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US3354189A - Metal (hydrocarbyl and acid hydrocarbyl pyrophosphates) and amine adducts - Google Patents

Metal (hydrocarbyl and acid hydrocarbyl pyrophosphates) and amine adducts Download PDF

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US3354189A
US3354189A US459089A US45908965A US3354189A US 3354189 A US3354189 A US 3354189A US 459089 A US459089 A US 459089A US 45908965 A US45908965 A US 45908965A US 3354189 A US3354189 A US 3354189A
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pyrophosphate
mono
monoacid
metal
hydrocarbyl
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US459089A
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Anthony J Revukas
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Citgo Petroleum Corp
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Cities Service Oil Co
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Assigned to CITIES SERVICE COMPANY A CORP. OF DE. reassignment CITIES SERVICE COMPANY A CORP. OF DE. MERGER (SEE DOCUMENT FOR DETAILS). DELAWARE, EFFECTIVE DEC. 20, 1978 Assignors: CITIES SERVICE OIL COMPANY
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
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    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
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    • C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • C—CHEMISTRY; METALLURGY
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085—Phosphorus oxides, acids or salts
    • C—CHEMISTRY; METALLURGY
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/108—Residual fractions, e.g. bright stocks
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
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    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/042—Metal salts thereof
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/02—Esters of silicic acids
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/08—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having metal-to-carbon bonds
    • C10M2227/082—Pb compounds
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    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/02—Unspecified siloxanes; Silicones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
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Definitions

  • ABSTRACT OF THE DISCLOURE Novel metal (hydrocarbyl pyrophosphates) and metal (acid hydrocarbyl pyrophosphates), as well as amine adducts of the metal acid hydrocarbyl pyrophosphates, are found to be useful as gasolene and lubricating oil additives.
  • This invention relates to novel metal organo pyrophosphates, and more particularly to metal (hydrocarbyl pyrophosphates) and metal (acid hydrocarbyl pyrophosphates), and to hydrocarbon compositions containing such compounds.
  • the invention relates to novel amine adducts of the metal (acid hydrocarbyl pyrophosphates) and to hydrocarbon compositions containing such amine adducts.
  • liquid hydrocarbon products such as fuels and lubricating oils contain additives for improving their performance characteristics.
  • additives are employed for improving various performance characteristics such as to assist in maintaining cleanliness of the carburetor, to resist surface ignition, and to inhibit rust and carburetor icing.
  • Lubricating com positions contain various additives such as those for improving viscosity index and lubricity. The additives vary in effectiveness and it is often necessary to use a number of additives in a single composition.
  • metal (hydrocarbyl pyrophosphates) and metal (acid hydrocarbyl pyrophosphates) are beneficial for imparting carburetor and intake system detergency, rust suppression, reduction in octane requirement increase, resistance to surface ignition of liquid hydrocarbon fuels, and friction and wear reduction in mineral oil lubricants. It has been further found that reaction products of amines and these metal (acid hydrocarbyl pyrophosphates) are especially advantageous for these purposes. It is to be understood that the term metal as used herein is intended to include silicon, which is normally considered to be a non-metal.
  • the metal organo pyrophosphates of the present invention may be generally represented by the formula:
  • M is a polyvalent metal
  • n is an integer of from 0 to 4
  • n is an integer from 0 to 2 and the sum of n plus 211' is equal to the valence of the metal and is an integer from 2 to 4
  • R, R, R" and R' are hydrocarbyl groups having from 1 to about 30 carbon atoms.
  • M in the above Formula I represents a polyvalent element having a valence of 2 to 4 and selected from the group consisting of manganese, chromium, molybdenum,
  • the metal organo pyrophosphates can have 0, 1, 2, 3, or 4 acid groups (OH) per metal atom, but preferably contain at least one acid group.
  • Particularly desirable compounds are the acid hydrocarbyl pyrophosphates of Group IVB metals, namely titanium, zirconium and hafnium.
  • R, R, R" and R may represent identical or different hydrocarbyl groups. While any hydrocarbyl groups having between 1 and about 30 carbon atoms and soluble to the required extent in gasoline may be used, the aliphatic hydrocarbyl groups, particularly branched-chain aliphatic hydrocarbyl groups of from 6 to about 22 carbon atoms are preferred. Such groups are generally more soluble in gasoline than other hydrocarbyl groups, thereby facilitating the use of the novel compounds as gasoline additives. Furthermore, the total number of carbon atoms per molecule of metal organo pyrophosphate can vary from about 2 to about 240, but preferably ranges from about 12 to about carbon atoms.
  • Typical R, R, R" and R groups may include, for instance, alkyl, alkenyl, aryl, alkylaryl, arylalkyl or alicyclic hydrocarbon radicals.
  • suitable hydrocarbyl radicals are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, isohexyl, 2,2,4- trimethylpentyl, Z-methylpentyl, 2,2 dimethylbutyl, 2,3- dimethylbutyl, heptyl, Z-methylhexyl, S-methylhexyl, 3,3- dimethylpentyl, octyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, Z-ethylhexyl, Z-ethylbutyl, nonyl, decyl, undecyl
  • the compounds of Formula I above may be prepared, for instance, by reacting 1 mole of phosphorous pentoxide with 2 moles of a hydroxy compound, or a mixture of hydroxy compounds, in which the hydroxy group is attached to a hydrocarbyl radical of 1 to about 30 carbon atoms to form a dihydrocarbyl diacid pyrophosphate.
  • the dihydrocarbyl diacid pyrophosphate so formed may then be reacted with a suitable amount of a halide of the desired metal dispersed .or dissolved in an organic solvent.
  • the metal tetrahalides may be reacted with dihydrocarbyl diacid pyrophosphates in molar ratios of 1:2, 1:3 and 1:4 to form, respectively, metal (IV) bis[di(hydrocarbyl) pyrophosphate]; metal (IV) di [monoacid di(hydrocarbyl) pyrophosphate] mono [di (hydrocarbyl) pyrophosphate] and metal (IV) tetra [monoacid di(hydrocarbyl) pyrophosphate].
  • metal trihalides may be reacted with dihydrocarbyl diacid pyrophosphates in molar ratios of 1:2 and 1:3 to form, respectively, metal (III) mono [monoacid di(hydrocarbyl) pyrophosphate] mono [di(hydrocarbyl) pyroph-ospate]; and metal (Ill) tri[monoacid di(hydrocarbyl) pyrophosphate].
  • metal dihalides may be reacted with dihydrocarbyl diacid pyrophosphates in molar ratios of 1:1 and 1:2 to form respectively, metal (II) mono[di(hydrocarbyl) pyrophosphate] and metal (H) bis [monoacid di(hydrocarbyl) pyrophosphate].
  • the metal organo pyrophosphates of Formula I may be prepared by reacting together, in a single step, the metal halide, phosphorous pentoxide and the hydroxy compound in the same relative proportions as given above.
  • the reactants may be combined in the proportions of 8 moles of hydroxy compound to 4 moles of phosphorous pentoxide to 1 mole of the metal tetrahalide.
