KR20240046009A - Gasoline additive composition for improved engine performance - Google Patents

Abstract

The present disclosure provides fuel additives comprising Mannich detergent additive(s) and succinimide detergent additive(s) that are effective in improving engine performance in both port fuel injection and gasoline direct injection engines.

Description

Gasoline additive composition for improved engine performance {GASOLINE ADDITIVE COMPOSITION FOR IMPROVED ENGINE PERFORMANCE}

The present disclosure relates to fuel additives for spark ignition engines that provide improved engine, intake valve, and/or injector performance, fuel compositions containing such additives, and methods of using such fuel additives in fuel compositions for improved performance. will be.

Automotive fuel compositions are continually being improved to improve various properties of the fuel to accommodate its use in newer, more advanced engines, including both gasoline port fuel injection engines as well as gasoline direct injection engines. Often, improvements in fuel composition focus on improved fuel additives and other components used in the fuel. For example, friction modifiers may be added to fuel to reduce friction and wear in an engine's fuel delivery system. Other additives may be included to reduce the corrosion potential of the fuel or improve its conductive properties. Additional additives may be blended with the fuel to improve fuel efficiency. Engine and Fuel Delivery System Deposits represent another concern in modern combustion engines, so other fuel additives often include various deposit control additives to control and/or alleviate engine deposit problems. Accordingly, fuel compositions typically include complex mixtures of additives.

However, challenges remain when attempting to balance this complex class of additives. For example, some of the conventional fuel additives may be beneficial to one characteristic or type of engine, but at the same time may be detrimental to other characteristics of the fuel. In some cases, fuel additives that are effective in a gasoline port fuel injection engine (PFI) do not necessarily provide comparable performance in a gasoline direct injection engine (GDI) and vice versa. In another situation, fuel additives often require unreasonably high processing rates to achieve the desired effect, which tends to place undesirable limits on the available amounts of other additives in the fuel composition. Still other fuel additives tend to be expensive and/or difficult to manufacture or incorporate into fuel.

In one embodiment or approach, a fuel additive or fuel additive package for a spark ignition engine described herein comprises the reaction of a hydrocarbyl substituted phenol or cresol, one or more aldehydes, and one or more amines to provide improved engine performance. Mannich detergent containing the product; Succinimide detergents prepared by reacting a hydrocarbyl substituted succinic acid acylating agent with an amine, polyamine, or alkyl amine having one or more primary, secondary, or tertiary amino groups; and the weight ratio of Mannich detergent to succinimide detergent is from about 15:1 to about 30:1. As discussed further herein, this weight ratio provides a synergistic effect with improved engine and/or injector performance in both port fuel injection (PFI) engines as well as gasoline direct injection (GDI) engines.

In other embodiments or approaches, the fuel additives of the previous paragraph may include one or more optional features or embodiments in any combination. Optional features or embodiments may include one or more of the following: the weight ratio of Mannich detergent to succinimide detergent is from about 20:1 to about 30:1; Mannich detergents have the structure of formula I:

wherein R ₁ of formula I is hydrogen or a C1 to C4 alkyl group, R ₂ of formula I is a hydrocarbyl group with a molecular weight of about 500 to about 3000, and R ₃ of formula I is a C1 to C4 alkylene or alkenyl group. group (preferably a C1 group), and R ₄ and R ₅ of formula I are independently hydrogen, a linear or branched C1 to C12 alkyl group, or a mono or di(C1 to C4)alkyl amino C1-C12 alkyl group. /or; R ₂ of Formula I is polyisobutenyl having a number average molecular weight of about 500 to about 1500; The succinimide detergent is a hydrocarbyl substituted mono-succinimide detergent, a hydrocarbyl substituted bis-succinimide detergent, or a combination thereof; The hydrocarbyl substituted succinic acid acylating agent is a hydrocarbyl substituted succinic anhydride, wherein the hydrocarbyl groups have a molecular weight of about 450 to about 3000, and the molar ratio of hydrocarbyl substituted succinic anhydride to amine, polyamine or alkyl amine is about 0.5. :1 to about 2:1 and/or; The hydrocarbyl substituted succinic anhydride is a polyisobutylene substituted succinic anhydride, the polyisobutylene having a number average molecular weight of about 500 to about 1200 as determined by GPC using polystyrene as a reference; The amine, polyamine, or alkyl amine is tetraethylene pentamine (TEPA), triethylenetetraamine (TETA), or a polyamine having the formula H ₂ N-((CHR ₂₀ -(CH ₂ ) _q -NH) _r -H or alkyl amines (wherein R ₂₀ 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/or mixtures thereof; amines, The polyamine or alkyl amine is tetraethylene pentamine (TEPA); and/or the fuel additive further comprises an alkoxylated alcohol, and the weight ratio of alkoxylated alcohol to Mannich detergent is about 1.0 or less (preferably 0.8 or less, 0.6 or less, or 0.5 or less) and/or the alkoxylated alcohol is a polyether prepared by reacting an alkyl alcohol or alkylphenol with an alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide, copolymers thereof, or combinations thereof. and/or the alkoxylated alcohol is a polyether having the structure III:

wherein R ₆ of formula III is an aryl group or a linear, branched or cyclic aliphatic group having 5 to 50 carbons, R ₇ of formula III is a C1 to C4 alkyl group and n is an integer from 5 to 100 and/or ; The fuel additive includes about 20 to about 60 weight percent Mannich detergent, about 0.5 to about 10 weight percent succinimide detergent, and about 5 to about 30 weight percent alkoxylated alcohol.

In another approach or embodiment, described herein are gasoline fuel compositions that provide improved engine and/or injector performance in both port fuel injection (PFI) engines as well as gasoline direct injection (GDI) engines. The gasoline fuel composition may comprise from about 15 to about 300 ppmw of a Mannich detergent comprising the reaction product of a hydrocarbyl substituted phenol or cresol, one or more aldehydes, and one or more amines; about 0.5 to about 20 ppmw of a succinimide detergent prepared by reacting a hydrocarbyl substituted succinic acid acylating agent with an amine, polyamine, or alkyl amine having one or more primary, secondary, or tertiary amino groups; and about 5 to about 150 ppmw of an alkoxylated alcohol; wherein the weight ratio of Mannich detergent to succinimide detergent is from about 15:1 to about 30:1. In a further embodiment, the gasoline fuel composition may also include any optional features or embodiments as described above with respect to fuel additives.

In another approach or embodiment, described herein is a method of reducing deposits in gasoline engines. The method includes operating a gasoline engine with a fuel composition containing a large amount of gasoline fuel and a small amount of fuel additives by injecting the gasoline fuel through one or more injectors; wherein the fuel additive is (i) a Mannich detergent comprising the reaction product of a hydrocarbyl substituted phenol or cresol, one or more aldehydes, and one or more amines; (ii) succinimide detergents prepared by reacting a hydrocarbyl substituted succinic acid acylating agent with an amine, polyamine, or alkyl amine having one or more primary, secondary, or tertiary amino groups; (iii) wherein the fuel additive is a weight ratio of Mannich detergent to succinimide detergent of about 15:1 to about 30:1; And fuel additives reduce deposits in gasoline engines.

