Gasoline additive composition for improving engine performance

Abstract

The present disclosure provides a fuel additive comprising a quaternary ammonium salt additive and a Mannich detergent additive, which effectively improves engine performance in both port fuel injection engines and direct injection engines.

Description

Technical Field

[0001] The present disclosure relates to fuel additives for internal combustion engines that provide enhanced engine and / or injector performance, fuel compositions comprising such additives, and methods of using such fuel additives in fuel compositions. Background Art

[0002] Fuel compositions for vehicles are continuously improved to enhance various properties of the fuel to accommodate their use in newer, more advanced engines, including both gasoline port fuel injection engines and direct injection engines. Generally, the improvement of fuel compositions focuses on improving fuel additives and other components used in the fuel. For example, friction modifiers can be added to the fuel to reduce friction and wear in the fuel delivery system of the engine. Other additives can be included to reduce the corrosion potential of the fuel or to improve the conductive properties. Other additives can also be blended with the fuel to improve fuel economy. Engine and fuel delivery system deposits represent another problem for modern internal combustion engines, and thus other fuel additives typically include various deposit control additives to control and / or mitigate engine deposit problems. Accordingly, fuel compositions generally include complex mixtures of additives.

[0003] However, challenges still exist when attempting to balance such complex classes of additives. For example, some conventional fuel additives can be beneficial for one property or one type of engine but detrimental to another property of the fuel at the same time. In some cases, fuel additives that are effective in gasoline port fuel injection engines do not necessarily provide comparable performance in direct injection engines, and vice versa. In still other cases, fuel additives typically require unreasonably high treatment rates to achieve the desired effects, which tend to impose undesirable limitations on the available amounts of other additives in the fuel composition. Yet other fuel additives tend to be expensive and / or difficult to manufacture or incorporate into the fuel. Such drawbacks are particularly true in the case of quaternary ammonium fuel additives, which are generally difficult to manufacture or are costly to manufacture and / or require relatively high treatment rates for performance. Summary of the Invention

[0004] In one aspect, provided herein are fuel additive packages, fuels, or methods that provide improved engine performance.

[0005] In one embodiment or method, a fuel additive package for an internal combustion engine is described herein to provide improved engine performance and comprises: a Mannich detergent comprising a reaction product of a hydrocarbyl-substituted phenol, one or more aldehydes, and one or more amines; and a quaternary ammonium salt additive having the structure of Formula II

[0006]

[0007] where each X is a divalent moiety selected from -O-, -N(R 12 )-, -C(O)-, -C(O)O- or -C(O)NR 12 ; each of R7, R8 and R9 is independently an alkyl group having 1 to 8 carbon atoms; R 10 and R 11 are independently selected from hydrogen, an alkyl group, an acyl group or a hydrocarbon group-substituted acyl group (optionally, R 10 and R 11 combine together with the N atom to which they are attached to form a ring moiety (e.g., succinimide)), and the hydrocarbon group substituents of one or both of R 10 and R 11 have a number average molecular weight of about 700 or greater (as further described herein); R 12 is independently hydrogen or a group selected from C 1-6 aliphatic, phenyl or alkylphenyl; each m is independently an integer of 0 or 1, where at least one m is 1; each n is independently an integer from 1 to 10; and is a carboxylate. The above internal combustion engine can be a spark ignition engine or a diesel engine.

[0008] In another embodiment or method, the fuel additive package of the previous paragraph may include optional features or embodiments in any combination. These optional features or embodiments include one or more of the following: further comprising an alkoxylated alcohol; and / or wherein the weight ratio of the alkoxylated alcohol to the Mannich detergent is about 1.0 or less; and / or wherein the alkoxylated alcohol is a polyether prepared by reacting an alkyl alcohol or an alkylphenol with an alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide, copolymers thereof or combinations thereof; and / or wherein the weight ratio of the Mannich detergent to the quaternary ammonium salt additive is about 4:1 to about 100:1; and / or wherein the Mannich detergent has the structure of formula I:

[0009]

[0010] wherein R1 is hydrogen or a C1 to C4 alkyl group, R2 is a hydrocarbon group having a number average molecular weight of about 500 to about 3000, R3 is a C1 to C4 alkylene or alkenyl group, and R4 and R5 are independently hydrogen, a C1 to C12 alkyl group or a C1 to C4 alkylamino C1-C12 alkyl group; and / or wherein the R 10 and R 11combine with the nitrogen atom to which they are attached to form a ring moiety; and / or wherein the carboxylate of the quaternary ammonium salt of formula II is oxalate, salicylate or a combination thereof; and / or wherein X of formula II is -O- or -NH- (preferably -O-); and / or wherein the quaternary ammonium salt is derived from 3-(2-(dimethylamino)ethoxy)propylamine, N,N-dimethyldipropylenetriamine or a mixture thereof; and / or wherein R 10 and R 11 combine with the nitrogen atom to which they are attached to form a hydrocarbyl-substituted succinimide; and / or wherein the hydrocarbyl substituent has a number average molecular weight of from about 700 to about 2,500; and / or wherein the X moiety of the quaternary ammonium salt of formula II is an oxygen atom, and wherein R 10 and R 11 combine with the nitrogen atom to which they are attached to form a hydrocarbyl-substituted succinimide, wherein the hydrocarbyl substituent has a number average molecular weight of from about 700 to about 1,500 as measured by GPC using polystyrene as a calibration reference; and / or wherein the alkoxylated alcohol is a polyether having the structure of formula Va:

[0011]

[0012] wherein R6 is an aryl group or a straight-chain, branched-chain or cyclic aliphatic group having 5 to 50 carbons, R7 of formula Va is a C1 to C4 alkyl group, and n is an integer from 5 to 100; and / or wherein the fuel additive package comprises from about 20 wt% to about 60 wt% of a Mannich detergent, from about 1 wt% to about 20 wt% of a quaternary ammonium salt additive, and from about 5 wt% to about 30 wt% of an alkoxylated alcohol; and / or further comprises a succinimide detergent prepared by reacting a hydrocarbyl-substituted succinic acylating agent with an amine, polyamine or alkylamine having one or more primary, secondary or tertiary amino groups; and / or wherein the fuel additive package comprises from about 0.1 wt% to about 10 wt% of the succinimide detergent; and / or wherein the succinimide detergent is a hydrocarbyl-substituted mono-succinimide detergent, a hydrocarbyl-substituted bis-succinimide detergent or a combination thereof; and / or further comprises one or more of a demulsifier, a corrosion inhibitor, an antiwear additive, an antioxidant, a metal deactivator, an antistatic additive, an antifogging agent, an antiknock additive, a lubricity additive and / or a combustion promoter.

[0013] In another aspect, the present disclosure provides a fuel comprising any embodiment of the fuel additive package described above for improving engine performance. In one embodiment or method, a gasoline fuel composition is provided, the gasoline fuel composition comprising: from about 15 ppmw to about 300 ppmw of a Mannich detergent, the Mannich detergent comprising the reaction product of a hydrocarbyl-substituted phenol, one or more aldehydes, and one or more amines; from about 0.1 ppmw to about 50 ppmw (or from about 0.1 ppmw to about 30 ppmw) of a quaternary ammonium salt additive having the structure of Formula II

[0014]

[0015] wherein each X is a divalent moiety selected from -O-, -N(R 12 )-, -C(O)-, -C(O)O-, or -C(O)NR 12 ; each R7, R8, and R9 is independently an alkyl group having 1 to 8 carbon atoms; R 10 and R 11 are independently selected from hydrogen, an alkyl group, an acyl group, or a hydrocarbyl-substituted acyl group (optionally, R 10 and R 11 combine with the N atom to which they are attached to form a ring moiety (such as a succinimide)), and the hydrocarbyl substituents of one or both of R 10 and R 11 have a number average molecular weight of about 700 or greater; R 12 is independently hydrogen or a group selected from C 1-6 aliphatic, phenyl, or alkylphenyl; each m is independently an integer of 0 or 1, where at least one m is 1; each n is independently an integer from 1 to 10; and is a carboxylate; and from about 5 ppmw to about 150 ppmw of an alkoxylated alcohol. In another embodiment or method, a diesel fuel composition is provided, the diesel fuel composition comprising: from about 15 ppmw to about 500 ppmw of a Mannich detergent, the Mannich detergent comprising the reaction product of a hydrocarbyl-substituted phenol, one or more aldehydes, and one or more amines; from about 0.1 ppmw to about 200 ppmw of the quaternary ammonium salt additive as described in any of the above embodiments.

[0016] In other embodiments, the fuels of the previous paragraph may include any embodiment of the fuel additive package described in the present disclosure.

