CA2336505A1 - Marine diesel engine lubricating oil composition having improved high temperature performance - Google Patents
Marine diesel engine lubricating oil composition having improved high temperature performance Download PDFInfo
- Publication number
- CA2336505A1 CA2336505A1 CA002336505A CA2336505A CA2336505A1 CA 2336505 A1 CA2336505 A1 CA 2336505A1 CA 002336505 A CA002336505 A CA 002336505A CA 2336505 A CA2336505 A CA 2336505A CA 2336505 A1 CA2336505 A1 CA 2336505A1
- Authority
- CA
- Canada
- Prior art keywords
- lubricating oil
- detergent
- overbased
- oil composition
- ashless dispersant
- 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.)
- Abandoned
Links
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 80
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 239000003599 detergent Substances 0.000 claims abstract description 80
- 239000002270 dispersing agent Substances 0.000 claims abstract description 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 32
- 239000011701 zinc Substances 0.000 claims abstract description 32
- 150000008052 alkyl sulfonates Chemical class 0.000 claims abstract description 30
- 230000001050 lubricating effect Effects 0.000 claims abstract description 13
- 239000002199 base oil Substances 0.000 claims abstract description 12
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 43
- 239000011575 calcium Substances 0.000 claims description 25
- 239000000654 additive Substances 0.000 claims description 24
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 22
- 229910052791 calcium Inorganic materials 0.000 claims description 22
- 239000012141 concentrate Substances 0.000 claims description 20
- 229960002317 succinimide Drugs 0.000 claims description 20
- 230000000996 additive effect Effects 0.000 claims description 19
- 238000002485 combustion reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000003085 diluting agent Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 159000000007 calcium salts Chemical class 0.000 abstract description 25
- 239000003921 oil Substances 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 description 4
- -1 nitrogen-containing compound Chemical class 0.000 description 4
- 229920001281 polyalkylene Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004711 α-olefin Substances 0.000 description 2
- WJECKFZULSWXPN-UHFFFAOYSA-N 1,2-didodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1CCCCCCCCCCCC WJECKFZULSWXPN-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical class ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- ZDMLGWPLXFTSNJ-UHFFFAOYSA-N CCCCCCCCCCCCC1=CC=CC([S+]=P([O-])([O-])[S-])=C1CCCCCCCCCCCC.CCCCCCCCCCCCC1=CC=CC([S+]=P([O-])([O-])[S-])=C1CCCCCCCCCCCC.[Zn+2].[Zn+2].[Zn+2] Chemical compound CCCCCCCCCCCCC1=CC=CC([S+]=P([O-])([O-])[S-])=C1CCCCCCCCCCCC.CCCCCCCCCCCCC1=CC=CC([S+]=P([O-])([O-])[S-])=C1CCCCCCCCCCCC.[Zn+2].[Zn+2].[Zn+2] ZDMLGWPLXFTSNJ-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- AOZDHFFNBZAHJF-UHFFFAOYSA-N [3-hexanoyloxy-2,2-bis(hexanoyloxymethyl)propyl] hexanoate Chemical compound CCCCCC(=O)OCC(COC(=O)CCCCC)(COC(=O)CCCCC)COC(=O)CCCCC AOZDHFFNBZAHJF-UHFFFAOYSA-N 0.000 description 1
- XYRMLECORMNZEY-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S XYRMLECORMNZEY-UHFFFAOYSA-B 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 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
- 239000004327 boric acid Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical compound O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000010779 crude oil Substances 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
- 239000007857 degradation product Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- GHKVUVOPHDYRJC-UHFFFAOYSA-N didodecyl hexanedioate Chemical compound CCCCCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCCCCC GHKVUVOPHDYRJC-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000013538 functional additive Substances 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
- 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 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C10M2207/028—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
- 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
- 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
-
- 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
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- 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
- C10N2030/08—Resistance to extreme temperature
-
- 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
- C10N2030/52—Base number [TBN]
-
- 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
- C10N2060/10—Chemical after-treatment of the constituents of the lubricating composition by sulfur or a compound containing sulfur
-
- 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
-
- 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
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
A lubricating oil composition containing a base oil of lubricating viscosity, overbased sulfurized alkylphenate detergent or its calcium salt, an overbased alkylsulfonate detergent or its calcium salt, an ashless dispersant, and a zinc dialkyldithiophosphate and/or zinc diaryldithiophosphate is described. The lubricating oil composition provides improved heat stability and anti-wear performance in marine diesel engines operated under severe conditions where the cylinder liner temperature reach 200 to 260°C.
Description
MARINE DIESEL ENGINE LUBRICATING OIL COMPOSITION HAVING
IMPROVED HIGH TEMPERATURE PERFORMANCE
The present invention relates to a lubricating oil composition for internal combustion engines, particularly two-stroke cross-head diesel engines such as marine engines. The lubricating oil composition of the present invention is highly effective under severe conditions in which cylinder liner temperatures may reach 200 to 260°C.
BACKGROUND OF THE INVENTION
For conventional two-stroke cross-head diesel internal combustion engines of large ships, a "marine cylinder lubricating oil" is used. Such lubricating oils usually contain various additives for improving durability and/or lubricating performance.
A typical lubricating oil for two-stroke cross-head diesel internal combustion engines of large ships comprises a lubricating base oil in which dissolved or dispersed are additives such as an overbased metal-containing detergent (e.g., calcium sulfonate, calcium phenate, calcium salicylate) and an ashless dispersant.
Metal-containing detergents help to neutralize acidic sulfur oxide (particularly sulfuric acid) that results from the burning of petroleum fuel such as fuel oil of grade C, which contains considerable amounts of sulfur (usually 1.0 to 4.0 wt %). Metal-containing detergents, along with ashless dispersants, also serve to disperse combustion residues, such as soot and sludge, which are produced as the fuel and the lubricating oil deteriorate and to prevent the residues from accumulating on the inner surface of the engine parts such as the pistons, piston grooves, and cylinder liner. While metal-containing detergents and ashless dispersants provide adequate heat stability and anti-wear performance under relatively moderate and high temperatures, their combination cannot give fully satisfactory performance under severe load conditions. In particular, in a two-stroke cross-head diesel engine having a large-caliber cylinder, the temperature at the top area of the cylinder liner wall (near the piston top ring groove) may rise up to 230 to 260°C, which is higher than the temperature in the conventional engine by 20% or more.
Accordingly, if the lubricating oil has insufficient heat stability or gives poor anti-wear performance at such high temperatures, combustion residues produced by thermal deterioration of the lubricating oil accumulate on the top area of the piston or on the piston groove to cause wearing or scuffing on the cylinder liner.
Accordingly, there is a need for a lubricating oil composition having high heat stability and anti-wear performance at high temperatures to comply with the severe load conditions in marine two-stroke cross-head diesel engines.
SUMMARY OF THE INVENTION
The present invention relates to a lubricating oil composition for internal combustion engines, particularly two-stroke cross-head diesel engines such as marine diesel engines. The lubricating oil composition of the present invention is useful in a method of improving the heat stability and anti-wear performance of marine diesel engines operated under severe conditions where cylinder liner temperatures may reach 200 to 260°C.
In its broadest aspect, the present invention comprises a lubricating oil composition having a major amount of a base oil of lubricating viscosity having a kinematic viscosity of 22 to 300 mm2/s at 40°C, overbased sulfurized alkylphenate detergent or its calcium salt, an overbased alkylsulfonate detergent or its calcium salt, an ashless dispersant, and a zinc dialkyldithiophosphate and/or zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent or its calcium salt and the overbased alkylsulfonate detergent or its calcium salt is in the range of 55:45 to 95:5.
