US3714043A - Polyphenyl thioether lubricating compositions - Google Patents
Polyphenyl thioether lubricating compositions Download PDFInfo
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- US3714043A US3714043A US00148123A US3714043DA US3714043A US 3714043 A US3714043 A US 3714043A US 00148123 A US00148123 A US 00148123A US 3714043D A US3714043D A US 3714043DA US 3714043 A US3714043 A US 3714043A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
Definitions
- Phenoxyphenylphosphinic acids and lubricating compositions comprising polyphenyl thioethers, polyphenyl ethers-thioethers or mixtures thereof and small amounts of said acids have improved lubricating properties over wide temperature ranges.
- This invention relates to phenoxyphenylphosphinic acids and to improved lubricating compositions compris ing polyphenyl thioethers, mixed polyphenyl ethers-thioethers and mixtures thereof, containing from 3 to 8 aromatic groups and a small amount of said phenoxyphenylphosphinic 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 this invention is to provide novel phenoxyphenylphosphinic acids having excellent lubricating additive properties.
- Another object of this invention is to provide improved lubricating compositions comprising polyphenyl thioethers, polyphenyl ether-thioethers, or mixtures thereof and a small amount of a phenoxyphenylphosphinic acid.
- the phenoxyphenylphosphinic acids of this invention can be represented by the formula wherein R and R are alkyl of not more than 4 carbon atoms, haloalkyl of not more than 4 carbon atoms and 3 halogen (Cl, Br and F) atoms, halogen (Cl, Br and F), hydroxyl or phenyl, and m and a are integers from 0 to 3.
- R and R in the above formula include alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and t-butyl and haloalkyl such as chloromethyl, bromomethyl, chloroethyl, bromoethyl, trichloromethyl, tribromomethyl, dichloroethyl, chloro- 3,714,643 Patented Jan. 30, 1973 n-propyl, bromo-n-pro'pyl, bromo-n-butyl, bromo-tertbutyl, 1,3,3-trichlorobutyl and 1,3,3-tribromobutyl.
- alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and t-butyl
- haloalkyl such as chloromethyl, bromomethyl, chloroethyl,
- Phenoxyphenylphosphinic acids represented by the above formula include, for example,
- p-phenoxyphenylphosphinic acid o-phenoxyphenylphosphinic acid, m-phenoxyphenylphosphinic acid, p-(p-rnethylphenoxy)phenylphosphinic acid, 0- (p-methylphenoxy) -p-methylphenylphosphinic acid, p-(o-methylphenoxy)phenylphosphinic acid, p-(p-ethylphenoxy) phenylphosphinic acid, p- (o-ethylphenoxy phenylphosphinic acid, o-(o-ethylphenoxy)phenylphosphinic acid, p- (p-butylphenoxy) phenylphosphinic acid, p-(p-chlorophenoxy)phenylphosphinic acid, 0- (m-chlorophenoxy) phenylphosphinic acid, p- (p-phenylphenoxy) phenylpho
- compositions of this invention comprise a major amount of a polyphenyl thioether-base fluid of the formula RY(R Y) R wherein R is phenyl, alkyl-substituted phenyl wherein the alkyl is of not more than 4 carbon atoms, alkoxy-substituted phenyl wherein the alkoxy is of no more than 4 carbon atoms or halogenated phenyl wherein the halogen is bromine, fluorine or chlorine, R is phenylene, alkyl or alkoxy-substituted phenylene where the alkyl contains no more than 4 carbon atoms or halogenated phenylene 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 1 to 6 and a lubricating additive amount of a phenoxyphenylphosphinic acid of the formula wherein
- the amount of phenoxyphenylphosphinic acid employed in the compositions of this invention can range from about 0.01 to about 0.5% by weight. It is preferred to employ the acids in the compositions of this invention in amounts of from about 0.05 to 0.2% by weight based upon the total composition.
- 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 wherein all of the Ys in the formula are sulfur. The term also includes those compounds which contain both oxygen and sulfur linkages between 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 composiiton 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 85% 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.
- the dialkyl hydrogen phosphites useful are those wherein the alkyl groups contain from 1 to 12 carbon atoms.
- the 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 invention are the bis(phenylmercapto)benzenes.
- the phenyl and phenylene of such compounds can contain substituents, such as alkyl of l to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and halogen such as chlorine, bromine and fluorine. Examples of such compounds are as follows:
- compositions of this invention are useful as lubricants under extreme conditions.
- the compositions are especially useful for steel on steel lubrication.
