EP0404650B1 - Overbased lubricating oil additives containing a molybdenun complex, process of preparation and compositions containing the same - Google Patents
Overbased lubricating oil additives containing a molybdenun complex, process of preparation and compositions containing the same Download PDFInfo
- Publication number
- EP0404650B1 EP0404650B1 EP90401695A EP90401695A EP0404650B1 EP 0404650 B1 EP0404650 B1 EP 0404650B1 EP 90401695 A EP90401695 A EP 90401695A EP 90401695 A EP90401695 A EP 90401695A EP 0404650 B1 EP0404650 B1 EP 0404650B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- amine
- molybdenum
- additives according
- complex
- additives
- 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.)
- Expired - Lifetime
Links
- 239000000654 additive Substances 0.000 title claims description 57
- 238000000034 method Methods 0.000 title claims description 28
- 239000000203 mixture Substances 0.000 title claims description 27
- 239000010687 lubricating oil Substances 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 82
- 239000011733 molybdenum Substances 0.000 claims description 82
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 80
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 35
- 239000003921 oil Substances 0.000 claims description 32
- 239000003599 detergent Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 150000001412 amines Chemical class 0.000 claims description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims description 22
- 229930195733 hydrocarbon Natural products 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- -1 alkali-metal molybdate Chemical class 0.000 claims description 15
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 13
- 239000000314 lubricant Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 11
- 239000003085 diluting agent Substances 0.000 claims description 11
- 239000012429 reaction media Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000693 micelle Substances 0.000 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 235000010755 mineral Nutrition 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- 239000005078 molybdenum compound Substances 0.000 claims description 7
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 7
- 150000003141 primary amines Chemical class 0.000 claims description 7
- 239000011684 sodium molybdate Substances 0.000 claims description 7
- 235000015393 sodium molybdate Nutrition 0.000 claims description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001246 colloidal dispersion Methods 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 150000004985 diamines Chemical class 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 229920000768 polyamine Polymers 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 150000003335 secondary amines Chemical class 0.000 claims description 5
- KLPPPIIIEMUEGP-UHFFFAOYSA-N 4-dodecylaniline Chemical compound CCCCCCCCCCCCC1=CC=C(N)C=C1 KLPPPIIIEMUEGP-UHFFFAOYSA-N 0.000 claims description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- IMBQZPYQVQWPTP-UHFFFAOYSA-N n-ethylhexan-2-amine Chemical compound CCCCC(C)NCC IMBQZPYQVQWPTP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003873 salicylate salts Chemical class 0.000 claims description 4
- NTWORZKWAKBVFS-UHFFFAOYSA-N 2-methyltridecan-2-amine Chemical compound CCCCCCCCCCCC(C)(C)N NTWORZKWAKBVFS-UHFFFAOYSA-N 0.000 claims description 3
- WXBXQUFGRJEKPL-UHFFFAOYSA-N 2-methylundecan-2-amine Chemical compound CCCCCCCCCC(C)(C)N WXBXQUFGRJEKPL-UHFFFAOYSA-N 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910015686 MoOCl4 Inorganic materials 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- SFPKXFFNQYDGAH-UHFFFAOYSA-N oxomolybdenum;tetrahydrochloride Chemical compound Cl.Cl.Cl.Cl.[Mo]=O SFPKXFFNQYDGAH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 4
- 150000001340 alkali metals Chemical class 0.000 claims 3
- 239000003963 antioxidant agent Substances 0.000 claims 1
- 125000005609 naphthenate group Chemical group 0.000 claims 1
- 125000003595 primary aliphatic amine group Chemical group 0.000 claims 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 claims 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000003513 alkali Substances 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000008096 xylene Substances 0.000 description 12
- 239000011575 calcium Substances 0.000 description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 150000002751 molybdenum Chemical class 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 7
- 150000003871 sulfonates Chemical class 0.000 description 7
- WECIKJKLCDCIMY-UHFFFAOYSA-N 2-chloro-n-(2-cyanoethyl)acetamide Chemical compound ClCC(=O)NCCC#N WECIKJKLCDCIMY-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 210000004534 cecum Anatomy 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 230000005587 bubbling Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000008030 elimination Effects 0.000 description 5
- 238000003379 elimination reaction Methods 0.000 description 5
- 238000010348 incorporation Methods 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- 235000011837 pasties Nutrition 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- AAIUWVOMXTVLRG-UHFFFAOYSA-N 8,8-dimethylnonan-1-amine Chemical compound CC(C)(C)CCCCCCCN AAIUWVOMXTVLRG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241001080024 Telles Species 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- TUFJPPAQOXUHRI-KTKRTIGZSA-N n'-[(z)-octadec-9-enyl]propane-1,3-diamine Chemical compound CCCCCCCC\C=C/CCCCCCCCNCCCN TUFJPPAQOXUHRI-KTKRTIGZSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 3
- IRXPXBIZOBAGTM-UHFFFAOYSA-N 2,3-didodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC(S(O)(=O)=O)=C1CCCCCCCCCCCC IRXPXBIZOBAGTM-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
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- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000005541 phosphonamide group Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000002966 varnish 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
-
- 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/18—Complexes with metals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/09—Complexes with metals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B1/00—Engines characterised by fuel-air mixture compression
- F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
- F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder
Definitions
- This invention relates to overbased additives for lubricating oils containing an organic complex of molybdenum practically insoluble in hydrocarbons.
- Overbased additives are alkali or alkaline earth metal salts of organic acids, overbased by carbonation with carbon dioxide.
- the term overbased is used to designate the excess of alkali or alkaline earth metal over the stoichiometric amount necessary to neutralize the organic acid used.
- the structure of the overbased additives is that of a colloidal dispersion, the micelles of which contain the alkali or alkaline earth metal carbonate formed during carbonation.
- the micelles are stabilized by the alkali or alkaline earth metal salts of organic acids which have a detergent effect.
- the salts of organic acids used in overbased additives are generally sulfonates, salicylates or sulfurized phenates, described respectively in US Patents 4,604,219, EP-A 279,493 and FR 2,305,494.
- overbased additives are particularly useful in lubricants used in internal combustion engines of the "gasoline” type or of the "diesel” type.
- molybdenum additives in lubricants as friction reducers.
- the most ancient product used is molybdenum disulphide in the form of a stable dispersion.
- oil-soluble compounds of molybdenum there may be mentioned the dithiocarbamates (EP-A 205 165), and the complexes of molybdenum with oxazoline (US 4,176,073).
- Molybdenum complexes with compounds containing basic nitrogen from succinimides, amides, phosphonamides or Mannich bases are used in the sulfurized form (US 4,263,152, US 4,369,119, US 4,395,343).
- molybdenum is incorporated in the form of an inorganic compound, during (US 4,601,837) or after (US 3,496,105) overbasing.
- molybdenum derivative is incorporated into the micelles of the colloidal dispersion with the alkali or alkaline earth metal carbonate.
- the incorporation of the molybdenum derivative into the micelle results in the formation of a single multifunctional additive, having the properties of overbased additives and those of molybdenum derivatives.
- the advantage of this multifunctional additive compared to mixtures of overbased detergents and oil-soluble derivatives of molybdenum, lies in their greater stability and the fact that there is no competition between the two additives for access to the metal surface to be lubricated.
- the additives according to the invention have antiwear, friction reducing and antioxidant properties in lubricant formulations.
- This invention therefore relates to overbased additives for lubricating oils, composed of at least one detergent and of an alkali or alkaline earth metal carbonate in a diluting oil which is in the form of a colloidal dispersion, the micelles of which contain said carbonate. characterized in that at least one organic complex of molybdenum practically insoluble in hydrocarbons is incorporated in the micelles of the colloidal dispersion.
- the amine-molybdenum complexes are particularly suitable.
- the amine-molybdenum complexes are prepared by the reaction of an inorganic molybdenum compound with an acid reaction, with an amine.
- molybdenum compounds can be listed molybdic acid, alkaline molybdates, sodium hydrogen molybdate, ammonium molybdate, MoOCl4, MoO2 Br2, Mo2O3Cl6 and molybdenum trioxide.
- Sodium molybdate and ammonium molybdate are preferably used.
- the amines used have an aliphatic or aromatic structure.
- primary, secondary or tertiary amines are suitable provided that they form complexes with molybdenum complexes which are practically insoluble in hydrocarbons.
- the use of primary amines, whose complexes with molybdenum are not very soluble in hydrocarbons is particularly recommended.
- the amine group can be attached to a primary carbon, as in the amines already mentioned, but also to a secondary or tertiary carbon, as in 1-amino-1,1-dimethyl-decane and 1-amino-1,1 -dimethyl-dodecane.
- secondary amines in which the total number of carbon does not exceed 12, generally give, with molybdenum, complexes insoluble in hydrocarbons.
- diamines having a primary amine group are also recommended.
- diamines of general formula (I) are sold by the company CECA S.A. under the name of DINORAM.
- R1 represents hydrogen and R2 represents saturated or unsaturated aliphatic radicals derived from fatty acids. They are generally mixtures containing C12 to C18 alkyl radicals.
- the amine-molybdenum complex is generally prepared in an aqueous medium.
- the amine is added to an aqueous solution of mineral molybdenum compound.
- the reaction medium is maintained at a temperature between 20 and 100 ° C, preferably between 50 and 90 ° C, for 0.5 to 3 hours after the addition of the amine.
- the amount of acid necessary for neutralizing the reaction medium is added before or after the introduction of the amine.
- a strong mineral acid is used, preferably sulfuric acid.
- the amine-molybdenum complex precipitates. It is recovered by filtration, washed with water and optionally dried.
- the complex has a solid or pasty appearance, depending on the type of amine used. Its color varies from white to blue. It is practically insoluble or very sparingly soluble in hydrocarbons.
- the atomic ratio of nitrogen to molybdenum in the complex is generally between 0.25 and 4 and preferably between 0.5 and 2.
- the molybdenum content of the complex varies depending on the nature of the amine used: it is between approximately 10 and 45%.
- organic molydene complexes mention may also be made of complexes with oxygenated compounds.
- glycols 1-2, 1-3 and 1-4 Particularly suitable are glycols 1-2, 1-3 and 1-4.
- ethylene glycol and propylene glycol are used.
- alkoxylated amines or polyamines, preferably with ethylene oxide or propylene oxide are also suitable.
- ethylene oxide or propylene oxide are also suitable.
- diethanolamine or tri-ethanolamine we can mention the derivatives of diethanolamine or tri-ethanolamine.
- the preparation of these complexes can be carried out by heating the oxygenated compound to 90-100 ° C., in the presence of a molybdenum compound, such as ammonium molybdate.
- a molybdenum compound such as ammonium molybdate.
- the water produced by the reaction is removed under a stream of nitrogen.
- the molybdenum content of the complexes obtained varies between 7 and 50% by weight, depending on the degree of elimination of the unreacted oxygenated compound.
- the organic molybdenum complex can be sulfurized for example by the action of sulfuric anhydride (H2S) on a suspension of the complex in an aromatic solvent such as xylene or toluene, at a temperature between 40 ° C and 100 ° C. As soon as sulfuric anhydride is introduced, the color of the suspension changes from blue-green to orange and then to red.
- the quantity of sulfuric anhydride introduced is such that the atomic ratio of sulfur to molybdenum is between approximately 1 and 3.
- the process for the preparation of overbased additives according to the invention consists in carbonating a mixture containing a detergent or a detergent precursor, a derivative of an alkali or alkaline earth metal, a nitrogenous and / or oxygenated promoter, optionally a hydrocarbon solvent, a diluent oil and / or water, characterized in that said mixture contains at least one organic complex of molybdenum practically insoluble in hydrocarbons.
- detergents which can be used in the context of the invention, there may be mentioned sulfonates, phenates, naphtenates, salicylates, phosphonates and thiophosphonates alkali or alkaline earth soluble in the hydrocarbon medium.
- the sulfonic acids used for the preparation of the sulfonates can be of petroleum or synthetic origin. Petroleum sulfonic acids are prepared by sulfonation of oils from the distillation of petroleum. Their structure does not correspond to a well defined formula but their average molecular weight must be at least equal to 300.
- Synthetic sulfonic acids are prepared by alkylation of aromatic compounds such as benzene, toluene, xylene or naphthalene with olefinic cuts and then by sulfonation of the alkylate obtained.
- aromatic compounds such as benzene, toluene, xylene or naphthalene with olefinic cuts and then by sulfonation of the alkylate obtained.
- the structure of the alkyl chains attached to the nucleus is linear or branched depending on the olefins used for the alkylation.
- the number of carbon atoms per alkyl chain is greater than or equal to 8.
- the preparation of the alkali or alkaline earth metal sulfonate is carried out by bringing the sulfonic acid into contact with an alkali or alkaline earth metal derivative (preferably oxide or hydroxide) in a hydrocarbon solvent, optionally in the presence of an alcohol.
