CN101012407B - 含钛润滑油组合物 - Google Patents
含钛润滑油组合物 Download PDFInfo
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- CN101012407B CN101012407B CN2006100639523A CN200610063952A CN101012407B CN 101012407 B CN101012407 B CN 101012407B CN 2006100639523 A CN2006100639523 A CN 2006100639523A CN 200610063952 A CN200610063952 A CN 200610063952A CN 101012407 B CN101012407 B CN 101012407B
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- acid
- titanium
- oil
- compound
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- 239000000203 mixture Substances 0.000 title claims abstract description 138
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 71
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000010936 titanium Substances 0.000 title claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 31
- 239000003921 oil Substances 0.000 claims abstract description 48
- 239000003607 modifier Substances 0.000 claims abstract description 42
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011575 calcium Substances 0.000 claims abstract description 29
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- -1 salt compound Chemical class 0.000 claims description 39
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000446 fuel Substances 0.000 claims description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 claims description 5
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- RYSNDQDGZQEOAL-UHFFFAOYSA-N calcium;phenol Chemical compound [Ca].OC1=CC=CC=C1 RYSNDQDGZQEOAL-UHFFFAOYSA-N 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 239000005639 Lauric acid Substances 0.000 claims description 3
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 3
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 3
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 3
- 229960004232 linoleic acid Drugs 0.000 claims description 3
- 229960004488 linolenic acid Drugs 0.000 claims description 3
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- PCMORTLOPMLEFB-ONEGZZNKSA-N sinapic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-ONEGZZNKSA-N 0.000 claims description 3
- PCMORTLOPMLEFB-UHFFFAOYSA-N sinapinic acid Natural products COC1=CC(C=CC(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 2
- 235000018262 Arachis monticola Nutrition 0.000 claims description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 235000020232 peanut Nutrition 0.000 claims description 2
- 241001553178 Arachis glabrata Species 0.000 claims 1
- 239000003599 detergent Substances 0.000 abstract description 4
- 230000001050 lubricating effect Effects 0.000 abstract description 3
- 235000019198 oils Nutrition 0.000 description 42
- 239000002585 base Substances 0.000 description 34
- 239000000654 additive Substances 0.000 description 26
- 239000002199 base oil Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 19
- 239000005864 Sulphur Substances 0.000 description 18
- 150000002430 hydrocarbons Chemical class 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 17
- 229930195733 hydrocarbon Natural products 0.000 description 17
- 239000004215 Carbon black (E152) Substances 0.000 description 16
- 230000000996 additive effect Effects 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 125000001183 hydrocarbyl group Chemical group 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 10
- 239000005078 molybdenum compound Substances 0.000 description 10
- 150000002752 molybdenum compounds Chemical class 0.000 description 10
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 8
- 239000004034 viscosity adjusting agent Substances 0.000 description 8
- 125000002723 alicyclic group Chemical group 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 150000004867 thiadiazoles Chemical class 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000005077 polysulfide Substances 0.000 description 6
- 229920001021 polysulfide Polymers 0.000 description 6
- 150000008117 polysulfides Polymers 0.000 description 6
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005987 sulfurization reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 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 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 229910000765 intermetallic Inorganic materials 0.000 description 4
- 239000010705 motor oil Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229960002317 succinimide Drugs 0.000 description 3
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 3
- LRTLEKVJKBCUQQ-KVVVOXFISA-N (z)-octadec-9-enoic acid;titanium Chemical compound [Ti].CCCCCCCC\C=C/CCCCCCCC(O)=O LRTLEKVJKBCUQQ-KVVVOXFISA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
