Xylene Isomers Score as Intermediates... - C&EN Global Enterprise

Nov 6, 2010 - NO STRIKINGLY NEW CLASSES of compounds made quite the splash in 1956 as did isocyanates and urethanes in 1955, but the chemical ...
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In 1956's closing weeks, two new ethylene ventures moved into the planning stages—a 200-miilion-pound-a year plant by Petroleum Chemicals for Lake Charles, La., a n d an 80-million-pound plant bf H u m b l e Oil for Baytown, Tex. —to join a 100-million-pound unit announced earlier by Union Oil for Los Angeles.

THE CHEMICAL. WORLD

Older, substituted aromatics got renewed scrutiny as chemical starting points. By mid-year, Standard of California had the first U. S. plant for isophthalic acid on stream at Richmond, Calif, ( a b o v e ) , in 1956's closing weeks, Standard Oil of Indiana licensed Scientific Design's xylene oxidation process, planned a million plant for various phthalic acids and esters And to round out hydrocarbon acetylene's picture for 1956, American Cyanamid will a d d to its Fortier plant capacity at Avondale for acrylonitrile, while at year's end Grace began talking about a possible acetylene unit at its Memphis plant. Acrylonitrile and vinyl chloride, important though they may be in tonnage, hardly scratch the surface of acetylene's potential as a building block. Just where acetylene can lead was highlighted last year by General Aniline & Film when it brought its $6 million plant for "Reppe chemicals" on stream at Calvert City. Products include 1,4butanediol, butynediol, butyrolactone, propargyl alcohol, propargyl bromide, and polyvinylpyrrollidone—all in commercial volume, some for the first time. Although G A F uses carbide-generated acetylene, its "first" in t h e U. S. in exploiting Reppe chemistry shows what market development men mean when they say, "Watch acetylene." No one could have predicted 15 years ago how far ethylene would go as a starting point, and t h e same is true today for acetylene. However, some indications can b e given as to where acetylene will make its play. So far, all hydrocarbon acetylene plants have been located in the Southwest (omitting Wulff Process' demonstration-scale plant in Los Angeles), and this region will have the inside track as long as natural gas doesn't go above about 20 cents a thousand cubic feet. Outside this area, acetylene based on calcium carbide will probably increase for t h e next year or two. While t h e tack to date has been for hydrocarbon acetylene producers to 32

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start from scratch and make acetylene primarily, another approach would be to make it as a co-product in an ethylene operation—and there's a lot of ethylene being produced in the U. S. today. Two straws in the wind last year: • Carbide & Carbon began cracking refinery gas to make ethylene for its polyethylene plant at Torrance, Calif. Some acetylene results, and Linde now takes this and bottles it for the welding industry. • Phillips will make ethylene a n d byproduct acetylene at Sweeny, Tex., with the ethylene going to Pasadena, Tex., for polyethylene production by Phillips, Celanese, and any other customers who will buy it. Acetylene will be ready for sale after mid-year, Phillips says. Meanwhile, a few acetylene developments came to light overseas last year. Hoechst has what is reported as a "redhot" possibility in a process giving a mixed ethylene-acetylene stream, supposedly giving it an edge over present processes under some conditions (the Wulff process, however, can also give a mixed ethylene-acetyl 3ne stream under some process conditions). A new acetylene process is also reported in the embryonic stage at Knapsack, Germany. T h e third European acetylene development is one by Société Belge de l'Azote at Liege, Belgium, in separating acetylene from other chemicals in the process stieam. Blaw-Knox announced in December it has a license for SBA's process. Acetylene may b e looked on as a bright spot in the future, but its alter ego, ethylene, can't b e dismissed yet.

