EP2371934B1 - Composition d'huile lubrifiante - Google Patents
Composition d'huile lubrifiante Download PDFInfo
- Publication number
- EP2371934B1 EP2371934B1 EP11159502.1A EP11159502A EP2371934B1 EP 2371934 B1 EP2371934 B1 EP 2371934B1 EP 11159502 A EP11159502 A EP 11159502A EP 2371934 B1 EP2371934 B1 EP 2371934B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricating oil
- oil composition
- salicylate
- dispersant
- detergent
- 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.)
- Active
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- 239000000203 mixture Substances 0.000 title claims description 113
- 239000010687 lubricating oil Substances 0.000 title claims description 91
- 239000002270 dispersing agent Substances 0.000 claims description 70
- 239000003599 detergent Substances 0.000 claims description 52
- 239000003921 oil Substances 0.000 claims description 47
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 31
- 229960001860 salicylate Drugs 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 20
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000000344 soap Substances 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 14
- 230000001050 lubricating effect Effects 0.000 claims description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical compound O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 0.000 claims description 11
- 229960002317 succinimide Drugs 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- 150000004982 aromatic amines Chemical class 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- SCJNCDSAIRBRIA-DOFZRALJSA-N arachidonyl-2'-chloroethylamide Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(=O)NCCCl SCJNCDSAIRBRIA-DOFZRALJSA-N 0.000 claims description 7
- 238000007906 compression Methods 0.000 claims description 7
- 230000006835 compression Effects 0.000 claims description 7
- MQHWFIOJQSCFNM-UHFFFAOYSA-L Magnesium salicylate Chemical compound [Mg+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O MQHWFIOJQSCFNM-UHFFFAOYSA-L 0.000 claims description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 5
- 229940072082 magnesium salicylate Drugs 0.000 claims description 5
- 238000010531 catalytic reduction reaction Methods 0.000 claims 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 claims description 2
- 238000005461 lubrication Methods 0.000 claims description 2
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical group C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims description 2
- -1 alkaline earth metal salt Chemical class 0.000 description 47
- 229910052751 metal Inorganic materials 0.000 description 40
- 239000002184 metal Substances 0.000 description 40
- 239000002585 base Substances 0.000 description 32
- 150000003839 salts Chemical class 0.000 description 23
- 239000000654 additive Substances 0.000 description 21
- 239000003446 ligand Substances 0.000 description 19
- 229910052717 sulfur Inorganic materials 0.000 description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 18
- 229910052750 molybdenum Inorganic materials 0.000 description 18
- 239000011733 molybdenum Substances 0.000 description 18
- 239000011593 sulfur Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 15
- 125000001183 hydrocarbyl group Chemical group 0.000 description 15
- 239000005078 molybdenum compound Substances 0.000 description 15
- 150000007524 organic acids Chemical class 0.000 description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 150000002752 molybdenum compounds Chemical class 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000002199 base oil Substances 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229920000768 polyamine Polymers 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 229920002367 Polyisobutene Polymers 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical class ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229910017464 nitrogen compound Inorganic materials 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 229920001281 polyalkylene Polymers 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229940014800 succinic anhydride Drugs 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005885 boration reaction Methods 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 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 3
- 235000011044 succinic acid Nutrition 0.000 description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 3
- CIRMGZKUSBCWRL-LHLOQNFPSA-N (e)-10-[2-(7-carboxyheptyl)-5,6-dihexylcyclohex-3-en-1-yl]dec-9-enoic acid Chemical compound CCCCCCC1C=CC(CCCCCCCC(O)=O)C(\C=C\CCCCCCCC(O)=O)C1CCCCCC CIRMGZKUSBCWRL-LHLOQNFPSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 238000001246 colloidal dispersion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical group O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 2
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- RLPSARLYTKXVSE-UHFFFAOYSA-N 1-(1,3-thiazol-5-yl)ethanamine Chemical compound CC(N)C1=CN=CS1 RLPSARLYTKXVSE-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 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
- AIUDKCYIGXXGIL-UHFFFAOYSA-N 2,4,6-trihydroxy-1,3,5,2,4,6-trioxatriborinane Chemical compound OB1OB(O)OB(O)O1 AIUDKCYIGXXGIL-UHFFFAOYSA-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
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- NUCFNMOPTGEHQA-UHFFFAOYSA-N 3-bromo-2h-pyrazolo[4,3-c]pyridine Chemical compound C1=NC=C2C(Br)=NNC2=C1 NUCFNMOPTGEHQA-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZJHYICNBERDKJB-UHFFFAOYSA-N 6-methylheptyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 ZJHYICNBERDKJB-UHFFFAOYSA-N 0.000 description 1
- 0 C*(*)(ON)OI Chemical compound C*(*)(ON)OI 0.000 description 1
- 125000006539 C12 alkyl 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 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004614 Process Aid Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- WLLCYXDFVBWGBU-UHFFFAOYSA-N bis(8-methylnonyl) nonanedioate Chemical compound CC(C)CCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC(C)C WLLCYXDFVBWGBU-UHFFFAOYSA-N 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- OSMZVRQRVPLKTN-UHFFFAOYSA-N calcium;1-nonyl-7-thiabicyclo[4.1.0]hepta-2,4-dien-6-ol Chemical compound [Ca].C1=CC=CC2(CCCCCCCCC)C1(O)S2 OSMZVRQRVPLKTN-UHFFFAOYSA-N 0.000 description 1
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- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- JLYVRXJEQTZZBE-UHFFFAOYSA-N ctk1c6083 Chemical compound NP(N)(N)=S JLYVRXJEQTZZBE-UHFFFAOYSA-N 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 229940100539 dibutyl adipate Drugs 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000001033 ether group Chemical group 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
- 230000007717 exclusion Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 150000002500 ions Chemical class 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 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
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000000214 vapour pressure osmometry Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000012991 xanthate 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
- 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
- C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- 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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/09—Complexes with metals
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
-
- 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
- C10N2030/02—Pour-point; Viscosity index
-
- 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
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/42—Phosphor free or low phosphor content compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/45—Ash-less or low ash content
-
- 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
- C10N2030/72—Extended drain
-
- 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
-
- 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
- C10N2040/252—Diesel engines
Definitions
- the present invention relates to lubricating oil compositions. More particularly, the present invention relates to lubricating oil compositions for use in engines comprising emission control systems.