  • the reactants may be simply mixed together at a temperature from about 10 C. to about 1.20 C., in an inert solvent.
  • the inert solvent is preferably a hydrocarbon such as an aliphatic or an aromatic hydrocarbon, e.g. benzene, toluene, heptane, octane, hexane, etc.
  • the inert organic solvent need not be a hydrocarbon, but instead any inert organic solvent such as an ether or halogenated hydrocarbon, e.g. ethyl ether, tetrahydrofuran, carbon tetrachloride, chlorobenzene, etc., can be employed.
  • identity of the hydrocarbyl groups present in the compounds represented by Formula I is determined by the identity of the hydrocarbyl groups present in the dihydrocarbyl diacid pyrophospates or hydroxy compounds used as reactants.
  • reaction mixtures resulting from the above-noted preparatory procedures may or may not contain minor quantities of additional compounds, not all of which have been identified, in addition to the metal organo pyrophosphates represented by Formula I. Regardless of their identity, these extraneous compounds do not impair the effectiveness of the metal organo pyrophosphate compounds of the present invention as gasoline and lubricating oil additives, and, therefore, need not be separated therefrom. Furthermore, although generally desirable, it is not necessary to separate the compounds of the present invention from the solvent in which they are prepared prior to use.
  • particularly desirable metal organo pyrophosphates of the present invention are those which contain at least one acid group (OH) per metal atom, i.e. the metal [acid hydrocarbyl pyrophosphates].
  • these metal [acid hydrocarbyl pyrophosphates] may be reacted with an organic amine to form amine adducts having exceptional properties as additives in liquid hydrocarbon compositions.
  • the novel amine adducts of this invention are useful as lubricant additives, anticorrosion additives, detergents, anti-stall additives, and to reduce octane requirement increase.
  • the amine adducts can be prepared by simply neutralizing the free acid group or groups of the metal[acid hydrocarbyl pyrophosphates]. Formation of the adduct takes place at a temperature between about C. and 60 C. Preferably each of the acid groups of the pyrophosphate is neutralized with basic nitrogen of the amine reactant, although this is not essential. Neutralization can be accomplished by simply adding the amine to the metal[acid hydrocarbyl pyrophosphate] to raise the pH thereof to at least 6 or 7. Also, the neutralization can be accomplished by adding a stoichiometric quantity of the amine to the metal[acid hydrocarbyl pyrophosphate].
  • the amine employed in preparing the amine adducts of the present invention can be any salt-forming amine having from 1 to about 30 carbon atoms.
  • primary, secondary, tertiary, aliphatic, aromatic or alicyclic amines may be used.
  • the cyclic amines can be carbocyclic or heterocyclic.
  • the amine can also be a mono-, di-, tri-, or other polyarnine.
  • the amine may be a [3- amine and may contain various substituent groups such as hydroxyl groups.
  • Preferred amines useful in the practice of the invention are aliphatic, monoor polyamines containing 6 to 22 carbon atoms arranged in an alkyl or alkenyl chain.
  • Suitable amines for preparing the amine adducts of the metal organo orthophosphates and pyrophosphates there can be mentioned: methylamine, ethylamine, diethylamine, propylamine, tn'propylamine, isopropylamine, butylamine, isobutylamine, hexylamine, 2- ethylhexylamine, octylamine, dodecylamine, 2-propylde- 6 cylamine, pentadecylamine, tetradecylamine, octadecylamine, 6-butyloctadecylamine, eicosamine, 6,6-dimethyl-ipropyldecylamine, 8-hexyl-10-isobutyloctadecylamine, dioctylamine, tribenzylamine, hexadecylamine, decylamine,
  • N-hexyloctylamine N,N-dimethyldodecylamine, oleylamine, linoleylamine, 1,IO-decamethylerrediamine, ethylenediamine, 1,2-propylenediamine, 1,12-dodecamethylenediamine, tetramethylenediamine, 1,6-heXamethylenediamine, tetramethylenediamine, 1,6-hexamethylenediamine, triethylenetetramine, 1,2-phenylenediamine, benzylamine, 3,3-biphenyldiamine, biphenylamine, l-naphthylamine, lfiuorenamine, aniline, N-methylaniline N,N-dimethylaniline, 2,3-phenylenediamine, piperazine, piperidine, furfurylamine, N-cyclohexylheptylamine, and the like.
  • the amines can also contain various substituent groups such as hydroxyl groups, eg alkanol amines, such as diethylanolamine, 3,3'-hydroxydipropanolamine, isopropanolamine, and the like.
  • fl-amine such as octyl-fl-amine, can also be used. Mixtures of amines may also be used to prepare the amine adducts of the present invention.
  • cocoamine which is a mixture of amines prepared from coconut oil fatty acids and contains predominantly n-dodecylamine
  • soya amine which is a mixture of amines containing 16 to 18 carbon atoms
  • the amine adducts provided by the invention may be represented by the following formula:
  • M is metal having a valence of 2 to 4 and particularly an element selected from the group consisting of manganese, chromium, molybdenum, copper, gold and silicon and the metals of Groups II, IV and VIII of the Periodic Table; each of R, R, R" and R' are hydrocarbyl groups having from 1 to about 30 carbon atoms;
  • n is an integrer from 1 to 4; n is an integer from 0 to 1;
  • n plus 2n is equal to the valence of the metal and is an integer from 2 to 4; and A is an amine containing from 1 to about 30 carbon atoms.
  • each R, R, R" and R' is a branched-chain hydrocarbyl radical having from 6 to 22 carbon atoms (e.g. Z-ethylhexyl), n is 0, n is 4, and A is an amine containing from 6 to 22 carbon atoms arranged in an aliphatic hydrocarbyl group, which may be alkyl or alkenyl.
  • the compositions of the present invention When used as gasoline additives, the compositions of the present invention, namely metal[hydrocarbyl pyrophosphates], metal[acid hydrocarbyl pyrophosphates] and amine salts of metal[acid hydrocarbyl pyrophosphate], are used in an amount between 10 and about 500 parts per million parts of gasoline by weight, preferably from to about 250 p.p.m. and particularly from about to 200 p.p.m.
  • the gasoline composition can be either leaded or unleaded, although leaded gasoline is preferred.
  • a gasoline composition is provided which comprises a major portion of leaded hydrocarbon base fuel boiling in the gasoline range and containing between 10 and 500 p.p.m.
  • amine salts represented by Formula 11 above and particularly the salts obtained by reacting an amine containing from 6 to 22 carbon atoms arranged in an aliphatic hydrocarbyl group with a metal (IV-B) [monoacid di(branched-chain C to C hydrocarbyl) pyrophosphate].
  • IV-B metal
  • gasoline, hydrocarbon base boiling in a gasoline range and similar terms refer to a petroleum fraction boiling in the gasoline range (e.g. between F. and about 450 F.).
  • leaded gasoline refers to gasoline to which there has been added a small amount, such as between 0.1 and about 6.0 ml. per gallon of metallo organic antiknock compound such as tetraethyl lead (TEL), tetramethyl lead (TML), tetraisopropyl lead, etc.
