Патент USA US2405608код для вставки
Patented Aug. 13, 1946‘ I ' accuses ‘ I cooonnpn LUBRICANT ' Dilworth'l‘. Rogers, Plain?eld, N. 3., assignor to Standard Oil Development Company,’ a oorpo-l ration o! Delaware ' No Application-ch 31, 1944, ' Serial No. 528,953 '12 Claims. , (c1. 252-3211) ' . . I _ 1 v This invention relates to a method of preventfi - conversion of the resulting product to a salt, as - ing the deterioration of organic materials, and it by reactionwith a metallic base. As pointed out ' Y relates more'particularly to a new type oi addi application Serial Number 457,1“, cheer the tive for improving the properties of mineral lubri~ ' - in functions of the aromatic material is to stabilize ‘ eating oils. _ é the sulfur present in the reaction product of the In co-pending application Serial No. 457,146, filed September 3,1942, the same being a joint application of Carl Winning and the present applicant, there were described additives ‘for lubris ' sulfur halidewith the ‘unsaturated compound. Although all or a greater part oi'the halogen presentlis removed by the second reaction as hin .drosen halide, thearomatic compound does not eating oils which were. prepared by reacting an m act-solely as a dehydrohalogenatingagent, since - unsaturated compound, such as ,diisobutylenaV an appreciable Proportion of the same actually , with a sulfur halide and further reacting the . enters into the ‘reaction and becomes a constitu~ product thus'tormed with an aromatic compound, ent of the reaction product, The resulting mate~ ' e. a. phenol. These products were shown to have , rial is a. mixture of compounds some of which the property of notably reducing‘ the corrosion of. ware believed to possess an aromatic ring strucq copper-lead and similar bearings when blended ture with a side chain containing sulfur in a sta into lubricating oils, and of notably improving engine cleanliness and reducing ring sticking, pigton' skirt varnish formation and the sludging ‘tendencies of oils used in automotive engines. 20 bilizecl form. Although the ‘Structure of the materials obtained in the ‘third step is not de? nitely known, the products do contamwmbine? phosbhoruswhich enhances their desirable Prop - ._ The- products were also found to be useful, as ' _ cities. and it is believed that organo-substituted general anti-oxidants fororganic materials. . ' thio acids of phosphorus are present. Itis not It has'now been found, in accordance with the ' intended that the invention be limited by any present invention, that when products of the type theory as to ‘the exact nature of the chemical described in application Serial Number 457,146 25 reactions that take. place was to any particular are further reactedwith a combination of the ole‘ > chemical structure of the intermediate or ?nal merits. phosphorus and sulfur, either in the form . .- products. ' _ - oia mixture of elemental phosphorus and ele . In the ?rst reaction of the process any sulfur mental sulfur or, more preferably, a phosphorus halide may be reacted with a ‘compound contain sul?de‘, the resulting products have properties to lug one or more unsaturated carbon-to-carbon which are notably superior to those shown to be ' [ linkage, e. g., a 0:6’ group or a CEC~ groupr possessed by the products before reacting with i which forms apart of a non-hcnzenoid organic the phosphorus and sulfur, particularly with re» group. -By- the term “non-benzenoid”'is meant gard to their e?ectiveness as blending agents for any organic group other than a ring structure .,mineral lubricating oils, since they are distinctly 35 having the typical benzene-like linkage found in superior in the property of reducing the corrosion . benzene and its homologs and in condensed struc~ ' of alloy bearings and in promoting engine cleans tures such as those of naphthalene, anthra/cene, liness. These products are described fully and and the like. 'The desired reactive unsaturated claimed in my 'co-pending application of even c1 ' . linkages may be found in'many types of groups lng date. It has further been found that salts ing, such as in ele?ns. in ole?nic side chains of or such products, obtained by reacting the prod aromatic compounds, in cycle-oleflns, in terrenes, nets with a metal, a metallic base or an organic in hetercyclic compcunds,_ etc. Thus, ylene, base, or in any other manner, are equally valu= 1 isobutylene, diisobutylene, triisobutyleue, the co‘ able.'especially as corrosion inhibitors, extreme dimer‘ of isobutylene and normal butene, cracked ‘ ‘ pressure agents and antieoxidants and as agents for promoting engine cleanliness, and in some cases distinctly superior; and these salts, their . preparation and uses form the subject matter of thepresent application. ' I 'The preparation of the new additives