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- AKPLSMYRLYRCQN-UHFFFAOYSA-N [(benzhydryldisulfanyl)-phenylmethyl]benzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)SSC(C=1C=CC=CC=1)C1=CC=CC=C1 AKPLSMYRLYRCQN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
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- 150000001721 carbon Chemical group 0.000 description 2
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- 125000005842 heteroatom Chemical group 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 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 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 150000004869 1,3,4-thiadiazoles Chemical class 0.000 description 1
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- BKCNDTDWDGQHSD-UHFFFAOYSA-N 2-(tert-butyldisulfanyl)-2-methylpropane Chemical compound CC(C)(C)SSC(C)(C)C BKCNDTDWDGQHSD-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 description 1
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- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- 239000000159 acid neutralizing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
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- 150000001356 alkyl thiols Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
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- 229960001860 salicylate Drugs 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
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940051851 sulfurated lime Drugs 0.000 description 1
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- PIZNQHDTOZMVBH-UHFFFAOYSA-N thionylimide Chemical compound N=S=O PIZNQHDTOZMVBH-UHFFFAOYSA-N 0.000 description 1
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- 229920002554 vinyl polymer Polymers 0.000 description 1
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- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
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- C10M2209/084—Acrylate; Methacrylate
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- C10M2219/106—Thiadiazoles
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- C10M2223/045—Metal containing thio derivatives
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Abstract
一种润滑油组合物,包含:a)具有润滑粘度的油,其粘度指数为至少约95;b)至少一种钙洗涤剂;c)至少一种油溶性钛化合物;d)至少一种摩擦改性剂;和e)至少一种二烃基二硫代磷酸金属盐化合物。该组合物的Noack挥发度为约15wt.%或更低,并含有来自钙洗涤剂的约0.05~约0.6wt.%的钙、来自钛化合物的钛金属量为至少约10ppm~约1500ppm的钛、和来自二烃基二硫代磷酸金属盐化合物的量最高达到约0.1wt.%的磷。
Description
技术领域
本发明涉及润滑油组合物,更具体而言,本发明涉及包括用于改进润滑工作性能的含钛化合物的润滑油组合物。
背景技术
用于润滑内燃机的润滑油组合物包含具有润滑粘度的基础油或这种油的混合物,和用于改善油品工作特性的添加剂。例如,添加剂被用于改善清洁性、减少发动机磨损、提供热稳定性和氧化稳定性、降低油耗、抑制腐蚀、作为分散剂并减少摩擦损失。一些添加剂可以提供多种好处,例如分散剂-粘度改性剂。而其它添加剂在改善润滑油的一种特性的时候,对其它特性具有副作用。因此,为了赋予润滑油最佳的综合性能,有必要表征和理解可用各种添加剂的全部作用,并认真平衡润滑油的添加剂含量。
在许多专利和文章中(例如美国专利号4,164,473、4,176,073、4,176,074、4,192,757、4,248,720、4,201,683、4,289,635和4,479,883)已经提出将油溶性钼化合物用作润滑油添加剂。尤其是,向油中添加钼化合物,特别是二硫代氨基甲酸钼化合物,为油品提供更好的边界摩擦特性,并且台架试验证明含有这种钼化合物的油品的摩擦系数普遍低于含有有机摩擦改性剂油品的摩擦系数。这种摩擦系数的降低导致了抗磨特性的改进,并且可以有助于提高汽油或柴油点火式发动机的燃料经济性,包括长期和短期燃料经济性(即燃料经济保持特性)。为了提供抗磨效果,一般钼化合物的添加量是向油品中引入约350ppm~2000ppm的钼。虽然钼化合物是有效的抗磨剂并且可以进一步提供燃料经济利益,但是这种钼化合物相对于传统的无金属(无灰)的有机摩擦改性剂是昂贵的。
美国专利6,300,291公开了一种具有特定Noack挥发度的润滑油组合物,该组合物包含具有特定粘度指数的基础油、钙基洗涤剂、二烃基二硫代磷酸锌(ZDDP)抗磨剂、钼化合物和含氮摩擦改性剂。钼化合物的使用量使配制的润滑油中含有高达350ppm的钼。与只含有钼化合物的组合物相比,要求保护的物质被描述为能提供燃料经济利益。尽管存在上述内容,但人们仍然需要具有更高成本效率的润滑油组合物,该润滑油组合物不含钼基摩擦改性剂时就能提供相等的或更好的性能。
发明内容
根据第一方面,本发明的一个示例性实施方案提供了一种改进的基本上不含钼化合物的润滑油组合物,该组合物可以提供相等的或更好的润滑特性。该润滑油组合物包括:具有润滑粘度的油,该油的粘度指数(VI)为至少约95;钙洗涤剂,其用量使引入组合物中的钙为约0.05~约0.6wt.%;一定量的二烃基二硫代磷酸金属盐化合物,其使引入组合物中的磷最高达到约0.1wt.%(1000ppm);至少一种钛化合物,其用量足以提供给组合物至少10ppm~约1500ppm的钛。该组合物的Noack挥发度低于约15%,并且含有有效量的至少一种摩擦改性剂。
根据第二方面,本发明涉及一种改进燃料经济性和/或内燃机的摩擦特性的方法,该方法包括使用第一方面的润滑油组合物润滑内燃机和运行发动机的步骤.
根据第三方面,本发明涉及将第一方面的润滑油组合物用于改进燃料经济性和/或内燃机的摩擦特性。
其它和进一步的目的、公开的实施方案的优点和特点可以通过引证下述内容加以理解。
具体实施方式
在此公开下列实施方案。
方案1.一种完全配制的润滑油组合物,包含:
a)具有润滑粘度的油,其粘度指数为至少约95;
b)至少一种钙洗涤剂;
c)至少一种油溶性钛化合物;
d)至少一种摩擦改性剂;和
e)至少一种二烃基二硫代磷酸金属盐化合物,
其中所述组合物基本不含钼,Noack挥发度为约15wt.%或更低,来自钙洗涤剂的钙为约0.05~约0.6wt.%,来自钛化合物的钛量为约10ppm~约1500ppm,和来自二烃基二硫代磷酸金属盐化合物的磷的量最高达到约0.1wt.%。
方案2.根据方案1的组合物,其中所述钙洗涤剂选自酚钙、水杨酸钙、磺酸钙及其混合物。
方案3.根据方案1的组合物,其中所述钙洗涤剂是高碱性磺酸钙。
方案4.根据方案3的组合物,其中所述高碱性磺酸钙的总碱值为约150~约450。
方案5.根据方案1的组合物,其中所述来自钛化合物的钛的存在量为约50ppm~约500ppm。
方案6.根据方案1的组合物,其中所述钛化合物包含烷氧化钛和约C6~约C25羧酸的反应产物。
方案7.根据方案6的组合物,其中所述羧酸基本上选自己酸、辛酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、花生脂酸、油酸、芥子酸、亚油酸、亚麻酸、环烷基羧酸、苯乙酸、苯甲酸、新癸酸及其混合物。
方案8.根据方案7的组合物,其中所述钛化合物包含新癸酸钛。
方案9.根据方案7的组合物,其中所述钛化合物包含油酸钛。
方案10.根据方案1的组合物,其中所述钛化合物包含基本不含硫和磷原子的化合物。
方案11.根据方案1的组合物,其中所述至少一种二烃基二硫代磷酸金属盐化合物中的金属选自碱金属、碱土金属、铝、铅、锡、钼、锰、镍、铜、钛和锌。
方案12.根据方案1的组合物,其中所述至少一种摩擦改性剂的存在量为约0.20wt.%~约2.0wt.%,基于组合物总重量计。
方案13.根据方案1的组合物,其中所述的至少一种摩擦改性剂包含酯。
方案14.根据方案13的组合物,其中所述酯包含甘油单油酸酯。
方案15.根据方案1的组合物,其中所述至少一种摩擦改性剂包含一种化合物,该化合物选自烷氧基化胺、烷氧基化醚胺和噻二唑.
