US3001938A - Lubricants containing salts of organic-substituted phosphorus - containing acids - Google Patents
Lubricants containing salts of organic-substituted phosphorus - containing acids Download PDFInfo
- Publication number
- US3001938A US3001938A US725489A US72548958A US3001938A US 3001938 A US3001938 A US 3001938A US 725489 A US725489 A US 725489A US 72548958 A US72548958 A US 72548958A US 3001938 A US3001938 A US 3001938A
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- Prior art keywords
- acid
- acids
- grease
- salts
- phosphonic
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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
- C10M5/00—Solid or semi-solid compositions containing as the essential lubricating ingredient mineral lubricating oils or fatty oils and their use
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/026—Butene
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
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- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
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- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix 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
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- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
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- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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- C10M2207/283—Esters of polyhydroxy compounds
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- C10M2207/28—Esters
- C10M2207/286—Esters of polymerised unsaturated acids
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- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
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- C10M2207/32—Esters of carbonic acid
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- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
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- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/11—Complex polyesters
- C10M2209/111—Complex polyesters having dicarboxylic acid centres
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- C10M2211/06—Perfluorinated compounds
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- C10M2213/02—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen and halogen only
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- C10M2213/06—Perfluoro polymers
- C10M2213/062—Polytetrafluoroethylene [PTFE]
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
- C10M2215/065—Phenyl-Naphthyl amines
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
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- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- 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
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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- C10M2223/042—Metal salts thereof
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- C10M2229/04—Siloxanes with specific structure
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- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S159/00—Concentrating evaporators
- Y10S159/10—Organic
Definitions
- This invention relates to lubricating compositions containing salts of phosphonic and phosphinic acids. Particularly, it relates to greases and lubricating fluids containing complexes of salts of carboxylic acids and salts of a hydroxy alkyl phosphonic acid and/or a salt of a hydroxy alkyl phosphinic acid, wherein said phosphoruscontaining acid has a carbon atom content of l to 5.
- This new type of complex may be incorporated in lubricating oil in amount-s of about 20 to 30 Weight percent, based on the total composition, to form greases having higher load-carrying ability, reduced wear characteristics and a higher degree of thixotropy than greases thickened with the aforementioned prior complexes.
- fluid lubricants may be formed which also have high load-carrying ability and reduced wear properties.
- the presence of the phosphonic or phosphinic acid salt in the complex acts as a color stabilizer and oxidation inhibitor.
- the salts of the phosphorus-containing acids tend to prevent crust formation and/or undue hardening of the greases during storage, particularly when soaps of high molecular weight fatty acids (C are present in the complex.
- hydroxy alkyl phosphonic or phosphinic acids utilized in the present invention can be defined by the general formula:
- R is hydrogen or a C to C alkyl group and R may be either hydrogen or an alkyl radical containing from 1 to 5, preferably 0 to 3, carbon atoms.
- the total atent 0 are known to the art. Examples of specific compounds which may be used include:
- the high molecular weight fatty acids or aliphatic monocarboxylic acids useful for forming the complexes of the invention include naturally-occurring or synthetic, substituted and unsubstituted, saturated and unsaturated, fattyacids havingabout 16 to 30, e.g. 16 to 22, carbon atoms per molecule.
- Examples of such acids include palmitic, stearic, dihydroxy stearic, behenic, montanic, linolinic, linoleic, arachidic, ricinoleic, oleic, hydrogenated fish oil, tallow acids, etc.
- the metal component of the complex thickeners of this invention may be either an alkali metal such as lithium, potassium, sodium or an alkaline earth metal such as calcium, strontium, barium and magnesium. Mixtures of the grease-forming metals may be employed if desired. The metals are usually reacted with the acids in the form of metal bases, such as hydroxides, oxides, carbonates, etc.
- compositions of the invention will comprise a major proportion of a lubricating oil and about 5 to 30 weight percent of the complex material.
- the composition Will contain about 10 to 30, e.g. 15 to 25, weight percent of the complex, while in the case of fluid lubricants, the composition will contain about 5 to 15, e.g. 5 to 10, weight percent of the complex. All of said weight percentages are based on the total weight of the composition.
- the thickener in turn, will contain the salts of about .1 to 10, e.g. .3 to 5.0, moles of the high and/or intermediate molecular weight fatty acid per one mole of phosphonic or phosphinic acid. If the salt of a low molecular weight 'carboxylic acid is also used in the prepara- .tion of the complex, then it will be present in ratios of number of carbon atoms in the compound should be.
- X may be a hydorxyl group, in which case hydrogen whereupon the formula represents a phosphinic acid.
- These compounds and their method of preparation about 5:1 to 30:1, e.g. 5:1 to 20:1, moles of the low molecular weight carboxylic acid per one mole of the phosphonic or phosphiuic acid. In terms of parts by weight, excellent mixed-salt complexes may be prepared from a mixture of 0.2. to 5.0, e.g.
- phosphonic'or phosphinic acid 1 to 20 parts by weight of either high or intermediate molecular Weight fatty acid or mixtures in any proportion of said high and intermediate molecular weight acid, about to 15, e.g. 6 to 12 parts by weight of low molecular weight fatty acid;- and sutficent metal base to substantially neutralize said corresponding in degree of saturation and acid number to commercial stearic acid) to 7 2.7 weight percent of mineral lubricating oil (naphthenic oil having a viscosity 1 10% lauric acid; 28 caprylic acid; 56% capric acid.
- mineral lubricating oil mineral lubricating oil having a viscosity 1 10% lauric acid; 28 caprylic acid; 56% capric acid.
- a 40% vention may be either a mineral lubricating oil or a synaqueous solution of sodium hydroxide was added in an thetic lubricating oil.
- Synthetic lubricating oils which amount equivalent to 5.3 weight percent of sodium hymay be used include esters of monobasic acids (e.g. C droxide and the mixture was further heated to 460 F. Oxo alcohol ester of C Oxo acid); esters of dibasic acids Heating was then discontinued and the grease cooled, (e.g.
- esters of glycols e.g. 10 while agitating, at the rate of 5 F. per minute to 200 F. C OX0 acid diester of tetraethylene glycol
- complex One weight percent of phenyl alpha naphthylarnine was esters e.g. the complex ester formed by reacting one next added and the grease was passed through a Gaulin mole of sebacic acid with two moles of tetraethylene homogenizer operating at 6000 p.s.i., then cooled to room glycol and two moles of Z-ethyl-hexanoic acid); esters of temperature.
- phosphoric acid e.g.
- 0.1 to 10.0 weight percent based t i g i out gi g f on the total weight of the composition for example, g 6 2 g 3 3 or detergents such as calcium petroleum sulfonate; oxidation 2 b e g f t gate to at inhibitors such as phenyl alpha naphthylamine; viscosity of adout 3 t lgating was 11161651112603- index improvers such as polyisobutylene; corrosion inthehgrease E a loweh to 25 hibitors; such as sorbitan monooleate; pour depressants; Y 1c pomt P enyl alp a napht ylamme was dlspefsc dyes; other grease thickfiners and the like.