In other embodiments or approaches, the methods described in the preceding paragraphs may include one or more optional features, method steps, or embodiments in any combination. Optional features, steps, or embodiments may include one or more of the following: the fuel additive reduces deposits in port fuel injection (PFI) engines, gasoline direct injection (GDI) engines, or both; or order; Reduced deposits are reduced injector deposits as measured by one of injector pulse width, injector duration, injector flow, or a combination thereof; The fuel additive reduces deposits when sprayed from an injector configured to spray droplets of about 10 to about 30 microns, about 120 to about 200 microns, or both; The weight ratio of Mannich detergent to succinimide detergent is from about 20:1 to about 30:1; Mannich detergent has the structure of formula I,

wherein one of R ₁ and R ₂ of formula I is hydrogen or a C1 to C4 alkyl group, the other of R ₁ and R ₂ is a hydrocarbyl group with a molecular weight of about 500 to about 3000, and R ₃ of formula I is is a C1 to C4 alkylene or alkenyl group, and R ₄ and R ₅ of formula I are independently hydrogen, a C1 to C12 alkyl group, or a mono or di(C1 to C4)alkyl amino C1-C12 alkyl group; R ₂ of Formula I is polyisobutenyl having a number average molecular weight of about 500 to about 1500; The succinimide detergent is a hydrocarbyl substituted mono-succinimide detergent, a hydrocarbyl substituted bis-succinimide detergent, or a combination thereof; The hydrocarbyl substituted succinic acid acylating agent is a hydrocarbyl substituted succinic anhydride, wherein the hydrocarbyl groups have a molecular weight of about 450 to about 3000, and the molar ratio of hydrocarbyl substituted succinic anhydride to amine, polyamine or alkyl amine is about 0.5. :1 to about 2:1 and/or; The hydrocarbyl substituted succinic anhydride is a polyisobutylene substituted succinic anhydride, the polyisobutylene having a number average molecular weight of about 500 to about 1200 as determined by GPC using polystyrene as a reference; The amine, polyamine, or alkyl amine is tetraethylene pentamine (TEPA), triethylenetetraamine (TETA), or a polyamine having the formula H ₂ N-((CHR ₂₀ -(CH ₂ ) _q -NH) _r -H or alkyl amines (wherein R ₂₀ 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/or mixtures thereof; amines, The polyamine or alkyl amine is tetraethylene pentamine (TEPA); The fuel additive further comprises an alkoxylated alcohol, and the weight ratio of alkoxylated alcohol to Mannich detergent is less than or equal to about 1.0; The alkoxylated alcohol is an alkyl alcohol. or is a polyether prepared by reacting an alkylphenol with an alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide, copolymers thereof, or combinations thereof; the alkoxylated alcohol has the structure of formula (III) It is polyether and:

wherein R ₆ of formula III is an aryl group or a linear, branched or cyclic aliphatic group having 5 to 50 carbons, R ₇ of formula III is a C1 to C4 alkyl group and n is an integer from 5 to 100 and/or ; The fuel additive includes about 20 to about 60 weight percent Mannich detergent, about 0.5 to about 10 weight percent succinimide detergent, and about 5 to about 30 weight percent alkoxylated alcohol.

In another approach or embodiment, a method as described by any of the embodiments herein is used to improve injector performance of port fuel injection (PFI) engines, gasoline direct injection (GDI) engines, or both PFI and GDI engines. Use of a fuel additive package or use of gasoline fuel as described by any embodiment of the fuel composition herein.

In any embodiment of the fuel additive package, fuel, method or use herein, the fuel additive package of the present disclosure may be free of quaternary ammonium salt detergents and preferably may contain any free anionic species obtained from amines or polyamines. There may be substantially no quaternary ammonium internal salt detergent. In this context, none means less than 0.5 ppmw, less than 0.1 ppmw, less than 0.05 ppmw, or preferably none at all.

1 is a graph showing GDI dirty-up (DU) and clean-up (CU) of fuel additives of comparative examples and the present invention.
2 is a graph showing GDI dirty-up (DU) and clean-up (CU) of fuel additives of comparative examples and the present invention.

The present disclosure discloses Mannich detergent(s) and succinic agents found to be effective at certain weight ratios to provide improved engine and/or injector performance in both port fuel injection (PFI) engines as well as gasoline direct injection (GDI) engines. A fuel additive comprising a combination of mead detergent(s) is provided. In some approaches, the fuel additive may also include an alkoxylated alcohol and, if so, a specific ratio of alkoxylated alcohol to Mannich detergent. Also provided herein are fuel compositions comprising the novel fuel additive combinations and methods of using or burning fuels comprising the fuel additive combinations to achieve improved engine, intake valve, and/or injector performance. do. As further noted below, the fuel additives herein have the Mannich detergent(s) and succinimide detergent(s) when used in a weight ratio of Mannich detergent to succinimide detergent(s) of about 15:1 to about 30:1. ) includes a synergistic combination of Mannich cleaner alone does not provide any clean-up performance in GDI engines, but surprisingly, improved clean-up is achieved when combined with succinimide cleaner in certain ratios.

In aspects or embodiments of the present disclosure, improved engine, intake valve, and/or injector performance of the fuel additive combinations herein includes 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 a PFI engine, a GDI engine, or both types of engines. Improved injector performance may also be one or more of improved fuel flow, improved fuel economy, and/or improved engine efficiency as determined through one or more of injector pulse width, injection duration, and/or injector flow.

Mannich Cleanser

In one aspect, the fuel additives and fuels herein first include one or more Mannich detergent(s). Suitable Mannich detergents include the reaction product(s) of alkyl substituted hydroxyaromatic or phenolic compounds, aldehydes, and amines, as discussed further below.

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

Alkylation of hydroxyaromatic or phenolic compounds is typically carried out in the presence of an alkylation catalyst at temperatures ranging from about 0 to about 200° C., preferably from 0 to about 100° C. Acidic catalysts are commonly used to catalyze Friedel-Crafts alkylation. Typical catalysts used in commercial production include sulfuric acid, BF ₃ , aluminum phenoxide, methanesulfonic acid, cationic exchange resins, acidic clays and modified zeolites.

Polyolefins suitable for forming the alkyl substituted hydroxyaromatic compounds of Mannich cleaners include polypropylene, polybutene, polyisobutylene, butylene and/or copolymers of butylene and propylene, butylene and/or isobutylene. and/or propylene and one or more mono-olefin comonomers copolymerizable therewith (e.g., ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene, etc.), wherein the copolymer The molecule contains at least 50% by weight of butylene and/or isobutylene and/or propylene units. Any comonomer polymerized with propylene or butene may be aliphatic and, if desired, may also contain non-aliphatic groups such as styrene, o-methylstyrene, p-methylstyrene, divinyl benzene, etc. Accordingly, the resulting polymers and copolymers used to form alkyl substituted hydroxyaromatic compounds are substantially aliphatic hydrocarbon polymers.

Polybutylene is preferred herein to form hydrocarbyl substituted hydroxyaromatic or phenolic compounds. Unless otherwise specified herein, the term “polybutylene” refers to a polymer prepared from “pure” or “substantially pure” 1-butene or isobutene, and two of 1-butene, 2-butene and isobutene or It is used in the general sense to include polymers prepared from mixtures of all three. Commercial grades of these polymers may also contain trace amounts of other olefins. So-called highly reactive polyisobutenes, which have a relatively high proportion of polymer molecules bearing terminal vinylidene groups, are also suitable for use in forming long-chain alkylated phenol reactants. Suitable highly reactive polyisobutenes include polyisobutenes containing at least about 20%, preferably at least 50%, and more preferably at least 70% of the more reactive methylvinylidene isomer. Suitable polyisobutenes include those made using a BF ₃ catalyst. The preparation of such polyisobutenes in which methylvinylidene isomers constitute 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.

