MXPA98000304A - The polyalykylphenoxyaminoalcanos and compositions for fuel containing the mis - Google Patents

Abstract

Polyalkylphenoxyaminoalkanes having the formula: (See Formula) wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000; R1 and R2 independently are 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 part of polyamine which it has about 2 to about 12 nitrogen atoms of amine and about > - up to approximately 40 carbon atoms. The compounds of formula I are useful as additives for fuel for the prevention and control of motor deposits.

Description

POLYALYCHINOPHYOXYAMINOALCANOS AND COMPOSITIONS FOR FUEL CONTAINING THE SAME BACKGROUND OF THE INVENTION Field of the Invention This invention relates to novel poly-alkyl-enoxyaminoalkanes. In a further aspect, this invention relates to the use of these compounds in fuel compositions. It will give rise to and control the engine deposits.

Description of the Referred Technique It is well known that automobile engines tend to form deposits on the surface of engine components, such as carburetor holes, valve bodies, fuel injectors, intake ports and intake valves. , due to the oxidation and polymerization of the hydrocarbon fuel, these deposits, even when they occur in relatively minor amounts, frequently cause problems of notable im- mobility, such as ref.- 026383 loss of speed and poor acceleration. In addition, engine deposits can significantly increase fuel consumption in the automobile and the production of exhaust pollutants. therefore, the development of detergents for effective fuels or additives for "deposit control" to prevent or control said deposits is of considerable importance and the number of such materials is known in the art.

For example, substituted phenols of aliphatic hydrocarbons are known to reduce engine deposits when used in compositions for fuel. The U.S. Patent No. 3,849,085, issued November 19, 1974 by Reuz et al., Describes a composition for motor fuel - which comprises a mixture of hydrocarbons in the boiling range of gasoline containing approximately 0.01 to 0.25 percent of a substituted phenol of the aliphatic hydrocarbon in which the aliphatic hydrocarbon radical has an average molecular weight in the range of about 500 to 3,500. This patent shows that gasoline compositions containing minor amounts of a substituted hydrocarbon phenol Aliphatic not only prevents or inhibits the formation of deposits in the valve and inlet holes in the gasoline engine, but also increases the performance of the fuel composition in engines designed to operate at high operating temperatures with a minimum of decomposition yf? mation of deposits in the engine distributor.

The U.S. Patent No. 4,259,086, issued March 31, 1981 by Achleder et al., Discloses a detergent additive for fuels and lubricating oils which comprises the reaction product of a substituted phenol of the aliphatic hydrocarbon, epichlorohydrin and a monoamine or polyamine first or secondary In addition, U.S. Pat. No. 4,048,081, issued September 13, -1 * 577 by Machleder et al., Describes a gasoline detergent additive which is the reaction product of a polyisobutene phenol with epichlorohydrin, followed by amination with diamine of ethylene or other polyamine.

Similarly, U.S. Pat. No. 4,134, 846, issued on January 16, 1979 by Machleder et al., Describes an additive composition for combustion. comprising a mixture of (1) the reaction product of a substituted phenol of the aliphatic hydrocarbon, of the epichlorohydrin and of a primary or secondary mono- or polyamine, and (2) a polyalkylene phenol. This patent shows that said compositions show an excellent system of induction, -carburetor and detergency in the combustion chamber when they are used in hydrocarbon fuels at low concentrations.

Aminophenols are also known to function as detergent / dispersing agents, antioxidants and anti-corrosives when used in fuel compositions. The U.S. Patent No. 4,320, 021, issued March 16, 1982 by R. M. Lange, for example, describes the amino phenols which have at least one substituent based on. the saturated hydrocarbon substantially of at least 30 carbon atoms. The amino phenols of this patent show that they impart. Useful and desirable properties for oil-based lubricants and normally liquid fuels.

In addition, polybutylamines have been shown to be useful for the prevention of defects in the intake system for internal combustion engines. For example, U.S. Pat. No. 4,832,702, issued May 23, 1089 by Kummer et al., Describes the compositions for fuels and lubricants containing polybutyl or -polyisobutylamine additives prepared by hydroforming a polybutene or polyisobutene and then subjecting the oxo product. resulting in a Mannich reaction or amination under hydrogenation conditions.

Additives for polyether amine fuels are also well known in the art for the prevention and control of engine deposits. These polyether additives have a polyoxyalkylene "backbone", ie, the polyether portion of the molecule consists of the repeating oxyalkylene units. The U.S. Patent No. 4,191,537, issued March 4, 1980 by Lewis et al., For example, describes a fuel composition that comprises a greater portion of hydrocarbons that boil in the range of gasoline and -from 30 to 2,000 ppm. a hydroxycarbonyloxyalkylene aminocarbamate having a molecular weight from about 600 to 10,000, and at least one basic nitrogen atom. The part of - Hydroxycarbyloxyalkylene is composed of oxyalkylene units having from 2 to 5 carbon atoms in each oxyalkylene unit. These compositions for fuels are shown for mají to have the cleaning of intake systems without contributing to deposits in the combustion chamber.

As well . is known in the art the aromatic compounds containing a part of poly (oxyalkylene). For example, the aforementioned U.S. Patent No. 4,191,537, discloses poly (oxyalkylene) alkylphenyl polymers which are useful as intermediates in the preparation of the poly (oxyalkylene) alkylphenyl aminocarbamates.

Similarly, U.S. Pat. No. 4,881,945, issued November 21, 1989 by Buckley, leaves a composition for fuel comprising of a hydrocarbon boiling in the range of gasoline or diesel and from about 30 to 5,000 parts per million of an aminocarbamate of alkyl. l-phenyl polyoxyalkylene having at least one basic nitrogen and an average molecular weight of -about 800 to 6,000 and wherein the alkyl group contains at least 40 carbon atoms.

The U.S. Patent No. 5,112,364, issued May 12, 1992 by Rath et al., Discloses gasoline engine fuels which contain small amounts of a polyetheramine and / or a polyetheramine derivative, where the polyetheramine is prepared by reductive amination of a polyether alcohol initiated by phenol or alkylphenol - with ammonia or a primary amine.

The Publication of the European Patent Solictud o. 310,875, published April 12, 1989, describes fuels for spark ignition engines containing a polyether amine additive prepared first by propoxylation and / or butoxylation of a primary or secondary alkanol or alkanoammonia and then amination of the resulting polyether with ammonia. or an aliphatic amine pritna ria.

