US2340036A

US2340036A - Lubricant composition

Info

Publication number: US2340036A
Application number: US424927A
Authority: US
Inventors: John C Zimmer; George M Mcnulty
Original assignee: Standard Oil Development Co
Current assignee: Standard Oil Development Co
Priority date: 1941-12-30
Filing date: 1941-12-30
Publication date: 1944-01-25
Anticipated expiration: 1961-01-25
Also published as: GB581243A

Description

Patented Jan. 25 1944 V flrzimmerand George M. McNulty, llnionr '1 1 N. J.,,;assignors to standard fl l Development s mnmmcmmt of e w r I we Drawing. nimationDecember-30,1941, E I f 1 S erlalNo.424,92 7- 1 I This invention relates tof me ges f ubiiems such as lubricating'oil andgreasecomposltiop intended for the lubrication of moving', metal parts which come into contact athigh' pressures, It relates especially to the preparationof improved lubricant compositions of higl'iffilm strength for bearing and engine lubrication ,'fto the prepa ration of improved extreme pressure lubricants for use especially for hypoid gears, and to 'the preparation of improved cutting oils for use in machining metals.

In the lubrication .ofhypoid and other gears, various materials containing chlorine or other halogens are used aloneon in combination with other metals efiective in increasing the extreme pressure lubricant characteristicsof the composi,

tion, such as sulfur or" phosphorus compounds. These compositions have a'serious disadvantage; however, in that they tend to rust the metal surfaces which are beinglubricated, me -jai of ause; corrosion and staining "ferrous-and copperbearing alloys used in bearings; bushings, pistons, etc; Also, the use in cuttingfluids of-sulfur or sulfur compounds, aloneorfinthepresence of chlorine compounds, usually'-'causes ablaclrstain' of copper sulfide oncopperalloys. i 7

of the present invention,'-.that this undesirable corrosion and staining of metals can be prevented by adding to the high film strength or extreme pressure lubricant a small proportion of an oilsoluble salt, preferably a metallic, ammonium or other onium base salt, of an auto-condensation product of a hydroxyarylalkyl amine.

A preferred type of condensation product for use in making thesalts-of this invention is pre-- pared as an ammonium derivative of an alkyl phenol-formaldehyde-hydrogen halide condensation product. These compounds are obtained with satisfactory oil solubility and effectiveness for the purposeof. this invention-my:condensing an alkyl phenol with formaldehyde in the presence of a hydrogen halide, thenireacting the resulting phenolic condensationproduct with ammonia or other strong base, e. g., an amino compound or other organic nitrogen base. Ammonia is the preferred base reactant;- Next in order come the aliphatic and aromatic amines, es-

1}, -{14 c1. 252f- 1), V I

tion" and use *ofthese agents is that their oilsolubility increases with the length of the substituent'in the phenol nucleus.

Even though the initial phenolic compound may containa' long alkyl'or aliphatic substituent group, whichin ordinary-types of reaction lowers the reactivity of the phenolic compounds, the reaction for preparing thedesired hydroxyarylalkyl amine goes with great ease. The complete reaction may be considered'as involving two stages: first, the introduction of a halogenated aliphatic radical'in the phenolic compound; and second, a splittingout of the halogen by condensation of alkyl the substituted phenolic compound with the base.

Very little halogen, andpre'ferably none, is left in the final product; The preparation of a typical product is illustrated by the following:

900 grams ofparaformaldehyde '(30 mols of formaldehyde) and 5,000 grams of concentrated hydrochloric acid' were placed in a 12-liter flask provided with a stirrer, a reflux condenser and a thermometen. ''A- solution of 2,060 grams mols) 0t: paraisooctylphe'nol (para-tetramethyl It has now been found, and is a primary object butylphenol) in :an equalweight of benzene was then added to. the'flask over. a period of to minutes, ,whilepassing hydrochloric acid gas continuously through the. solution throughout the reaction in order to keep the reaction mixture saturated/The stirrerwas'also operated continuouslytoprovide emcient contact between the two. liquidphases presentduring the reaction. The temperature of. the initial mixture of paraformaldehyde and-hydrochloric acid was 15 C. It increased to -50? Q. upon addition of the phenol and this temperature was thereafter maintained for 11/; hours whil constantly stirring and passing in hydrochloric acidgas. At the end of pecially the primaryandsecondary amines. .The

