FR2671084A1 - New phosphosulphur compounds and their use as additives in lubricating oils - Google Patents
New phosphosulphur compounds and their use as additives in lubricating oils Download PDFInfo
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- FR2671084A1 FR2671084A1 FR9016530A FR9016530A FR2671084A1 FR 2671084 A1 FR2671084 A1 FR 2671084A1 FR 9016530 A FR9016530 A FR 9016530A FR 9016530 A FR9016530 A FR 9016530A FR 2671084 A1 FR2671084 A1 FR 2671084A1
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- phosphosulfurized
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- 239000000654 additive Substances 0.000 title claims abstract description 14
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 8
- BTHAQRDGBHUQMR-UHFFFAOYSA-N [S]P(=O)=O Chemical class [S]P(=O)=O BTHAQRDGBHUQMR-UHFFFAOYSA-N 0.000 title abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract 2
- 229930195733 hydrocarbon Natural products 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- -1 polymethylene chain Polymers 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 230000001050 lubricating effect Effects 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000004679 31P NMR spectroscopy Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- 239000005069 Extreme pressure additive Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007866 anti-wear additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229940084106 spermaceti Drugs 0.000 description 1
- 239000012177 spermaceti Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
- C10M137/14—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/1411—Esters of phosphorous acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
- C10M137/105—Thio derivatives not containing metal
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Abstract
Description
La présente invention concerne de nouveaux composés phosphosoufrés (c'est à dire soufrés et phosphorés) particuliers et leur utilisation comme additifs pétroliers, notamment comme additifs antioxydants, antiusure, extrême-pression et anticorrosifs pour huiles lubrifiantes. The present invention relates to new particular phosphosulfur compounds (that is to say sulfur and phosphorus compounds) and their use as petroleum additives, in particular as antioxidant, antiwear, extreme pressure and anticorrosive additives for lubricating oils.
L'utilisation d'additifs antiusure et extrême-pression notamment dans les huiles moteurs, les fluides de transmission, les fluides hydrauliques se pratique depuis plusieurs décennies. De nombreux types d'additifs ont ainsi été développés et plusieurs d'entre eux ont permis de réduire très sensiblement la détéroration des mécanismes et ont, de ce fait, permis de prolonger leur durée de vie. The use of antiwear and extreme pressure additives, in particular in engine oils, transmission fluids and hydraulic fluids has been practiced for several decades. Numerous types of additives have thus been developed and several of them have made it possible to very appreciably reduce the deterioration of the mechanisms and have, as a result, made it possible to extend their lifespan.
Parmi les nombreux additifs antiusure et extrême-pression qui ont été étudiés, les dialkyles et diaryldithiophosphates et les dialkylditiocarbamates métalliques (ceux de zinc notamment), les alkylthiophosphates, le tricrésylphosphate, le di dodécyl phosphate, les terpènes sulfurés, l'huile de spermacéti soufrée et divers composés chlorés se sont montrés les plus actifs et ont connu un développement industriel important. Certains d'entre eux sont décrits dans les brevets US-A-2 364 283, 2 364 284, 2 365 938, 2 410 650, 2 438 876, 3 190 833.Il s'agit généralement de composés renfermant des hétêroatomes tels que le soufre et le phosphore, soit seuls (par exemple le tri crésyl phosphate, les terpènes soufrés, les dithiocarbamatesj, soit en association (par exemple des dialkyldithiophosphates métalliques, des alkylthiophosphates). Among the many antiwear and extreme pressure additives that have been studied, dialkyls and diaryldithiophosphates and metal dialkylditiocarbamates (those of zinc in particular), alkylthiophosphates, tricresylphosphates, di dodecyl phosphate, sulfurized terpenes, sulfurized spermaceti oil and various chlorinated compounds have been shown to be the most active and have experienced significant industrial development. Some of them are described in US-A-2,364,283, 2,364,284, 2,365,938, 2,410,650, 2,438,876, 3,190,833. They are generally compounds containing heteroatomas such as sulfur and phosphorus, either alone (for example tri cresyl phosphate, sulfur terpenes, dithiocarbamatesj, or in combination (for example metal dialkyldithiophosphates, alkylthiophosphates).
Les composés phosphosoufrés utilises précédemment présentent des quantités relatives de soufre et de phosphore qui sont imposées par la stoéchiométrie des réactions lors de leur synthèse et qui leur confèrent notamment des propritês antiusure et extrêmepression relatives sur lesquelles l'homme de l'art ne peut exercer aucune modification. The phosphosulfur compounds used previously exhibit relative amounts of sulfur and phosphorus which are imposed by the stoichiometry of the reactions during their synthesis and which in particular give them antiwear properties and relative extreme pressure on which a person skilled in the art can exert no effect. modification.
Il a maintenant été découvert de nouveaux composés phosphosoufrés particuliers, utilisables notamment comme additifs de lubrification, préparés de préférence par réaction de réactifs phosphorés conventionnels avec des alcools (poly)soufrés, avec des composés époxydes, avec du chlorure de thionyle puis avec des (poly)sulfures alcalins, ce qui permet de modifier à volonté les performances relatives antiusure et extrême-pression desdits composés. It has now been discovered new particular phosphosulfur compounds, usable in particular as lubricating additives, preferably prepared by reaction of conventional phosphorus reagents with (poly) sulfur alcohols, with epoxy compounds, with thionyl chloride then with (poly ) alkali sulphides, which allows the relative antiwear and extreme pressure performance of said compounds to be modified at will.
