CN117128110A - 用于控制微粒排放的发动机油配制物 - Google Patents
用于控制微粒排放的发动机油配制物 Download PDFInfo
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- CN117128110A CN117128110A CN202310597318.1A CN202310597318A CN117128110A CN 117128110 A CN117128110 A CN 117128110A CN 202310597318 A CN202310597318 A CN 202310597318A CN 117128110 A CN117128110 A CN 117128110A
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- Prior art keywords
- calcium
- magnesium
- gasoline
- particulate emissions
- lubricating composition
- Prior art date
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- 239000011777 magnesium Substances 0.000 claims abstract description 112
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 112
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- 230000002401 inhibitory effect Effects 0.000 description 1
- GAPFWGOSHOCNBM-UHFFFAOYSA-N isopropyl nitrate Chemical compound CC(C)O[N+]([O-])=O GAPFWGOSHOCNBM-UHFFFAOYSA-N 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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- 229910052744 lithium Inorganic materials 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
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- 229940098779 methanesulfonic acid Drugs 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- FROFFPBBKVQUFE-UHFFFAOYSA-N n'-(2,2-dimethylpropyl)propane-1,3-diamine Chemical compound CC(C)(C)CNCCCN FROFFPBBKVQUFE-UHFFFAOYSA-N 0.000 description 1
- NPMAKXHZQFPWHU-UHFFFAOYSA-N n'-tert-butylpropane-1,3-diamine Chemical compound CC(C)(C)NCCCN NPMAKXHZQFPWHU-UHFFFAOYSA-N 0.000 description 1
- LVZUNTGFCXNQAF-UHFFFAOYSA-N n-nonyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCCC)C1=CC=CC=C1 LVZUNTGFCXNQAF-UHFFFAOYSA-N 0.000 description 1
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- YHVAHDISAMDYQA-UHFFFAOYSA-N nitric acid;octane Chemical compound O[N+]([O-])=O.CCCCCCCC YHVAHDISAMDYQA-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- CMNNRVWVNGXINV-UHFFFAOYSA-N nonyl nitrate Chemical compound CCCCCCCCCO[N+]([O-])=O CMNNRVWVNGXINV-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
- QCOKASLKYUXYJH-UHFFFAOYSA-N octan-2-yl nitrate Chemical compound CCCCCCC(C)O[N+]([O-])=O QCOKASLKYUXYJH-UHFFFAOYSA-N 0.000 description 1
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- 229940049964 oleate Drugs 0.000 description 1
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- 150000002902 organometallic compounds Chemical class 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical class OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
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- RWRBSYOTDDOXKC-UHFFFAOYSA-N pentan-2-yl nitrate Chemical compound CCCC(C)O[N+]([O-])=O RWRBSYOTDDOXKC-UHFFFAOYSA-N 0.000 description 1
- WQZKKVJFBZPJSU-UHFFFAOYSA-N pentan-3-yl nitrate Chemical compound CCC(CC)O[N+]([O-])=O WQZKKVJFBZPJSU-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
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- NQHJWFYVHSKTLX-UHFFFAOYSA-N phosphoric acid;toluene Chemical compound OP(O)(O)=O.CC1=CC=CC=C1 NQHJWFYVHSKTLX-UHFFFAOYSA-N 0.000 description 1
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- 239000001205 polyphosphate Substances 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
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- 235000007686 potassium Nutrition 0.000 description 1
- OTRMXXQNSIVZNR-UHFFFAOYSA-N prop-2-enyl nitrate Chemical compound [O-][N+](=O)OCC=C OTRMXXQNSIVZNR-UHFFFAOYSA-N 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
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- 229940095064 tartrate Drugs 0.000 description 1
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
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- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 1
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- AZAKMLHUDVIDFN-UHFFFAOYSA-N tert-butyl nitrate Chemical compound CC(C)(C)O[N+]([O-])=O AZAKMLHUDVIDFN-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- JZALLXAUNPOCEU-UHFFFAOYSA-N tetradecylbenzene Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1 JZALLXAUNPOCEU-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 1
- DPNUIZVZBWBCPB-UHFFFAOYSA-J titanium(4+);tetraphenoxide Chemical class [Ti+4].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 DPNUIZVZBWBCPB-UHFFFAOYSA-J 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical class [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- VQOXUMQBYILCKR-UHFFFAOYSA-N tridecaene Natural products CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- OPSWAWSNPREEFQ-UHFFFAOYSA-K triphenoxyalumane Chemical compound [Al+3].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 OPSWAWSNPREEFQ-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
- C10M135/10—Sulfonic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/027—Neutral salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
