US3900410A - Lubricating oil compositions containing trialkyl-substituted phenols and benzotriazole - Google Patents

Lubricating oil compositions containing trialkyl-substituted phenols and benzotriazole Download PDF

Info

Publication number
US3900410A
US3900410A US353394A US35339473A US3900410A US 3900410 A US3900410 A US 3900410A US 353394 A US353394 A US 353394A US 35339473 A US35339473 A US 35339473A US 3900410 A US3900410 A US 3900410A
Authority
US
United States
Prior art keywords
tert
lubricating oil
butyl
benzotriazole
antioxidant
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
US353394A
Inventor
Robert E Malec
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.)
Ethyl Corp
Original Assignee
Ethyl Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ethyl Corp filed Critical Ethyl Corp
Priority to US353394A priority Critical patent/US3900410A/en
Application granted granted Critical
Publication of US3900410A publication Critical patent/US3900410A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
    • 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
    • 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
    • C10M2205/026—Butene
    • 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
    • C10M2207/02—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
    • 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts 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
    • 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
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • 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
    • C10M2215/22—Heterocyclic nitrogen 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226—Morpholines
    • 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
    • C10M2215/26—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
    • C10M2215/30—Heterocyclic 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. 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
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12

Definitions

  • ABSTRACT Lubricating oil is protected against oxidative degradation by inclusion of a 2,6-di-C -tert-alkyl-4-n-C alkylphenol,:.,e.g., 2,6-di-tert-butyl-4-n-dodecylphenol, and benzotriezole.
  • the dodecyl group appears to be a branched-chain secondary or tertiary alkyl because there is no method given for the preparation of the 4-n-alkyl derivative.
  • U.S. Pat. No. 3,717,611 the antioxidant use of 2,6-di-tert-butyl-4-dodecyl anisole and 2,6-di-trtbutyl-4-octadecyl anisole is disclosed.
  • the anisole derivatives are made from the corresponding phenol.
  • the dodecyl andoctadecyl groups appear to be secondary or tertiary since those compounds in which the alkyl is normal are so specified.
  • mineral lubricating oils are stabilized against oxidative degradation by the addition of a small antioxidant amount of a 2,6-ditert-alkyl-4-C -n-alkylphenol and a small promoter amount of benzotriazole.
  • 2 ,6-di-tert-eicosy-4-n-- groups These are represented by: 2,6-di-tert-butyl-4-ndecylphenol, 2,o-di-tert-butyl-4-n-dodecylphenol, 2,6- di-tert-butyl-4-n-tetradecylpheno], 2,6-di-tert-butyl-4- n-hexadecylphenol, 2,6-di-tert-butyl-4-noctadecylphenol, 2,6-di-tertbutyl-4-n-eicosylphenol, 2,6-di-tert-butyl-4-n-docosylphenol and 2,6-di-tertbutyl-4'n-tetracosylphenol.
  • Additives of this invention are made by heating a 2,6- di-tert-alkylphenol with a straight chain primary alcohol of the desired chain length in the presence of potassium hydroxide and a cupric oxide catalyst.
  • the alcohol is generally employed in stoichiometric excess. An amount of about 3-20 moles of alcohol per mole of phenol is satisfactory. Good results are obtained using about 0.5-0.2 mole of KOH per mole of alcohol. About 0.005-0.05 mole of cupric oxide per mole of 2,6-ditert-alkylphenol gives good results. Reaction temperatures of about 200250C. are preferred.