- exhaust gas after-treatment devices may include exhaust gas recirculation arrangements and cooled exhaust gas recirculation arrangements, catalytic converters, which can contain one or more oxidation catalysts, NO x storage catalysts, and/or NH 3 reduction catalysts and/or a particulate trap. OEM's are also looking at using selective catalytic reduction (SCR) systems to further reduce NO x emissions.
- SCR selective catalytic reduction
- Oxidation catalysts can become poisoned and rendered less effective by exposure to certain elements/compounds present in engine exhaust gasses, particularly by exposure to phosphorus and phosphorus compounds introduced into the exhaust gas by the degradation of phosphorus-containing lubricating oil additives.
- Reduction catalysts are sensitive to sulfur and sulfur compounds in the engine exhaust gas introduced by the degradation of both the base oil used to blend the lubricant, and sulfur-containing lubricating oil additives.
- Particulate traps can become blocked by metallic ash, which is a product of degraded metal-containing lubricating oil additives.
- OEM's also require lubricating oil compositions to be formulated to reduce the presence of detrimental materials in the exhaust gas stream. At the same time, the selected lubricating oil composition must provide adequate lubricant performance, including adequate wear protection and detergency.
- European patent application 1 167 497 A2 discloses a lubricating oil composition having restricted sulfur, phosphorous and sulfated ash content comprising an ashless dispersant with a certain nitrogen content, a metal-containing detergent containing an organic acid metal salt selected from the group comprising an alkali or alkaline earth metal salt of an alkyl salicylic acid and an alkali or alkaline earth metal salt of an alkylphenol derivative having a mannich base structure providing a certain sulphated ash content, a zinc dialkyldithiophosphate providing a specified phosphorus amount and an oxidiation inhibitor.
- Lubricating oils formulated in accordance with this patent application are stated to exhibit good high temperature detergency despite the lower sulfur, phosphorus and sulphated ash levels of the compositions.
- US 2006/0116300 discloses a lubricating oil composition which provides improved top ring wear protection comprising a calcium salicylate detergent, a magnesium detergent and a nitrogen containing dispersant.
- a lubricating oil composition having a phosphorus content of up to 0.12 wt%, a sulfated ash content of up to 1.2 wt% comprising, (a) a major amount of an oil of lubricating viscosity; (b) an alkaline earth metal alkyl salicylate lubricating oil detergent which is a calcium salicylate, a magnesium salicylate, or a combination thereof, providing from 7-15 mmol of salicylate soap per kilogram of lubricating oil composition; (c) one or more ashless, nitrogen-containing dispersants providing the lubricating oil composition with from at least 0.12 wt% to 0.20 wt% atomic nitrogen, based on the weight of the lubricating oil composition, and (d) 0.05 to 5 wt% of a dispersant-viscosity modifier which is an aromatic amine derivatized, maleic anhydride grafted ethylene-propylene
- a method of lubricating a vehicle engine comprising an exhaust gas recirculation (EGR) system comprising use in that engine of a lubricating oil composition according to the first aspect of the invention.
- EGR exhaust gas recirculation
- an alkaline earth metal alkyl salicylate lubricating oil detergent which is a calcium salicylate, a magnesium salicylate, or a combination thereof, providing from 7-15 mmol salicylate soap per kilogram of lubricating oil composition
- one or more ashless, nitrogen-containing dispersants providing the lubricating oil composition with from at least 0.12 wt% to 0.20 wt% atomic nitrogen, based on the weight of the lubricating oil composition
- a dispersant-viscosity modifier which is an aromatic amine derivatized, maleic anhydride grafted ethylene-propylene copolymer
- a fourth aspect of the present invention there is provided a method according to the second aspect, wherein the engine further comprises a selective catalytic reduction (SCR) system.
- SCR selective catalytic reduction
- the oil of lubricating viscosity may be selected from Group I, II, III, IV or V base stocks, synthetic ester base stocks or mixtures thereof.
- the base stock groups are defined in the American Petroleum Institute (API) publication " Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998 .
- the base stock will have a viscosity preferably of 3-12, more preferably 4-10, most preferably 4.5-8 mm 2 /s (cSt.) at 100°C.
- Esters useful as synthetic base stock oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
- the oil of lubricating viscosity comprises less than 50 wt% of a Fischer-Tropsch base oil, suitably less than 30 wt%, preferably less than 10 wt% and most preferably substantially no Fischer-Tropsch base oil; wherein substantially no Fischer-Tropsch base oil means no more than an impurity amount.
- Table A - Analytical Methods for Testing Base Stocks Property Test Method Saturates ASTM D2007 Viscosity Index ASTM D2270 Sulfur ASTM D2622, D4294, D4927, or D3120
- the present invention requires the presence of at least one alkaline earth metal lubricating oil salicylate detergent.
- the metal salicylate detergent may be C 8 -C 30 alkyl salicylates or mixtures thereof, with C 10 -C 20 alkyl salicylates being particularly preferred.
- the salicylate detergent will be a calcium and/or magnesium salicylate and will have a Total Base Number at 100% active mass (TBN) between 10 and 1000, more preferably between 20 and 850.
- TBN Total Base Number at 100% active mass
- the most preferred detergent for use in this invention is one or a mixture of overbased calcium alkyl salicylate detergents having a TBN between 300 and 600.
- the metal salicylate detergent comprises substantially no magnesium alkyl salicylate detergent.
