EP1036142A1 - Lubricating compositions - Google Patents

Lubricating compositions

Info

Publication number
EP1036142A1
EP1036142A1 EP98951402A EP98951402A EP1036142A1 EP 1036142 A1 EP1036142 A1 EP 1036142A1 EP 98951402 A EP98951402 A EP 98951402A EP 98951402 A EP98951402 A EP 98951402A EP 1036142 A1 EP1036142 A1 EP 1036142A1
Authority
EP
European Patent Office
Prior art keywords
zinc
grease
composition
lubricating
molybdenum disulphide
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Withdrawn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
EP98951402A
Other languages
German (de)
French (fr)
Inventor
Robert Anthony Fletcher
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.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
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 Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Priority to EP98951402A priority Critical patent/EP1036142A1/en
Publication of EP1036142A1 publication Critical patent/EP1036142A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C10M141/00—Lubricating 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
    • C10M141/10—Lubricating 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
    • 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
    • C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
    • 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
    • C10M119/00—Lubricating compositions characterised by the thickener being a macromolecular compound
    • C10M119/24—Lubricating compositions characterised by the thickener being a macromolecular compound containing nitrogen
    • 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/22—Compounds containing sulfur, selenium or tellurium
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
    • 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
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06—Mixtures of thickeners and additives
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
    • C10M2201/066—Molybdenum sulfide
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/08—Inorganic acids or salts thereof
    • C10M2201/084—Inorganic acids or salts thereof containing sulfur, selenium or tellurium
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/106—Carboxylix acids; Neutral salts thereof used as thickening agents
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/1206—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms used as thickening agents
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix 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
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/1406—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings used as thickening agents
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/2613—Overbased carboxylic acid salts used as thickening agents
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C10M2207/2626—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates used as thickening agents
    • 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
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl 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
    • C10M2217/044—Polyamides
    • 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
    • C10M2217/045—Polyureas; Polyurethanes
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal 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
    • 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
    • C10N2010/12—Groups 6 or 16

