EP0346283B1 - Composition lubrifiante - Google Patents

Composition lubrifiante Download PDF

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Publication number
EP0346283B1
EP0346283B1 EP89810410A EP89810410A EP0346283B1 EP 0346283 B1 EP0346283 B1 EP 0346283B1 EP 89810410 A EP89810410 A EP 89810410A EP 89810410 A EP89810410 A EP 89810410A EP 0346283 B1 EP0346283 B1 EP 0346283B1
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EP
European Patent Office
Prior art keywords
tert
alkyl
formula
carbon atoms
weight
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.)
Expired - Lifetime
Application number
EP89810410A
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German (de)
English (en)
Other versions
EP0346283A3 (en
EP0346283A2 (fr
Inventor
Samuel Dr. Evans
Rolf Dr. Schumacher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
Original Assignee
Ciba Geigy AG
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Publication of EP0346283A2 publication Critical patent/EP0346283A2/fr
Publication of EP0346283A3 publication Critical patent/EP0346283A3/de
Application granted granted Critical
Publication of EP0346283B1 publication Critical patent/EP0346283B1/fr
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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
    • C10M141/06—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 nitrogen-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/76—Esters containing free hydroxy or carboxyl groups
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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
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
    • C10M133/14—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
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    • C10M135/24—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
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    • C10M135/26—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
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    • C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives thereof
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    • C10M141/08—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 sulfur-, selenium- or tellurium-containing compound
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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
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    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/027—Neutral salts thereof
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    • C10M2219/088—Neutral salts
    • 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
    • C10M2219/08—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
    • C10M2219/089—Overbased salts
    • 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
    • C10N2040/25—Internal-combustion engines
    • 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
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol fueled engines
    • 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
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • 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
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines

Definitions

  • the invention relates to a phosphite-free lubricating oil composition with high stability against oxidative degradation.
  • thermo-oxidative requirement profile of modern engine oils has changed as a result of new engine designs in the field of internal combustion engines with spark ignition.
  • nitrogen oxides are increasingly formed, which in turn enter the crankcase as "blow-by" gases.
  • the lubricating oil in the upper piston ring and cylinder area takes over the fine sealing to the combustion chamber. This can lead to contamination with high-boiling fuel components. These conditions are exacerbated by the presence of NO x .
  • blow-by gases which have increasingly higher NO x contents, now cause the lubricating oil to be more susceptible to oxidation and "sludge germs" are formed, which ultimately lead to undesirable sludge deposits, which have become known as "black sludge”.
  • EP-A 0 149 422 describes an antioxidant based on diphenylamines.
  • additional additives such as hydroxylated thiophenyl ether, alkylidene bisphenols or thioesters of ⁇ - (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid can be used to further improve the basic properties.
  • antioxidant compositions for use with lubricants are known from WO 87/05320. Certain hydroxylated thiomethyl ethers are described which are used in a mixture with diphenylamines.
  • EP-A 0 049 133 describes a stabilizer composition which, inter alia, is also suitable for lubricating oils, known, containing diphenylamines, phosphites, thiodipropionic acid esters and optionally one or more polysubstituted phenols.
  • Phosphite as a constituent of a stabilizer, which is used in an engine lubricating oil, must be limited or preferably omitted in view of a possible deactivation of the catalyst by phosphorus compounds escaping with the exhaust gas.
  • New lubricant compositions and in particular lubricating oil compositions, have now been found which have further improved properties compared to the previously known products, are distinguished by high stability against oxidative degradation and in particular are able to sustainably reduce the negative effects of black sludge in spark ignition internal combustion engines.
  • R 1 has the meaning of H, alkyl having 1 to 18 C atoms, allyl, methallyl, benzyl or C 1 -C 11 alkyl-substituted benzyl,
  • composition according to the invention relates to phosphite-free lubricating oil compositions containing (a) a mineral oil or a synthetic oil or a mixture thereof and (b) a mixture as mentioned above.
  • the composition expediently relates to those of the type described above, in which the lubricating oil is an oil for spark-ignited internal combustion engines.
  • compositions represent motor oils for motor vehicles, and essentially for passenger car engines and commercial vehicle engines, which in the API classification (American Petroleum Institute) have the classification with the letters SF and CD or SG and CD, in the CRC classification (coordinating Research Council) the standardized "Caterpillar" test 1-G 1 or 1-G 2 and in the CCMC classification (Committee of Common Market Automobile Constructors) class 1 or 2.
  • API classification American Petroleum Institute
  • CRC classification coordinating Research Council
  • CCMC classification Common Market Automobile Constructors
  • compositions with the above-mentioned specifications can be derived analogously from the following description from the compounds of the formulas I and II designated as expedient or preferred.
