US3135692A - Oxidation resistant lubricant - Google Patents
Oxidation resistant lubricant Download PDFInfo
- Publication number
- US3135692A US3135692A US585981A US58598156A US3135692A US 3135692 A US3135692 A US 3135692A US 585981 A US585981 A US 585981A US 58598156 A US58598156 A US 58598156A US 3135692 A US3135692 A US 3135692A
- Authority
- US
- United States
- Prior art keywords
- oil
- sulfide
- barium
- reaction
- phenol
- 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
- 239000000314 lubricant Substances 0.000 title description 8
- 230000003647 oxidation Effects 0.000 title description 4
- 238000007254 oxidation reaction Methods 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims description 35
- -1 DITHIOPHOSPHORIC ACID DIESTERS Chemical class 0.000 claims description 26
- VCIDTZZDPJYIQQ-UHFFFAOYSA-N C12(C(C=CC=C1)S2)O.[Ba] Chemical compound C12(C(C=CC=C1)S2)O.[Ba] VCIDTZZDPJYIQQ-UHFFFAOYSA-N 0.000 claims description 25
- 239000003921 oil Substances 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 20
- 239000007795 chemical reaction product Substances 0.000 claims description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims description 20
- 239000011574 phosphorus Substances 0.000 claims description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims description 17
- 229910052788 barium Inorganic materials 0.000 claims description 15
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 15
- 239000010687 lubricating oil Substances 0.000 claims description 13
- 239000003208 petroleum Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 239000010688 mineral lubricating oil Substances 0.000 claims description 3
- 239000002195 soluble material Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 description 17
- 239000000654 additive Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000003460 sulfonic acids Chemical class 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 239000002480 mineral oil Substances 0.000 description 7
- 235000010446 mineral oil Nutrition 0.000 description 7
- WYLGULQOXHDWBD-UHFFFAOYSA-N barium;phenol Chemical compound [Ba].OC1=CC=CC=C1 WYLGULQOXHDWBD-UHFFFAOYSA-N 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 235000008504 concentrate Nutrition 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000005690 diesters Chemical class 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000158728 Meliaceae Species 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000001050 lubricating effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 159000000009 barium salts Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000000913 palmityl 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])[H] 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical group CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- CBQDTCDOVVBGMN-UHFFFAOYSA-N 2-methyl-3-octylphenol Chemical compound CCCCCCCCC1=CC=CC(O)=C1C CBQDTCDOVVBGMN-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- VMWWFBNLJBGUGJ-UHFFFAOYSA-N 4,6-dipentyl-7-thiabicyclo[4.1.0]hepta-2,4-dien-1-ol Chemical compound C(CCCC)C12C(C=CC(=C1)CCCCC)(O)S2 VMWWFBNLJBGUGJ-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- LJKQIQSBHFNMDV-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-2,4-dien-6-ol Chemical class C1=CC=CC2(O)C1S2 LJKQIQSBHFNMDV-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 208000035859 Drug effect increased Diseases 0.000 description 1
- 101100379081 Emericella variicolor andC gene Proteins 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- NRZWYNLTFLDQQX-UHFFFAOYSA-N p-tert-Amylphenol Chemical compound CCC(C)(C)C1=CC=C(O)C=C1 NRZWYNLTFLDQQX-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 1
- 125000002948 undecyl 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])[H] 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
- 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
- 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
- C07F9/04—Reaction products of phosphorus sulfur compounds with hydrocarbons
-
- 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
- C10M2201/04—Elements
- C10M2201/043—Sulfur; Selenenium; Tellurium
-
- 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
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
-
- 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
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
-
- 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
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/088—Neutral salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/089—Overbased salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/12—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
-
- 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
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the 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
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
- C10M2225/041—Hydrocarbon polymers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
Definitions
- the present invention relates to mineral oil ompositions and more particularly to the use of novel additives to impart anti-oxidant and detergent properties to lubricating oils.
- the metal derivatives of organic compounds are among the most Widely used additive agents to improve the detergent properties of a lubricating oil.
- these detergent additives perform satisfactorily in dispersing sludge and preventing lacquer deposits, many of these additives, particularly under extreme operating conditions, increase the rate of oxidation of the oil and effect increased concentrations of acidic oxidation products which thus increase the rate of corrosion to the bearings, pistons, valves and the like.
- novel detergent-antioxidant lubricating oil additives of this invention can be employed in amounts varying over a considerable range depending upon the intended purpose of the resultant composition and the conditions under which it is to be used.
- the amount of additive employed based on the total weight of the mineral oil composition may range from 0.01 to 25.0 weight percent, preferably is from about 0.5 to, 10.0 weight percent.
- the lubricant composition advantageously may contain from about 0.001 to Weight percent of anti-wear agents and anti-oxidants such as ele mental sulfur, zinc dithiophosphate or other organic sulfur compounds, such as sulfurized sperm oil and the like.
- the lubricant may contain other agents such as dyes, pour depressors, thickeners, viscosity index improvers and any of the agents conventionally used as additives for lubricating oils.
- the reaction between the basic barium phenol sulfide and the material selected from the group consisting of petroleum sulfonic acids, dithiophosphoric acid diesters and phosphorus sulfide-hydrocarbon reaction products is carried out by mixing the desired materials at a temperature from about room temperature to 500 F. or more, preferably about to 200 PI, until the reaction is complete. Ordinarily, after about one hour the reaction is considered complete, although after reacting at lower temperatures, eg to F. the product can be heated to about 250 to 309 F. to remove the water of reaction.