- an alkali or alkaline earth metal derivative preferably oxide or hydroxide
- the alkali or alkaline earth metal phenates are prepared under analogous or substantially different temperature conditions, from sulfurized alkylphenol or alkylphenol.
- the phenol ring can carry one or two linear or branched alkyl chains, having at least eight carbon atoms.
- the most common compound is dodecylphenol.
- the optional sulfurization of phenol is carried out by the action of sulfur monochloride S2 Cl2 or by the action of elemental sulfur at temperatures ranging from 150 to 200 ° C.
- the sulfurized product contains approximately 1 to 1.5 sulfur atoms per phenolic nucleus.
- the alkylsalicylic acids are prepared by alkylation of salicylic acid or by carboxylation under pressure of alkylphenols.
- the alkyl chain contains a minimum of 12 carbon atoms.
- the phosphonates and thiophosphonates are prepared by the action of P2O5 or P2S5 on a polyisobutene then neutralization with an alkali or alkaline earth oxide or hydroxide.
- the molecular weight of polyisobutene is between 300 and 2000.
- All of these detergents can be used in admixture with dispersants soluble in a hydrocarbon medium, for example of the alkylsuccinimide type or esters of alkylsuccinic acids with a molecular weight of 300 to 2500.
- reaction medium can contain the precursors. In this case, neutralization is carried out in the reaction medium just before carbonation.
- the alkali or alkaline earth metal derivatives can be oxides, hydroxides or alcoholates.
- the preferred derivatives are oxides and hydroxides.
- the reaction medium is added to stoichiometric excess relative to the detergent or its precursor.
- the stoichiometric excess can vary between 5: 1 and 30: 1.
- an oxygenated promoter is introduced into the reaction medium before carbonation, which is generally an aliphatic or aromatic alcohol, an alkoxyalkanol, a glycol or even an alkanolamine.
- reaction medium which is generally an aliphatic or aromatic alcohol, an alkoxyalkanol, a glycol or even an alkanolamine.
- aliphatic alcohols C1 to C20 or mixtures thereof.
- the aliphatic alcohols can be used in admixture with glycols, alkoxyalkanols or alkanolamines.
- the molar ratio of the oxygenated promoter to the detergent is generally between 1 and 30.
- nitrogenous promoter is optional.
- This nitrogenous promoter is generally chosen from ammonia, ammonium salts, primary, secondary or tertiary amines in C2 to C10 and their salts with carboxylic acids or boric acid, polyamines or even alkanolamines.
- ammonia, carbonate and ammonium chloride, ethylenediamine, ethanolamine or diethanolamine are preferred.
- the promoter to detergent molar ratio is generally between 1 and 30.
- the hydrocarbon solvent allows perfect homogenization of the various reagents as well as a lowering of the viscosity which will subsequently facilitate the recovery of solid carbonation residues.
- the solvent represents from 10 to 70% by weight of the reaction mixture.
- the solvents used are the aliphatic or aromatic compounds in C6 and C12.
- Preferred solvents are aromatic solvents such as benzene, toluene, xylene, ethylbenzene and chlorinated aromatics. Their choice is dictated by the characteristics of the additive collected, by their boiling point and by the boiling point of the azeotropes which they can form with oxygenated promoters and water.
- the handling of the molybdenum overbased additive obtained according to the invention is facilitated by the addition of oil.
- the oil represents approximately 20 to 50% by weight of the additive obtained. This can be added to the reaction medium before carbonation or even after this, that is to say just before the removal of the solvent.
- the diluent oils used are paraffinic in nature, of the 100 or 150 Neutral solvent type or predominantly naphthenic in nature such as 100 - 150 pale solvent.
- the carbonation reaction can be carried out after optional addition of water to the reaction medium.
- the addition of water is particularly beneficial when the alkali or alkaline earth metal derivative is an oxide.
- the amount of water added is such that the water / metal oxide molar ratio is of the order of 0.5.
- Neutralization of the detergent precursor is then carried out, followed by carbonation of the stoichiometric excess of the alkali or alkaline earth metal derivative at a temperature between room temperature and the reflux temperature of the mixture.
- the molar ratio of CO2 introduced to the stoichiometric excess of alkali or alkaline earth metal is between 0.6 and 1.2.
- the mixture is optionally stabilized by heating under vacuum or under a stream of nitrogen so as to eliminate the oxygenated promoters of low boiling point and the water added as well as the water produced by carbonation. Solid residues are removed by centrifugation and / or filtration using diatomaceous earth. If the diluent oil has not been added before carbonation, it is then added before possible elimination of the hydrocarbon solvent and heavy alcohols, by heating under vacuum at temperatures of the order of 100 to 200 ° C.
- the filtration operation can be carried out after recovery of the solvent.
- the overbased products containing molybdenum, obtained according to the invention are clear and stable, brown in color for the sulfonates, dark green for the phenates and black for the salicylates.
- the color is generally red for overbased detergents in the presence of a sulfurized complex.
- the rate of incorporation of molybdenum into the additive is close to 100%, significantly higher than the rates obtained during the incorporation of inorganic derivatives of molybdenum.
- the additive contains between 0.1 to 10% by weight and preferably 1 to 4% of molybdenum.
- overbased additives according to the invention are entirely soluble in hydrocarbons. They are incorporated into lubricating oils of natural or synthetic origin at a concentration of between 0.5 and 40% by weight and preferably between 1 and 30% by weight.
- the lubricant compositions thus obtained can contain other additives, with antiwear, dispersing, antioxidant effect, and polymers improving the viscosity index.
- the basicity of these overbased additives is characterized by their alkaline value (VA) expressed in mg of KOH per gram of product. It is determined by titration using a strong acid according to standard ASTM D-2896.
- a solution of 41.17 g of sodium molybdate Na2MoO4, 2H2O in 100 ml of water is produced.
- the medium is acidified by the addition of 55.6 g of 30% H2SO4 and then heated to 60 ° C.
- 21g Dinoram C from CECA SA is added.
- Dinoram C corresponds to the formula R-NH- (CH2) 3-NH2 where R is a mixture of linear and saturated alkyl radicals, 60% C de, 20% C14, 10% C16 and 5% C18.
- the aforementioned blue is recovered by filtration and then washed with water and methanol before drying. Finally recovered 47.1 g of blue solid containing 32.6% molybdenum and 4.4% nitrogen.
- Example A The procedure is as in Example A but the addition of Diroram C is carried out at 60 ° C before heating and before acidification.
- the pale blue solid recovered contains 34.1% molybdenum, 0.3% sodium and 4.46% nitrogen.
- a dispersion of 20 g of the complex prepared in Example A is produced in 200 ml of xylene.
- 6.7 g of H2S are injected; the dark red solid collected after removal of the solvent contains 28.4% molybdenum, 3.8% nitrogen and 23.7% sulfur.
- the procedure is as in the example, but 9.68 g of sodium molybdate in 35 ml of water are used. 4.8 g of Dinoram O (PM 270) from CECA SA are added at 65 ° C. before heating the medium for 1 hour at 60 ° C. Dinoram O is an N-alkyl-propylene-diamine. The alkyl radical corresponds to a mixture containing 80% of oleyl radical. We then observe the gradual formation of a white solid which turns blue during acidification. After washing and drying, 8.85 g of a blue solid are recovered containing 23% molybdenum.
- Noram C is a monoamine, R-NH2 where R is a mixture of linear and saturated alkyl radicals, 60% C de, 20% C14, 10% C16 and 5% C18. 11 g of a light blue solid containing 26.7% molybdenum are finally recovered.
- Example D The procedure is as in Example D but 6.74 g of stearylamine from CECA SA are used. 7.68 g of a pale blue solid containing 20.5% of molybdenum and 3.4% of nitrogen are recovered.
- Primene 81-R is a mixture of two monoamines, 1-amino-1,1-dimethyl-decane and 1-amino-1,1-dimethyl-dodecane. 15.75 g of a blue pasty product containing 12.5% molybdenum are collected.
- Example B The procedure is as in Example B, but 9.9 g of 98% ethyl-2-hexylamine are introduced over 20 minutes in an aqueous solution containing 15.44 g of sodium molybdate and maintained at 60 ° C. After heating for 45 minutes at 60 ° C., acidification is carried out with 23.1 g of 30% sulfuric acid, before washing and drying the product. This is in the form of a white solid containing 36.8% molybdenum and 4.38% nitrogen.
- Example A The procedure is as in Example A, but an aqueous solution containing 48.4 g of sodium molybdate is acidified with 65.4 g of 30% sulfuric acid. The solution being maintained at 60 ° C. 52.2 g of p-dodecyl aniline are added. The blue green pasty solid is dissolved in xylene in order to remove the water therefrom by azeotropic distillation. After removal of the solvent, 80 g of pasty solid containing 11.5% molybdenum and 3.41% nitrogen are recovered. It can be noted that the complexes prepared in Examples A to I are practically insoluble in hydrocarbon compounds as well as in water or in alcohols.
- the methanol and the water produced by the reaction are removed by heating the mixture under partial vacuum.
- the product is clear brown and stable when diluted in mineral or synthetic oils. No clouding or settling is observed after several weeks at 60 ° C.
- Example 2 The procedure is as in Example 1, but 219.2 g of alkyl aryl sulfonic acid with branched alkyl chain (didodecylbenzenesulfonic acid) are introduced, the molecular weight of which is 520 and at 70% of active material. The amount of diluent oil is 108g. The product is in the form of a brown liquid of VA 304. It is stable when diluted in lubricating oils.
- Example 2 The procedure is as in Example 1, but 32 g of the complex prepared in Example I are introduced before the other reagents in 520 ml of xylene. The procedure is identical to that of Example 1 except that the residues are removed by centrifugation.
- Example 2 The procedure is as in Example 1, but successively introduced into the reactor - 600 ml of xylene, 132 g of didodecylbenzene sulfonic acid of molecular weight 520g and at 70% of active material - 30g of the complex prepared in Example A - 104g of slaked lime - 52ml of methanol - 4.4ml of ammonia and 90g of diluent oil.
- the product collected is brown, clear and stable in oils.
- the calcium and molybdenum contents are 10 and 2.35 respectively.
- 77.8 g of dodecylphenol and 20 g of sulfur chloride are introduced at a temperature of 20 to 30 ° C. into a 250 ml reactor equipped with a temperature-regulating cooler and a gas bubbling device.
- the mixture is heated under nitrogen sweep and with stirring for one hour at 150 ° C then 1 hour at 180 ° C and finally 1 hour at 200 ° C.
- the sulfurized dodecylphenol is collected, the respective chlorine and sulfur contents of which are 2200 ppm and 11.4%.
- Example 14 The procedure is as in Example 14, but 27 g of the complex prepared in Example B are introduced before the lime.
- the product collected at the end of the operations and dark brown, stable in oils.
- VA 197, its molybdenum content of 1.77%.
- the performance of new overbased detergents containing molybdenum is examined in laboratory tests of wear, friction and oxidation.
- the test matrices correspond to lubricants for land engines on the one hand and for marine engines on the other.
- the products are tested in a lubricant formulation used in petrol engines (ELF Presti 15 W 40) by simply replacing the overbased detergent.
- the samples contain 1.25% overbased detergent.
- the test is carried out under the following conditions: Lapping 5 minutes under 200 lbs (normal load) 3 hours under 540 lbs (normal load) At the end of the test, the value of the friction torque, the wear in number of teeth of the ratchet wheel and the temperature of the oil bath tested are noted. (The wear is as much lower as the number of teeth, the friction torque and the temperature are lower). Table 1 shows that the overbased sulfonates containing an amine-molybdenum complex allow a reduction of 50 to 70% on average in the friction torque.
- the TFOUT test (thin film oxygen uptake test) is performed on the same essence formulations. It is carried out at 160 ° C. in a pressurized oxygen bomb (90 psi) in the presence of metal catalyst (Naphtenate of Pb, Cu, Fe, Mn and Sn), water and nitro petrol oxidized so as to partially simulate the conditions to which oil can be subjected in a petrol engine.
- Table 3 gives values of the induction time, that is to say the time between the start of the test and the start of the rapid pressure drop in the bomb.
- the increase in the induction time is significant in the presence of the additive containing the molybdenum-amine complex.
- overbased detergents containing molybdenum are then tested in a lubricant formulation for a marine engine (cylinder oil).
- the basicity of the oil is 70 mg KOH / g of which only 20 mg KOH / g provided by the overbased detergent.
- the oil also contains 0.5% DTPZ.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Description
Cette invention concerne des additifs surbasés pour huiles lubrifiantes renfermant un complexe organique du molybdène pratiquement insoluble dans les hydrocarbures.This invention relates to overbased additives for lubricating oils containing an organic complex of molybdenum practically insoluble in hydrocarbons.