  • the compounds in the mixture are expediently in a mixing ratio of 4 to 5 parts by weight, preferably 4.5 parts by weight, of the aromatic amine (s) of the formula to 1 part by weight the or the phenols of the formula II, or of phenols, at least one of which has the formula II.
  • the substituent R 2 in the compounds of the formula has the meaning of phenyl, naphthyl or phenyl, substituted by one or more alkyl groups having a total of 1 to 18 carbon atoms and preferably R 2 has the meaning of phenyl or Phenyl substituted with one or more alkyl groups with a total of 4 to 8 carbon atoms.
  • compositions according to the invention is the substituent R 1 in compounds of the formula IH.
  • compositions include those in which R 3 in compounds of the formula has the meaning of H, alkyl having 1 to 18 carbon atoms or aralkyl having 7 to 9 carbon atoms, and preference is given to the compounds in which R 3 has the meaning of H or alkyl having 4 to 8 carbon atoms.
  • R 3 is in the p- (or 4-) position.
  • Compositions are expedient in which R 3 'in compounds of the formula has the meaning of H or alkyl having 4 to 8 C atoms.
  • R 3 ' is in the o- (or 2-) position.
  • the present compositions comprise at least one compound of the formula II from the series of the phenols.
  • R 6 is C 1 to C 18 alkyl, and preferably A has the meaning of CH 2 -SY, where YC 8 -C 12 alkyl or means and R 6 has the meaning of C 8 to C 13 alkyl and in particular iso-C 8 to iso-C 13 alkyl.
  • compositions containing compounds of the formula 11 in which R 4 has the meaning of hydrogen or alkyl having 1 to 4 C atoms and preferably the meaning of alkyl having 4 C atoms and in particular tert-butyl are particularly useful.
  • compositions which correspond to an expedient embodiment are those in which R 5 in compounds of the formula II is alkyl with 1 to 4 carbon atoms, preferably alkyl with 4 carbon atoms and in particular tert-butyl.
  • R 13 iC 8 H 17 to iC 13 H 27 and in particular iC 8 H 17 or iC 13 H 27 .
  • R 1 , R 2 and R ' are alkyl having 1 to 18 carbon atoms, where, for example, are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl, Heptyl, 3-heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl, and further isoamyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl, 1,1,3,3, -Tetramethylbutyl, 1-methylhexyl, isoheptyl, 1-methylh
  • alkyl having 1 to 24 carbon atoms is mentioned, eicosyl, hemicosyl and docosyl are also included.
  • the meaning of cycloalkyl having 5 to 12 carbon atoms for R 2 , R 4 and R 5 can be cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclododecyl or, in addition, the C 5 -C 12 cycloalkyl group can optionally be by C 1 -C 4 alkyl may be substituted and represent, for example, 2- or 4-methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl or t-butylcyclohexyl.
  • R 2 represents substituted phenyl
  • the phenyl group can be substituted, for example, with C 1 -C 18 alkoxy, or with one or more alkyl groups with a total of 24 C atoms.
  • C 1 to C 8 alkoxy are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, 2-ethylhexoxy or octoxy.
  • C 7 to Cg aralkyl for example, benzyl and a-methylbenzyl can be mentioned.
  • Phenyl groups which are substituted by alkyl groups having 1 to 24 carbon atoms can be, for example, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-propylphenyl, 2-, 3- or 4-butylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-octylphenyl, 2-, 3- or 4-tert-octylphenyl, 2,4-di-tert-butylphenyl or 2,4-di-tert-octylphenyl.
  • C 1 -C 11 alkyl-substituted benzyl examples include 2-, 3- or 4-methylbenzyl, ethylbenzyl, propylbenzyl, n-butylbenzyl, tert-butylbenzyl, n-octylbenzyl, 3,5-di-tert-octylbenzyl or 2,4-di tert-butylbenzyl or 2,4-di-tert-octylbenzyl can be listed.
  • R 3 is C 7 to Cg-aralkyl
  • benzyl or methylbenzyl can be mentioned, for example.
  • R 4 , R 5 and R 6 can be alkyl with 1 to 24 carbon atoms.
  • R 4 and R 5 can also be cycloalkyl having 5 to 12 carbon atoms.
  • Corresponding examples of such alkyl groups and cycloalkyl groups are given above.
  • C 1 to C 8 alkyl for Y or R 10 , R 11 or R 12 can be taken from the above list of alkyl radicals.
  • Alkyl radicals with 8 to 13 carbon atoms, as they are called for R 6 can be found in the examples above, iso compounds are 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 1,1,3 -Trimethylhexyl and 1-methylundecyl.