方案16.根据方案1的组合物,其中所述组合物含有来自二烃基二硫代磷酸金属盐化合物的约0.025wt.%~约0.1wt.%的磷。
方案17.根据方案16的组合物,其中所述组合物含有来自二烃基二硫代磷酸金属盐化合物的约0.025wt.%~约0.075wt.%的磷。
方案18.根据方案17的组合物,其中所述组合物含有来自二烃基二硫代磷酸金属盐化合物的约0.025wt.%~约0.05wt.%的磷。
方案19.一种用于改进内燃机的燃料经济性和燃料经济保持特性的方法,该方法包括:(1)向所述发动机中添加方案1的润滑油组合物;和(2)运行该发动机。
方案20.一种用于改善内燃机的抗磨保护的方法,该方法包括以下步骤:(1)添加方案1的润滑油组合物;和(2)运行发动机。
具有润滑粘度的油可以是选自I类、II类和/或III类基础原料油中的至少一种油、或上述基础原料油的基础油共混物,条件是上述基础油或基础油共混物的粘度是至少95,并且允许配制的润滑油组合物的Noack挥发度低于15%,该挥发度根据ASTM D5880的方法确定油品在250℃蒸发1小时后的质量损失百分比而测定。另外,具有润滑粘度的油可以是一种或多种IV类或V类基础原料油或它们的组合,或含有一种或多种IV类或V类基础原料油与一种或多种I类、II类和/或III类基础原料油的组合的基础油混合物。其它基础油可包括至少部分含有由气体液化方法而得的基础油。
对于燃料经济保持性而言,最理想的基础油是:
(a)III类基础原料油与I类或II类基础原料油的基础油共混物,其中该组合的粘度指数为至少110;或
(b)III、IV或V类基础原料油,或一种以上的III类、IV类或V类基础原料油的基础油共混物,其中粘度指数在约120-约140之间。
在本发明中基础原料油和基础油的定义与美国石油学会(API)的出版物“Engine Oil Licensing and Certification System”,Industry Services Department,14版,1996年12月,附录1,1998年12月所公开的相同。所述出版物对基础原料油分类如下:
(a)I类基础原料油,包含饱和度小于90%,和/或硫大于0.03%,且粘度指数大于或等于80并且低于120,使用表1规定的方法测试。
(b)II类基础原料油,包含饱和度大于或等于90%,和硫低于或等于0.03%,且粘度指数大于或等于80并且低于120,使用表1规定的方法测试。
(c)III类基础原料油,包含饱和度大于或等于90%,和硫低于或等于0.03%,且粘度指数大于或等于120,使用表1规定的方法测试。
(d)IV类基础原料油,是聚α烯烃(PAO)。
(e)V类基础原料油,包括未包括在I、II、III或IV类之内的所有其它基础原料油。
表1
基础原料油的分析方法
性能 | 测试方法 |
饱和度 | ASTM D 2007 |
粘度指数 | ASTM D 2270 |
硫 | ASTM D 2662,ASTM D 4294,ASTM D 4927,ASTM D 3120 |
对于这里所公开的润滑油组合物而言,在润滑油组合物中可以使用具有摩擦改性和/或极压、和/或抗氧、和/或抗磨特性的任何合适的烃溶性的钛化合物。术语“烃溶的”、“油溶的”或“分散的”并不拟表示化合物以所有比例可溶、易溶、混溶或能够悬浮于烃化合物或油中。然而,这些确实意味着它们例如是可溶的或稳定分散在油中达到足以发挥它们在油品所使用环境中的预期效果的程度。此外,如果需要,额外加入的其它添加剂也可以允许特殊添加剂以更高的含量加入。
术语“烃基”指一种基团,该基团具有一个碳原子连接在分子剩余部分和具有主要的烃类特性。烃基基团的例子包括:
1、烃取代基,即脂族(例如烷基或链烯基)、脂环族(例如环烷基或环烯基)取代基,芳基、脂族和脂环族取代的芳核等,以及环状取代基,其中环完全穿过配位体的另一部分(即任意两个所示取代基可以一起形成脂环族基团)。
2、被取代的烃取代基,即那些含有非烃基团的基团,在本发明的上下文中,没有改变取代基的主要烃基特性。本领域技术人员会知道合适的基团(例如卤素,尤其是氯和氟,氨基,烷氧基,巯基,烷基巯基,硝基,亚硝基,硫氧基等)。
