EP1265975A1 - Lubricating oil compositions comprising a trinuclear compound antioxidant - Google Patents
Lubricating oil compositions comprising a trinuclear compound antioxidantInfo
- Publication number
- EP1265975A1 EP1265975A1 EP01920801A EP01920801A EP1265975A1 EP 1265975 A1 EP1265975 A1 EP 1265975A1 EP 01920801 A EP01920801 A EP 01920801A EP 01920801 A EP01920801 A EP 01920801A EP 1265975 A1 EP1265975 A1 EP 1265975A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- compound
- composition
- composition according
- basestock
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 150000001875 compounds Chemical class 0.000 title claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 10
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 9
- 239000003446 ligand Substances 0.000 claims abstract description 20
- 239000003921 oil Substances 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005864 Sulphur Substances 0.000 claims abstract description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 11
- 239000005078 molybdenum compound Substances 0.000 claims description 10
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000012990 dithiocarbamate Substances 0.000 claims description 2
- 150000004659 dithiocarbamates Chemical class 0.000 claims description 2
- 238000009877 rendering Methods 0.000 claims description 2
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- 239000002199 base oil Substances 0.000 description 10
- 239000002270 dispersing agent Substances 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- -1 nitroso, sulphoxy Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C10M123/00—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential
- C10M123/04—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential at least one of them being a macromolecular compound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- 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
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
-
- 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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/042—Mixtures of base-materials and additives the additives being compounds of unknown or incompletely defined constitution only
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/104—Aromatic fractions
- C10M2203/1045—Aromatic fractions used as base material
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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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/106—Naphthenic fractions
- C10M2203/1065—Naphthenic fractions used as base material
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/108—Residual fractions, e.g. bright stocks
- C10M2203/1085—Residual fractions, e.g. bright stocks used as base material
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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
- 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
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/10—Amides of carbonic or haloformic acids
- C10M2215/102—Ureas; Semicarbazides; Allophanates
- C10M2215/1026—Ureas; Semicarbazides; Allophanates used as thickening material
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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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/045—Polyureas; Polyurethanes
- C10M2217/0456—Polyureas; Polyurethanes used as thickening agents
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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
- 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
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- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/019—Shear stability
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- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
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- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/68—Shear stability
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- 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
Definitions
- This invention relates to lubricating oil compositions, especially lubricants used in internal combustion engines, comprising Group I base oils which are relatively low in saturates but high in sulphur with natural oxidation stability.
- Lubricating oil compositions are used for the smooth operation of internal combustion engines, power transmission components including automatic transmissions, shock absorbers and power steering devices and gears.
- the engine oils for internal combustion engines in particular serve to (i) lubricate various sliding interfaces eg between the piston ring and cylinder liner, in bearings of the crank shaft and the connecting rod, and in the valve driving mechanism including cams and valve lifters, (ii) cool the engine, (iii) clean and disperse the combustion products and (iv) prevent corrosion and consequent rust formation.
- the stringent requirements for high performance engines in recent years have meant greater demand from lubricants used in such engines.
- Lubricating oils used in such engines usually deteriorate due to oxidation by oxygen and/or nitrogen oxides (NOx) contained in the blow-by gas (ie gas leaking from the combustion chamaber gases into the crankcase at the piston/cylinder interface).
- NOx nitrogen oxides
- the concentration of NOx increases in the blow- by gas with increasing demand in performance of the engine.
- the deleterious effects of oxidation can be and have been mitigated by the use of various additives including antioxidants and by the use of base stocks which are relatively more stable to oxidation.
- lubricating compositions which comprise a Group II, III or IV basestocks which are relatively high in saturated hydrocarbons (hereafter "saturates") in preference to Group I basestocks which are relatively low in saturates because of the relatively high propensity of Group I base oils to oxidation.
- Group II, III and IV basestocks are typically more expensive than the conventional Group I basestocks.
- a feature of the present invention is the improvement of the oxidative stability of Group I basestocks.
- the present invention is a lubricating oil composition
- a lubricating oil composition comprising a major amount of a Group I base stock and an antioxidant comprising an oil soluble trinuclear organomolybdenum compound of the generic formula: Mo 3 S x -(Q) (I) wherein x is from 4 to 10, preferably 7, and Q is a core group, which may be a ligand.
