US2146584A - Lubricant - Google Patents

Lubricant Download PDF

Info

Publication number
US2146584A
US2146584A US84295A US8429536A US2146584A US 2146584 A US2146584 A US 2146584A US 84295 A US84295 A US 84295A US 8429536 A US8429536 A US 8429536A US 2146584 A US2146584 A US 2146584A
Authority
US
United States
Prior art keywords
oil
reaction
phosphorus
pressure
oils
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
US84295A
Inventor
Lipkin David
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.)
Atlantic Richfield Co
Original Assignee
Atlantic Refining 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 Atlantic Refining Co filed Critical Atlantic Refining Co
Priority to US84295A priority Critical patent/US2146584A/en
Application granted granted Critical
Publication of US2146584A publication Critical patent/US2146584A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M1/00Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40Fatty vegetable or animal oils
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40Fatty vegetable or animal oils
    • C10M2207/404Fatty vegetable or animal oils obtained from genetically modified species
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049Phosphite
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/12Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/044Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/046Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/22Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10Semi-solids; greasy

Definitions

  • the present invention relates to the art of lubrication, and more particularly to the lubrication of surfaces engaging under extreme pressure, as for example, the rubbing surfaces of hypoid gears, free wheeling transmissions, speed reducers and the like.
  • lubrication consists in maintaining a film of oil between the rubbing surfaces, thereby preventing them from coming into contact with one another and thus preventing wear. That this condition exists in well lubricated bearings is well known, but this conception of lubrication does not apply-to highly loaded gears. In well lubricated bearings the loads rarely exceed 2000 lbs. per sq. in. projected area and the rubbing speeds are generally high enoughto maintain a film of oil which separates 'the rubbing surfaces. In automobile gears, the pressures between gear teeth reach very high values and even the most viscous oils or greases cannot be retained between the surfaces of the teeth in a sufliciently thick film to prevent metal to metal contact, particularly when operating temperatures of 210 F. or higher are commonly encountered.
  • compounded lubricants such as, for example, mineral oils containing fatty oils, fatty acids, metallic soaps, sulfur or combined chlorine, possess lubricating qualities 40 which render them suitable for use under high operating pressures. These compounded oils function satisfactorily under conditions which would cause failure of an unblended mineral oil, if used alone. It is believed that the successful 5 use of such compounded oils depends upon the adsorption and reaction or union of certain components of these oils with the metal surfaces whereby a film of metallic compound, such as, for example, iron sulfide or chloride is formed.
  • metallic compound such as, for example, iron sulfide or chloride
  • These compounds may be prepared, in accordance with my invention, by the reaction of halogen and/or sulfur derivatives of phosphorus with primary and secondary amino compounds. More particularly, one or more compounds from the group phosphorus trichloride PCla; phosphorus pentachloride PCls; phosphorus oxychloride POCla; phosphorus sulfochloride PSCla; and the phosphorus sulfides Pass and P285 .may be reacted with a primary or secondary amino compound to yield products which may be described as the substituted amides of the phosphorus acids.
  • the amino compounds'which I may employ in the preparation of my reaction products comprehend one or a mixture of any of the primary and secondary aliphatic, aromatic, hydroaromatq- 10 and heterocyclic amines.
  • The. aliphatic amines include, for example, monoand dimethyl'amine and their homologues, ethyl-, propyl-, butylamines and the like, as well as the halogen substituted aliphatic amines, for example, chloro-butylamine and chloro-amylamine.
  • matic amino compounds may be represented, for example, by aniline, toluidine, xylidine, phenylene diamine, naphthylamine, anthramine, benzylamine, methylamline and the like.
  • the hydroaromatic amino compounds include cyclohexyl- 45 amine, tetrahydro-naphthylamine, methylcyclohexylamine and the like.
  • the heterocyclic amino compounds may be represented, for example, by furfurylamine,-piperidine, tetrahydroquinoline, aminopyrldine and the like.
  • Other 50 The arosubstituted ammonias containing at least one reactive hydrogen atom, such as phenylhydrazine, may be suitably employed.
  • the primary and secondary amino compounds contemplated have the following formulae:
  • R RNH and NH wherein R and R are of the group consisting of aliphatic, aromatic, hydroaromatic and heterocyclic radicals, and the substitution products thereof.
  • reaction product is to be understood to comprehend the compounds formed by the reaction of the halogen and sulfur derivatives of phosphorus with primary and secondary amino compounds.
