US2460025A - Lubricating oil composition - Google Patents

Description

Patented Jan. 25,1949- LUBRIOATING OIL C OMPOSITION John a. McNab, Cranford, and Jeilrey n. nialett, Westfield, N. 1., asig'norl to Standard on Development Company,

aware.

a corporation of Dela- No Application October 24, 1944,

Serial No. 580,191

Claims. (Cl. 252-42.?)

This invention relates to a method of preventing the deterioration of organic materials, and it relates more particularly to a new type of additive for improving the properties of mineral lubricate ins oils.

It is known that the addition of certain types of metal-containing organic compounds to lubricating oils improves various properties thereof, such as their oiliness characteristics and their detergent action in engines, particularly manifasted in the maintenance of a clean engine during operation. Certain of these metal-comtaining compounds have the additional property of inhibiting the corrosion of alloy bearings, such as those of cadmium-silver and copper-lead, now so widely used in automotive engines, and among suchcompounds which have been found to be particularly useful are the metal salts of alkylated phenol sulfides in which the alkyl groups are of the comparatively short chain type. containing from 41:0 8 carbon atoms each. Representative compounds of this type are the alkaline earth metal salts of tert.-amyl phenol sulfide, tert..-

octyl phenol sulfide, and di-tert.-amyl phenol sulfide.

Compounds of the above described type have been found to be somewhat limited in their usefulness perhaps because they have a limited solubility in many types of lubricating oils and have been found to be entirely satisfactory only when used with certain selectedbase stocks, such as a limited number of extracted Mid-Continent oils and certain types of extracted naphthenic stocks. These compounds are also often quite sensitive to water; that is, they are removed to some extent from a solution in oil by intimate contact with a small amount of water. In the case of the diamyl phenol sulfides thereis occasionally some difilculty in converting all of the phenolic groups into the metal derivatives.

Related types of compounds of the class which has been described are the wax-alkylated phenol sulfide salts. These have been disclosed in the art as additives for lubricating oils, but it has been found that these compounds, although containing relatively large side chains, do not show as satisfactory detergent qualities as the shorter chain compounds described above, and they appear to be somewhat unsatisfactory from a solubility standpoint. i

. 2 It has now been found. in accordance with the present invention, that metal salts of phenol sulfides which have highly branched long chain substituent aliphatic groups of 14 carbon atoms or more show unusually good detergent properties in lubricating oils which are used in both high and low temperature engine service. The preferred compounds are the salts of monosulfides disulfldes, polysulfides, and mixed sulfides of alkylated phenols having long branched chain groups. These compounds have also been found to exhibit better oil solubility thanthe shorter chain compounds. Furthermore, they are less liable to separate from an oil solution in the presence of water, and they have been found to be effective in almost any type of reasonably well refined mineral oil. In view of these advantageous properties, the compounds of the present invention are distinctly superior not only to the shorter branched chain alkyl substituted phenol sulfide salts, but likewise superior to the straight chain wax-alkylated phenol sulfide salts. These superior properties will be exhibited in greater detail in specific examples which will be described below.

Defined more exactly, the new additives of the present invention are the compounds of the formula- RAMXM) SAMX) ArR in which Ar represents an aromatic nucleus R. represents at least one branched chain aliph tic hydrocarbon radical containing at least 14 car on atoms, Xrepresents a nonmetallic element of group VI of the periodic table, M represents the hydrogen equivalent of a metal, S is sulfur, and a: is an integer from 1 to 4. The aromatic nucleus may be a single benzene nucleus. a group of linked benzene nuclei as in biphenyl, or a condensed ring system, as in the naphthalene, anthracene and similar nuclei. The hydrocarbon radical B. may be either saturated or unsaturated and preferably contains from 14 to 24 carbon atoms. The metals represented by M may be any of the metals, but those usually preferred are the divalent metals of group II of the periodic table. especially calcium, barium, strontium, magnesium or zinc; and in some cases other metals such as tin, nickel, aluminum, lithium, beryllium, and the like are desirabl r The sulfur may be replaced by selenium or tellurium. It is to be 3 inderstood that the above formula includes com-'- oounds in which hydrogen atoms of the aromatic nuclei are substituted by various atoms or groups, such as halogen atoms, alkyl groups, aryl groups, aralkyl groups or any of the following typical groups: OH, 4H, -OR', -SR', NH:, -SO3M, 'NO2, COH, -CO0R', -COOM,

C4 cut contains n-butane, isobutane, butene-1,

. uses, and converts the n-butene to secondary and the like, where R represents a hydrocarbon cresols, xylenols, phenyl phenol, petroleum phenols, resorcinol, alpha and beta naphthols, and the like.

