CN102753662B - 含抗磨剂的润滑组合物 - Google Patents
含抗磨剂的润滑组合物 Download PDFInfo
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- CN102753662B CN102753662B CN201080046848.8A CN201080046848A CN102753662B CN 102753662 B CN102753662 B CN 102753662B CN 201080046848 A CN201080046848 A CN 201080046848A CN 102753662 B CN102753662 B CN 102753662B
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- lubricating composition
- alkyl
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- acid
- carbon atoms
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- 239000000203 mixture Substances 0.000 title claims abstract description 104
- 230000001050 lubricating effect Effects 0.000 title claims abstract description 69
- -1 phosphorous acid ester Chemical class 0.000 claims abstract description 66
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 41
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002360 explosive Substances 0.000 claims abstract description 30
- 239000000314 lubricant Substances 0.000 claims abstract description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000003921 oil Substances 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 150000002148 esters Chemical class 0.000 claims description 19
- 239000002270 dispersing agent Substances 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000003599 detergent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 12
- 229910000838 Al alloy Inorganic materials 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 238000005461 lubrication Methods 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 230000005496 eutectics Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 235000019198 oils Nutrition 0.000 description 31
- 239000000654 additive Substances 0.000 description 18
- 230000000996 additive effect Effects 0.000 description 16
- 229940095064 tartrate Drugs 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 150000001412 amines Chemical class 0.000 description 14
- 239000010705 motor oil Substances 0.000 description 14
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 229920000768 polyamine Polymers 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 150000003949 imides Chemical group 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229960002317 succinimide Drugs 0.000 description 6
- 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 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 230000009931 harmful effect Effects 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000005078 molybdenum compound Substances 0.000 description 5
- 150000002752 molybdenum compounds Chemical class 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002924 oxiranes Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 3
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 3
