GB1570909A - Basic non-carbonated magnesium compositions and fuel lubricant and additive concetrate compositions containing same - Google Patents

Description

(54) BASIC NON-CARBONATED MAGNESIUM COMPOSITIONS AND FUEL, LUBRICANT AND ADDITIVE CONCENTRATE COMPOSITIONS CONTAINING SAME (71) We, THE LUBRIZOL CORPORATION, a corporation duly organized and existing under the laws of the State of Ohio, United States of America, of Box 17100 Euclid Station, Cleveland, Ohio 44117, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us and the method by which it is to be performed to be particularly described in and by the following statement:- This-invention concerns basic magnesium salts of an aromatic hydroxy-containing carboxylic compound and a process for preparing said salts. More specifically, this invention is directed to a process for preparing basic magnesium salts of the aromatic hydroxy-containing carboxylic acids and to the products obtained therefrom and to their use as additives in a variety of lubricating oils and fuels, e.g., gasoline, diesel fuels, etc., either alone or in combination, e.g. as dispersants, detergents or antioxidants.

Generally, it is known that the deterioration of a motor oil, for example, during the operation of an engine, causes the formation of sludge, varnish, etc., which ultimately obstructs the operation of the working parts. Presently, various dispersants, detergents and the like are used as additives in fuels and lubricants for gears, power-transmitting units, internal combustion engines, etc. Although many of these materials have achieved widespread acceptance, there is still need for other additives which, for example, not only inhibit the deterioration of the motor oil under actual service conditions, but also improve the general lubricating characteristics of the oil.

As the use of basic metal salts as additives for fuels and motor oils, etc., increases, it becomes important to provide improved methods for preparing these metal salts, e.g.

overbased magnesium sulfonates and carboxylates. For example, the basic magnesium salts presently available are prepared by utilizing a stoichiometric excess of a magnesium compound- in the presence of various promoters such as alcohols and phenols together with an acidic material, e.g., carbon dioxide, to promote the overbasing of the acids. Obviously, it would be an advantage to have a process for preparing these basic magnesium compositions, e.g. an overbased magnesium carboxylate, which does not rely on the use of an acidic material, e.g., carbon dioxide, to facilitate the overbasing. It has, for example, been found that such noncarbonated basic magnesium salts are particularly useful in lubricants used in railroad diesel engines and as non-gasforming stabilizers for polymers such as polyvinylchloride.

According to the present invention there is provided a process for preparing a noncarbonated, basic magnesium salt of a hydroxy-containing aromatic carboxylic acid having a magnesium content of at least l50V and not more than 500 /" of the stoichiometrically equivalent amount, based on the total amount of acid present, which comprises reacting, at a temperature in the range from 25"C to the decomposition temperature of a reactant, in the absence of any substantial amount of inorganic acid material, (A) at least one hydrocarbylsubstituted or substantially hydrocarbylsubstituted aromatic carboxylic acid which has a hydroxy substituent in the aromatic nucleus, or a salt or saponifiable derivative thereof, wherein the substantially hydrocarbon substituent contains not more than 10 weight percent of polar groups selected from mercapto, halogen, nitro, amino, nitroso, sulfo, keto, oxo groups and combinations thereof, and (B) a stoichiometric excess of not more than 15 equivalents of at least one compound selected from magnesium oxides, hydroxides and alkoxides for each equivalent of said acid salt or derivative thereof, in the presence of (C) at least 0.1 mole of water for each equivalent of magnesium compound; and (D) an amount not more than 0.25 equivalent for each equivalent of aromatic acid of at least one sulfonic acid or a derivative thereof, and then refluxing the resulting mixture for at least 0.5 hour; with the proviso that the reaction is carried out in the absence of any substantial amount of any organic acid other than (A) and (D).

It is a significant feature of this invention that the non-carbonated, basic magnesium salts of this invention are formed in the absence of any substantial amount of inorganic acid material (and in the absence of any added organic acid other than (A) and (D) as defined herein) In this specification and the appended claims this means that there is not present any amount of such inorganic acidic material or acid which will deleteriously affect the final product, or which will cause the formation of products which are not described herein as having the optimum properties. What is substantial may vary in each case but the amount of such acid should be kept under that which will undesirably modify the final product.

The hydrocarbon-substituted hydroxycontaining aromatic acids, e.g. substantially aliphatic hydrocarbon substituted aromatic hydroxy-containing carboxylic acids and the derivatives thereof which can be used in this invention include the hydroxy-containing aromatic carboxylic acids,the anhydrides or a derivative thereof characterized, for example, by the formulae:

I (Rti n(cooM) aroma C (OH)

wherein R, in the above formulae, is a substantially alkyl substituent, wherein at least one R group preferably has at least 8, and, more preferably, at least an average of 12 aliphatic carbon atoms; x is 1, 2 or 3; y is 1 or 2; z is 1, 2 or 3 and, M is selected from a metal, hydrogen, nitrogen and/or an alkyl group of I to 7 carbon atoms. Typically R has up to an average of 400 carbon atoms. In addition to the above, other saponifiable derivatives, e.g. amides, imides, halides, capable of being overbased with magnesium or the magnesium compounds hereinafter described can be used in place of these acids.

The substituents on the carboxylic acid are substantially hydrocarbyl, e.g.

substantially aliphatic hydrocarbyl, and these may contain small amounts of a nonhydrocarbyl group, e.g. polar groups as specified above. The aromatic ring and/or the alkyl substituent can be substituted with one or more polar groups, such as a halogen group, in amounts ranging from about zero up to 100/, by weight without adversely affecting the desired characteristics of the basic carboxylic magnesium salts of this invention.

Of the various substituted aromatic hydroxy-containing carboxylic acids and the derivatives thereof included in the above formulae, the preferred hydroxy-containing substituted aromatic carboxylic acids include the ortho, meta and parahydroxy alkyl substituted aromatic carboxylic acids such as the alkyl-substituted hydroxy benzoic acids and, more preferably the alkyl-substituted salicylic acids and derivatives thereof. The substituted salicylic acids and the derivatives, for purposes of this invention, also include analogous acids derived from the fused ring hydrocarbons, e.g. naphthols. Specific examples of some of the various substituted aromatic hydroxycontaining carboxylic acids and the derivatives thereof, e.g., the C16-C32 alkyl substituted hydroxy aromatic carboxylic acids include the mono- and polyhydroxycontaining alkyl-substituted aromatic carboxylic acids and the mono- and polycarboxylic hydroxy-containing alkylsubstituted aromatic carboxylic acids and the derivatives thereof such as, for example, the alkylated protocatechuic acids, i.e. an alkylated 3 4-dihydroxy-benzoic acid; an alkylated gallic acid, i.e. an alkyl-substituted 3,4,5-trihydroxy-benzoic acid; anacardic acid (o-pentadecadienyl salicylic acid); an alkylated gentisic acid, i.e. an alkylsubstituted 2,5-dihydroxy benzoic acid; an alkylated hydroxy-isophthalic acid e.g. an alkyl-substituted 4-hydroxy-benzene 1,3-dicarboxylic acid; an alkylated hydroxynaphthoic acid, e.g. an alkyl-substituted 1hydroxy-2-naphthoic acid or an alkylsubstituted 3-hydroxy-2-naphthoic acid; an alkylated 4,6-dihydroxy toluic acid, e.g. a C1 6-C24 alkyl-substituted ortho-orsellinic acid.

