US3419589A - Organic molybdenum compounds containing sulfur and method of preparation - Google Patents
Organic molybdenum compounds containing sulfur and method of preparation Download PDFInfo
- Publication number
- US3419589A US3419589A US492289A US49228965A US3419589A US 3419589 A US3419589 A US 3419589A US 492289 A US492289 A US 492289A US 49228965 A US49228965 A US 49228965A US 3419589 A US3419589 A US 3419589A
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- US
- United States
- Prior art keywords
- solution
- molybdenum
- sodium
- product
- dioxide
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- 238000000034 method Methods 0.000 title description 18
- 229910052717 sulfur Inorganic materials 0.000 title description 14
- 239000005078 molybdenum compound Substances 0.000 title description 8
- 150000002752 molybdenum compounds Chemical class 0.000 title description 8
- 238000002360 preparation method Methods 0.000 title description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title description 5
- 239000011593 sulfur Substances 0.000 title description 5
- 239000000243 solution Substances 0.000 description 79
- 239000000047 product Substances 0.000 description 61
- 235000015393 sodium molybdate Nutrition 0.000 description 46
- 239000011684 sodium molybdate Substances 0.000 description 46
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 46
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 40
- 229910017604 nitric acid Inorganic materials 0.000 description 40
- GCMDLPXRCVHIMG-UHFFFAOYSA-N dioxomolybdenum(2+) Chemical compound O=[Mo+2]=O GCMDLPXRCVHIMG-UHFFFAOYSA-N 0.000 description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000011734 sodium Substances 0.000 description 24
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 22
- 229910052708 sodium Inorganic materials 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- -1 molybdenum (VI) dioxide diamyldithiocarbamate Chemical compound 0.000 description 18
- 239000000654 additive Substances 0.000 description 17
- 241000605112 Scapanulus oweni Species 0.000 description 16
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 14
- 239000007800 oxidant agent Substances 0.000 description 14
- 239000000314 lubricant Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 230000020477 pH reduction Effects 0.000 description 12
- 230000000996 additive effect Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000012208 gear oil Substances 0.000 description 10
- ILNWEIMZWZNAKF-UHFFFAOYSA-M sodium;n,n-dipropylcarbamodithioate Chemical compound [Na+].CCCN(C([S-])=S)CCC ILNWEIMZWZNAKF-UHFFFAOYSA-M 0.000 description 10
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- 125000004430 oxygen atom Chemical group O* 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 125000004434 sulfur atom Chemical group 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- 239000007900 aqueous suspension Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 6
- 239000003879 lubricant additive Substances 0.000 description 6
- DWVJEMMXXKPJTE-UHFFFAOYSA-M sodium;n,n-dipentylcarbamodithioate Chemical compound [Na+].CCCCCN(C([S-])=S)CCCCC DWVJEMMXXKPJTE-UHFFFAOYSA-M 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000003849 aromatic solvent Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000002432 hydroperoxides Chemical class 0.000 description 5
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 5
- 150000001451 organic peroxides Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 5
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- SPHSHWSCSHKMAE-UHFFFAOYSA-N ethyl n-hexylcarbamodithioate Chemical compound CCCCCCNC(=S)SCC SPHSHWSCSHKMAE-UHFFFAOYSA-N 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- HUMLQUKVJARKRN-UHFFFAOYSA-M sodium;n,n-dibutylcarbamodithioate Chemical compound [Na+].CCCCN(C([S-])=S)CCCC HUMLQUKVJARKRN-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 231100000241 scar Toxicity 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- CXVCSRUYMINUSF-UHFFFAOYSA-N tetrathiomolybdate(2-) Chemical compound [S-][Mo]([S-])(=S)=S CXVCSRUYMINUSF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241001279686 Allium moly Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000288748 Chrysochloridae Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 1
