EP4127112A1 - Lubricant composition comprising a 2,5-dimercapto-1,3,4-thiadiazole alkyl polycarboxylate compound - Google Patents
Lubricant composition comprising a 2,5-dimercapto-1,3,4-thiadiazole alkyl polycarboxylate compoundInfo
- Publication number
- EP4127112A1 EP4127112A1 EP21714206.6A EP21714206A EP4127112A1 EP 4127112 A1 EP4127112 A1 EP 4127112A1 EP 21714206 A EP21714206 A EP 21714206A EP 4127112 A1 EP4127112 A1 EP 4127112A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- compound
- alkyl
- mass
- carboxylate
- group
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 159
- 150000001875 compounds Chemical class 0.000 title claims abstract description 92
- 239000000314 lubricant Substances 0.000 title abstract description 12
- 229920005646 polycarboxylate Polymers 0.000 title abstract description 5
- 239000000654 additive Substances 0.000 claims abstract description 49
- 230000001050 lubricating effect Effects 0.000 claims description 106
- -1 carboxylate compound Chemical class 0.000 claims description 75
- 125000000217 alkyl group Chemical group 0.000 claims description 49
- 239000000446 fuel Substances 0.000 claims description 34
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 29
- 239000002199 base oil Substances 0.000 claims description 29
- 230000000996 additive effect Effects 0.000 claims description 25
- 125000005599 alkyl carboxylate group Chemical group 0.000 claims description 20
- 150000007942 carboxylates Chemical class 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical class C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000010687 lubricating oil Substances 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 2
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 50
- 229910052750 molybdenum Inorganic materials 0.000 description 24
- 239000011733 molybdenum Substances 0.000 description 24
- 239000003446 ligand Substances 0.000 description 19
- 125000004430 oxygen atom Chemical group O* 0.000 description 17
- 239000003963 antioxidant agent Substances 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000003599 detergent Substances 0.000 description 9
- 229920006395 saturated elastomer Polymers 0.000 description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 239000003607 modifier Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000007866 anti-wear additive Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 125000004434 sulfur atom Chemical group 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 5
- DKVNPHBNOWQYFE-UHFFFAOYSA-M carbamodithioate Chemical compound NC([S-])=S DKVNPHBNOWQYFE-UHFFFAOYSA-M 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000012990 dithiocarbamate Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000005069 Extreme pressure additive Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000000392 cycloalkenyl group Chemical group 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000005078 molybdenum compound Substances 0.000 description 3
- 150000002752 molybdenum compounds Chemical class 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- MCLMZMISZCYBBG-UHFFFAOYSA-N 3-ethylheptanoic acid Chemical group CCCCC(CC)CC(O)=O MCLMZMISZCYBBG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 150000002751 molybdenum Chemical class 0.000 description 2
- 125000001421 myristyl 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])[H] 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 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 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 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 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- KUHJJSKJQLIHBS-UHFFFAOYSA-N 1,4-diaminobutan-1-ol Chemical compound NCCCC(N)O KUHJJSKJQLIHBS-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
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-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
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XYRMLECORMNZEY-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S Chemical class [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S XYRMLECORMNZEY-UHFFFAOYSA-B 0.000 description 1
- BTHAQRDGBHUQMR-UHFFFAOYSA-N [S]P(=O)=O Chemical compound [S]P(=O)=O BTHAQRDGBHUQMR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000001204 arachidyl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 125000002511 behenyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 description 1
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 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
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=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
- 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
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 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
- 150000002118 epoxides Chemical class 0.000 description 1
- 229930195712 glutamate Natural products 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002463 lignoceryl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001802 myricyl 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])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
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 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
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 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
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the 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
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
-
- 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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
- C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
-
- 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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
-
- 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
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
-
- 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
- C10N2010/06—Groups 3 or 13
-
- 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
- C10N2030/54—Fuel economy
-
- 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
- Lubricating composition comprising a 2,5-dimercapto-1,3,4-thiadiazole alkyl polycarboxylate compound
- the invention relates to the field of lubricating compositions, in particular the fuel economy properties known as fuel economy (FE or fueleco) of lubricating compositions. More specifically, the invention relates to an additive composition making it possible to maintain over time the fuel economy properties of a lubricating composition (FE retention or fuel eco retention). The invention also relates to the use in a lubricating composition of an additive composition according to the invention as well as the resulting lubricating composition.
- FE fuel economy
- fueleco fuel economy
- the invention also relates to the use in a lubricating composition of an additive composition according to the invention as well as the resulting lubricating composition.
- the oil change intervals are also very variable, from 5,000 km for some small diesel engines, they can go up to 100,000 km on modern commercial vehicle diesel engines.
- Lubricating compositions for motor vehicles must be adaptable to all of these conditions of use and thus must have improved properties and performance.
- the lubrication of the parts sliding over one another plays a decisive role, in particular in reducing the friction between these parts and consequently the wear thereof, in particular allowing fuel savings.
- Lubricating compositions for motor vehicles have an influence on the fuel consumption.
- Lubricating compositions for automobile engines allowing fuel savings are often referred to as fuel eco (FE), in English terminology.
- the improvement of the fuel eco performance level is constantly sought in the formulation of automotive lubricants.
- the organomolybdenum compound such as MoDTC forms two compounds M0S 2 (lamellar molybdenum disulphide) which reduces friction and molybdenum trioxide (M0O 3 ) which tends to increase wear.
- the Molybdenum forming part of the organomolybdenum compound oxidizes which is responsible for the loss of performance of the organomolybdenum compound over time and therefore a loss of performance of the Fuel Eco of the lubricating composition (and therefore of the fuel economy) in the weather.
- An objective of the present invention is to provide a lubricating composition having Fuel Eco properties that are prolonged over time and therefore to maintain a reduction in fuel consumption over time.
- Another objective of the present invention is to provide a lubricating composition which makes it possible to maintain a low coefficient of friction over time.
- Yet another object of the present invention is to provide a solution to the decrease in the effectiveness of the organomolybdenum compound over time.
- Yet another objective of the present invention is to provide a compound making it possible to protect the organomolybdenum compound of a lubricating composition from its degradation over time, in particular by oxidation.
- the invention relates first of all to a composition of additives for lubricating oil comprising:
- the invention also relates to a lubricating composition
- a lubricating composition comprising:
- the invention finally relates to the use of a 2, 5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound in a lubricating composition comprising at least one base oil and at least one organomolybdenum compound, preferably chosen from dinuclear organomolybdenum compounds.
- a 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound is used to maintain the fuel economy of an internal combustion engine over time.
- 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate ranges from 1: 100 to 100: 1, preferably from 1: 10 to 10: 1, more preferably from 1: 5 to 5: 1.
- the organomolybdenum compound is chosen from dinuclear organomolybdenum compounds, preferably from molybdenum dithiocarbamates.
- the 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound is chosen from the compounds of formula (IV) below: in which R 'represents a C1-C34 alkyl group substituted by at least one C 1 -C 34 alkyl carboxylate group, preferably at least two C 1 -C 34 alkyl carboxylate groups.
- the group R ′ is a C1-C30, preferably C1-C20, more preferably C1-C10, typically C1-C5 alkyl group, for example an ethyl group.
- the alkyl carboxylate group (s) are chosen, independently, from the alkyl carboxylate groups in C1-C30, preferably in C1-C20, more preferably in C1-C10, for example is a 2-ethylhexyl group.
- the compound 2, 5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate corresponds to the following formula (V):
- the lubricating composition comprises from 50% to 99.5% by mass of base oil, relative to the total mass of the lubricating composition.
- the content of molybdenum element in the lubricating composition ranges from 50 to 1,500 ppm by mass, preferably from 100 to 1,000 ppm by mass, relative to the total mass of the lubricating composition.
- the lubricating composition comprises from 0.2% to 1.0% by mass of 2,5-dimercapto-1, 3,4-thiadiazole, alkyl (poly) carboxylate compound, preferably 0.2 to 0.9 % by mass, for example 0.5% by mass, relative to the total mass of the lubricating composition.
- the lubricating composition has a sulfur content ranging from 0.01% to 5% by mass, preferably from 0.1% to 2% by mass, more preferably from 0.1% to 0.5% by mass, relative to the total mass of the composition.
- the compound 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate is more thermally stable than the other sulfur compounds used in lubricating compositions such as for example a polysulfide compound or a phospho-sulfur compound.
- the presence of the 2,5-dimercapto- 1,3,4-thiadiazole alkyl (poly) carboxylate compound in a lubricating composition comprising an organomolybdenum compound, such as for example molybdenum dithiocarbamate, also called MoDTC, makes it possible to reduce the oxidation of molybdenum or even to protect the molybdenum from oxidation and to promote the sulfurization of the organomolybdenum compound and of the sulfurized by-products of molybdenum and therefore to maintain over time the properties of the organomolybdenum compound, such as, for example, MoDTC.
- organomolybdenum compound such as for example molybdenum dithiocarbamate, also called MoDTC
- the invention relates to a lubricating oil additive composition
- a lubricating oil additive composition comprising:
- a subject of the invention is also a lubricating composition comprising: - at least one base oil,
- organomolybdenum compound according to the invention is meant any liposoluble organomolybdenum compound.
- the organomolybdenum compound according to the present invention can be chosen from organic molybdenum complexes comprising at least one chemical element molybdenum (Mo), preferably at least two chemical elements molybdenum (Mo), and at least one ligand such as a ligand. carboxylate, ester ligand, amide ligand, dithiophosphate ligand, dithiocarbamate ligand.
- the organic complexes of molybdenum with carboxylates, esters, amides can be obtained by reaction of molybdenum oxide or ammonium molybdates with fatty substances, glycerides, fatty acids or derivatives of fatty acids (esters , amines, amides, ).
- the carboxylate ligands, the ester ligands and the amide ligands are free from sulfur and phosphorus.
- the organomolybdenum compound of the invention is chosen from complexes of molybdenum with amide ligands, mainly prepared by reaction of a source of molybdenum, which may for example be molybdenum trioxide, and of a derivative of amine, and of fatty acids comprising, for example, from 4 to 36 carbon atoms, such as, for example, the fatty acids contained in vegetable or animal oils.
- a source of molybdenum which may for example be molybdenum trioxide, and of a derivative of amine
- fatty acids comprising, for example, from 4 to 36 carbon atoms, such as, for example, the fatty acids contained in vegetable or animal oils.
- the organomolybdenum compound is chosen from dinuclear organomolydbene compounds.
- nuclear organomolybdenum compound is meant within the meaning of the invention organomolybdenum compounds whose nucleus has two molybdenum atoms. We also speak of dimeric organomolydbene compounds.
- the organomolybdenum compound is chosen from organic complexes of molybdenum with amide ligands obtained by reaction:
- - X 1 represents an oxygen atom or a nitrogen atom
- - X 2 represents an oxygen atom or a nitrogen atom
- - n or m represents 1 when respectively X 1 or X 2 represents an oxygen atom
- - n or m represents 2 when respectively X 1 or X 2 represents a nitrogen atom
- molybdenum chosen from molybdenum trioxide or molybdates, preferably ammonium molybdate.
- the organomolybdenum compound may comprise from 0.1 to 30% by weight, preferably from 0.1 to 20%, more preferably from 2 to 8.5% by weight of molybdenum relative to to the total weight of the organomolybdenum complex.
- the organomolybdenum compound comprises at least one organic molybdenum complex of formula (I) or (II), alone or as a mixture: in which :
- X 1 represents an oxygen atom or a nitrogen atom
- X 2 represents an oxygen atom or a nitrogen atom
- n represents 1 when X 1 represents an oxygen atom and m represents 1 when X 2 represents an oxygen atom
- n represents 2 when X 1 represents a nitrogen atom and m represents 2 when X 2 represents a nitrogen atom
- R 1 represents a linear or branched, saturated or unsaturated alkyl group comprising from 4 to 36 carbon atoms, preferably from 4 to 20 carbon atoms, advantageously from 6 to 18 carbon atoms; in which :
- X 1 represents an oxygen atom or a nitrogen atom
- X 2 represents an oxygen atom or a nitrogen atom
- n represents 1 when X 1 represents an oxygen atom and m represents 1 when X 2 represents an oxygen atom
- n represents 2 when X 1 represents a nitrogen atom and m represents 2 when X 2 represents a nitrogen atom
- R 1 represents a linear or branched, saturated or unsaturated alkyl group comprising from 4 to 36 carbon atoms, preferably from 4 to 20 carbon atoms, advantageously from 6 to 18 carbon atoms;
- R2 represents a linear or branched, saturated or unsaturated alkyl group comprising from 4 to 36 carbon atoms, preferably from 4 to 20 carbon atoms, advantageously from 6 to 18 carbon atoms.
- organic molybdenum complex of formula (I) or (II) is prepared by reaction:
- molybdenum chosen from molybdenum trioxide or molybdates, preferably ammonium molybdate.
- the organic molybdenum complex of formula (I) consists of at least one compound of formula (la) or (lb), alone or as a mixture: (
- the organomolybdenum compound is chosen from organic complexes of molybdenum with dithiophosphate ligands or organic complexes of molybdenum with dithiocarbamate ligands.
- organic complexes of molybdenum with dithiophosphate ligands are also called molybdenum dithiophosphates or Mo-DTP compounds and organic complexes of molybdenum with dithiocarbamate ligands are also called molybdenum dithiocarbamates or Mo-DTC compounds .
- the organomolybdenum compound is chosen from molybdenum dithiocarbamates.
- Mo-DTC compounds are complexes formed from a metal nucleus of molybdenum bound to one or more ligands, the ligand being an alkyl dithiocarbamate group. These compounds are well known to those skilled in the art.
- the Mo-DTC compound can comprise from 1 to 40%, preferably from 2 to 30%, more preferably from 3 to 28%, advantageously from 4 to 15% by weight of molybdenum, relative to the total weight of the Mo-DTC compound.
- the Mo-DTC compound can comprise from 1 to 40%, preferably from 2 to 30%, more preferably from 3 to 28%, advantageously from 4 to 15% by weight of sulfur , relative to the total weight of the Mo-DTC compound.
- the Mo-DTC compound is a dimeric Mo-DTC compound.
- dimeric Mo-DTC compounds mention may be made of the compounds and their preparation processes as described in documents EP 0757093, EP 0719851, EP 0743354 or EP 1013749.
- the dimeric Mo-DTC compounds generally correspond to the compounds of formula (III): in which :
- R 3 , FU, R 5 , R 6 identical or different, independently represent a hydrocarbon group chosen from alkyl, alkenyl, aryl, cycloalkyl or cycloalkenyl groups,
- X 3 , X 4 , X 5 and Cb identical or different, independently represent an oxygen atom or a sulfur atom.
- alkyl group within the meaning of the invention, is meant a hydrocarbon group, linear or branched, saturated or unsaturated, comprising from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms.
- the alkyl group is chosen from the group formed by methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, l 'hexadecyl, stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-ethylhexyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl , 2-
- alkenyl group within the meaning of the present invention is meant a linear or branched hydrocarbon group comprising at least one double bond and comprising from 2 to 24 carbon atoms.
- the alkenyl group can be chosen from vinyl, allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl and oleic.
- aryl group is intended to mean a polycyclic aromatic hydrocarbon or an aromatic group, whether or not substituted by an alkyl group.
- the aryl group can contain from 6 to 24 carbon atoms.
- the aryl group can be selected from the group formed by phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenylphenyl, phenylphenyl, and -stylphenyl naphthyl.
- cycloalkyl group is intended to mean a polycyclic or cyclic hydrocarbon, whether or not substituted by an alkyl group.
- cycloalkenyl group means a polycyclic or cyclic hydrocarbon, substituted or not by an alkyl group, and comprising at least one unsaturation.
- Cycloalkyl groups and cycloalkenyl groups can have from 3 to 24 carbon atoms.
- the cycloalkyl groups and the cycloalkenyl groups can be chosen, without limitation, from the group consisting of cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl.
- R 3 , FU, R 5 and FÎ 6 independently represent an alkyl group comprising from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms or an alkenyl group comprising from 2 to 24 carbon atoms.
- X 3 , X 4 , X 5 and Cb may be identical and may represent a sulfur atom.
- X 3 , X 4 , X 5 and Cb may be the same and may be an oxygen atom.
- X 3 and X 4 can represent a sulfur atom and X 5 and Cb can represent an oxygen atom.
- X 3 and X 4 can represent an oxygen atom and X 5 and Cb can represent a sulfur atom.
- the ratio of the number of sulfur atoms relative to the number of oxygen atoms (S / O) of the Mo-DTC compound can vary from (1/3) to ( 3/1).
- the Mo-DTC compound of formula (III) can be chosen from a symmetrical Mo-DTC compound, an asymmetric Mo-DTC compound and their combination.
