US2252665A - Metal salts of alkyl substituted aryl ether acids and method of making them - Google Patents

Description

Patented Aug. 12-, 1941 METAL ABYL ETHEB ACIDS AND MAKING THEM Orland M. Beifl, was", N. 1.,

Philadelphia, Pa asslgnors to Socony- Incorporated, New York,

P. Otto,

Vacuum Oil Company,

SALTS F ALKYL SUBSTITUTED METHOD OF and Ferdinand N. Y., a corporation of New York No Drawing. Application August 17, 1938, Serial No. 225,422

11 Claims. (Cl. 260-429) This invention relates to the production of certain'new chemical compounds or compositions which may be generally designated as the metal salts of wast-substituted aryl-ether carboxylic acids. Although the invention is broadly concerned with chemical compounds or compositions coming within the above-designated general classification, it contemplates as a preferred group within such general classification those compounds or compositions which are soluble or miscible with mineral oil.

Our invention is based upon the discovery that the oil-miscible metal salts of wax-substituted aryl ether acids are of multifunctional activity when blended with viscous mineral oil fractions in that they effect improvement of several unrelated and related 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 effective, when blended in a minor proportion with mineral oil fractions of the lubricant type, to depress the pour point, improve the Viscosity Index (V. I.) and inhibit By inhibiting oxidation these oil-miscible salts act to retard the formation of sludge and acidic products of oxidation. They also have a peptizing action on such sludge as may eventually be formed. Thus, any one of these preferred oilmiscible 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 aproper choice of metal substituent (lead, copper, tin, or zinc, for example) the loadcarrying 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 oil fractions where one or more of the improved properties recited above is desired. In this regard it is to be understood that the present invention is not concerned with mineral oil compositions to which these preferred oil-soluble compounds have been added. Such oil compositions form the subject matter of our copending application Serial No. 229,876, filed September 14, 1988 (now issued as Patent 2,198,292) to which reference is field of invention, the invention is oxidation of the oil.

made herein for further details in the composition of these compounds,

It is to be understood, however, 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 not limited to such oil-miscible compounds or compositions, since this whole class of new materials is possessed of valuable properties irrespective of oilmiscibility. For example, these compounds or compositions may be used as such as oil-soluble resins for use in paints and varnishes or as intermediaries in the production of resins, resinlike 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 of a particular metal ether carboxylate substituent. Numerous other uses and applications of the compounds or compositions contemplated herein will be readily apparent to those skilled in the art from the following description of their composition and preferred methods of synthesis.

The oil-improving agents contemplated 'by this invention may be considered as wax-substituted hydroxyaromatic compounds in which the hydroxyl hydrogen is replaced with an organic acid group which in turn has its carboxyl hydrogen substituted with its equivalent weight of metal. Compounds of this general character derived from aliphatic acids may be considered as wax-substituted hydroxyaromatics (phenols) wherein the hydroxyl hydrogen is replaced with an aliphatic or alicyclic metal carboxylate group, and compoundsderived from aromatic acids may be considered as wax-substituted phenols wherein the hydroxyl hydrogen is replaced with a benzenoid or heterocyclic metal carboxylate group. These compounds or compositions are all characterized by the presence of. an aromatic nucleus in which at least one nuclear hydrogen has been substituted with a mono or poly-basic ether acid or an oxy acid substitutent having the hydrogen of at least one carboxyl group replaced with its equivalent weight of metal.

The compounds or compositions contemplated by this invention are further characterized by the fact that at least one hydrogen on the characterizing aryl hydroxide nucleus is substituted with an aliphatic hydrocarbon radical or group characteristic of an aliphatic hydrocarbon of high molecular weight which we may term a heavy alkyl group. For obtaining the preferred group of compounds or compositions which are miscible with mineral oil and which possess the multifunctional oil-improving properties, we have found that this "heavy alkylsubstituent in the aryl-ether acid salts under discussion must be derived from a predominantly straight chain aliphatic hydrocarbon of at least twenty carbon atoms such as characterize crystalline petroleum wax. As a matter of fact, paraflln wax is considered to be a preferred source of the heavy alkyl" substituent, and it is 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 aliphatic in nature and containing at least twenty carbon atoms which is susceptible of attachment to an aromatic nucleus-to provide a substituent which, in the proper proportions, will impart to the characterizing group the multifunctional oil-improving properties referred to.