- 150000002646 long chain fatty acid esters Chemical group 0.000 description 3
- 150000004668 long chain fatty acids Chemical class 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 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 3
- 230000003449 preventive effect Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 description 2
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 2
- 230000002929 anti-fatigue Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 2
- KAJZYANLDWUIES-UHFFFAOYSA-N heptadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCN KAJZYANLDWUIES-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002462 imidazolines Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 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
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 231100000241 scar Toxicity 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- UATFHWVUSDADRL-FPLPWBNLSA-N (z)-hexadec-9-en-1-amine Chemical compound CCCCCC\C=C/CCCCCCCCN UATFHWVUSDADRL-FPLPWBNLSA-N 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- QVXGKJYMVLJYCL-UHFFFAOYSA-N 2,3-di(nonyl)-N-phenylaniline Chemical compound C(CCCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCCC QVXGKJYMVLJYCL-UHFFFAOYSA-N 0.000 description 1
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical class CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-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
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- NKMZBGMEVYDZSR-UHFFFAOYSA-N 4-butoxy-2,3-dihydroxy-4-oxobutanoic acid Chemical compound CCCCOC(=O)C(O)C(O)C(O)=O NKMZBGMEVYDZSR-UHFFFAOYSA-N 0.000 description 1
- WTWGHNZAQVTLSQ-UHFFFAOYSA-N 4-butyl-2,6-ditert-butylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WTWGHNZAQVTLSQ-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- 239000005995 Aluminium silicate Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- UUNBFTCKFYBASS-UHFFFAOYSA-N C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC Chemical compound C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC UUNBFTCKFYBASS-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical group S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
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- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- UWHZIFQPPBDJPM-FPLPWBNLSA-M Vaccenic acid Natural products CCCCCC\C=C/CCCCCCCCCC([O-])=O UWHZIFQPPBDJPM-FPLPWBNLSA-M 0.000 description 1
- 235000021322 Vaccenic acid Nutrition 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
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- 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
- 239000003345 natural gas Substances 0.000 description 1
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- 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 1
- 230000036961 partial effect Effects 0.000 description 1