- symmetrical Mo-DTC compound according to the invention is meant an Mo-DTC compound of formula (V) in which the groups R 3 , FU, R 5 and R 6 are identical.
- asymmetric Mo-DTC compound according to the invention is meant an Mo-DTC compound of formula (V) in which the groups R 3 and R 4 are identical, the groups R 5 and R 6 are identical and the groups R 3 and R 4 are different from the R 5 and R 6 groups .
- the Mo-DTC compound is a mixture of at least one symmetrical Mo-DTC compound and at least one asymmetric Mo-DTC compound.
- R 3 and R 4 represent an alkyl group comprising from 5 to 15 carbon atoms, preferably from 8 to 13 carbon atoms
- R 5 and R 6 represent an alkyl group comprising from 5 to 15 carbon atoms, preferably from 8 to 13 carbon atoms
- the groups R 3 and R 4 are identical or different from the groups R 5 and R 6 .
- R 3 and R 4 represent an alkyl group comprising from 6 to 10 carbon atoms and R 5 and R 6 , identical, represent an alkyl group comprising from 10 to 15 carbon atoms, and the R 3 and R 4 groups are different from the R 5 and R 6 groups .
- R 3 and FU represent an alkyl group comprising from 10 to 15 carbon atoms and R 5 and FÎ 6 , identical, represent an alkyl group comprising from 6 to 10 atoms. carbon, and the R 3 and R 4 groups are different from the R 5 and R 6 groups .
- R 3 , R 4 , R 5 and R 6 which are identical, represent an alkyl group comprising from 5 to 15 carbon atoms, preferably from 8 to 13 carbon atoms.
- the Mo-DTC compound is chosen from the compounds of formula (III) in which:
- R 3 represents an alkyl group comprising 8 carbon atoms or an alkyl group comprising 13 carbon atoms
- R 4 represents an alkyl group comprising 8 carbon atoms or an alkyl group comprising 13 carbon atoms
- R 5 represents an alkyl group comprising 8 carbon atoms or an alkyl group comprising 13 carbon atoms
- R 6 represents an alkyl group comprising 8 carbon atoms or an alkyl group comprising 13 carbon atoms.
- the Mo-DTC compound is chosen from the compounds of formula (III-a)
- the Mo-DTC compound is a mixture:
- Mo-DTC compounds As examples of Mo-DTC compounds, mention may be made of the products Molyvan L®, Molyvan 807® or Molyvan 822® marketed by the company RT Vanderbilt Compagny® or the products Sakura-lube 200®, Sakura-lube 165®, Sakura-lube 525® or Sakura-lube 600® marketed by the company Adeka.
- the lubricating composition according to the invention comprises from 50 ppm to 1500 ppm by mass of molybdenum element, preferably from 100 ppm to 1000 ppm by mass, relative to the total mass of the lubricant composition.
- compound 2,5-dimercapto-1, 3,4 thiadiazole alkyl (poly) carboxylate is meant within the meaning of the invention a compound derivative of 2,5-dimercapto-1,3,4 thiadiazole in which at least one of the thiol groups is substituted by an alkyl (poly) carboxylate group.
- alkyl (poly) carboxylate group is meant within the meaning of the invention an alkyl group substituted by one or more carboxylate group. When it is substituted by a single carboxylate group, it is called an “alkyl carboxylate group”. When it is substituted by at least two carboxylate groups, it is called an “alkyl polycarboxylate group”.
- only one of the thiol groups is substituted by an alkyl (poly) carboxylate group.
- the 2,5-dimercapto-1, 3,4 thiadiazole alkyl (poly) carboxylate compound is chosen from the compounds of formula (IV) below: in which R ′ represents a linear, branched or cyclic, saturated or unsaturated, C1-C34 alkyl group substituted by at least one C1-C34 alkyl carboxylate group.
- R ′ represents a linear, branched or cyclic, saturated or unsaturated, C1-C34 alkyl group substituted by at least one C1-C34 alkyl carboxylate group.
- the group R ' is chosen from C 1 -C 30 alkyl groups, more preferably C1-C2 0 , even more preferably C1-C1 0 , and advantageously C 1 -C 5 , substituted with at least a C1-C34 alkyl carboxylate group.
- the R ′ group is chosen from methyl, ethyl, propyl, n-butyl, isobutyl, ferf-butyl, n-pentyl, iso-pentyl and neopentyl groups, substituted with at least one C alkyl carboxylate group. 1 -C 34 .
- the R ′ group is an ethyl group substituted with at least one C 1 -C 34 alkyl carboxylate group.
- the alkyl carboxylate group is chosen from C 1 -C 30 alkyl carboxylate groups, more preferably C 1 -C 2 0, even more preferably C 5 -C 1 0 .
- the alkyl group of the alkyl carboxylate group can be linear, branched or cyclic.
- the alkyl group of the alkyl carboxylate group is selected from branched alkyl groups.
- the alkyl group of the alkyl carboxylate group can be saturated or unsaturated.
- the alkyl group of the alkyl carboxylate group is saturated.
- the alkyl carboxylate group is a 2-ethylhexyl carboxylate group.
- the R ′ group is substituted by at least two C 1 -C 34 alkyl carboxylate groups.
- the alkyl carboxylate groups can be the same or different.
- the alkyl carboxylate groups are identical.
- the alkyl carboxylate groups are all 2-ethylhexyl carboxylate groups.
- the 2,5-dimercapto-1, 3,4 thiadiazole alkyl (poly) carboxylate compound corresponds to the following formula (V):
- V Such compounds are commercially available, in particular from Vanderbilt under the reference Vanlube® 871 (CAS No. 12610453-53-8).
- the organomolybdenum compound and the 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound are present in the additive composition according to the invention in a mass ratio ranging from 1: 100 to 100: 1, preferably 1: 10 to 10: 1, more preferably 1: 5 to 5: 1.
- the lubricating oil composition according to the invention comprises from 0.2% to 1.0% by mass of 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound, preferably 0, 2 to 0.9% by mass, for example 0.5% by mass, relative to the total mass of the lubricating composition.
- Base oil 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound, preferably 0, 2 to 0.9% by mass, for example 0.5% by mass, relative to the total mass of the lubricating composition.
- the base oil used in the lubricating compositions of the invention can be chosen from oils of mineral or synthetic origin belonging to groups I to V according to the classes defined by the API classification (or their equivalents according to the ATIEL classification (Table 1) or their mixtures.
- the mineral base oils of the invention include any type of base oil obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, deasphalting, solvent dewaxing, hydrotreating, hydrocracking, hydro-isomerization and hydrofinishing.
- Mixtures of synthetic and mineral oils can also be used.
- the base oils of the lubricating compositions according to the invention can also be chosen from synthetic oils, such as certain esters of carboxylic acids and alcohols, and polyalphaolefins.
- the polyalphaolefins used as base oil are for example obtained from monomers comprising from 4 to 32 carbon atoms, for example from octene or decene, and for which the viscosity at 100 ° C is between 1 , 5 and 15 mm2.s-1 according to ASTM D445.
- Their average molar mass is generally between 250 and 3000 according to the ASTM D5296 standard.
- the lubricating composition according to the invention comprises at least 50% by mass of base oils, preferably at least 60% by mass, more preferably at least 70% by mass, relative to the total mass of the base oil. composition.
- the lubricating composition according to the invention comprises from 50 to 99.5% by mass of base oils, preferably from 70 to 99.5% by mass of base oils, relative to the total mass of the composition.
- the preferred additives for the lubricating composition according to the invention are chosen from detergent additives, the friction modifying additives differ from the molybdenum compounds defined above, extreme pressure additives, dispersants, pour point activators, agents. defoamers, thickeners and mixtures thereof.
- the lubricating compositions according to the invention comprise at least one extreme pressure additive, or a mixture.
- Anti-wear additives and extreme pressure additives protect surface friction by forming a protective film adsorbed on its surfaces.
- the anti-wear additives are chosen from additives comprising phosphorus and sulfur such as the metals alkylthiophosphate, in particular zinc alkylthiophosphate, and more precisely zinc dialkyldithiophosphate or ZnDTP.
- the preferred compounds are of formula Zn ((SP (S) (OR) (OR ')) 2, in which R and R', identical or different, independently represent an alkyl group, preferably an alkyl group comprising from 1 to 18 carbon atoms.
- Amine phosphates are also antiwear additives which can be used in the lubricating compositions of the invention.
- the phosphorus atoms provided by these additives can act as a poison in automobile catalytic systems since they generate ash.
- additives which do not provide phosphorus such as, for example, polysulfides, in particular olefins containing sulfur.
- the lubricating compositions according to the invention can comprise from 0.01 to 6% by mass, preferably from 0.05 to 4% by mass, more preferably from 0.1 to 2% by mass relative to the total mass of lubricating composition, anti-wear and extreme pressure additives.
- the lubricating compositions according to the invention comprise from 0.01 to 6% by mass, preferably from 0.05 to 4% by mass, more preferably from 0.1 to 2% by mass relative to the total mass of composition.
- compositions according to the invention can comprise at least one friction modifier additive different from the molybdenum compounds of the invention.
- the friction modifying additives can in particular be chosen from compounds providing metallic elements and ashless compounds.
- the compounds providing metallic elements mention may be made of transition metal complexes such as Mo, Sb, Sn, Fe, Cu, Zn for which the ligands may be hydrocarbon compounds comprising oxygen or nitrogen atoms. , sulfur or phosphorus.
- the ashless friction modifier additives are generally of organic origin or can be chosen from fatty acid monoesters and polyols, alkoxylated amines, alkoxylated fatty amines, fatty epoxides, fatty epoxy borates, amines fatty or acid esters of glycerol.
- fatty compounds comprising at least one hydrocarbon group comprising from 10 to 24 carbon atoms.
- the lubricating composition according to the invention can comprise from 0.01 to 2% by mass or from 0.01 to 5% by mass, preferably from 0.1 to 1, 5% by mass or from 0.1 to 2 % by mass relative to the total mass of the lubricating composition, of friction modifier additive different from the molybdenum compounds according to the invention.
- the lubricating composition according to the invention can comprise at least one antioxidant additive.
- Antioxidant additives generally delay the degradation of the lubricating composition. This degradation is most often expressed by the formation of deposit, by the presence of sludge or by an increase in the viscosity of the lubricating composition.
- Antioxidant additives generally act as free radical inhibitors or destructive hydroperoxide inhibitors.
- antioxidants commonly used mention may be made of antioxidants of the phenolic type, antioxidants of the amine type, and antioxidants containing sulfur and phosphorus. Some of these antioxidants, for example those comprising sulfur and phosphorus, can generate ash.
- the phenolic antioxidant additives can be ash free or in the form of neutral or basic metal salts.
- the antioxidant additives can in particular be chosen from sterically hindered phenols, esters of sterically hindered phenols, sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted with at least one C1 to C12 alkyl group, N, N '-dialkyl-aryl-diamines and mixtures thereof.
- the sterically hindered phenols are chosen from compounds comprising a phenol group for which at least one of the carbon atoms in the vicinity of the carbon atom carrying the alcohol function is substituted by at least one alkyl group in C1 to C10, preferably a C1 to C6 alkyl group, preferably a C4 alkyl group, preferably a tert-butyl group.
- Amine compounds are another class of antioxidant additives which can be used, optionally in combination with phenolic antioxidant additives.
- amine compounds are aromatic amines, for example aromatic amines of formula NRaRbRc in which Ra represents an aliphatic group or an aromatic group, optionally substituted, Rb represents an aromatic group, optionally substituted, Rc represents a hydrogen atom, an alkyl group, an aryl group or a group of the formula RdS (0) zRe in which Rd represents an alkylene or alkenylene group, Re represents an alkyl group, an alkenyl group or an aryl group and z represents 0, 1 or 2.
- Sulfur-containing alkyl phenols or their alkali or alkaline earth metal salts can also be used as antioxidant additives.
- antioxidant additives are compounds comprising copper, eg copper thio- or dithiophosphate, copper and carboxylic acid salts, dithiocarbamates, sulfonates, phenates, copper acetylacetonates. Copper I and II salts, salts of succinic acid or succinic anhydride can also be used.
- the lubricating compositions according to the invention can also comprise any type of antioxidant known to those skilled in the art.
- the lubricating composition comprises at least one antioxidant additive free of ash.
- the lubricating composition according to the invention comprises from 0.1 to 2% by mass relative to the total mass of the composition, of at least one antioxidant additive.
- the lubricating composition according to the invention can also comprise at least one detergent additive.
- Detergent additives generally reduce the formation of deposits on the surface of metal parts by dissolving the by-products of oxidation and combustion.
- detergent additives which can be used in the lubricating compositions according to the invention are generally known to those skilled in the art.
- Detergent additives can be anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophobic head.
- the associated cation can be a metal cation of an alkali or alkaline earth metal.
- the detergent additives are preferably chosen from alkali or alkaline earth metal salts of carboxylic acid, sulfonates, salicylates, naphthenates, as well as salts of phenates.
- the alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium.
- metal salts generally include the metal in a stoichiometric amount or in excess, that is to say in a content greater than the stoichiometric content.
- overbased detergents the excess metal implying the overbased nature of the detergent additive is generally in the form of an oil insoluble metal salt, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
- the lubricating composition according to the invention can comprise from 0.5 to 8% or from 2 to 4% by mass of overbased detergent additive relative to the total mass of the lubricating composition.
- the lubricating composition according to the invention can also comprise an additive for lowering the pour point.
- the pour point depressant additive By slowing the formation of paraffin crystals, the pour point depressant additive generally improves the cold behavior of the lubricant composition according to the invention.
- alkyl polymethacrylates As an example of a pour point lowering additive, there may be mentioned, alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalene, alkyl polystyrenes.
- the lubricating composition according to the invention can also comprise a dispersing agent.
- the dispersing agents can be chosen from Mannich bases, succinimides and their derivatives.
- the lubricating composition according to the invention can comprise from 0.2 to 10% by mass of dispersing agent relative to the total mass of lubricating composition.
- the lubricating composition according to the invention can also comprise at least one additional polymer improving the viscosity index.
- additional polymer improving the viscosity index mention may be made of polymeric esters, homopolymers or copolymers, hydrogenated or not, of styrene, butadiene, and isoprene, polymethacrylates (PMA).
- the lubricating composition according to the invention can comprise from 1 to 15% by mass, relative to the total mass of lubricating composition, of additive improving the viscosity index.
- the lubricating composition according to the invention can also comprise at least one thickening agent.
- the lubricating composition according to the invention can also comprise an anti-foaming agent and a demulsifying agent.
- the lubricating composition according to the invention comprises:
- organomolybdenum compound from 0.1% to 1.5% by mass of organomolybdenum compound
- the lubricating composition according to the invention comprises:
- the lubricating composition has a sulfur content ranging from 0.01% to 5% by mass, preferably 0.1% to 2% by mass, more preferably from 0.1% to 0.5% by mass, relative to the total mass of the lubricating composition.
- the invention also relates to the use of a 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound to protect an organomolybdenum compound, for example MoDTC, from its degradation, preferably to protect the organomolybdenum compound, for example MoDTC.
- organomolybdenum compound, eg MoDTC from oxidation.
- the present invention also relates to the use of a 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound in a lubricating composition comprising at least one base oil and at least one organomolybdenum compound, for example an organic molybdenum complex with dithiocarbamate ligands, to maintain the Fuel Eco properties of the lubricating composition over time.
- a lubricating composition comprising at least one base oil and at least one organomolybdenum compound, for example an organic molybdenum complex with dithiocarbamate ligands
- the present invention also relates to a process for protecting the degradation, in particular by oxidation, of the organomolybdenum compound, for example MoDTC, of a lubricating composition comprising at least one base oil and an organomolybdenum compound, for example MoDTC, comprising l addition, in said lubricating composition, of a 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound.
- organomolybdenum compound for example MoDTC
- the present invention also relates to a process for maintaining the Fuel Eco properties over time of a lubricating lubricating composition comprising at least one base oil and an organomolybdenum compound, for example MoDTC, comprising the addition, in said lubricating composition of a 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound.
- organomolybdenum compound for example MoDTC
- the variants and embodiments detailed below for the organomolybdenum compound and for the 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound also apply to the different uses defined above.
- the maintenance of the Fuel Eco properties of a lubricating composition can typically be evaluated by determining the change in the coefficient of friction of the composition during the operation of an engine lubricated with the composition to be tested.
- a sample of the lubricating composition is taken.
- the measurement of the coefficient of friction of the composition is then carried out according to any method known to those skilled in the art. It can for example be carried out by means of a reciprocating ball-plane tribometer. It is understood that the lower the coefficient of friction is over time, the more the effects on the fuel eco properties of the lubricating composition are maintained over time.