- my new additives are described as reaction products, I do not wish to be bound by theory as there may in fact not be a reaction effected.
- the basic barium phenol sulfides which can be reacted with the material selected from the group consisting of petroleum sulfonic acids, dithiophosphoric acid diesters and phosphorus sulfide-hydrocarbon reaction products include the oil-soluble basic barium salts of alkyl phenol sulfides, for instance, those in which the total number of carbon atoms in the alkyl group or alkyl groups is about 8 to 24, such as dodecyl, n-decyl, cetyl, and the like.
- Suitable alkyl phenol sulfides which may be employed are tertiary-octyl phenol sulfide, 2,4-diamyl phenol sulfide, 2-ethylhexyl phenol sulfide, (I -C branched chain alkyl phenol sulfides and the like.
- the phenol radical is neutralized with a sufficient amount of a basic barium compound so as to obtain an oil-soluble basic salt which contains at least about 1.2 times the theoretical amount of metal required to form the normal barium salt.
- This reaction can be brought about by heating the metallic oxide or hydroxide directly with the phenol in the presence of a suitable solvent under conditions well known in the art.
- the phosphorus sulfide-hydrocarbon materials which are employed in the present invention to produce the novel lubricating oil additives are the oil-soluble reaction products of a sulfide of phosphorus with a suitable hydrocarbon material of lubricating viscosity, such as a material of natural petroleum origin, for example, a heavy hydrocarbon oil of lubricating viscosity having a molecular weight above 500, Le, residual lubricating oils, or a synthetic hydrocarbon material such as an olefin or olefin polymer having a molecular Weight of from about 400 to 2000 or more.
- a suitable hydrocarbon material of lubricating viscosity such as a material of natural petroleum origin, for example, a heavy hydrocarbon oil of lubricating viscosity having a molecular weight above 500, Le, residual lubricating oils, or a synthetic hydrocarbon material such as an olefin or olefin polymer having a molecular Weight of from about 400 to 2000
- the hydrocarbon material can be reacted with from about 1 to 50 Weight percent, and preferably 5 percent to 25 percent of a sulfide of phosphorus, such as P 5 P 8 P 8 or mixtures thereof, at a temperature of from about 200 to 500 F. in a non-oxidizing atmosphere such as an atmosphere of nitrogen.
- the final reaction product will usually contain from about 1 to 6 percent by weight of organically combined phosphorus.
- a hydrocarbon material such as a mineral oil bright stock or cylinder stock having a viscosity within a range of about 120 to 300 SUS at 210 F. is reacted with 7 to 17 weight percent of phosphorus pentasulfide at a temperature between about 400 to 500 F. for a period of about 1-0 to 20 hours.
- a phosphorus sulfide with a bright stock, for example, the formation of oil-soluble products which are pro-sludging in typical lubricating oil blends are greatly reduced as compared to the reaction with a lighter oil, such as a neutral oil, which affords a larger percentage of insoluble reaction products.
- reaction mixture contains insoluble products these materials can be removed by filtration or centrifugation performed at an elevated temperature, usually about 150 to 280 F.
- the final reaction product may be steam-treated until only trace amounts of hydrogen sulfide are evolved.
- suitable hydrocarbons which can be reacted with phosphorus sulfide include olefins such as cetene, melene, high molecular weight alkenes obtained by cracking petroleum oils, etc. and olefin polymers such as those obtained in the liquid phase polymerization of butylene, and isobutylene in the presence of a Friedel-Craftstype catalyst.
- the dithiophosphoric acid diesters which can be reacted with basic barium phenol sulfide to obtain the new composition of this invention are oil-soluble and include a wide variety of acid esters conventionally prepared by reacting a sulfide of phosphorus, preferably phosphorus pentasulfide, with a phenol, alcohol or mercaptan, under conditions of esterifieation well known in the art.
- the organic group in the acid diesters may be a straight chain, branched chain, aryl or cycloaliphatic hydrocarbon group which may or may not have other substituent groups such as sulfur, halogen or nitro groups attached thereto.
- Suitable alcohols used in the preparation of diester dithiophosphoric acids'contain from 6 to 18 carbon atoms include such alcohols as hexyl, heptyl, 2-ethyl amyl, octyl, iso-octyl, 2-propyl amyl, decyl, undecyl, dodecyl, hexadecyl, 2-ethy1 hexyl, methylisobutylcarbinol, cyclohexanol, methyl cyclohexanol, or a mixture of C primary and C secondary alcohols, etc.
- Suitable phenols which may be employed are the alkylated phenols such as octyl cresol, p-octyl phenol, p-tertiary amyl phenol, tertiary butyl cresol, dodecyl phenol and the like.
- the esterification reaction is carried out by reacting the desired alcohol, mixture of alcohols, phenol, or mercaptan with phosphorus pentasulfide at a temperature of about 120 to 350 F. until esterification is complete.
- Suitable sulfonic acids which may be employed in accordance with the present invention are the oil-soluble sulfonic acids and particularly the sulfonic acids produced in the treatment of petroleum hydrocarbons with a sulfonating agent such as sulfuric acid or sulfur trioxide.
- the preferentially oil-soluble sulfonic acids generally referred to as mahogany acids, are conveniently employed as a concentrate in the oil from which they are derived and may be prepared by sulfonating a suitable petroleum distillate with fuming sulfuric acid to obtain approximately a weight percent concentration of mahogany acids in the acid oil, or by sulfonating with sulfur trioxide in which case approximately a 20 weight percent concentration is obtained.