  • Product can be recovered by distillation. In a highly preferred embodiment the reaction mixture is distilled to remove 2,6-di-tert-alkylphenol and other more volatile components and the residue used as the phenolic antioxidant of this invention.
  • EXAMPLE 1 In a pressure reaction vessel was placed 326.] grams of 2,6-di-tert-butylphenol, 1000 grams of n-decanol, 32.8 grams of 86 per cent KOH and 0.95 gram of cupric oxide. This mixture was stirred and heated to 225C. and held at that temperature for 24 hours. Following this, the mixture was cooled, diluted with 250 ml toluene and washed with aqueous sodium bicarbonate. It was then washed with water until neutral and distilled under vacuum to isolate the product 2,6-di-tertbutyl-4-n-decylphenol (b.p. l55C., 0.250.3 mm Hg).
  • additives can be similarly prepared by substituting different straight chain alcohols containing from 8-24 carbon atoms.
  • the amount of antioxidant blended with the oil should be sufficient to impart the required degree of stability. Good results are achieved using about 0.01-3 weight per cent and, preferably, 0.05l.5 weight per cent.
  • the amount of benzotriazole should be an amount such that when used with the 2,6-di-tert-alkyl- 4-C -n-alkylphenol good overall performance is obtained. A useful range is from about 0.0l0.5 weight per cent.
  • simple lower alkyl-substituted benzotriazoles can be used such as the C alkylsubstituted benzotriazoles, e.g., 3-methylbenzotriazole, l,2,3-trimethylbenzotriazole, 6-sec-butylbenzotriazole, 4-tert-octylbenzotriazole, 4-sec-hexylbenzotriazole, and the like.
  • additives normally included in oil compositions can be beneficially used together with the additives of this invention.
  • These include zinc dialkyldithiophosphates, calcium aryl sulfonates, overbased calcium aryl sulfonates, magnesium aryl sulfonates, barium phenates, calcium phenates, barium polybutenyl ph phonates, V.l. improvers such as polybutene, ethylenepropylene copolymer, polylauryl mcthacrylate, dispersants such as polybutenyl kylenepolyamines, and the like.
  • EXAMPLE 3 In a blending vessel place 10,000 pounds of SAE-30 neutral mineral oil. To this add 100 pounds of zinc dialkyldithiophosphate (7 weight per cent zinc), 50 pounds of 2,6-di-tert-butyl-4-n-dodecylphenol, 50 pounds calcium aryl sulfonate (overbased with colloidal calcium carbonate), 250 pounds ethylenepropylene copolymer and 400 pounds of a 50 per cent oil solution of a C polybutenyl succinimide of tetraethylenepentamine. Stir the mixture until homogenous to obtain an oil composition suitable for. use in internal combustion engines.
  • Tests have been carried out to demonstrate the effectiveness of the present compositions. These are oxidationcorrosion tests in which oil samples are prepared containing the test additive, 0.1 per cent lead bromide and a copper-lead bearing. These are heated to 300F. and air bubbled through them for 48 hours at 48 liters per hour. Criteria of the additive effectiveness are the increase in acid number, increase in viscosity and bearing weight loss. The results obtained were as follows:
  • R and R are tert alkyl groups containing 4 to 7 about 20 carbon atoms and R is a straight chain primary alkyl group containing S te about 24 carbon atoms and an antioxidant promoter amount of a benzo triazole.
  • said antioxidant compounds are 2,6-di-tert-butyl-4-n- C8 -alkylphenols.
  • the phenolic additives are effective in preventing oxidative degradation but cause a large increase in bearing weight loss.
  • Inclusion of benzotriazole not only greatly reduces the bearing weight loss but, in addition, sharply reduces the acid number increase and viscosity increase, thus contributing to the overall effectiveness of the antioxidant.
  • composition of claim 1 wherein UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF GORECTION PATENT NO. 5,900, i1o

