GB2064547A

GB2064547A - Salts and Complexes of Alkylated Aminophenols

Info

Publication number: GB2064547A
Application number: GB8036238A
Authority: GB
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1979-11-19
Filing date: 1980-11-12
Publication date: 1981-06-17
Also published as: JPS5684796A; IN154056B; ES496979A0; ES8204409A1; FR2470155A1; ZA807160B

Abstract

Metal or metalloid salts and complexes of alkylated hydroxy- and amino-substituted phenols are useful as additives for lubricants and fuels. The alkyl group in such salts and complexes contains at least 30 aliphatic carbon atoms. Typical products are made by subjecting a polyisobutene/phenol reaction product to nitration, then reduction, then reaction with a compound of B, Li, Mg, Ca, Ba, Zn, Al, Cu or Cr. Overbased salts may be prepared, and reaction products with formaldehyde are also described.

Description

SPECIFICATION Alkylated Aminophenols This invention relates to compositions which may be used as additives for lubricants and fuels; the term "composition" as used herein includes a single compound. In its most general sense, the invention comprises metal and metalloid salts and complexes of at least one aminophenol of the formula

wherein Ar is an aromatic radical having no sulfur or amino linkages between aromatic nuclei thereof; R is a substantially saturated hydrocarbon-based radical having at least 30 aliphatic carbon atoms; and each of a, b and c is an integer from 1 to three times the number of aromatic nuclei in Ar.

In the above formula, Ar is an aromatic radical which may be mononuclear or polynuclear and which may or may not contain hetero atoms such as oxygen, nitrogen or sulfur. Mononuclear aromatic compounds from which Ar may be derived include benzene, pyridine, thiophene, furan and the like.

Polynuclear compounds may be of the fused ring type such as naphthalene, anthracene, phenanthrene, indole and carbazole. They may also be of the linked ring type provided the linkages do not contain sulfur or amino nitrogen atoms; illustrations of suitable linked ring polynuclear compounds are biphenyl, diphenyl ether, benzophenone and diphenylmethane. Other suitable Ar radicals are derived from polynuclear compounds containing more than one bridge between the nuclei (e.g., fluorene). The preferred Ar radicals, however, are the mononuclear ones and especially the carbocyclic mononuclear ones. Most preferred are compounds in which Ar is a phenyl-based radical (as defined hereinafter) and especially a phenyl radical.

The radical R is a substantially saturated hydrocarbon-based radical having at least 30 aliphatic carbon atoms. As used herein, the term "hydrocarbon-based radical" denotes a radical having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character within the context of this invention. Such radicals include the following: (1) Hydrocarbon radicals; that is, aliphatic (e.g., alkyl or alkenyl) and aromatic- or alicyclicsubstituted aliphatic radicals.

(2) Substituted hydrocarbon radicals; that is, radicals containing non-hydrocarbon substituents which, in the context of this invention, do not alter the predominantly hydrocarbon character of the radical. Those skilled in the art will be aware of suitable substituents (e.g., hydroxy, halo, carbalkoxy, nitro, sulfonic acid ester).

(3) Hetero radicals; that is, radicals which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for example, nitrogen, oxygen and sulfur.

In general, no more than about three substituents or hetero atoms, and preferably no more than one, will be present for each 10 carbon atoms in the hydrocarbon-based radical.

The term "phenyl-based radical" has a meaning analogous to the above with respect to the phenyl radical.

The R radical may contain up to about 750 (preferably from about 40 to about 500) aliphatic carbon atoms. Many suitable R radicals are derived from polymers of monoolefins and/or diolefins containing 2~10 carbon atoms, such as ethylene, propylene, 1 -butene, isobutene, butadiene and the like. Polymers of 1 -monoolefins, and especially of butene mixtures comprising predominantly isobutene, are preferred. The R radical can also be derived from a halogenated (usually chlorinated or brominated and especially chlorinated) polymer of this type. Other suitable sources of the R radical are monomeric high molecular weight alkenes such as 1 -tetracontene and chlorinated derivatives thereof, aliphatic petroleum fractions such as paraffin waxes, white oils, and the like.

The R radicals are substantially aliphatic; that is, they contain no more than one non-aliphatic (e.g., aromatic or alicyclic) substituent of 6 or less carbon atoms for every 10 aliphatic carbon atoms.

