EP0271437B1 - Additifs sulfurés pour lubrifiants - Google Patents

Additifs sulfurés pour lubrifiants Download PDF

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Publication number
EP0271437B1
EP0271437B1 EP87810639A EP87810639A EP0271437B1 EP 0271437 B1 EP0271437 B1 EP 0271437B1 EP 87810639 A EP87810639 A EP 87810639A EP 87810639 A EP87810639 A EP 87810639A EP 0271437 B1 EP0271437 B1 EP 0271437B1
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Prior art keywords
alkyl
hydrogen atom
formula
substituted
branched
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German (de)
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EP0271437A1 (fr
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Henri Dr. Dubas
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Novartis AG
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Ciba Geigy AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • 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
    • C10M135/34—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon only
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

  • the present invention relates to lubricant additives containing substituted thio-thiophene derivatives and new substituted thio-thiophene derivatives.
  • Lubricants are generally added to improve performance. Special requirements with regard to the load carrying capacity are placed on lubricants for the transmission of larger forces. By adding high-pressure and wear-reducing additives, the otherwise occurring negative phenomena are greatly reduced.
  • DE-OS 2 242 637 describes thio-thiophthenes substituted by hydrocarbon groups, which are used as oxidation inhibitors in lubricants.
  • R 1 represents a metal cation
  • it is preferably an alkali, alkaline earth or transition metal cation.
  • Zn 2+ and C U 2+ are particularly preferred among the transition metal cations.
  • Li ⁇ , Nae, K ⁇ , Mg 2+ and Ca 2+ are preferred among the alkali and alkaline earth metal cations.
  • both represent R 1 H, NH 4 ⁇ , Lie, Nae, K ⁇ , Mge, C a ⁇ , Zn 2+ and C U 2+ .
  • R1 in the meaning of primary, secondary, tertiary and quaternary ammonium can contain 1 to 40, preferably 1 to 30, carbon atoms.
  • the N atoms can be substituted with cyclo-substituted, linear or branched C 1 -C 20 -alkyl, optionally C 1 -C 6 -alkyl-substituted cycloalkyl or cycloalkyl-C 1 -C 2 -alkyl with 4 to 7 ring-C- Atoms, C 1 -C 12 alkyl substituted phenyl, benzyl or phenylethyl, or by optionally C 1 -C 4 alkyl substituted tri- or tetramethylene or 3-oxapentylene.
  • Both R 1 in formula I in the meaning of ammonium preferably correspond to the formulas or R 10 R 11 R 12 R 13 N ⁇ in which R 10 , R 11 , R12 and R13 independently of one another, optionally substituted by hydroxyl, linear or branched C 1 -C 18 alkyl, especially C 1 -C 12 alkyl and in particular C Are 1 -C 6 alkyl.
  • such ammonium compounds are expediently used in aqueous or aqueous-organic substrates in which R 10 , R 11 , R 12 and R 13 are C 1 -C 4 alkyl optionally substituted by hydroxyl.
  • Such organic compounds are expediently used in organic substrates in which the N atom is substituted by at least one long-chain alkyl group containing, for example, 6-20 C atoms.
  • a preferred group of such ammonium compounds is that in which, in the formulas given above, R 10 is linear or branched C 6 -C 18 alkyl and R 11 , R 12 and R 13 are linear or branched C 1 -C 4 alkyl.
  • R 1 in the meaning of ammonium are: methyl, ethyl, n and i-propyl, n, i and t-butyl, pentyl, hexyl, heptyl, octyl, nonyl -, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, hydroxyethyl, 2-hydroxypropyl, dimethyl, (methyl) (ethyl), diethyl, dihydroxyethyl, dibutyl , (Methyl) (butyl) -, (methyl) (hexyl) -, (methyl) (dodecyl) -, (methyl) (octadecyl), trimethyl, triethyl, trihydroxyethyl, tri-n-butyl, (hexyl ) (Di
  • R 1 represents unsubstituted alkyl, it is preferably linear or branched Ci-C 20 -, especially C 2 -C 18 -, in particular C 2 -C 12 - and very particularly C 4 -C 12 alkyl.
