US2263445A

US2263445A - Mineral oil compositions and improving agent therefor

Info

Publication number: US2263445A
Application number: US328872A
Authority: US
Inventors: Orland M Reiff
Original assignee: Socony Vacuum Oil Co Inc
Current assignee: ExxonMobil Oil Corp
Priority date: 1940-04-10
Filing date: 1940-04-10
Publication date: 1941-11-18
Anticipated expiration: 1958-11-18

Description

Patented Nov. 18, 1941 MINERAL OIL COMPOSITIONS AND IMPROV- ING AGENT THEREFOR Orland M. Beifl, Woodbury, N. 1., assignor to Company, Incorporated, New York, N. Y., a corporation of New York Snoo y-Vacuum Oil No Drawing.

Application April 10, 1940,

Serial No. 828,872

12 Claims.

This invention has to do in a general way with mineral oil compositions and is more particularly related to viscous mineral oil fractions of the type used for lubricants, dielectrics, and the like, which have been improved in one or more of their various properties by the addition thereto of an oil-improving agent. This invention is based upon the discovery of a novel class of mineral oil addition agents which will improve one or more important properties of the oil and has as its primary object the provision of mineral oil compositions containing such improving agents.

In my copending application Serial No. 222,755,

flied August 3, 1938, Patent No. 2,197,835 issued April 23, 1940, of which this application is a continuation in part, I have described a general class of metallo wax-aryl" compounds as mineral oil addition agents. These compounds are multifunctional in that they are effective to reduce the pour point, improve the viscosity index, and retard the deleterious effects of oxidation in the oil to which they are added. The present invention is predicated upon the discovery that the sulfides or sulfur derivatives, or more generally the sulfur, selenium, and tellurium derivatives, corresponding to the wax-aryl metallo compounds of my copending application have oilimproving properties substantially greater in certain respects than the corresponding compounds of the aforesaid copending application,

The preferred compounds of the present invention may be described as the oil-miscible sulfldes (monoand poly-sulfides and polymers thereof) of alkyl-substituted aromatic compounds in which the aryl nucleus carries one or more metallo complexes. As aforesaid, the invention also contemplates the corresponding derivatives of selenium and tellurium; and while the invention will be described herein with particular reference to the sulfur derivatives, it is to be understood that the corresponding derivatives of selenium and tellurium are in all cases contemplated.

Broadly, therefore, the oil addition agents contemplated herein may be described as oil-miscible metalorganic compounds characterized by the presence of at least two alkylated aryi nuclei interconnected by at least one atom of sulfur, selenium, or tellurium. The alkyl substituent in the aryl nucleus lends oil-miscibility to these aryl metallo sulfides, and the nuclei should carry a sufllcient number of substituents, or the substltuents should be derived from aliphatic hydrocarbons ot suiliciently high molecular weight, to render the product oil-soluble. I have discovered that if this oil-solubilizing alky substituent is derived from an aliphatic hydrocarbon or a mixture of aliphatic hydrocarbons predominantly comprised of compounds having at least 20 carbon atoms, in addition to imparting oil-solubility to the compound, these long chain or heavy alkyl snbstituents impart to the compound the properties of depressing the pour point and improving the viscosity index of the oil. As was pointed out in the aforesaid copending application, the presence of the metallo group with the long chain multifunctional-imparting substituent in many cases gives added effect to the lon chain alkyl substituent in the properties of improving the pour point and viscosity index. The .metallo constituent of the compounds in the aforesaid copending application served the purpose of inhibiting the deleterious effects of oxidation, as evidenced particularly in reducing the tendency of a motor oil containing the addition agent to cause ring-sticking and form sludge in motor operation. By the introduction of sulfur. I have found, the property of inhibiting the deleterious effects of oxidation is greatly in creased both in reduction of acid iormation and in retarding of ring-sticking mentioned above: and I have further found that in many instances the condensation of these wax-aryl metallo nuclei with a sulfur linkage forms products in which the pour point and viscosity index improving properties are increased over those of the corresponding wax-aryl metallo compounds.

The broad class of compounds or condensation products contemplated herein as oil addition agents may be characterized by the general formula a m n in which T represents an aromatic nucleus. which pie: wherein M represents the hydrogen equivalent of a metal and Z represents the elements oxygen, sulfur, selenium, or tellurium and the radicals R!) all all (-N==NA);

wherein R represents a radical selected from the group consisting of aryl, aralkyl, alkyl, and alkaryl; R" represents hydrogen, alkyl or aryl radicals; X, x' and x" represent elements selected from the group consisting of oxygen and sulfur: A represents (-x-), (-NR"), (-CX'X-l and (-SO:|); It represents one or more alkyl groups of sumcient aliphatic hydrocarbon content to impart oil-solubility to the compound, and for the preferred class of multifunctional addition agents It represents at least one aliphatic hydrocarbon group having at least 20 carbon atoms corresponding, for example, to the aliphatic hydrocarbons characterizing petroleum wax. 2 represents an element selected from the group consisting of sulfur, selenium, and tellurium; and n represents a whole number from 1 to 4.

In addition to the ,oil-solubilining aibl group R. the and nucleus may contain residual hydrogen, part or all of which may in turn be substituted with substituents which may have positive or negative or neutral solubilising effect; or the hydrogen content maybe increased by addition of hydrogen by hydrogenating the compound. Such hydrogen or substitucnts Just referred to are indicated by Y in the foregoing general formula, which character may be defined as having been selected from the group consisting of hydrogen, hydroxyl, ester, (organic or inorganic acyl groups) xanthate, keto, alkon, alhl sulfide, aroxy, ether alcohol, aldehyde, thioaldehyde, aldime, oxime, amide (organic and inorganic acyl groups), thioamide, carbamide, aralkyl, aryl, alkaryl, halogen, nitroso, amino. nitrosamine, amidine, imine. N-thio, diam, hydrazine, cyano, thiocyano, asos'y, sac, and hydrazo radicals. Of the foregoing Y" substituents, the sulfur-containing radicals are highly important, such substiments giving additional oxidation-inhibiting value to the compound. Bubstituents such as hydroxyl, inorganic acyl ester groups. oxlme, inorganic acyl amido groups, and amino radicals are also highly important substituents because of their antloxidant action.

In general it appears that any metal may be employed as the metal M in compounds 01' the condensation products of the type contemplated herein to provide valuable oil addition agents.

ofgroupsftovminclusiveoftheperiodic system and comprise the following: the alkali metals: lithium, sodium, potassium, rubidium, and caesium; the alkaline earth group: beryllium, magnesium, calcium, strontium, and barium; the metals zinc, cadmium, mercury, scandium: the metals aluminum, gallium, indium, thallium, titanium, zirconium, cerium, thorium; germanium, tin, and lead; vanadium, columbium, and tantalum; arsenic, antimony, and bismuth; chronium, molybdenum, tungsten, and uranium; rhenium, manganese, iron, cobalt, and nickel; ruthenium. rhodium, and palladium: osmium, iridium, and platinum.

