EP1702049B1 - Lubricating composition substantially free of zddp - Google Patents
Lubricating composition substantially free of zddp Download PDFInfo
- Publication number
- EP1702049B1 EP1702049B1 EP04814892.8A EP04814892A EP1702049B1 EP 1702049 B1 EP1702049 B1 EP 1702049B1 EP 04814892 A EP04814892 A EP 04814892A EP 1702049 B1 EP1702049 B1 EP 1702049B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- oil
- metal
- group
- ppm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Not-in-force
Links
- 239000000203 mixture Substances 0.000 title claims description 136
- 230000001050 lubricating effect Effects 0.000 title claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 34
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 25
- 239000011574 phosphorus Substances 0.000 claims description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims description 25
- 239000002270 dispersing agent Substances 0.000 claims description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 239000005864 Sulphur Substances 0.000 claims description 21
- 150000001412 amines Chemical class 0.000 claims description 15
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 12
- 239000000314 lubricant Substances 0.000 claims description 11
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- 230000003247 decreasing effect Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- 229920000193 polymethacrylate Polymers 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 230000003749 cleanliness Effects 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims 2
- 239000003921 oil Substances 0.000 description 69
- 235000019198 oils Nutrition 0.000 description 69
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 30
- 239000000654 additive Substances 0.000 description 25
- 239000010687 lubricating oil Substances 0.000 description 23
- -1 sechexyl Chemical group 0.000 description 21
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 17
- 239000011575 calcium Substances 0.000 description 17
- 229910052791 calcium Inorganic materials 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 239000003599 detergent Substances 0.000 description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- 231100000241 scar Toxicity 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000003085 diluting agent Substances 0.000 description 10
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 8
- 239000003607 modifier Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical group OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229960002317 succinimide Drugs 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 229920002367 Polyisobutene Polymers 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 229960004889 salicylic acid Drugs 0.000 description 4
- 239000010689 synthetic lubricating oil Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 3
- 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 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 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
- AFSHUZFNMVJNKX-UHFFFAOYSA-N 1,2-di-(9Z-octadecenoyl)glycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(CO)OC(=O)CCCCCCCC=CCCCCCCCC AFSHUZFNMVJNKX-UHFFFAOYSA-N 0.000 description 2
- AFSHUZFNMVJNKX-LLWMBOQKSA-N 1,2-dioleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](CO)OC(=O)CCCCCCC\C=C/CCCCCCCC AFSHUZFNMVJNKX-LLWMBOQKSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007866 anti-wear additive Substances 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012612 commercial material Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000010688 mineral lubricating oil Substances 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 150000000178 1,2,4-triazoles Chemical class 0.000 description 1
- RDAGYWUMBWNXIC-UHFFFAOYSA-N 1,2-bis(2-ethylhexyl)benzene Chemical class CCCCC(CC)CC1=CC=CC=C1CC(CC)CCCC RDAGYWUMBWNXIC-UHFFFAOYSA-N 0.000 description 1
- YEYQUBZGSWAPGE-UHFFFAOYSA-N 1,2-di(nonyl)benzene Chemical class CCCCCCCCCC1=CC=CC=C1CCCCCCCCC YEYQUBZGSWAPGE-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-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
- 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
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical class ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-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
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- 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
- LODHFNUFVRVKTH-ZHACJKMWSA-N 2-hydroxy-n'-[(e)-3-phenylprop-2-enoyl]benzohydrazide Chemical compound OC1=CC=CC=C1C(=O)NNC(=O)\C=C\C1=CC=CC=C1 LODHFNUFVRVKTH-ZHACJKMWSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical class CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- RKLRVTKRKFEVQG-UHFFFAOYSA-N 2-tert-butyl-4-[(3-tert-butyl-4-hydroxy-5-methylphenyl)methyl]-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 RKLRVTKRKFEVQG-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- AJHPGXZOIAYYDW-UHFFFAOYSA-N 3-(2-cyanophenyl)-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical compound CC(C)(C)OC(=O)NC(C(O)=O)CC1=CC=CC=C1C#N AJHPGXZOIAYYDW-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- RREANTFLPGEWEN-MBLPBCRHSA-N 7-[4-[[(3z)-3-[4-amino-5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidin-2-yl]imino-5-fluoro-2-oxoindol-1-yl]methyl]piperazin-1-yl]-1-cyclopropyl-6-fluoro-4-oxoquinoline-3-carboxylic acid Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(\N=C/3C4=CC(F)=CC=C4N(CN4CCN(CC4)C=4C(=CC=5C(=O)C(C(O)=O)=CN(C=5C=4)C4CC4)F)C\3=O)=NC=2)N)=C1 RREANTFLPGEWEN-MBLPBCRHSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000021357 Behenic acid Nutrition 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229920002368 Glissopal ® Polymers 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QVHMSMOUDQXMRS-UHFFFAOYSA-N PPG n4 Chemical class CC(O)COC(C)COC(C)COC(C)CO QVHMSMOUDQXMRS-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- GLOYGJPNNKTDIG-UHFFFAOYSA-N SC=1N=NSC=1S Chemical class SC=1N=NSC=1S GLOYGJPNNKTDIG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000005024 alkenyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- DZQISOJKASMITI-UHFFFAOYSA-N decyl-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound CCCCCCCCCCP(O)(O)=O DZQISOJKASMITI-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical class CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 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 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- LVZUNTGFCXNQAF-UHFFFAOYSA-N n-nonyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCCC)C1=CC=CC=C1 LVZUNTGFCXNQAF-UHFFFAOYSA-N 0.000 description 1
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- LQNPIBHEOATAEO-UHFFFAOYSA-N octanoate;octylazanium Chemical compound CCCCCCCCN.CCCCCCCC(O)=O LQNPIBHEOATAEO-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- PDEDQSAFHNADLV-UHFFFAOYSA-M potassium;disodium;dinitrate;nitrite Chemical compound [Na+].[Na+].[K+].[O-]N=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PDEDQSAFHNADLV-UHFFFAOYSA-M 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 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
- 239000010802 sludge Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 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
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000001911 terphenyls Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JZALLXAUNPOCEU-UHFFFAOYSA-N tetradecylbenzene Chemical class CCCCCCCCCCCCCCC1=CC=CC=C1 JZALLXAUNPOCEU-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical class OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 150000004072 triols Chemical class 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
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/027—Neutral salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/288—Partial esters containing free carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
-
- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
-
- 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
-
- 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
-
- 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
- C10N2030/50—Emission or smoke controlling properties
-
- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
Definitions
- the present invention relates to a lubricating oil composition containing a metal salixarate and other performance additives.
- the lubricating oil composition has antiwear and detergency performance in the absence of a metal hydrocarbyl dithiophosphate.
- lubricating oils It is well known for lubricating oils to contain a number of additives used to protect the engine from wear, the accumulation of sludge and filter plugging.
- Common additives for engine lubricating oils are zinc dialkyldithiophosphate (ZDDP) as an antiwear additive, and overbased calcium sulphonate detergents. It is believed that ZDDP antiwear additives protect the engine by forming a protective film on metal surfaces.
- Typical treatment quantities of ZDDP range from 1 to 2 weight percent based on the total weight of the lubricant. Detergents such as overbased calcium sulphonate help keep the engine parts clean of soot and other deposits, and offer an alkalinity reserve.
- Typical treatment quantities of detergents range from 0.05 to 10 weight percent based on the total weight of the lubricant.
- phosphates and sulphonates derived from engine lubricants have been shown to contribute in part to particulate emissions. Further, sulphur and phosphorus tend to poison the NO x catalysts used in catalytic converters, resulting in a reduction in performance of said catalysts. Any reduction in the performance of catalytic converters tends to result in increased amounts of greenhouse gases such as nitric oxide and/or sulphur oxides. However, reducing the amount of ZDDP will increase the amount of wear in an engine. Also reducing the amount of detergent will decrease engine cleanliness and result in increased soot deposits.
- US Patent Number 6,200,936 discloses compounds containing phenolic units and salicylic units in a lubricating composition.
- the compounds can be salted with calcium.
- the examples of lubricating compositions contain phenolic units with a dodecyl alkyl group.
- the compounds of the invention can be used as a detergent in gasoline or diesel fuel. They also stabilise gasoline or diesel compositions against thermal decomposition.
- European Patent Application 1 262 538 A2 discloses a metal detergent derived from an aromatic carboxylic acid, a metal detergent derived from phenol capable of imparting oxidation resistance in a lubricating oil composition.
- the aromatic carboxylic acid is a salicylic acid substituted with an alkyl group.
- US-A-2003/158048 discloses lubricants for internal combustion engines having low SASH ash, low P content derived from ZnDTP.
- EP-A-1167497 refers to fow P, low ash lubricants compositions for diesel engines using conventional detergents alone with other additives.
- composition of the present invention provides detergency and antiwear performance to an oil of lubricating viscosity often used in an engine oil and said composition is substantially free of a metal hydrocarbyl dithiophosphate.
- the present invention provides a composition comprising:
- the invention further provides method for lubricating an internal combustion engine comprising supplying thereto a lubricant comprising the composition mentioned above.
- Preferred embodiments of the invention are apparent from the dependent claims.
- composition of the invention imparts one or more of improved engine cleanliness, decreased wear, decreased NO x emissions and decreased particulate emissions.
- the present invention provides a composition as described above. Often the composition has a total sulphur content below 0.5 wt %, preferably below 0.3 wt %, more preferably 0.1 wt % and most preferably near 0 wt %. Often the major source of sulphur in the composition of the invention is derived from diluent oil. Usually the diluent oil is used in the manufacturing processes used for preparing many of the component additives mentioned below.
- the composition of the invention often have a sulphur content of 700 ppm or less, preferably 600 ppm or less, more preferably 300 ppm or less, even more preferably 100 ppm or less and most preferably 50 ppm or less such as less than 30 ppm, 25 ppm or less, 20 ppm or less and 15 ppm or less.
- the sulphur content of the composition is often increased by up to 800 ppm, preferably up to 600 ppm and most preferably up to 400 ppm, for instance 200 ppm or 300 ppm.
- the composition has a total phosphorus content below 0.1 wt %, preferably equal to or less than 0.085 wt %, more preferably equal to or less than 0.07 wt %, even more preferably equal to or less than 0.055 wt % and most preferably equal to or less than 0.05 wt % of the composition, such as 200 ppm or less, preferably 100 ppm or less, more preferably 50 ppm or less and most preferably 10 ppm or less.
- the phosphorus is present from 1 ppm or 10 ppm to 50 ppm or 200 ppm.
- the composition has a total ash content as determined by ASTM D-874 of below 1.5 wt %, preferably equal to or less than 1.1 wt %, more preferably equal to or less than 1.0 wt %, even more preferably equal to or less than 0.8 wt % and most preferably equal to or less than 0.5 wt % of the composition.