- the useful mahogany acids generally have a molecular weight of 300 to 500 or higher.
- the base mineral oil used in the preparation of the lubricating composition will ordinarily depend upon the Example I PREPARATION OF ACID OIL A 270 SUS at 100 F. viscosity Sweet West Texas gas oil fraction was treated with four 28 pound per barrel dumps of 20% oleum. The sludge was removed after each oleum dump. The acid-treated oil was freed of, S0 by air blowing to leave a solution of approximately 10% mahogany sulfonic acid in oil which had an acid No. of 14.1.
- Example III PREPARATION OF PzSs-HYDROCAR-BON PRODUCT 1106 gallons of a SUS at 210 F. viscosity Mid- Continent bright stock was charged to the reaction kettle and heated to 275 F. 1200 pounds of P 8 was added while stirring and the temperature was brought up to 440 F. for 14 hours. The reaction mixture was cooled to 275 F. and filtered with Super-Cel to leave a product which analyzed as follows:
- Example IV PREPARATION OF STEAMED PzSs-HYDROCARBON PRODUCT 1000 gallons of oil-P 8 reaction product concentrate, as prepared in Example III, was charged to the reaction kettle and heated to 285 F. Steam was passed through the reaction mixture for 8 hours with the temperature at 300325 F. After the steaming was completed the temperature was held at 300 F. for 15 minutes to dehydrate the product. Super-Cel was added and the product was filtered. It analyzed as follows:
- Example V PREPARATION OF BASIC BARIUM PHENOL SULFIDE CONCENTRATE 6309 grams of octyl phenol was placed in a 22 liter three neck flask. 6309 grams of toluene was added and the mixture was stirred until complete solution was attained. Stirring was continued while 2670 grams of SO1 was slowly added during a 6 hour period of 75-135 F. The mixture was then heated at reflux (about 240 F.) for 6 hours. The toluene was topped out by heating the mixture to 300 F. Dry nitrogen was bubbled through the product until toluene distillation ceased. 3000 grams of this product was dissolved in 6000 grams of a 200 SUS 'at 100 F.
- Example VI PREPARATION OF BASIC BARIUM PHENOL SULFIDE- SULFONIC ACID OIL REACTION PRODUCT CONCEN- TRATE 1000 grams of basic barium phenol sulfide as prepared in Example V was mixed with 3470 grams of acid oil, as prepared in Example I, at room temperature. A noticeable heat of reaction resulted which increased the temperature to 95 F. The mixture was slowly heated to 300 F. The amount of acid oil was calculated to be equivalent to one-half of the barium in the basic barium phenol sulfide. The product analyzed as follows:
- Example VIII PREPARATION OF BASIC BARIUM PHENOL SULFIDE AND OIL-Fess REACTION PRODUCT CONCENTBATE 1000 grams of basic barium phenol sulfide as prepared in Example V, was mixed with 1490 grams of oil-P 5 reaction product, as prepared in Example 111, and slowly heated to 300 F. The amount of oil-P 8 reaction product was calculated to be equivalent to one-half of the barium content of the basic barium phenol sulfide. The product analyzed as follows:
- compositions of the present invention are illustrated by the following comparative oxygen absorption tests applied to mineral oil blends containing the compositions of the type illustrated in Examples VI through TX.
- the oxygen absorption tests were carried out at a temperature of 360 F. in the presence of a copper-lead catalyst on compositions blended to give a barium content of 0.52% by weight in a solvent-treated Mid-Continent neutral oil having a viscosity of about 160 SUS at F.
- Basic Barium Phenol Sulfide- VIII 10. 8 1,210 cc. in 300 P S -Hydrocarbon. minutes.
- Basic Barium Phenol Sulticle- IX 5. 74 1,056 cc. in 300 Dithiophosphoric Acid minutes. Ester.
- the base oil is a solvent-treated Mid-Continent neutral of about 160 viscosity SU S at 100 F. with a viscosity index of 95. Each blend contained approximately 0.52% barium.
- a lubricating oil composition consisting essentially of a mineral lubricating oil and from 0.01 to 25.0 weight percent of a product obtained by reacting at a temperature from about room temperature to 500 F. an oilsoluble basic barium phenol sulfide with a quantity sufiicient theoretically to neutralize from one-half to all of the total barium content of the basic barium phenol sulfide of one oil-soluble material selected from the group consisting of petroleum sulfonic acid, dithiophosphoric acid diesters and phosphorus sulfide-hydrocarbon oil reaction products, and heating to remove water produced by said reacting.
- composition of claim 1 wherein said lubricating composition contains 0.5 to 10.0 weight percent of said reaction product.
- composition of claim 1 wherein quantities of said material selected from the group consisting of petroleum sulfonic acids, dithiophosphoric acid diesters and phosphorus sulfide-hydrocarbon oil reaction products equivalent to about half the barium in said basic barium phenol sulfide are reacted with said basic barium phenol sulfide.
- composition of claim 3 wherein said phosphorus sulfide-hydrocarbon oil product is prepared by reacting 7 to 17 weight percent of phosphorus pentasulfide with a mineral oil bright stock having a viscosity within the range of about to 300 SUS at 210 F. at a temperature between about 400 F. and 500 F. for a period of about 10 to 20 hours, and said dithiophosphoric acid diesters are prepared by reacting a mixture of C primary ,andC secondary alcohols with phosphorus pentasulfide;
- a lubricating oil composition consisting essentially of a mineral lubricating oil and from about 0.01 to 25.0 weight percent of a product obtained by reacting at a temperature from about room temperature to 500 F. an oil-soluble basic barium phenol sulfide with a quantity suflicient theoretically ,to neutralize from one-half to all of the total barium content of the basic barium phenol sulfide of a dithiophosphoric acid diester and heating to remove water produced by said reacting.
