US2980520A - Gasoline motor fuel - Google Patents

Description

ploy fuels having a high octane number.

2,980,520 GASOLINE MOTOR FUEL Helen I. Thayer, Pittsburgh, Pa., assignor to Gulf Re search & Development Company, Pittsburgh, Pa., a corporation of Delaware 1 No Drawing. Filed June 11, 1959, Ser. No. 819,568

' 9 Claims. c1. 44--69) result from increased compression ratios have been known in the automotive industry for some time as evidenced by the fact that automobile manufacturers have been marketing automobiles with engine compression ratios of 9:1 or higher. In order to obtain smooth engine performance at high compression ratios, it has been necessary to emquire the addition of organometallic anti-knock agents such as tetraethyl lead to obtain high octane numbers. The use of these additives has certain disadvantages in that the fuels containing them tend to leave deposits on the piston head, valves and walls of the combustion chamber of the engine and on the electrodes and insulators of the spark plugs. These deposits reduce the efiioiency of the engine and may offset increased eificiencies obtained by high compression ratios.

These deposits tend to build up in the engine and to increase theoctane numberrequirement of the'engine until an equilibrium octane number is reached. Thus, in engines that have been in operation for several hundred hours, the octane number required may be as much as 15 numbers higher than the requirement of that engine at the start of operation. For example, a clean engine which requires a gasoline having an octane rating of 75 in order not to knock may require octane values as high as 90 after the fuel deposits have accumulated on the engine parts.

These deposits comprising'decomposition products of tetraethyl lead are material factors inraising the equilibrium octane requirement-of an engine, but they are not the only cause of deposition inthe engine. Thus, an in crease in the octane number requirement is noted when gasolines to which no lead has been added'are used as fuels] The increase in octane number requirement in these fuels is the result of, deposits from incomplete combustion or decomposition of the gasoline and. of gasoline additives other than tetraethyl lead. However, the octane number requirement increase isusu'ally less with unleaded fuel than with; leaded fuel.

,Various scavenging agents have been addedto fuels toflovercome the detrimental-effects of the deposition of lead compounds. These additives change the form of the lead compounds so they are more volatile and thus less likely to be deposited in the engine. For example, various volatile. alkyl halides such as ethylene dibromide or ethylene dichloride'have been used with tetraethyl lead to produce the corresponding halides of lead which are more volatile than the oxides. These additives have not been completely successful in overcoming the deposition of decomposition products. The decomposition products comprise various salts including the oxides, sulfates, bromides and chlorides of lead which have been found to alterthe engine characteristics ad- .versely when deposited in the combustion chamber of the engine. g g .-.As a matter entirely apart from the problem of preignition due to engine deposits, it hasbeen foundthat" 2,980,20 Patented Apr. 18, 1961 "2 deterioration over a period of time. 'This difiiculty is probably due to the presence of certain undesirable constituents which are subject to oxidational change and result in the formation of gums and color-imparting bodies in the gasoline. In contrast to the sludges formed in fuel oil, the gums formed in gasolines are soluble therein and do not appear as such except upon the evaporation of the gasoline. It is probable that at least a part of the gum and color formation is due to the polymerization of olefinic, diolefinic and other unsaturated hydrocarbons.

I have found that improved gasoline fuel compositions are obtained by the addition of small amounts of a reaction product of (a) primary, secondary or tertiary alkyl Most fuels rc- 1 (cyclic or open-chain), alkenyl or alkylol monoor diamines whose substituents contain 2 to 22 carbon atoms, preferably alkyl and alkenyl monoand diamines, such as tertiarybutylamine or 3-tallow-aminopropylamine, and ([2) complex anhydrides prepared by reacting a partially esterified orthophosphoric acid that contains 1 to 2 organic substituents, at least one of which is a hydrocarbon radical containing 5 to 22 carbon atoms and the other of which when present is a hydrocarbon radical containing 1. to 22 carbon atoms, such as the monoand di(2-ethylhexyl) orthophosphates and a borylating agent such as boric acid, boric oxide or an anhydride of boric oxide and an aliphatic monocarboxylic acid, preferably a C unsubstituted acid such as acetic acid, in the ratio of about 0.5 to 6 moles of partially esterified orthophosphoric acid per mole of borylating agent, under conditions conducive to anhydride formation. The amines and the complex anhydrides are reacted in the ratio of 0.5 to 2 equivalents of anhydride per equivalent of amine. Good results are obtained by the use of about 0.002 to 1 percent of the reaction products, but other quantities can be used. The preferred gasoline solubile amine compounds for preignition suppressors are those which contain a large proportion ofphosphorus in the molecule, for example, the reaction products formed from the borylated partially esterified orthophosphates and lower molecular weight amines such as tertiarybutylamine, propylam'ine, isopropylamine, etc. The percentage of phosphorus in the molecule is relatively less important in the compounds used as additivesto suppress, oxidation of the gasoline. Thus, the'reaction products formed from the borylated partially esterified orthophosphates' and the gasoline soluble higher fatty alkyl diamines, such as 3-tallow-aminopropylamine have been found to give excellent results as oxidation inhibitors,