Of the various substituted aromatic hydroxy-containing carboxylic acids and the derivatives thereof that can be used for purposes of this invention, a number of the preferred carboxylic acids and derivatives thereof may be specifically illustrated and include, for example, the mono- and dialkali or alkaline earth metal salts of the ortho, meta or parahydroxy carboxylic substituted aromatic acids such as the monolithium alkyl-salicylates, the sodium alkylsalicylates, monolithium parahydroxy alkyl benzoates, lithium metahydroxy alkyl benzoates, the alkali metal salts of the alkylsubstituted hydroxy-phthalic acids or terephthalic acids, 2,4-dialkyl hydroxy benzoic acids octylsalicylic acid, pentadecenyl salicylic acid, octadecylsalicylic acid, octyl-4hydroxybenzoic acid and combinations thereof.

The alkali and alkaline earth metal salts of the alkyl-substituted hydroxybenzoic acids wherein the alkyl substituents contain at least 16 aliphatic carbon atoms are particularly preferred and can include the salts of mixtures of the alkyl hydroxybenzoic acids, such as mixtures obtained by reacting, for example, salicylic acid or 4-hydroxybenzoic acid with a mixture of alkenes, e.g., a mixture of alkenes obtained by cracking a paraffinic hydrocarbon. In addition, other metal salts include the mixtures obtained by alkylating phenols with one or more of a mixture of alkenes and subsequently converting the alkyl-substituted phenols to alkylsalicylic acids by the Kolbe-Schmidt reaction. As indicated, a particularly preferred class of substituted hydroxy-aromatic carboxylic acids include the alkyl-substituted salicylic acids and the derivatives thereof, e.g. metal salts, and especially the salicylic acids wherein the alkyl groups are substantially long chain aliphatic, substantially hydrocarbon groups. These substituted salicylic acids, etc., can be derived for example, from benzene of a phenol which has been alkylated with a hydrocarbon or substantially a hydrocarbon having at least 8 aliphatic carbon atoms and preferably at least 16 aliphatic carbon atoms, e.g. a substantially saturated aliphatic hydrocarbon. The alkyl or aliphatic hydrocarbon-substituted salicylic acids can include the individual acids, per se, or a mixture of said acids each having a different alkyl substituent including, for example, mixtures of alkyl-substituted salicylic acids having alkyl groups of from 8 to 18 aliphatic carbon atoms and alkyl groups of 16 to 32 carbon atoms. The hydroxy-containing aromatic carboxylic acids can be substituted with one or more alkyl groups, e.g.

substantially aliphatic hydrocarbon groups preferably having at least 8 carbon atoms and up to about 10,000 aliphatic carbon atoms. Generally, however, the hydrocarbon or substantially aliphatic hydrocarbon substituents can have average molecular weights ranging from 100 up to 100,000 or higher and preferably from 200 to 10,000. For example, the hydrocarbon or substantially aliphatic hydrocarbon substituents may be derived by polymerization of a low molecular weight olefin, e.g. a monoolefin having from 2 to 30 carbon atoms per molecule. A particularly preferred class of such hydrocarbon substituents are derived from polymers of the lower monoolefins such as polyethylene, polypropene, polyisobutene and copolymers of ethylene and propene having average molecular weights ranging from 100 to 10,000 and preferably from 300 to 700.

More specifically, polymers, including copolymers; terpolymers, etc. which may be used in preparing the alkyl or hydrocarbon substituted hydroxy-containing aromatic carboxylic acids include polymers of the monoolefins such as ethylene, propene, 1butene, isobutene, 1-hexe-ne, l-octene, 2 methyl- 1 -heptene, - 3-cyclohexyl- 1 -butene, 2,5-dimethyl- 1 -octene.

In addition, polymers of olefins wherein the olefinic linkage is not in the terminal position are likewise useful and can include, for example, polymers of 2-butene, 3pentene, 4-octene. Further interpolymers of the monoolefins that can be used include, for example, polymers of the monoolefins illustrated above with other interpolymerizable olefinic compounds such as the aromatic olefins, cyclic olefins, polyolefins. More specifically, the interpolymers - can be prepared, for example, by polymerizing isobutene with styrene, isobutene with butadiene; propene with isoprene; ethylene with propene; ethylene with piperylene; isobutene with chloroprene; diisobutene with pmethylstyrene; l-hexene with 1,3hexadiene; l-octene with l-hexene; 1heptene with l-pentene; 3-methyl-I -butene with 1-octene; 3,3-dimethyl- 1 -pentene with l-hexene; isobutene with styrene and piperylene.

The relative proportions of the monoolefin and the other monomers used in preparing the polymers influence the stability and oil-solubility of the magnesium carboxylate salts of this invention and therefore said polymers should be substantially aliphatic and preferably substantially saturated, aliphatic hydrocarbon polymers. More particularly, for purposes of this invention, it is preferred that the polymers contain at least 95% by weight of saturated units derived from aliphatic monoolefins and no more than 5% by weight of the olefinic linkages based on the total carbon-to-carbon covalent linkages in the hydrocarbon substituent. In a more preferred embodiment, the percent of olefin linkages should be less than 2% by weight of the total carbon-to-carbon covalent linkages in said substantially aliphatic hydrocarbon. Moreover, if an aryl substituted olefin is employed, e.g., styrene, the amount should be limited to provide no more than 10% by weight of the aryl substituent, e.g. 0 to 10% by weight.

Specific examples of the polymers .include, for example, a copolymer of 95% by weight of isobutene with 5% by weight of styrene; a terpolymer of 98% by weight of isobutene with 1% by weight of piperylene and 1% by weight of chloroprene; a terpolymer of 95% by weight of isobutene with 2% by weight of 1-butene and 3% by weight of l-hexene; a terpolymer of 60% by weight of isobutene with 20% by weight of 1pentene and 20% by weight of l-octene; a copolymer of 80% by weight of l-hexene and 20% by weight of l-heptene; a terpolymer of 90% by weight of isobutene with 2% by weight of cyclohexene and 8% by weight of propene; a copolymer of 80% by weight of ethylene and 20% by weight of propene. In addition, other hydrocarbon substituents include the substituted aliphatic hydrocarbons, e.g. obtained by halogenating polyisobutene, polypropene, polyethylene and copolymers of ethylene and propene, which may have average molecular weights ranging from 300 to 10,000 and preferably from 700 to 5000.