of the 4 present invention thus involves Your fundamental steps: (1) the reaction of an unsaturated organic compound with a sulfur halide; (2) a further re action with an aromatic compound: (3) a further gasoline fractions, cracked paramn wax,'medium or ‘high ‘molecular weight polybutene or. other viscous ole?n mlymers, cyclopentene, cyclohcx ene, butadiene, pentadiene, isoprene, styren .3, oleic acid, oleyl alcohol, pine oil; terpcnes and similar unsaturated materials may be ‘used. Oie?ns of less than four carbon atoms are in general not considered particularly suitable for the present invention, although This not intended that their use be excluded. Derivatives of the above de reaction with phosphorus and sulfur; and (4) 55 ‘scribed compoundscontainlng various substitueut _ _ 2,405,608 3 since the substituent groups normally do not in terfere with the principal reaction. The most suitable sulfur halides are sulfur di chloride and monochloride, especially the mono chloride. The ole?nic material and sulfur halide may be reacted in. any desired proportions, but 4 related compounds are phenol itself and its al kylated derivatives, such as the cresols, xylenols, groups and atoms may also be used to advantage, ‘ ' mesitol, butyl phenol, tert.—amyl phenol, di-tert. amyl phenol, tertiary octyl phenol, cetyl phenol, cashew nut shell phenol (cardanol), wax alkyl ated phenols, phenyl phenol, petroleum phenols} , and the like, as well as the naphthols. the more preferred ratio of ole?nic material to > ' Deriva tives of ‘such phenols containing substituents, such as halogen, nitro groups, amino groups, keto sulfur halide is within the range from about 3:1 groups, carboxyl groups, ester groups, aroxy 10 to 1:1 (molal ratio). Higher ratios may often groups, etc, may also be used, as well as the cor be used when a portion of the ole?nic material is responding thiophenols and compounds having to serve as a solvent to be. removed later as un more .than one hydroxyl or mercaptan group at reacted material. The temperatures which have Likewise metal been found most satisfactory for this reaction > , tached to the aromatic nucleus. are from about 20° to about 50° C. (about 70-125° 15 salts of the phenolic compounds may be em ployed. F), but the method may be carried out at con It may be mentioned that the chlorophenols siderably higher or lower temperatures if desired. and chlorinated aromatic hydrocarbons are par Catalysts are not required. ' ticularly valuable in forming compounds useful In the second reaction of the process, in which the reaction product of the sulfur halide with an 20 in extreme pressure lubricants. Another particularly preferred class of aro— ole?n or like material is further reacted with an matic compounds are the arylamines, such as aromatic compound, the ratio of about one part aniline, diphenyl amine, phenylene-diamine, ami by weight of aromatic materialto one-half to nophenols and the like. These are particularly ten parts by weight ofsulfur halide-ole?n reac because of the additional antioxidant prop tionproduct may be used. When the aromatic 25 useful erties of the attached amino groups. material is a phenol, the most preferred ratio is Aromatic compounds containing other substit about one part by weight of the phenol to three uent groups are also contemplated for use in to ten parts by weight of the sulfur halide-ole?n accordance with this invention. These include reaction product. a In reacting phenol itself with the diisobutylene-sulfur monochloride conden sate the most desirable ratio is about one part 30 of phenol to eight to ten parts of the conden sate. The temperature of the reaction may range from aboutfi0° to about 160° C. (about 100-320° F.) , but the most desirable range has been found to be between about 80° and about 140° C. (about 175-285" F.). ' ' ' , . compounds containing aryl, nitro, nitroso, nitrile, thiocyanate, aldehyde, carboxyl and ether groups, as well as groups containing sulfur which par tially ‘or wholly replaces the oxygen of these groups. Included also are compounds in which a'metal is present, as in a metal carboxylate group, an organo~metallic group, a metal alcohol ate group, or the like. ' ' .. Another particularly preferred class of aro matic compounds which may be reacted with the the first or second steps of the process because‘ of the nature of the reactants employed; For ex 40 sulfur halide-ole?nic reaction products to pro duce unusually valuable addition agents are the ample, when diisobutylene is used as the ole?n aromatic sul?des, particularly the phenol sul source, any excess of this which .is present un In general, solvents are not required in either doubtedly acts in a solvent capacity. Where an ole?nic material of higher molecular weight is used or where the