EP0390664A2 - New thiophosphorous compounds, a process for preparing same and use of said compounds as lubricant additives - Google Patents
New thiophosphorous compounds, a process for preparing same and use of said compounds as lubricant additives Download PDFInfo
- Publication number
- EP0390664A2 EP0390664A2 EP90400818A EP90400818A EP0390664A2 EP 0390664 A2 EP0390664 A2 EP 0390664A2 EP 90400818 A EP90400818 A EP 90400818A EP 90400818 A EP90400818 A EP 90400818A EP 0390664 A2 EP0390664 A2 EP 0390664A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition according
- mass
- phosphorus
- reaction
- overbased
- 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
- 150000001875 compounds Chemical class 0.000 title abstract description 19
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000003879 lubricant additive Substances 0.000 title 1
- 239000000654 additive Substances 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 19
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical class S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 hydrogen compound Chemical class 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 150000001408 amides Chemical class 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000011575 calcium Substances 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 230000001050 lubricating effect Effects 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000004519 grease Substances 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 239000005069 Extreme pressure additive Substances 0.000 abstract description 7
- 239000003599 detergent Substances 0.000 abstract description 6
- 239000007866 anti-wear additive Substances 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 41
- 239000000047 product Substances 0.000 description 41
- 239000003921 oil Substances 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000012360 testing method Methods 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 11
- 239000002585 base Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000012429 reaction media Substances 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- BTHAQRDGBHUQMR-UHFFFAOYSA-N [S]P(=O)=O Chemical compound [S]P(=O)=O BTHAQRDGBHUQMR-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001246 colloidal dispersion Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 2
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- QBCOASQOMILNBN-UHFFFAOYSA-N didodecoxy(oxo)phosphanium Chemical compound CCCCCCCCCCCCO[P+](=O)OCCCCCCCCCCCC QBCOASQOMILNBN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- KHFVGGRBRAHSFE-UHFFFAOYSA-N nonapotassium;triborate Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] KHFVGGRBRAHSFE-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- OTYNBGDFCPCPOU-UHFFFAOYSA-N phosphane sulfane Chemical compound S.P[H] OTYNBGDFCPCPOU-UHFFFAOYSA-N 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JJJPTTANZGDADF-UHFFFAOYSA-N thiadiazole-4-thiol Chemical class SC1=CSN=N1 JJJPTTANZGDADF-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- JWPRJFACDNAYPA-UHFFFAOYSA-L zinc;octan-3-yloxy-octan-3-ylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCC(CC)OP([O-])(=S)SC(CC)CCCCC.CCCCCC(CC)OP([O-])(=S)SC(CC)CCCCC JWPRJFACDNAYPA-UHFFFAOYSA-L 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
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic 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
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/14—Water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/24—Compounds containing phosphorus, arsenic or antimony
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
-
- 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/04—Hydroxy compounds
- C10M129/06—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
-
- 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/04—Hydroxy compounds
- C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
-
- 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/30—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms
-
- 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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
-
- 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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/16—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
- C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
-
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Definitions
- the present invention relates to new thiophosphorus compounds soluble in mineral oils obtained by reaction of at least one phosphorus sulfide with at least one so-called "overbased" detergent sulfonate.
- an overbased detergent sulfonate can be defined as consisting of a surfactant consisting essentially of an alkaline or alkaline earth salt of a sulfonic acid containing oleophilic groups and which keeps acid salts in colloidal dispersion.
- weak minerals such as CO2, H2S and alkaline or alkaline earth bases.
- the reaction product between the phosphorus sulfide and the overbased detergent sulfonate can optionally be treated with at least one active hydrogen compound which can be water, an alcohol, a phenol, a carboxylic acid, a ester-acid, a mineral acid, a mineral base, an amine, an amide or a mercaptan.
- active hydrogen compound can be water, an alcohol, a phenol, a carboxylic acid, a ester-acid, a mineral acid, a mineral base, an amine, an amide or a mercaptan.
- the present invention also relates to the preparation of these new thiophosphorus compounds and their use as additives in mineral and synthetic lubricants.
- these new additives have anti-wear and extreme pressure properties which are particularly advantageous for application to motor oils, gear oils, hydraulic fluids, lubricating greases or oils for working with metals. .
- Antiwear and extreme pressure additives are incorporated in 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.
- transmission oils two types of additive are widely used: phospho-sulfur additives and additives based on potassium borate dispersion.
- the main disadvantage of mineral oils containing phospho-sulfur additives is their thermal instability, which begins to manifest from 120-130 ° C. However, it is not uncommon for temperatures of 150 ° C to be reached in the transmissions of heavy goods vehicles or passenger cars used under severe conditions. Transmission oils based on potassium borate are significantly more thermally stable, but are sensitive to water, which is unacceptable for certain uses. More effective antiwear and extreme pressure additives, more thermally stable and having less interactions with the other additives in the formulations are actively sought.
- micellar thiophosphorus compounds of the present invention can be generally defined as being obtained by reaction of at least one overbased sulfonate (A) with a phosphorus sulfide (B), the reaction product possibly being brought into contact with at least one compound with hy active drogen (C).
- a and B, and optionally the subsequent treatment with C can advantageously be carried out in a solvent (D).
- Compound A is an overbased sulfonate obtained from at least one alkali or alkaline earth metal salt of at least one acid compound chosen from sulfonic acids, natural or synthetic.
- the overbasification of the alkali or alkaline earth metal salts of these acids is generally carried out in the presence of a promoter, by treating an excess of oxide or hydroxide of alkali or alkaline earth metal suspended in the reaction medium , by a weak acid such as CO2, SO2, H2S, or H3BO3.
- the most used cations for overbasification are sodium, magnesium, calcium and barium used in the form of their oxide or hydroxide.
- the promoter is an alcohol, particularly methanol, an alkylphenol or an amino compound such as ammonia, an amine or an amino alcohol.
- the most commonly used weak acid is CO2.
- overbased additives The preparation of overbased additives is well known and is described for example in the patents: US 2,865,956, 3,150,088, 3,537,996, 3,830,739, 3,865,737, 4,148,740 and 4,505,830 and the French patent 2 101 813.
- 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.
- the sulfonic acids for the manufacture of overbased sulfonates which can be used according to the invention are known and described in numerous patents, for example in French patent 2 101 813, pages 5 and 6.
- the hydrocarbon portion of the molecule advantageously has a molecular weight at less than 370 to ensure the miscibility of the corresponding sulfonates in mineral oils.
- They may be so-called "natural" acids, resulting from the sulfonation of petroleum cuts, or of synthetic acids prepared by sulfonation of charges prepared by synthetic route: alkenyl hydrocarbons, such as polyisobutenes (US Pat. 4,159,956), alkylaryl hydrocarbons such as for example post-dodecylbenzenes obtained as tail product of the manufacture of dodecylbenzene.
- overbased compounds A preferred according to the invention are the sodium or calcium sulfonates overbased with sodium carbonate or calcium carbonate.
- the overbased sulfonates A which can be used according to the invention have an alkalinity expressed in terms of TBN (equivalent alkalinity expressed in milligrams of KOH per g of product) between 50 and 550 (or from 0.9 to 10 basic equivalents per kg) and preferably between 150 and 450 (i.e. 2.7 to 8 basic equivalents per kg).
- TBN equivalent alkalinity expressed in milligrams of KOH per g of product
- 150 and 450 i.e. 2.7 to 8 basic equivalents per kg.
- Compound B is a phosphorus sulfide such as P4S7, P4S9, P4S10.
- P4S10 is the preferred phosphorus sulfide according to the invention.
- Compound C which can be optionally used is a compound containing an active hydrogen; it can be water, an alcohol such as methanol or isopropanol, a phenol, an acid such as a carboxylic acid such as acetic acid, an acid ester such as a dialkylphosphite, a mineral acid such as acid boric or phosphoric acid, a base such as ammonia or an amine, an amide, a mercaptan, such as dimercaptothiadiazole or its derivatives substituted formula
- the molar quantity of compound C introduced relative to the molar quantity of phosphorus provided by the phosphorus sulphide can vary in a ratio of between 0.1 and 5, and preferably between 0.3 and 3.
