EP2126010A1

EP2126010A1 - Fuel additives for use in alcohol-fuels

Info

Publication number: EP2126010A1
Application number: EP08744028A
Authority: EP
Inventors: Jonathan S. Vilardo
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 2007-03-21
Filing date: 2008-03-19
Publication date: 2009-12-02
Also published as: US20100107484A1; WO2008115939A1; BRPI0809048A2; CA2681498A1

Abstract

The present invention provides a fuel additive concentrate comprising a detergent, antioxidant; and a friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof. Additionally, the present invention further provides for a fuel composition comprising a fuel, which is a liquid at room temperature; and additive, wherein the additive is selected from the group consisting of: a detergent; antioxidant; friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof; and mixtures thereof.

Description

TITLE

Fuel Additives For Use In Alcohol-Fuels

BACKGROUND OF THE INVENTION

The present invention relates to fuel additive concentrate, the fuel additive concentrate in an alcohol fuel and the method for fueling an internal combustion engine, providing improved fuel economy and retention of fuel economy, deposit control, oxidation control, and wear and friction reduction.

Governments around the world are implementing the use of no nhydro carbonaceous fuels for economic and environmental reasons. Oxygenates such as ethanol, butanol, isopropanol, methanol, methyl tert butyl ether (MTBE) and ethyl tert butyl ether (ETBE) in particular are gaining ground as alcohol and ether fuels of choice as they present renewable and/or environmentally friendly alternatives to petroleum based fuels such as gasoline or diesel fuel. Additionally, fuels made from alcohol feedstocks benefit the agricultural sector and therefore, have the backing of political and pricing support. These factors in combination with rises in crude oil, desire for energy independence, and fears of global warming explain the recent growth in the alcohol fuel market. Brazil has a long history of using fuel alcohol, particularly ethanol.

Alcohol fuels can have unique effects on engine hardware and lubricant resulting in the tendency for increased engine deposits formation, accelerated lubricant oxidation, increased wear of vital engine components, and a loss of fuel economy. Some issues have been addressed through the development of new vehicle technology, while other issues will require new inventive additives technology.

The present invention, therefore, solves the problems of associated with alcohol fuels tendencies for engine deposits formation, lubricant oxidation, engine wear and a loss of fuel economy by providing fuel additives to the ethanol-gasoline blends that prevent engine deposits, slows lubricant oxidation, prevent wear and improve fuel economy. SUMMARY OF THE INVENTION

The present invention provides a fuel additive concentrate comprising: a. detergent; b. antioxidant; and c. a friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof wherein the detergent is soluble in a nonhydrocarbonaceous fuel.

The present invention further provides for a fuel composition comprising: a. a fuel which is a liquid at room temperature; and b. additive wherein the additive is selected from the group consisting of a detergent; antioxidant; friction modifier selected from the group consisting of an alkoxy- lated fatty amine, a fatty acid or derivative thereof, and mixture thereof; and mixtures thereof wherein the detergent is soluble in a nonhydrocarbonaceous fuel.

The present invention further provides a method for fueling an internal combustion engine, comprising:

A. supplying to an internal combustion engine: i. a fuel which is a liquid at room temperature; and ii. additive wherein the additive is selected from the group consisting of a detergent; antioxidant; friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof; and mixtures thereof wherein the detergent is soluble in a nonhydrocarbonaceous fuel.

The present invention further provides for a use of the fuel composition or fuel additive concentrate in an internal combustion engine providing at least one of the following: fuel system deposit control, injector deposit control, intake valve deposit control, combustion chamber deposit control, wear control, improved fuel economy, and emission reduction (CO2, NOx, or other gases). DETAILED DESCRIPTION OF THE INVENTION

Various preferred features and embodiments will be described below by way of non-limiting illustration.

Field of the Invention

This invention involves fuel additive concentrate that includes: a detergent, antioxidant, and a friction modifier selected the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof; wherein the detergent is soluble in a nonhydro carbonaceous fuel. The invention further involves a fuel composition that includes a fuel, which is a liquid at room temperature, and an additive wherein the additive is selected from the group consisting of a detergent; antioxidant; friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof; and mixtures thereof; wherein the detergent is soluble in a nonhydrocarbonaceous fuel.

The invention further involves a method of operating an internal combustion engine comprising supplying to the internal combustion engine a fuel which is a liquid at room temperature, and an additive wherein the additive is selected from the group consisting of a detergent; antioxidant; friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof; and mixtures thereof; wherein the detergent is soluble in a nonhydrocarbonaceous fuel.

The fuel additive concentrates, fuel compositions and methods of the present invention promote engine cleanliness and fuel economy, while controlling lubricant oxidation, which enables optimal engine operation.

Fuel

The present invention can comprise a fuel which is a liquid at room temperature and is useful in fueling an engine. The fuel is normally a liquid at ambient conditions e.g., room temperature (20 to 30⁰C). The fuel is a nonhydrocarbonaceous fuel. A nonhydrocarbonaceous fuel is a fuel obtained from processes other than fuel streams obtained through the refining of fossil fuels. The nonhydrocarbonaceous fuel can be obtained from fermentation processes using bio-feed stocks, such as, corn, cellulose; sugar cane; or other agricultural or natural plant sources. The nonhydrocarbonaceous fuel can be obtained synthetically from hydrocarbonaceous or nonhydrocarbonaceous ingredients. The nonhydrocarbonaceous fuel can be an oxygen containing composition, often referred to as a oxygenate, which can include alcohols, ethers, ketones, esters of a carboxylic acid, nitroalkanes, and mixtures thereof. The nonhydrocarbonaceous fuel can include, for example, methanol, ethanol, propanol, butanol, methyl t-butyl ether, ethyl t-butyl ether, methyl ethyl ketone, transesterified oils and/or fats from plants and animals such as rapeseed methyl ester and soybean methyl ester, and nitromethane. In several embodiments of this invention, the fuel can have a water content on a weight basis that is about 10 percent by weight, or about 7 percent by weight, or about 5 percent by weight, or about 3 percent by weight, or about 1 percent by weight, or less than 1 percent by weight or 0 percent by weight. In another embodiment, the fuel can be alcohol fuel, such as, punctilious alcohol or anhydrous alcohol or hydrous alcohol, such as, AlCool™. In another embodiment of the invention, the fuel can be denatured ethanol (that is a blend of ethanol with a denaturant).

