US2644792A

US2644792A - Compounded lubricating oil

Info

Publication number: US2644792A
Application number: US134879A
Authority: US
Inventors: Max W Hill
Original assignee: Standard Oil Development Co
Current assignee: Standard Oil Development Co
Priority date: 1949-12-23
Filing date: 1949-12-23
Publication date: 1953-07-07
Anticipated expiration: 1970-07-07

Description

Patented July 7, 1953 COMPOUNDED LUBRICATING OIL I Mexw. mu, Somei-ville, N. J., assignor to Standard-Oil Development Company, a corporation of. Delaware 7 No Drawing.

Application December 23, 1949, Serial No. 134,879

17 Claims. (Cl. 25232.7)

This invention relates to mineral oil compositions and particularly'to lubricants containing a detergent additive.

'This is a continuation-impart of copending application Serial Number 89,370, filed April 23, 1949, now U. S. Patent "2,613,205, issued on. October '7, 1952;

The art ofinetalli'c detergents forlubricating oil compositions adapted for use in internal combustion engines is'well known to those versed in this field and has resulted in substantial improvements in lubricants. These detergents are particularly useful in lubricating oil compositions which are'empl'oyed in internal combustion engines used in the Operations of automobiles,

aircraft and similar" vehicles, including diesel engines, to'improve their operation by preventing or retardingcorrosion, piston ring sticking, cylinder wear, and carbon and varnish formation. However, when metallic detergents are used in lubricating compositions where oil consumption is high and engine conditions are severe, such as in aircraft engines or where such concentrations of metallic detergents-are used to maintain engine cleanliness under conditions where high deposit fuels of cracked or high sulfur nature are used, such as in automobile and diesel operation, the ash content from the metallic detergent accumulates in the combustion chamber and causes pre-ignition, detonation, spark plug fouling, valve burning, and ultimate destruction of the engine.

It has been found, in accordance withthe present invention, that if the reaction product of a phosphorus sulfide with an essentially hydrocarbon product is neutralized with guanidineor any of its derivatives as hereinafter defined or with any other compound containing a guanyl radical, the product so formed is very stable at the temperatures of engine operation and serves 1 the purpose of a good detergent and anti-oxidant. When incorporated in mineral lubricating oil which is used in an internal combustion engine, and because it contains no metal, it is free from the objectionable feature of leaving a metallic deposit or ash. These compounds are eiiective not only when added directly to the crankcase lubricant but also when added to the engine fuel, since in the operation of the engine it will work its Way from the combustion chamber into the crankcase and there blend with the lubricant.

Guanidine and guanidine derivatives may be employed as the basic reagents for neutralizing the titratable acidity of the phosphorus sulfidehydrocarbon reaction product. The free 10 1 6 guanidine and its derivatives may be usedaaswell as basic acting salts of such bases, by which;

is meant salts of acids'whosestrength, measured on a pH scale, is less than thatof the acidic phos'-- phorus sulfide-hydrocarbon product. Such basic acting salts are, for example, the carbonates of guanidine and its derivatives. Alternatively, the final products may be formed by double decomposition of a salt of guanidine or guanidine'derivative, e. g., guanidine hydrochloride or sulfate, with a metal salt of. the phosphorus sulride-hydrocarbon reaction product. Although guanidine and its salts are preferred, substituted guanidines may be used. Broadly, the guanidine, type basic compounds which may be reacted in, accordance with the present invention may be defined by the formula lawn rem-chum",

in whichR, R, and R"represent hydrogen or" hydrocarbon groups containing 1 to 20 carbon atoms, e. g., straight chain 'alkyl groups, such as methyl, ethyl, propyl, butyl, also higher'straiglitl and branched chain alkyl groups, such as octyl,

isooctyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, cetyl and stearyl' radicals. -R,I R and R" may also represent cycloalkyl, arylalkyl, aryl or alkylaryl groups,.for example, methylcyclohexyl, phenylethyl, phenyl, cresyl, and tert.-butylphenyl groups. It will be understood that R, R. and R can be the same or differentatoms or groups in. the same molecule; However, in the case of a substituted guanidine it is most preferable to employ symmetrically tri-substituted compounds,

and alkyl. and cycloalkyl groups are the more preferred types of substituting groups. These include the symmetrical trialkyl; trinaphthenyl, and triarylalkyl ,guanidines. Also highly preferred classes of substituted guanidines include the monoalkyl, mononaphthenyl, and monoaralkyl guanidines; unsymmetrical dialkyl, dinaphthenyl, and diarylalkyl' guanidines. Somewhat less preierable but still useful classes are the symmetrical dialkyl, dinaphthenyl, and diarylalkyl guanidines, and the mono, di-, and triaryl guanidines. Still other substituted guanidines may be used, such as biguanide, dicyandiamide, and dicyandiamidine.

