US2252664A - Alkyl substituted metal aryl hydroxylate-metal carboxylate salts and a method of making them - Google Patents

Description

Patented Aug. 12, i941 ALKYL SUBSTITUTED METAL ARYL D B O X Y L A T-E-METAL CARBOXYLATE SALTS AND A METHOD OF MAKING THEM Orland Mnem', Woodbury, John .1. Giammaria, Riverside, and Horace E; Redman, Woodbury, N. J., assignors to Socony-Vacuum Oil Company, Incorporated, New

' notation of New York No Drawing. ApplicatlonIuly16,1938, Serial No. 219,594, I 7

Claims. (ol. 260-429);

; "This invention relates to the production of certain new chemical compounds or' compositions which may begenerally designated as waxsubstituted metaloxyaromatic-metal carboxylate salts. These products'may also be designated as salts of wax-substituted hydroxyaromatic carboxylic acids in which both the hydroxyl and carboxyl hydrogensare substituted with their equivalent weight of metal. Although the in- 'vention is broadly concerned with'chemical compounds or compositions coming within the abovedesignated general classification, it contemplates as a preferred group within such general classiflcation those compounds or compositions which are soluble or miscible with mineral oil.

. Our invention is based upon the discovery that the oil-miscible wax-substituted metaloxyarorustic-metal carboxylate salts of hydroxyaromatic. carboxylic acids are of multifunctional ac- I tivity when blen'ded with viscous mineral oil fractions in that they eiie'ct improvement of several unrelatedandlrelated properties of the oil. For example, this preferred oil-miscible group of compounds or compositions coming'within the general field of invention contemplated herein are efl'ective, when blended in a minor proportion with mineral oil fractions of the lubricant type, to depress the pour point, improve the viscosity 'index (V. 1.), and inhibit oxidation of the 011.

By inhibiting oxidation these oil-miscible metaloxyaromatic-metal carboxylate salts act to retard the formation of sludge and acidic products of oxidation. They also have a peptizin'g action on such sludge as may eventually be formed. Thus, .any one of these preferred oil-miscible compounds or compositions may, for example, be used in internal combustion engine lubricants to retard or prevent the sticking of piston rings or prevent the corrosion of bearings, particularly those formed of alloy metals normally susceptible to corrosion, etc., and at the same time it will act to depress the pour point and improve the viscosity index of the oil. Through a proper choice of metal substitue'nt (lead, copper, tin, or zinc, for example) the load-carrying capacity or "lubricity" of the oil may also be improved.

It should be understood that the use of these preferred oil-miscible compounds or compositions is not confined to lubricating-oils, but they may be employed in any-mineral ollfractions where one or more of the improved properties recited above is desired. In this regard it is'to be further understood that the presentinvention isfnot concerned with mineral oil compositions containing these preferred oil-soluble com- York, N. Y., a corpounds, such oil compositions forming the sub- 2,197,832) to which reference is made for further details in the compositlon 'of these compounds. ,It is also to be understood that while our invention contemplates oil-miscible compounds or compositions 'of the type above referred to as a preferred class or group within the general field of invention, the invention isnot limited to such oil-miscible compounds or compositions, since thiswhole class of new materials is possessed of valuable properties irrespective of oil-miscibility. For example, these compounds or composb tions may be used as intermediaries in the pro;- duction of resins, resin-like materials, rubber substitutes, etc. Certain of-the compounds or compositions'are possessed of valuable pharmaceutical, insecticidal, or similar properties,- such,

for, example, as those derived from the presence characterized by the'presence of an aromatic nucleus in which atleast'one nuclear hydrogen is substitutedwitha metaloxy group and an-= other nucl' I boxyl grou wnerem the carboxyl hydrogen is replaced with its equivalent weight of the some or a difierent metal.