In another aspect, the present invention relates to a lubricating oil additive concentrate containing a compatible organic diluent, overbased sulfurized alkylphenate detergent or its calcium salt, an overbased alkylsulfonate detergent or its calcium salt, an ashless dispersant, and a zinc dialkyldithiophosphate and/ or zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent or its calcium salt and the overbased alkylsulfonate detergent or its calcium salt is in the range of 55:45 to 95:5.
In a further aspect, the present invention relates to a method of improving the heat stability and anti-wear performance at high temperatures of an internal combustion engine, particularly a two-stroke cross-head diesel engine, by lubricating the engine with the lubricating oil composition of the present invention.
In still a further aspect, the present invention relates to a method of producing the lubricating oil composition of the present invention by blending a mixture of the components of the lubricating oil composition of the present invention.
The resulting lubricating oil composition having improved heat stability and anti-wear performance at high temperatures in an internal combustion engine.
Among other factors, the present invention relates to the use of an overbased sulfurized alkylphenate detergent or its calcium salt, an overbased alkylsulfonate detergent or its calcium salt, an ashless dispersant and a zinc dialkyldithiophosphate and/or of a zinc diaryldithiophosphate for improving the heat stability and anti-wear performance at high temperatures of a lubricating oil composition for two-stroke cross-head diesel engines comprising a major amount of a base oil of lubricating viscosity and an effective amount of an overbased sulfurized alkylphenate detergent or its calcium salt, an overbased alkylsulfonate detergent or its calcium salt, an ashless dispersant and a zinc dialkyldithiophosphate andlor of a zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent or its calcium salt and the overbased alkylsulfonate detergent or its calcium salt is in the range of 55:45 to 95:5.
DETAILED DESCRIPTION OF THE INVENTION
In its broadest aspect, the present invention involves a lubricating oil composition for internal combustion engines, particularly two-stroke cross-head diesel engines such as marine diesel engines, having improved heat stability and anti-wear performance.
The base oil of lubricating viscosity used in the lubricating oil composition of the present invention may be a mineral or a synthetic base oil having a kinematic viscosity of 22 to 300 mm2/s, preferably 22 to 140 mm2/s at 40°C.
Mineral oil employable for the invention can be obtained from crude oil by distillation (under atmospheric or reduced pressure) and purification such as solvent extraction, hydrogenolysis, solvent dewaxing or hydrogenation refining. Mineral oils for use as the base oil in this invention include, for example, paraffinic, naphthenic and other oils that are ordinarily used in lubricating oil compositions.
Synthetic oils include, for example, both hydrocarbon synthetic oils and synthetic esters and mixtures thereof having desired viscosity. Useful synthetic hydrocarbon oils include liquid polymers of alpha olefins having the proper viscosity. Especially useful are the hydrogenated liquid oligomers of to C~2 alpha olefins such as 1-decene trimer. Likewise, alkyl benzenes of proper viscosity, such as didodecyl benzene, can be used. Useful synthetic esters include the esters of monocarboxylic acids and polycarboxylic acids, as well as mono-hydroxy alkanols and polyols. Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, dilaurylsebacate, and the like. Complex esters prepared from mixtures of mono and dicarboxylic acids and mono and dihydroxy alkanols can also be used. Blends of mineral oils with synthetic oils are also usefuLThe overbased sulfurized alkylphenate detergent of the present invention is a metal salt of sulfurized alkylphenol having an alkyl group of about 8 to 30 carbon atoms. It may be incorporated in an amount of 5.0 to 35.0 wt %, preferably 20 to 30 wt %, based on the total amount of the lubricating oil composition. The wt includes a small amount of remaining hydrocarbon oil used in the preparation of the overbased sulfurized alkylphenate detergent. The overbased sulfurized alkylphenate detergent may also be a salt of an alkali or alkaline earth metal with a sulfurized alkylphenol having an alkyl group of about 8 to 30 carbon atoms. Examples of the salts include lithium salt, sodium salt, calcium salt, magnesium salt and barium salt. Calcium salt is preferred. In the case where a calcium salt of the overbased sulfurized alkyl phenate is used as the detergent, the calcium salt of the overbased sulfurized alkylphenate may be incorporated in an amount of 0.4 to 4.0 wt %, preferably 1.6 to 3.5 wt %, based on its calcium content. The overbased sulfurized alkylphenate or its calcium salt has a Total Base Number (TBN, defined by JIS-K 2501, in terms of mg KOH/g) greater than 200, preferably greater than 250.
If the overbased sulfurized alkylphenate detergent is present in the lubricating oil composition in an amount of less than 5.0 wt %, the lubricating oil composition will not have enough heat-stability at high temperatures to prevent thermal deterioration. On the other hand, even if the detergent is incorporated in an amount of more than 35.0 wt %, the effect corresponding to the increased amount of overbased sulfurized alkylphenate detergent is not brought about and the excess detergent is wasted.
The overbased alkylsulfonate detergent of the present invention is a sulfonate of mineral oil having a molecular weight of about 400 to 6,000 or a sulfonate of an aromatic compound having an alkyl group of about 8 to 30 carbon atoms. It may be incorporated in an amount of 2.5 to 20.0 wt %, preferably 5.0 to 11.25 wt %, based on the total amount of the lubricating oil composition. The wt % includes a small amount of remaining hydrocarbon oil used in the preparation of the overbased alkylsulfonate. The overbased alkylsulfonate detergent may also be a salt of an alkali or alkaline earth metal with a sulfonate of mineral oil having a molecular weight of about 400 to 6,000 or a sulfonate of an aromatic compound having an alkyl group of about 8 to 30 carbon atoms. Examples of the salts include lithium salt, sodium salt, calcium salt, magnesium salt and barium salt. Calcium salt is preferred. In the case where the overbased calcium alkylbenzenesulfonate is used as the detergent, the calcium salt of the overbased alkylsulfonate may be incorporated in an amount of 0.3 to 5.0 wt %, preferably 0.6 to 2.8 wt %, based on its calcium content. For example, an overbased alkyloxybenzenesulfonate prepared by the process described in Japanese Patent Provisional Publication (PCT) No. 9-511015 is employable. The overbased alkylsulfonate or its calcium salt has a Total Base Number (TBN, defined by JIS-K 2501, in terms of mg KOH/g) greater than 200, preferably greater than 250, more preferably greater than 350, and most preferably greater than 450.
If the overbased alkylsulfonate detergent is present in the lubricating oil composition in an amount of less than 2.5 wt %, the lubricating oil composition will not have enough heat-stability at high temperatures to prevent thermal deterioration. On the other hand, even if the detergent is incorporated in an amount of more than 20.0 wt %, the effect corresponding to the increased amount of overbased alkylsulfonate detergent is not brought about and the excess detergent is wasted.
The weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent must be in the range of 55:45 to 95:5 (former: latter), and is preferably 60:40 to 90:10.
In the lubricating oil composition of the present invention, an ashless dispersant is incorporated in an amount of 0.1 to 3.0 wt %, preferably 0.5 to 1.5 wt %, based on the total amount of the composition. In the dispersant, a hydrocarbon oil having been used in preparing the dispersant remains in a small amount, and therefore the above values include the amount of the remaining hydrocarbon oil.
