EP1785477A1 - A low sulfur and low phosphorus lubricating oil composition - Google Patents
A low sulfur and low phosphorus lubricating oil composition Download PDFInfo
- Publication number
- EP1785477A1 EP1785477A1 EP20060255466 EP06255466A EP1785477A1 EP 1785477 A1 EP1785477 A1 EP 1785477A1 EP 20060255466 EP20060255466 EP 20060255466 EP 06255466 A EP06255466 A EP 06255466A EP 1785477 A1 EP1785477 A1 EP 1785477A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricating oil
- oil composition
- weight percent
- sulfur
- total weight
- 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.)
- Ceased
Links
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 341
- 239000000203 mixture Substances 0.000 title claims abstract description 326
- 239000011593 sulfur Substances 0.000 title claims abstract description 125
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 125
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 124
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000011574 phosphorus Substances 0.000 title claims abstract description 104
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 104
- 239000002270 dispersing agent Substances 0.000 claims abstract description 69
- 239000003599 detergent Substances 0.000 claims abstract description 64
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 61
- 239000011701 zinc Substances 0.000 claims abstract description 61
- 239000011733 molybdenum Substances 0.000 claims abstract description 52
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 52
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 50
- 230000001050 lubricating effect Effects 0.000 claims abstract description 49
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 43
- 235000006708 antioxidants Nutrition 0.000 claims abstract description 43
- 239000003921 oil Substances 0.000 claims abstract description 43
- 239000005078 molybdenum compound Substances 0.000 claims abstract description 37
- 150000002752 molybdenum compounds Chemical class 0.000 claims abstract description 36
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 22
- 239000011575 calcium Substances 0.000 claims abstract description 22
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 22
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000002485 combustion reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002530 phenolic antioxidant Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims description 80
- 239000002184 metal Substances 0.000 claims description 80
- 239000003795 chemical substances by application Substances 0.000 claims description 49
- 239000003112 inhibitor Substances 0.000 claims description 48
- 239000003607 modifier Substances 0.000 claims description 39
- 239000000654 additive Substances 0.000 claims description 31
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 25
- 238000005260 corrosion Methods 0.000 claims description 25
- 230000007797 corrosion Effects 0.000 claims description 24
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims description 18
- 150000001340 alkali metals Chemical class 0.000 claims description 18
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 17
- 150000007942 carboxylates Chemical class 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 13
- 229960001860 salicylate Drugs 0.000 claims description 13
- 239000012141 concentrate Substances 0.000 claims description 12
- 239000006078 metal deactivator Substances 0.000 claims description 11
- 239000002518 antifoaming agent Substances 0.000 claims description 9
- 239000003502 gasoline Substances 0.000 claims description 9
- 239000003345 natural gas Substances 0.000 claims description 8
- 150000003873 salicylate salts Chemical class 0.000 claims 4
- -1 alkaline earth metal sulfonate Chemical class 0.000 description 52
- 238000009472 formulation Methods 0.000 description 31
- 239000002956 ash Substances 0.000 description 25
- 239000002199 base oil Substances 0.000 description 16
- 150000002148 esters Chemical class 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 16
- 239000000314 lubricant Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 12
- 229910019142 PO4 Inorganic materials 0.000 description 10
- 235000021317 phosphate Nutrition 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 8
- 229910052796 boron Inorganic materials 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 239000006260 foam Substances 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- 125000000217 alkyl group Chemical class 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 6
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 4
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 4
- SZAQZZKNQILGPU-UHFFFAOYSA-N 2-[1-(2-hydroxy-3,5-dimethylphenyl)-2-methylpropyl]-4,6-dimethylphenol Chemical compound C=1C(C)=CC(C)=C(O)C=1C(C(C)C)C1=CC(C)=CC(C)=C1O SZAQZZKNQILGPU-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 4
- 239000007866 anti-wear additive Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001083 polybutene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical class C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 2
- OIWIYLWZIIJNHU-UHFFFAOYSA-N 1-sulfanylpyrazole Chemical class SN1C=CC=N1 OIWIYLWZIIJNHU-UHFFFAOYSA-N 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 2
- GSOYMOAPJZYXTB-UHFFFAOYSA-N 2,6-ditert-butyl-4-(3,5-ditert-butyl-4-hydroxyphenyl)phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 GSOYMOAPJZYXTB-UHFFFAOYSA-N 0.000 description 2
- QHPKIUDQDCWRKO-UHFFFAOYSA-N 2,6-ditert-butyl-4-[2-(3,5-ditert-butyl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C(C)(C)C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 QHPKIUDQDCWRKO-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- XQESJWNDTICJHW-UHFFFAOYSA-N 2-[(2-hydroxy-5-methyl-3-nonylphenyl)methyl]-4-methyl-6-nonylphenol Chemical compound CCCCCCCCCC1=CC(C)=CC(CC=2C(=C(CCCCCCCCC)C=C(C)C=2)O)=C1O XQESJWNDTICJHW-UHFFFAOYSA-N 0.000 description 2
- RURPJGZXBHYNEM-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound C=1C=CC=C(O)C=1C=NC(C)CN=CC1=CC=CC=C1O RURPJGZXBHYNEM-UHFFFAOYSA-N 0.000 description 2
- GTLMTHAWEBRMGI-UHFFFAOYSA-N 2-cyclohexyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C2CCCCC2)=C1 GTLMTHAWEBRMGI-UHFFFAOYSA-N 0.000 description 2
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 description 2
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 description 2
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 2
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 2
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- HBEMHMNHYDTVRE-UHFFFAOYSA-N ClC(CCCCCCCCCCCCCCCCC(=O)OC)(Cl)Cl Chemical compound ClC(CCCCCCCCCCCCCCCCC(=O)OC)(Cl)Cl HBEMHMNHYDTVRE-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 2
- NEHDRDVHPTWWFG-UHFFFAOYSA-N Dioctyl hexanedioate Chemical compound CCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCC NEHDRDVHPTWWFG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000005069 Extreme pressure additive Substances 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical class O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- WERKSKAQRVDLDW-ANOHMWSOSA-N [(2s,3r,4r,5r)-2,3,4,5,6-pentahydroxyhexyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO WERKSKAQRVDLDW-ANOHMWSOSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- SNCZNSNPXMPCGN-UHFFFAOYSA-N butanediamide Chemical class NC(=O)CCC(N)=O SNCZNSNPXMPCGN-UHFFFAOYSA-N 0.000 description 2
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- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 239000010710 diesel engine oil Substances 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical class C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 2
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- 239000000344 soap Substances 0.000 description 2
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- 125000001424 substituent group Chemical group 0.000 description 2
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- 239000013638 trimer Substances 0.000 description 2
- WJECKFZULSWXPN-UHFFFAOYSA-N 1,2-didodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1CCCCCCCCCCCC WJECKFZULSWXPN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- MQHWFIOJQSCFNM-UHFFFAOYSA-L Magnesium salicylate Chemical class [Mg+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O MQHWFIOJQSCFNM-UHFFFAOYSA-L 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- HIKZOIYUQFYFBB-UHFFFAOYSA-N didodecyl decanedioate Chemical compound CCCCCCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCCCCCC HIKZOIYUQFYFBB-UHFFFAOYSA-N 0.000 description 1
- GHKVUVOPHDYRJC-UHFFFAOYSA-N didodecyl hexanedioate Chemical compound CCCCCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCCCCC GHKVUVOPHDYRJC-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000000153 supplemental effect Effects 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
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000004580 weight loss Effects 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
- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbased sulfonic acid 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
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/42—Phosphor free or low phosphor content compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
-
- 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
- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
- C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron
Definitions
- the present invention is directed to a low sulfur and low phosphorus lubricating oil composition
- a low sulfur and low phosphorus lubricating oil composition comprising (a) a major amount of an oil of lubricating viscosity and (b) one or more dispersants (c) one or more anti-oxidants and (d) one or more detergents, wherein the lubricating oil composition is essentially free of zinc di-alkyl di-thiophosphates and contains no more than 0.1 weight percent sulfur and provided the lubricating oil composition does not contain alkylated and non-alkylated aromatic amines and tri-nuclear molybdenum compounds.
