US2974022A - Gasoline compositions containing phosphated amino amides - Google Patents

Description

GASOLINE COMPOSITIONS CONTAINING PHOSPHATED AMINO AMIDES Eddie G. Lindstrom, Martinez, and Maurice R. Barusch, I

Richmond, Califl, assignors to California Research Corporation, San Francisco, Calif., a corporation of Delaware This invention relates to an improved hydrocarbon fuel composition suitable for operation in a spark-ignition internal combustion engine, and particularly to a gasoline composition containing a unique addition agent which functions to reduce deposits in the induction system of spark-ignition engines. More particularly it relates to a gasoline composition containing such an addition agent which, additionally, prevents undesirable emulsification of moisture in gasoline.

In certain types of automotive engine service, rough idling and engine stalling has long been a consistant problem and has required frequent carburetor adjustments and reconditioning in order to maintain satisfactory operation. This problem of poor idling has been accentuated and expanded with the increased traffic density in metropolitan areas and the use of multi-throat carburetors in private automobiles. It has been determined that a primary factor in poor idling operation is an accumulation of deposits in the throttle body section of the carburetor which causes an overrich mixture at idle and a reduction in idle speed. The accumulation of deposits in the induction system of the engine and, especially, in the throttle section of the carburetor is particularly pronounced in services requiring considerable idling, such as taxicab and door-to-door delivery service. In private automobile operation, this problem is particularly emphasized in the metropolitan areas where heavy city traffic is encountered with appreciable stop-and-go driving.

The critical accumulation point for these deposits is adjacent to the throttle plate, whose position controls the air-fuel ratio. As these deposits accumulate, the air flow at idle is restricted with no change in fuel flow, and a rich mixture results causing erratic idling and engine stalling. In order to compensate for the presence of these deposits, the throttle must be opened slightly by increasing the idle speed adjustment which, although allowing more air flow, automatically supplies more fuel. This requires a fuel correction by changing the idle mixture adjustment screw a compensating amount. The amount of idle adjustment required to maintain satisfactory idle performance is an indication of the deposit build-up. Furthermore, deposits will often form in the idle air passageway causing restriction which allows the manifold vacuum to draw more gasoline into the engine, again causing rich idle and engine stalling.

It has been established that the primary'source of these deposits is the contaminants in the intake air of the engine when operating at idle. The greatest source of these intake air contaminants is engine blowby, which accounts for approximately one-half of the deposits. Exhaust from other vehicles, dust, and other components range, of a small amount of an oil-soluble acyclic aminoalkylene amide, and preferably an acyclic amino-alkylene amide containing an aliphatic radical, such as an alkyl radical of less than carbon atoms, and preferably of 2 to 4 carbon atoms, attached to the amino group, will provide a fuel composition which will effec- States Patent 0 in which R is an acyclic hydrocarbon radical containing 11 to 17 carbon atoms, A is an alkylene radical and preferably an alkylene radical containing 2 to 4 carbon atoms, and in the two occurrences of R one is hydrogen and the other is an aliphatic radical containing 4' and fewer carbon atoms, such as an alkyl, a hydroxyalkyl, or an aminoalkyl radical. ternate positions of the aliphatic radical R in classed as' normal air pollutants contribute to the formation of deposits.

The hydrocarbon components of the gasoline fuel bear no direct relation to the formation of these deposits. Tests have indicated that unstable or aged gasolines having a high ASTMgum or high potential gum values produce no greater deposits than stable, low-gum gasolines under comparable operating conditions.

In contrast to the periodic mechanical adjustments and engine reconditioning necessary to compensate for the presence of the carburetor and induction system .deposits, it has now been found possible to provide a fuel composition which is capable of preventing an accumulation or build-up of these deposits and will also function to reduce the existing deposits. Thus, by operating a sprak-ignition engine with a fuel composition compounded in accordance with the present invention, it is possible to materially improve the idling operation of the engine and sustain this improved operation even under adverse conditions of intake air pollution.

In the patent application Serial No. 424,243, filed by the present applicants on April 19, 1954, and issued as US. Patent No. 2,839,372'on June 17, 1958, it has been shown and claimed that the incorporation in a hydrocarbon base fuel boiling within the gasoline boiling Formula' I are representative ofthe isomeric forms of the compound, both of which are normally present to a greater or lesser extent, depending upon the reaction employed in the preparation of these compounds. These isomeric forms may be conveniently referred to as a linear amino amide with reference to the form:

- R-(II[}NHA-NHR (II) and as an amino tertiary amide with respect to the following form:

o A-NHn (III) control the condensation to the elimination of one me].

