CN103717718A - 润滑油组合物 - Google Patents
润滑油组合物 Download PDFInfo
- Publication number
- CN103717718A CN103717718A CN201280037071.8A CN201280037071A CN103717718A CN 103717718 A CN103717718 A CN 103717718A CN 201280037071 A CN201280037071 A CN 201280037071A CN 103717718 A CN103717718 A CN 103717718A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- molybdenum
- lubricating oil
- quality
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 51
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 75
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 26
- 239000011733 molybdenum Substances 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 15
- 239000000314 lubricant Substances 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 48
- 239000005864 Sulphur Substances 0.000 claims description 21
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 5
- 239000002184 metal Substances 0.000 abstract description 46
- 239000002199 base oil Substances 0.000 abstract description 34
- 150000003839 salts Chemical class 0.000 abstract description 21
- 150000001875 compounds Chemical class 0.000 abstract description 20
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 125000004434 sulfur atom Chemical group 0.000 abstract 1
- 125000004014 thioethyl group Chemical group [H]SC([H])([H])C([H])([H])* 0.000 abstract 1
- -1 alkane hydrocarbon Chemical class 0.000 description 81
- 238000005987 sulfurization reaction Methods 0.000 description 47
- 239000002585 base Substances 0.000 description 31
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 30
- 238000004519 manufacturing process Methods 0.000 description 23
- 239000003921 oil Substances 0.000 description 23
- 239000003795 chemical substances by application Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 16
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 15
- 229960004889 salicylic acid Drugs 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 14
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 14
- 239000002480 mineral oil Substances 0.000 description 13
- 235000010446 mineral oil Nutrition 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 229920000768 polyamine Polymers 0.000 description 9
- 238000004517 catalytic hydrocracking Methods 0.000 description 8
- ALVPFGSHPUPROW-UHFFFAOYSA-N dipropyl disulfide Chemical compound CCCSSCCC ALVPFGSHPUPROW-UHFFFAOYSA-N 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 239000010779 crude oil Substances 0.000 description 7
- 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 7
- 229960002317 succinimide Drugs 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000005069 Extreme pressure additive Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 240000000203 Salix gracilistyla Species 0.000 description 5
