CA2531433A1 - Lubricating oil composition having improved oxidation stability at high temperatures - Google Patents
Lubricating oil composition having improved oxidation stability at high temperatures Download PDFInfo
- Publication number
- CA2531433A1 CA2531433A1 CA002531433A CA2531433A CA2531433A1 CA 2531433 A1 CA2531433 A1 CA 2531433A1 CA 002531433 A CA002531433 A CA 002531433A CA 2531433 A CA2531433 A CA 2531433A CA 2531433 A1 CA2531433 A1 CA 2531433A1
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- CA
- Canada
- Prior art keywords
- lubricating oil
- oil composition
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- expressed
- total amount
- 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.)
- Granted
Links
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 73
- 239000000203 mixture Substances 0.000 title claims abstract description 73
- 230000003647 oxidation Effects 0.000 title claims description 15
- 238000007254 oxidation reaction Methods 0.000 title claims description 15
- -1 calcium carboxylate Chemical class 0.000 claims abstract description 38
- 239000011575 calcium Substances 0.000 claims abstract description 26
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 24
- 229960002317 succinimide Drugs 0.000 claims abstract description 24
- 239000011701 zinc Substances 0.000 claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002199 base oil Substances 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000001050 lubricating effect Effects 0.000 claims abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000002485 combustion reaction Methods 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 3
- 229940126062 Compound A Drugs 0.000 claims description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 16
- 239000003921 oil Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 239000003599 detergent Substances 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 229920001083 polybutene Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229960001860 salicylate Drugs 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical class C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 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
- 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 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LMODBLQHQHXPEI-UHFFFAOYSA-N dibutylcarbamothioylsulfanylmethyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SCSC(=S)N(CCCC)CCCC LMODBLQHQHXPEI-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 229940113162 oleylamide Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 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
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- 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
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
-
- 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
- C10N2030/52—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
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 having a TBN in the range of 5 to 55 mg KOH/g and containing a major amount of a base oil of lubricating viscosity and a) 0.19 to 2.10 wt %, based on the total amount of the lubricating oil composition, of an overbased calcium carboxylate having a TBN of 100 mg KOH/g or more, wherein the wt % is expressed in terms of the calcium content;
b) 0.002 to 0.06 wt %, based on the total amount of the lubricating oil composition, of a bis-succinimide compound, wherein the wt % is expressed in terms of the nitrogen content; and c) 0.007 to 0.15 wt %, based on the total amount of the lubricating oil composition, of a zinc dialkyldithiophosphate having a secondary alkyl group, wherein the wt % is expressed in terms of the phosphorus content.
b) 0.002 to 0.06 wt %, based on the total amount of the lubricating oil composition, of a bis-succinimide compound, wherein the wt % is expressed in terms of the nitrogen content; and c) 0.007 to 0.15 wt %, based on the total amount of the lubricating oil composition, of a zinc dialkyldithiophosphate having a secondary alkyl group, wherein the wt % is expressed in terms of the phosphorus content.
Description
..
LUBRICATING OIL COMPOSITION HAVING IMPROVED OXIDATION
STABILITY AT HIGH TEMPERATURES
The present invention relates to a lubricating oil composition. More particularly, the present invention relates to a lubricating oil composition having improved oxidation stability at high temperatures when employed in an internal combustion engines.
BACKGROUND OF THE INVENTION
Diesel engines, particularly four stroke trunk piston diesel engines, are generally employed as internal combustion engines for generation of electric power and operation of marine vessels. These internal combustion engines are operated smoothly using a lubricating oil composition which contains various additives.
LUBRICATING OIL COMPOSITION HAVING IMPROVED OXIDATION
STABILITY AT HIGH TEMPERATURES
The present invention relates to a lubricating oil composition. More particularly, the present invention relates to a lubricating oil composition having improved oxidation stability at high temperatures when employed in an internal combustion engines.
BACKGROUND OF THE INVENTION
Diesel engines, particularly four stroke trunk piston diesel engines, are generally employed as internal combustion engines for generation of electric power and operation of marine vessels. These internal combustion engines are operated smoothly using a lubricating oil composition which contains various additives.
2~ Generally, most additives employed in lubricating oil compositions are metal-containing detergents. Specifically, an over-based metal-containing detergent which neutralizes sulfur oxide produced by the combustion of fuel and disperses combustion deposits such as sludge is generally employed. Particularly, a lubri-cating oil composition for marine diesel engines which is operated using high sulfur content fuel such as A-heavy oil or C-heavy oil should contain over-based metal-containing detergents. Most metal-containing detergents are alkaline earth metal sulfonates, alkaline earth metal phenates, and alkaline earth metal salicylates. An ashless dispersant such as succinimide is also generally employ-ed. Examples of other generally employable additives include a zinc dialkyldithio-phosphate compound which serves as an anti-oxidation agent and an extreme-pressure agent and an organic anti-oxidation agent such as phenol compound and amine compound.
Recently, the operation conditions of diesel engines for generation of electric power and operation of marine vessel have been getting severe. In addition, these diesel engines are forced to employ a low grade fuel having increased sulfur content. Moreover, the recent demand for economical operation and increase of maintenance efficiency requires extended service periods for using a lubricating oil with no substantial exchange. Therefore, the load applied to the lubricating oil has increased recently.
The lubricating oil is consumed during the operation of engines. Although a fresh lubricating oil is supplemented periodically to compensate the consumed portion, the amount of sulfur oxide compounds and combustion residues produced and deposited in the remaining lubricating oil increases. Therefore, after the engine is operated continuously for a long period of time, the lubricating oil suffers from deterioration and viscosity increase.
