US2923682A - Lubricating compositions containing mixed salts - Google Patents
Lubricating compositions containing mixed salts Download PDFInfo
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- US2923682A US2923682A US684409A US68440957A US2923682A US 2923682 A US2923682 A US 2923682A US 684409 A US684409 A US 684409A US 68440957 A US68440957 A US 68440957A US 2923682 A US2923682 A US 2923682A
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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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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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
- 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
- C10M2207/302—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
- C10M2207/304—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monohydroxy compounds, dihydroxy compounds and dicarboxylic acids only and having no free hydroxy or carboxyl groups
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
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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
- 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
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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
- 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
- C10M2209/11—Complex polyesters
- C10M2209/111—Complex polyesters having dicarboxylic acid centres
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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
- 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
- C10M2209/11—Complex polyesters
- C10M2209/112—Complex polyesters having dihydric acid centres
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/02—Unspecified siloxanes; Silicones
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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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Definitions
- This invention relates to lubricating compositions con- .taining salts of dialkyl dithiophosphoric acid and to the process for making them.
- it relates to greases and lubricating fluids containing co-neutralized mixtures. of ,salts of acetic acid, intermediate molecular weight carboxylic acids and'a dialkyl dithiophosphoric acid and to their methods of preparation.
- R is an aliphatic hydrocarbon radical having either a straight or branched chain and containing from 3 to 8 carbon atoms.
- .R' is the same or different from R and is also an aliphatic hydrocarbon radical having a carbon atoms. Examplesof specific compounds which can be used include:
- Di-n-propyl' dithiophosphoric acid Di-n-butyl dithiophosphoric acid] Dihexyl dithiophosphoric acid
- Dioctyl dithiophosphoric acid Propyl hexyl dithiophosphoric acid
- the metal component of the thickeners of this invention are chosen from the alkaline earth metals such as calcium, strontium, and barium. Calcium is particularly preferred due to its low cost and availability.- Mixtures of the above metals can be employed if desired. The metals are reacted with the acids in the form of metal bases such-as the alkaline earth metal hydroxides, oxides, and carbonates.
- the mol ratio of the dialkyl dithiophosphoric acid to the intermediate molecular weight monocarboxylic' acids in the thickeners is in the range of 1:1 to 1:4.
- the mol ratio of the dialkyl dithiophosphoric acid and the intermediate molecular weight carboxylic acids combined to the acetic acid is in the range of from 1:25 to 1:15.
- excellent thickeners can be prepared from a mixture of 1 to 4 parts, preferably one part of dialkyl dithiophosphoric acid; 4 to 1 parts, preferably 2 to 1 parts of intermediate molecular weight monocarboxylic acids; and to 1 parts, preferably 5 to 1 parts of acetic acid; with suflicient alkaline earth metal base to neutralize the mixture of acids.
- the lubricating compositions of the invention comprise from 50 to 98 wt. percent of a lubricating oil and from about 2 to 50 Wt. percent of the thickener.
- the composition will contain about 15 to 50 wt. percent, preferably to wt. percent of the thickener and about 50 to 85 wt. percent, preferably 60 I to 80 wt. percent lubricating oil; while for fluid lubricants the composition will contain from about 2 to 15 wt. percent, preferably 5 to 10 wt. percent of the thickener, and
- lubricating oil used as a menstruum for co-neutralization of the acids with an alkaline earth metal base depends on the particular use contemplated for the finished lubricant.
- a wide variety of mineral as well as synthetic lubricating oils can be used. In general, the
- ' lubricating oil has a viscosity within the range of about 60 to 2500 S.S.U. at 100? F. and about 35 to 200 S.S.U. at 210 F., a pour point of about +20 to -75 F. and a flash point of about 350 to 650 F. Oils having a viscosity index of 1007or higher are usually desirable, though oils having a low viscosity index can be employed.