  • my reaction product In preparing my lubricant, I add to a suitable mineral oil one or a mixture of two or more of my reaction products in quantity sufficient to improve the value of the oil as a lubricant to any desired extent, depending upon the operating conditions under which the lubricant is to be used. I have found that the quantity of reaction product required, in general, does not exceed substantially 5% by weight of my composition. Quantities as small as 3%, or even 1% or less, have been found to improve lubricating oils to a satisfactory extent. In certain instances, 0.1% to 0.5% by weight of the reaction product was sufficient to improve the lubricating oil to the desired extent.
  • I may obtain a homogeneous solution or stable suspension of my reaction product in mineral oil by agitating the mixture at normal or elevated temperatures, or I may dissolve the reaction product in a suitable solvent and add the resulting solution to the oil, thereafter removing the solvent by vaporization.
  • reaction prodnets in lubricating oils function to improve the sorption of the compounds upon the metal surfaces of the bearings or other lubricated parts, and the reaction or chemical combination of such compounds with the metal under the influence of localized high temperature and pressure to form a coating or plating having a low coeillcient of friction which is resistant to seizure under high operating pressures.
  • the following tables indicate some of the reaction products obtained by the treatment of primary and secondary amines with the phosphorus halides.
  • the treatment may be carried on in the presence of hydroxy and/or mercaptan compounds, whereby other groups are introduced into the reaction products. Or, the initial reaction products may subsequently be reacted with a hydroxy and/or mercaptan compound.
  • the resulting products more complex in structure, have been found suitable for use as addition agents for hydrocarbon oils.
  • R, and R. may be the same or different aliphatic, aromatic, hydroaromatic and heterocyclic radicals, while X" represents halogen, i. e., chlorine, bromine or fluorine.
  • the reaction product may be one or a mixture of compounds, depending upon the ratio of the reacting components, the time and temperature of the reaction, and the completeness of the reaction between the components.
  • the hydroxy and/or mercaptan compounds which may be employed in the reaction include, for example, methyl alcohol and mercaptan and their homologues; phenol and phenyl mercaptan and their homologues; cyclohexanol and cyclohexyl mercaptan and their homologues; and various heterocyclic compounds such as furfuryl alcohol, furfuryl mercaptan, hydroxyquinoline and pyridyl -mercaptan.
  • Phcn 1 benzylaminelphos hinate oBa a a) Table 4-Continued -Diisobuti'lnminephosphonic lacid chloride C1 Chlor821riilinepllosphonic acid chloride CIC H NHPOCL;
  • Example 1 0.1 mole of phosphorus oxychioride, POCla, in ether solution was added to 0.7 mole of mono-nbutylamine in ether solution with stirring. The mixture was refluxed on a steam bath for about 3 hours, removed and cooled, and thenwashed with dilute HCl solution and finally with water. The ether solution of the reaction product, N, N, N"-tri-n-butyi phosphoric acid amide, was dried over anhydrous K2CO3, the ether then removed by distillation and the reaction product, in the amount of about 1% by weight, was added to a hydrocarbon oil having a Saybolt universal viscosity of 304 seconds at 100 F. and an A. P. I. gravity of 29.5.
  • Example 2 0.1 mole of phosphorus oxychloride, POCla, in ether solution was added to 0.6 mole of di-nbutylamine in ether solution with stirring. The
  • reaction product in the amount of about 1% by weight was added to the hydrocarbon oil mentioned in Example 1 and the blended oil, when tested under the conditions set forth in Example 1, withstood a pressure of 15,000 lbs./sq.. in. projected bearing area before failure, whereas the unblended hydrocarbon oil failed at a pressure of 4,000 lbs/sq. in. projected bearing area.
  • Example 3 0.04 mole of phosphorus oxychloride, POCla, in benzene solution was added to 0.25 mole of di-nbutylamine in ether. solution with stirring. The mixture was refluxed on a steam bath for about hours, removed and cooled, and washed with water. The ether solution of the reaction product, di-n-butylamine-phosphonic acid chloride, was dried over anhydrous K2003, the ether evaporated off and the excess unreacted amine removed from the product by distillation under reduced pressure. The reaction product, in the amount of about 2% by weight, was added to the hydrocarbon oil mentioned in Example 1 and the blended oil, when tested under the conditions set forth in Example 1, withstood a pressure of 16,000
  • Example 4 0.07 mole of phosphorus sulfochloride, PSCla, in naphtha solution was added to 0.05 mole of mono- .n-butylamine in naphtha solution with stirring.
  • the mixture was refluxed on a steam bath for about 11 hours, removed and cooled, filtered and the filtrate washed with water.
  • the naphtha solution of the reaction product, N, N, N"-tr1-nbutyl phosphoric acid amide, was heated to a temperature sumcient to distill off the naphtha.