  • alkyl are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, n-pentyl, 2-methylbut-1-yl, n-hexyl-, 2-methylpent-1- yl, 2-ethylpent-1- or -2-yl, n-heptyl, 2-n-propylhept-1-yl, n-octyl, 2-ethylhex-1-yl, nonyl, decyl, undecyl, dodecyl, tridecyl, Tetradecyl, hexadecyl, octadecyl and eicosyl.
  • Ri in the meaning of aralkyl, preferably phenylalkyl, contains in particular 7 to 12 carbon atoms and is particularly benzyl, 1-phenyleth-2-yl, 1-phenyleth-1-yl, 1-phenyl-prop-1-, -2 - or -3-yl.
  • R 1 represents alkaralkyl
  • its aryl group is preferably phenyl and its alkylene group is preferably 1,1- or 1,2-ethylene and especially methylene.
  • the alkaralkyl preferably contains 1 to 3, in particular 1 or 2, alkyl groups which preferably contain 1 to 20, in particular 1 to 12, carbon atoms and can be linear or branched.
  • R 1 as alkaralkyl represents mono- or dialkylbenzyl having 8 to 20 carbon atoms.
  • alkaralkyl examples include methylbenzyl, 1- (methylphenyl) eth-2-yl, dimethylbenzyl, ethylbenzyl, n- or i-propylbenzyl, n- or t-butylbenzyl, di-t-butylbenzyl, hexylbenzyl, octylbenzyl, methylbutylbenzyl, nonylbenzyl, dioctyl or dinonylbenzyl, decylbenzyl, dodecylbenzyl, hexadecylbenzyl, octadecylbenzyl.
  • R 1 represents cycloalkyl or cycloalkylalkyl
  • the cycloalkyl groups are preferably cyclopentyl and especially cyclohexyl.
  • the alkylene group in cycloalkylalkyl is preferably ethylene and especially methylene. If the cycloalkyl groups are substituted by alkyl, the alkyl preferably contains 1 to 12 and in particular 1 to 6 carbon atoms.
  • the alkyl can be linear or branched.
  • Some examples are methyl, dimethyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 3,3,5-trimethylcyclohexyl, decylcyclohexyl or cyclopentyl, (methylcyclohexyl) methyl, cyclopentylmethyl, cyclohexylmethyl.
  • R 1 can be substituted as alkyl as previously defined.
  • the alkyl preferably contains 1 to 12, particularly 1 to 6, and in particular 1 to 3 carbon atoms.
  • R 1 can be substituted by amino or ammonium groups of the formulas -NR4R5 or - ⁇ NR4R5R6, in which R4, R5 and R6 independently, preferably for a hydrogen atom or optionally substituted by -OH, C 1 -C 18 -, especially C 1 -C 12 - and in particular C 1 -C 6 alkyl.
  • R4 is R5 or R6, if appropriate, particularly C 1 -C, through -OH-substituted C 1 -C 6 .- 4 alkyl or a hydrogen atom.
  • R 4 is C 6 -C 18 alkyl
  • R5 and R6 independently represent a hydrogen atom or C 1 -C 6 -, especially C 1 -C 4 represent alkyl.
  • alkyl groups have previously been listed for R1 in the meaning of ammonium.
  • R 1 can be substituted by -OR 7 or -SR 7 .
  • R 7 is preferably a hydrogen atom, linear or branched C 1 -C 12 -, especially C 1 -C 6 -alkyl, cyclohexyl optionally substituted by C 1 -C 4 -alkyl, or optionally by Ci-C 18 -, especially C 1 -C 12 alkyl substituted phenyl or benzyl. Examples of such alkyl groups have previously been listed for R 1 in the meaning of alkyl substituted cycloalkyl and alkaralkyl.
