GB2105743A - Fuel economy additives or lubricants - Google Patents

Abstract

Fuel economy of internal combustion engines, especially gasoline engines, is improved by lubricating such engines with lubricant compositions comprising A. at least one tartrate of the formula <IMAGE> wherein each R is independently a hydrocarbon-based group and the sum of carbon atoms in both the R groups is at least about 8; and B. at least one oil-soluble detergent and dispersant.

Description

SPECIFICATION Compositions, concentrates, lubricant compositions and methods for improving fuel economy of internal combustion engines Background of the invention This invention relates to compositions and methods for improving the operation of internal combustion engines, specifically by reducing the amount of fuel consumed by such engines. More particularly, the invention comprises lubricating composition which may be used in such engines to decrease fuel consumption, and a method of using such lubricating compositions to accomplish this purpose.

Efforts to reduce the amount of fuel consumed by internal combustion engines such as automobile engines have increased in recent years as a result of the petroleum shortage, the increased cost of petroleum products, and the desire for conservation of natural resources such as petroleum. It is recognized that a situation under which fuel consumption is minimized is desirable, both because of the conservation factor and because such a situation is economical for the user of the engine.

Many of the proposed solutions to the fuel conservation problem have been mechanical, as for example, adjusting the engine for a leaner burn or simply building smaller cars and smaller engines.

Other efforts have related to developing lubricants that reduce the overall friction of the engine thereby reducing energy requirements. Some synthetic lubricants have been developed and compounded for use in the automobile engine to reduce fuel consumption. A considerable amount of effort has been expended toward developing additives for use in mineral lubricating oils and greases to reduce the friction properties of the oils and greases.

Oil-soluble aliphatic polycarboxylic acids including those wherein the aliphatic group contains one or more hydroxyl groups have been suggested as additives for use in mineral lubricating oils and motor fuels to improve the performance of the oils and motor fuels. U.S. Patents 2,370, 299 and 2,370,300 describe compounded lubricants comprising lubricating oil containing organic esters which comprise an aliphatic alcohol of from 10 to 30 carbon atoms esterified with a hydroxy aliphatic acid having at least one hydroxyl group. The presence of the organic ester decreases the coefficient of friction between metal frictional surfaces at low rubbing speeds.

Lubricating oils and motor fuels containing derivatives of tartaric acid with various amines and amino alcohols are described in U.S. Patents 2,977,309; 2,865,723: 2,811,429; 3,183,069 and 4,237,022. In general, the rust inhibition and anti-oxidation properties of the lubricants and fuels are improved by these amino derivatives.

U.S. Patent 2,715,108 describes a lubricating oil useful particularly as a turbine oil which contains an additive amount of a mixture of an aliphatic polycarboxylic acid or partial ester thereof, and oil-soluble phenolic compound or its thio or seleno analogs, and an aromatic carboxylic acid. This mixture added to a turbine oil results in improved rust and corrosion inhibition and improved resistance to emulsification in the presence of water. Mineral oils containing a small amount of an ester of a trialkylammonium acid salt of a hydroxy aliphatic dicarboxylic acid and a primary, aliphatic, monohydric alcohol are described in U.S. Patent 2,585,877. In addition to the beneficial effects on rust inhibition, the additive improves the anti-wear properties and cutting efficiencies of mineral oils.Extreme pressure lubricants containing compounds obtained by reacting aliphatic hydroxy carboxylic acids and lower aliphatic polyhydric alcohols are described in U.S. Patent 2,755,250. Mineral transformer oils are described in U.S. Patent 2,397,332 which include a small amount of a tartaric di-acid ester of a cyclic alcohol. The extreme pressure properties of lubricants are reported to be improved in U.S. Patent 2,628,941 by incorporating into lubricating compositions a reaction product obtained by reacting a polyacidic compound containing from 1 to 3 free carboxylic acid groups and at least one hydroxy group with an alkylene oxide, an alkylene sulfide or an alkylene imine.

Summary of the invention In its broadest sense, the present invention provides a multicomponent composition comprising A. at least one tartrate of the formula

wherein each R is independently a hydrocarbon-based group and the sum of carbon atoms in both the R groups is at least about 8; and B. at least one oil soluble detergent and dispersant; and the use of such compositions in lubricating oils for internal combustion engines. Lubricating oils containing the compositions of the invention are effective in reducing the amount of fuel consumed by internal combustion engines. The invention also relates to a method of reducing the amount of fuel consumed by an internal combustion engine.The lubricants also can contain other additives such as corrosion- and oxidation-inhibiting agents, pour point depressing agents, viscosity-improving components, color stabilizers and anti-foam agents.

Description of the preferred embodiments As mentioned above, the multi-component compositions of the invention comprise, in the broadest sense, component A which is at least one tartrate and component B which is an oil-soluble detergent or dispersant, or mixtures thereof.

Component A-the tartrate Component A of the compositions of the invention is at least one tartrate of the formula

wherein each R is independently a hydrocarbon-based group, and the sum of the carbon atoms in both R groups is at least about 8.

One method of preparing the tartrates represented by the above formula involves esterification of tartaric acid with an alcohol or mixtures of alcohols which are preferably monohydric alcohols.

The monohydric alcohols which can be employed to provide the tartrate compounds with the desired R groups are well known and can comprise, for example, primary and secondary aliphatic alcohols. The preferred monohydric alcohols, however, are primary aliphatic alcohols, especially aliphatic hydrocarbon alcohols such as alkenols and alkanols of from about 4 to about 40 carbon atoms, and preferably from about 8 to about 40 carbon atoms. Mixtures of alcohols can be utilized provided that the total number of carbon atoms in the two R groups is at least about 8. More preferably, each R group is derived from a monohydric alcohol containing at least 8 carbon atoms.

Accordingly, examples of the preferred monohydric alcohols from which the R group is derived include 1 -octanol, 1 -decanol, 1 -dodecanol, 1 -tetradecanol, 1 -hexadecanol, 1 -octadecanol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, phytol, myricyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol.

Of course, commercial alcohols (mixtures) are contemplated herein, and these commercial alcohols may comprise minor amounts of alcohols which, although not specified herein, do not detract from the major purposes of this invention. Higher synthetic monohydric alcohols of the type formed by the Oxo process (e.g., 2-ethylhexyl), the aldol condensation, or by organoaluminum-catalyzed oligomerization of alpha-olefins (especially ethylene), followed by oxidation, also are useful.

Examples of some preferred monohydric alcohols and alcohol mixtures suitable for forming the tartrates useful in the compositions of the invention include commercially available "Alfol" alcohols marketed by Continental Oil Corporation. Alfol 810 is a mixture containing alcohols consisting essentially of straight chain, primary alcohols having from 8 to 10 carbon atoms. The Alfol 20+ alcohols are mixtures of C 18-C28 primary alcohols having mostly, on an alcohol basis, C20 alcohols as determined by GLC (gas-liquid-chromatography). The Alfol 22+ alcohols are C18-C28 primary alcohols having mostly, on an alcohol basis, C22 alcohols. These Alfol alcohols can contain a fairly large percentage (up to 40% by weight) of paraffinic compounds which can be removed before the esterification reaction if desired.

Another example of a commercially available alcohol mixture is Adol 60 which comprises about 75% by weight of a straight chain C22 primary alcohol, about 15% of a C20 primary alcohol and about 8% of C18 and C24 alcohols. Adol 60 is marketed by Ashland Chemical.

A variety of mixtures of monohydric fatty alcohols derived from naturally occurring triglycerides and ranging in chain length of from C8 to C18 are available from Procter 8 Gamble Company. These mixtures contain various amounts of fatty alcohols containing mainly 12, 14, 16, or 18 carbon atoms.

For example, CO-1214 is a fatty alcohol mixture containing 0.5% of C,O alcohol, 66.0% of C12 alcohol, 26.0% of C14 alcohol and 6.5% of C,6 alcohol.

Another group of commercially available mixtures include the "Neodol" products available from Shell Chemical Co. For example, Neodol 23 is a mixture of C12 and C13 alcohols; Neodol 25 is a mixture of C12 and C18 alcohols; and Neodol 45 is a mixture of C14 and Cas alcohols.

Fatty vicinal diols also are useful and these include those available from Ashland Oil under the general trade designation Adol 114 and Adol 158. The former is derived from a straight chain alpha olefin fraction of C11C14, and the latter is derived from a C18-C18 fraction.

Examples of preferred branched chain monohydric alcohols suitable for forming the tartrates useful in the present invention include, for example, commercial tridecyl alcohol corresponding in large part substantially to the formula CH3CH2CH (CH3)CH(CH3)CH(CH3)CH(CH3)CH2CH2CH20H prepared by the Oxo process and which is available from Exxon Corporation, hexadecyl alcohol prepared by the Oxo process, 1 2-methylpentadecyl alcohol, 6-methyídecyl alcohol, 8-ethyltetradecyl alcohol, 5,6-dipropyldecyl alcohol as well as mixtures of these alcohols. Branched chain alcohols of from 12 to 14 carbon atoms with one or more methyl branches are the more preferred.

The tartrates represented by the above formula can be obtained by esterification of tartaric acid with one or more of the above described alcohols under conditions which are typical for effecting esterification. Such conditions include, for example, a temperature of up to the reflux temperature of the mixture provided that the temperature is maintained at a level below the decomposition of the reaction mixture or any products thereof. Water normally is removed as the esterification proceeds.

These conditions optionally may include the use of an excess amount of alcohol over the stoichiometric requirements for complete esterification with the alcohols in order to facilitate the esterification reaction.

Generally, the esterification reaction is conducted in a substantially inert, normally liquid, organic solvent or diluent such as mineral oil, toluene, benzene, xylene and the like. Esterification catalysts are included in the mixture, and these catalysts include toluene sulfonic acid, sulfuric acid, aluminum chloride, boron trifluoride-triethylamine, methane sulfonic acid, hydrochloric acid, ammonium sulfate, phosphoric acid, sodium methoxide, etc.

The following examples illustrate the procedure for preparing the tartrates useful as component A in the compositions of the invention. Unless otherwise indicated, all parts and percentages are by weight.

Example 1-A A mixture of 1 53 parts of DL tartaric acid hydrate, 400 parts of Procter s Gamble's CO-1214, an alcohol mixture containing principally C12 and C14 aliphatic alcohols, one part of toluenesulfonic acid and 500 parts of toluene is heated to the reflux temperature of the mixture. Nitrogen is blown below the surface of the liquid and water is removed as the temperature reaches 1900 C. A total of 35 parts of water are collected. The residue is filtered through a filter aid, and the filtrate is the desired product.