- XYRMLECORMNZEY-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S XYRMLECORMNZEY-UHFFFAOYSA-B 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000005078 molybdenum compound Substances 0.000 description 5
- 150000002752 molybdenum compounds Chemical class 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229910052728 basic metal Inorganic materials 0.000 description 4
- 150000003818 basic metals Chemical class 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 230000001050 lubricating effect Effects 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 4
- 229960001860 salicylate Drugs 0.000 description 4
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical class [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 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 3
- 239000013530 defoamer Substances 0.000 description 3
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 3
- 239000012990 dithiocarbamate Substances 0.000 description 3
- 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 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000010721 machine oil Substances 0.000 description 3
- 125000002960 margaryl 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])[H] 0.000 description 3
- 125000001421 myristyl 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])[H] 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 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 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000913 palmityl 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])[H] 0.000 description 3
- 125000002958 pentadecyl 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])[H] 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 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 3
- 238000003860 storage Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 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 3
- 229960001124 trientine Drugs 0.000 description 3
- 125000002948 undecyl 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])[H] 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- YSQZSPCQDXHJDJ-UHFFFAOYSA-N 1-(pentyldisulfanyl)pentane Chemical compound CCCCCSSCCCCC YSQZSPCQDXHJDJ-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical group CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 238000006683 Mannich reaction Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QDAYJHVWIRGGJM-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QDAYJHVWIRGGJM-UHFFFAOYSA-B 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000002009 alkene group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
