WO1996037581A1 - Lubricating oil composition - Google Patents
Lubricating oil composition Download PDFInfo
- Publication number
- WO1996037581A1 WO1996037581A1 PCT/US1995/005144 US9505144W WO9637581A1 WO 1996037581 A1 WO1996037581 A1 WO 1996037581A1 US 9505144 W US9505144 W US 9505144W WO 9637581 A1 WO9637581 A1 WO 9637581A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- represent
- atom
- alkyl
- general formula
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 25
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 20
- 239000002199 base oil Substances 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 5
- -1 fatty acid esters Chemical class 0.000 claims description 51
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 20
- 239000000194 fatty acid Substances 0.000 claims description 20
- 229930195729 fatty acid Natural products 0.000 claims description 20
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- 229920006395 saturated elastomer Polymers 0.000 claims description 11
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical class [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 claims description 11
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 150000003857 carboxamides Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 150000002902 organometallic compounds Chemical class 0.000 abstract description 6
- 125000004429 atom Chemical group 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 description 34
- 239000003921 oil Substances 0.000 description 22
- 239000002480 mineral oil Substances 0.000 description 17
- 150000002430 hydrocarbons Chemical group 0.000 description 16
- 235000010446 mineral oil Nutrition 0.000 description 14
- 239000000654 additive Substances 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 9
- 239000010705 motor oil Substances 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 7
- CCBXBMKHVFTUMN-UHFFFAOYSA-L C(N)([S-])=S.[Mo+2]=S.C(N)([S-])=S Chemical class C(N)([S-])=S.[Mo+2]=S.C(N)([S-])=S CCBXBMKHVFTUMN-UHFFFAOYSA-L 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001638 boron Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 150000004659 dithiocarbamates Chemical class 0.000 description 2
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 2
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 125000006528 (C2-C6) alkyl group Chemical group 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical class C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- 0 CC(N(**)**)=O Chemical compound CC(N(**)**)=O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229940116335 lauramide Drugs 0.000 description 1
- 125000005645 linoleyl group Chemical group 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010937 tungsten Substances 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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/76—Esters containing free hydroxy or carboxyl 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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/16—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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M141/08—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 sulfur-, selenium- or tellurium-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
- 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
- C10M2207/28—Esters
- C10M2207/287—Partial esters
-
- 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
- C10M2207/287—Partial esters
- C10M2207/288—Partial esters containing free carboxyl 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
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/08—Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
-
- 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
- C10M2215/08—Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
- C10M2215/082—Amides [having hydrocarbon substituents containing less than thirty carbon atoms] containing hydroxyl groups; Alkoxylated derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/086—Imides [having hydrocarbon substituents containing less than thirty carbon atoms]
-
- 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
- C10M2215/12—Partial amides of polycarboxylic acids
-
- 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
- C10M2215/12—Partial amides of polycarboxylic acids
- C10M2215/122—Phtalamic acid
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
- C10M2215/28—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
-
- 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
-
- 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
- C10N2040/251—Alcohol-fuelled engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
- C10N2040/28—Rotary engines
Definitions
- the present invention relates to a lubricating oil composition, in particular, to a lubricating composition having excellent wear resistance and extreme-pressure lubricity and a low coefficient of friction.
- the lubricating oil composition of the present invention can be minimized in phosphorus content or made phosphorus-free, and usable in a wide variety of fields such as, for example, a lubricating oil for an internal combustion engineer or an engine oil.
- the engine oil is usually effective in lubricating various sliding parts such as a piston ring and a cylinder liner; bearings of a crankshaft and connecting rod; valve mechanisms including a cam and valve lifter; drivers such as an oil pump and distributor, and also in cooling the inside of an engine, deterging and dispersing combustion products and preventing the rusting and corrosion thereof.
- various properties are required of the engine oil and, in addition, the required properties are continuously changing according to improvements in performance and output of the engine and driving conditions which grow more and more severe. Therefore, various additives such as an antiwear agent, metallic detergent, ashless dispersant and oxidation inhibitor are incorporated into the engine oil for the purpose of satisfying the various properties required thereof.
- antiwear properties of the engine oil in the boundary lubrication state are usually realized by the addition of a zinc dialkyldithiophosphate (ZnDTP).
- ZnDTP zinc dialkyldithiophosphate
- ZnDTP has a problem that, since phosphorus (P) contained therein poisons catalyst and oxygen sensors, exhaust gas-control systems are deteriorated. Further, the wear resistance is inclined to be lost by an interaction between ZnDTP and other additives such as succinimide and alkylamine. Under these circumstances, a lubricating oil composition having a minimum phosphorus content or free from phosphorus is required.
- a friction modifier is added to a lubricating oil to be used for a gasoline engine in order to reduce the friction loss and fuel consumption, since the energy loss is high in friction parts in which the lubricatng oil is concerned in the gasoline engine.
- the friction modifier and extreme-pressure agent such as a molybdenum sulf ⁇ de dialkyldithiocarbamate or an oiliness agent such as octadecylamine is used, the molybdenum sulfide dialkyldithiocarbamate which is a dithiocarbamate-type organomolybdenum compound has a particularly excellent effect of reducing the friction.
- the object of the present invention is to provide a lubricating oil composition excellent in both wear resistance and friction characteristics.
- the object of the present invention is to provide a lubricating oil composition containing an extreme-pressure agent which is a dithiocarbamate- type organometallic compound having friction characteristics and wear resistance superior to those of an conventional extreme-pressure agent.
- Another object of the present invention is to provide a lubricating oil composition which contains also a dithiophosphate-type organometallic compound to further improve the wear resistance and friction characteristics.
- a dithiocarbamate-type organometal compound such as a molybdenum sulfide dialkyldithiocarbamate has such a structure that the alkyl group is bonded to the nitrogen atom through its primary carbon atoms (namely, -CH2-N ⁇ ).
- the friction characteristics and wear resistance of the lubricating oil composition of the present invention are further improved by adding ZnDTP and/or zinc dithiocarbamate (ZnDTC), in addition to the above-described metal dithiocarbamate, to the lube base oil.
- ZnDTC zinc dithiocarbamate
- ZnDTC zinc dithiocarbamate
- the metal dithiocarbamate of the present invention is used in combination with ZnDTP, ZnDTP content can be reduced to enable reduction of the phosphorus content, since the metal dithio ⁇ carbamate is excellent in the wear resistance and friction characteristics.
- the metal dithiocarbamate of the present invention is used solely or in combination with ZnDTC without using ZnDTP, the phosphorus-free lubricating oil composition can be obtained.
- the coefficient of friction of the lubricating oil composition of the present invention can be further reduced by adding a fatty acid ester and/or an organic amide compound.
- various other additives for lubricating oils can be added, if desired, to the lubricating oil composition of the present invention.
- the lubricating oil composition of the present invention is usable in wide fields in which excellent wear resistance and friction characteristics are necessitated, such as in the field of engine oils.