- synthetic as well as mineral lubricat'ing oils can be employed as part or all of the liquid phase of the grease, and they include-synthetic lubricating'o'ils of the hydrocarbon, hydrocarbon polymer, ester, complex ester, formal, mercaptal, polyalkylene oxide, silicone, and similar types.
- Synthetic oils such as the ple diesters can also be used, e.g. di-2-ethylhexy1 sebacate',
- dialkyl dithiophosphoric acids of the invention are prepared by reacting phosphorus pentasulfide with an ap- 4 of dihexyl dithiophosphoric ac'd was then added to the lime-oil dispersion slowly with agitation over 1 hour. No external heating was applied but the temperature rose to 160 F. during the addition.
- the mixtu heated to 320 F. in a steam kettle at 100 lbs. per square then be cooled, and a conventional additive added, 1 inch of steam pressure and the resultant semi.fluid ma. desired.
- the mixture can then be homogenized such. as f i l was G li homoggnized d bl d d wi h an by passing through a Gaulin homogenlzer orv a, Charlotte ual quantity of a lubricating oil having a viscosity 'of M 7 177.8 S.S.U. at 10.0 F. and a viscosity index of 110. lubllcatlllg QP U f tile.
- the co-neutralization can take place EXAMPLE IV in less than all but in at least a dispersing portion of;the I V s lubricating-oil usedin the finished composition and then I q'p p mi i0 X P Q I as eated additional lubricating oil blended therewith to form the f to m a steam kettle at p squ' s q fi i h d rodugt steam pressure and then Gaulin homogenized.
- Theho will be better understood by reference mogellized f was With an equal to the following examples which include the.
- Example II Example III
- the acids making up the salt mix- Oil having a viscosity of 45.3 S.S.U. at 210 F., a viscosity tures of the invention are co-neutralized in situ in mineral at F., and a viscosity index of 110. blend of 10.0 wt. percent of glacial acetic acid, 2.4wt. rcent' of Wecoline AAC acids, and 2.0 wt.” percent weeglinetkirkc. acids has the following cornposltion; 20%
- the thickener comprises a co-neutralized mixture of salts of acetic acid, intermediate molecular weight monocarboxylic acids and a dialkyl dithiophosphoric acid.
- additives can also be added to the lubricating compositions, such as detergents, oxidation inhibitors, viscosity index improvers, corrosion inhibitors, pour depressants, dyes, other grease thickeners, and the like, as known to those skilled in the art.
- a lubricating composition comprising from 50 to 98 wt. percent of a lubricating oil having a viscosity in the range of 60 to 2500 S.S.U. at 100 F., and from 2 to 50 wt.
- a thickener comprising a co-neutralized mixture of alkaline earth metal salts of acetic acid, intermediate molecular weight monocarboxylic acids having from 8 to 12 carbon atoms per molecule and a dialkyl dithiophosphoric acid having from 3 to 8 carbon atoms per alkyl group, the mole ratio of dithiophosphoric acid to intermediate molecular weight monocarboxylic acid being about 1:1 to 1:4, the mole ratio of dithiophosphoric acid and intermediate molecular weight monocarboxylic acids combined to acetic acid being in the range of from 1:2.5 to 1:15, said mixture being prepared ata temperature of about 150 to 350 F.
- a lubricating composition comprising from 50 to 98 wt. percent of a lubricating oil having a viscosity in the range of 60 to 2500 S.S.U. at 100 F., and from 2 to 50 wt. percent of a thickener comprising a co-neutralized mixture of alkaline earth metal salts of 10 to 1 parts by weight of acetic acid, 4 to 1 parts by weight of intermediate molecular weight monocarboxylic acids having from 8 to 12 carbon atoms per molecule and 1 to 4 parts by weight of a dialkyl dithiophosphoric acid having from 3 to 8 carbon atoms per alkyl group, said mixture being prepared at a temperature of about 150 to 350 F.
