EP2791294B1 - Lubricating compositions for transmissions - Google Patents
Lubricating compositions for transmissions Download PDFInfo
- Publication number
- EP2791294B1 EP2791294B1 EP12809233.5A EP12809233A EP2791294B1 EP 2791294 B1 EP2791294 B1 EP 2791294B1 EP 12809233 A EP12809233 A EP 12809233A EP 2791294 B1 EP2791294 B1 EP 2791294B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricant composition
- composition according
- mass
- ethylene
- preferentially
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims description 116
- 230000001050 lubricating effect Effects 0.000 title claims description 82
- 230000005540 biological transmission Effects 0.000 title claims description 16
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical class S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 claims description 36
- 239000004711 α-olefin Substances 0.000 claims description 34
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 30
- 239000005977 Ethylene Substances 0.000 claims description 29
- -1 amine thiophosphate Chemical class 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 239000000314 lubricant Substances 0.000 claims description 22
- 229920000193 polymethacrylate Polymers 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 10
- 239000002199 base oil Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229920002367 Polyisobutene Polymers 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- GLOYGJPNNKTDIG-UHFFFAOYSA-N SC=1N=NSC=1S Chemical group SC=1N=NSC=1S GLOYGJPNNKTDIG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- OTNSJAUBOYWVEB-UHFFFAOYSA-N 1,2,4-thiadiazolidine-3,5-dithione Chemical compound S=C1NSC(=S)N1 OTNSJAUBOYWVEB-UHFFFAOYSA-N 0.000 claims description 4
- AJBLKZFBURBYPT-UHFFFAOYSA-N 1,2,5-thiadiazolidine-3,4-dithione Chemical compound SC1=NSN=C1S AJBLKZFBURBYPT-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 150000003335 secondary amines Chemical class 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 description 23
- 229910052717 sulfur Inorganic materials 0.000 description 23
- 238000000034 method Methods 0.000 description 14
- 239000011593 sulfur Substances 0.000 description 14
- 125000004434 sulfur atom Chemical group 0.000 description 14
- 239000005069 Extreme pressure additive Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 239000007866 anti-wear additive Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 235000006708 antioxidants Nutrition 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229920006213 ethylene-alphaolefin copolymer Polymers 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 3
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- 201000008752 progressive muscular atrophy Diseases 0.000 description 3
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 3
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical class CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- BTHAQRDGBHUQMR-UHFFFAOYSA-N [S]P(=O)=O Chemical compound [S]P(=O)=O BTHAQRDGBHUQMR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- LMZSPXZNYGLPAV-UHFFFAOYSA-N butoxy-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCOP(O)(O)=S LMZSPXZNYGLPAV-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- 150000004867 thiadiazoles Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UGUHFDPGDQDVGX-UHFFFAOYSA-N 1,2,3-thiadiazole Chemical compound C1=CSN=N1 UGUHFDPGDQDVGX-UHFFFAOYSA-N 0.000 description 1
- YGTAZGSLCXNBQL-UHFFFAOYSA-N 1,2,4-thiadiazole Chemical compound C=1N=CSN=1 YGTAZGSLCXNBQL-UHFFFAOYSA-N 0.000 description 1
- UDGKZGLPXCRRAM-UHFFFAOYSA-N 1,2,5-thiadiazole Chemical compound C=1C=NSN=1 UDGKZGLPXCRRAM-UHFFFAOYSA-N 0.000 description 1
- MBIZXFATKUQOOA-UHFFFAOYSA-N 1,3,4-thiadiazole Chemical compound C1=NN=CS1 MBIZXFATKUQOOA-UHFFFAOYSA-N 0.000 description 1
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- DRHABPMHZRIRAH-UHFFFAOYSA-N 2,4,4,6,6-pentamethylhept-2-ene Chemical group CC(C)=CC(C)(C)CC(C)(C)C DRHABPMHZRIRAH-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- UZEFVQBWJSFOFE-UHFFFAOYSA-N dibutyl hydrogen phosphite Chemical class CCCCOP(O)OCCCC UZEFVQBWJSFOFE-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- CAVXVJGHUYVTRI-UHFFFAOYSA-N dihydroxy-octoxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCOP(O)(O)=S CAVXVJGHUYVTRI-UHFFFAOYSA-N 0.000 description 1
- ORDPXYVBSFJMAW-UHFFFAOYSA-N diphenoxy(phenylsulfanyl)phosphane Chemical compound C=1C=CC=CC=1OP(SC=1C=CC=CC=1)OC1=CC=CC=C1 ORDPXYVBSFJMAW-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- ISWBBUXCFWZBKC-UHFFFAOYSA-N dodecoxy-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCCCCCOP(O)(O)=S ISWBBUXCFWZBKC-UHFFFAOYSA-N 0.000 description 1
- FQERTQNSHXPBQS-UHFFFAOYSA-N dodecylsulfanylphosphonous acid Chemical compound CCCCCCCCCCCCSP(O)O FQERTQNSHXPBQS-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- OTYNBGDFCPCPOU-UHFFFAOYSA-N phosphane sulfane Chemical compound S.P[H] OTYNBGDFCPCPOU-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- TYQTYRXEMJXFJG-UHFFFAOYSA-N phosphorothious acid Chemical compound OP(O)S TYQTYRXEMJXFJG-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/024—Propene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral 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
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—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
- 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
- C10M2223/047—Thioderivatives not containing metallic elements
-
- 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
- C10M2223/049—Phosphite
-
- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
-
- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
Definitions
- the present invention relates to lubricating compositions for transmissions, in particular for gearboxes, comprising a specific combination of additives making it possible to reduce the coefficient of friction of said lubricating compositions, thus making it possible to limit the fuel consumption of motor vehicles.
- the compositions according to the invention are suitable for all types of vehicles, in particular light vehicles, and are particularly suitable for manual gearboxes, axles or double clutches.
- VI viscosity index
- ethylene / alpha-olefin copolymer which is known as a viscosity index improving polymer and not as a friction modifier, makes it possible to reduce the coefficient of friction of lubricating compositions, when it ci is in combination with a derivative of dimercaptothiadiazole and an amine thiophosphate.
- Dimercaptothiadiazole derivatives are known as inhibitors of corrosion and extreme pressure additives and not as a friction modifier.
- the Applicant has found that it is possible to formulate transmission oils with very low coefficients of friction from a composition containing a compound chosen from dimercaptothiadiazoles, a compound chosen from the group of ethylene-alphaolefin copolymers. and an amine thiophosphate.
- the lubricating compositions according to the invention exhibit low coefficients of friction without the addition of friction modifiers.
- the mixture containing at least one dimercaptothiadiazole, at least one ethylene-alphaolefin copolymer and at least one amine thiophosphate, has a synergistic effect on the lowering of the coefficient of friction.
- the present invention relates to a lubricating composition
- a lubricating composition comprising, relative to the total mass of the lubricating composition, one or more base oils, 0.1 to 10% by mass of at least one derivative of dimercaptothiadiazole, 1 to 20%. by mass of at least one copolymer of ethylene and of alphaolefin and 0.2 to 10% by mass of at least one amine thiophosphate of general formula (IVa) in which X 1 and X 2 are independently of each other a sulfur atom or an oxygen atom, at least one of them being a sulfur atom, R 1 and R 2 are either an atom of hydrogen or alkyl groups having between 1 to 22 carbon atoms, preferably between 6 to 18, M is an ammonium formed from a primary, secondary or tertiary amine, of formula R 3 R 4 R 5 R 6 N, where R 3 , R 4 , R 5 , R 6 are either a hydrogen atom or an alkyl group comprising from 1 to 18 carbon
- the lubricating composition according to the invention comprises at least one copolymer of ethylene and of an alpha-olefin comprising from 3 to 30 carbon atoms, preferably from 3 to 24, more preferably from 3 to 20, even more preferably from 3 to 10, even more preferably from 3 to 6.
- the copolymer of ethylene and of alphaolefin according to the invention has the general formula (I): in which R is an alkyl group having 1 to 8 carbon atoms, preferably 1 to 3 carbon atoms, x and y are such that the ratio x / y is between 0.5 and 2 and the sum x + y is between 50 to 150.
- the lubricating composition according to the invention comprises an amount of ethylene / alphaolefin copolymer of between 2 to 15% by mass, relative to the total mass of lubricating composition, preferably from 4 to 10%, more preferably from 5 to 9%.
- the dimercaptothiadiazole derivative according to the invention has the general formula of formula (II) or (III), taken alone or as a mixture: in which, R 1 and R 2 are, independently of one another, hydrogen atoms, linear and / or branched alkyl groups comprising from 1 to 24 carbon atoms, preferably from 2 to 18, more preferably from 4 to 16, even more preferably from 8 to 12 or aromatic substituents, n and m being, independently of one another, integers chosen from the group formed by the integers 1, 2, 3, or 4.
- the lubricating composition according to the invention comprises from 0.2 to 5% by mass of derivative of dimercaptothiadiazole, relative to the total mass of the lubricating composition, preferably from 0.3 to 2%, more preferably from 0, 5 to 1%.
- Particularly preferred compounds are dithiophosphates (X 1 and X 2 are sulfur atoms).
- the lubricating composition according to the invention has an amount of amine thiophosphate of formula (IVa) of between 0.5 to 8%, in mass, relative to the total mass of lubricating composition, preferably from 1 to 5%, more preferably from 2 to 4%.
- the lubricating composition according to the invention further comprises a polymethacrylate.
- the lubricating composition according to the invention further comprises a dispersant derived from polyisobutene.
- the lubricating composition according to the invention further comprises an anti-oxidant additive of amine type.
- the lubricating composition according to the invention further comprises an anti-corrosion additive of phenol type.
- the lubricating composition according to the invention has a kinematic viscosity at 100 ° C. according to the ASTM D445 standard of between 4 and 40 cSt, between 4.1 and 32.5 cSt and preferably between 6 and 18.5 cSt.
- the present invention relates to the use of a lubricating composition for lubricating transmissions such as gearboxes, axles, preferably manual gearboxes of motor vehicles.
- the invention relates to the use of a lubricating composition for lubricating transmissions to reduce the fuel consumption of vehicles, in particular of motor vehicles.
- the present invention relates to the use of at least one copolymer of ethylene and of alpha-olefin and of at least one derivative of dimercaptothiadiazole for reducing the coefficient of friction of a lubricating composition.
- the invention relates to the use of at least one copolymer of ethylene and of alpha-olefin, of at least one derivative of dimercaptothiadiazole and at least one amine thiophosphate for reducing the coefficient of friction of a lubricating composition.
- a subject of the invention is also a process for reducing the coefficient of friction of a lubricating composition, in which at least one base oil is added at least one copolymer of ethylene and of alpha-olefin and of minus a derivative of dimercaptothiadiazole.
- the invention relates to a process for reducing the coefficient of friction of a lubricating composition in which at least one lubricating base oil is added at least one copolymer of ethylene and of alpha-olefin, at least one derivative of dimercaptothiadiazole and at least one amine thiophosphate.
- One of the essential elements of the lubricating compositions according to the invention is a copolymer of ethylene and of alphaolefin.
- the ethylene / alpha-olefin copolymer while being a viscosity index improver such as the polymethacrylates that it can replace, provides the additional advantage that it can reduce the coefficient of friction of said lubricating compositions.
- the copolymer used in the present invention is an ethylene / alphaolefin copolymer.
- the alpha-olefin is an alpha-olefin comprising from 3 to 30 carbon atoms, preferably from 3 to 24, more preferably from 3 to 20, even more preferably from 3 to 10, even more preferably from 3 to 6.
- alpha-olefin which can be used are propylene, butene, pentene, hexene, heptene, octene, nonene, decene, in particular 1-butene, 1-pentene, 1- hexene, 1-octene.