- the present invention is also directed to a low sulfur and low phosphorus lubricating oil composition
- a low sulfur and low phosphorus lubricating oil composition comprising (a) an oil of lubricating viscosity (b) a borated dispersant and a non-borated dispersant (c) a molybdenum anti-oxidant and a phenolic anti-oxidant and (d) a high overbased and a low overbased calcium sulfonate, wherein the lubricating oil composition is essentially free of zinc di-alkyl di-thiophosphates and contains no more than 0.1 weight percent sulfur and provided the lubricating oil composition does not contain alkylated and non-alkylated aromatic amines and tri-nuclear molybdenum compounds.
- the present invention is also directed to method for lubricating internal combustion engines, which comprises lubricating with the low sulfur and low phosphorus lubricating oil compositions of the present invention.
- Future diesel engines will be equipped with exhaust gas after-treatment systems to allow them to comply with future emission legislation.
- Some of these systems have proven to be sensitive to the combustion products of the fuel and lubricant used in the engine.
- Certain types of systems are sensitive to phosphorus coming from the lubricant, others are sensitive to sulfur coming from both fuel and lubricant, yet others are sensitive to sulfated ash resulting from the combustion of fuel and lubricant.
- special lubricants are being developed that feature low levels of sulfated ash, sulfur and phosphorus. The most common of these lubricants provide low sulfated ash levels with reduced sulfur and phosphorus. Less common are low or no phosphorus lubricants that use specific, mostly sulfur or molybdenum based, zinc di-alkyl di-thiophosphate-replacement additives.
- the guidelines for low emission diesel lubricants that will be commercialized in 2007 and 2008 are : (1) the sulfated ash must be equal to or lower than 1.0 weight percent for diesel engine lubricating oils and equal to or lower than 0.5 weight percent for passenger car diesel engine lubricating oils, (2) according to some engine builders, sulfur content of the lubricating oil must be less than 0.2 weight percent, while other engine builders allow up to a maximum of 0.4 weight percent, and (3) some engine builders require the maximum amount of phosphorus to be 0.08 weight percent, while other engine builders allow up to 0.12 weight percent of phosphorus.
- a number of patents and patent applications have discussed methods for reducing emissions using low sulfur and low phosphorus lubricating oil compositions, but none have disclosed a low sulfur and low phosphorus lubricating oil composition comprising (a) borated dispersant and anon-borated dispersant (b) a molybdenum anti-oxidant and a phenolic anti-oxidant and (c) a low overbased sulfonate and a high overbased sulfonate, which despite containing essentially no zinc di-alkyl di-thiophosphate provides significant reduction in wear.
- U. S. Patent No. 4,623,473 discloses sulfur containing oil-soluble compositions which are useful as lubricating oil additives, particularly in lubricants containing little or no phosphorus.
- the compositions of the invention comprise (A) at least one metal salt of at least one dithiocarbamic acid and (B) at least one oil-soluble sulfurized Diels-Alder adduct.
- Such lubricating oil compositions exhibit improved oxidation-corrosion inhibiting properties, anti-wear properties, and/or extreme pressure properties.
- These lubricating oil compositions containing less than 0.1 weight percent phosphorus also exhibit good compatibility with nitrile seals.
- U. S. Patent No. 4,859,353 discloses sulfur-containing borate esters for use in lubricants appropriate to modern oil requirements with reduced or zero amounts of phosphorus and without the need for large amounts and/or expensive forms of anti-oxidant and additional anti-wear additives.
- U. S. Patent No. 4,990,271 discloses a lubricating oil composition which comprises a major amount of an oil of lubricating viscosity and a minor amount of an additive formed by contacting molybdenum hexacarboxyl with di-xanthogens of the formula (ROCS 2 ) 2 . Moreover, the lubricant compositions of this invention do not include phosphorus.
- U. S. Patent No. 6,159,911 discloses a diesel engine oil composition containing a lube oil base and one or more metallic detergents-dispersants selected from among a perbasic alkaline earth metal sulfonate, phenolate and salicylate.
- the total phosphorus content of the composition is suppressed to 100 parts per million by weight or less, to thereby provide diesel engine oil compositions having oxidation stability and wear resistance.
- U. S. Patent No. 6,162,770 discloses an un-sulfurized, alkali metal-free, detergent-dispersant composition having from about 40% to 60% alkylphenol, from 10% to 40% alkaline earth alkylphenol, and from 20% to 40% alkaline earth single aromatic-ring alkylsalicylate.
- This composition may have an alkaline earth double aromatic-ring salicylates as long as the mole ratio of single-ring alkylsalicylate to double aromatic ring alkylsalicylate is at least 8:1.
- U. S. Patent Nos. 6,331,510 and 6,610,637 disclose a lubricant containing (a) a synthetic base oil composition having an overall kinematic viscosity of at least about 4.8X10 -6 m 2 /s (4.8 cSt) at 100°C and a viscosity index of at least 110; (b) a dispersant-viscosity modifier; and (c) a sulfur-free functionalized hydrocarbyl-substituted phenol detergent provides improved valve train wear, with longer drain intervals, to heavy duty diesel engines.
- U. S. Patent No. 6,376,434 discloses a lube composition which is suitably used for diesel engines which exhaust large amounts of sulfur dioxides.
- the composition exhibits corrosion/wear preventive properties against sulfur dioxides.
