EP2652100B1 - Grease composition - Google Patents
Grease composition Download PDFInfo
- Publication number
- EP2652100B1 EP2652100B1 EP11805229.9A EP11805229A EP2652100B1 EP 2652100 B1 EP2652100 B1 EP 2652100B1 EP 11805229 A EP11805229 A EP 11805229A EP 2652100 B1 EP2652100 B1 EP 2652100B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- graphite
- grease
- composition according
- preferentially
- molybdenum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Not-in-force
Links
- 239000000203 mixture Substances 0.000 title claims description 65
- 239000004519 grease Substances 0.000 title claims description 39
- 239000000344 soap Substances 0.000 claims description 51
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 47
- 229910052782 aluminium Inorganic materials 0.000 claims description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- 229910002804 graphite Inorganic materials 0.000 claims description 37
- 239000010439 graphite Substances 0.000 claims description 37
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical class C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 claims description 30
- 239000002199 base oil Substances 0.000 claims description 28
- 239000002562 thickening agent Substances 0.000 claims description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims description 16
- 239000011733 molybdenum Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- 239000007866 anti-wear additive Substances 0.000 claims description 7
- 239000005069 Extreme pressure additive Substances 0.000 claims description 6
- 229920002367 Polyisobutene Polymers 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 238000005461 lubrication Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000004568 cement Substances 0.000 claims description 4
- 238000003466 welding Methods 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 235000010210 aluminium Nutrition 0.000 description 41
- 239000003925 fat Substances 0.000 description 37
- 150000004665 fatty acids Chemical class 0.000 description 12
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 230000006872 improvement Effects 0.000 description 7
- 239000000314 lubricant Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- -1 for example Substances 0.000 description 6
- 230000001050 lubricating effect Effects 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 229920002396 Polyurea Polymers 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920013639 polyalphaolefin Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical group CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 150000004668 long chain fatty acids Chemical class 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 3
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 150000004659 dithiocarbamates Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000016649 Copaifera officinalis Species 0.000 description 1
- 239000004859 Copal Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 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
- 235000019482 Palm oil Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- ZKZAYPCZGZAZAG-UHFFFAOYSA-J n,n-dibutylcarbamodithioate;molybdenum(4+) Chemical compound [Mo+4].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC ZKZAYPCZGZAZAG-UHFFFAOYSA-J 0.000 description 1
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- UAQJVNPFHGOEAH-UHFFFAOYSA-N oxido-oxo-phosphosulfanylphosphanium Chemical class O=P(=O)SP(=O)=O UAQJVNPFHGOEAH-UHFFFAOYSA-N 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003208 petroleum Substances 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
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000021391 short chain fatty acids Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229940032094 squalane Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 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 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 239000001993 wax 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
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
-
- 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
- C10M121/00—Lubricating compositions characterised by the thickener being a compound of unknown or incompletely defined constitution
-
- 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
- C10M125/22—Compounds containing sulfur, selenium or tellurium
-
- 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
- C10M169/06—Mixtures of thickeners 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
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
-
- 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
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
- C10M2201/0416—Carbon; Graphite; Carbon black used as thickening agents
-
- 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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
- C10M2207/1265—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic used as thickening agent
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
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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
- C10M2223/045—Metal containing thio derivatives
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/32—Wires, ropes or cables lubricants
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/38—Conveyors or chain belts
Definitions
- the present invention relates to grease compositions, particularly used in industrial applications or public works, requiring very good resistance to heavy loads and shocks.
- lubricating greases which are solid or semi-fluid substances resulting from the dispersion of a thickener in a liquid lubricant, incorporating additives which give them particular properties.
- lubricating greases are prepared with thickeners such as metal salts of fatty acids.
- the fatty acid is dissolved in the base oil at a relatively high temperature, and then the appropriate metal hydroxide is added. After having evaporated by cooking the water which forms during the reaction, it is cooled for a definite period of time to form the soap network.
- Hydroxides of Lithium, Sodium, Calcium, Barium, Titanium or Aluminum, or certain aluminum trimers are suitable for example as metal compounds for the manufacture of grease.
- Long-chain fatty acids of the order of C14 to C28, mainly C18, generally come from vegetable oils (castor oil for example) or animal oils (for example tallow). They can be hydrogenated.
- the best known derivative is 12-hydroxystearic acid from ricinoleic acid.
- short-chain acids typically comprising between 6 and 12 carbon atoms, for example azelaic acid or benzoic acid. Complex fats are then formed.
- Metallic soaps form a fibrous structure, except for aluminum soaps, which have a spherical gel structure.
- inorganic thickeners such as, for example, bentonite, silica gel can be used.
- Polycarbamides polyureas are also found in the thickeners.
- polyurea thickened greases do not have sufficient mechanical stability, especially because of their thixotropic nature, which leads them to destructure under mechanical stresses.
- Inorganic thickeners also have problems with mechanical strength and water resistance, which is detrimental in open systems.
- the metal soaps have, for their part, a very good mechanical strength.
- greases thickened with simple or complex aluminum soaps have a very good mechanical strength, are very resistant to water (in particular complex aluminum greases), and have a very good adhesiveness to metal surfaces.
- the patent FR 1 048 670 discloses for example a grease comprising an aluminum soap, allowing the lubrication of heavy parts in industry, which operate under stringent conditions of temperature and loads. The presence of aluminum soap prevents the separation of the base oil from the grease, and therefore the destructuring of the grease.
- Requirement FR 2 172 080 also describes particularly stable greases thickened with aluminum soaps, as well as the demand FR 2,012,238 , which also highlights their resistance to water.
- Requirement EP 0661378 discloses examples of greases thickened with complex aluminum soaps containing molybdenum dithiocarbamate (MoDTC), alone or in combination with zinc dithiophosphate (DTPZn). These compositions do not contain graphite. Their EP performance is poor, especially that of fat containing only MoDTC.
- MoDTC molybdenum dithiocarbamate
- DTPZn zinc dithiophosphate
- Thickened greases with complex aluminum soaps, and including antiwear, extreme pressure additives, as well as a friction modifier, molybdenum disulfide (MoS 2 ), are marketed under the name of COPAL MS 2 for applications on open gears in heavy industry such as cement plants, sugar mills (grinders, furnace control harnesses, slewing rings), or for public works machinery.
- MoS 2 molybdenum disulfide
- these fats have a high content of molybdenum (Mo), which it would be advantageous to reduce for environmental reasons, and extreme pressure properties which could be improved, in particular to withstand shocks and knocks, for example in the crushers and public works machinery.
- Mo molybdenum
- the greases may contain various solid lubricants known for their frictional and anti-wear properties, such as, for example, molybdenum or tungsten disulfide, graphite or polytetrafluoroethylene (PTFE).
- solid lubricants known for their frictional and anti-wear properties, such as, for example, molybdenum or tungsten disulfide, graphite or polytetrafluoroethylene (PTFE).
- Requirement FR 2,723,747 discloses high temperature greases for homokinetic joints comprising mineral and / or synthetic base oils, polyurea thickeners and MoS 2 as a solid lubricant, as well as graphite and at least one organic molybdenum compound, preferentially molybdenum dithiocarbamate.
- Solid graphite lubricants, MoDTC, PTFE can lower the MoS 2 costly solid lubricant content, but without substituting it completely.
- the molybdenum content of the compositions disclosed is at least of the order of 5000 ppm.
- the document WO 03/000831 relates to a polyalphaolefin based grease for use in applications requiring resistance to high loads.
- the grease contains a thickener based on soap and aluminum. It may also contain a solid lubricant such as graphite and molybdenum dithiocarbamate.
- thickened greases with aluminum soaps and comprising, as a friction modifier, a molybdenum dithiocarbamate combined with graphite, have improved extreme pressure properties;
- the compositions according to the invention can exhibit these improved properties with a reduced molybdenum content.
- compositions according to the invention comprise, as base oils (a), one or more mineral base oils, alone or as a mixture, and optionally one or more synthetic base oils.
- compositions according to the invention comprise at least one complex aluminum soap as thickener (b).
- the aluminum soap (s), simple (s) or complex (s) constitute at least 80% by weight of the thickener (b) in said compositions.
- the grease compositions according to the invention further comprise one or more additives chosen from antiwear and / or extreme pressure additives, preferably phosphosulfides, preferentially dithiophosphates.
- compositions according to one of claims 1 to 5 further comprising one or more polymers, preferably chosen from polyisobutenes.
- the molybdenum content is between 500 and 5000 ppm, preferably between 1000 and 4800 ppm.
- the mass content of graphite is between 0.5 and 3%, preferably between 0.7 and 2%.
- the present invention also relates to the use of a grease composition as described above for the lubrication of systems open, preferably open gears, wire ropes, chain drives.
- this use is made in the field of industry, preferably the cement industry, sugar, or steel, or in the field of public works.
- the present invention also relates to the use of an additive composition comprising molybdenum dithiocarbamate and graphite to increase the welding load, measured according to DIN 51350/4, of a thickened grease with simple aluminum soaps or complex.
- the present invention also relates to an open system, preferably open gear, wire rope, chain drive, comprising a grease composition as described above.
- the other base oil (s) used in the compositions according to the present invention may be oils of mineral or synthetic origin of groups I to V according to the classes defined in the API classification (American Petroleum Institute).
- 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, desalphating, solvent dewaxing, hydrotreatment, hydrocracking and hydroisomerization, hydrofinishing.