Preferably they contain no more than one such non-aliphatic group for every 50 carbon atoms, and in most cases they contain no non-aliphatic groups at all; that is, R is typically aliphatic. It is also substantially saturated; that is, it contains no more than one carbon-to-carbon double bond for every 10 carbon-to-carbon single bonds. The most preferred R radicals are alkyl and monoalkenyl radicals.

As will be apparent from the above formula, the aminophenols from which the compositions of this invention are derived contain at least one each of the R, hydroxy and amino groups. They may contain more than one of any or all of these groups, the upper limit being a situation in which each of the subscripts a, b and c is equal to 3 times the number of aromatic nuclei in Ar. Usually, however, each of a and c is 1 and b is 1 or 2, most often also 1. Thus, the preferred aminophenols are those derived from a monoalkylated mononuclear aminophenol. In such compounds, R may be ortho, meta or para to the hydroxy group but is usually para.

The word "metal" is used herein in its commonly understood physical and chemical sense, and refers to elements having the physical and chemical properties of metals. The word "metalloid" refers to elements having properties intermediate between metals and non-metals and includes such elements as boron and silicon. The compositions included within the scope of the present invention include salts and complexes of metals and metalloids. Most of the metal-containing compositions are most accurately described as salts, while those containing metalloids are for the most part more accurately described as complexes. In some cases, however, the compositions may have some characteristics of a salt and some of a complex and their precise chemical nature in this respect is considered immaterial.

The preferred metals and metalloids in the compositions of this invention are the Group IA, IIA and lIB metals, iron, cobalt, nickel, manganese, silicon, boron, aluminum, chromium, tin, molybdenum, tungsten, antimony, lead, copper and bismuth. Especially preferred are the Group IA, IIA and 118 metals and more especially sodium, potassium, magnesium, calcium, barium and zinc.

The metal salts of this invention may be conveniently prepared by the reaction of the aminophenol with a reactive metal or reactive metal compound. Suitable aminophenols may be prepared by nitrating a corresponding hydroxyaromatic compound and reducing the nitro group to an amino group. The nitration reaction is known in the art and suitable reducing agents for aromatic nitro compounds are also known; the latter include hydrazine, carbon monoxide and hydrogen, frequently used in the presence of metallic catalysts such as palladium, platinum and its oxides, nickel or copper chromite, Suitable methods for the preparation of such aminophenols are disclosed in U.S. Patent 4,100,082, which is incorporated by reference herein for its description of such methods.

Illustrative reactive metal compounds which may be reacted with the above-described aminophenols to produce salts of this invention include lithium oxide, lithium hydroxide, lithium carbonate, lithium pentyloxide, sodium oxide, sodium hydroxide, sodium carbonate, sodium methoxide, sodium propoxide, potassium oxide, potassium hydroxide, potassium carbonate, potassium methoxide, magnesium oxide, magnesium hydroxide, magnesium carbonat,e magnesium methoxide, magnesium propoxide, magnesium salt of ethylene glycol monomethyl ether, calcium oxide, calcium hydroxide, calcium carbonate, calcium methoxide, calcium propoxide, calcium pentyloxide, zinc oxide, zinc hydroxide, zinc carbonate, zinc propoxide, strontium oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, cadmium carbonate, cadmium ethoxide, barium oxide, barium hydroxide, barium carbonate, barium ethoxide, barium pentyloxide, aluminum oxide, aluminum isopropoxide, cupric acetate, lead oxide, lead hydroxide, lead carbonate, tin oxide, tin butoxide, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt pentyloxide, nickel oxide, nickel hydroxide, nickel chloride, nickel carbonate and chromium (II) acetate.

The salts of this invention may be acidic, neutral or basic salts. By "acidic salt" is meant a compound in which less than all of the phenolic hydroxy groups have been converted to salt groups.

Thus, an acidic salt may contain one free hydroxy group and one oxy-metal group in its molecular structure. Such a salt may be illustrated by the formula

wherein M is one equivalent of a metal ion and R is as previously defined. A divalent metal salt can result from the reaction, for example, of two moles of a diphenol with one mole of a compound of a divalent metal (e.g., calcium, barium, zinc or lead). The acidic salts are ordinarily prepared from a reaction mixture containing less than one and usually more than one-half equivalent of metal compound per equivalent of aminophenol.

The term "neutral salt" means a compound in which all phenolic hydroxy groups have been converted to salt groups. Neutral salts can be prepared from the reaction of one equivalent of the aminophenol with one equivalent (or very slightly more, such as 1.1 equivalent) of the metal compound.

