WO1986005492A1 - Sels metalliques d'acides phosphorodithioiques aromatiques a substitution hydrocarbyle - Google Patents

Sels metalliques d'acides phosphorodithioiques aromatiques a substitution hydrocarbyle Download PDF

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Publication number
WO1986005492A1
WO1986005492A1 PCT/US1986/000482 US8600482W WO8605492A1 WO 1986005492 A1 WO1986005492 A1 WO 1986005492A1 US 8600482 W US8600482 W US 8600482W WO 8605492 A1 WO8605492 A1 WO 8605492A1
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substituents
mixture
hydrocarbyl
metal salts
aromatic
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PCT/US1986/000482
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English (en)
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Alan Clark Curtis
Richard Yodice
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The Lubrizol Corporation
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Priority to IN154/DEL/86A priority Critical patent/IN166357B/en
Application filed by The Lubrizol Corporation filed Critical The Lubrizol Corporation
Publication of WO1986005492A1 publication Critical patent/WO1986005492A1/fr

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    • 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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26—Amines
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • 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
    • 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
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12

Definitions

  • the present invention relates to a mixture of metal salts containing low and/or high hydrocarbyl substituted aromatic phosphorodithioic acids. It also relates to aromatic phosphorodithioic acids having only low but different hydrocarbyl substituents, e.g. isomers, homologs, thereon. More specifically, the present invention relates to such metal salts which are oil-soluble and can be employed in the lubrication of at least internal combustion engines.
  • Metal salts of phosphorodithioic acids have been utilized as lubricant additives for inhibiting corrosion and oxidation as well as improving extreme pressure and anti-wear properties.
  • European Patent Application 0,024,146 relates to zinc dihydrocarbyl dithiophosphates wherein the hydrocarbyl compound includes alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic groups. These compounds are utilized in combination with copper containing lubricants.
  • a paper presented at the September 7-12, 1969, American Chemical Society, Division of Petroleum Chemistry, Inc., meeting at New York City, by Liston et al of Chevron Corporation, relates to various types of dihydrocarbon phosphorodithioic acids and salts there ⁇ of.
  • the alcohols utilized in making the salts can have at least two carbon atoms and generally five or more.
  • U.S. Patent 2,344,393 to Cook relates to metal dithiophosphates having one or more long chain alkyl groups to render them sufficiently soluble in lub ⁇ ricating oils. Moreover, it recognized that the zinc salt of diamylphosphorodithioic acid was oil-soluble.
  • U.S. Patent 2,480,673 to Reiff relates to re ⁇ acting a hydroxyaromatic compound with -? 2 S 5 an ⁇ -* there ⁇ after treating the product with finely divided zinc.
  • the amount of zinc utilized was small and related to removing impurities as generally opposed to forming a salt.
  • U.S. Patent 2,552,570 to McNab relates to di- hydrocarbyl phosphorodithioic acids wherein the hydro ⁇ carbon group can be either aliphatic or aromatic and contain a total of 10 carbon atoms in the combined aliphatic groups, whether or not attached to an aromatic nucleus.
  • U.S. Patent 3,000,822 to Higgins relates to zinc salts of a mixture of dialkyl phosphorodithioic acids wherein the alkyl groups comprise a mixture of lower molecular weight primary aliphatic hydrocarbon radicals having less than five carbon atoms and higher molecular weight primary aliphatic hydrocarbon radicals having at least five carbon atoms.
  • U.S. Patent 3,190,833 to Rhodes relates to oil-soluble metal phosphorodithioates which contain a total of at least 7.6 aliphatic carbon atoms per atom of phosphorus. To improve the oil-solubility of the metal salts, they are reacted with up to about 0.75 mole of an epoxide.
  • U.S. Patent 3,306,908 to LeSuer relates to Group II metal phosphorodithioates having substan ⁇ tially hydrocarbon radicals.
  • U.S. Patent 3,346,493 to LeSuer also relates to Group II metal hydrocarbon phosphorodithioates.
  • U.S. Patent 3,352,949 to Kawahara relates to certain thioesters of dithiophosphoric acid as motor fuel additives.
  • U.S. Patent 3,736,110 to Ownston relates to rust-inhibitors and more particularly to organic imidazoline salts of mono- and dicresylic phosphates.
  • U.S. Patent 3,843,530 to Niedzielski relates to preparing non-crystalline mixtures of basic or mixed basic and neutral zinc salts of dialkyldithio- phosphates containing from 1 to 13 carbon atoms in the alkyl group.
  • the mixtures of the zinc salts contain from 4 to 13 different alkyl groups, have an average carbon content of 3.5 to 4.5, and contain at least 12% by weight of zinc.
  • ⁇ .S. Patent 3,929,653 to Elliott relates to certain dithiophosphate compounds which are useful as additives.
  • It furthermore relates to a process of reacting a di (organo)dithiophosphoric acid and a monocyclic, non-conjugated olefin containing from 8 to 12 carbon atoms and at least two ethylenically unsaturated double bonds in the ring, and optionally bearing one or more alkyl, alkoxy or hydroxy groups on the ring.
