€&EN ANNUAL
REVIEW—1950
of oxidized cotton, photochemical degradation and differential dyeing tests. Research activity on rayon also continued at a high rate and numerous p u b lications on the preparation and properties of regenerated celluloses and its derivatives appeared during t h e year. Investigations continued on the nature of oxidation of alkali-cellulose, t h e fine structure of various types of rayon, mechanism of absorption of dyes and other chemicals, t h e relationship of chemical structure of mechanical properties, and the synthesis of m a n y derivatives. Methods are described for producing hollow rayon filaments by extruding viscose containing a gas-developing substance, crinkled filaments by regeneration under low tension, cross-linkages with trimethylolphenol, stable rayon fabrics by treatment with caustic solutions, and for protection against biological attack with alkali-metal salts of phenyl-salicylie acid. or derivatives of dihydroxybenzophenone. Processing, Dyeing, and Finishing N e w and novel approaches are replacing m a n y of the old, empirical methods of studying textiles and textile processing. Use is being m a d e of radioactive tracers in studying t h e mechanism of dyeing or to check changes in yarn blends, retention of alkali, oils, detergents and other materials. Exploratory experiments have been made on the use of ultrasonics for scouring, dyeing, fulling, and homogenizing sizes and dyes. Synthetic detergents continue to make inroads in the industry although solvent scouring of wool is attracting attention, especially in areas with stringent stream pollution laws. Another field of work that is somewhat catalyzed b y state laws is t h a t of flameproofing. Twenty-one chemicals used by dry cleaners have been tested by the National Institute of Cleaning a n d Dyeing and found to be effective.
New formulations with titanium compounds and a method involving phosphorylation with phosphorous oxychloride in pyridine show promise. Fluorescent dyes a r e achieving some popularity in sweaters, socks, shirts, etc., and interest is also rising in t h e so-called "optical bleaches." T h e dyeing of many of the new synthetic fibers continues to be a major problem with real progress being made. Dyeing of Dynel is enhanced by using p-phenyl phenol as a swelling agent. High temperatures continue to be studied in Orion dyeing, and similar a p proaches have been investigated for Fiber V using mixtures of acetate dyes and vat color pigments. In t h e wool industry, metallized dyes, Icueoesters of vat dyes, and Helindon vat dyes are finding increased use because of their ability to improve penetration, coverage, fastness to light, fulling, a n d peroxide bleaching. A process involving impregnating cotton, viscose, or linen cloth with d y e liquor and then passing it through a molten metal bath has been described. T h e metal used is an alloy of bismuth, cadmium, tin, and lead. T h e addition of a small amount of a water-soluble salt of a polymeric acrylic or methacrylic acid to a dye is said to inhibit migration of d y e particles during dyeing and also serve to level t h e dyes. Resistance to gas-fading of cellulose acetate is improved by incorporating an alkali-metal hydroxide in the alcoholic solvent d y e b a t h . Improvements in rayon stabilizing processes continue with the urea-formaldehyde, melamine and glyoxal processes continuing to lead the field. T h e use of urea or dicyandiamide is suggested for mill operations of resins w h e r e d a n g e r of odor development exists. N e w sizes or finishes include sodium cellulose sulfate for w a r p sizing or producing a chintzlike finish, and a variety of formulations based on polyvinyl alcohol and acetates, carboxy-
methyl cellulose, methyl cellulose, r u b b e r , silicones, a n d numerous other resin systems. A novel m e t h o d for imparting bulkiness to yarns involves a mixture of protein and other yarns and causing some of t h e fibers to shrink more t h a n others, and thereby p r o d u c i n g an arch-like effect. The Future It is of special interest to consider the implications of all of these developments in the chemical industry. T h e t r e m e n d o u s publicity given the newer fiber developments and t h e glamor connected with them have m a d e it a p p e a r that these fibers account for a larger part of our first consumption than is actually the case. W h e n it is r e m e m b e r e d that approximately 5 billion p o u n d s of cotton and u p to nearly a billion pounds of wrool h a v e accounted for a b o u t 8 5 % of t h e total annual fiber consumption in this country in recent years, it is a p p a r e n t that the synthetic fibers, including well over a billion p o u n d s annually, account for a relatively small proportion of the field. It is even more striking to note that nylon, although it has assumed one of the most important n a m e s in textiles, probably does not account for one per cent of t h e fibers used. S u c h data m a k e it immediately a p p a r e n t t h a t the development of a new synthetic fiber with its requirements in terms of monomers, solvents, dyestuffs a n d finishing agents can assume sizable proportions from a chemical manufacturer's p o i n t of view without necessarily m a k i n g a m a r k e d d e n t in t h e textile industry. Finally, although textiles have b e e n used by m a n since he has been on e a r t h , it is only 100 years since o n e of the earliest chemical finishing processes, the m e r cerizing process was discovered, and m u c h less than 50 years that t h e r e has b e e n a synthetic fiber industry. It can only b e concluded from this that the future of chemistry in textiles is bright indeed.
