[go: up one dir, main page]

US3677944A - Polyphenyl thioether lubricating compositions - Google Patents

Polyphenyl thioether lubricating compositions Download PDF

Info

Publication number
US3677944A
US3677944A US102154A US3677944DA US3677944A US 3677944 A US3677944 A US 3677944A US 102154 A US102154 A US 102154A US 3677944D A US3677944D A US 3677944DA US 3677944 A US3677944 A US 3677944A
Authority
US
United States
Prior art keywords
sulfide
bis
polyphenyl
diphenyl
phenylmercapto
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
US102154A
Inventor
Frank S Clark
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.)
Monsanto Co
Original Assignee
Monsanto Co
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 Monsanto Co filed Critical Monsanto Co
Application granted granted Critical
Publication of US3677944A publication Critical patent/US3677944A/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
    • 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
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/093—Coal
    • C10J2300/0936—Coal fines for producing producer gas
    • 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
    • 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
    • C10M2211/044—Acids; Salts or esters 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/06—Perfluorinated 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
    • C10M2217/042—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone
    • 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
    • C10M2217/043—Mannich bases
    • 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
    • C10M2219/086—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing sulfur atoms 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
    • 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
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium 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
    • 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
    • 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
    • C10M2223/042—Metal 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/061—Metal 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
    • 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
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • 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
    • C10N2040/12—Gas-turbines
    • 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
    • C10N2040/12—Gas-turbines
    • C10N2040/13—Aircraft turbines