- a lubricating composition comprising at least one base oil and one organomolybdenum compound, for example MoDTC; and or
- FIG. 1 represents the change in the coefficient of friction of a composition according to the invention and of a reference composition as a function of the operating time of the engine. Examples:
- base oil formulated base oil of grade OW-12.
- This base oil includes:
- MoDTC molybdenum dithiocarbarmate
- compositions C0 and C1 are prepared by mixing the various constituents according to the contents indicated in Table 2 below.
- the CO composition is a reference composition (base oil without additives).
- Composition C1 is a composition according to the invention.
- the friction coefficients of the lubricating compositions C0 and C1 are measured under engine test conditions according to the following method.
- Each lubricating composition (10 kg) is evaluated during a cleanliness test of a turbo-compressed gasoline engine.
- the engine has a displacement of 1.6 L for 4 cylinders. Its power is 115 kW.
- the test cycle duration is 30 hours, alternating idling speed (between 500 and 750 rpm) and severe circulation speed (between 2500 and 5800 rpm).
- the temperature of the lubricating composition is between 50 and 150 ° C and the temperature of the water in the cooling system is between 50 and 97 ° C. No draining or any addition of lubricating composition is carried out during the test. E10 fuel is used.
Abstract
Disclosed is a composition of additives for lubricant oil, comprising at least one organomolybdenum compound and at least one 2,5-dimercapto-1,3,4-thiadiazole alkyl polycarboxylate compound.
Description
Composition lubrifiante comprenant un composé 2,5-dimercapto-1,3,4-thiadiazole alkyl polycarboxylate Lubricating composition comprising a 2,5-dimercapto-1,3,4-thiadiazole alkyl polycarboxylate compound
L’invention concerne le domaine des compositions lubrifiantes, en particulier les propriétés d’économie de carburant dites fuel economy ( FE ou fueleco) des compositions lubrifiantes. Plus précisément, l’invention concerne une composition d’additifs permettant de maintenir dans le temps les propriétés de fuel economy d’une composition lubrifiante (FE rétention ou fuel eco rétention). L’invention concerne également l’utilisation dans une composition lubrifiante d’une composition d’additifs selon l’invention ainsi que la composition lubrifiante résultante. The invention relates to the field of lubricating compositions, in particular the fuel economy properties known as fuel economy (FE or fueleco) of lubricating compositions. More specifically, the invention relates to an additive composition making it possible to maintain over time the fuel economy properties of a lubricating composition (FE retention or fuel eco retention). The invention also relates to the use in a lubricating composition of an additive composition according to the invention as well as the resulting lubricating composition.
Les développements des moteurs et les performances des compositions lubrifiantes pour moteur sont indissociablement liés. Plus les moteurs ont une conception complexe, plus le rendement et l'optimisation de la consommation de carburant sont élevés et plus les performances de la composition lubrifiante doivent être améliorées. Engine developments and the performance of lubricating compositions for engines are inextricably linked. The more complex the engine design, the higher the efficiency and the optimization of fuel consumption, and the more the performance of the lubricating composition needs to be improved.
Les conditions d'utilisation des moteurs à essence et des moteurs diesel incluent aussi bien des parcours extrêmement courts que de longs trajets. En effet, 80 % des trajets des voitures d'Europe occidentale sont inférieurs à 12 kilomètres alors que des véhicules parcourent des kilométrages annuels allant jusqu'à 300 000 km. The conditions of use for gasoline and diesel engines include both extremely short and long journeys. In fact, 80% of car journeys in Western Europe are less than 12 kilometers while vehicles cover annual mileages of up to 300,000 km.
Les intervalles de vidange sont également très variables, de 5 000 km pour certains petits moteurs diesel, ils peuvent aller jusqu'à 100 000 km sur des moteurs diesel de véhicules utilitaires modernes. The oil change intervals are also very variable, from 5,000 km for some small diesel engines, they can go up to 100,000 km on modern commercial vehicle diesel engines.
Les compositions lubrifiantes pour véhicules à moteur doivent être adaptables à toutes ces conditions d’utilisations et ainsi doivent posséder des propriétés et des performances améliorées. Lubricating compositions for motor vehicles must be adaptable to all of these conditions of use and thus must have improved properties and performance.
Les compositions lubrifiantes pour moteur doivent remplir de nombreux objectifs. Engine lubricating compositions must serve many purposes.
La lubrification des pièces glissant les unes sur les autres joue un rôle déterminant, en particulier pour réduire le frottement entre ces pièces et par conséquent l'usure de celles- ci, permettant notamment des économies de carburant. The lubrication of the parts sliding over one another plays a decisive role, in particular in reducing the friction between these parts and consequently the wear thereof, in particular allowing fuel savings.
Une exigence essentielle des compositions lubrifiantes pour moteur concerne les aspects liés à l'environnement. Il est en effet devenu essentiel de réduire la consommation de carburant dans le but de réduire les émissions de CO2. An essential requirement of lubricating compositions for engines relates to environmental aspects. It has indeed become essential to reduce fuel consumption in order to reduce CO2 emissions.
La nature des compositions lubrifiantes pour moteur pour automobiles a une influence sur la consommation de carburant. Les compositions lubrifiantes pour moteur automobiles
permettant des économies de carburant sont souvent désignées fuel eco (FE), en terminologie anglo-saxonne. The nature of the lubricating compositions for motor vehicles has an influence on the fuel consumption. Lubricating compositions for automobile engines allowing fuel savings are often referred to as fuel eco (FE), in English terminology.
L'amélioration du niveau de performances fuel eco est constamment recherchée dans la formulation des lubrifiants pour automobile. The improvement of the fuel eco performance level is constantly sought in the formulation of automotive lubricants.
Toutefois, cette amélioration du niveau de performances n'est pas suffisante. Elle doit s'accompagner du maintien ou de la conservation dans le temps de ce niveau de performances fuel eco obtenues par la mise en œuvre des compositions lubrifiantes.However, this improvement in the performance level is not sufficient. It must be accompanied by the maintenance or conservation over time of this level of fuel eco performance obtained by the use of lubricating compositions.
Lors de l'utilisation d'une composition lubrifiante dans un moteur entraînant un vieillissement de celle-ci, les performances fuel eco doivent être maintenues autant que possible. En effet, une diminution de ces performances fuel eco en réduit d'autant les bénéfices. Ainsi, outre le besoin d'atteindre un niveau élevé de performances fuel eco, il est important de pouvoir maintenir ou conserver ce niveau de performances fuel eco d'une composition lubrifiante dans le temps, par exemple entre deux intervalles de vidange ou après un certain nombre de kilomètres parcourus. When using a lubricating composition in an engine causing aging thereof, fuel eco performance must be maintained as much as possible. Indeed, a decrease in these fuel eco performance reduces the benefits accordingly. Thus, in addition to the need to achieve a high level of fuel eco performance, it is important to be able to maintain or maintain this level of fuel eco performance of a lubricating composition over time, for example between two oil change intervals or after a certain period. number of kilometers traveled.
En particulier, il est important de pouvoir disposer de compositions lubrifiantes permettant de conserver un bon niveau d'économie de carburant d'un moteur, en particulier d'un moteur de véhicule. In particular, it is important to be able to have available lubricating compositions which make it possible to maintain a good level of fuel economy of an engine, in particular of a vehicle engine.
Il est connu d’ajouter aux compositions lubrifiantes des modificateurs de frottement tels que des composés organomolybdène pour faire baisser le coefficient de frottement. L’ajout de tels composés permet notamment des économies de carburant et confère au lubrifiant des propriétés FE. Parmi les modificateurs de frottement utilisés, le MoDTC (molybdène dithiocarbamate) est l’un des additifs les plus efficaces pour faire baisser le coefficient de frottement et par conséquent obtenir des économies de carburant. It is known to add friction modifiers such as organomolybdenum compounds to lubricating compositions to lower the coefficient of friction. The addition of such compounds allows in particular fuel savings and gives the lubricant FE properties. Among the friction modifiers used, MoDTC (molybdenum dithiocarbamate) is one of the most effective additives in lowering the coefficient of friction and therefore obtaining fuel savings.
Lors du fonctionnement du moteur, le composé organomolybdène tel que le MoDTC forme deux composés le M0S2 (bisulfure de molybdène lamellaire) qui permet la réduction du frottement et le trioxyde de molybdène (M0O3) qui tend à augmenter l’usure. During engine operation, the organomolybdenum compound such as MoDTC forms two compounds M0S 2 (lamellar molybdenum disulphide) which reduces friction and molybdenum trioxide (M0O 3 ) which tends to increase wear.
Le Molybdène formant une partie du composé organomolybdène s’oxyde ce qui est responsable de la perte de performance du composé organomolybdène dans le temps et donc une perte de performance du Fuel Eco de la composition lubrifiante (et donc de l’économie de carburant) dans le temps. The Molybdenum forming part of the organomolybdenum compound oxidizes which is responsible for the loss of performance of the organomolybdenum compound over time and therefore a loss of performance of the Fuel Eco of the lubricating composition (and therefore of the fuel economy) in the weather.
Pour remédier à ce problème, il est possible de mettre en œuvre des modificateurs de frottement organique qui sont cependant moins efficaces. Il a également été envisagé une augmentation de la quantité de composé organomolybdène. Une teneur élevée en élément molybdène représente toutefois un surcoût considérable de formulation. Par ailleurs, à une
teneur élevée, typiquement supérieure à 1 500 ppm, les compositions lubrifiantes ne sont plus stables, ces problèmes de stabilité se traduisant par un risque élevé d’encrassement du moteur et/ou de la corrosion du moteur, notamment des moteurs en cuivre. To remedy this problem, it is possible to use organic friction modifiers which are however less effective. An increase in the amount of organomolybdenum compound has also been envisaged. However, a high content of molybdenum element represents a considerable additional formulation cost. Moreover, to a high content, typically greater than 1500 ppm, the lubricating compositions are no longer stable, these stability problems resulting in a high risk of engine fouling and / or engine corrosion, in particular copper engines.
Il existe donc un besoin de disposer de compositions lubrifiantes pour moteur, notamment pour moteur de véhicule, qui permettent d’apporter une solution à tout ou partie des problèmes des compositions lubrifiantes de l’état de la technique. There is therefore a need to have lubricating compositions for an engine, in particular for a vehicle engine, which make it possible to provide a solution to all or part of the problems of lubricating compositions of the state of the art.
Un objectif de la présente invention est de fournir une composition lubrifiante ayant des propriétés de Fuel Eco prolongées dans le temps et par conséquent de maintenir une réduction de consommation de carburant dans le temps. An objective of the present invention is to provide a lubricating composition having Fuel Eco properties that are prolonged over time and therefore to maintain a reduction in fuel consumption over time.
Un autre objectif de la présente invention est de fournir une composition lubrifiante permettant le maintien d’un bas coefficient de frottement dans le temps. Another objective of the present invention is to provide a lubricating composition which makes it possible to maintain a low coefficient of friction over time.
Un autre objectif encore de la présente invention est de fournir une solution à la diminution de l’efficacité du composé organomolybdène dans le temps. Yet another object of the present invention is to provide a solution to the decrease in the effectiveness of the organomolybdenum compound over time.
Un autre objectif encore de la présente invention est de proposer un composé permettant de protéger le composé organomolybdène d’une composition lubrifiante de sa dégradation au cours du temps, notamment par oxydation. Yet another objective of the present invention is to provide a compound making it possible to protect the organomolybdenum compound of a lubricating composition from its degradation over time, in particular by oxidation.
D’autres objectifs encore apparaîtront à la lecture de la description de l’invention qui suit. Still other objects will become apparent on reading the following description of the invention.
Résumé de l’invention Summary of the invention
L’invention concerne tout d’abord une composition d’additifs pour huile lubrifiante comprenant : The invention relates first of all to a composition of additives for lubricating oil comprising:
- au moins un composé organomolybdène, et - at least one organomolybdenum compound, and
- au moins un composé 2,5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate. - at least one 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound.
L’invention concerne également une composition lubrifiante comprenant : The invention also relates to a lubricating composition comprising:
- au moins une huile de base, et - at least one base oil, and
- au moins une composition d’additifs telle que définie ci-dessus et de manière détaillée ci- dessous. - at least one additive composition as defined above and in detail below.
L’invention concerne enfin l’utilisation d’un composé 2, 5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate dans une composition lubrifiante comprenant au moins une huile de base et au moins un composé organomolybdène, de préférence choisi parmi les composés organomolybdène dinucléaires.
De préférence, le composé 2,5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate est utilisé pour maintenir dans le temps les économies de carburant d’un moteur à combustion interne. The invention finally relates to the use of a 2, 5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound in a lubricating composition comprising at least one base oil and at least one organomolybdenum compound, preferably chosen from dinuclear organomolybdenum compounds. Preferably, the 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound is used to maintain the fuel economy of an internal combustion engine over time.
Avantageusement, le ratio massique entre le composé organomolybdène et le composéAdvantageously, the mass ratio between the organomolybdenum compound and the compound
2,5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate va de 1 :100 à 100 :1 , de préférence de 1 :10 à 10 :1 , plus préférentiellement de 1 :5 à 5 :1. 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate ranges from 1: 100 to 100: 1, preferably from 1: 10 to 10: 1, more preferably from 1: 5 to 5: 1.
Avantageusement, le composé organomolybdène est choisi parmi les composés organomolybdène dinucléaires, de préférence parmi les dithiocarbamates de molybdène. Advantageously, the organomolybdenum compound is chosen from dinuclear organomolybdenum compounds, preferably from molybdenum dithiocarbamates.
Avantageusement, le composé 2,5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate est choisi parmi les composés de formule (IV) suivante :
dans laquelle R’ représente un groupement alkyle en C1-C34 substitué par au moins un groupement carboxylate d’alkyle en C1-C34, de préférence au moins deux groupements carboxylate d’alkyle en C1-C34. Advantageously, the 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound is chosen from the compounds of formula (IV) below: in which R 'represents a C1-C34 alkyl group substituted by at least one C 1 -C 34 alkyl carboxylate group, preferably at least two C 1 -C 34 alkyl carboxylate groups.
De préférence, le groupement R’ est un groupement alkyle en C1-C30, de préférence en C1- C20, plus préférentiellement en C1-C10, typiquement en C1-C5, par exemple est un groupement éthyle. Preferably, the group R ′ is a C1-C30, preferably C1-C20, more preferably C1-C10, typically C1-C5 alkyl group, for example an ethyl group.
De préférence, le ou les groupement(s) carboxylate d’alkyle sont choisi, de manière indépendante, parmi les groupements carboxylate d’alkyle en C1-C30, de préférence en C1- C20, plus préférentiellement en C1-C10, par exemple est un groupement 2-éthylhexyl. Preferably, the alkyl carboxylate group (s) are chosen, independently, from the alkyl carboxylate groups in C1-C30, preferably in C1-C20, more preferably in C1-C10, for example is a 2-ethylhexyl group.
Plus avantageusement, le composé 2, 5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate répond à la formule (V) suivante :
De préférence, la composition lubrifiante comprend de 50% à 99 ,5% en masse d’huile de base, par rapport à la masse totale de la composition lubrifiante. More advantageously, the compound 2, 5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate corresponds to the following formula (V): Preferably, the lubricating composition comprises from 50% to 99.5% by mass of base oil, relative to the total mass of the lubricating composition.
De préférence, la teneur en élément molybdène dans la composition lubrifiante va de 50 à 1 500 ppm en masse, de préférence de 100 à 1 000 ppm en masse, par rapport à la masse totale de la composition lubrifiante. Preferably, the content of molybdenum element in the lubricating composition ranges from 50 to 1,500 ppm by mass, preferably from 100 to 1,000 ppm by mass, relative to the total mass of the lubricating composition.
De préférence, la composition lubrifiante comprend de 0,2% à 1 ,0% en masse de composé 2,5-dimercapto-1 ,3,4-thiadiazole, alkyl (poly)carboxylate, de préférence 0,2 à 0,9% en masse, par exemple 0,5% en masse, par rapport à la masse totale de la composition lubrifiante. Preferably, the lubricating composition comprises from 0.2% to 1.0% by mass of 2,5-dimercapto-1, 3,4-thiadiazole, alkyl (poly) carboxylate compound, preferably 0.2 to 0.9 % by mass, for example 0.5% by mass, relative to the total mass of the lubricating composition.
Avantageusement, la composition lubrifiante présente une teneur en soufre allant de 0,01 % à 5% en masse, de préférence de 0,1 % à 2% en masse, plus préférentiellement de 0,1% à 0,5% en masse, par rapport à la masse totale de la composition. Advantageously, the lubricating composition has a sulfur content ranging from 0.01% to 5% by mass, preferably from 0.1% to 2% by mass, more preferably from 0.1% to 0.5% by mass, relative to the total mass of the composition.