- the lubricating oil compositions of the present invention are those that comprise a major amount of a Group I basestock as defined in API 1509.
- the Group I basestock may be mineral oils or blends thereof having a KNioo of 2-50 cSt, a viscosity index of 80-120, a saturates content of ⁇ 90% w/w, an aromatics content of > 10% w/w and a sulphur content of > 0.03% w/w (300 ppm).
- Group I basestocks are produced by solvent extration followed by dewaxing.
- Group I basestock include inter alia solvent neutral basestocks such as MCT 30 ( 94 VI, 78% w/w saturates, 0.28% w/w sulphur); while hydrocracked distillates and raffinates which have been dewaxed, eg by conventional or catalytic dewaxing techniques, represent Group II and Group III base stocks with a sulphur content of less than 0.03% w/w and an aromatics content of ⁇ 10% w/w such as RLOP 500R (106 VI, >97% w/w saturates, and Mobil Jurong 500 ⁇ (99VI, >97% w/w saturates). Polyalphaolefins represent Group IV basestocks.
- solvent neutral basestocks such as MCT 30 ( 94 VI, 78% w/w saturates, 0.28% w/w sulphur)
- hydrocracked distillates and raffinates which have been dewaxed eg by conventional or catalytic dewa
- the present invention is a method of improving the oxidative stability of a lubricant composition, said composition comprising a Group I base stock which has a kinematic viscosity at 100°C (KV 100 ) from about 2 cSt to 50 cSt (2 x 10 "6 to 50 x 10 "6 m 2 /sec), a saturates content of at less than 90% w/w, an aromatics content of > 10% w/w and a sulphur content of > 0.03% w/w (300 ppm) said method comprising adding to the basestock an effective amount of an antioxidant comprising an oil soluble trinuclear organomolybdenum compound of the generic formula:
- the trinuclear molybdenum compounds are of formula (I) Mo 3 S x -(Q) (I) wherein x is from 4 to 10, preferably 7, and Q is a core group, which may be a ligand.
- the trinuclear molybdenum compounds are of formula (I) Mo 3 S x -(Q) (I) wherein x is from 4 to 10, preferably 7, and Q is a core group.
- Trinuclear molybdenum compounds are relatively new and are claimed and described in our prior published US-A- 5,906,968. The matter disclosed in this prior US patent on the structure, preparation and properties of the trinuclear molybdenum compounds is incorporated herein by reference.
- the core group (Q) may be a ligand capable of rendering the organomolybdenum compound of formula (I) oil soluble and ensuring that said molybdenum compound is substantially charge neutral.
- the core group (Q) is generally associated with suitable ligands such as Ly wherein L is the ligand and y is of a sufficient number, type and charge to render the compound of formula (I) oil soluble and to neutralise the charge on the compound of formula (I) as a whole.
- suitable ligands such as Ly wherein L is the ligand and y is of a sufficient number, type and charge to render the compound of formula (I) oil soluble and to neutralise the charge on the compound of formula (I) as a whole.
- the trinuclear molybdenum compound used in the compositions of the present invention may be represented by the formula (II):
- the ligands "L” are suitably dihydrocarbyl dithiocarbamates of the structure (-S 2 CNR 2 ) wherein the dihydrocarbyl groups, R 2 impart oil solubility to the molybdenum compound.
- hydrocarbyl denotes a substituent having carbon atoms directly attached to the remainder of the ligand and is predominantly hydrocarbyl in character within the context of this invention.
- substituents include the following:
- hydrocarbon substituents ie, aliphatic (for example alkyl or alkenyl), alicyclic
- cycloalkyl or cycloalkenyl aromatic-, aliphatic- and alicyclic- substituted aromatic nuclei and the like, as well as cyclic substituents wherein the ring is completed through another portion of the ligand (that is, any two indicated substituents may together form an alicyclic group);
- substituted hydrocarbon substituents ie, those containing nonhydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbyl character of the substituent.
- suitable groups eg halo (especially chloro), amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulphoxy etc.
- hetero substituents ie, substituents which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms.
- the hydrocarbyl groups are preferably alkyl (e.g, in which the carbon atom attached to the remainder of the ligand "L" is primary, secondary or tertiary), aryl, substituted aryl and/or ether groups.