It will be noted' that the alof water. The higher fatty acid component of the reaction may be an acid such as lauric, myristic, palmitic, stearic, linoleic or oleic acid, while the polyarnine reactant may be a polyalkylene polyamine or an N-(alkylene oxide) derivative of an alkylene diamine. In all instances, the alkylene group is preferablyan ethylene, propylene or butylene group. Other methods of preparing the amides may also be employed.

'It is usually desirable to prepare or formulate these improving agents in the form of a concentrate to facilitate handling problems and permit a simple blending operation in the incorporationof the additive in the fuel. In the preparation of the concentrate, the improving agent is dissolved in a hydrocarbon solvent, and particularly an aromatic solvent, in a concentration range of at least 10 percent by weight, and up to about 70 percent by weight.

By reason of their unique efiectiveness, these oil-soluble acyclic amino-alkylene amides are incorporated in the hydrocarbon base fuel in relatively small amounts and, preferably, within the range of about 0.0003 to 0.1 percent by weight. Although larger concentrations may be employed, their effectiveness insofar as the reduction of carburetor deposit build-up is concerned, does not materially improve with additional concentration of the additive.

In a patent application Serial No. 717,572, filed by the present applicants on February 26, 1958, and now abandoned, as a continuation-in-part of the aforementioned application Serial No. 424,243, now US. Patent No. 2,839,372, it has been furthermore pointed out that salts of the aforedescribed amino amides with certain organic and inorganic acids may be used to provide added improving characteristics to the agents and to the gasoline compounded therewith. In particular, it was there pointed out that salts of the aminoalkylene amides with unsubstituted and substituted acids of phosphorus, such as phosphates, phosphonates and phosphites, are particularly attractive for this purpose, because of the known tendency of phosphorus to decrease surface-ignition in the combustion of gasoline in spark-ignition internal combustion engines. The amino amide salts of oxyphosphorus acids and of phosphorus acids having one or two organic radicals bound to the central phosphorus atoms, and of esters of these acids, particularly the phosphated amino amides derived from phosphoric acids (hydrates of P and organo-substittued phosphoric acids, are eminently suitable as additives to gasoline for the purpose of reducing their deposit-forming tendencies. The term amino amide salts of organo-substituted phosphoric acids, as employed in this description, is intended to include, in particular, salts of those phosphoric acids in which the organic substituent attached to the oxyphosphorus radical is a hydrocarbon radical, such as a phenyl, tolyl, cycloalkyl or alkyl radical. The amino amide salts of these organo-substituted phosphoric acids are found to be remarkably effective in reducing the carburetor deposits, especially the amino amide salts of alkyl phosphoric acids (monoalkyl dihydrogen phosphates) and dialkyl phosphoric acids (di'alkyl hydrogen phosphates). For all practical purposes, the number of carbon atoms in an alkyl substituent of an alkyl-substituted phosphoric acid which is reacted with an amino alkylene amide additive need not exceed 20, and preferably should be 16 and lower. As illustrative examples of operative phosphated amino amides there may be named: metaphosphates, pyrophosphates, monoethyl phosphates, diethyl phosphates, dicresyl phosphates, monoisoamyl phosphates, di-n-nonyl phosphates and the like. Amino amide salts of ortho-, meta-, and pyrophosphoric acids and those of lower alkyl phosphoric acids (having from one to eight carbon atoms per alkyl substituent) are particularly suitable for use in gasoline. When the improving agents are employed in the form of their salts and particularly as a multi-functional agent,-the incorporation of the additives in the gasoline may vary over a wider range such as, for example, from 0.0003 to 1.5 percent by weight. Amounts in the range from 0.01 to 1.0 percent by weight are preferred in ordinary practical applications.

Commercial gasolines, after their production at the refinery, are blended with different additives to bring these gasolines to the desired quality, prior to being transferred to bulk storage tanks whence they are eventually distributed to the consumer market. Moisture is invariably present in the air, and a certain percentage of this moisture is breathed in into the blending tanks, or otherwise enters therein as by having become admixed with gasoline in one way or another prior to the blending operation, to be ultimately condensed as liquid in the blending tanks.