Example 2-A A mixture of 95 parts of meso-tartaric acid, 226 parts of the alcohol mixture used in Example 1, and 0.5 part of toluene sulfonic acid is heated to reflux with nitrogen blowing. At a temperature of 16000, 25 parts of water are collected. The mixture is cooled to 145--1 550C and heated for an additional two hours. The reaction mixture is filtered through a filter aid, and the filtrate is the desired product.

Example 3-A A mixture of 800 parts of the alcohol mixture of Example 1 and 14 parts of water is heated to 5000 whereupon sulfuric acid (107 parts) is added dropwise over a period of two hours and the temperature of the mixture reaches 600 0. Potassium bitartrate (376 parts) is added over ten minutes using high speed stirring followed by heating to a temperature of about 9400 for one hour. Xylene (500 ml.) is added and the mixture is heated to reflux while collecting water. The temperature of the reaction mixture reaches 16500 near the end of the esterification. 85 parts of water are collected. The residue is stripped at 14000 and 30 mm. Hg. This residue is filtered through a filter aid, and the filtrate is the desired product.

Example 4-A A mixture of 1 50 parts of tartaric acid, 288 parts of Alfol 810 (a commercial mixture of C8 and C10 aliphatic alcohols), 1.12 parts of paratoluene sulfonic acid and 400 parts of toluene is heated to reflux while collecting water in a sidearm trap. A total of 34 parts of water was collected. The mixture is stripped to 1 5000/25 mm Hg. Calcium hydroxide (0.44 parts) is added with stirring for ten minutes at 800 C, and the mixture is filtered through a filter aid. The filtrate is the desired product.

Example 5-A A mixture of 75 parts of tartaric acid, 468 parts of Alfol 22+ S.P. and 1 part of para-toluene sulfonic acid is prepared and 400 parts of toluene is added. The mixture is heated to reflux for a total of thirteen hours and a total of 16 parts of water is collected. The residue is stripped at 12000/25 mm.

Hg. and filtered through a filter aid. The filtrate is the desired product having a saponification number of 96.3 (theory is 107).

Example 6-A A mixture of 199 parts of tartaric acid, 71 8 parts of commercial alcohol mixture available from Procter s Gamble under the general designation "C01895F" containing about 2% C,6 and 96% C18 fatty alcohols, and 1.1 part of para-toluene sulfonic acid is prepared and 500 parts of toluene is added.

This mixture is heated to reflux for a total heating time of about thirteen hours, and 47 parts of water is collected in a sidearm trap. The mixture is stripped at 135 C/25 mm. Hg. The residue is filtered through a filter aid, and the filtrate is the desired product having a saponification number of 1 71 (theory is 172) and a melting point of 8081 OC.

Example 7-A A mixture of 1 50 parts of tartaric acid, 590 parts of Aldol 1 58 (a commercial diol mixture available from Ashland Chemicals), 500 parts of toluene and 1.1 part of para-toluene sulfonic acid is heated to reflux while collecting 33 parts of water in a sidearm trap. The reaction mixture is stripped to 100 C/25 mm. Hg., and the residue is filtered through a filter aid. The filtrate is the desired product having a saponification number of 168 (repeat 157; theory is 159).

Example 8-A A mixture of 1 50 parts of tartaric acid, 414 parts of Neodol 23 (a commercial mixture of C12 and C13 alcohols), 1 part of para-toluene sulfonic acid and 500 parts of toluene is prepared and heated to reflux. Water (36 parts) is collected in a sidearm trap. The mixture then is stripped at 1 35 OC/27 mm.

Hg. and filtered through a filter aid. The filtrate is the desired product having a saponification number of 218 (theory is 212) and a melting point of 5556 C.

Example 9-A A mixture of 1 50 parts of tartaric acid, 436 parts of Neodol 45 (a commercial mixture of C14 and Cas alcohols), 1 part of para-toluene sulfonic acid and 500 parts of toluene is heated to reflux. Water (35 parts) is collected in a sidearm trap. The reaction mixture then is stripped at 1 100C/21 mm. Hg.

and filtered through a filter aid. The filtrate is the desired product having a saponification number of 189 (theory is 204).

Example 10-A A mixture of 112.5 parts of tartaric acid, 480 parts of Adol 60 (a commercially available alcohol containing about 75% by weight of a straight chain C22 primary alkanol, about 15% of a C20 alcohol and about 8% of a mixture of C18 and C24 alcohols), 400 parts of toluene and 1 part of paratoluene sulfonic acid is heated to reflux. Water (25.5 parts) is collected in a sidearm trap. The mixture is stripped at 11 50C/22 mm. Hg. and filtered through a filter aid. The filtrate is the desired product having a saponification number of 139 (theory is 149).

Example 11-A A mixture is prepared comprising 163 parts (2.2 moles) of n-butanol, 400 parts (2 moles) of the commercial mixture of alcohols of Example 1, 1 50 parts of tartaric acid (2 moles), 1 part of paratoluene sulfonic acid and 1000 parts of toluene. This mixture is heated to reflux while collecting water (76 parts) in a sidearm trap. The mixture is stripped at 1000C/17 mm. Hg. and filtered through a filter aid. The filtrate is the desired product having a saponification number of 260 (theory is 283).

Example 12-A A mixture of 1500 parts of tartaric acid, 4000 parts of the commercial alcohol mixture of Example 1, 2000 parts of toluene and 1 0 parts of para-toluene sulfonic acid is heated to reflux while removing 360 parts of water (theory is 360 parts). The reaction mixture is stripped at 1 050C/23 mm.

Hg. Calcium hydroxide (4 parts) is added at 1 000C with stirring for fifteen minutes. The reaction mixture is filtered through a filter aid, and the filtrate is the desired product.

Example 13-A A mixture of 1 50 parts of tartaric acid, 484 parts of an alcohol mixture available from Procter 8 Gamble under the trade designation CO-1418 (comprising 14% C,2; 35 47% C14; 1527% C,6 and 30--40% C18 alcohols), 400 parts of toluene and 2 parts of para-toluene sulfonic acid is prepared and heated to reflux while removing water through a sidearm trap. The mixture then is stripped to 1220C at 16 mm. Hg. The residue is filtered while hot through a filter aid, and the filtrate is the desired product.

Example 14-A A mixture of 1 020 parts of potassium bitartrate and 2000 parts of the alcohol mixture of Example 1 is prepared, and 737 parts of hydrochloric acid (37%) are added dropwise over a period of about twenty minutes. The mixture is heated while purging with nitrogen, and water is collected over a period of one hour of heating at about 105--1 150C. Heating is continued to 1400C over a period of seven hours while removing additional water. After cooling overnight, the mixture is reheated to about 1 550C and maintained at this temperature for about two hours while removing additional water. The mixture then is filtered at about 900C through a filter aid, and the filtrate is the desired product.

Example 15-A To a mixture of 2000 parts of the alcohol mixture of Example 1 and 49 parts of water there is added 383 parts of sulfuric acid (96%) over a period of twenty minutes, followed by the addition of 1 020 parts of potassium bitartrate over a period of ten minutes. This mixture is heated while purging with nitrogen, and water is removed beginning at about 1 200C and up to a temperature of about 1 550C. After cooling overnight, the mixture is reheated to a temperature of about 1 55-1 650C while removing additional water. The total heating time at esterification temperature is seven hours. The mixture is filtered at about 900C through a filter aid, and the filtrate is the desired product.

Example 16-A A mixture of 882 parts of maleic anhydride, 819 parts of water and 21.78 parts of anhydrous sodium molybdate is prepared and warmed gently until the maleic anhydride dissolves. The mixture is heated to about 750C under a vacuum of about 20 inches of mercury to allow gentle reflux. While maintaining the vacuum at about 1921 inches of mercury, 1525 parts of 30% aqueous hydrogen peroxide is added over a period of 3.75 hours at 73-780C with external heating applied only as necessary to maintain this temperature range. The yellow solution becomes orange-red indicating the absence of peroxide and the conversion of the maleic anhydride to tartaric acid.

A mixture of 2828 parts of the tartaric acid solution prepared above, 2994 parts of the alcohol mixture of Example 1, and 41 parts of phosphoric acid (85%) is prepared and heated under a nitrogen flow to 1 650C over several hours while removing water by distillation. The mixture is held at 1 650C for a total of twelve hours, and after cooling to 500 C, 30 parts of calcium hydroxide is added at once.

Vacuum is applied, and the mixture is heated to 1 450C at 20 mm. Hg. The reaction mixture is filtered through a filter aid, and the filtrate is the desired product.

Component B-the detergent or dispersant The terms "detergent" and"dispersant" as used in the lubricant art generally mean, respectively, a composition which is capable of removing deposits from engine parts and a composition which is capable of retaining such deposits in suspension in the oil once they are removed. For the most part, detergents comprise basic metal salts or complexes of various organic compositions (normally acidic) containing both a polar and a non-polar group, while dispersants comprise compositions also containing a polar and a non-polar group but which are metal-free or, if they contain metal, contain at most about 1.1 equivalents thereof per equivalent of acidic moieties. Both detergents and dispersants will be more fully characterized hereinafter, although their general nature is well known to the skilled lubricant chemist.

Detergents As noted above, most detergents are basic metal salts or complexes of a phenol, sulfonic acid, carboxylic acid or phosphorus acid. The metals are usually alkali metals or alkaline earth metals; that is, they are members respectively of Group IA and Group IIA of the Periodic Table. For the purpose of the present invention, alkaline earth metal salts are preferred. The preferred alkaline earth metals are magnesium, calcium, strontium and barium, particularly calcium or barium and still more particularly calcium.

The non-metallic moiety of the salt or complex is ordinarily the anion of an organic acidic compound. Examples of such compounds are phenols, sulfonic acids, carboxylic acids and phosphorus acids.

The word "phenol", as used herein, denotes any hydroxyaromatic compound including hydroxy compounds derived from fused-ring hydrocarbons (e.g., naphthols and the like). Especially preferred in the preparation of component B are phenols substituted with aliphatic or cycloaliphatic groups having at least about 6 carbon atoms and up to as many as 7000 carbon atoms. Examples of such groups are hexyl, cyclohexyl, heptyl, decyl, eicosyl, and groups derived from the polymerization of olefins such as ethylene, propylene, 1 -butene, 2-butene, isobutene and the like.Groups derived from polymers of propylene and commercial mixtures of butenes (comprising predominantly isobutene) are preferred, especially those having a number average molecular weight (as determined, for example, by gel permeation chromatography) of about 1 50-1750 (containing about 10-125 aliphatic carbon atoms). The substituent and the aryl nucleus of the phenol may contain other groups such as hydroxy, nitro, nitroso and sulfo groups.

