US2993771A - Process of preventing deposits in internal combustion and jet engines employing additives - Google Patents

Description

' tendencies. "fuel are primarily responsible for surface ignition phenomena such as preignition and octane requirement increase (ORI) which is the tendency of spark ignition atet new

Patented July 25, 1961 PROCESS OF PREVENTING DEPOSITS IN INTER- NAL COMBUSTION AND JET ENGINES EM- PLOYING ADDITIVES Verner L. Stromberg, Webster Groves, Mo, assignor to Petrolite Corporation, Wilmington, DeL, a corporation of Delaware No Drawing. Filed Feb. 2, 1959, Ser. No. 790,351 20 Claims. (Cl. 52.5)

This invention relates to deposit modifiers for substantially hydrocarbon fuels; More specifically, this invention relates to substantially hydrocarbon fuels containing deposit modifiers which inhibit and/or prevent the deposit-forming tendency of hydrocarbon fuels during combustion, and/ or modify the deleterious effect of the formed deposits, in both leaded and unleaded fuels, particularly in gasoline, jet fuels, etc., and to the process of inhibiting and/or preventing, and/or modifying the formation deposits in engines employing hydrocarbon fuels.

The smooth operation of an internal combustion engine depends upon the gradual propagation of the flame toward the cylinder walls and if the fuel-air mixture is ignited at many spots at the same time, progressive combustion is interrupted. If several compressive Waves are created, they subject the unburned charge to unduly high pressure and temperature so as to produce engine knock. This generally occurs if the cylinder deposits, which contain carbonaceous materials and lead compounds, retain sufficient heat to ignite the fuel-air mixture before the flame which had been originated by the spark plugs reaches all parts of the combustion chamber. Deposited lead compounds are believed to lower the temperature at which the deposits glow and ignite the fuel and it is desirable to reduce the deposits and/r neutralize the catalytic effect of such deposits in igniting the fuel. By so doing, these additives lower the octane number required to prevent knock or surface ignition.

As automobile manufacturers annually raise the compression ratio of their automobile engines in the race for higher horsepower, the need becomes greater for gasolines which burn cleanly, that is, have low deposit-forming Engine deposits which find their origin in the engines in service to require higher octane fuels for proper performance. As a consequence, gasoline manufacturers have placed increasing stress on reducing the depositforming tendencies of their fuels and have resorted to various additives either to reduce the amount of deposits or to minimize their effects.

The deposits formed in the combustion zone, particularly on the piston head and the exhaust valves, appear to have the most immediate effects upon engine performance in that their presence requires a fuel having a higher octane rating in order not to knock, thanis required by a new or clean engine. This means, in other words, that the octane value of a fuel required by an engine containing deposits in the combustion zone in order not to knock (referred to hereinafter as octane requirement) is higher than the octane requirement of a clean engine. For example, a clean engine which requires a gasoline having an octane rating of 60 in order not to knock is said to have an octane requirement of 60. If the same engine, when dirty, i.e., with deposits in the combustion chamber, requires a gasoline having an octane rating of 75 in order not to knock, such as engine is said to have an octane requirement of 75, or an octane requirement increase of 15. If a clean engine starts to get dirty, the octane requirement rises with continued use. Finally there is no more octane requirement increase with continued use and apparently the engine has then become as dirty as it is ever going to be with continued use, or if it becomes dirtier after a certain point, it does not require a gasoline of greater octane value in order not to knock.

It has been found, for example, that the weight of material deposited upon the top or head of the piston reaches a maximum in a single cylinder engine after approximately 20 hours of operation and that thereafter it decreases slightly, possibly due to a flaking action, until it levels off after about 40 hours of operation. It has also been found that the weight of the material deposited upon the exhaust valves reaches a maximum in the same engine after about 30 hours of operation and thereafter it decreases slightly and levels off after about 40 hours of operation. The fact that the weight of deposits in the combustion zone first reaches a maximum value and then levels oif to a somewhat lower value while the octane requirement levels off at the maximum value is believed to disprove the formerly accepted theory that the octane requirement of an engine is proportional to the weight of deposits in the combustion chamber.

The undesirable eifects of the deposits in the combustion chamber are further aggravated when tetraethyl lead is contained in the fuel because these deposits then are no longer primarily carbonaceous but contain appreciable quantities of lead. Accordingly, it has been found that the total weight of deposits formed in the combustion zone is appreciably greater when using a leaded fuel than when using a non-leaded fuel. The octane requirement increase of an engine operating on leaded fuel, however, is not in proportion to the difference in deposit weights. From this it is concluded that the octane requirement increase of an engine is determined not so much by the quantity of material deposited as by its presence and character.

It has also previously been found that the increase in octane requirement resulting from the formation of engine deposits is not attributable to a decrease in the thermal conductivity of the surfaces enclosing the combu'stion zone.

Since it has been found that the octane requirement increase of an engine is not determined solely by the quantity of material deposited in the combustion zone and that it is not due to a decrease in the thermal conductivity of the surfaces enclosing said zone, it is believed that it is due to a catalytic action wherein the deposits in the combustion zone act as catalysts to accelerate the oxidation of petroleum hydrocarbons. suggested that the proper approach to the problem of reducing the octane demand increase of an engine is that of adding to the fuel a substance having an anti-catalytic effect, or, in other words, the effect of suppressing or inhibiting the catalytic properties of the deposits formed, especially the troublesome lead-containing deposits. 7

The use of lead compounds in gasolines to increase the octane ratings thereof is extremely widespread. There are, however, several rather serious adverse effects which accompany the use of leaded gasolines. One of these effects, the deposition of various lead compounds within the combustion chambers of the engines, has been at least partially remedied by the use of halohydrocarbon scavengers such as ethylene dibromide and related compounds, for example those disclosed in US. Patents 2,398,281, 2,490,606, 2,479,900, 2,479,902, 2,479,901, 2,479,903, etc. Another adverse effect which has been attributed to the lead anti-knock compounds is mis-firing due to spark plug fouling. This spark plug fouling is quite prevalent under conditions of high temperature engine operation and, particularly in the case of aircraft engines is a very serious type of trouble.

As stated above, in recent years there has been .a

It has, therefore, been localities.

marked trend in the automotive industry toward utilizing internal combustion engines having high compression ratios in passenger cars and trucks. It has been found that this increase in compression ratios results in increased engine efiiciency whereby the motoring public is provided with both greater power availability and greater economy of operation. High compression engines almost uniformly require fuels of high octane number for most elficient operation. Of the several methods of raising the octane number of gasoline developed to date, that of utilizing an anti-knock agent, particularly of the organolead type, has been most successful. Although such anti-knock agents have been provided with corrective agents commonly known as scavengers, which effectively reduce the amount of metallic deposits in the engine by forming volatile metallic compounds which emanate from the engine in .the exhaust gas stream the accumulation of engine deposits in combustion chambers and on other engine parts such as pistons, valves, and the like cannot be entirely prevented. This accumulation of deposits .is particularly prevalent when the vehicles are operated under conditions of low speed and high load as encountered in metropolitan As a result of the notable improvements in fuel anti-knock quality, which have been-made in recent years, such deposits present but a few minor problems in low compression engines, whereas with engines of higher compression ratios, two more serious problems are becoming increasingly prevalent, those of detonation can successfully be obviated by the utilization of organolead anti-knock agents such as tetraethyllead, it has been found that the severity of the wild ping problem often increases with the octane quality of the fuel. Hence, the automotive industry is faced with the dilemma resulting from the fact that each time the octane quality of the fuel is raised to coincide with increases in compression ratio, deposit-induced auto-ignition generally becomes more severe.

Ordinary detonation in the internal combustion engine has been defined as the spontaneous combustion of an appreciable portion of the charge, which results in an extremely rapid local pressure rise and produces a sharp metallic knock. The control of ordinary detonation may be effected by retarding ignition timing, by operating under part throttle conditions, by reducing the compression ratio of the engine, and by using fuels having-high anti-knock qualities, that is, byusing an organolead-containing fuel. Deposit-induced autoignition may be defined as the erratic ignition of the combustible charge by combustion chamber deposits resulting in uncontrolled combustion and isolated bursts of audible and inaudible manifestations of combustion, somewhat similar to knocking. Aside from the nuisance experienced by the passenger car operator, deposit-induced autoignition or wild ping often produces deleterious effects inasmuch as it is a precurser of preignition. Therefore, wild ping results in rough engine operating conditions-and very often increases the wear of engine parts, piston burning and the like. In contrast to ordinary detonation, deposit-induced autoignition or wild ping cannot be satisfactorily controlled by retarding ignition timing nor by operating under part throttle conditions. Inasmuch as automotive engineers are desirous of utilizing in internal combustion engines the highest compression ratios permitted by the commercially available fuels, the reduction of compression ratios to eliminate this problem is not desirable nor feasible. Indeed, it is the consensus of opinion among the designers of internal combustion engines that engine developments have heretofore been greatly hindered by the limitations imposed by deposit-induced autoignition. It is-evident, therefore, that the present requirement for fuel having high anti-knock qualities shall be greatly surpassed by future requirements. Notwithstanding attempts to attain these qualities byalternative means, it is entirely probable that the most satisfactory method. for the attainment. of high. octane fuels .shall. continue tov be. the. use

of anti-knock agents, particularly of the organolead type. As a result, there is a paramount need existing for a new and improved method for altering the physical and chemical characteristics of deposits and for modifying the combustion process such that the detrimental effects of depositinduced autoignition may be markedly suppressed or be eliminated.

I have now found that a particular class of compounds effectively controls (by inhibiting and/ or preventing and/ or modifying) the deposit-forming tendencies of substantially hydrocarbon fuels, for example gasoline, jet fuels and the like, with resulting advantages. The hydrocarbon fuels of this invention are characterized by low depositforming tendencies with the result that an engine operated therewith shows exceptionally clean intake system combustion space, valves, ring belt area, cleaner spark plugs, etc. The low deposit level in the engine, spark plugs, etc., minimizes surface ignition in all its manifestations, for example preignition, knock, wild ping, spark plug fouling, etc. The low deposit level reduces the engines octane requirement increase, and deposits on surfaces contacted by the lubricating oi1,'such as piston skirts and cylinder walls, are very markedly reduced.