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Xylene Isomers Score as Intermediates . . . . . . and the chemical industry turns out new products at such a clip it's hard to get them tested. Result: more product evaluation

labs J N j o STRIKINGLY NEW CLASSES of COm-

pounds made quite t h e splash in 1956 as did isocyanates and urethanes in 1955, b u t the chemical industry was far from idle, turned out several new individual intermediates t h a t will leave their mark in 1957 and later. And in classes of compounds, one group of old timers, substituted aromatics, began getting a second look. Among them—nitrobenzene, chlorobenzene, phenol, a n d especially xylenes. Just where xylene isomers may fit in as stepping stones t o other chemicals was spotlighted by t w o events of 1956: By mid-year, Standard Oil of California had the first U . S. plant for isophthalic acid on stream. T h e starting xylene, the meta isomer, thus joined its ortho and para cousins as the route to a phthalic acid important in coatings and polymers. T h e n at year's end, Standard Oil of Indiana took t h e xylene isomer plunge, licensed Scientific Design's oxidation process, a n d laid plans for a $10 million plant for phthalic anhydride, isophthalic acid, terephthalic acid, benzoic acid, a n d several of their esters. Both events firm u p a trend to petroleum-based aromatics. (There may b e a trend to petroleum aromatics, b u t the coke oven industry didn't stand b y in 1956. Faced as it is with petroleum competition, the coke oven industry adopted petroleum refinery techniques to purify aromatic chemicals—benzene, toluene, xylene. Jones

& Laughlin took Esso's Hydrofining process to remove sulfur and UOP's Udex process to remove paraffins—both being chief contaminants. U.S. Steel selected a hydrogénation process licensed by Koppers to extract sulfur and then went to the UOP method to complete the purification.) Among other "chemical intermediate** highlights of 1956 were:

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• Carbide & Carbon's peracetic acid, which opened routes to a whole raft of epoxies. • Pfizer's dimethyl ester of acetonedicarboxylic acid, another in its series of fermentation-produced chemicals. • Union Carbide & Carbon's new class of carbon-functional silicones—two amino modified and two carbomethyoxy modified silane esters. That far from exhausts the list of new chemical intermediates coming out of the chemical industry last year, as any research director can tell you. In fact, new product turn-out has reached such a pace it is getting harder to launch new intermediates. In the past, chemical companies could bring out an interesting new molecule and be sure of getting widespread testing. If the product was good, it would find markets. Today, however, practically every chemical company comes up with new, reactive molecules that should be tried for "dyestuffs, intermediates, insecticides, and pharmaceuticals," as the now-famous phrase goes. With industry expanding and with fewer and fewer chemists available, there's a growing bind on application research, especially with someone else's product. The problem didn't crop u p suddenly last year, has instead been growing over the past few years to the point now that more and more market development men who are concerned with getting new products—or even old ones—into new markets line up with this prediction: For every dollar spent today developing a chemical—in taking it from test tube to tank car—you'll spend two dollars finding out what to use it for. And in five to 10 years, the ratio is going to be five or more to one. What is the chemical industry doing? "A laboratory which will tailor make products of research to meet specific needs of customers was dedicated here today." That is how Koppers put it last September 18 when it opened a new development lab for its chemical division. And Koppers wasn't alone in 1956, for others announced or completed similar expansions for applications research including: • Goodrich, for application studies on its own and other specialty acrylic polymers.

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X-RAY SPECTROSCDPiST NEEDED c REQUIREMENTS B.S. d e g r e e with major Sn Chem­ istry a n d a t least one y e a r e x p e r i ­ ence with fluorescence or diffrac­ tion X - r a y equipment. JOB DESCRIPTION Responsible for X - r a y analyses for l a r g e analytical group. Position in­ volves setting up equipment, mainly for fluorescence work. Duties con­ sist of development of methods, and application of p o w d e r diffrac­ tion techniques t o the study o f solid state reactions and utilization of X - r a y fluorescence in analytical procedures. OPPORTUNITY Here's your chance to get in on the "ground floor" o f a fast-moving new i n d u s t r y . . . with a company that will b e a vital force in atomic a g e developments. The position will provide you with b r o a d oppor­ tunity for utilizing your ability to think a n d to advance. Technical Personnel Office URANIUM DIVISION

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• W . R. Grace, also for polymer ap­ plications. • D u Pont, w h i c h completed a n elas­ tomer applications lab at Chestnut Run, Del., early in 1956, started expanding it about 2 0 % b y year's end.

