US2198292A - Mineral oil composition - Google Patents

Description

Patented Apr. 23, 1940 iTE rA'rEN'r orrlce MINERAL on. ooivmosrrron No Drawing.

Application September 14, 1938,

Serial No. 229,876

1? Claims.

This invention has 'to do in a general way with mineral oil compositions and is more particularly related to compositions comprised of mineral oil and a minor proportion of an added ingredient which will improve the oil in one or more important respects.

It is well known to those familiar with the art that mineral oil fractions refined for their various uses are in and of themselves usually deficient in in one or more respects, so that their practical utility is limited even in the particular field for which they have been refined. For example, mineral oil fractions refined for use as lubricants have a tendency to oxidize under conditions of use with 1.3 the formation of sludge or acidic oxidation products; also the lighter fractions such as gasoline and kerosene tend to oxidize with the formation of color bodies, gum, etc. In order to prevent the formation of these products and thereby extend the useful life of the oil fraction, it is common practice to blend with such oil fractions an additive ingredient which will have the efiect of inhibiting oxidation, such ingredients being generally known to the trade as oxidation inhibitors or sludge inhibitors, gum inhibitors, etc.

It is also the practice to add other ingredients to mineral oil fractions for the purpose of improving the oiliness characteristics and wearreducing action of such mineral oils when they 3% are used as lubricants, particularly when the oils are used for the purpose of lubricating metal surfaces which are engaged under extremely high pressures and at high rubbing speeds.

Other ingredients have been developed for the 35 purpose of depressingthe pour point of mineral oil fractions which have been refined for use as lubricants, such refinement leaving a certain amount of wax in the oil, which, without the added ingredient, would tend to crystallize at 4o temperatures which render the oil impracticable for use under low temperature conditions. Additive agents have also been developed for improving the viscosity index of lubricating oil fractions. In the case of internal combustion en- 45 gines, particularly those operating with high cylinder pressures, there is a decided tendency for the ordinary lubricating oil fractions to form, under such conditions of use, carbonaceous de- 5 posits which cause the piston rings to become stuck in their slots and which fill the slots in the oil ring or rings, thus materially reducing the efficiency of the engine. Ingredients have therefore been developed which, when added to the oil, will reduce the natural tendency of the oil to form deposits which interfere with the function of the piston rings. Aside from the corrosive action which attends theformation of acidic products of oxidation in mineral oil fractions of the lubricant range, it 5 has been discovered that certain types of recent- 1y, developed hard metal alloy bearing metals, such as cadmium-silver alloy bearings, are attacked by ingredients in certain types of oils, particularly oils of high viscosity index obtained by various methods of solvent refining. This corrosive action on alloys of the above type has led to the development of corrosion inhibitors which may be used in solvent-refined oils to protect such bearing metals against this corrosive action.

In the lighter mineral oil fractions. such as those used for fuel purposes, particularly in internal combustion engines, it has been found that the combustion characteristics of the fuel may be controlled and improved. by adding minor proportions of various improving agents thereto.

The various ingredients which have been developed for use in mineral oil fractions to improve such fractions in the various respects enumerated above are largely specific to their particular applications, and it has therefore been the practice to add a separate ingredient for each of the improvements which is to be effected.

It is a primary object of the present invention to provide a mineral oil composition which has been improved in one or more of the various properties enumerated above by the incorporation therein of a small quantity of a multifunctional compound selected from that group or class of metal-organic compounds which may be designated as the oil-soluble or oil-miscible metal salts of alkyl-substituted aryl ether acids. More specifically our invention contemplates as oil-improving agents the oil-miscible metal salts of alkyl-substituted aroxy aliphatic acids and alkylated aroxy-aromatic acids in which the hydrogen of the carboxyl group or groups is substituted with metal. We have discovered that metal salts of alkylated aryl ether acids of the general class above referred to may be added in small quantities to mineral oil fractions to form mineral oil compositions or blends superior to the unblended fractions in one or more important respects, and the present invention, therefore, is broadly directed to a mineral oil composition containing a 50 compound falling into the general class referred Our invention has as a further and more specific objectthe provision of a viscous mineral oil fraction which has been improved in one or more of the foregoing recited respects by having incorporated therein a minor proportion of an oil- Iniscible metal salt of an alkylated aryl ether acid.

The oil-improving; agents contemplated by this invention may be considered as alkylatedxhydroxyaromatic compounds in which the hydroxyl hydrogen is replaced with an organic acid groupsuch as an aromatic acid group or an aliphatic acid group in which acid group the carboxyl hydrogen is substituted with its equivalent weight of metal. The compounds or products which are preferred, particularly from'a standpoint of synthesis, may be considered as alkylated hydroxyaromatic compounds in which the hydroxyl hydrogen is replaced with an alkyl or aryl metal carboxylate group. Compounds or compositions of this type are characterized by the presence of an aromatic nucleus in which at least one nuclear hydrogen has been substituted with an ether acid or an oxy acid substituent, in which substituent the carboxyl hydrogen has been replaced with its equivalent weight of metal. This characterizing group may be represented by the formula: T (O.Z.COOM) in which T represents an aromatic nucleus; and (O.Z.COOM) represents at least one ether acid or oXy acid substituent in which Z represents an aromatic or aliphatic group having at least one carboxyl group, the hydrogen of whichis replaced with its equivalent weight of a metal M.

The metal salts of arylether acids of the type corresponding to the group represented by the above formula which are otherwise unsubstituted are not, in general, miscible with mineral oil, and it is, therefore, important that the improving agents containing the above characterizing group have additional nuclear hydrogen replaced with substituents of an oil solubilizing nature. In other words, it is important that the aryl nucleus T carry a substituent or substituents which will render the composition as a whole miscible with mineral. oil fractions. By the terms oil-miscible or oil-soluble as they are used herein, we have reference to that property of remaining uniformly dispersed in the mineral oil fraction either as a true solution or as a colloidal suspension during normal conditions of handling and use.

The improving agents contemplated by this invention are'characterized by the presence of alkyl substituents directly or indirectly substituted in the aryl nucleus T, and the improving agents preferred for use in viscous mineral oils are further characterized by the presence of 'alkyl or aliphatic substituents in the aryl nucleus T which will give other properties to the composition as a whole in addition to oil-miscibility. We have found, for example, that where this aryl nucleus is substituted with one or more aliphatic groups corresponding to certain aliphatic hydrocarbon compounds of relatively high molecular weight (such as aliphatic groups having at least. twenty carbon atoms, herein referred to as heavy alkyl groups), a com-- pound or composition can be obtained which will effect marked improvement in the viscosity index and the pour point as well as other important properties of viscous mineral oils.

