CN100564498C - Lubricating oil composition - Google Patents
Lubricating oil composition Download PDFInfo
- Publication number
- CN100564498C CN100564498C CNB031064795A CN03106479A CN100564498C CN 100564498 C CN100564498 C CN 100564498C CN B031064795 A CNB031064795 A CN B031064795A CN 03106479 A CN03106479 A CN 03106479A CN 100564498 C CN100564498 C CN 100564498C
- Authority
- CN
- China
- Prior art keywords
- lubricating oil
- quality
- oil composition
- engine
- base oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000000203 mixture Substances 0.000 title claims abstract description 133
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 127
- 239000000654 additive Substances 0.000 claims abstract description 70
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 57
- 239000002199 base oil Substances 0.000 claims abstract description 55
- 238000000746 purification Methods 0.000 claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000003749 cleanliness Effects 0.000 claims abstract description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- 239000005864 Sulphur Substances 0.000 claims abstract description 11
- 238000004088 simulation Methods 0.000 claims abstract description 8
- 238000005259 measurement Methods 0.000 claims abstract description 5
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 22
- SCJNCDSAIRBRIA-DOFZRALJSA-N arachidonyl-2'-chloroethylamide Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(=O)NCCCl SCJNCDSAIRBRIA-DOFZRALJSA-N 0.000 claims description 11
- 239000012459 cleaning agent Substances 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 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 claims description 5
- 230000000996 additive effect Effects 0.000 abstract description 49
- 239000003921 oil Substances 0.000 description 26
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- -1 molybdate compound Chemical class 0.000 description 17
- 239000006185 dispersion Substances 0.000 description 16
- 150000007524 organic acids Chemical class 0.000 description 13
- 239000004034 viscosity adjusting agent Substances 0.000 description 12
- 238000009472 formulation Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 9
- 239000003599 detergent Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000008186 active pharmaceutical agent Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000013543 active substance Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000003883 substance clean up Methods 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- RYSNDQDGZQEOAL-UHFFFAOYSA-N calcium;phenol Chemical compound [Ca].OC1=CC=CC=C1 RYSNDQDGZQEOAL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000994 depressogenic effect Effects 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 239000005749 Copper compound Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052728 basic metal Inorganic materials 0.000 description 3
- 150000003818 basic metals Chemical class 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910002476 CuII Inorganic materials 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- PFUVZUNNAOPQNQ-UHFFFAOYSA-N [Ca].[Ca].C1(=CC=CC=C1)O Chemical compound [Ca].[Ca].C1(=CC=CC=C1)O PFUVZUNNAOPQNQ-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005885 boration reaction Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- QUXMTKVAANIIFI-UHFFFAOYSA-N copper dihydroxy-sulfanyl-sulfanylidene-lambda5-phosphane Chemical compound [Cu].P(O)(O)(=S)S QUXMTKVAANIIFI-UHFFFAOYSA-N 0.000 description 1
- DZCLVBQEPZQZNN-UHFFFAOYSA-N copper;phenol Chemical compound [Cu].OC1=CC=CC=C1 DZCLVBQEPZQZNN-UHFFFAOYSA-N 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 108010011222 cyclo(Arg-Pro) Proteins 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000865 liniment Substances 0.000 description 1
- 229940040145 liniment Drugs 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000004441 surface measurement Methods 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/027—Neutral 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
- 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
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/2805—Esters used as base material
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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- 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
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- 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
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- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/088—Neutral salts
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- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
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- 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
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Abstract
A kind of heavy duty diesel engine lubricating oil composition, it contains or is mixed by following component: (A) by the quality of lubricating oil, the a large amount of lubricating oil that contain at least 35% (quality) III class base oil, by described base oil, it contains at the most, and 0.03% (quality) sulphur and viscosity index are 120, and by described base oil, more than or equal to 90% (quality) stable hydrocarbon; And the compositions of additives that (B) contains following component on a small quantity: (i) purification agent and (ii) one or more its ground additive; Press wherein that ASTM D2602 measures, the cold starting simulation viscosity of lubricating oil composition-25 ℃ under is less than 7000mPas, and by the quality of lubricating oil composition, the sulfate ash of pressing ASTM D874 measurement is less than 1.35% (quality).Described lubricating oil composition provides the piston cleanliness of improved heavy duty diesel engine.
Description
The present invention relates to be used for the particularly self-igniton engine lubricating oil composition of the crankcase of the heavy-duty engine of highway truck for example of lubricating engine.
For performance and the expected life of keeping engine, engine is cleaned as far as possible, the lubricated of explosive motor is necessary.
Because the extremely long life-span, heavy load truck market uses diesel motor as its preferred energy, and has developed various lubricant agent specials, to satisfy such heavy duty diesel engine performance requriements stricter more than car engine.
Have now found that, heavy-gravity lubricating oil composition ratio not heavy-gravity lubricating oil composition helps to provide better Engine Cleanliness Level: in the OM441LA testing of engine, this point is very clearly, has wherein assessed the degree of cleaning of piston on two notches of piston.
The possible method of improving the cleaning effect of oil composition comprises detergent additive, and for example calcium sulphonate or magnesium and phenol calcium or magnesium it is believed that it can improve the degree of cleaning of engine.But, be intended to reduce by waste gas component for example the regulation of the environmental pollution that causes of particulate matter and oxynitrides (NOx) promoting the content that lubricating oil composition reduces sulfate ash, so reduce the quantity of purification agent.This is that for example metal detergent, zinc compound and molybdate compound all produce sulfate ash because of metal additive.
Find that surprisingly using not, heavy-gravity can obtain satisfied piston cleanliness with the lubricating oil composition that contains the lesser amt detergent additive.
