Document pmNKnRqbB9pkppXNnY943xOa6

manufacture oi 1,1.1-trichloroethan- If mixed oxides of line, manganese, Acetone etc., all vinyl -chlbride is used to pro- chromium, and aluminum tre used dote polyvinyl chloride or co as the catalysts, pressure of 300 atm Average annual production: 1 x 10* polymers of vinyl chloride and other at 300 *C is required With a copper kg value in U5S. 7 x 10* monomers. catalyst, a lower pressure of 75 atm Polyvinyl chloride is used exten suffices at 300 C. Less by-product is sively in the building and construc formed at the lower pressures. Process: Acetone is one product tion industry, as piping, floor cover from the peroxidation of cumene (see ing. and exterior surface, weather Phenols it is also manufactured by resistant covering. It is used in the in Uses: Small amounts of methyl the catalytic dehydrogenation of sulation of electrical wiring, in alcohol are used directly as a solvent isopropyl alcohol using a irass or packaging as a film, m apparel as a but most of the methyl alcohol pro copper catalyst and 3 atm pressure at coating on fabric to impart a sup duced is raw material for the manu 500 *C. By-product hydrogen is recov--, posedly improved esthetic appear facture of other compounds. These ered, acetone distilled off. and unre ance or more practically, for rain include formaldehyde (which see), acted alcohol recycled. coats, etc Polyvinyl chloride is used acetic acid--bv carboxylation. meth- for wale' ho:e, for tarpaulins yl tertiary butyl ether dimethyl teTM- Uses: To some extent directly as a (sometimes with a fabric backing), in phthalate. methyl methacrylate, and solvent, for example in the manufac some paints, and for many other pur methyl derivatives such as the ture of acetate rayon, but largely as a poses too numerous to describe in amines and the halides. As a blend raw material for the manufacture of detail. Polyvinyl chloride is the single with tertiary butyl alcohol methyl derivatives. Some derivatives are most important polymeric substance alcohol has some promise as an oc useful as solvents themselves, and as in use today. tane booster in gasolines. precursors also: methyl isobutyl ketone, methyl isobutyl carbinol, Remarks: The alleged car diacetone alcohol Acetone is a raw cinogenicity of vinyl chloride il Remarks: The carbon monoxide material for the manufacture of lustrates that political influence of and hydrogen raw materials are ob methyl and higher methacrylates and vociferous minorities can overwhelm- tained from synthesis gat, a mixture of some pharmaceuticals the need for proper attention to of carbon monoxide and hydrogen in scientific questions in deciding approximately the correct propor socially important issues. The facts tions for methyl alcohol synthesis. Remarks: Acetone is another of the are these- Humans exposed to vinyl Synthesis gas is obtained by treating few chemicals involved in recent chloride by skin contact at frequent methane or Other hydrocarbons (for geopolitical hulor, Celiu.ate nitrate intervals for long periods of time will example, the heavy hydrocarbon sometimes develop a cancer--sar residues from petroleum refining) coma of the liver Experimental with carbon dioxide and water at 800 animals exposed to vinyl chloride C in the presence of a nickel vapor at fairly low concentrations catalyst. When properly controlled, wilt also develop liver sarcomas The the major products are carbon limited evidence of human exposure monoxide and hydrogen to vinvl chloride vapor strongly sug In the synthesis of methyl alcohol gests that such exposure cannot pro the maior by-products are dimethyl is an explosive and is used as 'smokeless powder". Its manufacture during World War I required large amounts of acetone as a solvent At that time, the maior source of ace tone was from the destructive distilla tion of wood. The requirements for acetone were so great in England in 1915-1916 that English forests weie duce liver sarcomas. Yet, without re ether and higher alcohols. almost exhausted. Without the wood, quiring any further scientific Methyl tertiary butyl ether is used black powder, a militarily much less evidence, vinyl chloride antagonists primarily as an octane booster in drsirable explosive, would have to be in the United States were able to gasolines. It is also used in substituted. Through the efforts of politically force the vinyl chloride in laboratories in place of the more the editor of the Manchester Guar dustry to take the steps necessary to common ethers, diethyl ether and dian newspaper. David Lloyd George. preclude worker exposure to vinyl isopropyl ether, because, unlike these England's Prime Minister, asked a chloride vapor--at costs reflected in ethers it has little tendency to form young chemistry professor at the otherwise unnecessary price in ether peroxides on standing in the University of Manchester if he could creases. presence of air. Since ether peroxides find a solution. In less than ihree are quite unstable and detonate oc weeks he found another source- the Methyl Alcohol casionally with only a slight touch or controlled fermentation of corn impact, the use of methyl tertiary starch Refusing a proffered knight butvl ether as a solvent in laboratory hood. the professot gamed the pro Xiver.iue annual production: 3.4 x 10* work can be expected to increase. mise of an unspecified favor to be kg value m USJ. 1 x 10' Methyl alcohol is an intoxicant granted later. Bv late 1917, a pro and is found in trace amounts in all pitious time, the Foreign Secretary, Process: Bv direct synthesis using fermented and even m distilled Arthur James Balfour, promulgated carbon monoxide and hydrogen to alcoholic beverages When present in the Balfour Declaration as the favor form methyl alcohol: larger amounts by deliberate addi to the professor. Chaim Wenmann tion. it causes