reaction mixture is not suffi ciently' fluid the reaction may be aided by the fides in which two groups are combined with one or more sulfur atoms. The phenol sul?des are conveniently prepared by reacting phenols and alkylated phenols with sulfur halides. Such ma terials are known to be useful in' themselves as anti-corrosion agents, and their usefulness is in hydrocarbon or the like. Also, with some types creased by reacting them or their metal salts with of reactants the presence of water, an alcohol 50 the sulfur halide product of the present inven or an ether will be found to'be bene?cial. _ tion to form products containing additional sul The aromatic materials which may be used in fur in stabilized form and further reacting these the process include all types. The aromatic hy products with a phosphorus sul?de. drocarbons, such as benzene, naphthalene, amyl If desired, the products after the reaction with benzene, wax alkylated naphthalene, and the like, the aromatic compound as described above may may be used, although compounds containing be further treated before reacting with a phos substituent groups, such as phenols, aniline, sal phorus sul?de or with phosphorus and sulfur. icylic acid, substituted salicylic acids, alpha For example, those obtained by reaction with naphthol, diphenyl oxide, etc., are more‘ readily phenols or with phenol sul?des may be con reacted. In such substituted compounds, how— verted to metal salts, such as those of tin, bari~ ever, there must always be present in the arc um, calcium, magnesium, zinc, nickel or alumi matic nucleus at' least one replaceable hydrogen num, and the metal derivatives thus formed fur atom. When unsubstituted hydrocarbons, par ther reacted with a phosphorus sul?de. Like ticularly those having no alkyl groups, are sinuse of an organic solvent such as a chlorinated wise, any free phenolic groups prcsent'may be to ester or ether groups. chloride, stannic chloride or the like, is usually 65 converted In the third basic step of the process the prod ployed, a condensing agent, such as aluminum ‘ necessary. In the case of more active compounds no catalyst is needed. ucts of the foregoing reactions are further re acted with the elements'phosphorus and sulfur. This may be accomplished by adding a mixture use‘ in accordance with thepresent invention are the phenols. vThese may be reacted with the 70 of the substances in elementary form to ‘the A preferred group'of aromatic‘compounds for sulfur halide-ole?nic reaction product without the use of a catalyst, and the products of reac tion are particularly useful in improving the properties of lubricating oils. The more desir able and readily obtainable types of phenols and heated reaction products, or by- adding a sul?de of phosphorus, such as P283, PzSs, P4S3, P487, eta, or-the like, or by treating with amixture of sul fur and/or phosphorus and a sul?de of phos phorus. or by treating with any other substance 2,405,808 5 5 or substances containing essentially only the ele ments phosphorus and sulfur, or phosphorus and sulfur in combination with elements-which do base. This may be done by heating the reactants in the presence of a suitable'solvent, such as an alcohol or lubricating oil. It is insome cases possible and desirable to conduct the third and fourth steps of the process simultaneously, e. not interfere with the reaction and which are not harmful to the ?nal product. When ele mentary phosphorus is used it may be either in the white (yellow) or red allotropic form, and sulfur may likewise be used in any of its allotropic forms. by reacting the ole?n~sulfur halide-aromatic condensate with a mixture of a phosphorus sul?de" and‘ a metallic oxide. . The salts which " r. em» ployed in accordance with the present; invention However, it is ordinarily more convenient to 10 include salts of all types, i. e., metal-salts as well as salts of non-metallic bases,v such as ‘onium use a sul?de of phosphorus in carrying out the reaction. The proportions of phosphorus sul?de to the sulfur halide—ole?nearomatic condensate salts of all‘ types, including ammoniun'i, alliyl~ ammonium, quaternary" ammonium, sulionium may vary over a considerable range. In general, and phosphonium salts, as well as amine salts and salts of organic bases generally. The most about 5% to about 25% and preferably about 8% to about 15% of phosphorus sul?de may be used, - preferred metallic salts are the salts of metals based on the weight of the product from the of group II, particularly the salts of caliciun, previous condensation of aromatic material with the sulfur halide-ole?ne product. ' ‘ . barium, magnesium and zinc, also the alkali , metal salts and salts of tin and aluminum.