- the base oils of the grease compositions according to the present invention can also be synthetic oils, such as certain esters, silicones, glycols, polybutene, polyalphaolefins (PAO), alkylbenzene, alkylnaphthalene.
- synthetic oils such as certain esters, silicones, glycols, polybutene, polyalphaolefins (PAO), alkylbenzene, alkylnaphthalene.
- the base oils may also be oils of natural origin, for example esters of alcohol and carboxylic acids, obtainable from natural resources such as sunflower oil, rapeseed oil, palm oil, soy....
- the grease compositions according to the invention contain a mixture of mineral oils, for example paraffinic mineral oils and naphthenic mineral oils, as base oils (a).
- they contain a mixture of mineral oil (s), for example paraffinic mineral oils and naphthenic mineral oils, and synthetic oils, for example polyalphaolefins.
- mineral oil for example paraffinic mineral oils and naphthenic mineral oils
- synthetic oils for example polyalphaolefins.
- the base oil mixture (a) is set so that its viscosity at 40 ° C. according to ASTM D 445 is between 100 and 500 cSt, preferably between 110 and 300 cSt, preferably between 150 and 250 cSt. .
- the greases according to the present invention are thickened to aluminum soaps, simple or complex, which have mechanical properties and adhesiveness to the upper surfaces, as well as excellent water resistance.
- the aluminum and fatty acid soaps can be prepared separately, or in situ during the manufacture of the fat (in the latter case, the fatty acid (s) is dissolved in the base oil, and then the compound is added. appropriate metal).
- the simple aluminum soaps are for example prepared from aluminum hydroxide Al (OH) 3 and one or more long-chain fatty acids, typically comprising from 10 to 28 carbon atoms, saturated or unsaturated, by example stearic acid.
- the complex aluminum soaps are prepared, for example, from stearic acid, benzoic acid and aluminum trimers corresponding to formula (I): Where R is a hydrocarbon radical, preferentially alkyl, for example isopropyl.
- the complex aluminum soaps have, compared to simple soaps, the advantage of better resistance to high temperature.
- the aluminum soaps are preferably used at levels of the order of 5 to 30% by weight, preferably 10 to 25% by weight, preferably from 105 to 20% by weight, typically 12% by weight in the greases. the invention.
- the amount of metallic soap (es) is generally adjusted so as to obtain greases of grade 00, grade 0, grade 1 or grade 2 according to the NLGI classification.
- the greases according to the invention mainly contain aluminum soaps, simple or complex, as thickeners. This means that these Soaps together represent the highest percentage by weight in the greases according to the invention, compared to the percentage by weight of other thickening materials.
- the amount of aluminum soap (s), simple or complex constitutes at least 80% by weight, based on the total weight of thickening materials, in the grease compositions according to the invention.
- the greases according to the invention can contain, as the major thickener, metal soap of simple or complex fatty acids, and smaller amounts of other thickeners, such as other metallic soaps, simple or complex, polyureas, or inorganic thickeners, type bentonite or alumino silicates.
- the greases according to the invention are free of polyurea thickeners, which are more technically complicated to manufacture, in particular because the components used in their manufacture, such as isocyanates and amines, are very toxic and unstable. in storage.
- the greases according to the invention exclusively contain simple or complex aluminum metal soaps as thickeners.
- the grease compositions according to the invention contain graphite and molybdenum dithiocarbamate. It has surprisingly been found, and even though graphite is known for its low resistance under heavy load, that this combination makes it possible to obtain thickened greases with aluminum soaps having very good extreme pressure properties, with reduced rate of molybdenum.
- compositions according to the invention contain molybdenum dithiocarbamates, friction modifying additives well known to those skilled in the art.
- molybdenum dithiocarbamate organometallic friction modifiers can for example be dialkyldithiocarbamates of molybdenum corresponding to formula (II): Where X 1 , X 2 , X 3 , X 4 are alkyl chains, preferably containing 2 to 13 carbon atoms, preferably 2 to 6 carbon atoms.
- the amount of MoDTC of the compositions according to the invention is adjusted so that their molybdenum content is between 500 and 5000, preferably between 1000 and 4800 ppm, preferably between 1500 and 4500 ppm, preferably between 2000 and 4000, preferentially between 2500 and 3000 ppm. Too low MoDTC content leads to poor extreme pressure properties, too high a content is detrimental to the environment.
- This content can be measured according to the usual techniques, plasma, atomic absorption, flurescence X.
- the mass content of dialkyldithiocarbamate compositions according to the invention is between 0.3 and 2%, preferably between 0.5 and 1.7%, preferably between 0.7 and 1.5%, preferably between 0.8 and and 1.2%, typically 1%.
- the Mo / [graphite] ratio between the molybdenum content, in ppm, and the mass percentage of graphite in said compositions is between 1000 and 4000, preferably between 1500 and 3500, preferably between 2000 and 3000, preferably between 2500 and 2900.
- This Mo / [graphite] ratio allows an optimization of the extreme pressure properties for a given quantity of MoDTC.
- the grease compositions according to the invention contain graphite, in any form that can be incorporated in fats.
- the graphite employed in the compositions according to the invention may be a powder of micrometric size, with particle sizes of between approximately 1 and 15 ⁇ m, and for example a size distribution characterized by a diameter D 50 of between 3 and 8 microns, preferably between 5 and 7 microns.
- the mass content of graphite compositions according to the invention is between 0.5 and 3%, preferably between 0.7 and 2%, preferably between 0.8 and 1.5%, preferably between 0.9 and 1.2 %.
- the greases according to the invention optionally contain sulfur-phosphorus anti wear and extreme pressure additives commonly used in the formulation of greases and lubricants. These are for example and not limited to thiophosphoric acid, thiophosphorous acid, esters of these acids, their salts, and dithiophosphates, preferably dithiophosphates, in particular zinc dithiophosphates (DTPZn).
- Zinc dithiophosphates of formula (III) are particularly preferred: or R 1 , R 2 , R 3 and R 4 are, independently of each other, linear or branched alkyl groups comprising from 1 to 24, preferably from 3 to 14 carbon atoms or optionally substituted aryl groups containing from 6 to 30 preferably 8 to 18 carbon atoms.
- These different compounds can be used alone or as a mixture in the grease compositions according to the invention.
- Their weight% is preferably between 0.5 and 5% by weight, preferably between 0.7 and 2% by weight, or between 0.8 and 1.5% by weight relative to the total weight of the composition.
- the lubricating compositions according to the present invention may also contain phosphorus anti-wear and extreme pressure additives, such as, for example, alkyl phosphates or alkyl phosphonates, phosphoric acid, phopsphorous acid, mono, di and triesters of phosphorous acid and phosphoric acid, and their salts.
- phosphorus anti-wear and extreme pressure additives such as, for example, alkyl phosphates or alkyl phosphonates, phosphoric acid, phopsphorous acid, mono, di and triesters of phosphorous acid and phosphoric acid, and their salts.
- the lubricating compositions according to the present invention may also contain sulfurous antiwear and extreme pressure additives, for example dithiocarbamates, thiadiazoles and benzothiazoles, sulfurized olefins.
- sulfurous antiwear and extreme pressure additives for example dithiocarbamates, thiadiazoles and benzothiazoles, sulfurized olefins.
- the greases according to the invention may also contain any type of additive adapted to their use, for example antioxidants, such as amines or phenolics, antirust which may be oxygenated compounds such as esters, for example sorbitan monoleate , oxidized waxes, copper passivants ...
- antioxidants such as amines or phenolics
- antirust which may be oxygenated compounds such as esters, for example sorbitan monoleate , oxidized waxes, copper passivants ...
- the greases according to the invention may also contain polymers, for example polyolefins, polyisobutene (PIB), polyethylenes, polypropylene, heavy PAOs, copolymer olefins (OCP), for example hydrogenated diene-styrene, polymethacrylates (PMA), at levels generally between 1 and 35%.
- polymers for example polyolefins, polyisobutene (PIB), polyethylenes, polypropylene, heavy PAOs, copolymer olefins (OCP), for example hydrogenated diene-styrene, polymethacrylates (PMA), at levels generally between 1 and 35%.
- These polymers are used to improve the cohesiveness of the greases, which are thus more resistant to centrifugation.
- These polymers also lead to a better adhesiveness (especially PIB) of the grease to the surfaces, and increase the viscosity of the base oil fraction, thus the thickness of the oil film between the friction parts.
- the greases according to the invention are preferably manufactured by forming the metal soap in situ.
- One or more fatty acids are dissolved in a fraction of the base oil or base oil mixture at room temperature. This fraction is generally of the order of 50% of the total amount of oil contained in the final fat.
- the fatty acids can be long acids, comprising from 14 to 28 carbon atoms, to form a simple soap, optionally combined with short fatty acids, comprising from 6 to 12 carbon atoms, to form complex soaps.
- the compounds containing aluminum, preferably of the aluminum trimer type as described above, are added at a temperature of approximately 60 to 80.degree.
- the reaction of the fatty acids with the aluminum-containing compound (s) is allowed to proceed by heating to about 200 ° C.
- the grease is then cooled, in particular by the remaining fraction of base oil.
- the additives are then incorporated at about 80 ° C. Kneading is then carried out for a time sufficient to obtain a homogeneous fat composition.
