FUEL ADDITIVE COMPOSITIONS CONTAINING POLY(OXYALKYLENE) HYDROXYAROMATIC ESTERS AND ALIPHATIC AMINES

Abstract: The combination of a poly(oxyalkylene) hydroxyaromatic ester and an aliphatic amine provides excellent deposit control performance in internal combustion engines.

Description: FUEL ADDITIVE COMPOSITIONS CONTAINING POLY(OXYALKYLENE) HYDROXYAROMATIC ESTERS AND ALIPHATIC AMINES BACKGROUND OF THE INVENTION Field of the Invention This invention relates to a fuel additive composition. Mor particularly, this invention relates to a fuel additive composition containing a poly(oxyalkylene) hydroxyaromatic ester and an aliphatic amine. Description of the Related Art it is well known that automobile engines tend to form deposits on the surface of engine components, such as carburetor ports, throttle bodies, fuel injectors, intake ports and intake valves, due to the oxidation and polymerization of hydrocarbon fuel. These deposits, even when present in relatively minor amounts, often cause noticeable driveability problems, such as stalling and poor acceleration. Moreover, engine deposits can significantly increase an automobile's fuel consumption and production of exhaust pollutants. Therefore, the development of effectiv fuel detergents or "deposit control" additives to prevent o control such deposits is of considerable importance and numerous such materials are known in the art. For example, aliphatic hydrocarbon-substituted phenols are known to reduce engine deposits when used in fuel compositions. U.S. Patent No. 3,849,085, issued November 19, 1974 to Kreuz et al., discloses a motor fuel composition comprising a mixture of hydrocarbons in the gasoline boiling range containing about 0.01 to 0.25 volume percent of a high molecular weight aliphatic hydrocarbon-substituted phenol in which the aliphatic hydrocarbon radical has an average molecular weight in the range of about 500 to 3,500. Thiβ patent teaches that gasoline compositions containing minor amount of an aliphatic hydrocarbon-substituted phenol not only prevent or inhibit the formation of intake valve and port deposits in a gasoline engine, but also enhance the performance of the fuel composition in engines designed to operate at higher operating temperatures with a minimum of decomposition and deposit formation in the manifold of the engine. Similarly, U.S. Patent No. 4,134,846, issued January 16, 1979 to Machleder et al., discloses a fuel additive composition comprising a mixture of (1) the reaction product of an aliphatic hydrocarbon-substituted phenol, epichlorohydrin and a primary or secondary mono- or polyamine, and (2) a polyalkylene phenol. This patent teaches that such compositions show excellent carburetor, induction system and combustion chamber detergency and, in addition, provide effective rust inhibition when used in hydrocarbon fuels at low concentrations. U.S. Patent No. 4,231,759 discloses a fuel additive composition comprising the Mannich condensation product of (1) a high molecular weight sulfur-free alkyl-substituted hydroxyaromatic compound wherein the alkyl group has a number average molecular weight of about 600 to 3,000 (2) an amine containing at least one active hydrogen atom, and (3) an aldehyde, wherein the respective molar ratio of reactants is 1:0.1-10 : 0.1-10. SUMMARY OF THE INVENTION The present invention provides a novel fuel additive composition comprising: (a) a poly(oxyalkylene) hydroxyaromatic ester having the formula: ) n -0-R 5 (I) or a fuel-soluble salt thereof; wherein R, and R-, are each independently hydrogen, hydroxy, lower alkyl having 1 to 6 carbon atoms, or lower alkoxy having 1 to 6 carbon atoms; R 3 and R 4 are each independently hydrogen or lower alkyl having 1 to 6 carbon atoms; R 5 is hydrogen, alkyl having 1 to 30 carbon atoms, phenyl, aralkyl or alkaryl having 7 to 36 carbon atoms, or an acyl group of the formula: wherein R 6 is alkyl having 1 to 30 carbon atoms, phenyl, or aralkyl or alkaryl having 7 to 36 carbon atoms; R 7 and R 8 are each independently hydrogen, hydroxy, lower alkyl having 1 to 6 carbon atoms, or lower alkoxy having 1 to 6 carbon atoms; n is an integer from 5 to 100; and x and y are each independently an integer from 0 to 10; and (b) an aliphatic amine having at least one basic nitrogen atom and containing a hydrocarbyl group which has sufficient molecular weight and carbon chain length t render the aliphatic amine soluble in hydrocarbons boiling in the gasoline or diesel fuel range. The present invention further provides a fuel composition comprising a major amount of hydrocarbons boiling in the gasoline or diesel range and an effective deposit-controlling amount of the novel fuel additive composition of the present invention. The present invention additionally provides a fuel concentrate comprising an inert stable oleophilic organic solvent boiling in the range of from about 150°F to 400°F and from about 10 to 70 weight percent of the fuel additiv composition of the present invention. Among other factors, the present invention is based on the surprising discovery that the unique combination of a poly (oxyalkylene) hydroxyaromatic ester and an aliphatic amine provides excellent deposit control performance in internal combustion engines. DETAILED DESCRIPTION OF THE INVENTION As used herein the following terms have the following meanings unless expressly stated to the contrary. The term "alkyl" refers to both straight- and branched-chai alkyl groups. The term "lower alkyl" refers to alkyl groups having 1 to about 6 carbon atoms and includes primary, secondary and tertiary alkyl groups. Typical lower alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl and the like. The term "lower alkoxy" refers to the group -0R a wherein R a is lower alkyl. Typical lower alkoxy groups include methoxy, ethoxy, and the like. The term "alkaryl" refers to the group: wherein R b and R c are each independently hydrogen or an alkyl group, with the proviso that both R b and R c are- not hydrogen. Typical alkaryl groups include, for example, tolyl, xylyl, cumenyl, ethylphenyl, butylphenyl, dibutylphenyl, hexylphenyl, octylphenyl, dioctylphenyl, nonylphenyl, decylphenyl, didecylphenyl, dodecylphenyl, hexadecylphenyl, octadecylphenyl, icosylphenyl, tricontylphenyl and the like. The term "alkylphenyl" refer to an alkaryl group of the above formula in which R b is alkyl and R c is hydrogen. The term "aralkyl" refers to the group: wherein R d and R e are each independently hydrogen or an alkyl group; and R f is an alkylene group. Typical alkaryl groups include, for example, benzyl, methylbenzyl, di ethylbenzyl, phenethyl, and the like. The term "hydrocarbyl" refers to an organic radical composed primarily of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combinations thereof, e.g., aralkyl or alkaryl. Such hydrocarbyl groups are generally relatively free of aliphatic unsaturation, i.e., olefinic or acetylenic unsaturation. The term "oxyalkylene unit" refers to an ether moiety having the general formula: , R h I I -O-CH-CH- wherein R„ and R h are each independently hydrogen or lower alkyl groups. The term "poly(oxyalkylene) " refers to a polymer or oligomer having the general formula: wherein R ~ and R h are as defined above, and z is an integer greater than 1. When referring herein to the number of poly(oxyalkylene) units in a particular poly(oxyalkylene) compound, it is to be understood that this number refers to the average number of poly(oxyalkylene) units in such compounds unless expressly stated to the contrary. The Poly(oxyalkylene) Hydroxyaromatic Ester The poly(oxyalkylene) hydroxyaromatic ester component of the present invention has the general formula: -CH) n -0-R 5 (I) or a fuel-soluble salt thereof; wherein R, , R-,, R 3 , R 4 , R 5 , n and x are as defined hereinabove. Preferably, R, is hydrogen, hydroxy, or lower alkyl having 1 to 4 carbon atoms. More preferably, R, is hydrogen or hydroxy. Most preferably, R, is hydrogen. R 2 is preferably hydrogen. Preferably, one of R 3 and R 4 is lower alkyl having 1 to 3 carbon atoms and the other is hydrogen. More preferably, one of R 3 and R 4 is methyl or ethyl and the other is hydrogen. Most preferably, one of R 3 and R 4 is ethyl and the other is hydrogen. 01 R 5 is preferably hydrogen, alkyl having 2 to 22 carbon 02 atoms, or alkylphenyl having an alkyl group containing 2 to 03 24 carbon atoms. More preferably, R 5 is hydrogen, alkyl 04 having 4 to 12 carbon atoms or alkylphenyl having an alkyl 05 group containing 4 to 12 carbon atoms. Most preferably, R 5 06 is alkylphenyl having an alkyl group containing 4 to 07 12 carbon atoms. 08 09 R 6 is preferably alkyl having 4 to 12 carbon atoms. 10 11 Preferably, R 7 is hydrogen, hydroxy, or lower alkyl having 1 12 to 4 carbon atoms. More preferably, R 7 is hydrogen or 13 hydroxy. Most preferably, R 7 is hydrogen. 14 15 R 8 is preferably hydrogen. 16 17 Preferably, n is an integer from 10 to 50. More preferably, 18 n is an integer from 15 to 30. Preferably, x is an integer 19 from 0 to 2. More preferably, x is 0. Preferably, y is an 20 integer from 0 to 2. More preferably, y is 0. 21 22 A preferred group of poly(oxyalkylene) hydroxyaromatic 23 esters for use in this invention are those of formula I 24 wherein R, is hydrogen, hydroxy, or lower alkyl having 1 to 25 4 carbon atoms; R 2 is hydrogen; one of R 3 and R 4 is hydrogen 26 __ and the other is methyl or ethyl; R 5 is hydrogen, alkyl 2 Q having 2 to about 22 carbon atoms or alkylphenyl having an 29 alkyl group containing 4 to about 24 carbon atoms; n is 15 30 to 30 and x is 0. 31 32 Another preferred group of poly(oxyalkylene) hydroxyaromatic 33 esters for use in this invention are those of formula I 34 wherein R j is hydrogen, hydroxy, or lower alkyl having 1 to 4 carbon atoms; R-, is hydrogen; one of R 3 and R 4 is hydrogen and the other is methyl or ethyl; R 5 is hydrogen, alkyl having 2 to about 22 carbon atoms or alkylphenyl having an alkyl group containing 4 to about 24 carbon atoms; n is 15 to 30 and x is 1 or 2. A more preferred group of poly(oxyalkylene) hydroxyaromatic esters for use in this invention are those of formula I wherein R, is hydrogen or hydroxy; R 2 is hydrogen; one of R 3 and R 4 is hydrogen and the other is methyl or ethyl; R 5 is hydrogen, alkyl having 4 to 12 carbon atoms or alkylphenyl having an alkyl group containing 4 to 12 carbon atoms; n is 15 to 30; and x is 0. A particularly preferred group of poly(oxyalkylene) hydroxyaromatic esters for use in this invention are those having the formula: wherein one of Rg and R 10 is methyl or ethyl and the other is hydrogen; R π is an alkyl group having 4 to 12 carbon atoms; and m is an integer from 15 to 30. It is especially preferred that the aromatic hydroxyl group or groups present in the poly(oxyalkylene) hydroxyaromatic esters employed in this invention be situated in a meta or para position relative to the poly(oxyalkylene) ester moiety. When the aromatic moiety contains one hydroxyl group, it is particularly preferred that this hydroxyl group be in a para position relative to the poly(oxyalkylene) ester moiety. The poly(oxyalkylene) hydroxyaromatic ester component of the present fuel additive composition will generally have a sufficient molecular weight so as to be non-volatile at normal engine intake valve operating temperatures (about 200-250°C) . Typically, the molecular weight of the poly(oxyalkylene) hydroxyaromatic ester component will range from about 600 to about 10,000, preferably from 1,000 to 3,000. Generally, the poly(oxyalkylene) hydroxyaromatic esters employed in this invention will contain an average of about 5 to about 100 oxyalkylene units; preferably, 10 to 50 oxyalkylene units; more preferably, 15 to 30 oxyalkylene units. Fuel-soluble salts of the poly(oxyalkylene) hydroxyaromatic esters are also contemplated to be useful in the fuel additive composition of the present invention. Such salts include alkali metal, alkaline earth metal, ammonium, substituted