- 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 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
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- 238000007789 sealing Methods 0.000 description 1
- 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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- 125000001424 substituent group Chemical group 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003899 tartaric acid esters Chemical class 0.000 description 1
- 210000001138 tear Anatomy 0.000 description 1
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- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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 1
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Classifications
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
- C10M129/44—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms containing hydroxy groups
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- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/44—Five-membered ring containing nitrogen and carbon only
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- C10M135/10—Sulfonic acids or derivatives thereof
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- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
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- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
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- C10M137/10—Thio derivatives
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2207/124—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms containing hydroxy groups; Ethers thereof
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- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/24—Epoxidised acids; Ester derivatives thereof
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- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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Abstract
本发明提供包含以下组分的润滑组合物：(a)润滑粘度的油，(b)具有至少一个含4个或更多碳原子的烃基的亚磷酸酯，和(c)衍生自羟基羧酸的化合物。本发明进一步涉及所述润滑组合物在内燃发动机中的用途。
Description
发明领域
本发明提供包含以下组分的润滑组合物：(a)润滑粘度的油，(b)具有至少一个含4个或更多碳原子的烃基的亚磷酸酯，和(c)衍生自羟基羧酸的化合物。本发明进一步涉及所述润滑组合物在内燃发动机中的用途。所述内燃发动机可以具有铝合金或铝复合材料的表面。
发明背景
已知润滑油包含用于保护内燃发动机免受腐蚀、磨损、烟炱沉积和酸累积的许多表面活性添加剂(包括抗磨剂、分散剂或清净剂)。通常，这样的表面活性添加剂可对(铁和铝基组件中的)发动机部件磨损，承受腐蚀或燃料经济性具有有害影响。用于发动机润滑油的常规抗磨添加剂是二烷基二硫代磷酸锌(ZDDP)。据信ZDDP抗磨添加剂通过在金属表面形成保护膜来保护发动机。ZDDP还可能对燃料经济性和效率和铜腐蚀具有有害影响。因此，发动机润滑剂还可以含有摩擦改进剂以消除ZDDP对燃料经济性的有害影响并含有缓蚀剂以消除ZDDP对铜腐蚀的有害影响。其它添加剂也可增加铅腐蚀。
发动机设计方面的开发已经获得采用含铁和/或非铁组件的发动机。通常，它们的非铁发动机组件基于铝合金、硅酸盐、氧化物或其它陶瓷材料。抗磨添加剂例如ZDDP被认为与铁基发动机相比在铝合金基发动机中导致更差的发动机磨损性能。
此外，已表明，含有磷化合物和硫的发动机润滑剂对颗粒物排放和其它污染物的排放起部分作用。此外，硫和磷易于使催化转换器中所用的催化剂中毒，而导致所述催化剂性能的降低。
考虑到向更严格的排放标准靠近和某些元素的有害影响，仍希望降低的发动机油中硫、磷和硫酸盐灰分的量。因此，已经减少含磷抗磨剂例如ZDDP、过碱性清净剂例如钙或镁磺酸盐和酚盐的量。结果，已经考虑无灰添加剂例如多元醇或含羟基酸的酯，包括单油酸甘油酯用来提供摩擦性能。
