EP0271437B1 - Sulphurized lubricant additives - Google Patents
Sulphurized lubricant additives Download PDFInfo
- 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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- European Patent Office
- Prior art keywords
- alkyl
- hydrogen atom
- formula
- substituted
- branched
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Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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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- Organic Chemistry (AREA)
- Lubricants (AREA)
Description
Die vorliegende Erfindung betrifft Schmiermittelzusätze, enthaltend substituierte Thio-thiophthenderivate, sowie neue substituierte Thio-thiophthenderivate.The present invention relates to lubricant additives containing substituted thio-thiophene derivatives and new substituted thio-thiophene derivatives.
Schmiermitteln werden im allgemeinen Additive zur Verbesserung der Gebrauchseigenschaften zugesetzt. Besondere Anforderungen in Bezug auf das Lasttragevermögen werden an Schmiermitteln zur Uebertragung grösserer Kräfte gestellt. Durch Zusatz von Hochdruck- und verschleissmindernden Additiven werden die ansonsten auftretenden negativen Erscheinungen stark reduziert.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.
In der DE-OS 2 242 637 sind mit Kohlenwasserstoffgruppen substituierte Thio-thiophthene beschrieben, die als Oxydationsinhibitoren in Schmiermitteln Verwendung finden.DE-OS 2 242 637 describes thio-thiophthenes substituted by hydrocarbon groups, which are used as oxidation inhibitors in lubricants.
Ein Gegenstand vorliegender Erfindung ist eine Zusammensetzung, enthaltend ein Schmiermittel oder eine Hydraulikflüssigkeit und mindestens eine Verbindung der Formel
- R2 und R3 unabhängig voneinander ein Wasserstoffatom, lineares oder verzweigtes C1-C20-Alkyl darstellen, oder R2 und R3 zusammen -CpH2p-bedeuten, worin p für eine ganze Zahl von 2 bis 9 steht.
- R 2 and R 3 independently of one another represent a hydrogen atom, linear or branched C 1 -C 20 alkyl, or R2 and R3 together mean -CpH 2 p-where p is an integer from 2 to 9.
Stellt R1 ein Metallkation dar, so handelt es sich vorzugsweise um ein Alkali-, Erdalkali- oder Uebergangsmetallkation. Unter den Uebergangsmetallkationen sind besonders Zn2+ und CU 2+ bevorzugt. Unter den Alkali- und Erdalkalimetallkationen sind Li⊕, Nae, K⊕, Mg2+ und Ca2+ bevorzugt. In einer bevorzugten Untergruppe stellen beide R1 H, NH4⊕, Lie, Nae, K⊕, Mge, Ca⊕, Zn2+ und CU 2+ dar.If R 1 represents a metal cation, then 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. In a preferred subgroup, both represent R 1 H, NH 4⊕ , Lie, Nae, K ⊕ , Mge, C a⊕ , Zn 2+ and C U 2+ .
R1 in der Bedeutung von primärem, sekundärem, tertiärem und quaternärem Ammonium kann 1 bis 40, vorzugsweise 1 bis 30 C-Atome enthalten. Die N-Atome können mit gegebenenfalls durch Hydroxyl substituiertem, linearem oder verzweigtem C1-C20-Alkyl, gegebenenfalls C1-C6-Alkyl substituiertem Cycloalkyl oder Cycloalkyl-C1-C2-alkyl mit 4 bis 7 Ring-C-Atomen, Cl-C12-Alkyl substituiertem Phenyl, Benzyl oder Phenylethyl, oder durch gegebenenfalls C1-C4-Alkyl substituiertem Tri- oder Tetramethylen oder 3-Oxapentylen, substituiert sein. Bevorzugt entsprechen beide R1 in Formel I in der Bedeutung von Ammonium den Formeln
Einige Beispiele für R1 in der Bedeutung von Ammonium sind: Methyl-, Ethyl-, n- und i-Propyl-, n-, i-und 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)(Dimethyl)-, (Octyl)(Dimethyl)-, (Dodecyl)(Dimethyl)-, (Octadecyl)(Dimethyl)-, Tetramethyl-, Tetraethyl-, Tetrabutyl-, (Trimethyl)ethyl-, (Dimethyl)(Dibutyl)-, (Trimethyl)(Hexyl)-, (Trimethyl)(Dodecyl)-, (Trimethyl)(Octadecyl)-, Cyclohexyl-, (Cyclohexyl)(Dimethyl)-, Cyclohexyl(Trimethyl)-, (Cyclohexyl)methyl-, (Methylphenyl)-, (Phenyl)(Dimethyl)-, (Methylbenzyl)-, (Methyl)(Benzyl)-, (Benzyl)Dimethyl-, (Dimethylbenzyl)-, (Nonylphenyl)-, (Decylphenyl)-, (Dodecylphenyl)-, (Octadecylphenyl)-, (Decylphenyl)(Dimethyl)ammonium.Some examples of 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 ) (Dimethyl) -, (Octyl) (Dimethyl) -, (Dodecyl) (Dimethyl) -, (Octadecyl) (Dimethyl) -, Tetramethyl-, Tetraethyl-, Tetrabutyl-, (Trimethyl) ethyl-, (Dimethyl) (Dibutyl ) -, (Trimethyl) (Hexyl) -, (Trimethyl) (Dodecyl) -, (Trimethyl) (Octadecyl) -, Cyclohexyl-, (Cyclohexyl) (Dimethyl) -, Cyclohexyl (Trimethyl) -, (Cyclohexyl) methyl-, (Methylphenyl) -, (Phenyl) (Dimethyl) -, (Methylbenzyl) -, (Methyl) (Benzyl) -, (Benzyl) Dimethyl-, (Dimethylbenzyl) -, (Nonylphenyl) -, (Decylphenyl) -, (dodecylphenyl) -, (octadecylphenyl) -, (decylphenyl) (dimethyl) ammonium.
