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Publication numberUS3701729 A
Publication typeGrant
Publication dateOct 31, 1972
Filing dateJun 1, 1970
Priority dateJun 1, 1970
Also published asCA965429A1, DE2127175A1, DE2127175C2
Publication numberUS 3701729 A, US 3701729A, US-A-3701729, US3701729 A, US3701729A
InventorsAlfred Fischer, Terry M Strawser
Original AssigneeTenneco Chem
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Oil-soluble mixed copper soap products
US 3701729 A
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Description  (OCR text may contain errors)

United States Patent 3,701,729 OIL-SOLUBLE MIXED COPPER SOAP PRODUCTS Alfred Fischer, Bronx, N.Y., and Terry M. Strawser, iSonnd Brook, N.J., assignors to Tenneco Chemicals nc. No Drawing. Filed June 1, 1970, Ser. No. 42,536 Int. Cl. C10m 3/18, 5/14 US. Cl. 252-1 28 Claims ABSTRACT OF THE DISCLOSURE Oil-soluble mixed copper soaps of structurally different organic monocarboxylic acids, the acids being selected from the group consisting of saturated aliphatic acids and olefinic acids, and solutions of such mixed soaps are provided.

It is desirable for many purposes to be able to obtain dissolved copper-containing hydrocarbon oils. Such dissolved copper is generally obtained by dissolving or dispersing an oil-soluble copper soap into the hydrocarbon oil. Such dispersed copper is especially useful in fuel oils for removing or preventing the deposition of soot when burning the oil in furnaces or other equipment such as locomotives and fire-up torches. Oil-soluble copper soaps are also useful as a source of soluble copper for use as catalysts for various liquid phase organic reactions, e.g. the preparation of adipic acid, and for the preparation of fungicides for use in oils or oil-miscible materials.

It has been recognized, heretofore, that various copper soaps are oil-soluble, including the copper soaps of the petroleum acids, i.e. the sulfonic acids, often referred to as the mahogany acids, and the naphthenic acids. These materials, however, are generally of a relatively high molecular weight so that in order to obtain a desired percentage of copper, by weight, dissolved in the oil, it was necessary to dissolve a relatively high percentage of the total soap in the oil.

Accordingly, it is desirable to use lower molecular weight copper soaps in order to obtain a higher proportion of copper dissolved for a given amount of soap added. Johnson, in US. Pat. No. 2,622,671, describes copper soaps of certain lower molecular weight acids which are soluble in turpentine and which can then be dissolved in fuel oils. Johnson describes these as the salts of branched chain acyclic aliphatic canboxylic acids having from 5 to 12 carbon atoms, in which the carboxyl group is attached to a carbon atom other than the central carbon atom in the longest hydrocarbon chain. It has been found, however, that all such soaps are not generally soluble in hydrocarbon nonpolar solvents, such as mineral spirits; Johnson asserts they are soluble in turpentine and then miscible with other materials. As these other nonpolar solvents are generally much less expensive to obtain or produce than turpentine, and, therefore, more likely to be commercially useful in such low cost, high volume uses as fuel oils, the need remains to obtain materials that provide a relatively high concentration of copper for as small a total amount of soap added as possible in an oil-miscible environment.

The present invention is directed to an oil-soluble mixed copper soap product comprising one or more soaps containing combined copper with acid groups derived from two structurally difierent organic monocarboxylic acids selected from the group consisting of saturated and olefinically unsaturated aliphatic carboxylic acids. This invention further provides a solution comprising a nonpolar hydrocarbon solvent or a halo-substituted nonpolar hydrocarbon solvent having dissolved therein the oil-soluble mixed copper soap composition as defined above.

The present invention includes an oil-soluble copper mixed soap comprising copper combined with two structurally diiferent acid groups derived from the organic monocarboxylic acids defined above, and stable solutions of the copper mixed soaps in a nonpolar hydrocarbon solvent or chlorinated nonpolar hydrocarbon solvent.

This invention further includes a coprecipitated mixture of copper soaps of two structurally different carboxylic acids selected from the above group consisting of saturated and olefinically unsaturated aliphatic monocarboxylic acids; a solution comprising a nonpolar hydrocarbon solvent or halo-substituted nonpolar hydrocarbon solvent containing dissolved therein a mixture of such salts is also a part of this invention.

The copper mixed soap product of this invention can broadly be prepared by the process comprising simultaneously reacting copper, in the form of combined or elemental copper, with acid group-containing compounds, there being present at least two structurally dilferent acid groups, as defined above. It is, however, often not possible to determine the precise structure of the product according to this process, i.e. whether it is a copper mixed soap, a coprecipitated mixture of two normal soaps, or a coprecipitated combination of a mixed soap and the two normal soaps. In such circumstances, defining the product in terms of the above preparation process is a complete definition of the product.

The mixed copper soap products of the present invention are in the form of a copper mixed soap or of the coprecipitated soap. The coprecipitated soaps can be prepared from a mixture of normal soaps, that are dissolved preferably from an intimate mixture, as by finely grinding together, and then removing the solvent.