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Abstract
提供的是一种具有低钼含量和优良减磨性的润滑油组合物。所述润滑油组合物在润滑油基础油中包含：(A)式(1)表示的磷酸酯金属盐、和(B)钼原子与硫原子的比为1:3.5以上的有机钼化合物。(式中，R1至R4表示可选地相同或不同的C1-30的烃基、C1-30的烷基或烯基或含C1-30烷基的烷基硫代乙基；X1、X2、X3和X4各表示硫原子或氧原子，其中X1和X2的一者为氧或两者都为氧，X3和X4的一者为氧或两者都为氧；Y表示金属元素。)
Description
技术领域
本发明涉及新型润滑油组合物，更具体地涉及通过共混具有磷酸酯金属盐和具有特定结构的钼摩擦调整剂的基础油来制造的并具有优良减磨性的润滑油组合物。特别地，本发明涉及适合用作内燃机润滑油的润滑油组合物。
背景技术
通常，润滑油已用于内燃机、变速机或以使其平滑运转的润滑脂。特别地，要求内燃机用润滑油(机油)显示更高水平的性能，因为内燃机的性能已经改善，输出增强并在严苛工作条件下使用。为了满足该要求，常规机油包含各种添加剂如抗磨剂、金属清洁剂、无灰分散剂和抗氧化剂(例如，参见以下专利文献1至3)。对于燃料节省性机油，由于在涉及润滑油的摩擦部能量损失大，因此为了减少摩擦损失和燃料消耗，已经使用包含组合了各种添加剂如摩擦调整剂(FM)的润滑油(参见，例如，专利文献4)。最常见的是二烷基二硫代磷酸锌(ZDTP)与钼化合物组合使用的减磨技术，但是除非以相对大量共混该钼化合物，否则不能获得优良减磨性。
此外，钼化合物和ZDTP两者均为金属系且如果在内燃机用润滑油中使用引起它们污染排气的后处理系统并因此降低其净化效率的麻烦。大量钼化合物的使用可由于其劣化导致沉积增加或密封材料的不利影响，并因此用尽可能少量的钼化合物期望显示充分的减磨效果。
引文列表
专利文献
专利文献1：日本专利申请特开公报2001-279287
专利文献2：日本专利申请特开公报2002-129182
专利文献3：日本专利申请特开平公报08-302378
专利文献4：日本专利申请特开平公报06-306384
发明内容
发明要解决的问题
本发明的目的是提供甚至以少量的钼便可显示优良减磨性的内燃机、自动变速机或润滑脂中使用的润滑油组合物并特别适合用作内燃机润滑油。
用于解决问题的方案
作为上述问题的广泛的调查和研究的结果，本发明的发明人已完成本发明。
即，本发明涉及润滑油组合物，其包含润滑油基础油、(A)式(1)表示的磷酸酯金属盐、和(B)钼与硫的比为1:3.5以上的有机钼化合物：
其中，R1至R4各自为具有1至30个碳数的烃基、具有1至30个碳数的烷基或烯基，或包含具有1至30个碳数的烷基的烷基硫代乙基，且它们可以彼此相同或不同；X1、X2、X3和X4各自为硫或氧，X1和X2的一者为氧或两者都为氧，X3和X4的一者为氧或两者都为氧；Y表示金属元素。
发明的效果
本发明可提供润滑油组合物，其可用少量的钼来抑制其性能劣化并缓和对排气的后处理系统的不利影响，且可在混合润滑条件下进一步地充分减少摩擦，且具有优良的摩擦损失降低性和燃料消耗降低性。
具体实施方式
以下将更详细地描述本发明。
本发明的润滑油组合物中使用的润滑油基础油实例(下文称为“本发明的润滑油基础油”)包含矿物油系基础油和/或合成系基础油。
矿物油系基础油的实例包括可通过使原油的常压和/或减压蒸馏来制造的润滑油馏分进行选自溶剂脱沥青、溶剂萃取、加氢裂化、加氢异构化、溶剂脱蜡、催化脱蜡、加氢精制、硫酸处理和粘土处理的任一或任何适当的组合的精制处理所制造的链烷矿物油系基础油；正链烷烃；和异链烷烃。
优选的矿物油系基础油的实例包括通过精制以下基础油(1)至(7)和/或通过回收润滑油馏分的给定处理从基础油(1)至(7)中回收的润滑油馏分制造的基础油：
(1)通过链烷烃系原油和/或混合系原油的拨顶原油(topped crude)的减压蒸馏所制造的全减压瓦斯油(whole vacuum gas oil，WVGO)；
(2)通过润滑油脱蜡处理生产的蜡和/或通过气体到液体(gas to liquid，GTL)处理生产的合成蜡(费托(Fischer-Tropsch)蜡，GTL蜡)；
(3)选自上述基础油(1)和(2)的一种或两种以上的混合油，或通过中度加氢裂化(mild-hydrocracking)所述混合油制造的油；
(4)选自上述(1)至(3)的两种以上的基础油的混合油；
(5)通过链烷烃系原油和/或混合系原油的拨顶原油的减压残渣油的脱沥青所制造的脱沥青油(DAO)；
(6)通过中度加氢裂化(MHC)所述基础油(5)制造的油；
(7)选自上述(1)至(6)的两种以上基础油的混合油。
上述给定精制处理优选为加氢精制(hydrorefining)如加氢裂化或氢化提纯(hydrofinishing)、溶剂精制如糠醛萃取、脱蜡如溶剂脱蜡和催化脱蜡、使用酸性粘土或活性粘土的粘土精制、或化学(酸或碱)精制如硫酸处理和氢氧化钠处理。本发明中，可以以任意组合或任意顺序使用这些精制处理的任一种或多种。
矿物油系基础油特别优选以下基础油(8)：
(8)通过使选自上述基础油(1)至(7)的基础油、或由此回收的润滑油馏分加氢裂化，并对所得产物、或通过蒸馏由此回收的润滑油馏分进行脱蜡处理如溶剂或催化脱蜡，可选地随后蒸馏所制造的加氢裂化的矿物油。
如有必要，可在制造上述润滑油基础油(8)的适当时机另外进行溶剂精制处理和/或氢化提纯处理。
矿物油系基础油的硫含量没有特别限制，然而，其优选100质量ppm以下，更优选50质量ppm以下，更优选10质量ppm以下，且特别优选5质量ppm以下，目的是进一步改善热/氧化稳定性并减少硫含量。
矿物油系基础油的%CA优选为2以下，更优选1以下，更优选0.8以下，特别优选0.5以下，最优选0。如果%CA大于2，那么所得组合物的粘度-温度特性，热/氧化稳定性和燃料节省性会趋于劣化。
本发明中使用的润滑油基础油可以是合成系基础油。合成系基础油的实例包含聚-α-烯烃及其氢化化合物；异丁烯低聚物及其氢化化合物；链烷烃；烷基苯；烷基萘；二酯类如二(十三烷基)戊二酸酯，二-2-乙基己基己二酸酯，二异癸基己二酸酯，二(十三烷基)己二酸酯和二-2-乙基己基癸二酸酯；多元醇酯如三羟甲基丙烷辛酸酯，三羟甲基丙烷壬酸酯，季戊四醇2-乙基己酸酯和季戊四醇壬酸酯；聚氧亚烷基二醇；二烷基二苯基醚；和聚苯基醚。优选的合成系润滑油基础油为聚-α-烯烃。聚-α-烯烃的典型实例包括具有2至32，优选6至16个碳数的α-烯烃的低聚物或共低聚物(cooligomer)，例如1-辛烯低聚物、癸烯低聚物、乙烯-丙烯共低聚物及其氢化化合物。
