US3558490A - Styryl phosphorodithioate esters to be used as antioxidants in lubricating oil - Google Patents
Styryl phosphorodithioate esters to be used as antioxidants in lubricating oil Download PDFInfo
- Publication number
- US3558490A US3558490A US733310A US3558490DA US3558490A US 3558490 A US3558490 A US 3558490A US 733310 A US733310 A US 733310A US 3558490D A US3558490D A US 3558490DA US 3558490 A US3558490 A US 3558490A
- Authority
- US
- United States
- Prior art keywords
- carbon atoms
- lubricating oil
- antioxidants
- styryl
- oil
- 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.)
- Expired - Lifetime
Links
- 239000010687 lubricating oil Substances 0.000 title abstract description 22
- 239000003963 antioxidant agent Substances 0.000 title abstract description 7
- -1 Styryl phosphorodithioate esters Chemical class 0.000 title description 7
- 239000002253 acid Substances 0.000 abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- 239000003921 oil Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 11
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 11
- 239000002199 base oil Substances 0.000 description 7
- 229920000768 polyamine Polymers 0.000 description 7
- 125000002947 alkylene group Chemical group 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 125000005037 alkyl phenyl group Chemical group 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001281 polyalkylene Polymers 0.000 description 3
- QLRRUWXMMVXORS-UHFFFAOYSA-N Augustine Natural products C12=CC=3OCOC=3C=C2CN2C3CC(OC)C4OC4C31CC2 QLRRUWXMMVXORS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-K dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [O-]P([O-])([S-])=S NAGJZTKCGNOGPW-UHFFFAOYSA-K 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical group [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000015241 bacon Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- UPCIBFUJJLCOQG-UHFFFAOYSA-L ethyl-[2-[2-[ethyl(dimethyl)azaniumyl]ethyl-methylamino]ethyl]-dimethylazanium;dibromide Chemical compound [Br-].[Br-].CC[N+](C)(C)CCN(C)CC[N+](C)(C)CC UPCIBFUJJLCOQG-UHFFFAOYSA-L 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
- C10M137/105—Thio derivatives not containing metal
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/18—Esters of thiophosphoric acids with hydroxyaryl 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/06—Well-defined aromatic 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
- 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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
-
- 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
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/142—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings polycarboxylic
-
- 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
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/044—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms having cycloaliphatic 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
-
- 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
- C10M2215/08—Amides
-
- 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
- C10M2215/08—Amides
- C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/086—Imides
-
- 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
- C10M2215/12—Partial amides of polycarboxylic 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/14—Containing carbon-to-nitrogen double bounds, e.g. guanidines, hydrazones, semicarbazones
-
- 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
- C10M2215/22—Heterocyclic nitrogen 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
- C10M2215/222—Triazines
-
- 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
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
- C10M2215/224—Imidazoles
-
- 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
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
-
- 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
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
- C10M2215/226—Morpholines
-
- 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
- C10M2215/26—Amines
-
- 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
- C10M2215/28—Amides; Imides
-
- 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
- C10M2215/30—Heterocyclic 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
- 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
- C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
-
- 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
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/047—Thioderivatives not containing metallic elements
Definitions
- R is alkyl of from 10 to 18 carbon atoms, having an average number of carbon atoms in the range of 12 to 15, preferably a branched chain alkyl, wherein any a branch is of from 1 to 2 carbon atoms, preferably 1 carbon atom (methyl), there being at least 1 branch every 4 carbon atoms along the chain; ,1) is phenyl, and Y is hydrogen or lower alkyl of from 1 to 3 carbon atoms, preferably hydrogen or methyl.
- Illustrative groups bonded to sulfur are u-phenylethyl, 2-phenyl-2-propyl, 2-phenyl2-butyl, etc.
- Illustrative alkyl groups bonded to the phenyl which is bonded to oxygen are polypropenyl, polyisobutenyl, etc.
- the phosphorodithioate esters used in this invention are readily prepared by first preparing the 0,0-di-substituted dithiophosphoric acid and reacting the acid at an elevated temperature with the desired olefin.
- the temperature will generally be in the range of about 50 to 125 C., more usually from to C.
- the reaction is carried out in the absence of air or other free radical initiator.
- the lubricating oils in which the phosphorodithioic acid esters are used may be derived from natural or synthetic sources. Lubricating oils generally have viscosities of from about 35 to 50,000 Saybolt Universal Seconds (SUS) at 100 F.