- detergents such as calcium petroleum sulfonate
- oxidation 2 b e g f t gate to at inhibitors such as phenyl alpha nap
- compositions of the invention will be then passed through a Gaulin homogenizer operating at prepared by coneutralization of the carboxylic acids and 6000 and finally cooled to mom temperature the phosphonic or phosphinic acid in situ in a lubricating EXAMPLES V1 TO VIII oil menstruum, by the addition of a metal base, followed by heating to a temperature and for a time necessary to More fluld lubncants were Prepared by P 1211x1111; form the complex. Generally the mixture will be heated the greases P III to r p p Wlth an to about 400 to 700 F., e.g. about 430 to 60 F.
- the additional portion of mineral lubricating oil. temperature may then immediately be allowed to drop, EXAM E I but preferably is maintained for /2 to 4 hours, e.g. l to 40 PL 3 hours in order to ensure the completion of the complex
- a grease was P p y chaffglllg f l 011 and formation.
- the mixture may then be cooled to about 111116 P 3 fire-heated kettle and lntlmalely them- 18 to 200 R, where conventional additives, if any, may T0 mllftllfe was addfid a blend of 12 Weight Percent be added.
- the mixture may then be homogenized such glaclal acetlc q 3 welght p f y yy as by passing through a Gaulin homogenizer or a Charethyl P Q P q and 3 We1ght P Q fi l lotte mill, followed by subsequent cooling to room tem- AAC Acld (l P t lallflc acid, Weight perature.
- the lubricating compositions may also be Percent p i/ mild and 56 Welght Percent p formed by heating the preformed salts together i th After the acid blend was stirred in, heating was initiated lubricating oil to complexing temperatures. and the mixture was heated to 460 F.
- excellent high temperature lubricants having high dropping points and excellent extreme pressure and anti-wear properties may be formed from complexes of the salts of the phosphonic acid in various combinations with salts of fatty acid.
- Examples I and II illustrate the use of the phosphonic acid and high molecular weight fatty acids. These complexes had 4-ball wear scar diameters of 0.45 to 0.04 mm. respectively, which is very good as prior commercial greases thickened with sodium complexes of comparable amounts of high molecular Weight fatty acid and acetic acid have wear scar diameters of about 0.65 mm. Also, the sodium greases of Examples I and II were waterinsoluble up to 150 R, which was surprising in view of the fact that sodium greases are invariably wa ter-soluble at much lower temperatures.
- Examples III to V illustrate calcium complex greases containing the phosphonic acid, high molecular weight fatty acid and acetic acid. These greases illustrate particularly preferred compositions of the invention since they had a high degree of thixotropy, i.e., they quickly revert to their solid form upon removal of shearing stresses, and also had very good extreme pressure and anti-wear properties. Furthermore, the greases of Examples III to V had either a very slight or no tendency at all to form a crust, while prior comparable greases containing complex salts of Hydrofol Acids 51 and acetic acid (e.g. in a 1/1 molar ratio) excessively harden on exposure to air to form undesirable crus ts.
- Hydrofol Acids 51 and acetic acid e.g. in a 1/1 molar ratio
- Examples III to V also illustrate the fact that by holding the proportion of acetic acid constant, and increasing the ratio of the phosphonic acid to the high molecular weight fatty acid, that products of increasing fluidity are obtained.
- This concept is of particular importance as it permits the formation of more fluid products which still have a high soap and correspondingly, a high metal content which imparts high extreme pressure properties to the lubricant.
- it was common practice to increase the extreme pressure properties of a lubricant by increasing the soap content however, this was rather a limited procedure since the increased soap content would unduly harden the grease.
- a method has now been found for obtaining good wear and extreme pressure properties and yet still be able to control the plasticity or fluidity of the grease.
- Examples VI to VIII illustrate the use of decreasing amounts of the complex to formmore fluid lubricants having high extreme pressure properties and low wear characteristics. Even these diluted materials illustrated some degree of thixotropy.
- the lubricant of Example VIII upon further dilution with an equal amount of mineral oil S.U.S. at 210 F.) still carried 8 Almen weights upon gradual loading and in a 4-ball wear test gave a .20 mm. dia. scar.
- These fluid and semi-fluid lubricants are particularly valuable for certain applications, as in upper cylinder lubrication of diesel engines where extreme pressure and anti-wear properties are necessary to prevent cylinder liner and ring wear.
- these lubricants are particularly good as they have a high degree of neutralization potential present, i.e. the calcium acetate portion of the complex will neutralize H 80 formed by the burning of the sulfur in the fuel.
- the soap or grease therefore present on the surface of the liner and rings also protects the metal from acid corrosion.
- Example IX illustrates a fluid lubricant prepared from the phosphonic acid, acetic acid, and a mixture of intermediate molecular weight fatty acids.
- Example IX is similar to Example V, the only difference being the use 7 of the intermediate molecular weight fatty acid instead of high molecular weight fatty acid. These examples illustrate the fact that more fluid products may also be obtained by using lower molecular weight fatty acids.
- complex thickeners comprising salts of a high molecular weight fatty acid and salts of acrylic acid by heating whole fat such as tallow, hog fat, lard oil, fish oil, or vegetable oils as rapeseed oil, mustard seed oil, etc., to high temperatures in the presence of a large excess of alkali, such as sodium or potassium alkali.
- the fat becomes saponified at about 350 F., then upon further heating to about 500 F., a portion of the fat breaks down to form glycerine which is dehydrated to acrolein which, in turn, is converted into salts of acrylic acid.
- Greases of the above type are readily prepared by dispersing a fat in lubricating oil, adding about 1.5 to 3.0 times the amount of alkali necessary for saponification, heating to a temperature of about 450 to 650 F., e.g. 500 to 550 F., for about 10 to 30 minutes, or until foaming due to hydrogen evolution ceases, cooling to about 250 to 300 F., then adding sufiicient l-hydroxy alkyl phosphonic acid to neutralize any excess alkali, then maintaining a temperature of about 200 to 400 F., e.g. 250 to 300 F. for about 20 to 45 minutes in order to ensure the complete reaction of the phosphonic acid with the excess alkali, followed by cooling to room temperature.
- EXAMPLE X-A A grease was prepared by charging mustard seed oil, mineral oil and sodium petroleum sulfonate (ave. mol. wt.480) to a kettle and then warming to 150 F., while mixing. A 40 percent aqueous solution of sodium hydroxide was added to the kettle and the contents further heated. Dehydration and foaming then occurred, which ceased at temperatures of about 350 F. On continued heating to 450 F., foaming again began due to hydrogen evolution. Heating was continued to 520 F. and the temperature maintained there for about 30 minutes, until foaming ceased. Heating was discontinued and the temperature was allowed to drop to 300 F., at which point the hydroxy phosphonic acid was added. The mixture was maintained at 300 F. for about 30 minutes. Then phenyl alpha naphthylamine was added and the grease cooled to 150 P. where it was passed through a Gaulin homogenizer operating at 6,000 p.s.i. The grease was then cooled to room temperature.
- EXAMPLE X-B A grease similar to that of Example X-A was prepared, except that the excess alkalinity was not neutralized with phosphonic acid.