- the consistency of a grease measures its hardness or fluidity at rest. It is quantified by the depth of penetration of a cone of given dimensions and mass. The fat is previously subjected to mixing. The conditions for measuring the consistency of a grease are defined by ASTM D 217.
- the fats are divided into 9 classes or 9 NLGI grades (National Lubricating Grease Institute) commonly used in the field of fats. These grades are shown in the table below.
- the greases according to the invention are preferably greases with a consistency of between 265 and 430, preferably between 310 and 430, and preferably between 265 and 340 tenths of a millimeter according to ASTM D217.
- they are NLGI grade 00, 0, 1 or 2, that is to say that their consistency is respectively between 400 and 430, or 355 and 385, or 310 and 340, or 265 and 295 tenths of a millimeter according to ASTM D217.
- Greases for open gears should adhere to the surfaces, but should not be too thick because they are applied by splashing the gear into a pan or spraying.
- the grades 0.00, or 1 will therefore be preferred, that is to say the greases of consistency respectively between 400 and 430, or 355 and 385, or 310 and 340 tenths of a millimeter according to ASTM D217.
- Fat compositions were prepared with a grease foot prepared from mineral base oil, and a complex aluminum soap obtained by reaction of benzoic acid, glycerol tri stearate (stearin), and a source of aluminum (aluminum trimer of formula (I) above).
- the base oil represents 82.50% by weight of the fat foot, and the aluminum soap complex 17.50% by weight. These fats are grade 2 according to the NLGI classification.
- This fat foot is used in a commercial grease comprising 2.5% MoS 2 , and various additives: an anti-wear additive (DTPZn), an extreme pressure and an anti-rust, which is taken as reference (reference 1).
- DTPZn anti-wear additive
- DTPZn extreme pressure
- anti-rust an anti-rust additive
- Table 1 groups together the compositions and the performances of fats A to E compared to reference 1.
- the greases D and E according to the invention have significantly improved pressure properties (EP) compared to the reference, and a much lower molybdenum content.
- Grease A which does not contain molybdenum, shows no improvement in the extreme pressure properties.
- Fats B and C show a slight improvement in the EP properties (lower than that observed with the D and E greases), but their molybdenum content remains very high.
- Fat compositions were prepared with a fat foot prepared from mineral base oil, and a single lithium soap obtained by reaction of 12-hydroxystearic acid and lithium hydroxide (LiOH, H 2 O) L base oil represents 90.00% by weight of the foot of fat, and the simple lithium soap 10.00% by weight. These fats are grade 2 according to the NLGI classification.
- This foot of fat is used in the composition of a grease taken as reference (reference 2) further comprising 1% MoS 2 , and various additives: an antiwear additive (DTPZn), an extreme pressure, and an anti-rust, which is taken as reference (reference 2).
- DTPZn antiwear additive
- DTPZn extreme pressure
- anti-rust anti-rust
- the fat compositions F and G were prepared with the same fat base and the same additivation as the reference fat 2, but the MoS 2 was replaced by graphite and MoDTC (identical to those of Example 1). .
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Lubricants (AREA)
- General Details Of Gearings (AREA)
Description
La présente invention est relative à des compositions de graisse, en particulier utilisables dans les applications industrielles ou travaux public, nécessitant une très bonne résistance aux fortes charges et aux chocs.The present invention relates to grease compositions, particularly used in industrial applications or public works, requiring very good resistance to heavy loads and shocks.
Il existe de nombreuses applications où les lubrifiants liquides ne conviennent pas parce qu'ils « dérivent » par rapport au point de graissage. Il s'agit en particulier des paliers à roulement et à glissement, des engrenages ouverts, des câbles métalliques et des entraînements par chaîne, et plus généralement des applications ne comportant pas de système d'étanchéité.There are many applications where liquid lubricants are unsuitable because they "drift" relative to the lubrication point. These are in particular rolling and sliding bearings, open gears, wire ropes and chain drives, and more generally applications that do not include a sealing system.
Pour ces applications, on utilise des graisses lubrifiantes, qui sont des substances solides ou semi fluides résultant de la dispersion d'un épaississant dans un lubrifiant liquide, intégrant des additifs qui leur confèrent des propriétés particulières.For these applications, lubricating greases are used which are solid or semi-fluid substances resulting from the dispersion of a thickener in a liquid lubricant, incorporating additives which give them particular properties.
La très large majorité des graisses lubrifiantes est préparée avec des épaississants de type sels métalliques d'acides gras. On dissout l'acide gras dans l'huile de base à une température relativement élevée, et on ajoute ensuite l'hydroxyde de métal approprié. Après avoir fait évaporer par cuisson l'eau qui se forme lors de la réaction, on refroidit pendant un laps de temps défini, pour former le réseau de savon.The vast majority of lubricating greases are prepared with thickeners such as metal salts of fatty acids. The fatty acid is dissolved in the base oil at a relatively high temperature, and then the appropriate metal hydroxide is added. After having evaporated by cooking the water which forms during the reaction, it is cooled for a definite period of time to form the soap network.
Des hydroxydes de Lithium, Sodium, Calcium, Baryum, Titane ou Aluminium, ou certains trimères d'aluminium, conviennent par exemple comme composés métalliques pour la fabrication de la graisse. Les acides gras à chaîne longue, de l'ordre de C14 à C28, principalement C18, proviennent généralement d'huiles végétales (huile de ricin par exemple), ou animales (par exemple suif). Ils peuvent être hydrogénés. Le dérivé le plus connu est l'acide 12 hydroxystéarique provenant de l'acide ricinoléique.Hydroxides of Lithium, Sodium, Calcium, Barium, Titanium or Aluminum, or certain aluminum trimers, are suitable for example as metal compounds for the manufacture of grease. Long-chain fatty acids, of the order of C14 to C28, mainly C18, generally come from vegetable oils (castor oil for example) or animal oils (for example tallow). They can be hydrogenated. The best known derivative is 12-hydroxystearic acid from ricinoleic acid.
On peut également utiliser, en combinaison avec les acides gras à longue chaîne, des acides à chaîne courte, comprenant typiquement entre 6 et 12 atomes de carbone, comme par exemple l'acide azélaique, l'acide benzoïque. Il se forme alors des graisses dites complexes.It is also possible to use, in combination with the long chain fatty acids, short-chain acids, typically comprising between 6 and 12 carbon atoms, for example azelaic acid or benzoic acid. Complex fats are then formed.
Les savons métalliques forment une structure fibreuse, sauf Les savons d'aluminium, qui présentent, eux, une structure de gel sphérique.Metallic soaps form a fibrous structure, except for aluminum soaps, which have a spherical gel structure.
D'autres épaississants inorganiques comme, par exemple, la bentonite, le gel de silice peuvent être utilisés. On trouve également parmi les épaississants des polycarbamides (polyurées).Other inorganic thickeners such as, for example, bentonite, silica gel can be used. Polycarbamides (polyureas) are also found in the thickeners.
Pour les applications où la graisse se trouve dans une enceinte non confinée (par exemple engrenages ouverts de cimenterie...), les graisses épaissies aux savons métalliques, et en particulier aux savons métalliques d'aluminium simples ou complexes sont bien supérieures aux autres graisses.For applications where the grease is in an unconfined enclosure (for example open cement gears, etc.), thickened greases with metallic soaps, and in particular with simple or complex aluminum metal soaps, are much better than other greases. .
En effet, les graisses épaissies aux polyurées n'ont pas une stabilité mécanique suffisante, notamment en raison de leur caractère thixotrope, qui les conduit à se déstructurer sous contraintes mécaniques.Indeed, polyurea thickened greases do not have sufficient mechanical stability, especially because of their thixotropic nature, which leads them to destructure under mechanical stresses.
Les épaississants inorganiques présentent également des problèmes de tenue mécanique et de résistance à l'eau, ce qui est préjudiciable dans les systèmes ouverts.Inorganic thickeners also have problems with mechanical strength and water resistance, which is detrimental in open systems.
Les savons métalliques présentent, quant à eux une très bonne tenue mécanique. En particulier, les graisses épaissies aux savons d'aluminium simple ou complexe présentent une très bonne tenue mécanique, sont très résistantes à l'eau (en particulier les graisses d'aluminium complexe), et présentent une très bonne adhésivité aux surfaces métalliques.The metal soaps have, for their part, a very good mechanical strength. In particular, greases thickened with simple or complex aluminum soaps have a very good mechanical strength, are very resistant to water (in particular complex aluminum greases), and have a very good adhesiveness to metal surfaces.
Le brevet
La demande
La demande
Des graisses épaissies aux savons d'aluminium complexe, et comprenant des additifs antiusure, extrême pression, ainsi qu'un modificateur de frottement, le bisulfure de molybdène (MoS2), sont commercialisées sous le nom de COPAL MS 2 pour des applications sur des engrenages ouverts en industrie lourde tels que les cimenteries, les sucreries (broyeurs, harnais de commandes de four, couronnes d'orientation), ou pour les engins de travaux publics. La présence de MoS2 garantit une bonne lubrification même en cas de surchauffe accidentelle et évite tout collage ou grippage des organes lubrifiés.Thickened greases with complex aluminum soaps, and including antiwear, extreme pressure additives, as well as a friction modifier, molybdenum disulfide (MoS 2 ), are marketed under the name of COPAL MS 2 for applications on open gears in heavy industry such as cement plants, sugar mills (grinders, furnace control harnesses, slewing rings), or for public works machinery. The presence of MoS 2 guarantees good lubrication even in case of accidental overheating and prevents any sticking or seizing of lubricated components.