Abstract

Lubricating oil is protected against oxidative degradation by inclusion of a 2,6-di-C4-20-tert-alkyl-4-n-C8-24 alkylphenol, e.g., 2,6-di-tert-butyl-4-n-dodecylphenol, and benzotriazole.

Description

United States Patent Malec LUBRICATING OIL COMPOSITIONS CONTAINING TRIALKYL-SUBSTITUTED PIIENOLS AND BENZOTRIAZOLE Robert E. Malec, Birmingham,
Mich.
Assignee: Ethyl Corporation, Richmond, Va.
Filed: Apr. 23, 1973 Appl. No.: 353,394
Inventor:
US. Cl 252/5L5 R; 252/50; 252/392 Int. Cl C.10m 1/32 Field of Search 252/5l.5 R, 50, 42.7, 392
References Cited UNITED STATES PATENTS 6/1940 Stevens et al. 252/52 X 10/1957 Pruett 252/5l5 R 11] 3,900,410 Aug. 19, 1975 Primary Exaniinr-Delbert E. Gantz Assistant Examiner-Andrew H. Metz Attorney, Agrit, 0r FirmDonald L. Johnson; Robert A. Linn; Josepli D. Odenweller [57] ABSTRACT Lubricating oil is protected against oxidative degradation by inclusion of a 2,6-di-C -tert-alkyl-4-n-C alkylphenol,:.,e.g., 2,6-di-tert-butyl-4-n-dodecylphenol, and benzotriezole.
9 Claims, No Drawings LUBRICATING OIL COMPOSITIONS CONTAINING TRIALKYL-SUBSTITUTED PI-IENOLS AND BENZOTRIAZOLE BACKGROUND Alkylphenols have been used to provide antioxidant protection for a broad range of organic materials. For example, 2,6-di-tert-butyl-4-methylphenol is a known commercial antioxidant used in polymers, rubber and as a food additive. Polyolefin use of 2,6-di-tert-butyl-4- dodecylphenol is disclosed in Neth. PatfNo. 64/08010. The dodecyl group appears to be a branched-chain secondary or tertiary alkyl because there is no method given for the preparation of the 4-n-alkyl derivative. In U.S. Pat. No. 3,717,611 the antioxidant use of 2,6-di-tert-butyl-4-dodecyl anisole and 2,6-di-trtbutyl-4-octadecyl anisole is disclosed. The anisole derivatives are made from the corresponding phenol. The dodecyl andoctadecyl groups appear to be secondary or tertiary since those compounds in which the alkyl is normal are so specified.
Synthetic ester lubricants containing benzotriazole in addition to other constituents are disclosed in US. Pat. No. 2,971,912. Lubricating oils containing phenylborate esters are reported in Br. Pat. No. 1,287,444 to give increased undercrown and piston skirt deposit which is said to be largely eliminated by inclusion of a heterocycle such as benzotriazole.
, SUMMARY According to the present invention, mineral lubricating oils are stabilized against oxidative degradation by the addition of a small antioxidant amount of a 2,6-ditert-alkyl-4-C -n-alkylphenol and a small promoter amount of benzotriazole.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The phenolic additives of this invention are compounds having the formula:
2 ,6-di-tert-eicosy-4-n-- groups. These are represented by: 2,6-di-tert-butyl-4-ndecylphenol, 2,o-di-tert-butyl-4-n-dodecylphenol, 2,6- di-tert-butyl-4-n-tetradecylpheno], 2,6-di-tert-butyl-4- n-hexadecylphenol, 2,6-di-tert-butyl-4-noctadecylphenol, 2,6-di-tertbutyl-4-n-eicosylphenol, 2,6-di-tert-butyl-4-n-docosylphenol and 2,6-di-tertbutyl-4'n-tetracosylphenol.
Additives of this invention are made by heating a 2,6- di-tert-alkylphenol with a straight chain primary alcohol of the desired chain length in the presence of potassium hydroxide and a cupric oxide catalyst. The alcohol is generally employed in stoichiometric excess. An amount of about 3-20 moles of alcohol per mole of phenol is satisfactory. Good results are obtained using about 0.5-0.2 mole of KOH per mole of alcohol. About 0.005-0.05 mole of cupric oxide per mole of 2,6-ditert-alkylphenol gives good results. Reaction temperatures of about 200250C. are preferred. Product can be recovered by distillation. In a highly preferred embodiment the reaction mixture is distilled to remove 2,6-di-tert-alkylphenol and other more volatile components and the residue used as the phenolic antioxidant of this invention.
The following example illustrates the manner by which the phenolic additives are prepared.
EXAMPLE 1 In a pressure reaction vessel was placed 326.] grams of 2,6-di-tert-butylphenol, 1000 grams of n-decanol, 32.8 grams of 86 per cent KOH and 0.95 gram of cupric oxide. This mixture was stirred and heated to 225C. and held at that temperature for 24 hours. Following this, the mixture was cooled, diluted with 250 ml toluene and washed with aqueous sodium bicarbonate. It was then washed with water until neutral and distilled under vacuum to isolate the product 2,6-di-tertbutyl-4-n-decylphenol (b.p. l55C., 0.250.3 mm Hg).
EXAMPLE 2 In a pressure reaction vessel was placed 247.5 grams of 2,6-di-tert-butylphenol, 894 grams of n-dodecanol,
26.9 grams 86 per cent KOH and 1.2 grams cupric oxide. The vessel was flushed with hydrogen and pressurized to 100 psig with hydrogen. While stirring, it was heated to 235C. and maintained at this temperature for 24 hours. Following this, it was cooled and discharged into dilute hydrochloric acid. Discharge was completed by adding 200 ml of toluene and 300 ml of hot water to the reaction vessel, which was combined with the discharged reaction mixture. The organic phase was washed with water until almost neutral (pH 6) and then dried over magnesium sulfate. Toluene and unreacted n-decanol was distilled from the reaction mixture, leaving 403 grams of residue which assayed per cent 2,6-di-tert-butyl-4-n-dodecylphenol by VPC.