- the lubricant ofclaim 5 in which the diester is the product of the reaction under esterification conditions of a sulfide of phosphorus with an alcohol of 6 to 18 carbon atoms.
- the lubricant of claim 5 in which the diester is the product of reaction of about 1 mol of P 8 with about 4 moles of mixed C -C alcohols.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Lubricants (AREA)
Description
United States Patent 3,135,692 GmATiGN RESlSTANT LUBRHEANT Manley Kjonaas, Hammond, Ind, assignor, by mesne as= signrnents, to Sinclair Research inc, New York, N.Y., a corporation oi Delaware No Drawing. Filed May 21, E56, Ser. No. 585,981 7 Claims. (Cl. 252-32.7)
The present invention relates to mineral oil ompositions and more particularly to the use of novel additives to impart anti-oxidant and detergent properties to lubricating oils.
Various detergent additives have heretofore been proposed for use in mineral oil compositions, such as heavy duty lubricating oils, which are suitable for use as crankcase lubricants for internal combustion engines, including automobile, diesel and marine engines, which operate for long periods of time at high temperatures and in which the lubricant comes in contact with metal surfaces. In general, the function of these detergent or dispersant type additives is to impart properties to the motor oil which will enable it to 'keep the pistons, ring and valves free of varnish and lacquer deposits by keeping oil oxidation products and other types of insoluble matter in suspension so that these materials will not settle out and adhere to metal surfaces. The metal derivatives of organic compounds, such as substituted phenols and sulfonic acids, are among the most Widely used additive agents to improve the detergent properties of a lubricating oil. However, While these detergent additives perform satisfactorily in dispersing sludge and preventing lacquer deposits, many of these additives, particularly under extreme operating conditions, increase the rate of oxidation of the oil and effect increased concentrations of acidic oxidation products which thus increase the rate of corrosion to the bearings, pistons, valves and the like.
in accordance with my invention, I have discovered new and useful detergent-anti-oxidant additives prepared by reacting an oil-soluble basic barium phenol sulfide with an oil-soluble material selected from the group consisting of petroleum sulfonic acids, dithiophosphoric acid diesters, and phosphorus sulfide-hydrocarbon reaction products. I have found that these combinations of constituents produce detergent materials having particularly desirable properties for use in lubricating oils, including sludge dispersant properties, anti-Wear properties and the prevention of varnish formation and lacquer-like deposits. The useful additives of my invention provide lubricating oil compositions with improved resistance to oxidative deterioration whereby the corrosion to valves, bearings, pistons and the like, is reduced rather than accelerated.
The novel detergent-antioxidant lubricating oil additives of this invention can be employed in amounts varying over a considerable range depending upon the intended purpose of the resultant composition and the conditions under which it is to be used. In compositions intended for use as crankcase lubricants for internal combustion engines, the amount of additive employed based on the total weight of the mineral oil composition, may range from 0.01 to 25.0 weight percent, preferably is from about 0.5 to, 10.0 weight percent. In addition, the lubricant composition advantageously may contain from about 0.001 to Weight percent of anti-wear agents and anti-oxidants such as ele mental sulfur, zinc dithiophosphate or other organic sulfur compounds, such as sulfurized sperm oil and the like.
Furthermore, the lubricant may contain other agents such as dyes, pour depressors, thickeners, viscosity index improvers and any of the agents conventionally used as additives for lubricating oils.
In carrying out the preparation of the additives of this invention, it is preferred to use ratios of the phosphorus sulfide-hydrocarbon, sulfonic acid or dithiophosphoric acid diester materials which would theoretically neutralize one-half of the total barium content in the basic barium phenol sulfide so as to obtain products which are substantially basic to pH 4. However, if a neutral oil blend is desired, then chemically equivalent quantities of the reactants can be employed.
The reaction between the basic barium phenol sulfide and the material selected from the group consisting of petroleum sulfonic acids, dithiophosphoric acid diesters and phosphorus sulfide-hydrocarbon reaction products is carried out by mixing the desired materials at a temperature from about room temperature to 500 F. or more, preferably about to 200 PI, until the reaction is complete. Ordinarily, after about one hour the reaction is considered complete, although after reacting at lower temperatures, eg to F. the product can be heated to about 250 to 309 F. to remove the water of reaction. Although my new additives are described as reaction products, I do not wish to be bound by theory as there may in fact not be a reaction effected.
The basic barium phenol sulfides which can be reacted with the material selected from the group consisting of petroleum sulfonic acids, dithiophosphoric acid diesters and phosphorus sulfide-hydrocarbon reaction products, include the oil-soluble basic barium salts of alkyl phenol sulfides, for instance, those in which the total number of carbon atoms in the alkyl group or alkyl groups is about 8 to 24, such as dodecyl, n-decyl, cetyl, and the like. Suitable alkyl phenol sulfides which may be employed are tertiary-octyl phenol sulfide, 2,4-diamyl phenol sulfide, 2-ethylhexyl phenol sulfide, (I -C branched chain alkyl phenol sulfides and the like.