In some approaches or embodiments, Mannich detergents can be prepared from alkylphenols or alkylcresols. However, other phenolic compounds may be used, including alkyl substituted derivatives of resorcinol, hydroquinone, catechol, hydroxydiphenyl, benzylphenol, phenethylphenol, naphthol, tolylnaphthol, among others. Preferred for the preparation of Mannich cleaners are polyalkylphenol and polyalkylcresol reactants, such as polypropyl phenol, polybutylphenol, polypropylcresol and polybutylcresol, wherein the alkyl groups are determined by GPC using polystyrene as reference. While the most preferred alkyl groups have a number average molecular weight ranging from about 500 to about 3000 or from about 500 to about 2100, the most preferred alkyl groups are from polyisobutylene having a number average molecular weight ranging from about 700 to about 1300 as determined by GPC using polystyrene as a reference. It is a derived polybutyl group.

A preferred configuration of alkyl substituted hydroxyaromatic compounds is that of para substituted mono-alkylphenol or para substituted mono-alkyl ortho-cresol. However, any hydroxyaromatic compound that reacts readily in the Mannich condensation reaction may be employed. Accordingly, Mannich products prepared from hydroxyaromatic compounds having only one ring alkyl substituent, or two or more ring alkyl substituents, are suitable for forming these detergent additives. Alkyl substituents are generally substantially saturated alkyl groups, although they may contain some residual unsaturation.

In an approach or embodiment, representative amine reactants suitable to form 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 polyethylene polyamine. Suitable alkylene polyamine reactants include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine and those having a nitrogen content corresponding to the alkylene polyamines of the formula H ₂ N--(A-NH--) _n H and mixtures of such amines, where A is dihydric ethylene or propylene and n is an integer from 1 to 10, preferably from 1 to 4. Alkylene polyamines can be obtained by reaction of ammonia with dihalo alkanes, such as dichloro alkanes.

The amine may 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 are N,N,N",N"-tetraalkyldialkylenetriamine (two terminal tertiary amino groups and one central secondary amino group), N,N,N',N"- Tetraalkyltrialkylene tetramine (1 terminal tertiary amino group, 2 internal tertiary amino groups and 1 terminal primary amino group), N,N,N',N",N'"-pentaalkyltri Alkylenetetramine (1 terminal tertiary amino group, 2 internal tertiary amino groups and 1 terminal secondary amino group), N,N'-dialkylamine, N,N-dihydroxyalkyl-alpha- , omega-alkylenediamine (one terminal tertiary amino group and one terminal primary amino group), N,N,N'-trihydroxyalkyl-alpha, omega-alkylenediamine (one terminal tertiary amino group) groups and one terminal secondary amino group), tris(dialkylaminoalkyl) aminoalkylmethane (three terminal tertiary amino groups and one terminal primary amino group), and similar compounds, wherein the alkyl groups are the same. or different and typically contain up to about 12 carbon atoms each, preferably 1 to 4 carbon atoms each. Most preferably these alkyl groups are methyl and/or ethyl groups. Preferred polyamine reactants are N,N-dialkyl-alpha, omega-alkylene diamines, 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, the alkyl groups being most preferred. They may be identical but different.Exemplary amines may include N,N-dimethyl-1,3-propanediamine and/or N-methyl piperazine.

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 participate directly in the Mannich condensation reaction to any significant extent are N-( tert -Butyl)-1,3-propanediamine, N-neopentyl-1,3-propane diamine-, N-( tert -butyl)-1-methyl-1,2-ethanediamine, N-( tert -butyl) -1-methyl-1,3-propane diamine, and 3,5-di( tert -butyl)aminoethylpiperazine.

In an approach or embodiment, representative aldehydes for use in the preparation of Mannich cleaners herein include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, stearaldehyde. do. Aromatic aldehydes that can be used include benzaldehyde and salicylaldehyde. Exemplary heterocyclic aldehydes for use herein include furfural and thiophene aldehydes. Formaldehyde generating reagents such as paraformaldehyde, or aqueous formaldehyde solutions such as formalin are also useful. Most preferred is formaldehyde or formalin.

Condensation reactions between alkylphenols, certain amine(s) and aldehydes can typically be carried out at temperatures ranging from 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. During the reaction process, water can be released and removed by azeotropic distillation. Typically, 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 to 2.0:1.0 to 3.0, respectively. Suitable Mannich base detergents include those described in US Pat. No. 4,231,759; US 5,514,190; US 5,634,951; US 5,697,988; US 5,725,612; and detergents taught in 5,876,468, the disclosures of which are incorporated herein by reference.

In another approach or embodiment, a Mannich detergent suitable for the fuel additives herein may have the structure of Formula I below:

wherein one of R ₁ and R ₂ of formula I is hydrogen or a C1 to C4 alkyl group, the other of R ₁ and R ₂ is a hydrocarbyl group having a molecular weight of about 500 to about 3000, and R ₃ of formula I is is a C1 to C4 alkylene or alkenyl linking group, and R ₄ and R ₅ of formula I are independently hydrogen, a C1 to C12 alkyl group, or a mono or di(C1 to C4)alkyl amino C1-C12 alkyl group. In one embodiment, R ₁ of Formula I is hydrogen or a C1 to C4 alkyl group, and R ₂ of Formula I has a molecular weight of about 500 to about 3000 (or about 500 to about 2100, or about 500 to about 1800, or about 500 to about 1500) is a hydrocarbyl group. In another embodiment, R ₁ of Formula I is hydrogen or a C1 to C4 alkyl group and R ₂ of Formula I is a polyisobutenyl group having a number average molecular weight of about 500 to about 1500.

The fuel additive or additive package may contain from about 20 to about 60 weight percent of the Mannich detergent described above, from about 25 to about 50 weight percent of the Mannich detergent, or from about 30 to about 45 weight percent of the Mannich detergent (the active only of the fuel additives). (based on the total weight of the Nihi detergent). When blended into a gasoline fuel, the fuel composition may comprise from about 15 ppmw to about 300 ppmw of the Mannich detergent described above, from about 25 ppmw to about 155 ppmw, or from about 55 ppmw to about 125 ppmw of the Mannich detergent. (active Mannich detergent treatment rate). In some embodiments, the fuel additive herein includes a single type of Mannich detergent.

Succinimide detergent

The fuel additive or fuel herein may also comprise one or more hydrocarbyl substituted dicarboxylic acid anhydride derivatives, and preferably one or more hydrocarbyl substituted succinimide detergents. In one approach, this additive can be prepared by reacting a hydrocarbyl substituted succinic acid acylating agent with an amine, polyamine, or alkyl amine bearing one or more primary, secondary, or tertiary amino groups. In some embodiments, hydrocarbyl substituted dicarboxylic acid anhydride derivatives include hydrocarbyl succinimide, succinamide, succinimide-amide, and succinimide-ester. Nitrogen-containing derivatives of these hydrocarbyl succinic acid acylating agents can be prepared by reacting a hydrocarbyl substituted succinic acid acylating agent with an amine, polyamine, or alkyl amine bearing one or more primary, secondary, or tertiary amino groups. The succinimide detergent may be mono-succinimide, bis-succinimide, or a combination thereof.

