MXPA98000316A

MXPA98000316A - Compositions of fuel additives containing polyalkylphenoxyaminoalcanes and poly (oxialquilen) ami

Info

Publication number: MXPA98000316A
Application number: MXPA/A/1998/000316A
Authority: MX
Inventors: E Cherpeck Richard; E Morris Jack; R Ahmadi Majid
Original assignee: Chevron Chemical Company
Priority date: 1996-05-14
Filing date: 1998-01-09
Publication date: 1998-11-16

Abstract

The present invention describes a fuel additive composition, comprising: (a) a polyalkylphenoxyaminoalkane compound of the formula: (See Formula) or a fuel soluble salt thereof, wherein R is a polyalkyl group having a weight average molecular in the range of about 600 to 5,000; R1 and R2 are independently hydrogen or lower alkyl having from 1 to 6 carbon atoms, and A is amino, N-alkyl amino having from 1 to about 20 carbon atoms in the alkyl, N, N-dialkyl amino group having about 1 to about 20 carbon atoms in each alkyl group, or a polyamine portion having about 2 to about 12 amine nitrogen atoms and about 2 to about of carbon atoms, and (b) a poly (oxyalkylene) amine having at least one basic nitrogen atom and a sufficient number of oxyalkylene units to render the poly (oxyalkylene) amine soluble in hydrocarbons boiling in the fuel range of gasoline or diesel. The fuel additive compositions of this invention are useful as fuel additives for the prevention and control of deposits in the fuel.

Description

COMPOSITIONS OF FUEL ADDITIVES CONTAINING POLYALYKYLPHENOXYAMINOALCANES AND POLY (OXYALQUYLENE) AMINES BACKGROUND OF THE INVENTION FIELD OF THE INVENTION This invention relates to additive compositions for fuels containing polyalkylphenoxyaminoalkanes and poly (oxyalkylene) amines. In a further aspect, this invention relates to the use of these additive compositions in fuel compositions to prevent and control the deposits in the engine. DESCRIPTION OF THE RELATED ART It is well known that automobile engines tend to form deposits on the surface of the engine components, such as the carburetor holes, the regulator bodies, the fuel injectors, the valves in the cylinder head for the entry of fuel, due to the oxidation and polymerization of the hydrocarbon fuel. These deposits, even when they are present in relatively small amounts, frequently cause considerable problems in the ability to be driven, such as loss of speed and poor acceleration. On the other hand, deposits in the engine can significantly increase fuel consumption by the automobile and the production of REF: 26380 contaminants in the exhaust pipe. Therefore, the development of effective detergents for fuel or additives for "tank control" to prevent or control such deposits is of considerable importance, and numerous materials are known in the art. For example, it is known that phenols substituted with aliphatic hydrocarbons reduce deposits in the engine when used in fuel compositions. U.S. Patent No. 3,849,085, filed November 19, 1974 and given to Kreuz et al., Discloses a motor fuel composition comprising a mixture of hydrocarbons in the boiling range of gasoline containing from about 0.01 to 0.25 volume percent of a phenol substituted with a high molecular weight aliphatic hydrocarbon, in which the aliphatic hydrocarbon radical has an average molecular weight in the range of about 500 to 3,500. This patent discloses that gasoline compositions containing small amounts of a phenol substituted with an aliphatic hydrocarbon not only prevent or inhibit the formation of deposits in the valve which is in the fuel inlet head and in the orifices in a gasoline engine. , but also improves the performance of a gasoline composition of engines designed to operate at higher operating temperatures with minimal decomposition and formation of deposits in the engine manifold. U.S. Patent No. 4,259,086, filed March 31, 1981 and given to Machleder et al., Discloses a detergent additive for fuels and lubricating oils comprising the reaction product of a phenol substituted with an aliphatic hydrocarbon, epichlorohydrin and a monoamine or primary or secondary polyamine. In addition, US Patent No. 4,048,081, filed September 13, 1977 and given to Machleder et al., Discloses a gasoline detergent additive, which is the reaction product of a polyisobutene phenol by epichlorohydrin, followed by amination with ethylenediamine or another polyamine. Similarly, U.S. Patent No. 4,13,846, filed January 16, 1979 and given to Machleder et al., Discloses a fuel additive composition comprising a mixture of (1) the reaction product of a substituted phenol with an aliphatic hydrocarbon, epichlorohydrin and a primary or secondary mono- or polyamine; and (2) a polyalkylenephenol. This patent teaches that such compositions show a detergency in the carburetor, the induction system and the excellent combustion chamber, and furthermore provides an effective rust inhibition when used in hydrocarbon fuels in low concentrations.

It is also known that amino phenols function as detergents / drsants, antioxidants and anti-corrosion agents when used in fuel compositions. U.S. Patent No. 4,320,021, filed March 16, 1982 and given to R. M. Lange, for example, discloses amino phenols having at least one substituent with a substantially saturated hydrocarbon base of at least 30 carbon atoms. The amino phenols of this patent are thought to impart useful and desirable properties to oil-based lubricants and normally liquid fuels. Furthermore, it has been described that polybutylamines are useful for preventing deposits in the fuel inlet system of internal combustion engines. For example, U.S. Patent No. 4,832,702, filed May 23, 1989 and given to Kummer et al., Discloses fuel and lubricant compositions containing additives of polybutyl or polybutobutylamine prepared by hydroformylating a polybutene or polyisobutene, and then holding the resulting oxo product to a Mannich reaction or amination under hydrogenation conditions. Polyether amine fuel additives are also well known in the art for the prevention and control of deposits in the engine. These polyether additives have a polyoxyalkylene "backbone", ie, the polyether portion of the molecule consists of repeated oxyalkylene units. U.S. Patent No. 4,191,537, filed March 4, 1980 and given to Lewis et al., For example, discloses a fuel composition comprising a major portion of hydrocarbons boiling in the gasoline range, and from 30 to 2,000 parts per million of a hydrocarbyl polyoxyalkylene aminocarbamate having a molecular weight from about 600 to 10,000, and at least one basic nitrogen atom. The polyoxyalkylene hydrocarbyl portion is composed of oxyalkylene units having from 2 to 5 carbon atoms in each oxyalkylene unit. These fuel compositions are thought to maintain the cleanliness of the inlet systems without contributing to the deposits in the combustion chamber. Aromatic compounds containing a portion of poly (oxyalkylene) are also known in the art. For example, U.S. Patent No. 4,191,537, mentioned above, discloses alkylphenyl poly (oxyalkylene) polymers which are useful as intermediates in the preparation of alkylphenyl poly (oxyalkylene) aminocarbamates. Similarly, U.S. Patent No. 4,881,945, filed November 21, 1989 and given to Buckley, discloses a fuel composition comprising a hydrocarbon boiling in the range of gasoline or diesel, and from about 30 to about 5,000 parts per million of a fuel-soluble alkylphenylpolyoxyalkyleneaminocarbatoate having at least one basic nitrogen atom and an average molecular weight of about 800 to 6,000, and wherein the alkyl group contains at least 40 carbon atoms. U.S. Patent No. 5,112,364, filed May 12, 1992 and given to Rath et al., Describes gasoline engine fuels containing small amounts of a polyetheramine and / or a polyetheramine derivative, wherein the polyetheramine is prepared by reductive amination of a polyether alcohol initiated with phenol or initiated with alkylphenol with ammonia or a primary amine. U.S. Patent No. 4,247,301, filed January 27, 1981 and given to Honnen, discloses hydrocarbyl substituted poly (oxyalkylene) polyamines, wherein the hydrocarbyl group contains from 1 to 30 carbon atoms, and the polyamine portion contains from 2 to 12 nitrogen atoms of amine and from 2 to 40 carbon atoms. This patent teaches that the additives can be prepared by the reaction of a suitable hydrocarbyl-terminated polyether alcohol with a halogenating agent, such as HCl or thionyl chloride, to form a polyether chloride, followed by reaction of the polyether chloride with a polyamine to form the desired poly (oxyalkylene) polyamine. This patent also teaches in Example 6 that the polyether chloride can be reacted with ammonia or dimethylamine to form the corresponding polyether amine or polyether dimethylamine. European Patent Application Publication No. 310,875, published on April 12, 1989 describes fuels for spark ignition engines containing a polyetheramine additive prepared first by propoxylating and / or butoxylating a primary or secondary alkanol or alkylmonoamine, and then by aminating the resulting polyether with ammonia or a primary aliphatic amine. French Patent No. 2,105,539, published on April 28, 1972, discloses carburettor detergent additives which are phenoxypropylamines which may be substituted with up to five hydrocarbon radicals of 1 to 30 carbon atoms on the aromatic ring. This patent also describes additives obtained by reacting such phenoxypropylamines with alkyl phosphoric acids. BRIEF DESCRIPTION OF THE INVENTION It has now been discovered that the combination of certain polyalkylphenoxyaminoalkanes with poly (oxyalkylene) amines provides excellent control of the deposits in the engine, especially the deposits in the inlet valve, when used as fuel additives in compositions made out of fuel. Accordingly, the present invention provides a novel fuel additive composition comprising: (a) A polyalkylphenoxyaminoalkane compound having the following formula, or a salt soluble in the fuel thereof: wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000; Ri and R2 are independently hydrogen or lower alkyl having from 1 to 6 carbon atoms; and A is amino, N-alkylamino having from about 1 to about 20 carbon atoms in the alkyl, N, N-dialkylamino group having from about 1 to about 20 carbon atoms in each alkyl group, or a polyamine portion having from about 2 to about 12 nitrogen atoms of amine and about 2 atoms to about 40 carbon atoms; and (b) a poly (oxyalkylene) amine having at least one basic nitrogen atom and a sufficient number of oxyalkylene units to render the poly (oxyalkylene) amine soluble in hydrocarbons boiling in the range of gasoline or fuel of diesel. The present invention further provides a fuel composition comprising a major amount of hydrocarbons boiling in the range of gasoline or diesel, and an amount effective to control the deposits of the fuel additive composition of the present invention. The present invention additionally provides a concentrate for fuel comprising an oleophilic, stable and inert organic solvent boiling in the range of about 65.5 ° C to 204.4 ° C (150 ° F to 400 ° F), and from about 10 to 70 percent by weight of the fuel additive composition of the present invention. Among other factors, the present invention is based on the surprising discovery that the unique combination of certain polyalkylphenoxyaminoalkanes with poly (oxyalkylene) amines provides excellent control of deposits in the engine, especially in the inlet valves, when used as additives. in compositions for fuel.