本发明中使用的润滑油基础油的粘度指数优选为110以上，更优选120以上，更优选125以上且优选160以下。低于110的粘度指数不仅会引起粘度-温度特性，热/氧化稳定性，挥发防止性劣化，而且会引起摩擦系数增加并引起抗磨性劣化。大于160的粘度指数会趋于劣化低温粘度特性。
此处提及的粘度指数是指依照JIS K2283-1993测量的粘度指数。
本发明中使用的润滑油基础油的100℃运动粘度优选为10mm2/s以下，更优选6mm2/s以下，更优选5.0mm2/s以下，特别优选4.5mm2/s以下，最优选4.2mm2/s以下。同时，运动粘度优选为1mm2/s以上，更优选1.5mm2/s以上，更优选2mm2/s以上，特别优选2.5mm2/s以上，最优选3mm2/s以上。此处提及的100℃运动粘度是指通过ASTM D-445定义的100℃时的运动粘度。如果润滑油基础油组分的100℃运动粘度大于6mm2/s，那么所得组合物的低温粘度特性会劣化且不能获得充分改善的燃料节省性。如果100℃运动粘度低于1mm2/s，那么所得润滑油组合物由于其在润滑点(lubricating sites)的油膜形成不足会导致润滑性差，且组合物的蒸发损失会变大。
上述润滑油基础油可单独使用或与一种以上其它类型的基础油组合使用。当本发明的基础油与其它基础油组合使用时，混合基础油中本发明的基础油的比例优选为30质量%以上，更优选50质量%以上，更优选70质量%以上。
与本发明的基础油组合使用的其它基础油没有特别限制。然而，其它矿物油系基础油的实例包含溶剂精制的矿物油，加氢裂化的矿物油，加氢精制的矿物油，和溶剂脱蜡的矿物油，所有这些的100℃运动粘度大于10mm2/s且200mm2/s以下。其它合成系基础油的实例包含具有1至10mm2/s范围外的100℃运动粘度的那些。
本发明的润滑油组合物的组分(A)为式(1)表示的磷酸酯金属盐。
式(1)中，R1至R4各自为具有1至30个碳数的烃基，具有1至30个碳数的烷基或烯基，或包含具有1至30个碳数的烷基的烷基硫代乙基，且它们可彼此相同或不同；X1、X2、X3和X4各自为硫或氧，X1和X2的一者为氧或两者均为氧，X3和X4的一者为氧或两者均为氧；Y为金属元素。
R1至R4表示的具有1至30个碳数的烃基的具体实例包括烷基、环烷基或烯基、烷基取代的环烷基、芳基、烷基取代的芳基和芳基烷基。
烷基的实例包含如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基和十八烷基(这些烷基可以是直链或支化的)的那些。
环烷基的实例包括具有5至7个碳数的那些，如环戊基、环己基和环庚基。
烷基环烷基的实例包含具有6至11个碳数的、且其中烷基可结合至环烷基的任何位置的那些，如甲基环戊基、二甲基环戊基、甲基乙基环戊基、二乙基环戊基、甲基环己基、二甲基环己基、甲基乙基环己基、二乙基环己基、甲基环庚基、二甲基环庚基、甲基乙基环庚基和二乙基环庚基。
烯基的实例包括可以是直链或支化的且双键的位置可以不同的那些，如丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一碳烯基、十二碳烯基、十三碳烯基、十四碳烯基、十五碳烯基、十六碳烯基、十七碳烯基和十八碳烯基。
芳基的实例包括如苯基和萘基的那些。
烷基芳基的实例包括具有7至18个碳数的、且其中烷基可以是直链或支化的并结合至芳基的任何位置的那些，如甲苯基、二甲苯基、乙基苯基、丙基苯基、丁基苯基、戊基苯基、己基苯基、庚基苯基、辛基苯基、壬基苯基、癸基苯基、十一烷基苯基和十二烷基苯基。
芳基烷基的实例包括具有7至12个碳数的、且其中烷基可以是直链或支化的那些，如苄基、苯基乙基、苯基丙基、苯基丁基、苯基戊基和苯基己基。
R1至R4表示的具有1至30个碳数的烃基优选为具有1至30个碳数的烷基或具有6至24个碳数的芳基，更优选具有3至18个碳数的烷基，最优选具有4至8个碳数的直链烷基。
Y表示的金属的具体实例包括碱金属如锂、钠、钾和铯，碱土金属如钙、镁和钡，重金属如锌、铜、铁、铅、镍、银、锰和钼。这些金属中，优选的是锌、钼，和碱土金属如钙。特别优选的是锌。
关于上述磷化合物金属盐，磷化合物的配位数根据该金属的化合价而不同，例如，二价的锌和钙可能形成其中两个磷化合物配位至一个金属原子的络合物。
本发明的润滑油组合物组分(A)的含量优选为0.005质量%以上，更优选0.02质量%以上，特别优选0.05质量%以上且还优选0.5质量%以下，更优选0.2质量%以下，特别优选0.1质量%以下，基于组合物总质量以磷计。如果组分(A)基于组合物总质量以磷计的含量低于0.005质量%，那么所得组合物的耐磨性效果较差。如果含量多于0.5质量%，则担心磷会不利地影响对排气的后处理系统。
本发明中使用的上述组分(A)中，在上述磷含量的范围内还可包含含硫化合物，且该化合物的含量以硫计优选为0.1质量%以下，更优选0.08质量%以下。
为了显著增强在NOx气氛下的碱值(base number)保持性并显示本发明所需的减磨效果，最优选不使用该含硫化合物。
本发明的润滑油组合物的组分(B)为有机钼化合物，其中钼与硫的比为1:3.5以上。
用作组分(B)的有机钼化合物的实例包括(B1)硫化二硫代氨基甲酸钼(sulfurized molybdenum dithiocarbamates)、(B2)硫化二硫代磷酸钼和(B3)油溶性三核钼-硫化合物。
组分(B1)，即，本发明中使用的硫化二硫代氨基甲酸钼为下式(2)表示的有机钼化合物，其中硫与钼的比为3.5以上。
上式(2)中，R1、R2、R3和R4彼此可以相同或不同且各自为烃基如具有2至24、优选4至13个碳数的烷基或具有6至24、优选8至15个碳数的芳基(包括烷基芳基)。X1、X2、X3和X4彼此可以相同或不同且各自为硫或氧。
