CN107001965B - 润滑油组合物 - Google Patents
润滑油组合物 Download PDFInfo
- Publication number
- CN107001965B CN107001965B CN201580068289.3A CN201580068289A CN107001965B CN 107001965 B CN107001965 B CN 107001965B CN 201580068289 A CN201580068289 A CN 201580068289A CN 107001965 B CN107001965 B CN 107001965B
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- China
- Prior art keywords
- lubricating oil
- oil composition
- base
- composition
- oil
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 169
- 239000010687 lubricating oil Substances 0.000 title claims description 92
- 239000002199 base oil Substances 0.000 claims abstract description 66
- 230000014759 maintenance of location Effects 0.000 claims abstract description 30
- 239000002551 biofuel Substances 0.000 claims abstract description 25
- 230000001050 lubricating effect Effects 0.000 claims abstract description 22
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 19
- 239000000194 fatty acid Substances 0.000 claims abstract description 19
- 229930195729 fatty acid Natural products 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 15
- 238000002485 combustion reaction Methods 0.000 claims description 13
- 239000003225 biodiesel Substances 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000010710 diesel engine oil Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 abstract description 26
- 238000007254 oxidation reaction Methods 0.000 abstract description 26
- -1 Verkade base compound Chemical class 0.000 abstract description 9
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 37
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- 235000019198 oils Nutrition 0.000 description 29
- 239000002253 acid Substances 0.000 description 27
- WFPZOAOJEXDUGP-UHFFFAOYSA-N 2,5-dimethyl-3-piperazin-1-ylpyrazine Chemical compound CC1=CN=C(C)C(N2CCNCC2)=N1 WFPZOAOJEXDUGP-UHFFFAOYSA-N 0.000 description 25
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 239000002283 diesel fuel Substances 0.000 description 7
- 239000000314 lubricant Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002956 ash Substances 0.000 description 6
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- 239000000047 product Substances 0.000 description 6
- WFHPXSHLCFHEIA-UHFFFAOYSA-N 4,6,11-tris(2-methylpropyl)-1,4,6,11-tetraza-5-phosphabicyclo[3.3.3]undecane Chemical compound C1CN(CC(C)C)P2N(CC(C)C)CCN1CCN2CC(C)C WFHPXSHLCFHEIA-UHFFFAOYSA-N 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000007655 standard test method Methods 0.000 description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 description 5
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 235000019482 Palm oil Nutrition 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 235000019484 Rapeseed oil Nutrition 0.000 description 4
- 239000007866 anti-wear additive Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
