Patent GB-687417-A (GB)
Title: Improvements in or relating to lubricating oil compositions
IPC: C09K23/00
Filed: 1950-02-07
Abstract: A phosphorus and sulphur containing compound suitable as a lubricating oil additive (see Group III), is obtained by reacting at elevated temperature one molecular proportion of a phosphorus sulphide with one to ten, preferably two to five molecular proportions of a hydrocarbon and further reacting the acidic product thus formed with 0.1 to 50 per cent of its weight of a hydrocarbon containing at least one olefinic double bond.  The preferred phosphorus sulphide is the pentasulphide but other phosphorus sulphides, e.g. P2S3, P4S3 and P4S7 may be used.  Mixtures of two or more phosphorus sulphides may also be employed.  The hydrocarbons which may be reacted with phosphorus sulphide may be paraffins, olefines, olefine polymers, diolefines, acetylenes, aromatic or alkyl aromatic hydrocarbons, cycloaliphatic hydrocarbons, petroleum fractions, such as lubricating oil fractions, petrolatums, waxes, cracked cycle stocks, condensation products of petroleum fractions, or solvent extracts of petroleum fractions. Essentially paraffinic hydrocarbons such as bright stock residuums and lubricating oil distillates may be employed as well as the products obtained by condensing any of the above paraffinic hydrocarbons, usually through first halogenating the hydrocarbon, with aromatic hydrocarbons in the presence of anhydrous inorganic halides such as aluminium chloride, zinc chloride, or boron fluoride.  Several hydrocarbons are specified as starting materials (see Group IV (b)).  The olefine polymers which may be used may be mono-olefine polymers of molecular weight ranging from 100 to 50,000 which may be obtained by the polymerization of low molecular weight monolefines such as ethylene, propylene, butylene, isobutylene, normal and isoamylenes, or hexenes, or by the copolymerization of any combination of these olefines.  The copolymers of a low molecular weight olefine and a diolefine or a non-aromatic hydrocarbon of the formula CnH2n-x in which x is 2 or a multiple of 2 in the presence of a Friedel-Crafts or peroxide type catalyst may also be used, the low molecular weight olefine being preferably an isoolefine or a tertiary olefine, e.g. isobutylene; 2-methyl-butene-1; 2-ethylbutene-1, secondary and tertiary amylenes and hexylenes. The non-aromatic hydrocarbon may be a conjugated diolefine, e.g. butadiene, isoprene, cyclopentadiene, 2,3-dimethylbutadiene, pentadiene-1,3, and hexadiene-2,4, or a diolefine such as 1,4-hexadiene in which the double bond is not conjugated, as well as the acetylenes.  The copolymerization is preferably carried out in the presence of aluminium chloride, boron fluoride or benzoyl peroxide and the copolymer preferably has a molecular weight of 1,000 to 30,000.  The phosphorus sulphide reaction product may be further treated by blowing with steam, alcohol, ammonia, or an amine at 200 DEG  to 600 DEG  F. to improve the odour thereof.  The product obtained by reacting the hydrocarbon with a phosphorus sulphide is then further reacted with an unsaturated hydrocarbon which may be any aliphatic, cycloaliphatic, terpenic or aliphatic aromatic hydrocarbon containing at least one double carbon-carbon linkage in a non-aromatic group, e.g. the olefines such as propylene, the isomeric butylenes, diisobutylenes, triisobutylenes, the codimer of isobutylene and n-butylene, cracked gasoline fractions, cracked paraffin wax, viscous olefine polymers such as medium or high molecular weight polybutene; cyclopentene, cyclohexene, butadiene, pentadiene, isoprene, dipentene, a -pinene, b -pinene, terpinolene, D 2,4(8)-p-menthadiene and styrene.  The further treatment with the olefinic hydrocarbon may be effected at room temperature or preferably at 150-380 DEG  F.  An excess of the olefinic hydrocarbon may be employed in which case a quantity of sulphur is then added, preferably with the addition of a vulcanizing accelerator.  The additives may be blended with lubricating oils which may be synthetic oils prepared by the polymerization olefines. The additives may also be used in dry cleaning fluids, in mineral spirit and aqueous paints, as flotation agents, as dispersants for insecticides in aqueous and non-aqueous solutions, as additives for synthetic rubber, as carbon black dispersants, as vulcanization accelerators, and as metal dispersants and antioxidants in colloidal iron electromagnetic clutches.  They are also useful dispersants in printing ink, asphalts, linoleum, roofing compositions, drilling muds, metal cleaners and pickling solutions.ALSO:A phosphorus and sulphur-containing compound suitable as a lubricating oil additive (see Group III) is obtained by reacting at elevated temperature one molecular proportion of a phosphorus sulphide with one to ten, preferably two to five molecular proportions of a hydrocarbon and further reacting the acidic product thus formed with 0.1 to 50 per cent of its weight of a hydrocarbon containing at least one olefinic double bond.  