When the addition products of this invention are used ingasoline in amountscorresponding to at least 0.1 times to preignite a gasoline air mixture. When used in any proportion described herein, they impart oxidation sta- "bility to the gasoline- It might appear that these compounds inhibit theoxidational changes and the polymerizationof the olefins, .d'olefins and other unsaturated V hydrocarbons present'in'the gasoline.

' 1cra'cl ed gasolines, polymer gasolines and blendscontain- Preferred reaction products included by the invention arerthe tertiarybutyl amine derivative of the anhydride" 'formed from boric. oxide and mono-di(2-ethylhexyl) orthophos'phate (1:3 molar ratio) wherein the acid-amine equivalent ratio is 151; the 3-tallow-aminopropylamine derivative of'the anhydride formed from boric oxide and mono-di(-2-ethylhexyl) orthophosphate (1:3 molar ratio) wherein the acid amine equivalent" ratio is 1.:2;.the' 3- tallow-arninopropylaminei derivative of the "anhydride formed from boric oxide and ethyl ,lauryl orthopl osphate.

ing these gasolines are unstable and te nd to undergo (1:1 molar ratio) wherein the acid-amine equivalent ratio or. a yiscous oily product is recovered. p i The process used in prepaging'the complex anhydride is also described briefly iri my copendingapplication Serial acid orthophosphate (1:0.8 molar ratio); the anhydrideof boric oxide and acetic acid and dioctyl monoacid orthophosphate (1:3 molar ratio); boric oxide and diamyl monoacid orthophosphate (1:3 molar ratio), boric oxide and monooctyl diacid orthophosphate (1:2 molar ratio); and one equivalent ofany of. the following: 2-ethylhexylamine, 3-isopropylarnine, tertiarybutylamine, n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine,

n-octadecenyla'mine, N,N dibuylisopropylamine, 3 isopropylaminopropylamine, N-octadecenyl ethylene diamine, 3-dodecylaminopropylaminc, and those monoand diamines where the respective nitrogen substftuents are mixed alkyl and alkenyl groups obtained from naturally occurring fats and oils, e.g'., tallow, soybean oil, coconut oil and the like. In such instances, the aliphatic N- substituent will be monovalent straight-chain hydrocarbon radicals containng an even number of carbon atoms from 8 to 22.. Examples of such mixtures are: 3-tallow aminopropylamine, 3 soya aminopropylamine, 3- coco-aminopropylamine, cocoamine, etc. I

From the foregoing discussion, it will be seen that the reaction products-whose use is included by this invention can be illustrated by the structuralformula where R is an alkyl, alkenyl or alkylol group containing 2 to22 carbon atoms, x is or 1, R and R" are hydrogen when x is greater than 0 or hydrogen, alkyl, alkenyl or alkylol groups of the same kind as R when x is 0, y is an integer from 0 to 3 but is zero only when x is zero, H is hydrogen, N is nitrogen, z is a number from 5 to 10, A is an acid radical derived from a borylated partially esterified orthophosphate of the kind described hereinabove, and w is 1 to 4, and z andw are not necessarily whole numbers.