  • the gasoline compositions of this invention can also include, for instance, light hydrocarbon lubricating oils having viscosities at 100 F. of between about 50 and about 200 Saybolt Universal Seconds (SSU) and viscosity indexes of between about 30 and about 130. Such oils may be present in suitable amounts such as between about 0.1 and about 1.0% by weight of the gasoline composition.
  • SSU Saybolt Universal Seconds
  • the additives provided by the present invention improve the boundary lubrication properties of the composition.
  • lubricants containing the additives of this invention inhibit the stick-slip sliding tendencies that are often found in automatic transmission clutching surfaces.
  • the amount of additive can vary over a wide range such as from 0.01% to about 3%, by weight, of the lubricant base material.
  • the amine salts of the metal[acid hydrocarbyl pyrophosphates] are particularly desirable lubricating oil additives.
  • Suitable mineral oil base materials include and 200 neutral oils, light and heavy intermediate mineral oils, bright stock as well as combinations of the foregoing. If a synthetic base material is used, it can be that of diesters, polyesters, silicones, silicates, fluorocarbons, phosphates and the like.
  • the additives of the present invention may also be used in other hydrocarbon compositions.
  • they may be used in minor quantities of diesel fuel oil compositions to impart anti-rust activity, etc. to the composition.
  • Titanium tetra[monoacid di(2-ethylhexyl) pyrophosphate] is obtained by reacting phosphorous pentoxide, titanium tetrachloride and 2-ethyl-1-hexanol as shown below:
  • R is 2-ethylhexyl
  • the product is very viscous and weighs g., which is 96% of theory based on the metal halide. Upon analysis, the product is found to contain 2.98% titanium and 15.36% phosphorous, theory being 2.89% titanium and 14.99% phosphorous.
  • Example 2 In the manner described in Example 1, a mixture of 0.4 mole (56.8 g.) of P and 0.1 mole (23.3 g.) of ZrCL; in 500 ml. of anhydrous n-heptane is reacted with 0.84 mole (133 g.) of isodecyl alcohol to form zirconium tetra[monoacid di(isodecyl)pyrophosphate], which is represented by the following formula:
  • R is isodecyl
  • Example 3 wherein two of the R groups are isodecyl and the two remaining R groups are octylphenol.
  • Example 4 A mixture of 0.2 mole (56.8 g.) of P 0 and 0.1 mole (27.2 g.) of cadmium bromide is finely dispersed by vigorous stirring in 400 ml. of a reaction medium consisting of equal volumes of n-heptane and toluene. Then 0.42 mole (55 g.) of iso-octanol is added in the manner described in Example 1. The reactants are heated under reflux at 98 C.105 C. until liberation of by-product HBr is completed. The solvent is removed by distillation at lower pressure to obtain as the residue cadmium bis [monoacid di(iso-octyl)pyrophosphate] as shown below:
  • R is iso-octyl
  • Example 5 To a mixture of 4 moles (568 g.) of P 0 and 1 mole (170 g.) of SiCl in 1500 ml. of dry n-heptane, there is added 8.4 moles (1683 g.) of tridecanol in the manner described in Example 1. Upon completion of the reaction, as evidenced by no further liberation of HCl at C., the n-heptane and any remaining tridecanol are removed by distillation at 120 C. and 2 mm., pressure. The remaining viscous product is silicon tetra[monoacid di(tridecyl)pyrophosphate].
  • Example 6 The titanium tetra[monoacid di(2-ethylhexyl)pyrophosphate] product of Example 1 is mixed with various amines to obtain products having a pH of 7. The reactants are thoroughly mixed at room temperature while protected from carbon dioxide in a vessel blanketed with air. The amounts of amines employed to obtain adducts of pH 7 are given in the following tabulation:
  • Example 8 A measure of the boundary lubricating ability of each of the amine adducts of titanium tetra[monoacid di(2- ethylhexyl)pyrophosphate] of Example 7 in lubricating oil, and consequently their effectiveness in reducing wear, is obtained by means of a special apparatus used to assess the boundary properties of lubricants in the 50 F.- 350" F. range. The measurment is reported as Normal Lubricity Indices, NLI, and values of 200 and above are considered very good.
  • Amine adduct of Noleyl-1, I i-propylene diamine and titanium tetra[monoacid di(2-ethylhexyl) pyrophosphate] 386 The following example illustrates the use of the amine adducts of Example 7 as additives in gasoline compositions.
  • Example 9 Gasoline compositions are prepared by employing each of the previously-noted amine adducts of titanium tetra [monoacid di(2-ethylhexyl) pyrophosphate] in an amount 1 1 of 50 p.p.m. in a base gasoline having the following characteristics:
  • ASTM rust tests are run at 75 F. with each of the additive-containing gasoline compositions using distilled water. Each of the compositions passed the test.
  • M is a Group lI-B metal
  • n is an integer from 0 to 4
  • n is an integer from 0 to 2
  • the sum of n plus 2n is equal to the valence of the metal and is an integer from 2 to 4
  • R, R, R", and R are hydrocarbyl groups having from 1 to about 30 carbon atoms.
  • R, R, R" and R are aliphatic hydrocarbyl groups.
  • R, R, R" and R' are branched-chain aliphatic hydrocarbyl groups having from about 6 to about 22 carbon atoms.
  • n is from 1 to 4 and n is from O to 1.

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Description

United States Patent Oflice 3,354,189 Patented Nov. 21, 1957 3,354,189 METAL (HYDROCARBYL AND ACID HYDRO- CARBYL PYROPHOSPHATES) AND AMINE ADDUCTS Anthony J. Revulras, Cranford, N.J., assignor to Cities Service Oil Company, Bartlesville, Okla, a corporation of Delaware No Drawing. Filed May 26, 1965, Ser. No. 459,089 Claims. (Cl. 260-429.5)
ABSTRACT OF THE DISCLOURE Novel metal (hydrocarbyl pyrophosphates) and metal (acid hydrocarbyl pyrophosphates), as well as amine adducts of the metal acid hydrocarbyl pyrophosphates, are found to be useful as gasolene and lubricating oil additives.
This application is a continuation-in-part of my copending application S.N. 350,113 filed Mar. 6, 1964.
This invention relates to novel metal organo pyrophosphates, and more particularly to metal (hydrocarbyl pyrophosphates) and metal (acid hydrocarbyl pyrophosphates), and to hydrocarbon compositions containing such compounds. In other aspects, the invention relates to novel amine adducts of the metal (acid hydrocarbyl pyrophosphates) and to hydrocarbon compositions containing such amine adducts.
Normally liquid hydrocarbon products such as fuels and lubricating oils contain additives for improving their performance characteristics. Thus, in fuels such as gasoline additives are employed for improving various performance characteristics such as to assist in maintaining cleanliness of the carburetor, to resist surface ignition, and to inhibit rust and carburetor icing. Lubricating com positions contain various additives such as those for improving viscosity index and lubricity. The additives vary in effectiveness and it is often necessary to use a number of additives in a single composition.