It should be understood that throughout the specification and in the claims the terms sulfide and disulfide are used in a generic sense and include not only the more or less pure sulfide or iisulfide but. also small amounts of polysulfides 3r mixtures of mono-, di-, or polysulfides as well as polymers of the phenol sulfides. When preparing alkyl phenol sulfides on a. commercial scale,-using technical grades of sulfur chlorides, ratios of 1.5 or so mols of sulfur halide to 2 mols of alkylated phenol will often be found desirable. in such a case, although the product obtained when using sulfur dichloride will be expected to ac essentially an alkyl phenol monosulfide, and when using sulfur monochloride an alkyl phenol disulfide, some quantities of polysulfides and of polymeric materials will also be formed.

As has been stated above, the phenol sulfide salt of the present invention should contain on each nucleus at least one highly branched chain aliphatic hydrocarbon group having at least 14 carbon atoms, the group being either saturated or unsaturated. The invention includes compounds with two or more such substituent'groups on each nucleus, but it is often preferable to have present only one such substltuent group on each nucleus.

To prepare the alkylated phenols to be used in the present invention the most satisfactory alkylating agents are olefin polymers such as those of ethylene, propene, butene, isobutene, amylenes and the like, the molecular weight of the polymers being so chosen as to furnish alkyl groups having preferably an average of 14 or more carbon atoms. Cracked petroleum fractions constitute a very convenient source of olefinic material. Thus, a C: out or C4 cut may be used and suitably treated toefiect the proper degree of polymerization, using such catalysts as clay, AlCls, BFs, H2804, ClSOaH, FSOaH, BF3.H2O, etc. Olefin polymers that occur as by-products in various refinery processes may also be employed, such as the bottoms from polymer gasoline manufacture.

One of the more preferable materials for alkylating the phenols is a butene polymer or copolymer known as naphtha rerun tower bottoms, occurring as a by-product in the manufacture of secondary butyl alcohol from a C4 cut obtained from refinery cracking operations. This chains, e. g., CacC24.

butyl sulfate and secondary butyl hydrogen sulfate which are later hydrolyzed to form sec-butyl alcohol. During this step some of the butene is converted to polymeric material which is recovered as naphtha rerun tower bottoms. This material is not entirely butene polymers, but is undoubtedly a complex product in which not only butene polymers but also copolymers with isobutene, butadiene, dilsobutene, and triisobutene are present.

To prepare the preferred alkyl phenols which are to be converted to the products of the present invention, that portion of the naphtha rerun tower bottoms boiling between about 400 F. and 600 F. is normally employed as alkylating material. This will give phenols having branched alkyl chains with an average of about 15 to 20 carbonatoms. In some cases a wider cut or a lower boiling cut may be employed, e. g., one boiling from 300450 F. to 500-600 F., in which case C1: to Cu alkylated phenols will also be included; Use of a cut having an end point above 600 F. will cause the introduction of longer alkyl It should be pointed out that under the conditions outlined above it appears to be necessary that small quantities of a diolefin be present in the feed stock for the treat ment with sulfuric acid, in order that any appreciable amount of material boiling above 400 F. may be obtained from the naphtha rerun tower bottoms.

Although a preferred source of alkylating materials has been described above, it should be understood that many other materials of a similar muth trichloride, antimony trichloride, stannic chloride, clay, etc. In the case of the more saturated hydrocarbons it is desirable to halogenate the same and then to condense with the phenol in the presence of a Friedel-Crafts catalyst. In some cases it may be desirable to halogenate the olefin polymer itself to facilitate alkylation of the phenol.

when alkylating phenol with the cut from the naphtha rerun tower bottoms described above, and when employing aluminum chloride as the alkylation catalyst, good results have been obtained by using the following procedure: (1) Add the phenol to the butene polymer and saturate the mixture with hydrogen chloride; (2) add the aluminum chloride catalyst to the agitated mixture at 807- F.; (3) react-for about 2 hours at 120 F.; (4) remove the catalyst and unreacted; phenol by water washing; and (5) distill theproduct with the aid of steam to a 400? F. end

point, taking overhead unreacted polymers and lower phenols. Yields with the aluminum chloride catalyst'in such a process are about 55%- 60%, based on the phenol used (amountof catalyst used==4.2% AlCla+7% 1101, based on the amountof olefin in the reaction). Yields of the order of 70% may be obtained if boron trifiuoride is employed as the catalyst (4.2% of catalyst, based on the olefin used). Additional catalyst increases the yields somewhat.

