US20220411713A1 - Lubricant composition for preventing corrosion and/or tribocorrosion of metalparts in an engine - Google Patents
Lubricant composition for preventing corrosion and/or tribocorrosion of metalparts in an engine Download PDFInfo
- Publication number
- US20220411713A1 US20220411713A1 US17/619,804 US202017619804A US2022411713A1 US 20220411713 A1 US20220411713 A1 US 20220411713A1 US 202017619804 A US202017619804 A US 202017619804A US 2022411713 A1 US2022411713 A1 US 2022411713A1
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- United States
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- weight
- formula
- engine
- compound
- lubricant composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 100
- 239000000314 lubricant Substances 0.000 title claims abstract description 63
- 238000005260 corrosion Methods 0.000 title claims description 27
- 230000007797 corrosion Effects 0.000 title claims description 27
- 239000002199 base oil Substances 0.000 claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 20
- -1 phosphorus ester compound Chemical class 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 239000003599 detergent Substances 0.000 claims description 45
- 229910052751 metal Inorganic materials 0.000 claims description 43
- 239000002184 metal Substances 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 31
- 230000001050 lubricating effect Effects 0.000 claims description 20
- 239000002270 dispersing agent Substances 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 229960001860 salicylate Drugs 0.000 claims description 5
- 150000003873 salicylate salts Chemical class 0.000 claims description 5
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 11
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 229910001018 Cast iron Inorganic materials 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 239000007866 anti-wear additive Substances 0.000 description 6
- 239000001117 sulphuric acid Substances 0.000 description 6
- 235000011149 sulphuric acid Nutrition 0.000 description 6
- 229920002367 Polyisobutene Polymers 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000010727 cylinder oil Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 125000005609 naphthenate group Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- WETFKKDVMGBTPY-UHFFFAOYSA-N C.C=P(C)(C)C Chemical compound C.C=P(C)(C)C WETFKKDVMGBTPY-UHFFFAOYSA-N 0.000 description 3
- CBWOUSQZZIMAQU-VXZUUKOOSA-N CCCCCCCC/C=C\CCCCCCCCOP(=O)(O)OC(C/C=C\CCCCCCCC)CCCCCC Chemical compound CCCCCCCC/C=C\CCCCCCCCOP(=O)(O)OC(C/C=C\CCCCCCCC)CCCCCC CBWOUSQZZIMAQU-VXZUUKOOSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- ZRPXDIXKMFEBBE-UHFFFAOYSA-N [H]P(=O)(OCCCCCCCC)OC(C)CCCCCC Chemical compound [H]P(=O)(OCCCCCCCC)OC(C)CCCCCC ZRPXDIXKMFEBBE-UHFFFAOYSA-N 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920013639 polyalphaolefin Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229960002317 succinimide Drugs 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 0 [1*]OP([3*])(=O)O[2*] Chemical compound [1*]OP([3*])(=O)O[2*] 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000010763 heavy fuel oil Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 231100000241 scar Toxicity 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- RREANTFLPGEWEN-MBLPBCRHSA-N 7-[4-[[(3z)-3-[4-amino-5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidin-2-yl]imino-5-fluoro-2-oxoindol-1-yl]methyl]piperazin-1-yl]-1-cyclopropyl-6-fluoro-4-oxoquinoline-3-carboxylic acid Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(\N=C/3C4=CC(F)=CC=C4N(CN4CCN(CC4)C=4C(=CC=5C(=O)C(C(O)=O)=CN(C=5C=4)C4CC4)F)C\3=O)=NC=2)N)=C1 RREANTFLPGEWEN-MBLPBCRHSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 101100068402 Arabidopsis thaliana GL3 gene Proteins 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BTHAQRDGBHUQMR-UHFFFAOYSA-N [S]P(=O)=O Chemical compound [S]P(=O)=O BTHAQRDGBHUQMR-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195712 glutamate Natural products 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005305 interferometry Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003443 succinic acid derivatives Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010729 system oil Substances 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
-
- 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
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/10—Metal oxides, hydroxides, carbonates or bicarbonates
-
- 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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/086—Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—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
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- 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
-
- 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
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- 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
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
- C10N2040/26—Two-strokes or two-cycle engines
Definitions
- the present invention relates to new lubricant compositions, in particular for engines, in particular useful for preventing corrosion and/or tribocorrosion of metal parts in an engine, and in particular in a two-stroke engine, such as a two-stroke marine engine.
- the present invention also relates to a method of passivating metal parts of an engine, in particular a two-stroke engine, such as a two-stroke marine engine.
- SO 3 sulphur oxides
- H 2 SO 4 sulphuric acid
- Other acids such as nitric acid, compounds with one or more carboxylic acid functions, or combinations of these acids, may also be responsible for corrosion and/or tribocorrosion of engine parts.
- Acidic corrosion is located in the tribological system in the ring-piston-liner area. In this area on a lubricated engine, the friction observed is of the reciprocating sliding type.
- lubricant compositions are classified into two categories: Cylinder oils, which provide lubrication to the piston-cylinder assembly, and system oils, which provide lubrication to all moving parts other than the piston-cylinder assembly.
- Typical engine lubricant compositions comprise a base oil to which dispersants and overbased detergents are added.
- These overbased detergents typically comprise a calcium carbonate (CaCO 3 ) core coated with a surfactant layer. Calcium carbonate reacts with sulphuric acid to form calcium sulphate (CaSO 4 ). The reduction of sulphuric acid in the medium allows the protection of parts against corrosion and/or tribocorrosion.
- the lubricant compositions used must be sufficiently basic (in particular to neutralise the acid), which implies increasing the quantity of detergents included in these compositions.
- lubricant compositions currently on the market have Base Numbers (BN) above 70.
- the increase in the amount of detergents in these lubricant compositions leads to an increase in the number of CaCO 3 and CaSO 4 particles responsible for polishing (or abrasive wear) of the surfaces of the metal engine parts, and in particular of the cylinders of two-stroke engines, such as two-stroke marine engines.
- the use of currently available lubricant compositions does not fully protect metal engine parts from corrosion and/or tribocorrosion, and in particular metal parts of the two-stroke engine from tribocorrosion, when the friction is of the reciprocating sliding type.