- the hydrocarbyl groups of the ligands should be such that they have a sufficient number of carbon atoms to render the compound (I) soluble or dispersible in the oil to which the trinuclear organomolybdenum compound containing the ligand is added.
- the total number of carbon atoms present among all of the hydrocarbyl groups of the organomolybdenum compounds' ligands is suitably at least 21, preferably at least 25, more preferably at least 30 and even more preferably at least 35, typically e.g., 21 to 800.
- the number of carbon atoms in each hydrocarbyl group will generally range from 1 to 100, preferably from 1 to 40 and more preferably from 3 to 20.
- the antioxidant which comprises the trinuclear organomolybdenum compounds will form a minor component of the total lubricant composition.
- the trinuclear organomolybdenum compounds will comprise from about 0.05 to 5.00% w/w of the total composition, ie the molybdenum metal is suitably present in an amount of about 25 to 3000 ppm, preferably from about 50 to 1000 ppm, and more preferably from about 100-500 ppm of the total composition.
- the antioxidant trinuclear molybdenum compound of the present invention can be used with any of the conventional dispersants used hitherto in the lubricating compositions.
- dispersants include inter alia the polyalkylene succinimides, Mannich condensation products of polylalkylphenol-formaldehyde polyamine and boronated derivatives thereof.
- ashless dispersants such as the ashless succinimides, especially the polyisobutenyl succinimides of a polyamine such as eg tetraethylenepentamine or its homologues, benzylamine ashless dispersants, and ester ashless dispersants.
- the dispersants are generally used in the compositions of the present invention in an amount ranging from about 2-10% by weight based on the total weight of the lubricant composition, preferably from about 4-8% by weight.
- these lubricating compositions may include additives commonly used in lubricating oils especially crankcase lubricants, such as antiwear agents, detergents, dispersants, rust inhibitors, viscosity index improvers, extreme-pressure agents, friction modifiers, corrosion inhibitors, emulsifying aids, pour point depressants, anti-foams and the like.
- crankcase lubricants such as antiwear agents, detergents, dispersants, rust inhibitors, viscosity index improvers, extreme-pressure agents, friction modifiers, corrosion inhibitors, emulsifying aids, pour point depressants, anti-foams and the like.
- a feature of the present invention is that lubricant compositions comprising relatively low saturates base oils and trinuclear organomolybdenum compounds provide unexpected improvement in oxidation control and significant benefits in fuel economy.
- Test oils were prepared. These oils were then tested in a bench oxidation test which was conducted at 165°C under a mixed nitrogen/air flow, with 40 ppm iron from added ferric acetylacetonate as catalyst. The flow rates of air and nitrogen were controlled at 500 ml/min and 350ml/min respectively. In these tests the following commercial materials have been used:
- Paranox® 106 is a polyisobutenylsuccinimide dispersant (ex Infenium, Linden, NJ)
- Molyvan® 822 is a dinuclear molybdenum dithiocarbamate (ex R T Vanderbilt Co)
- PDN 5203 is an experimental trinuclear molybdenum dithiocarbamate containing 5% w/w molybdenum.
- compositions of the test oils used in these Examples and their respective changes in viscosities after a 48 hour oxidation test are given in Table 1 below:
- Examples D-I show that the trinuclear molybdenum dithiocarbamate gives significantly better performance than conventional dinuclear molybdenum dithiocarbamate in oxidation control.
- the performance of the trinuclear molybdenum compound is further enhanced in Group I base oils when compared with Group II base oils.
- Example J-M demonstrate that trinuclear molybdenum dithiocarbamates give a better performance over an extended period of time than the conventional dinuclear molybdenum dithiocarbamates in oxidation control of Group I base oils.
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- Lubricants (AREA)
Abstract
This invention relates to a lubricating oil composition comprising a Group I basestock and an antioxidant comprising an oil soluble trinuclear organomolybdenum compound of the generic formula (I): Mo3Sx-(Q) wherein x is from 4 to 10 and Q is a core group, which may be a ligand, wherein the basestock has a kinematic viscosity at 100 °C (KV100) from about 2 cSt to 50 cSt (2 x 10-6 to 50 x 10-6 m2/sec), a saturates content of < 90 % w/w, an aromatics content of > 10 % w/w and a sulphur content of > 0.03 % w/w. The composition has an improved stability when compared with either a Group II, III or IV basestock containing the same antioxidant or a Group I basestock containing a dinuclear molybdenum dithiocarbamate.