Definitions

  • Lubricating compositions comprising polyphenyl thioethers, polyphenyl ethers-thioethers or mixtures thereof and containing small amounts of a perfluoro aliphatic dibasic acid have improved lubricating properties. These compositions are useful as lubricants over wide temperature ranges.
  • This invention relates to improved lubricating compositions comprising polyphenyl thioethers, mixed polyphenyl ethers-thioethers and mixtures thereof, containing from 3 to 8 aromatic groups and a small amount of a perfluoro aliphatic dibasic acid as a lubricating additive.
  • Polyphenyl thioethers and polyphenyl ether-thioether combinations have found wide application as functional fluids due to their excellent thermal stability and lubricity. For example they have been found to be valuable as hydraulic fluids and as lubricants in motor operation, particularly in jet engines.
  • an object of the present invention is to provide for improved lubricating compositions employing polyphenyl thioethers, polyphenyl ether-thioethers, or mixtures thereof as base stocks.
  • compositions consisting essentially of a major amount of a polyphenyl thioether base fluid having the formula tains 1 to 4 carbon atoms or a halogenated phenylene group wherein the halogen is fluorine, bromine or chlorine, and Y is selected from oxygen and sulfur but at least one of the Ys is sulfur and n is an integer having a Value of from 1 to 6 and an additive amount of a perfluorinated aliphatic dibasic acid, have unusual ability to lubricate under high loads at high temperatures.
  • the amount of the perfluoro aliphatic dibasic acid employed in the compositions of this invention can range from about 0.01 to about 0.2% by weight. It is preferred to employ the acids in the compositions of this invention in amounts of from about 0.05 to 0.1% by weight based upon the total composition.
  • n is an integer of from 1 to 6. It is particularly preferred to employ perfluorinated dibasic acids of Formula I wherein n is an integer of from 2 to 4.
  • Illustrative of the perfluorinated dibasic acids represented by Formula I are, for example perfluoro malonic acid, perfluoro succinic acid, perfluoro glutaric acid, perfluoro adipic acid, perfluoro pimelic acid, and perfluoro suberic acid.
  • the improvement in lubricity characteristics achieved by the addition of the perfluoro aliphatic dibasic acid to the polyphenyl thioether base fluid is unusual and surprising. Wear on a simulated bearing surface is especially decreased at test temperatures of 640 F. whereas when the base fluid is tested without the additive the lubricity of the base' fluid is not sufficient and the fluid fails the test after a short time.
  • the polyphenyl thioethers employed in the composition of this invention have from 3 to 8 benzene rings and from 1 to 7 sulfur atoms with the sulfur atoms joining the benzene rings in chains as ether linkages.
  • polyphenyl thioether as used herein is meant a compound or physical mixture of compounds represented by Formula I.
  • the term includes compounds wherein all of the Ys in Formula I are sulfur.
  • the term also includes those compounds which contain both oxygen and sulfur linkages betwen the benzene rings.
  • compositions of this invention contain a major amount of the polyphenyl thioether base stock, i.e., at least 50% by weight of the total composition comprises a polyphenyl thioether. It is preferred that at least 60% by weight of the composition be a polyphenyl thioether base stock and even more preferred that at least by weight of the total composition comprise a polyphenyl thioether.
  • Illustrations of the alkyl-substituents present in the phenyl and phenylene groups of the polyphenyl thioethers are for example, methyl, ethyl, propyl, butyl and the like. Illustrations of the alkoxy-substituents are, for example, methoxy, ethoxy, propoxy, butoxy and their isomers.
  • compositions of this invention can also contain from 0.01 to 10% by weight of the total composition of -a dialkyl hydrogen phosphite extreme pressure additive.
  • dialkyl hydrogen phosphites useful are those wherein the alkyl groups contain from 1 to 12 carbon atoms. These alkyl groups are for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, hexyl, decyl, isodecyl, dodecyl and the like.
  • polyphenyl thioethers which can be employed as base stocks for the compositions of this in vention are the bis(phenylmercapto)benzenes.
  • bromine and fluorine examples are as follows:
  • 4,4'-bis (m-trifiuoromethylphenylmercapto) diphenyl ether 3 ,4'-1b is m-trifluoromethylphenylmercapto diphenyl ether 2,3'-bis(m-trifluoromethylphenylmercapto)diphenyl ether 3,3'-bis(p-trifiuoromethylphenylmercapto)diphenyl ether 3,3'-bis (o-trifiuoromethylphenylmercapto)diphenyl ether 3,3'-bis(m-methoxyphenylmercapto)diphenyl ether 3,4'-bi's(rn-isopropoxyphenylmercapto)diphenyl ether 2-(m-tolyloxy)-2-phenylmercaptodiphenyl sulfide 2-(p-tolyloxy)-3'-phenylmercaptodiphenyl sulfide 2-(o-tolyloxy)
  • a polyphenyl thioether-polyphenyl ether-thioether lubricant composition is prepared by combining perfluoro glutaric acid (0.10 gram) with grams of a thioether of the following composition:
  • the resultant mixture was tested for lubricity on a high temperature wear machine.
  • This machine comprises a steel shaft rotating on a silvered-bronze disc so that there is line contact between the shaft and the disc.
  • This test simulates the cage wear of silver plated bronze bearing cages.
  • a lever movable about an axis permits the test disc to be loaded against the test shaft.
  • the heated steel shaft (640 F.) is rotated against the disc at 30,180 r.p.m.s at a load of 2.25 dekanewtons while the contacting surfaces are lubricated with the test oil at a flow rate of 1 ml. per minute.
  • Example 1 When the mixture of Example 1 was tested at 640 F. and also at 714 F. the shaft did not seize and the scar wear was not excessive.
  • the lubrication of the fluid from Example 1 was also shown with a slow speed four ball machine.
  • a slow speed four ball machine measures the boundary lubricity action of additives.
  • This test is a variation of the well known Shell Four Ball Test in which a ball is rotated against three stationary balls. Wear scars and/or seizure loads measure additive lubricity. In the slow speed instrument the three stationary balls are replaced with circular discs. Standard operating condition are:
  • the speed of rotation is very low, namely one r.p.m. This equals 0.88 inch/minute. This is done for two reasons. It insures boundary conditions, i.e., metal to metal contact. It also eliminates metal skin temperature flashes which can occur at high speeds. Thus the bulk oil temperature is equivalent to the metal surface temperature. Under these conditions wear is negligible and friction is used to follow lubrication. After covering the ball and disc with the test oil, the initial friction is recorded. The test sample is then heated at 700 F. with continuous recording of the friction. This gives a boundary friction-temperature profile for the experimental fluid over this temperature range.
  • Example 1 This mixture of Example 1 was tested by this procedure wherein R is a phenyl group or a substituted phenyl group, R is a phenylene group or substituted phenylene group, in which the substituents on said phenyl and phenylene groups are halogen, alkyl or alkoxy containing from 1 to 4 carbon atoms, In is an integer of from 1 to 6, Y is sulfur or oxygen provided that at least one of the groups represented by Y is sulfur, and mixtures of such thioethers and from about 0.01 to about 0.2% by weight of a perfluoro dibasic aliphatic acid of the formula wherein n is an integer of from 1 to 8.
  • a composition of claim 1 wherein said perfluoro dibasic aliphatic acid is perfluoroglutaric acid.
  • composition of claim 2 wherein said perfluoro dibasic aliphatic acid is perfluoroglutanc acid.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