- the amount of metal salicylate detergent used can vary broadly, but typically will be from about 0.1 to about 5 wt.%, preferably 0.5 to 1.5 wt.% based on the total weight of the composition, so as to provide from 7-15 mmoles of metal salicylate detergent per kilogram of the finished oil composition.
- the amount of metal salicylate detergent used in the present invention provides the composition with at least 8 mmol soap per kilogram of the finished oil composition.
- the amount of metal salicylate detergent used in the present invention provides the composition with no more than 11 mmol soap per kilogram of the finished oil composition.
- the metal salicylate detergent provides greater than 0.3 mass%, preferably at least 0.4 mass% metal as sulphated ash to the lubricating oil composition.
- the metal salicylate may be the sole metal lubricating oil detergent present in the lubricating oil compositions of the invention.
- other metal-containing detergents such as metal sulfonates or phenates, may be present in the lubricating composition.
- the lubricating oil composition comprises a mixture of detergent types
- the lubricating oil composition suitably comprises a mixture of metal salicylate and metal sulphonate detergents.
- the additional detergents may be either calcium or magnesium metal salts.
- the additional detergents are calcium metal salts and the lubricating oil composition comprises substantially no magnesium metal salts.
- the salicylate detergent provides the majority of the detergent additive in the lubricating oil composition.
- substantially no magnesium metal salt detergent and substantially no magnesium alkyl salicylate detergent it is meant no more than an impurity amount, such as an amount providing less than 50 ppm magnesium preferably less than 30 ppm magnesium and most preferably less than 10 ppm magnesium.
- Metal salts of organic acids typically used as lubricating oil detergents are present as stable colloidal dispersions of salt in oil.
- the components are generally made by neutralizing the organic acid with a strong metal base in the presence of process aids.
- the organic acid is neutralized with a strong metal base in the presence of an acidic gas (often carbon dioxide).
- an acidic gas often carbon dioxide
- the amounts of carbonate, sulfonate, and phenolic hydroxide present in a lubricant are inferred from the amounts present in the individual components that are blended to make the finished lubricant. And those amounts are in turn inferred from the charge ratios of raw materials used to make the detergents or by resort to analytical methods that can determine detectable moieties allowing inference of the remaining moieties.
- the moles of metal salt of an organic acid present can be determined directly in some cases and in others must be derived.
- the salt is a calcium sulfonate
- direct analysis is possible using the liquid chromatography method described in ASTM 3712.
- the moles of salt must be derived.
- titrimetry including two phase titrimetric methods, total acid number (TAN) as determined using ASTM D664, dialysis and other well known analytical techniques allow determination of the organic salt content.
- TAN total acid number
- phenates and carboxylates including salicylates
- the total amount of metal must be determined and allocated between organic and inorganic acids using a metal ratio.
- the total amount of metal present is conveniently determined by inductively coupled plasma atomic emission spectrometry--ASTM D4951.
- Metal ratio is defined as the total amount of metal present divided by the amount of metal in excess of that required to neutralize any organic acid present, i.e., the amount of metal neutralizing inorganic acids. Metal ratios are quoted by manufacturers of commercial detergents and can be determined by a manufacturer having knowledge of the total amount of salts present and the average molecular weight of the organic acid.
- the amount of metal salt present in a detergent may be determined by dialyzing the detergent and quantifying the amount of the residue.
- the residue from the dialyzed detergent can be treated with strong acid to convert the salt to its acid form, analyzed by chromatographic methods, proton NMR, and mass spectroscopy and correlated to acids of known properties. More particularly, the detergent is dialysed and then residue is treated with strong acid to convert any salts to their respective acid form. The hydroxide number of the mixture can then be measured by the method described in ASTM D1957.
- the detergent contains non-phenolic hydroxyl groups on the phenolic compound (e.g., alcoholic derivatives of ethylene glycol used in manufacture of commercial phenates or carboxylic acid groups on salicylic acid), separate analyses must be conducted to quantify the amounts of those hydroxyl groups so that the hydroxide number determined by ASTM D1957 can be corrected. Suitable techniques to determine the quantity of non-phenolic hydroxyl groups include analyses by mass spectroscopy, liquid chromatography, and proton NMR and correlation to compounds having known properties.
- non-phenolic hydroxyl groups on the phenolic compound e.g., alcoholic derivatives of ethylene glycol used in manufacture of commercial phenates or carboxylic acid groups on salicylic acid
- a second method for deriving the number of moles of metal salt of an organic acid present assumes that all of the organic acid charged to make the component is in fact converted to the salt.
- the two methods can give slightly different results, but both are believed to be sufficiently precise to allow determination of the amount of salt present to the precision required to practice the present invention.
- the total amount of detergent present is limited by the maximum 1.2 wt% sulfated ash content of the finished oil composition.
- the total soap content of the lubricating oil is suitably no more than 1.5 wt%, preferably no more than 1.2wt% and more preferably no more than 1.0 wt%.
- the total soap content of the lubricating oil composition is suitably at least 0.7 wt%, preferably at least 0.75 wt%.
- An ashless dispersant generally comprises an oil soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
- the dispersants comprise amine, alcohol, amide, or ester polar moieties attached to the polymer backbone often via a bridging group.
- the ashless dispersant of the present invention may be, for example, selected from oil soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons, long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine.
- the most common dispersant in use is the well known succinimide dispersant, which is a condensation product of hydrocarbyl-substituted succinic anhydride and a poly(alkyleneamine). Both mono-succinimide and bis-succinimide dispersants (and mixtures thereof) are well known.
- Preferred groups of dispersant include polyamine-derivatized poly ⁇ -olefin, dispersants, particularly ethylene/butene alpha-olefin and polyisobutylene-based dispersants.