Les composés phosphosoufrés selon la présente invention répondent à la formule générale suivante (I)
dans laquelle
R1 représente un groupement alkyle (par exemple méthyle, éthyle, tertiobutyle), alkényle (par exemple CH2=C(CH3)-CH2-) ou aryle, fonctionnalisé ou non, renfermant de 1 à 30 atomes de carbone ;
R2 et R3, indentques ou différents, représentent chacun un atome d'hydrogéne ou un radical de 1 à 30 atomes de carbone (par exemple méthyle, éthyle...), R2 et $3 pouvant être reliés entre eux pour
2 3 former une chaîne polyméthylènique ; par exemple, R2=H et R3=H ou CH3, de préférence R2=R3=H x est un nombre égal ou supérieur à 1, de préférence égal à 1, 2 ou
3 ; n est un nombre égal ou supérieur à 3, généralement compris entre 3 et
30 et par exemple égal à 3, 4, 5 ou 6 m est un nombre égal ou supérieur à 1, de préférence égal à 1, 2, 3 ou
4.The phosphosulfur compounds according to the present invention correspond to the following general formula (I)
in which
R1 represents an alkyl group (for example methyl, ethyl, tert-butyl), alkenyl (for example CH2 = C (CH3) -CH2-) or aryl, functionalized or not, containing from 1 to 30 carbon atoms;
R2 and R3, indent or different, each represent a hydrogen atom or a radical of 1 to 30 carbon atoms (for example methyl, ethyl ...), R2 and $ 3 can be linked together to
2 3 forming a polymethylene chain; for example, R2 = H and R3 = H or CH3, preferably R2 = R3 = H x is a number equal to or greater than 1, preferably equal to 1, 2 or
3; n is a number equal to or greater than 3, generally between 3 and
30 and for example equal to 3, 4, 5 or 6 m is a number equal to or greater than 1, preferably equal to 1, 2, 3 or
4.
Dans la définition de R1, on entend par groupement fonctionnalisé un groupement renfermant au moins un hétéroatome tel que, par exemple, le chlore ou le soufre, ou au moins une fonction chimique choisie par exemple parmi les fonctions acide carboxylique, aldéhyde, cétone, nitrile, hydroxyle et époxyde, plusieurs de ces fonctions pouvant être présentes dans le même groupement R
Parmi les composés phosphosoufrés selon la présente invention, on peut notamment citer ceux ayant l'une des formules suivantes (avec tBu = tertiobutyle = (CH3)3-C-) ::
((tBu-S(CH2)3-0-)2-P(S)-S-CH2-CH2)2S ((tBu-S-(CH2)3-0-)2-P(S) -S-CH2-CH2)2S2
((tBu-S-(CH2)3-0-)2-P(S)-S-CH2-CH2)2S3
((tBu-S2-(CH2 S2 (CH2)3-0-)2-P(S)-S-CH2-CH2)2s
((tBu-S2-(CH2)3-0-)2-P (S) -S-CH2-CH2)2S2
((tBu-S2-(CH2)3-0-)2-P(S)-S-CH2-CH2)2S3
La préparation des composés phosphosoufrés selon l'invention est illustrée dans les exemples.In the definition of R1, the term “functionalized group” is understood to mean a group containing at least one heteroatom such as, for example, chlorine or sulfur, or at least one chemical function chosen for example from carboxylic acid, aldehyde, ketone or nitrile functions. , hydroxyl and epoxide, several of these functions possibly being present in the same group R
Among the phosphosulfur compounds according to the present invention, mention may in particular be made of those having one of the following formulas (with tBu = tert-butyl = (CH3) 3-C-):
((tBu-S (CH2) 3-0-) 2-P (S) -S-CH2-CH2) 2S ((tBu-S- (CH2) 3-0-) 2-P (S) -S- CH2-CH2) 2S2
((tBu-S- (CH2) 3-0-) 2-P (S) -S-CH2-CH2) 2S3
((tBu-S2- (CH2 S2 (CH2) 3-0-) 2-P (S) -S-CH2-CH2) 2s
((tBu-S2- (CH2) 3-0-) 2-P (S) -S-CH2-CH2) 2S2
((tBu-S2- (CH2) 3-0-) 2-P (S) -S-CH2-CH2) 2S3
The preparation of the phosphosulfur compounds according to the invention is illustrated in the examples.
En raison notamment de leurs très bonnes propriétés antioxydantes, anticorrosives et surtout antiusure et extrême-pression, chaque composé phosphosoufré selon l'invention peut être avantageusement utilise comme additif pour huile lubrifiante (notamment minérale et/ou synthétique) à une concentration de 0,05 à 5 % en poids. Due in particular to their very good antioxidant, anticorrosive and especially antiwear and extreme pressure properties, each phosphosulfurized compound according to the invention can be advantageously used as an additive for lubricating oil (in particular mineral and / or synthetic) at a concentration of 0.05 at 5% by weight.
La présente invention a donc également pour objet une composition lubrifiante comprenant une proportion moyenne d'huile lubrifiante et une proportion de 0,05 à 5 % en poids d'au moins un composé phosphosoufré selon la présente invention. A subject of the present invention is therefore also a lubricating composition comprising an average proportion of lubricating oil and a proportion of 0.05 to 5% by weight of at least one phosphosulfurized compound according to the present invention.
Les exemples suivants 1 lustrent l'invention sans toutefois en limiter la portée. The following examples 1 illustrate the invention without, however, limiting its scope.
EXEMPLE 1 : Synthèse du composé (((CH3)3-C-S-(CH2)3-0-)2-P(S)-S-CH2-CH2-)2S a - Première étape, préparation de l'alcool monosoufré
(CH3)3-C-S-(CH2)3-OH
On introduit 150 cm3 d'alcool éthylique pur dans un réacteur tricol de 500 cm3, puis 18,6 g (0, 465 mole-g) d'hydroxyde de sodium. Après dissolution, on porte le mélange à 500C et on ajoute progressivement 41,9 g (0,465 mole-g) de 2-méthyl-2 propanethiol. A la fin de l'addition, on maintient la température 50 C pendant encore 0,5 heure puis on refroidit à 20 C.EXAMPLE 1 Synthesis of the compound (((CH3) 3-CS- (CH2) 3-0-) 2-P (S) -S-CH2-CH2-) 2S a - First step, preparation of the monosulfurized alcohol
(CH3) 3-CS- (CH2) 3-OH
150 cm3 of pure ethyl alcohol are introduced into a three-necked reactor of 500 cm3, then 18.6 g (0.465 mole-g) of sodium hydroxide. After dissolution, the mixture is brought to 500C and 41.9 g (0.465 mole-g) of 2-methyl-2 propanethiol are gradually added. At the end of the addition, the temperature is maintained at 50 C for a further 0.5 hour and then cooled to 20 C.