  • the reaction product in the amount of about 1% by weight was added to the hydrocarbon oil mentioned in Example 1 and the blended oil, when tested under the conditions set forth in Example 1, withstood a pressure of 17,000 lbs/sq. in. projected bearing area before failure, whereas the unblended hydrocarbon oil failed at a pressure of 4,000 lbs/sq. in. projected bearing area.
  • Example 5 0.1 mole of phosphorus sulfochloride, PSCla, was added to 0.2 mole of di-n-butylamine with stirring. The mixture was refluxed by means of an oil bath at a temperature of about 240 F. to 265 F. for about 3 hours, and thereafter was steam-distilled to produce a distillate and a residue. The distillate was extracted with ether and the ether extract was then heated to an elevated temperature in order to drive off the ether.
  • PSCla phosphorus sulfochloride
  • the reaction product, di-n-butylamine-thiophosv phonic acid chloride in the amount of about 1% by Weight was added to the hydrocarbon oil mentioned in Example 1 and the blended oil, when tested under the conditions set forth in Example 1, withstood a pressure of 22,000 lbs/sq. in. projected bearing area before failure, whereas the unblended hydrocarbon oil failed at a pressure of 4,000 lbs/sq. in. projected bearing area.
  • Example 6' 0.03 mole of phosphorus trichloride, PCla, in naphtha solution was added to 0.25 mole of din-butylamine in naphtha solution with stirring. The mixture was stirred at room temperature for about 2 hours, then filtered, and the filtrate Washed with water. The naphtha solution of the reaction. product, hexa-n-butyl phosphorus acid amide, was dried over anhydrous K2CO3, the naphtha evaporated oil and the excess unreacted amine removed from the product by distillation underreduced pressure.
  • reaction product in the amount of about 1% by weight was added to the hydrocarbon oil mentioned in Example 1 and the blended oil, when tested under the conditions set forth in Example 1, withstood a pressure of 22,000 lbs/sq. in. projected bearing area before failure, whereas the unblended hydrocarbon oil failed at a pressure of 4,000 lbs/sq. in. projected bearing area.
  • reaction products not only improve the load-bearing capacity of hydrocarbon oils but also impart thereto a marked resistivity to oxidation and sludge formation.
  • a lubricating oil containing about 1% by weight of N, N, N"-tri-n-butyl phosphoric acid amide when subjected to an oxidation test at 340 F. for 96 hours, developed only 18 milligrams of sludge per gram of oil, whereas the unblended lubricating oil, under the same test, produced 40 milligrams of sludge per gram bf oil.
  • my lubricant in operations such as the cutting and boring of metals, in which conditions of extreme pressure and temperature are normally encountered, and also in the lubrication of mechanisms operating under moderate pressures, as for example, the crankcase bearings and cylinder walls of internal combustion engines.
  • my compounded oil may be utilized as a base in the preparation of thickened oils, 1. e., greases, by the addition thereto of soaps or other conventional thickening agents, in order to obtain lubricants of desired viscosity.
  • My compounded oil may also be blended with fatty oils, fatty acids, synthetic esters and the'like, or the reaction products, per se, may be admixed with fatty oils, for the lubrication of mechanisms in which the presence of a fatty oil is desirable.
  • a lubricant comprising a hydrocarbon oil and a small proportion of a product of reaction of at least one compound from the group PCls, P0013, P8013, P283 and P285 with an aliphatic amine having at least one hydrogen atom directly connected to the nitrogen atom.
  • a lubricant comprising a hydrocarbon oil and a small proportion of a product of reaction of at least one compound from the group PC15,
  • a lubricating oil composition comprising a relatively large proportion of a lubricating oil of the type which normally tends to rupture at the surface of contact with a bearing-metal under relatively high bearing pressure, and in in-'- timate homogeneous combination therewith a small but sufilcient proportion of the oil-miscible, substantially water-insoluble condensation reaction product of phosphorus trichloride and an aryl amine having at least one hydrogen atom attached directly to the nitrogen atom to impart extreme pressure lubricating characteristics to said oil.
  • a lubricant comprising a hydrocarbon oil and a small proportion of a product of reactionof at least one compound from the group PCls,
  • POCla, PSCla, P283 and PzSs with an amine having at least one hydrogen atom directly connected to the nitrogen atom.
  • a lubricant comprising a hydrocarbon oil and a small proportion of a product of reaction of at least one compound from the group PCl5, POCla, PSCls, P233 and P235 with an aromatic amine having at least one hydrogen atom directly connected to the nitrogen atom.
  • a lubricant comprising hydrocarbonoil and a small proportion of a product of reaction of at least one compound from the group F615, P0013, P8013, 22S: and P285 with an amine having at least one hydrogen atom directly connected to the nitrogen atom and with a compound from the group consisting of hydroxy and mercaptan compounds. 5