Introduction of the aliphatic or cycloaliphatic substituent onto the phenol can be effected by mixing the hydrocarbon (or a halogenated derivative thereof, or the like) and the phenol at a temperature of about 50-2000C in the presence of a suitable catalyst, such as aluminum trichloride, boron trifluoride, zinc chloride or the like. The substituent can also be introduced by other alkylation processes known in the art. It is irrelevant which position on the phenolic ring is substituted; any single isomer, or a mixture of isomers, may be used. Polysubstituted materials such as dialkyl and trialkyl phenols may also be present, either alone or in admixture with monoalkyl phenols.

Additional suitable phenols are polyphenols containing sulfur or alkylene bridges, typically prepared by reaction of a simple phenol with sulfur, a sulfur halide such as sulfur monochloride or dichloride, or a lower aliphatic aldehyde (preferably formaldehyde). Polyphenols containing both sulfur and alkylene bridges are also suitable.

The equivalent weight of a phenol for the purpose of this invention is its molecular weight divided by the number of phenolic hydroxy groups therein. Thus, the equivalent weight of an alkylated phenol is equal to its molecular weight and that of an alkylated resorcinol is half its molecular weight.

The phosphorus acids useful in the preparation of component B may contain pentavalent or trivalent phosphorus. The pentavalent phosphorus acids, which are preferred, may be represented by the formula

wherein each R is independently hydrogen or a hydrocarbon-based group, at least one thereof being hydrocarbon-based: each X is independently oxygen or sulfur; and each a is independently 0 or 1. Thus, it will be appreciated that the phosphorus acid may be an organophosphoric, phosphonic or phosphinic acid, or a thio analog of any of these.

The term "hydrocarbon-based" as used herein denotes a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character within the context of this invention. Such groups include the following: (1) Hydrocarbon groups; that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatic- and alicyclic-substituted aromatic, aromatic-substituted aliphatic and alicyclic groups, and the like, as well as cyclic groups wherein the ring is completed through another portion of the molecule (that is, any two indicated substituents may together form an alicyclic group).

(2) Substituted hydrocarbon groups; that is, hydrocarbon based groups as defined above also containing non-hydrocarbon substituents which, in the context of this invention, do not alter the predominantly hydrocarbon character of the group. Those skilled in the art will be away of suitable substituents; examples include halo, nitro, hydroxy, alkoxy, alkylthio, carbalkoxy and acyl groups.

(3) Hetero groups; that is, groups 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 group.

Included among the suitable phosphorus acids are those prepared by the treatment of an olefin polymer (e.g., a polybutene having a molecular weight of about 1000) with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride.

The equivalent weight of a phosphorus acid is its molecular weight divided by the number of hydroxy groups bonded to phosphorus therein.

Carboxylic acids suitable for use in the preparation of component B include aliphatic, cycloaliphatic and aromatic mono- and polybasic carboxylic acids free from acetylenic unsaturation, including naphthenic acids, alkyl- or alkenyl-substituted cyclopentanoic acids, alkyl- or alkenylsubstituted cyclohexanoic acids, and alkyl- or alkenyl-substituted aromatic carboxylic acids (including salicylic acids). The aliphatic acids generally contain at least 8 and preferably at least 12 carbon atoms.

The cycloaliphatic and aliphatic carboxylic acids can be saturated or unsaturated. Specific examples include 2-ethylhexanoic acid, linolenic acid, propylene tetramer-substituted maleic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic acid, ricinoleic acid, undecylic acid, dioctylcyclopentanecarboxylic acid, myristic acid, dilauryldecahydronaphthalenecarboxylic acid, stearyl-octahydroindenecarboxylic acid, palmitic acid, acids formed by oxidation of petrolatum or of hydrocarbon waxes, and commercially available mixtures of two or more carboxylic acids such as tall oil acids, rosin acids, and the like. The equivalent weight of any such acid is its molecular weight divided by the number of carboxy groups present therein.

The sulfonic acids useful in the preparation of detergents suitable for use as component B include mahogany sulfonic acids, petrolatum sulfonic acids, mono- and polywax-substituted naphthalene sulfonic acids, cetylchlorobenzene sulfonic acids, cetylphenol sulfonic acids, cetylphenol disulfide sulfonic acids, cetoxycapryl benzene sulfonic acids, dicetyl thianthrene sulfonic acids, di-lauryl betanaphthol sulfonic acids, dicapryl nitro-naphthalene sulfonic acids, paraffin wax sulfonic acids, unsaturated paraffin wax sulfonic acids, hydroxy-substituted paraffin wax sulfonic acids, tetraisobutylene sulfonic acids, tetraamylene sulfonic acids, chloro-substituted paraffin wax sulfonic acids, nitroso-substituted paraffin wax sulfonic acids, petroleum naphthene sulfonic acids, cetylcyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic acids, mono- and polywax-substituted cyclohexyl sulfonic acids, postdodecylbenzene sulfonic acids, "dimer alkylate" sulfonic acids, and the like. These sulfonic acids are well known in the art and require no further discussion herein.

For the purpose of this invention, the equivalent weight of a sulfonic acid or derivative thereof is its molecular weight divided by the number of sulfonic acid groups or sulfonic acid derivative groups present therein. Thus, for a monosulfonic acid the equivalent weight is equal to the molecular weight.

The basic salts and complexes useful as component B are well known in the art and are disclosed in many United States patents of which the following are exemplary: 2,616,904 3,031,284 3,410,671 2,616,905 3,256,186 3,437,465 2,695,910 3,312,618 3,629,109 2,723,234 3,342,733 3,746,643 2,777,874 3,350,308 3,764,533 2,781,403 3,410,670 The above patents as well as German published application 1,243,915 are incorporated by reference herein for their disclosures of basic salts and complexes. The salts and complexes useful in the present invention are those disclosed in said patents both generically and in the working examples, and include those disclosed merely as intermediates for conversion into more highly basic salts and complexes.

The commonly employed method for the preparation of these basic salts and complexes involves heating a solution of the organic acid compound in a substantially inert, normally liquid organic diluent such as mineral oil with a stoichiometric excess of a metal neutralizing agent such as the oxide, hydroxide, carbonate, bicarbonate or sulfide at a temperature above 500C and filtering the resulting mass. A "promoter" is often used in the neutralization step to aid the incorporation of a large excess of metal.Examples of compounds useful as promoters include phenolic compounds such as phenol, naphthol, alkylphenols, thiophenols, sulfurized alkylphenols, and condensation products of phenols with formaldehyde; alcohols such as methanol, 2-propanol, actyl alcohol, Cellosolve, Carbitol, ethylene glycol, stearyl alcohol and cyclohexyl alcohol; and amines such as aniline, phenylene diamine, phenothiazine, phenyl-beta-naphthylamine and dodecylamine. It is also frequently preferred to further treat the basic compound prepared as described above with an acidic gas, especially carbon dioxide.

This treatment may be intermittent and followed by successive treatments with the metal neutralizing agent, and often enables the incorporation of still larger amounts of basic metal in the complex.

The preferred organic acidic compounds for use in the preparation of the detergent are the above described sulfonic and carboxylic acids, especially those having an equivalent weight of about 300500. The sulfonic acids are most often used, and a particular preference is expressed for alkylaromatic sulfonic acids and more particularly for alkylbenzene sulfonic acids.

The preferred detergents are the basic alkali or alkaline earth metal salts of carboxylic and sulfonic acids. Particularly useful as detergents are the oil-soluble basic calcium sulfonates.

Dispersants Oil-dispersible dispersants are particularly useful as component B in the present invention. As previously noted, these dispersants are generally metal-free or contain relatively small amounts of metal in comparison to the detergents described above. Their characterizing feature, with respect to molecular structure, is the presence of an oil-solubilizing aliphatic hydrocarbon-based group containing at least about 40 aliphatic carbon atoms bonded directly to a polar group. The dispersant may contain more than one of either of such groups per molecule, as will be apparent from the description hereinafter.

Many dispersants of this type are known in the art and are described in various patents. Any of such dispersants are suitable for use in the compositions and methods of this invention. The following are illustrative: (1) Reaction products of carboxylic acids (or dervatives thereof) containing at least about 44 and preferably at least about 54 aliphatic carbon atoms with nitrogen-containing compounds having at least one > NH group such as amines, ureas and hydrazines, with organic hydroxy compounds such as phenols and alcohols, and/or with reactive basic inorganic materials.Examples of these products, referred to herein as "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 aliphatic or alicyclic halides containing at least about 40 carbon atoms 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 40 carbon atoms with aliphatic aldehydes containing at most about 7 carbon atoms (especially formaldehyde) and amines (especially alkylene polyamines), which may be characterized as "Mannich dispersants".

The materials described in the following U.S. patents are illustrative: 2,459,112 3,442,808 3,591,598 2,962,442 3,448,047 3,600,372 2,984,550 3,454,497 3,634,515 3,036,003 3,459,661 3,649,229 3,166,516 3,461,172 3,697,574 3,236,770 3,493,520 3,725,277 3,355,270 3,539,633 3,725,480 3,368,972 3,558,743 3,726,882 3,413,347 3,586,629 3,980,569 (4) Polymers containing an oil-solubilizing group (e.g., a pendant alkyl group having at least about 8 carbon atoms) and a polar group. Illustrative are interpolymers of decyl methacrylate, vinyl decyl ether or a relatively high molecular weight olefin with aminoalkyl acrylates, aminoalkyl acrylamides or poly-(oxyalkylene)-substituted alkyl acrylates, as well as copolymers of styrene, alkyl maleates and maleic acid am ides or imides.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 3,687,843 3,519,565 3,702,300 (5) Products obtained by post-treating the carboxylic, amine, Mannish or polymeric dispersants with such reagents as sulfur, urea, thiourea, guanidine, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or the like.Products of these types are described in German published application (OLS) 2,551,256 and 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 4,161,475 The disclosures of all of the above-listed patents and applications are incorporated herein by reference.

The carboxylic and Mannich dispersants are preferred. Carboxylic dispersants may be most conveniently and accurately described in terms of the groups (B-l and 8-2) present therein. Group 8-1 is usually an acyl, acyloxy or acylimidoyl group containing at least about 44 carbon atoms. The structures of these groups, as defined by the International Union of Pure and Applied Chemistry, are as follows (each R2 individually representing a hydrocarbon or similar group): Acyl: Acyloxy:

Acylimidoyl:

Group B-2 is preferably at least one group in which a nitrogen or oxygen atom is attached directly to said acyl, acyloxy or acylimidoyl radical, said nitrogen or oxygen atom also being attached to a hydrocarbon-based group.The carboxylic dispersants are conveniently classified as "nitrogen-bridged dispersants" and "oxygen-bridged dispersants" wherein the atom attached directly to radical B-1 is nitrogen or oxygen respectively.