- DMVRKCXZQHAICB-UHFFFAOYSA-H [Mo+6].CCCCN(CCCC)C([S-])=S.CCCCN(CCCC)C([S-])=S.CCCCN(CCCC)C([S-])=S.CCCCN(CCCC)C([S-])=S.CCCCN(CCCC)C([S-])=S.CCCCN(CCCC)C([S-])=S Chemical compound [Mo+6].CCCCN(CCCC)C([S-])=S.CCCCN(CCCC)C([S-])=S.CCCCN(CCCC)C([S-])=S.CCCCN(CCCC)C([S-])=S.CCCCN(CCCC)C([S-])=S.CCCCN(CCCC)C([S-])=S DMVRKCXZQHAICB-UHFFFAOYSA-H 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012431 aqueous reaction media Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- JWHFYIKVRLMUCH-UHFFFAOYSA-N dipentylcarbamodithioic acid Chemical compound CCCCCN(C(S)=S)CCCCC JWHFYIKVRLMUCH-UHFFFAOYSA-N 0.000 description 1
- BQCRLWBELMWYQA-UHFFFAOYSA-N dipropylcarbamodithioic acid Chemical compound CCCN(C(S)=S)CCC BQCRLWBELMWYQA-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- UMOJXGMTIHBUTN-UHFFFAOYSA-N molybdenum(5+) Chemical class [Mo+5] UMOJXGMTIHBUTN-UHFFFAOYSA-N 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
Classifications
-
- 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
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/065—Sulfides; Selenides; Tellurides
- C10M2201/066—Molybdenum sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
-
- 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
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Definitions
- the invention relates generally to novel lubricant additives and methods of preparing the same. More particularly, the inventlon is concerned with organic, sulfur containing molybdenum compounds and their preparation.
- molybdenum disulfide M08 as a lubricant or additive
- M08 molybdenum disulfide
- molybdenum disulfide has certain disadvantages, for example, it is generally insoluble in lubricating oils and in certain instances difiicult even to suspend in in the oils.
- the present invention avoids these disadvantages by way of the discovery of certain organic molybdenum compounds and methods by which these compounds can be prepared in good yields. These organic molybdenum compounds contain sulfur and are readily suspendable or soluble in most lubricants.
- the method of using the compounds enables their operation in such a fashion as to still take advantage of the lubricating properties of molybdenum disulfide in that the compounds react with other constituents in the lubricants or within themselves to form a molybdenum sulfide film.
- This formation of molybdenum sulfide takes place at high temperature-s and/ or pressures resulting generally in the presence of molybdenum sulfide only at the place of contact between the mating surfaces of the parts to be lubricated. That is, the contact between the mating surfaces causes high temepratures and/ or pressures resulting in formation of molybdenum sulfide at the place of contact where it is most needed. This in return allows a more practical use of the lubricant additive.
- Another object is to provide certain new materials useful as lubricant additives, which materials are obtained by the treatment of molybdenum (VI) dialkyldithiocarbamates with hydrogen sulfide.
- a further object is to provide novel methods for the preparation and isolation of the molybdenum (V I) dioxide dialkyldithiocarbamates, and the hydrogen sulfide treated molybdenum (VI) dialkyldithiocarbamates, there by enabling their preparation in substantially high yields of commercial practicability.
- Still another object of this invention is to provide lubricant compositions utilizing the new lubricant additives such that their lubricating properties can be taken advantage of in an elfective manner.
- hexavalent (VI) molybdenum compounds or complexes of the present invention are termed molybdenum (VI) dioxide dialkyldithiocarbamates and certain materials believed to be thiomolybdates formed by hydrogen hulfide treatment of these molybdenum (VI) dioxide dialkyldithiocarbamates.
- the material is prepared by dilute nitric acid acidification of sodium dipropyldithiocarbamate and sodium molybdate.
- the dipropyldithiocarbamate can be conveniently prepared by adding a slight excess of carbon disulfide to an equimolar, aqueous suspension of di-n-propylamine and sodium hydroxide. After stirring for a period sufiicient to permit reaction, such as for example, one hour, the mixture is filtered giving a clear, light yellow solution of sodium di-n-propyldithiocarbamate.