- the copolymer of ethylene and of alphaolefin has the general formula (I): where is R is an alkyl group having 1 to 8 carbon atoms, preferably 1 to 3 carbon atoms, x and y are such that the ratio x / y is between 0.5 and 2 and the sum x + y is between 50 to 150.
- R represents a methyl group
- x and y are such that the ratio x / y is between 0.5 to 1.5 and the sum x + y is between 70 and 130.
- R is a methyl group
- x is equal to 40 and y is equal to 40.
- the ethylene and alphaolefin copolymer according to the invention is chosen from alphaolefin copolymers making it possible to limit the loss of viscosity of the lubricating composition measured at 100 ° C according to the standardized test KRL-45-99 to a lower value. or equal to 5%.
- the lubricating compositions according to the invention comprise from 1 to 20% by mass of ethylene / alpha-olefin copolymer, relative to the total mass of lubricating composition, preferably from 2 to 15%, more preferably from 4 to 10%, even more preferably from 5 to 9%.
- Lucant HC600 sold by the company MITSUI.
- the lubricating compositions according to the invention therefore comprise at least one derivative of dimercaptothiadiazole.
- Said derivative of dimercaptothiadiazole being a compound derived from 4,5-dimercapto-1,2,3-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 3,4-dimercapto-1,2,5 -thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, taken alone or as a mixture.
- Thiadiazoles are heterocyclic compounds comprising two nitrogen atoms, one sulfur atom, two carbon atoms and two double bonds, of general formula C 2 N 2 SH 2 , which can exist in the following forms, respectively 1,2,3 -thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole:
- dimercaptothiadiazole derivative according to the invention is understood to mean chemical compounds derived from the four molecules dimercaptothiadiazoles, 4,5-dimercapto-1,2,3-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 3, 4-dimercapto-1,2,5-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, below taken alone or as a mixture:
- 2,5-dimercapto-1,3,4-thiadiazole the derivatives of 2,5-dimercapto-1,3,4-thiadiazole are molecules of general formula (II) or ( III): in which, R 1 and R 2 are, independently of one another, hydrogen atoms, linear and / or branched alkyl groups comprising from 1 to 24 carbon atoms, preferably from 2 to 18, more preferably from 4 to 16, even more preferably from 8 to 12 or aromatic substituents, n and m being, independently of one another, integers chosen from the group formed by the integers 1, 2, 3 or 4.
- the lubricating compositions according to the invention comprise from 0.1 to 10% by mass, relative to the total mass of the lubricating composition, of dimercaptothiadiazole derivative, preferably from 0.2 to 5%, more preferably from 0.3 at 2%, even more preferably from 0.5 to 1%.
- dimercaptothiadiazole derivative As an example of a dimercaptothiadiazole derivative according to the invention, mention may be made of Anglamol 2198 sold by the company LUBRIZOL.
- Particularly preferred compounds of formula (IVa) are the dithiophosphates of amines in which X 1 and X 2 are sulfur atoms and M, R 3 , R 4 , R 5 , R 6 as defined above.
- the lubricating compositions according to the invention can contain any type of mineral, synthetic or natural, animal or plant lubricating base suitable for their use.
- the base oil (s) used in the lubricating compositions according to the present invention can be oils of mineral or synthetic origin of groups I to V according to the classes defined in the API classification (or their equivalents according to the ATIEL classification) as summarized. below, alone or in combination.
- the mineral base oils according to the invention include all types of bases obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, dealphating, solvent dewaxing, hydrotreatment, hydrocracking and hydroisomerization, hydrofinishing.
- the base oils of the compositions according to the present invention can also be synthetic oils, such as certain esters of carboxylic acids and alcohols, or polyalphaolefins.
- the polyalphaolefins used as base oils are for example obtained from monomers having from 4 to 32 carbon atoms (for example octene, decene), and a viscosity at 100 ° C between 1.5 and 15 cSt according to the standard ASTM D445.
- Their weight average molecular mass is typically between 250 and 3000 according to the ASTM D5296 standard. Mixtures of synthetic and mineral oils can also be used.
- lubricating base to produce the lubricating compositions according to the invention, except that they must have properties, in particular of viscosity, viscosity index, content of sulfur, resistance to oxidation, suitable for use in a gearbox, in particular in a gearbox of motor vehicles, in particular in a manual gearbox.
- the lubricating bases represent at least 50% by mass, relative to the total mass of the lubricating composition, preferably at least 60%, or even at least 70%. Typically, they represent between 75 and 90% by mass, relative to the total mass of the lubricating compositions according to the invention.
- the lubricating compositions according to the invention comprise mineral bases of group I and / or III, or synthetic bases of group IV according to the API classification.
- the lubricating compositions according to the invention have a kinematic viscosity at 100 ° C. measured according to the ASTM D445 standard of between 4 and 41 cSt, according to the SAE J 306 classification, preferably between 4.1 and 32.5 cSt.
- Preferred grades are all grades between grades 75W and 140, including grades 75W, 75W80 and 75W90.
- the lubricating compositions according to the invention have a viscosity index (VI) greater than 120 (standard ASTM 2270).
- the lubricating compositions according to the invention can also contain other additives such as anti-wear and / or extreme pressure additives.
- the phospho-sulfur antiwear and / or extreme pressure additives are for example and without limitation thiophosphoric acid, thiophosphorous acid, esters of these acids, their salts, and dithiophosphates, mono- or dithiophosphates other than the amine thiophosphates according to the invention, particularly the zinc dithiophosphates.
- phospho-sulfurized anti-wear and extreme pressure additives those which contain from 1 to 3 sulfur atoms, such as monobutylthiophosphate, monooctylthiophosphate, monolaurylthiophosphate, dibutylthiophosphate, dilaurylthiophosphate, triophiophiophosphate, triophiophosphate, phenophosphate, triophiophosphate, trilaurylthiophosphate, monobutylthiophosphate, monoctylthiophosphite, monolaurylthiophosphite, dibutylthiophosphite, dilaurylthiophosphite, tributylthiophosphite, trioctylthiophosphite, triphenylthiophosphite, trilaurylthiophosphite and their salts.
- sulfur atoms such as monobutylthiophosphate, monooctylthiophosphate, mono
- salts of esters of thiophosphoric acid and of thiphosphorous acid are those obtained by reaction with a nitrogenous compound such as ammonia or an amine or zinc oxide or zinc chloride.
- the phosphorus-sulfur antiwear and extreme pressure additives of the compositions according to the invention are thiophosphates, corresponding to formula (IVb): where X 1 and X 2 are independently of each other a sulfur atom or an oxygen atom, at least one of them being a sulfur atom, R 1 and R 2 are either an atom hydrogen or alkyl groups having between 1 and 22 carbon atoms, preferably between 6 and 18, M is a metal chosen from the group formed by groups IIA, III, VA, VIA, IB, VIB, VIII of the periodic table, n + being the valence of said metal.
- Particularly preferred compounds of formula (IVb) are dithiophosphates (X 1 and X 2 are sulfur atoms), preferably zinc.
- the lubricating compositions may also contain phosphorus-containing antiwear and extreme pressure additives, such as, for example, alkyl phosphates or alkyl phosphonates, phosphoric acid, phosphorous acid, mono-, di- and triesters of phosphorous acid and phosphoric acid, and their salts.
- phosphorus-containing antiwear and extreme pressure additives such as, for example, alkyl phosphates or alkyl phosphonates, phosphoric acid, phosphorous acid, mono-, di- and triesters of phosphorous acid and phosphoric acid, and their salts.
- the lubricating compositions can also contain sulfur antiwear and extreme pressure additives. Mention may be made, by way of example of sulfur-containing antiwear and extreme pressure additives, dithiocarbamates, thiadiazoles and benzothiazoles, and sulfur-containing olefins.
- SIBs The most common sulfur olefins are called SIBs, for “Sulfurized IsoButylenes”. These sulfur-containing olefins are generally obtained by a sulphurization reaction of olefins with sulfur, hydrogen sulphide or hydrated alkali metal sulphides, for example sodium sulphide. An example of processes for the preparation of such sulfur-containing olefins is for example described in the patents US 4344854 and US 5135670 . A very wide range of olefins can thus be sulfurized.
- sulfurized olefins are produced from isobutylene, diisobutylene, triisobutylene, tripropylene or tetrapropylene.
- the SIBs thus produced are mixtures of compounds of ill-defined structure comprising, among other impurities, trithiones, dithiolethiones and halogens, and a high content of active sulfur.
- the lubricating compositions according to the invention comprise from 0.2 to 10% by mass of antiwear and / or extreme pressure agents, relative to the mass of lubricating composition, preferably from 0.5 to 8%, from 1 at 5%, preferably from 2 to 4%.
- compositions according to the invention may also comprise, in addition to the copolymer of ethylene and of alpha-olefin, other polymers which improve the viscosity index (VI) such as polymethacrylates, polyacrylates, olefin copolymers. , Ethylene Propylene Diene Monomers (EPDM), polybutenes, copolymers of styrene and olefin, hydrogenated or not.
- EPDM Ethylene Propylene Diene Monomers
- the preferred polymers are polymethacrylates (PMA).
- the polymethacrylates will, for example, be linear polymethacrylates, non-dispersed, of low mass or of medium mass.
- low mass is understood to mean PMAs with a weight-average molecular mass Mw of less than 20,000 (standard ASTM D5296).
- average mass is meant PMAs with a weight average molecular mass Mw of between 30,000 and 90,000 (preferably around 50,000 (ASTM D5296).
- high mass PMAs with a weight average molecular mass Mw greater than 100,000 (ASTM D5296).
- the lubricating compositions according to the invention can also contain all types of additives suitable for their use in formulations of oils for transmissions, for example one or more additives chosen from antioxidant additives, corrosion inhibitors, dispersants, present in usual levels required for the application.
- the preferred dispersants are polyisobutylenes (PIB), polyisobutylene of succinic anhydride, amino derivatives of polyisobutylene of succinic anhydride (PIB succinimides).
- the preferred antioxidants are, for example, amino antioxidants, preferably diphenylamines such as octadiphenylamines, phenyl-alpha-naphthyl amines, or phenolic antioxidants (dibutylhydroxytoluene BHT and derivatives) or sulfur-containing antioxidants (sulfurized phenates).
- amino antioxidants preferably diphenylamines such as octadiphenylamines, phenyl-alpha-naphthyl amines, or phenolic antioxidants (dibutylhydroxytoluene BHT and derivatives) or sulfur-containing antioxidants (sulfurized phenates).
- the preferred anti-corrosion additives are phenolic derivatives, in particular phenolic derivatives ethoxylated and substituted by alkyl groups in the ortho position.
- the invention also relates to a method of lubricating transmissions such as gearboxes, axles, preferably manual gearboxes of motor vehicles, said method using a lubricating composition as defined above.
- this method makes it possible to reduce the fuel consumption of vehicles, in particular of motor vehicles.
- the invention also relates to a method for lubricating transmissions, such as gearboxes, axles, preferably manual gearboxes of motor vehicles, said method implementing at least one copolymer of ethylene and alphaolefin and at least one derivative of dimercaptothiadiazole.
- the invention relates to a method of lubricating at least one transmission member, the method comprising a step of bringing into contact a lubricating composition comprising at least one copolymer of ethylene and alpha- olefin and at least one derivative of dimercaptothiadiazole.
- the invention in another embodiment, relates to a method of lubricating at least one transmission member, the method comprising a step of bringing into contact a lubricating composition comprising at least one copolymer of ethylene and of alpha -olefin, at least one derivative of dimercaptothiadiazole and at least one amine thiophosphate.
