k
§ INDUSTRY & BUSINESS
Emery E x p a n d s Ozonolysis Plant Increase in capacity for azelaic and pelargonic acids means more viny! plasticizers,. jet lubricants V^oxrixG U P : A several-fold h i k e in azelaic and pelargonic acids capacity by E m e r y Industries, sole U. S. producer of t h e two fat-derived a c i d s . A $6 million plant expansion ( C & E N , Aug. 3 1 , p a g e 17) at Emery's Cincinnati, Ohio, works also calls for a hike in production of esters of the t w o acids. Esters of both acids find their main outlets as specialty vinyl plasticizers and jet engine lubricants. Pelargonic acid itself also goes into alkyd resins and vinyl stabilizers. T h e two acids are made mole-formole via ozone oxidation of oleic acid. Emery's plant, says the firm, is the world's only commercial ozonolysis plant. T h e process was d e v e l o p e d by E m e r y , and the original plant w a s built five years ago. In the process, o z o n e attacks oleic acid's double bond, cleaves it to give the two nine-carbon acids; azelaic is dibasic while pelargonic is monobasic. Azelaic acid's first and still major market is in vinyl plastics. Diesters of the acid, Emery's series of Plastolein Plasticizers, are used as low-temperature vinyl plasticizers. Most widely accepted: dioctyl azelate. Although low temperature materials m a d e u p only a fraction of last year's 4 1 7 million pound plasticizer p r o d u c t i o n (of w h i c h phthalates m a d e up 56'< ) , they comprise an important group of specialties. Production of azelates in 1 9 5 8 was just over 5.7 million pounds, down slightly from 1 9 5 7 Y 5 . 8 million p o u n d s . Sales, though, improved in 1958—5.4 million p o u n d s compared to less than 5.3 million in 1957. In 1959, E m e r y estimates, p r o d u c tion figures will about e q u a l 1958 figures with substantially b e t t e r sales. Price for the azelates last \ e a r was a b o u t 42 cents a pound, which also is the 1959 level. Vinyl p r o d u c t s m a d e with azelate plasticizers i n c l u d e auto and furniture upholstery, film a n d
sheeting, footware, luggage, and extruded products. Azelates also give vinyl film a h a n d and d r a p e which is d e e m e d especially desirable by coated fabric makers a n d buyers, thus have an e d g e over potential competitors. • Adipates N e a r e s t Competitors. A d i p i c a c i d esters, p a r t i c u l a r l y d i o c t y l
adipate (priced at 5 cents a pound less than dioctyl a z e l a t e ) , stack u p as t h e azelates' nearest potential competitor. Many ol the azelates' properties also are claimed for adipates. Although adipic acid also can be obtained from fats, it's made commercially by oxidizing cyclohexanol or cvclohexane.
Specialty plasticizers production and sales figures stock up like this against total plasticizer picture 1957 Sales
All plasticizers Phthalates Adipic acid esters Azelaic acid esters Sebacic acid esters
Production (1,000 lb.)
Amount {1,000 lb.)
Value {$1,000)
Unit price (per lb.)
442,085 251,157 8,975 5,854 1 2,553
362,810 200,714 7,092 5,271 9,724
1 1 3,655 56,370 3,002 2,388 5,260
$0.31 0.28 0.42 0.45 0.54
Production (1,000 lb.)
Amount (1,000 lb.)
Value ($1,000)
Unit ^rîce (peMb.)
41 7,21 4 237,464 9,439 5,748 1 1,370
355,365 197,266 6,544 5,409 10,424
1 10,835 55,1 2 Ï 2,614 2,495 5,776
SO.31 0.28* 0.4O 0.46 t 0.55
1958 Sales
All plasticizers Phthalates A d i p i c a c i d esters A z e l a i c acid esters Sebacic acid esters * J into and
This g r o u p makes u p more than h a l f o f t o t a l plasticizers. These a r e higher p r i c e d compounds. Most of the azelates go l o w temperature v i n y l plasticizers. O n l y some o f the adipates s e b a c a t e s d o so.
Source:
U. S. Tariff Commission
SEPT.
7.
1959
C&EN
25
I N D U S T R Y & BUSINESS
Total production of adipates in 1958 was more than 9.4 million pounds, in cluding dioctyl (2.1 million) and other esters. Adipates also are used as plasti cizers for rubber, miscellaneous resins, and for vinyl butyral in safety glass. There are several major adipates pro ducers. Some sebacic acid esters also go for similar uses. What share of 1958's nearly 11.4 million pounds* production wound up this way hasn't been gaged, but consensus is that the amount is negligible. Sebacates have a price disadvantage, sell for 10 to 15 cents more per pound than azelatcs. Other fat-derived materials also have a niche in t h e plasticizer field. Among these: epoxidized soybean oils and epoxidi/.ed esters based on fats. Neither sales nor production data are available on the compounds, which are made b> a number of companies in cluding Emery. Applications are specialized, and the epoxies also have stabilizing properties. In fact, most of the low-temperature plasticizer formu lations contain from one to 1 0 ' ' epoxy ί vs. 40 to 5 0 r r azelate, for example). But the surface of fat-based plasticizers has hardly been scratched, says ArcherDaniels-Midland, another major pro ducer of the epoxy and polymeric plas ticizers. • Jets, Resins Assure Pelargonic's Future. Pelargonie acid has a strong foothold in two markets. T h e first of these, resins (alkyd type) and poly mers, is already "considerable," says Emery. Here, pelargonie competes with coconut oil derivatives—capric, caprylic, caproic, and lauric acids. Pelargonic's claimed advantages: better quality (especially color), and some times lower prices. But the jet lubricants field is ap parently the comer, as far as pelargonie acid is concerned. Pelargonate esters' (Emolein diesters) use in jet engine lubrication is substantial, says Emery. And increasing consumption of the lubes is assured, says John J. Emery, president of Emery. Today's major demand is from the military. Com mercial jet aviation, though, is only be ginning a n d promises a large market. Since az.i'laic esters also go into jet lubes ( as do adipates ), and pelargonates cross over into the plasticizers, one outlet could take u p the slack if the other should falter—an unlikely pos sibility in the immediate future. 26
C&EN
SEPT.