Description

Patented F ch. 7, 1939 UNITED STATES PATENT OFFICE Atlantic Refining Company, Philadelphia, Pa., a. corporation of Pennsylvania.
No Drawing. Application June 9, 1936, Serial No. 84,295
6 Claims. (01. 87-9) The present invention relates to the art of lubrication, and more particularly to the lubrication of surfaces engaging under extreme pressure, as for example, the rubbing surfaces of hypoid gears, free wheeling transmissions, speed reducers and the like.
The general tendency in the design of modern machinery has been toward a higher ratio between power and dead weight.
ally true in the automotive industry, and in recent years certain types of gears and other mechanisms have been developed with the operating pressures on the working surfaces so high that ordinary mineral oil lubricants will not provide sufiicient lubrication for satisfactory operation.
Heretofore it has been thought that lubrication consists in maintaining a film of oil between the rubbing surfaces, thereby preventing them from coming into contact with one another and thus preventing wear. That this condition exists in well lubricated bearings is well known, but this conception of lubrication does not apply-to highly loaded gears. In well lubricated bearings the loads rarely exceed 2000 lbs. per sq. in. projected area and the rubbing speeds are generally high enoughto maintain a film of oil which separates 'the rubbing surfaces. In automobile gears, the pressures between gear teeth reach very high values and even the most viscous oils or greases cannot be retained between the surfaces of the teeth in a sufliciently thick film to prevent metal to metal contact, particularly when operating temperatures of 210 F. or higher are commonly encountered.
It has been known that compounded lubricants such as, for example, mineral oils containing fatty oils, fatty acids, metallic soaps, sulfur or combined chlorine, possess lubricating qualities 40 which render them suitable for use under high operating pressures. These compounded oils function satisfactorily under conditions which would cause failure of an unblended mineral oil, if used alone. It is believed that the successful 5 use of such compounded oils depends upon the adsorption and reaction or union of certain components of these oils with the metal surfaces whereby a film of metallic compound, such as, for example, iron sulfide or chloride is formed. 50 It appears that such a film or plating has a low This is especicoeflicient of friction and that satisfactory operation of heavily loaded bearings or gears depends upon the formation and maintenance of such a film, and not upon the retaining of a film of oil between the bearing surfaces. The hydro- 5 carbon oil constituent of an extreme pressure lubricant serves primarily to remove frictional heat, to wash away any solid particles which may result from wear, and to prevent oxidation of the engaging surfaces. 10 I have discovered that organic compounds of phosphorus and nitrogen, and more particularly the compounds which may be termed, in general, the substituted amides of the phosphorus acids, when admixed with hydrocarbon oils, are of special utility in the field of extreme pressure lubrication. These compounds may be prepared, in accordance with my invention, by the reaction of halogen and/or sulfur derivatives of phosphorus with primary and secondary amino compounds. More particularly, one or more compounds from the group phosphorus trichloride PCla; phosphorus pentachloride PCls; phosphorus oxychloride POCla; phosphorus sulfochloride PSCla; and the phosphorus sulfides Pass and P285 .may be reacted with a primary or secondary amino compound to yield products which may be described as the substituted amides of the phosphorus acids.
The amino compounds'which I may employ in the preparation of my reaction products comprehend one or a mixture of any of the primary and secondary aliphatic, aromatic, hydroaromatq- 10 and heterocyclic amines. The. aliphatic amines include, for example, monoand dimethyl'amine and their homologues, ethyl-, propyl-, butylamines and the like, as well as the halogen substituted aliphatic amines, for example, chloro-butylamine and chloro-amylamine. matic amino compounds may be represented, for example, by aniline, toluidine, xylidine, phenylene diamine, naphthylamine, anthramine, benzylamine, methylamline and the like. The hydroaromatic amino compounds include cyclohexyl- 45 amine, tetrahydro-naphthylamine, methylcyclohexylamine and the like. The heterocyclic amino compounds may be represented, for example, by furfurylamine,-piperidine, tetrahydroquinoline, aminopyrldine and the like. Other 50 The arosubstituted ammonias containing at least one reactive hydrogen atom, such as phenylhydrazine, may be suitably employed. In general. the primary and secondary amino compounds contemplated have the following formulae:
R RNH: and NH wherein R and R are of the group consisting of aliphatic, aromatic, hydroaromatic and heterocyclic radicals, and the substitution products thereof.
Herein, the term reaction product is to be understood to comprehend the compounds formed by the reaction of the halogen and sulfur derivatives of phosphorus with primary and secondary amino compounds.
In preparing my lubricant, I add to a suitable mineral oil one or a mixture of two or more of my reaction products in quantity sufficient to improve the value of the oil as a lubricant to any desired extent, depending upon the operating conditions under which the lubricant is to be used. I have found that the quantity of reaction product required, in general, does not exceed substantially 5% by weight of my composition. Quantities as small as 3%, or even 1% or less, have been found to improve lubricating oils to a satisfactory extent. In certain instances, 0.1% to 0.5% by weight of the reaction product was sufficient to improve the lubricating oil to the desired extent. In preparing my lubricant, I may obtain a homogeneous solution or stable suspension of my reaction product in mineral oil by agitating the mixture at normal or elevated temperatures, or I may dissolve the reaction product in a suitable solvent and add the resulting solution to the oil, thereafter removing the solvent by vaporization.