- transmission member is understood to mean, for example, an axle or a gearbox, in particular a gearbox for a motor vehicle.
- this process makes it possible to reduce the coefficient of friction of a lubricating composition.
- The% by weight of the components of the lubricating compositions are shown in Table I below, as well as the Cameron Plint results.
- the procedure used measures the coefficient of friction of a roller on a plane, all immersed in the test lubricant, under conditions of temperature (60 ° C, 100 ° C and 140 ° C), load (50, 100, 150 and 200N) and variable frequency (5, 10, 20 and 40 Hz) in order to reproduce the friction conditions encountered in the gearbox control mechanisms during use.
- the stroke of the roller on the plane that is to say the reciprocating movement back and forth, is fixed at 7 mm.
- the duration of the test is 10 min.
- Lubricating compositions 1 to 4 are control lubricating compositions.
- Lubricating compositions 6 and 7 are lubricating compositions according to the invention.
- Lubricating compositions 1, 3 and 5 do not contain an ethylene / alphaolefin copolymer.
- the measured friction coefficients correspond to those which can be expected from a person skilled in the art.
- Composition 8 is a lubricating composition not comprising amine thiophosphate.
- ethylene-alphaolefin copolymer a dimercaptothiadiazole and an amine thiophosphate in a lubricating composition improves the coefficient of friction of said composition.
- Example 7 exhibits a loss in viscosity measured at 100 ° C. according to the standardized test CEC L-45-99 of 2.6%; such a viscosity loss value being perfectly in line with the application of the composition in the lubrication of transmission members, and more particularly of gearboxes.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Description
La présente invention est relative à des compositions lubrifiantes pour transmissions, en particulier pour boîtes de vitesse, comprenant une combinaison spécifique d'additifs permettant de diminuer le coefficient de frottement desdites compositions lubrifiantes, permettant ainsi de limiter la consommation de carburant de véhicules à moteurs. Les compositions selon l'invention conviennent pour tous types de véhicules, notamment véhicules légers, et sont particulièrement adaptées aux boîtes de vitesse manuelles, ponts ou doubles embrayages.The present invention relates to lubricating compositions for transmissions, in particular for gearboxes, comprising a specific combination of additives making it possible to reduce the coefficient of friction of said lubricating compositions, thus making it possible to limit the fuel consumption of motor vehicles. The compositions according to the invention are suitable for all types of vehicles, in particular light vehicles, and are particularly suitable for manual gearboxes, axles or double clutches.
Les préoccupations environnementales actuelles, notamment en vue de réduire les émissions de CO2, conduisent à réduire la consommation de carburant des véhicules légers. Cette réduction de la consommation d'énergie peut s'effectuer via des organes tels que le moteur et/ou les transmissions, telles que les ponts ou doubles embrayages et notamment les boîtes de vitesse manuelles.Current environmental concerns, particularly with a view to reducing CO 2 emissions, lead to reducing the fuel consumption of light vehicles. This reduction in energy consumption can be effected via components such as the engine and / or transmissions, such as axles or double clutches and in particular manual gearboxes.
Pour réduire la consommation de carburant, on peut utiliser des polymères améliorant d'indice de viscosité (VI) pour jouer sur la viscosité du lubrifiant ou utiliser des modificateurs de frottements pour jouer sur le coefficient de frottement du lubrifiant.To reduce fuel consumption, it is possible to use polymers which improve the viscosity index (VI) to influence the viscosity of the lubricant or to use friction modifiers to influence the coefficient of friction of the lubricant.
Les documents
La demanderesse a maintenant constaté que l'utilisation d'un copolymère éthylène/alphaoléfine, qui est un connu comme polymère améliorant d'indice de viscosité et non comme modificateur de frottement, permet de diminuer le coefficient de frottement des compositions lubrifiantes, lorsque celui-ci est en combinaison avec un dérivé du dimercaptothiadiazole et un thiophosphate d'amine. Les dérivés du dimercaptothiadiazole sont connus en tant qu'inhibiteur de corrosion et additifs extrême-pression et non pas comme modificateur de frottement.The Applicant has now found that the use of an ethylene / alpha-olefin copolymer, which is known as a viscosity index improving polymer and not as a friction modifier, makes it possible to reduce the coefficient of friction of lubricating compositions, when it ci is in combination with a derivative of dimercaptothiadiazole and an amine thiophosphate. Dimercaptothiadiazole derivatives are known as inhibitors of corrosion and extreme pressure additives and not as a friction modifier.
De façon surprenante, la demanderesse a constaté qu'il est possible de formuler des huiles de transmissions à très bas coefficients de frottement à partir d'une composition contenant un composé choisi parmi les dimercaptothiadiazoles, un composé choisi dans le groupe des copolymères éthylène-alphaoléfine et un thiophosphate d'amine. Les compositions lubrifiantes selon l'invention présentent des coefficients de frottement faibles sans ajout de modificateurs de frottement.Surprisingly, the Applicant has found that it is possible to formulate transmission oils with very low coefficients of friction from a composition containing a compound chosen from dimercaptothiadiazoles, a compound chosen from the group of ethylene-alphaolefin copolymers. and an amine thiophosphate. The lubricating compositions according to the invention exhibit low coefficients of friction without the addition of friction modifiers.
Sans vouloir être lié par une quelconque théorie, le mélange, contenant au moins un dimercaptothiadiazole, au moins un copolymère éthylène-alphaoléfine et au moins un thiophosphate d'amine, a un effet de synergie sur l'abaissement du coefficient de frottement.Without wishing to be bound by any theory, the mixture, containing at least one dimercaptothiadiazole, at least one ethylene-alphaolefin copolymer and at least one amine thiophosphate, has a synergistic effect on the lowering of the coefficient of friction.
Par ailleurs, la composition lubrifiante comprenant un mélange de dimercaptothiadiazole, de copolymère éthylène-alphaoléfine et de thiophosphate d'amine présente aussi les avantages suivants :
- Faibles coefficients de frottement sans apport de modificateurs de frottement,
- Formulation améliorant le rendement des transmissions,
- Utilisation moindre de polymère dans l'huile,
- Formules à grande stabilité thermique.
- Low friction coefficients without contribution of friction modifiers,
- Formulation improving transmission efficiency,
- Less use of polymer in oil,
- High thermal stability formulas.
La présente invention a pour objet une composition lubrifiante comprenant, par rapport à la masse totale de la composition lubrifiante, une ou plusieurs huiles de base, 0,1 à 10% en masse d'au moins un dérivé du dimercaptothiadiazole, 1 à 20% en masse d'au moins un copolymère d'éthylène et d'alphaoléfine et 0,2 à 10% en masse d'au moins un thiophosphate d'amine de formule générale (IVa)
ledit dérivé du dimercaptothiadiazole étant un composé dérivé du 4,5-dimercapto-1,2,3-thiadiazole, du 3,5-dimercapto-1,2,4-thiadiazole, du 3,4-dimercapto-1,2,5-thiadiazole, du 2,5-dimercapto-1,3,4-thiadiazole, pris seuls ou en mélange.The present invention relates to a lubricating composition comprising, relative to the total mass of the lubricating composition, one or more base oils, 0.1 to 10% by mass of at least one derivative of dimercaptothiadiazole, 1 to 20%. by mass of at least one copolymer of ethylene and of alphaolefin and 0.2 to 10% by mass of at least one amine thiophosphate of general formula (IVa)
said derivative of dimercaptothiadiazole being a compound derived from 4,5-dimercapto-1,2,3-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 3,4-dimercapto-1,2,5 -thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, taken alone or as a mixture.
Préférentiellement, la composition lubrifiante selon l'invention comprend au moins un copolymère d'éthylène et d'une alphaoléfine comprenant de 3 à 30 atomes de carbone, de préférence de 3 à 24, plus préférentiellement de 3 à 20, encore plus préférentiellement de 3 à 10, encore plus préférentiellement de 3 à 6.Preferably, the lubricating composition according to the invention comprises at least one copolymer of ethylene and of an alpha-olefin comprising from 3 to 30 carbon atoms, preferably from 3 to 24, more preferably from 3 to 20, even more preferably from 3 to 10, even more preferably from 3 to 6.
Préférentiellement, le copolymère d'éthylène et d'alphaoléfine selon l'invention a pour formule générale (I) :
Préférentiellement, la composition lubrifiante selon l'invention comprend une quantité de copolymère d'éthylène et d'alphaoléfine comprise entre 2 à 15% en masse, par rapport à la masse totale de composition lubrifiante, de préférence de 4 à 10%, plus préférentiellement de 5 à 9%.Preferably, the lubricating composition according to the invention comprises an amount of ethylene / alphaolefin copolymer of between 2 to 15% by mass, relative to the total mass of lubricating composition, preferably from 4 to 10%, more preferably from 5 to 9%.
Préférentiellement, le dérivé du dimercaptothiadiazole selon l'invention a pour formule générale la formule (II) ou (III), pris seul ou en mélange :
Préférentiellement, la composition lubrifiante selon l'invention comprend de 0,2 à 5%en masse de dérivé de dimercaptothiadiazole, par rapport à la masse totale de la composition lubrifiante, de préférence de 0,3 à 2%, plus préférentiellement de 0,5 à 1%.Preferably, the lubricating composition according to the invention comprises from 0.2 to 5% by mass of derivative of dimercaptothiadiazole, relative to the total mass of the lubricating composition, preferably from 0.3 to 2%, more preferably from 0, 5 to 1%.
La composition lubrifiante selon l'invention comprend un thiophosphate d'amine de formule générale (IVa):
Des composés particulièrement préférés sont les dithiophosphates (X1 et X2 sont des atomes de soufre).Particularly preferred compounds are dithiophosphates (X 1 and X 2 are sulfur atoms).
Préférentiellement, la composition lubrifiante selon l'invention a une quantité de thiophosphate d'amine de formule (IVa) comprise entre 0,5 à 8%, en masse, par rapport à la masse totale de composition lubrifiante, de préférence de 1 à 5%, plus préférentiellement de 2 à 4%.Preferably, the lubricating composition according to the invention has an amount of amine thiophosphate of formula (IVa) of between 0.5 to 8%, in mass, relative to the total mass of lubricating composition, preferably from 1 to 5%, more preferably from 2 to 4%.
Préférentiellement, la composition lubrifiante selon l'invention comprend en outre un polyméthacrylate.Preferably, the lubricating composition according to the invention further comprises a polymethacrylate.
Préférentiellement, la composition lubrifiante selon l'invention comprend en outre un dispersant dérivé du polyisobutène.Preferably, the lubricating composition according to the invention further comprises a dispersant derived from polyisobutene.
Préférentiellement, la composition lubrifiante selon l'invention comprend en outre un additif anti-oxydant de type amine.Preferably, the lubricating composition according to the invention further comprises an anti-oxidant additive of amine type.
Préférentiellement, la composition lubrifiante selon l'invention comprend en outre un additif anti-corrosion de type phénol.Preferably, the lubricating composition according to the invention further comprises an anti-corrosion additive of phenol type.
Préférentiellement, la composition lubrifiante selon l'invention a une viscosité cinématique à 100°C selon la norme ASTM D445 comprise entre 4 et 40 cSt, entre 4,1 et 32,5 cSt et de préférence entre 6 et 18,5 cSt.Preferably, the lubricating composition according to the invention has a kinematic viscosity at 100 ° C. according to the ASTM D445 standard of between 4 and 40 cSt, between 4.1 and 32.5 cSt and preferably between 6 and 18.5 cSt.
La présente invention est relative à l'utilisation d'une composition lubrifiante pour la lubrification des transmissions telles que les boîtes de vitesse, les ponts, de préférence les boîtes de vitesse manuelles des véhicules automobiles.The present invention relates to the use of a lubricating composition for lubricating transmissions such as gearboxes, axles, preferably manual gearboxes of motor vehicles.