- the lube composition includes a lube base oil, a component (A) which is a compound selected from a group consisting of overbased sulfonates of alkaline earth metal, overbased phenates of alkaline earth metals and overbased salicylates of alkaline earth metals, and a component (B) which is a bis-type succinimide compound.
- U. S. Patent Nos. 6,408,812 and 6,588,393 disclose a low sulfur consumable lubricating oil composition
- a base oil an acylated nitrogen-containing compound having a substituent of at least about 10 aliphatic carbon atoms; a sulfur content of about 5 to about 250 parts per million; said composition being characterized by the absence of an extreme-pressure additive comprised of metal and phosphorus.
- U. S. Patent No. 6,588,393 discloses a low-sulfur consumable lubricating oil composition
- a base oil an acylated nitrogen-containing compound having a substituents of at least 10 aliphatic carbon atoms, and a sulfur content of about 5 to about 250 ppm, such composition being characterized by the absence of an extreme pressure additive comprised of metal and phosphorus.
- U.S. Patent No. 6,723,685 discloses a lubricating oil composition
- a lubricating oil composition comprising (a) an oil of lubricating viscosity having a viscosity index of at least 95; (b) at least one calcium detergent; (c) at least one oil-soluble molybdenum compound; (d) at least one organic ashless nitro-free friction modifier; and (e) at least one metal di-hydrocarbyl di-thiophosphate compound, the composition having a NOACK volatility of about 15 weight percent or less, from 0.05 to 0.6 weight percent calcium from the calcium detergent, molybdenum in an amount of at least 10 ppm from the molybdenum compound, and phosphorus from the metal di-hydrocarbyl di-thiophosphate compound in an amount up to about 0.1 weight percent.
- U. S. Patent No. 6,730,638 discloses a lubricating oil for internal combustion engines especially useful with fuels having less than 350 parts per million sulfur comprises a lubricating oil basestock, a boron containing ashless dispersant, a molybdenum containing friction reduction agent, a metal type detergent and zinc di-thiophosphate.
- U. S. Patent No. 6,777,378 discloses a lubricating oil composition
- a lubricating oil composition comprising: (A) a base oil; (B) a molybdenum and sulfur containing composition derived from a basic nitrogen containing compound, a molybdenum compound and carbon disulfide; (C) a boron-containing compound; and (D) optionally a phosphorus containing compound, provided the phosphorus content of the lubricating oil composition does not exceed about 0.1 weight percent.
- 6,784,143 discloses the use of a minor amount of a detergent composition comprising one or more metal detergents which comprises metal salts of organic acids , wherein the detergent composition comprises more than 50 mole percent, based on the moles of the metal salts of organic acids in the detergent composition, of: (I) a metal salt of an aromatic carboxylic acid, or (II) a metal salt of a phenol, or (III) both a metal salt of an aromatic carboxylic acid and a metal salt of a phenol, in a lubricating oil composition for improving oxidation resistance of the lubricating oil composition, wherein the amount of phosphorus and sulfur in the oil composition is less than 0.09 mass % and at the most 0.5 mass % respectively, based on the mass of the oil composition. It has also been found that a detergent composition comprising more than 50 mole % of a metal salt of an aromatic carboxylic acid improves the reduction in wear in an engine.
- U. S. Patent No. 6,852,679 discloses a lubricating oil composition having less than 0.2 weight percent sulfur, less than 50 ppm chlorine, less than 50 ppm phosphorus, a NOACK volatility of 15 weight percent or less comprising an organo-molybdenum compound, an overbased calcium or magnesium salicylates, a dispersant and a supplemental anti-oxidant.
- European Patent Application No. 92917678.2 (Publication No. EP 0 556 404 A2 ) discloses a lubricating oil composition prepared by compounding a base oil with a metal di-thiocarbamate and an oil-soluble amino compound.
- the composition contains scarcely any or no phosphorus and is excellent in wear resistance, extreme pressure properties, frictional characteristics, oxidation stability and coking resistance, thus being suitably usable as a lubricating oil for internal combustion engines of automobiles.
- European Patent Application No. 00302646.5 discloses a lubricating oil composition which contains from about 50 to 1,000, preferably 50 to 500 parts per million of molybdenum from a molybdenum compound which is oil-soluble and substantially free of reactive sulfur, about 1,000 to 20,000, preferably 1,000 to 10,000 parts per million of a di-arylamine and 2,000 to 40,000 parts per million of a phenate.
- This combination of ingredients provides improved oxidation control and improved deposit control to the lubricating oil.
- This composition is particularly suitable for use as a crankcase lubricant.
- European Patent Application No. 04016160.6 discloses an improved lubricating oil composition suitable for diesel engines comprising a major amount of at least one oil of lubricating viscosity and a minor amount of an alkylamine-alkylphosphate additive.
- the alkylamine-alkylphosphate additive comprises from at least 1.25 equivalents of alkylamine to 1.0 equivalents of alkylphosphate.
- U.S. Patent Application No. 10/344,696 (Publication No. US 2003/0182847 A1 ) discloses an additive used for a fuel oil or a lubricating oil composition for a diesel engine having a diesel particulate filter, and a fuel oil comprising the additive.
- the lubricating oil composition having a sulfated ash content of 1.0 weight percent or smaller, a sulfur content of 0.3 weight percent or smaller and a molybdenum content of 100 ppm or greater.
- U.S. Patent Application No. 10/277,295 discloses a lubricating oil composition having a total base number of at least about 8, comprising a major amount of oil of lubricating viscosity; an amount of one or more di-hydrocarbyl di-thiophosphate metal salt introducing into the lubricating oil composition no more than 0.06 weight percent of phosphorus; at least 1.2 weight percent of hindered phenol antioxidant; and boron and/or boron-containing compound or compounds in an amount providing the lubricating oil composition wit at least 200 ppm by weight of boron, all weight percentages being based on the total weight of the lubricating oil composition.
- U.S. Patent Application No. 10/649,572 discloses a lubricating oil composition for use in an internal combustion engine operated with a fuel having a sulfur content of less than 50 ppm, that contains a minor amount of at least one metal-containing detergent, which lubricating oil composition, when formulated for use in a diesel engine has a total ash content of less than 1.0 weight percent and when formulated for use in a gasoline engine has a total ash content of less than 0.7 weight percent.
- U.S. Patent Application No. 10/893,599 discloses a substantially zinc and phosphorus free lubricating oil meeting engine performance requirements contains an additive system containing metal detergents, at least one borated ashless dispersant, at least an amine anti-oxidant and a tri-nuclear molybdenum compound.
- the lubricant contains a minimum of 120 ppm boron and a minimum of 80 ppm molybdenum.