  • alkyl and cycloalkyl groups mentioned for R 8 and R 9 examples from the above lists can also be assigned in accordance with the C chain length.
  • a preferred composition contains a mixture of aromatic amines, the total amount of the amines among them being 100% by weight and a maximum of them a) 5% by weight diphenylamine, 8 to 15% by weight 4-tert-butyl-diphenylamine, 24-32% by weight of amines from the group 4-tert-octyldiphenylamine, 4,4'-di-tert-butyldiphenylamine, 2,4,4'-tris-tert-butyldiphenylamine, 23 to 34% by weight of amines from the group 4-tert-butyl-4'-tert-octyldiphenylamine, o, o ', m, m' or p, p'-di-tert-octyldiphenylamine, 2,4-di-tert-butyl-4'-tert-octyldiphenylamine and 21 to 34% by weight of 2,4-di-tert-oc
  • Another preferred composition contains a mixture of an aromatic amine of For mel and a phenol of the formula wherein the weight ratio of amine to phenol is 4 to 5: 1 and preferably 4.5: 1.
  • Another preferred composition contains a mixture of 4,4'-di-tert-octyldiphenylamine and one or both phenols of the formulas and or wherein the weight ratio of amine to total phenol is 4 to 5: 1 and preferably 4.5: 1.
  • a also preferred composition contains a mixture of aromatic amines, each based on the total amount of amines, a maximum of 5 wt .-% diphenylamine, 8 to 15 wt .-% 4-tert-butyldiphenylamine, 24-32 wt .-% amines the group 4-tert-octyldiphenylamine, 4,4'-di-tert-butyldiphenylamine, 2,4,4'-tris-tert-butyldiphenylamine, 23-34% by weight amines of the group 4-tert-butyl-4 ' -tert-octyldiphenylamine, o, o ', m, m' or p, p'-di-tert-octyldiphenylamine, 2,4-di-tert-butyl-4'-tert-octyldiphenylamine and 21 to 34% by weight 2,4-di-tert
  • composition comprising a mixture of 4,4'-di-tert-octyldiphenylamine and a phenol mixture in turn consisting of and wherein the weight ratio of amine to phenols is 4 to 5: 1 and preferably 4.5: 1.
  • a group of the diphenylamines as used according to the invention can be prepared, for example, by a process as described in EP-A 149 422 by reacting diphenylamine with diisobutylene in the presence of an active alumina catalyst.
  • the phenols are known and can be prepared, for example, by a process according to DE-A 23 64 121 or DE-A 23 64 126.
  • the mixture according to the invention can contain an amine and a phenol, but it is also possible that the mixture contains one or more amines and one or more phenols.
  • the amines and phenols are premixed with one another in the stated proportions.
  • This mixture can then be added, for example, in amounts of 0.01 to 10% by weight, advantageously 0.1 to 5% by weight and preferably 0.2 to 2% by weight, based on the finished lubricating oil .
  • the phenols and amines can also be mixed individually one after the other into the lubricating oil, the mixing and concentration ratios mentioned having to be observed.
  • oils or partially or fully synthetic oils are used as lubricating oils.
  • Such oils and related products are described, for example, in Schewe-Kobek, "The Lubricant Paperback”, Wilsonhig Verlag Heidelberg, 4th edition, 1974, or in Dieter Klamann, "Lubricants and Related Products", Ver was chemistry, Weinheim, 1982 described.
  • the lubricating oil can be based on a mineral oil, for example.
  • the mineral oils are based in particular on hydrocarbon compounds.
  • Examples of synthetic lubricants include lubricants based on the aliphatic or aromatic carboxylic esters, the polymeric esters, the polyalkylene oxides, the phosphoric acid esters, the poly-d-olefins or the silicones, a diester of a dibasic acid with a monohydric alcohol, e.g. Dioctyl sebacate or dinonyl adipate, a triester of trimethylolpropane with a monohydric acid or with a mixture of such acids, e.g.
  • mineral oils e.g. Poly-a-olefins, ester-based lubricants, phosphates, glycols, polyglycols and polyalkylene glycols.
  • the invention also relates to a method for preventing or reducing the formation of black sludge in lubricating oils of spark-ignited internal combustion engines, for keeping black sludge particles in the lubricating oil in suspension and for reducing black sludge deposits on the lubrication circuit system of spark-ignited internal combustion engines, which is characterized in that the lubricating oil circuit with a phosphite-free Lubricating oil composition, as described above, is operated.
  • the invention also relates to the use of the mixtures of phenols and amines described above as antioxidants in lubricating oils.
  • Appropriate and preferred lubricating oil compositions can be derived analogously from the above description, in particular of the compounds of the formula and the formula II and from their preferred compounds and the mixture ratios mentioned with one another.