On ajoute ensuite progressivement 43,95 g (0,465 mole-g) de n-chloropropanol, le mélange est ensuite porté au reflux de l'alcool pendant 6 heures puis il est refroidi à la température de l'ambiance. 43.95 g (0.465 mole-g) of n-chloropropanol are then gradually added, the mixture is then brought to reflux of the alcohol for 6 hours and then it is cooled to room temperature.
le NaCl forme est éliminé par filtration et la solution organique est acidifiée par une solution aqueuse d'HCl 2 N. On recueille la phase organique puis on extrait la phase aqueuse par du dichlorométhane. Les fractions organiques sont réunies, lavées à l'eau, séchées sur Na2S04 anydre et le dichloromethane est éliminé par évaporation sous pression réduite. the NaCl formed is removed by filtration and the organic solution is acidified with an aqueous solution of 2N HCl. The organic phase is collected and the aqueous phase is then extracted with dichloromethane. The organic fractions are combined, washed with water, dried over anhydrous Na2SO4 and the dichloromethane is removed by evaporation under reduced pressure.
La purification de l'alcool soufre est effectuée par distillation sous pression réduite (PE=84 C/1 mbar) ; on récupère 68,5 g de produit incolore dont l'analyse élémentaire est la suivante
The purification of the sulfur alcohol is carried out by distillation under reduced pressure (PE = 84 C / 1 mbar); 68.5 g of colorless product are recovered, the elemental analysis of which is as follows
<tb> <SEP> C <SEP> % <SEP> Masse <SEP> H <SEP> H <SEP> % <SEP> Masse <SEP> f <SEP> <SEP> S <SEP> % <SEP> Masse
<tb> <SEP> trouvé <SEP> théorie <SEP> X <SEP> <SEP> trouve <SEP> théorie <SEP> trouvé <SEP> théorie <SEP>
<tb> 56,81 <SEP> 56,73 <SEP> 10,79 <SEP> 10,81 <SEP> 27,84 <SEP> 21,66
<tb>
Par ailleurs les analyses infra-rouge, RMN 13C et 1H confirment la structure chimique du produit attendu.<tb><SEP> C <SEP>% <SEP> Mass <SEP> H <SEP> H <SEP>% <SEP> Mass <SEP> f <SEP><SEP> S <SEP>% <SEP> Mass
<tb><SEP> found <SEP> theory <SEP> X <SEP><SEP> find <SEP> theory <SEP> found <SEP> theory <SEP>
<tb> 56.81 <SEP> 56.73 <SEP> 10.79 <SEP> 10.81 <SEP> 27.84 <SEP> 21.66
<tb>
Furthermore, infrared, 13C and 1H NMR analyzes confirm the chemical structure of the expected product.
b - Seconde étape, préparation d'un acide diakyldithiophosphorique monosulfuré :
((CH3)3-C-S-(CH2)3-0-)2-P(S)-SH
Dans un réacteur de 250cm3 on introduit 19,0 g (0,128 mole-g) d'alcool monosulfuré préparé dans la première étape et 40 cm3 de chloroforme ; on porte le mélange à 600C puis on ajoute progressi 7,11 g (0,032 mole-g) de @ P2S5. Après totale dissolution, le mélange est conservé une heure supplémentaire à 60 C sous agitation.b - Second step, preparation of a monosulfurized diakyldithiophosphoric acid:
((CH3) 3-CS- (CH2) 3-0-) 2-P (S) -SH
19.0 g (0.128 mole-g) of monosulfurized alcohol prepared in the first step and 40 cm3 of chloroform are introduced into a 250 cm3 reactor; the mixture is brought to 600C and then 7.11 g (0.032 mole-g) of @ P2S5 are gradually added. After complete dissolution, the mixture is stored for an additional hour at 60 ° C. with stirring.
Après avoir éliminé le chloroforme sous pression réduite, on recueille 24 g de liquide jaune clair dont l'analyse élémentaire est la suivante
After removing the chloroform under reduced pressure, 24 g of clear yellow liquid are collected, the elemental analysis of which is as follows
<tb> C <SEP> % <SEP> Masse <SEP> H% <SEP> Masse <SEP> S <SEP> % <SEP> Masse <SEP> P <SEP> % <SEP> Masse
<tb> <SEP> Trouvé <SEP> Théorie <SEP> j <SEP> Trouvé <SEP> Théorie <SEP> Trouvé <SEP> Théorie <SEP> TrouvéîThéoriel <SEP>
<tb> 43,21 <SEP> 43,05 <SEP> 7,97 <SEP> 7,94 <SEP> 32,71 <SEP> 32,86 <SEP> 8,02 <SEP> 7,94
<tb>
Par ailleurs les analyses infra-rouge, RMN 13C et 1H confirment la structure chimique du produit attendu.<tb> C <SEP>% <SEP> Mass <SEP> H% <SEP> Mass <SEP> S <SEP>% <SEP> Mass <SEP> P <SEP>% <SEP> Mass
<tb><SEP> Found <SEP> Theory <SEP> j <SEP> Found <SEP> Theory <SEP> Found <SEP> Theory <SEP> FoundîTheory <SEP>
<tb> 43.21 <SEP> 43.05 <SEP> 7.97 <SEP> 7.94 <SEP> 32.71 <SEP> 32.86 <SEP> 8.02 <SEP> 7.94
<tb>
Furthermore, infrared, 13C and 1H NMR analyzes confirm the chemical structure of the expected product.