Description
LUBRIFICATING OIL COMPOSITIONS COMPRISING A TRINUC EAR COMPOUND ANTIOXIDANT
This invention relates to lubricating oil compositions, especially lubricants used in internal combustion engines, comprising Group I base oils which are relatively low in saturates but high in sulphur with natural oxidation stability.
Lubricating oil compositions are used for the smooth operation of internal combustion engines, power transmission components including automatic transmissions, shock absorbers and power steering devices and gears. The engine oils for internal combustion engines in particular serve to (i) lubricate various sliding interfaces eg between the piston ring and cylinder liner, in bearings of the crank shaft and the connecting rod, and in the valve driving mechanism including cams and valve lifters, (ii) cool the engine, (iii) clean and disperse the combustion products and (iv) prevent corrosion and consequent rust formation. The stringent requirements for high performance engines in recent years have meant greater demand from lubricants used in such engines. Lubricating oils used in such engines usually deteriorate due to oxidation by oxygen and/or nitrogen oxides (NOx) contained in the blow-by gas (ie gas leaking from the combustion chamaber gases into the crankcase at the piston/cylinder interface). The concentration of NOx increases in the blow- by gas with increasing demand in performance of the engine. The deleterious effects of oxidation can be and have been mitigated by the use of various additives including antioxidants and by the use of base stocks which are relatively more stable to oxidation.
The control of oxidation processes has been improved to some extent by the use of lubricating compositions which comprise a Group II, III or IV basestocks which are relatively high in saturated hydrocarbons (hereafter "saturates") in preference to Group I basestocks which are relatively low in saturates because of the relatively high propensity of Group I base oils to oxidation. Group II, III and IV basestocks are typically more expensive than the conventional Group I basestocks. To extend the use of Group I basestocks for future engine oil products, it is important to identify suitable additives to enhance their properties. A feature of the present invention is the improvement of the oxidative stability of Group I basestocks.
It has now been found that it is possible to achieve the desired degree of oxidation stability from Group I base oils by judicious choice of antioxidants without recourse to relatively expensive Group II, III and/or IV basestocks.
Accordingly, the present invention is a lubricating oil composition comprising a major amount of a Group I base stock and an antioxidant comprising an oil soluble trinuclear organomolybdenum compound of the generic formula:
Mo3Sx-(Q) (I) wherein x is from 4 to 10, preferably 7, and Q is a core group, which may be a ligand.
The lubricating oil compositions of the present invention are those that comprise a major amount of a Group I basestock as defined in API 1509. Thus, for instance the Group I basestock may be mineral oils or blends thereof having a KNioo of 2-50 cSt, a viscosity index of 80-120, a saturates content of <90% w/w, an aromatics content of > 10% w/w and a sulphur content of > 0.03% w/w (300 ppm). Group I basestocks are produced by solvent extration followed by dewaxing. Specific examples of Group I basestock include inter alia solvent neutral basestocks such as MCT 30 ( 94 VI, 78% w/w saturates, 0.28% w/w sulphur); while hydrocracked distillates and raffinates which have been dewaxed, eg by conventional or catalytic dewaxing techniques, represent Group II and Group III base stocks with a sulphur content of less than 0.03% w/w and an aromatics content of < 10% w/w such as RLOP 500R (106 VI, >97% w/w saturates, and Mobil Jurong 500Ν (99VI, >97% w/w saturates). Polyalphaolefins represent Group IV basestocks.