The nitrogen-bridged carboxylic dispersants, which will be described first, are those disclosed (for example) in the above-mentioned U.S. Patents 3,219,666 and 3,272,746 which also describe a large number of methods for their preparation.

The source of group B-1 in the nitrogen-bridged dispersants is an acylating agent comprising a carboxylic acid-producing compound containing a hydrocarbon or substituted hydrocarbon substituent which has at least about 40 and preferably at least about 50 carbon atoms. By "carboxylic acidproducing compound" is meant an acid, anhydride, acid halide, ester, amide, imide, amidine or the like; the acids and anhydrides are preferred.

The carboxylic acid-producing compound is usually prepared by the reaction (more fully described hereinafter) of a relatively low molecular weight carboxylic acid such as maleic acid, fumaric acid, maleic anhydride, etc., or derivative thereof with a hydrocarbon source containing at least about 40 and preferably at least about 50 carbon atoms. The hydrocarbon source is usually aliphatic and should be substantially saturated, i.e., at least about 95% of the total number of carbon-to-carbon covalent linkages should be saturated. It should also be substantially free from pendant groups containing more than about six aliphatic carbon atoms. It may be a substituted hydrocarbon source; by "substituted" is meant sources containing substituents which do not alter significantly their character or reactivity.

Examples are halide, hydroxy, ether, keto, carboxy, ester (especially lower carbalkoxy), amide, nitro, cyano, sulfoxy and sulfone radicals. The substituents, if present, generally comprise no more than about 10% by weight of the hydrocarbon source.

The preferred hydrocarbon sources are those derived from substantially saturated petroleum fractions and olefin polymers, particularly polymers of monoolefins having from 2 to about 30 carbon atoms and more particularly from 2-1 6 carbon atoms. Thus, the hydrocarbon source may be derived from a polymer of ethylene, propene, 1-butene, isobutene, 1-octene, 3-cyclohexyl-1-butene, 2-butene, 3-pentene or the like. Also useful are interpolymers of olefins such as those illustrated above with other polymerizable olefinic substances such as styrene, chloroprene, isoprene, p-methylstyrene, piperylene and dienes such as 1,3-hexadiene, isoprene, 1 ,4-hexadiene and 1,4-cyclohexadiene.In general, these interpolymers should contain at least about 80%, preferably at least about 95%, on a weight basis of units derived from the aliphatic monoolefins.

Another suitable hydrocarbon source comprises saturated aliphatic hydrocarbons such as highly refined high molecular weight white oils or synthetic alkanes.

In many instances, the hydrocarbon source should contain an activating polar group to facilitate its reaction with the low molecular weight acid-producing compound. The preferred activating groups are halogen atoms, especially chlorine, but other suitable groups include sulfide, disulfide, nitro, mercaptan, ketone and aldehyde groups.

As already pointed out, the hydrocarbon sources generally contain at least about 40 and preferably at least about 50 carbon atoms. Among the olefin polymers those having a number average molecular weight above about 600 are useful and those between about 1300 and about 5000 (as determined by gel permeation chromatography) are preferred, although higher polymers having molecular weights from about 10,000 to about 100,000 or higher may sometimes be used. The ratio of weight average to number average molecular weight (Mw/Mn) may be about 1.5-6.0 and is usually 1.54.0.

A first preferred class of polymers comprises those of terminal olefins such as propylene, 1- butene, isobutene and 1-hexene. Especially preferred within this class are polybutenes comprising predominantly isobutene units. A second preferred class comprises terpolymers of ethylene, a C 3-8 alpha-monoolefin and a polyene selected from the group consisting of non-conjugated dienes (which are especially preferred) and trienes.Illustrative of these terpolymers is "ortholeum 2052" manufactured by E. l. duPont de Nemours Et Company, which is a terpolymer containing about 48 mole percent ethylene groups, 48 mole percent propylene groups and 4 mole percent 1,4-hexadiene groups and having an inherent viscosity of 1.35 (8.2 grams of polymer in 100 ml. of carbon tetrachloride at 30 C).

Any one of a number of known reactions may be employed for the preparation of the carboxylic acid-producing compound. Thus, an alcohol of the desired molecular weight may be oxidized with potassium permanganate, nitric acid or a similar oxidizing agent; a halogenated olefin polymer may be reacted with a ketone; an ester of an active hydrogen-containing acid, such as acetoacetic acid, may be converted to its sodium derivative and the sodium derivative reacted with a halogenated high molecular weight hydrocarbon such as brominated wax or brominated polyisobutene; a high molecular weight olefin may be ozonized; a methyl ketone of the desired molecular weight may be oxidized by means of the haloform reaction; an organometallic derivative of a halogenated hydrocarbon or olefin polymer may be converted to a nitrile, which is subsequently hydrolized; or an olefin polymer or its halogenated derivative may undergo a reaction with an unsaturated carboxylic acid or derivative thereof such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, glutaconic acid, chloromaleic acid, aconitic acid, crotonic acid, methylcrotonic acid, sorbic acid, 3-hexenoic acid, 1 0-decenoic acid, 2-pentene-1,3,5-tricarboxylic acid, and the like, or with a halogen-substituted carboxylic acid or dervative thereof. This latter reaction is preferred, especially when the acid-producing compound is unsaturated and preferably when it is maleic acid or anhydride. The resulting product is then a hydrocarbon-substituted succinic acid or derivative thereof.The reaction leading to its formation involves merely heating the two reactants at a temperature from about 1000 to about 2000C. The mole ratio of the polymer to the maleic acid or anhydride may be equal to, greater than or less than 1, depending on the type of dispersant product desired. It is often preferred, however, to employ proportions such that the dispersant will contain an average of at least 1.3 succinic moieties per polymeric moiety; such dispersants are termed "polysuccinated dispersants". Especially preferred are polysuccinated dispersants containing about 1.43.5 succinic groups and most desirably about 1.52.5 succinic groups per polymer group.The substituted succinic acid or anhydride thus obtained, may, if desired, be converted to the corresponding acid halide by reaction with known halogenating agents such as phosphorus trichloride, phosphorus pentachloride or thionyl chloride.

The nitrogen-bridged carboxylic dispersants are prepared by reacting the acylating agent such as the substituted succinic acids or anhydrides with at least one nitrogen compound preferably having the structure NH wherein the two remaining valences of nitrogen are satisfied by hydrogen, amino or organic radicals bonded to said nitrogen atom through direct carbon-to-nitrogen linkages. These compounds include aliphatic, aromatic, heterocyclic and carbocyclic amines as well as substituted ureas, thioureas, hydrazines, guanidines, amidines, amides, thioamides, cyanamides and the like.

Among the amines useful in preparing the nitrogen-bridged dispersant are monoamines. These monoamines can be secondary, i.e., those containing only one hydrogen atom bonded directly to an amino nitrogen atom. Preferably, however, they contain at least one primary amino group, i.e., a group wherein an amino nitrogen atom is directly bonded to two hydrogen atoms. The monoamines are generally substituted with C,~30 hydrocarbon-based groups. Preferably these hydrocarbon-based groups are aliphatic in nature and free from acetylenic unsaturation and contain from about 1 to about 10 carbon atoms. Saturated aliphatic hydrocarbon groups are particularly preferred.

Among the preferred monoamines are those of the general formula HNR3R4, wherein R3 is an alkyl group of up to ten carbon atoms and R4 is hydrogen or an alkyl group of up to ten carbon atoms. Other preferred monoamines are aromatic monoamines of the general formula HNR5R6 wherein R5 is a phenyl, alkylated phenyl, naphthyl or alkylated naphthyl group of up to 10 carbon atoms and R6 is a hydrogen atom, an alkyl group of up to 10 carbon atoms, or a group similar to Rs. Examples of suitable monoamines are ethylamine, diethylamine, n-butylamine, di-n-butylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methyl laurylamine, oleylamine, aniline, methylaniline, Nmethylaniline, diphenylamine, benzylamine, tolylamine and methyl-2-cyclohexylamine.

Hydroxy amines are also included in the class of useful monoamines. Such compounds are the hydroxyhydrocarbyl-substituted analogs of the afore-described monoamines. Preferred hydroxy monoamines have the formulas HNR7R8 and HNR9R10, wherein R7 is an alkyl or hydroxy-substituted alkyl group of up to 10 carbon atoms, R8 is hydrogen or a group similar to R7, R9 is a hydroxysubstituted phenyl, alkylated phenyl, naphthyl or alkylated naphthyl group of up to 10 carbon atoms, anc R' is hydrogen or a group similar to R9, at least one of R7 and RB and at least one of R9 and R' being hydroxy-substituted.

Suitable hydroxy-substituted monoamines include ethanolamine, di-3-propanolamine, 4hydroxybutylamine, diethanolamine, N-methyl-2-propylamine, 3-hydroxyaniline, Nhydroxyethylethylene diamine, N,N-di-(hydroxypropyl)propylene diamine and tris)hydroxymethyl)methylamine. While in general, hydroxy amines containing only one hydroxy group will be employed as reactants, those containing more can also be used.

Heterocyclic amines are also useful in making the nitrogen-bridged dispersant, provided they contain a primary or secondary amine group. The heterocyclic ring can also incorporate unsaturation and can be substituted with hydrocarbon groups such as alkyl, alkenyl, aryl, alkaryl or aralkyl. In addition, the ring can also contain other hetero atoms such as oxygen, sulfur, or other nitrogen atoms including those not having hydrogen atoms bonded to them. Generally, these rings have from about 3 to about 10, preferably 5 or 6, ring members. Among such heterycycles are aziridines, azetidines, azolidines, pyridines, pyrroles, piperidines, imidazoles, indoles, piperazines, isoindoles, purines, morpholines, thiamorpholines, N-aminoalkyl morpholines. N-aminoalkyl thiamorpholines, azepines, azocines, azonines, azecines and tetrahydro-, dihydro- and perhydro- derivatives of each of the above.

Preferred heterocyclic amines are the saturated ones with 5- and 6-membered rings, especially the piperidines, piperazines and morpholines described above.