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- 239000002540 palm oil Substances 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000003549 soybean oil Substances 0.000 description 4
- 235000012424 soybean oil Nutrition 0.000 description 4
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- 235000004977 Brassica sinapistrum Nutrition 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
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- 239000003054 catalyst Substances 0.000 description 3
- 239000003240 coconut oil Substances 0.000 description 3
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- 238000010790 dilution Methods 0.000 description 3
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- 239000003112 inhibitor Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- FSXJJHHCBCMUEG-UHFFFAOYSA-N 1,4,6,11-tetraza-5-phosphabicyclo[3.3.3]undecane Chemical compound C1CNP2NCCN1CCN2 FSXJJHHCBCMUEG-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-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
- PCYSWBQHCWWSFW-UHFFFAOYSA-N 4,6,11-trimethyl-1,4,6,11-tetraza-5-phosphabicyclo[3.3.3]undecane Chemical compound C1CN(C)P2N(C)CCN1CCN2C PCYSWBQHCWWSFW-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 240000002791 Brassica napus Species 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 235000019486 Sunflower oil Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- 230000000994 depressogenic effect Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
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- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N linoleic acid group Chemical group C(CCCCCCC\C=C/C\C=C/CCCCC)(=O)O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 2
- 229960001860 salicylate Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002600 sunflower oil Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 239000001195 (9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid Substances 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RGMZCBSSMQHIRC-UHFFFAOYSA-N 2-benzyl-8-(2,2-dimethylpropyl)-9-(2-methylpropyl)-2,5,8,9-tetraza-1-phosphabicyclo[3.3.3]undecane Chemical compound CC(CN1P2N(CCN(CC1)CCN2CC1=CC=CC=C1)CC(C)C)(C)C RGMZCBSSMQHIRC-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-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
- DFRWCJYSXGNOFD-UHFFFAOYSA-N 4,6,11-tri(propan-2-yl)-1,4,6,11-tetraza-5-phosphabicyclo[3.3.3]undecane Chemical compound C1CN(C(C)C)P2N(C(C)C)CCN1CCN2C(C)C DFRWCJYSXGNOFD-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000014698 Brassica juncea var multisecta Nutrition 0.000 description 1
- 235000006008 Brassica napus var napus Nutrition 0.000 description 1
- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 description 1
- 244000188595 Brassica sinapistrum Species 0.000 description 1
- 235000016401 Camelina Nutrition 0.000 description 1