Prench's Attestation No. 2,105,539, pubU every April 28, 1972, describes the additives - detergents for the carburetor which are phenoxypropylase, which can be substituted - with up to 5 hydrocarbon radicals of 1 to 30 carbon atoms. carbon in the aromatic ring. "sta patent also describes the additives obtained by reacting said phenoxypropylamines with the alkyl phosphoric acids.

SUMMARY OF THE INVENTION Recently, certain polyalkylphenoxyaminoalkanes have been discovered, which provide excellent control of engine deposits, especially deposits in the intake valve, when they are used as fuel additives in fuel compositions.

The compounds of the present invention include those having the following formula and soluble salts for fuels thereof: (I) wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000; R. and R_ independently are hydrogen or lower alkyl having from 1 to 6 carbon atoms; Y A is amino, N-alkylamino having from about 1 to about 20 carbon atoms in the alkyl, N, -dialkylamino group having from about 1 to about 20 carbon atoms in each alauyl group, or a part of - Doliamine having from about 2 to about 12 nitrogen atoms of amine and from about 2 to about 40 carbon atoms.

The present invention further provides a fuel composition comprising a greater amount of hydrocarbons that boil in the range of gasoline or diesel and an effective amount that controls the deposition of a compound of the present invention.

The present invention further provides a concentrate for fuel comprising a stable inert oleophilic organic solvent boiling in the range from about 150 ° F to 400 ° F and from about 10 to 70 weight percent of a compound of the present invention Among other factors, the present invention is based on the surprising discovery that certain polyalkylphenoxyaminoalkanes provide excellent control of engine deposits, especially in intake valves, when used as additives in fuel compositions.

DETAILED DESCRIPTION OF THE INVENTION The polyalkylphenoxyaminoalkanes of the present invention have the general formula: wherein R, R,, R2 7 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 about 700 to 3,000, and more preferably about 9O-Q to 2,500.

Preferably, one of R. and R9 is hydrogen or lower alkyl of 1 to 4 carbon atoms, and the other is hydrogen. More preferably, -one of R. and "is hydrogen, methyl or ethyl, and the other is hydrogen. More preferably, R "is hydrogen, methyl or ethyl, and R. is hydrogen.

In general, A is amino, N-alkylamino having from about 1 to about -20 carbon atoms in the alkyl group, Dreferred from about 1 to about 6 carbon atoms; N. -diallylamino having from about 1 to about 20 carbon atoms in each alkyl group, preferably from about 1 to about 6 carbon atoms, more preferably about 1 up to about 4 carbon atoms; or a -part of polyamine having from about 2 to about 12 nitrogen atoms of amine and from about 2 to about 40 carbon atoms, preferably from about 2 to 12 nitrogen atoms of amine and from about 2 to 24 carbon atoms . More preferably, A is amino or a part of -polyamine derived from a polyalkylene polyamine, including the alkylene diamine. More preferably, A is amino or a part of polyamine derived from ethylene diamine or diethylene triamine.

It is preferred that the substituent R be located in the meta position or, more preferably, in the para position in the aromatic, i.e., para ring or meta relative to the ether group.

The compounds of the present invention will generally have a molecular weight sufficient to be non-volatile at normal engine inlet valve operating temperatures (approximately 200 ° -250 ° C). Typically, the molecular weight of the compounds of this invention will fluctuate from about 700 to about 3,500, preferably from about 700 to about 2, 00.

The soluble salts for fuels of the compounds of formula I can easily be prepared by those compounds which contain an amino or substituted amino group and said salts are considered to be useful for preventing and controlling engine deposits. Appropriate salts include, for example, those obtained by protonation of the amino part with a strong organic acid, such as an alkyl- or arylsulfonic acid. Preferred salts are derived from toluene sulfadic 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: -NH, The term "N-alkylamino" refers to the -group: -NHRa, wherein Ra is an alkyl group. The term ", N-dialkylamino" refers to the group: -N b c, where they are alkyl groups.

The term "hydrocarbyl" refers to an organic radical primarily composed of carbon and hydrogen, which may be aliphatic, alicyclic, aromatic or combinations thereof, for example, aralkyl or alkaryl. Such hydroxycarbyl groups are generally free of aliphatic unsaturation, ie, olefinic or acetylenic unsaturation, but may contain minor amounts of heteroatoms, such as oxygen or nitrogen, or halogens, such as chlorine.

The term "alkyl" refers to both straight and branched chain 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 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. The most preferred raono-olefins include propylene, butylene, particularly isobutylene, 1-octene and 1-decene. The fine polyols prepared from said mono-olefins include polypropylene, polybutene, especially polyisobutene, and polyolefins produced from 1-octene and 1-decene.

The term "fuel" or "hydrocarbon fuel" refers to normally liquid hydrocarbons having boiling points in the ranks of gasoline and diesel fuels.

General Synthesis Procedures The polyalkylphenoxyaminoalkanes of this invention can be prepared by the following general methods and procedures. It can be appreciated that when typical or preferred process conditions are met (for example, reaction temperatures, times, mole proportions of reagents, solvents, pressures, etc.), other conditions can also be used. process unless contrary statement. The optimum 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 carrying out the following synthesis procedures. In these cases, the protective group will serve to protect the functional group from the unwanted reactions or to block this unwanted reaction with other functional groups or with the reagents used to carry out the chemical transformations of seadas. The appropriate selection of a protecting group for a particular functional group will easily be apparent to a person 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 herein.

Synthesis The polyalkylphenoxyaminoalkanes of the present invention can be prepared by a process, which initially involves the hydroxyalkylation of a polyalkyl phenol of the formula: wherein R is as defined herein, with an alkylene carbonate of the formula: wherein R. and R-, are as defined herein, in the presence of a catalytic amount of an alkali metal hydride or hydrdide, or an alkali metal salt, to give a polyalkylphenoxyalkane-nol of the formula: where R, R. are as defined here.

The polyalkylphenols of formula II are well-known materials and will typically be pregnated - by the alkylation of phenol with the polyolefin or the desired chlorinated polyolefin. A subsequent discussion of the polyalkylphenols can be found, for example, in U.S. Pat. No. 4,744,921 and U.S. Pat. No. 5,300,701.

