CHEMICALS
Dow Offers Low-Cost Ethylenimine New process paves way to commercialization of highly reactive cyclic compound at low cost
Dow Chemical plans to produce and market ethylenimine monomer in commercial quantities for less than $1.00 per lb. A large plant for making the imine, planned for construction at Freeport, Tex., is scheduled to be on stream in late 1964. Until then, Dow will offer the compound in development quantities at $1.25 per lb. Ethylenimine, a highly reactive cyclic compound, has been marketed domestically at prices well over $5.00 per lb. in development quantities. As a result—despite its promise as a chemical building block for a variety of materials—the imine has never achieved any substantial or widespread use. Its availability in large volume and at lower prices should spark renewed interest in the compound and should pave the way to its greater use. Behind the imine's substantially lower price tag is a new, low-cost commercial process developed by Dow. The most commonly used approach is the ethanolamine process, which involves relatively costly raw materials. Dow isn't giving out any details about its approach, although it does say that the new process has fewer steps and better yields than the ethanolamine. Versatility. Ethylenimine is not a new compound. Research scientists have known about it for 75 years, and firms in Germany, where the first commercial process for making the imine was developed, have been producing it for a number of years. Very flammable and corrosive, it can be readily polymerized. The imine is very ver-
SEMIPLANT PRODUCTION. Operator checks gage at Dow Chemical's ethylenimine semiplant facility at Freeport, Tex., where development quantities are produced
satile, will react with acids, bases, metals, and many other materials. The reactivity and versatility of the imine stem from its being difunctional. It has the active hydrogen of an aliphatic secondary amine, thus undergoes many reactions similar to these amines. Because of its three-membered ring structure, ethylenimine easily undergoes ring-opening reactions. And, under appropriate conditions, it can be polymerized. The compound has been available in the U.S. for the past three years, primarily from German chemical companies. The major producer is Badische at its plant in Ludwigshafen, West Germany. Chemirad Corp., East Brunswick, N.J., both produces and imports the imine, also markets several of its derivatives. Other domestic producers include Borden Chemical and K & K Laboratories, Jamaica, N.Y., who make it in limited quantities. The ethanolamine process for making the imine consists of two basic steps. First, monoethanolamine is reacted with sulfuric acid to produce aminoethyl hydrogen sulfate. Then the sulfate is reacted with sodium hy-
droxide to yield ethylenimine. This route—the best available until now—is costly, though, and prices for the imine have reflected it. So, any extensive application of the compound has been discouraged. Current consumption is probably no more than 20,000 lb. per year. Now, at less than $1.00 per lb., many applications for the monomer will become economically feasible, Dow predicts. Also, availability of ethylenimine in large amounts should stimulate new research in this area. Capacity of the new Freeport plant will be over 1 million lb. per y e a r more than enough to supply any domestic needs, Dow points out. Derivatives. Derivatives of the imine also look promising. Several are currently finding use, although limited, for improving the properties of plastic films and for producing new kinds of flocculants and fireproofing materials. Two of the more promising ones: poly ethylenimine and tris(1-aziridinyl) phosphine oxide (APO). Dow already produces and markets polyethylenimine for specialty applications. Polymers of the imine can be JUNE
2 4, 196 3 C & E N
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tri fkiopoacettc hh)
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PRODUCT SPECIFICATIONS
(UUDUHJ
Assay by Titration Water Chloride Fluoride Sulfate Color
99.0% minimum 0.5% maximum 0.002% maximum 0.005% maximum 0.002% maximum Water White
Your copy of the NEW 16-page brochure on Trifluoroacetic acid is ready. Write today!