The substantially neutral metal salt of a substituted aromatic hydroxy-containing carboxylic acid to be subsequently overbased with the magnesium oxide can be obtained by reacting the substituted hydroxy-containing carboxylic acid or a derivative thereof, e.g. the anhydride, halide or ester, with one or more metals or metal compounds and particularly with a metal or metal compound wherein the metal is selected from the alkali and alkaline earth metals of Groups I and II of the Periodic Table.

Other metals or metal compounds which can be used either alone or in combination to prepare the metal carboxylate salt intermediates include, for example, aluminum, tin, cobalt, nickel. Specific examples of the metal compounds include lithium oxide, lithium hydroxide, lithium carbonate, lithium pentylate, sodium oxide, sodium hydroxide, sodium carbonate, sodium methylate, sodium propylate, sodium phenoxide, potassium oxide, potassium hydroxide, potassium carbonate, potassium methylate, silver oxide, silver carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium ethylate, magnesium propylate, magnesium phenoxide, calcium oxide, calcium hydroxide, calcium carbonate, calcium methylate, calcium propylate, calcium pentylate, zinc oxide, zinc hydroxide, zinc carbonate, zinc propylate, strontium oxide, strontium hydroxide, cadium oxide, cadmium hydroxide, cadmium carbonate, cadmium ethylate, barium oxide, barium hydroxide, barium carbonate, barium ethylate, barium pentylate, aluminum oxide, aluminum propylate, lead oxide, lead hydroxide, lead carbonate, tin oxide, tin butylate, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt pentylate, nickel oxide, nickel hydroxide, nickel carbonate, and mixtures thereof. The metal carboxylate salts for purposes of this invention can be classified as acidic salts, neutral salts or basic salts.

The term "acidic salts" includes, for example, a dicarboxylic acid wherein only one of the two carboxyl groups is converted to the salt leaving a free carboxyl group in its molecular structure. The term "neutral salt" includes a dicarboxylic acid, for example, wherein both of the carboxyl groups are converted to salt groups. These neutral salts may be prepared from the reaction of one chemical equivalent of a dicarboxylic acid with one chemical equivalent of a metal or metal compound.

In some instances, more than the calculated stoichiometric amount of metal may be incorporated into the carboxylic acid to form the basic salt. The "basic salt", therefore, includes a metal salt wherein the metal is present in a calculated stoichiometric amount greater than the acid radical. Thus, the basic metal salts of the aromatic hydroxy-containing carboxylic acids may be characterized as metal salts wherein the chemical equivalent of metal e.g. magnesium are in excess of the total chemical equivalents of acid groups.

A "basic salt" therefore is a metal salt, e.g. a basic magnesium salt, wherein the magnesium is present in a stoichiometrically greater amount than the organic acid radicals. These basic metal salts may be characterized as having a metal ratio greater than 1. The term "metal ratio" is the ratio of the total chemical equivalent of metal in the salt to the chemical equivalent of organic acid groups present. Thus, the metal ratio may be characterized as a measure of the calculated stoichiometric excess of a metal in a particular metal salt of one or more organic acids. This term and its use are well known in the art as particularly pointed out, for example, in U.S. patent 3,271,310. In addition to the substituted aromatic hydroxy-containing carboxylate metal salt derivatives, e.g. substituted salicylate metal salts, other derivatives including the anhydrides, halides, and lower alkyl esters, e.g. esters derived from lower aliphatic alcohols having 1.0 to 8 carbon atoms, can be used to prepare the basic carboxylic magnesium salts of this invention.

For purposes of this invention, magnesium is considered as an alkaline earth metal and as having two chemical equivalents per atom. Similarly, basically reactive magnesium compounds such as magnesium oxide or magnesium hydroxide, have two chemical equivalent per molecule.

Basically reactive magnesium compounds are those components that react with a carboxylic acid, salt or saponifiable derivative thereof to form an overbased magnesium salt. Among the basically reactive magnesium compounds useful in the present invention are lightly calcined magnesium oxide, freshly prepared magnesium hydroxides and magnesium alcoholates which have been stored out of contact with carbon dioxide. The amount of basic magnesium compound to be employed for purposes of preparing the basic magnesium carboxylate salts must be a stoichoimetric excess, i.e., as excess over that amount of magnesium normally required to obtain neutral salts of the total acid present and may range up to 15 chemical equivalents of magnesium, e.g., derived from magnesium oxide, for each chemical equivalent of the substituted aromatic hydroxy-containing carboxylic acid or a derivative thereof.

Preferably, an excess of up to 5 equivalents can be used. Among the basically reactive magnesium compounds which can be used to overbase the hydroxy-containing carboxylic acid or its derivatives are the commercially available magnesium oxides in lightly or actively calcined form. The lightly calcined form of magnesium oxide is preferred and is available from various sources e.g. as Morton Elastomag 20, Elastomag 100, Elastomag 170, Dow Synthetic Magnesite, Dow Tectum (Elastomag and Dow are Trade Marks).

In reacting the magnesium compound with the aromatic hydroxy-containing carboxylic acids or a derivative thereof, at least 0.1 mole of water must be present for each chemical equivalent of said magnesium oxide. Preferably, however, not more than 10 moles of water are present for each chemical equivalent of magnesium oxide. Generally, however, the ratio of water to magnesium oxide will range from 0.1 to 5.0 and 0.1 to 2.0 moles of water for each chemical equivalent of magnesium oxide present in the reaction.

In preparing the overbased magnesium carboxylate salts of this invention, the aromatic hydroxy-containing carboxylic acid or derivative thereof is reacted with the magnesium oxide in the presence of water and at least one sulfonic acid. Usually at least 0.05 equivalent, preferably 0.05 to 0.1 equivalent of such acid is used per equivalent of aromatic acid. Derivatives of sulfonic acids, e.g., anhydrides, salts, halides, esters, can be used in place of the acids.

The sulfonate salts are preferably the metal salts and the sulfonate esters are preferably derived from the lower aliphatic alcohols having up to 8 carbon atoms.