Accordingly, the polyalkylphenols of formula II can be prepared from the corresponding olefins by conventional procedures. For example, the Dolyalkylphenols of formula II above can be prepared by reaction of the appropriate olefin or a mixture of olefin with phenol in the presence of an alkaline catalyst at a temperature from about 25 ° C to about 150 °. C, and preferably from 30 ° C to 100 ° C either alone or in an inefficient solvent essentially at atmospheric pressure. A preferred alkylation catalyst is boron trifluoride. The proportions of the reactants can be used. Alternatively, the molar excesses of phenol, ie, from 2 to 3 equivalents of phenol per equivalent of olefin with the unreacted phenol recirculated can be employed. The subsequent process maximizes the monoalkylphenol. Examples of inert solvents include heptane, benzene, toluene, chlorobenzene and diluent 250 which is a mixture of aromatics, paraffins and naphthenes.

The polyalkyl substituent in the polyalkylphenols used in the invention are generally derived from the polyolefins which are polymers or copolymers of the mono-olefins, particularly the 1-phono-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. The mono-olefins which are more preferred include propylene, butylene, particularly isobutylene, 1-octene and 1-decene. Polyolefins prepared from said mono-olefins include polypropylene, polybutene, especially polyisobutene, and polyalphaolefins produced from 1-octene and 1-decene.

Preferred polyisobutenes used to prepare the polyalkylphenols used later are the polyisobutenes which comprise less of the more reactive methyl vinylidene isomer, preferably at least 50% and more preferably at least 70%. Suitable polyisobutenes include those prepared using the BF_ catalysts. The preparation of said polyisobutenes in which the methylvinylidene isomer comprises a high percentage of the total composition is described in U.S. Patent Nos. 4,152,499 and 4,605,808. Said polyisobutenes, known as "reactive" polyisobutenes, produce 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 high alkylvinylidene content include Ultravis 30, a polyisobutene having an average molecular weight number of about 1300 and a methyl vinylidene content of -about 7%, and Ultravis 10, a polyisobutene which has an average molecular weight number of approximately 950 and a methylvinylidene content of approximately 76%, both available from -Rritish Petroleum.

The alkylene carbonates of formula III are known compounds, which are are available or can be easily prepared using conventional procedures. 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 the polyalkylphenol and the alkylene carbonate can be any of the well-known hydroxyalkali catalysts. Hydroalkyl catalysts include alkali metal hydrides, such as lithium hydride, sodium hydride and potassium hydride, alkali metal hydroxides, such as alkali metal salts, for example, 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 generally range from about 0.01 to 1.0 equivalents, preferably from about 0.05 to 0.3 equivalents.

The polyalkylphenol and the alkali carbonate are generally reacted in equivalent amounts essentially 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 in the absence of a -nert solvent.

The reaction time will vary depending on the particular alkylphenol and alkylene carbonate reagents, the catalyst used and the reaction temperature. Generally, the reaction time will range from about 2 hours to about 5 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. Nos. 2,987,555; 2,967,892; 3,283,030 and 4,341, 905.

Alternatively, the polyalkyl phenoxyalkanol product of formula IV can be prepared by reaction of the polyalkylphenol of formula II with the alkylene oxide of the formula: wherein R. and R "are as defined herein, in the presence of a hydroxyalkylation catalyst as described above.

Suitable alkylene oxides of formula V include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2, 3-butylene, and the like. A preferred alkylene oxide is ethylene oxide.

In a manner similar to the reaction with the alkylene carbonate, the polyalkylphenol and the alkylene oxide are reacted in equimolar or equivalent amounts essentially in the present invention. 0.01 to 1.0 equivalents of a hydroxyalkylation catalyst such as sodium or 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 carried out in the presence or in the absence of an anhydrous inert solvent substantially. Suitable solvents include toluene, xylene, and the like. Generally, the reaction is carried out in a sufficient pressure to contain the reactants and any solvents present, typically at atmospheric or higher pressure. Upon completion of the reaction, Dolialkyl-phenoxyalkanol is isolated by conventional procedures.

The polyalkylphenoxyalkanol of formula IV is subsequently reacted, either directly or through an intermediate, with an amine - suitable to give the desired polyalkylphenoxyaminoalkanes of formula I. Suitable amine reactants which can be used to form the amine compound , that is, substituent A, of the polyalkylphenoxyaminoalkanes of the present invention are discussed more fully below. cyon The amine compound In general, the amine compound of the polyalkylphenoxyaminoalkanes will contain an average of at least about one basic nitrogen atom per molecule. A "basic nitrogen atom" is one that is titratable by a strong acid, for example, a primary, secondary, or tertiary amine nitrogen; as distinguished from, for example, a carbarayl nitrogen, for example, - -0C (0) NH-, which is not titratable with a strong acid. Preferably, at least one of the basic nitrogen atoms of the amine compound will be primary or secondary amine nitrogen, more preferably, at least one will be a primary amine nitrogen.

The amine compound of the polyalkylphenoxyaminoalkanes of this invention is preferably derived from ammonia, from a dialkyl-secondary or primary alkyl monoamine, or from a polyamine having a terminal amino nitrogen atom.

The primary alkyl monoamines useful in the preparation of compounds of the present invention contain 1 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 about 4 carbon atoms. Examples of suitable monoamines include N-methylamine, N-ethylamine, N-propylamine, N-isopropylamine, N-butyl-amine, N-isobutylamine, N-sec-butylamine, N-tert-amine. Butylamine, Nn-pentylamine, N-cyclopentyl-amine, 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, N- (2-methoxyethyl) amine, N- (-ethoxyethyl) amine and the like. The preferred primary amines are N-methylamine, N-ethylamine and N-n-propylamine.

The amine compound of the polyalkyl enoxy aminoalkanes present 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 - one will contain from about 1 to about 20 carbon atoms, more preferably from about 1 to about 6 carbon atoms, more preferably from about 1-to about 4 carbon atoms. One or both of the alkyl groups may also contain one or more oxygen atoms.

Preferably, the secondary alkyl groups independently are selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-hydroxyethyl and 2-methoxyethyl. Preferably, the alkyl groups are methyl, ethyl or propyl.

