C&EN'S ANNUAL REVIEW OF DEVELOPMENTS IN Likewise, considerable interest is b e i n g shown in t h e conversion of xylenes to trie t h r e e isomeric phthalic acids. HTerephthalic acid from p-xylene has, of course, b e e n m a d e for several years as a r a w material for t h e polyester fiber, Dacron; a second producer, at least, is n o w in t r i e field. T h e problem of utilizing isophthalic, of course, remains. However, first reports of its utility in alkyds, polyesters, and piasticizers were very encouraging and its u s e seems assured when it becomes available. Another expected development, which is apparently quietly under w a y , is the use of mixed phthalic acids for plasticizers. Possible production of tererphthalic acid from butylène was also pointed out in some German work o n reactions catalyzed with lithium aluminum hydride, In this process, yields of over 50% 73-xylene are obtained w i t h ethyl benzene a n d o-xylene a s t h e only other products. Since separation of these is much easier t h a n separating t h e three isomeric xylenes, this process, in which the hydride is a "true" catalyst and not consumed, has r e a l commercial possibilities. In addition to t h e increasing d e m a n d for t h e terephthalic polyester fibers, announcement was m a d e late in the year t h a t a full-scale p l a n t for t h e production of film from this same plastic will be started early in 1953. Experimental production of this Mylar film during the past year has shown it t o have outstanding strength characteristics and excellent stability even at extremes of temperature, i t s most important initial application wilî b e in t h e electrical field where high strength, stability, water resistance, and excellent electrical properties will be needed. Later, uses are envisioned in t a p e s of all types including sound record-
copolymers. These products s h o u l d be particularly useful as potting compounds, coatings, a n d sealants. Nylon expansion was also in the news a n d t h e long-hinted entrance of Allied Chemical i n t o t h e field with a caprolactam-type material was announced.
ing a n d in packaging a n d even for storm w i n d o w s where its excellent clarity and toughness make it u n i q u e among films. Polyvinyl chloride production, although it d i p p e d somewhat toward midyear, is again o n the increase with a t least one new monomer producer as well as several actual o r potential new polymer producers. Particularly noteworthy were t h e introduction of a number of improved polymers and copolymers a n d a n intensification of interest in fabrication of rigid material. There are also indications t h a t vinyl c o polymers may become an i m p o r t a n t ingredient of latex paints and displace some of the styrene resins n o w used. Improved styrene copolymers a n d " a l loys" a r e also one of t h e newest developments a n d have e x t e n d e d the use of these materials to a n u m b e r of fairly critical items w h e r e their improved toughness w a s highly essential, such a s refrigerator door liners weighing as m u c h as seven p o u n d s and b a t t e r y cases weighing 14 p o u n d s . The increase in size of injection m o l d i n g machines was a p p a r e n t l y not as spectacular as in other recent years, but capacities of at least 375 ounces a r e now available a n d plans for increasingly larger moldings are b e i n g m a d e . In spite of a price increase, the epoxy resins continue to gain to the point where production for t h e y e a r w a s p r o b a b l y about 12 million p o u n d s . Trie main uses for t h e s e versatile resins remain i n coatings, adhesives, a n d potting compounds, but t h e r e is increased interest in t h e m as laminating resins with glass fiber so t h a t this c o u l d become a major u s e . Considerable interest is being shown in blends of epoxies and liquid Thiokol polymers. T h e mercaptan end groups in t h e latter react with t h e epoxide group to give " t r u e "
Phenolics The supply of phenolic resins was greatly increased b y one n e w phenol plant which boosted U. S. production b y 60 million pounds, a n increase of 1 5 to 2 0 % . Hercules also has entered the field w i t h an oxidation process starting with isopropylbenzene. Ironically, the phenolics were hardest hit b y t h e first-of-the-year slump w i t h production of casting, laminating, a n d molding resins d o w n to 11.2 million pounds in July in contrast to 20 million pounds in October, 1 9 5 1 . On t h e utilization side, there w e r e no notable advances. The expected increase i n consumption in the foundry field, especially i n t h e relatively n e w shell-molding process, has been considerably b e h i n d expectations. Part of the difficulty c a n be attributed t o the tooling that h a s b e e n required to h a n d l e the resin-sand combination adequately in the foundry. A numb e r of designs h a v e b e e n developed and a r e undergoing production shakedowns. However, long-range prospects h e r e are still excellent and account for a fair share of the President's Materials Policy Commission—predicted consumption of 1950 million pounds of phenol in phenolic resins for the year 1975. T h e r e are some indications t h a t application of phenolic resins in t h e foundry may b e eased by prccoating of sand with t h e liquid resin prior to drying s o that the foundryman c a n buy sand ready for immediate use.