  • U.S. Patent 4, 085,053 to Caspari relates to a process for manufacturing metal dithiophosphates, and metal dithiophosphate compositions.
  • the alcohol often used is an alkyl alcohol.
  • U.S. Patent 4,105,571 to Shaub relates to a storage stable lubricating composition having improved anti-wear properties provided by a base oil composi ⁇ tion containing an additive combination of (1) a zinc dihydrocarbyl dithiophosphate, (2) an ester of a polycarboxylic. acid and a glycol, and (3) an ashless dispersant.
  • U.S. Patent 4,113,634 to Sabol relates to the manufacture of metal diaryl dithiophosphates by reacting -? 2 S 5 w --* tn a hydroxyaryl compound to form a dithiophosphoric acid and neutralizing said acid with metal in the presence of a promoter, said promoter comprising dialkyl dithiophosphoric acid.
  • U.S. Patent 4,306,984 to Ya aguchi relates to a procedure for rendering oil insoluble metal C 2 -C 3 dialkyl dithiophosphates oil-soluble by forming a complex between the dithiophosphate and an alkenyl or alkyl mono- or bis-succinimide.
  • U.S. Patent 4,466,895 to Schroeck relates to certain metal salts of one or more dialkylphosphoro- dithioic acids wherein the alkyl groups, the total number of carbon atoms per phosphorus atom and the like fall within specific ranges.
  • metal salts of hydrocarbyl sub ⁇ stituted aromatic phosphorodithioic acids comprise a mixture of one or more metal salts of the aromatic phosphorodithioic acids containing optionally (A) high hydrocarbyl substituents, optionally (B) low hydro ⁇ carbyl substituents, and a high and a low hydrocarbyl substituent.
  • metal salts of hydrocarbyl substi ⁇ tuted aromatic phosphorodithioic acids comprise one or more metal salts of the aromatic phosphorodithioic acids containing different low hydrocarbyl substi ⁇ tuents therein.
  • a mixture of metal salts of aromatic phosphorodithioic acids contains a high hydrocarbyl substituent and a low hydrocarbyl substituent, and optionally can contain only high hydrocarbyl substituents or only low hydrocarbyl substituents. That is, a high hydrocarbyl aromatic alcohol and a low hydrocarbyl aromatic alcohol are reacted with phosphorus sulfides to form aromatic phosphorodithioic acids.
  • the result approximates a statistical mixture of aromatic phosphorodithioic acids having only high hydrocarbyl substituents, only low hydrocarbyl substituents, or a high and a low hydrocarbyl substituent.
  • the latter components are generally present in a greater amount than either of the first two noted situations.
  • the aromatic component of the acid it generally can be naphthyl with phenyl being preferred.
  • only low but at least 2 different hydrocarbyl substituents are utilized and hence, the end product approximates a statistical mixture of aromatic phosphodithioic acids having only low but often different hydrocarbyl substituents within the same acid.
  • hydrocarbyl substituent or "hydrocarbyl group” is used throughout this specifica ⁇ tion and in the appended claims to denote a group having a carbon atom directly attached to the remainder of the molecule and having predominately hydrocarbon character within the context of this invention.
  • groups include the following:
  • Hydrocarbon groups that is, aliphatic (e.g., alkyl or alkenyl) , alicyclic (e.g., cycloalkyl or cycloalkenyl) , aromatic, aliphatic- and alicyclic- substituted aromatic, aromatic-substituted aliphatic and alicyclic groups, and the like, as well as cyclic groups wherein the ring is completed through another portion of the molecule (that is, the two indicated substituents may together form a cyclic group) .
  • Such groups are known to those skilled in the art; examples include methyl, ethyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl, eicosyl, cyclohexyl, phenyl and naphthyl (all isomers being included) .
  • Substituted hydrocarbon groups that is, groups containing non-hydrocarbon substituents which, in the context of this invention, do not alter pre ⁇ dominantly hydrocarbon character of the group.
  • suitable substit ⁇ uents e.g., halo, hydroxy, alkoxy, carbalkoxy, nitro, alkylsulfoxy
  • Hetero groups that is, groups which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for example, nitrogen, oxygen and sulfur.
  • the high hydrocarbyl substituent thereof generally has a total of from 4 to 18 carbon atoms, desirably from 6 to 12 carbon atoms and preferably from -about 6 to 8 carbon atoms with 7 carbon atoms being more preferred.
  • aromatic alcohol having the high hydrocarbyl substituent therein can be represented by the formula '
  • R' can be suitable hydrocarbyl group(s), desirably it is alkyl group and as noted, having a total of 4 to 18 carbon atoms, desirably from 6 to 12 and preferably from 6 to ' 8 carbon atoms.
  • the number of the R' group(s) , that is n, is from 1 to 3, with 1 being preferred.
  • alcohols include butyl phenol, isobutyl phenol, pentyl phenol, hexyl phenol, heptyl phenol, octyl phenol, nonyl phenol, decyl phenol, dodecyl phenol, octadecyl phenol, dibutyl phenol, dinonyl phenol, didodecyl phenol, triethyl phenol and tributyl phenol. Since n is preferably 1 and the number of carbon atoms is desirably 7, heptyl phenol is a preferred compound.
