EP0739405A4 - ADDITIVES FOR LUBRICANTS - Google Patents

ADDITIVES FOR LUBRICANTS

Info

Publication number
EP0739405A4
EP0739405A4 EP95907404A EP95907404A EP0739405A4 EP 0739405 A4 EP0739405 A4 EP 0739405A4 EP 95907404 A EP95907404 A EP 95907404A EP 95907404 A EP95907404 A EP 95907404A EP 0739405 A4 EP0739405 A4 EP 0739405A4
Authority
EP
European Patent Office
Prior art keywords
metallic
dithiocarbamate
dithiophosphate
product
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95907404A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0739405A1 (en
Inventor
John Phillips Doner
Liehpao Oscar Farng
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Oil Corp
Original Assignee
Mobil Oil Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mobil Oil Corp filed Critical Mobil Oil Corp
Publication of EP0739405A1 publication Critical patent/EP0739405A1/en
Publication of EP0739405A4 publication Critical patent/EP0739405A4/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
    • C10M137/10Thio derivatives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/12Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
    • C10M137/14Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond containing sulfur
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12Reaction products
    • C10M159/123Reaction products obtained by phosphorus or phosphorus-containing compounds, e.g. P x S x with organic compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • C10M2207/1265Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic used as thickening agent
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/128Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
    • C10M2207/1285Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066Thiocarbamic type compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066Thiocarbamic type compounds
    • C10M2219/068Thiocarbamate metal salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/045Metal containing thio derivatives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/12Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/12Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
    • C10M2223/121Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy of alcohols or phenols
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/02Groups 1 or 11
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/04Groups 2 or 12
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    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/08Groups 4 or 14
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/10Groups 5 or 15
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/12Groups 6 or 16
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/14Group 7
    • CCHEMISTRY; METALLURGY
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    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/16Groups 8, 9, or 10