- An objective of the present invention is to provide lubricant compositions for improving the protection of metal parts of an engine, typically a two-stroke engine, especially a two-stroke marine engine, against corrosion and/or tribocorrosion.
- the present invention is aimed more particularly at the supply of cylinder oils for two-stroke engines, in particular for two-stroke marine engines.
- a further objective of the present invention is to provide lubricant compositions with a reduced Base Number.
- a lubricant composition comprising:
- R′ represents a linear or branched alkyl moiety comprising from 1 to 36 carbon atoms, preferably from 2 to 30 carbon atoms, advantageously from 4 to 24 carbon atoms, or R′ represents a linear or branched alkenyl moiety comprising from 2 to 36 carbon atoms, preferably from 2 to 30 carbon atoms, advantageously from 4 to 24 carbon atoms.
- a lubricant composition comprising:
- the alkenyl moiety (R 1 and/or R 2 ) according to the invention comprises at least one double bond.
- said double bond is located at C-9, C-10 of the alkenyl moiety with respect to the phosphorus ester function.
- the R 1 , R 2 or R 3 moiety does not comprise a sulphur or nitrogen atom.
- a hydrocarbon moiety is a linear or branched, saturated, partially or totally unsaturated chain comprising from 1 to 36 carbon atoms, preferably from 2 to 30 carbon atoms, advantageously from 4 to 24 carbon atoms.
- the base oil included in the lubricating composition is selected from oils of mineral, synthetic or vegetable origin as well as mixtures thereof.
- the mineral or synthetic oils generally used in the application belong to one of the classes defined in the API classification as summarised in the table below.
- Table 1 API classification of base oils Saturated Sulphur Viscosity content content index
- Group 1 Mineral oils ⁇ 90% >0.03% 80 ⁇ VI ⁇ 120
- Group 2 Hydrocracked oils ⁇ 90% ⁇ 0.03% 80 ⁇ VI ⁇ 120
- Group 3 ⁇ 90% ⁇ 0.03% ⁇ 120 Hydro-isomerised oils
- Group 4 Polyalphaolefins (PAO) Group 5
- Other bases not included in bases in groups 1 to 4
- Group 1 mineral oils may be obtained by distillation of selected naphthenic or paraffinic crudes, followed by purification of these distillates by processes such as solvent extraction, solvent or catalytic dewaxing, hydrotreating or hydrogenation.
- Group 2 and 3 oils are obtained by more severe purification processes, for example a combination of hydrotreating, hydrocracking, hydrogenation and catalytic dewaxing.
- Group 4 and 5 synthetic bases include poly-alpha olefins, polybutenes, polyisobutenes, alkylbenzenes.
- base oils can be used alone or in a mixture.
- Mineral oil can be combined with synthetic oil.
- Marine diesel two-stroke cylinder oils have a viscosity grade of SAE-40 to SAE-60, generally SAE-50 equivalent to a kinematic viscosity at 100° C. of between 16.3 and 21.9 mm 2 /s.
- Grade 40 oils have a kinematic viscosity at 100° C. of between 12.5 and 16.3 mm 2 /s.
- Grade 50 oils have a kinematic viscosity at 100° C. of between 16.3 and 21.9 mm 2 /s.
- Grade 60 oils have a kinematic viscosity at 100° C. of between 21.9 and 26.1 mm 2 /s.
- cylinder oils for two-stroke marine diesel engines with a kinematic viscosity at 100° C. between 18 and 21.5, preferably between 19 and 21.5 mm 2 /s.
- This viscosity can be achieved by mixing additives and base oils, for example containing moiety 1 mineral bases such as Neutral Solvent bases (e.g. 500 NS or 600 NS) and Brightstock. Any other combination of mineral, synthetic or vegetable bases which, when mixed with additives, have a viscosity compatible with the SAE-50 grade may be used.
- moiety 1 mineral bases such as Neutral Solvent bases (e.g. 500 NS or 600 NS) and Brightstock.
- a conventional formulation of cylinder lubricant for marine two-stroke diesel engines is of grade SAE-40 to SAE-60, preferably SAE-50 (according to the SAE J300 classification) and comprises at least 50% by weight of lubricating base oil of mineral and/or synthetic origin, suitable for use in marine engines, for example, of API Group 1 class, i.e. obtained by distillation of selected crude oils followed by purification of these distillates by processes such as solvent extraction, solvent or catalytic dewaxing, hydrotreating or hydrogenation.
- Their Viscosity Index (VI) is between 80 and 120; their sulphur content is greater than 0.03% and their saturated content is less than 90%.
- the lubricant composition according to the invention comprises at least 50% by weight of base oil(s) relative to the total weight of the composition.
- the lubricant composition according to the invention comprises at least 60% by weight, or even at least 70% by weight, of base oil(s) relative to the total weight of the composition.
- the lubricant composition according to the invention comprises from 60% to 99.9% by weight of base oils, preferably from 70% to 98% by weight of base oils, relative to the total weight of the composition.
- the lubricant composition according to the invention further comprises at least one additive selected from detergents, dispersants and mixtures thereof.
- the detergents used in the lubricating compositions according to the present invention are well known to the person skilled in the art.
- detergents commonly used in the formulation of lubricating compositions are anionic compounds having a long lipophilic hydrocarbon chain and a hydrophilic head.
- the associated cation is a metal cation of an alkali or alkaline earth metal.
- the detergents are preferably selected from alkali or alkaline earth metal salts of carboxylic acids, sulphonates, salicylates, naphthenates, and phenate salts.
- the alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium.
- These metal salts may contain the metal in approximately stoichiometric amounts. In this case, they are called non-overbased or “neutral” detergents, although they also provide a certain basicity. These “neutral” detergents typically have a BN, measured according to ASTM D2896, of less than 150 mg KOH/g, or less than 100, or even less than 80 mg KOH/g.
- neutral detergents can contribute to the BN of the lubricants according to the present invention.