c - Troisième étape, préparation d'un alcool diakyldithiphosphorique
Mmonosulfuré :
((CH3)3-C-S-(CH2)3-0-)2-P(S)-S-CH2-CH2-OH
Dans un réacteur de 100 cm3 on introduit 22,0 g (0,0564 mole-g) d'acide dialkyldithiophosphorique soufre préparé dans l'étape précédente, puis on ajoute 2,8 g (0,064 mole-g) d'oxyde d'éthylène sous agitation et en refroidissant énergiquement pour conserver la température à 25 C. L'excès d'oxyde d'éthylène est éliminé par évaporation sous pression réduite et l'on recueille environ 24 g d'un liquide visqueux dont l'analyse élémentaire est la suivante
c - Third step, preparation of a diakyldithiphosphoric alcohol
Mmonosulfurized:
((CH3) 3-CS- (CH2) 3-0-) 2-P (S) -S-CH2-CH2-OH
22.0 g (0.0564 mole-g) of sulfur dialkyldithiophosphoric acid prepared in the previous step are introduced into a 100 cm3 reactor, then 2.8 g (0.064 mole-g) of oxide are added. ethylene with stirring and vigorous cooling to keep the temperature at 25 C. The excess ethylene oxide is removed by evaporation under reduced pressure and about 24 g of a viscous liquid are collected, the elemental analysis of which is the next one
<tb> C <SEP> C <SEP> % <SEP> Masse <SEP> ss <SEP> H <SEP> % <SEP> Masse <SEP> S <SEP> % <SEP> Masse <SEP> P <SEP> % <SEP> Masse <SEP> J
<tb> <SEP> Trouvé <SEP> IThéoriel <SEP> Trouvé <SEP> Théorie <SEP> J <SEP> Trouvé <SEP> Théorie <SEP> J <SEP> Trouvé <SEP> Théorie <SEP>
<tb> 1 <SEP> 44,09 <SEP> 1 <SEP> 44,22 <SEP> 1 <SEP> 8,12 <SEP> t <SEP> 8,06 <SEP> 1 <SEP> 29,32 <SEP> 1 <SEP> 29,53 <SEP> 1 <SEP> 7,03 <SEP> 1 <SEP> 7,14 <SEP> J
<tb>
Par ailleurs les analyses infra-rouge, RMN 13C 31P et 1H confirment la structure chimique du produit attendu.<tb> C <SEP> C <SEP>% <SEP> Mass <SEP> ss <SEP> H <SEP>% <SEP> Mass <SEP> S <SEP>% <SEP> Mass <SEP> P <SEP >% <SEP> Mass <SEP> J
<tb><SEP> Found <SEP> ITheoriel <SEP> Found <SEP> Theory <SEP> J <SEP> Found <SEP> Theory <SEP> J <SEP> Found <SEP> Theory <SEP>
<tb> 1 <SEP> 44.09 <SEP> 1 <SEP> 44.22 <SEP> 1 <SEP> 8.12 <SEP> t <SEP> 8.06 <SEP> 1 <SEP> 29.32 <SEP> 1 <SEP> 29.53 <SEP> 1 <SEP> 7.03 <SEP> 1 <SEP> 7.14 <SEP> J
<tb>
Furthermore, infrared, 13C 31P and 1H NMR analyzes confirm the chemical structure of the expected product.
d - Quatrième étape, préparation du chlorure correspondant à l'alcool dialkyldithiophosphorique monosulfure précédent
((CH3)3-C-S-(CH2)3-0-)2-P(S)-S-CH2-CH2-C1
Dans un réacteur de 100 cm3 on introduit 20,0 g (0,046 mole-g) d'alcool diaîkyldithiophosphorique monosulfuré préparé dans l'étape précédente, on ajoute 20 g de chloroforme, puis très progressivement 2,74 g (0,023 mole-g) de SOC12 en conservant la température réactionnelle vers 200C ; on porte ensuite le mélange à la température du reflux puis on ajoute de nouveau très progressivement la même quantité de SOC12.Après refroidissement le chloroforme est éliminé sous pression réduite pour recueillir environ 20 g de produit dont les analyses infra-rouge, RMN 13C, 1H et 31P correspondent à la structure chimique du produit attendu.d - Fourth step, preparation of the chloride corresponding to the previous dialkyldithiophosphoric alcohol monosulfide
((CH3) 3-CS- (CH2) 3-0-) 2-P (S) -S-CH2-CH2-C1
20.0 g (0.046 mole-g) of monosulfurized diayl dithiophosphoric alcohol prepared in the previous step are introduced into a 100 cm3 reactor, 20 g of chloroform are added, then very gradually 2.74 g (0.023 mole-g) SOC12 while maintaining the reaction temperature at around 200C; the mixture is then brought to reflux temperature and then the same amount of SOC12 is very gradually added again. After cooling, the chloroform is removed under reduced pressure to collect approximately 20 g of product, including infrared analyzes, 13 C NMR, 1 H and 31P correspond to the chemical structure of the expected product.
e - Cinquième et dernière étape, préparation du composé visé
((CH3)3-C-S-(CH2)3-0-)2-P(S)-S-CH2-CH2-)2S
Dans le réacteur de l'étape précédente on ajoute 20 g de chloroforme pour dissoudre le dérivé chloré, puis 1 g de chlorure de tetrabutylammonium (catalyseur de transfert de phase) et enfin très progressivement 20 cm3 d'une solution aqueuse contenant 7 g de Na2S, 9h20 (0,03 mole-g) en maintenant la température vers 20 C. On porte ensuite le mélange à la température du reflux pendant une heure, on refroidit, on sépare les phases.e - Fifth and last step, preparation of the target compound
((CH3) 3-CS- (CH2) 3-0-) 2-P (S) -S-CH2-CH2-) 2S
In the reactor of the previous step, 20 g of chloroform are added to dissolve the chlorinated derivative, then 1 g of tetrabutylammonium chloride (phase transfer catalyst) and finally very gradually 20 cm3 of an aqueous solution containing 7 g of Na2S 9:20 (0.03 mole-g) while maintaining the temperature at around 20 ° C. The mixture is then brought to reflux temperature for one hour, it is cooled and the phases are separated.