The term normal soap when used herein refers to the copper soap of a single acid, e.g. copper 2-ethylhexoate. The term coprecipitated soaps when used herein, refers to a combination of two copper soaps obtained by removing the solvent from a solution of the two soaps or by causing the simultaneous precipitation of the two soaps from a solution of the two soaps.

In the preferred embodiments of this invention, the normal copper soaps of the acids used are insoluble but the mixed soap products of this invention are oil-soluble, i.e. soluble at room temperature in nonpolar oil miscible liquids, to form a solution stable at room temperature.

The copper mixed soap and coprecipitated copper soaps of this invention are generally more readily dissolved in oils and nonpolar hydrocarbon solvents and halo-substituted nonpolar hydrocarbon solvents than are mere mixtures of the normal copper soaps of the same acids. In addition, the solutions containing the dissolved copper soaps show a decreased viscosity when the mixed copper soap products are present as compared to the viscosity when only one of the normal copper soaps of the same acids is soluble and is dissolved in the same total propertions. There is also generally an improvement in the viscosity of the final solution compared to solutions obtained from normal copper soaps that are soluble. This decrease in viscosity results in an improved product which can be more readily handled and more easily mixed and otherwise processed.

It has been found that the isolated copper mixed soaps and coprecipitated soaps of the present invention behave differently than a mixture of the normal copper soaps of the same two structurally difierent acids. The copper mixed soaps and coprecipitated soaps of the present invention are not crystalline granular material as are the normal copper soaps of most of these acids, but rather, appear as a soft plastic mass, noncrystalline in appearance. A mechanical mixture of the copper soaps of the same acids does not dissolve in a nonpolar solvent as readily as the mixed soap in many instances. But many mixtures of soaps can generally be dissolved by heating, e.g. in mineral spirits, generally to form a stable solution. The coprecipitated soaps can, of course, then be obtained by evaporating off the solvent. Accordingly, mixed copper soap products of this invention include broadly, all these types.

The copper mixed soaps of the present invention are believed to have the following structure:

OOC-R wherein R and R are structurally different and selected from among saturated aliphatic and olefinically unsaturated aliphatic groups. The RCOO and R'COO groups are the residue of the corresponding monocarboxylic acids. In the so-called normal soaps, R and R are the same. The group of acids is sub-divided into the following different structural groups. For example, the broad group: saturated aliphatic acids and olefinic acids, is subdivided according to whether there is branching, and if so, the position of the branch closest to the carboxyl group: these include the straight-chain acids, e.g. normal octanoic acid or caprylic acid, the alpha-substituted branched acids, e.g. Z-ethylhexanoic acid, the beta-substituted branchedchain acids, e.g. 3,5,5 trimethylhexanoic acid and the gamma-substituted branched acids, e.g. 4 ethyl 5,-5-dimethylhexanoic acid and delta-substituted, e.g. 5-ethyl-6- methylheptanoic acid. The position of, or even the existence of, further branching on the chain more than five carbon atoms removed from the carboxyl group has been found to have little or no effect in forming an oil-soluble mixed salt or a lower viscosity solution when mixed with a linear chain acid.

The alpha acids contain a first branched chain on the first carbon atom adjacent to the carboxyl group. The beta acids contain a first branched chain attached to the second carbon atom removed from the carboxyl group. In the gamma acids, the first branched chain is attached no closer than the third carbon atom from the carboxyl group.

Generally, the acid groups present in the copper mixed soap product or coprecipitated soaps of the present invention have at least five carbon atoms in the molecule. Preferably, the acid groups will have from about 5 to about 20 carbon atoms, the upper limit not being a limit as to the effectiveness of the material in forming a soluble soap but rather as reaching a point where the proportion of copper in the molecule is so low as to render uneconomical the use of such a soap as a source of copper. The optimum acid groups contain from about 6 to about 11 carbon atoms.

Generally, the most useful compounds are the hydrocarbon acids because these are the most readily available at the lowest prices. However, the mixed copper soaps or coprecipitated soaps of this invention also include the soaps of acids which contain various inert substituent groups attached onto the hydrocarbon chain, or side chain. Such inert substituent groups include, particularly, the halogen atoms, and especially chlorine, and oxygen atoms in the form of ether linkages along the chain of the carboxylic acid or in one of the branch chains.

