CA1138412A - Magnesium oxide-carboxylate complexes, method for their preparation, and compositions containing the same - Google Patents
Magnesium oxide-carboxylate complexes, method for their preparation, and compositions containing the sameInfo
- Publication number
- CA1138412A CA1138412A CA000337842A CA337842A CA1138412A CA 1138412 A CA1138412 A CA 1138412A CA 000337842 A CA000337842 A CA 000337842A CA 337842 A CA337842 A CA 337842A CA 1138412 A CA1138412 A CA 1138412A
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- magnesium
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- mixture
- complex
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
Abstract Thixotropic magnesium-containing complexes are prepared by heating a mixture of magnesium hydroxide, mag-nesium oxide, hydrated magnesium oxide or a magnesium alk-oxide; a carboxylic acid, a mixture thereof with a sulfonic or pentavalent phosphorus acid, or an ester or salt of either of these; water (optional under certain conditions);
and an organic solubilizing agent (which may be liquid or solid at ambient temperature) for the acid or ester. The amount of magnesium is such as to provide a basic compo-sition. The resulting complexes may be obtained in liquid or solid form, and are useful as additives for lubricants and fuels and as protective coating compositions for metal surfaces (such as automotive undercoats and frame coatings).
and an organic solubilizing agent (which may be liquid or solid at ambient temperature) for the acid or ester. The amount of magnesium is such as to provide a basic compo-sition. The resulting complexes may be obtained in liquid or solid form, and are useful as additives for lubricants and fuels and as protective coating compositions for metal surfaces (such as automotive undercoats and frame coatings).
Description
113841~
LF-1680-Ca This invention relates to new magnesium-containing compositions of matter and methods for their preparation.
In a general sense, the invention comprises thixotropic non-carbonated magnesium-containing complexes which are prepared by heating, at a temperature above about 30C., a mixture comprising:
(A) At least one of magnesium hydroxide, mag-nesium oxide, hydrated magnesium oxide and a magnesium alkoxide;
(B) At least one oleophilic organic reagent com-prising a carboxylic acid, a mixture of a major amount thereof with a minor amount of a sulfonic acid or pentavalent phosphorus acid, or an ester or alkali metal or alkaline earth metal salt of either of these;
`~
~F
113841~' (C) Water, if necessary to convert a substantial proportion of component A to magnesium hydroxide or hydrated magnesium oxide; and (D) At least one organic solubilizing agent for component B;
the ratio of equivalents of magnesium to the acid portion of component B being at least akout 5:1; and the amount of water present, if any, being sufficient to hydrate a substantial proportion of component A calculated as mag-10 nesium oxide.
Several methods are known for the preparation of basic magnesium compounds for use in lubricants, greases and the like. For example, U.S. Patent 3,865,737 describes the formation of a highly basic magnesium-containing liquid dis-15 persion by mixing an oil-soluble dispersing agent, magnesium oxide, a volatile aliphatic hydrocarbon solvent, alcohol, water and ammonia or an ammonium compound, treating the mix-ture with carbon dioxide, adding a non-volatile diluent oil and removing volatiles. Similarly, U.S. Patent 3,629,109 20 describes the carbonation of a mixture of an oil-soluble organic acid or salt thereof, magnesium oxide, a lower ali-phatic alcohol, water and an organic liquid diluent. The products obtained by these methods may be characterized, for the most part, as basic oleophilic magnesium carbonates 25 since an essential step in their preparation is reaction with carbon dioxide.
In accordance with the present invention, it has been discovered that highly basic, thixotropic magnesium complexes may be prepared without reaction with carbon 30 dioxide or similar acidic gases. The products obtained in accordance with the present invention, which may be charac-terized:as complexes of magnesium oxide or hydroxide and a magnesium salt of the acid comprising component B, and which are hereinafter sometimes referred to merely as "magnesium 35 complexes", have a wide variety of uses, including additives 113~34~'~
for lubricants and fuel oils and corrosion-resistant coat-ings or constituents thereof.
A principal object of the present invention, therefore, is to provide new oleophilic magnesium-containing compositions and a method for their preparation.
A further object is to provide a method for pro-ducing magnesium complexes which does not necessitate reac-tion with carbon dioxide or a similar acidic gas.
A further object is to provide basic thixotropic 10 magnesium compositions which may be obtained either in liquid or solid form.
Still another object is to provide thixotropic magnesium-containing compositions useful as greases, as detergent additives for lubricants or as corrosion inhi-15 bitors, vanadium scavengers and smoke suppressants forfuels, and in the formulation of corrosion-resistant coat-ings for metals.
Other objects will in part be obvious and will in part appear hereinafter.
20 Component A
Component A used in the method of this invention is magnesium hydroxide, magnesium oxide, hydrated magnesium oxide, a maynesium alkoxide, or a mixture of these. Magne-sium hydroxide and magnesium oxide are, of course, repre-25 sented by the formulas Mg(OH) 2 and MgO, respectively.Magnesium oxide exists in an inactive "dead burned" and a hydratable "reactive" form and the latter is the one which is useful in this invention although mixtures~of the "reac-tive" form with minor amounts of the "dead burned" form may 30 also be used. "Hydrated magnesium oxide", for the purpose of this invention, is magnesium oxide which is associated with water in an amount less than that required for con-version to magnesium hydroxide; that is, the amount of water is less than one mole per mole of magnesium oxide. As so 35 defined, "hydrated magnesium oxide" may actually be a mix-~138~12 ture of various proportions of magnesium oxide and magnesium hydroxide and its exact chemical nature is not critical to this invention. Typically, the amount of water present in "hydrated magnesium oxide" is at least about 0.7 mole per mole of the oxide.
The magnesium alkoxides, especially the lower alkoxides ti.e., those in which the alkyl groups contain 7 carbon atoms or less), are equivalent to magnesium oxide and hydroxide for the purpose of this invention; they are hydrolyzed by water to magnesium hydroxide under the con-ditions described hereinafter.
The equivalent weight of component A is half its molecular weight, since magnesium is a divalent element.
Component B
Component B is at least one oleophilic reagent comprising a carboxylic acid or a mixture thereof with a sulfonic acid, or salts or esters thereof. These acids include many of those known to be susceptible to overbasing and especially many of those disclosed in a number of U.S.
patents such as 2,616,904; 2,695,910; 3,312,618; 3,746,643;
3,764,533; and the aforementioned 3,629,109. Those patents disclose suitable acidic oleophilic reagents.
The carboxylic acids suitable for use as component B include aliphatic, cycloaliphatic and aromatic mono- and polybasic carboxylic acids free from acetylenic unsatur-ation, including naphthenic acids, alkyl- or alkenyl-sub-stituted cyclopentanoic acids, alkyl- or alkenyl-substituted cyclohexanoic acids, and alkyl- or alkenyl-substituted aromatic carboxylic acids. The aliphatic acids generally contain from about 8 to about 50, and preferably from about 12 to about 25, carbon atoms. The cycloaliphatic and ali-phatic carboxylic acids are preferred and they can be saturated or unsaturated. Specific examples include 2-ethylhexanoic acid, linolenic acid, propylene tetramer-substituted maleic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic 1~3~41Z
acid, lauric acid, oleic acid, ricinoleic acid, undecylic acid, dioctylcyclopentanecarboxylic acid, myristic acid, dilauryldecahydronaphthalenecarboxylic acid, stearyl-octa-hydroindenecarboxylic acid, palmitic acid, alkyl- and alkenylsuccinic acids, acids formed by oxidation of petro-latum or of hydrocarbon waxes, and commercially availablemixtures of two or more carboxylic acids such as tall oil acids, rosin acids, and the like.
The above-described carboxylic acids may be used in admixture with a minor amount of a sulfonic or penta-valent phosphorus acid; that is, component B may comprise a mixture containing more than 50~ by weight of carboxylic 10 acids and less than 50~ of sulfonic or pentavalent phos-phorus acids. Suitable sulfonic acids include those repre-sented by the formulas Rl(SO3H)r and (R2)XT(SO3H)y. In these formulas, Rl is an aliphatic or aliphatic-substituted cycloaliphatic hydrocarbon or essentially hydrocarbon radical free from acetylenic unsaturation and containing up to about 60 carbon atoms. When Rl is aliphatic, it usually 15 contains at least about 15 carkon atoms; when it is an aliphatic-substituted cycloaliphatic radical, the aliphatic substituents usually contain a total of at least about 12 carbon atoms. Examples of Rl are alkyl, alkenyl and alkoxy-alkyl radicals, and aliphatic-substituted cycloaliphatic radicals wherein the aliphatic substituents are alkyl, 20 alkenyl, alkoxy, alkoxyalkyl, carkoxyalkyl and the like.
Generally, the cycloaliphatic nucleus is derived from a cycloalkane or a cycloalkene such as cyclopentane, cyclo-hexane, cyclohexene or cyclopentene. Specific examples of Rl are cetylcyclohexyl, laurylcyclohexyl, cetyloxyethyl, octadecenyl, and radicals derived from petroleum, saturated and unsaturated paraffin wax, and olefin polymers including 25 polymerized monoolefins and diolefins containing about 2-E
carbon atoms per olefinic monomer unit. Rl can also contain 113t34~'~
other substituents such as phenyl, cycloalkyl, hydroxy, mercapto, halo, nitro, amino, nitroso, lower alkoxy, lower alkylmercapto, carboxy, carbalkoxy, oxo or thio, or inter-rupting groups such as -N~I-, -O- or -S-, as long as the essentially hydrocarbon character thereof is not destroyed.
R2 is generally a hydrocarbon or essentially hydrocarbon radical free from acetylenic unsaturation and containing from akout 4 to about 60 aliphatic carbon atoms, preferably an aliphatic hydrocarbon radical such as alkyl or 10 alkenyl. It may also, however, contain substituents or interrupting groups such as those enumerated above provided the essentially hydrocarbon character thereof is retained.
In general, the non-carbon atoms present in Rl or R2 do not account for more than 10% of the total weight thereof.
The radical T is a cyclic nucleus which may be derived from an aromatic hydrocarbon such as benzene, naphthalene, anthracene or biphenyl, or from a heterocyclic compound such aspyridine, indole or isoindole. Ordinarily, T is an aromatic hydrocarbon nucleus, especially a benzene 20 or naphthalene nucleus.
The subscript x is at least 1 and is generally 1-3. The subscripts r and y have an average value of about 1-4 per molecule and are generally also 1.
Illustrative sulfonic acids useful as part of 25 component B are mahogany sulfonic acids, petrolatum sulfonic acids, mono- and polywax-substituted naphthalene sulfonic acids, cetylchlorobenzene sulfonic acids, cetylphenol sul-fonic acids, cetylphenol disulfide sulfonic acids, cetoxy-capryl benzene sulfonic acids, dicetyl thianthrene sulfonic 30 acids, dilauryl ~-naphthol sulfonic acids, dicapryl nitro-naphthalene sulfonic acids, paraffin wax sulfonic acids, unsaturâted paraffin wax sulfonic acids, hydroxy-substituted paraffin wax sulfonic acids, tetraisobutylene sulfonic acids, tetra-amylene sulfonic acids, chloro-substituted 35 paraffin wax sulfonic acids, nitroso-substituted paraffin 113~4~Z
wa~ sulfonic acids, petroleum naphthene sulfonic acids, cetylcyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic acids, mono- and polywa~-substituted cyclohexyl sulfonic acids, postdodecylbenzene sulfonic acids, "dimer alkylate"
sulfonic acids, and the like. These sulfonic acids are well-known in the art and require no further discussion herein.
The pentavalent phosphorus acids useful as part of component B may be represented by the formula R3(Xl) \ ll R4(X 2 )/
wherein each of R3 and R4 is hydrogen or a hydrocarbon or essentially hydrocarbon radical preferably having from about 4 to about 25 carbon atoms, at least one of R3 and R4 being hydrocarbon or essentially hydrocarbon; each of Xl, X2, X3 15 and X4 is oxygen or sulfur; and each of a and b is O or 1.