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Abstract
通过用所选钙和镁碱性润滑油组合物润滑汽油发动机来减少来自该汽油发动机的微粒排放的方法。
Description
技术领域
本公开涉及减少来自汽油发动机的微粒排放的方法,并且特别是减少来自用所选润滑组合物润滑的汽油发动机的微粒排放的方法。
背景技术
全球范围内的监管和/或环境组织经常对机动车排放标准进行密切审查。目前正在制定标准,以不断降低各种类型的排放。在一些情况下,机动车微粒排放限制正在降低,并且现在包括对来自汽油/火花点火发动机以及其他发动机技术的微粒排放的限制。在汽油或火花点火发动机中,微粒排放限制的降低有时会得到解决,部分原因是机动车硬件设计的改善。例如,可注意到喷射技术,以改善燃烧,从而导致减少排放。然而,如果不进行优化,则喷射器结焦可能会导致不利的燃料喷射和微粒排放增加。
常规化学计量汽油发动机通常具有低微粒排放;然而,在某些情况下,汽油发动机可能具有增加的微粒排放,这取决于发动机类型、燃料组成、发动机构造和/或许多其他因素。在一些情况下,汽油微粒过滤器(GPF)可用于发动机以减少微粒排放,但微粒排放仍可受许多因素影响,包括过滤器寿命和/或性能、燃料组成和/或发动机特性、寿命或设置。因此,即使对于汽油发动机或甚至配备有GPF的汽油发动机,流体性质仍可对排气管排放具有有意义的影响。
发明内容
本文公开了减少来自汽油发动机的微粒排放的方法。在实施方案中,该方法包括在汽油发动机中燃烧汽油组合物,其中该汽油发动机用包含至少约1500ppm的钙和不超过约500ppm的镁的润滑组合物润滑。
在这些方法的其他实施方案中,任选的特征、方法步骤和/或限制可以任何组合来组合。此类任选特征、方法步骤或方法的限制可包括以下项中的一者或多者:其中在润滑组合物中由洗涤添加剂提供的钙与镁的重量比为约10∶1至约300∶1;并且/或者其中与用具有混合的钙和镁金属组合物的润滑组合物润滑时通过颗粒物数目测量的来自汽油发动机中汽油组合物的燃烧的微粒排放相比,通过颗粒物数目测量的来自汽油发动机中汽油组合物的燃烧的微粒排放减少,其中在该润滑组合物中由洗涤添加剂提供的钙与镁的重量比为约2:1至小于约10:1,并且其中根据US06驱动循环在汽油组合物的燃烧期间测量颗粒物数目;并且/或者其中汽油发动机配备有汽油微粒过滤器,并且在一个US06驱动循环之后微粒排放减少,而与汽油微粒过滤器的任何先前的灰分和/或烟灰积聚无关;并且/或者该方法进一步包括在执行US06驱动循环时测量微粒排放作为颗粒物数目;并且/或者其中根据黄金颗粒测量系统(GPMS)测量颗粒物数目;并且/或者其中汽油发动机是配备有汽油微粒过滤器的混合电动发动机;并且/或者其中润滑组合物包含约1,800ppm至约3,000ppm的钙和约10ppm至约100ppm的镁;并且/或者其中润滑组合物包含约3,000ppm至约5,000ppm的总矿物,并且其中总矿物的约40重量%至约60重量%为钙且总矿物的不超过约1重量%为镁;并且/或者其中润滑组合物的总矿物进一步包含选自钼、磷、锌、硼或它们的组合的矿物;并且/或者其中润滑组合物的总矿物包含约1重量%至约5重量%的钼、约15重量%至约15重量%的磷、约15重量%至约30重量%的锌和/或约1重量%至约10重量%的硼;和/或其中润滑组合物进一步包含一种或多种选自粘度指数改善剂、分散剂、消泡添加剂、抗氧化剂、抗磨添加剂、摩擦改性剂、倾点分散剂、洗涤剂或它们的组合的添加剂;并且/或者其中钙由中性至高碱性磺酸钙、酚钙或水杨酸钙中的一者或多者提供;并且/或者其中钙由总碱值为200mg KOH/g至500mg KOH/g的高碱性磺酸钙提供;并且/或者其中镁由选自磺酸镁、酚镁和水杨酸镁的洗涤添加剂提供;并且/或者其中汽油组合物包含约10ppm至约200ppm的曼尼希洗涤剂;并且/或者进一步包括测量贯穿一个US06驱动循环的颗粒物数目;并且/或者其中汽油发动机配备有汽油微粒过滤器;并且/或者其中润滑组合物包含至少约1,800ppm的钙和不超过约100ppm的镁;并且/或者其中润滑组合物包含至少约2,000ppm的钙和不超过约50ppm的镁;并且/或者其中润滑组合物包含至少约2,000ppm的钙和不超过约25ppm的镁;并且/或者其中在润滑组合物中由洗涤添加剂提供的钙与镁的重量比为约150:1至约300:1。
附图说明
图1是在基于EPA补充FTP驱动循环-US06的整个测试方案的机动车速度的图。
图2是在US06驱动循环测试方案中本发明方法的瞬时颗粒物数目、机动车速度和累积燃料经济性的图。
图3是将本发明方法与混合的钙/镁比较方法比较的几个US06驱动循环的颗粒物数目的柱状图;并且
图4是颗粒物数目的统计箱线图。
具体实施方式
在本公开中,使用一系列标准机动车测试驱动循环,诸如但不限于US06驱动循环(或等同循环),评价润滑组合物的矿物和/或金属含量对汽油发动机和包括汽油微粒过滤器(GPF)的汽油发动机的排气管微粒排放的影响。令人惊讶地,在这种驱动循环测试中,就微粒数目方面而言排放质量可立即得到改善,这是用于润滑汽油发动机的润滑剂化学品的所选成分的影响。由于与发动机或燃料的任何润滑剂化学品接触的时间短,由于过滤器(如果包括在机动车中的话)中有限的灰分积聚,以及/或者由于润滑剂和燃料之间的少量接触用于将润滑剂组分转移到燃烧室以在驱动循环测试期间提供任何效果,因此这种瞬时排放改善将是不可预期的。尽管测试时间短,但不管GPF的存在、GPF的预先存在条件和/或用于GPF的三效催化剂(TWC)的条件如何,选择包括特定的钙和镁润滑剂组合物的发动机润滑剂配制物就微粒物数目方面而言出乎意料地改善了排气管排放。
在一种方法或实施方案中,本文描述了通过在汽油发动机中燃烧汽油组合物来减少来自汽油发动机(诸如具有或不具有汽油微粒过滤器(GPF)的进气口喷射或直接喷射汽油发动机)的微粒排放的方法,其中汽油发动机用润滑组合物润滑,该润滑组合物包含具有至少约1500ppm的钙的所选钙和镁矿物分布以及具有不超过约500ppm的镁的贫镁矿物分布。润滑组合物中可由润滑组合物中的洗涤添加剂提供的钙与镁的重量比为约10:1至约300:1,并且其中与用具有混合的钙和镁金属组合物的润滑组合物润滑时通过颗粒物数目测量的来自汽油发动机中汽油组合物的燃烧的微粒排放相比,通过颗粒物数目测量的来自汽油发动机中汽油组合物的燃烧的微粒排放减少,其中在该润滑组合物中由洗涤添加剂提供的钙与镁的重量比为约2:1至小于约10:1。优选地,根据US06驱动循环(或等效循环)在汽油组合物分燃烧期间测量颗粒物数目,并且其中根据黄金颗粒测量系统(GPMS)或等效测量方案测量颗粒物数目。本文使用的US06补充联邦测试程序(SFTP)是由EPA开发的,旨在解决FTP-75测试循环在表现激进、高速和/或高加速驱动行为、快速波动以及启动后的驱动行为方面可能存在的缺陷。
在进一步的方法或实施方案中,用于降低本文排气管排放的所选钙和镁润滑组合物可包含至少约1,500ppm的钙或约1,800ppm至约3,000ppm的钙和小于约500ppm的镁或小于100ppm的镁(诸如约10ppm至约100ppm的镁),或者润滑组合物可包含约3,000ppm至约5,000ppm的总矿物(包括如下文所定义的金属和其他矿物),并且其中总矿物的约40重量%至约60重量%为钙,并且总矿物的不超过约1重量%(优选不超过约0.5重量%,并且更优选不超过0.25重量%)为镁。降低排气管排放的润滑组合物中的总矿物可包含(除了钙和残留水平的镁之外)选自金属钼和/或锌的矿物以及包括磷和/或硼的其他矿物或者此类矿物和金属的任何组合。例如并且在一些方法中,用于降低排气管排放的润滑组合物的总矿物除了上述钙和镁之外还包含约1重量%至约5重量%的钼、约15重量%至约15重量%的磷、约15至约30重量%的锌和约1重量%至约10重量%的硼(其中重量%基于矿物的总量)。如果需要,润滑组合物可进一步包含一种或多种选自粘度指数改善剂、分散剂、消泡添加剂、抗氧化剂、抗磨添加剂、摩擦改性剂、倾点分散剂、洗涤剂或它们的组合的其他添加剂。
本文发现了所选钙和镁润滑组合物,其在润滑汽油发动机时在US06驱动循环测试的背景下产生了瞬时排放改善的方法。如下文更详细论述的,本发明润滑组合物具有至少约1500ppm的钙、至少约1800ppm的钙或至少约2000ppm的钙和不超过500ppm的镁、不超过200ppm的镁、不超过100ppm的镁、不超过50ppm的镁、不超过25ppm的镁、不超过15ppm的镁、不超过10ppm的镁,其中钙与镁的比率范围为大于约10∶1至约300∶1,或者在其他方法中为约150∶1至约300∶1,或约200∶1至约300∶1(或在此类指出的端点内的任何其他范围)。优选地,钙由润滑剂组合物中的洗涤添加剂提供,诸如中性至高碱性磺酸钙、酚钙和/或水杨酸钙。镁如果存在的话,则也可由洗涤添加剂提供,包括磺酸镁、酚镁和/或水杨酸镁。合适的润滑组合物在下文进一步论述。
如以下示例中更多论述的,使用US06驱动循环作为基础开发了一种测试方案,并且该测试方案包括冷启动(在8小时浸泡或优选过夜浸泡之后),随后进行多次US06驱动循环,其中在每个后续循环之间进行热启动(一小时浸泡)。每次测试花费大约6小时。当测试需要换油时进行两次油冲洗。通过根据黄金微粒测量系统(GPMS)或等效系统测量的颗粒物数目来测量排放,并且在一些情况下,当用本文的所选润滑剂润滑发动机时,通过每个驱动循环的瞬时颗粒物数目测量具有不大于1.5×107个微粒,其中粒径在每立方厘米约20nm至约4μm之间。合适的测量设备可以是发动机排气冷凝颗粒物计数器(EECPC),型号3790或等同物(TSI Incorporated)和/或发动机排气颗粒物筛分器(EEPS),型号3090或等同物(TSIIncorporated)。
烃燃料
本文中的所谓“燃料”意指适用于燃烧系统操作的一种或多种烃燃料,包括汽油、无铅发动机和航空汽油以及所谓的再配制汽油,这些再配制汽油通常含有汽油沸程的烃和燃料可溶的含氧掺合剂,诸如醇、醚和其他合适的含氧有机化合物。合适的燃料包括含铅或无铅电动机汽油以及所谓的重新配制的汽油,其通常含有汽油沸点范围的烃和燃料可溶性含氧共混剂(“含氧物”),例如醇、醚和其他合适的含氧有机化合物。优选地,燃料为在汽油沸点范围内沸腾的烃的混合物。此燃料可由直链或支链链烷烃、环链烷烃、烯烃、芳香族烃或这些的任何混合物组成。汽油可衍生自直馏石脑油、聚合物汽油和天然汽油或来自沸点在约80℉至约450℉范围内的催化重整原料。汽油的辛烷值不重要,并且任何常规汽油可用于本发明的实践中。
适用于的含氧化合物包括甲醇、乙醇、异丙醇、叔丁醇、混合的C1至C5醇、甲基叔丁基醚、叔戊基甲基醚、乙基叔丁基醚和混合醚。当使用含氧化合物时,其在基础燃料中可以高达约90体积%并且优选仅高达约25体积%的量存在。
燃料可根据具体应用的需要包括多种添加剂,并且可包括辛烷增强剂、洗涤剂等添加剂。辛烷增强剂通常包括有机金属辛烷增强剂和其他辛烷增强剂。这些其他辛烷增强剂包括醚和芳族胺。