Therefore, first aspect the invention provides and contains or mixed by following component the heavy duty diesel engine lubricating oil composition that obtains:
(A) by the quality of lubricating oil, the a large amount of lubricating oil that contain at least 35% (quality) III class base oil, quality by described base oil, contain 0.03% (quality) sulphur at the most, viscosity index is 120 or bigger and by the quality of described base oil, and the stable hydrocarbon more than or equal to 90% (quality) is arranged; And
(B) contain the additive of following component on a small quantity:
(i) cleaning agent composition and
(ii) one or more other additives;
Wherein the cold starting of oil composition simulation viscosity (press ASTM D2602 measures) is less than 7000mPas (25 ℃), and by the quality of lubricating oil composition, sulfate ash (pressing ASTM D874 measurement) is less than 1.35% (quality).
Second aspect, the invention provides a kind of method of lubricated heavy duty diesel engine, the gross exhaust gas of described engine is at least 6.5 liters, and the free air delivery of every stroke is at least 1.0 liters/stroke, and described method comprises the lubricating oil composition supply engine with the first aspect regulation.
The third aspect the invention provides the combination of a kind of heavy duty diesel engine, and the gross exhaust gas of described engine is at least 6.5 liters, the free air delivery of each stroke is at least 1.0 liters/stroke, and lubricating oil composition is the first aspect defined.
Fourth aspect, the invention provides the application of lubricating oil, in the lubricating oil composition of the piston cleanliness of improving engine, by the quality of lubricating oil, contain the lubricating oil of at least 35% (quality) III class base oil, and by the quality of described base oil, contain 0.03% (quality) sulphur at the most, viscosity index is 120 or bigger, by the quality of described base oil, contains the stable hydrocarbon that is equal to or greater than 90% (quality).
The 5th aspect the invention provides and a kind ofly is added to the method for improving the engine piston degree of cleaning in the engine by the lubricating oil composition with first aspect regulation, particularly in the OM441LA testing of engine.
The 6th aspect, the invention provides a kind of heavy duty diesel engine lubricating oil composition, according to the CEC-L-52-T-97 program, obtain at least 25 piston cleanliness standard points and be not more than 4% supercharging loss in the OM441LA testing of engine, described oil composition contains or is obtained by following component mixing:
(A) a large amount of lubricating oil and
(B) contain the additive of following component on a small quantity:
(i) a kind of cleaning agent composition and
(ii) one or more other additives;
Wherein the cold starting of oil composition simulation viscosity (press ASTM D2602 measures) is 7000mPas (25 ℃) at least, and by the quality of oil composition, the sulfate ash of pressing ASTM D874 measurement is less than 1.35% (quality).
In this manual:
" in a large number " refers to surpass 50% (quality) of composition.
" on a small quantity " refers to 50% (quality) less than composition, with regard to respect to described additive with respect to regard to the total mass percentage ratio of all additives that exist in the composition, is used as the activeconstituents of additive.
" contain " or be used for determining the existence of described characteristic, step, composition or component, but can not get rid of the existence of one or more other characteristics, step, composition, component with the etymology speech.Here use under the situation that term " contains ", term " contain substantially " and with the etymology speech also in its scope, and be its embodiment preferred; Therefore term " contain " and with the etymology speech in the scope of " containing substantially ", and be its preferred embodiment.
" TBN " total basicnumber for measuring with ASTM D2896.
" oil-soluble " or " oil dispersible " not necessarily represent additive can any ratio dissolving, moltenly mix or be suspended in the lubricating oil.But they refer to that for example they can be enough to be dissolved in or stable being dispersed in the oil, reach the degree that is enough to produce desired effect in the environment that oil uses.And if desired, the adding of other additives also can allow to add more high-load special additive.
" ppm " refers to the quality by lubricating oil composition, with every ppm part of quality representation.
The word SAE that contracts represents Society of automotive engineers.
Unless add explanation in addition, listed percentage ratio all is the % (quality) by activeconstituents, does not just consider to carry oil or thinning oil.
Should be pointed out that lubricating oil composition of the present invention contains the additive of regulation, promptly before mixing with chemically can be identical or different independent components later.Therefore, the various components that will be appreciated that composition prescription, store or the condition used under and the present invention's product of also providing the result that can be used as any such reaction to obtain can be provided.
In addition, should also be noted that when specification sheets relates to the lubricating oil composition that contains the specified quantity sulfate ash that it means that lubricating oil composition has the sulfate ash of ASTM D874 regulation.
Characteristics of the present invention are now described in further detail.
Heavy duty diesel oil starts
Heavy duty diesel engine of the present invention is preferred for the land route vehicle, more preferably is used for large-scale road vehicle, for example large truck.The weight of road vehicle is generally more than 12 tons.The gross exhaust gas of the engine that in such vehicle, uses usually at least 6.5, preferably at least 8, more preferably at least 10, for example at least 15 liters; Preferred gross exhaust gas is the engine that 12-20 rises.Usually, gross exhaust gas greater than 24 liters engine not as terrestrial vehicle.Every stroke free air delivery of engine of the present invention also is at least 1.0 or at least 1.5, for example at least 1.75, preferably at least 2 liters/stroke.Usually, every stroke free air delivery of the heavy duty diesel engine in the road vehicle is at the most 3.5, for example at the most 3.0, preferred 2.5 liters/stroke at the most.With regard to explosive motor, term " heavy duty " is known in this specialty: referring to ASTM D4485 the 3.17th joint, wherein characterize the heavy-duty engine operation with V-bar, power output and internal temperature (usually near possible maximum value); So heavy duty diesel engine is considered to operate under such condition usually.