Thus, it will be appreciated that the phosphorus acid may be an organophosphoric, phosphonic or phosphinic acid, or a thio analog of any of these.
Usually, the phosphorus acids are those of the R30 \ 0 0 formula / -OH wherein R3 is a phenyl radical or (preferably) an alkyl radical having up to 18 carbon atoms, and R4 is hydrogen or a similar phenyl or alkyl radical.
Mixtures of such phosphorus acids are often preferred because of their ease of preparation.
Also useful as component B are the alkali metal and alkaline earth metal salts (e.g., sodium, potassium, magnesi~m, calcium, strontium or barium salts, with mag-nesium salts being preferred) and esters of the acids pre-viously described. The suitable esters include those with 30 monohydric alcohols free from acetylenic unsaturation and having from about 1 to about 25 carbon atoms, including 11384~Z
monohydric alcohols such as methanol, ethanol, the butanols, the hexanols, allyl alcohol, crotyl alcohol, stearyl alcohol and oleyl alcohol, and polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, sorbitan and similar carbohydrates and derivatives of carbohydrates.
It will be appreciated from the above description of component B that it comprises an organic acid or a com-pound hydrolyzable thereto. The ratio of equivalents of 10 magnesium to equivalents of acid is important in the context of the invention, and so the equivalent weight of the acid portion of component B must be defined.
Obviously, to the extent that co~ponent B is a free acid its equivalent weight is its molecular weight 15 divided ky the number of acidic groups present per molecule.
To the extent component B is an ester or salt of a car-boxylic or sulfonic acid, it is considered to be convertible to the free acid during the reaction with component ~ and water and its equivalent weight is similarly calculated. To 20 the extent that component B is a phosphorus acid or a salt or ester thereof, its equivalent weight is its molecular weight divided by the sum of the acidic hydroxy groups bonded to phosphorus (or salts thereof) and the number of ester groups hydrolyzable to such hydroxy groups (or salts 25 thereof) under the reaction conditions of the invention. If any ester groups remain unhydrolyzed, the ester is consi-dered inert to that extent for the purpose of calculating equivalent weight.
The preferred compounds for use as component B are 30 the above-described carboxylic acids having an equivalent weight b~etween about 200 and about 500 and mixtures thereof with sulfonic acids of similar molecular weight, especially alkylaromatic sulfonic acids and more particularly alkyl-benzenesulfonic acids.
One of the characteristics of component B is that it is oleophilic. This means that it is soluble or at least 1~3841Z
_9_ stably dispersible (as defined hereinafter) in oil or similar non-polar organic liquids such as hexane, naphtha, Stoddard solvent, benzene, toluene and the like. While component B need not be oil-soluble, the oil-soluble acids are preferred for the purposes of this invention. These oil-soluble compounds constitute a known subgenus of the previously described compounds useful as component B.
Component C
Component C is water, which may be used in the 10 liquid or vapor phase ard is under certain conditions op-tional (as described hereinafter). For the purpose of the present invention, the equivalent weight of water is con-sidered to be 9 (half its molecular weight).
Component D
-Component D is at least one organic solubilizing agent for component B. It may bé solid or liquid at room temperature, although liquids are often preferred. It need not be a solvent for component B, in the sense that com-ponent B is entirely soluble therein when in the liquid 20 state, but should be at least a partial solvent in the sense that relatively small proportions of component B, at least, when blended with component D in the liquid state will form a homogeneous mixture.
Materials useful as component D include substan-25 tially inert, normally liquid organic diluents. The term "substantially inert" as used herein is intended to mean that the diluent is inert to chemical or physical change under the conditions in which it is used so as not to materially interfere in an adverse manner with the pre-30 paration, storage, blending and/or functioning of the mag-nesium complex in the context of its intended use. For example:; small amounts of a diluent can undergo minimal reaction or degradation without preventing the making and using of the invention as described herein. In other words, 35 such reaction or degradation, while technically discernible, would not be sufficient to deter the practical worker of ~13~41Z
ordinary skill in the art from making and using the inven-tion for its intended purposes. "Substantially inert" as used herein is thus readily understood and appreciated ky those of ordinary skill in the art.
Among the preferred normally liquid diluents are non-polar compounds or mixtures of compounds such as naph-tha, hexane, kerosene, mineral oil, Stoddard solvent, benzene, toluene, xylene, low molecular weight polybutenes, and alkylbenzenes of the type present as unsulfonated 10 residue in alkylbenzenesulfonic acids. Also suitable are somewhat more polar liquids such as l-butanol, 2-butanol, ethylene glycol, propylene glycol, ethylene glycol mono-methyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol and its ethers, 15 wax-derived alcohol mixtures, methyl ethyl ketone, chloro-benzene, pyridine, indole, furan and tetrahydrofuran.
Also useful are substantially inert materials which are solid at ambient temperature, and which may be chemically similar to the above-described liquids. These 20 include the following:
1. Waxes, such as:
Crystalline (including microcrystalline) wax Paraffin wax Petrolatum wax Beeswax Bohemia wax Hydrogenated castor oil Lanolin Shellac wax Spermaceti Carnauba wax Candelilla wax Chlorinated naphthalene ~31341Z
~Taxy alcohol mixtures (e.g. ~ C2 0-4 0 aliphatic alcohols) Other waxy materials of the type dis-closed in Kirk-Othmer, T~ncyclopedia of Chemical Technology, Second Edition, vol. 22, pp. 156-173 (which is incorporated by refer-ence herein for such aisclosure)
LF-1680-Ca This invention relates to new magnesium-containing compositions of matter and methods for their preparation.
In a general sense, the invention comprises thixotropic non-carbonated magnesium-containing complexes which are prepared by heating, at a temperature above about 30C., a mixture comprising:
(A) At least one of magnesium hydroxide, mag-nesium oxide, hydrated magnesium oxide and a magnesium alkoxide;
(B) At least one oleophilic organic reagent com-prising a carboxylic acid, a mixture of a major amount thereof with a minor amount of a sulfonic acid or pentavalent phosphorus acid, or an ester or alkali metal or alkaline earth metal salt of either of these;
`~
~F
113841~' (C) Water, if necessary to convert a substantial proportion of component A to magnesium hydroxide or hydrated magnesium oxide; and (D) At least one organic solubilizing agent for component B;
the ratio of equivalents of magnesium to the acid portion of component B being at least akout 5:1; and the amount of water present, if any, being sufficient to hydrate a substantial proportion of component A calculated as mag-10 nesium oxide.
Several methods are known for the preparation of basic magnesium compounds for use in lubricants, greases and the like. For example, U.S. Patent 3,865,737 describes the formation of a highly basic magnesium-containing liquid dis-15 persion by mixing an oil-soluble dispersing agent, magnesium oxide, a volatile aliphatic hydrocarbon solvent, alcohol, water and ammonia or an ammonium compound, treating the mix-ture with carbon dioxide, adding a non-volatile diluent oil and removing volatiles. Similarly, U.S. Patent 3,629,109 20 describes the carbonation of a mixture of an oil-soluble organic acid or salt thereof, magnesium oxide, a lower ali-phatic alcohol, water and an organic liquid diluent. The products obtained by these methods may be characterized, for the most part, as basic oleophilic magnesium carbonates 25 since an essential step in their preparation is reaction with carbon dioxide.
In accordance with the present invention, it has been discovered that highly basic, thixotropic magnesium complexes may be prepared without reaction with carbon 30 dioxide or similar acidic gases. The products obtained in accordance with the present invention, which may be charac-terized:as complexes of magnesium oxide or hydroxide and a magnesium salt of the acid comprising component B, and which are hereinafter sometimes referred to merely as "magnesium 35 complexes", have a wide variety of uses, including additives 113~34~'~
for lubricants and fuel oils and corrosion-resistant coat-ings or constituents thereof.
A principal object of the present invention, therefore, is to provide new oleophilic magnesium-containing compositions and a method for their preparation.
A further object is to provide a method for pro-ducing magnesium complexes which does not necessitate reac-tion with carbon dioxide or a similar acidic gas.
A further object is to provide basic thixotropic 10 magnesium compositions which may be obtained either in liquid or solid form.
Still another object is to provide thixotropic magnesium-containing compositions useful as greases, as detergent additives for lubricants or as corrosion inhi-15 bitors, vanadium scavengers and smoke suppressants forfuels, and in the formulation of corrosion-resistant coat-ings for metals.
Other objects will in part be obvious and will in part appear hereinafter.
20 Component A
Component A used in the method of this invention is magnesium hydroxide, magnesium oxide, hydrated magnesium oxide, a maynesium alkoxide, or a mixture of these. Magne-sium hydroxide and magnesium oxide are, of course, repre-25 sented by the formulas Mg(OH) 2 and MgO, respectively.Magnesium oxide exists in an inactive "dead burned" and a hydratable "reactive" form and the latter is the one which is useful in this invention although mixtures~of the "reac-tive" form with minor amounts of the "dead burned" form may 30 also be used. "Hydrated magnesium oxide", for the purpose of this invention, is magnesium oxide which is associated with water in an amount less than that required for con-version to magnesium hydroxide; that is, the amount of water is less than one mole per mole of magnesium oxide. As so 35 defined, "hydrated magnesium oxide" may actually be a mix-~138~12 ture of various proportions of magnesium oxide and magnesium hydroxide and its exact chemical nature is not critical to this invention. Typically, the amount of water present in "hydrated magnesium oxide" is at least about 0.7 mole per mole of the oxide.
The magnesium alkoxides, especially the lower alkoxides ti.e., those in which the alkyl groups contain 7 carbon atoms or less), are equivalent to magnesium oxide and hydroxide for the purpose of this invention; they are hydrolyzed by water to magnesium hydroxide under the con-ditions described hereinafter.
The equivalent weight of component A is half its molecular weight, since magnesium is a divalent element.
Component B
Component B is at least one oleophilic reagent comprising a carboxylic acid or a mixture thereof with a sulfonic acid, or salts or esters thereof. These acids include many of those known to be susceptible to overbasing and especially many of those disclosed in a number of U.S.
patents such as 2,616,904; 2,695,910; 3,312,618; 3,746,643;
3,764,533; and the aforementioned 3,629,109. Those patents disclose suitable acidic oleophilic reagents.
The carboxylic acids suitable for use as component B include aliphatic, cycloaliphatic and aromatic mono- and polybasic carboxylic acids free from acetylenic unsatur-ation, including naphthenic acids, alkyl- or alkenyl-sub-stituted cyclopentanoic acids, alkyl- or alkenyl-substituted cyclohexanoic acids, and alkyl- or alkenyl-substituted aromatic carboxylic acids. The aliphatic acids generally contain from about 8 to about 50, and preferably from about 12 to about 25, carbon atoms. The cycloaliphatic and ali-phatic carboxylic acids are preferred and they can be saturated or unsaturated. Specific examples include 2-ethylhexanoic acid, linolenic acid, propylene tetramer-substituted maleic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic 1~3~41Z
acid, lauric acid, oleic acid, ricinoleic acid, undecylic acid, dioctylcyclopentanecarboxylic acid, myristic acid, dilauryldecahydronaphthalenecarboxylic acid, stearyl-octa-hydroindenecarboxylic acid, palmitic acid, alkyl- and alkenylsuccinic acids, acids formed by oxidation of petro-latum or of hydrocarbon waxes, and commercially availablemixtures of two or more carboxylic acids such as tall oil acids, rosin acids, and the like.
