US3615291A - Ethoxylated or propoxylated 1,2,4- or 1,2,5-trisubstituted imidazolines and lecithin mixtures and reaction products thereof - Google Patents

Abstract

Motor fuel multipurpose additives comprising ethoxylated or propoxylated 1,2,4- or 1,2,5-trisubstituted imidazolines or the mixtures of lecithin with said imidazolines.

Description

lJnited States Inventor Helen I. Thayer Oalrmont, Pa.

Aug. 29, 1969 Oct. 26, 1971 Gulf Research 8; Development Company Pittsburgh, Pa.

Continuation-impart of application Ser. No. 544,839, Apr. 25, 1966, now Patent No. 3,527,584.

The portion of the term oi the patent subsequent to Sept. 8, 1987, has been diselaimed.

IETHOXYLATIED 0R PROPOXYLATIEID 1,2,4- 01R 1,2,5-Tll11SUBSTlT UTlED llMlllDAZOlLlINlES AND lLlECllTl-HN MIXTURES AND REACTION PRODUCTS T1111E1R1E01F 2 Claims, No Drawings 1U.S. C1 44/58, 44/63, 44/66 51 11nt.C1 C10l11/26 50 lFieldoiSearch 44/63,66, 58-,252/50;260/309.6; 123/136 Primary Examiner-Daniel E. Wymam Assistant Examiner-Mrs. Y. H. Smith Attorneys-Meyer Neishloss, Deane 57 Keith and Alvin E.

Ring

ABSTRACT: Motor fuel multipurpose additives comprising ethoxylated or propoxylated 124- or 1,2,5-trisubstituted imidazolines or the mixtures of lecithin with said imidazolines.

ETHOXYLATED R PROPOXYLATED 1,2,4- 0R 1,2,5- TRllSUBSTITUTED IMIDAZOLINES AND LECITHIN MIXTURES AND REACTION PRODUCTS THEREOF This application is a continuation-in-part of Ser. No. 544,839, filed Apr. 25, 1966 now U.S. Pat. No. 3,527,584.

This invention relates to multipurpose additives for motor fuels and to motor fuel compositions containing a minor proportion of said additives. The additives of the present invention perform two primary functions in gasoline including (1) reduction of wear in cast iron piston rings of a gasoline-burning engine and (2) reduction of the tendency of gasoline to clog a fuel filter element. Therefore, this invention also relates to methods for improving the performance of gasoline-burning engines.

The additives of the present invention comprise ethoxylated or propoxylated l,2,4- or 1,2,5-trisubstituted imidazolines. The additives of the present invention also comprise mixtures of lecithin and ethoxylated or propoxylated 1,2,4- or 1,2,5- trisubstituted imidazolines or the reaction product of lecithin and said imidazolines.

It is surprising that the ethoxylated and propoxylated derivatives of trisubstituted imidazolines are capable of functioning as gasoline antiwear agents. The reason is that while nonalkoxylated disubstituted imidazolines are highly effective gasoline antiwear agents, nonalkoxylated trisubstituted imidazolines are not antiwear agents. However, in accordance with this invention it has been found that the alkoxylation of trisubstituted imidazolines with l to 3 mols of ethoxide or propoxide not only imparts antiwear characteristics thereto but furthermore imparts antiwear characteristics which are considerably superior as compared to the antiwear qualities of nonalkoxylated disubstituted imidazolines. The antiwear characteristics of alkoxylated trisubstituted imidazolines is still more surprising in view of the fact that when disubstituted imidazolines are alkoxylated they lose their antiwear characteristics. The critical distinction in chemical structure of the alkoxylated trisubstituted imidazolines of this invention over closely related alkoxylated and nonalkoxylated amines are set forth in greater detail below in this application and in applications Ser. No. 544,838 and Ser. No. 844,840, each entitled Motor Fuel Multipurpose Agents and filed on the same date as this application by the same inventor.