3、杂取代基,即在本发明的上下文中具有主要烃特性的取代基,该取代基在其余部分由碳原子组成的链或环上含有不同于碳的原子。
重要的是,配位体的有机基团具有充足的碳原子数使得化合物可溶或可分散在油或烃流体中。例如,每个基团中的碳原子数一般为约1~约100,优选约1~约30,更优选约4~约20。
适合在此使用的烃溶的钛化合物,例如作为摩擦改性剂、极压剂或抗氧剂,是由烷氧化钛和约C6~约C25羧酸的反应产物提供的。该反应产物可以由下式表示:
其中n是选自2、3和4的整数,和R是含有约5~约24个碳原子的烃基,或由下式表示:
其中R1、R2、R3和R4中的每一个都可以相同或不同,并且选自含有约5~约25个碳原子的烃基。前式的化合物基本不含有磷和硫。
在一个实施方案中,烃溶的钛化合物可以大体或基本不含硫和磷原子,以使含有烃溶的钛化合物的润滑油或配制的润滑油包含有约0.7wt.%或更少的硫和约0.12wt.%或更少的磷。
在另一个实施方案中,烃溶的钛化合物可以基本不含活性硫。“活性”硫是没有被完全氧化的硫。在使用时,活性硫在油中进一步氧化并变得更加具有酸性。
在另一个实施方案中,烃溶的钛化合物可以基本不含所有硫。在另外的实施方案中,烃溶的钛化合物可以基本不含所有磷。在另外的实施方案中,烃溶的钛化合物基本不含所有的硫和磷。例如,钛化合物可以被溶解于其中的基础油可以含有相对少量的硫,例如在一个实施方案中硫含量低于约0.5wt.%,而在另一个实施方案中硫含量为约0.03wt.%或更少(例如II类基础油),并且在另外的实施方案中,在基础油中硫和/或磷的量可以被限制到允许成品油在给定时间内就效果而言满足合适的发动机油对硫和/或磷的规定的量。
钛/羧酸产物的例子包括但不限于钛与主要选自己酸、辛酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、花生酸、油酸、芥子酸、亚油酸、亚麻酸、环烷基羧酸、苯乙酸、苯甲酸、新癸酸等的羧酸反应的产物。制备上述钛/羧酸产物的方法已经被描述,例如在美国专利5,260,466中,该专利的公开内容在此引入作为参考。
下面给出的例子是为了举例说明实施方案,并不拟以任何方式限制实施方案。
实施例1
新癸酸钛的合成
将新癸酸(约600g)置于配有冷凝器、Dean-Stark阱、温度计、热电偶和进气口的反应容器中。将氮气吹入酸中。在剧烈搅拌下将异丙氧化钛(约245g)慢慢加入到反应容器中。将反应物加热到约140℃,并且搅拌一个小时。将反应中顶部馏出物和冷凝物收集在阱中。对反应容器施加低于大气压的压力,并且反应物被另外搅拌约两个小时直到反应结束。产品分析说明产品在约100℃时的动态粘度为约14.3cSt,并且含钛量为约6.4重量%。
实施例2
油酸钛的合成
将油酸(约489g)置于配有冷凝器、Dean-Stark阱、温度计、热电偶和进气口的反应容器中.将氮气吹入酸中.在剧烈搅拌下将异丙氧化钛(约122.7g)慢慢地加入到反应容器中.将反应物加热到约140℃,并且搅拌一个小时.将反应中顶部馏出物和冷凝物收集在阱中.对反应容器施加低于大气压的压力,并且反应物被另外搅拌约两个小时直到反应结束.产品分析说明产品在约100℃时的动态粘度为约7.0cSt,并且含钛量为约3.8重量%.
在此描述的实施方案的烃溶的钛化合物被有利地加入到润滑油组合物中。因此烃溶的钛化合物可以直接加入到润滑油组合物中。然而,在一个实施方案中,烃溶的钛化合物被基本上是惰性的、通常是液体的有机稀释剂稀释如矿物油、合成油(例如二羧酸酯)、石脑油、烷基化(例如C10-C13烷基)苯、甲苯或二甲苯,使之形成金属添加剂浓缩液。钛添加浓缩液通常含有约0%~约99重量%的稀释油。
公开的实施方案中的润滑油组合物含有钛化合物,该钛化合物的量使得组合物含有至少10ppm的钛。已经发现来自钛化合物的至少10ppm的钛与第二摩擦改性剂结合有效地提供了燃料经济利益,所述第二摩擦改性剂选自含氮的摩擦改性剂、有机多硫化物摩擦改性剂、无胺摩擦改性剂和有机的、无灰的、无氮的摩擦改性剂。