. solubility and effectiveness are readily increased by subjecting the hydroxy. compounds to autocondensation conditions during their preparation, or'the simple reaction products may be prepared an t e ea t r s bi d u o-sandmantiontreatmenti y w Another very important faotor in the preparal this time thfe'stirring was stopped, whereupon an upper. phenolic benzene. layer separated from a lower fuming hydrochloric acid layer and was separately withdrawn from'the reaction vessel. The upper layerwas'washed severaltimes with water. Analysis of a small sample of the oil from which the be'nz'ol wasremoved showed it to contain 14.2% chlorine. 1 a v To 600 grams ofthis benzene solution there were slowly added (with thorough stirring) 50 grams of anhydrous'am'monia dissolved in 300 grams of 98% isor'iropyl alcohol. This reaction takes place with great evolution of heat and, on a larger scale, c'ool'ing'f'or pressure is necessary to prevent loss of solvent and ammonia. After complete addition of the ammonia, the mixture consisted off athick, tack y,1ye1low' slurry contaimngan excess (about l -0f%)"of ammonia. This mixture'wasthen placed inas'tainless steel bomb ofon'e liter capacity which was sealed and then heated for 20 hours at aut emp'erature of to C. It is possible .to'pass in gaseous ammonia at such a rate as to control the temperature,

. rather than use the ammonia in alcoholic solutained as a material completely soluble in the benzene-alcohol solvent present which also contained a fine suspension of insoluble ammonium chloride. This mixture was washed with water several times to remove the suspended salt and the alcohol. 500 grams of a refined paramnic lubricating oil having a viscosity Saybolt at 210 F. of 43 seconds were added and the mixture was blown with nitrogen at 120 to 130 Cffor' two hours to remove the benzene. After this, more oil was added to provide a concentrate of relatively low viscosity and clear red color containing 25% of the reaction product.

A small portion of the benzene solution was withdrawn for analysis prior to addition or the lubricating oil. Evaporation of the benzene produced a brittle, resinous material containin 2.8% nitrogen.

The heating of the ammonia condensation product is effective in obtaining a completely oilsoluble final product. The extent of heating which produces the desired result varies with the chlorine content of the intermediate product, materials containing 11% combined chlorine requiring only four to six hours heating, while materials containing 14.2% chlorine require 15 to 20 hours. Materials of still higher chlorine content did not yield completely oil-soluble products by this heat treatment, the degree of insolubility increasing with increase in chlorine content. The preparation of intermediate products containing about 12 to 14% chlorine is preferred, as the metallic salts of these products are very effective lubricating oil improving agents.

The chlorine content of the intermediate product may be controlled by the ratio of the formaldehyde and phenol used in the initial reaction. For example, when conducting the process as described in Example 1 with several different acter, though the described procedure is preferred. In these procedures the order'of the reactionsteps may be changed and similar reactants may be used. For example, the formaldehyde or other aldehyde may be first reacted with ammonia or amines to form alkylolamines for condensation with the phenol or alkyl phenol;

proportions of formaldehyde and para-isooctylphenol, the chlorine content of the intermediate product, and the nitrogen content of the final product, were observed to be as follows:

Intermediate product. Final prod- I een Instead of washing the heat treated reaction product with water as described above, the suspended ammonium chloride salt may be removed by filtration, preferably by filter pressing the suspension with the addition of a filter aid such as Hyflow. A suitable lubricating oil may then be added to the filtrate (if it is desired to produce directly an oil solution of the final product) and the alcohol-benzene solvent may then be removed by distillation.