'When employing aluminum chloride catalyst as in the procedure outlined above it may be found preferable in some cases to saturate the olefin polymer with HCl and then add this to an agitated mixture of the aluminum chloride and phenol. Also,instead of removing the alkylation catalyst by water washing, a dry method may be employed involving percolation of the alkylated phenol through clay, or the addition of clay to the crude alkylatedphenol followed b heating and filtering.

Although the yields described above are obtainable when equal molecular proportions of olefin and phenol are reacted, and these proportions are generally preferred, the percentage conversion of the phenol to alkylated phenol canbe increased by using higher olefin/phenol ratios, while the'percentage conversionof olefin can be increased by employing lower olefin/phenol ratios. Further'utilization of the olefinic material can often be efiected by recovering unreacted olefin from the reaction mixture and recycling it with fresh phenol and catalvst. V

In the alkylation of phenols by the use of alkylating agents and catalysts of the types described above temperatures of 50-250 F. may be used, although temperatures within the range of 120-150f F. appear to be the most desirable.

A reaction, time of 2-3 hours is generally adequate.

For converting the alhl phenols to phenol sulfides the conventional processes are used; that is, the alkylated phenols are reacted with sulfur monochloride or dichloride or mixtures of these in a ratio of 2 mols of phenol to 12 mols of sulfur halide in the presence of a suitable solvent such as ethylene dichloride, chloroform, benzene, petroleum naphtha. or the like. To prepare the metal salts, the alkyl phenol sulfides'are preferably dissolved in mineral oil and neutralized witha metal oxide or hydroxide, e. g.,

using a defoaming aid and plasticizer, such 'as stearyl alcohol. The metal salts may also be prepared by other methods such as by double decom position, from the sodium salt of the alkylphenol terioration in the presence of oxygen, as will be explained more fullyhereinafter. The quantity to be used in various materials will vary according to the nature of the material and its tendency to oxidize.

It is often convenient to prepare concentrates of the additives in oil, containing, say, 25 to 75% p of effective addition agent, the concentrate later being added to a suitable'lubrica ina oil base stock to give a finished blend containing the desired percentage of additive. Thus, when using a 40% concentrate, 2.5% of this material may be blended with a suitable base stock to give a finished oil containing 1% of effective additive.

Below are given several examples of the preparation of the alkylated phenol sulfide salts of the present invention and of tests of the usefulness of these salts when blended in lubricating oils.

EXAMPLE 1 400 F., taking overhead about 1635 grams of.

p duct o in in the range 01400-600" F. A mixture of 672 grams of'the butene, polymer thus obtained and 282 grams of phenol'was placed in I o a 2-liter, 3-neck fiask equipped with a stirrer,

dropping funnel and thermometer and immersed in an ice-water bath to provide cooling. Over a period of 1 /2 hours 297 grams of 95%IH2S04 wasadded dropwise to the stirred mixture, the temperature being maintained at -55 F. Stirring was continued for an additional 2% hours, the 7 temperature being allowedto rise to 65 F. forthe first hour and finally to 88 The mixture was then allowed'to stand overnight, after-which it was. again stirred. 712 grams of this product was mixed with 700 cc. of water and placed in a 7 2-liter copper-lined steel bomb where itwas heat,-

ed with shaking for about 3 hours at 100-'-170 C. in order to efi'ect hydrolysis of sulionic. acid groups present in the alkylated product.

mixture was removed from the bomb. the aqueous layer removed and the phenolic layer washed with water, .then with 5% sodium carbonate and again and 5.0%; and preferably from 0.1% to 2.0%, although larger amounts-may be employed.- The ingfconditions of' th'e enginein which the-lubri- V cant is to be employed. The additives are useful not only in lubricating oils but in organic mategrials generally for the'purpo'se of inhibiting de- 26-29 C. After an additional 30 ininutesof stir-7 with water. Final traces by blowing withnitrogen of water'were' removed at 220 F.;"a"nd the product was then distilled with fire and steam to, 350 I F. end point. giving 124 grams of distillate and 300 grams of bottoms. The latter was'filtered through Celite (acid-treated lrieseiguhr), giving 239 grams of finished alkylated phenols. Analysis of the final product sh'owedit to contain alkyl side chains of16 to 20 carbon atoms with-an average length of 19 carbon atoms.

.inalzlsis Carbon Q. '..'per cent 82.94 Hydrogen ..do' 13.36 Acetyl value mg. KOI-I/g. acetylated produ'cts.. 138.5

Exmts2 (a) A solution of grams of the alkylated phenol of Example 1 in 234 grams of chloroform was placed in a reactlonfiask equipped with stir rer andrefiux condenser. Over'a 35 minute'period' 24.3 grams SCI-z was addeddropwise tothe mixture, the temperature being maintained at ring the mixture was heated at refiux' temperature for 2 hours. The chloroform was then removed by evaporation at a maximum temperature contained 12.95% sulfur and was soluble in mineral lubricating 011.