Stellt R1 unsubstituiertes Alkyl dar, so handelt es sich bevorzugt um lineares oder verzweigtes Ci-C20-, besonders C2-C18-, insbesondere C2-C12- und ganz besonders C4-C12-Alkyl. Beispiele für Alkyl sind Methyl, Ethyl, n- und i-Propyl, n-, i- und t-Butyl, n-Pentyl, 2-Methylbut-1-yl, n-Hexyl-, 2-Me- thylpent-1-yl, 2-Ethylpent-1- oder -2-yl, n-Heptyl, 2-n-Propylhept-1-yl, n-Octyl, 2-Ethylhex-1-yl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Hexadecyl, Octadecyl und Eicosyl.If 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. Examples of 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 der Bedeutung von Aralkyl, bevorzugt Phenylalkyl, enthält besonders 7 bis 12 C-Atome und stellt besonders Benzyl, 1-Phenyleth-2-yl, 1-Phenyleth-1-yl, 1-Phenyl-prop-1-, -2- oder -3-yl dar.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.
Stellt R1 Alkaralkyl dar, so ist dessen Arylgruppe bevorzugt Phenyl und dessen Alkylengruppe bevorzugt 1,1- oder 1,2-Ethylen und besonders Methylen. Bevorzugt enthält das Alkaralkyl 1 bis 3, besonders 1 oder 2 Alkylgruppen, die vorzugsweise 1 bis 20, besonders 1 bis 12 C-Atome enthalten und linear oder verzweigt sein können. Insbesondere stellt R1 als Alkaralkyl Mono- oder Dialkylbenzyl mit 8 bis 20 C-Atomen dar. Beispiele für Alkaralkyl sind Methylbenzyl, 1-(Methylphenyl)eth-2-yl, Dimethylbenzyl, Ethylbenzyl, n- oder i-Propylbenzyl, n-oder t-Butylbenzyl, Di-t-butylbenzyl, Hexylbenzyl, Octylbenzyl, Methylbutylbenzyl, Nonylbenzyl, Dioctyl- oder Dinonylbenzyl, Decylbenzyl, Dodecylbenzyl, Hexadecylbenzyl, Octadecylbenzyl.If 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. In particular, R 1 as alkaralkyl represents mono- or dialkylbenzyl having 8 to 20 carbon atoms. Examples of alkaralkyl are 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.
Stellt R1 Cycloalkyl oder Cycloalkylalkyl dar, so handelt es sich bei den Cycloalkylgruppen bevorzugt um Cyclopentyl und besonders Cyclohexyl. Die Alkylengruppe im Cycloalkylalkyl ist bevorzugt Ethylen und besonders Methylen. Sofern die Cycloalkylgruppen durch Alkyl substituiert sind, enthält das Alkyl vorzugsweise 1 bis 12 und besonders 1 bis 6 C-Atome. Das Alkyl kann linear oder verzweigt sein. Einige Beispiele sind Methyl-, Dimethyl-, Ethyl-, Propyl-, Butyl-, Pentyl-, Hexyl-, Octyl-, 3,3,5-Trimethylcyclohexyl, Decylcyclohexyl- oder -cyclopentyl, (Methylcyclohexyl)methyl, Cyclopentylmethyl, Cyclohexylmethyl.If 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.
R1 kann als Alkyl wie zurvor definiert substituiert sein. Für diesen Fall enthält das Alkyl bevorzugt 1 bis 12, besonders 1 bis 6, und insbesondere 1 bis 3 C-Atome.R 1 can be substituted as alkyl as previously defined. In this case, the alkyl preferably contains 1 to 12, particularly 1 to 6, and in particular 1 to 3 carbon atoms.
R1 kann in der Bedeutung von Alkyl durch Amino- oder Ammoniumgruppen der Formeln -NR4R5 oder - ⊕ NR4R5R6 substituiert sein, worin R4, R5 und R6 unabhängig bevorzugt für ein Wasserstoffatom oder gegebenenfalls durch -OH substituiertes C1-C18-, besonders C1-C12- und insbesondere C1-C6-Alkyl stehen. In wässrigen oder wässrig-organischen Substraten werden zweckmässig solche Verbindungen der Formel I verwendet, in denen R4, R5 oder R6 gegebenenfalls durch -OH substituiertes C1-C6.-, besonders C1-C4-Alkyl oder ein Wasserstoffatom darstellen. In organischen Substraten werden vorteilhaft solche Verbindungen der Formel I verwendet, in denen R4 C6-C18-Alkyl und R5 und R6 unabhängig ein Wasserstoffatom oder C1-C6-, besonders C1-C4-Alkyl darstellen. Beispiele für Alkylgruppen sind zuvor für R1 in der Bedeutung von Ammonium aufgezählt worden.In the meaning of alkyl, 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. In aqueous or aqueous-organic substrates, such compounds of formula I are conveniently used in which R4 is R5 or R6, if appropriate, particularly C 1 -C, through -OH-substituted C 1 -C 6 .- 4 alkyl or a hydrogen atom. In organic substrates such compounds of formula I are advantageously used, in which R 4 is C 6 -C 18 alkyl, and R5 and R6 independently represent a hydrogen atom or C 1 -C 6 -, especially C 1 -C 4 represent alkyl. Examples of alkyl groups have previously been listed for R1 in the meaning of ammonium.
R1 kann in der Bedeutung von Alkyl durch -OR7 oder -SR7 substituiert sein. R7 ist bevorzugt ein Wasserstoffatom, lineares oder verzweigtes C1-C12-, besonders C1-C6-Alkyl, gegebenenfalls durch C1-C4-Alkyl substituiertes Cyclohexyl, oder gegebenenfalls durch Ci-C18-, besonders C1-C12-Alkyl substituiertes Phenyl oder Benzyl. Beispiele für solche Alkylgruppen sind zuvor für R1 in der Bedeutung von mit Alkyl substituiertem Cycloalkyl und Alkaralkyl aufgezählt worden. Beispiele für R7 als Alkylphenyl sind Methyl-, Dimethyl-, Ethyl-, n- oder i-Propyl-, n-, i- oder -t-Butyl-, Methyl-t-butyl-, Di-t-butyl-, Pentyl-, Hexyl-, Octyl-, Dioctyl-, Nonyl-, Decyl-, Dodecyl-, Hexadecyl-, Octadecyl-, Dinonyl-, Didecyl- und Didodecylphenyl.In the meaning of alkyl, 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. Examples of 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.