ammonium and sulfonium salts. Preferred metal salts are the alkali metal salts, particularly the sodium and potassium salts, and the substituted ammonium salts, particularly tetraalkyl-substituted ammonium salts, such as the tetrabutylammonium salts. General Synthetic Procedures The poly(oxyalkylene) hydroxyaromatic ester component of the present fuel additive composition may be prepared by the following general methods and procedures. It should be appreciated that where typical or preferred process conditions (e.g., reaction temperatures, times, mole ratios of reactants, solvents, pressures, etc.) are given, other process conditions may also be used unless otherwise stated. Optimum reaction conditions may vary with the particular reactants or solvents used, but such conditions can be determined by one skilled in the art by routine optimization procedures. The poly(oxyalkylene) hydroxyaromatic esters employed in the present fuel additive composition that have the formula: -0-R 12 (III) wherein n 11 annud x Λ a αirce a αso d ucefi iinnecdu a αbuouvvee a αniid is an alkyl, phenyl, aralkyl or alkaryl group, may be prepared by esterifying a hydroxyaromatic carboxylic acid having the formula: wherein R l r R 2 , and x are as defined above, with a poly(oxyalkylene) alcohol having the formula: R T R. I HO-(CH-CH-0) n -R, : (V) wherein R 3 , R 4 , R 12 and n are as defined above, using conventional esterification reaction conditions. The hydroxyaromatic carboxylic acids of formula IV are either known compounds or can be prepared from known compounds by conventional procedures. Suitable hydroxyaromatic carboxylic acids for use as starting materials in this invention are 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3 ,4-dihydroxybenzoic acid, 3,4 ,5-trihydroxybenzoic acid, 3-hydroxy-4-methoxybenzoic acid, 4-hydroxy-3-methoxybenzoic acid, 3-t-butyl-4-hydroxybenzoic acid, 3 , 5-di-t-butyl-4- hydroxybenzoic acid, 4-hydroxyacetic acid, 3-(4-hydroxyphenyl)propionic acid and the like. The poly(oxyalkylene) alcohols of formula V may also be prepared by conventional procedures known in the art. Such procedures are taught, for example, in U.S. Patent Nos. 2,782,240 and 2,841,479, which are incorporated herein by reference. Preferably, the poly(oxyalkylene) alcohols of formula V are prepared by contacting an alkoxide or phenoxide metal salt having the formula: R 12 OM (VI) wherein R 12 is as defined above and M is a metal cation, such as lithium, sodium, or potassium, with about 5' to about wherein R 3 and R 4 are as defined above. Generally, metal salt VI is prepared by contacting the corresponding hydroxy compound R 12 OH with a strong base, such as sodium hydride, potassium hydride, sodium amide and the like, in an inert solvent, such as toluene, xylene and the like, under substantially anhydrous conditions at a temperature in the range from about -10°C to about 120°C for about 0.25 to about 3 hours. Metal salt VI is generally not isolated, but is reacted in situ with the alkylene oxide VII to provide, after neutralization, the poly(oxyalkylene) alcohol V. This polymerization reaction is typically conducted in a substantially anhydrous inert solvent at a temperature of about 30°C to about 150°C for about 2 to about 120 hours. Suitable solvents for this reaction, include toluene, xylene and the like. The reaction will generally be conducted at a pressure sufficient to contain the reactants and the solvent, preferably at atmospheric or ambient pressure. The amount of alkylene oxide employed in this reaction will depend on the number of oxyalkylene units desired in the product. Typically, the molar ratio of alkylene oxide VII to metal salt VI will range from about 5:1 to about 100:1; preferably, from 10:1 to 50:1, more preferably from 15:1 to 30:1. 01 Suitable alkylene oxides for use in the polymerization 02 reaction include, for example, ethylene oxide; propylene 03 oxide; butylene oxides, such as 1,2-butylene oxide 04 (1,2-epoxybutane) and 2,3-butylene oxide (2 , 3-epoxybutane) ; 05 pentylene oxides; hexylene oxides; octylene oxides and the 06 like. Preferred alkylene oxides are propylene oxide and 07 ι,2-butylene oxide. 08 09 in the polymerization reaction, a single type of alkylene 10 oxide may be employed, e.g., propylene oxide, in which case 11 the product is a homopolymer, e.g., a poly(oxypropylene) . 12 However, copolymers are equally satisfactory and random 13 copolymers are readily prepared by contacting the metal salt 14 VI with a mixture of alkylene oxides, such as a mixture of 15 propylene oxide and 1,2-butylene oxide, under polymerization 16 conditions. Copolymers containing blocks of oxyalkylene 17 units are also suitable for use in the present invention. 18 Block copolymers may be prepared by contacting the metal 19 salt VI with first one alkylene oxide, then others in any 20 order, or repetitively, under polymerization conditions. 21 22 The poly(oxyalkylene) alcohol V may also be prepared by 23 living or immortal polymerization as described by S. Inoue 24 and T. Aida in Encyclopedia of Polymer Science and 25 Engineering, Second Edition, Supplemental Volume, J. Wiley 26. and Sons, New York, pages 412-420 (1989) . These procedures 27 are especially useful for preparing poly(oxyalkylene) 28 alcohols of formula V in which R 3 and R 4 are both alkyl 2 groups. 30 31 As noted above, the alkoxide or phenoxide metal salt VI is 32 generally derived from the corresponding hydroxy compound, 3 R p OH. Preferred hydroxy compounds for use in this 34 invention include straight- or branched-chain aliphatic alcohols having 1 to about 30 carbon atoms and phenols having the formula: wherein R 13 and R 14 are each independently hydrogen or an alkyl group having 1 to about 30 carbon atoms. Preferably, the straight- or branched-chain aliphatic alcohols employed in this invention will contain 2 to about 22 carbon atoms, more preferably 4 to 12 carbon atoms. Representative examples of straight- or branched-chain aliphatic alcohols suitable for use in this invention include, but are not limited to, n-butanol; isobutanol; sec-butanol; t-butanol; n-pentanol; n-hexanol; n-heptanol; n-octanol; isooctanol; n-nonanol; n-decanol; n-dodecanol; n-hexadecanol (cetyl alcohol) ; n-octadecanol (stearyl alcohol) ; alcohols derived from linear C 10 to C 30 alpha olefins and mixtures thereof; and alcohols derived from polymers of C to C 6 olefins, such as alcohols derived from polypropylene and polybutene, including polypropylene alcohols having 9 to about 30 carbon atoms. Particularly preferred aliphatic alcohols are butanols. The alkylphenols of formula VIII may be monoalkyl-substituted phenols or dialkyl-substituted phenols. Monoalkyl-substituted phenols are preferred, especially monoalkylphenols having an alkyl substituent in the para position. 1 Preferably, the alkyl group of the alkylphenols will contain 2 4 to about 24 carbon atoms, more preferably 4 to 12 carbon 3 atoms. Representative examples of phenols suitable include, 4 phenol, methylphenol, dimethylphenol, ethylphenol, 5 butylphenol, octylphenol, decylphenol, dodecyl ' phenol, 6 tetradecylphenol, hexadecylphenol, octadecylphenol, 7 eicosylphenol, tetracosylphenol, hexacosylphenol, 8 triacontylphenol and the like. Also, mixtures of 9 alkylphenols may be employed, such as a mixture of C 14 -C 18 ° alkylphenols, a mixture of C 18 -C 24 alkylphenols, a mixture of 1 C 20 -C 24 alkylphenols, or a mixture of C 16 -C-, 6 alkylphenols. 2 3 Particularly preferred alkylphenols are those derived from 4 alkylation of phenol with polymers or oligomers of C 3 to C 6 5 olefins, such as polypropylene or polybutene. These 6 polymers preferably contain 10 to 30 carbon atoms. An 7 especially preferred alkylphenol is prepared by alkylating 8 phenol with a propylene polymer having an average of 4 9 units. This polymer has the common name of propylene 0 tetramer and is commercially available. 1 As indicated above, the poly(oxyalkylene) hydroxyaromatic esters of formula III may be prepared by esterifying a hydroxyaromatic carboxylic acid of formula IV with a poly(oxyalkylene) alcohol of formula V under conventional 6 esterification reaction conditions. Typically, this reaction will be conducted by contacting a poly(oxyalkylene) alcohol of formula V with about 0.25 to about 1.5 molar equivalents of a hydroxyaromatic carboxylic acid of formula IV in the presence of acidic catalyst at a temperature in the range of 70°C to about 160°C for about 0.5 to about 48 hours. Suitable acid catalysts for this reaction include p-toluenesulfonic acid, ethanesulfonic acid and the like. The reaction may be conducted in the presence or absence of an inert solvent, such as benzene, toluene and the like. The water generated by this reaction is preferably removed during the course of the reaction by, for example, azeotropic distillation with an inert solvent, such as toluene. The poly(oxyalkylene) hydroxyaromatic esters of formula III may also be synthesized by reacting a poly(oxyalkylene) alcohol of formula V with an acyl halide having the formula: wherein X is a halide, such as chloride or bromide, and R I5 is a suitable hydroxyl protecting group, such as benzyl, tert-butyldimethylsilyl, methoxy ethyl, and the like; R, 6 and R 17 are each independently hydrogen, lower alkyl, lower alkoxy, or the group -OR 18 , wherein R 18 is a suitable hydroxyl protecting group. Acyl halides of formula IX may be prepared from hydroxyaromatic carboxylic acids of formula IV by first protecting the aromatic hydroxyl groups of IV to form a carboxylic acid having the formula: wherein R 15 -R 17 and x are as defined above, and then converting the carboxylic acid moiety of X into an acyl halide using conventional procedures. Protection of the aromatic hydroxyl groups of IV may be accomplished using well known procedures. The choice of a suitable protecting group for a particular hydroxyaromatic carboxylic acid will be apparent to those skilled in the art. Various protecting groups, and their introduction and removal, are described, for example, in T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis , Second Edition, Wiley, New York, 1991, and references cited therein. Alternatively, the protected derivatives X can be prepared from known starting materials other than the hydroxyaromatic compounds of formula IV by conventional procedures. The carboxylic acid moiety of X may be converted into an acyl halide by contacting X with an inorganic acid halide, such as thionyl chloride, phosphorous trichloride, phosphorous tribromide, or phosphorous pentachloride; or alternatively, with oxalyl chloride. Generally, this reaction will be conducted using about 1 to 5 molar equivalents of the inorganic acid halide or oxalyl chloride, either neat or in an inert solvent, such as diethyl ether, at a temperature in the range of about 20°C to about 80°C for about 1 to about 48 hours. A catalyst, such as N,N-dimethylformamide, may also be used in this reaction. in certain cases where the hydroxyaromatic carboxylic acids of formula IV having bulky alkyl groups adjacent to the hydroxyl group, such as 3 , 5-di-t-butyl-4-hydroxybenzoic acid, it will generally not be necessary to protect the hydroxyl group prior to formation of the acyl halide, since such hydroxyl groups are sufficiently sterically hindered so as to be substantially ,non-reactive with the acyl halide moiety. Reaction of acyl halide IX with poly(oxyalkylene) alcohol V provides an intermediate poly(oxyalkylene) ester having the formula: ) n -0-R 12 (XI) wherein R 3 , R 4 , R 12 , R 15 -R 17 , n and x are as defined above. Typically, this reaction is conducted by contacting V with about 0.9 to about 1.5 molar equivalents of IX in an inert solvent, such as toluene, dichloromethane, diethyl ether, and the like, at a temperature in the range of about 25°C to about 150°C. The reaction is generally complete in about 0.5 to about 48 hours. Preferably, the reaction is conducted in the presence