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Publication numberUS2197834 A
Publication typeGrant
Publication dateApr 23, 1940
Filing dateMay 26, 1938
Priority dateMay 26, 1938
Publication numberUS 2197834 A, US 2197834A, US-A-2197834, US2197834 A, US2197834A
InventorsJohn J Giammaria, Horace E Redman, Orland M Reiff
Original AssigneeSocony Vacuum Oil Co Inc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Mineral oil composition
US 2197834 A
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Description  (OCR text may contain errors)

Patented Apr. 1940 PATENT OFFICE MINERAL OIL COMPOSITION tion of New York No Drawing. Application May 26, 1938, Serial No. 210,160

28 Claims.

This invention has to do ina 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 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 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 effect 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 oiliness characteristics and the wear-reducing action of such mineral oils when they 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 purpose of depressing the 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 temperatures which render theoil impracticable for use'under low temperature conditions. Additivejagents have also been developed for improving'jfthe'viscosity index of lubricating oil fractions.

intliegcase of internal combustion engines, par- '45 ticuI rly'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 deposits which cause the piston rings to becomestuck 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 the formation of acidic products of oxidation in mineral oil fractions of the lubricant range, it has been discovered that certain types of recently developed hard metal alloy bearing metals, such 10 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 20 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 de-' veloped for use in mineral oil fractions to im- 5 prove 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 30 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 designatedas the oil-soluble or oil-miscible metal salts of alkyl-substituted hydroxyaromatic carboxylic acids in which both the hydroxyl and the carboxyl hydrogens are substituted with metal, We have discovered that metal oxyaromatic- .-metal carboxylate' salts 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 clear hydrogen has been substituted with a metaloxy group and another nuclear hydrogen is substituted with a carboxyl group in which the carboxyl hydrogen has been replaced with its equivalent weight of metal. This characterizing group may be represented by the formula:

T (OM) (COOM') in which T represents an aromatic nucleus; (OM) represents at least one hydroxyl group the hydrogen of which is replaced by its equivalent weight of metal M; and COOM' represents at least one carboxyl group in which the hydrogen is replaced with its equivalent weight of a metal,

7 M, which may be the same as, or different from,

the metal M. Both the (OM) group and the (COOM') group are attached to the nucleus T.

The metal salts of hydroxyaromatic carboxylic acids of the type'corresponding to thegroup-represented by the above formula which are otherwise unsubstituted are not 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 a solubilizing nature. In other words, it is important that the aryl nucleus carry asubstituent or substituents which will render the composition as a whole miscible with mineral oil fractions. By the terms "oilmiscible 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 in the aryl nucleus, 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 which will give other properties to the com-' position asa-whole in addition to oil-miscibility. We have found, for example, that where the aryl nucleus is substituted with one or more aliphatic groups corresponding to certain aliphatic hydrocarbon compounds of relatively high molecular weight (herein referred to as' heavy alkyl groups), a compound or composition can be obtained which will efi'ect marked improvement in the viscosity index and the pour point as well as other important properties of viscous mineral oils. I

As a general proposition, therefore, it may be said that the improving agents contemplated by this invention are metal salts of hydroxyaromatic carboxylic acid having the characterizing group T(OM) (COOM') described above, in which additional nuclear hydrogen is replaced with an oilsolubilizing substituent such as a predominantly aliphatic material, such substituent comprising a sufficient 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 rad- III.

icals or groups preferably being'high molecular weight-derivatives or heavy alkyl groups.

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

I. R(T(OM) (COOM')) 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 (OM) and (COOM') are 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 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:

II. R(T(OM) (COOM') Y) in which R, T, (OM) and (COOM') have the same significance indicated above and in which Y represents residual hydrogen 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 tri cyclic nuclei are illustrated by the following specific formulae:

R OM

in which'at least one R represents an aliphatic radical or group, preferably a heavy alkyl, group, and in which the remaining R's represent residual hydrogen which may be replaced with hydroxy, chlorine, alkoxy, aroxy, aralkyl, alkaryl, aryl, nitro and amino radicals or groups.

In the foregoing examples it will be observed that the aliphatic or allgvl substituent is a monovalent aliphatic hydrocarbon group, but, as will appear from the hereinafter described synthesis of our oil-improving agent, part or all of the aliphatic hydrocarbon material may be comprised of polyvalent aliphatic hydrocarbon radicals or groups in which the several valences are attached to separate aromatic nuclear groups. Compounds of this type are included under the following general formula representation:

in which T, (OM), and (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 valence only to at least one aromatic nucleus T, v

1 representing the valence of the aliphatic 'radi-.

the molecule represented by the formula whicharoma;

are attached to the aliphatic group or groups represented by R through the valences o.

