EP0072349A2 - Tetrahydrochinoline als Antioxidantien für Schmiermittel - Google Patents
Tetrahydrochinoline als Antioxidantien für Schmiermittel Download PDFInfo
- Publication number
- EP0072349A2 EP0072349A2 EP82810325A EP82810325A EP0072349A2 EP 0072349 A2 EP0072349 A2 EP 0072349A2 EP 82810325 A EP82810325 A EP 82810325A EP 82810325 A EP82810325 A EP 82810325A EP 0072349 A2 EP0072349 A2 EP 0072349A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- hydrogen
- butyl
- tert
- tetrahydroquinoline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 0 *C1*CCC1 Chemical compound *C1*CCC1 0.000 description 1
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- 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
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- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
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- C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
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- C10M2215/22—Heterocyclic nitrogen compounds
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- C10M2215/222—Triazines
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- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
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- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
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- C10M2215/28—Amides; Imides
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- C10M2215/30—Heterocyclic compounds
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/084—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
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- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/088—Neutral salts
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- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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- C10M2219/089—Overbased salts
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- 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
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- 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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- 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
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- 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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- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Definitions
- the present invention relates to lubricants stabilized with the help of quinolines.
- additives are generally added to mineral and synthetic lubricating oils, hydraulic liquids and greases to improve their performance properties.
- 1,2-dihydroquinolines are e.g. known from US-PS 3,910,918. According to this patent, these compounds can be polymerized in order to obtain highly active antioxidants for polymer plastics. From JP-OS 55-026.257 it is known to use such polymeric additives in combination with phenolic antioxidants as lubricant additives. However, these compounds and mixtures do not meet the high demands placed on a lubricant additive in every respect.
- US Pat. No. 2,030,033 describes hydroxy-substituted tetrahydroquinolines as fuel additives.
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as C 1 -C 18 alkyl, for example methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, t. -Butyl, amyl, n-hexyl, or branched or straight-chain octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl or octadecyl.
- R 1 preferably has 1-12 C atoms as alkyl.
- R 2 , R 3 , R 4 and R 6 as alkyl are preferably C 1 -C 12 alkyl, particularly preferably C 1 -C 6 alkyl and in particular methyl or ethyl.
- R ' 2 as C 1 -C 12 alkyl has the same exemplary meanings given above for R 1 -R 6 within its limits.
- R ' 2 is preferred as alkyl, methyl or ethyl.
- R 1 , R 2 , R ' 2 and R 5 is hydrogen.
- R 1 and R 2 are C 1 -C 18 alkoxy, for example methoxy, ethoxy, isopropyloxy, n-propyloxy, n-butyloxy, sec-butyloxy, t-butyloxy, straight-chain or branched hexyloxy, Octyloxy, decyloxy, dodecyloxy or octadecyloxy. Methoxy and ethoxy are preferred.
- R 1 and R 2 are as C 3 -C 4 alkenyloxy, for example 1-propenyloxy or 1-butenyloxy.
- R 3 and R 4 together with the carbon atom to which they are attached form C 5 -C 12 cycloalkyl, it is, for example, cyclooctyl, cyclodecyl or cyclododecyl, preferably cyclopentyl or cycloheptyl and in particular cyclohexyl.
- R 5 and R 6 together with the two carbon atoms to which they are attached form a C 5 -C 12 cycloaliphatic ring, they can have the meaning given above for R 3 and R 4 as examples of cycloalkyl.
- R 5 and R 6 together with the two carbon atoms to which they are attached form a C 5 -C 12 cycloaromatic ring, they can in particular result in a benzene or cyclooctatetraene ring.
- Preferred compounds of the formula I are those in which R 1 and R 2 independently of one another denote hydrogen, hydroxy, methoxy, ethoxy or C 1 -C 12 alkyl, and R ' 2 is hydrogen or together with R 2 forms a butadiene diyl radical, and R 3 and R 4 are independently C 1 -C 12 alkyl or R 3 and R 4 together with the carbon atom to which they are attached form a C 5 -C 7 spiro-cycloalkyl ring, and R S is hydrogen and R 6 is C 1 -C 12 alkyl, or R 5 and R 6 together with the two carbon atoms to which they are attached form a cyclohexane radical.