Toutefois, ces graisses ont une teneur élevée en molybdène (Mo), qu'il serait intéressant de réduire pour des raisons environnementales, et des propriétés extrême pression qui pourraient être améliorées, notamment pour supporter les chocs et les à coups, par exemple dans les broyeurs et les engins de travaux publics.However, these fats have a high content of molybdenum (Mo), which it would be advantageous to reduce for environmental reasons, and extreme pressure properties which could be improved, in particular to withstand shocks and knocks, for example in the crushers and public works machinery.
Les graisses peuvent contenir divers lubrifiants solides, connus pour leurs propriétés de friction et leurs propriétés anti usure, tels que par exemple du bisulfure de molybdène ou de tungstène, le graphite ou le polytetrafluoroethylene (PTFE).The greases may contain various solid lubricants known for their frictional and anti-wear properties, such as, for example, molybdenum or tungsten disulfide, graphite or polytetrafluoroethylene (PTFE).
La demande
Cette demande ne concerne pas le domaine des graisses pour systèmes ouverts, en industrie ou dans les travaux publics, et ne décrit pas de graisses épaissies aux savons d'Aluminium simples ou complexes. Le problème est de produire des graisses pour joints homocinétiques d'automobiles résistant à haute température, et ayant une durée de vie, un pouvoir lubrifiant, et une résistance sous charge permanente améliorée. Aucune mention n'est faite de l'amélioration des propriétés extrême pression.This application does not concern the field of greases for open systems, in industry or in public works, and does not describe thickened greases to simple or complex aluminum soaps. The problem is to produce high temperature resistant constant velocity automotive grease greases with improved service life, lubricity, and permanent load resistance. No mention is made of the improvement of the extreme pressure properties.
Le document
La publication
De manière surprenante, la demanderesse a constaté que des graisses épaissies aux savons d'aluminium, et comprenant, à titre de modificateur de friction, un dithiocarbamate de molybdène combiné à du graphite, présentaient des propriétés extrême pression améliorées ; Les compositions selon l'invention peuvent présenter ces propriétés améliorées avec une teneur en molybdène réduite.Surprisingly, the Applicant has found that thickened greases with aluminum soaps, and comprising, as a friction modifier, a molybdenum dithiocarbamate combined with graphite, have improved extreme pressure properties; The compositions according to the invention can exhibit these improved properties with a reduced molybdenum content.
La présente invention est relative à des compositions de graisse comprenant :
- (a) Une ou plusieurs huiles de base d'origine minérale, synthétique ou naturelle,
- (b) Un épaississant composé majoritairement d'un ou plusieurs savons d'aluminium simples ou complexes,
- (c) Un ou plusieurs dithiocarbamates de molybdène,
- (d) Du graphite,
dont la teneur en molybdène est comprise entre 500 et 5000 ppm,
dont la teneur massique en graphite est comprise entre 0,5 et 3%.The present invention relates to fat compositions comprising:
- (a) One or more base oils of mineral, synthetic or natural origin,
- (b) A thickener composed mainly of one or more simple or complex aluminum soaps,
- (c) One or more molybdenum dithiocarbamates,
- (d) graphite,
whose molybdenum content is between 500 and 5000 ppm,
whose mass content in graphite is between 0.5 and 3%.
Préférentiellement, les compositions selon l'invention comprennent, à titre d'huiles de base (a), une ou plusieurs huiles de base minérales, seules ou en mélange, et optionnellement une ou plusieurs huiles de base synthétiques.Preferably, the compositions according to the invention comprise, as base oils (a), one or more mineral base oils, alone or as a mixture, and optionally one or more synthetic base oils.
Selon un mode de réalisation, les compositions selon l'invention comprennent au moins un savon d'aluminium complexe à titre d'épaississant (b).According to one embodiment, the compositions according to the invention comprise at least one complex aluminum soap as thickener (b).
Dans les compositions selon l'invention, le ou les savon(s) d'aluminium, simple(s) ou complexe(s), constituent au moins 80 % en poids de l'épaississant (b) dans lesdites compositions. In the compositions according to the invention, the aluminum soap (s), simple (s) or complex (s), constitute at least 80% by weight of the thickener (b) in said compositions.
Selon un mode de réalisation, les compositions de graisse selon l'invention comprennent en outre un ou plusieurs additifs choisis parmi les additifs antiusure et/ou extrême pression, préférentiellement phosphosoufrés, préférentiellement les dithiophosphates.According to one embodiment, the grease compositions according to the invention further comprise one or more additives chosen from antiwear and / or extreme pressure additives, preferably phosphosulfides, preferentially dithiophosphates.
Selon un mode préféré, les compositions selon l'une des revendications 1 à 5 comprenant en outre un ou plusieurs polymères, préférentiellement choisis parmi les polyisobutènes.According to a preferred embodiment, the compositions according to one of claims 1 to 5 further comprising one or more polymers, preferably chosen from polyisobutenes.
Dans les compositions selon l'invention, la teneur en molybdène est comprise entre 500 et 5000 ppm, préférentiellement entre 1000 et 4800 ppm. In the compositions according to the invention, the molybdenum content is between 500 and 5000 ppm, preferably between 1000 and 4800 ppm.
Dans les compositions selon l'invention, la teneur massique en graphite est comprise entre 0,5 et 3%, préférentiellement entre 0,7 et 2%In the compositions according to the invention, the mass content of graphite is between 0.5 and 3%, preferably between 0.7 and 2%.
La présente invention est également relative à l'utilisation d'une composition de graisse telle que décrite ci-dessus pour la lubrification des systèmes ouverts, préférentiellement les engrenages ouverts, les câbles métalliques, les entraînements par chaîne.The present invention also relates to the use of a grease composition as described above for the lubrication of systems open, preferably open gears, wire ropes, chain drives.
Préférentiellement, cette utilisation est faite dans le domaine de l'industrie, préférentiellement l'industrie cimentière, sucrière, ou sidérurgique, ou dans le domaine des travaux publics.Preferentially, this use is made in the field of industry, preferably the cement industry, sugar, or steel, or in the field of public works.
La présente invention est également relative à l'utilisation d'une composition additive comprenant du dithiocarbamate de molybdène et du graphite pour augmenter la charge de soudure, mesurée selon la norme DIN 51350/4, d'une graisse épaissie aux savons d'aluminium simples ou complexes.The present invention also relates to the use of an additive composition comprising molybdenum dithiocarbamate and graphite to increase the welding load, measured according to DIN 51350/4, of a thickened grease with simple aluminum soaps or complex.
Enfin, la présente invention est également relative à un système ouvert, préférentiellement engrenage ouvert, câble métallique, entraînement par chaîne, comprenant une composition de graisse telle que décrite ci dessus.Finally, the present invention also relates to an open system, preferably open gear, wire rope, chain drive, comprising a grease composition as described above.
La ou les autres huiles de base utilisées dans les compositions 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 (American Petroleum Institute).The other base oil (s) used in the compositions according to the present invention may be oils of mineral or synthetic origin of groups I to V according to the classes defined in the API classification (American Petroleum Institute).
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, desalphating, solvent dewaxing, hydrotreatment, hydrocracking and hydroisomerization, hydrofinishing.
Les huiles de bases des compositions de graisses selon la présente invention peuvent également être des huiles synthétiques, tels certains esters, silicones, glycols, polybutène, polyalphaoléfines (PAO), alkylbenzene, alkylnaphtalene.The base oils of the grease compositions according to the present invention can also be synthetic oils, such as certain esters, silicones, glycols, polybutene, polyalphaolefins (PAO), alkylbenzene, alkylnaphthalene.
Les huiles de bases peuvent également être des huiles d'origine naturelle, par exemple des esters d'alcool et d'acides carboxyliques, pouvant être obtenus à partir de ressources naturelles telles que l'huile de tournesol, de colza, de palme, de soja....The base oils may also be oils of natural origin, for example esters of alcohol and carboxylic acids, obtainable from natural resources such as sunflower oil, rapeseed oil, palm oil, soy....
Selon un mode de réalisation, les compositions de graisse selon l'invention contiennent un mélange d'huiles minérales, par exemple des huiles minérales paraffiniques et des huiles minérales naphténiques, à titre d'huiles de base (a).According to one embodiment, the grease compositions according to the invention contain a mixture of mineral oils, for example paraffinic mineral oils and naphthenic mineral oils, as base oils (a).
Selon un autre mode de réalisation, elles contiennent un mélange d'huile(s) minérale(s), par exemple des huiles minérales paraffiniques et des huiles minérales naphténiques, et d'huiles synthétiques, par exemple polyalphaoléfines.According to another embodiment, they contain a mixture of mineral oil (s), for example paraffinic mineral oils and naphthenic mineral oils, and synthetic oils, for example polyalphaolefins.
Le mélange d'huiles de bases (a) est calé de façon à ce que sa viscosité à 40°C selon la norme ASTM D 445 soit comprise entre 100 et 500 cSt, préférentiellement entre 110 et 300 cSt, préférentiellement entre 150 et 250 cSt.The base oil mixture (a) is set so that its viscosity at 40 ° C. according to ASTM D 445 is between 100 and 500 cSt, preferably between 110 and 300 cSt, preferably between 150 and 250 cSt. .