Someoftherareearthmetalsaregiveninthe foregoing. Other rare earth metals suitable for use in the formation of the alkylated aryi metallo sulfide compounds contemplated by this invention are those now commercially available as the cerium and yttrium group: namely. a mixture of praseodymium, ne ymium, samarium, europium, gadolinium, terbium, -dypsprosium, holmium, erbium, thallium, and iutecium.

The selection of a metal will, of course, depend to a certain extent upon the character of the oil in which the addition agent is used and the conditions to be encountered by the oil in use. Certain metals such as lead, zinc, and tin, for example, may contribute to the oiliness characteristics of the oil. The alkali metals are not so desirable when the oil is to be used in the presence of water because of the tendency of certain of the derivatives containing same to cause emulsification. For the inhibition of acid formation in the oil under conditions where the oil is susceptible to oxidation special preference is given to tin.

As aforesaid, the aryl nucleus I of General Formula I may be monoor poly-cyclic, and it may contain substituents in addition to the oilsolubilizing alkyl groups and the metallo complex. The metallo complex, as indicated by the types of radicals listed under the symbol 2 in General Formula I. may be directly connected to the aryl nucleus as in the case of a phenate, an aryl carboxylate, and the like, or it may be in a side substituent which in turn may be a hydrocarbon chain or cyclic group. Condensation products of the general type represented by Formula I in which the aryl nucleus T is monocyclic 5 may be represented by the general formula ZM ZM Since the condensation reaction employed in synthesinng the sulfides or sulfur condensation products contemplated herein may be attended by a certain amount of condensation between groups of the type indicated in Formula II, such III. ZM Y ZM Y ZM Y z. -E3 I B R It Also, when alkylation of the aryl nucleus has been eifected to obtain a multifunctional product by a preferred procedure, which involves the Friedel-Crafts condensation of an aromatic compound or a hydroxyaromatic compound with a halogenated aliphatic hydrocarbon material of at least 20 carbon atoms, such condensation may result in the formation of compounds in which two or more aryl nuclei are interconnected by one or more aliphatic hydrocarbon chains. Compounds of this type, when further reacted to obtain the so-called sulfides or sulfur derivatives and the corresponding metallo derivatives of such sulfides, may result in the formation of compounds corresponding to the formula IV. E n a n H nc--e c c-cn a Y Y Y n ZM ZM ZM or compounds of the formula v. n n 1: a n

a no c on a H no e on H H n n in which the chains have the same significance as the preferred long chain substituent R hereinabove referred to.

The foregoing discussion is not intended as a development of the specific molecular composition or structure of the compounds or condensation products contemplated herein but is intended as indicative of the possible composition of these oil addition agen As aforesaid, the addition agents contemplated herein may be described as oil-miscible metalcrganic compounds which are characterized by the presence of at least two alkyiated aryl nuclei interconnected by at least one atom of an element selected from the group consisting of sulfur, selenium, and tellurium, and for purposes of definition or description herein these compounds may be described as condensation products which contain at least once the grouping represented by General Formula I. This characterization, it will be observed, is inclusive of the simple sulfide or polysulflde represented by Formula II as well as the so-called polymers represented by Formulae III, IV, and V. The term sulfide as used herein is inclusive of the monosuifldes, disulfides, trisultides, and tetrasulfldes-that is, it includes both monosulfides and polysulfldes and mixtures thereof-and it is also intended to include such polymers and related derivatives as may be formed by the illustrative procedures hereinafter employed to illustrate the synthesis of typical compounds coming within the general held of the invention.

Exemplary types of compounds or condensation products falling into the general class contemplated herein are illustrated in the following table, in which the formulae given are for illustrative purpos s only and show only the monocyclic nucleus which is unsubstituted except for wax, the metallo-complex substituent, and in certain instances (as in the case of keto. ether, and ester derivatives) typical Y substituents.

, TABLE I I. Metal oxides of wcar-hvdrozuarul sulfides h (War). 10 II. Metal salts of wax-oral mercapto sulfides MS as! u). (W III. Metal alcoholotes of win-arm alcohol sulfides (a) Mx-n' rr-xm zw (wm. (Wu). o Mxn'x" r-rvxm z. E (Wu). (we).

IV. Metal salts of waz-hudroxyarmnattc acid sulfides (a) no on Mx-c c-xM 40 it, it,

(Wax). t. (Waxh MX-i i-XM V. Metal salts of wam-hudrozyaromatic aliphatic acid sulfides (a) no on (wu).. -z.- (Wax). MX-C-B. rv-i-xru MO OM e0 (Wax)-- -z.- (War).

Mx-c-a w-c-xm JL. ii,

VI. Metal salts of wac-mercapto aromatic acid sulfides (n) HS SH do I'- h MX-O o-xM 15 i i m M B BM Ix. Metal derivative: 0! mm: keto sulfide:

(Wu). --z.- (Wu). (0) x o o x Q a mx-(Lw- (Liv-(Ln: MX-O c-xM I 1% (Wu) 2 u). a (c) H8 SH ('IXLQZ-GWHU- E E mx-m- B'-XM MXCR B'-CXM I I z. ((1 Ms SM 15 (wm- W).

(e) 0 0 2- (W {*3 {3 5 A (La MXCB zv-c-xm 20 (Wu). z. Wm. VII. Metal salts of warry! acid sulfides MXG c-xM (a) x' x' MIC-(ILL iE-XM X. Metal derivatives of wax-cry! eater sulfides (a) 1 0 0 so MX-W-O- (L-o-w-xM (Wax). (Wu),

u). (Wu). VIII. Meta: salts of was-am! ether acid sulfides o @-z; (a) X x v (W (W Mx-J; R'X" X"--R- XM u (c) o o n'o-g (Low w n (W'IJ' (Wu). z. (W88). (0 x' x' MX-E-X" W i -KM NIP-0 0-x1u XII. Metal salts of wax-am! amine sulfides (b1) XV. Metal salts of sulfides of wax-arm hydra- 3M NR'X" x'qa'n Mu zine,

H/ \K R" R" z (u \N n n 1 a -n N an N a (Wu)- (Wu)- M M XIII. Metal salts of sulfides of waxwryl amine acids (m) B a o uh (Wu)- o n" n \N-R"N-H' B'NB"-N/ m \M (Wu).- z.- (Wu)- 7 65 7 (Wu). (Wu)- I an XVI. Metal salts of sulfides of waz-arul carv in no bamum I (Wu). 2 l m). a" (Wu)! Mxo-xn 65 1P0 h (bl) li. n".