理想的是,来自钛化合物的钛含量为约10ppm~约1500ppm,例如10ppm~1000ppm,更理想的是约50ppm~500ppm,更加理想的是约75ppm~约250ppm,以润滑油的总重量计。因为这种钛化合物也可以提供给润滑油组合物抗磨作用,所以它们的使用允许所用的二烃基二硫代磷酸金属盐抗磨剂(例如ZDDP)的用量降低。工业趋势导致了减少ZDDP添加到润滑油中的量,以至于润滑油中磷含量降低至低于1000ppm,例如250ppm~750ppm,或250ppm~500ppm。为了在上述低磷润滑油组合物中提供充分的摩擦保护,钛化合物的用量应该为至少50ppm,以钛质量计。钛和/或锌的量可以使用ASTM D5185描述的方法,通过感应耦合等离子体(ICP)发射光谱测定。
以近似的方式,在润滑油组合物中使用钛化合物可以有助于降低润滑油组合物中抗氧剂和极压剂的用量。
摩擦改性剂
至少一种油溶性的摩擦改性剂必须被加入到在此所述的润滑油组合物中作为第二摩擦改性剂。第二摩擦改性剂可选自含氮的、无氮和/或无胺的摩擦改性剂。典型地,第二摩擦改性剂的用量可以为润滑油组合物的约0.02~2.0wt.%,优选0.05~1.0wt.%,更优选0.1~0.5wt.%。
这种含氮摩擦改性剂可以使用的例子包括但不限于咪唑啉、氨化物、胺、琥珀酰亚胺、烷氧基化胺、烷氧基化醚胺、氧化胺、酰胺基胺、腈、甜菜碱、季胺、亚胺类、胺盐、氨基胍(guanadine)、链烷醇酰胺,等等。
这种摩擦改性剂可以含有烃基,该烃基可以选自直链、支链或芳基烃基,或其混合基团,并且可以是饱和的或不饱和的。烃基基团主要由碳和氢组成,但是可以含有一个或多个杂原子,例如硫或氧。优选烃基基团具有12~25个碳原子并且可以是饱和的或不饱和的。更优选是带有线性烃基基团的烃基。
示例性的摩擦改性剂包括多胺的氨化物。这种化合物可以含有烃基,该烃基是线性的、或饱和或不饱和、或其混合基团,且含有不多于约12~约25个碳原子。
其它示例性的摩擦改性剂包括烷氧基化胺和烷氧基化醚胺,最优选的是每摩尔的氮含约两摩尔的环氧烷基的烷氧基化胺.这种化合物可以含有烃基,该烃基是线性的、或饱和、不饱和或其混合基团.它们含有的碳原子数不多于约12~约25,并且在烃基链上可以含有一个或多个杂原子.乙氧基化胺和乙氧基化醚胺是特别合适的含氮摩擦改性剂.胺和氨化物可以原样直接地使用,或者是以与硼化合物的加合物或反应产物的形式使用,上述硼化合物例如为氧化硼、卤化硼、偏硼酸盐、硼酸、或者是一-、二-或三-烷基硼酸酯.
可以用作摩擦改性剂的无灰有机多硫化合物包括以下式表示的有机化合物,例如油或脂肪或聚烯烃的硫化物,其中分子结构中存在具有相邻并且连接在一起的两个或多个硫原子的硫原子基团。
R1-Sx-R2
OHC-R3-S-S-R4-CHO
R1-C(O)O-R3-S-S-R4-OC(O)-R2
R1-OC(S)-S-S-C(S)O-R2
在上式中,R1和R2独立地表示直链、支链、脂环族或芳香族的烃基,其中直链、支链、脂环族单元和芳香族单元可以选择性地以任何组合方式包含在其中。可以包含不饱和键,但是优选饱和的烃基基团。其中,特别优选的是烷基基团、芳基基团、烷基芳基基团、苯甲基基团和烷基苯甲基团。
R2和R3独立地表示直链、支链、脂环族或芳香族烃基,该烃基具有两处键位,并且其中直链、支链、脂环族单元和芳香族单元可以选择性地以任何组合方式包含在其中。可以包含不饱和键,但是优选饱和的烃基基团。其中,特别优选的是亚烷基基团。
R5和R6独立地表示直链或支链的烃基,下标“x”和“y”独立地表示2或更大的整数。
具体地,例如可提及硫化鲸蜡油、硫化蒎烯油、硫化大豆油、硫化聚烯烃、二烷基二硫化物、二烷基多硫化物、二苯甲基二硫化物、二叔丁基二硫化物、聚烯烃多硫化物、诸如二烷基多硫烷基噻二唑的噻二唑型化合物、和硫化苯酚。在这些化合物中,优选二烷基多硫化物、二苯甲基二硫化物和噻二唑型化合物。特别优选二烷基多硫烷基噻二唑。
作为润滑油添加剂,可以使用含金属的化合物,诸如具有多硫化物键的酚钙.然而,因为这种化合物的摩擦系数很大,所以使用这种化合物可能并不总是合适的.相反,上述有机多硫化合物可以是不含金属的无灰化合物,并且当与其它摩擦改性剂组合使用的时候,在长时间保持低摩擦系数方面呈现出优异性能.
