DE102006006252A1 - Fuel additive composition - Google Patents

Abstract

Disclosed is an additive composition comprising a Mannich product, a polyetheramine, and a friction modifier. Also disclosed is a fuel composition comprising the fuel additive composition, an engine combusting the fuel composition, and a method of preventing and / or reducing formation of deposits in an engine.

Description

The The present invention relates to a fuel additive composition, a detergent such as a Mannich product, a dispersant such as a polyetheramine and a friction modifier such as an amide. The Fuel additive composition may be used in compositions such as Fuel compositions useful be.

introduction

In Fuels used in gasoline engines generally contain components the formation of unwanted Lead deposits on the engine. It is believed that these deposits affect engine performance, e.g. Fuel Supply Systems can clog. There has been extensive research to look for additives, which control the formation of deposits in gasoline engines (prevent or decrease). The production and identification of fuel additives, the the formation of unwanted deposits can control have been a focal point of this research.

In In recent years, various car manufacturers have in common new voluntary standards for control of gasoline deposits created. The purpose was a new class of commercial gasoline to define with improved detergent that as TOP PET detergent gasoline was designated. A document titled "TOP TIER Detergent Gasoline Deposit Control Performance Standards ", the disclosure of which is hereby incorporated by reference into this application became the 33rd Automotive Petroleum Industry on April 6, 2004 Forum presented by the American Petroleum Institute. These norms include the following test procedures: initial clean-up performance of intake valves, initial performance with respect to deposits in the combustion chamber, Initial performance with respect to pollution of the fuel injector, detection the performance of an additive with respect to the control of deposits as well as the initial performance regarding the Clogging of the intake valve.

Therefore there is a need in the industry for fuels and fuel additive that meet the TOP TIER performance standards.

Summary

According to different Aspects of the disclosure are provided: a fuel additive composition, a Mannich product, a polyether amine, and a friction modifier contains, as well a process for the preparation of a fuel additive, comprising the provision of a Mannich product, a polyetheramine and a friction modifier to a To give fuel additive.

Of course they are both the above general description and the following Description of various embodiments merely illustrative and illustrative, but not limiting.

description various embodiments

The disclosed fuel composition can in one embodiment contain a detergent such as a Mannich product. The Mannich product can be a fuel soluble Be reaction product formed by the reaction of i) an amine, ii) an alkyl-substituted hydroxyaromatic compound and iii) an aldehyde is. In one embodiment The Mannich product may be a reaction product produced by the Reaction of a substituted with a low molecular weight alkyl hydroxyaromatic compound, an aldehyde and an aminoalcohol is obtained. This is disclosed in US-A-6,176,886, the disclosure of which is incorporated herein by reference.

Amines suitable for use as component i) may comprise at least one primary or secondary amine group and also contain at least one hydroxyl group. In other embodiments, the amine reactants may be amino alcohols, alkoxylated amines, and mixtures thereof. Non-limiting examples of suitable amino alcohols include ethanolamine and diethanolamine. Non-limiting examples of alkoxylated amines include ethoxylated and propoxylated amines and polyamines ne. An example of these amines includes, for example, 2- (2-aminoethylamino) ethanol. In another embodiment, diethanolamine can be used.

Polyamines suitable for use as an amine in the preparation of the Mannich product may comprise at least two amine groups wherein at least one of the amine groups is a primary or secondary amine. Non-limiting examples of polyamines include alkylene polyamines which comprise at least one correspondingly reactive primary or secondary amino group in the molecule. Other substituents may also be present in the polyamine. In one embodiment, the alkylenepolyamine may be a polyethylenepolyamine. Suitable alkylene polyamine reactants include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethylenemoneamine, nonaethylene decamine, decaethyleneundecamine and mixtures of such amines having a nitrogen content equal to that of alkylene polyamines of the formula H ₂ N- (A-NH-) _n H, in A may be a divalent ethylene or propylene and n may be an integer from about 1 to about 10. The alkylene polyamines can be prepared by the reaction of ammonia and dihaloalkanes such as dichloroalkanes. Thus, the alkylene polyamines prepared by the reaction of from about 2 to about 11 moles of ammonia with from about 1 to about 10 moles of dichloroalkanes having from about 2 to about 6 carbon atoms and the chlorine atoms on different carbon atoms may be suitable alkylene polyamine reactants.

