Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino 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
  • 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
  • C10M3/00—Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
• • 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
  • C10M2207/28—Esters
  • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/283—Esters of polyhydroxy compounds
• • 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
  • C10M2207/28—Esters
  • C10M2207/286—Esters of polymerised unsaturated 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
  • 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
• • 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
  • C10M2207/28—Esters
  • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
• • 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene 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
  • 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
• • 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
  • C10M2215/064—Di- and triaryl amines
• • 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
  • C10M2215/064—Di- and triaryl amines
  • C10M2215/065—Phenyl-Naphthyl amines
• • 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
  • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
  • C10M2229/02—Unspecified siloxanes; Silicones
• • 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
  • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
  • C10M2229/04—Siloxanes with specific structure
  • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
• • 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
  • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
  • C10N2050/10—Form in which the lubricant is applied to the material being lubricated semi-solid; greasy

Definitions

• This invention relates to lubricant compositions having improved stability properties. More particularly the invention relates to lubricants to whichhave been added a small amount of an additive having the ability to reduce oxidative deterioration of suchlubricant.
• the oxidation of a lubricant may result in the loss of lubricating properties, and if such loss is severe enough and if it goes undetected long enough, the machine itself may become totally inoperative. This deterioration may be detected, however, because it is usually accompanied by an increase in acidity or an increase in-viscosity, or both. These can be determined using conventional tests.
• Another class of-known'a'ntioxidants are the t-alkylsubstituted"diarylamines.
• U.S;Pat. 3,414,618 discloses that tertiarylalky-substituted 'diphenyl-,L dinaphthyl-, or N- phenyl-naphthylamine may be used as antioxidants for a syntheticlubricant.
• a lubricant composition comprising a major amount of a 3,781,206 Patented Dec. 25, 1973 wherein Ar and Ar are selected from the group consisting of phenyl, naphthyl, phenanthryl and anthryl, R and R' are alkyls of from 1-20 carbon atoms, and m and n are 0 to 5, with at least one of them being at least 1.
• the invention also provides a new and unobvious method for preparing the above-defined compounds which comprises reacting the hydroxy derivative of the abovedefined compound (i.e., where R or R is hydrogen) with an alkyl halide in a dialkyl formamide solvent, or in dimethylsulfoxide or acetonitrile, in the presence of an alkali metal carbonate.
• one of the methods for preparing the alkoxy-substituted diarylamines of this invention is be lieved to be novel and unobvious from any known art.
• the known methods for producing the compounds involve the preparation of the alkali metal derivative of the starting hydroxy diarylamine prior to reaction with the alkyl halide. This is necessary in the known procedures because in the absence of the alkali metal derivative there is a substantial competitive reaction to the alkyl halide with the amine function.
• By running the reaction in the presence of an alkali metal carbonate and a suitable solvent as disclosed there is no need to make, as a separate first step, the alkali metal salt of the aminophenol.
• the reaction of the aminophenol with alkali metal carbonate (the alkali metal including sodium, lithium, potassium and cesium) is not merely an in situ reaction. It appears that the dimethyl sulfoxide, acrylonitrile or dialkyl formamides, and especially dimethylformamide, have a selective effect for giving etherification, yielding up to 97% of etherified product in the examples illustrated in detail hereinbelow. On the other hand, the same reaction when run in different solvents yields very substantial amounts of N-alkylation rather than etherification.
• good product yields can be expected within the range of from about C. to about 200 0., preferably from about to about C.
• the reaction can be completed in 2 to 3 hours, but may take several hours, e.g. up to 10 or 12, depending upon the temperature and specific reactants employed.
• the aminophenol and alkyl halide may be used up to a molar ratio of about 1:15 of the respective reactants, especially at the lower temperatures. Preferably, however, the ratio should be about 1:1.
• from about 1 to about 10 equiv alents of carbonate, preferably about 3 equivalents, can be used per equivalent of aminophenol.
• the lubricants which may be improved by the alkoxy diarylamines are mineral and synthetic lubricating oils and greases made therefrom.
• the mineral oils will be understood to embrace not only the parafiinic, but also the naphthenic members.
• synthetic oils are meant synthetic hydrocarbons, polyalkylene oxide oils, polyacetals, polysilicones and the like, as well as synthetic ester oils. Of the latter type there may be mentioned those esters made from monohydric alcohols and polycarboxylic acids, such as 2-ethylhexyl azelate and the like, and those made from polyhydric alcohols and aliphatic monocarboxylic acids.