- phenoxyphenylphosphinic acids of this invention are prepared by interaction of a phosphine of the formula wherein R R m and a are as defined above with ethyl alcohol and water.
- the interaction is carried out in the absence of a solvent by heating the admixture of the three components at temperatures up to and including reflux temperature. Pressure is not critical and subatmospheric, atmospheric and superatmospheric pressures can be employed. It is generally preferred to slowly add the phosphine to the ethyl alcohol and then to add the water to the admixture of phosphine and ethyl alcohol prior to heating. After reaction is complete, generally a period not exceeding more than or minutes, the excess ethyl alcohol and water are removed by azeotropic distillation with an azeotroping agent such as benzene.
- an azeotroping agent such as benzene.
- the separation of the desired phosphinic acid from the azeotroping agent is readily accomplished by conventional means well known to the art. For example, distillation, fractional distillation under reduced pressure, selective extraction, fractional distillation using a carrier gas, film distillation, evaporation, elution, or any suitable combination of these methods.
- Dichlorophenoxyphenylphosphines can be prepared by Friedel-Craft condensation of diphenyl ethers with phosphorus trichloride in accordance with the procedure set forth in Organic Synthesis, 31, p. 88 (1951).
- EXAMPLE 1 This exampyle describes the preparation of p-phenoxyphenylphosphiuic acid.
- One part of dichloro-p-phenoxyphenylphosphine (B.P. 13 8-143 C./0.5 mm. Hg) is slow- 1y added to five parts of absolute etyhl alcohol in a suitable vessel and then two parts of water are added to the alcohol phosphine admixture with continuous stirring. The resulting admixture is heated at reflux for about five minutes. Evaporation of alcohol and water produces an oily substance.
- a polyphenyl thioether-polyphenyl ether-thioether lubricant composition is prepared by combining p-phenoxyphenyl phosphinic acid (0.10 gram) with grams of a thioether of the following composition:
- Meta-bis (phenylmercapto)benzene 50 Bis(m-phenoxyphenyl)sulfide 12.5 (m-Phenoxyphenyl) (m phenylmercaptophenyl) sulfide 23.5
- the resultant admixture was tested for lubricity 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 cincular discs. Standard operating conditions 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. The base stock was also tested for control purposes.
- Composition comprising a major amount of a polyphenyl thioether having the formula wherein R is phenyl or a substituted phenyl, R is phenylene or substituted phenylene, in which the substituents of said phenyl and phenylene are halogen, alkyl or alkoxy containing from 1 to 4 carbon atoms, 11 is an integer of from 1 to 6, Y is sulfur or oxygen provided that at least one Y is sulfur, and mixtures of such thioethers and from 7 about 0.01 to about 0.5% by weight of a phenoxyphenylphosphinic acid compound of the formula wherein R and R are alkyl of not more than 4 carbon atoms, haloalkyl of not more than 4 carbon atoms and 3 halogen atoms, halogen, hydroxyl or phenyl, and m and a are integers from 0 to 3.
- composition of claim 1 wherein the phenoxy-phenylphosphinic acid is present in amounts of from about 0.05 to about 0.2% by weight.
- composition of claim 4 wherein the alkyl is methyl.
- composition of claim 1 wherein the compound is p-phenoxyphenylphosphinic acid.
- composition of claim 1 wherein the compound is o-phenoxyphenylphosphinic acid.
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Abstract
PHENOXYPHENYLPHOSPHINIC ACIDS AND LUBRICATING COMPOSITIONS COMPRISING POLYPHEYL THIOETHERS, POLYGENYL ETHERS-THIOETHERS OR MIXTURES THEREOF AND SMALL AMOUNTS OF SAID ACIDS HAVE IMPROVED LUBRICATING PROPERTIES OVER WIDE TEMPERATURE RANGES.
Description
United States Patent US. 'Cl. 252--46.7 7 Claims ABSTRACT OF THE DISCLOSURE Phenoxyphenylphosphinic acids and lubricating compositions comprising polyphenyl thioethers, polyphenyl ethers-thioethers or mixtures thereof and small amounts of said acids have improved lubricating properties over wide temperature ranges.
This invention relates to phenoxyphenylphosphinic acids and to improved lubricating compositions compris ing polyphenyl thioethers, mixed polyphenyl ethers-thioethers and mixtures thereof, containing from 3 to 8 aromatic groups and a small amount of said phenoxyphenylphosphinic 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 this invention is to provide novel phenoxyphenylphosphinic acids having excellent lubricating additive properties.
