CN101024794B - 润滑油组合物 - Google Patents
润滑油组合物 Download PDFInfo
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- CN101024794B CN101024794B CN2006101694674A CN200610169467A CN101024794B CN 101024794 B CN101024794 B CN 101024794B CN 2006101694674 A CN2006101694674 A CN 2006101694674A CN 200610169467 A CN200610169467 A CN 200610169467A CN 101024794 B CN101024794 B CN 101024794B
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- oil
- oils
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- alkyl
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- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 24
- 239000003921 oil Substances 0.000 claims description 82
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 42
- -1 hydrocarbyl phenol aldehyde Chemical class 0.000 claims description 40
- 150000003839 salts Chemical class 0.000 claims description 27
- 150000007524 organic acids Chemical class 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 238000004949 mass spectrometry Methods 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 238000003795 desorption Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 15
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract description 14
- 239000003112 inhibitor Substances 0.000 abstract description 13
- 235000019198 oils Nutrition 0.000 description 77
- 239000000654 additive Substances 0.000 description 28
- 235000013824 polyphenols Nutrition 0.000 description 21
- 230000000996 additive effect Effects 0.000 description 17
- 235000005985 organic acids Nutrition 0.000 description 17
- 239000002956 ash Substances 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- 230000001050 lubricating effect Effects 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- 150000002989 phenols Chemical class 0.000 description 10
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 10
- 239000011575 calcium Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 239000003599 detergent Substances 0.000 description 8
- 239000003607 modifier Substances 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 159000000007 calcium salts Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- 239000002199 base oil Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- 229960004889 salicylic acid Drugs 0.000 description 4
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 4
- 239000010689 synthetic lubricating oil Substances 0.000 description 4
- 239000003981 vehicle Substances 0.000 description 4
- 239000004034 viscosity adjusting agent Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 3
- 229960001860 salicylate Drugs 0.000 description 3
- 150000003870 salicylic acids Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 150000003752 zinc compounds Chemical class 0.000 description 3