[0017] In still other embodiments, a method of improving injector performance in an in - cylinder direct injection (GDI) engine is described herein. In still other embodiments, a method of improving injector performance in a gasoline port fuel injection (PFI) engine is described herein. In additional embodiments, a method of improving injector performance in both GDI and PFI engines is described herein. Further, the use of a fuel additive package or fuel for improving injector performance in GDI and / or PFI engines is also described herein. In the method or embodiment, the method or use includes operating an in - cylinder direct injection engine with a fuel composition that comprises a majority of gasoline fuel and a minor amount of any embodiment of the fuel additive package as described in the Summary of the Invention herein; and wherein the fuel additive package in the gasoline fuel improves the injector performance of the in - cylinder direct injection engine. In other methods, the improved injector performance is one of improved fuel flow, improved fuel economy, improved engine efficiency, or a combination thereof; and / or wherein the improved injector performance is measured by one of injector pulse width, injection duration, injector flow, or a combination thereof.

[0018] In still other embodiments, a method of improving diesel engine performance is described herein. In additional embodiments, a method of improving injector performance in a diesel engine is provided. Further, the use of a fuel additive package or fuel as described in any embodiment herein for improving injector performance in a diesel engine is also described herein. In the method or embodiment, the method or use includes operating a diesel engine with a fuel composition that comprises a majority of diesel fuel and a minor amount of any embodiment of the fuel additive package as described in the Summary of the Invention herein; wherein the fuel additive package in the diesel fuel improves the injector performance of the diesel engine (i.e., direct injection or indirect injection engine). In other methods, the engine performance is one of improved fuel flow, improved fuel economy, improved engine efficiency, or a combination thereof; and / or wherein the improved injector performance is measured by one of injector pulse width, injection duration, injector flow, or a combination thereof.

[0019] The methods or uses of the preceding paragraphs may include limitations of optional steps, features, or any combination thereof. The methods or embodiments of the method or use may include one or more of the following: wherein the improved injector performance is one of improved fuel flow, improved fuel economy, improved engine efficiency, or a combination thereof; and / or wherein the improved injector performance is measured by one of long - term fuel trim, injector pulse width, injection duration, injector flow, or a combination thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a graph showing the long - term fuel trim (LTFT) comparing a fuel additive and the fuel additive of the present invention. Detailed Description

[0021] The present disclosure relates to fuel additives, including a combination of Mannich detergents and quaternary ammonium salts, particularly a combination of Mannich detergents and hydrocarbon - substituted quaternary ammonium salts derived from high - molecular - weight polyamines and / or ether amines. It has been found that this combination effectively provides improved engine and / or injector performance in both port fuel injection (PFI) engines and gasoline direct injection (GDI) engines. In some methods, the fuel additive may further include alkoxylated alcohols, and when included, the ratio of the alkoxylated alcohol to the Mannich detergent is fixed. Also provided herein are fuel compositions comprising the novel fuel additive combination and methods of using or burning a fuel comprising the fuel additive combination of the present invention to achieve improved engine and / or injector performance.

[0022] In aspects or embodiments of the present disclosure, the improved engine and / or injector performance of the fuel additive combination herein may include controlling or reducing one or more of fuel injector deposits, intake valve deposits, combustion chamber deposits, and / or intake valve sticking. The improved injector performance may also be one or more of improved fuel flow, improved fuel economy, and / or improved engine efficiency as determined by one or more of long - term fuel trim, injector pulse width, injection duration, and / or injector flow.

[0023] The present disclosure also relates to fuel additives, including a combination of Mannich detergents and quaternary ammonium salts, particularly a combination of Mannich detergents and hydrocarbon - substituted quaternary ammonium salts derived from high - molecular - weight polyamines and / or ether amines. It has been found that this combination effectively provides improved engine and / or injector performance in diesel engines. Diesel engines include conventional distributor injection pumps, pump - nozzle systems (unit injector systems or unit pump systems), or common - rail systems.

[0024] In aspects or embodiments of the present disclosure, the improved engine and / or injector performance of the fuel additive combination herein may include controlling or reducing one or more of fuel injector deposits, intake valve deposits, combustion chamber deposits, and / or intake valve sticking. The improved injector performance may also be one or more of improved fuel flow, improved fuel economy, and / or improved engine efficiency as determined by one or more of long - term fuel trim, injector pulse width, injection duration, and / or injector flow.

[0025] Mannich detergent

[0026] In one aspect, the fuel additives and fuels of the present disclosure include Mannich detergents. Suitable Mannich detergents include the reaction products of alkyl-substituted hydroxyaromatic compounds or phenolic compounds, aldehydes, and amines, as discussed in more detail below.

[0027] In one method, the alkyl substituent of the hydroxyaromatic compound can include a long-chain hydrocarbon group on the benzene ring of the hydroxyaromatic compound and can be derived from an olefin or polyolefin having a number average molecular weight (Mn) of from about 500 to about 3000, preferably from about 700 to about 2100, as determined by gel permeation chromatography (GPC) using polystyrene as a reference. In some methods, the polyolefin can also have a polydispersity (weight average molecular weight / number average molecular weight) of from about 1 to about 10 (in other cases from about 1 to about 4 or from about 1 to about 2), as determined by GPC using polystyrene as a reference.

[0028] Alkylation of the hydroxyaromatic compound or phenolic compound is generally carried out in the presence of an alkylation catalyst at a temperature in the range of from about 0 °C to about 200 °C, preferably from 0 °C to 100 °C. Acid catalysts are generally used to facilitate Friedel-Crafts alkylation. Typical catalysts for commercial production include sulfuric acid, BF3, aluminum phenoxide, methanesulfonic acid, cation exchange resins, acidic clays, and modified zeolites.

[0029] The polyolefins for the alkyl-substituted hydroxyaromatic compounds suitable for forming Mannich detergents include polypropylene, polybutene, polyisobutene, butene, and / or copolymers of butene and propylene, copolymers of butene and / or isobutene and / or propylene, and one or more monoolefin comonomers copolymerizable therewith (e.g., ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene, etc.), wherein the copolymer molecules contain at least 50 wt% of butene and / or isobutene and / or propylene units. Any comonomer polymerized with propylene or butene can be aliphatic and can also contain non-aliphatic groups, such as styrene, o-methylstyrene, p-methylstyrene, divinylbenzene, etc., if desired. Thus, the resulting polymers and copolymers for forming the alkyl-substituted hydroxyaromatic compounds are substantially aliphatic hydrocarbon polymers.

[0030] Polybutene is preferably used to form the hydrocarbyl-substituted hydroxyaromatic compounds or phenolic compounds herein. Unless otherwise indicated herein, the term "polybutene" is used in its general sense to include polymers made from "pure" or "substantially pure" 1-butene or isobutene, as well as polymers made from mixtures of two or all three of 1-butene, 2-butene, and isobutene. Commercial grades of such polymers may also contain small amounts of other olefins. So-called highly reactive polyisobutenes having a relatively high proportion of polymer molecules with terminal vinylidene groups are also suitable for forming long-chain alkylated phenol reactants. Suitable highly reactive polyisobutenes include those polyisobutenes that contain at least about 20%, preferably at least 50%, and more preferably at least 70% of the more reactive methylvinylidene isomers. Suitable polyisobutenes include polyisobutenes prepared using a BF3 catalyst. The preparation of such polyisobutenes in which the methylvinylidene isomers are present in a high percentage of the total composition is described in US 4,152,499 and US 4,605,808, both of which are incorporated herein by reference.

[0031] In some methods or embodiments, Mannich detergents can be prepared from alkylphenols or alkylcresols. However, other phenolic compounds can be used, including alkyl-substituted derivatives of resorcinol, hydroquinone, catechol, hydroxydiphenyl, benzylphenol, phenylethylphenol, naphthol, tolylnaphthol, and the like. Preferred for the preparation of Mannich detergents are polyalkylphenol and polyalkylcresol reactants, such as polypropylphenol, polybutylphenol, polypropylcresol, and polybutylcresol, where the alkyl group has a number average molecular weight of about 500 to about 3000 or about 500 to about 2100 as measured by GPC using polystyrene as a reference, and the most preferred alkyl group is polybutyl derived from polyisobutene, which has a number average molecular weight in the range of about 700 to about 1300 as measured by GPC using polystyrene as a reference.

[0032] The preferred configuration of the hydrocarbyl-substituted hydroxyaromatic compound is the para-substituted monoalkylphenol or para-substituted monoalkyl-o-cresol configuration. However, any hydroxyaromatic compound that readily reacts in the Mannich condensation reaction can be employed. Thus, Mannich products made from hydroxyaromatic compounds having only one cycloalkyl substituent or two or more cycloalkyl substituents are suitable for forming the detergent additive. The alkyl substituent may contain some residual unsaturated groups, but is generally a substantially saturated alkyl group.

[0033] In a method or embodiment, representative amine reactants suitable for forming the Mannich detergents herein include, but are not limited to, alkylene polyamines having at least one suitably reactive primary or secondary amino group in the molecule. Other substituents such as hydroxyl, cyano, amido, etc. may be present in the polyamine. In one embodiment, the alkylene polyamine is a polyethylene polyamine. Suitable alkylene polyamine reactants include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and mixtures of such amines, the nitrogen content of which corresponds to the formula H2N--(A-NH--) n H of an alkylene polyamine, where A in this formula is a divalent vinyl or propenyl group, and n is an integer from 1 to 10, preferably from 1 to 4. The alkylene polyamine can be obtained by reacting ammonia with a dihaloalkane such as a dichloroalkane.