In the preparation of the basic barium salts of the above-mentioned phenol sulfides the phenol radical is neutralized with a sufficient amount of a basic barium compound so as to obtain an oil-soluble basic salt which contains at least about 1.2 times the theoretical amount of metal required to form the normal barium salt. This reaction can be brought about by heating the metallic oxide or hydroxide directly with the phenol in the presence of a suitable solvent under conditions well known in the art.
The phosphorus sulfide-hydrocarbon materials which are employed in the present invention to produce the novel lubricating oil additives are the oil-soluble reaction products of a sulfide of phosphorus with a suitable hydrocarbon material of lubricating viscosity, such as a material of natural petroleum origin, for example, a heavy hydrocarbon oil of lubricating viscosity having a molecular weight above 500, Le, residual lubricating oils, or a synthetic hydrocarbon material such as an olefin or olefin polymer having a molecular Weight of from about 400 to 2000 or more. In carrying out the phosphorus sulfidehydrocarbon reaction, the hydrocarbon material can be reacted with from about 1 to 50 Weight percent, and preferably 5 percent to 25 percent of a sulfide of phosphorus, such as P 5 P 8 P 8 or mixtures thereof, at a temperature of from about 200 to 500 F. in a non-oxidizing atmosphere such as an atmosphere of nitrogen. The final reaction product will usually contain from about 1 to 6 percent by weight of organically combined phosphorus.
In a preferred embodiment, a hydrocarbon material such as a mineral oil bright stock or cylinder stock having a viscosity within a range of about 120 to 300 SUS at 210 F. is reacted with 7 to 17 weight percent of phosphorus pentasulfide at a temperature between about 400 to 500 F. for a period of about 1-0 to 20 hours. By reacting a phosphorus sulfide with a bright stock, for example, the formation of oil-soluble products which are pro-sludging in typical lubricating oil blends are greatly reduced as compared to the reaction with a lighter oil, such as a neutral oil, which affords a larger percentage of insoluble reaction products. Ordinarily if the reaction mixture contains insoluble products these materials can be removed by filtration or centrifugation performed at an elevated temperature, usually about 150 to 280 F. Advantageously, the final reaction product may be steam-treated until only trace amounts of hydrogen sulfide are evolved. Other suitable hydrocarbons which can be reacted with phosphorus sulfide include olefins such as cetene, melene, high molecular weight alkenes obtained by cracking petroleum oils, etc. and olefin polymers such as those obtained in the liquid phase polymerization of butylene, and isobutylene in the presence of a Friedel-Craftstype catalyst.
The dithiophosphoric acid diesters which can be reacted with basic barium phenol sulfide to obtain the new composition of this invention are oil-soluble and include a wide variety of acid esters conventionally prepared by reacting a sulfide of phosphorus, preferably phosphorus pentasulfide, with a phenol, alcohol or mercaptan, under conditions of esterifieation well known in the art. The organic group in the acid diesters may be a straight chain, branched chain, aryl or cycloaliphatic hydrocarbon group which may or may not have other substituent groups such as sulfur, halogen or nitro groups attached thereto. Suitable alcohols used in the preparation of diester dithiophosphoric acids'contain from 6 to 18 carbon atoms and include such alcohols as hexyl, heptyl, 2-ethyl amyl, octyl, iso-octyl, 2-propyl amyl, decyl, undecyl, dodecyl, hexadecyl, 2-ethy1 hexyl, methylisobutylcarbinol, cyclohexanol, methyl cyclohexanol, or a mixture of C primary and C secondary alcohols, etc. Suitable phenols which may be employed are the alkylated phenols such as octyl cresol, p-octyl phenol, p-tertiary amyl phenol, tertiary butyl cresol, dodecyl phenol and the like. Similarly, if a higher sulfur content of the acid ester is desired, then the corresponding mercaptan of the abovedescribed materials can be employed. In general, the esterification reaction is carried out by reacting the desired alcohol, mixture of alcohols, phenol, or mercaptan with phosphorus pentasulfide at a temperature of about 120 to 350 F. until esterification is complete.
Suitable sulfonic acids which may be employed in accordance with the present invention are the oil-soluble sulfonic acids and particularly the sulfonic acids produced in the treatment of petroleum hydrocarbons with a sulfonating agent such as sulfuric acid or sulfur trioxide. The preferentially oil-soluble sulfonic acids, generally referred to as mahogany acids, are conveniently employed as a concentrate in the oil from which they are derived and may be prepared by sulfonating a suitable petroleum distillate with fuming sulfuric acid to obtain approximately a weight percent concentration of mahogany acids in the acid oil, or by sulfonating with sulfur trioxide in which case approximately a 20 weight percent concentration is obtained. The useful mahogany acids generally have a molecular weight of 300 to 500 or higher.
The base mineral oil used in the preparation of the lubricating composition will ordinarily depend upon the Example I PREPARATION OF ACID OIL A 270 SUS at 100 F. viscosity Sweet West Texas gas oil fraction was treated with four 28 pound per barrel dumps of 20% oleum. The sludge was removed after each oleum dump. The acid-treated oil was freed of, S0 by air blowing to leave a solution of approximately 10% mahogany sulfonic acid in oil which had an acid No. of 14.1.
Example II PREPARATION OF DITHIOPHOSPORIC ACID DIESTER.
Four moles (based on hydroxyl value) of mixed C and C alcohols were reacted with 1 mol of P 8 at 160- 170 F. to give a dithiophosphoric acid ester which analyzed as follows:
Percent sulfur 19.2 Percent phosphorus 9.72 Acid No. 155.8.