In some approaches or embodiments, the hydrocarbyl substituted dicarboxylic acid anhydride derivative may comprise a hydrocarbyl substituent having a molecular weight or number average molecular weight in the range of about 450 to about 3000 as determined by GPC using polystyrene as a reference. You can. Derivatives may be selected from diamides, acids/amides, acids/esters, diacids, amides/esters, diesters, and imides. These derivatives can be prepared by reacting a hydrocarbyl substituted dicarboxylic acid anhydride with ammonia, polyamines, or alkyl amines bearing one or more primary, secondary, or tertiary amino groups. In some embodiments, the polyamine or alkyl amine can be an amine such as tetraethylene pentamine (TEPA), triethylenetetramine (TETA), etc. In another approach, polyamines or alkyl amines have the formula H ₂ N-((CHR ₂₀ -(CH ₂ ) _q -NH) _r -H where R ₂₀ is hydrogen or an alkyl group with 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 another approach, a hydrocarbyl substituted dicarboxylic acid anhydride and its reacted ammonia, polyamine, or The molar ratio of alkyl amines may be from about 0.5:1 to about 2:1, in other approaches from about 1:1 to about 2:1, or in other approaches from about 1:1 to about 1.6:1.

In another approach, the hydrocarbyl substituted dicarboxylic acid anhydride can be a hydrocarbyl carbonyl compound of formula IV,

R ₁₀ of formula IV in the formula is a hydrocarbyl group derived from polyolefin. In some embodiments, the hydrocarbyl carbonyl compound may be a polyalkylene succinic anhydride reactant, where R _{10 is a polyalkylene succinic anhydride reactant, wherein R 10} has a number average molecular weight of from about 450 to about 3000, as determined by GPC using, for example, polystyrene as a reference. It is a hydrocarbyl moiety, such as an alkenyl radical. For example, the number average molecular weight of R ₁₀ may range from about 600 to about 2500, or from about 700 to about 1500, or from about 850 to about 1000, as measured by GPC using polystyrene as a reference. Particularly useful R ₁₀ of formula IV have a number average molecular weight of about 900 to about 1000 daltons (as determined by GPC using polystyrene as reference) and include polyisobutylene. Molecular weights herein, unless otherwise indicated, are number average molecular weights measured by GPC using polystyrene as a reference.

The R ₁₀ hydrocarbyl moiety of formula IV may comprise one or more polymer units selected from linear or branched alkenyl units. In some embodiments, alkenyl units can have from about 2 to about 10 carbon atoms. For example, the polyalkenyl radical may comprise one or more linear or branched polymer units selected from ethylene radicals, propylene radicals, butylene radicals, pentene radicals, hexene radicals, octene radicals and decene radicals. In some embodiments, the R ₁₀ polyalkenyl radical may be in the form of, for example, a homopolymer, copolymer, or terpolymer. In one aspect, the polyalkenyl radical is isobutylene. For example, the polyalkenyl radical can be a homopolymer of polyisobutylene comprising from about 10 to about 60 isobutylene groups, such as from about 20 to about 30 isobutylene groups. The polyalkenyl compound used to form the R ₁₀ polyalkenyl radical may be formed by any suitable method, such as conventional catalytic oligomerization of alkenes.

In some embodiments, highly reactive polyisobutenes with a relatively high proportion of polymer molecules having terminal vinylidene groups may be used to form the R ₁₀ groups. In one example, at least about 60%, such as about 70% to about 90%, of the polyisobutene comprises terminal olefinic double bonds. Highly reactive polyisobutenes are disclosed, for example, in US 4,152,499, the disclosure of which is incorporated herein by reference in its entirety.

In some embodiments, approximately 1 mole of maleic anhydride per mole of polyalkylene may be reacted, such that the resulting polyalkenyl succinic anhydride has from about 0.8 to about 1 succinic anhydride group per polyalkylene substituent. In other embodiments, the molar ratio of succinic anhydride groups to polyalkylene groups may range from about 0.5 to about 3.5, such as from about 1 to about 1.1.

Hydrocarbyl carbonyl compounds can be prepared using any suitable method. One example of a method to form a hydrocarbyl carbonyl compound involves blending a polyolefin and maleic anhydride. The polyolefin and maleic anhydride reactants are heated to a temperature, for example, from about 150° C. to about 250° C., optionally using a catalyst such as chlorine or peroxide. Another exemplary process for preparing polyalkylene succinic anhydride is described in US 4,234,435, which is incorporated herein by reference in its entirety.

In hydrocarbyl substituted dicarboxylic anhydride derivatives, the polyamine reactant may be an alkylene polyamine. For example, the polyamine may be selected from ethylene polyamine, propylene polyamine, butylene polyamine, etc. In one approach, the polyamines are ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and N,N'-(iminodi-2,1,ethanediyl)bis-1 It is an ethylene polyamine that can be selected from ,3-propanediamine. Particularly useful ethylene polyamines are compounds of the formula H ₂ N—((CHR ₁ —(CH ₂ ) _q —NH) _r —H, wherein R ₁ is hydrogen, q is 1, and r is 4.

In another approach, the hydrocarbyl substituted dicarboxylic anhydride derivative is a compound of formula V,

wherein R ₁₀ of Formula V is a hydrocarbyl group (such as polyisobutylene and/or other R ₁₀ moieties described above) and R ₁₁ of Formula V is hydrogen, an alkyl group, an aryl group, -OH, -NHR ₁₂ , or A polyamine, or an alkyl group containing one or more primary, secondary, or tertiary amino groups. In some approaches, R ₁₁ of Formula V is selected from ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylene pentamine, pentaethylene hexamine, N,N'-(iminodi-2,1,ethanediyl)bis. -Derived from 1,3-propanediamine and combinations thereof. In some embodiments, R ₁₀ of Formula V is a hydrocarbyl group and R ₁₁ is hydrogen, an alkyl group, an aryl group, -OH, -NHR ₁₂ , or a polyamine, wherein R ₁₂ is hydrogen or an alkyl group. In another embodiment, the additive of Formula V is ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylene pentamine, pentaethylene hexamine, N,N'-(iminodi-2,1,ethanediyl)bis. -hydrocarbyl substituted succinimides derived from -1,3-propanediamine and combinations thereof. In another embodiment, R ₁₀ in the compounds of Formula V is a hydrocarbyl group having a number average molecular weight of about 450 to about 3,000, and R ₁₁ is derived from tetraethylene pentamine and derivatives thereof.

In another approach, R ₁₁ is a radical of formula VI,

where A is NR ₁₂ or an oxygen atom, R ₁₂ , R ₁₃ , and R ₁₄ of Formula VI are independently hydrogen atoms or alkyl groups, and m and p are integers from 2 to 8; n is an integer from 0 to 4. In some approaches, R ₁₃ and R ₁₄ of Formula VI together with the nitrogen atom to which they are attached form a 5-membered ring.

In an approach or embodiment, the succinimide detergent herein is a hydrocarbyl substituted mono-succinimide detergent, a hydrocarbyl substituted bis-succinimide detergent, or a combination thereof. In one approach or embodiment, the succinimide detergent may be derived from polyisobutylene succinic anhydride and amine in a 1:1 to 1:6 molar ratio.

The fuel additive or fuel herein may contain from about 0.5 to about 10 weight percent of an active succinimide detergent, from about 0.5 to about 8 weight percent of a succinimide detergent, or from about 1 to about 5 weight percent of a succinimide detergent (fuel additive (based on the total weight of the active succinimide detergent). When blended into gasoline fuel, the fuel may contain from about 0.5 ppmw to about 20 ppmw of active succinimide detergent, from about 1 ppmw to about 10 ppmw, or from about 2 ppmw to about 5 ppmw (based on the total weight of active succinimide). ppmw of succinimide detergent may be included in the fuel.