Les additifs surbasés sont des sels de métaux alcalins ou alcalinoterreux d'acides organiques, surbasés par carbonatation avec l'anhydride carbonique. Le terme surbasé est utilisé pour désigner l'excès de métal alcalin ou alcalinoterreux par rapport à la quantité stoéchiométrique nécessaire pour neutraliser l'acide organique utilisé.Overbased additives are alkali or alkaline earth metal salts of organic acids, overbased by carbonation with carbon dioxide. The term overbased is used to designate the excess of alkali or alkaline earth metal over the stoichiometric amount necessary to neutralize the organic acid used.
La structure des additifs surbasés est celle d'une dispersion colloïdale dont les micelles renferment le carbonate de métal alcalin ou alcalinoterreux formé lors de la carbonatation. Les micelles sont stabilisés par les sels de métaux alcalins ou alcalinoterreux d'acides organiques qui ont un effet détergent.The structure of the overbased additives is that of a colloidal dispersion, the micelles of which contain the alkali or alkaline earth metal carbonate formed during carbonation. The micelles are stabilized by the alkali or alkaline earth metal salts of organic acids which have a detergent effect.
Les sels d'acides organiques utilisés dans les additifs surbasés sont en général les sulfonates, les salicylates ou les phénates sulfurisés, décrits respectivement des les brevets US 4 604 219, EP-A 279 493 et FR 2 305 494.The salts of organic acids used in overbased additives are generally sulfonates, salicylates or sulfurized phenates, described respectively in US Patents 4,604,219, EP-A 279,493 and FR 2,305,494.
Ces additifs surbasés sont particulièrement utiles dans les lubrifiants utilisés dans les moteurs à combustion interne du type "essence" ou du type "diesel".These overbased additives are particularly useful in lubricants used in internal combustion engines of the "gasoline" type or of the "diesel" type.
Grâce à leur effet détergent et dispersant, ils évitent la formation de laques et de vernis et maintiennent en dispersion les suies issues de la combustion incomplète du carburant.Thanks to their detergent and dispersing effect, they prevent the formation of lacquers and varnishes and keep the soot from the incomplete combustion of fuel dispersed.
Une autre fonction importante de ces additifs est la neutralisation des composés acides, comme des acides organiques formés par oxydation de l'huile et les acides formés lors de la combustion des produits soufrés apportés par les combustibles.Another important function of these additives is the neutralization of acidic compounds, such as organic acids formed by oxidation of the oil and the acids formed during the combustion of the sulfur products supplied by the fuels.
Cette fonction de neutralisation est particulièrement appréciée lors de l'utilisation de combustibles riches en soufre, comme les fuels lourds utilisés dans les moteurs marins.This neutralization function is particularly appreciated when using fuels rich in sulfur, such as heavy fuels used in marine engines.
Il est connu par ailleurs, d'utiliser dans les lubrifants des additifs au molybdène comme réducteurs de frottement. Le produit le plus anciennement utilisé est le bisulfure de molybdène sous forme de dispersion stable.It is also known to use molybdenum additives in lubricants as friction reducers. The most ancient product used is molybdenum disulphide in the form of a stable dispersion.
Pour éviter les opérations de broyage et de mise en dispersion stable du bisulfure de molybdène, on a proposé l'utilisation de composés organiques oléosolubles du molybdène, qui peuvent être incorporés directement dans les lubrifiants.To avoid the operations of grinding and stable dispersion of the molybdenum disulphide, the use of oil-soluble organic compounds of molybdenum has been proposed, which can be incorporated directly into the lubricants.
Parmi les composés oléosolubles du molybdène on peut citer les dithiocarbamates (EP-A 205 165), et les complexes du molybdène avec l'oxazoline (US 4 176 073). Les complexes du molybdène avec les composés renfermant un azote basique issu de succinimides, amides, phosphonamides ou bases de Mannich sont utilisés sous forme sulfurisées (US 4 263 152, US 4 369 119, US 4 395 343).Among the oil-soluble compounds of molybdenum there may be mentioned the dithiocarbamates (EP-A 205 165), and the complexes of molybdenum with oxazoline (US 4,176,073). Molybdenum complexes with compounds containing basic nitrogen from succinimides, amides, phosphonamides or Mannich bases are used in the sulfurized form (US 4,263,152, US 4,369,119, US 4,395,343).
On connait également des additifs surbasés au molybdène. Le molybdène est incorporé sous forme d'un composé minéral, pendant (US 4 601 837) ou après (US 3 496 105) le surbasage.There are also known additives overbased with molybdenum. The molybdenum is incorporated in the form of an inorganic compound, during (US 4,601,837) or after (US 3,496,105) overbasing.
Nous avons trouvé maintenant de façon inattendue qu'il était possible d'incorporer dans les additifs surbasés des dérivés du molybdène pratiquement insolubles dans les hydrocarbures, car ces dérivés se solubilisent pendant la réaction de surbasage.We have now unexpectedly found that it is possible to incorporate into overbased additives derivatives of molybdenum practically insoluble in hydrocarbons, since these derivatives dissolve during the overbasing reaction.
Nous ne voulons pas être limités par cette explication main nous suggérons que le dérivé du molybdène est incorporé dans les micelles de la dispersion colloïdale avec le carbonate de métal alcalin ou alcalinoterreux.We do not want to be limited by this explanation but we suggest that the molybdenum derivative is incorporated into the micelles of the colloidal dispersion with the alkali or alkaline earth metal carbonate.
L'incorporation du dérivé du molybdène dans la micelle résulte dans la formation d'un additif unique multifonctionnel, ayant les propriétés des additifs surbasés et ceux des dérivés du molybdène. L'avantage de cet additif multifonctionnel par rapport aux mélanges de détergents surbasés et de dérivés oléosolubles du molybdène, réside dans leur plus grande stabilité et le fait qu'il n'y a pas de compétition entre les deux additifs pour l'accès à la surface métallique à lubrifier.The incorporation of the molybdenum derivative into the micelle results in the formation of a single multifunctional additive, having the properties of overbased additives and those of molybdenum derivatives. The advantage of this multifunctional additive compared to mixtures of overbased detergents and oil-soluble derivatives of molybdenum, lies in their greater stability and the fact that there is no competition between the two additives for access to the metal surface to be lubricated.
Les additifs selon l'invention présentent des propriétés antiusure, réductrice de friction et antioxydante dans les formulations lubrifiantes.The additives according to the invention have antiwear, friction reducing and antioxidant properties in lubricant formulations.
Cette invention concerne donc des additifs surbasés pour huiles lubrifiantes, composés d'au moins un détergent et d'un carbonate de métal alcalin ou alcalino-terreux dans une huile diluante se présentant sous la forme d'une dispersion colloïdale dont les micelles renferment ledit carbonate caractérisés en ce que au moins un complexe organique du molybdène pratiquement insoluble dans les hydrocarbures est incorporé dans les micelles de la dispersion colloïdale.This invention therefore relates to overbased additives for lubricating oils, composed of at least one detergent and of an alkali or alkaline earth metal carbonate in a diluting oil which is in the form of a colloidal dispersion, the micelles of which contain said carbonate. characterized in that at least one organic complex of molybdenum practically insoluble in hydrocarbons is incorporated in the micelles of the colloidal dispersion.
Parmi les complexes organiques du molybdène conviennent tout particulièrement les complexes amine-molybdène.Among the organic molybdenum complexes, the amine-molybdenum complexes are particularly suitable.
Les complexes amine-molybdène sont préparés par réaction d'un composé minéral du molybdène a réaction acide, avec une amine.The amine-molybdenum complexes are prepared by the reaction of an inorganic molybdenum compound with an acid reaction, with an amine.
Parmi ces composés du molybdène on peut énumérer l'acide molybdique, les molybdates alcalins, le sodium hydrogène molybdate, le molybdate d'ammonium, le MoOCl₄, le MoO₂ Br₂, le Mo₂O₃Cl₆ et le trioxyde de molybdène.Among these molybdenum compounds can be listed molybdic acid, alkaline molybdates, sodium hydrogen molybdate, ammonium molybdate, MoOCl₄, MoO₂ Br₂, Mo₂O₃Cl₆ and molybdenum trioxide.
On utilise de préférence le molybdate de sodium et le molybdate d'ammonium.Sodium molybdate and ammonium molybdate are preferably used.
Les amines utilisées sont de structure aliphatiques ou aromatiques.The amines used have an aliphatic or aromatic structure.
Parmi les amines aliphatiques conviennent des amines primaires, secondaires ou tertiaires condition de former avec des composés du molybdène des complexes pratiquement insolubles dans les hydrocarbures. L'emploi des amines primaires, dont les complexes avec le molybdène sont très peu solubles dans les hydrocarbures est particulièrement recommandé.Among the aliphatic amines, primary, secondary or tertiary amines are suitable provided that they form complexes with molybdenum complexes which are practically insoluble in hydrocarbons. The use of primary amines, whose complexes with molybdenum are not very soluble in hydrocarbons is particularly recommended.
Parmi les amines primaires nous citerons l'oleylamine, la stéarylamine, la dodécylamine, la ter-dodécylamine, l'éthyl-2-hexylamine et la cyclohexylamine.Among the primary amines we will cite oleylamine, stearylamine, dodecylamine, ter-dodecylamine, ethyl-2-hexylamine and cyclohexylamine.
Le groupe amine peut être attaché à un carbone primaire, comme dans les amines déjà citées, mais également à un carbone secondaire ou tertiaire, comme dans le 1-amino-1,1-diméthyl-décane et le 1-amino-1,1-diméthyl-dodécane.The amine group can be attached to a primary carbon, as in the amines already mentioned, but also to a secondary or tertiary carbon, as in 1-amino-1,1-dimethyl-decane and 1-amino-1,1 -dimethyl-dodecane.
L'utilisation de certaines amines secondaires peut être recommandée. Ainsi les amines secondaires, dans lesquelles le nombre total de carbone ne dépasse pas 12, donnent en général avec le molybdène, des complexes insolubles dans les hydrocarbures.The use of certain secondary amines may be recommended. Thus secondary amines, in which the total number of carbon does not exceed 12, generally give, with molybdenum, complexes insoluble in hydrocarbons.
Parmi les amines aromatiques nous pouvons mentionner la para-dodécylaniline.Among the aromatic amines we can mention para-dodecylaniline.
L'utilisation des diamines ayant un groupe amine primaire est également recommandée.The use of diamines having a primary amine group is also recommended.
Les diamines de la formule générale R₁R₂N-(CH₂)n-NH₂(I) où R₁ et R₂ identiques ou différents représentent l'hydrogène ou un radical aliphatique linéaire ou ramifié, saturé ou insaturé en C₁ à C₃₀ et de préférence en C₈ à C₂₀, un des radicaux R₁ ou R₂ représentant obligatoirement un radical aliphatique et n étant compris entre 1 et 8 et de préférence entre 2 et 4, forment des complexes très peu solubles dans les hydrocarbures.The diamines of the general formula R₁R₂N- (CH₂) n -NH₂ (I) where R₁ and R₂ identical or different represent hydrogen or a linear or branched aliphatic radical, saturated or unsaturated in C en to C₃₀ and preferably in C₈ to C₂₀ , one of the radicals R₁ or R₂ necessarily representing an aliphatic radical and n being between 1 and 8 and preferably between 2 and 4, form complexes which are hardly soluble in hydrocarbons.
Certaines des diamines de formule générale (I) sont commercialisées par la société CECA S.A. sous la dénomination de DINORAM.Some of the diamines of general formula (I) are sold by the company CECA S.A. under the name of DINORAM.
Dans la série DINORAM, R₁ représente l'hydrogène et R₂ des radicaux aliphatiques saturés ou insaturés issus d'acides gras. Il s'agit en général de mélanges contenant des radicaux alkyle de C₁₂ à C₁₈.In the DINORAM series, R₁ represents hydrogen and R₂ represents saturated or unsaturated aliphatic radicals derived from fatty acids. They are generally mixtures containing C₁₂ to C₁₈ alkyl radicals.
Le complexe amine-molybdène est en général préparé en milieu aqueux. L'amine est ajoutée à une solution aqueuse de composé minéral de molybdène.The amine-molybdenum complex is generally prepared in an aqueous medium. The amine is added to an aqueous solution of mineral molybdenum compound.
Le milieu réactionnel est maintenu à une température comprise entre 20 et 100°C, de préférence entre 50 et 90°C, pendant 0,5 à 3 heures après l'addition de l'amine.The reaction medium is maintained at a temperature between 20 and 100 ° C, preferably between 50 and 90 ° C, for 0.5 to 3 hours after the addition of the amine.
La quantité d'acide nécessaire à la neutralisation du milieu réactionnel est ajoutée avant ou après l'introduction de l'amine. On utilise un acide minéral fort, de préférence l'acide sulfurique.The amount of acid necessary for neutralizing the reaction medium is added before or after the introduction of the amine. A strong mineral acid is used, preferably sulfuric acid.