In addition, these compounds have an anti-catalytic effect, or, in other words, have the effect of suppressing or inhibiting the catalytic properties of the deposits found, especially the troublesome lead-containing deposits. Furthermore, these compounds are also effective corrosion inhibitors.

The compositions of this invention are the reaction products of (l) ASA (alkenyl 'succinic anhydride) or its equivalents and (2) amines which are capable of undergoing reaction with ASA. These products also include the reaction products of ASA with amines containing other functional groups, for example, hydroxy groups. They also include amines which are incapable of reaction with ASA at the amino position but can be reacted at another position, for example at the hydroxy position, such as would occur where a hydroxylated tertiary amine such as NE (CH CH OH) or where a prior acyl-ated hydroxylated amine such as 0 CHZCHZOH RCN CHzCHzOH are reacted with ASA.

The reaction products advantageously contain some unreacted carboxylic groups. These products can be characterized by the following formula where is residue of the amine, Zis O-, NH, NR, or N% wherein R is a substitutedgroup, for example hydrocarbon group (methyl, ethyl, propyl, etc.), comprises an ASA residue and x and y are whole numbers. Since monoas well as polyamines can be employed, the amines which can be reacted with ASA include monoamines, polyamines, hydroxylmonoamines and hydroxylpolyarnines. Poly-amines include cyclic compounds containing more than one nitrogen group such as the cyclic amidines, for example imid'azolines, tetrahydropyrimidines, etc.

Substantially any amine capable of reaction with ASA may be employed provided the product forrned is sufficiently soluble in the fuel to be effective as deposit modifiers.

In addition, the products formed, where they contain unreact-ed carboxylic groups, can be employed in the form of their salts. Satisfactory salts, can be prepared from the amines disclosed.hereinbyernploying an excessof the .amine reactant, particularlvaftenthe main reaction,

i.e. amidification, esterifioation, is complete. Thus, the product would be wherein B is the basic material. Thus, B can be one of the basic amino constituents disclosed herein, for example, monoamine, hydroxylated monoamines, polyamines, hydroxylated polyamines, and other variations disclosed herein. Some specific examples of basic materials include butylamine, cyclohexylamine, toluidine, benzylamine, pyridine, and the like. However, the metals which form cations generally leave a residue on combustion and are not generally employed, such as alkali metals, alkali earths, etc. Thus, it should be understood thatthe claims encompass the amine salts disclosed herein.

MONOAMINES Monoamines may be defined by the formulae RNH R NH, R N, where R is a hydrocarbon or a substituted hydrocarbon group, for example, alkyl, cycloalkyl, aryl, alkenyl, substituted aryl, a heterocyclic radical, etc. Although the tertiary amine, R N, is obviously not capable of reaction with ASA to form an amide since it has no reactive nitrogen group, it is capable of forming salts which may be effective.

The monoamines most advantageously employed are those amines where R is as follows: octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl, octadecenyl, octadecadienyl, octadecatrienyl, mixtures of the foregoing radicals as derived from tallow, soybean, coconut oil and other animal and vegetable oils, and hydrocarbon radicals derived from the acids of rosin and tall oil, such as abietic acid, dehydroabietic acid, dihydroabietic acid and tetrahydroabietic acid.

Provided the final product is soluble in the fuel, the R group or the amine can vary widely, for example from 1-30 or more carbons, but preferably from 8-22 carbon atoms. Thus, when the ASA has suflicient hydrocarbon content to render the product soluble the R in the amine can be a lower hydrocarbon radical for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc. In addition, isomers, unsaturated analogues, etc., can also be employed, for example, isopropyl amine, isobutyl amine, secondary butyl amine, allyl amine, etc.

Examples of commercial primary amines which can be employed are the armeens manufactured and sold by Armour & Company of Chicago, Illinois, under the trade names Armeen CD, Armeen S Armeen 8D, Armeen 10D, Armeen 12D, Armeen 14D, Armeen 16D, and Armeen 18D. Armeen CD is a mixture of primary amines prepared from coconut oil, Armeen SD is a mixture of primary amines prepared from soybean oil, and the other Armeens are mixtures of primary amines containing predominantly the number of carbon atoms specified in the code number.

Examples of commercial secondary amines are Armeen 2C and Armeen 2HT as described in a circular entitled Secondary Armeens by Armour & Company.

Additional commercial amines that can be employed are those sold under the trademark Primene by Rohm & Haas, which are described in their Technical Bulletin SP-33, dated December 1951, and in their other bulletins. These amines have the general structure where R has a branched chain of from about l2l carbon atoms.

Aromatic amines include aniline, substituted anilines, benzylamines, naphthylamine, etc.

preparation.

Amines where R is a heterocyclic group include furyl amine. In certain instances the amine group may be part of the heterocyclic structure for example morpholine, pipen'd-ine, etc.

The proportions of the reactants can vary widely, for example from molar ratios of one mole of monoamine to one mole of ASA to 2 moles of amine to one mole of ASA. Where ratios outside this range are employed, there is obviously an excess of reactant, based on stoichiometry except that salts may be formed. Preferably the molar ratio of amine to ASA is 1 to 1.

Neither time nor temperature appear critical since the reaction of ASA with the monoamine is quite easily effected. However, for reasonable rates a temperature of at least 75 C. is apparently required, for example temperatures of 75-150, but preferably -140" C. It is desirable not to run the reaction above 150 because of possible deterioration of the reaction and products as Well as possible side reactions. The time of reaction does not appear critical; however, a reaction time of at least about /2 hour, for example from /2 hour-5 hours, but preferably 2-3 hours. Time and temperature are, however, interdependent, and a longer period of time is required at lower temperatures.

The products of the reaction can vary depending on the conditions of reaction, the mole ratios of reactants, the moles of water removed, etc. The reaction of the monoamine with one mole of ASA proceeds quite readily to yield R 0 0 R 1l l' l 0H However, when more extreme dehydrating conditions are employed such as when an azeotroping agent is employed, the reaction can proceed further by either cyclizing to form an imide or by reacting to form the diamide Some of all the above products may be present in the reaction mixture.

In general, the compositions of this invention are prepared by adding one mole to ASA to one mole of amine in about 200 ml. of solvent (Xylene is used in the examples) heating to about l40150 C., holding it at this temperature for about 15 minutes and then allowing the reaction mixture to spontaneously cool to room temperature (about 2 hours). The reaction vessel employed is equipped with a mechanical stirrer, thermometer and reflux condenser.

Example 16 One mole of a commercial C alkenyl succinic acid anhydride and one mole of Armeen 12D are placed in 200 ml. of xylene. When the reactants are stirred, an exotherm occurs. This reaction mixture is then heated to C., held there for about 15 minutes and then allowed to cool to room temperature with stirring. The reaction product is an amber colored liquid.

In view of the above description and the fact that the preparation of other compositions of this invention are prepared in the same manner, it would be unnecessary and burdensomely repetitious to repeat the details of each Therefore, the prepared compounds are:

summarized in Table I. In the examples the following amines are employed:

( l) Armeen CD (8) 'Cyclohexy] amine HYDROXYLATED MONOAMINE The hydroxylated monoamines employed in this invention are monoamines containing at least one hydroxy group, usually in the form of an alkanol group (ROII) and may contain as many of these groups as there are available positions in the molecule, particularly at the amino positions. Thus, they may be R/ '-1 rRoH for example monoethanol amine, diethylethanol amine, dipropylethanol amine, dipropylpropanol amine;

for example diethanol amine, ethyldiethanol amine, propyldiethanol amine;

NEmoH for example triethanol amine, tripropanol amine, tributanol amine; and the like, where R is hydrogen or a hydrocarbon or a substituted hydrocarbon group, for example alkenyl, alkyl, cycloalkyl, phenyl, and the like and R is a hydrocarbon group, for example, (CH where x is a whole number, preferably 2-8, CH z,

| CH3 C2115 and other members of the homologous series.

In addition, the R groups may be joined so as to form a heterocyclic ring, which nitrogen group contains a hydroxy group, for instance, in the case of piperidine and derivatives, for example alkyl piperidine, etc.

Monoamines can be treated with alkylene oxide, for

example, ethylene oxide, propylene oxide, butylene oxide,

pszt lme ox d nd other aliph t xi a y as w l as aromatic oxide such as styrene oxide and similar compounds to form hydroxylated amines having repetitious ether linkages. The hydroxylated amines may be described by the formula wherein X, Y, and Z are either hydrogen, hydrocarbon groups or (OR) H groups (Z is a whole number, for example ll0 or higher, but preferably 1) where R is the hydrocarbon moiety derived from alkylene oxide, provided that the compound has a group, whether amino or oxygen-containing, which is capable of reaction with ASA to form an amide and/or an ester group. In addition, where one reactive group is contained in the resulting molecule, one or more of the terminal OH groups in the molecule may be blocked by an ether or an ester linkage for example, compounds of the type These monoamines contain at least one hydroxyl radical and may have two or three or even more. For example, if a primary amine such as ethylamine, propylamine, butylamine or the like is reacted with two moles of glycide to form a tertiary amine one obtains a compound having four hydroxyl radicals. Similarly, if a mole of triethanol, tripropanol, or tributanol amine is reacted with three moles of glycide, one obtains a monoamine having as many as six hydroxyl radicals.

Thus, any of the primary and secondary amines described under monoa-mines may be oxyalkylated to form secondary or tertiary amines which can be reacted with ASA. In addition, the hydroxyamine formed from oxyalkylation may also be employed for example those having a carbon content in the main chain of greater than two for example in N(ROH) where R has more than two carbons in the main chain, as exemplified by di-npropanolamine, di-n-butanolamine, di-n-pentanolamine, mono-n-propanolamine, mono-n-butanolamine, ethyl din-butanolamine, hexyl-n-hexanolamine, etc.

The proportions of reactants can vary widely, depending on the number of active amino or hydroxy groups on the amine, for example, one mole of amine to one mole of ASA to one mole of amine to six or more moles of ASA to those amines having, more than one functional group.