FOSTER DEE 3NELL, Foster D. Snell, inc., New York, Ν. Υ.
Soaps arid Syndets . . .
Increased syndet research
may explain the 5 0 % foothold in household sales gained by syndets last y e a r S Y N T H E T I C detergents or syndets con tinued t h e same steady growth in pro duction in 1952 as in 1 9 5 1 , heading to w a r d a predicted 2 billion pounds in 1954 or 1955. T h e proportional increase in each case, over t h e previous year, was about 2 0 % . Soap, o n the other h a n d , de
38
clined about 6 % a s compared with a 2 0 % decline in 1951 from the previous year. The final production figures for solid soap and syndets for 1951 can be com pared with estimates for 1952, which are based on figures reported for the first nine months.
CHEMICAL
1951 1952 ( millions of pounds ) Solid soap 2444 2295 Syndets 1434 1717 Total 3878 4012 The increased total production in 1952
AND
ENGINEERING
NEWS
THE CHEMICAL AND CHEMICAL PROCESS INDUSTRIES
corresponds in part to population increase a n d in p a r t to a small increased p e r c a p ita consumption. T h e norm for postwar consumption is about 25 pounds p e r person per year. The revised 1951 figure is very close to this 25.1, t h a t estimated for 1952 is 25.6. Correlation of these figures w i t h reports on household sales indicates that syndets—unfortunately becoming known as detergents in popular u s a g e h a v e about half of the household market in 1952. The reason for this may b e that m u c h research continues on methods of improving syndets as heavy-duty a n d general-purpose detergents. Correspondingly, relatively little is done t o overcome t h e deficiencies of soaps, although some studies in this direction have b e e n reported. S o a p Progress T h e great improvement in syndet performance in washing cotton was b r o u g h t a b o u t by proper building. I t seems possible that new or better builders for soap c a n improve its effectiveness in h a r d water. There the trouble arises not so m u c h during t h e washing process itself— because excess sodium soap is a good dispersant for precipitated calcium a n d magnesium soaps—but in rinsing. Soap prese n t on washed fabrics, dishes, a n d glassw a r e is precipitated d u r i n g rinsing in h a r d water and remains adherent t o some degree o n the rinsed surfaces. Prelimin a r y results suggest that a m u c h greater degree of building soap with effective polyphosphates may give improved rinsi n g performance. This w o u l d m e a n r e placing much of t h e soda ash a n d trisodium phosphate formerly used, with t r i polyphosphate and similar séquestrants. T o counteract t h e too frequent dermatitis of industrial workers, antiseptic soaps which are definitely bactericidal have been developed. Some of these a r e superfatted to overcome t h e drying effect on t h e skin. The prices of r a w materials for soapmaking, on t h e average, have c h a n g e d relatively little. Inedible tallow is about
VOLUME
3 1, N O .