at another embodiment For example, the amine may be a polyamine having at least one primary or secondary Has amino group and at least one tertiary amino group in the molecule. examples for suitable polyamines include N, N, N ", N" -tetraalkyldialkylenetriamines (two terminal tertiary amino groups and a secondary one Amino group in the middle), N, N, N ', N "-tetraalkyltrialkylenetetramine (a terminal tertiary Amino group, two internal tertiary amino groups and one terminal primary amino group), N, N, N ', N''N' '' - pentaalkyltrialkylenetretramine (a terminal tertiary Amino group, two internal tertiary amino groups and one terminal secondary amino group), tris (dialkylaminoalkyl) aminoalkylmethanes (three terminal tertiary amino groups and a terminal one primary Amino group) and the like Compounds in which the alkyl groups are the same or different from one another can be different and each not more than about 12 carbon atoms, for example each may contain from about 1 to about 4 carbon atoms. For example can these alkyl groups be methyl and / or ethyl groups. For certain embodiments include the polyamine reactants N, N-dimethyl-1,3-propanediamine and N-methyl piperazine.

The ii) alkyl-substituted hydroxyaromatic compounds and iii) the aldehydes used to make the Mannich product can be can in compliance with the above restrictions, all those compounds which are known and used in the art.

Representative ii) alkyl-substituted hydroxyaromatic compounds which can be used to prepare the Mannich product Polypropylphenol (prepared by the alkylation of phenol with Polypropylene), polybutylphenols (prepared by the alkylation of phenol with polybutenes and / or polyisobutylene) and polybutyl-co-polypropylphenols (prepared by the alkylation of phenol with a copolymer butylene and / or butylene and propylene), but are not limited. In one embodiment For example, the alkylaromatic hydroxyaromatic compound can be selected from polyolefin substituted phenols such as polybutylene substituted ones Phenols, polypropylene-substituted phenols and example Polyisobutylcresols are produced.

It can other similar ones long-chain alkylphenols are used. Non-limiting examples include phenols made with copolymers of butylene and / or isobutylene and / or propylene and at least one copolymerizable therewith monoolefinic comonomer (e.g., ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene etc.), wherein the copolymer molecule contains at least 50% by weight of butylene and / or Isobutylene and / or propylene units comprises. The with propylene or such butenes polymerized comonomers may be aliphatic and also non-aliphatic groups such as styrene, o-methylstyrene, p-methylstyrene, Divinylbenzene and the like include. So in any case, the resulting Polymers and copolymers used to make the alkyl substituted ones hydroxyaromatic compounds are used, essentially be aliphatic hydrocarbon polymers. In one embodiment For example, the alkylphenol can be selected from cresols.

Polybutylphenol (made by the alkylation of phenol with polybutylene) can be used. Unless otherwise stated herein, the term "polybutylene" is used in the generic sense and encompasses polymers made from any "pure" or "substantially pure" 1-butene or isobutene, and polymers derived from Mixtures of two or all three of 1-butene, 2-butene and isobutene can be prepared. Commercially available grades of such polymers can also un significant amounts of other olefins. So-called highly reactive polybutylenes having relatively high levels of vinylidene-terminated polymer molecules prepared, for example, by the methods described in US-A-4,152,499 and West German Offenlegungsschrift 29 04 31, the disclosures of which are hereby incorporated herein by reference; may also be useful for preparing the long chain alkylated phenol reactant.

The Alkylation of the hydroxyaromatic compound may be in the presence an alkylation catalyst at a temperature in the range of about 50 to about 200 ° C carried out become. In general, can be acidic Catalysts for accelerating Friedel-Crafts alkylation be used.

Catalysts used in industrial production include, for example, sulfuric acid, BF ₃ , aluminum phenoxide, methanesulfonic acid, cationic exchange resin, acidic clay, and modified zeolites or other Lewis acids such as tin halides.

The long-chain alkyl substituent on the phenolic benzene ring Can connect of polyolefins with one determined by gel permeation chromatography number average molecular weight (Mn) of about 500 to about 3,000 (e.g., from about 500 to about 2001). In some embodiments For example, the polyolefin may have a polydispersity (weight average Molecular weight / number average molecular weight) in the range of about 1 to 4, e.g. about 1 to about 2.

The For example, Mannich product can be made from a long chain alkylphenol be prepared. It can however, other phenolic compounds are used, as well other high molecular weight alkyl substituted derivatives of resorcinol, hydroquinone, catechol, hydroxydiphenyl, benzylphenol, Phenethylphenol, naphthol and tolylnaphthol. In certain embodiments For example, the Mannich product can be prepared from polyalkylphenol reactants, e.g. polypropylphenol and polybutylphenol, whose alkyl group is a number average Has molecular weight of about 500 to about 2,100. It can the Alkyl group be a polybutyl group, that of a polybutylene having a number average molecular weight in the range of about 800 until about 1,300 is derived.

