JPS6248718B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a process for producing basic magnesium salts of hydroxy-containing substituted aromatic carboxylic acids.
More particularly, the present invention provides a process for the preparation of basic magnesium salts of hydroxy-containing substituted aromatic carboxylic acids and the products obtained thereby and their addition in various lubricating oils and fuels, such as gasoline and diesel fuel. This relates to its use as an agent. The basic magnesium salt of a hydroxy-containing substituted aromatic carboxylic acid contains at least one substantially hydrocarbon-substituted hydroxy-containing aromatic carboxylic acid containing at least about 0.1 mole of water and optionally at least one hydrocarbon, such as sulfuric acid. A stoichiometric excess of magnesium oxide is reacted in the presence of a sulfur-containing organic acid or derivative thereof at a temperature of at least about 25°C, and the resulting reaction mixture is heated for at least about 0.5 hours, preferably until substantially cloudy. Obtained by refluxing until it disappears.

The present invention provides basic magnesium salts of aromatic hydroxy-containing mono- and polycarboxylic acids obtained by the process of the present invention, and the use of these salts alone or in combination with other known additives as e.g. dispersants in oils and fuels. , including uses as detergents or antioxidants.

It is generally known that, for example, when motor oil deteriorates during operation of an engine, sludge, varnish, etc. are generated, which severely interferes with the operation of moving parts. Currently, various dispersants, detergents, and the like are used as additives in fuels and lubricants for gears, pressure transmission devices, internal combustion engines, and the like. Although many of these additives have been found to be effective,
For example, there is a need to develop additives that not only prevent motor oil degradation under actual operating conditions, but also improve the general lubricating properties of the oil.

With the increasing use of basic metal salts as additives for fuels, motor oils, etc., it would be desirable to provide improved methods for producing such metal salts, such as overbased sulfonic acids or magnesium carboxylates. It's becoming important. For example, currently available basic magnesium salts use a stoichiometric excess of magnesium in the presence of various promoters such as alcohols, phenols, and acidic substances that promote overbasing of acids, such as carbon dioxide. Manufactured by In producing such basic magnesium compounds, such as overbased magnesium carboxylate, it is clear that it would be advantageous to have a method that does not use acidic substances such as carbon dioxide to facilitate overbasing. Dew. For example, such non-carbonated basic magnesium salts are useful in lubricants used in railroad diesel engines and as non-gas producing stabilizers for polymers such as polyvinyl chloride. I understand.

According to the invention, a basic magnesium salt of a substantially hydrocarbon-substituted aromatic hydroxy-containing carboxylic acid is optionally prepared in the presence of water at least one
It has been found that it can be obtained using a stoichiometric excess of magnesium oxide in the presence of a seed sulfur-containing acid. The magnesium salt contains at least 150% to 500%, preferably 200%, of stoichiometric equivalents of magnesium based on the total amount of acid present.
%, more preferably up to 250%. The total amount of acid present can be determined by titration to phenolphthalein to the end point.

It is an object of this invention to prepare basic magnesium salts of alkylated aromatic hydroxy-containing carboxylic acids (e.g., alkyl-substituted hydroxybenzoic acids) that can be used as dispersants with antioxidant properties in various lubricating oils and fuels. An object of the present invention is to provide a manufacturing method. It is a further object of the invention to provide lubricating or normally liquid fuel compositions and additive concentrates containing the above magnesium salts.

The method for producing a basic magnesium salt of a substituted aromatic hydroxy-containing carboxylic acid (e.g., alkyl-substituted hydroxybenzoic acid), e.g., a basic magnesium salt of salicylic acid, according to the present invention includes: (A) the substantial hydrocarbon substituent is a mercapto group; A hydrocarbon substituted or substance containing up to 10% by weight of a polar group selected from the group consisting of a halogen group, a nitro group, an amino group, a nitroso group, a sulfo group, a keto group, an oxo group, and any combination thereof. At least one type of hydrocarbyl-substituted aromatic hydroxycarboxylic acid, its salt or saponifiable derivative is reacted with (B) at least one type of base selected from the group consisting of magnesium oxides, hydroxides and alkoxides. (C) in a stoichiometric excess to about 15 equivalents per equivalent of reactant (A), in the presence of at least about 0.1 mole of water per equivalent of magnesium compound (C), at about 25°C to reacting in the absence of a substantial amount of carboxylic acid other than said reactant (A) at a temperature up to the decomposition temperature of the reactants, and then refluxing the resulting reaction mixture for at least about 30 minutes. , optionally carrying out the reaction in a proportion of about 0.25 equivalents per equivalent of reactant (A).
This can be carried out in the presence of a sulfur-containing organic acid or a derivative thereof.

One of the major features of this invention is that the non-carbonated basic magnesium salt is formed in the absence of a substantial amount of inorganic acid and, as the case may be, in the absence of organic acids other than reactant (A). That's true. This means that no amount of inorganic acid is present that would have a detrimental effect on the final product or cause the formation of a product that is not described herein as having optimal properties. It means not. What is substantial will vary, but in any case the amount of acid should be limited so as not to undesirably modify the final product.

In some embodiments of this invention, the reactants (A), (B)
The reactions of (C) and (C) are carried out in the absence of a substantial amount of acid (organic or inorganic) other than reactant (A).

Hydrocarbon-substituted hydroxy-containing aromatic acids (e.g., substantially aliphatic hydrocarbon-substituted aromatic hydroxy-containing carboxylic acids) that can be used in this invention
and its derivatives include, for example, hydroxy-containing aromatic carboxylic acids represented by the following formulas, anhydrides and derivatives thereof.

In each of the above formulas, R is substantially an alkyl group, and at least one R is preferably at least 8, more preferably at least an average of about 12
aliphatic carbon atoms, x is 1, 2 or 3, y is 1 or 2, z is 1, 2 or 3, and M is metal, halogen, nitrogen and/or 1
an alkyl group containing 7 to 7 carbon atoms. Typically R has on average up to 400 carbon atoms. In addition to the above, other saponifiable derivatives that can be overbased with magnesium or magnesium compounds as described below, such as amides, imides, halides, etc., may also be used.

The carboxylic acid substituents are preferably substantially hydrocarbyl groups, such as substantially aliphatic hydrocarbyl groups, which may contain small amounts of non-hydrocarbyl groups, such as polar groups.
Any of the aromatic rings and/or alkyl substituents may contain from 0 to 10% by weight of one or more polar groups without adversely affecting the desirable properties of the basic carboxylic acid magnesium salts of this invention. It doesn't matter if it is replaced.

Among the various substituted aromatic hydroxy-containing carboxylic acids and derivatives thereof included in each of the above formulas, preferred are ortho-, meta-, or para-hydroxyalkyl-substituted aromatic carboxylic acids such as alkyl-substituted hydroxybenzoic acids, and particularly preferred are are alkyl-substituted salicylic acids and derivatives thereof. For purposes of this invention, the substituted salicylic acids and their derivatives also include similar acids derived from fused ring hydrocarbons such as naphthol.

As already mentioned, the alkyl substituent i.e. a hydrocarbyl group or substantially a hydrocarbyl group and/or the aryl nucleus of said hydroxy-containing aromatic carboxylic acid can be, for example, a mercapto group, a halogen group, a nitro group, an amino group, a nitroso group. , sulfo groups, keto groups, oxo groups, and any combination thereof, up to about 10% by weight, i.e. 0
The content may range from about 10% by weight to about 10% by weight. Various Substituted Aromatic Hydroxy-Containing Carboxylic Acids and Their Derivatives Some examples of _C16 - _C32 alkyl-substituted hydroxyaromatic carboxylic acids include alkylated protocatechuic acids, e.g. alkylated 3,4-dihydroxy aromatic carboxylic acids, Alkylated gallic acid e.g. alkyl substituted 3,4,5-
Trihydroxy aromatic carboxylic acids, anacardic acids (orthopentadecadienylsalicylic acid), alkylated gentisic acids e.g. alkyl-substituted 2,5-dihydroxybenzoic acids, alkylated isophthalic acids e.g. alkyl-substituted 4-hydroxy-1,3-benzenedicarbones acids, alkylated naphthoic acids, such as alkyl-substituted 1-hydroxy-2-naphthoic acids or alkyl-substituted 3-hydroxy-2-naphthoic acids, alkylated 4,6-dihydroxytoluic acids, such as _C16 - _C24 alkyl-substituted orthoorthelic acids. etc.