LUBRICATING COMPOSITIONS COMPRISING POLYPHENYL THIOETHERS, POLYPHENYL ETHERS-THIOETHERS OR MIXTURES THEROF AND CONTAINING SMALL AMOUNTS OF A PERFLUORO ALIPHATIC DIBASIC ACID HAVE IMPROVED LUBRICATING PROPERTIES. THESE COMPOSITIONS ARE USEFUL AS LUBRICANTS OVER WIDE TEMPERATURE RANGES.

Description

United States Patent O1 3,677,944 POLYPHENYL THIOETHER LUBRICATING COMPOSITIONS Frank S. Clark, St. Louis, Mo., assignor to Monsanto Company, St. Louis, M0. N Drawing. Filed Dec. 28, 1970, Ser. No. 102,154
Int. Cl. C10m 1/38, 1/30 US. Cl. 25248.4 Claims ABSTRACT OF THE DISCLOSURE Lubricating compositions comprising polyphenyl thioethers, polyphenyl ethers-thioethers or mixtures thereof and containing small amounts of a perfluoro aliphatic dibasic acid have improved lubricating properties. These compositions are useful as lubricants over wide temperature ranges.
This invention relates to improved lubricating compositions comprising polyphenyl thioethers, mixed polyphenyl ethers-thioethers and mixtures thereof, containing from 3 to 8 aromatic groups and a small amount of a perfluoro aliphatic dibasic acid as a lubricating additive.
'Polyphenyl thioethers and polyphenyl ether-thioether combinations have found wide application as functional fluids due to their excellent thermal stability and lubricity. For example they have been found to be valuable as hydraulic fluids and as lubricants in motor operation, particularly in jet engines.
Development of synthetic base stocks such as the polyphenyl thioether has provided lubricant fluids which are useful at elevated temperature such as 400 to 500 F. It is known that one of the aspects in which the polyphenyl thioether base stocks are considered deficient is in their lubricating characteristics. These lubricating characteristics include the load-carrying abilities and wear properties, especially under conditions of high pressures and temperatures reached in the advance design aircraft engines. Thus there is a demand for polyphenyl thioethers having improved lubricity properties.
-An object of the present invention is to provide for improved lubricating compositions employing polyphenyl thioethers, polyphenyl ether-thioethers, or mixtures thereof as base stocks.
These and other objects will become evident upon consideration of the following specification and examples.
It has now been found that compositions consisting essentially of a major amount of a polyphenyl thioether base fluid having the formula tains 1 to 4 carbon atoms or a halogenated phenylene group wherein the halogen is fluorine, bromine or chlorine, and Y is selected from oxygen and sulfur but at least one of the Ys is sulfur and n is an integer having a Value of from 1 to 6 and an additive amount of a perfluorinated aliphatic dibasic acid, have unusual ability to lubricate under high loads at high temperatures.
The amount of the perfluoro aliphatic dibasic acid employed in the compositions of this invention can range from about 0.01 to about 0.2% by weight. It is preferred to employ the acids in the compositions of this invention in amounts of from about 0.05 to 0.1% by weight based upon the total composition. a
3,677,944 Patented July 18, 1972 ice wherein n is an integer of from 1 to 6. It is particularly preferred to employ perfluorinated dibasic acids of Formula I wherein n is an integer of from 2 to 4.
Illustrative of the perfluorinated dibasic acids represented by Formula I are, for example perfluoro malonic acid, perfluoro succinic acid, perfluoro glutaric acid, perfluoro adipic acid, perfluoro pimelic acid, and perfluoro suberic acid.