加拿大专利CA1183125(于1981年9月10日由Barrer提交)公开了含烷基-酯酒石酸酯的汽油发动机用润滑剂，其中烷基上的碳原子之和是至少8。所述酒石酸酯公开为抗磨剂。公开酒石酸酯和/或酒石酰亚胺的其它参考文献包括国际公开WO2006/044411，和要求减少量的硫、硫酸盐灰分和磷的内燃发动机的美国专利申请。所述润滑组合物具有抗磨损或抗疲劳性能。所述润滑组合物适合于公路车辆。
美国专利4,237,022(于1980年12月2日由Barrer提交)公开了可用作润滑剂和燃料中的用于有效减少振鸣和摩擦以及改进燃料经济性的添加剂的酒石酰亚胺。
美国专利5,338,470(于1992年12月10日由Hiebert提交)和国际公开WO2005/087904(于2004年3月11日由Migdal提交)公开了含至少一种羟基羧酸酯或羟基多元羧酸(特别是柠檬酸酯或乙醇酸乙酯)的润滑剂。所述润滑组合物具有抗磨损或抗疲劳性能。
国际申请WO2008/070307(于2007年10月22日由Brown提交)公开了含基于丙二酸酯的抗磨剂的发动机润滑剂。
发明概述
本发明发明人已经发现能够提供抗磨，或摩擦改进中至少一项(尤其是用于提高燃料经济性)的润滑组合物。
本文所使用的存在于本文中公开的润滑组合物中的添加剂的量以无油基础计算，即活性材料的量。
在本发明一个实施方案中，提供了润滑组合物，其包含：(a)润滑粘度的油，(b)具有至少一个含4个或更多，或8个或更多，或12个或更多碳原子的烃基的亚磷酸酯，和(c)衍生自羟基羧酸的化合物。
在一个实施方案中，本发明提供了润滑组合物，其中具有至少一个含4个或更多碳原子的烃基的亚磷酸酯和衍生自羟基羧酸的化合物可以同时按在以下范围内的量存在：
(i)分别为润滑组合物的0.01wt％至5wt％和0.01wt％至5wt％，或
(ii)分别为润滑组合物的0.1wt％至3wt％和0.1wt％至3wt％，或
(iii)分别为润滑组合物的0.2wt％至1.5wt％和0.2wt％至1.5wt％，或
(iv)分别为润滑组合物的0.25wt％至1wt％和0.25wt％至1wt％，或
(v)分别为润滑组合物的0.5wt％至1wt％和0.5wt％至1wt％。
在本发明一个实施方案中，提供了润滑组合物，其包含：(a)润滑粘度的油，(b)具有至少一个含4个或更，或8个或更多，或12个或更多碳原子的烃基的亚磷酸酯，(c)衍生自羟基羧酸的化合物，和(d)二烷基二硫代磷酸锌，其中所述亚磷酸酯为所述润滑组合物递送至少0.01wt％至0.12wt％，或0.01wt％至0.08wt％的磷。
在一个实施方案中，具有至少一个含4个或更多碳原子的烃基的亚磷酸酯和衍生自羟基羧酸的化合物可以同时按分别为润滑组合物的0.5wt％至1wt％和0.5wt％至1wt％的量存在。
在一个实施方案中，本发明提供润滑内燃发动机的方法，包括将本文所公开的润滑组合物供给内燃发动机。
在一个实施方案中，本发明提供本文公开的润滑内燃发动机的方法，其中所述内燃发动机具有铝合金或铝复合材料的表面。
在一个实施方案中，本发明提供本文公开的润滑内燃发动机的方法，其中所述铝合金是低共熔或超低共熔铝合金(例如衍生自硅酸铝、氧化铝或其它陶瓷材料的那些)。
在一个实施方案中，本文所公开的润滑内燃发动机的方法，其中所述内燃发动机具有钢表面。
在一个实施方案中，本发明提供本文所公开的润滑内燃发动机的方法，其中所述内燃发动机包括具有铝合金、铝复合材料或铁表面的气缸孔(cylinderbore)、气缸柱(cylinderblock)或活塞环。
在一个实施方案中，本发明提供润滑剂用来为铝基表面(尤其是内燃发动机铝基表面)提供磨损保护性和/或燃料经济性(降低的摩擦改进性能)中至少一项的用途，其中所述润滑组合物包含(a)润滑粘度的油，(b)具有至少一个含4个或更，或8个或更多，或12个或更多碳原子的烃基的亚磷酸酯，和(c)衍生自羟基羧酸的化合物。
在一个实施方案中，本发明提供润滑剂用来为内燃发动机的金属表面(可以是铁或铝基，通常铝基金属表面)提供磨损保护性的用途，其中所述润滑组合物包含(a)润滑粘度的油，(b)具有至少一个含4个或更，或8个或更多，或12个或更多碳原子的烃基的亚磷酸酯，和(c)衍生自羟基羧酸的化合物。
发明详述
本发明提供上面公开的润滑组合物和润滑发动机的方法。
衍生自羟基羧酸的化合物
本发明提供含衍生自羟基羧酸的化合物的润滑组合物。所述衍生自羟基羧酸的化合物可以由下式表示：
其中
n和m可以独立地是1-5的整数；
X可以是脂族或脂环族基团，或碳链中含氧原子的脂族或脂环族基团，或取代的上述类型的基团，所述基团含有至多6个碳原子且具有n+m个可用的连接点；
每个Y可以独立地是-O-、＞NH或＞NR1或两个Y一起可以代表在两个羰基之间形成的酰亚胺结构R-N＜的氮；和
每个R和R1可以独立地是氢或烃基，条件是至少一个R或R1基团是烃基；每个R2可以独立地是氢、烃基或酰基，进一步条件是至少一个-OR2基团位于X内的对-C(O)-Y-R基团中的至少一个而言的α或β位的碳原子上。
衍生自羟基羧酸的化合物可以衍生自乙醇酸(n和m都等于1)，苹果酸(n＝2，m＝1)，酒石酸(n和m都等于2)，柠檬酸(n＝3，m＝1)，或它们的混合物。在一个实施方案中，衍生自羟基羧酸的化合物可以衍生自酒石酸。
衍生自羟基羧酸的化合物可以是羟基羧酸的酰胺、酯或酰亚胺衍生物，或它们的混合物。在一个实施方案中，衍生自羟基羧酸的化合物可以是羟基羧酸的酰胺、酯或酰亚胺衍生物。例如，酒石酸的酯或酰亚胺。
在一个实施方案中，衍生自羟基羧酸的化合物可以是羟基羧酸二酯、羟基羧酸二-酰胺、羟基羧酸二-酰亚胺、羟基羧酸单酰亚胺、羟基羧酸酯-酰胺、羟基羧酸酯-酰亚胺和羟基羧酸酰亚胺-酰胺中的至少一种。在一个实施方案中，羟基羧酸的酰胺、酯或酰亚胺衍生物可以衍生自由羟基羧酸二酯、羟基羧酸二-酰胺、羟基羧酸单酰亚胺和羟基羧酸酯-酰胺构成的组中的至少一种。
衍生自羟基羧酸的化合物中的每个R、R1和R2基团可以是各自含1-150，或8-30，或8-20个碳原子的直链或支化烷基。所述羟基羧酸的酯衍生物可以通过醇与羟基羧酸的反应形成。醇包括一元醇和多元醇。醇的碳原子可以是直链、支化链或它们的混合物。
适合的支化醇的实例包括2-乙基己醇、异十三烷醇、异辛基、格尔伯特醇(Guerbetalcohol)或它们的混合物。
一元醇的实例包括甲醇、乙醇、丙醇、丁醇、戊醇、己醇、庚醇、辛醇、壬醇、癸醇、十一烷醇、十二烷醇、十三烷醇、十四烷醇、十五烷醇、十六烷醇、十七烷醇、十八烷醇、十九烷醇、二十烷醇或它们的混合物。在一个实施方案中，一元醇含有8-20个碳原子。
