US3644393A

US3644393A - Lecithin mixtures and reaction products of 1 2-disubstituted imidazoline

Info

Publication number: US3644393A
Application number: US854277A
Authority: US
Inventors: Helen I Thayer
Original assignee: Gulf Research and Development Co
Current assignee: Chevron USA Inc; Gulf Research and Development Co
Priority date: 1969-08-29
Filing date: 1969-08-29
Publication date: 1972-02-22
Anticipated expiration: 1989-02-22

Abstract

THE MIXTURE AND REACTION PRODUCT OF LECITHIN AND CERTAIN 1,2-DISUBSTITUTED IMIDAZOLINES ARE USEFUL AS GASOLINE ANTIWEAR AND ANTIFILTER-CLOGGING AGENTS.

Description

United States Patent 3,644,393 LECITHIN MIXTURES AND REACTION PRODUCTS 0F 1,2-DISUBSTITUTED IMIDAZOLINE Helen I. Thayer, Oakmont, Pa., assignor to Gulf Research & Development Company, Pittsburgh, Pa. No Drawing. Continuation-impart of application Ser. No. 544,838, Apr. 25, 1966. This application Aug. 29, 1969, Ser. No. 854,277

' Int. Cl. C07d 49/34 U.S. Cl. 260309.6 2 Claims ABSTRACT OF THE DISCLOSURE The mixture and reaction product of lecithin and certain 1,2-disubstituted imidazolines are useful as gasoline antiwear and antifilter-clogging agents.

This application is a continuation-in-part of Ser. No. 544,838, filed Apr. 25, 1966, now US. Pat. No. 3,527,583.

This invention relates to multipurpose additives for motor fuels, to motor fuel compositions containing a minor proportion of said additives, and to methods of improving the performance of gasoline-burning engines with said compositions. 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.

The antiwear and antifilter-clogging gasoline additives 0f the present invention comprise either a mixture of or the reaction product of lecithin and a 1,2-disubstituted imidazoline. The imidazoline has an alkylamine substituent in the 1-position and an alkyl substituent containing 7 to 29 carbon atoms in the 2-position. A preferred 1,2-disubstituted imidazoline of this invention is prepared by reacting diethylene triamine and a mixture of saturated and unsaturated fatty acids to produce predominantly a 1-(2- aminoethyl)-2-alkylimidazoline having the general formula In the absence of lecithin, the 1,2-disubstituted imidazolines utilized in this invention impart an only partially beneficial effect when added to gasoline. The 1,2-disubstituted imidazolines per se impart antiwear properties to gasoline as evidenced by reduction in loss of metallic iron from cast iron piston rings. However, when the 1,2-disubstituted imidazolines are either mixed with or reacted with lecithin the product exerts an additional highly beneficial effect in gasoline, i.e. substantial reduction of the tendency of the gasoline to clog the filter through which it passes in its flow to an engine. The lecithin imidazolines 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 antifilter-clogging characteristic 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 reducing abrasion at said piston rings.

3,644,393 Patented Feb. 22, 1972 Therefore, the antiwear and antifilter-clogging characteristics of the 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 both the mixture of and the reaction product of lecithin and the 1,2- disubstituted imidazolines utilized in this invention is unexpected because neither lecithin by itself nor the imidazolines 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 1,2-disubstituted imidazolines of the invention exhibit high antifilter-clogging characteristics.

It is significant that imidazolines differing from the imidazolines of the present invention only by the addition of a methyl substituent to the imidazoline ring do not exhibit antiwear properties. While the reaction product of diethylene triamine and a fatty acid produces a l,2-disubstituted imidazoline which is a highly effective antiwear agent, the reaction product of dipropylenetriamine and the same fatty acid produces a 1,2,4 or 1,2,5-trisubstituted imidazoline containing a methyl substituent in either the 4 or 5 position of the imidazoline ring which is not an effective antiwear agent. Therefore, while N CH:

is an effective antiwear agent, the compound 17) N OH2 CH' NH2 N CH2 CH2 Ca 6H,

and methyl isomers thereof are not antiwear agents. Additional comparisons of the characteristics of closely rated compounds are found in applications Ser. No. 544,- 839 and Ser. No. 544,840, both entitled Motor Fuel Multipurpose Agents and filed on the same date as this application by the same inventor.

