US3297573A - Lubricants containing group ivb metal phosphates - Google Patents
Lubricants containing group ivb metal phosphates Download PDFInfo
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- US3297573A US3297573A US358113A US35811364A US3297573A US 3297573 A US3297573 A US 3297573A US 358113 A US358113 A US 358113A US 35811364 A US35811364 A US 35811364A US 3297573 A US3297573 A US 3297573A
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- Prior art keywords
- orthophosphate
- metal
- composition
- hydrocarbyl
- titanium
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- 239000000314 lubricant Substances 0.000 title claims description 11
- 229910001463 metal phosphate Inorganic materials 0.000 title description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 230000001050 lubricating effect Effects 0.000 claims description 15
- 230000000737 periodic effect Effects 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000010936 titanium Substances 0.000 description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 20
- 125000001183 hydrocarbyl group Chemical group 0.000 description 20
- 229910052719 titanium Inorganic materials 0.000 description 20
- -1 alkphenyl Chemical group 0.000 description 19
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 11
- 239000010687 lubricating oil Substances 0.000 description 11
- 229910052726 zirconium Inorganic materials 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- 244000126822 Albuca minor Species 0.000 description 1
- 241001598984 Bromius obscurus Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BLXFVJOQBWDBOW-UHFFFAOYSA-N bis(4-octylphenyl) hydrogen phosphate Chemical compound C1=CC(CCCCCCCC)=CC=C1OP(O)(=O)OC1=CC=C(CCCCCCCC)C=C1 BLXFVJOQBWDBOW-UHFFFAOYSA-N 0.000 description 1
- WFFZELZOEWLYNK-CLFAGFIQSA-N bis[(z)-octadec-9-enyl] hydrogen phosphate Chemical compound CCCCCCCC\C=C/CCCCCCCCOP(O)(=O)OCCCCCCCC\C=C/CCCCCCCC WFFZELZOEWLYNK-CLFAGFIQSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002362 hafnium Chemical class 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- FPLIHVCWSXLMPX-UHFFFAOYSA-M lithium 12-hydroxystearate Chemical compound [Li+].CCCCCCC(O)CCCCCCCCCCC([O-])=O FPLIHVCWSXLMPX-UHFFFAOYSA-M 0.000 description 1
- 235000015250 liver sausages Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- PFXYQVJESZAMSV-UHFFFAOYSA-K zirconium(iii) chloride Chemical compound Cl[Zr](Cl)Cl PFXYQVJESZAMSV-UHFFFAOYSA-K 0.000 description 1
Classifications
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- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2201/10—Compounds containing silicon
- C10M2201/102—Silicates
- C10M2201/103—Clays; Mica; Zeolites
-
- 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
- C10M2201/10—Compounds containing silicon
- C10M2201/105—Silica
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
-
- 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
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/042—Metal salts thereof
-
- 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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/02—Unspecified siloxanes; Silicones
-
- 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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
-
- 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
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Form in which the lubricant is applied to the material being lubricated semi-solid; greasy
Definitions
- This invention relates to lubricating compositions. More particularly this invention relates to lubricating compositions containing a .minor quantity of certain metal Edi(hydrocarbyl) orthophosphates].
- The. -[di(hydrocarbyl) orthophosphates] employed in the. lubricating compositions of this invention can be represented by the generic formula wherein M is a metal of Group IVB of the Periodic Table, each Ris a hydrocarbon group and n is equal to the valence.;of1the metal M. Since the metal can be trivalent or tetravalent M can be 3 or 4. Preferably the metal is tetravalent and n is then 4.
- the metal can be titanium, zirconium 1'01 hafnium and preferably titanium.
- a suitable :Periodic Table can be found on page 314 of the Handbook of Chemistry and Physics, T wenty-ninth Edition (1945).
- hydrocarbyl simply referred to as hydrocarbyl herein, as represented each by R in the above generic formulae can be. one having from about 2 to about 30carbon atoms. Preferably each hydrocarbyl has from about .6 to about 20 carbon atoms.