A Configuration of Alkyl Substituted Hydroxyaromatic Compound may be that of a para-substituted monoalkylphenol. It can however, any alkylphenol used in the Mannich condensation reaction reacts easily. The long-chain alkyl substituents may have something residual unsaturation but generally substantially saturated branched or linear alkyl groups.

Representative iii) comprise aldehydes for use in the preparation of the Mannich product aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, Butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde and stearaldehyde, but are not limited to this. Aromatic aldehydes that may be used include benzaldehyde and salicylaldehyde. Exemplary heterocyclic aldehydes which can be used here are furfural and thiophene aldehyde etc. Also useful formaldehyde-generating Reagents such as paraformaldehyde or aqueous formaldehyde solutions such as Be formalin. In one embodiment Formaldehyde or formalin can be used.

The Components i), ii) and iii) can be reacted under suitable Mannich reaction conditions, to make a Mannich product. The condensation reaction between the alkyl-substituted hydroxyaromatic compound, the Amine and the aldehyde may be at a temperature in the range of about 40 to about 200 ° C carried out become. The reaction can be carried out with bulk material (without thinner or Solvent) or in a solvent or thinner carried out become. This can cause water to form during the course of the reaction can be removed by azeotropic distillation. In one embodiment The Mannich product can be prepared by reacting the alkyl substituted ones hydroxyaromatic compound, amine and aldehyde in one molar ratio from 1.0: 0.2-8.8 : 1.0-4.0, e.g. 1: 0.5-5 : 1.5-2.5. The aldehyde may be present in a molar amount which is at least the Total molar amount of the existing amine compound corresponds.

The detergent may be present in the fuel additive composition in any amount sufficient to reduce and / or prevent the formation of deposits on, for example, intake valves and valves of the combustion chamber. In one embodiment, the Mannich product may comprise about 5 ptb to 300 ptb, eg, about 25 ptb to about 200 ptb or, as another example, about 75 to about 150 ptb of active material in the fuel additive composition. Commercially available examples of a Mannich product HiTEC ^® 6416 (Ethyl Corp., Richmond, VA) include.

The The disclosed fuel additive composition may be reaction products of the Mannich product. For example, the fuel additive composition in one embodiment up to 15% by weight unreacted polyisobutylene phenol and / or up to about 10% by weight of unreacted polyisobutylene.

The fuel additive composition may also include a dispersant such as a polyetheramine or a polyether. The disclosed polyetheramine can be represented by the formula R (OCH ₂ CH (R ¹ )) _n A. Therein, R may be a hydrocarbyl group of 1 to 30 carbon atoms, R ^{1 may be selected} from the group consisting of hydrogen, hydrocarbyl groups of about 1 to about 16 carbon atoms and mixtures thereof, n may be a number from about 2 to about 50 and A may be be selected from the group consisting of -OCH ₂ CH ₂ CH ₂ NR ² R ² and -NR ³ R ³ wherein each R ^{2 may} independently be hydrogen or hydrocarbyl of about 1 to 16 carbon atoms and each R ^{3 is} independently hydrogen, hydrocarbyl or - (R ⁴ N (R ⁵ )) _p R ⁶ where R _{4 may be} C ₂ -C ₁₀ alkylene and R ₅ and R _{6 may} independently be hydrogen or hydrocarbyl and p is from about 1 to about can be about 7.

These Polyetheramines can be prepared by first an alcohol or a Alkylphenol with an alkylene oxide, a mixture of alkylene oxides or with several alkylene oxides in succession, for. B. in a molar ratio of Hydrogen compound to alkylene oxide of 1: 2-50 condensed to a polyether intermediate manufacture. US-A-5,094,667, the disclosure of which is hereby incorporated by reference incorporated into this application describes the reaction conditions for the preparation of a polyether intermediate. US-A-5,952,261, the Disclosure also incorporated herein by reference provides double metal cyanide complex catalysts. These can be used for Polymerization of epoxides used to polyether polyols with a low level of unsaturation and / or high molecular weights to disposal to deliver.

The Alcohols can be linear or branched and about 1 to about 30 carbon atoms, e.g. from about 6 to about 20 carbon atoms or, as another example, have from about 10 to about 16 carbon atoms. The alkyl group the alkylphenol can be from about 1 to about 30 carbon atoms, e.g. have from about 10 to about 20 carbon atoms.

The Alkylene oxides can from the consisting of ethylene oxide, propylene oxide and butylene oxide Group selected become. The number of alkylene oxide units in the polyether intermediate may be about 10 to about 35, e.g. from about 18 to about 27.