Les graisses selon la présente invention sont épaissies aux savons d'aluminium, simples ou complexes, qui présentent des propriétés mécaniques et une adhésivité aux surfaces supérieures, ainsi qu'une excellente résistance à l'eau.The greases according to the present invention are thickened to aluminum soaps, simple or complex, which have mechanical properties and adhesiveness to the upper surfaces, as well as excellent water resistance.
Les savons d'aluminium et d'acides gras peuvent êtres préparés séparément, ou in situ lors de la fabrication de la graisse (dans ce dernier cas, on dissout le ou les acides gras dans l'huile de base, puis on ajoute le composé métallique approprié).The aluminum and fatty acid soaps can be prepared separately, or in situ during the manufacture of the fat (in the latter case, the fatty acid (s) is dissolved in the base oil, and then the compound is added. appropriate metal).
Les savons d'aluminium simples sont par exemple préparés à partir d'hydroxyde d'aluminium Al(OH)3 et d'un ou plusieurs acides gras à chaîne longue, comprenant typiquement de 10 à 28 atomes de carbone , saturés ou insaturés, par exemple l'acide stéarique.The simple aluminum soaps are for example prepared from aluminum hydroxide Al (OH) 3 and one or more long-chain fatty acids, typically comprising from 10 to 28 carbon atoms, saturated or unsaturated, by example stearic acid.
Les savons d'aluminium complexes sont par exemples préparés à partir d'acide stéarique, d'acide benzoique, et de trimères d'aluminium répondant à la formule (I) :
Les savons d'aluminium complexes présentent, par rapport aux savons simples, l'avantage d'une meilleure tenue à haute température.The complex aluminum soaps have, compared to simple soaps, the advantage of better resistance to high temperature.
Les savons d'aluminium sont préférentiellement employés à des teneurs de l'ordre de 5 à 30 % en poids, préférentiellement de 10 à 25 % en poids, préférentiellement de 105 à 20 % en poids , typiquement 12 % en poids dans les graisses selon l'invention. Dans les compositions selon l'invention, la quantité de savon(s) métallique(s) est généralement ajustée de manière à obtenir des graisses de grade 00, de grade 0, de grade 1 ou de grade 2 selon la classification NLGI.The aluminum soaps are preferably used at levels of the order of 5 to 30% by weight, preferably 10 to 25% by weight, preferably from 105 to 20% by weight, typically 12% by weight in the greases. the invention. In the compositions according to the invention, the amount of metallic soap (es) is generally adjusted so as to obtain greases of grade 00, grade 0, grade 1 or grade 2 according to the NLGI classification.
Les graisses selon l'invention contiennent majoritairement des savons d'aluminium, simples ou complexes, à titre d'épaississant. On entend par là que ces savons représentent ensemble le plus fort pourcentage en poids dans les graisses selon l'invention, comparé au pourcentage en poids des autres matières épaississantes.The greases according to the invention mainly contain aluminum soaps, simple or complex, as thickeners. This means that these Soaps together represent the highest percentage by weight in the greases according to the invention, compared to the percentage by weight of other thickening materials.
La quantité du ou des savons d'aluminium, simples ou complexes, constitue au moins 80 % en poids par rapport au poids total de matières épaississantes, dans les compositions de graisse selon l'invention. The amount of aluminum soap (s), simple or complex, constitutes at least 80% by weight, based on the total weight of thickening materials, in the grease compositions according to the invention.
Selon un mode de réalisation, les graisses selon l'invention peuvent contenir comme épaississant majoritaire des savons métalliques d'acides gras simples ou complexes, et de moindres quantités d'autres épaississants, tels que d'autres savons métalliques, simples ou complexes, des polyurées, ou des épaississants inorganiques, type bentonite ou alumino silicates.According to one embodiment, the greases according to the invention can contain, as the major thickener, metal soap of simple or complex fatty acids, and smaller amounts of other thickeners, such as other metallic soaps, simple or complex, polyureas, or inorganic thickeners, type bentonite or alumino silicates.
Préférentiellement, les graisses selon l'invention sont exemptes d'épaississants de type polyurées, qui sont plus compliqués techniquement à fabriquer, en particulier parce que les composants entrant dans leur fabrication, telles que les isocyanates et les amines, sont très toxiques et peu stables au stockage.Preferably, the greases according to the invention are free of polyurea thickeners, which are more technically complicated to manufacture, in particular because the components used in their manufacture, such as isocyanates and amines, are very toxic and unstable. in storage.
Encore plus préférentiellement, les graisses selon l'invention contiennent exclusivement des savons métalliques d'aluminium simples ou complexes à titre d'épaississant.Even more preferentially, the greases according to the invention exclusively contain simple or complex aluminum metal soaps as thickeners.
Les compositions de graisse selon l'invention contiennent du graphite et du dithiocarbamate de molybdène. Il a été constaté, de façon surprenante, et alors même que le graphite est connu pour sa faible résistance sous forte charge, que cette combinaison permet d'obtenir des graisses épaissies aux savons d'aluminium ayant de très bonnes propriétés extrême pression, avec un taux réduit de molybdène.The grease compositions according to the invention contain graphite and molybdenum dithiocarbamate. It has surprisingly been found, and even though graphite is known for its low resistance under heavy load, that this combination makes it possible to obtain thickened greases with aluminum soaps having very good extreme pressure properties, with reduced rate of molybdenum.
Il n'est pas souhaitable de supprimer totalement les composés au molybdène, car les graisses épaissies aux savons d'aluminium qui n'en contiennent pas, ou peu, ne présentent aucune amélioration des propriétés extrême pression. Par exemple, le graphite est connu pour présenter des problèmes de résistance sous forte charge, et une graisse ne contenant que du graphite, a des propriétés extrême pression médiocres.It is not desirable to completely remove the molybdenum compounds because the thickened greases of aluminum soaps that contain no or little of them show no improvement in the extreme pressure properties. For example, graphite is known to have resistance problems under heavy load, and a grease containing only graphite, has poor extreme pressure properties.
Par ailleurs, les graisses ne contenant que du dithiocarbamate de molybdène comme additifs ne garantissent pas une protection suffisante des pièces car le MoDTC nécessite une certaine température d'activation pour être efficace, et il est généralement utilisé en combinaison avec d'autres additifs, notamment phosphosoufrés. Les graisses épaissies aux savons d'aluminium (complexes) ne contenant que du MoDTC comme additif ont des performances extrême pression médiocres.Furthermore, greases containing only molybdenum dithiocarbamate as additives do not guarantee sufficient protection of the parts because the MoDTC requires a certain activation temperature to be effective, and it is generally used in combination with other additives, in particular phosphorosulphur. Fats thickened with (complex) aluminum soaps containing only MoDTC as an additive have poor extreme pressure performance.
Les compositions selon l'invention contiennent des dithiocarbamates de molybdène, additifs modificateurs de friction biens connus de l'homme du métier.The compositions according to the invention contain molybdenum dithiocarbamates, friction modifying additives well known to those skilled in the art.
Ces modificateurs de frottement organométalliques dithiocarbamate de molybdène peuvent par exemple être des dialkyldithiocarbamates de molybdène répondant à la formule (II) :
La quantité de MoDTC des compositions selon l'invention est ajustée de manière à ce que leur teneur en molybdène soit comprise entre 500 et 5000, préférentiellement entre 1000 et 4800 ppm, préférentiellement entre 1500 et 4500 ppm, préférentiellement entre 2000 et 4000, préférentiellement entre 2500 et 3000 ppm. Une trop faible teneur en MoDTC conduit à des propriétés extrême pression médiocre, une trop forte teneur est préjudicaible à l'environnement.The amount of MoDTC of the compositions according to the invention is adjusted so that their molybdenum content is between 500 and 5000, preferably between 1000 and 4800 ppm, preferably between 1500 and 4500 ppm, preferably between 2000 and 4000, preferentially between 2500 and 3000 ppm. Too low MoDTC content leads to poor extreme pressure properties, too high a content is detrimental to the environment.
Cette teneur peut être mesurée selon les techniques usuelles, plasma, absorption atomique, flurescence X.This content can be measured according to the usual techniques, plasma, atomic absorption, flurescence X.
Typiquement, la teneur massique en dialkyldithiocarbamate des compositions selon l'invention est comprise entre 0,3 et 2%, préférentiellement entre 0,5 et 1,7%, préférentiellement entre 0,7 et 1,5%, préférentiellement entre 0,8 et 1,2%, typiquement égale à 1%.Typically, the mass content of dialkyldithiocarbamate compositions according to the invention is between 0.3 and 2%, preferably between 0.5 and 1.7%, preferably between 0.7 and 1.5%, preferably between 0.8 and and 1.2%, typically 1%.
Selon un mode préféré, dans les compositions selon l'invention, le rapport Mo/[graphite] entre la teneur en molybdène, en ppm, et le pourcentage massique de graphite dans lesdites compositions, est compris entre 1000 et 4000, préférentiellement entre 1500 et 3500, préférentiellement entre 2000 et 3000, préférentiellement entre 2500 et 2900.According to a preferred embodiment, in the compositions according to the invention, the Mo / [graphite] ratio between the molybdenum content, in ppm, and the mass percentage of graphite in said compositions, is between 1000 and 4000, preferably between 1500 and 3500, preferably between 2000 and 3000, preferably between 2500 and 2900.