In the process of blending the aforementioned aminoalkylene amide additives with gasoline, using conventional mixing equipment and techniques, these aminoalkylenc amides, at higher concentrations, owing to the presence of moisture, tend to cause formation of emulsions which require an unduly long time to separate into two distinct phases; an upper bright gasoline phase, and a lower aqueous phase eventually settling at the bottom of the blending tank.

It is now found that salts of the aforementioned aminoalkylene amides with phosphoric acids, namely, their salts with orthoand pyrophosphoric acids, and more particularly their salts with unsubstituted and/or alkylsubstituted orthoand pyrophosphoric acids eliminate, or at least significantly reduce, the occurrence of emulsification due to the presence of moisture. The alkylsubstituted ort'hophosphoric acids (also designated in the art as acid monoand dialkyl esters of orthophosphoric acid, and alkyl monoand dihydrogen phosphates) suitable for the preparation of the amino amide salts effective as additives to gasoline for the purpose of eliminating formation of deposits without entailing the undesirable emulsificationare monoalkyl phosphoric acids, dialkyl phosphoric acids, and mixtures thereof, characterized by the presence of from 1 to about 8 alkyl carbon atoms in their molecular structure. Particularly effective aminoalkylene amide salt additives are those derived from orthophosphoric acid esters containing from 4 to 8 alkyl carbon atoms in their molecular structure. The corresponding amino amide salts of monoalkyl dihydrogen phosphates and dialkyl hydrogen phosphates of this kind, when present in gasoline in small amounts from about 0.0003 to about 1.5% by weight, instead of their corresponding free amino amides, are not only similarly effective as deposit-eliminating detergent additives but are more desirable, because they prevent formation of objectionable emulsions. Any emulsion which may form, owing to the presence of moisture in a gasoline blending tank, rapidly breaks down, when these phosphates are employed, with separation of water into the aqueous phase at the bottom of the tank. While operative amino amide salts of alkyl acid phosphates may be added to gasolines in amounts in the range from about 0.0003 to about 1.5% by weight, additions of about 0.0004 to about 0.04% by weight are generally preferred and found adequate for most practical purposes.

The aforedescribed amino amide salts of alkyl phosphoric acids to be used as improved detergent-action additives to gasoline may be prepared in any conventional manner, for instance, by reacting a fatty acid amide of an alkylene diamine with a suitable alkyl phosphoric acid in a mol to mol ratio. Ratios lower than 1:1 may also be employed, if desired, in which case the final additive product will contain a greater proportion of phosphorus, and thus, when added to gasoline, Will tend to contribute further to the minimization of surface-ignition in the engine. Ratios higher than 1:1 may also be employed, in which case the final additive product represents a combination of the amino amide alkyl phosphate salt and of the unreacted amino amide, both'of these components contributing their detergent ,eifects toward minimization of induction system and carburetor deposits. This combination is particularly recommended when employing orthophosphoric acid and lower alkyl phosphoric acids containing from 1 to 4 alkyl carbon atoms in their molecular structure to prepare gasoline additives containing amino amide phosphates. The use of an excess of the amino amide forestalls existence of the free acids in the additive product.

The preferred alkyl phosphate salts of amino amides of the present invention are quite stable at ambient and moderately elevated temperatures, and thus they retain their effectiveness in gasoline while stored in the tanks. 'I hese salts are readily soluble in commercial gasolines down to temperatures as low as -20 F., when added to the gasoline in the proportions ranging from about 0.0003 to about 1.5% by weight and preferably from about 0.0004% to about 0.04% by weight.

Moreover, it has been found that, similarly to the unphosphated amino amides, these preferred alkyl phosphate salts, when added to gasoline, materially improve the operation of the engines, by decreasing the occurrence of stalling caused by ice formation on the carburetor under certain weather conditions, and provide a generally smoother engine operation and, consequently, bette engine performance. 1

As in the case of the amino amides, it is desirable to formulate and to supply the preferred alkyl phosphates salts thereof in the form of concentrates, so as to facilitate handling and to permit a simple blending operation for incorporating the phosphate additive in the gasoline. These concentrates suitablefor shipping and handling, both inside and outside the refinery, are prepared by dissolving from about to about 70% by weight of a corresponding phosphate additive material in an organic solvent boiling substantially in the gasoline range, preferably in a hydrocarbon solvent, and, particularly, in an aromatic hydrocarbon solvent boiling in the range from about 300'to about 400 F.