The improvement in lubricity characteristics achieved by the addition of the perfluoro aliphatic dibasic acid to the polyphenyl thioether base fluid is unusual and surprising. Wear on a simulated bearing surface is especially decreased at test temperatures of 640 F. whereas when the base fluid is tested without the additive the lubricity of the base' fluid is not sufficient and the fluid fails the test after a short time.
The polyphenyl thioethers employed in the composition of this invention have from 3 to 8 benzene rings and from 1 to 7 sulfur atoms with the sulfur atoms joining the benzene rings in chains as ether linkages.
By the term polyphenyl thioether" as used herein is meant a compound or physical mixture of compounds represented by Formula I. The term includes compounds wherein all of the Ys in Formula I are sulfur. The term also includes those compounds which contain both oxygen and sulfur linkages betwen the benzene rings.
The compositions of this invention contain a major amount of the polyphenyl thioether base stock, i.e., at least 50% by weight of the total composition comprises a polyphenyl thioether. It is preferred that at least 60% by weight of the composition be a polyphenyl thioether base stock and even more preferred that at least by weight of the total composition comprise a polyphenyl thioether.
Illustrations of the alkyl-substituents present in the phenyl and phenylene groups of the polyphenyl thioethers are for example, methyl, ethyl, propyl, butyl and the like. Illustrations of the alkoxy-substituents are, for example, methoxy, ethoxy, propoxy, butoxy and their isomers.
The compositions of this invention can also contain from 0.01 to 10% by weight of the total composition of -a dialkyl hydrogen phosphite extreme pressure additive. The dialkyl hydrogen phosphites useful are those wherein the alkyl groups contain from 1 to 12 carbon atoms. These alkyl groups are for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, hexyl, decyl, isodecyl, dodecyl and the like.
Illustrative of the polyphenyl thioethers which can be employed as base stocks for the compositions of this in vention are the bis(phenylmercapto)benzenes. For example bis (m-phenylmercapto) benzene bis (o-phenylmercapto)benzene bis (p-phenylmercapto) benzene bis (m-phenylmercaptophenyl) sulfide bis (o-phenylmercaptophenyl) sulfide bis (p-phenylmercaptophenyl) sulfide (m-pllfiieinylmercaptophenyl) (o-phenylmercaptophenyl) su e p-phenylmercapto-m'-phenylmercapto diphenyl sulfide o-bis(o-phenylmercaptophenylmercapto) benzene p-bis (p-phenylmercaptophenylmercapto) benzene p-bis (o-phenylmercaptophenyhnercapto)benzene p-bis(m-pheny1mercaptophenylmercapto)benzene m-bis (p-phenylmercaptophenylmercapto)benzene o-bis (p-phenylmercaptophenylmercapto) benzene and the like and mixtures thereof.
Illustrative of the mixed polyphenyl ether-thioether compounds which can be employed as base stocks in the compositions of this invention are for example,
o-phenylmercapto-m-phenoxy benzene p-phenylmercapto-o-phenoxy benzene m-phenoxy-p-phenylmercapto benzene o-phenylmercapto-p-phenoxydiphenyl sulfide o-phenylmercapto-m-phenoxydiphenyl sulfide o-phenoxy-m'-phenylmercaptodiphenyl sulfide m-phenoxy-p'-phenylmercaptodiphenyl sulfide -phenoxy-p'-phenylmercaptodiphenyl sulfide p-phenoxy-p-phenylmercaptodiphenyl sulfide o-phenoxy-o'-phenylmercaptodiphenyl sulfide o,o' -bis (phenylmercapto)diphenyl ether o-phenylmercapto-m-phenyhnercaptodiphenyl ether 'o phenylmercapto-p-phenylrnercaptodiphenyl ether m-(m-phenylmercaptophenylmercapto) (m-phenoxypheny1mercapto)benzene [m-(m-phenylmercaptophenylmercapto)phenyl] [m- (m-phenoxyphenylmercapto) phenyl] sulfide 3 (m-phenylmercaptophenylmercapto) -3'- (m-phenylmercaptophenoxy)diphenyl