As a general proposition, therefore, it may be said that the improving agents contemplated by this invention are metalsalts of aryl ether acids having the characterizing group T(O-Z-COOM) described above, in which additional hydrogen on the aryl nucleus T is replaced with an oilsolubilizing substituent such as a predominantly aliphatic material, suchsubstituent comprising a suflicient proportion 'of the composition as a whole to render the same miscible with mineral oil fractions under normal. conditions of handling and use. As a further generalization, it may be said that at least one point on the aromatic nucleus T, and preferably two or more points on such nucleus, are substituted with aliphatic hydrocarbon radicals or groups, such aliphatic radicals or groups preferably being high molecular weight aliphatic derivatives or heavy alkyl groups.

The simplest type of compound satisfying the above requisites may be represented by the formula:

in which R represents at least one aliphatic hydrocarbon radical or group, such group or groups preferably corresponding to relatively high molecular weight aliphatic hydrocarbons and being attached to a mono or poly cyclic aromatic nucleus T and in which (O-Z-COOM) is as indicated above.

In addition to the aliphatic or alkyl substituent R, the compounds or compositions contemplated herein as mineral oil-improving agents may have additional nuclear hydrogen of the aryl nucleus T replaced with other substituents which may or may not have a solubilizing effect upon the composition as a whole. Such a compound in its simplest 'form may be represented by the formula:

in which R, T, and (O-Z-COOM) have the same significance indicated above and in which Y represents residual hydrogen of the aryl nucleus T which may be replaced by a radical from the group consisting of: chlorine, alkoxy, aroxy, aralkyl, alkaryl, aryl, nitro, and amino radicals or groups. Compounds of the above general formula-type having mono, di, and hi cyclic nuclei are illustrated by the following specific formulae:

in which at least one R represents an aliphatic radical or group, preferably a heavy alkyl group,

cals or groups in which the several valences are attached to separate aromatic nuclear groups T.

Compounds of this type are included under the following general formula representation:

in which T and (O-Z-COOM) have the same significance indicated above; R represents at least one aliphatic or alkyl radical or group, such alkyl group or groups being attached by one valance only to at least one aromatic nucleus T, 0 representing the valence of the aliphatic radical R", which may be one to four; Yb represents a monovalent element or group selected from the class identified above in connection with Y; b represents the number of Y's and is equal to zero or a whole number corresponding to the valences on the nucleus T not satisfied with R and (O-Z-COOM); and n represents a whole number from one to four and indicates the total number of groups (T(O'Z'COOM)Yb) present in the molecule represented by the formula which are attached to the aliphatic group or groups represented by R through the valences v.

In the foregoing general formula representation III it will be seen that the compounds represented thereby include those materials in which all of the aliphatic substituent is monovalent (12:1 and n=1) or in which all of the aliphatic substituent is polyvalent (v and n being equal to two, three, or four); or since R" is defined as being at least one aliphatic radical or group and may therefore include several'such groups, it will be seen that this general Formula 111 is inclusive of compounds I having aliphatic groups or radicals of different valences (from onev to four) in the same molecule. Also it will be observed that since 12 may be any whole number from one to four, the number of aromatic nuclei T in the molecule may likewise vary from one to four. It will be seen, therefore, that the relationship between n and v in Formula III, in its broadest aspect, is such that when n is=equal to one, 1) is equal to one; and when n is greater than one, the valence v of at least one of the its is equal to n (in 0rd to tie the several nuclei or T's together), the valence of any'remaining R's being any whole number equal to or less thann.

As stated above, and as will appear more fully later on from the description of their synthesis, these materials represented by general Formula III may contain both monovalent and polyvalent aliphatic substituents. Both the polyvalent ali- Dhatic substituent and the monovalent substituent, if both are present, may be introduced in the nucleus as part of an alkylation reaction, or all or part of the monovalent aliphatic substituent' may be present in the nucleus of a hydroxyin which T and (O-Z-COOM) have the same significance as indicated above; R represents at least one polyvalent aliphatic radical or group having a valence o of two, three, or four; Yb indicates the same group of substituents as described above for Y; Re represents monovalent :1 aliphatic radicals or groups; b represents the number of Yw's and is equal to'zero or a whole number corresponding to the valences on the nucleus T not satisfied with R (O-Z-COOM) and Re; 0 indicates the number of Re's and is equal to zero or a whole number corresponding to the valencebonds on the nucleus T not satis-v fied with R (O-Z-COOM) and Yb'; and n represents a whole number from two to four and indicates the total number of the groups present in the molecule represented by the formula which are attached to the aliphatic group or groups represented by R"' through the valances v.

In the above general Formulae III and IV it will be understood that since R and R are aliphatic hydrocarbon radicals of the chain type and are each attached by one valence bond only to each corresponding aromatic nucleus, the valence v or v of such radical or radicals is of necessity never greater than the number n, which indicates the number of aromatic nuclei in the molecule and in Formula III is always. equal to one when n equals one. Otherwise an R. or an R having a valence greater than the number (n or n) of aromatic nuclei would either have some of its valence bonds unsatisfied or else would form a condensed ring or rings .by attachment at two or more points to one and the A. O.Z.CO0M

H H C "CH H II In the aboveformula the chain represents the il-solubilizing alkyl substituent (R and Yb and (O-Z-COOM) have the same significance as has been heretofore given to these groups.

Since group R has been defined as at leastone, it will be apparent that there may be more than one heavy alkyl substituent attached to the nucleus T. Such a compound, where v and n are each onev and in which there are two. such monovalent R groups, may be represented by the following formula:

in which the chainsand the substituent characters have the same significance defined above;

Compounds of the type satisfying the general Formula III and the subgeneric Formula IV inwhich R (or R f) is polyvalent and v (or v) and n (or n) are more than one and in which there is only one such polyvalent R group may be illustrated by the following formula, in which the aryl nucleus T is again indicated for illustration as being monocyclic:

to.z.oooM

In the above formula C, Re is a monovalent alkyl group as defined above under Formula IV and is the same as monovalent'R. in Formula III.

Under this same type of compound indicated by Formula C there may also be more than one polyvalent R. group (represented by the chain), such a compound in which there are, for example, two polyvalent R" groups being illustrated by the following formula, in which thercharacteriz- 'ing groups have the same significance described above under FormulaC.

1). H H B.- H H Ho --o --o --o --CH H V l H 0.Z,COOM o.z.ooo1vr 0.Z.COM Y.-@-R kw-11, Yi-""' -R H H Ho --o --o --o --oH H H H H H The possible molecular structure of compounds in which the aryl nucleus '1- is polycyclic will be obvious from the foregoing exemplary Formu-- E. H H H H H Ho --o --o --o --cH H H o.z.oo0M o-.z.oooM 0.Z.OO0M

Y;B. Yv--- a. in- R.

H H 110 --c --o --oH H H H- H As to the possible number of R" and (Re) groups going to make up a single molecule, this will vary with the extent to which it is desired to effect substitution of the nucleus with oilsolubilizing aliphatic groups for obtaining the desired properties in the product and is, of course, limited by the number of valences on the arcmatic nucleus which are available for substitution. As will be apparent to those skilled in the art, the maximum possible number of R (and Re) groups which can be attached to a single aromatic nucleus will vary as the nucleus is mono or poly cyclic and also as the nucleus is otherwise substituted. It will also be app rent that available valenc'es on the nuclei may all be attached to polyvalent aliphatic substituents.