The sulfonic acids and the derivatives thereof include the aliphatic-substituted sulfonic acids wherein the aliphatic substituent or substituents contain at least 8 carbon atoms. These sulfonic acids include the alkylarylsulfonic acids, alkylalicyclic sulfonic acids, alkylheterocyclic sulfonic acids and aliphatic sulfonic acids wherein the aliphatic radicals contain at least 12 aliphatic carbon atoms. Specific examples of sulfonic acids and the derivatives thereof include the petroleum sulfonic acids, monoand polywax-substituted naphthalene sulfonic acids, phenol-sulfonic acids, diphenylethersulfonic acids, diphenyletherdisulfonic acids, naphthylenedisulfide sulfonic acids, naphthylenedisulfide disulfonic acids, diphenylamine disulfonic acids, diphenylamine sulfonic acids, thiophene sulfonic acids, chloronaphthalene sulfonic acids. Other substituted sulfonic acids include the cetylchlorobenzene sulfonic acids, cetylphenolsulfonic acids, cetylphenoldisulfide sulfonic acids, cetylphenolmonosulfide sulfonic acids, dilaurylbetanaphtholsulfonic acids, dicaprylnitronaphthalene sulfonic acids, the aliphatic sulfonic acids such as the paraffin wax sulfonic acids, the unsaturated paraffin wax sulfonic acids, the hydroxy-substituted paraffin wax sulfonic acids, tetraisobutene sulfonic acid, tetraamyl sulfonic acid, chloro-substituted paraffin wax sulfonic acids, nitroso-paraffin wax sulfonic acids, petroleum naphthalene sulfonic acids, the polywax-substituted cycloalkylsulfonic acids and various derivatives of these acids particularly the alkali and alkaline earth metal salts of these acids. The petroleum sulfonic acids include a well-known class of sulfonic acids derived from petroleum products as particularly disclosed, for example, in U.S. patents 2,480,638; 2,483,800; 2,718,265; 2,726,261; 2,794,829; 2,832,801, 3,225,086; 3,337,613; 3,351,655; 2,616,904; 2,616,905; 2,723,235; 2,723,236 and 2,777,874.

The aromatic hydroxy-containing carboxylic acid, e.g. alkyl substituted salicylic acid, can be overbased with magnesium oxide in the presence of water without relying on the use of a promoter, e.g. alcohol, phenol, and an inorganic acidic material, e.g. carbon dioxide, as required heretofore.

As stated above, the reaction is carried out at a temperature of at least 250C. The decomposition temperature which provides the upper temperature limit is generally in the range 1750C. to 2000C. Preferably, the temperature employed is at least 809C. and still more preferably the temperature is from 80"C. to 2000C. or 100"C. to 175"C.

The reaction is carried out, preferably, in the presence of at least one substantially inert organic liquid which may range up to 80% by weight of the total composition and preferably from 10% to 50% by weight of the composition. These organic liquids include various commercially available solvents and particularly mineral oils including, for example, Stoddard Solvent, the aliphatic, alicyclic and aromatic hydrocarbons, substituted hydrocarbons and the corresponding halogenated hydrocarbons such as chlorobenzene, and various combinations thereof. The inert organic liquid can be an oil soluble fluid preferably comprising mineral oil and at least one other diluent soluble in said mineral oil but substantially less viscous than the oil. These diluents may include, for example, a combination of mineral oil with one or more aliphatic, alicyclic or aromatic hydrocarbons and halogenated hydrocarbons including, for example, kerosene, xylene, toluene, ethylbenzene, propylbenzene, cumene, fluorobenzene, chlorobenzene, bromobenzene, fluorotoluene, heptene, octene, nonane, decane, trimethylpentane, cyclohexane, cycloheptane. ethylcyclohexane, cyclooctane and various combinations of these.

After the above-recited components are reacted the reaction mixture is refluxed for at least 0.5 hour. Usually the reaction mixture is refluxed until it is haze-free. A mixture is considered haze-free when no haze appears upon inspection by the naked eye against daylight. Normally this reflux period is from 0.5 to 5.0, usually 0.5 to 2.5 hours.

While the primary purpose of this invention is to provide an overbased or basic magnesium salt of a hydroxycontaining aromatic carboxylic acid, it it obvious that it is not necessary to have only magnesium as the metal present in the carboxylic composition. In fact, other metals selected from Groups I and II of the Periodic Table may be present in the basic carboxylic magnesium salts. For example, if an alkali or alkaline earth metal salt other than the magnesium salt is employed at the starting material, the basic magnesium salt will include that metal which was present in the starting material. When a metal salt, for example, is used, e.g. an alkali metal salt of an alkylated salicylic acid, the salt may be an acidic, neutral or basic salt, e.g. having a stoichiometric excess of one or more metals. As stated above, the products of this inventive process have magnesium content of at least 150%, preferably at least 200%, most preferably at least 250% of the stoichiometrically equivalent amount, based on the total equivalent of acid present. For example, if there were 0.9 equivalent of hydroxy aromatic acid and 0.1 equivalent of sulfonic acid present according to this invention the product of this invention would contain at least 1.5, preferably at least 2.0, most preferably at least 2.5 equivalents of magnesium present.

In the following Examples which illustrate the process and products of this invention, all parts and percentages are parts and percentages by weight unless stated to the contrary and the magnesium oxide is lightly calcined magnesium oxide unless otherwise noted.

EXAMPLE 1 A reaction mixture comprising about 512 parts by weight of a mineral oil solution containing about 0.5 equivalent of a substantially neutral magnesium salt of an alkylated salicylic acid wherein the alkyl group has an average of about 18 aliphatic carbon atoms and about 30 parts of weight of an oil mixture containing about 0.037 equivalent of an alkylated benzenesulfonic acid together with about 15 parts by weight (about 0.65 equivalent) of a magnesium oxide and about 250 parts by weight of xylene is added to a flask and heated to a temperature of about 600 C. to 700 C. The reaction mass is subsequently heated to about 85"C. and approximately 60 parts by weight of water are added. The reaction mass is held at a reflux temperature of about 95"C. to 100"C. for about 1-1/2 hours and subsequently stripped at a temperature of 155"C--I60"C., under a vacuum, and filtered. The filtrate comprises the basic magnesium carboxylate salt characterized by a sulfated ash content of 12.35% (ASTM D-874, IP 163), indicating that the salt contains 200% of the stoichiometrically equivalent amount of magnesium.

EXAMPLE 2 A reaction mixture comprising about 506 parts by weight of a mineral oil solution containing about 0.5 equivalent of a substantially neutral magnesium salt of an alkylated salicylic acid wherein the alkyl groups have an average of about 16 to 24 aliphatic carbon atoms and about 30 parts by weight of an oil mixture containing about 0.037 equivalent of an alkylated benzenesulfonic acid together with about 22 parts by weight (about 1.0 equivalent) of a magnesium oxide and about 250 parts by weight of xylene is added to a flask and heated to temperatures of about 60"C. to 70or. The reaction mixture is subsequently heated to about 85"C. and approximately 60 parts by weight of water are added to the reaction mass which is then heated to the reflux temperature. The reaction mass is held at the reflux temperature of about 950-1000C, for about 1-1/2 hours and subsequently stripped at about 155"C., under 40 mm Hg, and filtered. The filtrate comprises the basic carboxylate magnesium salts and is characterized by a sulfated ash content of 15.59% corresponding to 274% of the stoichiometrically equivalent amount.