The alkyl phenol sulfides were converted to metal salts in the following manner: 76 grams of the alkyl phenol sulfide from (a), 80 grams of the disulfide from (b), and 42 grams of commercial stearyl alcohol were dissolved in 210 grams of refined mineral lubricating oil of 52 seconds viscosity (Saybolt-210 F.) with-heating and stirring. While the temperature was held at.

105 0., there was added gradually over a 1 hour period 83 grams of Ba(OH) 2.81120, nitrogen being 1 blown through the mixture at the same time to facilitate water removal. After all of the barium hydroxide had been added the temperature was raised to 130-140 C. for 15 minutes, stirring and nitrogen blowing being continued. The mixture was then filtered with the aid of celite. The filtered product, obtained in a 403 gram yield, was essentially a 40% concentrate of barium salts of the mixed monosulfide and disulfides of c16- C20 branched chain alkyl phenols, the other components of the concentrate being 50% mineral oil and 10% stearyl alcohol. Analysis'of the concentrate showed it to contain 3.64% sulfur and 6.12% barium.

EXAMPLE 3 The alkylating material used in this example was similar to that employed in Example 1, namely butene polymers of 400-600 F. boiling range obtained from naphtha rerun tower bottoms. This material was used to alkylate phenol the yield of alkylated phenol. The amounts used,

in each batch are shown in the following table:

Gram

Grams Grams Batch Butene Polymer Phenol A101:

In batches a, b and e, 240 parts of butene polymer were employed for each 100 parts of phenol. In batches c and d the proportion was 400 parts of polymer for 100 parts of phenol. The procedure employed in each case was essentially as follows:

The phenol and the butene polymer were added to a reaction flask and the mixture was saturated with dry HCl, the temperature being maintained at about 85-100 F. The A1Cl3 catalyst was added gradually over a period of 1 to 2 hours, the mixture being stirred and kept at an average temperature of 90 F. (85 F. minimum, 98 F. maximum). A total reaction time of 18 hours was employed for batches a and b, 6 hours for batch c, 45 hours for batch d, and 25 hours for batch e, v

To stop the reaction, 200-300 cc. of isopropyl alcohol was added to the reaction mixture, followed by 350-400 cc. of water. The mixture was then washed four times with water and finally distilled with fire and steam to 400 F. end point. The desired alkylated phenol was obtained as the bottoms from this distillation. The products of the five batches were mixed together to obtain a supply of alkylated phenols for subsequent con- 10 version to phenol sulfides.

Analysis of the composite mixture Carbon per cent- 83.53 Hydrogen do 12.02 Acetyl No mg. KOH/gram acetylated product 140.6

Emu-i (a) A solution of 1100 grams of the mixed alkylated phenols of Example 3 in 2570 grams of chloroform was placed in a reaction flask. Then,

' while the temperature was maintained at -32 C., 350 grams of sulfur monochloride (Sack) was slowly added with stirring over a period of 1% hours. After an additional half hour of stirring the mixture was heated under reflux for three hours. The chloroform was then stripped off, leaving as a residue the desired alkylated phenol disulfide, containing 13.44% sulfur.

(b) Employing the same procedure as in (a). the corresponding alkylated phenol monosulfide was prepared by reaction of 268 grams of sulfur dichloride (SClz) with 1100 grams of alkylated phenols from Example 3, dissolved in. 2570 grams of chloroform. The product obtained after evaporation of the solvent contained 6.46% sulfur.

(c) 800 grams of the alkylated phenol disulfide of (a), 760 grams of the alkylated phenol monosulfide of (b), and 252 grams of commercial stearyl alcohol were dissolved in 2268 grams of a refined mineral lubricating oil of 52 seconds Saybolt viscosity (210 F.). Over a 3 hour period 900 grams of barium hydroxide octahydrate (Ba(OI-I)z.8H2O) was added gradually, the mixture being stirred and its temperature maintained in the range 110-130 C. During this period a stream of nitrogen was blown through the reaction mixture to facilitate removal of water. Following the barium hydroxide addition the temperature was raised to 140 C. for 15 minutes and the product then was filtered, using celite as a filter aid. There was obtained 4070 grams of filtered product, this being an additive concentrate containing 54% mineral oil, 6% stearyl alcohol and 40% barium salt of C1o-C2o branched chain alkylated phenol monosulflde-disulfide. This concentrate was found to contain 7.2% barium and 3.6% sulfur.