of a sufficient amount of an amine capable of neutralizing the acid generated during the reaction, such as triethyla ine, di (isopropyl) ethylamine, pyridine or 4-dimethylamino-pyridine. Deprotection of the aromatic hydroxyl group(s) of XI then provides a poly(oxyalkylene) hydroxyaromatic ester of formula III. Appropriate conditions for this deprotection step will depend upon the protecting group(s) utilized in the synthesis and will be readily apparent to those skilled in the art. For example, benzyl protecting groups may be removed by hydrogenolysis under 1 to about 4 atmospheres of hydrogen in the presence of a catalyst, such as palladium on carbon. Typically, this deprotection reaction is conducted in an inert solvent, preferably a mixture of ethyl acetate and acetic acid, at a temperature of from about 0°C to about 40°C for about 1 to about 24 hours. The poly(oxyalkylene) hydroxyaromatic esters employed in the present fuel additive composition that have the formula: ) n -OH (XII) wherein R [ -R 4 , n and x are as defined above, can be prepared from compounds of formula III or XI, wherein R p is a benzyl group, by removing the benzyl group using conventional hydrogenolysis procedures. Compounds of formula III or XI where R 12 represents a benzyl group may be prepared by employing a metal salt VI derived from benzyl alcohol in the above described synthetic procedures. Similarly, the poly(oxyalkylene) hydroxyaromatic esters employed in the present invention that have the formula: wherein R ] -R 4 , n and x are as defined above and R 19 is an acyl group having the formula: wherein R 6 -Rg and y are as defined above, can be synthesized in several steps from a compound of formula XI, wherein R r represents a benzyl group and R 15 (and optionally R 18 ) represents a hydroxyl protecting group that is stable to hydrogenolysis conditions, such as a tert-butyldimethyl- silyl group. The synthesis of XIII from such compounds may be effected by first removing the benzyl group using conventional hydrogenolysis conditions and then acylating the resulting hydroxyl group with a suitable acylating agent. Removal of the protecting group(s) from the aromatic hydroxyl group(s) using conventional procedures then provides a poly(oxyalkylene) hydroxyaromatic ester of formula XIII. Suitable acylating agents for use in this reaction include acyl halides, such as acyl chlorides and bromides; and carboxylic acid anhydrides. Preferred acylating agents are those having the formula: R 6 C(0)-X, wherein R 6 is alkyl having 1 to 30 carbon atom, phenyl, or aralkyl or alkaryl having 7 to 36 carbon atoms, and X is chloro or bromo; and those having the formula: wherein X is a halide, such as chloride or bromide, R, 0 is a suitable hydroxyl protecting group, R 2] and R,, are each independently hydrogen, lower alkyl, lower alkoxy, or the group -OR, 3 , wherein R, 3 is a suitable hydroxyl protecting group, and y is an integer from 0 to 10. A particularly preferred group of acylating agents are those having the formula: R, 4 C(0)-X, wherein R, 4 is alkyl having 4 to 12 carbon atoms.. Representative examples of such acylating agents include acetyl chloride, propionyl chloride, butanoyl chloride, pivaloyl chloride, octanoyl chloride, decanoyl chloride and the like. Another particularly preferred group of acylating agents are those of formula XIV, wherein R, 0 is benzyl; R,, is hydrogen, alkyl having 1 to 4 carbon atoms, or -OR, 5 , wherein R, 5 is a suitable hydroxyl protecting group, preferably benzyl; R,, is hydrogen; and y is 0, 1 or 2. Representative examples of such acylating agents include 4-benzyloxybenzoyl chloride, 3-benzyloxybenzoyl chloride, 4-benzyloxy-3-methylbenzoyl chloride, 4-benzyloxyphenylacetyl chloride, 3-(4-benzyloxyphenyl)propionyl chloride and the like. Generally, this acylation reaction will be conducted using about 0.95 to about 1.2 molar equivalents of the acylating agent. The reaction is typically conducted in an inert solvent, such as toluene, dichloromethane, diethyl ether and the like, at a temperature in the range of about 25°C to about 150°C for about 0.5 to about 48 hours. When an acyl halide is employed as the acylating agent, the reaction is preferably conducted in the presence of a sufficient amount of an amine capable of neutralizing the acid generated during the reaction, such as triethylamine, di (isopropyl) - ethylamine, pyridine or 4-dimethylaminopyridine. A particularly preferred group of poly(oxyalkylene) hydroxyaromatic esters of formula XIII are those having the same hydroxyaromatic ester group at each end the poly(oxyalkylene) moiety, i.e., compounds of formula XIII wherein R 19 is an acyl group having the formula: wherein R 7 is the same group as R, , R 8 is the same group as R,, and x and y are the same integer. These compounds may be prepared from a poly(oxyalkylene) diol having the formula: , HO-(CH-CH-0) n -H (XV) wherein R 3 , R 4 , and n are as defined above, by esterifying each of the hydroxyl groups present in XV with a hydroxyaromatic carboxylic acid of formula IV or an acyl halide of formula IX using the above described synthetic procedures. The poly(oxyalkylene) diols of formula XV are commercially available or may be prepared by conventional procedures, for example, by using sodium or potassium hydroxide in place of the alkoxide or phenoxide metal salt VI in the above described alkylene oxide polymerization reaction. The Aliphatic Amine The aliphatic amine component of the present fuel additive composition is an aliphatic amine having at least one basic nitrogen atom and containing a hydrocarbyl group which has sufficient molecular weight and carbon chain length to render the aliphatic amine soluble in hydrocarbons boiling in the gasoline or diesel range. Preferably, such aliphatic amines will also be of sufficient molecular weight so as to be nonvolatile at normal engine intake valve operating temperatures, generally in the range of about 175°C to 300°C. In general, the aliphatic amine will contain a hydrocarbyl group having a number average molecular weight in the range of about 250 to 3,000, preferably in the range of about 700 to 2,200, and more preferably, in the range of about 900 to 1,500. In a preferred embodiment, the aliphatic amine component of the present fuel additive composition is a fuel-soluble aliphatic amine selected from the group consisting of: (1) a straight or branched chain hydrocarbyl- substituted amine having at least one basic nitrogen atom wherein the hydrocarbyl group has a number average molecular weight of about 250 to 3,000. (2) a hydroxyalkyl-substituted amine comprising the reaction product of (i) a polyolefin epoxide derived from a branched-chain polyolefin having a number average molecular weight of about 250 to 3,000, and (ii) a nitrogen-containing compound selected from ammonia, a monoamine having from 1 to 40 carbon atoms, and a polyamine having from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms, and (3) a straight or branched chain hydrocarbyl- substituted succinimide comprising the reaction product of a straight or branched chain hydrocarbyl-substituted succinic acid or anhydride, wherein the hydrocarbyl group has a number average molecular weight of about 250 to 3,000, and a polyamine having from 2 to about 12 amine nitrogen atoms and 2 to about 40 carbon atoms. A. The Hydrocarbyl-Substituted Amine The hydrocarbyl-substituted amine employed as the aliphatic amine component of the present fuel additive composition is a straight or branched chain hydrocarbyl-substituted amine having at least one basic nitrogen atom wherein the hydrocarbyl group has a number average molecular weight of about 250 to 3,000. Preferably, the hydrocarbyl group will have a number average molecular weight in the range of about 700 to 2,200, and more preferably, in the range of about 900 to 1,500. The hydrocarbyl group may be either straight chain or branched chain. When the hydrocarbyl group is straight chain, a preferred aliphatic amine is oleyl amine. When employing a branched chain hydrocarbyl amine, the hydrocarbyl group is preferably derived from polymers of C, to C 6 olefins. Such branched-chain hydrocarbyl group will ordinarily be prepared by polymerizing olefins of from 2 to 6 carbon atoms (ethylene being copolymerized with another olefin so as to provide a branched-chain) . The branched chain hydrocarbyl group will generally have at least 1 branch per 6 carbon atoms along the chain, preferably at least 1 branch per 4 carbon atoms along the chain and, more preferably, at least 1 branch per 2 carbon atoms along the chain. The preferred branched-chain hydrocarbyl groups are polypropylene and polyisobutylene. The branches will usually be of from 1 to 2 carbon atoms, preferably 1 carbon atom, that is, methyl. In general, the branched-chain hydrocarbyl group will contain from about 18 to about 214 carbon atoms, preferably from about 50 to about 157 carbon atoms. In most instances, the branched-chain hydrocarbyl amines are not a pure single product, but rather a mixture of compounds having an average molecular weight. Usually, the range of molecular weights will be relatively narrow and peaked near the indicated molecular weight. The amine component of the branched-chain hydrocarbyl amines may be derived from ammonia, a monoamine or a polyamine. The monoamine or polyamine component embodies a broad class of amines having from 1 to about 12 amine nitrogen atoms and from 1 to 40 carbon atoms with a carbon to nitrogen ratio between about 1:1 and 10:1. Generally, the monoamine will contain from 1 to about 40 carbon atoms and the polyamine will contain from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms. In most instances, the amine component is not a pure single product, but rather a mixture of compounds having a major quantity of the designated amine. For the more complicated polyamines, the compositions will be a mixture of amines having as the major product the compound indicated and having minor amounts of analogous compounds. Suitable monoamines and polyamines are described more fully below in the discussion of hydroxyalkyl-substituted amines. When the amine component is a polyamine, it will preferably be a polyalkylene polyamine, including alkylenediamine. Preferably, the alkylene group will contain from 2 to 6 carbon atoms, more preferably from 2 to 3 carbon atoms. Examples of such polyamines include ethylene diamine, diethylene triamine, triethylene tetramine and tetraethylene pentamine. Preferred polyamines are ethylene diamine and diethylene triamine. A particularly preferred branched-chain hydrocarbyl amine is polyisobutenyl ethylene diamine. The branched-chain hydrocarbyl amines employed in the fuel additive composition of the invention are prepared by conventional procedures known in the art. Such branched-chain hydrocarbyl amines and their preparations are described in detail in U.S. Patent Nos. 3,438,757; 3,565,804; 3,574,576; 3,848,056 and 3,960,515, the disclosures of which are incorporated herein by reference. B. The Hydroxyalkyl-Substituted Amine The hydroxyalkyl-substituted amine additive employed in the fuel composition of the present invention comprises the reaction product of (a) a polyolefin epoxide derived from a branched chain polyolefin having an average molecular weight of about 250 to 3,000 and (b) a nitrogen-containing compound selected from ammonia, a monoamine having from 1 to 40 carbon atoms, and a polyamine having from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms. The amine component of this reaction product is selected to provide solubility in the fuel composition and deposit control activity. Polyolefin Epoxide Component The polyolefin epoxide component of the presently employed hydroxyalkyl-substituted amine reaction product is obtained by oxidizing a polyolefin with an oxidizing agent to give an alkylene oxide, or epoxide, in which the oxirane ring is derived from oxidation of the double bond in the polyolefin. The polyolefin starting material used in the preparation of the polyolefin epoxide is a high molecular weight branched chain polyolefin having an average molecular weight of about 250 to 3,000, preferably from about 700 to 2,200, and more preferably from about 900 to 1,500. Such high molecular weight polyolefins are generally mixtures of molecules having different molecular weights and can have at least one branch per 6 carbon atoms along the chain, preferably at least one branch per 4 carbon atoms along the chain, and particularly preferred that there be about one branch per 2 carbon atoms along the chain. These branched chain olefins may conveniently comprise polyolefins prepared by the polymerization of olefins of from 2 to 6 carbon atoms, and preferably from olefins of from 3 to 4 carbon atoms, and more preferably from propylene or isobutylene. When ethylene is employed, it will normally be copolymerized with another olefin so as to provide a branched chain polyolefin. The addition-poly erizable olefins employed are normally 1-olefins. The branch may be of from 1 to 4 carbon atoms, more usually of from 1 to 2 carbon atoms, and preferably methyl. in general, any high molecular weight branched chain polyolefin isomer whose epoxide is capable of reacting with an amine is suitable for use in preparing the presently employed fuel additives. However, sterically hindered epoxides, such as tetra-alkyl substituted epoxides, are generally slower to react. Particularly preferred polyolefins are those containing an alkylvinylidene isomer present in an amount at least about 20%, and preferably at least 50%, of the total polyolefin . composition. The preferred alkylvinylidene isomers include methylvinylidene and ethylvinylidene, more preferably the methylvinylidene isomer. 