Typical secondary amines which can be used in this invention include NN-dimethylamine, N, N-diethylaramine, N, N-di-n-propylamine, N, N-diisoproDylamine, N, N-di. -N-butylamine, N, N-di-sec-butylamine, NN-di-n-pentylaraine, N, N-di-n-hexylamine, N, -dicyclohexylamine, N, N-dioctylamine, N -ethyl-N-methylamine, N-methyl-N-propylamine, N-butyl-N-methylamine, N-ethyl-N-octylamine, N-ethyl-N-isopropylamine, N-ethyl-N- octylamine, N, N-di (2-hydroxyethyl) amine, N, -di (3-hydroxypropyl) amine, N, N-di (ethoxyethyl) amine, N, N-i (propoxy-ethyl) amine and the like. The secondary amines that are preferred are t N-diraethylamine, N-diethylamine and N, -di-n-propylamine.

The cyclic secondary amines can also be used to form the additives of this invention. In such cyclic compounds, the alkyl groups, when taken together, form one or more rings of 5- or 6-members containing up to about 20 carbon atoms. The ring containing the amine nitrogen atom is usually saturated, but one can also be fused 0 more saturated or unsaturated rings. The rings can be replaced with hydrocarbon groups from 1 to about 10 carbon atoms and may contain one or more oxygen atoms.

Suitable secondary cyclic amines include pineridine, 4-methyl oiperidine, pyrrolidine, morpholine, 2,6-dimethylmorpholine and the like.

The appropriate polyamines can have a straight-chain or branched structure and can be cyclic or acyclic or combinations of the same. Generally, the amine nitrogen atoms of said polyamines will be separated from each other by at least 2 carbon atoms, that is, the polyamines having an animal structure are not suitable. The polyamine may also contain one or more nitrogen atoms, typically present as an ether or as a hydroxyl group. Particular preference is given to polyamines having a carbon to nitrogen ratio of from about 1: 1 to about 10: 1.

In the preparation of the compounds of this invention using a polyamine where the various nitrogen atoms of Doliamine are not geometrically equivalent, several substitution isomers are possible and each of these possible isomers are encompassed within this invention.

Particularly a preferred group of polyamines for use in the present invention are the polyalkylene polyamines, including the alkylene diamines. Said polyalkylene polyamines will typically contain from about 2-to about 12 nitrogen atoms and from about 2 to about 40 carbon atoms, preferably about 2 to 24 carbon atoms. Preferably, the alkylene groups of said polyalkylene polyamines will contain from about 2 to about 6 carbon atoms, more preferably from about 2 to about 4 carbon atoms.

Examples of suitable polyalauylene polyamines include ethylenediamine, propylene diamine, isopropylene diamine, butylene diamine, pentylenediamine, hexylenediamine, diaethylene diamine, dipropylenetriamine, dimethylaminopropylamine, diisopropylenetriamine, dibutylenetriamine, di-sec-butylenetriamine. , triethylenetetramine, triproylentetraamine, triisobutylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, dimethylaminopropylamine, and mixtures thereof.

Particularly suitable polyalkylene polyamines are those having the formula: H N- (R_-NH) -H ¿i z where R-. is a straight-chain or branched alkyl 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, ie, ethylene (- CH_CH "-); and z is an integer from about 1 to about 4, preferably about 1 or about 2.

Particularly polyalkylene polyamines which are preferred are ethylenediaraine, diethylene diamine, triethylene tetraamine, and tetraethylenepentamine. The most preferred are ethylenediamine and diethyl entriamine, especially ethylenediamine.

Also contemplated for use in the present invention are cyclic polyamines having one or more 5- or 6-membered rings. Said cyclic polyamine compounds include piperazine, 2-methylpiperazine, N- (2-aminoethyl) piperazine, N- (2-hydroxyethyl piperazine, 1,2-bis- (N-piperazinyl) ethane, 3- aminooirrolidine, N- (2-aminoethyl) pyrrolidine, and the like. Among the polyamines c? - clicas, piperazines are preferred, Many of the polyamines suitable for use in the present invention are commercially available and others can be prepared by methods, which are well known in the art. For example, methods for the preparation of amines and their reactions are detailed in Sidgewick's "The Organic Chemistry of Nitrogen", Clarendon Press, Oxford, 1966; Noller's "Cheraistry of Organic Compounds," Saunders, Philadelphia, 2nd Ed., ~~ 1957; and Kirk-Othmer's "Encyclopedia of Chemical Technology", 2nd E. , especially Volume 2, pp. 99-116.

Preparation of polyalkylphenoxyaminoalkane As noted above, the polyalkyl-phenoxyaminoalkanes of the present invention can be conventionally prepared by reaction of the polyalkylphenoxyalkanol of formula TV, either directly or through an intermediate, with a nitrogen-containing compound, such as ammonia, a monoaraine. of secondary or primary alkyl, or a polyamine, as described herein.

Accordingly, the polyalkylphenoxyalkanol of formula IV can be converted to polyalayl phenoxyaminoalkane by a variety of methods known in the art.

For example, the terminal hydroxy group in the polyalkylphenoxyalkanol, it can first be converted to the appropriate leaving group, such as a me-silate, a chloride or a bromide, and the like, by reaction with an appropriate reagent, such as methanesulfonyl chloride. Then, the resulting polyalkylphenoxyalkylanyl mesylate or the equivalent intermediate can be converted to a -phthalimide derivative by reaction with the potassium phthalimide in the presence of an appropriate solvent, such as N, N-dimethylformamide. The polyalkylphenoxyalkyl phthalimide derivative is subsequently converted to the desired polyalkylphenoxyaminoalkane by reaction with an appropriate amine, such as the hydrazine. Alternatively, the leaving group can be converted to an azide, as described, for example, in Turnbull Scriven, Chemical eviews, vQlume 88, pages 297-368, 1988. Azide is subsequently converted to the desired polyallyl-phenoxyarainoalkane by reduction with hydrogen and a catalyst, such - such as palladium on carbon or a Lindlar catalyst.

The polyalkylphenoxyalkanol of formula IV, can also be converted to the corresponding polyalkyl phenoxyalkyl chloride by reaction with an appropriate halogenating agent, such as HCl, thionyl chloride, or epichlorohydrin, followed by displacement of the chloride with an amine suitable, such as ammonia, a primary or secondary alkyl monoamine, or a polyamine, as described, for example, in US Pat. -Do not. 4,247,301 by Honnen, the discovery which is incorporated herein by reference.