The polyether intermediate can be converted to a polyether amine by amination with ammonia, an amine or a polyamine. This produces a polyetheramine of the type in which A can be -NR ³ R ³ , where R ³ corresponds to the above definition. The published EP 0 310 875 , the disclosure of which is hereby incorporated by reference into this application, describes the reaction conditions for the amination reaction. Alternatively, the polyether intermediate may also be converted to a polyetheramine of the type wherein A is -OCH ₂ CH ₂ CH ₂ NR ² R ² by reaction with acrylonitrile followed by hydrogenation, where R ^{2 is as} defined above. US-A-5,094,667, the disclosure of which is hereby incorporated by reference into this application, describes the reaction conditions for the cyanoethylation and the subsequent hydrogenation.

In some embodiments, polyetheramines in which A is -OCH ₂ CH ₂ -CH ₂ NH ₂ can be used. Commercially available examples of suitable polyether amines are the TECHRON ^® series from Chevron, the JEFFAMINE ^® series of Huntsman and HiTEC ^® from Afton Chemical Corp.

The disclosed polyethers can be represented by the formula R ⁷ O (CH ₂ CH (R ⁸ ) O) _q H. Therein, R ⁷ may be a hydrocarbyl group having from about 1 to about 30 carbon atoms, R ⁸ may be selected from the group consisting of hydrogen, hydrocarbyl groups containing from about 1 to about 16 carbon atoms, and mixtures thereof, and q may be from about 2 to about 50 , The reaction conditions for the preparation as well as some embodiments of the disclosed polyethers have been described above in the description of the polyether amine for the polyether intermediate. A commercially available example of a polyether is the ACTACLEAR ^® series from Bayer. Suitable samples may also be obtained from Dow Chemicals, Huntsman, BASF and ICI.

The dispersant, such as the polyetheramine, may contain from about 5 ptb to about 300 ptb, eg, from about 25 ptb to about 200 ptb and, as another example, from about 75 to about 150 ptb of active material in the fuel composition. The dispersant may be present in the fuel additive composition in an amount from about 5 to about 60% by weight of active material based on the total weight of the composition. The disclosed fuel additive composition may contain reaction products of the polyetheramine. The fuel additive composition may also contain up to 25% by weight of unreacted starting material such as polyether alcohol.

at an embodiment For example, the polyetheramine disclosed herein may not be a friction modifier.

The The disclosed fuel additive composition also includes a friction modifier. The friction modifier may be an amide resulting from a reaction an amine with an acid was obtained. Both the amine and the acid can be monofunctional independently or be multifunctional. For example, a monoamine with a dimer acid to be reacted for use in the method of the invention produce suitable amide. Alternatively, a polyamine can be reacted with a monoacid to make an amide. A person of ordinary skill in the art should different types of acids and amines are known in different forms and combinations could be implemented, to make an amide.

at an embodiment For example, the friction modifier may be an amide such as a reaction product from a monocarboxylic fatty acid with an amine, e.g. Diethanolamine and its derivatives, for the preparation a monocarboxylic fatty acid amide be. Diethanolamine derivatives useful in this method as the amine to prepare the amine friction modifier, include fatty acid amides and esters of diethanolamine, and mixtures thereof, but are not limited to this. The fatty acid amides or esters of diethanolamine by preparing a mixture of a fatty acid and diethanolamine and heating the Mixture be formed to remove water. Possibly may be a water immiscible inert solvent such as toluene or Xylene can be used to aid in the removal of the water. Possibly can be a fatty acid ester for the above-described fatty acid substituted and reacted directly with the amine.

worin R ein Kohlenwasserstoffrest der Fettsäure sein kann.In preparing mixtures according to one embodiment of the invention, about 1 to about 3 moles of fatty acid can be used per mole of amine, such as diethanolamine. The reaction takes place and gives amide according to the following equation:

wherein R may be a hydrocarbon radical of the fatty acid.

A portion of the diethanolamine may also react to produce an ester according to the following equation:

und

The above reaction products may be separated by distillation and used separately in diesel or gasoline fuel compositions. For example, they can not be separated but used as mixtures. The mixtures may also contain fatty acid ester amides of diethanolamine. When the same molar mixtures of fatty acid and diethanolamine are reacted, only very little ester amide is formed. However, whenever more than 1 mole of fatty acid is reacted with one mole of diethanolamine, increased amounts of esteramide may form according to the following equations:

and

Such Esteramides are within the scope of the present disclosure.

at some embodiments can those useful in the preparation of the present invention Diethanolamine derivatives used fatty acids with about 8 to be about 20 carbon atoms. Non-limiting examples include caprylic, pelargonic, Capric acid, isostearic, undecylenic acid, Lauric acid, Tridecoinsäure, myristic, stearic acid, arachidic and their mixtures.