  • the various types of the high hydrocarbyl substituents on the aromatic nucleus are classified by the average number of total carbon atoms thereon.
  • the overall average number of substituent carbon atoms (R*)n is as above, that is from 4 to 18 with from 6 to 12 being desired and 6 to 8 being preferred.
  • the amount of the (A) high hydrocarbyl substituted aromatic alcohols or phenols is .generally a minority based upon 100% equivalents of said (A) ' high hydrocarbyl substituted aromatic alcohols and the (B) low hydrocarbyl substituted aromatic alcohols. From as low as about 5 percent to about 75 percent equivalents can be utilized with from about 10 to about 65 percent equivalents being desired and from about 15 to about 40 percent equivalents being preferred.
  • the (B) low hydrocarbyl substituted aromatic alcohols generally have a total of 4 or less carbon atoms in the hydrocarbyl substituent.
  • the hydrocarbyl group can generally be any suitable substituent such as aliphatic with an alkyl being preferred.
  • the (B) low hydrocarbyl substituted aromatic alcohol can be represented by the following formula
  • (R) can be suitable hydrocarbyl group(s) , desirably it is alkyl group(s) having from 0 to 4 carbon atoms, desirably from 1 to 4 carbon atoms with from 1 to 3 carbon atoms being preferred.
  • the number of the R group(s) is an integer of from 1 to 3 with 1 or 2 being preferred.
  • the low hydrocarbyl sub ⁇ stituted aromatic alcohol is simply phenol. Phenol is generally not desired in any large amount since it imparts poor solubility to products made therefrom.
  • a general class of compounds falling within the above formulation are generally referred to as the cresylic acids.
  • Such a group of compounds usually contain numerous different (B) low hydrocarbyl substituted aromatic alcohols including the cresols from which the name is derived.
  • Suitable alcohols thus include ortho-cresol, eta-cresol, para-cresol, the v * arious xylenols such as 2,6-xylenol, 2,4-xylenol, 2,5-xylenol, 2,3-xylenol, and 3,4-xylenol.
  • Another group of alcohols are the ortho, meta- and para- ethylphenols.
  • Still another group of alcohols are the propyl substituted phenols.
  • the various trimethyl substituted phenols constitute yet another group with specific examples including 2,3,5-trimethylphenol, 2, 3 , 4-trimethylphenol , 2,4,5- trimethylphenol, 3,4,5-trimethylphenol and the like.
  • An example of low hydrocarbyl substituted aromatic alcohols containing four substituted carbon atoms are the various tetra- methylphenols such as 2,3,5,6- tetramethylphenol, 2,3,4,5-tetramethylphenol, 2,3,4,6- tetramethylphenol, and the like.
  • a still further group of such aromatic alcohols include the various ethyl- ethylphenols such as 4-ethyl-2-methyl-phenol, 5-ethyl-2-methylphenol and the like.
  • the low hydrocarbyl substituent (R) contain an overall average of a small number of total carbon atoms. Accordingly, all of the low hydrocarbyl substituents, (R) m / generally contain an overall average number of from about 0 or from about 0.5 to 4 carbon atoms, desirably from about 1.0 to about 3.5 carbon atoms, and preferably from about 2.0 to about 3.0 carbon atoms.
  • the amount of the low hydrocarbyl substituted aromatic alcohols is generally from about 25 to about 90 percent equivalents, desirably from about 35 to about 90 percent equivalents, and preferably from
  • Sources of low hydrocarbyl substituted aromatic alcohols or cresylic acids are numerous.
  • a typical example is Product CA-33 from the Merichem Company of Houston, Texas. Such a product has an organic composition as determined by gas chromatograph and is set forth in Table I. TABLE I.
  • the average number of carbon atoms in the hydrocarbyl substituent is approximately 2.07.
  • cresylic acid composition is Product CA-57 of the Merichem Company which according to gas chromatograph has the following analysis as set forth in Table II.
  • the average number of carbon atoms in the hydrocarbyl substituent is approximately 2.05.
  • cresylic acid is Product XL-85 sold by the Productol Chemical Division of Ferro Corporation, Whittington, California. Gas chromatograph analysis revealed the following composition as set forth in Table III.
  • the average number of carbon atoms in the hydrocarbyl substituent is approximately 2.8.
  • only low hydrocarbyl substituents of the aromatic phosphorodithioic acid are utilized.
  • no high hydrocarbyl substituents are utilized and hence there is no mixture of metal salts of the aromatic phosphorodithioic acids containing high hydrocarbyl substituents.
  • the low hydrocarbyl substituted aromatic alcohols with regard to this embodiment can be the same as the above (B) alcohols. That is, the alcohols can be represented by the formula where R is an alkyl group having from 0 or 0.5 to 4 carbon atoms, desirably from 1 to 4 carbon atoms with from 1 to 3.5 or 3 carbon atoms being preferred.
  • R is an alkyl group having from 0 or 0.5 to 4 carbon atoms, desirably from 1 to 4 carbon atoms with from 1 to 3.5 or 3 carbon atoms being preferred.