- the hydrocarbon group can be aliphatic, cycloaliphatic or aromatic, e.g.
- alkyl alkenyl, phenyl, phenylalkyl, alkphenyl, cycloalkyl and the like.
- suitable hydrocarbon groups there can be mentioned those of isopropyl, butyl, isobutyl, tertiary butyl, Z-ethylhexyl, 3,4-diethyldodecyl, eicosyl, phenyl, ;4-octylphenyl, -n-butylphenyl, cycloh-exyl, 4-is-opropylcyclohexyl, oleyl, and the like.
- othrophosphate additives employed in this invention there can be mentioned; titanium tetra[di (isopropyl) orthophosphate]; zirconium tetra[di(3-butyloctyl) orthophosphate]; titanium tetra[di(2-ethyl-5-butyl tridecyl) orthophosphate]; zirconium tetra[di(2-propylethyl) orthophosphate];.
- each of the hydrocarbon groups of the orthophosphate should be soluble in the lubricant base at the concentrations employed.
- each of the hydrocarbon groups of the orthophosphate be branched chain alkyl, alkphenyl or phenalkyl, for example 2-ethylhexyl, 4-octylphenyl, or 8 phenyloctyl,
- the quantity of metal di(hydrocarbyl) orthophosphate in the lubricant compositions of this invention is in minor amounts such as that of from about 0.1% to about 5% by weight based on the weight of the lubricating composition and preferably from about 0.5% to about 3% by weight based on the weight of the lubricating composition.
- the orthophosphate additives of this invention may be prepared in any suitable manner.
- a suitable organic hydrogen orthophosphate e.g. di(oleyl) hydrogen orthophosphate, or a mixture of such phosphates is placed in a reaction flask together with about half its volume of a suitable solvent such as dry toluene.
- the reaction flask is preferably equipped with a mechanical stirrer, thermometer, gas inlet tube, reflux condenser and a pressure equalizing funnel with a long stem dipping into the solvent.
- the temperature of the reaction flask is raised to between about 110 C. to about 130 C.
- the tetrachloride is preferably introduced in amounts of about 1.1 moles of tetrachloride for each 4 moles of the organic hydrogen orthophos-p'hate.
- Hydrogen chloride is evolved copiously 'by the reaction. Stirring and heating under reflux to 130 C. is continued until evolution of hydrogen chloride stops. Removal of byproduct hydrogen chloride is promoted by flushing the reaction flask with dry nitrogen by means of the gas inlet tube. The solvent is removed by distillation and reduced pressure such as l080 millimeters, the final temperature being about 130 C.
- the yield of product can be between about to about of theory based on hydrogen orthophosphate reactant.
- the titanium or zirconium has a valence of 4.
- Similar compounds in which these metals have a valence of 3 may be prepared in a similar manner, e.g. by using titanium or zirconium trichloride rather than tetrachloride as a starting material and reacting the trichloride with about 3 moles of the organic hydrogen orthophosphate.
- a typical lubricating composition of this invention comprises a major portion of a mineral or synthetic base lubricant and a minor portion of a metal[di(hydrocarbyl) orthophosphate], suflicient to inhibit stick-slip tendencies,
- the lubricating compositions containing a lubricant base and the orthophosphate additive can be further improved to meet any desired lubricating requirement by incorporating therewith various other additives such as anti-oxidants, pour point depressants, viscosity index improvers, thickeners, soaps, and
- the solvent was removed by distillation at reduced pressure.
- the resulting solvent free crude product of titanium tetra[di(ethyhexyl) orthophosphate] was washed with water, taken up in half its volume of normal pentane, and then dried over anhydrous sodium sulphate. After filtering, the pentane was removed by distillation with the final temperature being 130 C. and 20 millimeters pressure.
- the yield of dark amber colored product was 1,900 grams or 95% of theory based on orthophosphate.
- the product has a viscosity at 100 F. of 1337 SUS and at 210 F. a viscosity of 180 SUS.
- the density of the product at 20 C. was 1.055.