- R 1 is hydrogen, methoxy, ethoxy or C 1 -C 12 alkyl
- R 2 is hydrogen, methoxy, ethoxy, methyl or ethyl
- R ' 2 is hydrogen or together with R 2 is one Forms butadiene diyl
- R 3 and R 4 are methyl or ethyl or R 3 and R 4 together with the carbon atom to which they are attached form a spiro-cyclohexyl ring
- R 5 is hydrogen and R 6 is methyl or ethyl.
- the quinolines to be used according to the invention are used in combination with sterically hindered phenolic antioxidants.
- Ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) -3- (n-dodecylthio ) butane or 4,4'-thiobis- (6-tert.butyl-3-methylphenol).
- Hydroxybenzyl aromatics such as e.g.
- monohydric or polyhydric alcohols e.g. with methanol, octadecanol, 1,6-hexanediol, ethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol, tris-hydroxyethyl isocyanurate.
- diphenolic spiro - diacetals or -diketale such as in 3-, 9- position with phenolic radicals substituted 2,4,8,10-tetra-oxaspiro- [5.5] undecane such as 3,9-bis ( 3,5-di-tert-butyl-4-hydroxyphenyl) -2,4,8,10-tetraoxaspiro- [5,5] -undecane, 3,9-bis- [1,1-dimethyl-2- (3rd , 5-ditert.butyl-4-hydroxyphenyl) ethyl] -2,4,8,10-tetraoxaspiro- [5,5) -undecane.
- the preparation of the compounds of formula I is e.g. known from US-PS 3,910,918. If there are also new compounds underneath, these also constitute an object of the invention and can be produced analogously.
- the phenolic antioxidants which are optionally to be used are likewise known compounds and can be prepared by known processes.
- the quinolines of the formula I can be used in concentrations of 0.05-10% by weight, based on the material to be stabilized. Preferred concentrations are 0.05-5% by weight, and in particular 0.1-2.5% by weight.
- phenolic antioxidants are used, these are used in concentrations of 0.05-5% by weight, based on the material to be stabilized.
- the preferred concentration range is 0.1-2% by weight.
- the ratio of the compounds of the formula I to be used according to the invention to phenolic antioxidants is 10: 1 to 1:10, preferably 1: 5 to 5: 1 and in particular 1: 3 to 3: 1.
- lubricants in question are familiar to the person skilled in the art and e.g. described in the "Lubricant Paperback (Hüthig Verlag, Heidelberg, 1974)".
- Poly-a-olefins, ester-based lubricants, phosphates, glycols, polyglycols and polyalkylene glycols are familiar to the person skilled in the art and e.g. described in the "Lubricant Paperback (Hüthig Verlag, Heidelberg, 1974)".
- Poly-a-olefins, ester-based lubricants, phosphates, glycols, polyglycols and polyalkylene glycols are examples of the lubricants.
- the lubricant formulations can additionally contain other additives which are added in order to improve certain usage properties, such as further antioxidants, metal passivators, rust inhibitors, viscosity index improvers, pour point depressants, dispersants / surfactants and wear protection additives.
- additives such as further antioxidants, metal passivators, rust inhibitors, viscosity index improvers, pour point depressants, dispersants / surfactants and wear protection additives.
- antioxidants examples are:
- metal passivators examples are:
- rust inhibitors are:
- viscosity index improvers examples include:
- Polymethacrylates vinyl pyrrolidone / methacrylate copolymers, polybutenes, olefin copolymers, styrene / acrylate copolymers.
- pour point lower examples are e.g.
- dispersants / surfactants examples include:
- Polybutenylsuccinic acid imides polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sulfonates and phenolates.
- wear protection additives examples include:
- Compounds containing sulfur and / or phosphorus and / or halogen such as sulfurized vegetable oils, zinc dialkyldithiophosphates, tritolyl phosphate, chlorinated paraffins, alkyl and aryl disulfides.
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Abstract
Description
- Die vorliegende Erfindung betrifft mit Hilfe von Chinolinen stabilisierte Schmiermittel.
- Mineralischen und synthetischen Schmierölen, hydraulischen Flüssigkeiten und Schmierfetten werden im allgemeinen verschiedene Zusatzstoffe zur Verbesserung ihrer Gebrauchseigenschaften beigegeben. Insbesondere besteht ein Bedarf an Additiven, welche die Oxidation bzw. Alterung des Schmierstoffs wirksam inhibieren und somit die Lebensdauer des Schmierstoffs beträchtlich erhöhen.
