US2523100A - Mineral oil composition and additive therefor - Google Patents

Description

Patented Sept. 19, 1950 1 I OIL COMPOSITION AND ADDITIVE Lawrence T. Eby, Roselle, N. J., assignor to Standard Oil Development Company, a, corporation, v

01 Delaware 1 No Drawing.

This invention relates to new chemical products and to improved lubricating oils containing such products as additives.

Many types of chemical compounds have been proposed for use as detergent additives for lubricating oils, for the purpose of dispersing sludge and maintainin a clean engine condition when such oils are employed as crankcase lubricants for internal combustion engines. Most of the additives which have been found effective for such use contain metals, and while their sludge dispersing properties are satisfactory, there'is the objection that a metal-containing deposit will be formed which gradually becomes forced into the engine cylinder and tends to foul the spark plugs and produce other undesirable effects. It is accordingly an object of the present invention to provide an additive which is an effective detergent and at the same time contains no metal and is accordingly entirely free from any tendency to form a deposit of the type described.

The new class of additives which are described herein are non-metallic and have been found to possess the required degree of sludge dispersing and detergent properties, and these have been found to possess in addition the property of inhibiting oxidation of the oil. They have also been found to be valuable additives for extreme pressure lubricants containing chlorine compounds which tend to evolve hydrogen chloride during storage, the additive having the efl'ect of neutralizing such corrosive products without at the same time producing an objectionable precipitate during periods of storage of a lubricant.

The new additives of the present invention, which are also new chemical compounds, are quaternary bases and salts formed by the alkylation of dialkylaminomethyl phenol sulfides containing certain oil-solubilizing alkyl groups, as specified hereinafter. The new additives may be defined broadly by the formulas in which R1, R2 and R3 are alkyl radicals with a total of at last 9 carbon atoms, X is a hyppllcation Main, 1941, SerialNo.748,85 a, 11 Claims. (01. 252-415) 4 and preferably 8 carbonatoms, 'andm, is a number from-1 to-" i'.-' The acid radicals which may be substituted for the hydroxyl groups of 'such quaternary bases maybe any acid radicals, whether inorganic or organic; ;The acid radicals which have been found to be particularly desirable for the purpose of the present droxyl group or an inorganic or organic acid radical, R4 is hydrogen or an alkyliradical, R and R are alkyl radicals, each containing at least invention and which maybe readilyintroduced into the compounds are those wh'ichare derived from the following acids: phosphoric, thiophosphoric, carbonic, thiocarbonic, sulfurous, sulfuric, mono-alkyl sulfuric, tetraisobute'nyl'sulfonic, thiocyanic, hydrochloric, nitric and boric.

In the preparation of the new compounds and additives of the present invention, alkylated phenols are first formed by reacting phenols with oleflns in the presence of an alkylating catalyst. From these the monosulfides and polysulfides may be formed by reaction with chlorides of sulfur. .The aminoalkylderivatives of such products may be formed by first preparing an alkylaminoalkyl-alkyl ether and then reacting the same in the presence of an alcohol with the alkylated phenol sulfide. From the productsthus formed a quaternary ammonium base maybe derived by treating with an alkylating agent,=such as a dialkyl sulfate or an alkyl halide, followed by reaction with a free base. Asan alternative method, the alkyl phenol sulfide may-first be converted into a chloralkyl derivative by reaction 'with an aldehyde in the presence of hydrogen chloride, further reacting the product thus formed with a tertiary amine, and finallyreacting the resulting chlorinated compound with a base. If it is desired to convert the base into a salt, the former may be reacted with anacid or with an acid anhydride. Phosphoric or thiophosphoric acid salts may thus be formed by reaction with anoxide or'sulfide of phosphorus. Similarly, a thiocarbonate salt may beformed by reaction with carbon disulfide. The preparation of a number of specific examples .of the compounds of the present-invention is described in detail below.

The quantity of the additives of the present invention which is most advantageously blended inthe mineral lubricating oil will depend uponr the property of the additive which it is most desired'to exploit' When employed for detergent and sludge dispersing purposes, the quantity most suitable will generally v'ary from Q1 't'o5%. For merely -inhibiting bearing corrosion andthe like the quantity most desirable will be, from 0.05% 't0*2%. When the additive is to be femployed as 'a corrosion inhibitor in an extreme pressure lubricant composition, it is desir'able to employ from 0.2% to 1%, particularly when "the lubricating" oil contains abo t .0% of. a chlorinated hydrocarbon containing, approximately 32% chlorine.