. b) H- -N N 1! 7 (Wu) 2 (Wu). (Wu) 2. Wu); A I E t a l mx-o-n BBC-$1M 6 areas XVII. Metal salts of war-dry! amide sulfides XVIII. Metal salts cl sulfides clause-owl amidines R all N (Wa (Wi h XIX. Metal compounds of sulfides of wax-and xx. Additive compounds of inorganic metal salts with sulfides of aromatic compounds Mel 2.14

(Wax). (Wax).

M2 ZM @z.

(Wu). (Wax)- In the foregoing exemplary formulae the symbol (Waxh is employed to indicate the preferred alkyl substituent of at least 20 carbon atoms which imparts multifunctional properties to the compounds. The term wax is used because I 0 have found that petroleum wax is a preferred source for substituents of this character, special preference being given to paraflin wax which is predominantly comprised of aliphatic hydrocarbons having at least 20 carbon atoms, but it is to 5 be understood that the invention is not restricted to petroleum wax in this regard, but that other high molecular weight aliphatic hydrocarbons or mixtures thereof or predominantly aliphatic materials such as ester waxes may be used: and that compounds such as high molecular weight alcohols, from which the desired alkyl halide for synthesis of the wax compound may be derived, are contemplated. Also, in these exemplary formulae X. X, and X" represent oxygen or sulfur or the related elements, selenium andtellurium. It represents an alkyl, aralkvl, aryl, or alkaryl group which may or may not be otherwise substituted. R" of groups XII, XV, XVII. XVIII. XIX represents hydrogen, alkyl, or aryl radicals;

0 R1" represents organic or inorganic acyl groups;

R" represents hydrogen, alkyl. aryl, or acyl radleafs: M1; in the formulae oi groups xn, XIV, xv. XVIII, xx represents double complex metal salts formed by addition of metal inorganic compounds to aromatic amines and to sulfur groups of aromatic compounds.

It will be observed from the foregoing illustrative examples that all of the formulasv represent metalorganic compounds which are characterized by the presence of at least two wax-subst tuted aryl nuclei interconnected by at least one ates:

' of sulfur, selenium, or tellurium (an). All of "these condensation products or sulfides '(in the case of the preferred products) may be considered 7 as compounds in which the metal is present in the radical or group -ZM, wherein M represents the hydrogen equivalent of a metal and Z represents orwgen or sulfur, or the radicals (-NH-i (N(R")2.Mn); (-R'N(R"):.Ma); (0013")- N(R" :Ma) ;(N=N.Mn) ;(NR' '-N(R") :Mn) and the like, wherein M represents the hydrogen equivalent of a metal: R is selected from the group consisting of aryl, aralkyl, alkyl, and alkaryl; R" is selected from the group consisting of hydrogen, alkyl, and aryl; x, x' and 1!" represent elements selected from the group consisting of oxygen and sulfur; A is selected from the group co of -x-); (-NR"-); CX'X); and (-80a): and (Mn) reprecents an inorganic metal compound.

In these typical compounds or condensation products it will be observed that the metal-bear,-

ing group includes a side substituent on the characterizing nucleus which may be an aryl or alkyl group. ether group, an ester group, or the like. In this latter regard it will be understood that when the metal-bearing group includes a side 'substituent R, which is an aryl radical, such aryl side substituent B may be waxor alkyisubstituted, and such aryl substituent may enter into the sulfur condensation reaction. It is also to be understood that when one or more of the aforesaid'Y substituents are present which contain methylene groups such as alkyl, keto, ether, ester, etc., these groups may also carry substituents such as halogen, hydroxy, amino, nitro, sulpho. cyano, etc. a

One general procedure for synthesizing the monoand poly-sulfides of alkylated aryl metallo compounds of the type discussed above is to start with the corresponding alkylated aryl compound before it has been metal-substituted. Such compound is reacted with a sulfur halide to form the sulfur condensation product, after which it is washed to remove the hydrochloric acid formed in the sulfur chloride reaction and then reacted'with an alkali metal such as sodium.

either in solution as the element or as the alcoholate, to introduce alkali metal into the metalcontaining complex. The corresponding derivative of a desired polyvalent metal is then obtained by double decomposition with an alcohol solution of an alcoholoiuble salt of the desired metal.

In the event sulfur dichloride is used in the general procedure described above, the condensation product will be in the nature of a monosulflde or polymers thereof; and sulfur monochloride will yield the corresponding disulilde or polymers thereof. If a mixture of sulfur monochloride and sulfur dichloride is used, the product will be a mixture of the sulfides. Elementary sulfur may be used as a condensation agent to obtain many of the compounds, but this is not considered the most desirable procedure except when it is desired to obtain sulfides of arylamines and the like wherein the aryl nucleus can be sulfurized without appreciable formation of N-thio groups. The formation of N-thio groups is common to all the wax-aryl aminotype of compounds when sulfurized with sulfur halides. In the formulae of Table I the l l-thio group is shown only in the case of amino acids (Type-Compound XIII), but the remaining metal-bearing group substituents illustrated in Table I are also contemplated in combination with N-thio groups. It is to be understood that in the formation of the N-thio group by the sulfurization of wax-aryl amino compounds with sulfur halides, the linkage Zn (where n is 1 or 2) is also produced.

Bulfur derivatives of higher sulfur content may be obtained by reacting a compound having a disuliide linkage (such as is obtained with sulfur monochloride) with alkali polysulfldes or with alkyl tetrasultldes. Such higher sulfur derivatives may also be obtained by first reducing the disulflde to form a mercaptan and then reacting the mercaptan with sulfur dichloride (to form the trisulflde) or with sulfur monochloride (to form the tetrasulilde).

In all cases it is suitable to effect the sulfur condensation before attempting to substitute polyvalent metal. but where a compound is available in the form of the alkali metal derivative of the alkylated aromatic compound and containing alkali stoichlometrically equivalent to both the sulfur chloride and chloride of the polyvalent metal-to be substituted. this may be reacted flrst with the metal chloride, followed by reaction with the sulfur chloride to form the p iflalent metal salt of the sulfide derivative, with formation of sodium chloride in the neutrallsation reaction as by-product. It will be understood that the oil-improving agents contemplated by this invention may be pure compounds satisfyin the general Formula I above with a monoor poly-cyclic nucleus as 'l and with orwithout oneormoreofthevariousY substituents. In case the compound is desired as an inhibitor of oxidation products only, in which event the alkyl substituent B may be of relatively low molecular weight, preferably containing a total of at least 10 carbon atoms, the starting material for the sulfur tion and subsequent introduction of polyvalent metal may he a commercially available alkyl-substituted aromatic or hydroxyaromatic compound which carries a .substituent susceptible of metal-substitution or which is itself susceptible of substitution with such a group. For the'multifunctional compounds, however, I consider it desirheavyalhyl group and in manufacturing the preferred oil-improving products of this invention by procedures in which wax-substitution is effected with a chlorinated petroleum wax (or similar high molecular weight aliphatic material) by the Friedel-Crai'ts reaction, the dual oilimprovingproductisnormallyorusuallya mixture of different compounds which vary in the alkyl substituent as the hydrocarbon constituents ofwaxvaryandwhichmayaisovaryastothe number of alkyl substituents on the aromatic nucleus and as several aromatic nuclei may be interconnected by was chains.