- Particularly preferred are ashless dispersants derived from polyisobutylene substituted with succinic anhydride groups and reacted with polyethylene amines, e.g., polyethylene diamine, tetraethylene pentamine; or a polyoxyalkylene polyamine, e.g., polyoxypropylene diamine, trimethylolaminomethane; a hydroxy compound, e.g., pentaerythritol; and combinations thereof.
- One particularly preferred dispersant combination is a combination of (A) polyisobutylene substituted with succinic anhydride groups and reacted with (B) a hydroxy compound, e.g., pentaerythritol; (C) a polyoxyalkylene polyamine, e.g., polyoxypropylene diamine, or (D) a polyalkylene diamine, e.g., polyethylene diamine and tetraethylene pentamine using about 0.3 to about 2 moles of (B), (C) and/or (D) per mole of (A).
- Another preferred dispersant combination comprises a combination of (A) polyisobutenyl succinic anhydride with (B) a polyalkylene polyamine, e.g., tetraethylene pentamine, and (C) a polyhydric alcohol or polyhydroxy-substituted aliphatic primary amine, e.g., pentaerythritol or trismethylolaminomethane, as described in U.S. Patent No. 3,632,511 .
- Mannich base condensation products Another class of ashless dispersants comprises Mannich base condensation products. Generally, these products are prepared by condensing about one mole of an alkyl-substituted mono- or polyhydroxy benzene with about 1 to 2.5 moles of carbonyl compound(s) (e.g., formaldehyde and paraformaldehyde) and about 0.5 to 2 moles of polyalkylene polyamine, as disclosed, for example, in U.S. Patent No. 3,442,808 .
- carbonyl compound(s) e.g., formaldehyde and paraformaldehyde
- Such Mannich base condensation products may include a polymer product of a metallocene catalyzed polymerization as a substituent on the benzene group, or may be reacted with a compound containing such a polymer substituted on a succinic anhydride in a manner similar to that described in U.S. Patent No. 3,442,808 .
- Examples of functionalized and/or derivatized olefin polymers synthesized using metallocene catalyst systems are described in the publications identified supra.
- the dispersant can be further post treated by a variety of conventional post treatments such as boration, as generally taught in U.S. Patent Nos. 3,087,936 and 3,254,025 .
- Boration of the dispersant is readily accomplished by treating an acyl nitrogen-containing dispersant with a boron compound such as boron oxide, boron halide boron acids, and esters of boron acids, in an amount sufficient to provide from about 0.1 to about 20 atomic proportions of boron for each mole of acylated nitrogen composition.
- Useful dispersants contain from about 0.05 to about 2.0 mass %, e.g., from about 0.05 to about 0.7 mass % boron.
- the boron which appears in the product as dehydrated boric acid polymers (primarily (HBO 2 ) 3 ), is believed to attach to the dispersant imides and diimides as amine salts, e.g., the metaborate salt of the diimide.
- Boration can be carried out by adding from about 0.5 to 4 mass %, e.g., from about 1 to about 3 mass % (based on the mass of acyl nitrogen compound) of a boron compound, preferably boric acid, usually as a slurry, to the acyl nitrogen compound and heating with stirring at from about 135°C to about 190°C, e.g., 140°C to 170°C, for from about 1 to about 5 hours, followed by nitrogen stripping.
- the boron treatment can be conducted by adding boric acid to a hot reaction mixture of the dicarboxylic acid material and amine, while removing water. Other post reaction processes commonly known in the art can also be applied.
- the dispersant may also be further post treated by reaction with a so-called "capping agent".
- a so-called "capping agent” nitrogen-containing dispersants have been "capped” to reduce the adverse effect such dispersants have on the fluoroelastomer engine seals.
- Numerous capping agents and methods are known. Of the known “capping agents", those that convert basic dispersant amino groups to non-basic moieties (e.g., amido or imido groups) are most suitable.
- alkyl acetoacetate e.g., ethyl acetoacetate (EAA)
- EAA ethyl acetoacetate
- the dispersant is a thermally maleated dispersant formed by reacting a polyalkenyl-substituted mono- or dicarboxylic acid, anhydride or ester; and a polyamine, having from greater than about 1.3 to less than about 1.7 mono- or dicarboxylic acid producing moieties per polyalkenyl moiety and wherein said polyalkenyl moiety has a molecular weight distribution (M w /M n ) of from 1.5 to 2.0 and a number average molecular weight (M n ) of from about 1800 to about 3000.
- M w /M n molecular weight distribution
- M n number average molecular weight
- the ashless dispersant is suitably present in an amount of from 4 to 10 wt.%, preferably about 5 to 8 wt.% on a 100% active matter basis.
- the dispersant should provide the lubricating oil composition with at least 0.12 wt % of atomic nitrogen.
- the dispersant provides the lubricating oil composition with no more than 0.2 wt % atomic nitrogen.
- the dispersant provides the lubricating oil composition with from 0.12 to 0.17 wt% atomic nitrogen.
- the nitrogen content provided to the lubricating oil composition by the dispersant can be determined in accordance with the procedures of ASTM D5762
- Preferred dispersants are borated or non-borated polyisobutenyl succinimide dispersants wherein the polyisobutenyl has a number average molecular weight (Mn) of about 400 to 3,000, preferably about 900 to 2,500.
- An embodiment of the present invention utilizes polyisobutenyl succinimide dispersants prepared using polyisobutylene prepared from a pure isobutylene stream or a Raffinate I stream to prepare reactive isobutylene polymers with terminal vinylidene olefins.
- these polymers referred to as highly reactive polyisobutylene (HR-PIB)
- HR-PIB highly reactive polyisobutylene
- HR-PIB highly reactive polyisobutylene
- HR-PIB highly reactive polyisobutylene
- the dispersant may comprise one dispersant or a combination of dispersants. If the dispersant comprises a combination of dispersants, the mixture suitable comprises a low molecular weight dispersant and a high molecular weight dispersant.