- 1,2-Dihydrochinoline sind z.B. aus der US-PS 3.910.918 bekannt. Gemäss dieser Patentschrift können diese Verbindungen polymerisiert werden, um hochaktive Antioxidantien für polymere Kunststoffe zu erhalten. Aus der JP-OS 55-026.257 ist bekannt, solche polymere Additive in Kombination mit phenolischen Antioxidantien als Schmiermittelzusätze zu verwenden. Diese Verbindungen und Gemische entsprechen jedoch nicht in jeder Hinsicht den hohen Anforderungen, welche an ein Schmiermittel-Additiv gestellt werden. Ausserdem sind in der US-PS 2,030,033 Hydroxysubstituierte Tetrahydrochinoline als Treibstoffzusätze beschrieben.
- Es wurde nun gefunden, dass monomere 1,2,3,4-Tetrahydrochinoline allein und insbesondere in Kombination mit phenolischen Antioxidantien in Schmiermitteln bei befriedigendem Korrosionsverhalten eine ausgezeichnete Antioxidationswirkung entfalten.
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- R1 und R2 unabhängig voneinander Wasserstoff, Hydroxy, C1-C18 Alkoxy, C3-C4 Alkenyloxy, Benzyloxy, C1-C18 Alkyl oder Benzyl bedeuten, und
- R'2 Wasserstoff oder C1-C12 Alkyl bedeutet oder zusammen mit R2 einen Butadiendiyl-Rest bildet, und
- R3 und R4 unabhängig voneinander C1-C18 Alkyl, Phenyl oder Benzyl sind, oder R3 und R4 zusammen mit dem Kohlenstoffatom, an welches sie gebunden sind, einen C5-C12 Spiro-Cycloalkylring bilden, und
- R5 Wasserstoff oder C1-C18 Alkyl und
- R6C1-C18 Alkyl ist, oder
- R5 und R6 zusammen mit den beiden Kohlenstoffatomen, an die sie gebunden sind, einen C5-C12 cycloaliphatischen Rest bedeuten.
- R1, R2, R3, R4, R5 und R6 sind als C1-C18- Alkyl z.B. Methyl, Ethyl, iso-Propyl, n-Propyl, n-Butyl, sec.-Butyl, t.-Butyl, Amyl, n-Hexyl, oder verzweigtes oder geradkettiges Octyl, Nonyl, Decyl, Undecyl, Dodecyl, Tetradecyl, Hexadecyl oder Octadecyl. R1 besitzt als Alkyl bevorzugt 1-12 C-Atome. R2, R3, R4 und R6 sind als Alkyl bevorzugt C1-C12 Alkyl besonders bevorzugt C1-C6 Alkyl und insbesondere Methyl oder Ethyl.
- R'2 als C1-C12 Alkyl besitzt in seinen Grenzen die gleichen oben für R1-R6 angegebenen beispielhaften Bedeutungen. Bevorzugt ist R'2 als Alkyl, Methyl oder Ethyl.
- Eine weitere Bevorzugung in den Bedeutungen von R1, R2, R'2 und R5 ist Wasserstoff.
- Sind R1 und R2 C1-C18 Alkoxy, so handelt es sich beispielsweise um Methoxy, Ethoxy, iso-Propyloxy, n-Propyloxy, n-Butyloxy, sec.-Butyloxy, t.-Butyloxy, geradkettiges oder verzweigtes Hexyloxy, Octyloxy, Decyloxy, Dodecyloxy oder Octadecyloxy. Bevorzugt sind Methoxy und Ethoxy.
- R 1 und R2 sind als C3-C4 Alkenyloxy z.B. 1-Propenyloxy oder 1-Butenyloxy.
- Bilden R3 und R4 zusammen mit dem Kohlenstoffatom, an welches sie gebunden sind C5-C12 Cycloalkyl, so handelt es sich beispielsweise um Cyclooctyl, Cyclodecyl oder Cyclododecyl, bevorzugt Cyclopentyl oder Cycloheptyl und insbesondere Cyclohexyl.
- Bilden R5 und R6 zusammen mit den beiden Kohlenstoffatomen, an welche sie gebunden sind, einen C5-C12 cycloaliphatischen Ring, so können sie die oben für R3 und R4 beispielhaft für Cycloalkyl angegebene Bedeutung haben.