The 1,2-disubstituted imidazolines of this invention have the general formula wherein A highly.effective commercialimidazoline whose; major.

component is 1- (Z-aminoethyl) -2-heptadecenylimidazoline having the formula is prepared by reacting a mixture of long chain fatty acids with diethylenetriamine. Another imidazoline can be prepared by reacting a fatty acid having 8 to 30 carbon atoms with N-aminomethyl ethylenediamine. The fatty acid mixture used in the synthesis of the above-mentioned commercial imidazoline comprised 37.0 percent linoleic acid, 6.0 percent conjugated linoleic acid, 52.5 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 and lignoceric acids.

Examples of suitable 1,2-disubstituted imidazoline compounds of this invention include 1- (2'-aminoethyl -2-undecylimidazoline,

1- 2'-aminoethyl) -2-heptadecylimidazoline,

1- (2'-aminoethyl -2-tridecylimidazoline,

1- (2'-aminoethyl -2- 8"-heptadecenyl -imidazoline,

1-(2'-N,N-dimethylaminoethyl)-2-(8",11"-heptadecadienyl imidazoline,

1-(2-N-methylaminomethyl -2-pentadecylimidazoline and l-aminomethyl-Z-heneicosylimidazoline.

Any commercial lecithin can be utilized in accordance with this invention, such as lecithin derived from soybean oil, corn oil, linseed oil or egg yolk.

A particular commercial lecithin which was advantageously both mixed with and reacted with an imidazoline as described above is a neutral oil solution of a filtered soybean lecithin with a moisture value less than 0.75 percent by Weight, an acetone-insoluble value of 70 percent by weight and a viscosity of 3046 centipoises. According to one method of preparation of the lecithin derivative of the 1,2-disubstituted imidazolines, base lecithin is reacted with the imidazoline at 5580 C. for 19 to 55 hours while stirring the reaction mixture. In one synthesis, grams of 1-(Z-aminoethyl)-Z-heptadecenylimidazoline and 60 grams of the commercial base lecithin were heated at 55-80 C. for 19 hours. The conditions of reaction of the base lecithin with the 1,2-disubstituted imidazoline are not critical and a wide range of reaction conditions can be utilized. In general, the reaction can be carried out at a temperature between about 40 C. to 100 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, if the 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 to 20 and about 20 to 1. All of these conditions are non-limiting and are presented for illustrative purposes only.

The concentration of the lecithin-imidazoline derivative or the mixture of lecithin and imidazoline in gasoline is not critical. For example, an additive of this invention can be present in gasoline in a general concentration range of 0.1 to 100 pounds per 1000 barrels, or a preferred concentration range of 1 to pounds per 1000 barrels. In terms of weight percentage, an additive of this invention can be present in gasoline in a general range of .00004 to .04 percent or a preferable range of .0004 to .01 percent. If the additive comprises'a mixture of lecithin and imidazoline, the ratio of lecithin to imidazoline can vary widely. For example, the ratio of'lecithin to imidazoline can be within the range 1:2 to 20: 1, generally, or within the range 2:1 to 8:1, preferably.

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 compositions can contain normal, branched-chain, and cyclic hydrocarbons having from 4 to 12 carbon atoms. The hydrocarbons portion of the gasoline compositions can comprise products prepared in the chemical conversion of hydrocarbons to produce gasoline such as 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 catalytic-cracking process, and about 20 percent of the aforementioned alkylate.

EXAMPLE 1 Radioactive piston ring wear tests were performed to demonstrate the high antiwear characteristics of a gasoline containing a compound of this invention and to also demonstrate the criticality of the chemical structure of the additives of this invention. Following is a description of the test procedure employed in the radioactive piston ring wear tests.

Test procedure Each radioactive ring wear test was performed with a CLR laboratory test, 4-stroke, single cylinder internal combustion engine equipped with a cast iron top compression ring which prior to use had been rendered radioactive by insertion into the pile of an atomic reactor. The engine provided with the radioactive ring was operated at constant speed for 10 hours under the following test conditions.

Speed: r.p.m. 2000.

Load: BHP 5.

Spark 15 before top center.

Air-fuel ratio l3.7/l.0.

Cylinder wall temp., F 112.

Sump oil temp. F 125.

Carburetor: Intake 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.

Table 1 shows the results of radioactive piston ring wear tests made with a gasoline sample containing 1-(2- aminoethyl)-2-heptadecenylimidazoline, which is a 1,2- disubstituted imidazoline of this invention, and with separate gasoline samples containing the imidazoline reac tion products of long chain fatty acids and ethoxylated and nonethoxylated diproplyene triamine, both of which are trisubstituted rather than disubstituted imidazolines and therefore not irnidazolines of this invention. As shown by the structural formulae in Table 1, the I-(Z-aminoethyl)-2-heptadecenylimidazoline of this invention differs primarily from the reaction product of long chain fatty acids and dipropylene triamine only by the absence of a methyl group on the imidazoline ring.