一组有机金属辛烷增强剂可含有锰。含锰的有机金属化合物的示例是三羰基锰化合物。可使用的合适的三羰基锰化合物包括三羰基环戊二烯基锰、三羰基甲基环戊二烯基锰、三羰基二甲基环戊二烯基锰、三羰基三甲基环戊二烯基锰、三羰基四甲基环戊二烯基锰、三羰基五甲基环戊二烯基锰、三羰基乙基环戊二烯基锰、三羰基二乙基环戊二烯基锰、三羰基丙基环戊二烯基锰、三羰基异丙基环戊二烯基锰、三羰基叔丁基环戊二烯基锰、三羰基辛基环戊二烯基锰、三羰基十二烷基环戊二烯基锰、三羰基乙基甲基环戊二烯基锰、三羰基茚基锰等,包括两种或更多种此类化合物的混合物。在一个示例中是在室温下为液体的三羰基环戊二烯基锰,诸如三羰基甲基环戊二烯基锰、三羰基乙基环戊二烯基锰、三羰基环戊二烯基锰和三羰基甲基环戊二烯基锰的液体混合物、三羰基甲基环戊二烯基锰和三羰基乙基环戊二烯基锰的混合物等。
一组有机金属辛烷增强剂的另一个示例是含铁的一组。这些含铁化合物包括二茂铁。
硝酸酯辛烷增强剂(通常也称为点火促进剂)包含取代或未取代的脂族或环脂族醇的硝酸酯,其可以是一元或多元的。有机硝酸酯可以是取代或未取代的烷基或环烷基硝酸酯,其具有至多约十个碳原子,例如二至十个碳原子。烷基基团可以是直链或支链(或直链和支链烷基基团的混合物)。适合用作硝酸酯燃烧改善剂的硝酸酯化合物的具体示例包括但不限于以下项:正丁基硝酸酯、乙基硝酸酯、正丙基硝酸酯、异丙基硝酸酯、烯丙基硝酸酯、正丁基硝酸酯、异丁基硝酸酯、仲丁基硝酸酯、叔丁基硝酸酯、正戊基硝酸酯、异戊基硝酸酯、2-戊基硝酸酯、3-戊基硝酸酯、叔戊基硝酸酯、正己基硝酸酯、正庚基硝酸酯、仲庚基硝酸酯、正辛基硝酸酯、2-乙基己基硝酸酯、仲辛基硝酸酯、正壬基硝酸酯、正癸基硝酸酯、环戊基硝酸酯、环己基硝酸酯、甲基环己基硝酸酯、异丙基环己基硝酸酯等。烷氧基取代的脂族醇的硝酸酯也是合适的,诸如2-乙氧基乙基硝酸酯、2-(2-乙氧基乙氧基)乙基硝酸酯、1-甲氧基丙基-2-硝酸酯和4-乙氧基丁基硝酸酯,以及二醇硝酸酯诸如1,6-六亚甲基二硝酸酯等。例如,还包括具有五至十个碳原子的烷基硝酸酯和二硝酸酯,并且最特别地包括伯戊基硝酸酯的混合物、伯己基硝酸酯的混合物、以及辛基硝酸酯诸如2-乙基己基硝酸酯。
其他补充添加剂还可包括分散剂/洗涤剂、抗氧化剂、载液、金属钝化剂、染料、标记物、腐蚀抑制剂、杀生物剂、抗静电添加剂、减阻剂、破乳剂、乳化剂、除雾剂、防冰添加剂、防爆添加剂、防阀座凹陷添加剂、润滑添加剂、表面活性剂、助燃剂以及它们的混合物。
一类洗涤剂是曼尼希碱洗涤剂。适用于本文中的燃料组合物的曼尼希碱洗涤剂包括高分子量烷基取代的羟基芳香族化合物、醛和胺的反应产物。如果使用的话,燃料组合物可包含约10ppm至约1000ppm的曼尼希碱洗涤剂(优选约10ppm至约200ppm,或更优选约45ppm至约200ppm)。
在一种方法中,如使用聚苯乙烯作为参考通过凝胶渗透色谱法(GPC)测定,羟基芳香族化合物的苯环上的高分子量烷基取代基可衍生自数均分子量(Mn)为约500至约3000、优选约700至约2100的聚烯烃。如使用聚苯乙烯作为参考通过GPC测定,聚烯烃的多分散性(重均分子量/数均分子量)还可为约1至约4(在其他情况下为约1至约2)。
羟基芳香族化合物的烷基化通常在烷基化催化剂存在下在约0℃至约200℃、优选0℃至100℃的范围内的温度下进行。酸性催化剂通常用于促进傅里德-克拉夫茨(Friedel-Crafts)烷基化。用于商业生产的典型催化剂包括硫酸、BF3、苯酚铝、甲磺酸、阳离子交换树脂、酸性粘土和改性沸石。
适用于形成被高分子量烷基取代的羟基芳香族化合物的聚烯烃包括聚丙烯、聚丁烯、聚异丁烯、丁烯和/或丁烯和丙烯的共聚物、丁烯和/或异丁烯和/或丙烯的共聚物以及一种或多种与其可共聚的单烯烃共聚单体(例如,乙烯、1-戊烯、1-己烯、1-辛烯、1-癸烯等),其中共聚物分子含有至少50重量%的丁烯和/或异丁烯和/或丙烯单元。与丙烯或此类丁烯聚合的共聚单体可以为脂肪族的,并且还可以含有非脂肪族基团,例如苯乙烯、邻甲基苯乙烯、对甲基苯乙烯、二乙烯基苯和其类似物。因此,在任何情况下,用于形成被高分子量烷基取代的羟基芳香族化合物的所得聚合物和共聚物基本上为脂肪族烃聚合物。
聚丁烯为优选的。除非本文另外说明,否则术语“聚丁烯”以一般含义使用以包括由“纯的”或“基本上纯的”1-丁烯或异丁烯制成的聚合物,以及由1-丁烯、2-丁烯和异丁烯中的两者或全部三者的混合物制成的聚合物。此类聚合物的商业等级也可含有少量的其他烯烃。具有相对高比例的具有末端亚乙烯基的聚合物分子的所谓高反应性聚异丁烯也适用于形成长链烷基化苯酚反应物。合适的高反应性聚异丁烯包括那些聚异丁烯,其包含至少约20%、优选至少50%并且更优选至少70%的反应性更高的甲基亚乙烯基异构体。合适的聚异丁烯包括使用BF3催化剂制备的聚异丁烯。其中甲基亚乙烯基异构体占总组合物的高百分比的此类聚异丁烯的制备描述于US 4,152,499和US 4,605,808中,其两者都以引用的方式并入本文中。
曼尼希洗涤剂可以由高分子量烷基酚或烷基甲酚制成。然而,可以使用其他酚类化合物,包括间苯二酚、对苯二酚、儿茶酚、羟基二苯基、苯甲基酚、苯乙基酚、萘酚、甲苯基萘酚等等的被高分子量烷基取代的衍生物。优选用于制备曼尼希洗涤剂的为聚烷基酚和聚烷基甲酚反应物,例如聚丙基酚、聚丁基酚、聚丙基甲酚和聚丁基甲酚,其中如通过使用聚苯乙烯作为参考的GPC测量,烷基的数均分子量为约500至约2100,而最优选的烷基为衍生自聚异丁烯的聚丁基,如通过使用聚苯乙烯作为参考的GPC测量,所述聚丁基的数均分子量在约700至约1300的范围内。
被高分子量烷基取代的羟基芳香族化合物的优选构形为对位取代的单烷基酚或对位取代的单烷基邻甲酚的构形。然而,可以采用在曼尼希缩合反应中容易反应的任何羟基芳香族化合物。因此,由仅具有一个环烷基取代基或两个或更多个环烷基取代基的羟基芳香族化合物制成的曼尼希产物适用于本发明。长链烷基取代基可含有一些残余不饱和基团,但通常为基本上饱和的烷基。
代表性胺反应物包括但不限于在分子中具有至少一个适当反应性伯氨基或仲氨基的亚烷基多胺。例如羟基、氰基、酰胺基等的其他取代基可以存在于多胺中。在优选实施方案中,亚烷基多胺为聚乙烯多胺。合适的亚烷基多胺反应物包括乙二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺和此类胺的混合物,其氮含量对应于式H2N--(A-NH--)nH的亚烷基多胺,其中这一式中的A为二价乙烯基或者丙烯基,并且n为1至10的整数,优选为1至4。亚烷基多胺可以通过使氨与如二氯烷烃的二卤代烷烃反应获得。
胺也可以为在分子中具有一个伯氨基或仲氨基和至少一个叔氨基的脂肪族二胺。合适的多胺的实例包括N,N,N",N"-四烷基二亚烷基三胺(两个末端叔氨基和一个中心仲氨基)、N,N,N',N"-四烷基三亚烷基四胺(一个末端叔氨基、两个内部叔氨基和一个末端伯氨基)、N,N,N',N",N'"-五烷基三亚烷基四胺(一个末端叔氨基、两个内部叔氨基和一个末端仲氨基)、N,N-二羟烷基-α-、ω-亚烷基二胺(一个末端叔氨基和一个末端伯氨基)、N,N,N'-三羟烷基-α、ω-亚烷基二胺(一个末端叔氨基和一个末端仲氨基)、三(二烷氨基烷基)氨基烷基甲烷(三个末端叔氨基和一个末端伯氨基)和类似的化合物,其中所述烷基相同或不同,并且通常各自含有不超过约12个碳原子,并且其优选各自含有1至4个碳原子。最优选地,这些烷基为甲基和/或乙基。优选的多胺反应物为N,N-二烷基-α、ω-亚烷基二胺,例如在亚烷基中具有3至约6个碳原子并且在每个烷基中具有1至约12个碳原子的那些,所述烷基最优选为相同的,但可以为不同的。最优选的为N,N-二甲基-1,3-丙二胺和N-甲基哌嗪。
具有一个可参与曼尼希缩合反应的反应性伯氨基或仲氨基和至少一个不能以任何显著程度直接参与曼尼希缩合反应的空间位阻氨基的多胺的示例包括N-(叔丁基)-1,3-丙二胺、N-新戊基-1,3-丙二胺-、N-(叔丁基)-1-甲基-1,2-乙二胺、N-(叔丁基)-1-甲基-1,3-丙二胺和3,5-二(叔丁基)氨基乙基哌嗪。
用于制备曼尼希碱产物的代表性醛包括脂肪族醛,如甲醛、乙醛、丙醛、丁醛、戊醛、己醛、庚醛、硬脂醛。可使用的芳香族醛包括苯甲醛和水杨醛。用于本发明的说明性杂环醛为糠醛和噻吩醛等。还可用的为产甲醛的试剂,如多聚甲醛,或甲醛水溶液,如福尔马林。最优选的为甲醛或福尔马林。
烷基酚、特定胺和醛之间的缩合反应可以在通常约40℃至约200℃的范围内的温度下进行。反应可以在本体(无稀释剂或溶剂)中或在溶剂或稀释剂中进行。在反应过程中排出水并且可以通过共沸蒸馏去除水。通常,曼尼希反应产物通过使被烷基取代的羟基芳香族化合物、胺和醛分别以1.0:0.5-2.0:1.0-3.0的摩尔比反应而形成。
合适的曼尼希碱洗涤剂包括在以下专利中教导的那些洗涤剂:US 4231759;US 5,514,190;US 5,634,951;US 5,697,988;US 5,725,612;和5876468,这些专利的公开内容以引用方式并入本文。
另一种合适的额外燃料添加剂可以为烃基胺洗涤剂。如果使用,则燃料组合物可包括约45ppm至约1000ppm的烃基胺洗涤剂。一种常见方法涉及卤化长链脂肪族烃,如乙烯、丙烯、丁烯、异丁烯的聚合物,或如乙烯与丙烯、丁烯与异丁烯和其类似物的共聚物,随后使所得卤化烃与多胺反应。如果需要,则可以通过用适当量的酸处理将至少一些产物转化成胺盐。通过卤化途径形成的产物通常含有少量残余卤素,如氯。产生合适的脂肪族多胺的另一种方式涉及受控氧化(例如用空气或过氧化物)例如聚异丁烯的聚烯烃,随后使氧化的聚烯烃与多胺反应。关于制备此类脂族多胺洗涤剂/分散剂的合成细节参见例如美国专利号3,438,757;3,454,555;3,485,601;3,565,804;3,573,010;3,574,576;3,671,511;3,746,520;3,756,793;3,844,958;3,852,258;3,864,098;3,876,704;3,884,647;3,898,056;3,950,426;3,960,515;4,022,589;4,039,300;4,128,403;4,166,726;4,168,242;5,034,471;5,086,115;5,112,364;和5,124,484;以及公开的欧洲专利申请384,086。每个前述文献的公开内容以引用的方式并入本文中。烃基胺洗涤剂的长链取代基最优选以烷基或烯基的形式含有平均40至350个碳原子(具有或不具有少量残余卤素取代)。衍生自合适分子量的聚-α-烯烃均聚物或共聚物(例如,丙烯均聚物、丁烯均聚物、C3和C4α-烯烃共聚物和其类似物)的烯基取代基为合适的。最优选地,取代基是由聚异丁烯形成的聚异丁烯基,其数均分子量(如通过凝胶渗透色谱法测定)在500至2000、优选600至1800、最优选700至1600的范围内。
聚醚胺为用于本公开方法的又另一种合适的额外洗涤剂化学品。如果使用,则燃料组合物可包括约45ppm至约1000ppm的聚醚胺洗涤剂。此类洗涤剂中的聚醚主链可以基于环氧丙烷、环氧乙烷、环氧丁烷或其混合物。最优选的为环氧丙烷或环氧丁烷或其混合物,以赋予良好的燃料可溶性。聚醚胺可以为单胺、二胺或三胺。市售聚醚胺的实例是以商品名JeffaminesTM购自亨茨曼化学公司(Huntsman Chemical company)的那些和购自雪佛龙化学公司(Chevron Chemical Company)的聚(氧基亚烷基)氨基甲酸酯。聚醚胺的分子量通常将在500至3000的范围内。其他合适的聚醚胺是在以下专利中教导的那些化合物:美国专利号4,191,537;4,236,020;4,288,612;5,089,029;5,112,364;5,322,529;5,514,190和5,522,906。
内燃机:
使用本文的所选钙和镁碱性润滑油组合物的方法可适用于各种发动机类型,诸如但不限于混合汽油-电动发动机、端口燃料喷射式发动机、汽油直接喷射(GDI)和/或汽油直接喷射发动机或具有汽油微粒过滤器的其他汽油发动机。汽油发动机可以是火花点火发动机。内燃机也可与电源或电池动力源组合使用。如此构造的发动机通常被称为混合发动机。内燃机可以是2-冲程、4-冲程或旋转发动机。
本文的任何发动机还可包括汽油微粒过滤器(GPF)。在一些构造中,一旦在过滤器中形成烟灰饼之后以滤饼过滤模式操作,则GPF对于减少微粒排放是有效的。GPF可以任选地涂覆有三效催化剂(TWC)。本公开涉及未涂覆的和涂覆的GPF。众所周知,GDI技术的一个问题是,新安装的汽油微粒过滤器(GPF)在GPF的孔隙中有足够的颗粒物积聚以允许在滤饼过滤模式下操作之前,在深床过滤模式下运行时,在一段时间内具有低过滤效率。新鲜GPF过滤效率可低至30%。这种低初始过滤效率将影响排放性能。GPF过滤机制具有两种主要过滤模式:深床过滤和滤饼过滤。在GPF使用的早期阶段,颗粒物将在称为深床过滤的过程中首先被捕集在GPF的孔隙中。该过滤阶段的特征在于相对低的过滤效率和背压的快速增加。当颗粒物继续进入GPF时,过滤介质孔隙被微粒物质填充以产生滤饼,一旦微粒沿通道壁沉积,就会导致从深床过滤模式转变到滤饼过滤模式。滤饼过滤将保持有效,直到过滤器达到阈值为止,在该阈值处积聚的滤饼由于通道阻塞而导致背压显著升高。然而,当积聚的滤饼足以阻塞过滤器时达到该阈值,这通常发生在过滤器的设计使用寿命之外。
润滑油组合物:
用于降低排气管排放的所选钙和镁润滑油组合物包括具有润滑粘度的基础油和特定添加剂组合物,以提供所述钙和镁水平等特征。当润滑汽油时,本公开的方法采用含有添加剂组合物的所选钙和镁润滑油组合物。如本文更详细描述的,当在火花点火发动机中燃烧汽油时,所选钙和镁润滑油组合物可令人惊讶地有效地瞬时减少微粒排放,并且在一些情况下,甚至用GPF改善排放,并且在一些情况下,帮助克服过滤器的初始不良性能。
用于本文方法的润滑油组合物具有所选钙和镁量以及相互关系。在一个实施方案中,本公开提供了润滑油组合物,基于润滑油组合物的总重量,该润滑油组合物具有大于50重量%的具有润滑粘度的基础油,与足够量的一种或多种洗涤添加剂组合以提供所选钙和镁量,并且任选的上述论述的量和比率的低镁矿物以实现排放降低。在一种方法中,洗涤添加剂可包含通过ASTM D-2896的方法测量的总碱值大于225mg KOH/g的高碱性含钙洗涤剂,以向润滑油组合物提供大于约1500ppm的钙。在一些方法中,洗涤添加剂也被耗尽或具有低水平的镁,因此也可包含低/残留量的一种或多种通过ASTM D-2896的方法测量的总碱值大于225mg KOH/g的高碱性含镁洗涤剂,其中由该一种或多种高碱性镁洗涤剂提供至润滑油组合物中的镁的总量不超过500ppm或如本文所述的其他水平。
本公开还提供了用于减少火花点火发动机中的排气管排放、特别是减少微粒排放和改善GPF性能的方法。在一种方法中,本文的方法包括以下步骤:用本文的润滑油组合物中的所选钙和镁量润滑火花点火内燃机,并且在用该润滑油组合物润滑时操作该发动机,由此与不用本文的所选钙和镁碱性润滑组合物润滑的发动机相比,减少了来自该发动机的微粒排放。在一些实施方案中,火花点火的直接喷射发动机或端口燃料喷射内燃机的燃烧室或气缸壁在发动机操作期间用所选钙和镁润滑油组合物润滑。
任选地,本公开的方法可包括以下步骤:当用本文的组合物润滑发动机时,根据US06驱动循环来测量来自汽油组合物的燃烧的微粒排放。在此类方法中,排放颗粒物数目的减少可以是15%或更大的减少、或20%或更大的减少、或30%或更大的减少(在其他方法中,15%至30%的减少)。通过US06驱动循环测量排放减少。
洗涤剂
本文所选钙和镁碱性润滑油组合物包含一种或多种高碱性钙洗涤剂,诸如磺酸钙、水杨酸钙和/或酚钙洗涤剂,并且可任选地包含其他洗涤剂,诸如一种或多种其他金属高碱性洗涤剂和/或一种或多种低碱性/中性洗涤剂,以提供所述的钙、镁和其他矿物水平。合适的洗涤剂基质包括苯甲酸盐、含硫苯甲酸盐、磺酸盐、杯甲酸盐、柳酸盐、水杨酸盐、羧酸、磷酸、单硫代磷酸和/或二硫代磷酸、烷基酚、硫偶联烷基酚化合物或亚甲基桥联酚。合适的洗涤剂及其制备方法更详细地描述于多个专利公开中,包括US 7,732,390和其中引用的参考文献。洗涤剂基质可以用例如但不限于以下的碱金属或碱土金属盐化:钙、镁、钾、钠、锂、钡或它们的混合物。在一些实施方案中,洗涤剂不含钡。合适的洗涤剂可包括石油磺酸和长链单或二烷基芳基磺酸的碱金属或碱土金属盐,其中所述芳基为苯甲基、甲苯基和二甲苯基。
合适的其他洗涤剂的示例包含但不限于苯酚钙、含硫苯酚钙、磺酸钙、杯芳烃醇钙、水杨酸醇钙、水杨酸钙、羧酸钙、磷酸钙、单和/或二硫代磷酸钙、烷基酚钙、硫偶联的烷基苯酚钙化合物、亚甲基桥接酚钙、苯酚镁、含硫苯酚镁、磺酸镁、杯芳烃醇镁、水杨酸醇镁、水杨酸镁、羧酸镁、磷酸镁、单和/或二硫代磷酸镁、烷基酚镁、硫偶联烷基苯酚镁化合物、亚甲基桥接酚镁、苯酚钠、含硫苯酚钠、磺酸钠、杯芳烃醇钠、水杨酸醇钠、水杨酸钠、羧酸钠、磷酸钠、单和/或二硫代磷酸钠、烷基酚钠、硫偶联的烷基苯酚钠化合物,或亚甲基桥接酚钠。
高碱性洗涤剂是本领域中众所周知的,并且可为碱金属或碱土金属高碱性洗涤剂。可通过使金属氧化物或金属氢氧化物与基质和二氧化碳气体反应来制备此类洗涤剂。基质通常为酸,例如以下酸:如被脂肪族取代的磺酸、被脂肪族取代的羧酸或被脂肪族取代的酚。
术语“高碱性”涉及金属盐,如具有磺酸、羧酸和酚的金属盐,其中存在的金属量超过化学计算量。这类盐可具有超过100%的转化水平(即,它们可包含大于将酸转化为其“正常”、“中性”盐所需的金属的理论量的100%)。表达“金属比率”通常缩写为MR,其用于表示根据已知化学反应性和化学计量,在高碱性盐中金属的总化学当量与中性盐中金属的化学当量的比率。在正常或中性盐中,金属比率是一,而在高碱性盐中,MR大于一。它们通常被称为高碱性、超碱性或超级碱性盐,并且可为有机硫酸、羧酸、或酚的盐。
高碱性洗涤剂的TBN如通过ASTM D2896的方法测量可大于170mg KOH/g,或作为其他示例,TBN为约250mg KOH/g或更大,或TBN为约300mg KOH/g或更大,或TBN为约350mgKOH/g或更大,或TBN为约375mg KOH/g或更大,或TBN为约400mg KOH/g或更大。
在任何前述实施方案中,该一种或多种高碱性磺酸盐洗涤剂具有至少225mg KOH/g的总碱值。在每个前述实施方案中,该一种或多种高碱性磺酸盐洗涤剂可具有至少250mgKOH/g的总碱值。在每个前述实施方案中,该一种或多种高碱性磺酸盐洗涤剂的总碱值可为约250mg KOH/g至约450mg KOH/g,或约250mg KOH/g至350mg KOH/g。
合适的高碱性洗涤剂的示例包括但不限于:高碱性酚钙、高碱性含硫酚钙、高碱性磺酸钙、高碱性杯芳酸钙、高碱性柳芳酸钙、高碱性水杨酸钙、高碱性羧酸钙、高碱性磷酸钙、高碱性单硫代磷酸钙和/或二硫代磷酸钙、高碱性烷基酚钙、高碱性硫偶联烷基酚钙化合物、高碱性亚甲基桥连酚钙、高碱性酚镁、高碱性含硫酚镁、高碱性磺酸镁、高碱性杯芳酸镁、高碱性柳芳酸镁、高碱性水杨酸镁、高碱性羧酸镁、高碱性磷酸镁、高碱性单硫代磷酸镁和/或二硫代磷酸镁、高碱性烷基酚镁、高碱性硫偶联烷基酚镁化合物、或高碱性亚甲基桥连酚镁。高碱性洗涤剂的金属与基质的比率可为1.1:1,或2:1,或4:1,或5:1,或7:1,或10:1。
在一些方法中,只要洗涤剂满足上述钙和镁关系,基于润滑油组合物的总重量,洗涤剂的总量就可以至多10重量%、或约至多8重量%、至多约4重量%、至多约2.0重量%、或大于约1重量%、大于约1.2重量%、大于约1.4重量%或大于约1.1重量%至约2.0重量%存在。在其他方法中,洗涤剂(和其他添加剂)的总量可以向润滑油组合物提供约1500ppm至约5000ppm总金属和矿物含量的量存在。在其他实施方案中,洗涤剂(和其他添加剂)可将约1500ppm至约4500ppm的金属和/或矿物、或约1800ppm至约4500ppm的金属和/或矿物、或约2000ppm至约4500ppm的金属和/或矿物提供至本文的润滑油组合物以及上述钙和镁限定剂内以实现降低的微粒排放。如本文所述,来自洗涤剂和其他添加剂的总矿物包含钼、磷、锌、硼、镁和钙。
在一些方法中,本公开内容的润滑油组合物包含至少一种具有如通过ASTM-D2896的方法测定的大于225mg KOH/克,在一些方法中大于250mg KOH/克,在其他方法中约250mgKOH/克至约400mg KOH/克,并且在其他方法中约300mg KOH/克至约400mg KOH/克(并且具有约10重量%至约15重量%钙)的TBN的高碱性磺酸钙洗涤剂,并且在一些方法中具有大于170mg KOH/克的TBN的任选的酚钙洗涤剂,以提供所述水平的钙。本公开还包括以下方法:在方法中使用此类润滑油组合物,或通过用润滑油组合物润滑发动机并运行发动机来的润滑发动机的方法。
本文的润滑组合物可包含许多来自洗涤剂(和其他添加剂)的矿物,包括例如钼、磷、锌、硼、镁和钙,并且可如本文论述富含钙,使得基于流体中总矿物,润滑组合物的矿物包含至少40重量%的来自该一种或多种高碱性钙洗涤剂的钙。在其他方法中,基于润滑油组合物中的总矿物,钙可为约40重量%至约60重量%(或约42重量%至约58重量%、约45重量%至约55重量%、或约50重量%至约55重量%)。在其他方法中,本文的润滑组合物的矿物还可被耗尽或具有低水平的镁,这意味着基于润滑剂中的总矿物,组合物的矿物包含小于1%的镁、小于0.5重量%的镁、小于约0.25重量%的镁,并且可任选地不含镁。在其他方法中,本文的润滑组合物的矿物还可包含约1重量%至5重量%的钼、约15重量%至约20重量%的磷、约15重量%至约30重量%的锌和/或约1重量%至约10重量%的硼,所有此类矿物基于润滑组合物的总矿物(总矿物包含钼、磷、锌、硼、镁和钙)。
在其他方法中,本文的润滑组合物可包含约0.15重量%至约0.3重量%钙(在其他方法中,约0.2重量%至约0.25重量%的钙)和小于约0.05重量%的镁(在其他方法中,小于约0.01重量%、小于约0.005重量%、小于约0.0025重量%或小于约0.01重量%镁)。在其他方法中,本文的润滑组合物还可包含约0.005重量%至约0.01重量%的钼、约0.05重量%至约0.1重量%的磷、约0.05重量%至约0.1重量%的锌和/或约0.01重量%至约0.05重量%的硼。
在其他方法中,基于润滑油组合物的总重量,本公开的润滑油组合物可具有来自高碱性洗涤剂的范围为约1500重量ppm至约3000重量ppm的钙的总量,或范围为至少约1500ppm、至少约1600ppm、至少约1700ppm、至少约1800ppm、至少约1900ppm、至少约2000ppm、至少约2100ppm、至少约2200ppm至不超过3000ppm、不超过2800ppm、不超过2700ppm、不超过2600ppm或不超过2500ppm的钙的量。
本公开的润滑油组合物可任选地包含另一种高碱性洗涤剂,其可以是少量的高碱性含镁洗涤剂。高碱性含镁洗涤剂可选自高碱性磺酸镁清洁剂、高碱性苯酚镁清洁剂和高碱性水杨酸镁洗涤剂。在某些实施方案中,高碱性含镁洗涤剂包括高碱性磺酸镁洗涤剂。在某些实施方案中,高碱性洗涤剂是一种或多种含镁洗涤剂,高碱性洗涤剂优选是磺酸镁洗涤剂。如果包含含镁洗涤剂,则本文的润滑组合物可仅包含低水平的此类洗涤剂,诸如基于润滑组合物的总矿物,不超过1重量%。高碱性含镁洗涤剂可具有约225mg KOH/g或更大、约250mg KOH/g或更大、约300mg KOH/g或更大,或在其他方法中,约300mg KOH/g至约450mgKOH/g的TBN。
