EP0639634A1 - Colloidal products containing calcium and/or magnesium as well as sulfur and nitrogen, their preparation and their use, especially as additives for lubricants - Google Patents
Colloidal products containing calcium and/or magnesium as well as sulfur and nitrogen, their preparation and their use, especially as additives for lubricants Download PDFInfo
- Publication number
- EP0639634A1 EP0639634A1 EP94401783A EP94401783A EP0639634A1 EP 0639634 A1 EP0639634 A1 EP 0639634A1 EP 94401783 A EP94401783 A EP 94401783A EP 94401783 A EP94401783 A EP 94401783A EP 0639634 A1 EP0639634 A1 EP 0639634A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- mass
- bis
- thiadiazole
- product according
- 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.)
- Granted
Links
- 239000011575 calcium Substances 0.000 title claims description 40
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims description 31
- 229910052791 calcium Inorganic materials 0.000 title claims description 30
- 229910052717 sulfur Inorganic materials 0.000 title claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 18
- 239000011593 sulfur Substances 0.000 title claims description 16
- 239000011777 magnesium Substances 0.000 title claims description 13
- 229910052749 magnesium Inorganic materials 0.000 title claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000000654 additive Substances 0.000 title abstract description 12
- 239000000314 lubricant Substances 0.000 title description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000010687 lubricating oil Substances 0.000 claims abstract description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 6
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 239000000693 micelle Substances 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 60
- -1 1,3,4 - thiadiazole -2,5 - diyl Chemical group 0.000 claims description 23
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229940072033 potash Drugs 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 235000015320 potassium carbonate Nutrition 0.000 claims description 12
- 150000007513 acids Chemical class 0.000 claims description 6
- 235000010338 boric acid Nutrition 0.000 claims description 5
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 3
- 229960001860 salicylate Drugs 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 239000004519 grease Substances 0.000 claims 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 abstract description 2
- 239000001095 magnesium carbonate Substances 0.000 abstract description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 abstract description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 59
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000008096 xylene Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000001914 filtration Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000002480 mineral oil Substances 0.000 description 11
- 235000010446 mineral oil Nutrition 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000003708 ampul Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000005069 Extreme pressure additive Substances 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 239000007866 anti-wear additive Substances 0.000 description 5
- 238000010533 azeotropic distillation Methods 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 230000002085 persistent effect Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- GAWAYYRQGQZKCR-REOHCLBHSA-N (S)-2-chloropropanoic acid Chemical compound C[C@H](Cl)C(O)=O GAWAYYRQGQZKCR-REOHCLBHSA-N 0.000 description 3
- KZZBPNSRBQBVII-UHFFFAOYSA-N 3-[5-(3-hydroxyphenyl)-1,3,4-thiadiazol-2-yl]phenol Chemical compound OC1=CC=CC(C=2SC(=NN=2)C=2C=C(O)C=CC=2)=C1 KZZBPNSRBQBVII-UHFFFAOYSA-N 0.000 description 3
- WSYXFYIAMXEAJT-UHFFFAOYSA-N 3h-dithiadiazole Chemical compound N1SSC=N1 WSYXFYIAMXEAJT-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 229960002645 boric acid Drugs 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GLOYGJPNNKTDIG-UHFFFAOYSA-N SC=1N=NSC=1S Chemical group SC=1N=NSC=1S GLOYGJPNNKTDIG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000005619 boric acid group Chemical class 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent 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
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
-
- 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
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
Definitions
- the present invention relates to new colloidal products containing calcium and / or magnesium, as well as sulfur and nitrogen, their preparation and their use in particular as additives in lubricating oils.
- Overbased detergent additives have been known for a long time. Some of them and their preparation have been described for example in US patents 2,865,956, 3,150,088, 3,537,996, 3,830,739, 3,865,737, 3,953,519, 3,966,621, 4,148,740 and 4,505 .830 and French patent 2,101,813.
- There are variants of the overbasing reaction which use in particular preformed carbonates from alkoxides and CO2 before being brought into contact with the alkaline or alkaline earth salt of the acid compound; they are described in particular in US patents 2,956,018, 3,932,289 and 4,104,180.
- French patent FR-B-2645168 describes thiophosphorus compounds obtained by reaction of a sodium or calcium sulfonate overbased with sodium or calcium carbonate, with a phosphorus sulfide, in general P4S10, this reaction being optionally followed by a reaction with an active hydrogen compound, which could be water, methanol, isopropanol, phenol, acetic acid, dialkylphosphite, boric acid, phosphoric acid, ammonia, an amide, dimercaptothiadiazole, or a derivative thereof.
- the compounds obtained, made soluble in a hydrocarbon medium by micellization can be used as antiwear and extreme pressure additives in lubricating oils.
- French patent FR-B-2681872 describes and claims colloidal products containing boron and phosphorus, obtained by a process in which an alkali or alkaline earth sulfonate borate overbased is prepared; a phosphorus sulfide is reacted on this product and the resulting product is separated. These products are also used as antiwear and extreme pressure additives in lubricating oils and greases. Mention may also be made of French patent FR-B 2689031, which describes and claims colloidal products, which can also be used as antiwear and extreme pressure additives in lubricating oils.
- an overbased detergent compound such as a sulfonate, a phenate, a salicylate or an alkaline or alkaline earth naphthenate overbased with a carbonate or an alkali or alkaline earth hydroxide
- each number a is 1 or 2
- x and z are each 1 or 2
- y is zero or 1.
- the sulfonates and / or phenates and / or overbased salycilates used as basic products for the preparation of the colloidal products of the invention have an alkaline reserve in the form of calcium or magnesium carbonate corresponding to a TBN (or base index total) which can go up to approximately 600 mg KOH / g of product.
- the dicarboxylic acids used for the preparation of the colloidal products of the invention can be obtained in particular by reaction of a compound containing a dimercaptothiadiazole group of general formula: with at least one substituted monocarboxylic acid of general formula: (III) X- (CH2) a -COOH optionally in the presence of elemental sulfur.
- y , n and a each have the same meaning as in formula (I) (Cf above) and X represents a halogen atom, for example chlorine, bromine, iodine or fluorine or a nitro group.
- the reaction described above can be carried out in a basic medium, for example, in the presence of an alkali metal hydroxide (in particular sodium hydroxide or potassium hydroxide), or ammonium hydroxide.
- an alkali metal hydroxide in particular sodium hydroxide or potassium hydroxide
- ammonium hydroxide At the end of the reaction, neutralization in a strong acid medium, such as for example hydrochloric acid, sulfuric acid or phosphoric acid will generally be carried out.
- the dicarboxylic acid obtained corresponds to the following general formula: which corresponds to formula (I) in which a would be replaced by c + 2 and x and z would each be equal to 1.
- the modification of the overbased sulfonates by the dicarboxylic acids defined above consists in at least partial neutralization of their basicity reserve (TBN).
- the preparation of the colloidal products according to the invention is generally carried out in an organic solvent which can more particularly consist of an aliphatic hydrocarbon (such as for example a hexane, a heptane, an octane or a nonane), a hydrocarbon cycloaliphatic (such as, for example, cyclohexane), an aromatic hydrocarbon (such as, for example, toluene or a xylene), optionally combined with tetrahydrofuran or methanol, used as co-solvents.
- an organic solvent which can more particularly consist of an aliphatic hydrocarbon (such as for example a hexane, a heptane, an octane or a nonane), a hydrocarbon cycloaliphatic (such as, for example, cyclohexane), an aromatic hydrocarbon (such as, for example, toluene or a xylene), optionally combined with tetrahydrofur
- a modification of the overbased sulfonate can be carried out jointly by reaction with other acids or various reagents which can be brought into play before or after sulfuric and nitrogenous dicarboxylic acid or at the same time as this.
- the additional acids and reagents considered can be for example metaboric or orthoboric acids, carboxylic acids containing sulfur such as those described in the French patent application EN 92/03 789 already cited above, or also phosphoric and alkyl acids and / or phosphoric aryls.
- the colloidal products obtained are stable, soluble in mineral and synthetic lubricants and are characterized by their nitrogen, sulfur and possibly boron content and by their calcium and / or magnesium content.
- Their sulfur content in the active material can range up to about 30% by mass and the nitrogen content up to approximately 15% by mass.
- Their calcium content in the active ingredient can range, for example, up to about 30% by mass and the magnesium content up to approximately 20% by mass.
- the colloidal nature of the products of the invention is checked by dialysis through a latex membrane.
- the nitrogen and sulfur analyzes locate these elements in the fraction that has not been dialyzed (concentrate) which constitutes the colloidal part of the additive.
- the colloidal compounds containing sulfur and nitrogen according to the invention constitute excellent antiwear and extreme pressure additives.
- Antiwear and extreme pressure additives are incorporated into lubricants when they are intended to lubricate organs subjected to significant mechanical stresses, such as distribution in heat engines, gears, bearings or stops. Significant mechanical stresses also appear during the machining of metals, whether cutting or forming.