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 3 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 having aliphatic groups or radicals of different valences (from one to four) in the same molecule. Also it will be observed that since n may be any whole number from one to four, the number of aromatic nuclei T in the molecule may likewisevary from one to four. It will be seen, therefore, that the relationship between n and v in Formula III, in itS 'b1O2-d6$t aspect, is such that when n is equal to one, u is equal to one; and when n is greater than one, the valence v of at least one of the R's is equal to n (in order to tie the several nuclei or T's together), the valence of any remaining R's beingany whole number equal to or less than 11.

As stated above and as will appear more fully later from the description of their synthesis, these materials represented'by general Formula III may contain both monovalent and polyvalent aliphatic substituents. Both the polyvalent aliphatic substituent and the monovalent substituent, if both are present, may be introduced in the nucleus as part ofan alkylation reaction, or all or part of the monovalent aliphatic substituent may be present in the nucleus of a hydroxy-aromatic starting material as low molecular weight aliphatic groups, such as methyl, ethyl, propyl groups, etc. 7

Compounds of the general type last described above, which include polyvalent substituted aliphatic substituents and may also include both the monovalent and the polyvalent substituents, are included under the subgeneric formula representation:

in which T, (OM), and (COOM) have the samesignificance as indicated above; R represents at least one polyvalent aliphatic radical orgroup having a valence v of two, three, or four; Yb indicates the same group of substituents as described above for Y; Rc represents monovalent aliphatic radicals or groups; b' represents the number 'of Ygys and is equal to zero or a whole number corresponding to the valences on the nucleus T not satisfied with R (OM), (COOM'), and Re; 0 indicates 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 (OM), (COOM'), and Ye; and n represents a whole number from two to four and indicates the total number of the groups ('I(OM) (CO0M')Yb'Rc-) present in the molecule represented by theformula'which are attached to the aliphatic group or groups represented by R through the valencesv'.

In the abovgeneral-Formulae III and IV it will be understoo'ri' thatsince R and 13. are ali phatic hydrocarbon i radicals of the chain -type and are each 'attacl'iefl'by one valence onlyto each corresponding aromatic nucleus, the valence'v or v' of such'ra'd numberofaromatkrnuclei inf- 5 uleanddn all or radicals is pf necessity. never. thef number 11, which indicates the 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 valences unsatisfied or else would form a condensed ring or rings byattachment at two or,m ore points to one and the same aromatic nucleus. Such latter compounds, as already indicated from the definition of R or R are not considered as characterizing the product of the present invention although probably formed in some instances in minor amounts as unobjectionable by-products by I certain of the methods of preparation herein disclosed.

A simple type of COIIIDOUIld coming under general Formula III in which 22 and n-is each equal to one and in which there is only one oil-solubilizing aliphatic group R may be illustrated by the following formula showing T for purposes of illustration as a monocyclic nucleus:

on COOM' 'one, 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 one and in which there are two such monolowing formula:

in which the chains and the substituent characters have the same significance defined above.

Compounds of the type satisfying the general Formula III and the subgeneric Formula IV in which R (or R is polyvalent and v (or v) I 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:

In the above formula 0, Re is a monovalent andj'sithe same as monova'lent R in Formula III. Under this same type of compound indicated V valent R groups, may be represented by the folalkyl'group as defined above under Formula IV characterizing groups have the same significance described above under Formula C.

H H H H H a no c c c on n I a M 000M 0 000M OM 000M A XX Y. -R. Yt"-- R. Irv-R. H 11 no 0 c on H H H H H The possible molecular structure of compounds in which the aryl nucleus T is polycyclic will be As to the possible number of R (and Rc groups going to make up a single molecule, this will vary with the extent to which it is desired toeffect substitution of the nucleus with Oil-solubilizing aliphatic groups for obtaining the desired properties in the product and is, of course, limited by the number of valences on the aromatic nucleus which are available for substitution. -As

1 will be apparent to those skilled in the art, the

maximum possible number of R" (and RC) 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 isotherwise substituted. It will also be apparent that available valences on the nuclei may all be attached to polyvalent aliphatic substituents.

It will be understood that the oil-improving agents contemplated by this invention may be pure compounds satisfying the general Formula III described above with any one of the various mono and poly cyclic aromatic nuclei as T and the various. substituents R (or R and Y) described, the only requisites being that at least one nuclear hydrogen be substituted with a metal-oxy (OM) group, at least one nuclear hydrogen be substituted with a (COOM') group, and at least one nuclear hydrogen be substituted with an oil-solubilizing aliphatic radical or group. However, in manufacturing the preferred oilimproving product of the present invention by the preferred methodv 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 o and to different num-- bers of aliphatic groups R As has been emphasized hereinabove, it is im-,

portant that the oil-improving agents as represented by general Formulae III and IV have nuclear hydrogen in the aromatic nucleus T 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 improving agents below which the product or agent will not satisfy the requirements for oil-miscibility. Expressing this in another way, it appears that the hydroxyaromatic constituent of the alkylated hydroxyaromatic compound from which the alkylated metaloxyaromatic-metal carboxylate 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 R (T(OH))n.