As used herein, term " gross exhaust gas " and " every stroke free air delivery " are that known (referring to " diesel motor book of reference ", B.Challen and R.Baranescu edit, second edition for being familiar with the explosive motor technical professional, 1999, the SAE international publishing).Briefly, term " free air delivery " is corresponding to the volume of cylinder in the engine that is moved decision by piston, and therefore " gross exhaust gas " is the relevant cumulative volume of number of cylinders; And term " every stroke free air delivery " be gross exhaust gas with engine in the ratio of number of cylinders.
Lubricating oil composition
The present invention be more particularly directed to multigrade oil composition (being also referred to as multistage all purpose grease), they usually are heavy-gravity not.Its viscometric properties of SAE J300 classification criterion determines, for example maximum cold-starting viscosity and pumping viscosity and the minimum and maximum kinematic viscosity under 100 ℃.
Preferably, of the present invention aspect each in, the cold-starting viscosity of lubricating oil composition or cold starting simulation viscosity less than 6000mPas (30 ℃), be more preferably less than 6200mPas (35 ℃), irrelevant with sulfate ash, measure with ASTM D2602.
Preferably, of the present invention aspect each, quality by lubricating oil composition, cold starting simulation viscosity less than 1.25 or 1.15, be more preferably less than in 1.05,1.00 and 0.95 any, for example less than 0.90, particularly less than 0.85, preferably less than 0.75% (quality), measure with ASTMD874.Sulfate ash is in 0～0.5 quality % scope.
In an embodiment preferred, as above the quantity of Gui Ding sulfate ash obtains from metallic additive only, and more preferably sulfate ash only obtains from metal detergent, for example calcium purification agent and/or magnesium purification agent.
Preferably, of the present invention aspect each, the TBN of lubricating oil composition is less than 11.2 or 10.5 or 9.8, preferably less than in 9.2,8.8 and 8.5 any, particularly less than 7.8, preferably less than 7.1.TBN can be in the scope of 2.1-5.5.
Preferably, of the present invention aspect each in, the metal content of lubricating oil composition (no matter being transition metal or alkaline-earth metal or basic metal) less than 4800 or 4400 or 4000, be more preferably less than in 3700,3500 and 3300 any, particularly less than 3000, preferably less than 2600ppm.Metal content can be in the scope of 0-1800ppm.
For those skilled in the art, the method for measuring metal content is that everybody is familiar with.
In the embodiment of the present invention aspect each, the largest motion viscosity of lubricating oil composition of the present invention under 100 ℃ less than 21.9 this, preferably less than 16.3 this, for example less than 12.5 this, particularly less than 9.3 these (irrelevant) with the quantity of cold starting simulation viscosity and sulphated ash.100 ℃ kinematic viscosity can for example be 16.3 to less than 21.9; Preferred 12.5 arrive less than 16.3; More preferably 9.3 to less than 12.5, arrives less than 9.3 as 5.6.
Therefore, lubricating oil composition of the present invention is the multigrade oil composition of SAE 10W-X or SAE 5W-X or OW-X viscosity grade, and wherein X represents in 20,30,40 and 50 any, and preferred X is 20 or 30 or 40, and more preferably X represents 40.
API, ACEA and JASO have stipulated the performance level that lubricating oil composition is required.The performance index that are called Global in addition, it comprises test and the performance level that is obtained by ACEA, API and JASO technical specification.
Therefore, lubricating oil composition of the present invention preferably satisfies the performance requriements of heavy duty diesel engine lubricating oil at least, for example satisfies API CG-4 at least; Preferably satisfy API CH-4 at least; API CI-4 at least particularly.In another embodiment, lubricating oil composition of the present invention (with to satisfy the API performance requriements irrelevant) particularly for piston cleanliness, satisfies ACEAE2-96 at least, more preferably satisfies ACEA E3-96 at least; Preferably satisfy ACEA E5-99 at least, particularly satisfy ACEA E4-99 at least.In another embodiment, lubricating oil composition of the present invention (with to satisfy API and ACEA performance requriements irrelevant) preferably satisfies JASO DH-1 or Global DHD-1.
Lubricating oil
Lubricating oil is the main liquid ingredient of lubricating oil composition.Lubricating oil comprises any oil that (a) is added to the oil in enriched material or the additive formulations and (b) exists in enriched material or additive formulations.
Lubricating oil can be the ucon oil that is selected from I, II, III, IV and V class base oil and mineral lubricating oils particulate matter and any two or more mixture.
Base oil can include but not limited to distillation, solvent treatment, hydrotreatment, oligomeric, esterification and refining with various method preparation.
API 1509 " Engine Oil Licensing and Certification System ",, point out that all base oils all can be divided into five general categories in December, 1996 by the 14 edition:
I class base oil contains less than 90% stable hydrocarbon and/or less than 0.03% sulphur, and viscosity index is more than or equal to 80 with less than 120;
II class base oil contains more than or equal to 90% stable hydrocarbon and is less than or equal to 0.03% sulphur, and viscosity index is more than or equal to 80 with less than 120;
III class base oil contains more than or equal to 90% stable hydrocarbon and is less than or equal to 0.03% sulphur, and viscosity index is more than or equal to 120;
IV class base oil is polyalphaolefin (PAO); And
V class base oil comprises every other base oil, but does not comprise I, II, III or IV class base oil.
Be used for determining that the test method of above-mentioned classification is ASTM D2007 (stable hydrocarbon), ASTMD2270 (viscosity index), ASTM D2622, one (sulphur) in 4294,4927 and 3120.
IV class base oil is the hydrogenation oligopolymer that polyalphaolefin (PAO) comprises alhpa olefin, and most important oligomerization process is free radical method, Ziegler catalysis method, a cation method and Fei Ruide-Kerafyrm catalysis method now.