烷基的优选实例包含乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基和十八烷基。这些烷基可以是伯、仲或叔烷基，且为直链或支化。(烷基)芳基的优选实例包括苯基、甲苯基、乙基苯基、丙基苯基、丁基苯基、戊基苯基、己基苯基、辛基苯基、壬基苯基、癸基苯基、十一烷基苯基和十二烷基苯基，所有这些中的烷基可以是伯、仲或叔烷基，且为直链或支化的。此外，所述(烷基)芳基包括所有位置异构物(positional isomer)，其中芳基可拥有在任何位置的烷基取代基。
组分(B1)(即，硫化二硫代氨基甲酸钼)的具体实例，包括硫化二乙基二硫代氨基甲酸钼、硫化二丙基二硫代氨基甲酸钼、硫化二丁基二硫代氨基甲酸钼、硫化二戊基二硫代氨基甲酸钼、硫化二己基二硫代氨基甲酸钼、硫化二辛基二硫代氨基甲酸钼、硫化二癸基二硫代氨基甲酸钼、硫化二(十二烷基)二硫代氨基甲酸钼、硫化二(丁基苯基)二硫代氨基甲酸钼、硫化二(壬基苯基)二硫代氨基甲酸钼、硫化二乙基二硫代氨基甲酸氧化钼(sulfurizedoxymolybdenum diethyldithiocarbamate)、硫化二丙基二硫代氨基甲酸氧化钼、硫化二丁基二硫代氨基甲酸氧化钼、硫化二戊基二硫代氨基甲酸氧化钼、硫化二己基二硫代氨基甲酸氧化钼、硫化二辛基二硫代氨基甲酸氧化钼、硫化二癸基二硫代氨基甲酸氧化钼、硫化二(十二烷基)二硫代氨基甲酸氧化钼、硫化二(丁基苯基)二硫代氨基甲酸氧化钼、和硫化二(壬基苯基)二硫代氨基甲酸氧化钼(所有这些的烷基可以是直链或支化的，且这些烷基可结合至苯基的任何位置)，和其混合物。此外，还优选使用在一个分子中具有各自彼此具有不同碳数和/或结构的烃基那些化合物。
组分(B2)，即，本发明中使用的硫化二硫代磷酸钼为下式(3)表示的有机钼化合物，其中硫与钼的比为3.5以上。
上式(3)中，R5、R6、R7和R8彼此可以相同或不同且各自为烃基如具有2至30、优选5至18、更优选5至12个碳数的烷基，或具有6至18个碳数的芳基(包括烷基芳基)。Y1、Y2、Y3和Y4彼此可以相同或不同且各自为硫或氧。
烷基的优选实例包括乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基和十八烷基。这些烷基可以是伯、仲或叔烷基，且可为直链或支化的。(烷基)芳基的优选实例包括苯基、甲苯基、乙基苯基、丙基苯基、丁基苯基、戊基苯基、己基苯基、辛基苯基、壬基苯基、癸基苯基、十一烷基苯基和十二烷基苯基，所有这些的烷基可以是伯、仲或叔烷基，且可为直链或支化的。此外，所述(烷基)芳基包含所有位置异构物，其中芳基可拥有在任何位置的烷基取代基。
组分(B2)(即，硫化二硫代磷酸钼)的具体实例，包括硫化二乙基二硫代磷酸钼、硫化二丙基二硫代磷酸钼、硫化二丁基二硫代磷酸钼、硫化二戊基二硫代磷酸钼、硫化二己基二硫代磷酸钼、硫化二辛基二硫代磷酸钼、硫化二癸基二硫代磷酸钼、硫化二(十二烷基)二硫代磷酸钼、硫化二(丁基苯基)二硫代磷酸钼、硫化二(壬基苯基)二硫代磷酸钼、硫化二乙基二硫代磷酸氧化钼、硫化二丙基二硫代磷酸氧化钼、硫化二丁基二硫代磷酸氧化钼、硫化二戊基二硫代磷酸氧化钼、硫化二己基二硫代磷酸氧化钼、硫化二辛基二硫代磷酸氧化钼、硫化二癸基二硫代磷酸氧化钼、硫化二(十二烷基)二硫代磷酸氧化钼、硫化二(丁基苯基)二硫代磷酸氧化钼、硫化二(壬基苯基)二硫代磷酸氧化钼(所有这些的烷基可以是直链或支化的，且烷基可结合至苯基的任何位置)，和其混合物。此外，还优选使用每分子中具有各自彼此具有不同碳数和/或结构的烃基的那些化合物。
组分(B3)，即，本发明中使用的油溶性三核钼-硫化合物为式(4)表示的有机钼化合物，其中硫与钼的比为3.5以上。
Mo3SkLnQz(4)
式(4)中，L是为具有足够的碳原子数从而使化合物可溶解或分散于油中的有机基团的配体，n为1至4的整数。当n为2至4的任一时，L彼此可以相同或不同。同时k为4至7的整数，Q选自中性给电子化合物如水、胺、醇、膦和醚，z为0至5的整数并包括非化学计量值。当z为2至5的任一时，Q彼此可以相同或不同。
L可独立地选自由-X-R、-(X1)(X2)CR、-(X1)(X2)CYR、-(X1)(X2)CN(R1)(R2)、-(X1)(X2)P(OR1)(OR2)、其混合物及其过硫基衍生物(perthio derivatives)组成的组。X、X1、X2和Y各自独立地选自氧和硫，R、R1和R2各自独立地选自氢和有机基团(可以是相同或不同类型)。优选地，该有机基团为烃基如烷基(例如，其中附着在配体的残基的碳原子为伯、仲或叔的烷基)、芳基、取代芳基和醚基。更优选地，所有配体都是相同的。
重要地，配体的有机基团具有足够数量的碳原子以使化合物可溶解或分散于油中。例如，各基团中碳原子数通常为1至100，优选1至30，更优选4至20。优选的配体包括二烷基二硫代磷酸酯、烷基黄原酸酯和二烷基二硫代氨基甲酸酯，其中特别优选的是二烷基二硫代氨基甲酸酯。包含两种以上的上述官能团的有机配体还能结合一个以上的核并作为配体。为了本发明中使用的化合物的形成，优选选择具有适当的电荷以平衡相应核的电荷的合适配体。
虽然硫化二硫代氨基甲酸钼、硫化二硫代磷酸钼或油溶性三核钼-硫化合物可各自单独用作组分(B)，但因效果或不含磷而优选硫化二硫代氨基甲酸钼。还优选配体不包含磷化合物的油溶性三核钼-硫化合物。此外，该配体更优选二烷基二硫代氨基甲酸酯。
然而，从性能的角度来看，(B1)硫化二硫代氨基甲酸钼与(B2)硫化二硫代磷酸钼的组合使用也是有效的。在这种情况下，组分(B1)的含量与组分(B1)和(B2)的总量的比以钼计优选为50至95质量%，更优选60至95质量%，更优选70至95质量%。
本发明的润滑油组合物中，组分(B)中硫与钼的比必须在3.5以上，优选4以上，更优选5以上。如果硫与钼的比低于3.5，那么低摩擦性会劣化。
从减磨效果的角度看，本发明的润滑油组合物中组分(B)的含量基于润滑油组合物的总质量以钼计优选为10质量ppm以上，更优选50质量ppm以上，更优选100质量ppm以上，特别优选200质量ppm以上。同时，从润滑油基础油中的溶解性、储藏稳定性、氧化稳定性及进一步的经济性的角度看，该含量优选为600质量ppm以下，更优选500质量ppm以下，特别优选300质量ppm以下。如果组分(B)的含量超过600质量ppm，并且特别地如果聚α-烯烃或其氢化化合物用作润滑油基础油，那么组分(B)可能不充分溶解于基础油且长期储藏期间可能沉淀。此外，从经济性的角度看不优选该含量。