Ce rapport Mo/[graphite] permet une optimisation des propriétés extrême pression pour une quantité donnée de MoDTC.This Mo / [graphite] ratio allows an optimization of the extreme pressure properties for a given quantity of MoDTC.
Les compositions de graisse selon l'invention contiennent du graphite, sous toute forme incorporable dans les graisses. Par exemple, le graphite employé dans les compositions selon l'invention peut être une poudre de taille micrométrique, avec des tailles de particules comprises environ entre 1 et 15 µm, et par exemple une distribution de taille caractérisée par un diamètre D50 compris entre 3 et 8 µm, préférentiellement entre 5 et 7 µm.The grease compositions according to the invention contain graphite, in any form that can be incorporated in fats. For example, the graphite employed in the compositions according to the invention may be a powder of micrometric size, with particle sizes of between approximately 1 and 15 μm, and for example a size distribution characterized by a diameter D 50 of between 3 and 8 microns, preferably between 5 and 7 microns.
La teneur massique en graphite des compositions selon l'invention est comprise entre 0,5 et 3%, préférentiellement entre 0,7 et 2%, préférentiellement entre 0,8 et 1,5%, préférentiellement entre 0,9 et 1,2%.The mass content of graphite compositions according to the invention is between 0.5 and 3%, preferably between 0.7 and 2%, preferably between 0.8 and 1.5%, preferably between 0.9 and 1.2 %.
Les graisses selon l'invention contiennent optionnellement des additifs anti usure et extrême pression phospho soufrés utilisés couramment dans la formulation de graisses et de lubrifiants. Ce sont par exemple et non limitativement l'acide thiophosphorique, l'acide thiophosphoreux, les esters de ces acides, leurs sels, et les dithiophosphates, préférentiellement les dithiophosphates, en particulier les dithiophosphates de Zinc (DTPZn).The greases according to the invention optionally contain sulfur-phosphorus anti wear and extreme pressure additives commonly used in the formulation of greases and lubricants. These are for example and not limited to thiophosphoric acid, thiophosphorous acid, esters of these acids, their salts, and dithiophosphates, preferably dithiophosphates, in particular zinc dithiophosphates (DTPZn).
On préférera en particulier les dithiophosphates de Zinc de formule (III) :
R1, R2, R3, R4 sont, indépendamment les uns des autres, des groupements alkyl linéaires ou ramifiés comprenant de 1 à 24, préférentiellement de 3 à 14 atomes de carbone ou des groupements aryl éventuellement substitués comportant de 6 à 30, préférentiellement de 8 à 18 atomes de carbone.Zinc dithiophosphates of formula (III) are particularly preferred:
R 1 , R 2 , R 3 and R 4 are, independently of each other, linear or branched alkyl groups comprising from 1 to 24, preferably from 3 to 14 carbon atoms or optionally substituted aryl groups containing from 6 to 30 preferably 8 to 18 carbon atoms.
Ces différents composés peuvent être employés seuls ou en mélange dans les compositions de graisse selon l'invention. Leur % massique est préférentiellement compris entre 0,5 et 5% en poids, préférentiellement entre 0,7 et 2% en poids, ou encore entre 0,8 et 1,5% en poids par rapport au poids total de la composition.These different compounds can be used alone or as a mixture in the grease compositions according to the invention. Their weight% is preferably between 0.5 and 5% by weight, preferably between 0.7 and 2% by weight, or between 0.8 and 1.5% by weight relative to the total weight of the composition.
Les compositions lubrifiantes selon la présente invention 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 phopsphoreux, les mono, di et triesters de l'acide phosphoreux et de l'acide phosphorique, et leurs sels.The lubricating compositions according to the present invention may also contain phosphorus anti-wear and extreme pressure additives, such as, for example, alkyl phosphates or alkyl phosphonates, phosphoric acid, phopsphorous acid, mono, di and triesters of phosphorous acid and phosphoric acid, and their salts.
Les compositions lubrifiantes selon la présente invention peuvent également contenir des additifs antiusure et extrême- pression soufrés, par exemple les dithiocarbamates, thiadiazoles et benzothiazoles, les oléfines sulfurisées.The lubricating compositions according to the present invention may also contain sulfurous antiwear and extreme pressure additives, for example dithiocarbamates, thiadiazoles and benzothiazoles, sulfurized olefins.
Les graisses selon l'invention peuvent également contenir tous type d'additifs adaptés à leur utilisation, par exemple des antioxydants, tels que les aminés ou phénoliques, des antirouille qui peuvent être des composés oxygénés tels que les esters, par exemple le monoleate de sorbitan, les cires oxydées, des passivants cuivre...The greases according to the invention may also contain any type of additive adapted to their use, for example antioxidants, such as amines or phenolics, antirust which may be oxygenated compounds such as esters, for example sorbitan monoleate , oxidized waxes, copper passivants ...
Ces différents composés sont généralement présents à des teneurs inférieures à 1%, ou encore à 0,5% en masse dans les graisses.These various compounds are generally present at levels of less than 1%, or else at 0.5% by weight in fats.
Les graisses selon l'invention peuvent également contenir des polymères, par exemple des polyoléfines, polyisobutène (PIB), des polyéthylènes, polypropylène, des PAO lourdes, des oléfines copolymères (OCP) par exemple diène - styrene hydrogéné, des polyméthacrylates (PMA), à des teneurs généralement comprises entre 1 et 35%. Ces polymères sont utilisés pour améliorer la cohésivité des graisses, qui résistent ainsi mieux à la centrifugation. Ces polymères entraînent également une meilleure adhésivité (notamment les PIB) de la graisse aux surfaces, et augmentent la viscosité de la fraction huile de base, donc l'épaisseur du film d'huile entre les pièces en frottement. La quantité incorporée varie en fonction de la masse molaire, de la viscosité, de l'effet recherché. On utilisera par exemple des PIB de masse molaire comprise entre 15 000 et 25 000 dalton à des teneurs comprises entre 1 et 10% en masse, pour augmenter l'adhésivité de la graisse aux surfaces métalliques.The greases according to the invention may also contain polymers, for example polyolefins, polyisobutene (PIB), polyethylenes, polypropylene, heavy PAOs, copolymer olefins (OCP), for example hydrogenated diene-styrene, polymethacrylates (PMA), at levels generally between 1 and 35%. These polymers are used to improve the cohesiveness of the greases, which are thus more resistant to centrifugation. These polymers also lead to a better adhesiveness (especially PIB) of the grease to the surfaces, and increase the viscosity of the base oil fraction, thus the thickness of the oil film between the friction parts. The amount incorporated varies according to the molar mass, the viscosity, the desired effect. For example, molar mass PIBs of between 15,000 and 25,000 daltons at levels of between 1 and 10% by weight will be used to increase the adhesiveness of the grease to metal surfaces.
Les graisses selon l'invention sont préférentiellement fabriquées en formant le savon métallique in situ.The greases according to the invention are preferably manufactured by forming the metal soap in situ.
On dissout ou plusieurs acides gras dans une fraction de l'huile de base ou du mélange d'huile de base à température ambiante. Cette fraction est généralement de l'ordre de 50% de la quantité totale d'huile contenue dans la graisse finale. Les acides gras peuvent être des acides longs, comprenant de 14 à 28 atomes de carbone, pour former un savon simples, éventuellement combinés à des acides gras courts, comprenant de 6 à 12 atomes de carbone, pour former des savons complexes.One or more fatty acids are dissolved in a fraction of the base oil or base oil mixture at room temperature. This fraction is generally of the order of 50% of the total amount of oil contained in the final fat. The fatty acids can be long acids, comprising from 14 to 28 carbon atoms, to form a simple soap, optionally combined with short fatty acids, comprising from 6 to 12 carbon atoms, to form complex soaps.
On ajoute, à une température d'environ 60 à 80°C, les composés contenant l'aluminium, préférentiellement de type trimère d'aluminium tel que décrit plus haut.The compounds containing aluminum, preferably of the aluminum trimer type as described above, are added at a temperature of approximately 60 to 80.degree.
On laisse se dérouler la réaction des acides gras avec le ou les composés contenant l'aluminium, en chauffant à environ 200°C. La graisse est ensuite refroidie, notamment par la fraction restante d'huile de base.The reaction of the fatty acids with the aluminum-containing compound (s) is allowed to proceed by heating to about 200 ° C. The grease is then cooled, in particular by the remaining fraction of base oil.
On incorpore ensuite les additifs à environ 80°C. On malaxage ensuite pendant un temps suffisant pour obtenir une composition de graisse homogène.The additives are then incorporated at about 80 ° C. Kneading is then carried out for a time sufficient to obtain a homogeneous fat composition.
La consistance d'une graisse mesure sa dureté ou sa fluidité au repos. Elle est chiffrée par la profondeur de pénétration d'un cône de dimensions et de masse donnée. La graisse est préalablement soumise à un malaxage. Les conditions de mesure de la consistance d'une graisse sont définies par la norme ASTM D 217.The consistency of a grease measures its hardness or fluidity at rest. It is quantified by the depth of penetration of a cone of given dimensions and mass. The fat is previously subjected to mixing. The conditions for measuring the consistency of a grease are defined by ASTM D 217.