- hydrocarbonaceous oils are parafiinic base, naphthenic base, asphaltic base and mixed base oils.
- Illustrative synthetic hydrocarbonaceous oils are polymers of various olefins, generally of from 2 to 8 carbon atoms, and alkylated aromatic hydrocarbons.
- the phosphorodithioic acid esters are preferably compounded with from 1 to 15 weight percent of a polyalkylene polyamine lubricating oil detergent.
- the polyalkylene polyamines will generally have from 2 to 6 nitrogen atoms and alkylene groups of from 2 to 3 atoms. Bonded to the alkylene polyamines will generally be from 1 to 2 oil soluble aliphatic hydrocarbon groups, usually a polymer of olefins of from 3 to 4 carbon atoms (propene and isobutylene).
- the hydrocarbon groups are bonded to the alkylene polyamine directly to nitrogen or through a nonoxocarbonyl group such as forrnyl or succinoyl.
- the aliphatic hydrocarbon group Will generally be of from 30 to 200 carbon atoms, more usually of from 50 to carbon atoms.
- additives may also be present, such as antirust agents, corrosion inhibitors, other detergents, additional oxidation inhibitors, oiliness agents, etc.
- the phosphorodithioic acid esters will generally be present in from 1 to 500 mm./ kg. of lubricating oil composition, more usually from about 5 to 50 mm./ kg. Above 100 mm./kg., the composition will be as a concentrate for dilution in use.
- the other additives will generally be present individually in from about 0.01 to 15 weight percent, more usually from about 0.05 to 10 weight percent.
- the alkylene polyamine detergent Will usually be present in from 2 to 15 weight percent.
- Example 0,0-di(alkylphenyl) phosphorodithioic acid (alkyl is polypropenyl of from 12 to 15 carbon atoms) was stirred, after flushing with nitrogen, at 150 F. for 2 hrs. in vacuo, followed by filtering through Celite.
- Into a 1-liter 3-necked flask equipped with stirrer, heating mantle, thermometer, addition funnel and water condenser was charged 820 g. (0.77 mole) of the acid described above. While stirring the acid at room temperature, 84 g. (0.8 mole) of styrene was slowly added, the temperature rising during the addition but being kept below about 170 F. While maintaining a nitrogen atmosphere, the mixture was stirred at 200 F. for 8 hrs. and then stripped while raising the pot temperature to 250 F. and reducing the pressure to about 2.5 mm. Hg. The residue was filtered through Celite.
- Compounded oils were prepared and tested in the L-38 Engine Test using a l-cylinder CLR engine. The test is carried out for 40 hrs. with an engine speed of 3,150 r.p.m. The results are reported in bearing weight loss for a copper-lead bearing and also the percent viscosity increase determined at 100 F. as SUS. The following table indicates the results obtained.
- A-s arprhenylethyl 0,0 di(alkylphenyl) phosphorodithioate alkyl 1s polypropenyl of 12 to 15 carbon atoms.
- the oil solution to be tested is maintained at 340 F. until 250 ml. of oxygen is absorbed.
- the results are reported as if a 100 g. sample was used and as the number of hours necessary to absorb 1 liter of oxygen.
- the lubricating oil was tested under extreme conditions in a test referred to as the 240 BMEP Caterpillar Engine Test (brake mean effective pressure).
- the conditions are for a supercharged Caterpillar test, wherein the pressure of the supercharged air is 76.5 in. Hg. abs., the water temperature of the cooling jacket is 200 F.-, the air temperature is F., the oil temperature at the bearing is F., the sulfur content of the fuel is 0.4 Weight percent, the speed of the engine is 1,200 r.p.m., and the rate of fuel input is at a rate which provides 6,900 B.t.u./min.
- the test was carried out for 60' hrs. using compounded oils. The following table indicates the results:
- the base oil was a Mid-Continent SAE 30 oil containing 6.25 wt. A, of polyisobutenyl succinimide of tetracthylcnc pentaminc (polyisobutw nyl of 1,000 average moi. weight; the amine is a mixture having the average composition of tetraethyleno pentaininu), and 0.1 weight percent tercphthalio acid.
- the styryl ester of the alkylphenyl phosphorodithioate esters provides excellent protection against oxidation of the oil as well as against wear under extremely severe conditions.
- the ester is frequently as good or superior to the metal salt analogs, yet avoids deposits caused by the presence of metal ions, such as zinc.