Definitions

  • the present invention relates to lubricating compositions, particularly to lubricating greases containing such compositions, and more particularly to lubricating greases for use in constant velocity joints of all types, e.g. to constant velocity fixed ball joints and to the plunging type constant velocity joint.
  • the primary purpose of lubrication is separation of solid surfaces moving relative to one another, to minimise friction and wear.
  • the materials most frequently used for this purpose are oils and greases.
  • the choice of lubricant is mostly determined by the particular application.
  • Lubricating greases are employed where heavy pressures exist, where oil drip from the bearings is undesirable or where the motion of the contacting surfaces is discontinuous so that it is difficult to maintain a separating film in the bearing. Because of design simplicity, decreased sealing requirements and less need for maintenance, greases are almost universally given first consideration for lubricating ball and roller bearings in electric motors, household appliances, automotive wheel bearings, machine tools or aircraft accessories. Greases are also used for the lubrication of small gear drives and for many slow- speed sliding applications.
  • Lubricating greases consist primarily of a fluid lubricant, such as an oil, and a thickener. Essentially, the same type of oil is employed in compounding a grease as would normally be selected for oil lubrication.
  • Fatty acid soaps of lithium, calcium, sodium, aluminium and barium are most commonly used as thickeners.
  • thickeners may be one of a variety of solid materials, including clays, soaps and complexes such as those of lithium, and urea-type compounds .
  • the base oil may be of mineral or synthetic origin. Base oils of mineral origin may be mineral oils, for example produced by solvent refining or hydro- processing. Base oils of synthetic origin may typically be mixtures of hydrocarbon polymers, for example liquid polymers of alpha-olefins .
  • the base oil may also be a mixture of these oils.
  • the base oil is that of mineral origin sold by the Royal Dutch/Shell Group of Companies under the designations "HVI” or "MVIN”, is a polyalphaolefin, or is a mixture of the two.
  • Synthetic hydrocarbon base oils for example those sold by the Royal Dutch/Shell Group of Companies under the designation "XHVI” (trade mark) may also be used.
  • a lubricating grease preferably contains 5 to 20% by weight of thickener.
  • Lithium soap thickened greases have been known for many years.
  • the lithium soaps are derived from C ⁇ _o-2 / preferably Ci5_ ⁇ _g, saturated or unsaturated fatty acids or derivatives thereof.
  • One particular derivative is hydrogenated castor oil, which is the glyceride of 12-hydroxystearic acid.
  • 12-Hydroxystearic acid is a particularly preferred fatty acid.
  • Greases thickened with complex thickeners are well known.
  • a complexing agent is incorporated into the thickener, which is commonly a low to medium molecular weight acid or dibasic acid or one of its salts, such as benzoic acid or boric acid or a lithium borate.
  • Urea compounds used as thickeners in greases include the urea group (-NHCONH-) in their molecular structure. These compounds include mono-, di- or polyurea compounds, depending upon the number of urea linkages.
  • Zinc dithiocarbamates are sometimes used as antioxidants and also as corrosion inhibitors in some lubricants such as diesel and gasoline engine oils and industrial oils.
  • Molybdenum disulphide (a non-organic molybdenum compound) is a known highly wear resistant solid lubricant and is used in a wide variety of lubricants.
  • MoDTC molybdenum dithiophosphates
  • ZnDTP zinc dialkyl dithiophosphate
  • Molybdenum disulphide thought by some to be such a decomposition product, was tested in a reference grease thickened with a lithium 12-hydroxy stearate soap and containing 0.5% mass zinc dibutyl dithiocarbamate as an oxidation inhibitor.
  • the resulting grease exhibited high (i.e. undesirable) friction and only moderate anti-wear properties; zinc compounds tested separately in the same reference grease also showed no reduced friction.
  • a friction reducing additive combination comprising molybdenum disulphide, zinc naphthenate and metal dithiophosphate optionally in combination with metal dithiocarbamates.
  • Example 22 it is shown that the presence of zinc naphthenate is essential.
  • molybdenum disulphide, zinc dithiocarbamate and a metal dithiophosphate in combination work synergistically as a friction reducing agent in lubricating compositions, especially greases, whilst retaining good, low anti- wear properties.
  • zinc naphthenate does not need to be present in this combination. Furthermore such combination is not thickener dependent. Tested against the use of molybdenum disulphide alone or in combination with one of the two other components, the friction reduction is shown to be quite unexpected.
  • the present invention accordingly provides a lubricating composition which comprises a base oil of mineral and/or synthetic origin and a combination of molybdenum disulphide, one or more zinc dithiocarbamates and one or more metal dithiophosphates which composition contains no substantial amount of zinc naphthenate.
  • the composition of the present invention contains no substantial amount of zinc naphthenate. This means that the composition contains less than 0.3% by weight of zinc naphthenate, based on total weight of lubricating composition.
  • the amount of zinc naphthenate is the amount of compound per se, excluding further compounds which may be present in a commercial product e.g. mineral oil.
  • the composition preferably contains less than 0.05% by weight of zinc naphthenate, more preferably less than 0.01% wt . Most preferably, the composition does not contain zinc naphthenate.
  • Preferred is the use of the friction reducing additive combination in a lubricating grease which comprises a base oil of mineral and/or synthetic origin and a thickener, which is preferably a lithium soap, either simple or complex, or a urea compound.
  • Such a lubricating grease preferably contains molybdenum disulphide in an amount of from 0.5 to 10% by weight, more preferably 1 to 4% by weight.