~ 5 Japanese Provisional Patent Publication 2000-63867, U.S. Patent 6,262,001 and Japanese Provisional Patent Publication 2000-87066 disclose a metal-containing overbased calcium carboxylate (i.e., overbased calcium hydrocarbyl-salicylate carboxylate) having high thermal stability and high detergency. It can be prepared with low production costs. These publications describe a variety of compositions for engine lubricating oils.
SUMMARY OF THE INVENTION
As previously mentioned, the present invention relates to a lubricating oil composition having high thermal oxidation stability at high temperatures which are favorably employable for lubricating various internal combustion engines such as diesel engines and gasoline engines. For example the lubricating oil composition of the present invention is very favorably employed in four stroke trunk piston diesel engines.
Accordingly, the present invention relates to a lubricating oil composition having a TBN in the range of 5 to 55 mg KOH/g comprising a base oil of lubricating viscosity and a) 0.19 to 2.10 wt %, based on the total amount of the lubricating oil composition, of an overbased calcium carboxylate having a TBN of 100 mg KOH/g or more, wherein the wt % is expressed in terms of the calcium (Ca) content;
b) 0.002 to 0.06 wt %, based on the total amount of the lubricating oil composition, of a bis-succinimide compound wherein, the wt % is expressed in terms of the nitrogen (N) content; and c) 0.007 to 0.15 wt %, based on the total amount of the lubricating oil composition, of a zinc dialkyldithiophosphate having a secondary ~ 0 alkyl group, wherein the wt % is expressed in terms of the phosphorus (P) content.
In a further embodiment the present invention relates to a method of improving the oxidation stability at high temperatures of an internal combustion engine, 5 particularly a four stroke trunk piston diesel engine, by operating the internal combustion engine with the lubricating oil composition of the present invention.
Among other factors, the present invention is based on the surprising discovery that a certain lubricating oil composition provides improved high temperature 20 oxidation stability when employed in internal combustion engines such as diesel engines and gasoline engines.
DETAILED DESCRIPTION OF THE INVENTION
25 In its broadest aspect, the present invention relates to a lubricating oil composition having a major amount of base oi! of lubricating viscosity and an overbased calcium carboxylate, bis-succinimide compound and a zinc dialkylthidiophosphate, wherein the TBN of the lubricating oil composition is in the range of 5 to 55 mg KOH/g.
Recently, the operation conditions of diesel engines for generation of electric power and operation of marine vessel have been getting severe. In addition, these diesel engines are forced to employ a low grade fuel having increased sulfur content. Moreover, the recent demand for economical operation and increase of maintenance efficiency requires extended service periods for using a lubricating oil with no substantial exchange. Therefore, the load applied to the lubricating oil has increased recently.
The lubricating oil is consumed during the operation of engines. Although a fresh lubricating oil is supplemented periodically to compensate the consumed portion, the amount of sulfur oxide compounds and combustion residues produced and deposited in the remaining lubricating oil increases. Therefore, after the engine is operated continuously for a long period of time, the lubricating oil suffers from deterioration and viscosity increase.
~ 5 Japanese Provisional Patent Publication 2000-63867, U.S. Patent 6,262,001 and Japanese Provisional Patent Publication 2000-87066 disclose a metal-containing overbased calcium carboxylate (i.e., overbased calcium hydrocarbyl-salicylate carboxylate) having high thermal stability and high detergency. It can be prepared with low production costs. These publications describe a variety of compositions for engine lubricating oils.
SUMMARY OF THE INVENTION
As previously mentioned, the present invention relates to a lubricating oil composition having high thermal oxidation stability at high temperatures which are favorably employable for lubricating various internal combustion engines such as diesel engines and gasoline engines. For example the lubricating oil composition of the present invention is very favorably employed in four stroke trunk piston diesel engines.
Accordingly, the present invention relates to a lubricating oil composition having a TBN in the range of 5 to 55 mg KOH/g comprising a base oil of lubricating viscosity and a) 0.19 to 2.10 wt %, based on the total amount of the lubricating oil composition, of an overbased calcium carboxylate having a TBN of 100 mg KOH/g or more, wherein the wt % is expressed in terms of the calcium (Ca) content;
b) 0.002 to 0.06 wt %, based on the total amount of the lubricating oil composition, of a bis-succinimide compound wherein, the wt % is expressed in terms of the nitrogen (N) content; and c) 0.007 to 0.15 wt %, based on the total amount of the lubricating oil composition, of a zinc dialkyldithiophosphate having a secondary ~ 0 alkyl group, wherein the wt % is expressed in terms of the phosphorus (P) content.
In a further embodiment the present invention relates to a method of improving the oxidation stability at high temperatures of an internal combustion engine, 5 particularly a four stroke trunk piston diesel engine, by operating the internal combustion engine with the lubricating oil composition of the present invention.
Among other factors, the present invention is based on the surprising discovery that a certain lubricating oil composition provides improved high temperature 20 oxidation stability when employed in internal combustion engines such as diesel engines and gasoline engines.
DETAILED DESCRIPTION OF THE INVENTION
25 In its broadest aspect, the present invention relates to a lubricating oil composition having a major amount of base oi! of lubricating viscosity and an overbased calcium carboxylate, bis-succinimide compound and a zinc dialkylthidiophosphate, wherein the TBN of the lubricating oil composition is in the range of 5 to 55 mg KOH/g.
3~
Base Oil of Lubricating Viscosity The base oil of lubricating viscosity employed in the lubricating oil composition of the present invention generally is a mineral oil or a synthetic oil having a dynamic :3 ~ viscosity in the range of 22 to 300 mm2/s at 40°C. There are no specific limitations with respect to the nature and other characteristics of the mineral oil and synthetic oil. However, the sulfur content of the base oil is preferably not less than 0.1 wt %, more preferably less than 0.03 wt %, most preferably less than 0.005 wt %.