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 criticalrange 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; (12) the aryl nucleus T (mono or poly cyclic); (c) the hydroxyl content of the aryl nucleus from which the final product is obtained (mono or polyhydric); (d) the character of aliphatic material comprising the substituent (straight or branched chain); (c) mono or poly substitution 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 alkylation than a monohydric nucleus; and that 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, expressed as:

'r on VII. aw

should not be greater than .17 when the weight .of the hydroxyaromatic nucleus or component net to the corresponding alkylated hydroxyaromatic nucleus or component therein should not be greater than about seventeen parts by weight of the former to about 100 parts by weight of the latter, or about seventeen 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 allphatic substituents and the hydroxyl group; 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 multifunctional 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 R" in the above general Formula III should, for the preferred multifuctional materials contemplated herein, contain at least thirty carbon atoms for each aromatic nucleus T.

The ratio of seventeen per cent, which we may term the phenolic ratio, represents what we consider a maximum figure for the preferred products contemplated herein, and in general it will be found that this figure will be lower, the actual ratio, of course, being dependent upon the variabie factors enumerated above. For example, as will later appear, 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 thirteen per cent.

A further general guide for the synthesis of the preferred improving agents for viscous oils is to alkylate the aromatic nucleus so that it is polysubstituted with aliphatic hydrocarbon radi cals 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 oil fractions, particularly of the viscous or lubricating oil type, to effect marked improvement in several important properties. The improvement effected may be varied somewhat with the aliphatic substituent, petroleum wax and allphatic hydrocarbons of similar characteristics such as ester wax, for example, giving products which effect a marked improvement in viscosity index and pour point in addition to other prop The efiecerties to be hereinafter pointed out. tiveness may also be varied with other substituents in the aryl nucleus-for example, alkoxy groups .may 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 oilmiscible salt of. any metalsatisfying 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 lead and zinc, may serve to increase the load-carrying capacity of lubricating oils.

The procedure whereby the oil-improving agents contemplated by this invention can be prepared may be broadly described as follows:

First the hydroxyl hydrogen in an alkylated hydroxy-aromatic compound is substituted with an alkali or alkaline earth metal to form an alkylated aryl oxide of the corresponding alkali or alkaline earth metal which is then carboxylated to form the alkali or alkaline earth metal salt of the alkaylated hydroxyaromatic carboxylic acid, the reactions being indicated by the following equation:

in which M indicates an alkali or alkaline earth metal, and the remaining characters have the same significance described above in connection with general Formula III. If it is desired to obtain a metal oxyaromatic carboxylate salt in which the carboxyl hydrogen is replaced with alkali or alkaline earth metal the product of the .above reactions may be used as an intermediate starting material for reactionic) to be hereinafter described.

When the desired product is one in which the carboxyl hydrogen is replaced with some metal other than an alkali or akaline earth metal, the next step in the process involves substitution of the alkali or alkaline earth metal in the salt product of reaction (a) with the desired metal by a process of double decomposition, such reaction being indicated by the following equation:

in which Alk(0M) indicates the alcoholate of the metal M which may be the same as or different, than the metal M. The metal substituents and the hydroxyl group of in the carboxyl group metals belonging to the silver, copper; tin,- alu-' minum, 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 improving agents described herein may be broadly classified as the 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 mono or poly cyclic, mono or 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 mono or poly cyclic hydroxyaromatic compound otherwise unsubstituted; or such compounds containing alkyl substituents; or in certain special cases (to be. hereinafter described) the starting material may be an alkyl-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 mono or poly cyclic hydroxyaromatic compound in which part of the nuclear hydrogen is substituted with a member or members of the group consisting of chlorine, hydroxy, alkoxy, aroxy, aryl, alkaryl, and aralkyl groups.

Examples of the hydroxyaromatic compounds which may be used as starting material for the alkylation reaction are: phenol, resorcinol, hydroquinone, catechol, cresol, xylenol, hydroxydiphenyl, benzylphenol, phenyl-ethyl-phenol,

4Q phenol resins, methyl-hydrcxydiphenyl, 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 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 H2504 as a catalyst. I

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 andobtaining the desired phenolic ratio for use in the preferred mineral oil compositions contemplated by this invention.

In this reaction an appropriate mono or poly chlorine-substitutedaliphatic compound or material is reacted with the desired hydroxyaromatic compound in the presence of a catalytic amount of aluminum chloride. Pure or substantially pure mono or 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 gree of alkylation of the product.

- drocarbons, such as a suitable petroleum fraction, 5

as the starting material for our preferred improving agents, converting it into a mixture of differentchlorine (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 suhstituent R" in Formula III above may be pure or mixed compounds typified by .those which characterize the l heavier products of petroleum, such as heavypetroleum oils of the lubricant type, petrolatum, V 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 120 F. Such specially preferred aliphatic hydrocarbon materials commonly have molecular weights of about 250 and have at least twenty carbon. atoms :3 in their molecules.

