Patent GB-722268-A (GB)
Title: Improvements in or relating to phosphosulphurisation processes
Inventor: JENSEN HANS CHRISTIAN HENRY
IPC: C07F9/04
Filed: 1951-11-28
Abstract: Phosphorus and sulphur-containing materials are obtained by reacting a predominantly hydrocarbon material at elevated temperature with a phosphorus sulphide or a mixture of elemental phosphorus and sulphur and then reacting the product, unfiltered and while still warm, at elevated temperature with a hydrocarbon containing at least one olefinic double bond.  The predominantly hydrocarbon material is preferably a mineral oil fraction (see Group IV (b)) or a polymer of one or more hydrocarbons derived from such fractions, e.g. a polymerized olefin such as polyisobutylene or a copolymer of an olefin with another hydrocarbon containing one or more double bonds e.g. a copolymer of isobutylene and styrene, butadiene or isoprene. The unsaturated material which is reacted with the phosphosulphurized product may be any aliphatic, cycloaliphatic, terpenic or aliphatic-aromatic hydrocarbon containing at least one olefinic double bond.  Specified materials are the olefines such as propylene, butylenes, diisobutylenes, triisobutylenes, the codimer of isobutylene and n-butylene, cracked gasoline fractions, cracked paraffin wax, viscous olefinic 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 or styrene.  Specified phosphorus sulphides are the pentasulphide, trisulphide, sesquisulphide, disulphide and heptasulphide.  A mixture of phosphorus sulphides may also be used.  The phosphosulphurization is preferably effected at 200 DEG  to 600 DEG  F. whilst the reaction between the phosphosulphurized intermediate and the olefinic material is preferably conducted at 150-450 DEG  F. The products are stated to be extreme pressure agents for lubricating oils, preferably mineral lubricating oils (see Group III).  Specifications 687,417 and 717,675, [Group IV (b)], are referred to.ALSO:Phosphorus and sulphur-containing materials are obtained by reacting a predominantly hydrocarbon material at elevated temperature with a phosphorus sulphide or a mixture of elemental phosphorus and sulphur and further reacting the product, unfiltered and while still warm, at elevated temperature with a hydrocarbon containing at least one olefinic double bond.  The predominantly hydrocarbon material is preferably a mineral oil fraction or a polymer of one or more hydrocarbons derived from such fractions.  Thus it may be a lubricating oil, distillate or residual, preferably a bright stock.  The lubricating oil fraction may have been subjected to a refining step such as adsorbent treatment, solvent extraction, distillation and dewaxing.  Useful polymers are the polymerized olefins, e.g. polyisobutylene. Copolymers of olefins with other hydrocarbons containing one or more double bonds may also be used (see Group IV (a)).  Specified phosphorus sulphides are the pentasulphide, trisulphide (P4S6), sesquisulphide (P4S3), disulphide (P3S6) and heptasulphide (P4S7).  A mixture of phosphorus sulphides may also be used.  The phosphosulphurization may be effected by heating at 200 DEG  to 600 DEG  F. using about 1 to 10, preferably 3 to 8 molar proportions of hydrocarbon to one of the phosphorus sulphide.  When the products are to be dissolved in mineral oils the reactants should be chosen so as to provide a product which is soluble in the oil base or which can be brought into solution with the aid of solubilizing agents such as high molecular weight alcohols or esters.  The unsaturated hydrocarbon which is reacted with the phospho-sulphurized hydrocarbon may be 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 olefins such as propylene, butylenes, diisobutylenes, triisobutylenes, the codimer of isobutylene and n-butylene, cracked gasoline fractions, cracked paraffin wax, viscous olefinic polymers, cyclopentene, cyclohexene, butadiene, pentadiene, isoprene, dipentene, alpha-pinene, beta-pinene, terpinolene, D 2,4(8)-p-menthadiene or styrene.  The reaction with the olefinic hydrocarbon is preferably conducted at 150-450 DEG  F. for a period up to 10 hours.  In an example, phosphorus pentasulphide is reacted at 425 DEG  F. with a propane de-asphalted, acid treated, de-waxed and decolourized Panhandle residuum of 170 Saybolt Universal Seconds at 210 DEG  F. and the product then reacted with 10 per cent of its weight of dipentene at 380 DEG  F.  Tables are given which compare the processing times and the properties of the product as a 10 per cent blend in gear oil base with those obtained from the same reactants in accordance with the prior art in which the phospho-sulphurization product is cooled and filtered prior to reaction with the dipentene.  The products are stated to be extreme-pressure agents for lubricating oils, preferably mineral lubricating oils (see Group II).  Specifications 687,417 and 717,675 are referred to.ALSO:A lubricating oil composition comprises a lubricating oil preferably a mineral lubricating oil having dissolved therein a minor proportion of a phosphorus and sulphur-containing material obtained by reacting a predominantly hydrocarbon material with a phosphorous sulphide or a mixture of elemental phosphorous and sulphur and then reacting the product, unfiltered and while still warm, at elevated temperature with a hydrocarbon containing at least one olefinic double bond (see Groups IV (a) and IV (b)). The hydrocarbon material is preferably a mineral oil fraction, e.g. a lubricating oil, distillate or residual, preferably a bright stock, or a polymer of one or more hydrocarbons derived from such fractions. The lubricating oil fraction may have been subjected to a refining step such as adsorbent treatment, solvent extraction, distillation and dewaxing.  Specified phosphorous sulphides are the pentasulphide, trisulphide (P4S6), sesquisulphide (P4S3, disulphide (P3S6) and heptasulphide (P4S7).  A mixture of phosphorous sulphides may also be used.  The unsaturated hydrocarbon which is reacted with the phosphosulphurized product may be any aliphatic, cycloaliphatic, terpenic or aliphatic-aromatic hydrocarbon containing at least one olefinic double bond.  Specified unsaturated hydrocarbons are the olefines, such as propylene, butylenes, diisobutylenes, triisobutylenes, the codimer of isobutylene and n-butylene, cracked gasoline fractions, cracked paraffin wax, viscous olefin polymers, e.g. 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 is reacted at 425 DEG F. with a propane deasphalted, acid treated, dewaxed and decoloured Panhandle residuum of 170 Saybolt Universal seconds at 210 DEG F. and the product then reacted with dipentene.  The properties of a 10 per cent. blend of the additive in gear oil base are tabulated.  Specifications 687,417 and 717,675 are referred to.