- the total ash content is present from 0.1 wt % or 0.2 wt % to 0.6 wt % or 0.7 wt%.
- the substrate of the metal salixarate of the invention is often represented by one or a mixture of substantially linear compounds comprising at least one unit of the formulae (I) or (II): or each end of the compound having a terminal group of formulae (III) or (IV): such groups being linked by divalent bridging groups, which may be the same or different for each linkage; wherein in formulas (I)-(IV) f is 1, 2 or 3, preferably 1 or 2; U is -OH, -NH 2 -NHR 1 , -N(R 1 ) 2 or mixtures thereof, R 1 is a hydrocarbyl group containing 1 to 5 carbon atoms; R 2 is hydroxyl or a hydrocarbyl group and j is 0, 1, or 2; R 3 is hydrogen or a hydrocarbyl group; R 4 is a hydrocarbyl group or a substituted hydrocarbyl group; g is 1, 2 or 3, provided at least one R 4 group contains 8 or more carbon atoms; and wherein the molecules on average contain
- the U group in formulae (i) and (iii) may be located in one or more positions ortho, meta, or para to the -COOR 3 group. Preferably the U group is located ortho to the -COOR 3 group.
- formulae (i) and (iii) are derived from 2-hydroxybenzoic acid (often called salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid or mixtures thereof.
- U is a -NH 2 group
- formulae (i) and (iii) are derived from 2-aminobenzoic acid (often called anthranilic acid), 3-aminobenzoic acid, 4-aminobenzoic acid or mixtures thereof.
- the divalent bridging group which may be the same or different in each occurrence, includes -CH 2 - (methylene bridge) and -CH 2 OCH 2 - (ether bridge), either of which may be derived from an aldehyde such as formaldehyde or a formaldehyde equivalent (e.g., paraform, formalin), ethanal or propanal.
- aldehyde such as formaldehyde or a formaldehyde equivalent (e.g., paraform, formalin), ethanal or propanal.
- the metal of the metal salixarate is often mono-valent, di-valent or mixtures thereof.
- the metal is selected from an alkali metal or alkaline earth metal such as magnesium, calcium, potassium or sodium, although magnesium, calcium, potassium or mixtures thereof are most preferred.
- each R 5 can be the same or different, and are hydrogen or an alkyl group, provided at least one R 5 is alkyl.
- R 5 is a polyisobutene group (especially of molecular weight 200 to 1,000, or about 550).
- Significant amounts of di-or trinuclear species may also be present containing one salicylic end group of formula (III).
- the salixarate detergent may be used alone or with other detergents.
- Salixarate derivatives and methods of their preparation are described in greater detail in U.S. -A-6,200,936 and PCT Publications WO-A-01/56968 and
- the metal salixarate is often present on an oil free basis at 0.01 to 20, preferably 0.1 to 10, more preferably 0.2 to 8 and most preferably 0.5 to 5 weight percent of the composition.
- additives are selected from the group consisting of (1) an antioxidant; (2) a friction modifier; (3) a dispersant; (4) a viscosity modifier; and (5) an antiwear agent other than a metal hydrocarbyl dithiophosphate. Often 2 or more and most preferably 3 or more of additives (1)-(5) are present in the invention.
- each of the additives (1)-(5) are present on an oil free basis at 0 to 25, preferably 0.1 to 20, more preferably 0.3 to 15 and most preferably 1 to 10 weight percent of the composition, with the proviso that at least one additive is present at 0.1 or more weight percent of the composition.
- the antioxidant often includes a diphenylamine antioxidant, a hindered phenol antioxidant, or mixtures thereof.
- antioxidant additives such as a molybdenum dithiocarboamate or a sulphurised olefin may also be added to the composition of the invention, although preferably the composition is substantially free of a molybdenum dithiocarboamate or a sulphurised olefin.
- the term "substantially free of a molybdenum dithiocarboamate or a sulphurised olefin” means the composition will contain a molybdenum dithiocarboamate or a sulphurised olefin present at less than 100 ppm, preferably less than 20ppm and most preferably 1 ppm or less.
- the diphenylamine suitable for the invention is often represented by the formula: wherein are independently a hydrocarbyl group; and z is zero or higher, provided that on at least one ring, z is non-zero.
- the hydrocarbyl group contains 1 to 24, preferably 2 to 18 and most preferably 4 to 12 carbon atoms.
- diphenylamine antioxidants examples include octyl diphenylamine, nonyl diphenylamine, bis-octyl diphenylamine, bis-nonyl diphenylamine or mixtures thereof.
- the diphenylamine is often present on an oil free basis at 0.01 to 20, preferably 0.05 to 10, more preferably 0.1 to 5 and most preferably 0.2 to 3 weight percent of the composition.
- the hindered phenol suitable for the invention is often represented by the formula: wherein R 8 and R 9 are independently branched or linear alkyl groups containing 1 to 24, preferably 4 to 18, and most preferably 4 to 12 carbon atoms; and E is hydrogen, a hydrocarbyl group, a bridging group linking to a second aromatic group, an ester-containing group, or mixtures thereof.
- R 8 and R 9 may be either straight or branched chain; branched is preferred. Suitable examples of R 8 and R 9 include secondary butyl and tertiary butyl.
- the hindered phenol of formula (VII) suitable for the invention are esters or acids represented by the formula: wherein R 8 and R 9 are as defined above and R 10 is hydrogen, a hydrocarbyl group or mixtures thereof.
- R 10 is a hydrocarbyl group
- R 10 is preferably selected from the group consisting of butyl, sec-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, sechexyl, n-octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and mixtures thereof.
- the hindered phenol of formula (VII) suitable for the invention contains a bridging group.
- suitable bridging groups include an alkylene bridge or an ether bridge, often containing 1 to 8, preferably 1 to 6, more preferably 1 to 4 and most preferably 1 to 2 carbon atoms.
- Examples of a suitable bridge group include -CH 2 -, -CH 2 CH 2 -, -CH 2 OCH 2 - and -CH 2 CH 2 OCH 2 CH 2 -.
- the hindered phenol with a bridging group is often represented by the formula: wherein R 11 and R 12 are defined above and Y is a bridging group.
- Examples of a methylene-bridged hindered phenol include 4,4'-methylene-bis-(6-tert-butyl-o-cresol), 4,4 -methylene-bis-(2-tert-amyl-o-cresol) and 4,4'-methylene-bis-(2,6-di-tertbutylphenol).
- the hindered phenol of the invention also includes compounds represented by the formula: wherein R 8 , E and Y are defined above.
- suitable methylene-bridged hindered phenol of formula (VIII) include 2,2 -methylene-bis-(4-methyl-6-tert-butylphenol), and 2,2 -methylene-bis-(4-ethyl-6-tert-butylphenol), 2,2 - methylene-bis-(4-propyl-6-tert-butylphenol).
- the hindered phenol is often present on an oil free basis at 0.01 to 25, preferably 0.1 to 20, more preferably 0.5 to 15 and most preferably 1 to 10 weight percent of the composition.
- the invention further includes a dispersant often derived from N-substituted long chain alkenyl succinimide or mixtures thereof.
- the dispersants can be used alone or in combination with other dispersants.
- the N-substituted long chain alkenyl succinimides have a variety of chemical structures and include a mono-succinimide and/or a di-succinimide.
- the long chain alkenyl group will have number average molecular weight of 350 to 10,000, preferably 400 to 7000, more preferably 500 to 5000 and most preferably 500 to 4000.
- the long chain alkenyl group is a polyisobutylene group, which has a number average molecular weight from 800 to 1600 and in another embodiment from 1600 to 3000.
- the succinimide is often prepared by the condensation of a hydrocarbyl-substituted acylating agent (e.g., hydrocarbyl-substituted succinic anhydride) with a polyamine or an amino alcohol, often a polyalkylene polyamine or poly(ethyleneamine) such as triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine or, in one embodiment, polyamine still bottoms.
- a hydrocarbyl-substituted acylating agent e.g., hydrocarbyl-substituted succinic anhydride
- a polyamine or an amino alcohol often a polyalkylene polyamine or poly(ethyleneamine) such as triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine or, in one embodiment, polyamine still bottoms.
- N-substituted long chain alkenyl succinimides dispersant additives and their preparation are disclosed, for instance, in US -A- 3,361,673 , 3,401,118 and 4,234,435 .
- Mannich bases are the reaction products of alkyl phenols in which the alkyl group typically contains at least 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines) and are described in more detail in U.S. -A- 3,634,515 .
- ashless dispersant is high molecular weight esters. These materials are similar to the above-described succinimides except that they may be seen as having been prepared by reaction of a hydrocarbyl acylating agent and a polyhydric aliphatic alcohol such as glycerol, pentaerythritol, or sorbitol. Such materials are described in more detail in U.S. -A- 3,381,022 .
- dispersants include polymeric dispersant additives, which are generally hydrocarbon-based polymers which contain polar functionality to impart dispersancy characteristics to the polymer.
- Dispersants may also be post-treated by reaction with any of a variety of agents. Among these are urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, and phosphorus compounds. References detailing such treatment are listed in U.S. -A- 4,654,403 .
- the dispersant is often present on an oil free basis at 0.01 to 20, preferably 0.1 to 15, more preferably 0.2 to 10 and most preferably 0.5 to 6 weight percent of the composition.
- the friction modifier can be a monoester of a polyol and an aliphatic carboxylic acid, often an acid containing 12 to 24 carbon atoms.
- the monoester of a polyol and an aliphatic carboxylic acid is in the form of a mixture with a sunflower oil or the like, which may be present in the friction modifier mixture from 5 to 95, preferably 10 to 90, more preferably 20 to 85 and most preferably 20 to 80 weight percent of said mixture.
- Polyols include diols, triols, and alcohols with higher numbers of alcoholic OH groups.
- Polyhydric alcohols include ethylene glycols, including di-, tri- and tetraethylene glycols; propylene glycols, including di-, tri- and tetrapropylene glycols; glycerol; butane diol; hexane diol; sorbitol; arabitol; mannitol; sucrose; fructose; glucose; cyclohexane diol; erythritol; and pentaerythritols, including di- and tripentaerythritol; preferably, diethylene glycol, triethylene glycol, glycerol, sorbitol, pentaerythritol and dipentaerythritol.
- the aliphatic carboxylic acids which form the esters are those acids containing 12 to 24 carbon atoms. Acids containing straight chain hydrocarbyl groups containing 12 to 24 carbon atoms are preferred, for instance, 14 to 20 or 16 to 18 carbon atoms. Such acids can be used in combination with acids with more or fewer carbon atoms as well.
- the acid is a monocarboxylic acid.
- carboxylic acids include dodecanoic acid, stearic acid, lauric acid, behenic acid, and oleic acid.
- esters used in the present invention are in particular the monoesters of such polyols and such carboxylic acids.
- a preferred ester is glycerol monooleate.