- U.S. Patent Application No. 10/666,356 (Publication No. US 2005/0026792 A1 ) discloses a lubricating oil composition with very low phosphorus content, and having long life as evidenced by a reduction in viscosity increase, oxidation and nitration, comprises a major amount of a base oil of lubricating viscosity and a minor amount of a mixer of neutral and overbased metallic detergents, at least a zinc di-alkyl di-thiocarbamate anti-wear additive and at least a di-hydrocarboxylthiocarbamoyl.
- U.S. Patent Application No. 10/951,356 (Publication No. US 2005/0137096 A1 ) discloses an engine lubricant that is substantially free of zinc and phosphorus contains an anti-wear additive comprising borated 1,2-epoxy mixed polybutenes having an average carbon number in the range of C 20 to C 120 .
- the present invention is directed to a low sulfur and low phosphorus lubricating oil composition
- a low sulfur and low phosphorus lubricating oil composition comprising (a) a major amount of an oil of lubricating viscosity and (b) one or more dispersants (c) one or more anti-oxidants and (d) one or more detergents, wherein the lubricating oil composition is essentially free of zinc di-alkyl di-thiophosphates and contains no more than 0.1 weight percent sulfur and provided the lubricating oil composition does not contain alkylated and non-alkylated aromatic amines and tri-nuclear molybdenum compounds.
- the present invention is also directed to a low sulfur and low phosphorus lubricating oil composition
- a low sulfur and low phosphorus lubricating oil composition comprising (a) an oil of lubricating viscosity (b) a borated dispersant and a non-borated dispersant (c) a molybdenum anti-oxidant and a phenolic anti-oxidant and (d) a high overbased and a low overbased calcium sulfonate, wherein the lubricating oil composition is essentially free of zinc di-alkyl di-thiophosphates and contains no more than 0.1 weight percent sulfur and provided the lubricating oil composition does not contain aromatics alkylated and non-alkylated aromatic amines and tri-nuclear molybdenum compounds.
- the present invention is also directed to method for lubricating internal combustion engines, which comprises lubricating the engine with a low sulfur and low phosphorus lubricating oil compositions of the present invention.
- the present invention is directed to a low sulfur and low phosphorus lubricating oil composition
- a low sulfur and low phosphorus lubricating oil composition comprising:
- the one or more detergents in (d) above is not an overbased metal phenate, an overbased metal salicylate or an overbased metal carboxylate.
- the concentration of the zinc di-alkyl di-thiophosphates is less than 0.2 weight percent based on the total weight of the lubricating oil composition. More preferably the concentration of the zinc di-alkyl di-thiophosphates is less than 0.1 weight percent based on the total weight of the lubricating oil composition, and most preferably the concentration of the zinc di-alkyl di-thiophosphates is less than 0.0 based on the total weight of the lubricating oil composition.
- the lubricating oil composition of the present invention has a low sulfated ash content.
- the sulfur content of the lubricating oil composition of the present invention is in the range of 0.0 weight percent to about 0.09 weight percent based on the total weight of the lubricating oil composition. More preferably the sulfur content of the lubricating oil composition of the present invention is in the range of 0.01 weight percent to about 0.07 weight percent based on the total weight of the lubricating oil composition. Most preferably the sulfur content of the lubricating oil composition of the present invention is in the range of 0.02 weight percent to about 0.05 weight percent based on the total weight of the lubricating oil composition.
- the phosphorus content of the lubricating oil composition of the present invention is in the range of 0.0 weight percent to about 0.03 weight percent based on the total weight of the lubricating oil composition. More preferably the phosphorus content of the lubricating oil composition of the present invention is in the range of 0.0 weight percent to about 0.02 weight percent based on the total weight of the lubricating oil composition. Even more preferably the phosphorus content of the lubricating oil composition of the present invention is in the range of 0.0 weight percent to about 0.01 weight percent based on the total weight of the lubricating oil composition and most preferably it is 0.0.
- Preferred dispersants that may be employed in the lubricating oil composition of the present invention are ashless dispersants.
- ashless dispersants are alkenyl succinimides and succinamides. These dispersants can be further modified by reaction with, for example, with boron or ethylene carbonate. Ester-based ashless dispersants derived from long chain hydrocarbon-substituted carboxylic acids and hydroxy compounds may also be employed. More preferred ashless dispersants are those derived from polyisobutenyl succinic anhydride.
- Preferred examples of anti-oxidants employable in the lubricating oil of the present invention are esters of thiodicarboxylic acids, di-thiocarbamates, such as 15-methylenebis(di-butyl di-thiocarbamate), salts of di-thiophosphoric acids, alkyl or aryl phosphates.
- Molybdenum compounds such as amine-molybdenum complex compound and molybdenum di-thiocarbamates may also be used as anti-oxidants and hindered phenols, such as 4,4'-methylene-bis(2,6-di-tert-butylphenol), 4,4'-bis(2,6-di-tert-butylphenol), 4,4'-bis(2-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol), 4,4'-isopropylidene-bis(2,6-di-tert-butylphenol), 2,2'-methylene-bis(4-methyl-6-nonylphenol), 2,2'-isobutylidene-bis(4,6-dimethylphenol), 2,2'-5-methylene-bis(4-methyl-6-cyclohexylphenol), 2,6-
- Examples of the preferred low and high overbased metal detergents that may be employed in the lubricating oil composition of the present invention are low and high overbased sulfonic acids or Mannich condensation products of alkylphenols, aldehydes and amines. More preferred are low and high overbased sulfonic acids. It is preferred that the overbased detergents do not include overbased salicylic acids, carboxylic acids and phenols. These detergents may be alkali metal detergents or alkaline earth metal detergents. Preferably they are alkaline earth metal detergents and more preferably they are calcium detergents. The TBN of these detergents is greater than 1 and about 500, or more.
- the one or more detergents in (d) above is not an overbased metal phenate, an overbased metal salicylate or an overbased metal carboxylate.
- the concentration of the zinc di-alkyl di-thiophosphates is less than 0.2 weight percent based on the total weight of the lubricating oil composition. More preferably the concentration of the zinc di-alkyl di-thiophosphates is less than 0.1 weight percent based on the total weight of the lubricating oil composition, and most preferably the concentration of the zinc di-alkyl di-thiophosphates is less than 0.0 based on the total weight of the lubricating oil composition.
- the sulfur content of the lubricating oil composition of the above embodiment is in the range of 0.0 weight percent to about 0.09 weight percent based on the total weight of the lubricating oil composition. More preferably the sulfur content of the lubricating oil composition of the present invention is in the range of 0.01 weight percent to about 0.07 weight percent based on the total weight of the lubricating oil composition. Most preferably the sulfur content of the lubricating oil composition of the present invention is in the range of 0.02 weight percent to about 0.05 weight percent based on the total weight of the lubricating oil composition.
