Boron manufacture

By far the most commercially important boron compound in terms of dollar sales is Na2B407.5H20. This pentahydrate is used in very large quantities in the manufacture of insulation fiberglass and sodium perborate bleach. 

Boric acid is also an important boron compound with major markets in textile products. Use of borax as a mild antiseptic is minor in terms of dollars and tons. Boron compounds are also extensively used in the manufacture of borosilicate glasses. Other boron compounds show promise in treating arthritis. 

Cera.micA.bla.tors, Several types of subliming or melting ceramic ablators have been used or considered for use in dielectric appHcations particularly with quartz or boron nitride [10043-11 -5] fiber reinforcements to form a nonconductive char. Fused siHca is available in both nonporous (optically transparent) and porous (sHp cast) forms. Ford Aerospace manufactures a 3D siHca-fiber-reinforced composite densified with coUoidal siHca (37). The material, designated AS-3DX, demonstrates improved mechanical toughness compared to monolithic ceramics. Other dielectric ceramic composites have been used with performance improvements over monolithic ceramics (see COMPOSITE MATERIALS, CERAMIC MATRIX). 

Diamond. Diamond [7782 0-3] is the hardest substance known (see Carbon, diamond, natural). It has a Knoop hardness of 78—80 kN/m (8000—8200 kgf/m ). The next hardest substance is cubic boron nitride with a Knoop value of 46 kN/m, and its inventor, Wentorf, beheves that no manufactured material will ever exceed diamond s hardness (17). In 1987 the world production of natural industrial diamonds (4) was about 110 t (1 g = 5 carats). It should be noted that whereas the United States was the leading consumer of industrial diamonds in 1987 (140 t) only 260 kg of natural industrial diamonds were consumed this is the lowest figure in 48 years (4), illustrating the impact that synthetic diamonds have made on the natural diamond abrasive market. 

Table 3. Manufacturers and Trade Names of Boron Flame Retardants...

Manufacture. Boron trifluoride is prepared by the reaction of a boron-containing material and a fluorine-containing substance in the presence of an acid. The traditional method used borax, fluorspar, and sulfuric acid. 

Manufacture, Shipping, and Waste Treatment. Fluoroboric acid (48%) is made commercially by direct reaction of 70% hydroduoric acid and boric acid, H BO (see Boron compounds). The reaction is exothermic and must be controlled by cooling. 

Isopropylnaphthalenes can be prepared readily by the catalytic alkylation of naphthalene with propjiene. 2-lsopropylnaphthalene [2027-17-0] is an important intermediate used in the manufacture of 2-naphthol (see Naphthalenederivatives). The alkylation of naphthalene with propjiene, preferably in an inert solvent at 40—100°C with an aluminum chloride, hydrogen fluoride, or boron trifluoride—phosphoric acid catalyst, gives 90—95% wt % 2-isopropylnaphthalene however, a considerable amount of polyalkylate also is produced. Preferably, the propylation of naphthalene is carried out in the vapor phase in a continuous manner, over a phosphoric acid on kieselguhr catalyst under pressure at ca 220—250°C. The alkylate, which is low in di- and polyisopropylnaphthalenes, then is isomerized by recycling over the same catalyst at 240°C or by using aluminum chloride catalyst at 80°C. After distillation, a product containing >90 wt % 2-isopropylnaphthalene is obtained (47). 

Phosgene can be employed in a variety of metal-recovery operations, eg, in the recovery of platinum, uranium, plutonium, and niobium (69—73). Phosgene has been proposed for the manufacture of aluminum chloride, beryllium chloride, and boron trichloride (74—76). Phosgene has been patented as a stabilizer, either by itself or in combination with thionyl chloride, for Hquid SO2 (77). 

Continuous-Flow Stirred-Tank Reactors. The synthesis of j )-tolualdehyde from toluene and carbon monoxide has been carried out using CSTR equipment (81). -Tolualdehyde (PTAL) is an intermediate in the manufacture of terephthabc acid. Hydrogen fluoride—boron trifluoride catalyzes the carbonylation of toluene to PTAL. In the industrial process, separate stirred tanks are used for each process step. Toluene and recycle HF and BF ... 

Approximately 5% of the U.S. consumption of is in agriculture. Boron is a necessary trace nutrient for plants and is added in small quantities to a number of fertilizers. Borates are also used in crop sprays for fast rehef of boron deficiency. Borates, when apphed at relatively high concentration, act as nonselective herbicides. Small quantities of borates are used in the manufacture of alloys and refractories (qv). Molten borates readily dissolve other metal oxides usage as a flux in metallurgy is an important apphcation. Other important small volume apphcations for borates are in fire retardants for both plastics and ceUulosic materials, in hydrocarbon fuels for fungus control, and in automotive antifreeze for corrosion control (see Corrosion and corrosion inhibitors). Borates are used as neutron absorbers in nuclear reactors. Several borates, which are registered with the Environmental Protection Agency (EPA) can be used for insecticidal purposes, eg, TIM-BOR. 

