GB1588067A

GB1588067A - Lubricants and fuels and concentrates containing demulsifier additive compositions

Info

Publication number: GB1588067A
Application number: GB19624/78A
Authority: GB
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1977-10-13
Filing date: 1978-05-15
Publication date: 1981-04-15
Also published as: FR2405987A1; JPS5464503A; FR2405987B1; CA1104120A

Description

(54) LUBRICANTS AND FUELS AND CONCENTRATES CONTAINING DEMULSIFIER ADDITIVE COMPOSITIONS (71) We, THE LUBRIZOL CORPORATION, a corporation organised and existing under the laws of the State of Ohio, United States of America, of 29400 Lakeland Boulevard, Wickliffe, Ohio 44092, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to lubricant and fuel compositions having improved demulsifying properties, and method and concentrates for preparing such compositions.

In particular, the invention is concerned with the use of a demulsifier additive in lubricants such as power transmitting fluids, crankcase lubricants, gear lubricants, marine diesel lubricants, and fuels such as gasoline and diesel coming into contact with water and moisture, especially during storage and/or handling and reclaiming operations.

It is well known that water is an undesirable contaminant in fuels and lubricants.

For not only does water reduce the effectiveness of the fuel or lubricant, it tends to form deleterious by-products, particularly in relation to the engine or parts in contact with or utilizing the lubricant. For instance, water present in a crankcase lubricant is responsible for the formation of objectionable mayonnaise-like sludge which in turn promotes the formation of hard-to-remove deposits on engine parts. Presumably the formation of the sludge is preceded by the water forming an emulsion with the lubricant oil. While water should be separable from an oil or lubricant due to immiscibility, often the additives in many lubricants have water solubility sufficient to form emulsions which are difficult to remove. Thus, it is important to minimize the presence of water in lubricants whereby to reduce or eliminate the formation of such emulsions.

Naturally, lubricants having minimum contact with water would not present the serious problems of water/oil emulsions. However, it is difficult to eliminate contact with water, particularly during storage and/or handling. One particular procedure which gives rise to water contamination involves factory-fill transmission fluids. During assembly and testing of automative drive-train parts, the transmissions, especially automatic transmissions, are filled with the proper water-free transmission fluid for testing and inspecting under running and operating conditions. After such testing, the fluid is allowed to drain into exposed troughs or collecting stations leading to a main collecting tank. The drained oil is not protected from the immediate environment and often contains, among other things, a considerable amount of water. For efficiency and economy the collected oil should be re-used with minimal processing including filtering and centrifugation. To do so an effective demulsifier must be added to the lubricant.

In the prior art many demulsifiers have been suggseted and used. Mainly these demulsifiers have comprised a polyoxyalkylene glycol or a polyoxypolyamine. These glycols and polyamines have not been entirelv satisfactory because of their limited use and inability to function except in specific lubricants or fuels. Thus, there has been the need to "custom-make" specific demulsifiers, which is costly.

The demulsifiers of the present invention have shown effectiveness in a variety of lubricants and fuels by substantially reducing the formation of emulsions in such lubricants and fuels. They have been of particular benefit to water-contaminated factory-fill automatic transmission fluids referred to above.

According to one aspect of the invention there is provided a lubricant composition comprising a major proportion of a lubricating oil and a minor proportion of at least one demulsifier additive comprising a mixture of: A) one or more reaction products of a hvdrocarbon-substituted succinic acid or anhydride with one or more poly-alkylene glycols or mono-ethers thereof, wherein said hydrocarbon substituent is an alkyl or alkenyl radical having at least 4 but less than 50 carbon atoms, B) one or more organic basic metal salts, and C) one or more alkoxylated amines.

According to another aspect of the invention, there is provided a fuel composition having demulsifying properties resulting from the incorporation of 1 to 200 parts per million based on the fuel of a demulsifier additive comprising a mixture of: (A) one or more reaction products of a hydrocarbon-substituted succinic acid or anhydride with one or more polyalkylene glycols or mono-ethers thereof, wherein said hydrocarbon substituents is an alkyl or alkenyl radical having at least 4 but less than 50 carbon atoms, (B) one or more organic basic metal salts, and (C) one or more alkoxylated amines.

According to a further aspect of the invention, there is provided a concentrate suitable for imparting demulsifying properties to normally liquid fuels and lubricating compositions which comprises a normally liquid, substantially inert diluent, and from 2 to 50% by weight of at least one additive comprising a mixture of: A) one or more reaction products of a hydrocarbon-substituted succinic acid or anhydride with one or more poly-alkylene glycols or mono-ethers thereof, wherein said hydrocarbon substituent is an alykyl or alkenyl radical having at least 4 but less than 50 carbon atoms, B) one or more organic basic metal salts, and C) one or more alkoxylated amines.

According to yet a further aspect of the invention, there is provided a method of preparing a normally liquid fuel or lubricant composition having a major proportion of a normally liquid fuel or lubricating oil, which comprises incorporating into said fuel or lubricating oil a minor proportion of at least one demulsifier additive comprising a mixture of: A) one or more reaction products of a hydrocarbon-substituted succinic acid or anhydride with one or more polyalkylene glycols or mono-ethers thereof, wherein said hydrocarbon substituent is an alkyl or alkenyl radical having at least 4 but less than 50 carbon atoms, B) one or more organic basic metal salts, and C) one or more alkoxylated amines.

Component (A) is an ester wherein the acid comprises a hydrocarbon-substituted succinic acid or anhydride in which the hydrocarbon substituent is an alkyl or alkenyl radical of at least 4 but less than 50 carbon atoms in the chain, preferably from 6 to 30 carbon atoms, and most preferably, from 8 to 16 carbon atoms e.g. dodecyl.

The sources of the succinic acid or anhydride hydrocarbon substituent include a variety of monomers, oligomers, prepolymers, and even polymers. Oligomers can be a combination of two or more monomers; prepolymers refer to polymeric species capable of undergoing the addition reaction with the maleic acid or anhydride.