It has now been found that metal (hydrocarbyl pyrophosphates) and metal (acid hydrocarbyl pyrophosphates) are beneficial for imparting carburetor and intake system detergency, rust suppression, reduction in octane requirement increase, resistance to surface ignition of liquid hydrocarbon fuels, and friction and wear reduction in mineral oil lubricants. It has been further found that reaction products of amines and these metal (acid hydrocarbyl pyrophosphates) are especially advantageous for these purposes. It is to be understood that the term metal as used herein is intended to include silicon, which is normally considered to be a non-metal.
The metal organo pyrophosphates of the present invention may be generally represented by the formula:
wherein M is a polyvalent metal; n is an integer of from 0 to 4; n is an integer from 0 to 2 and the sum of n plus 211' is equal to the valence of the metal and is an integer from 2 to 4; and R, R, R" and R' are hydrocarbyl groups having from 1 to about 30 carbon atoms.
M in the above Formula I represents a polyvalent element having a valence of 2 to 4 and selected from the group consisting of manganese, chromium, molybdenum,
copper, gold and silicon and the metals of Groups II, IV, and VIII of the Periodic Table. A suitable Periodic Table is shown on pp. 392-393 of the Handbook of Chemistry and Physics, Thirty-fifth Edition (1953). It can be seen from Formula I that the metal organo pyrophosphates can have 0, 1, 2, 3, or 4 acid groups (OH) per metal atom, but preferably contain at least one acid group. Particularly desirable compounds are the acid hydrocarbyl pyrophosphates of Group IVB metals, namely titanium, zirconium and hafnium. Compounds of this type are the metal (IVB) di[monoacid di (hydrocarbyl) pyrophosphate] mono [di(hydrocarbyl pyrophosphate], wherein n is 2 and n is l; and the metal (IVB) tetra [monoacid di (hydrocarbyl) pyrophosphate], wherein n is 4 and n is 0.
In Formula I above R, R, R" and R may represent identical or different hydrocarbyl groups. While any hydrocarbyl groups having between 1 and about 30 carbon atoms and soluble to the required extent in gasoline may be used, the aliphatic hydrocarbyl groups, particularly branched-chain aliphatic hydrocarbyl groups of from 6 to about 22 carbon atoms are preferred. Such groups are generally more soluble in gasoline than other hydrocarbyl groups, thereby facilitating the use of the novel compounds as gasoline additives. Furthermore, the total number of carbon atoms per molecule of metal organo pyrophosphate can vary from about 2 to about 240, but preferably ranges from about 12 to about carbon atoms.
Typical R, R, R" and R groups may include, for instance, alkyl, alkenyl, aryl, alkylaryl, arylalkyl or alicyclic hydrocarbon radicals. Exemplary of suitable hydrocarbyl radicals are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, isohexyl, 2,2,4- trimethylpentyl, Z-methylpentyl, 2,2 dimethylbutyl, 2,3- dimethylbutyl, heptyl, Z-methylhexyl, S-methylhexyl, 3,3- dimethylpentyl, octyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, Z-ethylhexyl, Z-ethylbutyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, tricontyl, phenyl, naphthyl, benzyl, o-cresyl, p-cresyl, rn-cresyl, dodecylphenyl, octaphenyl, ethylpenyl, diphenyl, pentadecyl, ,B-penylethyl, omegaphenylhexyl, cyclohexyl, cyclobutyl, cyclopentyl, butenyl, octenyl, 2,3-dimethylpentenyl, 2-ethylhexenyl, linoleyl, oleyl, etc.
The compounds of Formula I above may be prepared, for instance, by reacting 1 mole of phosphorous pentoxide with 2 moles of a hydroxy compound, or a mixture of hydroxy compounds, in which the hydroxy group is attached to a hydrocarbyl radical of 1 to about 30 carbon atoms to form a dihydrocarbyl diacid pyrophosphate. The dihydrocarbyl diacid pyrophosphate so formed may then be reacted with a suitable amount of a halide of the desired metal dispersed .or dissolved in an organic solvent. For example, the metal tetrahalides may be reacted with dihydrocarbyl diacid pyrophosphates in molar ratios of 1:2, 1:3 and 1:4 to form, respectively, metal (IV) bis[di(hydrocarbyl) pyrophosphate]; metal (IV) di [monoacid di(hydrocarbyl) pyrophosphate] mono [di (hydrocarbyl) pyrophosphate] and metal (IV) tetra [monoacid di(hydrocarbyl) pyrophosphate]. Likewise, metal trihalides may be reacted with dihydrocarbyl diacid pyrophosphates in molar ratios of 1:2 and 1:3 to form, respectively, metal (III) mono [monoacid di(hydrocarbyl) pyrophosphate] mono [di(hydrocarbyl) pyroph-ospate]; and metal (Ill) tri[monoacid di(hydrocarbyl) pyrophosphate]. Additionally, metal dihalides may be reacted with dihydrocarbyl diacid pyrophosphates in molar ratios of 1:1 and 1:2 to form respectively, metal (II) mono[di(hydrocarbyl) pyrophosphate] and metal (H) bis [monoacid di(hydrocarbyl) pyrophosphate].
Advantageously, the metal organo pyrophosphates of Formula I may be prepared by reacting together, in a single step, the metal halide, phosphorous pentoxide and the hydroxy compound in the same relative proportions as given above. For example, if it is desired to prepare a metal (IV) tetra[monoacid di(hydrocarbyl) pyrophosphate], the reactants may be combined in the proportions of 8 moles of hydroxy compound to 4 moles of phosphorous pentoxide to 1 mole of the metal tetrahalide. In a process of this type, the reactants may be simply mixed together at a temperature from about 10 C. to about 1.20 C., in an inert solvent. The inert solvent is preferably a hydrocarbon such as an aliphatic or an aromatic hydrocarbon, e.g. benzene, toluene, heptane, octane, hexane, etc. However, the inert organic solvent need not be a hydrocarbon, but instead any inert organic solvent such as an ether or halogenated hydrocarbon, e.g. ethyl ether, tetrahydrofuran, carbon tetrachloride, chlorobenzene, etc., can be employed.
In either method of preparation, identity of the hydrocarbyl groups present in the compounds represented by Formula I is determined by the identity of the hydrocarbyl groups present in the dihydrocarbyl diacid pyrophospates or hydroxy compounds used as reactants.
The reaction mixtures resulting from the above-noted preparatory procedures may or may not contain minor quantities of additional compounds, not all of which have been identified, in addition to the metal organo pyrophosphates represented by Formula I. Regardless of their identity, these extraneous compounds do not impair the effectiveness of the metal organo pyrophosphate compounds of the present invention as gasoline and lubricating oil additives, and, therefore, need not be separated therefrom. Furthermore, although generally desirable, it is not necessary to separate the compounds of the present invention from the solvent in which they are prepared prior to use.
