Patent GB-786902-A (GB)
Title: Quaternary phosphonium polyphosphates
Inventor: SEMMENS PETER WILLIAM BRETT
IPC: B01J47/00
Filed: 1955-04-20
Abstract: The invention comprises a quaternary phosphonium polyphosphate salt having (PO3) units forming substantially linear groups, each (PO3) unit being associated with a cation, the major proportion of such cations being quaternary phosphonium cations in each of which the four valencies of the phosphorus ion are attached to organic radicals.  The organic radicals in each quaternary phosphonium group may be all alike, or some or all may be different, and they may comprise alkyl, aryl, aralkyl, or alicyclic groups, or substituted derivatives thereof.  There may also be a minor proportion of sodium, potassium, or other cations associated with the (PO3) units.  These cations may be present as a result of their incomplete substitution in a polyphosphate salt by the quaternary phosphonium cations or they may be deliberately introduced during the preparation of the quaternary compounds.  The preferred compounds which are stated to be effective as boundary lubricants of ferrous metals (see Group III) are those in which at least one of the organic radicals includes at least one alkyl radical having six or more carbon atoms, specified organic radicals of this type being octyl, decyl, dodecyl, tetradecyl, cetyl, lauryl, and beta-p-tert.-octyl phenoxyethyl.  The preferred polyphosphate compounds are cetyl tripropyl-, didecyl dimethyl- and tetradecylphosphonium polyphosphates.  The quaternary phosphonium products may be obtained by bringing a solution of solubilized potassium polyphosphate into contact in solution with an aqueous solution of a quaternary phosphonium salt, such as the bromide, for example by mixing with stirring.  It is preferred to cool the phosphonium salt solution gradually and to stop when precipitation of the quaternary phosphonium compound is complete. The potassium polyphosphate may be obtained by first preparing potassium polyphosphate by heating potassium dihydrogen orthophosphate for about one hour at 650-700 DEG  C. and may be solubilized by one of the following methods (see Group III): (a) adding powdered potassium polyphosphate to water and contacting with the sodium salt of a cation exchange resin when it goes into solution as sodium-potassium-polyphosphate; (b) as in (a) except that the ammonium salt is used to give a solution of ammonium-potassium-polyphosphate; (c) allowing powdered potassium polyphosphate to stand in contact with a solution of a sodium salt, e.g. sodium chloride; and (d) treating with hydrogen peroxide, e.g. by adding potassium polyphosphate to hydrogen peroxide which is first neutralized by adding a small amount of alkali.  As an alternative to first solubilizing potassium polyphosphate, the products may be prepared by bringing powdered potassium polyphosphate into contact with an aqueous solution of a quaternary phosphonium salt, e.g. the bromide.  Examples are given for the production of cetyl tripropyl phosphonium polyphosphate by reacting the corresponding quaternary phosphonium bromide salt with solubilized potassium polyphosphate prepared as in methods (b), (c) and (d) above respectively.  The products may also be used as insecticides or to give water repellent finishes to glass or textiles.ALSO:A composition suitable for use as a boundary lubricant comprises at least one quaternary phosphonium polyphosphate salt (as defined below) dispersed in a liquid or solid vehicle which is preferably a lubricant.  The quaternary phosphonium polyphosphate salt is one having (PO3)- units forming substantially linear groups, each (PO3)- unit being associated with a cation, the major proportion of such cations being quaternary phosphonium cations in each of which the four valencies of the phosphorus ion are attached to organic radicals (see Group IV (b)).  The organic radicals may be the same or different and they may comprise alkyl, aryl, aralkyl, or alicyclic groups, or substituted derivatives thereof.  There may also be a minor proportion of sodium, potassium, or other cation associated with the (PO3)- units. The preferred quaternary salts are those in which at least one of the organic radicals includes at least one alkyl radical having six or more carbon atoms, specified radicals of this type being octyl, decyl, dodecyl, tetradecyl, cetyl, lauryl and beta-p.-tert. octyl phenoxyethyl.  The preferred compounds are cetyl tripropyl-, didecyl dimethyl- and tetradecylphosphonium polyphosphates.  Specified vehicles in which the quaternary compounds may be dispersed are mineral or vegetable oils or greases, esters of aliphatic dicarboxylic acids, polyalkylene glycols, polymethyl-phenyl siloxanes, mixtures of substantially completely halogenated aromatic hydrocarbons and petroleum jelly, or any combination of these.  A table is given to show the effectiveness as boundary lubricants of compositions comprising cetyl tripropyl phosphonium polyphosphate and a mineral oil, di (ethyl hexyl) sebacate, a polyalkylene glycol, a commercial mixture of substantially completely halogenated aromatic hydrocarbons and polymethyl-phenyl siloxane, respectively.  The quaternary phosphonium polyphosphate compounds may also be used to give water-repellent finishes to glass.  Potassium polyphosphate which may be used to prepare the quaternary phosphonium salts may be prepared by heating potassium dihydrogen orthophosphate, e.g. at 650 DEG  to 700 DEG  C., for about one hour and may be solubilized by one of the following methods: (a) adding to water and contacting with the sodium salt of a cation exchange resin, e.g. the sodium salt of a sulphonated polystyrene or of a sulphonated phenolic resin, when the polyphosphate goes into solution as a sodium-potassium polyphosphate; (b) as in (a) except that the ammonium salt of the cation exchange resin is used to form a solution of ammonium-potassium polyphosphate; (c) allowing powdered potassium polyphosphate to stand in contact with a solution of a sodium salt, e.g. sodium chloride, to give a viscous solution; and (d) treatment with hydrogen peroxide, e.g. by adding potassium polyphosphate to hydrogen peroxide, the latter being first neutralized by adding a small amount of alkali.  Examples of methods (b), (c) and (d) are given.