WO1995007964A1 - 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
WO1995007964A1
WO1995007964A1 PCT/GB1994/001971 GB9401971W WO9507964A1 WO 1995007964 A1 WO1995007964 A1 WO 1995007964A1 GB 9401971 W GB9401971 W GB 9401971W WO 9507964 A1 WO9507964 A1 WO 9507964A1
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Prior art keywords
lubricant composition
organo
phosphorus
compound
molybdenum
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PCT/GB1994/001971
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English (en)
Inventor
David Gary Lawton Holt
Patrick Desmond Fraser Vernon
John Ian Atherton
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Exxon Research And Engineering Company
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Publication date
Priority claimed from GB939318896A external-priority patent/GB9318896D0/en
Priority claimed from GB939318895A external-priority patent/GB9318895D0/en
Application filed by Exxon Research And Engineering Company filed Critical Exxon Research And Engineering Company
Priority to DE69415817T priority Critical patent/DE69415817T2/de
Priority to JP7509040A priority patent/JPH09506910A/ja
Priority to EP94926291A priority patent/EP0719314B1/fr
Priority to CA002171538A priority patent/CA2171538C/fr
Priority to KR1019960701290A priority patent/KR100237074B1/ko
Publication of WO1995007964A1 publication Critical patent/WO1995007964A1/fr
Priority to US08/990,052 priority patent/US6187723B1/en
Priority to HK98115423A priority patent/HK1014024A1/xx