Monomers comprise any fr-monoolefin of at least 4 but less than 50 carbon atoms.

vr-Monoolefins such as l-butene, isobutene, l-hexene, l-octene, 2-methyl-1-heptene, 3cyclohexyl-l-butene, and 2-methyl-3-propyl-1-hexene are quite useful. Preferably dimers, trimers, or tetramers of ethylene or propylene are used to especial advantage.

Polymers of medial olefins, i.e., olefins in which the olefinic linkage is not at the terminal position, likewise are useful. They are illustrated by 2-butene, 3-pentene, and 4-octene. It is preferred that polymers derived from 3 to 6 carbon atom monoolefins are used, such as polypropylene or polybutene.

The hydrocarbon-substituted succinic acid or anhydride is reacted with one or more polyalkylene glycol to form the ester. The polyalkylene glycols, e.g. polyethylene glycols, or their monoethers, contemplated by the present invention desirably have average molecular weights in the range of 200 to 1500, particularly 200 to 600.

Specifically, polyethylene glycol of 200, 300 and 600 molecular weights are especially useful. Similarly, polypropylene glycols having molecular weights in the same range of 200 to 1500 are likewise useful. These polyalkylene glycols and their monoethers which are commercially available products (marketed by Union Carbide Corp., New York, N.Y. as Carbowax-Trade Mark) can be obtained by reacting the glycol with ethylene or propylene oxide. Methods of preparing such glycols are known to those skilled in the art.

As to the monoethers of said pplyalkylene glycols, they are illustrated by ethers such as monomethyl ether of polyethylene glycol, monoethylether of polyethylene glycol, monopropyl- and monobutyl ethers of polyethylene glycols. Generally, mono alkyl ethers wherein the alkyl group contains from 1 to about 12 carbon atoms are contemplated herein with the proviso that the average molecular weight does not exceed 1500.

The esterification reaction is conducted under conventional esterification conditions whereby the hydrocarbon-substituted acid or anhydride is generally reacted with the glycol at temperatures above 100"C., preferably 1100 to 150"C. Higher temperatures of 150--300"C. can be used if desired. Ofcourse, the extent of esterifi cation can be controlled to produce substantially neutral esters, acidic esters, or mixtures of these. It has been found that the acidic esters are generally most effective and they are thus much preferred. Therefore, in conducting the esterification the reactants are introduced into the reactor at ratios designed to favour the rzrod1lction of the acid ester. For clarity, the acid ester is defined as the product formed from the reaction of a dibasic acid (or anhydride) with a polvol in such ratios that the carb oxvlic acid moieties are never completely esterified. Thus when one mole of a dihasic acid is reacted with one mole of alcohol. the half ester or acid ester is formed. Similarlv, if 2 moles of a dibasic acid (or anhydride) are reacted with a diol the half or acid ester is formed. The latter can be illustrated by the following representative reaction.

wherein R, is the hydrocarbon substituent of the succinic anhydride and R2 represents the polyalkylene group of the glycol. If the mono-ether such as methoxy polyalkylene glycol is used to prepare the acid ester the ratio becomes one mole of acid to one mole of the monoether as the latter has one hydroxyl moiety available for reaction.

Referring to component (B) of the demusifier additive it describes the well known class of basic metal organic salts in which the metal is present in a stoichiometrically greater amount than necessary to produce the neutral salt. These salts are often referred to as "basic salts", "overbased salts", "super-based salts" and "hynerhased salts".

Such basic metal salts are known in the art. Those which are contemplated herein include salts derived from oil-soluble sulfonic acids, oil-soluble carboxylic acids, oilsoluble phosphonic acids, oil-soluble phenolic acids and mixtures thereof, such as are described in U.S. Pat. Nos. 2,501,731: 2.616,904; 2616.905; 2.616.906; 2.616911; 2,616,924; 2,696,025; 2,617,049; 2,777,874; 3,207,305; 3,256,186; 3,282,835; 3,384,585; 3,373,108; 1,365,396; 3,342,733; 3,320,162; 2.312,618; and 3,318,809.

As an example of a particularly convenient process for the preparation of the basic salts used, an oil-soluble sulfonic acid, such as a synthetically prepared didodecylbenzene sulfonic acid, is mixed with an excess of lime (e.g. 10 equivalents per equivalent of the acid) and a promoter such as methanol, heptylphenol, or mixture thereof, and a solvent such as mineral oil, at 50PC--1500C. and the process mass is then carbonated until a homogeneous mass is obtained. Basic salts derived from sulfonic acids, carboxylic acids, and mixtures thereof are obtainable by processes such as are described in U.S. Pat. No. 3,312,618. Another example is the preparation of a magnesium sulfonate basic salt by carbonating a mixture of a sulfonic acid or normal magnesium salt thereof, an excess of magnesium oxide, water, and preferably also an alcohol promoter such as methanol.

The carboxylic acids useful for preparing sulfonate-carboxylate basic salts, and carboxylate basic salts, i.e. those obtainable from processes such as the above wherein a mixture of sulfonic acid and carboxylic acid or a carboxylic acid alone is used in lieu of the sulfonic acid, are oil-soluble acids and include primarilv fatty acids which have at least 12 aliphatic carbon atoms and not more than 24 aliphatic carbon atoms.

Examples of these acids include: palmitic, stearic, myristic, oleic, linoleic, dodecanoic and behenic. Cyclic carboxvlic acids may also be employed. These include aromatic and cyclo-aliphatic acids. The aromatic acids are those containing a benzenoid struc ture (i.e. benzene, naphthalene, etc.) and an oil-solubilizinz radical or radicals having a total of at least 1S carbon atoms, preferably from 13 to 200 carbon atoms. Examples of the aromatic acid include: stetarvl-benzoic acids phenyl-stearic acid, mono- or polywax-substituted benzoic or naphthoic acids wherein the wax group consists of at least 18 carbon atoms, cetyl-hvdroxybenzoic acids. The cycloaliphatic acids contem plated have at least 12, usually not more than 30 carbon atoms. Examnles of such acids are petroleum naohthenic acids, cetvl-cvclohexane-carboxvlic acids. di-laurvl decahydronaphthalene-carboxylic acids, and di-octyl-cyclopentane-carboxylic acids.