上述无灰有机多硫化物(此后简称“多硫化物)的添加量以硫(S)计为0.01~0.4wt.%,典型地0.1~0.3wt.%,和优选0.2~0.3wt.%,相对于润滑油组合物的总量。如果添加量低于0.01wt.%,则难以获得预期效果,然而如果添加量大于0.4wt.%,则增加了腐蚀磨损的危险。
在此处所公开的润滑油组合物中可以使用的有机的、无灰的(无金属的)、无氮的摩擦改性剂通常是已知的,并且包括羧酸和酸酐与链烷醇或乙二醇反应形成的酯,脂肪酸是特别合适的羧酸。其它有用的摩擦改性剂通常包括共价键结合到亲油的烃链上的极性端基(例如羧基或羟基)。美国专利4,702,850描述了羧酸和酸酐与链烷醇的酯。与钛化合物组合使用的特别理想的摩擦改性剂是一种酯,例如乙二醇单油酸酯(GMO)。
在此处所公开的润滑油组合物中包括上述第二摩擦改性剂,该摩擦改性剂与钛化合物组合使用,并且以有效的使用量允许组合物安全地通过连续VIB燃料经济测试。例如,第二摩擦改性剂被足量地添加到含钛润滑油组合物中,对于SAE 5W-20润滑油而言,使得保留燃料经济提高至少1.7%,对于5W-30润滑油而言提高至少1.1%,和对于10W-30润滑油而言提高至少0.6%,上述结果是在ASTM连续VIB燃料经济测试中在96小时(第II阶段性能)测量得到的。典型地,为了提供理想效果,第二摩擦改性剂的添加量可以为约0.25wt.%~约2.0wt.%(AI),以润滑油组合物的总重量为基准。
含金属洗涤剂
含金属或成灰洗涤剂既起到降低或除去沉渣的洗涤剂作用又起到酸中和剂或防锈剂的作用,由此降低磨损和腐蚀并且延长发动机寿命。洗涤剂通常包括带有长疏水尾部的极性头,该极性头包含酸性有机化合物的金属盐。该盐可含有基本上化学计量量的金属,其中它们通常被描述成中式盐或中性盐,并且可通过ASTM D-2896测定的总碱值(TBN)一般为0~80。通过使过量的金属化合物例如氧化物或氢氧化物与酸性气体例如二氧化碳反应,可能包括大量的金属碱。由此产生的高碱性洗涤剂包含中性的洗涤剂作为金属碱(例如碳酸盐)胶束的外层。这种高碱性洗涤剂的TBN值可为150或更大,并且典型地是250~450或更大。
已知的洗涤剂包括油溶性的中性和高碱性磺酸盐、酚盐、硫化酚盐、硫代磷酸盐、水杨酸盐和环烷酸盐及其它油溶性金属羧酸盐,尤其是碱金属或碱土金属,例如钠、钾、锂、钙和镁羧酸盐。最普遍使用的金属是钙和镁,其可以同时存在于用于润滑油的洗涤剂中,及钙和/或镁与钠的混合物。特别适宜的金属洗涤剂是中性和高碱性磺酸钙,其TBN值为约20~约450,而中性和高碱性酚钙和硫化酚盐的TBN值为约50~约450。
在公开的实施方案中,一种或多种钙基洗涤剂的用量可以将约0.05~约0.6wt.%的钙、钠或镁引入到组合物中。钙、钠或镁的用量可以通过感应耦合等离子体(ICP)发射光谱使用ASTM D5185中所述的方法测定。典型地,金属基洗涤剂是高碱性的,并且高碱性金属基洗涤剂的总碱值为约150~约450,更理想地,金属基洗涤剂是高碱性磺酸钙洗涤剂。公开的实施方案中的组合物可以进一步包括或中性或高碱性的镁基洗涤剂,然而,典型地,在此所公开的润滑油组合物是不含镁的。
抗磨剂
可以被添加到本发明的润滑油组合物中的二烃基二硫代磷酸金属盐抗磨剂包含二烃基二硫代磷酸金属盐,其中金属可以为碱或碱土金属、或铝、铅、锡、钼、锰、镍、铜、钛或锌。锌盐被最普遍地用于润滑油中。
二烃基二硫代磷酸金属盐可以根据已知的技术制备,首先形成二烃基二硫代磷酸(DDPA),通常使一种或多种醇或酚与P2S5反应,然后使用金属化合物中和形成的DDPA。例如,二硫代磷酸可以通过使伯醇和仲醇的混合物反应制备得到。可替代地,多种二硫代磷酸可以被制备,其中在一种之上的烃基本质上完全是仲碳,而在其它上的烃基本质上完全是伯碳。为了制备金属盐,可以使用任何碱性或中性的金属化合物,但是氧化物、氢氧化物和碳酸盐是最普遍使用的。市售添加剂经常含有过量的金属,因为在中和反应中使用过量的碱性金属化合物。
典型使用的二烃基二硫代磷酸锌(ZDDP)是油溶性的二烃基二硫代磷酸盐,并且可以用下式表示:
其中R7和R8可以是相同或不同的含1~18,典型地2~12个碳原子的烃基基团,其包括的基团例如为烷基、链烯基、芳基、芳烷基、烷芳基和环脂族基团。特别理想地,R7和R8基团是具有2~8个碳原子的烷基基团。因此该基团可以是例如乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、戊基、正己基、异己基、正辛基、癸基、十二烷基、十八烷基、2-乙基己基、苯基、丁基苯基、环己基、甲基环戊基、丙烯基、丁烯基。为了获得油溶性,二硫代磷酸中的碳原子总数(即R7和R8)通常为约5或更大。因此二烃基二硫代磷酸锌能包含二烷基二硫代磷酸锌。
为了限制由ZDDP引入润滑油组合物中的磷含量不多于0.1wt.%(1000ppm),ZDDP应该加入到润滑油组合物中的理想用量是不多于约1.1~1.3wt.%,以润滑油组合物的总重量为基准。
其它添加剂,例如下述的,也可以存在于在此所公开的润滑油组合物中。
无灰分散剂
无灰分散剂包含油溶性聚合烃骨架,该骨架含有能与要分散的颗粒缔合的官能团。典型地,分散剂包含极性部分通常通过桥连基团与聚合物骨架相连的胺、醇、酰胺或酯。无灰分散剂可以是例如选自油溶性盐、酯、氨基酯、酰胺、酰亚胺和长链烃基取代的一元和二元羧酸或其酸酐的噁唑啉;长链烃基的硫代羧酸盐衍生物;长链脂族烃,该烃含有直接与其相连的多胺;和使用甲醛和聚亚烷基多胺浓缩长链取代的苯酚制备而得的Mannich浓缩产物。
粘度改性剂
粘度改性剂(VM)的作用是提供给润滑油高温和低温的操作性能。所用的VM可以具有单一功能或者可以是多功能的。
有分散剂作用的多功能粘度改性剂也是已知的.合适的粘度改性剂是聚异丁烯、乙烯和丙烯及高级α烯烃的共聚物、聚甲基丙烯酸酯、聚烷基甲基丙烯酸酯、甲基丙烯酸酯共聚物、不饱和二元羧酸和乙烯基化合物的共聚物、苯乙烯和丙烯酸酯的内聚物、及苯乙烯/异戊二烯、苯乙烯/丁二烯和异戊二烯/丁二烯的部分氢化的共聚物,以及丁二烯和异戊二烯及异戊二烯/二乙烯基苯的部分氢化的均聚物.