Although a very satisfactory procedure for preparing the hydroxyarylalkyl amine product has been described with reference to the condensation of a nitrogen base with a condensation product of an alkyl phenol, formaldehyde, and hydrogen chloride, and the further auto-condensation of the resulting product, it is to be understood that other procedures may be employed for obtaining products of similar charor'it may be desired toalkylatethe base or the uct, e. g., with an alkylating agent such as diethyl sulfate, an alkyl halide, an alcohol, ketone, or olefin, by known alkylating methods, and with reduction by hydrogen, if needed or desired.

As in the case of many resin preparations, the exact mechanism of the reaction is not entirely understood. In the firststage the alkyl phenol may be regarded as condensing with the reaction product of the hydrogen halide and aldehyde, or as condensing with formaldehyde, the condensation product thereof being condensed with the hydrogen halide. The resulting product of this reaction is a complex mixture of various chlormethyl derivatives, having the following general formula:

in which the substituent groups may be attached to any position of the aryl nucleus indicated diagrammatically by the hexagon, R represents a hydrocarbon group of at least two and preferably an alkyl group of four or more carbon atoms, and X represents hydrogen or an organic radical, especially an alkyl, aryl or aralkyl radical which may in turn contain substituent groups. Among the compounds which have been found to be present in the products from such reaction are the following:

CHzCl Chlormethyl dilsobutyl phenol ClHiC CHaCl lHu Bis chlormethyl diisobutyl phenol on v on gem-00mm 5H" 3H" Chlormethyl bis (diisobutyl hydroxy phenyl) methane and on on owmcQcm-Qomm H11 :H11

Bis (diisobutyl chlormethyl hydroxy phenyl) methane In the second stage of reaction, the condensation products of the alkyl phenol, the formaldeheated as in Example 1 to givean oil-s 2,340,036 hyde, and the hydrogen halide split oil. halogen in undergoing a-iurthereondensationwith the nitrogen base, and thus, the alkyl' phenol-radi-.

cal becomes united with the base radical through the methylene (CH2) group, thereby forming compounds containing the following charac-:

The salts of the simplest non-resinous compounds containing a single hydroxy benzyl group are not very efiective, while the salts of compounds containing at least two hydroxy benzyl radicals in the molecule are more desirable, and the still more complex resinous typeof the agents herein disclosed have been found particularly effective for forming improving agents for lubricating oils. In the case ofproductsprepared from ammonia, this condensation and resiniflcation to form the preferred. resinous typeof products may take place even on standing at room temperature for along period of time; It is greatly hastened by heating, and such .heating is generally necessary to resinify and to, render eflective the products prepared iroznjgjamines. During the auto-condensation ammoniaor amines are liberated, so that the nitrogenfcontentof the final resinous product will correspqllqingly be decreased. 3 i o While the products describedjaboveare preferred for the preparationjoi addition agents'j of this invention, it is also possible to prepare suit-- able hydroxyarylalkyl" amines by a number of other methods, of which the iollowingfare'illustrative;

The hydrogen chloride and formaldehydniay first 'be reacted to form bis-chlorrnethyl",eth'ers such as ClCHzOCHzCl and C1CH2(O CH) ,iio cmici,

- in which n is an integer; and these chlorethfers may then be caused to ,reactwith the: phenol. This may be done bypassing dry; HClthrough t ispmixt re; tombtainithe clesiredzreaction prod- 1s 1mm:sin le-stage:reaotiomstz'lihis iproduct i thengeactediwithiammoniazand :tolgive a-resi;nous.;=product T- r :The; reaction oi=:hydrog en iehlorid aldehyde may also: be; conducted in heatedzas before a v of an alcohol, 2 for, example; methyl; alcohol; to

give an alphachlor alkyl ethenviflhig-smayi be done by passing idry; rHCl; into a suspension 0! paraformaldehyde in the alcohol. This ether may; be reacted" with the alk'yl phenol by heating with or Without a catalyst such as zinc I v v chloride, to give the alkyl:hydroxy b'enzyl chloride; "the original alcohol being forme i ag-1 by-product;