- 244000197813 Camelina sativa Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 235000019774 Rice Bran oil Nutrition 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 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 class [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 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010480 babassu oil Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 239000012043 crude product Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 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
- 229940069096 dodecene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
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- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
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- 238000005461 lubrication Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical class 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
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical class [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004032 superbase Substances 0.000 description 1
- 150000007525 superbases Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000003582 thiophosphoric acids Chemical class 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 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 description 1
- 239000003981 vehicle Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/16—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-nitrogen bond
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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Abstract
Description
技术领域
本发明涉及用于在柴油(压缩-点火)内燃发动机的曲轴箱中特定使用的润滑油组合物,其中内燃发动机可至少部分用生物柴油燃料提供燃料,并且涉及碱值保持性和酸值保持性的改善以及对此类润滑油组合物的氧化、腐蚀和淤渣形成的的抗性的改善。
背景技术
政府法规和市场需求持续强调在运输工业中化石燃料的节省。因此存在对于专门或部分用来自可再生或生物衍生来源(例如生物柴油燃料)的燃料提供燃料的车辆的增加的需求。
已知在柴油燃料组合物中包括脂肪酸烷基酯(FAAE),具体地说脂肪酸甲酯(FAME)。FAME在产生甲酯的催化剂存在下经由被称作酯基转移的化学过程用甲醇生产。FAME可由各种油衍生的原料(如大豆油、油菜籽油、葵花籽油、椰子油和使用的植物油)生产。出于多种原因可添加FAAE,包括降低燃料生产和消耗过程的环境影响或来改善润滑性。
然而,已发现用于润滑内燃发动机的润滑剂油组合物可常常变得被用于为发动机提供燃料的生物燃料稀释。生物柴油燃料包括在燃料喷射到发动机中之后减慢蒸发的低挥发性的组分。通常,生物柴油的未燃尽部分和所得部分燃烧分解产物中的一些变得与在汽缸壁上的润滑油组合物混合并且向下洗涤到油池中,由此污染曲轴箱润滑剂。在被污染的润滑剂中的生物柴油燃料可由于在发动机润滑期间的极端条件形成另外的分解产物。具体来说,已发现,用FAAE(如FAME)稀释润滑油组合物可导致对控制氧化稳定性和维持碱值的润滑油组合物的能力的不希望的影响。在生物柴油中烯双键和酯官能团的存在导致生物柴油燃料容易发生氧化降解,并且使得润滑油组合物氧化不稳定并且更易发生酸值(TAN)的增加、碱值(TBN)的减小以及淤渣和沉积物形成。在池中FAME的氧化导致酸的形成。如果不中和,那么这些酸可造成腐蚀。如果通过含有金属相对离子中和,那么它们可形成淤渣。另外,用于试图中和酸形成的过多的碱可导致在DPF上灰分形成。在油中的生物柴油污染越高,润滑油组合物的氧化稳定性越低。
此外,已发现,降低的氧化稳定性的此问题在采用迟延后喷射到汽缸中以在处理装置之后再生废气的柴油发动机(例如轻负荷、中负荷和客车柴油发动机)中显著更糟。在处理装置之后再生的此模式可导致在油中FAME稀释的较高水平。
因此,期望的是提供用于内燃发动机的曲轴箱的润滑油组合物,其在存在或不存在生物燃料(如FAME)的两种情况下具有改善的碱值保持性和酸值保持性。此外,还期望的是提供润滑油组合物,其提供此类改善的碱值保持性和酸值保持性,而不导致在DPF上的灰分形成。
还期望的是提供用于内燃发动机的曲轴箱的润滑油组合物,其降低当内燃发动机用生物燃料(如生物柴油)提供燃料时可出现的氧化稳定性的损失。此外,还期望的是提供润滑油组合物,其降低此类氧化稳定性的损失而不导致在DPF上的灰分形成。
Verkade碱为具有下式(1)的足球状含磷二环有机非离子超强碱(proazaphosphatrane)分子结构的化合物:
Verkade碱由于当(1)与质子反应时形成的质子化物质的异常稳定性而为非常强的碱。由于质子化形式的稳定性,Verkade碱作为路易斯碱比任何已知胺强约八个数量级。
Verkade碱已经成功地在多种有机反应中应用,如烷基化、脱卤化氢、酰化、用于碳-碳键形成的多种缩合和有机金属反应。式(1)的Verkade碱的第二特性为其充当用于连续加宽范围的反应(如在多步合成期间用各种硅烷基保护醇基、将异氰酸酯三聚成异氰尿酸酯和α,β-不饱和腈的合成)的优良催化剂的能力。