It will be understood that the oil-improving agents used in the mineral oil compositions contemplated by this invention may be pure compounds satisfying the general Formula 111 described above with any one of the various mono and poly cyclic aromatic nuclei as 'I and the various substituents R (or R and Y) described.

However, in manufacturing the preferred oil-improving product of the present invention by the preferred-method of procedure, as will appear more fully later on, the final oil-improving product obtained is normally or usually a mixture of different compounds corresponding to different values of n and v and to different numbers of aliphatic groups R".

As has been emphasized hereinabove, it is important that the oil-improving agents as represented by general Formulae III and IV have nuclear hydrogen in the aromatic nucleus 'I' substituted with predominantly aliphatic material which comprises a sufficient proportion of the composition as a whole to render the same miscible with the mineral. oil fraction in which the improving agent is used under normal conditions of handling and use. It appears from the results of our research that there is a critical range in the degree of alkylation of these im- ,the alkylated hydroxyaromatic compound from which the alkylated aryl ether acid salt is derived should not exceed a certain percentage of such alkylated hydroxyaromatic composition as a whole. This critical range of alkylation may be roughly expressed as the ratio by weight of (T(OH))n to RV(T(OH))1:. I

The degree of alkylation and the critical ranges within which operative and preferred compounds can. be obtained may also be expressed as the number of carbon atoms contained in the aliphatic substituents for each aryl nucleus in a given molecule or molecular structure.

The critical range in the degree of alkylation of the aryl nucleus in the improving agents contemplated herein may vary with: (a) the mineral oil fraction in which the improving agent is to be used; (b the aryl nucleus T (monoor polycyclic); (c) the hydroxyl content of the aryl nucleus from which the final product is obtained (monoor polyhydric);- (d) the character of aliphatic material comprising the substituent (straight or branched chain) (e) monoor polysubstitution of the aryl nucleus; and (f) other substituents on the nucleus T, which may be of positive or negative or of neutral solubilizing activity.

In general, it may be said that a polycyclic nucleus appears to require a higher degree of alkylation than a monocyclic nucleus; that a polyhydric nucleus requires a higher degree of alkylaand that tion than a monohydric nucleus; branched chain aliphatic substituents have a somewhat greater solubilizing action than straight chain solubilizing substituents.

In view of the foregoing variables, it would be impracticable and probably misleading to attempt to give an expression and figure which would indicate accurately the proper ratio of hydroxyaromatic constituent to the alkylated hydroxyaromatic constituent which would express a degree of aliphatic substitution satisfying all cases taking these variables into account. As a guide for preparing these improving agents, however, our research indicates that for a product having pour depressing and V. I. improving properties in addition to other valuable properties the ratio ment inseveralimportant properties. The imof (T(O Z-COOM)) to R'('I'(O-Z-COOM)) expressed as:

should not be greater than about .20 when the weight of the hydroiwaromatic nucleus or component (T(OH))n is expressed in terms of its chemically equivalent weight of phenol (C6H5OH) However, for mere oil-solubility with inhibition of oxidation we have found that this ratio may be raised to about 0.6 by substituting the nucleus with branched chain aliphatic groups. In general, it may be said that in the preferred improving agents contemplated herein the ratio by weight of the hydroxyaromatic component in the product to the corresponding alkylated hydroxyaromatic nucleus or component therein should not be greater than about twenty parts by weight of the former to about 100 parts by weight of the latter, or about twenty per cent, when the weight of the hydroxyaromatic nucleus or component is expressed in terms of its chemically equivalent weight of phenol. It will be observed that the ratio as represented by the Formula VII does not take into account any other substituent in the nucleus than the aliphatic substituents and the hydroxyl group or groups; but since the aliphatic substituent is primarily relied upon in the agents contemplated herein as the solubilizing substituent, it is believed that the foregoing expression and limits will serve as a working guide for the preparation of oil-soluble materials and the preferred multi-functional materials.

As stated above, the degree of alkylation may also be expressed by the number of carbon atoms contained in the aliphatic substituent for a given hydroxyaromatic nucleus T. As a; general guide here it may be said that the aliphatic substituents represented by 1'1. in the above general Formula III should, for the preferred multifunctional materials contemplated herein, contain a total of atleast twenty-five carbon atoms for each aromatic nucleus T.

The ratio oftwenty per cent, which we may term the phenolic ratio, represents what we consider a maximum figure for the preferred products contemplated herein, and in generalit will be found that for thes preferred multifunctional products this figure will be lower, the actual ratio, of course, being dependent upon the variable factors enumerated above. For example, as will later apear, an improving agent of. the preferred type in which the aliphatic substituent is derived from petroleum wax '(a predominantly straight chain aliphatic hydrocarbon of at least twenty carbon atoms) and in which the aromatic nucleus was derived from phenol otherwise unsubstituted may have a phenolic ratio, as expressed above, not substantially greater than about sixteen per cent.

A further general guide for the synthesis of the prefered improving agents for viscous oils is to alkylate the aromatic nucleus so that it is polysubstituted. with aliphatic hydrocarbon radicals or groups preferably of relatively high molecular weight.

As has been previously indicated, .it is one of the primary objects of the invention to provide an oil-improving agent which will have multifunctional improving activity in a mineral oil. Our research indicates that compounds satisfying the requisites of general Formula III above may be blended in minor proportions with mineral 01] fractions, particularly of the viscous or lubricating oil type, to effect marked improveprovement effected may be varied somewhat with aliphatic substituent, petroleum wax and allphatic hydrocarbons of similar characteristics such as ester wax, for example, giving products which eflectamarked improvement in viscosity index and pour point in addition to other properties to be hereinafter pointed out. The eifectiveness may also be varied with other substituents in the aryl nucleus for example, alkoxy groups contribute to solubility-and the properties of the agents may also be varied with the character of the metal substituent in the carboxyl group.

In general, it appears that the oil-miscible salt of any metal satisfying the requisites of Formula III above will act to inhibit oxidation in mineral oils and-reduce the formation of harmful oxidation products. Certain of the metals, such, for example, as copper, lead, and zinc, may serve to increase the load-carrying capacity of lubricating oils.

Procedures whereby the oil-improving agents contemplated by this invention in which the oxyacid substituent is derived from a fatty acid can be prepared, may be broadly described as follows:

First the hydroxyl hydrogen in an alkylated hydroxyaromatic compound is substituted with an alkali metal to form an alkylated aryl alkali metal oxide:

in which Cl-Z-COOM represents the sodium salt of a chlor aliphatic acid, Z' in this case being an aliphatic group. This reaction may also be expressed as follows:

(12) R (T(oM )Yb)n-|-C1(CnH2n) -000M R"(T(0- (CnHan) -COOM+MC1 Another desirable procedure for the formation of alkali metal salts of alkylated aryl ether acids in which the ether acid substituent is an aliphatic acid derivative consists in reacting anester of the chlor aliphatic acid instead of the alkali salt of the aliphatic acid with the alkylated aryl metal oxide, followed by saponification of the product according to the following equations:

Alkali metal ether acid salts formed in the foregoing exemplary procedures may be obtained with the alkali metal salts of any chlor-aliphatic acid such 'as sodium, chlor-acetate, butyrate, heptylate, palmitate, stearate, etc. It is preferred that the reactions be carried out in the presence of a non-aqueous medium.