Sans vouloir être lié par une quelconque théorie, le composé 2,5-dimercapto-1 ,3,4- thiadiazole alkyl (poly)carboxylate est plus stable thermiquement que les autres composés soufrés utilisés dans les compositions lubrifiantes comme par exemple un composé polysulfure ou un composé phospho-soufré. Ainsi, la présence du composé 2,5-dimercapto- 1 ,3,4-thiadiazole alkyl (poly)carboxylate dans une composition lubrifiante comprenant un composé organomolybdène, comme par exemple le dithiocarbamate de molybdène, également appelé MoDTC, permet de réduire l’oxydation du molybdène voire de protéger le molybdène de l’oxydation et de promouvoir la sulfuration du composé organomolybdène et des sous-produits sulfurés du molybdène et donc de maintenir dans le temps, les propriétés du composé organomolybdène, comme par exemple le MoDTC. Without wishing to be bound by any theory, the compound 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate is more thermally stable than the other sulfur compounds used in lubricating compositions such as for example a polysulfide compound or a phospho-sulfur compound. Thus, the presence of the 2,5-dimercapto- 1,3,4-thiadiazole alkyl (poly) carboxylate compound in a lubricating composition comprising an organomolybdenum compound, such as for example molybdenum dithiocarbamate, also called MoDTC, makes it possible to reduce the oxidation of molybdenum or even to protect the molybdenum from oxidation and to promote the sulfurization of the organomolybdenum compound and of the sulfurized by-products of molybdenum and therefore to maintain over time the properties of the organomolybdenum compound, such as, for example, MoDTC.
Sans vouloir être lié par une quelconque théorie, la combinaison d’un composé 2,5- dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate avec un composé organomolybdène, comme par exemple le MoDTC, permet un maintien du coefficient de frottement bas dans le temps, un maintien des propriétés FE du lubrifiant dans le temps et ainsi une économie de carburant dans le temps. Without wishing to be bound by any theory, the combination of a 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound with an organomolybdenum compound, such as for example MoDTC, allows the coefficient of low friction over time, maintaining the FE properties of the lubricant over time and thus fuel economy over time.
Description détaillée de l’invention Detailed description of the invention
L’invention concerne une composition d’additifs pour huile lubrifiante comprenant : The invention relates to a lubricating oil additive composition comprising:
- au moins un composé organomolybdène, et - at least one organomolybdenum compound, and
- au moins un composé 2,5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate. L’invention a également pour objet une composition lubrifiante comprenant :
- au moins une huile de base, - at least one 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound. A subject of the invention is also a lubricating composition comprising: - at least one base oil,
- au moins un composé organomolybdène, et - at least one organomolybdenum compound, and
- au moins un composé 2,5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate. - at least one 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound.
Le composé organomolybdène The organomolybdenum compound
Par composé organomolybdène selon l’invention on entend désigner tout composé organomolybdène liposoluble. By organomolybdenum compound according to the invention is meant any liposoluble organomolybdenum compound.
Le composé organomolybdène selon la présente invention, peut être choisi parmi les complexes organiques du molybdène comprenant au moins un élément chimique molybdène (Mo), de préférence au moins deux éléments chimiques molybdène (Mo), et au moins un ligand tel qu’un ligand carboxylate, un ligand ester, un ligand amide, un ligand dithiophosphate, un ligand dithiocarbamate. The organomolybdenum compound according to the present invention can be chosen from organic molybdenum complexes comprising at least one chemical element molybdenum (Mo), preferably at least two chemical elements molybdenum (Mo), and at least one ligand such as a ligand. carboxylate, ester ligand, amide ligand, dithiophosphate ligand, dithiocarbamate ligand.
Par exemple, les complexes organiques du molybdène avec des carboxylates, des esters, des amides peuvent être obtenus par réaction d’oxyde de molybdène ou de molybdates d’ammonium avec des corps gras, glycérides, acides gras ou dérivés d’acides gras (esters, amines, amides, ...). For example, the organic complexes of molybdenum with carboxylates, esters, amides can be obtained by reaction of molybdenum oxide or ammonium molybdates with fatty substances, glycerides, fatty acids or derivatives of fatty acids (esters , amines, amides, ...).
Au sens de l’invention, les ligands carboxylates, les ligands esters et les ligands amides sont exempts de soufre et de phosphore. For the purposes of the invention, the carboxylate ligands, the ester ligands and the amide ligands are free from sulfur and phosphorus.
Dans un mode de réalisation, le composé organomolybdène de l’invention est choisi parmi les complexes du molybdène avec des ligands amide, principalement préparés par réaction d’une source de molybdène, qui peut être par exemple le trioxyde de molybdène, et d’un dérivé d’amine, et d’acides gras comprenant par exemple de 4 à 36 atomes de carbone tels que par exemple les acides gras contenus dans les huiles végétales ou animales. In one embodiment, the organomolybdenum compound of the invention is chosen from complexes of molybdenum with amide ligands, mainly prepared by reaction of a source of molybdenum, which may for example be molybdenum trioxide, and of a derivative of amine, and of fatty acids comprising, for example, from 4 to 36 carbon atoms, such as, for example, the fatty acids contained in vegetable or animal oils.
La synthèse de tels composés est par exemple décrite dans les brevets US4889647, EP0546357, US5412130 ou EP1770153. The synthesis of such compounds is for example described in patents US4889647, EP0546357, US5412130 or EP1770153.
Selon un mode de réalisation préféré, le composé organomolybdène est choisi parmi les composés organomolydbène dinucléaires. According to a preferred embodiment, the organomolybdenum compound is chosen from dinuclear organomolydbene compounds.
Par « composé organomolybdène dinucléaire », on entend au sens de l’invention des composés organomolybdène dont le noyau présente deux atomes de molybdène. On parle également de composés organomolydbène dimériques. By "dinuclear organomolybdenum compound" is meant within the meaning of the invention organomolybdenum compounds whose nucleus has two molybdenum atoms. We also speak of dimeric organomolydbene compounds.
Dans un mode de réalisation préféré de l’invention, le composé organomolybdène est choisi parmi les complexes organiques du molybdène avec des ligands amide obtenus par réaction : In a preferred embodiment of the invention, the organomolybdenum compound is chosen from organic complexes of molybdenum with amide ligands obtained by reaction:
(i) d’un corps gras de type mono, di ou tri glycéride, ou acide gras,
(ii) d’une source aminée de formule (A) :
(i) of a fatty substance of mono, di or tri glyceride type, or fatty acid, (ii) from an amino source of formula (A):
Dans laquelle : In which :
- X1 représente un atome d’oxygène ou un atome d’azote, - X2 représente un atome d’oxygène ou un atome d’azote, - X 1 represents an oxygen atom or a nitrogen atom, - X 2 represents an oxygen atom or a nitrogen atom,
- n ou m représente 1 lorsque respectivement X1 ou X2 représente un atome d’oxygène,- n or m represents 1 when respectively X 1 or X 2 represents an oxygen atom,
- n ou m représente 2 lorsque respectivement X1 ou X2 représente un atome d’azote,- n or m represents 2 when respectively X 1 or X 2 represents a nitrogen atom,
(iii) et d’une source de molybdène choisie parmi le trioxyde de molybdène ou les molybdates, préférentiellement le molybdate d’ammonium. (iii) and a source of molybdenum chosen from molybdenum trioxide or molybdates, preferably ammonium molybdate.
Dans un mode de réalisation de l’invention, le composé organomolybdène peut comprendre de 0,1 à 30% en poids, de préférence de 0,1 à 20%, plus préférentiellement de 2 à 8,5% en poids de molybdène par rapport au poids total du complexe organomolybdène. De préférence, le composé organomolybdène comprend au moins un complexe organique du molybdène de formule (I) ou (II), seul ou en mélange :
dans laquelle : In one embodiment of the invention, the organomolybdenum compound may comprise from 0.1 to 30% by weight, preferably from 0.1 to 20%, more preferably from 2 to 8.5% by weight of molybdenum relative to to the total weight of the organomolybdenum complex. Preferably, the organomolybdenum compound comprises at least one organic molybdenum complex of formula (I) or (II), alone or as a mixture: in which :
X1 représente un atome d’oxygène ou un atome d’azote ; X2 représente un atome d’oxygène ou un atome d’azote ; n représente 1 lorsque X1 représente un atome d’oxygène et m représente 1 lorsque X2 représente un atome d’oxygène ; n représente 2 lorsque X1 représente un atome d’azote et m représente 2 lorsque X2 représente un atome d’azote ; Ri représente un groupement alkyle linéaire ou ramifié, saturé ou insaturé, comprenant de 4 à 36 atomes de carbone, préférentiellement de 4 à 20 atomes de carbone, avantageusement de 6 à 18 atomes de carbone ;
dans laquelle : X 1 represents an oxygen atom or a nitrogen atom; X 2 represents an oxygen atom or a nitrogen atom; n represents 1 when X 1 represents an oxygen atom and m represents 1 when X 2 represents an oxygen atom; n represents 2 when X 1 represents a nitrogen atom and m represents 2 when X 2 represents a nitrogen atom; R 1 represents a linear or branched, saturated or unsaturated alkyl group comprising from 4 to 36 carbon atoms, preferably from 4 to 20 carbon atoms, advantageously from 6 to 18 carbon atoms; in which :
X1 représente un atome d’oxygène ou un atome d’azote ; X 1 represents an oxygen atom or a nitrogen atom;
X2 représente un atome d’oxygène ou un atome d’azote ; n représente 1 lorsque X1 représente un atome d’oxygène et m représente 1 lorsque X2 représente un atome d’oxygène ; n représente 2 lorsque X1 représente un atome d’azote et m représente 2 lorsque X2 représente un atome d’azote ; X 2 represents an oxygen atom or a nitrogen atom; n represents 1 when X 1 represents an oxygen atom and m represents 1 when X 2 represents an oxygen atom; n represents 2 when X 1 represents a nitrogen atom and m represents 2 when X 2 represents a nitrogen atom;
Ri représente un groupement alkyle linéaire ou ramifié, saturé ou insaturé, comprenant de 4 à 36 atomes de carbone, préférentiellement de 4 à 20 atomes de carbone, avantageusement de 6 à 18 atomes de carbone ; R 1 represents a linear or branched, saturated or unsaturated alkyl group comprising from 4 to 36 carbon atoms, preferably from 4 to 20 carbon atoms, advantageously from 6 to 18 carbon atoms;
R2 représente un groupement alkyle linéaire ou ramifié, saturé ou insaturé, comprenant de 4 à 36 atomes de carbone, préférentiellement de 4 à 20 atomes de carbone, avantageusement de 6 à 18 atomes de carbone. R2 represents a linear or branched, saturated or unsaturated alkyl group comprising from 4 to 36 carbon atoms, preferably from 4 to 20 carbon atoms, advantageously from 6 to 18 carbon atoms.
Avantageusement, le complexe organique du molybdène de formule (I) ou (II) est préparé par réaction : Advantageously, the organic molybdenum complex of formula (I) or (II) is prepared by reaction:
(i) d’un corps gras de type mono, di ou tri glycéride, ou acide gras, (i) a fatty substance of the mono, di or tri glyceride type, or fatty acid,
(ii) de diéthanolamine ou de 2-(2-aminoéthyl) aminoéthanol, (ii) diethanolamine or 2- (2-aminoethyl) aminoethanol,
(iii) et d’une source de molybdène choisie parmi le trioxyde de molybdène ou les molybdates, préférentiellement le molybdate d’ammonium. (iii) and a source of molybdenum chosen from molybdenum trioxide or molybdates, preferably ammonium molybdate.
Plus avantageusement, le complexe organique du molybdène de formule (I) est constitué d’au moins un composé de formule (l-a) ou (l-b), seul ou en mélange :
(|-a) dans laquelle Ri représente un groupement alkyle linéaire ou ramifié, saturé ou insaturé, comprenant de 4 à 36 atomes de carbone, préférentiellement de 4 à 20 atomes de carbone, avantageusement de 6 à 18 atomes de carbone,
dans laquelle Ri représente un groupement alkyle linéaire ou ramifié, saturé ou insaturé, comprenant de 4 à 36 atomes de carbone, préférentiellement de 4 à 20 atomes de carbone, avantageusement de 6 à 18 atomes de carbone. More advantageously, the organic molybdenum complex of formula (I) consists of at least one compound of formula (la) or (lb), alone or as a mixture: (| -a) in which R 1 represents a linear or branched, saturated or unsaturated alkyl group comprising from 4 to 36 carbon atoms, preferably from 4 to 20 carbon atoms, advantageously from 6 to 18 carbon atoms, in which R 1 represents a linear or branched, saturated or unsaturated alkyl group comprising from 4 to 36 carbon atoms, preferably from 4 to 20 carbon atoms, advantageously from 6 to 18 carbon atoms.
Comme exemple de complexes de molybdène exempts de soufre selon l’invention, on peut citer le Molyvan 855® commercialisé par la société Vanderbilt. As an example of sulfur-free molybdenum complexes according to the invention, mention may be made of Molyvan 855® sold by the company Vanderbilt.
Dans un autre mode de réalisation de l’invention, le composé organomolybdène est choisi parmi les complexes organiques du molybdène avec des ligands dithiophosphates ou les complexes organiques du molybdène avec des ligands dithiocarbamates. In another embodiment of the invention, the organomolybdenum compound is chosen from organic complexes of molybdenum with dithiophosphate ligands or organic complexes of molybdenum with dithiocarbamate ligands.
Au sens de l’invention, les complexes organiques du molybdène avec des ligands dithiophosphates sont également appelés les dithiophosphates de molybdène ou composés Mo-DTP et les complexes organiques du molybdène avec des ligands dithiocarbamates sont également appelés les dithiocarbamates de molybdène ou composés Mo-DTC. For the purposes of the invention, organic complexes of molybdenum with dithiophosphate ligands are also called molybdenum dithiophosphates or Mo-DTP compounds and organic complexes of molybdenum with dithiocarbamate ligands are also called molybdenum dithiocarbamates or Mo-DTC compounds .
Dans un mode de réalisation plus préféré de l’invention, le composé organomolybdène est choisi parmi les dithiocarbamates de molybdène. In a more preferred embodiment of the invention, the organomolybdenum compound is chosen from molybdenum dithiocarbamates.
Les composés Mo-DTC sont des complexes formés d’un noyau métallique de molybdène lié à un ou plusieurs ligands, le ligand étant un groupement dithiocarbamate d’alkyles. Ces composés sont bien connus de l’homme du métier. Mo-DTC compounds are complexes formed from a metal nucleus of molybdenum bound to one or more ligands, the ligand being an alkyl dithiocarbamate group. These compounds are well known to those skilled in the art.
Dans un mode de réalisation de l’invention, le composé Mo-DTC peut comprendre de 1 à 40%, de préférence de 2 à 30%, plus préférentiellement de 3 à 28%, avantageusement de 4 à 15% en poids de molybdène, par rapport au poids total du composé Mo-DTC. In one embodiment of the invention, the Mo-DTC compound can comprise from 1 to 40%, preferably from 2 to 30%, more preferably from 3 to 28%, advantageously from 4 to 15% by weight of molybdenum, relative to the total weight of the Mo-DTC compound.
Dans un autre mode de réalisation de l’invention, le composé Mo-DTC peut comprendre de 1 à 40%, de préférence de 2 à 30%, plus préférentiellement de 3 à 28%, avantageusement de 4 à 15% en poids de soufre, par rapport au poids total du composé Mo-DTC.
Dans un mode de réalisation préféré de l’invention, le composé Mo-DTC est un composé Mo-DTC dimérique. In another embodiment of the invention, the Mo-DTC compound can comprise from 1 to 40%, preferably from 2 to 30%, more preferably from 3 to 28%, advantageously from 4 to 15% by weight of sulfur , relative to the total weight of the Mo-DTC compound. In a preferred embodiment of the invention, the Mo-DTC compound is a dimeric Mo-DTC compound.
Comme exemples de composés Mo-DTC dimériques, on peut citer les composés et leurs procédés de préparation tels que décrits dans les documents EP 0757093, EP 0719851 , EP 0743354 ou EP 1013749. As examples of dimeric Mo-DTC compounds, mention may be made of the compounds and their preparation processes as described in documents EP 0757093, EP 0719851, EP 0743354 or EP 1013749.
Les composés Mo-DTC dimériques correspondent généralement aux composés de formule (III) :
dans laquelle : The dimeric Mo-DTC compounds generally correspond to the compounds of formula (III): in which :
R3, FU, R5, R6, identiques ou différents, représentent indépendamment un groupement hydrocarboné choisi parmi les groupements alkyle, alcényle, aryle, cycloalkyle ou cycloalcényle, R 3 , FU, R 5 , R 6 , identical or different, independently represent a hydrocarbon group chosen from alkyl, alkenyl, aryl, cycloalkyl or cycloalkenyl groups,
X3, X4, X5 et Cb, identiques ou différents, représentent indépendamment un atome d’oxygène ou un atome de soufre. X 3 , X 4 , X 5 and Cb, identical or different, independently represent an oxygen atom or a sulfur atom.