- Lubricating oil compositions containing in an effective amount to inhibit oxidation and prevent wear, a composition of the formula:
- JHS wherein R is alkyl of from 10 to 18 carbon atoms, having an average number of carbon atoms in the range of 12 to 15, is phenyl and Y is hydrogen or lower alkyl of from 1 to 3 carbon atoms.
- a lubricating oil composition according to claim 1 having from 2 to 15 weight percent of an alkylene polyamine of from 2 to 6 nitrogen atoms, wherein the alkylene groups are of from 2 to 3 carbon atoms, having bonded to nitrogen from 1 to 2 oil soluble aliphatic hydrocarbon groups of from 30 to 200 carbon atoms, wherein References Cited UNITED STATES PATENTS 2,665,295 1/ 1954 Augustine 260-958 2,589,675 3/1952 Cook et a1 252-466 2,627,523 2/1953 Hook et a1 25246.6
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Abstract
STYRYL ESTER OF O,O-DI(ALKYLPHENYL) PHOSPHORODITHIC ACID ARE PROVIDED AS ANTIWEAR AND ANTIOXIDANT AGENTS FOR HIGH TEMPERATURE SURFACE IN LUBRICATING OILS.
Description
Patented Jan. 26, 1971 sTYavrQPHosPnoRonnmoATE ESTERS TO BE USED AS ANTIOXIDANTS IN LUBRICATING OIL Warren Lowe, El Cerrito, Califl, assignor to Chevron Research Company, San Francisco, Calif., a corporation of Delaware No Drawing. Filed May 31, 1968, Ser. N0. 733,310 Int. Cl. Cm 1/48, 3/42 US. Cl. 25246.6 6 Claims ABSTRACT OF THE DISCLOSURE Styryl esters of 0,0-di(alkylphenyl) phosphorodithioic acid are provided as antiwear and antioxidant agents for high temperature surfaces in lubricating oils.
BACKGROUND OF THE INVENTION Field of the invention In lubricating oils, particularly ash-free or low ash lubricating oils, used in internal combustion engines, it is common to add antioxidant and antiwear agents. Particularly common additives are the zinc salts of various phosphorodithioic acid esters. However, there have been continual efforts to reduce the amount of metal, as their ions, in lubricating oils. The metals during service frequently enhance deposit formation.
Description of the prior art SUMMARY OF THE INVENTION S-wphenylethyl 0,0-di(alkylphenyl) phosphorodithioates, wherein the alkyl group is of from 10 to 18 carbon atoms, having an average of from 12 to 15 carbon atoms, are used in lubricating oils as antioxidants and antiwear agents, particularly for high temperature service in internal combustion engines, e.g., diesel engines.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The phosphorodithioic acid esters which find use in the lubricating oils of this invention have the following formula:
wherein R is alkyl of from 10 to 18 carbon atoms, having an average number of carbon atoms in the range of 12 to 15, preferably a branched chain alkyl, wherein any a branch is of from 1 to 2 carbon atoms, preferably 1 carbon atom (methyl), there being at least 1 branch every 4 carbon atoms along the chain; ,1) is phenyl, and Y is hydrogen or lower alkyl of from 1 to 3 carbon atoms, preferably hydrogen or methyl.
Illustrative groups bonded to sulfur are u-phenylethyl, 2-phenyl-2-propyl, 2-phenyl2-butyl, etc. Illustrative alkyl groups bonded to the phenyl which is bonded to oxygen are polypropenyl, polyisobutenyl, etc.
The phosphorodithioate esters used in this invention are readily prepared by first preparing the 0,0-di-substituted dithiophosphoric acid and reacting the acid at an elevated temperature with the desired olefin. The temperature will generally be in the range of about 50 to 125 C., more usually from to C. The reaction is carried out in the absence of air or other free radical initiator.
The lubricating oils in which the phosphorodithioic acid esters are used may be derived from natural or synthetic sources. Lubricating oils generally have viscosities of from about 35 to 50,000 Saybolt Universal Seconds (SUS) at 100 F.
Among natural hydrocarbonaceous oils are parafiinic base, naphthenic base, asphaltic base and mixed base oils. Illustrative synthetic hydrocarbonaceous oils are polymers of various olefins, generally of from 2 to 8 carbon atoms, and alkylated aromatic hydrocarbons.