Stellt R1 durch Acyloxy substituiertes Alkyl dar, so enthält das Acyloxy bevorzugt 1 bis 12 und besonders 1 bis 6 C-Atome. Beispiele für Acyloxy sind Formyl-, Acetyl-, Propionyl-, Butanoyl-, Pentanoyl-, Hexanoyl-, Cyclohexanoyl-, Octanoyl-, Decanoyl-, Dodecanoyl-, Tetradecanoyl-, Hexadecanoyl-, Octadecanoyl- und Benzoyloxy.If 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.
R1 kann als Alkyl durch die Gruppe der Formel
R1 in der Bedeutung von Alkyl kann durch die Gruppe -C(O)OR9 substituiert sein. Für R9 in der Bedeutung von Metallkation und Ammonium gelten die für R1 in dieser Bedeutung gegebenen Bevorzugungen. R9 als Rest eines einwertigen Alkoholes enthält bevorzugt 1 bis 18, besonders 1 bis 12 und insbesondere 1 bis 8 C-Atome. Es kann sich um den Rest eines aromatischen und besonders aliphätischen Alkohols handeln. R9 kann z.B. lineares oder verzweigtes C1-C20-, vorzugsweise C1-C18- und besonders C1-C12-Alkyl, oder gegebenenfalls durch C1-C12-, besonders C1-C6-Alkyl substituiertes Cyclohexyl, Cyclopentyl, (Cyclohexyl)methyl, Phenyl oder Benzyl sein. Beispiele für solche Reste sind zuvor aufgezählt worden. Eine bevorzugte Ausführungsform der Erfindung ist dadurch gekennzeichnet, dass in Formel I beide R1 durch -C(O)OR9 substituiertes C1-C6-Alkyl sind, worin R9 die zuvor angegebene Bedeutung hat. Eine besonders bevorzugte Ausführungsform der Erfindung ist dadurch gekennzeichnet, dass beide R1 dem Rest der Formel -CH2C(O)OR9 entsprechen, worin R9 H, NH4ß, ein Metallkation, primäres, sekundäres, tertiäres oder quaternäres Ammonium oder C1-C20-Alkyl bedeutet.R 1 in the meaning of alkyl can be substituted by the group -C (O) OR 9 . For R9 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. A particularly preferred embodiment of the invention is characterized in that both R 1 correspond to the radical of the formula -CH 2 C (O) OR 9 , in which R9 is H, NH 4β , a metal cation, primary, secondary, tertiary or quaternary ammonium or C 1 -C 20 alkyl.
Stellen R2 und R3 Alkyl dar, so enthält es bevorzugt 1 bis 12, besonders 1 bis 6 C-Atome. Beispiele für Alkyl sind zuvor aufgezählt worden. In der Gruppe -CpH2p- steht p bevorzugt für eine ganze Zahl von 2 bis 5, besonders 2 oder 3 und insbesondere 3. Beispiele für die Gruppe -CpH2p- sind Ethylen, 1,2- oder 1,3-Propylen, 1,4-Butylen, 1,5-Pentylen, 2-Methyl-1,3-propylen, 1,6-Hexylen, 1,7-Heptylen, 1,8-Octylen, 1,9-Nonylen.If 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. In the 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.
In einer bevorzugten Ausführungsform stellen R2 und R3 ein Wasserstoffatom, Ci-C4-Alkyl oder R2 und R3 zusammen die Gruppe -CpH2p- dar, worin p für eine ganze Zahl von 2 bis 5, besonders 2 oder 3 steht.In a preferred embodiment, 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 .
Eine andere bevorzugte Ausführungsform der Erfindung ist dadurch gekennzeichnet, dass in Formel I beide R1 unabhängig voneinander ein Wasserstoffatom, ein Alkali-, Erdalkali- oder Uebergangsmetallkation, NH4S, primäres, sekundäres, tertiäres oder quaternäres Ammonium mit C1-C18-Alkylgruppen, lineares oder verzweigtes C1-C12-Alkyl, gegebenenfalls durch C1-C6-Alkyl substituiertes Cyclohexyl, C7-C12-Phenylalkyl oder C8-C30-Alkylbenzyl darstellen, wobei das C1-C12-Alkyl durch -NR4R5 oder - ⊕ NR4R5R6, -OR7 -SR7,
- R2 und R3 unabhängig voneinander ein Wasserstoffatom, lineares oder verzweigtes C1-C12-Alkyl oder R2 und R3 zusammen -CpH2p- darstellen, worin p für eine ganze Zahl von 2 bis 7 steht.
- R 2 and R3 independently of one another represent a hydrogen atom, linear or branched C 1 -C 12 alkyl or R 2 and R 3 together -CpH 2 p-, where p is an integer from 2 to 7.
Ein weiterer Gegenstand der Erfindung sind die neuen Verbindungen der Formel la
- R2 und R3 unabhängig voneinander ein Wasserstoffatom, lineares oder verzweigtes C1-C2o-Alkyl darstellen, oder R2 und R3 zusammen -CpH2p- bedeuten, worin p für eine ganze Zahl von 2 bis 9 steht.
- R2 and R 3 independently represent a hydrogen atom, linear or branched C 1 -C 2 o -alkyl, or R2 and R 3 together mean -CpH 2 p-, where p is an integer from 2 to 9.
Stellt R1 in Formel la Alkyl dar, so enthält es bevorzugt 6 bis 18, besonders 6 bis 12 C-Atome. Für die übrigen Bedeutungen von Rl, R2 und R3 in Formel la gelten die gleichen Bevorzugungen wie diese Bedeutungen für Ri, R2 und R3 in Formel I.If R 1 in formula la represents alkyl, it preferably contains 6 to 18, especially 6 to 12, carbon atoms. For the other meanings of 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.