sulfide 3,3 -bis m-phenylmercaptophenylmercapto) diphenyl ether '3-(m-phenylmercaptophenylmercapto)-3'-(m-phenoxyphenoxy) diphenyl sulfide 4- (m-phenylmercaptophenylmercapto -4'- nil-phenylmercaptophen-oxy) diphenyl ether 3- (m-phenylmercaptophenylmercapto) -3'- (m-phenoxyphenylmercapto) diphenyl ether 4,4'-bis(m-phenylmercaptophenoxy)diphenyl sulfide 4,4'-bis(m-phenoxyphenylmercapto)diphenyl sulfide 3 m-phenoxyphenylmercapto) -3 (m-phenylmercaptophenoxy)diphenyl sulfide 3,3-bis(m-phenylmercaptophenoxy)diphenyl ether '4- (m-phenylmercaptophenylmercapto)-4'-(m-phenoxyphenoxy)diphenyl ether 3- (p-phenylmercaptophenoxy) -3 (p-phenoxyphenoxy) diphenyl sulfide 3-(m-phenylmercaptophenoxy)-3'-(m-phenoxyphenylmercapto)diphenyl ether 3,3-bis(m-phenoxyphenylrnercapto)diphenyl ether and 3- (m-phenoxyphenylmercapto -3 (m-phenoxyphenoxy) diphenyl sulfide of 1 to 4 carbon atoms and halogen such as chlorine,
bromine and fluorine. Examples of such compounds are as follows:
4,4'-bis (m-trifiuoromethylphenylmercapto) diphenyl ether 3 ,4'-1b is m-trifluoromethylphenylmercapto diphenyl ether 2,3'-bis(m-trifluoromethylphenylmercapto)diphenyl ether 3,3'-bis(p-trifiuoromethylphenylmercapto)diphenyl ether 3,3'-bis (o-trifiuoromethylphenylmercapto)diphenyl ether 3,3'-bis(m-methoxyphenylmercapto)diphenyl ether 3,4'-bi's(rn-isopropoxyphenylmercapto)diphenyl ether 2-(m-tolyloxy)-2-phenylmercaptodiphenyl sulfide 2-(p-tolyloxy)-3'-phenylmercaptodiphenyl sulfide 2-(o-tolyloxy) -4'-phenylmercaptodiphenyl sulfide 3-(m-tolyloxy)-3'-phenylmercaptodiphenyl sulfide 3-(m-tolyloxy)-4'-phenylmercaptodiphenyl sulfide 4- (m-tolyloxy) -4'-phenylmercaptodiphenyl sulfide 3-xylyloxy-4-phenylmercaptodiphenyl sulfide 3-xylyloxy-3-phenylmercaptodiphenyl sulfide 3-phenoxy-3'-(m-tolylmercapto) diphenyl sulfide 3-phenoxy-4'(m-tolylmercapto)diphenyl sulfide 2-phenoxy-3'- (p-tolylmercapto)diphenyl sulfide 3-phenoxy-4'-(m-isopropylphenylmercapto)diphenyl sulfide 3-phenoxy-3 (m-isopropylphenylmercapto) diphenyl sulfide 3-m-toloxy-3'-(m-isopropylphenylmercapto1 diphenyl sulfide 4-(m-trifluoromethylphenoxy)-4-phenylmercaptodiphenyl sulfide 3- (m-trifiuoromethylphenoxy) -4'-phenylmercaptodiphenyl sulfide 2- (m-trifluoromethylphenoxy) -3 '-phenylmercaptodiphenyl sulfide 3 m-trifiuoromethylphenoxy) -3 '-phenylmercaptodiphenyl sulfide 3-(p-chlorophenoxy)-3-phenylmercaptodiphenyl sulfide 3- (m-bromophenoxy) -4-phenylmercaptodiphenyl sulfide bis[m-(m-chlorophenoxy)phenyl1sulfide m-bisE3-(p-methylphenylmercapto)phenoxy1benzene rn-bis[3-(m-trifluoromethylphenoxy)phenylmercapto]- benzene m-bis [3- m-bromophenoxy) phenylmercapto] benzene 3,3 '-bis[mp-methylphenylmercapto) phenoxy] diphenyl sulfide 3 A 3; [mp-methylphenylmercapto )phenoxy] diphenyl su e 3-(p-xenyloxy)-3'-phenylmercapto diphenyl sulfide,
EXAMPLE 1 A polyphenyl thioether-polyphenyl ether-thioether lubricant composition is prepared by combining perfluoro glutaric acid (0.10 gram) with grams of a thioether of the following composition:
Percent by wt. Meta-bis(phenylmercapto benzene 50 Bis (phenoxyphenyl) sulfide 12.5
( Phenoxyphenyl) (phenylmercaptophenyl) sulfide 23 .5 Bis (phenylmercaptophenyl)sulfide 12.65 3 ring and 5 ring thioethers -a--- 1.35
and containing 10 parts per million of a dimethyl silicone antifoam agent (Dow-Corning-ZOO, 350 cs. fluid). After stirring at 40 C. to dissolve the acid, the mixture is cooled to room temperature and filtered.