- glycerol monooleate is a mixture which includes such materials as glycerol, oleic acid, other long chain acids, glycerol dioleate, and glycerol trioleate.
- the commercial material is believed to include about 60 ⁇ 5 percent by weight of the chemical species "glycerol monooleate,” along with 35 ⁇ 5 percent glycerol dioleate, and less than about 5 percent trioleate and oleic acid.
- the amounts of the monoesters, described below, are calculated based on the actual, corrected, amount of polyol monoester present in any such mixture.
- friction modifiers that are suitable for the invention include fatty amines, fatty phosphites, fatty acid amides, fatty epoxides, alkoxylated fatty amines, metal salts of fatty acids, sulfurised olefins, fatty imidazolines, condensation products of carboxylic acids and polyalkylene-polyamines, amine salts of alkylphosphoric acids.
- the friction modifier is free of sulphur and/or phosphorus.
- the friction modifier is often present on an oil free basis at 0.01 to 20, preferably 0.05 to 10, more preferably 0.1 to 5 and most preferably 0.2 to 3 such as 0.5 to 2 weight percent of the composition.
- the viscosity modifier is often an olefin copolymer.
- the olefin copolymer backbone often contains two to four, preferably two to three and most preferably two different olefin monomers.
- the olefin monomers often contain 2 to 20, preferably 2 to 10, more preferably 2 to 6 and most preferably 2 to 4 carbon atoms.
- the viscosity modifiers are often present on an oil free basis at of 0.01 to 15, preferably 0.05 to 10, more preferably 0.1 to 5 and most preferably 0.2 to 3 weight percent of the composition.
- R 10 is a hydrocarbyl group, preferably an alkyl radical containing 1 to 18, preferably 1 to 10, more preferably 1 to 6 and most preferably 1 to 3 carbon atoms.
- the hydrocarbyl group includes an alkyl radical that has a straight chain, a branched chain or mixtures thereof.
- Suitable comonomers include propylene, 1-butene, 1-hexene, 1-octene, 4-methylpentene-1, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene or mixtures thereof.
- the comonomer is 1-butene, propylene or mixtures thereof.
- olefin copolymers include ethylenepropylene copolymers or ethylene-butene-1 copolymers.
- viscosity modifiers suitable for the invention include polymeric materials including hydrogenated styrene-butadiene rubbers, hydrogenated styrene-isoprene polymers, hydrogenated radical isoprene polymers, polymethacrylate acid esters, polyacrylate acid esters, polyalkyl styrenes, alkenyl aryl conjugated diene copolymers, polyalkylmethacrylates, esters of maleic anhydride-styrene copolymers or mixtures thereof.
- polymeric materials including hydrogenated styrene-butadiene rubbers, hydrogenated styrene-isoprene polymers, hydrogenated radical isoprene polymers, polymethacrylate acid esters, polyacrylate acid esters, polyalkyl styrenes, alkenyl aryl conjugated diene copolymers, polyalkylmethacrylates, esters of maleic anhydride-styrene copo
- the olefin copolymer of the invention is further grafted with an unsaturated dicarboxylic acid anhydride or derivatives thereof and an amine to form a dispersant viscosity modifier (often referred to as DVM), thus named because they also exhibit dispersant properties.
- DVM additives and their preparation are disclosed, for instance, in US - A - 6,107,258 and 6,107,257 .
- olefin copolymer DVM's examples include those commercially available from DSM as PA1250TM, PA1260TM and PA1274TM as well as Hitec 5777TM (commercially available from Ethyl Corporation).
- the dispersant viscosity modifier is selected from the group consisting of (a) an olefin copolymer grafted with an unsaturated dicarboxylic acid anhydride or derivatives thereof and an amine; (b) a polymethacrylate functionalised with an amine; (c) an esterified copolymer comprising (i) styrene, (ii) an unsaturated dicarboxylic acid anhydride or derivatives thereof, optionally functionalised with an amine; and mixtures thereof.
- DVM's derived from a polymethacrylate and/or a styrene copolymer are prepared by reacting with an amine as described in US - A - 6,107,258 and 6,107,257 .
- the DVM can be used alone or in combination with other DVM's.
- the dispersant viscosity modifier is present on an oil free basis at 0.01 to 6, preferably 0.05 to 6, more preferably 0.08 to 4 and most preferably 0.1 to 2 weight percent of the composition.
- composition of the invention may additionally contain an antiwear agent other than a metal hydrocarbyl dithiophosphate.
- Suitable antiwear agents include phosphoric acid esters or salt thereof; phosphites; and phosphorus-containing carboxylic esters, ethers, and amides or mixtures thereof.
- the composition of the invention is substantially free of phosphorus- and/or sulphur-containing antiwear agents. In one embodiment of the invention the composition is free of antiwear agents.
- the term "substantially free of antiwear agents containing sulphur and/or phosphorus" means the composition will contain antiwear agents present at less than 50 ppm, preferably less than 10 ppm and most preferably 1 ppm or less. In one embodiment of the invention no antiwear agents containing sulphur and/or phosphorus are present. In one embodiment of the invention 1 ppm to 15 ppm of antiwear agents containing sulphur and/or phosphorus are present.
- the lubricating oil composition of the present invention may be added to an oil of lubricating viscosity.
- the oil includes natural and synthetic oils, oil derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined and re-refined oils, or mixtures thereof.
- Unrefined oils are those obtained directly from a natural or synthetic source generally without (or with little) further purification treatment.
- Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
- Purification techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and the like.
- Re-refined oils are also known as reclaimed or reprocessed oils, and are obtained by processes similar to those used to obtain refined oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
- Natural oils useful in making the inventive lubricants include animal oils, vegetable oils (e.g., castor oil, lard oil), mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
- animal oils e.g., castor oil, lard oil
- mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
- Synthetic lubricating oils are useful and include hydrocarbon oils such as polymerised and interpolymerised olefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers); poly(1-hexenes), poly(1-octenes), poly(1-decenes), and mixtures thereof; alkyl-benzenes (e.g.
- dodecylbenzenes tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); alkylated diphenyl ethers and alkylated diphenyl sulphides and the derivatives, analogs and homologs thereof or mixtures thereof.
- the synthetic lubricating oils are free of alkylated diphenyl sulphides.
- synthetic lubricating oils include but are not limited to polyol esters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), and polymeric tetrahydrofurans.
- Synthetic oils may be produced by Fischer-Tropsch reactions and typically may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes.
- the synthetic lubricating oils are free of phosphorus-containing esters.
- Oils of lubricating viscosity may also be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
- the five base oil groups are as follows: Group I (sulphur content >0.03 wt %, and/or ⁇ 90 wt % saturates, viscosity index 80-120); Group II (sulphur content ⁇ 0.03 wt %, and ⁇ 90 wt % saturates, viscosity index 80-120); Group III (sulphur content ⁇ 0.03 wt %, and ⁇ 90 wt % saturates, viscosity index ⁇ 120); Group IV (all polyalphaolefins (PAO's)); and Group V (all others not included in Groups I, II, III, or IV).
- PAO's polyalphaolefins
- the oil of lubricating viscosity is selected from the group consisting of an API Group I, II, III, IV, V oil and mixtures thereof; preferably an API Group II, III, IV or V oil and mixtures thereof; and most preferably an API Group III, IV or V oil and mixtures thereof. If the oil of lubricating viscosity is an API Group II, III, IV or V oil there may be up to a maximum of 20 wt %, preferably up to a maximum of 10 wt %, more preferably up to a maximum of 5 wt % and most preferably up to a maximum of 1.5 wt % of the lubricating oil an API Group I oil.
- Suitable API Group III oils include NexbaseTM 3050, NexbaseTM 3043, YubaseTM 4, YubaseTM 6, and ShellTM XHVI 5.2.
- the oil of lubricating viscosity is often present at up to 99.98, preferably up to 99.8, more preferably up to 99.65 and most preferably up to 99.3 weight percent of the composition.
- the present invention is in the form of a concentrate (which can be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of each of the above-mentioned dispersant, as well as other components, to diluent oil is often 80:20 to 10:90 by weight.
- the invention is substantially free of to free of a metal hydrocarbyl dithiophosphate often represented by the formula: wherein R 11 and R 12 are independently hydrogen, hydrocarbyl groups or mixtures thereof, provided that at least one of R 11 and R 12 is a hydrocarbyl group, preferably alkyl or cycloalkyl with 1 to 30, preferably 2 to 20 and most preferably 2 to 15 carbon atoms.
- the term "substantially free of” means that the composition contains 400 ppm or less of phosphorus, preferably 300 ppm or less of phosphorus, more preferably 200 ppm or less of phosphorus, even more preferably 100 ppm or less of phosphorus and most preferably 100 ppm or less of phosphorus such as 50 ppm, 20 ppm or 1 ppm or less, derived from a metal hydrocarbyl dithiophosphate. In one embodiment of the invention the composition contains 0.5 ppm or 10ppm to 50 ppm of phosphorus derived from a metal hydrocarbyl dithiophosphate. In one embodiment of the invention the composition is free of a metal hydrocarbyl dithiophosphate.
- M' is a metal, and n is an integer equal to the available valence of M'.
- M' is mono- or di- or tri- valent, preferably divalent, more preferably a divalent transition metal.
- M' is zinc.
- M' is calcium.
- M' is barium.
- Examples of a metal hydrocarbyl dithiophosphate include zinc dihydrocarbyl dithiophosphates (often referred to as ZDDP, ZDP or ZDTP).
- composition of the invention optionally further includes other performance additives.
- the other performance additives selected from the group consisting of detergents other than those of component (a) of the invention, corrosion inhibitors, antiscuffing agents, foam inhibitors, demulsifiers, pour point depressants seal swelling agents and mixtures thereof.
- the total combined amount of the other performance additives present on an oil free basis is often from 0 to 20, preferably 0.01 to 15, more preferably 0.05 to 10 and most preferably 0.1 to 5 weight percent of the composition. Although one or more of the other performance additives may be present, it is common for the other performance additives to be present in different amounts relative to each other.
- Detergents other than those of component (a) of the invention include neutral or overbased, Newtonian or non-Newtonian, basic salts of alkali, alkaline earth and transition metals with one or more of a phenate, a sulphonate, a carboxylic acid, a phosphorus acid, a mono- and/or a dithiophosphoric acid, a saligenins, an alkylsalicylate or mixtures thereof.
- Commonly used metals include sodium, potassium, calcium, magnesium lithium or mixtures thereof. Most commonly used metals include sodium, magnesium and calcium.
- the composition of the invention is free of detergents containing sulphur and/or phosphorus.
- performance additives such as corrosion inhibitors including octylamine octanoate, condensation products of dodecenyl succinic acid or anhydride and a fatty acid such as oleic acid with a polyamine; metal deactivators including derivatives of benzotriazoles, 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles or 2-alkyldithiobenzothiazoles; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides; and seal swell agents including Exxon Necton-37TM (FN 13
- the components (a)-(c) are often mixed sequentially, separately for the composition of the invention.
