Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • 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
• • 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
  • 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
  • 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
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
• • 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/16—Naphthenic acids
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
  • C10M2215/062—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups bound to the aromatic ring

Definitions

• lubricating oils that are effective at elevated temperatures.
• Polyesters, polyolefins, polyglycols, polyphenyl ethers, phosphates, silicones, etc. have been used as suitable lubricating oils. These lubricating oils undergo oxidative degradation at elevated temperatures. Loss of lubricating properties due to oxidative breakdown of these oils may cause failure of a part, or parts, in contact with the oils.
• the prior art discloses the stabilization of lubricating oils using various amines including diphenyl- and substituted diphenylamines, p-phenylenediamine and substituted naphthylamine. There appears to be no recognition of the use of secondary amines wherein one of the groups attached the amino nitrogen is an aromatic or substituted aromatic ring and the other group is an aliphatic carbon which in turn is attached to an aromatic or substituted aromatic ring.
• U.S. Patent 1,469,245 discloses N-(o-Hydroxybenzyl) -N I -phenyl-p-phenylene diamine as an anti-degradant for rubber. This compound belongs to the class of phenylene diamines which are known anticxidants. Furthermore, its use as a stabilizer for lubricating oils is neither disclosed in that patent, nor elsewhere.
• U.S. Patent No. 2,108,147 teaches a method for preparing secondary and teritary amines including 1-anilino-1-phenylethane.
• Hickenbottom teaches a phenylamine compound designated as alpha-phenyl ethyl- p -toluidine; see Journal of the Chemical Society (1934) pages 319-322.
• Beilstein discloses a phenyl amine compound of the general formula wherein R can be phenyl; see Handbuch Der Organishen Chemie 4th Ed., Vol XII Pat. IV pages 2403-4. None of the aforegoing compounds are taught to be antioxidants.
• Y is: When Y is the moiety of formula (II), Z is H or C 1 to C 3 alkyl; and X and R 2 are each independently selected from the group consisting of hydrogen, C 1 -C 12 alkyl, C 1 -C 12 alkox y ; C 2 -C 18 carbalkoxy, halogen, or nitro and R 1 is hydrogen, C 1 -C 12 alkyl, C 1 -C 12 alk- oxy, C 2 -C 18 carbalkoxy, halogen, amino or nitro.
• R 1 and R 3 are each independently selected from the group of moieties set forth as R 1 above and R 2 is as previously defined.
• the compounds of this invention are novel compounds when X and Z are each independently selected from the group H and C 1 -C 3 alkyl; and R l and R 2 are as previously defined except that they may not simultaneously be hydrogen when Z is hydrogen.
• the antioxidants of this invention are used in conjunction with a metal deactivator and. a metal or metal salt.
• the preferred metal salts are oil soluble organic salts, e.g., metal naphthenates.
• This invention relates to a compound for the stabilizing lubricating oils against oxidation and sludge formation.
• this invention relates to stabilizing such oils utilizing phenylated benzylamines or phenylated tetrahydro naphthylamines, which may be substituted or unsubstituted, either alone or in conjunction with a metal deactivator and a metal compound.
• This stabilizer system provides a surprisingly high degree of resistance to oxidative breakdown of lubricating oils as well as resulting in dramatic reductions in sludge formation.
• Certain of the phenylated benzylamines and phenylated tetrahydro naphthylamines used in the practice of this invention are novel compounds.
• This invention relates to stabilizing a lubricating oil utilizing as the stabilizer an antioxidant which is an amino compound having the general formula .
• Y is: When Y is the moiety of formula (II), Z and X are each independently selected from the group consisting of H or C 1 to C 3 alkyl; R 2 is selected from the group consisting of hydrogen, C- 1 to C 12 alkyl, C l -C 12 alkoxy; C 2 -C 18 carbalkoxy, halogen, or nitro and R l is hydrogen, C 1 -C 12 alkyl, C 1 -C 12 alkox y , C 2 -C 18 carbalkoxy, halogen, amino or nitro.
• R 1 and R 3 are each independently selected from the group of moieties set forth as R 1 above and R 2 is as previously defined.
• the compounds of this invention are novel compounds when X and Z are each independently selected from the group consisting of H and C 1 -C 3 alkyl; and R 1 and R 2 are as previously defined except that they may not be simultaneously hydrogen when Z is hydrogen.