The resultant mixture was tested for lubricity on a high temperature wear machine. This machine comprises a steel shaft rotating on a silvered-bronze disc so that there is line contact between the shaft and the disc. This test simulates the cage wear of silver plated bronze bearing cages. A lever movable about an axis permits the test disc to be loaded against the test shaft. The heated steel shaft (640 F.) is rotated against the disc at 30,180 r.p.m.s at a load of 2.25 dekanewtons while the contacting surfaces are lubricated with the test oil at a flow rate of 1 ml. per minute. In the test the shaft requires 1 minute rotation to reach speed (30,180 r.p.m.) and is maintained at this speed for 5 minutes and is then allowed to coast to a stop (1 minute). The wear scar is then measured. A test failure is indicated by seizure of the shaft and disc or an excessive wear scar.
When the mixture of Example 1 was tested at 640 F. and also at 714 F. the shaft did not seize and the scar wear was not excessive.
When the base fluid was tested at 640 F. it failed the test.
The lubrication of the fluid from Example 1 was also shown with a slow speed four ball machine. A slow speed four ball machine measures the boundary lubricity action of additives. This test is a variation of the well known Shell Four Ball Test in which a ball is rotated against three stationary balls. Wear scars and/or seizure loads measure additive lubricity. In the slow speed instrument the three stationary balls are replaced with circular discs. Standard operating condition are:
3 kg. load 1 r.p.m. Room temperature to 700 F.
The speed of rotation is very low, namely one r.p.m. This equals 0.88 inch/minute. This is done for two reasons. It insures boundary conditions, i.e., metal to metal contact. It also eliminates metal skin temperature flashes which can occur at high speeds. Thus the bulk oil temperature is equivalent to the metal surface temperature. Under these conditions wear is negligible and friction is used to follow lubrication. After covering the ball and disc with the test oil, the initial friction is recorded. The test sample is then heated at 700 F. with continuous recording of the friction. This gives a boundary friction-temperature profile for the experimental fluid over this temperature range.
This mixture of Example 1 was tested by this procedure wherein R is a phenyl group or a substituted phenyl group, R is a phenylene group or substituted phenylene group, in which the substituents on said phenyl and phenylene groups are halogen, alkyl or alkoxy containing from 1 to 4 carbon atoms, In is an integer of from 1 to 6, Y is sulfur or oxygen provided that at least one of the groups represented by Y is sulfur, and mixtures of such thioethers and from about 0.01 to about 0.2% by weight of a perfluoro dibasic aliphatic acid of the formula wherein n is an integer of from 1 to 8.
'2. A composition of claim 1 wherein said perfluoro dibasic aliphatic acid is present in amounts of from about 0.05 to about 0.1% by weight.
3. A composition of claim 1 wherein said perfluoro dibasic aliphatic acid is perfluoroglutaric acid.
4. A composition of claim 2 wherein said perfluoro dibasic aliphatic acid is perfluoroglutanc acid.
5. A composition of claim 1 where n is from 1 to 3.
References Cited UNITED STATES PATENTS 2,262,773 11/1941 Lincoln et a1. 25254.6 3,284,355 1l/1966 P'apay 25254.6 X 3,412,140 11/1968 Seil et a1. 252-54.6 X 3,565,926 2/19'71 Furey 252--54.6 X 3,579,449 5/1971 Wann et a1 25254.6 X
FOREIGN PATENTS 10/ 1960 Great Britain.
DANIEL E. WYMAN, Primary Examiner W. H. CANNON, Assistant Examiner U.S. Cl. X.R. 25254.6
US102154A 1970-09-25 1970-12-28 Polyphenyl thioether lubricating compositions Expired - Lifetime US3677944A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US7575170A 1970-09-25 1970-09-25
US10215270A 1970-12-28 1970-12-28
US10215470A 1970-12-28 1970-12-28