Le complexe amine-molybdène précipite. Il est récupéré par filtration, lavé à l'eau et éventuellement séché.The amine-molybdenum complex precipitates. It is recovered by filtration, washed with water and optionally dried.
Le complexe présente un aspect solide ou pateux, selon le type d'amine utilisé. Sa couleur varie du blanc au bleu. Il est pratiquement insoluble ou très peu soluble dans les hydrocarbures.The complex has a solid or pasty appearance, depending on the type of amine used. Its color varies from white to blue. It is practically insoluble or very sparingly soluble in hydrocarbons.
Le rapport atomique de l'azote au molybdène dans le complexe est en général compris entre 0,25 et 4 et de préférence entre 0,5 et 2.The atomic ratio of nitrogen to molybdenum in the complex is generally between 0.25 and 4 and preferably between 0.5 and 2.
La teneur en molybdène du complexe varie en fonction de la nature de l'amine utilisée: elle est comprise entre environ 10 et 45 %.The molybdenum content of the complex varies depending on the nature of the amine used: it is between approximately 10 and 45%.
Parmi les complexes organique du molydène on peut également citer les complexes avec des composés oxygénés.Among the organic molydene complexes, mention may also be made of complexes with oxygenated compounds.
Conviennent tout particulièrement les glycols 1-2, 1-3 et 1-4. On utilise de préférence l'éthylène glycol et le propylène glycol.Particularly suitable are glycols 1-2, 1-3 and 1-4. Preferably ethylene glycol and propylene glycol are used.
Parmi les polyols nous pouvons mentionner le glycerol et le triméthylol propane.Among the polyols we can mention glycerol and trimethylol propane.
Certaines amines, ou polyamines alkoxylées, de préférence avec l'oxyde de l'éthylène ou l'oxyde de propylène conviennent également. Nous pouvons mentionner les dérivés de la diethanolamine ou de la tri-ethanolamine.Certain alkoxylated amines, or polyamines, preferably with ethylene oxide or propylene oxide are also suitable. We can mention the derivatives of diethanolamine or tri-ethanolamine.
La préparation de ces complexes peut être réalisée par chauffage à 90-100°C du composé oxygéné, en présence d'un composé du molybdène, comme le molybdate d'ammonium. L'eau produite par la réaction est éliminée sous courant d'azote.The preparation of these complexes can be carried out by heating the oxygenated compound to 90-100 ° C., in the presence of a molybdenum compound, such as ammonium molybdate. The water produced by the reaction is removed under a stream of nitrogen.
La teneur en molybdène des complexes obtenus varie entre 7 et 50 % poids, selon le degré d'élimination du composé oxygèné non réagi.The molybdenum content of the complexes obtained varies between 7 and 50% by weight, depending on the degree of elimination of the unreacted oxygenated compound.
Le complexe organique du molybdène peut être sulfurisé par exemple par action de l'anhydride sulfurique (H₂S) sur une suspension du complexe dans un solvant aromatique comme le xylène ou le toluène, à une température comprise entre 40°C et 100°C. Dès l'introduction de l'anhydride sulfurique, la couleur de la suspension passe du bleu-vert à l'orangé puis au rouge. La quantité d'anhydre sulfurique introduite est telle que le rapport atomique du soufre au molybdène soit compris entre environ 1 et 3.The organic molybdenum complex can be sulfurized for example by the action of sulfuric anhydride (H₂S) on a suspension of the complex in an aromatic solvent such as xylene or toluene, at a temperature between 40 ° C and 100 ° C. As soon as sulfuric anhydride is introduced, the color of the suspension changes from blue-green to orange and then to red. The quantity of sulfuric anhydride introduced is such that the atomic ratio of sulfur to molybdenum is between approximately 1 and 3.
Le procédé de préparation d'additifs surbasés selon l'invention consiste à carbonater un mélange renfermant un détergent ou un précurseur de détergent, un dérivé d'un métal alcalin ou alcalinoterreux, un promoteur azoté et/ou oxygéné, éventuellement un solvant hydrocarboné, une huile diluante et/ou de l'eau, caractérisé en ce que ledit mélange renferme au moins un complexe organique du molybdène pratiquement insoluble dans les hydrocarbures.The process for the preparation of overbased additives according to the invention consists in carbonating a mixture containing a detergent or a detergent precursor, a derivative of an alkali or alkaline earth metal, a nitrogenous and / or oxygenated promoter, optionally a hydrocarbon solvent, a diluent oil and / or water, characterized in that said mixture contains at least one organic complex of molybdenum practically insoluble in hydrocarbons.
Parmi les détergents utilisables dans le cadre de l'invention on peut citer les sulfonates, les phénates, les naphtenates, les salicylates, les phosphonates et les thiophosphonates alcalins ou alcalinoterreux solubles dans le milieu hydrocarboné.Among the detergents which can be used in the context of the invention, there may be mentioned sulfonates, phenates, naphtenates, salicylates, phosphonates and thiophosphonates alkali or alkaline earth soluble in the hydrocarbon medium.
Les acides sulfoniques utilisés pour la préparation des sulfonates peuvent être d'origine pétrolière ou synthétique. Les acides sulfoniques pétroliers sont préparés par sulfonation d'huiles issues de la distillation du pétrole. Leur structure ne correspond pas à une formule bien définie mais leur poids moléculaire moyen doit être au moins égal à 300.The sulfonic acids used for the preparation of the sulfonates can be of petroleum or synthetic origin. Petroleum sulfonic acids are prepared by sulfonation of oils from the distillation of petroleum. Their structure does not correspond to a well defined formula but their average molecular weight must be at least equal to 300.
Les acides sulfoniques synthétiques sont préparés par alkylation de composés aromatiques comme le benzène, toluène, xylène ou naphtalène avec des coupes oléfiniques puis par sulfonation de l'alkylat obtenu. La structure des chaînes alkyles fixées sur le noyau est linéaire ou ramifiée selon les oléfines utilisées pour l'alkylation. Le nombre d'atomes de carbone par chaine alkyle est supérieur ou égal à 8.Synthetic sulfonic acids are prepared by alkylation of aromatic compounds such as benzene, toluene, xylene or naphthalene with olefinic cuts and then by sulfonation of the alkylate obtained. The structure of the alkyl chains attached to the nucleus is linear or branched depending on the olefins used for the alkylation. The number of carbon atoms per alkyl chain is greater than or equal to 8.
La préparation du sulfonate de métal alcalin ou alcalinoterreux est réalisée par mise en contact de l'acide sulfonique avec un dérivé de métal alcalin ou alcalinoterreux (oxyde ou hydroxyde préférentiellement) dans un solvant hydrocarboné, éventuellement en présence d'un alcool.The preparation of the alkali or alkaline earth metal sulfonate is carried out by bringing the sulfonic acid into contact with an alkali or alkaline earth metal derivative (preferably oxide or hydroxide) in a hydrocarbon solvent, optionally in the presence of an alcohol.
Les phénates de métal alcalin ou alcalinoterreux sont préparés dans des conditions analogues ou sensiblement différentes pour ce qui est de la température, à partir d'alkylphénol ou d'alkylphénol sulfurisé. Le noyau phénol peut porter une ou deux chaines alkyl linéaires ou ramifiées, comptant au moins huit atomes de carbone. Le composé le plus répandu est le dodécylphénol.The alkali or alkaline earth metal phenates are prepared under analogous or substantially different temperature conditions, from sulfurized alkylphenol or alkylphenol. The phenol ring can carry one or two linear or branched alkyl chains, having at least eight carbon atoms. The most common compound is dodecylphenol.
La sulfurisation éventuelle du phénol est réalisée par action du monochlorure de soufre S₂ Cl₂ ou par action du soufre élémentaire à des températures allant de 150 à 200°C. Le produit sulfurisé contient environ 1 à 1,5 atomes de soufre par noyau phénolique.The optional sulfurization of phenol is carried out by the action of sulfur monochloride S₂ Cl₂ or by the action of elemental sulfur at temperatures ranging from 150 to 200 ° C. The sulfurized product contains approximately 1 to 1.5 sulfur atoms per phenolic nucleus.
Les acides alkylsalicyliques sont préparés par alkylation de l'acide salicylique ou par carboxylation sous pression des alkylphénols. La chaine alkyl contient un minimum de 12 atomes de carbone.The alkylsalicylic acids are prepared by alkylation of salicylic acid or by carboxylation under pressure of alkylphenols. The alkyl chain contains a minimum of 12 carbon atoms.
Les phosphonates et thiophosphonates sont préparés par action de P₂O₅ ou P₂S₅ sur un polyisobutène puis neutralisation par un oxyde ou hydroxyde alcalin ou alcalinoterreux. Le poids moléculaire du polyisobutène est compris entre 300 et 2000.The phosphonates and thiophosphonates are prepared by the action of P₂O₅ or P₂S₅ on a polyisobutene then neutralization with an alkali or alkaline earth oxide or hydroxide. The molecular weight of polyisobutene is between 300 and 2000.
Tous ces détergents peuvent être utilisés en mélange avec des dispersants solubles en milieu hydrocarboné par exemple du type alkylsuccinimide ou esters d'acides alkylsucciniques de poids moléculaire 300 à 2500.All of these detergents can be used in admixture with dispersants soluble in a hydrocarbon medium, for example of the alkylsuccinimide type or esters of alkylsuccinic acids with a molecular weight of 300 to 2500.
A la place des détergents, le milieu réactionnel peut renfermer les précurseurs. Dans ce cas la neutralisation est réalisée dans le milieu réactionnel juste avant la carbonatation.In place of detergents, the reaction medium can contain the precursors. In this case, neutralization is carried out in the reaction medium just before carbonation.
Les dérivés de métal alcalin ou alcalinoterreux peuvent être les oxydes, hydroxydes ou alcoolates. Les dérivés préférés sont les oxydes et hydroxydes.The alkali or alkaline earth metal derivatives can be oxides, hydroxides or alcoholates. The preferred derivatives are oxides and hydroxides.
Ceux-ci sont ajoutés au milieu réactionnel en excès stoéchiométrique par rapport au détergent ou à son précurseur. L'excès stoéchiométrique peut varier entre 5:1 et 30:1.These are added to the reaction medium in stoichiometric excess relative to the detergent or its precursor. The stoichiometric excess can vary between 5: 1 and 30: 1.
Dans le procédé selon l'invention, on introduit dans le milieu réactionnel avant carbonatation un promoteur oxygéné, qui est généralement un alcool aliphatique ou aromatique, un alkoxyalcanol, un glycol ou encore une alcanolamine. On utilise de préférence les alcools aliphatique en C₁ à C₂₀ ou leurs mélanges. Les alcools aliphatiques peuvent être utilisés en mélange avec des glycols, des alkoxyalcanols ou alcanolamines.In the process according to the invention, an oxygenated promoter is introduced into the reaction medium before carbonation, which is generally an aliphatic or aromatic alcohol, an alkoxyalkanol, a glycol or even an alkanolamine. Preferably used aliphatic alcohols C₁ to C₂₀ or mixtures thereof. The aliphatic alcohols can be used in admixture with glycols, alkoxyalkanols or alkanolamines.
Le rapport molaire du promoteur oxygéné au détergent est généralement compris entre 1 et 30.The molar ratio of the oxygenated promoter to the detergent is generally between 1 and 30.
L'utilisation d'un promoteur azoté est facultative. Ce promoteur azoté est généralement choisi parmi l'ammoniaque, les sels d'ammonium, les amines primaires, secondaires ou tertiaires en C₂ à C₁₀ et leurs sels avec les acides carboxyliques ou l'acide borique, les polyamines ou encore les alcanolamines.The use of a nitrogenous promoter is optional. This nitrogenous promoter is generally chosen from ammonia, ammonium salts, primary, secondary or tertiary amines in C₂ to C₁₀ and their salts with carboxylic acids or boric acid, polyamines or even alkanolamines.
Parmi les promoteurs azotés, on préfère l'ammoniaque, le carbonate et le chlorure d'ammonium, l'éthylènediamine, l'éthanolamine ou la diéthanolamine.Among the nitrogenous promoters, ammonia, carbonate and ammonium chloride, ethylenediamine, ethanolamine or diethanolamine are preferred.
Le rapport molaire du promoteur au détergent est généralement compris entre 1 et 30.The promoter to detergent molar ratio is generally between 1 and 30.