When the gasolines, which are to be improved by the addition of the preferred amino amide phosphates of the present invention, are intended for use in the areas of low winter temperatures, it may be desirable to replace a portion of the hydrocarbon solvent in the concentrate of the phosphate by a compatible aliph'aticalcohol, saturated aliphatic alcohols of 3 to 6 carbon atoms, such as isopropanol, methyl isobutyl carbinol, n-butanol, and the like, being suitable for the purposel V In addition to the improving agents hereinbefore described, other conventional fuel additives may be incorporated in the fuel composition. An added factor in the reduction of deposits within the air-fuel'induction system of the engine may be obtained by'the incorporation, in combination with the subject improving agents, of a nonvolatile oil, such as a light mineral lubricating oil or a petroleum spray oil, which functions as a carrier for the deposits dispersed by the amino amide improving agents. Satisfactory results have been obtained by incorporating a nonvolatile oil in the range of between 0.05 to 0.5 percent by volume and have shown effectiveness in the reduction of deposits in the area of the intake ports of the engine.

The following examples are presented to illustrate the preparation and unique characteristics of representative improving agents of the invention.

EXAMPLE I This example illustrates the general procedure for the preparation of the amino alkylene amide additive to gasoline.

100 grams (0.96 mol) of N-aminoethylethanolamine, 100 grams (0.34 mol) of methyl oleate, and 75 ml. of benzene were charged to a reaction flask fitted-With a 12- reaction temperature was held at to 120C. whilemethanol was removed through the column as abenzene azeotrope distilling at 59 C. The reaction was'continued until methanol formation was complete, which re,

quired about 10 hours. p

The reaction product was dissolved in 3 volumes of equal parts of benzene and mixed hexanes.

tion was washed four times with 10 percent aqueous sodium chloride solution to remove excess diamine. The

solvents were removed on the steam plate and a solid waxy product resulted on cooling. Titration of a product sample with hydrochloric acid using a Beckman glass electrode pH meter indicated that the product was substantially amino alkylene amide.

to a C. pot temperature at 2 millimeters pressure.

116 grams of product having an equivalent weight of 479' were recovered. This indicates that the total amino amide content was 77 percent based on a calculated equivalent weight of 368. The neutral impurity is probably methyl oleate.

By subsequent conventional purification techniques (recrystallization), pure linear amino amide may be recovered from this crude amide mixture. By a suitable modification of the reaction conditions one may vary the ratio of linear amino amides to tertiary amino amides in the crude amide mixture.

EXAMPLE II 'EXAMPLE III The amino amide monoisoamyl phosphate was prepared by making a mixture of about 53% of mono-oleoyl amide of N-Z-hydroxyethyl-1,2-ethylenediamine, 37% of aromatic hydrocarbon thinner (boiling from about 316 to about 330 F.), 4% n-butanohand water to make up 100% by weight, and combining the resulting solution with an equimolar amount of monoisoamyl phosphoric acid, based on the amino amide content of the solution.

The whole was stirred thoroughly to assure complete.

formation of the phosphated amino amide product.

A number of other phosphates were prepared in a similar manner using the amide solution and different substituted phosphoric acids. The products, because 'of the presence of the solvent, were either liquid or soft,"walx like solids. All of these phosphates were to be tested for their deposit-reducing tendency, in accordance with the i procedure set forth in the following example. a I

' EXAMPLE IV A laboratory test was developed to correlate the formation of carburetor deposits with field experience. In a this test, a glass throttle body is inserted between the float section and the cast iron throttle body of a conventional carburetor. This glass throttle body is a section of glass tubing Mt-inch thick, approximately 1% inches in diamter, and about 2 inches long. About A-inch down from the upper edge, holes are drilled diametrically to receive a conventional metal throttle plate and shaft. The carburetor and engine employed in the test are those of a 1952 Plymouth.