Among the various substituted aromatic hydroxy-containing carboxylic acids and derivatives thereof used in this invention, preferred ones include, for example, alkyl-substituted monolithium salicylate, alkyl-substituted sodium salicylate, monosodium 2-hydroxy-4-dialkylbenzoate, monolithium parahydroxyalkylbenzoate, lithium metahydroxyalkylbenzoate, or alkyl-substituted hydroxy-containing phthalic acid or terephthalic acid, 2,4-dialkylhydroxybenzoic acid, octylsalicylic acid,
Mono- or dialkali metal or alkaline earth metal salts of substituted ortho-, meta- or para-hydroxy aromatic carboxylic acids, such as the alkali metal salts of pentadecenylsalicylic acid, octadecylsalicylic acid and octyl-4-hydroxybenzoic acid, as well as combinations thereof. is included.

Particular preference is given to alkali metal or alkaline earth metal salts of alkyl-substituted hydroxybenzoic acids in which the alkyl substituents contain at least 16 aliphatic carbon atoms, such as for example salicylic acid or 4-hydroxybenzoic acid with alkene mixtures. Also included are salts of mixtures of alkylhydroxybenzoic acids, such as those obtained by reaction with mixtures of alkenes obtained by cracking paraffinic hydrocarbons. Additionally, other metal salts are obtained by alkylating phenols with one or more of the alkene mixtures and converting the resulting alkyl-substituted phenols to alkylsalicylic acids by a Kolbe-Schmidt reaction. There are also mixtures. As mentioned above, particularly preferred substituted hydroxy-containing aromatic carboxylic acids are alkyl-substituted salicylic acids and derivatives thereof, such as metal salts, and particularly preferred are substituted hydroxy-containing aromatic carboxylic acids, in which the alkyl groups are substantially long-chain aliphatic. It is an alkyl salicylic acid which is a hydrocarbon group. The substituted salicylic acid and the like can be substituted with a hydrocarbon or substantially hydrocarbon having at least about 8, preferably at least about 16 aliphatic carbon atoms, such as benzene or a substantially saturated aliphatic hydrocarbon. It can be derived from phenol. The alkyl- or aliphatic-substituted salicylic acids include single acids and/or alkyl-substituted salicylic acids with alkyl groups having, for example, 8 to 18 aliphatic carbon atoms and alkyl-substituted salicylic acids having 16 to 32 carbon atoms. Included are mixtures of acids, each having a different alkyl group, such as a mixture. Hydroxy-containing aromatic carboxylic acids are 1
It may be substituted with one or more alkyl groups, such as substantially aliphatic hydrocarbon groups preferably having at least 8 and up to about 10,000 aliphatic carbon atoms. Generally, however, the hydrocarbon group or substantially aliphatic hydrocarbon group has an average molecular weight of about 100 to about 10,000 or more, preferably about 200 to about 10,000.
For example, the hydrocarbon or substantially hydrocarbon groups can be derived by polymerizing low molecular weight olefins, such as monoolefins, having 2 to 30 carbon atoms per molecule. Particularly preferred such hydrocarbon groups have an average molecular weight of about 100 to about
10000, preferably about 300-700 polyethylene,
They are derived from polymers of lower monoolefins such as polypropylene, polyisobutylene, and copolymers of ethylene and propylene.
More specifically, polymers (including binary copolymers, ternary copolymers, etc.) that can be used in producing the alkyl- or hydrocarbon-substituted hydroxy-containing aromatic carboxylic acid include ethylene, propylene, 1-butene, 1-isobutene, 1-hexene, 1-octene, 2-methyl-1-heptene,
3-cyclohexyl-1-butene, 2-methyl-
It is a polymer of monoolefin such as 5-propyl-1-hexene.

Furthermore, polymers of olefins in which the olefin linkages are not located at the ends can be used as well, and include, for example, polymers of 2-butene, 3-pentene, or 4-octene.
Furthermore, interpolymers of monoolefins that can be used include, for example, polymers of the above-mentioned monoolefins and interpolymer olefin compounds such as aromatic olefins, cyclic olefins, and polyolefins. Such interpolymers include, for example:
Isobutene and styrene, isobutene and butadiene, propene and isoprene, ethylene and propylene, ethylene and piperylene, isobutene and chlorprene, diisobutene and paramethylstyrene, 1
-hexene and 1,3-hexadiene, 1-octene and 1-hexene, 1-heptene and 1-pentene, 3-methyl-1-butene and 1-octene,
It can be obtained by polymerizing 3,3-dimethyl-1-pentene and 1-hexene, isobutene, styrene, piperylene, etc., respectively.

The relative proportions of monoolefin and other monomers used to produce the above polymers affect the stability and oil solubility of the magnesium salts of this invention; The polymer must be an aliphatic polymer, preferably a substantially saturated aliphatic hydrocarbon polymer. For this invention, the polymers contain at least about 95% by weight saturated units derived from aliphatic monoolefins and contain about 5 olefinic bonds based on the total carbon-carbon covalent bonds in the hydrocarbon substituents. Preferably, it contains only up to % by weight. In a more preferred embodiment, the content of olefinic bonds is less than about 2% by weight of the total carbon-carbon covalent bonds in said substantially aliphatic hydrocarbon. Furthermore, when using an aryl-substituted olefin, such as styrene, the amount of aryl substituents is approximately
Must be limited to 10% by weight, 0 to about 10% by weight.

Specific examples of polymers include copolymers of 95% by weight of isobutene and 5% by weight of styrene, and isobutene.
Terpolymer of 98% by weight with 1% by weight of piperylene and 1% by weight of chlorprene, terpolymer of 95% by weight of isobutene with 2% by weight of 1-butene and 3% by weight of 1-hexene, 60% by weight of isobutene % and 1
- 20% by weight of pentene and 20% by weight of 1-octene
A terpolymer of 90% by weight of isobutene, 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, etc. Furthermore, other hydrocarbon substituents having an average molecular weight of about 300 to 10,000;
Preferably, substituted aliphatic hydrocarbons such as those obtained by halogenating polyisobutylene, polypropylene, polyethylene or copolymers of ethylene and propylene with a molecular weight of about 700 to 5000 are preferred.

As already mentioned, the oil-soluble basic magnesium salt of the present invention is prepared by combining either a substituted aromatic hydroxycarboxylic acid or a saponifiable derivative thereof, such as a metal salt, with a stoichiometric excess of a base-reactive magnesium compound. It is obtained by reacting in the presence of at least about 0.1 mole of water per equivalent of magnesium compound and refluxing the resulting reaction mixture until it is substantially clear.

A substantially neutral metal salt of a substituted aromatic hydroxy-containing carboxylic acid to be subsequently overbased with a magnesium compound is a substituted aromatic hydroxy-containing carboxylic acid or its derivatives i.e. anhydrides, halides, esters, etc. is obtained by reacting with one or more metals or metal compounds selected from the group consisting of alkali metals and alkaline earth metals of Groups and Groups of the Periodic Table.