EXAMPLE 5 (a) Employing essentially the procedure outlined in Example 3, a large batch of alkylated phenol was prepared in a glass lined reactor, starting with 24.6 kilograms of butene polymers, 10.4 kilograms of phenol, and 1 kilogram of A1011. The butene polymer-phenol mixture was saturated with HCl and the AlCh was added over a 3 hour period, a reaction temperature of 115"- 120" F. being employed. After a total of 6 hours reaction time, 2 gallons of 99% isoprop l alcohol was added followed by 5 gallons of water to remove the catalyst. The alkylated phenols were then washed with water and distilled as in Example 3. A composite of this batch of alkylated 75 phenols and of a similar batch prepared from the same quantities of reactants and catalyst but 'v'erte'd to alkyl phenol monosuliides I with 729 'gramspfsulfur dichloride. -'fisiniilarly,

had the following analysis:

Carbon per cent" 83.17 Hydrogen do 12.06 .Acetyl N o mg. KOH/gram acetylated product- 135.0

(b) Portions of the abovealkylated phenol.

composite were separately converted to monosulfides and disulfides by the-procedures outlined in Examples 4 (a) and 4 (b). ,Then.-2.7 kilograms of the monos'uliide, 2&9 kilograms of the disulfide, and 0.9 kilogram oi commer-. cial stearyl alcohol were dissolved in 8.1 kilograms of refined B. A. E. 20 grade mineral lubrieating oil at 100 C. The temperature was raised to 135 0.; then over a 3-hour eriod 3 kilograms of Ba(H)s.8I-lz0 was added gradually with stirring, the temperature being maintained at 135- 150 C. and nitrogen being blown through the mixture to facilitate the removal of water. Heat-- ing was continued at 150 C. for minutes after the barium hydroxide had been added. Themix-" ture was then filtered with -the use of celite filter aid, yielding.l2.8 kilograms of anoil concentrate or the desired additive material, barium salts of Cid-C branched chain allt'ylfphenol sulfide-disulfides. Theconcentrate -umand3.9% sulfur;- 7 g EJXAMPL-E6-." ,Branched chainCn-Czo alkyl. phenol was prepared in the following-manner, using boron fluoride catalyst. 1340 grams of- BFzi was injected into 13.2 kilograms of phenolwhich was placed in a glass lined reactor. During a two-hour period 31.4 kilograms of butene polymers of 400-600"- F. 1 boiling range (obtained from naphtha rerun tower bottoms as in previous examples) was add! ed. After the first 15 minutes the temperature. had risen from F. to F. Thetemperature;

was "allowed 'to rise to F. and held at this point during the addition of the remaining butene polymer. It was thenallowed to rise to period, the total' 're for an additional 4 hour action time being 6 hours.

The reac'tionmixture was then washed 5 times with hot water (170-185 F). 12 liters of water being used each time. The-crude productwasthen steam distilled up to 400 F. bottoms tom-- Iperature, the desired alkylated -phenols.being obtainedin 30.7 kilogram yield as the bottomsirom this distillation. 'Analysis of the distillate and of the water from the above washing'st'enindb, .cated that 77% olthe phenol and 76 %fot'the ,butene polymer had reacted.

. Employing the procedure described'in Example t 2, 3 kilograms of the above alkylated phenol fzwa's s l d-i '7 k l gr ms of chloroform, and con}.

another .-3 kilogram portion ofitheialliylated I phenolsfwas converted to fi kyllphenoljdisulfides by reaction, with 954grams, of,- SiGlai -760I :grains' offtheall'gvl phenol monosulflde; 780 grains of the fdisulflde and 270 grams in commercial stearylf alcohol were" dissolved in 2430 grains of refined S: 4. 20 grade mineral; lubricating oil heated to C. Over. aperipd r, amur's'sszjerams-pt 30 minutes at C; andthe productrwa's then filtered,- givingan: oil concentrate oi thedesired additive, salts of Cla -Cat alkylated-phenol contained 6.9% bariby reaction EXAMPLE 7 The effectiveness of the products prepared as described in the foregoing examples in inhibiting the corrosion of atypical lubricating oil toward the surfaces of copper-lead bearings was determined by a test which will be described below.

10 The base oil used was a well refined solvent extractbd'barafllnic lubrlcating'bil of S. A. E. 20

. grade. A blank sample of this oil and samples 01. the oil containing small quantities of the various additives, were submitted to the following 15 "corrosion te'sti 500 cc. of the oil was placed in a glass oxida tion-"tube (13" long and 2%" diameter) fitted at the bottom with a $4 bore air inlet tube perforatedfito" facilitate air distribution. 'The 1 oxidation tube was then immersed in a heating bath so that the oiltemperature was maintained at325 F. during; the test. Two quarter sections of automotive bearings of copper-lead alloy of known weight having a total area of 25 sq. cm. 25 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 efiicient agitation of the sample during the test. Air was then blown through the oil at the rate of 2 cu. ft.