- Neutral detergents such as carboxylates, sulphonates, salicylates, phenates, naphthenates of alkali and alkaline earth metals, e.g. calcium, sodium, magnesium, barium, are used.
- BN is high, e.g. above 150 mg KOH/g, typically between 200 and 700 mg KOH/g, usually between 250 and 450 mg KOH/g.
- the excess metal giving the overbased character to the detergent is in the form of oil-insoluble metal salts, e.g. carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
- oil-insoluble metal salts e.g. carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
- the metals of these insoluble salts may be the same as those of the oil-soluble detergents or they may be different. They are preferably chosen from calcium, magnesium, sodium or barium.
- the overbased detergents are thus in the form of micelles composed of insoluble metal salts kept in suspension in the lubricant composition by the detergents in the form of oil-soluble metal salts.
- Overbased detergents are said to be of the mixed type if the micelles comprise multiple types of detergents, which differ from each other by the nature of their hydrophobic chain.
- the oil-soluble metal salts are preferably carboxylates, phenates, sulphonates, salicylates, and mixed phenate-sulphonate and/or salicylate detergents of calcium, magnesium, sodium or barium.
- the insoluble metal salts providing the overbased character are alkali and alkaline earth metal carbonates, preferably calcium carbonate.
- the detergents used in the lubricating compositions according to the present invention are calcium carbonate overbased detergents selected from carboxylates, phenates, sulphonates, salicylates and mixed phenate-sulphonate-salicylate detergents.
- the lubricant composition according to the invention may comprise from 3% to 40%, preferably from 5% to 30%, advantageously from 10% to 25% by weight of detergent(s) based on the total weight of the lubricant composition.
- Dispersants are well-known additives used in the formulation of lubricating compositions, especially for marine applications. Their primary role is to keep in suspension the particles initially present or appearing in the lubricant composition during its use in the engine. They keep those particles from agglomerating by playing on steric hindrance. They may also have a synergistic effect on neutralisation.
- dispersants used as lubricant additives contain a polar moiety, associated with a relatively long hydrocarbon chain, generally containing from 50 to 400 carbon atoms.
- the polar moiety typically contains at least one nitrogen or oxygen element.
- Succinic acid derivatives are dispersants that are particularly used as lubrication additives.
- Succinimides obtained by condensation of succinic anhydrides and amines
- succinic esters obtained by condensation of succinic anhydrides and alcohols or polyols are used in particular.
- These compounds can then be treated with a variety of compounds including sulphur, oxygen, formaldehyde, carboxylic acids and boron or zinc containing compounds to produce, for example, borated succinimides or zinc blocked succinimides.
- Mannich bases obtained by polycondensation of alkyl-substituted phenols, formaldehyde and primary or secondary amines, are also compounds used as dispersants in lubricants.
- the dispersants according to the invention are chosen from succinimides, such as polyisobutylene bis-succinimides, optionally borated or zinc-blocked.
- the lubricant composition according to the invention may comprise from 0.01% to 10%, preferably from 0.1% to 5%, advantageously from 0.5% to 3% by weight of dispersant(s) based on the total weight of the lubricant composition.
- the lubricant composition may further comprise at least one anti-wear additive.
- the anti-wear additive is zinc dithiophosphate or ZnDTP.
- ZnDTP zinc dithiophosphate
- various phosphorus, sulphur, nitrogen, chlorine and boron compounds are included in this category.
- anti-wear additives there is a wide variety of anti-wear additives, but the most commonly used category is that of phospho-sulphur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTPs.
- phospho-sulphur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTPs.
- Amine phosphates, polysulphides, especially sulphur olefins, are also commonly used anti-wear additives.
- Anti-wear and extreme pressure additives of the nitrogenous and sulphurous type such as metal dithiocarbamates, in particular molybdenum dithiocarbamate, are also commonly found in lubricant compositions.
- Glycerol esters are also anti-wear additives. Examples include mono-, di- and trioleates, monopalmitates and monomyristates.
- the lubricant composition comprises, based on the total weight of the lubricant composition:
- the lubricant composition comprises, based on the total weight of the lubricant composition:
- the lubricant composition comprises, based on the total weight of the lubricant composition:
- the lubricant composition comprises, based on the total weight of the lubricant composition:
- the lubricant composition may also include any type of functional additives suitable for their use, for example anti-foaming additives which may be for example polar polymers such as polymethylsiloxanes, polyacrylates, anti-oxidant additives for example of the phenolic or amine type and/or anti-rust additives, for example organometallic compounds or thiadiazoles. These are known to the skilled person.
- anti-foaming additives which may be for example polar polymers such as polymethylsiloxanes, polyacrylates, anti-oxidant additives for example of the phenolic or amine type and/or anti-rust additives, for example organometallic compounds or thiadiazoles.
- the compound of formula (A) is the following compound (I):
- the compound of formula (B) is the following compound (I):
- the compound of formula (A) is the following compound (II):
- the compound of formula (B) is the following compound (II):
- the lubricant composition comprises, based on the total weight of the lubricant composition:
- the lubricant composition comprises, based on the total weight of the lubricant composition:
- the present invention also relates to the use of the lubricant composition according to the invention for the lubrication of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
- the use of the lubricant composition according to the invention prevents and/or reduces corrosion and/or tribocorrosion of said metal part of said engine.
- the present invention also relates to a method of lubricating at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine, comprising bringing said part of an engine in contact with the lubricating composition according to the invention.
- the present invention also relates to the use of a compound of formula (A) according to the invention in a lubricating composition comprising at least one base oil for preventing and/or reducing corrosion and/or tribocorrosion of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
- the present invention also relates to the use of a compound of formula (B) according to the invention in a lubricating composition comprising at least one base oil for preventing and/or reducing corrosion and/or tribocorrosion of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
- the present invention also relates to a method of preventing and/or reducing corrosion and/or tribocorrosion of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine, comprising lubricating said metal part with a lubricating composition according to the invention.
- the present invention also relates to the use of the lubricant composition according to the invention for the passivation of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
- the present invention also relates to a method of passivating at least one metal part of an engine comprising at least one step of bringing said metal part into contact with the lubricating composition according to the invention.