Polyamines are preferred for preparing the nitrogen-bridged dispersant. Among the polyamines are alkylene polyamines (and mixtures thereof) including those having the formula

wherein n is an integer between about 1 and about 10, preferably between 2 and 8; each A is independently hydrogen or a hydrocarbon or hydroxy-substituted hydrocarbon group having up to about 30 atoms; and R11 is a divalent hydrocarbon group having from about 1 to about 18 carbons.

Preferably A is an aliphatic group of up to about 10 carbon atoms which may be substituted with one or two hydroxy groups, and R" is a lower alkylene group having 110, preferably 2-6 carbon atoms.

Especially preferred are the alkylene polyamines wherein each A is hydrogen. Such alkylene polyamines include methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene polyamines and heptylene polyamines. The higher homologs of such amines and related aminoalkyl-substituted piperazines are also included.Specific examples of such polyamines include ethylene diamine, triethylene tetramine, tris(2-aminoethyl)amine, propylene diamine, trimethylene diamine, hexamethylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene)triamine, tripropyiene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di(trimethylene) triamine, 2-heptyl-3-(2 aminopropyl)imidazoline, 1 ,3-bis(2-aminoethyl)imidazoline, 1 -(2-aminopropyl)-piperazine, 1 ,4-bis(2- aminoethyl)piperazine and 2-methyl-1-(2-aminobutyl)-piperazine. Higher homologs, obtained by condensing two or more of the above-illustrated alkylene amines, are also useful, as are the polyoxyalkylene polyamines (e.g., "Jeffamines" available from Jefferson Chemical Co.).

The ethylene polyamines, examples of which are mentioned above, are especially useful for reasons of cost and effectiveness. Such polyamines are described in detail under the heading "Diamines and Higher Amines" in Kirk-Othmer, Encyclopedia of Chemical Technology, Second Edition, Vol. 7, pup.2239. They are prepared most conveniently by the reaction of an alkylene chloride with ammonia or by reaction of an ethylene imine with a ring-opening reagent such as ammonia. These reactions result in the production of the somewhat complex mixtures of alkylene polyamines, including cyclic condensation products such as piperazines. Becase of their availability, these mixtures are particularly useful in preparing the nitrogen-bridged dispersant. Satisfactory products can also be obtained by the use of pure alkylene polyamines.

Hydroxy polyamines, e.g., alkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atoms, are also useful in preparing the nitrogen-bridged dispersant. Preferred hydroxyalkyl-substituted alkylene polyamines are those in which the hydroxyalkyl group has less than about 10 carbon atoms. Examples of such hydroxyalkyl-substituted polyamines include N-(2hydroxyethyl)ethylene diamine, N,N'-bis(2-hydroxyethyl)-ethylene diamine, 1 -(2-hydroxyethyl)- piperazi ne, monohydroxypropyl-substituted diethylene triamine, dihydroxypropyltetraethylene pentamine and N-(3-hydroxybutyl)tetramethylene diamine. Higher homologs obtained by condensation of the above-illustrated hydroxyalkyl-substituted alkylene amines through amino groups or through hydroxy groups are likewise useful.

The dispersant can also be prepared from hydrazine or an organo-substituted hydrazine of the general formula

wherein each R12 is independently hydrogen or a C130 hydrocarbon radical, at least one R12 radical being hydrogen. Preferably, the others are C110 aliphatic groups. More preferably at least two R12 radicals are hydrogen, and most preferably at least two such groups bonded to the same nitrogen atom are hydrogen and the remaining ones are alkyl groups of up to 10 carbon atoms. Examples of suitable substituted hydrazines are methylhydrazine, N,N-dimethylhydrazine, N,N'-dimethylhydrazine, phenylhydrazine, N-phenyl-N'-ethylhydrazine, N-(p-tolyl)-N'-(n-butyl)hydrazine, N-(p-nitrophenyl)-Nmethylhydrazine, N,N'-di-(p-chlorophenyl)hydrazine and N-phenyl-N'-cyclohexylhydrazine.

For the formation of the nitrogen-bridged dispersant, the hydrocarbon-substituted succinic anhydride or acid, or other carboxylic acid-producing compound, and the alkylene polyamine or other nitrogen-containing reagent are heated to a temperature above about 800 C, preferably from about 1000 to about 2500C. The product thus obtained has predominantly amide, imide and/or amidine linkages (containing acyl or acylamidoyl groups). The process may in some instances be carried out at a temperature below 800C to produce a product having predominantly salt linkages (containing acyloxy groups). The use of a diluent such as mineral oil, benzene, toluene, naphtha or the like is often desirable to facilitate control of the reaction temperature.

The relative proportions of the carboxylic acid-producing compound and the alkylene polyamine or the like are such that at least about one-half the stoichiometrically equivalent amount of polyamine is used for each equivalent of carboxylic acid-producing compound. In this regard it will be noted that the equivalent weight of the alkylene polyamine is based upon the number of amine radicals therein, and the equivalent weight of the carboxylic acid-producing compound is based on the number of acidic or potentially acidic radicals. (Thus, the equivalent weight of a hydrocarbon-substituted succinic acid or anhydride is one-half its molecular weight). Although a minimum of one-half equivalent of polyamine per equivalent of acylating agent should be used, there does not appear to be an upper limit for the amount of polyamine.If an excess is used, it merely remains in the product unreacted without any apparent adverse effects. Ordinarily, about 1-2 equivalents of polyamine are used per equivalent of acylating agent.

In an alternative method for producing the nitrogen-bridged dispersant, the alkylene polyamine is first reacted with a low molecular weight, unsaturated or halogen-substituted carboxylic acid or derivative thereof (such as maleic anhydride or one of the others previously mentioned) and the resulting intermediate is subsequently reacted with the hydrocarbon source as previously described.

Oxygen-bridged carboxylic dispersants comprise the esters of the above-described carboxylic acids, as described (for example) in the aforementioned U.S. Patents 3,381,022 and 3,542,678. As such, they contain acyl or, occasionally, acylimidoyl groups as group B-1. (An oxygen-bridged dispersant containing an acyloxy group as group B-1 would be a peroxide, which is unlikely to be stable under all conditions of use of the compositions of this invention). These esters are preferably prepared by conventional methods, usually the reaction (frequently in the presence of an acidic catalyst) of the carboxylic acid-producing compound with a monohydric or polyhydric hydrocarbon-based alcohol or with an aromatic hydroxy compound such as a phenol or naphthol. The hydroxy compounds are usually alcohols containing up to about 40 aliphatic carbon atoms.These may be monohydric alcohols such as methanol, ethanol, the propanols, butanols, pentanols, isooctanol, dodecanol, cyclohexanol, neopentyl alcohol, monomethyl ether of ethylene glycol as well as the so-called fatty alcohols such as lauryl myristyl, cetyl, stearyl and behenyl alcohols and their mixtures, or polyhydric alcohols including ethylene glycol, diethylene glycol, dipropylene glycol, tetramethylene glycol, pentaerythritol, glycerol and the like. Fatty alcohols containing minor amounts of unsaturated (e.g., no more than about two carbon-to-carbon unsaturated bonds per molecule) also are useful. These are exemplified by palmitoleyl (C16H30O), oleyl (Ct8H36O) and eicosenyl (C20H40O) alcohols.

A further class of useful hydroxy compounds comprises the polyoxyalkylene compounds of the type commonly sold as demulsifiers. These include the "Ethomeens", "Ethoduomeens", "Pluronics", "Tergitols", "Tetronics", "Dow Polyglycols", etc. Carbohydrates (e.g., sugars, starches, cellulose) are also suitable as are partially esterified derivatives of polyhydric alcohols having at least three hydroxy radicals. Aliphatic polyols containing up to 10 carbon atoms and at least 3 hydroxy groups, especially those with up to 6 carbon atoms and 3-6 hydroxy groups, are preferred.

The esterification reaction is usually effected at a temperature above about 1 000C and typically from about 1500 to about 3000C. The esters may be neutral or acidic, or may contain unesterified hydroxy groups, according as the ratio of equivalents of acid-producing compound to hydroxy compound is equal to, greater than or less than 1:1.

It is possible to prepare mixed oxygen- and nitrogen-bridged dispersants by reacting the acylating agent simultaneously or, preferably, sequentially with nitrogen-containing and hydroxy reagents such as those described above. The relative amounts of the nitrogen-containing and hydroxy reagents may be between about 10:1 and 1:10, on an equivalent weight basis. The methods of preparation of the mixed oxygen- and nitrogen-bridged dispersants are generally the same as for the individual dispersants described, except that two sources of group 8-2 are used. Mixtures of independenty prepared dispersants are also suitable. Mixed dispersants of these types are frequently preferred for the purposes of this invention.

Illustrative reactive metal compounds which may be reacted with the carboxylic acids described above to produce dispersants 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 carbonate, 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.