- Bilden R5 und R6 zusammen mit den beiden Kohlenstoffatomen, an welche sie gebunden sind, einen C5-C12 cycloaromatischen Ring, so können sie insbesondere einen Benzol- oder Cyclooctatetraen-Ring ergeben.
- Bevorzugt werden Verbindungen der Formel I, worin R1 und R2 unabhängig voneinander Wasserstoff, Hydroxy, Methoxy, Ethoxy oder C1-C12 Alkyl bedeuten, und R'2 Wasserstoff ist oder zusammen mit R2 einen Butadiendiyl-Rest bildet, und R3 und R4 unabhängig voneinander C1-C12 Alkyl sind oder R3 und R4 zusammen mit dem Kohlenstoffatom, an welches sie gebunden sind, einen C5-C7 Spiro-Cycloalkylring bilden, und RS Wasserstoff und R6 C1-C12 Alkyl ist, oder R5 und R6 zusammen mit den beiden Kohlenstoffatomen, an die sie gebunden sind, einen Cyclohexanrest bilden.
- Von besonderer Bedeutung sind Verbindungen der Formel I, worin R1 Wasserstoff, Methoxy, Ethoxy oder C1-C12 Alkyl ist, R2 Wasserstoff, Methoxy, Ethoxy, Methyl oder Ethyl ist, R'2 Wasserstoff ist oder zusammen mit R2 einen Butadiendiyl-Rest bildet und R3 und R4 Methyl oder Ethyl sind oder R3 und R4 zusammen mit dem Kohlenstoffatom, an welches sie gebunden sind, einen Spiro-Cyclohexylring bilden und R5 Wasserstoff und R6 Methyl oder Ethyl ist.
- Beispiele für Verbindungen der Formel I sind:
- 1) 2,2,4-Trimethyl-1,2,3,4-tetrahydrochinolin
- 2) 2,2,4-Trimethyl-6-n-dodecyl-1,2,3,4-tetrahydrochinolin
- 3) 2-Methyl-2,4-diethyl-1,2,3,4-tetrahydrochinolin
- 4) 2,2,4,7-Tetramethyl-1,2,3,4-dihydrochinolin
- 5) 2,2,4,8-Tetramethyl-l,2,3,4-tetrahydrochinolin
- 6) 2,2,4,6-Tetramethyl-1,2,3,4-tetrahydrochinolin
- 7) 2,2,4,6,8-Pentamethyl-1,2,3,4-tetrahydrochinolin
- 8) 2,2,4-Trimethyl-8-methoxy-1,2,3,4-tetrahydrochinolin
- 9) 2,2,4-Trimethyl-8-methoxy-1,2,3,4-tetrahydrochinolin
- 10) 2-Methyl-2,4-diethyl-6-methoxy-1,2,3,4-tetrahydrochinolin
- In einer bevorzugten Ausführungsform der Erfindung werden die erfindungsgemäss zu verwendenden Chinoline in Kombination mit sterisch gehinderten phenolischen Antioxidantien eingesetzt.
- Als phenolische Antioxidantien eignen sich insbesondere
- 1. Einfache 2,6-Dialkylphenole, wie z.B. 2,6-Di-tert.butyl-4-methylphenol, 2,6-Di-tert.butyl-4-methoxy- methylphenol oder 2,6-Di-tert.butyl-4-methoxyphenol.
- 2. Bisphenole, wie z.B. 2,2'-Methylenbis-(6-tert.butyl-4-methylphenol), 2,2'-Methylen-bis-(6-tert.butyl-4-äthylphenol), 2,2'-Methylenbis-[4-methyl-6-(a-methylcyclohexyl)-phenol], 1,1-Bis-(5-tert.butyl-4-hydroxy-2-methylphenyl)-butan, 2,2-Bis-(5-tert.butyl-4-hydroxy-2-methylphenyl)-butan, 2,2-Bis-(3,5-di-tert.butyl-4-hydroxyphenyl)-propan, 1,1,3-Tris-(5-tert.butyl-4-hydroxy-2-methylphenyl)-butan, 2,2-Bis-(5-tert.butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercapto-butan, 1,1,5,5-Tetra-(5-tert.butyl-4-hydroxy-2-methylphenyl)-pentan,
- Aethylenglykolbis-[3,3-bis-(3'-tert.butyl-4'-hydroxyphenyl)-butyrat], 1,1-Bis-(3,5-dimethyl-2-hydroxyphenyl)-3-(n-dodecylthio)-butan oder 4,4'-Thiobis-(6-tert.butyl-3-methylphenol).