. Also; the 'alkyl --phenol% xmay' bbonverted to f the sodium-salt and this salt'g with no "excess alkali preseiitifmay then bebaiised to react with a an aldehyde to givea:dialkylol derivativ. ""This may beconverted =to the 'liloride y' 'reaCtIon with hydrogen *chlorid thenbe reacted withainmonia-{afid hatd as in 1 ,fa esfa .as I sii'chI 0 after. pur

Example 1 to give an oil iimejoijine'th yl oal Y I v s" purpos" iormaldehy ,eli n the iorfm..of, formalintcontainmg 37 EH20) .is, addedjftoljthisisolution and the j mixture allowed 't'q stand for about "42 hours. at z d p o d h ou h a we, w. sqliis dc, chloroa suspension of paraformaldehydein'ja' solvent such as benzene until "mostoi tlidiormaldehyde has reacted with theI-I'CI to give a soluble reaction product. Theen'tire reaction" mixture is then mixed with the alkyl phenolftd'giveljthe CH2C1 derivative, the reagents b n used preferably in a ratio. of about 2.5 mol equivalents of formaldehyde per mol "of, phenol. 'lf hisfintermediate product is. reacted with ammonia'fjand product. The bis-chlorinethyl ethers'rda so be Prepared by any otherv suitabl methndiithe mixed ether products may be'fra ctionatedseparate substantially" pure single others; anyQOne of which maybe tea; tedwithv thefpnenoh 111e,

to 24 hours. The mixture is then washed with water-'gto remove iso-propyl alcohol and ammoniu n chlor ide;andthe benzene solvent is then evaporated to; recover the complex reaction product. The latter is} a brittle solid resin, readily eating oils and soluble'in tufrbine oils of high viscosity index at temperatures above ab6iit 60 to 70 C.

Itis also possible rto cofiduct the reaction of the phenol formaldehyde andainmonia directly in a single stage placing agmixture of suitable proportions of t l'fese reagents in a' bomb and I e.- Eithei thfalkylol' lie-- rivative or; t the resultin'g halide derivative may soluble in asphaltic and'mixed base lubritheprocesses of the reaction. This is illustrated in the following example:

' y 3mm: 3

A stainless steel bomb was charged with 51.5 grams of iso-octylphenol. Then grams of 37% strength aqeuous formaldehyde and cc. of concentrated aqueous ammonia were added and the bomb was quickly sealed. It was then heated to 120 C. and held at this temperature for 16 hours. The bomb was then cooled, opened and the reaction mixture poured into water and extracted with ether. The ether extract was washed free of ammonia and was dried over sodium sulfate. Ether was then evaporated, leaving 50.5 grams of a soft red resin which contained 1.3% nitrogen.

EXAIPLI 4 A stainless steel bomb was charged with 150 cc. of absolute ethyl alcohol and 7.5 grams of trioxymethylene. The solution was then saturated with ammonia gas at 0 C. and the trioxymeth- 'ylene dissolved during the process of saturation,

17.5 grams of ammonia being absorbed. 55.5 grams of iso-octylphenol were then added, the bomb was quickly closed and then heated at 110 C. for 20 hours. opened and the reaction mixture poured into water and extracted with ether. The ether extract was washed free of ammonia with water and then dried over sodium sulfate. On evaporation of the ether, 62 grams of a soft light colored resin were obtained, which upon analysis was found to contain 2.52% nitrogen. This material was then heated at 200 C. for one-half hour under 3 mm. absolute pressure. Upon cooling the heated product, a brittle resin was obtained which had a nitrogen content of 0.56%.