[0034] The amine can also be an aliphatic diamine having one primary or secondary amino group and at least one tertiary amino group in the molecule. Examples of suitable polyamines include N,N,N",N"-tetraalkyl diethylene triamine (two terminal tertiary amino groups and one central secondary amino group), N,N,N',N"-tetraalkyl triethylene tetramine (one terminal tertiary amino group, two internal tertiary amino groups, and one terminal primary amino group), N,N,N',N",N'"-pentaalkyl triethylene tetramine (one terminal tertiary amino group, two internal tertiary amino groups, and one terminal secondary amino group), N,N'-dialkylamine, N,N-dihydroxyalkyl-α,ω-alkylenediamine (one terminal tertiary amino group and one terminal primary amino group), N,N,N'-trihydroxyalkyl-α,ω-alkylenediamine (one terminal tertiary amino group and one terminal secondary amino group), tris(dialkylaminoalkyl)aminomethyl methane (three terminal tertiary amino groups and one terminal primary amino group), and similar compounds, where these alkyl groups are the same or different and generally each contain no more than about 12 carbon atoms, and preferably each contains 1 to 4 carbon atoms. Most preferably, these alkyl groups are methyl and / or ethyl. Preferred polyamine reactants are N,N-dialkyl-α,ω-alkylenediamines, such as those having 3 to about 6 carbon atoms in the alkylene group and 1 to about 12 carbon atoms in each alkyl group, these alkyl groups being most preferably the same, but can be different. Exemplary amines can include N,N-dimethyl-1,3-propanediamine and / or N-methylpiperazine.

[0035] Examples of polyamines having one reactive primary or secondary amino group capable of participating in the Mannich condensation reaction and at least one sterically hindered amino group that cannot directly participate in the Mannich condensation reaction to any significant extent include N-(tert-butyl)-1,3-propanediamine, N-neopentyl-1,3-propanediamine, N-(tert-butyl)-1-methyl-1,2-ethylenediamine, N-(tert-butyl)-1-methyl-1,3-propanediamine, and 3,5-bis(tert-butyl)aminoethyl piperazine.

[0036] In a method or embodiment, representative aldehydes for preparing the Mannich detergents herein include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, heptanal, stearaldehyde. Aromatic aldehydes that can be used include benzaldehyde and salicylaldehyde. Illustrative heterocyclic aldehydes for the present invention are furfural and thiophene aldehyde, etc. Also useful are formaldehyde-yielding reagents such as paraformaldehyde, or aqueous formaldehyde solutions such as formalin. Most preferably is formaldehyde or formalin.

[0037] The condensation reaction between an alkylphenol, a specific amine and an aldehyde can be carried out at a temperature in the range of usually about 40 °C to about 200 °C. The reaction can be carried out in bulk (without diluent or solvent) or in a solvent or diluent. Water is removed during the reaction and can be removed by azeotropic distillation. Generally, the Mannich reaction product is formed by reacting an alkyl-substituted hydroxyaromatic compound, an amine and an aldehyde in a molar ratio of 1.0:0.5 - 2.0:1.0 - 3.0 respectively. Suitable Mannich base detergents include those detergents taught in the following patents: US 4231759; US 5,514,190; US 5,634,951; US 5,697,988; US 5,725,612; and 5876468, the disclosures of these patents are incorporated herein by reference.

[0038] In other methods or embodiments, the Mannich detergents suitable for the fuel additives herein may have the structure of Formula I:

[0039]

[0040] Wherein R1 is hydrogen or a C1 - C4 alkyl group, R2 is a hydrocarbon group having a number average molecular weight of about 500 to about 3,000 (or about 500 to about 2,100 or about 500 to about 1,800), R3 is a C1 - C4 alkylene or alkenyl linking group, and R4 and R5 are independently hydrogen, a C1 - C12 alkyl group or a C1 - C4 alkylamino C1 - C12 alkyl group.

[0041] The fuel additive or additive package may contain about 10 wt% to about 70 wt% of the above-mentioned Mannich detergent, about 20 wt% to about 60 wt% of the Mannich detergent or about 30 wt% to about 50 wt% of the Mannich detergent (based on the total weight of the active Mannich detergent in the fuel additive). When blended into a gasoline fuel, the fuel composition may contain about 15 ppmw to about 300 ppmw of the above-mentioned Mannich detergent in the fuel composition, about 25 ppmw to about 155 ppmw or about 55 ppmw to about 125 ppmw of the Mannich detergent (active Mannich detergent treatment rate).

[0042] Quaternary ammonium salt additive:In another method, the mixtures herein further include quaternary ammonium salt additives, particularly hydrocarbon group-substituted succinimide quaternary ammonium salt additives derived from polyamines or ether amines having high molecular weight hydrocarbon group substituents. In the method, the quaternary ammonium salts of the mixtures herein include quaternary ammonium salts formed by the reaction between an alkyl carboxylate and an amide or imide compound, which amide or imide compound is obtained by reacting a hydrocarbon group-substituted acylating agent such as a high molecular weight hydrocarbon group-substituted acylating agent with a polyamine or more preferably an ether amine.

[0043] In one method, the quaternary ammonium salt is a cationic salt having the structure of Formula II

[0044]

[0045] wherein each X is a divalent moiety selected from -O-, -N(R 12 )-, -C(O)-, -C(O)O- or -C(O)NR 12 ; each R7, R8 and R9 is independently an alkyl group containing 1 to 8 carbon atoms; R 10 and R 11 are independently selected from an alkyl group, an acyl group or a hydrocarbon group-substituted acyl group, and optionally, R 10 and R 11 combine with the N atom to which they are attached to form a ring moiety (such as succinimide), and the hydrocarbon group substituents of one or both of R 10 and R 11 have a number average molecular weight of about 700 or greater (as described herein); R 12 is independently hydrogen or a group selected from C 1-6 aliphatic, phenyl or alkylphenyl; each m is independently an integer of 0 or 1, where at least one m is 1; each n is independently an integer from 1 to 10; and is a carboxylate.

[0046] In one method, the polyamine or preferably ether amine used to form the quaternary ammonium salt additive of Formula II herein may have the structure of Formula III

[0047] H2N-(CH2) n -X m -(CH2) n -X m -(CH2) n -N(R7)(R8) (Formula III)

[0048] wherein X, R7, R8 and the integers n and m are as defined above. In a preferred method, the X moiety is an oxygen atom or a nitrogen atom, and more preferably an oxygen atom. In a preferred method, the amine is 3-(2-(dimethylamino)ethoxy)propylamine; N,N-dimethyldipropylenetriamine; or a mixture thereof.

[0049] Any of the foregoing tertiary amines can react with a hydrocarbyl-substituted acylating agent having the high molecular weight hydrocarbyl substituents described herein to form a quaternary ammonium salt additive. In the method, the hydrocarbyl-substituted acylating agent can be selected from hydrocarbyl-substituted mono-, di- or polycarboxylic acids or their reactive equivalents to form amide or imide compounds. Particularly suitable acylating agents are hydrocarbyl-substituted succinic acids, esters, anhydrides, monoacids / monoesters, or diacids. In some methods, the hydrocarbyl-substituted acylating agent is a hydrocarbyl-substituted dicarboxylic acid or its anhydride derivative, a fatty acid, or a mixture thereof. The hydrocarbyl substituent can have a number average molecular weight of 700 or greater, and preferably from about 700 to about 5,000 (or about 900 to about 2,500) as described above.

[0050] In other methods, the hydrocarbyl-substituted acylating agent can be a carboxylic acid or anhydride reactant. In one method, the hydrocarbyl-substituted acylating agent can be selected from stearic acid, oleic acid, linoleic acid, linolenic acid, palmitic acid, palmitoleic acid, lauric acid, myristic acid, myristoleic acid, capric acid, caprylic acid, arachidic acid, behenic acid, erucic acid, their anhydride derivatives, or combinations thereof.

[0051] In one method, the hydrocarbyl-substituted acylating agent suitable for the quaternary ammonium salt additive is a hydrocarbyl-substituted dicarboxylic anhydride of formula IV

[0052]

[0053] wherein R of formula IV 13 is a hydrocarbyl or alkenyl group having a high molecular weight as described above. In certain aspects, R 13 is a hydrocarbyl group having a number average molecular weight of from about 700 to about 5,000, from about 700 to about 2,500 or from about 700 to about 1,500. In other methods, R 13 can have a number average molecular weight in the range of about 700 to about 1300 as measured by GPC using polystyrene as a calibration reference. Particularly useful R 13 has a number average molecular weight of about 1000 daltons and contains polyisobutene.