DETAILED DESCRIPTION OF THE INVENTION Polyalkylphosphinoxyalkylamino The polyalkylphenoxyaminoalkane component of the present additive composition has the general formula: where R, Rx, R2 and A are as defined above. Preferably, R is a polyalkyl group having an average molecular weight in the range of about 600 to 3,000, more preferably from about 700 to 3,000 and more preferably from about 900 to 2,500. Preferably, one of R_ and R2 is hydrogen or lower alkyl of 1 to 4 carbon atoms, and the other is hydrogen. More preferably, one of Ri and R2 is hydrogen, methyl or ethyl and the other is hydrogen. More preferably, R2 is hydrogen, methyl or ethyl, and Ri is hydrogen. In general, A is amino, N-alkylamino having from about 1 to about 20 carbon atoms in the alkyl group, preferably from about 1 to about 6 carbon atoms, more preferably from about 1 to about 4 carbon atoms; N, N-dialkylamino having from about 1 to about 20 carbon atoms in each alkyl group, preferably about 1 to about 6 carbon atoms, more preferably from about 1 to about 4 carbon atoms; or a polyamine portion having from about 2 to about 12 nitrogen atoms of amine and from about 2 to about 40 carbon atoms, preferably about 2 to about 12 nitrogen atoms of amine and about 2 to about 24 carbon atoms. More preferably, A is amino or a polyamino portion derived from a polyalkylene polyamine, including alkylene diamine. More preferably, A is amino or a polyamine portion derived from ethylenediamine or diethylenetriamine. It is preferred that the R substituent be located in the meta position or, more preferably, the para position on the aromatic, i.e., para ring or meta relative to the ether group. The compounds used in the present invention will generally have a sufficient molecular weight to be non-volatile at the operating temperature of the normal engine inlet valve (about 200 ° -250 ° C). Typically, the molecular weight of the compounds employed in this invention will be in the range of from about 700 to about 3,500, preferably from about 700 to about 2,500.

The soluble salts in the fuel of the compounds of formula I can be easily prepared from those compounds containing an amino or substituted amino group, and such salts are contemplated to be useful for preventing or controlling deposits in the engine. Suitable salts include, for example, those obtained by protonazing the amino portion with a strong organic acid, such as an alkyl- or arylsulfonic acid. Preferred salts are derived from toluenesulfonic acid and methanesulfonic acid. Definitions As used herein, the following terms have the following meanings unless expressly stated otherwise. The term "amino" refers to the group: -NH2. The term "N-alkylamino" refers to the group -? HRa, wherein Ra is an alkyl group. The term "N, N-dialkylamino" refers to the group: -? RbRc, wherein Rb and e are alkyl groups. The term "hydrocarbyl" refers to an organic radical composed primarily of carbon and hydrogen, which may be aliphatic, alicyclic, aromatic or combinations thereof, for example, aralkyl or alkaryl. Such hydrocarbyl groups are generally free of aliphatic unsaturation, ie, olefinic or acetylenic unsaturation, but may contain small amounts of heteroatoms, such as oxygen or nitrogen, or halogens, such as chlorine. The term "alkyl" refers to both straight chain and branched alkyl groups. The term "lower alkyl" refers to alkyl groups having from 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 "polyalkyl" refers to an alkyl group, which is generally derived from polyolefins which are polymer or copolymers of mono-olefins, particularly 1-mono-olefins, such as ethylene, propylene, butylene, and the like. Preferably, the monoolefin employed will have from about 2 to about 24 carbon atoms, and more preferably, from about 3 to about 12 carbon atoms. More preferred mono-olefins include propylene, butylene, particularly isobutylene, 1-octene and 1-decene. Polyolefins prepared from such mono-olefins include polypropylene, polybutene, especially polyisobutene, and polyalphaolefins from 1-octene and 1-decene. The term "fuel" or "hydrocarbon fuel" refers to normally liquid hydrocarbons having boiling points in the range of gasoline and diesel fuels. General Synthetic Procedures The polyalkylphenoxyaminoalkanes employed in this invention can be prepared by the following general methods and procedures. It should be appreciated that when typical or preferred process conditions (for example, reaction temperatures, times, molar ratios of reagents, solvents, pressures, etc.) occur, other process conditions may also be used unless the contrary. Optimal reaction conditions may vary with the particular reagents or solvents used, but such conditions may be determined by one skilled in the art by routine optimization procedures. Those skilled in the art will also recognize that it may be necessary to block or protect certain functional groups while conducting the following synthetic procedures. In such cases, the protecting group will serve to protect the functional group from unwanted reactions, or to block its unwanted reaction with other functional groups or with the reagents used to carry out the desired chemical transformations. The proper selection of a protecting group for a particular functional group will be readily apparent to one skilled in the art. Various protecting groups and their introduction and removal are described, for example, in T. w. Greene and T. G. M. Uts, Protective Groups in Organic Synthesis, Second Edition, Wiley, New York, 1991, and references cited therein. Synthesis The polyalkylphenoxyaminoalkanes used in the present invention can be prepared by a process that initially involves the hydroxyalkylation of a polyalkylphenol of the formula: wherein R is as defined herein, with an alkylene carbonate of the formula: OR £ JR JR2 wherein R_ and R2 are as defined herein, in the presence of a catalytic amount of an alkali metal hydride or hydroxide, or alkali metal salt, to provide a polyalkylphenoxyalkanol of the formula: Rl R2 -h 4-o-CH-CH-OiH (IV) wherein R, Ri and R2 are as defined herein. The polyalkylphenols of the formula II are well known materials and are typically prepared by the alkylation of phenol with the desired polyolefin or chlorinated polyolefin. An additional discussion of polyalkylphenols can be found, for example, in U.S. Patent No. 4,744,921 and U.S. Patent No. 5,300,701. Accordingly, the polyalkylphenols of formula II can be prepared from the corresponding olefins by conventional methods. For example, the polyalkylphenols of formula II above can be prepared by reacting the appropriate olefin or mixture of olefins with phenol in the presence of an alkylation catalyst at a temperature close to • from 25 ° C to 150 ° C, and preferably 30 ° C to 100 ° C, either without solvent or in an essentially inert solvent at atmospheric pressure. A preferred alkylation catalyst is boron trifluoride. Molar ratios of reagents can be used. Alternatively, molar excesses of the phenol can be used, ie, from 2 to 3 equivalents of phenol per equivalent of olefin with phenol that did not react recycled. The latter process maximizes monoalkylphenol. Examples of inert solvents include heptane, benzene, toluene, chlorobenzene and thinner 250, which is a mixture of aromatic compounds, paraffins and naphtho s. The polyalkylphenol substituent on the polyalkylphenols used in the invention is generally derived from polyolefins which are polymers or copolymers of mono-olefins, particularly 1-mono-olefins, such as ethylene, propylene, butylene and the like. Preferably, the mono-olefin employed will have from 2 to about 24 carbon atoms, and more preferably, from about 3 to 12 carbon atoms. More preferred mono-olefins include propylene, butylene, particularly isobutylene, 1-octene and 1-decene. Polyolefins prepared from such mono-olefins include polypropylene, polybutene, especially polyisobutene, and polyalphaolefins produced from 1-octene and 1-decene.

The preferred polyisobutenes used to prepare the polyalkylphenols employed herein are polyisobutenes comprising at least about 20% of the most reactive methylvinylidene isomer, preferably at least 50% and more preferably at least 70%. Suitable polyisobutenes include those prepared using BF3 catalyst. The preparation of such polyisobutenes in which the methylvinylidene isomer comprises a high percentage of the total composition which is described in US Patent Nos. 4,152,499 and 4,605,808. Such polyisobutenes, known as "reactive" polyisobutenes, provide high molecular weight alcohols in which the hydroxyl group is at or near the end of the hydrocarbon chain. Examples of suitable polyisobutenes having a somewhat alkylvinylidene content include Ultravis 30, a polyisobutene having an average molecular weight of about 1300 and a methylvinylidene content of about 74%, and Ultravis 10, a polyisobutene having an average molecular weight of about 950 and a methylvinylidene content of about 76%, both available from British Petroleum. The alkylene carbonates of formula III are known compounds that are commercially available, or can be prepared easily using conventional methods. Suitable alkylene carbonates include ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate and the like. A preferred alkylene carbonate is ethylene carbonate. The catalyst employed in the reaction of polyalkylphenol and the alkylene carbonate can be any of the well known hydroxyalkylation catalysts. Typical hydroxyalkylation catalysts include alkali metal hydrides, such as lithium hydride, sodium hydride and potassium hydride, alkali metal hydroxides, such as sodium hydride and potassium hydride, and alkali metal salts, eg, halides of alkali metal, such as sodium chloride and potassium chloride, and alkali metal carbonates, such as sodium carbonate and potassium carbonate. The amount of catalyst employed will be in the range usually from about 0.01 to 1.0 equivalent, preferably from about 0.05 to 0.3 equivalents. The polyalkylphenol and the ethylene carbonate are generally reacted in essentially equivalent amounts in the presence of the hydroxyalkylation catalyst, at a temperature in the range of about 100 ° C to 210 ° C, and preferably from about 150 ° C to about 170 ° C. The reaction can take place in the presence or absence of an inert solvent. The reaction time will vary depending on the particular alkylphenol and alkylene carbonate reagents, the catalyst used and the reaction temperature. In general, the reaction time will be in the range from about two hours to about five hours. The progress of the reaction is typically monitored by the evolution of carbon dioxide. Upon completion of the reaction, the polyalkylphenoxyalkanol product is isolated using conventional techniques. The reaction of hydroxyalkylation of phenols with alkylene carbonates is well known in the art and is described, for example, in U.S. Patent Nos. 2,987,555; 2,967,892; 3,283,030 and 4,341.905. Alternatively, the polyalkylphenoxyalkanol product of formula IV can be prepared by reacting the polyalkylphenol of formula II with an alkylene oxide of the formula: (V) wherein Ri and R2 are as defined herein, in the presence of a hydroxyalkylation catalyst described above. Suitable alkylene oxides of formula V include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and the like. A preferred alkylene oxide is ethylene oxide. In a manner similar to the reaction with alkylene carbonate, the polyalkylphenol and the alkylene oxide are reacted in essentially equivalent or equimolar amounts in the presence of 0.01 to 1.0 equivalents of hydroxyalkylation catalyst, such as sodium and potassium hydride, at a temperature in the range of about 30 ° C to about 150 ° C, for about 2 to about 24 hours. The reaction can be conducted in the presence or absence of an inert solvent, substantially anhydrous. Suitable solvents include toluene, xylene, and the like. In general, the reaction is conducted at a pressure sufficient to contain the reagents and any solvents present, typically at atmospheric pressure or higher. The polyalkylphenoxyalkanol of formula IV is subsequently reacted, either directly or through an intermediary, with an appropriate amine to provide the desired polyalkyl phenoxyaminoalkanes of formula I. Suitable amine reactants that can be employed to form the amine component, ie, the A substituent, of the polyalkylphenoxyaminoalkanes used in the present invention are discussed more fully below. The Amine Component of the Polyalkylphenoxyaminoalkanes In general, the amine component of the polyalkylphenoxyaminoalkanes employed herein will contain an average of at least about one basic nitrogen atom per molecule. A "basic nitrogen atom" is one that is detectable by a strong acid, for example, a primary, secondary, or tertiary amine nitrogen; distinguishing, for example, a carbonyl nitrogen, for example, -OC (0) NH-, which is not titrated with a strong acid. Preferably, at least one of the basic nitrogen atoms of the amine component will be a primary or secondary amine nitrogen, more preferably at least one will be a primary amine nitrogen. The amine component of the polyalkylphenoxyaminoalkanes used in this invention is preferably derived from ammonia, a primary alkylmonoamine or secondary dialkyl 1-pionoamine, or a polyamine having an amino terminal nitrogen atom.