The mineral oil is preferably prepared by processing a mineral oil of lubricating oil distillate by an appropriate combination of solvent purification and hydrogenation processing. Most preferred is a mineral oil having been subjected to high hydrogenation processing (i.e., hydrogenation cracking) that advantageously shows a viscosity index in the range of 100 to 150 and has an aromatic component content of less than 5 wt %, a nitrogen content of less than 50 ppm, and a sulfur content of less than 50 ppm. The above-identified most preferred mineral oil can be a high viscosity index base oil which is prepared by processing synthetic wax by isomerization and hydrogenation cracking. The synthetic wax was prepared by mineral slack was (crude wax) or natural gas.
The synthetic oil (synthetic base oil) can be poly-a-olefin (polymer prepared from a-olefin having 3 to 12 carbon atoms), a sebacic acid compound such as dioctyl sebacate, a dialkyl diester prepared from a dibasic acid such as azelaic acid or adipic acid and an alcohol having 4 to 18 carbon atoms, a polyol ester prepared from 1-trimethylolpropane or pentaerythritol and a monobasic acid, or an alkylbenzene having alkyl of 9 to 40 carbon atoms.
The synthetic oil generally contains no sulfur compound and shows high thermal stability and high heat resistance. Moreover, the synthetic oil produces little soot and carbonaceous deposit. Therefore, the synthetic oil is preferred as the base oil for the lubricating oil composition of the present invention.
Each of the mineral base oil and synthetic base oil can be employed singly.
However, if desired, two or more of mineral base oils or two or more of synthetic base oils can be employed in combination. Further, if desired, one or more mineral base oils and one or more synthetic base oils can be employed in combination.
It is preferred to use a major amount of base oil of lubricating viscosity in the lubricating oil composition of the present invention. A major amount of base oil of lubricating viscosity as defined herein comprises 40 wt % or more. Preferred amounts of base oil comprise 40 wt % to 97 wt %, preferably greater than 50 wt to 97 wt %, more preferably 60 wt % to 97 wt % and most preferably 80 wt to 95 wt % of the lubricating oil composition. (When weight percent is used herein, it is referring to weight percent of the lubricating oil composition unless otherwise specified.) Overbased Calcium Carboxylate The overbased calcium carboxylate employed in the lubricating oil of the present invention has a TBN of 100 mg KOHIg or more and can be prepared in the manner described in the aforementioned references cited in the Background of the Invention. The overbased calcium carboxylate will be in the amount of 0.19 to 2.10 wt %, preferably 0.38 to 1.15 wt %, based on the total amount of the lubricating oil composition and expressed in terms of the calcium content. A
representative example of the overbased calcium carboxylate comprises a rela-tively large amount (more than 50 wt %) of the following compound A and a relatively small amount (less than 50 wt %) of the following compound B:
Compound A Compound B
O,Ca'O OH O
C-OCaOH
C' O
R
R
in which R is an alkyl group having 12 to 28 carbon atoms.
The lubricating oil composition of the present invention can contain other metal-3G containing detergents in addition to the overbased calcium carboxylate.
Examples of other metal-containing detergents employable in combination with the overbased calcium carboxylate include suifurized phenate (e.g., sulfurized calcium phenate), petroleum sulfonates or synthetic sulfonates (e.g., calcium sulfonate), and salicylate (e.g., calcium salicylate).
Bis-Succinimide Compound ~ 0 The lubricating oil composition of the present invention contains a bis-succinimide compound (i.e., succinimide or its derivatives) in the amount of 0.002 to 0.06 wt %, preferably 0.014 to 0.02 wt %, based on the total amount of the lubricating oil composition and expressed in terms of the nitrogen content. The bis-succinimide compound preferably is an alkenylsuccinimide or an alkylsuccinimide derived ~I 5 from a polyolefin compound or its derivatives. The bis-succinimide can be prepared, for example, by a reaction between succinic anhydride and a high molecular weight alkenyl or alkyl, followed by further reaction with a polyalkylenepolyamine containing 4 to 10, preferably 5 to 7, nitrogen atoms per molecule. For example, the bis-succinimide compound can be prepared by a 20 thermal reaction between a polybutene compound containing 50% or more methylvinylidene structure and malefic anhydride, followed by reaction of the resulting polybutenyl succinic anhydride with a polyalkylenepolyamine containing 4 to 10, preferably 5 to 7, nitrogen atoms per molecule. The high molecular weight alkenyl or alkyl group preferably is polybutene having a number-average 25 molecular weight in the range of approximately 900 to 5,000.
The bis-succinimide can be employed in the form of a modified succinimide which is obtained by reacting succinimide with boric acid, alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate (e.g., ethylene carbonate), or an organic acid.
30 Preferred is a boron-containing alkenyl- or alkylsuccinimide which is obtained by reaction with boric acid or a boron compound. The resulting modified succinimide compound exhibits high thermal stability and high anti-oxidation property.
The lubricating oil composition of the present invention can contain other ashless 35 dispersants such as nitrogen-containing ashless dispersants (e.g., mono-structure type alkenyl- or alkylsuccinimide, and an alkenylbenzylamine) and/or dispersants containing no nitrogen atoms such as an alkenyl succinic ester in addition to the bis-structure alkenyl or alkyl succinimide.