Hydrocarbon Oxidation. The oxidation of hydrocarbons (qv) and hydrocarbon derivatives can be significantly altered by boron compounds. Several large-scale commercial processes, such as the oxidation of cyclohexane to a cyclohexanol—cyclohexanone mixture in nylon manufacture, are based on boron compounds (see Cylcohexanoland cyclohexanone Eibers, polyamide). A number of patents have been issued on the use of borate esters and boroxines in hydrocarbon oxidation reactions, but commercial processes apparently use boric acid as the preferred boron source. The Hterature in this field has been covered through 1967 (47). Since that time the Hterature consists of foreign patents, but no significant appHcations have been reported for borate esters. 

Boron Triiodide. Boron ttiiodide is not manufactured on a large scale. Small-scale production of BI from boron and iodine is possible in the temperature range 700—900°C (70—72). Excess I2 can be removed as Snl by reaction with Sn, followed by distillation (71). The reaction of metal tetrahydroborates and I2 is convenient for laboratory preparation of BI (73,74). BI can also by synthesized from B2H and HI in a furnace at 250°C (75), or by the reaction of B with excess Agl or Cul between 450—700°C, under vacuum (76). High purity BI has been prepared by the reaction of I2 with mixtures of boron carbide and calcium carbide at elevated temperatures. 

Boron Trichloride. Approximately 75—95% of the BCl consumed iu the United States is used to prepare boron filaments by CVD (7). These high performance fibers are used to reinforce composite materials (qv) made from epoxy resius and metals (Al, Ti). The principal markets for such composites are aerospace industries and sports equipment manufacturers. 

Boron Bromide. Approximately 30% of BBr produced in the United States is consumed in the manufacture of proprietory pharmaceuticals (qv) (7). BBr is used in the manufacture of isotopicaHy enriched crystalline boron, as a Etiedel-Crafts catalyst in various polymerization, alkylation, and acylation reactions, and in semiconductor doping and etching. Examples of use of BBr as a catalyst include copolymerization of butadiene with olefins (112) polymerization of ethylene and propylene (113), and A/-vinylcarbazole (114) in hydroboration reactions and in tritium labeling of steroids and aryl rings (5). 

Boron Triiodide. There are no large-scale commercial uses of boron ttiiodide. It can cleave ethers without affecting aldehyde groups and thus finds use in the synthesis of the antibiotic fmstulosin (115,116). BI is used to prepare Snl, Sbl, and Til (117) in 99—100% yield. It is used to clean equipment for handling UE (118) and in the manufacture of lithium batteries (119). 

Dlbor ine(6). This compound is manufactured by Gallery Chemical Co. ia Gallery, Peimsylvania. Laboratory-scale preparations are given ia equations 4—64 5 6, of which the last may be the most convenient method. Diborane is the most important starting material for all the other boron hydrides. 

Diborane(6), B2H. This spontaneously flammable gas is consumed primarily by the electronics industry as a dopant in the production of siHcon wafers for use in semiconductors. It is also used to produce amine boranes and the higher boron hydrides. Gallery Chemical Co., a division of Mine Safety AppHances Co., and Voltaix, Inc., are the main U.S. producers of this substance. Several hundred thousand pounds were manufactured worldwide in 1990. 

Sodium tetrabydroborate [16940-66-2] NaBH, more commonly called sodium borobydride, is tbe most widely used commercial boron bydride. Tbe largest manufacturer is Morton International Specialty Chemicals Group, which has two plants in the United States and one in Europe (1). Oy Nokia Ab Chemicals (FN) (2) also produces commercial quantities. Smaller producers include Farbenfabrik Bayer A.G. and ChemetaH Gmbh in Germany (2). 

Boron tribromide [10294-33A], BBr, is used in the manufacture of diborane and in the production of ultra high purity boron (see Boron, ELEMENTAL BoRON COMPOUNDS). Anhydrous aluminum bromide [7727-15-3], AIBr., is used as an acid catalyst in organic syntheses where it is more reactive and more soluble in organic solvents than AlCl. Tballium bromide [7789AOA], TlBr, is claimed as a component in radiographic image conversion panels (39). 

Beryllium, calcium, boron, and aluminum act in a similar manner. Malonic acid is made from monochloroacetic acid by reaction with potassium cyanide followed by hydrolysis. The acid and the intermediate cyanoacetic acid are used for the synthesis of polymethine dyes, synthetic caffeine, and for the manufacture of diethyl malonate, which is used in the synthesis of barbiturates. Most metals dissolve in aqueous potassium cyanide solutions in the presence of oxygen to form complex cyanides (see Coordination compounds). 

Dihydroxyanthraquinone. This anthraquinone, also known as quinizarin [81-64-1] (29), is of great importance in manufacturing disperse, acid, and vat dyes. It is manufactured by condensation of phthalic anhydride (27) with 4-chlorophenol [106-48-9] (28) in oleum in the presence of boric acid or boron trifluoride (40,41). Improved processes for reducing waste acid have been reported (42), and yield is around 80% on the basis of 4-chlorophenol. 

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