The V class base oil of ester class form is preferred, also can commerce provide.Example comprises polyol ester, for example pentaerythritol ester, trihydroxymethylpropanyl ester and DOPCP; The diester class; C
36Dimeric dibasic acid ester; Trimellitate, just 1,2,4-benzene tricarbonic acid ester; And phthalic ester, just 1,2-benzenedicarboxylic acid ester.The preferred molecular formula RCO of the acid of preparation ester
2The monocarboxylic acid of H, wherein R is side chain, straight chain or the blended alkyl.Such acid for example can contain 6-18 carbon atom.
Quality by lubricating oil, the lubricating oil of first aspect, preferred the 6th aspect contains at least 35% (quality) III class base oil, and by the quality of described base oil, contain 0.03% (quality) sulphur at the most, and viscosity index is 120 or bigger, and, contain more than or equal to 90% (quality) stable hydrocarbon by the quality of described base oil.
Preferably, by the quality of lubricating oil, lubricating oil contains at least 40, more preferably at least 45, for example at least 50, particularly 55-95, preferred 65-90, for example described base oil of 70-80 or 85% (quality).In order to prevent uncertainty, the base oil that is provided by binder component in lubricating oil composition is provided lubricating oil.
In an embodiment preferred, the regulation ratio of described base oil is to be added in enriched material or the additive formulations.
Contain at lubricating oil under the situation of mixture of all kinds of base oils, preferably have I class and III class base oil and exist.
In an embodiment preferred, lubricating oil is mainly by III class base oil and one or more IV classes and V class base oil (ester-formin) and a small amount of those base oils that provided by the additive in the lubricating oil composition.
Compositions of additives
Aspect all, compositions of additives contains a kind of purification agent and one or more other additives of the present invention, and they can comprise other metallic additive, for example zinc dithiophosphates.
Cleaning agent composition contains purification agent.Purification agent is the additive that a kind of piston deposit that can reduce in engine generates, for example high temperature lacquer and lacquer deposits; It has in the acid and character also can make thin dispersible solid remain in the suspension.It is based on metal " soap ", and just the organic acid metal-salt is also referred to as tensio-active agent here.
The organic acid metal-salt has and is used for the hydrophobic tail of oil-soluble length.So organic acid has one or more functional groups usually, for example OH or COOH or SO
3H; And hydrocarbyl substituent.
The organic acid example comprises sulfonic acid; Phenols; Whitfield's ointment and sulphurated derivatives thereof; And carboxylic acid.
Purification agent of the present invention can contain the particulate matter (for example calcium carbonate granule thing) of organic acid metal-salt and alkaline, inorganic salts.
Therefore, each in the cleaning agent composition or metal detergent can be neutral or overbasic, and those skilled in the art understand such term.
The cleaning agent composition that contains one or more organic acid metal-salts can exist, for example metal organic sulfonate and metal phenates.
Purification agent of the present invention can be a kind of organic acid salt or multiple organic acid salt, for example compound purification agent.Preferably, they are a kind of organic acid salt.
Compound purification agent is for wherein basic metal is stable by more than one organic acids.Those skilled in the art will appreciate that one type organic acid can be contained in the same type organic acid mixture.For example, sulfonic acid can contain the mixture of the sulfonic acid of different molecular weight.Such organic acid composition is called a class.Therefore, compound purification agent is different with the mixture of two or more independent overbasic purification agent, and the example of such mixture is a kind of overbased calcium salicylate that overbasic phenol calcium purification agent is arranged.
This specialty has been described the example of the compound purification agent of high alkalinity.For example, the mixture that international patent application book 97-46643/4/5/6 and 7 has described by more than one acidic organic compounds that neutralize with alkaline metal cpds prepares mixed complex, makes the high alkalization of mixture then.The single alkaline micella of purification agent is therefore stable with various organic acid types.The example of compound purification agent comprises phenol calcium-calcium salicylate-calcium sulfonate detergents, phenol calcium-calcium sulfonate detergents and phenol calcium-calcium salicylate purification agent.
EP-A-0750659 discloses a kind of by phenol calcium carboxylation, makes the calcium salicylate-phenol calcium complexes of the mixture sulfuration and the high alkalization preparation of calcium salicylate and phenol calcium then.Such mixture can be described as " phenalates ".
Preferred compound purification agent is a Whitfield's ointment alkali purification agent, for example phenol calcium-calcium salicylate-calcium sulfonate detergents and " phenalatess ".
Purification agent, unit opinion compound or compound not, its total basicnumber (TBN) all 15 or 60 to 600, preferred 100-450, more preferably in the scope of 160-400.
In order to prevent uncertainty, cleaning agent composition also can contain ashless additive, promptly metal-free purification agent.
Cleaning agent composition preferably contains at least a high alkaline metal detergent.
The 1st and 2 family's metals preferably as the metal in the purification agent, more preferably calcium and magnesium, particularly preferably are calcium.
Preferably, of the present invention aspect each, the quantity of the alkaline-earth metal in the lubricating oil composition less than 3200 or 3000 or 2800, be more preferably less than in 2500,2400 and 2300 any, particularly less than 2000, preferably less than 1800ppm.The content of alkaline-earth metal can be in the 0-1200ppm scope.
Preferably, of the present invention aspect each, by the content of tensio-active agent, the quantity of cleaning agent composition in lubricating oil composition at the most 50, preferably at the most 30,20 mmoles tensio-active agent/kilogram lubricating oil composition at the most particularly.In one embodiment, by the content of tensio-active agent, the quantity of cleaning agent composition in lubricating oil composition is 10-15 mmole/kilogram.