The mechanism by which the reaction prodnets in lubricating oils function to improve the sorption of the compounds upon the metal surfaces of the bearings or other lubricated parts, and the reaction or chemical combination of such compounds with the metal under the influence of localized high temperature and pressure to form a coating or plating having a low coeillcient of friction which is resistant to seizure under high operating pressures.
The following tables indicate some of the reaction products obtained by the treatment of primary and secondary amines with the phosphorus halides. The treatment may be carried on in the presence of hydroxy and/or mercaptan compounds, whereby other groups are introduced into the reaction products. Or, the initial reaction products may subsequently be reacted with a hydroxy and/or mercaptan compound. The resulting products, more complex in structure, have been found suitable for use as addition agents for hydrocarbon oils. In the formulae given in tables, R, and R. may be the same or different aliphatic, aromatic, hydroaromatic and heterocyclic radicals, while X" represents halogen, i. e., chlorine, bromine or fluorine. The reaction product may be one or a mixture of compounds, depending upon the ratio of the reacting components, the time and temperature of the reaction, and the completeness of the reaction between the components. The hydroxy and/or mercaptan compounds which may be employed in the reaction include, for example, methyl alcohol and mercaptan and their homologues; phenol and phenyl mercaptan and their homologues; cyclohexanol and cyclohexyl mercaptan and their homologues; and various heterocyclic compounds such as furfuryl alcohol, furfuryl mercaptan, hydroxyquinoline and pyridyl -mercaptan.
Table 1 Reaction components Reaction products RNH BNH RNHri-PX; annex, rx RNH P RNH RNH X 0B BNH RNH:+PXa+B/0H RNHP/ BNHP r-oa' on on BNH x as" BNH RNH:+PX:+RSH lannr RNHP/ P-SR' an an RNH RzN BzN R|NH+PX| RaNPX: \PX RsN P Rm Rm x 011' RzN R1NH+PX:+R0H mNP RNP \POR OR or. RaN
X en mN amu+rxl+wsn RaNP RINP P-SR' an an am manner, a number of reaction products which may be suitably employed as addition agents for lubricants.
Table 4 Hexabutyl phosphorous acid amide [(Ce a 1 ]a Tris-cyclopenta ethylene phosphorous acid amide 1 8 Isobutg aminephosfihonic acid chloride H;) CHCH2 HPQCI Isobutglammgphosghomc acid anilide a) C CH, HP0( o s)2 Isobut lam ingihoighonic acid fiheglhydrazide a a HPO(NHN a )2 Benzziamme hosphonic acid chloride CHEM-IP00], Diphen l benz lamine hos honate CH.NEIPO (OEJI;
Hexaethyl phNoixpll ioric acid amide 2 2 3 'n-Pug) laminethiophosphonie acid chloridev gl NHPsCl Diethyl n-propylaminethiophosphonate C3H'INHPS( O z a 2 n-Pngpyiaminethlofihosfphomc acid amlide gHqNHPSSN C N,N',1 (I:"-trietl;ypghiophosphoric acid amide S 3 Diprop laminethiophosphonic acid chloride (cgHfl NPSCi Piperdinethiophosphinic acid chloride C H N PSCI HexaetIyI thigphosphoric acid amide I 2 5 2 n-Pro glaminephossinic acid chloride ,H-,NH),PO l
Phcn 1 benzylaminelphos hinate oBa a a) Table 4-Continued -Diisobuti'lnminephosphonic lacid chloride C1 Chlor821riilinepllosphonic acid chloride CIC H NHPOCL;
Typical examples of my improved lubricants and methods of preparing the same are as follows:
Example 1 0.1 mole of phosphorus oxychioride, POCla, in ether solution was added to 0.7 mole of mono-nbutylamine in ether solution with stirring. The mixture was refluxed on a steam bath for about 3 hours, removed and cooled, and thenwashed with dilute HCl solution and finally with water. The ether solution of the reaction product, N, N, N"-tri-n-butyi phosphoric acid amide, was dried over anhydrous K2CO3, the ether then removed by distillation and the reaction product, in the amount of about 1% by weight, was added to a hydrocarbon oil having a Saybolt universal viscosity of 304 seconds at 100 F. and an A. P. I. gravity of 29.5. This blended oil, when tested in an Almen extreme pressure lubricant testing machine at 200 R. P. M., withstood a pressure of 17,000 lbs/sq. in. projected bearing area before failure, whereas the unblended hydrocarbon oil failed at a pressure of only 4,000 lbs/sq. in. projected bearing area.
Example 2 0.1 mole of phosphorus oxychloride, POCla, in ether solution was added to 0.6 mole of di-nbutylamine in ether solution with stirring. The
mixture was refluxed on a steam bath for about 2 hours, and 0.6 mole of mono-n-butylamine was added. The refluxing was continued for about hours, the mixture then removed and cooled, and washed with water. The ether solution of the reaction product, poly-butylphosphoric acid amide, was dried over anhydrous KzCOa, the ether evaporated off and the excess unreacted amine removed from the product by distillation under reduced pressure. The reaction product, in the amount of about 1% by weight was added to the hydrocarbon oil mentioned in Example 1 and the blended oil, when tested under the conditions set forth in Example 1, withstood a pressure of 15,000 lbs./sq.. in. projected bearing area before failure, whereas the unblended hydrocarbon oil failed at a pressure of 4,000 lbs/sq. in. projected bearing area.
Example 3 0.04 mole of phosphorus oxychloride, POCla, in benzene solution was added to 0.25 mole of di-nbutylamine in ether. solution with stirring. The mixture was refluxed on a steam bath for about hours, removed and cooled, and washed with water. The ether solution of the reaction product, di-n-butylamine-phosphonic acid chloride, was dried over anhydrous K2003, the ether evaporated off and the excess unreacted amine removed from the product by distillation under reduced pressure. The reaction product, in the amount of about 2% by weight, was added to the hydrocarbon oil mentioned in Example 1 and the blended oil, when tested under the conditions set forth in Example 1, withstood a pressure of 16,000
lbs/sq. in. projected bearing area before failure,
whereas the unblended hydrocarbon oil failed at a pressure of 4,000 lbs./sq. in. projected bearing area.
Example 4 0.07 mole of phosphorus sulfochloride, PSCla, in naphtha solution was added to 0.05 mole of mono- .n-butylamine in naphtha solution with stirring.
The mixture was refluxed on a steam bath for about 11 hours, removed and cooled, filtered and the filtrate washed with water. The naphtha solution of the reaction product, N, N, N"-tr1-nbutyl phosphoric acid amide, was heated to a temperature sumcient to distill off the naphtha. The reaction product, in the amount of about 1% by weight was added to the hydrocarbon oil mentioned in Example 1 and the blended oil, when tested under the conditions set forth in Example 1, withstood a pressure of 17,000 lbs/sq. in. projected bearing area before failure, whereas the unblended hydrocarbon oil failed at a pressure of 4,000 lbs/sq. in. projected bearing area.