As stated above, the Friedel-Crafts synthesis affords a convenient means of controlling the de- This is accomplished bycontrolling: (a) the chlorination of the aliphatic hydrocarbon and (b) the reacting proportions of the chlorinated aliphatic hydrocarbon and the hydroxyaromatic compound used in the Friedel-Crafts reaction. As is well known to those skilled in the art, the replacement 3.3 of nuclear hydrogen in the hydroxyaromatic compound with an aliphatic group is, in the Friedel-Crafts synthesis, effected by reaction of such nuclear hydrogen with chlorine in the chlorinated aliphatic compound, the substitution in being effected with evolution of HCl. It will thus be seen that the number of chlorine substituents in a chlorinated aliphatic compound corresponds to the number of valences (22 in general Formula III) which will be satisfied by or attached to hydroxyaromatic nuclei in the product of the reaction. For example, in a reaction where a quantity of pure monochlor-aliphatic hydrocarbon containing say three atomic proportions of chlorine is reacted with one molecular proportion of hydroxyaromatic compound, the resulting alkylated product, R"(T( OH) Yb) 1],, is one in which 22 and n are equal to one and there are three aliphatic groups R attached to one nucleus T. On the other hand, assuming a reaction in which a quantity of pure trichlor-aliphatic hydrocarbon containing three atomic proportions of chlorine is reacted with one molecular proportion of hydroxyaromatic compound, the product would be one in which 1; and n of general Formula III are each equal to three, and the solubilizing action of a single aliphatic group would be distributed of the aliphatic substituent R", particularly where the aliphatic substituent is a wax derivative and the agent is to be used for multifunctional activityin viscous oils, is not obtained with materials predominantly comprised of a compound or compounds R (T(OM) (CO0M')Yb)a (Formula III) ally combined or used up in the alkylation syn in which 12 andn are greater than four. Hence, for use in the Friedel-Crafts reaction the chlorinated high molecular weight aliphatic material should be a compound, or should be predominantly comprised of compounds in which the chlorine content is not greater than a tetrachlor compound.

As will be readily. apparent to those skilled in the art, the chlorination of an aliphatic material such as a liquid petroleum fraction or a crystalline petroleum wax will normally or usually result in a mixture of monoand poly-chlor-aliphatic hydrocarbon compounds. Consequently, the product of a Friedel-Crafts reaction between such chlorinated material and a hydroxyaromatic compound will be a mixture of difierent compounds corresponding to different values of v and n in the formula R (T(OH)Yb)n and the final metal-oxyaromatic carboxylic acid salt derived therefrom according to the reaction of Equation 0 above will likewise be a mixture of compounds corresponding to difierent 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 different specific compounds present in such a mixture which characterize it as a product of the present invention.

However, in the case of a pure compound corresponding to general Formula III or in mixtures thereof, We have, as previously stated, discovered that for a satisfactory product, the *ratio by weight of hydroxyaromatic component (T(OH) )n to the corresponding alkylated hydroxyaromatic nucleus or component (R (T(.OH) )1.) should not be greater than a certain critical maximum ratio which varies with constituents, conditions of use, and properties desired, as discussed in detail hereinabove.

The above-mentioned ratio'of hydroxyaromatic component to the corresponding alkylated hydroxyaromatic component 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 the hydroxyaromatic compound used up in the alkylation 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 material is first chlorinated until the weight of chlorine absorbed indicates that the average composition of the chlorinated product comes-- ponds roughly to say a dichlor-aliphatic hydrocarbon. Such a product will, of course, contain tracted from the weight of the alkylated or aliphatic-substituted product to obtain the weight of hydroxyaromatic material ((T(OH) )n) actu- The reacting thesis. From this value and the weight of the alkylated product (R (T(OH))1.) the phenolic .ratio or phenol content can be readily calculated.

If there are other substituents (Yb) on the hydroxyaromatic nucleus in addition to the monoor polyvalent aliphatic groups, .a deductionv should: be made for them before calculating the phenolic ratio, an operation which will be apparent to those skilled in the art.

In the foregoing description of the Friedel- Crafts 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 hydroxyaromatic compound in which the alkyl group of the ether replaces one of the nuclear hydrogen atoms.

. that the alkylation be efiected with a hydroxyaromatic compound containing such alkoxy or aroxy group as a substituent and a high molecular weight unsaturated aliphatic hydrocarbon (such as polymerized isobutylene, dodecylene, tetradecylene, octadecylene, melene, etc.) or a higher alcohol (such as cetyl alcohol, myricyl alcohol, ceryl alcohol, octadecyl alcohol, etc.) using H2504 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 follow by substitution of one hydroxy 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 by treating 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 hydroxyaromatic compounds arealkylated 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.