The primary alkyl monoamines useful for preparing the compounds employed in the present invention contain a nitrogen atom and from about 1 to about 20 carbon atoms, more preferably from about 1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms. Examples of suitable monoamines include N-methylamine, α-T-ethylamine, N-propylamine, N-isopropylamine, N-butylamine, N-isobutylamine, N-sec-butylamine, N-tert-butylamine, N-pentylamine, N- cyclopentylamine, N-hexylamine, N-cyclohexylamine, N-octylamine, N-decylamine, N-dodecylamine, N-octadecylamine, N-benzylamine, N- (2-phenylethyl) amine, 2-aminoethanol, 3-amino-1-propanol , 2- (2-aminoethoxy) -ethanol,? - (2-ethoxyethyl) amine,? - (2-ethoxyethyl) amine and the like. ? -methylamine,? -ethylamine and? -n-propylamine are preferred primary amines. The component of. The amine of the polyalkylphenoxyaminoalkanes used herein can also be derived from a secondary dialkyl monoamine. The alkyl groups of the secondary amine may be the same or different, and generally each will contain from about 1 to about 20 carbon atoms, more preferably from about 1 to about 6 carbon atoms, more preferably from about about 1 to about 4 carbon atoms. One or both of the alkyl groups may also contain one or more oxygen atoms. Preferably, the alkyl groups of the secondary amine are independently selected from the group consisting of methylethyl, propyl, butyl, pentyl, hexyl, 2-hydroxyethyl and 2-methoxyethyl. More preferably, the alkyl groups are methyl, ethyl or propyl. Typical secondary amines that can be used in this invention include N, N-dimethylamine, N, N-diethylamine, N, N-di-n-propylamine, 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-Nn-propylamine, Nn-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. The preferred secondary amines are N, N-dimethylamine, N, N-diethylamine and N, N-di-n-propylamine. The cyclic secondary amines can also be used to form the additives used in this invention. In such cyclic compounds, the alkyl groups, 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 usually 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. Suitable polyamines may have a straight or branched chain structure, and may be cyclic or acyclic or combinations thereof. Generally, the amine nitrogen atoms of such polyamines will be separated from each other by at least two carbon atoms, ie polyamines having an aminal structure are not suitable. The polyamine may also contain one or more oxygen atoms, typically present as an ether or a hydroxyl group. Polyamines having a carbon to nitrogen ratio from about 1: 1 to about 10: 1 are particularly preferred. When preparing polyalkylphenoxyaminoalkane compounds using a polyamine wherein the various nitrogen atoms of the polyamine are not geometrically equivalent, several substitution isomers are possible, and each of these possible isomers is included within this invention. A particularly preferred group of polyamines for use in the present invention are polyalkylene polyamines, which include alkylene diamines. Such polyalkylene polyamines will typically contain from about 2 to about 12 nitrogen atoms and from about 2 to about 40 carbon atoms, preferably from about 2 to about 24 carbon atoms. Preferably, the alkylene groups of such polyalkylene polyamines will contain from about 2 to about 6 carbon atoms, more preferably from about 2 to about 4 carbon atoms. Examples of polyalkylene polyamines suitable include ethylenediamine, propylenediamine, isopropilendiamina, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, dipropylenetriamine, dimethylaminopropylamine, diisopropilentriamina, dibutylene triamine, di-sec-butilentriamina, triethylenetetramine, tripropilentretraamina, triisobutilentetraamina, tetra-etilenpentamina, pentaethylenehexamine, dimethylaminopropylamine , and mixtures thereof. Polyalkylene polyamines particularly suitable with those having the formula: H2N- (R3-NH) Z-H wherein R3 is a straight or branched chain alkylene group having from about 2 to about 6 carbon atoms, preferably from about 2 to about 4 carbon atoms, more preferably about 2 carbon atoms, i.e. , ethylene (-CH2CH2-); and z is an integer from about 1 to about 4, preferably about 1 or about 2. Particularly preferred polyalkylene polyamines are ethylenediamine, diethylenetriamine, triethylenetetraamine, and tetraethylenepentamine. The most preferred. they are ethylenediamine and diethylenetriamine, especially ethylenediamine. Also contemplated for use in the present invention are cyclic polyamines having one or more rings of 5 to 6 members. Such cyclic polyamine compounds include piperazine, 2-methylpiperazine, N- (2-aminoethyl) -piperazine, N- (2-hydroxyethyl) piperazine, 1,2-bis- (N-piperazinyl) heptane, 3-amino-pyrrolidine , N- (2-aminoethyl) pyrrolidine, and the like. Among the cyclic polyamines, piperazines are preferred. Many of the polyamines suitable for use in the present invention are commercially available, and others can be prepared by methods that are well known in the art. For example, the methods for preparing amines and their reactions are detailed in Sidgewick's book "The Organic Chemistry of Nitrogen", Clarendon Press, Oxford, 1966; Noller's book "Chemistry of Organic compounds", Saunders, Philadelphia, 2a. Edition, 1957; and Kirk-Othmer's book "Encyclopedia of Chemical Technology", 2a. Edition, especially Volume 2, pages 99-116. Preparation of the Polyalkylphenoxyaminoalkane As noted above, the polyalkylphenoxyaminoalkanes used in the present invention can be conveniently prepared by reacting the polyalkylphenoxyalkanol of formula IV, either directly or through an intermediate, with a nitrogen-containing compound, such as ammonia, a primary or secondary alkylmonoamine, or a polyamine, as described herein. Accordingly, the polyalkylphenoxyalkanol of formula IV can be converted to the desired polyalkylphenoxyalkylane by a variety of methods known in the art. For example, the terminal hydroxy group on the polyalkylphenoxyalkanol can be first converted to a suitable leaving group, such as a mesylate, chloride or bromide, and the like, by reaction with a suitable reagent, such as methanesulfonyl chloride. The resulting polyalkylphenoxyalkyl mesylate or equivalent intermediate can then be converted to a phthalimide derivative by reaction with potassium phthalimide in the presence of a suitable solvent, such as N, N-dimethylformamide. The polyalkylphenoxyalkyl phthalimide derivative is subsequently converted to the desired polyalkylphenoxy indoalkane by reaction with a suitable amine, such as hydrazine. Alternatively, the leaving group can be converted to an azide, as described, for example, in Turnbull Scriven, Chemical Reviews, Volume 88, pages 297-368, 1988. The azide is subsequently converted to the desired polyalkylphenoxyaminoalkane by reduction with hydrogen, and a catalyst, such as palladium on carbon or a Lindlar catalyst. The polyalkylphenoxyalkanol of formula IV can also be converted to the corresponding polyalkylphenoxyalkyl chloride by reaction with a suitable halogenating agent, such as HCl, thionyl chloride, or epichlorohydrin, followed by displacement of the chloride with a suitable amine, such as ammonia, a primary alkylmonoamine. or secondary, or a polyamine, as described, for example, in U.S. Patent No. 4,247,301 given to Honnen, the disclosure of which is incorporated herein by reference. Alternatively, the polyalkylphenoxyaminoalkanes used in the present invention can be prepared from the corresponding polyalkylphenoxyalkanol by a process commonly called reductive amination., as described in U.S. Patent No. 5,112,364 to Rath et al., and U.S. Patent No. 4,332,595 to Herbstman et al., the descriptions of which are incorporated herein by reference. In the reductive amination process, the polyalkylphenoxyalkanol is aminated with an appropriate amine, such as ammonia or a primary alkylmonoamine, in the presence of hydrogen and a hydro-dehydrogenation-hydrogenation catalyst. The amination reaction is typically carried out at temperatures in the range of about 160 ° C to about 250 ° C and pressures from about 70.3 kg / cm2 to about 351.5 kg / cm2 (about 1,000 to about 5,000 psig), preferably at about 105.45 kg / cm2 to about 210.9 kg / cm2 (about 1,500 to about 3,000 psig). Suitable hydrogenation-dehydrogenation catalysts include those containing platinum, palladium, cobalt, nickel, copper or chromium, or mixtures thereof. An excess of ammonia or amine reagent is generally used, such as about 5 times to about 60 times of molar excess, and preferably about 10 times to about 40 times of molar excess, of ammonia or amine. When the reductive amination is carried out with a polyamine reagent, the amination is preferably conducted using a two-step procedure described in the commonly assigned co-pending US Patent Application Serial No. 08 / 574,485, filed on December 19. 1995, and entitled "Reductive Amination Process for Manufacturing to Fuel Additive from Polyoxybutylene Alcohol wi th Ethyiene Diamine", the description of which is incorporated herein by reference in its entirety. According to this method, an appropriate alcohol is first contacted with a hydrogenation-dehydrogenation catalyst at a temperature of at least 230 ° C to provide a carbonyl-containing intermediate, which is subsequently reacted with a polyamine at a temperature below about 190 ° C in the presence of hydrogen and a hydrogenation catalyst to produce the desired polyamine adduct. In an alternative process for preparing the polyalkylphenoxyaminoalkanes used in the present invention, the polyalkylphenol of formula II can be reacted with an aziridine of the formula: wherein Ri and R2 are as defined herein, and R is hydrogen or alkyl of 1 to 20 carbon atoms. A preferred aziridine is one in which Ri is hydrogen, R 2 is hydrogen, methyl or ethyl, and R 4 is hydrogen. The reaction of aziridines with alcohols to produce beta-amino ethers is well known in the art and is discussed, for example, in Ham and Dermer, "Ethyleneimine and Other Aziridines", Academic Press, New York, 1969, pages 224-227 and 256-257. The Poly (Oxyalkylene) Amine The poly (oxyalkylene) amine component of the present fuel additive composition is a poly (oxyalkylene) amine having at least one basic nitrogen atom and a sufficient number of oxyalkylene units to render the poly (oxyalkylene) amine in hydrocarbons that boil in the range of gasoline or diesel. Preferably, such poly (oxyalkylene) amines will also be of a molecular weight sufficient to be non-volatile at the operating temperatures of the normal engine inlet valve, which are generally in the range of about 200 ° C to 250 ° C. ° C. In general, poly (oxyalkylene) amines suitable for use in the present invention will contain at least about 5 oxyalkylene units, preferably about 5 to 100, more preferably from about 8 to 100, and even more preferably about 10. to 100. Especially preferred poly (oxyalkylene) amines will range from about 10 to 25 oxyalkylene units. The molecular weight of the poly (oxyalkylene) amines employed herein will generally be in the range of from about 500 to about 10,000, preferably from about 500 to about 5,000. The poly (oxyalkylene) amine compounds suitable for use in the present invention include hydrocarbyl poly (oxyalkylene) polyamines described, for example, in U.S. Patent No. 4,247,301, filed January 27, 1981, and given to Honnen, the description of which is incorporated herein by reference. These compounds are hydrocarbyl poly (oxyalkylene) polyamines wherein the poly (oxyalkylene) moiety comprises at least one hydrocarbyl terminated poly (oxyalkylene) chain of oxyalkylene units of 2 to 5 carbon atoms, and wherein the poly (oxyalkylene) is attached through a terminal carbon atom to a nitrogen atom of a polyamine having from 2 to about 12 nitrogen atoms of amine and from 2 to about 40 carbon atoms, with a ratio of carbon to nitrogen between about 1: 1 and 10: 1. The hydrocarbyl group on these hydrocarbyl poly (oxyalkylene) polyamines will contain from about 1 to 30 carbon atoms. These compounds usually have molecular weights in the range of about 500 to 10,000, preferably from about 500 to 5,000, and more preferably from about 800 to 5,000. The hydrocarbyl poly (oxyalkylene) polyamines described above are prepared by conventional procedures known in the art, as taught, for example, in U.S. Patent No. 4,247,301. Other poly (oxyalkylene) amines suitable for use in the present invention are the poly (oxyalkylene) polyamines wherein the poly (oxyalkylene) moiety is connected to the polyamine portion through an oxyalkylenehydroxy type linkage derived from an epihalohydrin, such as epichlorohydrin or epibro ohydrin. This type of poly (oxyalkylene) amine having a linkage derived from epihalohydrin is described as, for example, in US Patent No. 4,261,704, filed April 14, 1981 and given to Langdon, the description of which is incorporated in the present by reference. Polyamines useful in preparing the poly (oxyalkylene) polyamines derived from epihalohydrin include, for example, alkylene polyamines, polyalkylene polyamines, cyclic amines, such as piperazines, and amino substituted amines. The poly (oxyalkylene) polyamines having an epihalohydrin derivative linkage between the poly (oxyalkylene) and polyamine portions are prepared using known procedures as taught, for example, in the North American Patent No. 4,261,704. Another type of poly (oxyalkylene) amine useful in the present invention is a highly branched alkyl poly (oxyalkylene) onoamine described, for example in U.S. Patent No. 5,094,667, filed March 10, 1992 and given to Schilowitz et al. , the description of which is incorporated herein by reference. These highly branched alkyl poly (oxyalkylene) onoamines have the general formula: R4-O- (C4H80) PCH2CH2CH2NH2 (VII) wherein R4 is a highly branched alkyl group containing from 12 to 40 carbon atoms, preferably an alkyl group having 20 carbon atoms which is derived from a Guerbet condensation reaction , and p is a number of up to 30, preferably from 4 to 8. The preferred alkyl group is derived from a Guerbet alcohol containing 20 carbon atoms having the formula: R5-CHCH2OH (VIII) CH2CH2R5 wherein R5 is a hydrocarbyl chain. The highly branched alkyl poly (oxyalkylene) monoamines of above are prepared using known methods as described, for example, in U.S. Patent No. 5,094,667. A preferred class of poly (oxyalkylene) amine for use in the fuel additive composition of the present invention are the hydrocarbyl poly (oxyalkylene) onoamines described, for example, in U.S. Patent No. 5,112,364, filed May 12, 1992. and given to Rath et al., the description of which is incorporated herein by reference. As described in U.S. Patent No. 5,112,364, such poly (oxyalkylene) monoamines can be prepared by reductive amination of a poly (oxyalkylene) alcohol initiated by phenol or initiated by alkylphenol as ammonia or a primary amine. In addition, US Patent No. 4,247,301 mentioned above and given to Honnen discloses hydrocarbyl poly (oxyalkylene) monoamines which are suitable for use in the present fuel additive composition. In particular, Example 6 of this patent discloses alkylphenyl poly (oxyalkylene) onoamines prepared from ammonia and dimethylamine. A particularly preferred type of hydrocarbyl poly (oxyalkylene) monoamine is an alkylphenyl poly (oxyalkylene) monoamine wherein the poly (oxyalkylene) moiety contains oxypropylene units or oxybutylene units or mixtures of oxypropylene and oxybutylene units. Preferably, the alkyl group on the alkylphenyl portion is a straight or branched chain alkyl of 1 to 24 carbon atoms. An especially preferred alkylphenyl portion is tetrapropenylphenyl, that is, wherein the alkyl group is a branched chain alkyl of 12 carbon atoms derived from the propylene tetramer. An additional discussion of the hydrocarbon-substituted poly (oxyalkylene) portion of the poly (oxyalkylene) amine component of the present fuel additive composition is found below. Another preferred class of poly (oxyalkylene) amine for use in the fuel additive composition of the present invention are the hydrocarbyl substituted poly (oxyalkylene) aminocarbamates described, for example, in U.S. Patent Nos. 4,288,612; 4,236,020; 4,160,648; 4,191,537; 4,270,930; 4,233,168; 4,197,409; 4,243,798 and 4,881,945, the description of each of which is incorporated herein by reference. The hydrocarbyl poly (oxyalkylene) aminocarbamates contain at least one basic nitrogen atom and have an average molecular weight of about 500 to 10,000, preferably about 500 to 5,000, and more preferably about 1,000 to 3,000. completely below, these hydrocarbyl poly (oxyalkylene) aminocarbamates contain (a) a poly (oxyalkylene) moiety, (b) an amino moiety and (c) a carbonate binding moiety. (oxyalkylene) The hydrocarbyl terminated poly (oxyalkylene) polymers which are used to prepare the hydrocarbyl poly (oxyalkylene) aminocarbamates employed in the present invention are monohydroxy compounds, for example, alcohols, often called monohydroxy polyethers, or monocarbyl esters of polyalkylene glycol, or "crowned" poly (oxyalkylene) glycols, and they are to be distinguished from poly (oxyalkylene) glycols (diols), or polyols, which are not ter mined with hydrocarbon, that is, they are not crowned. These hydrocarbyl poly (oxyalkylene) alcohols can be produced by the addition of lower alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, etc., to a hydroxy compound, R9OH, under polymerization conditions , where R? is the hydrocarbyl group that crowns the poly (oxyalkylene) chain. In the hydrocarbyl poly (oxyalkylene) aminocarbamates employed in the present invention, the hydrocarbyl group R9 will generally contain from about 1 to about 30 carbon atoms, preferably from 2 to about 20 carbon atoms, and is preferably aliphatic or aromatic, that is, an alkyl or alkylphenyl wherein the alkyl is a straight or branched chain from 1 to about 24 carbon atoms. More preferably, R9 is alkylphenyl wherein the alkyl group is a branched chain of 12 carbon atoms, derived from propylene tetramer, and commonly called tetrapropenyl.