The thiocarboxylic acid analogs of the above acids, wherein one or both of the oxygen atoms of the carboxylic group are replaced by sulfur, are also contemplated. The ratio of the sulfonic acid to the carboxylic acid in sulfonate-carboxylate mixtures is at least 1:1 (on a chemical equivalent basis) and is usually less than 5:1, preferably from 1:1 to 2:1.

In general, basic salts having metal ratios from 1.1 to 30 are contemplated for use in the present invention. Those prepared from Mg, Ca, Ba, Li, or Na and having metal ratios ranging from 2 to 20 are preferred.

The alkoxylated amines (Component C) of the present invention comprise alkylene oxide derivatives of aliphatic amines. These alkoxylated amines may be secondary or tertiary amines having one or more groups of the formula -NR1R2 wherein R1 is -(-O-alkylene-)-,OH, wherein alkylene is straight or branched chain and contains not more than 6 carbon atoms and usually 2 to 4 carbon atoms and n is a number of 1 to 10, and R2 is selected from hydrogen, an alkyl group of not more than 18 carbon atoms, and R1. Representative alkoxylated amines are the ethoxylated amines which are tertiary amines having one alkyl group and two polyoxy ethylene groups attached to the nitrogen:

wherein R' represents an alkyl group of not more than 18 carbon atoms, x and y are numbers ranging each from 1 to 8 with the proviso that the sum of x + y is not greater than 15. The source of the alkyl group R' is preferably a fatty acid such as coco, oleic, soya, tallow, or stearic fatty acids.

Also contemplated as the alkoxylated amine (Component C) are the ethoxylated amines obtainable by reacting ethylene oxide with a diamine. For example, N-alkyl trimethylene diamine can be reacted with ethylene oxide to produce a compound represented by the following:

wherein R', x and y are as above described and z is a number from 1 to 8 with the proviso that the sum of x, y and z does not exceed 15.

The alkoxylated amines of the present invention are commercially available products obtainable from various sources. Those marketed under the trade marks ETHOMEEN and ETHODUOMEEN (made by Armak Co., part of Akzona, Inc.) are particularly preferred.

Because of their availability ethylene oxide and propylene oxide represent the most practical alkylene oxide reagents for preparing the above alkoxylated amines.

However, butylene oxide, pentene oxide and others can be used, also. For most efficient use ethylene oxide (to make the corresponding ethoxylated amine) is preferred.

In preparing the demulsifier additive of the present invention Components (A), (B) and (C) are mixed physically to make a substantially homogeneous mixture for incorporation into lubricants or fuels or to make concentrates for subsequent addition to lubricants or fuels. Preferredly, the demulsifier additive is formed in stages whereby Components (A) and (B) are mixed and heated at about 50--125"C. for sufficient time, usually not more than 3 hours. Component (C), the alkoxylated amine, then is mixed with the above initial mixture/product of (A) and (B) just prior to preparation of the concentrate or prior to addition to the lubricant. Of course, the three components can be mixed together and heated at about 50--125"C. for not more than three hours to provide the demulsifier additive. While heating at about 50--125"C. is not essential, it has been found beneficial in providing optimum demulsifier additives. For best results, Components (A) and (B) are heated at the prescribed temperature range with (C) being admixed subsequently.

In terms of the lubricant composition the demulsifier additive generally comprises from 0.05 to 2% by weight of the total weight of the composition. Higher amounts can be added, if desired, but it is believed that amounts greater than 2% are not necessary and can contribute to higher costs. Specifically Component (A) can be from 0.03 to 1% by weight of the lubricant. Similarly, Component (B) can be from 0.01 to 1% by weight, and Component (C) can be from 0.001 to 1% by weight, respectively, of the lubricant.

The fuels to which the demulsifier additives of the invention are added are the normally liquid fuels, such as gasoline, diesel fuels, jet fuels, fuel oils, alcohols, alcohol mixtures, and distillate oils which do not utilize as much demulsifier additive as do lubricants. Thus, for effective demulsification of the fuel, usuallv 1 ppm to 200 ppm (parts per million) of the demulsifier additive is incorporated into the fuel.

The demulsifier additives of the present invention generally are soluble or stably dispersible in the normally liquid lubricant or fuel in which it is intended to function.

Lubricant compositions, by and large, contain lubricating oil as a major proportion.

Thus, the demulsifier should be at least stably dispersible in such lubricating oils.

To function properly the demulsifier need not be oil soluble. For clarity the term "oil soluble" as used herein does not necessarilv mean that all of the compositions in question are miscible or soluble in all proportions in all oils. Rather, it is intended to mean that the demulsifier additive composition herein described is soluble in an oil which is used for lubricating purposes at the concentrations described hereinbefore.

Similarly, it is not necessary that such solutions be true solutions in the strict physical or chemical sense. They may be instead microemulsions or colloidal dispersions which, for the purposes of this invention, would exhibit properties sufficiently close to those of true solutions to be for practical purposes interchangeable within the context of this invention. Also, the term "stably dispersible" in the normally liquid media as used herein is intended to mean a demulsifier composition which is capable of being dispersed in a given medium to an extent which allows it to function as a demulsifier.

Thus, the demulsifier additives of the present invention can be dispersed stably in a lubricating oil and impart to it the desired demulsifying properties. Such stable dispersion of the demulsifier can be achieved in various conventional ways, such as by physical agitation. Other means of suspending and/or dispersing a minor component in a major liquid component are very well known to those of ordinary skill in the art, that need not be described herein. For example, conventional dispersants and detergents normally present in lubricants promote the solubility and/or stable dispersion of the herein described demulsifier additives.

