Patent GB-684168-A (GB)
Title: Improvements in or relating to lubricating compositions
IPC: F02B3/06
Filed: 1950-02-23
Abstract: The Specification comprises as a new chemical product a product obtained either by reacting at an elevated temperature a phosphorus sulphide with a hydrocarbon and neutralizing the acidic reaction product with an organic basic reacting compound selected from the group consisting of (1) free bases of the composition <FORM:0684168/IV (a)/1> in which R, R1 and R11 represent hydrogen or hydrocarbon radicals containing 1-20 carbon atoms, and (2) basic reacting salts of the aforementioned free bases, or by double decomposition of a metal salt of said phosphorus sulphide reaction product with a salt of said free base.  Suitable hydrocarbons include the monoolefin polymers in which the molecular weight ranges from 100 to 50,000, preferably from about 250 to about 10,000.  The polymers may be obtained by the polymerization of low molecular weight mono-olefins such as ethylene, propylene, butylene, isobutylene, normal and isoamylenes, or hexenes, or by the copolymerization of any combination of these olefines.  High molecular weight copolymers of monoolefins and diolefines or acetylenes may also be used. The copolymer may be prepared by controlled copolymerization of an olefine and a non-aromatic hydrocarbon having the formula CnH2n-x, in which x is 2 or a multiple of 2, in the presence of a catalyst of the Friedel-Crafts or peroxide type. The olefin is preferably an iso-olefin or a tertiary olefin of less than 7 carbon atoms per molecule, e.g. isobutylene, 2-methyl-butene-1; 2-ethylbutene-1; secondary and tertiary amylene, and hexylenes.  The non-aromatic hydrocarbon may be a diolefin such as 1,4-hexadiene in which the double bond is not conjugated, as well as the acetylenes and the copolymerisation is preferably carried out in the presence of aluminium chloride, boron fluoride or benzoyl peroxide, the copolymer being preferably one of molecular weight 1,000 to 30,000.  The groups R, R1 and R11 may be the same or different and may be alkyl groups such as methyl, ethyl, propyl, butyl, octyl, iso-octyl, 2-ethyl hexyl, decyl, dodecyl, tetradecyl, cetyl and heptadecyl radicals or they may be cyclo-alkyl, arylalkyl, aryl or alkylaryl, e.g. methyl cyclohexyl, phenylethyl, phenyl, tolyl and tert.-butylphenyl.  A list of substituted guanidines which may be employed as such or in the form of carbonates is given.  The phosphorus sulphide may be P2S3, P2S5, P4S3 or P4S7 but is preferably P2S5.  The reaction of the phosphorus sulphide and hydrocarbon may be effected at 300 DEG  to 550 DEG  F. using 1 to 10, preferably 2 to 5, moles. of hydrocarbon per mol. of the phosphorus sulphide.  The product is then neutralized by treating with guanidine or guanidine derivative, e.g. by contacting the phosphorus sulphide reaction product either as such or dissolved in a suitable solvent such as naphtha with the basic compound preferably at 100 DEG  to 400 DEG  F.  Guanidine carbonate dissolved in or mixed with water yields superior products.  The neutralized reaction product may be further treated by blowing with steam or by treatment with alcohol, ammonia or an amine at 200-600 DEG  F. to improve its odour.  In examples: (1) polyisobutylene (molecular weight 1200) and phosphorus pentasulphide are reacted together at 400 DEG  F. and the mixture then blown with nitrogen, the product being then dissolved in a solvent-extracted Mid-Continent distillate oil and treated with guanidine carbonate in water at elevated temperature and filtered; (2) and (3) as in (1) except that polyethylene (molecular weight 400) and polybutene-1, respectively, are used instead of polyisobutylene.  The products are useful as detergent and anti-oxidant additives for lubricating oils especially mineral lubricating oils, and other detergent additives, and other agents such as dyes, pour depressors, heat-thickened fatty oils, sulphurized oils, organo-metallic compounds, metallic or other soaps, sludge dispersers, anti-oxidants, thickeners, viscosity index improvers, oiliness agents, resins, rubber, olefin polymers, volatilized fats, volatilized mineral oils and/or volatilized waxes and colloidal solids such as graphite or zinc oxide may also be used, as well as solvents and assisting agents (see Group III).  The products are stated to be powerful surface-active agents and may be used in dry-cleaning fluids, mineral, spirit and aqueous paints and as dispersants for insecticides in aqueous and non-aqueous solutions. They are also valuable antioxidants for natural and synthetic rubber.ALSO:The Specification comprises as a new chemical product a product obtained either by reacting at an elevated temperature a phosphorus sulphide with a hydrocarbon and neutralizing the acidic reaction product with an organic basic reacting compound which is either a free base of the composition <FORM:0684168/IV (b)/1> in which R, R1 and R11 represent hydrogen or hydrocarbon radicals containing 1 to 20 carbon atoms, or a basic reacting salt of the said base, or by double decomposition of a metal salt of said phosphorus sulphide reaction product with a salt of said free base.  