The imidazolines of this invention have an ethoxylated or propoxylated alkylamine substituent in the l-position; an alkyl substituent containing seven to 29 carbon atoms in the 2-position; and one methyl substituent in either the 4- or the 5-position. Although it is invariably expected that the presence or absence of a methyl substituent will be noncritical in a gasoline additive compound, the presence of a single methyl substituent in the 4- or 5-position of the imidazoline ring is critical in the alkoxylated imidazolines of this invention. A preferred trisubstituted imidazoline of this invention is prepared by reacting dipropylene triamine previously reacted with 2 mols of ethylene oxide with a mixture of saturated and unsaturated fatty acids to produce l-(N-hydroxyethoxyethyl- 2-(or l-)-methyl-2-aminoethyl)-2-long chain alkyl-4(or 5-)- methylimidazoline having the general formula or methyl isomers thereof, or the corresponding imidazolines having two separate hydroxyethyl groups attached to the side chain nitrogen.

in the absence of lecithin, the trisubstituted imidazolines of this invention per se impart a beneficial effect when added to gasoline. The trisubstituted imidazolines by themselves impart antiwear properties to gasoline as evidenced by reduction in loss of metallic iron from cast iron piston rings. However, when the trisubstituted imidazolines are either mixed with or reacted with lecithin, the product exerts an additional highly beneficial efiect in gasoline, namely, substantial reduction of the tendency of the gasoline to clog the fuel filter element through which it passes in its flow to an engine. The lecithinimidazolines of this invention probably reduce filter clogging by completely dissolving some of the dispersed solids in gasoline and by partially dissolving other dispersed solids to reduce the size thereof.

The antitilter-clogging characteristic of the lecithin-containing additives of this invention is highly important because in nearly all automobiles motor fuels are filtered during flow to an engine. Furthermore, reducing the level of solids in gasoline in itself tends to decrease wear of piston rings by reduction of abrasion at said piston rings. Therefore, the antiwear and antifilter-clogging characteristics of the lecithinimidazoline additives of this invention cooperate to produce a common advantageous effect: the antiwear function contributing directly to piston ring wear rate reduction and the antifilter-clogging function contributing indirectly to reduction of engine wear by completely dissolving a portion of the potentially abrasive solids in gasoline and by partially dissolving another portion of said solids to reduce the size thereof, thereby permitting easier removal of the remaining solids by filtration.

The antifilter-clogging characteristic of the mixture of or the reaction product of lecithin and the trisubstituted imidazolines of this invention is especially surprising since neither lecithin by itself nor the trisubstituted imidazolines of the invention by themselves impart antifilter-clogging characteristics to gasoline. On the other hand, gasoline compositions containing either the unreacted mixture of or the reaction product of lecithin and the trisubstituted imidazolines of this invention exhibit high antifilter-clogging characteristics.

A significant feature of the present invention is that imidazolines differing from the imidazolines of the present invention only by the omission of the methyl substituent from the imidazoline ring or only by omission of the ethoxyor propoxysubstituent do not exhibit antiwear properties. Therefore, while the trisubstituted imidazoline prepared by reacting fatty acid with dipropylene triamine plus 2 mols of ethylene oxide and having the formula or the methyl isomers thereof, or the corresponding imidazolines having two separate hydroxyethyl groups attached to the side chain nitrogen, is a highly effective antiwear agent, the disubstituted imidazoline prepared by reacting fatty acid with diethylene triamine plus two mols of ethylene oxide and having the formula or the corresponding imidazoline having two separate hydroxyethyl groups attached to the side chain nitrogen. is not an antiwear agent. Also, while the ethoxylated trisubstituted imidazoline of this invention is a highly effective antiwear agent, the same imidazoline in nonethoxylated form and having the formula or the mefiiyl isomers thereof, is not an antiwear agent. Therefore, the minor modifications of the trisubstituted imidazolines of this invention comprising deletion of the methyl substituent from the imidazoline ring or deletion of the ethoxy-derived substituent from the side chain nitrogen deprives the imidazoline of its antiwear properties.