THE PREFERRED HYDROXYLAT ED MONOAMINE EMBODIMENT In its preferred embodiment this invention relates to the reaction product of two moles of an alkenyl succinic acid or an anhydride thereof and one mole of an amino alkanol or substituted aminoal-kanol having at least three carbon atoms; and to the process of preparing this product. More particularly, this phase of the invention relates to a composition of matter prepared from the above reactants having one ester group, one amide group and two carboxylic acid groups per molecule (also referred to as an ester-amide-aicid). Still more particularly, this invention relates to a compound having the formula:

In addition, one may employ some of the corresponding imido compound either alone or in combination with the diacid, wherein Z is an alkylene or substituted alkylene radical having at least three carbon atoms, for example from 3 to 12 or more carbon atoms, but preferably 3 to 8 carbon atoms; wherein one of the Rs or R"s on each succinic moiety is an alkenyl radical having at least 2 carbons, for example 2 to 32 or more carbons, but preferably 8 to 18 carbons and the other R or R on each succinic moiety is hydrogen; and wherein Y is hydrogen or a hydrocarbon group, for example an aliphatic group preferably lower alkyl.

The aminoalkanols employed in preparing the product of this phase of the invention contain alkylene or sub stituted alkylene radicals having at least three carbon atoms and both an amino and a hydroxyl radical. These can be expressed by the formula:

H Y-1 IZ-H wherein Z is an alkylene radical having at least three carbon atoms, for example 3 to 12 or more, but preferably 3 to 8 carbons; and Y is hydrogen or a hydrocarbon galloup, for example an aliphatic group, preferably lower Thus, Z is an alkylene radical which can be straightchained or branched chain, for example propylene, butylene, pentylene, hexylene, heptylene, octy-lene, nony-lene, decylene, etc., and isomers thereof, for example-impropylene, isobutylene, isopentylene, isohexylcne, isoheptylene, isooctylene, isononylene, isodecylene, etc. The alkylene radical can be straight chained singly branched, for example CHz-OH: doubly branched CH3 CH3 C )H H- or multi-branched CH3 CH3 -CH2 H-HOHretc. In addition, the alkylene groups can be substituted with other groups, for example aromatic groups, for ex ample phenyl, tolyl, etc. In such instances the alkylene radical need not have three carbon atomsbut may have only two, for example it may be ethylene wherein the ethylene radical also contains an aromatic group such as a phenyl group, etc. The amino or alcohol group can be attached to the carbon atoms of the alkylene radical which are primary, secondary, or tertiary carbons. The carbons to which these radicals are attached need not be of the same type. For example, in isopropanol amine,

the preferred aminoalkanol, the alcohol radical is .attached to a secondary carbon atom while the amino group is attached to a primary carbon atom. Examples illustrating various positions of attachment of the functional groups are:

-amino-4-octanol, 1-amino-2-hexano1, 2-amino-3-hexanol, 2-amino-2-methyl-3-hexanol,

l-amino-4-hexanol, Z-amino-l-hexanol, 3-amino-2-hexanol, l-amino-Z-heptanol, Z-amino-S-heptanol, 3-amino 4-heptanol, l-amino-Z-octanol, 2-amino-3-octanol, 2-amino 21methyl,j j A B-octanol, 3-amino-4-octanol, I Z-amino-l-octanol, S-amino-Z-octanol, etc,

Although the above aminoalkanols are illustrated with aminoalkanol containing primary amino groups, it should be understood that corresponding compounds containing amidifiable secondary amino groups can also be employed. I

Thus, aminoalkanols corresponding to those mentioned herein except that they contain N-aliphatic groups, such as N-alkyl groups, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, octadecyl, cycloaliphatic, etc., isomeric alkyl groups, etc, can be employed in this invention. In addition, N alkenyl or N-alkinyl groups can also be employed.

One convenient method of preparing these aminoalkanols is to react ammonia or a primary amine with an alkylene oxide on another hydrocarbon oxide having at least 3 carbon atoms, for example propylene oxide, butyleno oxide, octylene oxide, styrene oxide, etc. Other methods of preparing these aminoalkanols are so well known to the art that it is unnecessary to repeat them here.

In general, the alkenyl succinic acid anhydride is reacted With the aminoalkanol in a proportion of 2 moles of alkenyl succinic acid anhydride for each mole of aminoalkanol. Of course, more than 2 moles of alkenyl succinic acid per mole of aminoalkanol can be employed, leaving an excess of alkenyl succinic anhydride in the reaction mixture.

For example, when two moles of an alkenyl succinic acid are reacted with one mole of an aminoalkanol or two moles of an alkenyl succinic acid anhydride are reacted with one mole of an aminoalkanol, a reaction product is produced, representing the complete chemical interaction of the reactants. However, when three moles of an alkenyl 'succinic acid anhydride reactant are reacted with the aminoalkanol, a product is produced which comprises a physical mixture of the reaction product plus the unreacted talkenyl succinic anhydride.

The reaction which takes place can be expressed by the following equation, wherein the units have the meaning heretofore specified:

is also formed. In addition, one obtains an imido containing compound of the formula:

In general, the compositions of this invention are prepared by adding two moles of ASA and one mole of the aminoalkanol to about 200 ml. of a suitable solvent (xylene is used in the examples), heating to 150 C., holding it at this temperature for 5-10 minutes and then allowing the reaction mixture to spontaneously cool to room temperature The reaction vessel employed is equipped With a mechanical stirrer thermometer and a reflux condenser.

Example 233 Two moles of tetna-propenyl succinic anhydride (532 grams) is stirred with 200 m1. of Xylene and one mole of isopropanol amine I NHiCHrGH-OH (75 grams) is then added. This mixture is then heated to reflux at 150 C., allowed to remain at this temperature for five minutes, and then allowed to cool spontaneously to room temperature. The product is the ester-amide-acid product corresponding to the reactants.

In view of the above description and the fact that the preparation of other compositions of this invention are prepared in the same manner, it would be unnecessary and repetitious to repeat the details of each preparation. Therefore, the compounds are summarized in the following Table II.

TABLE II n l i i i HOC(|JHC HO-N-ZO -(|3H('|JHCOH R R n R 2-4 do do H 2-5 "do do H2 $3 -CH2-O-H CH2(|JH- 2-6 do do H 2-7 do do CH3 2-8 dO do H (CH:)3--

2-9 Octenyl Octenyl H CH (Straight (Straight Chain). Chain) CH -OH 2-10 do do 0H3 2-11 "d0 d0 C2115 (EH3 CH 2-12 dodo i H -oHgcH:-

F CH 213 do do CH CHCH CH-?H- H CH 2-16 do do H (CH 2-17 Octenyl Octenyl H CH (Branched). (Branched). 2-18 rin rln CH -CH:CH 2-19 do dO .'C2H5 2-2fl rin rin H H 2-21 do do OH! I -CHr-CH TABLE II-Gontinued :E'xainpI' One of Re One of Rs Y z ''CH1?H 2 22 do do H 27-23 do do CH3 2-24 do do H (CH2)a 2-25 Decenyl Decenyl H (Straight (Straight CH2 C I CH3 CH2-CH CzHi F 2-28 do do H 2-29 do do on;

CH2-CH- CHg(I1H 2-30 do do H 231 do do CH3 2-32 --do. do H (CH2)3 2-33 Tetrapropenyl Tetrapropenyl H CH 2-34 do do CH3 1 2-35 do do CaH5 CHzCH- (llHs 2-36 do do H 2-37 do do CH3 -CH CH 238 do do H 'CHz'CH- 2-39 do do CH3 -CH CIH- -do do; H (CHz)3 2-41 Triisobutenyl. .Triisobutenyl. H CH3 o do CH3 l dO d0 C2115 -CHz-CH n v (EH3 2-44 do do H 2-45 do do CH CIJHZ -CH2CH H 2-46 do do H 2-47 do do CH d'o. 10 H -(CH)2 Dodeceiiyl" Dodecenyl H (csltlgraight gsfiraight E 31H am 2-50 do do CH CH3 2-51 do do; CzH5 CH2-CH $113 H ona ([3112 '-cHroH CHzCH 2-54 do. H 2-55 do'.-- CH3 Although the above compounds are preferred wherein 2 moles of ASA are reacted with 1 mole of the aminoalkanol, other ratios may also be employed, for example 1 to 2 moles or less of ASA to 1 mole of aminoalkanol.

PRE-ACYLATED HYDROXYAMINE Where the hydroxyamine contains an arnidifiable nitrogen group, it may be pre-reacted with a fatty acid to form an amidohydroxy amine, for example, compounds of the formulae is derived from the carboxylic acidand R and R" are hydrocarbon groups, preferably alkyl having 2 to 18 carbon atoms but preferably 2-8 carbon atoms. Thereupon, this prior acylated hydroxyarnine can be reacted with ASA. For purposes of illustration and to save repetition, I will illustrate this phase of the invention with acylated dialkanolamines. 7 V w 7 An advantageous aspect of the prior acylated phase of the present invention provides for new compositions of matter obtained by reacting a fatty acid preferably containing at least about five carbon atoms per molecule with a dialkanolamine, in a molar proportion of about 1:1, respectively, to produce an intermediate product, and then reacting an alkenyl succinic' 'acid anhydride with the intermediate product, for example, in .a molar proportion varying between about 1:1, respectively, and about 2:1 respectively.

In general, the dialkanolamine reactants utilizable herein are those compounds having the structural'for mula R-OH wherein R and R are alkylene radicals or hydrocarbonsubstituted alkylene radicals, having for example between about two and about seven or more carbon atoms per radical. These radicals can be similar or dissimilar radicals. Ordinarily, they will be the same in any given molecule. Since it is more diflicult to csterify secondary and tertiary alcohol groups, it is preferable that the alkylene radicals do not contain secondary or tertiary carbon atoms attached to the hydroxyl group, so as to form secondary and tertiary alcohol groups, respectively. However, because of their greater commercial availability, it is preferred to use diethanolamine and hydrocarbon-substituted diethanolarnines. These compounds have the structural formula, HN(CHRCHROH) wherein R is a hydrogen atom or a hydrocarbon radical, preferably an alkyl radical. Non-limiting examples of the dialkanolamine reactants are diethanolamine; dipropanolamine; di-iso-propanolamine; 2,2'-iminodibutanol-1; 3,3- iminodibutanol-l; 4,4-i.minodibutanol-1; di-tert-butanolamine; 3,3-iminodipentanol-2; 6,6'-im-inodihexanol-1 and 7,7-iminodiheptanol-1.