This invention is exemplified in the following examples. Examples 1-8 and 16A illustrate the preparation of Component (A); Example 14 illustrates the preparation of Component (B); Examples 9-13 and 15, 16 ,16 (B) and 17 illustrate the preparation of a mixture of Components (A) and (B); and Examples 18-20A illustrate the preparation of a mixture of Components (A), (B) and (C). Of course, these examples are not intended as limiting this invention as modification of the examples by ordinary expedient will be readily apparent to those of ordinary skill in the art.

In all examples, unless otherwise stated, all temperatures are in degrees Centigrade; all parts are parts by weight; and all percentages are percentages by weight.

Example 1.

A mixture of 133 parts (0.5 mole) of a tetrapropenyl-substituted succinic anhydride, 375 parts (0.5 mole) of a commercially available methoxy polyoxymethylene glycol (Carbowax 750) obtained from Union Carbide Corp.) having an average formula molecular weight of about 750, and 200 parts of toluene is heated to 1000C.

The reaction mixture is held at 100-1200C. for 8 hours, then stripped at 1200C.

under vacuum for one hour. The reaction mixture is filtered to yield the filtrate as the desired acid ester product.

Example 2.

The procedure for Example 1 is repeated except the methoxy polyoxyethylene glycol (Carbowax 750) having an average formula molecular weight of about 750 is replaced on equimolar basis by one having a formula molecular weight of 350 (Carbowax 350). The filtrate is the desired acid ester product.

Example 3.

A mixture of 347 parts (1.3 moles) of a tetrapropenyl-substituted succinic anhyride and 261 parts (0.65 mole) of a commercially available polyoxyethylene glycol (Carbowax 400) having an average formula molecular weight of about 400 is heated at 1200C. for 6 hours. The product is filtered to yield the filtrate as the desired acid ester product.

Example 4.

A mixture of 4256 parts (32 equivalents) of a tetrapropenyl-substituted succinic anhydride and 2400 parts (16 equivalents) of a commercially available polyoxyethylene glycol (Carbowax 300) having an average formula molecular weight of about 300 is heated at 1200C. for 3 hours. The residue is the desired ester product.

Example 5.

The procedure for Example 4 is repeated except the polyoxyethylene glycol (Carbowax 300) having a formula molecular weight of about 300 is replaced on an equimolar basis by a polyoxyethylene glycol (Carbowax 200) having a formula molecular weight of 200. The product is the desired ester product.

Example 6.

The procedure for Example 4 is repeated except the polyoxyethylene glycol (Carbowax 300) having an average formula molecular weight of about 300 is replaced on an equimolar basis by a polyoxyethylene glycol (Carbowax 1000) having an average formula molecular weight of about 1000. A similarly desired ester product is obtained.

Example 7.

The procedure for Example 3 is repeated except the polyoxyethylene glycol (Carbowax 400) is replaced on an equimolar basis by polyoxypropylene glycol having an average formula weight of about 425. The ester obtained is the desired ester product.

Example 8.

The procedure for Example 3 is repeated except the polyoxyethylene glycol (Carbowax 400) having an average formula molecular weight of about 400 is replaced on an equimolar basis by a polyoxypropylene glycol having an average formula molecular weight of about 1000.

Example 9.

A mixture of 466 parts (1 equivalent) of the acid ester prepared in Example 4 and 114 parts of a basic magnesium sulfonate commercially available from Witco Chemical Company, Chicago, Illinois, as Hybase M-400 Magnesium Sulfonate is heated at 1200--1300C. for 3 hours. The residue is the desired product.

Example 10.

A mixture of 6656 parts (16 equivalents) of the acid ester product prepared in Example 4 and 2272 parts (16 equivalents) of a basic magnesium sulfonate commercially sold by Witco Chemical Company as Hybase (Trade Mark) M-400 Magnesium Sulfonate is heated at l20-l300C. for 2 hours. The residue is the desired product.

Example 11.

A mixture of 466 parts (1 equivalent) of the acid ester product prepared in Example 4 and 284 parts (2 equivalents) of a basic magnesium sulfonate com mercially available from Witco Chemical Company as Hybase M-400 Magnesium Sulfonate is heated at 120--130"C. for 3 hours. The residue is the desired product.

Example 12.

The procedure for Example 9 is repeated except the acid ester product of Example 4 is replaced on an equivalent basis by the acid ester product of Example 1.

Example 13.

The procedure of Example 11 is repeated except the acid ester product of Example 4 is replaced on an equivalent basis by the acid ester product of Example 5.

Example 14.

A mixture of 331 parts of mineral oil, 69 parts of heptylphenol, 50 parts of water, 54 parts of a polybutenyl (Mn = 1000) substituted succinic anhydride, 58 parts of lithium hydroxide monohydrate and 465 parts of an alkyl benzene sulfonic acid having a molecular weight of about 390 is heated at reflux for one hour. An additional 150 parts lithium hydroxide monohydrate is added to the reaction mixture, which is then dried at 1500C. At 130-1330C. the reaction mixture is blown with 210 parts (5 equivalents) of carbon dioxide over a two-hour period.

The reaction mixture is stripped at 133-1600C. under nitrogen for one hour. The reaction mixture is filtered to yield the desired basic lithium sulfonate having 25% lithium sulfate ash.

Example 15.

A mixture of 416 parts (1 equivalent) of the acid ester product prepared in Example 4 and 261 parts (1 equivalent) of the basic lithium sulfonate prepared in Example 14 is heated at 100"C. for 3 hours. The residue is the desired product.

Example 16.

The procedure for Example 15 is repeated except the acid ester product prepared in Example 4 is replaced on an equivalent basis by the acid ester product of Example 3.

Example 16A.

A mixture is prepared from 200 parts each of polyethylene glycol (200), poly ethylene glycol (300) and polyethylene glycol (400) and 1000 parts of tetrapropenyl substituted succinic anhydride, said mixture is heated at 120"C. for about three hours.

-The residue is the desired mixed acid ester.

Example 16B.

To 400 parts of the mixed acid ester prepared in Example 1 6A is added 75 parts of basic magnesium sulfonate (Hybase M-400) and 25 parts of the basic lithium sulfonate prepared in Example 14. The admixture is heated at 100"C. for about 3 hours to yield the desired product.