Le solvant hydrocarboné permet une homogénéisation parfaite des différents réactifs ainsi qu'un abaissement de la viscosité ce qui facilitera ultérieurement la récupération des résidus solides de carbonatation. Le solvant représente de 10 à 70 % poids du mélange réactionnel. Les solvants utilisés sont les composés aliphatiques ou aromatiques en C₆ et C₁₂. Les solvants préférés sont les solvant aromatiques comme le benzène, toluène, xylène, éthylbenzène et les aromatiques chlorés. Leur choix est dicté par les caractéristiques de l'additif recueilli, par leur point d'ébullition et par le point d'ébullition des azéotropes qu'ils peuvent former avec les promoteurs oxygénés et l'eau.The hydrocarbon solvent allows perfect homogenization of the various reagents as well as a lowering of the viscosity which will subsequently facilitate the recovery of solid carbonation residues. The solvent represents from 10 to 70% by weight of the reaction mixture. The solvents used are the aliphatic or aromatic compounds in C₆ and C₁₂. Preferred solvents are aromatic solvents such as benzene, toluene, xylene, ethylbenzene and chlorinated aromatics. Their choice is dictated by the characteristics of the additive collected, by their boiling point and by the boiling point of the azeotropes which they can form with oxygenated promoters and water.
La manipulation de l'additif surbasé au molybdène, obtenu selon l'invention est facilitée par l'addition d'huile. L'huile représente environ 20 à 50 % poids de l'additif obtenu. Celle-ci peut être ajoutée au milieu réactionnel avant la carbonatation ou encore après celle-ci, c'est-à-dire juste avant l'élimination du solvant. Les huiles diluantes utilisées sont de nature paraffinique, du type 100 ou 150 Neutral solvant ou de nature majoritairement napthénique telle que la 100 - 150 pale solvant.The handling of the molybdenum overbased additive obtained according to the invention is facilitated by the addition of oil. The oil represents approximately 20 to 50% by weight of the additive obtained. This can be added to the reaction medium before carbonation or even after this, that is to say just before the removal of the solvent. The diluent oils used are paraffinic in nature, of the 100 or 150 Neutral solvent type or predominantly naphthenic in nature such as 100 - 150 pale solvent.
La réaction de carbonatation peut être réalisée après addition éventuelle d'eau au milieu réactionnel. L'addition d'eau s'avère particulièrement bénéfique lorsque le dérivé de métal alcalin ou alcalinoterreux est un oxyde. Généralement la quantité d'eau ajoutée est telle que le rapport molaire eau/oxyde de métal soit de l'ordre de 0,5.The carbonation reaction can be carried out after optional addition of water to the reaction medium. The addition of water is particularly beneficial when the alkali or alkaline earth metal derivative is an oxide. Generally the amount of water added is such that the water / metal oxide molar ratio is of the order of 0.5.
La mise en oeuvre du procédé selon l'invention consiste à introduire successivement dans un réacteur équipé d'un agitateur, d'une régulation de température, d'un dispositif de barbotage de gaz carbonique, d'un système de chauffage et de mise sous vide :
- 0 à 700 parties poids d'un solvant hydrocarboné
- 100 à 400 parties poids d'un détergent ou d'un précurseur de détergent
- un dérivé de métal alcalin ou alcalinoterreux en excès stoéchiométrique par rapport au détergent ou à son précurseur. Cet excès stoéchiométrique est compris entre 5:1 et 30:1
- un promoteur oxygéné dont le rapport molaire au détergent ou à son précurseur est compris entre 1 et 30
- éventuellement un promoteur azoté dont le rapport molaire au détergent est compris entre 1 et 30
- éventuellement une quantité d'eau telle que le rapport molaire eau/oxyde de métal soit de l'ordre de 0.5
- éventuellement de l'huile diluante en quantité telle que celle-ci représente 20 à 50 % poids de l'additif récupéré à la fin des opérations
- un complexe organique du molybdène décrit précédemment en quantité telle que la teneur en molybdène du produit fini soit comprise entre 0,1 et 10 % poids.
- 0 to 700 parts by weight of a hydrocarbon solvent
- 100 to 400 parts by weight of a detergent or a detergent precursor
- an alkali or alkaline earth metal derivative in stoichiometric excess relative to the detergent or its precursor. This stoichiometric excess is between 5: 1 and 30: 1
- an oxygenated promoter whose molar ratio to the detergent or to its precursor is between 1 and 30
- optionally a nitrogen promoter whose molar ratio to detergent is between 1 and 30
- optionally an amount of water such that the water / metal oxide molar ratio is of the order of 0.5
- optionally diluent oil in quantity such as this represents 20 to 50% by weight of the additive recovered at the end of the operations
- an organic complex of molybdenum described above in an amount such that the molybdenum content of the finished product is between 0.1 and 10% by weight.
Dans le cas où on utilise un précurseur de détergent il est préférable d'introduire successivement le précurseur, le complexe du molybdène et enfin l'excès de dérivé de métal alcalin ou alcalinoterreux.In the case where a detergent precursor is used, it is preferable to successively introduce the precursor, the molybdenum complex and finally the excess of alkali or alkaline earth metal derivative.
On réalise ensuite la neutralisation du précurseur du détergent, puis on procède à la carbonatation de l'excès stoéchiométrique du dérivé de métal alcalin ou alcalinoterreux à une température comprise entre la température ambiante et la température de reflux du mélange. Le rapport molaire du CO₂ introduit à l'excès stoéchiométrique de métal alcalin ou alcalinoterreux est compris entre 0,6 et 1,2. Le mélange est éventuellement stabilisé par chauffage sous vide ou sous courant d'azote de façon à éliminer les promoteurs oxygénés de bas point d'ébullition et l'eau ajoutée ainsi que l'eau produite par la carbonatation. Les résidus solides sont éliminés par centrifugation et/ou filtration à l'aide de terres à diatomées. Si l'huile diluante n'a pas été ajoutée avant carbonatation, elle est alors ajoutée avant élimination éventuelle du solvant hydrocarboné et des alcools lourds, par chauffage sous vide à des températures de l'ordre de 100 à 200°C.Neutralization of the detergent precursor is then carried out, followed by carbonation of the stoichiometric excess of the alkali or alkaline earth metal derivative at a temperature between room temperature and the reflux temperature of the mixture. The molar ratio of CO₂ introduced to the stoichiometric excess of alkali or alkaline earth metal is between 0.6 and 1.2. The mixture is optionally stabilized by heating under vacuum or under a stream of nitrogen so as to eliminate the oxygenated promoters of low boiling point and the water added as well as the water produced by carbonation. Solid residues are removed by centrifugation and / or filtration using diatomaceous earth. If the diluent oil has not been added before carbonation, it is then added before possible elimination of the hydrocarbon solvent and heavy alcohols, by heating under vacuum at temperatures of the order of 100 to 200 ° C.
Il faut remarquer que l'opération de filtration peut être réalisée après récupération du solvant.It should be noted that the filtration operation can be carried out after recovery of the solvent.
Les produits surbasés contenant du molybdène, obtenus selon l'invention, sont limpides et stables, de coloration brune pour les sulfonates, vert foncé pour les phénates et noire pour les salicylates. La couleur est généralement rouge pour les détergents surbasés en présence d'un complexe sulfurisé.The overbased products containing molybdenum, obtained according to the invention, are clear and stable, brown in color for the sulfonates, dark green for the phenates and black for the salicylates. The color is generally red for overbased detergents in the presence of a sulfurized complex.
Le taux d'incorporation du molybdène dans l'additif est proche de 100 %, nettement supérieur aux taux obtenus lors de l'incorporation de dérivés inorganiques du molybdène.The rate of incorporation of molybdenum into the additive is close to 100%, significantly higher than the rates obtained during the incorporation of inorganic derivatives of molybdenum.
L'additif renferme entre 0,1 à 10 % poids et de préférence 1 à 4 % de molybdène.The additive contains between 0.1 to 10% by weight and preferably 1 to 4% of molybdenum.
Les additifs surbasés selon l'invention sont entièrement solubles dans les hydrocarbures. Ils sont incorporés aux huiles lubrifiantes d'origine naturelle ou synthétique à une concentration comprise entre 0,5 et 40 % poids et de préférence entre 1 et 30 % poids.The overbased additives according to the invention are entirely soluble in hydrocarbons. They are incorporated into lubricating oils of natural or synthetic origin at a concentration of between 0.5 and 40% by weight and preferably between 1 and 30% by weight.
Les compositions lubrifiantes ainsi obtenues peuvent renfermer d'autres additifs, à effet antiusure, dispersant, antioxydant, et des polymères améliorant l'indice de viscosité.The lubricant compositions thus obtained can contain other additives, with antiwear, dispersing, antioxidant effect, and polymers improving the viscosity index.
Les exemples ci-dessous illustrent l'invention sans toutefois la limiter.The examples below illustrate the invention without, however, limiting it.
Dans les exemples la basicité de ces additifs surbasés est caractérisée par leur valeur alcaline (VA) exprimée en mg de KOH par gramme de produit. Elle est déterminée par titration à l'aide d'un acide fort selon la norme ASTM D-2896.In the examples, the basicity of these overbased additives is characterized by their alkaline value (VA) expressed in mg of KOH per gram of product. It is determined by titration using a strong acid according to standard ASTM D-2896.
Sauf indication contraire, tous les pourcentages sont en poids.Unless otherwise indicated, all percentages are by weight.
Dans un réacteur muni d'une régulation de température et d'un dispositif d'agitation on réalise un solution de 41,17g de molybdate de sodium Na₂MoO₄, 2H₂O dans 100 ml d'eau. Le milieu est acidifié par addition de 55,6g d'H₂SO₄ à 30 % puis chauffé à 60°C. On procède ensuite à l'addition de 21g Dinoram C de CECA SA.
Le Dinoram C correspond à la formule R-NH-(CH₂)₃-NH₂ où R est un mélange de radicaux alkyles linéaires et saturés, à 60 % de C₁₂, 20 % C₁₄, 10 % C₁₆ et 5 % C₁₈.
Le précité bleu est récupéré par filtration puis lavé à l'eau et au méthanol avant séchage.
On récupère finalement 47,1g de solide bleu contenant 32,6 % de molybdène et 4,4 % d'azote.In a reactor fitted with a temperature control and a stirring device, a solution of 41.17 g of sodium molybdate Na₂MoO₄, 2H₂O in 100 ml of water is produced. The medium is acidified by the addition of 55.6 g of 30% H₂SO₄ and then heated to 60 ° C. Next, 21g Dinoram C from CECA SA is added.
Dinoram C corresponds to the formula R-NH- (CH₂) ₃-NH₂ where R is a mixture of linear and saturated alkyl radicals, 60% C de, 20% C₁₄, 10% C₁₆ and 5% C₁₈.
The aforementioned blue is recovered by filtration and then washed with water and methanol before drying.
Finally recovered 47.1 g of blue solid containing 32.6% molybdenum and 4.4% nitrogen.
On opère comme dans l'exemple A mais l'addition de Diroram C est effectuée à 60°C avant chauffage et avant l'acidification.
Le solide bleu pale récupéré contient 34,1 % de molybdène 0,3 % de sodium et 4,46 % d'azote.The procedure is as in Example A but the addition of Diroram C is carried out at 60 ° C before heating and before acidification.
The pale blue solid recovered contains 34.1% molybdenum, 0.3% sodium and 4.46% nitrogen.
Dans un réacteur de 250 ml équipé d'une régulation de température, d'une agitation et d'un système de barbotage de gaz, on réalise une dispersion de 20g du complexe préparé à l'exemple A dans 200 ml de xylène. Dans la dispersion maintenue à 80°C on injecte 6,7g d'H₂S ; le solide rouge foncé recueilli après élimination du solvant contient 28,4 % de molybdène, 3,8 % d'azote et 23,7 % de soufre.In a 250 ml reactor equipped with temperature regulation, stirring and a gas bubbling system, a dispersion of 20 g of the complex prepared in Example A is produced in 200 ml of xylene. In the dispersion maintained at 80 ° C., 6.7 g of H₂S are injected; the dark red solid collected after removal of the solvent contains 28.4% molybdenum, 3.8% nitrogen and 23.7% sulfur.
On opère comme dans l'exemple mais on utilisé 9,68g de molybdate de sodium dans 35 ml d'eau. On ajoute à 65°C 4,8g de Dinoram O (PM 270) de CECA SA avant chauffage du milieu pendant 1 heure à 60°C
Le Dinoram O est une N-alkyle-propylène-diamine. Le radical alkyle correspond à un mélange renfermant 80 % de radical oléyle. On observe alors la formation progressive d'un solide blanc qui vire au bleu lors de l'acidification. Après lavage et séchage on récupère 8,85g d'un solide bleu
contenant 23 % de molybdène.The procedure is as in the example, but 9.68 g of sodium molybdate in 35 ml of water are used. 4.8 g of Dinoram O (PM 270) from CECA SA are added at 65 ° C. before heating the medium for 1 hour at 60 ° C.
Dinoram O is an N-alkyl-propylene-diamine. The alkyl radical corresponds to a mixture containing 80% of oleyl radical. We then observe the gradual formation of a white solid which turns blue during acidification. After washing and drying, 8.85 g of a blue solid are recovered
containing 23% molybdenum.