- 1,3,5-Tri-(3,5-di-tert.butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzol; 2,2-Bis-(3,5-di-tert.butyl-4-hydroxybenzyl)-malonsäure-di- octadecylester; 1,3,5-Tris-(3,5-di-tert.butyl-4-hydroxybenzyl)-isocyanurat oder 3,5-Di-tert,butyl-4-hydroxybenzyl-phosphonsäure- diäthylester.
- 1,3,5-Tris-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionyl)-hexahydro- s-triazin, N,N'-Di-(3,5-di-tert.butyl-4-hydroxyphenyl-propionyl)-hexamethylendiamin.
- ein- oder mehrwertigen Alkoholen, wie z.B. mit Methanol, Octadecanol, 1,6-Hexandiol, Aethylenglykol, Thiodiäthylenglykol, Neopentylglykol, Pentaerythrit, Tris-hydroxyäthyl-isocyanurat.
- diphenolische Spiro-diacetale oder -diketale, wie z.B. in 3-, 9-Stellung mit phenolischen Resten substituiertes 2,4,8,10-Tetra- oxaspiro-[5,5]-undecan, wie z.B. 3,9-Bis-(3,5-di-tert.butyl-4-hydroxyphenyl)-2,4,8,10-tetraoxaspiro-[5,5]-undecan, 3,9-Bis-[1,1-dimethyl-2-(3,5-ditert.butyl-4-hydroxyphenyl)-äthyl]-2,4,8,10-tetraoxaspiro-[5,5)-undecan.
- Besonders bevorzugte phenolische Verbindungen sind
- 4,4'-Bis-(2,6-diisopropylphenol)
- 2,4,6 -Triisopropylphenol
- 2,2'-Thio-bis-(4-methyl-6-tert.butyl-phenol)
- 4,4'-Methylen-bis-(2,6-di-tert.butyl-phenol)
- 1,3,5-Tri-(3,5-di-tert.butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzol Pentaerythrit-tetra-[3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionat] β-(3,5-Di-tert.butyl-4-hydroxyphenyl)-propionsäure-n-octadecylester Thiodiäthylenglykol-β-[4-hydroxy-3,5-di-tert.butyl-phenyl]-propionat 2,6-Di-tert.butyl-4-methyl-phenol.
- Die Herstellung der Verbindungen der Formel I ist z.B. aus der US-PS 3.910.918 bekannt. Sollten sich darunter auch neue Verbindungen befinden, so stellen diese auch einen Gegenstand der Erfindung dar und können analog hergestellt werden. Die gegebenenfalls mitzuverwendenden phenolischen Antioxidantien sind ebenfalls bekannte Verbindungen und können gemäss bekannter Verfahren hergestellt werden.
- Die Chinoline der Formel I können in Konzentrationen von 0,05-10 Gewichts-%, bezogen auf das zu stabilisierende Material, eingesetzt werden. Bevorzugte Konzentrationen sind 0,05-5 Gewichts-%, und insbesondere 0,1-2,5 Gewichts-%.
- Werden gemäss einer bevorzugten Ausführungsform der vorliegenden Erfindung phenolische Antioxidantien mit verwendet, so werden diese in Konzentrationen von 0,05-5 Gewichts-%, bezogen auf das zu stabilisierende Material, eingesetzt. Bevorzugter Konzentrationsbereich ist 0,1-2 Gewichts-%.
- Das Verhältnis der erfindungsgemäss zu verwendenden Verbindungen der Formel I zu phenolischen Antioxidantien beträgt 10:1 bis 1:10, bevorzugt 1:5 bis 5:1 und insbesondere 1:3 bis 3:1.
- Auf diese Weise ausgerüstete mineralische und synthetische Schmieröle, hydraulische Flüssigkeiten und Schmierfette zeigen ausgezeichnete Schmiereigenschaften, welche durch stark reduzierte Abnutzungserscheinungen der zu schmierenden Teile deutlich werden.