- a lubricating oil composition comprising a lube base oil and 0.01 to 10% by weight, based on the total weight of the composition, of a metal dithiocarbamate (A) represented by the general formula (1):
- Rj, R , R3 and R4 may be the same or different from one another and each represent a hydrogen atom, saturated or unsaturated C1-C20 al yl group, C6-C26 cycloalkyl or alkyl-substituted cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or such a hydrocarbon group as above which further contains an ester bond, ether bond, hydroxyl group or carboxyl group, with the proviso that at least one of the four symbols Rj, R2, R3 and R4 must be a C5-C20 alkyl group having a secondary carbon atom, through which the group is bonded to a nitrogen atom (N) in the formula, X ⁇ and X2 each represent an oxygen or sulfur atom, and Yj and Y2 each represent an oxygen or sulfur atom.
- N nitrogen atom
- the present invention provides the following lubricating oil compositions 2 to 6 as preferred embodiments:
- a lubricating oil composition which contains a lube base oil and, in addition to the above-mentioned metal dithiocarbamate (A), 0.01 to 7% by weight, based on the total weight of the composition, at least one organozinc compound selected from the group consisting of zinc dithiophosphates (B) of the general formula (2):
- R5, R , R7 and R$ may be the same or different from one another and each represent a hydrogen atom, saturated or unsaturated C1-C20 alkyl group, C6-C26 cycloalkyl or alkyl substituted cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or such a hydrocarbon group as above which further contains an ester bond, ether bond, hydroxyl group or carboxyl group, and zinc dithiocarbamates (C) of the general formula (3):
- R ⁇ , R 1 ⁇ R11 and W - may be the same or different from one another and each represent a hydrogen atom, saturated or unsaturated C1-C20 alkyl group, C6-C25 cycloalkyl or alkyl-substituted cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or such a hydrocarbon group as above which further contains as ester bond, ether bond, hydroxyl group or carboxyl group,
- a lubricating oil composition according to above item 1 or 2 wherein at least two of R 1 , R2, R3 and R"4 in the general formula (1) for the metal dithiocarbamate (A) each represent an alkyl group having a secondary carbon atom, through which the group is bonded to the nitrogen atom (N) in the formula,
- a lubricating oil composition according to any of above items 1 to 5, which comprises a lube base oil containing a fatty acid ester, a organic amide or a mixture of fatty acid ester and organic anide in addition to the metal dithiocarbamate (A) or in addition to the combination of the metal dithiocarbamate (A) with zinc dithiophosphate (B) and or zinc dithiocarbamate (C).
- the base oils usable in the present invention are not particularly limited, and include known mineral oils and synthetic oils.
- the mineral oils include raffinates obtained by solvent refining of a starting material for the lubricating oil with an aromatic solvent such as phenol or furfural; hydrotreated oils obtained by the hydrotreatment of the starting material with a hydrogena- tion catalyst such as cobalt or molybdenum supported on a silica/alumina carrier; and mineral oils such as a lubricating oil fraction obtained by isomerization of a wax. They include, for example, 60 neutral oil, 100 neutral oil, 150 neutral oil, 300 neutral oil, 500 neutral oil and bright stock.
- the synthetic oils include poly-a-olefins, polybutenes, alkylbenzenes, poly- alkylene glycol esters, polyol esters and dibasic acid esters. These base oils can be used singly or in the form of a mixture of two or more of them. A mixture of such a mineral oil and synthetic oil is also usable.
- the kinematic viscosity of the lube base oil is usually preferably in the range of 3 to 20 cSt at 100°C when the oil is used as the engine oil.
- the metal dithiocarbamates used in the present invention are organometallic compounds represented by the above-described general formula
- M represents a molybdenum atom (Mo) or tungsten atom (W).
- Mo molybdenum atom
- W tungsten atom
- the molybdenum atom is particularly preferred to the tungsten atom.
- X 1 , X ⁇ , ⁇ l and Y ⁇ represent an oxygen atom or sulfur atom independently from one another. These four atoms contain 0 to 3 oxygen atoms and 1 to 4 sulfur atoms in total.
- R 1 , R2, R3 and R"4 may be the same of different from one another and each represent a hydrogen atom, saturated or unsaturated C1-C20 alkyl group, C6-C26 cycloalkyl or alkyl-substituted cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or such a hydrocarbon group as above which further contains an ester bond, ether bond, hydroxyl group or carboxyl group.
- Each of R to R ⁇ is preferably a C5-C20 alkyl group, more preferably C_-C ⁇ % alkyl group.
- At least one of R*, R ⁇ , R3 and R ⁇ must be a C5-C20 alkyl group having a secondary carbon atom, through which the group is bonded to a nitrogen atom (N) in the above general formula.
- the alkyl groups having the secondary carbon atom include, for example, 1-methylpentyl, 1-ethylbutyl, 1-methylheptyl, 1-ethylhexyl, 1- methyloctyl, 1-ethylheptyl, 1-methylnonyl, 1-ethyloctyl, 1-methylundecyl, 1- ethyldecyl, 1-methylheptadecyl and 1-ethylhexadecyl groups.
- alkyl groups having the secondary carbon atom must be bonded to the nitrogen atom (N) in the general formula (1) through the secondary carbon atom.
- N nitrogen atom
- 1-methylnonyl group is bonded to the nitrogen atom through the secondary carbon atom thereof as shown by the following formula:
- [(CH 3 (CH2)3CH(C 2 H5)CH2-] contains a secondary carbon atom, it is not included in the above-defined alkyl group having the specified secondary carbon atom, since it is bonded to the nitrogen atom through the primary carbon atom.
- the groups other than the alkyl groups having the specified secondary carbon atoms are preferably C5-C20 hydrocarbon groups such as saturated or unsaturated alkyl groups and alkylaryl groups.
- hydrocarbon groups include saturated alkyl groups and unsaturated alkyl groups (alkenyl groups) such as n-hexyl, 2-ethylhexyl, n-octyl, nonyl, decyl, lauryl, tridecyl, oleyl and linoleyl groups, and alkylaryl groups such as nonylphenyl groups.
- alkylaryl groups such as nonylphenyl groups.
- particularly preferred are C -Ci 8 alkyl groups.
- metal dithiocarbamates (A) can be used either singularly or in combination of two or more of them.
- the relative amount of the metal dithiocarbamate (A) is about 0.01 to 10% by weight, preferably 0.05 to 7a% by weight and more preferably 0.1 to 5% by weight, based on the total weight of the whole lubricating oil composition.
- the relative amount of the metal dithiocarbamate (A) is insufficient, it is difficult to obtain sufficient friction characteristics and wear resistance and, on the contrary, an excess amount thereof is economically disadvantageous and causes reduction in the wear resistance.
- Zinc dithiophosphate (B and zinc dithiocarbamate (C) Zinc dithiophosphate (B and zinc dithiocarbamate (C).
- various lubricating oil additives can be incorporated into the lubricating oil composition of the present invention.
- a zinc dithiophosphate (B) of the above general formula (2) and/or zinc dithiocarbamate (C) of the above general formula (3) is particularly effective in further improving the wear resistance and reducing the coefficient of friction as intended in the present invention.