[0054] In some methods, R of formula IV 13 is a hydrocarbyl moiety that can include one or more polymer units selected from linear or branched alkenyl units. In some aspects, the alkenyl units can have from about 2 to about 10 carbon atoms. For example, the polyalkenyl group can contain one or more linear or branched polymer units formed from vinyl groups, propenyl groups, butenyl groups, pentenyl groups, hexenyl groups, octenyl groups, and decenyl groups. In some aspects, R 13The polyalkenyl group can be in the form of, for example, a homopolymer, copolymer, or terpolymer. In other aspects, the polyalkenyl group is polyisobutene. For example, the polyalkenyl group can be a homopolymer of polyisobutene containing from about 5 to about 60 isobutene groups, such as from about 15 to about 30 isobutene groups. For forming R 13 The polyalkenyl compound for the polyalkenyl group can be formed by any suitable method, such as by conventional catalytic oligomerization of olefins.

[0055] In some aspects, highly reactive polyisobutene having a relatively high ratio of polymer molecules to terminal vinylidene groups can be used to form R 13 groups. In one example, at least about 60%, such as from about 70% to about 90% of the polyisobutene contains terminal olefin double bonds. In some aspects, about one mole of maleic anhydride can react per mole of polyalkylene, such that the resulting polyalkenyl succinic anhydride has from about 0.8 to about 1.5 succinic anhydride groups on each polyalkylene substituent. In other aspects, the molar ratio of succinic anhydride groups to polyalkylene can range from about 0.5 to about 3.5, such as from about 1 to about 1.3.

[0056] Suitable alkylating or quaternizing agents for the quaternary ammonium salt additive are hydrocarbon group-substituted carboxylic acid esters, such as alkyl carboxylates or dialkyl carboxylates. In some methods or embodiments, the quaternizing agent is an alkyl carboxylate selected from alkyl oxalates, dialkyl oxalates, alkyl salicylates, and combinations thereof. In other methods or embodiments, the alkyl group of the alkyl carboxylate contains 1 to 6 carbon atoms and is preferably methyl. Suitable alkylating or quaternizing agents for the second quaternary ammonium salt additive herein can be dimethyl oxalate or methyl salicylate.

[0057] For alkylation with an alkyl carboxylate, in some methods it may be required that the corresponding acid pKa of the carboxylate is less than 4.2. For example, the corresponding acid of the carboxylate can have a pKa less than 3.8, such as less than 3.5, with a pKa less than 3.1 being particularly desirable. Examples of suitable carboxylates can include, but are not limited to, maleate, citrate, fumarate, phthalate, 1,2,4-benzenetricarboxylate, 1,2,4,5-benzenetetracarboxylate, nitrobenzoate, nicotinate, oxalate, glycinate, and salicylate. As described above, preferred carboxylates include oxalate, salicylate, and combinations thereof.

[0058] Examples of suitable quaternary ammonium salts obtained from the reactions described above for the quaternary ammonium salt additive include, but are not limited to, compounds of the following exemplary structures:

[0059]

[0060]

[0061] wherein X, R7, R8, R9, R 13 and M and the integers n and m are as described above. R 14 is a C1 to C30 hydrocarbyl group. Due to the length of the hydrocarbyl chain and the presence of a divalent moiety having an internal oxygen or nitrogen atom (i.e., the X moiety) in some methods, it is believed that the quaternary ammonium salts described herein include relatively sterically available quaternary nitrogen that is more useful for detergent activity than prior quaternary ammonium compounds.

[0062] The fuel additive or additive package may comprise from about 1 wt% to about 30 wt% of the above quaternary ammonium salt, from about 2 wt% to about 25 wt% of the quaternary ammonium salt, or from about 2 wt% to about 10 wt% of the quaternary ammonium salt (based on the total weight of the active detergent in the fuel additive). In other methods, the fuel composition comprises from about 1 ppmw to about 50 ppmw, in other methods from about 2 ppmw to about 25 ppmw, and in yet other methods from about 4 ppmw to about 15 ppmw of the quaternary ammonium salt additive. Other ranges within the recited endpoints are also within the scope of the present disclosure.

[0063] Alkoxylated alcohol

[0064] The fuel additive or fuel of the present disclosure may further include one or more optional alkoxylated alcohols. The alkoxylated alcohol is preferably a polyether prepared by reacting a long-chain alkyl alcohol or alkylphenol with an alkylene oxide. By one method, the alkoxylated alcohol may be one or more hydrocarbyl-terminated or hydrocarbyl-capped poly(alkylene oxide) polymers. Its hydrocarbyl moiety may be an aryl or aliphatic group and is preferably a straight-chain, branched-chain, or cyclic aliphatic chain, and most preferably a straight-chain aliphatic chain. In one method, the alkoxylated alcohol may have the structure of Formula Va, Vb, and / or Vc:

[0065]

[0066]

[0067] wherein R6 of Formula Va, Vb, and / or Vc is an aryl or straight-chain, branched-chain, or cyclic aliphatic group and preferably has 5 to 50 carbons (or 5 to 30 carbons), or may be a -C m H 2m+1 group, where m is an integer of 12 or greater, R7 of Formula Va, Vb, and / or Vc is a C1 to C4 alkyl group, and n is an integer from 5 to 100 (or as further discussed below).

[0068] In some methods, suitable alkoxylated alcohols are derived from lower alkylene oxides selected from ethylene oxide, propylene oxide, butylene oxide, copolymers thereof, and combinations thereof. Preferably, the lower alkylene oxide is propylene oxide or butylene oxide or a copolymer of ethylene oxide, propylene oxide, and butylene oxide (and any combination thereof). In another method, the alkylene oxide is propylene oxide. Any copolymer of such alkylene oxides can be a random or block copolymer. In one method, the alkoxylated alcohol can be terminated or capped with an aryl, alkyl, or hydrocarbyl group and can include one or more aryl or straight-chain, branched-chain, or cyclic aliphatic C5 to C30-capped alkoxylated alcohols, and in other methods, C16 to C18 (or blends thereof)-capped alkoxylated alcohols having 5 to 100, 10 to 80, 20 to 50, or 22 to 32 alkylene oxide repeat units (i.e., the integer n in the above formula). In some methods, the alkoxylated alcohol can have a weight-average molecular weight of about 1300 to about 2600, and in other methods, about 1600 to about 2200.

[0069] In some methods, the aliphatic hydrocarbyl-terminated alkoxylated alcohol can include about 20 wt% to about 70 wt% (in another method, about 30 wt% to about 50 wt%) of an aliphatic C16 alkoxylated alcohol having 24 to 32 alkylene oxide repeat units, and / or can include about 30 wt% to about 80 wt% (in another method, about 50 wt% to about 70 wt%) of an aliphatic C18 alkoxylated alcohol having 24 to 32 alkylene oxide repeat units. In other methods, the fuel additives herein (if including alkoxylated alcohols) can also have about 8% or less (in other methods, about 6% or less, and in still other methods, about 4% or less) of C20 or higher alkoxylated alcohols and / or about 4 wt% or less (or in other methods about 2 wt% or less, and in still other methods, about 1% or less) of C14 or lower alkoxylated alcohols.

[0070] Aryl- or hydrocarbyl-capped poly(alkylene oxide) alcohols can be produced by adding a lower alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide to a desired hydroxy compound R-OH (i.e., the starting alcohol) under polymerization conditions, where R is an aryl or hydrocarbyl group having 5 to 30 carbons or other chain lengths as described above and which caps the poly(alkylene oxide) chain. The alkoxylated alcohol can be prepared from any starting alcohol that provides the desired polyol distribution. By one method, the alkoxylated alcohol can be prepared by reacting a saturated straight-chain or branched-chain alcohol of the desired hydrocarbon size with a selected alkylene oxide and a bimetallic or basic catalyst. In one method, the alkoxylated alcohol can be a nonylphenol alkoxylated alcohol, such as nonylphenol propoxylated alcohol.

[0071] In other methods, in the polymerization reaction, a single type of alkylene oxide can be used, such as propylene oxide. In this case, the product is a homopolymer, such as poly(alkylene oxide) propanol. However, copolymers are also suitable, and random or block copolymers are easily prepared by contacting a hydroxy-containing compound with a mixture of alkylene oxides, such as a mixture of ethylene oxide, propylene oxide, and / or butylene oxide. When the reactivities of the oxides are relatively equal, it is easier to prepare random polymers. In some cases, when ethylene oxide is copolymerized with other oxides, the higher reactivity of ethylene oxide makes it difficult to prepare random copolymers. In either case, block copolymers can be prepared. Block copolymers are prepared by contacting a hydroxy-containing compound with a first alkylene oxide under polymerization conditions and then contacting it with other alkylene oxides in any order or repeatedly. In one example, a specific block copolymer can be represented by a polymer prepared by polymerizing propylene oxide on a suitable monohydroxy compound to form poly(propylene oxide) alcohol and then polymerizing butylene oxide on the poly(alkylene oxide) alcohol.

[0072] When included, the fuel additives or fuels herein may contain from about 5 wt% to about 30 wt% of alkoxylated alcohols, from about 8 wt% to about 20 wt% of alkoxylated alcohols, or from about 10 wt% to about 15 wt% of alkoxylated alcohols (based on the active alkoxylated alcohols in the fuel additive). When blended into gasoline fuels, the fuel may optionally contain from about 2 ppmw to about 150 ppmw of active alkoxylated alcohols, 5 ppmw to about 150 ppmw, from about 8 ppmw to about 50 ppmw, or from about 15 ppmw to about 40 ppmw of alkoxylated alcohols in the fuel.