Example 17 A mixture is prepared by the slow addition of 187 parts of a basic, carbonated calcium sulfonate having a metal ratio of 12 and prepared from a 430 molecular weight petroleum sulfonic acid according to the procedure described in U.S. Patent 3,350,308 to 416 parts (1 equivalent) of the acid ester product prepared in Example 4 and 200 parts of mineral oil at 600C. The reaction mixture is then heated at 110 1200C. for 1/2 hour. The residue is the desired product.

Example 18.

A mixture of 51 parts of the product prepared according to the procedure of Example 10 and 39 parts of Ethonzeen C/13 (a product of Armak Co., part of Akzona, Inc.) is heated to TOOC. for 1 hour. The residue is the desired demulsifier product.

Example 19.

A mixture of 70 parts of the product-prepared according to the procedure of Example 11 and 70 parts of Ethoduorneen T/13 (a product of Armak Co.) is heated at 50"C. for 1 hour. The residue is the desired demulsifier product.

Example 20.

A mixture of 60 parts of the product prepared according to the procedure of Examnle 16 and 40 parts of Ethomeen C/12 (a product of Armak Co.) is heated at 50"C. for 1 hour. The residue is the desired demulsifier product.

Example 20A.

A mixture of 120 parts of the product prepared in Example 16B and 60 parts of Ethomeen C/12, and 60 parts of Ethoduomeen T/13 is prepared and heated at 50"C. for 1 hour. The product obtained is the desired demulsifier product.

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 D43973 and diesel fuel or fuel oil as defined by ASTM Specification D-396. Normally liquid fuel compositions comprising non-hydrocarbonaceous materials such as alcohols, ethers, organic nitrocompounds and the like (e.g. methanol, ethanol, diethyl ether, methyl ethyl ester, 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 ethanol, 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 205"C. at the 90% distillation point.

Generally, these fuel compositions contain an amount of the demulsifier additive of this invention sufficient to impart the desired demulsifying properties to the fuel; usually this amount is 1 to 200 preferably 1 to 40 parts by weight of the reaction product per million parts by weight of fuel. The preferred gasoline-based fuel compositions generally exhibit excellent demulsifying properties.

The fuel compositions of this invention can contain, in addition to the demulsifier of this invention, other additives which are well known in those of skill in the art.

These can include antiknock agents such as tetralkyl lead compounds, lead scavengers such as halo-alkanes (e.g. ethylene dichloride and ethylene dibromide), deposit preventors or modifiers such as triaryl phosphates, dyes, cetane improvers, antioxidants such as 2,6-di-tertiary-butyl-4-methylphenol, rust inhibitors such as alkylated succinic acids and anhydrides, bacteriostatic agents, gum inhibitors, metal deactivators, upper cylinder lubricants, anti-icing agents and the like.

In certain preferred fuel compositions of the present invention, the afore-described demulsifier and additives are combined with an ashless dispersant in gasoline. Such ashless dispersants are preferably esters of a mono-, or pclyol and a high molecular weight mono- or polycarboxylic acid acylating agent containing at least 30 carbon atoms in the acyl moiety. Such esters are well known to those of skill in the art.

See, for example, French Patent 1,396,645, British Patents 981,850 and 1,055,337 and U.S. Patents 3,255,108; 3,311,558; 3,331,776; 3,346,354; 3,522,197; 3,579,450; 3,542,680; 3,381,022; 3,639,242; 3,697,428; 3,708,522; and British Patent Specification 1,306,529. Generally, the weight ratio of the demulsifier of this invention to the aforesaid ashless dispersants is 0.1 to 10, preferably 1 to 10 parts of demulsifier to 1 part ashless dispersant. In still another embodiment of this invention, the inventive additives are combined with Mannich condensation products formed from substituted phenols, aldehydes, polyamines, and substituted pyridines. Such condensation products are described in U.S. Patents 3,649,659; 3,558,743; 3,539,633; 3,704,308; and 3,723,277.

As previously indicated, the lubricant compositions of this invention contain a major proportion of a lubricating oil. These oils include diverse oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof. These oils more specifically include crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, including automobile and truck engines, two-strokeengines, aviation piston engines, and marine and railroad diesel engines. The compositions of the invention 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 lubri cating 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, propylene-isobutylene copolymers, chlorinated polybutylenes, poly( 1 -hexenes), poly (1-octenes), poly(1-decenes), and mixtures thereof]; alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes; polyphenyls (e.g. biphenyls, terphenyls, alkylated polyphenyls), alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, and analogs and homologs thereof.

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. methyl polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 5001i000, diethyl ether of polypropylene glycol having a molecular weight of 10001500 or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed Cs-C8 fatty acid esters, or the C1,, 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, alknyl-malonic acids with a variety of alcohols (e.g. butyl alcohol), hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol. 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, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.

Esters useful as synthetic oils also include those made from C2 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol.

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

tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4methyl-2-ethylhexyl) silicate, tetra- (p-tert-butylphenyl) silicate, hexa-(4-methyl-2 pentoxy) -disiloxane, poly(methyl) siloxanes, and poly(methylphenyl) siloxanes. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g.

tricresyl phosphate, trioctyl phosphate and diethyl ester of decylphosphonic acid), and polymeric tetrahydrofurans.

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 operation,~ 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 and percolation. 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 tne present invention contain an amount of the demulsifier additive sufficient to provide it with the desired demulsifying properties.

Normally this amount will be .05 to 2%, preferably 0.1 to 1 of the total weight of the lubricant. In lubricating oils operated under extremely adverse conditions, such as lubricating oils for marine diesel engines, the amount of demulsifier additive may be an amount of not more than 10% by weight.

The demulsifier additive can be added directly to the fuel or lubricant to form fuel or lubricant compositions of this invention or it can be diluted with a substantially inert, normally liquid organic solvent/diluent such as mineral oil, xylene, or a normally liquid fuel as described above, to form an additive concentrate which is then added to the fuel or lubricant in sufficient amounts to form the inventive fuel or lubricant composition described herein. These concentrates generally contain not more than 50% by weight, and preferably from 2 to 30 percent of the demulsifier additive of this invention. Moreover, these concentrates can contain in addition any of the abovedescribed conventional additives, particularly the aforedescribed ashless dispersants in the aforesaid proportions.