For example can the fatty acid an unsaturated one fatty acid like hypogeic acid, oleic acid, elaidic, erucic acid, brassidic and the like. As another example, the fatty acid may be oleic acid. Thus, suitable additives are N, N-bis (2-hydroxyethyl) oleamide, N- (2-hydroxyethyl) aminoethyl oleate and their mixtures. The for use in the inventive method suitable diethanolamine derivatives include those described in US-A-4,204,481, the disclosure of which is hereby incorporated by reference into this application will be taught.

The friction modifier may be present in a friction modifying amount in the fuel additive composition. Commercially available examples of friction modifiers that can be used in the disclosed fuel additive HiTEC ^® 4848A and HiTEC ^® 6457 include from Afton Chemical Corporation, Richmond, VA. A friction modifying amount is determined by ASTM D 6079. This is a standardized method for determining the lubricity in a "high frequency reciprocating rig" (HFRR = high frequency reciprocating arrangement). In various embodiments, oleaamides can be used. For example, Ethomide such as N- (hydroxyethyl) penta (oxyalkylene) oleamide and Schercomide such as ethoxylated fatty acid amides, for example Schercomid SOA-E (ethoxylated C ₁₈ fatty acid amide) and SCHERCOMID SL-ML be used.

The optionally disclosed fuel additive composition may also Fluidizing agents such as a polyether alcohol, e.g. polyether monool, include. The polyether alcohol can be used as an unreacted by-product the polyetheramide reaction in the fuel additive composition available.

The fuel additive composition according to the present disclosure may optionally also contain at least one supplemental additive. The at least one supplemental additive may be, for example, dispersants, detergents, antioxidants, carrier fluids, metal deactivators, dyes, labels, corrosion inhibitors, biocides, antistatic additives; friction-reducing agents, demulsifiers, Entnebelungsmitteln, antifreeze additives, anti-knock retardant additives, agents for inhibiting the retreat of the valve seat, lubricity additives, multifunctional additives (eg, methylcyclopentadienyl manganese tricarbonyl, MMT ^®, Afton Chemical Corp., Richmond, VA and / or other cyclopentadienyl compounds) as well as agents to improve the Combustion are selected. The at least one supplemental additive may be provided in an amount in the fuel composition necessary to achieve the desired effect.

The basic fuels used to formulate the fuel compositions of the present disclosure include all of the base fuels that are suitable for operating gasoline spark ignition engines, including leaded and unleaded gasoline for automobiles and aircraft, diesel and so-called reformulated gasolines, which are typically both gasoline hydrocarbons as well as fuel-soluble oxygenated cosolvents such as alcohols, ethers, and other suitable oxygen-containing organic compounds. Suitable oxygen-enriched compounds include, for example, methanol, ethanol, isopropanol, t-butanol, mixed C ₁ -C ₅ alcohols, methyl tert-butyl ether, tert-amyl methyl ether, ethyl tert-butyl ether, and mixed ethers. When oxygenated compounds are used, they are normally present in the base fuel in an amount below about 25% by volume, for example, in an amount which in the overall fuel has an oxygen content in the range of from about 0.5 to about 5% by volume Provides.

fuel compositions can a larger amount of a base fuel and a minor amount of a fuel additive composition contain. A "larger amount" can be about 50% or mean more. A smaller one Quantity "may be less than about 50% mean.

According to one Aspects of the present disclosure may combine the Mannich products with at least one liquid carrier or induction aids. Such carriers can be different Be type, such as liquid Poly-α-olefin oligomers, mineral oils, liquid Poly (oxyalkylene) compounds, liquid Alcohols or polyols, polyalkenes, liquid esters and the like liquid Carrier. It can too Mixtures of two or more such carriers can be used.

The used in the formulation of the fuels disclosed herein Additives can individually or in different sub-combinations in the basic fuel be mixed. However, in some cases it may be desirable to have all the components using an additive concentrate (i.e., additives plus diluents such as a hydrocarbon solvent) to interfere at the same time. When using an additive concentrate you can take advantage of mutual compatibility make that offers a combination of ingredients, if they are in the form of an additive concentrate. In addition, you can use it of a concentrate reduce the mixing time and the possibility reduce mixing errors.

The Fuel additive composition disclosed herein may come into contact come with a powered injector. Non-limiting examples for one powered injector include direct fuel injection, Fuel intake port fuel, sequential fuel injectors with central inlet (sequential central port fuel injectors) and Injectors with guide plate injectors.

at another embodiment For example, a fuel additive composition may be aliphatic with Hydrocarbyl substituted amine, a polyetheramine disclosed herein Type and a friction modifier of the type disclosed herein. In various aspects of this embodiment, the polyetheramine is possibly no friction modifier.