- the titanium content of the compound was 3.59% and phosphorous content was 9.29%.
- EXAMPLE 2 Following the procedure of Example 1, but by substituting equal molecular quantities of di(4-octylphenyl) hydrogen orthophosphate for the di(2-ethylhexyl) hydrogen orthophosphate there was produced titanium tetra- [di(4-octylphenyl) orthophosphate]. Similarly there can be substituted equal molar quantities of zirconium tetrachloride or hafnium tetrachloride to prepare the corresponding zirconium or hafnium derivatives of the organic hydrogen orthophosphates.
- a suitable lubricating oil composition is prepared by dissolving one part, by weight, of titanium tetra[di(2- ethylhexyl) orthophosphate] into 99 parts by weight of 100 neutral mineral oil.
- EXAMPLE 4 A suitable grease composition is prepared by intimately admixing parts of lithium 12 hydroxystearate and 1 part of titanium tetra[di(2-ethylhexyl) orthophosphate] dissolved in 89 parts of 300 SUS at 100 F., of mineral oil. All parts given herein are on a weight basis.
- a lubricating composition comprising a major quantity of a lubricant base and minor quantity sufiicient to inhibit squawk of a metal [di(hydrocarbyl) orthophosphate] wherein the metal is a Group IVB metal of the periodic table and each hydrocarbyl group contains from about 2 to about 30 carbon atoms.
- a lubricating composition comprising a major quantity of a hydrocarbon lubricating oil and a minor quantity suflicient to inhibit squawk of a metal [di'(hydrocarbyl) orthophosphate] wherein the metal is a Group IVB metal of the periodic table and each hydrocarbyl group contains from about 2 to about 30 carbon atoms.
- composition of claim 2 Where the metal has a valence of 4 and each hydrocarbyl group is branched chain alkyl of from about 6 to about 20 carbon atoms.
- a lubricating composition comprising a major quantity of a hydrocarbon lubricating oil and from about 0.1% to about 5.0% by weight of the hydrocarbon lubricating oil of an orthophosphate of the formula M[OlO(OR) dissolved in said oil wherein M is a Group IVB metal of the periodic table, R is a hydrocarbon group of from 2 to about 30 carbon atoms and n is equal to the valence of the metal M.
- composition of claim 5 wherein each R is branched chain alkyl.
- a lubricating composition comprising a major quantity of a hydrocarbon lubricating oil and from about 0.1% to about 5.0% by weight of the hydrocarbon lubricating oil of an orthophosphate of the formula Ti[OPO(OR) dissolved in said oil, wherein each R is hydrocanbyl having from about 6 to about 20 carbon atoms.
- composition of claim 9 wherein each R is 2- ethylhexyl.
- composition of claim 9 wherein each R is 4- octylphenyl.
- a lubricating composition comprising a major quantity of a hydrocarbon lubricating oil and from about 0.1% to about 5.0% by weight of the hydrocarbon lubricating oil of an orthophosphate of the formula Zr[OPO(OR) dissolved in said oil, wherein each R is a hydrocarbon group having from about 6 to about 20 carbon atoms.
- composition of claim 14 wherein each R is branched chain alkyl and the quantity of ort-hophosphate is from about 0.5% to about 3%, based on the Weight of the hydrocarbon lubricating oil.
- composition of claim 15 wherein each R is 2- ethylhexyl.
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Description
. slip tendencies;
similar materials fail to eliminate stick-slip tendencies at high operating temperatures.
nited States Pate t.
LUBRICANTS CONTAINING .GRQUP IVB METAL PHOSPHATES George. M.1Hain, New Brunswick, and Anthony J. Revukas, Cranford, NJ, assignors to Cities Service Oil Company, a corporation of Delaware No Drawing. Filed Apr. -7, 1964-, Ser. No. 358,113 16 Claims. (Cl. 252-325) This invention relates to lubricating compositions. More particularly this invention relates to lubricating compositions containing a .minor quantity of certain metal Edi(hydrocarbyl) orthophosphates].