The above-described carboxylic acids may be used in admixture with a minor amount of a sulfonic or penta-valent phosphorus acid; that is, component B may comprise a mixture containing more than 50~ by weight of carboxylic 10 acids and less than 50~ of sulfonic or pentavalent phos-phorus acids. Suitable sulfonic acids include those repre-sented by the formulas Rl(SO3H)r and (R2)XT(SO3H)y. In these formulas, Rl is an aliphatic or aliphatic-substituted cycloaliphatic hydrocarbon or essentially hydrocarbon radical free from acetylenic unsaturation and containing up to about 60 carbon atoms. When Rl is aliphatic, it usually 15 contains at least about 15 carkon atoms; when it is an aliphatic-substituted cycloaliphatic radical, the aliphatic substituents usually contain a total of at least about 12 carbon atoms. Examples of Rl are alkyl, alkenyl and alkoxy-alkyl radicals, and aliphatic-substituted cycloaliphatic radicals wherein the aliphatic substituents are alkyl, 20 alkenyl, alkoxy, alkoxyalkyl, carkoxyalkyl and the like.
Generally, the cycloaliphatic nucleus is derived from a cycloalkane or a cycloalkene such as cyclopentane, cyclo-hexane, cyclohexene or cyclopentene. Specific examples of Rl are cetylcyclohexyl, laurylcyclohexyl, cetyloxyethyl, octadecenyl, and radicals derived from petroleum, saturated and unsaturated paraffin wax, and olefin polymers including 25 polymerized monoolefins and diolefins containing about 2-E
carbon atoms per olefinic monomer unit. Rl can also contain 113t34~'~
other substituents such as phenyl, cycloalkyl, hydroxy, mercapto, halo, nitro, amino, nitroso, lower alkoxy, lower alkylmercapto, carboxy, carbalkoxy, oxo or thio, or inter-rupting groups such as -N~I-, -O- or -S-, as long as the essentially hydrocarbon character thereof is not destroyed.
R2 is generally a hydrocarbon or essentially hydrocarbon radical free from acetylenic unsaturation and containing from akout 4 to about 60 aliphatic carbon atoms, preferably an aliphatic hydrocarbon radical such as alkyl or 10 alkenyl. It may also, however, contain substituents or interrupting groups such as those enumerated above provided the essentially hydrocarbon character thereof is retained.
In general, the non-carbon atoms present in Rl or R2 do not account for more than 10% of the total weight thereof.
The radical T is a cyclic nucleus which may be derived from an aromatic hydrocarbon such as benzene, naphthalene, anthracene or biphenyl, or from a heterocyclic compound such aspyridine, indole or isoindole. Ordinarily, T is an aromatic hydrocarbon nucleus, especially a benzene 20 or naphthalene nucleus.
The subscript x is at least 1 and is generally 1-3. The subscripts r and y have an average value of about 1-4 per molecule and are generally also 1.
Illustrative sulfonic acids useful as part of 25 component B are mahogany sulfonic acids, petrolatum sulfonic acids, mono- and polywax-substituted naphthalene sulfonic acids, cetylchlorobenzene sulfonic acids, cetylphenol sul-fonic acids, cetylphenol disulfide sulfonic acids, cetoxy-capryl benzene sulfonic acids, dicetyl thianthrene sulfonic 30 acids, dilauryl ~-naphthol sulfonic acids, dicapryl nitro-naphthalene sulfonic acids, paraffin wax sulfonic acids, unsaturâted paraffin wax sulfonic acids, hydroxy-substituted paraffin wax sulfonic acids, tetraisobutylene sulfonic acids, tetra-amylene sulfonic acids, chloro-substituted 35 paraffin wax sulfonic acids, nitroso-substituted paraffin 113~4~Z
wa~ sulfonic acids, petroleum naphthene sulfonic acids, cetylcyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic acids, mono- and polywa~-substituted cyclohexyl sulfonic acids, postdodecylbenzene sulfonic acids, "dimer alkylate"
sulfonic acids, and the like. These sulfonic acids are well-known in the art and require no further discussion herein.
The pentavalent phosphorus acids useful as part of component B may be represented by the formula R3(Xl) \ ll R4(X 2 )/
wherein each of R3 and R4 is hydrogen or a hydrocarbon or essentially hydrocarbon radical preferably having from about 4 to about 25 carbon atoms, at least one of R3 and R4 being hydrocarbon or essentially hydrocarbon; each of Xl, X2, X3 15 and X4 is oxygen or sulfur; and each of a and b is O or 1.
Thus, it will be appreciated that the phosphorus acid may be an organophosphoric, phosphonic or phosphinic acid, or a thio analog of any of these.
Usually, the phosphorus acids are those of the R30 \ 0 0 formula / -OH wherein R3 is a phenyl radical or (preferably) an alkyl radical having up to 18 carbon atoms, and R4 is hydrogen or a similar phenyl or alkyl radical.
Mixtures of such phosphorus acids are often preferred because of their ease of preparation.
Also useful as component B are the alkali metal and alkaline earth metal salts (e.g., sodium, potassium, magnesi~m, calcium, strontium or barium salts, with mag-nesium salts being preferred) and esters of the acids pre-viously described. The suitable esters include those with 30 monohydric alcohols free from acetylenic unsaturation and having from about 1 to about 25 carbon atoms, including 11384~Z
monohydric alcohols such as methanol, ethanol, the butanols, the hexanols, allyl alcohol, crotyl alcohol, stearyl alcohol and oleyl alcohol, and polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, sorbitan and similar carbohydrates and derivatives of carbohydrates.
It will be appreciated from the above description of component B that it comprises an organic acid or a com-pound hydrolyzable thereto. The ratio of equivalents of 10 magnesium to equivalents of acid is important in the context of the invention, and so the equivalent weight of the acid portion of component B must be defined.
Obviously, to the extent that co~ponent B is a free acid its equivalent weight is its molecular weight 15 divided ky the number of acidic groups present per molecule.
To the extent component B is an ester or salt of a car-boxylic or sulfonic acid, it is considered to be convertible to the free acid during the reaction with component ~ and water and its equivalent weight is similarly calculated. To 20 the extent that component B is a phosphorus acid or a salt or ester thereof, its equivalent weight is its molecular weight divided by the sum of the acidic hydroxy groups bonded to phosphorus (or salts thereof) and the number of ester groups hydrolyzable to such hydroxy groups (or salts 25 thereof) under the reaction conditions of the invention. If any ester groups remain unhydrolyzed, the ester is consi-dered inert to that extent for the purpose of calculating equivalent weight.
The preferred compounds for use as component B are 30 the above-described carboxylic acids having an equivalent weight b~etween about 200 and about 500 and mixtures thereof with sulfonic acids of similar molecular weight, especially alkylaromatic sulfonic acids and more particularly alkyl-benzenesulfonic acids.
One of the characteristics of component B is that it is oleophilic. This means that it is soluble or at least 1~3841Z
_9_ stably dispersible (as defined hereinafter) in oil or similar non-polar organic liquids such as hexane, naphtha, Stoddard solvent, benzene, toluene and the like. While component B need not be oil-soluble, the oil-soluble acids are preferred for the purposes of this invention. These oil-soluble compounds constitute a known subgenus of the previously described compounds useful as component B.
Component C
Component C is water, which may be used in the 10 liquid or vapor phase ard is under certain conditions op-tional (as described hereinafter). For the purpose of the present invention, the equivalent weight of water is con-sidered to be 9 (half its molecular weight).
Component D
-Component D is at least one organic solubilizing agent for component B. It may bé solid or liquid at room temperature, although liquids are often preferred. It need not be a solvent for component B, in the sense that com-ponent B is entirely soluble therein when in the liquid 20 state, but should be at least a partial solvent in the sense that relatively small proportions of component B, at least, when blended with component D in the liquid state will form a homogeneous mixture.
Materials useful as component D include substan-25 tially inert, normally liquid organic diluents. The term "substantially inert" as used herein is intended to mean that the diluent is inert to chemical or physical change under the conditions in which it is used so as not to materially interfere in an adverse manner with the pre-30 paration, storage, blending and/or functioning of the mag-nesium complex in the context of its intended use. For example:; small amounts of a diluent can undergo minimal reaction or degradation without preventing the making and using of the invention as described herein. In other words, 35 such reaction or degradation, while technically discernible, would not be sufficient to deter the practical worker of ~13~41Z
ordinary skill in the art from making and using the inven-tion for its intended purposes. "Substantially inert" as used herein is thus readily understood and appreciated ky those of ordinary skill in the art.
Among the preferred normally liquid diluents are non-polar compounds or mixtures of compounds such as naph-tha, hexane, kerosene, mineral oil, Stoddard solvent, benzene, toluene, xylene, low molecular weight polybutenes, and alkylbenzenes of the type present as unsulfonated 10 residue in alkylbenzenesulfonic acids. Also suitable are somewhat more polar liquids such as l-butanol, 2-butanol, ethylene glycol, propylene glycol, ethylene glycol mono-methyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol and its ethers, 15 wax-derived alcohol mixtures, methyl ethyl ketone, chloro-benzene, pyridine, indole, furan and tetrahydrofuran.
Also useful are substantially inert materials which are solid at ambient temperature, and which may be chemically similar to the above-described liquids. These 20 include the following:
1. Waxes, such as:
Crystalline (including microcrystalline) wax Paraffin wax Petrolatum wax Beeswax Bohemia wax Hydrogenated castor oil Lanolin Shellac wax Spermaceti Carnauba wax Candelilla wax Chlorinated naphthalene ~31341Z
~Taxy alcohol mixtures (e.g. ~ C2 0-4 0 aliphatic alcohols) Other waxy materials of the type dis-closed in Kirk-Othmer, T~ncyclopedia of Chemical Technology, Second Edition, vol. 22, pp. 156-173 (which is incorporated by refer-ence herein for such aisclosure)
2. Hydrocarkon and similar resins, such as:
Olefin polymer resins and ~-axes (e.g., polyethylene, polypropylene) Terpene resins Coumarone-indene resins Phenolic and,alkylated phenolic resins Furan resins '~
Olefin polymer resins and ~-axes (e.g., polyethylene, polypropylene) Terpene resins Coumarone-indene resins Phenolic and,alkylated phenolic resins Furan resins '~
3. Matural resins, such as:
Copal ~anila chips Gum damar Accroides gum Rosin Hydroabietyl alcohol resin
Copal ~anila chips Gum damar Accroides gum Rosin Hydroabietyl alcohol resin
4. Addition polymer resins, such as:
Styrene-butadiene Hydrogenated styrene-butadiene 1138~12 Polystyrene and poly(~-methylstyrene) Olefin-vinyl acetate copolymers Polyvinyl acetate Polyvinyl chloride Vinyl acetate-vinyl chloride copolymers Acrylic resins Solid polybutenes
Styrene-butadiene Hydrogenated styrene-butadiene 1138~12 Polystyrene and poly(~-methylstyrene) Olefin-vinyl acetate copolymers Polyvinyl acetate Polyvinyl chloride Vinyl acetate-vinyl chloride copolymers Acrylic resins Solid polybutenes
5. Polyester resins
6. Solid plasticizers, such as:
Triethylene glycol dibenzoate Neopentyl glycol dibenzoate Glyceryl tribenzoate It is also within the scope of the invention to use mixtures of any of the materials described above. Such 15 mixtures may be of materials all of which are liquid at normal ambient temperatures ~e.g., about 20-30C.), such as mineral oil-toluene, Stoddard solvent-toluene, mineral oil-alkylbenzene, Stoddard solvent-alkylbenzene; of materials all of which are solid at normal ambient temperatures, such 20 as paraffin wax-polyethylene wax, paraffin wax-polyethylene wax-C2 0-4 0 alcohol wax; or of materials which are both liquid and solid at normal ambient temperatures, such as mixtures of the above-mentioned normally liquid diluents and a resin or hydrocarbon wax (e.g., paraffin wax-toluene, 25 polypropylene-toluene, polypropylene-mineral oil).
Component Proportions The relative proportions of components A, B, C and D are an important feature o' this invention since the physica~ state in which the magnesium complex is obtained 30 depends to a great extent on the proportions of the com-ponents used for their preparation.