The preparation of these compounds is not a part of this invention and they can be prepared in any suitable manner. The preferred method of preparing these compounds is disclosed in the copending application of Helen I. Thayer, Serial No. 819,566, filed of evcndate herewith. As described in that application, they can be prepared by adding the desired amine to a selected complex acidic anhydride of the kind defined above, inthe proportion described herein; preferably while maintaining the reaction temperature at 40? to 60 C. Heat is gen'er ally evolved in this additionso it normally desirable toadd the amine gradually to control temperatures. Although the reactions will take place spontaneously without addiants moderately before introducingthem into'the reaction is complete, the slurry is cooled' and asemi-solidmelt 7 same when an'anhydride of boric o-xide and an aliphatic -monocarboxylic acid is used as; the borylatfng agent in that the reaction progresses satisfactorily in the absence of the solvent. The temperature at which these reactions are carried out varies Withthe borylating agent and the nature of the by-product evolved in the reaction. The temperature must be high enough to driveoff the water I or aliphatic monocarboxylic ac'd evolved, but below the decomposition temperature of the product, Thus, the temperature may be as low as 50 .C. or as high as 145 C. Both the reaction involving formation of the anhydride and the subsequent reaction of this product are carried out at atmospheric pressure.

The addition agents of this invention are useful ina wide range of proportions. The amount used is dependout on the function to be performed bythe additive, for example, the amount of additive to be added to the gasoline in order to reduce the octane requirement increase, minimize preignition, effectively decrease wild ping count and decrease the. average noise-requirement, depends on the deposit forming characteristics of the fuel when burned in an internal combustion engine.

. '60 t qn of heat, it is sometimes desirable to heatthe reach.

When the'fuel is a leaded gasoline,the amount of compound to be added can be determined by the amount of tetraethyl lead which is present. The most satisfactory approach, in view of the fact that the molecular weights of the compounds vary from compound to compound, is to add that amountof compound necessary to convert the lead present to lead orthophosphate. -While improved results can be obtained with very small amounts, amounts corresponding to at least about 0.1 times that theoretically required to convert thelead to lead orthophosphate are preferred. Especially good results are obtained by using about 0.2 to about 0.5 times the theoretical amount required. In general, I prefer to use an amount not more than the amount theoretically required to convert all the lead to lead orthophosphate. Amounts greater than the theoretical amount can be employed, but for economic reasons, Iprefer to useonly the amount required to give the desired improvement. Therefore, I prefer to employ an amount equal to about 0.2 to about 0.5 times that theoretically required to convert the lead to lead ortho phosphate. In view of the fact that the amount of tetraethyl lead varies from gasoline to gasoline, it is diflicult to state on a weight basis the amount of a particular compound required; Most gasolines 1 marketed today contain between about land about 3 cubic centimeters of tetraethyl lead per gallon of gasoline. Based upon a gasoline having a gravity of about 54 API and containing about 1 cubic centimeter of tetraethyl lead, I have determined that the amount of the tertiarybutylamine derivative of borlyated mono-di(2-ethylhexyl) orthophosphate, forexarriple, corresponding to about'0.1 to about 1.0 theories is [about 0.004 to about 0.044 percent by. weight 'of the gasoline, i

If the same gasoline contains 3 cubic centimeters. of

"tetraethyl" lead, then the amount of tertiarybutylamine No. 819,566,and in greater detail'in mycopending application Serial No, 1 119,569, directedtliereto, Asindicatcd in the. latteiythe processfcan difierlsomewhat depending I o theibo ylat is agent e genera p ce'du i synth mingth'esej compounds when boric'oxide-orprtho ori cacid'is thejborylating agent comprises refluxinga concentrations. For most currently marketed commercial derivative of theborylated mono-di(2-ethylhexyl) orthophosphateis about 0.013 to about 0.13 percent by weight of the gasoline. Thus, the'normally useful concentration for a 54 API gasoline containing about 1 to about 3 cubic centimetersof tetraethyl lead per'gallon is about 0.004 to about 0.13 percent by weight of the gasoline. Although greater concentrations can be employed to advantage in some instances, no additional benefits with respectto' preignition are achieved by the use of greater gasolines,.about'0.001to about 0.15 weight percent of the a areness s a stirs at he: b r l ss. assagents, dyes .1 and the like. Gasolinecompositions of di(2-ethylhexyl) orthophosphate is usually sufiicient to achieve 'a satisfactory reduction of the preignition tendencies of the fuel. The amount within this range should, of course, be sufiicient to incorporate between 0.1 and about 1.0 times that theoretically required to convert the lead to lead orthophosphate.

It will be understood, of course, that the optimum amount on a weight basis for tertiarybutylamine reaction product may not be the optimum amount for another amine derivative of another borylated orthophosphate or another amine derivative of the borylated .mono-di(2- ethylhexyl) orthophosphate compound. One reason for this is that the effectiveness of the compounds may vary from one compound to another. Another reason is the obvious differences in the molecular weights of the compounds in this series so that to obtain an equivalent amount of phosphorus when using a compound having higher molecular weight it is necessary to use a different amount of the compound on a weight basis.