Other additives can be similarly prepared by substituting different straight chain alcohols containing from 8-24 carbon atoms.
The amount of antioxidant blended with the oil should be sufficient to impart the required degree of stability. Good results are achieved using about 0.01-3 weight per cent and, preferably, 0.05l.5 weight per cent. The amount of benzotriazole should be an amount such that when used with the 2,6-di-tert-alkyl- 4-C -n-alkylphenol good overall performance is obtained. A useful range is from about 0.0l0.5 weight per cent. Optionally, simple lower alkyl-substituted benzotriazoles can be used such as the C alkylsubstituted benzotriazoles, e.g., 3-methylbenzotriazole, l,2,3-trimethylbenzotriazole, 6-sec-butylbenzotriazole, 4-tert-octylbenzotriazole, 4-sec-hexylbenzotriazole, and the like.
Other additives normally included in oil compositions can be beneficially used together with the additives of this invention. These include zinc dialkyldithiophosphates, calcium aryl sulfonates, overbased calcium aryl sulfonates, magnesium aryl sulfonates, barium phenates, calcium phenates, barium polybutenyl ph phonates, V.l. improvers such as polybutene, ethylenepropylene copolymer, polylauryl mcthacrylate, dispersants such as polybutenyl kylenepolyamines, and the like.
The following example illustrates the preparation of a typical oil composition of this invention.
EXAMPLE 3 In a blending vessel place 10,000 pounds of SAE-30 neutral mineral oil. To this add 100 pounds of zinc dialkyldithiophosphate (7 weight per cent zinc), 50 pounds of 2,6-di-tert-butyl-4-n-dodecylphenol, 50 pounds calcium aryl sulfonate (overbased with colloidal calcium carbonate), 250 pounds ethylenepropylene copolymer and 400 pounds of a 50 per cent oil solution of a C polybutenyl succinimide of tetraethylenepentamine. Stir the mixture until homogenous to obtain an oil composition suitable for. use in internal combustion engines.
Tests have been carried out to demonstrate the effectiveness of the present compositions. These are oxidationcorrosion tests in which oil samples are prepared containing the test additive, 0.1 per cent lead bromide and a copper-lead bearing. These are heated to 300F. and air bubbled through them for 48 hours at 48 liters per hour. Criteria of the additive effectiveness are the increase in acid number, increase in viscosity and bearing weight loss. The results obtained were as follows:
succinimidesof almula:
wherein R and R are tert alkyl groups containing 4 to 7 about 20 carbon atoms and R is a straight chain primary alkyl group containing S te about 24 carbon atoms and an antioxidant promoter amount of a benzo triazole. 2. A lubricating oil said antioxidant compounds are 2,6-di-tert-butyl-4-n- C8 -alkylphenols.
3. A lubricatingoil composition of claim 2 wherein As the above results show, the phenolic additives are effective in preventing oxidative degradation but cause a large increase in bearing weight loss. Inclusion of benzotriazole not only greatly reduces the bearing weight loss but, in addition, sharply reduces the acid number increase and viscosity increase, thus contributing to the overall effectiveness of the antioxidant.
I claim:
l. A mineral lubricating oil composition containing an antioxidant amount of a compound having the for- 7. A lubricating oil composition of claim 2 wherein said antioxidant compound is 2,6-di-tert-butyl-4-nhexadecylphenol.
8. A lubricating oil composition of claim 2 wherein said antioxidant compound is 2,6-di-tert-butyl-4-noctadecylphenol.
9. A lubricating oil composition of claim 2 wherein said antioxidant compound is 2,6-di-tert-butyl-4-neicosylphenol.
composition of claim 1 wherein UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF GORECTION PATENT NO. 5,900, i1o
DATED August 9 975 mv om 1 Robert E. Melee it is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column i, in Claim 1, at lines 15-1 i, insert "about 0.01O.5 weight per cent of before "a benzoticietzole Signed and fiealed this fourteenth Day Of October 1975 [SEAL] Attest:
RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner oj'Patents and Trademarks UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,9OOA1O DATED August 19, 1975 INVENTORQI): Robert E. Malec It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column t, in Claim 1, art lines 151 t, insert "about 0.01O.5 weight per cent of" before e ioenzotriazole Signed and Sealed this fourteenth D ay Of October 1 9 75 [SEAL] A ttest:
RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ofParents and Trademarks UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 5,900,h10
DATED August 19, 1975 rNv ENT0R( s Robert E. Malec It is certified that error appears in the ab0ve-identified patent and that said Letters Patent are hereby corrected as shown below:
Column t, in Claim 1, at lines 15l t, insert about 0.01O.5 weight per cent of" before "a benzotriazole Signed and Scaled this fourteenth Day Of October 1975 [SEAL] A rtes t:
RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner of Patents and Trademarks