- Example XI The grease of Example X-A was further diluted with 25 weight percent of additional mineral oil.
- compositions of the above greases and their physical properties are shown in Table II.
- the greases prepared from the phosphonic acid had low wear scar diameters, better color stability and were more resistant to oxidation than a similar grease which did not contain the phosphonic acid.
- EXAMPLE XII A 5-liter 4-necked flask equipped with a stirrer, condenser, thermometer and dropping funnel was charged with 209 g. acetone (3.6 m.) and 412 g. PCl (3.0 m.). This mixture was stirred for 5 minutes, then allowed to stand overnight (16 hours) at room temperature. It was then cooled to 55 F. and maintained at 55 to 65 F. while 720 g. of glacial acetic acid was added over a 45 minute period. Stirring was continued at this temperature for another 2 hours, after which the total prodnot was transferred to a distillation flask and stripped in a short path still.
- the first part of the stripping was at atmospheric pressure until most of the HCl gas and acetyl chloride had been removed. Reduced pressure was then applied and the product stripped to a pot temperature of 93 C. with the vapor temperature at 65 C. under 2.5 mm. Hg. This left a residue of 467 g. having a neut. number of 819.3 mg. KOH/gm. crude material.
- This grease was prepared by charging the lime, mineral oil, Hydrofol Acids 51, and the crude phosphonic acid to a fire heated kettle and intimately mixing. Th glacial acetic acid was then added and the mixture was 10 where the grease was Gaulin homogenized at 6000 p.s.i. before being cooled to room temperature.
- the resulting grease had the following properties:
- a lubricant composition comprising a major proh n f r blended Wlth Varymg amounts of mineral portion of lubricating oil and an extreme-pressure imlubricating oils as shown in the following table: parting amount of a mixed-salt complex material com- T able III
- Example X11 Components (weight percent) A B O D Base composition so an 70 Mineral lubricating oil (80 SUS at 210 F.)...---. R0 40 in Mineral oil bright stock (about 191 SUS at 210 Properties Appearance Excellent... Excellent..-. Excellent-... Excellent. Dropping point F-. 500+ 500+ 500+. Penetration 77 F. InI1J./l0 1 Unworked... sen n 300 320.
- Stability Good Good Good 1 Base composition prepared from 11.4% glacial acetic acid, 6% hydrofol acids 51, 1.6 weight percent of phosphonic acid in acetic acid solution, 9.8% hydrated lime, 1.0% phenyl a-naphthylamine, and 70.2% mineral oil.
- greases having prising metal salts of fatty acids selected from the group varying degrees of thixotropy may be prepared from the crude phosphonic acid.
- a composition similar to that of Example XII-A was prepared using the purified acetone hydroxy phosphonic acid instead of the corresponding crude phosphonic acid.
- a phosphorus containing acid containing 1 to 5 carbon atoms selected from the group consisting of l-hydroxy alkyl phosphonic acid and l-hydroxy alkyl phosphinic acids, wherein the molar ratio of said fatty acids to said phosphorus-containing acid is about 0.1 to 10:0 moles of fatty acid per mole of said phosphorus-containing acid and wherein said metal is selected from the group con sisting of alkali metals and alkaline earth metals.
- a lubricant composition according to claim 1 which contains about 5 to 30 weight percent, based on the total composition, of said complex material.
- a lubricant composition according to claim 1, wherein said mixed-salt complex includes salts of C to C fatty acid in a molar ratio of said C to C fatty acid to said phosphorus-containing acid of about 5:1 to 30:1.
- a lubricating composition comprising a major proportion of lubricating oil and about 5 to 30 weight percent, based on the total composition, of a thickener comprising, in a molar ratio, metal salt of about 0.5 to 30.0
- C to C fatty acid metal salt of about .1 to moles of fatty acid selected from the group consisting of C to C fatty acid and C to C fatty acid, and mixtures thereof, and metal salt of one mole of a phosphoruscontaining acid selected from the group consisting of 1- hydroxy alkyl phosphonic and l-hydroxy alkyl phosphinic acid containing 1 to 5 carbon atoms, and wherein said metal is selected from the group consisting of alkali and alkaline earth metals.
- a lubricating composition comprising a major proportion of lubricating oil and 5 to 30 weight percent of a thickener which comprises metal salts of: 2 to 5 parts by Weight of a C to C of an organic phosphorus-containing acid selected from the group consisting of l-hydroxy alkyl phosphonic acid and l-hydroxy alkyl phosphinic acid, 1 to 20 parts by weight of fatty acid selected from the group consisting of C to C fatty acid and C to C fatty acid and mixtures thereof, and 0 to 15 parts by weight of C to C fatty acid, wherein said metal is selected from the group consisting of alkali metals and alkaline earth metals.
- a process for the preparation of lubricants which comprises coneutralizing with a metal base a dispersion of fatty acid selected from the group consisting of C to C fatty acids, C to C fatty acids and mixtures thereof, and a phosphorus-containing acid selected from the group consisting of l-hydroxy alkyl phosphonic and phosphinic acids in lubricating oil, then heating to a temperature of about 400 to 700 F. and then cooling, said metal base being selected from the group consisting of alkaline earth metal bases.
- a process for the preparation of a lubricant which comprises reacting a dispersion of whole fat in lubricating oil with about 1.5-3.0 times the amount of alkali needed for complete saponification of said fat at temperatures of about 450 to 650 F. until foaming substantially ceases, cooling to about 200 to 400 F., then neutralizing said excess alkali with a phosphorus-containing acid selected from the group consisting of l-hydroxy-alkyl phosphonic and phosphinic acids before final cooling to form said grease.
- a lubricant composition comprising lubricating oil and about 5 to 30 wt. percent, based on the total composition, of a mixed-salt material comprising metal salts of a fatty acid selected from the group consisting of C to C and C to C fatty acids and metal salts of a crude C to C l-hydroxy alkyl phosphonic acid material comprising a solution of said phosphonic acid in acetic acid ob tained by reacting a ketone and PCl adding acetic acid in excess and distilling to remove HCl and acetyl chloride to leave said crude phosphonic acid as a residue, wherein the molar ratio of said fatty acids to said phosphonic acid is about 0.1 to 10.0 moles of fatty acid per mole of said phosphonic acid and wherein said metal is selected from the group consisting of alkali metals and alkaline earth metals.
Description
United States This invention relates to lubricating compositions containing salts of phosphonic and phosphinic acids. Particularly, it relates to greases and lubricating fluids containing complexes of salts of carboxylic acids and salts of a hydroxy alkyl phosphonic acid and/or a salt of a hydroxy alkyl phosphinic acid, wherein said phosphoruscontaining acid has a carbon atom content of l to 5.
This application is a continuation-in-part of our prior pending application Serial Number 654,981, filed April 25, 1957, and now abandoned.