The oxyalkylene units in the poly (oxyalkylene) moiety preferably contain from 2 to about 5 carbon atoms but one or more units of a larger carbon number may also be present. Generally, each poly (oxyalkylene) polymer contains at least about 5 oxyalkylene units, preferably about 5 to about 100 oxyalkylene units, more preferably about 8 to about 100 units, still more preferably about 10. to 100 units, and more-preferably 10 to about 25 such units. The poly (oxyalkylene) portion of hydrocarbyl poly (oxyalkylene) aminocarbamates employed in the present invention is more fully described and exemplified in US Patent No. 4,191,537, filed March 4, 1990 and given to Lewis, the description of the which is incorporated herein by reference. Although the hydrocarbyl group on the poly (oxyalkylene) hydrocarbyl portion will preferably contain from 1 to about 30 carbon atoms, larger hydrocarbyl groups, particularly larger chain alkylphenyl groups, may also be employed. For example, alkylphenyl poly (oxyalkylene) aminocarbamates wherein the alkyl group contains at least 40 carbon atoms, as described in US Patent No. 4,881,945, filed November 21, 1989 and given to Buckley, are also contemplated for use in the present invention. The alkylphenyl group on the aminocarbamates of U.S. Patent No. 4,881,945 will preferably contain an alkyl group of 50 to 200 carbon atoms, and more preferably, an alkyl group of 60 to 100 carbon atoms. These larger chain alkyl groups will generally be derived from olefin polymers, such as polybutene. The disclosure of U.S. Patent No. 4,881,945 is incorporated herein by reference. Also contemplated for use in the present invention are the alkylphenyl poly (oxypropylene) aminocarbamates wherein the alkyl group is a substantially straight chain alkyl group of about 25 to 50 carbon atoms derived from an alpha olefin oligomer of alpha olefins of 8 to 20 carbon atoms, as described in PCT International Patent Application Publication No. WO 90/07564, published July 12, 1990, the disclosure of which is incorporated herein by reference. B. The Amine Portion The amine portion of the hydrocarbyl poly (oxyalkylene) -aminocarbamate is preferably derived from a polyamine having from 2 to about 12 nitrogen atoms of amine and from 2 to about 40 carbon atoms. The polyamine is preferably reacted with a hydrocarbyl poly (oxyalkylene) chloroformate to produce the hydrocarbyl poly (oxyalkylene) aminocarbamate fuel additive found to be used within the scope of the present invention. The chloroformate is likewise derived from the hydrocarbyl poly (oxyalkylene) alcohol by reaction with phosgene. The polyamine provides the hydrocarbyl poly (oxyalkylene) aminocarbamate with, on average, at least about one basic nitrogen atom per carbamate molecule, ie, a nitrogen atom titrable by strong acid. The polyamine preferably has a carbon to nitrogen ratio from about 1: 1 to about 10: 1. The polyamine may be substituted with substituents selected from hydrogen, hydrocarbyl groups from 1 to about 10 carbon atoms, acyl groups from 2 to about 10 carbon atoms, and monoketone, monohydroxy, mononitro, monocyano, alkyl and alkoxy derivatives of hydrocarbyl groups from 1 to 10 carbon atoms. It is preferred that at least one of the basic nitrogen atoms of the polyamine be a primary or secondary amino nitrogen atom. The amine portion of the hydrocarbyl poly (oxyalkylene) aminocarbamates employed in the present invention have been more fully described and exemplified in US Pat. No. 4, 191,537. A more preferred polyamine to be used for preparing the hydrocarbyl poly (oxyalkylene) aminocarbamates found to be used within the scope of the present invention is a polyalkylene polyamine, including alkylene diamine, and including substituted polyamines, for example, a polyalkylene polyamine substituted with hydroxyalkyl. Preferably, the alkyl group contains from 2 to 6 carbon atoms, preferably from 2 to 3 carbon atoms between the nitrogen atoms. Examples of such polyamines include ethylenediamine, diethylenetriamine, triethylene tetramine, di (trimethylene) triamine, dipropylenetriamine, tetraethylenepentamine, etc. Among the polyalkylene polyamines, polyethylene polyamine and polypropylene polyamine containing from 2 to about 12 nitrogen atoms of amine and from 2 to about 24 carbon atoms, in particular, the lower polyalkylene polyamines, for example ethylenediamine, diethylenetriamine, are particularly preferred. , propylene diamine, dipropylenetriamine, etc., are more preferred.