The compounds or compositions contemplated by this invention are further characterized by the fact that'at least one replaceable hydrogen on the aromatic nucleus is substituted with an "aliphatic hydrocarbon radical or group characteristic of an aliphatic hydrocarbon of high nice lecular weight which we may term a heavy alkyl group. For obtaining the preferred group oi. 1

compounds or compositions which are miscible with mineral oil and which possessi'the multifunctional oil-improving properties, we have found that this heavy alkyl substituent in the metaloxyaromatic-metal carboxylate salts under discussion must be derived from a predominantly straight chain aliphatic hydrocarbon of at least hydrogen is substituted with a car twenty carbon atoms such as characterize crystalline petroleum wax. As a matter of fact, petroleum wax is considered to be a preferred source of the heavy alkyl" substituent and itis for that reason that the compounds or compositions described herein are referred to as wax-substituted. It is to be understood, however, that the term wax" as used herein, is applied in abroad sense and is intended to include any pure compound or mixture of compounds predominantly ali hatic in nature and containing at least twenty carbon atoms which is susceptible of attachment 4 aasaooa.

metal carboxylate salts of wax (or heavy alkyl) -substitut'ed hydroxy-aromatic carboxylir acids preferred for use as oil-improving agents have the aryl nucleus substituted with heavy to an aromatic nucleus to provide a substituent which, in the proper proportions, will impart to the characterizing aryl metal phenate-metal carboxylate group or nucleus the multifunctional oilimproving properties referred to.

In the preferred group of compounds or commay or may not have a solubilizlng eifect upon the composition as a whole. a For example, part of the nuclear hydrogen may be substituted with a radical selected'from the group consistingof: aliphatic hydrocarbon groups having lessthan twenty carbon atoms, alkoxy, aroxy, aralkyl, alkaryl,- chlorinje, nitro, and amino radicals or groups. Compounds of the abovergeneral formule-type having mono-, di-, and tri cyclic nuclel are illustrated by the following specific formulae:

a OM 11' 0M 11' R 000M a 000m 11' oooM' a a a a a R! I I I I R! alkyl groups to an extent such that this heavy alkyl (wax) substituent comprises a sufilcieni proportion of the composition as a whole to render the sameoil-miscible so that it will form a mineral, oil solution or colloidal suspension which will remain stable as such under normal condi tions of handling and use. It appears that there is a critical range in the degree of wax-substitution below which these wax-substitutec salts will not satisfy the requirements for oilmiscibility.

The critical range in the degree of wax-substitution of the aryl nucleus in the preferrec compounds contemplated herein may vary with: (a) the mineral oil fraction in which the com pound is used; (b) whether the aryl 111101811;

is monoor polycyclic or monoor polyhydric- (c) monoor polysubstitution of the aryl nucleu: with'heavy alkyl groups; and (d) other substituents on the nucleus which may be of positivi .Or negative or of neutral oil-solubllizing activity In view; of theforegoing variables it would bi impracticable and probably misleading to attemp to give an expression and figure which W011i: indicate accurately the proper ratio of hydroxyaromatic constituent to the waif-substitute: hydroxyaromatic constituent in the starting ma terial which'would satisfyall cases taking thesr variables into account. Asa guide for prepar ing these preferred compounds, however, our re search indicates that in general the ratio, ex-

pressed as weight of hydroxyaromaticcomponen in the product to the corresponding wax-substi tuted hydroxyaromatic nucleus or componen therein, should not be greater thanvabout sev enteen parts by weight ofthe former to shun 100 parts by weight of thelatter, or about 1 in which at least one of the R's represents an aliphatic radical or group containing at least twenty carbon atoms and in which the remaining R's represent residual hydrogen which may be replaced with: aliphatic groups containing less than twenty carbon atoms, hydroxy, alkoxy, aroxy, alkaryl, aralkyl aryl, chlorine, nitro, and amino radicals or groups.

It will be understood that the compounds or compositions contemplated by this invention may be pure compounds satisfying the conditions enumerated above with any one of the various monoor polycyclic aromatic nuclei in the characterizing nuclear group. However, inmanufacturing the prefer-red composition by the'preferred proe o'edure, as will appear later on, the final product obtained is normally or usually a mixture of dif- 'ferent compounds the individual characteristics of which differ in their alkyl substituents (accordper cent, when the hydroxyaromatic componen is expressed in terms of its chemically equivalen weight of phenol. This ratio, hereinafter designated as the phenolic ratio, does not take inti account other substituents on the nucleus, but i will serve as a working guide for the prepara' tion of these preferred compounds. A furthe: general guide for the synthesis of these preferrei compounds is to substitute the aryl nucleus wit) parafiin wax or equivalent alkyl substituent s\ that it is polysubstituted.