Definitions

  • This invention is directed to combinations and reaction products of metallic dithiocarbamates and metallic dithiophosphates, and their use as additives in lubricants because of their synergistic properties. More particularly,it is directed to compositions of lubricants and greases containing such additives.
  • Antiwear additives and friction modifying additives are frequently blended with lubricants in order to prevent wear, reduce fuel consumption and increase the operating life of the machinery.
  • the term "anti-load” is in some instances used instead of "antiwear”, but the term “antiwear” is used throughout this disclosure.
  • various additives have been added in the past to lubricants to produce a protective surface film on the metal parts.
  • the antiwear lubricants may exhibit other unsatisfactory lubricating characteristics such as corrosive wear due to chemical reaction between the additive and the metal surfaces, and deterioration due to oxidation under high temperature conditions. Supplemental lubricating additives may subsequently be necessary in order to prevent such detrimental effects.
  • various friction- reducing additives have been added to lubricants to produce a smooth surface film.
  • the friction additives may dominate the metal surface and prevent the anti-wear additives from encountering the surface to form an effective film. Friction and wear are two different phenomena. Often,it is difficult to prevent wear and reduce friction simultaneously, even in the presence of both antiwear additives and friction-modifying additives.
  • the instant invention provides unexpected results by providing both low friction and low wear properties in a single additive formulation. Synergism can be obtained by the use of pre-blended combinations of specific antiwear and friction-modifying agents or reaction products of such agents. Synergistic behavior cannot be achieved through the simple component blending process (i.e., lubricant and grease formulation blending) . This invention is very significant to applications involving machinery,bearings and joint lubrication.
  • Lubricants such as lubricating oils and greases
  • Lubricants are subject to oxidative deterioration at elevated temperatures or upon prolonged exposure to the elements or exhaustion of useful life. Such deterioration is evidenced, in many instances, by an increase in both acidity and viscosity, and when the deterioration is severe enough, it can cause metal parts to corrode. Additionally, severe oxidation leads to a loss of lubrication properties, and in especially severe cases this may cause complete breakdown of the device being lubricated.
  • the metal salts of diorganodithiocarba ic acids have been described as multifunctional, antioxidant, antiwear and corrosion inhibiting additives for lubricants. They are also noted for their metal deactivating properties.
  • Metallic dithiophosphates are well-known for their use as effective corrosion/oxidation inhibitors as well as anti-wear additives in many lubricant and grease applications, including engine oils and industrial oils.
  • the beneficial effects of the of the instant invention are believed to be the result of an internal synergism between suitable metal groups, dithiophosphate groups, and dithiocarbamate groups within the same lubricant compositions.
  • the pre-blended combinations and reaction products of this invention show good stability and compatibility when used in the presence of other commonly used additives in grease or lubricant compositions.
  • U.S. Patent No. 5,002,674 discloses that ashless thiophosphates (such as 4,4-methylene bis(dibutyl dithiocarbamate) derived from dihydrocarbyl dithiocarbamates are effective multifunctional additives for lubricants, having antioxidant and antiwear properties.
  • U.S. Patent No. 4,290,202 discloses molybdenum dialkyl dithiophosphates which have utility as extreme pressure and antiwear agents.
  • Metallic dithiophosphates (such as zinc or molybdenum dialkyl dithiophosphates) are well known for their use as effective corrosion/oxidation inhibitors as well as antiwear additives in many lubricant and grease applications including engine oils and industrial oils.
  • U.S. Patent No. 4,360,438 discloses synergistic antiwear compositions comprising a sulfurized molybdenum dialkyldithiocarbamate and an organic sulfur compound selected from the group consisting of dithiocarbamate acid esters, sulfurized oils and polysulfurized olefins.
  • Dithiocarbanates are further discussed in an article coauthorized by one of the inventors of '438, H.H. Farmer. The chemistry of dithiocarbamates and their mechanisms are discussed in "Dithiocarbamate Additives in Lubricating Greases", A. F. Polishuk and H. H. Farmer, NLGI Spokesman, September, 1979, pp. 200-205.
  • U.S. Patent No. 2,492,314 discloses a process for the production of metal salts of substituted dithiocarbamic acids.
  • the preparation of a zinc salt of an alkyl dithiocarbanic acid is one salt disclosed.
  • the instant invention is directed to products of reaction and pre-blended combinations of metallic dithiocarbamates and metallic dithiophosphates, having synergistic anti-wear and friction reducing capacities.
  • the reaction products may vary according to the conditions employed, they are effective if their structures contain (a) metal dithiophosphates and (b) metal dithiocarbamates.
  • the metals maybe selected from nickel, antimony, molybdenum, copper, cobalt, iron, cadmium, zinc, manganese, sodium, magnesium, calcium and lead.
  • These products and combinations may be used as additives to lubricants and greases, providing enhanced friction- reducing, and antiwear properties at extreme pressures. They can significantly extend the service life of engines. Additional antioxidation, cleanliness, antifatigue, high temperature stabilizing, and anticorrosion properties are also potentially present.