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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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • 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
    • 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
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/18—Complexes with metals
    • 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
    • C10M2207/09—Metal enolates, i.e. keto-enol metal complexes
    • 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
    • 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
    • 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
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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
    • 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
    • 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.
  • an antiwear additive in lubricating oils such as engine oils. Wear results mainly from the rubbing together of two metal surfaces, i.e. in boundary lubrication regimes, such as is found in valve trains in internal combustion engines. It is believed that the antiwear additive acts to provide a protective film over the metal surfaces.
  • One well-known class of antiwear additives is the metal alkylphosphate, especially zinc dialkyldithiophosphate ("ZDDP").
  • ZDDP is employed at treat levels of 1 to 2 wt.% based on the total weight of the lubricant, which gives a phosphorus level in the lubricant typically in the range of from 0.05 to 0.15 wt.%, and a zinc level of from 0.1 to 0.2 wt.
  • Sulphur-containing organic phosphorus compounds are known to be used as "extreme pressure compounds" in heavy duty applications such as greases for constant velocity joints. It is also known to use sulphur-containing organic compounds of heavy metals such as molybdenum, tungsten and lead in such applications.
  • GB-A-2255346 describes an additive for grease used in constant velocity joints comprising in combination molybdenum sulphide dialkyldithiocarbamate, zinc dithiophosphate, a sulphur-phosphorus series extreme pressure
  • US-A-4648985 describes a lead-free extreme pressure additive, generally for lubricants based on asphalt, utilising an organic phosphate in combination with copper or molybdenum compounds selected from carboxylate, phosphate, thiophosphate and thiocarbamate, optionally with a metal-free thiocarbamate or in combination with a metal thiocarbamate (numerous metals being described).
  • the preferred metals are copper and zinc.
  • 0516461 describes a dispersant additive for lubricating oils showing improved compatibility with elastomeric seal material which comprises in combination a metal dihydrocarbyl dithiocarbamate or dithiocarbamate and a phosphorylated ashless dispersant.
  • Various metal compounds are described including molybdenum dithiophosphate.
  • EP-A-0316610 describes a multipurpose antiwear, antiseizure and corrosion inhibiting additive for lubricating oils utilising a combination of an organo-phosphorus compound selected from various phosphines and phosphites and an organo-molybdenum compound selected from oxysulphide alkylphosphorodithioates and oxysulphide alkyl dithiocarbamates.
  • GB-A- 1373588 describes an antiwear, antioxidant additive combination comprising a metal dialkyldithiocarbamate and/or a metal alkyl, aryl or aralkyl dithiophosphate and a metal- free phosphorus compound selected from sulphurised sperm oil esterified with dithiophosphate, sulphurised terpene esterified with dithiophosphate, sulphurised and phosphated sperm oil and phosphorus polysulphide. Many metals are mentioned including molybdenum, zinc and lead.
  • the present invention provides a lubricant composition
  • a lubricant composition comprising a base oil of viscosity from 3 to 26 cSt (mra ⁇ /s) at 100°C and an antiwear additive combination comprising (a) an oil soluble or oil dispersible phosphorus-free organo-molybdenum compound and (b) an ashless sulphur-containing organo-phosphorus compound.
  • compounds (a), (b) when used in combination with reduced levels of a selected zinc thiophosphate act synergisticaUy to provide better wear protection than that achieved using a comparable amount (i.e. an amount providing a similar total level of phosphorus) of the zinc thiophosphate alone.
  • the combination includes, in addition to (a) and (b), a zinc thiophosphate compound (c) selected from one or more of zinc dialkyldithiophosphate, zinc diaryldithiophosphate, zinc alkylaryldithiophosphate and zinc arylalkyldithiophosphate.
  • a zinc thiophosphate compound (c) selected from one or more of zinc dialkyldithiophosphate, zinc diaryldithiophosphate, zinc alkylaryldithiophosphate and zinc arylalkyldithiophosphate.
  • 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, indeed increasing the antiwear performance of the lubricant.
  • the organo-molybdenum compound may comprise a molybdenum carbamate, preferably a dicarbamate and more preferably a dithiocarbamate (MoDTC) the organo group(s) of which may be substituted with a hydrocarbyl groups and or one or more hetero atoms, with the proviso that the organo group selected results in an organo-molybdenum compound that is oil-soluble or oil-dispersible, preferably oil-soluble.
  • MoDTC dithiocarbamate
  • 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.
  • synergisms described above extend not only to carbamates of molybdenum but also to molybdenum compounds which are nitrogen free and which therefore do not decompose to free amine.
  • a preferred organo-molybdenum compound is also free from sulphur.
  • the organo-molybdenum compound is nitrogen-free. It is preferably selected from a carboxylate and a xanthate or mixtures thereof the organo group(s) of which may be substituted with a hydrocarbyl group, again with the proviso that the organo group selected results in an organo- molybdenum compound that is oil-soluble or oil-dispersible, preferably oil-soluble.
  • 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 an antiwear agent comprising a combination of (a) an organo-molybdenum compound as above described, (b) an ashless organo- phosphorus compound as above described and, optionally, (c) a zinc thiophosphate as above described.
  • the present invention provides the use in a lubricant composition of the combination of (a) an organo-molybdenum compound as above described, (b) an ashless organo-phosphorus compound as above described and, optionally, (c) a zinc thiophosphate as above described, as an antiwear agent.
  • the invention provides an additive concentrate comprising in combination: (a) an organo-molybdenum compound as above described, (b) an ashless organo- phosphorus compound as above described, optionally (c) a zinc thiophosphate as above described and a carrier fluid.
  • the organo-molybdenum compound is preferably a molybdenum dithiocarbamate of the formula :
  • R j , R 2 , R3 and R4 each independently represent a hydrogen atom, a C j to C20 alkyl group, a Cg to C 2 Q cycloalkyl, aryl, alkylaryl or aralkyl group, or a C3 to C 2 n hydrocarbyl group containing an ester, ether, alcohol or carboxyl group; and X j X 2 , Y j and Y each independently represent a sulphur or oxygen atom.
  • Rj, R 2 , R3 and R4 examples include 2-ethylhexyl, nonylphenyl, methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, n-hexyl, n-octyl, nonyl, decyl, dodecyl, tridecyl, lauryl, oleyl, linoleyl, cyclohexyl and phenylmethyl.
  • R j to R4 are each Cg to C j ⁇ alkyl groups, more preferably CJQ to C14.
  • X j and X 2 are the same, and Y j and Y 2 are the same. Most preferably X j and X 2 are both sulphur atoms, and Yj and Y are both oxygen atoms.
  • the organo-molybdenum compound is sulphurised oxymolybdenum dithiocarbamate wherein the thiocarbamate groups contain CJQ to C24 alkyl groups.