- each of R ⁇ to R ⁇ represents preferably a C2-C13 hydrocarbon group, more preferably C2-C13 alkyl group.
- each of R9 to R12 represents preferably a C2-C1 hydrocarbon group, more preferably C2-C13 alkyl group.
- the relative amount of the zinc dithiophosphate (B) or zinc dithiocarbamate (C) or mixture thereof is about 0.01 to 7% by weight, preferably 0.03 to 5% by weight and more preferably 0.05 to 2% by weight, based on the total weight of the whole lubricating oil composition.
- the relative amount of (B) or (C) or mixture thereof is insufficient, the effect obtained by the combination thereof with the metal dithiocarbamate (A) is insufficient for obtaining the sufficient effect of improving the wear resistance and reducing the coefficient of friction and, on the contrary, an excess amount thereof is economically disadvantageous and might impair the friction characteristics.
- the lubricating oil composition of the present invention may contain various additives, if desired, depending on the field in which it is used, such as engine oils.
- the additives include, for example, a friction modifier, metallic detergent, ashless detergent-dispersant, oxidation inhibitor, viscosity- index improver, rust inhibitor, antifoamer, corrosion inhibitor, pour-point depressant and wear resistant additive other than those described above.
- the friction modifiers include fatty acid esters such as fatty acid glycerol monoesters and diesters, and fatty acid/ sorbitan monoesters and diesters; and fatty acid amides such as oleamide and lauramide.
- fatty acid ester is used in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total weight of the whole composition, the wear resistance and friction characteristics are further improved.
- the organic amide compound is used in an amount of usually 0.01 to 5% by weight, preferably 0.05 to 2% by weight, based on the total weight of the whole composition, the copper-corroding properties are controlled and the coefficient of friction can be reduced from the initial stage.
- the fatty acid glycerides are monoesters and diesters of the following general formulae (4) and (5):
- R ⁇ 3, R*4 and R 1 ⁇ each represent a saturated or unsaturated C8-C22 alkyl group.
- the fatty acid esters are usable either singularly or in combina ⁇ tion of two or more of them.
- the metal dithiocarbamate (A) is used in combination with the fatty acid ester, wear resistance and friction characteristics more improved than those obtained when they are used separately can be obtained.
- the fatty acid ester is added to the combination of the metal dithiocarbamate (A) and zinc dithiophosphate (B) and/or zinc dithiocarbamate (C), a lubricating oil composition having improved wear resistance and friction properties and a remarkably reduced coefficient of friction can be obtained.
- organic amide compounds are those represented by the following general formula (6):
- R*6 and R 1 ⁇ may be the same or different from each other an each represent a hydrogen atom, C1-C20 alkyl group, C6-C26 cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or C2-C20 alkylene oxide group, and R 18 represents a hydrogen atom, C1-C20 alkyl group, C6-C26 cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or such a hydrocarbon group as above further containing an ester bond, ether bond, hydroxyl group or carboxyl group.
- alkylene oxide group in the general formula (6) are those represented by the following general formula (7) or (8):
- R 1 ⁇ and R ⁇ O each represent a hydrogen atom or methyl group, and n represents an integer of 1 to 10 inclusive.
- R 1 ⁇ and R*? each preferably represent a hydrogen atom, C2-C6 alkyl group, Cg-C ⁇ cycloalkyl group, C8-C14 alkylaryl group or alkylene oxide group wherein n represents 1 to 5, and R l8 preferably represents a saturated or unsaturated C ⁇ -Cis alkyl group, C12-C24 cycloalkyl group or C12-C24 alkylaryl group.
- the metallic detergents include, for example, phenates, sulfonates and phosphonates of barium (Ba), calcium (Ca) and magnesium (Mg). Among them, overbased Ca sulfonate, Mg sulfonate and Ca phenate and neutral Ca sulfonate are preferred.
- the metallic detergent is used usually in an amount of 0.1 to 10% by weight (based on the whole composition).
- the ashless detergent-dispersants include, for example, benzyl- amine, boron derivatives of benzylamine, alkenylsuccinimides and boron derivatives of alkenylsuccinimides.
- the ashless detergent dispersant is used usually in an amount of 0.5 to 15% by weight (based on the whole composi ⁇ tion).
- the oxidation inhibitors include, for example, amine oxidation inhibitors such as alkylated diphenylamines, pheyl- ⁇ -naphthylamines and alkylated ⁇ -naphthylamines; and phenolic oxidation inhibitors such as 2,6-di-t- butylphenol).
- the oxidation inhibitor is used usually in an amount of 0.05 to 2.0% by weight (based on the whole composition).
- the viscosity-index improvers include, for example, polymethyl methacrylates, polyisobutylenes, ethylene/propylene copolymers and hydro- genated styrene-butadiene copolymers.
- the viscosity-index improver is used usually in an amount of 0.5 to 35% by weight (based on the whole composi ⁇ tion).
- the rust inhibitors include, for example, alkenylsuccinic acids and partial esters of them, which can be suitably added to the composition.
- the antifoamers include, for example, dimethyl polysiloxanes and polyacrylates, which can be suitably added to the composition.
- the wear track diameter (mm) and coefficient of friction were determined by the Shell four-ball test 30 min. after the initiation of the test.
- the test conditions were as follows: load: 40 kg oil temperature: 90°C rotation rate: 1800 rpm, and test time: 30 minutes
- test oil was prepared by mixing a lube base oil and components given in Table 1. The components used were as follows:
- mineral oil 150 neutral oil having a kinematic viscosity at 100°C of 5.1 cSt (mm ⁇ /s), and synthetic oil: a mixed oil comprising 80% by weight of a poly- ⁇ -olefin and 20% by weight of diisodecyl adipate.
- Molybdenum dithiocarbamate molybdenum sulfide dithiocarbamates of the general formula (1) where X* and X ⁇ each represent an oxygen atom (O) and ⁇ l and Y ⁇ each represent a sulfur atom (S) was used, having the following different hydrocarbon groups as indicated in Table 1 :
- hydrocarbon group p-C8-C 13 alkyl: commercially available primary alkyl groups (mixed C8-C 3 alkyl groups) - containing molybdenum sulfide dithiocarbamate,
- hydrocarbon group p-C 13 alkyl: commercially available primary alkyl groups (C13 alkyl groups) - containing molybdenum sulfide dithiocarbamate,
- hydrocarbon group 1-methylheptyl: molybdenum sulfide dithio ⁇ carbamate wherein R 1 to R4 each represent a 1-methylheptyl group,
- Zinc dithiophosphate commercially available i-C3/s-C6 alkyl type
- Zinc dithiocarbamate commercially available n-C5/i-C5 alkyl type.
- test oil was prepared by mixing a lube base oil with components given in Table 2.
- the components used were as follows:
- R represents an oleyl group
- the lubricating oil composi ⁇ tion having wear resistance and friction characteristics far superior to those of a conventional metal sulfide dithiocarbamate containing composition can be provided.