Example 1.Di(di-n-octylmethylaminomethyl) tert-octyiphenol polysulflde hydroxide In a flask was placed 200 cc. of absolute ethyl alcohol, 120.5 g. (0.5 mol) of di-noctylamine and 15 g. (0.5 mol CHzO) of trioxymethylene. The mixture was stirred overnight to give a solution of 0.5 mol of di-n-octylaminomethyl ethyl ether.

A solution of 1030 g. mols) of distilled tertoctylphenol and 1000 cc. of chloroform was charged to a flask and stirred while 770 g. (7.5 mols) of sulfur dichloride was added during 2 hours, keeping the temperature below 30 C. The mixture was refluxed with stirring for 3 hours and then cooled, poured into water, extracted with ether, washed free of hydrochloric acid, dried over sodium sulfate, and the solvent removed by distillation, finishing at reduced pressure. The residue weighed 1506 g. and contained 15.61% sulfur (Parr Bomb), which corresponds to the formula on OK G CsHn C 51111 Half of the solution (0.25 mol) of di-n-octylhminomethyl ethyl etherdescribed abovewasadded to a solution of 49.3 g. (0.102 mol) of the sulfurized phenol described above in 200 cc. of absolute ethyl alcohol. The mixture was stirred and refluxed overnight. After cooling, 63 g. (0.5 mol) of dimethylsulfate was added and the mixture stirred overnight. The volatile constituents were removed by vacuum distillation, finishing over a boiling water bath at 2 mm. pressure. The residue weighing 173 g. was a brown viscous liquid which was found to contain 13.30% sulfur (Parr Bomb) and 1.95% nitrogen (Kjeldahl).

This di(di-n-octylmethylaminomethyl) -tertoctylphenol polysulflde di(methyl sulfate) was dissolved in ether and stirred with aqueous sodium hydroxide'overnight. The ether layer was separated, washed with water, dried over anhydrous potassium' carbonate, filtered, and the ether removed by distillation. The residue was a brown liquid less viscous than the methyl sulfate and contained 5.29% sulfur and 3.00% nitrogen. The product is di(di-n-octylmethylaminomethyl)-tert-octylphenol polysulflde hydroxide.

Example 2.-Di n octylmethylaminomethyltert-octylphenol polysulflde hydroxide The same procedure as that used in Example 1 was used, except that 98.5 g. (0.204 mol) of the alkylated phenol polysulflde was used. The din octylmethylaminomethyl tert octylphenol polysulflde was obtained as a brown viscous liquid weighing 217.2 g. and containing 13.73% sulfur and 1.53% nitrogen. The free base was obtained by reacting such product with sodium hydroxide solution as in Example 1, and was obtained as a brown viscous liquid not as viscous as the sulfate and containing 7.22% sulfur and 2.15% nitrogen.

Example 3.Thiophosphate of di(di-n-octylmethylaminomethyl) -tert-0ctylphenol polysulflde hydroxide 1030 g. (5 mols) of distilled tert-octylphenol and 1 l. of chloroform were placed in a flask equipped with stirrer, dropping funnel, return condenser and thermometer. 386 g. (3.75 mols) of sulfur dichloride was dropped into the mixture while stirring over a period of 6 hours, keeping the temperature below 30 C. The mixture was refluxed 6 hours, cooled and poured into water. The organic layer was removed, washed again with water and dried over anhydrous sodium sulfate. The mixture was filtered from the drying agent and stripped of solvent by vacuum distillation. The residue was a reddish brown resin-like solid when cooled and weighed 1081.7 g. The product contained 10.69% sulfur and thus corresponds approximately to the formula OH OH CaHn CaHn 228.8 g. (0.5 mol) of the phenol sulfide product described above, 600 cc. of absolute ethyl alcohol, 241 g. (1 mol) of di-n-octylamine and 30 g. (1 mol CHzO) of trioxymethylene were stirred together for one hour and then refluxed for one hour. The mixture was cooled to room temperature and 163.8 g. (1.3 mols) of dimethyl sulfate was added with stirring to produce a solution of di(di-n-octylmethylamlnomethyl)-tert-octylphenol polysulflde di-(methyl sulfate).