Illustrative of the metal (II) organo pyrophosphates represented generically by Formula I, there can be mentioned:
calcium mono[di(propyl) pyrophosphate] beryllium bis[monoacid di(isooctyl) pyrophosphate] magnesium bis[monoacid di(isobutyl) pyrophosphate] barium bis[monoacid di(2,4-dimethylhexyl) pyrophosphate] zinc bis[monoacid di(Z-ethylhexyl) pyrophosphate] cadmium mono[mono (4-octylphenyl) mono (octyl) pyrophosphate] copper bis[monoacid di(tricosyl) pyrophosphate] copper mono[di(benzyl) pyrophosphate] nickel mono[di(Z-ethylhexyl) pyrophosphate] nickel bis[monoacid di(Z-ethylhexyl) pyrophosphate] nickel mono[di(isodecyl) pyrophosphate] iron bis[monoacid mono (dodecyl) mono (heptadecyl) pyrophosphate] iron bis[monoacid di(butenyl) pyrophosphate] cobalt bis[monoacid di(isobutyl) pyrophosphate] cobalt bis[monoacid mono (butyl) mono (tert-butyl) pyrophosphate] manganese mono [di(decyl) pyrophosphate] manganese bis[monoacid mono (pentyl) mono (Z-methylpentyl) pyrophosphate] barium mono[mono (oleyl) mono (phenyl) pyrophosphate] palladium bis[monoacid di(3-methylhexyl) pyrophosphate] palladium mono[di(Z-ethylhexyl) pyrophosphate] platinum mono[mono (Z-ethylhexyl) mono (B-methylhexyl) pyrophosphate] chromium bis[monoacid di(2,3-dimethylhexyl) pyrophosphate] osmium bis[monoacid di(2,4-dimethylhexyl) pyrophosphate] osmium bis[monoacid di(cyclohexyl) pyrophosphate] strontium mono[di(Z-ethylhexenyl) pyrophosphate] Illustrative of the metal (III) organo pyrophosphates represented generically by Formula I, there can be mentioned:
gold tri[monoacid di(Z-ethylhexyl) pyrophosphate] gold mono[monoacid di(ethyl) pyrophosphate] mono[di(isohexyl) pyrophosphate] iron tri[monoacid mono (ethylphenyl) mono (dodecylphenyl) pyrophosphate] iron tri[monoacid di(3,3-dimethylpentyl) pyrophosphate] iron mono[monoacid di(eicosyl) pyrophosphate] mono[di(eicosyl) pyrophosphate] iron mono[monoacid di(Z-ethylhexyl) pyrophosphate] mono[di(Z-ethylhexyl) pyrophosphate] iron mono[monoacid di(triconyl) pyrophosphate] mono[di(triaconyl) pyrophosphate] nickel mono[monoacid di(nonyl) pyrophosphate] mono[di(nonyl) pyrophosphate] nickel tri[monoacid di(isodecyl) pyrophosphate] nickel mono[monoacid mono (heptyl) mono (hexyl) pyrophosphate] mono[mono (heptyl) mono (hexyl) pyrophosphate] nickel mono[monoacid di(Z-ethylhexyl) pyrophosphate] mono[mono (Z-ethylhexyl) mono (isooctyl) pyrophosphate] cobalt tri[monoacid di(2,2,4-trimethylpentyl) pyrophosphate] cobalt tri[monoacid di(diphenyl) pyrophosphate] cobalt mono[monoacid di(cyclopentyl) pyrophosphate] mono[di(cyclopentyl) pyrophosphate] cobalt mono[monoacid mono (pentyl) mono (tridecyl) pyrophosphate] mono[di(pentyl) pyrophosphate] cobalt mono[monoacid mono (hexyl) mono (triaconyl) pyrophosphate] mono[mono (hexyl) mono (triaconyl) pyrophosphate] ruthenium tri [monoacid di(2,2-dimethylbutyl) pyrophosphate] ruthenium tri[monoacid di(phenyl) pyrophosphate] ruthenium mono[monoacid di(Z-ethylhexyl) pyrophosphate] mono[di(Z-ethylhexyl) pyrophosphate] osmium mono[monoacid di(dodecyl) pyrophosphate] mono[di(dodecyl) pyrophosphate] rhodium mono[monoacid di(tetracosyl) pyrophosphate] mono[di(ethyl) pyrophosphate] rhodium tri[monoacid di(benzyl) pyrophosphate] iridium mono[monoacid di(undecyl) pyrophosphate] mono[di(undecyl) pyrophosphate] iridium tri[monoacid di(isononylene) pyrophosphate] molybdenum mono[monoacid di(2,4-dimethylhexyl) pyrophosphate] mono [di (2,4-dimethylhexyl) pyrophosphate] molybdenum tri[monoacid di(heptadecyl) pyrophosphate] chromium tri[monoacid di(naphthyl) pyrophosphate] chromium mono[monoacid di(isoheptyl) pyrophosphate] mono[di(isoheptyl) pyrophosphate] chromium mono[monoacid di(ethylphenyl) pyrophos phate] mono[di(ethylphenyl) pyrophosphate] titanium tri[monoacid di(isodecyl) pyrophosphate] titanium mono[monoacid di(isodecyl) pyrophosphate] mono[di(isodecyl) pyrophosphate] titanium tri[monoacid di(Z-ethylhexyl) pyrophosphate] titanium mono[monoacid di(Z-ethylhexyl) pyrophosphate] mono[di(Z-ethylhexyl) pyrophosphate] titanium tri[monoacid di(hexadecyl) pyrophosphate] titanium mono[monoacid mono (propyl) mono (butyl) pyrophosphate] mono[mono (amyl) mono (hexyl) pyrophosphate] Illustrative of the metal (IV) organo pyrophosphate represented generically by Formula I, there can be mentioned:
manganese bis[di(dodecylphenyl) pyrophosphate] manganese tetra[monoacid di(2,3-ethylbutyl) pyrophosphate] molybdenum tetra[monoacid di(linoleyl) pyrophosphate} molybdenum bis[di(nonacosyl) pyrophosphate] titanium bis[di(2-ethylhexyl) pyrophosphate] titanium tetra[monoacid di(Z-ethylhexyl) pyrophosphate] titanium di[monoacid di(2-ethylhexyl) pyrophosphate] mono[di(2-ethylhexyl) pyrophosphate] titanium tetra[monoacid mono (hexyl) mono (heptyl) pyrophosphate] titanium tetra[monoacid di(isodecyl) pyrophosphate] titanium bis[di(isodecyl) pyrophosphate] hafnium bis[di(tert-butyl) pyrophosphate] hafnium di[monoacid di(p-cresyl) pyrophosphate] mono [di(p-cresyl) pyrophosphate] hafnium tetra[monoacid di(Z-ethylhexyl) pyrophosphate] zirconium di[monoacid di(Z-methylhexyl) pyrophosphate] mono [di(methylhexyl) pyrophosphate] zirconium bis[di(docosyl) pyrophosphate] zirconium tetra[monoacid mono (Z-ethylhexyl) mono (benzyl) pyrophosphate] ruthenium tetra[monoacid di(butyl) pyrophosphate] platinum bis[di(ethyl) pyrophosphate] platinum tetra[monoacid di(decyl) pyrophosphate] osmium di[monoacid di(beta-phenylethyl) pyrophosphate] mono [di(hexyl) pyrophosphate] iridium di[monoacid di(hencosyl) pyrophosphate] mono [di(hencosyl) pyrophosphate] tin di[monoacid di(cyclohexyl) pyrophosphate] mono [di(hexyl) pyrophosphate] germanium di[monoacid di(m-cresyl) pyrophosphate] mono [di(m-cresyl) pyrophosphate] tin bis[di(2,3-dimethylpentenyl) pyrophosphate] lead bis[di(2-ethylhexyl) pyrophosphate] silicon tetra[monacid di(2-ethylbutyl) pyrophosphate] The metal organo pyrophosphates provided by the present invention are useful as gasoline and lubricant additives. As previously noted, particularly desirable metal organo pyrophosphates of the present invention are those which contain at least one acid group (OH) per metal atom, i.e. the metal [acid hydrocarbyl pyrophosphates]. These metal [acid hydrocarbyl pyrophosphates] may be reacted with an organic amine to form amine adducts having exceptional properties as additives in liquid hydrocarbon compositions. Thus, the novel amine adducts of this invention are useful as lubricant additives, anticorrosion additives, detergents, anti-stall additives, and to reduce octane requirement increase.