The engine is started with the throttle plate in the cast iron body controlling the speed, and the throttle plate in the glass body wide open. When the engine iswarmed inch fractionating column packed with glass helices. I The 75 up' so that no dangerof backfiring exists, the throttle in The solu The reaction product was dissolved in benzene, filtered, and solvent removed 7 the glass body is made to assume the throttling function, and the plate in the iron body is opened wide. Two small tubes carry the idle mixture from the float section to appropriate passageways in the cast iron throttle body.

The engine is operated a total of two hours on the test gasoline at about 500 rpm. idle, with five full-throttle, no-load accelerations, up to a speed of about 3000 rpm. every 15 minutes during the test period. During each run, all of the engine blowby is piped to the engines air cleaner atop the carburetor. At the end of the test run, the engine is shut down and the glass throttle body re moved and rated in accordance with the degree of deposits on a scale ranging from 1 to 7. A rating of 1" indicates a complete lack of deposits with the throttle body clean, and a rating of 7 indicates substantially complete coverage with black, opaque deposits. This test procedure and the rating of compounded gasolines obtained thereby have found excellent correlation with actual test operations in the field.

The following tabulation of several representative test runs, carried out in accordance with the aforedescribed test procedure, illustrates the beneficial deposit-reducing effect of the phosphate salts of the aminoalkylene amide additives.

Table I REDUCTION OF DEPOSITS DUE TO ADDITION OF PHOSPHA'IES Fuel Deposit Rating 1 Base Fuel- (0. Base Fuel +200 p.p.m. of orthophosphate of the aminoamide of Example II (average oi 3 runs) 4.1 Base Fuel +200 p.p.m. of dibutyl phosphate of the same amino amide (average of 2 runs) 3. 5 Base Fuel +200 p.p.m. 0t monoethyl phosphate of the same amino amide (average of 3 H1115) 4. 8 Base Fuel +200 p.p.n1. of mixed cetyl phosphate (50:50 monocetyl and dieetyl phosphates) of the same amino amide (average of 2 runs) A 3. 3 Base Fuel +80 ppm. of rnonoiscamyl phosphate of the same aminoamide (average of 4 runs) 3. 9

1 All deposit ratings corrected to a base iuel rating of 6.0.

The base fuel employed was a commercial leaded regular gasoline which is representative of nationally available commercial gasolines. As was previously mentioned, the hydrocarbon composition of the base fuel has a negligible effect upon the formation of carburetor deposits except as it influences the composition of the blowby, and the test results given above on the base fuel will be approximately the same, irrespective of the stability, gum content, or other characteristics of the hydrocarbon components of the fuel.

In addition to the foregoing test data, a gasoline composition compounded in accordance with the present invention was field tested in representative fieet service and private automobile operation over an extended period of time with periodic inspection of the air-fuel induction systems of the engines and, in particular, the carburetors. In all instances, the test fuel not only inhibited the formation of carburetor deposits, but also was effective in removing existing deposits within the carburetor and the intake manifold and permitted continuous satisfactory operation extending beyond periods where, normally, carburetor ovehauling was to be expected.

EXAMPLE V The effectiveness of amino amide phosphates in eliminating emulsion formation in gasolines is demonstrated by the results of the water tolerance test tabulated in Table II below. The test procedure consists of shaking vigorously for 2 minutes 80 milliliters of gasoline containing the phosphate additive and 20 milliliters of disstilled water in a 100-milliliter graduate, noting the time required for the separation of the shaken mixture into two distinct phases: an upper gasoline phase and a lower aqueous phase.

The additive phosphate, except in run 1) is present in an amount equal to 250 ppm. The commercial alkyl phosphoric acids used to prepare the phosphates for these tests were water-washed (three times) prior to the actual preparation of the amino amide phosphate additives to gasoline. As a representative amino amide, mono-oleoyl amide of N-2-hydroxyethyl-1,2-ethylenediamine, was employed for the reaction with the washed phosphoric acid. The abbreviation ppm. as used here and elsewhere in this specification means parts per million parts of the gasoline mixture.

1 Free amino amide (unre- Persistent acted with any acid). Emulsion. Orthophosphoric 3. Mixed methyl phosphoric. 50/50 1. 5 2. Mixed ethyl phosphoric... 84/16 2.3 1.5. Mixed isopropyl phos- 55/45 4. 3 5.

phoric. Monoisoamyl phosphoric. /0 5. 0 3.5. Mixed amyl phosphoric 82/18 5. 9 4. Monoisooetyl phosphoric 100/0 8. 0 7. Mixed oetyl phosphoric-.. 64/36 10.9 Persistent Emulsion. Mixed 2-ethyll1exyl phos- 50/50 12.0 Do.

phorie.