- Die in Frage kommenden Schmiermittel sind dem Fachmann geläufig und z.B. im "Schmiermittel-Taschenbuch (Hüthig Verlag, Heidelberg, 1974)" beschrieben. Besonders geeignet sind z.B. Poly-a-Olefine, Schmiermittel auf Esterbasis, Phosphate, Glykole, Polyglykole und Polyalkylenglykole.
- Die Schmiermittelformulierungen können zusätzlich noch andere Additive enthalten, die zugegeben werden, um gewisse Gebrauchs-Eigenschaften zu verbessern, wie weitere Antioxidantien, Metallpassivatoren, Rost-inhibitoren, Viskositätsindex-Verbesserer, Stockpunkterniedriger, Dispergiermittel/Tenside und Verschleissschutz-Additive.
-
- a) Alkylierte und nicht-alkylierte aromatische Amine und Mischungen davon, z.B.:
- Dioctyldiphenylamin, (2,2,3,3-Tetramethyl-butyl)-phenyl-a- und -ß-naphthylamine, Phenotriazin, Dioctylphenothiazin, Phenyl-a-naphthylamin, N,N'-Di-sec.butyl-p-phenylendiamin.
- b) Alkyl-, Aryl- oder Alkaryl-phosphite, z.B.:
- Trinonylphosphit, Triphenylphosphit, Diphenyldecylphosphit oder Tris-(2,4-Di-tert.butylphenyl)-phosphit.
- c) Ester von Thiodipropionsäure oder Thiodiessigsäure, z.B.:
- Dilaurylthiodipropionat oder Dioctylthiodiacetat.
- d) Salze von Carbamin- und Dithiophosphor-säuren, z.B.:
- Antimon-diamyldithiocarbamat, Zink-diamyldithiophosphat.
-
- a) für Kupfer, z.B.:
- Benzotriazol, Tetrahydrobenzotriazol, 2-Mercaptobenzotriazol, 2,5-Dimercaptothiadiazol, Salicyliden-propylendiamin, Salze von Salicylaminoguanidin.
- b) für Blei, z.B.:
- Sebacinsäurederivate, Chinizarin, Propylgallat.
-
- a) Organische Säuren, Ihre Ester, Metallsalze und Anhydride, z.B.:
- N-Oleoyl-sarcosin, Sorbitan-mono-oleat, Blei-naphthenat, Dodecenylbernsteinsäure-anhydrid.
- b) Stickstoffhaltige Verbindungen, z.B.:
- T. Primäre, sekundäre oder tertiäre aliphatische oder cycloaliphatische Amine und Amin-Salze von organischen und anorganischen Säuren, z.B. öllösliche Alkylammoniumcarboxylate.
- II. Heterocyclische Verbindungen, z.B.:
- Substituierte Imidazoline und Oxazoline.
- c) Phosphorhaltige Verbindungen, z.B.:
- Aminsalze von Phosphorsäurepartialestern.
- d) Schwefelhaltige Verbindungen, z.B.:
- Barium-dinonylnaphthalin-sulfonate, Calciumpetroleum-sulfonate.
- Polymethacrylate, Vinylpyrrolidon/Methacrylat-Copolymere, Polybutene, Olefin-Copolymere, Styrol/Acrylat-Copolymere.
- Polymethacrylat, alkylierte Naphthalinderivate.
- Polybutenylbernsteinsäure-imide, Polybutenylphosphonsäurederivate, basische Magnesium-, Calcium-, und Bariumsulfonate und -phenolate.
- Schwefel und/oder Phosphor und/oder Halogen enthaltende Verbindungen, wie geschwefelte pflanzliche Oele, Zinkdialkyldithiophosphate, Tritolyl-phosphat, chlorierte Paraffine, Alkyl- und Aryldisulfide.
- Folgende der oben erwähnten Chinoline wurden gemäss ASTM D 2272 in Mineralöl Vitrea 100 (ODX) Shell (Viskosität 10,6 mm2/s (100°C) gestestet. Der Versuch ist bei einem Druckabfall von 172,4 KPa (25 psi) beendet. Die in der untenstehenden Tabelle angegebenen Resultate bedeuten die Zeit in Minuten bis der angegebene Druckabfall eingetreten ist. Lange Zeiten entsprechen guter Stabilisatorwirksamkeit.