  • R 7 as alkylphenyl are methyl-, dimethyl-, ethyl-, n- or i-propyl-, n-, i- or -t-butyl-, methyl-t-butyl-, di-t-butyl-, Pentyl, hexyl, octyl, dioctyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, dinonyl, didecyl and didodecylphenyl.
  • R 1 represents alkyl substituted by acyloxy
  • the acyloxy preferably contains 1 to 12 and in particular 1 to 6 carbon atoms.
  • Examples of acyloxy are formyl, acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, cyclohexanoyl, octanoyl, decanoyl, dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl and benzoyloxy.
  • R 1 can be alkyl through the group of formula be substituted.
  • m preferably denotes an integer from 1 to 4 and n denotes a number from 1 to 12, particularly 1 to 6.
  • R 8 in the meaning of alkyl and acyl preferably contains 1 to 12, particularly 1 to 6, carbon atoms. Examples of alkyl and acyl have been enumerated previously. Examples of the CmH2m group are ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,5-pentylene and 1,6-hexylene.
  • R 1 in the meaning of alkyl can be substituted by the group -C (O) OR 9 .
  • R 9 in the meaning of metal cation and ammonium the preferences given for R1 in this meaning apply.
  • R 9 as the residue of a monohydric alcohol preferably contains 1 to 18, particularly 1 to 12 and in particular 1 to 8 carbon atoms. It can be the remainder of an aromatic and especially aliphatic alcohol.
  • R 9 can be, for example, linear or branched C 1 -C 20 -, preferably C 1 -C 18 - and especially C 1 -C 12 alkyl, or optionally substituted by C 1 -C 12 -, especially C 1 -C 6 alkyl Cyclohexyl, cyclopentyl, (cyclohexyl) methyl, phenyl or benzyl. Examples of such residues have been listed above.
  • a preferred embodiment of the invention is characterized in that in formula I both R 1 are C 1 -C 6 alkyl substituted by -C (O) OR 9 , in which R 9 has the meaning given above.
  • R 1 corresponds to the radical of the formula -CH 2 C (O) OR 9 , in which R9 is H, NH 4 ⁇ , a metal cation, primary, secondary, tertiary or quaternary ammonium or C 1 -C 20 alkyl.
  • R 2 and R 3 are alkyl, it preferably contains 1 to 12, especially 1 to 6, carbon atoms. Examples of alkyl have been enumerated previously.
  • group -CpH 2 p- p is preferably an integer from 2 to 5, particularly 2 or 3 and in particular 3. Examples of the group -CpH 2 p- are ethylene, 1,2- or 1,3-propylene , 1,4-butylene, 1,5-pentylene, 2-methyl-1,3-propylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene.
  • R 2 and R3 represent a hydrogen atom, C i -C 4 alkyl or R2 and R 3 together represent the group -CpH 2 p-, where p is an integer from 2 to 5, especially 2 or 3 .
  • R 1 in formula la represents alkyl, it preferably contains 6 to 18, especially 6 to 12, carbon atoms.
  • R 1 , R 2 and R 3 in formula la the same preferences apply as these meanings for R i , R 2 and R 3 in formula I.
  • the compounds of formula I can be prepared, for example, by using a compound of formula II wherein R 2 and R 3 have the meaning given in formula I, reacted with CS 2 in the presence of an alkali alcoholate and then either isolated the compound of formula I, in which both R i represent a hydrogen atom, or by reaction with R'X, compounds of formula I, in which R1 has the meaning of R ', where R' is unsubstituted or substituted alkyl, cycloalkyl, cycloalkylalkyl, aralkyl or alkaralkyl as defined for R i in formula I and X represents Cl, Br or J.
  • the reaction can be carried out at temperatures from -20 ° C to 40 ° C.
  • the reaction is expediently carried out in an inert solvent, for example aromatic hydrocarbons, such as benzene, toluene or xylene.
  • aromatic hydrocarbons such as benzene, toluene or xylene.