La fraction organique récupérée est lavée à l'eau, séchée sur NaSO4 anhydre puis filtrée pour recueillir 19 g de produit dont l'analyse élémentaire est la suivante
The organic fraction recovered is washed with water, dried over anhydrous NaSO4 and then filtered to collect 19 g of product, the elemental analysis of which is as follows
<tb> J <SEP> C <SEP> % <SEP> Masse <SEP> H <SEP> H <SEP> % <SEP> Masse <SEP> J <SEP> S <SEP> % <SEP> Masse <SEP> t <SEP> P <SEP> % <SEP> Masse
<tb> J <SEP> Trouvé <SEP> Théorie <SEP> J <SEP> Trouvé <SEP> (Théorie <SEP> ss <SEP> Trouve <SEP> Théorie <SEP> JirouvéJThéorieJ <SEP>
<tb> 44,89 <SEP> 44,31 <SEP> 1 <SEP> 7,99 <SEP> 1 <SEP> 7,85 <SEP> t <SEP> 32,47 <SEP> 33,30 <SEP> 1 <SEP> 7,01 <SEP> 1 <SEP> 7,15
<tb>
Par ailleurs les analyses infra-rouge, RMN 13C 31P et 1H confirment la structure chimique du produit attendu.<tb> J <SEP> C <SEP>% <SEP> Mass <SEP> H <SEP> H <SEP>% <SEP> Mass <SEP> J <SEP> S <SEP>% <SEP> Mass <SEP > t <SEP> P <SEP>% <SEP> Mass
<tb> J <SEP> Found <SEP> Theory <SEP> J <SEP> Found <SEP> (Theory <SEP> ss <SEP> Find <SEP> Theory <SEP> JfoundJTheoryJ <SEP>
<tb> 44.89 <SEP> 44.31 <SEP> 1 <SEP> 7.99 <SEP> 1 <SEP> 7.85 <SEP> t <SEP> 32.47 <SEP> 33.30 <SEP > 1 <SEP> 7.01 <SEP> 1 <SEP> 7.15
<tb>
Furthermore, infrared, 13C 31P and 1H NMR analyzes confirm the chemical structure of the expected product.
EXEMPLE 2 : Synthèse du composé
(((CH3)3-C-S2-(CH2)3-0-)2-P(S)-S-CH2-CH2-)2S
La première étape (a) de l'exemple 1 est reprise en ajoutant au milieu réactionnel 14,91 g (0,465 mole-g) de soufre élémentaire pour former statistiquement le composé bisulfure. EXAMPLE 2 Synthesis of the compound
(((CH3) 3-C-S2- (CH2) 3-0-) 2-P (S) -S-CH2-CH2-) 2S
The first step (a) of Example 1 is repeated by adding 14.91 g (0.465 mole-g) of elemental sulfur to the reaction medium to form the disulfide compound statistically.
Après réaction, l'alcool disulfuré brut obtenu est purifiée par chromatographie liquide sur gel de silice, par solution à l'hexane pour éliminer les impuretés, et à l'alcool méthylique qui, après évaporation sous pression réduite, permet de récupéré l'alcool disulfure purifié visé. After reaction, the crude disulfurized alcohol obtained is purified by liquid chromatography on silica gel, by solution with hexane to remove the impurities, and with methyl alcohol which, after evaporation under reduced pressure, allows the alcohol to be recovered. purified disulfide referred to.
L'expérimentation est ensuite poursuivie, en utilisant les mêmes proportions molaires de réactifs, pour obtenir au terme de la cinquième étape (e) un produit dont l'analyse élémentaire est la suivante
The experiment is then continued, using the same molar proportions of reagents, to obtain at the end of the fifth stage (e) a product whose elemental analysis is as follows
<tb> J <SEP> C <SEP> % <SEP> Masse <SEP> H <SEP> H <SEP> % <SEP> Masse <SEP> t <SEP> S <SEP> % <SEP> Masse <SEP> t <SEP> P <SEP> % <SEP> Masse <SEP> <SEP> J <SEP>
<tb> ss <SEP> Trouve <SEP> Théorie <SEP> J <SEP> Trouvé <SEP> Théorie <SEP> Trouvé <SEP> Théorie <SEP> {Trouve <SEP> JThéorieJ <SEP>
<tb> 1 <SEP> 38,97 <SEP> 1 <SEP> 38,60 <SEP> 1 <SEP> 7,05 <SEP> 1 <SEP> 6,84 <SEP> 1 <SEP> 41,02 <SEP> 1 <SEP> 41,90 <SEP> 1 <SEP> 6,01 <SEP> 1 <SEP> 6,23 <SEP> <SEP> J <SEP>
<tb>
En outre les analyses infra-rouge, RMN 13C et 31P correspondent globalement à la structure chimique du produit statistique attendu.<tb> J <SEP> C <SEP>% <SEP> Mass <SEP> H <SEP> H <SEP>% <SEP> Mass <SEP> t <SEP> S <SEP>% <SEP> Mass <SEP > t <SEP> P <SEP>% <SEP> Mass <SEP><SEP> J <SEP>
<tb> ss <SEP> Find <SEP> Theory <SEP> J <SEP> Found <SEP> Theory <SEP> Found <SEP> Theory <SEP> {Find <SEP> JTheoryJ <SEP>
<tb> 1 <SEP> 38.97 <SEP> 1 <SEP> 38.60 <SEP> 1 <SEP> 7.05 <SEP> 1 <SEP> 6.84 <SEP> 1 <SEP> 41.02 <SEP> 1 <SEP> 41.90 <SEP> 1 <SEP> 6.01 <SEP> 1 <SEP> 6.23 <SEP><SEP> J <SEP>
<tb>
In addition, the infrared, 13C and 31P NMR analyzes globally correspond to the chemical structure of the expected statistical product.
