Patent GB-695371-A (GB)
Title: Improvements in or relating to phosphorus and sulphur containing additives and mineral oil compositions containing them
IPC: C10M159/12
Filed: 1950-06-19
Abstract: Olefine polymers or copolymers are simultaneously reacted at an elevated temperature with a phosphorus sulphide or with phosphorus and sulphur and the product or a metal derivative thereof reacted either with a compound of formula <FORM:0695371/IV (a)/1> where R1, R2, R3, R4 and R5 ar hydrogen or hydrocarbon radicles of 1-20 C atoms, and X is O or S, or with an inorganic acid salt thereof when a metal salt of the first reaction product is present.  The hydrochloride or sulphate of the base may be reacted with the sodium, calcium or barium salt of the phosphorus and sulphur-containing polymer.  Reactions involving the free base are preferred.  The polymer may be treated with sulphur or a sulphur halide optionally followed by dehydrohalogenation, prior to reaction.  Representative of specified groups for R are methyl, 2-ethylhexyl, methylcyclohexyl, phenylethyl, phenyl and tert.-butylphenyl. Bases specified are 4-methyl-, 4-ethyl-, 4-phenyl-, 2-methyl-4-phenyl-, 2-ethyl-4-phenyl- and 1,2-dimethyl-4-phenyl-thiosemicarbazide and 1-ethyl-, 2-propyl- and 4-phenyl-semicarbazide.  P2S3, P4S3, P4S7 and preferably P2S5 are specified phosphorus sulphides.  Polymers specified are mono-olefine polymers of M.W. 100-50,000, preferably 250-10,000 obtained by polymerizing low M.W. olefines such as ethylene or hexene or copolymers thereof and copolymers of low M.W. olefines with diolefines or non-aromatic hydrocarbons of formula CnH2n-x, where x is 2 or a multiple thereof.  Preferre low M.W. olefines are iso-olefines or a tertiary base olefine of preferably less than 7 C atoms, e.g. isobutylene and 2-ethyl-butene-1, whilst non-aromatic hydrocarbons listed include 1,4-hexadiene, acetylenes, isoprene and cyclopentadiene. Preferably the copolymerization is effected in the presence of a catalyst, e.g. aluminium chloride, boron fluoride or benzoyl peroxide and the copolymer has a M.W. of 1000 to 30,000.  The phosphorizing and sulphurizing reaction is effected at 200-600 DEG , preferably 300-550 DEG  F., with preferably 1-3 mols. of polymer to 1 atom of P and at least a third of an atom of S in the phosphorus sulphide or mixture of P and S.  A non-oxidizing atmosphere, e.g. nitrogen, is an advantage.  Preferably the amount of phosphorus sulphide used is one that will react with all the polymer.  When monolefine polymers are treated with P2S5 preferably 1 mol. of sulphide is used to 2-5 mols. of polymer.  The reaction product may be further treated by blowing with steam, alcohol, ammonia or an amine at 200-600 DEG  F.  Reaction with the carbazide is preferably effected in a non-oxidizing atmosphere at 35-500 DEG  F., especially 200-350 DEG  F., and optionally dissolved in a solvent, e.g. naphtha. Preferably 1/2 -1 mol. of carbazide per mol. of hydrocarbon originally taken is used.  Advantageously water-soluble carbazides are reacted in the presence of water.  In examples polyisobutylene of M.W. 1200 is heated with P2S5 at 400 DEG  F. for 5 hours, blown with N2, filtered, dissolved in an oil distillate and reacted (1) in nitrogen at 310 DEG  F. for 3 1/2 hours with 5 per cent (based on active ingredients) of free semicarbazide prepared from the hydrochloride and aqueous KOH, (2) with thiosemicarbazide at 300 DEG F. for 3 hours.ALSO:An essentially hydrocarbon material is reacted at an elevated temperature with a phosphorus sulphide or simultaneously with phosphorus and sulphur and the product or a metal salt thereof reacted either with a compound of formula <FORM:0695371/IV (b)/1> where R1, R2, R3, R4 and R5 are hydrogen or hydrocarbon radicles of 1-20 C atoms, and X is O or S, or with an inorganic acid salt thereof when a metal salt of the first reaction product is present.  The hydrochloride or sulphate of the base can be reacted with the sodium, calcium or barium salt of the phosphorus and sulphur containing hydrocarbon.  reactions involving the free base are preferred.  The hydrocarbon material may be treated with sulphur or a sulphur halide optionally followed by dehydrohalogenation, prior to reaction. Representative of specified groups for R are methyl, 2-ethylhexyl, methylcyclohexyl, phenylethyl, phenyl and tert.-butylphenyl. Specified bases are 4-methyl-, 4-ethyl-, 4-phenyl-, 2-methyl-4-phenyl-, 2-ethyl-4-phenyl- and 1,2-dimethyl-4-phenyl-thiosemicarbazide and 1-ethyl-, 2-propyl- and 4-phenyl-semicarbazide.  P2S3, P4S3, P4S7 and preferably P2S5 are specified phosphorus sulphides.  Hydrocarbon material mentioned includes paraffins, olefines or polymer olefines, diolefines, acetylenes, aromatics or alkyl aromatics, cyclo aliphatics, petroleum fractions, petrolatums, waxes, cracked cycle stocks, condensation products of petroleum fractions, terpenes and solvent extracts of petroleum fractions.  Preferably the olefines have at least 20 C atoms per mol. with about 12-18, preferably at least 15, in a long chain.  