The 1,2,4-trisubstituted or 1,2,5-trisubstituted imidazolines of this invention have the general formula wherein R, is a saturated or unsaturated hydrocarbon radical containing seven to 29 carbon atoms, generally, and 11 to 17 carbon atoms, preferably.

R and R are either hydrogen or a methyl radical, with the provision that one is a methyl radical and the other is hydrogen.

R is a methylene, ethylene, or propylene (methylethylene which is either group,

and is preferably a propylene group.

R is hydrogen, a methyl, ethyl, hydroxyethyl, hydroxyethoxyethyl, hydroxyethoxyethoxyethyl, hydroxypropyl, hydroxypropoxypropyl or hydroxypropoxypropoxypropyl radical, and

R is hydrogen, a methyl, ethyl, hydroxyethyl, hydroxyethoxyethyl, hydroxyethoxyethoxyethyl, hydroxypropyl, hydroxypropoxypropyl or hydroxypropoxypropoxypropyl radical, with the provision that at least one of said R or R radicals is an hydroxyethyl, hydroxyethoxyethyl, hydroxyethoxyethoxyethyl, hydroxypropyl, hydroxypropoxypropyl or hydroxypropoxypropoxypropyl radical, preferably an hydroxyethoxyethyl radical.

Examples of suitable imidazolnes of this invention include l-( hydroxyethoxyethylaminopropylene )-2-( 8 '-heptadecenyl)--methylimidazoline; l-(hydroxyethylaminomethylethyl)- 2-heneicosyl-S-methylimidazoline; l-( N,N-dihydroxypropylaminopropylene)-2-(8',l0'-heptadecadienyl)-4- methylimidazoline; l-(N,N-dihydroxyethylaminopropylene)- 2-( undecyl)-5(or 4)-methylim idazoline; 1-( N-hydroxypropoxypropoxypropylaminopropylene )-2-( 8 '-pentadece nyl)-5(or 4)-methylimidazoline; and l-(N-hydroxyethoxyethoxyethyl)-2-heptadecyl-4(or 5 )-methylimidazoline.

A preferred commercial imidazoline whose major component is or the methyl isomers thereof, or the corresponding imidazoline having two separate hydroxyethyl groups attached to the side chain nitrogen, is prepared by reacting a mixture of long chain fatty acids with dipropylenetriamine which has previously been reacted with 2 mols of ethylene oxide. Other imidazolines of this invention can be prepared by reacting a fatty acid having eight to 30 carbon atoms with N- aminomethylpropylenediamine or N-aminoethylpropylenediamine previously reacted with ethylene oxide or propylene oxide. The fatty acid mixture used in the synthesis of the commercial imidazoline comprised 37.0 percent linoleic acid, 6.0 percent conjugated linoleic acid, 525 percent oleic acid, 0.5 percent palmitic acid, 0.5 percent palmitoleic acid, 2.5 percent stearic acid, and 1.0 percent of other acids. Other suitable acids that can be used in the synthesis include lauric, myristic, arachidic, behenic, cerotic, lignocerie and other saturated and unsaturated fatty acids.

Any lecithin can be utilized in accordance with this invention, such as lecithin derived from soybean oil, corn oil, linseed oil or egg yolk. A suitable commercial lecithin to be reacted with or admixed with an imidazoline of this invention is a neutral oil solution of a filtered soybean lecithin with moisture value less than 0.75 percent, an acetone-insoluble value of 70 percent, and a viscosity of 3,046 centipoises. According to one method of preparation of the lecithin derivative of the trisubstituted imidazoline, base lecithin is reacted with the imidazoline at 55-80 C. with stirring for a reaction time of from about 19 to 55 hours. The conditions for reaction of the base lecithin with the trisubstituted imidazoline of this invention are not critical. In general, the reaction can occur at a temperature between about 40 and l00 C. for a time duration of about 5 to 100 hours.