The reaction between the alkylated aminophenol and the reactive metal compound is usually effected between room temperature and the decomposition temperature of the reaction mixture, preferably between about 300 and about 1 500C. It is frequently preferred to conduct the reaction in a substantially inert, normally liquid organic diluent such as toluene, mineral oil, ethanol, isooctyl alcohol or the like in order to facilitate contact between the metal compound and the alkylated aminophenol.

After formation of the salt, volatile materials may be removed by distillation if desired and the product, which may be recovered in the form of a solution in a non-volatile diluent such as mineral oil, may be subjected to known operations such as filtration.

In some instances, more than the stoichiometric amount of metal may react with the aminophenol to form a basic salt. A "basic salt", therefore, is one in which the metal is present in amounts stoichiometrically in excess of the phenolic hydroxy groups. Such basic salts are characterized by a metal ratio substantially greater than 1. The term "metal ratio" as used herein is the ratio of the total equivalents of metal in the salt to the equivalents of organic anion therein. Thus, it is a measure of the stoichiometric excess of metal in a metal salt of an organic acidic compound. For example, a basic salt can be obtained by the reaction (under conditions similar to those described above with reference to acidic and neutral salts) of one equivalent of an aminophenol with two equivalents of a metal compound; such a salt would have a metal ratio of 2.

In preparing basic metal salts, it is sometimes advantageous to treat the reaction mixture, in the presence of a promoter, with an acidic gas such as carbon dioxide at a temperature within the range of from about 200C. to the reflux temperature of the mixture. This carbonation step is known in prior art.

Suitable promoters include lower alcohols, e.g., methanol or propanol, and phenolic compounds, e.g., heptylphenol or octylphenol. For example, a basic calcium salt having a metal ratio higher than 1 can be prepared by reacting one equivalent of an aminophenol with more than one equivalent of calcium hydroxide and carbonating the mixture in the presence of methanol. The carbonation step is not abr 'cutely necessary in preparing basic salts but it is beneficial in that it allows the incorporation of significantly more metal into the product and also may have a clarifying effect on both the process mixture and the product.

The carbon dioxide treatment is conducted in such a manner as to reduce substantially the titratable basicity of the reaction mass. There are essentially two materials in the reaction mass prior to carbonation which are susceptible to reaction with carbon dioxide; the free basic metal compound (that which is in excess of the stoichiometric quantity required to form the normal metal salt) and the normal metal salt. It is possible that each of these materials reacts with the carbon dioxide simultaneously, but it is more likely that the excess basic metal compound is carbonated first and the normal metal salt is subsequently carbonated.

The metal salts of this invention can also be prepared by double decomposition; for example, an aminophenol can be reacted with a basic alkali metal compound and the resulting alkali metal phenate can then be reacted with a metal halide (e.g., zinc chloride) to give the desired metal salt.

Metalloid complexes according to this invention are conveniently prepared by the reaction of a reactive metalloid compound such as boric acid or tetraethyl silicate with the alkylated aminophenol at a temperature between room temperature and the decomposition temperature of a reaction mixture and typically between about 500 C. and about 2250C. Alternatively, the metalloid compound may be reacted with the alkylated nitrophenol and the resulting product reduced to the aminophenol complex as previously described.

In an alternative method for preparing the compositions of this invention, an alkylated nitrophenol is reacted with a reactive metal or metalloid compound and a reducing agent other than elemental sulfur, usually one of the reducing agents described hereinabove. The two reactions may be carried out simultaneously or reduction may follow formation of the nitrophenol salt. In other respects, the procedures may be substantially the same as the ones described hereinabove for the formation of the aminophenol salt and the reduction of the free nitrophenol, respectively.

Also within the scope of the invention are compositions prepared by reacting the abovedescribed metal or metalloid salts or complexes with a formaldehyde-producing reagent such as formaldehyde, aqueous formaldehyde solutions, paraformaldehyde or trioxane. The reaction with the formaldehyde-producing reagent is typically effected between about 650 and about 1 500C. and may involve between about 0.5 and about 2.0 equivalents of formaldehyde per equivalent of salt or complex. (For this purpose, the equivalent weight of formaldehyde is equal to its molecular weight and that of the salt or complex is its molecular weight divided by the number of aromatic nuclei therein).

The precise molecular structure of the salts and complexes of this invention is not known with certainty. It is possible that some of the metal salts (for example) are simple phenates, while others may involve chelation with the amino group. The details of molecular structure are not believed critical to the invention.