225 cc. of 25% of aqueous sodium hydroxide solution and 275 cc. of water were added to the alcohol solution of di(di-n-octylmethylaminomethyl) -tert-octylphenol polysulflde di- (methyl sulfate) described above. The mixture was stirred for 3 hours. The organic material was extracted with 100 cc. of ether after dilution with 1 l. of water. The ether extract was stirred with 100 cc. of 25% aqueous sodium hydroxide solution and 100 cc. water for 3 hours. The organic layer was washed with three 500 cc. portions of water and dried over anhydrous potassium carbonate. After filtering, the volatile materials were removed by vacuum distillation, leaving 463.1 g. of brown viscousliquid residue which contained 4.86% sulfur and 2.61% nitrogen.

51.35 g. (0.05 mol) of di(di-n-octylmethylaminomethyl) -tert-octylphenol sulfide hydroxide, prepared as described in the preceding paragraph, and 3.53 g. (0.0167 mol) of P285 were stirred together at room temperature for 20 hours. Hydrogen sulfide Was liberated. cc. of etherwas added and the mixture stirred 24 hours. The ether was removed by distillation leaving a viscous dark reddish brown material containing 8.25% sulfur, 2.37% nitrogen, and 1.88% phosphorus. The product is thus a thiophosphate of di(di n octylmethylaminomethyl) tert octylphenol polysulflde hydroxide.

Example 4.--Thz'ophosphate of di(di-n-octylmethylaminomethyl) -tert-octylphen ol polysulfide hydroxide liberated. 50 cc. of ether was added and the mix- .mixture was refluxed overnight.

ture stirred 24 hours The ether was removed by distillation, leaving a viscous dark reddish brown material containing 8.83% sulfur, 2.24% nitrogen and 1.97% phosphorus.

Example 5.-- Thiocarbonate' of I di(di-n-octylmethylaminomethyl) -tert-octylphenol polysulfide hydroxide 51.35 g. (0.05 mol) of di(di-n-octy1methylaminomethyl)-tert-octylphenol polysulfide hydroxide, prepared asdescribed in Example 3, and 25 cc. of carbon bisulfide were stirred together for 20 hours. There was no apparent liberation of hydrogen sulfide, but a homogeneous solution formed with a rise in temperature of 3 C. The

solution was diluted with 50 cc. of ether and then stripped of volatile constituents by vacuum distillation over a boiling water bath. The residue, weighing 51.2 g. was a reddish brown v scous liquid which contained 6.49% sulfur and 2.58% nitrogen. The product is thus a thiocarbonate of di (di-n-octylmethylaminomethyl) -tert-octylphenol polysulflde hydroxide.

Example 6.Dioctylmethylaminomethyl-tert-octylphenol polysulfide methyl sulfate 1030 g. (5 mols) of distilled tert-octylphenol and 1 l. of chloroform were placed in a flask equipped with stirrer, dropping funnel, return condenser OH OH O aHn CaHn 228.5 g. (0.5 mol) of the product described above was dissolved in 600 cc. of absolute ethyl alcohol and placed in a flask equipped with a dropping funnel. A solution of 120.5 g. (0.5 mol) of di-n-octylamine and g. (0.5 mol CHzO) of trioxymethylene in 200 cc. of absolute ethyl alcohol was added slowly from the dropping funnel. The After cooling, 126 g. (1 mol) of dimethyl sulfate was added slowly with stirring. The mixture was stripped of volatile components by vacuum distillation and the residue was the brown very viscous liquid weighing 509.9 g. and containing 11.36% sulfur and 1.40% nitrogen. The product-was thus di-noctylmethylaminomethyl-tert-octylphenol polysulfide methyl sulfate.