Lubricating and fuel compositions made according to this invention are exemplified by the following: Example A.

The lubricating composition suitable for use as an automatic transmission fluid, is prepared, using as the base oil a mixture of 90% by volume of a 110Neutral mineral oil and 10% by volume of a 200Neutral mineral oil, and as additives, by weight; 4% of a mixed ester of a styrene-maleic anhydride copolymer reacted with a nitrogen-containing compound (prepared as in U.S. Patent No. 3,702,300); 3.0% of a commercially available, proprietary seal swell agent; 1% of the reaction product of a polyisobutenyl-substituted succinic anhydride, commercial tetraethylene pentamine, and boric acid prepared as in U.S. Patent No. 3,2S4,025; 0.3% of a commercially available diphenylamine-based oxidation inhibitor; 0.1% of a dialkylphosphite; 0.5% of a conventional friction modifier based on polyoxyethylene tallow amine (Ethomeen T/12); 0.3% of hydroxy thioether as described in U.S. Patent 4,031,023; 3.0% of the reaction product of poyisobutenyl-succinic anhydride and ethylene-polyamine; and as the demulsifier 0.2% of the product of Example 10 and 0.05% of Ethomeen C/1S.

Example B.

A lubricating composition suitable for use as an automatic transmission fluid is prepared using an ATF base and, as additives, 0.13% of the reaction product of a dialkylphosphite and an alkyl alpha-olefin epoxide as described in U.S. Patent 3,932,290; 1.75% of the reaction product of a polyisobutenyl-succinic anhydride and ethylene polyamine; 0.67% of the reaction product of boric acid with the reaction product of polyisobutenyl-succinic anhydride and polyethylene polyamine; 0.52% of a zinc salt of a phosphorodithioic acid; 0.10% of a tallow-substituted diethanolamine; 1.20% of a mixed ester-amide of maleic anhydride-styrene copolymer (12% in solution); 3.00% hydrocarbon resin seal swelling agent; 0.20% substituted diphenylamine; 0.02% of a silicone anti-foam agent; and as the demulsifier 0.25% of the product of Example 15 and 0.09% of Ethomeen C/1S.

Example C.

A gasoline having a Reid vapor pressure of 8.4 psi and containing 2.0 grams of lead per gallon and as additives: 20 ppm of a Mannich base prepared from tetrapropenyl-substituted phenol, formaldehyde and diethanolamine as in U.S. Patent No.

3,877,889; 89.6 ppm of the reaction product of polyisobutenyl (Mn = 1000)succinic anhydride with polyethylene polyamine mixture; 2.9 ppm of an ethoxylated reaction product of oleic-naphthenic acid mixture with polyethylene polvamine mixture; 42 ppm isooctyl alcohol; 118.5 ppm xylene; 3.0 ppm Nalco (Trade Mark) Proprietary Dehazer Composition; and as the demulsifier 4.0 ppm of the product of Example 20.

Example D.

A lubricating composition suitable for use as a crankcase lubricant is prepared using a 10W-40 mineral lubricating oil base and, as additives: 3.41% of a polyisodecyl acrylate viscosity improver; 4.2 of an ashless dispersant based on the reaction product of a polyisobutenyl-(Mn = 1000) succinic anhydride, pentaerythritol, and polyethylene polyamines; 1.57% of an overbased calcium sulfonate detergent; 0.82% of a zinc salt of a phcsehorodithioic acid; 40 ppm of a conventional anti-foam agent; and as a demulsifier 0.25% of the product of Example 17 and 0.05% of Ethoduomeen T/13.

Example E.

A lubricating composition suitable for use as an industrial gear lubricant is prepared using a SAE 90 base mineral lubricating oil, and as additives: 0.5% of a dialkyl phosphate derived from long-chain alcohols; 0.02% of a conventional antifoaming agent based upon a polymer of 2-ethylhexyl acrylate and ethyl acrylate; 0.25% of a sulfurized isobutylene; and as a demulsifier 0.04% of the product of Example 12 and 0.01% of Ethomeen C/12.

Example F.

A lubricating composition suitable for use as a marine diesel lubricant is prepared using a SAE 90 base mineral lubricating oil and 5.7% of an additive concentrate.

The additive concentrate is mineral oil based and comprises the following additives: 23.44% of the reaction product of a pGlybutenyl-(Mn = 1000) succinic anhydride; zinc oxide, and ethylene polyamines as in U.S. Reissue Patent 26,433; 17.05% of a calcium overbased sulfurized alkyl-phenol; 1.56 /r of a zinc salt of a phosphoro dithicic acid; 2.87% mineral oil; 8.2% of a slightly basic calcium sulfonate 46.88% of an overbased calcium sulfonate detergent; and as a demulsifier 0.9% of the product of Example 19.

Example G.

A lubricating composition suitable for use as a crankcase lubricant is prepared using a 10W-40 mineral lubricating oil base and, as additives: 4.41% of a polyisodecyl acrylate viscosity improver; 4.2% of an ashless dispersant based on the reaction product of a polyisobutenyl-(Mn = 1000) succinic anhydride, pentaerythritol, and polyethylene polyamines; 1.57% of an overbased calcium sulfonate detergent; 0.82% of a zinc salt of a phosphorodithioic acid; 40 ppm of a conventional anti-foam agent; and as a demulsifier 0.30% of the product of Example 20A.

To determine the effectiveness of the demulsifier additive in the exemplified lubricants and fuels, the standard method for "Demulsibility Characteristics of Lubricating Oils" as described in ANSI/ASTM D271 1-74 is followed. Modification in terms of liquid and/or demulsifier quantities have been made to provide more meaningful data for certain lubricants or fuels. In particular, 200 ml of the test fluid is utilized, which fluid is placed into a blender at room temDerature. The blender is operated at low speed for 30 seconds after which 20 mls. of distilled water is added and mixed for one more minute. The mixture is poured into 400 ml. beaker, covered and placed into an oven at 160 t 2"F. Extent and rate of separation of water and oil, as well as the interface (cuff) is observed at 2 and 4 hour intervals.