In general the procedure followed in effecting wax-substitution or heavy alkyl-substitution is as to chlorinate a petroleum wax such as paranln wax or other high molecular weight aliphatic material to a chlorine content of from 10 to 16 per cent and then condense the aliphatic material with the desired aromatic compound in a Friedei-Crafts reaction, using a catalyst such as anhydrous aluminum chloride. 'lhe details in this procedure and suggestive aromatic and aliphatic compounds which may be used are described in the aforesaid copending application.

Illustrative procedures which may be foflowed in syn typical compotmds or condensation products falling under the various typecompounds"c in'lablelabovewillnow bedescribed. Itisagain emphasisedthat while Table I shows only monocycilc aromatic derivatives, both monoand poly-cyclic compounds and derivatives thereof are contemplated herein ,andthatwherethetermwaxisusedtlhavereference to aliphatic hydrocarbon groups in general. particular preference being given to allphatic hydrocarbon groups having at least 20 carbon atoms or organic compounds or compositions such'as petroleum wax predominantly comprlsed of such heavy alkyl groups: or compounds such as high molecular weight-aleoholafrom which the desired alhyi halide for unthesis of the wax compound may be derived.

Tree-Comm I Metal oxides of war-hydrous! sulfides A typical compound or condensation product of this group is represented bythe formula reptinggroupIofTabieI. dsofthis maybeobtainedbyilrstreactlnganalkyiat'ed hydroxyaromatic compound with a sulfur haiideto form a corresponding 'alh ylated i suiilde (monoor poly-sulfide),

m m" then substituting the hvdrcxyi hv rqs with an 75 other cl of metal can be obtained by reacto able'to substitute the aromatic nucleus with m aikalimetaLfollowedbysubstitutionoftheaikali metal with the-t metal by metasuch a caution product with the monosulnde linkage is as follows:

Alkriated phenol 1 mol Sulfur dichloride A moi Carbon disuiflde. benzene,

chlorbenzene, or ethylene dichloride as solvent 1 partby weight A typical reaction for obtaining the disuli'lde linkage is as follows:

Alkylated phenol. 1 mol Sulfur monochloride...- l5 mol Carbon disulflde. b e n s e n e,

chlorbensene, or ethylene dichloride as solvent 1 part by weight In the foregoing reaction mixtures it is understood that the alkrlated phenol is for the preferred products a wax-substituted phenol prepared according to the procedure outlined in the aforesaid copendlng application having a thesizeofthereactlonmixtureandtherateof stirring. the rate of addition being such that the temperature will not rise unduly above 100 F. Higher reaction temperatures may be used, but the lower temperature (100 1".) favors formation of a product of better color. After addition of the sulfur halide. the mixture is stirred at 100 F. for a period of about 1 hour a to complete the reaction. Hydrogen chloride is evolved in the reaction, resulting in fixation of .suiiur in the aryl nucleus. After completion of this condensation reaction the mixture is waterwashed to remove the dissolved hydrochloric acid,

after which it is ready for metal-substitution.

By reacting a disuldde type of compound, obtained by using sulfur monochloride in the foreoing procedure; with alkali polysulndes or alkyl tetrasulfides the corresponding triand tetrasulndelinkagecanbeobtained. Theuseofalkyl tetrasulflde is preferred in this type of reaction. A typical reaction mixture is as follows:

Alkylated phenoldisulfldml--- lmol ll Ethyl tetrasulilde 18101 Carbon disuiflde or ethylene dichloride solvent lpartbyweight 7 IE, at which temperature it is treated with A theethyltetrasulfldeandrefluxedoveraperiod ofabout lhour to complete the addition of sulfur.

-A typical procedure for obtaining the metal derivatives of alkyiated phenol sulfides of the type described above is, in the case of alkali phenates, to react the hydroxyaromatic sulfide with an alkali aicoholate containing an amount of alkali metal equivalent to the hydroxyl hydrogen of the phenate. The metal derivatives of ing the alkali phenate with an alcohol-soluble inorganic salt or fatty acid salt or oxy salt of the desired metal. Another desirable procedure for forming the phenates of other classes of metals is to treat the hydroxyaromatic sulfide with an equivalent of the salt of the desired metal in alcohol solution, followed by reacting with an equivalent amount of sodium alcoholate, which results in the formation of the alcoholate of the desired metal as the initial reaction product. By heating the mixture to about 250-300 F. during a 1-hour period the metal alcoholate is reacted with the hydroxyl group, resulting in formation of the metal phenate derivative.

In general the procedures described in the aforesaid copending application for forming the wax-metal phenates can also be employed in synthesizing the metal derivatives of alkylated hydroxyaromatic sulfides.

Compounds or condensation products of the type obtained according to the foregoing procedure when wax-phenol is used may be broadly termed the metal phenates of wax-phenol sulfides; and when wax-naphthol is used as the reactant, they may be classified as the metal naphtholates of wax-naphthol sulfides.

TYPE-COMPOUND II Metal salts of waz-aryl mercapto sulfides Compounds of the Type-Formula II are to be prepared from the wax-hydroxyaryl sulfides by reaction with phosphorus pentasulflde, whereby the oxygen of the (-OH) group is replaced by sulfur to form the (-SH) group. The metal salts are to be prepared by methods used in the preparation of metal oxides of wax-hydroxyaryl sulfides as described under Type-Compound I.

TYPE-COMPOUND III Metal alcoholates of wax-aryl alcohol sulfides sulfides of wax-aromatic alcohols suitable for the preparation of Type-Compounds III (a) and b) are to be prepared as follows:

(a) Wax-aromatic hydrocarbons are to be chlorinated or brominated whereby the halogen is introduced into the alkyl group. The halogen is to be then substituted with the hydroxyl group by reaction with caustic soda under pressure. The product is then to be sulfurized by reaction with elementary sulfur to form the sulfide of the wax-aryl alcohol.

(b) Wax-phenol sulfide prepared by the procedure described under Type-Compound I is to be converted to the phenate by reaction with sodium butylate, followed by reaction with chlorhydrin or other halogenated alcohol at a temperature of about 200 F. during a two-hour period with stirring. The mixture is then waterwashed or dry-filtered to remove sodium chloride and any solvents removed by distillation to obtain the wax-aryl ether alcohol derivative.