Base Oil of Lubricating Viscosity The base oil of lubricating viscosity employed in the lubricating oil composition of the present invention generally is a mineral oil or a synthetic oil having a dynamic :3 ~ viscosity in the range of 22 to 300 mm2/s at 40°C. There are no specific limitations with respect to the nature and other characteristics of the mineral oil and synthetic oil. However, the sulfur content of the base oil is preferably not less than 0.1 wt %, more preferably less than 0.03 wt %, most preferably less than 0.005 wt %.
The mineral oil is preferably prepared by processing a mineral oil of lubricating oil distillate by an appropriate combination of solvent purification and hydrogenation processing. Most preferred is a mineral oil having been subjected to high hydrogenation processing (i.e., hydrogenation cracking) that advantageously shows a viscosity index in the range of 100 to 150 and has an aromatic component content of less than 5 wt %, a nitrogen content of less than 50 ppm, and a sulfur content of less than 50 ppm. The above-identified most preferred mineral oil can be a high viscosity index base oil which is prepared by processing synthetic wax by isomerization and hydrogenation cracking. The synthetic wax was prepared by mineral slack was (crude wax) or natural gas.
The synthetic oil (synthetic base oil) can be poly-a-olefin (polymer prepared from a-olefin having 3 to 12 carbon atoms), a sebacic acid compound such as dioctyl sebacate, a dialkyl diester prepared from a dibasic acid such as azelaic acid or adipic acid and an alcohol having 4 to 18 carbon atoms, a polyol ester prepared from 1-trimethylolpropane or pentaerythritol and a monobasic acid, or an alkylbenzene having alkyl of 9 to 40 carbon atoms.
The synthetic oil generally contains no sulfur compound and shows high thermal stability and high heat resistance. Moreover, the synthetic oil produces little soot and carbonaceous deposit. Therefore, the synthetic oil is preferred as the base oil for the lubricating oil composition of the present invention.
Each of the mineral base oil and synthetic base oil can be employed singly.
However, if desired, two or more of mineral base oils or two or more of synthetic base oils can be employed in combination. Further, if desired, one or more mineral base oils and one or more synthetic base oils can be employed in combination.
It is preferred to use a major amount of base oil of lubricating viscosity in the lubricating oil composition of the present invention. A major amount of base oil of lubricating viscosity as defined herein comprises 40 wt % or more. Preferred amounts of base oil comprise 40 wt % to 97 wt %, preferably greater than 50 wt to 97 wt %, more preferably 60 wt % to 97 wt % and most preferably 80 wt to 95 wt % of the lubricating oil composition. (When weight percent is used herein, it is referring to weight percent of the lubricating oil composition unless otherwise specified.) Overbased Calcium Carboxylate The overbased calcium carboxylate employed in the lubricating oil of the present invention has a TBN of 100 mg KOHIg or more and can be prepared in the manner described in the aforementioned references cited in the Background of the Invention. The overbased calcium carboxylate will be in the amount of 0.19 to 2.10 wt %, preferably 0.38 to 1.15 wt %, based on the total amount of the lubricating oil composition and expressed in terms of the calcium content. A
representative example of the overbased calcium carboxylate comprises a rela-tively large amount (more than 50 wt %) of the following compound A and a relatively small amount (less than 50 wt %) of the following compound B:
Compound A Compound B
O,Ca'O OH O
C-OCaOH
C' O
R
R
in which R is an alkyl group having 12 to 28 carbon atoms.
The lubricating oil composition of the present invention can contain other metal-3G containing detergents in addition to the overbased calcium carboxylate.
Examples of other metal-containing detergents employable in combination with the overbased calcium carboxylate include suifurized phenate (e.g., sulfurized calcium phenate), petroleum sulfonates or synthetic sulfonates (e.g., calcium sulfonate), and salicylate (e.g., calcium salicylate).
Bis-Succinimide Compound ~ 0 The lubricating oil composition of the present invention contains a bis-succinimide compound (i.e., succinimide or its derivatives) in the amount of 0.002 to 0.06 wt %, preferably 0.014 to 0.02 wt %, based on the total amount of the lubricating oil composition and expressed in terms of the nitrogen content. The bis-succinimide compound preferably is an alkenylsuccinimide or an alkylsuccinimide derived ~I 5 from a polyolefin compound or its derivatives. The bis-succinimide can be prepared, for example, by a reaction between succinic anhydride and a high molecular weight alkenyl or alkyl, followed by further reaction with a polyalkylenepolyamine containing 4 to 10, preferably 5 to 7, nitrogen atoms per molecule. For example, the bis-succinimide compound can be prepared by a 20 thermal reaction between a polybutene compound containing 50% or more methylvinylidene structure and malefic anhydride, followed by reaction of the resulting polybutenyl succinic anhydride with a polyalkylenepolyamine containing 4 to 10, preferably 5 to 7, nitrogen atoms per molecule. The high molecular weight alkenyl or alkyl group preferably is polybutene having a number-average 25 molecular weight in the range of approximately 900 to 5,000.
The bis-succinimide can be employed in the form of a modified succinimide which is obtained by reacting succinimide with boric acid, alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate (e.g., ethylene carbonate), or an organic acid.
30 Preferred is a boron-containing alkenyl- or alkylsuccinimide which is obtained by reaction with boric acid or a boron compound. The resulting modified succinimide compound exhibits high thermal stability and high anti-oxidation property.
The lubricating oil composition of the present invention can contain other ashless 35 dispersants such as nitrogen-containing ashless dispersants (e.g., mono-structure type alkenyl- or alkylsuccinimide, and an alkenylbenzylamine) and/or dispersants containing no nitrogen atoms such as an alkenyl succinic ester in addition to the bis-structure alkenyl or alkyl succinimide.