The amine adducts can be prepared by simply neutralizing the free acid group or groups of the metal[acid hydrocarbyl pyrophosphates]. Formation of the adduct takes place at a temperature between about C. and 60 C. Preferably each of the acid groups of the pyrophosphate is neutralized with basic nitrogen of the amine reactant, although this is not essential. Neutralization can be accomplished by simply adding the amine to the metal[acid hydrocarbyl pyrophosphate] to raise the pH thereof to at least 6 or 7. Also, the neutralization can be accomplished by adding a stoichiometric quantity of the amine to the metal[acid hydrocarbyl pyrophosphate].
The amine employed in preparing the amine adducts of the present invention can be any salt-forming amine having from 1 to about 30 carbon atoms. Thus, primary, secondary, tertiary, aliphatic, aromatic or alicyclic amines may be used. The cyclic amines can be carbocyclic or heterocyclic. The amine can also be a mono-, di-, tri-, or other polyarnine. Furthermore, the amine may be a [3- amine and may contain various substituent groups such as hydroxyl groups. Preferred amines useful in the practice of the invention are aliphatic, monoor polyamines containing 6 to 22 carbon atoms arranged in an alkyl or alkenyl chain.
Illustrative of suitable amines for preparing the amine adducts of the metal organo orthophosphates and pyrophosphates there can be mentioned: methylamine, ethylamine, diethylamine, propylamine, tn'propylamine, isopropylamine, butylamine, isobutylamine, hexylamine, 2- ethylhexylamine, octylamine, dodecylamine, 2-propylde- 6 cylamine, pentadecylamine, tetradecylamine, octadecylamine, 6-butyloctadecylamine, eicosamine, 6,6-dimethyl-ipropyldecylamine, 8-hexyl-10-isobutyloctadecylamine, dioctylamine, tribenzylamine, hexadecylamine, decylamine,
5 N-hexyloctylamine, N,N-dimethyldodecylamine, oleylamine, linoleylamine, 1,IO-decamethylerrediamine, ethylenediamine, 1,2-propylenediamine, 1,12-dodecamethylenediamine, tetramethylenediamine, 1,6-heXamethylenediamine, tetramethylenediamine, 1,6-hexamethylenediamine, triethylenetetramine, 1,2-phenylenediamine, benzylamine, 3,3-biphenyldiamine, biphenylamine, l-naphthylamine, lfiuorenamine, aniline, N-methylaniline N,N-dimethylaniline, 2,3-phenylenediamine, piperazine, piperidine, furfurylamine, N-cyclohexylheptylamine, and the like. The amines can also contain various substituent groups such as hydroxyl groups, eg alkanol amines, such as diethylanolamine, 3,3'-hydroxydipropanolamine, isopropanolamine, and the like. fl-amine, such as octyl-fl-amine, can also be used. Mixtures of amines may also be used to prepare the amine adducts of the present invention. For
' instance, cocoamine, which is a mixture of amines prepared from coconut oil fatty acids and contains predominantly n-dodecylamine, and soya amine, which is a mixture of amines containing 16 to 18 carbon atoms, are cspecially useful.
The amine adducts provided by the invention may be represented by the following formula:
wherein M is metal having a valence of 2 to 4 and particularly an element selected from the group consisting of manganese, chromium, molybdenum, copper, gold and silicon and the metals of Groups II, IV and VIII of the Periodic Table; each of R, R, R" and R' are hydrocarbyl groups having from 1 to about 30 carbon atoms;
n is an integrer from 1 to 4; n is an integer from 0 to 1;
the sum of n plus 2n is equal to the valence of the metal and is an integer from 2 to 4; and A is an amine containing from 1 to about 30 carbon atoms.
Representative of such amine adducts are:
pyrophosphate] rhodium tri[mono(benzylammonium) di(benzyl) pyrophosphate] molybdenum tri[mono(heptadecylammonium) di(heptadecyl) pyrophosphate] titanium tri[mono(6-butyloctyldecylammonium) di(isodecyl) pyrophosphate] titanium di[rnono(isobutylamine) mono(propyl)mono butyl) pyrophosphate] mono[mono(amyl) mono (hexyl) pyrophosphate] manganese tetra[mono(2-ethylbutylammonium) di(2- ethylbutyl) pyrophosphate] amine adduct of 1,6-tetrahexylenediamine and molybdenum tetra[monoacid di(octyl) pyrophosphate] titanium di[mono(oleylammonium) di(Z-ethylhexyl) pyrophosphate] mono[di(2-ethylhexyl) pyrophosphate] titanium tetra[mono(oleylammonium) di(Z-ethylhexyl) pyrophosphate] titanium tetra[mono(cocoammoniurn) di(Z-ethylhexyl) pyrophosphate] titanium di[mono(cocoarnmonium) di(Z-ethylhexyl) pyrophosphate] mono[di(2-ethylhexyl) pyrophosphate] titanium tetra[mono(isodecylammonium) di(isodecyl) pyrophosphate] hafnium di[mono(cyclopentylammonium di(p-cresyl) pyrophosphate] mono[di(p-cresyl) pyrophosphate] zirconium tetra[mono(butylammonium) mono(2 ethylhexyl) mono(benzyl) pyrophosphate] amine adduct of ethylenediamine and ruthenium tetra [monoacid di(butyl) pyrophosphate] amine adduct of aniline and platinum tetra[monoacid di (decyl) pyrophosphate] amine adduct of beta-aminooctadeeene and germanium tetra[monoacid di(decyl) pyrophosphate] Particularly preferred amine adducts for use in hydrocarbon compositions are those represented by Formula II above, wherein M is a Group IV-B metal (e.g. titanium), each R, R, R" and R' is a branched-chain hydrocarbyl radical having from 6 to 22 carbon atoms (e.g. Z-ethylhexyl), n is 0, n is 4, and A is an amine containing from 6 to 22 carbon atoms arranged in an aliphatic hydrocarbyl group, which may be alkyl or alkenyl.