Examples of the ashless dispersants include succinimide, succinic ester, benzylamine and their modified compounds with organic acid, inorganic acid, alcohol or ester. In the case that a succinimide is employed as the dispersant, the above-mentioned range corresponds to 0.001 to 0.1 wt %, preferably 0.005 to 0.05 wt %, in terms of nitrogen content. A preferred ashless dispersant in the present invention is a polyalkylene succinimide.
Polyalkylene succinimides are disclosed in numerous references and are well known in the art. Certain fundamental types of succinimides and the related materials encompassed by the term of art "succinimide" are described in U.S.
Patent Nos. 3,219,666; 3,172,892; and 3,272,746, the disclosures of which are hereby incorporated by reference. The term "succinimide" is understood in the art to include many of the amide, imide, and amidine species which may also be formed. The predominant product however is a succinimide and this term has been generally accepted as meaning the product of a reaction of an alkenyl- or alkyl-substituted succinic acid or anhydride with a nitrogen-containing compound such as a polyalkylene polyamine. The succinimide dispersant is, for example, prepared by a reaction between malefic anhydride and a polybutene having an average molecular weight of about 800 to 8,000 or a chlorinated polybutene having an average molecular weight of about 800 to 8,000 at 100 to 200°C to give a polybutenylsuccinic acid anhydride, and causing the obtained anhydride to react with a polyamine. Examples of the polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine.
The polyalkylene succinimides of the present invention can be prepared by conventional processes, such as disclosed in U.S. Patent No. 2,992,708;
3,018,250; 3,018,291; 3,024,237; 3,100,673; 3,172,892; 3,219,666;
3,272,746; 3,361,673; 3,381,022; 3,912,764; 4,234,435; 4,612,132;
IMPROVED HIGH TEMPERATURE PERFORMANCE
The present invention relates to a lubricating oil composition for internal combustion engines, particularly two-stroke cross-head diesel engines such as marine engines. The lubricating oil composition of the present invention is highly effective under severe conditions in which cylinder liner temperatures may reach 200 to 260°C.
BACKGROUND OF THE INVENTION
For conventional two-stroke cross-head diesel internal combustion engines of large ships, a "marine cylinder lubricating oil" is used. Such lubricating oils usually contain various additives for improving durability and/or lubricating performance.
A typical lubricating oil for two-stroke cross-head diesel internal combustion engines of large ships comprises a lubricating base oil in which dissolved or dispersed are additives such as an overbased metal-containing detergent (e.g., calcium sulfonate, calcium phenate, calcium salicylate) and an ashless dispersant.
Metal-containing detergents help to neutralize acidic sulfur oxide (particularly sulfuric acid) that results from the burning of petroleum fuel such as fuel oil of grade C, which contains considerable amounts of sulfur (usually 1.0 to 4.0 wt %). Metal-containing detergents, along with ashless dispersants, also serve to disperse combustion residues, such as soot and sludge, which are produced as the fuel and the lubricating oil deteriorate and to prevent the residues from accumulating on the inner surface of the engine parts such as the pistons, piston grooves, and cylinder liner. While metal-containing detergents and ashless dispersants provide adequate heat stability and anti-wear performance under relatively moderate and high temperatures, their combination cannot give fully satisfactory performance under severe load conditions. In particular, in a two-stroke cross-head diesel engine having a large-caliber cylinder, the temperature at the top area of the cylinder liner wall (near the piston top ring groove) may rise up to 230 to 260°C, which is higher than the temperature in the conventional engine by 20% or more.
Accordingly, if the lubricating oil has insufficient heat stability or gives poor anti-wear performance at such high temperatures, combustion residues produced by thermal deterioration of the lubricating oil accumulate on the top area of the piston or on the piston groove to cause wearing or scuffing on the cylinder liner.
Accordingly, there is a need for a lubricating oil composition having high heat stability and anti-wear performance at high temperatures to comply with the severe load conditions in marine two-stroke cross-head diesel engines.
SUMMARY OF THE INVENTION
The present invention relates to a lubricating oil composition for internal combustion engines, particularly two-stroke cross-head diesel engines such as marine diesel engines. The lubricating oil composition of the present invention is useful in a method of improving the heat stability and anti-wear performance of marine diesel engines operated under severe conditions where cylinder liner temperatures may reach 200 to 260°C.
In its broadest aspect, the present invention comprises a lubricating oil composition having a major amount of a base oil of lubricating viscosity having a kinematic viscosity of 22 to 300 mm2/s at 40°C, overbased sulfurized alkylphenate detergent or its calcium salt, an overbased alkylsulfonate detergent or its calcium salt, an ashless dispersant, and a zinc dialkyldithiophosphate and/or zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent or its calcium salt and the overbased alkylsulfonate detergent or its calcium salt is in the range of 55:45 to 95:5.
In another aspect, the present invention relates to a lubricating oil additive concentrate containing a compatible organic diluent, overbased sulfurized alkylphenate detergent or its calcium salt, an overbased alkylsulfonate detergent or its calcium salt, an ashless dispersant, and a zinc dialkyldithiophosphate and/ or zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent or its calcium salt and the overbased alkylsulfonate detergent or its calcium salt is in the range of 55:45 to 95:5.
In a further aspect, the present invention relates to a method of improving the heat stability and anti-wear performance at high temperatures of an internal combustion engine, particularly a two-stroke cross-head diesel engine, by lubricating the engine with the lubricating oil composition of the present invention.
In still a further aspect, the present invention relates to a method of producing the lubricating oil composition of the present invention by blending a mixture of the components of the lubricating oil composition of the present invention.
The resulting lubricating oil composition having improved heat stability and anti-wear performance at high temperatures in an internal combustion engine.
Among other factors, the present invention relates to the use of an overbased sulfurized alkylphenate detergent or its calcium salt, an overbased alkylsulfonate detergent or its calcium salt, an ashless dispersant and a zinc dialkyldithiophosphate and/or of a zinc diaryldithiophosphate for improving the heat stability and anti-wear performance at high temperatures of a lubricating oil composition for two-stroke cross-head diesel engines comprising a major amount of a base oil of lubricating viscosity and an effective amount of an overbased sulfurized alkylphenate detergent or its calcium salt, an overbased alkylsulfonate detergent or its calcium salt, an ashless dispersant and a zinc dialkyldithiophosphate andlor of a zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent or its calcium salt and the overbased alkylsulfonate detergent or its calcium salt is in the range of 55:45 to 95:5.
DETAILED DESCRIPTION OF THE INVENTION
In its broadest aspect, the present invention involves a lubricating oil composition for internal combustion engines, particularly two-stroke cross-head diesel engines such as marine diesel engines, having improved heat stability and anti-wear performance.
The base oil of lubricating viscosity used in the lubricating oil composition of the present invention may be a mineral or a synthetic base oil having a kinematic viscosity of 22 to 300 mm2/s, preferably 22 to 140 mm2/s at 40°C.
Mineral oil employable for the invention can be obtained from crude oil by distillation (under atmospheric or reduced pressure) and purification such as solvent extraction, hydrogenolysis, solvent dewaxing or hydrogenation refining. Mineral oils for use as the base oil in this invention include, for example, paraffinic, naphthenic and other oils that are ordinarily used in lubricating oil compositions.