Par groupement alkyle au sens de l’invention, on entend un groupement hydrocarboné, linéaire ou ramifié, saturé ou insaturé, comprenant de 1 à 24 atomes de carbone, de préférence de 4 à 18 atomes de carbone. By alkyl group within the meaning of the invention, is meant a hydrocarbon group, linear or branched, saturated or unsaturated, comprising from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms.
Dans un mode de réalisation de l’invention, le groupement alkyle est choisi dans le groupe formé par le méthyle, l’éthyle, le propyle, l’isopropyle, le n-butyle, l’iso-butyle, le tert-butyle, le n-pentyle, l’iso-pentyle, le néopentyle, l’hexyle, l’heptyle, l’octyle, le nonyle, le décyle, l’undécyle, le dodécyle, le tridécyle, l’isotridécyle, le tétradécyle, l’hexadécyle, le stéaryle, l’icosyle, le docosyle , le tétracosyle, le triacontyle, le 2-éthylhexyle, le 2-butyloctyle, le 2- butyldécyle, 2-hexyloctyle, 2-hexyldécyle, 2-octyldécyle, le 2-hexyldodécyle, le 2- octyldodécyle, le 2-décyltétradécyle, le 2-dodécylhexadécyle, le 2-hexadécyloctadécyle, le 2-tetradécyloctadécyle, le myristyle, le palmityle et le stéaryle. In one embodiment of the invention, the alkyl group is chosen from the group formed by methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, l 'hexadecyl, stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-ethylhexyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl , 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl, 2-hexadecyloctadecyl, 2-tetradecyloctadecyl, myristyl, palmityl and stearyl.
Par groupement alcényle au sens de la présente invention, on entend un groupement hydrocarboné linéaire ou ramifié comprenant au moins une double liaison et comprenant de 2 à 24 atomes de carbone. Le groupement alcényle peut être choisi parmi le vinyle, l’allyle, le propényle, le butényle, l’isobutényle, le pentényle, l’isopentényle, l’hexényle,
l’heptényle, l’octényle, le nonényle, le décényle, l’undécényle, le dodécényle, le tétradécényle et l’oléique. By alkenyl group within the meaning of the present invention is meant a linear or branched hydrocarbon group comprising at least one double bond and comprising from 2 to 24 carbon atoms. The alkenyl group can be chosen from vinyl, allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl and oleic.
Par groupement aryle au sens de la présente invention, on entend un hydrocarbure aromatique polycyclique ou un groupement aromatique, substitué ou non par un groupe alkyle. Le groupement aryle peut comprendre de 6 à 24 atomes de carbone. For the purposes of the present invention, the term “aryl group” is intended to mean a polycyclic aromatic hydrocarbon or an aromatic group, whether or not substituted by an alkyl group. The aryl group can contain from 6 to 24 carbon atoms.
Dans un mode de réalisation, le groupe aryle peut être choisi dans le groupe formé par le phényle, le toluyle, le xylyle, le cuményle, le mésityle, le benzyle, le phénéthyle, le styryle, le cinnamyle, le benzhydryle, le trityle, l’éthylphényle, le propylphényle, le butylphényle, le pentylphényle, le hexylphényl, le heptylphényle, le octylphényle, le nonylphényle, le decylphenyl, le undecylphenyl, le dodécylphényle, le phénylphényle, le benzylphényle, le phényle-styrène, p-cumylphényle et le naphtyle. In one embodiment, the aryl group can be selected from the group formed by phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenylphenyl, phenylphenyl, and -stylphenyl naphthyl.
Par groupement cycloalkyle au sens de la présente invention, on entend un hydrocarbure polycyclique ou cyclique, substitué ou non par un groupe alkyle. For the purposes of the present invention, the term “cycloalkyl group” is intended to mean a polycyclic or cyclic hydrocarbon, whether or not substituted by an alkyl group.
Par groupement cycloalcényle au sens de la présente invention, on entend un hydrocarbure polycyclique ou cyclique, substitué ou non par un groupe alkyle, et comprenant au moins une insaturation. For the purposes of the present invention, the term “cycloalkenyl group” means a polycyclic or cyclic hydrocarbon, substituted or not by an alkyl group, and comprising at least one unsaturation.
Les groupes cycloalkyle et les groupes cycloalcényle peuvent comprendre de 3 à 24 atomes de carbone. Cycloalkyl groups and cycloalkenyl groups can have from 3 to 24 carbon atoms.
Au sens de la présente invention, les groupes cycloalkyle et les groupes cycloalcényle peuvent être choisis, de façon non limitative, dans le groupe constitué par le cyclopentyle, le cyclohexyle, le cycloheptyle, le méthylcyclopentyle, le méthylcyclohexyle, le méthylcycloheptyle, le cyclopentényle, le cyclohexényle, le cycloheptényle, le méthylcyclopentenyle, le méthylcyclohexenyle. For the purposes of the present invention, the cycloalkyl groups and the cycloalkenyl groups can be chosen, without limitation, from the group consisting of cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl.
Dans un mode de réalisation préféré de l’invention, R3, FU, R5 et FÎ6, identiques ou différents, représentent indépendamment un groupement alkyle comprenant de 1 à 24 atomes de carbone, de préférence de 4 à 18 atomes de carbone ou un groupement alcényle comprenant de 2 à 24 atomes de carbone. In a preferred embodiment of the invention, R 3 , FU, R 5 and FÎ 6 , identical or different, independently represent an alkyl group comprising from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms or an alkenyl group comprising from 2 to 24 carbon atoms.
Dans un mode de réalisation de l’invention, X3, X4, X5 et Cb peuvent être identiques et peuvent représenter un atome de soufre. In one embodiment of the invention, X 3 , X 4 , X 5 and Cb may be identical and may represent a sulfur atom.
Dans un autre mode de réalisation de l’invention, X3, X4, X5 et Cb peuvent être identiques et peuvent être un atome d’oxygène.
Dans un autre mode de réalisation de l’invention, X3 et X4 peuvent représenter un atome de soufre et X5 et Cb peuvent représenter un atome d’oxygène. In another embodiment of the invention, X 3 , X 4 , X 5 and Cb may be the same and may be an oxygen atom. In another embodiment of the invention, X 3 and X 4 can represent a sulfur atom and X 5 and Cb can represent an oxygen atom.
Dans un autre mode de réalisation de l’invention, X3 et X4 peuvent représenter un atome d’oxygène et X5 et Cb peuvent représenter un atome de soufre. In another embodiment of the invention, X 3 and X 4 can represent an oxygen atom and X 5 and Cb can represent a sulfur atom.
Dans un autre mode de réalisation de l’invention, le ratio en nombre d’atomes de soufre par rapport au nombre d’atomes d’oxygène (S/O) du composé Mo-DTC peut varier de (1/3) à (3/1 ). In another embodiment of the invention, the ratio of the number of sulfur atoms relative to the number of oxygen atoms (S / O) of the Mo-DTC compound can vary from (1/3) to ( 3/1).
Dans un autre mode de réalisation de l’invention, le composé Mo-DTC de formule (III) peut être choisi parmi un composé Mo-DTC symétrique, un composé Mo-DTC asymétrique et leur combinaison. In another embodiment of the invention, the Mo-DTC compound of formula (III) can be chosen from a symmetrical Mo-DTC compound, an asymmetric Mo-DTC compound and their combination.
Par composé Mo-DTC symétrique selon l’invention, on entend un composé Mo-DTC de formule (V) dans laquelle les groupements R3, FU, R5 et R6 sont identiques. By symmetrical Mo-DTC compound according to the invention is meant an Mo-DTC compound of formula (V) in which the groups R 3 , FU, R 5 and R 6 are identical.
Par composé Mo-DTC asymétrique selon l’invention, on entend un composé Mo-DTC de formule (V) dans laquelle les groupements R3 et R4 sont identiques, les groupements R5 et R6 sont identiques et les groupements R3 et R4 sont différents des groupements R5 et R6. By asymmetric Mo-DTC compound according to the invention is meant an Mo-DTC compound of formula (V) in which the groups R 3 and R 4 are identical, the groups R 5 and R 6 are identical and the groups R 3 and R 4 are different from the R 5 and R 6 groups .
Dans un mode de réalisation préféré de l’invention, le composé Mo-DTC est un mélange d’au moins un composé Mo-DTC symétrique et d’au moins un composé Mo-DTC asymétrique. In a preferred embodiment of the invention, the Mo-DTC compound is a mixture of at least one symmetrical Mo-DTC compound and at least one asymmetric Mo-DTC compound.
Dans un mode de réalisation de l’invention, R3 et R4, identiques, représentent un groupement alkyle comprenant de 5 à 15 atomes de carbone, de préférence de 8 à 13 atomes de carbone, et R5 et R6, identiques, représentent un groupement alkyle comprenant de 5 à 15 atomes de carbone, de préférence de 8 à 13 atomes de carbone, et les groupements R3 et R4 sont identiques ou différents des groupements R5 et R6. In one embodiment of the invention, R 3 and R 4 , identical, represent an alkyl group comprising from 5 to 15 carbon atoms, preferably from 8 to 13 carbon atoms, and R 5 and R 6 , identical, represent an alkyl group comprising from 5 to 15 carbon atoms, preferably from 8 to 13 carbon atoms, and the groups R 3 and R 4 are identical or different from the groups R 5 and R 6 .
Dans un autre mode de réalisation préféré de l’invention, R3 et R4, identiques, représentent un groupement alkyle comprenant de 6 à 10 atomes de carbone et R5 et R6, identiques, représentent un groupement alkyle comprenant de 10 à 15 atomes de carbone, et les groupements R3 et R4 sont différents des groupements R5 et R6.
Dans un autre mode de réalisation préféré de l’invention, R3 et FU, identiques, représentent un groupement alkyle comprenant de 10 à 15 atomes de carbone et R5 et FÎ6, identiques, représentent un groupement alkyle comprenant de 6 à 10 atomes de carbone, et les groupements R3 et R4 sont différents des groupements R5 et R6. In another preferred embodiment of the invention, R 3 and R 4 , identical, represent an alkyl group comprising from 6 to 10 carbon atoms and R 5 and R 6 , identical, represent an alkyl group comprising from 10 to 15 carbon atoms, and the R 3 and R 4 groups are different from the R 5 and R 6 groups . In another preferred embodiment of the invention, R 3 and FU, identical, represent an alkyl group comprising from 10 to 15 carbon atoms and R 5 and FÎ 6 , identical, represent an alkyl group comprising from 6 to 10 atoms. carbon, and the R 3 and R 4 groups are different from the R 5 and R 6 groups .
Dans un autre mode de réalisation préféré de l’invention, R3, R4, R5 et R6, identiques, représentent un groupement alkyle comprenant de 5 à 15 atomes de carbone, de préférence de 8 à 13 atomes de carbone. In another preferred embodiment of the invention, R 3 , R 4 , R 5 and R 6 , which are identical, represent an alkyl group comprising from 5 to 15 carbon atoms, preferably from 8 to 13 carbon atoms.
De manière avantageuse, le composé Mo-DTC est choisi parmi les composés de formule (III) dans laquelle : Advantageously, the Mo-DTC compound is chosen from the compounds of formula (III) in which:
- X3 et X4 représentent un atome d’oxygène, - X 3 and X 4 represent an oxygen atom,
- X5 et Cb représentent un atome de soufre, - X 5 and Cb represent a sulfur atom,
- R3 représente un groupement alkyle comprenant 8 atomes de carbone ou un groupement alkyle comprenant 13 atomes de carbone, - R 3 represents an alkyl group comprising 8 carbon atoms or an alkyl group comprising 13 carbon atoms,
- R4 représente un groupement alkyle comprenant 8 atomes de carbone ou un groupement alkyle comprenant 13 atomes de carbone, - R 4 represents an alkyl group comprising 8 carbon atoms or an alkyl group comprising 13 carbon atoms,
- R5 représente un groupement alkyle comprenant 8 atomes de carbone ou un groupement alkyle comprenant 13 atomes de carbone, - R 5 represents an alkyl group comprising 8 carbon atoms or an alkyl group comprising 13 carbon atoms,
- R6 représente un groupement alkyle comprenant 8 atomes de carbone ou un groupement alkyle comprenant 13 atomes de carbone. - R 6 represents an alkyl group comprising 8 carbon atoms or an alkyl group comprising 13 carbon atoms.
Ainsi, de manière avantageuse, le composé Mo-DTC est choisi parmi les composés de formule (lll-a)
Thus, advantageously, the Mo-DTC compound is chosen from the compounds of formula (III-a)
(lll-a) dans laquelle les groupements R3, R4, R5 et R6 sont tels que définis pour la formule (III). (III-a) in which the groups R 3 , R 4 , R 5 and R 6 are as defined for formula (III).
De manière plus avantageuse, le composé Mo-DTC est un mélange : More advantageously, the Mo-DTC compound is a mixture:
- d’un composé Mo-DTC de formule (lll-a) dans laquelle R3, R4, R5 et R6 représentent un groupement alkyle comprenant 8 atomes de carbone, - a Mo-DTC compound of formula (III-a) in which R 3 , R 4 , R 5 and R 6 represent an alkyl group comprising 8 carbon atoms,
- d’un composé Mo-DTC de formule (lll-a) dans laquelle R3, R4, R5 et R6 représentent un groupement alkyle comprenant 13 atomes de carbone, et/ou
- d’un composé Mo-DTC de formule (lll-a) dans laquelle R3, FU représentent un groupement alkyle comprenant 8 atomes de carbone et R5 et R6 représentent un groupement alkyle comprenant 13 atomes de carbone. - a Mo-DTC compound of formula (III-a) in which R 3 , R 4 , R 5 and R 6 represent an alkyl group comprising 13 carbon atoms, and / or - of a Mo-DTC compound of formula (III-a) in which R3, FU represent an alkyl group comprising 8 carbon atoms and R 5 and R 6 represent an alkyl group comprising 13 carbon atoms.
Comme exemples de composés Mo-DTC, on peut citer les produits Molyvan L®, Molyvan 807® ou Molyvan 822® commercialisés par la société R.T Vanderbilt Compagny® ou les produits Sakura-lube 200®, Sakura-lube 165®, Sakura-lube 525® ou Sakura-lube 600® commercialisés par la société Adeka. As examples of Mo-DTC compounds, mention may be made of the products Molyvan L®, Molyvan 807® or Molyvan 822® marketed by the company RT Vanderbilt Compagny® or the products Sakura-lube 200®, Sakura-lube 165®, Sakura-lube 525® or Sakura-lube 600® marketed by the company Adeka.
De préférence, la composition lubrifiante selon l’invention comprend de 50 ppm à 1500 ppm en masse d’élément molybdbène, de préférence de 100 ppm à 1000 ppm en masse, par rapport à la masse totale de la composition lubrifiante. Preferably, the lubricating composition according to the invention comprises from 50 ppm to 1500 ppm by mass of molybdenum element, preferably from 100 ppm to 1000 ppm by mass, relative to the total mass of the lubricant composition.
Le composé 2,5-dimercapto-1 ,3,4 thiadiazole alkyl (poly)carboxylate Par « composé 2,5-dimercapto-1 ,3,4 thiadiazole alkyl (poly)carboxylate » on entend au sens de l’invention un composé dérivé du 2,5-dimercapto-1,3,4 thiadiazole dont l’un au moins des groupements thiol est substitué par un groupement alkyl (poly)carboxylate. The compound 2,5-dimercapto-1, 3,4 thiadiazole alkyl (poly) carboxylate By “compound 2,5-dimercapto-1, 3,4 thiadiazole alkyl (poly) carboxylate” is meant within the meaning of the invention a compound derivative of 2,5-dimercapto-1,3,4 thiadiazole in which at least one of the thiol groups is substituted by an alkyl (poly) carboxylate group.
Par « groupement alkyl (poly)carboxylate » on entend au sens de l’invention un groupement alkyl substitué par un ou plusieurs groupement carboxylate. Lorsqu’il est substitué par un unique groupement carboxylate, on parle de « groupement alkyl carboxylate ». Lorsqu’il est substitué par au moins deux groupements carboxylate, on parle de « groupement alkyl polycarboxylate ». By "alkyl (poly) carboxylate group" is meant within the meaning of the invention an alkyl group substituted by one or more carboxylate group. When it is substituted by a single carboxylate group, it is called an "alkyl carboxylate group". When it is substituted by at least two carboxylate groups, it is called an "alkyl polycarboxylate group".
De préférence, un seul des groupements thiol est substitué par un groupement alkyl (poly)carboxylate. Preferably, only one of the thiol groups is substituted by an alkyl (poly) carboxylate group.