Typical carboxylic dispersants suitable for use as component B are listed in Table I. "Reagent B1" and "Reagent 8-2" are, respectively, the sources of groups B-1 and 8-2 as previously defined. Table I Carboxylle dispersants Ratio of Reaction equivalents, temperature, Example Reagent B-1 Reagent B-2 B-1:B-2 C. Diluent 1-B Polybutenyl (mol.wt.Polyethylene amine mixture 0.48 150 Mineral oil about 900) succinic anhydride containing about 3-7 amino prepared from chlorinated groups per molecule polybutene comprising principally isobutene units 2-B Same as Example 1-B Pentaethylene hexamine 0.41 150 Mineral oil 3-B Like Example 1-B except Pentaethylene hexamine 0.61 150 Mineral oil polybutene mol. wt. ls about 850 4-B Like Example 1-B except Diethylene triamine 1.0 150 Mineral oil polybutene mol. wt. ls about 850 5-B Same as Example 4-B Ethylene diamine 1.0 150 Mineral oil 6-B Same as Example 4-B Di-(1,2-propylene)triamine 1.0 180-190 Mineral oil toluene 7-B Same as Example 4-B N-(2-hydroxyethyl)- 1.06 150-155 Mineral oil trimethylene diamine 8-B Same as Example 1-B Pantaerythritol, followed by 0.79 205-215 Xylenel oil polyethylene amine of Example 1-B (ratio of equivalents 3.4::1) 9-B Same as Example 1-B Same as Example 1-B 0.67 150 Mineral oil 10-B Same as Example 4-B Same as Example 1-B 1.33 150 Mineral oil- Table 1 (continued) Carboxylic dispersants Ratio of Reaction equivalents, temperature, Example Reagent B-1 Reagent B-2 B-1 : B-2 C Diluent 11-B Like Example 1-B, except Penthaerythritol, followed 0.44 150-210 Mineral oil polybutene mol. wt. polyethylene amine of is about 1100 Example 1-B (ratio of equivalents 7.7 : 1) 12-B Acid produced by reaction Ethylene diamine 2.0 150 Xylene of chlorinated (3.6% Cl) polybutene (mol. wt. 750) with KCN, followed by hydrolysis 13-B Methyl ester produced Triethylene tetramine 1.0 140-220 by reaction of chlorynated (4.7% Cl) polybutene (mol. wt. 1000) with methyl methacrylate 14-B Rection production Same as Example 1-8 0.4 150 Xylene Sodiomalonic ester with C76 brominated wax 15-B Reaction product of Penthaethylene hexamine 0.8 180-200 chlorinated (4.5% Cl) polybutene (mol. wt. 850) with acrylic acid 16-B Acid produced by halo- Same as Example 1-B 0.8 180-200 form reaction with methyl heptacontanyl ketone 17-B Same as Example 11-B Penthaerythritol 0.5 150-210 Mineral oil Table I (continued) Carboxylic dispersants Ratio of Reaction equivalents, temperature, Example Reagent B-1 Reagent B-2 B-1 :B-2 C Diluent 18-B Like Example 1-B, except Neopenthyl glycol 1.0 240-250 polybutene mol. wt. is about 1000 19-B Same as Example 18-B Methanol* Excess 50-65 Tolluene methanol 20-B Same as Example 18-B Polyethylene glycol (mol. wt. about 800) 2.0 240-250 21-B Same as Example 18-B Oleyl alcohol** 1.0 150-173 Xylene 22-B Like Example 15-B, except Sorbitol 0.48 115-205 Mineral oil polybutene mol. wt. is about 982 23-B Same as Example 22-B Pentaerythritol 1.0 180-205 24-B Reaction product of poly- Mannitol 0.33 115-205 Mineral oil butene (mol. wt. 1500) with chloroacethyl chloride * Hydrogen chloride catalyst ** p-Toluenesulfonic acid catalyst In the preparation of carboxylic dispersants such as those described in Examples 1 B-24B, reagent B-1 is normally prepared by reacting approximately equimolar amounts of the hydrocarbon source and the low molecular weight carboxylic acid or dervative thereof. It is also within the scope of the invention, however, to use as component B a nitrogen- or oxygen-bridged, or mixed nitrogen- and oxygen-bridged, dispersant prepared by initially reacting substantially more than one mole of acid or acid derivative with one mole of hydrocarbon source. In the preferred dispersants of this type, as in those previously described herein, the hydrocarbon source is an olefin polymer such as polybutene and the carboxylic acid derivative is maleic anhydride.Dispersants of this type usually contain up to about 3.5 and most often from about 1.5 to about 2.5 succinic groups for each group derived from the hydrocarbon source.

The method of preparation of dispersants of this type is basically the same as for the carboxylic dispersants already described. Reagent B-1, in particular, may be prepared by a one-step procedure in which the hydrocarbon source is reacted with maleic anhydride; by a two-step procedure in which the hydrocarbon source is chlorinated and the chlorinated intermediate is reacted with maleic anhydride; or by various combinations of the two procedures.

The following examples illustrate typical methods for the preparation of suitable dispersants of this type.

Example 25-B A mixture of 1000 parts (0.495 mole) of a polybutene comprising principally isobutene units and having a number average molecular weight of 2020 and a weight average molecular weight of 6049 and 115 parts (1.17 moles) of maleic anhydride is heated to 1 840C over 6 hours as 85 parts (1.2 moles) of chlorine is added beneath the surface. At 184-1 890C an additional 59 parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is stripped by blowing with nitrogen at 1 86- 1 900C for 26 hours to yield a polybutene-substituted succinic anhydride having a saponification number of 87 as determined by ASTM Procedure D94.

To 893 parts (1.38 equivalents) of this substituted succinic anhydride is added 1067 parts of mineral oil and 57 parts (1.38 equivalents) of a commercial ethylene polyamine mixture containing from about 3 to about 10 nitrogen atoms per molecule. The mixture is heated to 140-1 550C for 3 hours and is then stripped by blowing with nitrogen. The stripped liquid is filtered and the filtrate is the desired dispersant (approximately 50% solution in oil).

Example 26-B A mixture of 334 parts (0.52 equivalent) of the polybutenyl succinic anhydride of Example 25-B, 548 parts of mineral oil, 30 parts (0.88 equivalent) of pentaerythritol and 8.6 parts (0.0057 equivalent) of Polyglycol 112-2 demulsifier from Dow Chemical Company is heated at 1 50-21 00C for about 11 hours. The mixture is cooled to 1 900C and 8.5 parts (0.2 equivalent) of the ethylene polyamine mixture of Example 25-B is added. The mixture is stripped by blowing with nitrogen for 3 hours at 2050C and is filtered to yield the desired dispersant as an approximately 40% solution in oil.

Example 27-B A substituted succinic anhydride is prepared by the procedure of Example 26-B, using a similar polybutene with a Mn of 1457 and a7V [ w of 5808. A mixture of 5500 parts of this anhydride, 3000 parts of mineral oil and 236 parts of the ethylene polyamine mixture of Example 26-B is heated at 1 55-1 650C for 2 hours, stripped by blowing with nitrogen at 1 650C for 1 hour, and filtered to yield an oil solution of the desired dispersant.

Example 28-B A product is prepared by the procedure of Example 26-B from 1 equivalent of the substituted succinic anhydride of Example 25-B, 1-8 equivalents of pentaerythritol, 0.2 equivalent of the ethylene polyamine mixture of Example 26-B, and mineral oil in an amount to afford a 30% solution of the product in oil.

Example 29-B A product is prepared by the procedure of Example 25-B using a substituted succinic anhydride prepared by the reaction of 98 parts of maleic anhydride with 5670 parts of a 10% solution of "Ortholeum 2052" in mineral oil.

Oil-soluble metal salts of substituted succinic acid acylated aliphatic polyamines also are useful as detergents in the compositions of the invention. These are exemplified by the alkali, alkaline earth, lead, cadmium, zinc, nickel and cobalt salts of hydrocarbon-substituted succinic acid acylated alkylene polyamines. The principal sources of the hydrocarbon substituent include the high molecular weight petroleum fraction and olefin polymers as described above, and the substituent should be substantially saturated, that is, at least about 95% of the total number of carbon-to-carbon covalent linkages are saturated linkages.

The size of the hydrocarbon substituent of the succinic compound appears to determine the effectiveness of the additive as a dispersant. It is important, therefore, that the substituent be large, that is, that it have at least about 50 aliphatic carbon atoms. The molecular weight of the hydrocarbon substituent should be within the range of from 700 to about 100,000. The most common sources of the substantially aliphatic hydrocarbon substituents are the polyolefins such as polyethylene, polypropylene, polybutene, etc. A particularly preferred polyolefin is polyisobutene having a molecular weight of about 1000.

The basic metal reactant can be an alkali metal, alkaline earth metal, lead, cadmium and zinc oxides, hydroxides, carbonates and lower alcoholates and a combination of all of an alkali metal hydroxide and an inorganic metal salt selected from the group consisting of alkaline earth metal, lead, cadmium, zinc, nickel and cobalt halides and nitrates. Illustrative examples of the basic metal compounds include sodium oxide, sodium methylate, potassium hydroxide, potassium carbonate, lithium hydroxide, calcium hydroxide, calcium carbonate, calcium chloride, barium oxide, barium fluoride, magnesium ethylate, magnesium bromide, magnesium phenoxide, zinc hydroxide, zinc nitrate trihydrate, cadmium oxide, lead oxide, lead chloride, nickel hydroxide, nickel carbonate, cobalt hydroxide, cobaltous bromide, etc.

The amines which are useful in the preparation of these detergents include alkaline polyamines and hydroxyalkyl-substituted alkaline polyamines of the types described above with respect to the carboxylate dispersants.

These metal salts of substituted succinic acid acylated aliphatic polyamines can be prepared by either (1) first preparing the acylated amine of the hydrocarbon-substituted succinic compound and then reacting the acylated amine with the basic metal compound, or (2) first preparing the mono-metal salt of the hydrocarbon-substituted succinic compound and then reacting said mono-metal salt with an alkaline polyamine or hydroxyalkyl-substituted alkaline polyamine. In the first method, it is preferred that the succinic compound be the succinic anhydride and that trace amounts of water, that is, up to about 2.596 by weight, be present when the basic metal compound is an oxide. In the second method, it is preferred that the succinic compound be the succinic acid.In all cases, it is preferred that nitrogen or some inert gas be bubbled through the reaction mixtures to remove any water formed as a result of the acylation reaction.

The oil-soluble metal salts of substituted succinic acid acylated aliphatic polyamines and processes for their preparation are described in detail in U.S. Patent Re 26,433, and the disclosure of said Reissue Patent is incorporated herein by reference. The following examples illustrate the preparation of the oil-soluble metal salts of substituted succinic acid acylated aliphatic polyamines.

Example 30-B A polyisobutenyl succinic anhydride is prepared by the reaction of a chlorinated polyisobutylene (having an average chlorine content of 4.3 weight percent and an average of 70 carbon atoms) with maleic anhydride at about 2000C. The resulting polyisobutenyl succinic anhydride has an acid number of 103. To a mixture of 3,264 grams (6 equivalents) of this polyisobutenyl succinic anhydride, 2,420 grams of mineral oil and 75 grams of water, there is added at 80C to 1000C, 122.1 grams (3 equivalents) of zinc oxide. The addition is made portionwise over a period of 30 minutes. The mixture is maintained at a temperature of 90"--1000C for a period of 3 hours.Thereupon, the mixture is heated to 1 500C and maintained at this temperature until it is essentially dry. The mixture is cooled to 1 000C and there is added 245 grams (6 equivalents) of an ethylene polyamine mixture having an average composition corresponding to that of tetraethylene pentamine and an equivalent weight of 40.8. The addition is made portionwise over a period of 30 minutes whereupon the mixture is heated to a temperature of 150 160 C and maintained at this temperature for 5 hours. Throughout the 5-hour period, nitrogen is bubbled through the mixture to remove water formed as a result of acylation. The residue is filtered. The resulting filtrate has a zinc content of 1.63% and a nitrogen content of 1.39%.