Synthetic oils include, for example, both hydrocarbon synthetic oils and synthetic esters and mixtures thereof having desired viscosity. Useful synthetic hydrocarbon oils include liquid polymers of alpha olefins having the proper viscosity. Especially useful are the hydrogenated liquid oligomers of to C~2 alpha olefins such as 1-decene trimer. Likewise, alkyl benzenes of proper viscosity, such as didodecyl benzene, can be used. Useful synthetic esters include the esters of monocarboxylic acids and polycarboxylic acids, as well as mono-hydroxy alkanols and polyols. Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, dilaurylsebacate, and the like. Complex esters prepared from mixtures of mono and dicarboxylic acids and mono and dihydroxy alkanols can also be used. Blends of mineral oils with synthetic oils are also usefuLThe overbased sulfurized alkylphenate detergent of the present invention is a metal salt of sulfurized alkylphenol having an alkyl group of about 8 to 30 carbon atoms. It may be incorporated in an amount of 5.0 to 35.0 wt %, preferably 20 to 30 wt %, based on the total amount of the lubricating oil composition. The wt includes a small amount of remaining hydrocarbon oil used in the preparation of the overbased sulfurized alkylphenate detergent. The overbased sulfurized alkylphenate detergent may also be a salt of an alkali or alkaline earth metal with a sulfurized alkylphenol having an alkyl group of about 8 to 30 carbon atoms. Examples of the salts include lithium salt, sodium salt, calcium salt, magnesium salt and barium salt. Calcium salt is preferred. In the case where a calcium salt of the overbased sulfurized alkyl phenate is used as the detergent, the calcium salt of the overbased sulfurized alkylphenate may be incorporated in an amount of 0.4 to 4.0 wt %, preferably 1.6 to 3.5 wt %, based on its calcium content. The overbased sulfurized alkylphenate or its calcium salt has a Total Base Number (TBN, defined by JIS-K 2501, in terms of mg KOH/g) greater than 200, preferably greater than 250.
If the overbased sulfurized alkylphenate detergent is present in the lubricating oil composition in an amount of less than 5.0 wt %, the lubricating oil composition will not have enough heat-stability at high temperatures to prevent thermal deterioration. On the other hand, even if the detergent is incorporated in an amount of more than 35.0 wt %, the effect corresponding to the increased amount of overbased sulfurized alkylphenate detergent is not brought about and the excess detergent is wasted.
The overbased alkylsulfonate detergent of the present invention is a sulfonate of mineral oil having a molecular weight of about 400 to 6,000 or a sulfonate of an aromatic compound having an alkyl group of about 8 to 30 carbon atoms. It may be incorporated in an amount of 2.5 to 20.0 wt %, preferably 5.0 to 11.25 wt %, based on the total amount of the lubricating oil composition. The wt % includes a small amount of remaining hydrocarbon oil used in the preparation of the overbased alkylsulfonate. The overbased alkylsulfonate detergent may also be a salt of an alkali or alkaline earth metal with a sulfonate of mineral oil having a molecular weight of about 400 to 6,000 or a sulfonate of an aromatic compound having an alkyl group of about 8 to 30 carbon atoms. Examples of the salts include lithium salt, sodium salt, calcium salt, magnesium salt and barium salt. Calcium salt is preferred. In the case where the overbased calcium alkylbenzenesulfonate is used as the detergent, the calcium salt of the overbased alkylsulfonate may be incorporated in an amount of 0.3 to 5.0 wt %, preferably 0.6 to 2.8 wt %, based on its calcium content. For example, an overbased alkyloxybenzenesulfonate prepared by the process described in Japanese Patent Provisional Publication (PCT) No. 9-511015 is employable. The overbased alkylsulfonate or its calcium salt has a Total Base Number (TBN, defined by JIS-K 2501, in terms of mg KOH/g) greater than 200, preferably greater than 250, more preferably greater than 350, and most preferably greater than 450.
If the overbased alkylsulfonate detergent is present in the lubricating oil composition in an amount of less than 2.5 wt %, the lubricating oil composition will not have enough heat-stability at high temperatures to prevent thermal deterioration. On the other hand, even if the detergent is incorporated in an amount of more than 20.0 wt %, the effect corresponding to the increased amount of overbased alkylsulfonate detergent is not brought about and the excess detergent is wasted.
The weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent must be in the range of 55:45 to 95:5 (former: latter), and is preferably 60:40 to 90:10.
In the lubricating oil composition of the present invention, an ashless dispersant is incorporated in an amount of 0.1 to 3.0 wt %, preferably 0.5 to 1.5 wt %, based on the total amount of the composition. In the dispersant, a hydrocarbon oil having been used in preparing the dispersant remains in a small amount, and therefore the above values include the amount of the remaining hydrocarbon oil.
Examples of the ashless dispersants include succinimide, succinic ester, benzylamine and their modified compounds with organic acid, inorganic acid, alcohol or ester. In the case that a succinimide is employed as the dispersant, the above-mentioned range corresponds to 0.001 to 0.1 wt %, preferably 0.005 to 0.05 wt %, in terms of nitrogen content. A preferred ashless dispersant in the present invention is a polyalkylene succinimide.
Polyalkylene succinimides are disclosed in numerous references and are well known in the art. Certain fundamental types of succinimides and the related materials encompassed by the term of art "succinimide" are described in U.S.
Patent Nos. 3,219,666; 3,172,892; and 3,272,746, the disclosures of which are hereby incorporated by reference. The term "succinimide" is understood in the art to include many of the amide, imide, and amidine species which may also be formed. The predominant product however is a succinimide and this term has been generally accepted as meaning the product of a reaction of an alkenyl- or alkyl-substituted succinic acid or anhydride with a nitrogen-containing compound such as a polyalkylene polyamine. The succinimide dispersant is, for example, prepared by a reaction between malefic anhydride and a polybutene having an average molecular weight of about 800 to 8,000 or a chlorinated polybutene having an average molecular weight of about 800 to 8,000 at 100 to 200°C to give a polybutenylsuccinic acid anhydride, and causing the obtained anhydride to react with a polyamine. Examples of the polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine.
The polyalkylene succinimides of the present invention can be prepared by conventional processes, such as disclosed in U.S. Patent No. 2,992,708;
3,018,250; 3,018,291; 3,024,237; 3,100,673; 3,172,892; 3,219,666;
3,272,746; 3,361,673; 3,381,022; 3,912,764; 4,234,435; 4,612,132;
4,747,965; 5,112,507; 5,241,003; 5,266,186; 5,286,799; 5,319,030;
5,334,321; 5,356,552; 5,716,912, the disclosures of which are all hereby incorporated by reference in their entirety for all purposes.
The succinimide dispersant of the present invention preferably is a borated succinimide, and the preferred borated dispersant can be prepared, for example, by a reaction between the aforementioned succinimide and a boric acid or boric acid derivative.
If the ashless dispersant is present in the lubricating oil composition in an amount of less than 0.1 wt %, the composition will not show enough sludge dispersing power. Further, if water is present, that composition exhibits poor stability. On the other hand, if the dispersant is incorporated in an amount of more than 3.0 wt %, the composition is liable to have poor heat-stability.
In the lubricating oil composition of the present invention, a zinc dialkyldithiophosphate and/or a zinc diaryldithiophosphate (Zn-DTP) is further incorporated in an amount of 0.1 to 4.0 wt %, more preferably 0.1 to 2.0 wt %, and most preferably 0.1 to 1.5 wt %, based on the total amount of the composition. In Zn-DTP, a hydrocarbon oil having been used in preparing the compound remains in a small amount, and hence the above values include the amount of the remaining hydrocarbon oil. The above-mentioned range corresponds to 0.0075 to 0.3 wt %, more preferably 0.0075 to 0.2 wt %, and most preferably 0.0075 to 0.11 wt %, in terms of phosphorus content.
