Phosphorous-Free

Nesvadba, P. Krohnke, C. A new class of highly active phosphorous free processing stabilizers for polymers. Proceedings of the Sixth International Conference Additives 97, ECM New Orleans, 1997. 

Also copolymers have been prepared. These copolymers contain both a phosphorous containing moiety and a phosphor free moiety,... 

Features Thermally stable, stable to chlorine and oxidizing bloddes phosphorous free, and stable at all pH levels... 

The most important property of phosphorus(V) oxide is its great tendency to react with water, either free or combined. It reacts with ordinary water with great vigour, and much heat is evolved trioxo-phosphoric(V) acid is formed, but the local heating may convert some of this to tetraoxophosphoric(V) acid ... 

Place 45 g. of benzamide (Section IV, 188) and 80 g. of phosphorus pentoxide in a 250 ml. Claisen flask (for exact experimeutal details on the handling and weighing out of phosphoric oxide, see under Acetamide, Section 111,111). Mix well. Arrange for distillation (Fig.//, 29, 1 or Fig. II, 20, 1) under reduced pressure use a water pump with an air leak in the system so that a pressure of about 100 mm. is attained. Heat the flask with a free flame until no more liquid distils the nitrile will pass over at 126-130°/100 mm. Wash the distillate with a little sodium carbonate solution, then with water, and dry over anhydrous calcium chloride or magnesium sulphate. Distil under normal pressure (Fig. II, 13, 2 or II, 13, 6) from a 50 ml. flask the benzonitrile passes over as a colourless liquid at 188-189° (compare Section IV,66). The yield is 28 g. 

P-Cyanopyridine. Mix 25 g. of powdered nicotinamide with 30g. of phosphoric oxide in a 150 ml. distilling flask by shaking. Immerse the flask in an oil bath and arrange for distillation under a pressure of about 30 mm. Raise the temperature of the oil bath rapidly to 300°, then remove the oil bath and continue the heating with a free flame as long as a distillate is obtained. The nitrile crystallises on cooling to a snow-white solid. Redistil the solid at atmospheric pressure practically all of it passes over at 201° and crystallises completely on cooling. The yield of p-cyanopyridine, m.p. 49°, is 20 g. 

Copper and Copper Alloys. The coppers are divided into oxygen-bearing and oxygen-free coppers. Numerous copper alloys are of commercial importance, including those alloys with zinc (brasses), with tin (phosphor bronzes), and with aluminum (aluminum bronzes) all are weldable. 

At equihbrium, the specific composition of a concentrated phosphoric acid is a function of its P2 s content. Phosphoric acid solutions up to a concentration equivalent of about 94% H PO (68% P2O5) contain H PO as the only phosphoric acid species present. At higher concentrations, the orthophosphoric acid undergoes condensation (polymerization by dehydration) to yield a mixture of phosphoric acid species (Table 5), often referred to genericaHy as polyphosphoric or superphosphoric acid, H20/P20 = - 3, or ultraphosphoric acid, H20/P20 = - 1. At the theoretical P2O5 concentration for orthophosphoric acid of 72.4%, the solution is actually a mixture containing 13% pyrophosphoric acid and about 1% free water. Because the pyrophosphoric acid present is the result of an equihbrium state dependent on the P2 5 content of the solution, pure orthophosphoric acid can be obtained because of a shift in equihbrium back to H PO upon crystallization. 

Both monocalcium phosphate and dicalcium phosphate dissolve incongmently in water, disproportionating to more basic calcium phosphate and phosphoric acid. The extent of these reactions varies with the temperature and the amount of water. If water is added gradually to anhydrous monocalcium phosphate, equiUbrium conditions first correspond to a mixture of the anhydrous salt and its monohydrate. After conversion to the monohydrate, further reaction affords dicalcium phosphate plus free phosphoric acid. Dicalcium phosphate decomposes in aqueous solution to the more basic hydroxyapatite and phosphoric acid via intermediate octacalcium phosphate. The compHcated stepwise conversion of the acidic mono- and dicalcium phosphates to hydroxyapatite is summarized in equations 6—9. The kinetics are quite complex. 

Because monocalcium phosphate is incongmently soluble, it is typically contaminated with various amounts (6—10%) of dicalcium phosphate and free phosphoric acid resulting from in-process disproportionation of the monocalcium salt. Free phosphoric acid may render the product hygroscopic, and absorbed water plus acid catalyzes further decomposition to additional free acid and dicalcium phosphate. For this reason, industrial monocalcium phosphate may contain some dicalcium phosphate resulting from excess lime addition and then aged to ensure the removal of residual free phosphoric acid. 

Tricalcium phosphate, Ca2(P0 2> is formed under high temperatures and is unstable toward reaction with moisture below 100°C. The high temperature mineral whidockite [64418-26-4] although often described as P-tricalcium phosphate, is not pure. Whidockite contains small amounts of iron and magnesium. Commercial tricalcium phosphate prepared by the reaction of phosphoric acid and a hydrated lime slurry consists of amorphous or poody crystalline basic calcium phosphates close to the hydroxyapatite composition and has a Ca/P ratio of approximately 3 2. Because this mole ratio can vary widely (1.3—2.0), free lime, calcium hydroxide, and dicalcium phosphate may be present in variable proportion. The highly insoluble basic calcium phosphates precipitate as fine particles, mosdy less than a few micrometers in diameter. The surface area of precipitated hydroxyapatite is approximately... 

A 99.5% Cu—0.5% Te alloy has been on the market for many years (78). The most widely used is alloy No. CA145 (number given by Copper Development Association, New York), nominally containing 0.5% tellurium and 0.008% phosphorous. The electrical conductivity of this alloy, in the aimealed state, is 90—98%, and the thermal conductivity 91.5—94.5% that of the tough-pitch grade of copper. The machinahility rating, 80—90, compares with 100 for free-cutting brass and 20 for pure copper. 

Dicalcium Phosphate Dihydrate (DPD). Dicalcium phosphate cHhydrate is completely nonreactive at room temperature. At 65—71°C and in the presence of water, it dehydrates and decomposes into hydroxyapatite and acidic monocalcium phosphate, or a free phosphoric acid (18). It is used to some extent in cake mixes in combination with faster acting acid. Its primary function is to provide acidity late in the baking cycle and thus produce a neutral and palatable product. DPD has an NV of 33. It provides sufficient acidity only in products requiring long baking times. 

Fig. 29. Phosphoric acid etched A606. steel surface showing smut-free, smooth-walled crevice morphology [54].

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