It will be understood that when a mixture of aliphatic hydrocarbon compounds such as characterize petroleum wax, for example, is used to provide the heavy alkyl substituent, the resulting composition will be an intimate mixture of compounds or salts of alkyl-substituted aryl ether acids which differ from each other with respect to the nature of the alkyl substituent. In other words, where the alkylation of' the aryl nucleus has been efiected with a mixture of aliphatic hydrocarbons of at least twenty carbon atoms, the resulting composition will be a mixture of compounds differing in their alkyl substituents but having in common the characterizing nuclear group hereinabove referred to.

In addition to the heavy alkyl substituent, part or all of the nuclear hydrogen on the characterizing aromatic nucleus may be substituted with a radical from the group consisting of: monovalent alkyl groups containing less than twenty carbon atoms, chlorine, alkoxy, aroxy, aralkyl, alkaryl, aryl, nitro, and amino radicals or groups. Compounds of the above general formula-type having mono-, di-, and tri-cyclic nuclei are illustrated by the following specific formulae:

O'Z-COOM I I I in which Z represents an aliphatic, cycloaliphatic or aromatic radical, at least one B. represents an aliphatic radical orgroup containing at least twenty carbon atoms and in which the remaining R's represent residual hydrogen which may be replaced with alkyl groups containing less than twenty carbon atoms, hydroxy, chloacsaccs rine, alkoxy, aroxy. aralkyl, alkaryl, aryl, nitro, and amino radicals or groups.

As aforesaid, it is important that the heavy alkyl substituent in the aryl ether carboxylic acid salts, preferred for use as oil addition agents, contain heavy alkyl substituent in suflicient amount to render the compound or condensation product oil-miscible. The heavy alkyl substituent must comprisev a sufllcient proportion of the composition as a whole so that when blended with a mineral oil it will remain in solution or colloidal suspension under normal conditions of handling and use. It appears that there is a critical range in the degree of wax-substitution of the aryl nucleus characterizing the aryl hydroxide used as a starting material below which the product will not satisfy the requirements for oil-miscibility. The critical range in the degree of wax-substitution of the aryl nucleus in these preferred wax-aryl ether acid salts may vary with: (a) the mineral oil fraction in which the improving agent is to be used; (12) the character of the aryl nucleus (monocyclic or polycyclic and mohohydric or polyhydric); (c) monoor poly-substitution of the aryl nucleus; and (d) other substituents on the aryl nucleus which may be of positive or negative or of neutral solubilizing activity. For example, a polycyclic nucleus appears to require a higher degree of wax-substitution than a monocyclic nucleus and a polyhydric compound requires a higher degree of wax-substitution than a monohydric compounds.

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 aryl hydroxide constituent to the wax-substituted aryl hydroxide constituent which would express a degree of wax-substitution satisfying all cases taking these variables into account. In general, however, it may be said that in these preferred improving agents, the ratio by weight of the aryl hydroxide component in the wax-substituted product (from which the wax-aryl ether acid salt is obtained) to the corresponding wax-substituted aryl hydroxide should not be greater than about twenty parts by weight of the former to about parts by weight of the latter, or about 20 per cent, when the aryl hydroxide is expressed in terms of its chemically equivalent weight of phenol. This ratio, which is hereinafter designated as the phenolic ratio," does not take into account other possible substituents in the characterizing nucleus than the heavy alkyl or wax and hydroxyl group; but since the wax substituent is primarily relied upon in the preferred compounds or compositions contemplated herein as oil-improving agents, it is believed that the foregoing ratio and limit will serve as a working guide for preparation of these preferred materials.