Specific examples of basic acting compounds illustrating the above-described types are the.

following:

Guanidine e-Methylguanidine e-Ethylguanidine e-Hexylguanidine e-Heptylguanidine e-Phenylethylguanidine a-Benzylguanidine a-cyclohexylguanidine a-Decylguanidine e-fiexadecylguanidine e-octadecylguanidine a-Phenylguanidine e,a.-Dimethylguanidine a,u.-Diethylguanidine a,a-Diisoamylguanidine e,a-Dihexylguanidine a,a-Diheptylguanidine a,a-Diphenylethylguanidine a,a-Dibenzylguanidine a,-Dicyclohcxy1guanidine ,a-Didecylguanidine a,a-Dihexadecylguanidine a,a-Dioctadecylguanidine a,a.-Diphenylguanidine The i -substituted guanidines corresponding to the above-listed a e-substituted compounds. The following symmetrical tri-substituted guanidines:

Trimethylguanidine Triethylguanidine Trioctadecylguanidine Tricyclohexylguanidine Tribenzylguanidine Triphenylguanidine Carbonates of any of the above-listed compounds.

The sulfide of phosphorus which is employed in the reaction with hydrocarbon material may be P283, P285, P483, P48 or other phosphorus sulfide, and is preferably phosphorus pentasulfide, P285.

The hydrocarbon material which may be reacted with a phosphorus sulfide in the first step of the production of additives of the present invention may be paraflins, olefins or olefin polymers, diolefins, acetylenes, aromatics or alkyl aromatics, cyclic aliphatics, petroleum fractions, such as lubricating oil fractions, petrolatums, waxes, cracked cycle stocks, or condensation products of petroleum fractions, solvent extracts of petroleum fractions, etc.

Essentially paraifinic hydrocarbons such as bright stock residuums, lubricating oil distillates, petrolatums or parafiin waxes may be employed. There may also by condensing any of the foregoing hydrocarbons, usually through first halogenating the hydrocarbon, with aromatic hydrocarbons in the presence of anhydrous inorganic halides, such as aluminum chloride, zinc chloride, boron fluoride, and the like.

As examples of monoolefins may be mentioned isobutylene, acrolein, decene, dodecene, cetene (Cm), octadecene (C18), cerotene (C26), melene (C30), olefinic extracts from gasoline or gasoline itself, cracked cycle stocks and polymers thereof, resin oils from crude oil, hydrocarbon coal resins, cracked waxes, dehydrohalogenated chlorinated waxes, and any mixed high molecular weight alkenes obtained by cracking petroleum oils. A preferred class of olefins are those having at least 20 carbon atoms per molecule, of which from about 12 to about 18 carbon atoms, and preferably at least 15 carbon atoms, are in a long chain. Such olefins may be obtained by the dehydrogenation of paraffin waxes, by the dehydrohalogenation of long chain alkyl halides, by the synthesis of hydrocarbons from C and H2, by the dehydration of alcohols, etc.

be employed products obtained Another class of suitable oleflnic materials are the monoolefin polymers, in which the molecular weight ranges from to 50,000, preferably from about 250 to about 10,000. These polymers may be obtained by the polymerization of low molecular weight monoolefinic hydrocarbons, such as ethylene, propylene, butylene, isobutylene, normal and isoamylenes, or hexenes, or by the copolymerization of any combination of the above monoolefinic materials.

Diolefins which may be employed include well known materials such as butadiene, isoprene, chloroprene, cyclopentadiene, 2,3-dimethylbutadiene, pentadiene-l,3, hexadiene-2A, terpenes and the like. Acetylene and substituted acetylenes may similarly be employed.