As discussed further below, the fuel additives and fuels herein include selected weight ratios of Mannich detergent to succinimide detergent.

alkoxylated alcohol

Fuel additives or fuels of the present disclosure may also include one or more optional alkoxylated alcohols. The alkoxylated alcohol is preferably a long-chain alkyl alcohol or a polyether prepared by reacting an alkylphenol with an alkylene oxide. By one approach, the alkoxylated alcohol can be one or more hydrocarbyl terminated or hydrocarbyl capped poly(oxyalkylene) polymers. Their hydrocarbyl moieties can be aryl or aliphatic groups, preferably linear, branched or cyclic, and most preferably linear aliphatic chains. In one approach, the alkoxylated alcohol may have the structure IIIa, IIIb, and/or IIIc below:

R ₆ of the structure of formula III in the formula is an aryl group or a linear, branched or cyclic aliphatic group, preferably having 5 to 50 carbons (or 5 to 30 carbons), or a -C _m H _2m+1 group (provided that m is an integer of 12 or more), wherein R ₇ in the above Formula III structure is a C1 to C4 alkyl group, and n is an integer of 5 to 100 (or as further discussed below).

In some approaches, suitable alkoxylated alcohols are derived from lower alkylene oxides selected from the group consisting of 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 (as well as any combination thereof). In another approach, the alkylene oxide is propylene oxide. Any of these copolymers of alkylene oxides may be random or block copolymers. In one approach, the alkoxylated alcohol may be terminated or capped with an aryl, alkyl, or hydrocarbyl group and may include one or more aryl or linear, branched, or cyclic aliphatic C5 to C30 terminal alkoxylated alcohols; , in another approach, C16 to C18 (or these) with 5 to 100, 10 to 80, 20 to 50, or 22 to 32 repeat units of alkylene oxide therein (i.e., n integer in the above formula) A blend of) may include an alkoxylated alcohol at the terminal. In some approaches, the alkoxylated alcohol may have a weight average molecular weight of from about 1300 to about 2600, and in other approaches from about 1600 to about 2200.

In some approaches, the aliphatic hydrocarbyl terminated alkoxylated alcohol is present in an amount of from about 20 to about 70% by weight (in other approaches, from about 30 to about 50% by weight) of an aliphatic C16 alkoxylated alcohol having 24 to 32 repeat units of alkoxylene oxide. %) and/or may comprise from about 80 to about 30 wt. % (in another approach, from about 50 to about 70 wt. %) of an aliphatic C18 alkoxylated alcohol having 24 to 32 repeat units of alkoxylene oxide. You can. In another approach, the fuel additives herein, when comprising alkoxylated alcohols, contain up to about 8% (in another approach, up to about 6%, in another approach, up to about 4%) of C20 or higher alkoxylated alcohols and/ or up to about 4% by weight (or in another approach, up to about 2% by weight, in another approach, up to about 1%) by weight of a C14 or lower alkoxylated alcohol.

Aryl or hydrocarbyl capped poly(oxyalkylene) alcohols are prepared by adding a lower alkylene oxide, such as ethylene oxide, propylene oxide, or butylene oxide, to the desired hydroxy compound R-OH (i.e., starter alcohol) under polymerization conditions. may be generated, where R is an aryl or hydrocarbyl group having a chain length of 5 to 30 carbons or other chain length as mentioned above, which caps the poly(oxyalkylene) chain. Alkoxylated alcohols can be prepared with any starter alcohol that provides the desired polyol distribution. By one approach, alkoxylated alcohols can be prepared by reacting a saturated linear or branched alcohol of the desired hydrocarbon size with a selected alkylene oxide and a double metal or basic catalyst. In one approach, the alkoxylated alcohol may be a nonylphenol alkoxylated alcohol, such as nonylphenol propoxylated alcohol.

In another approach, a single type of alkylene oxide in the polymerization reaction may be employed, for example propylene oxide, in which case the product is a homopolymer, for example poly(oxyalkylene) propanol. However, copolymers are equally satisfactory, and random or block copolymers are readily prepared by contacting a hydroxyl-containing compound with a mixture of alkylene oxides, such as mixtures of ethylene, propylene, and/or butylene oxide. Random polymers are more easily prepared when the reactivity of the oxides is relatively equal. In certain cases, when ethylene oxide is copolymerized with other oxides, the higher reaction rate of ethylene oxide makes the preparation of random copolymers difficult. In either case, block copolymers can be prepared. Block copolymers are prepared by contacting a hydroxyl-containing compound first with one alkylene oxide and then with the others, in any order or repeatedly, under polymerization conditions. In one example, certain block copolymers are polymers prepared by polymerizing propylene oxide over a suitable mono-hydroxy compound to form a poly(oxypropylene) alcohol and then polymerizing butylene oxide over a poly(oxyalkylene) alcohol. It can be expressed as

The fuel additive or fuel herein, if included, may contain from about 5 to about 30 weight percent of an alkoxylated alcohol, from about 8 to about 20 weight percent of an alkoxylated alcohol, or from about 10 to about 15 weight percent of an alkoxylated alcohol (fuel Additives may include (based on active alkoxylated alcohol). When blended into a gasoline fuel, the fuel may contain from about 2 ppmw to about 150 ppmw of an activated alkoxylated alcohol, from about 5 to about 150 ppmw, from about 8 ppmw to about 50 ppmw, or from about 15 ppmw to about 40 ppmw of an alkoxylated alcohol. It can be included in fuel.

Fuel additives:

When formulating the fuel composition of the present application, the additives described above (including at least the Mannich detergent(s) and the succinimide detergent(s)) are used in the fuel system, combustion chamber and/or crankcase of the engine, and/or It can be employed in an amount sufficient to reduce or inhibit deposit formation in fuel injectors and in gasoline direct injection engines and/or port fuel injection engines. These additives may also be provided in amounts that improve injector performance as described herein. In some embodiments, the fuel additive or fuel additive package herein may include at least the Mannich detergent described above, a succinimide detergent, and an optional alkoxylated alcohol. The fuel additives herein may also include other optional additives as needed for particular applications, such as demulsifiers, corrosion inhibitors, anti-wear additives, antioxidants, metal deactivators, anti-static additives, dehazers, etc. , anti-knock additives, lubricity additives, and/or combustion improvers.

In some approaches or embodiments, the fuel additive or additive package herein may include from about 20 to about 60 weight percent of Mannich detergent and from about 0.5 to about 10 weight percent of succinimide detergent. In another approach, the fuel additive or additive package can also include about 5 to about 30 weight percent of an alkoxylated alcohol. Other ranges of Mannich detergents, succinimide detergents and optional alkoxylated alcohols may also be used in fuel additives, additive packages or fuels as described above in this disclosure.

In another approach, the gasoline fuel composition may include about 40 to about 750 ppmw of the fuel additive or additive package herein, and in other approaches, about 60 to about 380 ppmw, or about 135 to about 310 ppmw of the above-mentioned fuel additive or additive package. A fuel additive package may be included, which provides from about 15 to about 300 ppmw of the Mannich detergent and from about 0.5 to about 20 ppmw of the succinimide detergent to the fuel (or other ranges as noted above). In other embodiments, the fuel may also include from about 2 to about 90 ppmw of an optional alkoxylated alcohol (or other range as noted above). Additionally, it will be understood that any endpoint between the ranges set forth above is a range of amounts suitable for the particular application as needed. The amounts stated above reflect the additives on an active ingredient basis, meaning that the additives mentioned above are (i) unreacted components remaining and associated with the product manufactured and used, and (ii) if present, during or during its formation. It is meant to exclude the weight of solvent(s) used in the preparation of the product after formation.