01 The especially preferred high molecular weight polyolefins 02 used to prepare the instant polyolefin epoxides are 03 polyisobutenes which comprise at least about 20% of the more 04 reactive methylvinylidene isomer, preferably at least 50% 05 and more preferably at least 70%. Suitable polyisobutenes 06 include those prepared using BF 3 catalysts. The preparation 07 of such polyisobutenes in which the methylvinylidene isomer 08 comprises a high percentage of the total composition is 09 described in U.S. Patent Nos. 4,152,499 and 4,605,808. 10 11 Examples of suitable polyisobutenes having a high 1 alkylvinylidene content include Ultravis 30, a polyisobutene 13 having a molecular weight of about 1300 and a 14 methylvinylidene content of about 76%, available from 1 5 British Petroleum. 16 I 7 As noted above, the polyolefin is oxidized with a suitable i8 oxidizing agent to provide an alkylene oxide, or polyolefin I 9 epoxide, in which the oxirane ring is formed from oxidation 20 of the polyolefin double bond. 21 22 The oxidizing agent employed may be any of the well known 23 conventional oxidizing agents used to oxidize double bonds. 24 Suitable oxidizing agents include hydrogen peroxide, 25 peracetic acid, perbenzoic acid, performic acid, 6 monoperphthalic acid, percamphoric acid, persuccinic acid 7 and petrifluoroacetic acid. The preferred oxidizing agent 8 is peracetic acid. 9 0 When peracetic acid is used as the oxidizing agent, 1 generally a 40% peracetic acid solution and about a 5% 2 equivalent of sodium acetate (as compared to the peracetic 3 acid) is added to the polyolefin in a molar ratio of 4 per-acid to olefin in the range of about 1.5:1 to 1:1, preferably about 1.2:1. The mixture is gradually allowed to react at a temperature in the range of about 20°C to 90°C. The resulting polyolefin epoxide, which is isolated by conventional techniques, is generally a liquid or semi-solid resin at room temperature, depending on the type and molecular weight of olefin employed. Amine Component The amine component of the presently employed hydroxyalkyl- substituted amine reaction product is derived from a nitrogen-containing compound selected from ammonia, a monoamine having from 1 to 40 carbon atoms, and a polyamine having from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms. The amine component is reacted with a polyolefin epoxide to produce the hydroxyalkyl-substituted amine fuel additive finding use within the scope of the present invention. The amine component provides a reaction product with, on the average, at least about one basic nitrogen atom per product molecule, i.e. , a nitrogen atom titratable by a strong acid. Preferably, the amine component is derived from a polyamine having from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms. The polyamine preferably has a carbon-to-nitrogen ratio of from about 1:1 to 10:1. The polyamine may be substituted with substituents selected from (A) hydrogen, (B) hydrocarbyl groups of from 1 to about 10 carbon atoms, (C) acyl groups of from 2 to about ιo carbon atoms, and (D) monoketo, onohydroxy, mononitro, monocyano, lower alkyl and lower alkoxy derivatives of (B) and (C) . "Lower", as used in terms like lower alkyl or lower alkoxy, means a group containing from 1 to about 6 carbon atoms. At least one of the substituents on one of the basic nitrogen atoms of the polyamine is hydrogen, e.g., at least one of the basic nitrogen atoms of the polyamine is a primary or secondary amino nitrogen. Hydrocarbyl, as used in describing the ' amine components of this invention, denotes an organic radical composed of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combinations thereof, e.g., aralkyl. Preferably, the hydrocarbyl group will be relatively free of aliphatic unsaturation, i.e., ethylenic and acetylenic, particularly acetylenic unsaturation. The substituted polyamines of the present invention are generally, but not necessarily, N-substituted polyamines. Exemplary hydrocarbyl groups and substituted hydrocarbyl groups include alkyIs such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, etc., alkenyls such as propenyl, isobutenyl, hexenyl, octenyl, etc., hydroxyalkyls, such as 2-hydroxyethyl, 3-hydroxypropyl , hydroxy-isopropy1 , 4-hydroxybutyl, etc., ketoalkyls, such as 2-ketopropyl , 6-ketooctyl, etc., alkoxy and lower alkenoxy alkyls, such as ethoxyethyl, ethoxypropyl, propoxyethyl, propoxypropyl , diethyleneoxymethyl, triethyleneoxyethyl , tetraethyleneoxyethyl, diethyleneoxyhexyl, etc. The aforementioned acyl groups (C) are such as propionyl, acetyl, etc. The more preferred substituents are hydrogen, C [ -C 6 alkyls and C,-C 6 hydroxyalkyls. in a substituted polyamine, the substituents are found at any atom capable of receiving them. The substituted atoms, e.g., substituted nitrogen atoms, are generally geometrically unequivalent, and consequently the substituted amines finding use in the present invention can be mixtures of mono- and poly-substituted polyamines with substituent groups situated at equivalent and/or unequivalent atoms. The more preferred polyamine finding use within the scope of the present invention is a polyalkylene polyamine, including alkylene diamine, and including substituted polyamines, e.g., alkyl and hydroxyalkyl-substituted polyalkylene polyamine. Preferably, the alkylene group contains from 2 to 6 carbon atoms, there being preferably from 2 to 3 carbon atoms between the nitrogen atoms. Such groups are exemplified by ethylene, 1,2-propylene, 2 , 2-dimethyl- propylene, trimethylene, 1,3,2-hydroxypropylene, etc. Examples of such polyamines include ethylene diamine, diethylene triamine, di(trimethylene) triamine, dipropylene triamine, triethylene tetraamine, tripropylene tetraamine, tetraethylene pentamine, and pentaethylene hexamine. Such amines encompass isomers such as branched-chain polyamines and previously-mentioned substituted polyamines, including hydroxy- and hydrocarbyl-substituted polyamines. Among the polyalkylene polyamines, those containing 2-12 amino nitrogen atoms and 2-24 carbon atoms are especially preferred, and the C,-C 3 alkylene polyamines are most preferred, that is,, ethylene diamine, polyethylene polyamine, propylene diamine and polypropylene polyamine, and in particular, the lower polyalkylene polyamines, e.g., ethylene diamine, dipropylene triamine, etc. A particularly preferred polyalkylene polyamine is diethylene triamine. The amine component of the presently employed fuel additive also may be derived from heterocyclic polyamines, heterocyclic substituted amines and substituted heterocyclic compounds, wherein the heterocycle comprises one or more 5-6 membered rings containing oxygen and/or nitrogen. Such heterocyclic rings may be saturated or unsaturated and substituted with groups selected from the aforementioned (A) , (B) , (C) and (D) . The heterocyclic compounds are exemplified by piperazines, such as 2-methylpiperazine, N-(2-hydroxyethyl) -piperazine, 1, 2-bis-(N-piperazinyl) ethane and N,N'-bis(N-piperazinyl)piperazine, 2-methylimidazoline, 3-aminopiperidine, 3-aminopyridine, N-(3-aminopropyl) - morpholine, etc. Among the heterocyclic compounds the piperazines are preferred. Typical polyamines that can be used to form the additives employed in this invention by reaction with a polyolefin epoxide include the following: ethylene diamine, 1,2-propylene diamine, 1, 3-propylene diamine, diethylene triamine, triethylene tetramine, hexamethylene diamine, tetraethylene pentamine, dimethylaminopropylene diamine, N-(beta-aminoethyl)piperazine, N-(beta- aminoethyl)piperadine, 3-amino-N-ethylpiperidine, N-(beta- aminoethyl) morpholine, N,N'-di (beta-aminoethyl)piperazine, N,N'-di (beta-aminoethyl) imidazolidone-2 , N-(beta-cyanoethyl) ethane-1, 2-diamine, l-amino-3 , 6,9-triazaoctadecane, l-amino-3, 6-diaza-9-oxadecane, N- (beta-aminoethyl) diethanolamine, N'acetylmethyl-N-(beta-aminoethyl) ethane-l,2-diamine, N-acetonyl-1, 2-propanediamine, N-(beta- nitroethyl) -1, 3-propane diamine, 1, 3-dimethyl-5 (beta- aminoethyl)hexahydrotriazine, N-(beta-aminoethyl) - hexahydrotriazine, 5-(beta-aminoethyl) -1, 3 , 5-dioxazine, 2-(2-aminoethylamino) ethanol, and 2-[2- (2-aminoethylamino) ethylamino]ethanol. Alternatively, the amine component of the presently employed hydroxyalkyl-substituted amine may be derived from an amine having the formula: H-N-R, R, wherein R, and R, are independently selected from the group consisting of hydrogen and hydrocarbyl of 1 to about 20 carbon atoms and, when taken together, R j and R, may form one or more 5- or 6-membered rings containing up to about 20 carbon atoms. Preferably, R t is hydrogen and R, is a hydrocarbyl group having 1 to about 10 carbon atoms. More preferably, R, and R, are hydrogen. The hydrocarbyl groups -may be straight-chain or branched and may be aliphatic, alicyclic, aromatic or combinations thereof. The hydrocarbyl groups may also contain one or more oxygen atoms. An amine of the above formula is defined as a "secondary amine" when both R j and R, are hydrocarbyl. When R, is hydrogen and R, is hydrocarbyl, the amine is defined as a "primary amine"; and when both R, and R, are hydrogen, the amine is ammonia. Primary amines useful in preparing the fuel additives of the present invention contain 1 nitrogen atom and 1 to about 20 carbon atoms, preferably 1 to 10 carbon atoms. The primary amine may also contain one or more oxygen atoms. Preferably, the hydrocarbyl group of the primary amine is methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-hydroxyethyl or 2-methoxyethyl . More preferably, the hydrocarbyl group is methyl, ethyl or propyl. Typical primary amines are exemplified by N-methylamine, N-ethylamine, N-n-propylamine, N-isopropylamine, N-n-butylamine, N-isobutylamine, N-sec-butylamine, N-tert-butylamine, N-n-pentylamine, N-cyclopentylamine, N-n-hexylamine, N-cyclohexylamine, N-octylamine, N-decylamine, N-dodecylamine, N-octadecylamine, N-benzylamine, N-(2-phenylethyl) amine, 2-aminoethanol, 3-amino-l-proponal, 2-(2-aminoethoxy)ethanol, N-(2-methoxyethyl) amine, N- (2-ethoxyethyl) amine and the like. Preferred primary amines are N-methylamine, N-ethylamine and N-n-propylamine. The