In the foregoing examples the lubricants and fuels containing the demulsifier additive have shown excellent demulsifying properties. Automatic transmission fluids containing 0.1 to 1% of the demulsifier of the invention can be expected for use in factory filling operations with minimal filtering and centrifuging to remove the included water. Thus, the demulsified fluids provide convenience and economy unavail able heretofore.

WHAT WE CLAIM IS: 1. A lubricant composition comprising a major proportion of a lubricating oil and a minor proportion of at least one demulsifier additive comprising a mixture of: A) one or more reaction products of a hydrocarbon-substituted succinic acid or anhydride with one or more polyalkylene glycols or mono-ethers thereof, wherein said hydrocarbon substituent is an alkyl or alkenyl radical having at least 4 but less than 50 carbon atoms.

B) one or more organic basic metal salts, and C) one or more alkoxylated amines.

2. The lubricant composition of claim 1 wherein the glycol is selected from polyethylene glycol, its monoether, and mixtures thereof, and the hydrocarbon sub stituent on said succinic acid or its anhydride has 6 to 30 carbon atoms.

3. The lubricant composition of claim 1 or 2 wherein the polyalkylene glycol has an average molecular weight of 200 to 1500.

4. The lubricant composition of claim 1, 2 or 3 wherein the alkoxylated amine is a tertiary amine having one alkyl group of 12 to 18 carbon atoms, attached to the amino nitrogen.

5. The lubricant composition of claim 3 wherein the glycol is preponderantly polyethylene glycol of 200 to 1000 average molecular weight.

6. The lubricant composition of any preceding claim wherein the organic basic metal salt is an overbased alkaline earth sulfonate.

7. The lubricant composition of claim 6 wherein the salt is overbased magnesium sulfonate.

8. The lubricant composition of claim 2 wherein the glycol is polyethylene glycol of 200 to 600 average molecular weight and the hydrocarbon substituent contains about 12 carbon atoms.

9. A lubricant composition comprising a major proportion of a lubricating oil and a minor proportion of at least one demulsifier additive comprising a mixture of:

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

Claims

**WARNING** start of CLMS field may overlap end of DESC **. Example F. A lubricating composition suitable for use as a marine diesel lubricant is prepared using a SAE 90 base mineral lubricating oil and 5.7% of an additive concentrate. The additive concentrate is mineral oil based and comprises the following additives: 23.44% of the reaction product of a pGlybutenyl-(Mn = 1000) succinic anhydride; zinc oxide, and ethylene polyamines as in U.S. Reissue Patent 26,433; 17.05% of a calcium overbased sulfurized alkyl-phenol; 1.56 /r of a zinc salt of a phosphoro dithicic acid; 2.87% mineral oil; 8.2% of a slightly basic calcium sulfonate 46.88% of an overbased calcium sulfonate detergent; and as a demulsifier 0.9% of the product of Example 19. Example G. A lubricating composition suitable for use as a crankcase lubricant is prepared using a 10W-40 mineral lubricating oil base and, as additives: 4.41% of a polyisodecyl acrylate viscosity improver; 4.2% of an ashless dispersant based on the reaction product of a polyisobutenyl-(Mn = 1000) succinic anhydride, pentaerythritol, and polyethylene polyamines; 1.57% of an overbased calcium sulfonate detergent; 0.82% of a zinc salt of a phosphorodithioic acid; 40 ppm of a conventional anti-foam agent; and as a demulsifier 0.30% of the product of Example 20A. To determine the effectiveness of the demulsifier additive in the exemplified lubricants and fuels, the standard method for "Demulsibility Characteristics of Lubricating Oils" as described in ANSI/ASTM D271 1-74 is followed. Modification in terms of liquid and/or demulsifier quantities have been made to provide more meaningful data for certain lubricants or fuels. In particular, 200 ml of the test fluid is utilized, which fluid is placed into a blender at room temDerature. The blender is operated at low speed for 30 seconds after which 20 mls. of distilled water is added and mixed for one more minute. The mixture is poured into 400 ml. beaker, covered and placed into an oven at 160 t 2"F. Extent and rate of separation of water and oil, as well as the interface (cuff) is observed at 2 and 4 hour intervals. In the foregoing examples the lubricants and fuels containing the demulsifier additive have shown excellent demulsifying properties. Automatic transmission fluids containing 0.1 to 1% of the demulsifier of the invention can be expected for use in factory filling operations with minimal filtering and centrifuging to remove the included water. Thus, the demulsified fluids provide convenience and economy unavail able heretofore. WHAT WE CLAIM IS:

1. A lubricant composition comprising a major proportion of a lubricating oil and a minor proportion of at least one demulsifier additive comprising a mixture of: A) one or more reaction products of a hydrocarbon-substituted succinic acid or anhydride with one or more polyalkylene glycols or mono-ethers thereof, wherein said hydrocarbon substituent is an alkyl or alkenyl radical having at least 4 but less than 50 carbon atoms.

A) one or more reaction products of a hydrocarbon-substituted succinic acid or anhydride with one or more polyethylene glycols or mono-ethers thereof, wherein said hydrocarbon substituent is an alkyl or alkenyl radical having 6 to 30 carbon atoms, B) one or more organic basic alkaline earth metal salts, and C) one or more amines characterized by having at least one group of the formula --NR,R, wherein R1 is alkylene-O+DH wherein alkylene contains not more than 6 carbon atoms, and n is a number from 1 to 10, R1 is selected from hydrogen, alkyl or not more than 18 carbon atoms, and Rl

10. The lubricant composition of claim 9 wherein the hydrocarbon substituent on said succinic acid or anhydride has 8 to 16 carbon atoms.