EXAMPLE 3 A reaction mixture comprising about 4048 parts by weight of a mineral oil solution containing about 4.0 equivalents of a substantially neutral magnesium salt of an alkylated salicylic acid wherein the alkyl groups have an average of 16 to 24 aliphatic carbon atoms and about 240 parts by weight of an oil mixture containing about 0.3 equivalent of an alkylated benzenesulfonic acid together with about 176 parts by weight (about 8.0 equivalents) of a magnesium oxide and about 2000 parts by weight of xylene is added to a flask and heated to temperatures of about 60"--75"C. The reaction mass is subsequently heated to about 82"C. and approximately 480 parts by weight of water are added to the reaction which is then heated to the reflux temperature. The reaction mass is held at reflux temperature of about 95-1000C. for about 1 hour and subsequently stripped at a temperature of about 170C while blowing with nitrogen, and then further stripped at 155"C., under 40 mm Hg, and filtered. The filtrate comprises the basic magnesium carboxylate salts and has a sulfated ash content of 15.77% corresponding to 277% of the stoichiometrically equivalent amount.

EXAMPLE 4 A substantially neutral magnesium salt of an alkylated salicylic acid wherein the alkyl groups have from 16 to 2 aliphatic carbon atoms is prepared by reacting approximately stoichiometric amounts of magnesium chloride with a substantially neutral potassium salt of said alkylated salicylic acid. A reaction mass comprising approximately 6580 parts by weight of a mineral oil solution containing about 6.50 equivalents of said substantially neutral magnesium salt of the alkylated salicylic acid and about 388 parts by weight of an oil mixture containing about 0.48 equivalent of an alkylated benezenesulfonic acid together with approximately 285 parts by weight (14 equivalents) of a magnesium oxide and approximately 3252 parts by weight of xylene is added to a flask and heated to temperatures of about 550C. to 75"C. The reaction mass is then heated to about 82"C.

and approximately 780 parts by weight of water are added to the reaction which is subsequently heated to the reflux temperature. The reaction mass is held at the reflux temperature of about 95"- 100"C. for about 1 hour and subsequently stripped at a temperature of about 170"C., under 50 mm Hg, and filtered. The filtrate comprises the basic magnesium carboxylate salts and has a sulfated ash content of 15.7% corresponding to 276% of the stoichiometrically equivalent amount.

EXAMPLE 5 A reaction mixture comprising approximately 1025 parts by weight of a mineral oil solution containing about 1.0 equivalent of a substantially neutral magnesium salt of an alkylated salicylic acid wherein the alkyl group has an average of at least about 18 aliphatic carbon atoms and about 0.08 equivalent of a petroleum naphthenesulfonic acid together with approximately 60 parts -by weight (3.0 equivalents) of a magnesium oxide and about 750 parts by weight of xylene is added to a flask and heated to a temperature of about 75"C. The reaction mass is subsequently heated to about 85 C. and approximately 440 parts by weight of water are added to the reaction which is then heated to the reflux temperature. The reaction mass is held at the reflux temperature of about 950-l000C. for about 2 hours and subsequently stripped at a temperature of about 160"C., under 40 mm Hg, and filtered. The filtrate comprises the basic magnesium carboxylate salts.

EXAMPLE 6 A reaction mixture comprising approximately 1025 parts by weight of an oil solution containing about 1.0 equivalent of an alkylated hydroxybenzoic acid wherein the alkyl group has an average of about 18 aliphatic carbon atoms and an oil mixture containing about 0.08 equivalent of a sodium salt of an alkylated benzenesulfonic acid together with about 60 parts by weight (3.0 equivalents) of a magnesium oxide and about 500 parts by weight of a solvent containing xylene is added to a flask and heated to temperatures ranging from about 60"--75"C. The reaction mass is subsequently heated to about 85"C. and approximately 60 parts by weight of water are added to the mass which is then heated to the reflux temperature. The reaction mass is held at the reflux temperature of about 950C-1000C. for about 2 hours and subsequently stripped at a temperature of about 1500C., under 40 mm Hg, and filtered. The filtrate comprises the basic carboxylate salts.

EXAMPLE 7 A reaction mixture comprising approximately 1025 parts by weight of a mineral oil solution containing about 1.0 equivalent of a substantially neutral calcium salt of an alkylated salicylic acid wherein the alkyl groups have an average of about 16 to 24 aliphatic carbon atoms and an oil mixture containing about 0.12 equivalent of a sodium salt of an alkylated benzenesulfonic acid together with about 60 parts by weight (3.0 equivalents) of a magnesium oxide and about 750 parts by weight of an organic solvent containing xylene is added to a flask and heated to temperatures ranging from about 60"- 70"C. The reaction mass is subsequently heated to about 85"C. and approximately 200 parts by weight of water are added to the reaction which is then heated - to the reflux temperature. The reaction mass is held at the reflux temperature of about 95"C. to 1000C. for about 2 hours and subsequently stripped under a vacuum, at a temperature of about 165"C. The filtrate comprises the basic magnesium carboxylate salts.

EXAMPLE 8 A reaction mixture comprising approximately 1025 parts by weight of an oil solution containing about 1.0 equivalent of an alkylated gallic acid wherein the alkyl group has an average of about 18 aliphatic carbon atoms and an oil mixture containing about 0.1 equivalent of a sodium salt of a petroleum sulfonic acid together with about 60 parts of weight (3.0 equivalents) of a magnesium oxide and about 500 parts by weight of an organic solvent containing xylene is added to a flask and heated to temperatures ranging from about 600 C.- 75"C. The reaction mass is subsequently heated to about 85"C. and approximately 120 parts by weight of water are added to the reaction mixture which is then heated to the reflux temperature. The reaction mass is held at the reflux temperature of about 950--100"C. for about 2 hours and subsequently stripped at a temperature of about 160"C., under vacuum, and filtered.

The filtrate comprises the basic magnesium carboxylate salts.

EXAMPLE 9 (a) To 6240 grams of a potassium salt of a C18-C24 substituted salicylic acid in a mineral oil diluent is added, over a period of one hour, 309 grams of sulfur dichloride. The reaction mixture is held at 1500 C. during the addition. After the addition, the reaction is cooled to 1200C., and 700 grams of xylene and 300 grams of water are added to it. The mixture is refluxed for 0.75 hour and then stripped to a temperature of 165"C. while nitrogen is bubbled through it. Filtration through filter aid provides the desired diaryl sulfide intermediate.