30 per hour. At the end or each four-hour period the-bearings were removed, washed with naphtha. weighed to determine the amount of loss by corrosion. They were. then repolished (to in- The cumulative weightlosses of all the bearings 'used' in a given testat the endoi-the various iour hour periods are given in the following table. Theadditiv'eis des'ignated by the number 10: the example in the-present specification in which the additive is. described. It will readily be noted that the'additives of the present in- In theffollowing 'engine performance tests. .{samplesoiunblendedbase oil and of.- blends con-- .taining .tmsoi 1- with various alkylated phenol s Caterpillar Dieseiengine, each run being made for fiqihours' at8 50 R. P. M.,'.wltli 18.7 brake horse power-output;andzoil temperature of 200 E, and atmospheric tem rature of 140 F. At the, end

their/condition. An overall demerit rating was thenj calQ lht'edg the, individual demerit ;ratin'gs "beingweighted"according to the relative imi portance of theyar'ious engin'e parts. It should 1 ;be :notedftha't' thelower the demerit rating the "better the} engine condition, and hence the better the, oil iperiormed in lthe'engine. The results of crease theseverity oi the test), reweighed, and r :5 placed in the oil foranother four-hour period.

'yvention are-jvery eflective inhibitors of bearing ulfide a1ts were tested; in. a :single cylinder f -each tes .d vidual parts of the engine were inspectedz'andygiven demerit ratings based on 2,4eo,oae I 11 12 these engine tests are shown in the following The products or the present invention may table: 1, e be employed not only as the sole additives in Engine Demerlts on i htihl Ozvucrlizlgng 3??? Rings Rings Base Oil A 1.24 1.69 1.00 8.50 11.50 Base Oil A+l'7 Barium Wax Phenol Suliide-Disulflde +0.25% Stearyl Alcohol 1.48 1,32 1,12 14,00 ,0o Base Oil A+1 Barium tert.-Octyl Phenol Su1flde-Disulflde+0.26 a Stearyl AlcohoL 0.83 0. 79 0. 12 6.00 2. 50 Base Oil B+i Barium tert.-0ctyl Phenol Sulflde-Disulfide+0.25 Stearyl Alcohol 0.99 1. 14 0,33 ,51 3 50 Base Oil B+1 0 Barium CN'CM Branched Chain Alkyl Phenol Suiilde-Disuliidc (2.5% Concantrate of Example 2c)+0.25% Stcaryl Alcohol 0. 73

Base Oil A-Conventionally refined coastal oil of 55 seconds Baybolt Viscosity (210 F.). Balsa OiLB-gieflned aolaventkexltrgcted lparaiflniiehoghifi g-rade. Ph

ax p eno repare y a y a ng p eno w or on are n wax. enol suliid pared manner as [or add tives of the present invention. p eldlsumdo in month"? the It will be seen that the Cm-Czo branched chain 20 hydrocarbon lubricating oils but also in conjuncalkyl phenol sulfide salt was more satisfactory tion with other detergent type additives such than the Co alkyl phenol sulfide salt. By comas metal soaps, metal petroleum sulionates, metal parison, a Cit-C20 straight chain alkyl phenol phenates, metal alcoholates,, metal phenol 1- sulfide salt (wax phenol) was not satisfactory, fonates, other metal alkyl phenol sulfides, metal the blend being even worse than the base oil. organo phosphates, thiophosphates, phosphites Exm 9 and thiophosphites, metal salicylates, metal Another similar series of engine performance xanthates and thioxanthates, metal thiocarbamtests was carried out in a single cylinder caterates. reaction Products f metal phenates or m Diesel engine, each mm being made for metal phenol sulfides and sulfur, reaction prod- 126 hours at 1,000 R. P. M., with 19.8 brak nets of metal phenates or metal phenol sulfides horse power output, an oil temperature oi! 150 F,, and ph sp orus fides. a d the l e" 8., and jacket temperature of 180 F. the new additives of this invention may be used The results of the tests are shown in the followin lubricatin oils containing such' addition ing table, in which the data have the same meanagents as nickel oleate, barium octadecylate,

ing as in the preceding example. calcium phenyl stearate, zinc diisopropyi sali- Engine Demerits R Grooves and Oil ms Sides Over Ring Skirt all Zone Varnish #1 and 2 #4 and 6 Rings Rings Base Oil +1 Barium tert.-Octyl Phenol Bulflde-Disuliide +0.25% Ricaryl Alcohol I 0.83 0.78 0 6.60 4. 50 Base Oil+1 a Barium salts oi Kero phenol I Suliide-Disuliide+0.25% Stearyl Alcohol 1. ll 1. 41 0.31 9. 00 9. 50 Base Oil+l% Barium Cit-C20 Branched Chain Alkyl Phenol Sulflde-Disulflde-l-0.25%