Zinc Dialk ly dithiophosphate The zinc dialkyldithiophosphate employed in the lubrication oil composition of the present invention has a secondary alkyl group and will be in the amount of 0.007 to 0.15 wt %, preferably 0.036 to 0.072 wt %, based on the total amount of the lubricating oil composition and expressed in terms of the phosphorus content.
The alkyl group preferably contains 3 to 18 carbon atoms. All of the two alkyl groups of the zinc dialkyldithiophosphate can be secondary alkyl groups.
Otherwise, a portion (e.g., a relatively small portion such as less than 48 mole %) of the alkyl groups of the zinc diaikyldithiophosphate can be a primary alkyl group. The secondary-alkyl type zinc dialkyldithiophosphate can be employed in combination with a zinc dialkyldithiophosphate having a primary alkyl group.
In this case, the former zinc dialkyldithiophosphate is generally employed in an amount of 52 to 98 mole %, and the latter zinc dialkyldithiophosphate can be employed in an amount of 2 to 48 mole %.
Other Additives The lubricating oil composition of the present invention can further contain other oxidation inhibitors, such as phenol oxidation inhibitors and/or amine oxidation inhibitors, in an amount of 0.01 to 5 wt %, preferably 0.1 to 3 wt %.
The lubrication oil composition of the present invention can further contain a multi-functional molybdenum-containing compound in an amount of 0.01 to 5 wt %, preferably 0.1 to 3 wt %. The molybdenum-containing compound mainly serves as friction-modifier, oxidation inhibitor and anti-wear agent in the lubricating oil composition of the present invention. The molybdenum-containing compound further provides effective high temperatures detergency. The molybdenum-containing compound can be incorporated into the lubricating oil composition of the present invention in an amount of 10 to 2,500 ppm in terms of the molybdenum metal content. Examples of the molybdenum-containing compounds include, but not limited to, a sulfur-containing molybdenum complex compound of succinimide, sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum dithiophosphate, an amine-molybdenum complex compound, oxymolybdenum diethylateamide, and oxymolybdenum monoglyceride. The sulfur-containing molybdenum complex compound of succinimide is particularly effective to increase detergency at high temperatures.
The lubricating oil composition of the present invention can further contain a viscosity index improver in an amount of less than 20 wt %, preferably in an amount of 1 to 20 wt %. Examples of the viscosity index improvers are such polymers as poly(alkyl methacrylate), ethylene-propylene copolymer, styrene-butadiene copolymer, and polyisoprene. Dispersant-type viscosity index ~ 5 improvers and multi-functional viscosity index improvers which are obtained by adding dispersancy to the above-mentioned polymers are also employable. The viscosity index improvers can be employed singly or in combination.
The lubricating oil composition of the present invention can further contain a 2Q variety of subsidiary additives. Examples of the subsidiary additives include, but not limited to, oxidation inhibitors/anti-wear agents (e.g., zinc dithiocarbamate, methylene-bis(dibutyldithiocarbamate), oil-soluble copper compounds, sulfur-containing compounds such as sulfurized olefins, sulfurized esters and polysulfides, phosphate esters, phosphite esters, and organic amide compounds 25 such as oleylamide. Metal-deactivating compounds such as benzotriazol compounds and thiaziazol compounds also can be employed. Anti-rust agents and de-emulsifiers such as nonionic surfactants (e.g., polyoxyethylene alkylphenyl ether, and copolymer of ethylene oxide and propylene oxide) also can be employed. Friction modifiers such as amines, amides, amine salts, their 30 derivatives, and fatty acid esters of polyhydric alcohols and their derivatives also can be employed. Anti-foaming agents and pour point depressants also can be employed. Each of the subsidiary additives is generally contained in the lubricating oil composition of the present invention in an amount of less than 3 wt %, preferably in the range of 0.001 to 3 wt %.
EXAMPLES
The invention will be further illustrated by the following examples, which set forth particularly advantageous method embodiments. While the Examples are provided to illustrate the present invention, they are not intended to limit it.
Example 1 A lubricating oil composition (TBN: 30 mg~KOH/g, SAE viscosity grade: SAE 40) was prepared using the following additives and base oil:
1 ~ a) overbased calcium carboxylate (TBN: 145 mg~KOH/g, a mixture of a compound of the aforementioned formula in which R has 12 to 18 carbon atoms and a compound of the formula in which R has 20 to 28 carbon atoms, in a weight ratio of 50:50 in an amount of 1.15 wt % in terms of Ca content;
b) bis-structure succinimide dispersant (nitrogen content 0.018 wt %, prepared by reaction between polyalkylene polyamine (containing nitrogen atoms of 5.0 (mean number) in a molecule) and a product produced by thermal reaction of polybutene (number average molecular weight: approx. 1,000, having at least 50 mole % of methylvinylidene structure) and malefic anhydride) in an amount of 0.018 wt % in terms of N content;
c) zinc di(secondary)alkyldithiophosphate (P 0.049 wt %, Zn 0.054 wt %, S
0.14 wt %, prepared using a secondary alcohol containing 3 to 8 carbon atoms) in an amount of 0.05 wt % in terms of P content;
d) base oil (dynamic viscosity at 40°C: 140 mm2/sec.) of the remaining amount.
Comparative Example A
A lubricating oil composition having the same composition of Example 1 except for containing no bis-succinimide (component b) was prepared.
n Comparative Example B
A lubricating oil composition having the same composition of Example 1 except for containing neither bis-structure succinimide (component b) nor zinc di(secondary)alkyldithiophosphate (component c) was prepared.