Other metals or metal compounds that can be used alone or in combination in the production of the carboxylic acid metal salt intermediate include, for example, aluminum,
Examples include tin, cobalt, and nickel. Specific examples of 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, and water. Potassium oxide, 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, cadmium oxide, cadmium hydroxide, cadmium carbonate, cadmium ethylate, barium oxide, hydroxide Barium, barium hydrate, barium carbonate, barium ethylate,
Barium pentylate, aluminum oxide, aluminum propylate, lead oxide, lead hydroxide, lead carbonate, tin oxide, tin butyrate, cobalt oxide,
These include cobalt hydroxide, cobalt carbonate, cobalt pentylate, nickel oxide, nickel hydroxide, nickel carbonate, and mixtures thereof. For the purpose of this invention, metal salts of carboxylic acids can be classified into acid salts, neutral salts and basic salts. "Acidic salts" include, for example, dicarboxylic acids in which only one of the two carboxyl groups is converted to a salt and the other remains as a free carboxyl group. "Neutral salts" include, for example, dicarboxylic acids in which both carboxyl groups have been converted to salts. The neutral salt can be prepared by reacting one chemical equivalent of the dicarboxylic acid with one chemical equivalent of the metal or metal compound. In some cases, more than the calculated stoichiometric amount of metal can be introduced into the carboxylic acid to form a basic salt. Therefore, a "basic salt" refers to a metal salt in which the metal is present in stoichiometric excess over the acid group. That is, basic metal salts of aromatic hydroxy-containing carboxylic acids, such as magnesium salts, are characterized as having an excess of chemical equivalents of metal over the total number of chemical equivalents of acid groups. For purposes of this invention, the ratio of the total number of equivalents of metal, such as magnesium, to the total number of equivalents of acid is greater than 1.0, and up to about 15 chemical equivalents of metal are present for each chemical equivalent of acid.

The above basic metal salts can also be defined as having a metal ratio greater than 1.0. This "metal ratio" is the ratio of the total chemical equivalents of metals in the salt to the organic acid groups. The metal ratio can therefore be characterized as a measure of the stoichiometric excess of metal in one or more particular metals. This term and its use are well known in the art and as pointed out, for example, in US Pat. No. 3,271,310. In addition to the substituted aromatic hydroxy-containing carboxylic acid metal salt derivatives, such as substituted salicylic acid metal salts, other compounds such as anhydrides, halides and lower alkyl esters, such as esters derived from lower aliphatic alcohols having 1 to 8 carbon atoms, etc. Derivatives of can also be used in the preparation of the basic carboxylic acid magnesium salts of this invention.

In this invention, magnesium is considered an alkaline earth metal with two chemical equivalents per atomic weight. Similarly, base-reactive magnesium compounds such as magnesium oxide and magnesium hydroxide have two chemical equivalents per molecule. A base-reactive magnesium compound is a compound that reacts with a carboxylic acid or its salt or saponifiable derivative to produce an overbased magnesium salt. Base-reactive magnesium compounds useful in this invention include lightly calcined magnesium oxide, freshly prepared magnesium hydroxide, and magnesium alcoholates that have been stored without contact with carbon dioxide. The amount of base-reactive magnesium compound used to prepare the basic carboxylic acid magnesium salt is at least in stoichiometric excess, i.e., over the amount of magnesium normally required to obtain the neutral salt of all the acids present. An excess is necessary, for example up to about 15 chemical equivalents of magnesium, derived from magnesium oxide, per chemical equivalent of substituted aromatic hydroxy-containing carboxylic acid or derivative thereof. Preferably, about 0.5 to about 5.0 equivalent excess is used. Among the base-reactive magnesium compounds that can be used to overbased substituted aromatic hydroxy-containing carboxylic acids or derivatives thereof are commercially available lightly or actively calcined magnesium oxides. Magnesium oxide in lightly calcined form is preferred, including Morton Elastomag 20, Elastomag
100, Elastomag 170, Dow Synthetics
Some are commercially available under trade names such as Magnesite and Dow Tectum.

The reaction of the magnesium compound with the substituted aromatic hydroxy-containing carboxylic acid or derivative thereof requires the presence of at least about 0.1 mole of water per chemical equivalent of magnesium oxide. Preferably, from about 0.1 moles to about 10 moles of water are present per chemical equivalent of magnesium oxide. Generally, however, the ratio of water to magnesium oxide is from 0.1 to 0.5 moles, preferably from 0.1 to 2.0 moles of water per chemical equivalent of magnesium oxide.

As previously mentioned, the basic carboxylic acid magnesium salts of this invention are prepared by reacting a substituted aromatic hydroxy-containing carboxylic acid or derivative thereof with magnesium oxide in the presence of water. Optionally, this reaction can be carried out in the presence of at least one sulfur-containing organic acid. Usually about 0.05 to about 0.25 equivalents of sulfur-containing organic acid are used. Derivatives of sulfur-containing acids such as anhydrides, salts, halides, esters, etc. may also be used. The sulfur-containing acid or derivative thereof is approximately
Up to 0.25 chemical equivalents are used. Preferably, about 0.05 to about 0.25 chemical equivalents, preferably about 0.05 to about 0.1 chemical equivalents, of sulfur-containing acid or derivative thereof are used for each chemical equivalent of the substituted aromatic hydroxy-containing carboxylic acid or derivative thereof.

Particularly useful sulfur-containing organic acids and derivatives thereof are the acids themselves or acid-generating compounds or derivatives of the acids which can be overbased with metals such as magnesium. The acid or its derivatives are typically sulfonic acids or their derivatives such as metal salts, halides, anhydrides, and esters derived from lower aliphatic alcohols having up to 8 carbon atoms.

Sulfur-containing organic acids that can be used in this invention include sulfonic acids, sulfamic acids, sulfinic acids, thiosulfonic acids, and various derivatives thereof. Particularly useful among these are sulfonic acids and their derivatives, including aliphatic substituted sulfonic acids in which the aliphatic substituents contain at least 8 carbon atoms. The sulfonic acids include alkylarylsulfonic acids, alkylalicyclic sulfonic acids, alkylheterocyclic sulfonic acids, and aliphatic sulfonic acids, which have at least an aliphatic group.
Includes those containing 12 aliphatic carbon atoms. Specific examples of sulfonic acids and their derivatives include petroleum sulfonic acid, mono- or polywax-substituted naphthylene sulfonic acid, phenolsulfonic acid, diphenyl ether sulfonic acid, diphenyl ether disulfonic acid, naphthylene disulfide sulfonic acid, and naphthylene disulfonic acid. These include sulfide disulfonic acid, diphenylamine disulfonic acid, diphenylamine sulfonic acid, thiophene sulfonic acid, and chlornaphthylene sulfonic acid. Other substituted sulfonic acids include cetylchlorobenzenesulfonic acid, cetinophenolsulfonic acid, cetylphenol disulfide sulfonic acid, cetylphenol monosulfide sulfonic acid, dilauryl beta naphthol sulfonic acid, dicaprylnitronaphthylene sulfonic acid, Aliphatic sulfonic acids such as paraffin wax sulfonic acid, unsaturated paraffin wax sulfonic acid, hydroxy-substituted paraffin wax sulfonic acid, tetraisobutylene sulfonic acid, tetraamyl sulfonic acid, chloro-substituted paraffin wax sulfonic acid, nitroso-paraffin Mention may be made of wax sulfonic acids, petroleum naphthylene sulfonic acids, polywax-substituted cycloalkylsulfonic acids, and various derivatives of these acids, especially alkali metal and alkaline earth metal salts. Examples of the petroleum sulfonic acids include US Pat. No. 2480638, US Pat. No. 2483800, US Pat.
Same No. 2726261, Same No. 2794829, Same No. 2832801
No. 3225086, No. 3337613, No. 3337613, No. 3225086, No. 3337613, No.
3351655, 2616904, 2616905, 2723235, 2723236 and 2777874
These include the well-known sulfonic acids derived from petroleum products such as those described in No.

One of the important features of this invention is that an alkyl-substituted aromatic hydroxy-containing carboxylic acid such as an alkyl-substituted salicylic acid can be used in water without using an accelerator such as alcohol or phenol or an inorganic acidic substance such as carbon dioxide, which were conventionally required. In the presence of magnesium oxide, it can be overbased. In this invention, the aromatic hydroxy-containing carboxylic acid or derivative thereof is used in the presence of a stoichiometric excess, for example, about 0.1 to about 15 equivalents of base-reactive magnesium compound and water, optionally about 0.25 equivalents. at a temperature of at least about 25°C in the presence of at least one other sulfur-containing organic acid (e.g., sulfonic acid) or derivative thereof. Preferably, the reaction temperature is about 80°C to about 300°C, more preferably about 80°C to 200°C or 100°C to 175°C.