The alcohol fuel can be denatured ethanol as defined by ASTM specification D4806. In several embodiments of this invention, the denatured ethanol can have a denaturant content on a weight basis that is about 10 percent by weight, or about 7 percent by weight, or about 5 percent by weight, or about 3 percent by weight, or about 1 percent by weight, or less than 1 percent by weight or 0 percent by weight. In several embodiments the denaturant can be hydrocarbonaceous or nonhydrocarbonaceous. In one embodiment, the hydrocarbonaceous denaturant can be natural gasoline, refined gasoline, kerosene, diesel fuel, or benzene. The hydrocarbonaceous denaturant can be a petroleum distillate to include a gasoline as defined by ASTM specification

D4814 or a diesel fuel as defined by ASTM specification D975. In another embodiment the nonhydrocarbonaceous denaturant can be diethyl phthalate, isopropanol, phenylethyl alcohol, musk ketone, menthol, or benzyl salicylate.

In several embodiments of this invention, the fuel can have a sulfur content on a weight basis that is 5000 ppm or less, 1000 ppm or less, 300 ppm or less, 200 ppm or less, 30 ppm or less, or 10 ppm or less. In another embodiment, the fuel can have a sulfur content on a weight basis of 1 to 100 ppm. In one embodiment, the fuel contains 0 ppm to 1000 ppm, or 0 to 500 ppm, or 0 to 100 ppm, or 0 to 50 ppm, or 0 to 25 ppm, or 0 to 10 ppm, or 0 to 5 ppm of alkali metals, alkaline earth metals, transition metals or mixtures thereof. In another embodiment, the fuel contains 1 to 10 ppm by weight of alkali metals, alkaline earth metals, transition metals or mixtures thereof. It is well known in the art that a fuel containing alkali metals, alkaline earth metals, transition metals or mixtures thereof have a greater tendency to form deposits and therefore foul or plug injectors. The fuel of the invention can be present in a fuel composition in a major amount that is generally greater than 50 percent by weight, and in other embodiments is present at greater than 90 percent by weight, greater than 95 percent by weight, greater than 99.5 percent by weight, or greater than 99.8 percent by weight. Detergent The detergent of the present invention, which is soluble in a nonhydrocarbonaceous fuel can include polyetheramines, Mannich, succinimides, polyisobutylene amines, glyoxylates, and mixtures thereof.

Polyetheramines of present invention can include compounds having two or more consecutive ether groups and at least one primary, secondary or tertiary amine group where the amine nitrogen has some basicity. The polyetheramines of this invention can include poly(oxyalkylene) amines having a sufficient number of repeating oxyalkylene units to render the poly(oxyalkylene)amine soluble in a normally liquid fuel, such as, in hydrocarbons boiling in a gasoline or diesel fuel range and blends of hydrocarbon fuel with non-hydrocarbon fuel. Generally, poly(oxyalkylene)amines having at least about 5 oxyalkylene units are suitable for use in the present invention. Poly(oxyalkylene)amines can include: hydrocarbylpoly(oxyalkylene)amines, hydrocarbylpoly(oxyalkylene)polyamines, hydropoly(oxyalkylene)amines, hydropo Iy (oxy alky lene)po Iy amines, and derivatives of polyhydric alcohols having at least two poly(oxyalkylene)amine and/or poly(oxyalkylene)polyamine chains on the molecule of the derivative. In one embodiment, the poly(oxyalkylene)amine for use in the invention is represented by the formula RO(AO)mRlNR2R3 (I) wherein R is a hydrocarbyl group of 1 to 50 carbon atoms, or about 8 to about 30 carbon atoms; A is an alkylene group having 2 to 18 carbon atoms and preferably 2 to 6 carbon atoms; m is a number from 1 to about 50; Rl is an alkylene group having 2 to 18 carbon atoms or preferably 2 to 6 carbon atoms; and R2 and R3 are independently hydrogen, a hydrocarbyl group or -[R4N(R5)]nR6 wherein R4 is an alkylene group having 2 to 6 carbon atoms, R5 and R6 are independently hydrogen or a hydrocarbyl group, and n is a number from 1 to 7. In another embodiment, the poly(oxyalkylene)amine of the present invention can be represented by the formula:

RO[CH2CH(CH2CH3)O]mCH2CH2CH2NH2 (II) wherein R is an aliphatic group or alkyl-substituted phenyl group of about 8 to about 30 carbon atoms; and m is a number from about 12 to about 30. In yet another embodiment, the poly(oxyalkylene)amine of the present invention can be represented by the formula: CH3CH(CH3)[CH2CH(CH3)]2CH(CH3)CH2CH2O-

[CH2CH(CH2CH3)O]mCH2CH2CH2NH2 (III) wherein m is a number from about 16 to about 28. Poly(oxyalkylene)amines of the present invention can have a molecular weight in the range from about 300 to about 5,000.