Useful aliphatic acids are those having at least five carbon atoms and include the saturated linear fatty acids, such as valeric acid, caproic acid, caprylic acid (noctanoic), pelargonic acid, n-decanoic acid, undecanoic acid and lauric acid. The alpha-branched saturated acids include Z-ethyI-butanoic acid, 2-ethyl-4-methylpentanoic acid, 2-ethylhexanoic acid, 2,2,4,4-tetramethylpentanoic acid, 2-isopropyl-2,3-dimethylbutanoic acid, 2-propyl-4- methylpentanoic acid, 2-propylheptan0ic acid, Z-methylbutanoic acid, Z-methylpentanoic acid, 2,3-dimethy1pentanoic acid, 2,2-dimethylpentanoic acid, 2-ethyl-3-methylbutanoic acid, 2,5-dimethylhexanoic acid, 2,2-dimethylheptanoic acid, 2-ethyl-5-methylhexanoic acid, 2-methylnonanoic acid, 2-ethyloctanoic acid, 2-propylhexanoic acid, 2-propyl-5-methylhexanoic acid. Beta branched acids include 3-methylb-utanoic acid, 3,3-dimethylbutanoic acid, 3,3-dimethylpentanoic acid, 3-ethylpentanoic acid, 3,5-dimethylhexanoic acid, 3-ethyl-4-methylpentanoic acid, 3- methylactanoic acid, 3 propylhexanoic acid, 3,5,5-trimethylhexanoic acid, 3 ethylnonanoic acid. The gamma and delta branched acids include 4 methylpentanoic acid, 4 methylhexanoic acid, 5 methylhexanoic acid, 5 methylheptanoic acid, 4 ethyloctanoic acid, 4 ethyl 5,5 dimethylhexanoic acid, 4 methyldecanoic acid and 4,8-dimethylnonanoic acid. Olefinically unsaturated monocarboxylic acids include 4-pentenoic acid, 3-hexenoic acid, 2-ethyl-2-hexenoic acid and 10 undecenoic acid.

The presence or absence of unsaturation is not relevant to structural difference. The presence and position, if present, of branching determines structural difference, e.g. l0-undecenoic acid is structurally the same as n-nonanoic acid.

Generally, the saturated aliphatic 'monocarboxyclic acids are preferred for the practice of this invention as they are the most generally available and, therefore, the most economical acids to be used in the preparing of soluble copper mixed salts.

The mixed copper soaps of the present invention can generally be prepared by reacting a source of copper, i.e. copper metal or a copper compound, including a salt or a hydroxide, with the desired organic acids or soluble salts of the acids, especially the sodium salts. The reactions are preferably carried out in a nonpolar oil-miscible solvent so as to directly prepare the ultimately desired oilrniscible concentrated solution of copper. However, the reaction can also be carried out in an alcohol and/or water environment and the mixed soap separated as a solid before being dissolved.

Preparation from elemental copper can be carried out as follows: particulate finely divided copper metal plus two structurally different organic acids, as defined above, are dispersed in a mineral spirits solvent together with water. The mixture is heated to from about 60 to C. and is maintained at the temperature while it is agitated and air or oxygen is blown through the mixture as an oxidizing agent. The water is then distilled off after reaction is complete, leaving the solution of the mixed copper salt in the mineral spirits solvent. The general reaction equation is as follows:

wherein HA and HB are the structurally different acids.

A second method for preparing the copper mixed soap is by the reaction of cupric hydroxide with a mixture of the two organic carboxylic acids in mineral spirits solvent to prepare a solution of the mixed copper salt. Sufiicient amounts of the copper hydroxide and of the two acids are dispersed in mineral spirits to produce the desired concentration of copper in the final solution and reaction takes place at from about 30 to 70 C. The reaction mixture is then heated to above the boiling point of water formed. The final mineral spirits solution can then be used directly as a source of dissolved copper. The cupric hydroxide reagent which is used can also be a carbonated material having a formula (CuCO -Cu(OH) The copper mixed salt can also be obtained from a double decomposition reaction, where cupric sulphate is reacted with a mixture of the sodium salts of the two desired acids in an aqueous system to form a mixture of the mixed copper soap plus sodium sulphate. The sodium sulphate remains in solution in the Water system and the copper mixed soap precipitates out and is thus readily separated.

Another procedure for preparing these materials is as follows: a saturated solution of copper acetate and hot water is treated with hot ethanol. Before a precipitate can form a warm alcoholic solution of the two desired organic acids is added and the resulting solution kept Warm for about 15 minutes. The mixed soap is then separaetd from the solvent by suitable means.

In each of the above procedures the acid groups are preferably present in equimolar proportion; preferably the mixed acids are present slightly in excess of the amount of the copper present, preferably from to 15 percent of molar excess. The presence of additional acid, of course, does not interfere with the reaction but is wasteful.

The acids can, if desired, be mixed in other than equimolar proportions; however, this will result in a product which is actually a mixture of the copper mixed soap plus the copper soap of whichever acid is present in excess. Such a mixture of the mixed soapplus additional copper salt has been found to be soluble for mixtures containing up 200 percent molar excess of one of the acids. The excess amount of any acid that can be tolerated and still obtain a soluble product is at least in part dependent upon the solubility, in the mineral spirits or oil, of the salt of the acid present in excess. Even the most insoluble acid salt can be present in excess to a certain degree, apparently through some sort of solubilizing effect of the mixed soap. Preferably the maximum amount of excess is about 150 percent. Generally, even those acids that form the most insoluble salts of copper can be present up to about 50 percent in excess to form excess normal copper salt of that acid. The amount of the normal copper salt dissolved in the mineral spirits when formed from the excess acid can be above that which would be noramlly soluble in the nonpolar solvent, but it is soluble when present in solution with the mixed copper soap of the present invention.