现在本发明人已经出人意料地发现,Verkade碱可用于改善用于内燃发动机的曲轴箱的润滑油组合物的碱值保持性和酸值保持性,具体地说其中内燃发动机用生物燃料组合物(具体地说包含脂肪酸烷基酯的生物燃料组合物)提供燃料。
Verkade碱还可用于降低用于内燃发动机的曲轴箱的润滑油组合物的氧化稳定性的损失,其中内燃发动机用生物燃料组合物(具体地说包含脂肪酸烷基酯的生物燃料组合物)提供燃料。
发明内容
根据本发明的第一方面,提供包含(i)基础油和(ii)具有式(1)的化合物的润滑组合物:
其中R1、R2和R3各自独立地选自氢和饱和或不饱和、直链或分支链C1-C22烷基。
本发明尤其适用于其中以润滑油组合物的总重量计润滑油组合物被至少0.3重量%的生物燃料或其分解产物或其混合物污染的情况。
已经出人意料地发现,本发明的润滑组合物除了改善的氧化稳定性、降低的腐蚀特性和降低的形成於渣倾向之外呈现改善的碱值(TBN)保持性和改善的酸值(TAN)保持性。
根据本发明的第二方面,提供具有式(1)化合物:
在包含用于提供润滑组合物的改善的碱值保持性的基础油的润滑组合物中尤其在生物燃料(尤其其中生物燃料包含脂肪酸烷基酯如FAME)存在下的用途,其中R1、R2和R3各自独立地选自氢和饱和或不饱和、直链或分支链C1-C22烷基。
根据本发明的另一个方面,提供用于改善润滑油组合物(尤其用于润滑用优选地其中生物燃料组合物包含脂肪酸烷基酯的生物燃料组合物提供燃料的内燃发动机的曲轴箱的润滑油组合物)的碱值的方法,所述方法包含将式(1)化合物添加到润滑油组合物:
其中R1、R2和R3各自独立地选自氢和饱和或不饱和、直链或分支链C1-C22烷基。
具体实施方式
如本文所用,术语“生物燃料”意指至少部分从可再生生物资源衍生的燃料,优选地生物柴油燃料。
如上所述,众所周知,用于为压燃式发动机提供燃料的柴油燃料组合物可并入脂肪酸烷基酯(FAAE)如脂肪酸甲酯(FAME)作为燃料组分。然而,不利的是,FAME挥发性比常规柴油小的多,因此相对于化石衍生的柴油燃料在润滑剂中具有高的多得聚积倾向。因此,在柴油燃料中较高含量的FAME可导致在润滑剂中较高含量的燃料稀释,这继而可导致润滑剂的氧化稳定性的不希望的损失。
本发明尤其适用于其中以润滑油组合物的总重量计润滑油组合物被至少0.3重量%的生物燃料或其分解产物或其混合物污染的情况。
如本文所用,术语“改善碱值保持性”意指保持或促进已用生物燃料(例如脂肪酸烷基酯(FAAE)如FAME)稀释的润滑油组合物的总碱值(TBN)。在本发明的一个优选实施例中,润滑油组合物的TBN根据ASTM D-2896和ASTM D-4739测量,其为用于测量润滑油组合物的TBN的标准测试方法。
如本文所用,术语“改善酸值保持性”意指保持或降低已用生物燃料(例如脂肪酸烷基酯(FAAE)如FAME)稀释的润滑油组合物的总酸值(TAN)。在本发明的一个优选实施例中,润滑油组合物的TAN根据ASTM D-664测量,其为用于测量润滑油组合物的TAN的标准测试方法。
如本文所用,术语“降低氧化稳定性的损失”意指降低当润滑油组合物用生物燃料(例如脂肪酸烷基酯(FAAE)如FAME)稀释时经历的氧化稳定性的损失。
如本文所用,术语“改善氧化稳定性”意指增加已用生物燃料(例如脂肪酸烷基酯(FAAE),如FAME)稀释的润滑油组合物的氧化的起始时间,如通过ASTM D6186测量,其为用于通过压力差示扫描量热法(pDSC)测量润滑油组合物的氧化诱导时间的标准测试方法。
在优选实施例中,与已用FAME稀释但是不含式(1)的Verkade碱的等效润滑油组合物的碱值保持性相比,由本发明的润滑油组合物提供的碱值保持性的改善%为至少5%碱值保持性的改善,更优选地至少10%碱值保持性的改善,甚至更优选地至少15%改善,尤其至少20%碱值保持性的改善。
在优选实施例中,与已用FAME稀释但是不含式(1)的Verkade碱的等效润滑油组合物的酸值相比,由本发明的润滑油组合物提供的酸值的减小%为至少5%酸值的减小,更优选地至少10%酸值的减小,甚至更优选地至少20%减小,尤其至少60%酸值的减小。
在优选实施例中,与已用FAME稀释但是不含式(1)的化合物的等效润滑油组合物的氧化稳定性相比,由本发明的润滑油组合物提供的氧化稳定性的改善%为至少20%氧化稳定性的改善,更优选地至少30%氧化稳定性的改善,甚至更优选地至少50%改善,尤其至少60%氧化稳定性的改善。
如本文所用,术语“降低的腐蚀特性”意指(i)改善用生物燃料稀释的润滑油组合物的碱值保持性,和/或(ii)改善FAME稀释的润滑组合物的酸值保持性超过不含式(1)化合物的等效FAME稀释的润滑组合物的酸值保持性。
如本文所用,术语“改善抗氧化性”意指(i)降低当润滑油组合物用生物燃料稀释时经历的氧化稳定性的损失,和/或(ii)改善FAME稀释的润滑组合物的氧化稳定性超过不含式(1)化合物的等效FAME稀释的润滑的氧化稳定性。
在本发明的优选实施例中,润滑油组合物的氧化稳定性根据ASTM D6186测量,其为用于通过压力差示扫描量热法(pDSC)测量润滑油组合物的氧化诱导时间的标准测试方法。
FAAE将通常方便地在组合物被引入内燃发动机或将涉及组合物的其它系统中之前作为共混物(即物理混合物)添加到燃料组合物。其它燃料组分和/或燃料添加剂还可在添加FAAE之前或在其之后和在组合物在燃烧系统中使用之前或在其使用期间并入组合物中。
添加的FAAE的量将取决于所讨论的碱燃料和FAAE的性质并且取决于目标十六烷值。一般来说,在所得碱燃料/FAAE混合物中FAAE的体积分数v将小于如果应用线性共混规则需要的体积分数v′,其中v′将由以下等式限定:
X=A+v′(B-A)。
体积分数v和v′必须各自具有在0和1之间的值。当进行本发明的方法时,FAAE的实际体积分数v优选地比“线性”体积分数v′低至少0.02,更优选地低至少0.05或0.08或0.1,最优选地低至少0.2、0.3或0.5,并且最多比v′低0.6或0.8的情况。按绝对值计算,实际体积分数v优选地为0.25或更小,更优选地0.2或更小,又更优选地0.15或0.1或0.07或更小。它可例如为0.01到0.25,优选地0.05到0.25,更优选地0.05或0.1到0.2。
在总燃料组合物中(或至少在碱燃料/FAAE混合物中)FAAE的浓度优选地为25%v/v或更小,更优选地20%v/v或更小,又更优选地15%v/v或10%v/v或7%v/v或更小。作为最小值,它可为0.05%v/v或更大,优选地1%v/v或更大,更优选地2%或5%v/v或更大,最优选地7%或10%v/v或更大。如本文所用,B7 FAME是指在总燃料组合物中FAME的浓度为7%v/v。如本文所用,B100 FAME是指在总燃料组合物中FAME的浓度为100%v/v或100%纯FAME。如本文所用,B0意指无FAME柴油燃料。