The polyetheramines of the present invention can be prepared by initially condensing an alcohol or alkylphenol with an alkylene oxide, mixture of alkylene oxides or with several alkylene oxides in sequential fashion in a 1 : 1-50 mole ratio of hydric compound to alkylene oxide to form a polyether intermediate. U.S. Patent Nos. 5,112,364 and 5,264,006 provide reaction conditions for preparing a polyether intermediate.

The alcohols can be monohydric or polyhydric, linear or branched, saturated or unsaturated and having 1 to 50 carbon atoms, or from 8 to 30 carbon atoms, or from 10 to 16 carbon atoms. Branched alcohols of the present invention can include Guerbet alcohols, as described in U.S. Patent No.

5,264,006, which generally contain between 12 and 40 carbon atoms and can be represented by the formula RCH(CH2CH2R)CH2OH (IV) where R is a hydrocarbyl group. In one embodiment, the alkyl group of the alkylphenols can be 1 to 50 carbon atoms, or 2 to 24 carbon atoms, or 10 to 20 carbon atoms. In one embodiment, the alkylene oxides include 1,2-epoxyalkanes having 2 to about 18 carbon atoms, or 2 to about 6 carbon atoms. In yet another embodiment, the alkylene oxides can be ethylene oxide, propylene oxide and butylene oxide. Especially useful is propylene oxide, butylene oxide, or a mixture thereof. The number of alkylene oxide units in the polyether intermediate can be 1-50, or 12-30, or 16-28.

The polyether intermediates can be converted to polyetheramines by several methods. The polyether intermediate can be converted to a polyetheramine by a reductive amination with ammonia, a primary amine or a polyamine as described in U.S. Patent Nos. 5,1 12,364 and 5,752,991. In one embodiment, the polyether intermediate can be converted to a polyetheramine via an addition reaction of the polyether to acrylonitrile to form a nitrile which is then hydrogenated to form the poly ether amine. U.S. Patent No. 5,264,006 provides reaction conditions for the cyanoethylation of the polyether with acrylonitrile and the subsequent hydrogenation to form the polyetheramine. In yet another embodiment, the polyether intermediate or poly(oxyalkylene) alcohol is converted to the corresponding poly(oxyalkylene) chloride via a suitable chlorinating agent followed by displacement of chlorine with ammonia, a primary or secondary amine, or a polyamine as described in U.S. Patent No. 4,247,301.

The detergent of the present invention can be a Mannich detergent, sometimes referred to as a Mannich base detergent. Mannich detergent is a reaction product of a hydrocarbyl-substituted phenol, an aldehyde, and an amine or ammonia. The hydrocarbyl substituent of the hydrocarbyl-substituted phenol can have 10 to 400 carbon atoms, in another instance 30 to 180 carbon atoms, and in a further instance 10 or 40 to 110 carbon atoms. This hydrocarbyl substituent can be derived from an olefin or a polyolefin. Useful olefins include alpha-olefins, such as 1-decene, which are commercially available.

The polyolefins which can form the hydrocarbyl substituent can be prepared by polymerizing olefin monomers by well known polymerization methods and are also commercially available. The olefin monomers include monoolefins, including monoolefins having 2 to 10 carbon atoms such as ethylene, propylene, 1-butene, isobutylene, and 1-decene. An especially useful monoolefin source is a C₄ refinery stream having a 35 to 75 weight percent butene content and a 30 to 60 weight percent isobutene content. Useful olefin monomers also include diolefins such as isoprene and 1,3-butadiene. Olefin monomers can also include mixtures of two or more monoolefins, of two or more diolefins, or of one or more monoolefins and one or more diolefins. Useful polyolefins include polyisobutylenes having a number average molecular weight of 140 to 5000, in another instance of 400 to 2500, and in a further instance of 140 or 500 to 1500. The polyisobutylene can have a vinylidene double bond content of 5 to 69 percent, in a second instance of 50 to

69 percent, and in a third instance of 50 to 95 percent. The polyolefin can be a homopolymer prepared from a single olefin monomer or a copolymer prepared from a mixture of two or more olefin monomers. Also possible as the hydrocarbyl substituent source are mixtures of two or more homopolymers, two or more copolymers, or one or more homopolymers and one or more copolymers. The hydrocarbyl-substituted phenol can be prepared by alkylating phenol with an olefin or polyolefin described above, such as a polyisobutylene or polypropylene, using well-known alkylation methods.

The aldehyde used to form the Mannich detergent can have 1 to 10 carbon atoms, and is generally formaldehyde or a reactive equivalent thereof such as formalin or paraformaldehyde.

The amine used to form the Mannich detergent can be a monoamine or a polyamine, including alkanolamines having one or more hydroxyl groups, as described in greater detail above. Useful amines include those described above, such as ethanolamine, diethanolamine, methylamine, dimethylamine, ethylenediamine, dimethylaminopropylamine, diethylenetriamine and 2-(2- aminoethylamino) ethanol. The Mannich detergent can be prepared by reacting a hydrocarbyl-substituted phenol, an aldehyde, and an amine as described in U.S. Patent No. 5,697,988. In one embodiment of this invention the Mannich reaction product is prepared from an alkylphenol derived from a polyisobutylene, formaldehyde, and an amine that is a primary monoamine, a secondary monoamine, or an alkylenediamine, in particular, ethylenediamine or dimethylamine.

The Mannich reaction product of the present invention can be prepared by reacting the alkyl-substituted hydroxyaromatic compound, aldehyde and polyamine by well known methods including the method described in U.S. Patent 5,876,468.

The Mannich reaction product can be prepared by well known methods generally involving reacting the hydrocarbyl substituted hydroxy aromatic compound, an aldehyde and an amine at temperatures between 50 to 200⁰C in the presence of a solvent or diluent while removing reaction water as described in U. S. Patent No. 5,876,468.