  • the compounds can be isolated in the customary manner by hydrolysis of the reaction mixture with water, removal of the organic phase and subsequent distillation or crystallization.
  • the compounds of the formula I are liquid compounds of different viscosities or crystalline compounds. Compared to thiothiophthenes substituted by hydrocarbon radicals, they have improved solubility in aqueous and organic substrates. In addition, the solubility can be influenced in a targeted manner by the choice of the group R 1 and even water-soluble compounds can be provided, for example if R 1 and R 9 are a hydrogen atom, metal cation or ammonium. In the case of viscous representatives, dilution with, for example, a paraffin oil or a corresponding base oil offers an inexpensive form of confection.
  • the compounds of the formula I are outstandingly suitable as additives for lubricants and hydraulic fluids.
  • Another object of the invention is the use of the compounds of formula I as additives in lubricants and hydraulic fluids.
  • the addition of the compounds according to the invention leads to an improvement in the performance properties.
  • a surprising improvement in high-pressure and anti-wear properties is found for pure sulfur compounds. Since the compounds do not contain phosphorus, they are particularly suitable for motor oils, since damage to catalysts can be avoided. In aqueous systems, the absence of phosphorus means that there is less risk of attack by microorganisms.
  • the compounds of the formula I are advantageously added to the lubricants and hydraulic fluids in an amount of 0.01 to 10% by weight, preferably in an amount of 0.05 to 5% by weight, based on the lubricant or the hydraulic fluid.
  • 0.1-2% by weight is advantageously used in organic systems and 0.05-5% by weight is advantageously used in aqueous systems.
  • Such lubrication and hydraulic systems can be polar or non-polar in nature.
  • the selection criteria result from the solubility properties of the corresponding compounds.
  • lubricants in question are familiar to the person skilled in the art and e.g. in the "Lubricant Pocket Book” (Hüthig Verlag, Heidelberg, 1974) or by D. Klamann in “Lubricants and Related Products", Verlag Chemie, Weinheim (1982).
  • lubricants based on esters, phosphates, glycols, polyglycols and polyalkylene glycols, as well as their mixtures with water, and water itself, which preferably also contains a thickener to increase the viscosity.
  • the lubricants can additionally contain other additives which are added in order to further improve the basic properties of lubricants; these include: antioxidants, metal passivators, rust inhibitors, viscosity index improvers, pour point depressants, dispersants, detergents, thickeners, biocides, anti-foaming agents, demulsifiers and emulsifiers as well as other high-pressure additives and friction reducers.
  • additives include: antioxidants, metal passivators, rust inhibitors, viscosity index improvers, pour point depressants, dispersants, detergents, thickeners, biocides, anti-foaming agents, demulsifiers and emulsifiers as well as other high-pressure additives and friction reducers.
  • Zinc dialkyldithiophosphates with 1 to 18 carbon atoms, especially 1-12 carbon atoms in the alkyl groups, are particularly suitable. It is expedient to add 0.01 to 15, in particular 0.1 to 10,% by weight of zinc dialkyldithiophosphate, based on the lubricant or the hydraulic fluid.
  • esters of ⁇ - (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols e.g.
  • metal passivators examples are:
  • rust inhibitors are:
  • Heterocyclic compounds e.g .:
  • viscosity index improvers examples are:
  • Polymethacrylates vinyl pyrrolidone / methacrylate copolymers, polybutenes, olefin copolymers, styrene / acrylate copolymers, styrene / butadiene copolymers.
  • pour point depressants examples are:
  • dispersants / detergents examples are:
  • Polybutenylsuccinic acid imides polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sulfonates and phenolates.
  • wear protection additives are:
  • a suspension of 35 parts of sodium tertiary amylate (prepared by dissolving Na or NaH in t-amyl alcohol) in 220 parts of toluene is dissolved at 0 ° C. with a solution of 30 parts of 8,9-dithia-bicyclo- [4.3.0] A 1, 6-nonen-7-thione of the formula and 12 parts of CS 2 in 220 parts of toluene.