  • Such compounds are commercially available and are supplied, for example, by R.T. Vanderbilt Company.
  • organo group of the organo-molybdenum compound is a carboxylate
  • this is preferably a C j to C50, more preferably a Cg to Cjg, carboxylate group.
  • suitable carboxylates include octoate, 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 Cj to C30 hydrocarbyl group, preferably an alkyl group.
  • R is a Cj to C30 hydrocarbyl group, preferably an alkyl group.
  • the ashless organo-phosphorus compound is essentially free of metal, and preferably contains sulphur. Phosphorothiolothionates and phosphorothionates and mixtures thereof are preferred compounds
  • Phosphorothiolothionates have the general formula: S
  • R5, Rg and R ⁇ each independently represent a hydrocarbyl group which may be substituted with one or more functional groups or hetero atoms, or may be unsubstituted, and which may be branched or straight-chain.
  • R5 and Rg are each a Cj to C30 alkyl group, or a Cg to C30 cycloalkyl, aryl, aralkyl or alkylaryl group.
  • R7 is preferably a Cj to C30 alkyl group, a Cg to C30 cycloalkyl, aryl, aralkyl or alkylaryl group, or a C j to C30 hydrocarbyl group containing one or more carboxylic acid, ester, alcohol, ether or amine groups, or an ammonium ion, preferably one or more carboxylic acid groups.
  • Suitable phosphorothiolothionates which are commercially available include VANLUBE 727, VANLUBE 7611 both supplied by R.T. Vanderbilt Company, IRGALUBE 63 supplied by Ciba-Geigy, and ECA 6330 supplied by Exxon Chemical Company.
  • Phosphorothionates have the general formula:
  • Rg, Rg, and RJQ each represent a hydrocarbyl group which may be substituted with one or more functional groups or hetero atoms, or may be unsubstituted, and which may be branched or straight-chain.
  • Rg and Rg are each a C j to C30 alkyl group or a Cg to C30 cycloalkyl, aryl, aralkyl or alkylaryl group.
  • RJQ is preferably a Cj to C30 alkyl group or a Cg to C30 cycloalkyl, aryl, aralkyl or alkylaryl group, or a C j to C30 hydrocarbyl group containing one or more amine, carboxylic acid, ester, alcohol or ether groups, or an ammonium ion, preferably an amine group or ammonium ion.
  • Suitable phosphorothionates which are commercially available include IRGALUBE TPPT supplied by Ciba-Geigy. Phosphorus thionates may also be obtained from the reaction of amines with dialkyldithiophosphoric acids.
  • the zinc thiophosphate compound (c) has the general formula :
  • RJ J, Rj 2 , R13 and R14 each independently represent a hydrogen atom, a C j to C 2 o alkyl group, a Cg to C 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 RJJ to R14 is a C 2 to Cjg, 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 on the molecular weight of the R groups contained in the thiocarbamate groups, as defined in formula (I) above. Typically, however, the amount of molybdenum dithiocarbamate used is preferably from 0.01 to 3.0 wt.%, more preferably from 0.02 to 2.0 wt.%, and most preferably from 0.05 to 1.0 wt.%, based on the total weight of the lubricant composition.
  • 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 0.2 wt.%, based on the total weight of the lubricant composition.
  • the antiwear properties of the ashless organo-phosphorus compound (b) and the zinc thiophosphate, when used, are generally attributable to the presence of the phosphorus.
  • the total amount of phosphorus contained in the lubricant composition 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 ashless organo-phosphorus compound and zinc thiophosphate compound (when used) that this corresponds to depends on the relative proportions of these compounds and the molecular weights of the particular compounds selected.
  • the amount of ashless organo-phosphorus 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 amount of zinc thiophosphate compound is preferably from 0.01 to 3.0 wt, more preferably 0.1 to 2.0 wt.%, and most preferably 0.2 to 1.0 wt.% based on the total weight of the lubricant composition.
  • the ratio of organo-molybdenum compound (a) to ashless organo-phosphorus 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 weight ratio of phosphorus derived from the ashless organo-phosphorus compound (b) to zinc thiophosphate compound (c) (when used) is preferably from 10:1 to 1:20, more preferably from 5:1 to 1:15 and most preferably 1:1 to 1:10.
  • the base oil employed in the lubricant composition according to the invention may be any base oil having a 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, or a synthetic oil, or a mixture of two or more of these types of oils.
  • synthetic oils include hydroisomerised paraffins, 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), and (c) when used, 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.
  • 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 for internal combustion engines.
  • a number of engine oils were formulated by blending an organo-molybdenum compound and an ashless organo-phosphorus compound with a conventional engine oil formulation (the "basecase” oil) which was based on a conventionally refined mineral oil and contained standard engine oil additives except that ZDDP was omitted.
  • basecase oil a conventional engine oil formulation
  • further engine oils were formulated omitting one or more of the antiwear additives, and, in one example, ZDDP was added.
  • the organo-molybdenum compounds used were: (i) MOLYVAN 822 (trade name) a molybdenum dithiocarbamate supplied by R.T. Vanderbilt Company, (ii) MOLYNAPALL (trade name), a molybdenum naphthenate supplied by Mooney Chemicals, and (iii) MOLYHEXCEM (trade name), molybdenum 2-ethyl hexanoate supplied by Mooney Chemicals.
  • the molybdenum content of each of these compounds was determined using ICP (inductively-coupled plasma) analysis.
  • the ashless organo-phosphorus compounds used were: (i) IRGALUBE TPPT (trade name), a phosphorothionate supplied by Ciba-Geigy, (ii) VANLUBE 727 (trade name), a phosphorothiolothionate supplied by R.T. Vanderbilt Company, and (iii) "Amine DDP", an amine derivative of a phosphorothionate obtained by reacting the amine PRIMENE JMT (trade name) supplied by Rohm and Haas with dioctyldithiophosphoric acid.
  • the phosphorus content of each of these compounds was determined using X-ray fluorescent analysis according to standard test AMS 86.002.
  • the ZDDP compound used was PARANOX 14 supplied by Exxon Chemical Company.
  • the phosphorus content of this compound was also determined using the above X-ray fluorescent analysis technique.
  • the resulting engine oils were tested for valve train wear by measuring camshaft wear and tappet scuffing using a motored cylinder head test rig which is equivalent to the industry standard TU-3 engine test CEC L-38-T-87, which test procedure is available from the CEC Secretariat, 61 New Cavendish Street, London Wl 8AB.
  • PN 14 PARANOX 14
  • MV 822 MOLYVAN 822
  • I.TPPT IRGALUBE TPPT
  • VL 727 VANLUBE 727
  • Example Invention/ Basecase ZDDP Organo- Organo-P % Mo % P % Total Camshaft Tappet Comparison Oil Mo Active Wear ( ⁇ m) Scuffing
  • An engine oil was formulated by adding the following antiwear additives to a basecase oil consisting of conventional engine oil based on a conventionally refined mineral oil and containing standard engine oil additives other than ZDDP:
  • the amount of molybdenum contained in (a) was determined using ICP (inductively- coupled plasma) analysis.
  • the amount of phosphorus contained in each of (b) and (c) was determined using X-ray fluorescent analysis according to standard test AMS 86.002.
  • Comparative engine oils were formulated using the same basecase oil and omitting one or more of the above antiwear additives (a), (b) and (c).
  • the resulting engine oils were tested for valve train wear by measuring tappet wear according to the standard industry engine test VW 5106 Cam and Tappet Rig.