As previously noted, the ratio of equivalents of magnesium to the acid portion of component B is at least 11384~
about 5:1. This ratio is hereinafter sometimes referred to as the "magnesium ratio". tIt will be appreciated that the magnesium ratio is such as to produce a basic magnesium complex.) If component B is a free carboxylic acid or an ester or salt thereof with a metal other than magnesium, the ratio of component A to component B will be identical to the magnesium ratio. If component B is a magnesium salt, the ratio of component A to component B will be somewhat less than the magnesium ratio since part of the magnesium is 10 provided ky component s.
It has been found that magnesium complexes with relatively low maynesium ratios (e.g., from about 5:1 to about 21:1 and particularly from about 5:1 to about 10:1) are particularly useful as lubricant additives. Complexes 15 with a magnesium ratio above about 60:1 and preferably up to about 150:1 find utility principally as additives for fuel oils. As protective coatings for metals, it is preferred to employ complexes in which component D is entirely or pre-dominantly liquid and the magnesium ratio is between about 20 25:1 and about 60:1, or solid te-g., "hot melt") complexes in which component D is entirely or predominantly solid at ambient temperature and which typically have a magnesium ratio from about 5:1 to about 50:1.
The ratio of moles of water (component C) to 25 grams-atoms of magnesium in component A tsaid ratio herein-after sometimes designated the "water ratio") is also critical. ~Jhen component A is substantially all magnesium hydroxide or hydrated magnesium oxide, the prèsence of water is frequently not required. If water is not present, 30 however, complex preparation usually requires extremely efficie~t high-speed mixing te-g-, by mixers such as that sold under the trade ~K~"Dispersator" by Premier Mill Corporation) so as to produce a uniform product. When a substantial portion of component A is magnesium oxide or a 35 magnesium alkoxide, the presence of water as component C is required.
~J~3~1Z
Most often, the use of water is advantageous regardless of the identity of component A. When it is present, the amount of water should be at least sufficient to hydrate a substantial proportion of component A, cal-culated as magnesium oxide. The proportion of additionalwater over and above that amount will depend on the nature of the product desired and the intended use thereof. If component A is anhydrous magnesium oxide the water ratio should generally be at least about 0.7:1 so as to produce a 10 substantial proportion of the hydrated magnesium oxide referred to hereinabove.
A water ratio up to about 3.0:1, and especially from about 0.7:1 to about 3.0:1, is usually adequate to produce a composition of this invention. If larger amounts 15 Of water than this are used, it is frequently possible to remove excess water, at least some of which separates from the magnesium complex as a separate layer and the remainder of which can be removed by azeotropic distillation or the like. More water may be desirable for the preparation of 20 the complex in certain instances; for example, magnesium oxide frequently contains traces of sodium compounds whose presence may be undesirable in the complex, and if so, such compounds may be removed by using up to about 8 moles of water per mole of component A and removing the excess, which 25 has dissolved therein the sodium compounds. When the excess water has been removed, the molar ratio of remaining water to component A is usually below about 3:1 as noted above.
As among various magnesium complexes-with water ratios between about 0.7:1 and about 3.0:1, those having a 30 water ratio below about 1:1 are often particularly useful as lubricant additives or fuel oil additives, while those having a somewhat higher water ratio (e.g., between about 1:1 and 3:1) may be particularly useful in the preparation of corrosion-resistant coating compositions.
The ratio of component D to component A is not critical and may be varied so as to provide magnesium com-1138~1Z
plexes suitable for the particular use for which they are intended. For example, a complex suitable as a lubricant additive may frequently be obtained by employing as com-ponent D solely the unsulfonated alkylbenzene present as an impurity in the sulfonic acid used as component B. In that event, the weight ratio of component D to component A will usually be below about 1:1 and frequently as low as 0.5-0.7:1. In general, when a lubricant additive product is desired it is inaclvisable to use volatile materials as 10 component D.
When the magnesium complex is to be used as a fuel oil additive, higher amounts of component D are frequently preferred and these may include relatively volatile mat-erials such as toluene or xylene, less volatile materials 15 such as mineral oil or mineral seal oil, and mixtures of volatile and less volatile materials. The proportions of volatile and non-volatile solubilizing agents in such mixtures are subject to wide variation, but in any event it is usually found that the total weight ratio of component D
20 to component A should be from about 1.2:1 to about 1.8:1.
When a product useful in a protective metal coat-ing is desired, still higher ratios (e.g., from about 2:1 to about 3:1) are often employed with one of the solubilizing agents being a substantially volatile aliphatic hydrocarbon 25 such as naphtha or StOddard solvent, and the other being a somewhat less volatile material such as mineral oil. Ano-ther useful type of complex for metal coating is the solid (e.g., "hot melt") type briefly referred to hereinabove, in which component D comprises mostly or entirely materials 30 which are solid at ambient temperature, in which case the ratio of D to ~ may be between about 0.5:1 and about 6:1.
Prepara~ion of the Magnesium Complex The magnesium complexes of this invention are pre-pared by merely blending the components described herein-35 above and heating the resulting blend at a temperature above 113~41;~
about 30C. It is important that water (if present as component C) remain in the blend during substantially the entire period of preparation of the magnesium complex, and the maximum temperature thereof should be adjusted accord-ingly. ~lowever, said water may be present in the liquid orvapor state, i.e., as liquid water or as steam, though it will be apparent to those skilled in the art that the preparation of complexes involving a relatively large amount of water will be difficult if not impossible, at least at 10 atmospheric pressure, if the water is present as steam.
Therefore, it is generally found that temperatures between about 30 and about 125C. are most conveniently employed at atmospheric pressure, and the preparation should be carried out under superatmospheric pressure if the use of higher 15 temperatures is likely. Most often, a maximum temperature of about 100C. is convenient when component D is entirely or predominantly liquid and the preferred temperature range is then between about 40 and about 90C. Naturally, the temperature may be somewhat higher (e.g., between about 95 20 and about 150C.) when component D is entirely or predomi-nantly a solid at ambient temperature.
The order of addition of the various components is not critical. It is often convenient to first combine components A, B and D and subsequently to add component C
25 (water) either all at once or incrementally. It is also often found convenient to prepare an initial mixture con-taining only a relatively small portion of component A
(e.g., from about 5% to about 10% of the total`amount thereof) and to add the remainder at a later stage, typi-30 cally during or after the addition of water. Finally, it iswithin the scope of the invention to prepare the magnesium complex using only a portion of the amount of component D
intended, and to add the remainder after the complex has been prepared. The amount subsequently added is generally 35 less than about 50% and preferably less than about 40% by 1138~
weight of the total amount to be used. This subsequent addition of part of component D is most often useful when component D is partly or entirely solid (for example, when it comprises waxes and/or resins) and/or ~hen it imparts additional desirable properties such as modifying fluidity under the conditions of use.
The magnesium complexes of this invention are thixotropic; that is, they decrease in viscosity when agitated and return to approximately their original vis-10 cosity after agitation ceases. When component D is pre-dominantly liquid, the complexes are typically viscous liquids or heterogeneous dispersions in the form of greases or gels. When component D is predominantly solid, the magnesium complex may be a solid,"hot melt" type material.
The solid materials are useful for many purposes, such as for the formation of corrosion-resistant coatings as described hereinafter. For some other applications, such as those involving lubricants and fuels, the complex is pre-ferably obtained in the form of a relatively non-viscous, 20 easily flowable liquid. Such liquids may be obtained by methods well known to those of skill in the art, such as by maximizing the amount of liquid diluent present as component D or by decreasing the relative amount of component A or component C in the reaction mixture. Alternatively, a 30 viscous or solid complex can be further diluted with a substantially inert organic liquid diluent of the type described hereinabove to produce a homogeneous--solution.
One of the unique and desirable characteristics of the thixotropic compositions of this invention is their capa-.
11~8~12 bility of existing either as heterogeneous compositions or homogeneous, relatively dilute solutions or dispersions.
A method which is sometimes advantageous for incorporating relatively large amounts of magnesium while making possible the formation of a homogeneous solution or dispersion in mineral oil or the like is to prepare the complex in the presence of ammonium hydroxide, which may be prepared from ammonia and the water present as component C.
The amount of ammonium hydroxide required is small, gen-10 erally less than a~out 10~ by weight based on the waterpresent. Insoluble materials can then be removed by dilu-ting with a non-polar volatile organic liquid such as hexane or naphtha, centrifuging, and stripping the volatile liquid, or by equivalent means.
Another method for clarifying the magnesium complex for use in mineral oil, which may be employed in addition to or in place of preparation in the presence of ammonium hydroxide, is to add water or an acidic or kasic reagent after preparation of the complex. The acidic or 20 basic reagent may be organic or inorganic; suitable ones include sodium hydroxide, potassium hydroxide, ammonium hydroxide, triethanolamine, tartaric acid and citric acid.
The amount of water or acidic or basic reagent is generally less than about 10% by weight of the magnesium complex ~5 system.
The stability of the magnesium complexes of this invention is often improved if a minor effective amount of an oxidation inhibitor is incorporated therein. Suitable oxidation inhibitors include the hindered phenol type, 30 illustrated by 2,6-di-t-butylphenol and its derivatives; and the arylamine type, illustrated by phenyl-~-naphthylamine.
The amo~r;t of antioxidant required is usually between about 0.1~ and akout 2% and preferahly between about 0.2~ and 1%
by weight. Oxidation inhibitors are particularly useful in 35 the corrosion-resistant coating compositions of this inven-tion since they inhibit viscosity decreases thereof.
The preparation of the magnesium complexes of this invention is illustrated by the following examples. All parts are by weight.
Example 1 A mixture of 754 parts of water, 23 parts of magnesium oxide, 210 parts of mineral oil and 247 parts of Stoddard solvent is heated to about 40C. and 331 parts of a carboxylic acid having an equivalent weight of about 350 and obtained by oxidation of petrolatum, which acid has been preheated to about 50-60C., is added as the temperature of the mixture is maintained at 40-45C. An additional 350 parts of magnesium oxide is added, with stirring, and the temperature of the mixture is increased to 75C. An opaque dispersion is obtained which is screened to afford the desired magnesium oxide-carboxylate complex.
Example 2 A product similar to that of Example 1 is pre-pared, substituting about 300 parts of sorbitan trioleate for the oxidized petrolatum.
Example 3 A mixture of 16 parts of an alkylbenzenesulfonic acid having an equivalent weight of about 430 and containing about 22% unsulfonated alkylbenzene, 305 parts of mineral oil, 180 parts of magnesium oxide and 96 parts of the mixture sold under the trade mark "Hydrex 440", a mixture of hydrogenated fatty acids obtainable from Union Camp Corporation, is heated to 95C. and blown with steam for two hours. The temperature is increased to 145-150C., an additional 28 parts of mineral oil is added and the mixture is blown with air as the temperature is heated to 170C. over 15 minutes. The mixture is then cooled to room temperature and an additional 44 parts of mineral oil is added to yield the desired magnesium oxide-carboxylate-sulfonate complex having the consistency of a grease.
~13~9~1;2 Lubricants and Fuels When in the form of flowable liquids as previously described, the magnesium complexes of this invention are stably dispersible in the normally liquid media (e.g., oil, fuel, etc.) in which they are intended to function. Thus, for example, compositions intended for use in oils are stably dispersible in an oil in which they are to be used.
The term "stably dispersible" as used in the specification and appended claims is intended to mean the magnesium com-10 plex or other material is capable of being dispersed in agiven medium to an extent which allows it to function in its intended manner. Thus, for example, when a magnesium com-plex is used in an oil, it is sufficient that it be capakle of being suspended in the oil in an amount sufficient to 15 enable the oil to possess one or more of the desired pro-perties imparted to it by the suspended complex. Such suspension can be achieved in various conventional ways.