Any fatty acid, or its anhydride or acid halide, can be reacted with the dialkanolamine reactant to produce the intermediate products used in preparing the reaction products of the present invention. Fatty acids containing substituent groups, such as halogen atoms, nitro groups, amino groups, etc., are also applicable herein. The fatty acid reactants can be branched-chain or straightchain, and saturated or unsaturated aliphatic monocarboxylic acids, and the acid halides and acid anhydrides thereof. Accordingly, when the term fatty acid is used herein, it must be clearly understood that the term embraces fatty acids, fatty acid anhydrides, and fatty acid halides, and derivatives thereof. Particularly preferred are the fatty acids having relatively long carbon chain lengths, such as a carbon chain length of between about 8 carbon atoms and about 30 carbon atoms. Non-limiting examples of the fatty acid reactant are valeric acid; a-bromoisovaleric acid; hexanoic acid; hexanoyl chloride; caproic acid .anhydride; sorbic acid; aminovaleric acid; amino hexanoic acid; heptanoic acid; heptanoic acid anhydride; Z-ethylhexanoio acid; a-bromo-octanoic acid; decanoic acid; dodecanoic acid; undecylenic acid; tetradecanoic acid; myristoyl bromide; hexadecanoic acid; palrnitic acid; oleic acid, heptadecanoic acid; stearic acid; linoleic acid; phenyl-stearic acid; xylylstearic acid; adodecyltetradecanoic acid; arachidic acid; behenic acid; behenolic acid; erucic acid; erucic acid anhydride; erotic acid; selacholeic acid; heptacosanoic acid anhydride; montanic acid; melissic acid; ketotriacontic acid; naphthenic acids; and acids obtained from the oxidation of petroleum fractions.

The fatty acid reactant is reacted with the dialkanolamine reactant in a molar proportion of about 1:1. A molar excess of dialkanolamine reactant, as much as 25 mole percent or more, can be used advantageously to ensure complete reaction. After the reaction is complete, the excess, unreacted dialkanolamiue reactant will be removed by usual means, such as by Water washing or by distillation. In any event, the net result will be an intermediate product produced by reacting the reactants in a 1:1 molar proportion.

Without any intent of limiting the scope of the present invention, it is postulated that the reaction between the fatty acid reactant and the dialkanolamine reactant re sults in the formation of a dialkanolamide of the fatty acid. Thus, the reaction between valeric acid and the diethanolamine could proceed, theoretrically, in accordance with the following equation:

On the other hand, a secondary reaction could take place between the hydroxyl groups of the diethanolarnine to form morpholine, or reactions could occur simultaneously between two molecules of the fatty acid and both the amino hydrogen and a hydroxyl group of the dietbanolamine, as set forth in the following equation (2) CHzCHz OHnCH:

204E900 on+rtN oiuion)iolntoou +2Hz ornlon The reaction of Equation 3 would produce some unreacted diethanolamine in the reaction mixture, but this reaction probably does not occur to an appreciable extent. It will be apparent, however, that, in view of the foregoing, any designation assigned to these intermediate products could include all of the above products.

Without any intent of limitingthe scope of the present invention, it is postulated that the reaction products contemplated herein are esteramide products of the dialkanolarnine reactant having at least one free carboxylic 1 7 acid group. For example, when the amide of diethanol amine is reacted with two moles of decenyl succinic acid anhydride the reaction product can contain any, or several, products, such as those set forth in the following structural formulae:

HO (3-0 (H) 0101119 (331140 0 C-CH:

C4H9C ON 0 11 0 0 C-CH2 HO 0 0-0 (H) C (311140 0 C CHQCHC O O CgH4 NO C C4119 H20 0 O O C 114 HO O O OH CioHiv 021140 0 C CHflCHC O 0 (31H;

C4H9GON 7 000411 031140000152 HgCCOOCgHA HO O C CH HG C O OH I 0101119 (5101119 or isomers thereof. The reaction products probably contain other substances.

In the interest of brevity, they may be defined by reciting the reactants and the number of moles of each which are used. For example, the reaction product produced by reacting one mole of valeric acid with one mole of diethanolamine to produce an intermediate product, which is then reacted with two moles of decenyl succinic acid anhydride'may be defined as valen'c acid-l-diethanolamine+decenyl succinic acid anhydride (1:1:2).

Non-limiting examples of the reaction products contemplated herein are those produced by reacting the following combinations of reactants: valeric acid+diethanolamine+etheny1 succinic acid anhydride (1:1:2); la-bromoisovaleric acid+di-propanolamine+ethyl succinic acid (1:1:1,8);' hexanoic acid+di-iso-propanolamine-lpropenyl succinic acid anhydride (1:1:1); hexanoyl ch1o1ide+2,2-iminobutano1-l-I-sulfurized propenyl succinic acid anhydride (1: 1:2); caproic acid anhyd1ide+3,3'-iminodibutanol-l+butenyl succinic acid (1:2:4); sorbic acid|4,4 iminodibutanol 1+l,2 dichloropentyl succinic acid anhydride (1:1:1.5); aminovaleric acid+di-tert-butanolamine-I-hexenyl succinic acid (1:1:2); amino-hexanoic acid+3,3-iminodipentanol-2+sulfurized 3-methylpentenyl succinic acid anhydride (1:1:1.2); heptanoic acid+6,6'-iminodihexanol-l+2,3-dimethylbw tenyl succinic acid anhydride (1:1:2); heptanoic acid anhydride+7,7-i.minodi-heptano1-1+1,2-

dibromo-Z-ethylbutyl succinic acid (1:2:2); Z-ethylhexanoic acid+diethanolamine+hepteny1 succinic :acidanliydride (121:1.7); a-bromooctanoic acid+dipropanolamine+l,2-diiodooctyl succinic acid (1:1:1); decanoic acid+di-iso-propanolamine+octenyl succinic acid anhydride (1:1:2); dodecanoic -acid-|-2,2 imjnodibutanol 1+2 methylhepteny-l succinic acid anhydride (1:1:1); undecylenic 'acid+3,3'-iminodibutanol-1-[4-ethylhexenyl succinic acid (1:1:2); tetradecanoic acid+4,4-iminodibutanol-1+diisobuteny1 succinicacidanhydiide (1:1:2);. Y

myristoyl bromide+'di-tert-butanolamine+ 2-propylhexenyl succinic acid anhydride (1:1:1);

hexadecanoic acid+3,3'-iminodipentanol-2+decenyl succinic acid (1:l:1.6);

palmitic acid+6,6'-iminohexanol-l+decenyl succinic acid anhydride (1:1:2);

oleic acid+7,7'-iminodiheptanol-l+undecenyl succinic acid anhydride (1:1:1.4);

heptadecanoic acid+diethanolamine+1,2-dichloroundecyl succinic acid (1:1:2);

stearic acid-dipropanolamine-l-dodecenyl succinic acid linoleie acid-I-di iso propanolamine-I-2-propylnonenyl succinic acid anhydride (1:1:1);

xylylstearic acid+2,2' iminodibutanol l+triisobutenyl succinic acid anhydride (1:1:2); a dodecyl tetradecanoic acid+3,3' iminodibutanol 1 +hentriaconteny1 succinic acid anhydride (1: 1:1); arachidic acid+4,4-iminodibutanol-l+hexacosenyl succinic acid anhydride (1:1:2);

behenic acid+di-tert-butanolamine+hexacosenyl succinic acid (1:1:1.2);

behenolic acid+3,3'-iminodipentanol-2+1,2-diiodotetracosenyl succinic acid anhydride (1:1:2);

erucic acid+6,6'-iminodihexanol-1+2-octyldodecenyl succinic acid anhydride (1:1:1.4);

erucic acid anhydride+7,7'-iminodiheptanol-1(1:2:2.8);

cerotic acid+diethanolamine+eicosenyl succinic acid anhydride (1:1:2);

selacholeic acid+dipropanolamine+1,2-dibromo-2-methylpentadecenyl succinic acid anhydride (1:1:1);

heptacosanoic acid anhydride+di-iso-propanolarnine+octadecyl succinic acid anhydride (1:2:4);

montanic acid+2,2+-iminodibutanol-l 1 1 1 melissic acid+di-tert-butanolamine-|-sulfurized octadecenyl succinic acid anhydride (1: l :2); and

ketotriacontic acid+7,7-iminodiheptanol-l-l-hexadecenyl succinic acid anhydride (1:1:2).

THE POLYAMINES: (a) HYDROXYLATED (b) NON-HYDROXYLATED A wide variety of reactive polyamines can be employed, including aliphatic polyamines, clycloaliphatic polyamines, aromatic polyamines, heterocyclic polyamines and polyamines containing one or more of the above groups. Thus, the term polyaminesT includes compounds having one amino group on one kind of radical, for example, an aliphatic radical, and another amino group on the heterocyclic radical as in the case of the following formulae:

cyclic, having a reactive amino group. It also includes polyamines having other elements besides carbon, hy-

drogen and nitrogen, for example, those also containing oxygen, etc. The preferred embodiments of the polyamines are the alkylene polyamines, the hydroxylated alkylene polyamines and the cyclic amidines, and N-alkylated derivatives thereof.

Polyamines are available commercially and can be prepared by well-known methods. It is well known that olefin dichlorides, particularly those containing from 2 to 10 carbon atoms, can be reacted with ammonia or amines to give alkylene polyamines. If, instead of using ethylene dichloride, the corresponding propylene, bu;

tylene, amylene or higher molecular weight dichlorides are used, one then obtains the comparable homologues. One can also use alpha-omega dialkyl ethers such as CICI-I OCH CI; ClC-H CH OCH CH Cl, and the like. Such polyamines can be alkylated in the manner commonly employed for alkylating monoamines. Such alkylation results in products which are symmetrically or non-symmetrically alkylated. The symmetrically alkylated polyarnines are most readily obtainable. For instance, alkylated products can be derived by reaction between alkyl chlorides, such as propyl chloride, butyl chloride, amyl chloride, cetyl chloride, and the like and a polyamine having one or more primary amino groups. Such reaction results in the formation of hydrochloric acid, and hence the resultant product is an amine hydrochloridei The conventional method for conversion into the base is to treat with dilute caustic solution. Alkylation is not limited to the introduction of an alkyl group, but as a matter of fact, the radical introduced can be characterized by a carbon atom chain interrupted at least once by an oxygen atom. In other words, alkylation is accomplished by compounds which are essentially alkyloxyalkyl chlorides, as,for example, the following:

CH OC H Cl C H OC H Cl The reaction involving the alkylene dichlorides is not limited to ammonia, but also involves amines, such as ethylamine, propylamine, butylamine, octylarnine, decylamine, cetylamine, dodecylarnine, etc. Cycloaliphatic and aromatic amines are also reactive. Similarly, the reaction also involves the comparable secondary amines, in which various alkyl radicals previously mentioned appear twice and are types in which two dissimilar radicals appear, for instance, amyl butylamine, hexyl octylamine, etc. Furthermore, compounds derived by reactions involving alkylene dichorides and a mixture of ammonia amines, or a mixture of two different amines are useful. However, one need not employ a polyarnine having an alkyl radical. For instance, any suitable polyalkylene polyarnine, such as an ethylene polyamine, a propylene polyamine, etc., treated with ethylene oxide or similar oxyalkylating agent are useful. Furthermore,

various hydroxylated amines, such as monoethanolamine,

wherein z is an integer varying between about two and about six.