Alternatively, the polyalkylphenoxyaminoalkanes of the present invention can be prepared from the corresponding polyalkylphenoxyalkane by a process commonly referred to as "reductive amination," as described in U.S. Patent No. 5,112,364 by Rath et al. and U.S. Pat. -Do not. 4,332,595 by Herbstman et al., The discoveries 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 alkyl monoamine, in the presence of hydrogen and a hydrogenation-dehydrogenation catalyst. The amine reaction is typically brought to temperatures in the range of about -160 ° C to about 250 ° C and pressures of about 1,000 to about 5,000 psig, preferably from about 1,500 to about 3,000 psig. The "hydrogenation-dehydrogenation" catalysts include those containing platinum, palladium, cobalt, nickel, copper or chromium, or mixtures thereof. Generally, a molar excess of 5-fold to about 60-fold, and preferably about a 10-fold to about 40-fold molar excess of ammonia or amine is used.

When the reductive amination is carried out with a polyamine reagent, preferably the amination is carried out using a 2-step procedure as described in commonly assigned Co-pending US Patent Application Series No. 08 / 574,485 , presented on December 19, 1995, and entitled, "Reductive Amination Process for Manufacturing to Fuel Additive from Polyoxybutylene Alcohol with Etylene Diamine", the discovery which is hereby incorporated by reference in its entirety. According to this procedure, first an appropriate alcohol is contacted with a hydrogenation-dehydrogenation catalyst at a temperature of at least 230 ° C to give a carbonyl-containing intermediate, which subsequently is made 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 of the present invention, the polyalkylphenol of formula II may be reacted with an aziridine of the formula: wherein R. and R ~ are as described herein, and R, is hydrogen or alkyl of 1 to 20 carbon atoms. A preferred aziridine is a -where R. is hydrogen, R-, is hydrogen, methyl or ethyl, and R, 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.

Compositions for Fuel The compounds of the present invention are useful as additives in hydrocarbon fuels to prevent and control engine deposits, particularly deposits in the intake valve. The proper concentration of additive needed to achieve the desired deposit control varies depending on the type of fuel used, the type of engine, and the presence of other fuel additives.

In general, the concentration of the compounds of this invention in hydrocarbon fuel will range from about 50 to about 2500 parts per million (ppm) by weight, preferably from 75 to 1,000 ppm. When other additives for the control of deposits are presented, a smaller amount of the present additive may be used.

The compounds of the present invention can be formulated as a concentrate using a stable inert oleophilic organic solvent (ie, solvents in gasoline) that boil in the range of about 150 ° F to 400 ° F (about 65 ° C to 205 ° C). C). Preferably, an aliphatic or aromatic hydrocarbon solvent, such as benzene, toluene, xylene or higher boiling aromatic or aromatic diluents is used. The 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 will generally fluctuate from about - to about 70 percent by weight, preferably from 20 to 40 percent by weight. 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, anti-knock agents, such as methylcyclopentadienyl manganese tricarbonyl, and other dispersants / detergents, such as hydrocarbyl amines, hydrocarbyl poly (oxyalkylene) amines, hydrocarbyl poly (oxyalkylene) aminocarbamates, or succinimides. Additionally, antioxidants, metal deactivators and demulsifiers can be presented.

In diesel fuels, other well-known additives, such as spill point, flow improvers, cetane improvers, and the like, are to be used.

A non-volatile carrier oil or fluid soluble for fuel may also be used with the compounds of this invention. The carrier fluid is a liquid liquid carrier of chemically inert hydrocarbon which is substantially increases the non-volatile residue (NVR), or the solvent-free liquid fraction of the additive composition for fuel while overwhelmingly does not contribute to the increase of the octane requirement. The Dorter fluid can be a natural or synthetic oil, such as mineral oil, refined petroleum oils, synthetic polyalkanes and alkenes, including hydrogenated and non-hydrogenated polyalphaolefins, and synthetic polyoxyalkylene-derived oils, such as those described, for example, in Patent pS No. 4,191,537 by Lewis, and polyesters, such as those described, for example, in US Pat. Nos. 3,756,793 by Robinson and 5,004,478 by -Vogel et al., And European Patent Applications Nos. 356,726, published on March 7, 1990, and 382,159, published August 16, 1990.

The carrier fluids are believed to act as a carrier for the fuel additives of the present invention and to play a part in the removal and retardation of deposits. Also the carrier fluid may exhibit properties for the control of synergistic deposits when used in combination with a compound of this invention.

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 the carrier fluid to the additive for deposit control will range from about 0.5: 1 to about 10: 1, more preferably from 1: 1 to 4: 1, more 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 percent by weight, preferably from 30 to 50 percent by weight.

PREPARATIONS AND EXAMPLES A further understanding of the invention can be had in the following non-limited examples.

Where, unless expressly stated otherwise, -all temperatures and temperature ranges refer to the Centigrade system and the term "ambient" or "ambient temperature" refers to approximately 20 ° C-25 ° C. The term "percent" or "%" refers to percent by weight and the term "mol" or "moles" refers to grams-mol. The term "equivalent" refers to an amount of reactant equal in moles to the moles of the preceding or subsequent reagent referred to in that example in terms of finite moles or finite weight or volume. When given, the proton magnetic resonance spectrum (pmr or nmr) is determined at 300 mHz, the signals are assigned as multiplets of a single member (s), multiplets of a single broad member (bs), doublets (d) , double doublets (dd), triplets (t), double trioletes (dt), quartet (q), and multiplets (m), and the cps refers to the cycles per second.

Example 1 Preparation of Polyisobutyl Phenol 203.2 grams of phenol are added to a flask equipped with a magnetic stirrer, a reflux condenser, a thermometer, an addition funnel and a nitrogen inlet. E.1 phenol is heated to 40 ° C and the source of carbon is removed. lor Then, 73.5 milliliters of boron trifluoride etherate are added dropwise. 1040 grams of Ultravis 10 polyisobutene (molecular weight 950, 76% methylvinylidene, available from British Petroleum) are dissolved in 1,863 milliliters of hexa_no. The polyisobutene is added to the reaction at a ratio to maintain the temperature between -22 ° C-27 ° C. The reaction mixture is stirred for 16 hours at room temperature. Then, 400 milliliters of concentrated ammonium hydroxide is added, followed by 2,000 milliliters of hexane. The reaction mixture is washed with water (3 X 2,000 milliliters), dried over magnesium sulfate, filtered and the solvents are removed under vacuum to yield 1.056.5 grams of a crude reaction product.