At slow vsliding speeds, heavily loaded surfaces lubricated with petroleum oils or other. lubricants have a tend encytotexhibit stick-slip phenonoma. In an automatic transmission for a limited slip diflerential application, this tendency manifests itself as a Squawk. On machine tool table carriages stick-slip is evidenced by violet chatter in. the table travel and in inaccuracy in positioning the machine elements.
The cause of stick-slip motion is due to the sharp changesgin the coefficient of friction with speed of the ad- When the static coeflicient of To inhibit or sperm oil as additives to petroleum oil in order to reduce the static coefficient of friction sufflciently to prevent stick- However, the sulfurized sperm oil and ltthastnow been found that a lubricating composition containing a major quantity of a lubricant base and a minor quantity of a [di(hydrocarbyl) orthophosphate] of a Group. IVB :metal of the Periodic Table inhibits stickslip tendencies over a wide range of loads, speeds and temperatures.
The. -[di(hydrocarbyl) orthophosphates] employed in the. lubricating compositions of this invention can be represented by the generic formula wherein M is a metal of Group IVB of the Periodic Table, each Ris a hydrocarbon group and n is equal to the valence.;of1the metal M. Since the metal can be trivalent or tetravalent M can be 3 or 4. Preferably the metal is tetravalent and n is then 4. The metal can be titanium, zirconium 1'01 hafnium and preferably titanium. A suitable :Periodic Table can be found on page 314 of the Handbook of Chemistry and Physics, T wenty-ninth Edition (1945).
The hydrocarbon group, simply referred to as hydrocarbyl herein, as represented each by R in the above generic formulae can be. one having from about 2 to about 30carbon atoms. Preferably each hydrocarbyl has from about .6 to about 20 carbon atoms. The hydrocarbon group can be aliphatic, cycloaliphatic or aromatic, e.g.
alkyl, alkenyl, phenyl, phenylalkyl, alkphenyl, cycloalkyl and the like. Illustrative of suitable hydrocarbon groups there can be mentioned those of isopropyl, butyl, isobutyl, tertiary butyl, Z-ethylhexyl, 3,4-diethyldodecyl, eicosyl, phenyl, ;4-octylphenyl, -n-butylphenyl, cycloh-exyl, 4-is-opropylcyclohexyl, oleyl, and the like.
Illustrative of the othrophosphate additives employed in this invention there can be mentioned; titanium tetra[di (isopropyl) orthophosphate]; zirconium tetra[di(3-butyloctyl) orthophosphate]; titanium tetra[di(2-ethyl-5-butyl tridecyl) orthophosphate]; zirconium tetra[di(2-propylethyl) orthophosphate];. titanium tetra[di(2,4-diethyloctyl) orthophosphate]; titanium tetra[di(2-methyloctyl) orthophosphate]; titanium tetra [bis(Z-methylpropyl-met-hylethyl) orthophosphate]; titanium IV[di(2*ethylhexyl) orthophosphate-di(isobutyl) orthophosphate-di(Z-methylnonyl) orthophosphate-di(3-butyloctyl) orthophosphate]; titanium tri[di(2-ethylhexyl) orthophosphate]; Zirconium tetra[di(2-ethylhexyl) orthophosphate]; Zirconium tri[(2- ethylhexyl-Z-methylpropyl) orthophosphate]; titanium tetra[di(octylphenyl) orthophosphate]; zirconium tetra- [di(methylphenyl) orthophosphate]; titanium tetra[di(tricosylphenyl) orthophosphate]; zirconium tetra [di(pentylphenyl) orthophosphate]; titanium tetra[octylphenyl pentylphenyl orthophosphate] zirconium tetra[ (2-ethylhexyl) methylphenyl orthophosphate]; zirconium tetra[di(octyl) orthophosphate]; and the like.