The preparation of the salts and complexes of this invention is illustrated by the following examples. All parts are by weight unless otherwise indicated.

Example 1 An alkyl phenol is prepared by reacting, in the presence of a boron trifluoride-phenol complex, phenol with a polybutene having a number average molecular weight (as determined by vapor phase osmometry) of about 1000 and comprising principally isobutene units. To a solution of 609 parts of this alkyl phenol in 450 parts of mineral oil is added at about 58-630C., over 8 hours, 46.5 parts of nitric acid. The mixture is stirred for 1-1/2 hours at the same temperature and then heated to 1 420C.

and blown with nitrogen for about 1-1/2 hours. It is subsequently heated at 143--1450C. for 1/2 hour as volatiles are removed by distillation. The residual product is filtered to yield an oil solution of an alkylated nitrophenol.

Hydrazine (64%), 12 parts, is added over 6-1/4 hours at 1 600C. to 320 parts of the alkylated nitrophenol solution. The product is filtered to yield an oil solution of an alkylated aminophenol.

To 1863 grams of the alkylated aminophenol solution are added 29.1 grams (an equivalent amount) of lithium hydroxide monohydrate and 150 ml. of isopropyl alcohol. The mixture is heated under reflux and stirred for 2 hours and is then vacuum stripped at about 1 600 C. to remove volatiles.

The residue is filtered to yield an oil solution of the desired lithium salt of the alkylated aminophenol.

The product contains 1.97% lithium.

Example 2 A solution of 18.4 parts of nitric acid in 35 parts of water is added slowly to a solution of 265 parts of the alkyl phenol of Example 1. 1 76 parts of mineral oil and 42 parts of petroleum naphtha having a boiling point of about 200C. The mixture is stirred for 3 hours at about 30-450C. and is then vacuum stripped to yield an oil solution of an alkylated nitrophenol.

A mixture of 1500 parts of the alkylated nitrophenol solution, 642 parts of isopropyl alcohol and 7.5 parts of a nickel on kieselguhr catalyst is purged with nitrogen and hydrogenated at 100 psig. for 14.5 hours. It is then again purged with nitrogen, filtered and vacuum stripped to yield a mineral oil solution of an alkylated aminophenol.

A magnesium salt solution is prepared by dissolving 324 parts of magnesium in 6000 parts of ethylene glycol monomethyl ether. A solution of 336 parts of the alkylated aminophenol solution in 150 parts of toluene is prepared and 11 5 parts of the magnesium salt is added over 3 minutes at 56 62 OC. The mixture is heated with stirring at 55-700C. for about 2 hours; 2 parts of water is then added and heating is continued at 1 120C. (the reflux temperature) for about 3-3/4 hours. The mixture is then blown with carbon dioxide for 2-1/2 hours at 63-650C. and vacuum stripped. Upon filtration at 1 550C., there is obtained an oil solution of the desired basic magnesium salt of the alkylated aminophenol; it contains 8.85% magnesium sulfate ash.

Example 3 Magnesium methoxide is prepared by dissolving 13.8 parts of magnesium in 1000 parts of methanol. The product is blown with carbon dioxide until the reaction ceases, and 1100 parts of the alkylated aminophenol solution of Example 1 is added over 6 minutes. The mixture is heated to 900 C.

while being blown with nitrogen; 300 parts of isooctyl alcohol is added and heating is continued to 1 500C. The mixture is then blown with steam for about 20 minutes, vacuum stripped and filtered while hot. The filtrate is an oil solution of the desired basic magnesium salt. It contains 6.27% magnesium sulfate ash.

Example 4 To a mixture of 1555 parts of an alkylated nitrophenol solution prepared as described in Example 1,175 parts of a mixture of isobutyl and amyl alcohols, and 75 parts of water is added at 550C., with stirring, 31 parts of calcium hydroxide. The mixture is heated under reflux for 3 hours and is then stripped of volatiles at 125-1 600C., with the final stripping operation being under vacuum. The residue is filtered to yield an oil solution of a calcium salt of the alkylated nitrophenol.

To 85 parts of the above-described calcium salt is added 45 parts of isopropyl alcohol and 50 parts of toluene. Catalytic platinum, 0.04 part, is added and the solution is pressurized with 35-55 pounds of hydrogen and shaken for about 7 hours. The hydrogenated mixture is filtered and the filtrate is vacuum stripped; the residue is finally filtered to yield an oil solution of the desired basic calcium salt of the alkylated aminophenol. It contains 3.28% calcium sulfate ash.