According to a further embodiment, the present invention is a method of improving the oxidative stability of a lubricant composition, said composition comprising a Group I base stock which has a kinematic viscosity at 100°C (KV100) from about 2 cSt to 50 cSt (2 x 10"6 to 50 x 10"6 m2/sec), a saturates content of at less than 90% w/w, an aromatics content of > 10% w/w and a sulphur content of > 0.03% w/w (300 ppm) said method comprising adding to the basestock an effective amount of an antioxidant comprising an oil soluble trinuclear organomolybdenum compound of the generic formula:
Mo3Sx-(Q) (I) wherein x is from 4 to 10, preferably 7, and Q is a core group, which may be a ligand. The trinuclear molybdenum compounds are of formula (I) Mo3Sx-(Q) (I) wherein x is from 4 to 10, preferably 7, and Q is a core group. Trinuclear molybdenum compounds are relatively new and are claimed and described in our prior published US-A- 5,906,968. The matter disclosed in this prior US patent on the structure, preparation and properties of the trinuclear molybdenum compounds is incorporated herein by reference. In these compounds the core group (Q) may be a ligand capable of rendering the organomolybdenum compound of formula (I) oil soluble and ensuring that said molybdenum compound is substantially charge neutral. The core group (Q) is generally associated with suitable ligands such as Ly wherein L is the ligand and y is of a sufficient number, type and charge to render the compound of formula (I) oil soluble and to neutralise the charge on the compound of formula (I) as a whole. Thus, more specifically, the trinuclear molybdenum
compound used in the compositions of the present invention may be represented by the formula (II):
MO^xLy (II)
The ligands "L" are suitably dihydrocarbyl dithiocarbamates of the structure (-S2CNR2) wherein the dihydrocarbyl groups, R2 impart oil solubility to the molybdenum compound. In this instance, the term "hydrocarbyl" denotes a substituent having carbon atoms directly attached to the remainder of the ligand and is predominantly hydrocarbyl in character within the context of this invention. Such substituents include the following:
(1) hydrocarbon substituents, ie, aliphatic (for example alkyl or alkenyl), alicyclic
(for example cycloalkyl or cycloalkenyl), aromatic-, aliphatic- and alicyclic- substituted aromatic nuclei and the like, as well as cyclic substituents wherein the ring is completed through another portion of the ligand (that is, any two indicated substituents may together form an alicyclic group);
(2) substituted hydrocarbon substituents, ie, those containing nonhydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbyl character of the substituent. Those skilled in the art will be aware of suitable groups (eg halo (especially chloro), amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulphoxy etc.); and
(3) hetero substituents, ie, substituents which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms.
The hydrocarbyl groups are preferably alkyl (e.g, in which the carbon atom attached to the remainder of the ligand "L" is primary, secondary or tertiary), aryl, substituted aryl and/or ether groups.
Importantly, the hydrocarbyl groups of the ligands should be such that they have a sufficient number of carbon atoms to render the compound (I) soluble or dispersible in the oil to which the trinuclear organomolybdenum compound containing the ligand is added. The total number of carbon atoms present among all of the hydrocarbyl groups of the organomolybdenum compounds' ligands is suitably at least 21, preferably at least 25, more preferably at least 30 and even more preferably at least 35, typically e.g., 21 to 800. For instance, the number of carbon atoms in each hydrocarbyl group will generally range from 1 to 100, preferably from 1 to 40 and more preferably from 3 to 20.
The antioxidant which comprises the trinuclear organomolybdenum compounds will form a minor component of the total lubricant composition. For example, the trinuclear organomolybdenum compounds will comprise from about 0.05 to 5.00% w/w of the total composition, ie the molybdenum metal is suitably present in an amount of about 25 to 3000 ppm, preferably from about 50 to 1000 ppm, and more preferably from about 100-500 ppm of the total composition.
The antioxidant trinuclear molybdenum compound of the present invention can be used with any of the conventional dispersants used hitherto in the lubricating compositions. Examples of such dispersants include inter alia the polyalkylene succinimides, Mannich condensation products of polylalkylphenol-formaldehyde polyamine and boronated derivatives thereof. However, it is preferable to use ashless dispersants such as the ashless succinimides, especially the polyisobutenyl succinimides of a polyamine such as eg tetraethylenepentamine or its homologues, benzylamine ashless dispersants, and ester ashless dispersants. The dispersants are generally used in the compositions of the present invention in an amount ranging from about 2-10% by weight based on the total weight of the lubricant composition, preferably from about 4-8% by weight.
In general, these lubricating compositions may include additives commonly used in lubricating oils especially crankcase lubricants, such as antiwear agents, detergents, dispersants, rust inhibitors, viscosity index improvers, extreme-pressure agents, friction modifiers, corrosion inhibitors, emulsifying aids, pour point depressants, anti-foams and the like.