Example III PREPARATION OF PzSs-HYDROCAR-BON PRODUCT 1106 gallons of a SUS at 210 F. viscosity Mid- Continent bright stock was charged to the reaction kettle and heated to 275 F. 1200 pounds of P 8 was added while stirring and the temperature was brought up to 440 F. for 14 hours. The reaction mixture was cooled to 275 F. and filtered with Super-Cel to leave a product which analyzed as follows:
Percent sulfur 5.78 Percent phosphorus 3.13 Acid No 32.7
Example IV PREPARATION OF STEAMED PzSs-HYDROCARBON PRODUCT 1000 gallons of oil-P 8 reaction product concentrate, as prepared in Example III, was charged to the reaction kettle and heated to 285 F. Steam was passed through the reaction mixture for 8 hours with the temperature at 300325 F. After the steaming was completed the temperature was held at 300 F. for 15 minutes to dehydrate the product. Super-Cel was added and the product was filtered. It analyzed as follows:
Percent sulfur 1.55 Percent phosphorus 3.04 AcidNo. 68.7
Example V PREPARATION OF BASIC BARIUM PHENOL SULFIDE CONCENTRATE 6309 grams of octyl phenol was placed in a 22 liter three neck flask. 6309 grams of toluene was added and the mixture was stirred until complete solution was attained. Stirring was continued while 2670 grams of SO1 was slowly added during a 6 hour period of 75-135 F. The mixture was then heated at reflux (about 240 F.) for 6 hours. The toluene was topped out by heating the mixture to 300 F. Dry nitrogen was bubbled through the product until toluene distillation ceased. 3000 grams of this product was dissolved in 6000 grams of a 200 SUS 'at 100 F. viscosity 95 VI solvent treated Mid-continent neutral. 4000 grams of water and 3000 grams of barium oxide were added. The mixture was diluted with about 1% gallons of kerosene and stirred for 4 hours at 180- 200 F. The reaction mixture was dehydrated to 300 F., filtered with Super-Cel and vacuum topped to 350 F. at 0.5 mm. mercury absolute pressure to leave a product which analyzed as follows:
Percent barium 11.9 Percent sulfur 3.14 Base No. to pH 4 106.0
Example VI PREPARATION OF BASIC BARIUM PHENOL SULFIDE- SULFONIC ACID OIL REACTION PRODUCT CONCEN- TRATE 1000 grams of basic barium phenol sulfide as prepared in Example V was mixed with 3470 grams of acid oil, as prepared in Example I, at room temperature. A noticeable heat of reaction resulted which increased the temperature to 95 F. The mixture was slowly heated to 300 F. The amount of acid oil was calculated to be equivalent to one-half of the barium in the basic barium phenol sulfide. The product analyzed as follows:
Percent barium 2.62
Base No. to pH 4 14.8
Example VII PREPARATION OF BASIC BARIUM PHENOL SULFIDE- STEAMED OIL-Pass REACTION PRODUCT CONCEN- TRATE Percent barium 6.98 Percent phosphorus 1.33 Percent sulfur 2.42 Base No. to pH 4 45.6
Example VIII PREPARATION OF BASIC BARIUM PHENOL SULFIDE AND OIL-Fess REACTION PRODUCT CONCENTBATE 1000 grams of basic barium phenol sulfide as prepared in Example V, was mixed with 1490 grams of oil-P 5 reaction product, as prepared in Example 111, and slowly heated to 300 F. The amount of oil-P 8 reaction product was calculated to be equivalent to one-half of the barium content of the basic barium phenol sulfide. The product analyzed as follows:
Percent barium 4.8 Percent phosphorus 1.88 Percent sulfur 4.70 Base No. to pH 4 10.7
Example IX PREPARATION OF BASIC BARIUM PHE'NOL SULFIDE- DITHIOPHOSPHORIC ACID ESTER REACTION PROD- UCT CONCENTRATE 1000 grams of basic barium phenol sulfide, as prepared in Example V, was mixed with 313 grams of dithiophosphoric acid ester, as prepared in Example II. There was a noticeable heat of reaction. The mixture was slowly heated to 300 F. The amount of dithiophosphoric acid ester was calculated to be equivalent to onehalf of the barium in the basic barium phenol sulfide. The product analyzed as follows:
The benefits derived from the compositions of the present invention are illustrated by the following comparative oxygen absorption tests applied to mineral oil blends containing the compositions of the type illustrated in Examples VI through TX. The oxygen absorption tests were carried out at a temperature of 360 F. in the presence of a copper-lead catalyst on compositions blended to give a barium content of 0.52% by weight in a solvent-treated Mid-Continent neutral oil having a viscosity of about 160 SUS at F. As can be seen from the following table, a blend containing basic barium phenol sulfide absorbed 2200 cc. of oxygen in 232 minutes while a blend containing the new reaction product of basic barium phenol sulfide and dithiophosphoric acid ester as in Example IX, absorbed 1056 cc. in 300 minutes, or approx imately one-half as much oxygen in a time period of one-half again as long as the basic barium phenol sulfide. Improved results were also obtained with the other additives of this invention.