Selon leur consistance, les graisses sont réparties en 9 classes ou 9 grades NLGI (National Lubricating Grease Institute) couramment utilisés dans le domaine des graisses. Ces grades sont indiqués dans le tableau ci-dessous.Depending on their consistency, the fats are divided into 9 classes or 9 NLGI grades (National Lubricating Grease Institute) commonly used in the field of fats. These grades are shown in the table below.
Les graisses selon l'invention sont préférentiellement des graisses de consistance comprise entre et 265 et 430, préférentiellement entre 310 et 430, préférentiellement entre 265 et 340 dixièmes de millimètre selon ASTM D217. Préférentiellement, elles sont de grade NLGI 00, 0, 1 ou 2, c'est-à-dire que leur consistance est respectivement comprise entre 400 et 430, ou 355 et 385, ou 310 et 340, ou 265 et 295 dixièmes de millimètres selon ASTM D217.The greases according to the invention are preferably greases with a consistency of between 265 and 430, preferably between 310 and 430, and preferably between 265 and 340 tenths of a millimeter according to ASTM D217. Preferably, they are NLGI grade 00, 0, 1 or 2, that is to say that their consistency is respectively between 400 and 430, or 355 and 385, or 310 and 340, or 265 and 295 tenths of a millimeter according to ASTM D217.
Les graisses destinées aux engrenages ouverts doivent adhérer aux surfaces, mais ne doivent pas être trop consistantes car elles sont appliquées par barbotage de l'engrenage dans un bac ou par pulvérisation. Les grades 0,00, ou 1 seront donc préférés, c'est-à-dire les graisses de consistance respectivement comprise entre 400 et 430, ou 355 et 385, ou 310 et 340 dixièmes de millimètres selon ASTM D217.
Des compositions de graisses ont été préparées avec un pied de graisse préparé à partir d'huile de base minérale, et d'un savon d'aluminium complexe obtenu par réaction d'acide benzoïque, de tri stéarate de glycérol (stéarine), et d'une source d'aluminium (trimère d'aluminium répondant à la formule (I) ci dessus). L'huile de base représente 82,50 % en poids du pied de graisse, et le savon d'aluminium complexe 17,50% en poids.
Ces graisses sont de grade 2 selon la classification NLGI.Fat compositions were prepared with a grease foot prepared from mineral base oil, and a complex aluminum soap obtained by reaction of benzoic acid, glycerol tri stearate (stearin), and a source of aluminum (aluminum trimer of formula (I) above). The base oil represents 82.50% by weight of the fat foot, and the aluminum soap complex 17.50% by weight.
These fats are grade 2 according to the NLGI classification.
Ce pied de graisse entre dans la composition d'une graisse commerciale comprenant 2,5 % de MoS2, et divers additifs : un additif antiusure (DTPZn), un extrême pression ainsi qu'un anti rouille, qui est prise comme référence (référence 1).This fat foot is used in a commercial grease comprising 2.5% MoS 2 , and various additives: an anti-wear additive (DTPZn), an extreme pressure and an anti-rust, which is taken as reference (reference 1).
Les compositions de graisse ont été préparées avec le même pied de graisse et la même additivation que la graisse de référence commerciale, mais le MoS2 été totalement ou partiellement substitué par d'autres lubrifiants solides :
- Le graphite employé est une poudre micrométrique, de diamètre D50 = 6µm
- Le MoDTC employé est du di-n butyldithiocarbamate de molybdène, contenant 28% en masse de molybdène
- Le MoS2 employé est une poudre micrométrique constituée de particules de taille comprise entre 0,5 et 8µm, de D50 environ 2 µm.
- The graphite used is a micrometric powder, of diameter D50 = 6 μm
- The MoDTC used is di-n-butyldithiocarbamate molybdenum, containing 28% by weight molybdenum
- The MoS 2 used is a micrometric powder consisting of particles having a size of between 0.5 and 8 μm and a D50 of around 2 μm.
Les performances extrême pression de toutes ces graisses ont été mesurées selon la norme DIN 51350/4, en mesurant la charge de soudure dans le test 4 billes EP (mesure de la charge nécessaire à appliquer pour souder entre elles 4 billes disposées selon un arrangement déterminé et entre lesquelles une quantité déterminée de graisse a été introduite).The extreme pressure performance of all these greases was measured according to DIN 51350/4, by measuring the welding load in the test 4 balls EP (measurement of the necessary load to be applied to weld together 4 balls arranged according to a given arrangement and between which a determined amount of fat has been introduced).
Le tableau 1 regroupe les compositions et les performances des graisses A à E comparativement à la référence 1.Table 1 groups together the compositions and the performances of fats A to E compared to reference 1.
Les graisses D et E selon l'invention ont des propriétés extrême pression (EP) significativement améliorées par rapport à la référence, et une teneur en molybdène très inférieure.The greases D and E according to the invention have significantly improved pressure properties (EP) compared to the reference, and a much lower molybdenum content.
La graisse A, qui ne contient pas de molybdène, ne présente aucune amélioration des propriétés extrême pression.Grease A, which does not contain molybdenum, shows no improvement in the extreme pressure properties.
Les graisses B et C montrent une légère amélioration des propriétés EP (inférieure à celle observée avec les graisses D et E), mais leur teneur en molybdène demeure très élevée.Fats B and C show a slight improvement in the EP properties (lower than that observed with the D and E greases), but their molybdenum content remains very high.
Des compositions de graisses ont été préparées avec un pied de graisse préparé à partir d'huile de base minérale, et d'un savon de lithium simple obtenu par réaction d'acide 12-hydroxystéarique et de lithine (LiOH, H2O) L'huile de base représente 90,00 % en poids du pied de graisse, et le savon de lithium simple 10,00% en poids.
Ces graisses sont de grade 2 selon la classification NLGI.Fat compositions were prepared with a fat foot prepared from mineral base oil, and a single lithium soap obtained by reaction of 12-hydroxystearic acid and lithium hydroxide (LiOH, H 2 O) L base oil represents 90.00% by weight of the foot of fat, and the simple lithium soap 10.00% by weight.
These fats are grade 2 according to the NLGI classification.
Ce pied de graisse entre dans la composition d'une graisse prise comme référence (référence 2) comprenant en outre 1 % de MoS2, et divers additifs : un additif antiusure (DTPZn), un extrême pression, ainsi qu'un anti rouille, qui est prise comme référence (référence 2).This foot of fat is used in the composition of a grease taken as reference (reference 2) further comprising 1% MoS 2 , and various additives: an antiwear additive (DTPZn), an extreme pressure, and an anti-rust, which is taken as reference (reference 2).
Les compositions de graisse F et G ont été préparées avec le même pied de graisse et la même additivation que la graisse de référence 2, mais le MoS2 a été remplacé par du graphite et du MoDTC (identiques à ceux de l'exemple 1).The fat compositions F and G were prepared with the same fat base and the same additivation as the reference fat 2, but the MoS 2 was replaced by graphite and MoDTC (identical to those of Example 1). .
Les performances extrême pression de la référence 2 et des graisses F et G ont été mesurées selon la norme DIN 51350/4, en mesurant la charge de soudure dans le test 4 billes EP.
Le tableau 1 regroupe les compositions et les performances des graisse F et G comparativement à la référence 2.The extreme pressure performance of reference 2 and greases F and G were measured according to DIN 51350/4 by measuring the welding load in the 4-ball EP test.
Table 1 groups together the compositions and the performances of the F and G greases compared to the reference 2.
Aucune amélioration des propriétés extrême pression n'est constatée entre la référence 2 et la graisse F ou la graisse G. Dans cet environnement d'épaississant au savon de lithium, la combinaison MoDTC + graphite n'agit pas de la même manière que dans l'environnement d'épaississant à l'aluminium.
Sans vouloir être lié par une quelconque théorie, il semble que la structure de gel sphérique des savons d'aluminium, qui se distingue de la structure fibreuse des autres savons métalliques d'acides gras (notamment au lithium), utilisés comme épaississants, ait une influence sur le mode d'action et les performances des additifs.
Without wishing to be bound by any theory, it seems that the spherical gel structure of aluminum soaps, which is different from the fibrous structure of other metal soaps of fatty acids (especially lithium), used as thickeners, has a influence on the mode of action and the performance of the additives.
Claims (11)
- Grease composition comprising:(a) One or more base oils of mineral, synthetic or natural origin,(b) A thickener composed mainly of one or more simple or complex aluminium soaps,(c) One or more molybdenum dithiocarbamates,(d) Graphite,• wherein the simple or complex aluminium soap(s) constitutes at least 80% by weight of the thickener (b) in said composition,• the molybdenum content of which is comprised between 500 and 5000 ppm,• the content by mass of graphite of which is comprised between 0.5 and 3%.
- Composition according to claim 1 comprising as base oils (a) one or more mineral base oils, alone or in a mixture, and optionally one or more synthetic base oils.
- Composition according to one of claims 1 or 2 comprising at least one complex aluminium soap as thickener (b).
- Grease composition according to one of claims 1 to 3 comprising moreover one or more additives chosen from the anti-wear and/or extreme pressure additives, preferentially containing phosphorus and sulphur, preferentially the dithiophosphates.
- Grease composition according to one of claims 1 to 4 comprising moreover one or more polymers, preferentially chosen from the polyisobutenes.
- Composition according to one of claims 1 to 5 in which the molybdenum content is comprised between 1000 and 4800 ppm.