Example 5 0.1 mole of phosphorus sulfochloride, PSCla, was added to 0.2 mole of di-n-butylamine with stirring. The mixture was refluxed by means of an oil bath at a temperature of about 240 F. to 265 F. for about 3 hours, and thereafter was steam-distilled to produce a distillate and a residue. The distillate was extracted with ether and the ether extract was then heated to an elevated temperature in order to drive off the ether. The reaction product, di-n-butylamine-thiophosv phonic acid chloride in the amount of about 1% by Weight was added to the hydrocarbon oil mentioned in Example 1 and the blended oil, when tested under the conditions set forth in Example 1, withstood a pressure of 22,000 lbs/sq. in. projected bearing area before failure, whereas the unblended hydrocarbon oil failed at a pressure of 4,000 lbs/sq. in. projected bearing area.
Example 6' 0.03 mole of phosphorus trichloride, PCla, in naphtha solution was added to 0.25 mole of din-butylamine in naphtha solution with stirring. The mixture was stirred at room temperature for about 2 hours, then filtered, and the filtrate Washed with water. The naphtha solution of the reaction. product, hexa-n-butyl phosphorus acid amide, was dried over anhydrous K2CO3, the naphtha evaporated oil and the excess unreacted amine removed from the product by distillation underreduced pressure. The reaction product, in the amount of about 1% by weight was added to the hydrocarbon oil mentioned in Example 1 and the blended oil, when tested under the conditions set forth in Example 1, withstood a pressure of 22,000 lbs/sq. in. projected bearing area before failure, whereas the unblended hydrocarbon oil failed at a pressure of 4,000 lbs/sq. in. projected bearing area.
It will be seen, from the above examples, that the addition of my reaction products to a hydrocarbon oil improves the lubricating value of such an oil to a marked degree, and imparts to the oil certain properties which render it suitable substitution products thereof, are representative examples of this type of materials.
In another aspect of my invention, I have found that these reaction products not only improve the load-bearing capacity of hydrocarbon oils but also impart thereto a marked resistivity to oxidation and sludge formation. For example, a lubricating oil containing about 1% by weight of N, N, N"-tri-n-butyl phosphoric acid amide, when subjected to an oxidation test at 340 F. for 96 hours, developed only 18 milligrams of sludge per gram of oil, whereas the unblended lubricating oil, under the same test, produced 40 milligrams of sludge per gram bf oil.
Furthermore, the addition of my reaction products to lubricating oils, especially the highly parafllnic oils produced by solvent extraction processes, inhibits and in many cases prevents, the corrosion of copper-silver-cadmium and copperlead bearings of internal combustion engines lubricated with such oils.
While I have described my invention with reference to the lubrication of gears and bearings operating under heavy loads, I do not intend to limit myself thereto, but contemplate the use of my lubricant in operations such as the cutting and boring of metals, in which conditions of extreme pressure and temperature are normally encountered, and also in the lubrication of mechanisms operating under moderate pressures, as for example, the crankcase bearings and cylinder walls of internal combustion engines. Furthermore, my compounded oil may be utilized as a base in the preparation of thickened oils, 1. e., greases, by the addition thereto of soaps or other conventional thickening agents, in order to obtain lubricants of desired viscosity. My compounded oil may also be blended with fatty oils, fatty acids, synthetic esters and the'like, or the reaction products, per se, may be admixed with fatty oils, for the lubrication of mechanisms in which the presence of a fatty oil is desirable.
What I claim is:
1. A lubricant comprising a hydrocarbon oil and a small proportion of a product of reaction of at least one compound from the group PCls, P0013, P8013, P283 and P285 with an aliphatic amine having at least one hydrogen atom directly connected to the nitrogen atom.
2. A lubricant comprising a hydrocarbon oil and a small proportion of a product of reaction of at least one compound from the group PC15,
P0013, P SC13, P283 and PzSs with a butylamine having at least one hydrogen atom directly connected to the nitrogen atom.
3. A lubricating oil composition comprising a relatively large proportion of a lubricating oil of the type which normally tends to rupture at the surface of contact with a bearing-metal under relatively high bearing pressure, and in in-'- timate homogeneous combination therewith a small but sufilcient proportion of the oil-miscible, substantially water-insoluble condensation reaction product of phosphorus trichloride and an aryl amine having at least one hydrogen atom attached directly to the nitrogen atom to impart extreme pressure lubricating characteristics to said oil.
4. A lubricant comprising a hydrocarbon oil and a small proportion of a product of reactionof at least one compound from the group PCls,
POCla, PSCla, P283 and PzSs with an amine having at least one hydrogen atom directly connected to the nitrogen atom.
5. A lubricant comprising a hydrocarbon oil and a small proportion of a product of reaction of at least one compound from the group PCl5, POCla, PSCls, P233 and P235 with an aromatic amine having at least one hydrogen atom directly connected to the nitrogen atom.
6. A lubricant comprising hydrocarbonoil and a small proportion of a product of reaction of at least one compound from the group F615, P0013, P8013, 22S: and P285 with an amine having at least one hydrogen atom directly connected to the nitrogen atom and with a compound from the group consisting of hydroxy and mercaptan compounds. 5
DAVID mm.
US84295A 1936-06-09 1936-06-09 Lubricant Expired - Lifetime US2146584A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US84295A US2146584A (en) 1936-06-09 1936-06-09 Lubricant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US84295A US2146584A (en) 1936-06-09 1936-06-09 Lubricant