如有必要，本发明的润滑油组合物可根据其目的与已通常用于润滑油的任何添加剂共混以便进一步地增强性能。该添加剂的实例包含金属清洁剂、无灰分散剂、粘度指数改进剂、抗磨剂(或极压添加剂)、抗氧化剂、腐蚀防止剂、防锈剂、破乳剂、金属减活剂和消泡剂。
金属清洁剂的实例包含正常(normal)或碱性的碱金属或水杨酸碱土金属盐、正常或碱性的碱金属或碱土金属磺酸盐，和正常或碱性的碱金属或碱土金属酚盐。碱金属的实例包含钠和钾。碱土金属的实例包含镁、钙和钡。优选的是镁和钙。特别优选的是钙。
这些金属清洁剂中，从它们的减磨效果的观点，优选水杨酸碱金属或碱土金属盐系清洁剂(下文中指的是“水杨酸金属系清洁剂”)。
水杨酸金属盐系清洁剂的实例包括：通过以下制造的中性水杨酸金属盐：制备已加入等摩尔量烃基(例如，8至30个碳数的烯烃)的水杨酸或可选地通过向苯酚加入等摩尔量的烃基(例如，具有8至30个碳数的烯烃)随后用二氧化碳羧化进而使该水杨酸与化学计量的金属盐或金属碱作用所制造的具有8至30个碳数的烃基的水杨酸；通过在水存在下加热该中性水杨酸金属盐与过量的金属盐或金属碱(金属氢氧化物或氧化物)所制造的水杨酸碱性金属盐；在上述中性水杨酸金属盐存在下，通过使二氧化碳、硼酸或硼酸盐与碱如金属氢氧化物反应所制造的过碱性(超碱性，ultrabasic)水杨酸金属盐。这些反应通常在溶剂(脂族烃溶剂如己烷、芳香烃溶剂如二甲苯和轻质润滑油基础油)中进行。
用于水杨酸盐合成的具有8至30个碳数的烯烃通常大体分为8至19个碳数的烯烃组和20至30个碳数的烯烃组，并因此合成加入各烯烃的烃基的水杨酸。
烃基优选为从乙烯、丙烯或丁烯的聚合物或共聚物衍生的烷基，特别优选从直链α-烯烃如乙烯聚合物衍生的烷基。
本发明中，水杨酸金属盐系清洁剂可以是具有8至19个碳数的烃基(例如，8至19个碳数的烷基)的水杨酸金属盐(下文中通常称为“水杨酸金属盐C-a”)、或具有20至30个碳数的烃基(例如，20至30个碳数的烷基)的水杨酸金属盐(下文中通常称为“水杨酸金属盐C-b”)，或这两者单独或组合使用。从减磨效果的角度看，优选水杨酸金属盐C-b。然而，为了协同地改善储藏稳定性和低温流动性的目的，可组合使用水杨酸金属盐C-a和C-b。
通常通过在稀释剂如溶剂或润滑油基础油中反应来制造水杨酸金属盐系清洁剂。以该方式制造的水杨酸金属盐系清洁剂的金属含量的下限基于水杨酸金属盐系清洁剂的总质量优选1.0质量%以上，更优选2.0质量%以上，更优选5.0质量%以上，特别优选7.0质量%以上。金属含量上限优选20质量%以下，更优选15质量%以下，更优选12质量%以下，特别优选10质量%以下。
关于水杨酸金属盐系清洁剂的碱值，优选使用下限碱值调节至优选50mgKOH/g以上，更优选100mgKOH/g以上，更优选150mgKOH/g以上，特别优选200mgKOH/g以上的过碱性水杨酸盐系清洁剂作为主组分。还优选使用上限碱值调节至优选400mgKOH/g以下，更优选300mgKOH/g以下，更优选250mgKOH/g以下的过碱性水杨酸盐系清洁剂作为主组分。此处使用的术语“碱值”是指通过依照JIS K2501“石油产品和润滑油-中和价的测定(Petroleum products and lubricants-Determination of neutralization number)”第7节的高氯酸电位滴定法测量的值。
水杨酸金属盐系清洁剂的金属比没有特别限制。通常，可使用一种以上的金属比为20以下的清洁剂。金属比优选为低于4.5，更优选3以下。此处使用的术语“金属比”由(水杨酸盐系清洁剂中金属元素的化合价)×(金属元素含量(mole%))/(皂基含量(mole%))表示。金属元素是指钙和镁。皂基是指水杨酸基。
当水杨酸金属盐系清洁剂与本发明的润滑油组合物共混时，清洁剂的含量基于组合物的总质量优选为0.1质量%以上，更优选0.5质量%以上，更优选1质量%以上。该含量还优选15质量%以下，更优选10质量%以下，更优选5质量%以下，特别优选3质量%以下。如果含量低于0.1质量%，那么减磨效果将仅持续很短的时间。如果含量超过15质量%，那么将不能获得与含量相平衡的有利影响。金属含量的下限优选为0.01质量%以上，更优选0.05质量%以上，更优选0.1质量%以上，特别优选0.15质量%以上。上限优选为1.5质量%以下，更优选1.0质量%以下，更优选0.5质量%以下，特别优选0.3质量%以下。如果金属含量低于0.01质量%，那么减磨效果将仅持续很短的时间。如果金属含量超过1.5质量%，那么将不能获得与含量相平衡的有利影响。
无灰分散剂的实例包括在其分子中具有至少一个直链或支化的具有40至400个碳数的烷基或烯基的含氮化合物及其衍生物和烯基琥珀酸酰亚胺的改性物。选自这些无灰分散剂的任何一种以上可共混于本发明的润滑油组合物中。
无灰分散剂的烷基或烯基的碳数优选为40至400，更优选60至350。如果烷基或烯基的碳数少于40，那么无灰分散剂在润滑油基础油中的溶解性将趋于劣化。然而，如果烷基或烯基的碳数多于400，那么所得润滑油组合物的低温流动性将会劣化。烷基或烯基可以是直链或支化的，但优选为源自烯烃如丙烯、1-丁烯或异丁烯的低聚物或乙烯和丙烯的共低聚物的支化的烷基或烯基。
琥珀酰亚胺包括单型琥珀酰亚胺(mono-type succinimide)(其中将琥珀酸酐加到聚胺的一端，如式(5)所示)和双型琥珀酰亚胺(其中琥珀酸酐加到聚胺的两端，如式(6)所示)。
式(5)中，R9为具有40至400，优选60至350个碳数的烷基或烯基，并且p为1至5、优选2至4的整数。
式(6)中，R10和R11可彼此相同或不同，且各自独立为具有40至400，优选60至350个碳数的烷基或烯基，且特别优选聚丁烯基，并且q为0至4、优选1至3的整数。
本发明的润滑油组合物可包含单型和双型琥珀酰亚胺的一种或两种。
这些琥珀酰亚胺的制造方法没有特别限制。例如，可使用以下方法，其中将通过使具有40至400个碳数的烷基或烯基的化合物与马来酸酐在100至200℃的温度下反应所制造的烷基或烯基琥珀酰亚胺与聚胺反应。聚胺的实例包括二乙烯三胺、三乙烯四胺、四乙烯五胺和五乙烯六胺。
