Patent GB-717675-A (GB)
Title: Improvements in or relating to lubricant additives
Inventor: HAWKINS ELEANOR RUTH
IPC: C10M159/12
Filed: 1951-03-02
Abstract: In the production of a lubricating oil additive by reacting at elevated temperature a phosphorus sulphide or a mixture of elemental phosphorus and sulphur with a mineral lubricating oil and further reacting the phosphosulphurized product with an unsaturated hydrocarbon (as defined below), the phosphorus sulphide or mixture of phosphorus and sulphur is heated, prior to reaction with the mineral oil, to a temperature between 212 DEG  F. and the boiling or decomposition temperature, whichever is the lower, of the said phosphorus sulphide or mixture, a stream of inert gas, preferably nitrogen or carbon dioxide, is passed through the reaction mixture during the phosphosulphurization and the phosphosulphurized product is maintained at a temperature of between 212 DEG  F. and 40 DEG  F. for a period preferably less than 24 hours prior to reaction with the unsaturated hydrocarbon.  The mineral lubricating oil may be any treated or untreated mineral lubricating oil distillate or brightstock and specified phosphorus sulphides are phosphorus pentasulphide, trisulphide, sesquisulphide, disulphide and heptasulphide or mixtures thereof. The unsaturated hydrocarbon which is reacted with the phosphosulphurized product is defined as any aliphatic, cycloaliphatic, terpenic, or aliphatic-aromatic hydrocarbon containing at least one double bond carbon-to-carbon linkage in a non-aromatic group.  Specified unsaturated hydrocarbons are the olefines, e.g. propylene, butylenes, diisobutylenes, triisobutylenes, the codimer of isobutylene and n-butylene, cracked gasoline fractions, cracked paraffin wax, viscous olefin polymers such as medium or high molecular weight polybutene; cyclopentene, cyclohexene, butadiene, pentadiene, isoprene, dipentene, alpha-pinene, beta-pinene, terpinolene, D 2,4,(8)-p-menthadiene and styrene.  The phosphosulphurization may be carried out at about 200 DEG  F. to 600 DEG  F., preferably 300 DEG  to 550 DEG  F., using about 1 to 10, preferably 2 to 5 molecular proportions of hydrocarbon to one of phosphorus sulphide and the phosphosulphurized product is then further reacted with the unsaturated hydrocarbon at a temperature preferably between 150 DEG  and 450 DEG  F., the amount of the unsaturated hydrocarbon being preferably from 0.1 per cent to 50 per cent of the phosphosulphurised product.  A stream of inert gas, e.g. nitrogen or carbon dioxide, may also be passed through the reactants during this reaction stage.  In an example phosphorus pentasulphide preheated to 212 DEG  F. is added to a propane de-asphalted, acid treated, dewaxed and decolourized Panhandle residuum and the mixture heated to 410 DEG  F. and reacted at this temperature for 12 hours while bubbling nitrogen through the reaction mixture.  The mixture is then cooled and filtered, heated for 6 hours at 300 DEG  F., and then reacted with 20 per cent by weight of dipentene for 1 hour at 100 DEG  F. and the product cooled and filtered.  The properties of a straight mineral oil containing the product are compared with those of a straight mineral oil alone. Tables are also given to show the separate effects of (1) bubbling nitrogen through the reactants during the phosphosulphurization of a lubricating oil brightstock; (2) preheating phosphorus pentasulphide to 176 DEG  F., 360 DEG  F., and 383 DEG  F. respectively before its use in the phosphosulphurization reaction; and (3) maintaining the phosphosulphurized product at 300 DEG  F. for 6 hours prior to reaction with the unsaturated hydrocarbon.  Specification 687,417 is referred to.  According to the Provisional Specification the materials that may be submitted to the phosphosulphurization process also include petrolatums and paraffin waxes.ALSO:A lubricating composition comprises a mineral lubricating oil and an additive obtained by reacting at elevated temperature a phosphorus sulphide or a mixture of elemental phosphorus and sulphur with a mineral lubricating oil and further reacting the phosphosulphurized product thus obtained with an unsaturated hydrocarbon (as defined below) the phosphorus sulphide or mixture of elemental phosphorus and sulphur being heated, prior to reaction with the mineral oil, to a temperature between 212 DEG F. and the boiling or decomposition temperature whichever is the lower of the said phosphorus sulphide or mixture, a stream of inert gas, preferably nitrogen or carbon dioxide, being passed through the reaction mixture during the phosphosulphurization and the phosphosulphurization product being maintained at a temperature between 212 DEG F. and 400 DEG F. for a period preferably less than 24 hours prior to reaction with the unsaturated hydrocarbon (see Group IV (b)).  A stream of inert gas, e.g. nitrogen or carbon dioxide may also be passed through the reaction mixture during the reaction of the phosphosulphurized product with the unsaturated hydrocarbon.  The mineral lubricating oil submitted to the phosphosulphurization treatment may be any treated or untreated mineral lubricating oil distillate or brightstock and specified phosphorus sulphides are the pentasulphide, trisulphide, sesquisulphide and heptasulphide or mixtures thereof. The unsaturated hydrocarbon is defined as any aliphatic, cycloaliphatic, terpenic, or aliphaticaromatic hydrocarbon containing at least one double bond carbon-to-carbon linkage in a nonaromatic group.  Specified unsaturated hydrocarbons are the olefines, e.g. propylene, butylenes, di-isobutylenes, tri-isobutylenes, the codimer of isobutylene and n-butylene, cracked gasoline fractions, cracked paraffin wax, viscous olefin polymers such as medium or high molecular weight polybutene, cyclopentene, cyclohexene, butadiene, pentadiene, isoprene, dipentene, alpha-pinene, beta-pinene, terpinolene, D -2, 4, (8)-p-menthadiene and styrene.  In an example phosphorus pentasulphide preheated to 212 DEG F. is added to a propane de-asphalted, acid treated, dewaxed and decolorized. Panhandle residuum and the mixture heated to 410 DEG F. and reacted at this temperature for 12 hours while bubbling nitrogen through the mixture.  The mixture is then cooled and filtered, heated for 6 hours at 300 DEG F., and then reacted for 1 hour at 100 DEG F. with 20 per cent. by weight of dipentene and the product cooled and filtered. The properties of a straight mineral oil containing the product are compared with those of a straight mineral oil alone.  The mineral oils which are phosphosulphurized and the unsaturated hydrocarbon which is reacted with the phosphosulphurized product are chosen so as to provide a product which is soluble in the mineral oil base or which may be brought into solution with the aid of solubilizing agents such as high molecular weight alcohols or esters.  The products are effective as extreme pressure agents and may be added to mineral lubricating oils in amounts up to 50 per cent. by weight of the blend but they are preferably used in amounts less than 20 per cent., e.g. 10 per cent.  Specification 687,417 is referred to. According to the Provisional Specification the materials that may be submitted to the phosphosulphurization process also include petrolatums and paraffin waxes.