‘ It Although the reaction can be brought about 20 has been found to be somewhat preferable to by fusing the phosphorus and sulfur or phos4 react an amount of metal or base with the phos phorus sul?de with the above described reaction phorus sul?de treated product which is _at least productjit is‘more convenient to carry out. the equivalent to one atom of ‘a monovalent metal reaction with the aid of ‘solvents, particularly petroleum hydrocarbon solvents, or by the use‘ of an excess of the ole?nic reaction product when the entire series of reactions take place‘in for each atom of phosphorus present. ' As noted above, the additives oi the‘ present ‘ invention are particularly useful for reducing corrosiven‘ess of oils toward alloy bearings and. one reaction vessel. Chlorinated or aromatic for improving engine cleanliness as indicated by solvents may also be used. In'the reaction with the reduced quantities of deposits found in ring sul?des of phosphorus, temperatures in the range 30 grooves, on piston skirts and in other parts of of 60° to 200° C. may be employed, but tempera they engine in which lubricants compounded with tures of 90° to 150° C. are preferred. ' the additives are used. . _ , If desired, the reaction with'thesulfideof phos .Another noteworthy advantage of the additives phorus‘ may be conducted in a lubricating oil prepared in accordance with the presentr‘invenv medium. For example, a 50% concentrate of 35 tion is their ability to reduce exhaust valve stick the ole?n-sulfur halide-aromatic condensate may - ing in engine operation. In certainlts’pes of be prepared in lubricating oil as described ‘in service, such as in railway Diesel engines, oils Example 1 of the aforementioned ‘co-pending of otherwise satisfactory characteristics are often application Serial Number 457,146,, and then objectionable because of their tendency to cause treated with the sul?de of phosphorus and ?nally sticking or erratic action of the exhaust valves, ?ltered. _ ’ ‘.19. ‘ Ingen'eral', the preferred method of carrying out the ?rst three basic steps of the presentin vention is first to treat ‘the ole?n or other un saturated material with the sulfur halide, then react with the aromatic material, and ?nally add the phosphorus and sulfur or phosphorus sul?de. However, variations of this procedure may be employed, as by adding the sulfur halide to a mixture of the ole?n and aromatic material, provided the ole?n and aromatic material do not react directly with each other, and then further reacting with the phosphorus sul?de. ‘ It is to be understood that any of the products disclosed in or prepared by the methods den scribed in application Serial Number 451ml’; 1119;.’ be further reacted with a combination of phos phorus and sulfur to form a product which may be converted to a salt additive of the present invention. ' ' ‘ position presur'nabl;r products throughonthethe building hot portions'of up of oil the valve'stems. Additives of the present invention markedly retard this tendency in oils in which they are blended. Since fuel combustion prod~ ucts also come into contact with the valve parts. the additives may likewise be added to the fuels for both Diesel and gasoline engines to prevent or minimize the sticking of valves. Generally, the additives or" the present inven~ tion are most advantageously blended with lubri; eating oil base stocks in concentrations between the approximate limits of 9.02% and 5.0%, and preferably from 0.1% to 2.0%, although larger amounts may be employed. The exact amount to be used depends to a certain extent on the particular compounds used, the character of the mineral oil base and the operating conditions of the engine in which the lubricant is' to he em ' Products which, in the form of their salts, are especially adapted for use in extreme pressure lubricants may be‘ prepared by halogenating the extreme ployed. pressure ‘When thelubricants, additives concentration are to be usedof l to ‘15% are desirable and concentrations of 2 to 10% are preferred. ' phosphorus sul?de reaction products; or, the Concentrates of the additives oil may also halogen may be introduced by using compounds 65, be prepared in, say, 25% to. 75%in concentration containing phosphorus, sulfur andhalogen, e. g., - of additiveand the concentrate later'blended PSC13, PSBrg, PSBrClz, PzS'zBm, and the like, in with other oils‘to give a ?nal blend of lubricating place of or in addition to the phosphorus sul?de oil containing the desired precentage of additive. in the third step of the preparation. _' ' Such concentrates are often desirable, to save The fourth and final basic step of the process, 70 shipping weight and space ' and to vfacilitate i. e., the conversion of the‘ product of the ?rst blending operations. three steps into a salt, is generally accomplished Examples of the'preparation and utilization of simply'by