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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
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  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
  • C10M135/10—Sulfonic acids or derivatives thereof
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  • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
  • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
  • C10M137/04—Phosphate esters
  • C10M137/10—Thio derivatives
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  • C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
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  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
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  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/084—Acrylate; Methacrylate
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  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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  • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
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  • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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  • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2221/041—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving sulfurisation of macromolecular compounds, e.g. polyolefins
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  • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2221/043—Polyoxyalkylene ethers with a thioether group
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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
  • C10M2223/04—Phosphate esters
  • C10M2223/045—Metal containing thio derivatives
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  • 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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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
  • C10M2229/04—Siloxanes with specific structure
  • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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  • 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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  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/02—Groups 1 or 11
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  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/06—Groups 3 or 13
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  • C10N2010/00—Metal present as such or in compounds
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  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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  • C10N2070/00—Specific manufacturing methods for lubricant compositions
  • C10N2070/02—Concentrating of additives

Definitions

• This invention relates to a lubricating composition and more particularly to a light colored mineral lubricating oil composition having excellent thermal stability and rust-inhibiting characteristics.
• the present invention is based upon a particularly effective lubricating composition having good resistance to oxidation and sludge formation combined with good lubricating characteristics, and anti-corrosion and rust-inhibiting properties.
• the improved lubricating composition of this invention comprises a major proportion of a mineral lubricating oil and a minor proportion of each of (a) a metal salt of a thiophosphoric acid ester, (b) an oil-soluble alkaline earth metal sulfonate, and (c) an oil-soluble alkaline earth metal and sulfur containing, permanently thermoplastic, resinous condensation product of formaldehyde, a metal sulfide and an alkylated monohydric phenol.
• the lubricating oil to which the other constituents are added is advantageously a highly refined paralfinic oil.
• highly refined paratfinic oil we mean a pertoleum lubricating oil which has been refined by one of the more drastic refining methods known in the art, for example, by conventional aluminum chloride refining or by a solvent extraction adapted to remove all or substantially all of the unsaturated and aromatic constituents of the oil.
• Aluminum chloride refined and/ or solvent extracted paraflinic base oil such as a Pennsylanvia oil, provides an excellent base oil for the composition of the invention.
• drastically refined Mid-Continent and Gulf Coastal oil may also be used. Regardless of the type of oil employed, it is essential to use a light colored oil in order to obtain a final lubricating composition which has a light color.
• the metal salts of the thiophosphoric acid esters which can be used in accordance with the invention are advantageously those whose metal component is a metal of Group II of Mendelyeevfs periodic arrangement of the 2,966,460 Patented. Dec. 27, 1.960
• Particularly desirable metals within, this group are magnesium, calcium, zinc, strontium, cadmium and barium; In some instances other metals including aluminum and tin can also be employed.
• Group II metals we prefer zinc because the zinc salts when added to highly refined oils produce lubricating compositions having good antiwear and bearing corrosion inhibiting properties.
• the zinc salts of the thiophosphoric acid esters can impart these desirable properties to most oils, we have found that a relatively stable highly refined paraffinic lubricating oil containing a zinc salt of a thiophosphoric acid ester has a tendency to form sludge upon continued heating.
• Such zinc salts do not confer antirust characteristics to the oil.
• anti-sludging properties have been obtained in lubricating compositions by utilizing a detergent and/or dispersant.
• Suitable dispersants have included various oil-soluble organic sulfonates including particularly the alkaline earth metal petroleum mahogany sulfonates.
• an oil containing a combination of a metal salt of a thiophosphoric acid ester, an oil-soluble alkaline earth metal sulfonate, and an oil-soluble alkaline earth metal and sulfur containing, permanently thermoplastic, resinous condensation product of formaldehyde, a metal sulfide and an alkylated monohydric phenol will protect a ferrous metal surface against rusting for a period of time greater than the sum of the periods obtained with the same base oil containing each of the individual additives in proportions identical to those utilized in the combination.
• the metal salts of the thiophosphoric acid esters can be prepared by reacting a basic divalent metal compound with acidic thiophosphoric esters that are prepared in turn by reacting a monohydric alcohol with phosphorus pentasulfide.
• the monohydric alcohol can be either an open chain or cyclic aliphatic alcohol. Excellent additives for the purpose of our invention can be obtained with the alcohols containing an average of 6 to 8 carbon atoms. However, we can also use the aliphatic monohydric alcohols containing 6 to 14 carbon atoms on the average. Cyclohexanol and the OX0 octyl alcohols are exemplary of the alcohols which have given excellent additives for the purpose of our invention.
• the Oxo octyl alcohols comprise mixed isomeric branched chain octyl alcohols, principally dimethyl hexanols, prepared by subjecting mixed isomeric heptenes to the well-known Oxo synthesis process.
• Examples of other alcohols which can be used are hexanol, heptanol', Z-ethylhexyl alcohol, lauryl alcohol, methyl cyclopentanol, cycloheptanol, methyl cyclohexanol and propyl cyclohexanol.
• olefinic, alcohols including octenol and dodecenol are also contemplated. It is not essential that the alcohol component consist entirely of alcohols containing 6 or more carbon atoms, and mixed alcohols, for example, mixtures of say 80-90 percent octyl alcohol and 20-10 percent propyl alcohol can be used in preparing compositions useful in our invention.
• the alcohols need not be pure as mixtures of two or more can be used.
• the acidic thiophosphoric esters are prepared with relative ease at moderately elevated temperatures and most conveniently at atmospheric pressure. Suitable temperatures for this reaction are generally between about 130 and about 350 F. In the early stages of the reaction, temperatures in the lower part of the range are suitable, but when the reaction nears completion as evidenced by a reduced rate of evolution of hydrogen sulfide, the temperature is preferably raised to at least about 200 F., preferably about 300 F., in order to insure essentially complete reaction of the phosphorus pentasulfide.