- the sodium di-npropyldithiocarbamate is reacted with sodium molybdate in the proportion of about 1.5 moles to about 2 moles of the sodium di-n-propyldithiocarbamate per mole of sodium molybdate.
- the reaction is carried out in an aqueous liquid phase by dissolving the constituents, and thereafter acidifying with dilute nitric acid in an amount of about 2 moles to about 4 moles of diluted HNO per mole of sodium molybdate.
- the nitric acid is preferably introduced as a dilute solution of a more concentrated form ranging from about 1% to about 10% by weight. The nitric acid solution is slowly added to an agitated mixture of the sodium molybdate and sodium di-n-propyldithiocarbamate.
- the crude product from the acidification reaction can be readily recovered from the aqueous reaction medium, for example, by extracting with an organic solvent, such as chloroform, benzene or the like, and thereafter precipitating the extracted product to yield a relatively pure orange crystalline product of Mo O [(nC H-,) NCS
- the crystalline solids product is air-stable and melts at 1l0.01lO.5 C. It is readily soluble in aromatic and most polar organic solvents, but insoluble in Water and aliphatic hydrocarbons. It can be suspended as a lubrication additive in SAE- base gear oil by heating a mixture of the M0[ (n'C H NCS and the oil to C., resulting in a suspension wherein negligible settling occurs after two weeks.
- the molybdenum (VI) dioxide diamyldithiocarbamate has the formula:
- This material is prepared by the nitri acid acidification of sodium diarnyldithiocarbamate and sodium molybdate.
- the diamyldithiocarbamate can be conveniently prepared in the following manner: A commercial grade diamylamine in solution with NaOH is reacted with carbon disulfide to make the sodium salt, sodium diamyldithiocarbamate, which is put in aqueous solution with sodium molybdate and then acidified with dilute nitric acid, thereby producing a crude product including pentavalent molybdenum compounds in the form of a purple tar precipitate.
- the crude product is extracted with an organic solvent such as toluene, and the resultant solution is subjected to further oxidation to convert the pentavalent molybdenum compound to the hexavalent state.
- oxidizing agents of the type, including t-butyl hydroperoxide, t-butyl peroxide, or cumene hydroperoxide can be employed.
- the oxidizing agent is used in an amount of from about 0.2 to about 0.5 mole per mole of total molybdenum present.
- a toluene solution of the purple tar is then carefully oxidized with t-butyl hydroperoxide to give a solution of the hexavalent complex which is orange in color.
- Isolation of the product is then achieved by extraction with aromatic hydrocarbons and precipita tion in cold petroleum ether.
- the product is a dark orange tar. Infrared spectrum shows it to be a molybdenum (VI) complex.
- a further embodiment of the invention is molybdenum (VI) dioxide di-Z-ethylhexyldithiocarbamate having the formula:
- This material is again prepared by nitri acid acidification of sodium di-2-ethylhexyldithiocarbamate and sodium molybdate.
- the sodium di-2-ethylhexyldithiocarbamate can be conveniently prepared by adding carbon disulfide to an aqueous suspension of di-2-ethylhexylamine and sodium hydroxide. This mixture is filtered to obtain a solution, milky white in color. An aqueous solution of sodium molybdate is added to this filtrate. After cooling, the mixture is acidified with a cold solution of dilute nitric acid (temperature range, about C. to about 10 C.) to give a purple suspension and purple tar product.
- the complex is then extracted with a solvent such as benzene and oxidized with an oxidizing agent of the type such as t-butyl hydroperoxide, t-butyl peroxide or cumene hydroperoxide.
- a solvent such as benzene
- an oxidizing agent of the type such as t-butyl hydroperoxide, t-butyl peroxide or cumene hydroperoxide.