For example, in constantly circulating oil or oil in splash lubricating systems, physical agitation can keep the complex 20 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 magnesium complex. In any event, the complex will be "stably dis-25 persible" in the normally liquid media in which it will be used in at least the minimum concentrations set forth elsewhere herein. Thus, the terminology "stably disper-sible" is used in a conventional manner and will be un-derstood by those of ordinary skill in the art.
As previously indicated, the magnesium complexes of this invention may be homogeneously incorporated into lukrica~ts, in which they function primarily as ash-pro-ducing detergents. They can be employed in a variety of lubricants based on diverse oils of lubricating viscosity, 3S including natural and synthetic lubricating oils and mix-~13Ei 4~2 tures thereof. These lubricants include crankcase lubri-cating oils for spark-ignited and compression-ignited internal combustion engines, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad diesel engines, and the like. They can also be used in gas engines, stationary power engines and turbines and the like. Automatic transmission fluids, transaxle lubricants, gear lubricants, metal-working lubricants, hydraulic fluids and other lubricating oil and grease 10 compositions can also benefit from the incorporation therein of the compositions of the present invention.
Natural oils include animal oils and vegetable oils (e.g , castor oil, lard oil) as well as liquid petro-leum oils and solvent-treated or acid-treated mineral 15 lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and 20 interpolymerized olefins [e.g., polybutylenes, polypro-pylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(l-hexenes), poly(l-octenes), poly(l-decenes), etc. and mixtures thereof]; alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-25 ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls,terphenyls, alkylated polyphenyls, etc.), alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof and the like. ~
Alkylene oxide polymers and interpolymers and 30 derivatives thereof where the terminal hydroxyl groups have ~ -been modified by esterification, etherification, etc. con-stituteranother class of known synthetic lubricating oils.
These are exemplified by the oils prepared through poly-merization of ethylene oxide or propylene oxide, the alkyl 35 and aryl ethers of these polyoxyalkylene polymers (e.g., ~3841Z
methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a ~olecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters, or the C~ 3 OXO acid diester of tetraethylene glycol.
Another suitable class of synthetic lubrieating oils eomprises the esters of diearkoxylie aeids (e.g., 10 phthalie acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic aeid, azelaie aeid, suberie acia, sebacic acid, fumaric acid, adipic aeid, linoleic acid dimer, malonie acid, alkyl malonie aeids, alkenyl malonie aeids, ete.) with a variety of alcohols (e.g., butyl aleohol, 15 hexyl alcohol, dodecyl alcohol, ~-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glyeol, ete.). Speeifie examples of these esters inelude dibutyl adipate, di(2-ethylhexyl) sebaeate, di-n-hexyl fumarate, dioetyl sebaeate, diisooetyl azelate, diisodeeyl 20 azelate, dioetyl phthalate, dideeyl phthalate, dieieosyl sebaeate, the 2-ethylhexyl diester of linoleie aeid dimer, the eomplex ester formed by reaeting one mole of sebaeie aeid with two moles of tetraethylene glyeol and two moles of 2-ethylhexanoie aeid, and the like.
Esters useful as synthetie oils also inelude those made from Cs to Cl 2 monoearboxylie aeids and polyols and polyol ethers sueh neopentyl glyeol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, ete.
Silieon-based oils sueh as the polyalkyl-, poly-30 aryl-, polyalkoxy-, or polyaryloxy-siloxane oils and sili-eate oil-s eomprise another useful elass of synthetie lubri-eants ~e.g., tetraethyl silieate, tetraisopropyl silieate, tetra-(2-ethylhexyl) silieate, tetra-(4-methyl-2-ethylhexyl) silieate, tetra-(p-tert-butylphenyl) silieate, hexa-(4-35 methyl-2-pentoxy)-disiloxane, poly(methyl)-siloxanes, poly(methylphenyl)siloxanes, etc.). other synthetic lubri-cating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid, etc.), polymeric tetrahydrofurans and the like.
Unrefined, refined and rerefined oils (and mix-tures of each with each other) of the type disclosed here-inabove can be used in the lubricant compositions of the present invention. ~nrefined oils are those obtained 10 directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. ~efined oils 15 are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques are known to those of skill in the art such as solvent extraction, acid or base extraction, filtration, percol-20 ation, etc. Rerefined oils are obtained by processessimilar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques 25 directed to removal of spent additives and oil breakdown products.
Generally, the lubricants of the present invention contain an amount of the magnesium complex of~this invention sufficient to impart detergency thereto. Normally this 30 amount will be from about 0.05% to about 20%, preferably from about 0.5% to about 10%, of the total weight of the lubricant. In lubricating oils operated under extremely adverse conditions, such as lubricating oils for marine diesel engines, the magnesium complexes of this invention 35 may be present in amounts up to about 30%.
1138~1Z
-2~-The magnesium complexes of the present invention are also useful as corrosion inhibitors, vanadium scavengers and smoke suppressants in fuels. For that purpose, they are homogeneously incorporated in minor proportions in normally liquid fuels, usually hydrocarbonaceous fuels such as fuel oils, bunker fuels and the like. Normally liquid fuel com-positions comprising non-hydrocarbonaceous materials such as alcohols, ethers, organo-nitro compounds and the like (e.g., methanol, ethanol, diethyl ether, methyl ethyl ether, 10 nitromethane) are also within the scope of the invention as are liquid fuels derived from vegetable or mineral sources such as corn, alfalfa, shale and coal. Normally liquid fuels which are mixtures of one or more hydrocarbonaceous fuels and one or more non-hydrocarkonaceous materials are 15 also contemplated.
Generally, these fuel compositions contain an amount of the magnesium complex sufficient to impart corro-sion resistance thereto, suppress smoke or serve as a vana-dium scavenger; usually this amount is from about l to about 20 10,000, preferably from about 4 to about 1000, parts thereof by weight per million parts of fuel.
The invention also contemplates the use of other additives in combination with the magnesium complexes.
Other additives useful in lubricants include, for example, 25 auxiliary detergents and dispersants of the ash-producing or ashless type, corrosion- and oxidation-inhibiting agents, pour point depressing agents, extreme pressure agents, color stabilizers and anti-foam agents.
The auxiliary ash-producing detergents are exem-30 plified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, or organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage such as those prepared by the treatment of an olefin polymer (e.g., polyisobutene 35 having a molecular weight of 1000) with a phosphorizing lZ
agent such as phosphorus trichloride, phosphorus hepta-sulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphoro-thioic chloride. The most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, strontium and barium.
The term "basic salt" is used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical. The commonly 10 employed methods for preparing the basic salts involve heat-ing a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50C. and filtering the resulting mass.
15 The use of a "promoter" in the neutralization step to aid the incorporation of a large excess of metal likewise is known. Examples of compounds useful as the promoter include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation pro-20 ducts of formaldehyde with a phenolic substance; alcoholssuch as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-~-naphthylamine, and dodecylamine. A
25 particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter, and carbonating the mixture at an elevated tem-perature such as 60-200C.
Ashless detergents and dispersants are so called despite the fact that, depending on its constitution, the dispersânt may upon combustion yield a non-volatile material such as boric oxide or phosphorus pentoxide; however, it does not ordinarily contain metal and therefore does not 35 yield a metal-containing ash on combustion. Many types are known in the art, and any of them are suitable for use in the lubricants of this invention. The following are illus-trative:
(1) Reaction products of carboxylic acids (or derivatives thereof) containing at least about 34 and pre-ferably at least about 54 carbon atoms with nitrogen-con-taining compounds such as amine, organic hydroxy compounds such as phenols and alcohols, and/or basic inorganic mater-ials. Examples of these "carboxylic dispersants" are 10 described in British Patent 1,306,529 and in many U.S.
patents including the following:
3,163,603 3,351,552 3,541,012 3,184,474 3,381,022 3,542,678 3,215,707 3,399,1~1 3,542,680 15 3,219,666 3,415,750 3,567,637 3,271,310 3,433,744 3,574,101 3,272,746 3,444,170 3,576,743 3,281,357 3,448,048 3,630,904 3,306,908 3,448,049 3,632,510 20 3,311,558 3,451,933 3,632,511 3,316,177 3,454,607 3,697,428 3,340,281 3,467,668 3,725,441 3,341,542 3,501,405 Re 26,433 3,346,493 3,522,179 (2) Reaction products of relatively high molecu-lar weight aliphatic or alicyclic halides with amines, pre-ferably polyalkylene polyamines. These may be characterized as "amine dispersants" and examples thereof ar`e described for example, in the following U.S. patents:
3,275,554 3,454,555 3,438,757 3,565,804 (3) Reaction products of alkyl phenols in which the alkyl group contains at least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially 35 polyalkylene polyamines), which may be characterized as 1~3841Z
"Mannich dispersants". The materials described in the following U.S. patents are illustrative:
3,413,347 3,725,480 3,697,574 3,726,882 3,725,277 (4) Products obtained by post-treating the car-boxylic, amine or Mannich dispersants with such reagents as urea, thiourea, carbon disulfide, aldehydes, ketones, car-boxylic acids, hydrocarbon-substituted succinic anhyrides, nitriles, epoxides, boron compounds, phosphorus compounds or the like. Exemplary materials of this kind are described in the following U.S. patents:
3,036,003 3,282,955 3,493,520 3,639,~42 3,087,936 3,312,619 3,502,677 3,649,229 3,200,107 3,366,569 3,513,093 3,649,659 3,216,936 3,367,943 3,533,945 3,658,836 3,254,025 3,373,111 3,539,633 3,697,574 3,256,185 3,403,102 3,573,010 3,702,757 3,278,550 3,442,808 3,579,450 3,703,536 -3,280,234 3,455,831 3,591,598 3,704,308 3,281,428 3,455,832 3,600,372 3,708,522 (5) Interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, e.g. aminoalkyl acrylates or acrylamides and poly-(oxyethylene)-substituted acrylates. Thes~ may be characterized as "polymeric dispersants" and examples there-of are disclosed in the following U.S. patents:
3,329,658 3,666,730 3,449,250 3,687,849 3,519,565 3,702,300 The above-noted patents disclose ashless dispersants.
Extreme pressure agents and corrosion- and oxida-tion-inhibiting agents are exemplified by chlorinated ali-~"~ ., .
~, , .
:
'1138~1Z
phatic hydrocarbons such as chlorinated wax; organic sul-fides and polysulfides such as benzyl disulfide, bis(chloro-benzyl)disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpene; phosphosulfurized hy-drocarbons 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, 10 dicyclohe~yl phosphite, pentylphenyl phosphite, dipentyl-phenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecular weight 500)-substituted phenyl phosphite, diisobutyl-substituted phenyl phosphite; metal 15 thiocarbamates, such as zinc dioctyldithiocarbamate, and barium heptylphenyl dithiocarbamate; Group II metal phos-phorodithioates such as zinc dicyclohexylphosphorodithioate, zine dioetylphosphorodithioate, barium di(heptylphenyl)-phosphorodithioate, cadmium dinonylphosphorodithioate, and 20 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.
Other additives useful in fuels include deposit preventers or modifiers sueh as triaryl phosphates, ayes, 25 cetane improvers, antioxidants such as 2,6-di-tertiary-butyl-4-methylphenol, rust inhibitors such as alkylated succinic acids and anhydrides, baeteriostatic agents, gum inhibitors, metal deactivators, demulsifiers and the like.
The magnesium complexes of this invention can be 30 added directly to the lubricant or fuel. Preferably, how-ever, they are diluted with a substantially inert, normally liquid organic diluent sueh as those mentioned hereinabove, partieularly mineral oil, naphtha, benzene, toluene or xylene, to form an additive eoneentrate. These coneentrates 35 generally eontain about 20-90~ by weight of the magnesium 113B4~%
complex and may con-tain in addition, one or more of the other additives described hereinabove.