Example 5 An alkyl phenol is prepared substantially as described in Example 1 by reacting phenol with a polybutene having a number average molecular weight of about 600 (as determined by gel permeation chromatography) and comprising principally isobutene units. To a mixture of 2420 parts of this alkyl phenol and 900 parts of textile spirits is added over 2 hours with stirring, at 3O-350C., a solution of 270 parts of nitric acid in 300 parts of water. The mixture is stirred at 300 C. for 3-1/2 hours and is then vacuum stripped to yield an alkylated nitrophenol.

To a mixture of 625 parts of the alkylated nitrophenol, 105 parts of toluene, 70 parts of methanol and 280 parts of mineral oil is added at 350C., with stirring, 91 parts of calcium hydroxide. The mixture is blown with carbon dioxide at 51-560C. for about 50 minutes, vacuum stripped and filtered to yield a carbonated basic calcium salt of the nitrophenol.

Platinum oxide, 0.4 part, is added to a mixture of 120 parts of the basic calcium salt of the alkylated nitrophenol, 50 parts of isopropyl alcohol and 40 parts of toluene. The mixture is pressurized with 46 parts of hydrogen, heated to 50 C. and shaken for about 3-1/2 hours. It is then filtered, stripped under vacuum and filtered again to yield an oil solution of the basic carbonated calcium salt of the alkylated aminophenol. The product contains 3.91% calcium sulfate ash.

Example 6 A mixture of 1090 parts of an alkylated aminophenol solution prepared as described in Example 2 and 21 parts of calcium hydroxide is heated at 7O0C., with stirring, for 10 minutes. Paraformaldehyde (37% aqueous solution), 61 parts, is then added and the mixture is heated under reflux for 1 hour, after which volatile materials are removed by blowing with nitrogen at 1 550C. Upon filtration, there is obtained the desired oil solution of a formaldehyde-bridged calcium salt of the alkylated aminophenol.

It contains 2.5% calcium sulfate ash.

Example 7 A mixture of 306 grams of an alkylated aminophenol solution prepared as described in Example 2, 10 grams of barium oxide and 25 ml. of methanol is heated under reflux for 4 hours, after which volatiles are removed by distillation followed by vacuum stripping. Upon filtration, there is obtained an oil solution of the desired barium salt; it contains 5.59% barium sulfate ash.

Example 8 To a mixture of 500 grams of an alkylated aminophenol solution prepared in accordance with Example 2 and 60 ml. of methanol is added portionwise at 500C., with vigorous stirring, 61 grams of barium oxide. The mixture is heated under reflux for 1-1/2 hours, after which volatiles are removed by vacuum stripping. Upon filtration, there is obtained an oil solution of the desired basic barium salt of the alkylated aminophenol. It contains 6.8% barium sulfate ash.

Example 9 A mixture of 706 grams of an alkylated aminophenol solution prepared in accordance with Example 1 and 70 ml. of methanol is heated to 500 C. and 98 grams of barium oxide is added slowly.

The mixture is heated under reflux for 2 hours, after which volatiles are removed by vacuum stripping.

Toluene, 700 ml., is added and the mixture is filtered, after which the toluene is removed by vacuum stripping. The product is the desired oil solution of a basic barium salt of the alkylated aminophenol. It contains 8.29% barium sulfate ash.

Example 10 A mixture of 222 parts of an alkylated aminophenol solution prepared in accordance with Example 1 and 10 parts of cupric acetate monohydrate is heated for 12 hours at 100-1 600 C., after which any volatile materials are removed by vacuum stripping. The residue is filtered to yield an oil solution of the desired copper salt containing 2.45% copper.

Example 11 A mixture of 222 parts of an alkylated aminophenol solution prepared in accordance with Example 1 and 12.3 parts of chromium (íí) acetate monohydrate is heated at 100--1600C. for 12 hours and then vacuum stripped. The residue is filtered to yield the desired oil solution of a chromium salt which contains 0.035% chromium.

Example 12 A mixture of 512 parts of an alkylated aminophenol solution prepared according to Example 2, 1 6 parts of zinc oxide and 100 parts of ethanol is heated under reflux for 3 hours and then to 1400 C. as volatile materials are removed by distillation. It is finally vacuum stripped and filtered to yield an oil solution of the desired zinc salt of the aminophenol which contains 0.1 8% zinc.