- the product MOVIO2[(C8H17)2NCS2]2 is then precipitated from petroleum ether, and further recovery is effected by vacuum evaporation.
- the product is soluble in aromatic solvents, 10 percent soluble in ligroine at room temperature, and stable to storage. The product gives stable suspensions when added to gear oil as a ligroine solution.
- the nitric acid acidification can be carried out within the temperature range of about minus C. to about 50 C. However, best results were obtained when the acidification was carried out within a preferred temperature range of about 0 C. to about 25 C.
- the molar ratio of nitric acid to sodium molybdate in the acidification can vary from about 1:1 to about 6:1, with the preferred molar ratio being about 2:1 to about 4:1 within which the most suitable results are obtained.
- the nitric acid is introduced as a dilute solution prepared from a more concentrated nitric acid, said solution having an HNO content of about 1% to about by weight.
- the molar ratio of the sodium dialkyldithiocarbamate to sodium molybdate may vary within the range of about 1:1 to about 5:1. Best results were obtained at a preferred molar ratio of about 1.5 :1 to about 2.0: 1.
- oxidizing agents of the type t-butyl peroxide, t-butyl hydroperoxide or cumene hydroperoxide have been found suitable.
- the ratio of the moles of oxidizing agent present to the total moles of molybdenum present may vary from a molar ratio of about 0.1:1 to about 1:1. However, best results have been obtained when -a preferred molar ratio is used of about 0.2:1 to about 0.521.
- the molybdenum (VI) dioxide dialkyldithiocarbamate complexes can be subjected to further treatment with hydrogen sulfide to effect conversion thereof to what is believed to be a corresponding thiomolybdate complex. This is carried out by contacting a solution of the molybdenum dialkyldithiocarbamate with H S for a period of time sufiicient to elfect a replacement of an oxygen atom with a sulfur atom.
- An embodiment of the invention in this regard is the material formed by hydrogen sulfide treatment of molybdenum (VI) dioxide di-Z-ethylhexyldithiocarbamate.
- This complex in a solution of benzene is reacted with H 8 by bubbling H S through the solution.
- the product in good yield is recovered by vacuum evaporation resulting in a purple-black, fluid tar.
- This product believed to be a thiomolybdate, is soluble in most organic solvents and is 50 percent soluble in ligroine at room temperature. It is readily suspendable in SAE- gear oil, which suspension is stable.
- the formula of this product is believed to be MOOS[(C8H17)2NCS2].
- the molybdenum (VI) dioxide di-n-propyldithiocarbamate was prepared as follows: A solution of sodium din-propyldithiocarbamate was made by adding a slight excess of carbon disulfide to an equimolar, aqueous suspension of di-n-propylamine (0.060 g. mole) and sodium hydroxide. This solution was stirred for one hour, then filtered to obtain a clear, light yellow solution of sodium di-n-propyldithiocarbamate (0.060 g. mole) which was used immediately by placing it in solution with sodium molybdate dihydrate (Na MoO -2H O, 0.041 g. mole) and 250 ml. of water.
- sodium molybdate dihydrate Na MoO -2H O, 0.041 g. mole
- a solution of sodium di-n-propyldithiocarbamate was made by adding a slight excess of carbon disulfide to an equimolar, aqueous suspension of dipropylamine (0.60 g. mole) and sodium hydroxide. This solution was stirred for one hour, then filtered to obtain a clear, light yellow solution of sodium di-n-propyldithiocarbamate (0.60 g. mole) which was used immediately by placing it in solution with sodium molybdate dihydrate (Na MoO -2H O, 0.36 g. mole) and 1700 ml. of water. This solution was then acidified by the careful addition of dilute nitric acid, at a temperature range of about 0 C.