In naming the polyalkylenepolyamine reactants, the nitrogen atoms are considered to be attached to the terminal carbon atoms of the main carbon atom chain indicated in each compound name. For example, di- (l-methylamylene) triamine has the structural formula:

In numbering the main carbon atom chain, the carbon atom attached to a terminal -NH radical is designated as the carbon atom in the l-position. Similar alkylene groups recur throughout the molecule. Nonlimiting examples of the polyalkylenepolyamine reactants are diethylene'tn'amine; triethylenetetramine; tetraethylenepentamine; di-(methylethylene) tri amine; hexapropyleneheptamine; tri(ethylethylene) tetramine; pental-methylpropylene) -hexamine; tetrabutylenepentamine; hexa-(1,1-dimethylethylene) heptamine; di-(l-methylbutylene) triamine; pentaamylenehexamine; tri-(l,2,2- trimethylethylene) tetramine; di-( l-methylamylene) triamine; tetra-(l,S-dimethylpropylene)pentamine; pental,5-dimethylamylene-3-hexamine; di-( 1-methyl-4-ethylbutylene) -triamine; penta-( LZ dimethyll-isopropylethylene)hexamine; tetraoctylenepentamine; rtri-(l,4-diethylbutylene)tetramine; tridecylene-tetramine; tetra-(1,4-dipropylbutylene) pentamine; didodecylenetriarnine; tetratetradecylenepentamine; penta-(1-methyl-4nonybutylene) hexamine; tri-( 1,15 -dimethylepentadecylene) -tetramine; trioctadecylenetetrarnine; dieicosylenetramine; di-(l,2-dimethyll4-nonyltetradecylene) triamine; di-( 1,l8-dioctyloctadecylene) triamine; penta-(l-methyl-Z-benzylethylene)hexamine; tetra-(l-methyl-3-benzyl-propylene) pentamine; tri-(l-methyl-1-phenyl-3-propylpropylene) tetramine; and tetra-( l-ethyl-2-benzylethylene)pentamine.

The polyamine can be alkylated with any alkyl halide which contains at least one carbon atom and up to about thirty carbon atoms or more per molecule. It is especially preferred to use alkyl halides having between about eight and about eighteen carbon atoms per molecule. Those having between about 14 and about 18 carbon atoms are more particularly preferred for certain products. The halogen portion of the alkyl halide reactant molecule can be any halogen atom, i.e., chlorine, bromine, fluorine, and iodine. In practice, the alkyl bromides and chlo rides are used, due to their greater commercial availability. Some non-limiting examples of the alkyl halide reactant are n-but-yl bromide; n-butyl chloride; sec-butyl iodide; t-butyl fluoride; n-amyl bromide; isoamyl chloride; 'n-hexyl bromide; n-hexyl iodide; heptyl fluoride; 2- ethyl-hexyl chloride; n-octyl bromide; decyl iodide; dodecyl bromide; 7-ethyl-2-methyl-undecyl iodide; tetradecyl bromide; hexadecyl bromide; hexadecyl fluoride; heptadecyl chloride; octadecyl bromide; docosyl chloride; tetracosyl iodide; hexacosyl bromide; octacosyl chloride, and tr'iacontyl chloride.

The alkyl halides can be chemically pure compounds or of commercial purity. Mixture of alkyl halides, having carbon chain lengths falling within the range specified hereinbefore, can also be used. Examples-of such mixtures are mono-chlorinated Wax and mono-chlorinated kerosene. Complete instructions for the preparation 'of mono-chlorowax have been set forth'in United States Patent 2,238,790.

- The number of moles of alkyl halide reactant which is reacted with each mole of polyalkylene polyamine reactant varies between about one mole and about (xl) moles, wherein x is the number of nitrogen atoms in the polyalkylene-polyamine reactant molecule. In order to obtain an intermediate product-which can be used to produce the reaction products of this invention, it is essential that at least one nitrogen atom in the polyalkylenepolyamine reactant be left unsubstituted. Accordingly, the; maximum number ofmoles of alkyl halide reactant which is reacted with each mole ofpolyalkylene-polyamine reactant will be one lessthan the number of nitrogen atoms in the polyalkylene-polyamine molecule. In accordance with the present invention, a fewer number of moles of alkylhalide reactant can be used. For example, if tetraethylenepentamine is utilized as the polyalkylenepentamine reactant, one, two, three, or even four moles of an alkyl halide reactant can be reacted with each mole thereof to produce intermediate products suitable for thepurposes contemplated herein. When five moles of alkyl halide reactant are used, the intermediate product is not utilizable in the production of the reaction products of the present invention.

As to the introduction of a hydroxylated group, one can use any one of a number of well-knownprocedu'res such as alkylation, involving a-chlorohydrin, such as ethylene chlorohydrin; glycerol chloroh'ydrin, or the like.

Such reactions are entirely comparable to the alkylation reaction involving alkyl chlorides previously described. Other reactions involve the use of an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, octylene oxide, styrene oxide or the like. Glycide is advantageously employed. The type-of reaction just referred to is Well known and results in the introduction of a hydroxylated or polyhydroxylated radical in an amino hydrogen position. It is also possible to introduce a hydroxylated oxyhydrocarbon atom; for instance, instead of using the chlorohydrin corresponding to ethylene glycol, one employs the chlorohydrin corresponding to diethylene glycol. Similarly, instead of using the chlorohydrin corresponding to glycerol, one employs the chlorohydrin corresponding to diglycerol.

From the above description it can be seen that man of the above alkylene polyamines can be characterized by the general formula:

where the Rs, which are the same or diiferent, comprise hydrogen, alkyl, eycloalkyl, aryl, alkyloxyalkyl, hydroxylated alkyl, hydroxylated alkyloxyalkyl, etc., radicals, x is zero or a whole number of at least one, for example 1 to 10, but preferably 1 to 3, and n is a whole number, 2 or. greater, for exampleZ-lO, but preferably 2-5. Of course, it should be realized that the amino or hydroxyl group may be modified by acylation to form amides, esters or mixtures thereof, prior to reaction with ASA provided the resulting compound contains a residual group capable of reaction with ASA, which group can be hydroxyl and/ or amino.

Cyclic aliphatic polyamines having at least one secondary amino group such as piperazine, etc., can also be employed.

It should be understood that diamines containing a reactive amino group may be employed. Thus, where x in the linear polyalkylene amine is equal to zero, at least one of the Rs would have to be hydrogen, for example, a compound of the following formula:

Suitable polyamines also include polyamines wherein the alkylene group or groups are interrupted by an oxygen radical, for example,

R x R or mixturesof these groups and alkylene groups, for ex- R x R where R, n and x has the meaning previously stated for the linear polyamine.

For convenience the aliphatic polyamines have been classified as nonhydroxylated and hydroxylated alkylene polyamino amines. The following are representative members of the non-hydroxylated series:

Diethylene triamine, Dipropylene triamine, Dibutylene triamine, etc.,

Triethylene tetram'ine, Tripropylene tetramine, Tributylene tetramine, etc.,

' Tetraethylene pentamine,

Tetrapropylene pentamine, Tetrabutylene pentamine, etc., Mixtures of the above.

Mixed ethylene, propylene, and/or butylene, etc., polyamines and other members of the series.

The above polyamines modified with higher molecular weight aliphatic groups, for example, those having from 8-30 or more carbon atoms, a typical example of which 1s where the aliphatic group is derived from any suitable source, for example, from compounds of animal or vegetable origin, such as coconut oil, tallow, tall oil, soya, etc., are very useful. In addition, the polyamine can contain other alkylene groups, fewer amino groups, additional higher aliphatic groups, etc., provided the polyamine has at least one reactive secondary amino group. Compositions of this type are described in US. Patent 2,267,- 205.

Other useful aliphatic polyamines are those containing substituted groups on the chain, for example, aromatic groups, heterocyclic groups, etc., such as a compound of the formula where R is alkyl and Z is an alkylene group containing phenyl groups on some of the alkylene radicals.

In addition, the alkylene group substituted with a hydroxy group N Ca aNca tN Examples of polyamines having hydroxylated groups include the following:

'23 24 (HO C2114)nNGaH4NC2H4N(Ca 40 )a (!3Hz (l}Hg H N NH :115 (3:115 \0/ NczHagcz t Hl l'R HO 01m wherein R is a hydrocarbon group,

(3113 CH; GH -0H2 H I NCaHgNCaHuN N NE HOCIHA 0 114011 I 0 Hz 0 Ha EN (0 HQNH) 1H NCzH4NC2H4NC2H4N Where HO 01H; H H 02114015: 2-undecylimidazoline Z-heptadecylimidazohne 0H3 C a 2-oleylimidazoline NCZHNCQHNCZHNCBHN l-N-decylaminoethyl, Z-ethylimidazoline H H H t t Z-methyl, 1-hexadecylaminoethylaminoethylimidazoline CZECH 1-dodecylaminopropylimidazoline HO C2114 CZECH l-(stearoyloxyethyl)aminoethylimidazoline 1-stearamidoethylaminoethylirmdazoline NQENWENQRNWEN 2-heptadecyl,4-5-dimethylimidazoline CH3 0 3 1-dodecylaminohexylimidazoline 1-stearoyloxyethylaminohexylimidazoline The preparation of cychc lmidazohnes and tetrahydro- ZhePtadecYLLmethYlaminoethYl tetrahydmpyrimidine Pyramides is W611 known See Patents 2,466,517, 4-methyl,2-dodecyl,l-methylaminoethylaminoethyl tetra- 2,488,163, Re. 23,227. I hydropyrimidine Sultable cychc amldmes mdufle these shown In the It should also be realized in the preparation of the above Patents as well as the followmg cyclic amidine compounds that amides as well as cyclic N-CH: amidines maybe formed which can subsequently be reacted with ASA. By controlling the reaction of the carboxylic acids with polyamines so that one rather than 1?I'CH2 two moles of water are removed, one obtains amides H rather than cyclic amides. If these amides possess'reactive group they can subsequently be reacted with ASA. Examples of amido-polyamines are shown in U.S. Patent R-O 2,598,213.