Claims (9)

1. A MINERAL LUBRICATING OIL COMPOSITION CONTAINING AN ANTIOXIDANT AMOUNT OF A COMPOUND HAVING THE FORMULA:
2. A lubricating oil composition of claim 1 wherein said antioxidant compounds are 2,6-di-tert-butyl-4-n-C8-24 24-alkylphenols.
3. A lubricating oil composition of claim 2 wherein said antioxidant compound is 2,6-di-tert-butyl-4-n-octylphenol.
4. A lubricating oil composition of claim 2 wherein said antioxidant compound is 2,6-di-tert-butyl-4-n-decylphenol.
5. A lubricating oil composition of claim 2 wherein said antioxidant compound is 2,6-di-tert-butyl-4-n-dodecylphenol.
6. A lubricating oil composition of claim 2 wherein said antioxidant compound is 2,6-di-tert-butyl-4-n-tetradecylphenol.
7. A lubricating oil composition of claim 2 wherein said antioxidant compound is 2,6-di-tert-butyl-4-n-hexadecylphenol.
8. A lubricating oil composition of claim 2 wherein said antioxidant compound is 2,6-di-tert-butyl-4-n-octadecylphenol.
9. A lubricating oil composition of claim 2 wherein said antioxidant compound is 2,6-di-tert-butyl-4-n-eicosylphenol.
US353394A 1973-04-23 1973-04-23 Lubricating oil compositions containing trialkyl-substituted phenols and benzotriazole Expired - Lifetime US3900410A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US353394A US3900410A (en) 1973-04-23 1973-04-23 Lubricating oil compositions containing trialkyl-substituted phenols and benzotriazole

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US353394A US3900410A (en) 1973-04-23 1973-04-23 Lubricating oil compositions containing trialkyl-substituted phenols and benzotriazole

Publications (1)

Publication Number Publication Date
US3900410A true US3900410A (en) 1975-08-19

Family

ID=23388901

Family Applications (1)

Application Number Title Priority Date Filing Date
US353394A Expired - Lifetime US3900410A (en) 1973-04-23 1973-04-23 Lubricating oil compositions containing trialkyl-substituted phenols and benzotriazole

Country Status (1)

Country Link
US (1) US3900410A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55106297A (en) * 1979-02-09 1980-08-14 Toa Nenryo Kogyo Kk Lubricating oil composition
US4233207A (en) * 1979-07-09 1980-11-11 Ciba-Geigy Corporation Hydrolytically stable ortho-alkylated phenyl phosphonites and stabilized compositions
EP0028200A1 (en) * 1979-10-29 1981-05-06 The Goodyear Tire & Rubber Company Alkylation of 2,6-di-tert.-alkylphenols with alkanediols
US4306985A (en) * 1979-02-14 1981-12-22 Atlantic Richfield Company Stabilization of hydrocracked oils with certain nitrogen containing aromatic components and phenolic components
US4836943A (en) * 1987-07-15 1989-06-06 Texaco Inc. Anti-oxidant system
US6121209A (en) * 1994-12-09 2000-09-19 Exxon Chemical Patents Inc Synergistic antioxidant systems
JP2014091695A (en) * 2012-11-02 2014-05-19 Dic Corp Method for producing hindered phenol

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2202877A (en) * 1937-04-12 1940-06-04 Gulf Oil Corp Antioxidants and petroleum oils containing the same
US2809164A (en) * 1955-04-21 1957-10-08 American Cyanamid Co Oxidation inhibitors for lubricating oil
US2890170A (en) * 1956-09-06 1959-06-09 Dow Corning Organosiloxane greases
US3032502A (en) * 1959-08-17 1962-05-01 Standard Oil Co Lubricant compositions
US3173871A (en) * 1961-06-08 1965-03-16 Castrol Ltd Lubricating oils containing benzalcyclohexylamine and bis-phenols
US3413227A (en) * 1963-12-06 1968-11-26 Geigy Chem Corp Compositions containing substituted benzotriazoles