(b) To a mixture of 509 grams of the diaryl sulfide described in (a), 250 grams of xylene, 34 grams of the sulfonic acid described in Example 1, is added 33 grams of lightly calcined magnesium oxide. The reaction temperature is held at 600 C. during the addition. The temperature is then raised to 85"C. and 60 grams of water is added to it.

The reaction mixture is refluxed at 950C. for 1.0 hour, stripped to 1800C. at 30 mm Hg and filtered through filter aid to provide the final product. This product has a magnesium sulfate content of 15.76% indicating that it contains 270 /n of the stoichiometrically equivalent amount of magnesium.

EXAMPLE 10 A reaction charge composed of 256 parts of the mineral oil solution described in Example 1 and an oil mixture containing about 0.019 parts of the sulfonic acid described in Example 1 is added to a flask.

To this mixture is added a suspension containing 22 parts of freshly precipitated magnesium hydroxide formed by treating an aqueous solution containing 36 parts of magnesium chloride with 3.75 liters of 1 normal sodium hydroxide. One hundred twenty-five (125) parts of xylene is also added to the reactor and its contents are heated to about 600 C. to 700 C. The reaction mixture is subsequently treated with about 60 parts of water and held at reflux (950C. to 105"C.) for 1.5 hours. The desired product is obtained by stripping the reaction mixture with nitrogen blowing at 1550C. to 1600C. at a pressure of 39 mm Hg and filtering the residue.

EXAMPLE 11 A reaction mixture comprising about 2921 parts by weight of a mineral oil solution containing about 2.0 equivalents of a substantially neutral magnesium salt of an alkylated salicylic acid wherein the alkyl groups have an average of about 60 aliphatic carbon atoms and about 121 parts by weight of an oil mixture containing about 0.15 equivalent of an alkylated benzenesulfonic acid together with about 89 parts by weight (about 4.1 equivalents) of a magnesium oxide and about 2060 parts by weight of xylene is added to a flask and heated to temperatures of about 60"C. to 700C. The reaction mixture is subsequently heated to about 85"C. and approximately 540 parts by weight of water is added to the reaction mass which is then heated to the reflux temperature. The reaction mass is held at the reflux temperature of about 950-- 100"C. for about 1-1/2 hours and subsequently stripped at about 155"C., under 40 mm Hg, and filtered. The filtrate comprises the basic magnesium carboxylate salts and is characterized by a sulfated ash content of 8.18% (sulfated ash) corresponding to 228% of the stoichiometrically equivalent amount.

The magnesium carboxylate salts of this invention can be effectively employed in a variety of lubricating and fuel compositions.

The lubricating compositions includeprimarily crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines including automobile and truck engines, two-stroke engine lubricants, aviation piston engines, marine and railroad diesel engines and the like. In addition, however, automotive transmissions, trans-axle lubricants, gear lubricants, metal-working lubricants, hydraulic fluids and various other lubricating oils and greases can be improved by the incorporation therein of a small but effective amount of the carboxylate compositions of this invention.

More specifically, the magnesium aromatic hydroxy-containing carboxylate salts, e.g. particularly the overbased magnesium salts of the alkylated salicylic acids as described hereinabove, may be employed in effective amounts as an additive, e.g. as a dispersant having oxidation-inhibiting properties in amounts ranging up to 30% by weight of the composition. More specifically, these basic magnesium aromatic hydroxy-containing salts may be used in various oleaginous materials, including, for example, the synthetic and mineral lubricating oils, the normally liquid fuels, e.g. gasoline, diesel fuel, kerosene, in amounts ranging from 0.0001% up to 25% or 30% by weight of the total composition. Preferably, however, the basic magnesium carboxylate salts are used in amounts ranging from 0.01% to 30% by weight and more preferably in amounts ranging from 0.10/, to 10% by weight of the total composition. The optimum amount added to a particular oleaginous material will depend upon the particular type of surface or conditions to which the fuel or lubricant is to be subjected. For example, if the overbased carboxylate magnesium salts of this invention are to be added to a gasoline for an internal combustion engine, the amount added to the fuel may range from 0.0001 S to 1 /,, by weight. If, however, the basic magnesium salts are to be added to a gear lube or used in a diesel engine, hydraulic fluid, motor oil, etc., the amount may range as high as 25% by weight of the total composition. In some instances, even larger percentages, e.g., up to 30 /" or higher by weight of the overbased magnesium carboxylate salts, may be utilized depending upon the particular use of the lubricant or fuel.

When used in lubricants or fuel, the salts of this invention are dissolved or stably dispersed in the media in question. The term "stably dispersed" as used in this specification and appended claims means that a product (e.g., a single additive or compound, a mixture of two or more additives or compounds) is dispersed in a given medium to an extent which allows it to function in its intended manner. Thus, for example, where a product of this invention is used in an oil, it is sufficient that the composition be suspended in the oil in an amount sufficient to- enable the oil to possess one or more of the desired properties imparted to it by the suspended product. Such suspension of the products can be achieved in various conventional ways. For example, in constantly circulating oil or oil in splash lubricating systems, physical agitation can keep the products suspended in oil. Likewise, conventional dispersants (such as the acylated nitrogen dispersants disclosed in U.S. Patent 3,219,666) often found in lubricating oils and fuels promote the stable dispersion or suspension of the product. In any event, the intended products will be "soluble" or "stably dispersible" in the normally liquid media in which they will be used in at least the minimum concentrations set forth elsewhere herein. Thus, the terminology "soluble" and "stably dispersible" is used in a conventional manner and will be understood to those of ordinary skill in the art.

The salts of this invention can also the formulated into additive concentrates for use in fuels and lubricants. These concentrates contain, in addition to the salt, substantially inert solvent diluents, and, optionally, other additives as described herein.

As used in the specification and the appended claims, the term "substantially inert" when used to refer to solvents, diluents, base stocks, and the like, is intended to mean that the solvent, diluent, etc., is inert to chemical or physical change under the conditions which it is used so as not to materially interfere in an adverse manner with the preparation, storage, blending and/or functioning of the compositions, additive, compound, etc., of this invention in the context of its intended use. For example, small amounts of a solvent, diluent, etc., can undergo minimal reaction or degradation without preventing the making and using of the invention as described herein. In other words, such reaction or degradation, while technically discernible, would not be sufficient to deter the practical worker of ordinary skill in the art from making and using the invention for its intended purposes. "Substantially inert" as used herein is, therefore, readily understood and appreciated by those of ordinary skill in the art.

The additive concentrates of this invention contain 10 to 70% (by weight) of at least one substantially inert, organic solvent diluent and 90 to 30% of at least one magnesium salt of the invention.

The following illustrate oleaginous and fuel compositions of this invention.