- the preferred compounds C according to the invention are ammonia, isopropanol, dialkylphosphites, boric acid, mercaptans, in particular derivatives of dimercaptothiadiazole.
- the solvent D possibly used makes it possible to reduce the viscosity of the reaction medium and thus to improve the contact of the reactants.
- solvents which can be used according to the invention, mention may be made of cyclohexane, toluene, xylenes and in general hydrocarbon fractions having a boiling range of between 60 and 150 ° C. and preferably between 90 and 120 ° C.
- the additives obtained according to the invention can have a certain reactivity with respect to copper alloys.
- the use of sequestering additives of the dimercaptothiadiazole type in doses of between 0.25 and 0.75% by mass in the final formulations leads to entirely satisfactory behavior with respect to copper.
- the dose required is lower when compound C is itself a derivative of mercaptothiadiazole. It can go for example up to 0.5% by mass.
- Another characteristic of the present invention is that, within the defined limits, the products obtained retain the colloidal state by giving solutions in the hydrocarbons perfectly clear and stable over time.
- the process for manufacturing the compounds according to the invention comprises the following steps:
- Step 1
- the reaction of phosphorus sulfide on overbased sulfonate can be carried out at a pressure between atmospheric pressure and about 5 bar absolute (0.5 MPa), at a temperature between 60 and 130 ° C and preferably between 85 and 120 ° C.
- the reaction between the phosphorus sulphide, solid reagent and the overbased additive is facilitated by good stirring of the reaction medium and by the possible use of a hydrocarbon solvent D.
- the phosphorus sulphide can be gradually introduced into the reaction medium, but it can also be introduced entirely at the start of handling into the overbased compound optionally dissolved in a hydrocarbon solvent, provided that the temperature of the reaction medium is less than about 60 ° C.
- the reaction is then started by gradually raising the temperature in the ranges indicated above.
- Compound C with active hydrogen can be in gaseous, liquid or solid form and the means of introduction into the reaction medium will be appropriate to its physical state.
- the reaction can be carried out at a pressure between atmospheric pressure and about 5 bar absolute (0.5 MPa), at a temperature between 60 and 130 ° C and preferably between 25 and 120 ° C.
- filtration and elimination of solvents and any excess of reagent.
- the filtration step is not always necessary, steps 1 and 2 leading in most cases to homogeneous liquid mixtures.
- filtration can be carried out before the removal of solvent D, for example on simple cellulose disks, or on layers of filtering agents of the diatomite type or of natural silica of volcanic origin. Filtration can also be carried out after removal of the solvents. In this case, it is advantageous to carry out hot filtration, for example from 90 to 120 ° C and under a pressure of 2 to 5 bars.
- the distillation of the solvent can be carried out in the reactor itself.
- the elimination of the last traces is facilitated by a nitrogen stripping. It can also be carried out in a thin film evaporator.
- the product obtained after filtration and elimination of the toluene, ie 253.3 g, has the following characteristics: Ca: 14.2% mass P: 0.88% mass S: 2.25% mass
- Example 6 The procedure is as in Example 6 until complete reaction of the P4S10. The temperature being maintained at 90 ° C., 49.5 g of didodecylphosphite dissolved in 50 ml of toluene are introduced over 1 hour. Then the temperature is brought to 115 ° C. and is maintained for 3 hours.
- the products described in the previous examples were evaluated for their antiwear and extreme pressure properties in a lubricating oil.
- the base mineral oil used is a 130 Neutral with the following characteristics: Kinematic viscosity at 40 ° C: 25.5 mm2 / s Kinematic viscosity at 100 ° C: 4.7 mm2 / s Viscosity index: 101 Pour point: - 15 ° C Sulfur content: 0.46% mass
- the anti-wear efficiency is evaluated on a 4-ball machine operating for 1 hour under loads of 40 and 60 daN at a speed of 1500 rpm, according to the NF E48-617 method.
- the average footprint diameter observed on the 3 lower balls are as follows: Products Footprint diameter (mm) 40 daN 60 daN Oil 130 N 1.72 2.22 Oil + 5.3% of the product of Ex. 1 0.48 0.65 Oil + 12% of the product of Ex. 1 0.34 0.39 Oil + 5.3% of the product of Ex. 2 0.44 0.62 Oil + 5.3% of the product of Ex. 3 0.43 0.59 Oil + 5.3% of the product of Ex. 4 0.48 0.70 Oil + 5.3% of the product of Ex. 5 0.44 0.57 Oil + 5.3% of the product of Ex.
- the extreme pressure properties in the lubricating oils of the products according to the invention were measured on a FZG gear machine according to the CEC method L-07-A-71 with the procedure A / 16.6 / 90, that is to say ie using the gear type A, with a circumferential speed at the pitch diameter of 16.6 m / s and at the temperature of 90 ° C at the start of each load bearing.
- the mineral oil used is the base 130 N described above. Method B of visual rating was used.
- the extreme pressure efficiency is all the more pronounced the higher the load level reached.
- the temperature of the oil was also recorded at the end of the bearing 12 which is in relation to the forces dissipated in the friction.
- the objective of this test was to replace the antiwear additive and the detergent additive with an additive according to the invention.
- a conventional dispersant additive of the succinimide type usually used to satisfy the requirements of cold dispersivity was used.
- test bench is driven by an electric motor and operates according to the following cycle: 1 minute at 750 rpm 2 minutes at 1500 rpm
- the springs, under maximum lift, are rated at 1200 N.
- the duration of the test is 50 hours and the oil temperature is regulated at 50 ° C.
- the rockers are weighed and rated according to a scale which defines four typical aspects.
- This test uses a PEUGEOT PC7 bridge to which torque peaks of the order of 340 Nm are applied.
- the crown is examined without dismantling all the series of 20 torque peaks.
- the test is continued up to 80 peaks of torque, after which the bridge is dismantled and the surfaces of the pinion and the crown are examined.
- the result is given as a percentage of the bearing surface deteriorated by seizing (scoring).
- the additives are compared in an identical base oil (100 neutral solvent).
- a comparative test was carried out with an extreme pressure additive sold under the name of ANGLAMOL 99 (registered trademark), extreme pressure additive widely used in hypoid bridges.
- Product of Example 12 12.9 * 2.0 * 7.2% after deduction of the dilution oil.
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Abstract
On décrit une nouvelle classe d'additifs antiusure et extrême-pression constituée de composés thiophosphorés obtenus par réaction de sulfures de phosphore, et notamment de décasulfure de phosphore P₄S₁₀, avec des additifs détergents surbasiques. Le produit de réaction peut être éventuellement traité par au moins un composé à hydrogène actif: eau, alcool, phénol, acide, ammoniac, amine, amide et/ou mercaptan.A new class of anti-wear and extreme-pressure additives is described consisting of thiophosphorus compounds obtained by reacting phosphorus sulphides, and in particular phosphorus decasulphide P₄S₁₀, with overbased detergent additives. The reaction product can optionally be treated with at least one active hydrogen compound: water, alcohol, phenol, acid, ammonia, amine, amide and/or mercaptan.
Description
La présente invention concerne de nouveaux composés thiophosphorés solubles dans les huiles minérales obtenus par réaction d'au moins un sulfure de phosphore avec au moins un sulfonate détergent dit "surbasique".The present invention relates to new thiophosphorus compounds soluble in mineral oils obtained by reaction of at least one phosphorus sulfide with at least one so-called "overbased" detergent sulfonate.
D'une manière générale, un sulfonate détergent surbasique peut être défini comme constitué d'un agent tensioactif consistant essentiellement en un sel alcalin ou alcalino-terreux d'un acide sulfonique renfermant des groupes oléophiles et qui maintient en dispersion colloïdale des sels d'acides faibles minéraux tels que CO₂, H₂S et de bases alcalines ou alcalino-terreuses.In general, an overbased detergent sulfonate can be defined as consisting of a surfactant consisting essentially of an alkaline or alkaline earth salt of a sulfonic acid containing oleophilic groups and which keeps acid salts in colloidal dispersion. weak minerals such as CO₂, H₂S and alkaline or alkaline earth bases.