[0073] Succinimide detergent

[0074] The fuel additives or fuels herein may also contain one or more optional hydrocarbyl-substituted dicarboxylic anhydride derivatives, and preferably one or more optional succinimide detergents. In one method, the optional additive can be prepared by reacting a hydrocarbyl-substituted succinic acylating agent with an amine, polyamine, or alkylamine having one or more primary, secondary, or tertiary amino groups. In some embodiments, the hydrocarbyl-substituted dicarboxylic anhydride derivatives include hydrocarbyl succinimides, succinamides, succinimide-amides, and succinimide-esters. These nitrogen-containing derivatives of hydrocarbyl succinic acylating agents can be prepared by reacting a hydrocarbyl-substituted succinic acylating agent with an amine, polyamine, or alkylamine having one or more primary, secondary, or tertiary amino groups. The detergent can be a mono-succinimide, bis-succinimide, or a combination thereof.

[0075] In some methods or embodiments, the hydrocarbyl-substituted dicarboxylic anhydride derivatives may include hydrocarbyl substituents having a number average molecular weight in the range of about 450 to about 3000 as measured by GPC using polystyrene as a reference. The derivatives may be selected from diamides, acid / amide, acid / ester, diacids, amide / ester, diesters, and imides. Such derivatives can be prepared by reacting a hydrocarbyl-substituted dicarboxylic anhydride with ammonia, polyamines, or alkylamines having one or more primary, secondary, or tertiary amino groups. In some embodiments, the polyamine or alkylamine can be tetraethylenepentamine (TEPA), triethylenetetramine (TETA), and similar amines. In other methods, the polyamine or alkylamine may have the formula H2N—((CHR1—(CH2) q —NH) r —H, where R1 in the above formula is hydrogen or an alkyl group having 1 to 4 carbon atoms, q is an integer from 1 to 4, and r is an integer from 1 to 6, and mixtures thereof. In other methods, the molar ratio of the hydrocarbyl-substituted dicarboxylic anhydride to the ammonia, polyamine, or alkylamine may be from about 0.5:1 to about 2:1, and in other methods from about 1:1 to about 2:1.

[0076] In other methods, the hydrocarbyl-substituted dicarboxylic anhydride can be a hydrocarbyl carbonyl compound of formula VI:

[0077]

[0078] where R in formula VI 10 is a hydrocarbyl group derived from a polyolefin. In some aspects, the hydrocarbyl carbonyl compound can be a polyalkylene succinic anhydride reactant, where R 10 is a hydrocarbyl moiety, such as a polyenyl group having a number average molecular weight of about 450 to about 3000 as measured by GPC using polystyrene as a reference. For example, as measured by GPC using polystyrene as a reference, the number average molecular weight of R 10 can be in the range of about 600 to about 2,500 or about 700 to about 1,500. Particularly useful R in formula VI 10 can have a number average molecular weight of about 950 to about 1,000 daltons (as measured by GPC using polystyrene as a reference) and contains polyisobutene. Unless otherwise indicated, the molecular weights in this specification are number average molecular weights as measured by GPC using polystyrene as a reference.

[0079] In the method, R in formula VI 10 is a hydrocarbyl moiety that may include one or more polymer units selected from linear or branched alkenyl units. In some aspects, the alkenyl units may have about 2 to about 10 carbon atoms. For example, the polyenyl may contain one or more linear or branched polymer units selected from vinyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, and decenyl. In some aspects, R in formula VI10 The polyalkenyl group can be in the form of, for example, a homopolymer, copolymer or terpolymer. In one aspect, the polyalkenyl is isobutene. For example, the polyalkenyl group can be a homopolymer of polyisobutene containing from about 10 to about 60 isobutene groups, such as from about 20 to about 30 isobutene groups. For forming R 10 The polyalkenyl compound of the polyalkenyl group can be formed by any suitable method, such as by conventional catalytic oligomerization of olefins.

[0080] In some aspects, highly reactive polyisobutene having a relatively high ratio of polymer molecules to terminal vinylidene groups can be used to form R 10 groups. In one example, at least about 60%, such as from about 70% to about 90% of the polyisobutene contains terminal olefin double bonds. Highly reactive polyisobutene is disclosed, for example, in US 4,152,499, the disclosure of which is incorporated herein by reference in its entirety.

[0081] In some aspects, about one mole of maleic anhydride can react per mole of the polyalkylene such that the resulting polyalkenyl succinic anhydride has from about 0.8 to about 1 succinic anhydride group on each polyalkylene substituent. In other aspects, the molar ratio of succinic anhydride groups to polyalkylene can range from about 0.5 to about 3.5, such as from about 1 to about 1.1.

[0082] The hydrocarbyl carbonyl compound can be prepared using any suitable method. An example of a method for forming a hydrocarbyl carbonyl compound involves blending a polyolefin and maleic anhydride. The polyolefin and maleic anhydride reactants are heated to a temperature of, for example, from about 150 °C to about 250 °C, optionally in the presence of a catalyst such as chlorine or a peroxide. Another exemplary method for preparing polyalkenyl succinic anhydride is described in US 4,234,435, the disclosure of which is incorporated herein by reference in its entirety.

[0083] In the dicarboxylic anhydride derivative substituted with a hydrocarbyl group, the polyamine reactant can be an alkylene polyamine. For example, the polyamine can be selected from ethylene polyamines, propylene polyamines, butylene polyamines and the like. In one method, the polyamine is an ethylene polyamine, which can be selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and N,N'-(imino-di-2,1-ethanediyl)bis-1,3-propanediamine. A particularly useful ethylene polyamine is the compound of the formula H2N—((CHR1—(CH2) q —NH) r —H, where R1 is hydrogen, q is 1, and r is 4.

[0084] In still other methods, the hydrocarbyl-substituted dicarboxylic anhydride derivative is a compound of formula VII

[0085]

[0086] wherein R of formula VII 10 is a hydrocarbyl group (such as polyisobutene and / or other aforementioned R 10 moieties), and R of formula VII 11 is hydrogen, alkyl, aryl, -OH, -NHR 12 or polyamine or an alkyl group containing one or more primary, secondary or tertiary amino groups. In some methods, R of formula VII 11 is derived from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N,N'-(iminodi-2,1-ethanediyl)bis-1,3-propanediamine, and combinations thereof. In some embodiments of formula VII, R 10 is a hydrocarbyl group, and R 11 is hydrogen, alkyl, aryl, -OH, -NHR 12 or polyamine, and wherein R of this formula 12 is hydrogen or alkyl. In other embodiments, the formula VII additive comprises a hydrocarbyl-substituted succinimide derived from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N,N'-(iminodi-2,1-ethanediyl)bis-1,3-propanediamine, and combinations thereof. In some other embodiments, R in the formula VII compound 10 is a hydrocarbyl group having a number average molecular weight of about 450 to about 3,000, and R of formula VII 11 is derived from tetraethylenepentamine and its derivatives.

[0087] In still other methods, R of formula VII 11 is a compound of formula VIII

[0088]

[0089] wherein A is NR 12 or an oxygen atom, R of formula VIII 12 , R 13 and R 14 are independently a hydrogen atom or an alkyl group, m and p are integers from 2 to 8; and n is an integer from 0 to 4. In some methods, R of formula VIII 13 and R 14 together with the nitrogen atom to which they are attached form a 5-membered ring. In the method, the succinimide detergent is a hydrocarbyl-substituted mono-succinimide detergent, a hydrocarbyl-substituted bis-succinimide detergent, or a combination thereof.

[0090] When included, the fuel additives or fuels of the present disclosure may contain from about 0.1 wt% to about 10 wt% of an active succinimide detergent, from about 0.5 wt% to about 8 wt% of a succinimide detergent, or from about 1 wt% to about 5 wt% of a succinimide detergent (based on the total weight of the active succinimide in the fuel additive). When blended into a gasoline fuel, the fuel may optionally contain from about 0.5 ppmw to about 20 ppmw of an active succinimide detergent, from about 1 ppmw to about 10 ppmw, or from about 2 ppmw to about 5 ppmw of a succinimide detergent in the fuel.

[0091] Fuel additive :

[0092] When formulating the fuel compositions of the present application, the above additives (including at least Mannich detergents and quaternary ammonium salts) can be used in an amount sufficient to reduce or inhibit deposit formation in the combustion chambers of the fuel system, engine, and / or crankcase and / or within the fuel injectors and in direct-in-cylinder engines and / or port fuel injection engines. Such additives can also be provided in an amount that improves injector performance as described herein. In some aspects, the fuel additives or fuel additive packages of the present disclosure may at least include the above Mannich detergents, quaternary ammonium salts, optional alkoxylated alcohols, and optional succinimide detergents. The fuel additives of the present disclosure may also include other optional additives as needed for a particular application and may include, as needed, one or more of a demulsifier, a corrosion inhibitor, an antiwear additive, an antioxidant, a metal deactivator, an antistatic additive, an antifogging agent, an antiknock additive, a lubricity additive, and / or a combustion promoter.