- a low molecular weight dispersant is a dispersant with a polymeric hydrocarbon backbone having a number average molecular weight (Mn) of about 500 to 1750.
- a high molecular weight dispersant is a dispersant with a polymeric hydrocarbon backbone having a number average molecular weight (Mn) of about 1800 to 3000.
- the total dispersant present in the lubricating oil composition comprises less than 40 mass%, less than 35 mass% or less than 30 mass% of low molecular weight dispersants.
- Polymer molecular weight can be determined by various known techniques.
- One convenient method is gel permeation chromatography (GPC), which additionally provides molecular weight distribution information (see W. W. Yau, J. J. Kirkland and D. D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979 ).
- GPC gel permeation chromatography
- Another useful method for determining molecular weight, particularly for lower molecular weight polymers is vapor pressure osmometry (see, e.g., ASTM D3592).
- the viscosity index of the base stock is increased, or improved, by incorporating therein certain polymeric materials that function as viscosity modifiers (VM) or viscosity index improvers (VII).
- polymeric materials useful as viscosity modifiers are those having number average molecular weights (Mn) of from about 5,000 to about 250,000, preferably from about 15,000 to about 200,000, more preferably from about 20,000 to about 150,000.
- Suitable viscosity modifiers are polyisobutylene, olefin copolymers, such as copolymers of ethylene and propylene and higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, inter polymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene.
- Dispersant-viscosity modifiers are produced from grafting viscosity modifiers, such as those described above, with grafting materials such as, for example, maleic anhydride, and then reacting the grafted material with, for example, amines, amides, nitrogen-containing heterocyclic compounds or alcohol.
- grafting materials such as, for example, maleic anhydride
- the dispersant-viscosity modifier is an aromatic amine derivatized, maleic anhydride grafted ethylene-propylene copolymer.
- a preferred aromatic amine is N-phenyl -1,4 - phenylenediamine.
- the copolymer preferably has a number average molecular weight Mn of at least 5,000, preferably at least 8,000 and suitably at least 10,000.
- the copolymer may have an Mn as high as 100,000, but is suitably no more than 60,000 and preferably around 40,000.
- Suitable commercially available dispersant-viscosity modifiers include, but are not limited to, HiTec 5777, available from Afton Chemicals.
- the present invention comprises a dispersant-viscosity modifier. It is present in amounts of from 0.05 to 5 wt. %, preferably 0.5 to 3 wt.% on an active matter basis.
- a lubricating oil composition according to the present invention may additionally comprise one or more standard crankcase lubricating oil additives; examples or which are discussed below.
- Antioxidants reduce the tendency of base stocks to deteriorate in service which deterioration can be evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces and by viscosity growth.
- they are suitably present in amount of from 0.1 to 5.0 wt.%.
- Suitable oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, calcium nonylphenol sulfide, ashless oil soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, alkyl substituted diphenylamine, alkyl substituted phenyl and napthylamines, phosphorous esters, metal thiocarbamates, ashless thiocarbamates and oil soluble copper compounds as described in U.S. 4,867,890 .
- dialkyl substituted diphenylamines wherein the alkyl is C 4 -C 20 , such as dinonyl diphenylamine and the hindered phenols, such as isooctyl-3,5-di-tert-butyl-4-hydroxycinnamate and mixtures of same.
- Zinc dihydrocarbyl dithiophosphates are oil soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula: wherein R and R' may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R and R' groups are alkyl groups of 2 to 8 carbon atoms.
- the radicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.
- the total number of carbon atoms (i.e. R and R') in the dithiophosphoric acid will generally be about 5 or greater.
- the zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
- ZDDP is the most commonly used antioxidant/antiwear agent in lubricating oil compositions for internal combustion engines, and in conventional passenger car diesel engines formulated to meet present European ACEA specifications.
- the lubricating oil compositions of the present invention suitably contain an amount of ZDDP (or other dihydrocarbyl dithiophosphate metal salt) that introduces about 0.02 to 0.12 wt.%, preferably 0.02 to 0.1 wt.%, more preferably 0.05 to 0.08 wt.% of phosphorus into the lubricating oil composition.
- the phosphorus content of the lubricating oil compositions is determined in accordance with the procedures of ASTM D5185.
- any suitable oil soluble organo-molybdenum compound may be employed.
- the molybdenum compound is thought to function both as an antiwear and antioxidant additive.
- dimeric and trimeric molybdenum compounds are used.
- oil soluble organo-molybdenum compounds are the dialkyldithiocarbamates, dialkyldithiophosphates, dialkyldithiophosphinates, xanthates, thioxanthates, carboxylates and the like, and mixtures thereof.
- Particularly preferred are molybdenum dialkylthiocarbamates.
- Suitable molybdenum dialkyldithiocarbamates include dimeric molybdenum dialkyldithiocarbamates such as those having the following formula: R 1 through R 4 independently denote a straight chain, branched chain or aromatic hydrocarbyl group; and X1 through X4 independently denote an oxygen atom or a sulfur atom.
- the four hydrocarbyl groups, R 1 through R 4 may be identical or different from one another.
- organo-molybdenum compounds useful in the lubricating compositions of this invention are trinuclear (trimeric) molybdenum compounds, especially those of the formula Mo 3 S k L n Q z and mixtures thereof wherein the L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble in the oil, n is from 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At least 21 total carbon atoms should be present among all the ligands' organo groups, such as at least 25, at least 30, or at least 35 carbon atoms.
- the ligands are selected from the group consisting of -X-R 1, and and mixtures thereof, wherein X, X 1 , X 2 , and Y are independently selected from the group of oxygen and sulfur, and wherein R 1 , R 2 , and R are independently selected from hydrogen and organo groups that may be the same or different.
- the organo groups are hydrocarbyl groups such as alkyl (e.g., in which the carbon atom attached to the remainder of the ligand is primary or secondary), aryl, substituted aryl and ether groups. More preferably, each ligand has the same hydrocarbyl group.