The phosphorodithioic acid esters are preferably compounded with from 1 to 15 weight percent of a polyalkylene polyamine lubricating oil detergent. The polyalkylene polyamines will generally have from 2 to 6 nitrogen atoms and alkylene groups of from 2 to 3 atoms. Bonded to the alkylene polyamines will generally be from 1 to 2 oil soluble aliphatic hydrocarbon groups, usually a polymer of olefins of from 3 to 4 carbon atoms (propene and isobutylene). The hydrocarbon groups are bonded to the alkylene polyamine directly to nitrogen or through a nonoxocarbonyl group such as forrnyl or succinoyl. The aliphatic hydrocarbon group Will generally be of from 30 to 200 carbon atoms, more usually of from 50 to carbon atoms.
Illustrative polyalkylene polyamine detergents are found in US. Pats. Nos. 3,219,666, 3,275,554 and 3,087,686.
Other additives may also be present, such as antirust agents, corrosion inhibitors, other detergents, additional oxidation inhibitors, oiliness agents, etc.
The phosphorodithioic acid esters will generally be present in from 1 to 500 mm./ kg. of lubricating oil composition, more usually from about 5 to 50 mm./ kg. Above 100 mm./kg., the composition will be as a concentrate for dilution in use.
The other additives will generally be present individually in from about 0.01 to 15 weight percent, more usually from about 0.05 to 10 weight percent. The alkylene polyamine detergent Will usually be present in from 2 to 15 weight percent.
The following example is offered by way of illustration and not by way of limitation.
Example 0,0-di(alkylphenyl) phosphorodithioic acid (alkyl is polypropenyl of from 12 to 15 carbon atoms) was stirred, after flushing with nitrogen, at 150 F. for 2 hrs. in vacuo, followed by filtering through Celite. Into a 1-liter 3-necked flask equipped with stirrer, heating mantle, thermometer, addition funnel and water condenser was charged 820 g. (0.77 mole) of the acid described above. While stirring the acid at room temperature, 84 g. (0.8 mole) of styrene was slowly added, the temperature rising during the addition but being kept below about 170 F. While maintaining a nitrogen atmosphere, the mixture was stirred at 200 F. for 8 hrs. and then stripped while raising the pot temperature to 250 F. and reducing the pressure to about 2.5 mm. Hg. The residue was filtered through Celite.
Analysis-Percent: P, 2.8; acid No., 2.2 mg. KOH/g.
In order to demonstrate the excellent effectiveness of the phosphorodithioic acid esters utilized in the lubricating oils of this invention, a number of industry-recognized tests were performed.
Compounded oils were prepared and tested in the L-38 Engine Test using a l-cylinder CLR engine. The test is carried out for 40 hrs. with an engine speed of 3,150 r.p.m. The results are reported in bearing weight loss for a copper-lead bearing and also the percent viscosity increase determined at 100 F. as SUS. The following table indicates the results obtained.
TABLE I.L38 ENGINE TEST, 40 HOURS Phcsphoro- Viscosity dithioic 2 Cu-Pb increase Detergent, acid ester, bearing at 100 F., wt. percent n1ni./kg. loss, mg. percent To demonstrate the effectiveness of the lubricating oils under extreme pressure conditions, the oils were tested in the Falex Shear Test. The results are reported as load at failure in pounds.
TABLE II.FALEX SHEAR TEST Load at failure,
Formulation: lbs. Base oil 1 850 Base oil+18 mm./kg. A 2 1,475
480 neutral oil+ wt. percent polyis'obrrtenyl suecinirnide of tctraethylene pentamine (polyisobutenyl -1,000 mol. wt.) and 0.1 Wt. percent terephthalic acid (corrosion inhibitor).
A-s arprhenylethyl 0,0 di(alkylphenyl) phosphorodithioate (alkyl 1s polypropenyl of 12 to 15 carbon atoms).
To demonstrate the effectiveness of the subject additives as antioxidants in lubricating oil compositions, comparison compositions were tested in the Oxidator B Test. In this test, a 25 g. sample is prepared from 480 neutral oil containing the phosphorodithioic acid ester and various other additives normally compounded in a lubricating oil for internal combustion engines. To the 25 g. sample is added 0.2 cc. of a solution having 3,160 p.p.m. of copper, 2,670 p.p.m. of iron, 160 p.p.m. of manganese, 36,700 p.p.m. of lead and 1,630 p.p.m. of tin as their naphthenates. This is considered to be the distribution of metals which would be expected to be found in used crankcase oils after an L-4 Chevrolet Engine Test.
The oil solution to be tested is maintained at 340 F. until 250 ml. of oxygen is absorbed. The results are reported as if a 100 g. sample was used and as the number of hours necessary to absorb 1 liter of oxygen.