In Whatever form the copper and the structurally different acids are combined, i.e. as a true mixed salt, as a mixture of normal salts, or as a mixture of one or two normal salts and a mixed salt, the molar ratio of copperzacid type A:acid type B, preferably is 1:'0.81.2: 1.2-0.8. If there are more than two different acid groups present, but only two structural types of acids, e.g. n-octanoic, n-nonanoic and Z-ethylhexanoic acid, the acids of the same type are added together to determine the proportion of that type present. For example, 0.5 mole of n-octanoic acid, 0.6 mole of nnonanoic acid, and 1.1 moles of 2-ethylhexanoic acid, gives a ratio of acid type Azacid type B of 1:1.

The copper mixed soap of the present invention is believed to exist as a true compound and not merely a solid solution of the two normal salts. Based upon the equilibrium distribution of products from these chemical reactions, however, a mixture of the mixed salt plus proportions of the normal copper salts of each of the two acids is probably present. Accordingly, the copper mixed soap of the present invention can also be defined by the method by which it is prepared: a copper soap prepared by the simultaneous reaction with copper of the groups of two structurally dilferent organic monocarboxylic acids, of the acids defined above. The coprecipitated copper salts which are also soluble in the proportions found for the mixed salts can be formed from the solutions of individually prepared normal salts that are mixed and then coprecipitated. Generally, when the normal copper salts of any one of the above defined acids are prepared by the methods described above in mineral spirits solvent, an unstable solution is formed, from which the copper soap precipitates at varying times after cooling to room temperature. If the solutions were mixed before precipitation, a stable solution is formed; especially where the copper soaps are present in equimolar amounts, or within the range of excess described above for the mixed salt. When the solvent is removed to form a coprecipitate, the coprecipitate can be redissolved to form a stable solution.

Also, generally, the mixed soaps or coprecipitated soaps, can be prepared by any method used for the preparation of the normal copper soaps, merely substituting a mixture of two structurally different acids, preferably in about an aquimolar mixture, as explained above, to form the desired mixed acid soap. For such normal soap preparations see, for example, US. Pats. Nos. 2,584,041 and 2,113,496.

Generally, the alpha-branched saturated aliphatic carboxylic acids and the straight chain aliphatic acids provided salts of copper having the lowest solubility. The beta and the gamma-branched acids have somewhat higher solubilities in mineral spirits or other nonpolar hydrocarbon solvents; therefore the alpha-branched and straight chain acids should not be tolerated in as great an excess before precipitation would occur from an oil solution as the more soluble salts of the beta or gamma acids. Further, the copper salts of the branched chain acids having a quaternary carbon atom at the terminal point of the chain furthest away from the carboxyl group tend to be as insoluble as the salts of the alpha acids. A surprising aspect of the present invention, is that the mixed salts formed from mixtures of alpha-branched and straight chain saturated aliphatic acids are substantially as soluble as are the mixed salts formed from an alpha-branched and a betabranched acid or the mixed salt of a beta and a gamma acid, etc.

The oil-soluble mixed copper soap of the present invention is soluble in a hydrocarbon nonpolar solvent or halogenated such solvent. The hydrocarbon solvents include the liquid distillates, or mineral spirits (hydrocarbon distillates), such as gasoline, kerosene, the diesel fuels, 1, 2, and 3, the higher-boiling distillates, known as fuel oils 4, 5 and 6, as well as aromatic hydrocarbon oils. In addition, the mixed soaps are soluble in fuels which become liquid only when pre-heated, such as higher melting residual oils which are semi-solid in nature and must be heated to temperatures of the order of F. to increase their fluidity before they may be used as burning fuels of the liquid type. Other non-petroleum derivatives solvents for the oil-soluble mixed copper soaps include xylene, turpentine, toluene and ethyl benzene.

Useful chlorinated organic solvents include o-dichlorobenzene, carbon tetrachloride, ethylene dichloride and perchloroethylene.

As state above, the use of halogenated, e.g. chlorinated, acid is contemplated in the preparation of the mixed soap. The halogenated acids are not now sufliciently low in cost so as to be economically useful as an additive for a fuel oil. If in the future such chlorinated acids do become cheaply available, or if, in specific instances, there are such halogenated acids available as a side product or by-product from other reactions, they can be usefully used in accordance with the suggestion of Johnson, US. Pat. No. 2,622,671 to improve the effectiveness of the soot remover composition. Chlorinated organic compounds, generally, can provide a source of chlorine in the concentrate. The chlorine reacts with copper to reduce soot formation apparently by lowering the ignition temperature of soot deposits. Johnson suggests adding a separate chlorinated organic compound. However, where chlorinated acids are available, one of these could be used to form the mixed soap and another structurally different organic acid, or halogenated such acid, in lieu of a mixture of the soap plus a separate chlorinated hydrocarbon compound.