C. The Aminocarbamate Connection Group The hydrocarbyl poly (oxyalkylene) aminocarbamate used as the poly (oxyalkylene) amine component of the fuel additive composition of the present invention is obtained by joining the polyamine and the poly (oxyalkylene) alcohol of hydrocarbyl with one another through a carbamate link, that is, wherein the oxygen can be viewed as the oxygen of the terminal hydroxyl of the poly (oxyalkylene) alcohol, the nitrogen is derived from the polyamine and the carbonyl group -C (O) -, is preferably provided by a coupling agent, such as phosgene . In a preferred preparation method, the hydrocarbyl poly (oxyalkylene) alcohol is reacted with phosgene to produce a chloroformate, and the chloroformate is reacted with the polyamine. Since there could be more than one nitrogen atom of the polyamine which is capable of reacting with the chloroformate, the carbamate product can contain more than one portion of hydrocarbyl poly (oxyalkylene). The hydrocarbyl poly (oxyalkylene) aminocarbamate product containing, on average, about one portion of poly (oxyalkylene) per molecule is preferred (ie, it is a monocarbamate), although it is understood that this reaction path can lead to mixtures containing appreciable amounts of di- or higher substitution of the poly (oxyalkylene) chain on a polyamine containing several reactive nitrogen atoms. A particularly preferred aminocarbamate is alkylphenyl poly (oxybutylene) aminocarbamate, wherein the amine portion is derived from ethylenediamine or diethylenetriamine. Synthetic methods to avoid greater degrees of substitution, methods of preparation, and other characteristics of the aminocarbamates used in the present invention are described more fully and exemplified in US Patent No. 4,191,537. Fuel Compositions The fuel additive compositions of the present invention will generally be employed in hydrocarbon fuels to prevent and control engine deposits, particularly deposits in the inlet valve. The appropriate concentration of additive needed to achieve the desired control of the tank varies depending on the type of fuel used, the type of engine, in the presence of other fuel additives.

In general, the composition of fuel additives present will be employed in a hydrocarbon fuel at a concentration ranging from about 50 to about 5,000 parts per million (ppm) by weight, preferably from 100 to 2,500 ppm. In terms of individual components, the hydrocarbon fuels containing the fuel additive composition of this invention will generally contain from about 25 to 2,000 ppm of the polyalkylphenoxyaminoalkane component, and about 25 to 2,000 ppm of the poly (oxyalkylene) component. ) amine. The ratio of the polyalkylphenoxyaminoalkane to poly (oxyalkylene) amine is generally in the range of from about 0.05: 1 to about 5: 1, and preferably will be about 2: 1 or less. The fuel additive composition of the present invention can be formulated as a concentrate using a stable and inert oleophilic organic solvent (ie, dissolves in gasoline) that boils in the range of about 65.5 ° C to 204.4 ° C (close to from 150 ° F to 400 ° F). Preferably, an aliphatic or an aromatic hydrocarbon solvent, such as benzene, toluene, xylene, or higher boiling aromatics or aromatic thinners is used. Aliphatic alcohols containing from 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 will usually be in the range from about 10 to about 70 by weight, preferably from 10 to 50 percent by weight, more preferably from 20 to 40 percent by weight. In gasoline fuels, other fuel additives with the additive composition of the present invention may be employed, including, for example, oxygenated agents, such as t-butyl methyl ether, anti-knock agents, such as tricarbonyl methylcyclopentadienyl manganese, and others. dispersants / detergents, such as hydrocarbilamines, or succinimides. Additionally, antioxidants, metal deactivators, demulsifiers, and carburetor or fuel injector detergents may be present. In diesel fuels, other well-known additives may be employed, such as substances for lowering the thawing temperature, flow improvers, cetane improvers and the like. A carrier fluid or non-volatile oil, soluble in the fuel with the fuel additive composition of this invention, may also be used. The carrier fluid is a liquid, hydrocarbon-soluble, chemically inert carrier which substantially increases the non-volatile residue (NVR), or the solvent-free liquid fraction of the fuel additive composition while not overwhelmingly contributing to the increased requirement of octane. The carrier fluid can be a natural or synthetic fluid, such as mineral oil, refined petroleum oils, synthetic polyalkanes and alkenes, including hydrogenated and non-hydrogenated polyalphaolefins, and synthetic polyoxyalkylene-derived fluids, such as those described, for example, in U.S. Patent No. 4,191,537 given to Lewis, and polyesters, such as those described for example, in U.S. Patent Nos. 3,756,793 given to Robinson and 5,004,478 to Vogel et al., And in European Patent Applications Nos. 356,726 , published March 7, 1990 and 382,159, published August 16, 1990. It is believed that these carrier fluids act as a carrier for the fuel additive composition of the present invention, and to help eliminate and retard the deposits. The carrier fluid may also exhibit synergistic reservoir control properties when used in combination with the fuel additive composition of this invention.

Carrier fluids are typically employed in amounts ranging from about 25 to about 5000 ppm by weight of the hydrocarbon fuel, preferably from 100 to 3000 ppm of the fuel. Preferably, the ratio of the carrier fluid to the deposit control additive will be in the range of from about 0.2: 1 to about 10: 1, more preferably from 0.5: 1 to 3: 1. When employed in a concentrate for fuel, the carrier fluids will usually be present in amounts ranging from about 20 to about 60 weight percent, preferably from 30 to 50 weight percent. PREPARATIONS AND EXAMPLES A further understanding of the invention can be had in the following non-limiting Examples. Where, unless expressly stated otherwise, all temperatures and temperature ranges refer to the Celsius system, and the term "ambient" or "ambient temperature" refers to about 20 ° C-25 ° C. "percent" or "%" refers to percent by weight, and the term "mol" or "moles" refers to mol grams. The term "equivalent" refers to an amount of reactant equal in moles, to the moles of the preceding or succeeding reagent quoted in that example in terms of finite moles or finite weight or volume. When they occur, the pr magnetic resonance spectra (RMP or NMR) were determined at 300 mHz, the signals are assigned as singles (s), broad singles (sa), doublets (d), doublets of doubles (dd), triplets (t), double triplets (dt), quartets (q), and multiplets (m), and cps refers to cycles per second. Example 1 Preparation of Polyisobutylphenol To a flask equipped with a magnetic stirrer, reflux condenser, thermometer, addition funnel and nitrogen inlet was added 203.2 grams of phenol. The phenol was heated to 0 ° C and the heat source was removed. Then 73.5 milliliters of etched boron trifluoride was added dropwise. 1040 grams of Ultravis 10 Polyisobutene (molecular weight 950, 76% methylvinylidene, available from British Petroleum) were dissolved in 1,863 milliliters of hexane. The polyisobutene was added to the reaction at a rate to maintain the temperature between 22 ° C-27 ° C. The reaction mixture was stirred for 16 hours at room temperature. Then 400 milliliters of concentrated ammonium hydroxide was added, followed by 2,000 milliliters of hexane. The reaction mixture was washed with water (3 x 2,000 milliliters), dried over magnesium sulfate, filtered and the solvents were removed under vacuum to provide 1.056.5 grams of a crude reaction product. The crude reaction product was determined to contain 80% of the desired product by pr NMR and chromatography on silica gel eluting with hexane, followed by hexane: ethyl acetate: ethanol (93: 5: 2).