- the phosphorus content of the lubricating oil composition of the above embodiment is in the range of 0.0 weight percent to about 0.03 weight percent based on the total weight of the lubricating oil composition. More preferably the phosphorus content of the lubricating oil composition of the present invention is in the range of 0.0 weight percent to about 0.02 weight percent based on the total weight of the lubricating oil composition. Even more preferably the phosphorus content of the lubricating oil composition of the present invention is in the range of 0.0 weight percent to about 0.01 weight percent based on the total weight of the lubricating oil composition and most preferably it is 0.0.
- the lubricating oil composition of the present invention has low sulfated ash.
- the one or more detergents in (e) above is not an overbased metal phenate, an overbased metal salicylate or an overbased metal carboxylate.
- the sulfur content of the lubricating oil composition of the above embodiment is in the range of 0.0 weight percent to about 0.09 weight percent based on the total weight of the lubricating oil composition. More preferably the sulfur content of the lubricating oil composition of the present invention is in the range of 0.01 weight percent to about 0.07 weight percent based on the total weight of the lubricating oil composition. Most preferably the sulfur content of the lubricating oil composition of the present invention is in the range of 0.02 weight percent to about 0.05 weight percent based on the total weight of the lubricating oil composition.
- the phosphorus content of the lubricating oil composition of the above embodiment is in the range of 0.0 weight percent to about 0.03 weight percent based on the total weight of the lubricating oil composition. More preferably the phosphorus content of the lubricating oil composition of the present invention is in the range of 0.0 weight percent to about 0.02 weight percent based on the total weight of the lubricating oil composition. Even more preferably the phosphorus content of the lubricating oil composition of the present invention is in the range of 0.0 weight percent to about 0.01 weight percent based on the total weight of the lubricating oil composition and most preferably it is 0.0.
- the lubricating oil composition of the present invention may also contain viscosity index improvers such as olefin copolymers, examples of which are ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, polybutene, polyisobutylene, polymethacrylates, vinylpyrrolidone and methacrylate copolymers and dispersant type viscosity index improvers.
- viscosity index improvers such as olefin copolymers, examples of which are ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, polybutene, polyisobutylene, polymethacrylates, vinylpyrrolidone and methacrylate copolymers and dispersant type viscosity index improvers.
- Pour point depressants that lower the temperature at which the fluid will flow or can be poured may also be included in the lubricating oil composition of the present invention.
- Additives that optimize the low temperature fluidity of the lubricating oil are various copolymers, such as polymethacrylates.
- Rust inhibitors include nonionic polyoxyethylene surface active agents, such as polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol mono-oleate, and polyethylene glycol mono-oleate.
- nonionic polyoxyethylene surface active agents such as polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol mono-oleate, and polyethylene glycol mono-oleate.
- rust inhibitors include stearic acid and other fatty acids, di-carboxylic acids, metal soaps, fatty acid amine salts, metal salts of heavy sulfonic acid, partial carboxylic acid ester of polyhydric alcohol, and phosphoric ester.
- the more preferred rust inhibitors are those that do not contribute to the phosphorus or sulfur content of the lubricating oil.
- Friction modifiers employable in the lubricating oil composition of the present invention include ash-containing as well as ashless friction modifiers.
- Friction modifiers include, but are not limited to, fatty alcohols, fatty acids, such as stearic acid, isostearic acid, oleic acid and other fatty acids or salts and esters thereof, borated esters, amines, phosphates, and di-, and tri-hydrocarbyl phosphates, hydrocarbyl phosphites and phosphonates. Friction modifiers may also contain molybdenum, provided the molybdenum compounds do not include tri-nuclear molybdenum.
- the friction modifiers used in the lubricating oil composition of the present invention are ashless friction modifiers.
- Extreme pressure agents that may be used in the lubricating oil composition of the present invention include alkaline earth metal borated extreme pressure agents and alkali metal borated extreme pressure agents. Extreme pressure agents containing molybdenum may also be employed in the lubricating oil composition of the present invention, provided the molybdenum compounds do not include tri-nuclear molybdenum.
- Sulfurized olefins zinc dialky-1-dithiophosphate (primary alkyl, secondary alkyl, and aryl type), di-phenyl sulfide, methyl tri-chlorostearate, chlorinated naphthalene, fluoroalkylpolysiloxane, lead naphthenate, neutralized or partially neutralized phosphates, di-thiophosphates, and sulfur-free phosphates.
- the preferred extreme pressure agents are those that will not contribute to the phosphorus content of the lubricating oil.
- Preferred corrosion inhibitors contemplated for use in the lubricating oil of the present invention are derivatives of di-phenyl amines, derivatives of succinimides, sulfurized olefins and the co-sulfurized alkenyl esters/alpha olefin corrosion inhibitors.
- the corrosion inhibitors such as metal di-thiophosphates, especially zinc di-alkyl di-thiophosphate, are less desirable because they contribute to the zinc, phosphorus and sulfur content of the lubricating oil. More preferred corrosion inhibitors are the derivatives of succinimides.
- Metal deactivators that are employable in the lubricating oil of the present invention include di-salicylidene propylenediamine, triazole derivatives, mercaptobenzothiazoles, thiodiazole derivatives, and mercaptobenzimidazoles.
- the lubricating oil composition of the present invention may employ seal swell agents, including but are not limited to, di-esters such as di-2-ehtylhexylsebacate, di-octyladipate and di-2-ethylhexylphthalate, mineral oils with aliphatic alcohols, such as tri-decyl alcohol and trisphosphite ester in combination with a hydrocarbonyl-substituted phenol.
- seal swell agents including but are not limited to, di-esters such as di-2-ehtylhexylsebacate, di-octyladipate and di-2-ethylhexylphthalate, mineral oils with aliphatic alcohols, such as tri-decyl alcohol and trisphosphite ester in combination with a hydrocarbonyl-substituted phenol.
- Demulsifiers that may be employed in the lubricating oil of the present invention include, but are not limited to, addition product of alkylphenol and ethylene oxide, polyoxyethylene alkyl ether, and polyoxyethylene sorbitan ester.
- Useful foam inhibitors for the present invention are alkyl methacrylate.
- the sulfur content of the lubricating oil composition of the above embodiment is in the range of 0.0 weight percent to about 0.09 weight percent based on the total weight of the lubricating oil composition. More preferably the sulfur content of the lubricating oil composition of the present invention is in the range of 0.01 weight percent to about 0.07 weight percent based on the total weight of the lubricating oil composition. Most preferably the sulfur content of the lubricating oil composition of the present invention is in the range of 0.02 weight percent to about 0.05 weight percent based on the total weight of the lubricating oil composition.
- the phosphorus content of the lubricating oil composition of the above embodiment is in the range of 0.0 weight percent to about 0.03 weight percent based on the total weight of the lubricating oil composition. More preferably the phosphorus content of the lubricating oil composition of the present invention is in the range of 0.0 weight percent to about 0.02 weight percent based on the total weight of the lubricating oil composition. Even more preferably the phosphorus content of the lubricating oil composition of the present invention is in the range of 0.0 weight percent to about 0.01 weight percent based on the total weight of the lubricating oil composition and most preferably it is 0.0.