EXAMPLE A A lubricating composition is prepared by blending an SAE 10W-30 lubricating oil with 6.5% by weight of an acylated-nitrogen product obtained by reacting a high molecular weight polyolefin-substituted succinic acid with a polyamine, e.g.

polyethylene polyamine, 1.28% by weight of a zinc dialkylphosphorodithioate, 0.005% by weight of a poly(alkyl methacrylate) antifoam agent and 5.18% by weight of the basic magnesium carboxylate salt obtained by the process of Example 1 of this invention.

EXAMPLE B A blend is prepared with an SAE 10W-40 mineral lubricating oil, 1.0% by weight of the product of Example 1, 0.8% by weight of phosphorus as the adduct obtained by heating zinc dinonylphosphorodithioate with 0.25 mole of 1,2-hexene oxide at 120"C., 6% by weight of a polyisobutylene viscosity index improver having an average molecular weight of about 80,000; 0.005% by weight of a poly-(alkyl methacrylate) anti-foam agent and 0.5% by weight of lard oil.

EXAMPLE C A gasoline is blended with 0.001% by weight of the product of Example 8.

In addition to the basic magnesium salts of this invention, other known additives may be used in the fuel or lubricant. These additives include, for example, detergents of the ash-containing type, dispersants of the ashless type, viscosity-index improving agents, pour-point depressing agents, antifoam agents, extreme-pressure agents, rustinhibiting agents, oxidation and corrosion inhibiting agents and various mixtures of these materials in various proportions.

More particularly, the ash-containing detergents may be illustrated by the oil soluble neutral and basic salts of the alkali or alkaline earth metals of the sulfonic acids, carboxylic acids or the organic phosphorus acids. An additive may be prepared, for example, by the reaction of an olefin polymer, e.g. polyisobutene, having a molecular weight of about 2000 with a phosphorizing agent including, for example, phosphorus trhchloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide or phosphorothioic chloride. The additives most commonly used, however, are the salts of sodium, potassium, lithium, calcium, magnesium, strontium, barium and various mixtures thereof.

A method for preparing the basic salts comprises heating a mineral oil solution of the acid with a stoichiometric excess of a metal neutralizing agent, e.g. a metal oxide, hydroxide, carbonate, bicarbonate, sulfide, at temperatures above about 50"C. In addition, various promoters may be used in the neutralizing process to aid in the incorporation of the excess of metal. These promoters are presently known and include compounds as the phenolic compounds, e.g., phenols, naphthols, alkylphenols, thiophenols, sulfurized alkylphenols and the various condensation products of formaldehyde with the phenolic compounds, e.g., alcohols such as methanol, 2-propanol octyl alcohol, Cellosolve, Carbitol (Trade Marks), ethylene glycol, stearyl alcohol and cyclohexyl alcohol; amines such as aniline, phenylenediamine, phenothiazine, phenyl-beta-naphthylamine and dodecylamime. A particularly effective process for preparing the basic salts comprises mixing the acid with an excess of the alkaline earth metal in the presence of the phenolic promoter and a small amount of water and carbonating the mixture at an elevated temperature, e.g. 600 C to about 2000C.

The extreme pressure agents, corrosioninhibiting and oxidation-inhibiting agents are exemplified by the chlorinated aliphatic hydrocarbons such as chlorinated wax; organic sulfides and polysulfides such as benzyl disulfide, bis(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized sperm oil, sulfurized methyl oleate, sulfurized alkylphenol, sulfurized dipentene, sulfurized ferpene; phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate; phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite, dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl-4-pentyl phenyl phosphite, polypropene (molecular weight 500)-substituted phenyl phosphite, diisobutyl substituted phenyl phosphite; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenyl dithiocarbamate; Group II metal phosphorodithioates such as zinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, barium di(heptylphenyl)phosphorodithioate, cadmium dinonylphosphorodithioate, the zinc salt of a phosphorodithioic acid produced by the reaction of phosphorus pentasulfide with an equimolar mixture of isopropyl alcohol and n-hexyl alcohol.

The fuel or lubricating compositions may contain a metal detergent additive in amounts ranging from 0.001% to 15 /" by weight. In some applications, e.g. in lubricating marine diesel engines, the lubricating compositions may contain as much as 30% of a detergent additive. The compositions, e.g. lubricants of fuels, may contain extreme pressure agents, viscosityindex improving agents, pour-point depressing agents, etc., each in amounts within the range from 0.001% to 15% and preferably in amounts of 0.1% to 10%. One or more of the above-mentioned additives may be used either alone or in combination in various compositions, e.g. fuels or lubricating oils, with 0.0001% to 25% or 30% by weight of the basic carboxylic metal salts of this invention.

The oleaginous materials, e.g. lubricants and fuels, include animal and vegetable oils, e.g. castor oil, lard oil, as well as solventrefined or acid-refined mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are useful base oils. The synthetic lubricating oils include the hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g. polybutenes, propeneisobutene copolymers, chlorinated polybutenes); alkylbenzenes (e.g. dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2) ethylhexyl)benzene); polyphenyls (e.g.

biphenyls, terphenyls). The alkylene oxide polymers and interpoymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., comprise another class of known synthetic lubricating oils. These are exemplified by the oils prepared by polymerization of ethylene oxide, propylene oxide, the alkyl and aryl ethers of these oxyalkylene polymers, e.g. methyl polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500 to 1000, diethyl ether of polypropylene glycol having a molecular weight of 1000 to 1500, or monoand polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3- C8 fatty acid esters of the C130XO acid diester of tetraethylene glycol.

Other synthetic lubricating oils comprise the esters of dicarboxylic acids (e.g. phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer) with a variety of alcohols (e.g. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, pentaerythritol. Specific examples of these esters include dibutyl adipate, di(2- ethylhexyl)sebacate, - di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of 2ethylhexanoic acid and the like.

Silicone-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysiloxane oils and silicate oils comprise another class of synthetic lubricants (e.g.

tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexy)silicate, tetra-(p-tertbutylphenyl) silicate, hexa-(4-methyl-2pentoxy)-disiloxane, poly(methyl)disiloxanes, poly-(methyl-phenyl)siloxanes). Other synthetic lubricants include the liquid esters of phosphoruscontaining -acids (e.g. tricresyl phosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid), and polymeric tetrahydrofurans.

While this invention is described with a number of specific embodiments, it is obvious that there are other variations and modifications which can be made without departing from the spirit and scope of the invention as particularly set forth in the appended claims.