The reaction is preferably carried out in the presence of at least one substantially inert organic liquid, up to about 80% by weight of the total amount, preferably from about 10 to about 50%. These organic liquids include various commercially available solvents and, in particular, mineral oils, such as Stoddard solvents, aliphatic, cycloaliphatic or aromatic hydrocarbons, substituted hydrocarbons, and corresponding halogenated hydrocarbons such as chlorobenzene. includes combinations of these. The organic liquid may be an oil-soluble liquid, preferably consisting of a mineral oil and at least one diluent that is soluble in the mineral oil but has a lower viscosity than the mineral oil. The diluent includes, for example, mineral oil and, for example, kerosene, xylene, toluene, ethylbenzene, propylbenzene, cumene, fluorobenzene, chlorobenzene, bromobenzene, fluorotoluene, heptene, octene, nonane, decane, trimethylpentane. , cyclohexane, cycloheptane, ethylcyclohexane, cyclooctane, and various combinations thereof with one or more aliphatic, cycloaliphatic or aromatic hydrocarbons or halogenated hydrocarbons.

In producing the carboxylic acid metal salt of this invention, the method is performed at room temperature or higher.
It consists of contacting the species or more reactants in any order. Thus, for example, the acid or derivative thereof can be contacted and reacted with a magnesium compound in the presence of effective amounts of water and an organic diluent at temperatures up to about 300°C or higher. The upper limit of the reaction temperature is the decomposition temperature of either the reaction mixture or the individual reactants or products, preferably from about 175°C to about 200°C.

After reacting each of the previously mentioned components, the reaction mixture is refluxed for at least about 0.5 hours. Usually, the reaction mixture is allowed to react until it becomes cloudy. A reaction mixture is considered to be free of haze if no haze is visible when observed with the naked eye in sunlight. usually,
The above reflux time is 0.5 to 5.0 hours, usually 0.5 to 5.0 hours.
It is 2.5 hours.

As already mentioned, the overbased metal salts of substituted aromatic hydroxy-containing carboxylic acids of the present invention can be prepared by a variety of methods, and are preferably prepared using substituted aromatic hydroxy-containing carboxylic acids, their anhydrides or Using a metal salt, such as an alkylated magnesium salicylate salt, a stoichiometric excess of the magnesium compound is then added to give a metal ratio of 1.0 to about 15.
It can be produced in such a way that an excess of the carboxylic acid composition is obtained. Therefore, for example, first,
Metal salts of substituted aromatic hydroxy-containing carboxylic acids, such as alkali metal or alkaline earth metal salts, can be prepared and used as intermediates in subsequent overbasing with magnesium oxide to obtain the desired basic salt. . The main object of this invention is to provide overbased or basic magnesium salts of substituted aromatic hydroxy-containing carboxylic acids;
It will be clear that magnesium need not be the only metal present in the metal salt. actual,
Metals other than magnesium selected from the periodic group and group metals may be present in the basic carboxylic acid magnesium salt of the present invention. For example, when an alkali metal or alkaline earth metal salt other than magnesium is used as a starting material, the resulting basic magnesium salt will contain the metal other than magnesium present in the starting material. For example, when a metal salt, such as an alkali metal salt of alkylated salicylic acid, is used as an intermediate, the metal salt may be acidic, neutral, or basic. Any acidic, neutral or basic salt of this substituted aromatic hydroxy-containing carboxylic acid can be reacted with a stoichiometric excess of magnesium oxide to yield products with metal ratios up to about 15. As already mentioned, the product obtained by the process of this invention has a concentration of at least about 150%, preferably about 200%, based on the total number of acid equivalents present.
%, more preferably about 250% stoichiometric equivalents of magnesium. For example, if 0.9 equivalents of substituted aromatic hydroxy-containing carboxylic acid and 0.1 equivalents of sulfonic acid are present, the product of this invention will contain at least 1.5 equivalents, preferably 2.0 equivalents, more preferably 2.5 equivalents of magnesium.

Examples of this invention are described below. Unless otherwise indicated, all parts and percentages are by weight and magnesium oxide is lightly calcined magnesium oxide.

Example 1 About 512 parts of a mineral oil solution containing about 0.5 equivalents of a substantially neutral magnesium salt of an alkylated salicylic acid, the alkyl group of which contains on average about 18 aliphatic carbon atoms, and about dinonylbenzenesulfonic acid.
A reaction mixture consisting of about 30 parts of an oil mixture containing 0.037 equivalents was charged to a flask with about 15 parts of magnesium oxide (about 0.65 equivalents) and about 250 parts of xylene and heated to about 60°C to 70°C. The reaction mixture was then heated to about 85°C and about 60 parts of water was added.
The resulting reaction mixture was held at reflux temperature of about 95°C to 100°C for about 1.5 hours and then heated under reduced pressure at 155°C to 100°C.
It was stripped and filtered at a temperature of 160°C. The filtrate was a base characterized by a sulfated ash content of 12.35% (American Society for Testing and Materials (ASTM) D-874, Institute of Tetroleum (IP) Operation No. 163). is a magnesium carboxylic acid salt containing a stoichiometric equivalent amount of magnesium.
It consisted of a material containing 200% magnesium.

Example 2 About 506 parts of a mineral oil solution containing about 0.5 equivalents of a substantially neutral magnesium salt of an alkylated salicylic acid having an average of about 16 to 24 aliphatic carbon atoms and the same alkyl group as used in Example 1 A reaction mixture consisting of about 30 parts of an oil mixture containing about 0.037 equivalents of alkylated benzene sulfonic acid was charged to a flask with about 22 parts of magnesium oxide (about 1.0 equivalents) and about 250 parts of xylene and heated to about 60-70°C. The reaction mixture was then heated to about 85°C,
Approximately 60 parts of water was added and heated to reflux temperature. The reaction mixture was held at reflux temperature of about 95-100°C for about 1.5 hours, then stripped and filtered at about 155°C under a vacuum of 40 mm Hg. The filtrate consisted of basic carboxylic acid magnesium salts and had a sulfated ash content of 15.59% (corresponding to 274% of the stoichiometric amount).

Example 3 About 4048 parts of a mineral oil solution containing about 4.0 equivalents of an alkylated salicylic acid whose alkyl group has an average of 16 to 24 aliphatic carbon atoms and about 0.3 equivalents of the alkylated benzenesulfonic acid used in Example 1 are A reaction mixture consisting of about 240 parts of the oil mixture containing about 176 parts of magnesium oxide (about 8.0 equivalents) and about 2000 parts of xylene was charged into a flask, and about
Heat to 60-75°C. This reaction mixture is then diluted to approx.
It was heated to 82°C, about 480 parts of water was added thereto, and the resulting mixture was heated to reflux temperature. This reaction mixture is approximately
The mixture was maintained at a reflux temperature of 95-100°C for about 1 hour, then first stripped at about 170°C with nitrogen bubbling, then stripped at 155°C under a vacuum of 40 mmHg, and filtered. The filtrate consisted of basic carboxylic acid magnesium salts and had a sulphated ash content of 15.77%, corresponding to 277% of the stoichiometric amount.

Example 4 A substantially neutral potassium salt of an alkylated salicylic acid in which the alkyl group has an average of 16 to 24 aliphatic carbon atoms is reacted with a nearly stoichiometric amount of magnesium chloride to form the desired alkylated salicylic acid. A substantially neutral magnesium salt was prepared.
About 285 parts of magnesium oxide (14 equivalent) and about 3252 parts of xylene and heated to about 55-75°C. The reaction mixture was heated to about 82°C and water was added to about 82°C.
780 parts were added and the resulting reaction mixture was heated to reflux temperature. The reaction mixture was held at reflux temperature of about 95-100°C for about 1 hour, then stripped and filtered at about 170°C under a vacuum of 50 mm Hg. The filtrate consisted of a basic carboxylic acid magnesium salt and had a sulfated ash content of 15.7% (corresponding to 276% of the stoichiometric equivalent).