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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

On décrit une composition lubrifiante, en particulier pour les huiles à moteurs, comprenant une huile de base ayant une viscosité de 3 - 26 cSt (mm2/s) à 100 °C et une combinaison d'additifs anti-usure comprenant (a) un composé organo-molybdique exempt de phosphore, dispersible ou soluble dans l'huile, (b) un composé organo-phosphoré sans cendres contenant du soufre et éventuellement (c) un ou plusieurs thiophosphates de zinc choisis parmi le dialkyldithiophosphate de zinc, le diaryldithiophosphate de zinc, les alkylaryldithiophosphate de zinc et l'arylalkyldithiophosphate de zinc. Le composé molybdique peut être un carbamate, par exemple un dithiocarbamate de molybdène (MoDTC), mais il est de préférence exempt d'azote, et peut être, par exemple, un carboxylate.
PCT/GB1994/001971 1993-09-13 1994-09-09 Composition lubrifiante contenant une combinaison d'additifs anti-usure WO1995007964A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
DE69415817T DE69415817T2 (de) 1993-09-13 1994-09-09 Schmiermittelzusammensetzungen enthaltend eine kombination von verschleissschutz-additiven
JP7509040A JPH09506910A (ja) 1993-09-13 1994-09-09 摩耗防止用添加剤組合せ物を含有する潤滑剤組成物
EP94926291A EP0719314B1 (fr) 1993-09-13 1994-09-09 Composition lubrifiante contenant une combinaison d'additifs anti-usure
CA002171538A CA2171538C (fr) 1993-09-13 1994-09-09 Composition lubrifiante contenant une combinaison d'additifs contre l'usure
KR1019960701290A KR100237074B1 (ko) 1993-09-13 1994-09-09 내마모 첨가제 조합을 포함하는 윤활유 조성물
US08/990,052 US6187723B1 (en) 1993-09-13 1997-12-12 Lubricant composition containing antiwear additive combination
HK98115423A HK1014024A1 (en) 1993-09-13 1998-12-24 Lubricant composition containing antiwear additive combination

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9318896.9 1993-09-13
GB9318895.1 1993-09-13
GB939318896A GB9318896D0 (en) 1993-09-13 1993-09-13 Lubricant composition containing antiwear additive combination
GB939318895A GB9318895D0 (en) 1993-09-13 1993-09-13 Lubricant composition containing antiwear additive combination