In preparing the wax-aryl ether acid salts, an aryl hydroxide is first alkylated to substitute the aryl nucleus with heavy alkyl groups to the desired extent. The hydroxyl hydrogen is then substituted with an alkali metal to form the alkylated aryl alkali metal hydroxylate, which may then be reacted with the alkali metal salt of a halogenated organic carboxylic acid to form the ether acid salt. For example, the alkylated aryl alkali metal hydroxylate may be reacted with the corresponding alkali metal salt of a chlor-fatty acid to obtain the alkali metal salt of the alkylated aroxy-aliphatic carboxylic acid.

Alkali metal ether acid salts may be obtained cyclic and monoor poly-hydric.

. I aaeaees with the foregoing procedure by using thejal kali metal salt of any chlor-aliphatic acid in'the last-described step. Examplesof such salts are: sodium chloracetate, butyrate, octylate, palmitate, stearate, etc., and halogen-substituted poly Another desirable procedure consists in reacting an ester of the chlor-fatty acid instead of the alkali salt with the alkylated aryl hydroxylate and then saponifying the "ester group to form the salt.

The ether acid salts in which the ether acid or oxyacid substituent 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.COOM 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 a wax-substituted aryl alkali metal hydroxylate with a brom-aryl alkali metal carboxylate such as brom-sodium benzoate in the presence of a small percentage of powdered copper as a catalyst, the reaction mixture being heated to about 400 F.

The alkali metal ether acid salts obtained by the foregoing procedures, when purified, consti tute one group of metal salts contemplated by this invention. Corresponding salts of the other metals may be formed by double decomposition of the alkali metal salt in the presence of a suitable solvent with a salt of the desired metal which is soluble in a solvent for the ether acid salt and in which the corresponding alkali metal salt released in the double decomposition is insoluble. I

These other metal salts of wax-aryl ether acids can also be formed by first neutralizing the alkali metal salt to form the ether acid and then reacting the acid with the alcoholate of the desired metal.

The aryl hydroxide used as the initial reactant in the alkylation step may be monoor poly- Examples of these compounds are: phenol, resorcinol, hydroquinone, catechol, cresol, xylenol, hydroxy-diphenyl, benzylphenol, phenyl-ethyl-phenol, phenol resins, methyl-hydroxydiphenyl, guaiacol, 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 aryl hydroxide with heavy alkyl groups may be accomplished in various ways, such as' by a Friedel-Crafts reaction, using a halogenated high molecular weight aliphatic hydrocarbon compound or a mixture thereof such as a chlorinated petroleum wax, or by reaction with unsaturated high molecular weight aliphatic compounds or higher alcohols in the presence of H2804 as a catalyst.

In general it appears that any metal may be used in the ether acid salt substituent. The metals contemplated 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, va-

nadium, molybdenum, tungsten, uranium, and

platinum.

If it is desired to obtain a product having an alkoxy group as a substituent in the characterizing aryl nucleus, one desirable procedure is to alkylate an aryl hydroxide containing such substituent rather than attempt to introduce the substituent after the alkylation step. In this procedure the alkylation is efiected by reacting the alkoxy-substituted aryl hydroxide with a high molecular weight aliphatic hydrocarbon of at least twenty carbon atoms such as eicosylene, cerotene,.melene or the like, using H2804 as a catalyst. Similarly, the alkylation can be effected with higher alcohols of twenty or more carbon atoms such as myricyl alcohol, ceryl alcohol, etc.

When it is desired to obtain a nitro or amino group as a substituent in the characterizing aryl nucleus, the hydroxyaromatic compounds or aryl hydroxides 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.

The following description illustrates preferred procedures which may be followed in synthesizing the metal salts of wax aryl ether acids contemplated by this invention. The compounds or compositions obtained from the syntheses described below fall into that class or group of products hereinabove referred to as preferred" because of their oil-solubility or their multi-. functional activity when blended with mineral oil fractions. As will be apparent to those skilled in the art, compounds or compositions having a combined phenol content in excess of that necessary for oil-miscibility may be readily obtained by using a chlorinated wax having a chlorine content substantially higher than given below or by changing the ratio of the reactants (chlorwax and phenolic compound).