Comparative Example C
A lubricating oil composition having the same composition of Example 1 except for replacing the zinc di(secondary)alkyldithiophosphate (component c) with a zinc di(primary)alkyldithiophosphate was prepared. The phosphorus content of the latter di(primary)alkyldithiophosphate was the same as that of the former zinc di(secondary)alkyldithiophosphate.
Comparative Example D
2,, A lubricating oil composition having the same composition of Example 1 except for replacing the bis-succinimide (component b) with a mono-succinimide dispersant was prepared.
Evaluation of Thermal Stability at Hiqh Temperatures The thermal stability of the lubrication oil compositions at high temperatures was evaluated using the JIS (Japanese Industrial Standard) K2514 ISOT (Indiana Stirred Oxidation Test). This test is used to determine the oxidation stability of a lubricating oil composition in the presence of copper, steel and heat.
(1 ) ISOT test was performed under the following conditions:
Amount of oil: 250 mL
Temperature of the test oil: 165.5°C
Test period: continuous operation for 96 hours Test results are determined and expressed as follows:
1a Viscosity increase: determined at 40°C after the continuous operation, expressed as a relative value to the viscosity (as "1 ") of the test oil before the operation;
TBN retention (HCI): in terms of %, measured using HCI, and TBN retention (ASTM D2896): determined according to ASTM D2896.
(2) Test results Test results are set forth in the following Table:
Example Comparative Example Viscosity increase 0.97 1.21 1.19 1.18 1.16 TBN retention (HCI) 65.0 61.5 60.7 60.5 60.8 TBN retention (ASTM D2896) 92.4 89.9 86.3 87.1 88.8 Remarks: The lubricating oil composition of Example 1 gave a viscosity increase of 1.02 after additional 24 hours ISOT test (total: 120 hours).
The lubricating oil composition of the present invention provides low viscosity increase and shows high TBN retention. Accordingly, it is clear that the lubricating oil composition of the present invention has high anti-thermal oxidation property at high temperatures.
The alkyl group preferably contains 3 to 18 carbon atoms. All of the two alkyl groups of the zinc dialkyldithiophosphate can be secondary alkyl groups.
Otherwise, a portion (e.g., a relatively small portion such as less than 48 mole %) of the alkyl groups of the zinc diaikyldithiophosphate can be a primary alkyl group. The secondary-alkyl type zinc dialkyldithiophosphate can be employed in combination with a zinc dialkyldithiophosphate having a primary alkyl group.
In this case, the former zinc dialkyldithiophosphate is generally employed in an amount of 52 to 98 mole %, and the latter zinc dialkyldithiophosphate can be employed in an amount of 2 to 48 mole %.
Other Additives The lubricating oil composition of the present invention can further contain other oxidation inhibitors, such as phenol oxidation inhibitors and/or amine oxidation inhibitors, in an amount of 0.01 to 5 wt %, preferably 0.1 to 3 wt %.
The lubrication oil composition of the present invention can further contain a multi-functional molybdenum-containing compound in an amount of 0.01 to 5 wt %, preferably 0.1 to 3 wt %. The molybdenum-containing compound mainly serves as friction-modifier, oxidation inhibitor and anti-wear agent in the lubricating oil composition of the present invention. The molybdenum-containing compound further provides effective high temperatures detergency. The molybdenum-containing compound can be incorporated into the lubricating oil composition of the present invention in an amount of 10 to 2,500 ppm in terms of the molybdenum metal content. Examples of the molybdenum-containing compounds include, but not limited to, a sulfur-containing molybdenum complex compound of succinimide, sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum dithiophosphate, an amine-molybdenum complex compound, oxymolybdenum diethylateamide, and oxymolybdenum monoglyceride. The sulfur-containing molybdenum complex compound of succinimide is particularly effective to increase detergency at high temperatures.
The lubricating oil composition of the present invention can further contain a viscosity index improver in an amount of less than 20 wt %, preferably in an amount of 1 to 20 wt %. Examples of the viscosity index improvers are such polymers as poly(alkyl methacrylate), ethylene-propylene copolymer, styrene-butadiene copolymer, and polyisoprene. Dispersant-type viscosity index ~ 5 improvers and multi-functional viscosity index improvers which are obtained by adding dispersancy to the above-mentioned polymers are also employable. The viscosity index improvers can be employed singly or in combination.
The lubricating oil composition of the present invention can further contain a 2Q variety of subsidiary additives. Examples of the subsidiary additives include, but not limited to, oxidation inhibitors/anti-wear agents (e.g., zinc dithiocarbamate, methylene-bis(dibutyldithiocarbamate), oil-soluble copper compounds, sulfur-containing compounds such as sulfurized olefins, sulfurized esters and polysulfides, phosphate esters, phosphite esters, and organic amide compounds 25 such as oleylamide. Metal-deactivating compounds such as benzotriazol compounds and thiaziazol compounds also can be employed. Anti-rust agents and de-emulsifiers such as nonionic surfactants (e.g., polyoxyethylene alkylphenyl ether, and copolymer of ethylene oxide and propylene oxide) also can be employed. Friction modifiers such as amines, amides, amine salts, their 30 derivatives, and fatty acid esters of polyhydric alcohols and their derivatives also can be employed. Anti-foaming agents and pour point depressants also can be employed. Each of the subsidiary additives is generally contained in the lubricating oil composition of the present invention in an amount of less than 3 wt %, preferably in the range of 0.001 to 3 wt %.
EXAMPLES
The invention will be further illustrated by the following examples, which set forth particularly advantageous method embodiments. While the Examples are provided to illustrate the present invention, they are not intended to limit it.