Another class of unsaturated hydrocarbon materials which may be advantageously employed in the preparation of the additives of this invention are high molecular weight copolymers of low molecular weight monoolefins and diolefins. The copolymer is prepared by controlled copolymerization of a low molecular weight olefin and a non-aromatic hydrocarbon showing the general formula C71H27lr, in which a: is 2 or a multiple of 2, in the presence of a catalyst of the Friedel-Crafts or peroxide type. The low molecular weight olefin is preferably an isoolefln or a tertiary base olefin preferably one having less than 7 carbon atoms per molecule. Ex amples of such olefins are isobutylene, Z-methylbutene-1,2-ethylbutene-l, secondary and tertiary base amylene, hexylenes, and the like. Examples of the non-aromatic hydrocarbons of the above formula which can be used are the conjugated diolefins listed in the preceding paragraph, diolefins such as 1,4-hexadiene, in which the double bond is not conjugated, as well as the acetylenes. The copolymerization is preferably carried out in the presence of aluminum chloride, boron fluoride, or benzoyl peroxide, and the copolymer is preferably one having a molecular weight of about 1,000 to 30,000.

Another class of hydrocarbons which may be employed in a similar manner are aromatic hydrocarbons, such as benzene, naphthalene, anthracene, toluene, xylene, diphenyl, and the like, as well as aromatic hydrocarbons having alkyl substituents and aliphatic hydrocarbons having aryl substituents.

A still further class of hydrocarbons which may be employed in the reaction with sulfides of phosphorus are condensation products of halogenated aliphatic hydrocarbons with an aromatic compound, produced by condensation in the presence of aluminum chloride or other Friedel- Crafts type catalyst. The halogenated aliphatic hydrocarbon is preferably a halogenated long chain parafiin hydrocarbon having more than 8 carbon atoms, such as paraffin wax, petrolatum, ozocerite wax, etc. High viscosity paraffin oils, particularly heavy residual oil which has been treated with chemicals or extracted with propane or other solvents for the removal of asphalts, may be employed. The aromatic constituent may be naphthalene, fiuorene, phenanthrene, anthracene, coal tar residues, and the like.

Another type of hydrocarbon material which may be similarly employed is a resin-like oil which has a molecular weight of from about 1,000 to 2,000 or higher, obtained preferably from a paraffinic oil which has been dewaxed and which is then treated with a liquified normally gaseous hydrocarbon, e. g., propane, to precipitate a heavy propane-insoluble fraction. The

Example 2 A guanidine product in the form of a concentrate was prepared in the manner and from the materials described in Example 1, except that. in the step of neutralization with guanidinecarbonate 88 grams of the concentrate of PzSsoctadecene product was treated with a mixture grams of guanidine carbonate and 1 gram of water.

Example 3 Reactions were carried out as in Example 2, except that amixture of 5 grams of guanidine carbonate and 7 grams of water was used in the neutralization reaction.

Example 4 1200 grams of polyisobutylene of a molecular weight of about 1200 was placed in a three-liter, three-necked round bottom flask and heated to 300 F. 125 grams of phosphorus pentasulfide was added and the temperature raised to 400 F. over a two-hour period, and heating was continued at this temperature for three more hours with stirring. The mixture was blown with nitrogen for another five hours at 400 F. and then filtered. 200 grams of the phosphorus pentasulfide-treated polyisobutylene thus prepared was dissolved in 200 g. of a solvent extracted Mid- Continent distillate oil of 150 seconds (Saybolt) at 100 F. and treated with 25 g. of guanidine carbonate dissolved in 35 g. of water at 130 C. for three hours and filtered.

Example 5 152.5 grams of polyethylene of molecular weight of about 400 was placed in a reaction flask as in Example 4 and heated to 300 F. 30 grams of phosphorus pentasulfide was added and the temperature raised to 400 F. and held at this point for 6% hours, after which the reaction mixture was filtered. The product was diluted with 150 grams of a solvent extracted Mid-Continent distillate oil of 150 seconds (Saybolt) viscosity at 100 F. 200 grams of this solution was treated at 300 F. with 40 grams of guanidine carbonate dissolved in 100 grams of water and the mixture stirred at this temperature for 3 /2 hours and filtered.

Example 6 150 grams of polybutene-l having a. viscosity of 135 seconds (Saybolt) at 210 F. was placed in a reaction flask and 40 grams of phosphorus pentasulfide added at 300 F. This mixture was then heated at 400 F. for 6 hours with stirring and filtered. The product was diluted with 150 grams of the solvent oil employed in Example 5. 278 grams of this solution was treated with grams of guanidine carbonate dissolved in 50 grams of water and the mixture heated at 350 F. for 48/2 hours and filtered.