In another approach, the fuel additive package or fuel thereof may also have a specific weight ratio of alkoxylated alcohol to Mannich detergent of less than or equal to about 1.0 (i.e., less than or equal to about 1.0:1), less than or equal to about 0.8 (i.e., less than or equal to 0.8:1), or less than or equal to about 0.6. or less than or equal to about 0.5, less than or equal to about 0.4, or less than or equal to about 0.3, and greater than or equal to about 0.1 (i.e., greater than or equal to 0.1:1), greater than or equal to about 0.2, or greater than or equal to about 0.3.

In another approach, the fuel additive package or fuel thereof may also have a weight ratio of Mannich detergent to succinimide detergent of from about 15:1 to about 30:1, or from about 20:1 to about 30:1, or from about 22:1. It may be about 30:1 (where the weight ratio is activated Mannich detergent to activated succinimide detergent). In another approach, the fuel additive package or fuel thereof may have a weight ratio of Mannich detergent to succinimide detergent of about 15:1 to about 25:1, or about 20:1 to about 25:1, where the weight ratio is active Mannich detergent vs. activated succinimide detergent). In another approach, the fuel additive package or fuel thereof may have a weight ratio of Mannich detergent to succinimide detergent of about 25:1 to about 30:1, or about 26:1 to about 30:1, wherein the weight ratio is active Mannich detergent vs. activated succinimide detergent). As shown in the examples below, this weight ratio achieves surprising synergy of the detergent additives on engine performance.

Other additives

One or more optional compounds may be present in the fuel compositions of the disclosed embodiments. For example, fuels may 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, It may contain dispersants, antioxidants, heat stabilizers, conductivity improvers, metal deactivators, marker dyes, organic nitrate ignition accelerators, cyclomatic manganese tricarbonyl compounds, carrier fluids, etc. In some embodiments, the compositions described herein may contain up to about 10% by weight, or in other embodiments, up to about 5% by weight of one or more of the above optional additives, based on the total weight of the additive concentrate. Similarly, the fuel may contain suitable amounts of conventional fuel blending components such as methanol, ethanol, dialkyl ethers, 2-ethylhexanol, etc.

In some aspects of the disclosed embodiments, organic nitrate ignition accelerators may be used, which include aliphatic or cycloaliphatic nitrates in which the aliphatic or cycloaliphatic groups are saturated and contain up to about 12 carbons. Examples of organic nitrate ignition accelerators 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-amyl nitrate, 3-amyl nitrate, hexyl nitrate, heptyl nitrate, 2-heptyl nitrate, octyl nitrate, isooctyl nitrate, 2-ethyl Hexyl nitrate, nonyl nitrate, decyl nitrate, undecyl nitrate, dodecyl nitrate, cyclopentyl nitrate, cyclohexyl nitrate, methylcyclohexyl nitrate, cyclododecyl nitrate, 2-ethoxyethyl nitrate. nitrate, 2-(2-ethoxyethoxy)ethyl nitrate, tetrahydrofuranyl nitrate, etc. Mixtures of these materials may also be used.

Examples of suitable selective metal deactivators useful in the compositions of the present application are disclosed in U.S. Pat. No. 4,482,357, the disclosure of which is incorporated herein by reference in its entirety. These metal deactivators include, for example, salicylidene-o-aminophenol, disalicylidene ethylenediamine, disalicylidene propylenediamine, and N,N'-disalicylidene-1,2-diamino. Contains propane.

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

Other commercially available detergents may be used in combination with the reaction products described herein. These detergents include succinimides, Mannich base detergents, PIB amines, quaternary ammonium detergents, bis-aminotriazole detergents as generally described in U.S. Patent Application Serial No. 13/450,638, and hydrocarbyl substituted dicarboxylic detergents. Includes, but is not limited to, reaction products of aminoguanidine with carboxylic acids or anhydrides, wherein the reaction products contain 1 equivalent per molecule as generally described in U.S. Patent Application Serial Nos. 13/240,233 and 13/454,697. It has an amino triazole group.

The additives of this application and the optional additives used to formulate the fuels of this invention may be blended into the base fuel individually or in various sub-combinations. In some embodiments, the additive components of the present application can be simultaneously blended into fuel using an additive concentrate, taking advantage of the interchangeability and convenience provided by the combination of components when in the form of an additive concentrate. Additionally, the use of concentrates can reduce blending time and reduce the likelihood of blending errors.

fuel

The fuels of the present application can be applied in the operation of diesel, jet or gasoline engines, and preferably spark ignition or gasoline engines. Engines include both stationary engines (e.g., engines used in power generation plants, pumping stations, etc.) and mobile engines (e.g., engines used as prime movers in cars, trucks, road leveling equipment, military vehicles, etc.). It can be included. For example, fuels include any and all middle distillate fuels, diesel fuels, biorenewable fuels, biodiesel fuels, fatty acid alkyl esters, gas-to-liquid (GTL) fuels, gasoline, jet fuel, alcohols. , ether, kerosene, low sulfur fuels, synthetic fuels such as Fischer-Tropsch fuel, liquid petroleum gas, bunker oil, coal to liquid (CTL) fuel, biomass to liquid (BTL) fuel, goas Paltene fuels, fuels derived from coal (natural, refined and petcoke), genetically engineered biofuels and agricultural crops and extracts therefrom, and natural gas. Preferably, the additives herein are used in spark ignition fuels or gasoline. As used herein, “biorenewable fuel” is understood to mean any fuel derived from resources other than petroleum. These resources include corn, maize, soybeans and other crops; Grasses such as switchgrass, miscanthus and hybrid grass; Algae, seaweed, vegetable oils; natural fat; and mixtures thereof. In one aspect, the biorenewable fuel may include a monohydroxy alcohol, such as a monohydroxy alcohol containing from 1 to about 5 carbon atoms. Non-limiting examples of suitable monohydroxy alcohols include methanol, ethanol, propanol, n-butanol, isobutanol, t-butyl alcohol, amyl alcohol, and isoamyl alcohol. Preferred fuels include diesel fuel.

Accordingly, aspects of the present application are directed to controlling or reducing fuel injector deposits, controlling or reducing intake valve deposits, and reducing combustion chamber deposits in port injection engines, direct injection engines, and preferably both engine types. It relates to a method or use of the mentioned fuel additive package for controlling or reducing water and/or controlling or reducing intake valve sticking. In some approaches, the fuel additives and fuels herein are used to reduce deposits when sprayed from an injector in droplets of about 10 to about 30 microns, when sprayed from an injector in droplets of about 120 to about 200 microns, or both. It is composed of: As such, the fuel additives and fuels herein surprisingly provide improved engine performance as defined herein in both port fuel injection engines (PFI) as well as gasoline direct injection engines (GDI). In some aspects, the method may also include mixing at least one of the optional additional components described above into the fuel. Improved engine performance can be achieved according to the test protocol of ASTM D6201 or as described in 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 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, both of which are incorporated herein by reference. Inspiratory valve sticking can be evaluated using a testing protocol at the Southwest Research Institute (SWRI, San Antonio, Texas) or a similar test house.

As used herein, the term “hydrocarbyl substituent” or “hydrocarbyl group” is used in its conventional sense and is well known to those skilled in the art. Specifically, it refers to a group that has a carbon atom directly attached to the rest of the molecule and is predominantly hydrocarbon in character. Each hydrocarbyl group is independently selected from a hydrocarbon substituent and a substituted hydrocarbon substituent, wherein the substituted hydrocarbon substituent is a halo group, hydroxyl group, alkoxy group, mercapto group, nitro group, nitroso group, amino group, pyridyl group, furyl group, imidazolyl group, oxygen and nitrogen, wherein there are no more than 2 non-hydrocarbon substituents for every 10 carbon atoms in the hydrocarbyl group.