TABLE 1.RADIOACTIVE PISTON RING WEAR TESTS Percent change Additive in piston ring concentrawear rate as tion, grams compared to per gallon reference Additive of gasoline gasoline 1-(2-aminoethyD-Z-heptadeceriylimidazoline e 0. 270 33 The reaction product of long chain fa y acids and dipropylene triamine b 0. 140 +5 The reaction product of long chain fatty acids and dipropylene triamine plus 2 mols of ethylene oxide 0. 140 38 a The structural formula is-' (Ci7)C--N-CH2CHzNH2 N CH2 b A mixture comprising in major proportion: l

(Cn)(;JNOHzCHNHg N CH1 CH (IJH CH3 and methl isomer thereof.

A mixture comprising in major proportion:

(C17)fiNCHzCHNH(CHzCH2O)2H and methyl isomers thereof, and/or corresponding imidazolines wherein two separate hydroxyethyl groups are attached to the side chain mtrogen.

Table 1 shows that the disubstituted imidazoline of this invention reduced the piston ring wear rate 33 percent as compared to a reference gasoline sample, while a trisubstituted imidazoline differing from the imidazoline of this invention primarily only by the addition of a methyl group to the imidazoline ring was not an antiwear agent and actually increased the piston ring wear rate by 5 percent. Table 1, also shows that thetrisubstituted imidazoline can be transformed into an effective antiwear agent by adding ethylene oxide thereto, a procedure which adds considerably to the cost of. the additive as compared to the nonethoxylated imidazoline of this invention. Furthermore, it is shown in Example 2, below, that the addition of ethylene oxide to the disubstituted imidazoline of this invention actually deprives said imidazoline of its antiwear properties. Example 2 therefore reinforces the showing of criticality of the structure of disubstituted imidazolines as compared to trisubstituted imidazolines in regard to antiwear properties.

EXAMPLE 2 Table 2 shows the results of further radioactive piston ring wear tests. The tests of Table 2 compare the antiwear properties of gasolines containing ethoxylated and nonethoxylated disubstituted imidazolines of this invention prepared by reaction of fatty acids which diethylene triamine, with the antiwear properties of gasoline containing ethoxylated and nonethoxylated trisubstituted imidazolines prepared by reaction of fatty acids with dipropylene triamine, which are not additives of this invention.

As shown in Table 2, the disubstituted imidazoline of this invention is an antiwear agent in the nonethoxylated state, but is not an antiwear agent when ethoxylated. On the other hand, trisubstituted imidazoline is not an antiwear agent when nonethoxylated but must be ethoxylated to be converted to an antiwear agent. Because di-substituted imidazolines are effective antiwear agents in the nonalkoxylated state they are less expensive antiwear agents for gasoline than the trisubstituted imidazolines which require alkoxylation for impartation of antiwear characteristics.

TABLE 2.-RADIOACTIVE PISTON RING WEAR TESTS Concen- Control,

tration, iron wear, Fuel additive p.p.m. Piston rings Oil mg. Test, iron wear, mg. The reaction product of long chain fatty acids and diethyl- 98. 5 Radioactive Base motor oil free 8. 7 6.1.

ene triarnine. cast iron. of additives. The reaction product of long chain fatty acids with di- 98. 5 do -do 8.7 No significant change in ethylene triamine and 2 mols of ethylene oxide. weatr a? compared to con r0 The reaction product of long chain fatty acids with dipro- 98. 5 .do do 5. 5 4.3.

pylene triamine plus 2 mols of ethylene oxide. I The reaction product of long chain fatty acids and dipro- 98. 5 ..-do .-do 5. 5 No significant change in pylene triamine.

A commercial mixture comprising about to percent by weight of l-(Zaminoethyl)-2-heptadecenylimidazoline (Ci7)C--NCH2CH2NHg 0 A mixture containing in major proportion and/or corresponding imidazolines having two separate hydroxycthyl groups attached to the side chain nitrogen.

wear as compared to control.

0 A mixture containing in major proportion and methyl isomers thereof, and/or corresponding imidazolines having two separate hydroxyethyl groups attached to the side chain nitrogen.

d A mixture containing in major proportion and methyl isomers thereof.

