Union Carbide Alcohols

Diisobutyl Carbinol Etiionol, 95% 2 Etby hrx.ooot Isobutonol 

Isopropanol, Anhydrous Methyl Amyl Alcohol 2-Methyl Butonol n-Pentonol n-Proponol 

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Ma.nufa.cture. The principal manufacturers of vinyl ethers are BASF, GAF, and Union Carbide. The first two utilize vinylation of alcohols, whereas the last reportedly uses cracking of acetals. 

Secondary alcohols (C q—for surfactant iatermediates are produced by hydrolysis of secondary alkyl borate or boroxiae esters formed when paraffin hydrocarbons are air-oxidized ia the presence of boric acid [10043-35-3] (19,20). Union Carbide Corporation operated a plant ia the United States from 1964 until 1977. A plant built by Nippon Shokubai (Japan Catalytic Chemical) ia 1972 ia Kawasaki, Japan was expanded to 30,000 t/yr capacity ia 1980 (20). The process has been operated iadustriaHy ia the USSR siace 1959 (21). Also, predominantiy primary alcohols are produced ia large volumes ia the USSR by reduction of fatty acids, or their methyl esters, from permanganate-catalyzed air oxidation of paraffin hydrocarbons (22). The paraffin oxidation is carried out ia the temperature range 150—180°C at a paraffin conversion generally below 20% to a mixture of trialkyl borate, (RO)2B, and trialkyl boroxiae, (ROBO). Unconverted paraffin is separated from the product mixture by flash distillation. After hydrolysis of residual borate esters, the boric acid is recovered for recycle and the alcohols are purified by washing and distillation (19,20). 

The product secondary alcohols from paraffin oxidation are converted to ethylene oxide adducts (alcohol ethoxylates) which are marketed by Japan Catalytic Chemical and BP Chemicals as SOFTANOL secondary alcohol ethoxylates. Union Carbide Chemical markets ethoxylated derivatives of the materials ia the United States under the TERGlTOL trademark (23). 

DIBK can be produced by the hydrogenation of phorone which, in turn, is produced by the acid-catalyzed aldol condensation of acetone. It is also a by-product in the manufacture of methyl isobutyl ketone. Diisobutyl ketone ( 1.37/kg, October 1994) is produced in the United States by Union Carbide (Institute, West Virginia) and Eastman (Kingsport, Teimessee) (47), and is mainly used as a coating solvent. Catalytic hydrogenation of diisobutyl ketone produces the alcohol 2,6-dimethyl-4-heptanol [108-82-7]. 

Mixtures of isomeric amyl alcohols (1-pentanol and 2-methyl-1-butanol) are often preferred because the different degree of branching imparts a more desirable combination of properties they are also less expensive to produce commercially. One such mixture is a commercial product sold under the name Primary Amyl Alcohol by Union Carbide Chemicals and Plastics Company Inc. 

Commercial primary amyl alcohol is a mixture of 1-pentanol and 2-methyl-1-butanol, iu a ratio of ca 65 to 35 (available from Union Carbide Chemicals and Plastics Company Inc. iu other ratios upon request). Typical physical properties of this amyl alcohol mixture are Hsted iu Table 2 (17). 

Prior to 1975, reaction of mixed butenes with syn gas required high temperatures (160—180°C) and high pressures 20—40 MPa (3000—6000 psi), in the presence of a cobalt catalyst system, to produce / -valeraldehyde and 2-methylbutyraldehyde. Even after commercialization of the low pressure 0x0 process in 1975, a practical process was not available for amyl alcohols because of low hydroformylation rates of internal bonds of isomeric butenes (91,94). More recent developments in catalysts have made low pressure 0x0 process technology commercially viable for production of low cost / -valeraldehyde, 2-methylbutyraldehyde, and isovaleraldehyde, and the corresponding alcohols in pure form. The producers are Union Carbide Chemicals and Plastic Company Inc., BASF, Hoechst AG, and BP Chemicals. 

Union Carbide Chemicals and Plastics Company Inc. is the only producer of C-5 oxo derived alcohols (148,150) in the United States. About 75% of the 30,000 t of valeraldehyde and 2-methylbutyraldehyde produced by the oxo process was converted to the isomeric mixture of primary amyl alcohols in 1988 (150). The primary amyl alcohol mixture was available in tank car quantities for 1.02/kg in 1991. The Dow Chemical Company appears to have stopped commercial production of / fZ-amyl alcohol (151). 

Another significant appHcation for amyl alcohols is for production of amyl acetates. Production of amyl acetates in 1987 is estimated to have been 4.5-5.5 X 10 t about 50% of the domestic demand is for lacquers (150). Union Carbide Chemicals and Plastics Company Inc. is the only U.S. producer. 

UCAR Alcohols for Coatings Applications, Brochure F-48588, Solvents and Coatings Materials Division, Union Carbide Chemicals and Plastics Corp., Danbury, Conn., Sept. 1984. 

Company (Bayway, New Jersey). This was followed in 1921, by the start-up of isopropyl alcohol production in Clendenin, West Virginia, by the Carbide and Carbon Chemicals (Union Carbide) Corporation. The Shell Oil Company began production in the 1930s at Dominguez, California (55). These three companies are the principal domestic manufacturers as of the mid-1990s. 