- the present invention also relates to the use of a compound of formula (A) according to the invention in a lubricating composition comprising at least one base oil for passivating at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
- the present invention also relates to the use of a compound of formula (B) according to the invention in a lubricating composition comprising at least one base oil for passivating at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
- the metal part according to the invention is a cylinder or a piston.
- the metal part is made of cast iron.
- the engine according to the invention is a two-stroke engine.
- the engine is a two-stroke marine engine.
- the engine is a heavy fuel oil burning engine.
- “heavy fuel oil” means heavy fractions from the distillation of oil, possibly with additives.
- corrosion means the alteration of a material, preferably metal, by chemical reaction with an oxidant.
- this oxidant is an acid.
- this acid is sulphuric acid H 2 SO 4 .
- tribocorrosion means a process leading to the degradation and wear of a metallic material under the combined action of friction and corrosion as defined above.
- the compound of formula (A) defined herein is used in a cylinder lubricant composition for reducing acid tribocorrosion on the cylinders and pistons of a two-stroke engine, such as a two-stroke marine engine.
- the compound of formula (B) defined herein is used in a cylinder lubricant composition for reducing acid tribocorrosion on the cylinders and pistons of a two-stroke engine, such as a two-stroke marine engine.
- FIG. 1 shows the depth profiles of cast-iron plates obtained after a tribological test conducted in the presence of the lubricant composition according to the invention CL2 and the comparative composition CC1.
- compositions in Table 2 were prepared by mixing the dispersant and/or detergents and the additive in a base oil at 60° C.
- Tribological tests were carried out on an alternative Biceri tribometer using steel rods (EN31) with a diameter of 6 mm and a radius of curvature of 50 mm, and cast-iron platens (FT 25) polished with 800 grit SiC sandpaper.
- the steel rods were also polished to a roughness Ra of between 50 and 100 nm.
- the areas of the cast-iron plates outside the friction zone have been coated with a resin. This resin is removed at the end of the tests. In this way, the resin-coated areas are not corroded during testing and serve as a standard for measuring the depth of wear marks due to corrosion phenomena.
- the lubricant composition Prior to each test, the lubricant composition was heated to 100° C. and brought into contact with a 5 M sulphuric acid solution (27% by weight) at room temperature using a “T” arrangement. The lubricant composition is fed through the main channel and the acid solution is fed through a channel perpendicular to the main channel.
- the corrosion products are removed with anethylenediaminetetraacetic acid (EDTA) solution, and the wear of the cast iron plates is analysed by white light interferometry, which allows a 3D profile of the wear scar produced by corrosion and/or tribocorrosion to be obtained.
- EDTA ethylenediaminetetraacetic acid
- FIG. 1 shows the depth profiles of the cast-iron plates obtained after a tribological test as described above and conducted in the presence of the lubricant composition according to the invention CL2 and the comparative composition 001.
- compositions according to the invention make it possible to protect the cast-iron plate effectively against both corrosion (non-contact zones) and tribocorrosion (contact zone).
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Inorganic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
-
- at least one base oil; and
- from 0.1% to 30% by weight of a phosphorus ester compound of formula (A):
- in which
- s is 0 or 1; and
- the radicals X represent, independently of each other, —OR′ or R′ moieties, where R′ represents hydrogen or a linear or branched hydrocarbon moiety, preferably having from 1 to 36 carbon atoms, with the proviso that:
- when s is 0, the three X radicals represent —OR′ moieties, and
- when s is 1, at least two of the three X radicals are —OR′ moieties.
Description
- The present application is a U.S. National Phase Application under 35 U.S.C. § 371 of International Patent Application No. PCT/EP2020/068122 filed Jun. 26, 2020, which claims priority of French Patent Application No. 19 07180 filed Jun. 28, 2019. The entire contents of which are hereby incorporated by reference.
- The present invention relates to new lubricant compositions, in particular for engines, in particular useful for preventing corrosion and/or tribocorrosion of metal parts in an engine, and in particular in a two-stroke engine, such as a two-stroke marine engine. The present invention also relates to a method of passivating metal parts of an engine, in particular a two-stroke engine, such as a two-stroke marine engine.
- Since 2011, the presence of excessive or even uncontrolled corrosion has become prevalent when engines are operated at very low loads (25% and less of the maximum load). This excessive corrosion is also present with the latest and most severe engine designs. Although in the near future (2020), sulphur levels in marine fuels will be lowered to comply with regulations (SOx emissions), the problem of corrosion remains for many engine operators and more particularly for two-stroke engines.
- The combustion of fuel oils generates acidic gases, in particular sulphur oxides (SO3, formed by oxidation of SO2), which come into contact with the metal parts of the engine. In the presence of water, SO3 hydrolyses to sulphuric acid H2SO4, which is responsible for the corrosion of engine parts. Other acids, such as nitric acid, compounds with one or more carboxylic acid functions, or combinations of these acids, may also be responsible for corrosion and/or tribocorrosion of engine parts.
- Acidic corrosion is located in the tribological system in the ring-piston-liner area. In this area on a lubricated engine, the friction observed is of the reciprocating sliding type.
- In the case of marine engines, especially two-stroke marine engines, lubricant compositions are classified into two categories: Cylinder oils, which provide lubrication to the piston-cylinder assembly, and system oils, which provide lubrication to all moving parts other than the piston-cylinder assembly.
- When the engine is running, the cylinder oil is spread over the cylinder and forms a thin, oily film between the piston and the cylinder wall. This film plays three roles:
-
- ensure separation between the two surfaces to avoid bond wear,
- neutralise sulphuric acid drops formed in the combustion chamber before they reach the cylinder and cause corrosion wear and/or tribocorrosion, and
- disperse any deposits that may form on each surface to keep them clean.
- Currently used engine lubricant compositions, especially for marine engines, comprise a base oil to which dispersants and overbased detergents are added. These overbased detergents typically comprise a calcium carbonate (CaCO3) core coated with a surfactant layer. Calcium carbonate reacts with sulphuric acid to form calcium sulphate (CaSO4). The reduction of sulphuric acid in the medium allows the protection of parts against corrosion and/or tribocorrosion.