The following examples represent certain preferred embodiments of the present invention and the preparation of certain of the mixed soaps and mineral spirit concentrates containing the mixed soap dissolved in proportions of approximately 8 to 10 percent by weight of copper. The usual concentration of the mixed copper soap product in mineral spirits is about 6 to 15 percent by weight copper and preferably about 8 to 12 percent copper.

7 COMPARATIVE EXAMPLES AM A series of normal copper soaps were prepared by the following procedure, using 2,2-dimethylpentanoic acid as an example:

The acid (136 g.), mineral spirits (230 g.), and cupric hydroxide (49 g.) were charged to a flask at room temperature, heated, with mechanical agitation, to 75-80" C., and maintained at that temperature until all of the cupric hydroxide had dissolved. The mixture was then heated to 120 C. to eliminate the water formed. Where there was no immediate precipitation, the solution was diluted with mineral spirits to about 8 percent by weight copper (to about 398 g. total weight of solution) and filtered hot (l110 C.) to remove any unreacted copper hydroxide. These procedures are carried out with about 4 percent excess acid, which tends to promote solubility.

The appearance of the soap product obtained from each acid used is set out in Table 1, below. In each case the same amount of copper hydroxide was used (49 g.):

8 mineral spirits solvent was permitted to cool by standing, and the following results were observed.

Molar ratio of alpha acid to alpha plus beta acids: Observations 0.388 Considerable dark green granular material.

0.5 Stable solutions.

0.756 s Some dark green material deposited.

EXAMPLE 3 TABLE I.-NORMAL COPPER SOAPS Grams oi-- Comparative Acid Mineral example Acid group used spirits used Solubility of soap in mineral spirits solvent A 2,2-dimethylpentanoic 136 230 Partially) soluble in mineral spirits at room temperature (up to 2%, by wtcopper 2-ethyl-4-methylpentanoic. 150 216 Crystallized IOU-120 C. 0.. Z-ethylhexanoic 150 216 crystallized 95-105" 0. D 2-propyl4-methylpentanoic-. 165 201 crystallized at 110120 C. E 2-propylheptenoic 180 186 crystallized upon vooling to room temperature. F 2-ethyl-2-hexenoic 150 216 crystallized at 100l20 C. G 3,5,5-trimethylhexanoic 165 201 Orystallized slowly upon aging at room temperature after 3 days. H 4-ethyi-5,5dimethylhexanoic 180 186 solidified completely at room temperature. I -methyl pentanoic 121 245 Orystallized upon cooling at room temperature. I n-Oetanoie 150 216 solidified completely at room temperature' K n-Nonanoic 165 201 Do. L. 10-undecenoic. 194 172 Do. M n-Hexanoic 121 245 Substantially all crystallized at room temperature.

As shown by the results set out in Table I, none of the normal soaps of copper are sufiiciently oil-soluble to provide a stable solution in mineral spirits of 8 percent copper, and only one is soluble to more than 1 percent copper. Four of the soaps solidified completely, forming a gel in the mineral spirits solvent.

EXAMPLE 1 A stable solution of an oil-soluble copper mixed soap was obtained by mixing 1.07 g.-mols 2-ethylhexanoic acid, 1.07 g.mols, 3,5,5-trimethylhexanoic acid and 1.0 mol copper hydroxide (Cu(OI-I) in mineral spirits. The materials were mixed and heated to from to 70 C. until reaction was substantially completed. The solution was then heated to 120 C. to eliminate the water formed during the reaction, filtered to remove any unreacted copper hydroxide, and then diluted with sufiicient additional mineral spirits to produce a solution containing 8 percent by weight of copper of the mixed copper carboxylates.

The clear solution was then concentrated by distillation to 10 percent by weight copper; the viscosity of this solution was determined to be E (1.25 stokes) on the Gardner- Holdt scale. The mineral spirits used in this preparation had the following composition: 6.7% aromatics, 91.3% saturates and 2% olefins (Shell Mineral Spirits l4566 The solvent was then distilled OE and the solid mixed copper soap was obtained. The solid mixed soap was of a soft plastic consistency and was colored green. The mixed soap was then completely redissolved at room temperature in additional mineral spirits to prepare a stable solution containing 8 percent copper.

EXAMPLE 2 The procedure of Example 1 was repeated several times but in each case using different proportions of the Z-ethylhexanoic acid (alpha acid) and 3,5,5-trimethylhexanoic acid (beta acid). The solution of the mixed soap in the propeller agitator and fritted glass air injection tube extending to the bottom of the flask. The copper and the acids were dispersed into the mineral spirits and the dispersion was then heated to C. Water (25 g.) was then added to the mixture and air blown through the mixture while it was vigorously agitated. After the reaction had gone to completion, any remaining solid material was filtered out. The solution was vacuum distilled at C. and a pressure of 25 mm. Hg absolute, to remove any remaining water.