- colloidal compounds containing sulfur and nitrogen according to the invention are endowed with great thermal stability, which authorizes their use in lubricants subjected in service at very high temperatures which can reach 160 ° C., such as in some severe engine housings, in heavily loaded transmissions or high speed metal cutting.
- the products of the invention as additives for lubricating oils and greases, they can be incorporated into them, for example at an active material concentration of 0.1 to 25% by mass, preferably from 1 to 15 % by mass.
- Lubricating oils generally also contain one or more other additives such as additives improving the viscosity index, additives for lowering the pour point, antioxidants, anti-rust, anti-corrosion additives of copper, detergents, antiwear, antifoam, dispersants, friction reducers, with which the products of the invention are compatible.
- Examples A to F the synthesis of various acids which can be used in the preparation of the products according to the invention described in Examples 1 to 11 is described.
- Examples 12 and 13 describe tests carried out on some of these products.
- the product has the following characteristics (mass%):
- an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
- the medium is brought to 90 ° C. and then a solution of 5.93 g (0.0223 mole or 0.0446 acid equivalent) of 3.3 'acid is introduced over 1 hour using the ampoule.
- an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
- the medium is brought to 90 ° C. and then a solution of 6.55 g (0.0223 mole or 0.0446 acid equivalent) of 4.4 'acid is introduced over 1 hour using the ampoule.
- an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
- an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
- an overbased alkaline reserve magnesium sulfonate (TBN) equivalent to 400 are introduced into a reactor equipped with a stirrer, a condenser, a Dean & Stark separator and a dropping funnel.
- the medium is brought to 90 ° C. and then a solution of 6.3 g (0.0237 mol or 0.0474 acid equivalent) of 3.3 ′ acid is introduced over the course of one hour using the bulb.
- an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
- the medium is brought to 130 ° C. and then a solution of 10.8 g of an alkylarylsulfonic acid with a molar mass equivalent to 700 (or 0.0154 acid equivalent) in 100 cm3 of xylene is introduced over 30 minutes at this temperature.
- an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
- the medium is brought to 130 ° C. and then a solution of 10.8 g of an alkylarylsulfonic acid with a molar mass equivalent to 700 (or 0.0154 acid equivalent) in 100 cm3 of xylene is introduced over 30 minutes at this temperature.
- an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
- the medium is brought to 130 ° C. and then a solution of 10.8 g is introduced over 30 minutes at this temperature.
- an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
- the medium is brought to 130 ° C. and then a solution of 63.4 g of an alkylarylsulfonic acid with a molar mass equivalent to 700 (or 0.09 acid equivalent) in 100 cm3 of xylene is introduced over 30 minutes at this temperature.
- an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
- 4.11 g of orthoboric acid (0.066 mol) dispersed in 30 cm3 of methanol are introduced and then the medium is brought to reflux for 1 hour. After azeotropic distillation of methanol and of the reaction water formed, the medium is cooled to 90 ° C.
- an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
- the medium is brought to 90 ° C. and then a solution of 5.98 g (0.0167 mole or 0.0334 acid equivalent) of 5.5 'acid is introduced over 1 hour using the ampoule.
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Abstract
Description
La présente invention concerne de nouveaux produits colloïdaux renfermant du calcium et/ou du magnésium, ainsi que du soufre et de l'azote, leur préparation et leur utilisation notamment comme additifs dans les huiles lubrifiantes.The present invention relates to new colloidal products containing calcium and / or magnesium, as well as sulfur and nitrogen, their preparation and their use in particular as additives in lubricating oils.
Les additifs détergents surbasiques sont connus depuis longtemps. Certains d'entre eux et leur préparation ont été décrits par exemple dans les brevets US 2.865.956, 3.150.088, 3.537.996, 3.830.739, 3.865.737, 3.953.519, 3.966.621, 4.148.740 et 4.505.830 et le brevet français 2.101.813. Il existe des variantes de la réaction de surbasification qui font notamment appel à des carbonates préformés à partir d'alcoxydes et de CO₂ avant la mise en contact avec le sel alcalin ou alcalino-terreux du composé acide ; elles sont décrites notamment dans les brevets US 2.956.018, 3.932.289 et 4.104.180.Overbased detergent additives have been known for a long time. Some of them and their preparation have been described for example in US patents 2,865,956, 3,150,088, 3,537,996, 3,830,739, 3,865,737, 3,953,519, 3,966,621, 4,148,740 and 4,505 .830 and French patent 2,101,813. There are variants of the overbasing reaction which use in particular preformed carbonates from alkoxides and CO₂ before being brought into contact with the alkaline or alkaline earth salt of the acid compound; they are described in particular in US patents 2,956,018, 3,932,289 and 4,104,180.
Il est également connu de modifier des additifs détergents surbasiques par incorporation de dérivés du bore, comme décrit par exemple dans les brevets US 3.907.691, 3.929.650, 4.965.003 et 4.965.004.It is also known to modify overbased detergent additives by incorporating boron derivatives, as described for example in US patents 3,907,691, 3,929,650, 4,965,003 and 4,965,004.
Enfin, la modification d'additifs détergents surbasiques par certains acides carboxyliques, des acides boriques ou des acides phosphoriques a également été décrite dans le brevet US 4.328.111.Finally, the modification of overbased detergent additives by certain carboxylic acids, boric acids or phosphoric acids has also been described in US Pat. No. 4,328,111.
Par ailleurs, le brevet français FR-B-2645168 décrit des composés thiophosphorés obtenus par réaction d'un sulfonate de sodium ou de calcium surbasifié par du carbonate de sodium ou de calcium, avec un sulfure de phosphore, en général P₄S₁₀, cette réaction étant éventuellement suivie d'une réaction avec un composé à hydrogène actif, qui pouvait être l'eau, le méthanol, l'isopropanol, un phénol, l'acide acétique, un dialkylphosphite, l'acide borique, l'acide phosphorique, l'ammoniac, un amide, le dimercaptothiadiazole, ou un de ses dérivés. Les composés obtenus rendus solubles en milieu hydrocarboné par micellisation, sont utilisables comme additifs antiusure et extrême-pression dans les huiles lubrifiantes.Furthermore, French patent FR-B-2645168 describes thiophosphorus compounds obtained by reaction of a sodium or calcium sulfonate overbased with sodium or calcium carbonate, with a phosphorus sulfide, in general P₄S₁₀, this reaction being optionally followed by a reaction with an active hydrogen compound, which could be water, methanol, isopropanol, phenol, acetic acid, dialkylphosphite, boric acid, phosphoric acid, ammonia, an amide, dimercaptothiadiazole, or a derivative thereof. The compounds obtained, made soluble in a hydrocarbon medium by micellization, can be used as antiwear and extreme pressure additives in lubricating oils.
En outre, le brevet français FR-B-2681872 décrit et revendique des produits colloïdaux contenant du bore et du phosphore, obtenus par un procédé dans lequel on prépare un sulfonate alcalin ou alcalino-terreux surbasique boraté ; on fait réagir sur ce produit un sulfure de phosphore et on sépare le produit résultant. Ces produits sont également utilisés comme additifs antiusure et extrême-pression dans les huiles et graisses lubrifiantes. On peut encore citer le brevet français FR-B 2689031, qui décrit et revendique des produits colloïdaux, eux aussi utilisables comme additifs antiusure et extrême-pression dans les huiles lubrifiantes. Ils sont définis comme étant obtenus par réaction d'un composé détergent surbasé (tel qu'un sulfonate, un phénate, un salicylate ou un naphténate alcalin ou alcalino-terreux surbasé par un carbonate ou un hydroxyde alcalin ou alcalino-terreux) avec un acide carboxylique soufré.In addition, French patent FR-B-2681872 describes and claims colloidal products containing boron and phosphorus, obtained by a process in which an alkali or alkaline earth sulfonate borate overbased is prepared; a phosphorus sulfide is reacted on this product and the resulting product is separated. These products are also used as antiwear and extreme pressure additives in lubricating oils and greases. Mention may also be made of French patent FR-B 2689031, which describes and claims colloidal products, which can also be used as antiwear and extreme pressure additives in lubricating oils. They are defined as being obtained by reaction of an overbased detergent compound (such as a sulfonate, a phenate, a salicylate or an alkaline or alkaline earth naphthenate overbased with a carbonate or an alkali or alkaline earth hydroxide) with an acid sulfur carboxylic.