On opère comme dans l'exemple B mais on utilise 7g de monoamine primaire Noram C de CECA SA. La Noram C est une monoamine, R-NH₂ où R est un mélange de radicaux alkyles linéaires et saturés, à 60 % de C₁₂, 20 % C₁₄, 10 % C₁₆ et 5 % C₁₈. On récupère finalement 11g d'un solide bleu clair contenant 26,7 % de molybdène.The procedure is as in Example B, but 7 g of primary monoamine Noram C from CECA SA is used. Noram C is a monoamine, R-NH₂ where R is a mixture of linear and saturated alkyl radicals, 60% C de, 20% C₁₄, 10% C₁₆ and 5% C₁₈. 11 g of a light blue solid containing 26.7% molybdenum are finally recovered.
On opère comme dans l'exemple D mais on utilise 6,74g de stéarylamine de CECA SA.
On récupère 7,68g d'un solide bleu pale contenant 20,5 % de molybdène et 3,4 % d'azote.The procedure is as in Example D but 6.74 g of stearylamine from CECA SA are used.
7.68 g of a pale blue solid containing 20.5% of molybdenum and 3.4% of nitrogen are recovered.
On opère comme dans l'exemple D mais on utilise 8g de Primène 81-R ROHM et HAAS (PM 185 à 213).
Le Primène 81-R est un mélange de deux monoamines, le 1-amino-1,1-diméthyl-décane et le 1-amino-1,1-diméthyl-dodécane.
On recueille 15,75g d'un produit pateux bleu contenant 12,5% de molybdène.The procedure is as in Example D but 8g of Primene 81-R ROHM and HAAS are used (PM 185 to 213).
Primene 81-R is a mixture of two monoamines, 1-amino-1,1-dimethyl-decane and 1-amino-1,1-dimethyl-dodecane.
15.75 g of a blue pasty product containing 12.5% molybdenum are collected.
On opère comme dans l'exemple B mais on introduit en 20 minutes 9,9g d'ethyl-2-hexylamine à 98 % dans une solution aqueuse contenant 15,44g de molybdate de sodium et maintenue à 60°C. Après chauffage de 45 minutes à 60°C, on acidifie par 23,1g d'acide sulfurique à 30 %, avant lavage et séchage du produit . Celui-ci se présente sous la forme d'un solide blanc contenant 36,8 % de molybdène et 4,38 % d'azote.The procedure is as in Example B, but 9.9 g of 98% ethyl-2-hexylamine are introduced over 20 minutes in an aqueous solution containing 15.44 g of sodium molybdate and maintained at 60 ° C. After heating for 45 minutes at 60 ° C., acidification is carried out with 23.1 g of 30% sulfuric acid, before washing and drying the product. This is in the form of a white solid containing 36.8% molybdenum and 4.38% nitrogen.
On opère comme dans l'exemple A mais on acidifie par 65,4g d'acide sulfurique à 30 % une solution aqueuse contenant 48,4g de molybdate de sodium. La solution étant maintenue à 60°C on ajoute 52,2g de p-dodécyle aniline. Le solide pateux bleu vert est solubilisé dans le xylène afin d'en éliminer l'eau par distillation azéotropique. On récupère après élimination du solvant 80g de solide pateux contenant 11,5 % de molybdène et 3,41 % d'azote. On peut remarquer que les complexes préparés dans les exemples A à I sont pratiquement insolubles dans les composés hydrocarbonés ainsi d'ailleurs que dans l'eau ou les alcools.The procedure is as in Example A, but an aqueous solution containing 48.4 g of sodium molybdate is acidified with 65.4 g of 30% sulfuric acid. The solution being maintained at 60 ° C. 52.2 g of p-dodecyl aniline are added. The blue green pasty solid is dissolved in xylene in order to remove the water therefrom by azeotropic distillation. After removal of the solvent, 80 g of pasty solid containing 11.5% molybdenum and 3.41% nitrogen are recovered. It can be noted that the complexes prepared in Examples A to I are practically insoluble in hydrocarbon compounds as well as in water or in alcohols.
Leur incorporation dans les additifs surbasés ne se fait donc pas par dissolution dans la phase hydrocarbonée, mais par incorporation du complexe dans les particules colloidales de carbonate.Their incorporation into overbased additives is therefore not done by dissolution in the hydrocarbon phase, but by incorporation of the complex in the colloidal carbonate particles.
Dans un réacteur de 1 litre équipé d'une régulation de température d'un réfrigérant, d'un système d'agitation et d'un dispositif de barbotage de gaz on introduit successivement :
- 520 ml de toluène, 131,8g d'acide alkylxylènesulfonique à chaine alkyl linéaire en C₁₆-C₁₈, de poids moléculaire 430 et à 96 % de matière active, 168g d'huile diluante 100 Neutral solvent, 113,24g de chaux éteinte à 96 % de pureté et 48 ml de méthanol.
Après neutralisation de l'acide sulfonique par la chaux qui peut éventuellement être réalisée par chauffage à 60°C du milieu réactionnel pendant 30 minutes, on introduit alors 55,2g de gaz carbonique dans le mélange maintenu à une température de 42°C.
Après carbonatation, on élimine le méthanol et l'eau produite par la réaction en chauffant le mélange sous vide partiel. Le milieu est clarifié par filtration en utilisant 2 % poids de Diatomées Clarcel DICS de CECA SA.
Après élimination du solvant on récupère 400g de produit contenant 13,1 % de calcium.
VA=321. Le produit est brun limpide et stable en dilution dans les huiles minérales ou synthétiques. On n'observe aucun trouble ou aucune décantation après plusieurs semaines à 60°C.In a 1 liter reactor equipped with a temperature regulation of a refrigerant, a stirring system and a gas bubbling device, successively:
- 520 ml of toluene, 131.8 g of alkylxylenesulfonic acid with linear C₁₆-C₁₈ alkyl chain, of molecular weight 430 and 96% of active material, 168g of diluent oil 100 Neutral solvent, 113.24g of lime slaked at 96% purity and 48 ml of methanol.
After neutralization of the sulfonic acid with lime which can optionally be carried out by heating the reaction medium at 60 ° C. for 30 minutes, 55.2 g of carbon dioxide are then introduced into the mixture maintained at a temperature of 42 ° C.
After carbonation, the methanol and the water produced by the reaction are removed by heating the mixture under partial vacuum. The medium is clarified by filtration using 2% by weight of Diatomées Clarcel DICS from CECA SA.
After removing the solvent, 400 g of product containing 13.1% of calcium are recovered.
VA = 321. The product is clear brown and stable when diluted in mineral or synthetic oils. No clouding or settling is observed after several weeks at 60 ° C.
On opère comme dans l'exemple 1 mais on introduit 219,2g d'acide alkyl aryl sulfonique à chaine alkyl ramifiée (de l'acide didodecylbenzènesulfonique) dont le poids moléculaire est de 520 et à 70 % de matière active.
La quantité d'huile diluante est de 108g.
Le produit se présente sous la forme d'un liquide brun de VA 304. Il est stable en dilution dans les huiles lubrifiantes.The procedure is as in Example 1, but 219.2 g of alkyl aryl sulfonic acid with branched alkyl chain (didodecylbenzenesulfonic acid) are introduced, the molecular weight of which is 520 and at 70% of active material.
The amount of diluent oil is 108g.
The product is in the form of a brown liquid of VA 304. It is stable when diluted in lubricating oils.
On opère comme dans l'exemple 1 mais on met en dispersion 30g du complexe Dinoram C/Molybdène décrit dans l'exemple A, dans 520 ml de xylène, avant l'introduction des autres réactifs. Après carbonatation et élimination de l'eau et du méthanol, les résidus solides sont éliminés par centrifugation. Après évaporation du solvant on récupère 448g de sulfonate surbasé contenant du molybdène ; VA=300, sa teneur en calcium est de 11,7 % et sa teneur en molybdène de 2,17 %. Il est stable en dilution dans les huiles lubrifiantes.The procedure is as in Example 1, but 30 g of the Dinoram C / Molybdenum complex described in Example A are dispersed in 520 ml of xylene, before the introduction of the other reagents. After carbonation and removal of water and methanol, the solid residues are removed by centrifugation. After evaporation of the solvent, 448 g of overbased sulfonate containing molybdenum are recovered; VA = 300, its calcium content is 11.7% and its molybdenum content 2.17%. It is stable when diluted in lubricating oils.
On opère comme dans l'exemple 1 mais on introduit 28g du complexe préparé dans l'exemple B dans 520 ml de toluène avant l'addition des autres réactifs.
On récupère un sulfonate surbasé contenant du molybdène. VA=303, la teneur en calcium est de 11,9 % et la teneur en molybdène de 1,94 %. Il est stable en dilution dans les huiles.The procedure is as in Example 1, but 28 g of the complex prepared in Example B are introduced into 520 ml of toluene before the addition of the other reagents.
An overbased sulfonate containing molybdenum is recovered. VA = 303, the calcium content is 11.9% and the molybdenum content 1.94%. It is stable when diluted in oils.
On opère comme dans l'exemple 2 mais on introduit 28g du complexe préparé dans l'exemple A dans 520 ml de xylène. Après carbonatation, élimination de l'eau et du méthanol, récupération des résidus solides par centrifugation puis évaporation du solvant, on recueille 440g de produit, VA=290 et contenant 1,69 % de molybdène et 11,5 % de calcium. La stabilité en dilution dans l'huile est remarquable.The procedure is as in Example 2, but 28 g of the complex prepared in Example A are introduced into 520 ml of xylene. After carbonation, elimination of water and methanol, recovery of solid residues by centrifugation then evaporation of the solvent, 440 g of product are collected, VA = 290 and containing 1.69% of molybdenum and 11.5% of calcium. The stability when diluted in oil is remarkable.
On opère comme dans l'exemple 1 mais on met en suspension dans 520 ml de xylène, 28g de complexe Dinoram C/Molybdène sulfurisé comme décrit dans l'exemple C et ceci avant introduction des autres réactifs. La suite des opérations est identique à celle de l'exemple 1 à la différence près que les résidus sont éliminés par centrifugation. On recueille un sulfonate surbasé contenant du molybdène, VA=304. Les teneurs en molybdène, soufre et calcium sont respectivement de 1,63, 3,4 et 11,7 %. Le produit obtenu a une couleur brun rouge et il est stable en dilution dans les huiles lubrifiantes.The procedure is as in Example 1, but 28 g of Dinoram C / sulfurized Molybdenum complex as described in Example C is suspended in 520 ml of xylene before the introduction of the other reagents. The continuation of the operations is identical to that of Example 1 except that the residues are removed by centrifugation. An overbased sulfonate containing molybdenum is collected, VA = 304. The molybdenum, sulfur and calcium contents are respectively 1.63, 3.4 and 11.7%. The product obtained has a reddish brown color and is stable when diluted in lubricating oils.
On opère comme dans l'exemple 1 mais on met en suspension 28g du complexe préparé à l'exemple H dans 520 ml de xylène avant l'introduction des autres réactifs. La procédure est la même que dans l'exemple 1 à la différence près que les résidus sont éliminés par centrifugation. On recueille un produit brun VA=353. Les teneurs en calcium et molybdène sont respectivement de 12,2 et 1,97 %. La stabilité en dilution dans les huiles lubrifiantes est parfaite.The procedure is as in Example 1, but 28 g of the complex prepared in Example H are suspended in 520 ml of xylene before the introduction of the other reagents. The procedure is the same as in Example 1 except that the residues are removed by centrifugation. A brown product VA = 353 is collected. The calcium and molybdenum contents are respectively 12.2 and 1.97%. The dilution stability in lubricating oils is perfect.
On opère comme dans l'exemple 1 mais on introduit avant les autres réactifs 32g du complexe préparé dans l'exemple I dans 520 ml de xylène. La procédure est identique à celle de l'exemple 1 à la différence près que les résidus sont éliminés par centrifugation. Le sulfonate surbasé contenant du molybdène est brun foncé et stable dans les huiles, VA=311, ses teneurs en calcium et molybdène sont respectivement, 11,9 et 1,09 %.The procedure is as in Example 1, but 32 g of the complex prepared in Example I are introduced before the other reagents in 520 ml of xylene. The procedure is identical to that of Example 1 except that the residues are removed by centrifugation. The overbased sulfonate containing molybdenum is dark brown and stable in oils, VA = 311, its calcium and molybdenum contents are, respectively 11.9 and 1.09%.