本发明中，可使用选自上述琥珀酰亚胺和/或其衍生物的任何无灰分散剂，且它们的重均分子量优选为6,500以上，更优选7,000以上，更优选8,000以上，特别优选9,000以上。如果该重均分子量小于6,500，那么非极性基团聚丁烯基的分子量将会变小，因此淤渣分散性(sludge dispersibility)会变差，并且由于极性基团上的胺部分(其可为氧化劣化的活性位点)相对增加导致氧化稳定性变差，因此无法获得工作寿命延长效果。另一方面，上限没有特别限制。然而，为了防止低温粘度特性劣化，其优选为20,000以下，更优选15,000以下。
此处提及的重均分子量为基于聚苯乙烯的重均分子量，其通过使用串联装有两根Tosoh Corp.制造的GMHHR-M(7.8mm ID×30cm)柱的Japan watersCo.制造的150-CALC/GPC，以四氢呋喃为溶剂，温度为23℃，流速为1mL/min，样品浓度为1质量%，试样注射量为75μL和差示折光仪(RI)作为检测器进行测量。
无灰分散剂可以是苄基胺。苄基胺的优选实例包括式(7)表示的化合物：
式(7)中，R12为具有40至400，优选60至350个碳数的烷基或烯基，并且r为1至5、优选2至4的整数。
苄基胺的制造方法没有特别限制。它们可通过以下制造：使聚烯烃如丙烯低聚物、聚丁烯或乙烯-α-烯烃共聚物与苯酚反应以制造烷基苯酚，然后使该烷基苯酚与甲醛和聚胺如二乙烯三胺、三乙烯四胺、四乙烯五胺或五乙烯六胺进行曼尼希反应(Mannich reaction)。
上述聚胺的具体实例包括式(8)表示的化合物。
R13-NH-(CH2CH2NH)s-H(8)
式(8)中，R13为具有40至400，优选60至350个碳数的烷基或烯基，并且s为1至5，优选2至4的整数。
聚胺的制造方法没有特别限制。例如聚胺可通过以下制造：将聚烯烃如丙烯低聚物、聚丁烯或乙烯-α-烯烃共聚物氯化，并使氯化的聚烯烃与氨或聚胺如乙烯二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺和五乙烯六胺反应。
其他衍生物的具体实例包括通过以下制造的有机酸改性化合物：使上述含氮化合物的任一与具有1至30个碳数的一元羧酸(脂肪酸等)，具有2至30个碳数的聚羧酸如草酸、邻苯二甲酸、偏苯三甲酸和均苯四甲酸，或含氧化合物如醇、醛、酮、烷基酚、环状碳酸酯(例如，乙烯碳酸酯)、羟基(聚)亚烷基碳酸酯反应，以中和或酰胺化(amidize)残留氨基和/或亚氨基的全部或部分；和通过使上述含氮化合物的任一与硫化合物反应而制造的硫改性化合物。此外，还可使用硼改性化合物。
然而，对于本发明的润滑油组合物，无灰分散剂优选为上述没有用硼改性的氮化合物的任一。
当本发明的润滑油组合物包含无灰分散剂时，其含量基于润滑油组合物的总质量优选为0.01至20质量%，更优选0.1至10质量%。如果无灰分散剂含量低于0.01质量%时，那么所得组合物的减磨效果不充分。同时，如果含量超过20质量%，那么所得润滑油组合物的低温流动性将极度劣化。
粘度指数改进剂具体地为非分散型或分散型含酯基粘度指数改进剂。该粘度指数改进剂的实例包括非分散型或分散型聚(甲基)丙烯酸酯系粘度指数改进剂、非分散型或分散型烯烃-(甲基)丙烯酸酯共聚物系粘度指数改进剂、苯乙烯-马来酸酐酯共聚物系粘度指数改进剂，及其混合物。优选的是非分散型或分散型聚(甲基)丙烯酸酯系粘度指数改进剂。特别优选的是非分散型或分散型聚甲基丙烯酸酯系粘度指数改进剂。
粘度指数改进剂的其它实例包括非分散型或分散型乙烯-α-烯烃共聚物或其氢化化合物、聚异丁烯和其氢化化合物、苯乙烯-二烯氢化共聚物和聚烷基苯乙烯。
抗磨剂(或极压添加剂)可以是已用于润滑油的任何抗氧化剂或极压添加剂。例如，可使用硫系，磷系和硫磷系极压添加剂。具体实例包含二烷基二硫代磷酸锌(ZnDTP)、亚磷酸酯、硫代亚磷酸酯、二硫代亚磷酸酯、三硫代亚磷酸酯、磷酸酯、硫代磷酸酯、二硫代磷酸酯、三硫代磷酸酯、其胺盐、其金属盐或其衍生物、二硫代氨基甲酸盐(酯)、二硫代氨基甲酸锌、MoDTC、二硫化物、多硫化物和硫化油脂。这些抗磨剂中，优选的是硫系极压添加剂，且特别优选的是硫化油脂。
抗氧化剂可以是无灰抗氧化剂如酚系或胺系抗氧化剂，或金属系抗氧化剂如铜系或钼系抗氧化剂。酚系抗氧化剂的具体实例包括4,4'-亚甲基双(2,6-二-叔丁基苯酚)和4,4'-双(2,6-二-叔丁基苯酚)。胺系抗氧化剂的具体实例包括苯基-α-萘胺，烷基苯基-α-萘胺和二烷基二苯基胺。
腐蚀防止剂的实例包括苯并三唑系、甲苯基三唑系、噻二唑系和咪唑系化合物。
防锈剂的实例包括石油磺酸酯、烷基苯磺酸酯、二壬基萘磺酸酯、烯基琥珀酸酯，和多元醇酯。
破乳剂的实例包知聚亚烷基二醇系非离子表面活性剂如聚氧乙烯烷基醚、聚氧乙烯烷基苯基醚和聚氧乙烯烷基萘基醚。
金属减活剂的实例包括咪唑啉、嘧啶衍生物、烷基噻二唑、巯基苯并噻唑、苯并三唑及其衍生物、1,3,4-噻二唑多硫化物、1,3,4-噻二唑基-2,5-双二烷基二硫代氨基甲酸酯、2-(烷基二硫代)苯并咪唑和β-(邻硫代羧基苄基)丙腈(β-(o-carboxybenzylthio)propionitrile)。
消泡剂的实例包括25℃运动粘度为1000至100,000mm2/s的硅油、烯基琥珀酸衍生物、聚羟基脂族醇和长链脂肪酸的酯，甲基水杨酸和邻羟基苄醇的芳族胺盐。
当本发明的润滑油组合物包含这些添加剂时，基于组合物的总质量，以0.0005至1质量%的量包含消泡剂并以选自0.01至10质量%范围的量包含其它添加剂
实施例
本发明将参考以下实施例和比较例来描述，但并非局限于此。
(实施例1至8，比较例1至5)
制备根据本发明的润滑油组合物(实施例1至8)和比较用润滑油组合物(比较例1至5)。使用高频率，线性振荡摩擦测试仪(SRV，油温：110℃，负荷：400N，测试时间：30min)对这些组合物进行摩擦测试，并将结果示于表1。
如示于表1的结果所示，与参考油相比，实施例1至8的润滑油组合物的摩擦系数改善率优良，且其减磨性大幅优于不包含组分(A)或组分(B)的比较例1至5的组合物。
产业上的可利用性
本发明的润滑油组合物可通常用在需显示减磨效果的润滑油中。此外，该组合物可不仅适用于作为自动车的变速机或最终减速齿轮用齿轮油，而且还适用于两轮或四轮车辆、发电机和热电联产用的内燃机如汽油发动机、柴油发动机和燃气发动机。此外，该组合物还用于各种发动机如船和舷外马达用的那些。
Claims (3)
1.一种润滑油组合物，其包含润滑油基础油、(A)式(1)表示的磷酸酯金属盐、和(B)钼与硫的比为1:3.5以上的有机钼化合物：
