US2989564A - Nu-substituted aminopropylamine monosulfonates - Google Patents

Description

Un Ste Patent.

No Drawing. Filed Aug. 12, 1954, Ser. No. 449,496 4 Claims. (Cl. 260501) This invention relates to new chemical compounds.

j More particularly, the invention is concerned with the stabilization of mineral oils by incorporation therein of new salt compositions.

Various mineral oils tend to deposit oil-insoluble deterioration products that are formed during storage or service conditions. For example, straight run distillate fuel oils can form sludge during storage despite their high content of normally stable paraflinic hydrocarbons. Where sludge deposition occurs in such oils, it is usually attributed to the presence in the oils of materials that are not normally present, e.g., impurities picked up during refining, or perhaps remaining in the oil due to incomplete refining, rather than to the inherent instability of the oil itself. Sludge formation in straight run fuel oils is considered to be chiefly a problem of oxidation and the formation of insoluble oxygenated products.

Unlike straight run distillate fuel oils, catalytically cracked fuel oil distillates are rich in olefinic, aromatic and mixed olefinic-aromatic components. Sludging in the latter oils is considered to involve primarily condensation and/ or polymerization type reactions which result in the formation of insoluble reaction products of relatively high molecular weight.

Distillate fuel oil compositions containing mixed straight run and catalytically cracked fuel oil distillates have proved especially troublesome with regard to sludge deposition during storage at normal atmospheric temperatures. It has been found that the sludging characteristics of such mixed, or blended, fuel oil distillates are strikingly poor, much poorer than can be accounted for from the known sludging characteristics of the individual component fuel oil distillates alone. While the sludge formed in mixed distillate fuel oils no doubt contains some sludge of the type formed in each component oil, the sludge formed in the blended fuel oils is consistently greatly in excess of the amount that can be accounted for from the known sludging tendencies of the individual component oils, thus indicating the existence of a special problem.

Lubricating oils, on the other hand, such as those used for crankcase lubricants in internal combustion engines of the gasoline or diesel type, present still another problem, that is, such oils tend under service conditions to deposit oil oxidation products, fuel soots, resins and other oil-insoluble deterioration products on the metal surfaces with which the oil comes in contact.

- amounts of the novel salt compositions ofthis invention.

2,989,564 Patented June 20, 1961 The salts included by this invention are the monosulfonates of oil-soluble hydrocarbon sulfonic acids and 1,3-diaminopropanes having the general formula:

R HI I'CH5CHr-CH NH where R is an aliphatic radical containing from 8 to 30 carbon atoms.

The salts of this invention are prepared by partial neutralization, with an oil-soluble sulfonic acid, of a 1,3-diaminopropane that contains a long-chain aliphatic radicalsubstituted, secondary amino grouping. The aforesaid partial neutralization reaction normally takes place spontaneously at room temperature with evolution of heat, but in some cases moderate heating may be desirable in order to accelerate the reaction. In no case should the reaction be carried out at temperatures in excess of about F., since decomposition of the resulting ammonium salt may occur with prolonged exposure to temperatures substantially in excess of this limit. In order to produce the desired monosulfonate salts, the mol ratio 'of the reactants in the neutralization procedure should be formula: 30

where R is an aliphatic radical containing from 8 to 30 carbon atoms.

Thus, the present invention includes, for example, the use of monosulfonates of long-chain alkyl-, alkenyland alkadienylaminopropylamines. Specific examples of such diamino compounds are 3-octylaminopropylamine, 3-decylaminopropylamine, 3-tetradecylaminopropylamine, 3-tetradecenylaminopropylamine, 3- eicosylaminopropylamine, 3-eicosenylarninopropylarnine, 3-docosylaminopropylamine, 3-docosenylaminopropylamine, 3-docosodienylaminopropylamine, and 3-triacontanylaminopropylamine. Within the general class of 1,3-