• esters prepared from the trimethylols such as the ethane, propane and butane derivatives thereof, 2,2-disubstituted propane-diols and pentaerythritol with aliphatic monocarboxylic acids containing from about 4 to about 20 carbon atoms. Mixtures of such acids may be used to prepare the esters.
• Preferred in the practice of this invention are the esters prepared from pentaerythritol and a mixture of C -C acids. In making such esters, a generally acceptable product can be made from commercial pentaerythritol containing about 88% of the mono-form and about 12% of the di-form.
• the additives of this invention may be used at a concentration of from about 0.005 to about preferably from about 0.1 to about 5% by weight of the lubricant.
• EXAMPLE 1 4-n-octoxydiphenylamine A mixture of 19 g. of 4-hydroxydi'phenylamine, 16 g. of l-chlorooctane and 57.6 g. of anhydrous potassium carbonate in 150 ml. of N,N-dimethylformamide was refiuxed for 6.5 hours. The resulting reaction mixture was cooled below 100 and was poured into a large excess of cold water. The resulting crystalline solids were collected by filtration. There was thus obtained 29.5 g. (97%) of the 4-n-octoxydiphenylamine, melting point 4243.
• EXAMPLE 2 Z-methoxydiphenylamine
• a mixture of 50 g. of 2-ch1orobenzoic acid, 66.1 g. of anhydrous potassium carbonate, 79 g. of 2-methoxyaniline and 300 ml. of diethyleneglycol dimethyl ether was heated to 140 C.
• To this mixture about 1 g. of copper bronze and about 0.1 g. of copper iodide were added and heating at 140-145" while stirring was continued for about 3 hours.
• the reaction mixture was cooled to about 100 and poured into water.
• the aqueous mixture was filtered and the filtrate was acidified with acetic acid, heated to boiling and filtered. There was collected 58 g. (75%) of tan crystalline Z-methoxydiphenylamine-Z'- canboxylic acid, M.P. 171-172.
• EXAMPLE 4' 3-octoxy-4-tert-octyl diphenylamine A mixture of 75 g. of 3-octoxydiphenylamine and 39.2 g. of diisobutylene were heated to obtain a homogeneous solution. 1 g. of anhydrous aluminum chloride was added to the homogeneous solution and the whole was heated at 135 C. for 6 /2 hours. Following this heating period, the unreacted olefin was removed by distillation and the residue was dissolved in ethyl ether, washed with a dilute aqueous potassium hydroxide and finally withv water. After drying, the solvent was removed by distillation. The residue yielded the product boiling '235240 C. at less than 0.1 mm. of Hg pressure.
• Example- 5 4-ethoxy DPA' 2 6... 3-octoxy DPA. 1. 7- 4-0ctoxy DPA. 1 8.
• 4-oetoxy PAN I 9- 4-decoxy PAN. 1 10- dodecoxy DPA.. 1 11 4-dodecoxy DPA- 1 12.
• 4-octoxy PB 1 13-- -decoxy PBN. 1 14.- 4 oetadecoxy PBN 3 15 3-benzyloxy DPA.. 1 16.
• test composition A sample of the test composition is heated and air at the rate of about 5 liters per hour is passed through for a period of about 24 hours.
• Present in the test sample are specimens of iron, copper, aluminum, and lead.
• the kinematic viscosity is measured at 100 F. before and after treating to give the change inviscosity (percent KV Weight Initial Additive, percent Temp., Initial KV, cs. AKV, Example additive NN ANN at 100 F. percent Sludge N 425 5.9 22s Nil.
• the additional additives may include other antioxidants, such as amines, load carrying agents, metal suppressors and the like.
• the following table summarizes the results obtained using combinations of alkoxy diarylamines and other amines. In all cases, the same lubricant as above was used. All tests were at 450 F. and employed 1% by weight of each of the two additives.
• diarylamines are represented by the formula R,,Ar-NI-I-Ar'---R' wherein Ar and Ar are independently selected from the group consisting of phenyl and naphthyl, R and R are hydrogen or (E -C alkyl and x and y are 0 to the available positions on the ring. 75
• a lubricant composition comprising a major amount of a lubricant and an amount sufficient to improve the oxidation properties thereof a compound of the formula wherein Ar and AR are selected from the group consisting of naphthyl, anthryl and phenanthryl, R and R are benzyl groups or are alkyl groups containing from 1 to about 20 carbon atoms and each m and'n is from 0 to 5, at least one of m and n being at least 1.
• composition of claim 1 wherein said compound is present in said composition in an amount of from about 0.005 to about 10% by weight of said lubricant.
• composition of claim 1 wherein the lubricant is a lubricating oil or grease.
• composition of claim 3 wherein the lubricating oil is a synthetic ester oil.
• composition of claim 4 wherein the synthetic ester oil is made from pentaerythritol and an aliphatic monocarboxylic acid containing from 1 to about 20 carbon atoms.
• composition of claim 1 additionally having therein a minor amount of diarylamine of the formula wherein Ar and Ar are independently selected from the group consisting of phenyl and naphthyl, R and R are independently selected from the group consisting of hydrogen and C -C alkyl and x and y are 0 to the available positions on the ring.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Lubricants (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1971
  • 1971-11-05 US US00196203A patent/US3781206A/en not_active Expired - Lifetime
• 1972
  • 1972-07-13 CA CA147,042A patent/CA979879A/en not_active Expired
  • 1972-07-17 ZA ZA724901A patent/ZA724901B/xx unknown
  • 1972-07-18 GB GB3354472A patent/GB1393605A/en not_active Expired
  • 1972-08-16 DE DE2240298A patent/DE2240298A1/de active Pending
  • 1972-08-30 JP JP8638972A patent/JPS539241B2/ja not_active Expired
  • 1972-10-30 IT IT31125/72A patent/IT970082B/it active
  • 1972-11-03 FR FR7238995A patent/FR2158500B1/fr not_active Expired
  • 1972-11-03 NL NL7214937A patent/NL7214937A/xx not_active Application Discontinuation

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