PREPARATION OF WAX SUBSTITUTED PHENOXY-ARYL ETHER ACID SALTS (1) ALKYLATION or PHEXOL 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 its melting point to not over F., and one mole of phenol (CsHsOH) is admixed therewith. The mixture is heated to about 150 F., and a quantity of anhydrous aluminum chloride corresponding to say about three per cent of the weight of chlorwax is slowly added to the mixture vwith active stirring. The rate of addition of the aluminum chloride should be sufilciently 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 twenty-five minutes to a' temperature in the neighborhood of about 250 F. and then should be more slowly in creased to from about 300 F. to about 350 F. It 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 be heated appreciably above 350 F., nor should it be held at that temperature for. any extended length of time.

It is important that all unreacted or non-alkylated hydroxyaromatic material (phenol) remaining after the alkylation reaction be removed. Such removal can be effected generally by waterwashing, but it is preferable to treat the waterwashed product with super-heated steam, thereby insuring complete removal of the unreacted phenolic material and accomplishing the drying of the product in the same operation.

A wax-substituted phenol prepared according to the above procedure, in which a quantity of chlorwax containing three atomic proportions of chlorine (twenty per cent chlorine in the chlorwax) is reacted with one mole of phenol, may, for brevity herein, be designated as wax-phenol (13-20). Parenthetical expressions of this type (A-B) 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 chlo'r-aliphatic material. In the above example A=3 and B=20. This same designation will also apply to the Wax-aryl ether acid salts derived from the wax-phenolic compounds.

Wax-phenol (3-20) as obtained by the above procedure had a phenol content or a phenolic ratio of about sixteen per cent. Our research indicates that this phenolic ratio in the neighborhood of sixteen per cent may be considered as representing about the maximum for satisfactory miscibility with multifunctional activity in viscous oils of the aryl ether carboxylate metal salt derivatives of alkylated hydroxyaromatic compounds in which the .alkyl substituent is derived from wax and the hydroxyaromatic constituent is derived from phenol (CsHsOI-I). Effective oilimproving agents can, however, be obtained from wax-phenol (3-16) in which the phenol content or phenolic ratio is in the neighborhood of thirteen per cent.

(2) FORMATION or WAX-SUBSTITUTED ALKALI on ALKALINE EARTH METAL PHENATE As an example of 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 a two-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 wax-substituted alkali metal phenate according to the above procedure were:

500 grams wax-phenol (13.2 per cent combined phenol content) 16 grams sodium or equivalent amount of potassium (3) FORMATION or ETHER ACID SALTS mom WAX- ALKALI METAL PHENATE Example 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 wax-substituted phenoxy sodium acetate. By diluting the mixture sufliciently with Stoddard solvent or other appropriate diluent,

the mixture can be centrifuged to remove reac-- tion salts, thereafter removingthe 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 prodnot to remove reaction salts and drying to give a concentrated mineral oil blend of the finished product.

Example b.-200 grams of wax-phenoxy-sodium acetate (3-16) 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 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-phenoxy-zinc acetate (3-16) obtained can be purified by water-washing and distilling to remove the diluent.

Example c.Cobaltous ethylate is 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 is added to a mineral oil blend containing 200 grams of wax-phenoxyacetic acid (3-16) and the reaction mixture is heated to 350 F. and held at that temperature for a two-hour period during which the alcohol distills of! with completion of the reaction. The wax-phenoxy cobaltous acetate thus formed can be purified by settling and centrifuging or waterwashing to remove reaction salts.

Example d.The same general procedures described above have been used in preparing "waxphenoxy-acetate from wax-phenol (3-19) having a combined phenol content or phenolic ratio of 15.7%. Here the proportions of reactants for making the wax-sodium phenate were 200 grams of wax-phenol (15.7% combined phenol) in 800 grams of mineral oil and 8 grams of sodium as the sodium ethylate. 200 grams of wax-phenom acetic acid from the wax phenate obtained above was reacted with 76.8 grams of sodium ethylate to form the wax-phenoxy-sodium acetate (3-19).