• Z is H or methyl and X is methyl.
• the amines of this invention are useful in stabilizing a wide range of lubricating oils including polyester oils, mineral oils and synthetic hydrocarbon oils.
• the stabilizer 'system of this invention is particularly effective for use in polyolester lubricating oils.
• the polyolester lubricating oils for which the stabilizer systems of this invention are suitable are synthetic lubricants based upon one or more organic carboxylic acid esters.
• Illustrative examples of such oils are diesters such as dioctyl sebacate or dinonyl adipate prepared by the reaction of a dibasic acid and a monohydric alcohol; triesters such as trimethylolpropane tripelor- gonate or trimethylolpropane tricaprilate prepared by the reaction of trimethylol propane and a monobasic acid; tetraesters such as pentaerythritol tetracaprilate prepared by the reaction of pentaerythritol and a monobasic acid; esters of trimethylolpropane or pentaerythritol prepared by reaction with mixtures of monobasic acids; or complex esters prepared by reacting mixtures of monobasic acids, dibasic acids and polyhydric alcohols.
• the synthetic hydrocarbon oils to which the stabilizer system of this system of this invention may be added are oligomers of alpha olefins.
• the preferred alpha olefins are C 3 -C 14 alphaolefins.
• these hydrocarbon oils have a number average molecular weight of about 280 to about 2,000; preferably about 350 to about 1,500.
• These lubricating oils have low unsaturation preferably having an iodine number of less than 3.
• antioxidants when used in the specification and claims means the substituted phenylated amines and substituted tetrahydronaphthylamines of this invention.
• stabilizer system as used in the specification and claims means the aforegoing antioxidants in conjunction with a metal compound and a metal deactivator.
• the metal may be present either as the free metal or a salt of a metal.
• the salt must be soluble in the lubricating oil and is preferably an organometallic salt.
• the preferred salts include naphthenates, stearates, acetylacetonates, octoates, decanoates etc.
• the metal deactivators useful in the practice of this invention are benzotriazole and benzotriazole derivatives.
• the benzotriazole derivative can be alkyl substituted or dialkyl amino alkyl substituted; preferably dialkyl amino alkyl substituted. Substitution is on the secondary nitrogen of the triangle.
• the alkyl group can be a Cl to C20 alkyl and each alkyl may be the same or different than the others.
• the alkyl groups are selected to give the benzotriazole derivative sufficient oil solubility to be incorporated into the lubricant in an effective amount e.g. C S- C 12 alkyl. Typical of such compounds is Reomet 38 marketed by Ciba Geigy Co.
• the term "metal deactivator" as used in the specification and claims means a compound which when added to a lubricant will neutralize the catalytic effect of metals e.g. copper in promoting oxidation.
• the various components of the antioxidant system which may be added in any order are used in the following amounts.
• the antioxidant of this invention is used in amounts varying from about 0.5 to about 5.0 parts by weight per 100 parts of the oil, preferably, about 1.0 to about 4.0 parts; more preferably 2.0 to 2.5 parts.
• the metal deactivators can be used in amounts of about 0.05 to about 1.0 part by weight per 100 parts of the oil, preferably, 0.1 to 0.3 part.
• Metal or metal salts are used in the amounts of about 1 to about 25 parts of metal by weight per million parts of the oil; preferably 2 to 10 parts.
• the preferred metal is copper.
• polyolester as used in the specification and claims means a polyester prepared from a polyol by reacting the polyol with a stochiometric equivalent of mono basic acids.
• This example shows the unexpected ability of the antioxidant of the present invention to protect polyester based lubricating oils against oxidative degradation.
• the oil used was a commercially available polyolester fluid, Hercolube A (marketed by Hercules Inc.) and believed to be one prepared from pentaerythritol and a mixture of monocarboxylic acids, e.g., valeric acid and pelargonic acid.
• the neutralization number was determined by the color- indicator titration method according to ASTM Procedure D974-55T.
• the Kinematic Viscosity was determined according to ASTM Procedure D445-53T.
• the metal washers which were weighed initially, were then carefully washed and weighed again to determine the weight change in grams.
• This example demonstrates the effect of the addition of and changes in the levels of a metal deactivator such as Reomet-38, a benzotriazole derivative marketed by Ciba Geigy Co., on the stabilization of a polyolester based lubricating oil while the level of N-( alpha-methylbenzyl)aniline and copper are maintained constant.