Primary and secondary amines such as diethyl amine, diamyl amine, piperidine, aniline, di-

phenyl amine, substituted amines such as ethanol amine, and the like may be substituted for the ammonia in any of the above described processes to prepare similar amine condensation products. These upon heating also undergo further condensatlon and polymerization.

Similarly, more complex derivatives of hydroxy benzyl chloride may be prepared by any suitable methods and may be reacted with ammonia or a primary orsecondary amine and heated to secure resinous condensation and polymerization products suitable for use in this invention. Examplesof such hydroxy benzyl chlorides are on on a i OGHQCHEI and a on on anagram-@0320! The bomb was then cooled,

aseaosc proportions of iydrmbenayiaminessuch asthose having tbeenaraeteristicsh'uctwe on a' CK-N may also be heated to produce resinous autocondensation products suitable for use in forming the lubricant improvement agents of this invention. In the above formulae the substituent's may be linked toauy position of the aryl was prepared by reaction of equimolal amounts of ethoxy methyl diethyl amine (cimmcmocim with isooctyl phenol at the temperature of the steam bath for 24 hours. The product was distilled under 3 mm. mercury absolute pressure, obtaining about equal amounts of a clear liquid distillate fraction at 163 to 165C. and a residue which was a yellow, transparent, hard resin.

The phenols used in any of the above described oils, for example, cardinol, obtained from cashew nut shells, may be used. As indicated above, it is preferred that the phenols contain an alkyl group of at least 2, and preferably 4 or more carbon atoms attached to the nucleus. This may be accomplished by alkylating any of the abovedescribed phenols which do not already contain suitable alkyl groups. The alkyl phe'nols may be prepared by alkylation of phenols with oleflns, including mixtures of olefins such as are obtained in cracked petroleum fractions, and by alkylation of phenols with alkyl halides, including chlorinated paraflin wax and chlorinated petrolatums derived from petroleum. Such chlorinated waxes may contain dichlorides and polychlorides and may be used in alkylating phenols by the customary Friedel-Crafts type of synthesis to give complex alkylated phenols of high molecular weight in which several phenol radicals are linked by alkyl radicals in a single molecule. These high molecular weight complex alkyl phenolic products, when reacted with an aldehyde and a nitrogen base as described herein, and then converted into metallic salts, give products which are effective in reducing the pour point of waxy oils and in raising the viscosity index of lubricating oils as well as in improving their lubricating properties, such as film strength, and their stability and resistance to oxidation.

The foregoing description has related to methods of preparing the resinous auto-condensation products or hydroxyarylalkyl amines. The metallic salts of these products, which are the addireadily prepared by reacting the. products with metallic bases, alcoholates, etc.- For example, the octylphenol-fornialdehyde-hydrogen chloride-ammonia product of Example 1 may be reacted with barium hydroxide hydrate by heating with a dispersion of the latter in mineral oil or benzene to form a bariumsalt in which the metal replaces a hydroxy group. The same material may be reacted with an alcoholate, such as magnesium methylate or ethylate; or it may be reacted with caustic alkali, and the alkali salt so formed may be converted into other metallic salts by double decomposition, as in reacting with a salt of another metal. Chlorides of polyvalent metals, such as magnesium, zinc and the like, work satisfactorily in the double decomposition except in the case of barium, which is preferably used in the form of the bromide to secure suilicients olubility in absolute alcohol, which is the preferred medium for these reactions.

The onium salts of the resinous products of hydroxyarylalkyl amines may be prepared by reacting a halide of an onium base, e. g., a tetraalkyl ammonium chloride, a sulfonium chloride, or the like, with an alkali metal salt of the resinous hydroxyarylalkyl amine, preferably in an alcoholic solution. The alkali halide formed in the reaction is insoluble and may be conveniently removed.