HALOCARBOISI
bromides
60
New Varnish Is Usable in All Classes of Electric Insulation
Dow Corning is going after a bigger portion PRODLJCTS CORPORlXT,ON of the electrical insulation market. A new insulating varnish just 82 Burlews Court, Hackensack, N.J. introduced by the company can be used in electrical equipment designed for operation up to 200° C—including Class A, B, F, and H insulation systems. Called GP-77, it is an organosilicon copolymer, available at $7.60 per galPRODUCTS lon in 55-gal. drums. This is markCOMPANY edly less than the cost of Dow Coming's line of silicone varnishes, which 237 SOUTH STREET NEWARK 14, NEW JERSEY range from $8.50 to $14.50 per galManufacturers of Fine Chemicals lon and are designed for applications at 180° C. and above. Because of currently manufactu red to order GP-77's lower price, easy processing, n-AMYL BROMIDE i• n-HEXYL BROMIDE and good properties, it should find use (1 -Bromohexane) (1-Bromopen'tane) in motors, transformers, armatures, rotors, and coils now insulated with SEC. AMYL BROMIDE i• PROPARGYL BROMIDE epoxy and polyester varnishes. (2-Bromopentane) (2-Propyn-l -Bromide) The market for electrical varnishes PRIMARY ISOAMYL BROMIDE i• n-PROPYL BROMIDE breaks down like this: 20 to 25% (1 -Bromopropane) (1 -Bromo-3-Methylbutane) epoxies, 30 to 40% polyesters, and 35% alkyds, silicones, diphenyl oxides, n-BUTYL BROMIDE i• ISOPROPYL BROMIDE and the like. The lowest-price var(1-Bromobutane] (2-Bromopropane) nishes on the market are the polyesters, which range from about $2.00 ISOBUTYL BROMIDE i• BENZYL BROMIDE to $3.00 per gallon. They are mostly (alpha-Bromo Toluene) (1 -Bromo-2-Methylpropane) used in Class A (105° C.) or Class B SEC. BUTYL BROMIDE '• TETRAHYDROFURFURYL (130° C.) systems. Most epoxy var(2-Bromobutane) BROMIDE nishes cost from $4.00 to $5.00 per (Tetrahydro-2-Furan Bromo Methyl) gallon and find application in Class A ^ E SOLICIT YOUR REQUEST FOR QUOTATION AND SPECIFICATIONS and B as well as in Class F (155° C ) . FOR THESE AND OTHER SPECIAL ALKYL BROMIDES Class H (180° C.) and above is dominated by the silicone varnishes. page 523 - 1 9 6 3 Chemical Materials Catalog See page 70 - 1963 Chemical Week Buyers Issue PRODUCERS OF INDUSTRIAL FLUORO ORGANICS
See
made with molecular weights of 100,000 or greater. Potential uses include cationic flocculants for sewage treatment, and additives for imparting wet strength to paper. A very toxic, but good, general-purpose reactive material, APO is made by reacting phosphorus oxychloride with the monomer. It makes a good agent for imparting fire resistance to textiles. This stems from APO's affinity for reacting with cellulose—a reaction which chemically ties phosphorus into the fibers. APO also works well as a wrinkle- and crease-resistance additive and as an agent to tie reactive dyes to textiles, according to Dow. Chances are good that Dow will enter the APO business. Work, too, is under way to develop other derivatives. But for now, Dow stresses, the primary emphasis will be on producing and marketing the monomer. CI
C&EN
JUNE
24,
1963
Benzol
C&EN PROGRESS REPORT
INDUSTRIAL CHEMICAL SPECIALTIES
Companies added these products to their lines during the past month Material Polyelectrolyte complexes (loplex resins)
Company Amicon Corp. Cambridge, Mass.
Amorphous polypropylene (Oletac 100) Antitack agent (Paricin I)
Avisun Corp. Philadelphia, Pa. Baker Castor Oil Co. Bayonne, N.J.
Insecticide (Thuricide 90T)
Bioferm Corp. Skokie, III.
Water-treatment chemical (Dearborn 847)
Dearborn Chemical Co. Chicago, III.
Rubberlike compounds (Flexanes)
Devcon Corp. Danvers, Mass.
Refractory coating (Metco 404)
Metco, Inc. Westbury, N.J.
Silicon semiconductor crystals (Lopex) Corrosion-resistant coating (Leadox) Liquid microbicide (Troysan CMP)
Texas Instruments, Inc. Houston, Tex. Tropical Paint Co. Cleveland, Ohio Troy Chemical Co. Newark, N.J.
Features Available in development quantities for evaluation in electronic components and sensing devices Copolymer for use in adhesives, caulking compounds, and specialty coatings Eliminates mold release problems and surface tack in butyl rubber molding or extrusion operations Liquid insecticide contains live spores of Bacillus thuringiensis, is lethal only to leaf-eating caterpillars Formulated to control corrosion and prevent calcium and magnesium deposits in once-through potable and process water systems Room-temperature-cure compounds do not shrink while curing, can be either cast or used as a coating Nickel-jacketed aluminum grains form pore-free nickel aluminide coating when flame-sprayed High-purity crystals with low etch-pit density, low radial dislocation gradients Modified alkyd resin with lead pigment for coating metal surfaces For use in interior latex paints; being tested for exterior latexes
Available in commercial quantities unless otherwise noted.
All Classes. A big advantage of GP-77, says Dow Corning, is the fact that it can be used in any class of insulation just by varying the cure. With a cure of four to 12 hr. at 135° to 150° C , for instance, its bond strength at operating temperature is comparable to that of good Class A or B varnishes. With a cure of four to six hours at 200° C , it can be used for Class F or H service, according to the company. GP-77's performance flexibility stems from its makeup, which combines the best properties of organic compounds with much of the heat stability of the silicones. The varnish has a room-temperature bond strength of about 80 lb. At 150° C., after a cure of six hours at 250° C , it has a bond strength of over 30 lb. Samples tested for heat stability by the curved electrode method stand up for over 22,000 hr. at 200° C. without failure. Epoxies and polyesters can't come close to passing either of these tests, Dow Corning points out.