Another type of detergent, which can be used in the present invention, is a succinimide. Succinimide detergents are well known in the field of lubricants and include primarily what are sometimes referred to as "ashless" detergents because they do not contain ash-forming metals and they do not normally contribute any ash forming metals when added to a lubricant. Succinimide detergents are the reaction product of a hydrocarbyl substituted succinic acylating agent and an amine containing at least one hydrogen attached to a nitrogen atom. The term "succinic acylating agent" refers to a hydrocarbon- substituted succinic acid or succinic acid-producing compound (which term also encompasses the acid itself). Such materials typically include hydrocarbyl- substituted succinic acids, anhydrides, esters (including half esters) and halides. Succinic based detergents have a wide variety of chemical structures including typically structures such as

In the above structure, each R¹ is independently a hydrocarbyl group, which may be bound to multiple succinimide groups, typically a polyolefin- derived group having an Mn of 500 or 700 to 10,000. Typically the hydrocarbyl group is an alkyl group, frequently a polyisobutylene group with a molecular weight of 500 or 700 to 5000, or 1500 or 2000 to 5000. Alternatively expressed, the R¹ groups can contain 40 to 500 carbon atoms or at least 50 to 300 carbon atoms, e.g., aliphatic carbon atoms. The R² are alkylene groups, commonly ethylene (C₂H₄) groups. Such molecules are commonly derived from reaction of an alkenyl acylating agent with a polyamine, and a wide variety of linkages between the two moieties is possible beside the simple imide structure shown above, including a variety of amides and quaternary ammonium salts. Succinimide detergents are more fully described in U.S. Patents 4,234,435, 3,172,892, and 6,165,235.

The polyalkenes from which the substituent groups are derived are typically homopolymers and interpolymers of polymerizable olefin monomers of 2 to 16 carbon atoms; usually 2 to 6 carbon atoms.

The olefin monomers from which the polyalkenes are derived are polymerizable olefin monomers characterized by the presence of one or more ethylenically unsaturated groups (i.e., >C=C<); that is, they are mono-olefinic monomers such as ethylene, propylene, 1-butene, isobutene, and 1-octene or polyolefinic monomers (usually diolefinic monomers) such as 1 ,3 -butadiene, and isoprene. These olefin monomers are usually polymerizable terminal olefins; that is, olefins characterized by the presence in their structure of the group >C=CH₂. Relatively small amounts of non-hydrocarbon substituents can be included in the polyolefm, provided that such substituents do not substantially interfere with formation of the substituted succinic acid acylating agents.

Each R¹ group may contain one or more reactive groups, e.g., succinic groups, thus being represented (prior to reaction with the amine) by structures such as

in which y represents the number of such succinic groups attached to the R¹ group. In one type of detergent, y = 1. In another type of detergent, y is greater than 1, in one embodiment greater than 1.3 or greater than 1.4; and in another embodiment y is equal to or greater than 1.5. in one embodiment y is 1.4 to 3.5, such as 1.5 to 3.5 or 1.5 to 2.5. Fractional values of y, of course, can arise because different specific R¹ chains may be reacted with different numbers of succinic groups. The amines which are reacted with the succinic acylating agents to form the carboxylic detergent composition can be monoamines or polyamines. In either case they will be characterized by the formula R⁴R⁵NH wherein R⁴ and R⁵ are each independently hydrogen, hydrocarbon, amino-substituted hydrocarbon, hydroxy-substituted hydrocarbon, alkoxy-substituted hydrocarbon, amino, carbamyl, thiocarbamyl, guanyl, or acylimidoyl groups provided that no more than one of R⁴ and R⁵ is hydrogen. In all cases, therefore, they will be characterized by the presence within their structure of at least one H-N< group. Therefore, they have at least one primary (i.e., H₂N-) or secondary amino (i.e., H-N<) group. Examples of monoamines include ethylamine, diethylamine, n-butylamine, di-n-butylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine, and octadecylamine.

The polyamines from which the detergent is derived include principally alkylene amines conforming, for the most part, to the formula A — N-(alkylene-N), — H

A A wherein t is an integer typically less than 10, A is hydrogen or a hydrocarbyl group typically having up to 30 carbon atoms, and the alkylene group is typically an alkylene group having less than 8 carbon atoms. The alkylene amines include principally, ethylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines. They are exemplified specifically by: ethylene diamine, diethylene triamine, triethylene tetramine, propylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene) triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di(-trimethylene) triamine. Higher homologues such as are obtained by condensing two or more of the above-illustrated alkylene amines likewise are useful. Tetraethylene pentamine is particularly useful.

The ethylene amines, also referred to as polyethylene polyamines, are especially useful. They are described in some detail under the heading "Ethylene Amines" in Encyclopedia of Chemical Technology, Kirk and

Othmer, Vol. 5, pp. 898-905, Interscience Publishers, New York (1950).

Hydroxyalkyl-substituted alkylene amines, i.e., alkylene amines having one or more hydroxyalkyl substituents on the nitrogen atoms, likewise are useful. Examples of such amines include N-(2-hydroxyethyl)ethylene diamine, N,N'-bis(2-hydroxyethyl)-ethylene diamine, l-(2-hydroxyethyl)piperazine, monohydroxypropyl)-piperazine, di-hydroxypropy-substituted tetraethylene pentamine, N-(3 -hydro xypropyl)-tetra-methylene diamine, and 2-heptadecyl-l- (2-hydroxyethyl)-imidazoline.