Example 7 .Di di-n-octylmethylwminomethyl tert-octylphewol polysulfide di(methyl sulfate) Example 6 was repeated except-that 114.3 g. (0.25 mol) of the polysulfide product was used. The product was a very viscous brown liquid weighing 356.1 g. and containing 11.62% sulfur and 1.87% nitrogen. The product is di(di-n-octylmethylaminomethyl) -tert-octyphenol polysulfide di(methyl sulfate). I

Example 8.Di-n-octylmethylaminomethyl-tert- Octylphenol polysulfide hydroxide 374.2 g. of the productfrom Example 6'and 350 cc. of ether were placed in a flask and stirred with 250 cc. of aqueous sodium hydroxide solution. After stirring for 1.5 hours, the layers were allowed to separate and the ether layer again stirred with 20% aqueous sodium hydroxide solution. The layers were separated and the ether solution washed twice with water and then allowed to stand overnight to separate any residual water in the organic layer. The volatile constituents were removed from the organic layer by vacuum distillation. The residue was a brown viscous liquid weighing 290.5 g. and containing 6.54% 81111111 and 1.88% nitrogen. This product was di-n-octylmethylaminomethyl-tert-octylphenol polysulfide hydroxide.

- Example 9.Di(di-n-octylmethylaminomethyl) tert-octylphenol polysulflde hydroxide 299.4 g. of the product from Example 7, and 300 cc. of ether were placed in a flask and stirred with 200 cc. of 20% aqueous sodium hydroxide solution. After stirring for 1 hours the layers were allowed to separate and the ether layer again stirred with 20% aqueous sodium hydroxide solution. The layers were separated and the ether solution washed twice with water, dried over anhydrous potassium carbonate and stripped of vol v The atile constituents by vacuum distillation. residue was a brown viscous liquid weighing. 198.8 g. and containing 4.99% sulfur and 2.70% nitrogen. This product was dfldi-n-octylmethylaminomethyl)tert-octylphenol polysulfide hydroxide.

Til

Example 10.Di n butylmethylamlnomethyltert-butylphenol sulfide hydroxide A glass reaction flask was charged with 300.4 g. (2.0 'mols of p-tert-butylphenol and 500 ml. of chloroform. The mixture was stirred and 103.0 g. (1.0 mols) of sulfur dichloride was added from a dropping funnel over three hours while maintaining the temperature below 30 C. The solution was "heated under reflux for four hours, cooled, washed with water, then with aqueous sodium bicarbonate solution and dried over sodium sulfate. The drying agent was removed by filtration and the organic layer stripped ofsolventby distillation to a temperature of 115 C. at

The residue was p-tert-butyl:

cohol, and 65.1 g. of di-n-butylamine was added to the flask and stirred for one-half hour. The solution was heated under reflux for four hours. The solution was cooled and 126 g. (1 mol) of dimethyl sulfate was added after which the mixture was stirred for an additional two hours before stripping to remove unreacted reagents and solvent. Stripping was carried to C. at 2 mm. pressure to obtain 342.7 g. of residue, which is din butylaminomethyl-tert butylphenol sulfide methyl sulfate. This product was not soluble in 1% concentration in either a 100 V. I. or 28 V. I. mineral lubricating (S. A. E. 20) oil.

A glass flask was charged with 119.8 g. (0.205 mol) of di-n-butylmethylaminomethyl-tert-butylphenol sulfide methyl sulfate (prepared as described above), 200 ml. of benzene, and 100 nil. of aqueous 25% sodium hydroxide solution. The mixture was stirred for 1.5 hours and the aqueous layer then removed. Another 100 ml. of 25% sodium hydroxide was added and the mixture stirred for 1.5 hours. The organic layer was washed twice with distilled water. The second wash required centrifuging to remove the water. The organic layer was Stripped to a temperature of 100 C. at 1 mm. The residue weighed 72.0 g. and was not completely soluble in the 100 V. I. S. A. E. 20 oil but the 1% solution in the 28 V. I. oil was clear at room temperature. The residue was di n butylmethylaminomethyl-tert-butylphenol sulfide hydroxide.