Another object of this invention is to provide improved lubricating compositions comprising polyphenyl thioethers, polyphenyl ether-thioethers, or mixtures thereof and a small amount of a phenoxyphenylphosphinic acid.
These and other objects will become evident upon consideration of the following specification and examples.
The phenoxyphenylphosphinic acids of this invention can be represented by the formula wherein R and R are alkyl of not more than 4 carbon atoms, haloalkyl of not more than 4 carbon atoms and 3 halogen (Cl, Br and F) atoms, halogen (Cl, Br and F), hydroxyl or phenyl, and m and a are integers from 0 to 3.
Representative groups for R and R in the above formula include alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and t-butyl and haloalkyl such as chloromethyl, bromomethyl, chloroethyl, bromoethyl, trichloromethyl, tribromomethyl, dichloroethyl, chloro- 3,714,643 Patented Jan. 30, 1973 n-propyl, bromo-n-pro'pyl, bromo-n-butyl, bromo-tertbutyl, 1,3,3-trichlorobutyl and 1,3,3-tribromobutyl.
Phenoxyphenylphosphinic acids represented by the above formula include, for example,
p-phenoxyphenylphosphinic acid, o-phenoxyphenylphosphinic acid, m-phenoxyphenylphosphinic acid, p-(p-rnethylphenoxy)phenylphosphinic acid, 0- (p-methylphenoxy) -p-methylphenylphosphinic acid, p-(o-methylphenoxy)phenylphosphinic acid, p-(p-ethylphenoxy) phenylphosphinic acid, p- (o-ethylphenoxy phenylphosphinic acid, o-(o-ethylphenoxy)phenylphosphinic acid, p- (p-butylphenoxy) phenylphosphinic acid, p-(p-chlorophenoxy)phenylphosphinic acid, 0- (m-chlorophenoxy) phenylphosphinic acid, p- (p-phenylphenoxy) phenylphosphinic acid, o-(p-phenylphenoxy)phenylphosphinic acid, p- (o-hydroxyphenoxy phenylphosphinic acid, p- (m-bromophenoxy phenylphosphinic acid, p- (p-hydroxyphenoxy) phenylphosphinic acid, o-(m-phenylphenoxy)-phenylphosphinic acid 0- p-methylphenoxy -m-methylphenylpho sphinic acid, 0- (p-methylphenoxy -m-chloromethylphenylpho sphinic acid, p-(p-methylphenoxy)-m-trifluoromethylphenylphosphinic acid, p- (o-butylphenoxy) -o-trifluoromethylphenylphosphinic acid, m- (o-phenylphenoxy)-p-methylphenylphosphinic acid, m-(o-methylphenoxy)-o-butylphenylphosphinic acid, mo-chloromethylphenoxy) -o-methylphenylphosphinic acid, 0- (m-methylphenoxy ptrifluorometl1ylphenylphosphinic acid, 0- (m-hydroxyphenoxy) -p-hydroxyphenylpho sphinic acid, 0- m-phenylphenoxy) -m-chloromethylphenylphosphinic acid and pm-phenylphenoxy) -m-hydroxyphenylphosphinic acid.
The improved compositions of this invention comprise a major amount of a polyphenyl thioether-base fluid of the formula RY(R Y) R wherein R is phenyl, alkyl-substituted phenyl wherein the alkyl is of not more than 4 carbon atoms, alkoxy-substituted phenyl wherein the alkoxy is of no more than 4 carbon atoms or halogenated phenyl wherein the halogen is bromine, fluorine or chlorine, R is phenylene, alkyl or alkoxy-substituted phenylene where the alkyl contains no more than 4 carbon atoms or halogenated phenylene 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 1 to 6 and a lubricating additive amount of a phenoxyphenylphosphinic acid of the formula wherein R R m and a are as defined above. The compositions of this invention have unusual ability to lubricate under high loads at high temperatures.
The amount of phenoxyphenylphosphinic acid employed in the compositions of this invention can range from about 0.01 to about 0.5% by weight. It is preferred to employ the acids in the compositions of this invention in amounts of from about 0.05 to 0.2% by weight based upon the total composition.