Higher homologues, such as are obtained by condensation of the above- illustrated alkylene amines or hydroxy alkyl-substituted alkylene amines through amino radicals or through hydroxy radicals, are likewise useful. Condensed polyamines are formed by a condensation reaction between at least one hydroxy compound with at least one polyamine reactant containing at least one primary or secondary amino group and are described in U.S. Patent 5,230,714 (Steckel).

The succinimide detergent is referred to as such since it normally contains nitrogen largely in the form of imide functionality, although it may be in the form of amine salts, amides, imidazolines as well as mixtures thereof. To prepare the succinimide detergent, one or more of the succinic acid- producing compounds and one or more of the amines are heated, typically with removal of water, optionally in the presence of a normally liquid, substantially inert organic liquid solvent/diluent at an elevated temperature, generally in the range of 80⁰C up to the decomposition point of the mixture or the product; typically 100⁰C to 300⁰C.

The succinic acylating agent and the amine (or organic hydroxy compound, or mixture thereof) are typically reacted in amounts sufficient to provide at least one-half equivalent, per equivalent of acid-producing compound, of the amine (or hydroxy compound, as the case may be). Generally, the maximum amount of amine present will be about 2 moles of amine per equivalent of succinic acylating agent. For the purposes of this invention, an equivalent of the amine is that amount of the amine corresponding to the total weight of amine divided by the total number of nitrogen atoms present. The number of equivalents of succinic acid-producing compound will vary with the number of succinic groups present therein, and generally, there are two equivalents of acylating reagent for each succinic group in the acylating reagents. Additional details and examples of the procedures for preparing the succinimide detergents of the present invention are included in, for example, U.S. Pat. Nos. 3,172,892; 3,219,666; 3,272,746; 4,234,435; 6,440,905 and 6,165,235.

Yet another type of detergent, which can be used in the present invention, can be a polyisobutylene amine. The amine use to make the the polyisobutylene amine can be a polyamine such as ethylenediamine, 2-(2-aminoethylamino)- ethanol, or diethylenetri amine. The polyisobutylene amine of the present invention can be prepared by several known methods generally involving amination of a derivative of a polyolefin to include a chlorinated polyolefin, a hydroformylated polyolefin, and an epoxidized polyolefin. In one embodiment of the invention the polyisobutylene amine is prepared by chlorinating a polyolefin such as a polyisobutylene and then reacting the chlorinated polyolefin with an amine such as a polyamine at elevated temperatures of generally 100 to 15O⁰C as described in U. S. Patent No. 5,407,453. To improve processing a solvent can be employed, an excess of the amine can be used to minimize cross-linking, and an inorganic base such as sodium carbonate can be used to aid in removal of hydrogen chloride generated by the reaction.

Yet another type of detergent, which can be used in the present invention, is a glyoxylate. A glyoxylate detergent is a fuel soluble ashless detergent which, in a first embodiment, is the reaction product of an amine having at least one basic nitrogen, i.e. one >N-H, and a hydrocarbyl substituted acylating agent resulting from the reaction, of a long chain hydrocarbon containing an olefmic bond with at least one carboxylic reactant selected from the group consisting of compounds of the formula (I)

(R¹C(O)(R²)_nC(O))R³ (I)

and compounds of the formula (II)

wherein each of R¹, R³ and R⁴is independently H or a hydrocarbyl group, R² is a divalent hydrocarbylene group having 1 to 3 carbons and n is 0 or 1 :

Examples of carboxylic reactants are glyoxylic acid, glyoxylic acid methyl ester methyl hemiacetal, and other omega-oxoalkanoic acids, keto alkanoic acids such as pyruvic acid, levulinic acid, ketovaleric acids, ketobutyric acids and numerous others. The skilled worker having the disclosure before him will readily recognize the appropriate compound of formula (I) to employ as a reactant to generate a given intermediate.

The hydrocarbyl substituted acylating agent can be the reaction of a long chain hydrocarbon containing an olefin and the above described carboxylic reactant of formula (I) and (II), further carried out in the presence of at least one aldehyde or ketone. Typically, the aldehyde or ketone contains from 1 to about 12 carbon atoms.

Suitable aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, pentanal, hexanal. heptaldehyde, octanal, benzaldehyde, and higher aldehydes. Other aldehydes, such as dialdehydes, especially glyoxal, are useful, although monoaldehydes are generally preferred.

Suitable ketones include acetone, butanone, methyl ethyl ketone, and other ketones.

Typically, one of the hydrocarbyl groups of the ketone is methyl. Mixtures of two or more aldehydes and/or ketones are also useful. Compounds and the processes for making these compounds are disclosed in

U.S. Pat. Nos. 5,696,060; 5,696,067; 5,739,356; 5,777,142; 5,856,524; 5,786,490;

6,020,500; 6,114,547; 5,840,920 and are incorporated herein by reference. In another embodiment, the glyoxylate detergent is the reaction product of an amine having at least one basic nitrogen, i.e. one >N-H, and a hydrocarbyl substituted acylating agent resulting from the condensation product of a hydroxyaromatic compound and at least one carboxylic reactant selected from the group consisting of the above described compounds of the formula (I) and compounds of the formula (II). Examples of carboxylic reactants are glyoxylic acid, glyoxylic acid methyl ester methyl hemiacetal, and other such materials as listed above.

The hydroxyaromatic compounds typically contain directly at least one hydrocarbyl group R bonded to at least one aromatic group. The hydrocarbyl group

R may contain up to about 750 carbon atoms or 4 to 750 carbon atoms, or 4 to 400 carbon atoms or 4 to 100 carbon atoms. In one embodiment, at least one R is derived from polybutene. In another embodiment, R is derived from polypropylene.