Example 31-B To a mixture of 3,750 grams (6 equivalents) of a polyisobutenyl succinic anhydride (having an acid number of 89.8 and prepared, as in Example 30-B, from maleic anhydride and chlorinated polyisobutylene having an average chlorine content of 4.3 weight percent and an average of 81 carbon atoms), 2,632 grams of mineral oil and 75 grams of water, there is added, at 80C1 000C, 60 grams (3 equivalents) of magnesium oxide. The addition is made portionwise over a 10-minute period. The mixture is maintained at a temperature of 100"--1050C for 3 hours. During the first part of this 3-hour period, 50 grams of water is added.Thereupon, 113 grams (3 equivalents) of an amine mixture such as described in Example 30-B (but with an equivalent weight of 37.8) is added portionwise over a period of 30 minutes while the temperature of the mixture is maintained at 98c1 000C. The mixture is heated at 21 002 1 50C and maintained at this temperature for 4 hours. Throughout the 4-hour period, nitrogen is bubbled through the mixture to remove water resulting from acylation. The residue is filtered. The filtrate has a magnesium content of 0.55%, based on sulfate ash, and a nitrogen content of 0.64%.

Example 32-B To a mixture of 1,028 grams (2 equivalents) of a polyisobutenyl succinic anhydride (having an acid number of 109 and prepared, as in Example 30-B, from maleic anhydride and a chlorinated polyisobutylene having an average chlorine content of 4.3 weight percent and an average of 65 carbon atoms), 707 grams of mineral oil and 1,500 grams of benzene, there is added at 600C, 41 grams (1 equivalent) of an amine mixture such as described in Example 30-B (but with an equivalent weight of 41). The addition is made portionwise over a 30-minute period. The mixture is maintained at a temperature of 8 5 0--900 C for 7 hours. Throughout this 7-hour period, nitrogen is bubbled through the mixture to remove water resulting from acylation.To 1,034 grams of the above mixture and 52 grams of water, there is added 800--900C, 52 grams (0.67 equivalent) of barium oxide. The addition is made portionwise over a 30-minute period. The mixture is maintained at a temperature of 800--900C for 2 hours. Thereupon, the mixture is heated to 1 500C and stripped of the last traces of water. The residue is filtered. The filtrate has a barium content of 3.9% and a nitrogen content of 0.76%.

Example 33-B To a mixture of 4,200 grams (6 equivalents) of a polyisobutenyl succinic anhydride (having an acid number of 80 and prepared, as in Example 80-B, from maleic anhydride and chlorinated polyisobutylene having an average chlorine content of 4.3 weight percent and an average of 92 carbon atoms) and 2,930 grams of mineral oil, there is added at 800C, 390 grams of 1-(2hydroxyethyl)piperazine. The addition is made portionwise over a 30-minute period and the resulting mixture is maintained at a temperature of 1 80 0--205 OC for 5 hours. Throughout the 5-hour period, nitrogen is bubbled through the mixture to remove water resulting from acylation. To the above mixture, combined with 35 grams of water, there is added at 300 C, 1 59 grams (3 equivalents) of sodium carbonate.The addition is made portionwise over a 45-minute period. The temperature is maintained at 700--800C for 3 hours whereupon the mixture is heated to 1 500C and stripped of the last traces of water. The residue is filtered. The filtrate has a sodium content of 0.88 percent and a nitrogen content of 1.1 percent.

Example 34B To a mixture of 1,245 grams (2 equivalents) of a polyisobutenyl succinic anhydride (having an acid number of 90 and prepared, as in Example 30-B, from maleic anhydride and chlorinated polyisobutylene having an average chlorine content of 4.3 weight percent and an average of 81 carbon atoms), 871 grams of mineral oil and 25 grams of water, there is added at 800C, 56 grams (1 equivalent) of potassium hydroxide. The addition is made portionwise over a 30-minute period, after which the mixture is held at 85 0--95 OC for 1 hour, then dried by heating at 1350-1400Cfor 1 hour.

Thereupon, 104.2 grams (1 equivalent) of barium chloride is added portionwise over a period of 30 minutes, with the temperature at 800900C. The mixture then is heated at 1 3001 400C-for 9 hours, and filtered. To the filtrate there is added 41 grams (1 equivalent) of an amine mixture such as described in Example 30-B (but with an equivalent weight of 41). The addition is made portionwise over a 30-minute period, with the temperature at 11 001 400C. The mixture then is heated at 1600--1650C for 4 hours, throughout which period nitrogen is bubbled into the mixture to remove water resulting from acylation. The residue is filtered. The filtrate has a barium content of 2.7% and a nitrogen content of 0.61%.

Also preferred for use as component B, as an alternative to the carboxylic dispersants hereinabove described, are the Mannich dispersants. These are, as previously noted, reaction products of certain alkyl phenols with aldehydes (usually lower aliphatic aldehydes and especially formaldehyde) and amino compounds. The structure of the alkyl substituent on the phenol is subject to the same preferences as to source, structure, molecular weight and the like expressed hereinabove with respect to the carboxylic dispersant. The amino compounds are the same as those described with reference to nitrogen-bridged carboxylic dispersants and are subject to the same preferences.

Suitable Mannich dispersants for use as component B are illustrated in the working examples of the aforementioned U.S. Patent 3,980,569 and German Application 2,551,256. The following examples also are illustrative.

Example 35-B A mixture of 3740 parts (2 equivalents) of a polybutenyl phenol in which the polybutene substituent comprises principally isobutene units and has a molecular weight of about 1 600, 1250 parts of textile spirits and 2000 parts of isopropyl alcohol is stirred as 352 parts (2.2 equivalents) of 50% aqueous sodium hydroxide is added, followed by 480 parts (6 equivalents) of 38% aqueous formaldehyde solution. The mixture is stirred for 2 hours, allowed to stand for 2 days and then stirred again for 17 hours. Acetic acid, 150 parts (2.5 equivalents), is added and the mixture is stripped of volatile materials under vacuum. The remaining water is removed by adding benzene and distilling azeotropically; during the distillation, 1000 parts of mineral oil is added in two portions. The distillation residue is filtered.

To 430 parts (0.11 5 equivalent) of the filtrate is added with stirring, at 900C, 14.1 parts (0.345 equivalent) of the polyethylene amine mixture containing about 3 to 7 amino groups per molecule. The mixture is heated at 90--120"C for 2 hours and then at 150--1600C for 4 hours, with nitrogen blowing to remove volatiles. The resulting solution is filtered to yield the desired Mannich dispersant 152% solution in mineral oil) which contains 1.03% nitrogen.

Example 36-B A mixture of 564 parts (0.25 equivalent) of polybutenyl phenol in which the polybutene substituent comprises principally isobutene units and has a molecular weight of about 2020, 400 parts of mineral oil and 16.5 parts of isobutyl alcohol is heated to 650C, with stirring, and 2.15 parts (0.025 equivalent) of 50% aqueous sodium hydroxide solution is added, followed by 16.5 parts (0.5 equivalent) of paraformaldehyde. The mixture is stirred at 80-880C for 6 hours and then 5 parts (0.025 equivalent) of 18.5% aqueous hydrochloric acid is added slowly, with continued stirring, followed by 36 parts (0.875 equivalent) of polyethylene amine mixture containing about 3 to 7 amino groups per molecule, at 880C. Mixing is continued at 8891 C for 30 minutes.The mixture is then heated to about 1 580C with nitrogen blowing to remove volatiles.

Sulfur, 16 parts (0.5 mole), and 25 parts of a filter aid material are added slowly at 1 500 C, with stirring, after which the mixture is blown with nitrogen at 150155 C for 3 hours. The mixture is then cooled to 1320C and filtered to yield the desired sulfurized Mannich product as a 60% solution in mineral oil; it contains about 0.63% sulfur.

In general, the compositions of this invention comprise about 0.23.0 parts by weight of component A per part of component B. These proportions are of active chemicals; that is, they disregard any diluent such as mineral oil. The preferred proportions are about 0.31.0 part of component A per part of component B.

Specific examples of the multi-component compositions of the invention comprising mixtures of components A and B are as follows: Table II Multi-component compositions Composition Example ComponentA Component B Weight ratio A 1-A 3-B 1:2 B 12-A 26-B 0.3:1 C 12-A 2-B:4-B 0.3:0.5:0.5 D 13-A 30-B 0.4:1 E 6-A 3-B :32-B 0.3:0.4:0.4 F 8-A 36-B 1:1 As previously indicated, the compositions of this invention are also useful as additives for lubricants. They are particularly useful for lubricating machinery which operates at relatively high temperatures, and are effective over a wide range of concentrations.Moreover, they frequently result in a decrease in the amount of oxidation inhibiting additives (examples of which are listed hereinafter) which must be incorporated in the lubricant and in a decrease in fuel consumption.

The compositions 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, 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, metalworking 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 oils, lard oil) as well as mineral lubricating oil such as liquid petroleum oils and solvent-refined or acid-refined mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.Synthetic lubricating oils include hydrocarbon oils and halosubstituted 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), etc. and mixtures thereof); alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonyibenzenes, di-(2-ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls, terphenyls, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof, etc.

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 500-1 000, 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 C13Oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene 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 as trimethylol propane, pentaerythritol, dipentaerythritol, 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-methyl-2-tetraethyl)silicate, tetra-(p-tertbutylphenyl)silicate, hexyl-(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 decane phosphonic acid, etc.), polymeric tetrahydrofurans and the like.

Unrefined, refined and rerefined oils, either natural or synthetic (as well as mixtures of two or more of any of these) 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, secondary distillation, 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 this invention will contain an amount of the composition of the invention which is effective to reduce fuel consumption of engines lubricated with the lubricants of the invention. Normally this amount will be in the range of from about 0.05% to about 10% although amounts of 0.1 to 5% per 100 parts of the total finished lubricant weight are preferred.

The compositions of the present invention can contain, in addition to components A and B, other additives that are normally used in lubricants. Such additives include, for example, auxiliary detergents of the ash-forming and of the ashless type, viscosity index improving agents, pour-point depressants, anti-foam agents, extreme pressure agents, rust inhibiting agents, oxidation and corrosion inhibiting 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 trichloride, 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.

The term "basic salt" is used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical. The commonly employed methods for preparing the basic salts involve heating a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 500C and filtering the resulting mass. The use of a "promoter" in the neutralization step to aid the incorporation of a large excess of metal likewise is known. Examples of compounds useful as the promoter include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation products of formaldehyde with a phenolic substance; alcohols such as methanol,2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-betanaphthylamine, and dodecylamine. A particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter, and carbonating the mixture at an elevated temperature such as 60200 C.

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 are disclosed in patents including those listed hereinabove with respect to component B. Also useful as auxiliary dispersants are 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 which are incorporated by reference: 3,329,658 3,666,730 3,449,250 3,687,849 3,519,565 3,702,300 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 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 heptylphenyl 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 isopropylalcohol and n-hexyl alcohol.