- CIRMGZKUSBCWRL-LHLOQNFPSA-N (e)-10-[2-(7-carboxyheptyl)-5,6-dihexylcyclohex-3-en-1-yl]dec-9-enoic acid Chemical compound CCCCCCC1C=CC(CCCCCCCC(O)=O)C(\C=C\CCCCCCCC(O)=O)C1CCCCCC CIRMGZKUSBCWRL-LHLOQNFPSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical compound O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
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- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
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- 150000003873 salicylate salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
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- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- RDAGYWUMBWNXIC-UHFFFAOYSA-N 1,2-bis(2-ethylhexyl)benzene Chemical compound CCCCC(CC)CC1=CC=CC=C1CC(CC)CCCC RDAGYWUMBWNXIC-UHFFFAOYSA-N 0.000 description 1
- YEYQUBZGSWAPGE-UHFFFAOYSA-N 1,2-di(nonyl)benzene Chemical compound CCCCCCCCCC1=CC=CC=C1CCCCCCCCC YEYQUBZGSWAPGE-UHFFFAOYSA-N 0.000 description 1
- RLPSARLYTKXVSE-UHFFFAOYSA-N 1-(1,3-thiazol-5-yl)ethanamine Chemical compound CC(N)C1=CN=CS1 RLPSARLYTKXVSE-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
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- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- GPEJOYPHWFOWNM-UHFFFAOYSA-N 2-dodecylphenol;formaldehyde Chemical compound O=C.CCCCCCCCCCCCC1=CC=CC=C1O GPEJOYPHWFOWNM-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 description 1
- NUCFNMOPTGEHQA-UHFFFAOYSA-N 3-bromo-2h-pyrazolo[4,3-c]pyridine Chemical compound C1=NC=C2C(Br)=NNC2=C1 NUCFNMOPTGEHQA-UHFFFAOYSA-N 0.000 description 1
- KTJAIIUYEMVQEA-UHFFFAOYSA-N 3-ethyldodecan-3-ylphosphonic acid Chemical compound CCCCCCCCCC(CC)(CC)P(O)(O)=O KTJAIIUYEMVQEA-UHFFFAOYSA-N 0.000 description 1
- CLPFFLWZZBQMAO-UHFFFAOYSA-N 4-(5,6,7,8-tetrahydroimidazo[1,5-a]pyridin-5-yl)benzonitrile Chemical compound C1=CC(C#N)=CC=C1C1N2C=NC=C2CCC1 CLPFFLWZZBQMAO-UHFFFAOYSA-N 0.000 description 1
- ZDZVKPXKLLLOOA-UHFFFAOYSA-N Allylmalonic acid Chemical compound OC(=O)C(C(O)=O)CC=C ZDZVKPXKLLLOOA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
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- 238000007065 Kolbe-Schmitt synthesis reaction Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- MQHWFIOJQSCFNM-UHFFFAOYSA-L Magnesium salicylate Chemical compound [Mg+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O MQHWFIOJQSCFNM-UHFFFAOYSA-L 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate 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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- 239000002736 nonionic surfactant Chemical class 0.000 description 1