- a lubricating grease composition comprisinga major proportion of a mineral lubricating oil and from 20 to 40 wt. percent of a co-neutralized calcium salt mixture of from 10 to 1 parts by weight of acetic acid, 4 to 1 parts by weight of coconut oil acids and 1 to 4 parts by weight of dihexyl dithiophosphoric acid, said mixture being prepared at a temperature of about 150 to 350 F.
- a lubricating oil composition comprising a major proportion of a mineral lubricating oil and from S to 10 wt. percent of a coneutralized calcium salt mixture of from 10 to 1 parts by weight of acetic acid, 4 to 1 parts by weight of coconut oil acids and l to 4 parts by weight of dihexyl dithiophosphoric acid, said mixture being prepared at a temperature of about 150 to 350 F.
Description
IUBRICATINGCOMPOSI'IIONS CONTAINING. M 6
MIXED SALTS Arnold J. Morway, Clark, NJ., assignor to Esso Research 2 s andEngineering Company, a corporation of Delaware No Drawing. Application September 17, 1957 Serial N0. 684,409
7 Claims. (Cl. 25232.7)
This invention relates to lubricating compositions con- .taining salts of dialkyl dithiophosphoric acid and to the process for making them. In particular, it relates to greases and lubricating fluids containing co-neutralized mixtures. of ,salts of acetic acid, intermediate molecular weight carboxylic acids and'a dialkyl dithiophosphoric acid and to their methods of preparation.
Mixed salts of low molecular weight carboxylic acids and intermediate or high molecular weight carboxylic acids or both which are useful in lubricating oils are known. These known mixtures have been used as grease thickeners and for imparting certain desirable, properties to fluid type lubricants. It has now been found that greases and lubricating fluids can be prepared from thickeners comprising mix tures of salts of a dialkyl dithiophosphoric acid, acetic acid, and intermediate molecular weight monocarboxylic acids. The salt mixtures are formed by co-neutralization of the corresponding acids with an alkaline earth metal base in situ in lubricating oil to form greases having higher load-carrying ability, reduced wear characteristics,
and a lower degree of thixotropy than greases thickened with the aforementioned known mixtures. Furthermore, the presence of the dithiophosphoric acid salt in theconeutralized mixtures acts as an oxidation inhibitor. Moreover, such low thixotropic greases are very plastic and are particularly useful in centralized lubrication systems because of their ease of pumping and their good slumping properties. Also, under high shearing stresses,
the greases of the invention do not solidify or channel wherein R is an aliphatic hydrocarbon radical having either a straight or branched chain and containing from 3 to 8 carbon atoms. .R' is the same or different from R and is also an aliphatic hydrocarbon radical having a carbon atoms. Examplesof specific compounds which can be used include:
Di-n-propyl' dithiophosphoric acid Di-n-butyl dithiophosphoric acid] Dihexyl dithiophosphoric acid Dioctyl dithiophosphoric acid Propyl hexyl dithiophosphoric acid The-intermediate molecular weightmonocarboxylic unsubstituted aliphatic monocarboxylic acids containing from. 8 to 12 carbon atoms per molecule. a mixture of caprylic, capric, and lauric acids which are obtained from coconut oil can be used. at
The metal component of the thickeners of this invention are chosen from the alkaline earth metals such as calcium, strontium, and barium. Calcium is particularly preferred due to its low cost and availability.- Mixtures of the above metals can be employed if desired. The metals are reacted with the acids in the form of metal bases such-as the alkaline earth metal hydroxides, oxides, and carbonates.
The mol ratio of the dialkyl dithiophosphoric acid to the intermediate molecular weight monocarboxylic' acids in the thickeners is in the range of 1:1 to 1:4. The mol ratio of the dialkyl dithiophosphoric acid and the intermediate molecular weight carboxylic acids combined to the acetic acid is in the range of from 1:25 to 1:15. In terms of parts by weight, excellent thickeners can be prepared from a mixture of 1 to 4 parts, preferably one part of dialkyl dithiophosphoric acid; 4 to 1 parts, preferably 2 to 1 parts of intermediate molecular weight monocarboxylic acids; and to 1 parts, preferably 5 to 1 parts of acetic acid; with suflicient alkaline earth metal base to neutralize the mixture of acids.