diaminopropanes capable of forming the monosulfonates 'of this invention, the diamines in which the long-chain, aliphatic N-substituent of the secondary amino grouping is an alkyl or alkenyl group containing at least 12, and preferably from 12 to 18, carbon atoms are considered to form especially effective addition agents. Examples of 1,3-diaminopropanes which are considered to form exceptionally efiective monosulfonates for the purposes of this invention are the 3-dodecyl-, the 3-hexadecylaminopropylamines, and especially the 18 carbon alkyl-, alkenyl-, and alkadienyl-substituted 1,3-diaminopropanes,

such as the 3-octadecyl-, 3-octadecenyl-, and 3-octadecadienylaminopropylamines. Although aliphatic hydrocarbon N-substituted 1,3-diaminopropanes are preferred, the

invention also includes salts derived from diamines in which the N-substituent of the secondary amino grouping is itself substituted with one or more groups that contain elements such as oxygen, sulfur, nitrogen or halogen and that do not interfere with the oil-solubility of the salt. Representative examples of 1,3-diaminopropanes containing such substituents are 3-ricinoleylaminopropylamine and 3-(chlorostearyl)-aminopropylamine. Mix- 3 tures of 1,3-diaminopropanes such as are formed when the long-chain, aliphatic N-substituent in the secondary amino grouping is derived from mixed fatty acids obtained from naturally occurring fats and oils form highly effective monosulfonate salts within the scope of this invention. In such instances the aliphatic N-substituent in the secondary amino grouping will be a straight chain, mnovalent hydrocarbon radical containing from 8 to 20 carbon atoms. Examples of such mixtures of 1,3-diaminopropanes are 3-"tallow-aminopropylamine, 3- soya-aminopropylamine, and 3-cocoaminopropylamine, Where the respective N-substituents are mixed alkyl and unsaturated alkyl groups derived from animal tallow (C -C fatty acids, soybean (C -C fatty acids, and coconut (C -C fatty acids.

The sulfonic acids that form the monosulfonates included by this invention are'the'oil-soluble hydrocarbon sulfonic acids. Such acids may be represented by the generic formula R SO H, where R is an organic radical of at least predominantly hydrocarbon character which -is capable of imparting oil-solubility to the acid. These sulfonic acids may be oil-soluble aliphatic hydrocarbon sulfonic acids, including naphthenic hydrocarbon sulfonic acids, representative examples of the former of which are octyl, nonyl, decyl, undecyl, lauryl, tridecyl and myristyl sulfonic acids, and of the latter, the octyl-, dodecyl-, and dodecenyl-cyclopentyl and similarly substituted cyclohexyl sulfonic acids. Also satisfactory are the alkaryl sulfonic acids such as octyl, decyl, dodecyl and cetyl benzenesulfonic acids, as well as the so-called keryl, or kerosene, and wax-alkyl benzenesulfonic acids, including the corresponding dialkyl benzenesulfonic acids. The preferentially oil-soluble petroleum sulfonic acids, normally referred to as mahogany acids in order to differentiate them from the preferentially aqueous alcohol, distallation to remove the extraction solvent, and regeneration of the sulfonic acid by treatment of the residue with an equivalent amount of a mineral acid. Particularly suitable mahogany acids are those having an average molecular weight between about 400 and about 650.

The reaction products of the abovedescribed partial neutralization of the long-chain aliphatic N-substituted 1,3-diaminopropanes with substantially equimolar proportions of oil-soluble hydrocarbon sulfonic acids are simple addition salts having the following probable generic formula:

wherein R and R are as defined above. Although some product may be formed in which the sulfonic acid adds to the primary amino group, the above-indicated product tends to predominate in view of the greater basicity of the secondary amino group.

The preparation of the monosulfonates included by this invention, previously described in general, and a specific embodiment of the invention are illustrated by the following specific example:

Example Oil-soluble petroleum sulfonic acids having an average molecular weight of about 430 were prepared by two successive treatments of a commercially obtained mineral a 4 oil solution containing about 30 percent of the calcium salt of mahogany acids with 37 to 38 percent hydrochloric acid at 170 to 180 F., and extraction of the acidified product With benzene. The extract was then blown with nitrogen to dry. The calcium petroleum sulfonate employed had a molecular weight of 905 (calculated from the base number of the 30 percent mineral oil concentrate). Typical samples of said concentrate had the following properties:

Approximately 430 grams (one combining mol) of the oil-soluble petroleum sulfonic acid obtained as described above were dissolved in approximately 1000 grams of oil and 600 grams of benzene, and the resulting solution was added with stirring to 400 grams (one combining mo of mixed S-fatty alkyland alkenylaminopropylamines containing approximately percent active ingredient. The latter, designated as 3-tallowaminopropylamine, had a theoretical molecular weight of 320, a combining weight of approximately 400, and a melting range of approximately 44 to 48 C. The fatty alkyl andalkenyl substituents of the diamine were derived from animal tallow fatty acids. Accordingly, the 3-talloW-aminopropylamine contained predominantly 3-oleylaminopropylamine, or 3-octadecenylaminopropylamine, together with lesser proportions of 3-hexadecyland 3-octadecylaminopropylamines, and small amounts of 3-myristyland 3-linoleylaminopropylamines.

The crudeproduct of the foregoing reaction was a mixture of monosulfonates of mahogany acids and 3C alkyland alkenylaminopropylamines, the predominant component of which mixture was the monosulfonate of Gravity, API 26.0 Viscosity, SUV, F. 3682 Sulfur, percent 1.71 Nitrogen, percent 1.31 Acid number 34.8

The product obtained by reacting the undiluted sulfonic acids (obtained by extraction of a 45 weight percent oil concentrate thereof with about 5 volumes of a solvent comprising equal volumes of water and isopropyl alcohol) in the above-indicated mol ratio with 3-tallow-aminopropylamine was a soft tan grease at room temperature.

The foregoing example indicates the manner and ease of preparation of themonosulfonate salts of this invention and illustrates a specific embodiment of the invention. Specific examples of other salts included by this invention can be prepared by reaction of substantially equimolar proportions of other herein disclosed 1,3-diaminopropanes with the foregoing oil-soluble petroleum sulfonic acids, or with other members of the herein disclosed class of oil-soluble hydrocarbon sulfonic acids, in the aboveindicated molecular ratio.

The addition of minor amounts of the salts of this invention to mineral oils tending to deposit insoluble deterioration products has been found to diminish the deposition of such materials from the oils. For example, the addition of very small amounts of monosulfonate salts of the foregoing type to distillate fuel oils, such as blended distillate fuel oils cotnaining both straight run and catalyticallycracked components,.has been found to produce a markedimprovementin the sludgingtendenciesof the oils. Other distillate fuel oils are also improved by the salts of this invention. In addition, lubricating'oils containing minor amounts of the salts of this invention exsuch monosulfonate will depend to someextent upon the particular compound used. Also, the minimum effective inhibitor concentration can vary considerably according to the specific nature of the oil to be inhibited. In general,

however, the herein disclosed salts are useful in concentrations of as little as about 0.005 percent to about 25 percent by weight of the composition. Thus, major improvement of the sludging characteristics of distillate fuel oils is usually obtainable by incorporation therein of from about 0.01 to about 0.05 percent by weight of the herein disclosed class of monosulfonates. Nevertheless, in some cases it will be advantageous to add as much as about 0.1

.percent by weight of the inhibitor, and in unusual instances it may be found desirable to add as much as about 1.0 percent by weight of the inhibitor. The salts of this invention are important in lubricating oils in concentrations of from about 1 to about 25 percent by weight of the composition. Normally major improvement in detergency properties is obtainable by the use of between about 5 percent and about 15 percent by weight of the composition. In the instance of heavy-duty type oils,

.larger amounts, e.g., up to 25 percent by weight of the compositiomcan be used.

The monosulfonate inhibitors included by this invention may be incorporated in the oils to be inhibited in any suitable manner. Thus, the salts may be formed in situ in the oil, they may be added, per se, directly to the oil, or they may be added in the form of concentrates. In the case of a blended fuel oil they can be added either immediately after blending or after the mixture has been stored for a substantial period of time. Alternatively, the

salts of this invention may be formed in situ in, or added per se or in the form of concentrated solutions to one component of the blend, e.g., either the straight run or the catalytically cracked fuel oil distillate, prior to blending. Suitable concentrates containing the monosulfonate inhibitors of this invention comprise, for example, mineral oil solutions or dispersions containing from about 2 to 50 3 percent, and preferably from about 30 to 50 percent, ac-

tive ingredient. In the case of mineral oil dispersions it may be desirable to heat the dispersion and/or the oil that is to be inhibited, e.g., to a temperature of from about 100 to about 140 F., in order to facilitate blending. An

alternate practice involves blending at ordinary atmospheric temperatures, using a solution of the inhibitor in a solvent that has a large solubility therefor, e.g., benzene,

I isopropanol or methyl isobutyl ketone, and that does not adversely affect the stability of the oil.