- Grease composition according to one of claims 1 to 6 where the content by mass of graphite is comprised between 0.7 and 2%.
- Use of a grease composition according to one of claims 1 to 7 for the lubrication of open systems, preferentially open gear sets, metal cables, chain drives.
- Use according to claim 8 in the field of industry, preferentially the cement, sugar or steel industry, or in the field of public works.
- Use of an additive composition comprising molybdenum dithiocarbamate and graphite for increasing the welding load, measured according to the standard DIN 51350/4, of a grease thickened with simple or complex aluminium soaps.
- Open system, preferentially open gear sets, metal cable, chain drive, comprising a grease composition according to one of claims 1 to 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1060442A FR2968670B1 (en) | 2010-12-13 | 2010-12-13 | FAT COMPOSITION |
| PCT/IB2011/055622 WO2012080940A1 (en) | 2010-12-13 | 2011-12-12 | Grease composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2652100A1 EP2652100A1 (en) | 2013-10-23 |
| EP2652100B1 true EP2652100B1 (en) | 2016-05-25 |
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ID=43797602
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP11805229.9A Not-in-force EP2652100B1 (en) | 2010-12-13 | 2011-12-12 | Grease composition |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US20130267447A1 (en) |
| EP (1) | EP2652100B1 (en) |
| JP (1) | JP5873104B2 (en) |
| KR (1) | KR20130130016A (en) |
| CN (1) | CN103339242A (en) |
| AR (1) | AR084244A1 (en) |
| BR (1) | BR112013014825A2 (en) |
| CA (1) | CA2820456C (en) |
| ES (1) | ES2580208T3 (en) |
| FR (1) | FR2968670B1 (en) |
| MX (1) | MX2013006759A (en) |
| WO (1) | WO2012080940A1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2984350B1 (en) | 2011-12-16 | 2015-02-27 | Total Raffinage Marketing | FAT COMPOSITION |
| FR2992655B1 (en) | 2012-06-29 | 2015-07-31 | Total Raffinage Marketing | LUBRICANT COMPOSITION |
| FR3000103B1 (en) | 2012-12-21 | 2015-04-03 | Total Raffinage Marketing | LUBRICATING COMPOSITION BASED ON POLYGLYCEROL ETHER |
| FR3018079B1 (en) | 2014-02-28 | 2017-06-23 | Total Marketing Services | LUBRICATING COMPOSITION BASED ON METALLIC NANOPARTICLES |
| US20150335513A1 (en) * | 2014-05-20 | 2015-11-26 | Jeff Lichthardt | Portable percussive tissue massager |
| CN104087393B (en) * | 2014-07-01 | 2017-04-05 | 欧德力(厦门)汽车环保科技有限公司 | A kind of lubricant grease for brake system of car and preparation method thereof |
| WO2016124653A1 (en) * | 2015-02-06 | 2016-08-11 | Shell Internationale Research Maatschappij B.V. | Grease composition |
| CN105695047A (en) * | 2016-02-25 | 2016-06-22 | 天津高盛钢丝绳有限公司 | Steel wire rope hemp core lubricant formulation |
| FR3074809B1 (en) | 2017-12-11 | 2019-12-13 | Total Marketing Services | GREASE COMPOSITION HAVING IMPROVED ADHESIVITY |
| CN108485769A (en) * | 2018-05-07 | 2018-09-04 | 东莞市蓝鲸化工科技有限公司 | A kind of high temperature resistant luboil fat and preparation method thereof |
| EP4010454B1 (en) * | 2019-09-18 | 2023-10-25 | GKN Driveline International GmbH | A grease composition comprising copper sulfide for constant velocity joints |
| DE102019134330A1 (en) * | 2019-12-13 | 2021-06-17 | Klüber Lubrication München Se & Co. Kg | Use of a grease composition with a high upper service temperature |
| CN114591776A (en) * | 2022-03-14 | 2022-06-07 | 北京市政建设集团有限责任公司 | Sealing grease for shield machine and preparation method thereof |
| CN115161096B (en) * | 2022-06-01 | 2023-05-23 | 中国石油化工股份有限公司 | Aluminum-barium-based lubricating grease composition, and preparation method and application thereof |
| KR102686123B1 (en) * | 2022-08-18 | 2024-07-19 | 주식회사 루브캠코리아 | Lubricating Grease Containing Solid Lubricant |
| CN115340896B (en) * | 2022-08-19 | 2023-05-30 | 杭州得润宝油脂股份有限公司 | Groove drum lubricating grease for elasticizer and preparation method of groove drum lubricating grease |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE506779A (en) | 1951-03-29 | |||
| US3620975A (en) | 1968-07-03 | 1971-11-16 | Sun Oil Co | Mixed complex aluminum soap-clay grease composition |
| JPS4842928B1 (en) * | 1969-05-21 | 1973-12-15 | ||
| IT970178B (en) * | 1972-02-18 | 1974-04-10 | Labofina Sa | GREASES LUBRICANTS |
| CH550241A (en) * | 1972-02-18 | 1974-06-14 | Labofina Sa | LUBRICATING GREASES. |
| US4557842A (en) * | 1983-08-02 | 1985-12-10 | Joseph Ayers, Inc. | Aluminum soap greases |
| JPH07197072A (en) | 1993-12-29 | 1995-08-01 | Showa Shell Sekiyu Kk | Grease composition for constant velocity joints |
| WO1996002615A1 (en) * | 1994-07-15 | 1996-02-01 | Kyodo Yushi Co., Ltd. | Grease composition for constant velocity joints |
| US5670461A (en) | 1994-08-19 | 1997-09-23 | Gkn Automotive Ag | High temperature lubricating grease containing urea compounds |
| JP3954662B2 (en) * | 1995-09-12 | 2007-08-08 | 昭和シェル石油株式会社 | Grease composition for open gear |
| CN1151243C (en) * | 2000-12-01 | 2004-05-26 | 中国石油天然气股份有限公司 | Universal manual transmission oil composition |
| JP2003003186A (en) * | 2001-06-20 | 2003-01-08 | Dow Corning Asia Ltd | POLY-alpha-OLEFIN GREASE COMPOSITION |
| JP2003105367A (en) * | 2001-10-01 | 2003-04-09 | Asahi Denka Kogyo Kk | Lubricating composition |
| JP2004059604A (en) * | 2002-07-24 | 2004-02-26 | Nippon Oil Corp | Grease composition |
| WO2006043566A1 (en) * | 2004-10-18 | 2006-04-27 | Nsk Ltd. | Waterproof grease composition and roller bearing for wheel support |
| CN100443575C (en) * | 2005-11-30 | 2008-12-17 | 中国石油化工股份有限公司 | A kind of protective lubricating grease, its application and preparation method |
| CN100398632C (en) * | 2006-07-05 | 2008-07-02 | 鞍山海华油脂化学有限公司 | Composite aluminum base grease and its preparing method |
| JP2009138055A (en) * | 2007-12-04 | 2009-06-25 | Ntn Corp | Lubricating grease |
| CN101235338B (en) * | 2008-01-30 | 2011-05-11 | 益田润石（北京）化工有限公司 | Open-type gear grease composition |
| US8507421B2 (en) * | 2010-02-02 | 2013-08-13 | Fuchs Lubricants Co. | Lubricating greases and process for their production |
-
2010
- 2010-12-13 FR FR1060442A patent/FR2968670B1/en not_active Expired - Fee Related
-
2011
- 2011-12-12 EP EP11805229.9A patent/EP2652100B1/en not_active Not-in-force
- 2011-12-12 JP JP2013543940A patent/JP5873104B2/en not_active Expired - Fee Related
- 2011-12-12 BR BR112013014825A patent/BR112013014825A2/en not_active Application Discontinuation
- 2011-12-12 WO PCT/IB2011/055622 patent/WO2012080940A1/en not_active Ceased
- 2011-12-12 MX MX2013006759A patent/MX2013006759A/en active IP Right Grant
- 2011-12-12 AR ARP110104631A patent/AR084244A1/en not_active Application Discontinuation
- 2011-12-12 US US13/993,239 patent/US20130267447A1/en not_active Abandoned
- 2011-12-12 CA CA2820456A patent/CA2820456C/en not_active Expired - Fee Related
- 2011-12-12 CN CN2011800655281A patent/CN103339242A/en active Pending
- 2011-12-12 KR KR1020137018024A patent/KR20130130016A/en not_active Ceased
- 2011-12-12 ES ES11805229.9T patent/ES2580208T3/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| BR112013014825A2 (en) | 2016-10-04 |
| CN103339242A (en) | 2013-10-02 |
| ES2580208T3 (en) | 2016-08-22 |
| AR084244A1 (en) | 2013-05-02 |
| MX2013006759A (en) | 2013-08-01 |
| EP2652100A1 (en) | 2013-10-23 |
| FR2968670A1 (en) | 2012-06-15 |
| FR2968670B1 (en) | 2013-01-04 |
| WO2012080940A1 (en) | 2012-06-21 |
| KR20130130016A (en) | 2013-11-29 |
| US20130267447A1 (en) | 2013-10-10 |
| JP2014505127A (en) | 2014-02-27 |
| CA2820456A1 (en) | 2012-06-21 |
| JP5873104B2 (en) | 2016-03-01 |
| CA2820456C (en) | 2018-10-02 |
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