The metal [di(hydrocarbyl) orthophosphate] should be soluble in the lubricant base at the concentrations employed. For this purpose it is preferred that each of the hydrocarbon groups of the orthophosphate be branched chain alkyl, alkphenyl or phenalkyl, for example 2-ethylhexyl, 4-octylphenyl, or 8 phenyloctyl,
The quantity of metal di(hydrocarbyl) orthophosphate in the lubricant compositions of this invention is in minor amounts such as that of from about 0.1% to about 5% by weight based on the weight of the lubricating composition and preferably from about 0.5% to about 3% by weight based on the weight of the lubricating composition.
The orthophosphate additives of this invention may be prepared in any suitable manner. According to one method of preparation, a suitable organic hydrogen orthophosphate, e.g. di(oleyl) hydrogen orthophosphate, or a mixture of such phosphates is placed in a reaction flask together with about half its volume of a suitable solvent such as dry toluene. The reaction flask is preferably equipped with a mechanical stirrer, thermometer, gas inlet tube, reflux condenser and a pressure equalizing funnel with a long stem dipping into the solvent. The temperature of the reaction flask is raised to between about 110 C. to about 130 C. while stirring vigorously and titanium or zirconium tetrachloride with an equal volume of an organic solvent is added in spurts by means of the pressure equalizing delivery funnel. The tetrachloride is preferably introduced in amounts of about 1.1 moles of tetrachloride for each 4 moles of the organic hydrogen orthophos-p'hate. Hydrogen chloride is evolved copiously 'by the reaction. Stirring and heating under reflux to 130 C. is continued until evolution of hydrogen chloride stops. Removal of byproduct hydrogen chloride is promoted by flushing the reaction flask with dry nitrogen by means of the gas inlet tube. The solvent is removed by distillation and reduced pressure such as l080 millimeters, the final temperature being about 130 C. The yield of product can be between about to about of theory based on hydrogen orthophosphate reactant.
In the orthophosphate additives prepared as described hereinabove, the titanium or zirconium has a valence of 4. Similar compounds in which these metals have a valence of 3 may be prepared in a similar manner, e.g. by using titanium or zirconium trichloride rather than tetrachloride as a starting material and reacting the trichloride with about 3 moles of the organic hydrogen orthophosphate.
A typical lubricating composition of this invention comprises a major portion of a mineral or synthetic base lubricant and a minor portion of a metal[di(hydrocarbyl) orthophosphate], suflicient to inhibit stick-slip tendencies,
dissolved in the lubricant base. The lubricating compositions containing a lubricant base and the orthophosphate additive can be further improved to meet any desired lubricating requirement by incorporating therewith various other additives such as anti-oxidants, pour point depressants, viscosity index improvers, thickeners, soaps, and
Two-thousand grams of di(2-ethylhexyl) hydrogen orthophosphate (6 moles) Was placed in a reaction flask together with about 1 liter of dry toluene. The reaction flask was equipped with a mechanical stirrer, thermometer, gas inlet tube, reflux condenser and a pressure equalizing funnel with its long stem dipping into the solution. The temperature in the reaction flask was raised to about 120 C. while stirring vigorously and 330 grams (1.7 moles) of titanium tetrachloride dissolved in about 300 grams of toluene were added in spurts by means of the pressure equalizing delivery funnel to the orthophosphate. Hydrogen chloride was evolved copiously by the reaction. Stirring and heating under reflux to 130 C. was continued until evolution of hydrogen chlorides stopped. The solvent was removed by distillation at reduced pressure. The resulting solvent free crude product of titanium tetra[di(ethyhexyl) orthophosphate] was washed with water, taken up in half its volume of normal pentane, and then dried over anhydrous sodium sulphate. After filtering, the pentane was removed by distillation with the final temperature being 130 C. and 20 millimeters pressure. The yield of dark amber colored product was 1,900 grams or 95% of theory based on orthophosphate. The product has a viscosity at 100 F. of 1337 SUS and at 210 F. a viscosity of 180 SUS. The density of the product at 20 C. was 1.055. The titanium content of the compound was 3.59% and phosphorous content was 9.29%.