amine component of the presently employed fuel additive may also be derived from a secondary amine. The hydrocarbyl groups of the secondary amine may be the same or different and will generally contain 1 to about 20 carbon atoms, preferably 1 to about 10 carbon atoms. One or both of the hydrocarbyl groups may also contain one or more oxygen atoms. Preferably, the hydrocarbyl groups of the secondary amine are independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-hydroxyethyl and 2-methoxyethyl. More preferably, the hydrocarbyl groups are methyl, ethyl or propyl. Typical secondary amines which may be used in this invention include N,N-dimethylamine, N, N-diethylamine, N,N-di-n- propyla ine, N,N-diisopropylamine, N,N-di-n-butylamine, N,N-di-sec-butylamine, N,N-di-n-pentylamine, N,N-di-n-hexylamine, N,N-dicyclohexylamine, N,N-dioctylamine, N-ethyl-N-methylamine, N-methyl-N-n- propylamine, N-n-butyl-N-methylamine, N-methyl-N-octylamine, N-ethyl-N-isopropylamine, N-ethyl-N-octylamine, N,N-di(2-hydroxyethyl) amine, N,N-di (3-hydroxypropyl) amine, N,N-di (ethoxyethyl)amine, N, N-di (propoxyethyl) amine and the like. Preferred secondary amines are N,N-dimethylamine, N,N-diethylamine and N,N-di-n-propylamine. Cyclic secondary amines may also be employed to form the additives of this invention. In such cyclic Compounds, R, and R, of the formula hereinabove, when taken together, form one or more 5- or 6-membered rings containing up to about 20 carbon atoms. The ring containing the amine nitrogen atom is generally saturated, but may be fused to one or more saturated or unsaturated rings. The rings may be substituted with hydrocarbyl groups of from 1 to about 10 carbon atoms and may contain one or more oxygen atoms. Suitable cyclic secondary amines include piperidine, 4-methylpiperidine, pyrrolidine, morpholine, 2, 6-dimethylmorpholine and the like. In many instances the amine component is not a single compound but a mixture in which one or several compounds predominate with the average composition indicated. For example, tetraethylene pentamine prepared by the polymerization of aziridine or the reaction of dichloroethylene and ammonia will have both lower and higher amine members, e.g., triethylene tetraamine, substituted piperazines and pentaethylene hexamine, but the composition will be mainly tetraethylene pentamine and the empirical formula of the total amine composition will closely approximate that of tetraethylene pentamine. Finally, in preparing the compounds of this invention using a polyamine, where the various nitrogen atoms of the polyamine are not geometrically equivalent, several substitutional isomers are possible and are encompassed within the final product. Methods of preparation of amines and their reactions are detailed in Sidgewick's "The Organic Chemistry of Nitrogen", Clarendon Press, Oxford, 1966; Noller's "Chemistry of Organic Compounds", Saunders, Philadelphia, 2nd Ed., 1957; and Kirk-Oth er's "Encyclopedia of Chemical Technology", 2nd Ed., especially Volume 2, pp. 99-116. Preparation of the Hydroxyalkyl-Substituted Amine Reaction Product As noted above, the fuel additive finding use in the present invention is a hydroxyalkyl-substituted amine which is the reaction product of (a) a polyolefin epoxide derived from a branched chain polyolefin having an average molecular weight of about 250 to 3,000 and (b) a nitrogen-containing compound selected from ammonia, a monoamine having from 1 to 40 carbon atoms, and a polyamine having from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms. The reaction of the polyolefin epoxide and the amine component is generally carried out either neat or with a solvent at a temperature in the range of about 100°C to 250°C and preferably from about 180°C to about 220°C. A reaction pressure will generally be maintained in the range from about 1 to 250 atmospheres. The reaction pressure will vary depending on the reaction temperature, presence or absence of solvent and the boiling point of the amine component. The reaction usually is conducted in the absence of oxygen, and may be carried out in the presence or absence of a catalyst. The desired product may be obtained by water wash and stripping, usually by aid of vacuum, of any residual solvent. The mole ratio of basic amine nitrogen to polyolefin epoxide will generally be in the range of about 3 to 50 moles of basic amine nitrogen per mole of epoxide, and more usually about 5 to 20 moles of basic amine nitrogen per mole of epoxide. The mole ratio will depend upon the particular amine and the desired ratio of epoxide to amine. Since suppression of polysubstitution of the amine is usually desired, large mole excesses of the amine will generally be used. The reaction of polyolefin epoxide and amine may be conducted either in the presence or absence of a catalyst. When employed, suitable catalysts include Lewis acids, such as aluminum trichloride, boron trifluoride, titanium tetrachloride, ferric chloride, and the like. Other useful catalysts include solid catalysts containing both Bronsted and Lewis acid sites, such as alumina, silica, silica-alumina, and the like. The reaction may also be carried out with or without the presence of a reaction solvent. A reaction solvent is generally employed whenever necessary to reduce the viscosity of the reaction product. These solvents should be stable and inert to the reactants and reaction product. Preferred solvents include aliphatic or aromatic hydrocarbons or aliphatic alcohols. Depending on the temperature of the reaction, the particular polyolefin epoxide used, the mole ratios and the particular amine, as well as the presence or absence of a catalyst, the reaction time may vary from less than 1 hour to about 72 hours. After the reaction has been carried out for a sufficient length of time, the reaction mixture may be subjected to extraction with a hydrocarbon-water or hydrocarbon-alcohol- water medium to free the product from any low-molecular weight amine salts which have formed and any unreacted polyamines. The product may then be isolated by evaporation of the solvent. in most instances, the additive compositions used in this invention are not a pure single product, but rather a mixture of compounds having an average molecular weight. Usually, the range of molecular weights will be relatively narrow and peaked near the indicated molecular weight. Similarly, for the more complicated amines, such as polyamines, the compositions will be a mixture of amines having as the major product the compound indicated as the average composition and having minor amounts of analogous compounds relatively close in compositions to the dominant compound. c. The Hvdrocarbyl-Substituted Succinimide The hydrocarbyl-substituted succinimide which can be employed as the aliphatic amine component of the present fuel additive composition is a straight or branched chain hydrocarbyl-substituted succinimide comprising the reaction product of a straight or branched chain hydrocarbyl- substituted succinic acid or anhydride, wherein the hydrocarbyl group has a number average molecular weight of about 250 to 3,000, and a polyamine having from 2 to about 12 amine nitrogen atoms and 2 to about 40 carbon atoms. Preferably, the hydrocarbyl group will have a number average molecular weight in the range of about 700 to 2,200, and more preferably, in the range of about 900 to 1,500. The hydrocarbyl group may be either straight chain or branched 1 chain. Preferably, the hydrocarbyl group will be a branched 2 chain hydrocarbyl group. 3 4 When employing a branched chain hydrocarbyl-substituted 5 succinimide, the branched chain hydrocarbyl group is 6 preferably derived from polymers of C, to C 6 olefins. Such 7 branched chain hydrocarbyl groups are described more fully 8 above in the discussion of hydrocarbyl-substituted amines 9 and hydroxyalkyl-substituted amines. Preferably, the ° branched chain hydrocarbyl group will be derived from 1 polypropylene or polyisobutylene. More preferably, the 2 branched chain hydrocarbyl group will be derived from 3 polyisobutylene. 4 5 The succinimides employed in the present invention are 6 prepared by reacting a straight or branched chain 7 hydrocarbyl-substituted succinic acid or anhydride with a 8 polyamine having from 2 to about 12 amine nitrogen atoms and 9 2 to about 40 carbon atoms. 0 1 Hydrocarbyl-substituted succinic anhydrides are well known 2 in the art and are prepared by the thermal reaction of 3 olefins and maleic anhydride as described, for example, in 4 u.S. Patent Nos. 3,361,673 and 3,676,089. Alternatively, 5 hydrocarbyl-substituted succinic anhydrides can be prepared 6 by reaction of chlorinated olefins with maleic anhydride as 7 described, for example, in U.S. Patent No. 3,172,892. The 8 olefin employed in these reactions has a number average 9 molecular weight in the range of about 250 to about 3,000. 0 Preferably, the number average molecular weight of the i olefin is about 700 to about 2,200, more preferably about 2 900 to 1,500. 3 4 The reaction of a polyamine with an alkenyl or alkyl succinic acid or anhydride to produce a polyamino alkenyl or alkyl succinimide is well known is the art and is described, for example, in U.S. Patent Nos. 3,018,291; 3,024,237; 3,172,892; 3,219,666; 3,223,495; 3,272,746; 3,361,673 and 3,443,918. The Amine Component of the Succinimide The amine moiety of the hydrocarbyl-substituted succinimide is preferably derived from a polyamine having from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms. The polyamine is preferably reacted with a hydrocarbyl-substituted succinic acid or anhydride to produce the hydrocarbyl-substituted succinimide fuel additive finding use within the scope of the present invention. The polyamine, encompassing diamines, provides the product succinimide with, on the average, at least about one basic nitrogen atom per succinimide molecule, i.e., a nitrogen atom titratable by strong acid. The polyamine preferably has a carbon-to-nitrogen ratio of from about 1:1 to about 10:1. The polyamine may be substituted with substituents selected from hydrogen, hydrocarbyl groups of from 1 to about 10 carbon atoms, acyl groups of from 2 to about 10 carbon atoms, and monoketone, monohydroxy, mononitro, monocyano, alkyl and alkoxy derivatives of hydrocarbyl groups of from 1 to 10 carbon atoms. It is preferred that at least one of the basic nitrogen atoms of the polyamine is a primary or secondary amino nitrogen. The polyamine component employed in the present invention has been described and exemplified more fully in U.S. Patent No. 4,191,537. Hydrocarbyl, as used in describing the amine components used in this invention, denotes an organic radical composed of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combinations thereof, e.g., aralkyl. Preferably, the hydrocarbyl group will be relatively free of aliphatic unsaturation, i.e., ethylenic and acetylenic, particularly acetylenic unsaturation. ' The more preferred polyamine finding use within the scope of the present invention is a polyalkylene polyamine, including alkylenediamine, and including substituted polyamines, e.g., alkyl and hydroxyalkyl-substituted polyalkylene polyamine. Preferably, the alkylene group contains from 2 to 6 carbon atoms, there being preferably from 2 to 3 carbon atoms between the nitrogen atoms. Examples of such polyamines include ethylenediamine, diethylene triamine, triethylene tetra ine, di (trimethylene) triamine, dipropylene triamine, tetraethylene pentamine, etc. Among the polyalkylene polyamines, polyethylene polyamine and polypropylene polyamine containing 2-12 amine nitrogen atoms and 2-24 carbon atoms are especially preferred and in particular, the lower polyalkylene polyamines, e.g., ethylenediamine, diethylene triamine, propylene diamine, dipropylene triamine, etc. , are most preferred. Particularly preferred polyamines are ethylene diamine and diethylene triamine. Fuel Compositions The fuel additive composition