- 238000012634 optical imaging Methods 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Chemical group 0.000 description 1
- 239000001301 oxygen Chemical group 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 238000004525 petroleum distillation Methods 0.000 description 1
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- 150000003463 sulfur Chemical class 0.000 description 1
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- 150000001911 terphenyls Chemical class 0.000 description 1
- JZALLXAUNPOCEU-UHFFFAOYSA-N tetradecylbenzene Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1 JZALLXAUNPOCEU-UHFFFAOYSA-N 0.000 description 1
- MQHSFMJHURNQIE-UHFFFAOYSA-N tetrakis(2-ethylhexyl) silicate Chemical compound CCCCC(CC)CO[Si](OCC(CC)CCCC)(OCC(CC)CCCC)OCC(CC)CCCC MQHSFMJHURNQIE-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
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- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- ZAGXLQIHXTXRFW-UHFFFAOYSA-N tris(2-ethyl-4-methylhexyl)-tris(2-ethyl-4-methylhexyl)silyloxysilane Chemical compound CCC(C)CC(CC)C[Si](CC(CC)CC(C)CC)(CC(CC)CC(C)CC)O[Si](CC(CC)CC(C)CC)(CC(CC)CC(C)CC)CC(CC)CC(C)CC ZAGXLQIHXTXRFW-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M129/04—Hydroxy compounds
- C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
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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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
- C10M129/88—Hydroxy compounds
- C10M129/91—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
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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
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/20—Condensation polymers of aldehydes or ketones
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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- C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
-
- 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
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- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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- 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
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- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
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- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbased sulfonic acid salts
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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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/42—Phosphor free or low phosphor content compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/45—Ash-less or low ash content