  • the lubricating oil compositions contain phenols of the formula 11 or phenols, at least one of which has the formula II. If phenols, of which at least one has the formula II, are meant, it is a mixture of two or more phenols, of which at least one corresponds to the formula II and examples of one or more further phenols, for example the following list, e.g. under point 1. "Alkylated monophenols” and / or point 7. "Esters of ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid can be removed.
  • the lubricants can additionally contain other additives which are added in order to further improve the basic properties of lubricants. These include other antioxidants, metal passivators, rust inhibitors, viscosity index improvers, pour point depressants, dispersants, detergents, thickeners, biocides, anti-foaming agents, demulsifiers and emulsifiers, as well as high-pressure additives and friction reducers.
  • Esters of thiodipropionic acid or thiodiacetic acid, or salts of dithiocarbamide or dithiophosphoric acid are included in esters of thiodipropionic acid or thiodiacetic acid, or salts of dithiocarbamide or dithiophosphoric acid.
  • metal deactivators e.g. for copper
  • metal deactivators e.g. for copper
  • Triazoles benzotriazoles and their derivatives, tolutriazoles and their derivatives, 2-mercaptobenzthiazole, 2-mercaptobenztriazole, 2,5-dimercaptobenztriazole, 2,5-dimercaptobenzthiadiazole, 5,5'-methylenebisbenzotriazole, 4,5,6,7-tetrahydrobenztriazole, salicylides -propylenediamine, salicylaminoguanidine and its salts.
  • rust inhibitors are:
  • viscosity index improvers examples are:
  • Polyacrylates polymethacrylates, vinyl pyrrolidone / methacrylate copolymers, polyvinyl pyrrolidones, polybutenes, olefin copolymers, styrene / acrylate copolymers, polyethers.
  • pour point depressants examples are:
  • dispersants / surfactants examples are:
  • wear protection additives are:
  • Compounds containing sulfur and / or phosphorus and / or halogen such as sulfurized vegetable oils, zinc dialkyldithiophosphates, tritolyl phosphate, chlorinated paraffins, alkyl and aryl di- and tri-sulfides, triphenyl phosphorothionates, diethanolaminomethyltolyltriazole, di (2-ethylhexyl) aminol.
  • the thermal aging of the formulations is carried out in a differential scanning calorimetry (DSC).
  • the DSC cell thermal analysis system 1090 from DuPont
  • the DSC cell consists of a heating block made of silver.
  • a constantan plate containing the thermocouples Chromel-Alumel
  • Sample pans and reference pans are placed on the slightly elevated thermocouples.
  • the interior of the DSC cell is covered with a thin gold film (corrosion protection).
  • the reference pan remains empty, three drops of the respective formulation are poured into the sample pan.
  • the temperature difference between sample and reference pans is determined under isothermal conditions.
  • the enthalpy change dH / dt is given in mW. All measurements are carried out in air +400 ppm N0 2 .
  • the pressure is 8 bar.
  • Aral RL 136 a commercially available "black sludge reference oil", is used as the base oil. To increase the susceptibility to oxidation of the oil, 1% 1-decene is added to this oil.
  • the thermal aging of the oils is determined in a further, independent method.
  • a DSC pressure cell DuPont 770
  • the formulations are aged under the conditions of air + 400 ppm NO 2 , pressure 8 bar.
  • the samples aged in the temperature range of 120 ° C - 150 ° C are then examined by means of IR spectroscopy. For this purpose, the spectra are standardized to the same layer thickness.
  • two peaks at 1730 cm- 1 and at 1630 cm- 1 are evaluated [1730 cm -1 : 6-membered lactone and 1630 cm -1 : nitrate ester].