- the molybdenum (VI) dioxide di-n-butyldithiocarbamate was prepared as follows: A solution of sodium din-butyldithiocarbamate was made by adding a slight excess of carbon disulfide to an equimolar aqueous suspension of di-n-butylamine (0.40 g. mole) and sodium hydroxide. This solution was stirred for one hour, then filtered to obtain a clear, light yellow solution of sodium dibutyldithiocarbamate (0.40 g. mole) which was used immediately by placing it in solution with sodium molybdate dihydrate (0.29 g. mole) and 2000 ml. of water.
- This solution was then acidified by careful addition of dilute nitric acid at a temperature range of from C. to 6 C., with 890 ml. of an acid solution containing 0.87 g. mole HNO being added.
- the product of the acidification was a purple tar, and this was dissolved in toluene.
- t-butyl hydroperoxide was then slowly added to prevent excess oxidation, in an amount equalling 0.065 g. mole. This resulted in a pure crystalline product of 77 grams representing a yield of 72 percent.
- the product was an orange crystalline solid which was precipitated out of solution by the addition of petroleum ether and cooling.
- the product molybdenum (VI) dioxide di-n-butyldithiocarbamate, consisted of yellow-orange crystals with a meltingpoint of approximately 70 C. This product was soluble in aromatic solvents and halogenated solvents. At 25 C., 0.11 gram of the product dissolved in 100 ml. of ligroine (B.P. 66- 75 C.), while 0.36 gram dissolved in the same amount of solvent at 45 C. The complex could be dispersed in gear oil as a benzene solution to form a stable suspension.
- VI molybdenum
- Example 3 (C5H1 2 A commercial grade diamylamine (0.04 g. mole, 6.29 grams) was placed in equimolar aqueous suspension with NaOH. A slight molar excess of carbon disulfide was added to the aqueous suspension and the mixture was stirred for one hour, then filtered to obtain a solution of sodium diamyldithiocarbamate (0.04 g. mole). This solution was used fresh by placing it in solution with sodium molybdate dihydrate (0.03 g, mole, 7.26 grams); total water in the solution was approximately 150 ml. To this was carefully added a solution of 8 ml. of N nitric acid in 200 ml. of water.
- a commercial grade di-2-ethylhexylamine (48.4 grams, 0.20 mole) and NaOH (9.50 grams, 0.222 mole) were placed in aqueous suspension with 1200 ml. of water.
- carbon disulfide 17.6 grams, 0.231 mole
- the mixture was then filtered to obtain a milky white solution, and a solution of sodium molybdate dihydrate (26.00 grams, 0.17 mole) in 500 ml. of water was added to the filtrate.
- the mixture was acidified with a cold solution of 30 ml. of 15 N nitric acid in 400 ml. of water to obtain a purple suspension and purple tar.
- the complex was extracted with benzene, and after oxidizing the solution with t-butyl hydroperoxide (0.068 g. mole), it was allowed to stand overnight. A large amount of petroleum ether was then added and cooling caused 8.1 grams of a dark brown, thick tar to settle out. The decanted liquid was then vacuum evaporated on a water bath to obtain 41.4 grams of a dark, thick liquid. The yield of molybdenum (VI) di 2 ethylhexyldithiocarbamate complex was 63 percent. This product was soluble in aromatic solvents, ten percent soluble in ligroine (B.P. 66-75 C.), but was insoluble in petroleum ether (B.P. 3060 C.).
- Example treated MO O I (C H17)2NCS2] 2
- a benzene solution of the Mo" O [(C H NCS complex was reacted with hydrogen sulfide by bubbling H S through the solution for approximately three hours. This resulted in a product, which was recovered by vacuum evaporation, of a purple-black, fluid tar. A weight recovery of 95 percent was realized from the vacuum evaporation. It is believed that the H 8 reacted with the complex to form the corresponding thiomolybdate by replacement of oxygen with sulfur. The product of reacting H 8 with the above complex was obtained in good yields and is believed to have the formula:
- the product was soluble in most organic solvents and was at least 50 percent soluble in ligroine (B.P. 66-75" C.) at room temperature.