  • the grease preferably contains zinc dithiocarbamate in an amount of from 0.01 to 5% by weight, more preferably 0.3 to 2.4% by weight, for a urea thickened grease and a complex lithium soap thickened greases, and an amount of from 0.5 to 10% by weight, more preferably 1 to 4% by weight, for a simple lithium soap thickened grease.
  • a lubricating grease of the invention further preferably contains said one or more metal dithiophosphates in a total amount of from 0.15 to 10% by weight; more preferably 1 to 3% by weight. All amounts are based on total weight of the grease composition.
  • the three components are present in an interrelated or 3-way proportion such that, for a urea thickened grease and for a complex lithium soap thickened grease the weight ratio of molybdenum disulphide to metal dithiophosphate is in the range of from 1:0.15 to 1:1, the weight ratio of metal dithiophosphate to zinc dithiocarbamate is in the range of from 1:0.25 to 1:1.5, and the weight ratio of molybdenum disulphide to zinc dithiocarbamate is in the range of from 1:0.4 to 1:1.5.
  • the weight ratio of molybdenum disulphide to metal dithiophosphate preferably is in the range of from 1:0.15 to 1:1, the weight ratio of metal dithiophosphate to zinc dithiocarbamate is in the range of from 1:1 to 1:4.5 and the weight ratio of molybdenum disulphide to zinc dithiocarbamate is in the range of from 1:0.4 to 1:1.5.
  • the one or more metal dithiophosphates is/are selected from zinc dialkyl-, diaryl- or alkylaryl-dithiophosphates
  • the one or more zinc dithiocarbamates is/are selected from zinc dialkyl-, diaryl- or alkylaryl-dithiocarbamates, in which dithiophosphates and/or dithiocarbamates usefully any alkyl moiety is straight chain or branched and preferably contains from 1 to 12 carbon atoms.
  • the thickener of lubricating greases preferably comprises a urea compound, a simple lithium soap or a complex lithium soap.
  • a preferred urea compound is a polyurea compound.
  • Such thickeners are well known in lubricant grease technology. Surprisingly effective compositions of the invention use simple lithium soaps as thickeners.
  • Lubricating compositions of the invention may be prepared by incorporating the additive combination into a base oil in conventional manner. For greases this may be via hot or cold mixing followed by homogenisation to ensure uniform dispersion of the additive components. Other additives, e.g. antioxidants, may be included if necessary or desired.
  • a method of lubricating a constant velocity joint comprising packing it with a lubricating grease according to the present invention.
  • a constant velocity joint packed with a lubricating grease according to the present invention there is still further provided.
  • Example 1 The present invention will now be described by reference to the following Examples, in which all percentages are given by weight.
  • Example 1
  • a lithium soap grease was prepared by adding a slurry of 1.12% w LiOH.F ⁇ O and water in the proportions of 1 part LiOH.I ⁇ O to 5 parts water to 9.15% w hydrogenated castor oil fatty acid in cold base oil (a blend of MVIN and HVI oils) and heating the mix in a sealed autoclave to 150°C. The steam was vented off and heating continued to 220°C before the reaction mass was quick cooled (at a rate of 6 to 7°C per minute) and the product homogenised. Additives were incorporated into the grease. In all cases, as antioxidant, 0.5% w of an aromatic amine was used.
  • a grease of the present invention and a number of comparison greases were prepared and tested.
  • the amount of molybdenum disulphide, ZnDTC (zinc diamyl dithiocarbamate) and ZnDTP (4-methyl-2-pentyl zinc dithiophosphate) was varied as shown in Table 1.
  • the friction coefficient and wear scar diameter were evaluated for each grease; the results are also given in Table 1.
  • the friction and wear measurements were made using an oscillating SRV friction tester.
  • the oscillating SRV friction tester (from Optimol Instruments) was used with a 10 mm ball on a flat lapped surface as test geometry. An oscillation frequency of 50 Hertz and a stroke of 1.5 mm was used throughout. The friction coefficient was recorded after two hours of operation under the test conditions of a load of 300 Newtons at a temperature of 100°C.
  • Wear was assessed by measuring the diameter of the wear scar on the ball at the end of the two hour test using an optical graticule.
  • a grease of the present invention was compared with lithium greases having only molybdenum disulphide or molybdenum disulphide plus zinc dithiocarbamate or molybdenum disulphide plus zinc dithiophosphate all with the same base grease plus thickener plus antioxidant. It can be clearly seen from the results that the grease of the present invention has a significantly lower friction coefficient and wear scar diameter than any of the comparison greases.
  • Example 2
  • a urea grease C was prepared by heating 5% w of 4, 4 '-diphenylmethane diisocyanate in base oil (a mixture of 75% w HVI 160B and 25% w HVI 650) to 70°C and then adding 10.8% w stearylamine . The mixture was then further heated to 150°C before being cooled to 80°C. The other additives to be included in the formulation were then added. The formulated grease was then homogenised at ambient temperature.
  • a grease of the present invention and a number of comparison greases were prepared and tested. Again in all cases, an antioxidant, 0.5% w of an aromatic amine, was added and for each grease the amount of molybdenum disulphide, ZnDTC (zinc diamyl dithiocarbamate) and ZnDTP (4-methyl-2-pentyl zinc dithiphosphate) were varied. The friction coefficient and wear for each grease was evaluated as in Example 1. Results are given in Table 2.
  • a lithium complex grease was prepared by adding a 50%w slurry of LiOH.H0 and boric acid in water to hydrogenated castor oil fatty acid, calcium alkyl salicylate, and calcium octoate, in conventional proportions, in base oil, (a mixture of HVI oils) together with conventional antioxidants, and then heating the charge to 210°C with stirring. After slowly cooling the mixture to 160°C a quinoline and a hydroxyphenyl were added as additional antioxidants.
  • the grease obtained contained 3% w molybdenum disulphide, 1.5% w ZnDTC and 1.5% w ZnDTP as friction reducing additive.