Publications (1)

Publication Number Publication Date
US2146584A true US2146584A (en) 1939-02-07

Family

ID=22184042

Family Applications (1)

Application Number Title Priority Date Filing Date
US84295A Expired - Lifetime US2146584A (en) 1936-06-09 1936-06-09 Lubricant

Country Status (1)

Country Link
US (1) US2146584A (en)

Cited By (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2442581A (en) * 1945-07-28 1948-06-01 Tide Water Associated Oil Comp Rust-preventive composition
US2459113A (en) * 1945-07-06 1949-01-11 Socony Vacuum Oil Co Inc Mineral oil composition
US2459115A (en) * 1945-07-06 1949-01-11 Socony Vacuum Oil Co Inc Mineral oil composition
US2460301A (en) * 1945-03-30 1949-02-01 Lubrizol Dev Corp Lubricating oils
US2500762A (en) * 1947-01-02 1950-03-14 Standard Oil Dev Co Lubricant composition
US2506573A (en) * 1946-06-01 1950-05-09 Standard Oil Co Lubricant composition
US2506572A (en) * 1946-04-19 1950-05-09 Standard Oil Co Lubricant composition
US2508860A (en) * 1945-06-28 1950-05-23 Gen Aniline & Film Corp Production of benzamidocyclohexane
US2509594A (en) * 1945-04-12 1950-05-30 Gen Aniline & Film Corp Production of nicotinanilide
US2539424A (en) * 1946-05-18 1951-01-30 Standard Oil Co Esters of ps-amine reaction products as lubricating oil additives and lubricants containing same
US2552536A (en) * 1948-08-23 1951-05-15 Dow Chemical Co O, o-di-(methoxyphenyl) amidothiophosphate
US2552575A (en) * 1948-08-30 1951-05-15 Dow Chemical Co O, o-di(2-allylphenyl) n-alkylamidothiophosphates
US2552537A (en) * 1948-10-15 1951-05-15 Dow Chemical Co O-polyhalophenyl diamidothiophosphates
US2552576A (en) * 1948-08-30 1951-05-15 Dow Chemical Co Amidothiophosphates
US2552577A (en) * 1948-10-15 1951-05-15 Dow Chemical Co Diamidothiophosphates
US2552538A (en) * 1948-10-15 1951-05-15 Dow Chemical Co Diamidothiophosphates
US2615038A (en) * 1948-10-15 1952-10-21 Dow Chemical Co O,o-di(polyhalophenyl) n-substituted amidothiophosphates
US2615037A (en) * 1948-10-15 1952-10-21 Dow Chemical Co O,o-di(4-chlorophenyl) n-alkylamidothiophosphates
US2624707A (en) * 1949-06-07 1953-01-06 Shell Dev Lubricating composition
US2662095A (en) * 1948-07-09 1953-12-08 Southern Production Company In Dimethyl-phosphoric acid amide and its production
US2663705A (en) * 1951-07-25 1953-12-22 American Cyanamid Co Phosphoric acid derivatives and methods of preparing the same
US2671109A (en) * 1949-11-16 1954-03-02 Pest Control Ltd Preparation of bis-dialkylamino phosphonous anhydrides
US2703813A (en) * 1952-03-19 1955-03-08 Monsanto Chemicals Organic phosphorus compounds
US2706194A (en) * 1951-05-14 1955-04-12 Shell Dev Esters of phosphonic acids
US2730547A (en) * 1955-02-01 1956-01-10 Monsanto Chemicals Benzyltris (dialkylamino) phosphonium halides
US2760974A (en) * 1952-07-28 1956-08-28 Union Oil Co Separation of phosphoryl amide adducts of benzene dicarboxylic acids
US2774658A (en) * 1955-08-30 1956-12-18 Mousanto Chemical Company Herbicidal alkyl-amino-phosphonium halides
US2776311A (en) * 1953-06-16 1957-01-01 Dow Chemical Co Diamido anilido phosphine oxides and sulfides
US2786075A (en) * 1954-09-09 1957-03-19 Monsanto Chemicals Adducts of hexamethylphosphorous triamide and polyhalo compounds
US2882309A (en) * 1953-10-30 1959-04-14 Kellogg M W Co Production of organophosphorus compounds
US2882307A (en) * 1953-10-30 1959-04-14 Kellogg M W Co Production of organophosphorus compounds
US2882308A (en) * 1953-10-30 1959-04-14 Kellogg M W Co Production of organic phosphonyl halide
US2882305A (en) * 1953-10-30 1959-04-14 Kellogg M W Co Production of organic phosphonyl halide
US2882306A (en) * 1953-10-30 1959-04-14 Kellogg M W Co Production of organophosphorus compounds
US2882304A (en) * 1953-10-30 1959-04-14 Kellogg M W Co Production of organic phosphonyl halide
US2896400A (en) * 1953-02-16 1959-07-28 Standard Oil Co Rocket propulsion method
US2941001A (en) * 1956-06-25 1960-06-14 American Potash & Chem Corp Manufacture of aminophosphines
US2995596A (en) * 1956-09-01 1961-08-08 Benckiser Gmbh Joh A Production of phosphoric aciddialkylester-amines
US3031401A (en) * 1959-06-11 1962-04-24 Gulf Research Development Co Lubricating oil composition
US3070604A (en) * 1960-07-26 1962-12-25 Basic Res Corp Fire resistant compound
US3098824A (en) * 1957-11-15 1963-07-23 Pure Oil Co Lubricating composition
US3225090A (en) * 1963-05-17 1965-12-21 Olin Mathieson Bis(aminodiarylphosphine) decaboranes
US3268448A (en) * 1963-02-28 1966-08-23 Cities Service Oil Co Zinc chloride phosphothiourea compounds
US3309317A (en) * 1964-06-08 1967-03-14 Shell Oil Co Lubricating composition
US3321401A (en) * 1964-09-18 1967-05-23 British Petroleum Co Lubricating compositions
US3433623A (en) * 1965-10-20 1969-03-18 Rohm & Haas Phosphoric triamide derivatives as herbicides
US3468946A (en) * 1965-10-20 1969-09-23 Rohm & Haas Phosphoric triamide derivatives
US3859219A (en) * 1972-11-17 1975-01-07 Chevron Res Bisphosphoramide-sulfur compound containing lubricant
US3905908A (en) * 1971-12-20 1975-09-16 Texaco Inc Lube oil containing oligomeric phosphorodiamidate
US4281128A (en) * 1975-05-21 1981-07-28 S.A. Texaco Belgium N.V. Bispiperazido phosphorus compounds
US4755311A (en) * 1986-08-14 1988-07-05 The Lubrizol Corporation Phosphorus-, sulfur- and boron-containing compositions, and lubricant and functional fluid compositions containing same