Préférentiellement l'invention est relative à l'utilisation d'une composition lubrifiante pour la lubrification des transmissions pour réduire la consommation de carburant de véhicules, en particulier de véhicules automobiles.Preferably, the invention relates to the use of a lubricating composition for lubricating transmissions to reduce the fuel consumption of vehicles, in particular of motor vehicles.
La présente invention est relative à l'utilisation d'au moins un copolymère d'éthylène et d'alpha-oléfine et d'au moins un dérivé du dimercaptothiadiazole pour diminuer le coefficient de frottement d'une composition lubrifiante.The present invention relates to the use of at least one copolymer of ethylene and of alpha-olefin and of at least one derivative of dimercaptothiadiazole for reducing the coefficient of friction of a lubricating composition.
Dans un mode de réalisation, l'invention concerne l'utilisation d'au moins un copolymère d'éthylène et d'alpha-oléfine, d'au moins un dérivé du dimercaptothiadiazole et d'au moins un thiophosphate d'amine pour diminuer le coefficient de frottement d'une composition lubrifiante.In one embodiment, the invention relates to the use of at least one copolymer of ethylene and of alpha-olefin, of at least one derivative of dimercaptothiadiazole and at least one amine thiophosphate for reducing the coefficient of friction of a lubricating composition.
L'invention a également pour objet un procédé pour diminuer le coefficient de frottement d'une composition lubrifiante, dans lequel on ajoute à au moins une huile de base, au moins un copolymère d'éthylène et d'alpha-oléfine et d'au moins un dérivé du dimercaptothiadiazole.A subject of the invention is also a process for reducing the coefficient of friction of a lubricating composition, in which at least one base oil is added at least one copolymer of ethylene and of alpha-olefin and of minus a derivative of dimercaptothiadiazole.
Dans un mode de réalisation, l'invention concerne un procédé pour diminuer le coefficient de frottement d'une composition lubrifiante dans lequel on ajoute à au moins une huile de base lubrifiante, au moins un copolymère d'éthylène et d'alpha-oléfine, au moins un dérivé du dimercaptothiadiazole et au moins un thiophosphate d'amine.In one embodiment, the invention relates to a process for reducing the coefficient of friction of a lubricating composition in which at least one lubricating base oil is added at least one copolymer of ethylene and of alpha-olefin, at least one derivative of dimercaptothiadiazole and at least one amine thiophosphate.
Un des éléments essentiels des compositions lubrifiantes selon l'invention est un copolymère d'éthylène et d'alphaoléfine. Le copolymère d'éthylène et d'alphaoléfine, tout en étant un améliorant d'indice de viscosité comme les polyméthacrylates qu'il peut remplacer, apporte l'avantage supplémentaire qu'il peut diminuer le coefficient de frottement desdites compositions lubrifiantes.One of the essential elements of the lubricating compositions according to the invention is a copolymer of ethylene and of alphaolefin. The ethylene / alpha-olefin copolymer, while being a viscosity index improver such as the polymethacrylates that it can replace, provides the additional advantage that it can reduce the coefficient of friction of said lubricating compositions.
Le copolymère utilisé dans la présente invention est un copolymère d'éthylène et d'alphaoléfine. L'alpha-oléfine est une alpha-oléfine comprenant de 3 à 30 atomes de carbone, de préférence de 3 à 24, plus préférentiellement de 3 à 20, encore plus préférentiellement de 3 à 10, encore plus préférentiellement de 3 à 6. Des exemples d'alpha-oléfine utilisables sont le propylène, le butène, le pentène, l'hexène, l'heptène, l'octène, le nonène, le décène, en particulier le 1-butène, le 1-pentène, le 1-héxène, le 1-octène.The copolymer used in the present invention is an ethylene / alphaolefin copolymer. The alpha-olefin is an alpha-olefin comprising from 3 to 30 carbon atoms, preferably from 3 to 24, more preferably from 3 to 20, even more preferably from 3 to 10, even more preferably from 3 to 6. examples of alpha-olefin which can be used are propylene, butene, pentene, hexene, heptene, octene, nonene, decene, in particular 1-butene, 1-pentene, 1- hexene, 1-octene.
De préférence, le copolymère d'éthylène et d'alphaoléfine a pour formule générale (I) :
Préférentiellement, R représente un groupe méthyle, et x et y sont tels que le rapport x/y est compris entre 0,5 à 1,5 et la somme x+y est comprise entre 70 et 130.Preferably, R represents a methyl group, and x and y are such that the ratio x / y is between 0.5 to 1.5 and the sum x + y is between 70 and 130.
Préférentiellement, R est un groupe méthyle, x est égal à 40 et y est égal à 40.Preferably, R is a methyl group, x is equal to 40 and y is equal to 40.
Préférentiellement, le copolymère d'éthylène et d'alphaoléfine selon l'invention est choisi parmi les copolymères alphaoléfines permettant de limiter la perte de viscosité de la composition lubrifiante mesurée à 100°C selon le test normé KRL-45-99 à une valeur inférieure ou égale à 5%.Preferably, the ethylene and alphaolefin copolymer according to the invention is chosen from alphaolefin copolymers making it possible to limit the loss of viscosity of the lubricating composition measured at 100 ° C according to the standardized test KRL-45-99 to a lower value. or equal to 5%.
Les compositions lubrifiantes selon l'invention comprennent de 1 à 20% en masse de copolymère éthylène/alphaoléfine, par rapport à la masse totale de composition lubrifiante, de préférence de 2 à 15%, plus préférentiellement de 4 à 10%, encore plus préférentiellement de 5 à 9%.The lubricating compositions according to the invention comprise from 1 to 20% by mass of ethylene / alpha-olefin copolymer, relative to the total mass of lubricating composition, preferably from 2 to 15%, more preferably from 4 to 10%, even more preferably from 5 to 9%.
Comme exemple de copolymère éthylène/alphaoléfine selon l'invention, on peut citer le Lucant HC600 commercialisé par la société MITSUI.As example of an ethylene / alpha-olefin copolymer according to the invention, mention may be made of Lucant HC600 sold by the company MITSUI.
De façon surprenante, l'effet du copolymère éthylène/alphaoléfine sur l'abaissement du coefficient de frottement des compositions lubrifiantes selon l'invention, a été observé en présence d'un dérivé du dimercaptothiadiazole. En revanche, cet effet n'a pas été observé avec l'utilisation d'autres additifs.Surprisingly, the effect of the ethylene / alpha olefin copolymer on the lowering of the coefficient of friction of the lubricating compositions according to the invention was observed in the presence of a derivative of dimercaptothiadiazole. However, this effect was not observed with the use of other additives.
Les compositions lubrifiantes selon l'invention comprennent donc au moins un dérivé du dimercaptothiadiazole. Ledit dérivé du dimercaptothiadiazole étant un composé dérivé du 4,5-dimercapto-1,2,3-thiadiazole, du 3,5-dimercapto-1,2,4-thiadiazole, du 3,4-dimercapto-1,2,5-thiadiazole, du 2,5-dimercapto-1,3,4-thiadiazole, pris seuls ou en mélange. Les thiadiazoles sont des composés hétérocycliques comprenant deux atomes d'azote, un atome de soufre, deux atomes de carbone et deux doubles liaisons, de formule générale C2N2SH2, pouvant exister sous les formes suivantes, respectivement 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole :
Par dérivé du dimercaptothiadiazole selon l'invention, on entend des composés chimiques dérivés des quatre molécules dimercaptothiadiazoles, 4,5-dimercapto-1,2,3-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 3,4-dimercapto-1,2,5-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, ci-dessous pris seules ou en mélange :
En particulier, en prenant comme exemple, le 2,5-dimercapto-1,3,4-thiadiazole, les dérivés du 2,5-dimercapto-1,3,4-thiadiazole sont des molécules de formule générale (II) ou (III) :
Les compositions lubrifiantes selon l'invention comprennent de 0,1 à 10% en masse, par rapport à la masse totale de la composition lubrifiante, de dérivé de dimercaptothiadiazole, de préférence de 0,2 à 5%, plus préférentiellement de 0,3 à 2%, encore plus préférentiellement de 0,5 à 1%.The lubricating compositions according to the invention comprise from 0.1 to 10% by mass, relative to the total mass of the lubricating composition, of dimercaptothiadiazole derivative, preferably from 0.2 to 5%, more preferably from 0.3 at 2%, even more preferably from 0.5 to 1%.
Comme exemple de dérivé de dimercaptothiadiazole selon l'invention, on peut citer l'Anglamol 2198 commercialisé par la société LUBRIZOL.As an example of a dimercaptothiadiazole derivative according to the invention, mention may be made of Anglamol 2198 sold by the company LUBRIZOL.
Les compositions selon l'invention comprennent au moins un thiophosphate d'amine de formule (IVa) :
Des composés particulièrement préférés de formule (IVa) sont les dithiophosphates d'amines dans lesquels X1 et X2 sont des atomes de soufre et M, R3, R4, R5, R6 tel que définis ci-dessus.Particularly preferred compounds of formula (IVa) are the dithiophosphates of amines in which X 1 and X 2 are sulfur atoms and M, R 3 , R 4 , R 5 , R 6 as defined above.
Les compositions lubrifiantes selon l'invention peuvent contenir tout type de base lubrifiante minérale, synthétique ou naturelle, animale ou végétale adaptée(s) à leur utilisation.The lubricating compositions according to the invention can contain any type of mineral, synthetic or natural, animal or plant lubricating base suitable for their use.
La ou les huiles de base utilisées dans les compositions lubrifiantes selon la présente invention peuvent être des huiles d'origine minérales ou synthétiques des groupes I à V selon les classes définies dans la classification API (ou leurs équivalents selon la classification ATIEL) telle que résumée ci-dessous, seules ou en mélange.
Les huiles de base minérales selon l'invention incluent tous types de bases obtenues par distillation atmosphérique et sous vide du pétrole brut, suivies d'opérations de raffinage tels qu'extraction au solvant, désalphatage, déparaffinage au solvant, hydrotraitement, hydrocraquage et hydroisomérisation, hydrofinition.The mineral base oils according to the invention include all types of bases obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, dealphating, solvent dewaxing, hydrotreatment, hydrocracking and hydroisomerization, hydrofinishing.
Les huiles de bases des compositions selon la présente invention peuvent également être des huiles synthétiques, tels certains esters d'acides carboxyliques et d'alcools, ou des polyalphaoléfines. Les polyalphaoléfines utilisées comme huiles de base, sont par exemple obtenues à partir de monomères ayant de 4 à 32 atomes de carbone (par exemple octène, decène), et une viscosité à 100°C comprise entre 1,5 et 15 cSt selon la norme ASTM D445. Leur masse moléculaire moyenne en poids est typiquement comprise entre 250 et 3000 selon la norme ASTM D5296. Des mélanges d'huiles synthétiques et minérales peuvent également être employés.The base oils of the compositions according to the present invention can also be synthetic oils, such as certain esters of carboxylic acids and alcohols, or polyalphaolefins. The polyalphaolefins used as base oils, are for example obtained from monomers having from 4 to 32 carbon atoms (for example octene, decene), and a viscosity at 100 ° C between 1.5 and 15 cSt according to the standard ASTM D445. Their weight average molecular mass is typically between 250 and 3000 according to the ASTM D5296 standard. Mixtures of synthetic and mineral oils can also be used.