-PREPABATION or MEIALOXYABOMATIC-METAL CAR- BOXYLATE SALTS FROM WAX-SUBSTITUTED Pmnwor.

(1) Alkylation of phenol A paraflin wax melting at approximately F. and predominantly comprised of compounds having at least twenty carbon atoms in their molecules is melted and heated to about 200 ,F., after which chlorine is bubbled 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. Preferablythe chlorination is con- .tinued until about one-sixth the weight of the "chlqrwax 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 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 of about 250 F. and then should be more slowly increased to about 350 F. To control the evolution of HCl gas the temperature of the mixture is preferably raised from 250 F. to 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 H01 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 nonalkylated hydroxyaromatic material (phenol) re-. maining 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 material and accomplishing the drying of the product in the same operation.

The wax-substituted phenol thus obtained may be characterized by the general formula R (T(OH)Yh)n, in which R represents at least one aliphatic group or radical characteristic of parafiin wax having a valence v of from one to four; T represents a monocyclic aromatic nucleus; Yb represents residual hydrogen, 1) being a number corresponding. to the number of valences on the nucleus T not satisfied by R and (OH) and n as a number from one to four corresponding to the valences v on the aliphatic group or groups R which are satisfied by the I nuclear group or groups T (OH) Yb. At this step of the process, 12 in the above general formula should always beat least one, since residual hydrogen in the nucleus is important to the car-= boxylation step to be hereinafter described.

A wax-substituted phenol prepared according to the above procedure, in which a quantity of chlorwax containing three atomic proportions of chlorine (sixteen per cent chlorine in the chlorwax) is reacted with one mole of phenol, may, for

go ibrevity herein, be designated as wax-phenol (3-16)! Parenthetical expressions oi. 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 chlor-aliphatic material reacted with one mole of hydroxyaromatic compound in the Friedel-Crafts reaction, and (B) the chlorine content of the chlor-aliphatic material.

In the above example A=3 and 3:16. This same designation will also apply to the metal oxyaromatic-metal carboxylate derivatives.

Wax-phenol (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 (2) Formation of wax-substitute alkali or alkaline earth metal ph nate 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:

Grams Wax-phenol (13.2 per cent combined phenol content) 500 Sodium or equivalent amount of potassium" 16 Wax-substituted phenates of the alkali and alkali 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 (346) of 13.2 per cent combined phenol content was reacted with sixteen grams of sodium in the form of the ethyl sodium oxide by heating the mixture to about 300 F. during a one-hour period and allowing the alcohol released in the reaction to distill off, thereby obtaining the wax-substituted sodium phenate as the final product.

(3) Carboxylation to form alkali or alkaline earth metal salt ofwax-phenol carboxylic acid By rearrangement the carboxy group is transferred to the ring, giving the sodium salt of the phenol carboxylic acid:

OCOONa OH O OCOONa Other carboxylating reactions may be used in this step of the process, such as the reaction of is advantageous to dilute the wax-substituted (4) Formation of the salts ofpther metals With an alkali or alkaline earth metal salt, such as the sodium salt of the foregoing step, as the starting material, the corresponding salts of the other metals can be prepared by double decomposition of the first-mentioned salt with an alcohol-soluble inorganic or fatty acid salt of the desired metal. The use of alcohol as a solvent for the salt is desirable to insure proper solution and reaction, the reaction being conveniently carried out by heating the mixture at' 1'75 F. during a two-hour period.-

The reaction product of this double decomposition or the alkali or alkaline earth metal salt obtained in the previous step is used as an intermediary for obtaining the finalmetaloxyaromatic-metal carboxylate salt contemplated by this invention. I v

The reaction mixture employed in this double decomposition reaction may, for example, consist of one mole 'of'the sodium salt of wax-substituted phenol carboxylic acid and one mole equivalent of the inorganic or fatty acid salt of the desired metal in alcohol solution. One part by volume of Stoddard solvent may be employed as a diluent for the mixture. I (5) ,Formation of the metalomyaromatic-metal carboxylate type of salt As illustrated by equation (0) above the salts of Formula III are obtained by replacing-thehydroxyl hydrogen with the desired metal which with an alcoholate or alkyl oxide'of the desired I metal; The alkyl oxides may be conveniently formed by double decomposition of alkyl sodium oxide with an alcohol-soluble salt (such as a chloride) of the desired metal to form the metal 'alcoholate and the inorganic sodium salt. A

mixture is heated during a. one-hour period at 300 F., allowing the alcohol to distill to completethe formation of the metaloxyaromaticmetal carboxylate salt. (Formula m). The product thus obtained is separated from the inorganic reaction salts, which are insoluble, by settling, filtering, or centr fu ing, without resorting to water-washing. If desired, the reaction mix-.