在一个实施方案中，羟基羧酸的酰亚胺衍生物可以是酒石酰亚胺，通常含8-20个碳原子。用来制备酰亚胺的胺可以包括烷基胺(例如正己胺(己酰基胺)、正辛胺(辛酰基胺)、正癸胺(癸酰基胺)、正十二烷基胺(月桂胺)、正十四烷基胺(肉豆蔻基胺)、正十五烷基胺、正十六烷基胺(棕榈基胺)、十七烷基胺(margarylamine)、正十八烷基胺(硬脂胺))，不饱和胺(例如十二碳烯基胺、十四碳烯基胺(myristoleylamine)、十六碳烯基胺(palmitoleylamine)、油基胺和亚油基胺)，或醚胺(例如标示为SURFAMTMP14AB(支化C14)、SURFAMTMP16A(直链C16)和SURFAMTMP17AB(支化C17)的那些)。制备适合的酒石酰亚胺的方法(通过使酒石酸与伯胺反应)的详细说明公开于美国专利4,237,022中。
美国专利申请60/939949(于2007年5月24日提交；现WO2008/147704)和60/939952(于2007年5月24日提交；现US2010-0093573)更详细地公开了可用于本发明的羟基羧酸化合物。
加拿大专利1183125；美国专利公开号2006/0183647和US-2006-0079413；美国专利申请号60/867402(现WO2008/067249)和英国专利2105743A都公开了适合的酒石酸衍生物的有用实例。
衍生自羟基羧酸的化合物可以按润滑组合物的0.01wt％至5wt％，或0.1wt％至3wt％，或0.2wt％至1.5wt％，或0.25wt％至1wt％，或0.5wt％至1wt％存在。
亚磷酸酯
本发明提供了含亚磷酸酯的润滑组合物，该亚磷酸酯具有至少一个含4个或更多，或8个或更多，或12个或更多碳原子的烃基。烃基上的碳原子数目的典型范围包括8-30，或10-24，或12-22，或14-20，或16-18。亚磷酸酯可以是单烃基取代的亚磷酸酯、二烃基取代的亚磷酸酯或三烃基取代的亚磷酸酯。
在一个实施方案中，亚磷酸酯是无硫的，即所述亚磷酸酯不是硫代亚磷酸酯。
具有至少一个含4个或更多碳原子的烃基的亚磷酸酯可以由下式表示：
其中R3、R4和R5中至少一个可以是含至少4个碳原子的烃基且其它可以是氢或烃基。在一个实施方案中，R3、R4和R5都是烃基。所述烃基可以是烷基、环烷基、芳基、无环的或它们的混合物。在具有所有三个基团R3、R4和R5的通式中，化合物可以是三烃基取代的亚磷酸酯，即R3、R4和R5都是烃基。
烷基可以是直链或支化的，通常是直链的，且是饱和或不饱和的，通常是饱和的。R3、R4和R5的烷基的实例包括辛基、2-乙基己基、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、十八烷基、十八碳烯基、十九烷基、二十烷基或它们的混合物。
具有至少一个含4个或更多碳原子的烃基的亚磷酸酯可以按润滑组合物的0.01wt％至5wt％，或0.1wt％至3wt％，或0.2wt％至1.5wt％，或0.25wt％至1wt％，或0.5wt％至1wt％存在。
润滑粘度的油
该润滑组合物包含润滑粘度的油。这些油包括天然和合成油，衍生自加氢裂化、加氢化和加氢精制的油，未精炼的、精炼的、再精炼的油或它们的混合物。未精炼的、精炼的和再精炼的油的更详细描述提供在国际公开WO2008/147704的[0054]-[0056]段中。天然和合成润滑油的更详细描述分别描述在WO2008/147704的[0058]-[0059]段中。合成油也可以通过费-托反应(Fischer-Tropschreaction)制备并且通常可以是加氢异构化的费-托烃或蜡。在一个实施方案中，油可以通过费-托气-液合成程序以及其它气-液油制备。
润滑粘度的油也可以如“AppendixE-APIBaseOilInterchangeabilityGuidelinesforPassengerCarMotorOilsandDieselEngineOils”的2008年4月版本1.3节小标题1.3.“BaseStockCategories”中规定那样定义。在一个实施方案中，润滑粘度的油可以是API第I组，或第II组，或第III组或第IV组油。在一个实施方案中，润滑粘度的油可以是API第II组或第III组油。在一个实施方案中，润滑粘度的油可以是加氢裂化或剧烈加氢裂化的基础油料和/或API第II组或第III组油。
润滑粘度的油的存在量通常是在从100wt％中减去本发明化合物和其它性能添加剂的总量之后剩余的平衡量。
润滑组合物可以呈浓缩物和/或完全配制润滑剂形式。如果本发明的润滑组合物(包含本文公开的添加剂)呈浓缩物(它们可以与附加的油结合而完全或部分地形成成品润滑剂)形式，则这些添加剂与润滑粘度的油和/或稀释油的比例包括按重量1∶99-99∶1，或按重量10∶90-80∶20的范围。
其它性能添加剂
组合物任选地包含其它性能添加剂。其它性能添加剂包括金属减活剂、粘度改进剂、清净剂、摩擦改进剂、抗磨剂、缓蚀剂、分散剂、分散剂粘度改进剂、极压剂、抗氧化剂、泡沫抑制剂、破乳剂、倾点下降剂、密封溶胀剂和它们的混合物中的至少一种。通常，完全配制的润滑油将含有这些性能添加剂中的一种或多种。
在一个实施方案中，润滑组合物还包括其它添加剂。在不同的实施方案中，润滑组合物可以具有以下表中所述的组成：
脚注：
1-化合物如上所述为衍生自羟基羧酸的化合物
2-亚磷酸酯如上所述具有至少一个含4个或更多碳原子的烃基
在一个实施方案中，本发明提供了还包含分散剂、抗磨剂、分散剂粘度改进剂、摩擦改进剂、粘度改进剂、抗氧化剂、过碱性清净剂或它们的混合物中的至少一种的润滑组合物。
本发明的分散剂可以是琥珀酰亚胺分散剂，或它们的混合物。在一个实施方案中，分散剂可以作为单一分散剂存在。在一个实施方案中，分散剂可以按两种或三个不同分散剂的混合物存在，其中至少一种可以是琥珀酰亚胺分散剂。
琥珀酰亚胺分散剂可以衍生自脂族多胺，或它们的混合物。脂族多胺可以是脂族多胺例如亚乙基多胺、亚丙基多胺、亚丁基多胺或它们的混合物。在一个实施方案中，脂族多胺可以是亚乙基多胺。在一个实施方案中，脂族多胺可以选自乙二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、五亚乙基六胺、多胺蒸馏釜残液和它们的混合物。
分散剂可以是N-取代的长链烯基琥珀酰亚胺。N-取代的长链烯基琥珀酰亚胺的实例包括聚异丁烯琥珀酰亚胺。通常，衍生出聚异丁烯琥珀酸酐的聚异丁烯具有350-5000，或550-3000或750-2500的数均分子量。琥珀酰亚胺分散剂和它们的制备例如公开在美国专利3,172,892、3,219,666、3,316,177、3,340,281、3,351,552、3,381,022、3,433,744、3,444,170、3,467,668、3,501,405、3,542,680、3,576,743、3,632,511、4,234,435、Re26,433和6,165,235、7,238,650和EP专利申请0355895A中。