The lubricating compositions of the invention comprise from 50 to 98 wt. percent of a lubricating oil and from about 2 to 50 Wt. percent of the thickener. When a grease is desired, the composition will contain about 15 to 50 wt. percent, preferably to wt. percent of the thickener and about 50 to 85 wt. percent, preferably 60 I to 80 wt. percent lubricating oil; while for fluid lubricants the composition will contain from about 2 to 15 wt. percent, preferably 5 to 10 wt. percent of the thickener, and
about 85 to'98 wt. percent lubricating oil.
The choice of lubricating oil used as a menstruum for co-neutralization of the acids with an alkaline earth metal base depends on the particular use contemplated for the finished lubricant. A wide variety of mineral as well as synthetic lubricating oils can be used. In general, the
' lubricating oil has a viscosity within the range of about 60 to 2500 S.S.U. at 100? F. and about 35 to 200 S.S.U. at 210 F., a pour point of about +20 to -75 F. and a flash point of about 350 to 650 F. Oils having a viscosity index of 1007or higher are usually desirable, though oils having a low viscosity index can be employed. As previously mentioned, synthetic as well as mineral lubricat'ing oils can be employed as part or all of the liquid phase of the grease, and they include-synthetic lubricating'o'ils of the hydrocarbon, hydrocarbon polymer, ester, complex ester, formal, mercaptal, polyalkylene oxide, silicone, and similar types. Synthetic oils such as the ple diesters can also be used, e.g. di-2-ethylhexy1 sebacate',
straight branched chain andpcontaining f 3 3 ,di-isooctyl azelate and the complex esters For example,
sheet or. alcohols, or. both with dicarboxylic acids or monocarboxylic acids or both.
The dialkyl dithiophosphoric acids of the invention are prepared by reacting phosphorus pentasulfide with an ap- 4 of dihexyl dithiophosphoric ac'd was then added to the lime-oil dispersion slowly with agitation over 1 hour. No external heating was applied but the temperature rose to 160 F. during the addition.
propriate aliphatic alcohol or alcohols by techniques 5 allowed to cool and the agitation continued until the known to the art. temperature had subsided to about 100 to 120 F. The The reaction temperatures utilized for the co-neutralgrease was then passed through a Gaulin homogenizer ization of the acetic acid, intermediate molecular weight and inspected. monocarboxylic acids and the dialkyl dithiophosphoric EXAMPLE II acid in a lubricating oil menstruum are in the range of about l50 -'to 350FJ However, when temperatures in A grease was p ep e y first dlspsrsms 5 the lower end of this temperature range are utilized, the P Q6111; ydrated lime in 86.2 Percent Of K111161111 heat of reaction will generally increase, the temperature lubflcatlng l g a 3 0 of 1200 at of the reactionmixture." The temperature of reaction Then blend of -00 W Percent Of glaclal cet c is not critical, except that temperatures much above 350 mild, l f 0f Wecollnfi AAC acldst and F, hould not b e I d wt. percentof dlhexyl dithiophosphoric acid was added The reaction cantake'place by, intimately mixing th 0 mineral Oil at ifi p 0f 'I The metal base and lubricating oil and slowly'adding with resultmg product Was agitated, allqwsd to cool. nd-th n agitation a blend of the three. acids. The agitation can Passed through a Gaulin homogemlerbe continued and thetemperature allowed to dropto room temperature. However, the reaction temperature EXAMPLE HI P f ably is ai tained for about /2 h0 l1rS to A grease prepared in accordance with Example I was Sum compleflon