- the product was readily suspended in SAE- gear oil, and this suspension was found to be stable for a least twenty days.
- the products prepared in accordance with the invention were found to have highly beneficial properties as lubricant additives among other uses, such as for example, antioxidants, rubber accelerators and fungicides.
- the evaluation test data for lubricating properties of the compounds of the present invention are set out in the following Tables 2 and 3.
- the compounds were tested as additives to a commercially available lithium grease in Table 2, and as additives to a commercially available gear oil in Table 3.
- oscillation tests run on an oscillation friction testing machine. These tests consist of applying lubricant between two 1.0 inch diameter flat washers and thereafter oscillating the washers relative to each other under preselected loads and then counting the number of oscillations until seizure occurs.
- concentrations of about 1% to about 5% by weight are normally used; when used as additives to pastetype lubricants, such as the M08 type, pastes formed from oil-additive mixtures, and pastes for El. situations, concentrations up to about by weight may be employed.
- the compounds of the invention generally are not oil soluble, and therefore when used as additives to lubricants or hydrocarbon vehicles, they are normally added as dispersions or suspensions through the use of organic carrier solvents, or the additive in solid product form is dispersed or suspended in the lubricant as finely divided particles.
- the average particle size can vary up to about twenty microns. Generally, however, it is less than ten microns, with the preferred range being an average particle size of about one micron or less.
- oxidizing said first product with a strong oxidizing agent selected from the group consisting of t-butyl peroxide, t-butyl hydroper-oxide and cumene hydroperoxide, and
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Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL137307D NL137307C (US07582779-20090901-C00044.png) | 1965-10-01 | ||
US492289A US3419589A (en) | 1965-10-01 | 1965-10-01 | Organic molybdenum compounds containing sulfur and method of preparation |
DE19661568041 DE1568041A1 (de) | 1965-10-01 | 1966-09-23 | Organische schwefelhaltige Molybdaenverbindungen und Verfahren zu ihrer Herstellung |
FR77815A FR1559588A (US07582779-20090901-C00044.png) | 1965-10-01 | 1966-09-27 | |
BE687494D BE687494A (US07582779-20090901-C00044.png) | 1965-10-01 | 1966-09-28 | |
SE13186/66A SE331089B (US07582779-20090901-C00044.png) | 1965-10-01 | 1966-09-30 | |
GB43867/66A GB1087630A (en) | 1965-10-01 | 1966-09-30 | Molybdenum compounds containing sulphur |
NL6613882A NL6613882A (US07582779-20090901-C00044.png) | 1965-10-01 | 1966-09-30 | |
JP44035543A JPS4834729B1 (US07582779-20090901-C00044.png) | 1965-10-01 | 1969-05-10 | |
NL7208860A NL7208860A (US07582779-20090901-C00044.png) | 1965-10-01 | 1972-06-27 |
Applications Claiming Priority (1)
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US492289A US3419589A (en) | 1965-10-01 | 1965-10-01 | Organic molybdenum compounds containing sulfur and method of preparation |
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US3419589A true US3419589A (en) | 1968-12-31 |
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US492289A Expired - Lifetime US3419589A (en) | 1965-10-01 | 1965-10-01 | Organic molybdenum compounds containing sulfur and method of preparation |
Country Status (8)
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US4098705A (en) * | 1975-08-07 | 1978-07-04 | Asahi Denka Kogyo K.K. | Sulfur containing molybdenum dihydrocarbyldithiocarbamate compound |