The method of surface measurements promoting agent quantity is known for those skilled in the art.For example, those skilled in the art can calculate the quantity of final lubricating oil composition by the relevant data of the raw material that is used for producing purification agent (for example organic acid) quantity and from the quantity relevant data of the purification agent that is used for final lubricating oil composition.Various analytical procedures (for example dialysis, metal analysis, CO2 analysis, potentiometric titration and chromatogram) also can be used for measuring the quantity of tensio-active agent.
These professional those skilled in the art will appreciate that it is proximate that the method for mensuration metal salts of organic acids (being also referred to as tensio-active agent) quantity is filled base unit weight, and diverse ways always can accurately not provide identical result; But they are enough accurately for enforcement of the present invention.
Supplementary additive
Other additives also can exist in lubricating oil composition of the present invention.
Be applicable to that supplementary additive of the present invention comprises viscosity index improver, corrosion inhibitor, oxidation retarder or antioxidant, dispersion agent, rust-preventive agent, anti-wear agent, pour point depressant, emulsion splitter and kilfoam.
Viscosity index improver (or viscosity modifier) provides high temperature and cold operation for lubricating oil, and makes lubricating oil keep shear stable under heating up, and also has acceptable viscosity at low temperatures.The compound that is suitable as viscosity modifier is generally high molecular weight hydrocarbon polymer, comprises for example polymethacrylate of polyester; Poly-(ethylene, propylene) multipolymer and closely-related improvement thing thereof; Poly-(styrene butadiene or isoprene) polymkeric substance of hydrogenant and improvement thing; And poly-(styrene-maleic anhydride) polymkeric substance of esterification.The number-average molecular weight of oil soluble viscosity modifier is generally 15000-1000000, preferred 20000-600000 at least, with gel permeation chromatography or light scattering determining.Here with " chemistry of lubricating oil and engineering ", R.M.Mortier and S.T.Orzulik edit, first version, 1992, Blackie Academic﹠amp; The content of Professional chapter 5 is incorporated the present invention into.
Corrosion inhibitor reduces the corrosion of the metal part of lubricating oil composition contact.For example at US-A-2719125, disclosed thiadiazoles is the example of lubricating oil corrosion inhibitor in 2719126 and 3087932.
Oxidation retarder is that antioxidant descends the in use rotten tendency of mineral oil, and so rotten evidence for example is that similar paint film generates and sludge formation in the metallic surface, and viscosity increases.The oxidation retarder that is fit to comprises sulfurized alkylphenol and basic metal or alkaline earth salt; Hindered phenol; Diphenylamine; Phenyl naphthyl amines and sulphur phosphatization or the sulfurized hydro carbons.
Other oxidation retarder or the antioxidant that can be used for lubricating oil composition comprise oil-soluble copper compounds.Copper can be used as any stable oil-soluble copper compounds and is blended in the oil.The molten finger described compound under normal blending condition of so-called oil is soluble in oil or additive formulations.For example, copper can the dialkyl sulfo-or the form of phosphorodithioic acid copper exist.On the other hand, copper can be used as synthetic or natural carboxylic acid C for example
8-C
18The mantoquita of lipid acid (a kind of unsaturated acid or ramose carboxylic acid) adds.Oil soluble dithiocarbamic acid copper, sulfonic acid copper, phenol copper and Acetyl Acetone acid copper also are suitable for.The copper compound of particularly suitable for the alkalescence that obtains by alkenyl succinic or its acid anhydride, neutral or tart CuI and/or CuII mantoquita.
The consumption of copper antioxidant in final lubricating oil composition is generally about 5-500ppm weight copper.
Dispersion agent contains in use the oil-insoluble substance that is produced by oxidation at suspension in fluid, thereby prevents the sludge flocculation and deposit on metal parts.Compare with metallic (therefore generating ash) dispersion agent, so-called ashless dispersant is the organic substance that does not generate ash when burning basically.Metal-free dispersion agent of boration is also referred to as ashless dispersant here.The dispersion agent that is fit to for example comprises the carboxylic acid derivative that long chain hydrocarbon groups replaces, and wherein the number-average molecular weight of alkyl is often less than 15000, for example less than 5000; The example of such derivative is the derivative of the succsinic acid of high molecular alkyl replacement.The carboxylic acid that such alkyl replaces for example can react preferred with nitrogenous compound and the polyalkylene polyamine reaction, or reacts with alcohol.Particularly preferred dispersion agent is the reaction product of polyalkylene amine and alkenyl succinic anhydrides.The example that discloses the specification sheets of the up-to-date dispersion agent of mentioning type is US-A-3202678,3154560,3172872,3024195,3024237,3219666,3216936 and BE-A-662875.
The heavy duty diesel engine lubricating oil composition often has the nitrogen of comparatively high amts than car engine, is preferably obtained by dispersion agent, because generate more heavy wool insoluble substance, for example oil smoke in heavy duty diesel engine.Therefore, by the quality of lubricating oil, nitrogen content preferably at least 0.06, more preferably at least 0.08, for example at least 0.10, particularly at least 0.12% (quality).The quantity of nitrogen (preferably being obtained by dispersion agent) usually is not more than 0.2% (quality), and the quantity of nitrogen is pressed ASTMD4629 and measured.
In addition, dispersiveness can be provided by the polymerizable compound that can provide viscosity index to improve character and dispersiveness, and such compound is called multifunctional viscosity index improver.Such polymkeric substance is that with the different of traditional viscosity index improver they provide multiple performance, for example except that viscosity index is improved, also has dispersiveness and/or oxidation-resistance.