- In order to ensure this protection, the lubricant compositions used must be sufficiently basic (in particular to neutralise the acid), which implies increasing the quantity of detergents included in these compositions.
- Thus, lubricant compositions currently on the market have Base Numbers (BN) above 70.
- However, the increase in the amount of detergents in these lubricant compositions leads to an increase in the number of CaCO3 and CaSO4 particles responsible for polishing (or abrasive wear) of the surfaces of the metal engine parts, and in particular of the cylinders of two-stroke engines, such as two-stroke marine engines. On the other hand, the use of currently available lubricant compositions does not fully protect metal engine parts from corrosion and/or tribocorrosion, and in particular metal parts of the two-stroke engine from tribocorrosion, when the friction is of the reciprocating sliding type.
- There is therefore a benefit to providing lubricant compositions to improve the protection of metal parts of an engine, in particular a two-stroke engine, such as a two-stroke marine engine, against corrosion and/or tribocorrosion.
- There is also a benefit to providing lubricant compositions that reduce their Base Number.
- An objective of the present invention is to provide lubricant compositions for improving the protection of metal parts of an engine, typically a two-stroke engine, especially a two-stroke marine engine, against corrosion and/or tribocorrosion.
- The present invention is aimed more particularly at the supply of cylinder oils for two-stroke engines, in particular for two-stroke marine engines.
- A further objective of the present invention is to provide lubricant compositions with a reduced Base Number.
- Further objectives will become apparent from the following description of the invention.
- These objectives are fulfilled by the present invention which relates to a lubricant composition comprising:
-
- at least one base oil; and
- from 0.1% to 30%, preferably from 0.5% to 20%, advantageously from 1% to 10% by weight of a phosphorus ester compound of formula (A):
-
- in which
- s is 0 or 1; and
- the radicals X represent, independently of each other, —OR′ or R′ moieties, where R′ represents hydrogen or a linear or branched hydrocarbon moiety, preferably having from 1 to 36 carbon atoms, with the proviso that:
- when s is 0, the three X radicals represent —OR′ moieties, and
- when s is 1, at least two of the three X radicals are —OR′ moieties.
- Preferably, R′ represents a linear or branched alkyl moiety comprising from 1 to 36 carbon atoms, preferably from 2 to 30 carbon atoms, advantageously from 4 to 24 carbon atoms, or R′ represents a linear or branched alkenyl moiety comprising from 2 to 36 carbon atoms, preferably from 2 to 30 carbon atoms, advantageously from 4 to 24 carbon atoms.
- Preferentially, these objectives are fulfilled by the present invention which relates to a lubricant composition comprising:
-
- at least one base oil; and
- from 0.1% to 30%, preferably from 0.5% to 20%, advantageously from 1% to 10% by weight of a phosphorus ester compound of formula (B):
-
- in which:
- R1 and R2, which may be the same or different, independently represent a linear or branched alkyl moiety comprising from 1 to 36 carbon atoms, preferably from 2 to 30 carbon atoms, advantageously from 4 to 24 carbon atoms, or R1 and R2, which may be the same or different, independently represent a linear or branched alkenyl moiety comprising from 2 to 36 carbon atoms, preferably from 2 to 30 carbon atoms, advantageously from 4 to 24 carbon atoms; and
- R3 represents hydrogen or a hydroxyl moiety (OH).
- Preferably, the alkenyl moiety (R1 and/or R2) according to the invention comprises at least one double bond. Preferably, said double bond is located at C-9, C-10 of the alkenyl moiety with respect to the phosphorus ester function.
- Preferably, the R1, R2 or R3 moiety does not comprise a sulphur or nitrogen atom.
- According to the invention, a hydrocarbon moiety is a linear or branched, saturated, partially or totally unsaturated chain comprising from 1 to 36 carbon atoms, preferably from 2 to 30 carbon atoms, advantageously from 4 to 24 carbon atoms.
- According to a particular embodiment of the invention, the base oil included in the lubricating composition is selected from oils of mineral, synthetic or vegetable origin as well as mixtures thereof.
- The mineral or synthetic oils generally used in the application belong to one of the classes defined in the API classification as summarised in the table below.
-
TABLE 1 Table 1: API classification of base oils Saturated Sulphur Viscosity content content index Group 1 Mineral oils <90% >0.03% 80 ≤ VI < 120 Group 2 Hydrocracked oils≥90% ≤0.03% 80 ≤ VI < 120 Group 3 ≥90% ≤0.03% ≥120 Hydro-isomerised oils Group 4 Polyalphaolefins (PAO) Group 5 Other bases not included in bases in groups 1 to 4 - Group 1 mineral oils may be obtained by distillation of selected naphthenic or paraffinic crudes, followed by purification of these distillates by processes such as solvent extraction, solvent or catalytic dewaxing, hydrotreating or hydrogenation.
-
Group 2 and 3 oils are obtained by more severe purification processes, for example a combination of hydrotreating, hydrocracking, hydrogenation and catalytic dewaxing. - Examples of Group 4 and 5 synthetic bases include poly-alpha olefins, polybutenes, polyisobutenes, alkylbenzenes.
- These base oils can be used alone or in a mixture. Mineral oil can be combined with synthetic oil.
- Marine diesel two-stroke cylinder oils have a viscosity grade of SAE-40 to SAE-60, generally SAE-50 equivalent to a kinematic viscosity at 100° C. of between 16.3 and 21.9 mm2/s.
- Grade 40 oils have a kinematic viscosity at 100° C. of between 12.5 and 16.3 mm2/s.
-
Grade 50 oils have a kinematic viscosity at 100° C. of between 16.3 and 21.9 mm2/s. - Grade 60 oils have a kinematic viscosity at 100° C. of between 21.9 and 26.1 mm2/s.
- According to industry practice, it is preferred to formulate cylinder oils for two-stroke marine diesel engines with a kinematic viscosity at 100° C. between 18 and 21.5, preferably between 19 and 21.5 mm2/s.