WHAT WE CLAIM IS: 1. A process for preparing a noncarbonated, basic magnesium salt of a hydroxy-containing aromatic carboxylic acid having a magnesium content of at least 150% and not more than 500% of the stoichiometrically equivalent amount, based on the total amount of acid present, which comprises reacting, at a temperature in the range from 250C. to the decomposition temperature of a reactant, in the absence of any substantial amount of inorganic acid material, (A) at least one hydrocarbyl-substituted or substantially hydrocarbyl-substituted

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (18)

**WARNING** start of CLMS field may overlap end of DESC **. phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite, dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl-4-pentyl phenyl phosphite, polypropene (molecular weight 500)-substituted phenyl phosphite, diisobutyl substituted phenyl phosphite; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenyl dithiocarbamate; Group II metal phosphorodithioates such as zinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, barium di(heptylphenyl)phosphorodithioate, cadmium dinonylphosphorodithioate, the zinc salt of a phosphorodithioic acid produced by the reaction of phosphorus pentasulfide with an equimolar mixture of isopropyl alcohol and n-hexyl alcohol. The fuel or lubricating compositions may contain a metal detergent additive in amounts ranging from 0.001% to 15 /" by weight. In some applications, e.g. in lubricating marine diesel engines, the lubricating compositions may contain as much as 30% of a detergent additive. The compositions, e.g. lubricants of fuels, may contain extreme pressure agents, viscosityindex improving agents, pour-point depressing agents, etc., each in amounts within the range from 0.001% to 15% and preferably in amounts of 0.1% to 10%. One or more of the above-mentioned additives may be used either alone or in combination in various compositions, e.g. fuels or lubricating oils, with 0.0001% to 25% or 30% by weight of the basic carboxylic metal salts of this invention. The oleaginous materials, e.g. lubricants and fuels, include animal and vegetable oils, e.g. castor oil, lard oil, as well as solventrefined or acid-refined mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are useful base oils. The synthetic lubricating oils include the hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g. polybutenes, propeneisobutene copolymers, chlorinated polybutenes); alkylbenzenes (e.g. dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2) ethylhexyl)benzene); polyphenyls (e.g. biphenyls, terphenyls). The alkylene oxide polymers and interpoymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., comprise another class of known synthetic lubricating oils. These are exemplified by the oils prepared by polymerization of ethylene oxide, propylene oxide, the alkyl and aryl ethers of these oxyalkylene polymers, e.g. methyl polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500 to 1000, diethyl ether of polypropylene glycol having a molecular weight of 1000 to 1500, or monoand polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3- C8 fatty acid esters of the C130XO acid diester of tetraethylene glycol. Other synthetic lubricating oils comprise the esters of dicarboxylic acids (e.g. phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer) with a variety of alcohols (e.g. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, pentaerythritol. Specific examples of these esters include dibutyl adipate, di(2- ethylhexyl)sebacate, - di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of 2ethylhexanoic acid and the like. Silicone-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysiloxane oils and silicate oils comprise another class of synthetic lubricants (e.g. tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexy)silicate, tetra-(p-tertbutylphenyl) silicate, hexa-(4-methyl-2pentoxy)-disiloxane, poly(methyl)disiloxanes, poly-(methyl-phenyl)siloxanes). Other synthetic lubricants include the liquid esters of phosphoruscontaining -acids (e.g. tricresyl phosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid), and polymeric tetrahydrofurans. While this invention is described with a number of specific embodiments, it is obvious that there are other variations and modifications which can be made without departing from the spirit and scope of the invention as particularly set forth in the appended claims. WHAT WE CLAIM IS:

1. A process for preparing a noncarbonated, basic magnesium salt of a hydroxy-containing aromatic carboxylic acid having a magnesium content of at least 150% and not more than 500% of the stoichiometrically equivalent amount, based on the total amount of acid present, which comprises reacting, at a temperature in the range from 250C. to the decomposition temperature of a reactant, in the absence of any substantial amount of inorganic acid material, (A) at least one hydrocarbyl-substituted or substantially hydrocarbyl-substituted

aromatic carboxylic acid which has a hydroxy substituent in the aromatic nucleus, or a salt or saponifiable derivative thereof, wherein the substantially hydrocarbon substituent contains not more than 10 weight percent of polar groups selected from mercapto, halogen, nitro, amino, nitroso, sulfo, keto, oxo groups and combinations thereof and (B) a stoichoimetric excess of not more than 15 equivalents of at least one compound selected from magnesium oxides, hydroxides and alkoxides for each equivalent of said acid salt of derivative thereof, in the presence of (C) at least 0.1 mole of water for each equivalent of magnesium compound; and (D) an amount not more than 0.25 equivalent for each equivalent of aromatic acid of at least one sulfonic acid or a derivative thereof, and then refluxing the resulting mixture for at least 0.5 hour; with the proviso that the reaction is carried out in the absence of any substantial amount of any organic acid other than (A) and (D).

2. The process claimed in claim 1 wherein the aromatic hydroxy carboxylic acid (A) contains a hydrocarbyl substituent of at least 8 aliphatic carbons.

3. The process claimed in claim 2 wherein the aromatic hydroxy carboxylic acid is a monohydroxy carboxylic acid.

4. The process claimed in claim 2 or 3 wherein the substituted aromatic hydroxy carboxylic acid is a monocarboxylic acid.

5. The process claimed in claim 4 wherein the aromatic hydroxy carboxylic acid is a substituted salicylic acid or a derivative thereof.

6. The process claimed in claim 2, 3,4 or 5 wherein a salt of the substituted aromatic hydroxy carboxylic acid is used.

7. The process claimed in clain 6 wherein the metal salt is an alkali or alkaline earth metal salt.

8. The process claimed in clain 7 wherein the salt is a magnesium salt.

9. The process claimed in any one of claims 2 to 5 wherein the saponifiable derivative (A) is selected from organic acid anhydrides, esters and halides.

10. The process claimed in claim 2 wherein (A) is a hydrocarbon-substituted salicylic acid magnesium salt.

11. The process claimed in any one of claims 2-10 wherein the hydrocarbyl substituent contains an average of 12 to 400 carbon atoms.

12. The process claimed in claim 11 wherein the water is present in an amount in the range from 0.1 to 10 moles for each equivalent of said magnesium compound.

13. The process claimed in any one of claims 2 to 12 wherein the hydrocarbyl substituent is aliphatic.

14. A non-carbonated basic magnesium salt when prepared by the process as claimed in any preceding claim.

15. A fuel or lubricant composition comprising a major amount of lubricating oil or normally liquid fuel and an amount effective as a dispersant, detergent and/or anti-oxidant of the non-carbonated basic magnesium salt claimed in claim 14.

16. An additive concentrate containing 10 to 70% of a substantially inert liquid organic solvent/diluent and 90 to 30% of at least one non-carbonated basic magnesium salt as claimed in claim 14.

17. A non-carbonated basic magnesium salt when prepared by a process as claimed in claim 1, substantially as hereinbefore described in any of Examples 1 to 11.

18. A fuel or lubricant composition as claimed in claim 15 substantially as described in Example A, B or C.