As used herein, the term “weight percent” or “wt%” means the percentage represented by the recited component relative to the weight of the total composition, unless explicitly stated otherwise. Unless otherwise specified, all percentage numbers herein are percent by weight.

As employed herein, the term “alkyl” refers to a straight, branched, cyclic and/or substituted saturated chain moiety having from about 1 to about 200 carbon atoms. As employed herein, the term “alkenyl” refers to a straight, branched, cyclic and/or substituted unsaturated chain moiety having from about 3 to about 30 carbon atoms. As used herein, the term "aryl" refers to a single and aryl group that may contain alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and/or heteroatoms, including but not limited to nitrogen and oxygen. Refers to multi-ring aromatic compounds.

As used herein, molecular weight is determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (with Mp from about 162 to about 14,000 as a calibration reference). Molecular weight (Mn) for any of the embodiments herein can be determined using an instrument such as a gel permeation chromatography (GPC) instrument obtained from Waters and data processed with software such as Waters Empower Software. GPC instruments can be equipped with optional equipment such as the Waters Separations Module and Waters Refractive Index detector. GPC operating conditions may include a guard column with a column temperature of approximately 40°C, four Agilent PLgel columns (length 300×7.5 mm; particle size 5μ and pore size range 100-10000 Å). Tetrahydrofuran (THF), HPLC grade, which is not stable, can be used as solvent at a flow rate of 0.38 mL/min. GPC instruments can be calibrated with commercially available polystyrene (PS) standards with a narrow molecular weight distribution ranging from 500 to 380,000 g/mol. The calibration curve can be extrapolated to samples with a mass of less than 500 g/mol. Samples and PS standards are dissolved in THF, prepared at concentrations of 0.1 to 0.5% by weight, and can be used without filtration. GPC measurements are also described in US 5,266,223, which is incorporated herein by reference. GPC methods provide additional molecular weight distribution information; See, for example , WW Yau, JJ Kirkland and DD Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979, which is also incorporated herein by reference.

As used herein, unless the context suggests otherwise, a major amount refers to greater than 50 weight percent (greater than 60 weight percent, greater than 70 weight percent, greater than 80 weight percent, or greater than 90 weight percent) and a minor quantity refers to greater than 50 weight percent. % (less than 40% by weight, less than 30% by weight, less than 20% by weight, or less than 10% by weight).

Throughout this disclosure, the terms “comprise,” “include,” “contain,” etc. are considered open-ended and include any element, step, or ingredient not explicitly listed. Includes. The phrase “consists essentially of” includes any explicitly listed element, step or ingredient and any additional element, step or ingredient that does not materially affect the basic and novel aspects of the invention. It means to do. The present disclosure also provides that any composition described using the terms “comprise,” “include,” or “contains” may also “consist essentially of” or “consist of” those specifically listed components. It is contemplated that the disclosure should be construed to include the disclosure of the same composition.

Example

The following examples illustrate example embodiments of the present disclosure. In these examples, as well as elsewhere in the application, all ratios, parts and percentages are by weight unless otherwise indicated. These examples are intended to be presented for illustrative purposes only and are not intended to limit the scope of the invention disclosed herein. Specifications for base fuels A, B and C used in the examples are in Table 1 below.

Example 1

The fuel additive packages of the present invention and comparative examples shown in Table 2 below were manufactured. Mannich detergents were prepared from highly reactive polyisobutylene cresol, dibutylamine, and formaldehyde according to known methods (see, e.g., US 6,800,103, which is incorporated herein by reference); The propoxylated alcohol was a blend of commercially available C16-C18 propoxylated alcohols; The succinimide detergent was derived from polyisobutylene succinic anhydride (PIBSA) and tetraethylene pentamine (TEPA) in a 1:1 to 1.6:1 molar ratio, where the polyisobutylene had a molecular weight of about 950.

Each of the additives in Table 2 above was blended into base fuel A, B or C as specified in the footnotes of Table 3 below. Each fuel was then evaluated for intake valve deposits and/or injector deposits as described in Table 3 below.

In the context of GDI engines, a series of tests were carried out to evaluate the effect of additive packages on fuel injection deposits in gasoline direct injection engines (GDI). All tests were run using a consistent base fuel C during the dirty up (DU), clean up (CU) and/or keep clean (KC) phases of each test. The additive packages in Table 2 above were tested to evaluate the ability of each fuel additive to improve injector performance by reducing injector deposits in GDI engines. The results are shown in Table 3 as well as Figures 1 and 2.

For base fuel C, [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 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 (both papers incorporated herein by reference) on a gasoline direct injection GM LHU engine, pulse width or long-term fuel trim (long DU levels were investigated by indirect measurements of injector fouling, such as term fuel trim (LTFT).

To accelerate the DU phase of the base fuel, a combination of di-tert-butyl disulfide (DTBDS, 406 ppmw) and tert-butyl hydrogen peroxide (TBHP, 286 ppmw) is added to the base fuel and accelerate DU to 5 to 12%. A range of contamination was provided. The contamination percentage is calculated as follows:

A GDI Cleanup (CU) deposit test was performed to demonstrate removal of deposits formed in the fuel injectors during the dirty up (DU) phase. The additive package in Table 2 was blended into the base fuel C used in DU. The test procedure consisted of 114 hour cycles at 2000 rpm and 100 Nm torque, with continuous monitoring of injection pulse width to maintain stoichiometric air/fuel ratio on the GM LHU engine. After 66 hours of test operation, the fuel was changed to a additive formulation designed to have a cleanup effect. After completion of the 114 hour cycle, the percentage of injector pulse width increase and subsequent decrease is one parameter to evaluate the fouling or cleaning effectiveness of the fuel candidate. CU is calculated as in the following formula:

As shown in Table 3 above and Figures 1 and 2, samples of the present invention with both Mannich and succinimide detergents in ratios of 15:1 to 30:1 were used in combination with either the Mannich or succinimide detergents. It showed improved injector cleanup compared to the comparative example alone. Figure 1 shows the DU phase (open symbols) and CU phase (closed symbols) of comparative additive packages C-1 and C-2 relative to the inventive additive package I-1d. As shown in Table 3 and Figure 1, comparative sample C-1 with Mannich cleaner alone sustained the dirty up phase in the GDI engine (i.e., no cleanup performance), and inventive sample I-1d with Mannich cleaner alone. and succinimide detergent were both used in the stated ratios to demonstrate improved cleanup. Considering that fuel additives with only Mannich cleaners (e.g., C-1) do not have any cleanup performance in GDI engines (and rather sustain the dirty-up phase), both Mannich cleaners and succinimide cleaners are used. Inventive sample I-1d with demonstrated unexpected synergy in performance. That is, considering that the Mannich detergent alone does not provide cleanup performance (rather sustains DU), the cleanup performance using both succinimide and Mannich detergents is comparable to that of comparative sample C-2 containing only the succinimide detergent. It would not have been expected to be better than the cleanup performance of . Table 3 and Figure 2 show similar patterns by inventive sample I-2c (both Mannich and succinimide detergents) compared to C-1 (Mannich detergent only) and C-2 (succinimide detergent only). shows an unexpected synergistic effect.

Note that as used in this specification and the appended claims, the singular forms “a”, “an” and “the” include plural references unless explicitly and explicitly limited to a single reference. . Thus, for example, reference to “antioxidants” includes two or more different antioxidants. As used herein, the term "include" and its grammatical variations are intended to be non-limiting, and citation of an item in a list does not exclude other similar items that may be added to or replaced with the listed item. Make sure not to do so.