The A hydrocarbyl-substituted aliphatic amine can be a straightforward or branched-chain hydrocarbyl-substituted amine, which comprises at least one basic nitrogen atom. It has the Hydrocarbyl group has a number average molecular weight of about 700 to about 3,000, e.g. from about 750 to about 2,200 and as another Example from about 900 to about 1,500. In certain embodiments can the aliphatic amines have a sufficient molecular weight, at normal operating temperatures of the engine intake valve, e.g. in the range of about 175 ° C up to 300 ° C, nonvolatile to be.

When using a branched chain hydrocarbylamine, the hydrocarbyl group of polymers can be derived from C ₂ -C ₆ olefins. In certain embodiments, the branched-chain hydrocarbyl groups may be derived from polypropylene and polyisobutylene, and the branches may have from about 1 to about 2 carbon atoms, eg, a carbon atom such as a methyl. The branched chain hydrocarbyl amines may not be a pure single product but rather a mixture of compounds of average molecular weight.

The Amine component of the aliphatic substituted with hydrocarbyl Amines can be derived from ammonia, a monoamine or a polyamine be. The monoamine or polyamine component can be a broad class of amines having from about 1 to about 12 amine nitrogen atoms and about From 1 to about 40 carbon atoms with a carbon to nitrogen ratio in the range of about 1: 1 to 10: 1. In most cases it is the amine component may be not a pure individual product, but rather a mixture of compounds with a larger amount of said amine. The more complicated polyamines are the Compositions A mixture of amines, in which said Compound as main component and analogous compounds in lower Quantities are present. Suitable monoamines and polyamines are below described more fully.

If the amine component is a polyamine, it may be a polyalkyleneamine, including an alkylenediamine, in which the alkylene group is about From 2 to about 6 carbon atoms. Non-limiting examples for the Polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, Tetraethylenepentamine, di (trimethylene) triamine, propylenediamine, dipropylenetriamine, Tripropylenetetraamine and pentaethylenehexamine.

at an embodiment can the branched-chain hydrocarbylamines polyisobutenylethylenediamine and polyisobutylamine include, but are not limited to the polyisobutyl group is substantially saturated and the amine component may be derived from ammonia.

The term hydrocarbyl, which is used herein to describe the amine moiety on this invention Aliphatic amine used may refer to an organic radical comprising carbon and hydrogen which may be aliphatic, alicyclic, aromatic or a combination thereof, eg aralkyl. In certain embodiments, the hydrocarbyl group may be relatively free of aliphatic unsaturation, eg, ethylenic or acetylenic, for example, acetylenic unsaturation. Non-limiting examples of hydrocarbyl groups and substituted hydrocarbyl groups include alkyls such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, etc., alkenyls such as propenyl, isobutenyl, hexenyl, octenyl, etc., hydroxyalkyls such as 2-hydroxyethyl, 3-hydroxypropyl , Hydroxyisopropyl, 4-hydroxybutyl, etc., ketoalkyls such as 2-ketopropyl, 6-ketooctyl, etc., alkoxy and lower alkoxy such as ethoxyethyl, ethoxypropyl, propoxyethyl, propoxypropyl, diethyleneoxymethyl, triethyleneoxyethyl, tetraethyleneoxyethyl, diethyleneoxyhexyl, etc.

The Amine component may also be heterocyclic polyamines, heterocyclic substituted amines and substituted heterocyclic compounds be derived, wherein the heterocycle at least one five to comprises six-membered ring, the oxygen and / or nitrogen includes. Such heterocyclic rings can be saturated or unsaturated and be substituted.

Possible examples for the heterocyclic compounds are piperazines such as 2-methylpiperazine, N- (2-hydroxyethyl) piperazine, 1,2-bis (N-piperazinyl) ethane and N, N'-bis (N-piperazinyl) piperazine, 2-methylimidazoline, 3-aminopiperidine, 3-aminopyridine and N- (3-aminopropyl) morpholine etc.

The Aliphatic hydrocarbylamines used can be prepared by art known in the art conventional See US-A-5,993,499, 3,438,757, 3,565,804, 3,574,576, 3,848,056, 3,960,515 and 4,832,702, their disclosures are hereby incorporated by reference into this application.

Further Aspects of the invention include methods of reducing the formation or the retention of deposits, for example on the intake valve or in the combustion chamber of an engine and for elimination setting the valve in a spark ignition engine by using the Engine filled with the disclosed herein fuel composition and / or operates.