Example 1 A lubricating oil composition (TBN: 30 mg~KOH/g, SAE viscosity grade: SAE 40) was prepared using the following additives and base oil:
1 ~ a) overbased calcium carboxylate (TBN: 145 mg~KOH/g, a mixture of a compound of the aforementioned formula in which R has 12 to 18 carbon atoms and a compound of the formula in which R has 20 to 28 carbon atoms, in a weight ratio of 50:50 in an amount of 1.15 wt % in terms of Ca content;
b) bis-structure succinimide dispersant (nitrogen content 0.018 wt %, prepared by reaction between polyalkylene polyamine (containing nitrogen atoms of 5.0 (mean number) in a molecule) and a product produced by thermal reaction of polybutene (number average molecular weight: approx. 1,000, having at least 50 mole % of methylvinylidene structure) and malefic anhydride) in an amount of 0.018 wt % in terms of N content;
c) zinc di(secondary)alkyldithiophosphate (P 0.049 wt %, Zn 0.054 wt %, S
0.14 wt %, prepared using a secondary alcohol containing 3 to 8 carbon atoms) in an amount of 0.05 wt % in terms of P content;
d) base oil (dynamic viscosity at 40°C: 140 mm2/sec.) of the remaining amount.
Comparative Example A
A lubricating oil composition having the same composition of Example 1 except for containing no bis-succinimide (component b) was prepared.
n Comparative Example B
A lubricating oil composition having the same composition of Example 1 except for containing neither bis-structure succinimide (component b) nor zinc di(secondary)alkyldithiophosphate (component c) was prepared.
Comparative Example C
A lubricating oil composition having the same composition of Example 1 except for replacing the zinc di(secondary)alkyldithiophosphate (component c) with a zinc di(primary)alkyldithiophosphate was prepared. The phosphorus content of the latter di(primary)alkyldithiophosphate was the same as that of the former zinc di(secondary)alkyldithiophosphate.
Comparative Example D
2,, A lubricating oil composition having the same composition of Example 1 except for replacing the bis-succinimide (component b) with a mono-succinimide dispersant was prepared.
Evaluation of Thermal Stability at Hiqh Temperatures The thermal stability of the lubrication oil compositions at high temperatures was evaluated using the JIS (Japanese Industrial Standard) K2514 ISOT (Indiana Stirred Oxidation Test). This test is used to determine the oxidation stability of a lubricating oil composition in the presence of copper, steel and heat.
(1 ) ISOT test was performed under the following conditions:
Amount of oil: 250 mL
Temperature of the test oil: 165.5°C
Test period: continuous operation for 96 hours Test results are determined and expressed as follows:
1a Viscosity increase: determined at 40°C after the continuous operation, expressed as a relative value to the viscosity (as "1 ") of the test oil before the operation;
TBN retention (HCI): in terms of %, measured using HCI, and TBN retention (ASTM D2896): determined according to ASTM D2896.
(2) Test results Test results are set forth in the following Table:
Example Comparative Example Viscosity increase 0.97 1.21 1.19 1.18 1.16 TBN retention (HCI) 65.0 61.5 60.7 60.5 60.8 TBN retention (ASTM D2896) 92.4 89.9 86.3 87.1 88.8 Remarks: The lubricating oil composition of Example 1 gave a viscosity increase of 1.02 after additional 24 hours ISOT test (total: 120 hours).
The lubricating oil composition of the present invention provides low viscosity increase and shows high TBN retention. Accordingly, it is clear that the lubricating oil composition of the present invention has high anti-thermal oxidation property at high temperatures.
Claims (9)
1. A lubricating oil composition having a TBN in the range of 5 to 55 mg KOH/g comprising a major amount of a base oil of lubricating viscosity and a) 0.19 to 2.10 wt %, based on the total amount of the lubricating oil composition, of an overbased calcium carboxylate having a TBN of 100 mg KOH/g or more, wherein the wt % is expressed in terms of the calcium content;
b) 0.002 to 0.06 wt %, based on the total amount of the lubricating oil composition, of a bis-succinimide compound, wherein the wt % is expressed in terms of the nitrogen content; and c) 0.007 to 0.15 wt %, based on the total amount of the lubricating oil composition, of a zinc dialkyldithiophosphate having a secondary alkyl group, wherein the wt % is expressed in terms of the phosphorus content.
b) 0.002 to 0.06 wt %, based on the total amount of the lubricating oil composition, of a bis-succinimide compound, wherein the wt % is expressed in terms of the nitrogen content; and c) 0.007 to 0.15 wt %, based on the total amount of the lubricating oil composition, of a zinc dialkyldithiophosphate having a secondary alkyl group, wherein the wt % is expressed in terms of the phosphorus content.
2. The lubricating oil composition according to Claim 1, wherein the amount of the overbased calcium carboxylate having a TBN of 100 mg.cndot.KOH/g or more is in the range of 0.38 to 1.15 wt %, based on the total amount of the lubricating oil composition and expressed in terms of the calcium content.
3. The lubricating oil composition according to Claim 1, wherein the amount of the bis-succinimide compound is in the range of 0.014 to 0.02 wt %, based on the total amount of the lubricating oil composition and expressed in terms of the nitrogen content.
4. The lubricating oil composition according to Claim 1, wherein the amount of the zinc dialkyldithiophosphate having a secondary alkyl group is in the range of 0.036 to 0.072 wt %, based on the total amount of the lubricating oil composition and expressed in terms of the phosphorus content.
5. The lubricating oil composition according to Claim 1, wherein the overbased calcium carboxylate having a TBN of 100 mg KOH/g or more comprises more than 50 wt % of the following compound A and less than 50 wt % of the following compound B:
in which R is an alkyl group having 12 to 28 carbon atoms.
in which R is an alkyl group having 12 to 28 carbon atoms.