In another embodiment, the reaction of the hydroxyaromatic compound and the above described carboxylic acid reactant of formula (I) or (II) can be carried out in the presence of at least one aldehyde or ketone. The aldehyde or ketone reactant employed in this embodiment is a carbonyl compound other than a carboxy- substituted carbonyl compound. Suitable aldehydes include monoaldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, pentanal, hexanal, heptaldehyde, octanal, benzaldehyde, and higher aldehydes.

Other aldehydes, such as dialdehydes, especially glyoxal, are useful. Suitable ketones include acetone, butanone, methyl ethyl ketone, and other ketones. Typically, one of the hydrocarbyl groups of the ketone is methyl. Mixtures of two or more aldehydes and/or ketones are also useful. Compounds and the processes for making these compounds are disclosed in U.S. Pat. Nos. 3,954,808; 5,336,278; 5,620,949 and 5,458,793 and are incorporated herein by reference

The detergent additive of this invention can be present in a mixture of various detergents referenced above. In one embodiment, the detergent in the fuel composition may be present in an amount from about 1 to about 10000 ppm, or about 5 to about 5000, or about 20 to about 4000 or about 40 to about 3500 ppm.

In one embodiment, the detergent can be present in the fuel additive concentration in an amount from about 1 to about 99 percent by weight, or about 10 to about 80 percent by weight, or about 20 to about 60 percent by weight, or about 20 to about 50 percent by weight. Friction Modifier

The present invention can comprise a friction modifier. The friction modifier is selected from the group consisting of an alkoxyalted fatty amine, fatty acid or derivative thereof, and mixtures thereof.

In one embodiment, the friction modifier of the present invention can include an alkoxylated fatty amine, which can include amines represented by the formula:

wherein R is a hydrocarbyl group having about 4 to 30 carbon atoms, A¹ and A² are vicinal alkylene groups, and the sum of x and y is an integer that is at least 1. The hydrocarbyl group is a univalent radical of carbon atoms that is predominantly hydrocarbon in nature, but can have nonhydrocarbon substituent groups and can have heteroatoms. The hydrocarbyl group R can be an alkyl or alkylene group of about 4 to 30 carbon atoms, or about 10 to 22 carbon atoms. The vicinal alkylene groups A¹ and A² can be the same or different and include: ethylene(-CH2-), propylene (-CH2CH2CH2-) and butylene (- CH2CH2CH2CH2-) having the carbon to nitrogen and carbon to oxygen bonds on adjacent or neighboring carbon atoms. Examples of alkoxylated fatty amines can include: diethoxylated tallowamine, diethoxylated oleylamine, diethoxylated stearylamine, and the diethoxylated amine from soybean oil fatty acids. Alkoxylated fatty amines are commercially available from Akzo under the Ethomeen® series. In one embodiment, the friction modifier of the present invention can include a fatty acid or derivative thereof. The fatty acid or derivative thereof can have about 4 to 30 carbon atoms, or 8 to 26 carbon atoms, or 12 to 22 carbon atoms. Saturated and unsaturated monocarboxylic acids are useful and include capric, lauric, myristic, palmitic, stearic, behenic, oleic, petroselinic, elaidic, palmitoleic, linoleic, linolenic and erucic acid. Typical fatty acids are those derived from natural oil typically containing C6 or C22 fatty acid esters, i.e., glycerol fatty acid esters or triglycerides derived from natural sources, for use herein include, but are not limited to beef tallow oil, lard oil, palm oil, castor oil, cottonseed oil, corn oil, peanut oil, soybean oil, sunflower oil, olive oil, whale oil, coconut oil, palm oil, rape oil, and soya oil.

In another embodiment of this invention, the fatty acid can be the partial ester of a fatty carboxylic acid. The partial ester of the present invention has at least one free hydroxyl group and is formed by reacting at least one fatty carboxylic acid and at least one polyhydric alcohol.

The fatty carboxylic acid used to form the partial ester can be saturated or unsaturated aliphatic, can be branched or straight chain, can be a monocarboxylic or polycarboxylic acid, and can be a single acid or mixture of acids. The fatty carboxylic acid can have about 4 to 30 carbon atoms, or 8 to

26 carbon atoms, or 12 to 22 carbon atoms. Saturated and unsaturated monocarboxylic acids are useful and include capric, lauric, myristic, palmitic, stearic, behenic, oleic, petroselinic, elaidic, palmitoleic, linoleic, linolenic and erucic acid. The polyhydric alcohol used to form the partial ester has two or more hydroxyl groups and includes alkylene glycols, polyalkylene glycols, triols, polyols having more than three hydroxyl groups, and mixtures thereof. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, neopentyl glycol, glycerol, trimethylol propane, pentaerythritol, and sorbitol. The partial esters having at least one free hydroxyl group are commercially available or can be formed by a variety of methods well known in the art. These esters are derived from any of the above described fatty carboxylic acids and polyhydric alcohols or mixtures thereof. Preferred esters are derived from fatty carboxylic acids having about 12 to 22 carbon atoms and glycerol, and will usually be mixtures of mono- and diglycerides, such as, a mixture of glycerol monooleate and glycerol dioleate. In one embodiment, the friction modifier of the present invention is glycerol monooleate.

Another derivative of the fatty carboxylic acid is the amide of the fatty carboxylic acid. In general, these compounds are the reaction product of the natural fatty acid oils containing 6 to 22 carbon atoms and an amine. The fatty carboxylic acid of these amides can be saturated or unsaturated aliphatic, can be branched or straight chain, can be a monocarboxylic or polycarboxylic acid, and can be a single acid or mixture of acids. The fatty carboxylic acid can have about 6 to 30 carbon atoms, or 8 to 26 carbon atoms, or 12 to 22 carbon atoms. Saturated and unsaturated monocarboxylic acids are useful and include capric, lauric, myristic, palmitic, stearic, behenic, oleic, petroselinic, elaidic, palmitoleic, linoleic, linolenic and erucic acid.