Mixed salt complexes comprising salts of low molecular weight carboxylic acid in combination with salts of intermediate and/or high molecular weight carboxylic acid, are known. These prior complexes have been used as grease thickeners and for imparting certain desirable properties to fluid-type lubricants. However, it has now been found that greases and lubricating fluids may be prepared from complexes of salts of hydroxy alkyl phosphonic or phosphinic acid in various combinations with salts of low molecular weight carboxylic acid, intermediate and high molecular weight carboxylic acid. This new type of complex may be incorporated in lubricating oil in amount-s of about 20 to 30 Weight percent, based on the total composition, to form greases having higher load-carrying ability, reduced wear characteristics and a higher degree of thixotropy than greases thickened with the aforementioned prior complexes. By using smaller amounts, such as 5 to weight percent of the complex of the invention, fluid lubricants may be formed which also have high load-carrying ability and reduced wear properties. Furthermore, the presence of the phosphonic or phosphinic acid salt in the complex acts as a color stabilizer and oxidation inhibitor. .In addition, the salts of the phosphorus-containing acids tend to prevent crust formation and/or undue hardening of the greases during storage, particularly when soaps of high molecular weight fatty acids (C are present in the complex.
The hydroxy alkyl phosphonic or phosphinic acids utilized in the present invention can be defined by the general formula:
wherein R is hydrogen or a C to C alkyl group and R may be either hydrogen or an alkyl radical containing from 1 to 5, preferably 0 to 3, carbon atoms. The total atent 0 are known to the art. Examples of specific compounds which may be used include:
1-hydroxy-l-methylethylphosphonic acid l-hydroxyethylphosphonic acid l-hydroxy-l-methylpropylphosphonic acid 1-hydroxy-Z-methylpropylphosphonic acid l-hydroxybutylphosphinic acid l-hydroxymethylphosphinic acid l-hydroxy-l-ethylpropylphosphinic acid 1-hydroxy-3-methylbutylphosphinic acid l-hydroxypropylphosphonic acid anoic acid, lauric acid, etc.
The high molecular weight fatty acids or aliphatic monocarboxylic acids useful for forming the complexes of the invention include naturally-occurring or synthetic, substituted and unsubstituted, saturated and unsaturated, fattyacids havingabout 16 to 30, e.g. 16 to 22, carbon atoms per molecule. Examples of such acids include palmitic, stearic, dihydroxy stearic, behenic, montanic, linolinic, linoleic, arachidic, ricinoleic, oleic, hydrogenated fish oil, tallow acids, etc.
The metal component of the complex thickeners of this invention may be either an alkali metal such as lithium, potassium, sodium or an alkaline earth metal such as calcium, strontium, barium and magnesium. Mixtures of the grease-forming metals may be employed if desired. The metals are usually reacted with the acids in the form of metal bases, such as hydroxides, oxides, carbonates, etc.
The compositions of the invention will comprise a major proportion of a lubricating oil and about 5 to 30 weight percent of the complex material. When a grease is desired, the composition Will contain about 10 to 30, e.g. 15 to 25, weight percent of the complex, while in the case of fluid lubricants, the composition will contain about 5 to 15, e.g. 5 to 10, weight percent of the complex. All of said weight percentages are based on the total weight of the composition.
The thickener, in turn, will contain the salts of about .1 to 10, e.g. .3 to 5.0, moles of the high and/or intermediate molecular weight fatty acid per one mole of phosphonic or phosphinic acid. If the salt of a low molecular weight 'carboxylic acid is also used in the prepara- .tion of the complex, then it will be present in ratios of number of carbon atoms in the compound should be.
about 1 to 5. X may be a hydorxyl group, in which case hydrogen whereupon the formula represents a phosphinic acid. These compounds and their method of preparation about 5:1 to 30:1, e.g. 5:1 to 20:1, moles of the low molecular weight carboxylic acid per one mole of the phosphonic or phosphiuic acid. In terms of parts by weight, excellent mixed-salt complexes may be prepared from a mixture of 0.2. to 5.0, e.g. 0.5 to 4.0, parts of the phosphonic'or phosphinic acid, 1 to 20 parts by weight of either high or intermediate molecular Weight fatty acid or mixtures in any proportion of said high and intermediate molecular weight acid, about to 15, e.g. 6 to 12 parts by weight of low molecular weight fatty acid;- and sutficent metal base to substantially neutralize said corresponding in degree of saturation and acid number to commercial stearic acid) to 7 2.7 weight percent of mineral lubricating oil (naphthenic oil having a viscosity 1 10% lauric acid; 28 caprylic acid; 56% capric acid.
acid mixture. of 55 S.U.S. at 210 F.). This mixture was heated in a The lubricating oil used in the compositions of the infire-heated kettle to about 150 F At this point, a 40% vention may be either a mineral lubricating oil or a synaqueous solution of sodium hydroxide was added in an thetic lubricating oil. Synthetic lubricating oils which amount equivalent to 5.3 weight percent of sodium hymay be used include esters of monobasic acids (e.g. C droxide and the mixture was further heated to 460 F. Oxo alcohol ester of C Oxo acid); esters of dibasic acids Heating was then discontinued and the grease cooled, (e.g. di-Z-ethyl hexyl sebacate); esters of glycols (e.g. 10 while agitating, at the rate of 5 F. per minute to 200 F. C OX0 acid diester of tetraethylene glycol); complex One weight percent of phenyl alpha naphthylarnine was esters (e.g. the complex ester formed by reacting one next added and the grease was passed through a Gaulin mole of sebacic acid with two moles of tetraethylene homogenizer operating at 6000 p.s.i., then cooled to room glycol and two moles of Z-ethyl-hexanoic acid); esters of temperature. phosphoric acid (e.g. the ester formed by contacting three 15 EXAMPLE II moles of the monomethyl ether of ethylene glycol with I one mole of phosphorus oxychloride, etc.); halocarbon Examp 16 H was prepared m i same manner as Ex ample I, except that the proportions of the components OllS (e.g. the polymer of chlorotrifiuoroethylene containwere Chan ed as Shown in Table I ing twelve recurring units of chlorotrifiuoroethylene); g alkyl silicates(e.g. the methyl polysiloxanes);sulfite esters 20 EXAMPLES 111 To V (e.g. ester formed by reacting one mole of sulfur oXychloride with two moles of the methyl ether of ethylene These. i i a i f ig f g a i glycol, etc.); carbonates; mercaptals; formals,; etc. 9; g1 18 p 05p omc Various other additives may also be added to the lubri- 0 a W q g i; eating composition (e.g. 0.1 to 10.0 weight percent based t i g i out gi g f on the total weight of the composition), for example, g 6 2 g 3 3 or detergents such as calcium petroleum sulfonate; oxidation 2 b e g f t gate to at inhibitors such as phenyl alpha naphthylamine; viscosity of adout 3 t lgating was 11161651112603- index improvers such as polyisobutylene; corrosion inthehgrease E a loweh to 25 hibitors; such as sorbitan monooleate; pour depressants; Y 1c pomt P enyl alp a napht ylamme was dlspefsc dyes; other grease thickfiners and the like. in the grease. The grease was further cooled to 150 F., In general the compositions of the invention will be then passed through a Gaulin homogenizer operating at prepared by coneutralization of the carboxylic acids and 6000 and finally cooled to mom temperature the phosphonic or phosphinic acid in situ in a lubricating EXAMPLES V1 TO VIII oil menstruum, by the addition of a metal base, followed by heating to a temperature and for a time necessary to More fluld lubncants were Prepared by P 1211x1111; form the complex. Generally the mixture will be heated the greases P III to r p p Wlth an to about 400 to 700 F., e.g. about 430 to 60 F. The additional portion of mineral lubricating oil. temperature may then immediately be allowed to drop, EXAM E I but preferably is maintained for /2 to 4 hours, e.g. l to 40 PL 3 hours in order to ensure the completion of the complex A grease was P p y chaffglllg f l 011 and formation. The mixture may then be cooled to about 111116 P 3 fire-heated kettle and lntlmalely them- 18 to 200 R, where conventional additives, if any, may T0 mllftllfe was addfid a blend of 12 Weight Percent be added. The mixture may then be homogenized such glaclal acetlc q 3 welght p f y yy as by passing through a Gaulin homogenizer or a Charethyl P Q P q and 3 We1ght P Q fi l lotte mill, followed by subsequent cooling to room tem- AAC Acld (l P t lallflc acid, Weight perature. The lubricating compositions may also be Percent p i/ mild and 56 Welght Percent p formed by heating the preformed salts together i th After the acid blend was stirred in, heating was initiated lubricating oil to complexing temperatures. and the mixture was heated to 460 F. Heating was then The invention will be further understood by the follow- 0 discontinued and the grease cooled to 200 F., at which ing examples which include the preferred embodiments point the phenyl alpha naphthylamine was added. The of the invention. product was then cooled to 150 F. and passed through a EXAMPLE I Gaulin homogenizer operating at 6,000 p.s.i. The prod- A grease was prepared by adding 4 weight percent of net was cooled 10100111 temperature l-hydroxy-1-methylethyl phosphonic acid and 20 weight The compositions and properties of Examples I to IX percent of Hydrofol Acids 51 (hydrogenated fish oil acids are summarized in Tables I and I-A, which follow.