SYNDETS HIT FIRST BILLION POUND YEAR FOSTER DEE SNELL, Foster D. Snell, Inc., 29 West 15th St., N e w York 11, N. Y.
N e w production facilities and new applications further established surface-active agents or surfactants as basic industrial commodities
Or these the largest production is of synthetic detergents or syndets b a s e d on petroleum in t h e form of alkylate, a comb i n e d alkyl aryl h y d r o c a r b o n . Although t h e alkyl portion is always obtained from petroleum, t h e aryl portion may or m a y 36
not be. Soap continues to b e replaced by syndets for some uses where t h e latter do a better job. Syndets hit their first billion p o u n d year, p r e d i c t e d for 1950 as far back as 1947. T h e following table in w h i c h t h e figures C H E M I C A L
for 1950 are extrapolated by multiplying those for t h e first three quarters b y 1.33 says more t h a n words can about t h e competitive situation. T h e largest soap sales t o d a t e w e r e i n 1941 w h e n they approximated 2.5 billion A N D
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NEWS
D e v e l o p m e n t s in the ChemicaS a n d Process Sales in 1000-pound 1948 1949 Solid soap 1,936,762 1,871,755 Syndets 281,488 _531,133_ Total "2,218,250 2,402,888'
units 1950 2,326,656 J.,090,276 3,416,932
pounds. In 1950, soap approached this peak although the price of inedible tallow in late 1950 was 12 cents a pound—twice what it was at the same time in 1949. This reflects individual and corporate stockpiling due to conditions in Korea. Liquid syndets had a moderately greater rate of increase of production than the solid form, but not all the commercial liquid form is now of the nonionic type. Only one bar form of syndet has reached the market and continues to be sold only in test areas. In retail packages, pricewise, soap at 70 to 92% active plus builder competes on an equal basis with syndets at 18 to 4 0 % active plus builder. Production of syndets has shown a marked tendency to level off during the current months. One cannot expect sales of syndets to nearly double again in 1951. Barring special pressures for production a fair guess for 1951 is 1.25 billion pounds with soap a little over 2 billion. Contrasted with the early 1940's however petroleum derivatives for syndets have taken much of the pressure off inedible fat supplies so that in a predicted national economy of shortages there is no indication that such will apply to detergents— that is soap and syndets. Status of Soap No startling developments have occurred in the soap field. Commercial production by continuous methods marks application of previous trends by the major soap companies. Soap not only has tremendous competition from syndets, but its important by-product—glycerol—which bears part of the soap cost now has strong competition from the synthetic product. About 85 million pounds of synthetic glycerol are produced currently, with probable 1951 expansion of production facilities. The current open-market quotation of 42 to 45 cents a pound, which compares with 24 cents late in 1949, reflects the Korean situation. Present production of synthetic plus glycerol from the soap plant about meets the legitimate demand, but stockpiling has produced shortages. Antiseptic soaps of 1949 introduction met competition and were reduced in price by over 20%. Household soap prices of the big three went up 7.5% in September. Surgical scrub soaps containing G-ll largely took that market along with one syndet solution containing the same antiseptic. Surfactant Developments Eight companies, largely petroleum producers, now compete in producing alkylate suitable for conversion into syndets. These alkylates boil at approximately the range of dodecyl benzene. Some of these companies make syndets themselves, while VOLUME
2 9,
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industries
»
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Top, flake soap. Lower left, a spray-dried syndet. Lower right, a spray-dried built soap. All products are from commercial packages some sell all of their alkylate to sulfonators. One major company is installing capacity to combine tetramer with benzene by a sulfuric-acid process, competing with the existing Friedel-Kraft reaction with keryl chloride or unsaturates. The price of 13.5 to 16.5 cents a pound for alkylate is substantially the same as at the end of 1949, a striking contrast to doubling of soap-stock prices. The toluene-derived alkyl aryl sulfonate involves a problem of hygroscopicity not yet solved. So toluene alkylate has disappeared from the market, even though benzene is in short supply. This situation will