在某些实施方案中,该一种或多种高碱性含钙洗涤剂的总量可向成品流体提供约1500至约3000ppm钙。再如,并且如上论述的,该一种或多种高碱性含钙洗涤剂可以向不含或缺乏如上所述的镁的流体中的成品流体提供约1800ppm至约3000ppm钙、或约2000ppm至约2800ppm钙、或约2000ppm至2600ppm钙、或约2200ppm至2400ppm钙的量存在。
在每个前述实施方案中,本发明的润滑油组合物可任选地包含低碱性/中性洗涤剂,其具有至多170mg KOH/g或至多150mg KOH/g的TBN。低碱性/中性洗涤剂可包括含钙洗涤剂,只要总钙量满足上述限制即可。低碱性中性含钙洗涤剂可选自磺酸钙洗涤剂、苯酚钙洗涤剂和水杨酸钙洗涤剂。在一些实施方案中,低碱性/中性洗涤剂可为含钙洗涤剂或含钙洗涤剂的混合物。在一些实施方案中,低碱性/中性洗涤剂可为磺酸钙洗涤剂或苯酚钙洗涤剂。
在一些实施方案中,润滑油组合物任选地不含任何高碱性水杨酸钙洗涤剂。在其他实施方案中,润滑油可任选地不含任何含镁洗涤剂或不含镁。在本公开的任何实施方案中,基于润滑油组合物的总重量,润滑组合物中钠的量可限于不超过150ppm的钠,或以润滑油组合物的总重量计不超过50ppm的钠。
基础油
本文中用于润滑油组合物的基础油可选自美国石油学会(American PetroleumInstitute,API)基础油互换性指南中规定的第I-V组中的基础油中的任何一种。五类基础油如下:
表1
第I类、第II类和第III类是矿物油加工原料。第IV类基础油含有真正的合成分子种类,这些合成分子种类通过烯属不饱和烃的聚合制备。许多第V类基础油也是真正的合成产物,并且可包括二酯、多元醇酯、聚亚烷基二醇、烷基化芳族化合物、聚磷酸酯、聚乙烯醚和/或聚苯醚等,但也可以是天然存在的油,诸如植物油。应当注意,尽管第III类基础油衍生自矿物油,但这些流体经历的严格加工导致它们的物理性质非常类似于一些真正的合成油,诸如PAO。因此,衍生自第III类基础油的油在工业中可称为合成流体。
用于所公开的润滑油组合物中的基础油可为矿物油、动物油、植物油、合成油或其混合物。合适的油可衍生自加氢裂化、氢化、加氢精制、未精炼、精炼和再精炼的油以及它们的混合物。
未精炼的油是衍生自天然、矿物或合成来源的那些油,没有或几乎没有进一步纯化处理。精炼的油类似于未精炼的油,不同之处在于它们经过了一个或多个纯化步骤的处理,这可能会导致一种或多种特性的改善。合适的纯化技术的示例是溶剂萃取、二次蒸馏、酸或碱萃取、过滤、渗滤等。精炼到可食用品质的油可能有用也可能没用。食用油也可以称为白油。在一些实施方案中,润滑油组合物不含食用油或白油。
再精制油也称作再生油或再加工油。类似于精炼的油,使用相同或类似的加工获得这些油。通常这些油通过针对于去除废添加剂和油分解产物的技术进一步加工。
矿物油可包括通过钻井获得的油或来自植物和动物的油或它们的任何混合物。例如,此类油可包括但不限于蓖麻油、猪油、橄榄油、花生油、玉米油、大豆油和亚麻籽油,以及矿物润滑油,诸如液体石油和溶剂处理或酸处理的链烷、环烷或混合链烷-环烷类型的矿物润滑油。如果需要,此类油可部分或完全氢化。来源于煤或页岩的油也可以是适用的。
有用的合成润滑油可包括烃油,诸如聚合的、低聚的或共聚的烯烃(例如,聚丁烯、聚丙烯、丙烯异丁烯共聚物);聚(1-己烯)、聚(1-辛烯)、1-癸烯的三聚物或低聚物,例如聚(1-癸烯),此类材料通常被称为α-烯烃,以及它们的混合物;烷基-苯(例如,十二烷基苯、十四烷基苯、二壬基苯、二-(2-乙基己基)-苯);聚苯(例如联苯、三联苯、烷基化聚苯);二苯基烷烃、烷基化二苯基烷烃、烷基化二苯基醚和烷基化二苯基硫化物及其衍生物、类似物和同系物或它们的混合物。聚α-烯烃通常是氢化材料。
其他合成润滑油包括含磷酸的多元醇酯、二酯、液体酯(例如,磷酸甲苯、磷酸三辛酯和癸烷膦酸的二乙酯)或聚四氢呋喃。合成油可以通过费舍尔-托普希反应(Fischer-Tropschreaction)产生并且典型地可以是加氢异构化的费舍尔-托普希烃或蜡。在一个实施方案中,油可通过费托气液合成程序以及其他气液油制备。
润滑组合物中包括的大于50重量%的基础油可选自由以下组成的群组:第I类、第II类、第III类、第IV类、第V类以及前述的两种或更多种的组合,并且其中大于50重量%的基础油不是由在组合物中提供添加剂组分或粘度指数改善剂而产生的基础油。在另一实施方案中,润滑组合物中包括的大于50重量%的基础油可选自由以下组成的群组:第II类、第III类、第IV类、第V类以及前述的两种或更多种的组合。并且,基础油可选自第II类至第V类基础油或其任何两种或更多种的混合物。具有润滑油组合物的总重量,大于50重量%的基础油可以不是由向组合物提供添加剂组分或粘度指数改善剂而产生的稀释油。
具有润滑粘度的油的存在量可以是从100重量%中减去性能添加剂(包括粘度指数改善剂和/或降凝剂和/或其他顶处理添加剂)的总量之后剩余的余量。例如,可存在于成品流体中的润滑粘度的油可为大量,诸如大于约50重量%、大于约60重量%、大于约70重量%、大于约80重量%、大于约85重量%或大于约90重量%。
润滑油组合物可包含不超过10重量%的第IV类基础油,第V类基础油或它们的组合。在每个前述实施方案中,润滑油组合物可包含小于5重量%的第V类基础油。一些实施方案的润滑油组合物不含有任何第IV类基础油和/或不含有任何第V类基础油。
润滑油组合物的任何实施方案还可包括选自下面阐述的各种添加剂的一种或多种任选组分。
抗氧化剂
本文中的润滑油组合物还可任选地含有一种或多种抗氧化剂。抗氧化剂化合物是已知的,并且包含例如苯酚盐、苯酚硫化物、硫化烯烃、磷硫化萜、硫化酯、芳香族胺、烷基化二苯胺(例如,壬基二苯胺、二壬基二苯胺、辛基二苯胺、二辛基二苯胺)、苯基-α-萘胺、烷基化苯基-α-萘胺、受阻非芳香族胺、酚、受阻酚、油溶性钼化合物、大分子抗氧化剂或其混合物。抗氧化剂化合物可单独或组合使用。
受阻酚抗氧化剂可含有仲丁基和/或叔丁基作为空间受阻基团。酚基可以进一步被烃基和/或连接到第二芳族基团的桥连基团取代。合适的受阻酚抗氧化剂的示例包括2,6-二-叔丁基酚、4-甲基-2,6-二-叔丁基酚、4-乙基-2,6-二-叔丁基酚、4-丙基-2,6-二-叔丁基酚或4-丁基-2,6-二-叔丁基酚、或4-十二基-2,6-二-叔丁基酚。在一个实施方案中,受阻酚抗氧化剂可为酯,并且可包括例如可购自巴斯夫(BASF)的IRGANOXTML-135或衍生自2,6-二叔丁基酚和丙烯酸烷基酯的加成产物,其中烷基可含有约1至约18,或约2至约12,或约2至约8,或约2至约6,或约4个碳原子。另一种市售的受阻酚抗氧化剂可为酯,并且可包括可购自雅宝(Albemarle Corporation)的ETHANOXTM4716。
可用的抗氧化剂可包括二芳基胺和高分子量酚。在一个实施方案中,润滑油组合物可含有二芳基胺和高分子量酚的混合物,使得按润滑油组合物的最终重量计,每一抗氧化剂可以足以提供至多约5重量%的量存在。在实施方案中,基于润滑油组合物的最终重量,抗氧化剂可以是约0.3至约1.5重量%二芳基胺和约0.4至约2.5重量%高分子量酚的混合物。
可硫化以形成硫化烯烃的合适烯烃的示例包括丙烯、丁烯、异丁烯、聚异丁烯、戊烯、己烯、庚烯、辛烯、壬烯、癸烯、十一烯、十二烯、十三烯、十四烯、十五烯、十六烯、十七烯、十八烯、十九烯、二十烯或其混合物。在一个实施方案中,十六烯、十七烯、十八烯、十九烯、二十烯或其混合物,以及其二聚物、三聚物以及四聚物是特别适用的烯烃。另选地,烯烃可以是二烯(如1,3-丁二烯)与不饱和酯(如丙烯酸丁酯)的狄尔斯-阿尔德加合物(Diels-Alder adduct)。
另一类硫化烯烃包括硫化脂肪酸及其酯。脂肪酸通常获自植物油或动物油且典型地含有约4至约22个碳原子。合适脂肪酸及其酯的示例包括甘油三酯、油酸、亚油酸、棕榈油酸或其混合物。通常,脂肪酸获自猪油、松油、花生油、大豆油、棉籽油、葵花籽油或其混合物。脂肪酸和/或酯可以与烯烃(如α-烯烃)混合。
该一种或多种抗氧化剂可以约0重量%至约20重量%、或约0.1重量%至约10重量%、或约1重量%至约5重量%的范围存在于润滑油组合物中。
抗磨剂
本文中的润滑油组合物还可任选地含有一种或多种抗磨剂。合适的抗磨剂的示例包括但不限于金属硫代磷酸盐;二烷基二硫代磷酸金属盐;磷酸酯或其盐;磷酸酯;亚磷酸酯;含磷羧酸酯、醚或酰胺;硫化烯烃;含硫代氨基甲酸酯的化合物,包括硫代氨基甲酸酯、亚烷基偶联硫代氨基甲酸酯和双(S-烷基二硫代氨甲酰基)二硫化物;以及它们的混合物。合适的抗磨剂可以是二硫代氨基甲酸钼。含磷抗磨剂更全面地描述于欧洲专利612839中。在二烷基二硫基磷酸盐中的金属可以是碱金属、碱土金属、铝、铅、锡、钼、锰、镍、铜、钛或锌。适用的抗磨剂可以是二烷基二硫代磷酸锌。
合适的抗磨剂的又一示例包括钛化合物、酒石酸酯、酒石酰亚胺、磷化合物的油溶性胺盐、硫化烯烃、亚磷酸酯(如亚磷酸二丁酯)、膦酸酯、含硫代氨基甲酸酯的化合物(如硫代氨基甲酸酯、硫代氨基甲酸酯酰胺、硫代氨基甲酸醚、亚烷基偶联硫代氨基甲酸酯和双(S-烷基二硫代氨甲酰基)二硫化物)。酒石酸酯或酒石酰亚胺可含有烷基酯基团,其中烷基基团中的碳原子总和可为至少8。在一个实施方案中,抗磨剂可包括柠檬酸酯。
抗磨损剂可以存在于包括润滑油组合物的约0重量%至约15重量%、或约0.01重量%至约10重量%、或约0.05重量%至约5重量%、或约0.1重量%至约3重量%的范围内。
抗磨损化合物可为二烃基二硫代磷酸锌(ZDDP),其P:Zn的比率为约1:0.8至约1:1.7。ZDDP的二烃基可以由C3和C6醇的混合物形成。
含硼化合物
本文中润滑油组合物可任选地含有一种或多种含硼化合物。基于润滑油组合物的总重量,润滑油组合物中的硼的量小于200重量ppm,或基于润滑油组合物的总重量,小于100重量ppm,或基于润滑油组合物的总重量,小于50重量ppm。
含硼化合物的示例包括硼酸酯、硼酸化脂肪胺、硼酸化环氧化物、硼酸化洗涤剂和硼酸化分散剂,如硼酸化丁二酰亚胺分散剂,如美国专利号5,883,057中所公开。
该一种或多种含硼化合物如果存在的话,则可以足以向润滑油组合物提供小于200重量ppm硼或向润滑油组合物提供小于100重量ppm硼或向润滑油组合物提供小于50重量ppm硼的量加以使用。
分散剂
润滑油组合物可任选地进一步包含一种或多种分散剂或其混合物。分散剂通常称为无灰型分散剂,因为在润滑油组合物中混合之前,其不含有形成灰分的金属并且当添加到润滑剂中时其通常不促成任何灰分。无灰型分散剂的特征在于极性基团连接到相对较高分子量烃链。典型的无灰分散剂包括N-取代的长链烯基琥珀酰亚胺。N-取代长链烯基丁二酰亚胺的实例包括聚异丁烯丁二酰亚胺,其中聚异丁烯取代基的数均分子量在约350到约50,000或到约5,000或到约3,000范围内。琥珀酰亚胺分散剂及其制备公开于例如美国专利号7,897,696或美国专利号4,234,435中。可以由含有约2至约16、或约2至约8、或约2至约6个碳原子的可聚合单体来制备聚烯烃。琥珀酰亚胺分散剂通常是由多胺,通常是聚(亚乙基胺)形成的酰亚胺。
在实施方案中,本公开进一步包含至少一种聚异丁烯丁二酰亚胺分散剂,其衍生自数目平均分子量在约350至约50,000或至约5000或至约3000范围内的聚异丁烯。聚异丁烯琥珀酰亚胺可以单独或与其他分散剂组合使用。