The alkyl group in the zinc dialkyldithiophosphate is, for example, a straight or branched primary, secondary or tertiary alkyl group of about 2 to 18 carbon atoms. Examples of the alkyl groups include ethyl, propyl, iso-propyl, butyl, _g_ pentyl, hexyl, heptyl, octyl, decyl, dodecyl, and octadecyl. As the zinc diaryldithiophosphate, a zinc dialkylaryldithiophosphate is preferred. The alkylaryl group of the zinc dialkylaryldithiophosphate is, for example, a phenyl group having an alkyl group of about 2 to 18 carbon atoms, such as butylphenyl group, nonylphenyl group, and dodecylphenyl group.
If the zinc dialkyldithiophosphate and/or zinc diaryldithiophosphate is present in the lubricating oil composition in an amount of less than 0.1 wt %, the lubricating oil composition will not show satisfactory anti-oxidation stability. On the other hand, even if the compound is incorporated in an amount of more than 4.0 wt %, the effect corresponding to the increased amount is not brought about.
The lubricating oil composition of the present invention is useful in a method of improving the high temperature heat stability and anti-wear performance of internal combustion engines, particularly two-stroke cross-head diesel engines. In that method, the lubricating oil composition of the present invention is used to lubricate an internal combustion engine.
The lubricating oil composition of the present invention can be prepared by successively or simultaneously adding the additive components to a base oil of lubricating viscosity, or by beforehand preparing a lubricating oil additive concentrate, as herein described below, and then mixing it with a base oil of lubricating viscosity.
In a further embodiment, the lubricating oil composition of the present invention is produced by blending a mixture of the above components. The lubricating oil composition produced by that method might have a slightly different composition than the initial mixture, because the components may interact. The components can be blended in any order and can be blended as combinations of components.
_g_ The lubricating oil additive concentrate of the present invention usually includes the product produced by blending:
a) 1.0 to 50.0 wt % of a compatible organic diluent, b) 5.0 to 90.0 wt % of an overbased sulfurized alkylphenate detergent, c) 5.0 to 90.0 wt % of an overbased alkylsulfonate detergent, d) 0.5 to 50.0 wt % of an ashless dispersant, e) 0.5 to 20 wt % of a zinc dialkyldithiophosphate or of a zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent is in the range of 55:45 to 95:5.
The lubricating oil additive concentrate of the present invention may also include the product produced by blending:
a) 1.0 to 50.0 wt % of a compatible organic diluent, b) 0.4 to 9.0 wt %, based on its calcium content, of an overbased sulfurized alkylphenate detergent, c) 0.6 to 16.0 wt %, based on its calcium content, of an overbased alkylbenzenesulfonate detergent, d) 0.005 to 1.0 wt %, based on its nitrogen content, of a nitrogen-containirig ashless dispersant, e) 0.005 to 1.5 wt %, based on its phosphorus content, of a zinc dialkyldithiophosphate or of a zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent is in the range of 55:45 to 95:5.
The concentrates contain sufficient organic liquid diluent to make them easy to handle during shipping and storage. Typically, the concentrate will contain from 1.0 to 50.0 wt %, preferably 3.0 to 20.0 wt %, more preferably 5.0 to 10.0 wt %, of a compatible organic diluent.
Suitable compatible organic diluents which can be used include, for example, solvent refined 100N, i.e., Cit-Con 100N, and hydrotreated 100N, i.e., Chevron 100N, and the like. The organic diluent preferably has a viscosity of about from 1.0 to 20.0 cSt at 100°C.
The components of the lubricating oil additive concentrate can be blended in any order and can be blended as combinations of components. The concentrate produced by blending the above components might be a slightly different composition than the initial mixture because the components may interact.
ether Additives The following additive components are examples of some of the components that can be favorably employed in the present invention. These examples of additives are provided to illustrate the present invention, but they are not intended to limit it.
Examples of the auxiliary additives include extreme pressure agents, corrosion inhibitors, rust inhibitors, friction modifiers, anti-foaming agents, viscosity index improvers and pour point depressants. Also employable are anti-wear agents and multi-functional additives (e.g., an organic molybdenum compound such as molybdenum dithiophosphate). As the viscosity improver, polyalkyl methacrylate, ethylene-propylene copolymer, styrene-butadiene copolymer, or polyisobutylene is generally employed. Otherwise, a dispersion-s type or multi-functional viscosity index improver can be employed. The viscosity index improver can be used singly or in combination of various types. The amount of a viscosity index improver in the lubricating oil can vary depending upon the viscosity desired for the target engine oil.
EXAMPLES
The invention will be further illustrated by the following examples, which set forth particularly advantageous embodiments. While the Examples are provided to illustrate the present invention, they are not intended to limit it.
This application is intended to cover those various changes and substitutions that may be made by those skilled in the art without departing from the spirit and scope of the appended claims.
Examples 1-6 Cylinder lubricating oil compositions for marine diesel engine [SAE viscosity grade: 50, Total Base Number (TBN measured by D2896): 70] were prepared using the following components.
(1) overbased sulfurized alkylphenate detergent calcium phenate having TBN of 255 [Ca content: 9.25 wt %]
(2) overbased alkylbenzenesulfonate detergent (2A) calcium sulfonate having TBN of 400 [Ca content: 16.0 wt %]
(2B) calcium sulfonate having TBN of 490 [Ca content: 18.6 wt %]
(3) ashless dispersant (3A) succinimide [N content: 1.75 wt %]
(3B) borated succinimide [N content: 1.5 wt %, B content: 0.5 wt %]
(4) zinc dialkyldithiohosphate and/or zinc diaryldithiophosphate (Zn-DTP) (4A) zinc dithiophosphate, primary alkyl type [P content: 7.4 wt %]
(4B) zinc didodecylphenyldithiophosphate [P content: 2.85 wt %]
Comparative Examples A-D
Cylinder lubricating oil compositions for marine diesel engine [SAE viscosity grade: 50, Total Base Number (TBN measured by D2896): 70] were prepared using the above-mentioned components.
Comparative Examples E-F
Commercially available lubricating oil compositions for marine diesel engine [SAE viscosity grade: 50, Total Base Number (TBN measured by D2896): 70]
were obtained.
The components and the amounts thereof used for preparing each Example are set forth in Table 1. The concentration of ashless dispersants (3A and 3B) and zinc dithiophosphates (4A and 4B) was shown in terms of wt %. As to metallic detergents, the weight ratio between calcium phenate (1 ) and calcium sulfonate (2A or 2B) was shown, in total 100, wherein a total weight of the detergents was adjusted to yield a TBN of 70. The base oil (Viscosity:
263 mm2/s at 40°C, Viscosity Index: 95) for SAE50, used in Table 1, is a mixture of solvent-refined 500N and 150 bright stock.
Performance Evaluation The lubricating performance of each composition was evaluated by the following tests, and the results are set forth in Table 1.
1 ) Hot tube test The merit of each composition after the test at 330°C for 16 hours was evaluated (the value of a clean sample is set at 10).
2) Falex test at high temperature (measuring loss by wear in weight (mg) of a pin at 220°C) Conditions:
i) Temperature: 220°C, ii) Load: 900 Ib (408 kg), and iii) Time Period: 30 minutes.