Olefin copolymer dispersion agent and polymethacrylate dispersion agent are the examples of multi-functional viscosity modifier.Multi-functional viscosity modifier is by in that chemically for example amine, pure and mild acid amides are connected on the polymkeric substance and prepare with various funtion parts, the number-average molecular weight of described polymkeric substance is preferably at least 15000,20000-600000 for example, with gel permeation chromatography or light scattering determining.Those that describe in the relevant viscosity modifier above used polymkeric substance can be.So amine molecule can add, so that dispersiveness and/or oxidation-resistance are provided, and the phenol molecule also can add, so that improve oxidation-resistance.So specific example is and reactive monomer maleic anhydride graft for example, then for example with the ethylene-propylene copolymer of alcohol or amine reaction.
EP-A-24146 and EP-A-0854904 disclose the example of dispersion agent and dispersant viscosity modifiers, and therefore they here incorporate into.
Can use the rust-preventive agent that is selected from non-ionic type poly (oxyalkylene) Quito alcohol and ester, polyoxy alkylidene phenol and anionic alkylsulphonic acid.
Anti-wear agent such as their title comprise, and it reduces the wearing and tearing of metal parts.Dialkyl zinc dithiophosphate (ZDDPs) is widely used as anti-wear agent.The example that is used for the ZDDPs of oil-based composition is those molecular formula Zn[SP (S) (OR
1) (OR
2)]
2ZDDPs, R wherein
1And R
2Contain 1-18, preferred 2-12 carbon atom.
Sulfur-bearing also is the example of anti-wear agent with the compound that contains molybdenum.The compound of ashless phosphorous and sulfur-bearing also is suitable for.
Pour point depressant is also referred to as the mobile improving agent of lubricating oil, and it descends fluid flow or dumpable minimum temperature.Such additive is that everybody is familiar with.Polysiloxane type kilfoam for example silicone oil or polydimethylsiloxane can provide foam control.
Can use a small amount of deemulsification component.Preferred deemulsification component is open in EP-A-0330522.It makes by the affixture reaction that oxirane and di-epoxide and polyol reaction obtain.
Some above-mentioned additive can provide multiple effect; For example single additive can be used as dispersion agent-oxidation retarder.This approach is that everybody is familiar with, and does not here need to further specify.
Preferably, wear preventive additive for example dialkyl phosphorodithioic acid metal-salt (for example dialkyl zinc dithiophosphate) in lubricating oil composition of the present invention, exist.
When lubricating oil composition contained one or more above-mentioned additives that comprise dispersion agent, every kind of additive was usually can make additive provide the quantity of required function to be blended in the base oil.When being used for lubricating oil, representative effective quantity of such additive is as follows:
Additive % (quality) a.i.* % (quality) a.i.*
(wide region) (preferably)
Viscosity modifier 0.01-6 0.01-4
Corrosion inhibitor 0.01-5 0.01-1.5
Oxidation retarder 0.01-5 0.01-1.5
Antifriction liniment 0.01-5 0.01-1.5
Dispersion agent 0.1-20 0.1-8
Dispersant viscosity modifiers 0.01-5 0.05-5
Purification agent 0.01-6 0.01-3
Anti-wear agent 0.01-6 0.01-4
Pour point depressant 0.01-5 0.01-1.5
Rust inhibitor 0.001-0.5 0.01-0.2
Kilfoam 0.001-0.3 0.001-0.15
Emulsion splitter 0.001-0.5 0.01-0.2
* % (quality) activeconstituents is based on final lubricating oil composition
Available any method easily is added to additive in the lubricating oil (being also referred to as base oil).For example, can every kind of additive directly be added in the oil by additive is dispersed or dissolved in the oil by required concentration.Such blending can or heat up at normal temperature and can occur.Usually, additive provides as the mixture with base oil, so that its processing is easier.
When multiple additives was used, preparation contained a kind of of additive and thinner and multiple additives prescription (being also referred to as compositions of additives or enriched material) may be wished, though dispensable.Described thinner can be base oil, and therefore except that viscosity modifier, multi-functional viscosity modifier and pour point depressant, additive can be added in the base oil simultaneously, makes lubricating oil composition.Can mix by thinner or solvent and mitigation heating and promote that additive formulations is dissolved in the lubricating oil, but this point is dispensable.Usually preparation contains the additive formulations of proper amt additive, so that when additive formulations combines with the lubricating oil of pre-determined quantity, obtains required concentration in final prescription.For example, one or more purification agents can be added in the solvent (for example carrying oil or thinning oil) that a small amount of base oil or other can be compatible with desired additives by proper proportion, make and contain 2.5-90, preferred 5-75, the additive formulations of 8-60% (quality) additive (on the basis of activeconstituents) most preferably by the quality of additive formulations.Final prescription can contain 5-40% (quality) additive formulations usually, and all the other are lubricating oil.
In final lubricating oil composition, the quantity of additive is relevant with the type of lubricating oil composition usually, for example by the quality of lubricating oil composition, the heavy duty diesel engine lubricating oil composition contains 2-20, preferred 5-18, more preferably 7-16, for example 8-14% (quality) additive.
Therefore, the method that the prepares lubricating oil composition of the present invention additive formulations that can comprise lubricating oil and one or more additives or contain one or more additives mixes.
Improve engine particularly the method for self-igniton engine power output be included in its assembly turbocharger arranged.Turbocharger so that make more air send into cylinder, can make each given cylinder size that more fuel combustion is arranged by making the supercharging air that enters.
Usually drive turbocharger by the waste gas expellant gas, can make the loss in efficiency of turbocharger in the engine process in work-ing life like this, because contained species are deposited in the turbocharger in the waste gas.Find that also lubricating oil composition of the present invention can make the loss in efficiency of turbocharger reduce to minimum.The method of determination efficiency loss for example is the OM441LA test, and wherein provide the supercharging loss of representing with percentage ratio: the supercharging loss is high more, and loss in efficiency is big more.