7, 1 9 5 9
U. S. Eases Export Control
Mexic an Sulfur Unhurt Recent earthquake little harm to sulfur a n d docks INITIAL
reports to the contrary,
high-riding r.—r_
does plants
i-U..
Mexican ,U
*\—
sulfur
,w.^..f
the
industry
,....-«-U^ , 1 .
Λ
with only a few scratches. This despite the fact that mining and shipping op erations a r e concentrated on the Isth mus of Tehuantepec, which received the brunt of the quake. All four of t h e U. S.-backed sulfur companies operating on the isthmus re port only superficial damage and little, if any, delay in production. Only Pan American Sulphur cut back operations at its plant near Jaltipan, but this was to let its workers help with emer gency shelters in the town. Jaltipan itself was hard-hit; about 80r,'< of its buildings were destroyed and at least 12 people were killed. Texas Gulf Sulphur reports very lit tle damage to its plant at nearby Nopalapa. T h e quake caused a small crack in t h e levee of TGS's reservoir, but this was repaired without trouble. Neither Gulf Sulphur nor Texas In ternational Sulphur were badly hurt. Gulf estimates a few hundred dollars at the outside will fix u p its plant. TIS had no plant damage, but told O&EX that it plans to water-check its dome formation for fractures. T h e company only recently started u p its 300 ton-perday plant at Texistepec, 12 miles from Jaltipan. • Port City Suffers. T h o u g h the Gulf Coast city of Coatzacoalcos was another hard-hit area, the sulfur clocks there were spared serious damage-. A wall fell off a TGS storage shed; Gulf's loading belt was d a m a g e d but returned to work within a few hours; and Pan American's docks were n o t hit enough to stop operations there. Gulf probably suffered the biggest inconvenience of the sulfur companies when one of the city's water wells went out.
T h e well s u p p l i e s w a t e r for C^ulf's
filtering plant at the dock and through put had to he halted for a time. T h e company continued to filter sulfur at its dome, however. Though the sulfur docks fared well, the city itself didn't. Coatzacoalcos othcials reported at least 8 8 % of t h e city badly damaged a n d 20 dead.
l \ S. Department of Commerce eased up on its control of exports to East Europe ( Albania, Bulgaria. Czechoslovakia, East Germany, Estonia, Hungary, Latvia, Lithuania, Poland. Rumania, and the U.S.S.R.) in 1959's second quarter. Export license ap provals totaled $7.2 million in the sec ond quarter, compared with $6.6 mil lion in the first quarter of 1959. T h e second quarter also saw a drop in rejected export license applications by the Commerce Department—only $11.1 million worth of rejections com pared to S 15.2 million in the first three months. Just about all of the rejected licenses ($10.6 million worth) in 1959's second quarter were for export to the U.S.S.R. Items on the rejection list were $316,400 worth of electrolytic copper and $625,000 worth of chrome alumina catalyst. Polyethylene worth $88,850 was rejected for export to Hungary. Commodities approved for export to Czechoslovakia in the second quarter included η-butyl alcohol valued at $137,789; dimethyl terephthalate, $204,966; crude sulfur, $515,000; and caprolactam monomer, $23,600. Some of the items which got the green light for export to the U.S.S.R. in the second quarter were: synthetic staple fibers worth $612,132; n-butyl alcohol, $551,156; η-butyl acetate, $197,860; polyethylene, $157,088; and carbon black, $66,547. Second-quarter export license ap provals for Rumania included crude soybean oil worth $463,950; ethylene carbonate, $9135; and ethylene di amine, $1852. U. S. shipments to all eastern Eu.. .iUpCclIl
, »...:„,. ; . , *-U ~ C-~«- ^ , . . , . . t ^ . . ,,£ CULUiLiica m t u t ; m a i i j u a n t i v/i
1959 totaled $18.9 million, down slightly from the $21.4 million exported in the fourth quarter of 1958. Almost 80Vc ($15 million) of first quarter ex ports were to Poland, mostly agricul tural goods exported under general license. U. S. exports to t h e U.S.S.R. in 1959's first three months hit $2.4 mil lion—shipments to the U.S.S.R. for all of 1958 came to just $3.4 million. Most of the first-quarter exports ($2.1 million worth) were carbon steel sheet. Compared with total U. S. world trade for the three-month period, ex ports to East Europe amounted to less than 0.5 7
