Patent GB-706127-A (GB)
Title: Improvements in or relating to mineral oil additive
IPC: C10G29/20
Filed: 1951-07-10
Abstract: Phosphorus sulphides are reacted with polymers or copolymers of olefinic or diolefinic hydrocarbons and the acid reaction product neutralized with an organic basic compound which is either a free base of the composition R12 N-C(:NR)-NR112 in which R, R1 an R11 are each hydrogen or hydrocarbon radicals containing 1 to 20 carbon atoms, e.g. guanidine or substituted guanidine or a basic salt of the free base, e.g. guanidine carbonate.  Polymers of ethylene, propylene, butylene, isobutylene, n or isoamylenes or hexenes, butadiene, isoprene, cyclopentadiene, 2, 3-dimethylbutadiene, pentadiene-1, 3, hexadiene-2, 4, terpenes and acetylene or substituted acetylenes or copolymers of low molecular weight olefines and a non-aromatic hydrocarbon, CnH2n-x in which x is 2 or a multiple of 2, e.g. isobutylene, 2-methyl-butene-1, 2-ethyl butene-1, sec; and tertamylenes, and hexylenes, and diolefines and acetylenes may be used.  In a modification the polymeric hydrocarbons may be sulphurized by heating with sulphur at 250 to 450 DEG F., or sulphur may be reacted with the phosphorus sulphide or guanidine derivative. The products are used as antioxidant and detergent additives in mineral lubricating oils.ALSO:The invention comprises a product obtained by reacting a phosphorus sulphide with a hydrocarbon or sulphurized hydrocarbon, neutralizing the acidic reaction product with an organic basic compound which is either a free base of the composition R12N-C(:NR)-NR112 in which R1 R1 and R11 are eac members of the group consisting of hydrogen and hydrocarbon radicals containing 1 to 20 carbon atoms or a basic reacting salt of the aforementioned free base said neutralization being effected in the presence of water without the expulsion of all the water present and preferably by heating, the amount of water remaining being insufficient to cause phase separation, and preferably in excess of 0.5 per cent. by weight of the product and incorporating in such neutralized product an additional amount of said free base or basic reacting salt preferably in amount to give an alkaline A.S.T.M. neutralization number of from about 3.5 to about 12.  By a basic acting salt is meant a salt of an acid the strength of which, measured by pH is less than that of the phosphorus sulphide-hydrocarbon product, e.g. guanidine carbonate.  Compounds of the above formula may have straight or branched hydrocarbon groups. Mentioned are those having at one or more positions R1 R1 and R11, methyl, ethyl, propyl, butyl, iso-amyl, hexyl, heptyl, 2-ethyl-hexyl, decyl, dodecyl, tetra decyl, hexadecyl, stearyl, octadecyl, cyclohexyl, methyl cyclohexyl, benzyl, phenylethyl, phenyl, cresyl, and ter-butylphenyl groups.  The phosphorus sulphide may be P2S3, P4S3, P4S7 or preferably, P2S5.  The hydrocarbon material to be reacted with the phosphorus sulphide may be paraffins, olefins, olefin polymers, diolefins, acetylenes, aromatics, alkyl aromatics, cyclic aliphatics, or petroleum fractions, e.g. lubricating oil fractions, petrolatums, waxes, cracked cycle stocks or condensation products or solvent extracts.  Suitable are bright stock residiums, lubricating oils, petrolatums, paraffin waxes, or products obtained by condensing such hydrocarbons, usually after halogenation, with aromatic hydrocarbons in the presence of inorganic halides, e.g. aluminium chloride, zinc chloride or boron fluoride.  As olefins are mentioned isobutylene, amylene, decene, dodecene, cetene, octadecene, cerotene, melene, olefinic extracts from gasoline or gasoline itself, cracked cycle stocks and polymers thereof, hydrocarbon coal resins, cracked waxes, dehydrohalogenated chlorinated waxes, and mixed high molecular weight alkenes obtained by cracking petroleum oils, or olefins obtained by the dehydrogenation of paraffin waxes, the dehydrohalogenation of long chain alkyl halides, by the synthesis of hydrocarbons from carbon monoxide and hydrogen, or by the dehydration of alcohols.  Other suitable hydrocarbons are polymers of molecular weight 100 to 50,000 obtained by the polymerization or copolymerization of monoolefins, e.g. ethylene, propylene, butylene, isobutylene, n- or iso-amylenes or hexenes.  Diolefins may be employed, e.g. butadiene, isoprene, cyclopentadiene, 2, 3-dimethylbutadiene, pentadiene-1, 3, hexadiene-2, 4, and terpenes. Acetylene and substituted acetylenes may also be used.  