Example 7 (a) The hydrocarbon material used in this preparation was a lubricating oil bright stock derived from a Panhandle crude and having, before treatment, a viscosity of 150 seconds (Saybolt) at 210 F. This was submitted to propane deasphalting, propane dewaxing, and to phenol, sulfuric acid, and clay treatments. 138 lbs. of this material was placed in an 18 gallon enameled reactor equipped with a strip electric heater and a Lightning twin propeller mixer, and heated to 200-250 F. At this temperature 13.8 lbs. of powdered P285 was added slowly. The reactor was vented to a scrubber to remove the evolved HzS, nitrogen was introduced at the bottom of the reactor, and stirring was maintained at a speed sufliciently rapid to prevent the P285 from settling out. After the P285 had been added, the mixture was heated to 400 F. and stirred at this temperature for '7 hours. The mixture was then filtered through Hy-fio (a filter aid).

(b) The reactor which was used in (a) was thoroughly cleaned and 49 lbs. of the P285- bright stock reaction product (prepared as in (a) was introduced. This was then neutralized with 4.9 lbs. of guanidine carbonate in the form of a mixture with 9.95 lbs. of water. Thi mixture was heated to complete the solution of the salt and was added to the reactor while still hot, the temperature of the Pass-bright stock product being -140 F. The mixture was vigorously stirred and blown with nitrogen, and the evolved ms was vented to a scrubber. The mixture was then heated to 350370 F. over a 4 to 5 hour period to drive off the water. As the temperature was raised, the material became quite viscous until at approximately250 F. the material had a grease-like gel structure. This gel broke after heating at approximately 350 F. for one hour. The heating was continued until a sample of'the material which had been cooled to room temperature was still fiuid. "Ihe final product was filtered through Poly-eel, and contained not more than 0.5% of water.

Example 8 A preparation was carried out as in Example '7, using the same bright stock material, except that '70 lbs. of the bright stock and 7.8 lbs. of P285 were employed in the first step, and in the neutralization step 33 lbs. of Pass-bright stock product and 3.3 lbs of guanidine carbonate dissolved in 6.6 lbs. of water were employed.

Example 9 The guanidine products prepared by the methods of Examples 1 to '7 and 9 were blended in a lubricating oil base consisting of a solvent extracted Coastal naphthenic oil of 60 seconds viscosity (Saybolt) at 210 F. The blends contained 4 weight per cent of the products (or about 2 wt. per cent of active ingredients except in Examples '7 and 9 where the active ingredient content is not known). The blends were submitted to a standard twenty-hour Lauson engine test, which was conducted by operating the Lauson engine at 1800 R. P. M. for 20 hours with a 1.5

indicated.kilowattj'load, 300 F. D11 temperature ;inaperfectly clean surface is givena rating of 0,

while a rating of lo'isygiven to the worst condition which could ,be expected of that surface.

Base :11;. Base ,oil+4%;product.oLExample 1 .Base oil+6% product of Example zonedemerit rating was determined. The results are shown in the following table;

1 I Ring -Lubricant Zone 'Demerit 'Base' oil-F6%-productof Example '7 Base oil+6%product oExamp1e8 Theresults are shown m the following table:

"Cocncentfra- Pi t- "Hydrocarbon 'Gu i ine sill? Oil Composition Reaclt eg with Carbonate Varnish 2 in Aqueous Demerit Solution .Base oil 3.8 'Base oil+4%,product of iOctadecene...- Solid salt 0.8 IExam el. .Base-'oil+4%sproduct' of do 83% 0.4

' Exam e 2. .,Base.oil+4% product of ...do .42% 0.0

:Exam e3. Base oii+4% product of Polyisobutene. 42% 0.8

Example 4. Base oi1+4% product of Polyethylene- 29+ 1.4

"Example 5. Base oil-{4% product of Polybutene-l- 29% 1.4

xampie 6. "Base oil 4. 5 Base oil+4%1.product of .Bright.stock. .33%% 1.0. 25

Example 7. 1 Base'oil+4%"product 'of ;do 33%% 0.25

. .Example 9.

over the useof "solid guanidine carbonate. "Ihe mechanism by'which the use of water gives an improved product is not definitely known. However, it is apparently relatedto the effect of water or steam in causing a decrease'in'the sulfur content below the theoretical value.