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Abstract

A lubricating composition which comprises a base oil of mineral and/or synthetic origin and, as a friction reducing additive, a combination of molybdenum disulphide, one or more zinc dithiocarbamates and one or more metal dithiophosphates, which composition contains no substantial amount of zinc naphthenate.

Description

LUBRICATING COMPOSITIONS
The present invention relates to lubricating compositions, particularly to lubricating greases containing such compositions, and more particularly to lubricating greases for use in constant velocity joints of all types, e.g. to constant velocity fixed ball joints and to the plunging type constant velocity joint.
The primary purpose of lubrication is separation of solid surfaces moving relative to one another, to minimise friction and wear. The materials most frequently used for this purpose are oils and greases. The choice of lubricant is mostly determined by the particular application.
Lubricating greases are employed where heavy pressures exist, where oil drip from the bearings is undesirable or where the motion of the contacting surfaces is discontinuous so that it is difficult to maintain a separating film in the bearing. Because of design simplicity, decreased sealing requirements and less need for maintenance, greases are almost universally given first consideration for lubricating ball and roller bearings in electric motors, household appliances, automotive wheel bearings, machine tools or aircraft accessories. Greases are also used for the lubrication of small gear drives and for many slow- speed sliding applications.
Lubricating greases consist primarily of a fluid lubricant, such as an oil, and a thickener. Essentially, the same type of oil is employed in compounding a grease as would normally be selected for oil lubrication. Fatty acid soaps of lithium, calcium, sodium, aluminium and barium are most commonly used as thickeners. However, thickeners may be one of a variety of solid materials, including clays, soaps and complexes such as those of lithium, and urea-type compounds . The base oil may be of mineral or synthetic origin. Base oils of mineral origin may be mineral oils, for example produced by solvent refining or hydro- processing. Base oils of synthetic origin may typically be mixtures of hydrocarbon polymers, for example liquid polymers of alpha-olefins . They may also be conventional esters, for example polyol esters. The base oil may also be a mixture of these oils. Preferably the base oil is that of mineral origin sold by the Royal Dutch/Shell Group of Companies under the designations "HVI" or "MVIN", is a polyalphaolefin, or is a mixture of the two. Synthetic hydrocarbon base oils, for example those sold by the Royal Dutch/Shell Group of Companies under the designation "XHVI" (trade mark) may also be used. A lubricating grease preferably contains 5 to 20% by weight of thickener.
Lithium soap thickened greases have been known for many years. Typically, the lithium soaps are derived from Cη_o-2 / preferably Ci5_ι_g, saturated or unsaturated fatty acids or derivatives thereof. One particular derivative is hydrogenated castor oil, which is the glyceride of 12-hydroxystearic acid. 12-Hydroxystearic acid is a particularly preferred fatty acid. Greases thickened with complex thickeners are well known. In addition to a fatty acid salt, a complexing agent is incorporated into the thickener, which is commonly a low to medium molecular weight acid or dibasic acid or one of its salts, such as benzoic acid or boric acid or a lithium borate. Urea compounds used as thickeners in greases include the urea group (-NHCONH-) in their molecular structure. These compounds include mono-, di- or polyurea compounds, depending upon the number of urea linkages.
Various conventional grease additives may be incorporated into the lubricating greases, in amounts normally used in this field of application, to impart certain desirable characteristics to the grease, such as oxidation stability, tackiness, extreme pressure properties and corrosion inhibition. Suitable additives include one or more extreme pressure/antiwear agents, for example zinc salts such as zinc dialkyl or diaryl dithiophosphates, borates, substituted thiadiazoles, polymeric nitrogen/phosphorus compounds made, for example, by reacting a dialkoxy amine with a substituted organic phosphate, amine phosphates, sulphurised sperm oils of natural or synthetic origin, sulphurised