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2202877A (en) * 1937-04-12 1940-06-04 Gulf Oil Corp Antioxidants and petroleum oils containing the same
US2809164A (en) * 1955-04-21 1957-10-08 American Cyanamid Co Oxidation inhibitors for lubricating oil
US2890170A (en) * 1956-09-06 1959-06-09 Dow Corning Organosiloxane greases
US3032502A (en) * 1959-08-17 1962-05-01 Standard Oil Co Lubricant compositions
US3173871A (en) * 1961-06-08 1965-03-16 Castrol Ltd Lubricating oils containing benzalcyclohexylamine and bis-phenols
US3413227A (en) * 1963-12-06 1968-11-26 Geigy Chem Corp Compositions containing substituted benzotriazoles

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55106297A (en) * 1979-02-09 1980-08-14 Toa Nenryo Kogyo Kk Lubricating oil composition
JPH0152438B2 (en) * 1979-02-09 1989-11-08 Toa Nenryo Kogyo Kk
US4306985A (en) * 1979-02-14 1981-12-22 Atlantic Richfield Company Stabilization of hydrocracked oils with certain nitrogen containing aromatic components and phenolic components
US4233207A (en) * 1979-07-09 1980-11-11 Ciba-Geigy Corporation Hydrolytically stable ortho-alkylated phenyl phosphonites and stabilized compositions
EP0028200A1 (en) * 1979-10-29 1981-05-06 The Goodyear Tire & Rubber Company Alkylation of 2,6-di-tert.-alkylphenols with alkanediols
US4836943A (en) * 1987-07-15 1989-06-06 Texaco Inc. Anti-oxidant system
US6121209A (en) * 1994-12-09 2000-09-19 Exxon Chemical Patents Inc Synergistic antioxidant systems
JP2014091695A (en) * 2012-11-02 2014-05-19 Dic Corp Method for producing hindered phenol

Similar Documents

Publication Publication Date Title
US4178258A (en) Lubricating oil composition
US3211652A (en) Phenolic compositions
EP0020037B1 (en) Oil-soluble friction-reducing additive, process for the preparation thereof, and lubricating oil or fuel composition containing the additive
JPH08208563A (en) High-oleic-acid polyol ester,composition containing same,andlubricant,functional fluid,and grease
US4222884A (en) Antioxidant
EP0811631A2 (en) Sulfurized phenolic antioxidant composition, method of preparing same, and petroleum products containing same
ES8202056A1 (en) Additive compositions comprising sulphurized alkyl phenol and high molecular weight dispersant
JPH0260719B2 (en)
US3224975A (en) Lubricating oil compositions
US3900410A (en) Lubricating oil compositions containing trialkyl-substituted phenols and benzotriazole
CA1327592C (en) Dispersants for oleaginous compositions
CA1162935A (en) Thio-bis-(hydrocarbyl diacid materials) as oil additives
US4698169A (en) Reaction products of alkenylsuccinic compounds with aromatic amines and lubricant compositions thereof
US3156728A (en) Thiobis (2, 6-dialkylaniline) compounds
US3208859A (en) Organic compositions stabilized with 3, 5-dialkyl-4-hydroxybenzyl amine
US3385790A (en) Antioxidant compositions
US4803004A (en) Reaction products of alkenylsuccinic compounds with aromatic amines and hindered alcohols and lubricant compositions thereof
US2898299A (en) Ester-containing lubricant compositions
US4655949A (en) Lubricating oil compositions containing organometallic additives
US3883501A (en) Sulfurized phenolic materials
US3844964A (en) Extreme pressure lubricating oil additive
US4278554A (en) Antioxidant
US3992308A (en) Lubricating oil composition containing sulfurized reaction product of mixed tertiary alkyl phenols with formaldehyde
US3224972A (en) Stabilization with a 4,4'-thiobis (2,6-dialkylaniline)
US4895579A (en) Reaction products of alkenylsuccinic compounds with aromatic amines and hindered alcohols and lubricant and fuel compositions thereof