- This viscosity can be achieved by mixing additives and base oils, for example containing moiety 1 mineral bases such as Neutral Solvent bases (e.g. 500 NS or 600 NS) and Brightstock. Any other combination of mineral, synthetic or vegetable bases which, when mixed with additives, have a viscosity compatible with the SAE-50 grade may be used.
- Typically, a conventional formulation of cylinder lubricant for marine two-stroke diesel engines is of grade SAE-40 to SAE-60, preferably SAE-50 (according to the SAE J300 classification) and comprises at least 50% by weight of lubricating base oil of mineral and/or synthetic origin, suitable for use in marine engines, for example, of API Group 1 class, i.e. obtained by distillation of selected crude oils followed by purification of these distillates by processes such as solvent extraction, solvent or catalytic dewaxing, hydrotreating or hydrogenation. Their Viscosity Index (VI) is between 80 and 120; their sulphur content is greater than 0.03% and their saturated content is less than 90%.
- Advantageously, the lubricant composition according to the invention comprises at least 50% by weight of base oil(s) relative to the total weight of the composition.
- More advantageously, the lubricant composition according to the invention comprises at least 60% by weight, or even at least 70% by weight, of base oil(s) relative to the total weight of the composition.
- More particularly advantageously, the lubricant composition according to the invention comprises from 60% to 99.9% by weight of base oils, preferably from 70% to 98% by weight of base oils, relative to the total weight of the composition.
- Preferably, the lubricant composition according to the invention further comprises at least one additive selected from detergents, dispersants and mixtures thereof.
- The detergents used in the lubricating compositions according to the present invention are well known to the person skilled in the art.
- In the context of the present invention, detergents commonly used in the formulation of lubricating compositions are anionic compounds having a long lipophilic hydrocarbon chain and a hydrophilic head. The associated cation is a metal cation of an alkali or alkaline earth metal.
- The detergents are preferably selected from alkali or alkaline earth metal salts of carboxylic acids, sulphonates, salicylates, naphthenates, and phenate salts.
- The alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium.
- These metal salts may contain the metal in approximately stoichiometric amounts. In this case, they are called non-overbased or “neutral” detergents, although they also provide a certain basicity. These “neutral” detergents typically have a BN, measured according to ASTM D2896, of less than 150 mg KOH/g, or less than 100, or even less than 80 mg KOH/g.
- This type of so-called neutral detergents can contribute to the BN of the lubricants according to the present invention. Neutral detergents such as carboxylates, sulphonates, salicylates, phenates, naphthenates of alkali and alkaline earth metals, e.g. calcium, sodium, magnesium, barium, are used.
- When the metal is in excess (above the stoichiometric amount), we are dealing with so-called overbased detergents. Their BN is high, e.g. above 150 mg KOH/g, typically between 200 and 700 mg KOH/g, usually between 250 and 450 mg KOH/g.
- The excess metal giving the overbased character to the detergent is in the form of oil-insoluble metal salts, e.g. carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
- In the same overbased detergent, the metals of these insoluble salts may be the same as those of the oil-soluble detergents or they may be different. They are preferably chosen from calcium, magnesium, sodium or barium.
- The overbased detergents are thus in the form of micelles composed of insoluble metal salts kept in suspension in the lubricant composition by the detergents in the form of oil-soluble metal salts.
- Overbased detergents with only one type of detergent soluble metal salt will generally be named after the nature of the hydrophobic chain of that detergent salt.
- Thus, they will be said to be of the carboxylate, phenate, salicylate, sulphonate or naphthenate type depending on whether the detergent is a carboxylate, phenate, salicylate, sulphonate or naphthenate respectively.
- Overbased detergents are said to be of the mixed type if the micelles comprise multiple types of detergents, which differ from each other by the nature of their hydrophobic chain.
- For use in the lubricant compositions according to the present invention, the oil-soluble metal salts are preferably carboxylates, phenates, sulphonates, salicylates, and mixed phenate-sulphonate and/or salicylate detergents of calcium, magnesium, sodium or barium.
- The insoluble metal salts providing the overbased character are alkali and alkaline earth metal carbonates, preferably calcium carbonate.
- Preferably, the detergents used in the lubricating compositions according to the present invention are calcium carbonate overbased detergents selected from carboxylates, phenates, sulphonates, salicylates and mixed phenate-sulphonate-salicylate detergents.
- Advantageously, the lubricant composition according to the invention may comprise from 3% to 40%, preferably from 5% to 30%, advantageously from 10% to 25% by weight of detergent(s) based on the total weight of the lubricant composition.
- Dispersants are well-known additives used in the formulation of lubricating compositions, especially for marine applications. Their primary role is to keep in suspension the particles initially present or appearing in the lubricant composition during its use in the engine. They keep those particles from agglomerating by playing on steric hindrance. They may also have a synergistic effect on neutralisation.
- In the context of the present invention, dispersants used as lubricant additives contain a polar moiety, associated with a relatively long hydrocarbon chain, generally containing from 50 to 400 carbon atoms. The polar moiety typically contains at least one nitrogen or oxygen element.
- Succinic acid derivatives are dispersants that are particularly used as lubrication additives. Succinimides, obtained by condensation of succinic anhydrides and amines, succinic esters obtained by condensation of succinic anhydrides and alcohols or polyols are used in particular.
- These compounds can then be treated with a variety of compounds including sulphur, oxygen, formaldehyde, carboxylic acids and boron or zinc containing compounds to produce, for example, borated succinimides or zinc blocked succinimides.
- Mannich bases, obtained by polycondensation of alkyl-substituted phenols, formaldehyde and primary or secondary amines, are also compounds used as dispersants in lubricants.
- Preferably, the dispersants according to the invention are chosen from succinimides, such as polyisobutylene bis-succinimides, optionally borated or zinc-blocked.
- Advantageously, the lubricant composition according to the invention may comprise from 0.01% to 10%, preferably from 0.1% to 5%, advantageously from 0.5% to 3% by weight of dispersant(s) based on the total weight of the lubricant composition.
- The lubricant composition may further comprise at least one anti-wear additive.
- Preferably, the anti-wear additive is zinc dithiophosphate or ZnDTP. Also included in this category are various phosphorus, sulphur, nitrogen, chlorine and boron compounds.