Stearyl Alcohol (2.5% Concentrate of Example 0. 70 0 3, 75 2, Base Oii+1% Barium 016-020 Branched Chain Alkyl Phenol sulflde-Disuliide-i-o.25%

Stearyl Alcohol (2.5% Concentrate of Example 512) 0. 71 0 3. 50

1 Base Oil-S. A. E. 30 grade extracted Mid-Continent lubricating oil. I i 'Iert.-octyi phenol prepared by alkylating p l ieuol with diisobutyleno. Barium salts oi the phcnolmliide disulilde prepared in essentially l the same manner as for additives oi the present vention.

I Kero phenols prepared by alkylation of henol with chlorinated kerosene. Phenol suliide-disulilde salts prepared in essentially the same manner as for additives oi the present invent on.

Exmrm 10 cy'late, aluminum napthenate, calcium cetyl Another series of engine performance tests phosfphatei barium dl'tert-'amyl P sulfide was carried out under .the conditions described calcmm Petroleum simulate zinc methyl cyclo- Example 9 except that a murqqng piston hexyl thiophosphate, calcuim dichlorostearate,

was used in each case instead of a six -ring piston.

The results from these tests are shown in lubricating base stocks sedm the the following table, the data having the same compositions of this invention may be straight significance as in the preceding examples. mineral lubricating oils, or distillates derived from paraflinic, naphthenic, asphaltic or mixed Engine Demmts base crudes, or, if desired, various blended oils may be employed as well as residuals, particularly over Ring skin .65 those from which asphaltic constituents have all Zone Varnish been carefully removed. The oils may be refined byconventional methods using acid, alkali and/ Base o 1 2.24 2,32 0.21 or clay or other agents such as aluminum 2 5 ggggz ggg'ge gggg gtgeg chloride, or they may be extracted oils produced, B ale l 1.36 L1 0 for example, by solvent extraction with solvents J1 Chain Alkyl Phencil slants-1 3i: the type of Phenm, sulfur dioxide mrmmlsum -Y Alcohol 0 dichloro ethyl ether, nitrobenzene, crotonaldehyde, etc. Hydrogenated oils or white oils Reiined solvent extracted paraflinic oil oi'S.A.E.30grade. The may b em loyed a well a synthetic 0115 prebase oil employed in the blends was the same type of oil madein the same way from the samecrudesource but was; 91$,A, 15,20grade. 75 p for p by the P y ion f l the service contemplated.

oleiinsor, by the reaction of oxides of carbon with drogen 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 other natural products-rich in alcohols may be their hydrogenated or voltolized products may be employed, either alone or in admixture with mineral oils.

For the best results the base stock chosen should normally be that oil which without the new additives present gives the optimum performance in However, since one advantage of the additives is that theiriuse 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 essentials must of course be observed.

The 011 must possess the viscosity and volatility characteristics known to be required for the service contemplated. The oil must be asatisfactory solvent for the additive, although in some cases auxiliary solvent agents may be used. Thelubricating 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 lubrication 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 50.4

However, in certain types of Diesel service, particularly with high speed Diesel engines, and in gasoline engine service, oils of higher viscosity index are often required, for example up to 75 or 100, or even higher, viscosity index.

In addition to the materials to be added accord-'- ingto the. present invention, other agents mat also be used such as dyes, pour depressors, heat thickened fatty oils, sulfurized fatty oils, organo-= metallic compounds, metallic or other soaps, sludge disperser's, antioxidants, thickeners, 'vis= cosity index improvers, oiliness agents, defoaming- -or antifoaming 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 beemployed.

