EP0719314A1 - Schmiermittelzusammensetzungen enthaltend eine kombination von verschleissschutz-additiven - Google Patents

Schmiermittelzusammensetzungen enthaltend eine kombination von verschleissschutz-additiven

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Publication number
EP0719314A1
EP0719314A1 EP94926291A EP94926291A EP0719314A1 EP 0719314 A1 EP0719314 A1 EP 0719314A1 EP 94926291 A EP94926291 A EP 94926291A EP 94926291 A EP94926291 A EP 94926291A EP 0719314 A1 EP0719314 A1 EP 0719314A1
Authority
EP
European Patent Office
Prior art keywords
lubricant composition
organo
phosphorus
compound
molybdenum
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.)
Granted
Application number
EP94926291A
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English (en)
French (fr)
Other versions
EP0719314B1 (de
Inventor
David Gary Lawton Holt
Patrick Desmond Fraser Vernon
John Ian Atherton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
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Filing date
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 Co filed Critical Exxon Research and Engineering Co
Publication of EP0719314A1 publication Critical patent/EP0719314A1/de
Application granted granted Critical
Publication of EP0719314B1 publication Critical patent/EP0719314B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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

  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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 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.
  • 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.
  • the ashless organo-phosphorus compound is essentially free of metal, and preferably contains sulphur. Phosphorothiolothionates and phosphorothionates and mixtures thereof are preferred compounds
  • 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.
  • 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 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 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.
  • 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
  • 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).

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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)
EP94926291A 1993-09-13 1994-09-09 Schmiermittelzusammensetzungen enthaltend eine kombination von verschleissschutz-additiven Expired - Lifetime EP0719314B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
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
GB9318896 1993-09-13
GB9318895 1993-09-13
PCT/GB1994/001971 WO1995007964A1 (en) 1993-09-13 1994-09-09 Lubricant composition containing antiwear additive combination

Publications (2)

Publication Number Publication Date
EP0719314A1 true EP0719314A1 (de) 1996-07-03
EP0719314B1 EP0719314B1 (de) 1999-01-07

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EP94926291A Expired - Lifetime EP0719314B1 (de) 1993-09-13 1994-09-09 Schmiermittelzusammensetzungen enthaltend eine kombination von verschleissschutz-additiven

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EP (1) EP0719314B1 (de)
JP (1) JPH09506910A (de)
KR (1) KR100237074B1 (de)
AT (1) ATE175438T1 (de)
CA (1) CA2171538C (de)
DE (1) DE69415817T2 (de)
ES (1) ES2128581T3 (de)
HK (1) HK1014024A1 (de)
MY (1) MY116337A (de)
SG (1) SG47398A1 (de)
WO (1) WO1995007964A1 (de)

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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

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DE59813902D1 (de) * 1997-09-18 2007-03-29 Ciba Sc Holding Ag Schmierstoffzusammensetzungen mit Thiophosphorsäureestern und Dithiophosphorsäureestern
US5939364A (en) * 1997-12-12 1999-08-17 Exxon Research & Engineering Co. Lubricating oil containing additive comprising reaction product of molybdenum dithiocarbamate and dihydrocarbyl dithiophosphoric acid
KR20030090891A (ko) * 2002-05-22 2003-12-01 현대자동차주식회사 자동차 기어유 조성물
KR100488860B1 (ko) * 2002-07-25 2005-05-11 현대자동차주식회사 무단변속기유 조성물
US7884059B2 (en) 2004-10-20 2011-02-08 Afton Chemical Corporation Oil-soluble molybdenum derivatives derived from hydroxyethyl-substituted Mannich bases
MX2013005269A (es) 2010-11-19 2013-06-03 Chevron Usa Inc Lubricante para equipo de percusion.
WO2017171020A1 (ja) 2016-03-31 2017-10-05 出光興産株式会社 潤滑油組成物及びそれを使用した精密減速機
WO2017171019A1 (ja) * 2016-03-31 2017-10-05 出光興産株式会社 潤滑油組成物及びそれを使用した精密減速機
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
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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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

Also Published As

Publication number Publication date
KR960705009A (ko) 1996-10-09
SG47398A1 (en) 1998-04-17
CA2171538C (en) 2004-10-26
CA2171538A1 (en) 1995-03-23
EP0719314B1 (de) 1999-01-07
WO1995007964A1 (en) 1995-03-23
ES2128581T3 (es) 1999-05-16
MY116337A (en) 2004-01-31
DE69415817T2 (de) 1999-06-10
JPH09506910A (ja) 1997-07-08
DE69415817D1 (de) 1999-02-18
ATE175438T1 (de) 1999-01-15
HK1014024A1 (en) 1999-09-17
KR100237074B1 (ko) 2000-01-15

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