,ture prior 'to separation, may be diluted with aid the separation of the salt, such separation being followed by distillation of the diluent to ,obtain the finished material. It is to be understood that the foregoing procedure is merely illustrative of the methods which may be employed in synthesizing the various metaloxyaromatic-metal carboxylate salts of alkylated hydroxyaromatic acids contemplated bythis invention; that polycyclic hydroxyaromatic.

compounds may be used instead of phenol and that other aliphatic compounds or predominantly aliphatic materials may be used as the source of the solubilizing alkyl or aliphatic substituent (R in general Formula 111.

As will appear from the foregoing description, the oil-improving agents contemplated by this invention are characterized by the general Formula III (R"(T(OM) (COOM')Yb)n) described hereinabove, such compounds or products may also be characterized as oil-miscible alkylated or alkyl-substituted hydroxyaromatic carboxylic acids in which the hydroxyl and carboxyl hydrogens have been substituted-with their equivalent weight of metal; also as the metal salts of alkylated metaloxyaromatic carboxylic acidsfiit being understood that the terms alkyl and alkylatecl are used herein in a broad sense to include polyatomic or polyvalent, as well as monovalent aliphatic radicals or groups.

To demonstrate the'effectiveness of compounds or products of the type described above in the mineral oil compositions contemplated by this The improving agents used in these tests inj cludecl salts of the type above described in which both the carboxyl and hydroxyl hydrogens were substituted with the same metal and salts in which the carboxyl and hydroxyl hydrogens were. substituted with dilferent metals. Salts of the former type are designated as di salts, for

example dicobaltous salt of wax phenolic acid or di-cobaltous (phenate-carboxy) salts of wax. phenolic acid. In referring tosalts of the latter type the hydroxyl metal substituent is indicated with the suflix (0M) and the carboxyl metal substituent is indicated with the suflix (COOM') Thus, for example, a salt of wax-substituted phenol carboxylic acid in which the hydroxyl hydrogen is substituted with copper and the carboxyl hydrogen is'substituted with sodium will be referred to and indicated in the tables as the cupric (0M)-sodium (COOM') salt of wax phenol carboxylic acid.

' Slocum Inmnrrron This series of tests was conducted with mineral lubricating oil having a Saybolt viscosity of 244 seconds at 130 F. The test involved subjecting the oil and various oil blends to accelerated oxidizing conditions in the presence of metal at a temperature of 350 F. over an extended period of time, the amount of sludge formed during such test being expressed as the tar number.

The improvingagents used were prepared according to the procedure outlined hereinabove.

a. suitable solvent such as a light mineral oil to highly accelerated oxidizing conditions.

Table 1 Tar numbers on oil blends Inhibitor blended evaluated at 350 with motor oil of Saybolt viscosity 1;! 244 sec.

weight 10 11 Start 7days days days 14 days None 0 1s 0u ric(OM)-so d um(COOM') salt of wax phenol carboxylic acid... Dis it or I boxy cacld $4 0 0 Cobaltous (0M)- m a n g a n o u s (COOM) salt of wax henol carhoxyl c acid Distannous salt of wax henol carboxy 0 acid Dicohaltous salt of wax phenol carboxyl c acid Dii'erric salt of wax phenol carboxylc acid 4 0 0 Viscous 0 Trace Trace XXX 0 Trace 0 Viscous Poon Pomr DEPRESSION In addition to the property of inhibiting sludge formation the metal oxyaromatic-metal carboxylate salts of wax-substituted hydroxyaromatic acids are effective pour point depressants,

Table II A. S. T. M. pour Depressant blended with motor oil of Saybolt tests on blends viscosity of 244 sec. 130 F.

F. None +20 Cupric (OM)-sodium (COOM) salt of wax hcnol carboxylic acid 10 20 Disodium salt of wax phenol carboxylic acid--. -10 -20 Cobaltous (0M)-lnanganous (COOM) salt of wax phenol carboxylic a 5 15 25 20 20 OPERATION Tns'r 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 C. F. R. engine. The engine was operated continuously over a time interval of twentyeight 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 E, 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 (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 B is the same oil containing 4% of dicobaltous (phenate-carboxy) salt of wax phenolic acid.

Table III Ring condition Percent slots Carbon T on Degreesstuck fined (101mm NA.

. y V1!2|!34534V5 A 90 360 360 360 s60 20 so 5 18.08 2.! B so 0 4s 0 0 o 0 0 5.39 0.3

droxyaromatic 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 voil; and in the event an alkali or alkaline earth metal is presentas one or all of the metal substituents 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 alkylatlon, 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 sufiicient amount to eifect 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 I the properties desiredin the final oil composition. The metal oxyaromatic-metal carboxylate salts of the type described herein may be used in amounts ranging from one-sixteenth per cent 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 mineral oil having admixed therewith a minor proportion of-an oil-miscible metaloxyaromatic-metal carboxylate salt in which part of the hydrogen of the aromatic nucleus has been replaced with a mineral oil solubilizing substituent.

2. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metaloxyaromatic-metal carboxylate salt in which part of the hydrogen of the aromatic nucleus has been substituted with predominantly aliphatic organic material, said last-mentioned substituent comprising a suflicient proportion of the substituted metaloxyaromatic-metal carboxylate salt to render such salt miscible with said oil under normal conditions of handling and use.

3. An improved mineral oil composition comprising a mineral oil having admixed therewith in minor proportion: an oil-miscible wax-sub of an alkyl-substituted hydroxyaromatic carboxylic acid in which both the hydroxy hydrogen and the carboxyl hydrogen are substituted with the same metal.

6. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with different metals.

7. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible 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 comprises a high molecular weight hydrocarbon derivative.

8. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible 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 is derived from an aliphatic hydrocarbon having at least twenty carbon atoms.

9. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible 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 is derived from petroleum wax.

10. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil miscible metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid in which both the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal, the alkyl substituent in said salt being a high molecular weight aliphatic hydrocarbon derivative and the aryl nucleus being polysubstituted with said aliphatic derivative.

11. Animproved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid in which both the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal, the alkyl substituent in said salt being derived from an aliphatic hydrocarbon having at least twenty carbon atoms and the aryl nucleus thereof being poly-substituted with said aliphatic derivative.

12. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid in which both the hydroxyl hydrogen and carboxyl hydrogen are substituted with metal, the alkyl substituent in said salt being a derivative of petroleum wax and the aryl nucleus thereof being poly-substituted with said wax derivative.

13. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of an alkyl-substituted phenol-carboxylic acid in which both the hydroxyl hydrogen and the carboxyl hydrogen are replaced with metal.

14. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of an alkyl-substituted phenol-carboxylic acid in which both the hydroxyl hydrogen and the carboxyl hydrogen are replaced with metal, the alkyl substituent in said salt being a high molecular weight aliphatic hydrocarbon derivative.

15. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of an alkyl-substituted phenol-carboxylic acid in which both the hydroxyl hydrogen and the carboxyl hydrogen are replaced with metal, the alkyl substituent in said salt being a high molecular weight aliphatic hydrocarbon derivative and the aryl nucleus thereof being poly-substituted with said aliphatic derivative.

16. 'An improved mineral oil composition ccmprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of an alkyl-substituted phenol-carboxylic acid in which both the hydroxyl hydrogen and the carboxyl hydrogen are replaced with metal, the alkyl substituent in said salt being a derivative of petroleum wax.

17. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of an alkyl-substituted phenol-carboxylic acid in which both the hydroxyl hydrogen and the carboxyl hydrogen are. replaced with metal, the alkyl substituent in said salt being a derivative of petroleum wax and the aryl nucleus thereof being poly-substituted with said wax derivative.

18. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of a metal salt of a carboxylated-alkylated phenol in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal, the alkyl substituent being derived from petroleum wax and the proportion by weight of phenol in the parent alkylated-pheno] constituent being in the neighborhood of thirteen percent.

19. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of a metal salt of a carboxylated-alkylated hydroxyaromatic compound which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal, the alkyl substituent thereof being a derivative of petroleum wax and the proportion by weight of the hydroxyaromatic constituent in the parent alkylated hydroxyaromatic constituent being chemically equivalent to not more than about seventeen per cent phenol.

20. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-soluble metal salt of an allgyl-substituted hydroxyaromatic carboxylic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal, said metal substituents being selected from metals of the silver, copper, tin, aluminum, iron, alkaline earth and alkali analytical groups.

21. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of a product of the type obtained by: chlorinating petroleum wax until about one-sixth of the reaction product is chlorine; reacting the chlorinated Wax with a hydroxyaromatic compound in the proportion of one molof the latter to an amount of the chlorinated wax containing about three atomic proportions of chlorine to form a wax-substituted hydroxyaromatic compound; substituting the hydroxyl hydrogen thereof with metal to form a wax-substituted aryl metal oxide of. said metal; carboxylating said metal oxide to form a. metal salt of a wax-substituted hydroxyaromatic carboxylic acid; and substituting the hydroxyl hydrogen of said salt with a metal.

22. An improved mineral oil composition comprising a viscous mineral oil fraction having admixed therewith a minor proportion, from about one-sixteenth to about ten per cent of an oilmiscible alkyl -substituted metaloxyaromaticmetal carboxylate salt.'

23. An improved mineral oil composition comprising a viscous mineral oil fraction having admixed therewith a minor proportion, from about one-sixteenth to about ten per cent of an oilmiscible alkyl substituted metaloxyaromaticmetal carboxylate salt in which the alkyl substituent is derived from an aliphatic hydrocarbon having at least twenty carbon atoms.