As indicated, the salts of this invention are adapted to improve the stability of a variety of oils. The class of distillate fuel oils to which this invention is applicable includes those containing straight run and/ or catalytically .cracked fuel oil distillates such as are used for domestic heating and for some industrial heating purposes, typical of which are the so-called No. 2 fuel oils, i.e., distillate oils boiling within the approximate range of 350 to 750 F. and having a minimum API gravity of about 26. The

ratio of the volume of the catalytically cracked to the straight run oil is within the range of about 9:1 and about 1:9. It is especially advantageous when applied to mixed oils containing these oils in a volume ratio within the range of 4:1 and 1:4.

. Xe. Lubricating oils that are benefited by the salts-of this invention include those derived from Coastal, Mid- Continent and Pennsylvania crudes, whether acid treated -or solvent treated. The invention is especially important in the improvement of lubricating oils that are adapted for use as crankcase lubricants.

The utility of the herein disclosed class of monosulfonate salts of long-chain, aliphatic N-substituted 1,3-diaminopropanes has been demonstrated by subjecting various mineral oil compositions containing the same to standard test procedures designed to evaluate various characteristics of the oils. For example, mixtures of catalytically cracked and straight run fuel oil distillates containing various concentrations of representative salts of the class included by the invention have been subjected to a standard accelerated stability test. The test samples were made up -by adding the desired concentration ofeach additive to be tested to separate samples of various fuel oil mixtures containing 50 percent by volume of a straight run No. 2 fuel oil distillate and 50 percent by volume of a catalytically cracked fuel oil distillate, and having varying sludging characteristics.

The stability test referred to above was carried out on the mixed fuel oil compositions by heating 600 gram samples of the fuel oil compositions for a period of 16 hours at 210 F. in loosely stoppered, one-quart clear glass bottles. Following the heating period each test sample was cooled to room temperature and filtered by suction through a tared, medium porosity, fritted glass Goochtype crucible. The sludge in each crucible was washed with heptane. Complete removal of the sludge adhering to the inside of the bottles was obtained by means of a rubber policeman and heptane. The respective crucibles were dried in an oven maintained at 210 F. for 1 hour, cooled in a desiccator and reweighed. The increase in weight was recorded as milligrams of sludge per 600 grams of oil.

The efiectiveness of the herein disclosed class of monosulfonates to improve the sludging characteristics of distillate fuel oils is considered to be peculiar thereto and is demonstrated by the fact that corresponding disulfonate salts of the herein disclosed long-chain, aliphatic N-substituted 1,3-diaminopropanes and sulfonates of low molecular weight 1,3-diaminopropanes do not as a class exhibit appreciable sludge inhibition in distillate fuel oils. Similarly, no appreciable inhibition of sludge deposition in distillate fuel oils is obtained with monosulfonates of non-oil-soluble hydrocarbon sulfonic acids and long-chain, aliphatic N-substituted 1,3-diaminopropanes.

As illustrating the improvement obtainable with the class of monosulfonates included by this invention arid also by way of illustrating the unique nature of the properties of these compounds, the specific results obtained by testing fuel oil compositions containing the following additives are set forth in tabular form elsewhere hereinafter: 3-tallow-aminopropylamine mono-petroleum sulfonate (prepared in accordance with the foregoing specific example), 3-tallow-aminopropylarnine di-petroleum sulfonate (prepared by reacting the diamine and the petroleum sulfonic acid of the example in a 1:2 mol ratio), 3-laurylaminopropylarnine di-petroleum sul-fonate (prepared by reacting 3-laurylaminopropylamine and the petroleum sulfonic acid of the example in a 1:2 mol ratio), 3-tallow-aminopropylamine mono-toluene sulfonate, 3- isopropylaminopropylamine monosulfonate (prepared by reacting 3-isopropylaminopropylamine and the petroleum sulfonic acid of the example in a 1:1 mol ratio), the corresponding disulfonate, 3-diethylaminopropylamine monosulfonate (prepared by reacting diethylaminopropylamine with the petroleum sulfonic acid of the example in a 1:1 mol ratio), and the corresponding disulfonate.