Example 5 About 1025 parts of a mineral oil solution containing about 1.0 equivalents of a substantially neutral magnesium salt of an alkylated salicylic acid in which the alkyl group has an average of about 18 aliphatic carbon atoms and the alkyl used in Example 1 A reaction mixture consisting of about 60 parts of an oil mixture containing 0.04 equivalents of hydrogenated benzenesulfonic acid and about 0.04 equivalents of olefinic acid was mixed with about 60 parts of magnesium oxide and about 0.04 parts of xylene.
Pour into a flask with 500 parts and heat to about 65℃ or
It was heated to 75℃. This reaction mixture was then heated to approximately 90°C.
About 240 parts of water was added to this, and the mixture was heated to reflux temperature. The reaction mixture was held at reflux temperature of about 95-100°C for about 2 hours, then stripped and filtered at about 160°C. The filtrate consisted of the desired basic carboxylic acid magnesium salt.

Example 6 About 1500 parts of a mineral oil solution containing about 1.5 equivalents of a substantially neutral magnesium salt of an alkylated salicylic acid having an average of about 16 to 24 aliphatic carbon atoms in the mineral oil solution used in Example 1 A reaction mixture consisting of about 90 parts of an oil mixture containing 0.08 equivalents of alkylated benzenesulfonic acid and about 0.04 equivalents of tall oil fatty acids was added to the flask along with about 60 parts (3.0 equivalents) of magnesium oxide and about 500 parts of xylene, and about 65 It was heated to ℃. The reaction mixture was then heated to about 85° C., about 180 parts of water was added thereto, and the mixture was heated to reflux temperature. This reaction mixture was heated to approximately 95°C to 100°C.
The temperature was maintained at reflux temperature for about 2 hours, and then heated to 400 mmHg.
The solution was stripped and filtered at about 155°C under reduced pressure. The filtrate consisted of the desired basic carboxylic acid magnesium salt.

Example 7 A mineral oil solution containing about 1.0 equivalents of a substantially neutral magnesium salt of an alkylated salicylic acid having an average of at least about 18 aliphatic carbon atoms and about 0.08 equivalents of petroleum naphthenesulfonic acid. A reaction mixture consisting of about 60 parts (3.0 equivalents) of magnesium oxide, and about 750 parts of xylene was charged to a flask and heated to about 75°C. Then,
Heat the reaction mixture to about 85 °C and add about 440 °C of water to it.
1 part and heated to reflux temperature. The reaction mixture was heated to a reflux temperature of about 95-100°C for about 2 hours, then stripped at about 160°C under a vacuum of 40 mmHg,
Filtered. The filtrate consisted of the desired basic carboxylic acid magnesium salt.

Example 8 Alkylated hydroxybenzoic acid having an average of about 18 aliphatic carbon atoms, about 1.0
A reaction mixture consisting of about 1025 parts of an oil solution containing about 60 parts (3.0 equivalents) of magnesium oxide and about 0.08 parts of sodium salt of the alkylated benzenesulfonic acid used in Example 1 was added to the reaction mixture containing about 60 parts (3.0 equivalents) of magnesium oxide and xylene. The flask was charged with about 500 parts of solvent and heated to about 60-75°C. Then,
The reaction mixture was heated to about 85°C, to which about 60 parts of water was added and heated to reflux temperature. This reaction mixture is approx.
It was maintained at a reflux temperature of 95-100°C for about 2 hours, and then stripped at about 150°C under a reduced pressure of 40 mmHg.
Filtered. The filtrate consisted of the desired basic carboxylic acid magnesium salt.

Example 9 About 512 parts of an oil solution containing about 0.5 equivalents of a substantially neutral sodium salt of an alkylated salicylic acid in which the alkyl group has an average of about 16 to 24 aliphatic carbon atoms and A reaction mixture consisting of an oil mixture containing about 0.25 equivalents of alkylated benzenesulfonic acid was mixed with about 4.0 equivalents of magnesium oxide.
equivalent amount and about 5000 parts of xylene into a flask and heated to about 75°C. The reaction mixture was then heated to about 85°C, to which about 200 parts of water was added, and then heated to reflux temperature. This reaction mixture is approximately 95~
The mixture was kept under reflux temperature of 100°C for about 2 hours, then stripped and filtered under reduced pressure at about 150°C. The filtrate consisted of the desired basic carboxylic acid magnesium salt.

Example 10 About 1025 parts of a mineral oil solution containing about 1.0 equivalents of a substantially neutral calcium salt of an alkylated salicylic acid having an average of about 16 to about 24 aliphatic carbon atoms and an alkylated benzene sulfone. A reaction mixture consisting of an oil mixture containing about 0.12 equivalents of the sodium salt of the acid magnesium oxide
(3.0 equivalents) and approximately 750 parts of an organic solvent containing xylene.
It was heated to ℃. The reaction mixture was then heated to about 85° C., about 200 parts of water was added thereto, and the mixture was heated to reflux temperature. The reaction mixture was held at reflux temperature of about 95-100°C for about 2 hours, then stripped under reduced pressure at about 165°C and filtered. The filtrate consisted of the desired basic carboxylic acid magnesium salt.

Example 11 A mineral oil solution containing about 512 parts of about 0.5 equivalents of a substantially neutral magnesium salt of an alkylated hydroxybenzoic acid having an average of at least 18 carbon atoms in a mineral oil solution containing about 0.04 equivalents of naphthenic acid. About 60 parts (3.0 equivalents) of magnesium oxide and about xylene are added to the reaction mixture containing an oil mixture.
It was added to a flask along with 500 parts and heated to about 60-70°C. The reaction mixture was then heated to about 85°C,
Approximately 180 parts of water was added to this and heated to reflux temperature. The reaction mixture was held at reflux temperature of about 95°C to 100°C for about 2 hours, then stripped and filtered under reduced pressure at about 150°C. The filtrate consisted of the desired basic carboxylic acid magnesium salt.

Example 12 From an oil mixture containing about 1025 parts of an oil solution containing about 1.0 equivalents of an alkylated gallic acid, the alkyl group of which has an average of about 18 aliphatic carbon atoms, and about 0.1 equivalents of a sodium salt of a petroleum sulfonic acid. The reaction mixture was charged into a flask with about 60 parts (3.0 equivalents) of magnesium oxide and about 500 parts of an organic solvent containing xylene and heated to about 60-75°C. The reaction mixture was then heated to about 85°C, about 120 parts of water was added thereto, and the mixture was heated to reflux temperature. The reaction mixture was held at reflux temperature of about 95-100°C for about 2 hours, then stripped and filtered under reduced pressure at about 160°C. The filtrate consisted of the desired basic carboxylic acid magnesium salt.

Example 13 About 1000 parts of an oil solution containing about 1.0 equivalents of an alkylated 2,5-dihydroxybenzoic acid having an average of about 16 aliphatic carbon atoms and about 0.05 equivalents of petroleum sulfonic acid and tall oil fatty acids. about
A reaction mixture consisting of an oil mixture containing 0.05 equivalents was charged to a flask with about 160 parts (8.0 equivalents) of magnesium oxide and about 600 parts of an organic solvent containing xylene and heated to about 60-75°C. The reaction mixture was then heated to about 85°C and about 100% of water was added to it.
90 parts were added and heated to reflux temperature. The reaction mixture was maintained at a reflux temperature of about 95-100°C for about 3 hours,
It was then stripped at about 150° C. under reduced pressure and filtered. The filtrate consisted of the desired basic carboxylic acid magnesium salt.

Example 14 About 1575 parts of an oil solution containing about 1.5 equivalents of an alkylated 4-hydroxy-1,3-benzenedicarboxylic acid having an average of at least about 16 aliphatic carbon atoms and about 1575 parts of tall oil fatty acid.
A reaction mixture consisting of an oil mixture containing 0.5 equivalents was charged to a flask with about 120 parts (6.0 equivalents) of magnesium oxide and about 700 parts of an organic solvent containing xylene and heated to about 70-75°C. The reaction mixture was then heated to about 85° C., about 120 parts of water was added thereto, and the mixture was heated to reflux temperature. This reaction mixture is approx.
The mixture was kept under reflux temperature of 95-100°C for about 3 hours, then stripped and filtered under reduced pressure at about 155°C. The filtrate consisted of the desired basic carboxylic acid magnesium salt.