在一些实施方案中,聚异丁烯(当被包括时)可具有大于50mol%、大于60mol%、大于70mol%、大于80mol%或大于90mol%含量的末端双键。这类PIB也被称为高度反应性PIB(“HR-PIB”)。数均分子量在约800到约5000范围内的HR-PIB适用于本公开的实施方案。常规PIB通常具有小于50mol%、小于40mol%、小于30mol%、小于20mol%或小于10mol%含量的末端双键。
数均分子量在约900至约3000范围内的HR-PIB可为合适的。这类HR-PIB是可商购的或可以通过在非氯化催化剂(如三氟化硼)存在下聚合异丁烯来合成,如在Boerzel等人的美国专利号4,152,499和Gateau等人的美国专利号5,739,355中所描述。当用于前述热烯反应中时,由于增强的反应性,HR-PIB可以提高反应中的转化率,以及降低沉降物形成量。合适的方法描述于美国专利号7,897,696中。
在一个实施方案中,本公开进一步包含至少一种衍生自聚异丁烯琥珀酸酐(“PIBSA”)的分散剂。PIBSA平均每聚合物可具有约1.0和约2.0之间的琥珀酸部分。
可使用色谱技术确定烯基或烷基琥珀酸酐的活性%。这种方法描述于美国专利号5,334,321的第5栏和第6栏中。
使用美国专利号5,334,321的第5列和第6列中的等式,由活性%计算聚烯烃的转化百分比。
除非另外说明,否则所有百分比均以重量百分比计并且所有分子量均为数均分子量。
在一个实施方案中,分散剂可衍生自聚α烯烃(PAO)琥珀酸酐。
在一个实施方案中,分散剂可衍生自烯烃马来酸酐共聚物。例如,分散剂可被描述为聚PIBSA。
在实施方案中,分散剂可衍生自接枝到乙烯-丙烯共聚物的酸酐。
一类适合分散剂可以是曼尼希碱(Mannich base)。曼尼希碱为由较高分子量的、经烷基取代的酚、聚亚烷基多胺和醛(如甲醛)的缩合形成的材料。曼尼希碱更详细地描述于美国专利号3,634,515中。
适合类别的分散剂可以是高分子量的酯或半酯酰胺。
合适的分散剂也可由常规方法通过与各种试剂中的任一种反应进行后处理。在这些中为硼、脲、硫脲、二巯基噻二唑、二硫化碳、醛、酮、羧酸、烃取代琥珀酸酐、马来酸酐、腈、环氧化物、碳酸酯、环状碳酸酯、受阻酚酯以及磷化合物。US 7,645,726;US 7,214,649;和US 8,048,831全文以引用方式并入本文。
除了碳酸酯和硼酸后处理之外,两种化合物都可用被设计成改进或赋予不同特性的多种后处理法进行后处理或进一步后处理。这类后处理包括在美国专利号5,241,003的第27到29列中概述的那些,以引用的方式并入本文中。这类处理包括用以下处理:无机亚磷酸或无水物(例如美国专利号3,403,102和4,648,980);有机磷化合物(例如美国专利号3,502,677);五硫化磷;
如以上已提到的硼化合物(例如美国专利号3,178,663和4,652,387);
羧酸、聚羧酸、酸酐和/或酸卤化物(例如美国专利号3,708,522和4,948,386);环氧化物、聚环氧化物或硫代环氧化物(例如美国专利号3,859,318和5,026,495);醛或酮(例如美国专利号3,458,530);二硫化碳(例如美国专利号3,256,185);缩水甘油(例如美国专利号4,617,137);脲、硫脲或胍(例如美国专利号3,312,619;3,865,813;和英国专利GB 1,065,595);有机磺酸(例如美国专利号3,189,544和英国专利GB 2,140,811);烯基氰化物(例如美国专利号3,278,550和号3,366,569);双烯酮(例如美国专利号3,546,243);二异氰酸酯(例如美国专利号3,573,205);烷烃磺内酯(例如美国专利号3,749,695);1,3-二羰基化合物(例如美国专利号4,579,675);烷氧基化醇或酚的硫酸盐(例如美国专利号3,954,639);环状内酯(例如美国专利号4,617,138;4,645,515;4,668,246;4,963,275;和4,971,711);环状碳酸酯或硫代碳酸酯线性单碳酸酯或聚碳酸酯,或氯甲酸酯(例如美国专利号4,612,132;4,647,390;4,648,886;4,670,170);含氮羧酸(例如美国专利号4,971,598和英国专利GB 2,140,811);羟基保护的氯二羰基氧基化合物(例如美国专利号4,614,522);内酰胺、硫内酰胺、硫内酯或二硫内酯(例如美国专利号4,614,603和4,666,460);环状碳酸酯或硫代碳酸酯线性单碳酸酯或聚碳酸酯,或氯甲酸酯(例如美国专利号4,612,132;4,647,390;4,646,886;和4,670,170);含氮羧酸(例如美国专利号4,971,598和英国专利GB 2,440,811);羟基保护的氯二羰基氧基化合物(例如美国专利号4,614,522);内酰胺、硫内酰胺、硫内酯或二硫内酯(例如美国专利号4,614,603和4,666,460);环状氨基甲酸酯、环状硫代氨基甲酸酯或环状二硫代氨基甲酸酯(例如美国专利号4,663,062和4,666,459);羟基脂肪族羧酸(例如美国专利号4,482,464;4,521,318;4,713,189);氧化剂(例如美国专利号4,379,064);五硫化二磷和聚亚烷基聚胺的组合(例如美国专利号3,185,647);羧酸或醛或酮和硫或氯化硫的组合(例如美国专利号3,390,086;3,470,098);肼和二硫化碳的组合(例如美国专利号3,519,564);醛和酚的组合(例如美国专利号3,649,229;5,030,249;5,039,307);醛和二硫代磷酸的O-二酯的组合(例如美国专利号3,865,740);羟基脂肪族羧酸和硼酸的组合(例如美国专利号4,554,086);羟基脂肪族羧酸,然后甲醛和酚的组合(例如美国专利号4,636,322);羟基脂肪族羧酸与然后脂肪族二羧酸的组合(例如美国专利号4,663,064);甲醛和酚与然后乙醇酸的组合(例如美国专利号4,699,724);羟基脂肪族羧酸或草酸,并且然后二异氰酸酯的组合(例如美国专利号4,713,191);磷的无机酸或酸酐或其部分或全部硫类似物与含硼化合物的组合(例如美国专利号4,857,214);有机二酸、然后不饱和脂肪酸与然后亚硝基芳香族胺、任选地随后硼化合物以及然后乙醇酸化试剂的组合(例如美国专利号4,973,412);醛和三唑的组合(例如美国专利号4,963,278);醛和三唑,然后硼化合物的组合(例如美国专利号4,981,492);环状内酯和硼化合物的组合(例如美国专利号4,963,275和4,971,711)。以上提及的专利以其全文并入在本文中。
合适的分散剂的TBN在不含油基础上可为约10至约65,相当于如果对含有约50%稀释油的分散剂样品测量,那么为约5至约30TBN。
分散剂如果存在的话,则基于润滑油组合物的最终重量,可以足以提供至多约20重量%的量加以使用。可使用分散剂的另一量可以是,基于润滑油组合物的最终重量,约0.1重量%至约15重量%、或约0.1重量%至约10重量%、或约3重量%至约10重量%、或约1重量%至约6重量%、或约7重量%至约12重量%。在一些实施方案中,润滑油组合物利用混合的分散剂体系。可以使用按任何期望比率的单一类型分散剂或两种或更多种类型的分散剂的混合物。
摩擦改性剂
本文中的润滑油组合物还可任选地含有一种或多种摩擦改性剂。合适的摩擦改性剂可包含含金属和不含金属的摩擦改性剂,并且可包括但不限于咪唑啉、酰胺、胺、琥珀酰亚胺、烷氧基化胺、烷氧基化醚胺、胺氧化物、酰氨基胺、腈、甜菜碱、季胺、亚胺、胺盐、氨基胍、烷醇酰胺、膦酸酯、含金属化合物、甘油酯、硫化脂肪化合物和烯烃、葵花油、其他天然存在的植物或动物油、二羧酸酯、多元醇的酯或偏酯以及一种或多种脂肪族或芳香族羧酸等。
合适的摩擦改性剂可含有选自直链、支链或芳香族烃基或其混合物的烃基,并且可为饱和的或不饱和的。烃基基团可以由碳和氢或杂原子,如硫或氧构成。烃基可在约12到约25个碳原子的范围内。在一些实施方案中,摩擦改性剂可为长链脂肪酸酯。在另一个实施方案中,长链脂肪酸酯可以是单酯或二酯或(三)甘油酯。摩擦改性剂可以是长链脂肪酰胺、长链脂肪酯、长链脂肪环氧化物衍生物或长链咪唑啉。
其他合适的摩擦改性剂可包括有机、无灰(不含金属)、不含氮有机摩擦改性剂。此类摩擦改性剂可以包括通过使羧酸和酐与烷醇反应形成的酯,并且一般包含共价键结到亲油性烃链的极性端基(例如,羧基或羟基)。有机无灰无氮摩擦改性剂的示例通常已知为单油酸甘油酯(GMO),其可含有油酸的单酯、二酯和三酯。其他合适的摩擦改性剂描述于美国专利号6,723,685中,其全部内容以引用方式并入本文。
胺类摩擦改性剂可包括胺或多胺。此类化合物可具有直链、饱和或不饱和的烃基基团,或它们的混合物,并且可以含有约12到约25个碳原子。合适的摩擦改性剂的其他示例包括烷氧基化胺和烷氧基化醚胺。此类化合物可具有直链、饱和或不饱和的烃基,或其混合物。其可含有约12到约25个碳原子。示例包括乙氧基化的胺和乙氧基化的醚胺。
胺和酰胺可按原样使用或以与硼化合物(如氧化硼、卤化硼、偏硼酸酯、硼酸或硼酸单烷基酯、二烷基酯或三烷基酯)的加成物或反应产物形式使用。其他合适的摩擦改性剂描述于美国专利号6,300,291中,其全部内容以引用方式并入本文。
摩擦改性剂可任选地在范围诸如约0重量%至约10重量%、或约0.01重量%至约8重量%、或约0.1重量%至约4重量%内存在。
含钼组分
本文的润滑油组合物还可任选地包含一种或多种含钼化合物。油溶性钼化合物可具有抗磨剂、抗氧化剂、摩擦改性剂或它们的混合物的功能性能。油溶性钼化合物可包括二硫代氨基甲酸钼、二烷基二硫代磷酸钼、二硫代亚膦酸钼、钼化合物的胺盐、黄原酸钼、硫代黄原酸钼、硫化钼、羧酸钼、烷醇钼、三核有机钼化合物、和/或其混合物。硫化钼包括二硫化钼。二硫化钼可以是稳定分散体的形式。在一个实施方案中,油溶性钼化合物可选自二硫代氨基甲酸钼、二烷基二硫代磷酸钼、钼化合物的胺盐以及它们的混合物。在一个实施方案中,油溶性钼化合物可以是二硫代氨基甲酸钼。
可使用的钼化合物的合适示例包括以如下商标名出售的商业物质:来自范德比尔特有限公司(R.T.Vanderbilt Co.,Ltd.)的Molyvan 822TM、MolyvanTMA、Molyvan 2000TM和Molyvan 855TM和可购自艾迪科公司(Adeka Corporation)的Sakura-LubeTMS-165、S-200、S-300、S-310G、S-525、S-600、S-700和S-710、以及它们的混合物。合适的钼组分描述于US5,650,381;US RE 37,363 E1;US RE 38,929 E1;和US RE 40,595 E1中,其全文以引用方式并入本文。
另外,钼化合物可以是酸性钼化合物。包括钼酸、钼酸铵、钼酸钠、钼酸钾和其他碱金属钼酸盐和其他钼盐,例如钼酸氢钠、MoOCl4、MoO2Br2、Mo2O3Cl6、三氧化钼或类似的酸性钼化合物。另选地,这些组合物可通过碱性氮化合物的钼/硫络合物提供钼,如例如美国专利号4,263,152;4,285,822;4,283,295;4,272,387;4,265,773;4,261,843;4,259,195和4,259,194;以及US 2002/0038525中所述,这些专利的全部内容以引用方式并入本文。