Representative of specified hydrocarbon materials are bright stock residuums, acrolein, melene, dehydrohalogenated chlorinated waxes, polymers of, e.g., propylene or hexene, of M.W. 100-50,000, preferably 250-10,000, isoprene, cyclopentadiene, high M.W., e.g. 1000-30,000, copolymers of an olefine with a non-aromatic hydrocarbon of formula CnH2n-x, where x is 2 or a multiple thereof, in the presence of a Friedel-Crafts or peroxide catalyst (listed reactants and catalysts including 2-methyl-butene-1, 1,4-hexadiene, boron fluoride or benzoyl peroxide), benzene, toluene, diphenyl, the condensation product of naphthalene or fluorene with halogenated paraffin wax in the presence of Friedel-Craft catalysts, and resin-oil of M.W. 1000-2000, obtained by precipitating a dewaxed paraffin oil with propane. The phosphorizing and sulphurizing reaction is effected at about 200-600 DEG , preferably about 300-550 DEG  F. with preferably about 1-3 mols. of hydrocarbon to 1 atom of P and at least one-third of an atom of S in the phosphorus sulphide or mixture of P and S. A non-oxidizing atmosphere, e.g. nitrogen, is an advantage. Preferably the amount of phosphorus sulphide used is one that will react with all the hydrocarbon.  When mono-olefine polymers are treated with P2S5 preferably 1 mol. of sulphide is used to 2-5 mols. of polymer.  The reaction product may be further treated by blowing with steam, alcohol, ammonia or an amine at about 200-600 DEG F.  The reaction with the carbazide is preferably effected in a non-oxidizing atmosphere at 35-500 DEG  F., especially 200-350 DEG F., and optionally dissolved in a solvent, e.g. naphtha.  Preferably about 1/2 -1 mol. of carbazide per mol. of hydrocarbon originally taken is used.  Advantageously water-soluble carbazides are reacted dissolved in or mixed with water.  In examples, polyisobutylene of M.W. about 1200 is treated with P2S5 at 400 DEG  F. for 5 hours, blown with N2, filtered, dissolved in an oil distillate and reacted (1) in nitrogen at 310 DEG  F. for 3 1/2 hours with about 5 per cent (based on active ingredients) of free semi-carbazide prepared from the hydrochloride and aqueous KOH; (2) with thiosemicarbazide at 300 DEG  F. for 3 hours.ALSO:Surface-active agents are made by reacting an essentially hydrocarbon material with a phosphorus sulphide, or with phosphorus and sulphur, and reacting the product or a metal salt thereof either with a compound of formula <FORM:0695371/IV (c)/1> where R1, R2, R3, R4 and R5 are hydrogen or hydrocarbon radicles of 1-20 C atoms, and X is O or S, or with an inorganic acid salt thereof when a metal salt of the first reaction product is present.  The hydrocarbon material may be pretreated with sulphur or a sulphur halide optionally followed by dehydrohalogenation.  Many reactants and various reaction conditions are specified (see Group IV (b)). The agents are stated to be of use in dry cleaning fluids, mineral, spirit and aqueous paints, flotation agents and aqueous and non-aqueous insecticides and as dispersants for carbon black in rubber mixes.ALSO:An additive for liquid fuels or lubricating oils is made by reacting an essentially hydrocarbon material with a phosphorus sulphide, or with phosphorus and sulphur, and reacting the product or a metal salt thereof either with a compound of formula <FORM:0695371/III/1> where R1, R2, R3, R4 and R5 are hydrogen or hydrocarbon radicles of 1-20 C atoms and X is O or S, or with an inorganic acid salt thereof when a metal salt of the first reaction product is present.  The hydrocarbon material may be treated with sulphur or a sulphur halide, optionally followed by dehydrohalogenation, prior to reaction.  Many reactants and various reaction conditions are specified (see Group IV(b)).  The hydrocarbon material should provide products which are soluble in mineral oils or which may be plasticized with a high M.W. alcohol or ester.  Alcohols of 8-20 C atoms are preferred e.g. lauryl or stearyl alcohol. Preferably the mineral oil contains about 0.001-10.0 especially 1.0 to about 6.0 per cent of additive.  The additives are detergents and antioxidants and concentrated solutions containing 25-50 per cent of additive in oil may be prepared.  Other additives may be present representative of those specified being substances containing S and/or P such as elemental sulphur, sulphurized mineral oils and terpenes, sulphurized animal and vegetable oils, metal soaps, petroleum and phenol sulphonates, phenates, alcoholates, alkyl phenol sulphides, organo phosphates, thiophosphates, phosphites, thiophosphites, salicylates, xanthates, thioxanthates, thiocarbanates, amines and amine derivatives and reaction products of metal phenates and sulphur or phosphorus sulphides.  Other substances which may be added include dyes, heat-thickened fatty oils, sulphurized fatty oils, resins, rubber, olefine polymers, voltolized fats, mineral oils and/or waxes and colloidal solids such as graphite or zinc oxide.  Many types of mineral lubricating oil are specifi