Example e.The wax aryl ether acid salts obtained by the procedure of the foregoing examples are of the wax aroxy aliphatic carboxylate type. A wax aroxy aromatic carboxylate type of salt was obtained by mixing 102.8 grams of waxsodium phenate (3-16) with 28.9 grams of bromsodium benzoate and heating the mixture at a reaction temperature of 400 F. over a 4 hour period. In the presence of powdered copper as 4 catalyst, the product of this reaction may be termed wax-phenoxy-sodium-benzoate.

Wax-substituted aryl ether acid salts of the general character described above which are derived from wax phenol may be broadly classified as wax phenyl ether acid salts. Corresponding salts can be prepared from wax-substituted hydroxyaromatic compounds other than phenol (CsHsOH) either monoor poly-cyclic and substituted or unsubstituted, such, *for example, as wax-naphthol (3-14) having a combined naphthol content of sixteen per cent and equivalent phenol content or phenolic ratio or 10.4 per cent. Other high molecular weight aliphatic compounds or materials than petroleum wax may be used as the source for the heavy alkyl ("wax") substituent, and it is also-emphasized that the invention is not limited to products obtained from acetic acid or benzoic acid as a source for the ether acid substituent but that any halogenated aliphatic or aromatic acid (as the alkali salts thereof) may be used to obtain various aliphatic and aromatic radicals or groups in the ether acid salt or oxy acid salt substituent. Examples of the acids whose derivatives may be used in synthesizing the wax aryl ether acids contemplated by this invention are: monobasicaliphatic acidsv such as acetic, butyric, octoic, palmitic, stearic, naphthenic, etc.; polybasic acids such as maleic, succinic, adipic, etc.; aromatic acids such as benzoic, phthalic, cinnamic, iuroic, etc. Both aliphatic and aromatic acids may also carry substituents such as keto, nitro, amino and hydroxy groups, etc.

Wax-aryl ether acid salts of the type described above are highly viscous rubber-like products. which with the phenolic ratio properly controlled are readily soluble in mineral oils. Their color is such that they can be readily blended with light-colored mineral oil fractions without substantial darkening of the oil, which makes them particularly desirable for use in this connection.

Although products of the oil-miscible type are designated herein as preferred, because of their multifunctional improving properties in mineral oil blends, it is again emphasized that the invention is not limited to metal salts oi 'wax"- aryl ether acids in which the phenolic ratio is adjusted for oil-solubility, but that it is inclusive of this entire field of products irrespective of oil-solubility.

The following oil-miscible metal salts of waxsubstituted aryl ether acids have been synthesized, tested in lubricating oil blends, and found to be of multifunctional activity therein in that they stabilize the oil against the deleterious effects of oxidation and improve both the pour point and Viscosity Index.

Table Wax-phenoxy-zinc acetate Wax-phenoxy-sodium acetate Wax-phenoxy-cobaltous acetate Wax-phenoxy-sodium benzoate Wax-phenoxy-cobaltous benzoate It is to be understood that the foregoing specific examples are descriptive rather than limiting, and that the invention includes within its scope such changes and modifications as fairly come within the spirit of the appended claims.

we claim:

1. As a composition of matter, an intimate mixture of the metal salts of alkyl-substituted aroxyaliphatic carboxylic acids in which the carboxyl hydrogen is substituted with the same metal, the

said salts difiering from each other with respect to the nature of the alkyl substituent, the said alkyl substituents being attached to the aryl nuclei and comprising essentially aliphatic hydrocarbon groups having a composition corresponding substantially to the different aliphatic hydrocarbons contained in paraflin wax.

2. As a composition of matter, an intimate mixture of the metal salts or alkyl-substituted aroxyaromatic carboxylic acids in which the carboxyl hydrogen is substituted with the same metal, the said salts differing from each other with respect to the nature of the alkyl substituent, the said alkyl substituents being attached to the aryl nuclei and comprising essentially aliphatic hydrocarbon groups having a composition corresponding substantially to the different aliphatic hydrocarbons contained in paraflin wax.

3. As a composition of matter, an intimate mixture of the metal salts of alkyl-substituted phenoxy-aliphatic carboxylic acids in which the carboxyl hydrogen is substituted with the same .metal, the said salts differing from each other with respect to the nature of the alkyl substituent, the said alkyl substituents being attached to the aryl nuclei and comprising essentially aliphatic hydrocarbon groups having a composition corresponding substantially to the diflerent aliphatic hydrocarbons contained in parailln wax.