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
本发明涉及油溶性烃基酚醛缩合物作为润滑油组合物中的防锈剂的用途，该润滑油组合物的硫酸化灰分含量小于该组合物的1.0重量％，该无灰分的油溶性烃基酚醛缩合物具有下列结构：
Description
本发明涉及润滑油组合物，特别地、但并非排他地涉及显示改进的防锈作用的润滑油组合物。
用于曲轴箱发动机油的润滑油组合物包含主要量的基料油和次要量的改进发动机性能的添加剂。存在多种用于润滑油组合物的类型添加剂，每种添加剂在该油中起到一种或多种不同的功能。
由于硫酸化灰分许可值的降低，客车机动车中磷和硫(SAPS)排放减少了可以使用的常规添加剂如金属基清洁剂的含量。这样导致了通常用于客车机动车中的添加剂组合中的不平衡，并且导致配方者考虑新的添加剂组合物以满足车辆厂商的需求。
欧洲专利申请No.0 575 154公开了一种润滑油，其包括羧酸分散剂、含有烃基取代的羧酸和非离子表面活性剂的防锈剂组合、含有至少一种烃基取代的酚与醛的反应产物和任选的受阻酚的抗氧剂组合、和至少一种具有已与碱性金属物质反应的酸或酚官能团的材料，使得该组合物的总硫酸化灰分含量为0.25～1重量％。
本发明的优选实施方式提供了另外的润滑油组合物，其设法在较低SAPS的润滑油组合物中提供足够的发动机清洁度和抗腐蚀性，同时保持其它性能特征。
本发明提供了一种使用润滑油组合物通过ASTM D6557球锈蚀测试(Ball Rust Test)的方法，该润滑油组合物的硫酸化灰分含量小于该组合物的1.0重量％，上述润滑油组合物包括主要量的润滑粘度油和无灰分的、油溶性烃基酚醛缩合物，该缩合物由通式(I)所示：
式(I)
其中n为0～10，Y为二价桥基，且优选为烃基、优选具有1～4个碳原子；并且R为具有4～30个碳原子的烃基。
本发明另外提供了油溶性烃基酚醛缩合物作为润滑油组合物中的防锈剂的用途，该润滑油组合物的硫酸化灰分含量小于该组合物的1.0重量％；该无灰分的油溶性烃基酚醛缩合物具有下列结构：
式(I)
其中n为0～10，Y为二价桥基，且优选为烃基、优选具有1～4个碳原子；并且R为具有4～30个碳原子的烃基。
本发明的其它和进一步目的、优点和特征将参照下列说明得到理解。
本发明的烃基酚醛缩合物优选为烃基苯酚甲醛缩合物。本文中所使用的术语“烃基”指所关注的基团主要由氢和碳原子组成并通过碳原子连接到分子的其余部分，但不排除存在不足以降低基团基本烃性质的比例的其它原子或基团。烃基优选仅由氢和碳原子组成。有益的是，烃基为脂肪基团，优选为烷基或烯基，特别是烷基，它们可以为直链或支化的。R优选为烷基或烯基。R优选为支化的。
本发明的优选实施方式包括符合上面式(I)的酚醛缩合物，其中n优选1～8、更优选2～7、且最优选3～6，和/或R优选包含8～18、且最优选9～15个碳原子。
该烃基酚醛缩合物的重均分子量(Mw)优选为600～4000、优选800～3500、更优选1000～2000、甚至更优选1200～1900、且最优选1250～1680，重均分子量是通过MALDI-TOF[矩阵辅助激光解吸离子化-飞行时间(Matrix Assisted Laser Desorption Ionization-Time of Flight)]质谱分析测量的。
优选通过在酸催化剂(例如烷基苯磺酸)存在下将至少一种醛或酮或其反应性等价物和至少一种烃基酚进行缩聚反应制得烃基酚醛缩合物。产物优选通过进行分离除去任何未反应的烃基酚，优选到小于5重量％、更优选到小于3重量％、甚至更优选到小于1重量％的未反应的烃基酚。最优选地，产物含有少于0.5重量％(例如小于0.1重量％)的未反应的烃基酚。
虽然可以使用碱性催化剂，但优选酸性催化剂。酸性催化剂可以选自多种酸性化合物，例如磷酸、硫酸、磺酸、草酸和盐酸。酸也可以以固态物质的形式存在，例如酸处理过的粘土。酸催化剂的用量基于反应混合物总重为0.05～10重量％或更多，例如0.1～1重量％。
特别是，烃基酚醛缩合物优选为支化的十二烷基苯酚甲醛缩合物，例如四丙烯基四聚体苯酚甲醛缩合物。
本发明的无灰分烃基酚醛缩合物的总碱值(TBN)为0，因为其中该化合物中不存在金属离子。
用于实施本发明的润滑油组合物可以另外包括一种或多种清洁添加剂。适宜的清洁添加剂包括有机酸的高碱性金属盐。
适用于本发明内容的有机酸的高碱性金属盐通常包含具有长疏水性尾的极性头。该极性头包括酸性有机化合物的金属盐。在中性或正盐中，该盐可以含有基本上为化学计量的量的金属且通常的总碱值或TBN(可以 通过ASTM D 2896测量)为0～80。在高碱性金属盐中，可以通过使过量的金属化合物(如氧化物或氢氧化物)与酸性气体(如二氧化碳)反应来结合大量的金属碱。所获得的高碱性清洁剂包括作为金属碱(例如碳酸盐)胶束外层的中和的清洁剂。这样的高碱性清洁剂的TBN可以为150或更大，且通常其TBN为250～450或更大。
可以用于本发明清洁剂组合物中的有机酸的高碱性金属盐包括油溶性的高碱性磺酸盐，酚盐，硫酸化的酚盐，硫代膦酸盐，水杨酸盐，包括金属、尤其是碱金属或碱土金属(例如钡、钠、钾、锂、钙和镁)的羟基苯甲酸盐、环烷酸盐和其它油溶性羧酸盐。最常用的金属为钙、镁和钠，和其混合物钙和/或镁。
就本发明来说，特别便利的有机酸的高碱性金属盐为磺酸、酚、硫化酚和水杨酸的高碱性金属盐。
该金属盐的金属优选为钠、镁或钙，且更优选钙或镁。就本发明来说，用作清洁剂的更多种有机酸高碱性金属盐的一种可以包含多种不同的金属盐，其衍生自不同的有机酸且包含不同的金属。在一种实施方式中，多种高碱性金属盐包含衍生自相同或不同有机酸且每一种包含相同的金属的金属盐。例如，清洁剂可以包括多种有机酸的高碱性钙盐。另外，清洁剂可以包括多种有机酸的高碱性镁盐。作为另一种替换方式，清洁剂可以包含一种或多种有机酸的高碱性镁盐与一种或多种有机酸的钙盐的混合物。
磺酸盐可以由磺酸制得，磺酸通常通过磺化烷基取代的芳烃(如石油精馏中获得的那些)或通过烷基化芳烃来获得。实例包括通过烷基化苯、甲苯、二甲苯、萘、联苯或它们的卤代衍生物如氯苯、氯甲苯和氯萘而获得的那些。烷基化可以在催化剂的存在下使用具有约3到大于70个碳原子的烷基化试剂来进行。烷芳基磺酸盐通常含有每个烷基取代的芳族部分约9～约80个或更多的碳原子、优选为约16～约60个碳原子。