分散剂还可以通过常规方法通过与各种试剂中的任意试剂反应加以后处理。这些试剂包括硼化合物、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、环氧化物和磷化合物。
分散剂可以按润滑组合物的0.01wt％至20wt％，或0.1wt％至15wt％，或0.1wt％至10wt％，或1wt％至6wt％存在。
在一个实施方案中，本发明的润滑组合物还包含分散剂粘度改进剂。所述分散剂粘度改进剂可以按润滑组合物的0wt％至5wt％，或0wt％至4wt％，或0.05wt％至2wt％存在。
分散剂粘度改进剂可以包含官能化的聚烯烃，例如用酰化剂例如马来酸酐和胺官能化的乙烯-丙烯共聚物；用胺官能化的聚甲基丙烯酸酯，或与胺反应的苯乙烯-马来酸酐共聚物。分散剂粘度改进剂的更详细描述公开在国际公开WO2006/015130或美国专利4,863,623；6,107,257；6,107,258和6,117,825中。在一个实施方案中，分散剂粘度改进剂可以包括描述在美国专利4,863,623(参见第2栏第15行到第3栏第52行)或国际公开WO2006/015130(参见第2页[0008]段并且制备实施例描述在[0065]-[0073]段)中的那些。
在一个实施方案中，所述摩擦改进剂可以选自胺的长链脂肪酸衍生物、长链脂肪酯或长链脂肪环氧化物；脂肪咪唑啉；和烷基磷酸的胺盐。摩擦改进剂可以按润滑组合物的0wt％至6wt％，或0.05wt％至4wt％，或0.1wt％至2wt％存在。
在一个实施方案中，本发明提供了还包括二烷基二硫代磷酸锌或它们的混合物的润滑组合物。二烷基二硫代磷酸锌盐是本领域中已知的。抗磨剂可以按润滑组合物的0wt％至15wt％，或0.1wt％至10wt％，或0.1wt％至5wt％，或0.5wt％至2wt％，或0.75wt％至1.5wt％存在。在一个实施方案中，本发明提供了还包括按0wt％至0.05wt％，或0.01wt％至0.05wt％存在的二烷基二硫代磷酸锌的润滑组合物。
在一个实施方案中，本发明提供了还包含钼化合物的润滑组合物。钼化合物可以选自二烷基二硫代磷酸钼、二硫代氨基甲酸钼、钼化合物的胺盐和它们的混合物。所述钼化合物可以为润滑组合物提供0-1000ppm，或5-1000ppm，或10-750ppm，5ppm-300ppm，或20ppm-250ppm钼。
在一个实施方案中，本发明提供了还包含过碱性清净剂的润滑组合物。过碱性清净剂可以选自不含硫的酚盐、含硫酚盐、磺酸盐、萨利克拉特(salixarates)、水杨酸盐和它们的混合物。通常，过碱性清净剂可以是酚盐、含硫酚盐、磺酸盐、萨利克拉特和水杨酸盐的钠、钙或镁盐。过碱性酚盐和水杨酸盐通常具有180-450TBN的总碱值。过碱性磺酸盐通常具有250-600，或300-500的总碱值。过碱性清净剂是本领域中已知的。在一个实施方案中，磺酸盐清净剂可以是具有至少8的金属比的主要直链的烷基苯磺酸盐清净剂，如美国专利申请2005065045(以US7,407,919授权)的[0026]-[0037]段中描述那样。所述主要直链的烷基苯磺酸盐清净剂可以尤其用于帮助改进燃料经济性。过碱性清净剂是本领域中已知的。所述过碱性清净剂可以按于润滑组合物的0wt％至15wt％，或0.1wt％至10wt％，或0.2wt％至8wt％存。
在一个实施方案中，润滑组合物包含抗氧化剂，或它们的混合物。所述抗氧化剂可以按润滑组合物的0wt％至15wt％，或0.1wt％至10wt％，或0.5wt％至5wt％存在。
抗氧化剂包括硫化烯烃、烷基化二苯胺(通常二壬基二苯胺、辛基二苯胺、二辛基二苯胺)、位阻酚、钼化合物(例如二硫代氨基甲酸钼)或它们的混合物。
位阻酚抗氧化剂通常含有仲丁基和/或叔丁基作为空间位阻基团。酚基团可以进一步被烃基取代(通常直链或支化烷基)和/或连接到第二芳族基的桥联基。适合的位阻酚抗氧化剂的实例包括2，6-二叔丁基苯酚、4-甲基-2，6-二叔丁基苯酚、4-乙基-2，6-二叔丁基苯酚、4-丙基-2，6-二叔丁基苯酚或4-丁基-2，6-二叔丁基苯酚或4-十二烷基-2，6-二叔丁基苯酚。在一个实施方案中，受阻酚抗氧化剂可以是酯并且可以包括，例如得自Ciba的IrganoxTML-135。适合的含酯受阻酚抗氧化剂化学的更详细描述参见美国专利6,559,105。
适合的摩擦改进剂的实例包括胺、醇、酯或环氧化物的长链脂肪酸衍生物；脂肪咪唑啉例如羧酸和多亚烷基多胺的缩合产物；烷基磷酸的胺盐；或除了本发明描述的衍生自羟基羧酸的化合物之外的各种脂肪烷基酒石酯盐；脂肪烷基酒石酰亚胺；或脂肪烷基酒石酰胺。
摩擦改进剂还可以涵盖诸如硫化脂肪化合物和烯烃、二烷基二硫代磷酸钼、二硫代氨基甲酸钼、向日葵油或多元醇和脂族羧酸的单酯例如甘油单油酸酯(GMO)的材料。
在一个实施方案中，摩擦改进剂可以选自胺、酯或环氧化物的长链脂肪酸衍生物；脂肪烷基酒石酸酯；脂肪烷基酒石酰亚胺；和脂肪烷基酒石酰胺。所述脂肪烷基酒石酸酯；脂肪烷基酒石酰亚胺；和脂肪烷基酒石酰胺可以与上述羟基羧酸的酰胺、酯或酰亚胺衍生物相同或不同。
在一个实施方案中，摩擦改进剂可以是长链脂肪酸酯。在另一个实施方案中，长链脂肪酸酯可以是单酯，在另一个实施方案中，长链脂肪酸酯可以是甘油(三)酯。
其它性能添加剂例如缓蚀剂包括作为WO2006/047486公开的美国申请US05/038319的5-8段中描述的那些，辛胺辛酸盐、十二碳烯基琥珀酸或酸酐和脂肪酸例如油酸与多胺的缩合产物。在一个实施方案中，缓蚀剂包括缓蚀剂。缓蚀剂可以是氧化丙烯的均聚物或共聚物。缓蚀剂更详细地描述在具有FormNo.118-01453-0702AMS由DowChemicalCompany出版的产品手册中。该产品手册标题为“SYNALOXLubricants，High-PerformancePolyglycolsforDemandingApplications”。
可有用的是金属减活剂，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，包括含硅聚合物、丙烯酸乙酯和丙烯酸2-乙基己酯和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、聚氧化乙烯、聚氧化丙烯和(氧化乙烯-氧化丙烯)聚合物；倾点下降剂，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。可用于本发明组合物的泡沫抑制剂包括丙烯酸乙酯和丙烯酸2-乙基己酯和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、聚氧化乙烯、聚氧化丙烯和(氧化乙烯-氧化丙烯)聚合物。