The results tabulated in Table 11 clearly indicate the demulsifying effect of the amino amide phosphates as compared with the amino amide itself (run No. 1). Also, the data indicate the optimal demulsifying effect when employing phosphates of alkyl phosphoric acids characterized by the presence of 4 to 8 alkyl carbon atoms in their molecular structure (runs 5, 6, 7 and 8). When the molecule of the phosphate additive contains more than 8 alkyl carbon atoms, the emulsion separates but very slowly (runs 9 and 10). When less than 4 alkyl carbon atoms characterize the phosphate additive, some fioc or haziness is noticeable in the gasoline (runs 2, 3 and 4).

Particularly efiective are the amino amide alkyl phosphates with an average of 5 alkyl carbons in their structure. Gasolines containing them are not subject to appearance of floc or haziness, and their activity in preventing emulsification persists indefinitely at moderately elevated, ambient and low temperatures. Solutions of 250 p.p.m. and 1000 p.p.m. of mono-oleoyl amide of N-2- hydroxyethyl-1,2-ethylenediamine salt of monoisoamyl phosphoric acid in gasoline remain bright for 15 days and longer at -20 F.

A substantial anti-rusting eifect due to employment of the preferred amino amide C4-Cg-fllkY]. phosphates of the invention is shown by the following Table III containing illustrative data of a modified ASTM test for determining rust-preventing characteristics of steam turbine oils (ASTM-D-665-154), using synthetic sea-water. The difierence in the procedure from that of the unmodified test consisted in conducting the test at room temperature for 17 hours instead of 24 hours, and in employing a comparison rating scale from 1 to 7 to define the extent of rusting. Rating 1 indicates a substantial absence of rust, rating 7 refers to heavy rusting of more than 99% of a test steel coupons surface, and rating 4 corresponds to about 40% of the surface being lightly rusted. Rates 1 to 3, intermediate between 1 and 4, are deemed to be satisfactory.

Table III EFFECT OF AMINO AMIDE PHOSPHATES ON M01 Ratio of Mono- Concen- Run Amino Amide Salt alkylto tration Rust No. Dialkyl p.p.m. Rating Phosphoric Acid Orthophosphate 250 do 30 6 Mixed ethyl phosphate 84/16 250 6 Mixed lsoamyl phosphate 81. 5/18. 5 43 3 Monoisoamyl phosphate 100/0 100 3 Mixed isoamyl phosphate.-- 81. 5/18. 5 100 1. 5 Mixed isoamyl phosphate 81. 6 18. 5 366 2. 5 Mixed amyl phosphates.. 55/45 250 1 Dibutyl phosphate 0/100 30 1 Mono-octyl phosphate 100/0 30 1 Base gasoline (no salt added)- 6 The results given in Table III demonstrate that the amino amide salts of C -C alkyl phosphoric acids which contain no water-soluble phosphoric acids inhibitrusting, when added to gasolines in amounts from 0.0003 to 1.5% by weight in accordance with the invention.

A further advantage of the amino amide phosphates, which has been established by repeated tests in automobile engines, resides in that they reduce the occurrence of engine stalling by ice formation in the carburetor in the same degree as the free amino amides. Thus, when present in gasoline in the same amounts as have been found to be effective in the case of the amino amides, the corresponding phosphates assure a smooth operation of the engine employing the gasoline containing them.

In conclusion, it is to be understood that many modifications and variations of the invention, as set forth hereinbefore, may be made without departing from the spirit and scope thereof. Therefore, only such limitations should be imposed thereon as are indicated in the appended claims.

The present application is a continuation-in-part of application Serial No. 717,572, filed by the present applicants on February 25, 1958, and now abandoned.