- ,Assisting agentswhich are particularly desirable are the higher alcohols having eight .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 (CaI-InOI-I), lauryl alcohol (CmHatOI-D, cetyl' alcohol (C1aHaaOI-I), stearylfor some purposes, the. wool fat, sperm oil 'or used per se. Products prepared synthetically by chemical processes may also be used, such as alcohols prepared byv the oxidation of petroleum hydrocarbons, e. g., paraflin wax, petrolatum, etc. '-In addition to being employed in crankcase lubricants andin extreme pressure lubricants, the

- additives of the present invention may also be used in various industrialand process oilssuch as spindle oils, textile oils, metal cutting oils,

. engine flushing oils, turbine oils, insulatng and transformer oils, steaincylinder oils; slushing compositions, and greases, Also their use in motor fuels, Diesel fuels'andkerosene is contemplated. Since these additives exhibit antioxidant properties and are believed also to possess ability to modify surface activity, they may be employed in asphalts, road oils, waxes, fatty oils of'animal or vegetable origin, soaps, and plastics. naturaland synthetic rubber compounding both as vulcanization assistants and as antioxidants, and generally they may be used in any organic materials subjectto deterioration by atmospheric oxygen.

The present inventionis not to be considered as- .lim'ited'by any of the examples "described herein, which are givenby way of illustration only, but

is to be limited "solely pended'claims'.

We claim: .,A hydrocarbon -by the terms of the aprnaterial susceptible to deterior'ation 3 by. oxidation containing dissolved therein a small quantity, sufiicient to'stabilize said material against such oxidation, of a compound of the formula RAflXM) S=(MX) ArR in which Ar is an aromatic hydrocarbon nucleus, R is a branched chain aliphatic hydrocarbon radical containing 14 to 24 carbon atoms, X is a nor'nnetallic element of group VI of the periodic stabilize said oil against deterioration byoxidain which Ar is an aromatichydrocarbon nucleus, R is a branched chain aliphatic hydrocarbons.-

nonmetallic element of group'VI of the periodic. I

alcohol, sometimes referred ..to as octadecylaryl substituted alkylalcohols, for; instance, phenyl octyl alcohol, or. octadecyl benzyl alcohol alcohol, CiaI-IawOH ),'and the'like; the corre-n sponding oleflnlc alcohols, such as oleyl alcohol? cyclic alcohols, such as napthenio alcohols; and .65

or mixtures of thesevar'ious 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 knowny-to contain a substantial-percentage of alcohols having about 16 to181'carb0n atoms.) I and in sperm-Oil (which contains a high percentage oi'cetylalcoholly and although it 'preier-' able to'isoiatethe alcohols from'those materials,

table, M is the hydrogen equivalent of a metal, S is. sulfur, and 0:; is aninteger from 1 to i.

2. A mineral lubricating oil containing dissolved therein a small quantity, sumcient to tion, of acompound oi the formula RAr(Xl\/I)S=(MX)ArR radical containing 14 to 24 carbon atoms, X is a table, M is the hydrogen-eqnivalentof a metal, S is'sulfur, and a: lean integer from 1 to. 4.

atoms. Z 5.*A composition '6. A. mineral lubricating'oil additive conceny. trate containing 25-75%] ofa'metal salt bran alkylated phenol 'sulfideinwhich atxlea'st' one] branched chain. alkyl group. contain-inglito 24' f "carbon atoms is attached .'to;'=each-" benzene J nucleua'l I v J Similarly, they may be used in according t m n h the-metal of the metal salt is a divalent metal 1o q ctable.

7. A mineral lubricating oil additive concentrate containing about-10% of barium salts oi alkylated phenol sulfides in which at least one branched chain containing 16 to 20 carbon atoms is attached to each benzene nucleus, about 10% 01' stearyl alcohol, and about 50% 0! mineral lubricating oil.

8. As a new composition of matter a compound of the formula 16 10. A composition according to claim 9 in which the metal oi the metal salt is a divalent metal of group II oi the periodic table.

JOHN G. MCNAB. JEFFREY H. BAR'I'LE'IT.

REFERENCES crr n The following references are of record in the file of this patent UNITED STATES PATENFS Number Name Date 2,263,445 Reii! Nov. 18, 1941 2,342,887 Nelson Feb. 29, 1944 2,346,826 Cook et a]. Apr. 18, 1944 2,360,302 Etzler et a1. Oct. 10, 1944 2,361,804 Wilson M.-. Oct. 31, 1944 2,362,290 Miller Nov. '7, 1944 2,362,291 Winning Nov. 7, 1944 2,366,874

Relil' Jan. :9, 1945 Certificate of Correction PatentNo. 2,460,025 January 25, 1949 JOHN G. McNAB ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 14, lines 64 and 67, for the claim reference numeral 4 read 3;

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 7th day of March, A. D. 1950.

THOMAS F. MURPHY,

Assistant Gommz'ssz'oner of Patents.

M Certificate of Correction PatentNo. 2,460,025 January 25, 1949 JOHN G. McNAB ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 14, lines 64 and 67, for the claim reference numeral 4 read 3;

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 7th day of March, A. D. 1950.

THOMAS F. MURPHY,

Assistant Commissioner of Patents.