Embodiment
With this professional known method, under comparable TBN, be mixed into lubricating oil composition by lubricating oil and multifunctional additive for lubricating oils, here determine as embodiment A-D and embodiment 1-4.Embodiment A-D is a Comparative Examples, and embodiment 1-4 is embodiments of the invention.Table 1 is listed the detailed content of used lubricating oil and is generated the physical properties of lubricating oil composition.The comparative example A is blended into SAE 15W40 viscosity grade, and Comparative Examples B-D and embodiment 1-4 are blended into SAE 10W40 viscosity grade.
Comparative example A-D and embodiment 1-4 have pressed the CEC-L-52-T-97 program test in the OM441LA test piston cleanliness and supercharging loss.The result also lists table 1 in.
Table 1 shows that embodiment A SAE 15W40 lubricating oil composition provides better piston cleanliness and supercharging loss than Embodiment B, and in Embodiment B, lubricating oil composition contains the additive identical with embodiment A, but is blended into SAE 10W40 viscosity grade.
In addition, the result of table 1 shows that also along with the ratio increase of III class base oil in SAE 10W40 lubricating oil composition, piston cleanliness and supercharging loss are modified (seeing Embodiment B-embodiment 4).
ACEA E5-99 performance technologies specification is set at least 25 mark Huaihe River points (piston cleanliness) and the acceptability limit that loses of 4% supercharging at the most.Therefore, with regard to piston cleanliness and supercharging loss, in order to satisfy the scope that ACEA E5-99 sets, the III class base oil that contains 35% (quality) of having an appointment in lubricating oil at least may be needs.
Every kind of lubricating oil composition all contains the various additives of comparable measure, for example dispersion agent, viscosity modifier, antioxidant, zinc dithiophosphate, calcium purification agent and/or magnesium purification agent.
Claims (7)
1. heavy duty diesel engine lubricating oil composition, described lubricating oil composition has passed through APICG-4 or ACEA E2-96 testing of engine, and it contains or is mixed by following component:
(A) a large amount of lubricating oil, described lubricating oil contains the mixture of I class base oil and III class base oil, quality by lubricating oil, described lubricating oil contains at least 35% (quality) III class base oil, by described base oil, described III class base oil contains at the most that 0.03% (quality) sulphur and viscosity index are 120, and by described base oil, more than or equal to 90% (quality) stable hydrocarbon; And
(B) contain the compositions of additives of following component on a small quantity:
(i) purification agent; And
(ii) one or more other additives;
Press wherein that ASTM D2602 measures, the cold starting simulation viscosity of lubricating oil composition-25 ℃ under is less than 7000mPas, and by the quality of lubricating oil composition, the sulfate ash of pressing the ASTMD874 measurement is less than 1.35% (quality).
2. according to the lubricating oil composition of claim 1, wherein cleaning agent composition contains magnesium purification agent and/or calcium purification agent.
3. according to each lubricating oil composition in claim 1 or 2, wherein also contain the dialkyl zinc dithiophosphate.
4. the method for a lubricated heavy duty diesel engine, the gross exhaust gas of described engine is at least 6.5 liters, and the free air delivery of every stroke is at least 1.0 liters/stroke, and described method comprises sends the lubricating oil composition of each regulation among the claim 1-3 into engine.
5. the purposes of lubricating oil in the lubricating oil composition that improves the engine piston degree of cleaning, described lubricating oil contains the mixture of I class base oil and III class base oil, quality by lubricating oil, described lubricating oil contains at least 35% (quality) III class base oil, quality by described base oil, described III class base oil contains 0.03% (quality) sulphur at the most, its viscosity index is 120 or bigger, and by the quality of described base oil, contain more than or equal to 90% (quality) stable hydrocarbon, described lubricating oil composition has passed through APICG-4 or ACEA E2-96 testing of engine.
6. method that is added to the piston cleanliness of improving engine in the engine by lubricating oil composition with each regulation among the claim 1-3.
7. heavy duty diesel engine lubricating oil composition that according to the CEC-L-52-T-97 program at least 25 piston cleanliness standard points is arranged in the OM441LA testing of engine and be not more than 4% supercharging loss, described lubricating oil composition has passed through APICG-4 or ACEA E2-96 testing of engine, and described lubricating oil composition contains or is mixed and made into by following component:
(A) a large amount of lubricating oil, described lubricating oil contains the mixture of I class base oil and III class base oil, and by the quality of lubricating oil, described lubricating oil contains at least 35% (quality) III class base oil; And
(C) contain the compositions of additives of following component on a small quantity:
(i) purification agent; And
(ii) one or more other additives;
Press wherein that ASTM D2602 measures, the cold starting simulation viscosity of lubricating oil composition-25 ℃ under is less than 7000mPas, and by the quality of lubricating oil composition, sulfate ash is pressed ASTM D874 measurement less than 1.35% (quality).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP02251357A EP1340803A1 (en) | 2002-02-27 | 2002-02-27 | Lubricating oil compositions |