blindness and even Most historians agree that the CO + 2H,-wCH,OH death when ingested. Balfour Declaration was an essential 110 ucc 069024 maldehyde is the controlled oxida for several minutes until all o, th tion of methane or higher hydro phenol has been rubbed and .vera^e annual pfoJuclion: 2-7 a 10* v vaiie in USi: 5-5 * 10* carbons, the latter gwmg a variety of products that must be separated. This alternate is practical only when there scrubbed away. Alternate syntheses fr-r phenol in clude brine and benzene as the raw -Process: Catalytic vapor phase ox idation of methanol, using mixtures uf air and methanol. Silver or copper screen catalyst can be used, but a mixed outside catalyst (oxides of molybdenum, iron, vanadium) gives better yields--at higher cost. is a good market for the other prod ucts. , Formaldehyde polymerizes readily to the trimer, trioxane. and to higher not as well characterized polymers. It is often sold as a monomer in water solution with methanol as an in hibitor to minimize polymerization materials. The brine is electrolyzed to chlorine and sodium hydroxide (which see); chlorine plus benzene with an iron catalyst forms mono chlorobenzene (if controlled). The chlorobenzene reacts with sodium hydroxide to form phenol and sodium chloride, under acidic condi Uses: Formaldehyde is a raw material for the manufacture of a Trioxane. however, readily "monomerizes' in the presence of acid. tions. The sodium chloride is recy cled to chlorine and sodium hydrox wide variety of compounds. These irv ide. and so on. In the alkaline elude urea formaldehyde resins, hydrolysis of chlorobenzene, phenol formaldehyde resins, diphenyl ether is the expected major polyacetal resins, butanediol, hex Phenol side product. Its formation is amethylenetetramine. melamine for minimized by the deliberate addition maldehyde resins, tetrahydrofuran. and polyols such as pentaerythritrol and 2-ethyl-2(hydroxymethyl)-1, Average annual production: 1.2 x 10* kg; value m USS. 5 x 10* of diphenyl ether, an example of the application of Le Chatelieris principle. Another alternate is the oxidation 3-propanediol. The resins are partially co polymerized forms of their named components, used as adhesives, the resins are mixed with other solids (such as flakes of wood or other fibrous material) and the mixture heated under pressure. The resins then polymerize completely, binding the fibrous components to form a tough, durable structural material The other comoounds mentioned above are themselves the starting points for a wide variety of still other useful compounds: note that most of these derivatives are characterized Process: The peroxidation of cumene (isopropyl benzene) yields both phenol and acetone as the ma jor products, two steps are required: C.M,CH(CH,), + 0,-*C.M,C(CH,),OOH The process requires a pH near neutrality and 110 *C air supplies the needed oxygen, in the second step under acidic conditions, cumene hydroperoxide is decomposed into phenol and acetone. Other products include methylstyrene (sold or catalytically hydrogenated to cumene and recycled) and acetophenone of toluene to benzoic acid followed by the oxidation of this acid in the presence of a copper catalyst to phenol and carbon dioxide. This syn thesis is industrially useful only when the price of toluene is low and that of phenol high. Cumene is formed by the catalytic addition of benzene to propylene Doth are products (torn petroleum, often phenol plants are located near oil wells or shipping ports and are owned by the petroleum manufac turer. Some phenol is obtained as a by product of coke manuiacture by two or more active functional groups, amine or hydroxy in the ex amples mentioned, which provide (soldi: unreacted cumene is recyeJed. ^inyKlhloride ^ Uses: As a raw material for the the means for the preparation of a manufacture of phenol formalde Average annual production: 2.5 x variety of derivatives. hyde resins (see Formaldehyde) Sim 1C* kg; value in USS: 1.3 x 10' ilarly, for the manufacture of bisphen- Remarks: The oxidation of ol A (4,4Msopropylidene diphenol) from phenol and acetone--used in Process: 1,2-dichloroethane (socalled diehloroethvlene) is dehvdro- methanol to formaldehyde can be resin manufacture. Similarly, tor chlorinated using a charcoal or thought of as involving two reactions, polycarbonate resins. Some alkyl pumice catalyst at 3 atm and 500 C. dehydrogenation to form for derivatives of phenol can be used as The product vinyl chloride is quickly maldehyde. an endothermic process, surfactants. Phenol is used for the quenched with cold 1,2-dichloro and the. oxidation of methanol to for manufacture of adipic acid and of- ethane and then separated from the maldehyde and other products, an caorolactam. NH(CH,VCQ, both are quern-hant and from minor by-prod exothermic process. For optimum for precursors of nylon. ucts by distillation maldehyde production, the tempera The 1.2-dichloroethanc is itself pro ture should be about 500 *C to Remarks: The unique toxicity of duced in the same plant or m a achieve this, the ratio of air and phenol is not well-known--it is rapid separate but adiacent plant by the methanol introduced into the reac ly absorbed through the intact skin addition of chlorine to ethylene in tion region ii balanced so that the and unless the area of skin affected is the presence of 1.2-dibromoethane, endo- and exothermic reactions, quite small, the effect is known to be using an aluminum chloride or iron along with radiant heat lau, maintain fatal widen kt little as two minutes. (III) chloride catalyst at 50 C the reaction region at the Optimum The remedy is immediate and temperature. vigorous tubbing and scrubbing Uses: txfcpt for some very small An alternate preparation of for under flowing water with a cloth pad uses as the raw material for tfie 1 i\J ucc 069025