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 wherein all of the Ys in the formula are sulfur. The term also includes those compounds which contain both oxygen and sulfur linkages between 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 composiiton 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 85% 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. The 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 invention are the bis(phenylmercapto)benzenes. For example m-bis phenylmercapto benzene o-bis (phenylmercapto )benzene p-bis (phenylmercapto) benzene bis (m-phenylmercaptophenyl) sulfide bis (o-phenylmercaptophenyl) sulfide bis(p-phenylmercaptophenyl sulfide m-p henylmercaptophenyl) (o-phenylmereaptophenyl) sulfide pphenylmercapto-m-phenylmercapto diphenyl sulfide o-bis (0-phenylmercaptophenylmercapto benzene p-bis (p-phenylmercaptophenylmercapto benzene p-bis (o-phenylmercaptophenylmercapto) benzene p-bis (n1-phenylmercaptophenylmercapto) benzene m-bis (p-phenylmercapctophenylmercapto benzene o-bis (p-phenylmeracptophenylmercapto 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'-phenylmereaptodiphenyl sulfide m-phenoxy-p'-phenylmercaptodiphenyl sulfide o-phenoxy-p'-phenylmercaptodiphenyl sulfide p-phenoxy-p'-phenylmercaptodiphenyl sulfide o-phenoxy-o-phenylmercaptodiphenyl sulfide o,o'-bis (phenylmercapto )diphenyl ether o-phenylmercapto-m-phenylmercaptodiphenyl ether o-phenylmercapto-p-phenylmercaptodiphenyl ether mm-phenylmercaptophenylmercapto) (m-phenoxyphenylmercapto)benzene [m- (m-phenylmercaptophenylmercapto)phenyl] [m-(mphenoxyphenylmercapto)phenyl] sulfide 3- (m-phenylmercaptophenylmercapto) -3'- (m-phenylmercaptophenoxy) diphenyl sulfide 3,3-bis (m-phenylmercaptophenylmercapto) diphenyl ether 3- (m-phenylmereaptophenylmercapto -3'- (m-phenoxyphenoxy) diphenyl sulfide 4- (m-phenylmercaptophenylmercapto -4-(m-phenylmercaptophenoxy) diphenyl ether 3- m-phenylmercaptophenylmercapto -3'- (m-phenoxyphenyl-mereapto) diphenyl ether 4,4'-bis(m-phenylmereaptophen'oxy)diphenyl sulfide 4,4-bis (m-phenoxyphenylmercapto diphenyl sulfide 3- (m-phenoxyphenylmercapto) -3'- (m-phenylmercapto phenoxy) diphenyl sulfide 3,3-bis (m-phenylmercaptophenoxy) diphenyl ether 4- (m-phenylmercaptophenylmercatpo -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-phenoxyphenylmercapto diphenyl ether, and
3-(m-phenoxyphenylmercapto)-3'-(m-phenoxypl1enoxy)- diphenyl sufide.
In addition to the foregoing compounds, the phenyl and phenylene of such compounds can contain substituents, such as alkyl of l to 4 carbon atoms, alkoxy 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-tolylmercapto) diphenyl ether 3 3 '-bis m-tolylmere apto diphenyl ether 2,4'-bis (m-tolylmercapto diphenyl ether 3,4-bis (m-tolylmercapto) diphenyl ether 3,3'-bis(p-tolylmercapto)diphenyl ether 3,3 '-bis(xylylmercapto) diphenyl ether 4,4'-bis (xylylmercapto) diphenyl ether 3,4'-bis (xylylmercapto diphenyl ether 3,4'-bis m-isopropylphenylmercapto) diphenyl ether 3,3 '-bis (m-isopropylphenylrnercapto diphenyl ether 2,4'-bis (m-isopropylphenylmercapto) diphenyl ether 3,4'-bis (p-tert-butylphenylmercapto diphenyl ether 4,4'-bis (p-tert-butylphenyl-mercapto diphenyl ether 3 3 '-bis p-tert-butylphenylmercapto diphenyl ether 3 ,3 '-bis (2,4-di-tert-butylphenylmercapto diphenyl ether 3,3'-bis 3-chlorophenylmercapto) diphenyl ether 4,4'-bis 3-chlorophenylmercapto diphenyl ether 3,3-bis (m-trifluoromethylphenylmercapto diphenyl ether 4,4-bis (m-trifluoromethylphenylmercapto) diphenyl ether 3,4'-bis (m-trifluoromethylphenylmercapto diphenyl ether 2,3'-bis(rn-trifiuoromethylphenyl-mercapto)diphenyl ether 3 ,3 -bis (p-trifiuoromethylphenylmercapto) diphenyl ether 3 3 '-'b is o-trifiuoromethylphenylmercapto diphenyl ether 3 ,3 -bis (m-methoxyphenylmercapto diphenyl ether 3,4'-bis (m'isopropoxyphenylmercapto diphenyl ether 3 ,4'-bis (m-p erfiuorobutylphenylmercapto diphenyl ether 2-(m-tolyloxy-2-phenylmercaptodiphenyl sulfide 2- (p-tolyloxy) -3 -phenylmercaptodiphenyl sulfide 2- o-tolyloxy) -4'-phenylmercaptodiphenyl sulfide 3- m-tolyloxy) -3 '-phenylmercapto diphenyl 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-pl1enoxy-4'- (m-isopropylphenylmercapto diphenyl sulfide 3 -phenoxy-3 m-isopropylphenylmercapto) diphenyl