- the lubricating oil composition of the present invention can be minimized in the phosphorus content or made phosphorus-free.
- the lubricating oil composition of the present invention can be used in various fields such as a field of lubricating oils for internal combustion engines, etc.
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
The present invention provides a lubricating oil composition containing an extreme-pressure agent which is a dithiocarbamate-type organometallic compound containing wear resistance and friction characteristics superior to those conferred by conventional organometallic compound. The lubricating oil composition comprises a lube base oil and 0.01 to 10 % by weight, based on the whole composition, of a metal dithiocarbamate represent by general formula (1), wherein M represents a Mo or W atom, R?1, R2, R3 and R4¿ each represent a hydrocarbon group, with the proviso that at least one of the R?1, R2, R3 and R4¿ must be a C¿5?-C20 alkyl group having a secondary carbon atom, through which the group is bonded to a nitrogen atom (N) in formula (1), and X?1, X2, Y1 and Y2¿ each represent an oygen or sulfur atom.
Description
LUBRICATING OIL COMPOSITION
Background of the Invention
Field of the Invention
The present invention relates to a lubricating oil composition, in particular, to a lubricating composition having excellent wear resistance and extreme-pressure lubricity and a low coefficient of friction. The lubricating oil composition of the present invention can be minimized in phosphorus content or made phosphorus-free, and usable in a wide variety of fields such as, for example, a lubricating oil for an internal combustion engineer or an engine oil.
Description of the Related Art
The engine oil is usually effective in lubricating various sliding parts such as a piston ring and a cylinder liner; bearings of a crankshaft and connecting rod; valve mechanisms including a cam and valve lifter; drivers such as an oil pump and distributor, and also in cooling the inside of an engine, deterging and dispersing combustion products and preventing the rusting and corrosion thereof.
Thus, various properties are required of the engine oil and, in addition, the required properties are continuously changing according to improvements in performance and output of the engine and driving conditions which grow more and more severe. Therefore, various additives such as an antiwear agent, metallic detergent, ashless dispersant and oxidation inhibitor are incorporated into the engine oil for the purpose of satisfying the various properties required thereof.
An important basic function of the engineer oil is to insure smoothly ninning of engine while preventing it from wear and seizure under any conditions. Although a fluid lubrication state is usually realized in an engine lubricating part, a boundary lubrication state is apt to be realized in a valve mechanism system or at top and bottom dead centers of a piston. The
- 2 -
antiwear properties of the engine oil in the boundary lubrication state are usually realized by the addition of a zinc dialkyldithiophosphate (ZnDTP).
However, ZnDTP has a problem that, since phosphorus (P) contained therein poisons catalyst and oxygen sensors, exhaust gas-control systems are deteriorated. Further, the wear resistance is inclined to be lost by an interaction between ZnDTP and other additives such as succinimide and alkylamine. Under these circumstances, a lubricating oil composition having a minimum phosphorus content or free from phosphorus is required.
On the other hand, a friction modifier is added to a lubricating oil to be used for a gasoline engine in order to reduce the friction loss and fuel consumption, since the energy loss is high in friction parts in which the lubricatng oil is concerned in the gasoline engine. As the friction modifier, and extreme-pressure agent such as a molybdenum sulfϊde dialkyldithiocarbamate or an oiliness agent such as octadecylamine is used, the molybdenum sulfide dialkyldithiocarbamate which is a dithiocarbamate-type organomolybdenum compound has a particularly excellent effect of reducing the friction. However, the wear resistance and friction characteristics of the molybdenum sulfide dialkyldithiocarbamate used hitherto are yet insufficient, and further improve- ent in the properties of engine oils is demanded, since more reduction in the fuel consumption is eagerly demanded now.
Present Invention
The object of the present invention is to provide a lubricating oil composition excellent in both wear resistance and friction characteristics.
The object of the present invention is to provide a lubricating oil composition containing an extreme-pressure agent which is a dithiocarbamate- type organometallic compound having friction characteristics and wear resistance superior to those of an conventional extreme-pressure agent.
Another object of the present invention is to provide a lubricating oil composition which contains also a dithiophosphate-type organometallic compound to further improve the wear resistance and friction characteristics.
It was noted that an ordinary dithiocarbamate-type organometal compound such as a molybdenum sulfide dialkyldithiocarbamate has such a structure that the alkyl group is bonded to the nitrogen atom through its primary carbon atoms (namely, -CH2-N<). After intensive investigations on the alkyl group, it was found that when a metal dithiocarbamate which is a dithio- arbamate-type organometallic compound having such a structure that the alkyl group is bonded to the nitrogen atom through its secondary carbon atom (namely, >CH-N<), the metal atom being molybdenum or tungsten, is incorporated into a lube base oil, wear resistance and friction characteristics more excellent than those of a corresponding conventional lubricating oil can be obtained surprisingly.
The friction characteristics and wear resistance of the lubricating oil composition of the present invention are further improved by adding ZnDTP and/or zinc dithiocarbamate (ZnDTC), in addition to the above-described metal dithiocarbamate, to the lube base oil. When the metal dithiocarbamate of the present invention is used in combination with ZnDTP, ZnDTP content can be reduced to enable reduction of the phosphorus content, since the metal dithio¬ carbamate is excellent in the wear resistance and friction characteristics. Further, when the metal dithiocarbamate of the present invention is used solely or in combination with ZnDTC without using ZnDTP, the phosphorus-free lubricating oil composition can be obtained.
The coefficient of friction of the lubricating oil composition of the present invention can be further reduced by adding a fatty acid ester and/or an organic amide compound. As a matter of course, various other additives for lubricating oils can be added, if desired, to the lubricating oil composition of the present invention.
The lubricating oil composition of the present invention is usable in wide fields in which excellent wear resistance and friction characteristics are necessitated, such as in the field of engine oils.
The present invention has been completed on the basis of these findings.
Thus, the present invention provides
1. a lubricating oil composition comprising a lube base oil and 0.01 to 10% by weight, based on the total weight of the composition, of a metal dithiocarbamate (A) represented by the general formula (1):
wherein M represents a molybdenum atom or tungsten atom, Rj, R , R3 and R4 may be the same or different from one another and each represent a hydrogen atom, saturated or unsaturated C1-C20 al yl group, C6-C26 cycloalkyl or alkyl-substituted cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or such a hydrocarbon group as above which further contains an ester bond, ether bond, hydroxyl group or carboxyl group, with the proviso that at least one of the four symbols Rj, R2, R3 and R4 must be a C5-C20 alkyl group having a secondary carbon atom, through which the group is bonded to a nitrogen atom (N) in the formula, X\ and X2 each represent an oxygen or sulfur atom, and Yj and Y2 each represent an oxygen or sulfur atom.
The present invention provides the following lubricating oil compositions 2 to 6 as preferred embodiments:
2. a lubricating oil composition which contains a lube base oil and, in addition to the above-mentioned metal dithiocarbamate (A), 0.01 to 7% by weight, based on the total weight of the composition, at least one organozinc compound selected from the group consisting of zinc dithiophosphates (B) of the general formula (2):
wherein R^, R1^ R11 and W - may be the same or different from one another and each represent a hydrogen atom, saturated or unsaturated C1-C20 alkyl group, C6-C25 cycloalkyl or alkyl-substituted cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or such a hydrocarbon group as above which further contains as ester bond, ether bond, hydroxyl group or carboxyl group,
3. a lubricating oil composition according to above item 1 or 2, wherein at least two of R1, R2, R3 and R"4 in the general formula (1) for the metal dithiocarbamate (A) each represent an alkyl group having a secondary carbon atom, through which the group is bonded to the nitrogen atom (N) in the formula,
4. a lubricating oil composition according to above item 1 or 2, wherein at least three of \\\, R^, R3 and R^ in the general formula (1) for the metal dithiocarbamate (A) each represent an alkyl group having a secondary carbon atom, through which the group is bonded to the nitrogen atom (N) in the formula,
5. a lubricating oil composition according to any of above items 1 to 4, wherein R1, R^, R3? and R4 in the general formula (1) for the metal dithiocarbamate (A) each represent a C5-C20 alkyl group, and
6. a lubricating oil composition according to any of above items 1 to 5, which comprises a lube base oil containing a fatty acid ester, a
organic amide or a mixture of fatty acid ester and organic anide in addition to the metal dithiocarbamate (A) or in addition to the combination of the metal dithiocarbamate (A) with zinc dithiophosphate (B) and or zinc dithiocarbamate (C).
The detailed description will be made on the present invention.
Base Oil:
The base oils usable in the present invention are not particularly limited, and include known mineral oils and synthetic oils. The mineral oils include raffinates obtained by solvent refining of a starting material for the lubricating oil with an aromatic solvent such as phenol or furfural; hydrotreated oils obtained by the hydrotreatment of the starting material with a hydrogena- tion catalyst such as cobalt or molybdenum supported on a silica/alumina carrier; and mineral oils such as a lubricating oil fraction obtained by isomerization of a wax. They include, for example, 60 neutral oil, 100 neutral oil, 150 neutral oil, 300 neutral oil, 500 neutral oil and bright stock. Examples of the synthetic oils include poly-a-olefins, polybutenes, alkylbenzenes, poly- alkylene glycol esters, polyol esters and dibasic acid esters. These base oils can be used singly or in the form of a mixture of two or more of them. A mixture of such a mineral oil and synthetic oil is also usable. The kinematic viscosity of the lube base oil is usually preferably in the range of 3 to 20 cSt at 100°C when the oil is used as the engine oil.
Metal dithiocarbamate (A
The metal dithiocarbamates used in the present invention are organometallic compounds represented by the above-described general formula
(1).
In the general formula (1), M represents a molybdenum atom (Mo) or tungsten atom (W). The molybdenum atom is particularly preferred to the tungsten atom.
X1, X^, γl and Y^ represent an oxygen atom or sulfur atom independently from one another. These four atoms contain 0 to 3 oxygen atoms and 1 to 4 sulfur atoms in total.
R1, R2, R3 and R"4 may be the same of different from one another and each represent a hydrogen atom, saturated or unsaturated C1-C20 alkyl group, C6-C26 cycloalkyl or alkyl-substituted cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or such a hydrocarbon group as above which further contains an ester bond, ether bond, hydroxyl group or carboxyl group. Each of R to R^ is preferably a C5-C20 alkyl group, more preferably C_-C\% alkyl group.
At least one of R*, R^, R3 and R^ must be a C5-C20 alkyl group having a secondary carbon atom, through which the group is bonded to a nitrogen atom (N) in the above general formula. Preferably at least two, more preferably at least three of R1, R^, R3, or R each represent the C5-C20 alkyl group bonded to the nitrogen atom through the secondary carbon atom.
The alkyl groups having the secondary carbon atom include, for example, 1-methylpentyl, 1-ethylbutyl, 1-methylheptyl, 1-ethylhexyl, 1- methyloctyl, 1-ethylheptyl, 1-methylnonyl, 1-ethyloctyl, 1-methylundecyl, 1- ethyldecyl, 1-methylheptadecyl and 1-ethylhexadecyl groups.
These alkyl groups having the secondary carbon atom must be bonded to the nitrogen atom (N) in the general formula (1) through the secondary carbon atom. For example, 1-methylnonyl group is bonded to the nitrogen atom through the secondary carbon atom thereof as shown by the following formula:
Thus, for example, although 2-ethylhexyl group
[(CH3(CH2)3CH(C2H5)CH2-]
contains a secondary carbon atom, it is not included in the above-defined alkyl group having the specified secondary carbon atom, since it is bonded to the nitrogen atom through the primary carbon atom.
The groups other than the alkyl groups having the specified secondary carbon atoms are preferably C5-C20 hydrocarbon groups such as saturated or unsaturated alkyl groups and alkylaryl groups. Examples of such hydrocarbon groups include saturated alkyl groups and unsaturated alkyl groups (alkenyl groups) such as n-hexyl, 2-ethylhexyl, n-octyl, nonyl, decyl, lauryl, tridecyl, oleyl and linoleyl groups, and alkylaryl groups such as nonylphenyl groups. Among them, particularly preferred are C -Ci 8 alkyl groups.
These metal dithiocarbamates (A) can be used either singularly or in combination of two or more of them. The relative amount of the metal dithiocarbamate (A) is about 0.01 to 10% by weight, preferably 0.05 to 7a% by weight and more preferably 0.1 to 5% by weight, based on the total weight of the whole lubricating oil composition. When the relative amount of the metal dithiocarbamate (A) is insufficient, it is difficult to obtain sufficient friction characteristics and wear resistance and, on the contrary, an excess amount thereof is economically disadvantageous and causes reduction in the wear resistance.
Zinc dithiophosphate (B and zinc dithiocarbamate (C
In addition to the above-described metal dithiocarbamate (A), various lubricating oil additives can be incorporated into the lubricating oil composition of the present invention. Among them, a zinc dithiophosphate (B) of the above general formula (2) and/or zinc dithiocarbamate (C) of the above general formula (3) is particularly effective in further improving the wear resistance and reducing the coefficient of friction as intended in the present invention.
In the above-described general formula (2), each of R^ to R^ represents preferably a C2-C13 hydrocarbon group, more preferably C2-C13 alkyl group.
In the above-described general formula (3), each of R9 to R12 represents preferably a C2-C1 hydrocarbon group, more preferably C2-C13 alkyl group.
The relative amount of the zinc dithiophosphate (B) or zinc dithiocarbamate (C) or mixture thereof is about 0.01 to 7% by weight, preferably 0.03 to 5% by weight and more preferably 0.05 to 2% by weight, based on the total weight of the whole lubricating oil composition. When the relative amount of (B) or (C) or mixture thereof is insufficient, the effect obtained by the combination thereof with the metal dithiocarbamate (A) is insufficient for obtaining the sufficient effect of improving the wear resistance and reducing the coefficient of friction and, on the contrary, an excess amount thereof is economically disadvantageous and might impair the friction characteristics.