• the reaction of alcohol with phosphorus pentasulfide may be carried out in a solvent which does not interfere with the reaction, such as a mineral lubricating oil, naphtha or benzene, if desired. The reaction will normally be complete within 6 hours, the usual time being about 30 minutes to two hours.
• R and R are like or unlike ester-forming radicals derived from alcohols of the kind disclosed above.
• the phosphoruszsulfur mol ratio of such a product is obviously about 1:2. Also possible, but in lesser amounts,
• the metal salts of the thiophosphoric acid esters can be prepared by reacting the thiophosphoric acid ester with an excess of the corresponding metal or a basic metal compound. This reaction can be conducted at a temperature between room temperature, i.e., 60 to 70 F., and 300 F., the reaction generally requiring about 1 to 8 hours or more to effect substantial completion thereof. The exact amount of time required for this reaction to take place will vary principally according to the reaction temperature, lower temperatures generally requiring a longer time. The time is also somewhat dependent upon the quantity of reactants employed and the effectiveness of the contacting means.
• the metal salts of the thiophosphoric acid esters suitable for the purpose of our invention can comprise either a. single metal salt obtained as described above or mixed rnetal salts of zinc and an alkaline earth metal as defined in application Serial No. 618,459 to Charles B. Welsh, filed October 26, 1956.
• a crude thiophosphoric acid ester obtained as described above is reacted with zinc, or a basic ZUJC compound, preferably the latter, in a mol ratio of about 0.5 to about one mol of the zinc or basic zinc compound for each 2 mols of the crude thiophosphoric acld ester product. This corresponds to a ratio of about 0.5 to one mol of zinc or zinc compound per mol of phosphorus pentasulfide employed in the initial reaction.
• the salt forming reaction begins to take place spontaneously with evolution of heat with gradual addition of zinc or the Zinc compound, at atmospheric pressure, and at a temperature of 60 F., or above. In order to minimize side reactions, it is important to maintain the salt-forming reaction at a temperature not greater than 180 F. until the reaction is substantially complete. In this particular preparation, appreciable departure from the temperatures indicated will have a material effect on the ultimate composition.
• the reaction is further completed by raising the temperature to about 180 to about 280 F., preferably about 250 F., for at least 30 minutes, preferably about 2 hours.
• the product is then cooled, preferably to room temperature and filtered to remove unreacted zinc or zinc compound.
• the zinc thiophosphoric acid ester thus obtained is then reacted at a temperature of about 60 to about 300 F., preferably about 225 to about 275 F., with sufficient alkaline earth metal base to raise the pH of the reaction mixture to at least about 6 and preferably to about 7 and with about 0.5 to about 2 percent by weight of the mixture of benzoyl peroxide.
• the reeaction is usually complete in about 15 minutes to about 2 hours.
• the product is filtered to remove undesired solids.
• Examples of the preferred basic alkaline earth metal compounds are calcium hydroxide and calcium oxide.
• Other basic alkaline earth metal compounds which can be used include barium hydroxide, barium oxide, strontium hydroxide and the like.
• the final product comprises principally mixed zinc-alkaline earth metal salts of thiophosphoric acid esters wherein the phosphoruszsulfur mol ratio is substantially more than 1:2, normally about 2:3.
• Example I is illustrative of the preparation of mixed zinc and calcium salts of Oxo octyl esters of thiophosphoric acids which can be used in the compositions of our invention:
• EXAMPLE I A charge stock consisting of about 70 percent by weight of Oxo octyl alcohols (520 pounds) and 30 percent by weight of phosphorus pentasulfide (222 pounds) is charged to a stainless steel reaction vessel equipped with an agitator and means for heating and cooling. The mixture thus formed is reacted while maintaining the temperature of the reaction mixture between and 200 F., until the rate of reaction has diminished substantially as evidenced by substantial disappearance of solid phosphorus pentasulfide. The foregoing reactant proportions correspond to a mol ratio of about 4 mols of alcohl per mol of phosphorus pentasulfide.
• the Oxo octyl alcohols referred to in this example have the following typical characteristics:
• the temperature of the foregoing mixture is then raised to 300 F. for an hour to insure completion of the reaction.
• the reaction product consisting chiefly of the di Oxo octyl acid esters of dithiophosphoric acid, together with miscellaneous side reaction products, is then cooled to about 100 F., and zinc oxide (81 pounds) is; gradually and slowly added in a ratio of one mol per mol of phosphorus pentasulfide, or in other words until the make-up of the overall reaction mass corresponds to 89.7 percent by weight of the crude di Oxo octyl acid ester of dithiophosphoric acid calculated as such and 10.3 percent by weight of zinc oxide.
• the temperature a of the salt-forming reaction is kept just at or below about 180 F. during addition of most of the zinc oxide.
• the temperature of the reaction mixture is then raised to about 250 F., and maintained there for about 2 hours to complete the reaction, after which the mixture is cooled to room temperature.
• a product prepared essentially according to the foregoing procedure consists essentially of highly stable, light colored, mixed zinc and calcium salts of Oxo octyl esters of thiophosphoric acids and has the following typical characteristics:
• the metal salts of the thiophosphoric acid esters can be employed per se or they can be added to the lubricating oil in the form of a mineral oil concentrate. Formation of the thiophosphate is frequently facilitated by employing a solvent such as a light mineral oil, naphtha or benzene. When such a mineral oil solvent is used, the thiophosphate is readily recovered in the form of a mineral oil concentrate. This concentrate can then be added directly to the oil to be improved or it can be admixed with one or more of the other additive constituents.