油溶性磺酸盐或烷芳基磺酸可以用金属的氧化物、氢氧化物、醇盐、 碳酸盐、羧酸盐、硫化物、氢硫化物、硝酸盐、硼酸盐和醚来中和。考虑所期望的最终产物的TBN来选择金属化合物的用量，但是其用量通常为所需化学计量的量的约100～220重量％(优选至少125重量％)。
酚和硫化酚的金属盐通过与适当金属化合物如氧化物或氢氧化物的反应来制备，并且中性或高碱性产物可以通过本领域众所周知的方法获得。硫化酚可以通过使酚与硫或者含硫化合物如硫化氢、单卤代硫或二卤代硫反应来制得，由此形成通常为其中两个或多个酚通过含硫桥基桥连的化合物的混合物的产物。
羧酸盐清洁剂如水杨酸盐可以通过使芳族羧酸与适当的金属化合物如氧化物或氢氧化物反应来制备，且中性或高碱性产物可以通过本领域众所周知的方法获得。芳族羧酸的芳族部分可以含有杂原子，如氮和氧。优选地，该部分仅含碳原子；更优选地，该部分含有6个或更多的碳原子；例如苯为优选部分。芳族羧酸可以含有一个或多个芳族部分，如一个或多个苯环，其稠合或通过亚烷基桥连接。羧酸部分可以直接或者间接地连接于芳族部分。优选地，羧酸基团直接连接于芳族部分上的碳原子，如苯环上的碳原子。更优选地，该芳族部分也含有第二种官能团，如羟基或磺酸酯基，其可以直接或者间接地连接于芳族部分上碳原子。
芳族羧酸的优选实例为水杨酸和其硫化衍生物，包括羟基苯甲酸盐，如US 5,808,145或EP 933 417中所述的那些，如烃基取代的水杨酸和其衍生物。用于硫化例如烃基取代的水杨酸的方法是本领域技术人员所公知的。水杨酸通常通过羧基化(例如通过Kolbe-Schmitt工艺)酚盐来制得，此时其将通常在稀释剂中、以与未羧基化酚的掺混物形式获得。
油溶性水杨酸中优选的取代基为烷基取代基。在烷基取代的水杨酸中，烷基有利地含有5～100、优选9～30、尤其是14～20个碳原子。当存在一个以上烷基时，全部烷基中碳原子的平均数优选为至少9个，以确保足够的油溶性。
通常用于润滑油组合物配方中的有机酸的高碱性金属盐也包括与混合表面活性剂体系形成的“杂化”清洁剂，例如酚盐/水杨酸盐、磺酸盐/酚盐、磺酸盐/水杨酸盐、和磺酸盐/酚盐/水杨酸盐，例如如待审美国专利US 6,429,178、6,429,179、6,153,565和6,281,179中所述的那些。
适用于本发明的有机酸的高碱性金属盐适宜地总碱值(TBN)为至少250、且优选至少300。提供该清洁剂组合物的组份(A)的一种或多种有机酸高碱性金属盐可以包含具有不同TBN值的添加剂的组合。此时，有机酸的高碱性金属盐的平均TBN适宜地为至少250且优选为至少300。
有机酸的高碱性金属盐可以通过它们的金属比例来定义，该比例为金属总当量与和该金属反应的酸性有机化合物的总量的比。适用于本发明的有机酸的高碱性金属盐适宜地金属比例大于1、优选为至少5、更优选为至少10且可能高达25。
一种或多种有机酸的高碱性金属盐的用量适宜地使得该润滑油组合物的硫酸化灰分含量基于该润滑油组合物小于1.0重量％、优选小于0.5重量％且更优选小于0.3重量％。
适用于制备本发明润滑油组合物的润滑粘度油可以选自于天然的(植物、动物或矿物)和合成润滑油与其混合物。其粘度范围可以从轻馏分矿物油到重润滑油，如内燃机润滑油、矿物润滑油、机动车油、和载重柴油。通常，这些油在100℃下的粘度为2厘沲～30厘沲、特别是5厘沲～20厘沲。
天然油包括动物油和植物油(例如蓖麻油、猪油)；液体石油，和经过氢化精炼的、溶剂处理的或酸处理的石蜡、环烷烃和石蜡-环烷烃混合型的矿物油。由煤或页岩衍生的润滑粘度油也用作可用的基油。
合成润滑油包括烃油和卤代烃油，例如聚合和共聚的烯烃(例如聚丁烯、聚丙烯、丙烯-丁烯共聚物、氯化聚丁烯、聚(1-己烯)、聚(1-辛烯)、聚(1-癸烯))；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、联三苯、烷基化多酚)；和烷基化二苯醚与烷基化二苯硫醚及它们的衍生物、类似物和同系物。
环氧烷聚合物和互聚物以及它们的其中端羟基己通过酯化、醚化等改性的衍生物构成另一类公知的合成润滑油。它们的实例有通过环氧乙烷或环氧丙烷的聚合而制得的聚氧化烯聚合物，和聚氧化烯聚合物的烷基和芳基醚(例如，分子量为1000的聚异丙二醇甲基醚，或分子量为1000-15000的聚乙二醇二苯基醚)；和它们的单或多羧酸酯，例如乙酸酯、混合C3-C8 脂肪酸酯和四乙二醇的C13含氧酸二酯。
另一类合适的润滑油包括二元羧酸(例如邻苯二甲酸、琥珀酸、烷基琥珀酸和烯基琥珀酸、马来酸、壬二酸、辛二酸、癸二酸、富马酸、己二酸、亚油酸二聚体、丙二酸、烷基丙二酸、烯基丙二酸)与多种醇(例如丁醇、己醇、十二醇、2-乙基己醇、乙二醇、二乙二醇单醚、丙二醇)的酯。这种酯的实例包括己二酸二丁酯、癸二酸二(2-乙基己)酯、富马酸二正己酯、癸二酸二辛酯、壬二酸二异辛酯、癸二酸二异癸酯、邻苯二甲酸二辛酯、邻苯二甲酸二癸酯、癸二酸二(二十烷基)酯、亚油酸二聚体的二-2-乙基己酯，和通过使1摩尔癸二酸与2摩尔四乙二醇和2摩尔2-乙基己酸反应生成的复合酯。
适合作为合成油的酯还包括由C5-C12单羧酸与多元醇和多元醇酯(例如新戊二醇、三羟甲基丙烷、季戊四醇、二季戊四醇和三季戊四醇)制备的那些。
基于硅的油，如聚烷基、聚芳基、聚烷氧基或聚芳氧基硅油和硅酸酯油，构成另一类可用的合成润滑剂；这种油包括硅酸四乙酯、硅酸四异丙酯、硅酸四(2-乙基己)酯、硅酸四(4-甲基-2-乙基己)酯、硅酸四(对叔丁基苯)酯、六(4-甲基-2-乙基己基)二硅氧烷、聚(甲基)硅氧烷和聚(甲基苯基)硅氧烷。其它合成润滑油包括含磷的酸的液体酯(例如磷酸三甲苯酯、磷酸三辛酯、癸基膦酸的二乙酯)和聚四氢呋喃。
润滑粘度油可以包括I类、II类、III类、IV类或V类油，或上述油的混合物。润滑粘度油还可以包括I类油与II类、III类、IV类或V类油中一种或多种的混合物。
本文中所使用的油的定义与美国石油学院(API)出版物“Engine OilLicensing and Certification System”，工业服务部，第14版，1996，附录1，1998年12月中的意义相同。所述出版物对油进行了如下分类：
a)用下表1所规定的试验方法测定，含有小于90％的饱和物和/或大于0.03％的硫，其粘度指数大于或等于80且小于120的I类油。
b)用下表1所规定的试验方法测定，含有大于或等于90％的饱和物和小于或等于0.03％的硫，其粘度指数大于或等于80且小于120的II类油。虽然不是被API认可的单独分类，但粘度指数大于约110的II类油经常称为“II类+”油。