  • the mixture is allowed to stand at 20 ° C for 3 hours.
  • the reaction mixture is then mixed with 40 parts of ethyl chloroacetate at 5 ° C. and left to stand for a further 3 hours.
  • Example 1 Using the method according to Example 1 while maintaining the stoichiometry of ethyl chloroacetate by the chlorine compounds given in Table 1 (Examples 2-4) or compound A by the compound of the formula replaced.
  • the compound of Example 3 is an oil that is not further purified. The results are summarized in Table 1.
  • a suspension of 36 parts of sodium in 200 parts of toluene is at 0 ° C with a solution of 30 parts of 8,9-dithia-bicyclo [4.3.0] - ⁇ 1,6- non-7-thione of the formula (A) and 12 parts of CS 2 in 220 parts of toluene.
  • the mixture is left to stand at 20 ° C. for 3 hours.
  • 220 parts of water are added.
  • the aqueous phase is separated off and acidified with the exclusion of atmospheric oxygen with 180 parts of 10% sulfuric acid.
  • the precipitate is filtered off, washed with ice-cold water, a little ice-cold methanol and cyclohexane and dried in the dark under high vacuum.
  • 31.5 parts of the garnet-red product of the formula (C) are obtained, which can be converted into bismethylated derivative (D) (mp. 148 ° C.) with dimethyl sulfate in 67% yield:
  • Example 7 is esterified in toluene with 2-ethyl-hexanoyl chloride and triethylamine by conventional methods.
  • a dark red oil of the formula (F) is obtained:
  • a base oil from Shell (Catenex P 941®) and water containing 0.5% by weight of potassium hydroxide solution, 1.5% by weight of triethanolamine and 0.75% by weight of corrosion inhibitor are used as test liquids for the effectiveness of the additives.
  • the pH of this solution together with the additive is 8.5.
  • the results are shown in Table 2.
  • the evaluation of copper corrosion according to ASTM D-130 is given.
  • control measurements are carried out with a mixture of 50% by weight of water and 50% by weight of ethanol, wear values around 40 mm 2 being observed.
  • An oil of specification SAE 10W-30 is used as the test liquid for the effectiveness of the additives. It consists of a mixture of 72.8 wt% mineral oil (ISO VG 32), 11.2 wt% XOA 938 @ (Orogil) and 6 wt% Viscoplex 610 @ (Roehm). The results are summarized in Table 4 below.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (19)

1. Composition contenant un lubrifiant ou un liquide hydraulique et au moins un composé répondant à la formule I:
Figure imgb0027
dans laquelle:
les deux R1 représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène, un cation métallique, NH4 +, un radical ammonium primaire, secondaire, tertiaire ou quaternaire, un alkyle en C1-C24 linéaire ou ramifié, un radical cycloalkyle ou cycloalkyl-alkyle qui porte éventuellement un alkyle en C1-C18 et dont le cycle contient de 3 à 7 atomes de carbone, un aralkyle en C7-C16 ou un alkyl-aralkyle en C8-C40, l'alkyle en C1-C24 pouvant porter comme substituant(s) un radical -NR4R5, -N+R4R5R6, -OR7,
-SR7, -(CmH2mO)nR8 ou -C(O)OR9 ou un radical acyloxy en Ci-C2o, radicaux dans lesquels R4, R5 et R6 représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène ou un alkyle en C1-c20 éventuellement porteur d'un -OH, ou R4 et R5 forment ensemble un radical tétraméthylène, pentaméthylène ou oxa-3 pentylène, R7 représente un atome d'hydrogène, un alkyle en C1-C18 linéaire ou ramifié ou un radical cyclohexyle, phényle ou benzyle éventuellement porteur d'un alkyle en C1-C12, R8 représente un atome d'hydrogène, un alkyle en C1-C18 ou un acyle en C1-C20, et R9 représente un atome d'hydrogène, le radical d'un monoalcool amputé d'un radical hydroxy, un cation métallique, NH4 + ou un radical ammonium primaire, secondaire, tertiaire ou quaternaire, m représente un nombre entier de 1 à 6, et n représente un nombre de 1 à 20, et R2 et R3 représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène ou un alkyle en C1-C20 linéaire ou ramifié, ou forment ensemble un radical -CpH2p- dans lequel p désigne un nombre entier de 2 à 9.