• a solvent such as a light mineral oil, naphtha or benzene.
• thiophosphate is employed per se or in the form of an oil concentrate, an amount is used sufficient to incorporate about 0.5 to about 5.0 percent by weight of the thiophosphate in the final lubricating composition.
• a concentrate containing 50 percent of the thiophosphate and 50 percent of light mineral oil can be employed in amounts of about 1.0 to about 10.0 percent by weight.
• the amount of thiophosphate is preferably not more than one half the amount of sulfonate employed.
• the thiophosphate and the alkaline earth metal and sulfur containing, permanently thermoplastic, resinous condensation products are preferably employed in about equal amounts.
• the alkaline earth metal sulfonate which we employ can be prepared from sulfonic acids such as sulfonates obtained in the sulfonation of mineral oils or alkyl aryl compounds, such as didodecyl benzene, as well as sulfon'ates obtained in the sulfonation of organic acids including the naphthenic and fatty acids occurring in animal and vegetable oil.
• sulfonic acids such as sulfonates obtained in the sulfonation of mineral oils or alkyl aryl compounds, such as didodecyl benzene, as well as sulfon'ates obtained in the sulfonation of organic acids including the naphthenic and fatty acids occurring in animal and vegetable oil.
• a mixture of sulfonates such as a mixture of a petroleum sulfonate with one or more of the other named sulfonates.
• the 0 alkaline earth metal sulfonate or mixture of sulfonates be soluble in a mineral oil.
• the sulfonic acids derived from the sulfuric acid treatment of petroleum fractions we prefer to employ the sulfonic acids derived from the sulfuric acid treatment of petroleum fractions. Of these, the sulfonic acids having an average molecular weight of about 400 to about 450 are particularly advantageous.
• the sulfonates can be prepared by saponification of the corresponding acids With the metal oxide or hydroxide or an alkaline salt of a metal. In some instances we may start with an alkali metal sulfonate such as the sodium salt of the oil-soluble petroleum sulfonic acids.
• the sulfonate can be employed, per se, or it can be added to the lubricating oil in the form of a mineral oil concentrate.
• Example IT is illustrative of the preparation by double decomposition of a suitable mineral oil concentrate of calcium petroleum sulfonate which can be used in the compositions of our invention:
• EXAMPLE II Into a stainless steel reaction vessel equipped with an agitator and means for cooling are charged 1424 pounds of an oil-soluble sodium petroleum sulfonate having an average molecular weight of about 445. The sodium petroleum sulfonate is then heated to about 140 F, and thoroughly admixed with 219 pounds of calcium chloride dihydrate dissolved in an equal amount of water. The reaction mass is then heated to 270 F. and held at that temperature for about 30 minutes to complete the reaction. The reaction mass is then dried at a temperature not exceeding 300 F. The dried product is then admixed with about 3 pounds of hydrated lime to raise the pH of the sulfonate and to prevent gelling of the finished product.
• the resulting dried product is then diluted with about 1200 pounds of a dilution mineral oil having a viscosity of about 58 SUS at F., and 34.5 SUS at 210 F.
• the diluted product is then filtered to remove any undesired solids.
• the filtered product comprises a mineral oil concentrate containing 33 percent by weight active ingredient, i.e., calcium petroleum sulfonate.
• the concentrate thus obtained has the following typical properties:
• the amount of the sulfonate which we employ is between about 0.5 and about 5.0 percent by Weight based on the Weight of the total composition. While We can use more than about 5.0 percent of the sulfonate, We prefer to use the least amount required to give good detergent properties for obvious economic reasons. An amount less than about 0.5 percent is generally undesirable because the detergent properties given to the oil with such a small amount of sulfonate is generally insuflicient for modern engines. Higher concentrations are frequently required in heavy duty engines.
• Preferred compositions comprise about 1.5 to about 3.0 percent by weight of sulfonate, the ratio of sulfonate to thiophosphate being about 2 to 1.
• the concentrate When the sulfonate is employed in the form of a mineral oil concentrate, the concentrate is employed in an amount sufficient to incorporate between about 0.5 and about 5.0 percent by weight of sulfonate in the final composition.
• a concentrate containing 33 percent of sulfonate in a light mineral oil diluent can be employed in amounts between about 1.5 and about 15 percent by weight.
• alkaline earth metal and sulfur containing, permanently thermoplastic, resinous condensation product of formaldehyde, metal sulfide and alkylated monohydric phenol which we employ can be prepared directly or by metathesis according to the processes defined, respectively, in US. Patent Nos. 2,736,702 and 2,736,703, which issued February 28, 1956, to H. G. Smith, T. L. Cantrell and J. G. Peters.
• the condensation can be carried out in the presence of an alkali metal hydroxide or alkaline earth metal hydroxide in place of some of the alkali metal sulfide or alkaline earth metal sulfide in which case sufiicient of the sulfide is employed in relation to the hydroxide to yield not less than about 0.5 percent by weight of sulfur in the final resinous product.
• the total amount of metal compound employed that is, the amount of metal sulfide plus metal hydroxide is in the proportion of at least one equivalent of total metal compound for every two mols of the phenol. It will be understood, of course, that if an alkali metal is employed the salt so obtained is converted to an alkaline earth metal compound by metathesis with a water soluble salt of an alkaline earth metal.
• condensation product it is necessary not to permit substantial reaction between the phenol and formaldehyde in the absence of the alkali metal sulfide or alkaline earth metal sulfide and the alkali metal hydroxide or alkaline earth metal hydroxide, if the hydroxide is employed. Accordingly, it is preferred to mix all of the ingredients and react them simultaneously.