A three-step process involving the oxidation of acetophenone, hydrogenation of the ketone to a-phenylethanol, and dehydration of the alcohol to styrene was practiced commercially by Union Carbide (59) until the early 1960s. Other technologies considered during the infancy of the styrene industry include side-chain chlorination of ethylbenzene followed by dehydrochlotination or followed by hydrolysis and dehydration. 

There are two main processes for the synthesis of ethyl alcohol from ethylene. The eadiest to be developed (in 1930 by Union Carbide Corp.) was the indirect hydration process, variously called the strong sulfuric acid—ethylene process, the ethyl sulfate process, the esterification—hydrolysis process, or the sulfation—hydrolysis process. This process is stiU in use in Russia. The other synthesis process, designed to eliminate the use of sulfuric acid and which, since the early 1970s, has completely supplanted the old sulfuric acid process in the United States, is the direct hydration process. This process, the catalytic vapor-phase hydration of ethylene, is now practiced by only three U.S. companies Union Carbide Corp. (UCC), Quantum Chemical Corp., and Eastman Chemical Co. (a Division of Eastman Kodak Co.). UCC imports cmde industrial ethanol, CIE, from SADAF (the joint venture of SABIC and Pecten [Shell]) in Saudi Arabia, and refines it to industrial grade. 

Union Carbide refines cmde industrial alcohol imported from Saudi Arabia. Includes Russia. 

The most common BW antifoam employed today is UCON 50-HB-5100, from Union Carbide Corporation, which is the linear POP(33), POE(45) ether of butyl alcohol, or polyalkylene glycol monobutylether (PAGMBE). 

Isopropyl alcohol (IPA) or benzyl alcohol (toluol) often are used in the formulation (as early components in the order of addition) to dissolve the surfactant-detergent base [e.g., Duomeen OL (Akzo Nobel Chemicals, Inc.) or Triton N101 (Union Carbide Corp.)]. 

Tetrahydrobenzyl alcohol (( )3-cyclohexenene-l-methanol) and 30% aqueous hydrogen peroxide were purchased from Fluka, AG. 3-Cyclohexene-1-carboxylic acid and cis-4-cyclohexene-l,2-dicarboxylic acid were used as purchased from Lancaster Chemical Co. Methyl iodide, acetic anhydride, Oxone (potassium peroxymonosulfate), Aliquot 336 (methyl tri-n-octylammonium chloride), sodium tungstate dihydrate and N,N-dimethylaminopyridine (DMAP) were purchased from Aldrich Chemical Co. and used as received. 3,4-Epoxycyclohexylmethyl 3, 4 -epoxycyclohexane carboxylate (ERL 4221) and 4-vinylcyclohexene dioxide were used as purchased from the Union Carbide Corp. (4-n-Octyloxyphenyl)phenyliodonium hexafluoroantimonate used as a photoinitiator was prepared by a procedure described previously (4). 

The /-butyl alcohol was a commercial product obtained from Matheson Coleman and Bell, and the glacial acetic acid a commercial product obtained from Union Carbide. 

Union Carbide Corporation Unpublished data cited in Rowe VK, McCollister SB, Alcohols. In Clayton CD, Clayton FE (eds) Patty s Industrial Hygiene and Toxicology, 3rd ed, Vol 2C, Toxicolo, pp 4620-4623. New York, Wiley-Interscience, 1982... 

The oxidative coupling of CO in the presence of an alcohol to yield oxalate esters is under study by Ube Industries and Union Carbide. As oxidizing agent, oxygen or nitric oxide (Equation 8 and 9) can be used in the presence of a palladium catalyst (7 ). 

Union Carbide invented the industrial use of highly active ligand-modified rhodium complexes.90-93 [RhH(CO)(PPh3)3], the most widely used catalyst, operates under mild reaction conditions (90-120°C, 10-50 atm). This process, therefore, is also called low-pressure oxo process. Important features of the rhodium-catalyzed hydroformylation are the high selectivity to n-aldehydes (about 92%) and the formation of very low amounts of alcohols and alkanes. Purification of the reactants, however, is necessary because of low catalyst concentrations. 

Such as Tergitol 15-S-7, C11-C15 secondary alcohol ethoxylate (Union Carbide) or Genapol 24-L-60 linear alcohol ethoxylate (Hoechst Celanese). 

Anthony J. Papa, Union Carbide Chemicals and Plastics Company, Inc.. South Charleston, WV. http //www.unioncarbide.com/. Amyl Alcohols... 

The carbonyl functionality of MIBK can be hydrogenated over nickel catalysts to yield methyl isobutyl carbinol (4-methyl-2-pentanol or methyl amyl alcohol) [108-11-2]. Industrial processes coproduce methyl isobutyl carbinol during the hydrogenation of mesityl oxide to MIBK. The product ratio of methyl isobutyl carbinol—MIBK during this reaction can be shifted toward methyl isobutyl carbinol by adopting a higher than normal pressure and H2 organic ratio (59). Methyl isobutyl carbinol is used as an ore flotation frother and to produce zinc dialkyl dithiophosphate lube oil additives. It is produced in the United States by Shell and Union Carbide ( 1.12/kg, October 1994). 

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