2. Composition selon la revendication 1 caractérisée en ce, dans la formule I:
les deux R1 représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène, un cation métallique d'un métal alcalin, d'un métal alcalino-terreux ou d'un métal de transition, NH4 +, un radical ammonium primaire, secondaire, tertiaire ou quaternaire contenant des alkyles en C1-C18, un alkyle en C1-C12 linéaire ou ramifié, un cyclohexyle éventuellement porteur d'un alkyle en Ci-Ce, un phénylalkyle en C7-C12 ou un alkyl-benzyle en C8-C30, l'alkyle en C1-C12 pouvant porter un radical -NR4R5, -N+R4R5R6, - OR7, -SR7, CmH2mO)nRS ou -C(O)OR9 ou un acyloxy en C1-C12, radicaux dans lesquels R4, R5 et R6 représentent chacun, indépendamment les uns des autres, un atome d'hydrogène ou un alkyle en C1-C18,
R7 représente un atome d'hydrogène, un alkyle en C1-C12 linéaire ou ramifié ou un radical phényle ou benzyle éventuellement porteur d'un alkyle en C1-C12, R8 représente un atome d'hydrogène, un alkyle en C1-C12 ou un acyle en C1-C12, R9 représente un atome d'hydrogène ou le radical d'un monoalcool en C1-G20 amputé d'un radical hydroxy ou un alkyle en C1-C20 linéaire ou ramifié, m représente un nombre entier de 1 à 4 et n représente un nombre de 1 à 6, et R2 et R3 représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène ou un alkyle en C1-C12 linéaire ou ramifié, ou forment ensemble un radical -CpH2p- dans p désigne un nombre entier de 2 à 7.
3. Composition selon la revendication 1 caractérisée en ce que les deux symboles Ri, dans la formule I, représentent H, NH4, Li+, Na+, K+, Mg2+, Ca2+ CU2+ ou Zn2+.
4. Composition selon la revendication 1 caractérisée en ce que les deux symboles Ri, dans la formule 1, lorsqu'ils représentent des radicaux ammoniums, répondent à l'une des formules:
R10N+H3, R10R11N+H2, R10R11R12N+H et R10R11R12R13N+ dans lesquelles R10, R11, R12 et R13 représentent chacun, indépendamment les uns des autres, un alkyle en C1-C18, linéaire ou ramifié, éventuellement porteur d'un hydroxy.
5. Composition selon la revendication 4 caractérisée en ce que R10 représente un alkyle en C6-C18 linéaire ou ramifié et R11, R12 et R13 représentent chacun un alkyle en C1-C4 linéaire ou ramifié.
6. Composition selon la revendication 1 caractérisée en ce que R4, R5 et R6 représentent chacun, indépendamment les uns des autres, un atome d'hydrogène ou un alkyle en C1-C12 éventuellement porteur d'un -OH.
7. Composition selon la revendication 1 caractérisée en ce que, dans la formule I, les deux symboles R1 représentent chacun un alkyle en C2-C18 linéaire ou ramifié.
8. Composition selon la revendication 1 caractérisée en ce que, dans la formule I, les deux symboles R1 représentent chacun un alkyle en C1-C6 porteur d'un radical -C(O)OR9 et R9 a la signification qui lui a été donnée à la revendication 1.
9. Composition selon la revendication 1 caractérisée en ce que les deux symboles R1 représentent un radical -CH2C(O)OR9 dans lequel R9 représente NH4 +, un cation métallique, un ammonium primaire, secondaire, tertiaire ou quaternaire ou un alkyle en C1-C20.