The ether acid salts in which the ether acid or oxyacid substituents is derived from an allphatic acid are considered preferred from the standpoint of synthesis, but it is to be understood that similar salts may be obtained in which the group -Z-CO'OM in the ether acid substituent '(O-Z-COOM) represents the residue of an aromatic acid salt. Alkali salts of diaryl ether acids of this character can be synthesized by reacting an alkyl-substituted aryl alkali metal oxide with a brom-aryl alkali carboxylate in the presence of a small percentage of powdered copper as a catalyst, the reaction-mixture being heated to about 400 F. This reaction may be represented by the following equation:

in which MX indicates a salt of the metal M which is soluble in a solvent for the ether acid salt in which the corresponding alkali metal salt M X is insoluble.

Metal salts of alkylated aryl ether acids can also be formed by first neutralizing the alkali metal salt with mineral acid to form the ether acid, followed by water washing to purify the product, and then reacting the anhydrous acid with the alcoholate of the desired metal according to the following equation:

in which Alk OM) indicates an alcoholate of the metal M. v

The details of the foregoing procedure; will be discussed hereinafter with specific examples.

The metal substituents in the ether acid group attached to the aroxy nucleus of the improving agents described herein may be broadly classified as the metals belonging to the silver, copper. tin, aluminum, iron, alkali and alkaline earth analytical groups, which include: silver, mercury, lead, and thallium; bismuth, copper, and cadmium; arsenic, antimony, and tin; iron, cobalt, nickel, and manganese; barium, calcium, strontium, and magnesium; and sodium, potassium, and lithium, respectively. Other desirable metals include: titanium, cerium, thorium, vanadium, molybdenum, tungsten, uranium, and platinum.

The general reactions described and illustrated above, have shown an alkylated or an aliphaticsubstituted hydroxyaromatic compound as the starting material. Compounds of this nature, which satisfy the requirements of high alkylation for the preferred improving agents discussed above, or mixtures of such compounds can be readily prepared by alkylating a monoor polycyclic, monoor poly-hydric, substituted or unsubstituted hydroxyaromatic compound with aliphatic compounds or predominantly aliphatic materials.

The starting material for the hydroxyaromatic constituent in the alkylation reaction to obtain an alkylated hydroxyaromatic product R (T(oH)Yb)n, in which Yb, if present, is residual hydrogen, may be a monoor poly-cyclic hydroxy-aromatic compound otherwise unsubstituted; or such compounds containing alkyl substituents; or in certain special cases (to be hereinafter described) the starting material may be analkyl-aryl ether or an aralkyl-aryl ether. For obtaining an alkylated hydroxyaromatic product containing a Y substituent, in addition to or in place of residual hydrogen, the starting material for the hydroxyaromatic constituent may be .a monoor poly-cyclic hydroxyaromatic compound in which part of the nuclear hydrogen is substituted with a member or members of the group consisting chlorine, hydroxy, alkoxy, aroxy, aryl, alkaryl k nd aralkyl groups.

Examples of the droxyaromatic compounds which may be used as starting material for the alkylation reaction are: phenol, resorcinol, hy-. droquinone, catechol, cresol, xyl enol, .hydroxydiphenyl, benzylphenol, phenyl-ethyl-phenol, phenol resins, methyl-hydroxydiphenyl, alpha and beta naphthol, alpha and beta methyl naphthol, tolyl naphthol, xylyl naphthol, benzyl naphthol, anthranol, phenyl methyl naphthol, phenanthrol, anisole, beta naphthyl methyl ether, chlorphenol, and the like. Preference in general is to the monohydroxy phenols otherwise unsubstituted, particular preference being given to phenol and alpha and beta naphthol.

The alkylation of the hydroxyaromatic compound may be accomplished in various ways, such as by a Friedel-Crafts synthesis, using a halogenated aliphatic hydrocarbon, or by reaction with unsaturated high molecular weight aliphatic compounds or higher alcohols in the presence of H2SO4 as a catalyst.

We have found the Friedel-Crafts type of alkylation reaction to be particularly adapted to the step of preparing the alkylated hydroxyaromatic compounds from which the improving agents described herein are synthesized because it affords a convenient means for controlling the degree of alkylation and obtaining the desired phenolic ratio for use in the preferred mineral oil compositions contemplated by this invention.

In this reaction an appropriate mono or polychlorine-substituted aliphatic compound or material is reacted with the desired hydroxyaromatic compound in the presence of a catalytic amount of aluminum chloride. Pure or substantially pure monoor poly-chlorine-substituted aliphatic compounds may be used. However, as will be readily understood by those skilled in the art, since it is usually very diflicult to prepare or obtain high molecular weight aliphatic hydrocarbons in a pure or substantially pure state and since it is equally difilcult to prepare the chlorine (or other halogen) substitution products of such hydrocarbons in a pure or substantially pure state, we prefer to employ a mixture of such hydrocarbons, such as a suitable petroleum fraction, as the starting material for our preferred improving agents, converting it into a mixture of different chlorine (or other halide) substitution products by any suitable method for use in the alkylation step. In general, it may be said that the high molecular weight aliphatic hydrocarbons contemplated by this invention as preferred sources for the-alkyl or aliphatic substituent R, in Formula III above may be pure or mixed compounds typified by those which characterize the heavier products of petroleum, such as heavy petroleum oils of the lubricant type, petrolatum, and crystalline petroleum wax or other compounds or materials which will result in relatively long chain aliphatic substituents. Special preference is given to petroleum wax of melting point not substantially less than about I20 F. Such specially preferred aliphatic hyirocarbon materials commonly have molecular weights of about 350 and have at least twenty :arbon atoms in their molecules.