lard, sulphurised esters, sulphurised fatty acid esters, and similar sulphurised materials, organo- phosphates for example according to the formula (OR) 3P=0 where R is an alkyl, aryl or aralkyl group, and triphenyl phosphorothionate; one or more overbased metal-containing detergents, such as calcium or magnesium alkyl salicylates or alkylarylsulphonates; one or more ashless dispersant additives, such as reaction products of polyisobutenyl succinic anhydride and an amine or ester; one or more antioxidants, such as hindered phenols or amines, for example phenyl alpha naphthylamine; one or more antirust additives; one or more friction-modifying additives; one or more viscosity-index improving agents; one or more pour point depressing additives; and one or more tackiness agents. Solid materials such as graphite, finely divided molybdenum disulphide, talc, metal powders, and various polymers such as polyethylene wax may also be added to impart special properties.
Zinc dithiocarbamates are sometimes used as antioxidants and also as corrosion inhibitors in some lubricants such as diesel and gasoline engine oils and industrial oils.
In lubricants generally, the reduction of friction
(i.e. the increase of slideability) combined with the reduction of wear (i.e. the reduction of surface damage caused by mechanical and/or corrosive action) is highly desirable .
There have been a number of proposals to reduce friction levels using a variety of additives, usually incorporating organic molybdenum-based formulations. Often the friction reducing effect is thickener dependent, i.e. an additive will work well with one thickener type but not with another.
Molybdenum disulphide (a non-organic molybdenum compound) is a known highly wear resistant solid lubricant and is used in a wide variety of lubricants.
Equally common is the use of metal (dialkyl or diaryl) dithiophophates in lubricants as extreme pressure or anti wear agents.
Tribology Transactions, vol 33, no. 3, (1990) pages 345 to 354 reviews the effects of organic molybdenum compounds (such as molybdenum dialkyl dithiocarbamates
(MoDTC) and molybdenum dithiophosphates (MoDTP) ) on wear and friction with zinc dialkyl dithiophosphate (ZnDTP) -containing lubricant blends. In the early part of the review, tests on various components in a lubricating oil establishes inter alia that zinc compounds, including a zinc dithiocarbamate, exhibited similar high load antiwear performance to a molybdenum dithiocarbamate. Later in the review, a number of products commonly speculated to be decomposition products of MoDTC or MoDTP and ZnDTP additives, were suspended into a reference grease for independent evaluation to determine whether indeed any of those products gave good friction and antiwear properties. Molybdenum disulphide, thought by some to be such a decomposition product, was tested in a reference grease thickened with a lithium 12-hydroxy stearate soap and containing 0.5% mass zinc dibutyl dithiocarbamate as an oxidation inhibitor. The resulting grease exhibited high (i.e. undesirable) friction and only moderate anti-wear properties; zinc compounds tested separately in the same reference grease also showed no reduced friction.
In WO 97/03152, a friction reducing additive combination has been described comprising molybdenum disulphide, zinc naphthenate and metal dithiophosphate optionally in combination with metal dithiocarbamates. In Example 22 it is shown that the presence of zinc naphthenate is essential. It has now surprisingly been found that molybdenum disulphide, zinc dithiocarbamate and a metal dithiophosphate in combination work synergistically as a friction reducing agent in lubricating compositions, especially greases, whilst retaining good, low anti- wear properties. It has been found that zinc naphthenate does not need to be present in this combination. Furthermore such combination is not thickener dependent. Tested against the use of molybdenum disulphide alone or in combination with one of the two other components, the friction reduction is shown to be quite unexpected.
The use of lubricating oil compositions containing molybdenum disulphide, molybdenum dithiocarbamate and metal dithiophosphate has been described in WO 94/11470 and GB-A-2 255 103. WO 94/11470 or GB-A-2 255 103 neither teach nor hint that the molybdenum dithiocarbamate might be replaced by another metal dithiocarbamate .
