CN1305521A - 润滑油组合物 - Google Patents
润滑油组合物 Download PDFInfo
- Publication number
- CN1305521A CN1305521A CN99807400A CN99807400A CN1305521A CN 1305521 A CN1305521 A CN 1305521A CN 99807400 A CN99807400 A CN 99807400A CN 99807400 A CN99807400 A CN 99807400A CN 1305521 A CN1305521 A CN 1305521A
- Authority
- CN
- China
- Prior art keywords
- composition
- oil
- compound
- additive
- alkyl
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 32
- 239000003921 oil Substances 0.000 claims abstract description 74
- 150000001875 compounds Chemical class 0.000 claims abstract description 58
- 239000000654 additive Substances 0.000 claims abstract description 36
- 230000000996 additive effect Effects 0.000 claims abstract description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 239000005864 Sulphur Substances 0.000 claims description 26
- 239000003963 antioxidant agent Substances 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 239000000314 lubricant Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- 229910052711 selenium Chemical group 0.000 claims description 5
- 239000011669 selenium Chemical group 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000003463 sulfur Chemical class 0.000 claims description 2
- 235000019602 lubricity Nutrition 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 15
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract description 4
- 230000001050 lubricating effect Effects 0.000 abstract description 3
- 238000009877 rendering Methods 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 description 23
- 235000006708 antioxidants Nutrition 0.000 description 23
- 239000005078 molybdenum compound Substances 0.000 description 15
- 150000002752 molybdenum compounds Chemical class 0.000 description 15
- 235000016768 molybdenum Nutrition 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- 150000001721 carbon Chemical group 0.000 description 12