• the alkali metal sulfide or alkaline earth metal sulfide and formaldehyde, with or without the hydroxide can first be mixed and partially reacted followed by addition of the phenol to the reaction mass and further reaction; or the alkali metal sulfide or alkaline earth metal sulfide and phenol, with or without the hydroxide, can first be reacted followed by reaction with the formaldehyde.
• the condensation reaction takes place spontaneously at room temperature, but it is preferred to employ moderately elevated temperatures in order to obtain reasonably rapid reaction rates.
• the reaction sequence of first reacting the phenol and alkali metal sulfide or alkaline earth metal sulfide and then reacting the formaldehyde is followed, the phenol and alkali metal sulfide or alkaline earth metal sulfide, with or without the hydroxide, can be reacted first at temperatures as high as 400 F. Thereafter, for the subsequent reaction with formaldehyde, the reaction mass is cooled to about 120 to about 180 F. to avoid excessive volatilization of formaldehyde.
• reaction temperature of about 200 to about 210 F. in order to avoid loss of formaldehyde, although this loss can be reduced to some extent when employing temperatures higher than about 210 F. by the use of closed reaction vessels.
• the formaldehyde is most conveniently used in the form of commercial aqueous formalin, containing 37 percent by weight of formaldehyde, sufiicient water for the reaction is generally contained in the formalin solution.
• the alkali metal or alkaline earth metal sulfides, and the alkali metal or alkaline earth metal hydroxides may be conveniently dispersed and/or dissolved in water to form an aqueous slurry or solution even when formalin is used.
• alkali metal hydroxide or alkaline earth metal hydroxide When an alkali metal hydroxide or alkaline earth metal hydroxide is employed in place of some of the alkali metal sulfide or alkaline earth metal sulfide, it is necessary to use such an amount of hydroxide that the sulfur content of the resulting resin, which is derived from the alkali metal sulfide or alkaline earth metal sulfide, does not fall below about 0.5 percent by weight. In general, it is preferred that the relative molar proportions of alkali metal sulfide or alkaline earth metal sulfide to alkali metal hydroxide or alkaline earth metal hydroxide, respectively, should be about 1:1. The use of an alkali metal monosulfide or alkaline earth metal monosulfide is preferred.
• the product is subjected to dehydration as by distillation to distill off the water. Dehydration is completed as rapidly as possible to avoid darkening the product.
• an alkali metal product is prepared first, then conversion to the alkaline earth metal product by double decomposition is advantageously carried out prior to dehydration of the alkali metal product.
• the condensation reaction can be carried out solely in an aqueous medium, it is advantageous to use additionally a light naphtha solvent or a mineral lubricating oil of the same general type as the oil to which the resin is to be added.
• a concentrate of the alkaline earth metal resin in solution in the naphtha or mineral lubricating oil as the case may be. These concentrates are convenient for incorporating the additive into the lubricating composition.
• the phenolic compounds employed in preparing the condensation product are alkylated monohydric phenols having at least one alkyl group of at least four carbon atoms. As will be understood by those skilled in the art, such phenols must have at least one reactive position in the nucleus which is free of substituents. The presence of at least one alkyl group of at least four carbon atoms in the phenol insures oil solubility of the resinous condensation products prepared therefrom. Phenols not containing such groups tend to yield products which are insoluble in mineral lubricating oils.
• the alkylated phenols can readily be prepared by alkylating phenol or the simple monohydric homologues thereof, such as the naphthols, cresols, and ethyl and propyl phenols, with an alkyl halide or an alkanol in the presence of a Friedel-Crafts catalyst.
• alkylation can be performed with an olefin in the presence of concentrated sulfuric acid as a catalyst.
• alkyl halides, alkanols and olefins employed in these alkylation reactions contain at least four carbon atoms and are selected to yield such alkyl radicals as butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, stearyl and cetyl.
• the long chain groups derived from paraffin Wax are also suitable; these yield the so-called wax phenols.
• Alkyl substituents containing from four to twelve carbon atoms form a preferred class.
• the alkylation reactions described are conventional and need not be further elaborated here.
• alkyl phenols of the class described include n-butylphenol; sec-butylphenol; tert-butylphenol; 2- tert-butyl-4-methylphenol; 2,4-di-tert-butylphenol; 2,6-ditert-butylphenol; 2-tert-butyl-4-ethylpheno1; n-amylphenol; di-tert-amylphenol; hexyl phenols; heptyl phenols; n-octylphenol; iso-octyl phenol (alpha, alpha, gamma, gamma tetramethylbutyl phenol); nonyl phenol; decyl phenol; tri-isobutyl phenol; wax phenols; and the like.
• the alkali metal sulfides which can be used include the monoand poly-sulfides of sodium, potassium, lithium, rubidium and caesium.
• an alkali metal resin When an alkali metal resin is prepared it is converted to the corresponding alkaline methylbutyl phenol and dilution oil.
• the metathesis can 'be carried out by employing an alkaline earth metal nitrate, sulfate, chloride or alcohol-ate salt which is Water soluble.
• the alkaline earth metal sulfides which can be used include the monoand poly-sulfides of calcium, barium, strontium and magnesium.
• Examples 111 and IV are illustrative of the preparation of alkaline earth metal and sulfur containing, permanently thermoplastic, resinous products which can be used in the compositions of our invention.
• Example III illustrates the preparation of a calciumsulfur containing resin directly
• Example IV illustrates the preparation of a barium-sulfur containing resin by double decomposition of the corresponding sodium resin.