24. An improved mineral oil composition comprising a viscous mineral oil fraction having admixed therewith a minor proportion, from about one-sixteenth to about ten per cent of an oilmiscible alkyl substituted metaloxyaromaticmetal carboxylate salt in which the alkyl substituent is derived from petroleum wax.

25. A composition of matter comprising a mineral oil fraction and in admixture therwith a minor proportion of an oil miscible metalorganic compound having the general formula:

in which: T represents an aromatic nucleus; (OM) represents at least one hydroxyl group in which the hydroxyl hydrogen is replaced with its equivalent weight of a metal M, said group being attached to the nucleus T; (COOM') is attached to the nucleus T and represents at least one carboxyl group the hydrogen of which is replaced by its equivalent weight of a metal M; 1'1. represents at least one aliphatic group having a valence V of one to four, and is attached by one valence only to at least one nucleus T; Y represents a monovalent radical selected from the group consisting of residual hydrogen, and chlorine, alkoxy, aroxy, aralykl, alkaryl, aryl, nitro and amino radicals; b represents the number of TS and is equal to zero or a whole number corresponding to the valences on the nucleus T not satisfied by R". (OM), or (COOM); and n is a whole number from one to four; the substituent R comprising a suflicient proportion of the metalorganic' compound to render same miscible with said oil under normal conditions of handling and use.

26. 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(OM) (COOM') Yb) n in which: T represents an aromatic nucleus; (OM) represents at least one hydroxyl group in which the hydroxyl hydrogen is replaced by its equivalent weight of a metal M, said group being attached to the nucleus T; (COOM') is attached to the nucleus T and represents at least one carboxyl group the hydrogen of which is 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; Y represents a monovalent radical selected from the group consisting of residual hydrogen, and chlorine, alkoxy, aroxy, aralkyl, alkaryl, aryl, nitro, and amino radicals; b represents the number of Ys and is equal to zero -or a whole number corresponding to the valences on the nucleus T not satisfied by R", (OM) or (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 thirty for each nucleus T.

27. 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(OM) (COOM') Yb) n in which: T represents an aromatic nucleus; (OM) represents at least one hydroxyl group in which the hydroxyl hydrogen is replaced with its equivalent weight of metal M, said group being attached to the nucleus T; (COOM') is attached -to the nucleus T and represents at least one carvalent radical selected from the group consisting of residual hydrogen, and chlorine, alkoxy, aroxy, aralkyl, alkaryl, aryl, nitro, and amino radicals; b represents the number of Ys and is equal to zero or a whole number corresponding to the valences on the nucleus T not satisfied by R",

(OM) or (COOM'); and n is a whole number 75 mama's from one to four; the equivalent ratio of T(OH) to R (T(OI-I))n in said metalorganic compound being not greater than the chemical equivalent of twenty per cent phenol.

28. 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(OM) (COOM) YbRe) n in which: T represents an aromatic nucleus; (OM) represents at least one hydroxyl group in which the hydroxyl hydrogen is replaced with its equivalent weight of metal M, said group being attached to the nucleus T; (COOM) is attached to the nucleus T and represents at least one carboxyl group the hydrogen of which isreplaced by its equivalent weight of metal M; R represents at least one polyvalent aliphatic hydrocarbon group of at least twenty carbon atoms hav- -.ing a valence 'v' of from two to four; Yb represents a monovalent radical selected from the group consisting of residual hydrogen, chlorine, alkoxy, aroxy, alkaryl, aralkyl, aryl, nitro, and amino radicals; 12' represents the number of Ybs and is equal to zero or a whole number corresponding to the valences'on the nucleus '1 not satisfied by R (OM), (COOM) and Re; R0 represents monovalent aliphatic radicals; 0 represents the number of Rcs and is equal to zero or a whole number corresponding 130 the valences on the nucleus T not satisfied by R", (OM), (COOM) and Yb; and n is a whole numbeer from two to four.

ORLAND M. REIFF. JOHN J. GIAMMARIA. HORACE E. REDMAN.

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US5266225 *Dec 31, 1991Nov 30, 1993Action Testing And Consulting Laboratory, Inc.Lubricating oil and lubricating oil additives
US5281346 *Apr 16, 1992Jan 25, 1994The Lubrizol CorporationTwo-cycle engine lubricant and method of using same comprising alkali or alkaline earth metal salts of carboxylic aromatic acids
US5322634 *Sep 16, 1991Jun 21, 1994Ford Motor CompanyElectrorheological fluids comprising phenoxy organometallic salt particulate
US5356546 *Apr 16, 1992Oct 18, 1994The Lubrizol CorporationMetal carboxylates of alkylene bis/phenol alkanoic acids
US6596038Mar 9, 2001Jul 22, 2003The Lubrizol CorporationFuels additives enhance thermal stability; reaction of dodecylphenol, salicylic acid, and formaldehyde to form aromatic aldehyde resin, basic catalyst
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