The present invention accordingly provides a lubricating composition which comprises a base oil of mineral and/or synthetic origin and a combination of molybdenum disulphide, one or more zinc dithiocarbamates and one or more metal dithiophosphates which composition contains no substantial amount of zinc naphthenate.
The composition of the present invention contains no substantial amount of zinc naphthenate. This means that the composition contains less than 0.3% by weight of zinc naphthenate, based on total weight of lubricating composition. The amount of zinc naphthenate is the amount of compound per se, excluding further compounds which may be present in a commercial product e.g. mineral oil. The composition preferably contains less than 0.05% by weight of zinc naphthenate, more preferably less than 0.01% wt . Most preferably, the composition does not contain zinc naphthenate. Preferred is the use of the friction reducing additive combination in a lubricating grease which comprises a base oil of mineral and/or synthetic origin and a thickener, which is preferably a lithium soap, either simple or complex, or a urea compound.
Such a lubricating grease preferably contains molybdenum disulphide in an amount of from 0.5 to 10% by weight, more preferably 1 to 4% by weight. Independently, the grease preferably contains zinc dithiocarbamate in an amount of from 0.01 to 5% by weight, more preferably 0.3 to 2.4% by weight, for a urea thickened grease and a complex lithium soap thickened greases, and an amount of from 0.5 to 10% by weight, more preferably 1 to 4% by weight, for a simple lithium soap thickened grease. A lubricating grease of the invention further preferably contains said one or more metal dithiophosphates in a total amount of from 0.15 to 10% by weight; more preferably 1 to 3% by weight. All amounts are based on total weight of the grease composition.
It is especially useful if the three components are present in an interrelated or 3-way proportion such that, for a urea thickened grease and for a complex lithium soap thickened grease the weight ratio of molybdenum disulphide to metal dithiophosphate is in the range of from 1:0.15 to 1:1, the weight ratio of metal dithiophosphate to zinc dithiocarbamate is in the range of from 1:0.25 to 1:1.5, and the weight ratio of molybdenum disulphide to zinc dithiocarbamate is in the range of from 1:0.4 to 1:1.5. For a simple lithium soap thickened grease the weight ratio of molybdenum disulphide to metal dithiophosphate preferably is in the range of from 1:0.15 to 1:1, the weight ratio of metal dithiophosphate to zinc dithiocarbamate is in the range of from 1:1 to 1:4.5 and the weight ratio of molybdenum disulphide to zinc dithiocarbamate is in the range of from 1:0.4 to 1:1.5.
Preferably, the one or more metal dithiophosphates is/are selected from zinc dialkyl-, diaryl- or alkylaryl-dithiophosphates, and the one or more zinc dithiocarbamates is/are selected from zinc dialkyl-, diaryl- or alkylaryl-dithiocarbamates, in which dithiophosphates and/or dithiocarbamates usefully any alkyl moiety is straight chain or branched and preferably contains from 1 to 12 carbon atoms.
The thickener of lubricating greases, as mentioned hereinbefore, preferably comprises a urea compound, a simple lithium soap or a complex lithium soap. A preferred urea compound is a polyurea compound. Such thickeners are well known in lubricant grease technology. Surprisingly effective compositions of the invention use simple lithium soaps as thickeners.
Lubricating compositions of the invention may be prepared by incorporating the additive combination into a base oil in conventional manner. For greases this may be via hot or cold mixing followed by homogenisation to ensure uniform dispersion of the additive components. Other additives, e.g. antioxidants, may be included if necessary or desired. In accordance with the present invention there is further provided a method of lubricating a constant velocity joint comprising packing it with a lubricating grease according to the present invention. In accordance with the present invention there is still further provided a constant velocity joint packed with a lubricating grease according to the present invention.
The present invention will now be described by reference to the following Examples, in which all percentages are given by weight. Example 1