Die Verbindungen der Formel I sind teilweise bekannt oder können nach bekannten Verfahren hergestellt werden. Geeignete Verfahren sind z.B. von C. Portail et al. in Bull. Soc. Chim. Fr., 1966 (10), S. 3187-3189 beschrieben.Some of the compounds of the formula I are known or can be prepared by known processes. Suitable methods are e.g. by C. Portail et al. in Bull. Soc. Chim. Fr., 1966 (10), pp. 3187-3189.
Die Verbindungen der Formel I können z.B. hergestellt werden, indem man eine Verbindung der Formel II
Die Umsetzung kann bei Temperaturen von -20°C bis 40°C vorgenommen werden. Zweckmässig wird die Umsetzung in einem inerten Lösungsmittel, z.B. aromatischen Kohlenwasserstoffen, wie Benzol, Toluol oder Xylol, durchgeführt. Die Isolierung der Verbindungen kann in üblicher Weise durch Hydrolyse des Reaktionsgemisches mit Wasser, Abtrennen der organischen Phase und anschliessende Destillation oder Kristallisation erfolgen.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. 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.
Verbindungen der Formel I, worin R1 und R9 ein Metallkation oder Ammonium bedeuten, können hergestellt werden, indem man in bekannter Weise entsprechende Metall- oder Ammoniumbasen mit Verbindungen der Formel I, worin Ri und R9 in Formel I ein Wasserstoffatom bedeuten, umsetzt. Diese Umsetzung kann auch in situ in Schmiermitteln und Hydraulikflüssigkeiten erfolgen.Compounds of the formula I in which R 1 and R 9 represent a metal cation or ammonium can be prepared by known metal or ammonium bases with compounds of the formula I in which R i and R 9 in formula I represent a hydrogen atom, implements. This implementation can also take place in situ in lubricants and hydraulic fluids.
Bei den Verbindungen der Formel I handelt es sich um flüssige Verbindungen unterschiedlicher Viskosität oder um kristalline Verbindungen. Sie weisen gegenüber mit Kohlenwasserstoffresten substituierten Thiothiophthenen eine verbesserte Löslichkeit in wässrigen und organischen Substraten auf. Darüber hinaus kann durch die Wahl der Gruppe R1 die Löslichkeit gezielt beeinflusst werden und es können sogar wasserlösliche Verbindungen bereitgestellt werden, z.B. wenn R1 und R9 ein Wasserstoffatom, Metallkation oder Ammonium sind. Bei viskosen Vertretern bietet die Verdünnung mit z.B. einem Paraffinöl oder auch einem entsprechenden Grundöl eine günstige Konfektionsform. Die Verbindungen der Formel I eignen sich hervorragend als Zusätze zu Schmiermitteln und Hydraulikflüssigkeiten. Ein weiterer Gegenstand der Erfindung ist die Verwendung der Verbindungen der Formel I als Additive in Schmiermitteln und Hydraulikflüssigkeiten. Der Zusatz der erfindungsgemässen Verbindungen führt zu einer Verbesserung der Gebrauchseigenschaften. Hierbei wird eine für reine Schwefelverbindungen überraschende Verbesserung der Hochdruck- und Antiverschleisseigenschaften gefunden. Da die Verbindungen keinen Phosphor enthalten, sind sie besonders für Motorenöle geeignet, da eine Schädigung von Katalysatoren vermieden werden kann. In wässrigen Systemen besteht durch die Abwesenheit von Phosphor eine geringere Gefahr des Befalls mit Mikroorganismen.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.
Die Verbindungen der Formel I werden den Schmiermitteln und Hydraulikflüssigkeiten zweckmässig in einer Menge von 0,01 bis 10 Gew.-%, vorzugsweise in einer Menge 0,05 bis 5 Gew.-%, bezogen auf das Schmiermittel oder die Hydraulikflüssigkeit, zugesetzt. In organischen Systemen werden vorteilhaft 0,1-2 Gew.-% und in wässrigen Systemen vorteilhaft 0,05-5 Gew.-% verwendet.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.
Solche Schmier- und Hydrauliksysteme können von polarer oder unpolarer Natur sein. Die Auswahlkriterien ergeben sich aus den Löslichkeitseigenschaften der entsprechenden Verbindungen.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.
Die in Frage kommenden Schmiermittel sind dem Fachmann geläufig und z.B. im "Schmiermittel Taschenbuch" (Hüthig Verlag, Heidelberg, 1974) oder von D. Klamann in "Schmierstoffe und verwandte Produkte", Verlag Chemie, Weinheim (1982) beschrieben.The 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).
Besonders geeignet sind neben Minealölen z.B. Poly-a-Olefine, Schmiermittel auf Esterbasis, Phosphate, Glykole, Polyglykole und Polyalkylenglykole, sowie deren Mischungen mit Wasser, und Wasser selbst, welches bevorzugt zur Erhöhung der Viskosität zusätzlich noch einen Verdicker enthält.In addition to mineral oils, e.g. Poly-a-olefins, 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.
Die Schmiermittel können zusätzlich andere Additive enthalten, die zugegeben werden, um die Grundeigenschaften von Schmierstoffen noch weiter zu verbessern; dazu gehören: Antioxidantien, Metallpassivatoren, Rostinhibitoren, Viskositätsindex-Verbesserer, Stockpunkterniedriger, Dispergiermittel, Detergentien, Verdicker, Biozide, Antischaumittel, De- und Emulgatoren sowie andere Hochdruck-Zusätze und Reibungsverminderer.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.
Als besonders vorteilhaft hat sich die Mitverwendung von Zinkdialkyldithiophosphaten erwiesen, da die Wirkung der Verbindungen der Formel 1 erheblich gesteigert werden kann. Besonders geeignet sind Zinkdialkyldithiophosphate mit 1 bis 18 C-Atomen, besonders 1-12 C-Atomen in den Alkylgruppen. Zweckmässig werden 0,01 bis 15, besonders 0,1 bis 10 Gew.-% Zinkdiealkyldithiophosphate zugesetzt, bezogen auf das Schmiermittel oder die Hydraulikflüssigkeit.The use of zinc dialkyldithiophosphates has proven to be particularly advantageous since the action of the compounds of the formula 1 can be increased considerably. 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.