另一类合适的有机钼化合物是三核钼化合物,诸如式Mo3SkLnQz的那些及其混合物,其中S表示硫,L表示独立地选择的具有有机基团的配体,这些有机基团具有足够数目的碳原子以使得该化合物可溶或可分散在油中,n为1至4,k为4至7,Q选自中性供电子化合物诸如水、胺、醇、膦和醚,并且z范围为0至5并且包括非化学计量的值。在所有配体的有机基团中可存在总共至少21个碳原子,如至少25、至少30或至少35个碳原子。其他合适的钼化合物描述于美国专利号6,723,685中,其全部内容以引用方式并入本文。
油溶性钼化合物可以足以提供约0.5ppm至约2000ppm、约1ppm至约700ppm、约1ppm至约550ppm、约5ppm至约450ppm,或约90ppm至约350ppm的钼的量存在。
含钛化合物
另一类添加剂包含油溶性钛化合物。油溶性钛化合物可充当抗磨剂、摩擦改性剂、抗氧化剂、沉积物控制添加剂,或这些功能中的多于一种。在实施方案中,油溶性钛化合物可以是烷醇钛(IV)。烷醇钛可以由一元醇、多元醇或其混合物形成。一元烷醇盐可具有2到16、或3到10个碳原子。在实施方案中,烷醇钛可以是异丙醇钛(IV)。在实施方案中,烷醇钛可以是2-乙基己醇钛(IV)。在实施方案中,钛化合物可以是1,2-二醇或多元醇的烷醇盐。在实施方案中,1,2-二醇包括脂肪酸甘油单酯,如油酸。在实施方案中,油溶性钛化合物可以是羧酸钛。在实施方案中,羧酸钛(IV)可以为新癸酸钛。
在一实施方案中,油溶性钛化合物在润滑油组合物中可以提供从零至约1500重量ppm钛或约10重量ppm至500重量ppm钛或约25ppm至约150ppm的量存在。
含过渡金属的化合物
在另一实施方案中,油溶性化合物可为含过渡金属的化合物或类金属。过渡金属可包括但不限于:钛、钒、铜、锌、锆、钼、钽、钨等。适合的类金属包括但不限于:硼、硅、锑、碲等。
在一个实施方案中,油溶性化合物是含钛化合物,其以介于约0.8:1到约70:1范围内的Ca/M重量比使用,其中M是如上文所描述的润滑油组合物中的总金属。含钛化合物可起抗磨剂、摩擦改性剂、抗氧化剂、沉积物控制添加剂作用,或这些作用中的一种以上。在所公开技术中可使用的或可用于制备所公开技术的油溶性材料的含钛化合物中有各种Ti(IV)化合物,诸如氧化钛(IV);硫化钛(IV);硝酸钛(IV);钛(IV)醇盐,诸如甲醇钛、乙醇钛、丙醇钛、异丙醇钛、丁醇钛、2-乙基己醇钛;以及其他钛化合物或络合物,包括但不限于酚钛;羧酸钛,诸如2-乙基-1-3-己二酸钛(IV)或柠檬酸钛或油酸钛;和(三乙醇胺)异丙醇钛(IV)。在所公开技术内涵盖的其他形式钛包括磷酸钛,如二硫代磷酸钛(例如二烷基二硫代磷酸钛),和磺酸钛(例如烷基苯磺酸钛),或一般地,钛化合物与各种酸性材料反应以形成盐(如油溶性盐)的反应产物。钛化合物因此尤其可衍生自有机酸、醇和二醇。Ti化合物也可以二聚或寡聚形式存在,含有Ti--O--Ti结构。这类钛材料为可商购的或可容易通过本领域的技术人员显而易知的适当合成技术制备。其在室温下以固体或液体形式存在,这取决于具体化合物。其也可以在适当惰性溶剂中的溶液的形式提供。
在一个实施方案中,钛可供应为Ti改性的分散剂,如琥珀酰亚胺分散剂。这类材料可通过在钛醇盐和经烃基取代的丁二酸酐(如烯基(或烷基)丁二酸酐)之间形成钛混合酸酐制备。所得钛酸盐-琥珀酸盐中间体可以直接使用,或者它可以与许多材料中的任一种材料反应,诸如(a)具有游离、可缩合--NH官能团的基于多胺的琥珀酰亚胺/酰胺分散剂;(b)基于多胺的琥珀酰亚胺/酰胺分散剂的组分,即烯基-(或烷基-)琥珀酸酐和多胺,(c)通过取代的琥珀酸酐与多元醇、氨基醇、多胺或它们的混合物反应制备的含羟基聚酯分散剂。另选地,钛酸盐-琥珀酸盐中间体可与其他试剂,如醇、氨基醇、醚醇、聚醚醇或多元醇或脂肪酸反应,并且直接使用其产物来将Ti赋予润滑剂,或另外,如文所述另外与琥珀酸分散剂反应。例如,1份(按摩尔计)钛酸四异丙酯可与约2份(按摩尔计)被聚异丁烯取代的琥珀酸酐在140℃至150℃下反应5小时至6小时,以提供钛改性的分散剂或中间体。所得物质(30g)可进一步与来自被聚异丁烯取代的琥珀酸酐的琥珀酰亚胺分散剂和聚亚乙基多胺混合物(127克+稀释油)在150℃下反应1.5小时,以产生钛改性的琥珀酰亚胺分散剂。
另一种含钛化合物可以是钛醇盐与C6到C25羧酸的反应产物。反应产物可由下式表示:
其中n为选自2、3和4的整数,并且R为含有约5至约24个碳原子的烃基,或由下式表示
其中m+n=4且n在1至3范围内,R4是具有在1至8个范围内的碳原子的烷基部分,R1选自含有约6至25个碳原子的烃基,并且R2和R3相同或不同且选自含有约1至6个碳原子的烃基,或由下式表示
其中x在0到3范围内,R1选自含有约6到25个碳原子的烃基,R2和R3相同或不同且选自含有约1到6个碳原子的烃基,并且R4选自由H、或C6到C25羧酸部分组成的群组。
合适的羧酸可以包括但不限于己酸、辛酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、花生酸、油酸、芥酸、亚油酸、亚麻酸、环己烷羧酸、苯乙酸、苯甲酸、新癸酸等。
在一个实施方案中,油溶性钛化合物在润滑油组合物中可以提供0重量ppm至3000重量ppm钛,或25重量ppm至约1500重量ppm钛,或约35重量ppm至500重量ppm钛,或约50ppm至约300ppm的量存在。
粘度指数改善剂
本文中的润滑油组合物还可任选地含有一种或多种粘度指数改善剂。适合的粘度指数改善剂可以包含聚烯烃、烯烃共聚物、乙烯/丙烯共聚物、聚异丁烯、氢化苯乙烯-异戊二烯聚合物、苯乙烯/顺丁烯二酸酯共聚物、氢化苯乙烯/丁二烯共聚物、氢化异戊二烯聚合物、α-烯烃顺丁烯二酸酐共聚物、聚甲基丙烯酸酯、聚丙烯酸酯、聚烷基苯乙烯、氢化烯基芳基共轭二烯共聚物,或其混合物。粘度指数改善剂可包括星形聚合物,并且合适的实例描述于美国专利号8,999,905B2中。
本文中的润滑油组合物除了粘度指数改善剂之外或代替粘度指数改善剂,还可以任选地含有一种或多种分散剂粘度指数改善剂。合适的粘度指数改善剂可包括官能化聚烯烃,例如已经用酰化剂(诸如马来酸酐)和胺的反应产物官能化的乙烯-丙烯共聚物;用胺官能化的聚甲基丙烯酸酯,或与胺反应的酯化马来酸酐-苯乙烯共聚物。
粘度指数改善剂和/或分散剂粘度指数改善剂的总量可以是润滑油组合物的约0重量%至约20重量%、约0.1重量%至约15重量%、约0.1重量%至约12重量%、或约0.5重量%至约10重量%。
其他任选的添加剂
可选择其他添加剂以执行润滑流体需要的一种或多种功能。另外,一种或多种所提及的添加剂可为多官能的并且提供除了本文中规定官能之外的或不同于本文中指定官能的官能。
根据本公开的润滑油组合物可任选地包含其他性能添加剂。其他性能添加剂可为除了本公开的特定添加剂之外的添加剂和/或可包含以下中的一种或多种:金属钝化剂、粘度指数改善剂、无灰TBN增效剂、摩擦改性剂、抗磨剂、腐蚀抑制剂、防锈剂、分散剂、分散剂粘度指数改善剂、极压剂、抗氧化剂、泡沫抑制剂、破乳剂、乳化剂、降凝剂、密封溶胀剂以及它们的混合物。通常,全配方的润滑油将含有这些性能添加剂中的一种或多种。
合适的金属钝化剂可包括苯并三唑的衍生物(通常为甲苯基三唑)、二巯基噻二唑衍生物、1,2,4-三唑、苯并咪唑、2-烷基二硫代苯并咪唑或2-烷基二硫代苯并噻唑;泡沫抑制剂,包括丙烯酸乙酯和丙烯酸2-乙基己酯以及任选的乙酸乙烯酯的共聚物;破乳剂,包括磷酸三烷基酯、聚乙二醇、聚环氧乙烷、聚环氧丙烷和(环氧乙烷-环氧丙烷)聚合物;降凝剂,包括马来酸酐-苯乙烯的酯、聚甲基丙烯酸酯、聚丙烯酸酯或聚丙烯酰胺。
合适的泡沫抑制剂包括基于硅的化合物,如硅氧烷。
合适的降凝剂可以包括聚甲基丙烯酸甲酯或其混合物。倾点下降剂可以足以提供按润滑油组合物的最终重量计的约0wt.%至约1wt.%、约0.01wt.%至约0.5wt.%、或约0.02wt.%至约0.04wt.%的量存在。
合适的防锈剂可为具有抑制铁金属表面腐蚀的特性的单一化合物或化合物混合物。本文中有用的防锈剂的非限制性示例包括:油溶性高分子量有机酸,如2-乙基己酸、月桂酸、肉豆蔻酸、棕榈酸、油酸、亚油酸、亚麻酸、山嵛酸、以及蜡酸;以及包括二聚酸和三聚酸的油溶性聚羧酸,如由松油脂肪酸、油酸和亚油酸产生的那些。其他合适的腐蚀抑制剂包括分子量在约600至约3000范围内的长链α,ω-二羧酸,和其中烯基含有约10或更多个碳原子的烯基琥珀酸,如四丙烯基琥珀酸、十四烯基琥珀酸和十六烯基琥珀酸。另一种可用类型的酸性腐蚀抑制剂为在烯基中具有约8至约24个碳原子的烯基琥珀酸与醇(如聚乙二醇)的半酯。此类烯基琥珀酸的对应半酰胺也是有用的。有用的防锈剂为高分子量有机酸。在一些实施方案中,发动机油不含防锈剂。
防锈剂如果存在的话,则基于润滑油组合物的最终重量,可以足以提供约0重量%至约5重量%、约0.01重量%至约3重量%、约0.1重量%至约2重量%的量加以使用。
一般来说,合适的润滑剂可包括在下表中列出的范围中的添加剂组分。
表2
组分 | 重量%(广义) | 重量%(通常) |
分散剂 | 0.0-10% | 1.0-8.5% |
抗氧化剂 | 0.0-5.0 | 0.01-3.0 |
金属洗涤剂 | 0.1-15.0 | 0.2-8.0 |
无灰TBN促进剂 | 0.0-1.0 | 0.01-0.5 |
腐蚀抑制剂 | 0.0-5.0 | 0.0-2.0 |
金属二烃基二硫代磷酸盐 | 0.1-6.0 | 0.1-4.0 |
无灰胺磷酸盐 | 0.0-3.0 | 0.0-1.5 |
消泡剂 | 0.0-5.0 | 0.001-0.15 |
抗磨剂 | 0.0-10.0 | 0.0-5.0 |
降凝剂 | 0.0-5.0 | 0.01-1.5 |
粘度指数改善剂 | 0.0-20.00 | 0.25-10.0 |
分散剂粘度指数改善剂 | 0.0-10.0 | 0.0-5.0 |
摩擦改性剂 | 0.01-5.0 | 0.05-2.0 |
基础油 | 余量 | 余量 |
总 | 100 | 100 |
基于最终润滑油组合物的重量,以上每种组分的百分比表示每种组分的重量百分比。润滑油组合物的其余部分由一种或多种基础油组成。用于配制本文所描述的组合物的添加剂可以单独地或以各种子组合形式掺合到基础油中。然而,使用添加剂浓缩物(即,添加剂加稀释剂,诸如烃溶剂)同时掺合所有组分可以是合适的。用于配制本文所描述的组合物的添加剂可以单独地或以各种子组合形式掺合到基础油中。然而,使用添加剂浓缩物(即,添加剂加稀释剂,诸如烃溶剂)同时掺合所有组分可以是合适的。
完全配制的润滑剂通常含有添加剂包,在本文中称作分散剂/抑制剂包或DI包,其将供应配制物中所需的特征。例如在美国专利号5,204,012和6,034,040中描述了合适的DI包。包括在添加剂包中的添加剂类型可以是分散剂、密封溶胀剂、抗氧化剂、泡沫抑制剂、润滑剂、防锈剂、抗蚀剂、破乳剂、粘度指数改善剂等。这些组分中的几种组分是本领域技术人员众所周知的,并且通常以常规量与本文所述的添加剂和组合物一起使用。
实施例
以下实施例是本公开的示例性实施方案的说明。在这些实施例中,以及在本申请的其他地方,除非另有说明,反正所有比例、份数和百分比均按重量计。有意的是,这些实施例仅用于说明的目的而呈现,而不是用于限制本文所公开的本发明的范围。
实施例1
制备两种润滑油组合物用于评价当润滑汽油发动机时的微粒排放。下表3提供了用于本文方法的本发明润滑剂A和混合的钙/镁比较润滑剂B的分析结果。
表3.