7 EXAMPLE 3 A'further series of tests was conducted which utilized a method other than radioactivity to determine not only antiwear characteristics" but also engine cleanliness characteristics of a disubstituted imidazoline in gasoline. The

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 attain 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 10-minute warm-up before commencing the first 8-hour period of test operation.

Following are the conditions prevailing during the test:

Load: BHP 45:1.

Speed: r.m.p. 2500:25.

Spart advance 38:3 before top center at 2500 r.p.m.

Spark plug gap: in. 0.040.

Va-lve clearances-in:

Intake 0.008.

Exhaust 0.013.

Intake manifold Heat control locked in off position. Pistons Tin plated cast iron.

Water jacket coolant temperature:

Inlet: F. 85:5.

Outlet: F. 95:2.

Oil temperature: F. 155:5.

Air-fuel ratio l4.5:0.5/ 1.0.

Crankcase ventilation: c.f.m. 1.

Oil change: qt. 4 /2.

Crankcase lubricant Motor oil.

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 Oil Screen Cylinder Walls Crankcase Oil Pan Crankcase Oil Pan Rocker-Arm Assembly PushaRod Cover Plate Rocker-Arm Cover Plate Rocker-Arm Cover Plate Push-Rod Cover Plate The total engine rating is the sum of the ratings made on the ten parts listed above. Each part is rated on a scale of (heavy deposits) to (clean).

The piston rings were weighed before and after the test to ascertain the ring weight loss. The results of the test are shown in Table 3.

TABLE 3.EFFECT OF ADDITIVE ON ENGINE OLEANLINESS AND WEAR Fuel make-up, percent by volume:

G olme 100 100 5 Added:

Tetraethyl lead, mL/gaL 2. 5 2. 5 The reaction product of long chain fatty acids and diethylene triamine, lbs/1,000 bbls Oil make-up, percent by volume:

Light neutral oil 30. 25 Medium neutral oil .0 65. 00 Oil additive b 4. 25 10 on additive 0. 50 Oil additive 0. 01 ti-cylinder automobile engine cleanliness and wear test:

Total engine cleanliness rating (l00=clcan) (varnish and sludge) "80. 0 82. 0 Skirt varnish rating avg. piston (10=clean) 6. 5 7. 5 Ring weight loss: 1 First ring (compression): Average weight loss 1 for six pistons, mg .9 68

Second ring: Average weight loss for six pistons,

mg 34 f Third ring: Average weight loss for six pistons,

mg 54 s 34 Total average ring Weight loss, mg 180 132 I! A commercial mixture comprising about 90 to 95 percent by weight oi l-(2-aminocthyl)-2-hcptadecenylimidazoline v v Commercial antioxidant, bearing corrosion inhibitor detergent comprising barium sulfonatc, barium phosphonate, zinc dialkyl dithiophosphate and a nitrogen-containing compound.

0 Commercial detergent, pour point depressant and viscosity index improver.

Commercial antifoam agent comprisinga silicone polymer.

9 26% reduction in wear.

f 12% reduction in wear.

B 37% reduction in wear.

h 27% reduction in wear.

Table 3 shows the high utility of an additive of *thisinvention for purposes of both maintaining engine cleanliness and reducing piston ring wear.

The tests of Examples 4 and 5 were conducted to il lustrate the improvement imparted to gasoline by lecithin mixtures with disubstituted imidazolines. and lecithin derivatives of disubstituted imidazolines in regard to fuel filter-clogging characteristics.

EXAMPLE 4 Table 4 shows the results of gasoline circulation tests to determine the maximum possible throughput through of fuel filter until a 50 percent reduction in fuel flow rate through the filter element occurred. The tests were conducted with a gasoline control sample and with gasoline containing a lecithin-free disubstituted imidazoline.

TABLE 4.GASOLINE CIRCULATION TESTS Fuel make-up, percent by volume:

Gasoline 100 100 Added: J

Tetraethyl lead: ml. /gal 2. 5 2. 5 Solvent oil, percent by volume 0.5 The reaction product of long chain fatty acids and diethylene triamine, lbs/1,000 131315;. 15 Circulation test Fuel throughput in gallons until there is a 50 percent reduction in flow rate through filter 20 5 filter-clogging characteristics of gasoline. 1'

EXAMPLE 5 A further series of gasoline filter-clogging tests were conducted to illustrate the improvement imparted to gasoline in this respect by lecithin mixtures with and derivatives of a disubstituted imidazoline. These tests were conpercent by weight of ducted with gasoline containing lecithin alone, with gasoline containing a lecithin mixture with disubstituted imidazoline and with gasoline containing a lecithin derivative of disubstituted imidazoline. The results of these tests are shown in Table 5. In reference to the data of Table 5, it is noted that a gasoline is considered to exhibit satisfactory filter-clogging performance when there is less than 50 percent reduction in fuel fiow rate through a filter element at 20 gallons throughput.