Selon l'invention, le produit de réaction entre le sulfure de phosphore et le sulfonate détergent surbasique peut être éventuellement traité par au moins un composé à hydrogène actif qui peut être de l'eau, un alcool, un phénol, un acide carboxylique, un ester-acide, un acide minéral, une base minérale, une amine, un amide ou un mercaptan.According to the invention, the reaction product between the phosphorus sulfide and the overbased detergent sulfonate can optionally be treated with at least one active hydrogen compound which can be water, an alcohol, a phenol, a carboxylic acid, a ester-acid, a mineral acid, a mineral base, an amine, an amide or a mercaptan.
La présente invention concerne également la préparation de ces nouveaux composés thiophosphorés et leur utilisation comme additifs dans les lubrifiants minéraux et synthétiques. En particulier, on a découvert que ces nouveaux additifs présentaient des propriétés antiusure et extrême-pression particulièrement intéressantes pour l'application aux huiles pour moteurs, aux huiles d'engrenages, aux fluides hydrauliques, aux graisses lubrifiantes ou aux huiles pour le travail des métaux.The present invention also relates to the preparation of these new thiophosphorus compounds and their use as additives in mineral and synthetic lubricants. In particular, it has been discovered that these new additives have anti-wear and extreme pressure properties which are particularly advantageous for application to motor oils, gear oils, hydraulic fluids, lubricating greases or oils for working with metals. .
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.Antiwear and extreme pressure additives are incorporated in 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.
Les additifs antiusure les plus largement utilisés dans les moteurs sont les dialkyldithiophosphates de zinc, mais l'efficacité de ces additifs est atténuée par la présence de dispersants azotés, probablement à cause de la formation de complexes de coordination entre ces deux types d'additifs. Or les huiles moteurs modernes exigent des quantités importantes de dispersants, notamment pour être conformes à l'essai VE de la spécification SG de l'American Petroleum Institute. La teneur accrue en additif nécessaire pour maintenir constantes les qualités antiusure se traduit par une augmentation de la teneur en phosphore des huiles moteurs, alors que c'est précisément l'inverse qui est recherché pour l'efficacité maximale des pots catalytiques destinés à réduire la pollution par les gaz d'échappementThe most widely used wear additives in engines are zinc dialkyldithiophosphates, but the effectiveness of these additives is mitigated by the presence of nitrogen dispersants, probably due to the formation of coordination complexes between these two types of additives. However, modern motor oils require significant quantities of dispersants, in particular to comply with the VE test of the SG specification of the American Petroleum Institute. The increased content of additive necessary to keep the antiwear qualities constant results in an increase in the phosphorus content of engine oils, whereas it is precisely the reverse that is sought for the maximum efficiency of catalytic converters intended to reduce the exhaust gas pollution
En ce qui concerne les huiles de transmission, deux types d'additifs sont largement utilisés : les additifs phospho-soufrés et les additifs à base de dispersion de borate de potassium. Le principal inconvénient des huiles minérales renfermant des additifs phospho-soufrés est leur instablilité thermique, qui commence à se manifester dès 120-130°C. Or il n'est pas rare que des températures de 150°C soient atteintes dans les transmissions de poids lourds ou de voitures particulières utilisées dans des conditions sévères. Les huiles de transmission à base de borate de potassium sont nettement plus stables thermiquement, mais sont sensibles à l'eau, ce qui est rédhibitoire pour certains usages. Des additifs antiusure et extrême-pression plus efficaces, plus stables thermiquement et présentant moins d'interactions avec les autres additifs dans les formulations sont activement recherchés.With regard to transmission oils, two types of additive are widely used: phospho-sulfur additives and additives based on potassium borate dispersion. The main disadvantage of mineral oils containing phospho-sulfur additives is their thermal instability, which begins to manifest from 120-130 ° C. However, it is not uncommon for temperatures of 150 ° C to be reached in the transmissions of heavy goods vehicles or passenger cars used under severe conditions. Transmission oils based on potassium borate are significantly more thermally stable, but are sensitive to water, which is unacceptable for certain uses. More effective antiwear and extreme pressure additives, more thermally stable and having less interactions with the other additives in the formulations are actively sought.
Les composés thiophosphorés micellaires de la présente invention peuvent être définis d'une manière générale comme étant obtenus par réaction d'au moins un sulfonate surbasé (A) avec un sulfure de phosphore (B), le produit réactionnel pouvant être éventuellement mis au contact avec au moins un composé à hy drogène actif (C). La réaction entre A et B, et éventuellement le traitement subséquent par C, peut avantageusement être effectuée dans un solvant (D).The micellar thiophosphorus compounds of the present invention can be generally defined as being obtained by reaction of at least one overbased sulfonate (A) with a phosphorus sulfide (B), the reaction product possibly being brought into contact with at least one compound with hy active drogen (C). The reaction between A and B, and optionally the subsequent treatment with C, can advantageously be carried out in a solvent (D).
Le composé A est un sulfonate surbasique obtenu à partir d'au moins un sel de métal alcalin ou alcalino-terreux d'au moins un composé acide choisi parmi les acides sulfoniques, naturels ou synthétiques. La surbasification des sels de métaux alcalins ou alcalino-terreux de ces acides s'effectue en général en présence d'un promoteur, en traitant un excès d'oxyde ou d'hydroxyde de métal alcalin ou alcalino-terreux en suspension dans le milieu réactionnel, par un acide faible tel que CO₂, SO₂, H₂S, ou H₃BO₃. Les cations les plus utilisés pour la surbasification sont le sodium, le magnésium, le calcium et le baryum utilisés sous forme de leur oxyde ou hydroxyde. Le promoteur est un alcool, particulièrement le méthanol, un alkylphénol ou un composé aminé tel que l'ammoniaque, une amine ou un amino-alcool. L'acide faible le plus couramment utilisé est le CO₂.Compound A is an overbased sulfonate obtained from at least one alkali or alkaline earth metal salt of at least one acid compound chosen from sulfonic acids, natural or synthetic. The overbasification of the alkali or alkaline earth metal salts of these acids is generally carried out in the presence of a promoter, by treating an excess of oxide or hydroxide of alkali or alkaline earth metal suspended in the reaction medium , by a weak acid such as CO₂, SO₂, H₂S, or H₃BO₃. The most used cations for overbasification are sodium, magnesium, calcium and barium used in the form of their oxide or hydroxide. The promoter is an alcohol, particularly methanol, an alkylphenol or an amino compound such as ammonia, an amine or an amino alcohol. The most commonly used weak acid is CO₂.
La préparation des additifs surbasiques est bien connue et est décrite par exemple dans les brevets : US 2 865 956, 3 150 088, 3 537 996, 3 830 739, 3 865 737, 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.The preparation of overbased additives is well known and is described for example in the patents: US 2,865,956, 3,150,088, 3,537,996, 3,830,739, 3,865,737, 4,148,740 and 4,505,830 and the 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.
Les acides sulfoniques pour la fabrication des sulfonates surbasiques utilisables selon l'invention sont connus et décrits dans de nombreux brevets, par exemple dans le brevet français 2 101 813, pages 5 et 6. La portion hydrocarbonée de la molécule présente avantageusement une masse moléculaire au moins égale à 370 pour assurer la miscibilité des sulfonates correspondants dans les huiles minérales. Il peut s'agir d'acides dits "naturels", issus de la sulfonation de coupes pétrolières, ou d'acides synthétiques préparés par sulfonation de charges préparés par voie synthétique : les hydrocarbures alkényliques, tels que polyisobutènes (brevet US 4 159 956), les hydrocarbures alkylaryliques comme par exemple les post-dodécylbenzènes obtenus comme produit de queue de la fabrication de dodécylbenzène.The sulfonic acids for the manufacture of overbased sulfonates which can be used according to the invention are known and described in numerous patents, for example in French patent 2 101 813, pages 5 and 6. The hydrocarbon portion of the molecule advantageously has a molecular weight at less than 370 to ensure the miscibility of the corresponding sulfonates in mineral oils. They may be so-called "natural" acids, resulting from the sulfonation of petroleum cuts, or of synthetic acids prepared by sulfonation of charges prepared by synthetic route: alkenyl hydrocarbons, such as polyisobutenes (US Pat. 4,159,956), alkylaryl hydrocarbons such as for example post-dodecylbenzenes obtained as tail product of the manufacture of dodecylbenzene.