A lithium soap grease was prepared by adding a slurry of 1.12% w LiOH.F^O and water in the proportions of 1 part LiOH.I^O to 5 parts water to 9.15% w hydrogenated castor oil fatty acid in cold base oil (a blend of MVIN and HVI oils) and heating the mix in a sealed autoclave to 150°C. The steam was vented off and heating continued to 220°C before the reaction mass was quick cooled (at a rate of 6 to 7°C per minute) and the product homogenised. Additives were incorporated into the grease. In all cases, as antioxidant, 0.5% w of an aromatic amine was used.
A grease of the present invention and a number of comparison greases were prepared and tested. For each grease the amount of molybdenum disulphide, ZnDTC (zinc diamyl dithiocarbamate) and ZnDTP (4-methyl-2-pentyl zinc dithiophosphate) was varied as shown in Table 1. The friction coefficient and wear scar diameter were evaluated for each grease; the results are also given in Table 1.
The friction and wear measurements were made using an oscillating SRV friction tester. For friction measurements the oscillating SRV friction tester (from Optimol Instruments) was used with a 10 mm ball on a flat lapped surface as test geometry. An oscillation frequency of 50 Hertz and a stroke of 1.5 mm was used throughout. The friction coefficient was recorded after two hours of operation under the test conditions of a load of 300 Newtons at a temperature of 100°C.
Wear was assessed by measuring the diameter of the wear scar on the ball at the end of the two hour test using an optical graticule.
A grease of the present invention was compared with lithium greases having only molybdenum disulphide or molybdenum disulphide plus zinc dithiocarbamate or molybdenum disulphide plus zinc dithiophosphate all with the same base grease plus thickener plus antioxidant. It can be clearly seen from the results that the grease of the present invention has a significantly lower friction coefficient and wear scar diameter than any of the comparison greases. Example 2
A urea grease C was prepared by heating 5% w of 4, 4 '-diphenylmethane diisocyanate in base oil (a mixture of 75% w HVI 160B and 25% w HVI 650) to 70°C and then adding 10.8% w stearylamine . The mixture was then further heated to 150°C before being cooled to 80°C. The other additives to be included in the formulation were then added. The formulated grease was then homogenised at ambient temperature.
A grease of the present invention and a number of comparison greases were prepared and tested. Again in all cases, an antioxidant, 0.5% w of an aromatic amine, was added and for each grease the amount of molybdenum disulphide, ZnDTC (zinc diamyl dithiocarbamate) and ZnDTP (4-methyl-2-pentyl zinc dithiphosphate) were varied. The friction coefficient and wear for each grease was evaluated as in Example 1. Results are given in Table 2.
It can be seen that also for a urea-thickened grease a significantly low friction coupled with low wear is exhibited, but with a lower proportion of ZnDTC than for the lithium soap thickened grease of Example 1.
Table 1
Grease of Example Molybdenum Friction Wear Scar
No. Disulphide ZnDTC ZnDTP 3ef f icient Diameter
(%w) (%w) (%w) (nm)
1 3 2 1 0. ,055 0. 50
Comparison A - 0. ,143 0. 85
Comparison B 3 - - 0. .138 0. 84
Comparison C 3 2 - 0. ,075 0. 58
Comparison D 3 - 1 0. 075 0. 65
Table 2
Grease of Example Molybdenum Friction Wear Scar No. Disulphi .de ZnDTC ZnDTP Coefficient Diameter
(%w) (%w) (%w) (nm)
2 3 0.5 1 0.055 0.57 Comparison E - - - 0.100 0.46 Comparison F 3 - - 0.153 0.78 Comparison G 3 - 1 0.080 0.67 Comparison H 3 2 1 0.093 0.53
Exampl e 3
A lithium complex grease was prepared by adding a 50%w slurry of LiOH.H0 and boric acid in water to hydrogenated castor oil fatty acid, calcium alkyl salicylate, and calcium octoate, in conventional proportions, in base oil, (a mixture of HVI oils) together with conventional antioxidants, and then heating the charge to 210°C with stirring. After slowly cooling the mixture to 160°C a quinoline and a hydroxyphenyl were added as additional antioxidants.
The whole was then slowly cooled to ambient temperature and molybdenum disulphide, ZnDTC (zinc diamyl dithiocarbamate and ZnDTP ( -methyl-2-pentyl zinc dithiophosphate) were added; the resulting grease was then homogenised.
The grease obtained contained 3% w molybdenum disulphide, 1.5% w ZnDTC and 1.5% w ZnDTP as friction reducing additive.
Using the same test methods as described in Example 1 above, the friction coefficient and wear for the grease were measured at 300N and 100°C as 0.058 and 0.48 nm respectively. Thus the surprising low friction coefficient coupled with low wear properties are also given when using a lithium complex thickened grease.