  • a reduction in these absorption bands is a measure of a lower oxidation.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Claims (22)

1. Composition huileuse lubrifiante sans phosphites qui contient :
a) une huile minérale, une huile synthétique ou un mélange de telles huiles et
b) un mélange contenant au moins une amine aromatique répondant à la formule 1 :
Figure imgb0105
dans laquelle
R1 représente H, un alkyle contenant de 1 à 18 atomes de carbone, un allyle, un méthallyle, un benzyle ou un benzyle porteur d'un alkyle en C1-C11,
R2 représente un alkyle contenant de 1 à 18 atomes de carbone, un cycloalkyle en C5-C12, un cycloalkyle en C5-C12 porteur d'un alkyle en C1-C4, un phényle, un naphtyle, un phényle porteur d'un -OH, d'un radical
Figure imgb0106
d'un alcoxy en C1-C18, d'un aralkyle en C7-C9 ou d'un ou plusieurs alkyles contenant au total de 1 à 24 atomes de carbone, ou un radical :
Figure imgb0107
le symbole R' représentant H ou un alkyle en C1-C18,
R11 et R12 représentent chacun, indépendamment l'un de l'autre, H ou un alkyle en C1-C18,
R3 représente H, un alkyle en C1-C24 ou un aralkyle en C7-Cg et
R3' représente H ou un alkyle en C1-C24, et au moins un phénol répondant à la formule Il:
Figure imgb0108
dans laquelle
R4 représente H, un alkyle en C1-C24, un cycloalkyle en C5-C12, un cycloalkyle en C5-C12 porteur d'un alkyle en C1-C4, un phényle ou un radical -CH2-S-R10,
R5 représente un alkyle en C1-C24, un cycloalkyle en C5-C12, un cycloalkyle en C5-C12 porteur d'un alkyle en C1-C4, un phényle ou un radical -CH2-S-R10,
A représente un radical -CqH2q-Sx-Y ou
Figure imgb0109
Y représente H, un alkyle en C1-C18, un phényle, un phényle porteur d'un alkyle en C1-C24, un benzyle, un radical
Figure imgb0110
ou, lorsque q est égal à 0, un radical:
Figure imgb0111
dans lequel R4 et R5 ont chacun les significations qui leur ont été données ci-dessus,
b est égal à 1 ou à 2,
d est égal à 0, à 1, à 2 ou à 3,
q est égal à 0, à 1, à 2 ou à 3,
x est égal à 1, à 2, à 3 ou à 4,
R6 représente un alkyle en C1-C24,
R7 représente un radical répondant à l'une des formules :
Figure imgb0112
Figure imgb0113
Figure imgb0114
Figure imgb0115
dans lesquelles d est égal, pour chacune d'elles, à 0, à 1, à 2 ou à 3, t est égal à 2, à 3, à 4, à 5 ou à 6, et R4 et R5 ont chacun les significations qui leur ont été données ci-dessus,
R8 et R9 représentent chacun, indépendamment l'un de l'autre, H, un alkyle en C1-C12, un phényle ou un phényle porteur d'un ou de deux alkyles en C1-C4 et/ou -OH, ou
R8 et R9 forment ensemble, et avec l'atome de carbone qui les unit, un cycloalkyle en C5-C12, et
R10 représente un alkyle en C1-C18, un phényle ou un radical
Figure imgb0116
dans lequel b et R6 ont les significations qui leur ont été données plus haut, les composés étant présents, dans le mélange, en un rapport de 2 à 6 parties en poids de l'amine ou des amines aromatiques de formule l pour 1 partie en poids du ou des phénols de formule II ou de phénols dont au moins 1 répond à la formule II.
2. Composition selon la revendication 1 caractérisée en ce que, dans le mélange, les composés sont en des quantités telles qu'il y ait de 4 à 5 parties en poids de l'amine ou des amines aromatiques de formule 1 pour 1 partie en poids du ou des phénols de formule Il ou de phénols dont au moins 1 répond à la formule II.
3. Composition selon l'une des revendications 1 et 2 caractérisée en ce que, dans les composés de formule I, R2 représente un phényle, un naphtyle ou un phényle porteurs d'un ou de plusieurs alkyles renfermant au total de 1 à 18 atomes de carbone, et représente de préférence un phényle ou un phényle porteur d'un ou de plusieurs alkyles renfermant au total de 4 à 8 atomes de carbone.
4. Composition selon la revendication 1 caractérisée en ce que, dans les composés de formule l, R1 représente H.
5. Composition selon la revendication 1 caractérisée en ce que, dans les composés de formule l, R3 représente H, un alkyle contenant de 1 à 18 atomes de carbone ou un aralkyle contenant de 7 à 9 atomes de carbone, de préférence H ou un alkyle contenant de 4 à 8 atomes de carbone, et R3 occupe la position para.
6. Composition selon la revendication 1 caractérisée en ce que, dans les composés de formule 1, R3' représente H ou un alkyle contenant de 4 à 8 atomes de carbone, et occupe la position ortho.