TABLE I Additive Amount of Concen- Additive Rate of Oxygen Additive trate Pre- Concen- Absorption per pared as in trate Wt. 100 grams of Example Percent in Blend No. Base 011 1 Base Oil 1 none 2,200 co. in 202 minutes. Basic Barium Phenol Sulfide V 4. 37 2,200 cc. in 232 minutes. Basic Barium Phenol Sulfide- VI 15.3 1,634 cc. in 300 Sultonic Acid Oil. minutes. Basic Barium Phenol Sulfidc- VII 7. 43 1,309 cc. in 300 Steamed P S -Hydr0carminutes.
on. Basic Barium Phenol Sulfide- VIII 10. 8 1,210 cc. in 300 P S -Hydrocarbon. minutes. Basic Barium Phenol Sulticle- IX 5. 74 1,056 cc. in 300 Dithiophosphoric Acid minutes. Ester.
1 The base oil is a solvent-treated Mid-Continent neutral of about 160 viscosity SU S at 100 F. with a viscosity index of 95. Each blend contained approximately 0.52% barium.
I claim:
1. A lubricating oil composition consisting essentially of a mineral lubricating oil and from 0.01 to 25.0 weight percent of a product obtained by reacting at a temperature from about room temperature to 500 F. an oilsoluble basic barium phenol sulfide with a quantity sufiicient theoretically to neutralize from one-half to all of the total barium content of the basic barium phenol sulfide of one oil-soluble material selected from the group consisting of petroleum sulfonic acid, dithiophosphoric acid diesters and phosphorus sulfide-hydrocarbon oil reaction products, and heating to remove water produced by said reacting.
2. The composition of claim 1 wherein said lubricating composition contains 0.5 to 10.0 weight percent of said reaction product.
3. The composition of claim 1 wherein quantities of said material selected from the group consisting of petroleum sulfonic acids, dithiophosphoric acid diesters and phosphorus sulfide-hydrocarbon oil reaction products equivalent to about half the barium in said basic barium phenol sulfide are reacted with said basic barium phenol sulfide.
4. The composition of claim 3 wherein said phosphorus sulfide-hydrocarbon oil product is prepared by reacting 7 to 17 weight percent of phosphorus pentasulfide with a mineral oil bright stock having a viscosity within the range of about to 300 SUS at 210 F. at a temperature between about 400 F. and 500 F. for a period of about 10 to 20 hours, and said dithiophosphoric acid diesters are prepared by reacting a mixture of C primary ,andC secondary alcohols with phosphorus pentasulfide;
5. A lubricating oil composition consisting essentially of a mineral lubricating oil and from about 0.01 to 25.0 weight percent of a product obtained by reacting at a temperature from about room temperature to 500 F. an oil-soluble basic barium phenol sulfide with a quantity suflicient theoretically ,to neutralize from one-half to all of the total barium content of the basic barium phenol sulfide of a dithiophosphoric acid diester and heating to remove water produced by said reacting.
6. The lubricant ofclaim 5 in which the diester is the product of the reaction under esterification conditions of a sulfide of phosphorus with an alcohol of 6 to 18 carbon atoms.
7. The lubricant of claim 5 in which the diester is the product of reaction of about 1 mol of P 8 with about 4 moles of mixed C -C alcohols.
UNITED STATES PATENTS Neely June 22,' Buckmanu July 19, Barton et al. Feb. 24, Lowe July 19, Rogers et al. Sept. 4, Kane et al. Feb; 12, Buck et a1. ..July 2,- Davidson et al. Oct. 1, Scott etal June 17, Moody et al. Aug. 26, Bowden et al. Mar. 5, Knapp et al. Ian. 24,
Claims (1)
1. A LUBRICATING OIL COMPOSITION CONSISTING ESSENTIALLY OF A MINERAL LUBRICATING OIL AND FROM 0.01 TO 25.0 WEIGHT PERCENT OF A PRODUCT OBTAINED BY REACTING AT A TEMPERATURE FROM ABOUT ROOM TEMPERATURE TO 500*F. AN OILSOLUBLE BASIC BARIUM PHENOL SULFIDE WITH A QUANTITY SUFFICIENT THEORETICALLY TO NEUTRALIZE FROM ONE-HALF TO ALL OF THE TOTAL BARIUM CONTENT OF THE BASIC BARIUM PHENOL SULFIDE OF ONE OIL-SOLUBLE MATERIAL SELECTED FROM THE GROUP CONSISTING OF PETROLEUM SULFONIC ACID, DITHIOPHOSPHORIC ACID DIESTERS AND PHOSPHORUS SULFIDE-HYDROCARBON OIL REACTION PRODUCTS, AND HEATING TO REMOVE WATER PRODUCED BY SAID REACTING.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US585981A US3135692A (en) | 1956-05-21 | 1956-05-21 | Oxidation resistant lubricant |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US585981A US3135692A (en) | 1956-05-21 | 1956-05-21 | Oxidation resistant lubricant |
Publications (1)
Publication Number | Publication Date |
---|---|
US3135692A true US3135692A (en) | 1964-06-02 |
Family
ID=24343794
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US585981A Expired - Lifetime US3135692A (en) | 1956-05-21 | 1956-05-21 | Oxidation resistant lubricant |
Country Status (1)
Country | Link |
---|---|
US (1) | US3135692A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4153562A (en) * | 1977-12-23 | 1979-05-08 | Exxon Research & Engineering Co. | Antioxidants for low ash and medium ash lubricating oils |
US4328111A (en) * | 1978-11-20 | 1982-05-04 | Standard Oil Company (Indiana) | Modified overbased sulfonates and phenates |