BRIEFS Two partially hydrolyzed grades of polyvinyl alcohol have been introduced by Shawinigan Resins Corp., Springfield, Mass. Resins D-364 and D-369 are suggested for applications which require lower molecular weight and viscosity than are currently available in most grades of polyvinyl alcohol, according to the firm. Both resins will dissolve in cold water with minimum agitation. They will be useful as binders, the firm says. Because they lower the surface tension of water, they may also be useful as emulsifying agents, the firm adds. C2
An additive to be used as an aid in electrolytic cleaning has been developed by Panther Chemical Co., Inc., Fort Worth, Tex. Called EC-9 concentrate, the additive is a blend of detergents and synthetic surface-active agents. According to the firm, the additive will reduce reruns bv more
than 42%, will carry more than 150% of the work load of conventional reverse current cleaners. C3
Styrene-acrylic copolymer for highly durable floor sealer formulations has been introduced by Polyvinyl Chemicals, Inc., Peabody, Mass. Called NeoCryl CC-8, the copolymer can be used either as an undercoat or top finish. Films are clear, provide excellent wearing characteristics on resilient flooring, terrazo, flagstone, and cement, according to the company. C 4
Tungsten powder, of 99.999% purity, has been produced by Materials Research Corp., Orangeburg, N.Y. The powder is prepared from single-crystal tungsten rod, produced by electronbeam zone refining. The powder is available in limited quantities for research studies, is priced at $40 for 10 grams. Particle sizes ranging from —325 mesh may be specified. C 5 J U N E 2 4, 1963 C & E N
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PETROCHEMICALS... a little or n lot A N D RELATED C H E M I C A L S AT STRATEGIC DISTRIBUTION CENTERS
Say when SQV whete...
AMSCO'S THERE! Whatever you need in petrochemicals —in whatever amount— A M S C O will get them to you when and where you want 'em. Because of our newly expanded production facilities and a supply network second to none, A M S C O can promise —and make good on —the fastest delivery service in the industry. T h a t means you can forget about inventory problems! W h a t ' s more, you are assured of constantly uniform quality every time you take delivery. Remember . . . A M S C O can serve you, as it can serve all industry, large or small. If you have a special petrochemical problem, call us. We'll be there on the spot, on the dot. B E N Z E N E • X Y L E N E • NONENE • T O L U E N E • T E T R A P R O P Y L E N E
JklMfC©
AMERICAN MINERAL SPIRITS COMPANY A DIVISION OF T H E PURE OIL C O M P A N Y
N E W YORK SALES O F F I C E S IN PRINCIPAL CITIES
Tanker and Barge Loading Facilities at Convenient Supply Points © Direct Representation in England and on the Continent 62
C&EN
Alizarin blue for wool dyeing is being offered by American Cyanamid Co., Bound Brook, N.J. The new alizarin blue dye, called Calcocid SEB, is also suitable for dyeing nylon and Creslan acrylic fiber. It is recommended by the company as a self shade or as a component in combination with tan, brown, or gray. C6
One-step sealant that can be applied in any weather has been introduced by Sandell Mfg. Co., Inc., Cambridge, Mass. Poly-Tite fills and seals joints in metal, concrete, or any curtain wall construction, forming a barrier to moisture, wind, rain, cold, or heat, according to the firm. It is available in colors to match all construction materials currently marketed, the company adds. C7
Finish for synthetic and woven fabric has been introduced by Dexter Chemical Corp., New York, N.Y. The product, Ampitol CPE-70, is a cationicnonionic containing high melting, inert resins. It can be applied either by exhausting or by padding. It is compatible with thermosetting resins, according to the company. Abrasion resistance, sewing, and cutting are claimed to be greatly improved in both woven and knitted synthetic goods by use of the material, according to the firm. C8
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C h a p t e r 22 In Chapter 21, we stated that the chloroacetic esters are just the thing for carrying out Darzen's gtycidic ester synthesis of aldehydes. As an example, we can point to a patent issued in 1961 to a Pfizer group on an improved process for synthesis of what they call CJ4 aldehyde by this procedure. Our pharmaceutical chemistry friends nod their heads and say that CH aldehyde is a very important intermediate in the synthesis of vitamin A and that any improvements at this point of the s.ynthesis are doubly welcome. Since methyl and etlwl chloroacetates, which are mentioned prominently as leading to maximum yields, are also the cheapest of the esters, it stands to reason that someone is happy. Reaction of the chloroacetic esters with semicarbazones to form hydantoins has also been the subject of a patent. For instance, this reaction is reported: (CH3)2C = NNHCONH 2 + ClCH2COOR NaOMe CH3 O > \ / C = N—N—C CH3 I NH CH 2 —C=0 These (-ylideneamino) hydantoins have the useful property of being able to exchange smoothly with other carbonylcontaining molecules which do not form the aminoltydantoms so directly themselves. An example mentioned is the formation of the antibacterial, l-(5'nitro-2/-furfur%ylideneamino)-hydantoin. Several examples of a related reaction have been reported by Bon and Tisler where thiazolidones are obtained instead of the hydantoin derivative. S / NaOAc 0NHC NHNHo + ClCH2COOR >
/ N—NH2 0 These compounds were somewhat unexpected in view of previous reports that 1,3,4-thiadiazoles are formed in other similar cases. Anyway, whichever of these you are trying to* make, Kay-Fries has all of the chloroacetic ester you are likely to need. Technical data sheets are available. Just write for them or for the specific references to the reactions above.
Kay-Fries Chemicals, Inc. 360 Lexington Ave., New York 17, N. Y. JUNE
2 4, 1963
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