氧化抑制剂
氧化抑制剂或抗氧剂降低了基础原料油在使用期破坏的趋势,氧化产物和粘度增加能证明上述破坏,该氧化产物例如为淤渣和金属表面上的漆状沉渣。这种氧化抑制剂包括受阻酚、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、无灰油溶性酚盐和硫化酚盐、磷硫化的或硫化的烃、磷酯、硫代氨基甲酸金属盐和美国专利4,867,890中描述的油溶性铜化合物。
防锈剂
可以使用选自非离子聚氧亚烷基多元醇和其酯、聚氧亚烷基酚和阴离子烷基磺酸的防锈剂。
抗腐蚀剂
可以使用带有铜和铅的抗腐蚀剂,但一般不要求使用在本发明的调方中。典型地,这种化合物是含有5~50个碳原子的噻二唑多硫化物、它们的衍生物和它们的聚合物。1,3,4噻二唑的衍生物是典型的,例如那些描述在美国专利2,719,125、2,719,126和3,087,932中的。其它相似的物质描述在美国专利3,821,236、3,904,537、4,097,387、4,107,059、4,136,043、4,188,299和4,193,882中。其它添加剂是噻二唑的硫代和多硫代的亚磺酰胺,例如那些描述在英国专利说明书1,560,830中的。苯并三唑衍生物同样落在此类添加剂中。当润滑油组合物包含这些化合物的时候,以活性成分计,这些化合物的用量一般不超过0.2wt.%。
破乳剂
可以使用少量的破乳剂。合适的破乳剂组分描述在EP 330,522中。破乳组分可以通过使氧化烯与一种加合物反应制得,该加合物是通过二环氧化合物与多羟基醇制备而得。破乳组分的使用量可以不超过0.1质量%活性成分。0.001~0.05质量%活性成分的处理比例是适宜的。
倾点下降剂
倾点下降剂,另外被称作润滑油流动改进剂,降低流体流动或能被倾泻的最低温度。这种添加剂是众所周知的。那些典型的改进流体的低温流动性的添加剂是富马酸C8~C18二烷基酯/醋酸乙烯酯的共聚物、聚烷基甲基丙烯酸酯等。
消泡剂
许多化合物都能提供控制泡沫的作用,该化合物包括聚硅氧烷型消泡剂,例如聚硅油或聚二甲基硅氧烷。
一些上述添加剂可以提供多种效果;因此,例如一种单一的添加剂可以作为分散-氧化抑制剂。这种方法是众所周知的并且不需要进一步的细节。
单独的添加剂可以任何方便的方式加入到基础原料油中。因此,每种组分能够通过以所需的浓度分散或溶解在基础原料油或基础油共混物中而被直接加入到基础原料油或基础油共混物中。此种共混可以在环境温度或高温下进行。
优选,将除了粘度改性剂和倾点下降剂以外的所有添加剂都共混成在此被描述成添加剂包的浓缩物或添加剂包,然后共混到基础原料油中制备最终的润滑油。当浓缩物与预计量基础润滑油混合时,为了在最终调方中提供所需的浓度,浓缩物典型地被配制成含有适量的添加剂。
浓缩物优选根据美国专利4,938,880描述的方法制备。该专利描述了在至少约100℃的温度下预共混制备无灰分散剂和金属洗涤剂的预混合物。随后该预混合物被冷却到至少85℃,并加入其它组分。
最终的润滑油配制物可以使用约2~约20质量%,典型地约4~约18质量%,理想地约5~约17质量%的浓缩物或添加剂包,其余的是基础原料油。
实施例3
为了评价根据公开的实施方案制备的润滑油组合物的降低磨损的效果,使用连续IVA测试方法。连续IVA测试能测量发动机油抑制凸轮轴磨损的能力。使用Nissan 2.3升、每个汽缸3个阀门、4个汽缸发动机,使待评价的曲轴箱用油经历发动机连续运转100小时,从800rpm空转周期至短的1500rpm阶段,并再返回,循环100次,在非常精确的运行条件下控制。在测试结束时,移走凸轮轴并测量磨损。12个凸轮轴凸角中的每一个都在7个地方被检测,并且对测试计算平均凸角磨损。连续IVA测试方法的通过极限,对于API SL和ILSACGF-3要求平均凸轮磨损最大为120mm,而对于API SM和ILSAC GF-4要求则最大为90mm。
基础油是I类和II类油的混合物,粘度等级为5W-30。在连续IVA测试中,对比操作(操作1)使用一种完全配制的润滑油,该润滑油含有甘油单油酸酯作为摩擦改性剂。第二操作(操作2)使用一种含有钛化合物和甘油单油酸酯的润滑油组合物,以证明在完全配制的润滑油中组合的摩擦改性剂的效果。
表2:润滑油组合物和测试结果
操作1 | 操作2 | |
组分 | 量(wt.%) | 量(wt.%) |
2100MW聚异丁烯琥珀酰亚胺分散剂 | 1.30 | 1.30 |
1300MW聚异丁烯琥珀酰亚胺分散剂 | 3.30 | 3.30 |
135溶剂中性稀释油 | 0.514 | 0.344 |
消泡剂 | 0.006 | 0.006 |
芳胺抗氧剂 | 0.74 | 0.74 |
硫化异丁烯抗氧剂 | 0.80 | 0.80 |
操作1 | 操作2 | |
300TBN高碱性磺酸钙洗涤剂 | 1.80 | 1.80 |
聚甲基丙烯酸酯倾点下降剂 | 0.40 | 0.40 |
混合的伯和仲二烷基二硫代磷酸锌 | 0.94 | 0.94 |
烯烃共聚物粘度指数改进剂 | 9.80 | 9.80 |
I类,100N,基础油 | 60.60 | 60.60 |