  • the number of such R groups, that is m is an integer from 1 to 3 with 1 or 2 being preferred.
  • the des ⁇ cription thereof will not be repeated but rather is hereby fully incorporated by reference. However, it is essential that these two different or distinct alcohols be utilized to impart favorable solubility to the metal salt.
  • the alcohols are not identical or the same.
  • the term “different” includes not only different structural alcohols, but homologues of a particular aromatic alcohol as well as iso ers of the same alcohol. Thus, by way of example meta, ortho and paracresol are different alcohols.
  • the various xylenols constitutes a different type cf an aromatic alcohol, for example 2,6-xylenol, or 2,4-xylenol, or 3,4-xylenol or the like.
  • various sources of low hydrocarbyl aromatic alcohols which already contain at least two different types of alcohols therein can be utilized such as the various cresylic acids which are hereby incorporated by reference.
  • the amount of the various types of the low hydrocarbyl substituted aromatic alcohol is such that satisfactory solubility in a diluent oil is obtained.
  • the acids of the present invention are gener ⁇ ally prepared by reacting a solution containing a combination of both the low hydrocarbyl substituted aromatic alcohols as well as the high hydrocarbyl substituted aromatic alcohols, in a ratio as set forth within the above limits, with various types of phosphorus sulfides. When necessary, non-phosphorus containing sulfur compounds can be used.
  • the acids of the present invention are also generally prepared by reacting a solution containing a mixture of different low hydrocarbyl substituted aromatic alcohols, in a ratio as set forth within the above limits, with various types of phosphorus sulfides as well as optional non-phosphorus containing sulfur compounds.
  • various phosphorus sulfides include ⁇ 2 ⁇ ' ⁇ 4 ⁇ 2 ' " > 4 ⁇ 7*
  • optional sulfur compounds include sulfur and sulfurized olefins.
  • the phosphorus sulfides- are initially reacted with the mixture of high and low hydrocarbyl substituted aromatic alcohols and then optionally reacted with the phosphorus-free sulfur compounds.
  • the phosphorus sulfides are initially reacted with the mixture of solely the low hydrocarbyl substituted aromatic alcohols and then optionally reacted with the phosphorus-free sulfur compounds.
  • a preferred phosphorus-sulfur compound is phosphorus pentasulfide.
  • the preparation of the desired phosphoro ⁇ dithioic acids generally involves a reaction of from about 3 to about 5 moles and desirably about 4 moles of the alcohol mixture per mole of phosphorus pentasulfide in an inert atmosphere such as nitrogen.
  • the reaction is generally carried out within a temperature range of from about 50°C to about 200°C, desirably from about 80°C to about 200°C and preferably from about 110°C to atbout 140°C.
  • the reaction is normally completed in the time period of from about 1 to 3 hours with hydrogen sulfide being liberated during the reaction.
  • the metal salts of the hydrocarbyl substituted aromatic phosphorodithioic acids are readily formed by the reaction of the metal or the basic metal compound with the acid. Simply mixing and heating the two reactants together is sufficient to cause the reaction to take place. According to the present invention, it is important that the reaction temperature with regard to the formation of the metal salt be kept low to avoid excessive hydrolysis. Inasmuch as hydrolysis is to be avoided, the reaction temperature is generally from about 30°C to about 90°C and preferably from about 50°C to about 80°C.
  • a desired oil is a low viscosity (e.g. about 3-7 centistokes @ 40°C) naphthenic oil since it gives a fluid product.
  • a promoter is not required at the reaction temperature of the formation of the salt. That is, the reaction between the acid and the basic metal compound is free from any promoter.
  • a metal salt is desired which is neutral or basic and hence, an equivalent or a slight excess of the metal or the basic metal compound is utilized to yield such an end product.
  • the amount of metal or basic metal compound when utilized in an excess is from about 0 to about 20 per ⁇ cent with an excess of from about 5 percent to about 15 percent equivalents being desirable.
  • Types of metals suitable for the present invention include zinc, copper, nickel, cobalt, manganese, potassium, tin, sodium, calcium especially in combinations with other metals, as well as combinations of any of the previous metals.
  • basic metal compounds can be utilized such as various metal oxides, acetates and the like.
  • examples of specific basic metal compounds include zinc oxide, copper oxide, sodium hydroxide, potassium hydroxide, calcium oxide, zinc acetate, copper acetate, and the like.
  • Examples of preferred metals include copper and zinc with zinc being especially preferred.
  • Examples of preferred basic metal compounds include zinc oxide and copper oxide.
  • the metal salts of the present invention have been found to impart good anti-wear properties to various organic diluents. Moreover, in view of the fact that aromatic phosphorodithioates typically give poor anti-wear results, the fact that the mixtures of the present invention give good anti-wear results was actually unexpected.
  • Example 1A illustrates the prepara ⁇ tion of the phosphorodithioic acids and the metal salts thereof. All parts and percentages are by weight unless otherwise indicated.
