Phosphoric and Polyphosphoric Acids

Orthophosphoric (monophosphoric) add, H3PO4 (nsnaUy referred to as phosphoric acid), is the simplest oxyacid of phosphorus. It is stored and sold as an aqueous solution which is available in varions concentrations. The acid can be prepared by reacting phosphorus pentoxide with water (4.43). In the dry or thermal commercial process, the oxide is first prepared by bnming white phosphoms (Chapter 4.1). 

The greatest tonnage of phosphoric acid is, however, today prepared by the cheaper wet process which involves the direct treatment of apatite with snlphnric acid. The main reaction can, ideally, be represented by 

In earlier days, bones were nsed as the source of apatite. The product is less pure than thermal process acid and most of it is nsed in fertiliser manufactnre (Chapter 12.2). 

There has been a massive expansion of world prodnction capacity for wet process acid over the past 40 years. Since 1960, world ontput has risen by a factor of over 10 and capacity now stands at around 40 million tons (as P2O5) per annum. The increase has been particularly great in Arab phosphate rock-prodncing conntries snch as Morocco and Tnnis and also in China. Phosphoric acid ontput ranks abont ninth place compared to other industrial ch ical tonnages (Tables 5.1 and 5.2). 

Alternative (laboratory) methods for making phosphoric acid are the direct oxidation of white phosphorus with nitric acid and the oxidation of phosphorons acid (4.22), (5.216). 

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The synthesis of 2,4-dihydroxyacetophenone [89-84-9] (21) by acylation reactions of resorcinol has been extensively studied. The reaction is performed using acetic anhydride (104), acetyl chloride (105), or acetic acid (106). The esterification of resorcinol by acetic anhydride followed by the isomerization of the diacetate intermediate has also been described in the presence of zinc chloride (107). Alkylation of resorcinol can be carried out using ethers (108), olefins (109), or alcohols (110). The catalysts which are generally used include sulfuric acid, phosphoric and polyphosphoric acids, acidic resins, or aluminum and iron derivatives. 2-Chlororesorcinol [6201-65-1] (22) is obtained by a sulfonation—chloration—desulfonation technique (111). 1,2,4-Trihydroxybenzene [533-73-3] (23) is obtained by hydroxylation of resorcinol using hydrogen peroxide (112) or peracids (113). 

Phosphoric and polyphosphoric acid esters Perfluorinated anionics Sulfonic acid salts Strong surface tension reducers Good oil in water emulsifiers Soluble in polar organics Resistant to biodegradation High chemical stability Resistant to acid and alkaline hydrolysis... 

It is of interest to note that attachment of a basic side chain on carbon of an isomeric dibenzazepine affords a compound in which anticholinergic activity predominates, elantrine (50). Reaction of anthra-quinone (45) with the Grignard reagent from 3-chloro-N,N-dimethylaminopropane in THF in the cold results in addition to but one of the carbonyl groups to yield hydroxyketone 46. This is then converted to oxime 47 in a straightforward manner. Treatment of that intermediate with a mixture of phosphoric and polyphosphoric acids results in net dehydration of... 

A munber of nitrogen derivatives of phosphoric and polyphosphoric acid (ammonium polyphosphate, melamine pyrophosphate) are used for improving the flame retardance of polyurethanes and other polymers. In thermal decomposition these compounds produce ammonia and the corresponding phosphoric acids which catalyze dehydration and other reactions, causing polymer dehydration during combustion. The coke produced in this process is more or less foamed. Ammonium polyphosphate and melamine pyrophosphate are added to compositions of intumes-cent coatings used for fire protection of various structural elements in construction... 

Phosphoric and Polyphosphoric Acid Esters, R(OC2H4)xOP(0)(0 M+)2 and [R(OC2H4)xO]2P(0)0 M+ Mainly phosphated POE alcohols and phenols, some sodium alkyl phosphates (not oxyethylenated). The POE materials are available in free acid form or as sodium or amine salts. Products are mixtures of monobasic and dibasic phosphates. 

A number of protic acids have been used to catalyze acylation reactions. It is assumed that the reactions involve the generation of acylium ions. Polymeric reagents such as Nafion-H have been used for example 2-fluorobenzoyl chloride and toluene give the benzophenone derivatives with an ortho.para ratio of 4 81. ° A zeolite-catalyzed acylation (equation 6) has been reported to afford 4-dodecenoyltol-uene in 96% yield but the yields are low with short chain carboxylic acids. Early examples of the use of trifluoroacetic and perchloric acids reported good yields of products. Some more recent examples are shown in equations (7) to (9). Phosphoric and polyphosphoric acids have been used together with carboxylic acids (equation 10),anhydrides and acylureas (equation 11). °... 

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. 

If even less water is used for hydration, a product known as polyphosphoric acid results. Ordinary phosphoric acid is a solution of the monomer, H3P04, in water, and is called orthophosphoric acid. If a molecule of water is removed between two orthophosphate molecules, the dimer, pyrophosphoric acid, H4P207, is formed. Similarly, the trimerand higher polymers can be made. Superphosphoric acid is a mixture of orthophosphoric acid and polyphosphoric acid and is now made from wet process acid as described later in this chapter. 

Ethers are cleaved by HI faster than by HBr and HCl (Scheme 25). To prevent the undesirable reducing action of the reagent, KI and phosphoric or polyphosphoric acid are used to generate HI in situ (equation 32). The ether nd is also cleaved by trimethylsilyl iodide (equation 33). ... 

