WO1995007965A1 - Composition lubrifiante contenant une combinaison d'additifs anti-usure - Google Patents

Composition lubrifiante contenant une combinaison d'additifs anti-usure Download PDF

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Publication number
WO1995007965A1
WO1995007965A1 PCT/GB1994/001973 GB9401973W WO9507965A1 WO 1995007965 A1 WO1995007965 A1 WO 1995007965A1 GB 9401973 W GB9401973 W GB 9401973W WO 9507965 A1 WO9507965 A1 WO 9507965A1
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Prior art keywords
lubricant composition
zinc
organo
molybdenum
compounds
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PCT/GB1994/001973
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English (en)
Inventor
David Gary Lawton Holt
Patrick Desmond Fraser Vernon
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Exxon Research And Engineering Company
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Publication of WO1995007965A1 publication Critical patent/WO1995007965A1/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
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
    • 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
    • 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
    • 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
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less 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
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
    • 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
    • C10M2207/125—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
    • C10M2207/126—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 monocarboxylic
    • 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
    • C10M2207/16—Naphthenic 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
    • 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
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/09—Complexes with metals
    • 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
    • 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
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol fueled engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • This invention relates to a lubricant composition containing a combination of additives providing antiwear properties, and to the antiwear additive combination contained therein.
  • ZDDP zinc dialkyldithiophosphate
  • US-A-4178258 describes the use as a lubricating oil additive of molybdenum bis(dialkyldithiocarbamate) to reduce wear in diesel engines caused by the blow-by of soot, when such wear is aggravated by the presence in the oil of ZDDP.
  • US-A-4812246 describes the use in lubricating oils for internal combustion engines of molybdenum dithiocarbamate (MoDTC) or molybdenum dithiophosphate (MoDTP) to aid stability against the effects of NO x gases.
  • the additive package may include ZDDP.
  • EP-A-0113045 describes an antifriction additive combination for small, high power engines comprising a sulphurised oxymetal organophosphorodithionate and/or dithiocarbamate in combination with ZDDP, calcium alkylbenzene (or petroleum) sulphonate and an alkenyl succinic acid imide (or boron derivative).
  • MoDTC decomposes when heated in use to decomposition products which include free amine and carbon disulphide. Both such products are aggressive towards copper which is present in the engine bearings. Wear in bearings is particularly objectionable since repair involves complete dismantling of the engine. Carbon disulphide tends to boil off fairly rapidly and does not constitute a special problem. However even small amounts of free amine can cause damage.
  • synergism described above extends not only to dithiocarbamates of molybdenum but also to molybdenum compounds which are nitrogen free and which therefore do not decompose to free amine.
  • a preferred compound is also free from sulphur.
  • the present invention provides a lubricant composition
  • a lubricant composition comprising a base oil of viscosity from 3 to 26 cSt (mrn- ⁇ /s) at 100°C and an antiwear additive combination comprising (a) an oil soluble or oil dispersible, nitrogen and phosphorus free organo-molybdenum compound or mixture of compounds and (b) a zinc thiophosphate compound or mixture of compounds selected from zinc dialkyldithiophosphate, zinc diaryldithiophosphate, zinc alkylaryldithiophosphate, zinc arylalkyldithiophosphate and mixtures thereof.
  • an antiwear additive combination comprising (a) an organo-molybdenum compound or mixture of compounds as defined above and (b) a zinc thiophosphate compound or mixture of compounds as defined above.