EXAMPLE 2 Following the procedure of Example 1, but by substituting equal molecular quantities of di(4-octylphenyl) hydrogen orthophosphate for the di(2-ethylhexyl) hydrogen orthophosphate there was produced titanium tetra- [di(4-octylphenyl) orthophosphate]. Similarly there can be substituted equal molar quantities of zirconium tetrachloride or hafnium tetrachloride to prepare the corresponding zirconium or hafnium derivatives of the organic hydrogen orthophosphates.
EXAMPLE 3 A suitable lubricating oil composition is prepared by dissolving one part, by weight, of titanium tetra[di(2- ethylhexyl) orthophosphate] into 99 parts by weight of 100 neutral mineral oil.
EXAMPLE 4 A suitable grease composition is prepared by intimately admixing parts of lithium 12 hydroxystearate and 1 part of titanium tetra[di(2-ethylhexyl) orthophosphate] dissolved in 89 parts of 300 SUS at 100 F., of mineral oil. All parts given herein are on a weight basis.
All percentage values given herein are on a weight basis unless otherwise indicated.
What is claimed is:
1. A lubricating composition comprising a major quantity of a lubricant base and minor quantity sufiicient to inhibit squawk of a metal [di(hydrocarbyl) orthophosphate] wherein the metal is a Group IVB metal of the periodic table and each hydrocarbyl group contains from about 2 to about 30 carbon atoms.
2. A lubricating composition comprising a major quantity of a hydrocarbon lubricating oil and a minor quantity suflicient to inhibit squawk of a metal [di'(hydrocarbyl) orthophosphate] wherein the metal is a Group IVB metal of the periodic table and each hydrocarbyl group contains from about 2 to about 30 carbon atoms.
3. A composition of claim 2 Where the metal has a valence of 4 and each hydrocarbyl group is branched chain alkyl of from about 6 to about 20 carbon atoms.
4. A lubricating composition comprising a major quantity of a hydrocarbon lubricating oil and from about 0.1% to about 5.0% by weight of the hydrocarbon lubricating oil of an orthophosphate of the formula M[OlO(OR) dissolved in said oil wherein M is a Group IVB metal of the periodic table, R is a hydrocarbon group of from 2 to about 30 carbon atoms and n is equal to the valence of the metal M.
5. A composition of claim 4 wherein n is 4 and each R has from about 6 to about 20 carbon atoms.
6. The composition of claim 5 wherein each R is branched chain alkyl.
'7. A composition of claim 5 wherein each R is phenalkyl.
8. A composition of claim 4 wherein each R is alkphenyl.
9. A lubricating composition comprising a major quantity of a hydrocarbon lubricating oil and from about 0.1% to about 5.0% by weight of the hydrocarbon lubricating oil of an orthophosphate of the formula Ti[OPO(OR) dissolved in said oil, wherein each R is hydrocanbyl having from about 6 to about 20 carbon atoms.
10. A composition of claim 9 wherein R is branched chain alkyl and the quantity of the orthophosphate is from about 0.5% to about 3%, based on the weight of the hydrocarbon lubricating oil.
11. A composition of claim 9 wherein R is alkphenyl and the quantity of orthophosphate is from about 0.5 to about 3%, based on the weight of the hydrocarbon lubricating oil.
12. A composition of claim 9 wherein each R is 2- ethylhexyl.
13. A composition of claim 9 wherein each R is 4- octylphenyl.
14. A lubricating composition comprising a major quantity of a hydrocarbon lubricating oil and from about 0.1% to about 5.0% by weight of the hydrocarbon lubricating oil of an orthophosphate of the formula Zr[OPO(OR) dissolved in said oil, wherein each R is a hydrocarbon group having from about 6 to about 20 carbon atoms.
15. A composition of claim 14 wherein each R is branched chain alkyl and the quantity of ort-hophosphate is from about 0.5% to about 3%, based on the Weight of the hydrocarbon lubricating oil.
16. A composition of claim 15 wherein each R is 2- ethylhexyl.
References Cited by the Examiner UNITED STATES PATENTS 2,274,302 2/1942 Mulit 252-32.5 2,370,080 2/1945 Schreiber 25232.5 X 3,017,361 1/1962 Morris et a1 252- X 3,175,976 3/1965 Foehr 25275 DANIEL E. WYMAN, Primary Examiner. P. P. GARVIN, Assistant Examiner.
