Commercial uses

A number of commercial phosphoms-containing polyols have been made by the reaction of propylene oxide and phosphoric or polyphosphoric acid. Some have seen commercial use but tend to have hydrolytic stabiHty limitations and are relatively low in phosphoms content. BASF s Pluracol 684 is a high functionahty polyol containing 4.5% P, sold for Class 11 rigid foam use. 

Manufacture. For the commercial production of DPXN (di-/)-xylylene) (3), two principal synthetic routes have been used the direct pyrolysis of -xylene (4, X = Y = H) and the 1,6-Hofmaim elimination of ammonium (HNR3 ) from a quaternary ammonium hydroxide (4, X = H, Y = NR3 ). Most of the routes to DPX share a common strategy PX is generated at a controlled rate in a dilute medium, so that its conversion to dimer is favored over the conversion to polymer. The polymer by-product is of no value because it can neither be recycled nor processed into a commercially useful form. Its formation is minimised by careful attention to process engineering. The chemistry of the direct pyrolysis route is shown in equation 1  

Principal Adsorbent Types. Commercially useful adsorbents can be classified by the nature of their stmcture (amorphous or crystalline), by the sizes of their pores (micropores, mesopores, and macropores), by the nature of their surfaces (polar, nonpolar, or intermediate), or by their chemical composition. AH of these characteristics are important in the selection of the best adsorbent for any particular appHcation. 

Oligomeric Phosphate—Phosphonate. A commercially used reactive oligomeric alcohol, Akzo s Eyrol 51 [70715-06-9] has a stmcture approximately represented by (110)  

The only other petrochemical feedstock of significant commercial use is methane (natural gas) which is used primarily to produce ammonia and methanol. Consumption factors are about 28 GJ and 31 GJ per metric ton, respectively (58,300 and 64,700 BTU/lb) (8). Approximately 

Two ammoniation processes, ie, the THPOH—NH and the precondensate—NH processes, have seen considerable commercial use. 

Europium oxide is now widely used as a phospor activator and europium-activated yttrium vanadate is in commercial use as the red phosphor in color TV tubes. Europium-doped plastic has been used as a laser material. With the development of ion-exchange techniques and special processes, the cost of the metal has been greatly reduced in recent years. 

Sisal. The tme sisal fiber Fora Agave sisalana is the most important of the leaf fibers ia terms of quahty and commercial use. Originating ia the tropical western hemisphere, sisal has beea transplanted to East Africa, Indonesia, and the Philippines. It is named after the port ia the Yucatan from which it was first exported. 

Acrylonitrile and its comonomers can be polymerized by any of the weU-known free-radical methods. Bulk polymerization is the most fundamental of these, but its commercial use is limited by its autocatalytic nature. Aqueous dispersion polymerization is the most common commercial method, whereas solution polymerization is used ia cases where the spinning dope can be prepared directly from the polymerization reaction product. Emulsion polymerization is used primarily for modacryhc compositions where a high level of a water-iasoluble monomer is used or where the monomer mixture is relatively slow reacting. 

An organic Hquid extractant is used to remove the HCl and to shift the reaction in the desired direction. After concentration, the by-product hydrochloric acid is suitable for commercial use. 

Furfural—acetone resins have been used to form resin-aggregate mixtures referred to as organic concretes. Despite the reportedly excellent properties, there has been virtually no commercial use of such resins outside the former Soviet Union. The stmctures and polymerization mechanisms of these furfural—aldehyde—ketone polymers are discussed in a review (6). 

While hopes are high, heterogeneous photochemical systems seem not yet to have found major practical application. The photovoltaic cell or solar cell is the only system with important (although specialized) commercial use (see Ref. 343). 

Polymerization. In the absence of inhibitors, acrolein polymerizes readily in the presence of anionic, cationic, or free-radical agents. The resulting polymer is an insoluble, highly cross-linked soHd with no known commercial use. 

Acetylene-Based Routes. Walter Reppe, the father of modem acetylene chemistry, discovered the reaction of nickel carbonyl with acetylene and water or alcohols to give acryUc acid or esters (75,76). This discovery led to several processes which have been in commercial use. The original Reppe reaction requires a stoichiometric ratio of nickel carbonyl to acetylene. The Rohm and Haas modified or semicatalytic process provides 60—80% of the carbon monoxide from a separate carbon monoxide feed and the remainder from nickel carbonyl (77—78). The reactions for the synthesis of ethyl acrylate are 

Red Phosphorus. This aHotropic form of phosphoms is relatively nontoxic and, unlike white phosphoms, is not spontaneously flammable. Red phosphoms is, however, easily ignited. It is a polymeric form of phosphoms having thermal stabiUty up to ca 450°C. In finely divided form it has been found to be a powerful flame-retardant additive (26,45—47). In Europe, it has found commercial use ia molded nylon electrical parts ia a coated and stabilized form. Handling hazards and color have deterred broad usage. The development of a series of masterbatches by Albright Wilson should facihtate further use. 

Others would include the addition of materials aimed at increa sing the bioavailabiUty of the contaminant to the degrading organisms. The most studied compounds are surfactants, but cations have been reported to increase the bioavailabiUty of some organic compounds, and sorbents and clays are also considered. The dispersion of spilled oil on water by the appHcation of dispersants is perhaps the major commercial use of this idea. 

Aryl Phosphates. Aryl phosphates were introduced into commercial use early in the twentieth century for flammable plastics such as cellulose nitrate and later for cellulose acetate. CeUulosics are a significant area of use but are exceeded now by plastici2ed vinyls (93—95). Principal appHcations are in wire and cable insulation, coimectors, automotive interiors, vinyl moisture barriers, plastic greenhouses (Japan), furniture upholstery, conveyer belts (especially in mining), and vinyl foams. 

Typical nonsieve, polar adsorbents are siUca gel and activated alumina. Kquilihrium data have been pubUshed on many systems (11—16,46,47). The order of affinity for various chemical species is saturated hydrocarbons < aromatic hydrocarbons = halogenated hydrocarbons < ethers = esters = ketones < amines = alcohols < carboxylic acids. In general, the selectivities are parallel to those obtained by the use of selective polar solvents in hydrocarbon systems, even the magnitudes are similar. Consequendy, the commercial use of these adsorbents must compete with solvent-extraction techniques. 

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