• H 7
• EXAMPLE III Into a stainless steel reaction vessel equipped with an agitator and means for heating and cooling are charged 412 pounds (2 mols) of tetramethylbutyl phenol and 494 pounds of a dilution mineral oil having a viscosity of about 58 SUS at 100 F., and 34.5 SUS at 210 F. The mixture thus formed is agitated and heated to a temperature of about 160 F. While maintaining this temperature, 85 pounds (1 mol) of 85 percent calcium sulfide are slowly admixed with the tetramethylbutyl phenol and dilution oil. Thirty-six pounds *(2 mols) of water are then added and the mixture is heated to 185 F. for about one hour.
• the iron content of the water should preferably not exceed two parts per million parts of water.
• the mixture is then cooled to 160 F.
• One hundred sixty-two pounds (2 mols) of 37 percent formaldehyde are introduced below the surface of the reaction mass at a rate which will maintain the reaction temperature between about 160 and about 175' F. without the aid of external cooling.
• the iron content of the formaldehyde solution should preferably not exceed 150 parts per million.
• the reaction mass is heated at a temperature of 175 to 185 F. for two hours to complete the reaction.
• the reaction mass is then dried at a temperature not exceeding 300 F. as rapidly as possible in order to obtain a light colored product.
• the preferred method of drying this material utilizes a stainless steel flash evaporator.
• the dried product is then further diluted with 494 pounds of the dilution oil to obtain a concentrate containing '33 percent by weight active ingredient.
• the diluted product is filtered to remove any undesired solids. thus obtained has the following typical properties:
• EXAMPLE IV Into a stainless steel reaction vessel equipped with an agitator and means for heating and cooling are charged 752 pounds of tetramethylbutyl phenol and 943 pounds of a dilution mineral oil having a viscosity of about 58 SUS at 100 F., and 34.5 SUS at 210 F. The mixture thus formed is agitated and heated to a temperature of about 160 F. While maintaining this temperature, 208 pounds of sodium sulfide in an aqueous solution (297 pounds of water) are slowly admixed with the tetra- The iron content of the water should preferably not exceed two partsper million. The mixture is then heated to about 350 F.
• the concentrate V percent) are then introduced below the surface of thereaction mass at a rate which will maintain the reaction temperature between about and about F.
• the iron content of the formaldehyde solution should preferably not exceed 150 parts per million.
• the reaction mass is heated at a temperature of about 180 F. for two hours to complete the reaction. Double decomposition is then accomplished by adding 403 pounds of barium chloride in an aqueous solt'l'tion (297 pounds of water). The mixture is agitated and heated to 300 F. to dry the prod uct. Fast drying is preferred in order to avoid an undesired color change. Flash evaporation in a stainless steel flash evaporator is preferred. The dried product is "then filtered to remove any undesired solids.
• the dried product comprises a mineral oil concentrate con-
• the alkaline earth metal and sulfur containing, permanently thermoplastic, resinous condensation products diluted with a mineral lubricating oil obtained as described above can be added to the lubricating oil of our invention either per se or they can be further diluted with additional mineral oil if desired. While the condensation products can be prepared in the absence of dilution oil, their preparation is facilitated by the presence of oil.
• the condensation product is employed in the lubricating composition in amounts of about 0.5 to about 5.0 percent by weight based on the weight of the final lubricating composition.
• a concentrate containing 33 percent of active ingredient in a light mineral oil diluent can be employed in amounts of about 1.5 to about 15.0 percent by weight.
• condensation product and the thiophosphate are preferably employed in about equal amounts, the sum of the respective amounts being about equal to the amount of the sulfonate.
• a preferred ratio of condensation productzthiophosphate: sulfonate is 1:1:2.
• the lubricating oil compositions of this invention can contain other additive agents, if desired, to improve other specific properties without deleteriously affecting the bene ficial properties of the compositions.
• other additive agents for example, pour point depressors, viscosity and viscosity index improvers, dyes, and the like can be used.
• the oil can contain a foam inhibitor such as organi-silicon oxide condensation products, organo-silicol condensation products, and the like.
• composition of this invention may be added to the lubricating oil base in any order or simultaneously, either per se, or in the form of a mineral oil concentrate.
• the sulfonate can be added to the lubricating composition either prior or subsequent to the addition of a concentrate of the thiophosphate and metal sulfide phenol-formaldehyde condensation product, the sulfonate is compatible with the thiophosphate and condensation product thus permitting the preparation of a concentrate of all three constituents.
• the preparation of such a three component concentrate greatly facilitates the compounding and blending procedure.
• the weight ratio of sulfonate to thiophosphate is advantageously maintained between about 1:10 and :1; the weight ratio of sulfonate to alkaline earthsufur-containing phenol, formaldehyde resin is maintained between about 1:10 and 10:1; and the weight ratio of thiophosphate to alkaline earth-sulfur-containing phenol-formaldehyde resin is maintained between about 1:10 and 10:1.
• An example of a preferred concentrate within these weight ratios is one which contains about 2 parts of sulfonate, 1 part thiophosphate and 1 part alkaline earth-sulfur-containing phenol-formaldehyde resin.
• the advantages of the improved lubricating composition of the invention as compared with similar compositions containing the individual components are illustrated hereinafter with reference to several of the preferred embodiments of our invention but it is to be understood that they are given by way of illustration and not in limitation thereof.
• the base oil used in preparing the various compositions was a highly refined, aluminum chloride treated, pararfinic oil stock having an API gravity of about 293 and a viscosity of about 340 SUS at 100 F.
• the mixed zinc and calcium salts of Oxo octyl thiophosphate were prepared according to the procedure illustrated in Example I.
• the calcium and barium petroleum sulfonates were prepared by double decomposition from the corresponding sodium salts of the oil-soluble petroleum sulfonic acids having an average molecular weight of about 420.
• Example II is illustrative of the procedure employed.