The fuel oil mixture referred to as Blend A in the following table was a 1:1 by volume mixture of Eastern Venezuela straight run and fluid catalytically cracked No.

, tion.

2 fuel. oil distillates and had the following physical-properties:

Gravity, API 3.4.0 Viscosity, jSUS 35.2 Color, NPA 2.5 Pour point, F. Flash point, .00, F. 170 Carbon residue, Conradson 10.01 Neutralization value, base No 0.05 Distillation:

Initial boiling point, F. 376

End boiling point, F 632 Bromine No. 10.4 OIefins, wt. percent 14.0 Aromatics, vol. percent 21.5 Aniline point 135.7 Ash, oxide, wt. percent 0.01

The foregoing properties are typical of, although not necessarily identical with, similarly compounded Blends B, C, and E, and more complex Blend D.

TABLE A Sludge, lug/600 g. Oil, After 16 Hrs.

1. Blend A50/50 (vol) Mixture of Mid-Continent SR.

and F.C.C. No. 2 Fuel Oil Distillate 35. 8 2. Blend A plus 0.02 vol. percent 3-Tallow-aminopropylamine Mono-Petroleum Sulfonate 2. 8 3. Blend A plus 0.02 vol. percent 3-Tallow-aminopropylarnine Di-Petroleum Sultanate 74. 0 4. Blend A plus 0.04 vol. percent 3-Tallow-arni.no-

propylamine Di-Petroleum Sultanate 84. 6 5. Blend B50/50 (vol.) Mixture of E.V.S.R. and F.C.G.

No. 2 Fuel Oil Distillate 14.0 6. Blend B plus 0.02 wt. percent 3-Tal1ow"-aminopropylamine Mono-Petroleum Sulfonate 1. 7 7. Blend C50/50 (vol.) Mixture of E.V.S.R. and F No. 2 Fuel Oil Distillate 16. 3 8. Blend 0 plus 0.02 vol. percent 3-Laurylaminopropylamine Di-Petroleum Sulfonate 16. 4 9. Blend 0 plus 0.03 vol. percent 3-Laurylaminopropylamine Di-Petroleum Sull'onate 23. 3 10. Blend D-Mixture of )4 W.'I.S.R./% S.L S R./%

F.0.0. N0. 2 Fuel Oil Distillate 1 7. 2 11. Blend D plus 0.02 Wt. percent 3-Tallow"-aminopropylamine Mono-Toluene Sulfonate 98. 5 12. Blend E-50/50 (vol.) Mixture of Mid-Continent S.R.

and F.C.C. No. 2 Fuel Oil Distillate 18.0 13. Blend E plus 0.02 vol. percent 3-Is0propylaminopropylamine Mnnnsnlfnnate 0- 3 14. Blend E plus 0.02 vol. percent 3-Isopropylarninopropylamine Disulfonate 52. 4 15. Blend E plus 0.02 vol. percent,Diethylaminopropylamine Monosultonate 43.4 16. Blend E plus 0.02 vol. percent Diethylaminopropylamine Disnlfnnatp 54, 1

1 Blend 0133.33 vol. percent each of West Texas Straight Run, Southern Louisiana Straight Run, and Fluid Catalytically Cracked No. 2 Fuel on Distillates.