- the mixing conditions are often 15°C to 130°C, preferably 20°C to 120°C and most preferably 25°C to 110°C; and for a period of time in the range 30 seconds to 48 hours, preferably 2 minutes to 24 hours, more preferably 5 minutes to 16 hours and most preferably 10 minutes to 5 hours; and at pressures in the range 86 kPa to 266 kPa (650 mm Hg to 2000 mm Hg), preferably 91 kPa to 200 kPa (690 mm Hg to 1500 mm Hg), and most preferably 95 kPa to 133 kPa (715 mm Hg to 1000 mm Hg).
- the process optionally includes mixing other optional performance additives as described above.
- the optional performance additives are often added sequentially, separately or as a concentrate.
- composition of the present invention is useful in an internal combustion engines, for example diesel fuelled engines, gasoline fuelled engines, natural gas fuelled engines or a mixed gasoline/alcohol fuelled engines.
- composition of the invention provides a method for lubricating an internal combustion engine, comprising supplying thereto a lubricant comprising the composition as described herein.
- the use of the composition of the invention is capable of imparting one or more of the group selected from improved engine cleanliness, decreased wear, decreased NO x emissions and decreased particulate emissions.
- a sample of a salixarene substrate is prepared using a flange flask approximately 2 litres in volume, a flange and clip, overhead stirrer with paddle and polytetrafluoroethylene (PTFE) stirrer gland, Dean Stark trap and double surface condenser, an electric mantle/thermocouple/EurothermTM temperature controller system, the glassware from just above the mantle to just below the condenser being covered with glass wool.
- PTFE polytetrafluoroethylene
- the flask is filled with 475g polyisobutenyl phenol derived from high vinylidene polyisobutylene with a number average molecular weight of 550 (GLISSOPAL®550 commercially available from BASF) and 330g of mineral oil (SN 150) and heated to 30°C via a pressure equalizing dropping funnel 3.4g of 50% aqueous KOH is added.
- the contents of the flask are heated to 75°C and the temperature is kept constant for 30 minutes while 81.6g of 37% aqueous formaldehyde (formalin) is added.
- the reaction is charged with 51.6g of salicylic acid and heated to 140°C while controlling reflux. Water is removed using Dean Stark trap.
- the product is vacuum stripped at 140°C/13kPa (equivalent to 100mm Hg) for 30 minutes.
- a more detailed description of the reaction process is given in Examples 1 and 5 of International Publication WO03/018728 , pages 22 and 23.
- a vessel is charged with 1200g of the salixarene from Preparative Example 1, 25g of ethylene glycol, 130g of calcium hydroxide and 410g of 2-ethylhexanol.
- the vessel and contents are heated to 95°C and stirred under vacuum (64 kPa, which is equivalent to 480mm Hg).
- the vessel and contents are then subject to vacuum at 6.7 kPa (equivalent to 50mm Hg) for 15 minutes and heated to 130°C.
- the vessel is then charged with an additional 120g of ethylene glycol added dropwise over 10 minutes before carbon dioxide is added via a dip tube under a slight negative pressure at 1.0 g/minute or less until 48g are added.
- the dip tube Upon completion of carbon dioxide addition, the dip tube is removed and the temperature is increased to 200°C under a vacuum of 6.7 kPa (equivalent to 50mm Hg) to remove solvents. The residue is vacuum filtered through a 12mm diatomaceous earth pad in a sintered funnel yielding a viscous brown liquid.
- a vessel is charged with 560.5g of the salixarene from Preparative Example 1 with 433g of xylene.
- the vessel and contents are heated to 35°C under a nitrogen atmosphere where 53g of magnesium oxide is added.
- the vessel is then charged with 20.2g of glacial acetic acid and then a mixture of methanol (42g) and water (30g) is added.
- the vessel and contents are heated to 61°C and carbonated.
- the vessel and contents are held at 61°C for a further 2 hours and a further mixture of methanol (36g) and water (26.2g) is added.
- the vessel heated to 150°C and held for 1 hour.
- the product is vacuum stripped.
- a vessel is charged with 313g of the salixarene from Preparative Example 1, and heated under a nitrogen atmosphere to 80°C where 12.1g of potassium hydroxide in 7g of water is added dropwise followed by the addition of 85g of a diluent oil.
- the vessel and contents are heated to 110°C for 10 minutes, then heated to 120°C for 90 minutes and heated to 140°C for 3 hours.
- a dark brown product is formed.
- a composition is prepared by mixing (a) 42.5g of Nexbase TM3050 oil, (b) 34.4g of NexbaseTM 3043 oil, (c) on a an oil free basis 0.4g of an amine dispersant viscosity modifier, (d) on a an oil free basis 2.8g of polyisobutylene succinimide dispersants, (e) 5g of antioxidants including a diphenylamine and a hindered phenol, (f) 0.7g of an olefin copolymer viscosity modifier and (g) a glycerol monooleate friction modifier.
- the composition contains 0 wt % of calcium, 0 wt % of phosphorus, 190 ppm of sulphur and 0 wt % of zinc.
- the composition has a KV100 of 13.11 mm 2 /s (cSt) and a sulphated ash content of 0 wt %.
- Reference Example 2 is a successful European top tier passenger car oil formulation containing zinc dithiophosphate.
- the elemental analysis of the oil formulation indicates a calcium content of 3307ppm, a phosphorus content of 889ppm, a sulphur content of 2645ppm and a zinc content of 889ppm.
- the oil formulation has a KV100 of 11.3 mm 2 /s (cSt) and sulphated ash content of 1.26 wt %.
- Example 1 has the same composition as Reference Example 1 except 2.5g (on an oil free basis) of the product of Preparative Example 2 is also added.
- the phosphorus content is 0 wt % and the sulphur content is 190 ppm (all derived from diluent oil).
- Example 2 has the same composition as Reference Example 1 except 2.5g (on an oil free basis) of the product of Preparative Example 3 is also added.
- the phosphorus content is 0 wt % and the sulphur content is 190 ppm (all derived from diluent oil).
- Example 3 has the same composition as Reference Example 1 except 2.5g (on an oil free basis) of the product of Preparative Example 4 is also added.
- the phosphorus content is 0 wt % and the sulphur content is 190 ppm (all derived from diluent oil).
- a number of lubricating oil compositions are formed using Reference Example 1 and adding examples 1-3 at 2.5g on a oil free basis to the oil thus forming "Lubricating Oil Composition with Example 1",
- Example 2 is titled “Lubricating Oil Composition with Example 2” and "Lubricating Oil Composition with Example 3.”
- Reference example 1 and the corresponding Lubricating Oil Composition with examples 1-3 have a KV100 of 13.11 mm 2 /s (or cSt).
- Test 1 HFRR of Examples 1-3 and Reference Examples 1-2
- Lubricating Oil Composition with Example 1-3 are and Reference Example 1-2 are evaluated for wear performance in a programmed temperature high frequency reciprocating rig (HFRR) available from PCS Instruments.
- HFRR conditions for the evaluations are 200g load, 75 minute duration, 1000 micrometer stroke, 20 hertz frequency, and temperature profile of 15 minutes at 40°C followed by an increase in temperature to 160°C at a rate of 2°C per minute. Wear scar in micrometers and film formation as percent film thickness are measured with lower wear scar values and higher film formation values indicating improved wear performance.
- the percent film thickness is based on the measurement of electrical potential between an upper and a lower metal test plate in the HFRR.
- the film thickness is 100%, there is a high electrical potential for the full length of the 1000 micrometre stroke, suggesting no metal to metal contact.
- a film thickness of 0% there is no electrical potential suggesting continual metal to metal contact between the plates.
- the upper and lower metal test plate have a degree of metal to metal contact as well as other areas with no metal to metal contact.
- the Cameron Plint TE-77TM is a reciprocating wear tester. In this test a steel ball upper specimen is reciprocated against a steel flat lower specimen. The Cameron Plint is charged with 10ml of sample and heated to 50°C and held for 1 minute. The sample is then subject to a load of 100N over two minutes while at the same time the reciprocation is started at 10 Hz over 15mm stroke length. The sample is then heated to 250°C at 3°C per minute. At the end of the test the average diameter of the wear scar (in micrometers) on the ball (measured in the X and Y directions) is measured using a calibrated microscope. The results obtained are: Table 2: Cameron Plint Wear Scar Data Example Wear Scar Lubricating Oil Composition Example 1 396 Reference Example 1 753 Reference Example 2 517
- Test 3 4 Ball Wear Test Using ASTM D4172
- Example 4" contains 2g on a oil free basis of the product of Preparative Example 2 and delivering about 1900 ppm of calcium and a TBN of about 146; and “Example 5" contains 1.2g on a oil free basis of the product of preparative Example 2 and delivering about 1300 ppm of calcium and a TBN of about 146.
- Reference Example 3 has the same oil composition as Reference Example 1, except a calcium alkylsalicylate (commercially available from AC60CTM range of products from Infineum) is added in sufficient quantity to deliver about 1300 ppm of calcium and a TBN of about 146.
- Reference Example 4 has the same oil composition as Reference Example 1, except a magnesium saligenin (commercially available from The Lubrizol Corporation) is added in sufficient quantity to deliver about 1300 ppm of magnesium and a TBN of about 146.
- hydrocarbyl substituent or “hydrocarbyl group,” as used herein are used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group primarily composed of carbon and hydrogen atoms and is attached to the remainder of the molecule through a carbon atom and does not exclude the presence of other atoms or groups in a proportion insufficient to detract from the molecule having a predominantly hydrocarbon character. In general, no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group. A more detailed definition of the terms “hydrocarbyl substituent” or “hydrocarbyl group,” is described in US -A- 6, 583,092 .
- each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade. However, the amount of each chemical component is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, unless otherwise indicated.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Description
- The present invention relates to a lubricating oil composition containing a metal salixarate and other performance additives. The lubricating oil composition has antiwear and detergency performance in the absence of a metal hydrocarbyl dithiophosphate.
- It is well known for lubricating oils to contain a number of additives used to protect the engine from wear, the accumulation of sludge and filter plugging. Common additives for engine lubricating oils are zinc dialkyldithiophosphate (ZDDP) as an antiwear additive, and overbased calcium sulphonate detergents. It is believed that ZDDP antiwear additives protect the engine by forming a protective film on metal surfaces. Typical treatment quantities of ZDDP range from 1 to 2 weight percent based on the total weight of the lubricant. Detergents such as overbased calcium sulphonate help keep the engine parts clean of soot and other deposits, and offer an alkalinity reserve. Typical treatment quantities of detergents range from 0.05 to 10 weight percent based on the total weight of the lubricant.