Il n'existe aucune limitation quand à l'emploi de telle ou telle base lubrifiante pour réaliser les compositions lubrifiantes selon l'invention, si ce n'est qu'elles doivent avoir des propriétés, notamment de viscosité, indice de viscosité, teneur en soufre, résistance à l'oxydation, adaptées à une utilisation dans une boite de vitesse, en particulier dans une boite de vitesse de véhicules automobile, en particulier dans une boite de vitesse manuelle.There is no limitation when using this or that lubricating base to produce the lubricating compositions according to the invention, except that they must have properties, in particular of viscosity, viscosity index, content of sulfur, resistance to oxidation, suitable for use in a gearbox, in particular in a gearbox of motor vehicles, in particular in a manual gearbox.
Préférentiellement, les bases lubrifiantes représentent au moins 50% en masse, par rapport à la masse totale de la composition lubrifiante, préférentiellement au moins 60%, ou encore au moins 70%. Typiquement, elles représentent entre 75 et 90% en masse, par rapport à la masse totale des compositions lubrifiantes selon l'invention.Preferably, the lubricating bases represent at least 50% by mass, relative to the total mass of the lubricating composition, preferably at least 60%, or even at least 70%. Typically, they represent between 75 and 90% by mass, relative to the total mass of the lubricating compositions according to the invention.
Préférentiellement, les compositions lubrifiantes selon l'invention comprennent des bases minérales de groupe I et/ou III, ou des bases synthétiques de groupe IV selon la classification API.Preferably, the lubricating compositions according to the invention comprise mineral bases of group I and / or III, or synthetic bases of group IV according to the API classification.
Préférentiellement, les compositions lubrifiantes selon l'invention ont une viscosité cinématique à 100°C mesurée selon la norme ASTM D445 comprise entre 4 et 41 cSt, selon la classification SAE J 306, de préférence entre 4,1 et 32,5 cSt.Preferably, the lubricating compositions according to the invention have a kinematic viscosity at 100 ° C. measured according to the ASTM D445 standard of between 4 and 41 cSt, according to the SAE J 306 classification, preferably between 4.1 and 32.5 cSt.
Les grades préférés sont tous les grades compris entre les grades 75W et 140, notamment les grades 75W, 75W80 et 75W90.Preferred grades are all grades between grades 75W and 140, including grades 75W, 75W80 and 75W90.
Préférentiellement, les compositions lubrifiantes selon l'invention ont un indice de viscosité (VI) supérieur à 120 (norme ASTM 2270).Preferably, the lubricating compositions according to the invention have a viscosity index (VI) greater than 120 (standard ASTM 2270).
Les compositions lubrifiantes selon l'invention peuvent également contenir d'autres additifs tels que des additifs anti-usure et/ou extrême pression. On utilise des additifs anti-usure et/ou extrême pression de type phospho-soufrés, phosphorés ou soufrés, pris seuls ou en mélange.The lubricating compositions according to the invention can also contain other additives such as anti-wear and / or extreme pressure additives. Anti-wear and / or extreme pressure additives of the phospho-sulfur, phosphorus or sulfur type, taken alone or as a mixture, are used.
Les additifs anti-usure et/ou extrême-pression phospho-soufrés sont par exemple et non limitativement l'acide thiophosphorique, l'acide thiophosphoreux, les esters de ces acides, leurs sels, et les dithiophosphates, les mono- ou dithiophosphates autres que les thiophosphates d'amine selon l'invention, particulièrement les dithiophosphates de zinc.The phospho-sulfur antiwear and / or extreme pressure additives are for example and without limitation thiophosphoric acid, thiophosphorous acid, esters of these acids, their salts, and dithiophosphates, mono- or dithiophosphates other than the amine thiophosphates according to the invention, particularly the zinc dithiophosphates.
On peut citer, à titre d'exemples d'additifs anti usure et extrême pression phospho soufrés, ceux qui comportent de 1 à 3 atomes de soufre, tels que le monobutylthiophosphate, monooctylthiophosphate, monolaurylthiophosphate, dibutylthiophosphate, dilaurylthiophosphate, tributylthiophosphate, trioctylthiophosphate, triphenylthiophosphate, trilaurylthiophosphate, monobutylthiophosphate, monoctylthiophosphite, monolaurylthiophosphite, dibutylthiophosphite, dilaurylthiophosphite, tributylthiophosphite, trioctylthiophosphite, triphenylthiophosphite, trilaurylthiophosphite et leurs sels.Mention may be made, as examples of phospho-sulfurized anti-wear and extreme pressure additives, those which contain from 1 to 3 sulfur atoms, such as monobutylthiophosphate, monooctylthiophosphate, monolaurylthiophosphate, dibutylthiophosphate, dilaurylthiophosphate, triophiophiophosphate, triophiophosphate, phenophosphate, triophiophosphate, trilaurylthiophosphate, monobutylthiophosphate, monoctylthiophosphite, monolaurylthiophosphite, dibutylthiophosphite, dilaurylthiophosphite, tributylthiophosphite, trioctylthiophosphite, triphenylthiophosphite, trilaurylthiophosphite and their salts.
Des exemples de sels des esters de l'acide thiophosphorique et de l'acide thiphosphoreux sont ceux obtenus par la réaction avec un composé azoté tels que l'ammoniac ou une amine ou l'oxyde de zinc ou le chlorure de zinc.Examples of salts of esters of thiophosphoric acid and of thiphosphorous acid are those obtained by reaction with a nitrogenous compound such as ammonia or an amine or zinc oxide or zinc chloride.
Selon un mode de réalisation préféré, les additifs anti-usure et extrême pression phospho-soufrés des compositions selon l'invention sont des thiophosphates, répondant à la formule (IVb) :
Des composés de formule (IVb) particulièrement préférés sont les dithiophosphates (X1 et X2 sont des atomes de soufre), préférentiellement de zinc.Particularly preferred compounds of formula (IVb) are dithiophosphates (X 1 and X 2 are sulfur atoms), preferably zinc.
Les compositions lubrifiantes peuvent également contenir des additifs anti usure et extrême-pression phosphorés, tels que par exemple les phosphates d'alkyle ou phosphonates d'alkyle, l'acide phosphorique, l'acide phosphoreux, les mono-, di- et triesters de l'acide phosphoreux et de l'acide phosphorique, et leurs sels.The lubricating compositions may also contain phosphorus-containing antiwear and extreme pressure additives, such as, for example, alkyl phosphates or alkyl phosphonates, phosphoric acid, phosphorous acid, mono-, di- and triesters of phosphorous acid and phosphoric acid, and their salts.
Les compositions lubrifiantes peuvent également contenir des additifs anti-usure et extrême pression soufrés. On peut citer, à titre d'exemple d'additifs antiusure et extrême pression soufrés, les dithiocarbamates, thiadiazoles et benzothiazoles, les oléfines soufrées.The lubricating compositions can also contain sulfur antiwear and extreme pressure additives. Mention may be made, by way of example of sulfur-containing antiwear and extreme pressure additives, dithiocarbamates, thiadiazoles and benzothiazoles, and sulfur-containing olefins.
Les oléfines soufrées les plus courantes sont appelées SIBs, pour « Sulfurized IsoButylènes ». Ces oléfines soufrées s'obtiennent généralement par une réaction de sulfuration d'oléfines par du soufre, de l'hydrogène sulfuré ou de sulfures de métaux alcalin hydraté, par exemple sulfure de sodium. Un exemple de procédés de préparation de telles oléfines soufrées est par exemple décrit dans les brevets
Les compositions lubrifiantes selon l'invention comprennent de 0,2 à 10 % en masse d'agents anti-usure et/ou extrême pression, par rapport à la masse de composition lubrifiante, de préférence de 0,5 à 8%, de 1 à 5%, préférentiellement de 2 à 4%.The lubricating compositions according to the invention comprise from 0.2 to 10% by mass of antiwear and / or extreme pressure agents, relative to the mass of lubricating composition, preferably from 0.5 to 8%, from 1 at 5%, preferably from 2 to 4%.
Les compositions selon l'invention, peuvent également comprendre, en plus du copolymère d'éthylène et d'alpha-oléfine, d'autres polymères améliorant de l'indice de viscosité (VI) tels que des polyméthacrylates, des polyacrylates, des oléfines copolymères, des Ethylène Propylène Diène Monomères (EPDM), des polybutènes, des copolymères de styrène et d'oléfine, hydrogénés ou non. Les polymères préférés sont les polyméthacrylates (PMA).The compositions according to the invention may also comprise, in addition to the copolymer of ethylene and of alpha-olefin, other polymers which improve the viscosity index (VI) such as polymethacrylates, polyacrylates, olefin copolymers. , Ethylene Propylene Diene Monomers (EPDM), polybutenes, copolymers of styrene and olefin, hydrogenated or not. The preferred polymers are polymethacrylates (PMA).
Les polyméthacrylates seront par exemple des polyméthacrylates linéaires, non dispersés, de faible masse ou de masse moyenne. Par faible masse, on entend des PMA de masse moléculaire moyenne en poids Mw inférieure à 20000 (norme ASTM D5296). Par masse moyenne, on entend des PMA de masse moléculaire moyenne en poids Mw comprise entre 30 000 et 90 000, (préférentiellement autour de 50000 (ASTM D5296). Par forte masse, on entend des PMA de masse moléculaire moyenne en poids Mw supérieure à 100000 (ASTM D5296).The polymethacrylates will, for example, be linear polymethacrylates, non-dispersed, of low mass or of medium mass. The term “low mass” is understood to mean PMAs with a weight-average molecular mass Mw of less than 20,000 (standard ASTM D5296). By average mass is meant PMAs with a weight average molecular mass Mw of between 30,000 and 90,000 (preferably around 50,000 (ASTM D5296). By high mass is meant PMAs with a weight average molecular mass Mw greater than 100,000 (ASTM D5296).
Les compositions lubrifiantes selon l'invention peuvent également contenir tous types d'additifs adaptés pour leur utilisation dans les formulations d'huiles pour transmissions, par exemple un ou plusieurs additifs choisis parmi les additifs antioxydants, les inhibiteurs de corrosion, les dispersants, présents aux teneurs usuelles requises pour l'application.The lubricating compositions according to the invention can also contain all types of additives suitable for their use in formulations of oils for transmissions, for example one or more additives chosen from antioxidant additives, corrosion inhibitors, dispersants, present in usual levels required for the application.
Les dispersants préférés sont les polyisobutylènes (PIB), les polyisobutylène d'anhydride succinique, les dérivés aminés des polyisobutylène d'anhydride succinique (PIB succinimides).The preferred dispersants are polyisobutylenes (PIB), polyisobutylene of succinic anhydride, amino derivatives of polyisobutylene of succinic anhydride (PIB succinimides).
Les antioxydants préférés sont par exemple des antioxydants aminés, de préférence des diphénylamines telles que les octadiphénylamines, les phényl-alpha-naphtyl amines, ou des antioxydants phénoliques (dibutylhydroxytoluène BHT et dérivés) ou des antioxydants soufrés (phénates sulfurisés).The preferred antioxidants are, for example, amino antioxidants, preferably diphenylamines such as octadiphenylamines, phenyl-alpha-naphthyl amines, or phenolic antioxidants (dibutylhydroxytoluene BHT and derivatives) or sulfur-containing antioxidants (sulfurized phenates).
Les additifs anti-corrosion préférés sont des dérivés phénoliques, en particulier des dérivés phénoliques éthoxylés et substitués par des groupements alkyles en position ortho.The preferred anti-corrosion additives are phenolic derivatives, in particular phenolic derivatives ethoxylated and substituted by alkyl groups in the ortho position.
L'invention est aussi relative à un procédé de lubrification des transmissions telles que les boîtes de vitesse, les ponts, de préférence les boîtes de vitesse manuelles des véhicules automobiles, ledit procédé mettant en œuvre une composition lubrifiante telle que définie ci-dessus.The invention also relates to a method of lubricating transmissions such as gearboxes, axles, preferably manual gearboxes of motor vehicles, said method using a lubricating composition as defined above.