Fuel oil Compositions 2 and 6 in the foregoing table and the inhibitors used therein are specific embodiments Y of the invention, and the results shown in the Table for these compositions are considered typical of thoseobtainablewith the monosulfonate salts of the class included by the invention. Comparison of the results obtainedjfor Compositions 2 and'6 with corresponding blank Compositions 1 and 5 clearly indicates the marked improvement in sludging characteristics of mixed distillate fuel oils that is obtainable with the salts included by this inven- On the other hand, comparison of the sludging characteristics of Compositions 3 and 4 and-Compositions 8 and 9 with those for the respective blank Compositions 1 and 7 indicates that the corresponding disulfonate salts do not as a class function similarly as the monosulfonates included by this invention. Similarly, comparison of the results obtained for Composition 11 with those obtained with blank Composition clearly indicates that monosulfonate salts of non-oil-soluble hydrocarbon sulfonic acids also fail to improve the sludging characteristics of mixed catalytically cracked and straight run jfuel oils. Comparison of the, sludging characteristics for ,Compositions .13 to 16, inclusive, withthose for blank Composition 12 indicates that low molecular weight 1,3-diaminopropane sulfonates are unsatisfactory inhibitors.

' The addition agents of this invention are especially advantageous in that they are essentially ashless in character.

It will be understood that the foregoing examples of the invention are. merely illustrative and that other members of the class of sludge-inhibiting salts included by the invention can be used in the same concentrations, or in other concentrations within the herein disclosed ranges, to prepare mixed catalytically cracked and straight run fuel oil compositions having similarly improved sludging characteristics. Specific examples of other monosulfonate salts that are suitable for the purposes of this invention are the mono-lauryl sulfonates, mono-myristyl sulfonates, mono-dodecylcyclohexyl sulfonates, mono-naphthenyl sulfonates, mono-dodecylbenezene sulfonates, mono-cotylbenezene sulfonates, mono-kerosense-alkylbenezene sulfonates and mono-wax-alkylbenzene sulfonates of 3-dodecylaminopropylamine, 3-tetradecylaminopropylamine, 3-hexadecylaminopropylamine, 3-octadecylaminopropylamine and 3-octadecenylaminopropylamine. Other specific examples of suitable additive agents included by the invention are mono-sulfonates corresponding to those listed above of mixed fatty alkyl-and alkenylaminopropylamines such as 3-"ta1low-aminopropylamine, 3-cocoaminopropylamine and 3-soya-aminopropylamine. The foregoing additives can be substituted in the fuel oil composition exemplified by Compositions 2 and 6 in the same or equivalent proportions with beneficial results. Examples of other fuel oil blends are those containing catalytically cracked and straight run distillates in the volume proportions 1:9, 1:4, 4:1, 9:1. The above-listed compounds can be added to these blends in the proportions disclosed, for example, 0.01, 0.02, 0.03, 0.04, 0.05 percent by weight, with good results.

The monosulfonates of this invention also inhibit deposition of oil-insoluble deterioration products from other mineral oils. For example, a solvent refined lubricating oil derived from a Mid-Continent crude oil and having a viscosity of about 450 S.U.S. at F. was compared with a sample of the same oil containing 10.0 percent by weight of 3-"talloW-aminopropylamine mono-petroleum sulfonate prepared in accordance with the procedure of the foregoing example, and with another sample of the same oil containing 12.7 weight percent of 3-tallo aminopropylamine di-petroleum sulfonate. The sulfonates tested were in the form of oil concentrates, and the monosulfonate concentrate had the following inspection:

Acid number 31.30 Sulfur, percent 1.73 Nitrogen, percent 1.28

The inspection data for the base oil and for the oil sample containing the specific monosulfonate mentioned above are shown below:

The oil containing the above-indicatedmonoand disulfonates were subjected to Single Cylinder Lauson (Diesel ProcedureyEngine Tests. The tests-were carried out in the standard Lauson Model H-2 single cylinder,

9 liquid cooled, four cycle gasoline engine under the following conditions:

Fuel Laboratory supply of L-4 test fuel.

Jacket temperature 300:2" F.

Oil temperature 22Si2 F. sump temp.

Load Full 3 H.P.

Speed 1860 r.p.m.

Oil charge 2.1 lb.

Air-fuel ratio 13.0:1.

Piston Aluminum with 3 rings.