• the calcium and barium sulfur containing phenol-formaldehyde resins were prepared according to the procedures illustrated in Examples III and IV, re-
• the flask is then placed in an oil bath held at 392 F.- -1 F., the flask being immersed to a depth such that the surface of the oil of the oil bath is about one inch above the body of the flask.
• the flask remains in the oil bath for 2 /2 hours.
• the flask is then removed and cooled to room temperature.
• the contents of the flask are then removed with the aid of dilution naphtha and filtered through a Gooch crucible.
• the precipitate or sludge which remains in the crucible after being dried in a desiccator and drying oven at about 220 F. is weighed to the nearest milligram.
• the weight of sludge thus obtained constitutes the Sligh oxidation number.
• a Sligh oxidation number of 1 indicates a relatively thermally stable composition as compared with a composition having a much higher Sligh oxidation number.
• the make-up of the compositions and the results of the Sligh oxidation tests are shown in Table 1.
• the Sligh oxidation test comprises placing a ten gram sample of the oil to be tested in a Sligh oxidation flask. The air atmosphere over the oil is changed to oxygen by purging with oxygen delivered at a rate of about 5 liters per minute for a period of 30 seconds. The flask is then quickly stoppered with a ground glass stopper to which is attached a convection plug to confine It will be noted from the data in Table 1 that the base oil (Composition A) is substantially thermally stable as evidenced by the Sligh oxidation number of 1.
• composition E barium petroleum sulfonate
• Composition F calcium petroleum sulfonate
• Composition F as further evi- 14 istics, like the thermal stability, are unexpected in the light of the performance of the individual additives.
• the beaker is fitted with a cover provided with the mixed zinc-calcium Oxo octyl thiophosphate prodopenings for a stainless steel, motor-driven stirrer and uct of Example I, the resulting compositions are even for insertion of a standard steel test bar having a diameter less stable than Compositions .G and H as evidenced by 15 of 0.5 inch and a length of approximately 5.5 inches which the Sligh oxidation numbers of 63 and 68 for Composihas been carefully cleaned and polished according to a wn M and N, sp yprescribed procedure just prior to the test.
• the stirrer The sulfonates, llke the calcium-sulfur-containing prodis started and when the oil sample in the beaker reaches not of Example III, have the same detrimental effect on a temperature of 140 F., the test bar is lowered through the composition containing the zinc di-cyclohexyl dithiothe proper opening and is suspended from the beaker phosphate as evidenced by Compositions O and P where cover. After 30 minutes, 50 milli'iters of the oil are rethe Sligh oxidation numbers were increased from 42 to moved and replaced with 30 milliliters of synthetic sea 108 and 67, respectively, by the addition of calcium sulwater.
• compositions tained at a, temperature of 120 F., and a humidity of I, I, K and L compositions containing the zinc thio- 100 percent, The 100 percent humidity is achieved by phosphate compound in combination with the calcium or heating water in the bottom of the cabinet and simulbarium sulfonate and the calciumor bariumsuIfu-r-contaneously bubbling air through the water.
• the steel taining alkyl phenol-formaldehyde resins exhibit a thermal panels slowly revo ve around the inner periphery of the stability equal to that of the base oil. W i e the ca it m3 cabinet.
• compositions not have the same effect on compositions wherein the thioof the invention, Compositions I, J and K, containing all phosphate contains both zinc and an alkaline earth metal. three of the respective additives, are strikingly superior For example, when barium petroleum sulfonate and calto compositions containing only one of the additives.
• compositions have Sligh oxidation numbers of 19 and 3, respectively.
• the lubricating composition of this invention not only has excellent thermal stability but also has excellent rustwill be noted, for example, that the base oil, Composition A, the base oil in combination with the viscosity index improver (acrylate resin), Composition B, the base oil in combination with the barium-sulfur-containing inhibiting characteristics.
• Example Composltlon H each gave less than one y Barlum-sulfuqcontaintng product of Example IV of protection according to the JAN-H-792 test. While actlvemtlredienfil Calcium-sultur-contarmng product of Example III the base oil in combination with the barium and calcnlm (33% activeinqredient) 3.0
• compositions I, I and K did not fail to give l g ggig l Wuhwplmsphate pmduct 1 0 1 0 protection until 39, 48 and 45 days, respectively.
• phosphate is a single metal salt of a thiophosphoric acid garhon gtesid%e, ganggd s on percent 1 22 1.01
• compositions S, T and W as illustrated in Table 3 contain a mixture of calcium and barium salts in combination with the mixed zinc and calcium Oxo octyl thiophosphate product of Example I. These compositions, like those wherein the salts are not mixed, are substantially thermally stable compositions as evidenced by the fact that they have Sligh oxidation numbers of 1.
• the composition of this invention can contain other additive agents to improve other specific properties of the composition.
• other oxidation inhibitors including 2,4,6- tri-tert-butylphenol and 2,6-di-tert-butyl-4-rnethylphenol can be used in combination with the thiophosphoric acid ester, the sulfonate and permanently thermoplastic, resinous condensation product disclosed herein.
• the amounts of the various additives will vary depending upon the particular base oil employed and the severity of the conditions to which the lubricating composition is subjected. In any event, the respective additives are employed in amounts suificient to confer their desired eflfect on the resulting composition.
• Typical make-up and inspection properties of light lubricating oils within the scope of the invention containing the calcium and barium salts are shown in Table 4.
• Each of these compositions also contained 0.5 percent of an acrylate resin as a viscosity index improver, 0.00075 percent of a green dye and 0.0006 to 0.0009 percent of Dow-Corning silicone Fluid 200, as a foam inhibitor.
• the acrylate resin used in these compositions and the others reported hereinabove is known as Acryloid 618, which can be purchased from Rohm & Haas Co., Philadelphia, Pennsylvania.