  • the present invention provides the use in a lubricant composition of a combination of additives as an antiwear agent, the combination of additives comprising (a) an organo-molybdenum compound or mixture of compounds as defined above and (b) a zinc thiophosphate compound or mixture of compounds as defined above.
  • the preferred organo-molybdenum compound comprises a carboxylate. Not only do such compounds contain no nitrogen or phosphorus but they are relatively cheap and contain a higher proportion of molybdenum than the more complex compounds. As will be described in more detail, it is believed that the effective additive content is governed by the metal content. Thus only about one third of the amount e.g. of molybdenum 2-ethyl hexanoate need be used by comparison with molybdenum dithiocarbamate.
  • the present invention provides the use in a lubricant composition of one or more molybdenum carboxylate compounds as an antiwear agent.
  • the present invention has the advantage that the organo-molybdenum compound can replace some of the zinc thiophosphate compound used in lubricant compositions with the effect that the phosphorus level in the lubricant is reduced without substantially reducing the antiwear performance of the lubricant or increasing the tendency towards bearing corrosion.
  • the organo-molybdenum compound is preferably selected from a carboxylate and a xanthate and mixtures thereof, the organo groups of which may be substituted with a hydrocarbyl group, with the proviso that the organo group selected results in an organo- molybdenum compound that is oil-soluble or oil-dispersible, preferably oil-soluble.
  • organo group of the organo-molybdenum compound is a carboxylate
  • this is preferably a Ci to C50, more preferably a Cg to CJS, carboxylate group.
  • suitable carboxylates include octanoate, e.g. 2-ethyl hexanoate, naphthenate and stearate. These compounds may be prepared, for example, by reacting molybdenum trioxide with the alkali metal salt of the appropriate carboxylic acid under suitable conditions.
  • the organo group of the organo-molybdenum compound is a xanthate
  • the compound preferably has the formula :
  • R is a Ci to C30 hydrocarbyl group, preferably an alkyl group.
  • the zinc thiophosphate compound (b) has the general formula
  • R5, Rg, R7 and Rg each independently represent a hydrogen atom, a Ci to C20 alkyl group, a Cg to C 2 g cycloalkyl, aryl, alkylaryl or aralkyl group, or a C3 to C 2 Q hydrocarbyl group containing an ester, ether, alcohol or carboxyl group.
  • each of R5 to Rg is a C 2 to Cig, more preferably C3 to Cg, alkyl group which may be straight-chain or branched.
  • Such compounds are commercially available and are supplied by, for example, Exxon Chemical Company.
  • each of the antiwear additives (a) and (b) to be included in the lubricant composition according to the invention are the amounts that are effective in providing the desired level of antiwear performance, whilst reducing the amount of phosphorus to an acceptable level.
  • the antiwear properties of the organo-molybdenum compound (a) are generally attributable to the presence of the molybdenum.
  • the amount of molybdenum contained in the lubricant composition is from 0.001 to 0.5 wt.%, more preferably 0.005 to 0.2 wt.%, and most preferably 0.01 to 0.05 wt.%, based on the total weight of the lubricant composition.
  • the amount of organo- molybdenum compound that this corresponds to depends upon the type of compound selected.
  • the amount of compound used depends upon the molecular weight of the carboxylate group selected.
  • the amount of molybdenum carboxylate used is preferably from 0.005 to 2.5 wt.%, more preferably from 0.025 to 1.0 wt.%, and most preferably from 0.05 to 0.25 wt.%, based on the total weight of the lubricant composition.
  • the amount of compound used depends upon the molecular weight of the hydrocarbyl, e.g. alkyl, groups contained in the xanthate groups. Typically, however, the amount of molybdenum xanthate used is preferably from 0.003 to 2.0 wt.%, more preferably from 0.01 to 0.7 wt.% and most preferably from 0.03 to
  • the antiwear properties of the zinc thiophosphate compound (b) are generally attributable to the presence of the phosphorus.
  • the amount of zinc thiophosphate to incorporate one first needs to determine the desired amount of phosphorus in the lubricant composition due to the zinc thiophosphate compound.
  • this amount is from 0.001 to 0.3 wt.%, more preferably from 0.01 to 0.2 wt.%, and most preferably from 0.02 to 0.1 wt.%, based on the total weight of the lubricant composition.
  • the amount of zinc thiophosphate compound incorporated into the lubricant composition is preferably from 0.01 to 3.0 wt.%, more preferably from 0.1 to 2.0 wt.%, and most preferably from 0.2 to 1.0 wt.%, based on the total weight of the lubricant composition.