Table l Example Components (weight percent) I II III IV V VI VII V111 1X l-hydroxy-l-methylethylphosphonicacid .percent- 4.0 2.0 1.0 2.0 3.0 0.5 1.0 1.5 3.0 Hydrofol acids 51 do 20.0 10.0 5.0 4.0 3.0 2.5 2.0 1.5 Wecoline AAC acid 1 (in 3.0 Glacial acetic acid (in 12. 0 12. O 12.0 6. 0 0. 0 6.0 12. 0 Sodium hydroxide -do 5. 3 2. 7 Hydratedlime do 9.6 10.0 10.5 4.3 5.0 5.3 10.5 Phenyl a naphthylamine -do 1. 0 1. 0 1. 0 1. 0 1. 0 0. 5 0. 5 0. 5 1. 0 Mineral lubricating oil:
55 ans. v15. at 210F do- 69.7 84.3 71.4 71.0 70.5 35.7 35.5 35.2 70.5 so s.U.s. vis. at210 F (I 50.0 50.0 50.0 Mole ratio of high or intermediate molecular weight fatty acid to phosphonic acid 2. 5/1 2.5/1 2. 5/1 1/1 .5/1 2.5/1 1/1 0. 5 1 1.13 1 Mole ratio of acetic acid to phosphonic acid Table I-A Example Properties I II III IV V VI VII VIII IX Appearan Excellent, smooth, homogeneous lubricant Dropping point, F 500+ 500+ 600 500+ 500+ 500 500 Penetration 77 F. mun/10- Unworked 192 275 195 300 350 360 380 Worked 60 strokes 202 285 200 310 Worked 100,000 strokes (fine hole worker plate) 215 290 195 285 'Ihlxotropy and effect of temperature Not thixotropic G 1 thixotrpy 1 light thi xotropy 3 Penetrations at 300 F 320 340 375 Crust formation None None Slight None None None None None None Water solubility (boiling water) Up to 150 Insol. Insol. None None None Above 150 F. None None None Viscosities S.U. S. at
100 2, 100 210 F. 200 Transition point on her fine (6) Stability of dispersion Excellent 7 Extreme pressure properties: Almen Tests- Wgts. carried (gradual load) 15 15 13 15 15 15 \Vgts. carried (shock loading) 15 15 15 15 15 Pin Condition. 4 ball wear test scar spot dia. mm. (1,800 R.P.M.10
kg.1 hr. at 75 C. 0. 45 O. 40 0.22 0.20 0.22 0.28 0.20 0. 0. 24 Iimken machine test, 45 lbs. load Pass Pass Pass Norma Hoflmann oxidation hours to 5 p.s.i. drop 400 400+ 300 400 385 Lubrication life (hours) 250 F.l0,000 r.p.m 9 2, 500 3, 200+ 1, 500+ 3, 000+ 1 Semifluid. I Tends to set up harder after working.
3 Sets up solid on removal of shearing stress. Also tends to become harder on increasing temperature.
4 Slowly disintegrates.
5 Disintegrates.
6 Remains fluid up to 400 F.
7 No tendency to separate after 14 days at 210 F. 8 Excellent, polished.
9 Still running.
As seen from the above table, excellent high temperature lubricants, having high dropping points and excellent extreme pressure and anti-wear properties may be formed from complexes of the salts of the phosphonic acid in various combinations with salts of fatty acid.
Examples I and II illustrate the use of the phosphonic acid and high molecular weight fatty acids. These complexes had 4-ball wear scar diameters of 0.45 to 0.04 mm. respectively, which is very good as prior commercial greases thickened with sodium complexes of comparable amounts of high molecular Weight fatty acid and acetic acid have wear scar diameters of about 0.65 mm. Also, the sodium greases of Examples I and II were waterinsoluble up to 150 R, which was surprising in view of the fact that sodium greases are invariably wa ter-soluble at much lower temperatures.
Examples III to V illustrate calcium complex greases containing the phosphonic acid, high molecular weight fatty acid and acetic acid. These greases illustrate particularly preferred compositions of the invention since they had a high degree of thixotropy, i.e., they quickly revert to their solid form upon removal of shearing stresses, and also had very good extreme pressure and anti-wear properties. Furthermore, the greases of Examples III to V had either a very slight or no tendency at all to form a crust, while prior comparable greases containing complex salts of Hydrofol Acids 51 and acetic acid (e.g. in a 1/1 molar ratio) excessively harden on exposure to air to form undesirable crus ts. Examples III to V also illustrate the fact that by holding the proportion of acetic acid constant, and increasing the ratio of the phosphonic acid to the high molecular weight fatty acid, that products of increasing fluidity are obtained. This concept is of particular importance as it permits the formation of more fluid products which still have a high soap and correspondingly, a high metal content which imparts high extreme pressure properties to the lubricant. Generally, in the past, it was common practice to increase the extreme pressure properties of a lubricant by increasing the soap content, however, this was rather a limited procedure since the increased soap content would unduly harden the grease. However, a method has now been found for obtaining good wear and extreme pressure properties and yet still be able to control the plasticity or fluidity of the grease.