Beispiele für phenolische Antioxidantien als zusätzliche Additive sind:
- 1. Alkvlierte Monophenole 2,6-Di-tert-butyl-4-methylphenol
- 2,6-Di-tert-butylphenol
- 2-tert-Butyl-4,6-dimethylphenol
- 2,6-Di-tert-butyl-4-ethylphenol
- 2,6-Di-tert-butyl-4-n-butylphenol
- 2,6-Di-tert-butyl-4-iso-butylphenol
- 2,6-Di-cyclopentyl-4-methylphenol
- 2-(α-Methylcyclohexyl)-4,6-dimethylphenol
- 2,6-Di-octadecyl-4-methylphenol
- 3. Hydroxylierte Thiodiphenvlether 2,2'-Thio-bis-(6-tert-butyl-4-methylphenol)
- 2,2'-Thio-bis-(4-octylphenoi)
- 4,4'-Thio-bis-(6-tert-butyl-3-methylphenol)
- 4,4'-Thio-bis-(6-tert-butyl-2-methylphenol)
- 4. Alkyliden-Bisphenole 2,2'-Methylen-bis-(6-tert-butyl-4-methylphenol)
- 2,2'-Methylen-bis-(6-tert-butyl-4-ethylphenol)
- 2,2'-Methylen-bis-[4-methyl-6-(a-methylcyclohexyl)-phenol]
- 2,2'-Methylen-bis-(4-methyl-6-cyclohexylphenol)
- 2,2'-Methylen-bis-(6-nonyl-4-methylphenol)
- 2,2'-Methylen-bis-(4,6-di-tert-butylphenol)
- 2,2'-Ethyliden-bis-(4,6-di-tert-butylphenol)
- 2,2'-Ethyliden-bis-(6-tert-butyl-4-iso-butylphenol
- 2,2'-Methylen-bis-[6-(a-methylbenzyl)-4-nonylphenol]
- 2,2'-Methylen-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]
- 4,4'-Methylen-bis-(2,6-di-tert-butylphenol)
- 4,4'-Methylen-bis-(6-tert-butyl-2-methylphenol)
- 1,1-Bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butan
- 2,6-Di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol
- 1,1,3-Tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutan
- 6. Acylaminophenole 4-Hydroxy-laurinsäureanilid
- 4-Hydroxy-stearinsäureanilid
- 2,4-Bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazin
- N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbaminsäureoctylester.
- 7. Ester der β-(3,5-Di-tert-butyl-4-hydroxyphenyl)-propionsäure mit ein- oder mehrwertigen Alkoholen,
- wie z.B. mit
- MethanolDiethylenglycol
- OctadecanolTriethylenglycol
- 1,6-HexandiolPentaerythrit
- NeopentylglycolTris-hydroxyethyl-isocyanurat
- ThiodiethylenglycolDi-hydroxyethyl-oxalsäurediamid
- 1. Alkalized monophenols 2,6-di-tert-butyl-4-methylphenol
- 2,6-di-tert-butylphenol
- 2-tert-butyl-4,6-dimethylphenol
- 2,6-di-tert-butyl-4-ethylphenol
- 2,6-di-tert-butyl-4-n-butylphenol
- 2,6-di-tert-butyl-4-iso-butylphenol
- 2,6-di-cyclopentyl-4-methylphenol
- 2- (α-methylcyclohexyl) -4,6-dimethylphenol
- 2,6-di-octadecyl-4-methylphenol
- 3. Hydroxylated thiodiphenyl ether 2,2'-thio-bis- (6-tert-butyl-4-methylphenol)
- 2,2'-thio-bis- (4-octylphenoi)
- 4,4'-thio-bis- (6-tert-butyl-3-methylphenol)
- 4,4'-thio-bis- (6-tert-butyl-2-methylphenol)
- 4. Alkylidene bisphenols 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol)
- 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol)
- 2,2'-methylene-bis- [4-methyl-6- (a-methylcyclohexyl) phenol]
- 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol)
- 2,2'-methylene-bis- (6-nonyl-4-methylphenol)
- 2,2'-methylene-bis- (4,6-di-tert-butylphenol)
- 2,2'-ethylidene-bis- (4,6-di-tert-butylphenol)
- 2,2'-ethylidene bis (6-tert-butyl-4-iso-butylphenol
- 2,2'-methylene-bis- [6- (a-methylbenzyl) -4-nonylphenol]
- 2,2'-methylene-bis- [6- (α, α-dimethylbenzyl) -4-nonylphenol]
- 4,4'-methylene-bis- (2,6-di-tert-butylphenol)
- 4,4'-methylene-bis- (6-tert-butyl-2-methylphenol)
- 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane
- 2,6-di- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol
- 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane
- 6. Acylaminophenols 4-hydroxy-lauric anilide
- 4-hydroxy stearic anilide
- 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine
- N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamic acid octyl ester.