Example 11 :A blend containing 4% by-weight of the 50% concentrate of .guanidine product prepared as 'describedin Example ..1z(2% of active ingredi ent) in a solvent extracted paraflinic type 'of mineral lubricating 'oil'of. SAE 30 viscosity grade and a sample of the unblended oil base were emiployedras the crankcase. lubricant in 36 hourstests .witha Chevrolet engine operated at 30 brake horsepower, 3l50..R..P."M. speed, 280 oil .tem-

perature and 200.F. jacket temperature. The piston skirt varnish demerit was determined. The resultstareshown: in the following table Lubricant Varnish ".Demerit Base oi1 .0. 6 .Base oil+4% product of Example 1 .0. 3

Example 12 Blends containing 4% each :of the product of Example 1, and 6% each of the products of Examples 4, '7, and 8,-in a solvent extracted paraffinic type mineral lubricating oil of SAE 30 vis Yes served. The oil must possess'the viscosity and volatility characteristics known tobe required for the servicecontemplated. The oil mu'st'be arate, naphthenate, calcium -cetyl phosphate, barium di-tert-amylphenol sulfide, calcium petroleum sulfonate, zinc me'thylcyolohexyl thiophosphate,

The products-of the'present invention may-be employed'not only in ordinary hydrocarbonlubricating oilsbut also in-the"heavy duty type of lubricating 'oils which have been compounded with such detergent type additives as metalsoaps,

p'hites and thiophosphites, metal salicylates,

metal xanthates and 'thioxan'thates, metal 'thiocarbamates, amines and amine derivatives,:reaction products of metal phenates and sulfur, reaction products of metal-phenates andphosphorus sulfides, metal phenol sulfonates and the"like.

Thus the additives of thepresent invention may be used" in lubricating oils containing such'other addition'agents as'barium tert.-octyl-phenolsulfide, calcium 'tert.-amylphenol sulfide, nickel oleate, barium octadecylate, calcium phen'yl-stezinc --diisopropyl salicylate, aluminum calcium dichlorostearate, etc. Other types of additives such as phenols and phenol sulfides'may be employed.

The lubricatin oil base stocks used in the compositions ofthis invention may be straight mineral lubricating oii'syor distillates derived from paraflinic, naphthenic, asphaltic, or mixed base crudes, or, if desired, various blended oils maybe employed as well as residuals, particularly those from which asphaltic constituents have been carefully-removed. The oils may be refined by 'diethyl ether, nitrobenzene, 'crotonaldehyde, etc.

Hydrogenated oils, white oils, 'or shale oil may be employed aswell as synthetic oils, such as esters andpolyethers as well as those prepared, for example, by the polymerization of olefins'or 'by the reaction of oxidesof carbon with hydrogen or by the hydrogenation of'coal or its products. 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 norm-ally *be that 'oil which "without the new additive present gives the optimum performance in the service contemplated.

However, since one advantage of the additives is that their 'use also makes feasiblethe employment of 'less satisfactory mineral oils or other oils, "no strict rule'can belaid 'down for the choice'of'the' base stock. Certain essentialsmust of course-beoba satisfactory solvent for the additive, although in some cases "auxiliary solvent agents maybe used. The lubricating oils, however they may have been produced, may vary considerably in viscosity and other properties depending upon the particular 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 a Saybolt viscosity at 210 F. of 45 to 90 seconds and a viscosity index of 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, vis-' cosity index.

In addition to the material 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, organometallic compounds, metallic or other soaps, sludge dispersers, anti-oxidants, thickeners, viscosity index improvers, oiliness agents, resins, rubber, olefin polymers, voltolized fats, voltolized mineral oils, and/or voltolized waxes and colloidal solids such as graphite or zinc oxide, etc. Solvents and assisting agents, such as esters, ketones, alcohols, aldehydes, halogenated or nitrated compounds, and the like may also be employed.

Assisting agents which are particularly desirable as plasticizers and defoamers are the higher alcohols having 8 or more carbon atoms and preferably 12 to carbon atoms. The alcohols may be saturated straight and branched chain aliphatic alcohols such as octyl alcohol decyl alcohol (CmHnOI-I), heptadecyl alcohol (Cl'iHasOH) and the like; the corresponding olefinic alcohols such as oleyl alcohol; cyclic alcohols such as naphthenic alcohols; 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 substantial percentage of alcohols having about 16 to 18 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 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. paraflin wax, petrolatum, etc.