- There is a wide variety of anti-wear additives, but the most commonly used category is that of phospho-sulphur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTPs.
- Amine phosphates, polysulphides, especially sulphur olefins, are also commonly used anti-wear additives.
- Anti-wear and extreme pressure additives of the nitrogenous and sulphurous type, such as metal dithiocarbamates, in particular molybdenum dithiocarbamate, are also commonly found in lubricant compositions. Glycerol esters are also anti-wear additives. Examples include mono-, di- and trioleates, monopalmitates and monomyristates.
- According to a particular embodiment, the lubricant composition comprises, based on the total weight of the lubricant composition:
-
- from 50% to 96.9% by weight, preferably from 60 to 95% by weight, more preferably from 70 to 90% by weight, of base oil(s),
- from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 10% by weight, of one or more phosphorus ester compounds of formula (A), and
- from 3% to 40% by weight, preferably from 5% to 30% by weight, more preferably from 10% to 25% by weight, of detergent(s), and
- optionally from 0.01% to 10% by weight, preferably from 0.1 to 5% by weight, more preferably from 0.5% to 3% by weight, of dispersant(s).
- According to a particular embodiment, the lubricant composition comprises, based on the total weight of the lubricant composition:
-
- from 50% to 96.9% by weight, preferably from 60 to 95% by weight, more preferably from 70 to 90% by weight, of base oil(s),
- from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 10% by weight, of one or more phosphorus ester compounds of formula (B), and
- from 3% to 40% by weight, preferably from 5% to 30% by weight, more preferably from 10% to 25% by weight, of detergent(s), and
- optionally from 0.01% to 10% by weight, preferably from 0.1 to 5% by weight, more preferably from 0.5% to 3% by weight, of dispersant(s).
- According to a particular embodiment, the lubricant composition comprises, based on the total weight of the lubricant composition:
-
- from 60% to 99% by weight, preferably from 60 to 95% by weight, more preferably from 70 to 90% by weight, of base oil(s),
- from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 10% by weight, of one or more phosphorus ester compounds of formula (A), and
- from 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, of dispersant(s), and
- optionally from 3 to 40% by weight, preferably from 5 to 30% by weight, more preferably from 10 to 25% by weight, of detergent(s).
- According to a particular embodiment, the lubricant composition comprises, based on the total weight of the lubricant composition:
-
- from 60% to 99% by weight, preferably from 60 to 95% by weight, more preferably from 70 to 90% by weight, of base oil(s),
- from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 10% by weight, of one or more phosphorus ester compounds of formula (B), and
- from 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, of dispersant(s), and
- optionally from 3 to 40% by weight, preferably from 5 to 30% by weight, more preferably from 10 to 25% by weight, of detergent(s).
- The lubricant composition may also include any type of functional additives suitable for their use, for example anti-foaming additives which may be for example polar polymers such as polymethylsiloxanes, polyacrylates, anti-oxidant additives for example of the phenolic or amine type and/or anti-rust additives, for example organometallic compounds or thiadiazoles. These are known to the skilled person.
- According to one embodiment of the invention, the compound of formula (A) is the following compound (I):
- According to one embodiment of the invention, the compound of formula (B) is the following compound (I):
- According to another embodiment of the invention, the compound of formula (A) is the following compound (II):
- According to another embodiment of the invention, the compound of formula (B) is the following compound (II):
- According to a particular embodiment, the lubricant composition comprises, based on the total weight of the lubricant composition:
-
- from 50% to 96.9% by weight, preferably from 60 to 95% by weight, more preferably from 70 to 90% by weight, of base oil(s),
- from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 10% by weight, of one or more phosphorus ester compounds including at least one compound of formula (I) or formula (II) defined above, and
- from 3 to 40% by weight, preferably from 5 to 30% by weight, more preferably from 10 to 25% by weight, of detergent(s) comprising at least one phenate or sulphonate overbased detergent, and
- optionally from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, more preferably from 0.5 to 3% by weight, of dispersant(s).
- According to a particular embodiment, the lubricant composition comprises, based on the total weight of the lubricant composition:
-
- from 60% to 99% by weight, preferably from 60 to 95% by weight, more preferably from 70 to 90% by weight, of base oil(s),
- from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 10% by weight, of one or more phosphorus ester compounds including at least one compound of formula (I) or formula (II) defined above, and
- from 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, of dispersant(s) selected from succinimides, and
- optionally from 3 to 40% by weight, preferably from 5 to 30% by weight, more preferably from 10 to 25% by weight, of detergent(s).
- The present invention also relates to the use of the lubricant composition according to the invention for the lubrication of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
- Preferably, the use of the lubricant composition according to the invention prevents and/or reduces corrosion and/or tribocorrosion of said metal part of said engine.
- The present invention also relates to a method of lubricating at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine, comprising bringing said part of an engine in contact with the lubricating composition according to the invention.
- The present invention also relates to the use of a compound of formula (A) according to the invention in a lubricating composition comprising at least one base oil for preventing and/or reducing corrosion and/or tribocorrosion of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
- The present invention also relates to the use of a compound of formula (B) according to the invention in a lubricating composition comprising at least one base oil for preventing and/or reducing corrosion and/or tribocorrosion of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
- The present invention also relates to a method of preventing and/or reducing corrosion and/or tribocorrosion of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine, comprising lubricating said metal part with a lubricating composition according to the invention.
- The present invention also relates to the use of the lubricant composition according to the invention for the passivation of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
- The present invention also relates to a method of passivating at least one metal part of an engine comprising at least one step of bringing said metal part into contact with the lubricating composition according to the invention.
- The present invention also relates to the use of a compound of formula (A) according to the invention in a lubricating composition comprising at least one base oil for passivating at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
- The present invention also relates to the use of a compound of formula (B) according to the invention in a lubricating composition comprising at least one base oil for passivating at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
- Preferably, the metal part according to the invention is a cylinder or a piston.
- Advantageously, the metal part is made of cast iron.