or the salt formation. The mixtu heated to 320 F. in a steam kettle at 100 lbs. per square then be cooled, and a conventional additive added, 1 inch of steam pressure and the resultant semi.fluid ma. desired. The mixture can then be homogenized such. as f i l was G li homoggnized d bl d d wi h an by passing through a Gaulin homogenlzer orv a, Charlotte ual quantity of a lubricating oil having a viscosity 'of M 7 177.8 S.S.U. at 10.0 F. and a viscosity index of 110. lubllcatlllg QP U f tile. lHYeIltlon 2 The resulting blend was again Gaulin homogenized at prepared by co-neutrallzing the acids in all the lubricating I 5 000 lb per, square i h, oil which is required in the finished lubricating composition. Alternatively, the co-neutralization can take place EXAMPLE IV in less than all but in at least a dispersing portion of;the I V s lubricating-oil usedin the finished composition and then I q'p p mi i0 X P Q I as eated additional lubricating oil blended therewith to form the f to m a steam kettle at p squ' s q fi i h d rodugt steam pressure and then Gaulin homogenized. Theho The invention will be better understood by reference mogellized f was With an equal to the following examples which include the. preferred q y of a mmeral lubrlcatmg 011 havlng a vlscoslty 9 embodiments of the invention, 1200 S.S.U. at 100 F. The resulting blend Was again Gaulin homogenized at 5,000 lbs. per square inch. EXAMPLE I 40 The characteristics of the above lubricants and greases A grease was prepared by dispersing 7.8 wt. percent of are shown in the following Table I.
Table I Properties Example I Example II Example III Example IV- Appearance--. Smooth uniform. Smooth uniform Uniform fluid Uniform fluid grease. fluid. lubricant. lubricant. Dropping Point, F. 500+- Consistency:
Penetrations, 77 F., mm./10-
Unworked- ,310. Worked strokes. 320... Worked 100,000 Stroke 325.- Viscosity. S.S.U.:
100 19000-. 186.3 1395. 210 F 128.0--- 46.2 9018. Extreme pressure properties:
Almen test Gradual loading:
Wt. Carried 15; 1s 15- l5. 1 Pin Condition Excellent polished... Excellentpolished... Excellent polished... Excellent polished. Shock loading:
Wt. Carried 1H 15 15. 15. Pin Condition Excellent polished... Excellent polished... Excellent polished... Excellent polished. Timken Test: 50 lbs. load.. Pass; narrow scar-.. Pass; narrow scarv 4 Ball Wear Test: Scar Spot Diam., 0.23... 0.22-.- 0 0.22.
rzrgncflfioo r.p.m.l0 kg.1 hour i Centrifuge Test: hour, 1,500 r.p.m., i 1.5.... 0.75.. 0.5.
Percent Sediment.
hydrated lime in 77.8 wt. percent of a mineral lubricating As previously noted, the acids making up the salt mix- Oil having a viscosity of 45.3 S.S.U. at 210 F., a viscosity tures of the invention are co-neutralized in situ in mineral at F., and a viscosity index of 110. blend of 10.0 wt. percent of glacial acetic acid, 2.4wt. rcent' of Wecoline AAC acids, and 2.0 wt." percent weeglinetkirkc. acids has the following cornposltion; 20%
liiiirfc acid, 24% caprylic acid and 56% capric acid:
The mixture was thenv Table II LOAD-CARRYING TESTS N GREASES CONTAINING CALCIUM DIHEXYL DITHIOPHOSPHATE.
Grease similar in composition to Example II but formed Grease 0! Example I at 150 F. by separate addition of Calcium dihexyl ditbiophospbate Appearance Uniform fluid Product Calcium dihexyl dithiophospbate tends to settle out even after Gaulm homogenization. 4 Ball Wear Test: Scar Spot, Diam., mm 0.23-. 34. Almen Test:
Gradual Loading- Weights earried...-. 14 15. Pin Condition Excellent polished Slight scratching. Shock loading- Weights carried"... 1% 10. Pin Condition Excellent polished Sheared.