| EP02251357.6 | 2002-02-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1441038A CN1441038A (en) | 2003-09-10 |
| CN100564498C true CN100564498C (en) | 2009-12-02 |
Family
ID=27675749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031064795A Expired - Fee Related CN100564498C (en) | 2002-02-27 | 2003-02-27 | Lubricating oil composition |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20030162674A1 (en) |
| EP (1) | EP1340803A1 (en) |
| JP (1) | JP5203551B2 (en) |
| CN (1) | CN100564498C (en) |
| CA (1) | CA2420514C (en) |
| SG (1) | SG112875A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005343976A (en) * | 2004-06-01 | 2005-12-15 | Showa Shell Sekiyu Kk | Lubricating oil composition |
| JP5289670B2 (en) * | 2005-06-17 | 2013-09-11 | 出光興産株式会社 | Engine oil composition |
| US8759262B2 (en) * | 2005-12-28 | 2014-06-24 | Infineum International Limited | Lubricating oil compositions |
| EP1803793B1 (en) * | 2005-12-28 | 2015-06-17 | Infineum International Limited | Lubricating oil compositions |
| US20080236538A1 (en) * | 2007-03-26 | 2008-10-02 | Lam William Y | Lubricating oil composition for improved oxidation, viscosity increase, oil consumption, and piston deposit control |
| US20090143263A1 (en) * | 2007-12-03 | 2009-06-04 | Bloch Ricardo A | Lubricant composition comprising a bi-modal side-chain distribution lofi |
| WO2009140130A1 (en) * | 2008-05-13 | 2009-11-19 | The Lubrizol Corporation | Alkali metal salts to minimize turbo sludge |
| EP2291498B1 (en) * | 2008-05-13 | 2013-07-31 | The Lubrizol Corporation | Method to minimize turbo sludge with a polyether |
| CN102089414B (en) * | 2008-05-13 | 2015-08-05 | 路博润公司 | For turbine greasy filth is reduced to minimum amine antioxidants |
| US9909079B2 (en) * | 2013-10-18 | 2018-03-06 | Chevron Oronite Company Llc | Lubricating oil composition for protection of silver bearings in medium speed diesel engines |
| CN105733768B (en) * | 2016-02-23 | 2018-08-14 | 北京雅士科莱恩石油化工有限公司 | Special heavily loaded climbing diesel engine oil in a kind of mining area and preparation method thereof |
| CN110770331B (en) * | 2017-06-30 | 2023-01-24 | 雪佛龙奥伦耐有限责任公司 | Low Viscosity Engine Oil Containing Isomerized Phenolic Detergents |
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| US4420647A (en) * | 1982-04-26 | 1983-12-13 | Texaco Inc. | Semi-synthetic lubricating oil composition |
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| US6300291B1 (en) * | 1999-05-19 | 2001-10-09 | Infineum Usa L.P. | Lubricating oil composition |
| EP1167497A2 (en) * | 2000-06-02 | 2002-01-02 | Chevron Oronite Japan Limited | Diesel motor lubricating oil composition |
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| US4956122A (en) * | 1982-03-10 | 1990-09-11 | Uniroyal Chemical Company, Inc. | Lubricating composition |
| CA2013545C (en) * | 1989-04-03 | 1999-01-26 | Glen Paul Fetterman Jr. | Improved ashless lubricant compositions for internal combustion engines |
| GB2292747B (en) * | 1994-08-26 | 1998-09-16 | Exxon Research Engineering Co | Lubricant composition containing copolymer to improve seal compatability |
| US5942475A (en) * | 1996-09-06 | 1999-08-24 | Exxon Chemical Patents Inc. | Engine oil lubricants formed from complex alcohol esters |
| WO1999055808A1 (en) * | 1998-04-27 | 1999-11-04 | Infineum Holdings B.V. | Lubricating oil compositions |
| JP2000063876A (en) * | 1998-08-18 | 2000-02-29 | Showa Shell Sekiyu Kk | Lubricating oil composition for diesel engines |
| JP2000282990A (en) * | 1999-03-31 | 2000-10-10 | Komatsu Ltd | Fuel piping structure of diesel engine |
| US6333298B1 (en) * | 1999-07-16 | 2001-12-25 | Infineum International Limited | Molybdenum-free low volatility lubricating oil composition |
| DE60124645T2 (en) * | 2000-09-25 | 2007-09-13 | Infineum International Ltd., Abingdon | Low viscosity lubricant compositions |
| US6715473B2 (en) * | 2002-07-30 | 2004-04-06 | Infineum International Ltd. | EGR equipped diesel engines and lubricating oil compositions |
| US6331510B1 (en) * | 2001-02-13 | 2001-12-18 | The Lubrizol Corporation | Synthetic diesel engine lubricants containing dispersant-viscosity modifier and functionalized phenol detergent |
| US6784143B2 (en) * | 2001-05-11 | 2004-08-31 | Infineum International Ltd. | Lubricating oil composition |
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- 2002-02-27 EP EP02251357A patent/EP1340803A1/en not_active Withdrawn
-
2003
- 2003-01-27 US US10/351,947 patent/US20030162674A1/en not_active Abandoned
- 2003-02-26 SG SG200300797A patent/SG112875A1/en unknown
- 2003-02-27 CN CNB031064795A patent/CN100564498C/en not_active Expired - Fee Related
- 2003-02-27 CA CA002420514A patent/CA2420514C/en not_active Expired - Fee Related
- 2003-02-27 JP JP2003050335A patent/JP5203551B2/en not_active Expired - Fee Related
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|---|---|---|---|---|
| US4420647A (en) * | 1982-04-26 | 1983-12-13 | Texaco Inc. | Semi-synthetic lubricating oil composition |
| US6300291B1 (en) * | 1999-05-19 | 2001-10-09 | Infineum Usa L.P. | Lubricating oil composition |
| EP1087008A1 (en) * | 1999-09-21 | 2001-03-28 | Infineum International Limited | Multigrade crankcase lubricating oil compositions |
| EP1167497A2 (en) * | 2000-06-02 | 2002-01-02 | Chevron Oronite Japan Limited | Diesel motor lubricating oil composition |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1340803A1 (en) | 2003-09-03 |
| CN1441038A (en) | 2003-09-10 |
| CA2420514A1 (en) | 2003-08-27 |
| CA2420514C (en) | 2009-02-24 |
| SG112875A1 (en) | 2005-07-28 |
| JP2003253289A (en) | 2003-09-10 |
| US20030162674A1 (en) | 2003-08-28 |
| JP5203551B2 (en) | 2013-06-05 |
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