- the one or more detergents in (e) above is not an overbased metal phenate, an overbased metal salicylate or an overbased metal carboxylate.
- the oil of lubricating viscosity is not a liquid polymer of alpha olefins.
- the one or more detergents in (d) above is not an overbased metal phenate, an overbased metal salicylate or an overbased metal carboxylate.
- the one or more detergents in (e) above is not an overbased metal phenate, an overbased metal salicylate or an overbased metal carboxylate.
- a further embodiment of the present invention is directed to a method for lubricating internal combustion engines, which comprises lubricating the engine with a low sulfur and low phosphorus lubricating oil composition comprising:
- the engines are diesel engines, gasoline engines and natural gas engines.
- the one or more detergents in (d) above is not an overbased metal phenate, an overbased metal salicylate or an overbased metal carboxylate.
- Another embodiment of the present invention is directed to a method for lubricating internal combustion engines, which comprises lubricating the engine with a low sulfur and low phosphorus lubricating oil composition consisting essentially of:
- the engines are diesel engines, gasoline engines and natural gas engines.
- the one or more detergents in (e) above is not an overbased metal phenate, an overbased metal salicylate or an overbased metal carboxylate.
- alkali metal refers to Group IA metals of the Periodic Table.
- alkaline earth metal refers to Group II metals of the Periodic Table, such as calcium and magnesium.
- zinc di-alkyl di-thiophosphate content in the lubricating oil composition of the present invention refers to the zinc di-alkyl di-thiophosphate content in the lubricating oil composition of the present invention.
- zinc di-alkyl di-thiophosphate content in the lubricating oil composition is less than 0.2 weight percent based on the total weight of the lubricating oil composition. More preferably the zinc di-alkyl di-thiophosphate content in the lubricating oil composition is less than 0.1 weight percent based on the total weight of the lubricating oil composition. Even more preferably the zinc di-alkyl di-thiophosphate content in the lubricating oil composition is less than 0.05 weight percent based on the total weight of the lubricating oil composition. Most preferably the zinc di-alkyl di-thiophosphate content in the lubricating oil composition is 0.0 weight percent based on the total weight of the lubricating oil composition.
- low phosphorus refers to the phosphorus content of the lubricating oil.
- the phosphorus content of the lubricating oil is preferably in the range from about 0.0 weight percent to about 0.03 weight percent based on the total weight of the lubricating oil. More preferably the phosphorus content of the lubricating oil is in the range from about 0.0 weight percent to about 0.02 weight percent based on the total weight of the lubricating oil. Even more preferably the phosphorus content of the lubricating oil is in the range from about 0.0 weight percent to about 0.01 weight percent based on the total weight of the lubricating oil. Most preferably the phosphorus content of the lubricating oil is 0.0 weight percent based on the total weight of the lubricating oil.
- low sulfur refers to the sulfur content of the lubricating oil.
- the sulfur content of the lubricating oil is no more than 0.1 weight percent based on the total weight of the lubricating oil composition.
- the sulfur content is in the range from about 0.0 weight percent to about 0.09 weight percent based on the total weight of the lubricating oil.
- the sulfur content of the lubricating oil is in the range from about 0.0 weight percent to about 0.07 weight percent based on the total weight of the lubricating oil.
- the sulfur content of the lubricating oil is preferably in the range from about 0.0 weight percent to about 0.05 weight percent based on the total weight of the lubricating oil.
- overbased refers to alkali metal and alkaline earth metal alkyl sulfonates in which the ratio of the number of equivalents of an alkali metal or alkaline earth metal to the number of equivalents of the organic moiety is greater than 1.
- Low overbased refers to alkali metal or alkaline earth metal alkyl sulfonates having a Total Base Number (TBN) greater than 1 and less than 20
- medium overbased refers to alkali metal or alkaline earth metal alkyl sulfonates having a TBN greater than 20 and less than 200.
- High overbased refers to alkali metal or alkaline earth metal alkyl sulfonates having a TBN greater than 200.
- Total Base Number refers to the amount of base equivalent to milligrams of KOH in one gram of sample. Thus, higher TBN numbers reflect more alkaline products, and therefore a greater alkalinity. TBN was determined using ASTM D 2896 test.
- a low sulfur and low phosphorus lubricating oil composition of the present invention provides good wear control when used in diesel engines, gasoline engines and natural gas engines. Wear control in conventional lubricating oil compositions is achieved by the addition of metal salts of di-alkyl di-thiophosphates, for example zinc di-alkyl di-thiophosphates, however, the phosphorus causes inactivation of oxidation catalysts used in exhaust after-treatment devices.
- the lubrication oil composition of the present invention provides good wear control without contributing to high sulfur content, and because it contains essentially no phosphorus, it does not inactivate the oxidation catalysts.
- the lubricating oil formulation of the present invention featuring ultra-low or no phosphorus in combination with low sulfur and sulfated ash exhibited excellent cylinder liner wear control.
- the lubricating oil composition of the present invention may be prepared by simple blending or mixing of the compounds described in more detail below. These compounds may also be preblended as a concentrate or package with various other additives in appropriate ratios to facilitate blending of a lubricating oil composition containing the desired concentration of additives.
- Oil of lubricating viscosity, or base oil as used herein refer to lubricating oils which may be mineral oil or synthetic oils of lubricating viscosity and preferably useful in the crankcase of an internal combustion engine.
- Crankcase lubricating oils ordinarily have a viscosity of about 1300 centistokes at -17.8°C to 22.7 centistokes at 98.9°C.
- the lubricating oils may be derived from synthetic or natural sources.
- Mineral oil for use as the base oil in this invention includes paraffinic, naphthenic and other oils that are ordinarily used in lubricating oil compositions.
- Synthetic oils include hydrocarbon synthetic oils and synthetic esters.
- Useful synthetic hydrocarbon oils include liquid polymers of alpha-olefins having the proper viscosity. Especially useful are the hydrogenated liquid oligomers of C 6 to C 12 alpha-olefins such as 1-decene trimer. Similarly, alkyl benzenes of proper viscosity, such as didodecyl benzene, may be used.
- Useful synthetic esters include the esters of both mono-carboxylic acids and polycarboxylic acids as well as mono-hydroxy alkanols and polyols. Typical examples are didodecyl adipate, pentaerthritol tetracapoate, di-2-ethylhexyl adipate, di-laurylsebacate and the like. Complex esters prepared from mixtures of mono- and di-carboxylic acid and mono- and di-hydroxy alkanols can also be used.