Les composés A surbasiques préférés selon l'invention sont les sulfonates de sodium ou de calcium surbasés par le carbonate de sodium ou le carbonate de calcium.The overbased compounds A preferred according to the invention are the sodium or calcium sulfonates overbased with sodium carbonate or calcium carbonate.
Les sulfonates surbasiques A utilisables selon l'invention ont une alcalinité exprimée en terme de TBN (alcalinité équivalente exprimée en milligramme de KOH par g de produit) comprise entre 50 et 550 (soit de 0,9 à 10 équivalents basiques par kg) et de préférence entre 150 et 450 (soit de 2,7 à 8 équivalents basiques par kg).The overbased sulfonates A which can be used according to the invention have an alkalinity expressed in terms of TBN (equivalent alkalinity expressed in milligrams of KOH per g of product) between 50 and 550 (or from 0.9 to 10 basic equivalents per kg) and preferably between 150 and 450 (i.e. 2.7 to 8 basic equivalents per kg).
Le composé B est un sulfure de phosphore tel que P₄S₇, P₄S₉, P₄S₁₀. P₄S₁₀, est le sulfure de phosphore préféré selon l'invention. Le sulfure de phosphore est utilisé en quantité telle que le rapport P molaire/EB, où EB représente l'équivalent basique de l'additif surbasique, est compris entre 0,002 et 0,15 et de préférence entre 0,02 et 0,12. Au delà du rapport P molaire/EB = 0,15, la réaction entre l'additif surbasique et le sulfure de phosphore risque d'être incomplète.Compound B is a phosphorus sulfide such as P₄S₇, P₄S₉, P₄S₁₀. P₄S₁₀, is the preferred phosphorus sulfide according to the invention. The phosphorus sulfide is used in an amount such that the P mol / EB ratio, where EB represents the basic equivalent of the overbased additive, is between 0.002 and 0.15 and preferably between 0.02 and 0.12. Above the molar P / EB ratio = 0.15, the reaction between the overbased additive and the phosphorus sulphide may be incomplete.
Le composé C pouvant être éventuellement utilisé est un composé renfermant un hydrogène actif ; ce peut être de l'eau, un alcool tel que le méthanol ou l'isopropanol, un phénol, un acide tel qu'un acide carboxylique comme l'acide acétique, un ester acide comme un dialkylphosphite, un acide minéral comme l'acide borique ou l'acide phosphorique, une base comme l'ammoniac ou une amine, un amide, un mercaptan, tel que le dimercaptothiadiazole ou ses dérivés substitués de formule
La quantité molaire du composé C introduite par rapport à la quantité molaire de phosphore apporté par le sulfure de phosphore, peut varier dans un rapport compris entre 0,1 et 5, et de préférence entre 0,3 et 3.The molar quantity of compound C introduced relative to the molar quantity of phosphorus provided by the phosphorus sulphide can vary in a ratio of between 0.1 and 5, and preferably between 0.3 and 3.
Les composés C préférés selon l'invention sont l'ammoniac, l'isopropanol, les dialkylphosphites, l'acide borique, les mercaptans, en particulier les dérivés du dimercaptothiadiazole.The preferred compounds C according to the invention are ammonia, isopropanol, dialkylphosphites, boric acid, mercaptans, in particular derivatives of dimercaptothiadiazole.
Le solvant D éventuellement utilisé permet de réduire la viscosité du milieu réactionnel et ainsi d'améliorer le contact des réactifs. Comme exemples de solvants utilisables selon l'invention, on peut citer le cyclohexane, le toluène, les xylènes et de façon générale les coupes d'hydrocarbures ayant un intervalle d'ébullition compris entre 60 et 150°C et de préférence entre 90 et 120°C.The solvent D possibly used makes it possible to reduce the viscosity of the reaction medium and thus to improve the contact of the reactants. As examples of solvents which can be used according to the invention, mention may be made of cyclohexane, toluene, xylenes and in general hydrocarbon fractions having a boiling range of between 60 and 150 ° C. and preferably between 90 and 120 ° C.
Les additifs obtenus selon l'invention peuvent présenter une certaine réactivité vis-a-vis des alliages cuivreux. L'utilisation d'additifs séquestrants du type dimercaptothiadiazole à des doses comprises entre 0,25 et 0,75 % en masse dans les formulations finales conduit à un comportement entièrement satisfaisant vis-à-vis du cuivre. La dose requise est inférieure lorsque le composé C est lui-même un dérivé du mercaptothiadiazole. Elle peut aller par exemple jusqu'à 0,5 % en masse.The additives obtained according to the invention can have a certain reactivity with respect to copper alloys. The use of sequestering additives of the dimercaptothiadiazole type in doses of between 0.25 and 0.75% by mass in the final formulations leads to entirely satisfactory behavior with respect to copper. The dose required is lower when compound C is itself a derivative of mercaptothiadiazole. It can go for example up to 0.5% by mass.
La nature des composés formés au cours de la réaction n'est pas connue avec certitude. On peut supposer que les sulfures de phosphore réagissent sur la dispersion colloïdale du sel d'acide faible et de base alcaline ou alcanino-terreuse, pour former des thiophosphates minéraux alcalins ou alcalino-terreux. Cette hypothèse se trouve confortée par le fait que lors de la dialyse en milieu hydrocarbure des produits selon l'invention, la totalité du phosphore est retrouvée dans la fraction non dialysée.The nature of the compounds formed during the reaction is not known with certainty. It can be assumed that the phosphorus sulphides react on the colloidal dispersion of the salt of weak acid and of alkaline or alkaline earth base, to form alkaline or alkaline earth mineral thiophosphates. This hypothesis is supported by the fact that during dialysis in a hydrocarbon medium of the products according to the invention, all of the phosphorus is found in the non-dialyzed fraction.
Une autre caractéristique de la présente invention est que, dans les limites définies, les produits obtenus conservent l'état colloïdal en donnant des solutions dans les hydrocarbures parfaitement limpides et stables dans le temps.Another characteristic of the present invention is that, within the defined limits, the products obtained retain the colloidal state by giving solutions in the hydrocarbons perfectly clear and stable over time.
Le procédé de fabrication des composés selon l'invention comporte les étapes suivantes:The process for manufacturing the compounds according to the invention comprises the following steps:
La réaction du sulfure de phosphore sur le sulfonate surbasique peut être effectuée à une pression comprise entre la pression atmosphérique et environ 5 bars absolus (0,5 MPa), à une température comprise entre 60 et 130°C et de préférence entre 85 et 120°C. La réaction entre le sulfure de phosphore, réactif solide et l'additif surbasique est facilitée par une bonne agitation du milieu réactionnel et par l'emploi éventuel d'un solvant hydrocarboné D. Le sulfure de phosphore peut être introduit progressivement dans le milieu réactionnel, mais il peut également être introduit en totalité en début de manipulation dans le composé surbasique éventuellement dissous dans un solvant hydrocarboné, à condition que la température du milieu réactionnel soit inférieure à environ 60°C. La réaction est déclenchée alors en élevant progressivement la température dans les fourchettes indiquées ci-dessus.The reaction of phosphorus sulfide on overbased sulfonate can be carried out at a pressure between atmospheric pressure and about 5 bar absolute (0.5 MPa), at a temperature between 60 and 130 ° C and preferably between 85 and 120 ° C. The reaction between the phosphorus sulphide, solid reagent and the overbased additive is facilitated by good stirring of the reaction medium and by the possible use of a hydrocarbon solvent D. The phosphorus sulphide can be gradually introduced into the reaction medium, but it can also be introduced entirely at the start of handling into the overbased compound optionally dissolved in a hydrocarbon solvent, provided that the temperature of the reaction medium is less than about 60 ° C. The reaction is then started by gradually raising the temperature in the ranges indicated above.
Le composé C à hydrogène actif peut se présenter sous forme gazeuse, liquide ou solide et les moyens d'introduction dans le milieu réactionnel seront appropriés à son état physique. La réaction peut être effectuée à une pression comprise entre la pression atmosphérique et environ 5 bars absolus (0,5 MPa), à une température comprise entre 60 et 130°C et de préférence entre 25 et 120°C.Compound C with active hydrogen can be in gaseous, liquid or solid form and the means of introduction into the reaction medium will be appropriate to its physical state. The reaction can be carried out at a pressure between atmospheric pressure and about 5 bar absolute (0.5 MPa), at a temperature between 60 and 130 ° C and preferably between 25 and 120 ° C.