' The amount of the reaction products required to impart oxidation stability to the gasoline can be calculated on a different basis since the gum formation or discoloration is probably caused by the presence of polymers or com- .pounds containing oxygen or sulfur rather than to the presence of tetraethyl lead in the gasoline. Obviously the various salts of the herein disclosedclass do not possess exactly identical effectiveness, and the most advantageous concentration for each salt will depend to some extent upon the particular compound used. Also, the minimum effective inhibitor concentration may vary somewhat according to the specific nature of the gasoline to be inhibited. In. general, however, the herein disclosed salts 'manner. Thus, they can be added as such to the gasoline in the form of dispersions or solutions in solvents such as butanol, diethylene glycol, monobutyl ether, benzene, toluene, heptane, kerosene, gasoline, mineral oil or the like, which solvents do not themselves contribute to the preig'nitionor oxidation-inhibitive characteristics of the ultimate composition. If desired the amine derivatves of the borylated partially esterified orthophosphate antipreig'niti'on or anti-oxidant agents can be incorporated in the gasoline fuel compositions in admixture with other,

materials designed to improve one or more properties of the gasolinesuch as anti-stalling agents, corrosion 1nhibitors, anti knock agents, e.g., tetraethyl lead, deicmg illustrated by'the following specific examples: 11

" EXAMPLE 1.

I Amotor gasoline composition according to this invention was prepared by incorporating in a sample of conventional commercial gasoline, 0.479 gram per gallon (L017 weight'percent) of the tertiarybutylarnine-derivative of the anhydride prepared byreacting 1.0 mole of boric oxide with 3.1 moles of rmono-di(2-ethylhexyl) Y orthophosphate, a mixture o f rnon oand diesters, by adding the amine to the borylated mono-di(2-ethylhexyl) "orthophosphate while maintaining, the reaction temperatureatabout'40f 0, wherein the'anhydride-amine equivfalent ratio was 1:1. The base gasoline was'a blended gasoline made up of 22.1 parts catalytically cracked gasojliri i'e, 43.4 parts alkylate, 30.5, parts fPlatformate, and

.4.0 parts spent butane and contained about 1.9 cubic centimeters (about 3.13fgr'arns); of' gtetraethyl' 'lead 'per gallonj offgasoline. The tertiarybutylamine derivative of.

borylated mono-di(2l-.ethylhexyl) orthophosphate thus comprised 0.2 times the theoretical amount required to convert the tetraethyl lead to lead orthophosphate. Typical's'amples of the base gasoline and the base gasoline containing 0.479 gram per gallon of the tertiarybutylamine derivative of borylated mono-di(2-ethylhexy1) orthophosphate had the following inspections:

Inspection data Copper Strip Test, 122 F., 3 Hr 0 Copper Dish Gum, MQJIOU ml- 7 Existent Gum, MgJlOO m1 0' Oxidation Stability, 212 F., Min 1440 Acid Heat, F (38) Knock Rating:

Motor Method, Octane No 91. 0

Research Method, Octane N0 98. 9 TEL, mL/gal 1. 86 Vapor Pressure, Reid, 7.8 Bromine No 26 Distillation, Gasoline:

Over Point, F End Point, F 10% at, F 50%..

90%. .1 Recovery, Percent t tduetr t...

.,EX M E. 2 A gasoline composition demonstrating the excellent Wild ping count improvement characteristics of-these additives was prepared by incorporating 0.983 gram (0.035

mono-di(2-ethylhexyl) orthophosphate thus comprised about 0.43 times the theoretical amount required to con- 7 vert the tetraethyl lead to'lead orthophosphate. Typical a 55 this "invention can be further Copper Dish,Gum, M L/ ml.