As stated, the conditions for reaction of the lecithin with the imidazoline are not critical. For example, while temperatures of 40 to 100 C. are ordinarily suitable at atmospheric pressure, ifthe reaction is performed under a vacuum much higher temperatures can be employed. Also, a reaction time duration greater than 100 hours can be employed. The ratio of lecithin to imidazoline is also not critical and can vary within wide limits. For example, the ratio can be between about 1 and 20 and about 20 to 1. All of these conditions are nonlimiting and are presented for illustrative purposes only.

The concentration in gasoline of the additives of this invention is not critical. For example, the additives of this invention can be present in gasoline in a general concentration range of 0.1 to 100 pounds per 1,000 barrels, or a preferable concentration range of l to 25 pounds per 1,000 barrels. in terms of weight percentage, the additives can be present in gasoline in a general range of 0.00004 to 0.04 percent and a preferable range of 0.004 to 0.01 percent. if the additive to the gasoline comprises an unreacted mixture of lecithin and imidazoline, the components of the mixture can be present in a wide ratio. For example, the ratio of components in the mixture can range from substantially no lecithin to from about 1:100 to about 20:1 weight ratio of lecithin to amine.

The gasoline compositions of this invention contain as the hydrocarbon portion thereof any of the known gasoline hydrocarbons, such as, for example, hydrocarbons boiling in the range of about 90 to 400 or 425 F. The hydrocarbon portion of the gasoline composition can comprise normal, branched-chain, and cyclic hydrocarbons having from four to 12 carbon atoms. The gasoline also can comprise products prepared in the chemical conversion of hydrocarbons to produce gasoline. Such conversion products include the products prepared by isomerization, alkylation, polymerization, cracking, disproportionation, hydrogenation, dehydrogenation, and combinations of such processes. A common gasoline composition contains a major proportion of the gasoline hydrocarbons prepared by fluid catalytic cracking and a minor proportion of an alkylate prepared from isobutane and C and/or C olefins. The base fuel can comprise about percent of gasoline from the fluid 77 process, and about 20 percent of the aforementioned alkylate.

Example 1 A series of tests was performed utilizing radioactive piston rings to compare the gasoline antiwear properties of a disubstituted imidazoline, a nonethoxylated trisubstituted imidazoline and an ethoxylated trisubstituted imidazoline. Following is a description of the procedure that was utilized in these tests.

t Test Procedure h A mixture comprising in major proportion:

( M-C If-CHz-CHNHz N CH7 CH3 The radioactive ring wear test was performed with a labora' tory test, 4-stroke, single cylinder internal combustion engine equipped with a cast iron top compression ring which prior to 5 use had been rendered radioactive by insertion into the pile of 0H; an atomic reactor. The engine provided with the radioactive and/mmethyl isomers thereof ring was operated at constant speed for hours under the folb A i t r comprising in major proportion: lowing test conditions: (Cid-C If'*'CH2-CHNH(CHZCH20)2H N CH2 CH3 Speed: r.p.m. 2.000 \CH Load: our 5 Spark Before Top Center OH: All'jpuel 31/19 and/or methyl isomers thereof, or the corresponding imidazolines having Cylinder wall 1 5 two separate hydroxyethyl groups attached to the side chain nitrogen.

Temp. F. 1 l2 5 ump Oil Temp. F. 125 Carburetor: lnlake Air Temp. "F. 85

During the test the motor oil accumulated particles of the radioactive metal lost by the radioactive piston ring through wear. The radioactive metal content of the motor oil was continuously counted by means of a Geiger counter and recorded. At intervals oil samples were taken and the amount of dilution of oil by fuel was determined. Since dilution of oil by fuel tends to depress the radioactivity measurement, the amount of wear was calculated on the basis of radioactivity counts corrected by a factor corresponding to the amount of dilution of the motor oil with fuel.

ubstituted imidazoline caused loss of antiwear properties.