• a metal deactivator such as Reomet-38, a benzotriazole derivative marketed by Ciba Geigy Co.
• Table III shows that a stabilizer system containing N-( alpha-methylbenzyl)aniline and Reomet-38 is ineffective in the absence of copper (Sample A, Table III) in decreasing the amounts of sludge, maintaining low viscosity, low neutralization number, and protecting the metal washers from oxidation. In the absence of copper, Reomet 38 functions as a pro-degradant.
• the data in Table III further shows that increasing amounts of copper above 10 ppm causes the stabilizer system to exhibit a decrease in its efficiency in controlling oxidative breakdown.
• Sample II-D illustrates that when the amine, a metal deactivator and copper are present, the greatest protection is afforded to the oil.
• Sample I-B amine but no copper
• Sample I-C amine and copper
• Sample III-A amine and metal deactivator but no copper
• This example demonstrates how the stabilization of a polyolester based lubricating oil is affected by changes in the level of N-( alpha-methylbenzyl)aniline while maintaining constant Reomet-38 level in the presence of a constant amount of copper metal.
• the samples were prepared as in EXAMPLE I, using the amounts of ingredients as shown in Table V.
• This example demonstrates how various substituted N-benzylanilines effect the stabilization of a polyolester based oil while maintaining a constant Reomet-38 level in the presence of a constant amount of copper metal.
• N-benzylanilines were prepared by catalytic hydrogenation of the corresponding Schiff's bases. Five percent Pd/c was used as the catalyst and ethanol was used as the solvent for hydrogenating the Schiff's bases.
• Schiff's bases were prepared by the reaction of the appropriate ketones and anilines in the presence of molecular seives. About 40 grams of molecular sieves (Linde 5A) were added to 1.0 mole of ketone and 1.0 to 1.2 moles of aromatic amine in 200 ml. of benzene; see Kazuo Taguchi and F. H. Westheimer, J. ORG. CHEM. 36, 1570 (1971).
• reaction mixture was refluxed with continuous removal of water until almost no free ketone could be detected in the reaction mixture by I. R. spectroscopy.
• the mixture was then filtered and the molecular seives washed with benzene. The filtrate and washings were combined and evaporated to dryness under reduced pressure.
• the crude product was purified by either crystallization or by vacuum distillation.
• a preferred embodiment of this invention involves alkylation in the benzyl ring and/or the aniline ring of the parent alpha-methyl benzyl aniline. This is beneficial in that it results in decreased volatility of the parent compound.
• R 2 can be H, or a C 1 to C 12 alkyl group and R 1 can be H or a C 4 to C 12 alkyl group; provided that R 1 and R 2 are not simultaneously both hydrogen.
• R 2 can be a C 1 to C 12 alkyl group which may or may not be branched.
• R 1 can be an alkyl group, preferably in the para-position or a tertiary alkyl group such as those derived from isobutylene, isobutylene dimer, isobutylene trimer, propylene trimer, alpha-methyl styrene and the like.
• This example shows how phenylated- alpha-tetralylamine affects the stabilization of a polyolester based lubricating oil.
• Table VIII shows that the addition of phenylated- alpha-tetralylamine, a metal deactivator and copper or a copper salt to a polyolester lubricating oil such as Hercolube A stabilizes the said oil against oxidative breakdown.
• Example II To 100 parts of polyoctene synthetic hydrocarbon oil is added 2.0 parts of N-( alpha-methylbenzyl)aniline and 0.5 parts Reomet 38 as in Example II. E. The resulting blend is found to exhibit excellent antioxidant properties when an aging test is performed at elevated temperatures.
• N-alpha-methyl-p-nonyl benzylidene) aniline (XXX) 40g was hydrogenated using 5% Pd/C as the catalyst and 95% ethanol as the solvent.
• N-(alpha-methyl-p-nonyl benzyl) aniline (XXXI) was obtained by fractional distillation. XXXI had a boiling point of 183°C at 0.15 millimeter.
• the desired product II had a boiling point of 173 to 178°C at 0.025 millimeter.
• Nonyl benzene was prepared by alkylating benzene with mixed propylene trimer using Friedel Crafts reaction. Nonyl benzene was nitrated and reduced to give p-nonyl aniline. A solution of p-nonyl aniline (30g), acetophenone (60g), toluene (200ml) and pyridine (20ml) was refluxed with continuous removal pf water. N-( ⁇ -methyl benzylidene)-p-nonyl aniline (III) was obtained by fractional distillation. III had a boiling point of 194°C at 0.05 millimeter.