Cited By (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2460301A (en) * 1945-03-30 1949-02-01 Lubrizol Dev Corp Lubricating oils
US2509594A (en) * 1945-04-12 1950-05-30 Gen Aniline & Film Corp Production of nicotinanilide
US2508860A (en) * 1945-06-28 1950-05-23 Gen Aniline & Film Corp Production of benzamidocyclohexane
US2459113A (en) * 1945-07-06 1949-01-11 Socony Vacuum Oil Co Inc Mineral oil composition
US2459115A (en) * 1945-07-06 1949-01-11 Socony Vacuum Oil Co Inc Mineral oil composition
US2442581A (en) * 1945-07-28 1948-06-01 Tide Water Associated Oil Comp Rust-preventive composition
US2506572A (en) * 1946-04-19 1950-05-09 Standard Oil Co Lubricant composition
US2539424A (en) * 1946-05-18 1951-01-30 Standard Oil Co Esters of ps-amine reaction products as lubricating oil additives and lubricants containing same
US2506573A (en) * 1946-06-01 1950-05-09 Standard Oil Co Lubricant composition
US2500762A (en) * 1947-01-02 1950-03-14 Standard Oil Dev Co Lubricant composition
US2662095A (en) * 1948-07-09 1953-12-08 Southern Production Company In Dimethyl-phosphoric acid amide and its production
US2552536A (en) * 1948-08-23 1951-05-15 Dow Chemical Co O, o-di-(methoxyphenyl) amidothiophosphate
US2552575A (en) * 1948-08-30 1951-05-15 Dow Chemical Co O, o-di(2-allylphenyl) n-alkylamidothiophosphates
US2552576A (en) * 1948-08-30 1951-05-15 Dow Chemical Co Amidothiophosphates
US2552537A (en) * 1948-10-15 1951-05-15 Dow Chemical Co O-polyhalophenyl diamidothiophosphates
US2552538A (en) * 1948-10-15 1951-05-15 Dow Chemical Co Diamidothiophosphates
US2615038A (en) * 1948-10-15 1952-10-21 Dow Chemical Co O,o-di(polyhalophenyl) n-substituted amidothiophosphates
US2615037A (en) * 1948-10-15 1952-10-21 Dow Chemical Co O,o-di(4-chlorophenyl) n-alkylamidothiophosphates
US2552577A (en) * 1948-10-15 1951-05-15 Dow Chemical Co Diamidothiophosphates
US2624707A (en) * 1949-06-07 1953-01-06 Shell Dev Lubricating composition
US2671109A (en) * 1949-11-16 1954-03-02 Pest Control Ltd Preparation of bis-dialkylamino phosphonous anhydrides
US2706194A (en) * 1951-05-14 1955-04-12 Shell Dev Esters of phosphonic acids
US2663705A (en) * 1951-07-25 1953-12-22 American Cyanamid Co Phosphoric acid derivatives and methods of preparing the same
US2703813A (en) * 1952-03-19 1955-03-08 Monsanto Chemicals Organic phosphorus compounds
US2760974A (en) * 1952-07-28 1956-08-28 Union Oil Co Separation of phosphoryl amide adducts of benzene dicarboxylic acids
US2896400A (en) * 1953-02-16 1959-07-28 Standard Oil Co Rocket propulsion method
US2776311A (en) * 1953-06-16 1957-01-01 Dow Chemical Co Diamido anilido phosphine oxides and sulfides
US2882309A (en) * 1953-10-30 1959-04-14 Kellogg M W Co Production of organophosphorus compounds
US2882307A (en) * 1953-10-30 1959-04-14 Kellogg M W Co Production of organophosphorus compounds
US2882308A (en) * 1953-10-30 1959-04-14 Kellogg M W Co Production of organic phosphonyl halide
US2882305A (en) * 1953-10-30 1959-04-14 Kellogg M W Co Production of organic phosphonyl halide
US2882306A (en) * 1953-10-30 1959-04-14 Kellogg M W Co Production of organophosphorus compounds
US2882304A (en) * 1953-10-30 1959-04-14 Kellogg M W Co Production of organic phosphonyl halide
US2786075A (en) * 1954-09-09 1957-03-19 Monsanto Chemicals Adducts of hexamethylphosphorous triamide and polyhalo compounds
US2730547A (en) * 1955-02-01 1956-01-10 Monsanto Chemicals Benzyltris (dialkylamino) phosphonium halides
US2774658A (en) * 1955-08-30 1956-12-18 Mousanto Chemical Company Herbicidal alkyl-amino-phosphonium halides
US2941001A (en) * 1956-06-25 1960-06-14 American Potash & Chem Corp Manufacture of aminophosphines
US2995596A (en) * 1956-09-01 1961-08-08 Benckiser Gmbh Joh A Production of phosphoric aciddialkylester-amines
US3098824A (en) * 1957-11-15 1963-07-23 Pure Oil Co Lubricating composition
US3031401A (en) * 1959-06-11 1962-04-24 Gulf Research Development Co Lubricating oil composition
US3070604A (en) * 1960-07-26 1962-12-25 Basic Res Corp Fire resistant compound
US3268448A (en) * 1963-02-28 1966-08-23 Cities Service Oil Co Zinc chloride phosphothiourea compounds
US3225090A (en) * 1963-05-17 1965-12-21 Olin Mathieson Bis(aminodiarylphosphine) decaboranes
US3309317A (en) * 1964-06-08 1967-03-14 Shell Oil Co Lubricating composition
US3321401A (en) * 1964-09-18 1967-05-23 British Petroleum Co Lubricating compositions
US3433623A (en) * 1965-10-20 1969-03-18 Rohm & Haas Phosphoric triamide derivatives as herbicides
US3468946A (en) * 1965-10-20 1969-09-23 Rohm & Haas Phosphoric triamide derivatives
US3905908A (en) * 1971-12-20 1975-09-16 Texaco Inc Lube oil containing oligomeric phosphorodiamidate
US3859219A (en) * 1972-11-17 1975-01-07 Chevron Res Bisphosphoramide-sulfur compound containing lubricant
US4281128A (en) * 1975-05-21 1981-07-28 S.A. Texaco Belgium N.V. Bispiperazido phosphorus compounds
US4755311A (en) * 1986-08-14 1988-07-05 The Lubrizol Corporation Phosphorus-, sulfur- and boron-containing compositions, and lubricant and functional fluid compositions containing same

Similar Documents

Publication Publication Date Title
US2146584A (en) Lubricant
US2364284A (en) Modified lubricating oil
US2691000A (en) Lubricating oils
US2160915A (en) Lubricant
US2795553A (en) Lubricant compositions
US2343831A (en) Lubricating composition
US2109491A (en) Lubricant
US2353558A (en) Addition agent for lubricating oil and method of making same
US2403894A (en) Additives for lubricants
GB1569730A (en) 0,0-diiso-propyl-s-(2-carboethoxyethyl)-phosphorodithioate and lubricating oil compositions containing it
US2786812A (en) Mineral oil compositions containing tincontaining dithiophosphate compounds
US2410650A (en) Lubricant composition
US2354536A (en) Lubricating oil composition
US2696473A (en) Halogen containing extreme pressure lubricant stabilized with a polyalkylene polyamine
US2760937A (en) Phosphorus-containing lubricant additives
US2389527A (en) Lubricants
US2472517A (en) Addition agents for mineral oil lubricants
US3320163A (en) Phenolic corrosion inhibitors
US2149271A (en) Lubricant
US2289509A (en) Lubricant
US2494332A (en) Extreme pressure lubricants
US2506049A (en) Lubricant
US3030304A (en) Lubricating compositions
US2279218A (en) Mineral oil composition and improving agent therefor
US3317425A (en) Lubricating compositions containing a carbamoyl phosphine