Example 2 Table 1 shows that while a disubstituted nonethoxylated 2Q imidazoline is a highly effective antiwear agent, a nonethoxylated trisubstituted imidazoline is not an antiwear agent. However, table I further shows that ethoxylation of the trisubstituted imidazoline not only converted it into an antiwear agent but produced an antiwear agent superior to the disub- 25 stituted imidazoline. This showing is especially surprising in view of the showing in example 2 that ethoxylation of the dis- The results ofthe antiwear tests are shown in table ll. Table 2 Shows the results of TadiOactiVe P Ting tests conducted with a base motor oil to determine the an- TABLE 1.-RADIOACTIVE PISTON RING WEAR TESTS tiwear properties of disubstituted and trisubstituted Additive imidazolines in both the ethoxylated and nonethoxylated concen- Percent tates tratlon, change in 35 s v parts per piston As shown in table 2, the disubstituted imidazoline is a highly Additive mum) wear rate effective antiwear agent but ethoxylation thereof causes it to 1-(Mminoethyl)-2-heptadeceny1imidazoline. 98.5 33 lose its antiwear properties. Therefore, it would not be ex gg gfi igg iggg iggg gfigfi ffi 50 +5 pected that ethoxy lation could impart antiwear properties to a The reaction product 01 long chain fatty acids 40 closely related imidazoline compound. But, surprisingly, the

and dipropyleno triamine plus 2 mols of ethylene oxide table h ws that trisubstituted imidazoline is not a annwear agent but ethoxylation imparts antiwear properties thereto.

TABLE 2.RADIOACTIVE PISTON RING WEAR TESTS Concentra- Control iron tion, wear, Fuel additive p.p.m. Piston Rings Oil mg. Test-iron wear, mg.

The reaction product of long chain fatty acids and 98. 5 Radioactive Base motor oil free of 8.7 6.1.

diethylene triamino cast iron. additives. I D The reaction product of long chain fatty acids with 98. 5 ..do do 8.7 No significant change in Wear diiiatlh lene trlamine and 2 mols of ethylene as compared to control. ox e The reaction product 01' long chain fatty acids 98. 5 do...-.... do. 5. 5 4.8.

with dipropylene trisminc plus 2 mols of ethylene oxide The reaction product of long chain fatty acids and 98. 5 .do dam... 5. 5 No significant change in wear dlpropylene triamino as compared to the control.

A commercial mixture comprising about to percent by weight of l-(Z aminoethyl)-2-hcptadecenylimidazolinc:

b A mixture containing in major proportion:

and/or corresponding imidazolincs having two separate hydroxyetliyl groups attached to the side chain nitrogen.

s A mixture containing in major proportion: (Cm-El N-CHz-(, HNH(CH2CH20)7.H

N CH2 CH5 I CH3 7 Table Continued and/or methyl isomers thereof, or corresponding imidazolines having two separate hydroxyethyl groups attached to the side chain nitrogen.

d A mixture containing in maior proportion:

and/or methyl isomers thereof.

EXAMPLE 3 A further series of tests was conducted which utilized a method other than radioactivity to determine both antiwear characteristics and engine cleanliness characteristics of a gasoline sample containing an ethoxylated trisubstituted imidazoline of this invention and a gasoline sample containing a nonethoxylated disubstituted antiwear agent. The antiwear tests measured the individual wear rate of each of the three piston rings of each of the six cylinders in an automobile engine. The following procedure was utilized for conducting the tests of this example.