脂肪酸烷基酯(其中最常用于本上下文为甲酯)已经已知为可再生柴油燃料(所谓的“生物柴油”燃料)。它们含有长链羧酸分子(通常10个到22个碳原子长),每个具有附接到一端的醇分子。有机衍生油如植物油(包括回收的植物油)和动物脂肪可借助醇(通常C1到C5醇)进行酯基转移过程以形成相对应的脂肪酯,通常单烷基化。此过程(其适当地为酸催化或碱催化,如借助碱KOH)通过分离油的脂肪酸组分与其丙三醇主链将含在油中的甘油三酯转化成脂肪酸酯和游离丙三醇。
在本发明中,FAAE可为任何烷基化脂肪酸或脂肪酸的混合物。其(一种或多种)脂肪酸组分优选地衍生自生物来源,更优选地植物来源。它们可为饱和或不饱和的;如果为后者,那么它们可具有一个或多个双键。它们可为分支链或未分支链的。除了(一个或多个)酸基团-CO2H之外,适当地它们将具有10个到30个,更适当地10个到22个或12个到22个碳原子。FAAE将通常根据其来源包含不同链长度的不同脂肪酸酯的混合物。举例来说,一般可获得的油菜籽油含有棕榈酸(C16)、硬脂酸(C18)、油酸、亚油酸和亚麻酸(C18,分别具有一个、两个和三个不饱和碳-碳键)的混合物,并且有时还含有芥酸(C22)-其中,油酸和亚油酸形成主要部分。大豆油含有棕榈酸、硬脂酸、油酸、亚油酸和亚麻酸的混合物。棕榈油通常含有棕榈酸、硬脂酸和亚油酸组分的的混合物。
用于本发明的FAAE优选地衍生自天然脂肪油,例如植物油,如油菜籽油、大豆油、椰子油、葵花油、棕榈油、花生油、亚麻籽油、亚麻荠油、红花油、巴巴苏油、牛脂油或米糠油。具体地说,它可为油菜籽油、大豆油、椰子油或棕榈油的烷基酯(适当地甲酯)。
FAAE优选地为C1到C5烷基酯,更优选地甲酯、乙酯或丙酯(适当地异丙酯),又更优选地甲酯或乙酯并且具体地说甲酯。
它可例如选自由以下各项组成的群组:油菜籽甲酯(RME,也被称作油菜油甲酯或油菜甲酯)、大豆甲酯(soy methyl ester)(SME,也被称作大豆甲酯(soybean methylester))、棕榈油甲酯(POME)、椰子甲酯(CME)(具体地说未精制的CME;精制的产物基于粗产物,但是去除一些高级和低级烷基链的(通常C6、C8、C10、C16和C18)组分)及其混合物。一般来说,它可为天然或合成、精制或未精制的(“粗产物”)。
FAAE适当地遵守施加于燃料组合物的其余部分,和/或施加于添加到它的碱燃料的规范,考虑到组合物的既定用途(例如在哪个地理区域和在一年中的什么时间)。具体来说,FAAE优选地具有大于101℃的闪点(IP 34);1.9厘沲到6.0厘沲,优选地3.5厘沲到5.0厘沲的在40℃下动态粘度(IP 71);在15℃下845kg/m3到910kg/m3,优选地860kg/m3到900kg/m3的密度(IP 365,EN ISO 12185 EN ISO 3675);小于500ppm的含水量(IP 386);小于360℃的T95(95%的燃料已蒸发的温度,根据IP 123测量);小于0.8mgKOH/g,优选地小于0.5mgKOH/g的酸值(IP 139);以及每100g的燃料小于125,优选地小于120或小于115克的碘(I2)的碘值(IP 84)。它还优选地含有(例如通过NMR)小于0.2%w/w的游离甲醇,小于0.02%w/w的游离丙三醇和大于96.5%w/w酯。一般来说,对于FAAE可优选的是符合用作柴油燃料的脂肪酸甲酯的欧洲标准EN 14214。
测量的FAAE的十六烷数值(ASTM D613)适当地为55或更大,优选地58或60或65或甚至70或更大。
两种或更多种FAAE可分别地或作为预制备共混物添加到碱燃料,只要其联合效应使所得组合物的十六烷值增加以达到目标数值X。在这种情况下,如果线性共混规则应用于FAAE的两者或全部,那么两种或更多种FAAE的总量x′必须小于需要添加到碱燃料的FAAE的相同组合的量,以便实现目标十六烷值X。
FAAE优选地包含(即为或包括)RME或SEM。
FAAE可添加到燃料组合物用于除了希望增加十六烷值之外的一个或多个其它目的,例如降低生命周期温室气体排放,改善润滑性和/或降低成本。
除了一种或多种Verkade碱化合物之外,本文润滑油组合物通常包含基础油和一种或多种性能添加剂。
关于用于本文润滑油组合物的基础油不存在特定限制,并且可方便地使用各种常规矿物油、合成油以及天然衍生酯如植物油。
用于本发明的基础油可方便地包含一种或多种矿物油和/或一种或多种合成油的混合物;因此,本文术语“基础油”可涉及含有多于一种基础油的共混物。
用于本发明的润滑油组合物的合适的基础油为第I类至第III类矿物基础油(优选地第III类)、第IV类聚α烯烃(PAO)、第II类至第III类费舍尔-托普希衍生基础油(优选地第III类)、第V类基础油及其混合物。
本发明中通过“第I类”、“第II类”、“第III类”和“第IV类”和“第V类”基础油意指根据美国石油学会(API)对于类别I、II、III、IV和V的定义的润滑油基础油。这些API类别在API公布1509,第15版,附录E,2002年4月(API Publication 1509,15th Edition,AppendixE,April 2002)中定义。
矿物油包括液体石油和可通过加氢精制方法和/或脱蜡进一步精制的链烷烃、环烷烃或混合的链烷烃/环烷烃类型的溶剂处理或酸处理的矿物润滑油。
用于本文润滑油组合物的优选的基础油为费舍尔-托普希衍生基础油。费舍尔-托普希衍生基础油为本领域中已知的。通过术语“费舍尔-托普希衍生”意指基础油为,或衍生自费舍尔-托普希工艺的合成产物。费舍尔-托普希衍生基础油还可被称作GTL(气体到液体)基础油。可方便地用作在本发明的润滑油组合物中的基础油的合适的费舍尔-托普希衍生基础油为如例如在EP 0 776 959、EP 0 668 342、WO 97/21788、WO 00/15736、WO 00/14188、WO 00/14187、WO 00/14183、WO 00/14179、WO 00/08115、WO 99/41332、EP 1 029029、WO 01/18156和WO 01/57166中公开的那些。
通常,费舍尔-托普希衍生基础油的芳族物含量(适当地通过ASTM D 4629测定)将通常低于1wt.%,优选地低于0.5wt.%,并且更优选地低于0.1wt.%。适当地,基础油具有至少80wt.%,优选地至少85wt.%,更优选地至少90wt.%,又更优选地至少95wt.%并且最优选地至少99wt.%的总链烷烃含量。它适当地具有大于98wt.%的饱和含量(如通过IP-368测量)。优选地,基础油的饱和含量大于99wt.%,更优选地大于99.5wt.%。它进一步优选地具有0.5wt.%的最大正链烷烃含量。基础油还优选地具有0到小于20wt.%,更优选地0.5wt.%到10wt.%的环烷烃化合物的含量。