The mineral spirits solvent was evaporated to obtain the mixed soap of copper 2-ethylhexanoate/3,5,5-trimethylhexanoate. The solution was diluted with mineral spirits to a concentration of 10 percent copper, to form a dark green solution having the same properties as that obtained in Example 1. This material readily dissolves in the mineral spirits to form the desired 8 percent by weight copper solution.

EXAMPLE 4 The mixed soap of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid is also formed by the reaction of one mol of cupric sulphate mixed with 1.07 mols each of sodium Z-ethylhexanoate and sodium 3,5,5-trimethylhexanoate. The sodium salts are dissolved in water and heated to 70 C. The mixed soap of copper 2-ethy1hexanoate/3,5,5-trimethylhexanoate precipitated out and is readily separated as a soft plastic mass identical to that formed in Example 1. The solid material is dried and then readily dissolves in the mineral spirits of Example 1 to form a stable solution.

EXAMPLE 5 One g-mol of copper acetate is dissolved to form a saturated solution in hot water. To this saturated solution is added 200 mls. of hot ethanol at 70 C. Immediately thereafter, and before a precipitate could form, a solution in alcohol of 1.11 g.-mols each of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid is added to the copper acetate solution which is maintained at 70 C. for about 15 minutes. The alcohol and water mixture is heated away to leave the mixed copper salt.

EXAMPLE 6 The procedure of Example 1 was followed but Z-ethyl- 4-methylpentanoic acid is substituted for the 2-ethylhexanoic acid. The mixed copper soap of the two acids was obtained as a green plastic deposit, which readily redissolved in mineral spirits to form an 8 percent copper stable solution.

EXAMPLES 7-17 The procedure of Example 1 was followed but using COMPARATIVE EXAMPLE COMPARATIVE EXAMPLES P-R The procedure of Example 1 was repeated, but substituting the acid pairs and amounts set forth in Table IH. Each pair of acids in Examples P-R, respectively, are in the same structural group. The results obtained were as the acids and the proportions set forth in Table II, below. 15 follows:

TAB LE III Grams Comparative Acid Mineral Solubility of mixed soap in mineral example Acid pairs used spirits used spirits soiv ant P 2-ethyl hexanoic 75 216 Crystallized at lilo-110 C.

2-ethyl-4-methyl pentanoic. 75 Q Z-ethyl hexanoic 75 216 Do.

2-ethyl-2-hexenoic 75 R 2-eth yl hexanoic 75 223 Orystallized partially at 100-110" 0.; more 2,2-d1methyl pentanoic. 68 upon cooling to room temperature.

In each case 49 g. of copper hydroxide was used, and a stable solution containing 8 percent by weight of copper was prepared.

As shown, by each of Examples N-R, mixed soaps formed from two acids that are structurally the same are not oil-soluble where the normal copper soap of each TABLE II Acid Grams of 8% Mineral copper solu- Yield Example Acids used (A) (g.) (B) (g.) spir1ts(g.) tion obtained (percent) (A) 2,2-dimethyl pentauoic 7 gfifil-tliliilethtlg liexantole aieidn} 68 5 382 0 e y me y pen ano e 8 "{(B) 3,5,5-trimethyl hexanoie acid 75 5 5 385 8 (A) 4-ethyl-5,5-dimethyl 9 exam 0 82. 5 193. 5 393 98, 3

3,5I-trimelthy1hexanoie acid nonano c 3,5,5-timeth1y1 haxanoic acid. 5 5 201 395 2 10-un eceno e n gjki-trihznfithyl l'iexanoic acid.- 97 5 5 377 8 -e y exeno c 12 "{(B) 3,5,5-trimethyl hexanoic acid 5 5 (I) (a) (A) 4-ethyl-5,5-dimethyl 13 75 201 395 99. 2

(I3 2-eItIhy1 he ranoic acid 11- onano c 14 iethtyll liexaniic aicidn. 5 75 5 392 5 me y pen ano c E2; 2 1 F Y 60.5 60.5 245 382 96.0

me y pen ano c 16 "{(2) idtfifitrlirlpeghyllhexanoie acid 5 5 223 381 7 -e y u ano c 17 (B) 3,5,5-trimathyl h-sxanoic aeid 5 5 233 381 7 1 Thick, but clear solution obtained. I Not determined; estimated over 90%.

COMPARATIVE EXAMPLE N The procedure in Example 1 was repeated but substituting for the two acids used 2-ethylhexanoic acid and the mixed alpha acids known as Versatic 9 (56% 2,2,4,4-

tetramethylpentanoic acid and 27% 2-i sopropyl-2,3-di- 70 methylbutanoic acid). The material did not form a stable solution but immediately precipitated out as a dark green granular copper soap. The precipitation occurred at elevated temperatures of about 95 to C., even before the solution could cool.

acid is insoluble in the mineral spirits solvent.