The preferred phosphorus sulphide is the pentasulphide (P2S5) but other phosphorus sulphides, e.g. P2S3, P4S3 and P4S7 may be used.  Mixtures of two or more phosphorus sulphides may also be employed.  The hydrocarbon which may be reacted with the phosphorus sulphide may be paraffins, olefins, olefine polymers (see Group IV (a)), diolefines, acetylenes, aromatic or alkyl aromatic hydrocarbons, cycloaliphatic hydrocarbons, petroleum fractions, such as lubricating oil fractions, petrolatums, waxes, cracked cycle stocks, condensation products of petroleum fractions, or solvent extracts of petroleum fractions. Essentially paraffinic hydrocarbons such as bright stock residuums and lubricating oil distillates may be employed, as well as products obtained by condensing any of the above paraffinic hydrocarbons usually through first halogenating the hydrocarbon, with aromatic hydrocarbons in the presence of anhydrous inorganic halides, such as aluminium chloride, zinc chloride or boron fluoride.  Specified olefines are isobutylene, decene, dodecene, cetene (C16), octadecene, cerotene, melene, olefinic extracts from gasoline or gasoline itself, cracked cycle stocks and polymers thereof, resin oils from crude oil, hydrocarbon coal resins, cracked waxes, dehydrohalogenated chlorinated waxes, and any mixed high molecular weight alkenes obtained by cracking petroleum oils.  It is preferred to use olefines having at least 20 carbon atoms per molecule, of which from 12 to 18 carbon atoms are in a long chain, e.g. the olefins obtained by dehydrogenation of paraffin waxes, by the dehydrohalogenation of long-chain alkyl halides, by the synthesis of hydrocarbons from CO and H2, or by dehydration of alcohols.  Other suitable olefins are the mono-olefin polymers (see Group IV (a)), and diolefines such as butadiene, isoprene, cyclopentadiene, 2,3-dimethylbutadiene; pentadiene-1,3; hexadiene-2,4; and terpenes. Acetylene and substituted acetylenes may also be employed.  Other hydrocarbons which may be used are aromatic hydrocarbons such as benzene, naphthalene, anthracene, toluene, xylene and diphenyl, as well as aromatic hydrocarbons having alkyl substituents and aliphatic hydrocarbons having aryl substituents.  A resin-like oil of high molecular weight obtained preferably from a paraffinic oil which has been dewaxed and then treated with a liquefied normally gaseous hydrocarbon, e.g. propane, to precipitate a heavy propane insoluble fraction may also be used.  The phosphorus sulphide may be reacted with the hydrocarbon at 200 DEG  to 600 DEG  F., preferably in a non-oxidizing atmosphere, e.g. of nitrogen.  If desired, the reaction product may be further treated by blowing with steam, alcohol, ammonia, or an amine, at 200 DEG  to 600 DEG  F. to improve the odour thereof.  The reaction product is then reacted with the unsaturated hydrocarbon and this may be effected at room temperature or preferably at 150-380 DEG  F.  An excess of the unsaturated hydrocarbon may be employed in which case a quantity of sulphur is then added, preferably with the addition of a vulcanization accelerator.  The unsaturated hydrocarbon which is reacted with the phosphorus sulphide-hydrocarbon reaction product 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, e.g. the olefines such as propylene, the isomeric butylenes, diisobutylenes, triisobutylenes, the codimer of isobutylene and n-butylene, cracked gasoline fractions, cracked paraffin wax, viscous olefin polymers (see Group IV (a)), cyclopentene, cyclohexene, butadiene, pentadiene, isoprene, dipentene, a -pinene, b -pinene, terpinolene, D 2,4(8)-p.-menthadiene and styrene.  In examples: (1) phosphorus pentasulphide is reacted at 350-370 DEG  F. and in an atmosphere of nitrogen with a lubricating oil bright stock in the presence of benzoyl peroxide and the product is then heated with diisobutylene, nitrogen gas being bubbled through the reaction mixture; (2) as in (1) except that commercial dipentene (a mixture of terpinolene and a -pinene containing small amounts of a -pinene, a -terpineol, D -2,4(8)-p-menthadiene, and para-cymene) is used instead of diisobutylene.  The products in addition to being employed in lubricants may also be used in other mineral oil products and also have practical use in dry cleaning fluids, mineral spirit and aqueous paints, as flotation agents, as dispersants for insecticides in aqueous and non-aqueous solutions, as carbon black dispersants, and as metal dispersants and antioxidants in colloidal iron electromagnetic clutches.  They are also useful dispersants in printing ink, asphalts, linoleum, roofing compositions, drilling muds, metal cleaners and pickling solutions.ALSO:A lubricating composition comprises a lubricating oil, preferably a mineral lubricating oil, containing a detergent quantity of a product obtained by reacting