通常,当存在于本文润滑油组合物中时,费舍尔-托普希衍生基础油或基础油共混物具有在1mm2/s到30mm2/s(cSt),优选地1mm2/s到25mm2/s(cSt),并且更优选地2mm2/s到12mm2/s的范围内的在100℃下动态粘度(如通过ASTM D 7042测量)。优选地,费舍尔-托普希衍生基础油具有至少2.5mm2/s,更优选地至少3.0mm2/s的在100℃下动态粘度(如通过ASTM D 7042测量)。在本发明的一个实施例中,费舍尔-托普希衍生基础油具有至多5.0mm2/s,优选地至多4.5mm2/s,更优选地至多4.2mm2/s的在100℃下动态粘度(例如“GTL4”)。在本发明的另一个实施例中,费舍尔-托普希衍生基础油具有至多8.5mm2/s,至多8mm2/s的在100℃下动态粘度(例如“GTL 8”)。
另外,当存在于本文润滑油组合物中时,费舍尔-托普希衍生基础油通常具有10mm2/s到100mm2/s(cSt),优选地15mm2/s到50mm2/s的在40℃下动态粘度(如通过ASTM D7042测量)。
另外,用于本文的优选的费舍尔-托普希衍生基础油具有低于-30℃,更优选地低于-40℃,并且最优选地低于-45℃的倾点(如根据ASTM D 5950测量)。
费舍尔-托普希衍生基础油的闪点(如通过ASTM D92测量)优选地大于120℃,更优选地甚至大于140℃。
用于本文的优选的费舍尔-托普希衍生基础油具有在100到200的范围内的粘度指数(根据ASTM D 2270)。优选地,费舍尔-托普希衍生基础油具有至少125,优选地130的粘度指数。还优选的是粘度指数低于180,优选地低于150。
在费舍尔-托普希衍生基础油含有两种或更多种费舍尔-托普希衍生基础油的共混物的情况下,上述值应用于两种或更多种费舍尔-托普希衍生基础油的共混物。
本文润滑油组合物优选地包含80wt%或更大的费舍尔-托普希衍生基础油。
合成油包括烃油,如烯烃低聚物(包括聚α烯烃基础油;PAO)、二元酸酯、多元醇酯、聚亚烷基二醇(PAG)、烷基萘和脱蜡蜡质异构物。可方便地使用由壳牌集团(Shell Group)以商品名“Shell XHVI”(商标)出售的合成烃基础油。
聚α烯烃基础油(PAO)和其制造在本领域中是众所周知的。优选的可用于本发明的润滑油组合物的聚α烯烃基础油可衍生自线性C2到C32,优选地C6到C16α烯烃。用于所述聚α烯烃的特别优选的原料为1-辛烯、1-癸烯、1-十二碳烯和1-十四碳烯。
鉴于制造PAO的高成本,对于使用费舍尔-托普希衍生基础油优于PAO基础油存在强烈偏好。因此,优选地,基础油含有大于50wt.%,优选地大于60wt.%,更优选地大于70wt.%,甚至更优选地大于80wt.%。最优选地大于90wt.%费舍尔-托普希衍生基础油。在尤其优选的实施例中,不超过5wt.%,优选地不超过2wt.%的基础油不是费舍尔-托普希衍生基础油。甚至更优选的是,100wt%的基础油是基于一种或多种费舍尔-托普希衍生基础油。
相对于润滑油组合物的总量,并入本发明的润滑油组合物中的基础油的总量优选地在60wt.%到99wt.%的范围内,更优选地在65wt.%到90wt.%的范围内,并且最优选地在70wt.%到85wt.%的范围内。
通常如根据本发明使用的基础油(或基础油共混物)具有高于2.5cSt并且最多8cSt的在100℃下动态粘度(根据ASTM D445)。根据本发明的优选实施例,基础油具有在3.5cSt和8cSt之间的在100℃下动态粘度(根据ASTM D445)。在基础油含有两种或更多种基础油的共混物的情况下,优选的是,共混物具有在3.5cSt和7.5cSt之间的在100℃下动态粘度。
本文润滑组合物优选地具有低于15wt.%的Noack挥发性(根据ASTM D 5800)。通常,组合物的Noack挥发性(根据ASTM D 5800)在1wt.%和15wt.%之间,优选地低于14.6wt.%,并且更优选地低于14.0wt.%。
本发明的润滑油组合物包含具有下式(1)的一种或多种Verkade碱:
其中R1、R2和R3各自独立地选自氢和饱和或不饱和、直链或分支链C1-C22烷基。
在本发明的优选实施例中,R1、R2和R3各自独立地选自氢和饱和或不饱和、直链或分支链C1-C12烷基。合适的R1、R2和R3基团的实例为氢、CH3、CH2CH3、异-C3H7、CH2C(CH3)3、异-C4H9和CH2-p-C6H4OCH3。
在本发明的另一个优选实施例中,R1、R2和R3各自独立地选自饱和或不饱和、直链或分支链C3-C12烷基。优选地,R1、R2和R3各自独立地选自饱和、分支链C3-C12烷基。更优选地,R1、R2和R3各自独立地选自饱和、分支链C3-C6烷基。在特别优选的实施例中,其中R1、R2和R3为饱和、分支链C3或C4烷基。
在本发明的一个实施例中,R1、R2和R3相同。
用于本文的合适的Verkade碱的实例包括2,8,9-三异丁基-2,5,8,9-四氮杂-1-磷杂双环[3.3.3]十一烷、2,8,9-三异丙基-2,5,8,9-四氮杂-1-磷杂双环[3,3,3]十一烷和2,8,9-三甲基-2,5,8,9-四氮杂-1-磷杂双环[3,3,3]十一烷及其混合物。这些化合物中的全部可购自西格玛-奥德里奇公司(Sigma-Aldrich)。Verkade碱的其它实例为2,5,8,9-四氮杂-1-磷杂双环[3.3.3]十一烷、2,8-双(2-甲基丙基)、2,5,8,9-四氮杂-1-磷杂双环[3.3.3]十一烷、2-(2,2-二甲基丙基)-8-(2-甲基丙基)-9-(苯基甲基)-2,5,8,9-四氮杂-1-磷杂双环[3.3.3]十一烷。
用于本文的特别优选的Verkade碱为2,8,9-三异丁基-2,5,8,9-四氮杂-1-磷杂双环[3.3.3]十一烷。
按总润滑油组合物的重量计,式(1)的Verkade碱优选地以在0.01wt%到5wt%的范围内的量,更优选地以0.1wt%到3wt%的量,并且甚至更优选地以0.1wt%到1wt%的量存在。
除了式(1)的Verkade碱之外,本文润滑油组合物进一步包含一种或多种性能添加剂,如抗氧化剂、抗磨损添加剂、分散剂、清洁剂、高碱性清洁剂、极压添加剂、摩擦调节剂、粘度指数改善剂、倾点下降剂、金属钝化剂、腐蚀抑制剂、反乳化剂、消泡剂、密封相容剂和添加剂稀释剂基础油等。
由于本领域的普通技术人员熟悉上述和其它添加剂,所以这些在这里不进一步详细讨论。此类添加剂的具体实例在例如《Kirk-Othmer化学技术百科全书(Kirk-OthmerEncyclopedia of Chemical Technology)》第三版,第14卷,第477至526页中描述。