可用于本发明组合物的倾点下降剂包括聚α-烯烃、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。
工业应用
所述润滑组合物可以用于内燃发动机。所述内燃发动机可以具有或可以不具有废气再循环系统。所述内燃发动机可以装备有排放控制系统或涡轮增压器。排放控制系统的实例包括柴油机颗粒过滤器(DPF)，或采用选择性催化还原(SCR)的系统。
在一个实施方案中，内燃发动机可以是柴油燃料发动机(通常是重型柴油发动机)、汽油燃料发动机、天然气燃料发动机或混合汽油/醇燃料发动机。在一个实施方案中，内燃发动机可以是柴油燃料发动机，在另一个实施方案中，可以是汽油燃料发动机。
内燃发动机可以是2-冲程或4-冲程发动机。适合的内燃发动机包括船用柴油发动机、航空活塞发动机、低负荷柴油发动机、和汽车和卡车发动机。
内燃发动机的润滑剂组合物可以适合于任何发动机润滑剂，不管硫、磷或硫酸盐灰分(ASTMD-874)含量如何。发动机油润滑剂的硫含量可以是1wt％或更低，或0.8wt％或更低，或0.5wt％或更低，或0.3wt％或更低。在一个实施方案中，硫含量可以在0.001wt％至0.5wt％，或0.01wt％至0.3wt％的范围内。磷含量可以是0.2wt％或更低，或0.12wt％或更低，或0.1wt％或更低，或0.085wt％或更低，或0.08wt％或更低，或甚至0.06wt％或更低，0.055wt％或更低，或0.05wt％或更低。在一个实施方案中，磷含量可以是100ppm-1000ppm，或200ppm-600ppm。总硫酸盐灰分含量可以是2wt％或更低，或1.5wt％或更低，或1.1wt％或更低，或1wt％或更低，或0.8wt％或更低，或0.5wt％或更低或0.4wt％或更低。在一个实施方案中，硫酸盐灰分含量可以是0.05wt％至0.9wt％，或0.1wt％至0.2wt％或至0.45wt％。
在一个实施方案中，润滑组合物可以是发动机油，其中该润滑组合物可以表征为具有以下性质中至少一种：(i)0.5wt％或更低的硫含量，(ii)0.1wt％或更低的磷含量，和(iii)1.5wt％或更低的硫酸盐灰分含量。
下列实施例提供对本发明的说明。这些实施例并非穷举并且不打算限制本发明的范围。
实施例
润滑剂实施例1(EX1)是SAE5W-30发动机润滑剂，含有清净剂(包含磺酸钙和苯酚钙)、琥珀酰亚胺分散剂、0.5wt％酒石酸2-乙基己酯、0.5wt％二烷基二硫代磷酸锌和0.5wt％亚磷酸C16-18二烷基酯的混合物。
对比实施例1(CE1)是类似于EX1的SAE5W-30发动机润滑剂，不同在于它含有0.5wt％酒石酸2-乙基己酯和0.5wt％二烷基二硫代磷酸锌(即，没有亚磷酸C16-18二烷基酯)。CE1类似于WO2005/087904的实施例21，不同在于已经采用酒石酸2-乙基己酯而不是酒石酸丁酯(如实施例21中举例说明那样)。
对比实施例2(CE2)是类似于EX1的SAE5W-30发动机润滑剂，不同在于它含有1wt％酒石酸2-乙基己酯和0.5wt％二烷基二硫代磷酸锌(即，没有亚磷酸C16-18二烷基酯)。
对比实施例3(CE3)是类似于EX1的SAE5W-30发动机润滑剂，不同在于它含有0.5wt％亚磷酸C16-18二烷基酯和0.5wt％二烷基二硫代磷酸锌(即，没有酒石酸2-乙基己酯)
对比实施例4(CE4)是类似于EX1的SAE5W-30发动机润滑剂，不同在于它含有1wt％亚磷酸C16-18二烷基酯和0.5wt％二烷基二硫代磷酸锌(即，没有酒石酸2-乙基己酯)
对比实施例5(CE5)是类似于EX1的SAE5W-30发动机润滑剂，不同在于它含有0.5wt％二烷基二硫代磷酸锌(即，没有酒石酸2-乙基己酯和没有亚磷酸C16-18二烷基酯)。
试验：HFRR磨损
在可以从PCSInstruments获得的程序控制温度高频率往复移动装备(HFRR)中评价SAE5W-30润滑剂的磨损。用于评价的HFRR条件是500g负荷，75分钟持续时间，1000微米冲程，20赫兹频率，和在40℃下15分钟接着以2℃/分钟的速率提高到160℃的温度分布。上方试件是6mm直径钢球(ANSIE-52100，Rockwell‘C’硬度58-66和Ra＜0.05μm的表面光洁度)，下试样是扁平钢盘(ANSIE-52100，Vickers“HV30”硬度190-210和Ra＜0.02μm的表面光洁度)或相似尺寸的铝试样。上和下试样都可一起从PCSInstruments获得(部件号HFRSSP)。测量对于铝基发动机组件获得的磨损伤痕数据并提供在下表中：
| EX1 | CE1 | CE2 | CE3 | CE4 | CE5 | |
| 磨损伤痕(微米) | 172 | 207 | 213 | 255 | 227 | 274 |
总体上，给出的数据表明，本发明的润滑组合物(例如，内燃发动机润滑剂)提供与对比实施例润滑剂相比改进的抗磨损性能。数据证实具有铝基表面的内燃发动机的改进的性能。
已知，上述一些材料可以在最终配方中相互作用，以致最终配方的组分可能不同于最初添加的那些。由此形成的产物，包括本发明润滑剂组合物在其目标应用中使用时形成的产物，可能不容易描述。虽然如此，所有这些改进和反应产物包括在本发明范围内；本发明涵盖通过掺合上述组分制备的润滑剂组合物。
上面涉及的每篇文献通过引用并入本文。除了实施例中，或当另有明确说明时，该说明书中规定材料量、反应条件、分子量、碳原子数等的所有数值应理解由词语“大约”修饰。除非另有说明，本文涉及的每种化学物质或组合物应该解释为是商品级材料，它们可以包含异构体、副产物、衍生物和其它通常认为存在于商品级中的那些材料。然而，在不算任何溶剂或稀释油的情况下给出每种化学成分的量，所述溶剂或稀释油可以通常存在于商业材料中，除非另有说明。应该理解的是，本文给出的任何上限和下限量、范围和比例可以独立地结合。类似地，本发明每种要素的范围和量可以与任何其它要素的范围或量一起使用。
本文所使用的术语“烃基取代基”或“烃基”以其本领域技术人员熟知的普通含义使用。具体来说，它是指这样的基团，即其具有直接连接到分子其余部分的碳原子并主要具有烃性质。烃基的实例包括：烃取代基，包括脂族、脂环族和芳族取代基；取代的烃取代基，即，含有在本发明范围内不会改变取代基的主要为烃基的性质的非烃基团的取代基；和杂取代基，即相似地具有主要是烃的性质但是在环或链中含有除碳以外的原子的取代基。术语“烃基取代基”或“烃基”的更详细定义描述在国际公开WO2008147704的[0118]-[0119]段中。