probably be relieved in 1951 by substantial increase of the current 10 million gallons of benzene annually from petroleum. A major soaper selling fat-based, heavyduty syndets came on the market with a competitive petroleum-based product made by continuous sulfonation. The increase in volume of retail syndets has been largely of the heavy-duty type efficient for general laundering in hard water. Initial production of phosphorus from another plant permitted more liberal building of syndets with sodium tripolyphosphate to the optimum level. In late 1949 only one such product was so built. One result of this was initiation of litigation between two of the major soapers, based on patents which issued in late 1949 covering in general the heavy-duty type of syndet. Substantially all current soaps and syndets contain orptical bleaches. Light-duty syndets for dishwashing were improved by one producer by addition of an ingredient to make the product less harsh on the hands. Sodium oleyl methyl tauride was offered to formulators as a 28% solution. Patents on the product expired and IV-methyltaurine was made
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available in modest amounts, to be increased in 1951. The Food and Drug Administration in a preliminary decision being contested, banned polyethylene surfactants from bread. Monoglycerides which serve the same purpose, as well as being a possible basis for sulfated monoglycerides, became available in quantity from molecular distillation in a purity previously unattainable. Supplies are not yet freely available. A solid nonionic became available in late 1950. "No-rinse" advertising of synd^s appeared at the strategic time of an acute water shortage, notably in New York. One reason behind this advertising was that the suds from a syndet do not disappear as quickly in rinsing, as when soap is employed. Some users judged this to mean that detergent was still present, even though actually it might be an insignificant amount. With soap in the rinse water, suds disappear quickly because water hardness precipitates residual soap and so kills the suds. All three of the major soap companies came out sequentially with no-rinse advertising of their syndet products. Although rinsing is of less importance when washing with-a syndet than when washing with soap, a group organized to study such matters on a practical basis, expressed a published opinion that repeated washing without rinsing in time leaves linens less white. Several new anionic syndets are ammonium or amine salts rather than the customary sodium salts. These have the advantage of being available in concentrated solutions which remain clear, which makes them suitable for use as liquid detergents. 37
C&EN A N N U A L
REVIEW—1950
T h e first large-scale test was made of •street washing with syndets—10 days in Philadelphia with pressure-flush trucks. In general—unlike soap—prices of the basicsurfactants declined by 10 to 2 0 % , competition in nonionics being particularly severe. As the year ended some price raises were appearing. Use of quaternary a m m o n i u m compounds as sa~' izers, and nonionic-quaternary combinations as detergent-sanitizers expanded greatly. Soap-Syndet Combinations In D e v e l o p m e n t Stage Combinations of soap with syndet for household use are still in the development stage. At t h e high dilutions used in rinsing, hard-water salts precipitate residual soap. In the power laundry—which uses softened water—this is not a factor, and 2 5 % of soap has been advantageously replaced experimentally with an alkyl-aryl type of syndet. Combinations of 6 0 % soap with 1 5 % of syndet a n d 2 5 % of tetrasodium pyrophosphate give better washing results than soap alone in 150 p.p.m. hard water. T w o nonionics give better results than an alkyl-aryl type of syndet. This suggests a future economical and effective deter-
gent in moderately h a r d water comprises soap and syndet built with polyphosphate, with perhaps other additives. Recent patents suggest a few per cent of higher alcohols as suitable additives to reduce lime-curd formation of soap-syndet products at rinsing dilutions. Laboratory Washing M e t h o d s Opinions continue to differ as to t h e desirable composition of artificial soil, as to the conditions to b e used with standardized washing methods in t h e laboratory, and as to the best way of expressing t h e results. Although reproducibility and correlation with practical results are the general aims, most research laboratories still set up their own procedures. A step in t h e direction of greater standardization would be agreement on a reference detergent. That most used at present is tallow chip soap. Surfactants—particularly those from petroleum—have a firm economic background and undergo continued technical development. New forms and lower cost of some of the nonionic agents promise usefulness in both general and special fields of application. Nonionics appear to offer the greatest possibilities for new