Example 13 To 658 parts of an alkylated aminophenol solution prepared according to Example 1 is added over 10 minutes at 600 C., under nitrogen, 24 parts of a 50% sodium hydroxide solution. The mixture is stirred for 1 hour at 600C. and then 36 parts of nickel (II) chloride hexahydrate is added over 10 minutes, with stirring. The mixture is stirred for 3 hours at 800C. and then is blown with nitrogen and vacuum stripped to remove volatiles. Upon filtration, there is obtained an oil solution of the desired nickel salt containing 1.21% nickel.

Example 14 A mixture of 1 233 parts of the alkylated aminophenol solution of Example 1 and 20.4 parts of boric acid is heated to 1 800 C. and blown with nitrogen for 2 hours. Upon vacuum stripping and filtration, there is obtained the desired boron-containing complex of the alkylated aminophenol which contains 0.26% boron.

Example 15 A product similar to that of Example 14 is prepared from 1486 parts of the alkylated aminophenol solution and 443 parts of boric acid. It contains 4.35% boron.

Example 16 A mixture of 1405 parts of the alkylated aminophenol solution of Example 1 and 76.2 parts of aluminum isopropoxide is heated for 3 hours at 1 55-1 950C. as volatiles are removed by distillation. It is then vacuum stripped and filtered to yield the desired product containing 0.72% aluminum.

The compositions of this invention are useful as additives for lubricants and fuels, in which they function primarily as detergents and dispersants for suspending and removing deposits, sludge and the like. They can be employed in a variety of lubricants based on diverse oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof. These lubricants include crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, including automobile and truck engines, two-cycle engines (in which the compositions are particularly useful), 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 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 petroleum oils and solvent-treated or acid-treated mineral 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 interpolymerized olefins [e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers, chlorinated polybutylenes, poly( 1 -hexenes), poly( 1 -octenes), poly( 1 -decenes), etc. and mixtures thereof ] alkylbenzenes [e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-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 derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methylpolyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1 500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters, or the C13 Oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid alkyl malonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.).

Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like.

Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another useful class of synthetic lubricants [e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-rnethyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-pentoxy)-disiloxane, poly(methyl)-siloxanes, poly(methylphenyl)siloxanes, etc. ] . Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decyiphosphonic acid, etc.), polymeric tetrahydrofurans and the like.

Unrefined, refined and rerefined oils (and mixtures of each with each other) of the type disclosed hereinabove can be used in the lubricant compositions of the present invention. Unrefined oils are those obtained 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 distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils 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, percolation, etc. Rerefined oils are obtained by processes similar 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 directed to removal of spent additives and oil breakdown products.

Generally, the lubricants of the present invention contain an amount of the composition of this invention sufficient to provide detergent and/or dispersant properties. Normally this amount will be about 0.01 to about 20%, preferably about 0.1 to about 5%, of the total weight of the lubricant.

The invention also contemplates the use of other additives in combination with the compositions of this invention. Such additives include, for example, auxiliary detergents and dispersants of the ashproducing or ashless type, corrosion- and oxidation-inhibiting agents, pour point depressing agents, extreme pressure agents, color stabilizers and anti-foam agents.

The ash-producing detergents are exemplified 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 having a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichioride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride. The most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, strontium and barium.

Auxiliary ashless detergents and dispersants are so called despite the fact that, depending on its constitution, the dispersant 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 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 illustrative: (1) Reaction products of carboxylic acids (or derivatives thereof) containing at least about 34 and preferably at least about 54 carbon atoms with nitrogen-containing compounds such as amine, organic hydroxy compounds such as phenols and alcohols, and/or basic inorganic materials.Examples of these carboxylic dispersants" are 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 3,399,141 3,542,680 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 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 molecular weight aliphatic or alicyclic halides with amines, preferably polyalkylene polyamines.These may be characterized as "amine dispersants" and examples thereof are 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 polyalkylene polyamines), which may be characterized as "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 carboxylic, amine or Mannich dispersants with such reagents as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbonsubstituted succinic anhydrides, 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 3,639,242 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.These may be characterized as "polymeric dispersants" and examples thereof 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 are incorporated by reference herein for their disclosures of ashless dispersants.