The general procedure for the preparation 0 the compounds contemplated herein involves th alkylation or wax substitution of a hydroxyarc matic compound (aryl hydroxide), .after whicl the hydroxyl hydrogen thereof is substituted wit. an. alkali or alkaline earth metal. The result ant alkylated'aryl alkali (or alkaline earth) meta hydroxylate is then carboxylated to form th alkali or alkaline. earth metal salt of the alkylate hydroxyaromatic carboxylic acid. When the ul timate product is to be one containing 8. meta other than the alkali or alkaline earth metal con tainedtherein following carboxylation, such 0th er-metal is substituted in the carbox l group is double decomposition, using an alcohol-solubl inorganic or fatty acid salt of the desired meta In this, double decomposition some of the meta may replace hydrogen on the nucleus; but if suc' compounds are formed, they are in the minorit and in any event are not considered harmful t the product.

To form, the metaloxyaromatic-carboxylai salt, the hydroxyaromatic-carboxylate salt is re place. I

-phenols can be alkylated with higher alcohols or acted with an alcoholate or alkyloxide of the desired metal, thereby substituting metal for the hydroxyl hydrogen.

Examples 01' the hydroxyaromatic compounds or aryl hydroxides which can be used as startapparent to those skilled inthe art, compounds or compositionshaving 'acombined phenol com tent in excess of that necessary for oil-miscibility may be readily obtained by using a chlorinated wax having a chlorine content-substan= tially higher than that "given in the example below or by changingv the ratio of the reactants (chlorwax and phenolic compound) pound with the-heavy alkyl groups may be -a'c-- complished in various ways, such as by a Fried'el- Crafts synthesis, using a halogenatedhigh molecular weight aliphatic hydrocarbon compound containing at least twenty carbon atoms; or-a halogenated hydrocarbon materlal'such aschlorinated petroleum wax predominantly comprised of aliphatic hydrocarbons containing at least twenty carbon atoms. The alkylation may also be eflected by, reaction of the aryl hydroxide with unsaturated high molecular weight aliphatic compounds or higher. alcohols in the presence of H2804 as a catalyst.

The Friedel-Craits alkylation reaction may be used with an alkyl-aryl ethenor an .aralkyl-aryl ether as the starting material instead of the aryl hydroxide. In this event the ether undergoes a substantial rearrangement to form an alkylated hydroxyaromatic. compound. in which the alkyl or aralkyl group of the ether replaces one of the nuclear hydrogen atoms.

In the event it *is desired to produce a product which contains an alkoxy or aroxy group as a substituent on the aryl nucleus, it is preferable to use an aryl hydroxide containing such substituent and effect the alkylation with a high molecular weight unsaturated aliphatic hydrocarbon (such as eicosylene, carotene, melen'e, etc.) or'a higher alcohol (such as myricyl alcohol, ceryl alcohol, etc.), using HaSO4 asa catalyst. By this procedure the hydroxyaromatic ether can be alkylated without substantial rearrangement taking As an alternative procedure, polyhyclric high molecular weight aliphatics or by Friedel- Crafts reaction, followed by substitution or one hydroxyl hydrogen with a low molecular weight alkyl group, which substitution can be effected by treating the alkylated polyhydric phenol with an alkali alcoholate to-substitutean OH group PREPARATION OF wax-sons'rrru'rno ""ME'IALOXYAROMATIC-METAL CARBOX-.

. YLATE SALTS (1)1;AL-xYLxr1on or PHENOL,

' Aparafiin'wax melting at'approximately 120 Ffand predominantly comprised of compounds having at"least twenty carbon atoms in their molecules is melted andheate'd' to about 200 F., after which chlorine is bubbled therethrough until the wax has absorbed from sixteen per cent tof twenty-percent of cl'ilorine, such product havin'gan average composition between a monochlor wax and adichIor'Wai': or corresponding roughly to a dichlor wax. Preferably the chlorination is continued until about one-sixth the weight of the with alkali metal and then treating with the desired alkyl halide whereby the substitution is When it is desired to obtain a nitro' or amino substituent, the aryl hydroxide is alkylated or wax-substituted when free or such's'ubstituent.

This is followed by nitration to introduce the 'nitro group. The amino group'can be obtained by reduction of the nitro group. i g

In general it appears that any metal may be employed as the metal substituent, but preference is given to the group comprising copper, tin,

iron, and cobalt.