II类,基础油 | 19.50 | 19.50 |
甘油单油酸酯 | 0.30 | 0.30 |
新癸酸钛 | 0.00 | 0.17 |
分析数据 | ppm | ppm |
磷 | 726 | 754 |
钙 | 2072 | 2099 |
锌 | 905 | 915 |
硼 | 240 | 229 |
钛 | 0.00 | 109 |
连续IVA测试结果 | 微米 | 微米 |
平均凸轮凸角磨损(最大90微米) | 88.18 | 26.56 |
操作2得到的连续IVA测试结果清楚地证明了钛添加剂在磨损控制中的效果,这一点通过与不含钛润滑油组合物(操作1)的结果比较得到证明。钛添加剂作为抗磨剂的应用不限于此实施例所示的组合物。相应地,在I类油中包含钛添加剂的完全配制的润滑油组合物可以包括II类、II+类、III类和IV类、基础油及其混合物。
相信本发明所公开的实施方案在不使用钼添加剂的情况下,能够显著地改进发动机磨损控制。这种不含钼的润滑油组合物可以使客车发动机油满足或胜过ILSAC GF-4和API SM规格的机油。同样,在此所描述的组合物可以有效地满足连续IVA或其它任何磨损测试的一些OEM内部标准的更严格要求。
在本说明书的很多地方,参考了很多的美国专利和出版物。所有此类被引用的文件都被明确地全部引入本发明,就好像全部在这里列出一样。
前述的实施方案在其实施中易有较大变化。因此,实施方案并不拟限制到此前所列的具体实施例。然而前述的实施方案在所附权利要求的要旨和范围内,在法律问题方面,包括其等同物。
专利权所有人并不打算提供任何公开的实施方案给公众,在一定程度上,任何已公开的改进或改变虽然不能在字面上直接落入权利要求的范围,但它们在等同物原则上被认为是其中的一部分。
Claims (10)
1.一种完全配制的润滑油组合物,包含:
a)具有润滑粘度的油,其粘度指数为至少95;
b)至少一种钙洗涤剂;
c)至少一种油溶性钛化合物,其中所述钛化合物包含烷氧化钛和C6~C25羧酸的反应产物;
d)至少一种摩擦改性剂;和
e)至少一种二烃基二硫代磷酸金属盐化合物,
其中所述组合物不含有钼,Noack挥发度为15wt.%或更低,来自钙洗涤剂的钙为0.05~0.6wt.%,来自钛化合物的钛量为10ppm~1500ppm,和来自二烃基二硫代磷酸金属盐化合物的磷的量最高达到0.1wt.%。
2.根据权利要求1的组合物,其中所述来自钛化合物的钛的存在量为50ppm~500ppm。
3.根据权利要求1的组合物,其中所述钙洗涤剂选自酚钙、水杨酸钙、磺酸钙及其混合物。
4.根据权利要求1的组合物,其中所述钛化合物包含不含硫和磷原子的化合物。
5.根据权利要求1的组合物,其中所述摩擦改性剂包含甘油单油酸酯。
6.根据权利要求1的组合物,其中所述组合物含有来自二烃基二硫代磷酸金属盐化合物的0.025wt.%~0.075wt.%的磷。
7.根据权利要求1的组合物,其中所述羧酸选自己酸、辛酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、花生脂酸、油酸、芥子酸、亚油酸、亚麻酸、环烷基羧酸、苯乙酸、苯甲酸、新癸酸及其混合物。
8.根据权利要求7的组合物,其中所述钛化合物包含新癸酸钛。
9.一种用于改进内燃机的燃料经济性和燃料经济保持特性的方法,该方法包括:(1)向所述发动机中添加权利要求1的润滑油组合物;和(2)运行所述发动机。
10.一种用于改善内燃机抗磨保护的方法,该方法包括以下步骤:(1)添加权利要求1的润滑油组合物;和(2)运行所述发动机。
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- 2006-12-08 JP JP2006332305A patent/JP2007162021A/ja active Pending
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EP1795582A8 (en) | 2008-08-20 |
JP2011042801A (ja) | 2011-03-03 |
CN101012407A (zh) | 2007-08-08 |
JP5298097B2 (ja) | 2013-09-25 |
AU2006249220B2 (en) | 2009-01-15 |
US20070132274A1 (en) | 2007-06-14 |
EP1795582A3 (en) | 2011-03-02 |
AU2006249220A1 (en) | 2007-06-28 |
US7776800B2 (en) | 2010-08-17 |
SG133516A1 (en) | 2007-07-30 |
EP1795582B1 (en) | 2016-05-04 |
JP2007162021A (ja) | 2007-06-28 |
EP1795582A2 (en) | 2007-06-13 |
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