- In recent years phosphates and sulphonates derived from engine lubricants have been shown to contribute in part to particulate emissions. Further, sulphur and phosphorus tend to poison the NOx catalysts used in catalytic converters, resulting in a reduction in performance of said catalysts. Any reduction in the performance of catalytic converters tends to result in increased amounts of greenhouse gases such as nitric oxide and/or sulphur oxides. However, reducing the amount of ZDDP will increase the amount of wear in an engine. Also reducing the amount of detergent will decrease engine cleanliness and result in increased soot deposits.
- International Publication
WO03/18728 (Cressey et al. -
US Patent Number 6,200,936 (Moreton ) discloses compounds containing phenolic units and salicylic units in a lubricating composition. The compounds can be salted with calcium. The examples of lubricating compositions contain phenolic units with a dodecyl alkyl group. The compounds of the invention can be used as a detergent in gasoline or diesel fuel. They also stabilise gasoline or diesel compositions against thermal decomposition. - International Publication
WO99/25793 (Taylor - International Publication
WO01/56968 (Taylor et al. - European Patent Application
1 262 538 A2 (Locke et al. ) discloses a metal detergent derived from an aromatic carboxylic acid, a metal detergent derived from phenol capable of imparting oxidation resistance in a lubricating oil composition. In a preferred embodiment the aromatic carboxylic acid is a salicylic acid substituted with an alkyl group. -
US-A-2003/158048 discloses lubricants for internal combustion engines having low SASH ash, low P content derived from ZnDTP. -
EP-A-1167497 refers to fow P, low ash lubricants compositions for diesel engines using conventional detergents alone with other additives. - It has now been found that the composition of the present invention provides detergency and antiwear performance to an oil of lubricating viscosity often used in an engine oil and said composition is substantially free of a metal hydrocarbyl dithiophosphate.
- The present invention provides a composition comprising:
- (a) a metal salixarate;
- (b) 0.01 to 6 weight percent of the composition on an oil-free basis, of a dispersant viscosity modifier selected from the group consisting of (a) an olefin copolymer grafted with an unsaturated dicarboxylic acid anhydride or derivatives thereof and an amine; (b) a polymethacrylate functionalised with an amine; (c) an esterified copolymer comprising (i) styrene, (ii) an unsaturated dicarboxylic acid anhydride or derivatives thereof, optionally functionalised with an amine; and mixtures thereof;
- (c) an oil of lubricating viscosity,
- The invention further provides method for lubricating an internal combustion engine comprising supplying thereto a lubricant comprising the composition mentioned above.
Preferred embodiments of the invention are apparent from the dependent claims. - The use of the composition of the invention imparts one or more of improved engine cleanliness, decreased wear, decreased NOx emissions and decreased particulate emissions.
- The present invention provides a composition as described above. Often the composition has a total sulphur content below 0.5 wt %, preferably below 0.3 wt %, more preferably 0.1 wt % and most preferably near 0 wt %. Often the major source of sulphur in the composition of the invention is derived from diluent oil. Usually the diluent oil is used in the manufacturing processes used for preparing many of the component additives mentioned below. Excluding the diluent oil, the composition of the invention often have a sulphur content of 700 ppm or less, preferably 600 ppm or less, more preferably 300 ppm or less, even more preferably 100 ppm or less and most preferably 50 ppm or less such as less than 30 ppm, 25 ppm or less, 20 ppm or less and 15 ppm or less. When sulphur from the diluent oil is included, the sulphur content of the composition is often increased by up to 800 ppm, preferably up to 600 ppm and most preferably up to 400 ppm, for instance 200 ppm or 300 ppm.
- Often the composition has a total phosphorus content below 0.1 wt %, preferably equal to or less than 0.085 wt %, more preferably equal to or less than 0.07 wt %, even more preferably equal to or less than 0.055 wt % and most preferably equal to or less than 0.05 wt % of the composition, such as 200 ppm or less, preferably 100 ppm or less, more preferably 50 ppm or less and most preferably 10 ppm or less. In one embodiment the phosphorus is present from 1 ppm or 10 ppm to 50 ppm or 200 ppm.
- The composition has a total ash content as determined by ASTM D-874 of below 1.5 wt %, preferably equal to or less than 1.1 wt %, more preferably equal to or less than 1.0 wt %, even more preferably equal to or less than 0.8 wt % and most preferably equal to or less than 0.5 wt % of the composition. In one embodiment the total ash content is present from 0.1 wt % or 0.2 wt % to 0.6 wt % or 0.7 wt%.
- The substrate of the metal salixarate of the invention is often represented by one or a mixture of substantially linear compounds comprising at least one unit of the formulae (I) or (II):
- The U group in formulae (i) and (iii) may be located in one or more positions ortho, meta, or para to the -COOR3 group. Preferably the U group is located ortho to the -COOR3 group. When the U group is a -OH group, formulae (i) and (iii) are derived from 2-hydroxybenzoic acid (often called salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid or mixtures thereof. When U is a -NH2 group, formulae (i) and (iii) are derived from 2-aminobenzoic acid (often called anthranilic acid), 3-aminobenzoic acid, 4-aminobenzoic acid or mixtures thereof.
- The divalent bridging group, which may be the same or different in each occurrence, includes -CH2- (methylene bridge) and -CH2OCH2- (ether bridge), either of which may be derived from an aldehyde such as formaldehyde or a formaldehyde equivalent (e.g., paraform, formalin), ethanal or propanal.
- The metal of the metal salixarate is often mono-valent, di-valent or mixtures thereof. Preferably the metal is selected from an alkali metal or alkaline earth metal such as magnesium, calcium, potassium or sodium, although magnesium, calcium, potassium or mixtures thereof are most preferred.
- It is believed that a significant fraction of salixarate molecules (prior to neutralisation) may be represented on average by the following formula:
- Salixarate derivatives and methods of their preparation are described in greater detail in
U.S. -A-6,200,936 andPCT Publications WO-A-01/56968 -
WO-A-03/18728 - The metal salixarate is often present on an oil free basis at 0.01 to 20, preferably 0.1 to 10, more preferably 0.2 to 8 and most preferably 0.5 to 5 weight percent of the composition.
- Further additives are selected from the group consisting of (1) an antioxidant; (2) a friction modifier; (3) a dispersant; (4) a viscosity modifier; and (5) an antiwear agent other than a metal hydrocarbyl dithiophosphate. Often 2 or more and most preferably 3 or more of additives (1)-(5) are present in the invention.
- Often the amount of each of the additives (1)-(5) are present on an oil free basis at 0 to 25, preferably 0.1 to 20, more preferably 0.3 to 15 and most preferably 1 to 10 weight percent of the composition, with the proviso that at least one additive is present at 0.1 or more weight percent of the composition.
- When present in the invention the antioxidant often includes a diphenylamine antioxidant, a hindered phenol antioxidant, or mixtures thereof.
- Other antioxidant additives such as a molybdenum dithiocarboamate or a sulphurised olefin may also be added to the composition of the invention, although preferably the composition is substantially free of a molybdenum dithiocarboamate or a sulphurised olefin. As used herein the term "substantially free of a molybdenum dithiocarboamate or a sulphurised olefin" means the composition will contain a molybdenum dithiocarboamate or a sulphurised olefin present at less than 100 ppm, preferably less than 20ppm and most preferably 1 ppm or less.
- When present, the diphenylamine suitable for the invention is often represented by the formula:
- Examples of suitable diphenylamine antioxidants include octyl diphenylamine, nonyl diphenylamine, bis-octyl diphenylamine, bis-nonyl diphenylamine or mixtures thereof.
- When present, the diphenylamine is often present on an oil free basis at 0.01 to 20, preferably 0.05 to 10, more preferably 0.1 to 5 and most preferably 0.2 to 3 weight percent of the composition.
- When present, the hindered phenol suitable for the invention is often represented by the formula:
- R8 and R9 may be either straight or branched chain; branched is preferred. Suitable examples of R8 and R9 include secondary butyl and tertiary butyl.
-
- When R10 is a hydrocarbyl group, R10 is preferably selected from the group consisting of butyl, sec-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, sechexyl, n-octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and mixtures thereof.
- In one embodiment, the hindered phenol of formula (VII) suitable for the invention contains a bridging group. Examples of suitable bridging groups include an alkylene bridge or an ether bridge, often containing 1 to 8, preferably 1 to 6, more preferably 1 to 4 and most preferably 1 to 2 carbon atoms. Examples of a suitable bridge group include -CH2-, -CH2CH2-, -CH2OCH2- and -CH2CH2OCH2CH2-.
- When present, the hindered phenol with a bridging group is often represented by the formula:
- The hindered phenol of the invention also includes compounds represented by the formula:
- When present, the hindered phenol is often present on an oil free basis at 0.01 to 25, preferably 0.1 to 20, more preferably 0.5 to 15 and most preferably 1 to 10 weight percent of the composition.
- When present, the invention further includes a dispersant often derived from N-substituted long chain alkenyl succinimide or mixtures thereof. The dispersants can be used alone or in combination with other dispersants.
- The N-substituted long chain alkenyl succinimides have a variety of chemical structures and include a mono-succinimide and/or a di-succinimide. Often the long chain alkenyl group will have number average molecular weight of 350 to 10,000, preferably 400 to 7000, more preferably 500 to 5000 and most preferably 500 to 4000. In one embodiment the long chain alkenyl group is a polyisobutylene group, which has a number average molecular weight from 800 to 1600 and in another embodiment from 1600 to 3000. The succinimide is often prepared by the condensation of a hydrocarbyl-substituted acylating agent (e.g., hydrocarbyl-substituted succinic anhydride) with a polyamine or an amino alcohol, often a polyalkylene polyamine or poly(ethyleneamine) such as triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine or, in one embodiment, polyamine still bottoms.
- N-substituted long chain alkenyl succinimides dispersant additives and their preparation are disclosed, for instance, in
US -A- 3,361,673 ,3,401,118 and4,234,435 . - Another class of suitable dispersants include Mannich bases, which are the reaction products of alkyl phenols in which the alkyl group typically contains at least 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines) and are described in more detail in
U.S. -A- 3,634,515 . - Another class of ashless dispersant is high molecular weight esters. These materials are similar to the above-described succinimides except that they may be seen as having been prepared by reaction of a hydrocarbyl acylating agent and a polyhydric aliphatic alcohol such as glycerol, pentaerythritol, or sorbitol. Such materials are described in more detail in
U.S. -A- 3,381,022 . - Other dispersants include polymeric dispersant additives, which are generally hydrocarbon-based polymers which contain polar functionality to impart dispersancy characteristics to the polymer.
- Dispersants may also be post-treated by reaction with any of a variety of agents. Among these are urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, and phosphorus compounds. References detailing such treatment are listed in
U.S. -A- 4,654,403 . - When present, the dispersant is often present on an oil free basis at 0.01 to 20, preferably 0.1 to 15, more preferably 0.2 to 10 and most preferably 0.5 to 6 weight percent of the composition.