- Blends of hydrocarbon oils and synthetic oils may also be used. For example, blends of 10 weight percent to 25 weight percent hydrogenated 1-decene trimer with 75 weight percent to 90 weight percent 683 centistokes at 37.8°C mineral oil gives an excellent oil base. Fischer-Tropsch derived base oils may also be employed in the lubricating oil composition of the present invention.
- the oil of lubricating viscosity employed for preparing the lubricating oil composition of the present invention is a low sulfur base oil.
- a low sulfur base oil assists in obtaining a lubricating oil composition which is ultra low in sulfur content.
- Sulfur content of base oils is well known by persons skilled in the art, thus, selection of a low sulfur base oil may be conveniently made for the purpose of the present invention.
- the lubricating oil composition of the present invention contains dispersants.
- the ashless dispersants are nitrogen-containing dispersants formed by reacting alkenyl succinic acid anhydride with an amine.
- examples of such dispersants are alkenyl succinimides and succinamides.
- These dispersants can be further modified by reaction with, for example, boron or ethylene carbonate.
- Ester-based ashless dispersants derived from long chain hydrocarbon-substituted carboxylic acids and hydroxy compounds may also be employed.
- Preferred ashless dispersants are those derived from polyisobutenyl succinic anhydride. A large number of dispersants are commercially available.
- Anti-oxidants are used in lubricating oils for inhibition of decomposition processes that occur naturally in lubricating oils as they age or oxidize in the presence of air. These oxidation processes may cause formation of gums, lacquers and sludge resulting in an increase in acidity and viscosity.
- antioxidants such as 4,4'-methylene-bis(2,6-di-tert-butylphenol), 4,4'-bis(2,6-di-tertbutylphenol), 4,4'-bis(2-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol), 4,4'-isopropylidene-bis(2,6-di-tert-butylphenol), 2,2'-methylene-bis(4-methyl-6-nonylphenol), 2,2'-isobutylidene-bis(4,6-dimethylphenol), 2,2'-5-methylene-bis(4-methyl-6-cyclohexylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethy
- alkylated and non-alkylated aromatic amines are alkylated diphenylamine, phenyl-alpha-naphthylamine, and alkylated-alpha-naphthylamine.
- Other classes of anti-oxidants are esters of thiodicarboxylic acids, salts of di-thiophosphoric acids, alkyl or aryl phosphates and molybdenum compounds, such as amine-molybdenum complex compound and molybdenum di-thiocarbamates may also be used as anti-oxidants, provided the molybdenum compounds do not include tri-nuclear molybdenum. However, their addition of the will contribute to the phosphorus, sulfur and sulfated ash content of the lubricating oil.
- Examples of the low and medium overbased metal detergents employed in the lubricating oil composition of the present invention are low, medium or high overbased sulfonic acids or Mannich condensation products of alkylphenols, aldehydes and amines. It is preferred that the overbased detergents do not include overbased salicylic acids, carboxylic acids and phenols.
- These detergents may be alkali metal detergents or alkaline earth metal detergents. Preferably they are alkaline earth metal detergents and more preferably they are calcium detergents.
- the TBN of these detergents is greater than 1 and about 500, or more. These detergents are well known in the art and are commercially available.
- the lubricating oil composition of the present invention may also contain, in addition to the additives discussed above, other additives used to impart desirable properties to the lubricating oil composition of the present invention.
- the lubricating oil may contain one or more of additives, such as viscosity index improvers, pour point depressants, demulsifiers, extreme pressure agents and foam inhibitors. These additional additives are described in more detail below.
- Viscosity index improvers are added to lubricating oil to regulate viscosity changes due to the change in temperature.
- Some commercially available examples of viscosity index improvers are olefin copolymers, such as ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, polybutene, polyisobutylene, polymethacrylates, vinylpyrrolidone and methacrylate copolymers and dispersant type viscosity index improvers.
- Extreme pressure agents that may be used in the lubricating oil composition of the present invention include alkaline earth metal borated extreme pressure agents and alkali metal borated extreme pressure agents. Extreme pressure agents containing molybdenum may also be employed in the lubricating oil composition of the present invention, provided the molybdenum compounds do not include tri-nuclear molybdenum.
- Sulfurized olefins zinc dialky-1-dithiophosphate (primary alkyl, secondary alkyl, and aryl type), di-phenyl sulfide, methyl tri-chlorostearate, chlorinated naphthalene, fluoroalkylpolysiloxane, lead naphthenate, neutralized or partially neutralized phosphates, di-thiophosphates, and sulfur-free phosphates.
- the preferred extreme pressure agents are those that will not contribute to the phosphorus content of the lubricating oil.
- Polymethyl methacrylate is an example of a pour point depressant useful for addition to the lubricating oil of the present invention.
- Rust inhibitors include nonionic polyoxyethylene surface active agents, such as polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol mono-oleate, and polyethylene glycol mono-oleate.
- nonionic polyoxyethylene surface active agents such as polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol mono-oleate, and polyethylene glycol mono-oleate.
- rust inhibitors include stearic acid and other fatty acids, di-carboxylic acids, metal soaps, fatty acid amine salts, metal salts of heavy sulfonic acid, partial carboxylic acid ester of polyhydric alcohol, and phosphoric ester.
- preferred rust inhibitors are those that do not contribute to the phosphorus or sulfur content of the lubricating oil.
- Corrosion inhibitors are included in lubricating oils to protect vulnerable metal surfaces. Such corrosion inhibitors are generally used in very small amounts in the range of from about 0.02 weight percent to about 1.0 weight percent. Examples of corrosion inhibitors that may be used are sulfurized olefin corrosion inhibitor and the co-sulfurized alkenyl ester/alpha olefin corrosion inhibitor.
- the corrosion inhibitors should not be a metal di-thiophosphates, especially zinc di-alkyl di-thiophosphate because addition of this corrosion inhibitor will contribute to the zinc, phosphorus and sulfur content of the lubricating oil.
- Friction modifiers that are employable in the lubricating oil composition of the present invention include both ash-containing as well as ashless friction modifiers.
- Friction modifiers include, but are not limited to, fatty alcohols, fatty acids, such as stearic acid, isostearic acid, oleic acid and other fatty acids or salts and esters thereof, borated esters, amines, phosphates, and di-, and tri-hydrocarbyl phosphates, hydrocarbyl phosphites and phosphonates. hydrocarbyl phosphites. Friction modifiers may also contain molybdenum, provided the molybdenum compounds do not include tri-nuclear molybdenum.
- the friction modifiers used in the lubricating oil composition of the present invention are ashless friction modifiers.
- Metal deactivators that may be employed in the lubricating oil composition of the present invention include but are not limited to di-salicylidene propylenediamine, triazole derivatives, mercaptobenzothiazoles, thiodiazole derivatives, and mercaptobenzimidazoles.