Publications (1)

Publication Number Publication Date
WO1995007964A1 true WO1995007964A1 (fr) 1995-03-23

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JP (1) JPH09506910A (fr)
KR (1) KR100237074B1 (fr)
AT (1) ATE175438T1 (fr)
CA (1) CA2171538C (fr)
DE (1) DE69415817T2 (fr)
ES (1) ES2128581T3 (fr)
HK (1) HK1014024A1 (fr)
MY (1) MY116337A (fr)
SG (1) SG47398A1 (fr)
WO (1) WO1995007964A1 (fr)

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WO1999031205A1 (fr) * 1997-12-12 1999-06-24 Infineum Usa L.P. Huile lubrifiante contenant un additif renfermant le produit de reaction de dithiocarbamate de molybdene et d'acide dihydrocarbyle dithiophosphorique
KR100538777B1 (ko) * 1997-09-18 2006-04-28 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 티오인산에스테르및디티오인산에스테르를포함하는개선된윤활제조성물 및 농축물
US7884059B2 (en) 2004-10-20 2011-02-08 Afton Chemical Corporation Oil-soluble molybdenum derivatives derived from hydroxyethyl-substituted Mannich bases
EP3438232A4 (fr) * 2016-03-31 2019-11-27 Idemitsu Kosan Co., Ltd. Composition d'huile lubrifiante et réducteur de précision l'utilisant
US10800991B2 (en) 2016-03-31 2020-10-13 Idemitsu Kosan Co., Ltd. Lubricating oil composition, and precision reduction gear using same
CN116515549A (zh) * 2023-04-28 2023-08-01 安徽金德润滑科技有限公司 一种长寿命风电齿轮油及其制备方法

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KR20030090891A (ko) * 2002-05-22 2003-12-01 현대자동차주식회사 자동차 기어유 조성물
KR100488860B1 (ko) * 2002-07-25 2005-05-11 현대자동차주식회사 무단변속기유 조성물
CN101007977B (zh) * 2006-01-27 2011-12-21 广东高奇能源工程有限公司 用于机动车发动机的油路纳米护理剂
BR112013010721B1 (pt) 2010-11-19 2018-11-27 Chevron U.S.A. Inc. lubrificante para equipamento de percussão
CN109652171B (zh) * 2017-10-12 2021-12-14 中国石油化工股份有限公司 一种工业机器人关节rv减速机专用油组合物

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100538777B1 (ko) * 1997-09-18 2006-04-28 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 티오인산에스테르및디티오인산에스테르를포함하는개선된윤활제조성물 및 농축물
WO1999031205A1 (fr) * 1997-12-12 1999-06-24 Infineum Usa L.P. Huile lubrifiante contenant un additif renfermant le produit de reaction de dithiocarbamate de molybdene et d'acide dihydrocarbyle dithiophosphorique
US7884059B2 (en) 2004-10-20 2011-02-08 Afton Chemical Corporation Oil-soluble molybdenum derivatives derived from hydroxyethyl-substituted Mannich bases
US7960321B2 (en) 2004-10-20 2011-06-14 Afton Chemical Corporation Oil-soluble molybdenum derivatives derived from hydroxyethyl-substituted Mannich bases
EP3438232A4 (fr) * 2016-03-31 2019-11-27 Idemitsu Kosan Co., Ltd. Composition d'huile lubrifiante et réducteur de précision l'utilisant
US10647940B2 (en) 2016-03-31 2020-05-12 Idemitsu Kosan Co., Ltd. Lubricating oil composition, and precision reduction gear using same
US10800991B2 (en) 2016-03-31 2020-10-13 Idemitsu Kosan Co., Ltd. Lubricating oil composition, and precision reduction gear using same
CN116515549A (zh) * 2023-04-28 2023-08-01 安徽金德润滑科技有限公司 一种长寿命风电齿轮油及其制备方法

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MY116337A (en) 2004-01-31
SG47398A1 (en) 1998-04-17
KR960705009A (ko) 1996-10-09
JPH09506910A (ja) 1997-07-08
ES2128581T3 (es) 1999-05-16
KR100237074B1 (ko) 2000-01-15
EP0719314B1 (fr) 1999-01-07
CA2171538C (fr) 2004-10-26
EP0719314A1 (fr) 1996-07-03
ATE175438T1 (de) 1999-01-15
DE69415817D1 (de) 1999-02-18
CA2171538A1 (fr) 1995-03-23
DE69415817T2 (de) 1999-06-10
HK1014024A1 (en) 1999-09-17

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