6. The lubricating oil composition according to Claim 1, wherein the bis-succinimide compound is prepared by a thermal reaction between a poly-butene compound containing 50% or more methylvinylidene structure and maleic anhydride, followed by further reaction of the resulting polybutenyl succinic anhydride with a polyalkylenepoiyamine containing 4 to 10 nitrogen atoms per molecule.
7. The lubricating oil composition according to Claim 1, wherein the zinc dialkyldithiophosphate having a secondary alkyl group comprises alkyl groups independently having 3 to 8 carbon atoms.
8. A method of improving the oxidation stability at high temperatures of an internal combustion engine, said method comprising operating the internal combustion engine with a lubricating oil composition having a TBN in the range of 5 to 55 mg KOH/g comprising a base oil of lubricating viscosity and a) 0.19 to 2.10 wt %, based on the total amount of the lubricating oil composition, of an overbased calcium carboxylate having a TBN of 100 mg KOH/g or more, wherein the wt % is expressed in terms of the calcium content;
b) 0.002 to 0.06 wt %, based on the total amount of the lubricating oil composition, of a bis-succinimide compound, wherein the wt % is expressed in terms of the nitrogen content; and c) 0.007 to 0.15 wt %, based on the total amount of the lubricating oil composition, of a zinc dialkyldithiophosphate having a secondary alkyl group, wherein the wt % is expressed in terms of the phosphorus content.
b) 0.002 to 0.06 wt %, based on the total amount of the lubricating oil composition, of a bis-succinimide compound, wherein the wt % is expressed in terms of the nitrogen content; and c) 0.007 to 0.15 wt %, based on the total amount of the lubricating oil composition, of a zinc dialkyldithiophosphate having a secondary alkyl group, wherein the wt % is expressed in terms of the phosphorus content.
9. The method according to Claim 8, wherein the internal combustion engine is a four stroke trunk piston diesel engine.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2004380522A JP5198719B2 (en) | 2004-12-28 | 2004-12-28 | Lubricating oil composition |
JP2004-380522 | 2004-12-28 |
Publications (2)
Publication Number | Publication Date |
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CA2531433A1 true CA2531433A1 (en) | 2006-06-28 |
CA2531433C CA2531433C (en) | 2014-02-18 |
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CA2531433A Expired - Fee Related CA2531433C (en) | 2004-12-28 | 2005-12-23 | Lubricating oil composition having improved oxidation stability at high temperatures |
Country Status (4)
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EP (1) | EP1676902B1 (en) |
JP (1) | JP5198719B2 (en) |
CA (1) | CA2531433C (en) |
SG (1) | SG123779A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US9175237B2 (en) * | 2007-12-12 | 2015-11-03 | Chevron Oronite Technology B.V. | Trunk piston engine lubricating oil compositions |
CA2827438A1 (en) | 2011-02-17 | 2012-08-23 | The Lubrizol Corporation | Lubricants with good tbn retention |
US20130157910A1 (en) * | 2011-12-16 | 2013-06-20 | Chevron Oronite Company Llc | Diesel engine oils |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
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US5744430A (en) * | 1995-04-28 | 1998-04-28 | Nippon Oil Co., Ltd. | Engine oil composition |
JP3615267B2 (en) * | 1995-04-28 | 2005-02-02 | 新日本石油株式会社 | Engine oil composition |
JP3941889B2 (en) * | 1995-06-15 | 2007-07-04 | 新日本石油株式会社 | Engine oil composition |
EP0933417B1 (en) * | 1998-01-30 | 2003-04-02 | Chevron Chemical S.A. | Unsulfurized, alkali metal-free, additive for lubricating oils |
DE69827625T2 (en) * | 1998-09-09 | 2005-12-08 | Chevron Chemical S.A. | Process for the preparation of alkaline earth metal salts with high basicity, in particular of a ring-bound hydrocarbyl salicylate carboxylate |
JP2000192069A (en) * | 1998-12-28 | 2000-07-11 | Oronite Japan Ltd | Lubricating oil composition and additive composition for diesel internal combustion engine |
JP3722472B2 (en) * | 2000-06-02 | 2005-11-30 | シェブロンテキサコジャパン株式会社 | Lubricating oil composition |
JP4643030B2 (en) * | 2001-01-29 | 2011-03-02 | 日産自動車株式会社 | Diesel engine oil composition |
JP4185307B2 (en) * | 2001-09-20 | 2008-11-26 | 新日本石油株式会社 | Lubricating oil composition for internal combustion engines |
JP4643087B2 (en) * | 2001-09-25 | 2011-03-02 | 日産自動車株式会社 | Lubricating oil composition for internal combustion engines |
JP4017514B2 (en) * | 2002-12-27 | 2007-12-05 | コスモ石油ルブリカンツ株式会社 | Engine oil |
JP4515797B2 (en) * | 2004-03-19 | 2010-08-04 | 新日本石油株式会社 | Lubricating oil composition for diesel engines |
-
2004
- 2004-12-28 JP JP2004380522A patent/JP5198719B2/en active Active
-
2005
- 2005-12-23 EP EP05258039.6A patent/EP1676902B1/en active Active
- 2005-12-23 CA CA2531433A patent/CA2531433C/en not_active Expired - Fee Related
- 2005-12-27 SG SG200508401A patent/SG123779A1/en unknown
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SG123779A1 (en) | 2006-07-26 |
JP2006182987A (en) | 2006-07-13 |
EP1676902A1 (en) | 2006-07-05 |
JP5198719B2 (en) | 2013-05-15 |
CA2531433C (en) | 2014-02-18 |
EP1676902B1 (en) | 2019-03-20 |
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