  • the ratio of organo-molybdenum compound (a) to zinc thiophosphate compound (b) is preferably such that the weight ratio of molybdenum to phosphorus in the lubricant composition, due to the presence of compounds (a) and (b), is from 1:50 to 100:1, more preferably from 1:10 to 20: 1, and most preferably from 1:1 to 10:1.
  • the molybdenum replaces at least 50% by weight of the phosphorus that would otherwise be contained in the lubricant composition if the sole antiwear additive were ZDDP.
  • the base oil employed in the lubricant composition according to the invention may be any base oil of viscosity suitable for use of the lubricant in an engine e.g. as a crankcase oil or gear oil.
  • the base oil may be, for example, a conventionally refined mineral oil, an oil derived from coal tar or shale, a vegetable oil, an animal oil, a hydrocracked oil, a hydroisomerised oil, or a synthetic oil, or a mixture of two or more of these types of oils.
  • synthetic oils include polyalphaolefins, polybutene, alkylbenzenes, polyglycols, esters such as polyol esters or dibasic carboxylic acid esters, alkylene oxide polymers, and silicone oils.
  • the viscosity of the base oil depends upon the intended use, but generally is in the range of from 3 to 26 cSt (mm 2 /s) at 100°C, preferably from 3 to 20 cSt (mm 2 /s) at 100°C.
  • the antiwear additive compounds (a) and (b) may be mixed directly with the base oil, but, for ease of handling and introduction of the compounds to the base oil, are preferably in the form of additive concentrate comprising the additive compound, or mixture of both compounds, contained in a carrier fluid.
  • an additive concentrate comprising (a) an organo-molybdenum compound as defined above, (b) a zinc thiophosphate compound as defined above, and (c) a carrier fluid.
  • the carrier fluid is typically an oil and may be, for example, any of the oils mentioned above in the description of the base oil. Alternatively, it may be an organic solvent, for example naphtha, benzene, toluene, xylene and the like.
  • the carrier fluid should be compatible with the base oil of the lubricant composition, but otherwise is preferably inert.
  • the concentrate will comprise from 10 to 90 wt.% of - the additive(s), preferably from 30 to 70 wt.%, the balance being the carrier fluid.
  • the lubricant composition according to the invention may also contain other additives, which may be added directly to the base oil, as a separate additive concentrate, or included in the concentrate of the antiwear additives.
  • other additives that may be incorporated include one or more of a detergent, dispersant, antioxidant, corrosion inhibitor, extreme pressure agent, antifoaming agent, pour point depressant and viscosity index improver.
  • a detergent dispersant
  • antioxidant corrosion inhibitor
  • extreme pressure agent antifoaming agent
  • pour point depressant pour point depressant and viscosity index improver.
  • Such additives are well-known and the selection of appropriate additives could readily be determined by a person skilled in the art of lubricant formulating.
  • the lubricant composition may find use in any application where the parts to be lubricated are subject to wear. It is especially suitable for use as an engine oil (i.e. crankcase oil) for internal combustion engines.
  • engine oil i.e. crankcase oil
  • a number of engine oils were formulated as listed below using as a basecase oil a conventional engine oil formulation based on a conventionally refined mineral oil and containing standard engine oil additives except that zinc dialkyldithiophosphate (ZDDP) was omitted.
  • the engine oil had a viscosity of 14 cSt at 100°C.
  • the ZDDP used was PARANOX 14 (trade name) supplied by Exxon Chemical Company Ltd.
  • a treat level of 1.0 wt.% of this ZDDP provides 0.08 wt.% phosphorus measured using X-ray fluorescent analysis, standard test AMS 86.002.
  • the organo-molybdenum compound used in the comparative examples was MOLYVA 822 (trade name), a sulphurised oxy-molybdenum dithiocarbamate C'MoDTC") supplied by R.T. Vanderbilt Company Ltd.
  • a treat level of 1.0 wt.% of this MoDTC provides 0.05 wt.% molybdenum measured using ICP (inductively-coupled plasma) analysis.
  • Engine Oil 1A Basecase Oil containing no ZDDP and no MoDTC
  • An engine oil was formulated using the same basecase engine oil as in Example 1 and containing 0.63 wt.% of the ZDDP compound PARANOX 14, and 0.07 wt.% of MOLYHEXCEM (trade name), molybdenum 2-ethyl hexanoate available from Mooney Chemicals, which provides 0.01 wt.% molybdenum measured using IPC analysis.
  • Engine Oil 2 The resulting engine oil, labelled Engine Oil 2, was tested for valve train wear as described in Example 1, and the results are given in Table 1 below.