Plus préférentiellement, le composé 2,5-dimercapto-1 ,3,4 thiadiazole alkyl (poly)carboxylate est choisi parmi les composés de formule (IV) suivante :
dans laquelle R’ représente un groupement alkyle, linéaire, branché ou cyclique, saturé ou insaturé, en C1-C34 substitué par au moins un groupement carboxylate d’alkyle en C1-C34.
De préférence, le groupement R’ est choisi parmi les groupements alkyle en C1-C30, plus préférentiellement en C1-C20, encore plus préférentiellement en C1-C10, et avantageusement en C1-C5, substitués par au moins un groupement carboxylate d’alkyle en C1-C34. More preferably, the 2,5-dimercapto-1, 3,4 thiadiazole alkyl (poly) carboxylate compound is chosen from the compounds of formula (IV) below: in which R ′ represents a linear, branched or cyclic, saturated or unsaturated, C1-C34 alkyl group substituted by at least one C1-C34 alkyl carboxylate group. Preferably, the group R 'is chosen from C 1 -C 30 alkyl groups, more preferably C1-C2 0 , even more preferably C1-C1 0 , and advantageously C 1 -C 5 , substituted with at least a C1-C34 alkyl carboxylate group.
Plus préférentiellement, le groupement R’ est choisi parmi les groupements méthyle, éthyle, propyle, n-butyl, isobutyl, ferf-butyl, n-pentyle, iso-pentyle et néopentyle, substitués par au moins un groupement carboxylate d’alkyle en C1-C34. More preferably, the R ′ group is chosen from methyl, ethyl, propyl, n-butyl, isobutyl, ferf-butyl, n-pentyl, iso-pentyl and neopentyl groups, substituted with at least one C alkyl carboxylate group. 1 -C 34 .
Avantageusement, le groupement R’ est un groupement éthyle substitué par au moins un groupement carboxylate d’alkyle en C1-C34. Advantageously, the R ′ group is an ethyl group substituted with at least one C 1 -C 34 alkyl carboxylate group.
De préférence, le groupement carboxylate d’alkyle est choisi parmi les groupements carboxylate d’alkyle en C1-C30, plus préférentiellement en C1-C20, encore plus préférentiellement en C5-C10. Preferably, the alkyl carboxylate group is chosen from C 1 -C 30 alkyl carboxylate groups, more preferably C 1 -C 2 0, even more preferably C 5 -C 1 0 .
Le groupement alkyle du groupement carboxylate d’alkyle peut être linéaire, branché ou cyclique. The alkyl group of the alkyl carboxylate group can be linear, branched or cyclic.
De préférence, le groupement alkyle du groupement carboxylate d’alkyle est choisi parmi les groupements alkyles ramifiés. Preferably, the alkyl group of the alkyl carboxylate group is selected from branched alkyl groups.
Le groupement alkyle du groupement carboxylate d’alkyle peut être saturé ou insaturé.The alkyl group of the alkyl carboxylate group can be saturated or unsaturated.
De préférence, le groupement alkyle du groupement carboxylate d’alkyle est saturé. Avantageusement, le groupement carboxylate d’alkyle est un groupement carboxylate de 2-éthylhéxyl. Preferably, the alkyl group of the alkyl carboxylate group is saturated. Advantageously, the alkyl carboxylate group is a 2-ethylhexyl carboxylate group.
Selon un mode de réalisation, le groupement R’ est substitué par au moins deux groupements carboxylates d’alkyle en C1-C34. According to one embodiment, the R ′ group is substituted by at least two C 1 -C 34 alkyl carboxylate groups.
Les groupements carboxylate d’alkyle peuvent être identiques ou différents. The alkyl carboxylate groups can be the same or different.
De préférence, selon ce mode de réalisation, les groupements carboxylate d’alkyle sont identiques. Preferably, according to this embodiment, the alkyl carboxylate groups are identical.
Plus préférentiellement, les groupements carboxylate d’alkyles sont tous des groupements carboxylates de 2-éthylhéxyle. More preferably, the alkyl carboxylate groups are all 2-ethylhexyl carboxylate groups.
Selon un mode de réalisation préféré, le composé 2,5-dimercapto-1 ,3,4 thiadiazole alkyl (poly)carboxylate répond à la formule (V) suivante :
De tels composés sont disponibles commercialement, notamment auprès de Vanderbilt sous la référence Vanlube® 871 (N°CAS 12610453-53-8). Avantageusement, le composé organomolybdène et le composé 2,5-dimercapto-1 ,3,4- thiadiazole alkyl (poly)carboxylate sont présents dans la composition d’additifs selon l’invention selon un ratio massique allant de 1 :100 à 100 :1 , de préférence de 1 :10 à 10 :1 , plus préférentiellement de 1 : 5 à 5 : 1 . De préférence, la composition d’huile lubrifiante selon l’invention comprend de 0,2% à 1.0% en masse de composé 2,5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate, de préférence de 0,2 à 0,9% en masse, par exemple 0,5% en masse, par rapport à la masse totale de la composition lubrifiante. L’huile de base According to a preferred embodiment, the 2,5-dimercapto-1, 3,4 thiadiazole alkyl (poly) carboxylate compound corresponds to the following formula (V): Such compounds are commercially available, in particular from Vanderbilt under the reference Vanlube® 871 (CAS No. 12610453-53-8). Advantageously, the organomolybdenum compound and the 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound are present in the additive composition according to the invention in a mass ratio ranging from 1: 100 to 100: 1, preferably 1: 10 to 10: 1, more preferably 1: 5 to 5: 1. Preferably, the lubricating oil composition according to the invention comprises from 0.2% to 1.0% by mass of 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound, preferably 0, 2 to 0.9% by mass, for example 0.5% by mass, relative to the total mass of the lubricating composition. Base oil
L’huile de base utilisée dans les compositions lubrifiantes de l’invention peut être choisie parmi des huiles d’origine minérale ou synthétique appartenant aux groupes I à V selon les classes définies par la classification API (ou leurs équivalents selon la classification ATIEL (Tableau 1) ou leurs mélanges. The base oil used in the lubricating compositions of the invention can be chosen from oils of mineral or synthetic origin belonging to groups I to V according to the classes defined by the API classification (or their equivalents according to the ATIEL classification (Table 1) or their mixtures.
Tableau 1
Table 1
Les huiles de base minérales de l’invention incluent tout type d’huile de base obtenue par distillation atmosphérique et sous vide de pétrole brute, suivi par des opérations de raffinage telle que l’extraction par solvant, désasphaltage, déparaffinage au solvant, hydrotraitement, hydrocraquage, hydro-isomérisation et hydrofinissage. The mineral base oils of the invention include any type of base oil obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, deasphalting, solvent dewaxing, hydrotreating, hydrocracking, hydro-isomerization and hydrofinishing.
Des mélanges d’huiles synthétiques et minérales peuvent aussi être utilisés. Mixtures of synthetic and mineral oils can also be used.
Les huiles de base des compositions lubrifiantes selon l’invention peuvent aussi être choisies parmi les huiles synthétiques, tels que certains esters d’acides carboxyliques et d’alcools, et les polyalphaoléfines. Les polyalphaoléfines utilsées en tant qu’huile de base sont par exemple obtenues à partir de monomères comprenant de 4 à 32 atomes de carbone, par exemple à partir d’octène ou décène, et pour lesquels la viscosité à 100°C est comprise entre 1 ,5 et 15 mm2.s-1 selon la norme ASTM D445. Leur masse molaire moyenne est généralement comprise entre 250 et 3000 selon la norme ASTM D5296.The base oils of the lubricating compositions according to the invention can also be chosen from synthetic oils, such as certain esters of carboxylic acids and alcohols, and polyalphaolefins. The polyalphaolefins used as base oil are for example obtained from monomers comprising from 4 to 32 carbon atoms, for example from octene or decene, and for which the viscosity at 100 ° C is between 1 , 5 and 15 mm2.s-1 according to ASTM D445. Their average molar mass is generally between 250 and 3000 according to the ASTM D5296 standard.
De manière avantageuse, la composition lubrifiante selon l’invention comprend au moins 50 % en masse d’huiles de base, de préférence au moins 60 % en masse, plus préférentiellement au moins 70 % en masse, par rapport à la masse totale de la composition. Advantageously, the lubricating composition according to the invention comprises at least 50% by mass of base oils, preferably at least 60% by mass, more preferably at least 70% by mass, relative to the total mass of the base oil. composition.
De manière plus particulièrement avantageuse, la composition lubrifiante selon l’invention comprend de 50 à 99,5% en masse d’huiles de base, de préférence de 70 à 99,5 % en masse d’huiles de base, par rapport à la masse totale de la composition. More particularly advantageously, the lubricating composition according to the invention comprises from 50 to 99.5% by mass of base oils, preferably from 70 to 99.5% by mass of base oils, relative to the total mass of the composition.
Additifs optionnels Optional additives
De nombreux additifs optionnels peuvent également être présents dans les compositions lubrifiantes selon l’invention. Many optional additives can also be present in the lubricating compositions according to the invention.
Les additifs préférés pour la composition lubrifiante selon l’invention sont choisis parmi les additifs détergents, les additifs modificateurs de frottement diffèrent des composés molybdène définis ci-dessus, des additifs extrême pression, des dispersants, des activateurs du point d'écoulement, des agents anti-mousse, des épaississants et leurs mélanges. The preferred additives for the lubricating composition according to the invention are chosen from detergent additives, the friction modifying additives differ from the molybdenum compounds defined above, extreme pressure additives, dispersants, pour point activators, agents. defoamers, thickeners and mixtures thereof.
De préférence, les compositions lubrifiantes selon l’invention, comprennent au moins un additif extrême pression, ou un mélange.
Les additifs anti-usure et les additifs extrême pression protègent les frictions des surfaces en formant un film de protection adsorbé sur ses surfaces. Preferably, the lubricating compositions according to the invention comprise at least one extreme pressure additive, or a mixture. Anti-wear additives and extreme pressure additives protect surface friction by forming a protective film adsorbed on its surfaces.
Il existe une grande variété d’additifs anti-usure. De préférence, pour les compositions lubrifiantes de l’invention, les additifs anti-usure sont choisis parmi les additifs comprenant du phosphore et du soufre tels que les métaux alkylthiophosphate, en particulier zinc alkylthiophosphate, et plus précisément le zinc dialkyldithiophosphate ou ZnDTP. Les composés préférés sont de formule Zn((SP(S)(OR)(OR'))2, dans laquelle R et R', identique ou différent, représente indépendamment un groupe alkyle, de préférence un groupe alkyle comprenant de 1 à 18 atomes de carbone. There is a wide variety of antiwear additives. Preferably, for the lubricating compositions of the invention, the anti-wear additives are chosen from additives comprising phosphorus and sulfur such as the metals alkylthiophosphate, in particular zinc alkylthiophosphate, and more precisely zinc dialkyldithiophosphate or ZnDTP. The preferred compounds are of formula Zn ((SP (S) (OR) (OR ')) 2, in which R and R', identical or different, independently represent an alkyl group, preferably an alkyl group comprising from 1 to 18 carbon atoms.
Les phosphates d’amine sont également des additifs anti-usure qui peuvent être utilisés dans les compositions lubrifiantes de l’invention. Cependant, les atomes de phosphore apportés par ces additifs peuvent agir comme poison des systèmes catalytiques des automobiles puisqu’ils génèrent des cendres. Il est possible de minimiser ces effets en substituant une partie des phosphates d’amine avec des additifs n’apportant pas de phosphore, tels que par exemple les polysulfides, notamment les oléfines contenant du soufre. Amine phosphates are also antiwear additives which can be used in the lubricating compositions of the invention. However, the phosphorus atoms provided by these additives can act as a poison in automobile catalytic systems since they generate ash. These effects can be minimized by substituting part of the amine phosphates with additives which do not provide phosphorus, such as, for example, polysulfides, in particular olefins containing sulfur.
Avantageusement, les compositions lubrifiantes selon l’invention peuvent comprendre de 0,01 à 6% en masse, de préférence de 0,05 à 4% en masse, plus préférentiellement de 0,1 à 2% en masse par rapport au masse total de composition lubrifiante, d’additifs anti-usure et extrême pression. Advantageously, the lubricating compositions according to the invention can comprise from 0.01 to 6% by mass, preferably from 0.05 to 4% by mass, more preferably from 0.1 to 2% by mass relative to the total mass of lubricating composition, anti-wear and extreme pressure additives.
Avantageusement, les compositions lubrifiantes selon l’invention comprennent de 0,01 à 6% en masse, de préférence de 0,05 à 4% en masse, plus préférentiellement de 0,1 à 2% en masse par rapport au masse total de composition lubrifiante, d’additifs anti-usure (ou composé anti-usure). Advantageously, the lubricating compositions according to the invention comprise from 0.01 to 6% by mass, preferably from 0.05 to 4% by mass, more preferably from 0.1 to 2% by mass relative to the total mass of composition. lubricant, anti-wear additives (or anti-wear compound).
Avantageusement, les compositions selon l’invention peuvent comprendre au moins un additif modificateur de friction différents des composés molybdène de l’invention. Les additifs modificateurs de friction peuvent notamment être choisis parmi les composes apportant des éléments métalliques et des composes sans cendres. Parmi les composes apportant des éléments métalliques il peut être fait mention des complexes de métaux de transition tels que Mo, Sb, Sn, Fe, Cu, Zn pour lesquels les ligands peuvent être des composés hydrocarbonés comprenant des atomes d’oxygène, d’azote, de soufre ou de phosphore. Les additifs modificateurs de friction sans cendres sont généralement d’origine organique ou peuvent être choisis parmi les monoester d’acide gras et de polyols, les amines alcoxylées, les amines grasses alcoxylées, les époxydes gras, les borates d’époxydes gras, les amines grasses ou les esters d’acide de glycérol. Selon l’invention,
les composes gras comprenant au moins un groupe hydrocarboné comprenant de 10 à 24 atomes de carbone. Advantageously, the compositions according to the invention can comprise at least one friction modifier additive different from the molybdenum compounds of the invention. The friction modifying additives can in particular be chosen from compounds providing metallic elements and ashless compounds. Among the compounds providing metallic elements, mention may be made of transition metal complexes such as Mo, Sb, Sn, Fe, Cu, Zn for which the ligands may be hydrocarbon compounds comprising oxygen or nitrogen atoms. , sulfur or phosphorus. The ashless friction modifier additives are generally of organic origin or can be chosen from fatty acid monoesters and polyols, alkoxylated amines, alkoxylated fatty amines, fatty epoxides, fatty epoxy borates, amines fatty or acid esters of glycerol. According to the invention, fatty compounds comprising at least one hydrocarbon group comprising from 10 to 24 carbon atoms.
Avantageusement la composition lubrifiante selon l’invention peut comprendre de 0,01 à 2% en masse ou de 0,01 à 5% en masse, de préférence de 0,1 à 1 ,5% en masse ou de 0,1 à 2% en masse par rapport au masse total de la composition lubrifiante, d’additif modificateur de friction différent des composés molybdène selon l’invention. Avantageusement, la composition lubrifiante selon l’invention peut comprendre au moins un additive antioxydant. Advantageously, the lubricating composition according to the invention can comprise from 0.01 to 2% by mass or from 0.01 to 5% by mass, preferably from 0.1 to 1, 5% by mass or from 0.1 to 2 % by mass relative to the total mass of the lubricating composition, of friction modifier additive different from the molybdenum compounds according to the invention. Advantageously, the lubricating composition according to the invention can comprise at least one antioxidant additive.
Les additifs antioxydant généralement retardant la dégradation de la composition lubrifiante. Cette dégradation s’exprime le plus souvent par la formation de dépôt, par la présence de boues ou par une augmentation de la viscosité de la composition lubrifiante. Les additifs antioxydants agissent généralement comme inhibiteurs radicalaires ou inhibiteurs destructeurs de l'hydroperoxyde. Parmi les antioxydants couramment utilisés on peut citer les antioxydants de type phénolique, les antioxydants de type amine, les antioxydants contenant du soufre et du phosphore. Certains de ces antioxydants, par exemple ceux comprenant du soufre et du phosphore peuvent générer des cendres. Les additifs antioxydants phénoliques peuvent être exempt de cendres ou bien être sous la forme de sels métalliques neutres ou basiques. Les additifs antioxydants peuvent notamment être choisis parmi les phénols stériquement encombrés, des esters de phénols stériquement encombrés, des phénols stériquement encombrés comprenant un pont thioéther, des diphénylamines, des diphénylamines substituées avec au moins un groupe alkyl en C1 à C12, des N,N’-dialkyl-aryl-diamines et leurs mélanges. Antioxidant additives generally delay the degradation of the lubricating composition. This degradation is most often expressed by the formation of deposit, by the presence of sludge or by an increase in the viscosity of the lubricating composition. Antioxidant additives generally act as free radical inhibitors or destructive hydroperoxide inhibitors. Among the antioxidants commonly used, mention may be made of antioxidants of the phenolic type, antioxidants of the amine type, and antioxidants containing sulfur and phosphorus. Some of these antioxidants, for example those comprising sulfur and phosphorus, can generate ash. The phenolic antioxidant additives can be ash free or in the form of neutral or basic metal salts. The antioxidant additives can in particular be chosen from sterically hindered phenols, esters of sterically hindered phenols, sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted with at least one C1 to C12 alkyl group, N, N '-dialkyl-aryl-diamines and mixtures thereof.