Publications (1)

Publication Number Publication Date
US3677944A true US3677944A (en) 1972-07-18

Family

ID=27372743

Family Applications (3)

Application Number Title Priority Date Filing Date
US00075751A Expired - Lifetime US3720614A (en) 1970-09-25 1970-09-25 Polyphenyl thioether lubricating compositions
US00102152A Expired - Lifetime US3718590A (en) 1970-09-25 1970-12-28 Polyphenyl thioether lubricating compositions
US102154A Expired - Lifetime US3677944A (en) 1970-09-25 1970-12-28 Polyphenyl thioether lubricating compositions

Family Applications Before (2)

Application Number Title Priority Date Filing Date
US00075751A Expired - Lifetime US3720614A (en) 1970-09-25 1970-09-25 Polyphenyl thioether lubricating compositions
US00102152A Expired - Lifetime US3718590A (en) 1970-09-25 1970-12-28 Polyphenyl thioether lubricating compositions

Country Status (8)

Country Link
US (3) US3720614A (en)
JP (1) JPS544025B1 (en)
BE (1) BE773019A (en)
CA (1) CA952509A (en)
DE (1) DE2147807C3 (en)
FR (2) FR2107992B1 (en)
GB (3) GB1353315A (en)
NL (1) NL7113060A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6191080B1 (en) * 1995-06-16 2001-02-20 Tonen Corporation Heat resistant lubricating oil composition

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1399236A (en) * 1971-06-02 1975-06-25 Shell Int Research Phosphorus acid esters and oil compositions containing them
US6326337B1 (en) * 2001-04-04 2001-12-04 The United States Of America As Represented By The Secretary Of The Air Force Perfluoropolyalkylether lubricant formulation with improved stability
US6789341B1 (en) 2002-05-07 2004-09-14 Mark L. Badura Firearm safety device