- When present in the invention, the friction modifier can be a monoester of a polyol and an aliphatic carboxylic acid, often an acid containing 12 to 24 carbon atoms. Often the monoester of a polyol and an aliphatic carboxylic acid is in the form of a mixture with a sunflower oil or the like, which may be present in the friction modifier mixture from 5 to 95, preferably 10 to 90, more preferably 20 to 85 and most preferably 20 to 80 weight percent of said mixture.
- Polyols include diols, triols, and alcohols with higher numbers of alcoholic OH groups. Polyhydric alcohols include ethylene glycols, including di-, tri- and tetraethylene glycols; propylene glycols, including di-, tri- and tetrapropylene glycols; glycerol; butane diol; hexane diol; sorbitol; arabitol; mannitol; sucrose; fructose; glucose; cyclohexane diol; erythritol; and pentaerythritols, including di- and tripentaerythritol; preferably, diethylene glycol, triethylene glycol, glycerol, sorbitol, pentaerythritol and dipentaerythritol.
- The aliphatic carboxylic acids which form the esters are those acids containing 12 to 24 carbon atoms. Acids containing straight chain hydrocarbyl groups containing 12 to 24 carbon atoms are preferred, for instance, 14 to 20 or 16 to 18 carbon atoms. Such acids can be used in combination with acids with more or fewer carbon atoms as well.
- Generally the acid is a monocarboxylic acid. Examples of carboxylic acids include dodecanoic acid, stearic acid, lauric acid, behenic acid, and oleic acid.
- The esters used in the present invention are in particular the monoesters of such polyols and such carboxylic acids. A preferred ester is glycerol monooleate. It is to be understood that glycerol monooleate, as is the case with other such materials, in its commercially available grade, is a mixture which includes such materials as glycerol, oleic acid, other long chain acids, glycerol dioleate, and glycerol trioleate. The commercial material is believed to include about 60 ± 5 percent by weight of the chemical species "glycerol monooleate," along with 35 ± 5 percent glycerol dioleate, and less than about 5 percent trioleate and oleic acid. The amounts of the monoesters, described below, are calculated based on the actual, corrected, amount of polyol monoester present in any such mixture.
- Other friction modifiers that are suitable for the invention include fatty amines, fatty phosphites, fatty acid amides, fatty epoxides, alkoxylated fatty amines, metal salts of fatty acids, sulfurised olefins, fatty imidazolines, condensation products of carboxylic acids and polyalkylene-polyamines, amine salts of alkylphosphoric acids. Preferably the friction modifier is free of sulphur and/or phosphorus.
- When present, the friction modifier is often present on an oil free basis at 0.01 to 20, preferably 0.05 to 10, more preferably 0.1 to 5 and most preferably 0.2 to 3 such as 0.5 to 2 weight percent of the composition.
- When present in the invention the viscosity modifier is often an olefin copolymer. The olefin copolymer backbone often contains two to four, preferably two to three and most preferably two different olefin monomers. The olefin monomers often contain 2 to 20, preferably 2 to 10, more preferably 2 to 6 and most preferably 2 to 4 carbon atoms.
- When present, the viscosity modifiers are often present on an oil free basis at of 0.01 to 15, preferably 0.05 to 10, more preferably 0.1 to 5 and most preferably 0.2 to 3 weight percent of the composition.
- The olefin copolymer preferably contains an ethylene monomer and at least one other comonomer derived from an alpha-olefin having the formula H2C=CHR10, wherein R10 is a hydrocarbyl group, preferably an alkyl radical containing 1 to 18, preferably 1 to 10, more preferably 1 to 6 and most preferably 1 to 3 carbon atoms. The hydrocarbyl group includes an alkyl radical that has a straight chain, a branched chain or mixtures thereof.
- Examples of suitable comonomers include propylene, 1-butene, 1-hexene, 1-octene, 4-methylpentene-1, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene or mixtures thereof. Preferably the comonomer is 1-butene, propylene or mixtures thereof. Example of olefin copolymers include ethylenepropylene copolymers or ethylene-butene-1 copolymers.
- Other viscosity modifiers suitable for the invention include polymeric materials including hydrogenated styrene-butadiene rubbers, hydrogenated styrene-isoprene polymers, hydrogenated radical isoprene polymers, polymethacrylate acid esters, polyacrylate acid esters, polyalkyl styrenes, alkenyl aryl conjugated diene copolymers, polyalkylmethacrylates, esters of maleic anhydride-styrene copolymers or mixtures thereof.
- Optionally the olefin copolymer of the invention is further grafted with an unsaturated dicarboxylic acid anhydride or derivatives thereof and an amine to form a dispersant viscosity modifier (often referred to as DVM), thus named because they also exhibit dispersant properties. DVM additives and their preparation are disclosed, for instance, in
US - A - 6,107,258 and6,107,257 . - Examples of olefin copolymer DVM's include those commercially available from DSM as PA1250™, PA1260™ and PA1274™ as well as Hitec 5777™ (commercially available from Ethyl Corporation).
- The dispersant viscosity modifier is selected from the group consisting of (a) an olefin copolymer grafted with an unsaturated dicarboxylic acid anhydride or derivatives thereof and an amine; (b) a polymethacrylate functionalised with an amine; (c) an esterified copolymer comprising (i) styrene, (ii) an unsaturated dicarboxylic acid anhydride or derivatives thereof, optionally functionalised with an amine; and mixtures thereof. Often DVM's derived from a polymethacrylate and/or a styrene copolymer are prepared by reacting with an amine as described in
US - A - 6,107,258 and6,107,257 . The DVM can be used alone or in combination with other DVM's. - According to the invention, the dispersant viscosity modifier is present on an oil free basis at 0.01 to 6, preferably 0.05 to 6, more preferably 0.08 to 4 and most preferably 0.1 to 2 weight percent of the composition.
- The composition of the invention may additionally contain an antiwear agent other than a metal hydrocarbyl dithiophosphate. Suitable antiwear agents include phosphoric acid esters or salt thereof; phosphites; and phosphorus-containing carboxylic esters, ethers, and amides or mixtures thereof. Preferably the composition of the invention is substantially free of phosphorus- and/or sulphur-containing antiwear agents. In one embodiment of the invention the composition is free of antiwear agents.
- As used herein the term "substantially free of antiwear agents containing sulphur and/or phosphorus" means the composition will contain antiwear agents present at less than 50 ppm, preferably less than 10 ppm and most preferably 1 ppm or less. In one embodiment of the invention no antiwear agents containing sulphur and/or phosphorus are present. In one embodiment of the invention 1 ppm to 15 ppm of antiwear agents containing sulphur and/or phosphorus are present.
- The lubricating oil composition of the present invention may be added to an oil of lubricating viscosity. The oil includes natural and synthetic oils, oil derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined and re-refined oils, or mixtures thereof.
- Unrefined oils are those obtained directly from a natural or synthetic source generally without (or with little) further purification treatment.
- Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Purification techniques are known in the art and include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and the like.
- Re-refined oils are also known as reclaimed or reprocessed oils, and are obtained by processes similar to those used to obtain refined oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
- Natural oils useful in making the inventive lubricants include animal oils, vegetable oils (e.g., castor oil, lard oil), mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
- Synthetic lubricating oils are useful and include hydrocarbon oils such as polymerised and interpolymerised olefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers); poly(1-hexenes), poly(1-octenes), poly(1-decenes), and mixtures thereof; alkyl-benzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); alkylated diphenyl ethers and alkylated diphenyl sulphides and the derivatives, analogs and homologs thereof or mixtures thereof. Preferably the synthetic lubricating oils are free of alkylated diphenyl sulphides.
- Other synthetic lubricating oils include but are not limited to polyol esters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), and polymeric tetrahydrofurans. Synthetic oils may be produced by Fischer-Tropsch reactions and typically may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes. Preferably the synthetic lubricating oils are free of phosphorus-containing esters.
- Oils of lubricating viscosity may also be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are as follows: Group I (sulphur content >0.03 wt %, and/or <90 wt % saturates, viscosity index 80-120); Group II (sulphur content ≤0.03 wt %, and ≥90 wt % saturates, viscosity index 80-120); Group III (sulphur content ≤0.03 wt %, and ≥90 wt % saturates, viscosity index ≥120); Group IV (all polyalphaolefins (PAO's)); and Group V (all others not included in Groups I, II, III, or IV). The oil of lubricating viscosity is selected from the group consisting of an API Group I, II, III, IV, V oil and mixtures thereof; preferably an API Group II, III, IV or V oil and mixtures thereof; and most preferably an API Group III, IV or V oil and mixtures thereof. If the oil of lubricating viscosity is an API Group II, III, IV or V oil there may be up to a maximum of 20 wt %, preferably up to a maximum of 10 wt %, more preferably up to a maximum of 5 wt % and most preferably up to a maximum of 1.5 wt % of the lubricating oil an API Group I oil.
- Examples of suitable API Group III oils include Nexbase™ 3050, Nexbase™ 3043, Yubase™ 4, Yubase™ 6, and Shell™ XHVI 5.2.
- The oil of lubricating viscosity is often present at up to 99.98, preferably up to 99.8, more preferably up to 99.65 and most preferably up to 99.3 weight percent of the composition.
- If the present invention is in the form of a concentrate (which can be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of each of the above-mentioned dispersant, as well as other components, to diluent oil is often 80:20 to 10:90 by weight.
- The invention is substantially free of to free of a metal hydrocarbyl dithiophosphate often represented by the formula:
- The term "substantially free of" means that the composition contains 400 ppm or less of phosphorus, preferably 300 ppm or less of phosphorus, more preferably 200 ppm or less of phosphorus, even more preferably 100 ppm or less of phosphorus and most preferably 100 ppm or less of phosphorus such as 50 ppm, 20 ppm or 1 ppm or less, derived from a metal hydrocarbyl dithiophosphate. In one embodiment of the invention the composition contains 0.5 ppm or 10ppm to 50 ppm of phosphorus derived from a metal hydrocarbyl dithiophosphate. In one embodiment of the invention the composition is free of a metal hydrocarbyl dithiophosphate.
- M' is a metal, and n is an integer equal to the available valence of M'. M' is mono- or di- or tri- valent, preferably divalent, more preferably a divalent transition metal. In one embodiment M' is zinc. In one embodiment M' is calcium. In one embodiment M' is barium. Examples of a metal hydrocarbyl dithiophosphate include zinc dihydrocarbyl dithiophosphates (often referred to as ZDDP, ZDP or ZDTP).
- The composition of the invention optionally further includes other performance additives. The other performance additives selected from the group consisting of detergents other than those of component (a) of the invention, corrosion inhibitors, antiscuffing agents, foam inhibitors, demulsifiers, pour point depressants seal swelling agents and mixtures thereof.
- The total combined amount of the other performance additives present on an oil free basis is often from 0 to 20, preferably 0.01 to 15, more preferably 0.05 to 10 and most preferably 0.1 to 5 weight percent of the composition. Although one or more of the other performance additives may be present, it is common for the other performance additives to be present in different amounts relative to each other.