The amine can be an alkyl amine having from about 2 to about 10 carbon atoms, or about 4 to about 6 carbon atoms. A typical amine can be the alkanol amines. The alkanolamine used in the reaction with the fatty acid can be a primary or secondary amine, which possesses at least one hydroxy group. The alkanolamine corresponds to the general formula HN(RiOH)₂-XHx wherein Ri is a lower hydrocarbyl having from about two to about six carbon atoms and x is 0 or 1. The expression "alkanolamine" is used in its broadest sense to include compounds containing at least one primary or secondary amine and at least one hydroxy group, such as, for example, monoalkanolamines, dialkanolamines, and so forth. It is believed that almost any alkanolamine can be used, although preferred alkanolamines are lower alkanolamines having form about two to about six carbon atoms. The alkanolamine can possess an O or N functionality, in addition to the one amino group (that group being a primary of secondary amino group), and at least one hydroxy group. Suitable alkanolamines for use herein include: monoethanolamine, diethanolamine, propanolamine, isopropanolamine, dipropanolamine, di-isopropanolamine, butanolamines, aminoethylaminoethanols, e.g., 2-(2-aminoethylamino)ethanol, and the like with diethanolamine being preferred. It is also contemplated that mixtures of two or more alkanolamines can be employed.

In one embodiment, the friction modifier can be present in the fuel additive concentrate in an amount from about 1 to about 99 percent by weight, or about 2 to about 50 percent by weight, or about 5 to about 40 percent by weight, or about 5 to about 30 percent by weight, in yet another embodiment from about 8 to about 25 percent by weight.

In one embodiment, the friction modifier of this invention can be present in a fuel composition on a weight basis from about 1 to about 10,000 ppm (parts per million), and in other embodiment from about 5 to about 8,000 ppm, or about 10 to about 7000 ppm, or about 20 to about 5000 ppm, or about

30 to about 2000 ppm, or about 50 to about 1500, or about 40 to about 1000 ppm, or about 40 to about 650 ppm.

Antioxidant The present invention can include one or more antioxidants. The antioxidants for use in the present invention are well known and include a variety of chemical types including phenate sulfides, phosphosulfurized ter- penes, sulfurized esters, aromatic amines, and hindered phenols. In one embodiment, the present invention can contain an antioxidant selected from the group consisting of hindered phenol or derivatives thereof, aromatic amines or derivatives thereof, and mixtures thereof.

Aromatic amines are typically of the formula

wherein R⁵ is a phenyl group or a phenyl group substituted by R⁷, and R⁶ and R⁷ are independently a hydrogen or an alkyl group containing 1 to 24 carbon atoms. Preferably R⁵ is a phenyl group substituted by R⁷ and R⁶ and R⁷ are alkyl groups containing from 4 to 20 carbon atoms. In one embodiment, the antioxidant can be an alkylated diphenylamine, such as, nonylated diphenyl- amine containing typically some of the formula

Hindered phenol antioxidants are typically alkyl phenols of the formula

wherein R , 4 is an alkyl group containing 1 to 24 carbon atoms and m is an integer of 1 to 5. In certain embodiments, R 4 contains 4 to 18 carbon atoms or 4 to 12 carbon atoms. R⁴ may be either straight chained or branched chained, especially branched. Suitable values of m include 1 to 4, such as 1 to 3 or, particularly, 2. In certain well-known embodiments, the phenol is a butyl substituted phenol containing 2 or 3 t-butyl groups. When a is 2, the t-butyl groups may occupy the 2,6-positions, that is, the phenol is sterically hindered:

The antioxidant can be, and typically is, further substituted at the 4-position with any of a number of substituents, such as hydrocarbyl groups or groups bridging to another hindered phenolic ring.

Also included among the antioxidants are hindered ester substituted phenols such as those represented by the formula:

t-alkyl wherein t-alkyl can be, among others, t-butyl, R is a straight chain or branched chain alkyl group containing about 1 to about 22 carbon atoms, or about 2 to about 22, or about 2 to about 8, or about 4 to about 8 carbon atoms. R may be a 2-ethylhexyl group, isooctyl or an n-butyl or n-octyl group. Hindered ester substituted phenols can be prepared by heating a 2,6-dialkylphenol with an acrylate ester under base catalysis conditions, such as, aqueous KOH. The antioxidants of the present invention can also include sulfurized olefins, such as, mono-, or disulfides or mixtures thereof. These materials generally have sulfide linkages having 1 to 10 sulfur atoms, or 1 to 4, or 1 or 2 sulfur atoms. Materials, which can be sulfurized to form the sulfurized organic compositions of the present invention, include: oils, fatty acids and esters, olefins and polyolefins made thereof, terpenes, or Diels-Alder adducts. Details of methods of preparing some such sulfurized materials can be found in U.S. Pat. Nos. 3,471,404 and 4,191,659. Molybdenum compounds can also serve as antioxidants. The use of molybdenum and sulfur containing compositions as antioxidants is known. In certain embodiment, a mixture of antioxidants are employed, such as, both a phenolic and an aromatic amine antioxidant, or mixtures thereof, or alternatively phenolic, or aromatic amine, or phosphosulfurized olefin antioxidants or molybdenum antioxidant or mixtures thereof.

In one embodiment, the amount of the antioxidant in the fuel composition can be present in an amount from about 1 to about 1000 ppm, or about 1 to about 5000, or about 2 to about 500, or about 4 to about 200 or about

5 to about 100 ppm.

