker. G . E., and Ranauto, H. J., Snal:, Sunit. Chemicals, 27, 1-0. G , 43 (1951).
ui
(3) Black, E. J. (to General Aniline & Film Corp.), U. S. Patent 2,555,285 (May 29, 1951). (4) Cross, J. N., Proc. Chem. Speciulties M f r s . Assoc., pp. 135-Y9 143 (June 1950). ( 5 ) Fineman, 11.N., Soup, Sunit. Cheniicals, 29, No. 2, 46 (1953). (8) Zbid., No. 3 , p. 50. (7) Harris, J. C., and Kosmin, AI, (to Monsanto Chemical C o . ) , U. S.Patent 2,594,431 (dpril 29, 1952). (8) Jelinek, C. F., and Nayhew, R. L., Testile Research J., 24, 765 (1954). (9) Kosinin, M., and Harris, J. C. (to Nonsanto Chemical Co.). U. 8. Patent 2,594,453 (hpril 29, 1952). (10) Lehmicke, D . J., Am. Dyestu$ Rcptr., 38, 863 (1949). (11) Ilayhew, R . L., and Hyatt, R. C., ,I. Am. Oil Chemists' Suc., 23, 357 (1952). (12) Sanders, H. L. (to General Bniline 8: Film Corp.), E.S.Patcnt 2,623,856 (December 30, 1952). (13) Sanders, H.L., and Knagg., A. E., Soap, Sanit. Chemicals, 29, S o . 8. 45 (1953). (14) Sanders, H . L., and Lambert, J. M., Teztile Research .I., 21, 680 (1951). (15) Sanders, 1%.L., and Yeager, J. A , , IND.EXG.CHEX, 43, 8GO (1951). (16) U. S.Tariff Commission, Wazhington 25. D . C., Rept. Synthetic Organic Chemicals, 1952. (17) T-aughn, T. H . , Jackson, D. R., and Lundsted, L. G., J . Am. 8 1 7 2 . Oil C h ~ i i s t s S' O C . , 29, 240 (1952). (16) Vaughn, T. €I., Suter. El. R.,Lundsted, L. G., and Kramer, AI. F.,Ibid., 28, 294 (1931). RECEIVE for; ~review ?.larch 2.5 1 0 , i l .
1954.
e TFHOtL4hS H. j-.4UGHNi, H. R. SUTER, 4s'~ 31. G. IBRAtIEK f 7 y a n d o t t e C h e m i c a l s C a r p . , Wyandotte, Mich.
A
wide variety o f inorganic and organic builders i s used to give detergents specific attributes required for specialized uses and to improve their performance properties. Builders are an important outlet for chemical production. The function of builders in altering the chemical and physical properties of synthetic detergents and the specific effect of such alterations in the laundering of cotton, as measured by laboratory test methods, is discussed in this paper' A classification of builders, with designation of principal uses, is presented. NORGA4KICbuilders have been associated n-ith the use of eurface active agents since their earliest inception. In some instances thie came about coincidentally-for example, via neutralization of excess sulfuric acid used in sulfonation. I n fact, the use of a syndet without' builders is uncommon, except in certain nonionic detergents used in the textile indust'ry and in synthetic emulsifiers. Generally, 1007Gactive organic syndet's are unsuitable in one way or another for most' uses. The difficulties may lie eit,her in physical form, performance properties, or economy. I n t,he case of many of the early synthetic detergents, sodiuni sulfate served to overcome these shortcomings. Today a variety of inorganic and organic builders is used to provide the specific attributes required for specialized uses and, generally, performance properties of the detergents are greatly improved. Builders are materials that are added to improve the utility of a detergent. The syndete considered in this paper are members of t'he broad classifications of anionic and nonionic detergents. Although certain cationic detergents such as higher fatty amines 1
Present address, Colgate-Palmolive Co., Jersey City 2, X. J.
1934
are known to possess detergent propel ties, this class is technologically relatively unimportant in the cleaning industr) a t present. I n addition, builders have assumed substantial economic importance and they represent a major outkt for a variety of chemical pioducts. The consumption of builders in household synthetic detergent products may be estimated roughly by referener to the rcpoits of the Association of American Soap and Glycerin Producers, Inc., in which I952 sales of built jyndets are ieported to be 1,530,000,000 pounds. By assuming an average active agent content of 25%, the consumption of builders is estimated a t 1,147,500,000 pounds. Estimates published by SnelI (11) in January of 1953 indicate the sales of syndets in 1853 increaeed over 1952 by about 24YG. This brings consumption of builder^ to close to 1,500,000 pounds in 1953. I n addition, large quantities of inorganic builders are used in products for industrial use, and proprietary builders are sold in large voIume for commercia1 laundering in conjunction Kith either soap or synthetic detergents. Together with the builders used in soap products for household uee, sales of which are approximately equal to those of syndets, it is probable that the total production of builders for
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 46, No. 9