De préférence selon l’invention, les phénols stériquement encombrés sont choisis parmi les composés comprenant un groupe phénol pour lequel au moins un des atomes de carbone au voisinage de l’atome de carbone portant la fonction alcool est substitué par au moins un groupe alkyle en C1 à C10, de préférence un groupe alkyle en C1 à C6, de préférence un groupe alkyle en C4, de préférence un groupe ter-butyle. Preferably according to the invention, the sterically hindered phenols are chosen from compounds comprising a phenol group for which at least one of the carbon atoms in the vicinity of the carbon atom carrying the alcohol function is substituted by at least one alkyl group in C1 to C10, preferably a C1 to C6 alkyl group, preferably a C4 alkyl group, preferably a tert-butyl group.
Les composes amines sont une autre classe d’additifs antioxydants qui peuvent être utilises, optionnellement en combinaison avec des additifs antioxydants phénoliques. Des exemples de composes amines sont les amines aromatiques, par exemple les amines aromatiques de formule NRaRbRc dans laquelle Ra représente un groupe aliphatique ou un groupe aromatique, optionnellement substitué, Rb représente un groupe aromatique, optionnellement substitué, Rc représente un atome d’hydrogène, un groupe alkyle, un groupe aryle group ou un groupe de groupe de formule RdS(0)zRe dans lequel Rd représente un groupe alkylène ou alkenylène, Re représente un groupe alkyle, un groupe alkényle ou un groupe aryle et z représente 0, 1 ou 2.
Les alkyl-phénols contenant du soufre ou leurs sels de métaux alcalins ou alcalino-terreux peuvent aussi être utilisés comme additifs antioxydants. Amine compounds are another class of antioxidant additives which can be used, optionally in combination with phenolic antioxidant additives. Examples of amine compounds are aromatic amines, for example aromatic amines of formula NRaRbRc in which Ra represents an aliphatic group or an aromatic group, optionally substituted, Rb represents an aromatic group, optionally substituted, Rc represents a hydrogen atom, an alkyl group, an aryl group or a group of the formula RdS (0) zRe in which Rd represents an alkylene or alkenylene group, Re represents an alkyl group, an alkenyl group or an aryl group and z represents 0, 1 or 2. Sulfur-containing alkyl phenols or their alkali or alkaline earth metal salts can also be used as antioxidant additives.
D’autres classes d’additifs antioxydants sont les composés comprenant du cuivre, par exemple thio- ou dithio-phosphate de cuivre, des sels de cuivre et d’acides carboxylique, des dithiocarbamates, des sulfonates, des phénates, des acétylacétonates de cuivre. Les sels de cuivre I et II, les sels d’acide ou d’anhydride succinique peuvent également être utilisés. Other classes of antioxidant additives are compounds comprising copper, eg copper thio- or dithiophosphate, copper and carboxylic acid salts, dithiocarbamates, sulfonates, phenates, copper acetylacetonates. Copper I and II salts, salts of succinic acid or succinic anhydride can also be used.
Les compositions lubrifiantes selon l’invention peuvent également comprendre tout type d’antioxydant connu de l’homme du métier. The lubricating compositions according to the invention can also comprise any type of antioxidant known to those skilled in the art.
Avantageusement, la composition lubrifiante comprend au moins un additif antioxydant exempt de cendres. Advantageously, the lubricating composition comprises at least one antioxidant additive free of ash.
Egalement avantageusement la composition lubrifiante selon l’invention comprend de 0,1 à 2% en masse par rapport au masse total de la composition, d’au moins un additive antioxydant. Also advantageously, the lubricating composition according to the invention comprises from 0.1 to 2% by mass relative to the total mass of the composition, of at least one antioxidant additive.
La composition lubrifiante selon l’invention peut également comprendre au moins un additif détergent. The lubricating composition according to the invention can also comprise at least one detergent additive.
Les additifs détergents permettent généralement de réduire la formation de dépôts à la surface des parties métalliques par dissolution des produits secondaires d’oxydation et de combustion. Detergent additives generally reduce the formation of deposits on the surface of metal parts by dissolving the by-products of oxidation and combustion.
Les additifs détergents pouvant être utilisés dans les compositions lubrifiantes selon l’invention sont généralement connus de l’homme du métier. Les additifs détergents peuvent être des composés anioniques comprenant une longue chaîne hydrocarbonée lipophilique et une tête hydrophobe. Le cation associé peut être un cation métallique d’un métal alcalin ou alcalino-terreux. The detergent additives which can be used in the lubricating compositions according to the invention are generally known to those skilled in the art. Detergent additives can be anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophobic head. The associated cation can be a metal cation of an alkali or alkaline earth metal.
Les additifs détergents sont de préférence choisis parmi les sels de métaux alcalins ou alcalino-terreux d’acide carboxylique, les sulfonates, les salicylates, les naphténates, ainsi que les sels de phénates. Les métaux alcalins et alcalino-terreux sont de préférence le calcium, le magnésium, le sodium ou le baryum. The detergent additives are preferably chosen from alkali or alkaline earth metal salts of carboxylic acid, sulfonates, salicylates, naphthenates, as well as salts of phenates. The alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium.
Ces sels métalliques comprennent généralement le métal en quantité stoechiométrique ou en excès, c’est-à-dire dans une teneur supérieure à la teneur stoechiométrique. Ceux-ci sont alors des détergents surbasés; l’excès de métal impliquant la nature surbasée de l’additif détergent est généralement sous la forme d’un sel métallique insoluble dans l’huile, par exemple carbonate, hydroxyde, oxalate, acétate, glutamate, de préférence carbonate. Avantageusement, la composition lubrifiante selon l’invention peut comprendre de 0,5 à 8% ou de 2 à 4% en masse d’additif détergents surbasés par rapport au masse total de la composition lubrifiante.
Egalement de manière avantageuse, la composition lubrifiante selon l’invention peut aussi comprendre un additif d’abaissement du point d’écoulement. These metal salts generally include the metal in a stoichiometric amount or in excess, that is to say in a content greater than the stoichiometric content. These are then overbased detergents; the excess metal implying the overbased nature of the detergent additive is generally in the form of an oil insoluble metal salt, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate. Advantageously, the lubricating composition according to the invention can comprise from 0.5 to 8% or from 2 to 4% by mass of overbased detergent additive relative to the total mass of the lubricating composition. Also advantageously, the lubricating composition according to the invention can also comprise an additive for lowering the pour point.
En ralentissant la formation de cristaux de paraffine, l’additif d’abaissement du point d’écoulement améliore généralement le comportement à froid de la composition lubrifiante selon l’invention. By slowing the formation of paraffin crystals, the pour point depressant additive generally improves the cold behavior of the lubricant composition according to the invention.
Comme exemple d’additif d’abaissement du point d’écoulement on peut mentionner, les alkyles polyméthacrylates, polyacrylates, polyarylamides, polyalkylphénols, polyalkylnaphtalène, les alkyls polystyrènes. As an example of a pour point lowering additive, there may be mentioned, alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalene, alkyl polystyrenes.
Avantageusement, la composition lubrifiante selon l’invention peut aussi comprendre un agent dispersant. Advantageously, the lubricating composition according to the invention can also comprise a dispersing agent.
Les agents dispersants peuvent être choisis parmi les bases de Mannich bases, les succinimides et leurs dérivés. The dispersing agents can be chosen from Mannich bases, succinimides and their derivatives.
Egalement de manière avantageuse, la composition lubrifiante selon l’invention peut comprendre de 0,2 à 10% en masse d’agent dispersant par rapport au masse total de composition lubrifiante. Also advantageously, the lubricating composition according to the invention can comprise from 0.2 to 10% by mass of dispersing agent relative to the total mass of lubricating composition.
Avantageusement, la composition lubrifiante selon l’invention peut également comprendre au moins un polymère additionnel améliorant l’indice de viscosité. Comme exemple de polymère additionnel améliorant l’indice de viscosité, on peut citer les esters polymériques, homopolymères ou copolymères, hydrogénés ou non, de styrène, de butadiène, et d’isoprène, les polyméthacrylates (PMA). Egalement avantageusement, la composition lubrifiante selon l’invention peut comprendre de 1 à 15% en masse par rapport au masse total de composition lubrifiante, d’additif améliorant l’indice de viscosité. Advantageously, the lubricating composition according to the invention can also comprise at least one additional polymer improving the viscosity index. As an example of an additional polymer improving the viscosity index, mention may be made of polymeric esters, homopolymers or copolymers, hydrogenated or not, of styrene, butadiene, and isoprene, polymethacrylates (PMA). Also advantageously, the lubricating composition according to the invention can comprise from 1 to 15% by mass, relative to the total mass of lubricating composition, of additive improving the viscosity index.
La composition lubrifiante selon l’invention peut également comprendre au moins un agent épaississant. The lubricating composition according to the invention can also comprise at least one thickening agent.
La composition lubrifiante selon l’invention peut également comprendre un agent antimousse et un agent démulsifiant. The lubricating composition according to the invention can also comprise an anti-foaming agent and a demulsifying agent.
La composition lubrifiante The lubricating composition
Avantageusement, la composition lubrifiante selon l’invention comprend : Advantageously, the lubricating composition according to the invention comprises:
- de 50 % à 99,5 % en masse d’huile de base, - from 50% to 99.5% by mass of base oil,
- de 0,1 % à 1 ,5 % en masse de composé organomolybdène, - from 0.1% to 1.5% by mass of organomolybdenum compound,
- de 0,2 % à 1 ,0 % en masse de composé 2,5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate, - from 0.2% to 1.0% by mass of 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound,
- optionnellement, de 0.1% à 45% en masse d’additifs, par rapport à la masse totale de la composition de lubrifiant.
Plus avantageusement, la composition lubrifiante selon l’invention comprend : - optionally, from 0.1% to 45% by mass of additives, relative to the total mass of the lubricant composition. More advantageously, the lubricating composition according to the invention comprises:
- de 60 % à 99,5 % en masse d’huile de base, - from 60% to 99.5% by mass of base oil,
- de 0,1 % à 1 % en masse de composé organomolybdène, - from 0.1% to 1% by mass of organomolybdenum compound,
- de 0,2 % à 0,9 % en masse de composé 2,5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate, - from 0.2% to 0.9% by mass of 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound,
- optionnellement, de 0.5% à 40% en masse d’additifs, par rapport à la masse totale de la composition de lubrifiant. - optionally, from 0.5% to 40% by mass of additives, relative to the total mass of the lubricant composition.
De préférence, la composition lubrifiante a une teneur en soufre allant de 0,01% à 5% en masse, de préférence 0,1% à 2% en masse, plus préférentiellement de 0,1 % à 0,5% en masse, par rapport à la masse totale de la composition lubrifiante. Preferably, the lubricating composition has a sulfur content ranging from 0.01% to 5% by mass, preferably 0.1% to 2% by mass, more preferably from 0.1% to 0.5% by mass, relative to the total mass of the lubricating composition.
Utilisations Uses
L’invention concerne également l’utilisation d’un composé 2,5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate pour protéger un composé organomolybdène, par exemple le MoDTC, de sa dégradation, de préférence pour protéger le composé organomolybdène, par exemple le MoDTC, de l’oxydation. The invention also relates to the use of a 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound to protect an organomolybdenum compound, for example MoDTC, from its degradation, preferably to protect the organomolybdenum compound, for example MoDTC. organomolybdenum compound, eg MoDTC, from oxidation.
La présente invention concerne également l’utilisation d’un composé 2,5-dimercapto-1 ,3,4- thiadiazole alkyl (poly)carboxylate dans une composition lubrifiante comprenant au moins une huile de base et au moins un composé organomolybdène, par exemple un complexe organique du molybdène avec des ligands dithiocarbamates, pour maintenir les propriétés de Fuel Eco de la composition lubrifiante dans le temps. The present invention also relates to the use of a 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound in a lubricating composition comprising at least one base oil and at least one organomolybdenum compound, for example an organic molybdenum complex with dithiocarbamate ligands, to maintain the Fuel Eco properties of the lubricating composition over time.
La présente invention concerne également un procédé de protection de la dégradation, notamment par oxydation, du composé organomolybdène, par exemple le MoDTC, d’une composition lubrifiante comprenant au moins une huile de base et un composé organomolybdène, par exemple du MoDTC, comprenant l’addition, dans ladite composition lubrifiante, d’un composé 2,5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate. The present invention also relates to a process for protecting the degradation, in particular by oxidation, of the organomolybdenum compound, for example MoDTC, of a lubricating composition comprising at least one base oil and an organomolybdenum compound, for example MoDTC, comprising l addition, in said lubricating composition, of a 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound.
La présente invention concerne également un procédé de maintien dans le temps des propriété Fuel Eco d’une composition lubrifiante lubrifiante comprenant au moins une huile de base et un composé organomolybdène, par exemple du MoDTC, comprenant l’addition, dans ladite composition lubrifiante d’un composé 2, 5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate.
Les variantes et les modes de réalisations détaillés ci-dessous pour le composé organomolybdène et pour le composé 2,5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate s’appliquent également aux différentes utilisations définies ci-dessus. The present invention also relates to a process for maintaining the Fuel Eco properties over time of a lubricating lubricating composition comprising at least one base oil and an organomolybdenum compound, for example MoDTC, comprising the addition, in said lubricating composition of a 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound. The variants and embodiments detailed below for the organomolybdenum compound and for the 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound also apply to the different uses defined above.
Le maintien des propriétés Fuel Eco d’une composition lubrifiante peut typiquement être évalué par détermination de l’évolution du coefficient de frottement de la composition au cours du fonctionnement d’un moteur lubrifié avec la composition à tester. The maintenance of the Fuel Eco properties of a lubricating composition can typically be evaluated by determining the change in the coefficient of friction of the composition during the operation of an engine lubricated with the composition to be tested.
Au cours du fonctionnement du moteur et à intervalles de temps régulier, un échantillon de la composition lubrifiante est prélevé. During engine operation and at regular time intervals, a sample of the lubricating composition is taken.
La mesure du coefficient de frottement de la composition est ensuite réalisée selon toute méthode connue de l’homme du métier. Elle peut par exemple être réalisée au moyen d’un tribomètre alternatif bille-plan. Il est entendu que plus le coefficient de frottement est bas au cours du temps, plus les effets sur les propriétés fuel eco de la composition lubrifiante sont maintenues dans le temps. The measurement of the coefficient of friction of the composition is then carried out according to any method known to those skilled in the art. It can for example be carried out by means of a reciprocating ball-plane tribometer. It is understood that the lower the coefficient of friction is over time, the more the effects on the fuel eco properties of the lubricating composition are maintained over time.
Ainsi, et de manière particulièrement avantageuse, la mise en œuvre d’un composé 2,5- dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate combinée avec un composé organomolybdène, de préférence composé organomolybdène dinucléaire, permet : Thus, and in a particularly advantageous manner, the use of a 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound combined with an organomolybdenum compound, preferably a dinuclear organomolybdenum compound, allows:
- la prolongation dans le temps des propriétés du composé organomolybdène, par exemple du MoDTC, en particulier comme agent de lubrification, de préférence comme modificateur de frottement ; the prolongation over time of the properties of the organomolybdenum compound, for example MoDTC, in particular as a lubricating agent, preferably as a friction modifier;
- le maintien dans le temps des propriétés Fuel Eco d’une composition lubrifiante comprenant au moins une huile de base et un composé organomolybdène, par exemple du MoDTC ; et/ou - the maintenance over time of the Fuel Eco properties of a lubricating composition comprising at least one base oil and one organomolybdenum compound, for example MoDTC; and or
- le maintien dans le temps de l’économie de carburant. - maintenance of fuel economy over time.
Les caractéristiques particulières, avantageuses ou préférées de l'utilisation combinée selon l'invention définissent des combinaisons particulières, avantageuses ou préférées utilisables selon l'invention. The particular, advantageous or preferred characteristics of the combined use according to the invention define particular, advantageous or preferred combinations which can be used according to the invention.