O N O
O
O
-a w m r E
' > o ~
ca a o ca M ~ i i i i i ~ U
O O
_ O
U ~ M ~ ~ ~ ~ ~ C ~ o o cri m M ~ i i i i i ~ ~ O
00 ~ p I~ O
f~
G
O
O O N
Q fn ~ ~ i i ~ N i ~ U O
. ~ O ~ O tn O _ C m O
O
LIJCD C M f~ i M i i N C O
J O O ~ O ~ O I~
m L
Q a 0 M ~ I~ o O ~ N ~ a ~ tI) O O ' ~' ~ O ' ~ ' O (O 1~
L
N
p O O
N CO ~ ~ O ~ N ~ ~ O (O
O p M O ~ O 1~ N
~
O
M M ~ i i N N i a O 00 p r' ~ O I~ N
~
O
M I~ QO N a O ~t' N M '" ~ O ~ ~ ~ O I~ N
' O
M I~ ~ ~ ~ N ~ a O o0 00 ~ ~ p ' O ' O I~
C
nU
a m Q m Q m - ~ ~
d ' N N M M ~f' ~1'~ ~ ' yj O
E Q .'''~,~ N
U m Z t~
The data presented in Table 1 indicate that the lubricating oil compositions of the present invention (Examples 1-6) exhibit such excellent heat-stability in the hot tube test that they produce little lubricating oil oxidation or degradation product to defile the tube. Also, the results in Table 1 indicate that the lubricating oil compositions of the present invention cause very little wear in the Falex test at high temperature. On the other hand, Comparative Examples A-F cause severe wear in the Falex test at high temperature. Further, Comparative Examples A and D, where the wt % of overbased calcium sulfonate is greater than the wt % of the calcium phenate, caused the tube to be blocked in the hot tube test due to heavy oxidation. This suggests that the lubricating oil oxidation products may be liable to block the pistons of a marine diesel engine if the composition of Comparative A or B is used under very severe conditions.
The succinimide dispersant of the present invention preferably is a borated succinimide, and the preferred borated dispersant can be prepared, for example, by a reaction between the aforementioned succinimide and a boric acid or boric acid derivative.
If the ashless dispersant is present in the lubricating oil composition in an amount of less than 0.1 wt %, the composition will not show enough sludge dispersing power. Further, if water is present, that composition exhibits poor stability. On the other hand, if the dispersant is incorporated in an amount of more than 3.0 wt %, the composition is liable to have poor heat-stability.
In the lubricating oil composition of the present invention, a zinc dialkyldithiophosphate and/or a zinc diaryldithiophosphate (Zn-DTP) is further incorporated in an amount of 0.1 to 4.0 wt %, more preferably 0.1 to 2.0 wt %, and most preferably 0.1 to 1.5 wt %, based on the total amount of the composition. In Zn-DTP, a hydrocarbon oil having been used in preparing the compound remains in a small amount, and hence the above values include the amount of the remaining hydrocarbon oil. The above-mentioned range corresponds to 0.0075 to 0.3 wt %, more preferably 0.0075 to 0.2 wt %, and most preferably 0.0075 to 0.11 wt %, in terms of phosphorus content.
The alkyl group in the zinc dialkyldithiophosphate is, for example, a straight or branched primary, secondary or tertiary alkyl group of about 2 to 18 carbon atoms. Examples of the alkyl groups include ethyl, propyl, iso-propyl, butyl, _g_ pentyl, hexyl, heptyl, octyl, decyl, dodecyl, and octadecyl. As the zinc diaryldithiophosphate, a zinc dialkylaryldithiophosphate is preferred. The alkylaryl group of the zinc dialkylaryldithiophosphate is, for example, a phenyl group having an alkyl group of about 2 to 18 carbon atoms, such as butylphenyl group, nonylphenyl group, and dodecylphenyl group.
If the zinc dialkyldithiophosphate and/or zinc diaryldithiophosphate is present in the lubricating oil composition in an amount of less than 0.1 wt %, the lubricating oil composition will not show satisfactory anti-oxidation stability. On the other hand, even if the compound is incorporated in an amount of more than 4.0 wt %, the effect corresponding to the increased amount is not brought about.
The lubricating oil composition of the present invention is useful in a method of improving the high temperature heat stability and anti-wear performance of internal combustion engines, particularly two-stroke cross-head diesel engines. In that method, the lubricating oil composition of the present invention is used to lubricate an internal combustion engine.
The lubricating oil composition of the present invention can be prepared by successively or simultaneously adding the additive components to a base oil of lubricating viscosity, or by beforehand preparing a lubricating oil additive concentrate, as herein described below, and then mixing it with a base oil of lubricating viscosity.
In a further embodiment, the lubricating oil composition of the present invention is produced by blending a mixture of the above components. The lubricating oil composition produced by that method might have a slightly different composition than the initial mixture, because the components may interact. The components can be blended in any order and can be blended as combinations of components.
_g_ The lubricating oil additive concentrate of the present invention usually includes the product produced by blending:
a) 1.0 to 50.0 wt % of a compatible organic diluent, b) 5.0 to 90.0 wt % of an overbased sulfurized alkylphenate detergent, c) 5.0 to 90.0 wt % of an overbased alkylsulfonate detergent, d) 0.5 to 50.0 wt % of an ashless dispersant, e) 0.5 to 20 wt % of a zinc dialkyldithiophosphate or of a zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent is in the range of 55:45 to 95:5.
The lubricating oil additive concentrate of the present invention may also include the product produced by blending:
a) 1.0 to 50.0 wt % of a compatible organic diluent, b) 0.4 to 9.0 wt %, based on its calcium content, of an overbased sulfurized alkylphenate detergent, c) 0.6 to 16.0 wt %, based on its calcium content, of an overbased alkylbenzenesulfonate detergent, d) 0.005 to 1.0 wt %, based on its nitrogen content, of a nitrogen-containirig ashless dispersant, e) 0.005 to 1.5 wt %, based on its phosphorus content, of a zinc dialkyldithiophosphate or of a zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent is in the range of 55:45 to 95:5.
The concentrates contain sufficient organic liquid diluent to make them easy to handle during shipping and storage. Typically, the concentrate will contain from 1.0 to 50.0 wt %, preferably 3.0 to 20.0 wt %, more preferably 5.0 to 10.0 wt %, of a compatible organic diluent.
Suitable compatible organic diluents which can be used include, for example, solvent refined 100N, i.e., Cit-Con 100N, and hydrotreated 100N, i.e., Chevron 100N, and the like. The organic diluent preferably has a viscosity of about from 1.0 to 20.0 cSt at 100°C.
The components of the lubricating oil additive concentrate can be blended in any order and can be blended as combinations of components. The concentrate produced by blending the above components might be a slightly different composition than the initial mixture because the components may interact.
ether Additives The following additive components are examples of some of the components that can be favorably employed in the present invention. These examples of additives are provided to illustrate the present invention, but they are not intended to limit it.
Examples of the auxiliary additives include extreme pressure agents, corrosion inhibitors, rust inhibitors, friction modifiers, anti-foaming agents, viscosity index improvers and pour point depressants. Also employable are anti-wear agents and multi-functional additives (e.g., an organic molybdenum compound such as molybdenum dithiophosphate). As the viscosity improver, polyalkyl methacrylate, ethylene-propylene copolymer, styrene-butadiene copolymer, or polyisobutylene is generally employed. Otherwise, a dispersion-s type or multi-functional viscosity index improver can be employed. The viscosity index improver can be used singly or in combination of various types. The amount of a viscosity index improver in the lubricating oil can vary depending upon the viscosity desired for the target engine oil.
EXAMPLES
The invention will be further illustrated by the following examples, which set forth particularly advantageous embodiments. While the Examples are provided to illustrate the present invention, they are not intended to limit it.