US4208292A (en) * | 1979-01-29 | 1980-06-17 | Mobil Oil Corporation | Phosphomolybdate compounds and their use as lubricant additives |
US4214058A (en) * | 1976-10-20 | 1980-07-22 | Bridgestone Tire Company | Vulcanizable rubber composition containing _metal organic compounds |
US4265773A (en) * | 1979-06-28 | 1981-05-05 | Chevron Research Company | Process of preparing molybdenum complexes, the complexes so-produced and lubricants containing same |
US4500439A (en) * | 1980-09-25 | 1985-02-19 | Standard Oil Company (Indiana) | Hydrocarbon-soluble polyamine-molybdenum compositions, lubricants and gasoline containing same |
US4681957A (en) * | 1985-09-03 | 1987-07-21 | Exxon Research And Engineering Company | Method of preparing hydrocarbon substituted dithiocarbamates of molybdenum |
US4683316A (en) * | 1986-01-02 | 1987-07-28 | Exxon Research And Engineering Company | Method of preparation of dithiocarbamate complexes of molybdenum (VI) |
WO1987005045A1 (en) * | 1986-02-21 | 1987-08-27 | The Lubrizol Corporation | Novel carbamate additives for functional fluids |
US4730064A (en) * | 1985-03-14 | 1988-03-08 | Exxon Research And Engineering Company | Heterometallic thiocubanes (C-2044) |
US4978464A (en) * | 1989-09-07 | 1990-12-18 | Exxon Research And Engineering Company | Multi-function additive for lubricating oils |
US4990271A (en) * | 1989-09-07 | 1991-02-05 | Exxon Research And Engineering Company | Antiwear, antioxidant and friction reducing additive for lubricating oils |
US4992186A (en) * | 1989-09-07 | 1991-02-12 | Exxon Research And Engineering Company | Enhancing antiwear and friction reducing capability of certain molybdenum (V) sulfide compounds |
US5019283A (en) * | 1989-09-07 | 1991-05-28 | Exxon Research And Engineering Company | Enhancing antiwear and friction reducing capability of certain xanthate containing molybdenum sulfide compounds |
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US5445749A (en) * | 1993-02-01 | 1995-08-29 | The Lubrizol Corporation | Thiocarbamates for metal/ceramic lubrication |
WO1996037584A1 (en) * | 1994-05-20 | 1996-11-28 | Exxon Research And Engineering Company | Lubricating oil composition |
US5824627A (en) * | 1996-12-13 | 1998-10-20 | Exxon Research And Engineering Company | Heterometallic lube oil additives |
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 |
US6103674A (en) * | 1999-03-15 | 2000-08-15 | Uniroyal Chemical Company, Inc. | Oil-soluble molybdenum multifunctional friction modifier additives for lubricant compositions |
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US20030224951A1 (en) * | 2001-03-23 | 2003-12-04 | Mcconnachie Jonathan M. | Lubricant compositions |
US20050065044A1 (en) * | 2001-05-08 | 2005-03-24 | Migdal Cyril A | Nanosized particles of molybdenum sulfide and derivatives,method for its preparation and uses thereof as lubricant additive |
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Publication number | Priority date | Publication date | Assignee | Title |
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US4098705A (en) * | 1975-08-07 | 1978-07-04 | Asahi Denka Kogyo K.K. | Sulfur containing molybdenum dihydrocarbyldithiocarbamate compound |
US4214058A (en) * | 1976-10-20 | 1980-07-22 | Bridgestone Tire Company | Vulcanizable rubber composition containing _metal organic compounds |
US4208292A (en) * | 1979-01-29 | 1980-06-17 | Mobil Oil Corporation | Phosphomolybdate compounds and their use as lubricant additives |
US4265773A (en) * | 1979-06-28 | 1981-05-05 | Chevron Research Company | Process of preparing molybdenum complexes, the complexes so-produced and lubricants containing same |