have failed. T h e new ones may b e the same because of the w a y they are being developed—by making compounds structurally similar to known drugs or by operating screening programs based on effects of known drugs. But m e n t a l illness may be accom­ N o t so surprising is the fact that panied b y major metabolic deviations m u c h of 1956's expansion in applica­ untouched b y drugs we now have, tions research centered on plastics. which would provide a n e w point of Take polyethylene. Until fairly re­ attack for n e w kinds of drugs. H o w cently, only t w o companies made poly­ will t h e s e b e turned u p ? Perhaps in ethylene in t h e U. S. Today, about a the s a m e way so m a n y successful drugs dozen are in, a n d 1957 will see even have b e e n discovered in t h e past—by more as the n e w , l o w pressure poly- chance. Or perhaps they will come ethylenes come out. Products of com­ from greater understanding of how peting companies m a y be identical or tranquilizers act and how the brain q u i t e similar, a n d t h e only margin of functions. superiority m a y b e application research And in 1956, we d i d find out more offered. Applications research thus about h o w t h e tranquilizers act. In­ serves n o t only to get products tested; creasingly, researchers turned u p evi­ it also becomes a w a y to win new custo­ dence that serotonin, a compound pres­ mers. T h e p a r a d e t o such labs is defi­ ent in the brain, has a n important role nitely on the upswing, a n d we'll see in brain function a n d tranquilizer ac­ other companies, some in other indus­ tion. Bernard B. Brodie, National tries, joining this year. Heart Institute, has a d d e d to this evi­ dence b y showing t h a t reserpine causes release of serotonin from the central nervous system. Chlorpromazine, on tbc other h a n d , apparently acts by 1 9 5 6 blocking out norepinephrine, another neuron or m on al substance in the brain. D. W . Woolley a n d Ε. Ν . Shaw at Rockefeller Institute a p p r o a c h the sero­ tonin p r o b l e m from t h e antimetabolite point of view. One of t h e compounds they synthesized, l-benzyl-2,5-dimethyl serotonin, is now being investigated clinically to treat hypertension. Synthesis of radioactive reserpine may also h e l p show h o w this tran­ quilizer acts by permitting studies that might pinpoint its metabolic role. Rob­ ert B. W o o d w a r d , H a r v a r d , synthesized . . . including mental reserpine last year. Synthesis of so complex a molecule within a year of illness and cancer, while its structure determination testifies to biochemists learn more the a d v a n c e s m a d e i n recent years in about steroids. 'Tailor- the synthetic chemistry of natural products. m a d e " is a solid trend • C a n c e r . T h e chemotherapy attack on cancer w e n t into high gear in 1956 for drugs in 1957 —first full year for operation of the C a n c e r Chemotherapy National Serv­ During t h e year, CGNSC J V L E N T A L ILLNESS w a s t h e watchword ice Center. for many biochemists in 1956. Reser­ a r r a n g e d to screen 11,000 synthetic pine and chlorpromazine have had a compounds against experimental tu­ tremendous impact and in some cases mors i n mice. Before t h e service cen­ h a v e reversed the u p w a r d trend in ter's advent, a few t h o u s a n d compounds mental hospital populations for the w e r e screened a year—mostly at Sloanfirst time. Still, clinical experience Kettering, Southern Research Institute, indicates these drugs cannot cure and a n u m b e r of universities. C C N S C mental illness. T h e y merely quiet many expects to screen 15,000 t o 20,000 syn­ patients and m a k e t h e m more receptive thetics in 1957. to therapy. Side effects also remain By year's end, t h e committee got «* problem. heavily into screening antibiotic fil­ It will probably T h e pharmaceutical industry spent trates, or "beers." 1956 r e a d y i n g n e w compounds, b u t screen 20,000 beers this year (Sloanmany feel these m a y b e "more of the Kettering h a s screened 17,000 t h e past same"—only with the possibility of few y e a r s ) . One b e e r "in 100 shows fewer side effects or more potency so e n o u g h activity in mice to w a r r a n t they m a y b e useful where earlier drugs further study, vs. o n e in 1000 for syn-

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