On opère comme dans l'exemple 1 mais on introduit 30g du complexe préparé dans l'exemple A dans les 520 ml de toluène avant addition des autres réactifs. La suite des opérations est identique à celle de l'exemple 1 à ceci près que l'on introduit 52,7g de CO₂ lors de la carbonatation. On récupère après centrifugation 448g de sulfonate surbasé contenant du molybdène. VA=298. Les teneurs en calcium et molybdène sont respectivement de 11,7 % et 2,1 %. La stabilité dans les huiles est remarquable.The procedure is as in Example 1, but 30 g of the complex prepared in Example A are introduced into the 520 ml of toluene before addition of the other reagents. The following operations are identical to that of Example 1 except that 52.7 g of CO₂ are introduced during carbonation. 448 g of overbased sulfonate containing molybdenum are recovered after centrifugation. VA = 298. The calcium and molybdenum contents are 11.7% and 2.1% respectively. The stability in oils is remarkable.
On opère comme dans l'exemple 9 mais on récupère après filtration sur Diatomées, 440g de sulfonate surbasé contenant du molybdène, VA=292. La teneur en molybdène est de 1,96 % et le produit est limpide et stable en dilution dans les huiles.The procedure is as in Example 9, but after filtration through diatomaceous earth, 440 g of overbased sulfonate containing molybdenum, VA = 292, are recovered. The molybdenum content is 1.96% and the product is clear and stable when diluted in oils.
On opère comme dans l'exemple 1 mais on introduit successivement dans le réacteur - 600 ml de xylène, 132 g d'acide didodecylbenzène sulfonique de poids moléculaire 520g et à 70 % de matière active - 30g du complexe préparé à l'exemple A - 104g de chaux éteinte - 52ml de méthanol - 4,4ml d'ammoniaque et 90g d'huile diluante.
Le produit recueilli est brun, limpide et stable dans les huiles. Les teneurs en calcium et molybdène sont respectivement de 10 et 2,35.The procedure is as in Example 1, but successively introduced into the reactor - 600 ml of xylene, 132 g of didodecylbenzene sulfonic acid of molecular weight 520g and at 70% of active material - 30g of the complex prepared in Example A - 104g of slaked lime - 52ml of methanol - 4.4ml of ammonia and 90g of diluent oil.
The product collected is brown, clear and stable in oils. The calcium and molybdenum contents are 10 and 2.35 respectively.
Dans un réacteur de 250 ml muni d'un réfrigérant d'une régulation de température et d'un dispositif de barbotage de gaz, on introduit 77,8g de dodécylphénol et 20g de chlorure de soufre à une température de 20 à 30°C. On chauffe le mélange sous balayage d'azote et sous agitation pendant une heure à 150°C puis 1 heure à 180°C et enfin 1 heure à 200°C. On recueille le dodécylphénol sulfurisé dont les teneurs respectives en chlore et en soufre sont de 2200 ppm et 11,4%.77.8 g of dodecylphenol and 20 g of sulfur chloride are introduced at a temperature of 20 to 30 ° C. into a 250 ml reactor equipped with a temperature-regulating cooler and a gas bubbling device. The mixture is heated under nitrogen sweep and with stirring for one hour at 150 ° C then 1 hour at 180 ° C and finally 1 hour at 200 ° C. The sulfurized dodecylphenol is collected, the respective chlorine and sulfur contents of which are 2200 ppm and 11.4%.
Dans un autre réacteur de 250 ml muni d'un système d'agitation, d'une régulation de température et d'un dispositif de barbotage de gaz on introduit successivement 43g de dodécylphénol sulfurisé, 30g d'huile diluante 100 Neutral solvent, 90 ml de xylène, 11,8g d'oxyde de calcium, 66 ml de methanol et 2g de nitrate de calcium Ca(NO₃)₂, 4H₂O. Le mélange est porté à reflux pendant 45 minutes avant élimination de l'eau produite par la neutralisation. On ajoute 66 ml de méthanol au mélange avant de carbonater par le gaz carbonique l'excès stoéchiométrique de chaux, à une température de 50°C. Après carbonatation on élimine par chauffage sous vide partiel l'eau résiduelle et le méthanol avant de récupérer les résidus solides par filtration. Après évaporation du solvant, on recueille un dodécylphénol sulfurisé surbasé de couleur brun vert, stable dans les huiles. VA=240.In another 250 ml reactor fitted with a stirring system, a temperature control and a gas bubbling device, 43 g of sulfurized dodecylphenol, 30 g of diluent oil 100 Neutral solvent, 90 ml are successively introduced. xylene, 11.8 g of calcium oxide, 66 ml of methanol and 2 g of calcium nitrate Ca (NO₃) ₂, 4H₂O. The mixture is brought to reflux for 45 minutes before elimination of the water produced by neutralization. 66 ml of methanol are added to the mixture before carbonating with carbon dioxide the stoichiometric excess of lime, at a temperature of 50 ° C. After carbonation, the residual water and methanol are removed by heating under partial vacuum before recovering the solid residues by filtration. After evaporation of the solvent, an overbased sulfurized dodecylphenol of brown green color is collected, stable in oils. VA = 240.
On opère comme dans l'exemple 12 mais on introduit dans le milieu réactionnel, juste après l'élimination de l'eau de neutralisation, 5,6g du complexe amine/molybdène préparé à l'exemple B. On récupère un phénate surbasé, VA=243 et dont la teneur en molybdène est de 1,89 %. Le produit est stable en dilution dans l'huile.The procedure is as in Example 12, but 5.6 g of the amine / molybdenum complex prepared in Example B is introduced into the reaction medium, just after the elimination of the neutralization water. An overbased phenate, VA is recovered = 243 and whose molybdenum content is 1.89%. The product is stable when diluted in oil.
On opère comme dans l'exemple 1 mais on introduit dans le réacteur 312g d'acide (C₁₄, C₁₈-alkyl)salicylique, 37,5g de chaux éteinte, 150ml de méthanol et 100g d'huile diluante. Après neutralisation et carbonatation à 42°C par 7,65g de CO₂, on rajoute 30g de chaux que l'on carbonate par 10g de CO₂. On recueille un additif de couleur brun foncé stable dans les huiles. Sa teneur en calcium est de 7,6 %, VA=205.The procedure is as in Example 1, but 312g (C₁₄, C₁₈-alkyl) salicylic acid, 37.5g of slaked lime, 150ml of methanol and 100g of diluent oil are introduced into the reactor. After neutralization and carbonation at 42 ° C with 7.65g of CO₂, 30g of lime is added which is carbonated with 10g of CO₂. A stable dark brown additive is collected in the oils. Its calcium content is 7.6%, VA = 205.
On opère comme dans l'exemple 14 mais on introduit avant la chaux, 27g du complexe préparé à l'exemple B. Le produit recueilli à, la fin des opérations et brun foncé, stable dans les huiles. VA=197, sa teneur en molybdène de 1,77 %.The procedure is as in Example 14, but 27 g of the complex prepared in Example B are introduced before the lime. The product collected at the end of the operations and dark brown, stable in oils. VA = 197, its molybdenum content of 1.77%.
Les performances des nouveaux détergents surbasés contenant du molybdène sont examinées sur des essais en laboratoire d'usure, de frottement et d'oxydation. Les matrices d'essai correspondent à des lubrifiants pour moteurs terrestre d'une part et pour moteurs marins d'autre part.
Tout d'abord les produits sont testés dans une formulation lubrifiante utilisée dans les moteurs à essence (ELF Presti 15 W 40) en simple substitution du détergent surbasé.The performance of new overbased detergents containing molybdenum is examined in laboratory tests of wear, friction and oxidation. The test matrices correspond to lubricants for land engines on the one hand and for marine engines on the other.
First of all, the products are tested in a lubricant formulation used in petrol engines (ELF Presti 15 W 40) by simply replacing the overbased detergent.
Les échantillons renferment 1,25 % de détergent surbasé.The samples contain 1.25% overbased detergent.
L'essai est réalisé dans les conditions suivantes :
Rodage 5 minutes sous 200 lbs (normal load)
3 heures sous 540 lbs (normal load)
En fin d'essai on note la valeur du couple de frottement, de l'usure en nombre de dents de la roue à rochet et de la température du bain d'huile testée. (L'usure est autant plus faible que le nombre de dents, le couple de frottement et la température sont moins élevés). Le tableau 1 permet de constater que les sulfonates surbasés contenant un complexe amine-molybdène permettent une réduction de 50 à 70 % en moyenne du couple de frottement. L'utilisation d'un réducteur de frottement au molybdène classique, associé à un sulfonate de référence donne un résultat catastrophique (Exemple 1 + 1,2 % MOLYVAN L) bien que la teneur en molybdène dans ce dernier cas soit de l'ordre de 1200ppm contre 250ppm pour les huiles formulées avec les sulfonates surbasés contenant du molybdène selon l'invention.
On remarque aussi une forte diminution de l'échauffement liée à la réduction de frottement apportée par les sulfonates surbasés selon l'invention.The test is carried out under the following conditions:
Lapping 5 minutes under 200 lbs (normal load)
3 hours under 540 lbs (normal load)
At the end of the test, the value of the friction torque, the wear in number of teeth of the ratchet wheel and the temperature of the oil bath tested are noted. (The wear is as much lower as the number of teeth, the friction torque and the temperature are lower). Table 1 shows that the overbased sulfonates containing an amine-molybdenum complex allow a reduction of 50 to 70% on average in the friction torque. The use of a conventional molybdenum friction reducer, combined with a reference sulfonate gives a catastrophic result (Example 1 + 1.2% MOLYVAN L) although the molybdenum content in the latter case is of the order of 1200 ppm versus 250 ppm for oils formulated with overbased sulfonates containing molybdenum according to the invention.
There is also a strong reduction in heating due to the reduction in friction provided by the overbased sulfonates according to the invention.
Les conditions d'essai sont les suivantes
- vitesse
- : 1500 tr/minutes
- Durée
- : 1 heure
- Charge
- : 60 Kg
Le tableau 2 donne les résultats obtenus après oxydation du lubrifiant pendant 24 heures à 160°C sous débit d'oxygène 15 l/heure. La cotation est obtenue par détermination du diamètre d'empreinte.
On constate l'effet bénéfique de l'emploi des additifs au molybdène sur les performances antiusure du lubrifiant après oxydation.The test conditions are as follows
- speed
- : 1500 rpm
- Duration
- : 1 hour
- Charge
- : 60 Kg
Table 2 gives the results obtained after oxidation of the lubricant for 24 hours at 160 ° C under an oxygen flow rate of 15 l / hour. The rating is obtained by determining the diameter of the imprint.
The beneficial effect of the use of molybdenum additives on the anti-wear performance of the lubricant after oxidation is noted.
Le test TFOUT (thin film oxygen uptake test) est pratiqué sur les mêmes formulations essence. Il est réalisé à 160°C dans une bombe pressurisée à l'oxygène (90 psi) en présence de catalyseur métallique (Naphténate de Pb, Cu, Fe, Mn et Sn), d'eau et d'essence nitro oxydée de façon à simuler, en partie les conditions auxquelles l'huile peut être soumise dans un moteur à essence. Le tableau 3 donne des valeurs du temps d'induction c'est-à-dire le temps entre le début de l'essai et le début de la chute rapide de pression dans la bombe.The TFOUT test (thin film oxygen uptake test) is performed on the same essence formulations. It is carried out at 160 ° C. in a pressurized oxygen bomb (90 psi) in the presence of metal catalyst (Naphtenate of Pb, Cu, Fe, Mn and Sn), water and nitro petrol oxidized so as to partially simulate the conditions to which oil can be subjected in a petrol engine. Table 3 gives values of the induction time, that is to say the time between the start of the test and the start of the rapid pressure drop in the bomb.
L'augmentation du temps d'induction est significative en présence de l'additif contenant le complexe molybdène-amine.
Les détergents surbasés contenant du molybdène sont ensuite testés dans une formulation lubrifiante pour moteur marin (huile cylindre).The overbased detergents containing molybdenum are then tested in a lubricant formulation for a marine engine (cylinder oil).
La basicité de l'huile est de 70 mg KOH/g dont seulement 20 mg KOH/g apportés par le détergent surbasé.The basicity of the oil is 70 mg KOH / g of which only 20 mg KOH / g provided by the overbased detergent.
L'huile contient en outre 0,5 % de DTPZ.The oil also contains 0.5% DTPZ.
- Conditions
- : Rodage 5 minutes sous 300 lbs
3 heures
Charge 700 lbs (normal load)
Ces conditions sont proches de l'extrême pression. Le tableau 4 permet de constater que l'huile cylindre pour moteurs marin formulée avec les détergents surbasés selon l'invention permet de réduire significativement voire de supprimer totalement l'usure sur machine Falex.
- Conditions
- : Break-in 5 minutes under 300 lbs
3 hours
Load 700 lbs (normal load)
These conditions are close to extreme pressure. Table 4 shows that the cylinder oil for marine engines formulated with the overbased detergents according to the invention makes it possible to significantly reduce or even completely eliminate wear on Falex machines.
Claims (29)
- Over-based additives for lubricating oils, composed of at least one detergent and one carbonate of an alkali metal or an alkaline earth metal in a diluent oil, in the form of a colloidal dispersion of which the micelles include the said carbonate, characterized in that at least one organic molybdenum complex which is practically insoluble in hydrocarbons is incorporated in the micelles of the colloidal dispersion.