Vapor Pressure, R

'Bi'ornine'Nolnn.

samples of the base gasoline and base gasoline containing 0.035 weight percentof the tertiarybutylamine derivative of borylated mono-di(2-ethylhexyl) orthophosphat had the following inspections:

Inspection data Plus 0.035 Wt. Percent'lcrtiarybutylamine With noTertiarybutylamine derivative of Inspections borylated i mono-di(2- ethylhexyl) orthophosphate Gravity, APL.-. Doctor,-Fed. 530.3.2 Sulfur, L, Percent; Copper Strip; Test, 122 F. 3 Hr Existent Gum, Mg./100 ml; .1

Oxidation Stability, 212 F., Min. Acid Heat,- F 91 Knock, Rating:v

Motor Method, 0ctane No. 5 r Research Method, Octane N o TEL, mL/gal Distillation, Gasoline:

Over Point, F End Point, F 7,, at, r

7 EXAMPLE 3 A suitable composition was prepared in'the manner of the foregoing Example 2, by incorporating 2.45 grams per gallon (approximately 0.088 weight percent) of the reaction product of Example 1 in a'sample of conventional commerical gasoline. The tertiarybutylamine derivative of borylated mono di(2 ethylhexyl) orthophosphate was equivalent to about 1.08 times the theoretical amount required to convert the lead of the tetraethyl lead to lead orthophosphate.

EXAMPLE 4 Gravity, API Color, Saybolt +16 Doctor, Fed. 520.3.2 Bad Copper strip test, 122 F., 3 hr. Oxidation stability, min. 121 Acid test, F. 112 Vapor'pressure, Reid, lb. 102 Distillation, gasoline: y l V i Over point, F. 90 End point, F. 372 evaporated at, F 126 50% 242 90% 326 Recovery, percent .L 97 Residue, percent 1 Loss, percent 2 EXAMPLE 5 Another suitable composition was prepared in accorance with the foregoing Example4 by incorporating in the base gasoline of Example 4, 4.3 grams per gallon (approximately 0.155 weight percent) of the reaction product prepared by reacting 2 equivalents of, 3-tallow"- aminopropylamine with 1 equivalent of. the anhydride formed in the reaction of lrnole of boric oxide with 2 moles of monooctyl diacid orthophosphate, by adding the amine to the borylated orthophosphate while maintaining the reaction temperature at about 40 to 60 C.

EXAMPLE 6 An addition suitable composition was prepared in ac cordance with the foregoing Example 4 by incorporating in the base gasoline of Example 4, 2.0 grams per gallon (0.072, weight percent) of the derivative prepared by reacting 1' equivalent of 3-itallow-aminopropylamine with of 1 mole of boric oxide with 3 moles of-the mdno-' d i(2- ethylhexyl) orthophosphate of Example ;1 by adding the amine to the borylated orthophosphate while maintaining the reaction temperature at about 40 to 60 -C. l

EXAMPLE T Another" preferred composition ;was prepared by incorporating the same compounds and thesame gasoline in the same proportions as in Example 6 with the exception that the compound was prepared to havean acid to' amine 2 equivalents of the anhydride preparedfrom the reaction '8 example, whenthe compositions described in these examples are burned in an internal combustion engine operated under conditions .wherein noise including preignition, knock. and rumble would normally be encountered, such engine noise is considerably less than the noise encountered when the base gasoline is used.

In order to illustrate the improved preignition characteristics obtained with a fuel of this invention, a test was employed in which the fuel was burned in a multicylinder Cadillac engine. This engine has a compression ratio of 10:1.

In this test the engine was operated on a cycling schedule consisting of 3 minutes at 1500 r.p.m. at 15 brake horsepower load followed by 1 minute idle at 460 r.p.m. The spark advance in eaclrinstance was the manufacturers setting. The coolant temperatures in and out were l50i5 F. and :5" F., respectively. The oil temperature in all instances was :5 F. At theend of each 24 hour period during the above-described cycling schedule noise requirement determinations were made. After the noise requirement determinations were made, the engine was put back on the cycling schedule for another 24 hours. The cycling and noise requirement tests were continued for nine 24-hour periods. The noise requirement determinations were made according to 3 successive steps. If noise was encountered in step 1, then steps 2 and 3 were omitted. If noise was encountered in step 2, then only step 3 was omitted. Noise in this test is intended to includepreignition, normal knocking and rumble. The 3 successive steps of the test are as "follows: l g

(1) At a speed of 1100 r.p.m. the throttle is'opened to detent (that is, the rear barrels of the carburetor are just open) at 1 inch mercuryintake manifold vacuum.

(2) The engine speed is increased to 1300 r.p.m. at 3 inch vacuum.

(3) The engine is accelerated at 10 inch vacuum from 1300 to 2000 r.p.m., standard spark,.and held at this setting for 3 seconds (throttle wide open at end of 3 seconds period).