Examples VI to VIII illustrate the use of decreasing amounts of the complex to formmore fluid lubricants having high extreme pressure properties and low wear characteristics. Even these diluted materials illustrated some degree of thixotropy. The lubricant of Example VIII, upon further dilution with an equal amount of mineral oil S.U.S. at 210 F.) still carried 8 Almen weights upon gradual loading and in a 4-ball wear test gave a .20 mm. dia. scar. These fluid and semi-fluid lubricants are particularly valuable for certain applications, as in upper cylinder lubrication of diesel engines where extreme pressure and anti-wear properties are necessary to prevent cylinder liner and ring wear. In view of the current tendency to burn the more economical high sulfur-containing residual fuel oils in diesel engines, these lubricants are particularly good as they have a high degree of neutralization potential present, i.e. the calcium acetate portion of the complex will neutralize H 80 formed by the burning of the sulfur in the fuel. The soap or grease therefore present on the surface of the liner and rings also protects the metal from acid corrosion.
Example IX illustrates a fluid lubricant prepared from the phosphonic acid, acetic acid, and a mixture of intermediate molecular weight fatty acids. Example IX is similar to Example V, the only difference being the use 7 of the intermediate molecular weight fatty acid instead of high molecular weight fatty acid. These examples illustrate the fact that more fluid products may also be obtained by using lower molecular weight fatty acids.
It had been known to form complex thickeners comprising salts of a high molecular weight fatty acid and salts of acrylic acid by heating whole fat such as tallow, hog fat, lard oil, fish oil, or vegetable oils as rapeseed oil, mustard seed oil, etc., to high temperatures in the presence of a large excess of alkali, such as sodium or potassium alkali. The fat becomes saponified at about 350 F., then upon further heating to about 500 F., a portion of the fat breaks down to form glycerine which is dehydrated to acrolein which, in turn, is converted into salts of acrylic acid. However, the large excess of alkali necessary for such reactions tends to make the grease more abrasive and therefore undesirable from a dermatitis standpoint. It has now been found that by neutralizing the excess alkali with the phosphonic acids of the invention such as l-hydroxy-l-methylethyl phosphonic acid, that the extreme pressure and anti-wear properties of the grease are much improved along with highly improved resistance to oxidation, while the abrasiveness due to the excess alkali is eliminated. This concept of the invention is illustrated by the following examples.
Greases of the above type are readily prepared by dispersing a fat in lubricating oil, adding about 1.5 to 3.0 times the amount of alkali necessary for saponification, heating to a temperature of about 450 to 650 F., e.g. 500 to 550 F., for about 10 to 30 minutes, or until foaming due to hydrogen evolution ceases, cooling to about 250 to 300 F., then adding sufiicient l-hydroxy alkyl phosphonic acid to neutralize any excess alkali, then maintaining a temperature of about 200 to 400 F., e.g. 250 to 300 F. for about 20 to 45 minutes in order to ensure the complete reaction of the phosphonic acid with the excess alkali, followed by cooling to room temperature.
EXAMPLE X-A A grease was prepared by charging mustard seed oil, mineral oil and sodium petroleum sulfonate (ave. mol. wt.480) to a kettle and then warming to 150 F., while mixing. A 40 percent aqueous solution of sodium hydroxide was added to the kettle and the contents further heated. Dehydration and foaming then occurred, which ceased at temperatures of about 350 F. On continued heating to 450 F., foaming again began due to hydrogen evolution. Heating was continued to 520 F. and the temperature maintained there for about 30 minutes, until foaming ceased. Heating was discontinued and the temperature was allowed to drop to 300 F., at which point the hydroxy phosphonic acid was added. The mixture was maintained at 300 F. for about 30 minutes. Then phenyl alpha naphthylamine was added and the grease cooled to 150 P. where it was passed through a Gaulin homogenizer operating at 6,000 p.s.i. The grease was then cooled to room temperature.
EXAMPLE X-B A grease similar to that of Example X-A was prepared, except that the excess alkalinity was not neutralized with phosphonic acid.
EXAMPLE XI The grease of Example X-A was further diluted with 25 weight percent of additional mineral oil.
The compositions of the above greases and their physical properties are shown in Table II.
Table 11 Example Components (parts by weight) X-A X-B XI Mustard seed oil 22.00 22.00 16. 50 Sodium hydroxide..- 4. 4. 75 3. 71 Sodium sulfonate 1.00 .75 Mineral lubricating oil (55 S 77.25 77. 17 l-hydroxy-l-methylothyl phosphonic acid.- 1. 50 1. 12 Phcnyl alpha naphthylamine 1.00 1 00 .75
Properties Appearance Dropping point, F 500+ 500+ 480 Penetration 77 F. rum/10:
Unworlred 2G5 Worked 60 strokes 180 275 275 Worked 100,000 strokcs 340 325 Lubrication test 2 (204 bearing time and temperature rise 4-ba1l wear test scar dia., mm. (1,800 r.p.m.l0
kg. ld.1 hr. at 75 C. 0. 40 0. 65 0.35 Color stability, 3 weeks at 250 F Norma Hofimann oxidation, hours to 5 l.
drop 305 225 350 l Excellent, smooth grease.
2 Anti-Friction Bearing Manufacturers Association-National Lubricating Grease Institute Cooperative Test for Lubrication Life.
3 10 min., 50 F. rise.
4 Excellent, no crust formation or darkening of grease.
i Poor-dark. Slight crust formation.
As seen from the above data, the greases prepared from the phosphonic acid had low wear scar diameters, better color stability and were more resistant to oxidation than a similar grease which did not contain the phosphonic acid.
While the preceding examples utilized a purified l-hydroxy-l-methylethyl phosphonic acid, it was also found that a crude phosphonic acid product resulting from the commercial preparation of the acid is suitable and can be more easily and less expensively manufactured. Thus in the commercial preparation of the acid, equal molar quantities of a ketone, e.g. acetone, and phosphorous trichloride were reacted together. Acetic acid in excess of 2 moles was then added and the acetyl chloride and HCl which formed were removed by vacuum distillation. The resulting phosphonic acid material was then hydrolyzed and recrystallized from the excess acetic acid. It has now been found that after distillation to remove the HCl and acetyl chloride, the crude dispersion or solution of the phosphonic acid in acetic acid may be employed directly in preparing the grease. This concept is illustrated by the following example.
EXAMPLE XII A 5-liter 4-necked flask equipped with a stirrer, condenser, thermometer and dropping funnel was charged with 209 g. acetone (3.6 m.) and 412 g. PCl (3.0 m.). This mixture was stirred for 5 minutes, then allowed to stand overnight (16 hours) at room temperature. It was then cooled to 55 F. and maintained at 55 to 65 F. while 720 g. of glacial acetic acid was added over a 45 minute period. Stirring was continued at this temperature for another 2 hours, after which the total prodnot was transferred to a distillation flask and stripped in a short path still. The first part of the stripping was at atmospheric pressure until most of the HCl gas and acetyl chloride had been removed. Reduced pressure was then applied and the product stripped to a pot temperature of 93 C. with the vapor temperature at 65 C. under 2.5 mm. Hg. This left a residue of 467 g. having a neut. number of 819.3 mg. KOH/gm. crude material.