- hydrocarbyl denotes a substituent having carbon atoms directly attached to the remainder of the ligand and is predominantly hydrocarbyl in character within the context of this invention.
- substituents include the following:
- the organo groups of the ligands should have a sufficient number of carbon atoms to render the compound soluble in the oil.
- the number of carbon atoms in each group will generally range between about 1 to about 100, preferably from about 1 to about 30, and more preferably between about 4 to about 20.
- Preferred ligands include dialkyldithiophosphate, alkylxanthate, carboxylates, dialkyldithiocarbamate, and mixtures thereof. Most preferred are the dialkyldithiocarbamates. Those skilled in the art will realize that formation of the compounds requires selection of ligands having the appropriate charge to balance the core's charge (as discussed below).
- Oil-soluble trinuclear molybdenum compounds are preferred and can be prepared by reacting in the appropriate liquid(s)/solvent(s) a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 ⁇ n(H 2 O), where n varies between 0 and 2 and includes non-stoichiometric values, with a suitable ligand source such as a tetralkylthiuram disulfide.
- a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 ⁇ n(H 2 O), where n varies between 0 and 2 and includes non-stoichiometric values
- oil-soluble trinuclear molybdenum compounds can be formed during a reaction in the appropriate solvent(s) of a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 ⁇ n(H 2 O), a ligand source such as tetralkylthiuram disulfide, dialkyldithiocarbamate, or dialkyldithiophosphate, and a sulfur abstracting agent such cyanide ions, sulfite ions, or substituted phosphines.
- a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 ⁇ n(H 2 O)
- a ligand source such as tetralkylthiuram disulfide, dialkyldithiocarbamate, or dialkyldithiophosphate
- a sulfur abstracting agent such cyanide ions, sulfite ions, or substituted phosphines.
- a trinuclear molybdenum-sulfur halide salt such as [M'] 2 [Mo 3 S 7 A 6 ], where M' is a counter ion, and A is a halogen such as Cl, Br, or I, may be reacted with a ligand source such as a dialkyldithiocarbamate or dialkyldithiophosphate in the appropriate liquid(s)/solvent(s) to form an oil-soluble trinuclear molybdenum compound.
- the appropriate liquid/solvent may be, for example, aqueous or organic.
- the ligand chosen must have a sufficient number of carbon atoms to render the compound soluble in the lubricating composition.
- oil-soluble does not necessarily indicate that the compounds or additives are soluble in the oil in all proportions. It does mean that they are soluble in use, transportation, and storage.
- a basic nitrogen compound selected from the group consisting of succinimide, a carboxylic acid amide, a hydrocarbyl monoamine, a phosphoramide, a thiophosphoramide, a Mannich base, a dispersant-viscosity index improver, or a mixture thereof.
- the sulfurized molybdenum containing compositions may be generally characterized as a molybdenum/sulfur complex of a basic nitrogen compound.
- the precise molecular formula of these molybdenum compositions is not known with certainty. However, they are believed to be compounds in which molybdenum, whose valences are satisfied with atoms of oxygen or sulfur, is either complexed by, or the salt of one or more nitrogen atoms of the basic nitrogen containing compound used in the preparation of these compositions.
- the lubricating compositions of the present invention may contain a minor amount of an oil soluble molybdenum compound. If present an amount of at least 10 ppm up to about 600 ppm of molybdenum from a molybdenum compound may be present in the lubricating oil composition. Preferably, about 10 ppm to 300 ppm of molybdenum from a molybdenum compound is used. More preferably, no more than 100 ppm of molybdenum from a molybdenum compound is used. These values are based upon the weight of the lubricating composition.
- the lubricating oil composition may contain an organic oil-soluble friction modifier.
- the friction modifier may make up about 0.02 to 2.0 wt.% of the lubricating oil composition.
- Friction modifiers include such compounds as aliphatic amines or ethoxylated aliphatic amines, aliphatic fatty acid amides, aliphatic carboxylic acids, aliphatic carboxylic esters of polyols such as glycerol esters of fatty acids as exemplified by glycerol oleate, which is preferred, aliphatic carboxylic ester-amides, aliphatic phosphonates, aliphatic thiophosphates, etc., wherein the aliphatic group usually contains above about eight carbon atoms so as to render the compound suitably oil soluble.
- aliphatic substituted succinimides formed by reacting one or more aliphatic succinic acids or anhydrides with ammonia.
- pour point depressants otherwise known as lube oil flow improvers, lower the minimum temperature at which the fluid will flow or can be poured.
- Such additives are well known. Typical of those additives which improve the low temperature fluidity of the fluid are C 8 to C 18 dialkyl fumarate/vinyl acetate copolymers, polyalkylmethacrylates and the like. These may be used in amounts of from 0.01 to 5.0 wt.%, preferably about 0.1 to 3.0 wt.%. They are preferably used when mineral oil base stocks are employed but are not generally required when the base stock is a PAO or synthetic ester.
- Foam control can be provided by many compounds including an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
- additives can provide a multiplicity of effects; thus for example, a single additive may act as a dispersant-oxidation inhibitor. This approach is well known and does not require further elaboration.
- each of the components can be added directly to the base stock or base oil blend by dispersing or dissolving it in the base stock or base oil blend at the desired level of concentration. Such blending may occur at ambient temperature or at an elevated temperature.
- the invention comprising the product results from the admixture of the additive components to form a lubricating oil composition.
- the additives are blended together to form a concentrate or additive package that is subsequently blended into base stock to make the finished lubricant.
- the concentrate or additive package may contain the viscosity modifier, or the viscosity modifier may be added separately from the concentrate or additive package to form the lubricating oil composition.
- the concentrate will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the final formulation when the concentrate is combined with a predetermined amount of a base lubricant.
- the final crankcase lubricating oil formulation may employ from 10 to 50 mass %, preferably 15 to 40 mass% of the concentrate or additive package, with the remainder being base stock.