On a maintenant découvert, et c'est l'un des objets de la présente invention, qu'il était possible de préparer de nouveaux produits colloïdaux contenant du calcium et/ou du magnésium, ainsi que du soufre et de l'azote, par modification de produits colloïdaux comprenant un sulfonate surbasique et/ou un phénate surbasique et/ou un salycilate surbasique chargé de carbonate de calcium et/ou de magnésium sous la forme de micelles, ladite modification consistant en une réaction de neutralisation partielle ou totale de la réserve de basicité (représentée par le TBN ou indice de base total du produit) des micelles au moyen d'au moins un acide dicarboxylique répondant à la formule générale suivante :
dans laquelle les symboles a représentent chacun indépendamment l'un de l'autre un nombre entier de 1 à 8, x et z représentent chacun séparément un nombre de 1 à 4, y représente un nombre entier de 0 à 4 et n prend la valeur 1 ou 2; en particulier, quand n a la valeur 1, g est en général 0; et quand n a la valeur 2 y peut être 1 ou plus.It has now been discovered, and this is one of the objects of the present invention, that it is possible to prepare new colloidal products containing calcium and / or magnesium, as well as sulfur and nitrogen, by modification of colloidal products comprising an overbased sulfonate and / or an overbased phenate and / or an overbased salycilate charged with calcium carbonate and / or magnesium in the form of micelles, said modification consisting in a reaction of partial or total neutralization of the reserve of basicity (represented by the TBN or total base index of the product) of the micelles by means of at least one dicarboxylic acid corresponding to the following general formula:
in which the symbols a each independently represent an integer from 1 to 8, x and z each independently represent a number from 1 to 4, y represents an integer from 0 to 4 and n takes the value 1 or 2; in particular, when na has the value 1, g is generally 0; and when na the value 2 y can be 1 or more.
Plus particulièrement encore dans la formule (I), chaque nombre a est 1 ou 2, x et z sont chacun 1 ou 2 et y est zéro ou 1.More particularly still in formula (I), each number a is 1 or 2, x and z are each 1 or 2 and y is zero or 1.
Les sulfonates et/ou les phénates et/ou les salycilates surbasiques utilisés comme produits de base pour la préparation des produits colloïdaux de l'invention ont une réserve alcaline sous forme de carbonate de calcium ou de magnésium correspondant à un TBN (ou indice de base total) qui peut aller jusqu'à environ 600 mg KOH/g de produit.
Les acides dicarboxyliques mis en jeu pour la préparation des produits colloïdaux de l'invention peuvent être obtenus notamment par réaction d'un composé à groupement dimercaptothiadiazole de formule générale :
avec au moins un acide monocarboxylique substitué de formule générale :
(III) X-(CH₂)a-COOH éventuellement en présence de soufre élémentaire. Dans les formules (II) et (III), y, n et a ont chacun la même signification que dans la formule (I) (Cf supra) et X représente un atome d'halogène, par exemple chlore, brome, iode ou fluor ou un groupement nitro.The sulfonates and / or phenates and / or overbased salycilates used as basic products for the preparation of the colloidal products of the invention have an alkaline reserve in the form of calcium or magnesium carbonate corresponding to a TBN (or base index total) which can go up to approximately 600 mg KOH / g of product.
The dicarboxylic acids used for the preparation of the colloidal products of the invention can be obtained in particular by reaction of a compound containing a dimercaptothiadiazole group of general formula:
with at least one substituted monocarboxylic acid of general formula:
(III) X- (CH₂) a -COOH optionally in the presence of elemental sulfur. In formulas (II) and (III), y , n and a each have the same meaning as in formula (I) (Cf above) and X represents a halogen atom, for example chlorine, bromine, iodine or fluorine or a nitro group.
Lorsque l'on met en jeu du soufre élémentaire la proportion considérée est de x + z - 2 atome-gramme par mole de composé de formule (II), x et z étant définis comme dans la formule (I). On remarque que si x et z sont chacun égaux à 1, la quantité de soufre élémentaire à mettre en jeu est nulle.When elemental sulfur is brought into play the proportion considered is x + z - 2 gram atoms per mole of compound of formula (II), x and z being defined as in formula (I). We note that if x and z are each equal to 1, the quantity of elemental sulfur to be brought into play is zero.
La réaction décrite ci-dessus peut être réalisée en milieu basique, par exemple, en présence d'un hydroxyde de métal alcalin (en particulier soude ou potasse), ou d'hydroxyde d'ammonium. En fin de réaction, une neutralisation en milieu acide fort, tel que par exemple l'acide chlorhydrique, l'acide sulfurique ou l'acide phosphorique sera en général effectuée.The reaction described above can be carried out in a basic medium, for example, in the presence of an alkali metal hydroxide (in particular sodium hydroxide or potassium hydroxide), or ammonium hydroxide. At the end of the reaction, neutralization in a strong acid medium, such as for example hydrochloric acid, sulfuric acid or phosphoric acid will generally be carried out.
Une autre méthode pouvant conduire à certains des acides dicarboxyliques de formule (I), en particulier ceux dans lesquels chaque a prend une valeur de 2 à 8 consiste à faire réagir sur un composé répondant à la formule (II) un acide monocarboxylique insaturé de formule générale (IV) H₂C = CH-(CH₂)c-COOH dans laquelle c a une valeur entière de 0 à 6. L'acide dicarboxylique obtenu répond à la formule générale suivante :
qui correspond à la formule (I) dans laquelle a serait remplacé par c + 2 et x et z seraient chacun égaux à 1.Another method which can lead to some of the dicarboxylic acids of formula (I), in particular those in which each a takes a value of 2 to 8, consists in reacting on a compound corresponding to formula (II) an unsaturated monocarboxylic acid of formula general (IV) H₂C = CH- (CH₂) c -COOH in which c has a integer value from 0 to 6. The dicarboxylic acid obtained corresponds to the following general formula:
which corresponds to formula (I) in which a would be replaced by c + 2 and x and z would each be equal to 1.
Comme exemples d'acides dicarboxyliques de formule (I) que l'on peut utiliser dans la préparation des produits colloïdaux de l'invention, on peut citer :
- · l'acide 3,3' -(1,3,4 - thiadiazole -2,5 - diyl) bis (3-thiapropanoïque) ;
- · l'acide 4,4' -(1,3,4 - thiadiazole -2,5 - diyl) bis (4-thiabutanoïque) ;
- · l'acide 4,4' -(1,3,4 - thiadiazole -2,5 - diyl) bis (3,4-dithiabutanoïque) ;
- · l'acide 5,5' -(1,3,4 - thiadiazode -2,5 -diyl) bis (4,5-dithiapentanoïque)
- · l'acide bis (3-(5 thio-1,3,4-thiadiazole-2-yl)-3-thiapropanoïque) ;
- · et l'acide bis (4-(5 thio-1,3,4-thiadiazole-2-yl)-4-thiabutanoïque).
- 3.3 '- (1,3,4 - thiadiazole -2,5 - diyl) bis (3-thiapropanoic) acid;
- · 4.4 '- (1,3,4 - thiadiazole -2,5 - diyl) bis (4-thiabutanoic) acid;
- 4.4 '- (1,3,4 - thiadiazole -2,5 - diyl) bis (3,4-dithiabutanoic) acid;
- 5.5 '- (1,3,4 - thiadiazode -2,5 -diyl) bis (4,5-dithiapentanoic) acid
- Bis (3- (5 thio-1,3,4-thiadiazole-2-yl) -3-thiapropanoic acid);
- And bis (4- (5 thio-1,3,4-thiadiazole-2-yl) -4-thiabutanoic acid).
Certains acides répondant à la formule (I) ont déjà été décrits antérieurement. Ainsi par exemple le document DE-A-1921 740 décrit une méthode de synthèse des composés de formule :
Les documents EP-A-146 087 et US-A-4.371.610 décrivent l'utilisation de tels composés dans des procédés photographiques.The documents EP-A-146 087 and US-A-4 371 610 describe the use of such compounds in photographic processes.
La modification des sulfonates surbasiques par les acides dicarboxyliques définis ci-dessus consiste en une neutralisation au moins partielle de leur réserve de basicité (TBN).The modification of the overbased sulfonates by the dicarboxylic acids defined above consists in at least partial neutralization of their basicity reserve (TBN).
La préparation des produits colloïdaux selon l'invention est en général réalisée au sein d'un solvant organique qui peut consister plus particulièrement en un hydrocarbure aliphatique (tel par exemple qu'un hexane, un heptane, un octane ou un nonane), un hydrocarbure cycloaliphatique (tel par exemple que le cyclohexane), un hydrocarbure aromatique (tel par exemple que le toluène ou un xylène), éventuellement associés à du tétrahydrofuranne ou du méthanol, utilisés comme co-solvants.The preparation of the colloidal products according to the invention is generally carried out in an organic solvent which can more particularly consist of an aliphatic hydrocarbon (such as for example a hexane, a heptane, an octane or a nonane), a hydrocarbon cycloaliphatic (such as, for example, cyclohexane), an aromatic hydrocarbon (such as, for example, toluene or a xylene), optionally combined with tetrahydrofuran or methanol, used as co-solvents.
Lorsque la neutralisation est partielle, on peut réaliser conjointement une modification du sulfonate surbasique par réaction avec d'autres acides ou divers réactifs qui peuvent être mis en jeu avant ou après l'acide dicarboxylique soufré et azoté ou en même temps que celui-ci.When the neutralization is partial, a modification of the overbased sulfonate can be carried out jointly by reaction with other acids or various reagents which can be brought into play before or after sulfuric and nitrogenous dicarboxylic acid or at the same time as this.