EXAMPLE 18 A freshly prepared solution of copper 3,5,5-trimethyl hexanoate in mineral spirits as prepared in Comparative 60 Example G (398 g., 8% copper) was maintained at 100 C. and mixed with a solidified copper 4-ethyl-5,S-dimethyl hexanoate solution (398 g., 8% copper) as prepared in Comparative Example H. The mixture was heated up to C. to form a uniform solution, and held there for 5 5-10 minutes. The temperature was cooled down to room temperature and the solution remained clear and stable. A coprecipitate can be obtained by evaporating the mineral spirits solvent. The coprecipitate can be readily redissolved in mineral spirits at room temperature.

EXAMPLES 19 AND 20 The procedure of Example 18 was repeated but substituting the salts in accordance with Table IV below. The mixture is dissolved at the temperature indicated in 75 Table IV to form a stable solution in each case.

TABLE IV Dissolution tempera- Condition on cooling Example Salt A and (condition) Salt B and (condition) ture, C. to room temperature 19--- Copper 3,5,5-trimethyl hexanoate Copper-nonanoate 2 80 Clear and stable solution. 20 do Copper-caprylate/n-nonanoate 74 Do.

1 Solution (Example G).

2 solidified solution (Example K).

3 solidified solution (Example Both Examples 19 and 20 formed solutions of the mixed salts that were clear and stable. They could be evaporated to form a coprecipitated mixture of salts that could be redissolved in mineral spirits solvent.

EXAMPLE 21 A stable, clear solution in o-dichlorobenzene of an oilsoluble mixed copper soap product was obtained by mixing 1.07 g.-mols 2,2-dimethylpentanoic acid, 1.07 g.-mols 3,5,5-trimethylhexanoic acid and 1.0 mol copper hydroxide (Cu(OH) in o-dichlorobenzene. The materials were mixed and heated to from 30 to 70 C. until reaction was substantially completed. The solution was then heated to 120 C. to eliminate any water formed during the reaction and then diluted with sufficient additional o-dichlorobenzene to produce a clear green solution containing 8 percent by weight of copper of the mixed copper soaps.

EXAMPLE 22 The procedure of Example 21 was repeated but substituting xylene for the o-dichlorobenzene. After preparing the solution, the xylene can be readily boiled away and the solid mixed copper soap obtained. The mixed soap was colored green and had a soft plastic consistency. The mixed soap was then readily redissolved in xylene at room temperature to prepare a stable solution containing 8 percent copper.

The concentrated mineral spirit solutions of the mixed copper soaps prepared above are suitable for directly mixing with a fuel oil or other hydrocarbon fuel to add the desired amount of the soluble copper as a soot remover additive. Generally, a concentrated solution containing 8 percent by weight of the copper metal is added in a one part per thousand ratio to fuel oil; higher molecular weight, i.e. higher boiling point fuel oils, and the semi-solid so-called residual oils that generally have a higher carbon content will require a somewhat higher percentage or proportion of the concentrate perhaps from about one part per 200 to about 800 parts of the fuel oil. Broadly, the concentrated solution is preferably added in a proportion of one part to from about 200 to about 2000 parts of fuel oil.

The following is claimed as the patentable embodiment of the above defined invention:

1. An oil-soluble mixed copper soap product comprising combined copper combined with acid groups derived from two structurally different organic monocarboxylic acids wherein the diflerence in structure is defined in terms of the presence and position of branching in the acid groups and wherein the acids are selected from the group consisting of saturated and olefinically unsaturated aliphatic acids, the normal copper soaps of at least one of said acids being insoluble in oil at room temperature.

2. The soap product of claim 1, wherein the aliphatic acids are selected from the group consisting of straight chain acids, alpha-substituted branched chain acids, betasubstituted branched chain acids, gamma-substituted branched chain acids and delta-substituted branched chain acids.

3. A stable solution containing at least 6 percent by weight of dissolved copper comprising a solvent selected from the group consisting of nonpolar hydrocarbon solvents and chlorinated nonpolar hydrocarbon solvents and an oil-soluble mixed copper soap product according to claim 1.

4. Oil soluble mixed soap products in accordance with claim 1 wherein the aliphatic acids contain from about 6 to about 11 carbon atoms.

5. An oil-soluble copper mixed soap of two structurally difierent organic monocarboxylic acids wherein the difference in structure is defined in terms of the presence and position of branching in the acid groups and wherein the acids are selected from the group consisting of saturated and olefinically unsaturated aliphatic acids, the normal copper soaps of at least one of said acids being insoluble in oil at room temperature.

6. A mixed soap in accordance with claim 5, wherein the acids each contain at least five carbon atoms.

7. A mixed soap in accordance with claim 6, wherein the acids each contain from five to twenty carbon atoms.

8. A mixed soap in accordance with claim 5, wherein the acids comprise at least one saturated aliphatic acid.

9. A mixed soap in accordance with claim 8, wherein at least one saturated aliphatic acid is an alpha or a betasubstituted branched chain acid or a straight chain acid.