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 11
- -1 molybdenum sulfur halide salt Chemical class 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000005987 sulfurization reaction Methods 0.000 description 5
- 239000005749 Copper compound Substances 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 4
- 150000001880 copper compounds Chemical class 0.000 description 4
- 239000003879 lubricant additive Substances 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 244000299461 Theobroma cacao Species 0.000 description 3
- 235000009470 Theobroma cacao Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 108091064702 1 family Proteins 0.000 description 1
- BKCNDTDWDGQHSD-UHFFFAOYSA-N 2-(tert-butyldisulfanyl)-2-methylpropane Chemical compound CC(C)(C)SSC(C)(C)C BKCNDTDWDGQHSD-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 108010021119 Trichosanthin Proteins 0.000 description 1
- JNVCSEDACVAATK-UHFFFAOYSA-L [Ca+2].[S-]SSS[S-] Chemical compound [Ca+2].[S-]SSS[S-] JNVCSEDACVAATK-UHFFFAOYSA-L 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001356 alkyl thiols Chemical class 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 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
- SVOAENZIOKPANY-UHFFFAOYSA-L copper;octadec-9-enoate Chemical compound [Cu+2].CCCCCCCCC=CCCCCCCCC([O-])=O.CCCCCCCCC=CCCCCCCCC([O-])=O SVOAENZIOKPANY-UHFFFAOYSA-L 0.000 description 1
- WNCLUZLXMODRRZ-UHFFFAOYSA-N copper;oxolane-2,5-dione Chemical compound [Cu].O=C1CCC(=O)O1 WNCLUZLXMODRRZ-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000010688 mineral lubricating oil Substances 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229960003531 phenolsulfonphthalein Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 150000003336 secondary aromatic amines Chemical class 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 229940051851 sulfurated lime Drugs 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000010698 whale oil 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/18—Complexes with metals