Filtration et élimination des solvants et de l'excès éventuel de réactif. L'étape de filtration n'est pas toujours nécessaire, les étapes 1 et 2 conduisant dans la plupart des cas à des mélanges liquides homogènes. Lorsque la filtration s'impose, elle peut être réalisée avant l'élimination du solvant D, par exemple sur de simples disques de cellulose, soit sur des couches d'agents filtrants de type diatomite ou de silice naturelle d'origine volcanique. On peut également procéder à la filtration après élimination des solvants. Dans ce cas, il est avantageux d'effectuer la filtration à chaud, par exemple de 90 à 120°C et sous une pression de 2 à 5 bars.Filtration and elimination of solvents and any excess of reagent. The filtration step is not always necessary, steps 1 and 2 leading in most cases to homogeneous liquid mixtures. When filtration is required, it can be carried out before the removal of solvent D, for example on simple cellulose disks, or on layers of filtering agents of the diatomite type or of natural silica of volcanic origin. Filtration can also be carried out after removal of the solvents. In this case, it is advantageous to carry out hot filtration, for example from 90 to 120 ° C and under a pressure of 2 to 5 bars.
La distillation du solvant peut être réalisée dans le réacteur lui-même. L'élimination des dernières traces est facilitée par un stripping à l'azote. Elle peut être également effectuée dans un évaporateur à film mince.The distillation of the solvent can be carried out in the reactor itself. The elimination of the last traces is facilitated by a nitrogen stripping. It can also be carried out in a thin film evaporator.
Les exemples suivants illustrent l'invention. Ils ne doivent en aucune manière être considérés comme limitatifs.The following examples illustrate the invention. They should in no way be considered as limiting.
Dans un réacteur agité et sous couverture d'azote, on introduit 292,8 g d'un sulfonate de calcium surbasé par du carbonate de calcium dont le TBN est de 410 mg KOH/g (soit un nombre d'équivalents basiques de 7,32 par kg) et 300 ml de toluène. Lorsque le mélange est homogène, 25,7 g (0,058 mole) de P₄S₁₀ sont introduits dans le réacteur et la température est progressivement portée à 90°C, puis maintenue à ce niveau pendant 2 heures. Les effluents gazeux sont absorbés dans une solution de potasse à 10 %. Le mélange réactionnel est alors porté au reflux ; la température se stabilise à 115°C. Après 2 heures à cette température, le toluène est distillé sous courant d'azote, puis le produit de réaction est maintenu à 155°C pendant 2 heures tandis que le barbotage d'azote est poursuivi. Le produit est finalement flltré sur terre filtrante à 100°C, sous pression de 3 bars d'azote. On obtient finalement 301 g d'un produit ayant l'analyse élémentaire suivante:
Ca : 14,7 % masse
P : 2,00 % masse
S : 4,2 % masse292.8 g of a calcium sulfonate overbased with calcium carbonate, the TBN of which is 410 mg KOH / g (ie a number of basic equivalents of 7, are introduced into a stirred reactor under nitrogen blanket) 32 per kg) and 300 ml of toluene. When the mixture is homogeneous, 25.7 g (0.058 mole) of P₄S₁₀ are introduced into the reactor and the temperature is gradually brought to 90 ° C, then maintained at this level for 2 hours. The gaseous effluents are absorbed in a 10% potash solution. The reaction mixture is then brought to reflux; the temperature stabilizes at 115 ° C. After 2 hours at this temperature, the toluene is distilled under a stream of nitrogen, then the reaction product is kept at 155 ° C. for 2 hours while the nitrogen bubbling is continued. The product is finally filtered on filter earth at 100 ° C, under pressure of 3 bars of nitrogen. 301 g of a product are finally obtained having the following elementary analysis:
Ca: 14.7% mass
P: 2.00% mass
S: 4.2% mass
Il est procédé comme à l'exemple 1 jusqu'à la fin du reflux de 2 heures à 115°C. A ce moment, on fait barboter 12 g d'ammoniac (0,706 mole) dans le mélange réactionnel. La durée d'introduction est de 1,5 heures. On fait ensuite passer un courant d'azote pour chasser l'excès d'ammoniac et le mélange réactionnel est filtré sur terre filtrante. Le toluène est distillé du mélange réactionnel à l'évaporateur rotatif. On recueille finalement 307,4 g d'un produit dont l'analyse est la suivante :
Ca : 14,5 % masse
P : 2,06 % masse
S : 4,25 % masse
M : 0,58 % masseThe procedure is as in Example 1 until the end of the 2 hour reflux at 115 ° C. At this point, 12 g of ammonia (0.706 mol) are bubbled into the reaction mixture. The introduction time is 1.5 hours. A stream of nitrogen is then passed to remove the excess ammonia and the reaction mixture is filtered on filter earth. The toluene is distilled from the reaction mixture on a rotary evaporator. 307.4 g of a product are finally collected, the analysis of which is as follows:
Ca: 14.5% mass
P: 2.06% mass
S: 4.25% mass
M: 0.58% mass
Dans un réacteur agité et sous couverture d'azote, 293,7 g du sulfonate surbasique utilisé dans les exemples précédents sont dissous dans 300 ml de toluène. 23 g (0,052 mole) de P₄S₁₀ sont alors progressivement introduits dans le réacteur à la température de 90°C. Après la fin de l'introduction de P₄S₁₀, le mélange réactionnel est maintenu à cette température pendant encore 2 heures, puis le mélange est porté à reflux à 115°C pendant 1 heure pour s'assurer que la réaction est complète. La température est alors ramenée à 65°C et l'on introduit progressivement 29,7 g (0,495 mole) d'isopropanol dilués dans 50 ml de toluène, puis le milieu réactionnel est maintenu à 75°C pendant 3 heures. Après refroidissement, le mélange est filtré sur terte d'infusoire et les composés volatils sont éliminés à l'évaporateur rotatif. On obtient finalement 313,2 g d'un produit dont l'analyse est la suivante:
Ca : 14,2 % masse
P : 1,87 % masse
S : 3,25 % masseIn a stirred reactor and under a nitrogen blanket, 293.7 g of the overbased sulfonate used in the previous examples are dissolved in 300 ml of toluene. 23 g (0.052 mole) of P₄S₁₀ are then gradually introduced into the reactor at the temperature of 90 ° C. After the end of the introduction of P₄S₁₀, the reaction mixture is maintained at this temperature for another 2 hours, then the mixture is brought to reflux at 115 ° C for 1 hour to ensure that the reaction is complete. The temperature is then brought back to 65 ° C. and 29.7 g (0.495 mol) of isopropanol diluted in 50 ml of toluene are gradually introduced, then the reaction medium is maintained at 75 ° C. for 3 hours. After cooling, the mixture is filtered on a diatomaceous earth and the volatile compounds are eliminated on a rotary evaporator. 313.2 g of a product are finally obtained, the analysis of which is as follows:
Ca: 14.2% mass
P: 1.87% mass
S: 3.25% mass
IL est procédé comme à l'exemple 3 à la différence près que l'on introduit progressivement 5 g (0,278 mole) d'eau à la place de l'isopropanol dilué dans le toluène. On récupère finalement 294,1 g d'un produit ayant la composition suivante:
Ca : 14,4 % masse
P : 1,84 % masse
S : 2,85 % masseIT is carried out as in Example 3 with the difference that 5 g (0.278 mole) of water are gradually introduced in place of the isopropanol diluted in toluene. Finally recovered 294.1 g of a product having the following composition:
Ca: 14.4% mass
P: 1.84% mass
S: 2.85% mass
La réaction est effectuée dans les mêmes conditions qu'à l'exemple 3, à la différence près que l'alcool utilisé est le méthanol. La quantité de méthanol introduite dans les mêmes conditions que ci-dessus est de 16 g (0,5 mole). Après flltration, puis élimination des composés volatils, on recueille finalement 310,7 g d'un produit dont l'analyse est la suivante:
Ca : 14,4 % masse
P : 1,99 % masse
S : 3,8 % masse
The reaction is carried out under the same conditions as in Example 3, with the difference that the alcohol used is methanol. The amount of methanol introduced under the same conditions as above is 16 g (0.5 mole). After filtration, then elimination of the volatile compounds, 310.7 g of a product are finally collected, the analysis of which is as follows:
Ca: 14.4% mass
P: 1.99% mass
S: 3.8% mass
Dans un réacteur agité et sous couverture d'azote sont introduits 244,75 g du sulfonate surbasique utilisé dans les exemples précédents et 250 ml de toluène. Le mélange est porté à 85-90°C. On introduit alors 18,7 g (0,042 mole) de P₄S₁₀ en 1 heure, les effluents gazeux sont recueillis dans une solution de potasse à 10 %. Le mélange est maintenu agité à la température de 90°C pendant 3 heures supplémentaires. Tout le P₄S₁₀ est alors entré en réaction. On introduit ensuite 10,2 g d'un dérivé de dimercaptothiadiazole vendu par la société AMOCO sous la dénomination commerciale AMOCO 153 en solution dans une masse équivalente de toluène. La température est portée à 115°C et est maintenue pendant 1,5 heure. Le toluène est ensuite distillé sous courant d'azote. On récupère finalement 263,1 g d'un liquide visqueux dont les concentrations en calcium, phosphore soufre et azote sont les suivantes :
Ca : 14,3 % masse
P : 1,71 % masse
S : 5,3 % masse
N : 0,31 % masse244.75 g of the overbased sulfonate used in the previous examples and 250 ml of toluene are introduced into a stirred reactor under a nitrogen blanket. The mixture is brought to 85-90 ° C. Then introduced 18.7 g (0.042 mole) of P₄S₁₀ in 1 hour, the gaseous effluents are collected in a 10% potassium hydroxide solution. The mixture is kept stirred at the temperature of 90 ° C for an additional 3 hours. All the P₄S₁₀ then entered a reaction. Then introduced 10.2 g of a dimercaptothiadiazole derivative sold by the company AMOCO under the trade name AMOCO 153 in solution in an equivalent mass of toluene. The temperature is brought to 115 ° C. and is maintained for 1.5 hours. The toluene is then distilled under a stream of nitrogen. 263.1 g of a viscous liquid are finally recovered, the calcium, phosphorus sulfur and nitrogen concentrations of which are as follows:
Ca: 14.3% mass
P: 1.71% mass
S: 5.3% mass
N: 0.31% mass
Il est procédé comme à l'exemple 1, mais avec les quantités suivantes de réactifs:
- sulfonate surbasique utilisé dans les examples précédents = 247,7 g
- P₄S₁₀ = 8,25(0,019 mole)
- toluène = 250 mlThe procedure is as in Example 1, but with the following amounts of reactants:
- overbased sulfonate used in the previous examples = 247.7 g
- P₄S₁₀ = 8.25 (0.019 mole)
- toluene = 250 ml
Le produit obtenu après filtration et élimination du toluène, soit 253,3 g, présente les caractéristiques suivantes :
Ca : 14,2 % masse
P : 0,88 % masse
S : 2,25 % masseThe product obtained after filtration and elimination of the toluene, ie 253.3 g, has the following characteristics:
Ca: 14.2% mass
P: 0.88% mass
S: 2.25% mass
IL est procédé comme à l'exemplè 5 jusqu'à réaction complète du P₄S₁₀. On introduit alors en une heure 24,5 g d'acide borique. Le mélange est ensuite porté à reflux à 115°C pendant 1,5 heure. Après filtration sur filtre de cellulose et évaporation du solvant, on obtient 266,3 g d'un produit dont l'analyse est la suivante :
Ca : 14,0 % masse
P : 1,69 % masse
S : 4,2 % masse
B : 1,51 % masseIT is carried out as in Example 5 until complete reaction of the P₄S₁₀. 24.5 g of boric acid are then introduced in one hour. The mixture is then brought to reflux at 115 ° C for 1.5 hours. After filtration through a cellulose filter and evaporation of the solvent, 266.3 g of a product are obtained, the analysis of which is as follows:
Ca: 14.0% mass
P: 1.69% mass
S: 4.2% mass
B: 1.51% mass
Il est procédé comme à l'exemple 6 jusqu'à réaction complète du P₄S₁₀. La température étant maintenue à 90°C, on introduit en 1 heure 49,5 g de didodécylphosphite en solution dans 50 ml de toluène. Puis la température est portée à 115°C et est maintenue pendant 3 heures.The procedure is as in Example 6 until complete reaction of the P₄S₁₀. The temperature being maintained at 90 ° C., 49.5 g of didodecylphosphite dissolved in 50 ml of toluene are introduced over 1 hour. Then the temperature is brought to 115 ° C. and is maintained for 3 hours.
Le toluène est ensuite distillé sous courant d'azote. On récupère finalement 302 g d'un liquide visqueux dont l'analyse est la suivante:
Ca : 12,2 % masse
P : 2,78 % masse
S : 3,45 % masseThe toluene is then distilled under a stream of nitrogen. Finally, 302 g of a viscous liquid are recovered, the analysis of which is as follows:
Ca: 12.2% mass
P: 2.78% mass
S: 3.45% mass
La réaction est effectuée avec les mêmes quantités de réactifs et dans les mêmes conditions qu'à l'exemple 3, à la différence près que la réaction est effectuée dans un réacteur sous pression en Hastelloy (marque déposée), muni d'un système d'agitation magnétique rigoureusement étanche. Après refroidissement, le réacteur est ramené à la pression atmosphérique et on procède à la filtration et à l'élimination des composés volatils. Après ces opérations, on récupère 315,1 g d'un produit de composition suivante:
Ca : 14,1 % masse
P : 1,95 % masse
S : 4,5 % masseThe reaction is carried out with the same quantities of reagents and under the same conditions as in Example 3, with the difference that the reaction is carried out in a pressure reactor made of Hastelloy (registered trademark), equipped with a system rigorously sealed magnetic stirring. After cooling, the reactor is brought back to atmospheric pressure and the volatile compounds are filtered and eliminated. After these operations, 315.1 g of a product of the following composition are recovered:
Ca: 14.1% mass
P: 1.95% mass
S: 4.5% mass
La réaction est effectuée dans les mêmes conditions qu'à l'exemple 1, à la différence près que l'on utilise comme composé A, 324,5 g d'un sulfonate de sodium surbasé par du carbonate de calcium ayant un TBN de 370 mg KOH/g (soit un nombre d'équivalents basiques de 6,6/kg). On récupère finalement 342,1 g d'un produit de composition suivante:
Ca : 11,3 % masse
Ma : 1,30 % masse
P : 1,92 % masse
S : 3,70 % masseThe reaction is carried out under the same conditions as in Example 1, with the difference that 324.5 g of a sodium sulfonate overbased with calcium carbonate having a TBN of 370 is used as compound A mg KOH / g (i.e. a number of basic equivalents of 6.6 / kg). 342.1 g of a product of the following composition are finally recovered:
Ca: 11.3% mass
Ma: 1.30% mass
P: 1.92% mass
S: 3.70% mass
La réaction est effectuée avec les mêmes quantités de réactifs et dans les mêmes conditions qu'à l'exemple 3, à la différence près qu'à la suite du reflux de 1 heure à 115°C et avant l'introduction de l'isopropanol, 6,4 g (0,043 mole) de 2,5 dimercapto-1,3,4-thiadiazole sont ajoutés progressivement au milieu réactionnel dont la température a été préalablement ramenée à 90°C.
L'addition d'isopropanol et la fin de la fabrication sont ensuite conduits selon les indications de l'exemple 3. On obtient finalement 323,4 g d'un liquide visqueux dont l'analyse est la suivante:
Ca : 14,0 % masse
P : 1,94 % masse
S : 4,62 % masse
N : 0,45 % maseThe reaction is carried out with the same amounts of reagents and under the same conditions as in Example 3, with the difference that after refluxing for 1 hour at 115 ° C. and before the introduction of isopropanol 6.4 g (0.043 mole) of 2.5 dimercapto-1,3,4-thiadiazole are gradually added to the reaction medium, the temperature of which has previously been brought to 90 ° C.