EXEMPLE 3 : Synthèse du composé
(((CH3)3-C-S-(CH2)3-0-)2-P(S)-S-CH2-CH2-)2S2
L'expérimentation de l'exemple 1 est reprise intégralement jusqu'à la cinquième dans laquelle on utilise 25 cm3 d'une solution aqueuse contenant 7 g de Na2S, 9H20 (0,03 mole-g) et I g de soufre élémentaire (0,03 atome-g) et pour former statistiquement le composé bisulfure. EXAMPLE 3: Synthesis of the compound
(((CH3) 3-CS- (CH2) 3-0-) 2-P (S) -S-CH2-CH2-) 2S2
The experiment of Example 1 is repeated in full until the fifth in which 25 cm3 of an aqueous solution containing 7 g of Na2S, 9H20 (0.03 mol-g) and I g of elemental sulfur (0 , 03 atom-g) and to statistically form the disulfide compound.
On obtient ainsi un produit dont l'analyse élémentaire est la suivante
We thus obtain a product whose elementary analysis is as follows
<tb> <SEP> C <SEP> % <SEP> Masse <SEP> H <SEP> % <SEP> Masse <SEP> S <SEP> % <SEP> Masse <SEP> P <SEP> % <SEP> Masse <SEP> j
<tb> Trouvé <SEP> Théorie <SEP> Trouvé <SEP> Théorie <SEP> Trouvé <SEP> Théorie <SEP> Théorie <SEP> Théorie
<tb> 43,22 <SEP> i <SEP> 42,73 <SEP> 1 <SEP> 7,85 <SEP> 1 <SEP> 7,57 <SEP> 34,89 <SEP> 1 <SEP> 35,68 <SEP> 6,73 <SEP> 1 <SEP> 6,90 <SEP> <SEP> J <SEP>
<tb>
En outre les analyses infra-rouge, RMN 13C, 1H et 31P correspondent globalement à la structure chimique du produit statistique attendu.<tb><SEP> C <SEP>% <SEP> Mass <SEP> H <SEP>% <SEP> Mass <SEP> S <SEP>% <SEP> Mass <SEP> P <SEP>% <SEP> Mass <SEP> j
<tb> Found <SEP> Theory <SEP> Found <SEP> Theory <SEP> Found <SEP> Theory <SEP> Theory <SEP> Theory
<tb> 43.22 <SEP> i <SEP> 42.73 <SEP> 1 <SEP> 7.85 <SEP> 1 <SEP> 7.57 <SEP> 34.89 <SEP> 1 <SEP> 35 , 68 <SEP> 6.73 <SEP> 1 <SEP> 6.90 <SEP><SEP> J <SEP>
<tb>
In addition, infrared, 13C, 1H and 31P NMR analyzes globally correspond to the chemical structure of the expected statistical product.
EXEMPLE 4 : Synthèse du compose
(((CH3)3-C-S2-(CH2)3-0-)2-P(S)-S-CH2-CH2-)2S3
L'expérimentation de exemple 2 est reprise pour préparer l'alcool diaîkyîdithiophosphoré bisulfure soufré.EXAMPLE 4: Synthesis of the compound
(((CH3) 3-C-S2- (CH2) 3-0-) 2-P (S) -S-CH2-CH2-) 2S3
The experiment of Example 2 is repeated in order to prepare the disulfurized disulfide diaîkidithiophosphorus alcohol.
L'expérimentation est poursuivie, toutes proportions molaires entre réactifs conservées, jusqu'à la cinquième étape dans laquelle on utilise 25 cm3 d'une solution aqueuse constituée par 7 g de Na2S, 9H20 (0,03 mole-g) et 2 g de soufre élémentaire (0,06 atome-g) pour former le composé statistiquement trisulfuré visé. The experiment is continued, all molar proportions between reagents preserved, until the fifth stage in which 25 cm3 of an aqueous solution consisting of 7 g of Na2S, 9H20 (0.03 mole-g) and 2 g of elemental sulfur (0.06 atom-g) to form the target statistically trisulfurized compound.
On obtient ainsi un produit dont l'analyse élémentaire est la suivante
We thus obtain a product whose elementary analysis is as follows
<tb> C <SEP> C <SEP> % <SEP> Masse <SEP> H <SEP> % <SEP> Masse <SEP> S <SEP> % <SEP> Masse <SEP> t <SEP> P <SEP> % <SEP> Masse <SEP>
<tb> Trouvé <SEP> Théorie <SEP> Trouvé <SEP> Théorie <SEP> Théorie <SEP> Théorie <SEP> Théorie <SEP> Théorie
<tb> 36,86 <SEP> 1 <SEP> 36,26 <SEP> 6,78 <SEP> 1 <SEP> 6,42 <SEP> 1 <SEP> <SEP> 44,71 <SEP> 1 <SEP> 45,42 <SEP> 1 <SEP> 5,34 <SEP> 1 <SEP> 5,85 <SEP> 1 <SEP>
<tb>
En outre les analyses infra-rouge, RMN 13C, 1H et 31P correspondent globalement à la structure chimique du produit statistique attendu.<tb> C <SEP> C <SEP>% <SEP> Mass <SEP> H <SEP>% <SEP> Mass <SEP> S <SEP>% <SEP> Mass <SEP> t <SEP> P <SEP >% <SEP> Mass <SEP>
<tb> Found <SEP> Theory <SEP> Found <SEP> Theory <SEP> Theory <SEP> Theory <SEP> Theory <SEP> Theory
<tb> 36.86 <SEP> 1 <SEP> 36.26 <SEP> 6.78 <SEP> 1 <SEP> 6.42 <SEP> 1 <SEP><SEP> 44.71 <SEP> 1 <SEP> 45.42 <SEP> 1 <SEP> 5.34 <SEP> 1 <SEP> 5.85 <SEP> 1 <SEP>
<tb>
In addition, infrared, 13C, 1H and 31P NMR analyzes globally correspond to the chemical structure of the expected statistical product.
EVALUATION DES PROPRIETES EXTREME-PRESSION ET ANTIUSURE
DES ADDITIFS DE L'INVENTION.EVALUATION OF EXTREME PRESSURE AND ANTIWEAR PROPERTIES
ADDITIVES OF THE INVENTION.