其中，R1至R4各自为具有1至30个碳数的烃基、具有1至30个碳数的烷基或烯基或包含具有1至30个碳数的烷基的烷基硫代乙基，且它们可以彼此相同或不同；X1、X2、X3和X4各自为硫或氧，X1和X2的一者为氧或两者都为氧，X3和X4的一者为氧或两者都为氧；Y表示金属元素。
2.根据权利要求1所述的润滑油组合物，其中R1至R4各自为具有4至8个碳数的直链烷基。
3.根据权利要求1或2所述的润滑油组合物，其进一步包含不含硼的无灰分散剂。
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| JP2693698B2 (ja) | 1993-04-22 | 1997-12-24 | 株式会社ジャパンエナジー | 省燃費型潤滑油 |
| WO1995007963A1 (en) * | 1993-09-13 | 1995-03-23 | Exxon Chemical Patents Inc. | Mixed antioxidant composition |
| CA2170503C (en) * | 1994-07-05 | 2005-08-16 | Noriyoshi Tanaka | Engine oil composition |
| JP3615267B2 (ja) | 1995-04-28 | 2005-02-02 | 新日本石油株式会社 | エンジン油組成物 |
| US5858931A (en) * | 1995-08-09 | 1999-01-12 | Asahi Denka Kogyo K.K | Lubricating composition |
| CN1175973A (zh) * | 1995-12-22 | 1998-03-11 | 株式会社日本能源 | 内燃机用润滑油 |
| CA2313408A1 (en) * | 1997-12-12 | 1999-06-24 | Jonathan Martin Mcconnachie | Method for the preparation of trinuclear molybdenum-sulfur compounds and their use as lubricant additives |
| JP4416261B2 (ja) | 2000-03-29 | 2010-02-17 | 新日本石油株式会社 | エンジン油組成物 |
| JP4856305B2 (ja) | 2000-10-30 | 2012-01-18 | Ｊｘ日鉱日石エネルギー株式会社 | エンジン油組成物 |
| JP4327519B2 (ja) * | 2002-06-28 | 2009-09-09 | 新日本石油株式会社 | 潤滑油組成物 |
| US7790659B2 (en) * | 2002-06-28 | 2010-09-07 | Nippon Oil Corporation | Lubricating oil compositions |
| JP5027426B2 (ja) * | 2006-02-17 | 2012-09-19 | 昭和シェル石油株式会社 | 潤滑剤組成物 |
| JP5658066B2 (ja) * | 2011-03-23 | 2015-01-21 | 昭和シェル石油株式会社 | 潤滑油組成物 |
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2011
- 2011-05-26 JP JP2011117733A patent/JP5756342B2/ja not_active Expired - Fee Related
-
2012
- 2012-01-20 EP EP12790030.6A patent/EP2716743A4/en not_active Withdrawn
- 2012-01-20 WO PCT/JP2012/051219 patent/WO2012160840A1/ja active Application Filing
- 2012-01-20 US US14/122,074 patent/US20140100148A1/en not_active Abandoned
- 2012-01-20 CN CN201280037071.8A patent/CN103717718B/zh not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010053751A1 (en) * | 2000-03-29 | 2001-12-20 | Mcconnachie Jonathan M. | Manufacture of lubricant additives |
| CN1671827A (zh) * | 2002-06-28 | 2005-09-21 | 新日本石油株式会社 | 润滑油组合物 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111187649A (zh) * | 2020-02-05 | 2020-05-22 | 新疆工程学院 | 一种基于嵌段聚酯化学改性的偏苯三甲酸酯润滑油基础油及其制备方法 |
| CN111187649B (zh) * | 2020-02-05 | 2022-01-28 | 新疆工程学院 | 一种基于嵌段聚酯化学改性的偏苯三甲酸酯润滑油基础油及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103717718B (zh) | 2016-01-20 |
| US20140100148A1 (en) | 2014-04-10 |
| JP5756342B2 (ja) | 2015-07-29 |
| JP2012246362A (ja) | 2012-12-13 |
| WO2012160840A1 (ja) | 2012-11-29 |
| EP2716743A1 (en) | 2014-04-09 |
| EP2716743A4 (en) | 2014-11-19 |
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