EXAMPLE 6 145 grams of the ammonia derivative of chloromethyl diisobutyl phenol, obtained, for example, as in Example 1, was refluxed with 145 grams of C. P. benzene and 215 grams of Ba(dH)z.8HzO

for 60 hours, water being removed from the reaction mixture through a trap in the reflux condenser. The mixture was filtered to give an approximately 50% solution of the barium salt in benzene. Analysis showed that the product, on a benzene-free basis, contained 11.13% barium. A product containing 10.87% of barium on a solvent free basis may, however, be obtained after only eight hours of refluxing. On removal of the solvent the dry material was a brown powdery mass.

The invention thus contemplates the use as improving agents for extreme pressure lubricants of metal salts of high molecular weight resinous autocondensation products of hydroxyarylalkyl amines containing the characteristic structure in which R is an alkyl linkage such as in which R represents either H or alkyl or aryl groups or substituted alkyl or aryl groups and tion agents of the present invention, may be hydroxy alkyl benzyl radical. The desired compounds are also, characterized by having at least four carbon atoms in alkyl groups joined to the aryl nucleus and/or to the amine'radical (N=) and are further characterized in having'undergone an auto-condensation reaction to produce a resinous, viscous liquid to solid product of high molecular weight which is soluble in hydrocarbon oils. In this, as in all the other structural formulae given in this application, the location of the substituent radicals in regard to the aryl nucleus is given merely as an illustration, and the various substituent radicals may be attached to any positions of the aryl nucleus, ortho, meta and/or cant Testing Machine (S. A.

may represent similar or different groups in the same molecule, n represents asmall whole number, and X represents hydrogen or one or more organic radicals attached to the aryl nucleus, especially analkyl, aryl or aralkyl radical which para to the hydroxyl group and to each other. The preferred compounds for use according to this invention come within the above definition and are salts of resinous auto-condensation prod-' ucts of materials havingthe characteristic structure on tallic salts the corresponding salts containing basic radicals instead of metals, such as onium sa1ts,-e. g., the ammonium, alkylammonium, suL fonium, phosphonium and pyridonium salts, may be used to advantage.

Illustrations of the use of the products described above as extreme pressure lubricant improving agents in accordance with this invention are presented in the following example:

EXAMPLE 7 An extreme pressure lubricant concentrate was prepared as described in U. S. Patent 2,124,598 by heating chlorinated kerosene (40% chlorine, prepared by chlorination of kerosene at 200 F.- with chlorine gas) with a mixture of sulfur and aqueous alkaline sodium hydrosulfide, sodium hydroxide and isopropyl alcohol under reflux for several hours. The reaction mixture was then permitted to settle and a middle layer of the desired reaction product was separated from a lower aqueous layer of inorganic salts and an upperalcohol layer was then stripped free of alcohol. There was thus obtained a sulfurized chlorinated kerosene containing'about 7% by weight of sulfur and 32% by weight of chlorine, both in effective form to increase extreme pressure lubricant properties of mineral oils, as evidenced by the ability of a 10% blend of this concentrate in a mineral lubricating oil to carry more than a 325 pound load on an S. A. E. Extreme Pressure Lubri- E. Trans 1936, page 293). I j

This sulfur-chlorine extreme pressure concentrate was subjected to the Chrysler-Almen corrosion test (described below) as follows:

Ten parts by weight of this extreme pres sure mayin turn contain substituent groups. suchasa portion of this blend containing no addition agmt and other portions containing, respectively.0.2$olthebarium-ltoltheauto-eoudensationproductcltheammouiaderivativeoi chioromethyl dihobuipiphencl, prepared as in lxampie6,0.3%ofthecalciumsaltofthesame, 0.3%ofthesincsaltoithesameandamkture 0.2% of the auto-condensation product of the derivative of chloromethyl diisobutyl phenol and 0.1% of the barium salt of the some were subjected separately to-the Chrysler-Almen corrosion test. The test pieces resulting from the test on the unblended lubricant were-badly stained and showed considerable rust. The tests on blends of the lubricant with the various metal salts showed no evidence of corrodon, stain or rust in any case.