• N-( ⁇ -methyl benzylidene)-p-nonyl aniline (III) (16.5g) prepared by the procedure described in Example IIA was hydrogenated suing 5% Pd/C as the catalyst and 95% ethanol as the solvent.
• N-( ⁇ -methyl benzyl)-p-nonyl aniline (IV) was obtained by fractional distillation. IV had a boiling point of 180-184°C at 0.025 millimeter.
• N-( ⁇ -methyl benzylidene)-p-anisidine (VII) prepared by the procedure described in example IVA was hydrogenated using 5% Pd/C as the catalyst and 95% ethanol as the solvent to give N-( ⁇ -methyl benzyl)-p-anisidine (VIII). VIII had a melting point of 64°C.
• N-(ex-methyl benzylidene)-p-carbethoxyaniline (XI) prepared by the procedure described in example XXIIA was hydrogenated using 5% Pd/C as the catalyst and 95% ethanol as the solvent to give N-( ⁇ -methyl benzyl)-p-carbethoxy aniline (XII).
• XII had a m.p. of 88°C.
• N-( ⁇ -methyl benzylidene)m-carbethoxyaniline (27g) prepared by the procedure described in example VIIA was hydrogenated using 5% Pd/C as the catalyst and 95% ethanol as the solvent.
• N-( ⁇ -methyl benzyl m-carbethoxy aniline (XIV) was obtained by fractional distillation. XIV had a boiling point of 156°C at 0.1 millimeter.
• XIX m-Chloro-N-( ⁇ -methyl benzylidene) aniline (XIX) (24g) prepared by the procedure described in example XXVIIA was hydrogenated using 5% Pd/C as the catalyst and 95% ethanol as the solvent. m-Chloro-N-( ⁇ -methyl benzyl) aniline (XX) was obtained by fractional distillation. XX had a boiling point of 133°C at 0.15 millimeter.
• o-Chloro-N-( ⁇ -methyl benzylidene) aniline (XXI) (15g) prepared by the procedure described in example XXVIIIA was hydrogenated using 5% Pd/C as the catalyst and 95% ethanol as the solvent.
• o-Chloro-N-( ⁇ -methyl benzyl) aniline (XXII) was obtained by fractional distillation.
• XXII had a boiling point of 134°C at 1.2 millimeter.
• XXIII p-Acetyl-N-( ⁇ -methylbenzylidene) aniline (XXIII) (30g) prepared by the procedure described in Example XXIXA was hydrogenated using 5% Pd/C as the catalyst and 95% ethanol as the solvent.
• p-Acetyl-N-( ⁇ -methyl benzyl) aniline (XXIV) was obtained by fractional distillation.. XXIV had a boiling point of 165°C at 0.1 millimeter.
• XXVII N-(1,2,3,4-tetrahydronaphthylidene) aniline (38g) prepared as described in example XXXIA was hydrogenated using 5% Pd/C as the catalyst and 95% ethanol as the solvent. The crude product was crystallized from ethanol to give 1-(p-dodecyl- anilino)-1,2,3,4-tetrahydronaphthalene (XXVII). XXVII had a melting point of 34°C.
• N-(1,2,3,4-Tetrahydronaphthylidene)-p-carbethoxy- aniline (XXVIII) (30g) prepared by the procedure described in example XXXIIA was hydrogenated using 5% Pd/C as the catalyst and 95% ethanol to give 1-(p-carbethoxy-anilino)-1,2,3,4-tetrahydronaphthalene (XXIX).
• XXIX had a melting point of 34°C.

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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)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Anti-Oxidant Or Stabilizer Compositions (AREA)

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• 1979
  • 1979-08-22 CA CA000334239A patent/CA1138472A/fr not_active Expired
• 1980
  • 1980-05-20 BR BR8003141A patent/BR8003141A/pt unknown
  • 1980-05-30 EP EP19800200511 patent/EP0022281B1/fr not_active Expired
  • 1980-05-30 DE DE8080200511T patent/DE3064808D1/de not_active Expired
  • 1980-05-31 JP JP7364580A patent/JPS55161894A/ja active Granted

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