sulfide 3-m-toloxy-3'- (m-isopropylphenylmercapto) diphenyl sulfide 4- m-trifluoromethylphenoxy) -4'-phenylmercaptodiphenyl sulfide 3- (m-trifluoromethylphenoxy) -4-phenylmercaptodiphenyl sulfide 2- (m-trifluoromethylphenoxy) -3'-phenylmercaptodiphenyl sulfide 3- m-trifluoromethylphenoxy -3 '-phenylmercaptodiphenyl sulfide 3- (p-chlorophenoxy) -3-phenylmercaptodiphenyl sulfide 3- (m-bromophenoxy) -4'-phenylmercaptodiphenyl sulfide bis [m- (m-chlorophenoxy) phenyl] sulfide m-bis 3- (p-methylphenylmercapto) phenoxy] benzene m-bis [3- (m-trifluoromethylphenoxy) phenylmercapto] benzene m-bis [3 (m-bromophenoxy phenylmercapto] benzene 3,3 '-bis [m- (p-methylphenylmercapto) phenoxy] diphenyl sulfide 3 ,4'-bis [m- (p-methylphenylmercapto phenoxy] diphenyl sulfide 3-(p-xenyloxy)-3'-phenylmercapto diphenyl sulfide,
and the like and mixtures thereof. It is also contemplated within the scope of this invention to employ mixtures of polyphenyl ether-thioethers as base stocks.
The compositions of this invention are useful as lubricants under extreme conditions. The compositions are especially useful for steel on steel lubrication.
The phenoxyphenylphosphinic acids of this invention are prepared by interaction of a phosphine of the formula wherein R R m and a are as defined above with ethyl alcohol and water.
The interaction is carried out in the absence of a solvent by heating the admixture of the three components at temperatures up to and including reflux temperature. Pressure is not critical and subatmospheric, atmospheric and superatmospheric pressures can be employed. It is generally preferred to slowly add the phosphine to the ethyl alcohol and then to add the water to the admixture of phosphine and ethyl alcohol prior to heating. After reaction is complete, generally a period not exceeding more than or minutes, the excess ethyl alcohol and water are removed by azeotropic distillation with an azeotroping agent such as benzene.
The separation of the desired phosphinic acid from the azeotroping agent is readily accomplished by conventional means well known to the art. For example, distillation, fractional distillation under reduced pressure, selective extraction, fractional distillation using a carrier gas, film distillation, evaporation, elution, or any suitable combination of these methods.
Dichlorophenoxyphenylphosphines can be prepared by Friedel-Craft condensation of diphenyl ethers with phosphorus trichloride in accordance with the procedure set forth in Organic Synthesis, 31, p. 88 (1951).
The following examples serve to further illustrate the invention. All parts are parts by weight unless otherwise expressly set forth.
EXAMPLE 1 This exampyle describes the preparation of p-phenoxyphenylphosphiuic acid. One part of dichloro-p-phenoxyphenylphosphine (B.P. 13 8-143 C./0.5 mm. Hg) is slow- 1y added to five parts of absolute etyhl alcohol in a suitable vessel and then two parts of water are added to the alcohol phosphine admixture with continuous stirring. The resulting admixture is heated at reflux for about five minutes. Evaporation of alcohol and water produces an oily substance. Residual alcohol and water are removed EXAMPLE 2 A polyphenyl thioether-polyphenyl ether-thioether lubricant composition is prepared by combining p-phenoxyphenyl phosphinic acid (0.10 gram) with grams of a thioether of the following composition:
Percent by wt. Meta-bis (phenylmercapto)benzene 50 Bis(m-phenoxyphenyl)sulfide 12.5 (m-Phenoxyphenyl) (m phenylmercaptophenyl) sulfide 23.5 Bis (m-phenylmercaptophenyl)sulfide 12.65 3 ring and 5 ring thioethers 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 admixture was tested for lubricity 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 cincular discs. Standard operating conditions 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. The base stock was also tested for control purposes. When the mixture of Example 2 was tested by this procedure on M-50 tool steel, the observed coefficient of friction was substantially lower than that for the base fluid over the temperature range from 340 F. to 700 F. Moreover a decrease in the coefficient of friction began at 340 F. with the resultant admixture and not until 480 F. with the base stock.