Test Procedure The test is performed with a 216 cu. in 6-cylinder automobile engine in five 8-hour test periods. Following each of the first four periods of operation the engine is shut down for a 4- hour interval. Preceding the first 8-hour test period there is a progressive break-in over a 4-hour period in order to reach test conditions by the end of the last hour of the break-in period. At the end of the break-in period the crankcase oil is drained, the crankcase refilled and the engine operated for a lO-minute warmup before commencing the first 8-hour period of test operation.

Following are the conditions prevailing during the test:

Load: BHP Speed: r.p.m. Spark Advance Spark Plug Gap: in. Valve Clearances: in.

intake Exhaust intake Manifold 38:3 Before Top Center at 2,500 r.p.m.

Heat control locked in "off position At the end of the test, the engine is disassembled and rated visually for deposits on the following parts to establish the total engine cleanliness rating.

Varnish Deposits Sludge Deposits Piston Skirts Cylinder Walls crankcase Oil Pan Push-rod Cover Plate Rocker-Arm Cover Plate Oil Screen crankcase Oil Pan Rocker-arm Assembly Rocker-Arm Cover Plate Push-Rod Cover Plate The total engine rating is the sum of the ratings made on the i partslis te'd above. Each part is rated on a scale of 0 (heavy deposits) to (clean).

The piston rings were weighed before and after the test to ascertain the ring weight loss.

The results of the tests of this example are shown in table 3.

TABLE 3.--Efiect 0t Additives on Engine Cleanliness and Wear Fuel Make-up: Percent by Volume Gasoline 100 100 100 100 Added:

Tetraethyl lead m.l./gal 2. 5 2. 5 2. 5 2. 5 The reaction product of long chain fatty acids and diethylcne triamine' lb./ 1,000 bbls 25 The reaction product of long chain iatty acids with dipropylene triamine plus 2 mols eth lene oxide lbs/1,000 bbls 25 Oil Make-up: Percent by Volume Light neutral oil 30. 25 30. 25 30. 25 30. 25 Medium neutral oil. 65.00 65.00 65. 0O 65. 00 4. 25 4. 25 4. 25 0. 50 0. 50 0. 50 0. 01 0. 01 0. 01

6-Cylinder Automobile Engine Cleanliness and Wear Test Total en ine cleanliness rating (l00=cloan) (varnis and sludge) 80. 0 82.0 81.0 85. 5 Skirt varnish rating avg. piston (10=clean) 6. 5 7. 5 7. 0 7. 5

Ring Weight Loss First ring (compression): average weight loss for six pistons, mg 92 68 74 z 44 Second ring: average weight loss for six pistons, mg 34 h 30 35 i 18 Third ring: average weight loss. 54 i 34 38 k 27 Total average ring weight 180 l 132 147 s a A commercial mixture comprisin about to percent by weight of 1-(2aminoethyl)-2-heptadecenylim dazoiine:

b A mixture comprising in major proportion:

and/or methyl isomers thereof or corresponding imidazolines having two separate hydroxyethyl groups attached to the side chain nitrogen.

v Commercial antioxidant, bearing corrosion inhibitor and detergent comprising barium sulionate, barium phosphonate, zinc dialkyl dithiophosphate and a nitrogen-containing compound.

Lm Commercial detergent, pour point depressant and viscosity index prover.

Commercial antifoam agent comprising a silicone polymer.

1 26 percent reduction in wear.

8 40 percent reduction in wear.

12 percent reduction in wear.

48 percent reduction in wear.

1 37 percent reduction in wear.

is 29 percent reduction in wear.

I 27 percent reduction in wear.

Table 3 shows that the ethoxylated trisubstituted imidazoline of this invention achieved a total average reduction in piston ring wear of 40 percent as compared to a total average reduction in piston ring wear of 27 percent for the disubstituted imidazoline antiwear agent. Table 3 also shows the high utility of an additive of this invention in regard to engine cleanliness.

Examples 4 and 5 show the results of tests conducted to illustrate the improvement imparted to gasoline by lecithin mixtures with ethoxylated trisubstituted imidazoline and lecithin derivatives of ethoxylated trisubstituted imidazoline in regard to gasoline filter-clogging characteristics.