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL43896C (en) * 1935-12-02
US2174019A (en) * 1936-11-27 1939-09-26 Standard Oil Co Lubricant
US2262773A (en) * 1937-03-19 1941-11-18 Lubri Zol Dev Corp Lubrication
US2274291A (en) * 1938-11-26 1942-02-24 Standard Oil Co Compounded mineral oil
US2957931A (en) * 1949-07-28 1960-10-25 Socony Mobil Oil Co Inc Synthesis of compounds having a carbonphosphorus linkage
US2730499A (en) * 1951-08-01 1956-01-10 Exxon Research Engineering Co Lubricants for heavy journal bearings operating at elevated temperatures
NL233984A (en) * 1957-12-09
US2921874A (en) * 1958-01-21 1960-01-19 Aluminum Res Corp Cold forming lubricant and method of applying same
NL272801A (en) * 1960-12-23
US3116248A (en) * 1960-12-23 1963-12-31 Shell Oil Co Lubricating oil composition
US3226323A (en) * 1963-04-30 1965-12-28 Monsanto Res Corp Lubricant composition containing a haloalkanoic compound
US3284355A (en) * 1963-09-12 1966-11-08 Mobil Oil Corp Lubricating compositions
IL23789A (en) * 1964-07-01 1969-05-28 Monsanto Co Functional fluid compositions
US3426075A (en) * 1964-07-01 1969-02-04 Monsanto Co Mixed polyphenyl ethers-thioethers
DE1275535B (en) * 1966-09-03 1968-08-22 Zentrales Buero Fuer Neuererwe Process for the preparation of mixtures from liquid polyphenylthioethers
GB1162443A (en) * 1966-11-10 1969-08-27 Mobil Oil Corp Additives for Organic Lubricants.
US3579449A (en) * 1968-09-26 1971-05-18 Procter & Gamble Lubricant composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6191080B1 (en) * 1995-06-16 2001-02-20 Tonen Corporation Heat resistant lubricating oil composition
US6586376B1 (en) 1995-06-16 2003-07-01 Exxonmobil Research And Engineering Company Heat resistant lubricating oil composition

Also Published As

Publication number Publication date
DE2147807B2 (en) 1981-06-25
GB1352828A (en) 1974-05-15
JPS544025B1 (en) 1979-03-01
US3718590A (en) 1973-02-27
FR2107992B1 (en) 1974-03-29
FR2107992A1 (en) 1972-05-12
CA952509A (en) 1974-08-06
DE2147807A1 (en) 1972-03-30
BE773019A (en) 1972-03-24
GB1351651A (en) 1974-05-01
DE2147807C3 (en) 1982-04-22
US3720614A (en) 1973-03-13
FR12427E (en)
GB1353315A (en) 1974-05-15
NL7113060A (en) 1972-03-28

Similar Documents

Publication Publication Date Title
US2691000A (en) Lubricating oils
US3274107A (en) Lubricant composition containing a sulfide
US2160915A (en) Lubricant
US3748269A (en) Polyphenyl thioether lubricating compositions
NL9400493A (en) Use of bismuth joints in high pressure grease lubricant compositions for long life rolling bearing applications.
US3677944A (en) Polyphenyl thioether lubricating compositions
US3169925A (en) High temperature lubricants and phosphorus containing polymers
JP2728736B2 (en) Urea grease composition
US3704277A (en) Polyphenyl ether lubricating compositions
US3492229A (en) Functional fluid compositions
Sharma et al. High temperature lubricants—oils and greases
US3714043A (en) Polyphenyl thioether lubricating compositions
RU2202601C2 (en) Average-temperature lubricant for heavily loaded units friction, roller and slider units
US2154098A (en) Extreme pressure lubricant
JP4977360B2 (en) Lubricating grease composition
US2138835A (en) Lubricant
US4755310A (en) Silicone grease composition containing a chlorinated alicyclic compound
US3413225A (en) Functional fluid containing azo benzene derivatives as antioxidants
US3778472A (en) Phenoxyphenylphosphinic acids and improved polyphenyl thioether lubricating compositions
US2424204A (en) Extreme pressure lubricants
US3189548A (en) Polyphenyl ethers containing an extreme pressure additive
RU2057792C1 (en) Plastic lubricant
US3226323A (en) Lubricant composition containing a haloalkanoic compound
US3088912A (en) Lubricating composition
US3706668A (en) Polyphenyl ether lubricating compositions