本文所使用的术语“脂肪”，如在脂肪酸(及其它本文所使用的表述)中，包括含4-150，或4-30，或6-16个碳原子的烃基链。
虽然已经根据本发明的优选实施方案对其进行了说明，但是应该理解的是，本发明的各种修改对阅读了本说明书的本领域技术人员是显而易见的。因此，应该理解的是，在此公开的本发明旨在涵盖属于所附权利要求书范围内的那些修改。
Claims (14)
1.润滑组合物，其包含：
(a)润滑粘度的油，
(b)0.1wt％至5wt％的具有至少一个含4个或更多碳原子的烃基的亚磷酸酯，其中该具有至少一个含4个或更多碳原子的烃基的亚磷酸酯由下式表示：
或
其中R3、R4和R5中至少一个是含至少4个碳原子的烃基且其它是氢或烃基，和
(c)0.01wt％至5wt％的衍生自羟基羧酸的酯的化合物，其中所述羟基羧酸选自乙醇酸、苹果酸、柠檬酸或它们的混合物，和
(d)过碱性镁磺酸盐清净剂，其具有250-600的总碱值，其中过碱性镁磺酸盐清净剂以0.2wt％至8wt％的量存在，
其中所述润滑组合物特征在于具有(i)0.5wt％或更低的硫含量，(ii)0.1wt％或更低的磷含量，和(iii)1.5wt％或更低的硫酸盐灰分含量。
2.权利要求1所述的润滑组合物，其中所述衍生自羟基羧酸的酯的化合物按润滑组合物的0.5wt％至1wt％的量存在。
3.权利要求1所述的润滑组合物，其中R3和R4都是烃基。
4.权利要求1所述的润滑组合物，其中所述亚磷酸酯具有至少一个含14-20个碳原子的烃基。
5.上述权利要求1-4中任一项所述的润滑组合物，其中所述具有至少一个含4个或更多碳原子的烃基的亚磷酸酯按润滑组合物的0.1wt％至3wt％存在。
6.上述权利要求1-4中任一项所述的润滑组合物，其中所述具有至少一个含4个或更多碳原子的烃基的亚磷酸酯和衍生自羟基羧酸的化合物同时按在以下范围内的量存在：
(i)分别为润滑组合物0.1wt％至3wt％和0.1wt％至3wt％。
7.上述权利要求1-4中任一项所述的润滑组合物，还包含二烷基二硫代磷酸锌或它们的混合物。
8.权利要求7所述的润滑组合物，其中所述二烷基二硫代磷酸锌按润滑组合物的0.1wt％至5wt％存在。
9.上述权利要求1-4中任一项所述的润滑组合物，还包含抗磨剂、分散剂粘度改进剂、摩擦改进剂、粘度改进剂、抗氧化剂、过碱性清净剂或它们的混合物中的至少一种。
10.上述权利要求1-4中任一项所述的润滑组合物，还包含分散剂粘度改进剂。
11.润滑内燃发动机的方法，包括为所述内燃发动机供应上述权利要求1-10中任一项所述的润滑组合物。
12.权利要求11所述的方法，其中所述内燃发动机具有铝合金或铝复合材料的表面。
13.权利要求12所述的方法，其中所述铝合金是低共熔或超低共熔铝合金。
14.权利要求11所述的方法，其中所述内燃发动机具有钢表面。
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| TWI577931B (zh) * | 2015-05-28 | 2017-04-11 | 建準電機工業股份有限公司 | 具有發光模組之吊扇馬達 |
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2010
- 2010-08-11 BR BR112012003702A patent/BR112012003702A2/pt not_active IP Right Cessation
- 2010-08-11 WO PCT/US2010/045154 patent/WO2011022266A2/en active Application Filing
- 2010-08-11 CA CA2772116A patent/CA2772116A1/en not_active Abandoned
- 2010-08-11 US US13/389,517 patent/US20120196778A1/en not_active Abandoned
- 2010-08-11 ES ES10805861.1T patent/ES2453146T3/es active Active
- 2010-08-11 PL PL10805861T patent/PL2467460T3/pl unknown
- 2010-08-11 CN CN201080046848.8A patent/CN102753662B/zh active Active
- 2010-08-11 EP EP10805861.1A patent/EP2467460B1/en active Active
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1946833A (zh) * | 2004-03-11 | 2007-04-11 | 科聚亚公司 | 含有羟基多羧酸酯的润滑剂和燃料组合物 |
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| Publication number | Publication date |
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| ES2453146T3 (es) | 2014-04-04 |
| PL2467460T3 (pl) | 2014-05-30 |
| EP2467460A2 (en) | 2012-06-27 |
| US9738849B2 (en) | 2017-08-22 |
| US20160168503A1 (en) | 2016-06-16 |
| CA2772116A1 (en) | 2011-02-24 |
| WO2011022266A2 (en) | 2011-02-24 |
| BR112012003702A2 (pt) | 2019-09-24 |
| US20120196778A1 (en) | 2012-08-02 |
| CN102753662A (zh) | 2012-10-24 |
| EP2467460B1 (en) | 2013-12-25 |
| WO2011022266A3 (en) | 2011-05-19 |
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