  • Example 1A illustrates the prepara ⁇ tion of the phosphorodithioic acids and the metal salts thereof. All parts and percentages are by weight unless otherwise indicated.
  • a mixture of 2945 parts (24 equivalents) of Cresylic Acid 57 and 1152 parts (6.0 equivalents) of heptylphenol is heated to 105°C under a nitrogen atmosphere whereupon 1665 parts (15 equivalents) of phosphorus pentasulfide are added in portions over a period of 3 hours while maintaining the temperature of the mixture between about 115°-120°C.
  • the mixture is maintained at ' this temperature for an additional 1.5 hours upon completion of addition of the phosphorus pentasulfide and then cooled to room temperature.
  • the reaction mixture is filtered through a filter aid, and the filtrate is the desired phosphorodithioic acid.
  • Zinc oxide (541 parts, 13.3 equivalents), 14.4 parts (0.24 equivalents) of acetic acid and 1228 parts of mineral oil are charged to a 12 liter flask.
  • a vacuum (100-100 mm) is applied while raising the temperature to about 70°C.
  • the phosphorodithioic acid (4512 parts, 12.0 equivalents) prepared in Example 1A is added over a period of about 5 hours while maintaining the temperature at 68°-72°C.
  • the water is removed as it forms.
  • the temperature is maintained at 68-72°C for 2 hours after the addition of phosphorodithioic acid is complete.
  • vacuum is adjusted to about 10 mm and the temperature is raised to about 105°C and maintained at this temperature for 2 hours.
  • the residue is filtered and the filtrate is the desired product.
  • the product contains 6.26% P (6.09% theory) and 6.84% Zn (6.38% theory).
  • Example ID Cuprous oxide (78.7 parts, 1.1 equivalents) and 112 parts of mineral oil are charged to a one-liter flask and 384 parts (1.0 equivalents) of the phosphoro ⁇ dithioic acid prepared in Example 1A are added over a period of 2 hours while raising the temperature grad ⁇ ually to about 55°C. Upon completion of the addition of the acid, the reaction mixture is maintained at about 50°C. Upon completion of the addition of the acid, the reaction mixture is maintained at about 50°C for about 3 hours. A vacuum is applied while raising the tempera ⁇ ture to about 80°C. The residue is filtered and the filtrate is the desired product. The product is a clear liquid containing 12.0% sulfur (11.5% theory) and 12.0% copper (11.4% theory) .
  • Example ID Example ID
  • Zinc oxide (537 parts, 13.2 equivalents), 97 parts of water and 1223 parts of mineral oil are charged to a 12-liter flask.
  • the phosphorodithioic acid (4512 parts, 12.0 equivalents) prepared in Example 1A is added over a period of about 2 hours.
  • the temperature is allowed to increase from 25°C to 48°C during the addition.
  • the temperature is increased to and main ⁇ tained at about 70°C for 3 hours after the addition of phosphorodithioic acid is complete.
  • a vacuum about 15 mm Hg
  • the residue is filtered and the filtrate is the desire product.
  • the product contains 6.29% P (6.09% theory) and 6.80% Zn (6.39% theory) .
  • Zinc oxide (175 parts, 2.2 equivalents) 3.55 parts (0.06 equivalents) of acetic acid, 250 parts of heptane are charged to a 3-liter flask. A vacuum is applied while raising the temperature to about 50°C.
  • the phosphorodithioic acid (1145 parts, 3.5 equivalents) prepared in Example 2A is added over a period of about 2 hours while maintaining the temperature at about 60°- 65°C. The temperature is raised to about 80°C and kept at this temperature for 3 hours. The residue is filtered and the filtrate is the desired product.
  • the product contains 9.01% P (8.59% theory) and 9.11% Zn (9.06% theory) .
  • Example 3A Example 3A
  • Heptylphenol (1540 parts, 8.0 equivalents) is heated to 125°C under a nitrogen atmosphere whereupon 444 parts (4.0 equivalents) of phosphorus pentasulfide are added in portions over a period of 1 hour while maintaining the temperature of the mixture at about 145°C.
  • the mixture is held at this temperature for an additional 4 hours upon completion of the addition of the phosphorus pentasulfide and then cooled to room temperature.
  • the reaction mixture is filtered through a filter aid and the filtrate is the desired phosphoro ⁇ dithioic acid.
  • Example 3B Example 3B
  • Zinc oxide (90.5 parts, 2.22 equivalents), 2.54 parts (0.04 equivalents) of acetic acid, 2.54 parts of water, and 919 parts of mineral oil are charged to a 3 liter flask.
  • the mixture is heated to about 70°C and 1000 parts (1.83 equivalents) of the phosphorodithioic acid of Example 3A are added over a period of 1 hour while maintaining the temperature at 70°-75°C.
  • the temperature is maintained at 70°-75°C for 3 hours. Vacuum is applied and the temperature is raised to about 105°C.
  • the residue is filtered and the filtrate is the desired product.
  • the product is a clear liquid and contains 3.0% P.
  • Zinc oxide (90.5 parts, 2.22 equivalents), 2.54 parts (0.04 equivalents) of acetic acid, 2.54 parts of water, and 597 parts of mineral oil are charged to a 3 liter flask.