We claim:

1. An improved gasoline composition which comprises a major portion of a hydrocarbon base fuel boiling within the gasoline boiling range, having incorporated therein from about 0.0003 to about 1.5% by weight of a salt of a phosphoric acid, selected from the group con sisting of unsubstituted phosphoric acids and organesubstituted phosphoric acids in which the organo-substituent is attached to the oxyphosphorus radical and is a hydrocarbon radical, and an acyclic aminoalkylene amide of the following formula:

wherein R is an acyclic hydrocarbon radical containing 11 to 17 carbon atoms, A is an alkylene radical containing 2 to 4 carbon atoms, and in the two occurrences of R one is hydrogen and the other is an aliphatic radical containing 4 and fewer carbon atoms and selected from the group consisting of alkyl, hydroxyalkyl and aminoalkyl radicals.

2. An improved gasoline composition which comprises a major portion of a hydrocarbon base fuel boiling within the gasoline boiling range, having incorporated therein about 0.0003 to 1.5 percent by'weight of a mixture of salts of a phosphoric acid, selected from the group consisting of unsubstituted phosphoric acids and organosubstituted phosphoric acids in which the organo substituent is attached to the oxyphosphorus radical and is a I .10 hydrocarbon radical, and amino amides of the following formulas:

and

wherein R is an acyclic hydrocarbon radical containing 11 to 17 carbon atoms, A is an alkylene radical containing 2. to 4 carbon atoms, and R is an aliphatic radical containing 4 and fewer carbon atoms and selected from the group consisting of alkyl, hydroxyalkyl and aminoalkyl radicals. p

3. An improved gasoline composition which comprises a major portion of a hydrocarbon base fuel boiling within the gasoline boiling range, having incorporated therein from about 0.0003 to about 1.5% by weight of a salt of an alkylph'osphoric acid having from 1 to 20 carbon atoms per alkyl substituent and an acyclic amino alkylene amide of the following formula:

wherein R is an acyclic hydrocarbon radical containing l'l to 17 carbon atoms, A is an alkylene radical containing 2 to 4 carbon atoms, and in the two occurrences of R one is hydrogen and the other is an aliphatic radical containing 4 and fewer carbon atoms and selected from the group consisting of alkyl, hydroxyalkyl and aminoalkyl radicals.

4. The gasoline composition of claim 1, containing, in addition, from 0.05 to 0.5% by volume of a nonvolatile light mineral oil. I

5. An improved gasoline composition as defined in claim 3, wherein the amino amide salt of alkyl phosphoric acid is a salt ofa C -C alkyl phosphoric acid.

6. An improved gasoline composition as defined in claim 3, wherein the amino amide salt of phosphoric acid is orthophosphate.

7. An additive concentrate capable of incorporation into a gasoline, consisting essentially of a hydrocarbon solvent boiling substantially within the gasoline boiling range and having dissolved therein an amount ranging from about 10 to about 70%-by weight of a salt of a phosphoric acid selected from the group consisting of unsubstituted phosphoric acids and organo-substituted phosphoric acids in which the organo-substituent is attached to the oxyphosphorus radical and is a hydrocarbon radical and of an oil-soluble acyclic amjnoalkylene amide of the formula:

wherein R is an acyclic hydrocarbon radical containing 11 to 17 carbon atoms, A is an alkylene radical containing 2 to 4 carbon atoms, and in the two occurrences of R one is hydrogen and the other is an aliphatic radical containing 4 and fewer carbon atoms and selected from the group consisting of alkyl, hydroxyalkyl and aminoalkyl radicals.

8. An additive concentrate as defined in claim 7, wherein the phosphoric acid salt is a salt of an alkyl phosphoric acid having from 1 to 20 carbon atoms per alkyl substituent.

9. An improved gasoline composition which comprises a major portion of a hydrocarbon base fuel boiling within the gasoline boiling range, having incorporated therein from about 0.0003 to about 1.5% by weight of a salt of an alkyl phosphoric acid having an average from 1.1 4 to 8'alky1 carbonatoms in its molecular structure and an acyclic amino alkylene amide of the formula wherein R is an acyclic hydrocarbon radical containing 11 to 17 carbon atoms, A is an alkylene radical containing 2 to 4 carbon atoms, and in the two occurrences of R one is hydrogen and the other is an aliphatic radical containing 4 and fewer carbon atoms and selected from the group consisting of alkyl, hydroxyalkyl and aminoalkyl radicals.

10. An improved gasoline composition as defined in claim 9, wherein the amino amide salt of alkyl phosphoric acid is a salt of an alkyl phosphoric acid having an average of 5 alkyl carbon atoms in its molecular structure.