c)用下表1所规定的试验方法测定，含有大于或等于90％的饱和物和小于或等于0.03％的硫，其粘度指数大于或等于120的III类油。
d)IV类油为聚α-烯烃(PAO)。
e)V类油为所有不包括在I、II、III或IV类之内的其它基料。
表1
| 性能 | 测试方法 |
| 饱和物 | ASTM D 2007 |
| 粘度指数 | ASTM D 2270 |
| 硫 | ASTM D 4294 |
润滑粘度油优选具有至少65％、更优选至少75％的饱和物，例如至少85％。更优选地，所述润滑粘度油具有大于90％的饱和物。优选地，润滑粘度油具有小于1质量％、优选小于0.6质量％、更优选小于0.3质量％的硫，例如0～0.3质量％。
按照Noack试验(ASTM D 5880)测量，该润滑粘度油的挥发性小于或等于约40质量％，如小于或等于约35质量％；优选小于或等于约32质量％，如小于或等于约28质量％；更优选小于或等于约16质量％。优选地，该润滑粘度油的粘度指数(VI)为至少85、优选至少100、最优选 约105-140。
依据本发明的润滑油组合物的TBN在一定程度上取决于该组合物的应用。对于润滑内燃机的曲轴箱来说，该组合物的TBN适宜地小于20、优选小于15、且更优选小于10。
适用于本发明的润滑油组合物的硫酸化灰分含量在一定程度上也取决于该组合物的应用和当前的市场需求。适用于本发明的润滑油组合物的总硫酸化灰分含量可以具有小于0.8质量％、更优选小于0.5质量％且潜在地小于0.1质量％的硫酸化灰分含量。
依据本发明的润滑油组合物适宜地具有基于该润滑油组合物小于1.0质量％、优选小于0.5质量％且更优选小于0.3质量％的硫含量。
依据本发明的润滑油组合物，适宜地具有小于0.5质量％、优选小于0.3质量％且更优选小于0.1重量％或更小的磷含量。
适用于本发明的润滑油组合物可以另外包括一种或多种其它性能改进添加剂，这些添加剂选自于：无灰分分散剂、抗磨剂、氧化抑制剂或抗氧剂、无灰份并且含金属的摩擦改性剂和节油剂(fuel economy agent)、消泡剂和腐蚀抑制剂、和多烯基酰化剂。通常，在配制润滑剂时，将添加剂以一种或多种、优选单一浓缩的添加剂包(经常称为DI(分散剂-抑制剂)包)提供给配方设计者，而以第二包提供VI改进剂和/或VI改进剂和LOFI。
无灰分分散剂将在磨耗或燃烧期间因油的氧化而产生的油不溶物保持为悬浮状态。它们对于防止油泥的沉积和漆膜的形成是特别有利的，尤其在汽油发动机中。
二烃基二硫代磷酸酯金属盐经常用作抗磨剂和抗氧剂。该金属可以是碱金属或碱土金属，或铝、铅、锡、钼、锰、镍或铜。锌盐最常用于润滑油且可以依照公知技术通过下述步骤制得：首先通常使一种或多种醇或酚与P2S5反应生成二烃基二硫代磷酸(DDPA)，然后用锌化合物中和形成的DDPA。例如，二硫代磷酸可通过使伯醇和仲醇混合物反应而制得。另外， 可以制备复合二硫代磷酸，其中一个上的烃基在性质上完全为仲烃基，而在其它上的烃基在性质上完全为伯烃基。为了制备锌盐，可以使用任何碱性或中性的锌化合物，但最常用的为氧化物、氢氧化物和碳酸盐。由于中和反应中使用了过量的碱性锌化合物，因此商品添加剂常常含有过量的锌。
氧化抑制剂或抗氧剂降低了矿物油在使用过程中变质的趋势。氧化变质可以通过润滑剂中的油泥、金属表面上的类漆膜沉积以及粘度的增大表现出来。此类氧化抑制剂包括受阻酚、优选具有C5～C12烷基侧链的烷基酚硫酯的碱土金属盐、壬基酚硫化钙、油溶性酚盐和硫化的酚盐、磷硫化或硫化的烃、亚磷酸酯、硫代氨基甲酸金属盐、如美国专利4,867,890中所述的油溶性铜化合物、以及含钼的化合物和芳族胺。
公知的含金属的摩擦改性剂包括油溶性有机钼化合物。这种有机钼摩擦改性剂也为润滑油组合物提供了抗氧化和抗磨损的性质。作为这种油溶性有机钼化合物的实例，可以列举的是：二硫代氨基甲酸盐、二硫代磷酸盐、二硫代亚膦酸盐、黄原酸盐、硫代黄原酸盐、硫化物等，以及它们的混合物。特别优选的是二硫代氨基甲酸钼、二烷基二硫代磷酸钼、烷基黄原酸钼和烷基硫代黄原酸钼。
无金属的摩擦改性剂通常公知为有机摩擦改性剂，且包括含有至少一个选自羟基和胺基的极性基团的油溶性化合物，该化合物能够降低流体力学条件和混合流体力学/边界层条件下的摩擦。这种材料的实例包括高级脂肪酸的甘油酯，例如单油酸甘油酯；长链多羧酸与二醇的酯，例如二聚不饱和脂肪酸的丁二醇酯；唑啉化合物；和烷氧基化烷基取代的单胺、二胺和烷基醚胺，例如乙氧基化牛脂胺和乙氧基化牛脂醚胺。特别优选的表面活性试剂包括油酸甘油酯、尤其是单油酸甘油酯，和乙氧基化胺、尤其是乙氧基化牛脂胺。
通过聚硅氧烷类型的消泡剂，例如硅油或聚二甲基硅氧烷，可以对泡沫加以控制。
适宜地，依据本发明的润滑油组合物不含除式(I)的无灰分的、油溶性烃基酚醛缩合物之外的防锈剂。特别地，该润滑油组合物优选地不含非离子型表面活性防锈剂或者烃基取代的羧酸或其衍生物防锈剂，如EP 0 575154第4页第16-48行中所述的那些。
上述某些添加剂可以提供多重效果；例如，单一添加剂可以用作分散剂-氧化抑制剂。这一措施是公知的，无需在此作进一步的详细阐述。
当用于全配方曲轴箱润滑剂时，这种附加添加剂的代表性有效量列于下面表2中：
表2
| 添加剂 | 重量％(宽泛的) | 重量％(优选的) |
| 无灰分的分散剂 | 0.1-20 | 1-8 |
| 缓蚀剂 | 0-5 | 0-1.5 |
| 二烃基二硫代磷酸金属盐 | 0.1-6 | 0.1-4 |
| 抗氧剂 | 0-5 | 0.01-2 |
| 倾点下降剂 | 0.01-5 | 0.01-1.5 |
| 消泡剂 | 0-5 | 0.001-0.15 |
| 补充型抗磨剂 | 0-1.0 | 0-0.5 |
| 摩擦改性剂 | 0-5 | 0-1.5 |
| 基料 | 余量 | 余量 |
参照阐述本发明的下列实施例，本发明将得到进一步的理解。
实施例
实施例1
混合具有下面表3中所述组成的油，并使用其进行ASTM D 6557球锈蚀测试(该测试测量铁腐蚀)。在进行球锈蚀测试时，将各自含有试验油和样本的多个试管置于连接了机械振荡器的支架中。控制振荡器速率和温度。在18小时内向每个试管中连续地喂入空气和酸性溶液，由此形成腐 蚀环境。随后取出样本，冲洗并通过为了定量化每种油的耐锈能力而设计的光学成像体系来进行分析。ASTM D 6557球锈蚀测试为测量平均灰度值的指标试验，其中数值越高表示铁锈形成越少。