The crude reaction product determines that COJI has 80% of the desired product by proton NMR - and by chromatography on silica gel, eluting with hexane, followed by hexane: ethyl acetate: ethanol (93: 5: 2).

Example 2 Preparation of PB (molecular weight - 950) The potassium hydride (1.1 grams of a 35 weight percent dispersion of a mineral oil) and the 4-polyisobutyl phenol (99.7 grams, prepared as in Example 1) are added to a flask equipped with a magnetic stirrer. , a reflux condenser, a nitrogen inlet and a thermometer. The reaction is heated to 130 ° C for one hour and then cooled to 100 ° C. The ethylene carbonate (8.6 grams) is added and the mixture is heated to 160 ° C for 16 hours. The reaction is cooled to room temperature and 1 milliliter of isopropanol is added. The reaction mixture is diluted with one liter of hexane, washed 3 times with water and once with brine. The organic layer is dried over anhydrous magnesium sulfate, filtered and the solvents are removed under vacuum to produce 98.0 grams of the desired product as a yellow oil.

Example 3 Preparation of PB (molecular we g t - 950) The alcohol of Example 2 (20.0 grams), triethylamine (2.9 mL), and non-anhydrous dichloromethane (200 mL) were combined. The solution is cooled to -0 ° C and methan-sulfonyl chloride (1.5 mL) is added dropwise. The reaction is stirred at room temperature under nitrogen for 16 hours. The solution is diluted with dichloromethane (600 mL) and washed 2 times with saturated aqueous sodium bicarbonate solution and once with brine. The organic layer is dried over anhydrous sodium sulfate, filtered and the solvents are removed in vacuo. to produce 20.4 grams as an oil loves lio.

Example 4 Preparation of H PB (molecular weig t - 950) Ethylenediamine (12.3 mL) and anhydrous toluene (100 mL) are combined under nitrogen. The product of Example 3 (20.4 grams, dissolved in -100 mL of anhydrous toluene) is added dropwise. The resulting solution is refluxed for 16 hours. The solution is diluted with hexane (600 mL) and washed once with a saturated aqueous sodium bicarbonate solution, 3 times with water and once with brine. The organic layer is dried over anhydrous sodium sulfate, filtered and the solvents are eliminated in vacuo to yield 15.1 grams as a yellow oil, The oil is chromatographed on silica gel, eluting with hexane / diethyl ether (50:50), then with hexane / diethyl ether / methanol / isopropylamine (40: 40: 15: 5) to yield 10.3 grams of the desired product as a yellow oil. H NMR (CDClg) d 7.25 (d, 2H), 6.8 (d, 2H), 4.1 (t, 2H), 3.0 (t, 2H), 2.85 (t, 2H), 2.75 (t, 2H). 1.95 (bs, 3H), 1.5-0.7 (m, 137H).

Example 5 Preparation of The mesylate prepared as described in Example 3 (406.5 grams), sodium azide (198.2 grams), Adogen 464, a methyltrialkyl ammonium chloride (Co0-C, 1n0) available from Ashland Chemical (8.0 mL) is combined. ), N, N-dimethylformamide (800 mL) and toluene (1.2 L). The reaction is refluxed for 16 hours and cooled to room temperature. The mixture is filtered and the solvent is removed in vacuo. The residue is diluted with hexane (3.0 L) and washed three times with water and once with brine. The organic layer is dried over anhydrous magnesium sulfate, filtered and the solvents are removed in vacuo to yield 334.3 grams of the desired azide as a yellow oil.

Example 6 Preparation of A solution of the product of Example 5 (334.3 grams) in ethyl acetate (750 mL) and toluene (750 mL), containing palladium in 10% charcoal (7.0 grams) is hydrogenated at 35-40 psi for 16 hours in a Low Pressure Hydrogenator Parr. Filtration of the catalyst and removal of the solvent in vacuo yields 322.3 grams of the desired product as a yellow oil.

! H NMR (CDClg) d 7.25 (d, 2H), 6.8 (d, 2H), 4.0 (t, 1H), 3.1 (t, 2H), 2.35 (bs, 2H), 0.7-1.6 (m, 137H).

Example 7 Preparation of P B (molecular weight - 950) The potassium hydride (15.1 grams of a 35 weight percent dispersion of mineral oil) and the 4-polyisobutyl phenol (1378.5 grams, prepared as in Example 1) are added to a flask equipped with a magnetic stirrer, a reflux condenser, a nitrogen inlet and a thermometer. The reaction is heated to 130 ° C by one hour and then cool to 100 ° C. Propylene carbonate (115.7 milliliters) is added and the mixture is heated at 160 ° C for 16 hours. The reaction is cooled to room temperature and 10 milliliters of isopropanol are added. The reaction is diluted with 10 liters of hexane, washed three times with water and once with brine. the organic layer is dried over anhydrous magnesium sulfate, filtered and the solvents are removed in vacuo to yield 1301.7 grams of the desired product as a yellow oil.

Example 8 Pre paration of - 950) The alcohol of Example 7 (50.0 grams), triethylamine (7.0 mL), and anhydrous dichloromethane (500 mL) are combined. The solution is cooled to 0 ° C and methan-sulfonyl chloride (3.7 mL) is added dropwise. the reaction is stirred at room temperature under nitrogen for 16 hours. The solution is diluted with dichloromethane (1.5 L) and washed 3 times with a saturated aqueous sodium bicarbonate solution and once with brine. The organic layer is dried over anhydrous sodium sulfate, filtered and the solvents are removed in vacuo to yield 57.7 grams as a yellow oil.

Example 9 Preparation of The mesylate of Example 8 (57.7 grams), sodium azide (27.1 grams), Adogen 464 (1.0 mL), N-diethylformamide (400 mL) and toluene (600 mL) are combined. The reaction is refluxed for -16 hours and cooled to room temperature. The mixture is filtered and the solvents are removed in vacuo. The residue is diluted with hexane (1.5 L) and washed three times with water and once with sajl dies. The organic layer is dried over anhydrous magnesium sulfate, filtered and the solvents are removed in vacuo to yield 43.1 grams of the desired azide as a yellow oil.