US4500439A (en) * | 1980-09-25 | 1985-02-19 | Standard Oil Company (Indiana) | Hydrocarbon-soluble polyamine-molybdenum compositions, lubricants and gasoline containing same |
US4730064A (en) * | 1985-03-14 | 1988-03-08 | Exxon Research And Engineering Company | Heterometallic thiocubanes (C-2044) |
US4681957A (en) * | 1985-09-03 | 1987-07-21 | Exxon Research And Engineering Company | Method of preparing hydrocarbon substituted dithiocarbamates of molybdenum |
US4683316A (en) * | 1986-01-02 | 1987-07-28 | Exxon Research And Engineering Company | Method of preparation of dithiocarbamate complexes of molybdenum (VI) |
WO1987005045A1 (en) * | 1986-02-21 | 1987-08-27 | The Lubrizol Corporation | Novel carbamate additives for functional fluids |
US4846983A (en) * | 1986-02-21 | 1989-07-11 | The Lubrizol Corp. | Novel carbamate additives for functional fluids |
US4978464A (en) * | 1989-09-07 | 1990-12-18 | Exxon Research And Engineering Company | Multi-function additive for lubricating oils |
US4990271A (en) * | 1989-09-07 | 1991-02-05 | Exxon Research And Engineering Company | Antiwear, antioxidant and friction reducing additive for lubricating oils |
US4992186A (en) * | 1989-09-07 | 1991-02-12 | Exxon Research And Engineering Company | Enhancing antiwear and friction reducing capability of certain molybdenum (V) sulfide compounds |
US5019283A (en) * | 1989-09-07 | 1991-05-28 | Exxon Research And Engineering Company | Enhancing antiwear and friction reducing capability of certain xanthate containing molybdenum sulfide compounds |
US5281347A (en) * | 1989-09-20 | 1994-01-25 | Nippon Oil Co., Ltd. | Lubricating composition for internal combustion engine |
US5445749A (en) * | 1993-02-01 | 1995-08-29 | The Lubrizol Corporation | Thiocarbamates for metal/ceramic lubrication |
WO1996037584A1 (en) * | 1994-05-20 | 1996-11-28 | Exxon Research And Engineering Company | Lubricating oil composition |
US5824627A (en) * | 1996-12-13 | 1998-10-20 | Exxon Research And Engineering Company | Heterometallic lube oil additives |
US6358894B1 (en) | 1996-12-13 | 2002-03-19 | Infineum Usa L.P. | Molybdenum-antioxidant lube oil compositions |
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 |
US6153564A (en) * | 1998-06-17 | 2000-11-28 | Infineum Usa L.P. | Lubricating oil compositions |
US6211123B1 (en) | 1998-06-17 | 2001-04-03 | Infineum Usa L.P. | Lubricating oil compositions |
US6103674A (en) * | 1999-03-15 | 2000-08-15 | Uniroyal Chemical Company, Inc. | Oil-soluble molybdenum multifunctional friction modifier additives for lubricant compositions |
US6541429B2 (en) | 2000-03-29 | 2003-04-01 | Infineum International Ltd. | Lubricant compositions |
EP1138752A1 (en) * | 2000-03-29 | 2001-10-04 | Infineum International Limited | Lubricant compositions comprising organic molydenum complexes |
US20030224951A1 (en) * | 2001-03-23 | 2003-12-04 | Mcconnachie Jonathan M. | Lubricant compositions |
US6953771B2 (en) | 2001-03-23 | 2005-10-11 | Infineon International Limited | Lubricant compositions |
US20050065044A1 (en) * | 2001-05-08 | 2005-03-24 | Migdal Cyril A | Nanosized particles of molybdenum sulfide and derivatives,method for its preparation and uses thereof as lubricant additive |
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Also Published As
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NL6613882A (US07582779-20090901-C00044.png) | 1967-04-03 |
DE1568041A1 (de) | 1970-02-05 |
BE687494A (US07582779-20090901-C00044.png) | 1967-03-01 |
JPS4834729B1 (US07582779-20090901-C00044.png) | 1973-10-23 |
FR1559588A (US07582779-20090901-C00044.png) | 1969-03-14 |
SE331089B (US07582779-20090901-C00044.png) | 1970-12-14 |
GB1087630A (en) | 1967-10-18 |
NL137307C (US07582779-20090901-C00044.png) |
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