The residue obtained above and consisting of about 70 wt. percent crude phosphonic acid and 30 wt. percent 9 acetic acid was then used to prepare a grease having the following composition:
Mineral lubricating oil having a viscosity of 55 SUS at 210 F 70.2
This grease was prepared by charging the lime, mineral oil, Hydrofol Acids 51, and the crude phosphonic acid to a fire heated kettle and intimately mixing. Th glacial acetic acid was then added and the mixture was 10 where the grease was Gaulin homogenized at 6000 p.s.i. before being cooled to room temperature. The resulting grease had the following properties:
Appearance-excellent, smooth uniform grease Dropping point500 F.+ Penetration, 77 F., mm./10:
Unworked240 Worked, 6O strokes-under shearing stress the grease becomes semi-fluid. Upon removal of stress the grease hardened immediately.
B. 80 wt. percent of the grease prepared above was diluted with 20 wt. percent of additional mineral lubricating oil (80 SUS at 210 F.), then Gaulin-homogeno a 15 ized at 5000 p.s.i. A smooth solid grease resulted havgeattid toh4601 F. Elb 'ii f i to i mg an A.S.T.M. unworked penetration of 310 min/l t L' iig a e s ur er 3 at 77 F.; a high degree of thixotropy; good storage h w ere e 9 grease 1 ase was stability; and which carried Almen weights and gave omogemzed at 6,000 p.s.1., then coo ed to room tema wear scar dia. 019,025 in the 447211 Wear test. P What is claimed is:
The homogelllled base mateQal P p abov? Was 1. A lubricant composition comprising a major proh n f r blended Wlth Varymg amounts of mineral portion of lubricating oil and an extreme-pressure imlubricating oils as shown in the following table: parting amount of a mixed-salt complex material com- T able III Example X11 Components (weight percent) A B O D Base composition so an 70 Mineral lubricating oil (80 SUS at 210 F.)...---. R0 40 in Mineral oil bright stock (about 191 SUS at 210 Properties Appearance Excellent... Excellent..-. Excellent-... Excellent. Dropping point F-. 500+ 500+ 500+ 500+. Penetration 77 F. InI1J./l0 1 Unworked... sen n 300 320.
Worked 60 strokes Semifiuid-.. Semi-fluid.-- Semi-fluid... 380 to fluid} Time to recover to original consistency 10 min 3min 15 secs Instantaneous. 4-ball wear test scar spot dia. 111111.- 0.25.. .23.- .24.
Stability Good Good Good 1 Base composition prepared from 11.4% glacial acetic acid, 6% hydrofol acids 51, 1.6 weight percent of phosphonic acid in acetic acid solution, 9.8% hydrated lime, 1.0% phenyl a-naphthylamine, and 70.2% mineral oil.
2 Fluid while mixing or exerting shearing stress. B No tendency to solidify or crust formation after storage for 30 days.
As seen from the above compositions, greases having prising metal salts of fatty acids selected from the group varying degrees of thixotropy may be prepared from the crude phosphonic acid. For comparison, a composition similar to that of Example XII-A was prepared using the purified acetone hydroxy phosphonic acid instead of the corresponding crude phosphonic acid. However, there were no significant diiferences between the properties of the two compositions.
To illustrate the use of a phosphinic acid in preparing the grease compositions of the invention, the following example was carried out:
EXAMPLE XIII A. A grease was prepared having the following composition:
Percent Glacial acetic acid 12.0 Hydrofol acids 51 5.0 l-hydroxy-l-methyl propyl phosphinic acid 1.0 Hydrated lime 9.6 Phenyl a-naphthylamine 1.0 Diol 55---- 71.4
consisting of intermediate and high molecular weight fatty acids and mixtures thereof, and metal salts of a phosphorus containing acid containing 1 to 5 carbon atoms selected from the group consisting of l-hydroxy alkyl phosphonic acid and l-hydroxy alkyl phosphinic acids, wherein the molar ratio of said fatty acids to said phosphorus-containing acid is about 0.1 to 10:0 moles of fatty acid per mole of said phosphorus-containing acid and wherein said metal is selected from the group con sisting of alkali metals and alkaline earth metals.
2. A lubricant composition according to claim 1, which contains about 5 to 30 weight percent, based on the total composition, of said complex material.
3. A lubricant composition according to claim 1, wherein said fatty acid comprises a mixture of C to C fatty acid and C to C fatty acid.
4. A lubricant composition according to claim 1, wherein said phosphorus-containing acid is a phosphinic acid.
5. A lubricant composition according to claim 1, wherein said phosphorus-containing acid is a phosphonic acid.
6. A lubricant composition according to claim 1, wherein said mixed-salt complex includes salts of C to C fatty acid in a molar ratio of said C to C fatty acid to said phosphorus-containing acid of about 5:1 to 30:1.
7. A lubricant composition according to claim 1, wherein said oil is a mineral oil.
8. A lubricating composition comprising a major proportion of lubricating oil and about 5 to 30 weight percent, based on the total composition, of a thickener comprising, in a molar ratio, metal salt of about 0.5 to 30.0
moles of C to C fatty acid, metal salt of about .1 to moles of fatty acid selected from the group consisting of C to C fatty acid and C to C fatty acid, and mixtures thereof, and metal salt of one mole of a phosphoruscontaining acid selected from the group consisting of 1- hydroxy alkyl phosphonic and l-hydroxy alkyl phosphinic acid containing 1 to 5 carbon atoms, and wherein said metal is selected from the group consisting of alkali and alkaline earth metals.
9. A lubricating composition comprising a major proportion of lubricating oil and 5 to 30 weight percent of a thickener which comprises metal salts of: 2 to 5 parts by Weight of a C to C of an organic phosphorus-containing acid selected from the group consisting of l-hydroxy alkyl phosphonic acid and l-hydroxy alkyl phosphinic acid, 1 to 20 parts by weight of fatty acid selected from the group consisting of C to C fatty acid and C to C fatty acid and mixtures thereof, and 0 to 15 parts by weight of C to C fatty acid, wherein said metal is selected from the group consisting of alkali metals and alkaline earth metals.
10. A process for the preparation of lubricants which comprises coneutralizing with a metal base a dispersion of fatty acid selected from the group consisting of C to C fatty acids, C to C fatty acids and mixtures thereof, and a phosphorus-containing acid selected from the group consisting of l-hydroxy alkyl phosphonic and phosphinic acids in lubricating oil, then heating to a temperature of about 400 to 700 F. and then cooling, said metal base being selected from the group consisting of alkaline earth metal bases.
11. A process for the preparation of a lubricant which comprises reacting a dispersion of whole fat in lubricating oil with about 1.5-3.0 times the amount of alkali needed for complete saponification of said fat at temperatures of about 450 to 650 F. until foaming substantially ceases, cooling to about 200 to 400 F., then neutralizing said excess alkali with a phosphorus-containing acid selected from the group consisting of l-hydroxy-alkyl phosphonic and phosphinic acids before final cooling to form said grease.