7. Composition selon la revendication 1 qui contient plusieurs amines aromatiques de formule l, en l'espèce les suivantes :
a) la diphénylamine,
b) la 4-tert-butyl-diphénylamine,
c) i) la 4-tert-octyl-diphénylamine,
c) ii) la 4,4'-di-tert-butyl-diphénylamine,
c) iii) la 2,4,4'-tris-tert-butyl-diphénylamine,
d) i) la 4-tert-butyl-4'-tert-octyl-diphénylamine
d) ii) la o,o'-, m,m'- ou p,p'-di-tert-octyldiphènylamine,
d) iii) la 2,4-di-tert-butyl-4'-tert-octyl-diphénylamine,
e) i) la 4,4'-di-tert-octyl-diphénylamine,
e) ii) la 2,4-di-tert-octyl-4'-tert-butyl-diphénylamine,
avantageusement au plus 5% en poids - à chaque fois par rapport à la quantité totale des amines - de la diphénylamine a), de 8 à 15% en poids de la 4-tert-butyldiphénylamine b), de 24 à 32% en poids de composés du groupe c), de 23 à 34% en poids de composés du groupe d) et de 21 à 34% en poids de composés du groupe e).
8. Composition selon la revendication 1 caractérisée en ce que, dans le composé de formule II, A représente un radical -CqH2q-Sx-Y dans lequel q est égal à 0 ou à 1, x est égal à 1 ou à 2 et Y représente un alkyle contenant de 4 à 18 atomes de carbone, un phényl, un phényl porteur d'un alkyle en C2-C8 ou un radical -(CH2-
Figure imgb0117
le svmbole R6 désianant un alkvle en C1-C18.
9. Composition selon la revendication 8 caractérisé en ce que, dans les composés de formule II, A représente un radical :
Figure imgb0118
dans lequel x est égal à 1 ou à 2, R4 représente H ou un alkyle contenant de 1 à 5 atomes de carbone et R5 représente un alkyle contenant de 1 à 5 atomes de carbone.
10. Composition selon la revendication 1 caractérisée en ce que, dans les composés de formule II, Arepré- sente un radical
Figure imgb0119
' dans lequel d est égal à 2 ou à 3 et R7 représente un radical répondant à l'une des formules suivantes :
Figure imgb0120
Figure imgb0121
Figure imgb0122
Figure imgb0123
dans lesquelles d est à chaque fois égal à 2 ou à 3, R4 et R5 ont les significations qui leur ont été données à la revendication 1, et R8 et R9 représentent chacun, indépendamment l'un de l'autre, l'hydrogène, un alkyle en C1-C9, un phényle ou un radical :
Figure imgb0124
11. Composition selon la revendication 1 caractérisée en ce que, dans la formule II, R4 représente l'hydrogène ou un alkyle contenant de 1 à 4 atomes de carbone.
12. Composition selon la revendiction 1 caractérisée en ce que, dans la formule II, R5 représente un alkyle contenant de 1 à 4 atomes de carbone, de préférence un radical tert-butyle.
13. Composition selon la revendication 1 qui contient, comme composé(s) de formule II, un composé de formule :
Figure imgb0125
et/ou un composé de formule :
Figure imgb0126
le symbole R13 représentant un radical iSO-C8Hl7 à iso-C13H27.
14. Composition selon la revendication 1 qui contient un mélange d'amines aromatiques, à savoir (les pourcentages sont rapportés à chaque fois à la quantité totale des amines) au plus 5% en poids de diphénylamine, de 8 à 15% en poids de 4-tert-butyl-diphénylamine, de 24 à 32% en poids d'amines du groupe formé par la 4-tert-octyldiphénylamine, la 4,4'-di-tert-butyl-diphénylamine et la 2,4,4'-tris-tert-butyl-diphénylamine, de 23 à 34% en poids d'amines du groupe formé par la 4-tert-butyl-4'-tert-octyldiphénylamine, l'o,o'-, m,m'- ou p,p'- di-tert-octyldiphénylamine et la 2,4-di-tert-butyl-4'-tert-octyldiphénylamine, et de 21 à 34% en poids de 2,4-di-tert-octyl-4'-tert-butyl-diphénylamine et/ou de 4,4'-di-tert-octyldiphénylamine, et un phénol de formule :
Figure imgb0127
le rapport pondéral de l'amine au phénol étant compris entre 4 : 1 et 5 : 1.
15. Composition selon la revendication 1 qui contient un mélange d'une amine aromatique de formule :
Figure imgb0128
et d'un phénol de formule :
Figure imgb0129
le rapport pondéral de l'amine au phénol étant compris entre 4 : 1 et 5 : 1.
16. Composition selon la revendication 1 qui contient un mélange de 4,4'-di-tert-octyl-diphénylamine et d'un des deux ou des deux phénols de formules :
Figure imgb0130
et
Figure imgb0131
le rapport pondéral de l'amine au phénol total étant compris entre 4 : 1 et 5 : 1.