Claims

C L A I M S
1. A lubricating composition which comprises a base oil of mineral and/or synthetic origin and a combination of molybdenum disulphide, one or more zinc dithiocarbamates and one or more metal dithiophosphates, which composition contains no substantial amount of zinc naphthenate.
2. A composition as claimed in claim 1, wherein the one or more zinc dithiocarbamates are selected from zinc dialkyl-, diaryl-, and alkylaryl dithiocarbamates.
3. A composition as claimed in claim 1 or claims 2, wherein the one or more metal dithiophosphates are selected from zinc dialkyl-, diaryl- and alkylaryl dithiophosphates .
4. A composition as claimed in any one of claims 1 to 3, which is a grease and further contains a thickener.
5. A composition as claimed in claim 4, wherein the thickener is a simple lithium soap.
6. A composition as claimed in claim 5, wherein the weight ratio of molybdenum disulphide to metal dithiophosphate is in the range of from 1:0.15 to 1:1, the weight ratio of metal dithiophosphate to zinc dithiocarbamate is in the range of from 1:1 to 1:4.5 and the weight ratio of molybdenum disulphide to zinc dithiocarbamate is in the range of from 1:04 to 1:1.5.
7. A composition as claimed in claim 4, wherein the thickener is a urea compound or a complex lithium soap and wherein the weight ratio of molybdenum disulphide to metal dithiophosphate is in the range of from 1:0.15 to 1:1, the weight ratio of metal dithiophosphate to zinc dithiocarbamate is in the range of from 1:0.25 to 1:1.5, and the weight ratio of molybdenum disulphide to zinc dithiocarbamate is in the range of from 1:0.4 to 1:1.5.
8. A method of lubricating a constant velocity joint comprising packing it with a lubricating grease as claimed in any one of claims 4 to 7.
9. A constant velocity joint packed with a lubricating grease as claimed in any one of claims 4 to 7.
EP98951402A 1997-09-12 1998-09-11 Lubricating compositions Withdrawn EP1036142A1 (en)

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Publication number Priority date Publication date Assignee Title
JP3960725B2 (en) * 1999-11-30 2007-08-15 Ｎｔｎ株式会社 Constant velocity universal joint with boots
JP2005226038A (en) * 2004-02-16 2005-08-25 Kyodo Yushi Co Ltd Grease composition for constant-velocity joint for steering and constant-velocity joint for steering
EP2075314A1 (en) 2007-12-11 2009-07-01 Shell Internationale Research Maatschappij B.V. Grease formulations
FR2968669B1 (en) * 2010-12-13 2014-02-28 Total Raffinage Marketing FAT COMPOSITION
EP2559748B1 (en) * 2011-08-19 2016-06-08 Infineum International Limited Lubricating oil composition
CN103289569B (en) * 2013-05-09 2016-01-20 安徽工业大学 A kind of self-lubricating passivating solution and the pot galvanize self-lubricating coat in use steel plate with its coating
CN104164286A (en) * 2014-08-05 2014-11-26 中国石油化工股份有限公司 Lubricating grease composition for steering ball joint and preparation method of lubricating grease composition
DE102014018718A1 (en) * 2014-12-17 2016-06-23 Klüber Lubrication München Se & Co. Kg High temperature lubricants
CN104974827A (en) * 2015-05-26 2015-10-14 安徽不二越精工轴承有限公司 Novel lubricating oil
CN104974818B (en) * 2015-07-16 2017-07-28 合肥学院 A kind of method that lubricating oil in esters greasy property declines caused by suppression carbon smoke pollution
CN106080149A (en) * 2016-07-22 2016-11-09 安徽省地坤汽车天窗科技有限公司 A kind of pole structure for the assembling of skylight deflector
CN106635302A (en) * 2016-09-21 2017-05-10 广西大学 A cold stamping lubricant composition for 625 alloys
WO2020131441A1 (en) 2018-12-19 2020-06-25 Exxonmobil Research And Engineering Company Grease compositions having improved performance

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4536308A (en) * 1984-10-01 1985-08-20 Texaco Inc. Lithium soap grease additive
JP2915611B2 (en) * 1991-04-01 1999-07-05 協同油脂株式会社 Grease composition for constant velocity joints
GB9223945D0 (en) * 1992-11-14 1993-01-06 Gkn Technology Ltd Greases
US5650380A (en) * 1995-07-11 1997-07-22 Shell Oil Company Lubricating grease

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9914292A1 *

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