of the present invention will generally be employed in hydrocarbon fuels to prevent and control engine deposits, particularly intake valve deposits. The proper concentration of the additive composition necessary to achieve the desired level of deposit control varies depending upon the type of fuel employed, the type of engine, and the presence of other fuel additives. Generally, the present fuel additive composition will be employed in hydrocarbon fuel in a concentration ranging from about 75 to about 5,000 parts per million (ppm) by weight, preferably from 200 to 2,500 ppm. in terms of individual components, hydrocarbon fuel containing the fuel additive composition of this invention will generally contain about 50 to 2,500 ppm of the poly(oxyalkylene) hydroxyaromatic ester component and about 25 to 1,000 ppm of the aliphatic amine component. The ratio of the poly(oxyalkylene) hydroxyaromatic ester to aliphatic amine will generally range from about 0.5:1 to about 10:1, and will preferably be about 1:1 or greater. The fuel additive composition of the present invention may be formulated as a concentrate using an inert stable oleophilic (i.e., dissolves in gasoline) organic solvent boiling in the range of about 150°F to 400°F (about 65°C to 205°C) . Preferably, an aliphatic or an aromatic hydrocarbon solvent is used, such as benzene, toluene, xylene or higher-boiling aromatics or aromatic thinners. Aliphatic alcohols containing about 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, n-butanol and the like, in combination with hydrocarbon solvents are also suitable for use with the present additives. In the concentrate, the amount of the additive composition will generally range from about 10 to about 70 weight percent, preferably 10 to 50 weight percent, more preferably from 20 to 40 weight percent. in gasoline fuels, other fuel additives may be employed with the additives of the present invention, including, for example, oxygenates, such as t-butyl methyl ether, antiknock agents, such as methylcyclopentadienyl manganese tricarbonyl, and other dispersants/detergents, such as hydrocarbyl amines or succinimides. Additionally, antioxidants, metal deactivators and demulsifiers may be present. in diesel fuels, other well-known additives can be employed, such as pour point depressants, flow improvers, cetane " improvers, and the like. A fuel-soluble, nonvolatile carrier fluid or oil may also be used with the fuel additive composition of this invention. The carrier fluid is a chemically inert hydrocarbon-soluble liquid vehicle which substantially increases the nonvolatile residue (NVR) , or solvent-free liquid fraction of the fuel additive composition while not overwhelmingly contributing to octane requirement increase. The carrier fluid may be a natural or synthetic oil, such as mineral oil, refined petroleum oils, synthetic polyalkanes and alkenes, including hydrogenated and unhydrogenated polyalphaolefins, and synthetic poly(oxyalkylene) -derived oils, such as those described, for example, in U.S. Patent No. 4,191,537 to Lewis. These carrier fluids are believed to act as a carrier for the fuel additive composition of the present invention and to assist in removing and retarding deposits. The carrier fluid may also exhibit synergistic deposit control properties when used in combination with the fuel additive composition of this invention. The carrier fluids are typically employed in amounts ranging from about 100 to about 5000 ppm by weight of the hydrocarbon fuel, preferably from 400 to 3000 ppm of the fuel. Preferably, the ratio of carrier fluid to deposit control additive will range from about 0.5:1 to about 10:1, more preferably from 1:1 to 4:1, most preferably about 2:1. When employed in a fuel concentrate, carrier fluids will generally be present in amounts ranging from about 20 to about 60 weight percent, preferably from 30 to 50 weight percent. EXAMPLES The following examples are presented to illustrate specific embodiments of the present invention and synthetic preparations thereof; and should not be interpreted as limitations upon the scope of the invention. Example 1 Preparation of 4-Benzyloxybenzoyl Chloride To a flask equipped with a magnetic stirrer and drying tube was added 10.0 grams of 4-benzyloxybenzoic acid and 100 L of anhydrous diethyl ether and then 19.1 L of oxalyl chloride. The resulting mixture was stirred at room temperature for 16 hours and then the solvent was removed in vacuo to yield 10.8 grams of the desired acid chloride. Example 2 Preparation of g- (4-Benzyloxybenzoyl) -ω-4-dodecylphenoxypoly (oxybutylene! O CH,CH 3 PhCH,-0-<( J V-C-(0-CHCH,) _ 19 sr * l o 4-Benzyloxybenzoyl chloride (10.8 grams) from Example 1 was combined with 72.2 grams of α-hydroxy-ω-4-dodecylphenoxy- poly(oxybutylene) having an average of 19 oxybutylene units (prepared essentially as described in Example 6 of U.S. Patent No. 4,160,648) and 150 mL of anhydrous toluene. Triethylamine (6.41 mL) and 4-dimethylaminopyridine (0.54 grams) were then added and the resulting mixture was heated to reflux under nitrogen for 16 hours. The reaction was then cooled to room temperature and diluted with 300 mL of diethyl ether. The organic layer was washed twice with 1% aqueous hydrochloric acid, twice with saturated aqueous sodium bicarbonate solution, and once with saturated aqueous sodium chloride. The organic layer was then dried over anhydrous magnesium sulfate, filtered and the solvents removed in vacuo to yield 76.5 grams of a light brown oil. The oil was chromatographed on silica gel, eluting with hexane/diethyl ether/ethanol (8:1.5:0.5) , to yield 43.2 grams of the desired product as a colorless oil. Example 3 Preparation of g-(4-Hvdroxybenzoyl) -ω-4-dodecylphenoxypoly(oxybutylene) A solution of 15.9 grams of the product from Example 2 in 50 mL of ethyl acetate and 50 mL of acetic acid containing 3.48 grams of 5% palladium on charcoal was hydrogenolyzed at 35-40 psi for 16 hours on a Parr low-pressure hydrogenator. Catalyst filtration and removal of residual acetic acid with toluene in vacuo yielded 14.6 grams of the desired product as a colorless oil. The product had an average of 19 oxybutylene units. IR (neat) 1715 cm "1 ; Η NMR (CDC1 3 ) δ 7.9, 7.3 (AB quartet, 4H) , 7.1-7.25 (m, 2H) , 6.7-6.9 (m, 2H) , 5.05-5.15 (m, IH) , 3.1-4.0 (m, 56H) , 0.5-1.9 (m, 120H) . Similarly, by using the above procedures and the appropriate starting materials and reagents, the following compounds can by prepared: α-(4-hydroxybenzoyl) -ω-n-butyloxypoly(oxybutylene) ; α-(4-hydroxybenzoyl) -ω-4-t-butylphenoxypoly(oxybutylene) ; α-(4-hydroxybenzoyl) -ω-4-octacosylphenoxypoly(oxybutylene) ; α-(4-hydroxy-3-methoxybenzoyl) -ω-4-dodecylphenoxy- poly(oxybutylene) ; α-(4-hydroxy-3-methybenzoyl) -ω-4-dodecylphenoxy- poly(oxybutylene) ; and - (3 ,4-dihydroxybenzoyl) -ω-4-dodecylphenoxy- poly(oxybutylene) . Example 4 Preparation of g- (4-Hydroxybenzoyl)-ω-n-butoxypoly(oxypropylene. H,) _, 5 -0-(CH,) 3 CH 3 To a flask equipped with a magnetic stirrer, thermometer, Dean-Stark trap, nitrogen inlet and reflux condenser was added 4.52 grams of 4-hydroxybenzoic acid, 50.0 grams of α-hydroxy-ω-n-butoxypoly(oxypropylene) having an average of 25 oxypropylene units (commercially available from Union Carbide as LB385) and 0.56 grams of p-toluenesulfonic acid. The reaction was heated to 120°C for 16 hours and then cooled to room temperature. Diethyl ether (750 mL) was added and the organic phase was washed twice with saturated aqueous sodium bicarbonate, and once with saturate aqueous sodium chloride solution. The organic layer was then dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo to afford 51.7 grams of a brown oil. The oil was . chromatographed on silica gel, eluting with hexane/ethyl acetate/ethanol (49:49:2) to yield 25.2 grams of the desired product as a yellow oil. The product had an average of 25 oxypropylene units. IR (neat) 1715 cm "1 ; Η NMR (CDC1 3 ) δ 7.9, 6.85 (AB quartet, 4H) , 5.05-5.15 (m, IH) , 3.1-4.0 (m, 76H) , 1.4-1.6 (m, 2H) , 1.25-1.4 (m, 2H) , 0.9-1.4 (m, 75H) , 0.75-0.9 (t, 3H) . Similarly, by using the above procedures and the appropriate starting materials and reagents, the following compounds can by prepared: a- (4-hydroxybenzoyl) -ω-4-t-butylphenoxypoly (oxypropylene) ; -(4-hydroxybenzoyl) -ω-4-dodecylphenoxypoly(oxypropylene) ; -(4-hydroxy-3-methoxybenzoyl) -ω-n-butoxypoly(oxypropylene) ; α- (4-hydroxy-3-methybenzoyl) -ω-n-butoxypoly(oxypropylene) ; and a- (3, 4-dihydroxybenzoyl) -ω-n-butoxypoly(oxybutylene) . Example 5 Preparation of 2-Benzyloxybenzoyl Chloride To a flask equipped with a magnetic stirrer and drying tube was added 15.0 grams of 2-benzyloxybenzoic acid and 150 mL of anhydrous dichloromethane followed by 28.7 mL of oxalyl chloride. The reaction was stirred at room temperature for 16 hours, and then the solvent was removed in vacuo to yield 16.2 grams of the desired acid chloride. Example 6 Preparation of g- (2-Benzyloxybenzoyl) -ω-4-dodecylphenoxypolv(oxybutylene) 2-Benzyloxybenzoyl chloride (16.2 grams) from Example 5 was combined with 108.3 grams of α-hydroxy-ω-4-dodecylphenoxy- poly(oxybutylene) having an average of 19 oxybutylene units (prepared essentially as described in Example 6 of U.S. Patent No. 4,160,648) and 225 mL of anhydrous toluene. Triethylamine (9.6 mL) and 4-dimethylaminopyridine (0.8 grams) were added and the reaction was heated to reflux under nitrogen for 16 hours, then cooled to room temperature and diluted with 500 mL of diethyl ether. The organic layer was washed twice with 1% aqueous hydrochloric acid, twice with saturated aqueous sodium bicarbonate solution, and once with saturated aqueous sodium chloride. The organic layer was then dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo to yield 119.2 grams of a light brown oil. The oil was chromatographed on silica gel, eluting with hexane/diethyl ether/ethanol (8:1.5:0.5) to yield 73.0 grams of the desired product as a light brown oil. Example 7 Preparation of g-(2-Hydroxybenzoyl) -ω-4-dodecylphenoxypoly(oxybutylene) A solution of 30.8 grams of the product from Example 6 in 95 mL of ethyl acetate and 95 mL of acetic acid containing 3.39 grams of 10% palladium on charcoal was hydrogenolyzed at 35-40 psi for 16 hours on a Parr low-pressure hydrogenator. Catalyst filtration and removal of solvent in vacuo followed by azeotropic removal of residual acetic acid with toluene under vacuum yielded 28.9 grams of the desired product as a light brown oil. The product had an average of 19 oxybutylene units. IR (neat) 1673 cm "1 , Η NMR (CDCL3) δ 10.85 (s, IH) , 7.8-8.2 (m, 8H) , 5.1-5.3 (m, IH) , 3.2-4.1 (m, 56H) , 0.5-1.9 (m, 21H) . Example 8 Preparation of g-(3-Hydroxybenzoyl) -ω-4-dodecylphenoxypolv(oxybutylene) To a flask equipped with a magnetic stirrer, thermometer, Dean-Stark trap, nitrogen inlet and reflux condenser was added 5.08 grams of 3-hydroxybenzoic acid, 50.0 grams of α-hydroxy-ω-4-dodecylphenoxy-poly(oxybutylene) having an average of 19 oxybutylene units (prepared essentially as described in Example 6 of U.S. Patent No. 4,160,648) and 0.53 grams of p-toluenesulfonic acid. The reaction was heated to 130°C for 48 hours and then cooled to room temperature. Diethyl ether (750 mL) was added and the organic phase was washed twice with saturated aqueous sodium bicarbonate and once with saturated aqueous sodium chloride solution. The organic layer was then dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo to afford 47.8 grams of a brown oil. The oil was chromatographed on silica gel, eluting with hexane/ethyl acetate/ethanol (78:20:2) to yield 16.5 grams of the desired product as a yellow oil. The product had an average of 19 oxybutylene groups. IR (neat) 1716 cm "1 ; Η NMR (CDC1 3 ) δ 6.6-7.6 (m, 8H) , 4.9-5.2 (m, IH) , 3.1-4.0 (m, 56H) , 0.5-1.9 (m, 21H) . 