TABLE 5.-GASOLINE CIRCULATION TESTS Additives:

Lecithin Reaction product of lecithin and the reaction product of long chain fatty acids and diethylene triamine Mixture of lecithin and the reaction product of long chain fatty acids and diethylene triamine b Gasoline tests:

Gasoline circulation test percent reduction in flow rate at stated gallons fuel throughput (more than 50 percent reduction in flow rate at 20 gallons fuel throughput is unsatisfactory) Intake System Deposit Test percent reduction in carburetor-type gum deposits 1 50% at -15 gals. 2 25% at 20 gals. B 22% at 20 gals.

e A commercial neutral oil solution of a filtered soybean lecithin with moisture value less than 0.75 percent by Weight, an acetoneinsoluble value of 70 percent by Weight and a viscosity of 3,046 centipoises.

b A commercial mixture comprising about 90 to 95 percent by Weight of l-(2-aminoethyl)-2-heptadecenylimidazoline (Cm-g III-CHzCH2NHg N CH2 For the Gasoline Circulation Tests additive concentrations were 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 of Sediment and Additives in Gasoline to Clogging of Filters in Automotive Fuel Systems, presented at Philadelphia, Pennsylvania, Meetings, October 29- November 2, 1962.

d For the Intake System Deposit Tests the concentration of additives Was 15 lbs. per 1,000 barrels of gasoline. The test simulates deposition of gum carried by gasoline in a carburetor and involves forming a gum deposit in a test apparatus by evaporating additive-containing, high gum content fuel flowing counterourrent to a stream of heated air. At the end of the test, the Weight of the adhering gum is determined and compared to a reference run Without additive for an appraisal of the additives detergency action. The test employs the same apparatus described by J. L. Keller and F. S. Liggett, Induction System Gum-Engine Versus Bench Test, Symposium onVapor Phase Oxidation of Gasoline, ASTM Special Technical Publication No. 202, pp. 21-40 (1956), but a somewhat different procedure is employed in order to appraise detergency action of additives. A gum deposit is formed on the Walls of a steam-jacketed glass U-tube 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 0.1. 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 100105 C., cooled and Weighed. Results of runs using the same gasoline with and Without additive are compared to determine detergency action.

As noted above, satisfactory filter-clogging performance is achieved when there is less than 50 percent reduction in the fuel flow rate through a filter element at gallons throughput. The data in Table 4 indicate that disubstituted imidazoline Without lecithin did not produce a gasoline composition meeting this filter-clogging perform- 5 ance requirement. Also, Table 5 shows that lecithin without imidazoline did not produce a gasoline composition meeting this filter-clogging performance requirement. However, Table 5 shows that both the mixture of lecithin with disubstituted imidazoline and the lecithin derivatives of disubstituted imidazoline produced a gasoline compo sition which easily satisfied required filter-clogging performance levels. Table 5 also shows that use of either the mixture of lecithin with disubstituted imidazoline or the lecithin derivative of disubstituted 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 departing from the spirit of this invention or the scope thereof as defined in the following claims.

I claim:

1. The reaction product of a 1,2-disubstituted imidazoline having the formula wherein R is alkyl/or alkenyl containing 7 to 29 carbon atoms, R is a methylene group or an ethylene group, and R and R are hydrogen, methyl or ethyl radicals, with lecithin, the reaction occurring at 40 to C. with a ratio of lecithin to imidazoline between about 1 to 20 and about 20 to 1. 2. The reaction product of claim 1 wherein R contains 11 to 17 carbon atoms, R is an ethylene group, and R and R are hydrogen.

References Cited UNITED STATES PATENTS 2,355,837 8/1944 Wilson 260-309.6

2,794,808 6/1957 Albrecht et al. 260-309.6

3,291,731 12/1966 Crowley et a1. 260-309.6

3,313,607 4/1967 Gaston 44-58 FOREIGN PATENTS 846,693 8/ 1960 Great Britain 44-58 OTHER REFERENCES Hackhs Chemical Dictionery, 4th ed. (1969) ed. Julius Grant, p. 384.

HENRY R. JILES, Primary Examiner S. D. WINTERS, Assistant Examiner U.S. Cl. X.R. 44-63