Claims (15)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH5130/81 | 1981-08-10 | ||
CH513081 | 1981-08-10 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0072349A2 true EP0072349A2 (de) | 1983-02-16 |
EP0072349A3 EP0072349A3 (en) | 1984-07-25 |
EP0072349B1 EP0072349B1 (de) | 1987-05-13 |
Family
ID=4288438
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82810325A Expired EP0072349B1 (de) | 1981-08-10 | 1982-08-04 | Tetrahydrochinoline als Antioxidantien für Schmiermittel |
Country Status (5)
Country | Link |
---|---|
US (1) | US4692258A (de) |
EP (1) | EP0072349B1 (de) |
JP (1) | JPS5837092A (de) |
CA (1) | CA1199623A (de) |
DE (1) | DE3276326D1 (de) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0273868A2 (de) | 1986-12-30 | 1988-07-06 | Ciba-Geigy Ag | N-substituierte Tetrahydrochinoline als Antioxidantien für Schmiermittel |
EP0356677A1 (de) * | 1988-07-18 | 1990-03-07 | Ciba-Geigy Ag | Schmierstoffzusammensetzung |
EP0463996A2 (de) * | 1990-06-29 | 1992-01-02 | Ciba-Geigy Ag | Azofarbstoffe, Verfahren zu deren Herstellung und deren Verwendung |
EP0466639A1 (de) * | 1990-06-28 | 1992-01-15 | Ciba-Geigy Ag | Schmierstoffzusammensetzung |
EP0480875A1 (de) * | 1990-10-08 | 1992-04-15 | Ciba-Geigy Ag | Schmierstoffzusammensetzung |
US10414697B2 (en) | 2015-02-25 | 2019-09-17 | Pb Clermont | Tocopherol stabilisers for nitrocellulose-based propellants |
Families Citing this family (21)
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US4919832A (en) * | 1986-12-30 | 1990-04-24 | Ciba-Geigy Corporation | N-substituted tetrahydroquinolines for use as antioxidants in lubricants |
US5273669A (en) * | 1988-07-18 | 1993-12-28 | Ciba-Geigy Corporation | Lubricant composition |
GB2253411B (en) * | 1991-01-08 | 1994-12-07 | Ciba Geigy Ag | Lubricant compositions |
EP0497735A1 (de) * | 1991-01-31 | 1992-08-05 | Ciba-Geigy Ag | Hydrochinolinverbindungen |
JPH05125378A (ja) * | 1991-05-14 | 1993-05-21 | Dow Chem Co:The | 安定化ブレーキ液 |
JPH08143883A (ja) * | 1994-11-17 | 1996-06-04 | Dow Corning Asia Ltd | 耐熱性グリース組成物 |
CA2202790C (en) * | 1994-12-09 | 2004-02-24 | Raymond Frederick Watts | Synergistic antioxidant systems |
US6696459B1 (en) | 1994-12-22 | 2004-02-24 | Ligand Pharmaceuticals Inc. | Steroid receptor modulator compounds and methods |
US5688810A (en) * | 1994-12-22 | 1997-11-18 | Ligand Pharmaceuticals Incorporated | Steroid receptor modulator compounds and methods |
US6726855B1 (en) | 1998-12-02 | 2004-04-27 | Uniroyal Chemical Company, Inc. | Lubricant compositions comprising multiple antioxidants |
US6235686B1 (en) * | 2000-08-16 | 2001-05-22 | R.T. Vanderbilt Company, Inc. | Lubricating compositions containing aromatized 1,2-dihydro-2,2,4-trimethylquinoline polymers |
DE10356830A1 (de) * | 2003-12-05 | 2005-07-07 | Robert Bosch Gmbh | Fahrzeugscheibenantenne |
US8003583B2 (en) * | 2005-12-21 | 2011-08-23 | Chevron Oronite Company Llc | Benzo[b]perhydroheterocyclic arylamines and lubricating oil compositions |
US7501386B2 (en) * | 2005-12-21 | 2009-03-10 | Chevron Oronite Company, Llc | Synergistic lubricating oil composition containing a mixture of a benzo[b]perhydroheterocyclic arylamine and a diarylamine |
US7285518B2 (en) * | 2005-12-21 | 2007-10-23 | Chevron Oronite Company Llc | Dibenzo[b]perhydroheterocyclic amines and lubricating oil compositions |
US7928045B2 (en) * | 2006-02-28 | 2011-04-19 | Chemtura Corporation | Stabilizing compositions for lubricants |