4 TABLE III.OXIDATOR B TEST Hrs. to absorb one liter of 0 Base oil +18 mm./kg. of A 2 9.4 Compounded base oil 3 +18 mm./kg. of A 1- 8.7 Base oil -1.0
1 480 Neutral oil. 2 See Table II for definition,
3 480 neutral 0i1+5% of the succinimide described in Table II and 0.1% terephthalic acid.
Finally, the lubricating oil was tested under extreme conditions in a test referred to as the 240 BMEP Caterpillar Engine Test (brake mean effective pressure). The conditions are for a supercharged Caterpillar test, wherein the pressure of the supercharged air is 76.5 in. Hg. abs., the water temperature of the cooling jacket is 200 F.-, the air temperature is F., the oil temperature at the bearing is F., the sulfur content of the fuel is 0.4 Weight percent, the speed of the engine is 1,200 r.p.m., and the rate of fuel input is at a rate which provides 6,900 B.t.u./min. The test was carried out for 60' hrs. using compounded oils. The following table indicates the results:
TABLE IV.240 BMEP CAllfggtgLLAR ENGINE TESIX G O Formulation 1 1 The base oil was a Mid-Continent SAE 30 oil containing 6.25 wt. A, of polyisobutenyl succinimide of tetracthylcnc pentaminc (polyisobutw nyl of 1,000 average moi. weight; the amine is a mixture having the average composition of tetraethyleno pentaininu), and 0.1 weight percent tercphthalio acid.
2 ASee Table II for definition; BZinc-0,0-di(alkylphenyl) phosphorodithioate (alkyl is polypropenyl of 1215 carbon atoms).
3 Groove deposits rated on the basis of 0-100, 100 being completely filled grooves. Land deposits rated on the basis of 0-800, 800 being completely black. Underhead deposits rated on the basis of 0-10, 10 being completely clean.
It is evident from the above results that the styryl ester of the alkylphenyl phosphorodithioate esters provides excellent protection against oxidation of the oil as well as against wear under extremely severe conditions. The ester is frequently as good or superior to the metal salt analogs, yet avoids deposits caused by the presence of metal ions, such as zinc.
As will be evident to those skilled in the art, various modifications of this invention can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.
I claim:
1. Lubricating oil compositions containing in an effective amount to inhibit oxidation and prevent wear, a composition of the formula:
( JHS wherein R is alkyl of from 10 to 18 carbon atoms, having an average number of carbon atoms in the range of 12 to 15, is phenyl and Y is hydrogen or lower alkyl of from 1 to 3 carbon atoms.
2. A lubricating oil composition according to claim 1, wherein Y is hydrogen and R is branched alkyl.
3. A lubricating oil composition according to claim 2, wherein R is polypropenyl.
4. A lubricating oil composition according to claim 1 having from 2 to 15 weight percent of an alkylene polyamine of from 2 to 6 nitrogen atoms, wherein the alkylene groups are of from 2 to 3 carbon atoms, having bonded to nitrogen from 1 to 2 oil soluble aliphatic hydrocarbon groups of from 30 to 200 carbon atoms, wherein References Cited UNITED STATES PATENTS 2,665,295 1/ 1954 Augustine 260-958 2,589,675 3/1952 Cook et a1 252-466 2,627,523 2/1953 Hook et a1 25246.6
DANIEL E.
6 Hook et a1 252-400 Augustine 252-958 Crosby et a1 252-466 Bacon 260-978 Thompson 252-46.6 LeSuer 252-466 Wagenaar 252-50 WYMAN, Primary Examiner 10 J. M. HICKEY, Assistant Examiner US. Cl. X.R.
Patent No.
UNITED STATES PATENT OFFICE Dated January 26 1971 Inventor(s) (SEAL) Attest:
Attesting Officer EDWARD M.FLETCHER,JR.