- 7. esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols,
- like with
- Methanol diethylene glycol
- Octadecanol triethylene glycol
- 1,6-hexanediol pentaerythritol
- Neopentyl glycol tris hydroxyethyl isocyanurate
- Thiodiethylene glycol di-hydroxyethyl oxalic acid diamide
- MethanolDiethylenglycolMethanol diethylene glycol
- OctadecanolTriethylenglycolOctadecanol triethylene glycol
- N,N'-Di-isopropyl-p-phenylendiaminN, N'-di-isopropyl-p-phenylenediamine
- N,N'-Di-sec-butyl-p-phenylendiaminN, N'-di-sec-butyl-p-phenylenediamine
- N,N'-Bis(1,4-dimethyl-pentyl)-p-phenylendiaminN, N'-bis (1,4-dimethylpentyl) p-phenylenediamine
- N,N'-Bis(1-ethyl-3-methyl-pentyl)-p-phenylendiaminN, N'-bis (1-ethyl-3-methylpentyl) p-phenylenediamine
- N,N'-Bis(1-methyl-heptyl)-p-phenylendiaminN, N'-bis (1-methyl-heptyl) -p-phenylenediamine
- N,N'-Diphenyl-p-phenylendiaminN, N'-diphenyl-p-phenylenediamine
- N,N'-Di-(naphthyl-2)-p-phenylendiaminN, N'-di- (naphthyl-2) -p-phenylenediamine
- N-Isopropyl-N'-phenyl-p-phenylendiaminN-isopropyl-N'-phenyl-p-phenylenediamine
- N-(1,3-Dimethyl-butyl)-N'-phenyl-p-phenylendiaminN- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine
- N-(1-Methyl-heptyl)-N'-phenyl-p-phenylendiaminN- (1-methyl-heptyl) -N'-phenyl-p-phenylenediamine
- N-Cyclohexyl-N'-phenyl-p-phenylendiaminN-cyclohexyl-N'-phenyl-p-phenylenediamine
- 4-(p-Toluol-sulfonamido)-diphenylamin4- (p-toluenesulfonamido) diphenylamine
- N,N'-Dimethyl-N,N'-di-sec-butyl-p-phenylendiaminN, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine
- DiphenylaminDiphenylamine
- 4-lsopropoxy-diphenylamin4-isopropoxy-diphenylamine
- N-Phenyl-1-naphthylaminN-phenyl-1-naphthylamine
- N-Phenyl-2-naphthylaminN-phenyl-2-naphthylamine
- octyliertes Diphenylaminoctylated diphenylamine
- 4-n-Butylaminophenol4-n-butylaminophenol
- 4-Butyrylamino-phenol4-butyrylamino-phenol
- 4-Nonanoylamino-phenol4-nonanoylamino-phenol
- 4-Dodecanoylamino-phenol4-dodecanoylamino-phenol
- 4-Octadecanoylamino-phenol4-octadecanoylamino-phenol
- Di-(4-methoxy-phenyl)-aminDi- (4-methoxyphenyl) amine
- 2,6-Di-tert-butyl-4-dimethylamino-methyl-phenol2,6-di-tert-butyl-4-dimethylamino-methyl-phenol
- 2,4'-Diamino-diphenylmethan2,4'-diamino-diphenylmethane
- 4,4'-Diamino-diphenylmethan4,4'-diamino-diphenylmethane
- N,N,N',N'-Tetramethyl-4,4'-diamino-diphenylmethanN, N, N ', N'-tetramethyl-4,4'-diamino-diphenylmethane
- 1,2-Di-[(2-methyl-phenyl)-amino]-ethan1,2-di - [(2-methylphenyl) amino] ethane
- 1,2-Di-(phenylamino)-propan1,2-di (phenylamino) propane
- (o-Tolyl)-biguanid(o-tolyl) biguanide
- Di-[4-(1' ,3'-dimethyl-butyl)-phenyl)aminDi- [4- (1 ', 3'-dimethylbutyl) phenyl) amine
- tert-octyliertes N-Phenyl-1-naphthylamintert-octylated N-phenyl-1-naphthylamine
- Gemisch aus mono- und dialkylierten tert-Butyl-/tert-Octyldiphenyl-aminen.Mixture of mono- and dialkylated tert-butyl / tert-octyldiphenyl amines.
-
für Kupfer, z.B.:
Triazol, Benztriazol und deren Derivate, 2-Mercaptobenzthiazol, 2,5-Dimercaptothiadiazol, Salicylidenpropylendiamin, Salze von Salicylaminoguanidin.for copper, for example:
Triazole, benzotriazole and their derivatives, 2-mercaptobenzothiazole, 2,5-dimercaptothiadiazole, salicylidene propylene diamine, salts of salicylaminoguanidine.
- a) Organische Säuren, ihre Ester, Metallsalze und Anhydride, z.B.: N-Oleoyl-sarcosin, Sorbitan-mono-oleat, Blei-naphthenat, Dodecenylbernsteinsäure-anhydrid, Alkenylbernsteinsäure-Halb-ester, 4-Nonylphenoxy-essigsäure.a) Organic acids, their esters, metal salts and anhydrides, e.g. N-oleoyl sarcosine, sorbitan mono-oleate, lead naphthenate, dodecenylsuccinic anhydride, alkenylsuccinic acid half-ester, 4-nonylphenoxyacetic acid.
- b) Stickstoffhaltige Verbindungen, z.B.:b) Nitrogen-containing compounds, e.g .:
- I. Primäre, sekundäre oder tertiäre aliphatische oder cycloaliphatische Amine und Amin-Salze von organischen und anorganischen Säuren, z.B. öllösliche Alkylammoniumcarboxylate.I. Primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, e.g. oil-soluble alkylammonium carboxylates.
Substituierte Imidazoline und Oxazoline.
- c) Phosphorhaltige Verbindungen, z.B.: Aminsalze von Phosphorsäurepartialestern.
- d) Schwefelhaltige Verbindungen, z.B.: Barium-dinonylnaphthalin-sulfonate, Calciumpetroleum-sulfonate.
- c) phosphorus-containing compounds, for example: amine salts of phosphoric acid partial esters.
- d) Sulfur-containing compounds, for example: barium dinonylnaphthalene sulfonates, calcium petroleum sulfonates.
Polymethacrylate, Vinylpyrrolidon/Methacrylat-Copolymere, Polybutene, Olefin-Copolymere, Styrol/Acrylat-Copolymere, Styrol/Butadien-Copolmere.Polymethacrylates, vinyl pyrrolidone / methacrylate copolymers, polybutenes, olefin copolymers, styrene / acrylate copolymers, styrene / butadiene copolymers.
Polymethacrylat, alkylierte Naphthalinderivate.Polymethacrylate, alkylated naphthalene derivatives.