对于润滑剂,各自包括第III类基础油和添加剂包,所述添加剂包包括粘度指数改善剂、分散剂、消泡剂、胺类抗氧化剂、ZDDP抗磨剂、硫化烯烃抗氧化剂、摩擦改性剂、倾点下降剂和洗涤剂体系。本发明润滑剂A包含1.8重量%的提供钙的TBN为300的高碱性磺酸钙,并且比较润滑剂B包含1.1重量%的高碱性磺酸钙以及0.63重量%的提供镁的TBN为约405的高碱性磺酸镁。
本发明润滑剂A的钙与镁的重量比为约280∶1,并且总矿物(其中总矿物包含钼、磷、锌、硼、镁和钙)的约53重量%为钙,并且总矿物的约0.19重量%为镁。对于比较润滑剂B,其钙与镁的重量比为约2.6∶1,并且总矿物的约35重量%为钙,并且总矿物的约14重量%为镁。
实施例2
基于US06驱动循环的测试方案用于评价汽油发动机的排气管微粒排放。该方案总结在下表4中并且以冷启动US06循环(在至少8小时浸泡之后)开始,并且随后是四个连续的热启动US06循环(在每个循环之间有1小时浸泡),其中机动车速度如图1中所示。附图中提供了示例性机动车速度。每次测试花费大约6小时。测试在使用本发明润滑剂A和比较润滑剂B的运行之间交替进行。当测试需要换油时进行两次油冲洗。用于测试的机动车是2011Nissan Juke,其具有1.6L直接喷射汽油发动机并改装了GPF过滤器,以用于本文的测试。汽油是EEE燃料。
表4.
在整个驱动循环中使用黄金微粒测量系统(GPMS)测量颗粒物数目,如欧盟委员会理事会联合研究中心并且名称为“Particle Measurement Programme(PMP)Light-DutyInter-laboratory Correlation Exercise(ILCE_LD)Final Report dated 2007”(EUR22775 EN)的报告所述,该报告以引用方式并入本文。所用设备是发动机排气冷凝颗粒物计数器(型号3790)和发动机排气颗粒物筛分器(型号3090),两者都来自TSI公司。具有速度轨迹的示例性单驱动循环瞬时颗粒物数目测量显示在图2中,并且比较本发明润滑剂A和比较润滑剂B的每个循环的总颗粒物数目结果显示在图3中。这些结果的统计学分析显示在图4中。
如图中所示,与混合金属比较润滑剂B相比,在用本发明润滑剂A润滑的发动机中燃烧汽油的方法的排气管颗粒物数目排放显著(并且统计学上显著)降低。图4所示的统计分析/箱线图说明了使用本发明润滑油A的方法的排气管微粒数目降低。平均而言,燃烧用本发明润滑油A润滑的汽油的方法比用混合金属比较润滑油B润滑的汽油得到更低的微粒数目排放结果。如箱线图(其中1是本发明润滑剂A,2是比较润滑剂B,CS是指冷启动方案,并且WS是指热启动方案)所示,微粒数目的减少在95%置信水平下是统计学上显著的。
应注意,除非明确地且肯定地限于一个指示物,否则如本说明书和所附权利要求书中所使用,单数形式“一(a/an)”和“所述(the)”包括多个指示物。因此,例如,提及“抗氧化剂”包括两种或更多种不同抗氧化剂。如本文所用的术语“包括”及其语法变体旨在为非限制性的,以使得列表中的项目的叙述不排除可以被取代或添加到所列项目中的其他类似项目。
对于本说明书和所附权利要求书来说,除非另有说明,否则在说明书和权利要求书中使用的表示数量、百分比或比例的所有数字以及其他数值应理解为在所有情况下都被术语“约”修饰。因此,除非相反地指示,否则以下说明书和所附权利要求书中所阐述的数值参数是可以取决于试图通过本公开获得的所需特性而变化的近似值。最低限度地,并且不试图限制等效物原则应用于权利要求书的范围,至少应根据所报告的有效数字的数目并且通过应用一般四舍五入技术来解释每个数值参数。
应理解,本文所公开的每种组分、化合物、取代基或参数应解释为公开以单独地或与本文所公开的每一种其他组分、化合物、取代基或参数中的一个或多个组合使用。
应另外理解,本文所公开的每个范围应解释为具有相同有效数字数值的在所公开范围内的每个具体值的公开。因此,例如,1到4的范围应解释为值1、2、3和4以及此类值的任何范围的明确公开。
应另外理解,本文所公开的每个范围的每个下限应解释为与本文中针对相同组分、化合物、取代基或参数所公开的每个范围的每个上限和每个范围内的每个具体值组合公开。因此,本公开应解释为通过将每个范围的每个下限与每个范围的每个上限或与每个范围内的每个具体值组合、或通过将每个范围的每个上限与每个范围内的每个具体值组合衍生的所有范围的公开。也就是说,还应另外理解,本文还论述在宽范围内的端点值之间的任何范围。因此,1到4的范围还意指1到3、1到2、2到4、2到3等的范围。
此外,本说明书或实施例中所公开的组分、化合物、取代基或参数的特定量/值应解释为一定范围的下限或上限的公开,并且因此可以与针对本公开中其他地方所公开的相同组分、化合物、取代基或参数的范围的任何其他下限或上限或特定量/值组合,以形成那种组分、化合物、取代基或参数的范围。
虽然已经描述特定实施方案,但是申请人或本领域的其他技术人员可想到当前未预见到或当前可能未预见到的替代方案、修改、变化、改进和实质性等同方案。因此,如提交并且如其可以被修正的所附权利要求书旨在涵盖所有此类替代方案、修改、变化、改进和实质性等同方案。
Claims (15)
1.一种减少来自汽油发动机的微粒排放的方法,所述方法包括:在汽油发动机中燃烧汽油组合物,其中所述汽油发动机用包含至少约1500ppm的钙和不超过约500ppm的镁的润滑组合物润滑。
2.根据权利要求1所述的减少微粒排放的方法,其中在所述润滑组合物中由洗涤添加剂提供的钙与镁的重量比为约10:1至约300:1。
3.根据权利要求1所述的减少微粒排放的方法,其中与用具有混合的钙和镁金属组合物的润滑组合物润滑时通过颗粒物数目测量的来自所述汽油发动机中所述汽油组合物的燃烧的微粒排放相比,通过颗粒物数目测量的来自所述汽油发动机中所述汽油组合物的燃烧的所述微粒排放减少,其中在所述润滑组合物中由洗涤添加剂提供的钙与镁的重量比为约2:1至小于约10:1,并且其中根据US06驱动循环在所述汽油组合物的所述燃烧期间测量颗粒物数目。
4.根据权利要求3所述的减少微粒排放的方法,其中所述汽油发动机配备有汽油微粒过滤器,并且在一个US06驱动循环之后所述微粒排放减少,而与所述汽油微粒过滤器的任何先前的灰分和/或烟灰积聚无关。
5.根据权利要求1所述的减少微粒排放的方法,所述方法进一步包括在执行US06驱动循环时测量微粒排放作为颗粒物数目;并且/或者其中根据黄金颗粒测量系统(GPMS)测量颗粒物数目。
6.根据权利要求1所述的减少微粒排放的方法,其中所述汽油发动机是配备有汽油微粒过滤器的混合电动发动机。
7.根据权利要求1所述的减少微粒排放的方法,其中所述润滑组合物包含约1,800ppm至约3,000ppm的钙和约10ppm至约100ppm的镁;并且/或者其中所述润滑组合物包含约3,000ppm至约5,000ppm的总矿物,并且其中所述总矿物的约40ppm至约60重量%为钙且所述总矿物的不超过约1重量%为镁。
8.根据权利要求7所述的减少微粒排放的方法,其中所述润滑组合物的所述总矿物进一步包含选自钼、磷、锌、硼或它们的组合的矿物。
9.根据权利要求8所述的减少微粒排放的方法,其中所述润滑组合物的所述总矿物包含约1重量%至约5重量%的钼、约15重量%至约15重量%的磷、约15重量%至约30重量%的锌和约1重量%至约10重量%的硼。
10.根据权利要求1所述的减少微粒排放的方法,其中所述润滑组合物进一步包含一种或多种选自粘度指数改善剂、分散剂、消泡添加剂、抗氧化剂、抗磨添加剂、摩擦改性剂、倾点分散剂、洗涤剂或它们的组合的添加剂。
11.根据权利要求1所述的减少微粒排放的方法,其中钙由中性至高碱性磺酸钙、酚钙或水杨酸钙中的一者或多者提供;并且/或者其中钙由总碱值为200mg KOH/g至500mg KOH/g的高碱性磺酸钙提供;并且/或者其中镁由选自磺酸镁、酚镁和水杨酸镁的洗涤添加剂提供。
12.根据权利要求1所述的减少微粒排放的方法,其中所述汽油组合物包含约10ppm至约200ppm的曼尼希洗涤剂。
13.根据权利要求1所述的减少微粒排放的方法,其中所述汽油发动机配备有汽油微粒过滤器。
14.根据权利要求1所述的减少微粒排放的方法,其中所述润滑组合物包含至少约1,800ppm的钙和不超过约100ppm的镁;并且/或者其中所述润滑组合物包含至少约2,000ppm的钙和不超过约50ppm的镁;并且/或者其中所述润滑组合物包含至少约2,000ppm的钙和不超过约25ppm的镁。
15.根据权利要求1所述的减少微粒排放的方法,其中在所述润滑组合物中由洗涤添加剂提供的钙与镁的重量比为约150:1至约300:1。
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JP5952846B2 (ja) * | 2014-01-31 | 2016-07-13 | 出光興産株式会社 | 潤滑油組成物 |
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-
2022
- 2022-05-26 US US17/825,532 patent/US20230383211A1/en active Pending
-
2023
- 2023-05-23 JP JP2023084584A patent/JP2023174583A/ja not_active Abandoned
- 2023-05-25 CN CN202310597318.1A patent/CN117128110A/zh active Pending
- 2023-05-25 EP EP23175481.3A patent/EP4282937A1/en active Pending
Also Published As
Publication number | Publication date |
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EP4282937A1 (en) | 2023-11-29 |
JP2023174583A (ja) | 2023-12-07 |
US20230383211A1 (en) | 2023-11-30 |
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