In order to form the metal alcoholates of Type-Formula III, the wax-aryl alcohol sulfides prepared as above described are to be reacted with metallic sodium in an amount equivalent to the hydroxyl value of the compound. In order to form the alcoholates of polyvalent metals, the sodium alcoholate is to be reacted with a soluble inorganic or fatty acid salt of the desired metal and then dry-filtered through Hi Flow" to remove sodium chloride formed by the double decomposition and obtain thereby the purified product.

TYra-Courounn IV Metal salts of war-hydrozyaromatic acid sulfides Compounds of this type, which are typified by the Formula IV (a) ,may be obtained by reacting the alkali metal phenate-carboxylate salt of a wax-substituted hydroxyaromatic acid with a sulfur halide to obtain the corresponding alkali metal "carboxylate salt of wax-hydroxyaromatic acid sulfide. The corresponding salt of a. polyvalent metal can be obtained by double decomposition. The sodium salt of the wax-phenolic acid, for example, such as obtained by the carboxylation procedure described in my aforesaid application, may be used. such salt being obtained from the carboxylation or Kolbe synthesis in solution in mineral oil. A typical reaction mixture for obtaining the stannous carboxylate salt of wax-phenolic acid disulfide is as follows:

Parts by weight Sodium phenate-carboxylate salt of waxphenolic acid (316) Mineral oil diluent for the sodium salt--- 300 Sulfur monochloride 9.8 Anhydrous stannous chloride 14 A preferred procedure to be followed is to dilute the sodium salt of wax-phenolic acid and mineral oil with 100 parts by weight of butanol, followed by addition of the sulfur halide at a temperature in the neighborhood of 100 F. and at a rate sufficiently slow that the heat of reaction will not cause appreciable rise in tempera ture. The sodium carboxylate salt of the waxphenolic acid disulfide is formed at this stage of the reaction. To form the stannous salt, the stoichiometric equivalent (or excess) of anhydrous stannous chloride in solution in about 50 parts by weight of butanolis added and the mixture heated to the reflux temperature over a sufficient period of time (about 1 hour) to complete the reaction.

Sodium chloride is formed in this reaction, and it can be completely removed by first distilling suflicient alcohol so that about 100 parts by weight remain. About 10 parts by weight of water are added, and the mixture is heated to a temperature of about 200 F. and stirred for a substantial period of time, depending upon the rate of stirring, the size of the batch. etc. Normally about 3 hours are sufficient. The alco- 1101 and water are then distilled off and the reaction product filtered through a suitable filter aid such as Hi Flo, followed by steam-treating at 250 to 300 F. to remove all traces of the alcohol. A current of nitrogen may then be passed through the mixture while it is cooled to remove the steam vapors and yield the finished product, which with the reaction mixture and procedure given above is about a blend of the stannous carboxylate of wax-phenolic acid disulfide in mineral oil.

Compounds of Type-Formula IV(b) are prepared from the same base materials used in the preparation of compounds of Type-Formula IV(a). A typical reaction mixture for obtaining the stannous phenate-stannous-carboxylate salt of wax-phenolic acid disulflde is as follows:

Parts by weight Sodium phenate-carboxylate salt of waxphenolic acid (3-16) 100 Mineral oil diluent 300 Sulfur monochloride 9.8 Anhydrous stannous chloride 28 Sodium (as sodium butylate)- 2.9

In order to completely remove sodium chlo-' ride from the reaction mixture, the mixture is desalted and filtered as described in the preparation of the stannous carboxylate salt.

acted with phosphorus An excess of stannous chloride can be used to advantage in preparation of the stannous phenate-stannous carboxylate salt, resulting in the formation of clear filtrates after the desalting procedure, whereas the use of sodium butylate in excess of the stannous chloride should be avoided as there is a tendency to produce turbid filtrates after desalting with water in an alkaline medium.

Tyre-Couscous V Metal salts of waz-hydroxyoromatic aliph tic acid sulfides Compounds of Type-Formula V are obtained from wax-hydroxyaryl aliphatic acids, the preparation of such acids having been described in my aforesaid application by the reaction of waxphenols with unsaturated or halogenated aliphatic acids. The free acid or sodium salt thereof is sulfurized by reaction with a sulfur halide, followed by conversion of the wax-hydroxyaryl aliphatic acid sulfide to the desired metal salt by Procedures described in the preparation of the compounds of Type IV.

A typical reaction mixture for obtaining the stannous carboxylate salt of wax-phenol stearic acid disulflde of Type-Formula We) is as follows:

Parts by weight sodium phenate-sodium carboxylate salt of wax-phenol stearic acid (8-14) 100 Mineral oil diluent 300 Sulfur monochloridc..- 5.1 Anhydrous stannous chloride l. 3

For the preparation of the stannous phcnatestannous carboiwlate salt of wax-phenol stearlc acid disulflde of Type-Formula V(b), the stannous carboxylate is further treated with ston nous chloride and sodium butylate in an amount equivalent to the hydroxyl value of the compound.

The sodium chloride tamed y double decomposition in the preparation of metal salts of the wax-hydroxyaryl aliphatic acid dinilfldcs can be separated by filtering through "Hi Flow without desalting the mixture with water.

Tarn-Comm VI Metal salts of wcr-mercopto aromatic acid sulfides The wax-mercaptoaromatlc acid sulfides are prepared from the wan, and wax-hydroxyaryl aliphatic scidsuliide'c, preparatlon of the latter compounds having been described under compounds of Types IV and V.

' cedures described in my aforesaid The wax-hydroxyaryl acid sulfides are ren ntasulnde whereby the group is convcrtedto the mercaptan (-8111) group, followed by conversion to the desired metal salts by procedures described under preparation of ype-Compounds IV and TYrs-Courom VII Metal salts of wax-arr! acid sulfides In my aforesaid application, methods are given for the preparation of wax-aryl carboxylic acids with the carboxyl group attached either directly to the aryl nucleus or as an aliphatic side chain substituent. For the preparation of the waxaromatic acids with the carbcxyl group attached directly to the arylnucleus, an additional method of preparation has been developed, consisting in conversion of a wax-hydroxyaromatic acid to the wax-aromatic acid by reacting the hydroxyl group with PCIs whereby the hydroxyl group is replaced by a (Cl) group, followed by removal of the halide group by reduction, whereby the wax-aromatic carboxylic acid is obtained.

By sulfurizing the wax-aryl carboxyllc acids containing either a nuclear or aliphatic side chain carboxyl, with sulfur halides, by the standard procedure described under compounds of Type-Formula IV, the wax-aryl carboxylic acid sulfides can be obtained.