Example 2 Preparation of molecular 950) Potassium hydride (1.1 grams of a dispersion of 35 percent by weight in mineral oil) and 4-polyisobutylphenol (99.7 grams, prepared as in Example 1) were added to a flask equipped with a magnetic stirrer, reflux condenser, inlet of nitrogen and thermometer. The reaction was heated to 130 ° C for one hour and then cooled to 100 ° C. Ethylene carbonate (8.6 grams) was added and the mixture was heated to 160 ° C for 16 hours. The reaction was cooled to room temperature and one milliliter of isopropanol was added. The reaction was diluted with one liter of hexane, washed three times with water and once with saturated saline. The organic layer was dried over anhydrous magnesium sulfate, filtered and the solvents were removed in vacuo to provide 98.0 grams of the desired product as a yellow oil.

Example 3 Preparation of The alcohol of Example 2 (20.0 grams), triethylamine (2.9 ml), and anhydrous dichloromethane (200 ml) were combined. The solution was cooled to 0 ° C and methanesulfonyl chloride (1.5 ml) was added dropwise. The reaction was stirred at room temperature under nitrogen for 16 hours. The solution was diluted with dichloromethane (600 ml) and washed twice with saturated aqueous sodium bicarbonate solution and once with saline. The organic layer was dried over anhydrous sodium sulfate, filtered and the solvents were removed in vacuo to give 20.4 grams as a yellow oil.

Example 4 Preparation of Ethylenediamine (12.3 ml) and anhydrous toluene (100 ml) were combined under nitrogen. The product of Example 3 (20.4 grams, dissolved in 100 ml of anhydrous toluene) was added dropwise. The resulting solution was heated to reflux for 16 hours. The solution was diluted with hexane (600 ml) and washed once with saturated aqueous sodium bicarbonate solution, three times with water and once with saline. The organic layer was dried over anhydrous sodium sulfate, filtered and the solvents were removed in vacuo to give 15.1 grams as a yellow oil. The oil was chromatographed on silica gel, eluting with hexane / diethyl ether (50:50), then hexane / diethyl ether / methanol / isopropylamine (40: 40: 15: 5) to provide 10.3 grams of the desired product as a yellow oil NMR of XH (CDC13) d 7.25 (d, 2 H), 6.8 (d, 2 H), 4.1 (t, 2 H), 3.0 (t, 2 H), 2.85 (t, 2 H), 2.75 (t , 2 H), 1.95 (sa, 3 H), 1.5-0.7 (m, 137 H).

E p e 5 Preparation of molecular J 950) A mesylate prepared as described in Example 3 (406.5 grams), sodium azide (198.2 grams), Adoben 464, a methyltrialkyl (8 to 10 carbon atoms) ammonium chloride available from Ashland Chemical (8.0 ml), N, N-dimethylformamide (800 ml) and toluene (1.2 1) were combined. The reaction was heated to reflux for 16 hours and cooled to room temperature. The mixture was filtered and the solvent was removed in vacuo. The residue was diluted with hexane (3.0 1) and washed three times with water and once with saline. The organic layer was dried over anhydrous magnesium sulfate, filtered and the solvents removed in vacuo to provide 334.3 grams of the desired azide as a yellow oil.

Example 6 Preparation of 950) A solution of the product of Example 5 (334.3 grams) in ethyl acetate (750 ml) and toluene (750 ml), containing 10% palladium on carbon (7.0 grams) was hydrogenated at 2.46-2.8 kg / cm2 (35- 40 psi) for 16 hours in a Parr low pressure hydrogenator. Filtration of the catalyst and removal of the solvent in vacuo gave 322.3 grams of the desired product as a yellow oil. NMR of lH (CDC13) d 7.25 (d, 2 H), 6.8 (d, 2 H), 4.0 (t, 1 H), 3.1 (t, 2 H), 2.35 (sa, 2 H), 0.7-1.6 (m, 137 H).

Example 7 Preparation of molecular n 950) Potassium hydride (15.1 grams of a 35 weight percent dispersion in mineral oil) and 4-polyisobutylphenol (1378.5 grams, prepared as in Example 1) were added to a flask equipped with a mechanical stirrer, reflux condenser, inlet of nitrogen and thermometer. The reaction was heated to 130 ° C for one hour and then cooled to 100 ° C. Propylene carbonate (115.7 milliliters) was added, and the mixture was heated to 160 ° C for 16 hours. The reaction was cooled to room temperature and ten milliliters of isopropanol was added. The reaction was diluted with ten liters of hexane, washed three times with water and once with saline. The organic layer was dried over anhydrous magnesium sulfate, filtered and the solvents were removed in vacuo to provide 1301.7 grams of the desired product as a yellow oil.

Example 8 Preparation of The alcohol of Example 7 (50.0 grams), triethylamine (7.0 ml), and anhydrous dichloromethane (500 ml) were combined. The solution was cooled to 0 ° C and methanesulfonyl chloride (3.7 ml) was added dropwise. The reaction was stirred at room temperature under nitrogen for 16 hours. The solution was diluted with dichloromethane (1.5 1) and washed three times with saturated aqueous sodium bicarbonate solution and once with saline. The organic layer was dried over anhydrous sodium sulfate, filtered and the solvents were removed in vacuo to give 57.7 grams as a yellow oil.

Example 9 Preparation of molecular 950) The mesylate of Example 8 (57.7 grams), sodium azide (27.1 grams), Adoben 464, (1.0 ml), N, N-dimethylformamide (400 ml) and toluene (600 ml) were combined. The reaction was heated to reflux for 16 hours and cooled to room temperature. The mixture was filtered and the solvent was removed in vacuo. The residue was diluted with hexane (1.5 1) and washed three times with water and once with saline. The organic layer was dried over anhydrous magnesium sulfate, filtered and the solvents were removed in vacuo to give 43.1 grams of the desired azide as a yellow oil.

Example 10 Preparation of cular 950) A solution of the product of Example 9 (43.1 grams) in ethyl acetate (100 ml) and toluene (100 ml), containing 10% palladium on carbon (2.0 grams) was hydrogenated at 2.46-2.8 kg / cm2 (35-). 40 psi) for 16 hours in a Parr low pressure hydrogenator. Filtration of the catalyst and removal of the solvent in vacuo gave 41.5 grams of the desired product as a yellow oil. NMR of aH (CDC13) d 7.25 (d, 2 H), 6.85 (d, 2 H), 3.9 (broad c, 1 H), 3.35 (m, 1 H), 1.9 (broad s, 2 H), 0.7 -1.6 (m, 140 H).

EXAMPLE 11 Preparation of Dodecylphenoxy Poly (oxybutylene) poly (oxypropylene) amine A dodecylphenoxypoly (oxybutylene) -poly (oxypropylene) amine was prepared by the reductive amination with ammonia from the random copolymer of poly (oxyalkylene) -alcohol, dodecylphenoxy poly (oxybutylene) poly (oxypropylene) -alcohol, wherein the alcohol has an average molecular weight of about 1598. The poly (oxyalkylene) alcohol was prepared from dodecylphenol using a 75/25 weight / weight ratio of butylene oxide and propylene oxide, in accordance with the procedures described in U.S. Patent Nos. 4,191,537; 2,782,240 and 2,841,479, as well as in Kirk-Othmer's book, "Encyclopedia of Chemical Tehcnology", 4th edition, Volume 19, 1996, page 722. The reductive amination of the poly (oxyalkylene) alcohol was carried out using conventional techniques described in U.S. Patents Nos. 5,112,364; 4,609,377 and 3,440,029. Example 12 Testing in a Monocilindrical Motor The test compounds were mixed in gasoline and their deposit reduction capacity was determined in an ASTM / CFR single cylinder engine test.

A single-cylinder Waukesha CFR engine was used. Each run was carried out for 15 hours, and at the end of this time the inlet valve was removed, washed with hexane and weighed. The previously determined weight of the clean valve was subtracted from the weight of the valve at the end of the run. The differences between the two weights is the weight of the deposit. A smaller amount of deposit indicates a higher additive. The operating conditions of the test were as follows: water jacket temperature 93.3 ° C (200 ° F); vacuum in the intake manifold or distributor of 0.414 kg / cm2 (12 inches of mercury), air-fuel ratio of 12, ignition spark regulation of 40 ° BTC; Motor speed is 1800 rpm; the engine oil is a commercial grade SAE 30. The amount of carbonaceous deposits in milligrams on the inlet valves is reported for each of the test compounds in Table I and Table II.

TABLE I Weight of the Deposit at the Inlet Valve (in milligrams) Sample1 Run 1 Run 2 Average Base Fuel 333.5 354.9 344.2 Example 4 22.5 22.7 22.6 To 150 parts per million assets (ppma).

TABLE II Weight of the Tank in the Inlet Valve (in milligrams) Sample Run 1 Run 2 Average Base Fuel 323.8 312.1 318.0 Example 6 12.1 21.0 16.6 lA 125 parts per million assets (ppma).