The following description illustrates the prochlorwax formed is chlorine. A quantity of chlorwax thus obtained. containing three (or four, with twenty per cent chlorine in the chlorwax). atomic proportions of chlorine, is heated to a temperature varying from just above its melting point to not .over F., and one mole of phenol (CsHsOH) is: admixed therewith. The mixture is heated toabout 150 F., and aquantity of anhydrous aluminum. chloride corresponding to about three per cent of the weight of chlorwax in the mixture is slowlyadded to the mixture with active stirring. The rate of addition of the aluminum chloride should be sufiiciently slow to avoid violent foaming, and during such. addition the temperature should be held at about 150 F. After the aluminum chloride been added, the temperature of the mixture may be increased slowly ov era period 01' from. fifteen to twenty-five minutes to a temperature of about 250 F. and then should be more slowly increased .to about 350 F. Tocontrol the evolution of 1101 gas the temperature of the mixture is preferably raised from250" F. to'350" F. at a rate oi. 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 a short time to allow completion of the reaction. But, to avoid possible cracking of the wax, the mixture should not beheated appreciably above 350 F., nor should it be heldat that temperature for any extended lengthoftimei: i

It is important, particularly where an oilmiscible product is desired, that all unreacted or non-alkylated hydroxy-aromatic material (phenol) remaining after the alkylation reaction be removed. Such removal can be efiected generally by water-washing, but it is preferable to treat the water-washed product with superheated steam, thereby insuring complete removal of the unreacted material and accomplishing the drying of the product in the same operation.

" A wax-substitutedphenol prepared according to vthe "above procedure, in which; a quantity of chlorwax containing three atomic proportions of -chlorine (sixteen per cent chlorine in'the chlor- '-wax) is reacted with one mole ot phenol, may, for brevity herein, I be designated as waxmhenol (346). Parenthetical expressions of this type (A-E) will be used hereinafter in connection with the alkylated hydroxyaromatic compounds to designate (A) the number of atomic proportions of chlorine in chloraliphatic material reacted with one mole of hydroxyaromatic compound in the Friedel-Crafts reaction, and (B) the chlorine content of the chloraliphatic material. In the above example A=3 and 3:16. This same designation will also apply to the salts of the carboxylic acids of these alkylated hydroxyaromatic compounds.

Waxephenol (3-16) as obtained by the above procedure'had a phenol content or a phenolic ratio of about thirteen per cent and wax-phenol (4-20) had a "phenolic ratio of about 12.5 per cent. Our research indicates that this phenolic ratio in the neighborhood of thirteen per cent may be considered as representing about the maximum for satisfactory miscibility in viscous oils of the metaloxy-metal carboxylate derivatives o1 alkylated hydroxyaromatic compounds in which the alkyl'substituent is derived from petroleum wax and the hydrcxyaromatic constituent is derived from phenol (CaHsOI-I).

(2) FORMATION or WAX-SUBSTITUTED ALKALI on ALKALINE, EARTH METAL PHENATE As an example 01' this step in the preparation of our oil-improving agents, wax-substituted.sodium phenate can be prepared by the reaction of wax-phenol with metallic sodium in the presence of a non-oxidizing gas., The reaction .mixture is heated at 500 F. during atwo-hour period with rapid stirring to produce finely divided sodium and thereby accelerate the reaction. The proportions of reactants which were used in preparing a weal-substituted alkali'metal phenate according to the above procedure were:

Gram Wax-phenol (13.2% combined phenol content) I 500 Sodium or equivalent amount of potassium 16 Wax-substituted 'phenates of the allrali and alkaline earth metals may also be prepared by reacting a wax-phenol with the desired alcoholate or alkyl metal oxide of an alkali or alkaline earth metal; For this purpose anhydrous methyl and ethyl alcohols are usually most suitable for use in preparing the alkyl metal oxides. As an example, 500 grams of wax-phenol (3-16) of 13.2 per cent combined phenol content was-reacted with sixteen grams of sodium in the term 01' the ethyl sodium oxide byiheating the mixture to about 300 F. during a one-hourperiod'a'nd allowing the alcohol released in the reaction to distill oil, thereby obtaining the wax-substituted sodium phenate as the final product.