For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or ratios, and other numerical values, as used in the specification and claims, in all instances refer to the term "about". It should be understood as being modified by. Accordingly, unless otherwise indicated, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending on the desired properties sought to be achieved by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

It is understood that each element, compound, substituent or parameter disclosed herein should be construed as disclosed for use alone or in combination with one or more of each and every other element, compound, substituent or parameter disclosed herein. It has to be.

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

Each lower limit of each range disclosed herein should be construed as disclosed in combination with each upper limit of each range disclosed herein and each specific value within each range for the same element, compound, substituent or parameter. It is further understood. Accordingly, the present disclosure combines each lower limit of each range with each upper limit of each range or each specific value within each range, or by combining each upper limit of each range with each specific value within each range. It should be construed as a disclosure of the entire range resulting from combination with. That is, it is also understood that any range between endpoint values within a broad range is also discussed herein. Accordingly, a range of 1 to 4 also means a range of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

Additionally, specific amounts/values of elements, compounds, substituents or parameters disclosed herein or in the Examples should be construed as disclosures of lower or upper limits of ranges, thereby preventing the same elements, compounds, substituents or parameters disclosed elsewhere in this application. A range for a parameter or a particular amount/value may be combined with any other lower or upper limit to form a range for that element, compound, substituent or parameter.

Claims (16)

As a fuel additive for spark ignition engines,
Mannich detergents comprising the reaction product of a hydrocarbyl substituted phenol or cresol, one or more aldehydes, and one or more amines;
Succinimide detergents prepared by reacting a hydrocarbyl substituted succinic acid acylating agent with an amine, polyamine or alkyl amine having one or more primary, secondary or tertiary amino groups;
A fuel additive wherein the weight ratio of Mannich detergent to succinimide detergent is from about 15:1 to about 30:1. According to claim 1,
The weight ratio of Mannich detergent to succinimide detergent is from about 20:1 to about 30:1; Mannich detergent has the structure of formula I,

where R ₁ is hydrogen or a C1 to C4 alkyl group, R ₂ is a hydrocarbyl group with a molecular weight of about 500 to about 3000, R ₃ is a C1 to C4 alkylene or alkenyl group, and R ₄ and R ₅ are Fuel additive, independently hydrogen, C1 to C12 alkyl group, or mono or di(C1 to C4)alkyl amino C1 to C12 alkyl group. According to claim 2,
and R ₂ is polyisobutenyl having a number average molecular weight of about 500 to about 1500. According to claim 1,
The succinimide detergent is a hydrocarbyl substituted mono-succinimide detergent, a hydrocarbyl substituted bis-succinimide detergent, or a combination thereof; The hydrocarbyl substituted succinic acid acylating agent is a hydrocarbyl substituted succinic anhydride, wherein the hydrocarbyl groups have a molecular weight of about 450 to about 3000, and the molar ratio of hydrocarbyl substituted succinic anhydride to amine, polyamine or alkyl amine is about 0.5. :1 to about 2:1, fuel additive. According to claim 4,
Hydrocarbyl substituted succinic anhydride is a polyisobutylene substituted succinic anhydride, wherein the polyisobutylene has a number average molecular weight of about 500 to about 1200 as measured by GPC using polystyrene as a reference. According to claim 5,
The amine, polyamine, or alkyl amine is tetraethylene pentamine (TEPA), triethylenetetraamine (TETA), or a polyamine having the formula H ₂ N-((CHR ₂₀ -(CH ₂ ) _q -NH) _r -H or Alkyl amines, where R ₂₀ 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. According to claim 6,
Amines, polyamines or alkyl amines are tetraethylene pentamine (TEPA), a fuel additive. According to claim 1,
further comprising an alkoxylated alcohol, and/or the weight ratio of alkoxylated alcohol to Mannich cleaner is less than or equal to about 1.0; A fuel additive, wherein the alkoxylated alcohol is a polyether prepared by reacting an alkyl alcohol or alkylphenol with an alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide, copolymers thereof, or combinations thereof. According to claim 8,
Alkoxylated alcohols are polyethers having the structure III,

wherein R ₆ of formula III is an aryl group or a linear, branched or cyclic aliphatic group having 5 to 50 carbons, R ₇ of formula III is a C1 to C4 alkyl group and n is an integer from 5 to 100. . According to claim 1,
A fuel additive comprising from about 20 to about 60 weight percent of a Mannich detergent, from about 0.5 to about 10 weight percent of a succinimide detergent, and from about 5 to about 30 weight percent of an alkoxylated alcohol. As a gasoline fuel composition,
About 15 to about 300 ppmw of a Mannich detergent comprising the reaction product of a hydrocarbyl substituted phenol or cresol, one or more aldehydes, and one or more amines;
about 0.5 to about 20 ppmw of a succinimide detergent prepared by reacting a hydrocarbyl substituted succinic acid acylating agent with an amine, polyamine or alkyl amine having one or more primary, secondary or tertiary amino groups; and
comprising from about 5 to about 150 ppmw of an alkoxylated alcohol,
A gasoline fuel composition wherein the weight ratio of Mannich detergent to succinimide detergent is from about 15:1 to about 30:1. A method for reducing deposits in a gasoline engine, comprising:
operating the gasoline engine with a fuel composition containing a large amount of gasoline fuel and a small amount of fuel additives by injecting the gasoline fuel through one or more injectors,
Fuel additives include (i) a Mannich detergent comprising the reaction product of a hydrocarbyl substituted phenol or cresol, one or more aldehydes, and one or more amines; (ii) succinimide detergents prepared by reacting a hydrocarbyl substituted succinic acid acylating agent with an amine, polyamine, or alkyl amine having one or more primary, secondary, or tertiary amino groups; and (iii) the fuel additive has a weight ratio of Mannich detergent to succinimide detergent of about 15:1 to about 30:1; and
A fuel additive reduces deposits in a gasoline engine. According to claim 12,
Fuel additives reduce deposits in port fuel injection (PFI) engines, gasoline direct injection (GDI) engines, or both; The method of claim 1, wherein reduced deposits are reduced injector deposits measured by one of injector pulse width, injector duration, injector flow, or a combination thereof. According to claim 12,
wherein the fuel additive reduces deposits when sprayed from an injector configured to spray droplets of about 10 to about 30 microns, about 120 to about 200 microns, or both. According to claim 12,
The weight ratio of Mannich detergent to succinimide detergent is from about 20:1 to about 30:1; Mannich detergent has the structure of formula I,

where R ₁ is hydrogen or a C1 to C4 alkyl group, R ₂ is a hydrocarbyl group with a molecular weight of about 500 to about 3000, R ₃ is a C1 to C4 alkylene or alkenyl group, and R ₄ and R ₅ are independently hydrogen, a C1 to C12 alkyl group, or a mono or di(C1 to C4)alkyl amino C1 to C12 alkyl group. According to claim 12,
The fuel additive further comprises an alkoxylated alcohol and/or the weight ratio of alkoxylated alcohol to Mannich detergent is less than or equal to about 1.0; The alkoxylated alcohol is a polyether prepared by reacting an alkyl alcohol or alkylphenol with an alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide, copolymers thereof, or combinations thereof; The method of claim 1, wherein the fuel additive comprises from about 20 to about 60 weight percent of a Mannich detergent, from about 0.5 to about 10 weight percent of a succinimide detergent, and from about 5 to about 30 weight percent of an alkoxylated alcohol.