Example 11.-Carbon black dispersion tests A series of carbon black dispersion tests were carried out, as described in U. S. Patent 2,390,342, to measure the comparative efiectiveness of the additives of the present invention as agents for dispersing sludge in lubricating oil. In these tests 6% by weight of activated carbon was added to the oil blend containing the additive and thoroughly dispersed in the oil by stirring with an "egg beater" type mixer for minutes while the temperature of the oil was maintained at 250 F. 250 cc. of the blend was then placed in a 250 cc. graduated cylinder and allowed to settle for 24 hours while the temperature was maintained at 200 F. If an additive is not a dispersing agent, the carbon black settles rapidly at this point leaving clear oil at the top in an hour or two. A very effective disperser will maintain the carbon black in suspension so that no change in the opaque slurry is apparent even after a 24- hour period. With all but the most potent dispersing agents stratification occurs with a black layer at the botton (high concentration of carbon black) and a blue opaque layer at the top (reduced carbon black concentration). Cases of this type, known as "blue line separations, are only detectable in reflected light and the top oil contains smaller particles of dispersed carbon black. Base oil A used in this test was a paraf- 8 lubricating oil of S. A. E. 20 grade. The test was applied to the unblended base oil as well as to the blends. The test was conducted as follows: 500 cc. of the oil was placed in a glass oxidation tube (13 inches long and 2% inches in diameter) fitted at the bottom with a inch air inlet tube perforated to facilitate air distribution. The oxidation tube was then immersed in a heatin bath so that the oil temperature was maintained at 325 F. during the test. Two quarter sections of automotive bearings of copper-lead alloy of known weight having a totalarea of 25 sq. cm. were attached to opposite sides of a. stainless steel rod which was then immersed in the test oil and rotated at 600 R. P. M., thus providing sufficient agitation of the sample during the test. Air was then blown through the oil at the rate of 2 cu. ft. per hour. At the end of each 4-hour period the bearings were removed, washed with naphtha and weighed to determine the amount of loss by corrosion. The bearings were then repolished (to increase the severity of the test), reweighed,

' and then subjected to the test for additional finic oil of S. A. E. 20 grade, while base oil B was a naphthenic oil of seconds viscosity Saybolt at 210 F. The results of the test when applied to blends containing the products of Examples 1,

2, and 10 are shown in the following table, in

which the results are shown as the volume of oil below the line of demarcation and containing essentially all of the dispersed carbon black after the settling period.

Add Carbon Black 87 (top oil is clear).

Base Oil A 234 ("blue line" separation).

Base oil A+l% di (di-n-oetyl-methylaminomethyl)-tert-oetyl-phenol polysulfide hydroxide (Example 1).

Base oil A+l% di-n-octyl-methylaminomethyl-tert-octyl-phenol polysulflde hydroxide (Example 2).

Base oil B Base oil B+1% di'n-butyl-methylaminomethyl-tert-butyl-phenol sulfide hydroxide (Example 10).

182 (blue line" separation).

115 (top 011 is deal). 134 ("blue line" separation).

Emample 12.Bearing corrosion tests Cc. Oil Containing Dispersed 4-hour periods in like manner. The results are given in the following table as corrosion life," which indicates the number of hours required for the hearings to lose 100 mg. in weight, determined by interpolation of the data. obtained in the various periods.

Example 13.-Ea:treme pressure lubricant corrosion and stability tests The ability of the additives of the present invention to prevent corrosion due to the extreme pressure agent of an extreme pressure lubricant was tested by incorporating 0.4% 01 each of several examples of such additives in an extreme pressure lubricant consisting of of an acid and clay treated Coastal oil distillate having a viscosity of 70 seconds Saybolt at 210 F. and 10% of an extreme pressure lubricant consisting'of a sulfurized and chlorinated kerosene containing 6 to 7% sulfur and about 32% chlorine, and testing such blends in an S. A. E. Extreme Pressure Testing Machine. The machine was operated for 30 seconds at 20 pounds load and then at 50 pounds load for 5 minutes. The test ring was placed in a desiccator containing a saturated solution of sodium carbonate for 24 hours, washed with benzene and observed for evidence of corrosion. The amount of corrosion is given as the percentage of the entire area which showed corrosion. a

Results are as follows:

Additive Per cent Blank Dioctylmethylaminomethyl-tert-octylpbenol polysuiiidc methyl sulfate (Example 6) Di (di-n-octylmethylaminomethyl) iert-octylphenol polysulfide di-(mcthyl sulfate) (Example 7) Dioctylmethylaminomethyl-tert-octylphenol polysulfide hydroxide (Example 8) Di (di-n-octylmethylaminomethyl) hydroxide (Example 9) preparing an extreme pressure agent described above containing 4 of an additive of the present invention, then storing such concentrate in a glass vessel in the presence of a steel strip for 24 hours at 150 F., after which the material was cooled and blended in 10% portions in a base stock consisting of a Panhandle bright stock, which is a highly parafiinic oil, and observing the condition of the oil after 10 days storage at room temperature. Blends prepared with dioctylmethylaminomethyl-tert-octylphenol polysulfide methyl sulfate and with dioctylmethylaminomethyl-tert-octylphenol polysulfide hydroxide, the same being two of the additives tested for corrosion preventing ability in this example, showed the additives to be completely soluble after the storage period.