Corrosion-Resistant Coatin~s and Other Uses -The thixo-trop~ magnesium complexes of -this inven-tion, especially those that are viscous or solid at ambient temperatures, are useful as corrosion-resistant coatings for metal (e.g. ferrous metal, galvanized, aluminum or mag-nesium) surfaces, especially in the nature of undercoats for automotive bodies, coatings for structural members such as automotive frames, and the like. They may be employed as such alone or in combination with various adjuvants known to be useful in such coatings, such as other basic metal sul-fonates lof the type disclosed in U.S. Patent 3,453,124), acidic phosphate esters, and waxes and resins as disclosed hereinabove with reference to component D.
For coating automotive frames and the like, a solid "hot melt" composition is suitable. Frequently, a dye or pigment is added to the "hot melt" composition.
For corrosion-inhibiting purposes, the viscoùs or solid composition of this invention may be applied to the metal surface by any ordinary method such as brushing, spraying, dip-coating, flow-coating, roller-coating and the like, with heating if necessary (as to liquefy a solid composition). The viscosity may be adjusted for the par-ticular method of application selected by adding, if neces-sary, a diluent which may be a substantially inert, normally liquid inorganic diluent, an analogous solid, or a mixture of liquids and solids; suitable materials are described herein-above with reference to component D. The coated metal surface may then be dried either by exposure to air or by baking, although drying frequently takes place without a separate drying step. If the coating composition is of a ~384~Z
suitable viscosity to allow direct applieation to the metal surface, no solvent is used and no drying procedure need ke followed. A more viscous grease ean be diluted to produee a less viscous grease which is suitable for application as previously noted. The film thic~ness is not eritieal al-though a eoating of about 50-2000 mg. per square foot of surfaee in the ease of an undereoat, and up to about 10,000 mg. per square foot in the ease of a eoating for frames or other struetural members, is usually suffieient to provide 10 adequate protection. Heavier coatings can be used if desired, but they normally contribute little in the way of additional protection.
The magnesium eomplexes of this invention are also useful as lubrieant greases and as stabilizers for resinous 15 eompositions, typieally polyvinyl ehloride, to proteet them against oxidative degradation.
Triethylene glycol dibenzoate Neopentyl glycol dibenzoate Glyceryl tribenzoate It is also within the scope of the invention to use mixtures of any of the materials described above. Such 15 mixtures may be of materials all of which are liquid at normal ambient temperatures ~e.g., about 20-30C.), such as mineral oil-toluene, Stoddard solvent-toluene, mineral oil-alkylbenzene, Stoddard solvent-alkylbenzene; of materials all of which are solid at normal ambient temperatures, such 20 as paraffin wax-polyethylene wax, paraffin wax-polyethylene wax-C2 0-4 0 alcohol wax; or of materials which are both liquid and solid at normal ambient temperatures, such as mixtures of the above-mentioned normally liquid diluents and a resin or hydrocarbon wax (e.g., paraffin wax-toluene, 25 polypropylene-toluene, polypropylene-mineral oil).
Component Proportions The relative proportions of components A, B, C and D are an important feature o' this invention since the physica~ state in which the magnesium complex is obtained 30 depends to a great extent on the proportions of the com-ponents used for their preparation.
As previously noted, the ratio of equivalents of magnesium to the acid portion of component B is at least 11384~
about 5:1. This ratio is hereinafter sometimes referred to as the "magnesium ratio". tIt will be appreciated that the magnesium ratio is such as to produce a basic magnesium complex.) If component B is a free carboxylic acid or an ester or salt thereof with a metal other than magnesium, the ratio of component A to component B will be identical to the magnesium ratio. If component B is a magnesium salt, the ratio of component A to component B will be somewhat less than the magnesium ratio since part of the magnesium is 10 provided ky component s.
It has been found that magnesium complexes with relatively low maynesium ratios (e.g., from about 5:1 to about 21:1 and particularly from about 5:1 to about 10:1) are particularly useful as lubricant additives. Complexes 15 with a magnesium ratio above about 60:1 and preferably up to about 150:1 find utility principally as additives for fuel oils. As protective coatings for metals, it is preferred to employ complexes in which component D is entirely or pre-dominantly liquid and the magnesium ratio is between about 20 25:1 and about 60:1, or solid te-g., "hot melt") complexes in which component D is entirely or predominantly solid at ambient temperature and which typically have a magnesium ratio from about 5:1 to about 50:1.
The ratio of moles of water (component C) to 25 grams-atoms of magnesium in component A tsaid ratio herein-after sometimes designated the "water ratio") is also critical. ~Jhen component A is substantially all magnesium hydroxide or hydrated magnesium oxide, the prèsence of water is frequently not required. If water is not present, 30 however, complex preparation usually requires extremely efficie~t high-speed mixing te-g-, by mixers such as that sold under the trade ~K~"Dispersator" by Premier Mill Corporation) so as to produce a uniform product. When a substantial portion of component A is magnesium oxide or a 35 magnesium alkoxide, the presence of water as component C is required.
~J~3~1Z
Most often, the use of water is advantageous regardless of the identity of component A. When it is present, the amount of water should be at least sufficient to hydrate a substantial proportion of component A, cal-culated as magnesium oxide. The proportion of additionalwater over and above that amount will depend on the nature of the product desired and the intended use thereof. If component A is anhydrous magnesium oxide the water ratio should generally be at least about 0.7:1 so as to produce a 10 substantial proportion of the hydrated magnesium oxide referred to hereinabove.
A water ratio up to about 3.0:1, and especially from about 0.7:1 to about 3.0:1, is usually adequate to produce a composition of this invention. If larger amounts 15 Of water than this are used, it is frequently possible to remove excess water, at least some of which separates from the magnesium complex as a separate layer and the remainder of which can be removed by azeotropic distillation or the like. More water may be desirable for the preparation of 20 the complex in certain instances; for example, magnesium oxide frequently contains traces of sodium compounds whose presence may be undesirable in the complex, and if so, such compounds may be removed by using up to about 8 moles of water per mole of component A and removing the excess, which 25 has dissolved therein the sodium compounds. When the excess water has been removed, the molar ratio of remaining water to component A is usually below about 3:1 as noted above.
As among various magnesium complexes-with water ratios between about 0.7:1 and about 3.0:1, those having a 30 water ratio below about 1:1 are often particularly useful as lubricant additives or fuel oil additives, while those having a somewhat higher water ratio (e.g., between about 1:1 and 3:1) may be particularly useful in the preparation of corrosion-resistant coating compositions.
The ratio of component D to component A is not critical and may be varied so as to provide magnesium com-1138~1Z
plexes suitable for the particular use for which they are intended. For example, a complex suitable as a lubricant additive may frequently be obtained by employing as com-ponent D solely the unsulfonated alkylbenzene present as an impurity in the sulfonic acid used as component B. In that event, the weight ratio of component D to component A will usually be below about 1:1 and frequently as low as 0.5-0.7:1. In general, when a lubricant additive product is desired it is inaclvisable to use volatile materials as 10 component D.
When the magnesium complex is to be used as a fuel oil additive, higher amounts of component D are frequently preferred and these may include relatively volatile mat-erials such as toluene or xylene, less volatile materials 15 such as mineral oil or mineral seal oil, and mixtures of volatile and less volatile materials. The proportions of volatile and non-volatile solubilizing agents in such mixtures are subject to wide variation, but in any event it is usually found that the total weight ratio of component D
20 to component A should be from about 1.2:1 to about 1.8:1.
When a product useful in a protective metal coat-ing is desired, still higher ratios (e.g., from about 2:1 to about 3:1) are often employed with one of the solubilizing agents being a substantially volatile aliphatic hydrocarbon 25 such as naphtha or StOddard solvent, and the other being a somewhat less volatile material such as mineral oil. Ano-ther useful type of complex for metal coating is the solid (e.g., "hot melt") type briefly referred to hereinabove, in which component D comprises mostly or entirely materials 30 which are solid at ambient temperature, in which case the ratio of D to ~ may be between about 0.5:1 and about 6:1.
Prepara~ion of the Magnesium Complex The magnesium complexes of this invention are pre-pared by merely blending the components described herein-35 above and heating the resulting blend at a temperature above 113~41;~
about 30C. It is important that water (if present as component C) remain in the blend during substantially the entire period of preparation of the magnesium complex, and the maximum temperature thereof should be adjusted accord-ingly. ~lowever, said water may be present in the liquid orvapor state, i.e., as liquid water or as steam, though it will be apparent to those skilled in the art that the preparation of complexes involving a relatively large amount of water will be difficult if not impossible, at least at 10 atmospheric pressure, if the water is present as steam.
Therefore, it is generally found that temperatures between about 30 and about 125C. are most conveniently employed at atmospheric pressure, and the preparation should be carried out under superatmospheric pressure if the use of higher 15 temperatures is likely. Most often, a maximum temperature of about 100C. is convenient when component D is entirely or predominantly liquid and the preferred temperature range is then between about 40 and about 90C. Naturally, the temperature may be somewhat higher (e.g., between about 95 20 and about 150C.) when component D is entirely or predomi-nantly a solid at ambient temperature.
The order of addition of the various components is not critical. It is often convenient to first combine components A, B and D and subsequently to add component C
25 (water) either all at once or incrementally. It is also often found convenient to prepare an initial mixture con-taining only a relatively small portion of component A
(e.g., from about 5% to about 10% of the total`amount thereof) and to add the remainder at a later stage, typi-30 cally during or after the addition of water. Finally, it iswithin the scope of the invention to prepare the magnesium complex using only a portion of the amount of component D
intended, and to add the remainder after the complex has been prepared. The amount subsequently added is generally 35 less than about 50% and preferably less than about 40% by 1138~
weight of the total amount to be used. This subsequent addition of part of component D is most often useful when component D is partly or entirely solid (for example, when it comprises waxes and/or resins) and/or ~hen it imparts additional desirable properties such as modifying fluidity under the conditions of use.
The magnesium complexes of this invention are thixotropic; that is, they decrease in viscosity when agitated and return to approximately their original vis-10 cosity after agitation ceases. When component D is pre-dominantly liquid, the complexes are typically viscous liquids or heterogeneous dispersions in the form of greases or gels. When component D is predominantly solid, the magnesium complex may be a solid,"hot melt" type material.
The solid materials are useful for many purposes, such as for the formation of corrosion-resistant coatings as described hereinafter. For some other applications, such as those involving lubricants and fuels, the complex is pre-ferably obtained in the form of a relatively non-viscous, 20 easily flowable liquid. Such liquids may be obtained by methods well known to those of skill in the art, such as by maximizing the amount of liquid diluent present as component D or by decreasing the relative amount of component A or component C in the reaction mixture. Alternatively, a 30 viscous or solid complex can be further diluted with a substantially inert organic liquid diluent of the type described hereinabove to produce a homogeneous--solution.
One of the unique and desirable characteristics of the thixotropic compositions of this invention is their capa-.
11~8~12 bility of existing either as heterogeneous compositions or homogeneous, relatively dilute solutions or dispersions.
A method which is sometimes advantageous for incorporating relatively large amounts of magnesium while making possible the formation of a homogeneous solution or dispersion in mineral oil or the like is to prepare the complex in the presence of ammonium hydroxide, which may be prepared from ammonia and the water present as component C.
The amount of ammonium hydroxide required is small, gen-10 erally less than a~out 10~ by weight based on the waterpresent. Insoluble materials can then be removed by dilu-ting with a non-polar volatile organic liquid such as hexane or naphtha, centrifuging, and stripping the volatile liquid, or by equivalent means.
Another method for clarifying the magnesium complex for use in mineral oil, which may be employed in addition to or in place of preparation in the presence of ammonium hydroxide, is to add water or an acidic or kasic reagent after preparation of the complex. The acidic or 20 basic reagent may be organic or inorganic; suitable ones include sodium hydroxide, potassium hydroxide, ammonium hydroxide, triethanolamine, tartaric acid and citric acid.
The amount of water or acidic or basic reagent is generally less than about 10% by weight of the magnesium complex ~5 system.
The stability of the magnesium complexes of this invention is often improved if a minor effective amount of an oxidation inhibitor is incorporated therein. Suitable oxidation inhibitors include the hindered phenol type, 30 illustrated by 2,6-di-t-butylphenol and its derivatives; and the arylamine type, illustrated by phenyl-~-naphthylamine.
The amo~r;t of antioxidant required is usually between about 0.1~ and akout 2% and preferahly between about 0.2~ and 1%
by weight. Oxidation inhibitors are particularly useful in 35 the corrosion-resistant coating compositions of this inven-tion since they inhibit viscosity decreases thereof.
The preparation of the magnesium complexes of this invention is illustrated by the following examples. All parts are by weight.
Example 1 A mixture of 754 parts of water, 23 parts of magnesium oxide, 210 parts of mineral oil and 247 parts of Stoddard solvent is heated to about 40C. and 331 parts of a carboxylic acid having an equivalent weight of about 350 and obtained by oxidation of petrolatum, which acid has been preheated to about 50-60C., is added as the temperature of the mixture is maintained at 40-45C. An additional 350 parts of magnesium oxide is added, with stirring, and the temperature of the mixture is increased to 75C. An opaque dispersion is obtained which is screened to afford the desired magnesium oxide-carboxylate complex.
Example 2 A product similar to that of Example 1 is pre-pared, substituting about 300 parts of sorbitan trioleate for the oxidized petrolatum.
Example 3 A mixture of 16 parts of an alkylbenzenesulfonic acid having an equivalent weight of about 430 and containing about 22% unsulfonated alkylbenzene, 305 parts of mineral oil, 180 parts of magnesium oxide and 96 parts of the mixture sold under the trade mark "Hydrex 440", a mixture of hydrogenated fatty acids obtainable from Union Camp Corporation, is heated to 95C. and blown with steam for two hours. The temperature is increased to 145-150C., an additional 28 parts of mineral oil is added and the mixture is blown with air as the temperature is heated to 170C. over 15 minutes. The mixture is then cooled to room temperature and an additional 44 parts of mineral oil is added to yield the desired magnesium oxide-carboxylate-sulfonate complex having the consistency of a grease.
~13~9~1;2 Lubricants and Fuels When in the form of flowable liquids as previously described, the magnesium complexes of this invention are stably dispersible in the normally liquid media (e.g., oil, fuel, etc.) in which they are intended to function. Thus, for example, compositions intended for use in oils are stably dispersible in an oil in which they are to be used.
The term "stably dispersible" as used in the specification and appended claims is intended to mean the magnesium com-10 plex or other material is capable of being dispersed in agiven medium to an extent which allows it to function in its intended manner. Thus, for example, when a magnesium com-plex is used in an oil, it is sufficient that it be capakle of being suspended in the oil in an amount sufficient to 15 enable the oil to possess one or more of the desired pro-perties imparted to it by the suspended complex. Such suspension can be achieved in various conventional ways.
For example, in constantly circulating oil or oil in splash lubricating systems, physical agitation can keep the complex 20 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 magnesium complex. In any event, the complex will be "stably dis-25 persible" in the normally liquid media in which it will be used in at least the minimum concentrations set forth elsewhere herein. Thus, the terminology "stably disper-sible" is used in a conventional manner and will be un-derstood by those of ordinary skill in the art.
As previously indicated, the magnesium complexes of this invention may be homogeneously incorporated into lukrica~ts, in which they function primarily as ash-pro-ducing detergents. They can be employed in a variety of lubricants based on diverse oils of lubricating viscosity, 3S including natural and synthetic lubricating oils and mix-~13Ei 4~2 tures thereof. These lubricants include crankcase lubri-cating oils for spark-ignited and compression-ignited internal combustion engines, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad diesel engines, and the like. They can also be used in gas engines, stationary power engines and turbines and the like. Automatic transmission fluids, transaxle lubricants, gear lubricants, metal-working lubricants, hydraulic fluids and other lubricating oil and grease 10 compositions can also benefit from the incorporation therein of the compositions of the present invention.
Natural oils include animal oils and vegetable oils (e.g , castor oil, lard oil) as well as liquid petro-leum oils and solvent-treated or acid-treated mineral 15 lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and 20 interpolymerized olefins [e.g., polybutylenes, polypro-pylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(l-hexenes), poly(l-octenes), poly(l-decenes), etc. and mixtures thereof]; alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-25 ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls,terphenyls, alkylated polyphenyls, etc.), alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof and the like. ~
Alkylene oxide polymers and interpolymers and 30 derivatives thereof where the terminal hydroxyl groups have ~ -been modified by esterification, etherification, etc. con-stituteranother class of known synthetic lubricating oils.
These are exemplified by the oils prepared through poly-merization of ethylene oxide or propylene oxide, the alkyl 35 and aryl ethers of these polyoxyalkylene polymers (e.g., ~3841Z
methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a ~olecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters, or the C~ 3 OXO acid diester of tetraethylene glycol.
Another suitable class of synthetic lubrieating oils eomprises the esters of diearkoxylie aeids (e.g., 10 phthalie acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic aeid, azelaie aeid, suberie acia, sebacic acid, fumaric acid, adipic aeid, linoleic acid dimer, malonie acid, alkyl malonie aeids, alkenyl malonie aeids, ete.) with a variety of alcohols (e.g., butyl aleohol, 15 hexyl alcohol, dodecyl alcohol, ~-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glyeol, ete.). Speeifie examples of these esters inelude dibutyl adipate, di(2-ethylhexyl) sebaeate, di-n-hexyl fumarate, dioetyl sebaeate, diisooetyl azelate, diisodeeyl 20 azelate, dioetyl phthalate, dideeyl phthalate, dieieosyl sebaeate, the 2-ethylhexyl diester of linoleie aeid dimer, the eomplex ester formed by reaeting one mole of sebaeie aeid with two moles of tetraethylene glyeol and two moles of 2-ethylhexanoie aeid, and the like.
Esters useful as synthetie oils also inelude those made from Cs to Cl 2 monoearboxylie aeids and polyols and polyol ethers sueh neopentyl glyeol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, ete.
Silieon-based oils sueh as the polyalkyl-, poly-30 aryl-, polyalkoxy-, or polyaryloxy-siloxane oils and sili-eate oil-s eomprise another useful elass of synthetie lubri-eants ~e.g., tetraethyl silieate, tetraisopropyl silieate, tetra-(2-ethylhexyl) silieate, tetra-(4-methyl-2-ethylhexyl) silieate, tetra-(p-tert-butylphenyl) silieate, hexa-(4-35 methyl-2-pentoxy)-disiloxane, poly(methyl)-siloxanes, poly(methylphenyl)siloxanes, etc.). other synthetic lubri-cating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid, etc.), polymeric tetrahydrofurans and the like.
Unrefined, refined and rerefined oils (and mix-tures of each with each other) of the type disclosed here-inabove can be used in the lubricant compositions of the present invention. ~nrefined oils are those obtained 10 directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. ~efined oils 15 are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques are known to those of skill in the art such as solvent extraction, acid or base extraction, filtration, percol-20 ation, etc. Rerefined oils are obtained by processessimilar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques 25 directed to removal of spent additives and oil breakdown products.
Generally, the lubricants of the present invention contain an amount of the magnesium complex of~this invention sufficient to impart detergency thereto. Normally this 30 amount will be from about 0.05% to about 20%, preferably from about 0.5% to about 10%, of the total weight of the lubricant. In lubricating oils operated under extremely adverse conditions, such as lubricating oils for marine diesel engines, the magnesium complexes of this invention 35 may be present in amounts up to about 30%.
1138~1Z
-2~-The magnesium complexes of the present invention are also useful as corrosion inhibitors, vanadium scavengers and smoke suppressants in fuels. For that purpose, they are homogeneously incorporated in minor proportions in normally liquid fuels, usually hydrocarbonaceous fuels such as fuel oils, bunker fuels and the like. Normally liquid fuel com-positions comprising non-hydrocarbonaceous materials such as alcohols, ethers, organo-nitro compounds and the like (e.g., methanol, ethanol, diethyl ether, methyl ethyl ether, 10 nitromethane) are also within the scope of the invention as are liquid fuels derived from vegetable or mineral sources such as corn, alfalfa, shale and coal. Normally liquid fuels which are mixtures of one or more hydrocarbonaceous fuels and one or more non-hydrocarkonaceous materials are 15 also contemplated.
Generally, these fuel compositions contain an amount of the magnesium complex sufficient to impart corro-sion resistance thereto, suppress smoke or serve as a vana-dium scavenger; usually this amount is from about l to about 20 10,000, preferably from about 4 to about 1000, parts thereof by weight per million parts of fuel.
The invention also contemplates the use of other additives in combination with the magnesium complexes.
Other additives useful in lubricants include, for example, 25 auxiliary detergents and dispersants of the ash-producing or ashless type, corrosion- and oxidation-inhibiting agents, pour point depressing agents, extreme pressure agents, color stabilizers and anti-foam agents.
The auxiliary ash-producing detergents are exem-30 plified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, or organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage such as those prepared by the treatment of an olefin polymer (e.g., polyisobutene 35 having a molecular weight of 1000) with a phosphorizing lZ
agent such as phosphorus trichloride, phosphorus hepta-sulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphoro-thioic chloride. The most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, strontium and barium.
The term "basic salt" is used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical. The commonly 10 employed methods for preparing the basic salts involve heat-ing a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50C. and filtering the resulting mass.
15 The use of a "promoter" in the neutralization step to aid the incorporation of a large excess of metal likewise is known. Examples of compounds useful as the promoter include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation pro-20 ducts of formaldehyde with a phenolic substance; alcoholssuch as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-~-naphthylamine, and dodecylamine. A
25 particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter, and carbonating the mixture at an elevated tem-perature such as 60-200C.
Ashless detergents and dispersants are so called despite the fact that, depending on its constitution, the dispersânt may upon combustion yield a non-volatile material such as boric oxide or phosphorus pentoxide; however, it does not ordinarily contain metal and therefore does not 35 yield a metal-containing ash on combustion. Many types are known in the art, and any of them are suitable for use in the lubricants of this invention. The following are illus-trative:
(1) Reaction products of carboxylic acids (or derivatives thereof) containing at least about 34 and pre-ferably at least about 54 carbon atoms with nitrogen-con-taining compounds such as amine, organic hydroxy compounds such as phenols and alcohols, and/or basic inorganic mater-ials. Examples of these "carboxylic dispersants" are 10 described in British Patent 1,306,529 and in many U.S.
patents including the following:
3,163,603 3,351,552 3,541,012 3,184,474 3,381,022 3,542,678 3,215,707 3,399,1~1 3,542,680 15 3,219,666 3,415,750 3,567,637 3,271,310 3,433,744 3,574,101 3,272,746 3,444,170 3,576,743 3,281,357 3,448,048 3,630,904 3,306,908 3,448,049 3,632,510 20 3,311,558 3,451,933 3,632,511 3,316,177 3,454,607 3,697,428 3,340,281 3,467,668 3,725,441 3,341,542 3,501,405 Re 26,433 3,346,493 3,522,179 (2) Reaction products of relatively high molecu-lar weight aliphatic or alicyclic halides with amines, pre-ferably polyalkylene polyamines. These may be characterized as "amine dispersants" and examples thereof ar`e described for example, in the following U.S. patents:
3,275,554 3,454,555 3,438,757 3,565,804 (3) Reaction products of alkyl phenols in which the alkyl group contains at least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially 35 polyalkylene polyamines), which may be characterized as 1~3841Z
"Mannich dispersants". The materials described in the following U.S. patents are illustrative:
3,413,347 3,725,480 3,697,574 3,726,882 3,725,277 (4) Products obtained by post-treating the car-boxylic, amine or Mannich dispersants with such reagents as urea, thiourea, carbon disulfide, aldehydes, ketones, car-boxylic acids, hydrocarbon-substituted succinic anhyrides, nitriles, epoxides, boron compounds, phosphorus compounds or the like. Exemplary materials of this kind are described in the following U.S. patents:
3,036,003 3,282,955 3,493,520 3,639,~42 3,087,936 3,312,619 3,502,677 3,649,229 3,200,107 3,366,569 3,513,093 3,649,659 3,216,936 3,367,943 3,533,945 3,658,836 3,254,025 3,373,111 3,539,633 3,697,574 3,256,185 3,403,102 3,573,010 3,702,757 3,278,550 3,442,808 3,579,450 3,703,536 -3,280,234 3,455,831 3,591,598 3,704,308 3,281,428 3,455,832 3,600,372 3,708,522 (5) Interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, e.g. aminoalkyl acrylates or acrylamides and poly-(oxyethylene)-substituted acrylates. Thes~ may be characterized as "polymeric dispersants" and examples there-of are disclosed in the following U.S. patents:
3,329,658 3,666,730 3,449,250 3,687,849 3,519,565 3,702,300 The above-noted patents disclose ashless dispersants.
Extreme pressure agents and corrosion- and oxida-tion-inhibiting agents are exemplified by chlorinated ali-~"~ ., .
~, , .
:
'1138~1Z
phatic hydrocarbons such as chlorinated wax; organic sul-fides and polysulfides such as benzyl disulfide, bis(chloro-benzyl)disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpene; phosphosulfurized hy-drocarbons 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, 10 dicyclohe~yl phosphite, pentylphenyl phosphite, dipentyl-phenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecular weight 500)-substituted phenyl phosphite, diisobutyl-substituted phenyl phosphite; metal 15 thiocarbamates, such as zinc dioctyldithiocarbamate, and barium heptylphenyl dithiocarbamate; Group II metal phos-phorodithioates such as zinc dicyclohexylphosphorodithioate, zine dioetylphosphorodithioate, barium di(heptylphenyl)-phosphorodithioate, cadmium dinonylphosphorodithioate, and 20 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.
Other additives useful in fuels include deposit preventers or modifiers sueh as triaryl phosphates, ayes, 25 cetane improvers, antioxidants such as 2,6-di-tertiary-butyl-4-methylphenol, rust inhibitors such as alkylated succinic acids and anhydrides, baeteriostatic agents, gum inhibitors, metal deactivators, demulsifiers and the like.
The magnesium complexes of this invention can be 30 added directly to the lubricant or fuel. Preferably, how-ever, they are diluted with a substantially inert, normally liquid organic diluent sueh as those mentioned hereinabove, partieularly mineral oil, naphtha, benzene, toluene or xylene, to form an additive eoneentrate. These coneentrates 35 generally eontain about 20-90~ by weight of the magnesium 113B4~%
complex and may con-tain in addition, one or more of the other additives described hereinabove.
Corrosion-Resistant Coatin~s and Other Uses -The thixo-trop~ magnesium complexes of -this inven-tion, especially those that are viscous or solid at ambient temperatures, are useful as corrosion-resistant coatings for metal (e.g. ferrous metal, galvanized, aluminum or mag-nesium) surfaces, especially in the nature of undercoats for automotive bodies, coatings for structural members such as automotive frames, and the like. They may be employed as such alone or in combination with various adjuvants known to be useful in such coatings, such as other basic metal sul-fonates lof the type disclosed in U.S. Patent 3,453,124), acidic phosphate esters, and waxes and resins as disclosed hereinabove with reference to component D.
For coating automotive frames and the like, a solid "hot melt" composition is suitable. Frequently, a dye or pigment is added to the "hot melt" composition.
For corrosion-inhibiting purposes, the viscoùs or solid composition of this invention may be applied to the metal surface by any ordinary method such as brushing, spraying, dip-coating, flow-coating, roller-coating and the like, with heating if necessary (as to liquefy a solid composition). The viscosity may be adjusted for the par-ticular method of application selected by adding, if neces-sary, a diluent which may be a substantially inert, normally liquid inorganic diluent, an analogous solid, or a mixture of liquids and solids; suitable materials are described herein-above with reference to component D. The coated metal surface may then be dried either by exposure to air or by baking, although drying frequently takes place without a separate drying step. If the coating composition is of a ~384~Z
suitable viscosity to allow direct applieation to the metal surface, no solvent is used and no drying procedure need ke followed. A more viscous grease ean be diluted to produee a less viscous grease which is suitable for application as previously noted. The film thic~ness is not eritieal al-though a eoating of about 50-2000 mg. per square foot of surfaee in the ease of an undereoat, and up to about 10,000 mg. per square foot in the ease of a eoating for frames or other struetural members, is usually suffieient to provide 10 adequate protection. Heavier coatings can be used if desired, but they normally contribute little in the way of additional protection.
The magnesium eomplexes of this invention are also useful as lubrieant greases and as stabilizers for resinous 15 eompositions, typieally polyvinyl ehloride, to proteet them against oxidative degradation.
Claims (25)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for preparing a thixotropic non-carbonated magnesium-containing complex which comprises heating, at a temperature above about 30°C., a mixture comprising:
(A) At least one of magnesium hydroxide, mag-nesium oxide, hydrated magnesium oxide, and a magnesium alkoxide;
(B) At least one oleophilic organic reagent comprising a carboxylic acid, a mixture of a major amount thereof with a minor amount of a sulfonic acid or pentavalent phosphorus acid, or an ester or alkali metal or alkaline earth metal salt of either of these;
(C) Water, if necessary to convert a substantial proportion of component A to magnesium hydroxide or hydrated magnesium oxide; and (D) At least one organic solubilizing agent for component B;
the ratio of equivalents of magnesium to the acid portion of component B being at least about 5:1, and the amount of water present, if any, being at least sufficient to hydrate a substantial proportion of component A calcu-lated as magnesium oxide.
(A) At least one of magnesium hydroxide, mag-nesium oxide, hydrated magnesium oxide, and a magnesium alkoxide;
(B) At least one oleophilic organic reagent comprising a carboxylic acid, a mixture of a major amount thereof with a minor amount of a sulfonic acid or pentavalent phosphorus acid, or an ester or alkali metal or alkaline earth metal salt of either of these;
(C) Water, if necessary to convert a substantial proportion of component A to magnesium hydroxide or hydrated magnesium oxide; and (D) At least one organic solubilizing agent for component B;
the ratio of equivalents of magnesium to the acid portion of component B being at least about 5:1, and the amount of water present, if any, being at least sufficient to hydrate a substantial proportion of component A calcu-lated as magnesium oxide.
2. A method according to claim 1 wherein com-ponent D is at least one substantially inert, normally liquid organic diluent.
3. A method according to claim 2 wherein com-ponent B is a mixture of at least one alkylbenzenesulfonic acid and at least one carboxylic acid containing from about 8 to about 30 carbon atoms.
4. A method according to claim 1 wherein com-ponent D is at least one substantially inert organic material which is solid at ambient temperature.
5. A method according to claim 4 wherein component B
is a mixture of at least one alkylbenzenesulfonic acid and at least one carboxylic acid containing from about 8 to about 30 carbon atoms.
is a mixture of at least one alkylbenzenesulfonic acid and at least one carboxylic acid containing from about 8 to about 30 carbon atoms.
6. A method according to claim 1 wherein component D is a mixture of at least one substantially inert organic material which is solid at ambient temperature with at least one substan-tially inert, normally liquid inorganic diluent.
7. A method according to claim 6 wherein component B is a mixture of at least one alkylbenzenesulfonic acid and at least one carboxylic acid containing from about 8 to about 30 carbon atoms.
8. A thixotropic complex prepared by the method of claim 2.
9. An additive concentrate comprising a substantially inert, normally liquid organic diluent and a complex according to claim 8.
10. A composition comprising a major amount of a lubricating oil and a minor amount of a complex according to claim 8.
11. A composition comprising a major amount of a normally liquid fuel and a minor amount of a complex according to claim 8.
12. A thixotropic complex prepared by the method of claim 4.
13. A complex according to claim 12 which is solid at ambient temperature.
14. A composition comprising a complex according to claim 12 to which a portion of component D has been added after preparation thereof.
15. A composition comprising a complex according to claim 13 to which a portion of component D has been added after preparation thereof.
16. A composition comprising a complex according to claim 12 and a minor effective amount of an oxidation inhibitor.
17. A composition comprising a complex according to claim 13 and a minor effective amount of an oxidation inhibitor.
18. A composition comprising a complex according to claim 14 and a minor effective amount of an oxidation inhibitor.
19. A composition comprising a complex according to claim 15 and a minor effective amount of an oxidation inhibitor.
20. An article of manufacture comprising a metal object coated with a thixotropic non-carbonated magnesium-containing complex prepared by heating, at a temperature above about 30°C., a mixture comprising:
(A) At least one of magnesium hydroxide, mag-nesium oxide, hydrated magnesium oxide, and a magnesium alkoxide;
(B) At least one oleophilic organic reagent com-prising a carboxylic acid, a mixture of a major amount thereof with a minor amount of a sulfonic acid or pentavalent phosphorus acid, or an ester or alkali metal or alkaline earth metal salt of either of these;
(C) Water, if necessary to convert a substantial proportion of component A to magnesium hydroxide or hydrated magnesium oxide; and (D) At least one organic solubilizing agent for component B;
the ratio of equivalents of magnesium to the acid portion of component B being at least about 5:1, and the amount of water present, if any, being at least sufficient to hydrate a substantial proportion of component A calcu-lated as magnesium oxide.
(A) At least one of magnesium hydroxide, mag-nesium oxide, hydrated magnesium oxide, and a magnesium alkoxide;
(B) At least one oleophilic organic reagent com-prising a carboxylic acid, a mixture of a major amount thereof with a minor amount of a sulfonic acid or pentavalent phosphorus acid, or an ester or alkali metal or alkaline earth metal salt of either of these;
(C) Water, if necessary to convert a substantial proportion of component A to magnesium hydroxide or hydrated magnesium oxide; and (D) At least one organic solubilizing agent for component B;
the ratio of equivalents of magnesium to the acid portion of component B being at least about 5:1, and the amount of water present, if any, being at least sufficient to hydrate a substantial proportion of component A calcu-lated as magnesium oxide.
21. An article according to claim 20 wherein component D is at least one substantially inert organic material which is solid at ambient temperature.
22. An article according to claim 20 wherein component D is a mixture of at least one substantially inert organic material which is solid at ambient temperature with at least one substantially inert, normally liquid organic diluent.
23. An article according to claim 20 wherein component B is a mixture of at least one alkylbenzenesulfonic acid and at least one carboxylic acid containing from about 8 to about 30 carbon atoms.
24. An article according to claim 23 wherein component C is present in a ratio of moles thereof to gram-atoms of magnesium in component A of at least about 0.7:1.
25. An article according to claim 24 wherein component A is magnesium oxide.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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CA000337842A CA1138412A (en) | 1979-10-17 | 1979-10-17 | Magnesium oxide-carboxylate complexes, method for their preparation, and compositions containing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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CA000337842A CA1138412A (en) | 1979-10-17 | 1979-10-17 | Magnesium oxide-carboxylate complexes, method for their preparation, and compositions containing the same |
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CA1138412A true CA1138412A (en) | 1982-12-28 |
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CA000337842A Expired CA1138412A (en) | 1979-10-17 | 1979-10-17 | Magnesium oxide-carboxylate complexes, method for their preparation, and compositions containing the same |
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CA (1) | CA1138412A (en) |
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1979
- 1979-10-17 CA CA000337842A patent/CA1138412A/en not_active Expired
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