Example 15 An oil solution containing about 0.5 equivalents of an alkylated 1-hydroxy-2-naphthoic acid in which the alkyl group has an average of at least about 16 aliphatic carbon atoms.
A reaction mixture consisting of an oil mixture containing 500 parts and 0.25 equivalents of petroleum sulfonic acid was charged to a reactor along with about 30 parts (1.5 equivalents) of magnesium oxide and about 250 parts of organic solvent and heated to about 60-75°C. The reaction mixture was then heated to about 85°C and about 100% of water was added to it.
30 parts were added and heated to reflux temperature. The reaction mixture is maintained at a reflux temperature of about 95-100°C for about 2 hours,
The mixture was then slipped at about 150° C. under reduced pressure and filtered. The filtrate consisted of the desired basic carboxylic acid magnesium salt.

Example 16 (a) Diluent To 6240 grams of the potassium salt of a _C16 - _C24 substituted salicylic acid in mineral oil was added 309 grams of sulfur dichloride over one hour. The reaction mixture was kept at 150°C during this addition. After the addition was complete, the reaction mixture was cooled to 120° C. and to it were added 700 grams of xylene and 300 grams of water. this mixture
Reflux for 0.75 h and 165 hr under nitrogen bubbling.
Stripped to ℃. Filtration through a filter aid yielded the desired diaryl sulfide intermediate.

(b) To a mixture consisting of 509 grams of the diaryl sulfide intermediate described above, 250 grams of xylene, and 34 grams of the sulfonic acid of Example 1 was added 33 grams of magnesium oxide. During this addition, the temperature
It was maintained at 60°C. Then, increase the temperature to 85℃,
Added 60 grams of water. This reaction mixture was heated to 95°C.
Reflux for 1.0 hour, strip to 180° C. under 30 mm Hg vacuum, and filter through filter aid to yield the desired final product. The product had a magnesium sulfate content of 15.76%, indicating that it contained 270% of the stoichiometric equivalent of magnesium.

Example 17 An oil mixture containing 256 parts of the mineral oil solution of Example 1 and about 0.019 parts of the sulfonic acid of Example 1 was added to a flask. Add magnesium chloride 36 to this mixture.
A suspension containing 22 parts of magnesium hydroxide produced by treating an aqueous solution containing 1 part of magnesium hydroxide with 3.75 liters of 1N sodium hydroxide was added. Additionally, 125 parts of xylene was added and the resulting mixture was heated to about 60-70°C. Next, approximately 60 parts of water was added to this reaction mixture, and the mixture was heated under reflux (95 to 105°C).
It was held for 1.5 hours. 30mmHg while blowing nitrogen
The desired product was obtained by stripping at 155-160°C under a pressure of

Example 18 About 512 parts of a mineral oil solution containing about 0.5 equivalents of a substantially neutral magnesium salt of an alkylated salicylic acid having an average of about 16 to 24 aliphatic carbon atoms in about 15 parts of magnesium oxide. (0.75 equivalents) and about 250 parts of xylene from about 60 to
The reactor was charged at 70°C. The reaction mixture was then heated to about 85°C, to which about 60 parts were added and heated to reflux temperature. This reaction mixture was heated to about 95 to 100 °C.
The mixture was kept at reflux temperature for 1.5 hours, then stripped and filtered at about 155°C under a vacuum of 40 mmHg.
The filtrate consisted of the desired basic carboxylic acid magnesium salt.

Example 19 About 472 parts of a mineral oil solution containing about 0.333 equivalents of a substantially neutral magnesium salt of an alkylated salicylic acid in which the alkyl group has an average of about 60 aliphatic carbon atoms and the alkyl used in Example 1 A reaction mixture consisting of about 26 parts of an oil mixture containing about 0.333 equivalents of hydrogenated benzenesulfonic acid was charged to a flask with about 15 parts of magnesium oxide (about 0.69 equivalents) and about 340 parts of xylene and heated to about 60-70°C. The reaction mixture was then heated to about 85° C., about 65 parts of water was added thereto, and the mixture was heated to reflux temperature. The reaction mixture was held at reflux temperature of about 95-100°C for about 1 hour. Add an additional 18 parts MgO (approx.
0.83 equivalents) was added. The resulting reaction mixture was heated to approx.
Hold at reflux temperature of ~100°C for about 2 hours, then
Stripped to 200℃ under 18mmHg vacuum,
Filtered. The filtrate was a solution of the desired product in mineral oil.

Example 20 About 2921 parts of a mineral oil solution containing about 2.0 equivalents of a substantially neutral magnesium salt of an alkylated salicylic acid in which the alkyl group has an average of about 60 aliphatic carbon atoms and the alkyl used in Example 1 An oil mixture containing about 0.15 equivalents of benzenesulfonic acid
A mixture of 121 parts was charged to a flask with about 89 parts of magnesium oxide (about 4.1 equivalents) and about 2060 parts of xylene and heated to about 60-70°C. The reaction mixture was then heated to about 85°C and about 100% of water was added to it.
540 parts were added and heated to reflux temperature. The reaction mixture was kept under reflux temperature of about 95-100°C for about 1.5 hours,
It was then stripped and filtered at about 155° C. under a reduced pressure of 40 mmHg. The filtrate consists of the desired basic carboxylic acid magnesium salt and has a sulfated ash content of 8.18%, which is 228% of the stoichiometric equivalent amount.
%.

Example 21 5423 grams (3.75 equivalents) of a potassium salicylate salt alkylated with a monoalkyl polypropylene having an average of 50 carbon atoms and some having more than 100 carbon atoms, 825 grams of mineral oil,
and 195 grams of water were charged into the reaction vessel. The contents were slowly heated to about 70°C and 199 grams (3.75 equivalents) of 93% sulfuric acid was added over 30 minutes at 70-75°C. After adding another 1346 grams of mineral oil to this,
338 grams of xylene, 190 grams (0.278 equivalents) of C24 monoalkylbenzene sulfonic acid, and 237 grams (11.28 equivalents) of magnesium oxide were added. Heat this mixture to 80°C, add 274 grams of water, raise the temperature to reflux point, and at that temperature
It was held for 1.25 hours. Then, magnesium sulfate 10
After adding grams, the mixture was heated to 150°C for 3 hours. The mixture was then stripped to 160° C. at 15 mm Hg and filtered to obtain the desired product.

Example 22 3875 grams (3.11 equivalents) of a magnesium salicylate salt alkylated with a monoalkyl polypropylene having an average of 50 carbon atoms and some containing more than 100 carbon atoms, 1363 grams mineral oil, 2500 grams xylene , and 196 grams (0.23 equivalents) of a C16 dialkylbenzenesulfonic acid were charged to a reaction vessel. Stir the contents, 60
After heating to 0.degree. C., 135 grams (6.24 equivalents) of magnesium oxide were added. Add water to this mixture at 85°C.
Add 410 grams, raise the temperature to reflux point,
It was held at that temperature for 1 hour. This mixture was blown with nitrogen at a rate of 2 cubic feet per hour.
Volatiles were removed by heating to 160°C. The mixture was then stripped to 170° C. at 15 mm Hg and filtered to obtain the desired product.

Example 23 708 grams (0.5 equivalents) of a polyisobutenyl salicylic acid magnesium salt having an average of 60 carbon atoms and containing up to 180 carbon atoms, each alkyl group having 8 carbon atoms 29 grams (0.037 equivalents) of dialkylbenzene sulfonic acid and 500 grams of xylene were charged to the reaction vessel. The mixture was heated to reflux and 22 grams (1.0 equivalents) of magnesium oxide was added before heating to 95°C. Add 60 grams of water slowly to this, and make 96
It was refluxed at −98°C. After 2 hours of refluxing, it was stripped to 153° C. with nitrogen bubbling at 1 cubic foot per hour. After adding 135 grams of mineral oil, vacuum stripping to 162° C. at 19 mm Hg and filtration afforded the desired product.