As seen form the above tables, excellent solid greases and fluid lubricants can be prepared wherein the thickener comprises a co-neutralized mixture of salts of acetic acid, intermediate molecular weight monocarboxylic acids and a dialkyl dithiophosphoric acid.
Various other additives can also be added to the lubricating compositions, such as detergents, oxidation inhibitors, viscosity index improvers, corrosion inhibitors, pour depressants, dyes, other grease thickeners, and the like, as known to those skilled in the art.
What is claimed is:
l. A lubricating composition comprising from 50 to 98 wt. percent of a lubricating oil having a viscosity in the range of 60 to 2500 S.S.U. at 100 F., and from 2 to 50 wt. percent of a thickener comprising a co-neutralized mixture of alkaline earth metal salts of acetic acid, intermediate molecular weight monocarboxylic acids having from 8 to 12 carbon atoms per molecule and a dialkyl dithiophosphoric acid having from 3 to 8 carbon atoms per alkyl group, the mole ratio of dithiophosphoric acid to intermediate molecular weight monocarboxylic acid being about 1:1 to 1:4, the mole ratio of dithiophosphoric acid and intermediate molecular weight monocarboxylic acids combined to acetic acid being in the range of from 1:2.5 to 1:15, said mixture being prepared ata temperature of about 150 to 350 F.
2. A lubricating grease composition according to claim 1 wherein the composition has from to 40 wt. percent thickener.
3. A fluid lubricating composition according to claim 1 wherein the composition has from 2 to 15 wt. percent thickener.
4. A lubricating composition comprising from 50 to 98 wt. percent of a lubricating oil having a viscosity in the range of 60 to 2500 S.S.U. at 100 F., and from 2 to 50 wt. percent of a thickener comprising a co-neutralized mixture of alkaline earth metal salts of 10 to 1 parts by weight of acetic acid, 4 to 1 parts by weight of intermediate molecular weight monocarboxylic acids having from 8 to 12 carbon atoms per molecule and 1 to 4 parts by weight of a dialkyl dithiophosphoric acid having from 3 to 8 carbon atoms per alkyl group, said mixture being prepared at a temperature of about 150 to 350 F.
5. A lubricating grease composition comprisinga major proportion of a mineral lubricating oil and from 20 to 40 wt. percent of a co-neutralized calcium salt mixture of from 10 to 1 parts by weight of acetic acid, 4 to 1 parts by weight of coconut oil acids and 1 to 4 parts by weight of dihexyl dithiophosphoric acid, said mixture being prepared at a temperature of about 150 to 350 F.
6. A lubricating oil composition comprising a major proportion of a mineral lubricating oil and from S to 10 wt. percent of a coneutralized calcium salt mixture of from 10 to 1 parts by weight of acetic acid, 4 to 1 parts by weight of coconut oil acids and l to 4 parts by weight of dihexyl dithiophosphoric acid, said mixture being prepared at a temperature of about 150 to 350 F.
7. The process of preparing a lubricating composition comprising co-neutralizing with an alkaline earth metal base, and in a dispersingportion of a lubricating oil having a viscosity in the range of to 2500 S.S.U. at F., a mixture of acetic acid, intermediate molecular weight monocarboxylic acids having from 8 to 12 carbon atoms per molecule, and a dialkyl dithiophosphoric acid having from 3 to 8 carbon atoms per alkyl group at a temperature in the range of to 350 F., the mole ratio of dithiophosphoric acid and intermediate molecular weight monocarboxylic acids combined to acetic acid being in the rangeof from 1:2.5 to 1:15 and the mole ratio of dithiophosphoric acid to intermediate molecular weight monocarboxylic acid being about 1:1 to 1:4.