- Lubricating oil composition Oil A was prepared by mixing an additive package comprising 4.8 mass% of a polyisobutenyl succinimide dispersant made from a polyisobutenyl with a number average molecular weight (Mn) of 2225, 1.08 mass% of polyisobutenyl succinimide dispersants made from a polyisobutenyl with a number average molecular weight (Mn) of 950, 0.74 mass% of a 321 TBN overbased calcium salicylate detergent and 0.34 mass% of a 565 TBN overbased calcium salicylate detergent, 0.43 mass% of 709 TBN overbased magnesium sulfonate detergent, 0.84 mass% of HiTec 5777 dispersant-viscosity modifier, and additional zinc dialkyl dithiophosphate, organic molybdenum dithiocarbamate and antioxidant into a base stock comprising a mixture of Group I and Group III base oils.
- Mn number average molecular weight
- Mn number average molecular weight
- Oil A comprised 0.96 wt% sulphated ash, 0.08 wt% phosphorous, 0.21 wt% sulfur, 130 ppm of atomic boron, 50 ppm molybdenum, 0.153 mass % calcium and 0.069 mass% magnesium.
- the salicylate soap content of Oil A was 8.8mmol and the total soap content of the Oil was 0.85 mass% soap.
- the calcium salicylate detergents provide the lubricating oil composition with 0.5 mass% calcium as sulphated ash.
- the dispersants provide the lubricating oil composition with 0.135 mass% nitrogen, with 0.096 mass% N being provided by the high molecular weigh dispersant and 0.039 mass% being provided by low molecular weight dispersant.
- Oil A was then run in the ASTM D7422 engine test, more commonly known as the Mack T-12.
- the Mack T-12 test is designed to evaluate the ability of an oil to minimize wear in an engine equipped with an EGR system.
- the Mack T-12 engine test is part of the API CJ-4 and ACEA E6 performance categories.
- the engine used is a modified Mack E7 E-Tech 460 rated at 460 bhp and 1,800 rpm, with EGR system.
- the test runs over 300 hours and at the end of the test piston ring wear, cylinder liner wear, lead bearing corrosion, oil consumption and oxidation are evaluated.
- Lubricating oil composition Oil B was prepared by mixing an additive package comprising 4.8 mass% of a polyisobutenyl succinimide dispersant made from a polyisobutenyl with a number average molecular weight (Mn) of 2225, 1.08 mass% of polyisobutenyl succinimide dispersants made from a polyisobutenyl with a number average molecular weight (Mn) of 950, 0.84 mass% of a 321 TBN overbased calcium salicylate detergent and 0.34 mass% of a 565 TBN overbased calcium salicylate detergent, 0.43 mass% a 709 TBN of overbased magnesium sulfonate detergent, 0.84 mass% of HiTec 5777 dispersant-viscosity modifier, and zinc dialkyl dithiophosphate, molybdenum dithiocarbamate and antioxidant, into a base stock comprising a mixture of Group I and Group III base oils.
- Mn number average molecular weight
- Mn number average molecular
- Oil B comprised 1.0 wt% sulphated ash, 0.08 wt% phosphorous, 0.21 wt% sulfur, 130 ppm of atomic boron 50 ppm molybdenum, 0.165 mass% calcium and 0.069 mass% magnesium.
- the salicylate soap content of Oil B was 9.8mmol and the total soap content of the Oil was 0.92mass% soap.
- the calcium salicylate detergents providing the lubricating oil composition with 0.54 mass% calcium as sulphated ash.
- the dispersants provide the lubricating oil composition with 0.135 mass% nitrogen, with 0.096 mass% nitrogen being provided by high molecular weight dispersant and 0.039 mass% being provided by low molecular weight dispersant.
- Oil B was then run in the Mercedes-Benz OM646 LA (CEC L-99-08) engine test, which is part of the ACEA and Daimler specifications.
- This 300-hour test uses the 2.2L common rail diesel OM646 DE 22 LA engine to evaluate engine lubricant performance with respect to engine wear and overall cleanliness, as well as piston cleanliness and ring sticking.
- Oil B passes the OM646LA engine test at the required performance level for ACEA E6.
- the test also achieves all of the necessary parameters for the more stringent MB 228.51 specification level.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Claims (16)
- Composition d'huile lubrifiante ayant une teneur en phosphore allant jusqu'à 0,12 % en poids, une teneur en cendre sulfatée allant jusqu'à 1,2 % en poids, comprenant :a. une quantité dominante d'une huile de viscosité propre à la lubrification ;b. un détergent pour huiles lubrifiantes du type alkylsalicylate de métal alcalino-terreux qui est un salicylate de calcium, un salicylate de magnésium ou une de leurs associations, fournissant 7 à 15 mmol de savon de salicylate par kilogramme de composition d'huile lubrifiante ;c. un ou plusieurs dispersants azotés sans cendre fournissant à la composition d'huile lubrifiante au moins 0,12 % en poids à 0,20 % en poids d'azote atomique, sur la base du poids de la composition d'huile lubrifiante, etd. 0,05 à 5 % en poids d'un dispersant-modificateur de viscosité qui est un copolymère éthylène-propylène transformé en dérivé avec une amine aromatique et greffé avec de l'anhydride maléique.
- Composition d'huile lubrifiante suivant la revendication 1, dans laquelle la teneur en phosphore est non supérieure à 0,08 % en poids.
- Composition d'huile lubrifiante suivant la revendication 1 ou 2, dans laquelle la teneur en cendre sulfatée est non supérieure à 1,0 % en poids.
- Composition d'huile lubrifiante suivant la revendication 1, 2 ou 3, dans laquelle le détergent pour huiles lubrifiantes du type alkylsalicylate de métal alcalino-terreux fournit 8 à 11 mmol de savon de salicylate par kilogramme de composition d'huile lubrifiante.
