Ammonium polyphosphate
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Ammonium polyphosphate is an inorganic salt of
polyphosphoric acid A phosphoric acid, in the general sense, is a phosphorus oxoacid in which each phosphorus (P) atom is in the oxidation state +5, and is bonded to four oxygen (O) atoms, one of them through a double bond, arranged as the corners of a tetrahedron. ...
and
ammonia Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous wa ...
containing both chains and possibly branching. Its chemical formula is H4 PO3sub>n(OH)2 showing that each
monomer In chemistry, a monomer ( ; '' mono-'', "one" + ''-mer'', "part") is a molecule that can react together with other monomer molecules to form a larger polymer chain or three-dimensional network in a process called polymerization. Classification ...
consists of an
orthophosphate A phosphoric acid, in the general sense, is a phosphorus oxoacid in which each phosphorus (P) atom is in the oxidation state +5, and is bonded to four oxygen (O) atoms, one of them through a double bond, arranged as the corners of a tetrahedron. ...
radical of a
phosphorus Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ear ...
atom with three
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as ...
s and one negative charge neutralized by an ammonium cation leaving two bonds free to
polymerize In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many for ...
. In the branched cases some monomers are missing the ammonium anion and instead link to three other monomers. The properties of ammonium polyphosphate depend on the number of monomers in each molecule and to a degree on how often it branches. Shorter chains (n<100) are more water sensitive and less thermally stable than longer chains (n>1000), but short polymer chains (''e.g.'' pyro-, tripoly-, and tetrapoly-) are more soluble and show increasing solubility with increasing chain length. Ammonium polyphosphate can be prepared by reacting concentrated phosphoric acid with ammonia. However, iron and aluminum impurities, soluble in concentrated phosphoric acid, form gelatinous precipitates or "sludges" in ammonium polyphosphate at pH between 5 and 7. Other metal impurities such as copper, chromium, magnesium, and zinc form granular precipitates. However, depending on the degree of polymerization, ammonium polyphosphate can act as a
chelating agent Chelation is a type of bonding of ions and molecules to metal ions. It involves the formation or presence of two or more separate coordinate bonds between a polydentate (multiple bonded) ligand and a single central metal atom. These ligands ar ...
to keep certain metal ions dissolved in solution. Ammonium polyphosphate is used as a food additive, emulsifier, ( E number: E545) and as a
fertilizer A fertilizer (American English) or fertiliser (British English; see spelling differences) is any material of natural or synthetic origin that is applied to soil or to plant tissues to supply plant nutrients. Fertilizers may be distinct from ...
. Ammonium polyphosphate (APP) is also used as a
flame retardant The term flame retardants subsumes a diverse group of chemicals that are added to manufactured materials, such as plastics and textiles, and surface finishes and coatings. Flame retardants are activated by the presence of an ignition source and ...
in many applications such as paints and coatings, and in a variety of polymers: the most important ones are polyolefins, and particularly polypropylene, where APP is part of intumescent systems. Compounding with APP-based flame retardants in polypropylene is described in. Further applications are thermosets, where APP is used in unsaturated polyesters and gel coats (APP blends with synergists), epoxies and polyurethane castings (intumescent systems). APP is also applied to flame retard
polyurethane Polyurethane (; often abbreviated PUR and PU) refers to a class of polymers composed of organic units joined by carbamate (urethane) links. In contrast to other common polymers such as polyethylene and polystyrene, polyurethane is produced from ...
foams. Ammonium polyphosphates as used as flame retardants in polymers have long chains and a specific crystallinity (Form II). They start to decompose at 240 °C to form ammonia and phosphoric acid. The phosphoric acid acts as an acid catalyst in the dehydration of carbon-based poly-alcohols, such as cellulose in wood. The phosphoric acid reacts with alcohol groups to form heat-unstable phosphate
ester In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides a ...
s. The esters decompose to release carbon dioxide and regenerate the phosphoric acid catalyst . In the gas phase, the release of non-flammable carbon dioxide helps to dilute the oxygen of the air and flammable decomposition products of the material that is burning. In the condensed phase, the resultant carbonaceous char helps to shield the underlying polymer from attack by oxygen and radiant heat. Use as an
intumescent An intumescent is a substance that swells as a result of heat exposure, leading to an increase in volume and decrease in density. Intumescent materials are typically used in passive fire protection and require listing, approval, and compliance in ...
is achieved when combined with starch-based materials such as pentaerythritol and melamine as expanding agents. The mechanisms of intumescence and the mode of action of APP are described in a series of publications.Bourbigot, S.; Le Bras, M. Intumescence flame retardants and char formation, p. 139 f, in Troitzsch, J. Ed. Plastics flammability handbook, 3rd Ed., Hanser Publishers, Munich, 2004


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External links

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Specialchem4polymers.com
{{Ammonium salts Food additives Polymers Ammonium compounds Inorganic fertilizers Flame retardants