reacting the product with a metal, useful products in ‘accordance iv"?! the method metal oxide, metal hydroxide, or other suitable metal compounds, or with a suitable non-metallic exampleswhich of the ‘present invention follow, but will it be is to desbe--under ed in 2,406,608 } the bearings used in a given test at the end of the various four-hour periods are given in that these example; do not limit the scope of the invention in any way. the table. “’ - I ' Example - 1 I 1233 grams of diisobutylene was placed in a‘ reaction ?ask equipped with a‘ heater, stirrer Table Cumulative bearing weight loss (mg. and re?ux condenser. Then, over a period of three to four-‘hours, 472 grams of S201: was added . with stirring, the reaction temperature being kept at 40°-45° C. After stirring for an addi 10 tional period of approximately an hour 94 grams -' of phenol was added rapidly, the temperature Oil 4 8 12 16 20 24 28 32 86 hrs. hrs. hrs. hrs. hrs. hrs. hrs. hrs. hrs. _ Base BaseoiLoil 1%‘ product ' of Exampei .......... .l_._ ' - raised to 100° 0., and the stirring continued for per25sq.cm.aurtace) . 5' 181 0 0_ 0 0 0 0 0 10 29 an additional period of about two hours. 71 grams ofPzsa was then added over a 15 minute 15 The products of the present invention may period while the temperature was maintained at ‘ be employed not only in ordinary hydrocarbon > 100° 0. Heating was continued with stirring at . lubricating oils but also in the "heavy duty" type 100°-105° C. for an additional period of about two hours. ‘The product was allowed to cool to room temperature 1 and then ?ltered through of lubricating oils which have been compounded so with such detergent type additives as metal soaps, metal petroleum suli'onates, metal phen ates, metal alcoholates, metal phenol sulfonates. metal alkyl phenol sul?des, metal organo phos ‘ one portion was steam distilled at 100° 0., yield phates, thiophosphates, phosphites and thio ing 282 grams of colorless, water-insoluble dis tillate. The distillation residue was separated as phosphites, metal salicylates, metal xanthates Hy-?o, leaving a-very slightresidue. The ?ltrate was divided intovtwo parts (850 cc. each) and and thioxanthates, metal thiccanbamates, reac- . from the water presentand then dried‘ in a stream of nitrogen fornan hour at 105° C. The ?nal product had the following analysis: Percent so - 26.94 0.52 tion products of metal phenates and sulfur, re action products of metal phenates- and phos phorus sul?des, and the like. Thus the new ad ditives of this invention may be used in lubricat ing oils containing such addition agents as To 300 grams of the product prepared as de barium tern-cetyl phenol sul?des, calcium tert amyl phenol sul?de, nickel oleate, barium octa'e decylate, calcium phenyl stearate,‘ zinc diiso scribed above 10 grams of zinc oxide was added and the mixture heated to 80° 0. Then 250 cc.‘ cium cetyl phosphate, barium di-tert.-amyl 0.30 r propyl salicylate, aluminum naphthenate, cal phenol sul?de, calcium petroleum sulfonate, of isopropyl alcohol was added and heating was continued for two hours at 100° C, while a stream of nitrogen was blown through the mixture. The material, which had become free of the alcohol by heating,- was then ?ltered through Hy-?o, giving as a. ?nal product a light-colored, viseo liquid soluble in lubricating oil. ' zinc methyl cyclohexyl thiophosphate, calcium dichlorostearate, etc. - asphaltic 'or mixed base crudes, or, if desired, ~ _ _ Example ' The lubricating 011 base stocks of this inven tion may be straight mineral lubricating oils, or distillates derived from paraf?nlc, naphthenic, 2 - ' various blended oils may be employed as well 45 as residuals, particularly those from which as ‘ ' . ‘ The e?ectiveness ‘of the product prepared as phaltic. constituents have been carefully removed. described in Example 1 in inhibiting the cor , The oils may be re?ned by conventionalnmethods rosion of a typical lubricating oil toward the. surfaces of copper-lead bearings was determined ‘such as aluminum chloride, or they may be ex - by a test which will be‘ described below. The base oil used was a re?ned mineral lubricating: ‘oil of SAE 20 grade. A blank sample of, this oil as well as a sample of the oil. to which 1% of the additive vwas added were submitted to the following corrosion test: ' V ‘500 cc. of the oil were placed in a glass oxi dation tube (13" long and 2%’! diameter) ?tted at the ‘bottom with a 1/4", bore air inlet tube perforated to ‘facilitate air distribution.» The using acid. alkali and/or clay or other agents tracted' oils produced, for‘ example, by solvent vextractionwith solvents of the type of phenol, sulfur dioxide, furfural, dichloro ethyl ether, propane, nitrobenzene, crotonaldehyde,"'etc. Hy drogenated oils or white oils