Further suitable hydrocarbons are copolymers of mono olefins, preferably iso- or tertiary olefines of less than 7 carbon atoms, with the diolefins of formula Cn H2n-x, where x is 2 or a multiple of 2, or non-conjugated di-olefins such as 1:4-hexadiene, or with acetylenes. Copolymerization may be effected in the presence of aluminium chloride, boron fluoride or benzoyl peroxide, the product preferably having a molecular weight 1,000 to 30,000. Aromatic hydrocarbons and alkylaryl hydrocarbons may also be used. Yet further suitable hydrocarbons are condensation products of aromatic hydrocarbons (e.g. naphthalene, fluorene, phenanthrene, anthracene and coal tar residues) with halogenated aliphatic hydrocarbons, e.g. halogen derivatives of long chain paraffins of more than 8 carbon atoms, such as paraffin wax, petrolatum and ozocerite, or high viscosity paraffin oils preferably which have been treated for the removal of asphalts. A resin-like oil (molecular weight 1,000 to 2,000 or higher) obtained from a dewaxed paraffinic oil by treatment with propane to remove asphalt forms another suitable hydrocarbon.  Sulphurized hydrocarbons produced, e.g. by reaction with sulphur at about 250 DEG F. to 450 DEG F. are also suitable for use as starting material.  Sulphur may also be similarly introduced after reaction with the phosphorus sulphide or guanidine derivative.  Reaction of the hydrocarbon with the phosphorus sulphide preferably is effected at about 200 DEG F. to 600 DEG F. in an inert atmosphere.  The proportions are preferably chosen so that all the phosphorus sulphide reacts.  The neutralized product may be prepared by contacting the phosphorus sulphide-hydrocarbon reaction product, which may be dissolved in naphtha, with the basic compound, e.g. at 100 DEG F. to 400 DEG F. in an inert atmosphere.  In examples a lubricating oil bright stock is prepared by submitting a Mid-continent crude to propane deasphalting, propane dewaxing, and to phenol, sulphuric acid and clay treatments, and the product is in different examples reacted with P2S5 at various temperatures, and neutralized with excess aqueous guanidine carbonate solution with heating.  In some cases, for comparison, all the water is removed.  The products are blended with lubricating oil bases and results are given of tests in a Sanson engine.  Various other compounds may be added in forming mineral oil compositions (see Group III).ALSO:A hydrocarbon oil contains a detergent quantity of a product obtained by reacting a phosphorus sulphide with a hydrocarbon or sulphurised, neutralising the acid reaction product with an organic basic reacting compound which is either a free base of the composition R12N-C(:NR)-CNR112 in which R1R1 and R11 are each members of the group consisting of hydrogen and hydrocarbon radicals containing 1 to 20 carbon atoms or a basic reacting salt of the aforementioned free base said neutralisation being effected in the presence of water without the expulsion of all the water present and preferably by heating, the amount of water remaining being insufficient to cause phase separation, and incorporating in such neutralised product an additional amount of said base or basic reacting salt, preferably in amount to give an A.S.T.M. neutralisation number of from about 3.5 to about 12.  By a basic acting salt is meant a salt of an acid the strength of which, measured by pH is less than that of the phosphorus sulphide-hydrocarbon reaction product e.g. guanidine carbonate. Compounds of the above formula may have straight or branched hydrocarbon radicals.  Mentioned are those having at one or more of the positions R1R1 and R11 methyl, ethyl, propyl, butyl, iso amyl, hexyl, heptyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, stearyl, octadecyl, cycohexyl, methylcyclohexyl, benzyl, phenylethyl, phenyl, cresyl and ter-butyl phenyl.  The phosphorus sulphide may be P2S3, P4S3, P4S7 or preferably P2S5.  The hydrocarbon material to be reacted with the phosphorus sulphide may be paraffins, olefins, olefin polymers, diolefins, acetylenes, aromatics, alkyl aromatics, cyclic aliphatics or petroleum fractions, e.g. lubricating oil fractions, petrolatums, waxes, cracked cycle stocks, or condensation products or solvent extracts.  Suitable hydrocarbons are bright stock residuums, lubricating oils, paraffin waxes or products obtained by condensing such hydrocarbons, usually after halogenation, with aromatic hydrocarbons in the presence of inorganic halides, e.g. aluminium chloride, zinc chloride or boron fluoride.  As olefines are mentioned isobutylene, amylene, decene, dodecene, cetene, octadecene, cerotene, melene, olefinic extracts from gasoline or gasoline itself, cracked cycle stocks, and polymers thereof hydrocarbon coal resins, cracked waxes, dehydrohalogenated chlorinated waxes, and mixed high molecular weight alkenes obtained by cracking petroleum oils, or olefins obtained by the dehydrogenation of paraffin waxes, the dehydrohalogenation of long chain alkyl halides, by the synthesis of hydrocarbons from carbon monoxide and hydrogen, or by the dehydration of alcohols.  Other suitable hydrocarbons are polymers of molecular weight, 100 to 50,000 obtained by the polymerisation or copolymerisation of mono-olefins, e.g. ethylene, propylene, butylene, isobutylene, n-or isoamylenes or hexenes. Diolefins may be used e.g. butadiene, cyclopentadiene, 2, 3-dimethyl-butadiene, isoprene, pentadiene-1, 3, hexadiene -2, 4 terpenes.  Acetylenes and substituted acetylenes may also be u