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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)

Abstract

L'invention concerne une composition lubrifiante comprenant une huile de base présentant une viscosité de 3 à 26 cSt (mm2/s) à 100 °C et une combinaison anti-usure comprenant: (a) un ou plusieurs composés organo-molybdiques solubles ou dispersibles dans l'huile, exempts d'azote et de phosphore, par exemple un xanthate ou un carboxylate et (b) un thiophosphate de zinc ou un mélange de thiophosphates de zinc choisis parmi le dialkyldithiophosphate de zinc, le diaryldithiophosphate de zinc, l'alkylaryldithiophosphate de zinc et l'arylalkyldithiophosphate de zinc.
PCT/GB1994/001973 1993-09-13 1994-09-09 Composition lubrifiante contenant une combinaison d'additifs anti-usure WO1995007965A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB939318923A GB9318923D0 (en) 1993-09-13 1993-09-13 Lubricant composition containing antiwear additive combination
GB9318923.1 1993-09-13

Publications (1)

Publication Number Publication Date
WO1995007965A1 true WO1995007965A1 (fr) 1995-03-23

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PCT/GB1994/001973 WO1995007965A1 (fr) 1993-09-13 1994-09-09 Composition lubrifiante contenant une combinaison d'additifs anti-usure

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GB (1) GB9318923D0 (fr)
WO (1) WO1995007965A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0825247A2 (fr) * 1996-08-21 1998-02-25 The Lubrizol Corporation Compositions contenant des thiocarbonates et des composés d'azote acylés
DE112011103822T5 (de) 2010-11-19 2013-08-22 Chevron U.S.A. Inc. Schmiermittel für Schlagwerkausrüstung

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4239633A (en) * 1979-06-04 1980-12-16 Exxon Research & Engineering Co. Molybdenum complexes of ashless polyol ester dispersants as friction-reducing antiwear additives for lubricating oils
US4383931A (en) * 1981-12-02 1983-05-17 Gulf Research & Development Company Lubricating oils containing molybdenyl chelates
EP0323151A1 (fr) * 1987-12-28 1989-07-05 Exxon Research And Engineering Company Huiles lubrifiantes
US4966719A (en) * 1990-03-12 1990-10-30 Exxon Research & Engineering Company Multifunctional molybdenum and sulfur containing lube additives
US4990271A (en) * 1989-09-07 1991-02-05 Exxon Research And Engineering Company Antiwear, antioxidant and friction reducing additive for lubricating oils
EP0416909A1 (fr) * 1989-09-07 1991-03-13 Exxon Research And Engineering Company Composition d'huile lubrifiante
JPH05186789A (ja) * 1992-01-09 1993-07-27 Tonen Corp 潤滑油組成物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4239633A (en) * 1979-06-04 1980-12-16 Exxon Research & Engineering Co. Molybdenum complexes of ashless polyol ester dispersants as friction-reducing antiwear additives for lubricating oils
US4383931A (en) * 1981-12-02 1983-05-17 Gulf Research & Development Company Lubricating oils containing molybdenyl chelates
EP0323151A1 (fr) * 1987-12-28 1989-07-05 Exxon Research And Engineering Company Huiles lubrifiantes
US4990271A (en) * 1989-09-07 1991-02-05 Exxon Research And Engineering Company Antiwear, antioxidant and friction reducing additive for lubricating oils
EP0416909A1 (fr) * 1989-09-07 1991-03-13 Exxon Research And Engineering Company Composition d'huile lubrifiante
US4966719A (en) * 1990-03-12 1990-10-30 Exxon Research & Engineering Company Multifunctional molybdenum and sulfur containing lube additives
JPH05186789A (ja) * 1992-01-09 1993-07-27 Tonen Corp 潤滑油組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 9334, Derwent World Patents Index; AN 93-270010 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0825247A2 (fr) * 1996-08-21 1998-02-25 The Lubrizol Corporation Compositions contenant des thiocarbonates et des composés d'azote acylés
EP0825247A3 (fr) * 1996-08-21 1998-04-22 The Lubrizol Corporation Compositions contenant des thiocarbonates et des composés d'azote acylés
DE112011103822T5 (de) 2010-11-19 2013-08-22 Chevron U.S.A. Inc. Schmiermittel für Schlagwerkausrüstung

Also Published As

Publication number Publication date
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