-
- 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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
提供了润滑油组合物,包括占主要量的润滑粘性油和次要量的作为添加剂的至少一种包括金属芯和连接到其上能使该化合物具备油溶性或油可分散性的一个或多个配体的化合物,至少一个配体有至少两个烃基,其中一个有1—7个碳原子,另一个有更多碳原子。
Description
本发明的领域
本发明涉及润滑油组合物和它的含有金属芯化合物的浓缩物。
本发明的背景
某些油溶性或油可分散性的金属芯化合物,即有连接到一个或多个配体上的金属芯的化合物,作为润滑油组合物(或润滑剂)的添加剂(或添加剂组分)用来改进组合物的性质和性能是已知的。配体赋予了化合物的油溶性。例如,某些油溶性含钼和含硫化合物已经被建议和作为润滑剂添加剂来考察。US-A-2,951,040;-3,419,589;-3,840,463;-4,966,719;-4,995,996;和-4,978,464是描述含钼和含硫化合物的专利说明书的代表。
现有技术中描述的用作润滑剂添加剂的钼化合物主要是二核钼化合物,以氧化态的Mo(Ⅴ)为特征。然而,国际专利申请No.PCT/IB97/01656描述了三核钼化合物作为润滑剂添加剂的用途,即以不同氧化态(Mo(Ⅳ))为特征;与二核钼化合物相比,三核钼化合物作为润滑添加剂具有改进的性能,这可由在上述国际专利申请中的测试结果证实,如此缓解了应初始设备制造商(OEM)的要求来提供改进的润滑剂性能的问题。
作为用作润滑油组合物和/或用于它的浓缩物中的添加剂的化合物,上述国际专利申请描述了有结构式Mo3SkLn或它们的混合物的那些,其中:L表示与当n大于1时由L表示的其它配体保持独立性的配体;
n为1-4;和
k为至少4,例如在4-10,如4-7,优选4或7。
或有结构式Mo3SkExLn或它们的混合物的那些,其中L和n如上所定义,k为至少1,E是氧或硒,x为至少1,以及k和x的总数为至少4。
它进一步陈述了配体L可含有有机基,优选是烃基如烷基。
US-A-5,627,146描述了使用配体化学来改进某些钼芯化合物的性能。因此,它描述了一种润滑油组合物,它包括由矿物油和/或Ⅵ为至少115和在100℃的粘度在2-50cSt范围内的合成油组成的高Ⅵ油和由通式(1)表示的不对称类型的二硫代氨基甲酸钼:
其中R1和R2二者各表示有支链的C8-C13烷基,R3和R4的每一个各表示有支链和/或直链的C8-C13烷基,条件是R1-R4中没有相同的,以及X表示硫原子或氧原子。不对称性据说获得了性能上的优点。
然而在上述US专利中所述的化合物在它们烷基中的碳原子数目上受到了限制;例如C8是最小的和C15是最大的。这又限制了仲胺的范围。例如,它可用于制备化合物的配体前体。
本发明解决了该问题,通过使用在不对称化合物中有低于8个碳原子的基团,但没有产生所不希望的而预计当使用有这样低数目碳原子的基团会带来的低油溶性。它还扩展了化合物类型的范围,超出了描述在US专利中的那些,没有被限制到二核钼化合物,以及扩大了应用范围,超出了描述在US专利中的那些,没有被限制到特定的基油。而且,使用这类不对称化合物作为润滑油组合物中的添加剂获得了改进的抗氧化性能。
本发明的概述
在第一方面,本发明是润滑油组合物,包括或通过混合以下组分来制备:占主要量的润滑粘性油和次要量的作为添加剂的至少一种包括金属芯和连接到其上的能使该化合物具备油溶性或油可分散性的一个或多个配体的化合物,这个配体或配体中至少一个,优选全部配体含有至少两个烃基,其中一个有1-7个,如1-5个碳原子,另一个比上述那个烃基的碳原子多至少1个,优选多至少5个,如至少10个,最优选多至少15个。
如上所述,差异可以是至少1个碳原子,如至少2,3或4个碳原子,也如所述那样,如至少5或至少10或至少15个碳原子。
化合物可提供基于组合物的重量的至少1,例如1-2000,如5-1000,优选20-1000ppm的按重量计的金属(以金属原子表示)。
优选的是,金属芯,作为包括一个以上金属原子的金属簇合物芯,为元素周期表VIB族金属芯,如可以是二核或三核钼芯。它可含有全部或部分由硫构成的非金属原子。优选它由三核钼和硫构成。配体可以例如是双齿配体,例如通过两个硫原子键接于芯。
根据本发明第一方面的润滑油组合物有优异的耐磨、抗氧化,和减摩性能;它也与用于配制商品润滑油组合物的其它添加剂相容,并能够从容易获得的起始原料制备。
在第二方面,本发明是用来与润滑粘性油掺混的添加剂浓缩物,它包括或通过混合以下两种组分来制备:油性载体和按金属重量(以金属原子表示)计1-200,000,例如50-150,000,如50-100,000ppm的在本发明第一方面所定义的添加剂,基于浓缩物的重量。
在第三方面,本发明是润滑内燃机的方法,包括使发动机运转和用本发明第一方面的润滑油组合物润滑发动机。
在第四方面,本发明是在本发明第一方面定义的添加剂用于增强润滑油组合物的一种或多种润滑油性能的用途。
在第五方面,本发明为制备润滑油组合物或添加剂浓缩物的方法,包括将在本发明第一方面定义的添加剂与润滑粘性油或油性载体混合。
在本说明书中:
采用“包括”或任何同类的词语来说明所述特征,整数,步骤或组分的存在,但不排除一种或多种其它特征,整数,步骤,组分或它们的组合的存在或增加。
“占主要量”意思是超过组合物的50重量%。
“次要量”意思是低于组合物的50重量%,同时相对于所述的添加剂和相对于存在于组合物中的全部添加剂的总重量%而言,计算为添加剂或所有添加剂的活性成分。
本发明也提供了作为在配制、贮存或使用的条件下在组合物或浓缩物的各种添加剂组分之间的任何反应的结果获得或可获得的产品,基本的以及通常的和最佳的。
本文所用的“油溶性”或“可分散性”未必是指按全部比例在油中可溶、可溶解、混溶或悬浮的化合物或添加剂。然而,意思是它们例如以足够在油所使用的环境中施加它们预期的效果的程度溶于或稳定分散在油中。而且,如果需要,另外其它添加剂的引入也允许引入更高水平的特定添加剂。
本发明的详细描述
润滑组合物的油
该油可选自植物油,动物油,矿物油或合成油,该油可在粘度从轻馏分矿物油到重润滑油如燃气机油,矿物润滑油,汽车油,和重型柴油中变化。油可以是未提炼的,提炼的和重新提炼的。该油可以是使用过的油。
总之,在100℃下油的粘度在2-30,尤其在5-20mm2s-1的范围内。油例如可以是无硫的。
化合物
优选的是,烃基为烷基(例如,其中连接配体剩余部分的碳原子是伯碳,仲碳或叔碳),它们独立为直链或支链。更优选的是,全部配体是相同。
重要的是,配体的烃基有足够数目的碳原子以使化合物具备油溶性或油分散性。化合物的油溶性或分散性可受配体中碳原子数目的影响。所选择的配体优选有足够数目的碳原子以使化合物具备油溶性或油分散性。在本发明中的化合物中,在所有化合物配体的烃基当中存在的碳原子总数一般为至少21,例如21-800,如至少25,至少30或至少35。例如,在各烷基中的碳原子数一般在1-100的范围,优选1-40和更优选3和20之间。
和它们的混合物,以及它们的过硫衍生物,其中X,X1,X2和Y独立选自氧和硫,和其中R1和R2独立表示上述至少两个烃基。
优选的配体包括二烷基二硫代磷酸根(“ddp”),黄原酸根,硫代黄原酸根,二烷基磷酸根,二烷基二硫代氨基甲酸根(“dtc”)和羧酸根,以及在这些当中dtc是更优选的。
化合物例如可以是式Mo3SkLn或它们的混合物,其中:
L表示与当n大于1时由L表示的其它配体保持独立性的一个或多个配体;
n是在1-4的范围内;和
k是至少4,例如在4-10的范围,如4-7,优选4或7。
化合物还可以是式Mo3SkExLn或它们的混合物,其中L和n如上所定义,k为至少1,E是氧或硒,x为至少1,以及k和x的总数为至少4。
上式(Mo3SkLn和Mo3SkExLn)可各自另外包括结构部分Qz,其中Q表示中性给电子化合物如水,胺,醇,磷化氢和醚,以及z在0-5的范围和包括非化学计量值。
在上式中的Mo3Sk芯有+4的净电荷。因此,为了中和该芯,即在Mo3SkLn中所有配体L的总电荷必须是-4。4个单阴离子配位体L是优选的。如在式中所示那样,据信氧和/或硒可在芯中取代硫。然而,除了三核钼以外,芯应含有至少一个,和优选主要是硫(即大于50%)。最优选的是单独由钼和硫构成的芯。如果有的话,平衡原子是氧和/或硒。
当芯仅由三核钼和硫构成时,它由式Mo3Sk表示,以及有配体连接的话由式Mo3SkLn表示。
给电子化合物Qz仅仅存在于前式中以填充三核钼化合物中的任何空白配合位。
所属技术领域的那些技术人员将会认识到,化合物的形成需要选择有适宜电荷的适当配位体以平衡相应的芯的电荷。
术语“烃基”指有碳原子直接连接配体的残余部分的取代基,它在本发明的上下文中主要是烃基属性。这类取代基包括下列基团:(1)烃取代基,即脂族(例如烷基或链烯基),脂环族(例如环烷基或环烯基)取代基,芳族-,脂族-和脂环族-取代的芳族核,以及其中环由配体的另一部分完成的环状取代基(也就是说,任何两个所指取代基可一起形成脂环族基团);(2)取代的烃取代基,即在本发明的上下文中,含有非烃基团的、不会改变取代基的主要烃基属性的那些。所属技术领域的技术人员会知道那些适宜的基团(例如卤(尤其氯和氟),氨基,烷氧基,巯基,烷基巯基,硝基,亚硝基,硫氧基等);(3)杂原子取代基,即,在本发明上下文中主要为烃属性的同时,取代基在另外由碳原子组成的链或环上存在有非碳原子。
式Mo3SkLnQz的化合物有被阴离子配体环绕的阳离子芯,可以由以下描述的结构(Ⅰ)和(Ⅱ)表示。或一般,含三核钼的化合物能够通过将适合的钼源与配体源,以及任选与硫提取剂反应来制备。这可以在适合的液体介质中如含水或有机介质中进行。油溶性或油可分散性的三核钼化合物能够例如通过在适当的溶剂中让(M1)2Mo3S13n(H2O)(其中n在0和2之间变化并包括非化学计量值)与适合的配体源如二硫化四烷基秋兰姆反应来制备。其它油溶性或油可分散性的三核钼化合物能够通过将(M1)2Mo3S13n(H2O)(其中n在0和2之间变化并包括非化学计量值),配体源如二硫化四烷基秋兰姆,二烷基二硫代氨基甲酸盐或二烷基二硫代磷酸盐,以及硫提取剂如氰根,亚硫酸根,或取代的膦反应来形成。另外,三核钼硫卤化物盐如[M1][Mo3S7A6](其中A=Cl,Br,或I)可与配体源如二烷基二硫代氨基甲酸盐或二烷基二硫代磷酸盐在适当的溶剂中反应来形成油溶性或油可分散性的三核钼化合物。在上式中,M1是相反离子如NH4。三核钼化合物与钼芯中的硫原子数相关。在公开的范围内,在芯中的硫原子数可通过将硫提取剂如氰化物和取代的膦,或给硫体如元素硫和有机三硫化物加到三核钼化合物中来改变。
总之,三核钼化合物能够通过众所周知的技术如色层分离法来纯化;然而,可不必要纯化该化合物。
组合物和浓缩物
本发明的润滑油组合物可通过将有效的、次要量的至少一种化合物和如果需要的话,一种或多种下文所述的助添加剂的混合物加到润滑粘性油中来制备。该制备可通过将化合物直接加到油中或通过首先将化合物在合适的载液中混合以获得油溶性或分散性,再将混合物加到润滑油中来完成。在化合物的添加之前,同时或之后,可由所属技术领域的那些技术人员已知的任何方法来将助添加剂加到油中。
如果需要,三核钨化合物和助添加剂在适宜的油性(一般是烃)载液中的浓缩物提供了在它们使用前处理它们的便利方式。如上述那些润滑粘性油以及脂族,环烷族,和芳族烃类是浓缩物的适合载体的实例。这些浓缩物可含有1-90重量%的添加剂,基于浓缩物的重量;优选是1-50,更优选20-70重量%。
由混合(或掺混)含有至少一种这些类类型的并以这里所述的用量使用的化合物和任选的助添加剂的润滑粘性油制成的润滑油组合物可用来润滑尤其内燃机如火花点燃式或压缩点火式发动机的机械发动机组件,这是通过将该润滑油加到它们的曲轴箱中来实现的。
助添加剂
其它润滑剂添加剂也可用来在本发明的润滑油组合物中掺合。它们包括分散剂,洗涤剂,例如单种或混合金属洗涤剂体系,倾点下降剂,粘度改进剂,抗氧化剂,表面活性剂,耐磨剂,和减摩剂。它们能以所属技术领域已知的比例结合。例如,能够制备含磷和/或硫化合物的添加剂如二烷基二硫代磷酸锌(ZDDP)并与本发明的化合物一起使用。然而,本发明的化合物当用于无或基本上无所添加的磷和/或硫(即,除了在化合物本身中含有的磷或硫以外的磷和/或硫)时也是有效的或甚至拥有改进的性能。基本上无磷和/或硫的润滑油组合物是这样一种油,在其中磷和/或硫的量不多于存在于润滑级粘度基油中的固有量。
尤其值得注目的是抗氧化剂与该化合物的结合使用。
适合的抗氧化剂的实例选自含铜抗氧化剂,含硫抗氧化剂,含芳族胺抗氧化剂和酚类抗氧化剂。
适合的含铜抗氧化剂的实例包括描述在EP-B-24 146,EP-A-280 579和EP-A-280 580中的油溶性铜化合物。因此,例如,铜可以油溶性合成或天然羧酸的铜盐形式被掺合到油中。羧酸(从它衍生出合适的铜盐)的实例包括C2-C18羧酸(例如乙酸,和脂肪酸如硬脂酸和棕榈酸),不饱和酸(例如油酸),支化羧酸(例如,分子量在200-500的环烷酸,新癸酸和2-乙基己酸),和烷基-或链烯基-取代的二羧酸(例如多链烯基取代的琥珀酸如十八烯基琥珀酸,十二烯基琥珀酸和多异丁烯基琥珀酸)。在一些情况下,适合的化合物可从酸酐,例如从取代的琥珀酸酐衍生。铜抗氧化剂例如可以是二硫代氨基甲酸铜或二硫代磷酸铜。其它含铜和含硫抗氧化剂,例如,硫醇铜,黄原酸铜,和硫代黄原酸铜也适合根据本发明使用,它们是铜的磺酸盐,酚盐(任选硫化的)和乙酰丙酮酸盐。可根据本发明使用的其它铜化合物是高碱性的铜化合物。这类化合物和它们的制备方法的实例描述在US-A-4,664,822和EP-A-0 425 367中。铜化合物可以是一价铜或二价铜形式。
适合的含芳族胺抗氧化剂的实例是有至少一个直接连接到至少一个胺属氮原子上的芳族基团的芳族胺。仲芳族胺,尤其有连接同一胺属氮原子的两个芳基的那些是优选的,但也不排除使用其它芳族胺。胺可含有一个或多个芳基,例如至少两个芳基。其中有两个芳基的情况下,二者优选直接连接到同一胺属氮上。可使用其中两个芳基通过共价键或通过原子或基团(例如,氧或硫原子,或-CO-,-SO2-或亚烷基)连接的化合物。芳环,优选芳族烃环,可以是未取代的或被选自烷基,环烷基,烷氧基,芳氧基,酰基,酰氨基,羟基和硝基的一个或多个取代基取代的。含有烷基取代的芳族烃环的胺是优选的,尤其含有两个烷基取代的苯基的那些。根据本发明使用的优选的N-芳基胺是萘基胺和尤其二苯基胺,包括烷基取代的二苯基胺,其中烷基可以是相同的或不同的,有1-28个碳原子。其它含氮抗氧化剂例如吩噻嗪类化合物也可用于本发明。
酚类抗氧化剂的实例包括(a)位阻叔烷基化一羟基酚,如更详细描述在US-A-2,944,086;-3,043,775;和-3,211,652中的那些;以及(b)亚甲基桥接的叔烷基多元酚,如4,4’-亚甲基双(2,6-二-叔丁基酚)和2,2’-亚甲基双(4,6-双-(1,1,2-三甲基丙基)酚),以及(a)和(b)的混合物,如更详细地描述在EP-B-0456925中的那些。
含硫抗氧化剂(化合物)的实例是有优选C5-C10烷基侧链的烷基酚硫酯的碱土金属盐,壬基酚硫化钙,无灰油溶性酚盐和硫化酚盐,磷硫化或硫化烃类,磷酯和其它含硫和含钼化合物。含硫抗氧化剂的其它实例是二烃基二硫代磷酸或二烃基二硫代氨基甲酸金属盐化合物,其中金属选自Zn,Mn,Ni,Al,1族和2族金属。其它含硫化合物包括描述在EP-A-699 759中的那些,例如,油类,脂肪或聚烯烃的硫化物,其中有两个或多个硫原子的硫基在分子结构中被结合和键接在一起。实例包括硫化的鲸油,硫化的蒎烯油,硫化豆油,硫化酯,二烷基二硫化物,二烷基多硫化物,二苄基二硫化物,二叔丁基二硫化物,聚烯烃多硫化物,噻重氮类化合物如双烷基多硫化噻重氮,以及硫化酚。
优选的抗氧化剂是含铜抗氧化剂,包括二苯基胺和它的效果可与二苯基胺相当的衍生物在内的含芳族胺化合物,以及它们的混合物。含铜抗氧化剂的实例包括多异丁烯琥珀酸酐铜(“铜PIBSA”)和油酸铜,以及二苯基胺包括全部有效的二苯基胺的衍生物。
因此,本发明的润滑油组合物可包括次要量的至少一种抗氧化剂和至少一种油溶性或油可分散性的化合物。组合物可包括该化合物和在本文中公开的这些类型的抗氧化剂,润滑油和/或本身在本文公开的其它添加剂,和/或由于混合物的结果而产生的任何中间产物和反应产物的混合物。在混合物中,抗氧化剂和化合物以次要的、有效的量存在以获得增强的润滑性能,尤其油中的减摩,减摩保持,抗氧化和/或耐磨性能。
实施例
参照以下实施例,将更完全理解本发明,其中实施例1涉及用于本发明的化合物的制备,以及实施例P涉及用于对比的化合物的制备。
实施例1 制备不对称Mo3S7(dtc)4