This application is intended to cover those various changes and substitutions that may be made by those skilled in the art without departing from the spirit and scope of the appended claims.
Examples 1-6 Cylinder lubricating oil compositions for marine diesel engine [SAE viscosity grade: 50, Total Base Number (TBN measured by D2896): 70] were prepared using the following components.
(1) overbased sulfurized alkylphenate detergent calcium phenate having TBN of 255 [Ca content: 9.25 wt %]
(2) overbased alkylbenzenesulfonate detergent (2A) calcium sulfonate having TBN of 400 [Ca content: 16.0 wt %]
(2B) calcium sulfonate having TBN of 490 [Ca content: 18.6 wt %]
(3) ashless dispersant (3A) succinimide [N content: 1.75 wt %]
(3B) borated succinimide [N content: 1.5 wt %, B content: 0.5 wt %]
(4) zinc dialkyldithiohosphate and/or zinc diaryldithiophosphate (Zn-DTP) (4A) zinc dithiophosphate, primary alkyl type [P content: 7.4 wt %]
(4B) zinc didodecylphenyldithiophosphate [P content: 2.85 wt %]
Comparative Examples A-D
Cylinder lubricating oil compositions for marine diesel engine [SAE viscosity grade: 50, Total Base Number (TBN measured by D2896): 70] were prepared using the above-mentioned components.
Comparative Examples E-F
Commercially available lubricating oil compositions for marine diesel engine [SAE viscosity grade: 50, Total Base Number (TBN measured by D2896): 70]
were obtained.
The components and the amounts thereof used for preparing each Example are set forth in Table 1. The concentration of ashless dispersants (3A and 3B) and zinc dithiophosphates (4A and 4B) was shown in terms of wt %. As to metallic detergents, the weight ratio between calcium phenate (1 ) and calcium sulfonate (2A or 2B) was shown, in total 100, wherein a total weight of the detergents was adjusted to yield a TBN of 70. The base oil (Viscosity:
263 mm2/s at 40°C, Viscosity Index: 95) for SAE50, used in Table 1, is a mixture of solvent-refined 500N and 150 bright stock.
Performance Evaluation The lubricating performance of each composition was evaluated by the following tests, and the results are set forth in Table 1.
1 ) Hot tube test The merit of each composition after the test at 330°C for 16 hours was evaluated (the value of a clean sample is set at 10).
2) Falex test at high temperature (measuring loss by wear in weight (mg) of a pin at 220°C) Conditions:
i) Temperature: 220°C, ii) Load: 900 Ib (408 kg), and iii) Time Period: 30 minutes.
O N O
O
O
-a w m r E
' > o ~
ca a o ca M ~ i i i i i ~ U
O O
_ O
U ~ M ~ ~ ~ ~ ~ C ~ o o cri m M ~ i i i i i ~ ~ O
00 ~ p I~ O
f~
G
O
O O N
Q fn ~ ~ i i ~ N i ~ U O
. ~ O ~ O tn O _ C m O
O
LIJCD C M f~ i M i i N C O
J O O ~ O ~ O I~
m L
Q a 0 M ~ I~ o O ~ N ~ a ~ tI) O O ' ~' ~ O ' ~ ' O (O 1~
L
N
p O O
N CO ~ ~ O ~ N ~ ~ O (O
O p M O ~ O 1~ N
~
O
M M ~ i i N N i a O 00 p r' ~ O I~ N
~
O
M I~ QO N a O ~t' N M '" ~ O ~ ~ ~ O I~ N
' O
M I~ ~ ~ ~ N ~ a O o0 00 ~ ~ p ' O ' O I~
C
nU
a m Q m Q m - ~ ~
d ' N N M M ~f' ~1'~ ~ ' yj O
E Q .'''~,~ N
U m Z t~
The data presented in Table 1 indicate that the lubricating oil compositions of the present invention (Examples 1-6) exhibit such excellent heat-stability in the hot tube test that they produce little lubricating oil oxidation or degradation product to defile the tube. Also, the results in Table 1 indicate that the lubricating oil compositions of the present invention cause very little wear in the Falex test at high temperature. On the other hand, Comparative Examples A-F cause severe wear in the Falex test at high temperature. Further, Comparative Examples A and D, where the wt % of overbased calcium sulfonate is greater than the wt % of the calcium phenate, caused the tube to be blocked in the hot tube test due to heavy oxidation. This suggests that the lubricating oil oxidation products may be liable to block the pistons of a marine diesel engine if the composition of Comparative A or B is used under very severe conditions.
Claims (28)
1. A lubricating oil composition comprising:
a) a major amount of a base oil of lubricating viscosity having a kinematic viscosity of 22 to 300 mm2/s at 40°C, b) 5.0 to 35.0 wt % of an overbased sulfurized alkylphenate detergent, c) 2.5 to 20.0 wt % of an overbased alkylsulfonate detergent, d) 0.1 to 3.0 wt % of an ashless dispersant, and e) 0.1 to 4.0 wt % of a zinc dialkyldithiophosphate or of a zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent is in the range of 55:45 to 95:5.
a) a major amount of a base oil of lubricating viscosity having a kinematic viscosity of 22 to 300 mm2/s at 40°C, b) 5.0 to 35.0 wt % of an overbased sulfurized alkylphenate detergent, c) 2.5 to 20.0 wt % of an overbased alkylsulfonate detergent, d) 0.1 to 3.0 wt % of an ashless dispersant, and e) 0.1 to 4.0 wt % of a zinc dialkyldithiophosphate or of a zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent is in the range of 55:45 to 95:5.
2. The lubricating oil composition according to Claim 1, wherein the weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent is in the range of 60:40 to 90:10.
3. The lubricating oil composition according to Claim 1, wherein the overbased sulfurized alkylphenate detergent has a TBN greater than 200.
4. The lubricating oil composition according to Claim 1, wherein the overbased alkylsulfonate detergent has a TBN greater than 250.
5. The lubricating oil composition according to Claim 1, wherein the ashless dispersant is a succinimide with a polybutenyl group having a molecular weight of 800 to 8,000.
6. The lubricating oil composition according to Claim 5, wherein the ashless dispersant is a borated succinimide.
7. A lubricating oil composition comprising:
a) a major amount of a base oil of lubricating viscosity having a kinematic viscosity of 22 to 300 mm2/s at 40°C, b) 0.4 to 4.0 wt %, based on its calcium content, of an overbased sulfurized calcium alkylphenate detergent, c) 0.3 to 5.0 wt %, based on its calcium content, of an overbased calcium alkylbenzenesulfonate detergent, d) 0.001 to 0.1 wt %, based on its nitrogen content, of a nitrogen-containing ashless dispersant, and e) 0.0075 to 0.3 wt %, based on its phosphorus content, of a zinc dialkyldithiophosphate or of a zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized calcium alkylphenate detergent and the overbased calcium alkylbenzenesulfonate detergent is in the range of 55:45 to 95:5.
a) a major amount of a base oil of lubricating viscosity having a kinematic viscosity of 22 to 300 mm2/s at 40°C, b) 0.4 to 4.0 wt %, based on its calcium content, of an overbased sulfurized calcium alkylphenate detergent, c) 0.3 to 5.0 wt %, based on its calcium content, of an overbased calcium alkylbenzenesulfonate detergent, d) 0.001 to 0.1 wt %, based on its nitrogen content, of a nitrogen-containing ashless dispersant, and e) 0.0075 to 0.3 wt %, based on its phosphorus content, of a zinc dialkyldithiophosphate or of a zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized calcium alkylphenate detergent and the overbased calcium alkylbenzenesulfonate detergent is in the range of 55:45 to 95:5.