A feature of the present invention is that lubricant compositions comprising relatively low saturates base oils and trinuclear organomolybdenum compounds provide unexpected improvement in oxidation control and significant benefits in fuel economy.
The present invention is further illustrated with reference to the following Examples:
EXAMPLES
General Procedure:
A series of Test oils were prepared. These oils were then tested in a bench oxidation test which was conducted at 165°C under a mixed nitrogen/air flow, with 40 ppm iron from added ferric acetylacetonate as catalyst. The flow rates of air and nitrogen were controlled at 500 ml/min and 350ml/min respectively.
In these tests the following commercial materials have been used:
Paranox® 106 is a polyisobutenylsuccinimide dispersant (ex Infenium, Linden, NJ) Molyvan® 822 is a dinuclear molybdenum dithiocarbamate (ex R T Vanderbilt Co) PDN 5203 is an experimental trinuclear molybdenum dithiocarbamate containing 5% w/w molybdenum.
Examples A-C
Comparison between Group I and Group II base oils:
The compositions of the test oils used in these Examples and their respective changes in viscosities after a 48 hour oxidation test are given in Table 1 below:
TABLE 1
* containing 11.5% wt of molybdenum From the above it can be seen that the trinuclear molybdenum dithiocarbamate unexpectedly gives a better performance in Group I low saturates base oils than in the Group II high saturates base oils.
EXAMPLES D-I
Comparison between a trinuclear molvbdenum compound and a dinuclear molvbdenum compound
The compositions of the test oils in Examples D-I and their respective changes in viscosity data after a 32-hour oxidation test on each are shown in Table 2 below:
TABLE 2
Examples D-I show that the trinuclear molybdenum dithiocarbamate gives significantly better performance than conventional dinuclear molybdenum dithiocarbamate in oxidation control. The performance of the trinuclear molybdenum compound is further enhanced in Group I base oils when compared with Group II base oils.
Examples J-M
The changes in viscosity after a 48 hour oxidation test in Examples J-M is shown in Table 3 below:
TABLE 3
Example J-M demonstrate that trinuclear molybdenum dithiocarbamates give a better performance over an extended period of time than the conventional dinuclear molybdenum dithiocarbamates in oxidation control of Group I base oils.
Claims
1. A lubricating oil composition comprising a major amount of a Group I basestock and an antioxidant comprising an oil soluble trinuclear organomolybdenum compound of the generic formula:
Mo3Sx-(Q) (I) wherein x is from 4 to 10 and Q is a core group, which may be a ligand.
2. A composition according to Claim 1 wherein said basestock has a KVioo in the range from 2-20 cSt, a sulphur content of > 0.03% w/w (300 ppm) and a saturates content of < 90% w/w.
3. A composition according to any one of the preceding Claims wherein the core group Q is a ligand capable of rendering the organomolybdenum compound of formula (I) oil soluble and ensuring that said molybdenum compound is substantially charge neutral.
4. A composition according to any one of the preceding Claims wherein the trinuclear organomolybdenum compound is represented by the formula (II): Mo3SxLy (II) wherein L is the ligand and y is of a sufficient number, type and charge to render the compound of formula (I) oil soluble and to neutralise the charge on the compound of formula (I) as a whole..
5. A composition according to Claim 4 wherein the ligands "L" are dihydrocarbyl dithiocarbamates of the structure (-S2CNR2) wherein the dihydrocarbyl groups, R2 impart oil solubility to the molybdenum compound.
6. A composition according to Claim 5 wherein the group R is a substituent having carbon atoms directly attached to the remainder of the ligand and is predominantly hydrocarbyl in character.
7. A composition according to any one of the preceding Claims 4-7 wherein the total number of carbon atoms present among all of the hydrocarbyl groups of the organomolybdenum compounds' ligands is at least 21.
8. A composition according to any one of the preceding Claims wherein the trinuclear organomolybdenum compound is present in said composition in an amount from about 0.05 to 5.0 % w/w of the total composition.
9. A composition according to any one of the preceding Claims wherein the molybdenum metal is present in said composition in an amount from about 25 to 3000 ppm of the total composition.