structures a n d modifications of the basic molecules. Major technical problems which confront the surfactant industry are— 1. Production from petroleum or other cheap raw materials of syndets with the excellent foaming and skin-conditioning qualities of the fatty alcohol sulfonates and monoglyceride sulfates. It still takes more of a petroleum-derived syndet than of a fat-derived to give equivalent effect. 2. Use of inexpensive salts as builders to give results comparable with those now obtained using relatively expensive molecularly-dehydrated phosphates, currently in somewhat short supply. 3. Overcoming hygroscopicity associated with alkyl toluene sulfonates and, to a lesser extent, with other sulfonates. 4. Preparation of nonionic agents with the advantages of present nonionics plus improved foaming. 5. Production, for special purposes, of efficient syndets with no foaming tendency. 6. Production of entirely satisfactory syndet bars at costs competitive with soap bars. Appreciation is expressed of suggestions and editorial assistance by Cornelia T. Snell, Irving Reich, and John R. Skeen.
FERTILIZER USE TIED TO FARM PRICES F. S. LODGE, The National Fertilizer Association, Washington 5, D. C
The past year saw fertilizer use vary as farmers were concerned about price supports and acreage controls . . . Present mobilization plans should send him scurrying for all he can get JL H E calendar year 1949 saw an increase in t h e consumption in the United States of fertilizers of about half a million tons to a record high of 16,534,000 tons. T h e increase was not consistent throughout the country, however. New England, the East North Central states, and the western states particularly the Pacific Coast states generally showed decreases while t h e other areas h a d increases which more t h a n offset them. T h e crop planting year of 1949—50 was one of uncertainties for agriculture. T h e r e was the fear of lower farm prices with resultant decreased farm income; there was the uncertainty of future government price supports for the principal crops; there was the likelihood of crop acreage allotments—all tending to m a k e t h e farmer hesitate. F o r many years t h e pattern of fertilizer consumption has closely paralleled that of farm income. W h e n t h e farmer saw hi£ income beginning to drop, his first 38
impulse was to buy less fertilizer because that represented a cash outlay. As a matter of fact, he would in nearly all cases have been better off if he had bought more fertilizer and used it on less acres. By so doing h e could have produced t h e same amount of total crops with less labor, less seed, less gasoline, and less overhead. These enumerated uncertainties tend to cause the farmers to delay t h e purchase of their fertilizer requirements till the last moment, in fact often till crop planting time. Most superphosphate plants and mixed fertilizer plants are designed with the idea of production turnover. In other words the capacity to manufacture far exceeds the capacity to store and the superphosphate storage must b e emptied by making mixed fertilizers or by shipment to other dry-mix ing plants, if consumption requirements are to b e met. The d e m a n d for fertilizers has more than doubled during the past 10 years, a period C H E M I C A L
during which construction has been most difficult. Even after war building restrictions were removed, it was next to impossible in many localities to obtain building materials and equipment. By working two shifts, it has b e e n possible to double production providing the storages could be emptied and refilled, b u t it was also a period of labor shortages and transportation difficulties in many areas. W h e n shipping orders are held up till the peak of the planting season, it is impossible to meet the demand. T h e only assurance the grower will have that his needs can be met will be for him to purchase and receive his fertilizers early a n d store them in a good dry place on his own farm. It appears that w e may be entering another emergency period when goods of all sorts will b e scarce, if n o t under priority or allocation. E v e n should an actual major war not eventuate, any program of extensive preparedness will proAND
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