The products are particularly useful as detergent and antioxidant additives for lubricating oils (see Group III).  The groups R, R1 and R11 may be the same or different and may be alkyl groups such as methyl, ethyl, propyl, butyl, octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, cetyl and heptadecyl radicals or they may be cycloalkyl, arylalkyl, aryl or alkylaryl, e.g. methyl cyclohexyl, phenylethyl, phenyl, tolyl and tert.-butylphenyl groups.  A list of substituted guanides which may be employed either as such or in the form of carbonates is given.  The phosphorus sulphide may be P2S3, P2S5, P4S3, L4S7 and is preferably P2S5.  The hydrocarbon material may be paraffins, olefins or olefin polymers, diolefins, acetylenes, aromatics or alkyl aromatics, cyclo aliphatic hydrocarbons, petroleum fractions, such as lubricating oil fractions, bright stock residuums, petrolatums, waxes, cracked cycle stocks, or condensation products of petroleum fractions, or solvent extracts of petroleum fractions. Specified mono-olefins are isobutylene, decene, dodecene, cetene, 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.  Preferred olefins are those having at least 20 carbon atoms per molecule and which may be obtained by the dehydrogenation of paraffin waxes, by the dehydrohalogenation of long-chain alkyl halides, by the synthesis of hydrocarbons from CO and H2 and by the dehydration of alcohols. Diolefines which may be employed include butadiene, isoprene, cyclopentadiene, 2,3-dimethylbutadiene, pentadiene, 1,3, hexadiene-2,4; and terpenes.  Acetylene and substituted acetylenes and aromatic hydrocarbons such as benzene, naphthalene, anthracene, toluene, xylene, and diphenyl may also be used.  Condensation products of halogenated aliphatic hydrocarbons with an aromatic compound in the presence of a Friedel-Crafts type catalyst, e.g. aluminium chloride, zinc chloride or boron fluoride may also be used, the halogenated hydrocarbon being preferably derived from a paraffin hydrocarbon having more than 8 carbon atoms, e.g. paraffin wax, petrolatum and ozocerite wax, or a high viscosity paraffin oil, particularly heavy residual oil which has been extracted with propane or other solvents for the removal of asphalts.  The aromatic constituent may be naphthalene, fluorene, phenanthrene, anthracene and coal tar residues.  A high molecular weight hydrocarbon material obtained from a paraffinic oil which has been dewaxed and then treated with a liquified normally gaseous hydrocarbon, e.g. propene, to precipitate a heavy propane insoluble fraction may also be used. Other hydrocarbon starting materials are the mono-olefin polymers and copolymers and copolymers of mono-olefins with diolefines or acetylenes (see Group IV(a)).  The reaction of the phosphorus sulphide and hydrocarbon may be effected at 300 DEG  to 550 DEG  F. using 1 to 10, preferably 2 to 5 moles of hydrocarbon per mol of the phosphorus sulphide.  The product is then neutralized p  by treating with guanidine or guanidine derivative, e.g. by contacting the phosphorus sulphide reaction product, either as such or dissolved in a suitable solvent such as naphtha, with the basic compound, preferably at 100 DEG  to 400 DEG  F.  An excess of the basic compound over that required to neutralize the titratable acidity of the phosphorus sulphide reaction product may be used and superior products are obtained when a water-soluble basic salt of the organic base, e.g. guanidine carbonate, is dissolved in or mixed with water when contacted with the phosphorus sulphide reaction product.  The neutralized reaction product may be further treated by blowing with steam or by treatment with alcohol, ammonia, or an amine at 200-600 DEG  F. to improve the odour thereof.  In examples: (1) to (3) octadecene is dissolved in conventionally refined Coastal distillate oil and treated with phosphorus pentasulphide at 144 DEG  C. in an atmosphere of nitrogen. The hot solution was then filtered and the concentrate of the P2S5 treated octadecene heated to 125 DEG  C. and guanidine carbonate added and the temperature maintained at 144 DEG C. for two hours.  The products are stated to be powerful surface-active agents and may be used in dry cleaning fluids, mineral oil, spirit and aqueous paints and as dispersants for insecticides in aqueous and non-aqueous solutions.  They are also valuable anti-oxidants for natural and synthetic rubber.ALSO:A lubricating composition comprises a lubricating oil containing a detergent quantity of a product obtained either by reacting at elevated tempe