Other additives
The lubricating oil composition of the present invention may contain various additives, if desired, depending on the field in which it is used, such as engine oils. The additives include, for example, a friction modifier, metallic detergent, ashless detergent-dispersant, oxidation inhibitor, viscosity- index improver, rust inhibitor, antifoamer, corrosion inhibitor, pour-point depressant and wear resistant additive other than those described above.
Preferred examples of the friction modifiers include fatty acid esters such as fatty acid glycerol monoesters and diesters, and fatty acid/ sorbitan monoesters and diesters; and fatty acid amides such as oleamide and lauramide. When the fatty acid ester is used in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total weight of the whole composition, the wear resistance and friction characteristics are further improved. When the organic amide compound is used in an amount of usually 0.01 to 5% by weight, preferably 0.05 to 2% by weight, based on the total weight of the whole composition, the copper-corroding properties are controlled and the coefficient of friction can be reduced from the initial stage.
The fatty acid glycerides are monoesters and diesters of the following general formulae (4) and (5):
CH20C0R13
(4) CHOH
I
CH2OH
CH2OCOR14
CHOCOR15
(5) I
CH2OH
wherein Rχ3, R*4 and R1^ each represent a saturated or unsaturated C8-C22 alkyl group.
The fatty acid esters are usable either singularly or in combina¬ tion of two or more of them. When the metal dithiocarbamate (A) is used in combination with the fatty acid ester, wear resistance and friction characteristics more improved than those obtained when they are used separately can be obtained. Particularly when the fatty acid ester is added to the combination of the metal dithiocarbamate (A) and zinc dithiophosphate (B) and/or zinc dithiocarbamate (C), a lubricating oil composition having improved wear resistance and friction properties and a remarkably reduced coefficient of friction can be obtained.
The organic amide compounds are those represented by the following general formula (6):
The alkylene oxide group in the general formula (6) are those represented by the following general formula (7) or (8):
wherein R1^ and R^O each represent a hydrogen atom or methyl group, and n represents an integer of 1 to 10 inclusive.
In the general formula (6), R1^ and R*? each preferably represent a hydrogen atom, C2-C6 alkyl group, Cg-C ^ cycloalkyl group, C8-C14 alkylaryl group or alkylene oxide group wherein n represents 1 to 5, and Rl8 preferably represents a saturated or unsaturated C^-Cis alkyl group, C12-C24 cycloalkyl group or C12-C24 alkylaryl group.
The metallic detergents include, for example, phenates, sulfonates and phosphonates of barium (Ba), calcium (Ca) and magnesium (Mg). Among them, overbased Ca sulfonate, Mg sulfonate and Ca phenate and neutral Ca sulfonate are preferred. The metallic detergent is used usually in an amount of 0.1 to 10% by weight (based on the whole composition).
The ashless detergent-dispersants include, for example, benzyl- amine, boron derivatives of benzylamine, alkenylsuccinimides and boron derivatives of alkenylsuccinimides. The ashless detergent dispersant is used usually in an amount of 0.5 to 15% by weight (based on the whole composi¬ tion).
The oxidation inhibitors include, for example, amine oxidation inhibitors such as alkylated diphenylamines, pheyl-α-naphthylamines and alkylated α-naphthylamines; and phenolic oxidation inhibitors such as 2,6-di-t- butylphenol). The oxidation inhibitor is used usually in an amount of 0.05 to 2.0% by weight (based on the whole composition).
The viscosity-index improvers include, for example, polymethyl methacrylates, polyisobutylenes, ethylene/propylene copolymers and hydro- genated styrene-butadiene copolymers. The viscosity-index improver is used usually in an amount of 0.5 to 35% by weight (based on the whole composi¬ tion).
The rust inhibitors include, for example, alkenylsuccinic acids and partial esters of them, which can be suitably added to the composition.
The antifoamers include, for example, dimethyl polysiloxanes and polyacrylates, which can be suitably added to the composition.
The following Examples and Comparative Examples will further illustrate the present invention, which by no means limit the invention.
The properties were evaluated by a method described below.
Friction and Wear Characteristics
The wear track diameter (mm) and coefficient of friction were determined by the Shell four-ball test 30 min. after the initiation of the test. The test conditions were as follows:
load: 40 kg oil temperature: 90°C rotation rate: 1800 rpm, and test time: 30 minutes
Example 1:
A test oil was prepared by mixing a lube base oil and components given in Table 1. The components used were as follows:
(1) base oil:
mineral oil: 150 neutral oil having a kinematic viscosity at 100°C of 5.1 cSt (mm^/s), and synthetic oil: a mixed oil comprising 80% by weight of a poly-α-olefin and 20% by weight of diisodecyl adipate.
(2) Molybdenum dithiocarbamate: molybdenum sulfide dithiocarbamates of the general formula (1) where X* and X^ each represent an oxygen atom (O) and γl and Y^ each represent a sulfur atom (S) was used, having the following different hydrocarbon groups as indicated in Table 1 :
1. hydrocarbon group = p-C8-C 13 alkyl: commercially available primary alkyl groups (mixed C8-C 3 alkyl groups) - containing molybdenum sulfide dithiocarbamate,
2. hydrocarbon group = p-C 13 alkyl: commercially available primary alkyl groups (C13 alkyl groups) - containing molybdenum sulfide dithiocarbamate,
3. hydrocarbon group = 1-methylheptyl: molybdenum sulfide dithio¬ carbamate wherein R1 to R4 each represent a 1-methylheptyl group,
4. hydrocarbon group = 1-methylnonyl: molybdenum sulfide dithio¬ carbamate wherein R to R4 each represent a 1-methylnonyl group,
5. hydrocarbon group = 50% of a p-C 13 alkyl and 50% of 1-methyl- nonyl: molybdenum sulfide dithiocarbamate where R to R4 each represent a mixed alkyl group comprising a primary alkyl group (C13 alkyl group) and 1-methylnonyl group in a ratio of 50:50,
(3) Zinc dithiophosphate: commercially available i-C3/s-C6 alkyl type, and
(4) Zinc dithiocarbamate: commercially available n-C5/i-C5 alkyl type.
In Table 1, the relative amount of each of the additives is given in terms of percent by weight based on the whole composition, and die balance is the base oil (total: 100% by weight). The amount of added molybdenum sulfide dithiocarbamate is given in terms of the molybdenum atom content. The results are given in Table 1.