Example 24 400 grams (5.6 equivalents) of dry methyl cellosolve (ethylene glycol monomethyl ether) was charged to a reaction vessel. 100− of this methyl cellosolve
The mixture was heated to 120° C. and 24 grams (2.0 equivalents) of magnesium metal was added in 8 grams portions. This metallic magnesium reacted with methyl cellosolve to generate Mg(-O-ethylene-O-methyl) ₂ while generating hydrogen vigorously. The reaction mixture was swept with nitrogen and held at 100-120° C. until hydrogen evolution ceased and all magnesium was consumed.

Poly-n-
Oil solution of magnesium butenyl salicylate (oil 45
%) added 1400 grams. The reaction mixture was heated to 160° C. while removing excess methyl cellosolve by distillation with a nitrogen sweep. After removing the excess methyl cellosolve, this mixture was reduced to ca.
Cool to ℃ and add 500 grams of xylene. After the mixture was further cooled to about 90° C., 130 grams of water was added. The reaction mixture was refluxed at about 90°C for about 1 hour to produce Mg(-O-ethylene-O-methyl).
₂ was hydrolyzed. This was stripped at 30 mmHg to about 160°C to remove xylene, water, and methyl cellosolve. The residue was filtered to obtain the desired overbased product.

Example 25 Magnesium poly-n-butenylsalicylate used in Example 24 3500 grams (3.55 equivalents), carbon number
24 Branched Monoalkylbenzene Sulfonic Acid 2432
(3.55 equivalents), 1185 grams of xylene, and 1330 grams of mineral oil were charged to the reaction vessel. After heating the mixture to 55°C, 348 grams (16.06 equivalents) of magnesium oxide were added followed by 444 grams of water;
Refluxed. After 1 hour of reflux, the temperature was increased to 150°C while blowing nitrogen at a rate of 2 cubic feet/hour.
Stripped up to. Finally, 160 at 12mmHg
Stripping to <0>C and filtration yielded the desired product.

Example 26 4023 grams (4.48 equivalents) of potassium poly-n-butenylsalicylate and 1074 grams of mineral oil were charged to a reaction vessel. Slowly heat this mixture to about 70℃.
474 grams (4.88 equivalents) of 37% hydrochloric acid was heated to
It was added over 60 minutes at 70-75°C. Then, mineral oil
685 grams, 468 grams of xylene, 286 grams (0.36 equivalents) of dialkylbenzene sulfonic acids in which each alkyl group has 8 carbon atoms and are linear and branched, respectively, and 307 grams (14.2 equivalents) of magnesium oxide. Ta. After heating the mixture to 80° C., 319 grams of water were added and the temperature was increased to reflux and held for 1 hour. The mixture was slowly heated to 150° C. with nitrogen bubbling at 2 cubic feet per hour, vacuum stripped to 160° C. at 12 mm Hg, and filtered to yield the desired product.

The basic magnesium carboxylic acid salts of this invention can be effectively used in a variety of lubricating and fuel compositions. Lubricating compositions primarily include crankcase lubricants for spark-ignited and compression-ignited internal combustion engines, such as automotive and truck engines, two-stroke engines, aircraft piston engines, marine and railroad diesel engines. . Furthermore, by adding an effective amount of the basic magnesium carboxylate salt of the present invention to automatic transmission fluids, transmission shaft lubricants, gear lubricants, metal processing lubricants, pressure fluids, and other various lubricating oils and greases, various effects can be achieved. Characteristics can be improved.

More specifically, basic magnesium salts of substituted aromatic hydroxy-containing carboxylic acids, particularly overbased magnesium salts of alkylated benzoic acids, such as the aforementioned alkylated salicylic acids, can be used as additives in effective amounts, such as antioxidant properties. Up to about 30% by weight can be used as a dispersant with a Basic magnesium salts of substituted aromatic hydroxy-containing carboxylic acids can be present in various oily substances, such as synthetic and mineral lubricating oils, normally liquid fuels such as gasoline, diesel fuel, kerosene, etc. in total amounts of about
From 0.0001 to about 25% or 30% by weight can be used. Preferably, the basic magnesium salt is used in a proportion of about 0.01 to 30% by weight, more preferably about 0.1 to 10% by weight of the total amount. The optimum amount to add to a particular oily substance will vary depending on the surface and conditions to which the fuel or lubricant will be applied. For example, when the basic magnesium salt of the present invention is added to gasoline for internal combustion engines, the amount added is about 0.0001 to about 1.0% by weight. On the other hand, when this basic magnesium salt is added to gear lubricants or used in diesel engine, pressure fluid, motor oils, the amount can be as high as 25% by weight of the total amount. In some cases, it may be used in proportions as high as about 30% by weight or even more.

When used in lubricants or fuels, the basic magnesium salts of this invention are dissolved or stably dispersed in the medium. "Stably dispersed" means that a substance (e.g., a single additive or compound, a mixture of two or more additives or compounds, etc.) is dispersed in a particular medium to the extent that it can function as intended. means to disperse within. Thus, for example, when the basic magnesium salts of this invention are used in an oil, the dispersed basic magnesium salt may be sufficient to cause the oil to have one or more desired properties. It is sufficient if it can be dispersed or suspended in oil. Such dispersion or suspension can be accomplished by various conventional methods. for example,
In constantly circulating oil or oil in a splash lubrication system, the basic magnesium salts of this invention can be suspended in the oil by physical agitation. Similarly, stable dispersions or suspensions of basic magnesium salts can be obtained by means of conventional dispersants often used in lubricating oils and fuels (e.g., the acylated nitrogen-based dispersants described in U.S. Pat. No. 3,219,666). can be promoted. In any event, the basic magnesium salt used will be "dissolved" or "stably dispersed" in the normally liquid medium to which it is added, to at least the minimum concentrations mentioned herein. That is,
The terms "dissolve" and "stably disperse" are used interchangeably and will be readily understood by those skilled in the art.

The basic magnesium salts of this invention can be made into additive concentrates for use in fuels or lubricants. This concentrate contains, in addition to the basic magnesium salt of this invention, a substantially inert solvent.
Diluents and optionally other additives as described herein may also be included.

The term "substantially inert" as used in this specification and claims with respect to solvents, diluents, base stocks, etc. means that the solvent, diluent, etc. is It is used in the sense that it is inert to chemical or physical changes and does not substantially adversely affect the preparation, storage, incorporation and/or action of the compounds, additives, etc. of this invention when used. ing. For example, a small amount of solvent, diluent, etc. may react or deteriorate slightly as long as it does not impede the implementation of the present invention. In other words, such reactions and deterioration, although perceivable from a purely technical point of view, do not preclude the practice of this invention.

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

Examples of the lubricating or fuel composition of the present invention are shown below.

Reference Example A A SAE10W-30 lubricating oil was mixed with 6.5% by weight of an acylated nitrogen-based product obtained by the reaction of a high molecular weight polyolefin-substituted succinic acid with a polyamine such as polyethylene polyamine, 1.28% by weight of zinc dialkylphosphorodithioate, A lubricating composition was obtained by mixing with 0.005% by weight of the (alkyl methacrylate) antifoaming agent and 5.18% by weight of the basic carboxylic acid magnesium salt obtained in Example 1.

Reference example B SAE10W-40 lubricating mineral oil, 1.0% by weight of the basic carboxylic acid magnesium salt obtained in Example 1, and an adduct obtained by heating zinc dinonylphosphorodithioate with 1,2-hexene oxide at 120°C A blend was prepared using 0.8% by weight of phosphorus, 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) antifoam agent, and 0.5% by weight of lard oil.

Reference Example C Gasoline was mixed with 0.001% by weight of the product of Example 12.

Reference example D Kerosene was mixed with the product of Example 6.

In addition to the basic magnesium salts of this invention, other known additives may be added to lubricating or fuel compositions. Such additives include, for example:
These include ash-containing detergents, ashless dispersants, viscosity index improvers, pour point depressants, antifoam agents, extreme pressure agents, rust inhibitors, oxidation and corrosion inhibitors, and various combinations thereof. Examples of ash-containing detergents are oil-soluble neutral or basic alkali metal or alkaline earth metal salts of sulfonic acids, carboxylic acids or organic phosphorous acids. One of the additives is e.g.
By reacting an olefin polymer having a molecular weight of about 2000, such as polyisobutene, with a phosphating agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and sulfur halide, or phosphorothioyl chloride. can be manufactured. However, the most commonly used ones are sodium, potassium, lithium, calcium, magnesium,
Salts of strontium, barium or various mixtures thereof.

The method for producing basic salts involves adding a mineral oil solution of the acid to approximately 50%
It consists of heating with a stoichiometric excess of a neutralizing agent such as a metal oxide, hydroxide, carbonate, bicarbonate, sulfide, etc. at a temperature above 0.degree. Various promoters can be used to assist in the introduction of excess metal in this step. Such accelerators are now well known and include, for example, phenolic compounds such as phenols, naphthols, alkylphenols, thiophenols, sulfurized alkylphenols, and also various condensation products of formaldehyde and phenolic compounds; Alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol and cyclohexyl alcohol, aniline,
There are amines such as phenylene diamine, phenothiazine, phenyl beta naphthylamine and dodecylamine. A particularly effective method of making basic salts is to mix the acid with an excess of alkaline earth metal in the presence of a phenolic promoter and a small amount of water, and to heat the mixture to a temperature of, for example, 60 to about 200°C. It carbonates under warm conditions.

Examples of extreme pressure agents, corrosion inhibitors, and antioxidants include basic aliphatic hydrocarbons such as chlorinated waxes, benzyl disulfide, bis(chlorobenzyl) disulfide, dibutyltetrasulfide, and sulfurized whale oil. , sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene,
Organic sulfides and polysulfides such as sulfurized terpenes, phosphosulfide hydrocarbons such as the reaction products of phosphorus sulfide with turpentine or methyl oleate, dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phosphite. enyl, dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethylnaphthyl phosphite, oleyl-4-pentylphenyl phosphite, polypropylene phosphite (molecular weight
500) Phosphorus-containing esters containing mainly dihydrocarbon and trihydrocarbon phosphites such as substituted phenyl, diisobutyl substituted phenyl phosphite, metal thiocarbamates such as zinc dioctyl dithiocarbamate and barium heptyl phenyl dithiocarbamate; Zinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, barium di(heptyl phenyl)phosphorodithioate, cadmium dinonylphosphorodithioate, by reaction of phosphorus pentasulfide with an equimolar mixture of isopropyl alcohol and n-hexyl alcohol The resulting group metal salts of phosphorodithioic acid, such as the zinc salt of phosphorodithioic acid.

Fuel or lubricating compositions contain approximately metal-based detergents.
It may be contained in a proportion of 0.001 to about 15% by weight. In some applications, such as marine diesel engine lubrication, lubricating compositions contain as much as 30% by weight detergent. These compositions contain extreme pressure agents, viscosity index improvers, pour point depressants, etc.
It may be contained in a proportion of 15%, preferably 0.1 to about 10%. One or more of the above additives may be used alone or in an amount of from about 0.0001 to about 25% by weight of the basic carboxylic acid metal salts of this invention;
It can be used in combination with 30% by weight in various compositions such as fuel or lubricating compositions.

Oily substances such as lubricating oils and fuels include animal and vegetable oils (e.g. castor oil and lard oil), as well as paraffinic, naphthenic or mixed paraffinic-naphthenic solvent-treated or acid-treated mineral lubricating oils. be. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
Synthetic lubricating oils include homopolymerized and interpolymerized olefins (e.g., polybutylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.)
hydrocarbon oils and halo-substituted hydrocarbon oils, such as
Alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes, etc.), polyphenyls (e.g., biphenyls,
terphenyls, etc.). Homopolymers and interpolymers of alkylene oxide, as well as derivatives thereof whose terminal hydroxyl groups have been modified by esterification, etherification, etc., also constitute another group of known synthetic lubricating oils. Examples of this include oils obtained by polymerizing ethylene oxide and propylene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers (e.g. methylpolyisopropylene glycol ether with an average molecular weight of 1000, diphenyl ether of polyethylene glycol, diethyl ether of polypropylene glycol with a molecular weight of 1000 to 1500, etc.) or their mono- and polycarboxylic acid esters, such as acetic acid esters, mixed C ₃ to
It is a C ₈ fatty acid ester or a C ₁₃ oxoacid diester of tetraethylene glycol.

Other suitable groups of synthetic lubricating oils include dicarboxylic acids (e.g. phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, etc.) and various Alcohol (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, pentaerythritol, etc.)
Consists of esters of Specific examples of these esters are as follows. Namely, dibutyl adipate, di(2-ethylhexyl) sebacate, dinormalhexyl fumarate,
Dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, 1 mole of sebacic acid and 2 moles of tetraethylene glycol and 2-ethyl caprone. acid 2
complex esters with moles, etc.

Silicone-based oils such as polyalkyl, polyaryl, polyalkoxy, or polyaryloxy-siloxane oils and silicate oils also constitute another useful group of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl silicate, silicate Acid tetra(2-ethylhexyl), silicate tetra(4-methyl-2-tetraethyl), silicate tetra(para-tert-butylphenyl), hexyl-(4-methyl-2-pentoxy)-disiloxane, poly(methyl) disiloxanes, poly(methylphenyl)siloxanes, etc.). Other synthetic lubricants include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid, etc.), polymerized tetrahydrofuran, and the like.

Claims (1)

[Scope of Claims] 1 Substantially hydrocarbyl-substituted aromatic hydroxycarboxylic acids having about 8 to about 400 carbon atoms, and their salts, anhydrides, amides,
At least one reactant (A) selected from the group consisting of imides and halides is combined with magnesium in a stoichiometric excess up to about 15 equivalents per equivalent of reactant (A). Reactant (B) is at least one magnesium compound selected from the group consisting of oxides, hydroxides and alkoxides of
and the reactant (A) in the presence of at least about 0.1 mole of water (C) per equivalent of the magnesium compound.
in the presence or absence of at least one sulfonic acid (D) in a proportion of up to about 0.25 equivalents per equivalent;
and in the substantial absence of organic acids other than the reactants (A) and (D) at a temperature from about 25°C to the decomposition temperature of the reactants in the substantial absence of inorganic acidic substances. , and then the resulting reaction mixture at least about
An uncarbonated basic magnesium substituted aromatic hydroxy-containing carboxylic acid containing from 150% to about 500% of the stoichiometric equivalent amount of magnesium based on the total amount of acid present, characterized in that it is refluxed for 0.5 hours. Method of manufacturing salt. 2. The manufacturing method according to claim 1, wherein the substituted aromatic hydroxycarboxylic acid is a monohydroxycarboxylic acid. 3. The manufacturing method according to claim 1, wherein the substituted aromatic hydroxycarboxylic acid is a monocarboxylic acid. 4. The manufacturing method according to claim 3, wherein the reactant (A) is substituted salicylic acid or a derivative thereof. 5. The manufacturing method according to claim 3, wherein the reactant (A) is a salt. 6. The manufacturing method according to claim 5, wherein the salt is an alkali metal salt or an alkaline earth metal salt. 7. The manufacturing method according to claim 6, wherein the salt is a magnesium salt. 8. The manufacturing method according to claim 1, wherein the reactant (A) is a hydrocarbon-substituted magnesium salicylate salt. 9 An average of about 12 hydrocarbyl groups to about
The manufacturing method according to claim 1, having 400 carbon atoms. 10. The method of claim 9, wherein water is present in a proportion of about 0.1 to about 10 moles per equivalent of the magnesium compound. 11. The production method according to claim 1, wherein the reaction is carried out in the absence of reactant (D). 12. The production method according to claim 11, wherein the reactant (A) is substituted salicylic acid or a derivative thereof. 13. The production method according to claim 12, wherein the reactant (A) is a magnesium salt. 14 Average of about 12 to about 14 hydrocarbyl groups
Claim 13 with 400 carbon atoms
Manufacturing method described in section.