A fuel additive composition comprising 23 wt .-% of polyetheramine, 23 wt .-% of a Mannich product from a Polyisobutylencresol with high reactivity (HiTEC ^® 6416, Ethyl Corp., Richmond, VA), 12 wt .-% of a polyether alcohol (ACTACLEAR 2400 ^® , Bayer Corporation, Pittsburgh, PA) and 42% by weight of a solvent (A100, Exxon, Paulsboro, NJ) was blended into a fuel and tested according to ASTM D6421 on a SwRI PFI assembly.

ASTM D6421 is on a test bench by run Test method with which the tendency of a gasoline for motor vehicles with spark ignition engine, the electronic fuel inlet injectors (PFI = port fuel injectors) to be polluted. at The test procedure uses an apparatus equipped with Bosch injectors equipped which is for use in a 2.2-liter turbocharged engine from Chrysler, 1985-1987, are specified. This test procedure is based on a test that developed by the Coordinating Research Council (CRC) to support the Tendency of fuel for Spark ignition engines predict deposits in the small Dosierfreiräumen of Injectors in a PFI engine (see CRC report No. 5922). This test procedure is for fuels for spark ignition engines applicable, the antioxidants, corrosion inhibitors, metal deactivators, Dyestuffs, additives for the control of deposits, demulsifiers, oxygenated compounds or a combination may contain.

The Data is as follows.

pass 1: 80 ptb (0.864 g / gallon) of the above fuel additive were added to a gas.

• = 24.9% average

Run 2: 80 ptb (0.864 gram / gallon) of the above fuel additive and 20 ptb (0.216 g / gal) of a friction modifier (HiTEC ^® 6457, Afton Chemical Corp., Richmond, VA) was the same gasoline as in Run 1 in the same series of fuel injectors, however, cleaned between tests. The friction modifier was a low molecular weight amide of a branched (C ₁₈ ) fatty acid reacted with diethanolamine.

• = 5.1% average

Run 3: Basic fuel gasoline without fuel additive composition

• = 24.1% average

Example 2

The in Example 1 was designated fuel additive composition in a base fuel with and without the addition of a friction modifier (as the disclosed amide) used. The fuel was in one GM Astro VAN, model 2000 to 2002, with a 4.3-liter V-6 engine tested with a sequential central fuel injector (sequential central port fuel injection = SCPI) was equipped. you used the standard for the initial performance the pollution of the fuel injector, in detail in the April 2004 adopted "TOP Animal Detergent Gasoline Deposit Control Performance Standards "are laid down. The test is passed if not more than one injection device in the Vehicle "hangs".

• n.e. = nicht erfindungsgemäß
• e. = erfindungsgemäß

The data is as follows:

• ne = not according to the invention
• e. = according to the invention

HiTEC ^® 6457, which is a reaction product of isostearic acid and diethanolamine was used as friction modifiers.

As from the data, it came in a vehicle with a fuel composition, the one fuel additive composition without a friction modifier contained compared to a fuel composition with a A fuel additive composition with a modifier at a higher percentage of deposits (see Run 1 of Example 1) and more hanging Injectors (see Test Nos. 1 and 2 of Example 2).

Example 3

A mileage test with accumulated miles was performed on a chassis dynamometer with a mixed cycle of highway and city traffic. Specifically, one drive cycle was 76 miles over 99:46 minutes at an average speed of 45.7 miles / hour. Two runs of different formulations were tested. The first did not contain a friction modifier. The second pass used a friction modifier. The test used a Mercury Marquis 4.6-liter V8 engine built in 2000. Average intake valve deposits were measured after 1500 miles of PUL fuel contamination. In addition, the average deposits at the top of the chamber and at the top of the flask after 5000 miles of cleaning were measured on the fuel additive in the PUL fuel at rates as indicated in the table (ptb).

• N. E. = not according to the invention
• e. = according to the invention

As you see, showed up on the second pass with the wording, containing a friction modifier, on average less Deposits at the top of the chamber and at the top of the flask and thus less total deposits in the chamber.

For the purpose This description and the appended claims apply to all numbers which Quantities, percentages or relationships and other numerical terms used in the specification and claims Values in all cases as supplemented by the term "about", provided nothing else is stated.

consequently can the numerical parameters in the description and the appended claims there, Unless otherwise indicated, approximations may vary the wished Properties that one wishes to achieve through the invention vary can. At least, not as an attempt, the validity of Equivalent Theory on the scope of the claims restrict should be any numerical parameter at least in the light of the number significant digits and using common Rounding techniques are interpreted.

regardless the fact that the numerical ranges and parameters that the huge Framework of the invention, are approximate, are the numerical values in the specific examples as accurately as possible. Each numeric value contains however, inherently certain mistakes that are inevitable from the resulting in the respective test measurements standard deviation. About that In addition, all of the areas disclosed herein should be understood as that they also include all subsummarized subsets. For example includes an area "less as 10 "all too intervening subregions, including the minimum value 0 and the maximum value 10, that is all sub-ranges with a minimum value of 0 or greater and a maximum value of 10 or less, e.g. 1 to 5.