Aural observations are made at steps 1, 2and 3 and preignition, rumble and knock are recorded. 1

Ratings are made on the tank fuel (99 research octan number) and the actual noise requirement determined by the use of a set of commercial reference fuels having octane numbers up to an octane n'umber of 113.5. -For noise requirements in the range of 113.5 to 120, leaded isooctane was used. Octane numbers above 100 are expressed in the approved extension scale Wiese octane numbers, which are: i

V Perf ormancge Nor-100 +100 The data set forth in Table I summarizes the results obtained when thetestengine was operatedu'nder the above test procedure with the base gasoline and the base gasoline containingOl times the theoretical amount of the tertiarybutylamine derivative of mono-di(2-ethylhexyl) 'orthophosphate of Example 1 required to convert the lead to lead phosphate. TABLE I.MAXIMUM NOISE RE UIREMENTS.

. it OOTAN ENOQ F Base-Gasoline Example 1 Composition .TxBLEnrnHou-n rnnrons 'ro svrr ON TANK FUEL 70 Example 1 Composition Base Gasoline 8+ p ."ila

Examplel Composition Base Gasoline The data in Table I indicate that a reduction in engine octane requirements for a noise-free operation is obtained by the use of the gasoline compositions of this invention. Thus, the octane requirement was reduced from 117 in the base gasoline to 100 in the gasoline containing the additive. The data in Table II clearly indicate that the addition agents of this invention effect a remarkable increase in the average time in which the engine can be operated before violent preignition occurs. Thus, Where the engine was able to operate for only 36 hours without sustained violent preignition (SVPI) when using the base fuel, the same engine was able to operate for more than 192 hours without violent preignition using the gasoline composition of Example 1. The data in Table III show a much smaller increase in the compression ratio when the fuel composition of Example 1 is compared with the base gasoline. V

The gasoline composition of Example 1 was tested in a single cylinder. engine and compared with an uninhibited base fuel to show the effect of-the additives on the octane requirement increase. This test was conducted in a single cylinder L-head engine with a 7:1 compression ratio.

The octane requirement evaluation was made under conditions of the full throttle part of the cycle. Reference fuel blends of isooctane and normal heptane were used.

Knock determinations were made aurally as the ignition time was varied to the point of trace knock. Three or more reference fuel blends which knock between 5 ATC and 15 BTC were rated and the requirements at TDC were interpolated from the plot of these data. I

Throughout. the test a wild ping counter in the form of a second dummy plug detected any uncontrolled combustion which occurred during 153 BTC and 7 ATC of the cycles. The number of cycles during the test in which such spontaneous ignition of the fuel charge occurred were counted. The wild ping counts gave a quantitative indication of the efiectiveness of the fuel incontrolling preignition. The results of this test are .tabulated' below:

TABLE IY.OCTANE REQUIREMENT INCREASE TEST Example 1 Base Gaso- Composition line Octane Requirement, Hrs 77. 5@160 78. @162 Wild Ping Count Accumulation 590 5000 The data in Table IV indicate no adverse effect upon octane requirement and an exceptional decrease in the wild ping count over a period of 160 hours. Thus the agents disclosed herein to the standard oxidation stability" understood that the invention is not limited to such extest ASTM D525-4 9. In this test the gasoline sample is introduced into an oxidation bomb and oxygen is added to a pressure about pounds p.s.i. The charged bomb is placed in a boiling water bath and the gas pressure in the bomb is recorded. The end of the induction period, i.e., the point at which rapid absorption of the oxygen by the gasoline takes place, is the time when a sharp drop in pressure (at least 2 p.s.i. in 15 minutes) occurs, is noted. The results obtained by the foregoing test are presented in Table V below:

I TABLE V.ADDITIVE CONCENTRATION G ./100 Induction grams Gas- Period in oline Minutes 1. Base gasoline 121 2. Gasoline composition of Example 4. 355 3. Gasoline composition of Example 5. 383 4. Gasoline composition of Example 6. 218 5. Gasoline composition of Example 7 0. 0721 279 Compositions 2, 3, 4 and 5 in Table V are specific embodiments of this invention. Comparison of the induction periods of these compositions with those for the base gasoline composition 1 indicates the remarkable improvement obtainable by the salts of this invention. Comparison of compositions 4 and 5 show the improved properties when the acid-amine equivalent ratio is changed from 2:1 to 1:2.

It will be understood that the foregoing embodiments of this invention are merely illustrative and that other members of the class of addition agents of this invention can be substituted therein in the same or equivalent concentrations within the herein disclosed range to prepare gasoline compositions having greatly improved characteristics.