The following examples are presented for purposes of C H 40 illustration. It must be strictly understood that this in- 2 4 2 vention is not limited to the particular reactants and the molar ratios employed or in the operations and manipulations described therein. A wide variety of other reactants and molar ratios, as set forth hereinbefore, may

NOH1 be used. JZHr-NH-C2HANHI Examples 3-6 N CH2 CHPN One mole of an'alkylated polyamme (Duomeen T) H RC\ /0R RN-CHzCHzCHzNH;

N CHFI? (R is derived from tallow) is reacted with onemole of a f C ASA by heating the above reactants with an equal 11 amount of benzene at 130 C. for about three hours.

The product is an amber liquid. %NOH2 In view ofthe above description and thefact that the preparation of other compositions are prepared in the same manner, it would be unnecessary and repetitious to repeat the details of each preparation. There, the com- 01H4 NH C1H4 NH C1H4 NH1 pounds are summarized in the following table:

TABLE III Alkenyl ASA/poly- Example Group of Polyalmne amine, SA Molar Ratio diethylene triamine 2:1 triethyleue tetramine 2:1 tetraethylene pentaminm 1:1 3-4 heptadecenyl dipropyleno triamiue 3:1

3-5 oetadecenyl... DuomeenS 1:1

Alkenyl A Al ly- Example Group of Polyamine amine, ASA Molar Ratio 3-6 tetrapropenyL Duorneen '1 fi 1:1

RN CHQ3NH2 R derived from tallow.

3-7 octadeoenyl... OxyalkylatedgDuomeen S 1:1

RN(CH2)sNCz 4OH 3-8 heptadecenyL. Oxyalkylated Duomeen T 2:1

RN(CH2)5EC;1H4OH 3-9 tetrapropnyl- Amine 0LT (Monsanto) 2:1

12 2rCzH|NOnH4NH2 3-10 tetradeceny1 Oxyethylated Amine OLI 2:1

C12H25NC2H4NCH4NC2H4OH octenyl Dioetadecyl tetraethylene pentamine 3:1 tetrapropeny1 dibutyl tetraethylenepentamine 2:1 do dioetyltetraethylene pentamine 3:1 octenyl trioctadecyl tetraethylenepenta 2:1 tetrapropenyl octadecyl diethylenetriamine- 1 1 -do dacyldiethylenetriamine 1:1 3- octadeeenyl--- Hydroxyethylethylenediamine 1:1

N-CH: 3 18 tetradeceny1 C11Haa0\ l 1:1 N H2 C2H4NH1 N--CH2 3-19. do 012E250 2:1

OzH4NCzH4NCiu aa N-CH; a 3-20 do CaHnC CH2 1:1

CQHiNHfl N-CHz 3-21 do Ci1 asC i 1;1

N- Hg aHsN-CzHsOH 3-22 do Oleic acid prior acylated triethylene tetramine 1:1

(1:1 molar ratio). 3-23 heptadecenyL- Stearic acid prior acylated tetraethylene penta- 1:1

mine (1:1 molar ratio).

| HOOC or an isomer thereof. The reaction products probably contain other substances, such as cyclic imides of the formula The reaction product produced by reacting one mole of octyl bromide with one mole of triethylenetetramine to produce an intermediate product which is then reacted With two moles of decenyl succinic acid anhydride may be defined as the reaction product of octyl bromide (I)-triethy1ene-tetramine(I)-decenyl succinic acid anhydride(II).

Non-limiting examples of the reaction products contemplated herein are those produced by reacting the following combinations of reactants: n-butyl bromide(II)-+ tetraethylenepentamine(I) +hexacosenyl succinic acid as hydrogen, sulfur, bromine, chlorine, or.iodine.' It is obvious, of course, that there must be at least two carbon atoms in the alkenyl radical, but there is no real upper limit to the number of carbon atoms therein. However, it is preferred to use an alkenyl succinic acid anhydride reactant having between about 8 and about 18 carbon atoms per alkenyl radical. In order to produce the reaction products of this invention, however, an alkenyl succinic acid anhydride or the corresponding acid must be used. Succinic acid anhydride and succinic acid are not-utilizable herein. For example, the reaction product produced by reacting with succinic acid anhydride is unsatisfactory. Although their use is less desirable, the alkenylsuccinic acids also react, in accordance with this invention; to produce satisfactory reaction products. It has been found, however, that their use necessitates the removal of water formed during the reaction and also often causes undesirable side reactions to occur to some extent. 'Nevertheless, .the alkenyl succinic acid anhydrides and the alkenyl succinic acids are interchangeable for the purposes of the present invention. Accordingly, when theterm alkenyl succinic acid anhydride, is used herein, it must be clearly understood that it embraces the alkenyl succinic acids as well as their anhydrides, and the derivatives thereof in which the olefinic double bond has been saturated as set forth hereinbefore. Thus, it includes the hydrogenated alkenyl group, i.e. alkyl succinic acids and anhydrides. Non-limiting examples of the alkenyl'succinic acid anhydride reactant are ethenyl succinieacid 'anhydrides; ethenyl succinic acid; ethyl succinic acid anhydride; propenyl succinic acid anhydride; sulfurized propenyl succinic acid anhydride; butenyl succinic acid; Z-methyl-butenyl succinic acid anhydride; 1,2- dichloropentyl succinic acid anhydride; hexenyl succinic acid anhydride; hexyl succinic acid; sulfurized S-methylpentenyl succinic acid anhydride; 2,3-dimethyl-butenyl succinic .:acid anhydride; 3,3-dimethyl-butenyl succinic acid; 1,2-Ldibr'omo-2-ethylbntyl succinic acid; heptenyl succinic acid anhydride; 1,2-diiodooctyl succinic acid; octenyl succinic acid anhydride; 2-methylheptenyl succinic acid anhydride; 4-ethylhexenyl succinic acid; 2-isopropylpentenyl succinicacid anhydride; nonenyl succinic acid anhydride; f2 propylhexenyl succinic acid anhydride; decenyl succinic acid; decenyl succinic acid anhydride; '5-methyl- 2+isopropylhexenyl succinic acid anhydride; 1,2-dibromo- 2-ethyloctenyl succinic acid anhydride; decyl succinic acid anhydride; undecenyl succinic acid anhydride; 1,2-dichloro-undecyl succinic acid;- 3-ethyl-2-t-butylpentenyl succinic acid anhydride; dodecenyl succinic. acid .anhydride; dodecenyl succinic acid; 2-propylnonenyl succinic acid anhydride; 3-butyloctenyl succinic acid anhydride; tridecenyl succinic acid anhydride; tetradecenyl succinic acid anhydride; hexadecenyl succinic acid anhydride; sulfurized oetadecenyl succinic acid; octadecyl succinic acid anhydride; 1,2-dibromo 2 methylpentadecenyl succinic acid anhydride; 8-propylpentadecyl succinic acid anhydride; eicosenyl succinic acid anhydride; 1,2-dichloro-2- methylnonadecenyl succinic acid anhydride; 2-octyldodecenyl succinic acid; 1,2-diiodotetracosenyl succinic acid anhydride; hexacosenyl succinic acid; hexacosenyl succinic acid; hexacosenyl succinic acid anhydride; and hentriacontenyl succinic acid anhydride.

The methods of preparing the alkenyl succinic acid anhydrides are well known to those familiar with the art. The most feasible method is by the reaction of an olefin with maleic acid anhydride. Since relatively pure olefins are diflicult to obtain, and when thus obtainable, are often too expensive for commercial use, alkenyl succinic acid anhydrides are usually prepared as mixtures by reacting mixtures of olefins with maleic acid anhydride. Such mixtures, as well as relatively pure anhydrides, are utilizable' herein. V

Thereaction between the alkenyl succinic acid anhydrideandthe above amines takes place at any temperature ranging from ambient temperatures and upwards.

This reaction results in an amide and/or ester-formation reaction effected by the well known reaction of the anhydride group with an amino and an alcohol group. This reaction proceeds at any temperature, but temperatures of above C. are preferred. Thus, the reaction can take place at 20 to 200 C., but preferably 100 to C.

The reaction between the alkenyl succinic acid anhydride reactant and amines proceeds smoothly in the absence of solvents. However, the occurrence of undesirable side reactions is minimized when a solvent is employed and therefore its use of a solvent is preferable. Since a small amount of water might be formed when an alkenyl succinic acid anhydride is used in the reaction, the solvent employed may be one which will form an azeotropic mixture with water.

The time of reaction is dependent on the size of the charge, the reaction temperature selected, and the means employed for removing any water from the reaction mixture. Ordinarily, the addition of the anhydride reactant is substantially complete within a few minutes. The same products can be produced at temperatures below 100 C. for a reaction time of less than one hour. In order to insure complete reaction, particularly when the alkenyl succinic acid is employed, one may continue heating for several hours. For example when benzene is used as the solvent at a temperature of 100110 C., and water is removed, as occurs with alkenyl succinic acid, heating may be continued for about five hours. When water is formed during the reaction, as when an alkenyl succinic acid is used, the completion of the reaction is indicated by a substantial decrease in the formation of water. In general, the reaction time will vary between several minutes and about ten hours.

Certain reaction products of this invention will be very viscous, or even solid, rendering handling very diflicult from a commercial standpoint. These difficulties can often be alleviated by producing the reaction products in a solutionor dispersion. The solvent can be added to the reaction mixture of the aminoalkanol and alkenyl succinic acid anhydride reactant, before they are reacted with each other. In an alternate procedure, the reaction product can be produced by the methods mentioned hereinbefore, and then the solvent can be added to the reaction product while it is still hot. Dependent on the type of reaction product involved and of final product desired, the solvent can be used in any amount, thereby produc ing reaction products containing from about one percent by weight of solvent up to as much as 99 percent by weight of solvent.