The addition of isopropanol and the end of the production are then carried out according to the indications in Example 3. Finally, 323.4 g of a viscous liquid are obtained, the analysis of which is as follows:
Ca: 14.0% mass
P: 1.94% mass
S: 4.62% mass
N: 0.45% mase
Les produits décrits dans les exemples précédents ont été évalués pour leur propriétés antiusure et extrême-pression dans une huile lubrifiante. L'huile minérale de base utilisée est une 130 Neutral de caractéristiques suivantes :
Viscosité cinématique à 40°C : 25,5 mm²/s
Viscosité cinématique à 100°C : 4,7 mm²/s
Index de viscosité : 101
Point d'écoulement : - 15°C
Teneur en soufre : 0,46 % masseThe products described in the previous examples were evaluated for their antiwear and extreme pressure properties in a lubricating oil. The base mineral oil used is a 130 Neutral with the following characteristics:
Kinematic viscosity at 40 ° C: 25.5 mm² / s
Kinematic viscosity at 100 ° C: 4.7 mm² / s
Viscosity index: 101
Pour point: - 15 ° C
Sulfur content: 0.46% mass
L'efficacité antiusure est évaluée sur machine à 4 billes fonctionnant pendant 1 heure sous des charges de 40 et 60 daN une vitesse de 1500 t/min, selon la méthode NF E48-617. Les moyennes du diamètre d'empreinte observées sur les 3 billes inférieures sont les suivantes :
Les propriétés extrême-pression dans les huiles lubrifiantes des produits selon l'invention ont été mesurées sur machine d'engrenages FZG selon la méthode CEC L-07-A-71 avec la procédure A/16,6/90, c'est-à-dire utilisant l'engrenage de type A, avec une vitesse circonférentielle au diamètre primitif de 16,6 m/s et à la température de 90°C au début de chaque palier de charge. L'huile minérale utilisée est la base 130 N décrite ci-dessus. La méthode B de cotation visuelle a été utilisée. L'efficacité extrême-pression est d'autant plus prononcée que le palier de charge atteint est plus élevé. Lorsque cela a été possible, on a également relevé la température de l'huile à la fin du palier 12 qui est en relation avec les forces dissipées dans les frottements. Une température plus basse traduit un coefficient de frottement plus faible dans les conditions de l'essai. Les résultats obtenus figurent dans le tableau suivant :
L'ensemble de ces résultats montrent que les produits selon l'invention ont des propriétés extrême-pression très prononcées et que le coefficient de frottement est inférieur à celui des additifs extrême-pression classiques puisque les températures enregistrées en fin de palier 12 sont nettement inférieures, ce qui constitue un avantage évident dans des conditions sévères d'utilisation: boîtes de vitesse et pont-arrière de poids lourds à faible vitesse sous couple élevé, réducteurs ferroviaires de trains à grande vitesse, réducteurs d'hélicoptères, etc...All of these results show that the products according to the invention have very pronounced extreme pressure properties and that the coefficient of friction is lower than that of conventional extreme pressure additives since the temperatures recorded at the end of level 12 are much lower. , which is an obvious advantage under severe conditions of use: gearboxes and rear axle of heavy goods vehicles at low speed with high torque, railway reducers for high speed trains, helicopter reducers, etc.
En vue de déterminer le comportement d'additifs selon l'invention dans la lubrification des moteurs, il a été procédé à des essais d'usure sur une maquette de distribution came-basculeurs de moteur PEUGEOT XL5. L'arbre à cames est en fonte coulée trempée, les basculeurs sont en acier 42C2 trempé et nitruré en bain de sel sans cyanure (procédé SURSULF). La base lubrifiante est une 175 Neutral Solvant dont les principales caractéristiques sont les suivantes:
Viscosité cinématique à 40°C : 33,7 mm²/s
Viscosité cinématique à 100°C : 5,7 mm²/s
Index de viscosité : 108
Point d'écoulement : -9°CIn order to determine the behavior of additives according to the invention in the lubrication of the engines, wear tests were carried out on a cam-rocker distribution model of the PEUGEOT XL5 engine. The camshaft is made of hardened cast iron, the rockers are made of hardened and nitrided 42C2 steel in a salt bath without cyanide (SURSULF process). The lubricant base is a 175 Neutral Solvent, the main characteristics of which are as follows:
Kinematic viscosity at 40 ° C: 33.7 mm² / s
Kinematic viscosity at 100 ° C: 5.7 mm² / s
Viscosity index: 108
Pour point: -9 ° C
L'objectif visé dans cet essai était de remplacer l'additif antiusure et l'additif détergent par un additif selon l'invention. Par contre, un additif dispersant classique de type succinimide habituellement utilisé pour satisfaire les exigences de dispersivité à froid a été utilisé.The objective of this test was to replace the antiwear additive and the detergent additive with an additive according to the invention. On the other hand, a conventional dispersant additive of the succinimide type usually used to satisfy the requirements of cold dispersivity was used.
Le banc d'essai est entrainé par un moteur électrique et fonctionne selon le cycle suivant:
1 minute à 750 t/min
2 minutes à 1500 t/minThe test bench is driven by an electric motor and operates according to the following cycle:
1 minute at 750 rpm
2 minutes at 1500 rpm
Les ressorts, sous levée maximale, sont tarés à 1200 N. La durée de l'essai est de 50 heures et la température de l'huile est régulée à 50°C. A l'issue de l'essai, les basculeurs sont pesés et cotés selon une échelle qui définit quatre aspects-types.The springs, under maximum lift, are rated at 1200 N. The duration of the test is 50 hours and the oil temperature is regulated at 50 ° C. At the end of the test, the rockers are weighed and rated according to a scale which defines four typical aspects.
La formulation I comportant un additif selon l'invention a la composition suivante:
-produit de l'exemple 6 = 5,3 % en masse
- additif dispersant = 5 % en masse
- base 175 N = 89,7 % en masseThe formulation I comprising an additive according to the invention has the following composition:
-product of Example 6 = 5.3% by mass
- dispersing additive = 5% by mass
- base 175 N = 89.7% by mass
A titre de comparaison, une huile II à base d'additifs conventionnels a été essayée dans des conditions identiques. Sa composition est la suivante:
-Additifs antiusure (dialkyldithiophosphate de zinc) correspondant à 1400 ppm de zinc) = 1,70 % en masse
- additif détergent = 3,6 % en masse
- additif dispersant = 5 % en masse
- base 175 N = 89,7 % en masseFor comparison, an oil II based on conventional additives was tested under identical conditions. Its composition is as follows:
-Anti-wear additives (zinc dialkyldithiophosphate) corresponding to 1400 ppm zinc) = 1.70% by mass
- detergent additive = 3.6% by mass
- dispersing additive = 5% by mass
- base 175 N = 89.7% by mass
Les résultats obtenus sont indiqués ci-dessous:
Ils montrent une moindre usure et un meilleur aspect des basculeurs avec la formule utilisant l'additif selon l'invention.They show less wear and a better appearance of the rockers with the formula using the additive according to the invention.
Le banc utilisé et les conditions d'essais sont décrits en détail dans une communication au 7ème Colloque international sur la lubrification automobile. Esslingen ; 16-18 janvier 1990. (The screening of E.P. oil formulas by the use of a new hypoïd gear axle test. G. VENIZELOS, G. LASSAU, P. MARCHAND).The bench used and the test conditions are described in detail in a communication to the 7th International Symposium on automotive lubrication. Esslingen; January 16-18, 1990. (The screening of EP oil formulas by the use of a new hypoid gear axle test. G. VENIZELOS, G. LASSAU, P. MARCHAND).
Cet essai utilise un pont PEUGEOT PC7 sur lequel on applique des pics de couple de l'ordre de 340 N.m. La couronne est examiné sans démontage toutes les séries de 20 pics de couple. En l'absence d'usure anormale, l'essai est poursuivi jusqu'à 80 pics de couple, après quoi le pont est démonté et les surfaces du pignon et de la couronne sont examinées. Le résultat est donné en pourcentage de la surface portante détériorée par grippage (scoring).