De préférence, ce procédé permet de réduire la consommation de carburant de véhicules, en particulier de véhicules automobiles.Preferably, this method makes it possible to reduce the fuel consumption of vehicles, in particular of motor vehicles.
L'invention est aussi relative à un procédé de lubrification des transmissions, telles que les boîtes de vitesse, les ponts, de préférence les boîtes de vitesse manuelles des véhicules automobiles ledit procédé mettant en œuvre au moins un copolymère d'éthylène et d'alphaoléfine et au moins un dérivé du dimercaptothiadiazole.The invention also relates to a method for lubricating transmissions, such as gearboxes, axles, preferably manual gearboxes of motor vehicles, said method implementing at least one copolymer of ethylene and alphaolefin and at least one derivative of dimercaptothiadiazole.
Dans un mode de réalisation, l'invention concerne un procédé de lubrification d'au moins un organe de transmission, le procédé comprenant une étape de mise en contact d'une composition lubrifiante comprenant au moins un copolymère d'éthylène et d'alpha-oléfine et au moins un dérivé du dimercaptothiadiazole.In one embodiment, the invention relates to a method of lubricating at least one transmission member, the method comprising a step of bringing into contact a lubricating composition comprising at least one copolymer of ethylene and alpha- olefin and at least one derivative of dimercaptothiadiazole.
Dans un autre mode de réalisation, l'invention concerne un procédé de lubrification d'au moins un organe de transmission, le procédé comprenant une étape de mise en contact d'une composition lubrifiante comprenant au moins un copolymère d'éthylène et d'alpha-oléfine, au moins un dérivé du dimercaptothiadiazole et au moins un thiophosphate d'amine.In another embodiment, the invention relates to a method of lubricating at least one transmission member, the method comprising a step of bringing into contact a lubricating composition comprising at least one copolymer of ethylene and of alpha -olefin, at least one derivative of dimercaptothiadiazole and at least one amine thiophosphate.
Par organe de transmission on entend au sens de la présente invention, par exemple un pont ou une boîte de vitesse, notamment une boîte de vitesse pour véhicule automobile.For the purposes of the present invention, the term “transmission member” is understood to mean, for example, an axle or a gearbox, in particular a gearbox for a motor vehicle.
De préférence, ce procédé permet de diminuer le coefficient de frottement d'une composition lubrifiante.Preferably, this process makes it possible to reduce the coefficient of friction of a lubricating composition.
On prépare des compositions lubrifiantes selon l'invention et des compositions lubrifiantes témoins à partir :
- d'huile de base de groupe III de viscosité à 100°C de 3cSt selon la norme ASTDM D445 et de 125 d'indice de viscosité, selon la norme ASTM 2270.
- de copolymère d'éthylène et d'alphaoléfine de formule générale (I) avec R est un groupe méthyle, x est égal à environ 40 et y est égal à environ 40 et de masse moléculaire moyenne en poids Mw égale à environ 8880, selon la norme ASTM D5296,
- de dérivé du dimercaptothiadiazole qui est un mélange de produits de formule générale (II) et/ou (III) avec R1 et R2 des groupes alkyles linéaires saturés comprenant un nombre moyen d'atomes de carbone de 12, n étant égal à 1,
- de thiophosphate d'amine qui a pour formule générale (IVa) avec X1 et X2 des atomes de soufre, R1 et R2 sont des groupes alkyles ayant 6 atomes de carbone, M est un ammonium formé à partir d'une amine primaire de formule R3R4R5N, où R3, R4, R5 sont respectivement des atomes d'hydrogène et un groupement alkyl de 11 atomes de carbone, et n=1,
- d'un polyméthacrylate qui est un composé linéaire non dispersé, de masse moléculaire moyenne en poids Mw égale à 16190 (ASTM D5296), de masse moléculaire moyenne en nombre Mn égale à 9990 (ASTM D5296), d'indice de polydispersité IP (IP=Mw/Mn) égal à 1,6 et de viscosité cinématique mesurée selon l'ASTM D445 d'au moins 170 cSt à 100°C. Dans la suite, ce composé est appelé PMA de faible poids moléculaire,
- d'un polyméthacrylate linéaire non dispersé de masse moléculaire moyenne en poids Mw égale à 60 000 (ASTM D5296). Dans la suite, ce composé est appelé PMA de poids moléculaire moyen,
- de dispersant qui est un dérivé du polyisobutylène, en particulier un dérivé du polyisobutylène succinimide,
- d'antioxydant aminé qui est de type diphénylamine,
- d'additif anticorrosion phénolique qui est de type phénolique éthoxylé,
- de dithiophosphate de zinc qui est un alkyldithiophosphate de zinc comprenant des chaînes alkyles en C4, C6 et C8,
- de sulfonates qui sont des alkylbenzènes sulfonates de calcium ou de sodium,
- d'alkylphosphites qui sont des dibutyl phosphites,
- d'oléfines soufrés qui sont des penténes, 2,4,4-triméthyl sulfurés,
- d'huile de dilution de Groupe I.
- of group III base oil with a viscosity at 100 ° C of 3 cSt according to standard ASTDM D445 and of 125 viscosity index according to standard ASTM 2270.
- of an ethylene-alpha-olefin copolymer of general formula (I) with R being a methyl group, x is equal to approximately 40 and y is equal to approximately 40 and of a weight average molecular mass Mw equal to approximately 8880, according to the ASTM D5296 standard,
- of dimercaptothiadiazole derivative which is a mixture of products of general formula (II) and / or (III) with R 1 and R 2 linear alkyl groups saturates comprising an average number of carbon atoms of 12, n being equal to 1,
- of amine thiophosphate which has the general formula (IVa) with X 1 and X 2 sulfur atoms, R 1 and R 2 are alkyl groups having 6 carbon atoms, M is an ammonium formed from an amine primary of formula R 3 R 4 R 5 N, where R 3 , R 4 , R 5 are respectively hydrogen atoms and an alkyl group of 11 carbon atoms, and n = 1,
- of a polymethacrylate which is a non-dispersed linear compound, of weight average molecular mass Mw equal to 16190 (ASTM D5296), of number average molecular mass Mn equal to 9990 (ASTM D5296), of polydispersity index IP (IP = Mw / Mn) equal to 1.6 and a kinematic viscosity measured according to ASTM D445 of at least 170 cSt at 100 ° C. In the following, this compound is called low molecular weight PMA,
- of a non-dispersed linear polymethacrylate of weight average molecular mass Mw equal to 60,000 (ASTM D5296). In the following, this compound is called PMA of average molecular weight,
- of dispersant which is a derivative of polyisobutylene, in particular a derivative of polyisobutylene succinimide,
- an amino antioxidant which is of the diphenylamine type,
- phenolic anticorrosion additive which is of the ethoxylated phenolic type,
- zinc dithiophosphate which is a zinc alkyldithiophosphate comprising C 4 , C 6 and C 8 alkyl chains,
- sulfonates which are calcium or sodium alkylbenzene sulfonates,
- alkylphosphites which are dibutyl phosphites,
- sulfur olefins which are pentenes, 2,4,4-trimethyl sulfides,
- Group I dilution oil.
Les % massiques des composants des compositions lubrifiantes sont indiqués dans le Tableau I ci-dessous, ainsi que les résultats Cameron Plint.The% by weight of the components of the lubricating compositions are shown in Table I below, as well as the Cameron Plint results.
Les propriétés de frottement des formules ont été évaluées à l'aide d'un tribomètre alternatif de type Cameron-Plint TE-77. Le principe de fonctionnement est par exemple décrit dans la publication « Friction Force Measurement in Reciprocating Tribometers » de A G Plint, publiée par STLE (Society of Tribologists and Lubrification Engineers) en 2011.The frictional properties of the formulas were evaluated using a Cameron-Plint TE-77 type reciprocating tribometer. The Principe of fonctionment is for example described in the publication “Friction Force Measurement in Reciprocating Tribometers” by AG Plint, published by STLE (Society of Tribologists and Lubrification Engineers) in 2011.
La procédure utilisée mesure le coefficient de frottement d'un rouleau sur un plan, le tout immergé dans le lubrifiant d'essai, dans des conditions de températures (60°C, 100°C et 140°C), de charge (50, 100, 150 et 200N) et de fréquence (5, 10, 20 et 40 Hz) variables afin de reproduire les conditions de frottement rencontrées dans les mécanismes de commande des boîtes de vitesse en cours d'utilisation.The procedure used measures the coefficient of friction of a roller on a plane, all immersed in the test lubricant, under conditions of temperature (60 ° C, 100 ° C and 140 ° C), load (50, 100, 150 and 200N) and variable frequency (5, 10, 20 and 40 Hz) in order to reproduce the friction conditions encountered in the gearbox control mechanisms during use.
La course du rouleau sur le plan, c'est-à-dire le mouvement alternatif de va et vient, est fixé à 7 mm. La durée de l'essai est de 10 min.The stroke of the roller on the plane, that is to say the reciprocating movement back and forth, is fixed at 7 mm. The duration of the test is 10 min.
La réduction du frottement dans ces conditions d'essai permet d'indiquer une diminution des efforts de passage des vitesses et des pertes par frottement dans les engrenages de la boîte de vitesse fonctionnant avec le type de lubrifiant étudié.
Les compositions lubrifiantes 1 à 4 sont des compositions lubrifiantes témoin. Les compositions lubrifiantes 6 et 7 sont des compositions lubrifiantes selon l'invention.Lubricating compositions 1 to 4 are control lubricating compositions. Lubricating compositions 6 and 7 are lubricating compositions according to the invention.
Les compositions lubrifiantes 1, 3 et 5 ne contiennent pas de copolymère d'éthylène et d'alphaoléfine. Les coefficients de frottement mesurés correspondent à ceux qui peuvent être attendus de l'homme du métier.Lubricating compositions 1, 3 and 5 do not contain an ethylene / alphaolefin copolymer. The measured friction coefficients correspond to those which can be expected from a person skilled in the art.
La composition 8 est une composition lubrifiante ne comprenant pas de thiophosphate d'amine.Composition 8 is a lubricating composition not comprising amine thiophosphate.
Dans les compositions lubrifiantes 2, 4 et 6 un copolymère d'éthylène et d'alphaoléfine a été ajouté.In lubricating compositions 2, 4 and 6, an ethylene / alphaolefin copolymer was added.
Dans les compositions lubrifiantes 2 et 4, cet ajout n'entraîne pas de baisse du coefficient de frottement.In lubricating compositions 2 and 4, this addition does not lead to a drop in the coefficient of friction.
En revanche, il est remarquable d'observer que dans la composition lubrifiante 6, cet ajout entraîne une baisse du coefficient de frottement.On the other hand, it is remarkable to observe that in the lubricating composition 6, this addition causes a drop in the coefficient of friction.
Il est encore plus remarquable d'observer que la composition lubrifiante 7 selon l'invention présente de manière inattendue un coefficient de frottement très bas.It is even more remarkable to observe that the lubricating composition 7 according to the invention unexpectedly exhibits a very low coefficient of friction.
Il est également remarquable d'observer que la présence de thiophosphate d'amine dans la composition lubrifiante permet de diminuer significativement le coefficient de frottement, comparativement à la composition 8 ne comprenant pas de thiophosphate d'amine.It is also remarkable to observe that the presence of amine thiophosphate in the lubricating composition makes it possible to significantly reduce the coefficient of friction, compared to composition 8 not comprising amine thiophosphate.