11. An additive concentrate capable of incorporation into a gasoline, consisting essentially of an organic solvent boiling substantially in the gasoline'range and selected from the group consisting of hydrocarbon solvents and mixtures of these hydrocarbon solvents and saturated C -C aliphatic alcohol solvents, and having dissolved in said organic solvent an amount. ranging from about to about 70% by weight of a salt of an alkyl phosphoric acid having an average from 4 to 8 alkyl carbon atoms in its molecular structure and an amino alkylene amide of the formula wherein R is an acyclic hydrocarbon radical containing 11 to 17 carbon atoms, A is an alkylene radical containing 2 to 4 carbon atoms, and in the two occurrences of R one is hydrogen and the other is an aliphatic radical containing 4 and fewer carbon atoms and selected from the group consisting of alkyl, hydroxyalkyl and aminoalkyl radicals.

12. An additive concentrate as defined in claim 11 wherein the salt of aminoalkylene amide and alkyl phosphoric acid is a salt of an alkyl phosphoric acid having an average of 5 'alkyl carbon atoms in its molecular structure.

13. An additive concentrate capable of incorporation into a gasoline, said concentrate consisting essentially of an organic solvent boiling substantially within the gasoline-boiling range and selected from the group consisting of hydrocarbon solvents and mixtures of these hydrocarbon and aliphatic saturated C -C alcohol solvents, and having dissolved in said organic solvent from about 10 to about by weight a phosphoric acid salt of an oil-soluble acyclic aminoalkylene amides of the formula wherein R is an acyclic hydrocarbon radical containing 11 to 17 carbon atoms, A is an alkylene radical containing 2 to 4 carbon atoms, and in the two occurrences of R, one is hydrogen and the other is an aliphatic radical containing 4 and fewer carbon atoms and selected from the group consisting of alkyl, hydroxyalkyl, and aminoalkyl radicals, and the phosphoric acid being selected from the group consisting of unsubstituted phosphoric acids and organo-substituted phosphoric acids in which the organic substituent is attached to the oxyphosphorus radical and is a hydrocarbon radical.

References Cited in the file of this patent UNITED STATES PATENTS 2,014,924 Benedict Sept. 17, 1935 2,312,082 Dietrich Feb. 23, 1943 2,340,881 Kelley et al Feb. 8, 1944 2,387,501 Dietrich Oct. 23, 1945 2,508,924 Mertens et a1. May 23, 1950 2,568,876 White et al. Sept. 25, 1951 2,728,647 Vaughn Dec. 27, 1955 2,794,721 Bartleson June 4, 1957 I UNiTED STATES rATENT OFFICE v RTIFICATE OF CORRECTION Patent No; 237 022 March L 1961 Eddie G, Lindstrom et. a1.

5 It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent. should read as "corrected below Column 1, line 67 beginning with "range of a small", strike out; all to and including "aliphatic radical R in" in li'he 21, column 2, and insert the same after "boilingfl, second occurrence, in line 4L6 same column 2; same column 2 line 37 for sprwalwignition read spark-ignition column 3 line 417 for "organo -substittued" read organo-substituted column 9, line 43, for "February 25, 1958" read February 26 1958 column 1O line 43 for the claim reference numeral 3" read l Signed and sealed this 10th day of October 1961,

'(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD A ng O f Commissioner of Patents USCOMM-DC

Claims (1)

13. AN ADDITIVE CONCENTRATE CAPABLE OF INCORPORATION INTO A GASOLINE, SAID CONCENTRATE CONSISTING ESSENTIALLY OF AN ORGANIC SOLVENT BOILING SUBSTANTIALLY WITHIN THE GASOLINE-BOILING RANGE AND SELECTED FROM THE GROUP CONSISTING OF HYDROCARBON SOLVENTS AND MIXTURES OF THESE HYDROCARBON AND ALIPHATIC SATURATED C3-C6 ALCOHOL SOLVENTS, AND HAVING DISSOLVED IN SAID ORGANIC SOLVENT FROM ABOUT 10 TO ABOUT 70% BY WEIGHT A PHOSPHORIC ACID SALT OF AN OIL-SOLUBLE ACYCLIC AMINOALKYLENE AMIDES OF THE FORMULA