8. The lubricating oil composition according to Claim 7, wherein the weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent is in the range of 60:40 to 90:10.
9. The lubricating oil composition according to Claim 7, wherein the overbased sulfurized calcium alkylphenate detergent has a TBN greater than 110.
10. The lubricating oil composition according to Claim 7, wherein the overbased calcium alkylbenzenesulfonate detergent has a TBN greater than 120.
11.The lubricating oil composition according to Claim 7, wherein the nitrogen-containing ashless dispersant is a succinimide with a polybutenyl group having a molecular weight of 800 to 8,000.
12. The lubricating oil composition according to Claim 11, wherein the ashless dispersant is a borated succinimide.
13.A lubricating oil additive concentrate comprising:
a) 1.0 to 50.0 wt % of a compatible organic diluent, b) 5.0 to 90.0 wt % of an overbased sulfurized alkylphenate detergent, c) 5.0 to 90.0 wt % of an overbased alkylsulfonate detergent, d) 0.5 to 50.0 wt % of an ashless dispersant, e) 0.5 to 20 wt % of a zinc dialkyldithiophosphate or of a zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent is in the range of 55:45 to 95:5.
a) 1.0 to 50.0 wt % of a compatible organic diluent, b) 5.0 to 90.0 wt % of an overbased sulfurized alkylphenate detergent, c) 5.0 to 90.0 wt % of an overbased alkylsulfonate detergent, d) 0.5 to 50.0 wt % of an ashless dispersant, e) 0.5 to 20 wt % of a zinc dialkyldithiophosphate or of a zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent is in the range of 55:45 to 95:5.
14. The lubricating oil additive concentrate according to Claim 13, wherein the weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent is in the range of 60:40 to 90:10.
15.The lubricating oil additive concentrate according to Claim 13, wherein the overbased sulfurized alkylphenate detergent has a TBN greater than 200.
16. The lubricating oil additive concentrate according to Claim 13, wherein the overbased alkylsulfonate has a TBN greater than 200.
17.The lubricating oil additive concentrate according to Claim 13, wherein the ashless dispersant is a succinimide with a polybutenyl group having a molecular weight of 800 to 8,000.
18. The lubricating oil additive concentrate according to Claim 17, wherein the ashless dispersant is a borated succinimide.
19.A lubricating oil additive concentrate comprising:
a) 1.0 to 50.0 wt % of a compatible organic diluent, b) 0.4 to 9.0 wt %, based on its calcium content, of an overbased sulfurized alkylphenate detergent, c) 0.6 to 16.0 wt %, based on its calcium content, of an overbased alkylbenzenesulfonate detergent, d) 0.005 to 1.0 wt %, based on its nitrogen content, of a nitrogen-containing ashless dispersant, e) 0.005 to 1.5 wt %, based on its phosphorus content, of a zinc dialkyldithiophosphate or of a zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent is in the range of 55:45 to 95:5.
a) 1.0 to 50.0 wt % of a compatible organic diluent, b) 0.4 to 9.0 wt %, based on its calcium content, of an overbased sulfurized alkylphenate detergent, c) 0.6 to 16.0 wt %, based on its calcium content, of an overbased alkylbenzenesulfonate detergent, d) 0.005 to 1.0 wt %, based on its nitrogen content, of a nitrogen-containing ashless dispersant, e) 0.005 to 1.5 wt %, based on its phosphorus content, of a zinc dialkyldithiophosphate or of a zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent is in the range of 55:45 to 95:5.
20.The lubricating oil additive concentrate according to Claim 19, wherein the weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent is in the range of 60:40 to 90:10.
21.The lubricating oil additive concentrate according to Claim 19, wherein the overbased sulfurized calcium alkylphenate detergent has a TBN greater than 200.
22.The lubricating oil additive concentrate according to Claim 19, wherein the overbased calcium alkylbenzenesulfonate detergent has a TBN greater than 200.
23.The lubricating oil additive concentrate according to Claim 19, wherein the nitrogen-containing ashless dispersant is a succinimide with a polybutenyl group having a molecular weight of 800 to 8,000.
24.The lubricating oil additive concentrate according to Claim 23, wherein the ashless dispersant is a borated succinimide.
25. A method of improving the heat stability and anti-wear performance at high temperatures of an internal combustion engine, said method comprising lubricating the internal combustion engine with a lubricating oil composition according to Claim 1.
26.A method of improving the heat stability and anti-wear performance at high temperatures of an internal combustion engine according to Claim 25, wherein the internal combustion engine is a two-stroke cross-head diesel engine.
27.A method for producing a lubricating oil composition comprising blending the components according to Claim 1.
28.A lubricating oil composition produced by the method according to Claim 27.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000034652A JP4011815B2 (en) | 2000-02-14 | 2000-02-14 | Lubricating oil composition for two-cycle crosshead diesel internal combustion engine and additive composition for lubricating oil composition |
| JP2000-034652 | 2000-02-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2336505A1 true CA2336505A1 (en) | 2001-08-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002336505A Abandoned CA2336505A1 (en) | 2000-02-14 | 2001-02-14 | Marine diesel engine lubricating oil composition having improved high temperature performance |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20010019999A1 (en) |
| EP (1) | EP1126010A1 (en) |
| JP (1) | JP4011815B2 (en) |
| CA (1) | CA2336505A1 (en) |
| SG (1) | SG95628A1 (en) |
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| KR102613191B1 (en) * | 2014-11-06 | 2023-12-14 | 셰브런 오로나이트 테크놀로지 비.브이. | Marine diesel cylinder lubricant oil compositions |
| JP2017533329A (en) * | 2014-11-06 | 2017-11-09 | シェブロン・オロナイト・テクノロジー・ビー．ブイ． | Marine diesel cylinder lubricating oil composition |
| CN106190495B (en) * | 2016-07-18 | 2019-03-29 | 烟台思欧特润滑油有限公司 | A kind of preparation method of rare earth ship machine oil |
| CN106479633A (en) * | 2016-09-20 | 2017-03-08 | 中国石油化工股份有限公司 | Marine diesel fluid composition and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4375418A (en) * | 1981-10-28 | 1983-03-01 | Texaco Inc. | Lubricating oil composition |
| US4871465A (en) * | 1987-09-30 | 1989-10-03 | Amoco Corporation | Chlorine-free silver protective lubricant composition (II) |
| GB8804171D0 (en) * | 1988-02-23 | 1988-03-23 | Exxon Chemical Patents Inc | Dispersant for marine diesel cylinder lubricant |
| FR2774387B1 (en) * | 1998-02-02 | 2000-12-01 | Elf Antar France | MARINE LUBRICANT FOR TWO-STROKE ENGINE |
-
2000
- 2000-02-14 JP JP2000034652A patent/JP4011815B2/en not_active Expired - Lifetime
-
2001
- 2001-02-09 US US09/780,294 patent/US20010019999A1/en not_active Abandoned
- 2001-02-13 SG SG200100768A patent/SG95628A1/en unknown
- 2001-02-14 CA CA002336505A patent/CA2336505A1/en not_active Abandoned
- 2001-02-14 EP EP01301248A patent/EP1126010A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001226691A (en) | 2001-08-21 |
| SG95628A1 (en) | 2003-04-23 |
| US20010019999A1 (en) | 2001-09-06 |
| JP4011815B2 (en) | 2007-11-21 |
| EP1126010A1 (en) | 2001-08-22 |
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