Specific examples of other reaction products that are suitable for the purposes of this invention are the amine derivatives of 0.5, 1 or 2 equivalents of the anhydrides formed from boric oxide and ethyl lauryl monoacid orthophosphate (1:1 molar ratio); boric acid' and di(2- eth'ylhexyl) monoacid orthophosphate (1.3:1 molar ratio); the anhydride of boric oxide and acetic acid and dioctyl monoacid orthophosphate (0.3:1 molar ratio); boric oxide and diamyl monoacid orthophosphate (0.3:1 molar ratio); boric oxide and monooctyl diacid orthophosphate (0.5:1 molar ratio); and one equivalent'of any of the following: Z-ethylhexylamine, 3-is opropylamine, V tertiarybutylamine, n-octylamine, n-decylamine, n-dode- N,N'-di secondary-butyl-para-phenylenediamine 2,4-dimethyl-6-tertiary-butylphenol 2,6-ditertiarybutylA-methylphenol,

and other conventional additives. 1

While my invention is described above with reference to various specific examples and embodiments, it 'will be amples and embodiments and may be variously practiced within the scope of the claims hereinafter-made.

I claim: v

1. A gasoline motor fuel comprising a major amount of a hydrocarbon mixture boiling-in the gasoline range and containing about 0.001 to about lpercent by weight of the composition of a reaction product of (a) an amine amines whose substituents each contain. 2 to 22 carbon.

atoms, and (b) an anhydride prepared by reacting a par tially esterifi ed orthophosphoric acid that contains 1 to 2 organic substituents per molecule, at least one of whose substituents is a hydrocarbon radical containing 5 to 22 carbon atoms, and theother substituentof which when present is a hydrocarbon radical containing 1 to 22 carbon atoms, with a borylating agent selected from the group consisting of boric acid, boric oxide, and an anhydride of boric oxide and an aliphatic. monocarboxylic acid, in the ratio of about 0.5 to 6 moles of said partially esterified orthophosphoric acid to one mole of borylating agent under conditions conducive to anhydride formation, said amine and said anhydride being reacted in the proportion range of about 0.5 to 2 equivalents of anhydride per equivalent of amine.

2. A gasoline motor fuel comprising a'major amount of a hydrocarbon mixture boiling in the gasoline range and containing tetraethyl lead in an amount normally tending to. cause preignition of said fuel in the combustion chamber of a spark ignition, reciprocating internal combustion engine, and'a minor amount, sufficient to inhibit such preignition, of a reaction product of (a) an amine selected from the group consisting of primary, secondary and tertiary alkyl, alkenyl and alkylol. monoand diamines whose substituents. each contain 2 to 22 carbon atoms, and (b) an anhydride prepared by reacting a partially esterifiedorthophosphoric acid that con-. tains 1 to-2 organic substituents per molecule, at least oneof whose substituents is a hydrocarbonradical containing 5 to 22 carbon atoms, and the other substituent of which when present is ahydrocarbon radical containing 1 to 22 carbon atoms, with a borylating. agent selected from the group consisting of boric acid, boric oxide, and an anhydride of boric oxide and an aliphatic monocarboxylic acid, in the ratio of about 0.5 to about 6 moles of said partially esterified orthophosphoric acid per mole of borylating agent, under conditions conducive to anhydride formation, said amine and said anhydride being reacted in the proportion range of about 0.5 to about 2 equivalents of anhydride per equivalent of amine.

3. The gasoline composition of claim 2 where said minor amount is about 0.1 to 1 times the theoretical amount required to convert the lead in the tetraethyl lead to leadorthophosphate.

4. The gasoline composition ofclaim 2 where said minor amount is about 0.2 to 0.5 times the theoretical amount required to convert the lead in the tetraethyl lead to lead orthophosphate.

5. The gasoline composition of claim 1 where the amine is tertiarybutylamine, the partially esterifi'ed orthophosphate acid is mono-di(2-ethylhexyl) orthophosphate, the borylating agent is boric oxide, the molar ratio of borylating agent to phosphate is about 1:3, and the amine to anhydride equivalent ratio is about 1:1.

6. The gasoline composition of claim 1 where the amine is 3-tallow-aminopropy1amine, the partially esterified orthophosphate acid is ethyl lauryl orthophosphate, the borylating agent is boric oxide, the molar ratio of borylating agent to phosphate is about 1:1, and

the amine to anhydride equivalent ratio is about 2:1.