may be employed 65 as well‘ as synthetic oils prepared. for example, by the'polymerization oi oleiins or by the re- _ . action of oxides of carbon with hydrogen or by the hydrogenation of coal or its products. In certain instances cracking coal tarfractions and oxidation tube was then immersed in a heating so coal tar or shale oil 'distillates may also be used. Also, for special'applications, animal, vegetable bath so that the oil temperature was maintained - or-?sh oils or their hydrogenated or voltolized at 325° F. during the test. Two'quarter sec tions of automotive bearings of copper-lead alloy products may beemployed, either alone or in of known weight having a total area of 25 sq. cm. - admixture with mineral oils. For the best results the base stock chosen were attached to opposite sides of a stainless steel 65 should normally be that oil which without the rod which was then immersed in the test oil and rotated at 600 R. P. M., thus providing su?icient agitation of the sample during the test. Air new additives present gives the optimum perform ance in the service contemplated. However, since one‘advantage of the additives is that their use also makes feasible the employment or less satis was then blown through the oil at the rate of 2 cu. ft. per hour. At the end of each four 70 factory mineral oils or other oils, no strict rule hour period the bearing surfaces were repolished. can be laid down for the choice of the base stock. Each time the bearings were removed they were washed with naphtha and weighed to determine the amount of loss by corrosion (prior to re Certain essentials must of course-m observed. The oil must possess the viscosity and volatility polishing). The cumulative weight losses of all 75 characteristics known to be required for the 2,405,608 seryice contemplated. The oil must be a satis factory solvent for the additive, although in some synthetic rubber compounding both as vulcaniza tion assistants and as antioxidants, and generally cases auxiliary solvent agents may be used. ,The ' they may be used many organic materials subject lubricating oils, however they may have been produced, may vary considerably in viscosity and to deterioration by atmospheric oxygen. The present invention is not to be considered as, limited by any of the examples described here, in, which are given by way of illustration only, but'is to be limited solely by the terms, of the appendedv claims. - 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 lubrication ofcertain low and medium speed Diesel engines the general practice has often been to use a lubricating oil > _1. A lubricant comprising a mineral lubricating oil base stock and a small proportion, sufficient to stabilize the said oil against deterioration, of . 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 0 to 50. a metal salt of a reaction product of a combi However, in certain types of Diesel service, particularly with high speed Diesel engines, and iii-gasoline engine service, oils of higher viscosity nation of the elements sulfur and phosphorus with a product'obtainecl by reacting phenol with ’ sulfur chloride derivative of an ole?n. index are often required, for example up to 75 or , _ 2. ,A lubricant comprising a mineral lubricating ‘100, or even higher, viscosity index. oil base stock and a small proportion, sufiicient ' In additionto the materials to be added ac cording to the. present invention, other agents 20. to stabilize the said oil against deterioration, of may also be. used such as dyes, pour depressors, heat thickened fatty oils, sulfurized fatty oils, organo metallic compounds, metallic or other 'l. soaps, sludge dlspersers, antioxidants, thickeners, viscosity index improvers,‘ oiliness agents, de foaming or antifoaming agents, resins, rubber, ole?n polymers, voltolized fats, voltolized mineral a metal salt of a reaction product of a combie _ nation of-the- elements sulfur and. phosphorus with a product obtained by reacting phenol with ' a sulfur monochloride derivative of diisobutylene. 25»' 3. A lubricant comprising a minerallubricating oil base stock and about 0.1% to about‘ 2.0%by weight of a metal salt of a reaction product of ‘a vcombination of the elements sulfur and phos waxes and colloidal solids , _ phorus with a product obtained by reactingabout such as graphite or zinc oxide, 'etc. Solvents and 30 one part by 'weightof phenol with about eight assisting agents, such as esters, k'etones, alcohols, I ' to ten parts by weight of a sulfur monochloride aldehydes, halogenated 0r nitrated compounds, oils, and/or voltolized and the like, may also be employed. derivative of diisobutylene. , , . 