US5256319A (en) * | 1989-03-30 | 1993-10-26 | Institut Francais Du Petrole | New thiophosphoretted compounds, their preparation and their use as additives for lubricants |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2322307A (en) * | 1939-06-20 | 1943-06-22 | Standard Oil Co California | Compounded oil |
US2476812A (en) * | 1945-05-23 | 1949-07-19 | Union Oil Co | Lubricating composition |
US2629693A (en) * | 1947-07-01 | 1953-02-24 | Shell Dev | Lubricating composition |
US2713557A (en) * | 1951-12-06 | 1955-07-19 | California Research Corp | Basic phenates to inhibit silver corrosion in thiophosphate-containing lubricating oils |
US2761845A (en) * | 1955-03-28 | 1956-09-04 | Exxon Research Engineering Co | Foam inhibition of oils |
US2781403A (en) * | 1952-10-01 | 1957-02-12 | Exxon Research Engineering Co | High barium-content phenolic compounds |
US2798045A (en) * | 1954-09-27 | 1957-07-02 | Shell Dev | Lubricating compositions |
US2808377A (en) * | 1956-03-30 | 1957-10-01 | Exxon Research Engineering Co | Process for preparing neutralized alkyl phenol sulfides |
US2839471A (en) * | 1955-05-17 | 1958-06-17 | Exxon Research Engineering Co | Extreme pressure lubricants |
US2849398A (en) * | 1953-08-19 | 1958-08-26 | Exxon Research Engineering Co | Mineral-base lubricating oils and methods for using same |
US2885362A (en) * | 1955-12-28 | 1959-05-05 | Pure Oil Co | Paper-machine oils |
US2969324A (en) * | 1958-02-20 | 1961-01-24 | Exxon Research Engineering Co | Phosphosulfurized detergent-inhibitor additive |
-
1956
- 1956-05-21 US US585981A patent/US3135692A/en not_active Expired - Lifetime
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2322307A (en) * | 1939-06-20 | 1943-06-22 | Standard Oil Co California | Compounded oil |
US2476812A (en) * | 1945-05-23 | 1949-07-19 | Union Oil Co | Lubricating composition |
US2629693A (en) * | 1947-07-01 | 1953-02-24 | Shell Dev | Lubricating composition |
US2713557A (en) * | 1951-12-06 | 1955-07-19 | California Research Corp | Basic phenates to inhibit silver corrosion in thiophosphate-containing lubricating oils |
US2781403A (en) * | 1952-10-01 | 1957-02-12 | Exxon Research Engineering Co | High barium-content phenolic compounds |
US2849398A (en) * | 1953-08-19 | 1958-08-26 | Exxon Research Engineering Co | Mineral-base lubricating oils and methods for using same |
US2798045A (en) * | 1954-09-27 | 1957-07-02 | Shell Dev | Lubricating compositions |
US2761845A (en) * | 1955-03-28 | 1956-09-04 | Exxon Research Engineering Co | Foam inhibition of oils |
US2839471A (en) * | 1955-05-17 | 1958-06-17 | Exxon Research Engineering Co | Extreme pressure lubricants |
US2885362A (en) * | 1955-12-28 | 1959-05-05 | Pure Oil Co | Paper-machine oils |
US2808377A (en) * | 1956-03-30 | 1957-10-01 | Exxon Research Engineering Co | Process for preparing neutralized alkyl phenol sulfides |
US2969324A (en) * | 1958-02-20 | 1961-01-24 | Exxon Research Engineering Co | Phosphosulfurized detergent-inhibitor additive |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4153562A (en) * | 1977-12-23 | 1979-05-08 | Exxon Research & Engineering Co. | Antioxidants for low ash and medium ash lubricating oils |
US4328111A (en) * | 1978-11-20 | 1982-05-04 | Standard Oil Company (Indiana) | Modified overbased sulfonates and phenates |
US5256319A (en) * | 1989-03-30 | 1993-10-26 | Institut Francais Du Petrole | New thiophosphoretted compounds, their preparation and their use as additives for lubricants |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2409687A (en) | Sulfur and metal containing compound | |
US2451345A (en) | Compounded lubricating oil | |
US2471115A (en) | Lubricating oil | |
US2526497A (en) | Mineral lubricating oil containing polysulfides of thiophosphorous and thiophosphoric acid esters | |
US3388066A (en) | Reaction products of dihydrocarbon dithiophosphoric acid and phosphite | |
US2416281A (en) | Mineral oil composition | |
US2406564A (en) | Compounded lubricating oil | |
US2451346A (en) | Compounded lubricating oil | |
US2895913A (en) | Magnesium containing organic compositions and method of preparing the same | |
US2493217A (en) | Mineral oil composition | |
US2378820A (en) | Lubricating oil | |
US2733235A (en) | Table ii | |
US2658062A (en) | Mineral oil additive | |
US2758971A (en) | Blending agents for mineral oils | |
US2640053A (en) | Compounded lubricating oil | |
US2368000A (en) | Lubricating compositions | |
US2528732A (en) | Reaction products of diesters of dithiophosphoric acid and mineral oil compositions containing the same | |
US2785128A (en) | Metal salts of organic acids of phosphorus | |
US2636858A (en) | Mineral oil additive | |
US2743235A (en) | Mineral oil composition | |
US2623855A (en) | Lubricating compositions | |
US3135692A (en) | Oxidation resistant lubricant | |
US2483505A (en) | Compounded lubricating oil | |
US2420893A (en) | Compounded lubricating oil | |
US2905639A (en) | Lubricating oil compositions |