可方便地用于本发明的润滑油组合物中的常规抗氧化剂包括二苯胺(如可购自汽巴精化(Ciba Specialty Chemicals)的“IRGANOX L-57”),如例如公开于WO 2007/045629和EP 1 058 720 B1中,酚醛抗氧化剂等。WO 2007/045629和EP 1 058 720B1的传授内容在此以引入方式并入。
可方便地使用的抗磨损添加剂包括含锌化合物(如选自二烷基-、二芳基-和/或烷基芳基-二硫代磷酸锌的二硫代磷酸锌化合物)、含钼化合物、含硼化合物和无灰抗磨损添加剂,如经取代或未经取代的硫代磷酸,和其盐。
此类含钼化合物的实例可方便地包括二硫代氨基甲酸钼、三核钼化合物(例如如描述于WO 98/26030中)、钼的硫化物和二硫代磷酸钼。
可方便地使用的含硼化合物包括硼酸酯、硼酸化脂肪胺、硼酸化环氧化物、碱金属(或混合的碱金属或碱土金属)硼酸盐和硼酸化高碱性金属盐。
所用的分散剂优选地为无灰分散剂。无灰分散剂的合适的实例为聚丁烯丁二酰亚胺多元胺和曼尼希碱类分散剂。
所用的清洁剂优选地为高碱性清洁剂或含有例如水杨酸盐、磺酸盐和/或苯酚盐型清洁剂的清洁剂混合物。
可方便地用于本发明的润滑油组合物的粘度指数改善剂的实例包括苯乙烯-丁二烯星形共聚物、苯乙烯-异戊二烯星形共聚物和聚甲基丙烯酸酯共聚物以及结晶和非结晶类型的乙烯-丙烯共聚物(也被称作烯烃共聚物)。分散剂粘度指数改善剂可用于本发明的润滑油组合物中。然而,以组合物的总重量计,优选地根据本发明的组合物含有小于1.0wt.%,优选地小于0.5wt.%的粘度指数改善剂浓缩物(即VI改善剂加“载体油”或“稀释剂”)。最优选地,组合物不含粘度指数改善剂浓缩物。如下文所用的术语“粘度调节剂”意指将与上述术语“粘度指数改善剂浓缩物”相同。
优选地,组合物含有至少0.1wt.%的倾点下降剂。作为一实例,烷基化萘和酚醛聚合物、聚甲基丙烯酸酯、顺丁烯二酸酯/富马酸酯共聚物酯可方便地用作有效倾点下降剂。优选地使用不超过0.3wt.%的倾点下降剂。
此外,化合物如烯基丁二酸或其酯部分、苯并三唑类化合物和噻二唑类化合物可方便地作为腐蚀抑制剂用于本文润滑油组合物中。
化合物,如聚硅氧烷、二甲基聚环己烷和聚丙烯酸酯可方便地作为消泡剂用于本文润滑油组合物中。
可方便地作为密封固定或密封相容性剂用于本文润滑油组合物中的化合物包括例如可商购的芳香族酯。
本文润滑油组合物可方便地通过将式(1)的Verkade碱与基础油和一种或多种附加性能添加剂掺合制备。
上述性能添加剂以润滑油组合物的总重量计通常以在0.01wt.%到35.0wt.%的范围内的量,优选地以润滑油组合物的总重量计,以在0.05wt.%到25.0wt.%,更优选地1.0wt.%到20.0wt.%的范围内的量存在。
优选地,组合物含有至少8.0wt.%,优选地至少10.0wt.%,更优选地至少11.0wt%的包含抗磨损添加剂、金属清洁剂、无灰分散剂、抗氧化剂、摩擦改质剂和消泡剂的添加剂包。
本文润滑油组合物可为所谓的的“低SAPS”(SAPS=硫酸化灰分、磷和硫)、“中SAPS”或“常规SAPS”调配物。
对于乘用车马达油(PCMO)发动机油,上述范围意指:
-分别最多0.5wt.%,最多0.8wt.%并且最多1.5wt.%的硫酸化灰分含量(根据ASTM D 874);
-分别最多0.05wt.%,最多0.08wt.%并且通常最多0.1wt.%的磷含量(根据ASTMD 5185);以及
-分别最多0.2wt.%,最多0.3wt.%并且最多0.5wt.%的硫含量(根据ASTM D5185)。
对于重负荷柴油发动机油,上述范围意指:
-分别最多1wt.%,最多1wt.%并且最多2wt.%的硫酸化灰分含量(根据ASTM D874);
-分别最多0.08wt.%(低SAPS),并且最多0.12wt.%(中SAPS)的磷含量(根据ASTMD 5185);以及
-分别最多0.3wt.%(低SAPS),并且最多0.4wt.%(中SAPS)的硫含量(根据ASTM D5185)。
参照以下实例来描述本发明,这些实例并不意欲以任何方式限制本发明的范围。
实例
比较实例1(油A)为可商购的5W-30重负荷柴油发动机油,其具有3.5的在150℃下(如通过ASTM D5481测量)的HTHS(高温高剪切)并且含有16wt%的添加剂(其包括水杨酸盐清洁剂、分散剂、锌类抗磨剂、胺化和酚醛抗氧化剂的混合物以及腐蚀抑制剂),最多10wt%的聚合物粘度调节剂和剩余部分第III类基础油的共混物。
比较实例2(油B)为95wt%油A+5wt%B7 FAME的共混物。
比较实例3(油C)为90wt%油A+10wt%B100 FAME的共混物。
实例1为99.5wt%比较实例1(油A)与0.5wt%的Verkade碱(2,8,9-三异丁基-2,5,8,9-四氮杂-1-磷杂双环[3.3.3]十一烷,可商购自西格玛-奥德里奇公司)的共混物。实例1通过使用常规润滑共混程序将比较实例1与Verkade碱混合获得。
实例2为99.5wt%比较实例2(油B)与0.5wt%的Verkade碱(2,8,9-三异丁基-2,5,8,9-四氮杂-1-磷杂双环[3.3.3]十一烷,可商购自西格玛-奥德里奇公司)的共混物。实例2通过使用常规润滑共混程序将比较实例2与所述Verkade碱混合获得。
实例3为99.5wt%比较实例3(油C)与0.5wt%的Verkade碱(2,8,9-三异丁基-2,5,8,9-四氮杂-1-磷杂双环[3.3.3]十一烷,可商购自西格玛-奥德里奇公司)的共混物。实例3通过使用常规润滑共混程序将比较实例3与所述Verkade碱混合获得。
为了测量实例和比较实例的氧化稳定性,润滑油组合物中的每种进行以下氧化测试。
氧化测试
在此测试中,曲轴箱润滑剂的氧化通过在无金属催化剂的情况下将空气泡鼓进入加热的油样品来模拟。将300g油样品称量到玻璃氧化室中。打开加热,并且使加热块单元达到期望的温度(155℃)。将所述室放入加热单元中并且连接空气起泡器。打开气流并且将空气调节到期望水平(200cc/min每管)。将恒定加热和气流维持测试的持续时间(3至7天)。定期(通常每24小时)抽出样品用于需要的测试。样品中的每个进行ASTM D-664,其为用于测量总酸值(TAN)的标准测试方法。此外,样品中的每个进行ASTM D-2896和ASTM D-4739,其测量总碱值(TBN)。这些测试测量的结果在表1中陈述。
表1
讨论
从在表1中的结果可看出,通过用5%B7 FAME稀释比较实例1的润滑组合物(油B),看出在测试的持续时间(测试开始到第4天)内TBN的减小(通过ASTM D-2896和ASTM D-4739两者)。对于用10%B100 FAME稀释比较实例1的润滑组合物(油C),在测试的持续时间内TBN的进一步减小(通过ASTM D-2896和ASTM D-4739两者)。另外,在第4天测试结束时油B和油C的TAN比油A高得多。在测试结束时在油B和油C两者中TBN的减小和TAN的增加指示酸形成增加。