Extreme pressure agents and corrosion- and oxidation-inhibiting agents are exemplified by chlorinated aliphatic hydrocarbons such as chlorinated wax; organic sulfides and polysulfides such as benzyl disulfide, bis(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpene; phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate; phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite.

diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecular weight 500)-substituted phenyl phosphite, diisobutyl-substituted phenyl phosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate, and barium heptyiphenyl dithiocarbamate; Group II metal phosphorodithioates such as zinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, barium di(heptylphenyl)-phosphorodithioate, cadmium dinonylphosphorodithioate, and 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.

Illustrative lubricants of this invention are listed in the following table. All proportions except those for mineral oil and the products of the examples herein are exclusive of mineral oil used as diluent.

Parts by weight Ingredient Lubricant A B C D E F Mineral oil 92.38 96.23 96.00 92.38 96.03 96.03 Product of Example 1 3.30 - - - - - Product of Example 2 1.13 - - - - Product of Example 4 - - 4.00 - - Product of Example 8 - - - 3.30 - Product of Example 14 - - - - 0.50 Product of Example 16 - - - - - 0.50 Polybutenyl succinic 2.50 - - 2.50 - anhydride-alkylene polyamine-alcohol reaction product Polybutenyl-substituted - 2.64 - - - - aminophenol Basic calcium petroleum 0.66 - - 0.66 - - sulfonate Reaction product of alkyl - - - - 0.006 0.006 phenol, formaldehyde and 2,5-dimercapto-1 3,4- thiadiazole Zinc dialkylphosphoro- 0.99 - - 0.99 - dithioate Alkyl fumarate-vinyl 0.17 - - 0.17 - - acetate-vinyl ether terpolymer C11-14 tertiary alkyl primary - - - - 0.21 0.21 amine Fatty amide mixture - - - - 0.007 0.007 Sulfurized isobutene - - - - 3.15 3.15 Amine salt of phosphoric - - - - 0.10 0.10 acid ester Silicone anti-foam agent 0.005 - - 0.005 0.006 0.006 The fuel compositions of the present invention contain a major proportion of a normally liquid fuel, usually a hydrocarbonaceous petroleum distillate fuel such as motor gasoline as defined by ASTM Specification D439-73 or diesel fuel or fuel oil as defined by ASTM Specification D396. Normally liquid fuel compositions comprising non-hydrocarbonaceous materials such as alcohols, ethers, organo-nitro compounds and the like (e.g., methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane) are also within the scope of this 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-hydrocarbonaceous materials are also contemplated.

Examples of such mixtures are combinations of gasoline and methanol or ethanol or of diesel fuel and ether. Particularly preferred is gasoline, that is, a mixture of hydrocarbons having an ASTM boiling point of about 600C. at the 10% distillation point to about 2050C. at the 90% distillation point.

The compositions of this invention are normally added to fuels in amounts of about 0.0001- 0.1% by weight The fuel compositions can contain, in addition, other additives which are well known to those of skill in the art. These can include antiknock agents such as tetra-alkyl lead compounds, lead scavengers, such as haloalkanes (e.g., ethylene dichloride and ethylene dibromide), deposit preventers or modifiers such as triaryl phosphates, dyes, cetane improvers, antioxidants such as 2,6-di-tertiarybutyl-4-methylphenol, rust inhibitors such as alkylated succinic acids and anhydrides, bacteriostatic agents, gum inhibitors, metal deactivators, demulsifiers, upper cylinder lubricants, anti-icing agents and the like.

The compositions of this invention can be added directly to the lubricant or fuel. Preferably, however, they are diluted with a substantially inert, normally liquid organic diluent such as mineral oil, naphtha, benzene, toluene or xylene, to form an additive concentrate. These concentrates usually contain about from about 20% to about 90% by weight of the composition of this invention and may contain, in addition, one or more other additives known in the art or described hereinabove.

Claims

1. A composition comprising a metal or metalloid salt or complex of at least one aminophenol of the formula

wherein Ar is an aromatic radical having no sulfur or amino linkages between aromatic nuclei thereof; R is substantially saturated hydrocarbon-based radical having at least 30 aliphatic carbon atoms; and each of a, b and c is an integer from 1 to three times the number of aromatic nuclei in Ar.

2. A composition according to claim 1 wherein Ar is a phenyl-based radical.

3. A compostion according to claim 2 wherein Ar is a phenyl radical.

4. A composition according to claim 3 wherein a and c are each 1 and b is 1 or 2.

5. A composition according to claim 4 wherein b is 1.

6. A composition according to claim 5 wherein R is a hydrocarbon radical having from 30 to about 750 aliphatic carbon atoms.