As stated above, the Friedel-Orafts synthesis lfl'ords a convenient means of controlling the degree of alkylation of the product. This is accomplished by controlling: (a) the chlorinaion of the aliphatic hydrocarbon and (b) the 'eacting proportions of the chlorinated aliphatic iydrocarbon and the hydroxyaromatic comound used in the Friedel-Crafts reaction. As well known to those skilled in the art, the eplacement of nuclear hydrogen in the hydroxy- Lrom'atic compound with an aliphatic group is, n the Friedel-Craits synthesis, eiiected by re- .ction of such nuclear hydrogen with chlorine n the chlorinated aliphatic compound, the subtitution being efiected with evolution of H01. t will thus be seen that the number of chlorine ubstituents in a chlorinated aliphatic compound orresponds to the number of valences (v in genral Formula III) which will be satisfied by or ttached to hydroxvaromaticnuclei in the prodlct of the reaction. For example, in a reaction where a quantity of pure monochloraliphatic lydrocarbon containing say three atomic proortions of chlorine is reacted with one molecular roportion of hydroxyaromatic compound, the reulting alkylated product, RF(T(OH)Yb) n, is one :1 which 2: and n are equal to one and there re three aliphatic groups R" attached to one .ucleus T. On the other hand,assuming a rection in which a quantity of pure trichloralihatic hydrocarbon containing three atomic proortions of chlorine is reacted with one molecun' proportion of hydroxyaromatic compound. he product would be one in which 0 and n of eneral Formula III are each equal to three, and he solubilizing action of a single aliphatic group ould be distributed among three nuclear hyroxyaromatic groups. It is due to this latter ondition that we consider it preferable that the umber of valence bonds 1) (in R" of Formulae II, etc.) be maintained within the range of rom one to four hereinahove specified. In other ords, it appears that the required oil-solubiliz- 1g and oil-improving action of the aliphatic ubstituent R", particularly where the aliphatic ubstituent is a wax derivative and the agent to be used for multifunctional activity in v'isous oils, is not obtained with materials preominantly comprised of a-compound or comounds R (T(OZ'COOM)Yb)n (Formula III) in hich uand 11. are greater than four. Hence, Jr use in the Friedel-Crafts reaction thechlorrated high molecular weight aliphatic material could be a compound, or should be predominant- Y comprised of compounds in which the chlorine antent is not greater than a tetrachlor .comound.

As will be readily apparent to those skilled in ac art, the chlorination of an aliphatic maarial such as a liquid petroleum fraction or a rystalline petroleum wax will normally or usually esult in a mixture of monoand poly-chloralihatic hydrocarbon compounds. Consequently, 1e product of a Friedel-Crafts reaction between 1011 chlorinated material and a hydroxyaroia'tic compound will be a mixture of diiferent ompounds corresponding to difierent values of and n in the formula R"(T(0I-)Yb)n and 1e final 'alkylated aryl ether acid salt derived iereirom according to the reactions of equations b", d, etc., above will likewise be a mixture of compounds corresponding to different values of n and v in general Formula III. It will be understood, therefore, that the specific values for v and n in the above formula, as well as the formula itself, relate to the diiferent specific compounds present in such a mixture which charhereinabove.

The above-mentioned ratio of hydroxyaromatic component to the corresponding alkylated hydroxyaromatic component I ))i\ in which the hydroxyaromatic component is calculated as phenol and which is therefore herein referred to as the phenol content or phenolic ratio, is usually calculated from the weight of -th'e hydroxyaromatic compound used up in the all-aviation reaction and from the total weight of alkylated compound resulting from such alkylation reaction, as will be readily understood by those skilled in the art.

For example, when the Friedel-Crafts synthesis is used for alkylation, the aliphatic hydrocarbon materialis first chlorinated until the weight of chlorine'absorbed indicates that the average composition of the chlorinated product corresponds roughly (in the case of a high molecular weight aliphatic hydrocarbon) to say a dichloraliphatic hydrocarbon. Such a product will, of course, contain some mono and. trlchlor compounds and probably some tetrachlor compounds. The reacting proportions (based on atomic proportions of chlorine to one mole of .hydroxyaromatic compound) are then selected so that the theoretical product of the Friedel- Crafts reaction will give the approximate phenolic ratio desired. After the Friedel-Crafts reaction and purification of the product the Weight of alir phatic material in the chlorinated aliphatic starting material is subtracted from the weight of the alkylated or aliphatic-substituted product to obtain the weight of hydroxyaromatic material ((T(OI-I) )n) actually combined or used up in the alkylation synthesis. From this value and the weight of the alkylated product (R"(T(0H))n) the phenolic ratio or phenol content can be readily calculated. If there are other substituents 1 (Yb) on the hydroxyaromatic nucleus in addition to the monoor poly-valent aliphatic groups, a deduction should be made for them before calculating the phenolic ratio, an operation which will be apparent to those skilled in the art.

In theforegoing description of the Friedel- Craits alkylation reaction we have referred to a hydroxyaromatic compound as a starting material. This same reaction may be used with an alkyl-aryl ether or an aralkyl-aryl ether which undergoes a substantial rearrangement during Friedel-Crafts alkylation to form an alkylated' hydroxyaromatlc compoundin which the alkyl group of the ether replaces one of thenuclear hydrogen atoms.

In the event it is desired to obtain a product R"(T(O-Z-COOM) Yb) n which contains an alkoxy group as the substituent-Yb, it is preferable that the alkylation be effected with a'"hydroxyaro- 'matic compoundcontainingsuch' alkoxy or aroxy group as 'a substituent and a high molecular weight unsaturated aliphatic hydrocarbon (such as polymerized isobutylenef dodecyl ene, tetradecylene, octadecylene, melene, etc.) or a higher alcohol (such as cetylalcohol,-myricyl' alcohol, ceryl alcohol, octadecylalcohol, etc.) 'using H2804 as a catalyst. By this procedure, the hydroxyaromatic ether can be alkylated without substantial rearrangement taking place. As an alternative procedure, polyhydric phenols can be alkylated by reaction with alcohols or unsaturates or by Friedel-Crafts reaction followed by substitution of one hydroxyl hydrogen with a low molecular weight alkyl group. In carrying out this latter procedure, the alkylated polyhydric phenol is treated with an alkali alcoholate to introduce alkali metal into the OH group followed with the desired alkyl halide, whereby the substitution is effected.

When it is desired to obtain a nitro or amino group as the substituent Yb" in general Formula III, the hydroxy aromatic compounds are. alkylated when free of nitro or amino groups, and such alkylation is followed by nitration of the alkylated compound to introduce the nitro substituent.

The amino group can be obtained by reduction of the nitro group.

PREPARATION OF WAX-SUBSTITUTED PHENYL E'I'HER ACID SALTS 1) ALKYLarroN or PHENOL after which chlorine isbubbled therethrough' until the wax has absorbed from-sixteen per cent to twenty per cent of chlorine, such product having an average composition between a monochlor wax and a dichlor wax or corresponding roughly -to-a dichlor wax. Preferably the chlorination is continued until'about one-fifth the weight of the chlorwax formed is chlorine. A quantity of chlorwax thus obtained, containing three atomic proportions of chlorine, is heated to a temperature varying from just above ts melting point to not over F., and one mole of phenol (CsHaOH) is admixed therewit The mixture is heated to about 150 F., and a quantity of anhydrous aluminum chloride corresponding to about three per cent of the weight of chlorwaxin the mixture is slowly added to the mixture with active stirring. The rate of addition of the aluminum chloride should be sufficiently slow to avoid violent foaming, and during such .addition the temperature should be held at about 150 F. After the aluminum chloride has been added, the temperature of the mixture -may be increased slowly over a period of from fifteen to twentyfive minutes to 'a' temperature of about 250 F. and then should be more-slowly increased to around 300 F.-350 F. To control the evblution of 1101 gas the temperature of the mixture is preferably raised from 250 F. to 300 E 350? F. at a rate of approximately one degree per minute, the whole heating operation occupying approximately two hours from the time'of adding the' aluminum chloride. If the emission of HCl gas has not ceased when the final temperature is reached, 'the mixture may be held at 350 F. for I a short time to allow completion of the reaction. 'But, to avoid possible cracking of the wax, the mixture should not be heated appreciably above 350 F., nor should it be held at that temperature for any extended length of time. 1

It is impo'tant that allunreacted or nonalkylated hydioxyaromatic material (phenol) remaining after'the alkylation reaction be removed. Such removal'can be efiected generally by water-washing, but it is preferable to treai the water-washed product with super-heatec steam, thereby insuring complete removal of the unreacted material and accomplishing the drying of the product in the same operation.