All of the above compounds appear to be effective. However, for more efl'ective action solubility in the fuel is highly desirable. To eifect such solubility there is an inter-relation between the number of carbons'on the alkenyl group and the number of carbons on the amine. In general, compoundscontaining a total of at least 10 carbons, for example 10 to 50 carbons, but preferably 15 to 30 carbons can be employed, although those havirig lesser or more carbons can be employed under certain circumstances. Taken in view of the above considerations, itcan be seen that'the number of carbons of the amineand the alkenyl succinic acid can vary widely. However, in'practice I preferto employ an amine having at least one carbon, for example from one to fifty carbons, but preferably three to' twenty-two carbons. In regard to the alkenyl .succinic anhydride the alkenylside chain should'have at least three'carbons, for example from three to twenty-four carbons, but preferably four to eighteen carbons. 1

' In general, deposit-preventing, inhibiting and/or modifying amounts of the compounds are employed. For example, the products of this invention areelfective as a deposit-control additives in concentrations between 0.001 and 2.0 weight percent of the fuel. Generally, dirtier fuels having a higher concentration of olefinic components require higher concentrations whereas cleaner burning premium fuels are improved with respect to depositforming' characteristics by smaller concentrations. In general, dirtier gasolines require a concentration between 0.01 and 1.0 percent whereas clean-burning premium fuels" only need a concentration of between 0.001 and 0.5 percent. There is no critical upper limit from a functional viewpoint but economics dictate that the concentration be less than one percent.

The compounds in this invention are effective in controlling deposits in hydrocarbon fuels having boiling points up to about 500 F. or higher, although benefits also result when they are added to fuels containing residual stocks of higher boiling point. The major application of the additive is in gasoline for automotive engines wherein fuel-derived engine deposits have become a particularly vexing problem. The deposit-forming properties of fuels designed for use in jets are aslo improved by the compounds of this invention. They find particular application in jet fuels which are used as cooling mediums prior to their consumption. The compound-containing jet fuel is an excellent heat exchange medium since it is relatively free from deposits in the cooling system and burner nozzle where deposits cannot be tolerated.

The deposit-forming properties of both regular and premium gasolines, and aviation gasoline, whether leaded and of the non-leaded type are improved by the addition of these compounds. The gasolines to which they are added can be broadly defined as hydrocarbon fuels having a boiling point up to approximately 450 F.

Representaive compounds for the above classes are incorporated for example in fuels used in automobile, aircraft, and jet engines. Laboratory tests are carried out employing these fuels in such systems.

EXAMPLES Test I Performance tests show that the present invention produces substantial improvement in engine cleanliness, as compared to the same fuel not containing the additive. The test procedure involves a 40 hour engine run on a dynamometer under conditions chosen to correlate, on an accelerated scale, with field performance. In this test a 216.5 cubic-inch, six-cylinder Chevrolet engine is run continuously for forty hours as a speed of 1900 r.p.m. (plus or minus 25 r.p.m.) under an engine load of 36 BIL-P. (plus or minus 1 B.H.-P.). The jacket coolant inlet temperature is kept at 155 F. minimum, the jacket coolant outlet temperature is kept within two degrees of 170 F., and the crankcase oil temperature is kept within two degrees of 190 F. The air-fuel ratio is 14.5 (plus or minus 0.5) to 1. The spark advance is 35 (plus or minus 3); The spark plug gap, ignition cam angle, valve clearance, exhaust back pressure and other similar conditions are also maintained at predetermined values. Before the test, the engine is disassembled and cleaned, and a new set of piston rings is installed. The engine is given a standard two-hour break-in before the actual test is begun.

After the test run of 40 hours, the engine is dismantled and inspected, and is rated on ten items, as follows:

(1) Piston skirt varnish rating. (2) Cylinder wallvarnish rating.

'(3) Intake valve stem deposit rating.

(4) Intake valve tulip deposit rating.

(5 Intake port deposit rating.

(6) Overall engine sludge'rating; (7) Overall engine varnish rating.

On these first seven items, the rating runs between 0 for dirty to 10 for clean.

a4 (l0) Tight ring rating (10 minus 0.5 demerit for each tight ring).

A perfectly clean engine will thus rate 100. A total rating of is considered acceptable if the piston skirt varnish is 7.5 or better.

The gasoline employed in the tests is composed of about 50% mixed thermal naphtha having about 95 400 F. boiling range, about 20% light straight-run naphtha having 95 250 F. boiling range, about 25% heavy cracked (catalytic) naptha having 270-400 F. boiling range, and about 5% of light natural gasoline. It contains as additives about 1.75 ml. per gallon of tetraethyllead and an amine inhibitor in normal amounts. It analyzes 0.11% sulfur. Gum is present at about 2 to 5 mg. per 100 ml. in the ASTM test and the copper dish test shows about 16-26 mg. of gum per 100 ml. The gasoline has the following volatility specifications: 10% evaporated at 134150 'F., 50% at 244-250 F., and at about 360 F. The approximate composition of the gasoline is:

Percent Parafiins and naphthalenes, about 66 Olefins, about 16 Aromatics, about 18 Sulfur, about 0:1 Phenols, about 0.4 Nitrogen, about 0.001

The ASA-amine reaction products shown in the above tables when tested in concentrations of 0001-05 Weight percent give cleaner engines and therefore higher ratings than the control containing no additive.

An example of a high quality premium grade fuel with which similar results are obtained comprises mainly fluid catalytically cracked stock and straight run gasoline. This fuel has a A.S.T.M. research octane rating, contains 2.74 ml. of TEL fluid per gallon, had an API gravity of 60 to 65 and a boiling point range between and 400 F. the base fuel is negative in the copper corrosion test and has an oxidation stability in the A.S.T.M. test of 240 minutes minimum. This fuel also contains minor amounts of conventional gasoline inhibitors, namely, approximately 6 pounds of N,N'-disecondary butyl-p-phenylenediamine, a gum inhibitor, per thousand barrels of gasoline, about 1.2 pounds of N,N'-disalicylidene-1,2-diaminopropane, a metal deactivator, per thousand barrels of gasoline, and about 1.1 pounds of lecithin, a tetraethyl lead stabilizer, per thousand barrels of gasoline.

Similar results are obtained with a high quality regular grade gasoline comprising a mixture of thermal cracked stock, fluid catalytically cracked stock and straight run gasoline. This regular base fuel has an 87.0 A.S.T.M Research octane rating, contained 2.90 ml. of TEL per gallon, has an API gravity of 58.0 and a boiling range between 100 F. and 450 F.; the base fuel is negative in the copper corrosion test and has an oxidation stability in the A.S.T.M. test of 530 minutes minimum. The reference fuel also contains minor amounts of gasoline inhibitors, namely N,N'-disecondary butyl-pphenylenediamine, lecithin, and N,N'-disalicylidene-1,2- diaminopropane.

These compositions are also similarly effective when tested in an aviation grade gasoline as exemplified by a /130 grade aviation gasoline containing 4.6 m1. of tetraethyl lead.

The motor fuels employed in this invention comprise a mixture of hydrocarbons boiling in the gasoline boiling range. For instance, the gasoline employed can be a straight-run gasoline or a gasoline obtained from a conventional cracking process, or mixtures thereof. The gasoline can also include components obtained from processes other than cracking such as alkylation, isomerization, hydrogenation, polymerization, hydrodesulfuriza- 75 tion, hydroforming, platforming or combinations thereof,

35 as well as synthetic gasoline obtained from the Fischer- Tropsch and related processes.

Test ll SPARK PLUG FOULING A production model 1956 Oldsmoble Super 88 engine is used accomplish the evaluation. The engine is connected directly to a power absorption dynamometer through a conventional multiple disc coupling. The dynamometer and engine are fully instrumented to control operating conditions and to indicate data which are recorded hourly throughout the test.

Preparation of the engine for the test includes a thorough cleaning, inspection and measurement of all components. The engine is assembled according to the manufacturers specifications. After subjecting the engine to an eight hour break-in a thirty-two hour oil consumption check follows. During this check a speed of 2000 rpm. and 50 B.H.P. is maintained. At eight hour intervals the oil is drained and weighed. Having established oil consumption stability the cylinder compression pressures are measured to indicate valve condition. The cylinder heads are removed and all combustion chamber deposits eliminated.

The cylinder heads are assembled to the engine and preselected test spark plugs are installed for the first time. The engine starts on test schedule with an electromechanical intermittent controller attached to the throttle and dynamometer control which timed and actuated the throttle opening and dynamometer resistance for engine speed and load change. These changes are 2000 rpm. at 37.5 B.H.P. for five minutes and 450 rpm. at idle for one minute. Fifty of these cycles or hours comprised one interval. At the completion of each interval a check is made for misfiring at 2400 rpm. at full load. If no misfiring is observed the test continued for another interval of five hours. In the event of misfiring, it is determined whether one or more spark plugs are failing. A criterion for test termination is three fouled plugs in three different cylinders. If less than three plugs fouled simultaneously the fouled plug or plugs are replaced with a new plug and the test continued until a total of three plugs fouled in three different cylinders. The reasons for replacing the fouled plugs with new plugs before continuing the test were:

A. To prevent upsetting test conditions which would effect fouling in other cylinders.

B. To assure that misfiring is caused by the plug or plugs in question.

C. To confirm that some abnormal condition in the cylinder is not causing unusually early fouling.

The foregoing procedure and conditions are observed for the first 139 hours of each test phase. At the end of 139 hours the conditions conducive to spark plug fouling are further enhanced. Consideration is carefully given to future possibility of test duplication before making any change. Beginning with the 140th hour of each test phase and continuing until phase termination the following changes are in effect:

(1) The air fuel ratio is decreased from 12.4:1 to 11.1:1.

(2) The speed and load cycling is discontinued and changed to a constant speed of 2200 r.p.m. at 41.2 B.H.P.

(3) As a consequence of the above changes the fuel flow increases from 27.0 lbs/hr. to 40.0 lbs/hr.

(4) Instead of checking the spark plugs at five hour intervals at full load, an observation with the Du Mont Engine Analyzer is made each hour Without changing the speed or load unless plug fouling is detected.