10. Composition selon la revendication 1 caractérisée en ce que R2 et R3 représentent chacun un atome d'hydrogène ou un alkyle en C1-C4 ou forment ensemble un radical -CpH2p- dans lequel p désigne un nombre entier de 2 à 5, de préférence égal à 2 ou à 3.
11. Composition selon la revendication 1 caractérisée en ce que le composé de formule 1 s'y trouve en une quantité de 0,01 à 10% en poids par rapport au lubrifiant ou au liquide hydraulique.
12. Composition selon la revendication 1 caractérisée en ce qu'elle contient en outre de 0,01 à 15% en poids, par rapport au lubrifiant, ou au liquide hydraulique, d'un dithiophosphate de zinc et de dialkyle.
13. Composés répondant à la formule la:
Figure imgb0028
dans laquelle:
les deux R1 représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène, un cation métallique, NH4 + , un radical ammonium primaire, secondaire, tertiaire ou quaternaire, un radical cycloalkyle ou cycloalkyl-alkyle qui porte éventuellement un alkyle en C1-C18 et dont le cycle contient de 3 à 7 atomes de carbone, un aralkyle en C7-C16, un alkyl-aralkyle en C8-C40, un alkyle en C3-C24 linéaire ou ramifié ou un alkyle en C1-C24 qui porte un radical -NR4R5, -N+R4R5R6, -OR7, -SR7, -(CmH2mO)nR8 ou
-C(O)OR9 ou un acyloxy en Ci-C20, radicaux dans lesquels R4, R5 et R6 représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène ou un alkyle en C1-C20 éventuellement porteur d'un -OH, ou R4 et R5 forment ensemble un radical tétraméthylène, pentaméthylène ou oxa-3 pentylène, R7 représente un atome d'hydrogène, un alkyle en C1-C18 linéaire ou ramifié ou un radical cyclohexyle, phényle ou benzyle éventuellement porteur d'un alkyle en C1-C12, R8 représente un atome d'hydrogène, un alkyle en C1-C18 ou un acyle en Ci-C20, R9 représente un atome d'hydrogène, le radical d'un monoalcool amputé d'un radical hydroxy, un cation métallique, NH4 + ou un radical ammonium primaire, secondaire, tertiaire ou quaternaire, m représente un nombre entier de 1 à 6, et n représente un nombre de 1 à 20, et R2 et R3 représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène ou un alkyle en C1-C20 linéaire ou ramifié, ou forment ensemble un radical -CpH2p- dans lequel p désigne un nombre entier de 2 à 9.
14. Composés selon la revendication 13 dans la formule la desquels les deux symboles R1 représentent chacun un alkyle en C6-C18.
15. Composés selon la revendication 13 dans la formule la desquels les deux symboles R1 représentent chacun un alkyle en C1-C6 porteur d'un radical -C(O)OR9 dont le symbole R9 a la signification qui lui a été donnée à la revendication 13.
16. Composés selon la revendication 15 dans lesquels les deux symboles R1 représentent chacun un radical -CH2C(O)OR9 dans lequel R9 représente H, NH4, un cation métallique, un ammonium primaire, secondaire, tertiaire ou quaternaire ou un alkyle en Ci-C20.
17. Composés selon la revendication 13 dans la formule la desquels R2 et R3 représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène ou un alkyle en C1-C4 ou forment ensemble un radical -CpH2p- dans lequel p désigne un nombre entier de 2 à 5, de préférence égal à 2 ou à 3.
18. Application de composés de formule I selon la revendication 1 comme additifs dans des lubrifiants ou dans des liquides hydrauliques.
19. Application de composés de formule 1 selon la revendication 13 comme additifs dans des lubrifiants ou dans des liquides hydrauliques.
EP87810639A 1986-11-12 1987-11-06 Additifs sulfurés pour lubrifiants Expired - Lifetime EP0271437B1 (fr)

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