EXAMPLE 4 Table 4 shows the results of gasoline circulation tests made with gasoline samples with and without an ethoxylated trisub- TABLE 4.-GASOLINE CIRCULATION TESTS Fuel Make-up: Percent by Volume Gasoline 100 100 Added:

Tetraethyl Lead: mL/gal. 3. 3. 0 100/2 Texas Oil: percent by volume. 0. 0. 5

Solvent oil: percent by volume The reaction product of long chain fatty acids and dipropylene triamine plus 2 mols of ethylene oxide,

lbs/1,000 bbls Circulation Test Fuel throughput in gallons until there is a 50 percent reduction in flow rate through filter 5 e A mixture comprising in major proportion:

(On)-tiJNCH2-CHNH(OH:CHO)2H (I311 CH3 and/or methyl isomers thereof, or corresponding imidazolines having two separate hydroxyethyl groups attached to the side chain nitrogen.

b Gasollne Circulation Test procedure is described in SAE Reprint No. 61013, G. E. Gaston and J. J. Thomas, Contribution of Sediment and Additives in Gasoline to Clogging oi Filters in Automotive Fuel Systems, presented at Philadelphia, Pennsylvania, Meetings, October 29-November 2, 1962.

Table 4 shows that in the absence of lecithin, an ethoxylatcd trisubstituted imidazoline of this invention does not have a favorable effect upon gasoline filter-clogging characteristics.

EXAMPLE 5 A further series of gasoline filter-clogging tests was conducted to illustrate the improvement imparted to gasoline by lecithin mixtures with and derivatives of alkoxylated trisubstituted imidazolines of this invention. These tests were conducted with a gasoline sample containing a lecithin mixture with ethoxylated trisubstituted imidazoline, and with a gasoline sample containing a lecithin derivative of cthoxylated trisubstituted imidazoline. The results of these tests are shown in table 5. in interpreting the results of table 5, is is noted that a gasoline is considered to exhibit satisfactory filter-clogging characteristics when there is less than 50 percent reduction in fuel flow rate through a filter element at 20 gallon's throughput.

TABLE 5.GASOLINE CIRCULATION TESTS Gasoline additives Lecithin a X Reaction product of lecithin a and the reaction product of long chain fatty acids and dipropylene triamine plus 2 mols of ethylene oxide b Mixture of lecithin a and the reaction product of long chain fatty acids and dipropylene trianiine plus 2 mole of ethylene oxide b Gasoline Tests a A commercial neutral oil solution of a filtered soybean lecithin with moisture value less than 0.75 percent by weight, an acetone-insoluble value of 70 percent by weight and a viscosity of 3,046 centipoises.

b A mixture comprising in major proportion: 1

and/or methyl isomers thereof, or corresponding imidazolincs having two separate hydroxyethyl groups attached to the side chainnitrogen.

c For the Gasoline Circulation Tests additive concentrations were 15 lbs. per 1,000 barrels of gasoline plus 0.5 percent by volume solvent oil. Gasoline Circulation Test procedure is described in SAE Reprint No. 610 B, G. E. Gaston and J. J. Thomas, Contribution oi Sediment llii) and Additives in Gasoline to Clogging oi Filters in Automotive Fuel Systems," presented at Philadelphia, Pennsylvania, Meetings, October 29-November 2, 1962.