  • the products of this invention show good stability and compatibility when used in the presence of other commonly used additives in grease or lubricant compositions. They are useful at low concentrations in lubricants.
  • This invention is directed to additives suitable for use in lubricant oils which are prepared in a process comprising reacting in an appropriate reaction zone (or mixing in pre-blended combinations) a metallic dithiocarbamate and a metallic dithiophosphate.
  • the preferred dithiocarbamates are zinc, nickel and antimony dialkyl dithiocarbamates.
  • the most preferred dithiocarbamate is antimony dialkyl dithiocarbamate.
  • the alkyl groups are preferably 2-30 carbons, more preferably 8 to 15 carbons, in length. Antimony dialkyl dithiocarbamate is illustrated below:
  • the dithiocarbamates are dark amber liquids, with a viscosity at 100°C of about 50 SUS(7.25 mm 2/s) .
  • the flash point(open cup) is about 17l°C (340°F) .
  • the pour point is about -23°C(-10°F) .
  • Metallic dithiocarbamates such as antimony dialkyl dithiocarbamates, may be obtained commercially from the R.T. Vanderbilt Chemical Company (under the trade name VanLube 73)as well as from other sources. Metallic dithiocarbamates may also be synthesized.
  • Sodium dialkyl dithiocarbamates can be synthesized by reacting equal molar amounts of sodium hydroxide, a secondary dialkyl amine, and carbon disulfide in aqueous media or organic solution depending on conditions as illustrated below:
  • Sodium dialkyl dithiocarbamates can also be used to prepare other metal dialkyl dithiocarbanates, such as those containing antimony or zinc. Preparation of an antimony dialkyl dithiocarbamate is illustrated below:
  • Zinc dialkyl dithiocarbanates may be made by reacting sodium dialkyl carbamates with ZnSo 4 , ZNC1 2 or Zn(OH) 2 .
  • the general blending or reaction conditions when the metallic dithiocarbamate and the metallic dithiophosphate phosphate are combined may be any suitable conditions known in the art. Temperatures will usually vary from -20° to 250°C. The temperature is preferably between 50°C and 150°C. Reaction rather than blending will usually occur if the temperature is between 70°C and 100"C. If a solvent is used the reaction conditions may vary. Usually atmospheric or ambient pressure is used. However, higher or lower pressures may be used if desired. The time required for reaction will vary primarily with the temperature, pressure and solvent used, if any. If a solvent is used it may be polar or non-polar. Polar solvents include acetones, alcohols, ethers and esters. Non-polar solvents include both aliphatic and aromatic hydrocarbons.
  • Metallic dithiophosphates useful in the instant invention include molybdenum, zinc, copper, lead, magnesium and cadmium dithiophosphates.
  • Molybdenum dialkyl phosphorothioate is commercially available from several sources. It is sold by R.T. Vanderbilt Chemical Company under the trade name Molyvan L.
  • the most preferred compounds useful in the instant invention are sulfurized oxymolybdenum organophosphorodithioates, illustrated below:
  • R represents alkyl or alkylaryl
  • m 2 to 3
  • n 2 to 1
  • m+n 4.
  • R may be an alkyl, cycloalkyl, aryl, or alkaryl radical. In most cases it is an alkyl chain of 2 to 30 carbons.
  • dithiophosphates also known as phosphoro- dithioates
  • the flash po ⁇ nt(open cup) is about 166°C(330°F) .
  • the pour point is about -37°C(-
  • the reaction product may be solid or liquid depending on the organic radical in the phosphorodithioic acid reactant. If the molybdenum-containing product is a solid, it is recovered by filtration. If the molybdenum- containing product is a liquid, it is recovered by filtering out any solid by-products and by distilling to remove the solvent.
  • the dithiophosphates may be prepared by dissolving molybdic oxide in a solution of alkali metal hydroxide, magnesium hydroxide, beryllium hydroxide or ammonium hydroxide and by incorporating subsequently an approximately equivalent amount, based on hydroxide, of a strong mineral acid, such as sulfuric acid.
  • An organophosphorodithioic acid reactant may be alternately prepared by treating a monohydric alcohol or phenol with phosphorus pentasulfide in the mole ratio of 4:1. The phosphorodithioic acid reactant is then added to the molybdate solution with subsequent finishing operations to form a sulfurized oxymolybdenum organophosphorodithioate.
  • reaction time is generally 1 to 5 hours.
  • the base lubricants which are useful with the additives of this invention may be any oil of lubricating viscosity, whether natural or synthetic.
  • the natural oils include paraffinic, naphthenic oils, or mixtures of them, neutral distillates and bright stocks.
  • polyolefin (synthetic hydrocarbon) fluids such as the polyolefins and hydrogenated polyolefins, especially the poly (alpha) olefins and hydrogenated poly (alpha) olefins.
  • synthetic hydrocarbon synthetic hydrocarbon
  • these are derived from olefins with 5 to 20 carbon atoms, particularly from 8 to 14 carbon atoms such as the poly 1-decenes and hydrogenated poly 1-decenes, as well as polybutenes including polyisobutenes.
  • Esters of dibasic acids may also be used as synthetic oils. These include the esters of C 6 - C 9 dibasic acids such as sebacic, azelaic and adipic acids having branched chain alcohols, such as 2-ethylhexanol or the C 8 - C 10 oxoalcohols. Useful esters include di(2-ethylhexyl)- sebacate, di(2-ethylhexyl)adipate, and dibutylphthalate.
  • C 6 - C 9 dibasic acids such as sebacic, azelaic and adipic acids having branched chain alcohols, such as 2-ethylhexanol or the C 8 - C 10 oxoalcohols.