  • the mixture is heated to about 70°C and 1271 parts (1.83 equivalents) of the phosphorodithioic acid of example 4A are added over a period of 1 hour while maintaining the temperature at 70°-75°C.
  • the temperature is maintained at 70°-75°C for 3 hours. Vacuum is applied and the temperature is raised to about 105°C.
  • the residue is filtered and the filtrate is the desired product.
  • the product is a clear liquid and contains 3.2% P.
  • Cresylic Acid 57 (356 parts, 2.9 equivalents) is heated to about 113°C under a nitrogen atmosphere whereupon 161 parts (1.45 equivalents) of phosphorus pentasulfide are added in portions over a 1.5 hour period while maintaining the temperature at 110°-115°C. The mixture is held at this temperature for an additional 2 hours upon completion of the addition of phosphorus pentasulfide and then cooled to room temperature. The reaction mixture is filtered through a filter aid and the filtrate is the desired phosphorodithioic acid.
  • Example 5B Example 5B
  • Example 5A Zinc oxide (45.1 parts, 1.1 equivalents), 1.2 parts (0.02 equivalents) of acetic acid, and 96.1 parts of mineral oil are charged to a 1 liter flask. A vacuum (about 100 mm) was applied and the temperature was raised to about 70°C. The phosphorodithioic acid (352 parts, 1.0 equivalents) of Example 5A is added over a 2 hour period while maintaining the temperature at 72°-79°C. Water was removed as it formed. Upon completion of the phosphorodithioic acid addition, the temperature is held at 70°-75°C for an additional 3 hours. The mixture is filtered and the filtrate is the desire.d product. The product is a clear liquid. Example 6A
  • Zinc oxide (45.1 parts, 1.1 equivalents), 1.2 parts (0.02 equivalents) of acetic acid, and 99.3 parts of mineral oil are charged to a 1 liter flask.
  • a vacuum (about 100 mm) is applied while raising the temperature to about 75°C.
  • the phosphorodithioic acid (365 parts, 1.0 equivalents) prepared in Example 6A is added over a period of 2 hours while maintaining the temperature at 75°-80°C.
  • the water is remove as it forms.
  • the temperature is maintained at about 77°C for 3 hours after the phosphorodithioic acid addition is complete.
  • the vacuum is reduced to about 10 mm and the temperature is raised to about 100°C and held at that temperature for 1 hour.
  • the residue is filtered and the filtrate is the desired product.
  • the product contains 7.06% Zn (6.53% theory) .
  • Example 7A Example 7A
  • Zinc oxide (45.1 parts, 1.1 equivalents), 1.2 parts (0.02 equivalents) of acetic acid, and 107 parts of mineral oil are charged to a 1 liter flask.
  • the phosphorodithioic acid (395 parts, 1.0 equivalents) prepared in Example 7A is added over a period of 1 hour while allowing the temperature to rise to about 56°C.
  • the temperature is raised to about 70°C and held there for 15 minutes.
  • a vacuum is applied and the temperature is raised to about 100°C.
  • the residue is filtered and the filtrate is the desired product.
  • the product contains 5.94% P (5.79% theory) and 6.78% Zn (6.07% theory) .
  • Zinc oxide 64 parts, 1.57 equivalents, 1.6 parts (0.026 equivalents) of acetic acid, and 218 parts of xylene, are charged to a 2-liter flask. Vacuum (about 96 mm) is applied and the mixture is heated to about 76°C.
  • the phosphorodithioic acid (465 parts, 1.3 equivalents) prepared in Example 8A is added over a 7 hour period. Water is removed as it is formed. After- the phosphorodithioic acid addition is complete, the temperature is raised to about 89°C and held at that temperature for 1.5 hours. Mineral oil (127 parts) is added. The pressure was reduced to about 10 mm and the temperature was increased to about 95°C to remove the xylene. The residue is filtered and the filtrate is the desired product. The product contains 6.68% P (6.33% theory) .
  • Example 9h Example 9h
  • Zinc oxide 49.2 parts, 1.21 equivalents
  • 1.2 parts (0.02 equivalents) of acetic acid and 218 parts of xylene are charged to a 1 liter flask.
  • Vacuum about 94 mm Hg
  • the phosphorodithioic acid (442 parts, 1.0 equivalents) prepared in Example 9A is added over a 1 hour period.
  • the temperature is maintained at about 89°C for 3 hours after the phosphorodithioic acid addition is completed.
  • Mineral oil (118 parts) is added.
  • the vacuum is adjusted to about 10 mm Hg and the temperature is raised to about 100°C to remove xylene.
  • the residue is filtered and the filtrate is the desired product.
  • the product contains 5.51% P (5.19% theory) and 5.72% Zn (5.44% theory).
  • Example 10A Example 10A
  • Zinc oxide (112 parts, 2.75 equivalents) and 186 parts of mineral oil are charged to a 2 liter flask.
  • the phosphorodithioic acid (1045 parts, 2.5 equivalents) prepared in Example 10A is added over a 2 hour period while allowing the temperature of the reaction mixture to increase to • about 50°C.