Throughout the entire test a careful check is kept on oil consumption. At each 20 hours, as the test progressed, the engine is shut down for a crankcase oil level check. At each 60 hours the oil changed.

The fuel treated with the additive for the second phase of the test was blended as follows:

A 4000 gallon capacity storage tank is flushed with the base fuel. 1200 gallons of base fuel are pumped into the tank. A circulating pump is placed in operation with the intake at one end of the tank and the delivery at the opposite end of the required amount of additive is mixed with five gallons of the base gasoline. This mixture is slowly fed into the delivery stream of the fuel from the circulating pump. The fuel blend is recirculated for sixteen hours before start of the test.

The spark plugs selected for the test are AC-43. This spark plug is one degree colder in the heat range than the engine manufacturer recommends for this model. Twenty-four plugs are inspected and pre-tested under air pressure for firing for each test phase. From each batch of 24 plugs eight are selected which were nearly uniform in resistance at maximum pressure. All electrode gaps are adjusted to- .040.

Max. brake horsepower, at 4400 rpm. 240.

Carburetor Rochester 4-barrel Front Rear A/F Barrel Barrel Ratio Jet sizes Jet sizes Standard Equipment 49 51 13.1 1 0-139 hours of test 55 51 12. 4 l hours to termination of test 59 55 11.1 1

Equipment air cleaner used. The air-fuel ratio was determined by a Cambridge Exhaust Gas Tester.

Dynamometer: Mid West eddy current water cooled HP. capacity. Torque reaction measured by a Fairbanks Morse beam scale.

Instrumentation: The following temperatures were measured by means of mercury thermometers:

Jacket coolant in Jacket coolant out Intake air at carburetor Motor oil in oil pan sump Wet bulb Dry bulb Exhaust back pressures and intake manifold vacuum are measured by means of mercury manometers. Barometric pressures are observed on a conventional mercury barometer and was corrected for temperature. Engine oil pressures are measured by a standard Bourdontype gage.

The rate of fuel consumption is determined on a weight basis using a tip balance. A flowmeter in the supply line provides a check upon engine fuel consumption determined by weighing.

Engine speed is determined by an electronic counter.

Spark plug performance characteristics are observed by means of a multiple trace oscilloscope.

Both incipient fouling and 100% fouling of each spark plug is recorded in hours.

The base fuel used for the test operations is described as follows: CompositionMixture of straight run and catalytically cracked gasolines:

Gravity, API 58.8 Bromine number 53 Doctor Negative Sulfur, percent wt. 0.017 Corrosion, Cu. strip, 3 hrs. at 122 F. None Gum, A.S.T.M., mg. 2.8

Oxidation stability, A.S.T.M., minutes 600 Octane number:

Fuels containing the compositions of this invention in weight percent of 0.001 to 0.5% according to this test are superior to corresponding fuels containing no additive.

Since spark plug fouling is a function of the lead content of the gasoline, the optimum amount will vary with such content. Although weight ratios of 0.001-2% or more can be employed in gasolinescontains about 3 cc. of tetraethylene lead or its equivalent/gallon of gasoline, generally 0.0011% is usually sufficient for antifouling purposes. However, it should be understood that the optimum amount or the weight bases for one particular compound may not be the optimum amount for another compound. One reason for this is that the efiect-iveness of the compounds vary from one compound to another. Another reason is the variance of molecular weights so that one compound may be twice the molecular weight of another on weight basis. However, by proper adjustment of concentrations, anti-fouling can be effected. These principles also apply to the other ratios herein stated.

Test III These compounds in the above table are also tested in a 100 hour full scale reciprocity engine test employing Military Specification MILG5572A grade 115/ 145 fuel in a Wright R3350-30W compound engine operated according to the following cycle:

Time per cycle (min) Idle 10 Take-off power and speed 5 Normal rated power and speed 30 Cruise 90 normal rated power and 93% normal rated 30 Cruise 90 Total 255 Test IV The compounds in the above tables are also tested in a hour full scale gas turbine engine test in a Pratt & Whitney J57-P29 gas turbine engine employing Specification MILJ-5624D Grade JP-4 fuel. The engine is operated for 100 hours and cycled in accordance with the Specification MIL-E-5009 Model qualification test. After 100 hours of operation, the engine combustion components and turbine sections are disassembled and inspected for deposits and deleterious effects.

Fuels containing the compositions of this invention in weight ratios of 0.001 to 0.5 by weight according to this test are superior to corresponding fuels containing no additive.

Although the present invention has been described with preferred embodiments, it is to be understood that modifications may be resorted to without departing from the spirit and scope thereof. For example, the invention includes the reaction product of other amines besides those specifically stated above, for example heterocyclie amines, such as aminooxazolenes, for example wherein R is a hydrocarbon, and homologous thereof,

wherein R and R are for example alkyl or hydrogen,

I] ]TH NH2-(CH2)ioC-NH2, etc.

In addition, the invention includes various fuels such as all grades of gasolines which may contain a wide variety of additives such as anti-oxidants, organolead stabilizers, organic dyes, solubilizers, etc., as well as the halide scavengers generally employed such as ethylene dibromide and/or ethylene dichloride and other scavengers for example those disclosed in the patents listed above relating to such compositions. Such variations and modifications are considered to be within the purview and scope of the appended claims.

Having thus described my invention, what I claim as new and desire to obtain by Letters Patent is:

1. A process of preventing, inhibiting and modifying the formation of deposits in internal combustion and jet engines employing a substantially hydrocarbon fuel which comprises burning in such engines a fuel consisting of a liquid hydrocarbon having a boiling point up to about 500 F. and a minor amount in the range of approximately 0.001 to 2 weight percent of said fuel, suflicient to prevent, inhibit and modify such deposits, of a reaction product of (1) a member selected from the group consisting of an alkenyl succinic acid and the anhydride thereof, having 3-32 carbon atoms on the alkenyl group and (2) an amine having at least one carbon atom, the sum of the carbons on said acid and said anhydride plus the carbons on said amine totalling from approximately 10 to approximately 82 carbon atoms, said reaction product being soluble in said liquid hydrocarbon and being composed of only carbon, hydrogen, nitrogen and oxygen.

jet engines employing asubstantially hydrocarbon fuel which comprises burning in such engines a fuel consisting of a liquid hydrocarbon having a boiling point up to about 500 F. and a minor amount in the range of approximately 0.001 to 2 weight percent of said fuel, sufficient to prevent, inhibit and modify such deposits, of a reaction product of (1) two moles of a member selected for the group consisting of an alkenyl succinic' acid and the anhydride thereof, having three thirty-two carbon atoms on the alkenyl group and (2) one mole of an aminoalkanol having at least three carbon atoms, the sum of the carbons on said acid and said anhydride plus the carbons on said amine totaling from axxporixately to approximately 82 carbon atoms, said reaction product being soluble in said liquid hydrocarbon and being composed of only carbon, hydrogen, nitroegn and oxygen.

3. The process of claim 1 wherein the hydrocarbon fuel is gasoline.

4. The process of claim 3 where the amine is a monoamine.

5. The process of claim 3 where the amine is a polyamine.

6. The process of claim 3 where the amine is a hydroxyl monoamine.

7. The process of claim 3 where the amine is a hydroxyl polyamine.

8. The process of claim 1 wherein the hydrocarbon fuel is a jet fuel.

9. The process of claim 8 where the amine is a monoamine.

10. The process of claim 8 where the amine is a polyamine.

1-1. The process of claim 8 where the amine is a hydroxyl monamine.

12. The process of claim 8 where the amine is a hydroxyl polyamine.

13. The process of claim 2 wherein the substantially hydrocarbon fuel is gasoline.

14. The process of claim 13 wherein the alkenyl group has 8-18 carbon atoms and the aminoalkanol has 38 carbon atoms.

15. The process of claim 13 wherein the alkenyl group has 8-18 carbon atoms and the aminoalkanol is 16. The process of claim 2 wherein the substantially hydrocarbon fuel is a jet fuel.

17. The process of claim 16 wherein the alkenyl group has 818 carbon atoms and the aminoalkanol has 38 carbon atoms.

18. The process of claim 16 wherein the alkenyl group has 8-18 carbon atoms and the aminoalkanol is 19. The process of claim 15 wherein the alkenyl group is tetrapropenyl.

2 0. The process of claim 18 wherein the alkenyl group is tetrapropenyl.

References Cited in the file of this patent UNITED STATES PATENTS 2,386,445 De Groote Oct. 9, 1945 2,450,221 Ashburn et a1 Sept. 28, 1948 2,568,746 Kirkpatrick Sept. 25, 1951 2,715,108 Francis Aug. 9, 1955 2,733,235 Cross et al. Jan. 31, 1956

Claims (1)

1. IN A PROCESS OF PREVENTING, INHIBITING AND MODIFYING THE FORMATION OF DEPOSITS IN INTERNAL COMBUSTION AND JET ENGINES EMPLOYING A SUBSTANTIALLY HYDROCARBON FUEL WHICH COMPRISES BURNING IN SUCH ENGINES A FUEL CONSISTING OF A LIQUID HYDROCARBON HAVING A BOILING POINT UP TO ABOUT 500*F. AND A MINOR AMOUNT IN THE RANGE OF APPROXIMATELY 0.001 TO 2 WEIGHT PERCENT OF SAID FUEL, SUFFICIENT TO PREVENT, INHIBIT AND MODIFY SUCH DEPOSITS, OF A REACTION PRODUCT OF (1) A MEMBER SELECTED FROM THE GROUP CONSISTING OF AN ALKENYL SUCCINIC ACID AND THE ANHYDRIDE THEREOF, HAVING 3-32 CARBON ATOMS ON THE ALKENYL GROUP AND (2) AN AMINE HAVING AT LEAST ONE CARBON ATOM, THE SUM OF THE CARBONS ON SAID ACID AND SAID ANHYDRIDE PLUS THE CARBONS ON SAID AMINE TOTALLING FROM APPROXIMATELY 10 TO APPROXIMATELY 82 CARBON ATOMS, SAID REACTION PRODUCT BEING SOLUBLE IN SAID LIQUID HYDROCARBON AND BEING COMPOSED OF ONLY CARBON, HYDROGEN, NITROGEN AND OXYGEN.