On a réalisé des essais mettant en évidence les propriétés extrême-pression et antiusure des additifs de l'invention, à l'aide d'une machine 4 billes selon la procédure de 1'ASTM D 2783, à des concentrations telles que la teneur en soufre de l'huile minérale SAE 80W90 soit égale à 0,22 % en masse ; les résultats obtenus sont rassembles dans le tableau 1. Tests were carried out demonstrating the extreme pressure and antiwear properties of the additives of the invention, using a 4-ball machine according to the procedure of ASTM D 2783, at concentrations such as the content of sulfur in mineral oil SAE 80W90 is equal to 0.22% by mass; the results obtained are collated in Table 1.
On constate au vu des résultats que les additifs de l'invention possèdent de bonnes propriétés antiusure et extrême-pression, et que celles-ci peuvent être modifiées en fonction de la quantité de soufre élémentaire utilisée dans les synthèses. On constate en particulier, qu'à concentration de soufre égale, les composés comportant des motifs polysulfures sont plus efficaces que ceux comportant des motifs monosulfures, d'ou la possibilité de régler à volonté les performances mécaniques de ces produits. In view of the results, it can be seen that the additives of the invention have good antiwear and extreme pressure properties, and that these can be modified as a function of the amount of elemental sulfur used in the syntheses. It is observed in particular, that at an equal sulfur concentration, the compounds comprising polysulfide units are more effective than those comprising monosulfide units, hence the possibility of adjusting the mechanical performance of these products at will.
Cette amélioration peut être mise à profit dans la formulation d'huiles lubrifiantes pour engrenages ou pour le travail des métaux. This improvement can be used in the formulation of lubricating oils for gears or for metalworking.
TABLEAU 1
TABLE 1
ADDITIF <SEP> QUANTITE <SEP> QUANTIVE <SEP> QUANTITE <SEP> EXTREME-PRESSION <SEP> USURE
<tb> DE <SEP> DE <SEP> S <SEP> DANS <SEP> D'ADDITIF <SEP> DE <SEP> S <SEP> DANS <SEP> INDICE <SEP> CHARGE <SEP> CHARGE <SEP> AVANT <SEP> CHARGE <SEP> DE <SEP> DIAMETRE <SEP> D'EMPREINTE <SEP> (mm)
<tb> L'EXEMPLE <SEP> L'ADDITIF <SEP> DANS <SEP> L'HUILE <SEP> L'HUILE <SEP> USURE <SEP> SOUDURE <SEP> SOUDURE <SEP> 1 <SEP> H <SEP> SOUS <SEP> CHARGE <SEP> DE
<tb> <SEP> (% <SEP> poids) <SEP> (% <SEP> poids) <SEP> (% <SEP> poids)
<tb> <SEP> Kgf <SEP> Newt <SEP> Kgf <SEP> Newt <SEP> Kgf <SEP> Newt <SEP> 40 <SEP> Kgf <SEP> 60 <SEP> Kgf <SEP> 80 <SEP> Kgf
<tb> <SEP> 392,4 <SEP> Newt <SEP> 588,6 <SEP> Newt <SEP> 784,8 <SEP> Newt
<tb> - <SEP> - <SEP> 0 <SEP> - <SEP> 28,0 <SEP> 274,7 <SEP> 50 <SEP> 490,5 <SEP> 150 <SEP> 1471,6 <SEP> 1,47 <SEP> 1,90 <SEP> 2,50
<tb> 1 <SEP> 32,47 <SEP> 0,68 <SEP> 0,22 <SEP> 33,8 <SEP> 331,6 <SEP> 80 <SEP> 784,8 <SEP> 200 <SEP> 1962,0 <SEP> 0,40 <SEP> 0,58 <SEP> 1,07
<tb> 2 <SEP> 41,02 <SEP> 0,54 <SEP> 0,22 <SEP> 43,0 <SEP> 421,8 <SEP> 100 <SEP> 981,0 <SEP> 200 <SEP> 1962,0 <SEP> 0,39 <SEP> 0,55 <SEP> 0,98
<tb> 3 <SEP> 34,89 <SEP> 0,63 <SEP> 0,22 <SEP> 36,0 <SEP> 353,2 <SEP> 80 <SEP> 784,8 <SEP> 200 <SEP> 1962,0 <SEP> 0,39 <SEP> 0,65 <SEP> 0,95
<tb> 4 <SEP> 44,71 <SEP> 0,49 <SEP> 0,22 <SEP> 55,1 <SEP> 540,5 <SEP> 126 <SEP> 1236,1 <SEP> 250 <SEP> 2452,5 <SEP> 0,35 <SEP> 0,60 <SEP> 0,89
<tb> ADDITIVE <SEP> QUANTITY <SEP> QUANTIVE <SEP> QUANTITY <SEP> EXTREME-PRESSURE <SEP> WEAR
<tb> OF <SEP> OF <SEP> S <SEP> IN <SEP> OF ADDITIVE <SEP> OF <SEP> S <SEP> IN <SEP> INDEX <SEP> LOAD <SEP> LOAD <SEP> BEFORE <SEP> LOAD <SEP> OF <SEP> DIAMETER <SEP> OF FOOTPRINT <SEP> (mm)
<tb> EXAMPLE <SEP> ADDITIVE <SEP> IN <SEP> OIL <SEP> OIL <SEP> WEAR <SEP> WELD <SEP> WELD <SEP> 1 <SEP> H <SEP > UNDER <SEP> LOAD <SEP> OF
<tb><SEP> (% <SEP> weight) <SEP> (% <SEP> weight) <SEP> (% <SEP> weight)
<tb><SEP> Kgf <SEP> Newt <SEP> Kgf <SEP> Newt <SEP> Kgf <SEP> Newt <SEP> 40 <SEP> Kgf <SEP> 60 <SEP> Kgf <SEP> 80 <SEP> Kgf
<tb><SEP> 392.4 <SEP> Newt <SEP> 588.6 <SEP> Newt <SEP> 784.8 <SEP> Newt
<tb> - <SEP> - <SEP> 0 <SEP> - <SEP> 28.0 <SEP> 274.7 <SEP> 50 <SEP> 490.5 <SEP> 150 <SEP> 1471.6 <SEP > 1.47 <SEP> 1.90 <SEP> 2.50
<tb> 1 <SEP> 32.47 <SEP> 0.68 <SEP> 0.22 <SEP> 33.8 <SEP> 331.6 <SEP> 80 <SEP> 784.8 <SEP> 200 <SEP > 1962.0 <SEP> 0.40 <SEP> 0.58 <SEP> 1.07