(3) CARBOXYLATIOWN TO'F'ORM ALKALI a ALKALINE EARTH METAL SA T OF WAX-PHENOL CARBQXYLIC ACID A product of the foregoing step,'such as the wax-substituted sodium phenate, is heated to a temperature of about 350 F., andCOz is introduced at a rate suflicient to maintain" this temperature. The pressure is graduallymaised to about 500 pounds persquare inch to complete the reaction at this temperature duringn a two-hour period. glhe carboxylationj can also be carried out at atmospheric pressure by introducing a current of CO: at about 400 with stirring for about four hours. The reaction' may be illusas the sodium salt of the foregoing step, as the ONa r v v 0 +00:

is introduced under pressure at trated with unsubstituted sodium phenate by the following equations: 1 I

- ocoom By rearrangement the carboxy group is transferred to the ring, giving the sodium salt of the phenol carboxylic acids,

- Other. carboxylating reactions-may be used in this step of the process, suchlauthe reaction of the alkali metal wax-phenate with carbonyl chloride or carbon tetrachloride; but since the salt formed in the presence of CO2 is obtained in high yield and in a pure state, this is the preferred carboxylation procedure.

Because 01' the high viscosityof the mixture it is advantageous to dilute the1wax-sub5tituted phenol initially with one or two'parts of mineral oil. When a diluent has been used, the mixture can be stirred more readily, making it suitable to introduce CO: at alower temperature. In carboxylating the wax-alkali oxyaromatic compound under pressure the temperature can be more readily controlled by introducing the 00: under pressure at room temperature and gradually raising the mixture to about 350 F. When 00: 350 F., rapid changes in viscosity occur, making it more difficult to'control the temperature of the reaction mixture. The product of this step, where the starting materialv was wax-substituted sodium phenate,-is the sodium salt of wax-substituted phenol carboxyl acid.

FoBMA'rIoN i01 THE SaL'rs or OTHER METALS With an alkali or alkaline earth metal salt, such starting material, the corresponding salts of the other metals canbe prepared. by double decomposition ofthe first-mentioned salt with an alcohol-soluble inorganic or fatty acid salt of the desired metal.-, ,-'I'he use of alcohol as a solvent for the salt is and reaction,

carried out by heating the mixture at 175 F. dura two-hour period. t

desirable to insureproper solution The reaction productof thisdouble decomposition or the alkali or alkaline earth metal salt obtained in the previous stepis used as an intermediaryior obtaining the final metaloxyaromatic-metal'carboxylate salt contemplated by this invention.

The reaction mixture employed in this double decomposition reaction may, for example, consist 01' one mole ofthe sodium salt 01' wax-substituted one mole equivalent oi the inorganic or fatty acidsalt of the desired metal in-alcohol solution. One part by volume oi. Stoddard-solvent may be employed as a diluent for the mixture.- v v (5) FORMATION or THE lila'mrox rsno mric-Mnrlin CABBOXYLATE TYPE or SALT The substitution of the hydroxyl hydrogen in the salt of the hydroxyaromatic (phenol carboxylic) acid obtained in steps (3) or (4) dethe reaction being conveniently.

The alkyl-substituted hydroxyaromatic acid salt may be added to the alkyl metal oxide mixture without separating the sodium salt (chloride) from the pure alkyl metal oxide. The mixture is heated during a one-hour period at 300 F., allowing the alcohol to distill to complete the formation of the metaloxyaromatic-metal carboxylate salt. The product thus obtained is sepa- The alkyl oxides may be conveniently rated from the inorganic reaction salts, which are insoluble, by settling, filtering, or centrifuging, without resorting to water-washing. If desired, the reaction mixture, prior to separation, may be diluted witha suitable solvent'such as a light mineral oil to aid the separation of the salt, such separation being followed by distillation of the diluent to obtain the finished material.

Compounds or compositions obtained according to the foregoing procedure, in which' ,phenol (CeHsOH) was used as the source of the aryl nucleus and petroleum wax as the source of the heavy alkyl (wax) substituent, may beidentified as wax-substituted metal phenate-metal carboxylate salts, or as wax-substituted metaloxy-phenyl metal carboxylate salts or as the metal salts of waxesubstituted phenol carboxylic acids in which both the hydroxyl hydrogen and the carboxyl hydrogen are replaced with metal. Corresponding salts or-metal-organic compounds can be prepared from substituted phenols, and from polycyclic hydroxyaromatic compounds by following the same general procedure described above. For example, the same general procedure described above can be followed in preparing wax-substituted metaloxy-naphthyl-metal carboxylate salts or metal salts of'wax-substituted naphthol carboxylic acid in which the hydroxyl and carboxyl hydrogens are both substituted with metal. A wax-substituted naphthol which may be conveniently used as the starting material for such products is one having a combined naphthol content of sixteen per cent or equivalent phenol content or phenolic ratio of 10.4 per cent.

