Commercial products peroxides

Di-teo-propyl ether. The commercial product usually contains appreciable quantities of peroxides these should be removed by treatment with an acidified solution of a ferrous salt or with a solution of sodium sulphite (see under Diethyl ether). The ether is then dried with anhydrous calcium chloride and distilled. Pure di-iao-propyl ether has b.p. 68-5°/760 mm. 

Hexafluoiopiopylene and tetiafluoioethylene aie copolymerized, with trichloiacetyl peroxide as the catalyst, at low temperature (43). Newer catalytic methods, including irradiation, achieve copolymerization at different temperatures (44,45). Aqueous and nonaqueous dispersion polymerizations appear to be the most convenient routes to commercial production (1,46—50). The polymerization conditions are similar to those of TFE homopolymer dispersion polymerization. The copolymer of HFP—TFE is a random copolymer that is, HFP units add to the growing chains at random intervals. The optimal composition of the copolymer requires that the mechanical properties are retained in the usable range and that the melt viscosity is low enough for easy melt processing. 

The electrolytic processes for commercial production of hydrogen peroxide are based on (/) the oxidation of sulfuric acid or sulfates to peroxydisulfuric acid [13445-49-3] (peroxydisulfates) with the formation of hydrogen and (2) the double hydrolysis of the peroxydisulfuric acid (peroxydisulfates) to Caro s acid and then hydrogen peroxide. To avoid electrolysis of water, smooth platinum electrodes are used because of the high oxygen overvoltage. The overall reaction is... 

In spite of widespread usage of these compounds, the stmctures of only the calcium, barium, and strontium compounds are reasonably weU-estabhshed. The materials are generally made by trituratiag the oxides, or hydroxides, with aqueous hydrogen peroxide and dryiag the soHd products. The commercial products are typically mixtures of the peroxides with varyiag amounts of hydroxides, oxides, carbonates, hydrates, and peroxohydrates. 

Calcium Peroxide. Pure calcium peroxide [1305-79-9] Ca02, has been prepared, but the commercial product is a mixture made by reaction of calcium hydroxide and hydrogen peroxide. Commercial material contains either 60 or 75% Ca02 the remainder is a poorly defined mixture of calcium oxide, hydroxide, and carbonate. A well-defined octahydrate [60762-59-6] 8H20, can be crysta11i2ed from aqueous systems. 

Zinc Peroxide. Zinc peroxide [1314-22-3] is a yellow soHd, generally similar to magnesium peroxide. The commercial product is a pale... 

Decomposition Hazards. The main causes of unintended decompositions of organic peroxides are heat energy from heating sources and mechanical shock, eg, impact or friction. In addition, certain contaminants, ie, metal salts, amines, acids, and bases, initiate or accelerate organic peroxide decompositions at temperatures at which the peroxide is normally stable. These reactions also Hberate heat, thus further accelerating the decomposition. Commercial products often contain diluents that desensitize neat peroxides to these hazards. Commercial organic peroxide decompositions are low order deflagrations rather than detonations (279). 

Calendering processes, of great importance in the production of sheet materials from PVC compounds, are little used with polyethylene because of the difficulty in obtaining a smooth sheet. Commercial products have, however, been made by calendering low-density polymer containing a small amount of a peroxide such as benzoyl peroxide to give a stiff but crinkly sheet (Crinothene) which was suitable for lampshades and other decorative applications. 

In concentrated sulfuric acid solutions at HAP, the adsorbed HS04 ions are converted, according to reaction (15.57), to HS 04 radicals which dimerize, forming peroxydisulfuric (persulfuric) acid H2S2O8. This acid is the intermediate for one of the commercialized methods of hydrogen peroxide production. The first efforts toward the electrosynthesis of peroxydisulfuric acid go back to 1878 commercial production started in 1908. The standard electrode potential of the overall reaction... 

Monomethylhydrazine is a clear, colorless liquid (Trochimowicz 1994). Upon contact with strong oxidizers (e.g., hydrogen peroxide, nitrogen tetroxide, chlorine, fluorine) spontaneous ignition may occur. It is used in military applications as a missile and rocket propellant in chemical power sources (USAF 1989), and is used also as a solvent and chemical intermediate (Trochimowicz 1994). There are are no reports of current commercial production (HSDB 1996) and, therefore, overall production may be considered sporadic (Chemical Economics Handbook 2000). 

Tetrahydrofuran freshly distilled from lithium aluminum hydride should be used. A commercial product with a peroxide content giving a positive iodine test must be treated with about 0.3% of cuprous chloride (boiling for 30 minutes and distillation) before the addition of the hydride. 

In conjunction with the chiral anion TRIP (156) (10 mol%), diamine 157 (10 mol%) can be used in the catalytic asymmetric epoxidation of a,p-unsaturated ketones (>90% ee) [196], while the secondary amine 158 (10 mol%) can be used for the epoxidation of both di- and trisubstituted a,P-unsaturated aldehydes (92-98% ee) (Fig. 15) [211], The facile nature of these reactions, using commercially available peroxides as the stoichiometric oxidant, together with the synthetic utility of the epoxide products suggests application in target oriented synthesis. 

Barium peroxide was used in commercial production of oxygen in the past. Heating harium oxide in air at 500°C forms barium peroxide, which decomposes at 800°C to yield oxygen ... 

Studies carried out with complete cells in vivo, cell membranes and other cell fractions point to the selective oxidation of phosphatidylserine (26) to a hydroperoxide (PS-OOH) on oxidative stress caused by toxic agents such as H2O2, t-BuOOH and cumyl hydroperoxide (27). Formation of PS-OOH is observed during apoptosis. These phenomena are important because of the cytotoxic effects of various peroxides used in commercial products coming into direct contact with the human body, as is the case of epidermal keratinocytes in contact with cosmetic formulations" ". The toxic effects of f-BuOOH are associated with vasoconstriction and damage to the vascular smooth muscles ". Global determination methods for primary lipid oxidation products are discussed in Section IV.B. 

The work of Kuchta (Ref 16) confirms that the relative concns of Hydrogen Peroxide /org subs are more important in defining the explosibility of a mixt than the type of org subst used. He points out that detonation can be initiated in certain H202 purge liquors that may form in commercial production of Hydrogen Peroxide... 

The commercial product of the Lucidol Division contains a minimum of 95% of peroxide active oxygen 5.8% (min). It is a white fine powder mp 60-65°... 

Compositions and functions of typical commercial products in the 2-alkyl-l-(2-hydroxyethyl)-2-imidazolines series are given in Table 29. 2-Alkyl-l-(2-hydroxyethyl)-2-imidazolines are used in hydrocarbon and aqueous systems as antistatic agents, corrosion inhibitors, detergents, emulsifiers, softeners, and viscosity builders. They are prepared by heating the salt of a carboxylic acid with (2-hydroxyethyl)ethylenediamine at 150—160°C to form a substituted amide 1 mol water is eliminated to form the substituted imidazoline with further heating at 180—200°C. Substituted imidazolines yield three series of cationic surfactants by ethoxylation to form more hydrophilic products quatemization with benzyl chloride, dimethyl sulfate, and other alkyl halides and oxidation with hydrogen peroxide to amine oxides. 

Sodium dioxide is an important commercial product the other alkali peroxides are more of the character of chemical curiosities. According to J. Scott,28 sodium dioxide has a micro-crystalline structure. Some of the properties of the dioxide are tabulated in the following scheme ... 

Solid acetyl peroxide is not accepted for shipping but its 25% soln in dimethyl phthlate, the commercial product which serves as an oxidizer, Is acceptable for shipment by commercial carriers (Refs 14,... 

Commercial Dibenzoyl peroxide is manufd in this country under the name "Lucidol "by the Luc idol Division of Wallace Tiernan Inc, Buffalo, NY. Other trade names of the coml product are Luperco"(finely dispersed with an org or inorg filler) and "Luperox" (pastes, dispersed in water or oils of various types)... 

O 16.06% active 0 8.04%. The commercial product of the Lucidol Div, contains a minimum of 95.0% of dilauroyl peroxide with. min active O 3.76%. It consists of wh soft granules with mp 48—50° insol in w si sol in alcohols sol in esters, vegetable oils and petr solvents very sol in chlorobenzene, chlf, CS2, CC14, toluene, dichloromethane, ethylenedichlotide and trichloroethylene. 

Hydrogen peroxide is a very weak acid and in aqueous solutions only dissociates slightly (eq. 14) Ka = 1.78 x 10-12. Undissociated hydrogen peroxide is relatively stable, and for this reason all commercial products are adjusted to an acid pH (62). 

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