<tb> 2 <SEP> 41.02 <SEP> 0.54 <SEP> 0.22 <SEP> 43.0 <SEP> 421.8 <SEP> 100 <SEP> 981.0 <SEP> 200 <SEP > 1962.0 <SEP> 0.39 <SEP> 0.55 <SEP> 0.98
<tb> 3 <SEP> 34.89 <SEP> 0.63 <SEP> 0.22 <SEP> 36.0 <SEP> 353.2 <SEP> 80 <SEP> 784.8 <SEP> 200 <SEP > 1962.0 <SEP> 0.39 <SEP> 0.65 <SEP> 0.95
<tb> 4 <SEP> 44.71 <SEP> 0.49 <SEP> 0.22 <SEP> 55.1 <SEP> 540.5 <SEP> 126 <SEP> 1236.1 <SEP> 250 <SEP > 2452.5 <SEP> 0.35 <SEP> 0.60 <SEP> 0.89
<tb>
Claims (8)
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9016530A FR2671084B1 (en) | 1990-12-27 | 1990-12-27 | NOVEL PHOSPHOSULFUR COMPOUNDS AND THEIR USE AS ADDITIVES FOR LUBRICATING OIL. |
DE69120752T DE69120752T2 (en) | 1990-08-24 | 1991-08-19 | Phosphorus sulfur compounds and their use as lubricating oil additives |
EP91402268A EP0477048B1 (en) | 1990-08-24 | 1991-08-19 | Compounds containing phosphorus and sulfur and their use as additives for lubricant oil |
ES91402268T ES2091891T3 (en) | 1990-08-24 | 1991-08-19 | NEW PHOSPHOSUFRATED COMPOUNDS AND THEIR USE AS ADDITIVES FOR LUBRICATING OIL. |
DK91402268.6T DK0477048T3 (en) | 1990-08-24 | 1991-08-19 | Newly known phosphorus sulfur compounds and their use as additives in lubricating oil |
CA002049744A CA2049744A1 (en) | 1990-08-24 | 1991-08-23 | Phosphosulfurated compounds and their use as additives for lubricating oil |
MX9100797A MX9100797A (en) | 1990-08-24 | 1991-08-23 | COMPOSITE OF SULFUR AND PHOSPHORUS |
JP3213328A JPH04230691A (en) | 1990-08-24 | 1991-08-26 | Novel phosphorous sulfide compound and usage thereof as additive to lubricating oil |
US07/749,783 US5306436A (en) | 1990-08-24 | 1991-08-26 | New phosphosulfides compounds and use thereof as oil lubricants |
CN91112817A CN1036716C (en) | 1990-12-27 | 1991-12-27 | Phosphosulfides compounds |
US08/186,077 US5463132A (en) | 1990-08-24 | 1994-01-25 | Process for the preparation of phosphosulfide compounds useful as oil lubricants |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9016530A FR2671084B1 (en) | 1990-12-27 | 1990-12-27 | NOVEL PHOSPHOSULFUR COMPOUNDS AND THEIR USE AS ADDITIVES FOR LUBRICATING OIL. |
Publications (2)
Publication Number | Publication Date |
---|---|
FR2671084A1 true FR2671084A1 (en) | 1992-07-03 |
FR2671084B1 FR2671084B1 (en) | 1993-04-09 |
Family
ID=9403867
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
FR9016530A Expired - Fee Related FR2671084B1 (en) | 1990-08-24 | 1990-12-27 | NOVEL PHOSPHOSULFUR COMPOUNDS AND THEIR USE AS ADDITIVES FOR LUBRICATING OIL. |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN1036716C (en) |
FR (1) | FR2671084B1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4563114B2 (en) * | 2004-08-30 | 2010-10-13 | 出光興産株式会社 | Additive for lubricant |
US9944879B2 (en) * | 2014-10-08 | 2018-04-17 | Afton Chemical Corporation | Phosphorous-containing compounds and uses thereof |
US9481696B1 (en) * | 2015-08-19 | 2016-11-01 | Afton Chemical Corporation | Thiophosphates and thiophosphate derivatives as lubricant additives |
CA3042044A1 (en) * | 2016-10-31 | 2018-05-03 | Afton Chemical Corporation | Phosphorous containing compounds and uses thereof |
US10329511B2 (en) * | 2016-10-31 | 2019-06-25 | Afton Chemical Corporation | Lubricant compositions comprising thiophosphates and thiophosphate derivatives |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA515666A (en) * | 1955-08-16 | S. Fletcher Beatrice | O,o,o',o'-tetraalkyl s,s'-oxydialkylene bis (thiophosphates) |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3591475A (en) * | 1968-12-09 | 1971-07-06 | Exxon Research Engineering Co | Preparation of unsymmetrical thiol-allene diadducts |
US3944495A (en) * | 1974-02-19 | 1976-03-16 | Texaco Inc. | Metal dialkyldithiophosphates |
DE2608836C3 (en) * | 1976-03-04 | 1982-02-18 | Rhein-Chemie Rheinau Gmbh, 6800 Mannheim | Sulfurized phosphoric acid ester salts |
-
1990
- 1990-12-27 FR FR9016530A patent/FR2671084B1/en not_active Expired - Fee Related
-
1991
- 1991-12-27 CN CN91112817A patent/CN1036716C/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA515666A (en) * | 1955-08-16 | S. Fletcher Beatrice | O,o,o',o'-tetraalkyl s,s'-oxydialkylene bis (thiophosphates) |
Also Published As
Publication number | Publication date |
---|---|
FR2671084B1 (en) | 1993-04-09 |
CN1063493A (en) | 1992-08-12 |
CN1036716C (en) | 1997-12-17 |
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