- Detergents other than those of component (a) of the invention are known and include neutral or overbased, Newtonian or non-Newtonian, basic salts of alkali, alkaline earth and transition metals with one or more of a phenate, a sulphonate, a carboxylic acid, a phosphorus acid, a mono- and/or a dithiophosphoric acid, a saligenins, an alkylsalicylate or mixtures thereof. Commonly used metals include sodium, potassium, calcium, magnesium lithium or mixtures thereof. Most commonly used metals include sodium, magnesium and calcium. Preferably the composition of the invention is free of detergents containing sulphur and/or phosphorus.
- Other performance additives such as corrosion inhibitors including octylamine octanoate, condensation products of dodecenyl succinic acid or anhydride and a fatty acid such as oleic acid with a polyamine; metal deactivators including derivatives of benzotriazoles, 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles or 2-alkyldithiobenzothiazoles; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides; and seal swell agents including Exxon Necton-37™ (FN 1380) and Exxon Mineral Seal Oil (FN 3200); may also be used in the composition of the invention.
- In a process for the preparation of a composition as described above, the components (a)-(c) are often mixed sequentially, separately for the composition of the invention. The mixing conditions are often 15°C to 130°C, preferably 20°C to 120°C and most preferably 25°C to 110°C; and for a period of time in the range 30 seconds to 48 hours, preferably 2 minutes to 24 hours, more preferably 5 minutes to 16 hours and most preferably 10 minutes to 5 hours; and at pressures in the range 86 kPa to 266 kPa (650 mm Hg to 2000 mm Hg), preferably 91 kPa to 200 kPa (690 mm Hg to 1500 mm Hg), and most preferably 95 kPa to 133 kPa (715 mm Hg to 1000 mm Hg).
- The process optionally includes mixing other optional performance additives as described above. The optional performance additives are often added sequentially, separately or as a concentrate.
- The composition of the present invention is useful in an internal combustion engines, for example diesel fuelled engines, gasoline fuelled engines, natural gas fuelled engines or a mixed gasoline/alcohol fuelled engines.
- In one embodiment of the invention provides a method for lubricating an internal combustion engine, comprising supplying thereto a lubricant comprising the composition as described herein. The use of the composition of the invention is capable of imparting one or more of the group selected from improved engine cleanliness, decreased wear, decreased NOx emissions and decreased particulate emissions.
- The following examples provide an illustration of the invention.
- A sample of a salixarene substrate is prepared using a flange flask approximately 2 litres in volume, a flange and clip, overhead stirrer with paddle and polytetrafluoroethylene (PTFE) stirrer gland, Dean Stark trap and double surface condenser, an electric mantle/thermocouple/Eurotherm™ temperature controller system, the glassware from just above the mantle to just below the condenser being covered with glass wool. The flask is filled with 475g polyisobutenyl phenol derived from high vinylidene polyisobutylene with a number average molecular weight of 550 (GLISSOPAL®550 commercially available from BASF) and 330g of mineral oil (SN 150) and heated to 30°C via a pressure equalizing dropping funnel 3.4g of 50% aqueous KOH is added. The contents of the flask are heated to 75°C and the temperature is kept constant for 30 minutes while 81.6g of 37% aqueous formaldehyde (formalin) is added. The reaction is charged with 51.6g of salicylic acid and heated to 140°C while controlling reflux. Water is removed using Dean Stark trap. The product is vacuum stripped at 140°C/13kPa (equivalent to 100mm Hg) for 30 minutes. A more detailed description of the reaction process is given in Examples 1 and 5 of International Publication
WO03/018728 - A vessel is charged with 1200g of the salixarene from Preparative Example 1, 25g of ethylene glycol, 130g of calcium hydroxide and 410g of 2-ethylhexanol. The vessel and contents are heated to 95°C and stirred under vacuum (64 kPa, which is equivalent to 480mm Hg). The vessel and contents are then subject to vacuum at 6.7 kPa (equivalent to 50mm Hg) for 15 minutes and heated to 130°C. The vessel is then charged with an additional 120g of ethylene glycol added dropwise over 10 minutes before carbon dioxide is added via a dip tube under a slight negative pressure at 1.0 g/minute or less until 48g are added. Upon completion of carbon dioxide addition, the dip tube is removed and the temperature is increased to 200°C under a vacuum of 6.7 kPa (equivalent to 50mm Hg) to remove solvents. The residue is vacuum filtered through a 12mm diatomaceous earth pad in a sintered funnel yielding a viscous brown liquid.
- A vessel is charged with 560.5g of the salixarene from Preparative Example 1 with 433g of xylene. The vessel and contents are heated to 35°C under a nitrogen atmosphere where 53g of magnesium oxide is added. The vessel is then charged with 20.2g of glacial acetic acid and then a mixture of methanol (42g) and water (30g) is added. The vessel and contents are heated to 61°C and carbonated. The vessel and contents are held at 61°C for a further 2 hours and a further mixture of methanol (36g) and water (26.2g) is added. The vessel heated to 150°C and held for 1 hour. The product is vacuum stripped.
- A vessel is charged with 313g of the salixarene from Preparative Example 1, and heated under a nitrogen atmosphere to 80°C where 12.1g of potassium hydroxide in 7g of water is added dropwise followed by the addition of 85g of a diluent oil. The vessel and contents are heated to 110°C for 10 minutes, then heated to 120°C for 90 minutes and heated to 140°C for 3 hours. A dark brown product is formed.
- A composition is prepared by mixing (a) 42.5g of Nexbase ™3050 oil, (b) 34.4g of Nexbase™ 3043 oil, (c) on a an oil free basis 0.4g of an amine dispersant viscosity modifier, (d) on a an oil free basis 2.8g of polyisobutylene succinimide dispersants, (e) 5g of antioxidants including a diphenylamine and a hindered phenol, (f) 0.7g of an olefin copolymer viscosity modifier and (g) a glycerol monooleate friction modifier. The composition contains 0 wt % of calcium, 0 wt % of phosphorus, 190 ppm of sulphur and 0 wt % of zinc. The composition has a KV100 of 13.11 mm2/s (cSt) and a sulphated ash content of 0 wt %.
- Reference Example 2 is a successful European top tier passenger car oil formulation containing zinc dithiophosphate. The elemental analysis of the oil formulation indicates a calcium content of 3307ppm, a phosphorus content of 889ppm, a sulphur content of 2645ppm and a zinc content of 889ppm. The oil formulation has a KV100 of 11.3 mm2/s (cSt) and sulphated ash content of 1.26 wt %.
- Example 1 has the same composition as Reference Example 1 except 2.5g (on an oil free basis) of the product of Preparative Example 2 is also added. The phosphorus content is 0 wt % and the sulphur content is 190 ppm (all derived from diluent oil).
- Example 2 has the same composition as Reference Example 1 except 2.5g (on an oil free basis) of the product of Preparative Example 3 is also added. The phosphorus content is 0 wt % and the sulphur content is 190 ppm (all derived from diluent oil).
- Example 3 has the same composition as Reference Example 1 except 2.5g (on an oil free basis) of the product of Preparative Example 4 is also added. The phosphorus content is 0 wt % and the sulphur content is 190 ppm (all derived from diluent oil).
- A number of lubricating oil compositions are formed using Reference Example 1 and adding examples 1-3 at 2.5g on a oil free basis to the oil thus forming "Lubricating Oil Composition with Example 1", Example 2 is titled "Lubricating Oil Composition with Example 2" and "Lubricating Oil Composition with Example 3." Reference example 1 and the corresponding Lubricating Oil Composition with examples 1-3 have a KV100 of 13.11 mm2/s (or cSt).
- Lubricating Oil Composition with Example 1-3 are and Reference Example 1-2 are evaluated for wear performance in a programmed temperature high frequency reciprocating rig (HFRR) available from PCS Instruments. HFRR conditions for the evaluations are 200g load, 75 minute duration, 1000 micrometer stroke, 20 hertz frequency, and temperature profile of 15 minutes at 40°C followed by an increase in temperature to 160°C at a rate of 2°C per minute. Wear scar in micrometers and film formation as percent film thickness are measured with lower wear scar values and higher film formation values indicating improved wear performance.
- The percent film thickness is based on the measurement of electrical potential between an upper and a lower metal test plate in the HFRR. When the film thickness is 100%, there is a high electrical potential for the full length of the 1000 micrometre stroke, suggesting no metal to metal contact. Conversely for a film thickness of 0% there is no electrical potential suggesting continual metal to metal contact between the plates. For intermediate film thicknesses, there is an electrical potential suggesting the upper and lower metal test plate have a degree of metal to metal contact as well as other areas with no metal to metal contact. The wear scar and film formation results obtained are presented in Table 1:
Table 1: HFRR Wear Scar and Film Formation Data Example Wear Scar Film Formation Lubricating Oil Composition Example 1 128 70 Lubricating Oil Composition Example 2 174 19 Lubricating Oil Composition Example 3 169 30 Reference Example 1 189 12 Reference Example 2 126 88 - The Cameron Plint TE-77™ is a reciprocating wear tester. In this test a steel ball upper specimen is reciprocated against a steel flat lower specimen. The Cameron Plint is charged with 10ml of sample and heated to 50°C and held for 1 minute. The sample is then subject to a load of 100N over two minutes while at the same time the reciprocation is started at 10 Hz over 15mm stroke length. The sample is then heated to 250°C at 3°C per minute. At the end of the test the average diameter of the wear scar (in micrometers) on the ball (measured in the X and Y directions) is measured using a calibrated microscope. The results obtained are:
Table 2: Cameron Plint Wear Scar Data Example Wear Scar Lubricating Oil Composition Example 1 396 Reference Example 1 753 Reference Example 2 517 - The "Lubricating Oil Composition Example 4" and "Lubricating Oil Composition Example 5" used in this test are the same as the "Lubricating Oil Composition Example 1" except "Example 4" contains 2g on a oil free basis of the product of Preparative Example 2 and delivering about 1900 ppm of calcium and a TBN of about 146; and "Example 5" contains 1.2g on a oil free basis of the product of preparative Example 2 and delivering about 1300 ppm of calcium and a TBN of about 146. Reference Example 3 has the same oil composition as Reference Example 1, except a calcium alkylsalicylate (commercially available from AC60C™ range of products from Infineum) is added in sufficient quantity to deliver about 1300 ppm of calcium and a TBN of about 146. Reference Example 4 has the same oil composition as Reference Example 1, except a magnesium saligenin (commercially available from The Lubrizol Corporation) is added in sufficient quantity to deliver about 1300 ppm of magnesium and a TBN of about 146.