01 Example 9 02 03 Preparation of 3.5-Di-t-butyl-4-hydroxybenzoyl Chloride 04 05 TO a flask equipped with a magnetic stirrer, reflux 06 condenser and nitrogen inlet was added 1.88 grams of 07 3,5-di-t-butyl-4-hydroxybenzoic acid and 15 mL of thionyl 08 chloride. The reaction was refluxed for 2 hours and stirred 09 at room temperature for 16 hours. The excess thionyl 10 chloride was removed in vacuo to yield 2.2 grams of the 11 desired acid chloride as a white solid. 12 13 Example 10 I 4 15 Preparation of α-(3 ,5-Di-t-butyl-4-hydroxybenzoyl) - 16 ω-4-dodecylphenoxypolv(oxybutylene) 2 3 , 5-Di-t-butyl-4-hydroxybenzoyl chloride (2.2 grams) from 3 Example 9 was combined with 13.6 grams of α-hydroxy-ω-4- 4 dodecylphenoxy-poly(oxybutylene) having an average of 19 5 oxybutylene units (prepared essentially as described in 6 Example 6 of U.S. Patent No. 4,160,648) and 50 mL of 7 anhydrous toluene. Triethylamine (1.17 mL) and 8 4-dimethylaminopyridine (0.1 grams) were added and the 9 reaction was heated to reflux under nitrogen for 16 hours, 0 and then cooled to room temperature and diluted with 100 L 1 of hexane. The organic layer was washed twice with water, 2 once with saturated aqueous sodium bicarbonate solution and 3 once with saturated aqueous sodium chloride. The organic 4 01 layer was dried over anhydrous magnesium sulfate, filtered 02 and concentrated in vacuo to give an oil. The oil was 03 chromatographed on silica gel, eluting with hexane/diethyl 04 ether/ethanol (6:3.5:0.5) to yield 3.0 grams of the desired 05 product as a yellow oil. IR (neat) 1715 cm '1 ,- Η NMR (CDC1 3 ) 06 <S 7.8 (s, 2H) , 7.1-7.25 (m, 2H) , 6.7-6.9 (m, 2H) , 5.7 (s, 07 IH) , 7.1-7.25 (m, 2H) , 6.7-6.9 (m, 2H) , 5.7 (s, IH) , 08 5.05-5.15 ( , IH) , 3.1-4.0 (m, 56H) , 0.5-1.9 (m, 138H) . 09 10 Example 11 11 12 Preparation of - (3 , 5-Di-t-butyl-4-hydroxybenzoyl) 13 ω-n-butoxypolv(oxypropylene) 14 H,) _, 5 -0-(CH,) 3 CH 3 19 3 , 5-Di-t-butyl-4-hydroxybenzoyl chloride (8.0 grams) 20 prepared as described in Example 9 was combined with 21 46.2 grams of α-hydroxy-ω-n-butoxypoly(oxypropylene) having 22 an average of 25 oxypropylene units (commercially available 23 from Union Carbide as LB385) and 200 mL of anhydrous 24 toluene. Triethylamine (4.4 mL) and 4-dimethylaminopyridine 25 (0.37 grams) were added and the reaction was heated to 6 reflux under nitrogen for 16 hours, and then cooled to room 7 temperature and diluted with 500 mL of hexane. The organic 8 layer was washed twice with water, once with saturated 9 aqueous sodium bicarbonate solution and once with saturated 0 aqueous sodium chloride. The organic layer was dried over 1 anhydrous magnesium sulfate, filtered and concentrated in 2 vacuo to give an oil. The oil was chromatographed on silica 3 gel, eluting with hexane/diethyl ether/ethanol (6:3.5:0.5) 4 01 to yield 42.0 grams of the desired product as a yellow oil, 02 The product had an average of 25 oxypropylene units. IR 03 (neat) 1715 cm "1 ; Η NMR (CDC1 3 ) δ 7.8 (s, 2H) , 5.7 (s, IH) , 0 5.05-5.15 ( , IH) , 3.2-3.9 (m, 75H) , 0.9-1.6 (m, 97H) , 05 0.75-0.9 (t, 3H) . 06 07 Example 12 08 09 Preparation of α-[ (4-Hydroxyphenyl)acetyl) - 1° ω-4-dodecylphenoxypolv(oxybutylene) 11 I 2 0 CH,CH 3 13 HO- )V-CH,C-(O-CHCH,) _ 19 -0— )Vc 12 H 25 14 15 16 To a flask equipped with a magnetic stirrer, thermometer, 17 Dean-Stark trap, nitrogen inlet and reflux condenser was 18 added 4.66 grams of 4-hydroxyphenylacetic acid, 50.0 grams 19 of α-hydroxy-ω-4-dodecylphenoxypoly(oxybutylene) having an 0 average of 19 oxybutylene units (prepared essentially as 1 described in Example 6 of U.S. Patent No. 4,160,648) and 2 0.63 grams of p-toluenesulfonic acid. The reaction was 3 heated to 120°C for 16 hours and then cooled to room 4 temperature. Diethyl ether (750 mL) was added and the 5 organic phase was washed twice with saturated aqueous sodium 6 bicarbonate, and then once with saturated aqueous sodium 7 chloride solution. The organic layer was dried over 8 anhydrous magnesium sulfate, filtered and concentrated in 9 vacuo to afford 51.6 grams of a brown oil. The oil was 0 chromatographed on silica gel, eluting with hexane/ethyl 1 acetate/ethanol (93:5:2) to yield 26.2 grams of the desired 2 product as a yellow oil. The product had an average of 19 3 oxybutylene units. IR (neat) 1742 cm "1 ; l H NMR (CDC1 3 ) δ 4 6.7-7.25 ( , 8H) , 4.8-5.0 (m, IH) , 3.1-4.05 (m, 58H) , 0.5-1.9 (m, 120H) . Example 13 Preparation of α-[3-(4-Hydroxyphenyl)propionyl) ω-4-dodecylphenoxypolv(oxybutylene) To a flask equipped with a magnetic stirrer, thermometer, Dean-Stark trap, nitrogen inlet and reflux condenser was added 5.09 grams of 3-(4-hydroxyphenyl)propionic acid, 50.0 grams of α-hydroxy-ω-4-dodecylphenoxypoly(oxybutylene) having an average of 19 oxybutylene units (prepared essentially as described in Example 6 of U.S. Patent No. 4,160,648) and 0.63 grams of p-toluenesulfonic acid. The reaction was heated to 120°C for 16 hours and then cooled to room temperature. Diethyl ether (750 L) was added and the organic phase was washed twice with saturated- aqueous sodium bicarbonate, and once with saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo to afford 52.7 grams of a brown oil. The oil was chromatographed on silica gel, eluting with hexane/ethyl acetate/ethanol (93:5:2) to yield 37.5 grams of the desired product as a yellow oil. IR (neat) 1735 cm '1 ; Η NMR (CDC1 3 ) <S 6.7-7.25 (m, 8H) , 4.8-5.0 ( , IH) , 3.1-4.05 (m, 56H) , 2.9 (t, 2H) , 2.55 (t, 2H) , 0.5-0.9 (m, 120H) . Example 14 Preparation of α-Benzyloxy-ω-4-hvdroxypoly(oxybutylene) To a flask equipped with a mechanical stirrer, thermometer, addition funnel, reflux condenser and nitrogen inlet was added 1.59 grams of a 35 wt.% dispersion of potassium hydride in mineral oil. Benzyl alcohol (5.0 grams) dissolved in 250 mL of anhydrous toluene was added dropwise. After hydrogen evolution had subsided, the reaction was heated to reflux for 3 hours and then cooled to room temperature. 1, 2-Epoxybutane (99.6 mL) were then added dropwise and the reaction was refluxed for 16 hours. The reaction was cooled to room temperature, quenched with 5 mL of methanol and diluted with 500 mL of diethyl ether. The resulting mixture was washed with saturated aqueous ammonium chloride, followed by water and saturated aqueous sodium chloride. The organic layer was dried over anhydrous magnesium sulfate, filtered and the solvents removed in vacuo to yield 64.1 grams of a yellow oil. The oil was chromatographed on silica gel, eluting with hexane/ethyl acetate/ethanol (90:8:2) to afford 40 grams of the desired product as a light yellow oil. Example 15 Preparation of -(4-Benzyloxybenzoyl) -ω-benzyloxypoly(oxybutylene! PhCH,-0 4-Benzyloxybenzoyl chloride (10.8 grams) from Example 1 was combined with α-benzyloxy-ω-hydroxy-poly(oxybutylene) (15.0 grams) from Example 14 and 50 mL of anhydrous toluene. Triethylamine (1.3 mL) and 4-dimethylaminopyridine (0.55 grams) were then added and the resulting mixture was heated to reflux under nitrogen for 16 hours. The reaction was then cooled to room temperature and diluted with 100 mL of diethyl ether. The organic layer was washed twice with 1% aqueous hydrochloric acid, twice with saturated aqueous sodium bicarbonate solution, and once with saturated aqueous sodium chloride. The organic layer was then dried over anhydrous magnesium sulfate, filtered and the solvents removed in vacuo to yield 16.8 grams of the desired product as a yellow oil. Example 16 Preparation of g-(4-Hvdroxybenzoyl) -ω-hvdroxypolv(oxybutylene) O CH,CH *,3 HO- f ) V-C-(0-CHCH,) _,,-OH A solution of 16.8 grams of the product from Example 15 in 100 mL of ethyl acetate and 100 mL of acetic acid containing 3.0 grams of 5% palladium on charcoal was hydrogenolyzed at 35-40 psi for 16 hours on a Parr low-pressure hydrogenator. Catalyst filtration and removal of residual acetic acid with toluene in vacuo yielded 14.8 grams of the desired product as a yellow oil. The product had an average of 21 oxybutylene units. IR (neat) 1715 cm "1 ; Η NMR (CDC1 3 ) δ 7.9, 6.8 (AB quartet, 4H) , 5.05-5.15 (m, IH) , 3.1-3.9 (m, 62H) , 0.6-1.9 (m, 105H) . Example 17 Single-Cylinder Engine Test The test compounds were blended in gasoline and their deposit reducing capacity determined in an ASTM/CFR single-cylinder engine test. A Waukesha CFR single-cylinder engine was used. Each run was carried out for 15 hours, at the end of which time the intake valve was removed, washed with hexane and weighed. The previously determined weight of the clean valve was subtracted from the weight of the value at the end of the run. The differences between the two weights is the weight of the deposit. A lesser amount of deposit indicates a superior additive. The operating conditions of the test were as follows: water jacket temperature 200°F; vacuum of 12 in Hg, air-fuel ratio of 12, ignition spark timing of 40° BTC; engine speed is 1800 rpm; the crankcase oil is a commercial 30W oil. The amount of carbonaceous deposit in milligrams on the intake valves is reported for each of the test compounds in Table I. TABLE I . Intake Valve Deposit Weight (in milligrams) Sample 1 Base Fuel Example 3 Example 4 Example 7 Example 8 Example 10 Example 11 Example 12 Example 13 Example 16 At 200 parts per million actives (ppma) The base fuel employed in the above single-cylinder engine tests was a regular octane unleaded gasoline containing no fuel detergent. The test compounds were admixed with the base fuel to give a concentration of 200 ppma (parts per million actives) . The data in Table I illustrates the significant reduction in intake valve deposits provided by the poly(oxyalkylene) hydroxyaromatic ester component of the present fuel additive composition (Examples 3, 4, 7, 8, 10, 11, 12, 16) compared to the base fuel. Example 18 Multicylinder Engine Test The fuel additive composition of the present invention was tested in a laboratory multicylinder engine to evaluate their intake valve and combustion chamber deposit control performance. The test engine was a ' 4.3 liter, TBI (throttle body injected) , V6 engine manufactured by General Motors Corporation. The major engine dimensions are set forth in Table II: Table II • Engine Dimensions Bore 10.16 cm Stroke 8.84 cm Displacement Volume 4.3 liter Compression Ratio 9.3:1 The test engine was operated for 40 hours (24 hours a day) on a prescribed load and speed schedule representative of typical driving conditions. The cycle for engine operation during the test is set forth in Table III. Table I I I En ine Driving Cycle , All steps, except step number 3, include a 15 second transition ramp. Step 3 includes a 20 second transition ramp. All of the test runs were made with the same base gasoline, which was representative of commercial unleaded fuel. The results are set forth in Table IV. Table IV Multicylinder Engine Test Results Combustion Cone. Intake Valve Chamber Sample (ppma) Deposits 1 Deposits 1 Base Fuel 972 1902 Poly(oxyalkylene) Hydroxyaromatic Ester 2 400 48 2189 Aliphatic Amine/neutral oil 3 200/800 291 2900 Poly(oxyalkylene) Hydroxyaromatic Ester/ Aliphatic 400/200 57 2501 Amine 4 Average of two runs, in milligrams (mg) . α-(4-Hydroxybenzoyl) -ω-4-dodecylphenoxy- poly(oxybutylene) prepared as described in Example 3. Mixture of 200 ppm polyisobutyl (MW=1300) ethylene diamine and 800 ppm of Chevron 500R neutral oil. The polyisobutyl group was derived from Parapol 1300 polyisobutene. Mixture of 400 ppm of α- (4-Hydroxybenzoyl) -ω-4- dodecylphenoxypoly(oxybutylene) and 200 ppm of polyisobutyl (MW=1300) ethylene diamine. The base fuel employed in the above multicylinder engine tests contained no fuel detergent. The test compounds were admixed with the base fuel at the indicated concentrations. The data in Table IV demonstrates that the combination of a poly(oxyalkylene) hydroxyaromatic ester and an aliphatic amine gives significantly better intake valve deposit control than the aliphatic amine component individually. Moreover, the data in Table IV further demonstrates that the combination produces fewer combustion chamber deposits than the aliphatic amine component alone.