The compositions of this invention also can contain at least one viscosity improving component; that is, at least one component capable of substantially improving the viscosity properties thereof. For the purposes of this invention, a substance is considered to substantially improve the viscosity properties of a composition if its incorporation in the composition in operative amounts causes an increase in its viscosity index (as determined by ASTM procedure D2270) of at least 6 units.

A number of types of viscosity improvers are known in the art, and many of these are described in Ranney, LubricantAdditives (Noyes Data Corporation, 1973), pp. 93-119. Illustrative viscosity improvers include various olefin polymers such as polybutene (especially containing predominantly isobutene units); ethylene-propylene copolymers; copolymers of ethylene and other low molecular weight olefins (especially alpha-olefins); terpolymers of ethylene, propylene and various dienes (especially non-conjugated dienes); polybutadiene; hydrogenated styrene-butadiene copolymers; alkylated polystyrenes; polymers of alkyl methacrylates; alkylene polyethers; and polyesters prepared from polyols, short-chain dicarboxylic acids and monobasic carboxylic acid terminators (useful predominantly in lubricants in which the lubricating oil is a synthetic ester).

It is also within the scope of the invention to use as component B a composition which improved viscosity properties as well as serving as a dispersant or detergent. When component B also improves viscosity properties, it may be possible to decrease the amount of auxiliary viscosity improver used or to eliminate it entirely.

The present invention contemplates two materials as being particularly useful as combination viscosity improvers and detergents or dispersants. The first comprises the dispersants containing more than one succinic moiety per molecule, particularly those prepared from a hydrocarbon source having a number average molecular weight (Mn) of at least about 1300 and usually about 13005000 as determined by gel permeation chromatography. Examples 25B-29B hereinabove illustrate suitable dispersants of this type which also have viscosity improving properties.

The second type of preferred viscosity improver having dispersant or detergent properties comprises interpolymers being substantially free of titratable acidity and containing carboxylic ester groups in which part of the alcohol moieties have at least 8 aliphatic carbon atoms and another part have no more than 7 aliphatic carbon atoms, and also containing carbonylpolyamino groups in which the polyamino group is derived from a compound having one primary or secondary amino group. These polymers are described in U.S. Patent 3,702,300, which is incorporated by reference for such description.Preferred are interpolymers prepared by first copolymerizing styrene with maleic anhydride and subsequently esterifying a portion of the carboxylic acid groups with a mixture of primary alcohols having the numbers of carbon atoms noted above, and neutralizing the remaining carboxylic acid groups with a suitable amine. The working examples of U.S. Patent 3,702,300 illustrate specific suitable polymers.

A further component in the phosphorus acid salt compositions of this invention can be at least one compound of the formula

wherein each of R'3 and R'4 is independently a hydrocarbon-based group having from about 3 to about 20 carbon atoms and M is a Group I metal, a Group II metal, aluminum, tin, iron, cobalt, lead, arsenic, molybdenum, manganese, nickel, or a mixture of any said metals. These phosphorus acid salts, when present, provide load carrying an oxidation inhibiting properties to the lubricant.

Each of R'3 and R'4 is preferably an alkyl group, although it may be an aryl or substituted aryl group (e.g., phenyl, tolyl, chlorophenyl). Suitable alkyl groups include propyl, butyl, octyl, decyl, hexadecyl, octadecyl, eicosyl and mixtures thereof. Most often, each of R13 and R'4 is an alkyl group containing from about 6 to about 20 and preferably from about 6 to about 10 carbon atoms. Branched groups (e.g., isooctyl, 2-ethylhexyl) are especially preferred.

The metal (M) of the phosphorus acid salt is preferably zinc or molybdenum and especially zinc.

As previously noted, it is within the scope of the invention to use salts of more than one metal or to use a mixed salt of two or more metals (e.g., zinc and arsenic, zinc and nickel, molybdenum and manganese).

The compositions of this invention can be added directly to the lubricant. 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 2090% 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.

Illustrative concentrates of this invention are listed in Table Ill and illustrative lubricants of this invention are listed in Table IV. All amounts except those for the products of Examples are exclusive of diluents such as mineral oil.

Table Ill Concentrate Examples Parts by weight Ingredient Concentrate A B C D E Mineral oil (100 neutral) - 30.0 Mineral oil (200 neutral) - - - - 50.0 Mineral oil (200 neutral-45% by volume; 75.0 - 82.34 - 100 neutral-55% by volume) Diluent mineral oil - - 7.18 60.0 Product of Example 1-A 10.0 30.0 1.99 15.0 15 Product of Example 12-A 13.0 40.0 0.41 1 5 Product of Example 2-B - - 2.72 5.0 Product of Example 32-B - - - 20.0 20 Basic calcium alkylphenol sulfide - - 0.72 - Hydroxypropyl esteroftetrapropenyl- 0.35 succinic acid Zinc dialkylphosphorodithioate containing - - 0.43 - C3-6 branched chain alkyl groups Silicone anti-foam agent - - 0.005 0.05 0.005 Table IV Lubricant Examples Parts by weight Ingredient Lubricant A B C D E Mineral oil 92.92 91.75 88.25 98.0 98.0 Product of Example 1-A 1.50 - 1.09 0.5 Product of Example 8-A - 1.17 - - 1.0 Product of Example 3-B 2.50 2.50 - 1.5 Product of Example 25-B - - 7.14 - 1.0 Reaction product of polybutenyl (mol. wt. - 1.38 - - about 1000) succinic anhydride with pentaerythritol and ethylene polyamine mixture Basic calcium petroleum sulfonate 0.67 0.53 1.32 - Basic magnesium petroleum sulfonate 0.59 0.49 - Zincdialkylphosphorodithioate 1.18 1.16 1.19 - Alkylfumarate-vinyl acetate-vinyl - 0.21 0.14 - - ether terpolymer Sulfur- and methylene-bridged polybutenyl 0.54 - - (mol. wt. about 2000) phenol "Ortholeum 2052" - 0.80 0.52 - Sulfurized alkyl cyclohexenecarboxylate 0.27 Tetrapropenyl succinic anhydride - - 0.27 - Poly(alkyleneoxide) demulsifier 0.10 - - Hindered phenol antioxidant - 0.01 0.01 - Silicone anti-foam agent 0.011 0.01 0.007 The fuel consumption of internal combustion engines is reduced when the engines are lubricated with the compositions of this invention. This can be shown by the Pinto Friction Horsepower Test, in which a Ford Pinto engine is driven by a dynamometer at constant temperature while engine r.p.m. and torque are measured by a digital tachometer and a precision dial manometer, respectively. Friction horsepower, as calculated from these values, is roughly proportional to fuel consumed and thus decreases with improved fuel economy.

Claims (25)

Claims

1. A multi-component composition comprising (A) at least one tartrate of the formula:

wherein each R is independently a hydrocarbon-based group and the sum of carbon atoms in both R groups is at least about 8; and (B) at least one oil-soluble detergent or dispersant.

2. The composition of claim 1 wherein each R group is about 8-20 carbon atoms.

3. The composition of claim 1 wherein at least one R group contains an uninterrupted chain of at least about eight-CH2- units.

4. The composition of claim 1,2 or 3 wherein the detergent is a basic alkali or alkaline earth metal salt or complex of a phenol, sulfonic acid, carboxylic acid or phosphorus acid.

5. The composition of claim 4 wherein the detergent is a basic alkali or alkaline earth metal salt.

6. The composition of claim 5 wherein the detergent is a basic calcium sulfonate.

7. The composition of claim 1, 2 or 3 wherein the dispersant is characterized by the presence of an oil-solubilizing group containing at least about 40 aliphatic carbon atoms bonded directly to a polar group.

8. The composition of claim 7 wherein the dispersant is a carboxylic dispersant, a Mannich dispersant, an amine dispersant, a polymeric dispersant, or a post-treatment product of any of the foregoing.

9. The composition of claim 8 wherein the dispersant is a carboxylic dispersant characterized by the presence within its molecular structure of an acyl, acyloxy or acylimidoyl group containing at least about 44 carbon atoms and a group in which a nitrogen or oxygen atom is attached directly to said acyl, acyloxy or acylimidoyl group, said nitrogen or oxygen atom also being attached to a hydrocarbonbased group.

10. The composition of claim 9 wherein the dispersant is prepared by reaction of a substantially saturated hydrocarbon-substituted or halohydrocarbon-substituted succinic acid compound with at least one alcohol or an alkylene polyamine.

11. The composition of claim 10 wherein the substantially saturated hydrocarbon-substituted succinic acid compound is prepared by reaction of more than one mole of maleic anhydride with one mole of an olefin polymer.

12. The composition of claim 11 wherein the substituted succinic acid contains an average of 1.3 to 3.5 succinic acid groups for each olefin polymer derived group.

13. The composition of claim 10 wherein the hydrocarbon substituent on the succinic acidproducing compound contains at least about 50 aliphatic carbon atoms and the dispersant is prepared by the reaction of said succinic acid-producing compound with at least one alcohol.

14. The composition of claim 13 wherein the alcohol is pentaerythritol.

1 5. The composition of claim 10 wherein the substituent on the succinic acid-producing compound contains at least about 50 aliphatic carbon atoms and the dispersant is prepared by the reaction of said succinic acid-producing compound with at least one alkylene polyamine.

16. The composition of claim 15 wherein the alkylene polyamine is an ethylene polyamine.

1 7. The composition of claim 8 wherein the dispersant is a Mannich dispersant comprising the reaction product of an alkyl phenol in which the alkyl group contains at least about 40 carbon atoms with an aliphatic aldehyde containing at least about 7 carbon atoms and an amine.

18. The composition of claim 17 wherein the aldehyde is formaldehyde and the amine is an alkylene polyamine.

19. The composition of claim 18 wherein the amine is an ethylene polyamine.

20. The composition of claim 1,2 or 3 wherein both a detergent and a dispersant are present.

21. The composition of claim 20 wherein the detergent is a basic alkali or alkaline earth metal sulfonate and the dispersant is prepared by reaction of a hydrocarbon substituted succinic acidproducing compound with at least one alcohol or an alkylene polyamine.

22. An additive concentrate comprising from 10 to 80 parts of an inert liquid solvent or diluent and from 20 to 90 parts of the composition of any one of claims 121.

23. A lubricant comprising a major proportion of oil and a minor proportion of the composition of any one of claims 121.

24. A method of reducing fuel consumption in an internal combustion engine which comprises lubricating said engine during operation with a lubricant comprising a composition according to any one of claims 121.

25. The invention in its several novel aspects.