The base fuel used in the single-cylinder engine tests above was a regular octane unleaded gasoline containing no fuel detergent. The test compounds were mixed with the base fuel to give the concentrations indicated in the tables.

The data in Table I and Table II illustrate the significant reduction in inlet valve deposits provided by the polyalkylphenoxyaminoalkanes used in the present invention (Examples 4 and 6) compared to the base fuel. The combination of polyalkylphenoxyaminoalkane and poly (oxyalkylene) amine was also tested in the single-cylinder engine test, and the amount of carbonaceous deposit in milligrams on the inlet valves is reported in Table III.

TABLE III Weight of the Tank at the Inlet Valve (in milligrams) Sample Run Concentration 1 Run 2 Average (ppna) Base Fuel 250.3 253.1 251.6 Polyalkylphenoxy- 50/50 188 149.8 169 aminoalkane / Carrier Fluid1 Polyalkylphenoxy- 50/50 9.4 4.1 6.75 aminoalkane / Poly (oxyalkylene) amine2 Polyalkylphenoxy- 50/50 21.2 14.3 17.8 aminoalkane / Poly (oxyalkylene) amine3 Polyalkylphenoxy50 / 50 131.8 111.5 121.6 aminoalkane / Carrier Fluid'1 Polyalkylphenoxy- 50/50 aminoalkane / Poly (oxyalkylene) amine5 Polyalkylphenoxy- 50/50 1.2 1.1 aminoalkane / Poly. { oxyalkylene) amine6 Mixture of 50 ppma of polyisobutylphenoxyaminoalkane prepared as described in Example 10 and 50 ppm of a carrier fluid of dodecylphenyl poly (oxybutylene) alcohol. 2 50 ppma blend of polyisobutylphenoxyaminoalkane prepared as described in Example 10 and 50 ppma of dodecylphenoxypoly (oxybutylene) poly (oxypropylene) amine prepared as described in Example 11. 3Mix of 50 ppma of polyisobutylphenoxyaminoalkane prepared as described in Example 10 and 50 ppma of a dodecylphenyl poly (oxybutylene) ethylenediamine carbamate (molecular weight about 1600), prepared essentially as described in Examples 6-8 of US Patent No. 4,197,537. 4 50 ppma blend of polyisobutylphenoxyaminoalkane prepared as described in Example 6 and 50 ppm of a carrier fluid of dodecylphenyl poly (oxybutylene) alcohol. 50 ppma blend of polyisobutylphenoxyaminoalkane prepared as described in Example 6 and 50 ppma of dodecylphenoxypoly (oxybutylene) poly (oxypropylene) amine prepared as described in Example 11. 6 50 ppma blend of polyisobutylphenoxyaminoalkane prepared as described in Example 6 and 50 ppma of a dodecylphenyl poly (oxybutylene) ethylenediamine carbamate (molecular weight about 1600), prepared essentially as described in Examples 6-8 of US Patent No. 4,197,537.

The data in Table III demonstrate that the combination of a polyalkylphenoxyaminoalkane and a poly (oxyalkylene) amine has a beneficial effect and gives a control of the deposit in the inlet valve significantly better than. the polyalkylphenoxyaminoalkane component with a carrier fluid.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, property is claimed as contained in the following:

Claims

CLAIMS 1. A fuel additive composition, characterized in that it comprises: (a) a polyalkylphenoxyaminoalkane compound of the formula: or a fuel soluble salt thereof, wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000; Ri and R2 are independently hydrogen or lower alkyl having from 1 to 6 carbon atoms; and A is amino, N-alkyl amino having from 1 to about 20 carbon atoms in the alkyl, N, N-dialkyl amino group having about 1 to about 20 carbon atoms in each alkyl group, or polyamine portion having about 2 to about 12 nitrogen atoms of amine and about 2 to about 40 carbon atoms; and (b) a poly (oxyalkylene) amine having at least one basic nitrogen atom and a sufficient number of oxyalkylene units to render the poly (oxyalkylene) amine soluble in hydrocarbons boiling in the gasoline or diesel fuel range .
2. The fuel additive composition according to claim 1, characterized in that one of Ri and R2 is hydrogen or lower alkyl of 1 to 4 carbon atoms, and the other is hydrogen.
3. The fuel additive composition according to claim 2, characterized in that one of Ri and R2 is hydrogen, methyl or ethyl, and the other is hydrogen.
4. The fuel additive composition according to claim 3, characterized in that R2 is hydrogen, methyl or ethyl, and Ri is hydrogen.
5. The fuel additive composition according to claim 1, characterized in that R is a polyalkyl group having an average molecular weight in the range of about 600 to 3,000.
6. The fuel additive composition according to claim 5, characterized in that R is a polyalkyl group having an average molecular weight in the range of about 700 to 3,000.
The fuel additive composition according to claim 6, characterized in that R is a polyalkyl group having an average molecular weight in the range of about 900 to 2,500.
The fuel additive composition according to claim 1, characterized in that R is a polyalkyl group derived from polypropylene, polybutene, or a polyalphaolefin oligomer of 1-octene or 1-decene.
9. The fuel additive composition according to claim 8, characterized in that R is a polyalkyl group derived from polyisobutene.
10. The fuel additive composition according to claim 9, characterized in that the polyisobutene contains at least about 20% of a methylvinylidene isomer.
11. The fuel additive composition according to claim 1, characterized in that A is amino, N-alkyl amino or a polyamine portion.
12. The fuel additive composition according to claim 11, characterized in that A is amino or N-alkyl amino having from about 1 to about 4 carbon atoms in the alkyl group.
13. The fuel additive composition according to claim 12, characterized in that A is amino.
14. The fuel additive composition according to claim 11, characterized in that A is a polyamino portion having from about 2 to about 12 nitrogen atoms of amine, and from about 2 to about 40 carbon atoms.
15. The fuel additive composition according to claim 14, characterized in that A is a polyamino derivative derived from a polyalkylene polyamine containing from about 2 to about 12 polyamine atoms of amine nitrogen, and from about 2 to about 24 nitrogen atoms.
16. The fuel additive composition according to claim 15, characterized in that the polyalkylene polyamine has the formula: H2N- (R3-NH) ZH wherein R3 is an alkylene group having from about 2 to about 6 atoms of carbon, and z is an integer from about 1 to about 4.
17. The fuel additive composition according to claim 16, characterized in that R3 is an alkylene group having from about 2 to about 4 carbon atoms.
18. The fuel additive composition according to claim 17, characterized in that the polyalkylene amine is ethylene diamine or diethylene triamine.
19. The fuel additive composition according to claim 18, characterized in that the polyalkylene amine is ethylene diamine.
20. The fuel additive composition according to claim 1, characterized in that R is a polyalkyl group derived from polyisobutene, Ri and R2 are hydrogen, and A is amino or a polyamine portion derived from ethylene diamine.
21. The fuel additive composition according to claim 1, characterized in that the poly (oxyalkylene) amine has a molecular weight in the range of about 500 to about 10,000.
22. The fuel additive composition according to claim 1, characterized in that the poly (oxyalkylene) amine contains at least about 5 oxyalkylene units.
23. The fuel additive composition according to claim 1, characterized in that the poly (oxyalkylene) amine is a hydrocarbyl poly (oxyalkylene) polyamine
24. The fuel additive composition according to claim 1, characterized because the poly (oxyalkylene) amine is a hydrocarbyl poly (oxyalkylene) -aminocarbamate
25. The fuel additive composition according to claim 24, characterized in that the hydrocarbyl group of the hydrocarbyl poly (oxyalkylene) -aminocarbamate contains from 1 to about 30 carbon atoms
26. The fuel additive composition according to claim 25, characterized in that the hydrocarbyl group of the hydrocarbyl poly (oxyalkylene) aminocarbamate is an alkylphenyl group.
27. The fuel additive composition according to claim 26, characterized in that the alkyl portion of the alkylphenyl group is tetrapropenyl.
28. The fuel additive composition according to claim 24, characterized in that the amine portion of the hydrocarbyl poly (oxyalkylene) aminocarbamate is derived from a polyamine having from 2 to 12 nitrogen atoms of amine, and from 2 to 40 carbon atoms.
29. The fuel additive composition according to claim 28, characterized in that the polyamine is a polyalkylene polyamine having from 2 to 12 nitrogen atoms of amine, and from 2 to 24 carbon atoms.
30. The fuel additive composition according to claim 29, characterized in that the polyoxyalkylene polyamine is selected from the group consisting of ethylene diamine, propylene diamine, diethylenetriamine, and dipropylenetriamine.
31. The fuel additive composition according to claim 24, characterized in that the poly (oxyalkylene) portion of the hydrocarbyl poly (oxyalkylene) -aminocarbamate is derived from oxyalkylene units of 2 to 5 carbon atoms.
32. The fuel additive composition according to claim 24, characterized in that the hydrocarbyl poly (oxyalkylene) aminocarbamate is an alkylphenyl poly (oxybutylene) aminocarbamate, wherein the amine portion is derived from ethylenediamine or diethylenetriamine.
33. The fuel additive composition according to claim 1, characterized in that the poly (oxyalkylene) amine is a hydrocarbyl poly (oxyalkylene) monoamine.
34. The fuel additive composition according to claim 33, characterized in that the hydrocarbyl poly (oxyalkylene) monoamine is an alkylphenyl poly (oxyalkylene) monoamine, wherein the poly (oxyalkylene) moiety contains oxypropylene units or units. of oxybutylene, or mixtures thereof.
35. The fuel additive composition according to claim 34, characterized in that the alkylphenyl group is tetrapropenylphenyl.
36. A fuel composition characterized in that it comprises a major amount of hydrocarbons boiling in the range of gasoline or diesel, and an effective amount for controlling the deposits of a fuel additive composition comprising: (a) a compound of polyalkylphenoxyaminoalkane of the formula: or a fuel soluble salt thereof, wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000; Ri and R2 are independently hydrogen or lower alkyl having from 1 to 6 carbon atoms; and A is amino, N-alkyl amino having from 1 to about 20 carbon atoms in the alkyl, N, N-dialkyl amino group having about 1 to about 20 carbon atoms in each alkyl group, or polyamine portion having about 2 to about 12 nitrogen atoms of amine and about 2 to about 40 carbon atoms; and (b) a poly (oxyalkylene) amine having at least one basic nitrogen atom and a sufficient number of oxyalkylene units to render the poly (oxyalkylene) amine soluble in hydrocarbons boiling in the gasoline or diesel fuel range .
37. The fuel composition according to claim 36, chaerized in that one of Ri and R2 is hydrogen, methyl or ethyl, and the other is hydrogen.
38. The fuel additive composition according to claim 37, chaerized in that R2 is hydrogen, methyl or ethyl, and Ri is hydrogen.
39. The fuel composition according to claim 36, chaerized in that R is a polyalkyl group having an average molecular weight in the range of about 700 to 3,000.
40. The fuel composition according to claim 1, chaerized in that R is a polyalkyl group derived from polypropylene, polybutene, or a polyalphadefine oligomer of 1-octene or 1-decene.
41. The fuel composition according to claim 40, chaerized in that R is a polyalkyl group derived from polyisobutene.
42. The fuel additive composition according to claim 1, chaerized in that A is amino, N-alkyl amino or a polyamine portion.
43. The fuel composition according to claim 42, chaerized in that A is amino.
44. The fuel composition according to claim 42, chaerized in that A is a polyamine portion derived from a polyalkylene polyamine containing from about 2 to about 12 polyamine atoms of amine nitrogen, and from about 2 to about 24 carbon atoms.
45. The fuel composition according to claim 44, chaerized in that the polyalkylene polyamine has the formula: H 2 N- (R 3 -NH) 2-H wherein R 3 is an alkylene group having from about 2 to about 6 atoms of carbon, and z is an integer from about 1 to about 4.
46. The fuel composition according to claim 45, chaerized in that the polyalkylene amine is ethylene diamine or diethylene triamine.
47. The fuel additive composition according to claim 1, chaerized in that R is a polyalkyl group derived from polyisobutene, Ri and R2 are hydrogen, and A is amino or a polyamine portion derived from ethylene diamine.
48. The fuel composition according to claim 36, chaerized in that the poly (oxyalkylene) amine is a hydrocarbyl poly (oxyalkylene) -aminocarbamate.
49. The fuel composition according to claim 48, chaerized in that the hydrocarbyl group of the hydrocarbyl poly (oxyalkylene) aminocarbamate contains from 1 to about 30 carbon atoms; and wherein the amino portion of the hydrocarbyl poly (oxyalkylene) aminocarbamate is derived from a polyamine having from 2 to 12 amine nitrogen atoms, and from 2 to 40 carbon atoms.
50. The fuel composition according to claim 49, chaerized in that the hydrocarbyl group of the hydrocarbyl poly (oxyalkylene) aminocarbamate is an alkylphenyl group; and wherein the polyalkylene polyamine is selected from the group consisting of ethylenediamine, propylene diamine, diethylenetriamine, and dipropylenetriamine.
51. The fuel composition according to claim 50, characterized in that the alkyl portion of the alkylphenyl group is tetrapropenyl.
52. The fuel composition according to claim 48, characterized in that the hydrocarbyl poly (oxyalkylene) aminocarbamate is an alkylphenyl poly (oxybutylene) aminocarbamate, wherein the amine portion is derived from ethylenediamine or diethylenetriamine.
53. The fuel composition according to claim 36, characterized in that the poly (oxyalkylene) amine is a hydrocarbyl poly (oxyalkylene) monoamine.
54. The fuel composition according to claim 53, characterized in that the hydrocarbyl poly (oxyalkylene) monoamine is an alkylphenyl poly (oxyalkylene) monoamine, wherein the poly (oxyalkylene) moiety contains oxypropylene units or oxybutylene units. , or mixtures thereof.
55. The fuel composition according to claim 54, characterized in that the alkylphenyl group is tetrapropenylphenyl.
56. The fuel composition according to claim 36, characterized in that the composition contains from about 25 to about 2,000 parts per million by weight of the polyalkylphenoxyaminoalkane compound, and about 25 to about 2,000 parts per million of the poly. (oxyalkylene) amine.
57. The fuel composition according to claim 36, characterized in that the composition additionally contains from about 25 to about 5,000 parts per million by weight of a non-volatile carrier fluid, soluble in the fuel.
58. A concentrate for fuel, characterized in that it comprises an oleophilic, stable and inert organic solvent, boiling in the range from about 65.5 ° C to 204.4 ° C (about 150 ° F to 400 ° F), and from about 10 to about 70 percent by weight of a fuel additive composition comprising: (a) a polyalkylphenoxyaminoalkane compound of the formula: or a fuel soluble salt thereof, wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000; Ri and R2 are independently hydrogen or lower alkyl having from 1 to 6 carbon atoms; and A is amino, N-alkyl amino having from 1 to about 20 carbon atoms in the alkyl, N, N-dialkyl amino group having about 1 to about 20 carbon atoms in each alkyl group, or polyamine portion having about 2 to about 12 nitrogen atoms of amine and about 2 to about 40 carbon atoms; and (b) a poly (oxyalkylene) amine having at least one basic nitrogen atom and a sufficient number of oxyalkylene units to render the poly (oxyalkylene) amine soluble in hydrocarbons boiling in the gasoline or diesel fuel range .
59. The concentrate for fuel according to claim 58, characterized in that one of Ri and R2 is hydrogen or lower alkyl of 1 to 4 carbon atoms, and the other is hydrogen.
60. The concentrate for fuel according to claim 59, characterized in that R2 is hydrogen, methyl or ethyl, and Ri is hydrogen.
61. The concentrate for fuel according to claim 58, characterized in that R is a polyalkyl group having an average molecular weight in the range of about 700 to 3,000.
62. The concentrate for fuel according to claim 58, characterized in that R is a polyalkyl group derived from polypropylene, polybutene, or a polyalphaolefin oligomer of 1-octene or 1-decene.
63. The concentrate for fuel according to claim 62, characterized in that R is a polyalkyl group derived from polyisobutene.
64. The concentrate for fuel according to claim 58, characterized in that A is amino, N-alkyl amino or a polyamine portion.
65. The concentrate for fuel according to claim 64, characterized in that A is amino.
66. The concentrate for fuel according to claim 64, characterized in that A is a polyamine portion derived from a polyalkylene polyamine having from about 2 to about 12 polyamine atoms of amine nitrogen, and from about 2 to about 24 carbon atoms.
67. The concentrate for fuel according to claim 66, characterized in that the polyalkylene polyamine has the formula: H 2 N- (R 3 -NH) ZH wherein R 3 is an alkylene group having from about 2 to about 6 carbon atoms , and z is an integer from about 1 to about 4.
68. The concentrate for fuel according to claim 67, characterized in that the polyalkylene amine is ethylene diamine or diethylene triamine.
69. The concentrate for fuel according to claim 58, characterized in that R is a polyalkyl group derived from polyisobutene, Ri and R2 are hydrogen, and A is amino or a polyamine portion derived from ethylene diamine.
70. The concentrate for fuel according to claim 58, characterized in that the concentrate for fuel additionally contains from about 20 to about 60 weight percent of a non-volatile carrier fluid, soluble in the fuel.
71. The concentrate for fuel according to claim 58, characterized in that the poly (oxyalkylene) amine is a hydrocarbyl poly (oxyalkylene) -aminocarbamate.
72. The concentrate for fuel according to claim 71, characterized in that the hydrocarbyl group of the hydrocarbyl poly (oxyalkylene) aminocarbamate contains from 1 to about 30 carbon atoms; and wherein the amine portion of the hydrocarbyl poly (oxyalkylene) aminocarbamate is derived from a polyamine having from 2 to 12 amine nitrogen atoms, and from 2 to 40 carbon atoms.
73. The concentrate for fuel according to claim 72, characterized in that the hydrocarbyl group of the hydrocarbyl poly (oxyalkylene) aminocarbamate is an alkylphenyl group; and wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, propylene diamine, diethylenetriamine, and dipropylenetriamine.
74. The concentrate for fuel according to claim 73, characterized in that the alkyl portion of the alkylphenyl group is tetrapropenyl.
75. The concentrate for fuel according to claim 71, characterized in that the hydrocarbyl poly (oxyalkylene) aminocarbamate is an alkylphenyl poly (oxybutylene) aminocarbamate, wherein the amine portion is derived from ethylenediamine or diethylenetriamine.
76. The concentrate for fuel according to claim 58, characterized in that the poly (oxyalkylene) amine is a hydrocarbyl poly (oxyalkylene) monoamine.
77. The fuel concentrate according to claim 76, characterized in that the hydrocarbyl poly (oxyalkylene) monoamine is an alkylphenyl poly (oxyalkylene) monoamine, wherein the poly (oxyalkylene) moiety contains oxypropylene units or oxybutylene units. , or mixtures thereof.
78. The concentrate for fuel according to claim 77, characterized in that the alkylphenyl group is tetrapropenylphenyl. SUMMARY OF THE INVENTION The present invention describes an additive composition for fuel, comprising: (a) a polyalkylphenoxyaminoalkane compound of the formula: or a fuel soluble salt thereof, wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000; Ri and R2 are independently hydrogen or lower alkyl having from 1 to 6 carbon atoms; and A is amino, N-alkyl amino having from 1 to about 20 carbon atoms in the alkyl, N, N-dialkyl amino group having from about 1 to about 20 carbon atoms in each alkyl group, or a polyamine portion having about 2 to about 12 nitrogen atoms of amine and about 2 to about 40 carbon atoms; and (b) a poly (oxyalkylene) amine having at least one basic nitrogen atom and a sufficient number of oxyalkylene units to render the poly (oxyalkylene) amine soluble in hydrocarbons boiling in the gasoline fuel range or die -to the . The fuel additive compositions of this invention are useful as fuel additives for the prevention and control of deposits in the engine.