  • the temperature is increased to and maintained at about 75°C for 3 hours.
  • Vacuum (about 15 mm Hg) is applied and the temperature of the reaction mixture increased to about 100°C.
  • the residue is filtered and filtrate is the desired product.
  • the product contains 5.98% P (5.93% theory) and 6.79% Zn (6.22% theory).
  • test cup and block surfaces are merely “wetted” with test lubricant (approx ⁇ imately 5 drops on block) . No test sample is recirculated over the surfaces during the test.
  • Test duration is 5 minutes under load.
  • compositions of the present ' invention are useful as additives for lubricants and functional fluids. They can be employed in a variety of lubricants based on diverse oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof.
  • the lubricants include crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad diesel engines, and the like. Also contemplated are lubricants for gas engines, stationary power engines and turbines and the like.
  • Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of lubrica ⁇ ting viscosity derived from coal or shale oil can also be included as the base oil.
  • Synthetic lubricating oils include hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpoly erized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene, copolymers, chlorinated polybutylenes, etc.); polyd- hexenes) , poly(1-octenes) , poly(1-decenes) , etc.
  • hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpoly erized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene, copolymers, chlorinated polybutylenes, etc.); polyd- hexenes) , poly(1-octenes) , poly(1-decenes) , etc.
  • alkylbenzenes e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl) benzenes, etc.
  • polyphenyls e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic oils. These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g.
  • methylpolyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500, etc.) or mono-, and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters, or the Ci3 Oxo acid diester of tetraethylene glycol.
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, di- ethylene glycol monoether, propylene glycol, etc.).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adip
  • esters include dibutyl adipate, di- ( 2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, di- isodecyl acelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like.
  • Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
  • Silicon-based oils such as the polyaikyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another class of synthetic oils (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra- (p-tertbutylphenyl) silicate, hexa- (4-methyl- 2-pentoxy) -disiloxane, poly(methyl) siloxanes, poly (methylphenyl)siloxanes, etc.).
  • synthetic oils e.g., tetraethyl silicate, tetraisopropyl silicate, tetra- (p-tertbutylphenyl) silicate, hexa- (4-methyl- 2-pentoxy) -disiloxane, poly(methyl) siloxanes, poly (methylphenyl)siloxanes, etc.
  • liquid esters of phosphorus-containing acids e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid, tc
  • polymeric tetra- hydrofurans and the like.
  • Unrefined, refined and rerefined oils (and mixtures of each with each other) of the type disclosed hereinabove can be used in the lubricants and functional fluids of the present invention.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • a shale oil obtained directly from retorting operations a petroleum oil obtained directly from distillation or an ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil.
  • Refined oils are similar to the unrefined oils except they have been further treatment in one or more purification steps to improve one or more properties.
  • Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
  • the lubricants and functional fluids of the present invention contain an amount of the com- positions of this invention sufficient to provide it with antioxidant • and/or anti-wear properties. Normally this amount will be about 0.25 percent to about 10 percent, preferably about 0.4 percent to about 7.5 percent of the total weight of the fluid.
  • additives include, for example, detergents and dispersants of the ash-producing or ashless type, corrosion- and auxiliary oxidation- inhibiting agents, pour point depressing agents, auxiliary extreme pressure agents, color stabilizers and anti-foam agents.
  • the ash-producing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, or organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage such as those prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a phosphorizing pentasulfide, phosphorus tri ⁇ chloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride.
  • the most commonly used salts of such acids are those of sodium, potassium, litium, calcium, magnesium, strontium and barium.
  • basic salt is used to designate metal salts wherein the metal is present in stoichio- metrically larger amounts than the organic acid radical.
  • the commonly employed methods for preparing the basic salts involve heating a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50°C and filtering the resulting mass.
  • a “promoter” " in the neutralization step to aid the incorporation of a large excess of metal likewise is known.
  • Examples of compounds useful as the • promoter include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation products of formaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylenedia ine, phenothiazine, phenyl-beta- naphthyla ine, and dodecylamine.
  • phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation products of formaldehyde with a phenolic substance
  • alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl
  • a particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter, and carbonating the mixture at an elevated temperature such as 60-200°C.
  • Ashless detergents and dispersants are so called despite the fact that, depending on its constitution, the dispersant may upon combustion yield a non-volatile material such as boric oxide or phosphorus pentoxide; however, it does not ordinarily contain metal and therefore does not yield a metal-containing ash on combustion.
  • Many types are known in the art, and any of them are suitable for use in the lubricants of this invention. The following are illustrative:
  • Reaction products are carboxylic acids (or derivatives thereof) containing at least about 34 and preferably at least about 54 carbon atoms with nitrogen- containing -compounds such as amine, organic hydroxy compounds such as phenols and alcohols, and/or basic inorganic materials.