In case polyvalent metal salts are desired, the wax-aryl carboxylic acid sulfides may be treated with an'equivalent amount of aqueous caustic, followed by double decomposition with an aqueous solution of an inorganic salt of the desired metal; or the metal salt may be prepared in non-aqueous medium by treating the free acid with sodium alcoholate, followed by double decomposition with an alcohol solution of an inorganic salt of the desired metal. The metal salt is then purified by water-washing or by dry-filtering through Hi Flo. In case alkali salts of the wax-aryl carborwlic acids are desired as the end product, it is preferred to prepare such compounds in non-aqueous medium in order to avoid formation of water emulsions.

Tyr s-Comm VIII Metal salts of was-owl ether acid sulfides The wax-aryl ether acids are prepared by proapplication, i'ollowcd by sulfurizing the free acids or alkali metal salts thereof by reaction with a sulfur halid to form the wax-aryl ether acid sulfides. from which the metal salts are derived to form Type-Compounds VIII.

Wax-aryl ether alkyl thio acids are also to be prepared by the reaction of wax-alkali phehates with ethylene sulfide to form the wax-aryi ether slkyl hydrosulfide, followed by reaction with sodium chloracetate or the sodium salt of other halogenated acids to form the wax-am ether alkyl thioacid. Sulfur is to be then introduced into the aryl nucleus by reaction with sulfur halides as above.

'Ihe alkali metal and polyvalcnt metal salts of the ether acids are prepared by the standard procedure described under Type-Compound VII.

Tran-Comm 1! Metal derivatives of war-ml Iccto sulfides In the preparation of wax-cry! kcto sulfides of ype Zia), wax-naphthalene is to be sulturiled by reaction with a sulfur halide, followed by condensation with phthalic anhydrlde by the procedure described in my aforesaid application for the condensation of wax-naphthalene with phthalic anhydride, followed by conversion to the metal salt.

As an example of the preparation of Type- Compound xw), wax-benzoic acid sulfide is to be prepared by the procedure described under Type-Compound VII, followed by reaction with thionyl chloride to form the acid chloride and then condensed with wax-phenol in the presence of sumcient A161: to form the wax-hydroxyaryl keto sulfide. The phenolic (-OH) group will then be converted to the (-01!) group by procedures described under Typ Compound I.

In the preparation of Type-Compound xm, a sulfide of wax-benzoic acid is to be condensed with an acid chloride to introduce the keto group, followed by conversion of the sulfide of the wax-keto acid to the metal carboxylate salt.

TYrs-Coisromvn X Metal derivatives of war-am! ester sulfides Pres-Comm 21 Metal salts of wax-ml sullonic acid sulfides The wax-aryl sulfonic acids are to be prepared by methods described in my aforesaid application and sulfurized by reaction with sulfur halides, followed by conversion to metal salts by methods used in the preparation of metal salts of carboxylic acids, to form compounds of typeformulae in group XI.

Turn-'Conromm xn Metal salts of war-cry! amine sulfides The type compounds represented by the formulae in group xn are prepared by sulfnrlzing the wax-aryl amines by reaction with elementary sulfur at a temperature of about 300' I"., followed by conversion to the metal salts by procedures outlined in my aforesaid application.

'i'rrs-Courom 1111 Metal salts of sulfides of roam-owl amino acids Wax-aryl carbonlic acids prepared by pro cedures described in my aforesaid application,

are nitrated by reaction with nitric acid and reduced by methods used in the reduction of arcmatic nitro compounds in general, to form the wax-aryl amino acids. The sulfides used in the preparation of Type-Compounds mm) (b) are prepared by reaction of the wax-aryl amino acids with elementary sulfur at a temperature of about 300' 1".

A highly important class of compounds of Type min), (b) are the inorganic acyl derivatives. particularly those of phosphorus and silicon. which are preparedby reaction of the sulfide of the wax-aryi amino acids with phosphorus trichloride or silicon tetrachloride, followed by conversion of the inorganic acyl compounds to the metal salts.

By sulfurizinz the wax-aryl amino acids by reaction with sulfur halides instead of elementary sulfur, compounds predominantly of the type represented by Type-Formulae 1311(0), (d) are obtained, wherein an N-thio group is formed.

By reaction ofthe sulfurlzed wax-aryl amino acids, above described, with a metal alcoholate in an amount equivalent to the carboxyl content, compounds of Type 3111 (or), (in), (c), (d) are formed. By use of sufiicient metal alcoholate, compounds of Type xlllmz) (in) can be formed, wherein both the carboxyl and amino groups are substituted with metal.

Reactions generally applicable to the substitution of carbonyl hydrogen with metal can be used in the preparation of metal salts from sulfides of the appropriate wax-aryl amino carboxylic acids to form Type-Compounds XIIHm) (in), (c), (d).

Trrs-Coilromm XIV Metal salts of sulfides of war-arm diazo compounds By dlazotizing the wax-aryl amines sulfides described under type-compounds XIII, the disco group (-N=N)' may be introduced from which double salts represented by xrva can be prepared by reaction with inorganic metal salts.

By reactions well-known to the art, the product resulting from the diazotization may be converted to compounds of the general formula (N=NA) wherein Amay be (-OH) (-SH): (-80:H--); cx'xnfrom which metal salts of Type XIVia) may be derived.

Trrs-Courom XV Metal salts of sulfides of war-owl hudrazines This method is also applicable to Type-Com poimds xva where the nitrogen is in the side chain. Thehydraainesofthistypearetobe converted to the sulfide derivatives and metal salts thereof as described above.

'lrrs-Courom XVI Metal salts of sulfides o! wax-cry! carbamldes By the reaction of wax-aryl amine sulfides, prepared as described under Type-Formula XIII,

with carbon disulfide in alkaline medium, the sulfides of wax-aryl carbamides can be formed.

Compounds of Type XVI are prepared therefrom by reaction with metal alcoholates, whereby the metal substituent is introduced.

TYPE-COMPOUND XVII Metal salts of sulfides of wax-aryl amides Compounds of Type-Formula XVlI(a), (b), (c) are to be prepared from the sulfides of waxaryl acids, the latter having been described under Type-Compounds IV, V, VII, and VIII. The waxaryl acid sulfides are to be reacted with thionyl chloride to form the acid chloride, followed by reaction with ammonia or primary amines to form the sulfide of the wax-aryl amide derivative, and then converted to the metal salts by procedures described under Type-Formula XII.

Compounds of Type-Formulae XVIHdi), (dz) are prepared from the sulfides of wax-aryl amines described under Typ Formula XII. The waxaryl amine sulfides are reacted with organic or inorganic acid chlorides to form the amide followed by conversion to metal salts. The inorganic acyl derivatives, particularly those of phosphorus and silicon, are the most important of this group.