d For the Intake System Deposit Tests thc conccntratlon of additives was 15 lbs. per 1,000 barrels of gasoline. The test similates deposition of gum carried by gasoline in a carburetor and involves forming a gum 5 deposit in a test apparatus by evaporating additive-containing, high gum content fuel flowing countercurrcnt to a stream of heated air. Atthe end of the test, the weight of the adhering gum is dctermincd and compared to a reference run without additive for an appraisal of the additives detcrgency action. The test employs the same apparatus described by J. L. Keller and F. S. Liggett, Induction System Gum- Engine Versus Bench Test, Symposium on Vapor Phase Oxidation oi Gasoline, ASTM Special Technical Publication No. 202, pp. 21-40 (1956), but a somewhat different procedure is employed in order to appraise dctcrgency action of additives. A gum deposit is formed on the walls of a steam-iacketed glass U-tnbe by evaporating two liters of gasoline distillate admitted to the system countercurrent to a stream of preheated air. The U-tube is then washed with a number of portions of naphtha until a final wash shows no discoloration. The amount of gum adhering to the apparatus is then determined by extracting with C. P. acetone and evaporating the acetone extract with filtered, heated air to obtain a gum residue which is heated in an oven for one-half hour at l00l05 C., cooled and weighed. Results oi runs using the same gasoline with and without additive are compared to determine detcrgency action.

a At 10-15 gallons. At 20 gallons.

20 As noted above, satisfactory filter-clogging performance is achieved when there is less than 50 percent reduction in fuel flow rate through a filter element at 20 gallons throughput. The data in table 41 indicated that ethoxylated trisubstituted imidazoline without lecithin did not produce a gasoline com- 5 position meeting this filter-clogging performance requirement. Also, table 5 shows that lecithin without cthoxylated trisubstituted imidazoline did not produce a gasoline composition meeting this filter-clogging performance requirement. However, table 5 shows that both the mixture of lecithin with ethoxylated trisubstituted imidazoline and the lecithin derivative of ethoxylated trisubstituted imidazoline produced a gasoline composition which easily satisfied required performance levels. Table 5 also shows that use of both the mixture oflecithin with ethoxylated trisubstituted imidazoline and the derivative of lecithin with ethoxylated trisubstituted imidazoline resulted in reduced formation of carburetor-type gum deposits as compared to the performance of lecithin alone in this regard.

Various changes and modifications can be made without dcparting from the spirit of this invention or the scope thereof as defined in the following claims.

Iclaim:

l. A gasoline antiwear and antifilter-clogging agent comprising a lecithin derivative of or mixture with a trisubstituted imidazoline having the formula wherein R, is an alkyl radical containing seven to 29 carbon atoms, R and R are either hydrogen or a methyl radical, with the provision that one is a methyl radical and the other is hydrogen, R is a methylene, ethylene, or propylene group and R and R are selected from the group consisting of hydrogen, methyl, ethyl, hydroxyethyl, hydroxyethoxyethyl, hydroxyethoxyethoxyethyl, hydroxypropyl, hydroxypropoxypropyl and hydroxypropoxypropoxypropyl, with the provision that at least one of said R and R radicals is an hydroxyethyl, hydroxyethoxyethyl, hydroxyethoxyethoxyethyl, hydroxypropyl, hydroxypropoxypropyl, or hydr0xypropoxypropoxypropyl radical. 2. A lecithin derivative of or mixture with a trisubstituted 70 imidazoline having the formula provision that one is a methyl radical and the other is hydrogen, and R is a propylene group.

ggz gg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,615,291 Dat d October 26, 1971 Inventor(s) Helen I. Thayer It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

ABS'I'RAC'I, last line, after second "imidazolines" insert --o;1: the reaction product of lecithin with said imidazolines- Column 4, line 66, delete "77" and insert --catalytic cracking-- Signed and sealed this 30th day of May 1972.

(SEAL) Attest:

ROBERT GOTTSCHALK EDWARD M.FLETCHER, JR.

Commissioner of Patents Attesting Officer

Claims (1)

1. 2. A lecithin derivative of or mixture with a trisubstituted imidazoline having the formula wherein R1 is an alkyl radical containing seven to 29 carbon atoms, R2 and R3 are either hydrogen or a methyl radical, with the provision that one is a methyl radical and the other is hydrogen, and R4 is a propylene group.