7. A composition according to claim 1 prepared from at most about 1.1 equivalent of metal compound per equivalent of aminophenol.

8. A composition according to claim 1 prepared from about one-half to one equivalent of metal compound per equivalent of aminophenol.

9. A composition according to claim 1 prepared from substantially more than one equivalent of metal compound per equivalent of aminophenol.

10. A composition according to any of claims 1-6 wherein the metal or metalloid is at least one of the following: Group IA, IIA or IIB metals, iron, cobalt, nickel, manganese, silicon, boron, aluminum, chromium, tin, molybdenum, tungsten, antimony, lead, copper and bismuth.

11. A composition according to claim 10 wherein R is an alkyl radical having from about 40 to about 500 carbon atoms.

12. A composition according to claim 11 wherein the metal is at least one Group IA, IIA or lIB metal.

13. A composition according to any of claims 4-6 wherein R is para to the hydroxyl group.

14. A composition according to claim 13 wherein the metal or metalloid is at least one of the following: Group IA, IIA or lIB metals, iron, cobalt, nickel, manganese, silicon, boron, aluminum, chromium, tin, molybdenum, tungsten, antimony, lead, copper and bismuth.

1 5. A composition according to claim 14 wherein R is an alkyl radical having from about 40 to about 500 carbon atoms.

16. A composition according to claim 15 wherein the metal is at least one Group IA, IIA or lIB metal.

17. A composition according to any of claims 1-6 which has additionally been reacted with a formaldehyde-producing reagent.

18. A composition according to claim 17 wherein the metal is a Group IA, IIA or lIB metal.

19. A composition according to claim 18 wherein R is an alkyl radical having from about 40 to about 500 carbon atoms.

20. A method of preparing a composition according to any of claims 1-6 which comprises reacting at least one corresponding nitrophenol of the formula

with at least one reactive metal, reactive metal compound or metalloid compound and a reducing agent other than elemental sulfur.

21. A method according to claim 20 wherein the metal or metalloid is a Group IA, IlA or lIB metal.

22. A method according to claim 21 wherein R is an alkyl radical having from about 40 to about 500 carbon atoms.

23. An additive concentrate comprising a substantially inert, normally liquid organic diluent and from about 20% to about 90% by weight of a composition according to claim 1, 2,4 or 6.

24. An additive concentrate comprising a substantially inert, normally liquid organic diluent and from about 20% to about 90% by weight of a composition according to claim 10.

25. An additive concentrate comprising a substantially inert, normally liquid organic diluent and from about 20% to about 90% by weight of a composition according to claim 12.

26. An additive concentrate comprising a substantially inert, normally liquid organic diluent and from about 20% to about 90% by weight of a composition according to claim 14.

27. An additive concentrate comprising a substantially inert, normally liquid organic diluent and from about 20% to about 90% by weight of a composition according to claim 16.

28. An additive concentrate comprising a substantially inert, normally liquid organic diluent and from about 20% to about 90% by weight of a composition according to claim 17.

29. A lubricant comprising a major amount of a lubricating oil and a minor amount of a composition according to claim 1, 2, 4 or 6.

30. A lubricant comprising a major amount of a lubricating oil and a minor amount of a composition according to claim 10.

31. A lubricant comprising a major amount of a lubricating oil and a minor amount of a composition according to claim 12.

32. A lubricant comprising a major amount of a lubricating oil and a minor amount of a composition according to claim 14.

33. A lubricant comprising a major amount of a lubricating oil and a minor amount of a composition according to claim 16.

34. A lubricant comprising a major amount of a lubricating oil and a minor amount of a composition according to claim 17.

35. A fuel composition comprising a major amount of a normally liquid fuel and a minor amount of a composition according to claim 1,2, 4 or 6.

36. A fuel composition comprising a major amount of a normally liquid fuel and a minor amount of a composition according to claim 10.

37. A fuel composition comprising a major amount of a normally liquid fuel and a minor amount of a composition according to claim 12.

38. A fuel composition comprising a major amount of a normally liquid fuel and a minor amount of a composition according to claim 14.

39. A fuel composition comprising a major amount of a normally liquid fuel and a minor amount of a composition according to claim 16.

40. A fuel composition comprising a major amount of a normally liquid fuel and a minor amount of a composition according to claim 17.

41. The invention in its several novel aspects.