It It should be noted that in this specification and the appended claims Singular forms "one / one" and "the" also the plural include, unless specifically stated and unmistakable limited to the singular are. So close For example, the reference to a "friction modifier" also two or more Friction modifier. As used herein, the term "include" and its grammatical Variants should not be limiting so be the enumeration of items on a list does not exclude other items that the said objects added or for this can be substituted.

For professionals is obvious that the various embodiments described here can be modified and modified without this being a deviation from the scope or content of the present teaching. Thus, should the various embodiments described herein also other modifications and modifications, which come within the scope of the appended claims and their equivalents fall, cover.

Claims (34)

A fuel additive composition comprising a) a Mannich product, b) a polyetheramine and c) a friction modifier. A composition according to claim 1, wherein the Mannich product a reaction product of an alkyl-substituted hydroxyaromatic Compound, an aldehyde and an amine is. A composition according to claim 2, wherein the alkyl substituted hydroxyaromatic compound is selected from alkylphenols. A composition according to claim 3, wherein the alkylphenols selected from cresols are. A composition according to claim 2, wherein the alkyl substituted hydroxyaromatic compound substituted with polyolefin Phenols selected is. A composition according to claim 5, wherein the polyolefin substituted phenols from polybutylene-substituted phenols and polypropylene-substituted phenols. A composition according to claim 5, wherein the polyolefin substituted phenols are polyisobutylcresols. A composition according to claim 2, wherein the amine an alkylene polyamine. A composition according to claim 1, which further comprises a Polyether alcohol comprises. A composition according to claim 2 wherein the aldehyde Formaldehyde or a precursor it is. A composition according to claim 1, wherein the friction modifier an amide is. A composition according to claim 11, wherein the amide an alkanolamide. A composition according to claim 11, wherein the amide a reaction product of an acid and an amine. A composition according to claim 13 wherein the acid is the group consisting of a monofunctional acid and a multifunctional acid, selected becomes. A composition according to claim 13, wherein the amine from the group consisting of a monoamine and a polyamine selected becomes. A composition according to claim 13 wherein the acid is a Monocarboxylic fatty and the amine is diethanolamine. A composition according to claim 1, wherein the Mannich product with at least one liquid carrier combined. Process for the preparation of a fuel additive, comprising providing a Mannich product, a polyetheramine and a friction modifier to add a fuel additive win. The method of claim 18, wherein the friction modifier in the fuel additive in a friction modifying amount according to ASTM D 6079 is present. A fuel composition comprising (A) one Fuel in a larger amount and (B) a fuel additive composition according to claim 1 in a smaller amount. A composition according to claim 20, wherein the fuel Includes gasoline. A composition according to claim 20, wherein the Mannich product about 5 ptb to about 300 ptb of active material in the fuel composition includes. A composition according to claim 22, wherein the Mannich product about 25 ptb to about 200 ptb of active material in the fuel composition includes. A composition according to claim 20, wherein the polyetheramine about 5 ptb to about 300 ptb of active material in the fuel composition includes. A composition according to claim 24, wherein the polyetheramine about 25 ptb to about 200 ptb of active material in the fuel composition includes. A composition according to claim 20, which further comprises at least contains an additive, selected the group consisting of dispersants, detergents, antioxidants, Carrier fluids, Metal deactivators, dyes, markers, corrosion inhibitors, Biocides, antistatic additives, friction reducing agents, Demulsifiers, defogging agents, antifreeze additives, anti-knock Additives, means for inhibiting the retraction of the valve seat, Lubricity additives and means for improving combustion. Method of prevention and / or reduction the formation of deposits in an engine, including the supply and the operation of this engine with a fuel composition according to claim 20. The method of claim 27, wherein the deposits Deposits in the combustion chamber are. Engine containing a fuel additive composition Burns according to claim 1. Engine comprising a fuel composition according to claim 20 burns. Powered injector that in contact comes with a fuel additive composition according to claim 1. Powered injector that in contact comes with a fuel composition according to claim 20. Injection device according to claim 31, wherein the driven injector is selected from the group consisting from direct fuel injectors, fuel inlet injectors (port fuel injectors), sequential fuel injectors with central inlet (sequential central port fuel injectors) and injectors with Director plate injectors. A fuel additive composition comprising: a) an aliphatic hydrocarbyl-substituted amine, b) a polyether amine and c) a friction modifier