Warren Lowe It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1 and Column 4 in the formulae Signed and sealed this 15th day of June 1971 WILLIAM E. SCHUYLER, J] Commissioner of Patent:
; FORM PO-105O (IO-69]
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US73331068A | 1968-05-31 | 1968-05-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3558490A true US3558490A (en) | 1971-01-26 |
Family
ID=24947084
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US733310A Expired - Lifetime US3558490A (en) | 1968-05-31 | 1968-05-31 | Styryl phosphorodithioate esters to be used as antioxidants in lubricating oil |
Country Status (1)
Country | Link |
---|---|
US (1) | US3558490A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4152275A (en) * | 1977-12-23 | 1979-05-01 | Mobil Oil Corporation | Sulfurized olefin adducts of phosphorodithioic acids and organic compositions containing same |
US4153562A (en) * | 1977-12-23 | 1979-05-08 | Exxon Research & Engineering Co. | Antioxidants for low ash and medium ash lubricating oils |
US20050148476A1 (en) * | 2004-01-07 | 2005-07-07 | The Lubrizol Corporation | Automatic transmission fluids with phthalic acid corrosion inhibitor |
US20090005478A1 (en) * | 2007-02-26 | 2009-01-01 | Gelbin Michael E | Liquid styrenated phenolic compositions and processes for forming same |
US20090011961A1 (en) * | 2007-07-06 | 2009-01-08 | Jun Dong | Lubricant compositions stabilized with styrenated phenolic antioxidant |
-
1968
- 1968-05-31 US US733310A patent/US3558490A/en not_active Expired - Lifetime
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4152275A (en) * | 1977-12-23 | 1979-05-01 | Mobil Oil Corporation | Sulfurized olefin adducts of phosphorodithioic acids and organic compositions containing same |
US4153562A (en) * | 1977-12-23 | 1979-05-08 | Exxon Research & Engineering Co. | Antioxidants for low ash and medium ash lubricating oils |
US20050148476A1 (en) * | 2004-01-07 | 2005-07-07 | The Lubrizol Corporation | Automatic transmission fluids with phthalic acid corrosion inhibitor |
WO2005068591A1 (en) * | 2004-01-07 | 2005-07-28 | The Lubrizol Corporation | Automatic transmission fluids with phthalic acid corrosion inhibitor |
JP2007517963A (en) * | 2004-01-07 | 2007-07-05 | ザ ルブリゾル コーポレイション | Fluid for automatic transmission with phthalic acid corrosion inhibitor |
US7429554B2 (en) | 2004-01-07 | 2008-09-30 | The Lubrizol Corporation | Automatic transmission fluids with phthalic acid corrosion inhibitor |
JP4938461B2 (en) * | 2004-01-07 | 2012-05-23 | ザ ルブリゾル コーポレイション | Fluid for automatic transmission with phthalic acid corrosion inhibitor |
US20090005478A1 (en) * | 2007-02-26 | 2009-01-01 | Gelbin Michael E | Liquid styrenated phenolic compositions and processes for forming same |
US7902280B2 (en) | 2007-02-26 | 2011-03-08 | Chemtura Corporation | Liquid styrenated phenolic compositions and processes for forming same |
US20090011961A1 (en) * | 2007-07-06 | 2009-01-08 | Jun Dong | Lubricant compositions stabilized with styrenated phenolic antioxidant |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3185647A (en) | Lubricant composition | |
US3184411A (en) | Lubricants for reducing corrosion | |
US3876550A (en) | Lubricant compositions | |
US2795553A (en) | Lubricant compositions | |
US3634493A (en) | Oil-soluble azo compounds | |
US3224975A (en) | Lubricating oil compositions | |
US2599761A (en) | Extreme pressure lubricant | |
US3224968A (en) | Lubricating oil compositions | |
US3666662A (en) | Alkali metal succinamate compositions for lubricating oils | |
US3808131A (en) | Coordinated metal complexes in lubricating oils and hydrocarbon fuels | |
US3844960A (en) | Lubricant compositions | |
US3558490A (en) | Styryl phosphorodithioate esters to be used as antioxidants in lubricating oil | |
US2796404A (en) | Extreme pressure lubricant compositions | |
US3337654A (en) | Oxyalkylenated hydroxyhydrocarbon thiophosphates | |
US3505227A (en) | Lubricating oil compositions containing bis-alkenyl succinimides of xylylene diamines | |
US3184412A (en) | Lubricants inhibited against oxidation | |
US3296137A (en) | Lubricants containing aldehydohydrocarbon sulfides | |
US4118328A (en) | Amine phosphate salts | |
US3537999A (en) | Lubricants containing benzothiadiazole | |
US2713557A (en) | Basic phenates to inhibit silver corrosion in thiophosphate-containing lubricating oils | |
US4118329A (en) | Amine phosphate salts and phosphoramides | |
US3846318A (en) | Antioxidant and extreme pressure lubricating oil additive | |
US2599341A (en) | New phosphorus containing compounds | |
US3185646A (en) | Corrosion inhibited lubricants | |
US3813336A (en) | Reaction products of amines and dithiophosphoric acids or salts |