This test consists of a series of 24 hour runs continued for a total of 216 hours unless ring sticking or excessive piston deposits warrant stopping the test earlier. The oil is rated on the following basis:

(1) Piston Varnish Rating in which the piston is compared to a set of standard pistons and visually classified. The rating ranges from 10 for a completely clean piston to for a heavily varnished and lacquered piston.

(2) Number of stuck rings.

(3) Merit Rating which is a visual rating and consists of evaluating over-all engine cleanliness and takes into consideration the following factors: ring sticking, oilring plugging, and piston skirt deposits. A merit rating of 100 is perfect (no stuck or plugged rings, no piston skirt deposits).

The results of the test oils are shown below together with the results obtained with a typical sample of the uninhibited base oil:

1 Test stopped because of poor piston varnish rating.

Composition 2 in the foregoing Table B is a specific embodiment of the invention, and the results obtained therewith are considered typical of those obtainable with other lubricating oil compositions within the scope of the invention. Comparison of the test results for Compositions 1 and 2 of the foregoing Table illustrates the improvement obtainable with the salts of this invention. Comparison of the test results for Compositions 2 and 3 in the foregoing table shows that the advantageous properties of the salts of this invention are peculiar to the monosulfonates.

The foregoing embodiment of the invention is illustrative; other of the monosulfonate salts of this invention can be substituted in the foregoing lubricant composition in the same or equivalent concentrations with beneficial results. Examples of other compositions included by the invention are lubricating oils containing from 1 to 25 percent by weight of the composition, e.g., 5, 10, 15, 20 percent, of the mono-lauryl sulfonates, mono-myristyl sulfonates, mono-dodecylcvyclohexyl sulfonates, mono-naphthenyl sulfonates, mono-dodecylbenzene sulfonates, monocetylbenzene sulfonates, mono-kerosene-alkylbenzene sulfonates of 3-dodecylaminopropylamine, 3-tetradecylaminopropylamine, 3-hexadecylaminopropylamine, 3-octadecylaminopropylamine and 3-octadeceneylaminopropylamine.

It will be understood that the oil compositions of this invention may contain, in addition to the additives disclosed herein, other improvement agents adapted to improve the oils in one or more respects. For example, the stable fuel oil compositions of this invention may contain additionally oxidation inhibitons, flash point control agents, corrosion inhibitors, anti-foam agents, ignition quality improvers, combustion improvers and other additives adapted to improve the oils in one or more respects. The lubricating oil compositions of this invention may contain additionally, for example, anti-oxidants, detergents, pour point improvers, viscosity index improvers, thickencrs, corrosion inhibitors, anti-foam agents and other additives for improving the properties of the oil.

It will be apparent to those skilled in the art that many variations of the invention may be resorted to without departing from the spirit thereof. Accordingly, only such limitations should be imposed as are indicated in the claims appended hereto.

We claim:

1. A monosulfonate of an oil-soluble hydrocarbon sulfonic acid and a 1,3-diaminopropane having the general formula:

where R is an aliphatic radical containing from 8 to 30 carbon atoms.

2. A monosulfonate of an oil-soluble petroleum sulfonic acid and a 1,3-diaminopropane selected from the group consisting of 3-alkyland 3-alkenylamino-propylamines wherein the alkyl and alkenyl substituents contain from 12 to 18 carbon atoms.

3. The monosulfonate of oil-soluble petroleum sulfonic acids and 3-oleylaminopropylamine.

4. The monosulfonate of oil-soluble petroleum sulfonic acids and mixed 3-alkyland 3-alkenylamino-propylamines wherein said alkyl and alkenyl substituents contain from 14 to 18 carbon atoms.

References Cited in the file of this patent UNITED STATES PATENTS 2,130,947 Carothers Sept. 30, 1938 2,321,496 Liberthson June 8, 1943 2,533,302 Watkins Dec. 12, 1950 2,684,292 Caron et al July 20, 1954 2,736,658 Pfohl et a1 Feb. 28, 1956 2,771,348 Meguerian Nov. 20, 6

Claims (1)

1. A MONOSULFONATE OF AN OIL-SOLUBLE HYDROCARBON SULFONIC ACID AND A 1,3-DIAMINOPROPANE HAVING THE GENERAL FORMULA: