Chlorinated phosphates

An overview is provided of ongoing risk assessments on halogenated phosphate ester flame retardants in Europe. On the basis of the so-called second and fourth Priority lists on Existing Chemicals (Council Regulation No793/93) three chlorinated phosphate ester flame retardants are selected. The selection is based on their hazard profile, volume and use pattern. The three substances involved are TCPP, TDCP and TCEP (Antiblaze V6 from Albemarle is also involved but, due to confidentiality, is not discussed. An outline is provided from a European point of view on topics such as methodology of risk analyses, data-gaps and worst case approach, industry involvement, downstream participation and possible impact of final report on industry. 2 refs. 

Chlorines Chlorinated paraffins Tris (dichloropropyl) phosphate, methyl pentachlorostearate, and other chlorinated phosphates Cycloaliphatic chlorine Chlorendic anhydride LDPE film and flexible PVC Urethane foam and topical fabric Polypropylene and nylon Reactive intermediate in making polyester and epoxy flame-retardant resins Amspec Chemical, Asahi Denka Kogyo, ICC Industries-Dover, Kettlitz Chemie, Lehmann Voss, OxyChem, Polytechs... 

Important categories are the phosphate esters, extensively used in flexible PVC, modified polyphenylene oxide and some cellulosic polymers and chlorinated phosphates, commonly used in polyurethane formulations. 

The flammability of roofing foam blown with pentanes may have to be kept low by the use of flame retardant additives such as chlorinated phosphates. 

Bayer markets a dimethylpropane phosphonate-based FR called Levagard VP SP 51009 to enable rigid PU foam to meet fire regulations. Clariant offers liquid phosphorus polyols for the protection of polyether flexible and slabstock moulded automotive foams. Flexible PU is also commonly flame retarded in Europe with chlorinated phosphate esters. Borates have not shown... 

Flame retardant system Antiblaze AB-100 chlorinated phosphate ester (5 wt%) total additive... 

Chlorinated Phosphate Akzo Nobel Fyrol FR2,PCF,38. 25. FR-2LV Acrylic, Epoxy, Phenolic, Cellulose, UFf... 

Electrolytes and Osmotic Regulators.—Cathions of Sodium, Potassium, Calcium, Magnesium anions of Chlorine, Phosphate... 

Peroxide-Ketazine Process. Elf Atochem in France operates a process patented by Produits Chimiques Ugine Kuhhnaim (PCUK). Hydrogen peroxide (qv), rather than chlorine or hypochlorite, is used to oxidize ammonia. The reaction is carried out in the presence of methyl ethyl ketone (MEK) at atmospheric pressure and 50°C. The ratio of H202 MEK NH2 used is 1 2 4. Hydrogen peroxide is activated by acetamide and disodium hydrogen phosphate (117). Eigure 6 is a simplified flow sheet of this process. The overall reaction results in the formation of methyl ethyl ketazine [5921-54-0] (39) and water ... 

Hydrogen Chloride as By-Product from Chemical Processes. Over 90% of the hydrogen chloride produced in the United States is a by-product from various chemical processes. The cmde HCl generated in these processes is generally contaminated with impurities such as unreacted chlorine, organics, chlorinated organics, and entrained catalyst particles. A wide variety of techniques are employed to treat these HCl streams to obtain either anhydrous HCl or hydrochloric acid. Some of the processes in which HCl is produced as a by-product are the manufacture of chlorofluorohydrocarbons, manufacture of aUphatic and aromatic hydrocarbons, production of high surface area siUca (qv), and the manufacture of phosphoric acid [7664-38-2] and esters of phosphoric acid (see Phosphoric acid and phosphates). 

Miscellaneous. Both whiting and hydrated lime are used as diluents and carriers of pesticides, such as lime—sulfur sprays, Bordeaux, calcium arsenate, etc. The most widely used bleach and sterilizer, high test calcium hypochlorite, is made by interacting lime and chlorine (see Bleaching AGENTS). Calcium and magnesium salts, such as dicalcium phosphate, magnesium chloride, lithium salts, etc, are made directly from calcific and dolomitic lime and limestone. 

Trisodium phosphate is strongly alkaline many of its appHcations depend on this property. For example, many heavy-duty cleaning compositions contain trisodium phosphate as a primary alkalinity source. The crystalline dodecahydrate itself is marketed as a cleaning compound and paint remover. Traditionally, trisodium phosphate has been used in water softening to remove polyvalent metal ions by precipitation as insoluble phosphates. Because the hypochlorite complex of trisodium phosphate provides solutions that are strongly alkaline and contain active chlorine, it is used in disinfectant cleaners, scouring powders, and automatic dishwashing formulations. 

Nitrogen and sodium do not react at any temperature under ordinary circumstances, but are reported to form the nitride or azide under the influence of an electric discharge (14,35). Sodium siHcide, NaSi, has been synthesized from the elements (36,37). When heated together, sodium and phosphoms form sodium phosphide, but in the presence of air with ignition sodium phosphate is formed. Sulfur, selenium, and tellurium form the sulfide, selenide, and teUuride, respectively. In vapor phase, sodium forms haHdes with all halogens (14). At room temperature, chlorine and bromine react rapidly with thin films of sodium (38), whereas fluorine and sodium ignite. Molten sodium ignites in chlorine and bums to sodium chloride (see Sodium COMPOUNDS, SODIUM HALIDES). 

Manufacture. Trichloromethanesulfenyl chloride is made commercially by chlorination of carbon disulfide with the careful exclusion of iron or other metals, which cataly2e the chlorinolysis of the C—S bond to produce carbon tetrachloride. Various catalysts, notably iodine and activated carbon, are effective. The product is purified by fractional distillation to a minimum purity of 95%. Continuous processes have been described wherein carbon disulfide chlorination takes place on a granular charcoal column (59,60). A series of patents describes means for yield improvement by chlorination in the presence of dihinctional carbonyl compounds, phosphonates, phosphonites, phosphites, phosphates, or lead acetate (61). 

Flame Retardants. Because PVC contains nearly half its weight of chlorine, it is inherently flame-retardant. Not only is chlorine not a fuel, but it acts chemically to inhibit the fast oxidation in the gas phase in a flame. When PVC is diluted with combustible materials, the compound combustibiHty is also increased. Por example, plastici2ed PVC with > 30% plastici2er may require a flame retardant such as antimony oxide, a phosphate-type plastici2er, or chlorinated or brominated hydrocarbons (145,146). 

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