- Composition d'huile lubrifiante suivant l'une quelconque des revendications précédentes, dans laquelle le ou les dispersants fournissent à la composition d'huile lubrifiante au moins 0,12 % en poids à 0,17 % en poids d'azote atomique, sur la base du poids de la composition d'huile lubrifiante.
- Composition d'huile lubrifiante suivant l'une quelconque des revendications précédentes, dans laquelle le détergent pour huiles lubrifiantes du type alkylsalicylate de métal alcalino-terreux est un détergent ou un mélange de détergents de type alkylsalicylate de calcium surbasique ayant un indice de basicité total (TBN) entre 300 et 600.
- Composition d'huile lubrifiante suivant l'une quelconque des revendications précédentes, comprenant en outre un détergent pour huiles lubrifiantes de type alkylsulphonate de métal alcalino-terreux.
- Composition d'huile lubrifiante suivant l'une quelconque des revendications précédentes, dans laquelle le dispersant est un dispersant du type polyisobuténylsuccinimide.
- Composition d'huile lubrifiante suivant l'une quelconque des revendications précédentes, qui satisfait les critères à la fois de la spécification API-CJ4 et de la spécification ACEA E6.
- Composition d'huile lubrifiante suivant l'une quelconque des revendications précédentes, dans laquelle ladite amine aromatique du copolymère éthylène-propylène transformé en dérivé avec une amine aromatique et greffé avec de l'anhydride maléique est la N-phényl-1,4-phénylènediamine.
- Composition d'huile lubrifiante suivant l'une quelconque des revendications précédentes, dans laquelle le copolymère éthylène-propylène du dispersant-modificateur de viscosité a une moyenne en nombre du poids moléculaire (Mn) d'au moins 5000.
- Composition d'huile lubrifiante suivant l'une quelconque des revendications précédentes, ladite composition d'huile lubrifiante ne comprenant pratiquement pas de détergent pour huiles lubrifiantes du type alkylsalicylate de magnésium, détergent présent en une quantité fournissant moins de 50 ppm de magnésium à la composition d'huile lubrifiante.
- Procédé pour la lubrification d'un moteur de véhicule comprenant un système de recirculation des gaz d'échappement (EGR), comprenant l'utilisation dans ce moteur d'une composition d'huile lubrifiante suivant l'une quelconque des revendications 1 à 12.
- Procédé suivant la revendication 13, dans lequel le moteur est un moteur à allumage par compression.
- Procédé suivant l'une quelconque des revendications 12 à 14, dans lequel le moteur comprend en outre un dispositif de réduction catalytique sélective.
- Utilisation, dans la lubrification d'un moteur à allumage par compression comprenant un système de recirculation des gaz d'échappement EGR, d'une association : (i) d'un détergent pour huile lubrifiante pour huile de type alkylsalicylate de métal alcalino-terreux qui est un salicylate de calcium, un salicylate de magnésium ou une de leurs associations, fournissant 7 à 15 mmol de savon de salicylate par kilogramme de composition d'huile lubrifiante ; (ii) d'un ou plusieurs dispersants azotés sans cendre fournissant à la composition d'huile lubrifiante au moins 0,12 % en poids à 0,20 % en poids d'azote atomique, sur la base du poids de la composition d'huile lubrifiante ; (iii) 0,05 à 5 % en poids d'un dispersant-modificateur de viscosité qui est un copolymère éthylène-propylène transformé en dérivé avec une amine aromatique et greffé avec de l'anhydride maléique, dans une composition d'huile lubrifiante comprenant une quantité dominante d'une huile de viscosité propre à la lubrification, ladite composition d'huile lubrifiante ayant une teneur en phosphore allant jusqu'à 0,12 % en poids, une teneur en cendre sulfatée ayant jusqu'à 1,2 % en poids, pour réduire au minimum l'usure dans le moteur à allumage par compression.
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EP11159502.1A EP2371934B1 (fr) | 2010-03-31 | 2011-03-24 | Composition d'huile lubrifiante |
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EP10158789 | 2010-03-31 | ||
EP11159502.1A EP2371934B1 (fr) | 2010-03-31 | 2011-03-24 | Composition d'huile lubrifiante |
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EP2371934A1 EP2371934A1 (fr) | 2011-10-05 |
EP2371934B1 true EP2371934B1 (fr) | 2017-03-15 |
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US (1) | US20110245120A1 (fr) |
EP (1) | EP2371934B1 (fr) |
JP (1) | JP5738054B2 (fr) |
CN (1) | CN102206535B (fr) |
BR (1) | BRPI1101393B1 (fr) |
CA (1) | CA2735498C (fr) |
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2011
- 2011-03-24 EP EP11159502.1A patent/EP2371934B1/fr active Active
- 2011-03-30 BR BRPI1101393A patent/BRPI1101393B1/pt active IP Right Grant
- 2011-03-30 US US13/075,223 patent/US20110245120A1/en not_active Abandoned
- 2011-03-30 CA CA2735498A patent/CA2735498C/fr active Active
- 2011-03-31 CN CN201110079689.8A patent/CN102206535B/zh active Active
- 2011-03-31 JP JP2011092460A patent/JP5738054B2/ja active Active
Non-Patent Citations (1)
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None * |
Also Published As
Publication number | Publication date |
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JP2011214004A (ja) | 2011-10-27 |
CA2735498A1 (fr) | 2011-09-30 |
CN102206535B (zh) | 2015-01-28 |
CA2735498C (fr) | 2018-01-16 |
BRPI1101393B1 (pt) | 2018-11-21 |
JP5738054B2 (ja) | 2015-06-17 |
CN102206535A (zh) | 2011-10-05 |
EP2371934A1 (fr) | 2011-10-05 |
US20110245120A1 (en) | 2011-10-06 |
BRPI1101393A2 (pt) | 2012-08-14 |
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