Patent GB-727573-A (GB)
Title: Improvements in or relating to phospho-sulphurisation of organic materials
Inventor: POTTER EDWARD BARRIE VERNON
IPC: C07F9/04
Filed: 1951-07-30
Abstract: In a process for reacting a phosphorus sulphide, or a mixture of phosphorus sulphides, or a mixture of phosphorus and sulphur with organic materials known to react therewith, the process is carried out in the presence of a finely divided, inert, refractory, dispersed solid.  The refractory materials used as dispersed solids are those which do not react with the reactants or reaction products and include sand, silica gel, clays such as attapulgus clay or moutmorillonite, brick dust, powdered silicate rocks, e.g. felspar, augite and mica; pumice, kieselguhr and cracking catalyst (synthetic silica-magnesia or silica-alumina). The organic materials that may be used are preferably predominantly hydrocarbon materials such as paraffins, olefins or olefin polymers, diolefines, acetylenes, aromatics, alkyl aromatics, cyclic aliphatics, liquid hydrocarbons derived from mineral oil such as naphthas, gas oils or lubricating oils, petroleum waxes, cracked cycle stocks, condensation products of petroleum fractions, bright stock residuum, lubricating oil distillates, and Friedel-Crafts condensates of halogenated hydrocarbons and aromatics and particularly mineral lubricating oil bright stocks which may be untreated petroleum fractions or residue, or oils refined by any conventional treatment such as dewaxing, solvent extractions and deasphalting.  Other compounds which may be used include fatty bodies such as fatty oils-animal, vegetable and marine such as sperm oil, lard oil, linseed oil, and olive oil, fatty acids, sulphurized fatty oils, halogenated hydrocarbons, terpenes, such as alpha pinene and dipentene, polyterpenes, rosin, vegetable and mineral waxes such as spermaceti, carnauba and candellila waxes, ceresine, lanoline, lecithin and paraffin wax.  The inert material should preferably have a particle size between 100 and 20 mesh and is preferably used in an amount of between 1 and 5 per cent by weight. The phosphosulphurization may be effected by heating the components at 200 DEG  to 600 DEG  F., preferably 300 DEG  to 550 DEG  F. using about 1 to 10 parts by weight of organic material to one of the phosphosulphurization reagent.  The products may be further reacted with a predominantly hydrocarbon material containing at least one olefinic double bond, e.g. as disclosed in Specifications 687,417 and 713,337 respectively.  Any or all of the steps disclosed in Specification 717,675 may also be included in the present process. These steps involve heating the phosphorus sulphide or mixture of elemental phosphorus and sulphur to a temperature between 212 DEG  F. and the boiling or decomposition temperature thereof prior to the phosphosulphurization, passing a stream of inert gas through the reaction mixture during the phosphosulphurization and maintaining the phosphosulphurized product at between 212 DEG  F. and 400 DEG  F. prior to reaction with the unsaturated hydrocarbon containing at least one olefinic double bond.  Specified phosphorus sulphides are the pentasulphide, trisulphide, sesquisulphide, disulphide and heptasulphide.  A table is given to show that the reaction time is reduced when phosphorus pentasulphide is reacted with a mid-Continent bright stock in the presence of 3 per cent by weight of powdered fuller's earth as compared with reaction in the absence of the earth.ALSO:In the production of additives for use in lubricating oils by reacting a phosphorus sulphide or a mixture of phosphorus sulphides, or a mixture of phosphorus and sulphur, with organic materials known to react therewith, the reaction is carried out in the presence of a finely divided, inert, refractory, dispersed solid, e.g. sand, silica gel, clays such as attapulgus clay or montmorillonite, brick dust, powdered silicate rocks, e.g. felspar, augite and mica; pumice, kieselguhr and cracking catalyst (i.e. synthetic silica magnesia or synthetic silica-alumina).  The preferred organic material is a predominantly hydrocarbon material such as a mineral lubricating oil bright stock, but several other materials may be used, including hydrocarbons, fatty oils, fatty acids, terpenes, polyterpenes, rosin, vegetable and mineral waxes, ceresine, lanoline, lecithin and paraffin wax (see Group IV (b)). When the products are to be dissolved in mineral oils the reactants should be chosen so as to give a product soluble in the oil base or which can be brought into solution with the aid of solubilizing agents such as esters or alcohols of high molecular weight.  The products may be further reacted with a predominantly hydrocarbon material containing at least one olefinic double bond,e.g. as disclosed in Specifications 687,417 and 713,337.  A table is given to show the properties of the additive obtained by reacting a mid-Continent bright stock with phosphorus pentasulphide in the presence of 3 per cent. by weight of Fuller's earth.  Specification 717,675 is also referred to and it is stated that any of the steps disclosed in the latter may be included in the present process. These steps involve heating the phosphorus sulphide or mixture of phosphorus and sulphur to a temperature between 212 DEG  F. and the boiling or decomposition temperature thereof, prior to the phosphosulphurization reaction, passing a stream of inert gas through the reaction mixture during the phosphosulphurization, and maintaining the phosphosulphurized product at between 212 DEG  F. and 400 DEG  F. prior to reaction with the unsaturated hydrocarbon containing at least one olefinic double bond.