La figure 1 représente l’évolution du coefficient de frottement d’une composition selon l’invention et d’une composition de référence en fonction du temps de fonctionnement du moteur.
Exemples: FIG. 1 represents the change in the coefficient of friction of a composition according to the invention and of a reference composition as a function of the operating time of the engine. Examples:
Les compositions détaillées ci-après ont été préparées à partir des composés suivants :The compositions detailed below were prepared from the following compounds:
- huile de base : huile de base formulée de grade OW-12. - base oil: formulated base oil of grade OW-12.
Cette huile de base comprend : This base oil includes:
- 81 ,7 % en masse d’huile de base, - 81.7% by mass of base oil,
- 17,8 % en masse d’additifs usuels (4,4% additif améliorant l’indice de viscosité, 0,5% additif oxydant, 0,20% additif permettant d’abaisser le point d’écoulement et 12,7% d’un paquet d’additifs), et - 17.8% by mass of usual additives (4.4% additive improving the viscosity index, 0.5% oxidizing additive, 0.20% additive allowing to lower the pour point and 12.7% a packet of additives), and
- 0,05% en masse de molybdène dithiocarbarmate (noté ci-après MoDTC), par rapport à la masse totale de l’huile de base. - 0.05% by mass of molybdenum dithiocarbarmate (hereinafter referred to as MoDTC), relative to the total mass of the base oil.
- le composé 2,5-dimercapto-1 ,3,4-thiadiazole alkyl polycarboxylate : composé de formule (V) défini ci-dessus, noté ci-après Thiadiazole. the 2,5-dimercapto-1, 3,4-thiadiazole alkyl polycarboxylate compound: compound of formula (V) defined above, denoted below as Thiadiazole.
Exemple 1 : Préparations des compositions Example 1: Preparations of the compositions
Les compositions C0 et C1 sont préparés par mélanges des différents constituants selon les teneurs indiquées dans le tableau 2 ci-dessous. Compositions C0 and C1 are prepared by mixing the various constituents according to the contents indicated in Table 2 below.
La composition CO est une composition de référence (huile de base non-additivée). The CO composition is a reference composition (base oil without additives).
La composition C1 est une composition selon l’invention. Composition C1 is a composition according to the invention.
Tableau 2
Table 2
Exemple 2 : Essais moteurs Example 2: Engine tests
Les coefficients de frottement des compositions lubrifiantes C0 et C1 sont mesurées dans des conditions d’essai moteur selon la méthode suivante. The friction coefficients of the lubricating compositions C0 and C1 are measured under engine test conditions according to the following method.
Chaque composition lubrifiante (10 Kg) est évaluée lors d'un essai de propreté d'un moteur essence turbo-compressé. Le moteur a une cylindrée de 1 ,6 L pour 4 cylindres. Sa puissance est de 115 kW. La durée de cycle de l'essai est de 30 heures en alternant régime de ralenti (entre 500 et 750 tours/minutes) et régime de circulation sévérisé (entre 2500 et
5800 tours/min). La température de la composition lubrifiante est comprise entre 50 et 150 °C et la température de l'eau du système de refroidissement est comprise entre 50 et 97 °C. Aucune vidange, ni aucun appoint de composition lubrifiante ne sont effectués durant l'essai. On utilise du carburant E10. Au cours de l'essai, à T= Oh, 48h, 72h, 96h, 120h, 144h et 168h, un échantillon de 2-3 mL de la composition lubrifiante est prélevé et le coefficient de frottement de cette composition est mesuré au moyen d’un tribomètre avec un contact bille trois plans rotatif présentant les caractéristiques suivantes : Each lubricating composition (10 kg) is evaluated during a cleanliness test of a turbo-compressed gasoline engine. The engine has a displacement of 1.6 L for 4 cylinders. Its power is 115 kW. The test cycle duration is 30 hours, alternating idling speed (between 500 and 750 rpm) and severe circulation speed (between 2500 and 5800 rpm). The temperature of the lubricating composition is between 50 and 150 ° C and the temperature of the water in the cooling system is between 50 and 97 ° C. No draining or any addition of lubricating composition is carried out during the test. E10 fuel is used. During the test, at T = Oh, 48h, 72h, 96h, 120h, 144h and 168h, a sample of 2-3 mL of the lubricating composition is taken and the coefficient of friction of this composition is measured by means of '' a tribometer with a three-plane rotary ball contact having the following characteristics:
- diamètre des billes : 5 mm, - température : 100°C, - diameter of the balls: 5 mm, - temperature: 100 ° C,
- fréquence : 5 Hz, - frequency: 5 Hz,
- pression maximale de contact : 700 MPa, - maximum contact pressure: 700 MPa,
- longueur de trace : 5 mm - track length: 5 mm
- durée : 1h. Les résultats obtenus sont regroupés dans le tableau 3 ci-dessous mais également représentés sur la figure 1 . - duration: 1 hour. The results obtained are collated in Table 3 below but also shown in Figure 1.
Tableau 3
Table 3
Ces résultats (Tableau 3) ainsi que les courbe de la figure 1 montrent que l’utilisation d’un composé 2,5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate lorsqu’il est présent dans une composition lubrifiante comprenant un composé organomolybdène permet de conserver un coefficient de frottement bas des compositions lubrifiantes selon l’invention mises en œuvre lors d’un essai moteur contrairement aux compositions comparatives comprenant un composé organomolybdène seul. II est donc démontré au moyen d’essai moteur simulant les conditions réelles de mises en œuvre du lubrifiant dans un moteur que l’utilisation d’un composé 2, 5-dimercapto-1 ,3,4- thiadiazole alkyl (poly)carboxylate dans une composition comprenant un composé
organomolybdène, tel que le MoDTC, permet de protéger au cours du temps le composé organomolybdène de l’oxydation et par conséquent, permet d’obtenir un coefficient de frottement bas pour la composition lubrifiante dans le temps. Il est entendu que plus le coefficient de frottement est bas au cours du temps, plus les effets sur les propriétés fuel eco de la composition lubrifiante sont maintenues dans le temps.
These results (Table 3) as well as the curves of FIG. 1 show that the use of a 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound when it is present in a lubricating composition comprising an organomolybdenum compound makes it possible to maintain a low coefficient of friction of the lubricating compositions according to the invention used during an engine test, unlike the comparative compositions comprising an organomolybdenum compound alone. It is therefore demonstrated by means of engine tests simulating the real conditions of use of the lubricant in an engine that the use of a compound 2, 5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate in a composition comprising a compound organomolybdenum, such as MoDTC, makes it possible to protect the organomolybdenum compound over time from oxidation and consequently, makes it possible to obtain a low coefficient of friction for the lubricating composition over time. It is understood that the lower the coefficient of friction is over time, the more the effects on the fuel eco properties of the lubricating composition are maintained over time.
Claims
1. Composition d’additifs pour huile lubrifiante comprenant : 1. A lubricating oil additive composition comprising:
- au moins un composé organomolybdène, et - au moins un composé 2,5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate. - at least one organomolybdenum compound, and - at least one 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound.
2. Composition d’additifs selon la revendication 1 , dans laquelle le composé organomolybdène est choisi parmi les composés organomolybdène dinucléaires, de préférence parmi les dithiocarbamates de molybdène. 2. Additive composition according to claim 1, wherein the organomolybdenum compound is selected from dinuclear organomolybdenum compounds, preferably from molybdenum dithiocarbamates.
3. Composition d’additifs selon la revendication 1 , dans laquelle le composé 2,5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate est choisi parmi les composés de formule (IV) suivante :
dans laquelle R’ représente un groupement alkyle en C1-C34 substitué par au moins un groupement carboxylate d’alkyle en C1-C34, de préférence au moins deux groupements carboxylate d’alkyle en C1-C34. 3. Additive composition according to claim 1, in which the 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound is chosen from the compounds of formula (IV) below: in which R 'represents a C 1 -C 34 alkyl group substituted by at least one C 1 -C 34 alkyl carboxylate group, preferably at least two C1-C34 alkyl carboxylate groups.
4. Composition d’additifs selon la revendication 3, dans laquelle le groupement R’ est un groupement alkyle en C1-C30, de préférence en C1-C20, plus préférentiellement en C1-C10, typiquement en C1-C5, par exemple est un groupement éthyle. 4. Additive composition according to claim 3, in which the group R 'is an alkyl group in C1-C30, preferably in C1-C20, more preferably in C1-C10, typically in C1-C5, for example is a ethyl group.
5. Composition d’additifs selon l’une quelconque des revendications 3 et 4, dans laquelle le ou les groupement(s) carboxylate d’alkyle sont choisi, de manière indépendante, parmi les groupements carboxylate d’alkyle en C1-C30, de préférence en C1- C20, plus préférentiellement en C1-C10, par exemple est un groupement 2-éthylhexyl. 5. Additive composition according to any one of claims 3 and 4, in which the alkyl carboxylate group (s) are selected, independently, from C1-C30 alkyl carboxylate groups, from preferably C1-C20, more preferably C1-C10, for example is a 2-ethylhexyl group.
6. Composition d’additifs selon l’une quelconque des revendications précédentes, dans laquelle le composé 2,5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate répond à la formule (V) suivante :
6. An additive composition according to any one of the preceding claims, in which the 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound corresponds to the following formula (V):
7. Composition d’additifs selon l’une quelconque des revendications 1 à 4, dans laquelle le ratio massique entre le composé organomolybdène et le composé 2,5- dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate va de 1 :100 à 100 :1 , de préférence de 7. An additive composition according to any one of claims 1 to 4, wherein the mass ratio between the organomolybdenum compound and the 2,5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound ranges from 1 : 100 to 100: 1, preferably
1 :10 à 10 :1 , plus préférentiellement de 1 :5 à 5 :1 . 1: 10 to 10: 1, more preferably 1: 5 to 5: 1.
8. Composition lubrifiante comprenant : 8. Lubricating composition comprising:
- au moins une huile de base, et - at least one base oil, and
- au moins une composition d’additifs telle que définie à l’une quelconque des revendications précédentes. - at least one additive composition as defined in any one of the preceding claims.
9. Composition lubrifiante selon la revendication 8, comprenant de 50% à 99 ,5% en masse d’huile de base, par rapport à la masse totale de la composition lubrifiante. 9. A lubricating composition according to claim 8, comprising from 50% to 99.5% by mass of base oil, relative to the total mass of the lubricating composition.
10. Composition lubrifiante selon l’une quelconque des revendications 8 et 9, dans laquelle la teneur en élément molybdène va de 50 à 1 500 ppm en masse, de préférence de 100 à 1 000 ppm en masse, par rapport à la masse totale de la composition lubrifiante. 10. A lubricating composition according to any one of claims 8 and 9, in which the content of molybdenum element ranges from 50 to 1,500 ppm by mass, preferably from 100 to 1,000 ppm by mass, relative to the total mass of the lubricating composition.
11. Composition lubrifiante selon l’une quelconque des revendications 8 à 10, comprenant de 0,2% à 1 ,0% en masse de composé 2,5-dimercapto-1 ,3,4-thiadiazole, alkyl (poly)carboxylate, de préférence 0,2 à 0,9% en masse, par exemple 0,5% en masse, par rapport à la masse totale de la composition lubrifiante. 11. A lubricating composition according to any one of claims 8 to 10, comprising from 0.2% to 1.0% by weight of compound 2,5-dimercapto-1, 3,4-thiadiazole, alkyl (poly) carboxylate, preferably 0.2 to 0.9% by mass, for example 0.5% by mass, relative to the total mass of the lubricating composition.
12. Composition lubrifiante selon l’une quelconque des revendications 8 à 11 , présentant une teneur en soufre allant de 0,01 % à 5% en masse, de préférence de 0,1 % à 2% en masse, plus préférentiellement de 0,1% à 0,5% en masse, par rapport à la masse totale de la composition. 12. Lubricating composition according to any one of claims 8 to 11, having a sulfur content ranging from 0.01% to 5% by mass, preferably from 0.1% to 2% by mass, more preferably from 0, 1% to 0.5% by mass, relative to the total mass of the composition.
13. Utilisation d’un composé 2, 5-dimercapto-1 ,3,4-thiadiazole alkyl (poly)carboxylate dans une composition lubrifiante comprenant au moins une huile de base et au moins un composé organomolybdène. 13. Use of a 2, 5-dimercapto-1, 3,4-thiadiazole alkyl (poly) carboxylate compound in a lubricating composition comprising at least one base oil and at least one organomolybdenum compound.
14. Utilisation selon la revendication 13, pour maintenir les économies de carburant dans le temps d’un moteur à combustion interne. 14. Use according to claim 13, for maintaining the fuel economy over time of an internal combustion engine.
15. Utilisation selon l’une quelconque des revendications 13 et 14, dans laquelle le composé organomolybdène est choisi parmi les composés organomolybdène dinucléaires.
15. Use according to any one of claims 13 and 14, wherein the organomolybdenum compound is selected from dinuclear organomolybdenum compounds.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2003253A FR3108914B1 (en) | 2020-04-01 | 2020-04-01 | Lubricant composition comprising a 2,5-dimercapto-1,3,4-thiadiazole alkyl polycarboxylate compound |
| PCT/EP2021/058073 WO2021198131A1 (en) | 2020-04-01 | 2021-03-29 | Lubricant composition comprising a 2,5-dimercapto-1,3,4-thiadiazole alkyl polycarboxylate compound |
Publications (1)
| Publication Number | Publication Date |
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| EP4127112A1 true EP4127112A1 (en) | 2023-02-08 |
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|---|---|---|---|
| EP21714206.6A Pending EP4127112A1 (en) | 2020-04-01 | 2021-03-29 | Lubricant composition comprising a 2,5-dimercapto-1,3,4-thiadiazole alkyl polycarboxylate compound |
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| Country | Link |
|---|---|
| US (1) | US20230220294A1 (en) |
| EP (1) | EP4127112A1 (en) |
| JP (1) | JP2023519736A (en) |
| KR (1) | KR20220157501A (en) |
| CN (1) | CN115362243B (en) |
| FR (1) | FR3108914B1 (en) |
| WO (1) | WO2021198131A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4889647A (en) | 1985-11-14 | 1989-12-26 | R. T. Vanderbilt Company, Inc. | Organic molybdenum complexes |
| US5137647A (en) | 1991-12-09 | 1992-08-11 | R. T. Vanderbilt Company, Inc. | Organic molybdenum complexes |
| US6017858A (en) * | 1993-01-19 | 2000-01-25 | R.T. Vanderbilt Co., Inc. | Synergistic organomolybdenum compositions and lubricating compositions containing same |
| JPH07197068A (en) | 1993-12-30 | 1995-08-01 | Tonen Corp | Lubricating oil composition |
| US5412130A (en) | 1994-06-08 | 1995-05-02 | R. T. Vanderbilt Company, Inc. | Method for preparation of organic molybdenum compounds |
| JP3454593B2 (en) | 1994-12-27 | 2003-10-06 | 旭電化工業株式会社 | Lubricating oil composition |
| JPH0931483A (en) | 1995-07-20 | 1997-02-04 | Tonen Corp | Lubricant composition |
| JP4201902B2 (en) | 1998-12-24 | 2008-12-24 | 株式会社Ａｄｅｋａ | Lubricating composition |
| US6806241B2 (en) * | 2001-09-21 | 2004-10-19 | R.T. Vanderbilt Company, Inc. | Antioxidant additive compositions and lubricating compositions containing the same |
| CN100412178C (en) * | 2003-10-10 | 2008-08-20 | R.T.范德比尔特公司 | Lubricating compositions containing synthetic ester base oil, molybdenum compounds and thiadiazole-based compounds |
| US7205423B1 (en) | 2005-09-23 | 2007-04-17 | R.T. Vanderbilt Company, Inc. | Process for the preparation of organo-molybdenum compounds |
| FR2961823B1 (en) * | 2010-06-25 | 2013-06-14 | Total Raffinage Marketing | LUBRICATING COMPOSITIONS FOR AUTOMOTIVE TRANSMISSIONS |
| FR2998303B1 (en) * | 2012-11-16 | 2015-04-10 | Total Raffinage Marketing | LUBRICANT COMPOSITION |
| ES2657163T3 (en) * | 2013-09-17 | 2018-03-01 | Vanderbilt Chemicals, Llc | Method of reducing aqueous separation in an emulsion composition suitable for an engine fueled with E85 fuel |
| JP6872299B2 (en) * | 2016-10-11 | 2021-05-19 | 株式会社Adeka | Friction reduction method and sliding mechanism |
| JP2018076411A (en) * | 2016-11-08 | 2018-05-17 | 株式会社Adeka | Lubricating oil composition |
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| US20230220294A1 (en) | 2023-07-13 |
| CN115362243A (en) | 2022-11-18 |
| FR3108914A1 (en) | 2021-10-08 |
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| CN115362243B (en) | 2023-08-25 |
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