  • nitrogen- containing -compounds such as amine, organic hydroxy compounds such as phenols and alcohols, and/or basic inorganic materials. Examples of these "carboxylic dispersants" are described in British Patent 1,306,529 and in many U.S. patents including the following:
  • chlorinated aliphatic hydrocarbons such as chlorinated wax
  • organ-ic. sulfides and polysulfides such as benzyl .disulfide, bis(chlorobenzyl)disulfide, dibutyl tetra- sulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpene
  • phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate
  • phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclo- hexyl phosphite, pentylphenyl phosphite, dip
  • pour- point depressants are a particularly useful type of additive often included in the lubricating oils described herein.
  • the use of such pour point depressants in oil-based composition to improve low temperature properties of oil-based compositions is well known in the art. See, for example, page 8 of "Lubricant Additives" by C. V. Smalheer and R. Kennedy Smith (Lezius-Hiles Co. publishers, Cleveland, Ohio, 1967) .
  • pour point depressants examples include polymethacrylates, polyacrylates; polyacryla ides; condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers; and terpolymers of dialkylfu arates, vinylesters of fatty acids and alkylvinylethers.
  • Pour point depressants useful for the purposes of this invention techniques for their preparation and their uses are described in U.S. Patent Nos. 2,387,501; 2,015,748; 2,655,479; 1,815,022; and 3 250,715 which are hereby incorporated by reference for their relevant disclosures.
  • the metal salt compositions of this invention can be added directly to the lubricant.
  • the amount of the metal salt compositions is such that the amount of phosphorus in said lubricating composition from about 0.001 to about 0.15 parts by weight per 100 parts by weight of the lubricant composition.
  • a more desirable amount of the metal salts of hydrocarbyl substituted aromatic phosphorodithioic acids is from 0.025 to about 0.1 parts by weight of the phosphorus in said lubricant composition.
  • they are often diluted with a substantially inert, normally liquid organic diluent such as mineral oil, naphtha, benzene, toluene, xylene, or the like to form an additive concentrate.
  • concentrates usually contain from about 3 to about 90 percent by weight of the metal salts of the present invention, as set forth in Table V. Additionally, the concentrates can contain one or more additive known in the art or described hereinabove. The remainder of the concentrate is substantially inert normally liquid diluent.
  • the amount of the metal salts contained in the lubricant composition is generally a minor amount with a major amount being the lubricating oil.

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Abstract

Un mélange de sels d'acides phosphorodithioïques aromatiques contient éventuellement A) des substituants à haute teneur en hydrocarbyle, éventuellement B) des substituants à faible teneur en hydrocarbyle, et, à la fois, les substituants à haute teneur en hydrocarbyle et les substituants à faible teneur en hydrocarbyle. Dans une variante, les substituants à substitution hydrocarbyle d'un acide phosphorodithioïque aromatique peuvent n'être que des dérivés à faible teneur en hydrocarbyle mais différents. Le composant d'acide phosphorodithioïque à faible teneur en hydrocarbyle (B) peut être obtenu en utilisant des mélanges d'acides crésyliques. Ces sels métalliques sont solubles dans l'huile et sont utiles en tant qu'inhibiteurs de corrosion et comme agents anti-usure, notamment dans des compositions d'huiles lubrifiantes.
PCT/US1986/000482 1985-03-12 1986-03-10 Sels metalliques d'acides phosphorodithioiques aromatiques a substitution hydrocarbyle WO1986005492A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5739089A (en) * 1987-11-24 1998-04-14 Exxon Chemical Patents Inc. Dihydrocarbyl dithiophosphates

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE914007C (de) * 1951-12-25 1954-06-24 Basf Ag Verfahren zur Herstellung von Schmieroelverbesserungsmitteln
DE1018428B (de) * 1954-02-23 1957-10-31 Basf Ag Verfahren zur Herstellung von Schmieroelverbesserungsmitteln
US3361668A (en) * 1965-10-19 1968-01-02 Lubrizol Corp Lubricating compositions containing light-colored and improved group ii metal phosphorodithioates
US4113634A (en) * 1977-03-01 1978-09-12 Standard Oil Company (Indiana) Metal aryl dithiophosphates and their manufacture
US4116871A (en) * 1977-06-29 1978-09-26 Chevron Research Company Preparation of phosphorus-containing acids and salts

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE914007C (de) * 1951-12-25 1954-06-24 Basf Ag Verfahren zur Herstellung von Schmieroelverbesserungsmitteln
DE1018428B (de) * 1954-02-23 1957-10-31 Basf Ag Verfahren zur Herstellung von Schmieroelverbesserungsmitteln
US3361668A (en) * 1965-10-19 1968-01-02 Lubrizol Corp Lubricating compositions containing light-colored and improved group ii metal phosphorodithioates
US4113634A (en) * 1977-03-01 1978-09-12 Standard Oil Company (Indiana) Metal aryl dithiophosphates and their manufacture
US4116871A (en) * 1977-06-29 1978-09-26 Chevron Research Company Preparation of phosphorus-containing acids and salts

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5739089A (en) * 1987-11-24 1998-04-14 Exxon Chemical Patents Inc. Dihydrocarbyl dithiophosphates

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MX170731B (es) 1993-09-10
CA1273333A (fr) 1990-08-28
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EP0214283A1 (fr) 1987-03-18

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