The products of the present invention may be employed not only in ordinary hydrocarbon lubricating oils but also in the heavy duty type of lubricating oils which have been compounded with such detergent type additives as metal soaps, metal petroleum sulfonates, metal phenates, metal alcoholates, metal alkyl phenol sulfides, metal organo phosphates, thiophosphates, phosphites and thiophosphites, metal salicylates,

metal xanthates and thioxanthates, metal thiocarbamates, amines and amine derivatives, reaction products of metal phenates and sulfur, re-

phenyl stearate, zinc diisopropyl salicylate, 1,

aluminum naphthenate, calcium cetyl phosphate, barium di-tert-amylphenol sulfide, calcium petroleum sulfonate, zinc methyl cyclohexyl thiophosphate, calcium dichlorostearate, etc. Other types of additives, such as phenols and phenol sulfides may also be employed.

The lubricating oil base stocks used in the compositions of this invention may be straight mineral lubricating oils or distillates derived from parafiinic, naphthenic, asphaltic or mixed base crudes, or, if desired, various blended oils maybe employed as well as residuals, particularly those from which alphaltic constituents have been carefull removed. The oils may be refined by conventional methods using acid, alkali and/or clay or other agents such as aluminum chloride, or they may be extracted oils produced, for example, by solvent extraction with solvents of the type of phenol, sulfur dioxide, furfural, di-

chlorodiethyl ether, nitrobenzene, crotonalde-- hyde, etc. Hydrogenated oils or white oils may be employed as well as synthetic oil prepared, for example, by the polymerization of olefins or by the reaction of oxides of carbon with hydrogen or by the hydrogenation of coal or its products. In certain instances cracking coil tar fractions and coal tar or shale oil distillates may also be used. Also, for special applications, animal, vegetable or fish oils or their hydrogenated or voltolized products may be employed in admixture with mineral oils.

For the best results the base stock chosen should normally be that oil which without the new additive present gives the optimum performance in the service contemplated. However,

1'0 since one advantage of the additives is that their use also makes feasible the employment of less satisfactory mineral oils or other oils, no strict rule can be laid down for the choice of the base stock. Certain essentialsmust of course be observed. -The oil must possess the viscosity and volatility characteristics known to be required for the service contemplated. The oil must be a satisfactory solvent for the additive, although in some cases auxiliarysolvent agents may be used. The lubricating oils, however they may have been .produced, may vary considerably in viscosity and other properties depending upon the patricular use for which they are desired. but they usually range from about 40, to 150 seconds Saybolt viscosity. at 210 F. ,For the lubricating of certain low and medium speed Diesel engines the general practice has often been to use a lubricating oil base stock prepared from naphthenic or aromatic crudes and having aSaybolt viscosity at 210 F. of 45 to 90 seconds and a viscosity index of 0 to 50. However, in certain types of Diesel engine and other gasoline engine service, oils of higher viscosity index are often preferred, for example, up to 75 to 100, or even higher, viscosity index. 7

In addition to the materials to be added according to the present invention, other agents may also be used such as dyes, pour depressors,

heat thickened fatty oils, sulfurized fatty oils,

organo-metallic compounds, metallic .or other soaps, sludge dispersers, antioxidants, thickeners,

viscosityindex improvers, oiliness agents, resins, I

rubber, olefin polymers, voltolized fats, voltolized mineral oils, and/or voltalized waxes and colloidal solidssuch as graphite or zinc oxide, etc. Solvents and assisting agents, such as esters, ketones,

referred to as. octadecyl alcohol (CmHa'rOH), heptadecyl-alcohol (C17H35OH), and the like, the

corresponding olefinic alcohols such as oleyl alcohol; cyclic alcohols such as naphthenic alco-- hols; and aryl substituted alkyl alcohols, for instance, phenyl octyl alcohol, or octadecyl benzyl alcohol or mixtures of these various alcohols, which may be pure or substantially pure synthetic alcohols. One may also use mixed naturally occurring alcohols such as those found in wool fat (which is known to contain a substane tial percentage of alcohols having about 16 to 8 carbon atoms) and in sperm oil (which contains a high percentage of cetyl alcohol); and although it is preferable to'isolate the alcohols from those materials, for some purposes, the wool fat, sperm oil or other natural products rich in alcohols may be used per se. Products prepared synthetically by chemical processes may also be used, such as .alcohols prepared by the oxidation of petroleum hydrocarbons, e. g., paraffln wax, petrolatum, etc.