Les acides et réactifs additionnels considérés peuvent être par exemple les acides métaborique ou orthoborique, des acides carboxyliques renfermant du soufre tels que ceux décrits dans la demande de brevet français E.N. 92/03 789 déjà citée plus haut, ou encore les acides phosphoriques et alkyles et/ou aryles phosphoriques.The additional acids and reagents considered can be for example metaboric or orthoboric acids, carboxylic acids containing sulfur such as those described in the French patent application EN 92/03 789 already cited above, or also phosphoric and alkyl acids and / or phosphoric aryls.
Les produits colloïdaux obtenus sont stables, solubles dans les lubrifiants minéraux et synthétiques et sont caractérisés par leur teneur en azote, en soufre et éventuellement en bore et par leur teneur en calcium et/ou en magnésium.The colloidal products obtained are stable, soluble in mineral and synthetic lubricants and are characterized by their nitrogen, sulfur and possibly boron content and by their calcium and / or magnesium content.
Leur teneur en soufre dans la matière active peut aller jusqu'à environ 30 % en masse et la teneur en azote jusqu'à environ 15 % en masse.Their sulfur content in the active material can range up to about 30% by mass and the nitrogen content up to approximately 15% by mass.
Leur teneur en calcium dans la matière active peut aller par exemple jusqu'à environ 30 % en masse et la teneur en magnésium jusqu'à environ 20 % en masse.Their calcium content in the active ingredient can range, for example, up to about 30% by mass and the magnesium content up to approximately 20% by mass.
Le caractère colloïdal des produits de l'invention est vérifié par dialyse à travers une membrane en latex. Les analyses d'azote et de soufre localisent ces éléments dans la fraction n'ayant pas dialysé (concentrat) qui constitue la partie colloïdale de l'additif.The colloidal nature of the products of the invention is checked by dialysis through a latex membrane. The nitrogen and sulfur analyzes locate these elements in the fraction that has not been dialyzed (concentrate) which constitutes the colloidal part of the additive.
Les composés colloïdaux renfermant du soufre et de l'azote selon l'invention constituent d'excellents additifs antiusure et extrême-pression. Les additifs antiusure et extrême-pression sont incorporés aux lubrifiants lorsque ceux-ci sont destinés à lubrifier des organes soumis à des contraintes mécaniques importantes, tels que la distribution dans les moteurs thermiques, les engrenages, les roulements ou les butées. Des contraintes mécaniques importantes apparaissent également lors de l'usinage des métaux, qu'il s'agisse de coupe ou de formage.The colloidal compounds containing sulfur and nitrogen according to the invention constitute excellent antiwear and extreme pressure additives. Antiwear and extreme pressure additives are incorporated into lubricants when they are intended to lubricate organs subjected to significant mechanical stresses, such as distribution in heat engines, gears, bearings or stops. Significant mechanical stresses also appear during the machining of metals, whether cutting or forming.
En outre, les composés colloïdaux renfermant du soufre et de l'azote selon l'invention sont doués d'une grande stabilité thermique, ce qui autorise leur emploi dans les lubrifiants soumis en service à des températures très élevées pouvant atteindre 160 °C, comme dans certains carters de moteurs sévères, dans des transmissions très chargées ou la coupe de métaux à grande vitesse.In addition, the colloidal compounds containing sulfur and nitrogen according to the invention are endowed with great thermal stability, which authorizes their use in lubricants subjected in service at very high temperatures which can reach 160 ° C., such as in some severe engine housings, in heavily loaded transmissions or high speed metal cutting.
Dans l'utilisation des produits de l'invention comme additifs pour huiles lubrifiantes et graisses, on peut les incorporer à celles-ci par exemple à une concentration en matière active de 0,1 à 25 % en masse, de préférence de 1 à 15 % en masse.In the use of the products of the invention as additives for lubricating oils and greases, they can be incorporated into them, for example at an active material concentration of 0.1 to 25% by mass, preferably from 1 to 15 % by mass.
Les huiles lubrifiantes (ou les graisses) contiennent en outre en général un ou plusieurs autres additifs tels que les additifs améliorant l'indice de viscosité, des additifs d'abaissement du point d'écoulement, des antioxydants, des antirouille, des additifs anticorrosion du cuivre, des détergents, des antiusure, des antimousse, des dispersants, des réducteurs de frottements, avec lesquels les produits de l'invention sont compatibles.Lubricating oils (or greases) generally also contain one or more other additives such as additives improving the viscosity index, additives for lowering the pour point, antioxidants, anti-rust, anti-corrosion additives of copper, detergents, antiwear, antifoam, dispersants, friction reducers, with which the products of the invention are compatible.
Les exemples suivants illustrent l'invention. Dans les exemples A à F, on décrit la synthèse de divers acides utilisables dans la préparation des produits selon l'invention décrite dans les exemples 1 à 11. Les exemples 12 et 13 décrivent des tests effectués sur certains de ces produits.The following examples illustrate the invention. In Examples A to F, the synthesis of various acids which can be used in the preparation of the products according to the invention described in Examples 1 to 11 is described. Examples 12 and 13 describe tests carried out on some of these products.
À une solution de 15,0 g (0,1 mole) de dimercapto-2,2'-thiadiazole et 8,0 g (0,2 mole) de soude dans 100 cm³ d'eau, on ajoute à température ambiante en 2 heures une solution de 18,9 g (0,2 mole) d'acide chloroacétique, 8,0 g (0,2 mole) de soude dans 100 cm³ d'eau. Après une heure supplémentaire à température ambiante, le milieu est porté à 90 °C pendant 2 heures, puis, après retour à la température ambiante, on introduit sous agitation de l'acide chlorhydrique concentré jusqu'à apparition d'un pH acide persistant. On procède alors à la filtration du précipité obtenu. Après lavage à l'eau et séchage, on isole 21,5 g (92 %) de produit.To a solution of 15.0 g (0.1 mole) of dimercapto-2,2'-thiadiazole and 8.0 g (0.2 mole) of sodium hydroxide in 100 cm³ of water, the mixture is added at room temperature in 2 hours one solution of 18.9 g (0.2 mole) of chloroacetic acid, 8.0 g (0.2 mole) of soda in 100 cm³ of water. After an additional hour at ambient temperature, the medium is brought to 90 ° C. for 2 hours, then, after returning to ambient temperature, concentrated hydrochloric acid is introduced with stirring until a persistent acid pH appears. The precipitate obtained is then filtered. After washing with water and drying, 21.5 g (92%) of product are isolated.
Le produit présente les caractéristiques suivantes (% masse) :
À une solution de 15,0 g (0,1 mole) de dimercapto-2,2'-thiadiazole et 8,0 g (0,2 mole) de soude dans 100 cm³ d'eau , on ajoute à température ambiante en 2 heures une solution de 32.5 g (0,3 mole) d'acide chloropropionique,12,0 g (0,3 mole) de soude dans 100 cm³ d'eau. Après une heure supplémentaire à température ambiante, le milieu est porté à 90 °C pendant 2 heures, puis après retour à la température ambiante, on introduit sous agitation de l'acide chlorhydrique concentré jusqu'à apparition d'un pH acide persistant. On procède alors à la filtration du précipité obtenu. Après lavage à l'eau et séchage, on isole 28,8 g (98 %) de produit.To a solution of 15.0 g (0.1 mole) of dimercapto-2,2'-thiadiazole and 8.0 g (0.2 mole) of sodium hydroxide in 100 cm³ of water, the mixture is added at room temperature in 2 hours a solution of 32.5 g (0.3 mole) of chloropropionic acid, 12.0 g (0.3 mole) of soda in 100 cm³ of water. After an additional hour at ambient temperature, the medium is brought to 90 ° C. for 2 hours, then after returning to ambient temperature, concentrated hydrochloric acid is introduced with stirring until a persistent acid pH appears. The precipitate obtained is then filtered. After washing with water and drying, 28.8 g (98%) of product are isolated.
Le produit présente les caractéristiques suivantes (% masse) :
À une solution de 15,0 g (0,1 mole) de dimercapto 2,2' dithiadiazole dans 250 cm³ d'eau et 50 cm³ d'éthanol, on ajoute, à température ambiante, en 30 minutes, une solution de 21,6 g (0,3 mole) d'acide acrylique, 12,0 g (0,3 mole) de soude et 25 mg de paraméthoxyphénol dans 250 cm³ d'eau. On porte ensuite le milieu à reflux pendant 3 heures, puis, après retour à la température ambiante, on ajoute de l'acide chlorhydrique concentré jusqu'à apparition d'un pH acide. On procède à la filtration et au lavage à l'eau du précipité blanc obtenu. Après séchage on recueille 25,5 g (87 %) de produit.To a solution of 15.0 g (0.1 mole) of dimercapto 2,2 'dithiadiazole in 250 cm³ of water and 50 cm³ of ethanol, a solution of 21 is added at room temperature over 30 minutes, 6 g (0.3 mole) of acrylic acid, 12.0 g (0.3 mole) of sodium hydroxide and 25 mg of paramethoxyphenol in 250 cm³ of water. The medium is then brought to reflux for 3 hours, then, after returning to ambient temperature, concentrated hydrochloric acid is added until an acidic pH appears. The white precipitate obtained is filtered and washed with water. After drying, 25.5 g (87%) of product are collected.