12. A lubricant composition comprising lubricating oil and about 5 to 30 wt. percent, based on the total composition, of a mixed-salt material comprising metal salts of a fatty acid selected from the group consisting of C to C and C to C fatty acids and metal salts of a crude C to C l-hydroxy alkyl phosphonic acid material comprising a solution of said phosphonic acid in acetic acid ob tained by reacting a ketone and PCl adding acetic acid in excess and distilling to remove HCl and acetyl chloride to leave said crude phosphonic acid as a residue, wherein the molar ratio of said fatty acids to said phosphonic acid is about 0.1 to 10.0 moles of fatty acid per mole of said phosphonic acid and wherein said metal is selected from the group consisting of alkali metals and alkaline earth metals.
References Cited in the file of this patent UNITED STATES PATENTS 2,513,680 Schott et a1. July 4, 1950 2,628,949 Butcosk Feb. 17, 1953 2,758,971 Mikeska Aug. 14, 1956 2,837,481 Hotten et a1. June 3, 1958 2,846,392 Morway et a1 Aug. 5, 1958 FOREIGN PATENTS 549,296 Great Britain Nov. 16, 1942
Claims (1)
1. A LUBRICANT COMPOSITION COMPRISING A MAJOR PROPORTION OF LUBRICATING OIL AND AN EXTREME-PRESSURE IMPARTING AMOUNT OF A MIXED-SALT COMPLEX MATERIAL COMPRISING METAL SALTS OF FATTY ACIDS SELECTED FROM THE GROUP CONSISTING OF INTERMEDIATE AND HIGH MOLECULAR WEIGHT FATTY ACIDS AND MIXTURES THEREOF, AND METAL SALTS OF A PHOSPHORUS CONTAINING ACID CONTAINING 1 TO 5 CARBON ATOMS SELECTED FROM THE GROUP CONSISTING OF 1-HYDROXY ALKYL PHOSPHONIC ACID AND 1-HYDROXY ALKYL PHOSPHINIC ACIDS, WHEREIN THE MOLAR RATIO OF SAID FATTY ACIDS TO SAID PHOSPHORUS-CONTAINING ACID IS ABOUT 0.1 TO 10.0 MOLES OF FATTY ACID PER MOLE OF SAID PHOSPHORUS-CONTAINING ACID AND WHEREIN SAID METAL IS SELECTED FROM THE GROUP CONSISTING OF ALKALI METALS AND ALKALINE EARTH METALS.
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US725489A US3001938A (en) | 1958-04-01 | 1958-04-01 | Lubricants containing salts of organic-substituted phosphorus - containing acids |
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US725489A US3001938A (en) | 1958-04-01 | 1958-04-01 | Lubricants containing salts of organic-substituted phosphorus - containing acids |
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US3001938A true US3001938A (en) | 1961-09-26 |
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US725489A Expired - Lifetime US3001938A (en) | 1958-04-01 | 1958-04-01 | Lubricants containing salts of organic-substituted phosphorus - containing acids |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3143505A (en) * | 1961-04-28 | 1964-08-04 | Exxon Research Engineering Co | Oil compositions containing mixed metal salts |
US3542679A (en) * | 1968-05-29 | 1970-11-24 | Universal Oil Prod Co | Amine salts of phosphinic acid or carboxylic acid esters thereof as antioxidants for organic materials |
WO1990009386A1 (en) * | 1989-02-08 | 1990-08-23 | The Lubrizol Corporation | Hydroxyalkane phosphonic acids and derivatives thereof and lubricants containing the same |
US20080103330A1 (en) * | 2006-10-25 | 2008-05-01 | Leo Zhaoqing Liu | Process for the preparation of highly purified, dialkydithiophosphinic compounds |
US20080106019A1 (en) * | 2006-11-08 | 2008-05-08 | Hilti Aktiengesellschaft | Positioning device with actuating switching means for a hand-held setting tool |
US20090137707A1 (en) * | 2007-11-26 | 2009-05-28 | Clariant International Ltd. | Mixed salts of diorganylphosphinic acids and carboxylic acids |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB549296A (en) * | 1941-04-12 | 1942-11-16 | Du Pont | Manufacture of improved lubricants |
US2513680A (en) * | 1949-01-18 | 1950-07-04 | Socony Vacuum Oil Co Inc | Lime base grease |
US2628949A (en) * | 1951-02-14 | 1953-02-17 | Socony Vacuum Oil Co Inc | Stabilized lithium base grease |
US2758971A (en) * | 1952-05-20 | 1956-08-14 | Exxon Research Engineering Co | Blending agents for mineral oils |
US2837481A (en) * | 1955-03-31 | 1958-06-03 | California Research Corp | Metal alkyl phosphonate thickened lubricating oils |
US2846392A (en) * | 1953-10-21 | 1958-08-05 | Exxon Research Engineering Co | Metal soap-salt complexes and lubricants containing same |
-
1958
- 1958-04-01 US US725489A patent/US3001938A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB549296A (en) * | 1941-04-12 | 1942-11-16 | Du Pont | Manufacture of improved lubricants |
US2513680A (en) * | 1949-01-18 | 1950-07-04 | Socony Vacuum Oil Co Inc | Lime base grease |
US2628949A (en) * | 1951-02-14 | 1953-02-17 | Socony Vacuum Oil Co Inc | Stabilized lithium base grease |
US2758971A (en) * | 1952-05-20 | 1956-08-14 | Exxon Research Engineering Co | Blending agents for mineral oils |
US2846392A (en) * | 1953-10-21 | 1958-08-05 | Exxon Research Engineering Co | Metal soap-salt complexes and lubricants containing same |
US2837481A (en) * | 1955-03-31 | 1958-06-03 | California Research Corp | Metal alkyl phosphonate thickened lubricating oils |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3143505A (en) * | 1961-04-28 | 1964-08-04 | Exxon Research Engineering Co | Oil compositions containing mixed metal salts |
US3542679A (en) * | 1968-05-29 | 1970-11-24 | Universal Oil Prod Co | Amine salts of phosphinic acid or carboxylic acid esters thereof as antioxidants for organic materials |
WO1990009386A1 (en) * | 1989-02-08 | 1990-08-23 | The Lubrizol Corporation | Hydroxyalkane phosphonic acids and derivatives thereof and lubricants containing the same |
US20080103330A1 (en) * | 2006-10-25 | 2008-05-01 | Leo Zhaoqing Liu | Process for the preparation of highly purified, dialkydithiophosphinic compounds |
US7572931B2 (en) | 2006-10-25 | 2009-08-11 | Rhodia Inc. | Process for the preparation of highly purified, dialkydithiophosphinic compounds |
US20080106019A1 (en) * | 2006-11-08 | 2008-05-08 | Hilti Aktiengesellschaft | Positioning device with actuating switching means for a hand-held setting tool |
US7597227B2 (en) | 2006-11-08 | 2009-10-06 | Hilti Aktiengesellschaft | Positioning device with actuating switching means for a hand-held setting tool |
US20090137707A1 (en) * | 2007-11-26 | 2009-05-28 | Clariant International Ltd. | Mixed salts of diorganylphosphinic acids and carboxylic acids |
US8221658B2 (en) * | 2007-11-26 | 2012-07-17 | Clariant Finance (Bvi) Limited | Mixed salts of diorganylphosphinic acids and carboxylic acids |
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