Polybutenylbernsteinsäure-imide, Polybutenylphosphonsäurederivate, basische Magnesium-, Calcium-, und Bariumsulfonate und -phenolate.Polybutenylsuccinic acid imides, polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sulfonates and phenolates.
Schwefel und/oder Phosphor und/oder Halogen enthaltende Verbindungen, wie geschwefelte pflanzliche Oele, Zinkdialkyl- oder Zinkdiaryldithiophosphate, Tritolyl-phosphat, chlorierte Paraffine, Alkyl-und Aryldisulfide, Carbamate.Compounds containing sulfur and / or phosphorus and / or halogen, such as sulfurized vegetable oils, zinc dialkyl or zinc diaryl dithiophosphates, tritolyl phosphate, chlorinated paraffins, alkyl and aryl disulfides, carbamates.
Die nachfolgenden Beispiele erläutern die Erfindung näher. Teile sind Gewichtsteile, sofern es nicht anders angegeben ist.The following examples explain the invention in more detail. Parts are parts by weight unless otherwise specified.
Eine Suspension von 35 Teilen Natriumtertiäramylat (hergestellt durch Lösen von Na oder NaH in t-Amylalkohol) in 220 Teilen Toluol wird bei 0°C mit einer Lösung von 30 Teilen 8,9-Dithia-bicyclo-[4.3.0]A1,6-nonen-7-thion der Formel
Mit der Methode gemäss Beispiel 1 wird unter Beibehaltung der Stöchiometrie Chloressigsäureethylester durch die in Tabelle 1 angegebenen Chlorverbindungen (Beispiele 2-4) bzw. Verbindung A durch die Verbindung der Formel
Eine Suspension von 36 Teilen Natrium in 200 Teilen Toluol wird bei 0°C mit einer Lösung von 30 Teilen 8,9-Dithia-bicyclo[4.3.0]-Δ1,6-nonen-7-thion der Formel (A) und 12 Teilen CS2 in 220 Teilen Toluol versetzt. Man lässt das Gemisch 3 Stunden bei 20°C stehen. Danach werden 220 Teile Wasser zugegeben. Die wässrige Phase wird abgetrennt und unter Ausschluss von Luftsauerstoff mit 180 Teilen 10%iger Schwefelsäure angesäuert. Der Niederschlag wird abgesaugt, mit eiskaltem Wasser, wenig eiskaltem Methanol und Cyclohexan gewaschen und im Dunkeln unter Hochvakuum getrocknet. Man erhält 31,5 Teile des granatroten Produktes der Formel (C), welches mit Dimethylsulfat in 67%iger Ausbeute ins bismethylierte Derivat (D) (Smp. 148°C) überführt werden kann:
5 Teile des Produktes (C) aus Beispiel 6 werden in 39 Teilen 1 n-Natronlauge gelöst und mit 3 Teilen 2-Chlor-ethanol bei Raumtemperatur versetzt. Nach einigen Minuten fällt das Produkt unter Wärmetönung aus. Das Reaktionsgemisch wird 2 Stunden weitergerührt, dann abgesaugt und mit Wasser gewaschen. Das feuchte Rohprodukt wird 30 Minuten mit 150 Teilen Methanol zum Rückfluss erhitzt, dann kalt abgesaugt. Man erhält 6 Teile eines rotorangen Produktes der Formel (E)
Das Produkt des Beispieles 7 wird in Toluol mit 2-Ethyl-hexanoyl-chlorid und Triethylamin nach üblichen Verfahren verestert. Man erhält ein dunkelrotes Oel der Formel (F):
Mit der Methode gemäss Beispiel 7 wird unter Beibehaltung der Stöchiometrie Chlorethanol durch 1-(2-Chlor-ethyl-)pyrrolidin ersetzt. Man erhält das Produkt der Formel (G)
Mit der Methode gemäss Beispiel 7 wird unter Beibehaltung der Stöchiometrie Chlorethanol durch 2-Chlorethyl-ethylether ersetzt. Man erhält das rote Produkt der Formel (H)
Mit dem Shell-Vierkugel-Apparat (IP 239/73) Extreme pressure and wear lubricant test for oils and greases four ballmachine, ASTM D 2783-81) werden folgende Werte bestimmt:
- 1. W.L. = Weld load (Schweisslast). Das ist die Last, bei der die-4 Kugeln innerhalb von 10 Sekunden zusammenschweissen.
- 2. W.S.D. = Wear Scar Diameter in mm: Das ist der mittlere Verschleissdurchmesser bei einer Belastung von 40 kg während 10 bzw. 30 Minuten.
- 1. WL = Weld load. This is the load that the 4 balls weld together within 10 seconds.
- 2. WSD = Wear Scar Diameter in mm: This is the average wear diameter with a load of 40 kg for 10 or 30 minutes.
Als Testflüssigkeit für die Wirksamkeit der Additive wird ein Basisöl der Firma Shell (Catenex P 941®) und Wasser, das 0,5 Gew.-% Kalilauge, 1,5 Gew.-% Triethanolamin und 0,75 Gew.-% Korrosions-inhibitor (Reocor 184®, Ciba-Geigy) enthält, verwendet. Der pH-Wert dieser Lösung mitsamt dem Additiv beträgt 8,5. Die Ergebnisse sind in Tabelle 2 angegeben. Zusätzlich ist die Bewertung der Kupferkorrosion gemäss ASTM D-130 angegeben.
Mit der Reibverschleisswaage nach Reichert (Reichert Wear Test DBGM 1749247) wird die Verschleisskalotte bestimmt (Kadmer et al., Mineralöltechnik 1958(2), 1-17).With the friction wear scales according to Reichert (Reichert Wear Test DBGM 1749247) the Ver wear cap determined (Kadmer et al., Mineralöltechnik 1958 (2), 1-17).