The decrease in coeflicient of friction indicates an improved performance in Falex tests for the compositions of this invention.
The embodiments of this invention in which an exclusive property or privilege is claimed are defined as follows:
1. Composition comprising a major amount of a polyphenyl thioether having the formula wherein R is phenyl or a substituted phenyl, R is phenylene or substituted phenylene, in which the substituents of said phenyl and phenylene are halogen, alkyl or alkoxy containing from 1 to 4 carbon atoms, 11 is an integer of from 1 to 6, Y is sulfur or oxygen provided that at least one Y is sulfur, and mixtures of such thioethers and from 7 about 0.01 to about 0.5% by weight of a phenoxyphenylphosphinic acid compound of the formula wherein R and R are alkyl of not more than 4 carbon atoms, haloalkyl of not more than 4 carbon atoms and 3 halogen atoms, halogen, hydroxyl or phenyl, and m and a are integers from 0 to 3.
2. Composition of claim 1 wherein the phenoxy-phenylphosphinic acid is present in amounts of from about 0.05 to about 0.2% by weight.
3. Composition of claim 1 wherein m and a are 0.
4. Composition of claim 1 wherein m is 1, R is alkyl and a is 1 and R is alkyl.
5. Composition of claim 4 wherein the alkyl is methyl.
6. Composition of claim 1 wherein the compound is p-phenoxyphenylphosphinic acid.
8 7. Composition of claim 1 wherein the compound is o-phenoxyphenylphosphinic acid.
References Cited UNITED STATES PATENTS DANIEL E. WYMAN, Primary Examiner W. H. CANNON, Assistant Examiner US. Cl. X.R.
PC4050 I UNITEU STATES PATENT @FFKQE (5/69) t u m QE'llFi-(IATE @F CREQ i? l@ Patent No. 3 $714,043 Dated January 30, 1973 Inventor) Frank S. Clark It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
w Column 1, in the formula beginning at line 53 "R shbuld read R Column l,' in the formula beginning at line 53 "R I should read R I Column 2,' in the formula beginning at line 61 "R should read R Signed and sealed this 3rd day Of'July' 1973,
(SEAL) Attest:
EDWARD MELETCHERJR. Rene Tegtme'yer Attestfmg ev Acting Commissioner of Patents
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14812371A | 1971-05-28 | 1971-05-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3714043A true US3714043A (en) | 1973-01-30 |
Family
ID=22524383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00148123A Expired - Lifetime US3714043A (en) | 1971-05-28 | 1971-05-28 | Polyphenyl thioether lubricating compositions |
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| Country | Link |
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| US (1) | US3714043A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4092254A (en) * | 1976-08-26 | 1978-05-30 | Mobil Oil Corporation | Process of preparing monoaryl phosphonates and lubricant compositions containing same |
| US4130496A (en) * | 1976-08-26 | 1978-12-19 | Mobil Oil Corporation | Process of preparing monoaryl phosphonates and lubricant compositions containing same |
| US4485052A (en) * | 1981-11-21 | 1984-11-27 | Hoechst Aktiengesellschaft | Process for the preparation of phosphonous acids |
| US6191080B1 (en) * | 1995-06-16 | 2001-02-20 | Tonen Corporation | Heat resistant lubricating oil composition |
| US6218344B1 (en) * | 2000-01-21 | 2001-04-17 | The United States Of America As Represented By The Secretary Of The Air Force | Antiwear additives for spacecraft lubricants |
-
1971
- 1971-05-28 US US00148123A patent/US3714043A/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4092254A (en) * | 1976-08-26 | 1978-05-30 | Mobil Oil Corporation | Process of preparing monoaryl phosphonates and lubricant compositions containing same |
| US4130496A (en) * | 1976-08-26 | 1978-12-19 | Mobil Oil Corporation | Process of preparing monoaryl phosphonates and lubricant compositions containing same |
| US4485052A (en) * | 1981-11-21 | 1984-11-27 | Hoechst Aktiengesellschaft | Process for the preparation of phosphonous acids |
| 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 |
| US6218344B1 (en) * | 2000-01-21 | 2001-04-17 | The United States Of America As Represented By The Secretary Of The Air Force | Antiwear additives for spacecraft lubricants |
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