TABLE 1
Zinc dithio¬ Zinc dithio¬ Wear track
Experiment Molybdenum Dithiocarbamate phosphate carbamate Diameter Coefficient Number Base Oil Hydrocarbon Group Mo Content ppm % % mm of Friction
1 * mineral oil — ~ 0.10 — 0.48 0.1 15
2* mineral oil P-CR-C Π alkyl 700 0.10 — 0.34 0.066
3* mineral oil p-C 1 -t alkyl 700 0.10 — 0.59 0.060
4 mineral oil 1-methylheptyl 300 0.10 — 0.45 0.048
5 mineral oil 1 -methylnonyl 700 0.10 — 0.48 0.043
6 mineral oil p-C |3 alkyl 50% 700 0.10 ~ 0.42 0.045 l-menthylnonyl 50%
7* mineral oil P-CR-C Π alkyl 700 — 0.10 0.55 0.075
8 mineral oil 1 -methylnonyl 700 — 0.10 0.43 0.057 g* synthetic oil P-CR-C Π alkyl 700 0.10 — 0.49 0.070
10 synthetic oil 1 -methylnonyl 700 0.10 — 0.42 0.050
Experiment Examples with the symbol "*" are comparative examples, and others are examples of the present invention.
It is apparent from Table 1 that the lubricating oil compositions of the present invention (Experiment Nos. 4 to 6, 8 and 10) containing the speci¬ fied secondary alkyl group have a wear resistance and a reduced coefficient of friction which were far superior to those of the lubricating oil compositions (Experiment Nos. 2, 3, 7 and 8) containing ordinary molybdenum sulfide di¬ thiocarbamate bonded to the nitrogen atom through the primary carbon atom.
Example 2
A test oil was prepared by mixing a lube base oil with components given in Table 2. The components used were as follows:
(1) the base oil, molybdenum sulfide dithiocarbamate and zinc dithio¬ phosphate were the same as those identified in Example 1.
(2) Fatty acid glyceride:
CH2OCOR CH2OCOR
I I
CHOH 50 wt% CHOCOR 50 wt%
I I
CH2OH CH2OH
wherein R represents an oleyl group.
(3) Organic amide compound: oleamide
The results are given in Table 2
TABLE 2
Zinc dithio¬ Fatty Acid Fatty Acid Coefficient
Experiment Molybdenum Dithiocarbamate phosphate Glyceride Amide of Number Base Oil Hydrocarbon Group Mo Content ppm % % % Friction
1 1 mineral oil 1 -methylnonyl 700 0.10 0.10 — 0.039
12 mineral oil p-C 13 alkyl 50% 700 0.10 0.10 ~ 0.043 1 -methylnonyl 50%
I
13* mineral oil p-C π alkyl 700 0.10 0. 10 0.059
14 mineral oil 1 -methylnonyl 700 0.10 — 0.10 0.040
15 synthetic oil 1 -methylnonyl 700 0.10 0.10 — 0.048
Experiment Examples with the symbol "*" are comparative examples, and others are examples of the present invention.
It is apparent from the results given in Table 2 that the coefficient of friction is further reduced when the fatty acid ester or fatty acid amide is added.
According to the present invention, the lubricating oil composi¬ tion having wear resistance and friction characteristics far superior to those of a conventional metal sulfide dithiocarbamate containing composition can be provided. The lubricating oil composition of the present invention can be minimized in the phosphorus content or made phosphorus-free. Thus, the lubricating oil composition of the present invention can be used in various fields such as a field of lubricating oils for internal combustion engines, etc.
Claims
1. A lubricating oil composition comprising a lube base oil and 0.01 to 10% by weight, based on the total weight of the composition, of a metal dithiocarbamate (A) represented by the general formula (1):
wherein M represents a molybdenum atom or tungsten atom,
R1, R2, R3 and R4 may be the same or different from one another and each represent a hydrogen atom, saturated or unsaturated C1-C20 alkyl group, C5-C26 cycloalkyl or alkyl-substituted cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or such a hydrocarbon group as above which further contains an ester bond, ether bond, hydroxyl group or carboxyl group, with the proviso that at least one of Rl, R^, R3 and R4 must be a C5-C20 alkyl group having a secondary carbon atom, through which the group is bonded to a nitrogen atom (N) in the formula,
χl and X^ each represent an oxygen or sulfur atom, and
γl and Y^ each represent an oxygen or sulfur atom.
2. The lubricating oil composition according to Claim 1, which contains a lube base oil and, in addition to the metal dithiocarbamate (A) as set forth in Claim 1, 0.01 to 7% by weight, based on the total weight of the composition, of at least one organozinc compound selected from the group consisting of zinc dithiophosphates (B) of the general formula (2):
~Q S S 1 1
* \* C II S Zn S C II N /-* (2)
R1C \l2 wherein R^, R6} R7 and R8 may be the same or different from one another and each represent a hydrogen atom, saturated or unsaturated C1-C20 alkyl group, C6-C26 cycloalkyl or alkyl-substituted cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or such a hydrocarbon group as above which further contains an ester bond, etiier bond, hydroxyl group or carboxyl group, and
zinc dithiocarbamates (C) of the general formula (3):
wherein R^, R10? R11 and R1^ may be the same or different from one another and each represent a hydrogen atom, saturated or unsaturated C1-C20 alkyl group, C6-C26 cycloalkyl or alkyl-substituted cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or such a hydrocarbon group as above which further contains as ester bond, etiier bond, hydroxyl group or carboxyl group.
3. The lubricating oil of claim 1 or 2 further containing fatty acid esters, organic amides used in an amount of 0.01 to 5% by weight based on the total weight of the whole composition or a mixture of fatty acid esters and organic amides, wherein the fatty acid esters are of the following general formula:
CH2OCORl3
I
CHOH
I
CH2OH
and
CH2OCOR14
CHOCOR15
CH OH wherein RΪ , Rl and Rl5 each represent a saturated or unsaturated C_ to C22 alkyl group, and the organic amides are of the general formula:
wherein R^ and R 7 may be the same or different from each other and each represent a hydrogen atom, C 1 to C20 alkyl group, C6-C26 cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group or C2-C20 alkylene oxide group and R*8 represents a hydrogen atom C1-C20 alkyl group, C6-C26 cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group or such a hydrocarbon group as above further containing an ester bond, ether bond, hydroxyl group or carboxyl group, and wherein the alkylene oxide group is represent by the general formula
20 -J- H
wherein R1^ and R^O each represent a hydrogenation or methyl group an n represent an integer of 1 to 10 inclusive.
4. The lubricating oil composition of claim 1 or 2 wherein at least two of R1, R^, R and R4 in general formula 1 for the metal dithio¬ carbamate each represent a C5-C20 alkyl group bonded to the nitrogen atom through the secondary carbon atom.