Le produit présente les caractéristiques suivantes (% masse) :
À une dispersion de 29,8 g (0,1 mole) de dimercapto-2,2' dithiadiazole dans 100 cm³ d'eau et 100 cm³ de méthanol en présence de 8,0 g (0,2 mole) de soude, on ajoute à température ambiante en 2 heures une solution de 28,9 g (0,3 mole) d'acide chloroacétique, 12,0 g (0,3 mole) de soude dans 100 cm³ d'eau. Après une heure supplémentaire à température ambiante, le milieu est porté à reflux pendant 2 heures, puis, après retour à la température ambiante, on introduit sous agitation de l'acide chlorhydrique concentré jusqu'à apparition d'un pH acide persistant. Après évaporation du méthanol, on procède à la filtration du précipité obtenu. Après lavage à l'eau et séchage, on isole 32,6 g (79 %) de produit.To a dispersion of 29.8 g (0.1 mole) of dimercapto-2,2 'dithiadiazole in 100 cm³ of water and 100 cm³ of methanol in the presence of 8.0 g (0.2 mole) of sodium hydroxide, add at room temperature over 2 hours a solution of 28.9 g (0.3 mole) of chloroacetic acid, 12.0 g (0.3 mole) of sodium hydroxide in 100 cm³ of water. After an additional hour at ambient temperature, the medium is brought to reflux for 2 hours, then, after returning to ambient temperature, concentrated hydrochloric acid is introduced with stirring until a persistent acid pH appears. After evaporation of the methanol, the precipitate obtained is filtered. After washing with water and drying, 32.6 g (79%) of product are isolated.
Le produit présente les caractéristiques suivantes (% masse) :
À une dispersion de 29,8 g (0,1 mole) de dimercapto- 2,2' dithiadiazole dans 100 cm³ d'eau et 100 cm³ de méthanol en présence de 8,0 g (0,2 mole) de soude, on ajoute à température ambiante en 2 heures une solution de 32,5 g (0,3 mole) d'acide chloropropionique, 12,0 g (0,3 mole) de soude dans 100 cm³ d'eau. Après une heure supplémentaire à température ambiante, le milieu est porté à reflux pendant 2 heures, puis, après retour à la température ambiante, on introduit sous agitation de l'acide chlorhydrique concentré jusqu'à apparition d'un pH acide persistant. Après évaporation du méthanol, on procède à la filtration du précipité obtenu. Après lavage à l'eau et séchage, on isole un produit présentant les caractéristiques suivantes (% masse) :
À une solution de 15,0 g (0,1 mole) de dimercapto-2,2'-thiadiazole et 8,0 g (0,2 mole) de soude dans 100 cm³ d'eau, on ajoute une solution de 6,4 g (0,2mole) de soufre dans 40 cm³ d'éthanolamine, puis à température ambiante en 2 heures 32.5 g (0,3 mole) d'acide chloropropionique ,12,0 g (0,3 mole) de soude dans 100 cm³ d'eau. Après une heure supplémentaire à température ambiante, le milieu est porté à 90 °C pendant 2 heures, puis, après retour à la température ambiante, on introduit sous agitation de l'acide chlorhydrique concentré jusqu'à apparition d'un pH acide persistant. On procède alors à l'extraction du milieu par deux fois 150 cm³ d'éther éthylique. Après lavage à l'eau et séchage de la phase éthérée, on isole 28,8 g (98 %) de produit.To a solution of 15.0 g (0.1 mole) of dimercapto-2,2'-thiadiazole and 8.0 g (0.2 mole) of sodium hydroxide in 100 cm³ of water, a solution of 6 is added, 4 g (0.2 mole) of sulfur in 40 cm³ of ethanolamine, then at room temperature in 2 hours 32.5 g (0.3 mole) of chloropropionic acid, 12.0 g (0.3 mole) of soda in 100 cm³ of water. After an additional hour at ambient temperature, the medium is brought to 90 ° C. for 2 hours, then, after returning to ambient temperature, concentrated hydrochloric acid is introduced with stirring until a persistent acid pH appears. The medium is then extracted with twice 150 cm³ of ethyl ether. After washing with water and drying the ethereal phase, 28.8 g (98%) of product are isolated.
Le produit présente les caractéristiques suivantes (% masse) :
Dans un réacteur équipé d'un agitateur, d'un condenseur, d'un séparateur de Dean & Stark et d'une ampoule de coulée, on introduit 50 g d'un sulfonate de calcium surbasique de réserve alcaline (TBN) équivalente à 500 milliéquivalents de potasse par gramme de produit et contenant 18,70 % de calcium soit 0.4456 équivalent basique, 15 g d'une huile minérale 130 Neutral et 300 cm³ de xylène. On porte le milieu à 90 °C puis on introduit en 1 heure à l'aide de l'ampoule une solution de 5,93 g ( 0,0223 mole soit 0,0446 équivalent acide) d'acide 3,3'-(1,3,4-thiadiazole-2,5-diyl) bis (3-thiapropanoïque) dans 70cm³ de tétrahydrofuranne. On maintient le milieu à cette température une heure supplémentaire, puis on distille le tétrahydrofuranne et l'eau de réaction .Après filtration, on procède à l'évaporation du xylène sous pression réduite. On recueille un produit liquide et limpide dont la composition en masse est la suivante :
Ca= 13,1 % S= 4,9% N= 0,8%50 g of an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel. milliequivalents of potash per gram of product and containing 18.70% of calcium, ie 0.4456 basic equivalent, 15 g of a 130 Neutral mineral oil and 300 cm³ of xylene. The medium is brought to 90 ° C. and then a solution of 5.93 g (0.0223 mole or 0.0446 acid equivalent) of 3.3 'acid is introduced over 1 hour using the ampoule. 1,3,4-thiadiazole-2,5-diyl) bis (3-thiapropanoic) in 70cm³ of tetrahydrofuran. The medium is maintained at this temperature for an additional hour, then the tetrahydrofuran and the reaction water are distilled. After filtration, the xylene is evaporated off under reduced pressure. A liquid and clear product is collected, the mass composition of which is as follows:
Ca = 13.1% S = 4.9% N = 0.8%
Dans un réacteur équipé d'un agitateur, d'un condenseur, d'un séparateur de Dean & Stark et d'une ampoule de coulée, on introduit 50 g d'un sulfonate de calcium surbasique de réserve alcaline (TBN) équivalente à 500 milliéquivalents de potasse par gramme de produit et contenant 18,70 % de calcium soit 0.4456 équivalent basique, 20 g d'une huile minérale 130 Neutral et 300 cm³ de xylène. On porte le milieu à 90 °C puis on introduit en 1 heure à l'aide de l'ampoule une solution de 6,55 g ( 0,0223 mole soit 0,0446 équivalent acide) d'acide 4,4'-(1,3,4-thiadiazole-2,5-diyl) bis (3-thiabutanoïque) dans 70cm³ de tétrahydrofuranne. On maintient le milieu à cette température une heure supplémentaire, puis on distille le tétrahydrofuranne et l'eau de réaction .Après filtration, on procède à l'évaporation du xylène sous pression réduite. On recueille un produit liquide et limpide dont la composition en masse est la suivante :
Ca= 12,8 % S= 5,5 % N= 0,8 %50 g of an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel. milliequivalents of potash per gram of product and containing 18.70% of calcium, ie 0.4456 basic equivalent, 20 g of a 130 Neutral mineral oil and 300 cm³ of xylene. The medium is brought to 90 ° C. and then a solution of 6.55 g (0.0223 mole or 0.0446 acid equivalent) of 4.4 'acid is introduced over 1 hour using the ampoule. 1,3,4-thiadiazole-2,5-diyl) bis (3-thiabutanoic) in 70cm³ of tetrahydrofuran. The medium is maintained at this temperature for an additional hour, then the distilled tetrahydrofuran and reaction water. After filtration, the xylene is evaporated off under reduced pressure. A liquid and clear product is collected, the mass composition of which is as follows:
Ca = 12.8% S = 5.5% N = 0.8%