- Additives according to Claim 1, characterized in that they include from 0.1 to 10% by weight, preferably from 1 to 4%, of molybdenum.
- Additives according to Claim 1 or Claim 2, characterized in that the organic molybdenum complex is formed with an amine.
- Additives according to any one of Claims 1 to 3, characterized in that the amine-molybdenum complex is prepared by the reaction of a mineral molybdenum compound having acid reactions, with an amine.
- Additives according to Claim 4, characterized in that the mineral molybdenum compound is molybdic acid, an alkali-metal molybdate, sodium hydrogen molybdate, ammonium molybdate, MoOCl₄, MoO₂Br₂, Mo₂O₂Cl₆ or molybdenum trioxide, preferably sodium molybdate or ammonium molybdate.
- Additives according to Claim 4, characterized in that the amine is a primary, secondary or tertiary aliphatic amine.
- Additives according to Claim 6, characterized in that the amine is a primary amine such as oleylamine, stearylamine, dodecylamine, terdodecylamine, ethyl-2-hexylamine, cyclohexylamine, 1-amino-1,1- dimethyldecane and 1-amino-1,1-dimethyldodecane.
- Additives according to Claim 6, characterized in that the amine is a secondary amine of which the total number of carbon atoms does not exceed 12.
- Additives according to Claim 4, characterized in that the amine is an aromatic amine such as paradodecylaniline.
- Additives according to Claim 4, characterized in that the amine is a diamine having a primary amine group.
- Additives according to Claim 10, characterized in that the diamine corresponds to the general formula R₁R₂N-(CH₂)n-NH₂ (I) where R₁ and R₂ are the same or different and represent hydrogen or a linear or branched saturated or unsaturated C₁ to C₃₀, preferably C₈ to C₂₀, aliphatic radical, one of the R₁ and R₂ radicals must necessarily represent an aliphatic radical, and n is between 1 and 8 and preferably between 2 and 4.
- Additives according to Claim 11, characterized in that, in the general formula (I), R₁ is hydrogen and R₂ is a saturated or unsaturated radical derived from fatty acids or mixtures of fatty acids.
- Additives according to Claim 12, characterized in that R₂ corresponds to at least one saturated or unsaturated C₁₂ to C₁₈ alkyl radical.
- Additives according to any one of Claims 3 to 13, characterized in that the atomic ratio of nitrogen to molybdenum in the complex is between 0.25 and 4 and preferably between 0.5 and 2 and its molybdenum content is between 10 and 45% by weight.
- Additives according to any one of Claims 3 to 14, characterized in that the amine-molybdenum complex is prepared by the addition of the amine to an aqueous solution of the mineral molybdenum compound, the temperature being kept between 20 and 100°C, preferably between 50 and 90°C, for 0.5 to 3 hours after the addition of the amine.
- Additives according to Claim 15, characterized in that the reaction medium is neutralized by the addition of a strong mineral acid, preferably sulphuric acid, before or after the introduction of the amine.
- Additives according to Claim 1 or Claim 2, characterized in that the organic molybdenum complex is formed with an oxygenated compound.
- Additives according to Claim 17, characterized in that the oxygenated compound is an alkoxylated amine or polyamine.
- Additives according to Claim 18, characterized in that the amine or polyamine is alkoxylated with ethylene oxide or propylene oxide.
- Additives according to Claim 18 or Claim 19, characterized in that the alkoxylated amine or polyamine is a derivative of diethanolamine or of triethanolamine.
- Additives according to Claim 17, characterized in that the oxygenated compound is a 1,2, 1,3 or 1,4 glycol, preferably ethylene glycol or propylene glycol.
- Additives according to Claim 17, characterized in that the oxygenated compound is a polyol such as glycerol or trimethylolpropane.
- Additives according to any one of Claims 17 to 22, characterized in that the organic molybdenum complex includes between 7 and 60% by weight of molybdenum.
- Additives according to any one of Claims 1 to 23, characterized in that the organic molybdenum complex is used in the sulphurized form.
- Additives according to Claim 24, characterized in that the complex is sulphurised by hydrogen sulphide.
- Method of preparing over-based additives according to Claims 1 to 25 by the carbonation of a mixture including a detergent or a detergent precursor, an alkali-metal or alkaline-earth metal derivative, a nitrogenous and/or oxygenated promoter and, optionally, a hydrocarbon solvent, a diluent oil and/or water, characterized in that the mixture to be carbonated includes at least one organic molybdenum complex which is practically insoluble in hydrocarbons.
- Method according to Claim 26, characterized in that the detergent is selected from sulphonates, phenates, naphthenates, salicylates, phosphonates and thiophsophonates of alkali metals and alkaline earth metals.
- Lubricant composition, characterized in that it includes a lubricating oil of natural or synthetic origin and 0.5 to 40% by weight, preferably from 1 to 30% by weight, of an additive according to Claims 1 to 25.
- Composition according to Claim 28, characterized in that it includes anti-wear, dispersant, and antioxidant additives and polymers for improving viscosity.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8908095A FR2648473B1 (en) | 1989-06-19 | 1989-06-19 | SUB-BASED ADDITIVES FOR LUBRICATING OILS CONTAINING A MOLYBDENE COMPLEX, THEIR PREPARATION PROCESS AND COMPOSITIONS CONTAINING SAID ADDITIVES |
| FR8908095 | 1989-06-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0404650A1 EP0404650A1 (en) | 1990-12-27 |
| EP0404650B1 true EP0404650B1 (en) | 1993-10-27 |
Family
ID=9382866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90401695A Expired - Lifetime EP0404650B1 (en) | 1989-06-19 | 1990-06-15 | Overbased lubricating oil additives containing a molybdenun complex, process of preparation and compositions containing the same |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5143633A (en) |
| EP (1) | EP0404650B1 (en) |
| JP (1) | JP2883167B2 (en) |
| DE (1) | DE69004163T2 (en) |
| ES (1) | ES2060977T3 (en) |
| FR (1) | FR2648473B1 (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3436084A1 (en) * | 1984-10-02 | 1986-04-03 | Karl Pfisterer Elektrotechnische Spezialartikel Gmbh & Co Kg, 7000 Stuttgart | CONNECTING DEVICE FOR A CABLE MEASURING AND TESTING DEVICE |
| WO1996037585A1 (en) * | 1995-05-26 | 1996-11-28 | The Lubrizol Corporation | Lubricants with molybdenum containing compositions and methods of using the same |
| US5650381A (en) * | 1995-11-20 | 1997-07-22 | Ethyl Corporation | Lubricant containing molybdenum compound and secondary diarylamine |
| USRE38929E1 (en) * | 1995-11-20 | 2006-01-03 | Afton Chemical Intangibles Llc | Lubricant containing molybdenum compound and secondary diarylamine |
| GB9807843D0 (en) | 1998-04-09 | 1998-06-10 | Ethyl Petroleum Additives Ltd | Lubricating compositions |
| US6103674A (en) * | 1999-03-15 | 2000-08-15 | Uniroyal Chemical Company, Inc. | Oil-soluble molybdenum multifunctional friction modifier additives for lubricant compositions |
| US6300291B1 (en) | 1999-05-19 | 2001-10-09 | Infineum Usa L.P. | Lubricating oil composition |
| JP2001164281A (en) * | 1999-09-30 | 2001-06-19 | Asahi Denka Kogyo Kk | Lubricant and lubricating composition |
| US6329327B1 (en) * | 1999-09-30 | 2001-12-11 | Asahi Denka Kogyo, K.K. | Lubricant and lubricating composition |
| ATE466921T1 (en) | 1999-12-22 | 2010-05-15 | Lubrizol Corp | LUBRICANT WITH A MIXTURE OF A MOLYBDENUM COMPONENT, PHOSPHORUS COMPONENT AND DISPERSANT |
| US6509303B1 (en) * | 2000-03-23 | 2003-01-21 | Ethyl Corporation | Oil soluble molybdenum additives from the reaction product of fatty oils and monosubstituted alkylene diamines |
| US6528463B1 (en) * | 2000-03-23 | 2003-03-04 | Ethyl Corporation | Oil soluble molybdenum compositions |
| KR100446813B1 (en) * | 2001-01-06 | 2004-09-01 | 이근희 | Bank protection block and method of constructing river side vegetation support using the same |
| JP4066132B2 (en) * | 2001-10-15 | 2008-03-26 | 株式会社Ａｄｅｋａ | Lubricant and lubricating composition |
| US6645921B2 (en) | 2002-02-08 | 2003-11-11 | Ethyl Corporation | Molybdenum-containing lubricant additive compositions, and processes for making and using same |
| JP4078345B2 (en) * | 2004-10-19 | 2008-04-23 | 新日本石油株式会社 | Antioxidant composition and lubricating oil composition using the same |
| EP1803799A4 (en) | 2004-10-19 | 2012-09-05 | Nippon Oil Corp | Lubricant composition and antioxidant composition |
| US7935663B2 (en) | 2007-03-06 | 2011-05-03 | R. T. Vanderbilt Company, Inc. | Molybdenum compounds |
| US7683017B2 (en) | 2007-06-20 | 2010-03-23 | Chevron Oronite Company Llc | Synergistic lubricating oil composition containing a mixture of a nitro-substituted diarylamine and a diarylamine |
| ES2627698T3 (en) * | 2007-10-04 | 2017-07-31 | Infineum International Limited | A lubricating oil composition |
| EP2077315B1 (en) | 2007-12-20 | 2012-10-31 | Chevron Oronite Company LLC | Lubricating oil compositions containing a tetraalkyl-napthalene-1,8 diamine antioxidant and a diarylamine antioxidant |
| KR101114829B1 (en) | 2011-07-21 | 2012-03-13 | (주)엔나노텍 | Lubricant additive composition having excellent wear resistance and method of the composition |
| AU2016307780B2 (en) | 2015-08-14 | 2019-02-21 | Vanderbilt Chemicals, Llc | Additive for lubricant compositions comprising an organomolybdenum compound, and a derivatized triazole |
| CN112175690B (en) * | 2020-09-01 | 2022-04-12 | 清华大学天津高端装备研究院 | Preparation method of non-sulfur-phosphorus oil-soluble organic molybdenum additive |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2795552A (en) * | 1954-06-29 | 1957-06-11 | California Research Corp | Lubricant compositions |
| NL252257A (en) * | 1959-06-05 | |||
| NL281035A (en) * | 1961-07-17 | |||
| US3223625A (en) * | 1963-11-12 | 1965-12-14 | Exxon Research Engineering Co | Colloidal molybdenum complexes and their preparation |
| US3281355A (en) * | 1963-11-15 | 1966-10-25 | Exxon Research Engineering Co | Stable colloidal dispersions of molybdenum sulfide |
| US3541014A (en) * | 1967-07-12 | 1970-11-17 | Lubrizol Corp | Molybdenum-containing lubricant compositions |
| US3496105A (en) * | 1967-07-12 | 1970-02-17 | Lubrizol Corp | Anion exchange process and composition |
| CA1174032A (en) * | 1979-06-28 | 1984-09-11 | John M. King | Process of preparing molybdenum complexes, the complexes so produced and lubricants containing same |
| DE3444553A1 (en) * | 1984-12-06 | 1986-06-12 | Optimol-Ölwerke GmbH, 8000 München | LUBRICANT ADDITION |
| US4692256A (en) * | 1985-06-12 | 1987-09-08 | Asahi Denka Kogyo K.K. | Molybdenum-containing lubricant composition |
| US4601837A (en) * | 1985-09-06 | 1986-07-22 | Amoco Corporation | Process for the preparation of overbased, molybdenum-alkaline earth metal sulfonate dispersions |
-
1989
- 1989-06-19 FR FR8908095A patent/FR2648473B1/en not_active Expired - Fee Related
-
1990
- 1990-06-15 ES ES90401695T patent/ES2060977T3/en not_active Expired - Lifetime
- 1990-06-15 EP EP90401695A patent/EP0404650B1/en not_active Expired - Lifetime
- 1990-06-15 DE DE90401695T patent/DE69004163T2/en not_active Expired - Fee Related
- 1990-06-18 US US07/539,856 patent/US5143633A/en not_active Expired - Lifetime
- 1990-06-19 JP JP2161179A patent/JP2883167B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US5143633A (en) | 1992-09-01 |
| JP2883167B2 (en) | 1999-04-19 |
| EP0404650A1 (en) | 1990-12-27 |
| FR2648473B1 (en) | 1994-04-01 |
| DE69004163D1 (en) | 1993-12-02 |
| JPH0335094A (en) | 1991-02-15 |
| ES2060977T3 (en) | 1994-12-01 |
| FR2648473A1 (en) | 1990-12-21 |
| DE69004163T2 (en) | 1994-05-11 |
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