在表1中的结果还表明以以0.5wt%的处理比率将Verkade碱添加在润滑组合物中(实例1、实例2和实例3)提供在测试开始时TBN的提高(通过ASTM D-2896和ASTM D-4739两者)。
实例1表明以0.5wt%的处理比率使用Verkade碱将在比较实例1中的润滑组合物的TBN保持性在测试的持续时间(测试开始到第4天)内提高了9%至14%。此外,从测试开始到第4天TAN的显著降低(>10%)见于其中添加0.5wt%的Verkade碱实例1中,指示降低酸形成并且因此降低腐蚀性。
实例2表明甚至在存在5wt%B7 FAME的情况下,以0.5wt%的处理比率使用Verkade碱将在比较实例2中的润滑组合物的TBN保持性提高>7%(测试开始到第3天)。同样,从测试开始到第3天TAN的降低(>18%)见于其中添加0.5wt%的Verkade碱的实例2中。在第4天,保持TBN和TAN并且类似于比较实例2。
实例3表明在存在10wt%B100 FAME的情况下,以0.5wt%的处理比率使用Verkade碱将TBN保持性提高>9%,并且在测试开始处TAN降低了>60%。通过测试的持续时间,虽然实例3的TBN类似于比较实例3,但是实例3的TAN仍降低>8%。这指示在实例3中的润滑油组合物的TBN保持能力,同时维持低TAN并且因此低的导致增加腐蚀性的酸形成。虽然不希望受理论限制,但是缺少TBN保持的可见提高可归因于以较高处理比率使用Verkade碱的溶解性限制,然而本领域的普通技术人员应认识到这可通过例如调节用于制备润滑组合物温度来修正。
Claims (17)
2.根据权利要求1所述的润滑油组合物,其中R1、R2和R3各自独立地选自饱和或不饱和、直链或分支链C3-C12烷基。
3.根据权利要求1所述的润滑油组合物,其中R1、R2和R3各自独立地选自饱和或不饱和、分支链C3-C12烷基。
4.根据权利要求1所述的润滑油组合物,其中R1、R2和R3各自独立地选自饱和、分支链C3-C12烷基。
5.根据权利要求1所述的润滑油组合物,其中R1、R2和R3各自独立地选自饱和、分支链C3-C6烷基。
6.根据权利要求1所述的润滑油组合物,其中R1、R2和R3相同。
7.根据权利要求6所述的润滑油组合物,其中R1、R2和R3为饱和、分支链C3或C4烷基。
8.根据权利要求1到7中任一项所述的润滑油组合物,其中按所述润滑油组合物的重量计,所述式(1)化合物以0.01wt%到5wt%的含量存在。
9.根据权利要求1到7中任一项所述的润滑油组合物,其中按所述润滑油组合物的重量计,所述式(1)化合物以0.1wt%到3wt%的含量存在。
10.根据权利要求1到7中任一项所述的润滑油组合物,其中按所述润滑油组合物的重量计,所述式(1)化合物以0.1wt%到1wt%的含量存在。
11.根据权利要求1到7中任一项所述的润滑油组合物,其中以所述润滑油组合物的总重量计,所述润滑油组合物被至少0.3wt%的生物燃料或其分解产物,或其混合物污染。
12.根据权利要求1到7中任一项所述的润滑油组合物,其中所述基础油包含费舍尔-托普希衍生基础油。
13.根据权利要求1到7中任一项所述的润滑油组合物,其另外包含性能添加剂。
14.根据权利要求1到7中任一项所述的润滑油组合物,其中所述润滑油组合物为重负荷柴油发动机油。
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- 2015-12-14 RU RU2017124805A patent/RU2683646C2/ru active
- 2015-12-14 US US15/536,166 patent/US10160927B2/en active Active
- 2015-12-14 CN CN201580068289.3A patent/CN107001965B/zh active Active
- 2015-12-14 BR BR112017012857A patent/BR112017012857B8/pt active IP Right Grant
- 2015-12-14 JP JP2017533323A patent/JP6698660B2/ja active Active
- 2015-12-14 EP EP15808432.7A patent/EP3234077B1/en active Active
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Patent Citations (2)
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WO2013127054A1 (en) * | 2012-02-27 | 2013-09-06 | 3M Innovative Properties Company | Basic compositions including inorganic oxide nanoparticles and an organic base, coated substrates, articles, and methods |
CN103881789A (zh) * | 2012-12-21 | 2014-06-25 | 雅富顿化学公司 | 含摩擦改性剂和清净剂的添加剂组合物 |
Also Published As
Publication number | Publication date |
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US20170362529A1 (en) | 2017-12-21 |
RU2017124805A (ru) | 2019-01-23 |
RU2017124805A3 (zh) | 2019-02-06 |
US10160927B2 (en) | 2018-12-25 |
JP6698660B2 (ja) | 2020-05-27 |
EP3234077B1 (en) | 2018-10-10 |
BR112017012857A2 (pt) | 2017-12-26 |
WO2016096758A1 (en) | 2016-06-23 |
BR112017012857B8 (pt) | 2022-05-10 |
JP2017538843A (ja) | 2017-12-28 |
CN107001965A (zh) | 2017-08-01 |
BR112017012857B1 (pt) | 2021-10-13 |
EP3234077A1 (en) | 2017-10-25 |
RU2683646C2 (ru) | 2019-04-01 |
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