When used as gasoline additives, the compositions of the present invention, namely metal[hydrocarbyl pyrophosphates], metal[acid hydrocarbyl pyrophosphates] and amine salts of metal[acid hydrocarbyl pyrophosphate], are used in an amount between 10 and about 500 parts per million parts of gasoline by weight, preferably from to about 250 p.p.m. and particularly from about to 200 p.p.m. The gasoline composition can be either leaded or unleaded, although leaded gasoline is preferred. In accordance with the preferred embodiment of the invention a gasoline composition is provided which comprises a major portion of leaded hydrocarbon base fuel boiling in the gasoline range and containing between 10 and 500 p.p.m. of the amine salts represented by Formula 11 above, and particularly the salts obtained by reacting an amine containing from 6 to 22 carbon atoms arranged in an aliphatic hydrocarbyl group with a metal (IV-B) [monoacid di(branched-chain C to C hydrocarbyl) pyrophosphate]. It will be understood that the terms gasoline, hydrocarbon base boiling in a gasoline range and similar terms refer to a petroleum fraction boiling in the gasoline range (e.g. between F. and about 450 F.). The term leaded gasoline refers to gasoline to which there has been added a small amount, such as between 0.1 and about 6.0 ml. per gallon of metallo organic antiknock compound such as tetraethyl lead (TEL), tetramethyl lead (TML), tetraisopropyl lead, etc.
In addition to the additives of the present invention and optionally the lead anti-knock compounds, the gasoline compositions of this invention can also include, for instance, light hydrocarbon lubricating oils having viscosities at 100 F. of between about 50 and about 200 Saybolt Universal Seconds (SSU) and viscosity indexes of between about 30 and about 130. Such oils may be present in suitable amounts such as between about 0.1 and about 1.0% by weight of the gasoline composition.
When employed in lubricating compositions, such as lubricating oils, the additives provided by the present invention improve the boundary lubrication properties of the composition. Thus, lubricants containing the additives of this invention inhibit the stick-slip sliding tendencies that are often found in automatic transmission clutching surfaces.
In preparing lubricant compositions with the additives of this invention, it has been found that the amount of additive can vary over a wide range such as from 0.01% to about 3%, by weight, of the lubricant base material. The amine salts of the metal[acid hydrocarbyl pyrophosphates] are particularly desirable lubricating oil additives. In preparing lubricant compositions a wide variety of both mineral oil and synthetic base stock, including mixtures of the same, can be used. Suitable mineral oil base materials include and 200 neutral oils, light and heavy intermediate mineral oils, bright stock as well as combinations of the foregoing. If a synthetic base material is used, it can be that of diesters, polyesters, silicones, silicates, fluorocarbons, phosphates and the like.
In addition to gasoline and lubricating oil compositions, the additives of the present invention may also be used in other hydrocarbon compositions. For example, they may be used in minor quantities of diesel fuel oil compositions to impart anti-rust activity, etc. to the composition.
The invention will now be further described with reference to the following specific and illustrative examples:
Example 1 Titanium tetra[monoacid di(2-ethylhexyl) pyrophosphate] is obtained by reacting phosphorous pentoxide, titanium tetrachloride and 2-ethyl-1-hexanol as shown below:
wherein R is 2-ethylhexyl.
To a suitable reaction vessel equipped with a mechanical stirrer, stoppered pressure equalizing addition funnel, thermometer, gas inlet tube, and a reflux condenser protested with a drying tube, there are added 400 ml. of anhydrous n-heptane and 61.0 g. (0.43 mole) of phosphorous pentoxide. With the stirrer operating at a rate to insure a uniform dispersion, 20.4 g. (0.11 mole) of titanium tetrachloride are added next. Finally, 112 g. (0.86 mole) of 2-ethy1-1-hexanol, contained in the pressure equalizing addition funnel, is charged into the reaction vessel at a rate such that the temperature of the reactants does not rise above 36 C. When this step is completed, the solution is homogeneous. The reactants are then heated under reflux at 88 C. to 100 C., and when evolution of hydrogen chloride moderates, dry air is passed through the solution to displace the acid gas more rapidly and to accelerate the reaction. When evolution of hydrogen chloride ceases, as revealed by Congo Red indicator, the n-heptane and any unreacted 2-ethyl-1- hexanol are removed by distillation in vacuo. The final temperature of the light yellow residual product in the reaction vessel is C. at 6 mm. The product is very viscous and weighs g., which is 96% of theory based on the metal halide. Upon analysis, the product is found to contain 2.98% titanium and 15.36% phosphorous, theory being 2.89% titanium and 14.99% phosphorous.
Example 2 In the manner described in Example 1, a mixture of 0.4 mole (56.8 g.) of P and 0.1 mole (23.3 g.) of ZrCL; in 500 ml. of anhydrous n-heptane is reacted with 0.84 mole (133 g.) of isodecyl alcohol to form zirconium tetra[monoacid di(isodecyl)pyrophosphate], which is represented by the following formula:
wherein R is isodecyl.
Example 3 wherein two of the R groups are isodecyl and the two remaining R groups are octylphenol.
Example 4 A mixture of 0.2 mole (56.8 g.) of P 0 and 0.1 mole (27.2 g.) of cadmium bromide is finely dispersed by vigorous stirring in 400 ml. of a reaction medium consisting of equal volumes of n-heptane and toluene. Then 0.42 mole (55 g.) of iso-octanol is added in the manner described in Example 1. The reactants are heated under reflux at 98 C.105 C. until liberation of by-product HBr is completed. The solvent is removed by distillation at lower pressure to obtain as the residue cadmium bis [monoacid di(iso-octyl)pyrophosphate] as shown below:
wherein R is iso-octyl.
Example 5 To a mixture of 4 moles (568 g.) of P 0 and 1 mole (170 g.) of SiCl in 1500 ml. of dry n-heptane, there is added 8.4 moles (1683 g.) of tridecanol in the manner described in Example 1. Upon completion of the reaction, as evidenced by no further liberation of HCl at C., the n-heptane and any remaining tridecanol are removed by distillation at 120 C. and 2 mm., pressure. The remaining viscous product is silicon tetra[monoacid di(tridecyl)pyrophosphate].
Example 6 Example 7 The titanium tetra[monoacid di(2-ethylhexyl)pyrophosphate] product of Example 1 is mixed with various amines to obtain products having a pH of 7. The reactants are thoroughly mixed at room temperature while protected from carbon dioxide in a vessel blanketed with air. The amounts of amines employed to obtain adducts of pH 7 are given in the following tabulation:
Grams Amine to Make Adduct 'of pH 7 with 10 grams of Titanium tetra[monoacid di (Z-ethylhexyl) pyrophosphate] Amine:
Cocamine (Cg-18) 8.51 Soya Amine (C -18) 10.30 Oleylamine (C 11.20 'N-oleyl-l, 3-propylene diamine 7.94
The following example illustrates the use of each of the above-noted amine adducts as an additive in lubricants.