表3中给出的数量为全配方油组合物的总质量的质量％。
表3
| 组份 | 油1 | 油2 | 油3 | 油4 |
| 清洁剂1 | - | - | 1.00 | - |
| 清洁剂2 | - | - | 0.61 | 1.10 |
| 清洁剂3 | 1.51 | - | - | - |
| 清洁剂4 | 0.95 | 1.33 | - | - |
| 烃基酚醛缩合物 | - | 0.54 | - | 0.50 |
| 添加剂包1 | 10.20 | 10.20 | 10.20 | 10.20 |
| 基油+粘度改性剂 | 87.34 | 87.93 | 88.19 | 88.2 |
| 硫酸化灰分％ | 0.56 | 0.56 | 0.56 | 0.56 |
| 皂质量 | 0.77 | 0.76 | 0.58 | 0.62 |
| Ca％ | 0.035 | 0.000 | 0.054 | 0.000 |
| Mg％ | 0.072 | 0.100 | 0.056 | 0.100 |
| P％ | 0.05 | 0.05 | 0.05 | 0.05 |
| S％ | 0.18 | 0.18 | 0.21 | 0.18 |
清洁剂1是TBN为145的酚钙清洁剂。清洁剂2是TBN为400的磺酸镁清洁剂。清洁剂3是TBN为64的水杨酸钙清洁剂，清洁剂4是TBN为342的水杨酸镁清洁剂。
烃基酚醛缩合物符合上述式(I)，且其数均分子量为1500。
油1、2、3和4的每一个均含有相同量的额外添加剂，其在上面称为添加剂包1。添加剂包1含有分散剂、二烷基二硫代磷酸锌、摩擦改性剂、抗氧剂和消泡剂。用于油1、2、3和4的每一个的基料和粘度改性剂是相同的，但是由于清洁剂量的变化而使得添加剂包中稀释油的量存在细微差别。使每种油中清洁剂和烃基酚醛缩合物的量均衡，以至于由1与2和3 与4的每一个具有相等的硫酸化灰分、皂、磷和硫含量。
从表3中可以看出，油1和3为对比实施例，油2和4是依据本发明的。
球锈蚀测试的结果在下面表4中给出。
表4
| 油 | 油1 | 油2 | 油3 | 油4 |
| 结果 | 80 | 106 | 67 | 110 |
表4清楚地表明，使用无灰分的烃基酚醛缩合物，恒定的硫酸化灰分实现了ASTM D 6557球锈蚀测试中的改进性能。
实施例2
混合下面表5中所述的油，并且如上所述对其进行ASTM D 6557球锈蚀测试。表5中给出的数量为全配方油组合物的总质量的质量％。
表5
| 组份 | 油5 | 油6 | 油7 | 油8 |
| 清洁剂5 | - | - | 0.77 | 0.98 |
| 清洁剂6 | 0.92 | 0.70 | - | - |
| 烃基酚醛缩合物的钙盐 | - | 0.95 | 0.90 | - |
| 烃基酚醛缩合物 | 0.80 | - | - | 0.75 |
| 添加剂包2 | 14.13 | 14.13 | 14.13 | 14.13 |
| 添加剂包稀释剂 | 1.05 | 1.12 | 1.10 | 1.04 |
| 基油+粘度改性剂 | 83.1 | 83.1 | 83.1 | 83.1 |
| 硫酸化灰分％ | 0.54 | 0.54 | 0.54 | 0.54 |
| 皂质量 | 0.66 | 0.66 | 0.66 | 0.66 |
| Ca％ | 0.115 | 0.114 | 0.114 | 0.114 |
| P％ | 0.05 | 0.05 | 0.05 | 0.05 |
| S％ | 0.125 | 0.124 | 0.133 | 0.137 |
清洁剂5是TBN为300的磺酸钙清洁剂。清洁剂6是TBN为344的水杨酸钙清洁剂。
油5和8的烃基酚醛缩合物符合上述式(I)，且数均分子量为1500。油6和7的烃基酚醛缩合物的钙盐为油5和8中所用烃基酚醛缩合物的钙盐。
油5、6、7和8的每一个均含有相同量的额外添加剂，在上面称为添加剂包2。添加剂包2含有分散剂、二烷基二硫代磷酸锌、摩擦改性剂、抗氧剂和消泡剂。用于油5、6、7和8的每一个的稀释油基料和粘度改性剂是相同的，但是由于清洁剂量的变化而使得添加剂包中稀释油的量存在细微差别。使每种油中清洁剂和烃基酚醛缩合物的量均衡，以至于由5与6和7与8的每一个具有相等的硫酸化灰分、皂、钙、磷和硫含量。
从表5中可以看出，油6和7为对比实施例，油5和8是依据本发明的。
球锈蚀测试的结果在下面表6中给出。
表6
| 测试 | 油5 | 油6 | 油7 | 油8 |
| 88 | 68 | 61 | 69 | |
| 烃基酚醛缩合物相对于钙盐的改进％ | 29 | 12 |
表6清楚地表明，相对于烃基酚醛缩合物的钙盐来说，使用无灰分的烃基酚醛缩合物，恒定的硫酸化灰分和皂含量实现了ASTM D 6557球锈蚀测试中的改进性能。
此处和所附权利要求中的含有、组成为或基本上组成为多种特定组分的组合物的表述，应解释为还包括通过将所述多种特定组份混合而制成的组合物。
Claims (11)
1.无灰、油溶性烃基酚醛缩合物的用途，作为润滑油组合物中的防锈剂，其硫酸化灰分含量小于该组合物的1.0重量％，所述无灰分、油溶性烃基酚醛缩合物由通式(I)所示：
式(I)
其中n为0～10，Y为二价桥基；并且R为具有4～30个碳原子的烃基。
2.权利要求1的用途，其中二价桥基为具有1～4个碳原子的烃基。
3.权利要求1或2的用途，其中油溶性烃基酚醛缩合物的重均分子量(Mw)为600～4000，通过MALDI-TOF[矩阵辅助激光解吸离子化-飞行时间]质谱分析测量。
4.权利要求3的用途，其中油溶性烃基酚醛缩合物的重均分子量(Mw)为800～3500。
5.权利要求4的用途，其中油溶性烃基酚醛缩合物的重均分子量(Mw)为1250～1680。
6.权利要求1或2的用途，其中n为1～8。
7.权利要求6的用途，其中n为3～5。
8.权利要求1或2的用途，其中R为具有8～18个碳原子的烃基。
9.权利要求8的用途，其中R为具有9～15个碳原子的烃基。
10.权利要求1或2的用途，其中润滑油进一步包含一种或多种有机酸的高碱性金属盐。
11.权利要求10的用途，其中一种或多种有机酸的高碱性金属盐包含
(a)(i)苯酚、(ii)磺酸或(iii)水杨酸的碱金属盐或碱土金属盐，或者