- Preferably, the engine according to the invention is a two-stroke engine. Preferably, the engine is a two-stroke marine engine.
- Preferably, the engine is a heavy fuel oil burning engine. For the purposes of this invention, “heavy fuel oil” means heavy fractions from the distillation of oil, possibly with additives.
- For the purposes of this invention, “corrosion” means the alteration of a material, preferably metal, by chemical reaction with an oxidant. Preferably, this oxidant is an acid. Preferably, this acid is sulphuric acid H2SO4.
- For the purposes of this invention, “tribocorrosion” means a process leading to the degradation and wear of a metallic material under the combined action of friction and corrosion as defined above.
- Advantageously, the compound of formula (A) defined herein is used in a cylinder lubricant composition for reducing acid tribocorrosion on the cylinders and pistons of a two-stroke engine, such as a two-stroke marine engine.
- Even more advantageously, the compound of formula (B) defined herein is used in a cylinder lubricant composition for reducing acid tribocorrosion on the cylinders and pistons of a two-stroke engine, such as a two-stroke marine engine.
-
FIG. 1 shows the depth profiles of cast-iron plates obtained after a tribological test conducted in the presence of the lubricant composition according to the invention CL2 and the comparative composition CC1. - The present invention will now be described with the help of non-limiting examples.
- The compositions in Table 2 (CL: lubricant composition according to the invention; CC: comparative lubricant composition) were prepared by mixing the dispersant and/or detergents and the additive in a base oil at 60° C.
-
TABLE 2 Table 2: Lubricant compositions according to the invention and comparative lubricant compositions Phenate Sulphonate Base oil Dispersant detergent detergent Additive Lubricating (% by (% by (% by (% by (% by composition weight) weight) weight) weight) weight) CL1 mixture of Polyisobutylene phenate sulphonate Compound two group I succinimide with a BN with a of base oils (1.1%) of 250 BN of 400 formula (I) (75.3%) (13.6%) (5.3%) (5%) CL2 mixture of Polyisobutylene phenate sulphonate Compound two group I succinimide with a BN with a of base oils (1.1%) of 250 BN of 400 formula (II) (75.3%) (13.6%) (5.3%) (5%) CC1 mixture of Polyisobutylene phenate sulphonate — two group I succinimide with a BN with a base oils (1.2%) of 250 BN of 400 (79.2%) (14.3%) (5.3%) - Tribological tests were carried out on an alternative Biceri tribometer using steel rods (EN31) with a diameter of 6 mm and a radius of curvature of 50 mm, and cast-iron platens (FT 25) polished with 800 grit SiC sandpaper. The steel rods were also polished to a roughness Ra of between 50 and 100 nm. In addition, the areas of the cast-iron plates outside the friction zone have been coated with a resin. This resin is removed at the end of the tests. In this way, the resin-coated areas are not corroded during testing and serve as a standard for measuring the depth of wear marks due to corrosion phenomena.
- Prior to each test, the lubricant composition was heated to 100° C. and brought into contact with a 5 M sulphuric acid solution (27% by weight) at room temperature using a “T” arrangement. The lubricant composition is fed through the main channel and the acid solution is fed through a channel perpendicular to the main channel.
- The conditions for these tests are as follows:
-
- Temperature: 100° C.
- Pressure: 0.67 GPa
- Speed: 0.02 m/s
- Trace length: 5 mm
- Duration: 6 hrs.
- At the end of each test, the corrosion products are removed with anethylenediaminetetraacetic acid (EDTA) solution, and the wear of the cast iron plates is analysed by white light interferometry, which allows a 3D profile of the wear scar produced by corrosion and/or tribocorrosion to be obtained.
- These 3D profiles provide depth profiles of the wear scar.
FIG. 1 shows the depth profiles of the cast-iron plates obtained after a tribological test as described above and conducted in the presence of the lubricant composition according to the invention CL2 and the comparative composition 001. - The results of these tests show that in the absence of an additive, the cast-iron plate corrodes in the areas not in contact with the steel rod (non-contact areas), and tribocorrosion wear is also observed in the area in contact with the rod. The presence of additives improves the protection against corrosion and tribocorrosion. Indeed, without wishing to be bound by any theory, the additives make it possible to create a second layer of protection which is added to the neutralisation of the acid drops by the detergent by forming a physical barrier between the surface of the metal part and the oil of the lubricant composition, which prevents corrosion phenomena.
- The lubricant compositions according to the invention, and more particularly the compositions comprising the compounds of formula (I) or (II) (CL1 and CL2), make it possible to protect the cast-iron plate effectively against both corrosion (non-contact zones) and tribocorrosion (contact zone).
Claims (10)
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FRFR1907180 | 2019-06-28 | ||
FR1907180A FR3097875B1 (en) | 2019-06-28 | 2019-06-28 | Lubricating composition for preventing corrosion and/or tribocorrosion of metal parts in an engine |
PCT/EP2020/068122 WO2020260650A1 (en) | 2019-06-28 | 2020-06-26 | Lubricant composition for preventing corrosion and/or tribo-corrosion of metal parts in an engine |
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US17/619,804 Pending US20220411713A1 (en) | 2019-06-28 | 2020-06-26 | Lubricant composition for preventing corrosion and/or tribocorrosion of metalparts in an engine |
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US (1) | US20220411713A1 (en) |
EP (1) | EP3990591A1 (en) |
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2019
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- 2020-06-26 JP JP2021577876A patent/JP2022539199A/en active Pending
- 2020-06-26 CN CN202080047553.6A patent/CN114026208B/en active Active
- 2020-06-26 WO PCT/EP2020/068122 patent/WO2020260650A1/en active Application Filing
- 2020-06-26 EP EP20734083.7A patent/EP3990591A1/en active Pending
- 2020-06-26 US US17/619,804 patent/US20220411713A1/en active Pending
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FR3097875B1 (en) | 2022-03-04 |
JP2022539199A (en) | 2022-09-07 |
KR20220059470A (en) | 2022-05-10 |
CN114026208B (en) | 2022-10-25 |
FR3097875A1 (en) | 2021-01-01 |
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CN114026208A (en) | 2022-02-08 |
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