[0093] In some methods or embodiments, the fuel additives or additive packages of the present disclosure may contain from about 20 wt% to about 60 wt% of a Mannich detergent and from about 1 wt% to about 20 wt% of a quaternary ammonium salt (or any other range therebetween). In other methods, the fuel additive or additive package may also contain from about 5 wt% to about 20 wt% of an alkoxylated alcohol and / or from about 0.1 wt% to about 10 wt% of a succinimide detergent (or any other range therebetween).

[0094] In other methods, the gasoline fuel composition can contain from about 40 ppmw to about 750 ppmw of the fuel additives or additive packages herein, in other methods, from about 60 ppmw to about 380 ppmw, or from about 135 ppmw to about 310 ppmw of the above fuel additive packages, and which provide to the fuel from about 15 ppmw to about 300 ppmw of Mannich detergents and from about 0.1 ppmw to about 50 ppmw of quaternary ammonium salts. In other embodiments, the fuel can further contain from about 2 ppmw to about 90 ppmw of alkoxylated alcohols and / or from about 0.5 ppmw to about 20 ppmw of succinimide detergents. It should also be understood that any endpoints between the ranges described above are also suitable range amounts according to the needs of a particular application. The above amounts reflect the additives on an active ingredient basis, which means that the above additives do not include (i) the weight of unreacted components associated with and remaining in the product such as produced and used, and (ii) the weight of (one or more) solvents (if present) used in its manufacture during or after product formation.

[0095] In other methods, the fuel additive package or the fuel thereof also has a specific weight ratio of alkoxylated alcohol to Mannich detergent of 1.0 or less (i.e., 1.0:1 or less), about 0.8 or less, about 0.6 or less, about 0.5 or less, about 0.4 or less, or about 0.3 or less, and about 0.1 or greater (i.e., 0.1:1), about 0.2 or greater, or about 0.3 or greater. In still other methods, the fuel additive package or the fuel thereof can also have a weight ratio of Mannich detergent to quaternary ammonium salt of from about 4:1 to about 100:1, or from about 4:1 to about 50:1, or from about 6:1 to about 10:1 (where the weight ratio is of active Mannich detergent to active quaternary ammonium salt additive).

[0096] Other additives

[0097] One or more optional compounds can be present in the fuel compositions of the disclosed embodiments. For example, the fuel can contain conventional amounts of cetane improvers, octane improvers, corrosion inhibitors, cold flow improvers (CFPP additives), pour point depressants, solvents, demulsifiers, lubricity additives, friction modifiers, amine stabilizers, combustion improvers, detergents, dispersants, antioxidants, heat stabilizers, electrical conductivity improvers, metal deactivators, marker dyes, organic nitrate ignition promoters, cyclic tricarbonyl manganese compounds, carrier fluids, etc. In certain aspects, based on the total weight of the additive concentrate, the compositions described herein can contain about 10 wt% or less, or in other aspects, about 5 wt% or less of one or more of the above optional additives. Similarly, the fuel can contain suitable amounts of conventional fuel blend components such as methanol, ethanol, dialkyl ethers, 2-ethylhexanol, etc.

[0098] In certain aspects of the disclosed embodiments, organic nitrate ignition promoters can be used, which include aliphatic or cycloaliphatic nitrates, where the aliphatic or cycloaliphatic group is saturated and contains up to about 12 carbons. Examples of organic nitrate ignition promoters that can be used are methyl nitrate, ethyl nitrate, propyl nitrate, isopropyl nitrate, allyl nitrate, butyl nitrate, isobutyl nitrate, sec-butyl nitrate, tert-butyl nitrate, amyl nitrate, isoamyl nitrate, 2-pentyl nitrate, 3-pentyl nitrate, hexyl nitrate, heptyl nitrate, 2-heptyl nitrate, octyl nitrate, isooctyl nitrate, 2-ethylhexyl nitrate, nonyl nitrate, decyl nitrate, undecyl nitrate, dodecyl nitrate, cyclopentyl nitrate, cyclohexyl nitrate, methylcyclohexyl nitrate, cyclododecyl nitrate, 2-ethoxyethyl nitrate, 2-(2-ethoxyethoxy)ethyl nitrate, tetrahydrofuran nitrate, etc. Mixtures of such materials can also be used.

[0099] Examples of optional metal deactivators suitable for the compositions of the present application are disclosed in U.S. Patent No. 4,482,357, the disclosure of which is incorporated herein by reference in its entirety. Such metal deactivators include, for example, salicylidene-o-aminophenol, disalicylideneethylenediamine, disalicylidenepropylenediamine, and N,N'-disalicylidene-1,2-diaminopropane.

[0100] Suitable optional cyclic tricarbonyl manganese compounds that can be employed in the compositions of the present application include, for example, cyclopentadienyl tricarbonyl manganese, methylcyclopentadienyl tricarbonyl manganese, indenyl tricarbonyl manganese, and ethylcyclopentadienyl tricarbonyl manganese. Further examples of suitable cyclic tricarbonyl manganese compounds are disclosed in U.S. Patent No. 5,575,823 and U.S. Patent No. 3,015,668, the disclosures of which are incorporated herein by reference in their entireties.

[0101] Other commercially available detergents can be used in combination with the reaction products described herein. Such detergents include, but are not limited to, succinimides, Mannich base detergents, PIB amines, quaternary ammonium detergents, diamino triazole detergents, as generally described in U.S. Patent Application Serial No. 13 / 450,638, and reaction products of hydrocarbon-substituted dicarboxylic acids or acid anhydrides with aminoguanidine, where the reaction product has less than 1 equivalent of amino triazole groups per molecule, as generally described in U.S. Patent Application Serial Nos. 13 / 240,233 and 13 / 454,697.

[0102] The additives of the present application and optional additives for formulating the fuel of the present invention can be blended into the base fuel individually or in various sub-combinations. In certain embodiments, the additive components of the present application can be blended into the fuel simultaneously using an additive concentrate, as this takes advantage of the compatibility and convenience provided by the combination of ingredients when in the form of an additive concentrate. Additionally, using a concentrate can reduce blending time and the likelihood of blending errors.

[0103] Fuel

[0104] The fuel of the present application is suitable for operating diesel, jet, or gasoline engines, preferably spark-ignition or gasoline engines. The engines can include stationary engines (e.g., engines for power generation units, pumping stations, etc.) and mobile engines (such as engines serving as prime movers for automobiles, trucks, road grading equipment, military vehicles, etc.). For example, the fuel can include any and all middle distillate fuels, diesel fuels, bio-renewable fuels, biodiesel fuels, fatty acid alkyl esters, gas-to-liquid (GTL) fuels, gasoline, jet fuels, alcohols, ethers, kerosene, low-sulfur fuels, synthetic fuels such as Fischer-Tropsch fuels, liquefied petroleum gas, marine fuels, coal-to-liquid (CTL) fuels, biomass-to-liquid (BTL) fuels, high-asphaltene fuels, fuels derived from coal (natural, clean, and petroleum coke), genetically engineered biofuels and crops and their extracts, and natural gas. Preferably, the additives herein are used in spark-ignition fuels or gasoline. As used herein, "bio-renewable fuel" is understood to mean any fuel derived from resources other than petroleum. Such resources include, but are not limited to, grains, corn, soybeans, and other crops; grasses such as switchgrass, miscanthus, and hybrid grasses; algae, seaweed, vegetable oils; natural fats; and mixtures thereof. In one aspect, the bio-renewable fuel can contain monohydric alcohols, such as those containing from 1 to about 5 carbon atoms. Non-limiting examples of suitable monohydric alcohols include methanol, ethanol, propanol, n-butanol, isobutanol, tert-butanol, pentanol, and isopentanol. Preferred fuels include diesel fuel.

[0105] Accordingly, aspects of the present application relate to the following methods or uses of the fuel additive package for controlling or reducing fuel injector deposits, controlling or reducing intake valve deposits, controlling or reducing combustion chamber deposits, and / or controlling or reducing intake valve sticking in one of an intake port injection engine and a direct injection into cylinder engine (preferably both engine types). In certain aspects, the method may further include mixing at least one of the optional additional components described above into the fuel. Improved engine performance can be evaluated according to the test procedure of ASTM D6201 or by the methods presented in the following two SAE publications: Smith, S. and Imoehl, W., “Measurement and Control of Fuel Injector Deposits in Direct Injection Gasoline Vehicles,” SAE Technical Paper 2013-01-2616, 2013, doi:10.4271 / 2013-01-2616; and / or Shanahan, C., Smith, S. and / or Sears, B., “A General Method for Fouling Injectors in Gasoline Direct Injection Vehicles and the Effects of Deposits on Vehicle Performance,” SAE Int. J. Fuels Lubr. 10(3):2017, doi:10.4271 / 2017-01-2298, which are incorporated herein by reference. The intake valve sticking can be evaluated using the test procedures in Southwest Research Institute (SWRI, San Antonio Texas) or a similar testing agency.