  • Useful esters include di(2-ethylhexyl)- sebacate, di(2-ethylhexyl)adipate, and dibutylphthalate.
  • Esters of polyols such as the neopentyl polyols including neopentyl glycol, trimethylol propane, triethylol propane and pentaerythritol may also be used as synthetic hydrocarbon oils.
  • the esters of such polyols with monobasic carboxylic acids such as the C 5 - C 9 acids or mixtures of acids are examples.
  • Polyglycols such as polypropylene glycol, polyethylene glycol, and mixed polyoxyalkylene glycols can also be used as synthetic oils.
  • the base lubricant contemplated may also be a grease formulated by adding a grease-forming quantity of a thickening agent to one of the oils mentioned above.
  • a wide variety of materials may be employed.
  • These thickening agents or gelling agents may include any of the conventional metal salts or soaps which are dispersed in the lubricating oil in grease-forming quantities in such degree as to impart to the resulting grease the desired consistency.
  • Other thickening agents that may be employed in the formulation may comprise non- soap thickeners, such as modified clays and silicas and aryl ureas.
  • the lubricant compositions should contain from 0.01 to 8 wt.% and more preferably from 1.5 to 6 wt.% of the previously described synergistic preparation. Any other lubricant additives may be also incorporated, up to about 15 wt. % into the lubricant compositions for their known purposes.
  • molybdenum di-2-ethylhexyl dithiophosphate (commercially obtained from R.T. Vanderbilt Chemical Company under the trade name Molyvan L) and 3 gm of antimony diamyl dithiocarbamate (commercially obtained from R.T. Vanderbilt Chemical Company under the trade name Vanlube 73) were blended together in a mixer at room temperature for one hour. Thereafter, approximately 20 gm of yellow-green liquid was recovered as desired blending product.
  • molybdenum di-2-ethylhexyl dithiophosphate (commercially obtained from R.T. Vanderbilt Chemical Company under the trade name Molyvan L) and 3 gm of antimony diamyl dithiocarbamate (commercially obtained from R.T. Vanderbilt Chemical Company under the trade name Vanlube 73) were blended together in a mixer at 80°C for an hour. Thereafter, approximately 20 gm of yellow-green liquid was recovered as desired blending product.
  • a Reaction Product of Molybdenum Dithiophosphate and Antimony Dithiocarbamate Approximately 14 gm of molybdenum di-2-ethylhexyl dithiophosphate and 6 gm of antimony diamyl dithiocarbamate were blended together in a mixer at 80°C for one hour. Thereafter, approximately 20 gm of yellow-green liquid was recovered as desired product.
  • Base grease paraffinic-naphthenic mineral 0.525 0.096 oils plus a lithium thickener made from a (0.633)* (0.092)* a blend of 12-hydroxy and tallow fatty acids
  • Example 3 in base grease 0.430 0.065 3%
  • Example 6 in base grease 0.393 0.073 3%
  • Example 8 in base grease 0.458 0.044
  • Example 1 in base grease 0.379 0.083 1.5%
  • Example 4 in base grease 0.420 0.073
  • the Cameron-Plint Wear test measures frictional force employing a reciprocating friction machine.
  • the machine employs a line contact as opposed to a point contact (a point contact uses a ball on a flat surface) .
  • the line contact specimen configuration operates at 50 Hz, 100 N load, and a 0.76 mm stroke. The temperatures are ramped from 50 to 165°C. The duration of the test was 30 minutes.
  • Sample specimens consisted of a hardened steel (62 Rockwell C) ground gauge plate, finished to a surface roughness of 0.45 microns, and a 16 mm long nitride steel dowel pin as the contact (6mm diameter, 60 Re) .
  • Metallurgy for the plate and line contact are defined in British Standards BS 4659 and BS 1804 respectively. The steel specimens were immersed in approximately 10 ml of lubricant. Friction coefficients were calculated from frictional force by dividing by the load value,typically 100N, and were generally repeatable to +/-0.005.
  • Base grease paraffinic- 0.270 0.079 naphthenic mineral oils plus a lithium thickener made from a blend of 12- hydroxy and tallow fatty acids
  • the Optimal SRV Friction and Wear Test evaluates the friction, wear and breakaway torque characteristics of lubricants and materials under high-speed oscillation.
  • a mobile specimen oscillates on a fixed specimen to simulate rolling and sliding friction. Point, line and area contact geometries can be simulated.
  • the load in this case 100 N, is maintained at 50°C for 30 minutes.
  • the oscillation frequency is 50Hz.
  • the stroke, for measuring sliding friction is 1mm.
  • a 10 mm steel ball is oscillated under a specific load on a lapped steel disk lubricated with the grease or lubricant being tested until seizure occurs.
  • the bottom disk is cleaned with heptane and the wear scar is measured using a profilometer. Both scar depth and width measurements are recorded as an indication of the wear that occurred during the test. From these, the coefficient of friction can be calculated.
  • Base grease paraffinic-naphthenic mineral oils plus a lithium thickener made from a blend of 12-hydroxy and tallow fatty acids 0.120 Plus 6%
  • Example 3 0.095
  • each example demonstrated a lower coefficient of friction than that of the base grease. There was a tendency, however, for the coefficient of friction to be lower in the examples where blending had occurred at an elevated temperature (apparently in which a reaction had occurred)than in the examples where the components had merely been mixed.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP95907404A 1994-01-13 1995-01-11 ADDITIVES FOR LUBRICANTS Withdrawn EP0739405A4 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US18113594A 1994-01-13 1994-01-13
US181135 1994-01-13
PCT/US1995/000424 WO1995019411A1 (en) 1994-01-13 1995-01-11 Additives for lubricants