The wax-substituted metaloxyaromatic-metal carboxylate salts obtained 'by the exemplary procedures described above are,as the result of their relatively low phenolic ratio or combined phenol content; all oil-miscible or oil-soluble products. Although products of this type are designated herein as preferred because of their multifunctional oil-improving properties, it is again emphasized that the invention is not limited to wax-substituted 'metaloxyaromatic-metal carboxylate salts which are oil miscible but is inclusive of this entire field of products irrespective of oil-miscibility.

Compounds or'compositions of both the oilmiscible and non-miscible types have been prepared, and of' the oil-miscible products synthesizedall have been tested as additive agents for viscous mineral oils and have been found to be of multifunctional activity, improving the pour point and viscosity index and inhibiting oxidation of viscous mineral oil fractions. The following list (table) is illustrative of the various oil-miscible metal salts of wax-substituted metaloxyaromatic-metal carboxylate salts which we value as additive agents for viscous mineral oils. As has been previously pointedout, the present invention contemplates metaloxy-metal carboxylate "salts in which both the hydroxyl and carboxyl hydrogen are substituted with the same metal and salts in which the hydroxyl hydrogen and carboxyl hydrogen are replaced with diifere'nt metals. Salts of the former type are designated in the table below as di salts, for example dicobaltous (phenate-carboxylate) salt of wax phenolic acid. In referring to salts of the latter type, the hydroxyl metal substituent is indicated with the sufiix (OM) and the carboxyl metal substituent is indicated with the suflix (COOM). Thus, forexample, a salt of wax-substituted phenol carboxylic acid in which the hydroxyl hydrogen is substituted with cop- Table I Cupric(OM) -s0dium(CO0M') phenol carboxylic acid Di-sodium(phenate-carboxylate) phenol carboxylic acid Cobaltous(OM)-manganous(COOM-') I salt wax-phenol carboxylic acid b Distannous (phenate-carboxylate) salt of waxphenol carboxylic acid Dicobaltous (phenate-carboxylatelsalt of waxphenol carboxylic acid Diferric (phenate-carboxylate) phenol carboxylic acid We claim;

1. A metal salt of an alkyl-substituted hydroxyaromatic'carboxylic acid in which both the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal and in which the alkyl substituent contains at least twenty carbon atoms and is attached to the aryl nucleus;

2. A metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid in which both the hydroxyl hydrogen and the carboxyl hydrogen are substituted'with metal and in which the alkyl substituent contains at least twenty carbon atoms and is attached to the aryl nuceus, saidcomposition being miscible with mineral oil and possessing the property of improving the pour point and viscosity index and inhibiting oxidation of a viscous mineral oil fraction when admixed therewith. v

3. A metal salt of an alkyl-substituted phenol carboxylic acid in which both the hydroxyl hydrogen andv the carboxyl hydrogen are substituted with metal and in which the alkyl substituent contains at least twenty carbon atoms and is attached to the aryl nucleus.

4. A metal salt ,of an alkyl-substituted phenol carboxylic acid in which both the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal and in which the alkyl substitutent contains at least twenty carbon atoms and is attached to the aryl nucleus, said composition being miscible with mineral oil: and possessing the property of improving the pour point and viscosity index and inhibiting oxidation of a viscous mineral oil fraction when admixed salt or. waxsalt of waxsalt of waxhave prepared and tested to demonstrate their therewith.

5. A metal salt of an alkyl-substituted naphthol carboxylic acid in which both the hydroxyl hydrogen and the carboxyl hydrogen are substihydrogen and carboxyl hydrogen are substituted 7 with metal and in which the alkyl substituent contains at least twenty carbon atoms and is attached to the aryl nucleus, said composition being miscible with mineral oil and possessing the property of improving the pour point and viscosity index and inhibiting oxidation of a viscous mineral oil fraction when admixed therewith.

CII

sisting of alkali and alkaline earth metals to form the wax-phenate of said metal; carboxylating said wax phenate to form the corresponding metal salt of wax-phenol carboxylic acid; and finally replacing the hydroxyl hydrogen on said wax-phenol carboxylic acid with a metal.