References Cited in the file of this patent UNITED STATES PATENTS 2,252,985 Rutherford et a1 Aug. 19, 1941 2,343,213 Ashley Feb. 29, 1944 2,344,392 Cook et al. Mar. 14, 1944 2,364,283 Freuler Dec. 5, 1944 2,364,284 Freuler Dec. 5, 1944
Claims (1)
1. A LUBRICATING COMPOSITION COMPRISING FROM 50 TO 98 WT. PERCENT OF A LUBRICATING OIL HAVING A VISCOSITY IN THE RANGE OF 60 TO 2500 S.S.U. AT 100*F., AND FROM 2 TO 50 WT. PERCENT OF A THICKENER COMPRISING A CO-NEUTRALIZED MIXTURE OF ALKALINE EARTH METAL SALTS OF ACETIC ACID, INTERMEDIATE MOLECULAR WEIGHT MONOCARBOXYLIC ACIDS HAVING FROM 8 TO 12 CARBON ATOMS PER MOLECULE AND A DIALKYL DITHIOPHOSPHORIC ACID HAVING FROM 3 TO 8 CARBON ATOMS PER ALKYL GROUP, THE MOLE RATIO OF DITHIOPHOSPHORIC ACID TO INTERMEDIATE MOLECULAR WEIGHT MONOCARBOXYLIC ACID BEING ABOUT 1:1 TO 1:4, THE MOLE RATIO OF DITHIOPHOSPHORIC ACIDS AND INTERMEDIATE MOLECULAR WEIGHT MONOCARBOXYLIC ACIDS COMBINED TO ACETIC ACID BEING IN THE RANGE OF FROM 1:2.5 TO 1:15, SAID MIXTURE BEING PREPARED AT A TEMPERATURE OF ABOUT 150* TO 350*F.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US684409A US2923682A (en) | 1957-09-17 | 1957-09-17 | Lubricating compositions containing mixed salts |
GB28130/58A GB832059A (en) | 1957-09-17 | 1958-09-02 | Lubricating compositions containing mixed salts |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US684409A US2923682A (en) | 1957-09-17 | 1957-09-17 | Lubricating compositions containing mixed salts |
Publications (1)
Publication Number | Publication Date |
---|---|
US2923682A true US2923682A (en) | 1960-02-02 |
Family
ID=24747922
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US684409A Expired - Lifetime US2923682A (en) | 1957-09-17 | 1957-09-17 | Lubricating compositions containing mixed salts |
Country Status (2)
Country | Link |
---|---|
US (1) | US2923682A (en) |
GB (1) | GB832059A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3025238A (en) * | 1959-11-06 | 1962-03-13 | Texaco Inc | Lubricating oils thickened to a grease consistency with calcium salts of lower fatty acids and phosphorus sulfide-hydrocarbon reaction products |
US3087950A (en) * | 1959-01-22 | 1963-04-30 | Exxon Research Engineering Co | Extreme pressure lubricant additive |
US3389085A (en) * | 1964-03-31 | 1968-06-18 | Exxon Research Engineering Co | Lubricants containing mixed metal salts of mono- and polybasic acids |
FR2457874A1 (en) * | 1979-05-31 | 1980-12-26 | Lubrizol Corp | MIXED AND LUBRICANT METAL SALTS AND FUNCTIONAL FLUIDS CONTAINING THEM |
US4308154A (en) * | 1979-05-31 | 1981-12-29 | The Lubrizol Corporation | Mixed metal salts and lubricants and functional fluids containing them |
EP0580335A1 (en) * | 1992-07-10 | 1994-01-26 | The Lubrizol Corporation | Grease compositions |
EP0580331A1 (en) * | 1992-07-10 | 1994-01-26 | The Lubrizol Corporation | Grease compositions |
US5362409A (en) * | 1992-07-10 | 1994-11-08 | The Lubrizol Corporation | Grease compositions |
US6063742A (en) * | 1999-03-01 | 2000-05-16 | The Lubrizol Corporation | Grease compositions |
US6100226A (en) * | 1998-05-20 | 2000-08-08 | The Lubrizol Corporation | Simple metal grease compositions |