Bei diesem Reibungsprüfgerät wird über ein Doppelhebelsystem eine fest eingespannte Prüfrolle an einen umlaufenden Schleifring angepresst, der mit seinem unteren. Drittel in die zu prüfende Flüssigkeit taucht, deren Druckaufnahmevermögen beurteilt werden soll. Bei unlaufendem Schleifring entstehen je nach Druckaufnahmevermögen der Flussigkeit auf die Prüfrolle Abschliffflächen (Verschleisskalotten), deren Grösse von der Tragfähigkeit des Prüfstoffes abhängt.In this friction tester, a firmly clamped test roller is pressed onto a rotating slip ring with a lower lever system. Dip a third in the liquid to be tested, the pressure absorption capacity of which is to be assessed. When the slip ring is not running, depending on the pressure absorption capacity of the liquid on the test roller, there are abraded surfaces (wear spheres), the size of which depends on the load-bearing capacity of the test substance.
Prüfbedingungen des Gerätes:
Als Testflüssigkeit für die Wirksamkeit der Additive wird Wasser, welches 0,75 Gew.-% Korrosionsinhibitor (Reocor 184@), 0,5 Gew.-% Kalilauge, 1,5 Gew.-% Triethanolamin und 2,5 Gew.-% Additiv (pH 8,5) enthält, verwendet. Das Ergebnis ist in Tabelle 3 angegeben.Water, which contains 0.75% by weight of corrosion inhibitor (Reocor 184 @), 0.5% by weight of potassium hydroxide solution, 1.5% by weight of triethanolamine and 2.5% by weight, is used as the test liquid for the effectiveness of the additives. Contains additive (pH 8.5). The result is shown in Table 3.
Vor und nach dem eigentlichen Messlauf werden Kontrollmessungen mit einer Mischung aus 50 Gew.- % Wasser und 50 Gew.-% Ethanol durchgeführt, wobei Verschleisswerte um 40 mm2 beobachtet werden.
Mit dem Nocken-Stösselgerät wird nach "Tribologie und Schmierungstechnik" 31/3, S. 164 (1984) das Schadlastverhalten untersucht. In Abänderung dieser Beschreibung wird je eine Stunde bei 1000 N, 1100 N, 1200 N usw. bis höchstens 2000 N oder bis zum Auftreten von nennenswertem Verschleiss gemessen. Messgrösse ist die Schadenlast.With the cam follower device, the load behavior is examined according to "Tribology and Lubrication Technology" 31/3, p. 164 (1984). In a modification of this description, one hour at 1000 N, 1100 N, 1200 N etc. up to a maximum of 2000 N or until significant wear occurs. The measure is the damage burden.
Als Testflüssigkeit für die Wirksamkeit der Additive wird ein Oel der Spezifikation SAE 10W-30 verwendet. Es besteht aus einer Meschung aus 72,8 Gew.-% Mineralöl (ISO VG 32), 11,2 Gew.-% XOA 938@ (Orogil) und 6 Gew.-% Viscoplex 610@ (Roehm). Die Ergebnisse sind in nachfolgender Tabelle 4 zusammengefasst.
Mit Hilfe der Methode, welche von C.S. Ku und S.M. Hsu in Lubrication Engineering Vol. 40(2), 75-83 [1984] beschrieben wird (Thin-film Oxygen Uptake Test, "TFOUT")i, wird bestimmt, wie lange ein Additiv in der Lage ist, Schmiermittel vor einem durch Metallionen katalysierten oxydativem Abbau zu bewahren. Die angegebenen Werte sind Mittelwerte zweier unabhängigen Testläufe. Als Testflüssigkeit wird ein typisches Motorenöl (Zusammensetzung: Mineralöl 82,05 % (ISO-VG32); Detergent/Dispersant 11,2 %; VI-improver 6,0 %; ZnDDP 0,75 %) verwendet, welches aber lediglich die Hälfte des üblicherweise zugesetzten Zinkdialkyldithiophosphates enthält. Die Resultate sind in der Tabelle 5 enthalten.With the help of the method developed by C.S. Ku and S.M. Hsu in Lubrication Engineering Vol. 40 (2), 75-83 [1984] (Thin-film Oxygen Uptake Test, "TFOUT") i, it is determined how long an additive is able to protect lubricants from metal ions to preserve catalyzed oxidative degradation. The values given are mean values of two independent test runs. A typical motor oil (composition: mineral oil 82.05% (ISO-VG32); detergent / dispersant 11.2%; VI improver 6.0%; ZnDDP 0.75%) is used as the test liquid, but this is only half of the usually contains added zinc dialkyldithiophosphates. The results are shown in Table 5.
Claims (19)
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CH4521/86 | 1986-11-12 | ||
CH452186 | 1986-11-12 |
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EP0271437B1 true EP0271437B1 (en) | 1990-10-03 |
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EP87810639A Expired - Lifetime EP0271437B1 (en) | 1986-11-12 | 1987-11-06 | Sulphurized lubricant additives |
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US (1) | US4822506A (en) |
EP (1) | EP0271437B1 (en) |
JP (1) | JPS63135494A (en) |
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US5344577A (en) * | 1992-05-14 | 1994-09-06 | The United States Of America As Represented By The Secretary Of Commerce | Methods for reducing wear on silicon carbide ceramic surfaces |
US7787572B2 (en) * | 2005-04-07 | 2010-08-31 | Rambus Inc. | Advanced signal processors for interference cancellation in baseband receivers |
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GB1575202A (en) * | 1977-01-28 | 1980-09-17 | Exxon Research Engineering Co | Azathiapentalenes and their use as lubricating oil additives |
US4116812A (en) * | 1977-07-05 | 1978-09-26 | Petrolite Corporation | Organo-sulfur compounds as high temperature antifoulants |
-
1987
- 1987-11-04 US US07/116,931 patent/US4822506A/en not_active Expired - Fee Related
- 1987-11-06 DE DE8787810639T patent/DE3765399D1/en not_active Expired - Lifetime
- 1987-11-06 EP EP87810639A patent/EP0271437B1/en not_active Expired - Lifetime
- 1987-11-12 JP JP62286436A patent/JPS63135494A/en active Pending
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US4822506A (en) | 1989-04-18 |
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EP0271437A1 (en) | 1988-06-15 |
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