[0106] As used herein, the terms “hydrocarbyl substituent” or “hydrocarbyl group” are used in their ordinary meaning, which is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly connected to the remainder of the molecule and predominantly having hydrocarbon characteristics. Each hydrocarbyl group is independently selected from hydrocarbyl substituents and substituted hydrocarbyl substituents containing one or more halogen groups, hydroxy groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furyl groups, imidazolyl groups, oxygen, and nitrogen, and wherein there are no more than two non-hydrocarbyl substituents for every ten carbon atoms in the hydrocarbyl group.

[0107] As used herein, unless otherwise expressly stated, the term “weight percent” or “wt%” means the percentage by weight of the component in the entire composition. Unless otherwise specified, all percentages herein are weight percentages.

[0108] As used herein, the term "alkyl" refers to straight-chain, branched-chain, cyclic, and / or substituted saturated chain moieties of from about 1 to about 200 carbon atoms. As used herein, the term "alkenyl" refers to straight-chain, branched-chain, cyclic, and / or substituted unsaturated chain moieties of from about 3 to about 30 carbon atoms. As used herein, the term "aryl" refers to monocyclic and polycyclic aromatic compounds, which may include alkyl, alkenyl, alkylaryl, amino, hydroxy, alkoxy, halogen substituents, and / or heteroatoms including, but not limited to, nitrogen and oxygen.

[0109] As used herein, molecular weight is determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (having an Mp of about 162 to about 14,000 as a calibration reference). The molecular weight (Mn) of any embodiment herein can be measured using an instrument such as a gel permeation chromatography (GPC) instrument obtained from Waters, and the data can be processed using software such as Waters Empower software. The GPC instrument can be equipped with a Waters separation module and a Waters refractive index detector (or similar optional equipment). The GPC operating conditions can include a guard column, 4 Agilent PLgel columns (length 300 × 7.5 mm; particle size 5 μm, and pore size range of ), column temperature of about 40 °C. Unstabilized HPLC grade tetrahydrofuran (THF) can be used as the solvent, and the flow rate is 0.38 mL / min. The GPC instrument can be calibrated using commercially available polystyrene (PS) standards having a narrow molecular weight distribution in the range of 500 g / mol to 380,000 g / mol. For samples with a mass less than 500 g / mol, the calibration curve can be extrapolated. The samples and PS standards can be dissolved in THF and prepared at a concentration of 0.1 wt% to 0.5 wt% and used without filtration. GPC measurements are also described in US 5,266,223, which is incorporated herein by reference. The GPC method also provides molecular weight distribution information; see, for example, W.W. Yau, J.J. Kirkland, and D.D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979, which is also incorporated herein by reference.

[0110] It should be understood that throughout this disclosure, the terms "comprising", "including", "containing", etc. are considered to be open-ended and include any elements, steps, or ingredients not explicitly listed. The phrase "consisting essentially of" means including any explicitly listed elements, steps, or ingredients and any additional elements, steps, or ingredients that do not substantially affect the basic and novel aspects of the invention. This disclosure also contemplates that any composition described using the terms "comprising", "including", "containing" is also to be interpreted as including the disclosure of the same composition "consisting essentially of its specifically listed components" or "consisting of its specifically listed components".

[0111] Example

[0112] The following examples are illustrative of the exemplary embodiments of the present disclosure. In these examples and elsewhere in this application, all ratios, parts, and percentages are by weight unless otherwise indicated. These examples are presented for illustrative purposes only and are not intended to limit the scope of the invention disclosed herein. The specifications of the base fuels A, B, and C used in the examples are shown in Table 1 below.

[0113] Table 1: Fuel specifications 。

[0114]

[0115]

[0116] Example 1

[0117] In a 4-liter glass reaction vessel, 1999.98 grams (2.10 moles) of Dovermulse H 1000 polyisobutenyl succinic anhydride (PIBSA prepared using 1000 MW polyisobutene, purchased from Dover Chemical) and 1 drop of silicone fluid (as an antifoaming agent) were mixed and heated to 167 °C under nitrogen protection. Once the mixture reached 167 °C, 307.21 grams (2.10 moles) of 3-(2-(dimethylamino)ethoxy)propylamine (DMAEPA) were added over 11 minutes. Once the DMAEPA was added, a vacuum (26”Hg) was applied to the mixture to remove the water generated during the imide formation process. The mixture was stirred and held at 167 °C under vacuum for 2 hours. The IR spectrum of the product confirmed the formation of a brown viscous liquid polyisobutenyl succinimide (PIBSI).

[0118] In a 4-liter glass reaction vessel, 1600.02 grams (1.48 moles) of PIBSI and 198.00 grams of Solvesso150ND aromatic solvent (purchased from ExxonMobil Chemical) were mixed and heated to 125 °C under nitrogen protection. Subsequently, 183.62 grams (1.55 moles) of dimethyl oxalate were added, and the mixture was maintained at 125 °C for 3 hours with continuous stirring. The 13 13C NMR spectrum of the brown viscous liquid product confirmed the formation of the quaternary ammonium salt. For ease of handling, an additional 566.45 grams of Solvesso150ND were added to bring the mixture to 70 / 30 weight % product / solvent.

[0119] Example 2

[0120] The fuel additive packages of the present invention and comparative fuel additive packages were prepared in base fuel A at the treatment ratios shown in Table 2 below. The Mannich detergent was prepared from highly reactive polyisobutylene cresol, dibutylamine, and formaldehyde according to known methods (see, for example, US6,800,103, which is incorporated herein by reference); the quaternary ammonium salt was from Example 1; the propoxylated alcohol was a commercially available blend of C16-C18 propoxylated alcohols; and the succinimide detergent was a polyisobutenyl mono-succinimide derived from tetraethylenepentamine (TEPA) with a number average molecular weight of 950.

[0121] Table 2: Treatment ratios in base fuel A

[0122]

[0123] The additive packages of Table 2 were blended into base fuel A at the treatment ratios listed in Table 2. Each additive package of Table 2 also contained other non-detergent components such as demulsifiers, corrosion inhibitors, and solvents. Then, the intake valve deposits of the fuel and the improvement relative to the base fuel without additives were evaluated as determined by ASTM D6201.

[0124] Table 3: IVD(ASTM D6201)

[0125]

[0126] As shown in Table 3 above, the samples of the present invention showed the best IVD results compared to the base fuel.

[0127] Example 3

[0128] A series of tests were conducted to evaluate the effect of the additive package of Example 1 at the treatment ratio of Table 2 on fuel injection deposits in a gasoline direct injection (GDI) engine. All tests were conducted with a consistent base fuel C during the contamination (DU), clean (CU), and / or keep clean (KC) phases of the respective tests.

[0129] The DU level of each base fuel was studied by indirectly measuring injector fouling on a 2008 Pontiac Solstice vehicle, such as by pulse width or long-term fuel trim (LTFT), in accordance with the RIFT method as described in Smith, S. and Imoehl, W., “Measurement and Control of Fuel Injector Deposits in Direct Injection Gasoline Vehicles,” SAE Technical Paper 2013-01-2616, 2013, doi:10.4271 / 2013-01-2616; and / or Shanahan, C., Smith, S. and / or Sears, B., “A General Method for Fouling Injectors in Gasoline Direct Injection Vehicles and the Effects of Deposits on Vehicle Performance,” SAE Int. J. Fuels Lubr. 10(3):2017, doi:10.4271 / 2017-01-2298, which is incorporated herein by reference.

[0130] To accelerate the DU phase of the base fuel, a combination of di-tert-butyl disulfide (DTBDS 406 ppmw) and tert-butyl hydroperoxide (TBHP, 286 ppmw) was added to the base fuel, and the DU was accelerated to provide fouling in the range of 5% - 12%.

[0131] The DU program was run between 2000 miles - 3000 miles to achieve a ΔLTFT (Δ = DU end - DU start) of about 6.0% or more. At the end of DU, the fuel was changed to an additive formulation designed to have a cleaning effect. The percentage (%) of CU was calculated as follows:

[0132]

[0133] As Figure 1As generally shown, when using the combination of Mannich and quaternary ammonium salt additives of Example 1 in the sample 1 of the present invention, the cleaning rate is 58.5%, while in the comparative sample 2, the cleaning rate using only Mannich is only 9.3%, and the purification rate using only quaternary ammonium salt is 45.3%. Therefore, the cleaning rate of this combination is synergistically superior to either individual additive.

[0134] Table 4: Cleaning performance

[0135]

[0136] As shown in Table 4 above, the examples of the present invention show improved injector cleaning relative to the comparative examples. Figure 1 Also shown are the LTFTs of Comparative Example 1, Comparative Example 2, and the present invention 1 during the tested contamination and cleaning phases. As Figure 1 and shown in Tables 3 and 4, the fuel additive of the present invention 1 comprising Mannich detergents and quaternary ammonium salts exhibits a synergistic effect not expected for each additive individually.