TYPE-COMPOUND XVIII Metal salts of sulfides of wax-oral amtdines Wax-aryl amidine sulfides are to be prepared from the sulfides of wax-aryl amides by reactions well-known to the art for the conversion of amides to amidines, whereby the oxygen or suliur of the amide is replaced by (NH) or (NR"). From the sulfides of the wax-aryl amidines, salts of the amine type are to be prepared to give compounds of Type-Formula XVIII.

Tree-Couscous XIX Metal compounds of sulfides of wax-aw! oximes An example of a wax-aryl aldehyde suitable for the preparation of Type-Compound XIXM) is wax-phenol aldehyde, which can be prepared by reaction of wax-phenol with chloroform in the presence of caustic.

Wax-aryl ketones suitable for the preparation of Type-Compound XIXM), can be prepared by the reaction of wax-aromatic hydrocarbons with acid chlorides.

Wax-aryl cyanides for use in preparation of Type-Compounds XIXUJ) are to be prepared by the chlorination or bromination of wax-aromatic hydrocarbons, whereby the halogen is introduced in the side chain, followed by reaction with alkali cyanide to form the (-CN) group.

The wax-aryl aldehydes, wax-aryl ketones, and

wax-aryl cyanides described herein are to be sul-" furized by reaction with a sulfur halide, followed by reaction with hydroxylamine to form the waxaryl oxime and then converted to the metal derivative to form Type-Compound XIX.

Titre-Commune xx Additive compounds of inorganic metal salts with sulfides of war-aromatic compounds Type-compounds represented by xxm) are to be prepared by the reaction of sulfides of waxaromatic compounds with metal halides, such as BnCli, HgCl-z, AszCh, etc., whereby compounds are formed by addition. Since aliphatic sulfides are known to form additive compounds with inorganic metal salts, the sulfides of wax-aromatic compounds containing aliphatic sulfide substituents are also to be reacted with inorganic metal halides to form additive compounds.

In the preparation of Type-Compounds XXGJ), the metal salt of the sulfide of the waxaromatic compound is to be prepared first by double decomposition as described above under Type-Compounds I to XIX inclusive, followed by reaction with inorganic metal halides to form the additive metal group.

In the foregoing description oi methods of preparation of type-compounds of Table I where X represents oxygen or sulfur, examples have been given which generally illustrate the preparation of only oxy groups. In Type-Compounds II and VI it has been pointed out that the (-OH) group can be converted to the (-SH) group by reaction with P285. Under Type-Compounds VIII, a method has been given for the formation of thio-carboxylic acids and metal salts thereof. For the conversion of the carboxyl group to the thiollc group, reaction with hydrogen sulfide is the general procedure: or the carboxyl group can be converted to the acid chloride by reaction with thionyl chloride, followed by reaction with sodium sulflde to form the corresponding thiollc acid. For the conversion of an amide group to the thioamide; or the conversion oi a keto group to the thioketo group, reaction with hydrogen sulfide is also applicable. In some cases the sulfur group is formed directly, instead of by conversion indirectly from the oxy group. For example, the xanthic acids are formed by reaction of the alkali phenates or alcoholates with carbon disulfide. 'Ihioamides can be formed by the reaction of wax-aryl oyanides with hydrogen sulfide. But in general the methods applicable to the formation of wax-aryl thio derivatives of Table I are well understood by those skilled in the art.

Numerous compounds or condensation products falling within the broad general class contemplated herein have been synthesized and testedin mineral oil fractions of the viscous or lubricant type; and where the alkyl group R of General Formula I has been derived from petroleum wax (a mixture of high molecular weight aliphatic hydrocarbons having a chain length oi at least 20 carbon atoms). such compounds or condensation products have been found to he possessed of multifunctional oil-improving properties in that they efiect improvement in at least two of the following properties 0! the oil: namely, pour point, viscosity index, and inhibition of oxidation, the oxidation-inhibiting action being evidenced by reduced acid formation in the oil and a reduction in the tendency of internal combustion engine lubricants to cause ring-sticking, etc. These products may, be used in viscous mineral oil fractions in varying amounts ranging from 5 per cent to 10 per cent, depending upon the oil, the conditions of use, and the property or properties which are to be emphasized in the oil blend. As aforesaid, the addition agents contemplated herein lend themselves to a wide variety of applications and their properties may be varied by using different metal substituents, varyim the degree of substitution with metal, varying the degree of alkylation, varying the Y substituents and varying the aryl nucleus. In Table ILhelow we have listed a number of typical been synthesized and have been demonstrated to have multifunctional oil-improving properties.

TABLE II Cobaltous phenate of wax-phenol disulflde. Stannous phenate of wax-phenol disulflde. Aluminum phenate oi wax-phenol di'sulflde. Sodium phenate of wax-phenol disuliide. Cobaltous phenate of wax-phenol monosulfide.

Stannous naphtholate of wax-naphthol disulfide.

Stannous salt of wax-amino phenol sulfide.

Stannous carboxylate of wax-phenolic acid monosulfide.

Stannous phenate-stannous carboxylate of waxphenolic acid monosulfide.

Aluminum carboxylate of wax-phenolic acid monosulflde.

Aluminum phenatee-aluminum carbcxylate of wax-phenolic acid monosulflde.

Zinc carboxylate of wax-phenolic acid monosulfide.

Zinc phenate-zinc carboxylate of wax-phenolic acid monosulflde.

Chromium carboxylate monosulfide.

Chromium phenate-chromium carboxylate of wax-phenolic acid monosulfide.

Cobaltous carboxylate of wax-phenolic acid monosuli'lde.

Cobaltous phenate-cobaltous carboxylate of waxphenolic acid monosulfide.

Nickelous carboxylate of wax-phenolic acid monosulfide.

Nickelous phenate-nickelous carboxylate of waxphenolic acid monosulflde. Stannous carboxylate of wax-phenolic acid tetrasulflde. Stannous phenate-stannous carboxylate of waxphenolic acid tetrasulflde.

Stannous carboxylate of wax-alpha-naphtholic acid monosnlfide.

Stannous naphtholate-stannous carboxylate of wax-alpha-naphtholic acid monosulflde.

Stannous carboxylate of wax-naphtholic acid disulfide.

Stannous naphtholate-stannous carboxylate of wax-naphtholic acid disulfide.

Stannous carboxylate of ethanol xanthate of wax-phenolic acid disulflde.

of wax-phenolic acid Stannous carboxylate of wax-phenol stearic acid Stannous phenate-stannous carboxylate of waxphenol stearic acid disulflde.

Stannous carboxylate of wax-phenoxyphenyl stearic acid disulflde.

Cobaltous carboxylate of wax-phenoxyphenyl stearic acid disulflde.

Stannous carboxylate of wax-phenoxy acetic acid disulflde.

Stannous carboxylate of phthalyl ester of waxphenolic acid disulfide.