10. A mixed soap in accordance with claim 8, wherein the acids comprise one alpha-branched and one betabranched saturated acid.

11. A mixed soap in accordance with claim 8, where the acids contain from about six to about eleven carbon atoms.

12. A mixed soap in accordance with claim 5, wherein the acids comprise at least one olefinic acid.

13. A mixed soap in accordance with claim 12, wherein at least one olefinic acid is an alpha or a beta-substituted branched chain acid or a straight chain acid.

14. A mixed soap in accordance with claim 5, wherein the acids are Z-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid.

15. The oil soluble copper mixed soaps in accordance with claim 5 wherein the aliphatic acids contain from about 6 to about 11 carbon atoms.

16. An oil soluble mixed copper soap product containing combined copper and organic monocarboxylic acid groups derived from two structurally different organic monocarboxylic acids wherein the dilference in structure is defined in terms of the presence and position of branching in the acid groups and wherein the acids are selected from the group consisting of saturated and olefinically unsaturated aliphatic acids, the normal copper soaps of at least one of said acids being insoluble in oil at room temperature, the soap product being prepared by a process comprising simultaneously reacting copper, in the form of either combined or elemental copper, with acid groupcontaining compounds containing two structurally difierent organic monocarboxylic acid groups.

17. The compound of claim 16, wherein the acid group-containing compounds are selected from the group consisting of the acids and the salts of the acids.

18. The product of claim 16, wherein copper hydroxide is reacted with a mixture of two structurally different acids.

19. The product of claim 16, wherein copper metal is reacted with a mixture of two structurally different acids.

20. The product of claim 16, wherein a water-soluble copper salt is reacted with a mixture of the sodium salts of two structurally different acids in an aqueous solution.

21. The product of claim 20, wherein the copper salt is copper sulphate.

22. The product of claim 16, wherein copper acetate is reacted with two structurally different organic acids.

23. The product of claim 16, wherein the mol ratio of a first acid to a structurally different acid is from about 2:1 to 1:2.

24. An oil-soluble coprecipitated mixture of copper soaps of two structurally different organic monocarboxylic acids wherein the difference in structure is defined in terms of the presence and position of brar iching in the acid groups and wherein the acids are selected from the :group consisting of saturated and olefinically unsaturated aliphatic acids, the normal copper soaps of; at least one of said acids being insoluble in oil at room temperature, the coprecipitated mixture being sufiiciently soluble in mineral spirits to form a solution containing by weight of copper.

25. The coprecipitated mixture of claim 24, wherein the mole ratio of one structurally different acid group to a second structurally different acid group being from about 2:1 to about 1:2.

26. A stable solution comprising a solvent selected from the group consisting of nonpolar hydrocarbon solvents and chlorinated nonpolar hydrocarbon solvents, combined copper and acid groups derived from two structurally different organic monocarboxylic acids wherein the difference in structure is defined in terms" of the presence and position of branching in the acid groups and wherein the acids are selected from the groiip consisting of saturated and olefinically unsaturated aliphatic acids,

References Cited UNITED STATES PATENTS 2,584,041 1/ 1952 Nowak 260-97.5 2,528,803 11/ 19 Unkefer 260--97.5 2,373,387 4/1945 Elliott 260-97.5 X 2,471,153 5/1949 Hoover 260-975 X 2,622,671 9/1953 Johnson 4313 3,446,737 5/1969 Panzer 252 ROBERT F. BURNETT, Primary Examiner M. E. MCCAMISH, Assistant Examiner US. Cl. X.R.

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US4486448 *Oct 14, 1982Dec 4, 1984Societe Anonyme Dite: L'orealCopper lanolate and anti-acne compositions containing the same for topical application to the skin
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US4826694 *Apr 4, 1986May 2, 1989Balfour Manufacturing CompanyRuminant feedstuffs, their production and apparatus for use therein
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US6300373May 22, 1995Oct 9, 2001American Biogenetic Sciences, Inc.Antiproliferative and neurotrophic molecules
US6458840Apr 23, 2001Oct 1, 2002American Biogenetic Sciences, Inc.Use of valproic acid analog for the treatment and prevention of migraine and affective illness
US7176240Jul 15, 2002Feb 13, 2007Ono Pharmaceutical Co., Ltd.Such as 5-fluoro-2-propylpentanoic acid for improving GABA (gamma-aminobutyric acid) receptor responses; treatment of neurodegenerative diseases
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Classifications
U.S. Classification252/1, 554/161, 554/74, 554/158, 554/157, 502/170, 44/363
International ClassificationC07C53/126, C07C53/128, C07C57/03, C10L1/18, C07F1/00, C10L1/188
Cooperative ClassificationC07F1/005, C07C57/03, C07C53/128, C07C53/126, C10L1/1881
European ClassificationC10L1/188B, C07C53/128, C07C53/126, C07F1/00B, C07C57/03
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Dec 30, 1982ASAssignment
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Effective date: 19821222