six cents a pound, down a cent or so from a year ago, .while coconut oil is a few cents a p o u n d more than a year ago. Caustic soda remains the same. Granular soap products as a rule run to about 6 5 % fat content, a higher proportion than in the earlier years of built soaps. A 2 to 4r/o cut in the price of packaged products b y the large soap companies in 1952 resulted in a lower dollar return, although this did not mean a decrease in the volume of sales. Glycerol T h e decrease in soap production during the last year results in a corresponding decrease in saponification glycerol. Synthetic glycerol was produced at the rate of 4 to 4.5 million pounds a m o n t h until a strike tied up production completely for 60 days, with a loss of about 8 million pounds. Production has increased in volume since the strike. It is estimated that present stocks are about 50 million pounds. T h e price has tended d o w n w a r d during the past year. GLYCEROL PRICES PER POUND
Saponification crude, soap lye 8 0 % C.P. 9 5 %
1951
1952
$0.38 0.55
$0.27 0.39
Syndet Progress T h e alkyl aryl sulfonates continue as the big leader a m o n g syndets; production is three to four times that of t h e nearest competitor, the alkyl sulfates. Sulfonation by absorption of sulfur trioxide vapor has been in t h e laboratory and pilot plant stage for several years, and is now approaching large-scale use. This will make possible a product well over 9 0 % active. The method avoids separation of a large excess of sulfuric acid as is necessary when oleum is used and the separation of active agent from sodium sulfate to produce a high active-agent product for some uses.
1 » » » JANUARY
5,
1953
The r a w materials for syndets attained a satisfactory production level in 1952. T h e estimated new capacity of sulfur p r o duction i n 1952 w a s 1,250,000 long tons. E s t i m a t e d increase over 1951 production was 410,000 long tons. Several large installations for production of sulfuric acid b y the contact process h a v e b e e n m a d e . As a result sulfuric acid is n o w in a p proximate balance with d e m a n d nationally. Despite the period of nonproduction of benzene from coal tar d u r i n g the extended steel strike, total production for 1952 is estimated at a b o u t 2 3 0 million gallons a s against 210 million gallons in 1951. In 1951 production of b e n z e n e from petroleum was 28 million gallons, t h e 1952 estimate was 45 million. Construction was begun on 13 n e w plants for p r o duction from petroleum, with five more being planned. T h e price of both b e n zene a n d sulfuric acid is the same as a year a g o . T h e "keryl" fraction, as t h e alkyl portion of alkyl a r y l sulfonate, h a s largely been replaced by propylene tetramer. A n e w competitor for t h e market has a p p e a r e d . Potential oversupply of inedible tallow resulting in long-range, lowprice forecasts has promoted its reduction to fatty alcohols a n d their sulfonation to sodium palmityl a n d stearyl sulfates. T h u s , fat-derived surfactants a r e freed of t h e incubus of the tax carried by coconut oil since depression days. Expiration of p a t ents in t h i s field in recent years has b e e n a contributing factor. Production of sodium tripolyphosphate, whose major outlet is for the building of soaps a n d syndets, increased 10 to 15%? over 1 9 5 1 . Production of tripolyphosphate is now greater t h a n the total of all t h e other sodium phosphates. Yet t h e production was negligible a d e c a d e ago. It is currently about four times t h a t of tetrasodium pyrophosphate. T h e estimate for tripolyphosphate is about 350,000 short tons. N e w Physical F o r m s Liquid syndets are n o t n e w on t h e market b u t many new brands are n o w available. Production a n d sales of these as light-duty detergents for washing dishes a n d fine fabrics showed increase in 1952. Some of these are nonionics, some are anionics. As a rule, t h e latter can b e m a d e less expensively. E t h y l e n e oxide, so important for m a k i n g nonionics, has been removed from the scarce materials list. T h e supply h a s increased from 37.8 million pounds in 1948 to 8 1 . 2 in 1951. T h e price rose in t h e same period from 14 to 18 cents per p o u n d . A b o u t 2 5 % of t h e production now goes i n t o syndets. P r o pylene oxide permits a solid nonionic which c a n be flaked. The increasing popularity of liquid syndet products is believed t o be d u e to lack of dustiness a n d rapid solubility. They are less harsh on the h a n d s than most built syndets. Use is s p r e a d i n g for commer39
C&EÏM'S A N N U A L REVIEW O F DEVELOPMENTS IN cial dishwashing as well as in the household. Acceptance of liquid light-duty products may have a bearing on the fact that one well-known brand of granular light-duty syndet has been changed to an all-purpose product, sold under the same name as before. Three new syndet bars—at least one containing some so» p—have appeared for test marketing, a field where there was previously only one. They are higher in price than soap but are described as longer lasting. Indications are that people buy a detergent more on satisfactory performance than on price, providing the latter is within reason, which suggests that syndet bars may be headed toward taking some substantial portion of this half-billion-pound market. The Federal Trade Commission rendered a decision in November that the manufacturers of well-known syndets should stop claiming that these wash clothes "just as clean" without rinsing as with rinsing. Meanwhile, no-rinse has died a natural death to be replaced by claims of syndets washing clothes as clean without bleaching as soap will with bleaching. The presence of optical bleach, in use now for some years, is the answer.