7. A product obtained by condensing an hydroxyaromatic compound with chlorinated paramn wax in proportions such that the hydroxyaromatic constituent in the resulting wax-hydroxyaromatic product comprises a substantially smaller proportion of said product than the wax with a metal selected from the group consisting of alkali and alkaline earth metals to form a wax-.

substituted aryl oxide of said metal; carboxylating said aryl metal oxide'to form the corresponding'metal salt of a wax-substituted hy droxyaromatic carboxylic acid; and then replacing the hydroxyl'hydrogen of saidfsalt with a metal. -f

8. A product obtained by condensing an hydroxyaromatic compound with chlorinated paraflin wax in proportions such that the hydroxyaromatic constituent in the resulting wax-hydroxyaromatic product comprises a a substantially smaller proportionoi said product than the wax substituent; substituting the hydroxyl hydrogen with a metalselected from the group consisting of alkali andalkaline earth metals to form a wax-substituted aryl oxide of said metal; carboxylating said'aryl metaloxide to form the salt of a wax-substituted hydroxyaromatic carboxylic acid in which the carboxyl hydrogen is substituted with said metalj replacing the metal on the carboxyl group with another metal; and finally replacing the hydroxyl hydrogen with a metal. 1 1

9. A product obtained-by condensing an hydroxyaromatic compound with chlorinated par- 11. A product obtainedby condensing phenol with chlorinated paraffin wax in proportions such that the wax-phenol formed has a combined phenol content not to exceed seventeen per cent; replacing the hydroxyl hydrogen of said waxphenol with a metal selected from the group consisting of alkali and alkaline earth metals to form the wax-phenate of said metal; carboxylating said wax-phenate to form the corresponding metal salt of wax-phenol carboxylic acid; replacing the metal on the carboxyl group with another metal; and finally replacing the hydroxylhydrogenon said wax-phenol carboxylic acid with a metal.

12. The'method of preparing a wax-substi- .tuted metal oxyaromatic-metal carboxylate salt substituent; substituting the hydroxyl hydrogen which comprises: condensing a chlorinated paraflinwax with a hydroxyaromatic compound in the presence of aluminum chloride toform' a wax-substituted hydroxyaromatic compound, reacting said wax-substituted hydroxyaromatic compound with a finely divided alkali metal at an elevated temperature and with rapid stirring to form a wax-substituted aryl alkali metal oxide; carboxylating the product. of the preceding step to form the alkali metal salt of a wax-substituted hydroxyaromatic carboxylic acid; and finally reacting said hydroxyaromatic carboxylic acid salt with a metal alcoholate to replace the hydroxyl hydrogen of said hydroxyaromatic acid salt with the metal of said alcoholate. I

'13. In' the 'method of preparing a parafiln wax-substituted metaloxyaromatic-metal carboxylate salt, the step which includes reacting a metal salt of aparafiin wax-substituted hydroxyaromatic carboxylic acid with a metal alcoeholate to'replace the hydroxyl hydrogen of said affin wax to form a' 'wax-substituted hydroxy- I aromatic compound; substituting the hydroxyl hydrogen in said wax-substituted hydroxyaromatic compound with a metalselected from the group consisting of alkali and alkaline earth metals to form a wax-substituted aryl oxide of said metal; carboxylating said aryl metal oxide to Iorm'the wax-substituted hydroxyaromatic carboxylic acid salt of said metal; and then re-' placing the hydroxyl hydrogen oI-said salt with a metal. i

10. A product obtained by condensing phenol with chlorinated paraflln wax in proportions such that the wax-phenol formed has a combined phenol content'not toexceed seventeen per cent; replacing the hydroxyl hydrogen of said waxphenol with a metal selected from the group conl In. the method of preparing a wax-substituted metaloxyaromatic-metal hydroxyaromatic acid salt with the metal of said alcoholate. paraflin carboxylate salt, the step which includes reacting a metal salt of a paraiiin wax-substituted hydroxyaromatic carboxylic acid with a metal alcoholate at a temperature in the neighborhood of 300 F. during a period of substantially one hour to replace the hydroxyl hydrogen of said hydroxyaromatic acid salt with the metal of saidalcoholate.

, 15. A metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid in, which both the hydroxyl and the carboxyl hydrogens are substituted with metal and in which the alkyl substituent contains at least twenty carbon atoms and 'is attached to the aryl nucleus, the metal substituents being selected from the group consisting of copper, tin, iron, and cobalt.

,ORLAND M. Rm.

JOHN J. GIAMMARIA. HORACE E. REDMAN.