Later a breakthrough came when a series of weak base catalysts were discovered that are more active than sodium carbonate or tertiary amines. Alkali metals salts of phosphoric, polyphosphoric, phosphorous, and hypophosphorous acids were proven effective [376,385-389]. 

Hame retardants that contain phosphorous release polyphosphoric acid and are effective in the condensed phase. These agents form a protective layer. The polyphosphoric acid also splits water out of organic plastics, resulting in formatiOTi of an additional protective carbon layer. 

Some phosphorus compounds decompose in the condensed phase to form phosphoric or polyphosphoric acids. These can act as dehydration catalysts, reacting with cellulosics for example, to form a good char. Char yield is also increased with rigid polyurethanes. The polyphosphoric acid can also form a viscous molten surface layer or surface glass. This layer can shield the polymeric substrate from the flame (heat) and oxygen. Intumescence, which requires an acid such as phosphoric acid, results in a dense carbon char on the polymer surface protecting the substrate from heat and oxygen. 

The principal phosphation reagents used to manufacture phosphate esters are phosphoric anhydride (P4O10), phosphorus oxychloride [P(0)Cl3], and polyphosphoric acid. It is important to understand the physical and chemical characteristics of each raw material. The structure of the phosphation agent affects its reactivity and selectivity, resulting in variation in the monoester, diester, and triester product distribution. 

In the first step, the alcohol, phosphation reagent, and water (or its equivalent in phosphoric or polyphosphoric acid, calculated as a composite of phosphoric anhydride and water) are combined in accord with the following equation ... 

A patent review [4] showed that early intumescent formulations incorporated in polymers contained a precursor of phosphoric or polyphosphoric acid, a pentaerythritol type char source, and melamine, as typical formulations of intumescent coatings. Further developments tried to reduce the complexity of the additive system, for example by using a binary combination of the add precursor with nitrogen-containing compounds, which also act as a char source. While the add source is generally APP, typical examples of the second component are produds of condensation of formaldehyde with substituted ureas products of readions between aromatic diisocyanates and pentaerythritol or melamine polymers containing the piperazine ring in the main chain, also combined with substituted s-triazine, hydroxyalkyl isocyanurate etc. 

For the high-temperature PEFC the temperature limits range from 10 to 200°C, the membrane needs to be of a temperature-resistant type (e.g., polybenzimidazole doped with phosphoric acid as developed, e.g., by Celanese) and the media in contact with the sealing are air, hydrogen gas, water, water vapor, phosphoric acid and polyphosphoric acid. 

Commercial condensed phosphoric acids are mixtures of linear polyphosphoric acids made by the thermal process either direcdy or as a by-product of heat recovery. Wet-process acid may also be concentrated to - 70% P2O5 by evaporation. Liaear phosphoric acids are strongly hygroscopic and undergo viscosity changes and hydrolysis to less complex forms when exposed to moist air. Upon dissolution ia excess water, hydrolytic degradation to phosphoric acid occurs the hydrolysis rate is highly temperature-dependent. At 25°C, the half-life for the formation of phosphoric acid from the condensed forms is several days, whereas at 100°C the half-life is a matter of minutes. 

Pyrophosphoric (diphosphoric) acid, H4P2O2, is the only condensed phosphoric acid definitely obtainable ia crystalline form. It has a theoretical P2O5 content of 79.8%. However, Hquid polyphosphoric acid of such content shows by analysis only 42.5% the remainder is phosphoric acid and... 

Polyphosphoric acid supported on diatomaceous earth (p. 342) is a petrochemicals catalyst for the polymerization, alkylation, dehydrogenation, and low-temperature isomerization of hydrocarbons. Phosphoric acid is also used in the production of activated carbon (p. 274). In addition to its massive use in the fertilizer industry (p. 524) free phosphoric acid can be used as a stabilizer for clay soils small additions of H3PO4 under moist conditions gradually leach out A1 and Fe from the clay and these form polymeric phosphates which bind the clay particles together. An allied though more refined use is in the setting of dental cements. 

In 1909, Robinson demonstrated the utility of acylamidoketones as intermediates to aryl-and benzyl-substituted 1,3-oxazoles through cyclization with sulfuric acid. Extension of sulfuric acid cyclization conditions to alkyl-substituted oxazoles can give low yields, for example 10-15% for 2,5-dimethyl-l,3-oxazole. Wiegand and Rathbum found that polyphosphoric acid can provide alkyl-substituted oxazoles 4 in yields equal to or greater than those obtained with sulfuric acid. Significantly better yields are seen in the preparation of aryl- and heteroaryl-substituted oxazoles. For example, reaction of ketoamides 5 with 98% phosphoric acid in acetic anhydride gives oxazoles 6 in 90-95% yield. ... 

Proceeding from 5 -0-acetylazauridine (80), a mixture of 2 - and 3 -monophosphates (81, 82) was prepared by phosphorylation with polyphosphoric acid, and these were converted into the 2, 3 -cyclic phosphate (83). From the 2, 3 -0-isopropylidene derivative of 3-methyl-6-azauridine the 5 -phosphate was prepared by treatment with cyanoethylphosphate and the corresponding diphosphate from its morpholidate through the action of phosphoric acid. ° Furthermore, a diribonucleoside phosphate (85) with a natural 3 -5 internucleotide linkage was prepared from 6-azauridine, The starting material for the preparation of such derivatives was 5 -0-acetyl-2 -0 -tetrahydro-pyranyluridine-3 -phosphate (84) which was condensed with di-G-acetylazauridine (86) or with 2b3 -0-isopropylidene-6-azauridine (76) with the aid of dicyclohexylcarbodiimide. ... 

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