Foreign Four of t h e leading granular syndets are now made in Britain on modified formulations by subsidiaries of the three leading American soap companies. Shortages of phosphates dictate modifications there. Plants for the production of syndets are in operation in many countries; one was opened in Pern in August. Theoretical Correlation of various published x-ray measurements suggests that there are three main types of micellar configuration of detergents, whether soap or synthetic in nature, and equilibrium between different types may exist in a solution. Laboratory studies continue to emphasize the difference in performance of detergents in soft and hard water. For example, sodium alkyl aryl sulfonate plus sodium sulfate only, is reported in Launderometer studies to give better detergency on wool in 300 parts per million hard water than does a commercial phosphate-built detergent. In distilled water the opposite is true. At high concentrations, 0.2% or more, commercial soap gives better detergency than either of the syndet products in distilled water, but
much poorer results than either in 300 parts per million water. Sorption studies made with use of radioactive tracers (sulfur-35 for a sulfonate, and carbon-14 for soap) show that both soap and alkyl aryl sulfonate are sorbed to a greater degree o n wool than on cotton. On wool both physical and chemical sorption occur, the former rapidly, the latter slowly. Soap is sorbed by cotton more slowly than alkyl aryl sulfonate, but is much more difficult to desorb. Builders, temperature, a n d t h e hardness of the water affect the result. In distilled water it is probably the fatty acid which is sorbed; in hard water, the calcium and magnesium soaps. These and other investigations suggest that sorption of the detergent by fabric may b e one of t h e important factors in the over-all detergent process. The effect of builders on such sorption may enter into their useful functioning, also the sorption of detergent and builders by soil. As detergency studies become a little less empirical, more and more factors are brought to light which can affect the result. (The author expresses appreciation for the editorial assistance of Cornelia T. Snell. )
ROBERT B. HOBBS and WILLIAM K. WILSON, National Bateau of Sî&rsd&rds, Washington, D, C
Pulp a n d Paper . .
•
Industry
displays
its
optimism
with a $ 6 0 0 million outlay for n e w mills and modernization in the period 1952—54 PRODUCTION in the paper and paperboard industry was again showing a definite upward trend toward the end of 1952, following a weakness that had extended from mid-summer of 1951 to July, 1952. The American Paper and Pulp Association's production ratio (production as percentage of normal capacity) had gradually declined from 100 in June, 1951 to 76 in July 1952 but recovered to a level of 91 for October. The paperboard operating ratio of the National Paperboard Association had shown a similar, but sharper, de40
cline from 103 in June 1951 to 71 in July 1952 but rose in even more decided fashion to 96 for October. This optimism in the industry is reflected in a huge volume of spending and plans for new mills and modernization in the three-year period 1952-54. Some of the larger projects, a s listed by "Paper Mill News," are summarized in the table. The total new capital for these and other projects was estimated b y the same source at $600 million. Our Canadian neighbors are experiencCHEMICAL
ing a similar trend. Prominent projects include a 300,000-ton expansion of newsprint production by Bowater in Newfoundland, a new $65-million pulp and newsprint mill by Celgar Development Co. in British Columbia, trie $21-million Elk Falls mill in British Columbia, which began operation in September 1952, St. Lawrence Corp.'s $22-million expansion program in Quebec, and Westminster Paper Co/s $25miliion bleached sulfate mill planned for British Columbia. An interesting major foreign development is a $45-million AND
ENGINEERING
NEWS