• the acrylate resin is a viscous liquid at room temperature having a specific gravity of 0.8927 at 60/60 F., a furol viscosity of 395 seconds at 210 F., a flash point (P-M) of 250 F., a fire point (OC) of 375 F., a pour point of +20 F., an ASTM Union color of 1.25, a neutralization number (ASTM D974) of 0.13 and only a trace of water.
• Dow-Corning silicone Fluid 200 can be purchased from Dow-Corning Corporation, Midland, Michigan. This antifoam agent is a liquid polymer of a dialkyl silicone.
• Typical properties of this antifoam agent are: specific gravity at 60/60 F., 0.9779; viscosity at F., 3696 SUS; viseosity at 210 F., 1532 SUS; flash point (CC), 650 F.; and a pour point, below 50 F.
• a lubricating composition having improved resistance to sludge formation upon continued heating and assures first inhibiting characteristics comprising a major pro-portion of a highly refined mineral lubricating oil and minor proportions consisting of about 0.5 to about 5.0 percent by weight of a zinc salt or" a thiophosphoric acid ester obtained by reacting phosphorus pentasulfide with a monohydric alcohol containing 6 to 14 carbon atoms on the average in a mol ratio, respectively, of about 1:4 at a temperature of about 130 to 350 F., and reacting the resultant product with a member selected from the group consisting of zinc metal and a basic zinc compound in a mol ratio of about 0.5 to about 1 mol of said member per mol of phosphorus pentasulfide at a temperature of about 60 to 300 F.; about 0.5 to about 5.0 percent by weight of an oil-soluble alkaline earth metal sulfonate; and about 0.5 to about 5.0 percent by weight of an oil-soluble alkaline earth
• a lubricating composition having improved resistance to sludge formation upon continued heating and rust inhibiting characteristics comprising a major proportion of a highly refined mineral lubricating oil and minor proportions consisting of about 0.5 to about 5.0 percent by weight of a mixed metal salt of a thiophosphoric acid ester, wherein the mixed metal is zinc and an alkaline earth and the mixed metal salt is obtained by reacting phosphorus pentasulfide and an aliphatic monohy'dric alcohol containing 6 to 14 carbon atoms per molecule on the average in a mol ratio, respectively, of about 1:4, said reaction being eiiected at a temperature of about 130 to 350 F., and reacting the resultant product with a member selected from the group consisting of zinc metal and a basic zinc compound in la mol ratio of about 0.5 to 1 mol of said member per mol of phosphorus pentasulfide at temperatures of about 6 to about 180 R, then reacting the resulting reaction product with sufiicient basic alka
• a lubricating composition having improved resistance to sludge formation upon continued heating and rust inhibiting characteristics comprising a major proportion of a highly refined mineral lubricating oil and minor proportions consisting of about 0.5 to about 5.0 percent by weight of zinc dicyclohexyl dithiophosphate; about 0.5 to about 5.0 percent by weight of an oil-soluble calcium sulfonate; and about 0.5 to 5.0 percent by weight of the calcium and sulfur containing condensaton product obtained by condensing in an aqueous medium reactants consisting essentially of formaldehyde, calcium sulfide and tetramethylbutyl phenol, at least one mol of formaldehyde being employed for every two mols of the phenol, and at least one equivalent of calcium sulfide being employed for every two mols of the phenol, the condensation being conducted to avoid any substantial reaction between the phenol and formaldehyde in the absence of the calcium sulfide.
• a lubricating composition having improved resist ance to sludge formation upon continued heating and rust inhibiting characteristics comprising a major proportion of a highly refined mineral lubricating oil and minor proportions consisting of about 0.5 to about 5.0 percent by weight of a mixed metal salt of zinc and calcium branched chain octyl thiophosphate obtained by reacting phosphorus pentasulfide and a mixture of branchedchain octyl alcohols in a mol ratio, respectively, of about 1:4 at a temperature of about to 350 F., and reacting the resultant product with a member selected from the group consisting of zinc metal and a basic zinc compound in a mol ratio of about 05 to 1 mol of said member per mol of phosphorus pentasulfide at temperatures of about 60 to about 180 R, then reacting the resulting reaction product with sufiicient basic calcium compound to raise the pH of the reaction mixture to at least about 6 and about 0.5 to about 2 percent by weight of benzoyl per
• a lubricating composition having improved resistance to sludge formation upon continued heating and rust inhibiting characteristics comprising a major proportion of a highly refined mineral lubricating oil and minor proportions consisting of about 0.5 to about 5.0 percent by weight of a mixed metal salt of zinc and calcium branched chain octyl thiophosphate obtained by reacting phosphorus pentasulfide and a mixture of branched-chain octyl alcohols in a mol ratio, respectively, of about 1:4 at a temperature of about 130 to 350 F., and reacting the resultant product with a member selected from the group consisting of zinc metal and a basic zinc compound in a mol ratio of about 0.5 to 1 mol of said member per mol of phosphorus pentasulfide at temperatures of about 60 to about 180 F., then reacting the resulting reaction product with sufficient basic calcium compound to raise the pH of the reaction mixture to at least about 6 and about 0.5 to about 2 percent by weight of benzoyl peroxide,
• a lubricating composition having improved resistance to sludge formation upon continued heating and rust inhibiting characteristics comprising a major proportion of a highly refined mineral lubricating oil and minor proportions consisting of about 0.5 to about 5.0 percent by weight of a mixed metal salt of zinc and calcium branched chain octyl thiophosphate obtained by reacting phosphorus pentasulfide and a mixture of branched-chain octyl alcohols in a mol ratio, respectively, of about 1:4 at a temperature of about 130 to 350 F., and reactIng the resultant product with a member selected from the group consisting of zinc metal and a basic zinc compound in a mol ratio of about 0.5 to 1 mol of said member per mol of phosphorus pentasulfide at temperatures of about 60 to about 180 F., then reacting the resulting reaction product with sufficient basic calcium compound to raise the pH of the reaction mixture to at least about 6 and about 0.5 to about 2 percent by weight of benzoyl peroxide