17. Composition selon la revendication 1 qui contient un mélange d'amines aromatiques, à savoir (les pourcentages sont rapportés à chaque fois à la quantité totale des amines) au plus 5% en poids de diphénylamine, de 8 à 15% en poids de 4-tert-butyl-diphénylamine, de 24 à 32% en poids d'amines du groupe formé par la 4-tert-octyldiphénylamine, la 4,4'-di-tert-butyl-diphénylamine et la 2,4,4'-tris-tert-butyl-diphénylamine, de 23 à 34% en poids d'amines du groupe formé par la 4-tert-butyl-4'-tert-octyldiphénylamine, l'o,o'-, m,m'- ou p,p'- di-tert-octyldiphénylamine et la 2,4-di-tert-butyl-4'-tert-octyldiphènylamine, et de 21 à 34% en poids de 2,4-di-tert-octyl-4'-tert-butyl-diphénylamine et/ou de 4,4'-di-tert-octyldiphénylamine, et un phénol de formule :
Figure imgb0132
le rapport pondéral de l'amine au phénol étant compris entre 4 : 1 et 5 : 1.
18. Composition selon la revendication 1 qui contient un mélange de 4,4'-di-tert-octyl-diphénylamine et d'un mélange de phénols, lui-même constitué de :
30% en poids de
Figure imgb0133
30% en poids de
Figure imgb0134
et 40% en poids de
Figure imgb0135
le rapport pondéral de l'amine aux phénols étant compris entre 4 : 1 et 5 : 1.
19. Composition selon la revendication 1 dans laquelle l'huile lubrifiante est une huile pour moteurs à combustion interne à allumage commandé.
20. Procédé pour empêcher ou pour diminuer la formation de boue noire dans des huiles lubrifiantes de moteurs à combustion interne à allumage commandé, pour maintenir des particules de boue noire en suspension dans l'huile lubrifiante et pour détruire des dépôts de boue noire sur le système à circuit de lubrification de moteurs à combustion interne à allumage commandé, procédé caractérisé en ce qu'on fait fonctionner le circuit d'huile lubrifiante avec une composition huileuse lubrifiante sans phosphites selon la revendication 1.
21. Application d'un mélange contenant au moins une amine aromatique de formule et au moins un phénol de formule Il selon la revendication 1 comme antioxydant dans des huiles lubrifiantes.
EP89810410A 1988-06-09 1989-06-01 Composition lubrifiante Expired - Lifetime EP0346283B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH2196/88 1988-06-09
CH219688 1988-06-09

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EP0346283A2 EP0346283A2 (fr) 1989-12-13
EP0346283A3 EP0346283A3 (en) 1990-03-28
EP0346283B1 true EP0346283B1 (fr) 1992-07-29

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JP (1) JP3101818B2 (fr)
KR (1) KR0125793B1 (fr)
CN (1) CN1019984C (fr)
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DE (1) DE58901932D1 (fr)
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Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0406826B1 (fr) * 1989-07-07 1993-08-11 Ciba-Geigy Ag Composition de lubrifiant
ES2091236T3 (es) * 1989-11-08 1996-11-01 Ciba Geigy Ag Composiciones de lubricantes.
US5366648A (en) * 1990-02-23 1994-11-22 The Lubrizol Corporation Functional fluids useful at high temperatures
SG48102A1 (en) * 1992-09-14 1998-04-17 Oronite Japan Ltd Lo phosphorous engine oil compositions and additives compositions
JPH0693281A (ja) * 1992-09-14 1994-04-05 Oronaito Japan Kk エンジン油組成物
JP2859077B2 (ja) * 1993-04-09 1999-02-17 出光興産株式会社 潤滑油組成物
WO1996012780A2 (fr) * 1994-10-25 1996-05-02 Exxon Research And Engineering Company Antioxydants pour huile lubrifiante
JP3401348B2 (ja) * 1994-12-07 2003-04-28 新日本石油株式会社 潤滑油組成物
JP3401349B2 (ja) * 1994-12-07 2003-04-28 新日本石油株式会社 潤滑油組成物
CN1045464C (zh) * 1996-12-11 1999-10-06 中国石油化工总公司 一种合成油锂基润滑脂的制备方法
US6150309A (en) * 1998-08-04 2000-11-21 Exxon Research And Engineering Co. Lubricant formulations with dispersancy retention capability (law684)
GB2359089A (en) * 2000-02-14 2001-08-15 Exxonmobil Res & Eng Co Lubricating oil compositions
GB2368848B (en) 2000-09-21 2002-11-27 Ciba Sc Holding Ag Lubricants with 5-tert.-butyl-hydroxy-3-methylphenyl substituted fatty acid esters
US7056967B2 (en) * 2001-04-10 2006-06-06 Ciba Specialty Chemicals Corporation Stabilized medium and high voltage cable insulation composition
MXPA05002726A (es) * 2002-09-19 2005-05-23 Ciba Sc Holding Ag Semi-amidas del acido succinico, como agentes anti-corrosivos.