Example 10 Preparation of PB (molecular eight ~ 950) A solution of the product of Example 9 (43.1 grams) in ethyl acetate (100 mL) and toluene (100 mL), containing palladium in 10"charcoal (2.0 grams) is hydrogenated at 35-40 psi for 16 hours in a Parr low pressure hydrogenator. Catalyst filtration and solvent removal in vacuo yields 41.5 grams of the desired product as a yellow oil.H NMR (CDC13) d 7.25 (d, 2H), 6.85 (d, 2H), 3.9 (abq, 1H), 3.65 (abq, 1H), 3.35 (m, 1H), 1.9 (bs, 2H), 0.7-1.6 (m, 140H).

Example 11 Test in a Cylinder Motor The test compounds are mixed in lino gas and their capacity to reduce deposits is determined in a test on a cylinder motor, A one cylinder CFR Waukesha engine is used. Each run is carried out for 15 hours, at the end of that time the intake valve is removed, washed with hexane and weighed.

The previously determined weight of the clean valve is subtracted from the weight of the valve at the end of the run. The differences between the 2 pesos, is the weight of the deposit. A smaller amount of deposit indicates a higher additive. The operating conditions of the test are as follows: the temperature of the cooling jacket 2Q0 ° P; the vacuum of 12 inches of mercury, the air-fuel ratio of 12, the setting of the spark ignition engine of 400 BTC; the motor speed is 1800 rpm; Crankcase oil is a commercial 30W oil.

The amount of carbonaceous deposit in iligrams in the intake valves is reported for each of the test compounds in Table I and Table II.

TABLE I Weight of the tank in the intake valve (in milligrams) Sample 1 run 1 Run 2 Average Base Fuel 333. 5 354. 9 344. 2 Example 4 22. 5 22. 7 22. 6 150 active parts per million (ppma) TABLE II Weight of the reservoir in the intake valve (in milligrams) Sample 1 Run 1 Run 2 Average Base Fuel 323.8 312.1 318.0 Example 6 12.1 21.0 16.6 1a 125 active parts per million (opma) The base fuel used in the previous cylinder engine tests is a regular octane unleaded gasoline that does not contain fuel oil. The test compounds are 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 of deposits in the intake valve given by the polyalkyl phenoxyaminoalkanes of the present invention (Examples 4 and 6) compared to the base fuel.

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

Having described the invention as above, the content of the following is claimed as property.

Claims (63)

1. A compound of the formula or a soluble salt for fuel thereof, characterized in that R is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000; 1 and R-, independently are hydrogen or lower aluyl having 1 to 6 carbon atoms; Y A is amino, N-alkylamino having from about 1 to about 20 carbon atoms in the alkyl, N-dialkylamino group having aoxy from 1 to about 20 carbon atoms in each alouyl group, or a polyamine part which has about 2 to about 12 nitrogen atoms of amine and about from about 2 to about 40 carbon atoms.

The compound according to claim 1, characterized in that one of R "is hydrogen or lower alkyl of 1 to 4-carbon atoms, and the other is hydrogen

3. Pl composed according to claim 2, characterized in that one of R, y is hydrogen, methyl or ethyl, and the other "is hydrogen.

4. The compound according to claim 3, characterized by "is hydrogen, methyl or ethyl, and R- is hydrogen.

5. The compound 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 compound according to claim 5, characterized in that R is a polyalauyl group having an average molecular weight in the range of about 700 to 3,000.

7. The compound 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.

8. The compound according to claim 1, characterized in that R is a polyalkyl group derived from polypropylene, polybutylene, or a polyalphaolefin oligomer of 1-octene or -1-decene.

9. The compound according to claim 8, characterized in that R is a polyalkyl group derived from polyisobutene.

10. The compound according to claim 9, characterized in that the polyisobutene COJI has at least about 20% of a methylvinylidene isomer.

11. The compound according to claim 1, characterized in that A is amino, N-alkylamino or a part of polyamine.

12. The compound according to the claim 11, characterized in that A is amino or N-alkylamino having from about 1 to about 4 carbon atoms in the -alkyl group.

13. The compound according to claim 12, characterized in that A is amino.

14. The compound according to claim 11, characterized in that A is a part of polyamine having from about 2 to about 12 nitrogen atoms of amine and from about 2 to about 40 carbon atoms.

15. The compound according to claim 14, characterized in that A is a part of polyamine derived from a polyalkylene polyamine containing from about 2 to about 12 polyamine nitrogen atoms of amine and from about 2 to about 24 carbon atoms.

16. The compound according to claim 15, characterized in that the polyamine of > olialq uíleno has the formula: H2N- (R3- Ntn z -H wherein R "is an alkylene group having from about 2 to about 6 carbon atoms and z is an integer from about 1 - up to about 4.

17. The compound according to claim 16, characterized in that R_ is urT alkylene group having from about 2 to about 4 carbon atoms.

18. The compound according to claim 17, characterized in that the polyalkylene polyamine is the ethylene diamine or the diethylene triamine. 1Q.

The compound according to claim 18, characterized in that the polyalkylene polyamine is the ethylene diamine.

20. The compound according to claim 1, characterized in that R is a group - polyalkyl derivative of the polyisobutene, R ^ and ^ 2 are hydrogen and A is amino or a part of polyamine -derivated from the diamine < I etiieno.

21. A composition for fuel, characterized in that it comprises a greater amount of hydrocarbons that boil in the range of gasoline or diesel and a quantity controlled by the effective deposit of a compound of the formula: or a soluble salt for fuel thereof, wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000; R, and 2 independently are hydrogen or lower alkyl having 1 to 6 carbon atoms; Y A is amino, N-alkylamino having from about 1 to about 20 carbon atoms in the alkyl, N-dialkylamino group having about 1 to 20 carbon atoms in each alkyl group, or a part of polyamine having about from 2 to about 12 nitrogen atoms of amine and from about 2 to about 40 carbon atoms.

22. The composition for fuel according to claim 21, characterized in that one of R. and R-, is hydrogen or lower alkyl of 1 to 4 carbon atoms, and the other is hydrogen.

23. The composition for fuel according to claim 22, characterized in that one of R. and R "is hydrogen, methyl or ethyl, and the other is hydrogen.

24. The composition for fuel according to claim 23, characterized in that R ~ is hydrogen, methyl or ethyl, and R. is hydrogen.

25. The composition for COJI fuel according to claim 21, characterized in that R is a polyalkyl group having an average molecular weight in the range of about 600 to 3,000.

26. The composition for COI fuel according to claim 25, characterized in that R is a polyalkyl group having an average molecular weight in the range of about -700 to 3,000. ~~

27. The composition for fuel according to claim 26, characterized in that R. is a polyalkyl group having an average molecular weight in the range of about Q00 to 2,500.