Dans un réacteur équipé d'un agitateur, d'un condenseur, d'un séparateur de Dean & Stark et d'une ampoule de coulée, on introduit 50 g d'un sulfonate de calcium surbasique de réserve alcaline (TBN) équivalente à 500 milliéquivalents de potasse par gramme de produit et contenant 18,70 % de calcium soit 0.4456 équivalent basique, 50 g d'une huile minérale 130 Neutral et 300 cm³ de xylène. On porte le milieu à 90 °C puis on introduit en 1 heure à l'aide de l'ampoule une solution de 6,45 g (0,0223 mole soit 0,0446 équivalent acide) d'acide bis [3-(5-thio-1,3,4-thiadiazol-2-yl)-3-thiapropanoïque] dans 70cm³ de tétrahydrofuranne. On maintient le milieu à cette température une heure supplémentaire, puis on distille le tétrahydrofuranne et l'eau de réaction. Après filtration, on procède à l'évaporation du xylène sous pression réduite. On recueille un produit liquide et limpide dont la composition en masse est la suivante :
Ca= 8,5% S= 5,1 % N= 1,1 %50 g of an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel. milliequivalents of potash per gram of product and containing 18.70% of calcium, ie 0.4456 basic equivalent, 50 g of a 130 Neutral mineral oil and 300 cm³ of xylene. The medium is brought to 90 ° C. and then a solution of 6.45 g (0.0223 mole or 0.0446 acid equivalent) of bis acid [3- (5 -thio-1,3,4-thiadiazol-2-yl) -3-thiapropanoic] in 70cm³ of tetrahydrofuran. The medium is maintained at this temperature for an additional hour, then the tetrahydrofuran and the reaction water are distilled. After filtration, the xylene is evaporated off under reduced pressure. A liquid and clear product is collected, the mass composition of which is as follows:
Ca = 8.5% S = 5.1% N = 1.1%
Dans un réacteur équipé d'un agitateur, d'un condenseur, d'un séparateur de Dean & Stark et d'une ampoule de coulée, on introduit 50 g d'un sulfonate de calcium surbasique de réserve alcaline (TBN) équivalente à 500 milliéquivalents de potasse par gramme de produit et contenant 18,70 % de calcium soit 0.4456 équivalent basique, 50 g d'une huile minérale 130 Neutral et 300 cm³ de xylène. On porte le milieu à 90 °C puis on introduit en 1 heure à l'aide de l'ampoule une solution de 4,92 g ( 0,0113 mole soit 0,0226 équivalent acide) d'acide bis [4-(5-thio-1,3,4-thiadiazol-2-yl)-4-thiabutanoïque] dans 70cm³ de tétrahydrofuranne. On maintient le milieu à cette température une heure supplémentaire, puis on distille le tétrahydrofuranne et l'eau de réaction. Après filtration, on procède à l'évaporation du xylène sous pression réduite. On recueille un produit liquide et limpide dont la composition en masse est la suivante :
Ca= 8,6% S= 3,1 % N= 0,7 %50 g of an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel. milliequivalents of potash per gram of product and containing 18.70% of calcium, ie 0.4456 basic equivalent, 50 g of a 130 Neutral mineral oil and 300 cm³ of xylene. The medium is brought to 90 ° C. and then a solution of 4.92 g (0.0113 mole or 0.0226 acid equivalent) of bis acid [4- (5 -thio-1,3,4-thiadiazol-2-yl) -4-thiabutanoic] in 70cm³ of tetrahydrofuran. The medium is maintained at this temperature for an additional hour, then the tetrahydrofuran and the reaction water are distilled. After filtration, the evaporation of the xylene under reduced pressure. A liquid and clear product is collected, the mass composition of which is as follows:
Ca = 8.6% S = 3.1% N = 0.7%
Dans un réacteur équipé d'un agitateur, d'un condenseur, d'un séparateur de Dean & Stark et d'une ampoule de coulée, on introduit 50 g d'un sulfonate de magnésium surbasique de réserve alcaline (TBN) équivalente à 400 milliéquivalents de potasse par gramme de produit et contenant 9,4 % de magnésium soit 0.356 équivalent basique, 40 g d'une huile minérale 130 Neutral et 300 cm³ de xylène. On porte le milieu à 90 °C puis on introduit en une heure à l'aide de l'ampoule une solution de 6,3 g (0,0237mole soit 0,0474 équivalent acide) d'acide 3,3'-(1,3,4-thiadiazole-2,5-diyl) bis (3-thiapropanoïque) dans 70cm³ de tétrahydrofuranne. On maintient le milieu à cette température une heure supplémentaire, puis on distille le tétrahydrofuranne et l'eau de réaction . Après filtration, on procède à l'évaporation du xylène sous pression réduite. On recueille un produit liquide et limpide dont la composition en masse est la suivante :
Mg= 4,4 % S= 3,4 % N= 0,7 %50 g of an overbased alkaline reserve magnesium sulfonate (TBN) equivalent to 400 are introduced into a reactor equipped with a stirrer, a condenser, a Dean & Stark separator and a dropping funnel. milliequivalents of potash per gram of product and containing 9.4% magnesium or 0.356 basic equivalent, 40 g of a 130 Neutral mineral oil and 300 cm³ of xylene. The medium is brought to 90 ° C. and then a solution of 6.3 g (0.0237 mol or 0.0474 acid equivalent) of 3.3 ′ acid is introduced over the course of one hour using the bulb. , 3,4-thiadiazole-2,5-diyl) bis (3-thiapropanoic) in 70cm³ of tetrahydrofuran. The medium is maintained at this temperature for an additional hour, then the tetrahydrofuran and the reaction water are distilled. After filtration, the xylene is evaporated off under reduced pressure. A liquid and clear product is collected, the mass composition of which is as follows:
Mg = 4.4% S = 3.4% N = 0.7%
Dans un réacteur équipé d'un agitateur, d'un condenseur, d'un séparateur de Dean & Stark et d'une ampoule de coulée, on introduit 50 g d'un sulfonate de calcium surbasique de réserve alcaline (TBN) équivalente à 500 milliéquivalents de potasse par gramme de produit et contenant 18,70 % de calcium soit 0.4456 équivalent basique, 15 g d'une huile minérale 130N et 300 cm³ de xylène. On porte le milieu à 130 °C puis on introduit en 30 minutes à cette température une solution de 10,8 g d'un acide alkylarylsulfonique de masse molaire équivalente à 700 (soit 0,0154 équivalent acide) dans 100 cm³ de xylène. Après distillation azéotropique de l'eau de réaction formée, on refroidit le milieu à 90 °C puis on introduit en 1 heure à l'aide de l'ampoule une solution de 11,85 g (0,0446 mole soit 0,0891 équivalent acide) d'acide 3,3'-(1,3,4-thiadiazole-2,5-diyl) bis (3-thiapropanoïque) dans 70cm³ de tétrahydrofuranne. Le milieu est maintenu à cette température une heure supplémentaire, puis on distille le tétrahydrofuranne et l'eau de réaction. Après filtration, on procède à l'évaporation du xylène sous pression réduite. On recueille un produit liquide et limpide dont la composition en masse est la suivante :
Ca= 8,5 % S= 5,1 % N= 1,1 %50 g of an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel. milliequivalents of potash per gram of product and containing 18.70% of calcium, ie 0.4456 basic equivalent, 15 g of a 130N mineral oil and 300 cm³ of xylene. The medium is brought to 130 ° C. and then a solution of 10.8 g of an alkylarylsulfonic acid with a molar mass equivalent to 700 (or 0.0154 acid equivalent) in 100 cm³ of xylene is introduced over 30 minutes at this temperature. After azeotropic distillation of the reaction water formed, the medium is cooled to 90 ° C. and then a solution of 11.85 g (0.0446 mol or 0.0891 equivalent) is introduced over 1 hour using the ampoule. acid) 3.3 '- (1,3,4-thiadiazole-2,5-diyl) bis (3-thiapropanoic) acid in 70cm³ of tetrahydrofuran. The medium is maintained at this temperature for an additional hour, then the tetrahydrofuran and the reaction water are distilled. After filtration, the xylene is evaporated off under reduced pressure. A liquid and clear product is collected, the mass composition of which is as follows:
Ca = 8.5% S = 5.1% N = 1.1%
Dans un réacteur équipé d'un agitateur, d'un condenseur, d'un séparateur de Dean & Stark et d'une ampoule de coulée, on introduit 50 g d'un sulfonate de calcium surbasique de réserve alcaline (TBN) équivalente à 500 milliéquivalents de potasse par gramme de produit et contenant 18,70 % de calcium soit 0.4456 équivalent basique, 50 g d'une huile minérale 130N et 300 cm³ de xylène. On porte le milieu à 130 °C puis on introduit en 30 minutes à cette température une solution de 10,8 g d'un acide alkylarylsulfonique de masse molaire équivalente à 700 (soit 0,0154 équivalent acide) dans 100 cm³ de xylène. Après distillation azéotropique de l'eau de réaction formée, on refroidit le milieu à 90 °C puis on introduit en 1 heure à l'aide de l'ampoule une solution de 13,1 g (0,0446 mole soit 0,0891 équivalent acide) d'acide 4,4'-(1,3,4-thiadiazole-2,5-diyl) bis (3-thiabutanoïque) dans 70cm³ de tétrahydrofuranne. Le milieu est maintenu à cette température une heure supplémentaire, puis on distille le tétrahydrofuranne et l'eau de réaction. Après filtration, on procède à l'évaporation du xylène sous pression réduite. On recueille un produit liquide et limpide dont la composition en masse est la suivante :
Ca= 7,6 % S= 4,9 % N= 1,1 %50 g of an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel. milliequivalents of potash per gram of product and containing 18.70% of calcium, ie 0.4456 basic equivalent, 50 g of a 130N mineral oil and 300 cm³ of xylene. The medium is brought to 130 ° C. and then a solution of 10.8 g of an alkylarylsulfonic acid with a molar mass equivalent to 700 (or 0.0154 acid equivalent) in 100 cm³ of xylene is introduced over 30 minutes at this temperature. After azeotropic distillation of the reaction water formed, the medium is cooled to 90 ° C. and then a solution of 13.1 g (0.0446 mol or 0.0891 equivalent) is introduced over 1 hour using the ampoule. acid) of 4,4 '- (1,3,4-thiadiazole-2,5-diyl) bis (3-thiabutanoic) acid in 70cm³ of tetrahydrofuran. The medium is maintained at this temperature for an additional hour, then the tetrahydrofuran and the reaction water are distilled. After filtration, the xylene is evaporated off under reduced pressure. A liquid and clear product is collected, the mass composition of which is as follows:
Ca = 7.6% S = 4.9% N = 1.1%
Dans un réacteur équipé d'un agitateur, d'un condenseur, d'un séparateur de Dean & Stark et d'une ampoule de coulée, on introduit 50 g d'un sulfonate de calcium surbasique de réserve alcaline (TBN) équivalente à 500 milliéquivalents de potasse par gramme de produit et contenant 18,70 % de calcium soit 0.4456 équivalent basique, 50 g d'une huile minérale 130N et 300 cm³ de xylène. On porte le milieu à 130 °C puis on introduit en 30 minutes à cette température une solution de 10,8 g d'un acide alkylarylsulfonique de masse molaire équivalente à 700 (soit 0.0154 équivalent acide) dans 100 cm³ de xylène. Après distillation azéotropique de l'eau de réaction formée, on refroidit le milieu à 90 °C puis on introduit en 1 heure à l'aide de l'ampoule une solution de 14,7 g (0,0322 mole soit 0,0664 équivalent acide) d'acide bis [4-(5-thio-1,3,4-thiadiazole-2-yl)-4-thiabutanoïque] dans 70cm³ de tétrahydrofuranne. Le milieu est maintenu à cette température une heure supplémentaire, puis on distille le tétrahydrofuranne et l'eau de réaction . Après filtration, on procède à l'évaporation du xylène sous pression réduite. On recueille un produit liquide et limpide dont la composition en masse est la suivante :
Ca= 7,2% S= 4,1% N= 1,0%50 g of an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel. milliequivalents of potash per gram of product and containing 18.70% of calcium, ie 0.4456 basic equivalent, 50 g of a 130N mineral oil and 300 cm³ of xylene. The medium is brought to 130 ° C. and then a solution of 10.8 g is introduced over 30 minutes at this temperature. an alkylarylsulfonic acid with a molar mass equivalent to 700 (or 0.0154 acid equivalent) in 100 cm³ of xylene. After azeotropic distillation of the reaction water formed, the medium is cooled to 90 ° C. and then a solution of 14.7 g (0.0322 mol or 0.0664 equivalent) is introduced over 1 hour using the ampoule. acid) of bis [4- (5-thio-1,3,4-thiadiazole-2-yl) -4-thiabutanoic acid] in 70cm³ of tetrahydrofuran. The medium is maintained at this temperature for an additional hour, then the tetrahydrofuran and the reaction water are distilled. After filtration, the xylene is evaporated off under reduced pressure. A liquid and clear product is collected, the mass composition of which is as follows:
Ca = 7.2% S = 4.1% N = 1.0%
Dans un réacteur équipé d'un agitateur, d'un condenseur, d'un séparateur de Dean & Stark et d'une ampoule de coulée, on introduit 50 g d'un sulfonate de calcium surbasique de réserve alcaline (TBN) équivalente à 500 milliéquivalents de potasse par gramme de produit et contenant 18,70 % de calcium soit 0.4456 équivalent basique, 80 g d'une huile minérale 130N et 300 cm³ de xylène. On porte le milieu à 130° C puis on introduit en 30 minutes à cette température une solution de 63,4 g d'un acide alkylarylsulfonique de masse molaire équivalente à 700 (soit 0,09 équivalent acide) dans 100 cm³ de xylène. Après distillation azéotropique de l'eau de réaction formée, on refroidit le milieu à 90 °C puis on introduit en 1 heure à l'aide de l'ampoule une solution de 47,2 g (0,177mole soit 0,354 équivalent acide) d'acide 3,3'-(1,3,4-thiadiazole-2,5-diyl)bis(3-thiapropanoïque) dans 70 cm³ de tétrahydrofuranne. Le milieu est maintenu à cette température une heure supplémentaire, puis on distille le tétrahydrofuranne et l'eau de réaction. Après filtration, on procède à l'évaporation du xylène sous pression réduite. On recueille un produit liquide et limpide dont la composition en masse est la suivante :
Ca= 3,7 % S= 8,7 % N= 2,3 %50 g of an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel. milliequivalents of potash per gram of product and containing 18.70% of calcium, ie 0.4456 basic equivalent, 80 g of a 130N mineral oil and 300 cm³ of xylene. The medium is brought to 130 ° C. and then a solution of 63.4 g of an alkylarylsulfonic acid with a molar mass equivalent to 700 (or 0.09 acid equivalent) in 100 cm³ of xylene is introduced over 30 minutes at this temperature. After azeotropic distillation of the reaction water formed, the medium is cooled to 90 ° C. and then a solution of 47.2 g (0.177 mol or 0.354 acid equivalent) of 3.3 '- (1,3,4-thiadiazole-2,5-diyl) bis (3-thiapropanoic) acid in 70 cm³ of tetrahydrofuran. The medium is maintained at this temperature for an additional hour, then the tetrahydrofuran and the reaction water are distilled. After filtration, the xylene is evaporated off under reduced pressure. A liquid and clear product is collected, the mass composition of which is as follows:
Ca = 3.7% S = 8.7% N = 2.3%
L'examen de ce produit par spectroscopie infrarouge confirme la totale consommation de la réserve alcaline initiale constituée de carbonate de calcium (absence de signal à 862 cm ⁻¹).The examination of this product by infrared spectroscopy confirms the total consumption of the initial alkaline reserve made up of calcium carbonate (absence of signal at 862 cm ⁻¹).