In addition to being employed in crankcase lubricants the additives of the present invention may also be used in extreme pressure lubricants, engine flushing oils, industrial oils, general machinery oils, process oils, rust preventive compositions and greases.

but is to be limited solely by the terms of the appended claims.

I claim:

l. A composition consisting essentially of a hydrocarbon base containing 0.05 to of a compound of the formula OH on I }s-E I I wherein R and R are alkyl radicals each containing at least 4 carbon atoms, 11. is a number from 1 to 4, and wherein there is attached to the benzene nuclei one to two radicals, not more than one such radical to a given benzene nucleus, of the formula R: i wherein R1, R2, and Rs are alkyl radicals containing an overall total of at least 9 carbon atoms and X is a member of the group consisting of hydroxyl radicals and acid radicals derived from water-soluble acids having an ionization constant at least as great as 3.5 x

2. A mineral lubricating oil containing 0.05 to 5% of a compound of the formula wherein R and R' are alkyl radicals each containing. at least 4 carbon atoms, 12. is a number from 1 to 4, and wherein there is attached to the benzene nuclei one to two radicals, not more than onesuch radical to a given benzene nucleus, of the formula wherein R1, R2, and R3 are alkyl radicals containing an overall total of at least 9 carbon atoms and X is a member of the group consisting oi hydroxyl radicals and acid radicals derived from water-soluble acids having an ionization constant at least as great as 3.5 x 10".

3. A mineral lubricating oil composition according to claim 2 in which X of the formula is OH, and R and R are each CaHn.

4. A mineral lubricating oil composition according to claim 2 in which X of the formula is OH, R1, R2, R, and R are each CaH17, and Rs is CH3.

5. A mineral lubricating oil composition according to claim 2 in which X is a thiophosphate radical, R1, R2, R, and R are each CaHn, and R3 is CHa.

6. A mineral lubricating oil composition according to claim 2 in which X is a thiocarbonate radical, R1, R21, R, and R are each CaHu, and R3 is CH3.

7. As a new compound a compound of the formula on OH I 3-$E I wherein R and R are alkyl radicals each containing at least 4 carbon atoms, n is a number from 1 to 4, and wherein there is attached to the benzene nuclei one to two radicals, not more than one such radical to a given benzene nucleus, of the formula wherein R1, R2, and Rs are alkyl radicals containing an overall total of at least 9 carbon atoms. and X is a member of the group consisting of hydroxyl radicals and acid radicals derived from water-soluble acids having an ionization constant at least as great as 3.5 x 10-".

8. A compound according to claim 7 in which X of the formula is OH, and R and R are each CaHi'z.

9. A compound according to claim 7 in which X is OH, R1, R2, R and R are each CeHn, and Ra is CH3.

10. A compound according to claim 7 in which X is a thiophosphate radical, R1, R2, R and R are each CaHvz, and R3 is CH3.

11. A compound according to claim 7 in which X is a thiocarbonate radical, R1, R11, R, and R are each CsHn, and R3 is CH3.

LAWRENCE T. EBY.

REFERENCES CITED The following references are of record in the flle of this patent:

UNITED STATES PATENTS Number Name Date 2,218,739 Bruson Oct. 22, 1940 2,260,967 Bruson Oct. 28, 1941 2,334,594 Zimmer et a1 Nov. 16, 1943 2,345,239 Cook et al Mar. 28, 1944 2,363,134 McCleary Nov. 21, 1944 2,416,265 Mac Mullen et al. Feb. 18, 1947 2,431,011 Zimmer et al Nov. 18, 1947

Claims (1)

1. A COMPOSITION CONSISTING ESSENTIALLY OF A HYDROCARBON BASE CONTAINING 0.05 TO 5% OF A COMPOUND OF THE FORMULA