Claims (1)
1. A LUBRICATING COMPOSITION COMPRISING A MAJOR QUANTITY OF A LUBRICANT BASE AND MINOR QUANTITY SUFFICIENT TO INHIBIT SQUAWK OF A-METAL (DI(HYDROCARBYL) ORTHOPHOSPHATE) WHEREIN THE METAL IS A GROUP IVB METAL OF THE PERIODIC TABLE AND EACH HYDROCARBYL GROUP CONTAINS FROM ABOUT 2 TO ABOUT 30 CARBON ATOMS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US358113A US3297573A (en) | 1964-04-07 | 1964-04-07 | Lubricants containing group ivb metal phosphates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US358113A US3297573A (en) | 1964-04-07 | 1964-04-07 | Lubricants containing group ivb metal phosphates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3297573A true US3297573A (en) | 1967-01-10 |
Family
ID=23408361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US358113A Expired - Lifetime US3297573A (en) | 1964-04-07 | 1964-04-07 | Lubricants containing group ivb metal phosphates |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3297573A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3389082A (en) * | 1964-03-06 | 1968-06-18 | Cities Service Oil Co | Lubricating composition |
| US6153564A (en) * | 1998-06-17 | 2000-11-28 | Infineum Usa L.P. | Lubricating oil compositions |
| JP2002302691A (en) * | 2001-02-02 | 2002-10-18 | Nippon Oil Corp | Lubricating oil composition |
| US6730640B2 (en) * | 2000-10-23 | 2004-05-04 | The Lubrizol Corporation | Method for lubricating a continuously variable transmission |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2274302A (en) * | 1940-01-22 | 1942-02-24 | Standard Oil Co | Compounded oil |
| US2370080A (en) * | 1943-02-03 | 1945-02-20 | Atlantic Refining Co | Stabilized lubricant composition |
| US3017361A (en) * | 1956-09-05 | 1962-01-16 | Texaco Inc | Non-squawking automatic transmission fluid |
| US3175976A (en) * | 1965-03-30 | Automatic transmission fluids |
-
1964
- 1964-04-07 US US358113A patent/US3297573A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3175976A (en) * | 1965-03-30 | Automatic transmission fluids | ||
| US2274302A (en) * | 1940-01-22 | 1942-02-24 | Standard Oil Co | Compounded oil |
| US2370080A (en) * | 1943-02-03 | 1945-02-20 | Atlantic Refining Co | Stabilized lubricant composition |
| US3017361A (en) * | 1956-09-05 | 1962-01-16 | Texaco Inc | Non-squawking automatic transmission fluid |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3389082A (en) * | 1964-03-06 | 1968-06-18 | Cities Service Oil Co | Lubricating composition |
| US3388978A (en) * | 1964-03-06 | 1968-06-18 | Cities Service Oil Co | Hydrocarbon fuel composition |
| US6153564A (en) * | 1998-06-17 | 2000-11-28 | Infineum Usa L.P. | Lubricating oil compositions |
| US6730640B2 (en) * | 2000-10-23 | 2004-05-04 | The Lubrizol Corporation | Method for lubricating a continuously variable transmission |
| JP2002302691A (en) * | 2001-02-02 | 2002-10-18 | Nippon Oil Corp | Lubricating oil composition |
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Legal Events
| Date | Code | Title | Description |
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| AS | Assignment |
Owner name: CITGO PETROLEUM CORPORATION, A CORP OF DE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:CITIES SERVICE COMPANY;REEL/FRAME:004225/0709 Effective date: 19830830 |
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| AS | Assignment |
Owner name: CITIES SERVICE COMPANY A CORP. OF DE. Free format text: MERGER;ASSIGNOR:CITIES SERVICE OIL COMPANY;REEL/FRAME:004561/0817 Effective date: 19781220 |