28. The composition for fuel according to claim 21, characterized in that R is a polyalkyl group derived from polypropylene, polybutene, or a polyalphaolefin oligomer of 1-octene or 1-decene.

29, The composition for fuel of con- according to claim 28, characterized in that R is a polyalkyl group derived from polyisobutene.

30. The composition for conformance fuel according to claim 29, characterized in that the polyisobutene contains at least about 20% of a methylvinylidene isomer.

31. The composition for conformance fuel to claim 21, characterized in that A is amino, N-alkylaraine or a part of polyamine.

32. The fuel composition according to claim 31, characterized in that A is amino or N-alkylamino having from about 1 to about 4 carbon atoms in the alkyl group.

33. The conforming fuel composition of claim 32, characterized in that A is amino.

34. The fuel composition according to claim 31, characterized in that A is a part of polyamine having from about 2 to about 12 nitrd atoms. amine atom and from about 2 to about 40 carbon atoms.

35. The fuel composition according to claim 34, characterized in that A is a part of polyamine derived from a polyalkylene polyamine containing from about 2 to about 12 polyamine atoms of amine nitrogen and from about 2 to about 24 atoms. of carbon.

36. The composition for fuel according to claim 35, characterized in that - the polyalkylene polyamine has the formula: where R-. is an alkylene group having from about 2 to about 6 carbon atoms and z is an integer from about 1 to about 4.

37. The composition for fuel according to claim 36, characterized in that Rg is an alkylene group having from approx. 2 to about 4 carbon atoms,

38. The composition for fuel according to claim 37, characterized in that the polyalkylene polyaraine is the ethylene diamine or the diethylene monomer.

39. The fuel composition according to claim 38, characterized in that the polyalkylene polyamine is the ethylene diamine.

40. The composition for confor fuel; The claim 21, characterized in that R is a polyalkyl group derived from the polyisobutene, R- and R-, are hydrogen and A is amino or a part of polyamine derived from the diariein of -ethylene.

41. The composition for fuel according to claim 21, characterized in that the composition contains from about 50 to about 2,000 parts per million by weight of said compound.

42. The fuel composition according to claim 21, characterized in that the composition further contains from about 100 to about 5,000 parts per million by weight of a non-volatile carrier fluid, soluble for fuel.

43. A concentrate for fuel, caracterj. Because it comprises an inert oleophilic solvent which boils in the range from about 150 ° F to 400 ° F and from about 10 to about 70 weight percent of a -compound of the formula: or a soluble salt for fuel thereof, wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000; R- and R "independently are hydrogen or lower alkyl having from 1 to 6 carbon atoms; Y 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 part of polyamine having from about 2 to about 12 nitrogen atoms of amine and from about 2 to about 40 carbon atoms.

44. The concentrate for fuel according to claim 43, characterized in that one of R .. and R "is hydrogen or lower alkyl of 1 to 4 carbon atoms, and the other is hydrogen no.

45. The concentrate for fuel according to claim 44, characterized in that one of R. and R ~ is hydrogen, methyl or ethyl, and the other is hydrogen.

46. The confound fuel concentrate as claimed in claim 45, characterized in that it is hydrogen, methyl or ethyl, and R. is hydrogen.

47. The concentrate for fuel according to claim 43, characterized in that R is a polyalkyl group having an average molecular weight in the range of about 600 to 3,000.

48. The concentrate for fuel according to claim 47, characterized in that R is a polyalkyl group having an average molecular weight in the range of about 700 to 3,000.

49. The concentrate for fuel according to claim 48, characterized in that R is a polyalkyl group having an average molecular weight in the range of about 900 to 2,500.

50. The concentrate for fuel according to claim 43, characterized in that R is a polyalkyl group derived from polypropylene, polybutene, or a polyalphaolefin ollgomero of 1-octene or 1-decene.

51. The concentrate for fuel according to the indication 50, characterized in that R - is a polyalkyl group derived from the polyisobutene.

52. The conforming fuel concentrate according to claim 51, characterized in that the polyisobutene contains at least about 20% of a methylvinylidene isomer.

53. The concentrate for fuel according to claim 43, characterized in that A - is amino, N-alkylamino or a part of polyamine.

54. The concentrate for conforming fuel to claim 53, characterized in that A is amino or N-alkylamino having from about 1 to about 4 carbon atoms in the alkyl group.

55. The concentrate for fuel according to claim 54, characterized in that A is amino.

56. The fuel composition according to claim 53, characterized in that A is a part of polyamine having from about 2 to about 12 nitrogen atoms of amine and from about 2 to about 40 carbon atoms.

57. The concentrate for fuel according to claim 56, characterized in that A is a part of polyamine derived from the polyalkylene polyamine containing from about 2 to about 12 polyamine atoms of amine nitrogen and from about 2 to about 24 carbon atoms.

58. The concentrate for fuel according to claim 57, characterized in that the polyalkylene polyamine has the formula: H2N- (R3-NH) z-H wherein R "is an alkylene group having from about 2 to about 6 carbon atoms carbon and z is an integer from about 1 - to about 4.

59. The concentrate for fuel according to claim 58, characterized in that R "is an alkylene group having from about 2 to about 4 carbon atoms.

60. The concentrate for fuel according to claim 59, characterized in that the polyalkylene polyamine is the ethylene diamine or the diethylene triamine.

61. The concentrate for fuel according to claim 60, characterized in that the polyalkylene polyamine is the ethylene diamine.

2. The fuel concentrate according to claim 43, characterized in that R is a polyalkyl group derived from the polyisobutene, R. and "are hydrogen and A is amino or a part of polyamine derived from the ethylene diamine.

63. The concentrate for confounding fuel of claim 43, characterized in that the concentrate for fuel further contains from about 20 to about 60 weight percent of a non-volatile carrier fluid, soluble for fuel. SUMMARY OF THE INVENTION The polyalkylphenoxyaminoalkanes having the formula: wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000; R1 and R- are independently hydrogen or lower alkyl having from 1 to 6 carbon atoms; 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. carbon in each alkyl group, or a part of polyamine having from about 2 to about 1 nitrogen atoms of amine and about 2 to about 40 carbon atoms. The compounds of formula I are useful as additives for fuel for the prevention and control of engine deposits.