In addition to being employed in lubricants the additives of the present invention may also be used in motor fuels, hydraulic fluids, torque converter fluids, cutting oils, flushing oils, turbine oils or transformer oils, industrial oils, process oils and generally as anti-oxidants in mineral oil products. They may also be used in gear lubricants and greases. Since they are owerful surface active agents, they have practical use in dry cleaning fluids, mineral, spirit and aqueous paints, in flotation agents, and as dispersants for insecticides in aqueous and non-aqueous solutions. They are also valuable anti-oxidants for natural and synthetic rubbers.

What is claimed is: v

1. A mineral oil containing a detergent quantity of a product obtained by reacting one molecular proportion of a phosphorus sulfide with 1 to 10 molecular proportions of a hydrocarbon at about 200 to about 600 F. and treating the acidic reaction product at about 100 to about 400 F. with an amount suilicient to neutralize the titratable acidity of such reaction product of an organic basic reaction compound selected from the group consisting of: r (1) free bases of the composition- "in which R, R and R" are each members of the group consisting of hydrogen and hydrocarbon radicals containing 1 to 20 carbon atoms,

and (2) basic reacting salts of the aforementioned free bases, said basic reacting salts being salts of acids whose strength, measured on a pH scale, is less than that of the said acidic reaction product.

2. A composition according to claim 1 in which the mineral oil is a lubricating oil fraction.

3. A composition according to claim 2 in which R, R and R" of the formula each represent the same atom or group.

4. A composition according to claim 2 in which R, R and R, of the formula represent alkyl groups.

5. A composition according to claim 2 in which R, R and R" each represent hydrogen.

6. A composition according to claim 1 in which the compound employed to neutralize the phosphorus sulfide-hydrocarbon reaction product is guanidine carbonate.

7. A composition according to claim 1 in which the acidic reaction product is obtained by reacting phosphorus pentasulfide with a monoolefln.

8. A composition according to claim '7 in which the phosphorus pentasulfide-monoolefin reaction product is neutralized with guanidine carbonate.

9. A composition according to claim 7 in which the monoolefin is polyisobutylene.

10. A composition according to claim 8 in which the guanidine carbonate is contacted with the acidic product in the form of a mixture with water, said mixture containing 30-70% by weight, of guanidine carbonate.

11. A minerallubricating oil containing a detergent quantity of a product obtained by reacting about one molecular proportion of phosphorus pentasulfide with two to five molecular proportions of polyisobutylene at a temperature of about 300 to about 550 F., and neutralizing the product thus obtained with guanidine carbonate.

' containing 30-70% by weight of guanidine carbonate.

13. A composition consisting essentially of a mineral lubricating oil and a product as defined in'claim 1, the amount of said product in the composition being 25 to 50% by weight.

14. A composition consisting essentially of a mineral lubricating oil and a product as defined in claim 8, the amount of said product in the composition being 25 to 50% by weight.

15. A composition according to claim 1 in which the hydrocarbon which is reacted with a phosphorus sulfide is a lubricating oil bright stock.

16. A mineral lubricating oil containing a detergent quantity of a product obtained by reacting about one molecular proportion of phosphorus pentasulfide with one to ten molecular proportions of a lubricating oil bright stock at a temperature of 200 to 600 F., and then treating the acidic reaction product at about 100-400 F. with an amount sufiicient to neutralize the titratable acidity of such reaction product of guanidine carbonate.

17. A mineral lubricating oil containing a detergent quantity of a product obtained by heating a lubricating oil bright stock with onetenth its weight of phosphorus pentasulfide at a temperature of about 400 F. for a period of about seven hours, then neutralizing the resulting reaction product at l20-14.0 F. with an aqueous solution of guanidine carbonate, and heating the final product at about 350-370v F. until the Water content was not greater than about 0.5%.

References Cited in the file of this patent UNITED STATES PATENTS

Claims

1. A MINERAL OIL CONTAINING A DETERGENT QUANTITY OF PRODUCT OBTAINED BY REACTING ONE MOLECULAR PORTION OF A PHOSPHORUS SULFIDE WITH 1 TO 10 MOLECULAR PROPORTIONS OF A HYDROCARBON AT ABOUT 200 TO 600* F. AND TREATING THE ACIDIC REACTION PRODUCT AT ABOUT 100 TO 400 F. WITH AN AMOUNT SUFFICIENT TO NEUTRALIZE THE TITRATABLE ACIDITY OF SUCH REACTION PRODUCT OF AN ORGANIC BASIC REACTION COMPOUND SELECTED FROM THE GROUP CONSISTING OF: (1) FREE BASES OF THE COMPOSITION-