Claims: WHAT IS CLAIMED IS: 1. A fuel additive composition comprising: (a) a poly(oxyalkylene) hydroxyaromatic ' ester having the formula: or a fuel-soluble salt thereof; wherein R, and R, are each independently hydrogen, hydroxy, lower alkyl having 1 to 6 carbon atoms, or lower alkoxy having 1 to 6 carbon atoms; R 3 and R 4 are each independently hydrogen or lower alkyl having 1 to 6 carbon atoms; R 5 is hydrogen, alkyl having 1 to 30 carbon atoms, phenyl, aralkyl or alkaryl having 7 to 36 carbon atoms, or an acyl group having the formula: wherein R 6 is alkyl having 1 to 30 carbon atoms, phenyl, or aralkyl or alkaryl having 7 to 36 carbon atoms; R 7 and R 8 are each independently hydrogen, hydroxy, lower alkyl having 1 to 6 carbon atoms, or lower alkoxy having 1 to 6 carbon atoms; n is an integer from 5 to 100; and x and y are each independently an integer from 0 to 10; and (b) an aliphatic amine having at least one basic nitrogen atom and containing a hydrocarbyl group which has sufficient molecular weight and carbon chain length to render the aliphatic amine soluble in hydrocarbons boiling in the gasoline or diesel fuel range. 2. The fuel additive composition according to Claim 1, wherein n of said poly(oxyalkylene) hydroxyaromatic ester is an integer ranging from 10 to 50. 3. The fuel additive composition according to Claim 2, wherein n of said poly(oxyalkylene) hydroxyaromatic ester is an integer ranging from 15 to 30. 4. The fuel additive composition according to Claim 2, wherein R j of said poly(oxyalkylene) hydroxyaromatic ester is hydrogen, hydroxy, or lower alkyl having 1 to 4 carbon atoms; and R, is hydrogen. The fuel additive composition according to Claim 4, wherein R 5 of said poly(oxyalkylene) hydroxyaromatic ester is hydrogen, alkyl having 2 to 22 carbon atoms, or alkylphenyl having an alkyl group containing 4 to 24 carbon atoms. 6. The fuel additive composition according to Claim 5, wherein R j of said poly(oxyalkylene) hydroxyaromatic ester is hydrogen or hydroxy. 7. The fuel additive composition according to Claim 6, wherein R 5 of said poly(oxyalkylene) hydroxyaromatic ester is hydrogen, alkyl having 4 to 12 carbon atoms, or alkylphenyl having an alkyl group containing 4 to 12 carbon atoms. 8. The fuel additive composition according to Claim 7, wherein one of R 3 and R 4 of said poly(oxyalkylene) hydroxyaromatic ester is lower alkyl having 1 to 3 carbon atoms and the other is hydrogen. 9. The fuel additive composition according to Claim 8, wherein one of R 3 and R 4 of said poly(oxyalkylene) hydroxyaromatic ester is methyl or ethyl and the other is hydrogen. 10. The fuel additive composition according to Claim 9, wherein x of said poly(oxyalkylene) hydroxyaromatic ester is 0, 1 or 2. 11. The fuel additive composition according to Claim 10, wherein R, of said poly(oxyalkylene) hydroxyaromatic ester is hydrogen, R 5 is alkylphenyl having an alkyl group containing 4 to 12 carbon atoms, and x is 0. 12. The fuel additive composition according to Claim 1, wherein said aliphatic amine contains a hydrocarbyl group having a molecular weight in the range of about 250 to about 3,000. 13. The fuel additive composition according to Claim 1, wherein said aliphatic amine is selected from the group consisting of: (l) A straight or branched chain hydrocarbyl-substituted amine having at least one basic nitrogen atom wherein the hydrocarbyl group has a number average molecular weight of about 250 to 3,000; (2) A hydroxyalkyl-substituted amine comprising the reaction product of (i) a polyolefin epoxide derived from a branched-chain polyolefin having a number average molecular weight of about 250 to 3,000, and (ii) a nitrogen-containing compound selected from ammonia, a monoamine having from 1 to • 40 carbon atoms, and a polyamine having from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms; and (3) A straight or branched chain hydrocarbyl- substituted succinimide comprising the reaction product of a straight or branched chain hydrocarbyl-substituted succinic acid or anhydride, wherein the hydrocarbyl group has a number average molecular weight of about 250 to 3,000, and a polyamine having from 2 to about 12 amine nitrogen atoms and 2 to about 40 carbon atoms. 14. The fuel additive composition according the Claim 13, wherein the hydrocarbyl or hydroxyalkyl substituent on the aliphatic amine of component (b) has a number average molecular weight of about 700 to 2,200. 15. The fuel additive composition according to Claim 14, wherein the hydrocarbyl or hydroxyalkyl substituent on the aliphatic amine of component (b) has a number average molecular weight of about 900 to 1,500. 16. The fuel additive composition according to Claim 13, wherein the aliphatic amine of component (b) is a straight or branched chain hydrocarbyl-substituted amine. 17. The fuel additive composition accord to Claim 16, wherein the aliphatic amine of component (b) is a branched chain hydrocarbyl-substituted amine. is. The fuel additive composition according to Claim 17, wherein the aliphatic amine of component (b) is a polyisobutyl amine. 19. The fuel additive composition according to Claim 16, wherein the amine moiety of the aliphatic amine is derived from a polyamine having from 2 to 12 amine nitrogen atoms and from 2 to 40 carbon atoms. 20. The fuel additive composition according to Claim 19, wherein the polyamine is a polyalkylene polyamine having 2 to 12 amine nitrogen atoms and 2 to 24 carbon atoms. 21. The fuel additive composition according to Claim 20, wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine and tetraethylene pentamine. 22. The fuel additive composition according to Claim 21, wherein the polyalkylene polyamine is ethylene diamine or diethylene triamine. 23. The fuel additive composition according to Claim 13, wherein the aliphatic amine of component (b) is hydroxyalkyl-substituted amirie. 24. The fuel additive composition according to Claim 23, wherein the hydroxyalkyl-substituted amine is derived from a branched chain polyolefin selected from polypropylene or polyisobutene. 25. The fuel additive composition according to Claim 24, wherein the branched chain polyolefin is polyisobutene. 26. The fuel additive composition according to Claim 23, wherein the hydroxyalkyl-substituted amine is derived from a polyamine having from 2 to about 12 amine nitrogen atoms and 2 to about 40 carbon atoms. 27. The fuel additive composition according to Claim 24, wherein the polyamine ia a polyalkylene polyamine wherein the alkylene group contains from 2 to 6 carbon atoms and the polyalkylene polyamine contains from 2 to 12 nitrogen atoms and from 2 to 24 carbon atoms. 28. The fuel additive composition according to Claim 27, wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, polyethylene polyamine, propylene diamine and polypropylene polyamine. 29. The fuel additive composition according to Claim 13, wherein the aliphatic amine of component (b) is a straight or branched chain hydrocarbyl-substituted succinimide. 30. The fuel additive composition according to Claim 29, wherein the aliphatic amine is a branched chain hydrocarbyl-substituted succinimide. 31. The fuel additive composition according to Claim 30, wherein the branched chain hydrocarbyl substituent is polyisobutyl. 32. The fuel additive composition according to Claim 29, wherein the hydrocarbyl-substituted succinimide is derived from a polyalkylene polyamine having 2 to 12 amine nitrogen atoms and 2 to 24 carbon atoms. 33. The fuel additive composition according to Claim 32, wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine and tetraethylene pentamine. 34. The fuel additive composition according to Claim 33, wherein the polyalkylene polyamine is ethylene diamine or diethylene triamine. 35. A fuel composition comprising a major amount of hydrocarbons boiling in the gasoline or diesel range and an effective detergent amount of a fuel additive composition comprising: (a) a poly(oxyalkylene) hydroxyaromatic ester having the formula: ) n -0-R 5 or a fuel-soluble salt thereof; wherein R j and R, are each independently hydrogen, hydroxy, lower alkyl having 1 to 6 carbon atoms, or lower alkoxy having 1 to 6 carbon atoms; R 3 and R 4 are each independently hydrogen or lower alkyl having 1 to 6 carbon atoms; R 5 is hydrogen, alkyl having 1 to 30 carbon atoms, phenyl, aralkyl or alkaryl having 7 to 36 carbon atoms, or an acyl group having the formula: wherein R 6 is alkyl having 1 to 30 carbon atoms, phenyl, or aralkyl or alkaryl having 7 to 36 carbon atoms; R 7 and R 8 are each independently hydrogen, hydroxy, lower alkyl having 1 to 6 carbon atoms, or lower alkoxy having 1 to 6 carbon atoms; n is an integer from 5 to 100; and x and y are each independently an integer from 0 to 10; and (b) an aliphatic amine having at least one basic nitrogen atom and containing a hydrocarbyl group which has sufficient molecular weight and carbon chain length to render the aliphatic amine soluble in hydrocarbons boiling in the gasoline or diesel fuel range. 36. The fuel composition according to Claim 35, wherein R, of said poly(oxyalkylene) hydroxyaromatic ester is hydrogen, hydroxy, or lower alkyl having 1 to 4 carbon atoms; R, is hydrogen; one of R 3 and R 4 is hydrogen and the other is methyl or ethyl; R 5 is hydrogen, alkyl having 2 to 22 carbon atoms, or alkylphenyl having an alkyl group containing 4 to 24 carbon atoms; n is 15 to 30 and x is 0, 1 or 2. 37. The fuel composition according to Claim 36, wherein R, of said poly(oxyalkylene) hydroxyaromatic ester is hydrogen or hydroxy; R 5 is hydrogen, alkyl having 4 to 12 carbon atoms, or alkylphenyl having an alkyl group containing 4 to 12 carbon atoms; and x is 0. 38. The fuel composition according to Claim 37, wherein R ] of said poly(oxyalkylene) ester is hydrogen, and R 5 is alkylphenyl having an alkyl group containing 4 to 12 carbon atoms. 39. The fuel composition according to Claim 35, wherein said aliphatic amine is a polyisobutyl amine. 40. The fuel composition according to Claim 39, wherein the amine moiety is derived from a polyamine having from 2 to 12 amine nitrogen atoms and from 2 to 40 carbon atoms. 41. The fuel composition according to Claim 40, wherein said polyamine is selected from the group consisting of ethylenediamine, propylenediamine, diethylenetriamine and dipropylenetriamine. 42. The fuel composition according to Claim 41, wherein the amine moiety is derived from ethylenediamine or diethylenetriamine. 43. The fuel composition according to Claim 35, wherein said composition contains about 50 to about 2,500 pa^ts per million by weight of said poly(oxyalkylene) hydroxyaromatic ester and about 25 to about 1,000 parts per million of said aliphatic amine. A fuel concentrate comprising an inert stable oleophilic organic solvent boiling in the range of from about 150°F to 400°F and from about 10 to about 70 weight percent of a fuel additive composition comprising: (a) a poly(oxyalkylene) hydroxyaromatic ester having the formula: or a fuel-soluble salt thereof; wherein R ] and R, are each independently hydrogen, hydroxy, lower alkyl having 1 to 6 carbon atoms, or lower alkoxy having 1 to 6 carbon atoms; R 3 and R 4 are each independently hydrogen or lower alkyl having 1 to 6 carbon atoms; R 5 is hydrogen, alkyl having 1 to 30 carbon atoms, phenyl, aralkyl or alkaryl having 7 to 36 carbon atoms, or an acyl group having the formula: OH wherein R 6 is alkyl having 1 to 30 carbon atoms, phenyl, or aralkyl or alkaryl having 7 to 36 carbon atoms; R 7 and R 8 are each independently hydrogen, hydroxy, lower alkyl having 1 to 6 carbon atoms, or lower alkoxy having 1 to 6 carbon atoms; n is an integer from 5 to 100; and x and y are each independently an integer from 0 to 10; and (b) an aliphatic amine having at least one basic nitrogen atom and containing a hydrocarbyl group which has sufficient molecular weight and carbon chain length to render the aliphatic amine soluble in hydrocarbons boiling in the gasoline or diesel fuel range. 45. The fuel concentrate according to Claim 44, wherein R, of said poly(oxyalkylene) hydroxyaromatic ester is hydrogen, hydroxy, or lower alkyl having 1 to 4 carbon atoms; R, is hydrogen; one of R 3 and R 4 is hydrogen and the other is methyl or ethyl; R 5 is hydrogen, alkyl having 2 to 22 carbon atoms, or alkylphenyl having an alkyl group containing 4 to 24 carbon atoms; n is 15 to 30 and x is 0, 1 or 2. 46. The fuel concentrate according to Claim 45, wherein R, of said poly(oxyalkylene) hydroxyaromatic ester is hydrogen or hydroxy; R s is hydrogen, alkyl having 4 to 12 carbon atoms, or alkylphenyl having an alkyl group containing 4 to 12 carbon atoms; and x is 0. 47. The fuel concentrate according to Claim 46, wherein R, of said poly(oxyalkylene) hydroxyaromatic ester is hydrogen, and R 5 is alkylphenyl having an alkyl group containing 4 to 12 carbon atoms. 48. The fuel concentrate according to Claim 44, wherein said aliphatic amine is a polyisobutyl amine. 49. The fuel concentrate according to Claim 48, and wherein the amine moiety is derived from a polyamine having from 2 to 12 amine nitrogen atoms and from 2 to 40 carbon atoms. 50. The fuel concentrate according to Claim 49, wherein said polyamine is selected from the group consisting of ethylenediamine, propylenediamine, diethylenetriamine and dipropylenetriamine. 51. The fuel concentrate according to Claim 50, wherein the amine moiety is derived from ethylenediamine or diethylenetriamine.

Inventors: CHERPECK RICHARD E, CHERPECK, RICHARD, E.
Applicants: CHEVRON RES & TECH, CHEVRON RESEARCH AND TECHNOLOGY COMPANY
Application year: 1993
Main classification: C10L1
IPC codes: C10L1, C10L10