- The ASTM D4172 test is run on a number of examples using the modified B conditions indicated on page Section 8 of ASTM D 4172 - 94 (reapproved 1999). The wear scar is measured in micrometers. The results obtained are:
Table 2: ASTM D4172 Wear Scar Data Example Wear Scar Lubricating Oil Composition Example 4 416 Lubricating Oil Composition Example 5 433 Reference Example 1 583 Reference Example 4 483 Reference Example 5 482 - Overall the analysis of the data from Test 1 and Test 2 shows the compositions of the invention produce good antiwear and film formation results compared with reference example 1. The analysis also indicates that the lubricating oil composition example 1 has antiwear and film formation results comparable with a successful European top tier passenger car oil formulation containing zinc dithiophosphate.
- In this specification the terms "hydrocarbyl substituent" or "hydrocarbyl group," as used herein are used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group primarily composed of carbon and hydrogen atoms and is attached to the remainder of the molecule through a carbon atom and does not exclude the presence of other atoms or groups in a proportion insufficient to detract from the molecule having a predominantly hydrocarbon character. In general, no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group. A more detailed definition of the terms "hydrocarbyl substituent" or "hydrocarbyl group," is described in
US -A- 6, 583,092 . - Unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade. However, the amount of each chemical component is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, unless otherwise indicated.
Claims (6)
- A composition comprising:(a) a metal salixarate;(b) 0.01 to 6 weight percent of the composition on an oil-free basis, of a dispersant viscosity modifier selected from the group consisting of (a) an olefin copolymer grafted with an unsaturated dicarboxylic acid anhydride or derivatives thereof and an amine; (b) a polymethacrylate functionalised with an amine; (c) an esterified copolymer comprising (i) styrene, (ii) an unsaturated dicarboxylic acid anhydride or derivatives thereof, optionally functionalised with an amine; and mixtures thereof;(c) an oil of lubricating viscosity,wherein the composition contains 400 ppm or less of phosphorus derived from a metal hydrocarbyl dithiophosphate; and wherein the total sulphated ash content is below 1.5 weight percent.
- The composition of claim 1, wherein the metal of the metal salixarate is an alkali metal or alkaline earth metal.
- The composition of claim 1, wherein the metal salixarate is present on an oil free basis at 0.01 to 20 weight percent of the composition.
- The composition of claims 1 to 3, wherein the total sulphur content is below 0.5 weight percent and the total posphorus content is below 0.07 weight percent.
- A method for lubricating an internal combustion engine, comprising supplying thereto a lubricant comprising the composition of any one of claims 1 to 4.
- The use of the composition of any one of claims 1 to 4 for imparting one or more of the group selected from improved engine cleanliness, decreased wear, decreased NOx emissions and decreased particulate emissions.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/751,809 US20050148477A1 (en) | 2004-01-05 | 2004-01-05 | Lubricating composition substantially free of ZDDP |
PCT/US2004/042758 WO2005068590A1 (en) | 2004-01-05 | 2004-12-17 | Lubricating composition substantially free of zddp |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1702049A1 EP1702049A1 (en) | 2006-09-20 |
EP1702049B1 true EP1702049B1 (en) | 2018-02-21 |
Family
ID=34711508
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04814892.8A Not-in-force EP1702049B1 (en) | 2004-01-05 | 2004-12-17 | Lubricating composition substantially free of zddp |
Country Status (5)
Country | Link |
---|---|
US (1) | US20050148477A1 (en) |
EP (1) | EP1702049B1 (en) |
JP (2) | JP2007517937A (en) |
CA (1) | CA2552606A1 (en) |
WO (1) | WO2005068590A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090156446A1 (en) * | 2004-10-25 | 2009-06-18 | Mcatee Rodney J | Corrosion Inhibition |
RU2451062C2 (en) * | 2006-02-21 | 2012-05-20 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Lubricating oil composition |
US7863229B2 (en) * | 2006-06-23 | 2011-01-04 | Exxonmobil Research And Engineering Company | Lubricating compositions |
US20090061234A1 (en) * | 2007-09-04 | 2009-03-05 | Baker Hughes Incorporated | Method for Inhibiting Corrosion of Metal in Distillation Units Caused by Organic Acids |
CN101945981A (en) * | 2008-12-05 | 2011-01-12 | 卢布里佐尔公司 | Be used for the marine diesel cylinder lubrication agent of improved fuel efficiency |
US8969273B2 (en) * | 2009-02-18 | 2015-03-03 | Chevron Oronite Company Llc | Lubricating oil compositions |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US441516A (en) * | 1890-11-25 | Blotter | ||
US4169799A (en) * | 1976-12-27 | 1979-10-02 | Texaco Inc. | Lubricating oil composition |
US4502970A (en) * | 1982-06-08 | 1985-03-05 | Exxon Research & Engineering Co. | Lubricating oil composition |
US5102566A (en) * | 1987-10-02 | 1992-04-07 | Exxon Chemical Patents Inc. | Low ash lubricant compositions for internal combustion engines (pt-727) |
CA2085614A1 (en) * | 1991-04-19 | 1992-10-20 | Mary F. Salomon | Lubricating compositions |
US5236610A (en) * | 1992-02-03 | 1993-08-17 | The United States Of America As Represented By The Secretary Of The Commerce | Stable high temperature liquid lubricant blends and antioxidant additives for use therewith |
US6310011B1 (en) * | 1994-10-17 | 2001-10-30 | The Lubrizol Corporation | Overbased metal salts useful as additives for fuels and lubricants |
US5863873A (en) * | 1997-04-08 | 1999-01-26 | Exxon Chemical Patents Inc | Fuel economy additive and lubricant composition containing same |
JP2001508084A (en) * | 1997-11-13 | 2001-06-19 | ルブリゾール アディビス ホールディングズ(ユーケイ)リミテッド | Salicyclic calixarenes and their use as lubricant additives |
EA200000515A1 (en) | 1997-11-13 | 2000-12-25 | Бп Ойл Интернэшнл Лимитед | FUEL COMPOSITION AND MIXTURE |
US6444624B1 (en) * | 2000-08-31 | 2002-09-03 | Juliet V. Walker | Lubricating oil composition |
EP1254100A1 (en) | 2000-02-07 | 2002-11-06 | Bp Oil International Limited | Calixarenes and their use as lubricant additives |
JP3722472B2 (en) * | 2000-06-02 | 2005-11-30 | シェブロンテキサコジャパン株式会社 | Lubricating oil composition |
US6569818B2 (en) | 2000-06-02 | 2003-05-27 | Chevron Oronite Company, Llc | Lubricating oil composition |
EP1262538B1 (en) | 2001-05-11 | 2014-11-26 | Infineum International Limited | Anti-wear and Anti-oxidant Additives for Lubricating Oil Compositions |
DE60204784T2 (en) | 2001-08-24 | 2006-06-01 | The Lubrizol Corp., Wickliffe | LINEAR COMPOUNDS CONTAINING PHENOL AND SALICYLIC ACID UNITS |
EP1442105B1 (en) * | 2001-11-05 | 2005-04-06 | The Lubrizol Corporation | Lubricating composition with improved fuel economy |
US6642191B2 (en) * | 2001-11-29 | 2003-11-04 | Chevron Oronite Company Llc | Lubricating oil additive system particularly useful for natural gas fueled engines |
US6730638B2 (en) * | 2002-01-31 | 2004-05-04 | Exxonmobil Research And Engineering Company | Low ash, low phosphorus and low sulfur engine oils for internal combustion engines |
US6673751B1 (en) * | 2002-11-06 | 2004-01-06 | The Lubrizol Corporation | Boron containing overbased calixarates and lubricants and methods thereof |
US7285516B2 (en) * | 2002-11-25 | 2007-10-23 | The Lubrizol Corporation | Additive formulation for lubricating oils |
WO2004096957A1 (en) * | 2003-04-24 | 2004-11-11 | The Lubrizol Corporation | Diesel lubricant low in sulfur and phosphorus |
WO2005026299A2 (en) * | 2003-09-05 | 2005-03-24 | The Lubrizol Corporation | Lubricated part having partial hard coating allowing reduced amounts of antiwear additive |
-
2004
- 2004-01-05 US US10/751,809 patent/US20050148477A1/en not_active Abandoned
- 2004-12-17 EP EP04814892.8A patent/EP1702049B1/en not_active Not-in-force
- 2004-12-17 JP JP2006547216A patent/JP2007517937A/en active Pending
- 2004-12-17 WO PCT/US2004/042758 patent/WO2005068590A1/en not_active Application Discontinuation
- 2004-12-17 CA CA002552606A patent/CA2552606A1/en not_active Abandoned
-
2011
- 2011-07-28 JP JP2011165988A patent/JP2011214013A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
CA2552606A1 (en) | 2005-07-28 |
JP2011214013A (en) | 2011-10-27 |
EP1702049A1 (en) | 2006-09-20 |
JP2007517937A (en) | 2007-07-05 |
US20050148477A1 (en) | 2005-07-07 |
WO2005068590A1 (en) | 2005-07-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8304374B2 (en) | Antiwear agent and lubricating composition thereof | |
EP2723837B1 (en) | Lubricating compositions containing salts of hydrocarbyl substituted acylating agents | |
EP2523935B1 (en) | Overbased alkylated arylalkyl sulfonates | |
EP2231840B1 (en) | Lubricating composition containing detergent | |
EP3228684B1 (en) | Lubricant compositions having improved frictional characteristics and methods of use thereof | |
EP3492567A1 (en) | Lubricating oil additives | |
JP2011214013A (en) | Lubricating composition substantially free of zddp | |
EP1692249B1 (en) | Lubricating composition containing metal salixarate as detergent | |
EP3858954B1 (en) | Lubricant formulations with silicon-containing compounds | |
EP2909292B1 (en) | Method with lubricating composition containing a detergent | |
US20080051307A1 (en) | Lubricating Compositions Containing An Ester Of A Polycarboxylic Acylating Agent | |
WO2006041810A1 (en) | Lubricating compositions containing sulphonates | |
EP3243892A1 (en) | Lubricant compositions having improved frictional characteristics and methods of use thereof | |
CN111479908A (en) | Alkyl phenol cleaning agent | |
US11788027B2 (en) | Engine oil formulation with improved sequence VIII performance | |
EP4430147A1 (en) | High efficiency engine oil compositions | |
EP3882330A1 (en) | Low viscosity lubricating oil composition | |
WO2006014950A2 (en) | Lubricating compositions containing an ester of a polycarboxylic acylating agent | |
EP3613831A1 (en) | Lubricants for use in boosted engines |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20060703 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR GB |
|
DAX | Request for extension of the european patent (deleted) | ||
RBV | Designated contracting states (corrected) |
Designated state(s): DE FR GB |
|
17Q | First examination report despatched |
Effective date: 20080225 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20170914 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602004052399 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602004052399 Country of ref document: DE |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20181122 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20191231 Year of fee payment: 16 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602004052399 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210701 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20221227 Year of fee payment: 19 Ref country code: FR Payment date: 20221227 Year of fee payment: 19 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230426 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20231217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231231 |