• a lubricating composition having improved resistance to sludge formation upon continued heating and rust inhibiting characteristics comprising a major proportion of a highly refined mineral lubricating oil and minor proportions consisting of about 0.5 to about 5.0 percent by weight of a mixed metal salt of zinc and calcium branched chain octyl thiophosphate obtained by reacting phosphorus pentasulfide and a mixture of branchedchain octyl alcohols in a mol ratio, respectively, of about 1:4 at a temperature of about 130 to 350 F., and reacting the resultant product with a member selected from the group consisting of zinc metal and a basic zinc compound in a mol ratio of about 0.5 to 1 mol of said member per mol of phosphorus pentasulfide at temperatures of about 60 to about 180 F., then reacting the resulting reaction product with sufficient basic calcium compound to raise the pH of the reaction mixture to at least about 6 and about 0.5 to about 2 percent by weight of benzoyl peroxide, at
• a lubricating composition having improved resistance to sludge formation upon continued heating and rust inhibiting characteristics comprising a major proportion of a highly refined mineral lubricating oil and minor proportions consisting of about 1 percent by weight of a mixed metal salt of zinc and calcium branched chain octyl thiophosphate obtained by reacting phosphorus pentasulfide and a mixture of branched-chain octyl alcohols in a mol ratio, respectively, of about 1:4 at a temperature of about to 350 F., and reacting the resultant product with a member selected from the group consisting of zinc metal and a basic zinc compound in a mol ratio of about 0.5 to 1 mol of said member per mol of phosphorus pentasulfide at temperatures of about 60 to about 180 F., then reacting the resulting reaction product with sufiicient basic calcium compound to raise the pH of the reaction mixture to at least about 6 and about 0.5 to about 2 percent by weight of benzoyl peroxide, at least
• a lubricating composition having improved resistance to sludge formation upon continued heating and rust inhibiting characteristics comprising a major proportion of a highly refined mineral lubricating oil and minor proportions consisting of about 1 percent by weight of a mixed metal salt of zinc and calcium branched chain octyl thiophosphate obtained by reacting phosphorus pentasulfide and a mixture of branched-chain octyl alcohols in a mol ratio, respectively, of about 1:4 at a temperature of about 130 to 350 F., and reacting the resultant product with a member selected from the group consisting of zinc metal and a basic zinc compound in a mol ratio of about 0.5 to 1 mol of said member per mol of phosphorus pentasulfide at temperatures of about 60 to about 180 F., then reacting the resulting reaction product with sufficient basic calcium compound to raise the pH of the reaction mixture to at least about 6 and about 0.5 to about 2 percent by weight of benzoyl peroxide, at a temperature of
• a lubricating composition having improved resistance to sludge formation upon continued heating and rust inhibiting characteristics comprising a major proportion of a hghly refined mineral lubricating oil and minor proportions consisting of about 1 percent by weight of acumen a "mixed nieft'al sal t of zine and calcium branched chain octyl thiophosphate obtained by reacting phosphorus-pent'asulnde and a mixture of branched-chain octyl alcohols in a mol ratio, respectively, of about 1:4 at a temperature of about 130 to 350 F., and reacting the resultant product with a member selected from the group consisting of zinc metal and a basic zinc compound in a mol ratio of about 0.5 to 1 mol of said member per mol of phosphorus pentasulfide at temperatures of about 60 to about 180 F., then reacting the resulting reaction product with sufficient basic calcium compound to raise the pH of the reaction mixture to at least about 6 and about 0.5 to
• the condensation being conducted to avoid any substantial reaction between the phenol and formaldehyde in the absence of the calcium sulfide; and a viscosity index improving amount of an acrylate resin.
• a lubricating composition having improved resistance to sludge formation upon continued heating and rust inhibiting characteristics comprising a major proportion of a highly refined mineral lubricating oil and minor proportions consisting of about 0.5 to about 5.0 percent by weight of a mixed metal salt of zinc and calcium branched chain octyl thiophosphate obtained by reacting phosphorus pentasulfide and a mixture of branched-chain octyl alcohols in a mol ratio, respectively, of about 1:4 at a temperature of about to 350 F., and reacting the resultant product with a member selected from the group consisting of zinc metal and a basic zinc compound in a mol ratio of about 0.5 to 1 mol of said member per mol of phosphorus pentasulfide at temperatures of about 60 to about 180 F., then reacting the resulting reaction product with suflicient basic calcium compound to raise the pH of the reaction mixture to at least about 6 and about 0.5 to about 2 percent by weight of benzoyl peroxid
• a lubricating composition having improved resistance to sludge formation upon continued heating and rust inhibiting characteristics comprising a major proportion of a highly refined mineral lubricating oil and minor proportions consisting of about 0.5 to about 5.0 percent by weight of a mixed metal salt of zinc and calcium branched chain octyl thiophosphate obtained by reacting phosphorus pentasulfide and a mixture of branched-chain octyl alcohols in a mol ratio, respectively, of about 1:4 at a temperature of about 130 to 350 F, and reacting the resultant product with a member selected from the group consisting of zinc metal and a basic zinc compound in a mol ratio of about 0.5 to 1 mol of said member per mol of phosphorus nentasulfide at temperatures of about 60 to about 180 F., then reacting the resulting reaction product with suflicient basic calcium compound to raise the pH of the reaction mixture to at least about 6 and about 0.5 to about 2 percent by weight of benzoyl per

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