4. As a composition of matter, an intimate mixture of the metal salts of alkyl-substituted phenoxy-aromatic carboxylic' acids in which the carboxyl hydrogen is substituted with the same metal, the said salts differing from each other with respect to the nature of the alkyl substituent, the said alkyl substituents being attached to the aryl nuclei and comprising essentially aliphatic hydrocarbon groups having a composition corresponding substantially to the different aliphatic hydrocarbons contained in paramn wax.

5. As a composition of matter, an intimate mixture of the metal salts of alkyl-substituted phenoxy-acetic carboxylic acids in which the carboxyl hydrogen is substituted with the same metal, the said salts difiering from each other with respect to the nature of the alkyl substituent, the said alkyl substituents being attached to the aryl nuclei and comprising essentially aliphatic hydrocarbon groups having a composition corresponding substantially to the different aliphatic hydrocarbons contained in paraflin wax.

6. As a composition of matter, an intimate mixture of the metal salts of alkyl-substituted phenoxy-benzoic carboxylic acids in which the carboxyl hydrogen is substituted with the same metal, the said salts differing from each other with respect to the nature of the alkyl substituent, the said alkyl substituents being attached to the aryl nuclei and comprising essentially aliphatic hydrocarbon groups having a composition corresponding substantially to the diilferent aliphatic hydrocarbons contained in paraflln wax.

'7. As a composition of matter, an intimate mixture of the metal salts of alkyl-substituted aroxy-allphatic carboxylic acids in which the carboxyl hydrogen is substituted with a metal selected from the group consisting of zinc and cobalt, the said salts differing from each other with respect to the nature of the alkyl substituent, the said alkyl substituents being attached to the aryl nuclei and comprising essentially aliphatic hydrocarbon groups having a composition corresponding substantially to the diflerent aliphatic hydrocarbons contained in paraflin wax.

8. A product obtained by condensing an hydroxyaromatic hydrocarbon compound with chlorinated parafiln in proportions such that the hydroxyaromatic constituent in the resulting wax-hydroxyaromatic product comprises a substantially smaller proportion of said product than the wax substituent; substituting the hydroxyl hydrogen of said wax-substituted hydroxyaromatic compound with an alkali metal; and reacting the products of the last-mentioned reaction with the metal salt of a halogenated organic carboxylic acid to form a corresponding metal salt of a wax-substituted-aryl ether acid.

9, A product obtained by condensing an aryl hydroxide with chlorinated paraihn wax in pro-.

portions such that the aryl hydroxide constituent in the resulting wax-substituted aryl hydroxide comprises a substantially smaller proportion of said product than the wax substituent; substituting the hydroxyl hydrogen of said wax-substituted aryl hydroxide with an alkali metal;

and reacting the product of the last-mentioned reaction with the metal salt of a chlor-aliphatic acid to form the wax-aroxy-aliphatic metalcarboxylate.

10. A product obtained by condensing phenol with chlorinated paramn wax in proportions such that the wax-phenol formed has a combined phenol content not to exceed twenty per cent; replacing the hydroxyl hydrogen of said waxphenol with an alkali metal to form a waxsubstituted metal phenate; and reacting the wax phenate with a metal salt or a chlor-aliphatic acid to form a wax-phenoxy-aliphatic metal-carboxylate.

11. The method of preparing a wax-aryl ether acid salt which comprises: condensing a chlorinated petroleum wax predominantly comprised of aliphatic hydrocarbons of at least twenty carbon atoms with a hydroxyaromatic compound in the presence of a Friedel-Crafts catalyst to form a wax-hydroxyaromatic compound; reacting the wax-hydroxyaromatic compound with the alcoholate or an alkali metal to form the wax-aryl oxide of said metal; and then reacting the wax-aryl metal oxide with an alkali metal salt of a halogenated organic acid to form the corresponding salt of a wax-aryl ether acid.

- ORLAND M. REIFF.

FERDINAND P. O'I'IO.