US7683017B2 (en) * | 2007-06-20 | 2010-03-23 | Chevron Oronite Company Llc | Synergistic lubricating oil composition containing a mixture of a nitro-substituted diarylamine and a diarylamine |
JP2011057718A (ja) * | 2007-12-10 | 2011-03-24 | Adeka Corp | 酸化防止性能に優れた潤滑油組成物 |
AR070686A1 (es) * | 2008-01-16 | 2010-04-28 | Shell Int Research | Un metodo para preparar una composicion de lubricante |
JP5872300B2 (ja) * | 2012-01-18 | 2016-03-01 | 協同油脂株式会社 | グリース組成物及び軸受 |
CN115368957B (zh) * | 2019-08-14 | 2023-10-13 | 胜牌全球产品知识产权有限公司 | 含有无灰tbn分子的润滑剂组合物 |
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US1768910A (en) * | 1927-06-22 | 1930-07-01 | Harry K Ihrig | Oil-composition |
US2136788A (en) * | 1936-05-05 | 1938-11-15 | Sinclair Refining Co | Art of refining |
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NL263274A (de) * | 1959-04-22 | |||
US3121691A (en) * | 1960-05-24 | 1964-02-18 | Sinclair Research Inc | Lubricant composition |
JPS5526257A (en) * | 1978-08-14 | 1980-02-25 | Kao Corp | Lubricant treating agent composition for synthetic fiber |
-
1982
- 1982-08-04 EP EP82810325A patent/EP0072349B1/de not_active Expired
- 1982-08-04 DE DE8282810325T patent/DE3276326D1/de not_active Expired
- 1982-08-06 CA CA000408866A patent/CA1199623A/en not_active Expired
- 1982-08-10 JP JP57139087A patent/JPS5837092A/ja active Pending
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1985
- 1985-12-18 US US06/810,543 patent/US4692258A/en not_active Expired - Lifetime
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FR1000429A (fr) * | 1949-01-26 | 1952-02-12 | Standard Oil Dev Co | Antioxydant |
GB728728A (en) * | 1952-11-12 | 1955-04-27 | Us Rubber Co | Improvements in antioxidants |
US2846435A (en) * | 1953-07-27 | 1958-08-05 | Monsanto Chemicals | 6-ether substituted 1, 2, 3, 4-tetrahydroalkylquinolines |
US2881061A (en) * | 1956-03-12 | 1959-04-07 | Socony Mobil Oil Co Inc | Anti-knock gasoline containing hydrogenated quinolines and indoles |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0273868A2 (de) | 1986-12-30 | 1988-07-06 | Ciba-Geigy Ag | N-substituierte Tetrahydrochinoline als Antioxidantien für Schmiermittel |
EP0273868A3 (en) * | 1986-12-30 | 1990-05-02 | Ciba-Geigy Ag | N-substituted tetrahydroquinolines as antioxidants for lubricants |
EP0356677A1 (de) * | 1988-07-18 | 1990-03-07 | Ciba-Geigy Ag | Schmierstoffzusammensetzung |
AU621910B2 (en) * | 1988-07-18 | 1992-03-26 | Ciba Specialty Chemicals Holding Inc. | Lubricant composition |
EP0466639A1 (de) * | 1990-06-28 | 1992-01-15 | Ciba-Geigy Ag | Schmierstoffzusammensetzung |
EP0463996A2 (de) * | 1990-06-29 | 1992-01-02 | Ciba-Geigy Ag | Azofarbstoffe, Verfahren zu deren Herstellung und deren Verwendung |
EP0463996A3 (en) * | 1990-06-29 | 1992-03-11 | Ciba-Geigy Ag | Azodyes, process for their preparation and the use thereof |
EP0480875A1 (de) * | 1990-10-08 | 1992-04-15 | Ciba-Geigy Ag | Schmierstoffzusammensetzung |
US10414697B2 (en) | 2015-02-25 | 2019-09-17 | Pb Clermont | Tocopherol stabilisers for nitrocellulose-based propellants |
Also Published As
Publication number | Publication date |
---|---|
US4692258A (en) | 1987-09-08 |
EP0072349B1 (de) | 1987-05-13 |
JPS5837092A (ja) | 1983-03-04 |
CA1199623A (en) | 1986-01-21 |
DE3276326D1 (en) | 1987-06-19 |
EP0072349A3 (en) | 1984-07-25 |
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