(b)含有(i)苯酚、(ii)磺酸或(iii)水杨酸的碱金属盐或碱土金属盐的任意两种的组合的复合清洁剂。
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| US20080139430A1 (en) * | 2006-12-08 | 2008-06-12 | Lam William Y | Additives and lubricant formulations for improved antiwear properties |
| CN102459543A (zh) | 2009-06-04 | 2012-05-16 | 吉坤日矿日石能源株式会社 | 润滑油组合物及其制造方法 |
| EP2712911A3 (en) | 2009-06-04 | 2014-08-06 | JX Nippon Oil & Energy Corporation | Lubricant oil composition |
| JP5785682B2 (ja) * | 2009-06-18 | 2015-09-30 | 出光興産株式会社 | 潤滑油組成物 |
| US8927469B2 (en) | 2011-08-11 | 2015-01-06 | Afton Chemical Corporation | Lubricant compositions containing a functionalized dispersant |
| US9145530B2 (en) * | 2012-12-10 | 2015-09-29 | Infineum International Limited | Lubricating oil compositions containing sterically hindered amines as ashless TBN sources |
| EP2931851A1 (en) * | 2012-12-17 | 2015-10-21 | The Lubrizol Corporation | Process for producing an overbased metal detergent |
| CN111635799B (zh) * | 2020-05-15 | 2021-09-03 | 清华大学 | 润滑油组合物及其用途 |
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| US5259967A (en) * | 1992-06-17 | 1993-11-09 | The Lubrizol Corporation | Low ash lubricant composition |
| CN1644665A (zh) * | 2003-12-22 | 2005-07-27 | 切夫里昂奥罗尼特有限责任公司 | 含有碱金属清净剂的润滑油组合物 |
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| US6002051A (en) * | 1992-10-16 | 1999-12-14 | The Lubrizol Corporation | Tertiary alkyl alkylphenols and organic compositions containing same |
| DE69617761T2 (de) * | 1995-02-01 | 2002-08-08 | The Lubrizol Corp., Wickliffe | Schmiermittelzusammensetzung mit geringem Aschegehalt |
| US6310009B1 (en) * | 2000-04-03 | 2001-10-30 | The Lubrizol Corporation | Lubricating oil compositions containing saligenin derivatives |
| WO2001096503A2 (de) * | 2000-06-15 | 2001-12-20 | Clariant International Ltd | Additive zur verbesserung von kaltfliesseigenschaften und lagerstabilität von rohölen |
| EP1304368A1 (en) * | 2001-09-28 | 2003-04-23 | Infineum International Limited | A gas engine lubricating oil composition |
| US20040010965A1 (en) * | 2002-07-09 | 2004-01-22 | Clariant Gmbh | Oxidation-stabilized lubricant additives for highly desulfurized fuel oils |
| US7851421B2 (en) * | 2004-06-11 | 2010-12-14 | Infineum International Limited | Detergent additives for lubricating oil compositions |
| US7786060B2 (en) * | 2004-11-16 | 2010-08-31 | Infineum International Limited | Lubricating oil additive concentrates |
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| US5259967A (en) * | 1992-06-17 | 1993-11-09 | The Lubrizol Corporation | Low ash lubricant composition |
| CN1644665A (zh) * | 2003-12-22 | 2005-07-27 | 切夫里昂奥罗尼特有限责任公司 | 含有碱金属清净剂的润滑油组合物 |
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