The wax-substituted phenol thus obtainec may be characterized by the general formula R (T(OH)Yb) n, in which R. represents at leas one aliphatic group or radical characteristic 0 paraffin wax having a valence v of from on to four; T represents a monocyclic aromatic nu cleus; Yb represents residual hydrogen, b be ing a number corresponding to the number 0 valences on the nucleus T not satisfied by R and (OI-I); and n is a number from one to fou corresponding to the valences v on the aliphatir group or groups R' which are satisfied by the nu clear group or groups T(OH) Yb.

4 wax-substituted phenol prepared accordln "to the above procedure, in which a quantity 0 chlorwax containing three atomic proportions o chlorine (twenty per cent chlorine in the chlor wax) is reacted with one mole of phenol, may, fo brevity herein, be designated as wax-phenc (3-20). Parenthetical expressions of this typ (A-B) will be used hereinafter in connectio: with the alkylated hydroxyaromatic compound to designate (A) the number of atomic propor tions of chlorine in chloraliphatic material re acted with one mole'of hydroxyaromatic com pound in the Friedel-Crafts reaction, and (B the chlorine content of the chlor-aliphatic mate rial. In the above example A=3 and B=20. Thi samedesignation will also apply to the arox metal salt carboxylate derivatives.

Wax-phenol (3-20) as obtained by the 'abov procedure had a phenol content or a phenolic ra tio of about sixteen per cent. Our research in dicates that this phenolic ratio in the neighbor hood of sixteen or seventeen per cent may 11 considered as representing about the maximui for satisfactory miscibility and multifunction: activity in viscous oils of the aroxy carboxylal metal salt derivatives of alkylated hydroxyarc matic compounds in which the alkyl substituent: derived from wax and the hydroxyaromatic con stituent is derived from"phenol (Cd-BOH). Ei fective oil-improving agents can, however. be ok tained from wax-phenol(3- 16), in which tl: phenol content or phenolic ratio is in the neigr borhood of twelve or thirteen per cent.

(2) Foamxrron or Wax-Sunsrrrurm ALKALI ALKALINE EAa'rn Mrrmr. Pursue As an example of this step in the preparatic of our oil-improving agents, wax-substituted S( .dium phenate can be prepared by the reaction wax-phenol with metallic sodium in the presem of a non-oxidizing gas. The-reaction mixture.

heated at 500 F; during a two-hour period wit rapid stirring "to produce finely divided sodiu:

and thereby accelerate the reaction. The prc portions of reactants which were used in prepai completion of the reaction.

ing a wax-substituted alkali metal phenate according to the above procedure were:

- Grams Wax-phenol (13.2 per cent combined phenol content) 500 Sodium or equivalent amount of potassium 16 It will be understood, of course. that other reactions may be employed to efiect the alkali metal substitution.

(3) FORMATION OF ETHER Acln SALTS FROM VAX- ALKALI METAL PHENATE (a) 24.7 grams of monochloracetic acid in cc. of absolute ethyl alcohol was converted to sodium chloracetate by adding dropwise a standard alcohol solution of sodium hydroxide, maintaining the temperature of the reaction mixture below 100 F. This sodium chloracetate mixture was then added to a solution of 200 grams of wax-phenol (3-16) as the wax-sodium phenate,

in 600 grams of mineral oil (Say. Vis. 244 sec. at F.), and the reaction mixture was held at F. during a two-hour period to form the waxsubstituted phenoxy sodium acetate. By diluting the mixture sufllciently with Stoddard solvent or other appropriate diluent, the mixture can be centrifuged to remove reaction salts, thereafter removing the light diluent by distillation to obtain the pure product.

The wax-phenoxy acetic acid used in certain of the hereinafter described procedures can be obtained by neutralizing the reaction mixture, before purification, with hydrochloric acid. The free acid is purified by water-washing the product to remove reaction salts and drying to give a concentrated .mineral oil blend of the finished product.

(b) 200 grams of wax-phenoxy-sodium acetate (Ii-16) in mineral oil solution was reacted with 17.68 grams of zinc chloride by adding dropwise an alcoholic solution of zinc chloride to the sodium ether acid salt (Wax-phenoxy sodium ace-, tate) and holding the temperature of the reaction mixture at a temperature of F. during a two-hour period to complete the reaction. The mixture may be diluted with Stoddard solvent or other suitable diluent and the wax-phenoxyzinc acetate (3-16) obtained can be purified by water-washing and distilling to remove the diluent.

c) Cobaltous ethylate was formed by adding an alcoholic solution of 16.7 grams anhydrous cobaltous chloride to sodium ethylate (5.97 gm. Na content.) Without purification, the cobaltous ethylate was added to a mineral oil blend containing 200 grams of wax-phenoxy-acetic acid 3-16) and the reaction mixture was heated to 350 F. and held at that temperature for a two-hour period during which the alcohol distilled off with The wax-phenoxy cobaltous acetate thus formed can be purified'by settling and centrifuging or water-washing to remove reaction salts.

(d) The same general. procedures described above have been used in preparing wax-phenoxyacetates from wax-phenol (3-19) having a combined phenol content or phenolic ratio of 15.7 per cent. Here the proportions of reactants for making the wax-sodium phenate were 200 grams of wax-phenol (15.7 per cent combined phenol) in 800 grams of mineral oil and eight grams of sodium as the sodium ethylate. 200 grams of wax-phenoxy acetic acid prepared from the wax phenate obtained above was reacted with 76.8

grams of sodium as sodium ethylate to form the wax-phenoxy-sodium acetate (3-19).