将二硫化N,N’-二异丙基-N,N’-双十八烷基秋兰姆(63.3g)和甲苯(86.5g)加到装有搅拌器,水冷凝器,温度控制器和氮喷雾装置的500ml反应烧瓶中。搅拌该混合物,再加入多硫化钼铵{(NH4)2Mo3S132H2O}(25.8g)和甲醇(124.5g)。氮喷雾以20升/小时的速度开始。将混合物在20分钟内缓慢加热到60℃,然后在该温度下保持12小时,在此期间,H2S和NH3散发出来。放出的气体在苛性碱溶液中被吸收。在12小时后,氮喷雾被设定在相同的速度的氮气氛围代替,再加入ESN 150稀释剂油(80.3g)。然后将该装置改变为蒸馏构型。将混合物在30分钟内由60℃加热到75℃。然后施加500毫巴的真空,在30分钟的期间内将温度提高到125℃。然后将压力进一步降到绝对125毫巴,温度再在125℃下保持30分钟。
在冷却后,获得了暗褐/红色、中等粘度、油溶性产物,它含有6.34重量%的钼,是由式Mo3S7(dtc)4表示的化合物,其中dtc表示二硫代氨基甲酸根配体,其中各N原子被异丙基和十八烷基取代。
实施例P 制备对称Mo3S7(dtc)4化合物作为对比实施例
重复实施例1的工序,只是使用二硫化四可可基秋兰姆(72.6g)作为二硫化四烷基秋兰姆,以及使用89.6g的ESN 150稀释剂油。
在冷却后,获得了暗褐/红色、中等粘度、油溶性产物,它含有5.67重量%的钼,是由式Mo3S7(dtc)4表示的化合物,其中dtc表示二硫代氨基甲酸根配体,其中各N原子被可可基取代。“可可”是一般为C8-C18的烷基链或不同的偶数碳原子的链的混合物。
将实施例1和P的每一种产品以提供150和500ppm(按重量计)的钼(表示为钼原子)到油中的浓度掺混到充分调配好的润滑油中。油的配方(A-D)在下表中列出,其中给出了命名组分的重量%;A-D中每一种还含有分散剂;高碱性的磺酸镁洗涤剂;中性磺酸钙;二烷基二硫代磷酸锌耐磨添加剂;多异丁烯琥珀酸酐;消泡剂和粘度改性剂,在每一种油中以同样的比例存在。
油 | 实施例1 产品 | 实施例P 产品 | 稀释剂油 |
A | 0.237 | 88.772 | |
B | 0.265 | 88.744 | |
C | 0.790 | 88.219 | |
D | 0.883 | 88.126 |
如上所示,油A和B含有150ppm的钼,油C和D含有500ppm的钼。
四种油,A-D,各自在曲轴箱内油的氧化试验中进行测试,其中在油的温度保持在165℃的同时,将空气以固定的速度吹经油。在试验的开始加入氧化催化剂,一种提供40ppm铁的油溶性铁盐。定期取出油的样品,使用HAKEE粘度计测量它们的粘度。氧化的程度被测量为氧化油的粘度与它的最初粘度之间的粘度增加的百分数。获得了以下结果。
油 | A | B | C | D |
在16小时的粘度增加百分数 | 0 | 0 | 0 | 0 |
在24小时的粘度增加百分数 | 14.2 | 35.3 | 0 | 0 |
在40小时的粘度增加百分数 | 308.3 | 656.6 | 2.6 | 2.8 |
在48小时的粘度增加百分数 | 441.0 | - | 63.7 | 70.9 |
在64小时的粘度增加百分数 | - | - | 578.6 | 680.3 |
*破折号表示产物的粘度太粘不能被测量出。
以上结果证实,使用含有不对称钼化合物(A和C)的油得到的粘度增加值要低于使用对称钼化合物(B和D)得到的那些。使用150ppm的钼尤其证实了该效果,其中(本发明)油A的粘度比(对比)油B的保持了长得多的可测量时间。
本说明书也描述了包括以下组分或通过混合以下组分制备的润滑油组合物:占主要量的润滑粘性油和次要量的作为添加剂的至少一种包括金属芯和连接到其上能使该化合物具备油溶性或油可分散性的配体的化合物,配体中的至少一个含有至少两个其碳原子数不同的烃基,其差别为至少1个,优选至少5个,如至少10个,最优选至少15个碳原子。
Claims (20)
1、润滑油组合物,包括或通过混合以下组分来制备:占主要量的润滑粘性油和次要量的作为添加剂的至少一种化合物,该化合物包括金属芯和连接到其上的能使其具备油溶性或油可分散性的一个或多个配体,配体中的至少一个含有至少两个烃基,其中一个有1-7个,如1-5个碳原子,另一个比上述那个烃基的碳原子多至少1个,优选多至少5个,如至少10个,最优选多至少15个。
2、权利要求1的组合物,其中烃基独立是直链或支链的烷基。