cnmur-slm corr sion m:

The lubricant in question is run on the Almen machine with six weights for twenty minutes. The Almen test pieces and the lubricant is then placed in a bottle and stored in an oven at a especially the active chlorine, to be used will, of

course, depend upon the severtiy of the conditions under which the lubricant is to be used but will generally vary between the approximate limits of 5% to 50% (preferably above about 32%) in the chlorinated organic compounds or between the approximate limits of .05% and 10% based on the total weight of lubricant (exclusive of any water which may be used as in the preparation of water-soluble type cutting oil).

.In preparing extreme pressure lubricants of the halogen type, it is frequently desirable to in: corporate sulfur compounds especially to increase the stability of the lubricant at high temto the particular service for which the blended lubricant is intended.

Although the mechanism and the operation of the presentinvention are not thoroughly understoodanditisnotdesiredtobelimitedtoanyparticular theory as to the operation thereof, it is believed that the active chlorine compounds present in the extreme pressure lubricant are capable of carrying very high loads between metal surfaces by means of the formation of microscopic films of metal halides such as ferrous or ferric chloride which prevent metal to metal contact and resultant welding and scoring. These films, particularly in the presence of moisture which is almost always present in gear cases tend to hydrolyze into metal oxides and hydrochloric acid. Also the chlorine compounds in the lubricant itself tend to hydrolyze with the liberation of hydrochloric acid (HCl) and this acid in turn attacks the metal surface because iron and steel and various alloys in general are quite susceptible to attack or corrosion by hydrochloric acid and other strong halogen acids. 0n the other hand, in lubricants containing a substantial amount of active sulfur, the latter, particularly in the presence of moisture and at elevated temperature and -pressures produced between gear teeth or over a long period of time,

tends to 'be converted into hydrogen sulfide and the latter tends to react with the metal to pioduce the corresponding metal sulfides which are generally black, such as iron and copper sulfides.

perature and for this purpose a sulfurized fatty or mineral oil or a sulfur compound such as an organic sulfide, mercaptan, dior polysulfides, xanthates, xanthogen sulfides, thio carbonates,

' etc., may be used in which generally from about 1% to 30% (and preferably about 7%) of sulfur is incorporated in the active or combined state. Based on the total weight of lubricant, the proportion of sulfur should normally be between the I limits of about 0.2% and 10%.

Instead-of using separate chlorine compounds and sulfur compounds, it is possible to use single materials in which both sulfur and halogen have been incorporated by treatment of suitable unsaturated organlc compounds, such as cracked wax and fatty oils of the drying and semi-drying types, with a sulfur halide, or by reacting an organic halogen compound with an inorganic sulflde, poly-sulfide, thio carbonate or xanthate.

A further advantage of the improving agents of this invention is that they are soluble in highly aramnic lubricating oils and may be used to prepare stable extreme pressure lubricants and cutting oils with highly refined petroleum base 7 lubricants having a viscosity index 01.80 to 103 and even higher.

Such oils may be obtained directly as distillate and residual fractions of If desired, other known addition agents or lubricants may be incorporated in the lubricant prepared according to the present invention; for instance, fatty oils, fatty acid or naphthenic acid soaps, esters, thickeners such as polyisobutylene having a molecular weight above 1,000, pour depressants, antioxidants, oil-soluble metal soaps, dyes, etc., may be added.

It is not intended that this invention be limited to any of the particular examples which have been given for illustration only, nor .by any of the theories as to the operation of the invention but only by the appended claims in which it is intended to claim all novelty inherent in the invention as broadly as the prior art permits.

We claim:

1. A lubricant composition comprising a major proportion of a minerallubricating 011, an oilsoluble halogen-containing compound of a kind and in sumcient quantity to substantially increase the load carrying capacity of the lubricant but tending to form a hydro-halogenic acid in the presence of said 011, and a small proportion of an oil-soluble salt of an auto-condensation product of a hydroxyarylalkylamine, said amine having alkyl groups which contain aitotal of at leastt carbon atoms per molecule.