Wax-substituted aryl ether acid salts of the general character described above can be prepared from other wax-substituted hydroxyaromatic compounds, either monoor poly-cyclic and substituted or unsubstituted, such, for example, as wax-naphthol (319) having a combined naphthol content of sixteen per cent and equivalent phenol content or phenolic ratio of 9.7 per cent. They may also be obtained with other alkyl substituents than petroleum wax, although, as indicated above, alkylated hydrocarbons of the wax type (having at least twenty carbon atoms) are preferred because of the multifunctional activity of their products. It is also emphasized that the invention is not limited to products obtained from acetic acid as a source for the ether. acid substituent but that any chloraliphatic acid (as the alkali salt thereof) may be used to obtain various alkyl chains or groups,

in the ether acid or oxy-acid substituent. Also, as we have previously pointed out, the waxphenoxy-aromatic carboxylate types of salts are contemplated herein. Such compounds can best be prepared from a wax-alkali phenate and brom-aromatj c acid, the reaction being carried out at elevated temperature in the presence of be broadly characterized as oil-miscible metal salts of alkylated aroxy-carboxylic acids in which part of the hydrogenin the aroxy nucleus is replaced with a mineral oil-solubilizing substituent. Compounds of this general type may be further characterized as oil-miscible, metal salts of alkylated or alkyl-substituted aryl ether acids in which the carboxyl hydrogen has been substituted with its equivalent weight of metal; also as alkylated hydroxyaromatic compounds in which the hydroxyl hydrogen has been substituted with an organic acid salt radical or group, it being understood that the terms alkyl and a1kylated are used herein in a broad sense to include polyatomic or polyvalent, as well as monovalent aliphatic radicals or groups, and that an organic acid salt radical or group is an aliphatic, alicyclic, or aromatic carboxylic acid residue having one carbon valence-available for attachment to the, oxygen of a hydroxyaromatic compound to forman aryl ether linkage.

To demonstrate the efiectiveness of compounds or products of the type described above in the mineral oil compositions contemplated by this invention, we have conducted several comparative tests, the, results of which are listed below, with representativev mineral oils alone. and with the same oils blended with the improving agents contemplated by this invention.

POUR POINT DEPRESSION Table I A. S. T. M. pour tests Depressant blended with motor oil of on on and on blends Saybolt viscosity of 244 sec. at'130 F.

F. F. F. Wax-phenoxy-zinc acetate (3-16) +20 -20 10 Wax-phenoxy-cobaltous acetate (3-16) +20 -20 15 Wax-phenoxy-sodium acetate (3-19) +20 25 -10 Wax-phenoxy-cobaltous acetate (3-19) +20 15 10 Wax-phenoxy-cobaltous benzoate (3-16). +20 20 -15 V. I. IMIPROVENIENT Another property of the mineral oil compositions contemplated by this invention which has been investigated and found to have been improved by metal salts of certain of the alkylated aryl-ether acids is the viscosity index. The effectiveness of the wax-aryl ether acid salts as V. I. improvers is demonstrated by the data in Table II below. In obtaining this data the viscosity index was obtained in the conventional manner from the Saybolt viscosity of the oil and the oil blends at F. and 210 F. The oil used was a viscous mineral oil of the lubricant type.

OPERATION TEST In addition to the foregoing tests we have also made tests of an oil and an oil blend containing a representative improving agent of the type contemplated by this invention to determine the comparative behavior of the unblended oil and the improved oil under actual operating conditions. The test was carried out in a single cylinder 0. F. R. engine. The engine was operated continuously over a time interval of twenty-eight hours, with the cooling medium held at a temperature of about 390 F., at a speed of 1200 R. P. M., which is equivalent to a road speed of about twenty-five miles per hour. The oil temperature was held at about F. during the test.

The oil used in this test was a lubricating oil stock of 120 seconds Saybolt Universal viscosity at 210 F., and the conditions observed at the end of the test were (a) the extent to which the piston rings were stuck, b) the extent to which the slots in the oil rings were filled with deposit, (0) the amount of carbonaceous deposits in the oil, and (d)' the acidity or neutralization number as indicated by the results tabulated below.

(N. N.) ,of the oil at the end of the test. The oil indicated as A in Table III below is the unblended oil, and oil 18" is the same oil containing of wax-phenoxy-cobaltous acetate. The results of this test indicate a substantial inhibition against the deleterious effects of oxidation.

Table III Ring condition 1 Oil Degrees stuck gg gfig 325 32;: N. N.

A. 360 360 360 360 50 50 0 17. 25 l 1. 7 B l. 0 0 0 0 O 0 0 0 6. 53 0. 4

Table IV below shows the effectiveness of amyl phenoxy cobaltous acetate as an inhibitor. The oil indicated as A was blended with one-third per cent of this inhibitor to give oil B.

From the foregoing results it will be apparent that metal salts of alkylated aryl ether acids of the type contemplated by this invention are efiective oil-improving agents and the preferred wax-substituted products are characterized by the fact that they have, through the presence of the wax-substituted aryl nucleus and the metal substituents, multifunctional activity. Although we do not wish to be bound in any regard by any theory as to the function which the metal substituents have, it is believed that such sub'stituents act by promoting the preferential oxidation of the alkylated aryl-ether acid molecule, thereby taking up active oxygen and acting as a direct antioxidant; also by acting as a peptizing agent on any sludge that is formed in the oxidation" of the oil; and in the event an alkali or alkaline earth metal is present as the metal substituent, the salts act by neutralizing strong acids in the oil, particularly sulfur acids such as may be formed by oxidation. The improved properties obtained and the degree of improvement in a particular property may be varied with the metal substituents, the aryl constituents, and the degree of alkylation of the aryl nucleus.

As to the degree of alkylation, it is important that the aryl nucleus be sufficiently alkylated to provide a final product which is soluble or miscible in the particular mineral oil fraction with which it is to be blended; that is, one which will remain uniformly dispersed in the oil in suflicient amount to effect the desired improvement under normal conditions of storage and use.

The amount of improving agent used may be varied, depending upon the mineral oil or the mineral oil fraction with which it is blended and the properties desired in the final oil composition. The alkylated aryl ether acid salts of the type described herein may be used in amounts ranging from one-sixteenth per cent to ten per cent, and in general compositions of the desired improved properties may be obtained with these improving agents in amounts .of from one-sixteenth per cent to two per cent..

It is to be understood that while we have described certain preferred procedures which may be followed in the preparation of the alkylated aryl-ether acid salts used as improving agents in the mineral oil compositions contemplated by this invention and have referred to various representative constituents in these improving agents, such procedures and examples have been used for illustrative purposes only. The invention, therefore, is not to be considered as limited by-the specific examples given but includes within its scope such changes and modifications as fairly come within the spirit of the appended claims.

We claim:

1. An improved mineral oil composition comprising a viscous mineral oil fraction having admixed therewith a minor proportion of an oilmiscible metal salt of an aryl ether acid in which part of the hydrogen on the aryl nucleus has been substituted with predominantly aliphatic organic material, said last-mentioned substituent comprising a suflicient proportion of the aryl ether acid saltv to render said salt miscible with said oil under normal conditions of handling and use.

2. An improved mineral oil composition comprising a mineral oil having admixed therewith in minor proportion: an oil-miscible metal salt of a wax-substituted aroxy-aliphatic carboxylic acid.