11. The lubricant composition of claim 9 wherein (A) represents the reaction product of a dodecyl-succinic acid or anhydride with a polyethylene glycol of about 300 average molecular weight, and (C) represents a tertiary amine RNR1R2 wherein R is an alkyl of not more than 18 carbon atoms, and the number n for the alkylene-O+lH in R1 is from 1 to 8

12. The lubricant composition of claim 11 in which the tertiary amine has R2 the same as R1 with n being 2 to 4, and wherein R is an alkyl group of 12 to 18 carbon atoms.

13. The lubricant composition of claim 11 or 12 wherein the organic basic metal salt is overbased magnesium sulfonate.

14. An automatic transmission fluid having a major proportion of lubricating oil and minor proportion of one or more additives selected from seal swellers, viscosity modifiers, dispersants, detergents, extreme pressure agents and anti-wear agents, antirust agents and corrosion inhibitors, and also at least one demulsifier additive comprising a mixture of: A) one or more reaction products of a hydrocarbon-substituted succinic acid or anhydride with one or more polyalkylene glycols or mono-ethers thereof, wherein the hydrocarbon substituent on said acid or anhydride is an alkyl or alkenyl radical having 6 to 30 carbon atoms, and said polyalkylene glycols have an average molecular weight of 200 to 1500, B) one or more organic basic alkaline earth metal salts, and C) one or more amines characterized by having at least one group of the formula -NR1R2 wherein Rl is alkylene-O+DH wherein alkylene contains not more than 6 carbon atoms, and n is a number from 1 to 10, and R2 is selected from hydrogen, alkyl of not more than 18 carbon atoms, atnd R1.

15. The fluid of claim 14 wherein the hydrocarbon substituent on the succinic acid or anhydride has 8 to 16 carbon atoms and the glycol is a polyethylene glycol of an average molecular weight of 200 to 600.

16. The fluid of claim 15 wherein the substituent on said succinic acid or anhydride is a dodecyl radical.

17. The fluid of claim 16 wherein the organic basic salt is an overbased magnesium sulfonate.

18. The fluid of claim 17 wherein said amine is a tertiary amine RNR1R, with R representing an alkyl group of not more than 18 carbon atoms.

19. The fluid of claim 18 wherein the amine has R2 the same as R1 with n being 2 to 4 and R an alkyl group of 12 to 18 carbon atoms.

20. A concentrate suitable for imparting demulsifying properties to normally liquid fuels and lubricating compositions which comprises a normally liquid, substantially inert diluent, and from 2 to 50% by weight of at least one additive comprising a mixture of: A) one or more reaction products of a hydrocarbon-substituted succinic acid or anhydride with one or more polyalkylene glycols or mono-ethers thereof, wherein said hydrocarbon substituent is an alkyl or alkenyl radical having at least 4 but less than 50 carbon atoms, B) one or more organic basic metal salts, and C) one or more alkoxylated amines.

21. A method of preparing a normally liquid fuel or lubricant composition having a major proportion of a normally liquid fuel or lubricating oil which comprises incorporating into said fuel or lubricating oil a minor proportion of at least one demulsifier additive comprising a mixture of: A) one or more reaction products of a hydrocarbon-substituted succinic acid or anhydride with one or more polyalkylene glycols or mono-ethers thereof, wherein said hydrocarbon substituent is an alkyl or alkenyl radical having at least 4 but not less than 50 carbon atoms, B) one or more organic basic metal salts, and (C) one or more alkoxylated amines.

22. The concentrate of claim 20 wherein the demulsifier additive constitutes not more than 30% by weight of said concentrate.

23. The concentrate of claim 22 wherein the hydrocarbon substituent is component (A) has 6 to 30 carbon atoms.

24. The concentrate of claim 22 or 23 wherein the metal salt in component (B) is an alkaline earth metal salt.

25. The concentrate of claim 22, 23 or 24 wherein the alkoxylated amine is selected from ethoxylated and propoxylated tertiary and secondary amines.

26. The concentrate of claim 23 wherein the hydrocarbon substituent in (A) has from 8 to 16 carbon atoms and the basic metal salt in (B) is an alkaline earth metal salt.

27. The concentrate of claim 26 wherein the alkoxylated amine has at least one group of the formula -NR1R2 wherein R1 is salkylene-O+,H in which alkylene contains not more than 6 carbon atoms, and n is a number of 1 to 10, and R2 is selected from hydrogen, alkyl or not more than 18 carbon atoms, and R1.

28. The concentrate of claim 27 wherein the alkoxylated amine is a tertiary amine having from 2 to 1S (!M alkylene-O) units.

29. The concentrate of claim 27 wherein the hydrocarbon substituent in (A) is a dodecyl group, the salt (B) is a magnesium salt, and the alkoxylated amine is an ethoxylated tertiary amine having 5 ethenoxy groups.

30. The method of claim 21 in which components (A) and (B) are mixed first and heated at 50--125"C. for not more than 3 hours.

31. The method of claim 30 wherein (A) is the reaction product of a hydro carbon-substituted succinic anhydride with polyoxyethylene glycol having an average molecular weight of 200 to 600, and (B) is a basic alkaline earth metal salt.

32. The method of claim 31 wherein the hydrocarbon substituent of (A) has from 6 to 30 carbon atoms and the alkoxylated amine of (C) is a tertiary amine.

33. A fuel composition having demulsifying properties resulting from the incorporation of 1 to 200 parts per million based on the fuel of a demulsifier additive comprising a mixture of: (A) one or more reaction products of a hydrocarbon-substituted succinic acid or anhydride with one or more polyalkylene glycols or mono-ethers thereof, wherein said hydrocarbon substituent is an alkyl or alkenyl radical having at least but less than 50 carbon atoms, (B) one or more organic basic metal salts, and (C) one or more alkoxylated amines.

34. A lubricant composition according to claim 1 substantially as described in any of Examples A to G.

35. A normally liquid fuel or lubricant composition having a major proportion of a normally liquid fuel or lubricating oil, said composition having been prepared by a method according to any one of claims 21 and 30 to 32.