[0137] It should be noted that, unless explicitly and affirmatively limited to one indicator, as used in this specification and the appended claims, the singular forms "a" and "the" include plural indicators. Thus, for example, reference to "an antioxidant" includes two or more different antioxidants. The term "comprising" and its grammatical variants as used herein are intended to be non - restrictive, such that the recitation of items in a list does not exclude other similar items that may be substituted or added to the listed items.

[0138] For this specification and the appended claims, unless otherwise indicated, all numbers and other numerical values representing quantities, percentages, or ratios used in the specification and claims should be understood to be modified in all instances by the term "about". Thus, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties sought to be obtained by this disclosure. At a minimum, and without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in accordance with the number of significant digits reported and by applying ordinary rounding techniques.

[0139] It should be understood that each component, compound, substituent, or parameter disclosed herein should be construed as being disclosed for use individually or in combination with one or more of each of the other components, compounds, substituents, or parameters disclosed herein.

[0140] It should be further understood that each range disclosed herein should be construed as an explicit disclosure of each specific value within the disclosed range having the same numerical value of significant digits. Thus, for example, a range of 1 to 4 should be construed as an explicit disclosure of the values 1, 2, 3, and 4 and any range of such values.

[0141] It should be further understood that each lower limit of each range disclosed herein should be construed as being disclosed in combination with each upper limit of each range and each specific value within each range for the same component, compound, substituent, or parameter disclosed herein. Thus, the present disclosure should be construed as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is to say, it should be further understood that any range between the endpoint values within a broad range is also discussed herein. Thus, a range of 1 to 4 also means ranges of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0142] In addition, a specific amount / value of a component, compound, substituent, or parameter disclosed in this specification or in the examples should be construed as a disclosure of a lower limit or an upper limit of a certain range, and thus can be combined with any other lower limit or upper limit or specific amount / value of a range of the same component, compound, substituent, or parameter disclosed elsewhere in the present disclosure to form a range of that component, compound, substituent, or parameter.

Claims

1. A fuel additive package for a spark ignition engine, the fuel additive package comprising: A Mannich detergent comprising a reaction product of a hydrocarbyl-substituted phenol, one or more aldehydes, and one or more amines, wherein the Mannich detergent has a structure of Formula I: wherein R1 is hydrogen or C1 to C4 alkyl, R2 is a hydrocarbon group having a number average molecular weight of 500 to 3000, R3 is a C1 to C4 alkylene or alkenyl group, and R4 and R5 are independently hydrogen, C1 to C12 alkyl or C1 to C4 alkylamino C1-C12 alkyl; A quaternary ammonium salt additive having a structure of formula II wherein each X is selected from -O-, -N(R 12 )-, -C(O)-, -C(O)O- or -C(O)NR 12 Each R7, R8 and R9 is independently an alkyl group containing 1 to 8 carbon atoms; R 10 and R 11 R is independently selected from hydrogen, alkyl, acyl or alkyl-substituted acyl, 10 and R 11 One or both of the hydrocarbyl substituents have a number average molecular weight of 700 or greater; R 12 are independently hydrogen or selected from C 1-6 an aliphatic, phenyl or alkylphenyl group; each m is independently an integer of 0 or 1, wherein at least one m is 1; each n is independently an integer of 1 to 10; and is a carboxylate; An alkoxylated alcohol, wherein the weight ratio of the alkoxylated alcohol to the Mannich detergent is 0.8 or less, wherein the alkoxylated alcohol is a polyether having a structure of Formula Va: wherein R6 is an aryl group or a linear, branched or cyclic aliphatic group having 5 to 50 carbons, R7 is a C1 to C4 alkyl group, and n is an integer from 5 to 100; wherein the weight ratio of the Mannich detergent to the quaternary ammonium salt additive is 4:1 to 10:1; and The fuel additive package comprises 20 wt % to 70 wt % of the Mannich detergent, 1 wt % to 20 wt % of the quaternary ammonium salt additive, and 5 wt % to 30 wt % of the alkoxylated alcohol.

2. The fuel additive package of claim 1, wherein the alkoxylated alcohol is a polyether prepared by reacting an alkyl alcohol or an alkyl phenol with an alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide, copolymers thereof, or combinations thereof.

3. The fuel additive package according to claim 1, wherein R of the quaternary ammonium salt of formula II 10 and R 11 Together with the nitrogen atom to which they are attached they form part of a ring.

4. The fuel additive package of claim 1, wherein the carboxylate of the quaternary ammonium salt of Formula II is oxalate, salicylate, or a combination thereof.

5. The fuel additive package according to claim 4, wherein X of formula II is -O- or -NH-.

6. The fuel additive package of claim 5, wherein the quaternary ammonium salt is derived from 3-(2-(dimethylamino)ethoxy)propylamine, N,N-dimethyldipropylenetriamine, or mixtures thereof.

7. The fuel additive package of claim 1, wherein R of the quaternary ammonium salt of formula II 10 and R 11 Together with the nitrogen atom to which they are attached, they combine to form a hydrocarbyl-substituted succinimide.

8. The fuel additive package of claim 7, wherein the hydrocarbyl substituent has a number average molecular weight of 700 to 2,500.

9. The fuel additive package of claim 1, wherein the X portion of the quaternary ammonium salt of Formula II is an oxygen atom, and wherein R 10 and R 11 Together with the nitrogen atom to which they are attached, they combine to form a hydrocarbyl-substituted succinimide, wherein the hydrocarbyl substituent has a number average molecular weight of 700 to 1,500 as measured by GPC using polystyrene as a calibration reference.

10. The fuel additive package of claim 1, wherein the fuel additive package comprises 20 wt% to 60 wt% of the Mannich detergent.

11. The fuel additive package of claim 1 further comprising a succinimide detergent prepared by reacting a hydrocarbyl-substituted succinic acylating agent with an amine, polyamine or alkylamine having one or more primary, secondary or tertiary amino groups.

12. The fuel additive package of claim 11, wherein the fuel additive package comprises 0.1 wt% to 10 wt% of the succinimide detergent.

13. The fuel additive package of claim 12, wherein the succinimide detergent is a hydrocarbyl-substituted monosuccinimide detergent, a hydrocarbyl-substituted bissuccinimide detergent, or a combination thereof.

14. The fuel additive package of claim 12, further comprising one or more of a demulsifier, a corrosion inhibitor, an anti-wear additive, an antioxidant, a metal deactivator, an antistatic additive, an anti-fogging agent, an anti-knock additive, a lubricity additive, and / or a combustion improver.

15. A gasoline fuel composition, comprising: 55 ppmw to 125 ppmw of a Mannich detergent, the Mannich detergent comprising the reaction product of a hydrocarbyl-substituted phenol, one or more aldehydes, and one or more amines, wherein the Mannich detergent has the structure of Formula I: wherein R1 is hydrogen or C1 to C4 alkyl, R2 is a hydrocarbon group having a number average molecular weight of 500 to 3000, R3 is a C1 to C4 alkylene or alkenyl group, and R4 and R5 are independently hydrogen, C1 to C12 alkyl or C1 to C4 alkylamino C1-C12 alkyl; 4 ppmw to 15 ppmw of a quaternary ammonium salt additive having a structure of Formula II wherein each X is selected from -O-, -N(R 12 )-, -C(O)-, -C(O)O- or -C(O)NR 12 Each R7, R8 and R9 is independently an alkyl group containing 1 to 8 carbon atoms; R 10 and R 11 R is independently selected from hydrogen, alkyl, acyl or alkyl-substituted acyl, 10 and R 11 One or both of the hydrocarbyl substituents have a number average molecular weight of 700 or greater; R 12 are independently hydrogen or selected from C 1-6 an aliphatic, phenyl or alkylphenyl group; each m is independently an integer of 0 or 1, wherein at least one m is 1; each n is independently an integer of 1 to 10; and is a carboxylate; and 15 ppmw to 40 ppmw of an alkoxylated alcohol, wherein the weight ratio of the alkoxylated alcohol to the Mannich detergent is 0.8 or less, wherein the alkoxylated alcohol is a polyether having a structure of Formula Va: wherein R6 is an aryl group or a linear, branched or cyclic aliphatic group having 5 to 50 carbons, R7 is a C1 to C4 alkyl group, and n is an integer from 5 to 100; and The weight ratio of the Mannich detergent to the quaternary ammonium salt additive is 4:1 to 10:

1.

16. A method for improving injector performance of a GDI engine, the method comprising: operating the direct injection engine with a fuel composition comprising gasoline fuel and 40 ppmw to 750 ppmw of the fuel additive package according to claim 1; and wherein the fuel additive package in the gasoline fuel improves the injector performance of the direct injection engine, Wherein the improved injector performance is one of improved fuel flow, improved fuel economy, improved engine efficiency, or a combination thereof. 17 . The method of claim 16 , wherein the improved injector performance is measured by one of injector pulse width, injection duration, injector flow, or a combination thereof.

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