7. The gasoline composition of claim 1 where the amine is 3-tallow"-aminopropylamine, the partially esterified orthophosphateacid is monooctyl diacid ortho phosphate, the borylating agent is boric oxide, the molar ratio ofborylating agent to phosphate is about 1:2, and the amine to anhydride equivalent ratio is about 2:1.

8. The'gasoline composition of claim 1 where the amine is 3-tallow-aminopropylamine, the partially esterified orthophosphate acid is mono-di(2-ethylhexyl) orthophosphate, the borylating agent is boric oxide, the molar ratio of borylating agent to phosphate is about 1:3, and the amine to anhydride equivalent ratio is about 2: 1.

9. .The gasoline composition of claim 1 where the amine is 3-tallow-aminopropylamine, the partially esterified'orthophosphate acid is mono di(2-ethylhexyl)' orthophosphate, the borylating agent isboric oxide, the molar ratio of borylating agent tophosphate is about 1:3, and the amine to anhydride equivalent ratio. is about 1:2. 7

References Cited in the file of this patent UNITED STATES PATENTS Thompson Sept. 29, 1942 2,297,114 2,848,414 Chenicek Aug. 19; 1958 2,863,74 t Cantrell a a1. Dec. 9, a FOREIGN PATENTS Great Britain May 14, .1958

' (SEA-L) UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2 980 520 April 18V 1961 Helen I, Thayer 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 3 lines. 34 to 37, the formula should appear as shown below instead of as in the patent:

RI! R(NH) (CH) -1? (A) Signed and sealed this 19th day of September 1961.,

Attest:

ERNEST W. SWIDER Attesting Officer DAVID L. LADD Commissioner of Patents USCOMM-DC- corrected below.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2 980 520 April 18 1961 Helen 1., Thayer It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as Column 3 lines 34 to 37 the formula should appear as shown below instead of as in the patent:

l R(NH)X(CH N (M (SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Commissioner of Patents Attesting Officer USCOM M-DC-

Claims (1)

1. 2. A GASOLINE MOTOR FUEL COMPRISING A MAJOR AMOUNT OF A HYDROCARBON MIXTURE BOILING IN THE GASOLINE RANGE AND CONTAINING TETRAETHYL LEAD IN AN AMOUNT NORMALLY TENDING TO CAUSE PREIGNITION OF SAID FUEL IN THE COMBUSTION CHAMBER OF A SPARK IGNITION, RECIPROCATING INTERNAL COMBUSTION ENGINE, AND A MINOR AMOUNT, SUFFICIENT TO INHIBIT SUCH PREIGNITION, OF A REACTION PRODUCT OF (A) AN AMINE SELECTED FROM THE GROUP CONSISTING OF PRIMARY SECONDARY AND TERTIARY ALKYL, ALKENYL AND ALKYLOL MONOAND DIAMINES WHOSE SUBSTITUENTS EACH CONTAIN 2 TO 22 CARBON ATOMS, AND (B) AN ANHYDRIDE PREPARED BY REACTING A PARTIALLY ESTERIFIED ORTHOPHOSPHORIC ACID THAT CONTAINS 1 TO 2 ORGANIC SUBSTITUENTS PER MOLECULE, AT LEAST ONE OF WHOSE SUBSTITUENTS IS A HYDROCARBON RADICAL CONTAINING 5 TO 22 CARBON ATOMS, AND THE OTHER SUBSTITUENT OF WHICH WHEN PRESENT IS A HYDROCARBON RADICAL CONTAINING 1 TO 22 CARBON ATOMS, WITH A BORYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF BORIC ACID, BORIC OXIDE, AND AN ANHYDRIDE OF BORIC OXIDE AND AN ALIPHATIC MONOCARBOXYLIC ACID, IN THE RATIO OF ABOUT 0.5 TO ABOUT 6 MOLES OF SAID PARTIALLY ESTERIFIED ORTHOPHOSPHORIC ACID PER MOLE OF BORYLATING AGENT, UNDER CONDITIONS CONDUCTIVE TO ANHYDRIDE FORMATION, SAID AMINE AND SAID ANHYDRIDE BEING REACTED IN THE PROPORTION RANGE OF ABOUT 0.5 TO ABOUT 2 EQUIVALENTS OF ANHYDRIDE PER EQUIVALENT OF AMINE.