4. A lubricant comprising a mineral lubricating ' Assisting agents which are particularly desir~ able are the higher alcohols‘ having eight or more carbon atoms and preferably 12 to 20 carbon atoms. The alcohols may be saturated straight ‘- oil base stock and asmali proportion, sumcient to stabilize the ,said oil against deterioration, of a metal salt of a reaction product of a'phos . phorus sul?dewith a product obtained by react ' ing a phenol with a sulfur chloride derivative of _ and branched chain aliphatic alcoholssuch as octyl alcohol, CsHrzOH, lauryl alcohol, ClilHiibOH, , an ole?n; ‘ cetyl alcohol, CrcHaaOH, stearyl alcohol, some .40 " 5. 'A lubricant comprising a mineral lubricating times referred to as octadecyl alcohol, CmHa'rOI-I, . ~ oil base stock and a small proportion, su?icient and the like; the corresponding ole?nic alcohols ‘to stabilize the said-oil against deterioration, of such as oleyl alcohol; cyclic alcohols, such' a metal saltfof a reaction product of a phos ' as naphthenic , alcohols; and aryl substituted alkyl alcohols, for instance, phenyl octyl 1 45 phorus sul?de with'a product obtained by re acting phenol with a sulfur .monochloride deriv or octadecyl benzyl alcohol or mix ative of diisobutylene. , - alcohol, tures of these various alcohols, which may be pure 'or substantially pure synthetic alcohols. ’ One may also use mixed naturally occurring - .6. A composition according to claim 5 in which ' the metal of the salt is a metal of group II of alcohols such as those found in wool fat (which 50 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 the periodic table. - . - '7.‘ A lubricant comprising a mineral lubricating - oil base stock and about 0.02% to about 5% of . a, product obtained by reacting about 1 to about 3 molecular propo rtions of an ole?n with 1 mo cetyl alcohol); and although it is preferable to lecular proportion isolate the alcohols from those materials, for some 55 acting about -3' to of a sulfur halide, further re about 10 parts by weight of purposes, the wool fat, sperm oil or other natural > the product thus formed with 1 part by weight products rich in alcohols may be used per se. of a phenol, further reacting the product thus' Products prepared synthetically by chemical formed with about 5% to' about 25% of its weight processes. mayalso be used, such as alcohols pre pared by the ‘oxidation of petroleum hydro 60.' of a phosphorus sulfide, and ?nally ‘converting the product thus formed into a metal salt of the carbons, e. g., parafiin wax, petrolatum, etc. same by reaction with a' metal-containing sub vIn addition to being employed in crankcase stance, the amount of metal so reacted being at lubricants and in extreme pressure lubricants, the ' least equivalent, on a valence basis, to 1 atom of . additives or the present invention may also be a monovalent metal‘ for each atom of phosphorus used in spindle oils, textile oils, metal cutting oils, introduced by means of the said phosphorus engine ?ushing oils, turbine oils, insulating and transformer oils,‘ steam cylinder oils, slushing compositions, and greases. Also their use ,in sul?de. - I ' , ’ -8. A lubricant comprising a mineral lubricating ' oil base stock and a small proportion, sumcient motor fuels, Diesel fuels and kerosene is con to stabilize the oil against deterioration, of a templated. Since these additives exhibit anti 70 metal salt of'a reaction product of phosphorus oxidant properties and‘are believed also to possess - pentasul?de with a product obtained by reacting ~‘ability to modify surface activity, they may be a phenol with a sulfur chloride derivative of an employed in asphalts, road oils, waxes, fatty oils ole?n, ‘the metal of the salt being a metal of of animal or vegetable origin, soaps, and plastics, Similarly, they may be used in natural and ‘it group II of the periodic table. 9. A lubricant comprising a mineral lubricating ' 2,405,608 ' oil base stock and a small proportion, sufilcient to stabilize the oil against deterioration, of a metal salt ot-a reaction product of phosphorus pentasul?de with a product obtained by reacting phenol with a sulfur monochloride- derivative of Cl diisobutylene, the metal of the salt being a metal of group H of theperiodic table. 10. A lubricant composition vaccording to claim 12 of a phosphorus sul?de with a product obtained by reacting a phenol with a sulfur halide deriv ative of a compound containing an ole?nic linkage. . e ' 12. An extreme pressure lubricant comprising a mineral lubricating oil base stock and about 2 to about-10% or a metal salt of a reaction product of a phosphorus sul?de with a product obtained by reacting a chlorophenol with a sulfur halide .11. An extreme pressure lubricant comprising 10 derivative of anole?n. a 'mineral lubricating oil base stock and about 2 Dniwort'm 'r.- ROGERS. toabout 10% of a metal salt of a reaction product 9 in which the metal salt is a zinc salt.