US6843922B1 (en) * | 1999-09-01 | 2005-01-18 | Ricura Technologies, Llc | Bead and process for removing dissolved metal contaminants |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2252985A (en) * | 1939-05-06 | 1941-08-19 | Standard Oil Co | Compounded oil |
US2343213A (en) * | 1942-04-10 | 1944-02-29 | American Cyanamid Co | Preparation of barium salts of dithiophosphoric acid esters |
US2344392A (en) * | 1941-11-08 | 1944-03-14 | American Cyanamid Co | Crankcase lubricant and chemical compound therefor |
US2364283A (en) * | 1941-10-21 | 1944-12-05 | Union Oil Co | Modified lubricating oil |
US2364284A (en) * | 1941-06-17 | 1944-12-05 | Union Oil Co | Modified lubricating oil |
-
1957
- 1957-09-17 US US684409A patent/US2923682A/en not_active Expired - Lifetime
-
1958
- 1958-09-02 GB GB28130/58A patent/GB832059A/en not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2252985A (en) * | 1939-05-06 | 1941-08-19 | Standard Oil Co | Compounded oil |
US2364284A (en) * | 1941-06-17 | 1944-12-05 | Union Oil Co | Modified lubricating oil |
US2364283A (en) * | 1941-10-21 | 1944-12-05 | Union Oil Co | Modified lubricating oil |
US2344392A (en) * | 1941-11-08 | 1944-03-14 | American Cyanamid Co | Crankcase lubricant and chemical compound therefor |
US2343213A (en) * | 1942-04-10 | 1944-02-29 | American Cyanamid Co | Preparation of barium salts of dithiophosphoric acid esters |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3087950A (en) * | 1959-01-22 | 1963-04-30 | Exxon Research Engineering Co | Extreme pressure lubricant additive |
US3025238A (en) * | 1959-11-06 | 1962-03-13 | Texaco Inc | Lubricating oils thickened to a grease consistency with calcium salts of lower fatty acids and phosphorus sulfide-hydrocarbon reaction products |
US3389085A (en) * | 1964-03-31 | 1968-06-18 | Exxon Research Engineering Co | Lubricants containing mixed metal salts of mono- and polybasic acids |
FR2457874A1 (en) * | 1979-05-31 | 1980-12-26 | Lubrizol Corp | MIXED AND LUBRICANT METAL SALTS AND FUNCTIONAL FLUIDS CONTAINING THEM |
US4308154A (en) * | 1979-05-31 | 1981-12-29 | The Lubrizol Corporation | Mixed metal salts and lubricants and functional fluids containing them |
EP0580331A1 (en) * | 1992-07-10 | 1994-01-26 | The Lubrizol Corporation | Grease compositions |
EP0580335A1 (en) * | 1992-07-10 | 1994-01-26 | The Lubrizol Corporation | Grease compositions |
US5362409A (en) * | 1992-07-10 | 1994-11-08 | The Lubrizol Corporation | Grease compositions |
EP0651043A2 (en) * | 1993-10-25 | 1995-05-03 | The Lubrizol Corporation | Grease compositions |
EP0651043A3 (en) * | 1993-10-25 | 1995-08-30 | Lubrizol Corp | Grease compositions. |
US6100226A (en) * | 1998-05-20 | 2000-08-08 | The Lubrizol Corporation | Simple metal grease compositions |
US6063742A (en) * | 1999-03-01 | 2000-05-16 | The Lubrizol Corporation | Grease compositions |
US6843922B1 (en) * | 1999-09-01 | 2005-01-18 | Ricura Technologies, Llc | Bead and process for removing dissolved metal contaminants |
Also Published As
Publication number | Publication date |
---|---|
GB832059A (en) | 1960-04-06 |
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