Publications (2)

Publication Number Publication Date
EP0739405A1 EP0739405A1 (en) 1996-10-30
EP0739405A4 true EP0739405A4 (en) 1997-01-22

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EP95907404A Withdrawn EP0739405A4 (en) 1994-01-13 1995-01-11 ADDITIVES FOR LUBRICANTS

Country Status (6)

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EP (1) EP0739405A4 (ja)
JP (1) JPH09508156A (ja)
KR (1) KR970700759A (ja)
AU (1) AU1564795A (ja)
CA (1) CA2179814A1 (ja)
WO (1) WO1995019411A1 (ja)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5814587A (en) * 1996-12-13 1998-09-29 Exxon Research And Engineering Company Lubricating oil containing an additive comprising the reaction product of molybdenum dithiocarbamate and metal dihydrocarbyl dithiophosphate
US5824627A (en) * 1996-12-13 1998-10-20 Exxon Research And Engineering Company Heterometallic lube oil additives
US6358894B1 (en) 1996-12-13 2002-03-19 Infineum Usa L.P. Molybdenum-antioxidant lube oil compositions
US5888945A (en) * 1996-12-13 1999-03-30 Exxon Research And Engineering Company Method for enhancing and restoring reduction friction effectiveness
JP3808609B2 (ja) * 1997-10-21 2006-08-16 新日本石油株式会社 転がり軸受用グリース組成物
US5939364A (en) * 1997-12-12 1999-08-17 Exxon Research & Engineering Co. Lubricating oil containing additive comprising reaction product of molybdenum dithiocarbamate and dihydrocarbyl dithiophosphoric acid
JPH11246581A (ja) * 1998-02-28 1999-09-14 Tonen Corp 亜鉛−モリブデン系ジチオカルバミン酸塩誘導体、その製造方法およびそれを含有する潤滑油組成物
CN102453587B (zh) * 2010-10-27 2014-04-30 中国石油化工股份有限公司润滑油研发(北京)中心 一种柴油发动机磨合油补强剂

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4648985A (en) * 1984-11-15 1987-03-10 The Whitmore Manufacturing Company Extreme pressure additives for lubricants
EP0275351A1 (de) * 1987-01-22 1988-07-27 MAX GRILL Ges.mbH Schmierfähige Hydraulikflüssigkeit, insbesondere Bremsflüssigkeit, Verfahren zu ihrer Herstellung und ihre Verwendung
EP0286140A1 (de) * 1987-04-10 1988-10-12 Erasmus Dr. Froeschmann Schmiermittel bzw. Schmiermittelkonzentrat

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US2492314A (en) * 1945-01-16 1949-12-27 Sharples Chemicals Inc Process for producing metal salts of substituted dithiocarbamic acids
US3494866A (en) * 1965-10-28 1970-02-10 Vanderbilt Co R T Molybdenum compounds in lubricants
US4290902A (en) * 1979-12-03 1981-09-22 Texaco Inc. Oxymolybdenum dialkyldithiophosphates and lubricants containing same
US4360438A (en) * 1980-06-06 1982-11-23 R. T. Vanderbilt Company, Inc. Organomolybdenum based additives and lubricating compositions containing same
US4692256A (en) * 1985-06-12 1987-09-08 Asahi Denka Kogyo K.K. Molybdenum-containing lubricant composition
DE3610205A1 (de) * 1986-03-26 1987-10-01 Tribol Lubricants Gmbh Schmiermittel und verfahren zu dessen herstellung
US4919830A (en) * 1988-12-30 1990-04-24 Mobil Oil Corporation Dithiocarbamate-derived phosphates as antioxidant/antiwear multifunctional additives

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4648985A (en) * 1984-11-15 1987-03-10 The Whitmore Manufacturing Company Extreme pressure additives for lubricants
EP0275351A1 (de) * 1987-01-22 1988-07-27 MAX GRILL Ges.mbH Schmierfähige Hydraulikflüssigkeit, insbesondere Bremsflüssigkeit, Verfahren zu ihrer Herstellung und ihre Verwendung
EP0286140A1 (de) * 1987-04-10 1988-10-12 Erasmus Dr. Froeschmann Schmiermittel bzw. Schmiermittelkonzentrat

Non-Patent Citations (1)

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Title
See also references of WO9519411A1 *

Also Published As

Publication number Publication date
WO1995019411A1 (en) 1995-07-20
AU1564795A (en) 1995-08-01
EP0739405A1 (en) 1996-10-30
JPH09508156A (ja) 1997-08-19
KR970700759A (ko) 1997-02-12
CA2179814A1 (en) 1995-07-20

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