2. A lubricant composition comprising a major proportion of a mineral lubricating 011, an oil--v soluble organic halide of a kind and in sumcient quantity to impart extreme pressure character- 'istics to .said lubricant but tending to form a hydro-halogenic acid in the presence of said oil ase ose and a small proportion of an oil-soluble metal salt of an auto-condensation product of an alkyl hydroxy benzyl amine having at least four carbon atoms in the alkyl group.

3. An extreme pressure lubricant comprising a major proportion of a mineral lubricating oil, a small proportion of an oil-soluble organic halide of a kind and in sufiicient quantity to increase substantially the extreme pressure. lubricant characteristics of said oil but tending to form a hydro-halogenic acid in the presence of said oil, and a small proportion of an oil-soluble salt of an auto-condensation product of an hydroxyarylalkyl amine, the uncondensed amine having the characterizing structure I R n in which R is an alkyl linkage, R is hydrogen or an alkyl or aryl radical or a substituted alkyl or aryl radical, n is a small whole number, and X is hydrogen or an organic radical.

wherein It represents at least one alkyl group substituent in the aromatic nucleus Ar, the subscripts m and n are integers to satisfy valence requirements, and X represents a nitrogen base radical in which the nitrogen is linked to the methylene group.

5. A composition as described in claim 4 in which the subscript n is an integer from one to three, and in which X is a nitrogen base radical in which the nitrogen is linked to the aryl nucleus, Ar, through or in a methylene group, -CH2-.

6. An extreme pressure lubricant comprising a major proportion of a mineral lubricating oil, a substantial proportion of an oil-soluble organic halide of a kind and in suiiicient quantity to impart extreme pressure characteristics to said treme pressure characteristics to said lubricant portion of an oil-soluble metal salt of a resinous auto-condensationproduct of an alkyl hydroxy benzyl amine having the characterizing structure R -C HiNHi in which R represents an alkyl group of at least four carbon atoms.

7. A composition as described in claim 6 in v which the salt is a salt of a divalent metal.

8. A composition as described in claim 6 in which the salt is a salt of an alkaline earth metal. 9. A composition as described in claim 6 in which the salt is a barium salt,

10. A composition as describedin claim 6 in which the salt is a salt of an alkali metal.

- 11. A composition'as described in claim 6 in which the salt is an onium base salt.

12. An extreme pressure lubricant comprising a major proportion of a mineral lubricating oil, a substantial proportion of an oil-soluble organic compound containing chlorine and sulfur and of a kind and in suflicient quantity to impart exbut tending .to form hydrochloric acid in the I presence-of said oil, and a small proportion of a lubricant but tending to form a hydro-halogenic add in the presence of said oil, and a small prometal salt of an oil-soluble auto-condensation product of an ammonium derivative of an alkyl phenol formaldehyde hydrogen chloride condensation product, in which the alkyl substituent of the phenol contains at least four carbon atoms and in which a nitrogen base radical is linked through a methylene group to the aryl nucleus of the alkyl phenol.

. 13. A composition as described in claim 12 in which the alkyl phenol is a para-iso-octyl-phenol.

'14. An extreme pressure lubricant comprising a major proportion of a mineral lubricating oil, a minor proportion, effective to increase substantially the extreme pressure lubrication characteristic of said oil, of a sulfurized chlorinated" naphtha containing at least 7% by weight of sulfur and 32% by weight of chlorine and also containing as an anti-corrosion agent effective in suppressing the corrosive tendencies oi said suliu'rized halogenated naphtha. and a small proportion or an oil-soluble metal salt of a resinous condensation product of ammonia with an alkyl hydroxy benzyl chloride.

JOHN c. aaoaon M. McNUm'r.