5. The lubricating oil composition of claim 3 wherein at least two of R1, R2, R and R4 in general formula 1 for the metal dithiocarbamate each represent a C5-C20 alkyl group bonded to the nitrogen atom through the secondary carbon atom.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6027477A JPH07216378A (en) | 1994-01-31 | 1994-01-31 | Lubricating oil composition |
| EP95922076A EP0830444A4 (en) | 1995-05-24 | 1995-05-24 | Lubricating oil composition |
| PCT/US1995/005144 WO1996037581A1 (en) | 1994-01-31 | 1995-05-24 | Lubricating oil composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6027477A JPH07216378A (en) | 1994-01-31 | 1994-01-31 | Lubricating oil composition |
| PCT/US1995/005144 WO1996037581A1 (en) | 1994-01-31 | 1995-05-24 | Lubricating oil composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1996037581A1 true WO1996037581A1 (en) | 1996-11-28 |
Family
ID=26365406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1995/005144 WO1996037581A1 (en) | 1994-01-31 | 1995-05-24 | Lubricating oil composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH07216378A (en) |
| WO (1) | WO1996037581A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000071649A1 (en) * | 1999-05-19 | 2000-11-30 | Infineum International Limited | Lubricating oil composition containing less than 350 ppm molybdenum |
| US6172013B1 (en) | 1997-09-17 | 2001-01-09 | Exxon Chemical Patents Inc | Lubricating oil composition comprising trinuclear molybdenum compound and diester |
| US6536492B2 (en) | 1998-07-22 | 2003-03-25 | Michelin Recherche Et Technique S.A. | Silica-containing rubber composition vulcanizable with sulfur |
| EP1652908A1 (en) * | 2004-11-01 | 2006-05-03 | Infineum International Limited | Lubricating Compositions |
| WO2006137928A3 (en) * | 2004-11-04 | 2007-03-22 | Pratt & Whitney | Lubricants containing multifunctional additive packages therein for improving load-carrying capacity, increasing surface fatigue life and reducing friction |
| EP2248878A1 (en) * | 2009-05-01 | 2010-11-10 | Shell Internationale Research Maatschappij B.V. | Lubricating composition |
| RU2451720C2 (en) * | 2006-10-27 | 2012-05-27 | Идемицу Козан Ко., Лтд. | Lubricating oil composition |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006265493A (en) * | 2005-03-25 | 2006-10-05 | Nippon Oil Corp | Lubricating oil composition |
| US10443008B2 (en) * | 2017-06-22 | 2019-10-15 | Exxonmobil Research And Engineering Company | Marine lubricating oils and method of making and use thereof |
| JP7168342B2 (en) * | 2018-04-27 | 2022-11-09 | 株式会社Adeka | Molybdenum dithiocarbamate composition and method for producing molybdenum dithiocarbamate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4280916A (en) * | 1980-03-31 | 1981-07-28 | Shell Oil Company | Lubricant composition |
| US4529526A (en) * | 1982-11-30 | 1985-07-16 | Honda Motor Co., Ltd. | Lubricating oil composition |
| US4867890A (en) * | 1979-08-13 | 1989-09-19 | Terence Colclough | Lubricating oil compositions containing ashless dispersant, zinc dihydrocarbyldithiophosphate, metal detergent and a copper compound |
-
1994
- 1994-01-31 JP JP6027477A patent/JPH07216378A/en active Pending
-
1995
- 1995-05-24 WO PCT/US1995/005144 patent/WO1996037581A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4867890A (en) * | 1979-08-13 | 1989-09-19 | Terence Colclough | Lubricating oil compositions containing ashless dispersant, zinc dihydrocarbyldithiophosphate, metal detergent and a copper compound |
| US4280916A (en) * | 1980-03-31 | 1981-07-28 | Shell Oil Company | Lubricant composition |
| US4529526A (en) * | 1982-11-30 | 1985-07-16 | Honda Motor Co., Ltd. | Lubricating oil composition |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP0830444A4 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6172013B1 (en) | 1997-09-17 | 2001-01-09 | Exxon Chemical Patents Inc | Lubricating oil composition comprising trinuclear molybdenum compound and diester |
| US6536492B2 (en) | 1998-07-22 | 2003-03-25 | Michelin Recherche Et Technique S.A. | Silica-containing rubber composition vulcanizable with sulfur |
| WO2000071649A1 (en) * | 1999-05-19 | 2000-11-30 | Infineum International Limited | Lubricating oil composition containing less than 350 ppm molybdenum |
| US6300291B1 (en) | 1999-05-19 | 2001-10-09 | Infineum Usa L.P. | Lubricating oil composition |
| EP1652908A1 (en) * | 2004-11-01 | 2006-05-03 | Infineum International Limited | Lubricating Compositions |
| WO2006137928A3 (en) * | 2004-11-04 | 2007-03-22 | Pratt & Whitney | Lubricants containing multifunctional additive packages therein for improving load-carrying capacity, increasing surface fatigue life and reducing friction |
| WO2007001445A3 (en) * | 2004-11-04 | 2007-03-22 | Pratt & Whitney | Multifunctional lubricant additive package |
| RU2451720C2 (en) * | 2006-10-27 | 2012-05-27 | Идемицу Козан Ко., Лтд. | Lubricating oil composition |
| US8367591B2 (en) | 2006-10-27 | 2013-02-05 | Idemitsu Kosan Co., Ltd. | Lubricating oil composition |
| EP2248878A1 (en) * | 2009-05-01 | 2010-11-10 | Shell Internationale Research Maatschappij B.V. | Lubricating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07216378A (en) | 1995-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0700425B1 (en) | Lubricating oil composition | |
| US5672572A (en) | Lubricating oil composition | |
| EP0528610B1 (en) | Low phosphorous engine oil composition and additive compositions | |
| JP3556355B2 (en) | Lubricating oil composition | |
| JP3554757B2 (en) | Engine oil composition | |
| JPH05279686A (en) | Lubricant oil composition for internal-combustion engine | |
| JPH07316577A (en) | Lubricating oil composition | |
| JP3556348B2 (en) | Lubricating oil composition | |
| JPH08209178A (en) | Lubricating oil composition | |
| WO1996037581A1 (en) | Lubricating oil composition | |
| WO1997008280A1 (en) | Lubricating oil composition | |
| CA2210974C (en) | Lubricating oil composition | |
| JPH07150169A (en) | Lubricating oil composition | |
| JP3609526B2 (en) | Lubricating oil composition | |
| AU2004203101B2 (en) | Low sulfur, low ash, and low phosphorous lubricant additive package using an alkylamine salt of a dialkylmonothiophosphate | |
| EP0588561A1 (en) | Low phosphorous engine oil compositions and additive compositions | |
| JPH07150173A (en) | Lubricating oil composition | |
| KR19980701400A (en) | LUBRICATING OIL FOR INTERNAL COMBUSTION ENGINE | |
| JPH07150170A (en) | Lubricating oil composition | |
| JPH11106776A (en) | Lubricating oil composition | |
| EP0830444A1 (en) | Lubricating oil composition | |
| JPH07331269A (en) | Lubricating oil composition | |
| JP2000053991A (en) | Lubricating oil composition for internal combustion engines | |
| JPH06207191A (en) | Lubricating oil composition | |
| JP2006182987A (en) | Lubricating oil composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): CA US |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE |
|
| DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| WWE | Wipo information: entry into national phase |
Ref document number: 1995922076 Country of ref document: EP |
|
| WWP | Wipo information: published in national office |
Ref document number: 1995922076 Country of ref document: EP |
|
| NENP | Non-entry into the national phase |
Ref country code: CA |