Dans un réacteur équipé d'un agitateur, d'un condenseur, d'un séparateur de Dean & Stark et d'une ampoule de coulée, on introduit 50 g d'un sulfonate de calcium surbasique de réserve alcaline (TBN) équivalente à 500 milliéquivalents de potasse par gramme de produit et contenant 18,70 % de calcium soit 0.4456 équivalent basique, 50 g d'une huile minérale 130N et 300 cm³ de xylène. On introduit 4,11 g d'acide orthoborique (0,066 mole) dispersé dans 30 cm³ de méthanol puis on porte le milieu à reflux pendant 1 heure. Après distillation azéotropique du méthanol et de l'eau de réaction formée, on refroidit le milieu à 90 °C puis on introduit en 1 heure à l'aide de l'ampoule une solution de 4,74 g (0,0178 mole soit 0,0356 équivalent acide) d'acide 3,3'-(1,3,4-thiadiazole-2,5-diyl)bis(3-thiapropanoïque) dans 70 cm³ de tétrahydrofuranne. Le milieu est maintenu à cette température une heure supplémentaire, puis on distille le tétrahydrofuranne et l'eau de réaction. Après filtration, on procède à
l'évaporation du xylène sous pression réduite. On recueille un produit liquide et limpide dont la composition en masse est la suivante :
Ca= 7,8 % S=2,6 % N=0,6 % B=0,5%50 g of an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel. milliequivalents of potash per gram of product and containing 18.70% of calcium, ie 0.4456 basic equivalent, 50 g of a 130N mineral oil and 300 cm³ of xylene. 4.11 g of orthoboric acid (0.066 mol) dispersed in 30 cm³ of methanol are introduced and then the medium is brought to reflux for 1 hour. After azeotropic distillation of methanol and of the reaction water formed, the medium is cooled to 90 ° C. and then a solution of 4.74 g (0.0178 mol or 0) is introduced over 1 hour using the ampoule. , 0356 acid equivalent) of 3,3 '- (1,3,4-thiadiazole-2,5-diyl) bis (3-thiapropanoic) acid in 70 cm³ of tetrahydrofuran. The medium is maintained at this temperature for an additional hour, then the tetrahydrofuran and the reaction water are distilled. After filtration, we proceed to
evaporation of xylene under reduced pressure. A liquid and clear product is collected, the mass composition of which is as follows:
Ca = 7.8% S = 2.6% N = 0.6% B = 0.5%
Dans un réacteur équipé d'un agitateur, d'un condenseur, d'un séparateur de Dean & Stark et d'une ampoule de coulée, on introduit 50 g d'un sulfonate de calcium surbasique de réserve alcaline (TBN) équivalente à 500 milliéquivalents de potasse par gramme de produit et contenant 18,70 % de calcium soit 0.4456 équivalent basique, 50 g d'une huile minérale 130 Neutral et 300 cm³ de xylène. On porte le milieu à 90 °C puis on introduit en 1 heure à l'aide de l'ampoule une solution de 5,98 g ( 0,0167 mole soit 0,0334 équivalent acide) d'acide 5,5'-(1,3,4-thiadiazole-2,5-diyl) bis (4,5-dithiapentanoïque) dans 70cm³ de tétrahydrofuranne. On maintient le milieu à cette température une heure supplémentaire, puis on distille le tétrahydrofuranne et l'eau de réaction. Après filtration, on procède à l'évaporation du xylène sous pression réduite. On recueille un produit liquide et limpide dont la composition en masse est la suivante :
Ca= 8,0 % S= 3,5 % N= 0,6 %50 g of an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel. milliequivalents of potash per gram of product and containing 18.70% of calcium, ie 0.4456 basic equivalent, 50 g of a 130 Neutral mineral oil and 300 cm³ of xylene. The medium is brought to 90 ° C. and then a solution of 5.98 g (0.0167 mole or 0.0334 acid equivalent) of 5.5 'acid is introduced over 1 hour using the ampoule. 1,3,4-thiadiazole-2,5-diyl) bis (4,5-dithiapentanoic) in 70cm³ of tetrahydrofuran. The medium is maintained at this temperature for an additional hour, then the tetrahydrofuran and the reaction water are distilled. After filtration, the xylene is evaporated off under reduced pressure. A liquid and clear product is collected, the mass composition of which is as follows:
Ca = 8.0% S = 3.5% N = 0.6%
Les produits des exemples 1 à 7 et 10 précédents sont soumis à une dialyse en solution dans l'heptane normal à travers une membrane en latex. Pour chaque éssai, on détermine la fraction massique ayant dialysé (dialysat) et celle n'ayant pas dialysé (concentrat), cette dernière constituant la partie colloïdale. On détermine également pour chaque fraction la concentration en soufre et/ou en azote. Les résultats sont rassemblés dans le tableau n°1. La localisation de l'azote et du soufre exclusivement dans les concentrats confirme le caractère colloïdal des carboxylates de calcium ou de magnésium des différents acides considérés.The products of Examples 1 to 7 and 10 above are subjected to dialysis in solution in normal heptane through a latex membrane. For each test, the mass fraction having dialyzed (dialysate) and that not having dialyzed (concentrate) are determined, the latter constituting the colloidal part. The sulfur and / or nitrogen concentration is also determined for each fraction. The results are collated in Table 1. The location of nitrogen and sulfur exclusively in concentrates confirms the colloidal nature of the calcium or magnesium carboxylates of the various acids considered.
Les produits des exemples 1 à 7, 10 et 11 précédents sont évalués pour leurs propriétés anti-usure et extrême-pression dans une huile lubrifiante minérale 130 Neutral. Les performances sont évaluées sur machine 4 billes selon la méthode ASTM D 2783. Les résultats sont rassemblés dans le tableau n° 2. On a donné à titre de comparaison les résultats obtenus à la même concentration dans l'huile avec un sulfonate de calcium surbasique équivalent non modifié selon le procédé décrit dans l'invention. Les résultats confirment les performances accrues des produits de l'invention : les indices charge/usure et les charges de soudure sont très nettement améliorés alors que le diamètre d'empreinte après un heure sous charge de 40 daN reste dans tous les cas inférieur à 0,50 mm.
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9310128 | 1993-08-18 | ||
| FR9310128A FR2709076B1 (en) | 1993-08-18 | 1993-08-18 | Colloidal products containing calcium, and / or magnesium, as well as sulfur and nitrogen, their preparation and their use in particular as additives in lubricating oils. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0639634A1 true EP0639634A1 (en) | 1995-02-22 |
| EP0639634B1 EP0639634B1 (en) | 1999-12-29 |
Family
ID=9450315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94401783A Expired - Lifetime EP0639634B1 (en) | 1993-08-18 | 1994-08-03 | Colloidal products containing calcium and/or magnesium as well as sulfur and nitrogen, their preparation and their use, especially as additives for lubricants |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5462682A (en) |
| EP (1) | EP0639634B1 (en) |
| JP (1) | JPH0780280A (en) |
| AT (1) | ATE188241T1 (en) |
| DE (1) | DE69422348T2 (en) |
| ES (1) | ES2142916T3 (en) |
| FR (1) | FR2709076B1 (en) |
| PT (1) | PT639634E (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996030467A1 (en) * | 1994-03-03 | 1996-10-03 | Institut Français Du Petrole | Colloidal products containing calcium, barium and/or magnesium as well as bismuth, and being modified by sulphur- and optionally nitrogen-containing carboxylic acid activity |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5585029A (en) * | 1995-12-22 | 1996-12-17 | Exxon Research And Engineering Company | High load-carrying turbo oils containing amine phosphate and 2-alkylthio-1,3,4-thiadiazole-5-alkanoic acid |
| US5731274A (en) * | 1996-09-11 | 1998-03-24 | Exxon Research And Engineering Company | Lithium complex grease with extended lubrication life |
| GB9900035D0 (en) * | 1999-01-04 | 1999-02-24 | Infineum Uk Ltd | Overbased metal detergents |
| US20050061734A1 (en) * | 2003-09-22 | 2005-03-24 | Alltrista Zinc Products, L.P. | Anti-corrosive engine oil system components |
| US20050065042A1 (en) * | 2003-09-22 | 2005-03-24 | Alltrista Zinc Products, L.P., An Indiana Limited Partnership | Anti-corrosive engine oil system components |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0390664A2 (en) * | 1989-03-30 | 1990-10-03 | Institut Français du Pétrole | New thiophosphorous compounds, a process for preparing same and use of said compounds as lubricant additives |
| EP0536020A1 (en) * | 1991-09-30 | 1993-04-07 | Institut Francais Du Petrole | Colloidal products containing boron, sulphur and phosphorus, their preparation and their use as additives for lubricants |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5256319A (en) * | 1989-03-30 | 1993-10-26 | Institut Francais Du Petrole | New thiophosphoretted compounds, their preparation and their use as additives for lubricants |
| FR2689031B1 (en) * | 1992-03-26 | 1994-05-27 | Inst Francais Du Petrole | OVERLOCKED COLLOUIDAL PRODUCTS CONTAINING ORGANIC SULFUR AND THEIR USE AS DETERGENT ADDITIVES WITH ANTI-WEAR AND EXTREME-PRESSURE ACTION IN LUBRICATING OILS. |
-
1993
- 1993-08-18 FR FR9310128A patent/FR2709076B1/en not_active Expired - Fee Related
-
1994
- 1994-08-03 AT AT94401783T patent/ATE188241T1/en not_active IP Right Cessation
- 1994-08-03 PT PT94401783T patent/PT639634E/en unknown
- 1994-08-03 DE DE69422348T patent/DE69422348T2/en not_active Expired - Fee Related
- 1994-08-03 ES ES94401783T patent/ES2142916T3/en not_active Expired - Lifetime
- 1994-08-03 EP EP94401783A patent/EP0639634B1/en not_active Expired - Lifetime
- 1994-08-17 JP JP6192654A patent/JPH0780280A/en active Pending
- 1994-08-18 US US08/292,004 patent/US5462682A/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0390664A2 (en) * | 1989-03-30 | 1990-10-03 | Institut Français du Pétrole | New thiophosphorous compounds, a process for preparing same and use of said compounds as lubricant additives |
| EP0536020A1 (en) * | 1991-09-30 | 1993-04-07 | Institut Francais Du Petrole | Colloidal products containing boron, sulphur and phosphorus, their preparation and their use as additives for lubricants |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996030467A1 (en) * | 1994-03-03 | 1996-10-03 | Institut Français Du Petrole | Colloidal products containing calcium, barium and/or magnesium as well as bismuth, and being modified by sulphur- and optionally nitrogen-containing carboxylic acid activity |
| US5696062A (en) * | 1994-03-03 | 1997-12-09 | Institut Francais Du Petrole | Colloidal products containing calcium barium and/or magnesium also bismuth modified by the action of carboxylic acids containing sulphur and optionally nitrogen |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2142916T3 (en) | 2000-05-01 |
| JPH0780280A (en) | 1995-03-28 |
| PT639634E (en) | 2000-04-28 |
| ATE188241T1 (en) | 2000-01-15 |
| FR2709076A1 (en) | 1995-02-24 |
| DE69422348D1 (en) | 2000-02-03 |
| DE69422348T2 (en) | 2000-06-08 |
| FR2709076B1 (en) | 1995-10-06 |
| US5462682A (en) | 1995-10-31 |
| EP0639634B1 (en) | 1999-12-29 |
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