Ainsi la combinaison d'un copolymère éthylène-alphaoléfine, d'un dimercaptothiadiazole et d'un thiophosphate d'amine dans une composition lubrifiante améliore le coefficient de frottement de ladite composition.Thus, the combination of an ethylene-alphaolefin copolymer, a dimercaptothiadiazole and an amine thiophosphate in a lubricating composition improves the coefficient of friction of said composition.
Il est à noter que la composition de l'exemple 7 présente une perte de viscosité mesurée à 100°C selon le test normé CEC L-45-99 de 2,6%; une telle valeur de perte de viscosité étant parfaitement en adéquation avec l'application de la composition dans la lubrification d'organes de transmission, et plus particulièrement de boîtes de vitesse.It should be noted that the composition of Example 7 exhibits a loss in viscosity measured at 100 ° C. according to the standardized test CEC L-45-99 of 2.6%; such a viscosity loss value being perfectly in line with the application of the composition in the lubrication of transmission members, and more particularly of gearboxes.
Claims (14)
- Lubricant composition comprising, based on the total mass of lubricant composition,- one or more base oils,- 0.1 to 10% by mass of at least one dimercaptothiadiazole derivative,- 1 to 20% by mass of at least one ethylene and alpha-olefin copolymer, and- 0.2 to 10% by mass of at least one amine thiophosphate of general formula (IVa).
the said dimercaptothiadiazole derivative being a compound that is a derivative of 4,5-dimercapto-1,2,3-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 3,4-dimercapto-1,2,5-thiadiazole, and 2,5-dimercapto-1,3,4-thiadiazole, used alone or in a mixture. - Lubricant composition according to claim 1 in which the ethylene and alpha-olefin copolymer is an ethylene and alpha-olefin copolymer comprising from 3 to 30 carbon atoms, preferably from 3 to 24, preferentially from 3 to 20, even more preferentially from 3 to 10, even more preferentially from 3 to 6.
- Lubricant composition according to claim 1 or 2 in which the ethylene and alpha-olefin copolymer has the general formula (I):
- Lubricant composition according to claim 1, 2 or 3 in which the quantity of ethylene and alpha-olefin copolymer is comprised between 2 and 15% by mass, with respect to the total mass of lubricant composition, preferably from 4 to 10%, more preferentially from 5 to 9%.
- Lubricant composition according to any one of claims 1 to 4 in which the dimercaptothiadiazole derivative has, as general formula, formula (II) or (III), used alone or in a mixture:
- Lubricant composition according to any one of claims 1 to 5 in which the quantity of dimercaptothiadiazole derivative is comprised between 0.2 and 5% by mass, with respect to the total mass of the lubricant composition, preferably from 0.3 to 2%, more preferentially from 0.5 to 1%.
- Lubricant composition according to any one of claims 1 to 6 in which the quantity of amine thiophosphate is comprised between 0.5 to 8% by mass, with respect to the total mass of lubricant composition, preferably from 1 to 5%, more preferentially from 2 to 4%.
- Lubricant composition according to any one of claims 1 to 7 moreover comprising a polymethacrylate.
- Lubricant composition according to any one of claims 1 to 8 moreover comprising a dispersant derived from polyisobutene.
- Lubricant composition according to any one of claims 1 to 9 moreover comprising an amine-type antioxidant additive.
- Lubricant composition according to any one of claims 1 to 10 moreover comprising a phenol-type anti-corrosion additive.
- Lubricant composition according to any one of claims 1 to 11 having a kinematic viscosity at 100°C according to the standard ASTM D445 comprised between 4 and 40 cSt, preferably between 4.1 and 32.5 cSt, preferably between 6 and 18.5 cSt.
- Use of a lubricant composition according to any one of claims 1 to 12 for lubricating transmissions such as the gearboxes, the axles, preferably the manual gearboxes of motor vehicles.
- Use of a lubricant composition according to any one of claims 1 to 12 for reducing the fuel consumption of vehicles, in particular of motor vehicles.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1161856A FR2984348B1 (en) | 2011-12-16 | 2011-12-16 | LUBRICATING COMPOSITIONS FOR TRANSMISSIONS |
| PCT/EP2012/075645 WO2013087889A1 (en) | 2011-12-16 | 2012-12-14 | Lubricating compositions for transmissions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2791294A1 EP2791294A1 (en) | 2014-10-22 |
| EP2791294B1 true EP2791294B1 (en) | 2020-09-02 |
Family
ID=47471795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP12809233.5A Active EP2791294B1 (en) | 2011-12-16 | 2012-12-14 | Lubricating compositions for transmissions |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US9334462B2 (en) |
| EP (1) | EP2791294B1 (en) |
| JP (1) | JP6067027B2 (en) |
| KR (1) | KR101984065B1 (en) |
| CN (1) | CN104066827B (en) |
| AR (1) | AR089276A1 (en) |
| BR (1) | BR112014014490A2 (en) |
| CA (1) | CA2858927A1 (en) |
| FR (1) | FR2984348B1 (en) |
| MX (1) | MX343664B (en) |
| RU (1) | RU2612803C2 (en) |
| WO (1) | WO2013087889A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3009309B1 (en) * | 2013-08-02 | 2016-10-07 | Total Marketing Services | LUBRICATING COMPOSITIONS FOR TRANSMISSIONS |
| FR3018079B1 (en) * | 2014-02-28 | 2017-06-23 | Total Marketing Services | LUBRICATING COMPOSITION BASED ON METALLIC NANOPARTICLES |
| WO2016136873A1 (en) * | 2015-02-27 | 2016-09-01 | Ｊｘエネルギー株式会社 | Lubricating oil composition for final reduction gear |
| EP3423554B1 (en) * | 2016-03-03 | 2022-08-10 | The Lubrizol Corporation | Lubricating oil composition having improved air release |
| JP2018119059A (en) * | 2017-01-25 | 2018-08-02 | 出光興産株式会社 | Lubricant composition for transmission, method of lubricating transmission and transmission |
| US10808198B2 (en) * | 2019-01-16 | 2020-10-20 | Afton Chemical Corporation | Lubricant containing thiadiazole derivatives |
| CN114381320B (en) * | 2020-10-21 | 2023-09-26 | 中国石油天然气股份有限公司 | Gear oil additive composition and preparation method and application thereof |
Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4101427A (en) * | 1977-02-09 | 1978-07-18 | Exxon Research & Engineering Co. | Lubricant composition |
| US4575431A (en) | 1984-05-30 | 1986-03-11 | Chevron Research Company | Lubricant composition containing a mixture of neutralized phosphates |
| EP0395258A1 (en) | 1989-04-14 | 1990-10-31 | Ethyl Petroleum Additives, Inc. | Process for preparing sulfurized branched alkyl phosphite lubricant additive |
| CN1081198A (en) | 1992-07-10 | 1994-01-26 | 广东石油化工专科学校科技开发公司 | A kind of heat-conducting oil for electric heating device |
| US5439605A (en) | 1993-06-03 | 1995-08-08 | Khorramian; Behrooz A. | Phosphorus and phosphours-free low and light ash lubricating oils |
| US6133207A (en) | 1999-12-22 | 2000-10-17 | Ethyl Corporation | Odor reduction of lubricant additives packages |
| US6238316B1 (en) | 1999-04-23 | 2001-05-29 | Gary Lee Sturm | Differential axle speed sensing mechanism |
| US6251840B1 (en) | 1995-09-12 | 2001-06-26 | The Lubrizol Corporation | Lubrication fluids for reduced air entrainment and improved gear protection |
| CN1076393C (en) | 1998-10-30 | 2001-12-19 | 中国石化兰州炼油化工总厂 | Automobile automatic drive liquid composition |
| EP1191090A2 (en) | 2000-09-19 | 2002-03-27 | Ethyl Corporation | Gear oil formulations having enhanced perfomance |
| WO2002102946A1 (en) | 2001-06-13 | 2002-12-27 | Nippon Oil Corporation | Rubricating oil composition |
| US20030092585A1 (en) | 2001-11-13 | 2003-05-15 | The Lubrizol Corporation | Lubricating compositions and concentrates containing an antiwear amount of a thiadiazole |
| US20040214729A1 (en) | 2003-04-25 | 2004-10-28 | Buitrago Juan A. | Gear oil composition having improved copper corrosion properties |
| US20080015131A1 (en) | 2003-10-08 | 2008-01-17 | The Lubrizol Corporation | Lubricants Containing Olefin Copolymer and Acrylate Copolymer |
| CN101280240A (en) | 2007-04-05 | 2008-10-08 | 株式会社日本能源 | Gear oil composition |
| CN100497562C (en) | 2004-07-29 | 2009-06-10 | 中国石油化工股份有限公司 | Combination of general gear oil |
| US20090312211A1 (en) | 2006-08-03 | 2009-12-17 | Idemitsu Kosan Co., Ltd. | Lubricant composition |
| EP2159275A2 (en) | 2009-10-14 | 2010-03-03 | Shell Internationale Research Maatschappij B.V. | Lubricating composition |
| CN102344849A (en) | 2010-07-29 | 2012-02-08 | 中国石油化工股份有限公司 | Turbine oil additive composition |
| EP2502976A1 (en) | 2009-11-19 | 2012-09-26 | JTEKT Corporation | Lubricant oil, friction member, and gear-type differential having limited slip function |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4344854A (en) | 1975-03-21 | 1982-08-17 | The Lubrizol Corporation | Sulfurized compositions |
| US4584114A (en) * | 1980-12-19 | 1986-04-22 | Mobil Oil Corporation | Multifunctional lubricant additives and compositions thereof |
| US4707301A (en) * | 1986-07-11 | 1987-11-17 | The Lubrizol Corporation | Norbornyl dimer ester and polyester additives for lubricants and fuels |
| US5135670A (en) | 1990-06-22 | 1992-08-04 | Mobil Oil Corporation | Sulfurized olefin extreme pressure/antiwear additives and compositions thereof |
| JP4836298B2 (en) * | 1998-08-20 | 2011-12-14 | 昭和シェル石油株式会社 | Lubricating oil composition |
| GB9901667D0 (en) * | 1999-01-26 | 1999-03-17 | Ici Plc | Lubricant composition |
| JP2000273480A (en) * | 1999-03-29 | 2000-10-03 | Asahi Denka Kogyo Kk | Lubricating composition |
| EP1227145B1 (en) * | 2001-01-24 | 2013-03-13 | Nippon Mitsubishi Oil Corporation | Lubricating oil compositions |
| EP1379617B1 (en) * | 2001-04-11 | 2006-12-13 | The Lubrizol Corporation | Process for lubricating a driveline using lubricants containing olefin copolymer and acrylate copolymer |
| EP1344810A1 (en) * | 2002-03-13 | 2003-09-17 | Infineum International Limited | Fuel additive compositions for diesel engine equipped with a particulate trap |
| ES2329446T3 (en) | 2002-07-30 | 2009-11-26 | Chevron Oronite S.A. | ADDITIVE COMPOSITION FOR TRANSMISSION OIL CONTAINING A HYDRAATED ALKALINE METAL BORATE AND HEXAGONAL BORUS NITRIDE. |
| US20040176256A1 (en) * | 2002-11-07 | 2004-09-09 | Nippon Oil Corporation | Lubricating oil composition for transmissions |
| JP2004217797A (en) * | 2003-01-15 | 2004-08-05 | Ethyl Japan Kk | Gear oil composition having long life and excellent thermal stability |
| ES2403780T3 (en) | 2003-11-28 | 2013-05-21 | Chevron Oronite S.A. | Composition of additive for transmission oil |
| ES2666595T3 (en) | 2006-10-24 | 2018-05-07 | Total Marketing Services | Use of a multifunctional lubricating fluid |
| FR2925520B1 (en) | 2007-12-21 | 2011-02-25 | Total France | LUBRICATING COMPOSITIONS FOR TRANSMISSIONS |
| FR2936812B1 (en) * | 2008-10-03 | 2010-10-15 | Total France | LUBRICATING COMPOSITIONS FOR TRANSMISSIONS. |