10. A method of improving the oxidative stability of a lubricant composition comprising a Group I basestock which has a kinematic viscosity at 100°C (KVioo) from about 2 cSt to 50 cSt (2 x 10"6 to 50 x 10"6 m2/sec) and a saturates content of <90% w/w, an aromatics content of > 10% w/w and a sulphur content of > 0.03% w/w (300 ppm), said method comprising adding to the basestock an effective amount of an antioxidant comprising an oil soluble trinuclear organomolybdenum compound of the generic formula:
Mo3Sx-(Q) (I) wherein x is from 4 to 10, preferably 7, and Q is a core group, which may be a ligand.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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GB0003383 | 2000-02-14 | ||
GB0003383A GB2359091A (en) | 2000-02-14 | 2000-02-14 | Lubricating oil compositions |
PCT/US2001/009731 WO2001060956A1 (en) | 2000-02-14 | 2001-02-08 | Lubricating oil compositions comprising a trinuclear compound antioxidant |
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EP01920801A Withdrawn EP1265975A1 (en) | 2000-02-14 | 2001-02-08 | Lubricating oil compositions comprising a trinuclear compound antioxidant |
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EP (1) | EP1265975A1 (en) |
JP (1) | JP2003523454A (en) |
AR (1) | AR027301A1 (en) |
AU (1) | AU2001247820A1 (en) |
BR (1) | BR0108333A (en) |
CA (1) | CA2398072A1 (en) |
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JP5175462B2 (en) | 2006-09-04 | 2013-04-03 | 出光興産株式会社 | Lubricating oil composition for internal combustion engines |
JP5468728B2 (en) | 2007-05-29 | 2014-04-09 | 出光興産株式会社 | Lubricating oil composition for internal combustion engines |
KR102654520B1 (en) * | 2018-10-18 | 2024-04-03 | 현대자동차주식회사 | Automatic transmission oil composition |
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KR100516268B1 (en) * | 1996-12-13 | 2005-09-20 | 엑손 리써치 앤드 엔지니어링 컴파니 | Lubricating oil compositions containing organic molybdenum complexes |
US6010987A (en) * | 1996-12-13 | 2000-01-04 | Exxon Research And Engineering Co. | Enhancement of frictional retention properties in a lubricating composition containing a molybdenum sulfide additive in low concentration |
US5837657A (en) * | 1997-12-02 | 1998-11-17 | Fang; Howard L. | Method for reducing viscosity increase in sooted diesel oils |
JP4528439B2 (en) * | 1997-12-12 | 2010-08-18 | インフィニューム ユーエスエイ リミテッド パートナーシップ | Process for producing trinuclear molybdenum-sulfur compounds and their use as additives for lubricants |
US5906968A (en) * | 1997-12-12 | 1999-05-25 | Exxon Research & Engineering Company | Method of synthesizing Mo3 Sx containing compounds |
US6143701A (en) * | 1998-03-13 | 2000-11-07 | Exxon Chemical Patents Inc. | Lubricating oil having improved fuel economy retention properties |
US5895779A (en) * | 1998-03-31 | 1999-04-20 | Exxon Chemical Patents Inc | Lubricating oil having improved fuel economy retention properties |
GB9813070D0 (en) * | 1998-06-17 | 1998-08-19 | Exxon Chemical Patents Inc | Lubricant compositions |
-
2000
- 2000-02-14 GB GB0003383A patent/GB2359091A/en not_active Withdrawn
-
2001
- 2001-01-26 AR ARP010100358A patent/AR027301A1/en unknown
- 2001-02-08 BR BR0108333-3A patent/BR0108333A/en not_active Application Discontinuation
- 2001-02-08 EP EP01920801A patent/EP1265975A1/en not_active Withdrawn
- 2001-02-08 AU AU2001247820A patent/AU2001247820A1/en not_active Abandoned
- 2001-02-08 JP JP2001560328A patent/JP2003523454A/en active Pending
- 2001-02-08 WO PCT/US2001/009731 patent/WO2001060956A1/en not_active Application Discontinuation
- 2001-02-08 CA CA002398072A patent/CA2398072A1/en not_active Abandoned
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AU2001247820A1 (en) | 2001-08-27 |
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AR027301A1 (en) | 2003-03-19 |
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BR0108333A (en) | 2003-03-11 |
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