Stannous carboxylate of wax-naphthyl stearic acid disulflde.

Stannous carboxylate of wax-methoxybenzoic acid disulflde.

Stannous salt or wax-aniline sulfide Stannous salt of wax-amino phenyl stearic acid sulfide.

All of the products listed in the above table can be broadly identified as oil-miscible metalorganic compounds which are characterized by the presence of at least two slim-substituted aryl nuclei which are interconnected by at least one atom of sulfur. These sulfur condensation products, as aforesaid, constitute the preferred class of oil addition agents coming within the scope of my invention, but it is again emphasized til that my invention contemplates the related derivatives of selenium and tellurium.

It is to be. understood that certain of these compounds or compositions may be preferred for use in certain mineral oil fractions and that certain of the compounds or compositions may be preferred to others, depending upon the conditions or properties which are to be improved, but it is, as stated above, a characteristic of all of the preferred products wherein the allryl substituent is derived from a wax such as petroleum wax that they have multifunctional oilimproving properties which may vary in magnitude and character with the oil and constituents of the compounds. Some of these compounds or condensation products falling into the various sub-groups may be preferred to others from the standpoint o1 cost, ease of synthesis, odor, color, etc., but it is not my intention in the present application to draw any preferential differentiation or distinction between the various sub-groups since they are being made the subject matter of aditional applications. It is emphasized, therefore, that the invention is not limited to the specific examples or illustrative procedures described above but includes within its scope such variations and modifications as fairly come within the spirit of the appended claims.

I claim:

1. A mineral oil composition comprising: a mineral oil fraction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound characterized by the presence of at least two wax-substituted aryl nuclei interconnected by at least one atom of an element selected from the group consisting of sulfur, selenium, and tellurium.

2. A mineral oil composition comprising: a mineral oil fraction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound characterized by the presence of at least two wax-substituted aryl nuclei interconnected by at least one atom of sulfur.

3. A mineral oil composition comprising: a

viscous mineral oil fraction and in admixture therewith an oil-miscible metalorganic compound which is characterized by the presence of at least two wax-substituted aryl nuclei interconnected bY at least one atom of an element selected from the group consisting of sulfur,

selenium, and tellurium, said metalorganic comwith from about per cent to about 10 per cent of an oil-miscible metalorganic compound characterized by the presence of at least two wax-substituted aryl nuclei interconnected by at least one atom of an element selected from the group consisting of sulfur, selenium, and tellurium.

5. A mineral oil composition comprising a viscous mineral oil fraction and in admixture therewith an oil-miscible metalorganic compound which is characterized by the presence of at least two wax-substituted aryl nuclei interconnected by at least one atom of sulfur, said metalorganic compound being present in the oil in an amount sufficient to improve the oil in at least two of the following respects: improvement in pour point; improvement in viscosity index; and inhibition of oxidation products.

6. A mineral oil composition comprising a viscous mineral oil traction and in admixture therewith from about per cent to about 10 per cent of an oil-miscible metalorganic compound characterized by the presence of at least two waxsuhstituted aryl nuclei interconnected by at least one atom of sulfur.

'1. A mineral oil composition comprising: a mineral oil traction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound characterized by the presence of at least two wax-substituted aryl nuclei interconnected by at least one atom of an element selected from the group consisting oi sulfur, selenium, and tellurium and the metal being present in at least one substituent on the aryl nucleus selected iron the group consisting of:

RM (NEDXM): (-F C (N mxM);

/RII M (-N(R"):.Ma) (R'N(R"):|.Mn) (-C(NR")-N(R")2.Mn) (--N=N.Ms); and (--NR."-N(R")5Mn) wherein M represents the hydrogen equivalent of a metal; R. is selected irom the group consisting of aryl, aralkyl, alkyl, and alkaryl; R" is selected from the group consisting of hydrogen, alkyl, and aryl: x, X and X" represent elements selected from the group consisting of oxygen and sulfur; A is selected from the group consisting of (-X-): (NR"-): (-CX'X): and (409-); and Mn represents an inorganic metal compound.

8. A mineral oil composition comprising: a mineral oil traction and in admixture therewith a minor proportion of an oil-miscible metalorganic condensation product characterised by having at least once the A general formula in which '1 represents an aromatic nucleus: It represents at least one alkyl group corresponding to an aliphatic hydrocarbon of the type characterizing petroleum wax; ZM represents at least one metal-containing group wherein M represents the hydrogen equivalent of a metal and Z represents a radical selected from the group consisting of oxygen, sulfur, selenium, tellurium, and

wherein R. is selected from the group consisting of aryl, aralkyl, alkyl, and alkaryl: R" is selected from the group consisting of hydrogen, alkyl, and aryl; X, X and x" represent elements selected from the group consisting of ougen and sulfur: and A is selected from the group consisting oi (X-- (-CX'X-l, and (-SOa-i; Y of said general formula is selected from the group consisting of hydrogen, hydroxyl, ester, keto, alkoiw, alkyl sulfide, aroxy, ether alcohol, aldehyde, thioaldehyde, aldime, oxime, amide, thioamide, carbamide, aralkyl, aryl, alkaryl, halogen, nitroso, amino, nitrosamine, amidine, imine, N-thio. diazo, hydrazine, cyano, azcxy, azo, and hydrazo radicals; n represents an element selected from the group consisting oi sulfur, selenium, and tellurium; and n represents a whole number from one to tour.

9. A mineral oil composition comprising: a mineral oil traction and in admixture therewith a minor proportion 01' an oil-miscible metalorganic compound characterized by the presence 01' at least two alkylated aryl nuclei in which the alkyl substituents contain at least twen y carbon atoms, said nuclei being interconnected by atleast one atom of an element selected from the group consisting of sulfur, selenium, and tellurium.

10. A mineral oil composition, comprising: a mineral oil fraction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound characterized by the presence of at least two alkylated aryl nuclei in which the alkyl substituents contain at least twen y carbon atoms. said nuclei being interconnected by at least one atom of sulfur.

11. A mineral oil composition comprising: a mineral oil fraction and in admixture therewith a minor proportion, irom about k per cent to about 10 per cent, of an oil-miscible metalorganic compound characterized by the presence oi at least two alkylated aryl nuclei in which the ailgvl substituents contain at least twenty carbon atoms, said nuclei being interconnected by at least one atom of an element selected from the group consisting of sulfur, selenium, and tellurium.

12. A mineral oil composition comprising: a mineral oil traction and in admixture therewith a minor porportion, from about h per cent to about 10 per cent, of an oil-miscible metalorganic compound characterized by the presence of at least two alkylated aryl nuclei in which the alkyl substituents contain at least twenty carbon atoms, said nuclei being interconnected by at 5 least one atom of sulfur.

ORLANP M. REIFF.