| US20100160196A1 (en) * | 2008-12-23 | 2010-06-24 | Clarke Dean B | Power Transmission Fluids with Improved Viscometric Properties |
| FR2945754A1 (en) | 2009-05-20 | 2010-11-26 | Total Raffinage Marketing | NEW ADDITIVES FOR TRANSMISSION OILS |
| FR2961823B1 (en) | 2010-06-25 | 2013-06-14 | Total Raffinage Marketing | LUBRICATING COMPOSITIONS FOR AUTOMOTIVE TRANSMISSIONS |
| FR2968669B1 (en) | 2010-12-13 | 2014-02-28 | Total Raffinage Marketing | FAT COMPOSITION |
-
2011
- 2011-12-16 FR FR1161856A patent/FR2984348B1/en active Active
-
2012
- 2012-12-14 WO PCT/EP2012/075645 patent/WO2013087889A1/en active Application Filing
- 2012-12-14 MX MX2014007278A patent/MX343664B/en active IP Right Grant
- 2012-12-14 CA CA2858927A patent/CA2858927A1/en not_active Abandoned
- 2012-12-14 JP JP2014546551A patent/JP6067027B2/en not_active Expired - Fee Related
- 2012-12-14 AR ARP120104759A patent/AR089276A1/en not_active Application Discontinuation
- 2012-12-14 BR BR112014014490-7A patent/BR112014014490A2/en not_active Application Discontinuation
- 2012-12-14 US US14/364,988 patent/US9334462B2/en not_active Expired - Fee Related
- 2012-12-14 RU RU2014124015A patent/RU2612803C2/en not_active IP Right Cessation
- 2012-12-14 EP EP12809233.5A patent/EP2791294B1/en active Active
- 2012-12-14 CN CN201280061291.4A patent/CN104066827B/en not_active Expired - Fee Related
- 2012-12-14 KR KR1020147016039A patent/KR101984065B1/en active IP Right Grant
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4101427A (en) * | 1977-02-09 | 1978-07-18 | Exxon Research & Engineering Co. | Lubricant composition |
| US4575431A (en) | 1984-05-30 | 1986-03-11 | Chevron Research Company | Lubricant composition containing a mixture of neutralized phosphates |
| EP0395258A1 (en) | 1989-04-14 | 1990-10-31 | Ethyl Petroleum Additives, Inc. | Process for preparing sulfurized branched alkyl phosphite lubricant additive |
| CN1081198A (en) | 1992-07-10 | 1994-01-26 | 广东石油化工专科学校科技开发公司 | A kind of heat-conducting oil for electric heating device |
| US5439605A (en) | 1993-06-03 | 1995-08-08 | Khorramian; Behrooz A. | Phosphorus and phosphours-free low and light ash lubricating oils |
| US6251840B1 (en) | 1995-09-12 | 2001-06-26 | The Lubrizol Corporation | Lubrication fluids for reduced air entrainment and improved gear protection |
| CN1076393C (en) | 1998-10-30 | 2001-12-19 | 中国石化兰州炼油化工总厂 | Automobile automatic drive liquid composition |
| US6238316B1 (en) | 1999-04-23 | 2001-05-29 | Gary Lee Sturm | Differential axle speed sensing mechanism |
| US6133207A (en) | 1999-12-22 | 2000-10-17 | Ethyl Corporation | Odor reduction of lubricant additives packages |
| EP1191090A2 (en) | 2000-09-19 | 2002-03-27 | Ethyl Corporation | Gear oil formulations having enhanced perfomance |
| WO2002102946A1 (en) | 2001-06-13 | 2002-12-27 | Nippon Oil Corporation | Rubricating oil composition |
| US20030092585A1 (en) | 2001-11-13 | 2003-05-15 | The Lubrizol Corporation | Lubricating compositions and concentrates containing an antiwear amount of a thiadiazole |
| US20040214729A1 (en) | 2003-04-25 | 2004-10-28 | Buitrago Juan A. | Gear oil composition having improved copper corrosion properties |
| US20080015131A1 (en) | 2003-10-08 | 2008-01-17 | The Lubrizol Corporation | Lubricants Containing Olefin Copolymer and Acrylate Copolymer |
| CN100497562C (en) | 2004-07-29 | 2009-06-10 | 中国石油化工股份有限公司 | Combination of general gear oil |
| US20090312211A1 (en) | 2006-08-03 | 2009-12-17 | Idemitsu Kosan Co., Ltd. | Lubricant composition |
| CN101280240A (en) | 2007-04-05 | 2008-10-08 | 株式会社日本能源 | Gear oil composition |
| EP2159275A2 (en) | 2009-10-14 | 2010-03-03 | Shell Internationale Research Maatschappij B.V. | Lubricating composition |
| EP2502976A1 (en) | 2009-11-19 | 2012-09-26 | JTEKT Corporation | Lubricant oil, friction member, and gear-type differential having limited slip function |
| CN102344849A (en) | 2010-07-29 | 2012-02-08 | 中国石油化工股份有限公司 | Turbine oil additive composition |
Non-Patent Citations (6)
| Title |
|---|
| "Chemistry and Technology of Lubricants 3rd EDITION", 1 January 2010, SPRINGER NETHERLANDS, Dordrecht, ISBN: 978-1-4020-8662-5, article ROY M. MORTIER ·, MALCOLM F. FOX · STEFAN T. ORSZULIK: "3 Friction, Wear and the Role of Additives in Controlling Them", pages: 93,341 - 342, XP055951690 |
| "Lubricants and Lubrication", 1 January 2007, article THEO MANG, WILFRIED DRESEL: " 6.8 Antiwear (AW) and Extreme Pressure (EP) Additives", pages: 107,110,117 - 119,668, XP055951693 |
| ANONYMOUS: "lubricant additives T561 CAS#59656-20-1", BOSSGOO.COM, 21 June 2019 (2019-06-21), XP055951698, [retrieved on 20220816] |
| DATABASE CAS retrieved from STN Database accession no. 13539-13-4 |
| DATABASE CAS retrieved from STN Database accession no. 59656-20-1 |
| RUDNICK LESLIE R: "Lubricant Additives Chemistry and Applications Second Edition", LUBRICANT ADDITIVES CHEMISTRY AND APPLICATIONS SECOND EDITION, 1 January 2009 (2009-01-01), pages 7,216,225 - 229,298,331,486, XP055951687, [retrieved on 20220816] |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2858927A1 (en) | 2013-06-20 |
| US20150218481A1 (en) | 2015-08-06 |
| EP2791294A1 (en) | 2014-10-22 |
| BR112014014490A2 (en) | 2019-10-01 |
| KR20140110861A (en) | 2014-09-17 |
| MX2014007278A (en) | 2014-08-01 |
| FR2984348B1 (en) | 2015-02-27 |
| FR2984348A1 (en) | 2013-06-21 |
| JP6067027B2 (en) | 2017-01-25 |
| MX343664B (en) | 2016-11-16 |
| RU2612803C2 (en) | 2017-03-13 |
| RU2014124015A (en) | 2016-02-10 |
| AR089276A1 (en) | 2014-08-13 |
| CN104066827B (en) | 2016-11-16 |
| JP2015500385A (en) | 2015-01-05 |
| US9334462B2 (en) | 2016-05-10 |
| CN104066827A (en) | 2014-09-24 |
| KR101984065B1 (en) | 2019-05-30 |
| WO2013087889A1 (en) | 2013-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2791294B1 (en) | Lubricating compositions for transmissions | |
| EP2652100B1 (en) | Grease composition | |
| EP3274432B1 (en) | Lubricating composition | |
| EP3289054A1 (en) | Ultra-fluid lubricating composition | |
| JP5941316B2 (en) | Lubricating oil composition | |
| FR3009309A1 (en) | LUBRICATING COMPOSITIONS FOR TRANSMISSIONS | |
| EP2814918A1 (en) | Lubricating compositions for transmissions | |
| WO2014001521A1 (en) | Lubricant composition | |
| EP3430109A1 (en) | Polyalkylene glycol-based lubricant composition | |
| EP3325583B1 (en) | Long duration fuel economy lubricating composition | |
| EP3481927B1 (en) | Lubricant composition for a gas engine | |
| FR3048977A1 (en) | LUBRICATING COMPOSITION BASED ON POLYALKYLENE GLYCOLS | |
| WO2020201126A1 (en) | Use of a lubricant composition for transmission | |
| WO2017191215A1 (en) | Hydraulic composition for extreme cold temperatures | |
| WO2024110560A1 (en) | Lubricating composition for a motor vehicle drive train | |
| WO2024110561A1 (en) | Lubricant composition for a motor vehicle transmission | |
| FR3112792A1 (en) | Oxidation stable automotive transmission lubricant composition. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 20140530 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| DAX | Request for extension of the european patent (deleted) | ||
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
| 17Q | First examination report despatched |
Effective date: 20181109 |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: TOTAL MARKETING SERVICES |
|
| TPAC | Observations filed by third parties |
Free format text: ORIGINAL CODE: EPIDOSNTIPA |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
| INTG | Intention to grant announced |
Effective date: 20200327 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1308813 Country of ref document: AT Kind code of ref document: T Effective date: 20200915 Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602012072132 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: FRENCH |
|
| REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201202 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201202 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201203 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20200902 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1308813 Country of ref document: AT Kind code of ref document: T Effective date: 20200902 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210104 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210102 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R026 Ref document number: 602012072132 Country of ref document: DE |
|
| PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
| PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 |
|
| 26 | Opposition filed |
Opponent name: AFTON CHEMICAL CORPORATION Effective date: 20210602 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 |
|
| REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20201231 |
|
| PLBB | Reply of patent proprietor to notice(s) of opposition received |
Free format text: ORIGINAL CODE: EPIDOSNOBS3 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201214 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201214 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201231 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201231 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200902 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201231 |
|
| P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230523 |
|
| PLCK | Communication despatched that opposition was rejected |
Free format text: ORIGINAL CODE: EPIDOSNREJ1 |
|
| APBM | Appeal reference recorded |
Free format text: ORIGINAL CODE: EPIDOSNREFNO |
|
| APBP | Date of receipt of notice of appeal recorded |
Free format text: ORIGINAL CODE: EPIDOSNNOA2O |
|
| APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |
|
| APBQ | Date of receipt of statement of grounds of appeal recorded |
Free format text: ORIGINAL CODE: EPIDOSNNOA3O |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20231220 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20231221 Year of fee payment: 12 Ref country code: DE Payment date: 20231214 Year of fee payment: 12 |
|
| APBY | Invitation to file observations in appeal sent |
Free format text: ORIGINAL CODE: EPIDOSNOBA2O |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R100 Ref document number: 602012072132 Country of ref document: DE |
|
| APBU | Appeal procedure closed |
Free format text: ORIGINAL CODE: EPIDOSNNOA9O |
|
| APCA | Receipt of observations in appeal recorded |
Free format text: ORIGINAL CODE: EPIDOSNOBA4O |
|
| PLBN | Opposition rejected |
Free format text: ORIGINAL CODE: 0009273 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: OPPOSITION REJECTED |
|
| 27O | Opposition rejected |
Effective date: 20240322 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 602012072132 Country of ref document: DE Owner name: TOTALENERGIES ONETECH, FR Free format text: FORMER OWNER: TOTAL MARKETING SERVICES, PUTEAUX, FR |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E Free format text: REGISTERED BETWEEN 20240530 AND 20240605 |