Les additifs sont comparés dans une huile de base identique (100 neutral solvant). Un essai comparatif a été effectué avec un aditif extrême-pression commercialisé sous la dénomination d'ANGLAMOL 99 (marque déposée), additif extrême-pression largement utilisé dans les ponts hypoïdes.
The additives are compared in an identical base oil (100 neutral solvent). A comparative test was carried out with an extreme pressure additive sold under the name of ANGLAMOL 99 (registered trademark), extreme pressure additive widely used in hypoid bridges.
Claims (10)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8904345A FR2645168B1 (en) | 1989-03-30 | 1989-03-30 | NOVEL THIOPHOSPHORUS COMPOUNDS, THEIR PREPARATION AND THEIR USE AS LUBRICANT ADDITIVES |
FR8904345 | 1989-03-30 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0390664A2 true EP0390664A2 (en) | 1990-10-03 |
EP0390664A3 EP0390664A3 (en) | 1990-12-12 |
EP0390664B1 EP0390664B1 (en) | 1993-08-04 |
Family
ID=9380324
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90400818A Expired - Lifetime EP0390664B1 (en) | 1989-03-30 | 1990-03-23 | New thiophosphorous compounds, a process for preparing same and use of said compounds as lubricant additives |
Country Status (8)
Country | Link |
---|---|
US (1) | US5080812A (en) |
EP (1) | EP0390664B1 (en) |
JP (1) | JP2916644B2 (en) |
CA (1) | CA2013458C (en) |
DE (1) | DE69002511T2 (en) |
DK (1) | DK0390664T3 (en) |
ES (1) | ES2060085T3 (en) |
FR (1) | FR2645168B1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0639634A1 (en) * | 1993-08-18 | 1995-02-22 | Institut Français du Pétrole | Colloidal products containing calcium and/or magnesium as well as sulfur and nitrogen, their preparation and their use, especially as additives for lubricants |
FR2716891A1 (en) * | 1994-03-03 | 1995-09-08 | Inst Francais Du Petrole | New colloidal prods. useful as anti-wear and extreme pressure additives in oil and grease lubricants |
Families Citing this family (8)
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 |
FR2681872B1 (en) * | 1991-09-30 | 1993-12-24 | Inst Francais Du Petrole | COLLOUIDAL PRODUCTS CONTAINING BORON AND PHOSPHORUS, THEIR PREPARATION AND THEIR USE AS ADDITIVES FOR LUBRICANTS. |
MX9305120A (en) * | 1992-09-04 | 1994-03-31 | Lubrizol Corp | SULFURATED OVERBASED COMPOSITIONS. |
FR2698018B1 (en) * | 1992-11-18 | 1995-01-20 | Inst Francais Du Petrole | Colloidal products containing boron, and / or sulfur, and / or phosphorus, their preparation and their use as additives for lubricants. |
FR2698019B1 (en) * | 1992-11-18 | 1995-02-24 | Inst Francais Du Petrole | Colloidal products containing calcium and / or magnesium, as well as boron and / or phosphorus and / or sulfur, their preparation and their use as additives for lubricants. |
FR2755377B1 (en) * | 1996-11-06 | 1999-01-08 | Inst Francais Du Petrole | COLLOIDAL THIO-PHOSPHORUS PRODUCTS DERIVED FROM COLLOIDAL LIME, PREPARATION AND USES |
US5985805A (en) * | 1994-07-06 | 1999-11-16 | Institut Francais Du Petrole | Colloidal thio-phosphorous products derived from colloidal lime, their preparation and uses |
FR2733165B1 (en) * | 1995-04-20 | 1997-06-13 | Inst Francais Du Petrole | COLLOIDAL ALKALINE OR ALKALINE-EARTH CARBONATES CONTAINING A COMPOUND OF CALCIUM, PHOSPORUS AND SULFUR IN MISCELLANEOUS FORM |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3132101A (en) * | 1956-05-21 | 1964-05-05 | Sinclair Research Inc | Detergent and anti-oxidant lubricant |
DE1926505A1 (en) * | 1968-05-24 | 1969-12-04 | Mobil Oil Corp | Multipurpose lubricating oil |
US4328111A (en) * | 1978-11-20 | 1982-05-04 | Standard Oil Company (Indiana) | Modified overbased sulfonates and phenates |
US4804489A (en) * | 1987-10-29 | 1989-02-14 | The Lubrizol Corporation | Low molecular weight viscosity modifying compositions |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB590885A (en) * | 1944-01-17 | 1947-07-31 | Standard Oil Dev Co | Improvements relating to petroleum hydrocarbon products and the manufacture of addition agents therefor |
US2451345A (en) * | 1944-10-24 | 1948-10-12 | Standard Oil Dev Co | Compounded lubricating oil |
US2698296A (en) * | 1952-07-28 | 1954-12-28 | Standard Oil Co | Process for preparing lubricating oil additive and products |
US2956018A (en) * | 1955-07-01 | 1960-10-11 | Continental Oil Co | Metal containing organic compositions and method of preparing the same |
BE668916A (en) * | 1957-12-06 | |||
US3492231A (en) * | 1966-03-17 | 1970-01-27 | Lubrizol Corp | Non-newtonian colloidal disperse system |
US3474035A (en) * | 1967-03-20 | 1969-10-21 | Texaco Inc | Lubricating oil containing overbased sulfurized calcium alkylphenolate |
US3489682A (en) * | 1968-03-01 | 1970-01-13 | Lubrizol Corp | Metal salt compositions |
-
1989
- 1989-03-30 FR FR8904345A patent/FR2645168B1/en not_active Expired - Fee Related
-
1990
- 1990-03-23 DK DK90400818.2T patent/DK0390664T3/en active
- 1990-03-23 EP EP90400818A patent/EP0390664B1/en not_active Expired - Lifetime
- 1990-03-23 DE DE90400818T patent/DE69002511T2/en not_active Expired - Fee Related
- 1990-03-23 ES ES90400818T patent/ES2060085T3/en not_active Expired - Lifetime
- 1990-03-29 US US07/500,827 patent/US5080812A/en not_active Expired - Fee Related
- 1990-03-30 JP JP2087308A patent/JP2916644B2/en not_active Expired - Lifetime
- 1990-03-30 CA CA002013458A patent/CA2013458C/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3132101A (en) * | 1956-05-21 | 1964-05-05 | Sinclair Research Inc | Detergent and anti-oxidant lubricant |
DE1926505A1 (en) * | 1968-05-24 | 1969-12-04 | Mobil Oil Corp | Multipurpose lubricating oil |
US4328111A (en) * | 1978-11-20 | 1982-05-04 | Standard Oil Company (Indiana) | Modified overbased sulfonates and phenates |
US4804489A (en) * | 1987-10-29 | 1989-02-14 | The Lubrizol Corporation | Low molecular weight viscosity modifying compositions |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0639634A1 (en) * | 1993-08-18 | 1995-02-22 | Institut Français du Pétrole | Colloidal products containing calcium and/or magnesium as well as sulfur and nitrogen, their preparation and their use, especially as additives for lubricants |
FR2709076A1 (en) * | 1993-08-18 | 1995-02-24 | Inst Francais Du Petrole | 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. |
US5462682A (en) * | 1993-08-18 | 1995-10-31 | Institut Francais Du Petrole | Colloidal products containing calcium and/or magnesium, as well as sulfur and nitrogen, their preparation and their use particularly as additives in lubricating oils |
FR2716891A1 (en) * | 1994-03-03 | 1995-09-08 | Inst Francais Du Petrole | New colloidal prods. useful as anti-wear and extreme pressure additives in oil and grease lubricants |
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 |
---|---|
JPH02286791A (en) | 1990-11-26 |
FR2645168B1 (en) | 1993-02-05 |
DE69002511T2 (en) | 1993-11-18 |
EP0390664B1 (en) | 1993-08-04 |
EP0390664A3 (en) | 1990-12-12 |
JP2916644B2 (en) | 1999-07-05 |
FR2645168A1 (en) | 1990-10-05 |
CA2013458C (en) | 2002-04-23 |
ES2060085T3 (en) | 1994-11-16 |
CA2013458A1 (en) | 1990-09-30 |
US5080812A (en) | 1992-01-14 |
DE69002511D1 (en) | 1993-09-09 |
DK0390664T3 (en) | 1993-12-06 |
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