Example 8 A measure of the boundary lubricating ability of each of the amine adducts of titanium tetra[monoacid di(2- ethylhexyl)pyrophosphate] of Example 7 in lubricating oil, and consequently their effectiveness in reducing wear, is obtained by means of a special apparatus used to assess the boundary properties of lubricants in the 50 F.- 350" F. range. The measurment is reported as Normal Lubricity Indices, NLI, and values of 200 and above are considered very good.
One part by weight of the various amine adducts is blended with 99 parts by weight of a neutral oil having a viscosity of 100 SUS at 100 F. The NLI values are set forth in the following tabulations:
Amine adduct of Noleyl-1, I i-propylene diamine and titanium tetra[monoacid di(2-ethylhexyl) pyrophosphate] 386 The following example illustrates the use of the amine adducts of Example 7 as additives in gasoline compositions.
Example 9 Gasoline compositions are prepared by employing each of the previously-noted amine adducts of titanium tetra [monoacid di(2-ethylhexyl) pyrophosphate] in an amount 1 1 of 50 p.p.m. in a base gasoline having the following characteristics:
ASTM rust tests are run at 75 F. with each of the additive-containing gasoline compositions using distilled water. Each of the compositions passed the test.
While the invention has been described above with respect to certain preferred embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as expressed in the appended claims.
Therefore, I claim:
1. A compound having the formula:
12 wherein M is a Group lI-B metal; n is an integer from 0 to 4; n is an integer from 0 to 2; the sum of n plus 2n is equal to the valence of the metal and is an integer from 2 to 4; and R, R, R", and R are hydrocarbyl groups having from 1 to about 30 carbon atoms.
2. A compound of claim 1 wherein M is titanium.
3. A compound of claim 1 wherein, R, R, R" and R are aliphatic hydrocarbyl groups.
4. A compound of claim 3 wherein R, R, R" and R' are branched-chain aliphatic hydrocarbyl groups having from about 6 to about 22 carbon atoms.
5. A compound of claim 1 wherein n is from 1 to 4 and n is from O to 1.
6. A compound of claim 1 wherein n is 2 and n is 1.
7. A compound of claim 1 wherein n is 4 and n is 0.
8. An amine adduct of the compound of claim 5 wherein said amine contains from 1 to about 30 carbon atoms.
9. An amine adduct of the compound of claim 6 wherein said amine is an aliphatic amine containing from about 6 to about 22 carbon atoms.
10. An amine adduct of the compound of claim 7 wherein said amine is an aliphatic amine containing from about 6 to about 22 carbon atoms.
References Cited UNITED STATES PATENTS l/l94l Farrington et al. 260-438.5 XR l/1957 Asseif 26O431 XR UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,354,189 November 21, 1967 Anthony J. Revukas It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 1, Formula I should appear as shown below instead of as in the patent:
O=P P=O f\ O- -0 O M O ca I -o \OR/ n m O 1 column 10, line 15, for "100 C." read 110C. column 1 the last formula should appear as shown below instead of as i the patent:
column 12, line 1, for "Group II-B" read Group IVB Signed and sealed this 1st day of April 1969.
(SEAL) Attest:
EDWARD J. BRENNER Commissioner of Patents EDWARD M.FLETCHER,JR. Attesting Officer

Claims (3)

1. A COMPOUND HAVING THE FORMULA:
5. A COMPOUND OF CLAIM 1 WHEREIN N IS FROM 1 TO 4 AND N'' IS FROM 0 TO 1.
8. AN AMINE ADDUCT OF THE COMPOUND OF CLAIM 5 WHEREIN SAID AMINE CONTAINS FROM 1 TO ABOUT 30 CARBON ATOMS.
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3441585A (en) * 1966-12-12 1969-04-29 Gen Electric Copolymeric organopolysiloxane lubricant composition
US3478088A (en) * 1966-07-18 1969-11-11 Cities Service Oil Co Metal fluorocarbyl phosphates
US3511623A (en) * 1969-04-14 1970-05-12 Sinclair Research Inc Gasoline composition containing a metal salt of an azole compound
US3544609A (en) * 1966-11-10 1970-12-01 British Petroleum Co Zinc complexes
US3544288A (en) * 1966-07-18 1970-12-01 Cities Service Oil Co Liquid hydrocarbon fuels containing metal fluorocarbyl phosphates
EP0024899A1 (en) * 1979-08-29 1981-03-11 Kenrich Petrochemicals, Inc. Pyrophosphato titanate adducts and methods for treating particulate fillers using such adducts
US4623738A (en) 1985-04-22 1986-11-18 Kenrich Petrochemicals, Inc. Neoalkoxy organo-titanates and organo-zirconates useful as coupling and polymer processing agents
US4634785A (en) * 1984-09-14 1987-01-06 Kenrich Petrochemicals, Inc. Titanium and zirconium pyrophosphates, their preparation and use
US11352582B2 (en) * 2015-11-06 2022-06-07 The Lubrizol Corporation Lubricant with high pyrophosphate level
US11384308B2 (en) 2016-07-20 2022-07-12 The Lubrizol Corporation Alkyl phosphate amine salts for use in lubricants

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2228659A (en) * 1938-11-21 1941-01-14 Standard Oil Co Compounded mineral oil
US2777874A (en) * 1952-11-03 1957-01-15 Lubrizol Corp Metal complexes and methods of making same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2228659A (en) * 1938-11-21 1941-01-14 Standard Oil Co Compounded mineral oil
US2777874A (en) * 1952-11-03 1957-01-15 Lubrizol Corp Metal complexes and methods of making same

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3478088A (en) * 1966-07-18 1969-11-11 Cities Service Oil Co Metal fluorocarbyl phosphates
US3544288A (en) * 1966-07-18 1970-12-01 Cities Service Oil Co Liquid hydrocarbon fuels containing metal fluorocarbyl phosphates
US3544609A (en) * 1966-11-10 1970-12-01 British Petroleum Co Zinc complexes
US3441585A (en) * 1966-12-12 1969-04-29 Gen Electric Copolymeric organopolysiloxane lubricant composition
US3511623A (en) * 1969-04-14 1970-05-12 Sinclair Research Inc Gasoline composition containing a metal salt of an azole compound
EP0024899A1 (en) * 1979-08-29 1981-03-11 Kenrich Petrochemicals, Inc. Pyrophosphato titanate adducts and methods for treating particulate fillers using such adducts
US4634785A (en) * 1984-09-14 1987-01-06 Kenrich Petrochemicals, Inc. Titanium and zirconium pyrophosphates, their preparation and use
US4623738A (en) 1985-04-22 1986-11-18 Kenrich Petrochemicals, Inc. Neoalkoxy organo-titanates and organo-zirconates useful as coupling and polymer processing agents
US11352582B2 (en) * 2015-11-06 2022-06-07 The Lubrizol Corporation Lubricant with high pyrophosphate level
US11384308B2 (en) 2016-07-20 2022-07-12 The Lubrizol Corporation Alkyl phosphate amine salts for use in lubricants

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