- the lubricating oil composition of the present invention may employ seal swell agents, including but are not limited to, di-esters such as di-2-ehtylhexylsebacate, di-octyladipate and di-2-ethylhexylphthalate, mineral oils with aliphatic alcohols, such as tri-decyl alcohol and Trisphosphite ester in combination with a hydrocarbonyl-substituted phenol.
- seal swell agents including but are not limited to, di-esters such as di-2-ehtylhexylsebacate, di-octyladipate and di-2-ethylhexylphthalate, mineral oils with aliphatic alcohols, such as tri-decyl alcohol and Trisphosphite ester in combination with a hydrocarbonyl-substituted phenol.
- Addition product of alkylphenol and ethylene oxide, polyoxyethylene alkyl ether, and polyoxyethylene sorbitan ester may be employed in the lubricating oil composition of the present invention.
- Useful foam inhibitors for the present invention are alkyl methacrylate polymers, dimethyl silicone polymers and polysiloxane type foam inhibitors.
- the lubricating oil may contain a compatible combination of additives of each of the above classes of additives in effective amounts.
- the low sulfur and low phosphorus lubricating oil composition of the present invention was evaluated for its anti-wear performance in formulations prepared as described in Example 1 and Table I below.
- Comparative Formulation A and Test Formulation B contained two dispersants, two anti-oxidants, a low overbased and a high overbased sulfonate, a corrosion inhibitor and an anti-foaming agent. Base oil was used to make-up a 100 percent of each of Comparative Formulation A and Test Formulation B.
- Test Formulation B The anti-wear performance of Test Formulation B was compared with Comparative Formulation A which contained zinc di-alkyl di-thiophosphate in addition to the other components given above.
- the degree of wear control with Test Formulation B was determined as a reduction in cylinder liner wear compared with Comparative Formulation A.
- Comparative Formulation A and Test Formulation B are described in more detail in Table II below.
- the amounts of the components in the lubricating oil formulations are given in Table II in weight percent active additive.
- Table II Component Formulation (weight %) Comparative Formulation A Test formulation B Base Oil Borated Dispersant 1.0 1.0 Non-borated Dispersant 5.7 5.7 Low Overbased Calcium Sulfonate 0.4 0.4 High Overbased Calcium Sulfonate 0.8 0.8 0.8 Molybdenum Antioxidant 0.12 0.12 Phenolic Antioxidant 0.11 0.11 Corrosion Inhibitor 0.8 0.8 Foam Inhibitor 0.02 0.02 Zinc Di-alkyl Di-thiophosphate 1.4 0.0
- Table III below shows the amount of the sulfur and phosphorus in Comparative Formulation A and Test Formulation B.
- Table III Component (weight %) Comparative Formulation A Test Formulation C Sulfur 0.35 0.04 Phosphorus 0.16 0.00
- Test Formulation B The anti-wear control of Test Formulation B was compared to Comparative Formulation A was evaluated as described below.
- Wear measurements were performed in a Mack Diesel Engine, installed in an engine test laboratory.
- the engine stand configuration was in conformance to the Mack T-10 engine test procedure known as ASTM Test Method D-6987.
- the engine was equipped with radiated cylinder liners and a system to circulate the engine lubricant through an external reservoir.
- a detector was placed in the reservoir to count the gamma-rays from the oil being circulated past the detector. The increase in the gamma-ray count over a fixed period of time is a measure of the amount of metal weight loss from the radiated area, in this case the cylinder liner area around the top ring reversal point.
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| US11/273,952 US20070111904A1 (en) | 2005-11-14 | 2005-11-14 | Low sulfur and low phosphorus lubricating oil composition |
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| EP3250664A4 (en) * | 2015-01-29 | 2018-02-07 | Bestline International Research, Inc. | Motor oil blend and method for reducing wear on steel and eliminating zddp in motor oils by modifying the plastic response of steel |
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| US8361940B2 (en) * | 2006-09-26 | 2013-01-29 | Chevron Japan Ltd. | Low sulfated ash, low sulfur, low phosphorus, low zinc lubricating oil composition |
| JP5079407B2 (ja) * | 2007-06-28 | 2012-11-21 | シェブロンジャパン株式会社 | 省燃費ディーゼルエンジン潤滑用潤滑油組成物 |
| US8383563B2 (en) * | 2007-08-10 | 2013-02-26 | Exxonmobil Research And Engineering Company | Method for enhancing the oxidation and nitration resistance of natural gas engine oil compositions and such compositions |
| US20100081591A1 (en) * | 2008-09-30 | 2010-04-01 | Chevron Oronite Company Llc | Lubricating oil compositions |
| US8969273B2 (en) * | 2009-02-18 | 2015-03-03 | Chevron Oronite Company Llc | Lubricating oil compositions |
| US20100206260A1 (en) * | 2009-02-18 | 2010-08-19 | Chevron Oronite Company Llc | Method for preventing exhaust valve seat recession |
| US8288326B2 (en) * | 2009-09-02 | 2012-10-16 | Chevron Oronite Company Llc | Natural gas engine lubricating oil compositions |
| EP2550346B1 (en) * | 2010-03-25 | 2020-11-04 | Vanderbilt Chemicals, LLC | Ultra low phosphorus lubricant compositions |
| US20140187453A1 (en) * | 2012-12-28 | 2014-07-03 | Chevron Oronite LLC | Ultra-low saps lubricants for internal combustion engines |
| US9885004B2 (en) * | 2013-12-23 | 2018-02-06 | Exxonmobil Research And Engineering Company | Method for improving engine fuel efficiency |
| US20150175923A1 (en) * | 2013-12-23 | 2015-06-25 | Exxonmobil Research And Engineering Company | Method for improving engine fuel efficiency |
| US10190072B2 (en) * | 2013-12-23 | 2019-01-29 | Exxonmobil Research And Engineering Company | Method for improving engine fuel efficiency |
| JP6300686B2 (ja) * | 2014-01-31 | 2018-03-28 | Ｅｍｇルブリカンツ合同会社 | 潤滑油組成物 |
| WO2022090946A1 (en) * | 2020-10-28 | 2022-05-05 | Chevron U.S.A. Inc. | Lubricating oil composition with renewable base oil, having low sulfur and sulfated ash content and containing molybdenum and boron compounds |
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| EP3250664A4 (en) * | 2015-01-29 | 2018-02-07 | Bestline International Research, Inc. | Motor oil blend and method for reducing wear on steel and eliminating zddp in motor oils by modifying the plastic response of steel |
Also Published As
| Publication number | Publication date |
|---|---|
| US20070111904A1 (en) | 2007-05-17 |
| JP2007138165A (ja) | 2007-06-07 |
| CA2567263A1 (en) | 2007-05-14 |
| JP5431641B2 (ja) | 2014-03-05 |
| SG132615A1 (en) | 2007-06-28 |
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