- 3. An improved mineral oil composition comprising a viscous mineral oil fraction having admixed therewith in minor proportion: an oilmiscible metal salt of an alkyl-substituted aryl ether-carboxylic acid.

4. An improved mineral oil composition comprising a viscous mineral oil fraction having admixed therewith in minor proportion: an oil- .miscible metal salt of an alkyl-substituted aryluent is a high molecular weight aliphatic hydrocarbon group and in which the 'aryl nucleus is poly-substituted with said alkyl substituent.

'7. An improved mineral oil composition comprising aviscous mineral oil fraction having admixed therewith a minor proportion of an oil-miscible metal salt of an alkyl-substituted phenoxy-aliphatic carboxylic acid.

8. An improved mineral oil composition comprising a. viscous mineral oil fraction having admixed therewith a minor proportion of an oil-miscible metal salt of any alkyl-substituted naphthoxyealiphatic carboxylic acid.

9. Animproved mineral oil composition comprising a mineral oil having admixed therewith a minorproportion of an oil-miscible metal salt of a wax-substituted phenoxy-aliphatic carboxylic acid.

10. An improved mineral oil composition com-. prising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of a wax-substituted naphthoxy-aliphatic carboxylic acid.

11. An improved .mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of a wax-substituted phenoxy-aliphatic carboxylic acid in which the metal substituent is selected from the group consisting of sodium, zinc, and cobalt.

12. An improved mineral oil composition comprising a viscous mineral oil fraction having admixed, therewith a minor proportion, from about one-sixteenth per cent .to about ten per cent, of an oil-miscible metal salt of an alkylsubstituted aryl-ether carboxylic acid.

cent of an oil-miscible metal salt of an alkylsubstituted aryl-ether carboxylic acid in which said alkyl substituent is derived from petroleum wax.

14. A composition of matter comprising a mineral oil fraction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound having the general formula: R (T(O'ZCOOM)Yb)n in which: T represents an aromatic nucleus} (O-Z-COOM) represents at least one ether acid salt subs'tituent attached to T and wherein 0 represents oxygen, Z represents an aliphatic or an aromatic group and COOM represents at least one carboxyl group, the hydrogen thereof being replaced by its equivalent weight of a metal M; R represents at least one aliphatic .group having a valence v of from one to four, and attached by one valence only to at least one nucleus T; Yb. represents a monovalent radical attached to T and selected from the group consistingof residual hydrogen, andchlorine, alkoxy, aroxy, aralkyl, alkaryl, aryl, nitro, and amino radicals; b represents the number of Ybs and is equal. to zero or a whole number corresponding to the valences on the nucleus T not satisfied with R and (O-Z-COOM) and n is a whole number-from one to four, the substituent R comprising a suflicient proportion of the metalorganic compound as a Whole to render the same miscible with saidmineral oil under normal conditions of handling and use.

15. A composition of matter comprising a mineral oil fraction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound having the general formula: R (T(O-Z-COOM)Y1,).in which: T represents an aromatic nucleus; (O-Z-CQOM) represents at least one ether acid salt substituent attached to T and wherein 0 represents oxygen, Z represents an aliphatic or an aromatic group and COOM represents at least one carboxyl group the hydrogen thereof being replaced by its equivalent weight of a metal M; R. represents at least one aliphatic group having a valence v of one to four, and attached by one valence only to at least one nucleus T; Yb represents .a monovalent radical attached to T and selected from the group consisting of residual hydrogen, and chlorine, alkoxy, aroxy, aralkyl, alkaryl, aryl, nitro, and amino radicals; b represents the number of Yes and is equal to sewer a whole number corresponding to the valences on the nucleus T not satisfied with R. and (O-Z-COOM) and n is a whole number from one to four, the total number of carbon atoms in all of the aliphatic groups taken together in said metalorganic compound being not less than about twenty-five for each nucleus T.

16. A composition of matter comprising a mineral oil fraction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound having the'general formula: R (T(O'Z'COOM)Yb)n in which; T represents an aromatic nucleus; (O-Z-COOM) represents at least one ether acid salt substituent attached to T and wherein 0 represents oxygen, Z represents an aliphatic or an aromatic group and COOM represents at least one carboxyl group the hydrogen thereof being replaced by its equivalent weight of a metal M; R represents at least one aliphatic group having a valence v of one to four and attached by one valence bond only to at least one nucleus T; Yb represents a monovalent radical attached to T and selected from the group consisting of residual hydrogen,

.and chlorine, alkoxy, aroxy, aralkyl, alkaryl, aryl,

nitro, and amino radicals; b represents the number of Ybs and is equal to zero or' a whole number corresponding to the valences on the nucleus T not satisfied with R and (O-Z-COOM); andn is a whole number from one to four, the ratio of (T(O'Z'COOM))12 to R (T(O-Z-C0OM))11 in said metalorganic compound expressed as attached to T and wherein 0 represents oxygen, Z represents an aliphatic or an aromatic group and COOM represents at least one carboxyl group, the hydrogen of which is replaced with its equivalent weight of a metal M; R"' represents at least one polyvalent aliphatic hydrocarbon group of at least twenty carbon atoms having a valence v of from two to four; Yb represents a monovalent radical attached to T and selected from the group consisting of residual hydrogen, chlorine, alkoxy, aroxy, alkaryl, aralkyl, aryl, nitro, and amino radicals; b represents the number of Yb"s and is equal to zero or a whole number corresponding to the valences on the nucleus T not satisfied by R', (O-Z-COOM) or Re; Re rep? resents monovalent aliphatic radicals; c represents the number of Rcs and is equal to zero or a whole number corresponding to the valences on the nucleus T not satisfied with R (O-Z-COOM) and Yb; and n is a whole number from two to four. l

' ORLAND M. REIFF.

FERDINAND P. OTTO.

cERTIErcAT-E 0F CORRECTION.

Patent No. 2,198,292.

April 25, 19!;0.

ORLAND n. REIFF, ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 10, first column, line 20, in the right-hand column in the heading of Table 1, for

"-1/2 read -1/ 2";

and that the said Letters Patent shouldbe read with thisvcorrection therein that the same may conform to the record ofthe case in the Patent Office.

Signed and sealed this 18th day of March, A. D. l9lil.

(Seal) Henry Van Arsdale, Acting Commissioner of Patents.

represents at least one ether acid salt substituent l A; ,..l.

CERTIFICATE OF CORRECTION.

Patent No. 2,19 ,292, Apr-i125, 191w.

' 0mm) :1. REIFF, ET AL.

It is hereby certified that error appears in the printed Specification of the above numbered patent requiring correction as follows: Page 10, first 601m, line 20; in the right-hand oolumn inthe heading of Table 1, for "1/2 read --1/3 and that the said Letters Patent shouldbe read with this correction therein that the same may conform to the record ofthe case in the Patent Office.

Signed and sealed this 18th day of March, A. D. 19in.

Henry Van Arsdale, 7 Acting Commissioner of Patents.