In one embodiment, the amount of antioxidant can be present in the fuel additive concentration in an amount from about 1 to about 99 percent by weight, or from about 1 to about 40 percent by weight, or from about 2 to about 30 percent by weight, or from about 2 to about 20 percent by weight.

Fuel Composition

In one embodiment, the fuel composition contains a fuel, which is a liquid at room temperature, and an additive wherein the additive is selected from the group consisting of: a detergent; antioxidant; friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof; and mixtures thereof; wherein the detergent is soluble in a nonhydrocarbonaceous fuel. The fuel, which is a liquid at room temperature, and additives of the fuel composition are described above.

Fuel Additive Concentrate

In one embodiment, the fuel additive concentrate of the present invention can be present in a fuel in an amount from about 1 to about 10000 ppm, in another embodiment about 5 to about 8000 ppm, in another embodiment about 10 to about 5000 ppm or about 20 to about 5000 ppm, in yet another embodiment about 100 to about 4000 ppm, and in another embodiment about 200 to about 2000, or about 300 to about 2000 or about 300 to aboutlOOO ppm.

Miscellaneous

The fuel additive concentrate compositions and fuel compositions of the present invention can contain other additives that are well known to those of skill in the art. These can include corrosion inhibitors, dyes, bacteriostatic agents, auxiliary, gum inhibitors, marking agents, metal deactivators, detergents, demulsifϊers, or mixtures thereof.

Industrial Application In one embodiment the present invention can be used in an internal combustion engine. The internal combustion engine includes a 2-stroke or 4- stroke engine fuelled with alcohol. The internal combustion engine includes a direct injection or spark ignited engine.

As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include: hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring); substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo

(especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); hetero substituents, that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl. In general, no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group. It is known that some of the materials described above may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. For instance, metal ions (of, e.g., a detergent) can migrate to other acidic or anionic sites of other molecules. The products formed thereby, including the products formed upon employing the composition of the present invention in its intended use, may not be susceptible of easy description. Nevertheless, all such modifications and reaction products are included within the scope of the present invention; the present invention encompasses the composition prepared by admixing the components described above.

Each of the documents referred to above is incorporated herein by reference. Except in the Examples, or where otherwise explicitly indicated, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word "about." Unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade. However, the amount of each chemical component is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, unless otherwise indicated. It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used together with ranges or amounts for any of the other elements. As used herein, the expression "consisting essentially of permits the inclusion of substances that do not materially affect the basic and novel characteristics of the composition under consideration.

Claims

What we claim:

1. A fuel additive concentrate comprising: a. detergent; b. antioxidant; and c. a friction modifier selected from the group consisting of an alkoxy- lated fatty amine, a fatty acid or derivative thereof, and mixture thereof wherein the detergent is soluble in a nonhydrocarbonaceous fuel.

2. The fuel additive concentration of claim 1, wherein the detergent is a polyetheramine.

3. The fuel additive concentrate of claim 2, wherein the polyetheramine is represented by the formula RO(AO)_nJR¹NR²R³; wherein R is a hydrocarbyl group of about 8 to about 30 carbon atoms; A is an alkylene group having 2 to 6 carbon atoms; m is a number from 1 to about 50; R¹ is an alkylene group having 2 to 6 carbon atoms; and R² and R³ are independently hydrogen, a hydrocarbyl group or - [R⁴N(R⁵)]_nR⁶ wherein R⁴ is an alkylene group having 2 to 6 carbon atoms, R⁵ and

R⁶ are independently hydrogen or a hydrocarbyl group, and n is a number from 1 to 7.

4. The fuel additive concentrate of claim 3, wherein the polyetheramine is repre- sented by the formula RO[CH₂CH(CH₂CH₃)O]_1nCH₂CH₂CH₂NH₂; wherein R is an aliphatic group or alkyl-substituted phenyl group of about 8 to about 30 carbon atoms; and m is a number from about 12 to about 30.

5. The fuel additive concentrate of claim 4, wherein the polyetheramine is represented by the formula

CH3CH(CH3)[CH2CH(CH3)]2CH(CH3)CH2CH2O[CH2CH(CH2CH3)O]mCH2C

H2CH2NH2; wherein m is a number from about 16 to about 28.

6. The fuel additive concentrate of claim 1 , wherein the antioxidant is selected from the group consisting of hindered phenol or derivatives thereof, aromatic amines or derivatives thereof, and mixtures thereof.

7. The friction modifier of claim 1 , wherein the friction modifier is glycerol monooleate.

8. A fuel composition comprising: a. a fuel which is a liquid at room temperature; and b. additive wherein the additive is selected from the group consisting of: a detergent; antioxidant; friction modifier selected from the group consisting of an alkoxy- lated fatty amine, a fatty acid or derivative thereof, and mixture thereof; and mixtures thereof wherein the detergent is soluble in a nonhydrocarbonaceous fuel.

9. The fuel composition of claim 8, wherein the detergent is a poly- etheramine.

10. The fuel composition of claim 8, wherein the fuel which is a liquid at room temperature is a nonhydrocarbonaceous fuel.

11. The fuel composition of claim 10, wherein the nonhydrocarbonaceous fuel is methanol, ethanol, butanol, or mixtures thereof.

12. A method of fueling an internal combustion engine comprising: A. supplying to the internal combustion engine: i. a fuel which is a liquid at room temperature; and ii. additive wherein the additive is selected from the group consisting of: a detergent; antioxidant; friction modifier selected from the group consisting of an alkoxy- lated fatty amine, a fatty acid or derivative thereof, and mixture thereof; and mixtures thereof; wherein the detergent is soluble in a nonhydrocarbonaceous fuel.

13. The fuel composition of claim 12, wherein the detergent is a polyetheramine.