US6645920B1 (en) 2002-11-14 2003-11-11 The Lubrizol Corporation Additive composition for industrial fluid
US7494960B2 (en) * 2004-02-03 2009-02-24 Crompton Corporation Lubricant compositions comprising an antioxidant blend
US7928045B2 (en) * 2006-02-28 2011-04-19 Chemtura Corporation Stabilizing compositions for lubricants
US20090011961A1 (en) * 2007-07-06 2009-01-08 Jun Dong Lubricant compositions stabilized with styrenated phenolic antioxidant
EP2291497B1 (fr) * 2008-05-13 2013-07-10 The Lubrizol Corporation Méthode pour rendre minimale la boue de turbo avec des anti-oxydants aminiques
CN102089415A (zh) * 2008-07-14 2011-06-08 科聚亚公司 用于稳定润滑剂组合物的液态添加剂
US8110532B2 (en) * 2008-11-24 2012-02-07 Chemtura Corporation Antioxidant compositions
AU2012271126B2 (en) * 2011-06-17 2016-10-13 Biosynthetic Technologies, Llc Estolide compositions exhibiting high oxidative stability
CN103013643B (zh) * 2011-09-21 2014-11-05 山西太钢不锈钢股份有限公司 一种钢铁行业水上浮油的处理方法
WO2014019911A1 (fr) 2012-08-01 2014-02-06 Basf Se Procédé d'amélioration de la thermostabilité d'huiles lubrifiantes dans des moteurs à combustion interne
US20140034004A1 (en) * 2012-08-01 2014-02-06 Basf Se Process for improving thermostability of lubricant oils in internal combustion engines
US20180105679A1 (en) * 2016-10-19 2018-04-19 Veyance Technologies, Inc. Severely Hydrotreated Naphthenic Distillate Containing Rubber Compositions
CN109266422A (zh) * 2018-09-30 2019-01-25 镇江宝海船舶五金有限公司 一种适用船用锚链的润滑剂及其制备方法

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2009480A (en) * 1932-06-10 1935-07-30 Goodrich Co B F Antioxidant
US2691632A (en) * 1952-03-01 1954-10-12 California Research Corp Oil compositions resistant to oxidation
BE604078A (fr) * 1960-05-25
GB1093945A (en) * 1963-11-12 1967-12-06 Monsanto Chemicals Thermally stable alkyldiaryl sulphides and their use as functional fluids
US3452056A (en) * 1966-04-07 1969-06-24 Uniroyal Inc Substituted diphenylamines
US3368975A (en) * 1966-06-02 1968-02-13 Eastman Kodak Co Antioxidants
EP0059168B1 (fr) * 1981-02-19 1985-10-02 Ciba-Geigy Ag Elastomères organiques et huiles lubrifiantes minérales et synthétiques contenant des esters phénolmercaptocarboxyliques comme stabilisants
US4370434A (en) * 1981-04-10 1983-01-25 The Goodyear Tire & Rubber Company Mercapto acid ester antioxidants for polymers
EP0079855A1 (fr) * 1981-11-12 1983-05-25 Ciba-Geigy Ag Esters hydroxyphénylthioalcanoiques alcoylés
GB8332797D0 (en) * 1983-12-08 1984-01-18 Ciba Geigy Ag Antioxidant production
EP0165209B1 (fr) * 1984-06-12 1989-07-19 Ciba-Geigy Ag Phénols o'-substitués, o,p-bifonctionnalisés
US4741846A (en) * 1984-08-02 1988-05-03 Ciba-Geigy Corporation 2,4,6-trifunctionalized phenols
US4704219A (en) * 1985-07-05 1987-11-03 The B. F. Goodrich Company Novel composition of para-butylated and octylated, ortho-ethylated diphenylamines
US4846985A (en) * 1986-03-10 1989-07-11 The Lubrizol Corporation Antioxidant compositions
US4963276A (en) * 1987-12-24 1990-10-16 Ciba-Geigy Corporation Lubricant composition

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CN1038299A (zh) 1989-12-27
CN1019984C (zh) 1993-03-03
US5091099A (en) 1992-02-25
DE58901932D1 (de) 1992-09-03
KR910001008A (ko) 1991-01-30
ES2043092T3 (es) 1993-12-16
EP0346283A3 (en) 1990-03-28
CA1335891C (fr) 1995-06-13
JPH0238493A (ja) 1990-02-07
KR0125793B1 (ko) 1997-12-18
HK11795A (en) 1995-02-03
JP3101818B2 (ja) 2000-10-23
EP0346283A2 (fr) 1989-12-13

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