4、权利要求3的组合物,其中该配体或上述至少一个配体为二烷基二硫代磷酸根或二烷基二硫代氨基甲酸根配体。
5、前述权利要求中任一项的组合物,其中金属芯是钼芯,如三核钼芯。
6、前述权利要求中任一项的组合物,其中芯含有全部或部分由硫构成的非金属原子。
7、权利要求5或6的组合物,其中芯由钼和硫构成。
8、权利要求5-7中任一项的组合物,其中化合物为式Mo3SkLn或它们的混合物,其中:
L表示上述一个或多个配体;
n是在1-4的范围内;和
k是至少4,例如在4-10的范围,如4-7,优选4或7。
9、权利要求5-7中任一项的组合物,其中化合物为式Mo3SkExLn或它们的混合物,其中L和n如权利要求8所定义,k为至少1,E是氧或硒,x为至少1,以及k和x的总数为至少4。
10、权利要求8或9的组合物,其中该结构式另外包括结构部分Qz,其中Q表示中性给电子化合物如水,胺,醇,磷化氢和醚,以及z在0-5的范围和包括非化学计量值。
11、前述权利要求中任一项的组合物,其中上述至少两个烃基中的另一个有8-100,例如15-40,再如15-20个碳原子。
12、前述权利要求中任一项的组合物,其中化合物的金属重量为基于组合物重量的至少1,例如1-2000,如5-1000,优选20-1000ppm。
13、前述权利要求中任一项的组合物,其中在全部配体中的碳原子总数为至少21,如21-800。
14、前述权利要求中任一项的组合物,其中润滑粘性油无硫。
15、前述权利要求中任一项的组合物,它进一步包括至少一种抗氧化剂添加剂或通过混合该添加剂来制备。
16、前述权利要求中任一项的组合物,它进一步包括一种或多种分散剂,洗涤剂,倾点下降剂,粘度改进剂,表面活性剂和耐磨剂,或通过混合它们来制备。
17、用于与润滑粘性油掺混的添加剂浓缩物,它包括或通过混合以下两种组分来制备:油性载体和按金属重量计1-200,000,例如50-150,000,再如50-100,000ppm的权利要求1-13中任一项所定义的添加剂,基于浓缩物的重量。
18、权利要求17的添加剂浓缩物,它进一步包括至少一种抗氧化剂添加剂,或通过混合该添加剂来制备,从而浓缩物含有1-90,如1-50重量%的添加剂,基于浓缩物的重量。
19、润滑内燃机的方法,包括运转发动机和用权利要求1-16中任一项所要求的润滑油组合物润滑该发动机。
20、在权利要求1-16中任一项定义的添加剂用于增强润滑油组合物的一种或多种润滑性能的用途。
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-
1998
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1999
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- 1999-06-15 WO PCT/EP1999/004152 patent/WO1999066013A1/en active Application Filing
- 1999-06-15 JP JP2000554823A patent/JP2002518547A/ja not_active Abandoned
- 1999-06-15 CA CA002335178A patent/CA2335178A1/en not_active Abandoned
- 1999-06-15 EP EP99929235A patent/EP1088050A1/en not_active Withdrawn
- 1999-06-17 US US09/335,126 patent/US6153564A/en not_active Expired - Fee Related
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JP2002518547A (ja) | 2002-06-25 |
WO1999066013A1 (en) | 1999-12-23 |
EP1088050A1 (en) | 2001-04-04 |
CA2335178A1 (en) | 1999-12-23 |
GB9813070D0 (en) | 1998-08-19 |
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